V E R S I O N

1 . 5

EChem
Users Guide
& using Chart & Scope software for
Electrochemistry
Please check for the release of the EChem v2 manual on the
eDAQ web site at [Link]

PowerLab System

[Link]

This document was, as far as possible, accurate at

the time of printing. Changes may have been made
to the software and hardware it describes since
then, though: ADInstruments Pty Ltd reserves the
right to alter specications as required. Latebreaking information may be supplied separately.

EChem 1.3 software: Michael Macknight, Peter

Bromley, Bruce Warrington, and Michael Hamel.
EChem 1.5 software written byLev Possajennikov.
Documentation written by Paul Duckworth.

Trademarks of ADInstruments
MacLab and PowerLab are registered trademarks
of ADInstruments Pty Ltd. Specic model names
of data recording units, such as MacLab/8e and
PowerLab/400, are trademarks of ADInstruments
Pty Ltd.
Chart, EChem, Histogram, Peaks, Scope,
DoseResponse, UpdateMaker, and UpdateUser
(software), and PowerChrom (software and
hardware) are trademarks of ADInstruments Pty
Ltd.
Other Trademarks

Document Number: U-MS600-UG-03A

Copyright July 1999
ADInstruments Pty Ltd
Unit 6, 4 Gladstone Road
Castle Hill, NSW 2154
AUSTRALIA
e-mail: info@[Link]
[Link]
All rights reserved. No part of this document may
be reproduced by any means without the prior
written permission of ADInstruments Pty Ltd.

Apple, the Apple logo, AppleTalk, Geneva,

HyperCard, ImageWriter, LaserWriter, Macintosh,
and StyleWriter are registered trademarks of
Apple Computer, Inc. Finder, MacOS, Power
Macintosh PowerBook, PowerTalk, Quadra,
QuickDraw, System 7, and TrueType are
trademarks of Apple Computer, Inc. Windows,
Windows 95, Windows 98 and Windows NT are
trademarks of Microsoft Corporation..
PostScript is a registered trademark of Adobe
Systems, Incorporated.
BAS is a trademark of Bioanalytical Systems Inc.
PAR and EG&G PARC are trademarks of EG&G
Princeton Applied Reasearch. Polarecord is a
trademark of Metrohm Ltd. HEKA is a trademark
of HEKA Electronik. PINE is a trademark of PINE
Instrument Company. Cypress is a trademark of
Cypress Systems Inc. AMEL is a trademark of
AMEL srl.

IGOR & IGOR Pro (software) are trademarks of

Wavemetrics Inc.

ii

EChem Users Guide

Contents
Contents

The Axes 40
Dragging and Stretching the Axes 42
Graph Lines, Patterns & Colors 43
Navigating 44
Overlaying Pages 45
The Zoom Window 47
Display and Printer Resolution 49
Making Measurements 50
Using the Marker 50
Setting and Removing Baselines 51
The Marker Miniwindow 52
Background Subtraction 54
The Data Pad 55
Adding Data to the Data Pad 57
Setting Up the Columns 57
Data Pad Miniwindow 59
Printing the Data Pad 59
Computed Functions 59
Sampling Speed 60
Channel Functions 61
Math 62
Function 63
The Notebook 64
The Page Comment window 65

iii

1 Getting Started

Learning to Use EChem 2

Computer Requirements 3
The EChem System 4
Installation Instructions 6
Opening EChem for the rst time 6

2 EChem Basics

An Overview of EChem 10
Opening an EChem File 12
Closing or Quitting an EChem File 14
The Main Window 14
Recording 19

3 Setting Up EChem

23

Using 3rd Party Potentiostats 24

Connecting to PowerLab 24
Adjusting the Input Range 25
Using the Input Amplier Dialog Box 26
Units Conversion 29
The ADInstruments Potentiostat 31
Changing Potentiostat settings 31
The Potentiostat Dialog Box 31

4 Data Display and Analysis

5 Working With Files

Selecting Data 68
Editing Data 68
Transferring Data 69
Measuring From the Waveform 71
Using the Marker 72

37

The Main EChem Window 38

EChem Users Guide

67

iii

Setting and Removing Baselines 73

Saving Options 74
Appending Files 77
Text Files 77
Printing 79
Page Setup 80
The Print Command 82

6 Customizing EChem

87

Preferences 88
Menus 88
Controls 90
Options 91
Start-Up 92
Emergency Access! 92
Macros 94
Recording a Macro 95
Playing a Macro 96
Deleting a Macro 96
Macros That Call Other Macros 97
Options When Recording Macros 98
Macro Commands 101

7 EChem Techniques

107

Introduction 108
General Considerations 110
Linear Sweep Voltammetry 116
Square Wave Voltammetry 121
Normal Pulse Voltammetry 126
Differential Pulse Voltammetry 130
Stripping Techniques 135
Cyclic Voltammetry 140
MultiPulse Voltammetry 146
MultiPulse Amperometry 154
The Apply Technique... command 159
Polarographic Techniques 160

8 Additional Techniques

Chronocoulometry 173
Chronopotentiometry 175
The Potentiostat as a Galvanostat 175
Controlled Potential Electrolysis 178
Controlled Current Electrolysis 179
Rotating Ring Disk Electrodes 180
Amperometric Titrimetry 180
Liquid Chromatography Detectors 181
Biosensors 182
Potentiometric sensors 182
pH Electrodes 182
Ion Selective Electrodes 183
Potentiometric Redox Electrodes 184
Dissolved CO2 and NH3 Electrodes 184
Electrode Behaviour 184
Multiple Point Calibration 185
pH and ISE Calibration 189
Temperature Compensation 194
Isopotential Point 196
Potentiometric Titrimetry 197
Dissolved Oxygen, dO2, Sensors 198
Conductivity Sensors 198
Simple Galvanic Cells 199
Quartz Crystal Microbalance 200
Electrochemical Noise Experiments 200
Corrosion Measurements 201

9 Using 3rd Party Equipment

Introduction 206
EG&G PARC 206
BAS 210
PINE 214
Metrohm 215
Schlumberger 216
Radiometer 216
HEKA 217
Cypress 218
AMEL 220

161

Introduction 162
AC Voltammetry 163
Fast Scan Techniques 163
Low Current Experiments 166
Chronoamperometry 167

iv

EChem Users Guide

205

Purication of solvents 264

Supercritical Fluids 265
The Mercury Electrode 265

Appendices
A Menus & Commands

223

F Potentiostat Designs 267

Menus 223
Keyboard Shortcuts 226

B Troubleshooting

Two electrode systems 267

Three electrode systems 268
Four electrode systems 270

227

Technical Support 227

Solutions to Common Problems 229

C Technique Summary

Bibliography

241

Linear Sweep Voltammetry 242

Square Wave Voltammetry 243
Normal & Reverse Pulse
Voltammetry 244
Differential Pulse Voltammetry 245
Cyclic Voltammetry 246
Multi Pulse Voltammetry 247

D Electrochemical Equations

The Internet 273

Text Books 274
Journals 279

Glossary

281

249

Linear Sweep and Cyclic Voltammetry, The

Randles-Sevcik Equation 249
Differential Pulse Techniques, The ParryOsteryoung Equation 251
Chronoamperometry, The Cottrell
Equation 252
Chronocoulometry, The Integrated Cottrell
Equation 253

Index

285

Licensing & Warranty Agreement

E Cyclic Voltammetry, Solvents &

Electrolytes 255
Solubility Rules 255
Solvent Stability 256
Use of Large Ions as Electrolytes 256
Electrode and Cell Design for Organic
Solvents 259
Synthesis of Selected Electrolytes 261

Chapter Contents

273

295

vi

EChem Users Guide

C H A P T E R

O N E

Getting Started
Welcome to the ADInstruments PowerLab/EChem electrochemistry
system. EChem software lets you use your computer* and PowerLab
analog-to-digital interface unit as an electrochemistry workstation
suitable compatible with a wide variety of potentiostats and patch
and voltage clamps. EChem causes the PowerLab unit to generate the
potential waveform for most staircase ramp and pulse voltammetric
techniques, as well as pulsed amperometric experiments, samples
and signal averages the current signal at appropriate times, and
displays the results in real time. Chapter 7 has a full description of the
techniques available. In addition, when used with the ADInstruments
Potentiostat, full software control of gain ranges, lter settings and
polarity convention is available.

Many other types of electrochemistry experiment can be performed

with the Chart and Scope software included with your PowerLab
system. Consult Chapter 8 for further details of these experiments.

This chapter contains instructions on the installation of EChem

software, and its hardware requirements.

*. EChem software, version 1.5, is suitable for use with Macintosh, Windows 95,
98, NT, 2000 or Me computers.

EChem Users Guide

Learning to Use EChem

Where to Start
To install and use EChem you should be familiar with the operating
system of your computer.
You will nd that EChem works similarly to other programs that you
use on your computer. If you have used earlier versions of EChem
software, you should nd that although this version has much in
common, it also has many new features.
Start by reading the introductory chapters in your Getting Started with
PowerLab booklet which describes how to connect the PowerLab unit
to your computer. If you are not using an ADInstruments Potentiostat
then you should also read Chapter 9 before using the system. If you
are new to electrochemical techniques, then rst familiarise yourself
with the various terms dened in the Glossary at the end of this
guide.

How to Use this Guide

If you are in a hurry at least read the rest of this chapter, and the
Overview of EChem in the next chapter, to familiarise yourself with
some of the key features of EChem before you begin your
experiments.
We recommend, however, that you work through this guide in front
of your computer. The information in the following chapters is set out
in the order you will probably require it. If you are unfamiliar with
electrochemical methods then read Chapters 7 and 8. The appendices
also have much useful information including electrolyte syntheses,
solvent purication methods, and sources of general information.
The rest of this chapter, covers system congurations and installing
and personalising your copy of EChem.
If you are using a third party potentiostat with EChem then please
read the potentiostat operators manual carefully to determine its
limitations safe operating procedure. In particular be aware of the

EChem Users Guide

Note
The pictures used as
illustrations in this guide
are from a monochrome
monitor. There may be
slight differences in
appearance when using
EChem on a greyscale or
color monitor.

maximum potential and current that your potentiostat can generate.

Never touch the electrodes while the potentiostat is in operation as
this is extremely dangerous with high powered models.

Computer Requirements
Your particular needs will determine the computing requirements
and hence which model of computer you use. Your ADInstruments
representative will be happy to discuss your requirements and
suggest suitable congurations.

Apple Macintosh
Minimum: The minimum requirement is a Macintosh computer with
a 68020 microprocessor and a hard disk, System 7, 8MB RAM, and a
13 inch monitor. If you own an early model Apple Macintosh then we
can supply EChem version 1.3 on request. Although EChem 1.3 has
fewer features than EChem 1.5, it will run even on early model 68000
Apple Macintosh computers with System 6 or System 7, and on
computers with 9 or 12 inch black and white or color monitors (for
example a Mac SE with system 6 will happily run EChem version
1.3). Data les collected with EChem 1.3 can also be opened with
EChem 1.5.

Note
Owners of Apple
Macintosh PowerBooks
will need a suitable SCSI
cable or adaptor, available
from your computer
dealer, to connect the
PowerBook to the
PowerLab unit. Recent
Macintosh models have a
USB port which can be
used as an alternative to
the SCSI connection with
PowerLab units with USB
ports.

Chapter 1 Getting Started

Chart and Scope software, versions 3.3.8, are also available for use
with PowerLab units used with early model Apple Macintosh
computers.
Recommended: a Power Macintosh G3, with a hard disk, System 8,
32 MB RAM, and a 14-inch or larger color monitor.
Printers: there are numerous printers available that can be used to
produce reports from EChem. Some recommended printers are: the
Apple Color StyleWriter 2500, a color inkjet printer producing high
quality color printouts at near laser printer quality; and the Apple
LaserWriter series. If you buy a laser printer ensure that it has true
PostScript capability which will ensure that you get the highest
quality graphic output for plotting your results.

Microsoft Windows

Note
Your Windows computer
will need a suitable SCSI
card and cable to connect
to the PowerLab unit.
Depending an your
computer you may need
an ISA, PCI or PCMCIA
SCSI card, available from
ADInstruments or your
local computer supplier.
Old SCSI cards originally
installed in Windows 3
computers will probably
not work.

Minimum: An IBM compatible computer with Pentium

microprocessor with Windows 95, Windows 98, or Windows NT
(v4.0) operating system, and 16 MB RAM (32 MB for NT), and a 14
inch or larger monitor, a color VGA card and a CD ROM or oppy
disk drive. A suitable SCSI card will need to be installed (contact
ADInstruments for names of suitable brands).
Recommended: An IBM compatible computer with Pentium-level or
faster CPU and a fast hard disk, Windows 98 or Windows NT (v4.0)
operating system, at least 32 MB RAM (48 for NT), an accelerated
color Super VGA card (or equivalent), and a 16-inch or larger
monitor, and a CD ROM. A suitable SCSI card will need to be
installed (contact ADInstruments for names of suitable brands).
Printers: there are numerous printers available that can be used to
produce reports from EChem, most Windows compatible printers
will be suitable but dot matrix and other low resolution printers
may not give you the graphic resolution you require for publication
quality diagrams. If you buy a laser printer ensure that it has true
PostScript capability which will ensure that you get the highest
quality output when plotting your results.

The EChem System

The EChem/PowerLab system is an integrated hardware and
software system designed to record, display, and analyse
experimental data. The PowerLab hardware interface is connected
between the potentiostat and the computer. EChem software runs on
the computer to which the PowerLab is connected. You must have
installed software on the computer and connected the PowerLab
hardware to the computer to collect experimental data. However, preexisting data les can be opened with, analysed by, and printed from
the software, whether or not the PowerLab unit is connected.
Data collected with EChem software on a Windows computer can be
read by the Macintosh version of EChem and vice versa. You can

EChem Users Guide

transfer data between computers on Windows formatted oppy disks

(Macintosh computers read Windows formatted disks).
Other ADinstruments software that runs with PowerLab units,
includes Chart and Scope software (supplied with the PowerLab
unit). Other software that can be used with your PowerLab hardware
is available separately and includes PowerChrom software (for
chromatographic data collection), and DoseResponse software (for
pharmacological studies).

Compatible MacLab or PowerLab Units

EChem 1.5 software can be used with the following new and older
models of PowerLab and MacLab.
PowerLab e systems:
PowerLab/200, MacLab/200, MacLab/2e
PowerLab/400, MacLab/400, MacLab/4e, MacLab/4
PowerLab/800, MacLab/8e, MacLab/8
PowerLab S systems:
PowerLab/4SP, PowerLab/4s, MacLab/4s
PowerLab/8SP, PowerLab/8s, MacLab/8s
PowerLab/16SP, PowerLab/16s, MacLab/16s
PowerLab/4ST
The PowerLab/410 is unsuitable for use with EChem software.
Consult your ADInstruments representative for the latest information
on our range of products. Please note that MacLab units have now
been superseded by the PowerLab range.

Optional Analysis
For general purpose data analysis and the production of specialist
plots for theses, reports, slides, and publications we recommend IGOR
Pro software (WaveMetrics). Other suitable graphing software
includes Origin (Microcal) and Kaleidagraph (Synergy).

Chapter 1 Getting Started

Installation Instructions
You will have been provided with a CD ROM which contains the
EChem installer software. If your computer does not have CD ROM
capability then contact your ADInstruments representative who can
arrange installation from a set of oppy disks. You will need at least 3
MB of free space on your hard disk for the installation. It is
recommended that you rst install the Chart and Scope software that
also came with your PowerLab system. To install EChem:
1. Insert the EChem PowerLab CD ROM into the appropriate drive.
2. Double click the installer icon.
The installation creates an EChem folder (directory) in which you will
nd the EChem program and sample data les. On Macintosh
systems the Potentiostat driver software is also placed in the
ADInstruments folder in the System Folder. On a Windows system
the Potentiostat driver is part of the EChem software. This driver is
only required if you are using the ADInstruments Potentiostat.
If you have used an earlier version of EChem it is strongly
recommended that you remove these versions from your Macintosh
hard disk before you install EChem 1.5. On Windows systems older
versions of software will be automatically uninstalled. Data les from
earlier versions of EChem will open with EChem version 1.5. If there
are multiple versions of a program present on your hard disk then
you may accidentally use the older version for your experiments.
Keep your installer CD ROM in a safe place after the installation.
Please remember that each purchased copy only licenses you to use
the software on one computer at any one time. Please enquire about a
costsaving departmental license if you want to run multiple copies
in your workplace.

Opening EChem for the rst time

Figure 11
The EChem program icon

Ensure that the PowerLab unit is connected properly to your

computer (this is covered in the Owners Guide that came with your
PowerLab unit), and that it is turned on. Click the EChem icon and
select Open from the File menu (or double-click the icon). There may
be a short delay while the program initialises the PowerLab unit.
EChem Users Guide

Figure 12 Enter your

name and that of your
organization when you first
use EChem.

When you start EChem for the rst time, a dialog box will appear
(Figure 12), asking you to name the copy of the application. If the
computer has an owners name already assigned (for le sharing),
then the name will be put into the Name box. Just start typing if you
want to overwrite it.
If the PowerLab unit is not connected, then the dialog box in Figure 1
3 will appear. If this dialog box appears when the PowerLab unit is
properly connected and turned on, see the Owners Guide that came
with your PowerLab for help. Some of the information about start-up
problems from the Owners Guide is also repeated in Appendix B at
the back of this manual.
The PowerLab is not connected or not turned
on. Click on the Analysis button to open a data
le for further analysis or for printing.

Figure 13 Dialog boxes

that appear (Macintosh
upper, Windows lower) if the
PowerLab is not present or
not connected.

The SCSI card has not been installed

correctly or the computer was turned on
before the PowerLab unit.

Chapter 1 Getting Started

The the PowerLab unit is not turned on or not

connected. Click on the Analysis button to open
a data le for further analysis or for printing.

Quitting EChem
If you want to exit EChem after naming your copy of the software,
choose Quit from the File menu. If you want to proceed, working
through this guide, you can leave the le open.

EChem Users Guide

C H A P T E R

T W O

EChem Basics
EChem is a sophisticated program for performing voltammetric and
amperometric electrochemical experiments. This chapter provides a
general overview of EChem, looks at the main graphic window, and
deals with the basics of recording data.

EChem Users Guide

An Overview of EChem
EChem, together with the PowerLab hardware and computer, gives
you the display capabilities of a two-channel storage oscilloscope, as
well as the features of a versatile waveform generator. You can
perform a variety of electrochemical techniques with any potentiostat
that has an external input and analog (XY, or chart recorder) outputs.

Display ControlsChapter 4
Your results are displayed in the main EChem window which can be
resized, and the control panels moved to where you want them. The
data display can be set to show I (current), E (potential) and t (time)
in different formats:
I vs E, with I on the Y and E on the X axis.
E vs I, with E on the Y axis and I on the X axis.
I and E on separate graphs versus time.
I versus time (for amperometric experiments).
The current and potential axes can be dragged, stretched, or set to
exact values for optimum data display. The current range can be
adjusted. If an ADInstruments Potentiostat is connected then its
controls can also be accessed through the software. Display colors,
patterns, and grids can be altered.

Display and AnalysisChapter 4

EChem records data in sweeps, like a normal oscilloscope, however
each new sweep is recorded to a different page, creating a set of
recorded scans numbered for easy reference, or for overlaying. Thus a
new le does not have to be created for each experiment. You can add
your own written comments to each page of data to emphasize
features of interest, or to log standard concentrations. There is also a
Notebook feature for making general observations about a data le.
When you have nished recording, you can move through your data
using the page controls and make measurements directly from the
recording you are given a direct read-out, with no chance of

10

EChem Users Guide

measurement errors. You can measure from a selected reference point,

using the Marker, or a baseline (which you can also set). EChem
allows you to overlay data from any selection of pages, for direct
comparison. The Data Pad feature enables you to make and store
parameters such as peak height, potential at peak height, etc. EChem
has a Zoom window for examining a section of the recording in more
detail. Refer to Chapter 5 for more details.

Working with FilesChapter 5

EChem results can be printed, edited, and saved to a disk for later
review. You can also save settings les empty data les that are
precongured for particular experiments so that any experiment
can be repeated quickly and easily, without having to go through the
process of entering all the sweep parameters again. Pages of data can
be printed in a variety of formats, or cut, copied, and pasted between
EChem les, and whole les can be appended to the end of an open
le, allowing you to produce summaries in a single le. Data can be
transferred as text to spreadsheets or word processors and,
conversely, correctly formatted text can even be pasted into an
EChem le.

Techniques Chapters 7 and 8

EChem provides a range of electrochemical methods from simple
staircase linear sweep voltammetry through to complicated pulse
sequences. You can dene the sampling periods for each step or pulse.

Customising and Automating Chapter 6

EChem can be extensively customised for your purposes. Controls,
and menus and their commands (and Command-key/Control-key
equivalents) can be locked, hidden, or altered, and the appearance of
EChem simplied, say, for student or technician use. Macros can also
be created to automate complex, or repetitive tasks.

Chapter 2 EChem Basics

11

Figure 21
EChem desktop icons:
double-click one to open
EChem

Opening an EChem File

To open an EChem le,:
1. click on one of the EChem icons in the Finder to select it, and
choose Open from the File menu; or
2. double-click the icon (see Figure 21).
There will be a short delay while EChem initialises the PowerLab.
The top icon in Figure 21 shows the EChem application, which will
open a new untitled le if double-clicked. The second icon shows a
le of prerecorded data. The last two icons show a settings le and
macro le these are like the template or stationery les used in
some spreadsheet or word processor documents. If you open ether of
these then an empty, but precongured, document will be opened
ready to begin a new experiment.
It is best to have the sample EChem data le open while working
through this section, so that you can try the commands, controls, and
settings as they are discussed in the text. First, make sure that the
PowerLab unit is properly connected to your computer, and that it is
turned on. You may also wish to learn EChem without the PowerLab
if you have taken a copy for your home computer for instance. In
this case, on opening a le, a dialog box will offer the Analysis option,
which allows you to use EChem to view and manipulate existing data
without the PowerLab attached. Unusable controls appear dimmed.
In each case, EChem opens and the EChem window will appear. By
default, a new, untitled le will ll the screen. Its size can then be
readjusted if need be.
Once the EChem application has already been loaded, you can open
another le or create a new one by choosing Open or New from the
File menu. The Open dialog box appears (Figure 22). By default only
EChem les are shown in the scrolling list. You can navigate through
your hard disk to nd the le you want. EChem allows you to open
only one le at a time.
There are two radio buttons and three checkboxes at the bottom of the
Open directory dialog box. The radio buttons allow you to choose

12

EChem Users Guide

Radio buttons

Figure 22
The Open file dialog box

Check boxes
Appearance may vary (as shown)
depending your computer and
operating system. Radio buttons are
full when on and empty when off.
Check boxes show a tick or cross
when on, and are empty when off.

between opening EChem les, or ASCII text les which may have
come from other electrochemical systems. Only the selected type of
le is displayed in the scrolling list and is able to be opened. The
checkboxes allow you to append a le to a currently open le, to load
the settings of the new le, and whether to discard macros when the
le is opened. Opening text les and appending les are discussed in
Chapter 5.
The information in an EChem le is made up of data and settings.
Data refers to the recorded waveforms, which are normally loaded
when opening a le. Settings are of two types:
1. Recording settings: those that affect recording, such as the
current ranges, technique settingsscan rate, pulse height etc.;
and
2. Display settings: those that affect the way the data looks, such
as the window size, display settings, and menu conguration.
(Macros are also stored in a settings le.)
Note
To start EChem with its
factory default settings,
hold down the Command
key (Macintosh) or
Control key (PC)
immediately after you
start the software by
double-clicking the icon.
Release the key when the
alert box appears, and
click the OK button.

Chapter 2 EChem Basics

When you start EChem by double clicking an existing data le, or a

settings le, then both types of settings are loaded. However, if
EChem is already open and you use the Open... dialogue then there
are several possibilities.
If the Load Settings checkbox is on (marked with a tick or cross
depending on the computer and operating system) when opening a
data le, then the data and recording settings are loaded. These
settings will apply to a subsequent experiment. All settings are
retained in memory, and used for all subsequent recording, until
changed by loading new settings. Opening a settings le (which
13

contains no data) with the Load Settings checkbox off will load only
display settings, not those affecting recording of data.
If you have a le open when opening a second le, then the rst le
will be closed. If there are any unsaved changes to the rst le, an
alert box will appear asking if you want to save them before opening
the new le. If the Load Settings checkbox is on, then both the
settings and the data will be loaded, otherwise the current settings
from the rst le are retained.
Using the sample data le as you work through this users guide will
show you some real data and perhaps give a better idea of what is
going on in EChem.

Closing or Quitting an EChem File

To close an EChem le, choose Close from the File menu or click in
the close box in the Main window (upper left corner, Figure 23). To
quit EChem, choose Quit from the File menu. In either case, if you
have made any changes, a dialog box will appear, asking you if you
wish to save your work. Click the Save button if you wish to keep the
changes you have made. Click the Dont Save button if you want to
discard the changes.

The Main Window

The essential controls for recording data are provided in the Main
window and its various control panels, illustrated in Figure 23.
These controls are discussed below, and in greater detail elsewhere in
this manual. The window itself consists of, the data display area,
which contains recorded data; and some controls at the bottom of the
window. Various movable control panels surround the window
proper. The menu bar at the top of the screen contains the EChem
menus (see Appendix A), allowing you to set up and modify the way
EChem looks and behaves. The EChem Window command from the
Windows menu returns to this window from another, or opens a new,
untitled le if the window has been closed.

14

EChem Users Guide

Basic Window Controls

The close box, title bar, zoom box, and size box all work as they do in
other software.
Click the close box to close an open EChem le (this is the same as
choosing Close from the File menu). The title bar shows the title of
the le, and has horizontal lines across it if it is active (that is, the
frontmost window). Drag the title bar to move the EChem window to
another area of the screen, or to another monitor if you have one
attached (you can do this while recording). Drag the size box to set
the size of the window: this is useful if you want other applications
on the screen, and does not affect recording delity the resolution
of recorded data is independent of the resolution of the display. Click
Figure 23
The Main window of a newly
created file showing the i vs E
display mode
Title bar

File title

Zoom box

Close box
Scale
pop-up
menu

Cursor information
panel
i Channel
control
panel
Range
pop-up
menu

The data display area is empty

when opening a new le

Input
Amplier
dialog
button

Axis label

Technique
description

Vertical space
Marker
Page Comment
button

Page buttons

Scale
pop-up
menu

Display pop-up menu

(i vs E display selected)

Chapter 2 EChem Basics

15

Page Corner
controls
Size box

Start/Stop
button

the zoom box to toggle the EChem window between a set size and the
full size of the screen.
The three control panels (Cursor, i Channel, and Sample) cannot be
resized, but they can be moved independently around the screen if
necessary. Blank panels appear behind the control panels to reduce
clutter: these, too, can be moved.

Navigating
Page Corner controls

Active
page

Blank
page

EChem stores sweeps of data as if they were pages in a pad of paper.

The numbered Page buttons along the bottom of the EChem window
and the Page Corner controls (the dog-ears) at the bottom right of
the data display area allow you to move through multiple pages of an
EChem le. The highlighted Page button indicates the page of data
currently viewed. EChem will always have one blank page, the last
one, in a le. As pages of data are recorded, they are numbered
consecutively, with the blank page remaining at the right. New data is
recorded to this page.
Click the upper, folded corner of the Page Corner controls to move to
the next, and the lower corner to move back to the previous page.
Clicking the numbered Page buttons takes you immediately to that
page, or choose Go To Page from the Display menu, or type
Command-G (or Control-G), and enter the number in the dialog box
that appears. If there are too many pages to show all the buttons
along the bottom of the window, then left and right arrow scrolling
buttons will appear at either side: click them to move a page left or
right, or press them to scroll left or right through many pages.

Scrolling buttons

You can also move a page left or right by pressing, respectively, the
left and right arrow keys on the keyboard. Hold down the Command
(or Control) key while pressing the left or right arrow key to go to the
beginning or the end of the le (the rst or last numbered pages).

The EChem Axes

When EChem is displaying both I and E versus time, or I versus time,
there will be a horizontal Time axis, above the Page buttons along the
bottom of the Main window. This shows the time from the start of
sampling, When the I versus E display mode is chosen, the horizontal

16

EChem Users Guide

axis becomes the applied potential (E) and the vertical axis the
recorded cell current (I). This is reversed for the E versus I mode.
Note that the graph area remains blank until some data is actually
recorded. The scale for each axis is initially set by the current range
control on the right side of the window and the chosen technique.
Both i and E axes can be stretched or dragged using the pointer.
Display options can be chosen from the Scale pop-up menu.

The i Channel (current) Control

Figure 24
The i Channel control panel:
for 3rd party potentiostats,
and (lower) for the
ADInstruments Potentiostat

The current scale settings are located at the right of the main window.
The control panel is labelled i Channel, Figure 24.
The i Channel panel, controls the current sensitivity and setup of
either the PowerLab Channel 1 input amplier, or the ADInstruments
Potentiostat, if connected.
If you are using the ADInstruments Potentiostat press the Range popup menu to choose the full scale current range (20 nA to 100 mA).
Click on the Potentiostat button to bring up a dialog that allows you
to adjust the Potentiostat settings lters, polarity, dummy/real cell
setting, etc.
If you are using another brand of potentiostat then click the Input
Amplier button to bring up a dialog box to adjust the Channel 1
controls of the PowerLab. The signal for the potentiostat is a voltage
level that represents the current signal. You will have to adjust the
input sensitivity to your potentiostat full scale output (often 1 or 10 V
read the potentiostat manual). For example if you are using a BAS
CV-27 potentiostat, which you have adjusted to a setting of (say) 1
A/V, you will still need to keep the PowerLab i Channel setting at
10 V because this is the maximum output from the plotter
connections of the CV-27, that is, the CV-27 can report currents of up
to 10 A when set at 1 A/V.

Technique Description Panel

The area under the i Channel settings displays information about to
the selected sweep including the its name, start and end potential,
sweep rate, etc. Once the scan has been completed the time and date
are also displayed.
Chapter 2 EChem Basics

17

Data Display Area

Data is displayed in the Main Window in the area bounded by the i
and E axes, or the i, E and time axes when in the iE vs t mode. When
the iE vs time display mode is chosen, two channels are displayed.
The channel separator between them can be dragged by the black
handle at its right end up or down to vary the size of the channel
display areas. Dragging it to the top of the display or double-clicking
it will overlay channels A and B in the one display, Chapter 4.

Cursor Panel
The Cursor panel shows the value of the coordinates of the cursor
position as the pointer is moved over the data display area. For
voltammetric experiments it displays the current (I), potential (E),
and time (t) values which are updated constantly as you move the
cursor along the waveform. For amperometric experiments viewed in
the I vs t mode only time and current are reported. The Cursor
display will be blank if the pointer is not over the waveform display
area. If the Marker (see below) is positioned on the trace then the
differences, , in current, potential, and time between the marker and
cursor positions are also displayed.

The Marker
The marker can be
dragged onto the trace

The Marker can be found in the box at the bottom left of the EChem
window. It can be dragged onto the data display area to a particular
data point on the voltammogram which becomes the zero reference
point. Relative measurements can now be made. Double-clicking the
Marker or clicking its box sends it back home. You can also drag the
marker close to its lair and let go of the mouse button. The marker
will automatically nd its way back.

Page Comment Button

The page comments
button changes
appearance when a
comment is added

18

The Page Comment button can be found at the bottom left of the
EChem window, to the right of the Marker. Click it to bring up the
Page Comment window for noting down comments about particular
pages of data, for example you might want to enter the
concentrations of metal ions in a standard solution. When there are

EChem Users Guide

comments noted down for the active page, the button icon changes
from a blank note to a marked one.

Start Button
To start recording, click the Start button in the Sample panel. The
button then changes to Stop click it, if required, to stop recording.
The button may show a dimmed Wait while starting or stopping.
After the rst sweep in a new le you will be asked to save the le.
Second and subsequent sweeps will be automatically saved at the end
of each sweep. This autosave feature can be turned off from the
Preferences/Options command in the Edit menu.

Pointer
The pointer can be a cross,
I-beam, or arrow shape

The pointer will change shape as you move it about the EChem
window, giving you an indication of its function in certain areas it
becomes an I-beam over a text entry area, and a cross in the graph
area, for instance. It becomes dimmed when it cannot effect a function
under particular conditions. Do not confuse the pointer (controlled
by the mouse) with the cursor that follows the pointer when it is in
the data display area, but which remains on the trace. It is the
coordinates of the cursor that are reported in the Cursor Panel, and in
the Data Pad.

Recording
Note
EChem does not record in
the background: it must be
the active (top) application
to function.

To start recording (sampling), click the Start button in the Sample

panel in the lower right hand corner of the screen. The button then
changes to Stop click it, if required, to stop recording. The button
may show a dimmed Wait while starting or stopping.
EChem emulates some of the basic functions of a standard
oscilloscope, proving a visual image of an electrical signal against
time. However, unlike oscilloscopes EChem lets you record a large
number of sweeps as different pages of data, creating a series of
recorded waveforms, automatically stored and numbered for easy
reference. EChem can overlay any selection of these stored sweeps.
Also a single background sweep can be subtracted from sweeps that
were recorded under similar conditions (same scan rate, start and
nish potentials etc.).

Chapter 2 EChem Basics

19

Display While Recording

At slow sampling speeds you will see data drawn on the screen as it
is recorded. A short vertical line segment, the Trace Indicator, moves
left to right across the top of the data display area, tracking the front
edge of the advancing waveform as it is drawn on screen.
At fast scan rates, it will appear that the whole scan of data is drawn
at once, and no Trace Indicator is seen.

Interruptions While Recording

You can stop sampling mid way through a scan, by clicking the Stop
button in the Sampling panel, or typing Command-period (Controlperiod) or Command-spacebar (Control-spacebar). EChem will stop
the scan but retain the data already recorded (as long as the Keep
Partial Data box is checked in the Preferences/Options... command
of the Edit menu).
Please note that EChem does not record in the background. It must be
the active, or top, application while recording. If you switch to
another application (including the Finder) by choosing it from the
Application menu or clicking outside the area of the EChem window
and its control panels, then EChem will stop recording. On switching
back to EChem, the experiment will restart.

Length of Recording
The number of pages of data that you can record depends primarily
on the memory that you have allocated to EChem. If you nd that
you run out of memory, you can increase EChems memory allocation
on Macintosh by quitting, selecting the application icon in the Finder,
choosing Get Info from the File menu (or typing Command-I, or
Control-I), and typing a larger value in the Preferred size box. There
is an upper limit of 1000 pages in any one le.
The amount of memory available for recording on Macintosh can be
seen in the lower portion of the EChem dialog box, Figure 25, by
selecting the About EChem command from the Apple () menu
(click the dialog box to make it go away again).

20

EChem Users Guide

Figure 25
The available memory
indicator bar on a Macintosh.

On a Windows PC the amount of memory is allocated by the

operating system and you can record data until you run out of hard
disk space (or exceed 1000 pages).
Data is compressed while it is being recorded, the efciency of
compression depending on how the signal varies: signals that change
very slowly, such as a straight line or gradual curve, can be
compressed a great deal, while complex and rapidly changing signals
may not compress much at all. The extent of compression is usually
in the order of 2533%.
On a Macintosh EChem uses a certain amount of memory for an offscreen buffer to speed up data display. If the EChem window is large
and the display is grayscale or color, more memory is used, especially
if the monitor display has been set to thousands (16 bit color) or
millions (24 bit color) of colors. If the EChem window lled a 14"
monitor displaying millions of colors, the memory used by this
would be about 1.25 MB. If you nd yourself running out of memory,
you can use less by shrinking the EChem window to a smaller size
and changing the display to 256 colors (or even grayscale or black
and white). Since EChem only uses eight colors there is no advantage
to be gained by running in thousands or millions of colors.
The largest EChem data le, 1000 pages at about 10 K per page, could
take, at worst, up to 10 megabytes of memory (but probably more like
78 Mb), plus the overhead necessary for EChem to maintain the offscreen buffer. Of course it is much more likely that your experiment
will only have a relatively few pages of data and that it will occupy
much less space (usually much less than a megabyte).

Chapter 2 EChem Basics

21

22

EChem Users Guide

C H A P T E R

T H R E E

Setting Up EChem
EChem software supports the use of many third party potentiostats
as well as the ADInstruments Potentiostat.

This chapter describes connection of third party potentiostats to the

PowerLab, and basic settings controls such as the current range and
units conversion. Also described is the use of the ADInstruments
Potentiostat with EChem software.

For more information about third party potentiostats see Chapter 12.

EChem Users Guide

23

Using 3rd Party Potentiostats

CAUTION
Many potentiostats are
capable of producing
dangerous, even possibly
lethal, current/voltage
combinations. You should
not attempt to use a
potentiostat before reading
its manual and thoroughly
acquainting yourself with
any possible hazards that
may be associated with its
use.

EChem can be used with numerous third party potentiostats. If you

are using an ADInstruments Potentiostat you can skip this section
and start reading from The ADInstruments Potentiostat.
If you own an existing potentiostat then there is a good chance that it
will be able to be used with an EChem system. Chapter 12 lists a wide
variety of compatible third party equipment. You should refer to this
chapter to determine if your potentiostat is compatible with EChem.
More information can be obtained by emailing us at
support@[Link]. Please contact your ADInstruments
representative if you wish to make specic enquiries regarding
compatibility with your equipment.

Connecting to PowerLab
Many commercial potentiostats are suitable for connection to a
PowerLab unit and can be operated with the EChem software. These
instruments must have the ability to accept an external waveform.
You may need to consult Chapter 12 or your potentiostats user
manual to see if an external input is available.
You will need to connect the analog output of the PowerLab to the
external input of the potentiostat. This will usually be located on the
potentiostat front or back panel and will be labelled E in, External
Input, Ext. In., or something similar. Connect the potentiostat
external input to the PowerLab Output + (or Output 1) BNC front
panel connector.
Different manufacturers use opposite conventions about whether a
negative potential corresponds to reduction or oxidation at the
working electrode. If you nd that after connecting to the PowerLab
that your peak potentials are the opposite polarity to that which you
expect (for example a peak is found at +0.25 V when it should be at
0.25 V) then remove the cable from the PowerLab Output + (or
Output 1) connector and attach it to the PowerLab Output (or
Output 2) connector. This reverses the polarity of the potential
waveform signal, which in turn will change a reducing potential to an
oxidising potential (and vice versa) at the working electrode.

24

EChem Users Guide

CAUTION
Do not connect a third
party potentiostat to
channels 1 and 2 at the
front of a PowerLab unit
while an ADinstruments
Potentiostat is connected.
The results obtained will
be very unpredictable.
Similarly if a third party
potentiostat is connected
to a PowerLab unit via the
rear Multiport connector
then the channel 1 and 2
connectors at the front of
the PowerLab should not
be connected to any other
instrument.

Please note that the

MacLab/2e and /4e units
have been superseded by
the PowerLab /200 and
/400 models

In order to record current and potential data you will need to locate
the potential and current outputs located on your third party
potentiostat. These are often labelled as Applied E, App. E, E out,
E monitor, I monitor, I out, or something similar. The current (I)
output of the potentiostat should be connected to the CH1+ connector
of the PowerLab. If you need to sample the potential values, then the
potential (E) output of the potentiostat should be connected to the
CH2+ connector of the PowerLab. Potential monitoring can be done
in EChem in the Multi Pulse method if potential sampling is selected.
For most methods in EChem the potential values that are used for
plotting are the calculated potentials it is assumed that the
potentiostat will accurately follow these. Thus the points are always
exactly evenly spaced along the potential axis. Note, however, that
even if you do not connect the potentiostat to channel 2, EChem still
uses this channel to store the potential values, and thus channel 2
cannot be used for connecting to other instruments.
It is possible to alter the cable that links your potentiostat to the back
of the PowerLab /200 or /400 via the Multiport. Consult the PowerLab
Owners Guide for the functions of the different pins. However, you
should exercise care when modifying such a cable to ensure that
shorts do not occur between channels, or between signal lines and
power rails. Construction of such a cable should only be attempted by
a competent technician. If you have a special requirement then please
contact your ADInstruments representative.

Adjusting the Input Range

When a third party potentiostat is used with EChem you will have to
adjust the range of the i Channel (channel 1 of the PowerLab) to
match the output of your potentiostat. Many potentiostats have a full
scale output of 1 V or 10 V representing current ranges of 1 A, 10 A,
100 A, 1 mA, 10 mA, 100 mA, and 1 A.
As an example, if the potentiostat produces an I(out) output of 1 V
representing the full scale setting for the 1 mA current range, then the
i Channel range should be set to 1 V. If the output from the
potentiostat was 10 V representing the full scale current range of
1 mA then the i Channel range should be set to 10 V (Figure 31).

Chapter 3 Setting Up EChem

25

Use this pop-up menu to set

the range of the i channel to
match the output range of the
potentiostat

Figure 31
Adjusting the i Channel range
to match the output range of
the potentiostat

If you are dealing with very low currents (which do not give full scale
output on the potentiostat, even at its most sensitive settings) you can
try choosing a smaller range from the i Channel range pop-up menu.
This causes the PowerLab unit to amplify the incoming signal and
may give you a better result but bear in mind that any incoming
noise will also be magnied.
You can also adjust the i Channel range inside the Input Amplier
dialog box. This is discussed in the next section.

Using the Input Amplier Dialog Box

The Input Amplier dialog box (Figure 32) allows, among other
things, software control of the current recording channel in the
PowerLab. For EChem this is channel 1 of the PowerLab. The signal
present at that channels input is displayed so that you can
immediately see the effects of any changes. This allows you to
measure the current signal from the potentiostat and use it to check or
calibrate this channel to appropriate current units. Once you have
changed the settings in the dialog box, click the OK button if you
wish to apply the changes to the channel. The Input Amplier dialog
box appears when you click the Input Amplier button in the i
Channel panel. The dialog box in Figure 32 will appear.

Signal Display
The input current signal is displayed so that you can see the effect of
changing the settings. Data is not actually being recorded while you
do this as it disappears from the screen it is lost. The incoming
signal value is displayed at the top left of the display area. Slowly
changing signals will be represented quite accurately, whereas very
quickly changing signals will be displayed as a solid dark area
showing only the envelope (shape) of the signal formed by the
minimum and maximum recorded values.

26

EChem Users Guide

Pause/Scroll button

Figure 32
The Input Amplifier dialog box.

Range popup menu

Signal amplitude
Low pass
lter

Current
Amplitude
axis

PowerLab /200 and /400 Input Amplier Dialog. PowerLab /800 does not have the Positive and
Negative boxes.
Filter:

PowerLab /4SP, /8SP

and /16SP models
have a choice of low
pass lters from 1 Hz
to 20 kHz

PowerLab/4SP, /8SP and /16SP Input Amplier Dialog. PowerLab/4SP, also features Positive and
Negative boxes (not shown here).

Chapter 3 Setting Up EChem

27

The scroll button

changes when
clicked on and off

If your potentiostat has positive feedback resistance compensation (iR

compensation), you can use this window to monitor the signal while
you adjust the amount of compensation. After setting the gain simply
increase the resistance compensation until the current signal is driven
to oscillation, then decrease the amount of compensation slightly
(usually by about 10%) so that potential control is re-established.
You can stop the signal scrolling by clicking the Pause button at the
top right of the data display area (it looks like the pause button on a
tape player). It then changes to the Scroll button (like the play button
on a tape player): click it to start scrolling again. The incoming signal
is shown
You can shift and stretch the vertical Current Amplitude axis to make
the best use of the available display area drag a tick label on the
axis to stretch or shrink, or drag the area between the labels to offset
the axis. Apart from being at the right rather than the left, it is the
same as the Amplitude axis in the main window, and the controls
function identically. The Scale pop-up menu to the right of the axis is
also the same. Changes made in the Amplitude axis here will be
reected in the main window.

Setting the Range

The Range pop-up menu lets you select the full scale input range, or
sensitivity, of the i channel (normally channel 1). Changing the range
in the Input Amplier dialog box is equivalent to changing it in the
main window. All dialog box changes are made in the main window
on clicking the OK button.
The range menu will always display full scale volts or millivolts,
irrespective of the application of units conversion. The range menu
starts at +10 V full scale and can be set as low as 2 mV full scale.

Filtering
PowerLab /200, /400, /800 units can apply a 50 Hz, 2-pole Bessel,
low pass lter to the incoming signal which may aid in the removal of
high frequency noise. With other PowerLab models such as the /4SP,
/8s, and /16s, you can select an appropriate low pass lter (1 Hz to
20 kHz) from a menu, Figure 32. Your Potentiostat may also have
lter settings which can also be used. However, remember that for
28

EChem Users Guide

high speed scans, or for work with short period pulses, you will need
to keep ltering to a minimum.

Differential or Single-ended Inputs?

Most potentiostats provide a single ended output and the current
signal needs to be connected to the CH1+ of the PowerLab unit. If
your potentiostat is giving an exceptionally noisy signal you may also
want to try connecting it differentially as this can sometimes reduce
noise levels. The PowerLab /200, /400, /4s, /4SP, /4ST, and older
MacLab/2e and /4e units, can accept a differential signal. Use either
the front panel BNC connectors labelled CH1+ and CH1, or via the
front panel DIN connectors see the PowerLab Owners Guide. You
will also need to make sure that you cross both the Positive and
Negative checkboxes to activate the differential input.

Inverting the Signal

The Invert checkbox allows you to invert the current signal from the
potentiostat. It provides a simple way to change the direction of the
recorded current signal without having to reconnect leads. Use this if
you nd that your peaks are going to negative current values when
you would prefer them to go to positive current values (or vice versa).

Units
Clicking the Units button brings up the Units Conversion dialog
box, allowing you to display the signal from the potentiostat in the
correct units of current. This provides an easy way to calibrate the
channel to the range of the potentiostat. Using Units Conversion is
discussed in the next section.

Units Conversion
To bring up the Units Conversion dialog box (Figure 33) click the
Units button in the Input Amplier dialog box.
Units conversion lets you scale the i Channel Axis so that the
incoming current signal from the potentiostat (which is actually a
voltage signal) is displayed in appropriate current units such as mA
or A.
Chapter 3 Setting Up EChem

29

Figure 33 The Units

Conversion Dialog box.

Voltage value, use

units of mV or V

Equivalent current value

Current units
pop-up menu

Converting Units
Note
There must be a
proportional relationship
between the recorded
voltage and the new units
for the units conversion to
work properly. Most
potentiostats provide such
a signal.

Before using the Units Conversion feature you must turn it on by

clicking the On button. Underneath there are two edit text boxes: the
left-hand box is used to enter the potential value, and the right-hand
box is used to enter the equivalent current value. Both of the boxes
must have values in order to calculate the relationship between
potential and current. You can press Tab to move between the elds.
If, for instance, you are using a potentiostat that produces a 10 V
signal for a full scale current of 1 mA then you would type in 10 in
the left box and 1 in the right box. Then choose mA from the
Current units pop-up menu. Once you click the OK button the i
Channel axis will now display the correct units of current.
You can turn units conversion off or on without losing the values you
have entered by clicking the Off or On buttons.

Applied Potential
The applied potential slider control allows you to adjust the control
voltage sent to the external input of the potentiostat. To change the
value simply drag the control left or right to set an appropriate
potential or click on the A-button to enter an exact value.

30

EChem Users Guide

The ADInstruments Potentiostat

If you are using an ADInstruments Potentiostat the EChem interface
will be slightly different as the Potentiostat is designed to be
completely controlled from within EChem. First connect the
Potentiostat to the PowerLab unityou should read Chapter 9 for
details.

Changing Potentiostat settings

When the Potentiostat is properly connected to the PowerLab and
you run EChem you should see the i Channel control panel shown in
Figure 34.
Figure 34 The i Channel
control panel.

Current range pop-up menu

Click this button to access the
Potentiostat dialog box

You should see the Potentiostat button at the bottom of the panel. If
the button says Input Amplier then quit, turn off the PowerLab
unit, recheck the Potentiostats connections, and try again. If you are
using a PowerLab/200 or /400 with Multiport connection to the
Potentiostat ensure that there is nothing connected to the CH1 and
CH2 front panel input connectors of the PowerLab unit.

Adjusting the Current Range

The Potentiostat range control reads directly in full scale current
values. The Potentiostat supports ranges from 100 mA down to 20
nA. To adjust the current range choose an appropriate full scale
current from the range pop-up menu in the i Channel control panel.

The Potentiostat Dialog Box

The
current
range popup menu

The additional controls of the ADInstruments Potentiostat can be

accessed by clicking the Potentiostat button in the i Channel control
panel.

Chapter 3 Setting Up EChem

31

Pause Button

Figure 35
The Potentiostat Input
Amplifier dialog box

Filter popup menu

Signal amplitude

Range popup menu

Cell
connection
modes

Applied potential
slider control

Applied potential
slider control

This dialog (Figure 35) allows you to adjust the current range,
ltering and cell connection settings. Galvanostat functions are only
enabled when using Chart or Scope software, see Chapter 8.

Signal Display
The current signal from the connected cell is shown in the scrolling
display area. By using the Dummy or Real modes the effect of an
applied potential can be seen prior to actually recording the data. No
data is actually recorded when the Potentiostat dialog box is open.
When the dialog is closed the signal trace is lost.
You can stop the signal scrolling by clicking the Pause button at the
top right of the display area (it looks like the pause button on a tape
player). It then changes to the Scroll button (like the play button on a
tape player): click it to start scrolling again.
You can shift or stretch the vertical Amplitude axis to make the best
use of the available display area. Apart from being at the right rather
32

EChem Users Guide

than the left, it is the same as the amplitude axis in the main EChem
window.

Setting the Range

The range pop-up menu lets you select the input current range or
sensitivity of the Potentiostat. Changing the range here also changes
the range in the Scope and Chart window. The default setting is
100 mA and goes to 20 nA in 1, 2, 5 steps.

Filtering

The lter
pop-up
menu

The Potentiostat has a number of low pass lter settings, for removal
of high frequency noise at 10 kHz, 1 kHz, 100 Hz, 50 Hz, and 10 Hz.
The pop-up menu can be used to select the appropriate lter. The 10
Hz setting is very effective in removing 50 or 60 Hz mains hum but be
careful that it does not distort your voltammograms. As a rough
approximation the 10 Hz lter can be used safely for linear sweep or
cyclic voltammograms up to about 100 mV/s, or for pulse techniques
where the pulses are longer than about 100 ms.
For very high speed scans or for work with millisecond pulses you
will need to use the 10 kHz lter setting.

Inverting the Current Signal

The Invert checkbox allows you to invert the signal on the screen. It
provides a simple way to change the direction of the recorded current
signal. This will allow you to display your data according to whether
you prefer that a current signal greater than zero represents an
oxidation or a reduction process at the working electrode. If you nd
that your voltammetry experiments have peaks that point to greater
negative currents when they should point to greater positive currents
(or vice versa) use the invert checkbox.

Cell Control
Three modes are provided to control the way in which the
Potentiostat connects to the cell. Each of these modes is analogous to
the settings found on traditional potentiostats.

Chapter 3 Setting Up EChem

33

Standby the external cell is disconnected and the internal dummy

cell is connected to the Potentiostat. When the Potentiostat dialog is
closed and the Chart, Scope or EChem start button is clicked the
external cell will be connected to enable the experiment. This mode is
used if you do not wish to connect to the external cell until the
experiment is actually performed. The Applied Potential control is
disabled in this mode.
Dummy the Potentiostat is connected to the internal dummy cell
(an internal 100 k resistor network). You can use the Applied
Potential slider control to vary the voltage applied to the dummy cell.
The Potentiostat will remain connected to the dummy cell even when
the Potentiostat dialog is closed and Chart, Scope or EChem is
recording. This is useful for testing a method using the dummy cell.
Real the external cell is connected to the Potentiostat while you are
in the Potentiostat dialog. The Applied Potential slider control can be
used to adjust the voltage applied to the external cell. When you close
the Potentiostat dialog the external cell will be disconnected until the
Start button is pressed and Chart, Scope or EChem begins to record
an new experiment. This is similar to the Standby mode except it
allows you to modify the applied potential before the method is
started.

Applied Potential
The applied potential slider control is enabled in either
Dummy or Real modes. It allows you to adjust the voltage
applied to either the dummy cell or external cell
depending on the mode selected. To change the value
simply drag the control left or right to set an appropriate potential
or click on the A-button to enter an exact value.

Reverse Polarity
Depending on your local convention you may wish to dene a more
oxidizing potential at the working electrode as either a more
positive, or as a more negative potential.
If the Reverse Polarity box is crossed then the Potentiostat will
produce oxidizing potentials at the working electrode at more

34

EChem Users Guide

positive applied potentials. If the box is unchecked then the working

electrode becomes more reducing at more positive potentials.
In practice what you might nd is that your voltammogram exhibits a
peak at (say) 300 mV when it should be at 300 mV. The chances are
that the polarity setting is the opposite of what you want. Reverse the
polarity and try again.
You can save your preferred polarity convention as the default StartUp, or as a settings le.

Chapter 3 Setting Up EChem

35

36

EChem Users Guide

C H A P T E R

F O U R

Data Display and

Analysis
EChem allows you great exibility in displaying data. You can change
the lines, patterns, and colors of the display. You can resize the
EChem window, change the size of the channels display, or overlay
the voltage and current channel, or invert or interchange the current
and potential axes. You can zoom to see a small section of data in
great detail, or overlay data from any selection of pages in a le.

The whole purpose of recording data, of course, is to nd things out

through analysis of the recording. Voltammograms can be measured
using the Cursor, to give absolute coordinates or relative readings
from marker. A background page can be set, so that the
voltammogram on it is subtracted from all others in the le. The
inbuilt Data Pad calculates and stores statistics about recorded data,
calculates peak maxima, and areas. The current signal can also be
smoothed, integrated or differentiated according to your
requirements.

This chapter describes the display options available in EChem, from

the basic settings through to Amplitude axis manipulation and the
Zoom window, and also discusses the available analysis options.

EChem Users Guide

37

The Main EChem Window

The
display
mode popup menu

Recorded data is displayed in EChems main window. By default, the

current and potential data is displayed in an XY plot with current on
the vertical axis and potential on the horizontal axis (I vs E). You can
also change the display mode to show both potential and current
against time (IE vs t), potential versus current (E vs I), or current
versus time (I vs t), Figure 41. To change the display choose the
appropriate mode from the display mode pop-up menu at the bottom
left of the Main window.

Figure 41
There are four main display
modes that can be accessed
by the display mode pop-up
menu.

38

I vs E mode, current on the Y axis

and potential on the X axis.

E vs I mode, current on the X axis

and potential on the Y axis.

IE vs t mode, current and potential on

separate Y axes and time on the X axis.

I vs t mode, time on the X axis and

current on the Y axis.

EChem Users Guide

IE vs t Display Extra Features

When the display is in the IE vs t mode you can vary the relative sizes
of the channel display areas Figure 42.

Move the pointer over the channel separator. It

changes shape:

Figure 42 Changing
relative heights of the
channels and overlaying
current and potential data in
the IE vs t display mode.

Drag the channel separator (the short black bar)

up and down, to the desired position middle
picture; or double click the separator to overlay
the channels bottom picture.

After you have resized the two channels you can

double click the separator to return to equal
spacing.

Position of channel separator in overlay mode.

Double click to show separate channels.

By dragging the separator to the top of the

window you can overlay the current and
potential traces.

By dragging the channel separator to the top of the window you can
overlay the current and voltage signals the current axis is on the
left, and the potential axis is on the right, Figure 42. Both Y axes can
be shifted and stretched independently to adjust the graphs as
required. The channel separator handle moves to the top right of the
window double-click it to toggle back to separate channel display.

Chapter 4 Data Display and Analysis

39

The Axes
The limits and direction of the current and potential axes can be set
from the Scale pop-up menu. The button for which, Figure 43, is
located on the left-hand side of the current axis (when it is the Y axis)
or the lower right hand side of the current axis (when it is the X axis,
in E vs I display mode). There is a similar button on the potential axis.
The Bipolar and Single Sided options are disabled if Units Conversion
is already applied.
Location of
the axis
menu
button

Figure 43
Using the current axis
controls. Similar controls are
found on the potential axis.

The set scale dialog allows you to

enter exact limits for the axis.

Units Conversion (current axis

only) allows you to rescale the
output of the potentiostat so
it displays the correct units.

40

EChem Users Guide

The current axis

pop-up menu

Computed Functions allow

you to transform the data

Single Sided. Shifts the axis so that zero is located at the bottom (or
left) of the display area. This option can be used if you wish to view
only current signals larger than zero. Any readings below zero will be
off the screen (to see them, select the Bipolar option). If the axis is in
bipolar display (below) double clicking it will make it single sided
display.
Bipolar. This is the default mode for each channel. It displays zero at
the centre of the axis. Double clicking the axis will make it return to
bipolar display.
Set Scale. This option allows you to adjust the axis directly to display
the range of values you desire. It works whether Units Conversion is
on or off. When you choose Set Scale, the Scale Range dialog box
appears (Figure 43), allowing you to type in directly the lower and
upper limits of the axis to be displayed.
Note that Set Scale is meant for ne-tuning the scale setting rather
than for use as a gross magnication tool, and will allow expansion or
compression to no more than twice the original range chosen, with
neither the upper or lower value being over three times the original
limit. First set the range approximately from the Range pop-up menu
for the channel, and then set the axis to the precise values required. If
you are trying to enlarge very small features you should consider
using the Zoom window, or (preferably) recording the data at a
higher gain.
Invert Axis. This will reverse the direction of the axis. Useful if you
want positive current values to go in the downwards direction (or
towards the left when current is on the X axis). The direction of the
potential axis can also be reversed so that oxidative potentials can be
displayed to the left or right.
Units Conversion Choosing the Units Conversion item brings up
the Units Conversion dialog box (current axis only) which allows you
to readjust the conversion factors for the current signal. You have a
choice of reassigning conversion factors for all the pages in the le of
just for a particular page. See Chapter 3 for more details of Units
Conversion.
Computed Functions Choosing this item is the same as selecting
Computed Functions... from the Display menu, and is discussed more

Chapter 4 Data Display and Analysis

41

fully later in this Chapter. You can smooth, and perform various
mathematical transformation on the current signal. You can offset the
potential signal (if you want to set a new reference potential).

Dragging and Stretching the Axes

Figure 44 The pointer
changes shape as it moves
over different parts of the
axes.
Normal pointer
Pointer as it appears
between tick labels
move axis
Pointer when
over tick labels
stretch axis

The scale of the potential and current axes can be independently

dragged (offset) or stretched for optimum data display. This allows
you to enlarge the signal viewed on the screen, for instance, or move
it to better t in the display area.
The pointer changes as it is moved over the axis area as shown in
Figure 44. In the data display area, it is a normal, leftward-pointing
arrow. Over the axes, though, the pointer leans to the right, and a
small marker appears beside it. Between the axis tick labels, a doubleheaded arrow indicates that dragging will move the axis. If the
pointer is near an axis tick labels then dragging will stretch or
compress the axis.
Dragging or compressing the scale allows you to set the axis to three
times the range limit, and stretching allows you to expand the axis up
to 20 times.
Double-clicking in the axis area returns the scale to its normal,
unstretched position, with zero at the mid-point of the axis. Doubleclicking again toggles between this Bipolar display and the Single
Sided display, which has zero at the bottom of the display area.

Figure 45
The Display Settings dialog
box for changing line types
and colors.

Background
buttons
Graticule
buttons

Colour pop-up
menu

42

Line type
buttons

EChem Users Guide

Graph Lines, Patterns & Colors

The Graph Lines, Patterns & Colors dialog box allows you to set the
type, pattern, and color of the voltammogram for each channel, the
pattern and color of the graticule (the display grid), and whether the
background is white or black. The exibility over the display will
depend on which display mode you are using, IE vs t or I vs E. The
differences in the dialog controls is shown in Figure 45. To bring up
the dialog box, choose Graph Lines & Colors from the Display menu.

The Color Menus

Figure 46
The Color pop-up menu

The Color pop-up menus, Figure 46, for the graticule and channels
let you choose the pattern and color of each. Press them to bring up
the options. The choices are the basic system colors; black, red, blue,
green, magenta, cyan, and yellow; and lighter patterns of the solid
colors: gray, light red, and so on. Colors appear as greys on a grayscale monitor. Colors and greys can be printed as well as displayed, if
you have an appropriate printer.

Other Controls

Graticule buttons

Background buttons

Line type buttons

The Graticule buttons let you choose the form of the display grid.
Click to select a button it is highlighted with a heavy border. You
can choose to have a dot graticule (the default setting, no graticule at
all, or a line graticule.
The Background buttons let you choose whether the background of
the voltammogram is white or black. Click to select a button it is
highlighted with a heavy border.
The Line type buttons for each channel give you the choice of
displaying the data points joined by lines, as unjoined dots
(individual data points), or as a solid ll. Click to select a button it
is highlighted with a heavy border. A continuous line is the default
for EChem.

Chapter 4 Data Display and Analysis

43

Overlay Display Settings

By default, the voltammogram shown on the active page is colored
black and those on the overlaid pages are in gray. You can change
colors and patterns of the active and overlaid voltammograms by
choosing Overlay Display Settings from the Display menu. The
Overlay Display Settings dialog box will be displayed. The controls in
the Overlay Display Settings dialog, Figure 47, work in the same
way as those in the ordinary Display Settings dialog, Figure 45,
except that they dene the settings for overlaid data only.

Figure 47
The Overlay Display Settings
dialog.

Colour pop-up
menu

Line type
buttons

Navigating
Page Corner controls

Active
page

Scrolling buttons

44

Blank
page

EChem stores sweeps of data as if they were pages in a pad of paper.

The numbered Page buttons along the bottom of the EChem window
and the Page Corner controls (the dog-ears) at the bottom right of
the data display area allow you to move through multiple pages of a
EChem le. The highlighted Page button indicates the page of data
being viewed, the active page.
Click the upper folded corner of the Page Corner controls to move a
page right, and the lower corner to move left. You can also move a
page left or right by pressing, respectively, the left and right arrow
keys on the keyboard. Hold down the Command key (Macintosh), or
Control key (Windows PC), while pressing the left or right arrow key
to go to the beginning or the end of the le (the rst or last numbered
pages).

EChem Users Guide

To go to a specic page, choose Go To Page from the Display menu,

or type Command-G (Macintosh) or Control-G (Windows PC). The
Go To Page dialog box appears (Figure 48): and you type the
number of the page in the text entry box (which will be selected) and
click the OK button (or press Return or Enter).

Figure 48
The Go To Page dialog box.

You can also click a numbered Page button to go to that page. If there
are too many pages to show all the buttons along the bottom of the
window, then left and right arrow buttons will appear at either side:
click them to move a page left or right, or press them to scroll left or
right through many pages.

Overlaying Pages
You can overlay pages of data recorded at different times or under
different conditions one atop the other.
Choose the Show Overlay from the Display menu. The nominated
pages selected can be seen through the active page as if each
voltammogram were on a pad of transparent plastic sheets. The menu
command then changes to Hide Overlay and only the active page is
visible. These commands turn the page overlaying display on or off,
respectively, and do not affect which particular pages have been
selected for overlay.
To overlay all pages, choose Overlay All from the Display menu, or
type Command-A (Macintosh), or Control-A (Windows). The data in
all pages appears, drawn atop each other. By default, the data shown
on the active page is black and other, overlaid, pages are in gray
(these settings can be changed). To remove all pages from the overlay,
choose Overlay None from the Display menu, or type Command-H
(Macintosh), or Control-H (Windows PC). Only the active page
remains visible, and none of the others is selected for overlaying.

Chapter 4 Data Display and Analysis

45

Using the Page Buttons

The Page buttons along the bottom of the main window indicate the
status of pages. The active page is highlighted; Pages selected for
overlaying have icons containing black rectangles and those not
selected have icons with gray rectangles.

Figure 49
Overlaying pages.

Blank
page

Selected
page

Not included
in overlay

Included
in overlay

As mentioned, you can click a numbered Page button to go to that

page. The active page does not need to be included in overlaying,
since it will always appear (so that you can, for instance, quickly
check a set of overlays against a set of reference pages which are not
themselves overlaid). Command-click (Macintosh), or Control-click
(Windows PC), or double-click a Page button to add the page to or
remove it from the set of overlaid pages. Option-click (Alt-click) a
Page button to hide all pages except the one whose icon was clicked.
Press and hold a Page button to activate the pop-up menu which
duplicates the various overlay and navigation functions (Figure 410).

In case you press rather than click the Page button

Figure 410
The Page Button menu

Command-click (Control-click) or double-click

Command-click (Control-click) or double-click
Option-click (Alt-click)

Click and hold the mouse down

The Scale of Overlaid Pages

When you overlay pages with different vertical ranges, data on other
pages is automatically shown scaled to the range of the active page.
However in IE vs t, and I vs t, modes the horizontal time axis is not

46

EChem Users Guide

scaled and the overlaid pages, which could have different time bases,
may not be shown to scale.

The Zoom Window

With the Zoom window, you can look at a small section of data in
great detail. To zoom in on a data selection, drag to select an area of
interest in the main window, and then choose Zoom Window from
the Windows menu: the Zoom window appears (Figure 411).

First make a selection of the voltammogram to be

enlarged, then choose the Zoom Window command
from the Windows menu

Figure 411
The Zoom Window

You can make a further selection in the data display area of the Zoom
window: this automatically zooms in further on that data. If the
selection contains less than four data points, the Zoom window will
appear gray. If this happens, you should reselect an area in the main
EChem window.

Data Display
The Zoom window does not have the Display pop-up menu to switch
between I vs E, or IE vs t etc., but has the other controls (Marker and
page buttons etc.) of the Main window.

Chapter 4 Data Display and Analysis

47

In IE vs t display mode, if the selection covers only one channel, then

only one channel is displayed, and the separator handle is dimmed
(see Figure 4-12). If the selection covers two channels, then by default
the channels are overlaid, but as in the Main window, double-clicking
or dragging the channel separator handle will separate them.
Channel overlaying is independent of that in the Main window: you
can have the channels separate there and overlaid in the Zoom
window, for instance.
The channel separator in overlay mode.
Double click to show separate channels.

Figure 412
The Zoom Window in IE vs t
display mode

Drag the channel separator (the short

black bar) up and down, to the
desired position or double click the
separator to overlay the channels
top picture.

The scale of the vertical axis of each channel can be independently

dragged or stretched for optimum data display, just as in the main
EChem window.
When moving between pages, the selection area remains the same
with regard to the raw data (and will remain in the same relative
position in the EChem window).
The Marker from the Main window knows about the Marker in the
Zoom window moving it onto a voltammogram in one window
will do the same in the other, double-clicking it will send it to its lair

48

EChem Users Guide

 and the Page Comment button will bring up the Page Comment
window for the active page.
As you move the pointer across the data display area, the Cursor
tracks the displayed data, and the current (i) and potential (E)
readings at the tracking point are indicated in the Cursor panel.

Printing the Zoom Window

When the Zoom window is active, then when Print is chosen from
the File menu, the contents of the Zoom window are printed, after the
appropriate dialog boxes have been dealt with. The printed page is
headed with the window title and the number of the EChem page.

Display and Printer Resolution

EChem allows a exible data display, so that the display can be
rescaled and resized. The controls are not difcult to get used to,
especially since the axes are always visible, but they may make the
voltammogram look abnormal if you expect it to have the same size
and aspect ratio of a standard chart or XY recorder.
The screen display on a monitor is generally about 72 dots per inch,
so the apparent resolution is not that good if the display is kept small.
The signal might appear jagged and unresolved on a small screen.
However, the resolution of the recorded data is independent of the
resolution of the display: sampled data is always recorded at 12 bit
(0.024%) delity at each sensitivity setting. The one important rule is
to record your data at the maximum sensitivity (gain) that will keep
your voltammogram within the full scale range.
High-resolution printing will show the selected voltammogram
accurately. A print-out might not appear as smooth as the pen output
of a standard pen recorder if you are using a low resolution dot
matrix printer. To get high quality output you should use a laser
printer or inkjet printer with a resolution of 300 dpi or greater. Laser
printers that use Adobe PostScript are recommended for maximum
quality output.
It is important to check display settings carefully when examining a
data, to be sure that what you are looking at is what you think you

Chapter 4 Data Display and Analysis

49

are looking at, especially if the settings on your machine might have
been altered. A trace may end up looking very strange if it has been
stretched vertically or had an inappropriate baseline subtracted.

Making Measurements
When you have nished recording you can make direct or relative
measurements from the voltammogram (or amperomogram).
When the pointer is over the data display area, the Cursor tracks the
voltammogram, Figure 413. In this case, The Cursor panel shows the
current, potential, and time coordinates at the cursor location
The Cursor only gives discrete measurements, jumping from data
point to data point (you can see this more clearly in the Zoom
window). It cannot provide a reading on the line that is drawn
between the individual data points.
Current, potential and time (I, E and t)
cursor coordinates
Figure 413
Use of the Pointer and Cursor.

The pointer is positioned

with the mouse.

The cursor is attached to

the trace but follows the
pointer.

Using the Marker

The Marker can be found in its lair, a box at the bottom left of the
EChem window. It is used to set a particular data point as a zero
reference point, so that relative measurements can be made with
respect to that point, Figure 414. To set the Marker, drag it from its

50

EChem Users Guide

lair into the voltammogram it will lock onto the voltammogram

when you release the mouse button. Option-drag the Marker to
position it the anywhere on the screen. Use the display in the Cursor
panel to help to select a data point. If you need ner control of the
Marker position, use the Zoom window to look at a selection in more
detail: the Marker is duplicated there, and can more easily be
assigned to a particular data point.
Double-clicking the Marker or clicking its box at the bottom left of the
EChem (or Zoom) window sends it back to its lair.
Once the Marker is in position, measurements relative to it (preceded
by ) are given in the display in the Cursor panel. The symbol
before a value indicates that it is a difference, not a direct reading. If
the channels are overlaid and the Marker is not on a voltammogram,
the voltammogram closest to it is the one for which relative readings
are made.
Time, current and potential of the
cursor position relative to Marker

Pointer

Cursor

Figure 414
Using the Marker tool
Marker

Marker
lair

Setting and Removing Baselines

The Marker is also used for setting relative measurements where the
baseline of the voltammogram (or amperomogram) is not zero. If you
nd that the baseline value is not zero when it should be that is,
there is some slight offset a baseline may already be set up. Place
the Marker at a point you want the baseline to intersect. Then
Command-drag (Macintosh), or Control-drag (Windows PC), from
Chapter 4 Data Display and Analysis

51

the Marker lair (or from the Marker itself) a duplicate Marker, which
can be placed to set the second point dening the baseline
(Command-Option-drag, or Control-Alt-drag, to place this duplicate
Marker off the curve). The baseline is displayed as a dotted line
passing through the two Markers, Figure 415. The baseline can only
be positioned when you are in I vs t, or IE vs t, display modes. You
cannot set a baseline when in the I vs E, or E vs I, display modes.
Vertical distance of cursor to baseline

Pointer

Cursor
Figure 415
Using the Marker tools to
create a baseline

Duplicate Marker
Marker

Baseline dened
by the two markers

Marker
lair

The value along the baseline is set at zero: the Cursor panel shows the
absolute time and potential, but the current signal at the cursor is
shown relative to the baseline.
Note that the baseline is set for a particular channel on a particular
page of data. When moving between pages, the baseline may move
considerably if locked to the voltammogram; if independent, it will
remain static. Removing one Marker removes both Markers, and the
baseline. Attempting to set a vertical or near-vertical slope will also
remove the baseline and send the Marker and its duplicate home.

The Marker Miniwindow

To display the exact Marker position, or both Marker positions when
a baseline is set, choose Marker from the Windows menu: the Marker
miniwindow appears, Figure 416. The Marker miniwindow oats
in front of the active window, can be moved around with its title bar,
and can only be dismissed by clicking its close box. It has a display
area divided into three panels, showing the channel (i or E) in which
52

EChem Users Guide

the Marker is active, and the time and signal readings at the Marker
position, Figure 416. If the Marker is inactive, the two lower panels
are blank and the top panel displays Off.

Figure 416
The Marker miniwindow

marker not on
graph

marker on I vs E
graph

marker on i
channel in IE vs t
graph

marker on E
channel in IE vs t
graph

Clicking the Set button brings up the Set Marker Position dialog
box, Figure 417,which allows you to alter or dene the Marker or
baseline position by typing values into the text entry boxes, then
clicking the OK button to apply them to the EChem window.

Figure 417
Positioning the Marker

Clicking the Off radio button turns the Marker off, clicking one of the
other radio buttons selects the channel in which the Marker will
appear. If the Lock Marker to Waveform checkbox is on, the Marker
will position itself on the signal, and the text entry box for I or E
values is inactivated (appears dimmed). If the checkbox is off, the
Marker is independent of the voltammogram, and you can enter the I
or E and hence assign the vertical position of the marker. Entering
values into the Marker 2 text entry boxes as well as those of Marker 1
will create a straight baseline joining the two markers.
In the I vs E (or E vs I) display mode, the Marker miniwindow shows
On in the top panel, and I and E values in the other two panels.
Since there is only the one Marker and you cannot set a baseline, the

Chapter 4 Data Display and Analysis

53

Set Marker Position dialog box is simplied for the I vs E display,

Figure 418. The Marker is set independently of the signal trace if you
use this dialog box to position it.

Figure 418
Positioning the Marker when
in the I vs E (or E vs I) display
modes

Background Subtraction
It is possible to set up a background page, the voltammogram from
which is subtracted from all other pages in a le with the same
settings (potential range, scan rate, and so on). This has a number of
uses, for instance, non-linear baseline subtraction. A reference
voltammogram can be made of a blank sample, then standard
additions could be made and the blank trace subtracted to give the
readings for the analytes of interest. Background subtraction can also
be used a to isolate a small signal from a noisy background, or from a
sloping baseline.
To set up background subtraction, go to the page you want to use as a
background page, and choose the Subtract Background command
from the Display menu. The voltammogram on the active page is
subtracted from itself (so it shows a line at zero current), and all other
pages in the same le that have been recorded under the same
conditions (potential range, scan rate, etc. if these settings were
different, distortion and clipping would result.). Note that scans
recorded at different sensitivities (but otherwise identical settings)
can be subtracted. The Page button for the background page shows
the page number underlined.

The Background page is

underlined

54

Once a background page has been set, EChem stores it in memory, so

it does not have to be in the same le as the voltammograms from
which it is subtracted. This means that you can set up les of
calibration pages to subtract from new data, set the appropriate
background page, and then open a new le to sample with
EChem Users Guide

background subtraction. It also means you will not necessarily see the
background page button, but the menu commands Subtract
Background and Clear Background in the Display menu will be
undimmed when a background page is in memory, so this will tell
you if such a page has been set.
The Subtract Background command toggles with the Dont Subtract
Background command. Both leave the background page in memory,
but will subtract it or not subtract it, respectively, from
voltammograms in the open le, so that you can compare
voltammograms before and after subtraction.
Choosing Clear Background from the Display menu clears the
background page from memory, and restores the raw data.

The Data Pad

The Data Pad can store large amounts of data (cursor coordinates,
peak maxima and minima etc.) in spreadsheet format up to 32
columns with 32,000 rows, with each cell having at most 255
characters to a maximum of 2000 characters per row. Its contents can
be saved as a text le, or copied to the Clipboard for transfer to other
software, or printed directly. To bring up the Data Pad, Figure 419,
choose Data Pad from the Windows menu.
The Data Pad window is a normal window with a close box, size box,
and title bar, and can be moved around the screen or left in the
background while the EChem window is active. It can be resized
using the size box at its bottom right corner. Click the zoom box to
toggle the window between the set size and the full size of the screen.
Information on the current selection or active point is displayed
immediately above and beneath the column headings: the readings
beneath the column headings are separated from recorded data by a
heavy line, and are centered rather than left-justied to help to
distinguish them. In EChem, the active point is the last point clicked
in the data display area.
As data is added to the Data Pad, new rows of values are created
below existing rows in the data area. Use the scroll bars to move
down or across through rows and columns. There are two tools that

Chapter 4 Data Display and Analysis

55

Column headings. Drag these panels onto

the voltammogram to create Miniwindows

Figure 419
The Data Pad window

Data Pad Pop-up menu

Row button
Cell button
Data in the current
selection

Drag heading
dividers to
alter column
width

Points entered
in the Data Pad

can be used to deal with the data in the pad, indicated by the buttons
at the top left of the window. By default the Row button is selected
and the Pointer appears as a heavy cross when over the data area.
Click to select a row, Shift-click or Shift-drag to select contiguous
rows, or Command-click (or Control-click) to select or deselect rows
individually; the data can then be cleared, or cut or copied to the
Clipboard as tab-separated text, using the commands in the Edit
menu. If the Cell button (with the A) is clicked, the pointer changes to
an I-beam when over the data area, and text in each cell can be edited
in the normal way. Clicking the Cell button deselects all selected rows.
The Data Pad pop-up menu allows you to add blank rows to the Data
Pad, or to add the current column headings to it as three lines
which is useful to keep track of changed settings, or when
transferring data to other software. You can also choose whether or
not to save the Data Pad settings when a new le is opened: a tick
appears beside this menu command when it is active. It applies only
to the current le. The Auto Add command adds the dened data to
the Data Pad for every sweep, whether single, multiple,
superimposed, or average, and whether or not each sweep is on a
new page.

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The width of columns can be changed to suit the displayed data and
headings. You might want to narrow columns to display more on
screen, for example, or have a wide column to the right in which to
add comments. Position the pointer on the heavy dividing line
between column headings, so that it changes into the resizing pointer,
drag until the column is the desired width a gray line appears, to
indicate position then release the mouse button.

Adding Data to the Data Pad

To add data from a selection in the EChem window to the Data Pad,
choose Add to Data Pad from the Windows menu, or type CommandD (Macintosh) or Control-D (Windows PC). If you want to add data
on the whole page, the whole page must be selected. Some timebased functions (such as Integral) will only operate when you are in
the IE vs t, or I vs t, display modes. If there is no selection, data at the
active point is transferred. As a shortcut, you can double-click in the
data display area to transfer data at a point (which becomes the active
point). This can also be done from the Zoom window; the
magnication it provides may prove useful in locating particular
features.
The data recorded will depend on the choices made in the Data Pad
Column Setup dialog box.

Setting Up the Columns

As previously noted, the data recorded will depend on the choices
made in the Data Pad Column Setup dialog box. This dialog box
appears on clicking a column heading panel,Figure 420, and will
have the column number (1 32) in its title.
Figure 420
Setting up the Data Pad
columns

Chapter 4 Data Display and Analysis

57

To move to the dialog boxes of adjacent columns (and set up many

columns quickly), click the arrows by the dialog box title, or press the
right or left arrow keys on the keyboard.
The channel that data is taken from is selected in the Channel pop-up
menu at the right of the dialog box. Two scrolling lists let you select
from the many forms of information that could be recorded, whether
derived or direct. The left-hand list gives the general information
type, and the right-hand one options available in that set. The
selected option is briey explained in a box beneath the two lists.
Off simply turns the column off: no data is recorded in it.
General Statistics offers calculation of the mean, standard deviation,
standard error of the mean, or integration (with respect to time, [Link])
of the selected region of the current signal. The value of the largest or
smallest data points in the selection (or the difference between them),
the times at which they were recorded, or the number of data points
in the selection can also be obtained for the current signal.
Selection Information. If there is a selection, this function will report
the start time, end time, or duration.
Cursor. These functions report the time, current and/or potential (t, I
and E values) at the active point, if there is one. It does nothing if
there is a selection of more than one point.
Slope gives the maximum or minimum slopes (with respect to time,
di/dt) found in a selected area of the voltammogram (or
amperomogram), the average slope of a selection (the equivalent of
tting a straight line through a selection of data points), or the slope
of the curve at the active point.
E values can return the magnitude of the potential at the points at
which the maximum or minimum current signal (i values) in a
selection.
Its various functions make the Data Pad very useful for quickly
extracting information about a voltammogram. You can leave the
Data Pad, set up to display the required information, as a small
visible background window that will be updated as you skip from
page to page or as new entries are made.

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Data Pad Miniwindow

Miniwindows can be created to display the current values of statistics
or measurements set up in the Data Pad, Figure 421. Click the
Miniwindow checkbox in the Data Pad Column Setup dialog box to
show or hide the miniwindow for a column, or drag a column
heading to the main EChem window. Drag the miniwindow by its
title bar to where you want it, click the close box to dismiss it, or click
its body to bring up the dialog box again.

Figure 421
Data Pad Miniwindows

Printing the Data Pad

When the Data Pad window is active, then the Print option in the File
menu changes to Print Data Pad, so that the contents of the Data
Pad window are printed rather than those of the EChem window. The
Data Pad will print across two or more pages if it is wide enough, but
individual columns will remain intact.

Computed Functions
By default, EChem records the raw current data in the I Channel and
does not apply any computed function. Sometimes, though, some

Chapter 4 Data Display and Analysis

59

derived or altered signal is of more interest or use, or can throw more

light on the original signal. For instance, you could measure the
charge transferred at the working electrode by integrating the current
signal with respect to time. EChem has a number of computed
functions that can be applied singly or in combination, before or after
recording. EChem always retains the raw data in memory, so the
unaltered voltammogram (or amperomogram) can be retrieved at any
time simply by turning all computed functions off. The E Channel
allows only one computed function to add or subtract a constant
value.
The Computed Functions dialog box, Figure 422, lets you set up data
manipulation of various sorts. Choose the Computed Functions
command from the Display menu, or type Command-F (Macintosh)
or Control-F (Windows PC). The function, or functions, chosen will
apply to all pages in the le until you change the settings.

Figure 422
The Computed Functions
dialog

Sampling Speed
Computed functions do not affect sampling speeds, or scan rates, but
they may affect the delay between consecutive sweeps. The speed
with which computations are applied to the data is directly related to
the speed of the computer, so slower models will give longer delays.
If this proves to be a problem, perform computed functions after the
data has been collected.

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Channel Functions
The dialog box has one panel for I Channel and one for the E
Channel, in which functions for the two channels can be set
independently. If multiple functions are applied, their order is from
the top to the bottom of the panel: the waveform is rst smoothed,
then shifted, and so on. The display panel at the bottom of the dialog
box indicates this order (and the display settings, as well).

Figure 423
Smoothing of data

No smoothing

Smoothing value of 1

Smoothing value of 20 too much

smoothing gives distorted peak shapes

Smooth
Data can be smoothed to remove noise in the current signal. If the
control is set to zero, then smoothing is off (the default); the larger the
number entered, the greater the smoothing, Figure 423. Click the
up/down arrow buttons to alter the degree of smoothing; hold the
mouse down continuously to increase or decrease the number

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61

rapidly; or type a value in the text box to directly set the degree of
smoothing, from 1 to 50. For n point smoothing, at each data point
p the values of the data points in the range pn are averaged (i.e. a
moving point average is taken). At the very start and end of the
voltammogram (or amperomogram) there may be insufcient points
to complete a full n point smoothing and the amount of smoothing
will not be as great. Smoothing will affect different waveforms in
different ways: voltammograms with sharp peaks cannot be
smoothed too much without distortion, but those with broad peaks
can be smoothed a lot more.

Math
The Math control lets you add, subtract, multiply or divide the data
by a constant amount. By default, the setting is None (no operation is
applied) and the text entry box and units control are dimmed. Choose
an operation from the Math pop-up menu, Figure 422
Add or Subtract. If you choose one of these, the text entry box and
units control become usable. You can add or subtract a constant
amount from the signal. Type the value in the text box: it can be up to
30,000, and be set to four decimal places. The units are set by using
the up/down arrow buttons. You may want to add or subtract a
constant value to the E Channel if you have recorded a
voltammogram with a Ag/AgCl electrode but want to change the
display so that zero volts corresponds to use of a calomel or standard
hydrogen electrode.
Multiply or Divide. If you choose one of these, the text entry box
becomes usable. (The units control does not, since you are
multiplying by a scalar number.) Type the value in the text box: it can
be up to 30,000, and be set to four decimal places, although you
cannot enter zero.
Invert. If you choose Invert, the text entry box and units control
remain dimmed. Invert changes the sign of the signal, effectively
multiplying it by minus one: positive values become negative, and
vice-versa. This is usefulness the E channel if you recorded data with
one polarity convention (say, more negative potentials mean greater
reduction) but then later want to display data with the opposite
polarity convention (more negative potentials mean greater
reduction).
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Function
The Function pop-up menu gives a range of available functions that
can be applied to a signal. By default, the setting is None; if you want
a function applied, choose it from the pop-up menu.
Reciprocal. This function displays the reciprocal of the current signal,
that is, 1i for any data point of value i (so zero values will become
innite).

Figure 424
Integration of data

Original voltammogram

Integrated voltammogram

Voltammogram after blank page subtraction

Integration of subtracted voltammogram

Integrate. The Integrate function measures the area under a

waveform, calculated as the sum of the data points multiplied by the
sample time interval. The integral over a time with of the current
signal will have units of charge (an [Link] is a coulomb).
The integral function works best when the voltammogram or
amperomogram has a at baseline close to zero current, Figure 424.

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63

Apply the Integrate function rst, then use the Subtract Background
command to subtract a blank run to achieve a better result. If you
Subtract Background rst, then integrate this will NOT work!
.Differentiate. This function gives the rst-order derivative of the
current signal with respect to time (di/dt), Figure 425. It is useful
when the voltammogram shows ill dened peaks or shoulders where
the differential may give a resolved signal. The Differentiate function
is particularly sensitive to noise, so its use with the Smooth function,
is often necessary.

Figure 425
Differentiation of data

Original voltammogram

Differentiated voltammogram

The Notebook
You can enter your observations and notes in the Notebook, Figure
426, which is saved along with the EChem le. To use the Notebook,
choose Notebook from the Windows menu.
The Notebook has a total of eight numbered pages that can be used
for general notes about a le. Each page can contain up to 32,000
characters, and you can scroll vertically through the contents using
the up and down arrow keys on your keyboard.
Clicking the dog-ears at the lower left of the window turns the pages
back and forth. Click the Date or Time buttons at the bottom of the
window to add the date or time to your notes at the insertion point.
The commands Cut, Copy, Paste, and Clear can be used to edit text
normally, although you cannot paste graphics into the Notebook. You
can also paste text from the Notebook into word processor documents.

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Figure 426
The Notebook window

Write your notes

here

Click here to
move to
next page

Click here to
move back a
page

Click this button to

add the time at the
insertion point
Click this button to add the
date at the insertion point

Printing the Notebook

When the Notebook window is active, then the Print option in the
File menu changes to Print Notebook, and if the command is
selected, the contents of this window are printed rather than those of
the EChem window. The Print dialog box allows you to print the
entire contents of the Notebook, or any selected page range (EChem
will not print empty Notebook pages). The pages are printed out as
they appear on screen. You can copy the contents of the Notebook to
the Clipboard for pasting into a word processor if this is more
convenient.

The Page Comment window

The page comments feature allows you to annotate your individual
voltammograms. (The Notebook, above, allows you to make more
general comments about the recording as a whole.) Comments must
be entered after recording, and once entered, can be edited.
The Page Comment button can be found at the bottom left of the
EChem window, to the right of the Marker (Figure 23). When there
are comments noted down for the active page, the button icon
changes from a blank note to a marked one. Click the button to bring
up the Page Comment window, Figure 427.

Chapter 4 Data Display and Analysis

65

Figure 427
The Page Comment window

Comment text can be typed in here

and edited normally
Information on the date the page
was modied or the number of
pages averaged is given here

A comment can be typed in (or pasted into) the window, and text
there can be edited normally. For practical purposes, the text should
not be too lengthy (say over 300 characters), since more than that will
make the comments difcult to read in the window, although you can
autoscroll up and down through them using the arrow keys.
The box at the bottom of the window shows the time and date the
page was recorded or otherwise modied.

Printing Page Comments

Whenever a EChem page is printed, Page Comments are printed
beneath the waveform pictures. If comments are lengthy, the
voltammograms will be printed in a reduced area. If the comments
are very lengthy, they may also be truncated.

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C H A P T E R

F I V E

Working With Files

EChem data les can be edited, printed, and saved to disk in various
formats. This chapter describes these operations, and such features as
creating a single le summarising results from many les, and saving
settings to allow easy repetition of an experiment. Other topics
covered include the transfer of data to other programs, such as
spreadsheets and graphing software, and the use of page comments
and the Notebook.

EChem Users Guide

67

Selecting Data
Figure 51
A selection rectangle in the
Main window

To select a region of data position the pointer, then click and drag to
highlight a rectangular area. When in the i vs E display mode, the
minimum horizontal extent of any selection in the Main window is
four data points.
When in the iE vs t mode only the vertical extent of the selection
rectangle can be varied, with the horizontal extent being the whole
page. If the channels are split (not overlaid) then you can select a
region on the rst channel then, holding the Shift key, select a region
on the second channel. If the two channels are overlaid, simply drag
to create a common selection rectangle over both channels.

Figure 52
Examples of selection
rectangles in the two different
display modes: above is the
i vs E mode, and at bottom
the iE vs t mode

Editing Data
The Cut, Copy, Paste, and Clear commands appear in the Edit menu.
These commands can be used to copy selection of the text entries in
the Page Comment or Notebook windows and to paste the text into
word processor or spreadsheet documents.

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When the Main window is active, the commands work with whole
pages of EChem data rather than selections. Cut removes the active
page from the le and places it on the Clipboard. Copy places a copy
of the active page on the Clipboard. Paste adds a page already on the
Clipboard to the le before the currently selected page. Clear removes
the active page from the le. If the Zoom window is active, the active
page is still affected rather than the selection that the Zoom window
is showing, for most purposes.
All these commands are able to be undone (only a single level of
undo is supported). The Undo command, appears in the Edit menu,
and changes to reect your last action. If you have just, for instance,
removed a page from the le by choosing Clear from the Edit menu,
then the menu command will change to Undo Clear Data. (Should
you choose the command again, it becomes Redo Clear Data.)
The editing commands allow you to move pages about and to delete
those you do not want. You can move a page between les by placing
it on the Clipboard and opening another le (closing the current one,
since Scope can only have one le open at a time), then pasting it
where it is wanted. Paste inserts the page on the clipboard
immediately before the active page.

Transferring Data
You can transfer graphs from EChem to other applications, such as a
spreadsheet or drawing program. The Cut and Copy commands
place the Main and Zoom windows on the Clipboard as a picture.
(The same pictures you would see if the windows were printed, with
title, page comments, and so on, but without overlaid pages.) The
Clipboard contents can then be pasted into drawing software such as
Canvas or CorrelDraw which have extra features to modify the
picture for presentation purposes. However the best results are
usually obtained by transferring the data itself to a specialist
graphing program.
An EChem data le can be saved as an ASCII text le able to be
opened by any application that can import text, such as a word
processor, spreadsheet, or graphing program such as Igor Pro,
Kaleidagraph or Origin (to do this, choose the Save As menu
command from the File menu.)

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69

Special Copying
EChem also has a more powerful method of copying text or graphics
to the Clipboard for data transfer, the Copy Special command, in
the Edit menu. It allows the copying of overlays in pictures (which
the Copy command itself does not), and the copying of multiple
pages or even an entire le, as text. Choosing the Copy Special
command when the Main window is active brings up the Copy to
Clipboard dialog box (Figure 53).
Figure 53
The Copy to Clipboard dialog
box.

The dialog box lets you choose one of two options: copying the Main
window as a picture; or copying it as text. If the Append to Clipboard
checkbox is turned on, data in text form from the Main window can
be appended to the contents of the Clipboard, rather than replacing
its contents. The control is dimmed and unavailable if you are
copying a picture.
As a Picture. If this radio button is on, then the EChem window,
including visible overlaid pages, is placed on the Clipboard as a
QuickDraw picture. (The same picture you would see if the window
were printed, with title, page comments, and so on.)
As Text. If this radio button is on, then the data from the EChem le
is placed on the Clipboard as tab-delimited text. The Copy page
numbers checkbox allows you to precede the data with the page
number if required. If page overlaying is turned on, then the data for
entire le will be copied to the clipboard, regardless of which overlaid
pages are visible (if any); if it is off, only the active page will be
copied. Use this option for pasting data into spreadsheet or graphing
applications.

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A similar dialog box appears when you choose Copy Special with
the Zoom window active. When the Zoom window is active, the
picture copied is conned to the selection that the Zoom window
displays.

The Clipboard
Whenever data is cut or copied from EChem, it is stored in the
Clipboard. You can choose Show Clipboard from the Edit menu to see
what is copied: the Clipboard window appears (Figure 54). The
Clipboard window is a normal window with a close box, zoom box,
size box, and title bar, and can be moved around the screen or left in
the background while the EChem window is active.
Figure 54
The Clipboard window as it
might appear after copying:
Copy from the EChem window
produces a picture (near
right); Copy Special, as text,
with potential values in volts
and current in amperes (far
right). Other text format
options allow time and page
number to be copied as well.

The Clipboard window shows either a representation of a picture

(sized to t the window), or rows and columns of data in text format,
depending on what has been copied. If a very large selection is made,
the process of copying may take some time.

Measuring From the Waveform

When you have nished recording, you can go though your data and
make measurements directly from the recording since everything
is digital, you are given a direct read-out, with no chance of the errors
in reading that could occur in analysing a paper-and-ink record. You
can make direct or relative measurements.
When the pointer is over the data display area, the Waveform Cursor
tracks the waveform. The display in the Cursor panel shows the

Chapter 5 Working With Files

71

current and potential value at the waveform cursor location. This is

irrespective of the display mode.
Waveform Cursor

Current and
potential values
at waveform
cursor position

Figure 55
Operation of the waveform
cursor in the main window

The pointer appears as a cross over the data display area. The
Waveform Cursor only gives discrete measurements, jumping from
data point to data point (you can see this more clearly in the Zoom
window). It cannot provide a reading on the line that is drawn
between the points.

Using the Marker

The Marker can be found in a box at the bottom left of the Main
window (Figure 56). It is used to set a particular data point as a zero
reference point, so that relative measurements can be made with
respect to that point. To set the reference point, drag the Marker from
its lair into the main window: it will lock onto the waveform when
you release the mouse button (Figure 56). Option-drag to position
the Marker independently of the waveform. Use the Waveform
Cursor display in the Cursor panel to help to select a data point. If
you need ner control of where the Marker ends up, use the Zoom
window to look at a selection in more detail: the Marker is duplicated
there, and can more easily be assigned to a particular data point.
When moving between pages, the Marker will remain at the same
time position: if locked to the waveform, it will lock to the new
waveform amplitude at that time; if independent, it will remain static.
Double-clicking the Marker or clicking its box at the bottom left of the
main (or Zoom) window sends it back home.

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Once the Marker is in position, current measurements relative to it

(preceded by ) are given in the Waveform Cursor display. The
potential at the Waveform Cursor position is absolute. The symbol
before the current value indicates that it is a difference, not a direct
reading.
Amplitude of current at
the Waveform Cursor
position relative to Marker

Marker
Figure 56
The operation of the marker
and waveform cursor in the
main window.

Markers lair

Setting and Removing Baselines

In iE vs t display mode the Marker can also used for setting relative
amplitude measurements where the baseline of a channel is not zero.
Once you have recorded a waveform, you may nd that the baseline
value is not at zero potential (or set units) when it should be that is,
there is some slight offset. You may want to measure features of a
waveform relative to a series of other features. In either case, a
baseline should be set up for the channel of interest. To do this, place
the Marker at a point you want the baseline to intersect. Then
Command-drag from the Marker lair or the Marker itself: this creates
a duplicate Marker, which can be placed in the same channel to set
the second point the baseline intersects (Command-Option-drag to
place this duplicate independently of the waveform). The baseline is
displayed as a dotted line passing through the two Markers.
The value along the baseline is set at zero: the Waveform Cursor
display in the Cursor panel shows the absolute potential, and the
amplitude of the current relative to the baseline (Figure 57).
Note that the baseline is set for a particular page of data. When
moving between pages, the baseline may move considerably if locked
to the waveform; if independent, it will remain static. Removing one
Marker removes both Markers, and the baseline.
Chapter 5 Working With Files

73

Figure 57
Setting a baseline in the main
window in iE vs t display mode

Current relative to
pointer position

Pointer
Cursor

Potential at Cursor
position

Marker
Duplicate Marker

Baseline

Attempting to set a vertical or near-vertical slope will also remove the

baseline and send the Marker and its duplicate home. The marker has
no effect if placed on the potential (E) waveform.

Saving Options
To save a le of recorded data, choose Save from the File menu, or
type Command-S. When this is done, an already existing le will
have any changes made to it saved to disk. The rst time that you
save a le, or on any occasion that you choose Save As from the File
menu, the Save As dialog box will appear (Figure 58).

Figure 58
The Save As Text dialog box

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EChem Users Guide

The dialog box allows you to navigate through the le system of the
Macintosh to choose where your le will be saved. (You should be
familiar with this process; if not, see your Macintosh Users Guide for
directions.) Once you have typed in a name for the le, you can select
a le format by clicking one of the radio buttons in the lower portion
of the dialog box, and then save the le by clicking the Save button.
You can save multiple copies of a le in any format or formats,
provided that the copies have different names or are in different
folders.

Data File
In this format, which is the default, both data and settings (including
macros) are saved. The le chronicles the entire recording, and is the
usual way you would want to save data. EChem can open only one
le at a time. Opening a data le will close an already opened le.

Settings File
This format does not save any recorded data, only the settings.
Settings include the technique, current range, and those that affect the
way the data looks, such as the window size, display settings, and
menu conguration. Macros are also stored as settings. Using settings
les, you can build up a library of settings for many different
experiments, to enable quick and easy preparation for recording.
Settings les have a different icon from other EChem les. Doubleclicking on a settings le icon from the Finder will automatically load
the settings from that le into a new untitled EChem le. Opening a
settings le using the Open directory dialog box with the Load
Settings checkbox selected loads the settings into the current le.

Text File
This format saves data as a standard text le able to be opened by any
application that can import text, such as a word processor, spreadsheet, or statistics package. Each data point is stored as a row of
numbers comprising the page number, time (t, in seconds), potential
(E, in volts) and current (I, in amperes) values, in that order, separated
by tabs.

Chapter 5 Working With Files

75

Figure 59
The Save as Text dialog box

Before the a text le is saved, you will be presented with the Save as
Text dialog box (Figure 59). The save page numbers checkbox allows
you to omit or include the page number and time data from the le.
Additionally you can save the calculated current (i.e. the currents as
they are displayed) or the raw current data. There may be up to four
current sampling periods, i1, i2, i3, and i4 for each displayed data
point. Differential methods (for example differential pulse
voltammetry) require two of these sampling periods but normally
only display the difference (for example i1 -i2). Usually you want to
save the data as it is displayed but by selecting Raw currents you
can save the actual data collected separately for the i1 and i2 periods.
See Chapter 7 for more details about sampling periods.
Thus at most one row of the text le could have seven items: page
number, time, potential, i1, i2, i3, and i4. For simple regraphing of a
voltammogram using a spreadsheet, however, you only require three
items: page number, potential and calculated current. If you only
want to regraph a few voltammograms from a le then it will
probably be easier to use the Copy Special command in the Edit
menu and to paste the data directly into the spreadsheet or graphing
program.
The size of a text le is typically much greater than the size of the
EChem data le it is created from, and saving the data of a le as text
can be relatively slow. While a le is being saved as text, the
percentage of the le currently saved is displayed. To stop the
creation of a text le, type Commandperiod (or Controlperiod).
The EChem Data File format actually contains much more
information (names of the techniques used, date and time of
experiment, user annotations, range settings etc.) and all in a much
more compact format than a text le, so you should always keep the
original data as an EChem Data File and only ever use a text le to
transfer data to another application. You can always regenerate a text
le from an original EChem Data File if required.

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Macro File
This format saves any macros currently in memory as a separate le,
which can be opened by EChem as required. It is useful to save
particular groups of macros together.
Macro les have a different icon from other EChem les. Doubleclicking on a macro le icon from the Finder will automatically load
the macros from that le into a new untitled EChem le. Opening a
macro le using the Open directory dialog box (whether or not the
Load Settings checkbox is on) loads the macro into the current le.

Appending Files
This feature allows any EChem data le to be appended to the end of
an already open le in order to produce a single le with the desired
contents. By combining this feature with EChems ability to cut and
paste pages of data in a le or between les, summary les can be
created using only those segments of recordings that have
signicance. Appending a le is an option provided in the Open
directory dialog box: choose Open from the File menu. (If you have
made changes to your le since last you saved, you will be asked if
you want to save them.) The Open directory dialog box appears
(Figure 510) and by default only EChem les are shown in the
scrolling list. You can navigate through your hard disk using the
Macintosh hierarchical le system to nd the le you want.
Click the Append to Current File checkbox to turn it on. Note that the
Load Settings checkbox becomes dimmed and unusable, since the
appended le takes on the settings currently in memory. This may
result in some scale changes, but the raw data will not be altered.
Select the EChem le you wish to append to the currently open le,
and click the Open button to perform the operation. The pages will be
added on to the end of the current le.

Text Files
EChem can open text les, or append them to already open les. To
do this, choose Open from the File menu. The Open directory
dialog box appears (Figure 510) click the Text Files radio button

Chapter 5 Working With Files

77

Figure 510
The Open dialog box with the
Append option selected

so that only text les will appear in the scrolling list. The Load
Settings checkbox becomes dimmed and unusable, since text les
cannot contain settings data. The text le must can have several
different formats and the items in each row must be separated by
tabs, commas, or semicolons. Typical formats are:

potential (E, in volts) in column 1, and current (I, in amperes) in

columns 2.

current (I, in amperes) in column 1, and potential (E, in volts) in

columns 2.

time (t, in seconds) in column 1, potential (E, in volts) in column

2, and current (I, in amperes) in columns 3, 4, 5, and 6 (these will
be read as current sampling periods i1, i2, i3, and i4). Columns 4,
5, and 6 are optional.

You can navigate through your hard disk using the Macintosh or
Windows le system to nd the le you want. After a text le has
been selected in the Open directory dialog box and the OK button has
been clicked, the Read Text Options dialog box appears (Figure 511).
Read Time Values. If this checkbox is on, EChem reads in the rst
column of numbers as time values. EChem expects a constant
difference between time values: a discontinuity is treated as the start
of a new page of data. The minimum selection in EChem is four data

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EChem Users Guide

Figure 511
The Read Text Options
dialog box

points: thus any times read in must have at least three consecutive
intervals the same to create a new EChem page of data. If times are
not read in, then the EChem Time axis will have no units.
The Time Units radio buttons allow you to specify the time units of
the time values.
EChem rst scans the le to see if it is in order. If there is a problem,
such as erratic time values or text where it expected numbers, it alerts
you and does not load the le. It also allows you to

Pasting in Text
Copied text from data les (such as Scope software) of other software
can be pasted into EChem directly. The text copied to the clipboard
must be in a correct format.

Printing
Printing an EChem le or parts of it will give you a hard copy of your
data for use in reports and presentations. There are two menu
commands in the File menu concerned with printing: Page Setup
and the basic Print command (with a keyboard equivalent of
Command-P, or Control-P), which may change depending on what
can be printed at the time.

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79

Page Setup
The Page Setup dialog box that appears when you select the Page
Setup command will depend on your chosen printer (and system
software). A typical Page Setup dialog is shown in Figure 512. The
users guide that came with your printer will explain most of what is
involved. Choose the paper size that you will be using, page
orientation, and so on.

Figure 512
A Page Setup dialog box for
an Apple LaserWriter 12/640
on Macintosh (upper) and on
a Windows PC (lower). Other
printers will exhibit different
options.

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EChem Users Guide

Waveform Print Layout

Click the appropriate Waveform Print Layout buttons to print one,
two, three, four, or six EChem pages per printed sheet of paper. By
default, the leftmost button is selected, and one EChem page appears
on a printed sheet. The page range specied when printing refers to
EChem pages, not pieces of paper produced: printing six pages
would, if the rightmost Waveform Print Layout button were selected,
produce one printed sheet with the six data pages on it.
On a Macintosh this feature will work in conjunction with the Layout
option in the LaserWriter 8 Print dialog box, which gives you the
choice of one, two, or four, eight or sixteen pages per sheet of paper,
so that you could print up to 48 EChem pages per sheet but this
would results in tiny graphs!

High-Resolution Printing

Note
For the best possible
printing, ensure that you
are using the latest
version printer driver for
your particular printer.
Many manufacturers
allow you to download the
latest printer drivers from
their web sites.

Some printers support several modes of resolution. Checking this

option allows you to print the EChem or Zoom windows at the
maximum resolution of the printer. For example, if you are using a
600 dpi laser printer, EChem will print with a resolution of 600 dots
per inch. This will result in output of the best possible quality, but,
since every data point and connecting line is drawn at full resolution,
printing may be slow.
Without high-resolution printing, the accuracy of positioning items
(data points, axis tick marks and labels, etc.) is not as accurate on the
printed page. This may still be adequate for drafts and overviews,
and will result in quicker printing.

Faster Printing
If Faster Printing is not selected, EChem passes the recorded data to
the printer driver, which generates a set of instructions which are
passed to the printer. If there are many data points in the le, the
printer driver software has to work harder at converting the data
points into the printer instructions, which will take more time.
When Faster Printing is selected, EChem attempts to speed up
printing by creating a bitmapped image of the data to be printed.

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81

Since the le itself, the chosen resolution, the printer, and the type of
computer all have a bearing on the speed of the process, this will not
always result in faster printing. Try a few pages with your setup to
establish relative speeds using this method and printing normally.
When faster printing and high-resolution printing are both selected,
EChem determines the resolution of the printer and generates a
bitmap at that resolution (if the printer resolution cannot be
determined EChem just generates a low resolution bitmap). This
rasterised image is then transferred to the printer directly rather than
having to be converted to PostScript, or other printer instructions.
The time saving can be quite signicant on les with large numbers
of data points, with little or no loss in resolution, but it is possible that
it could take longer with some systems. On Macintosh computers
EChem must be given enough memory to image the data at high
resolution. An alert box will warn you if memory is insufcient.

Print Using Color

Checking this option enables color printing of your data. You can set
the data display colors using the Display Settings dialog box (and
similar dialog boxes). Some colors may not be supported by certain
color printers, or the colors actually printed may differ from those
that appear on a color monitor. Try a few samples with your
equipment to establish color compatibility.

The Print Command

If the Page Comment or Clipboard windows are active, the Print
command is dimmed and cannot be chosen. In other circumstances
the command will be enabled and will appear slightly differently
depending on which window is active (Table 51).
Print Command
Table 51
The results of the various
print commands

82

Active (Top) Window

What Prints

Print

Main

Page range or current page

Print

Zoom

Zoom window contents

Print Data Pad...

Data Pad

Data Pad contents

Print Notebook

Notebook

Notebook contents

EChem Users Guide

When a Print command is chosen, the Print dialog box for your
printer appears. EChem provides special options: the Print Current
Page Only and Print Sweep Description [Link] the Print
Current Page Only checkbox is on, the active page prints regardless of
the specied page range. To print a range of pages, turn off the
checkbox and enter the page numbers as usual. When the Print
Sweep Description checkbox is on, the parameters displayed in the
Technique Description panel (Figure 23) are also printed underneath
each graph.

Figure 513
A Print dialog box for an Apple
LaserWriter 12/640 on
Macintosh (upper) and on a
Windows PC (lower). Other
printers will exhibit different
options.

Chapter 5 Working With Files

83

When printing the contents of the EChem or Zoom windows, the

Page Layout dialog box pops up after you click OK in the Print dialog
box. This dialog box lets you adjust the size, location, and proportions
of the image. Drag the image to reposition it on the page (the gray
border shows where it will go), and drag the gray box at the bottom
right of the image to adjust its size.

Figure 514
The Page Layout dialog box

Drag the
image to
where
you want
it on the
page

Turn off this

checkbox to
reshape the
image
Drag the gray box to
resize the image

You can also double-click the image to scale it to the maximum size
that will t on the page. If the Keep Shape checkbox is checked, then
the image is scaled in proportion to its original dimensions (which
depend on the window settings), otherwise it can be reshaped at will.
If, however, you are printing multiple EChem pages on a page (using
the Waveform Print Layout controls in the Page Setup dialog box),
you will see a number of rectangles in the page area rather than the
image of one page, and the Keep Shape checkbox will not appear.
The le title, page number, and any page comments are included in
the printed EChem page. Long comments mean the area used for the
drawing is reduced; very long comments will be truncated.
The Notebook is printed out looking much like it does on screen, but
empty columns are not included in the hard copy.
On a Macintosh printed text will appear in the Geneva font, unless
you have a PostScript LaserWriter and check Font Substitution in its
Page Setup dialog box, in which case Helvetica will be used. If you
are using the TrueType Geneva font in your Mac OS, the text will be
printed at the maximum resolution of the printer on any printer.
Faster printing always produces a bitmap with no substitution of
fonts taking place.

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On a Windows PC a default font will be used.

While the le is printing (or being spooled, if you are printing in the
background) a small dialog box appears. Click its Cancel button to
stop printing (or type Command-period, or Control-Period, or press
the Return, Enter, or Esc keys).

Chapter 5 Working With Files

85

86

EChem Users Guide

C H A P T E R

S I X

Customizing &
Automating EChem
You can to customise and to automate functions within EChem,
greatly increasing its convenience and ease of use. It can be simplied
or modied by:

locking or hiding menus or commands with the Menu Editor

altering controls, menus, and menu commands, and moving

control panels then store your changes as a Settings File or as
the Default Startup.

storing techniques with precongured parameters (initial and

nal potentials, scan rates, pulse heights etc.) as Settings Files.

automate complex tasks by creating multi-step Macro

commands which can be stored as new commends in new or
existing menus.

This chapter looks in detail at these various ways of altering EChem

to suit your experimental requirements.

EChem Users Guide

87

Preferences
The options in the display settings and recording controls allow basic
customizing of EChem. You can also choose to lock, hide, or alter
controls, menus, and menu commands (and their keyboard
equivalents). This can be particularly useful in simplifying EChem for
teaching purposes.
The Preferences submenu in the Edit menu contains four menu
commands: Options; Menus; Controls; and Start-Up. These allow you
to alter various aspects of EChem performance and display.

Menus
The six EChem menus (File, Edit, Technique, Display, Windows,
Macro: see Appendix A1) and their commands can be modied from
the default settings by using the Menus dialog box (Figure 61),
which appears on selecting the Menus submenu command. You
can hide or lock any menu or menu command to create a very simple
EChem setup, limiting the actions that can be performed. This is
particularly useful when you want inexperienced students or
technicians to be able to use some features of EChem, but not to edit,
delete, or change the data in les.
Figure 61
The Menus dialog box

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EChem Users Guide

The dialog box will initially display the File menu. To move to the
dialog boxes of adjacent menus, click the arrows by the dialog box
title, or press the right or left arrow keys on the keyboard. Click the
OK button to apply any changes you have made.
Menus that are too long to t entirely within the dialog box will have
a downwards pointing arrow at their base: click it (or press the down
arrow key on the keyboard) to move through the menu; click the
arrow that appears at the top of the menu (or press the up arrow key)
if you need to move up again. By default, the menu title and all items
within the menu will have a tick to their left, and all menu commands
will have an open padlock beside them, indicating that everything is
visible and unlocked.
Clicking the tick beside the menu title will hide the menu (a cross
appears): it will not appear in the menu bar when you return to the
EChem window. Clicking the tick beside a menu command or a
dividing line will hide it: it will not appear in the menu, and neither
will any Command-key equivalent work. Clicking a cross will change
it to a tick, and show the previously hidden item beside it.
Clicking an open padlock changes it to a closed padlock, and locks
the menu command beside it. The command will still appear in the
menu, but it will be dimmed and cannot be activated (if there is a
Command-key then this will also be inactivated). Clicking a closed
padlock changes it to an open padlock, and unlocks the previously
locked menu command beside it.

Command-Key Equivalents
Some menu commands have Command-key equivalents. The
equivalent key appears selected in the text entry box, and you can
either change it, or delete it so that no Command-key equivalent is
available.
Command-key equivalents for menu commands can also be added or
changed. Click a menu command to select it: the Cmd Key area of the
dialog box becomes active. Type a single lower-case letter (a, b, c, ...)
or number (1, 2, 3, ...) in the text entry box (letters are automatically
capitalized; invalid characters will be rejected) and click the Set
button to assign a keyboard equivalent. If you choose a character in

Chapter 6 Customizing & Automating EChem

89

use elsewhere, an alert box will warn you. If you choose the character
anyway, your choice overrides the previous assignment.

Controls
On selecting the Controls submenu command, the Control Options
dialog box appears, Figure 61. It lets you modify the display of the
various EChem Control Panels, Figure 23. By default, all items will
have a tick to their left, and the icons show the tall window to the left
in front of the panel to the right, indicating that everything is visible
and that panels will appear behind the Main window in case of
overlap. You can hide any EChem panel to create a very simple
EChem setup, if you want to limit the actions that can be performed.

Figure 62
The Control Options dialog

Clicking a tick will change it to a cross, and deactivate the panel: it

will not be visible when you return to the EChem window. Clicking a
cross will change it to a tick, and return the previously hidden item to
view.
Panel in
front
Main window
in front

The icons show two overlapping rectangles. By default, the tall left
rectangle is in front (the panel to appear behind the main EChem
window in case of overlap). Click the icon, to make the short right
rectangle appear in front, if you want the panel to appear on top of
the EChem window. Click it again to revert to the default setting.
You can also change the overlap order can be by Option-clicking the
tile of a panel in the main EChem window.

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The vertical space (the blank space above the sample panel), and
EChem title can also be hidden.

Moving Control Panels

The panels represented in the Control Options dialog box can all be
moved around your Macintosh screen if you want to alter the default
arrangement. When you hold the Shift key down you can drag a
panel by its title to move it. The pointer changes to an arrow-headed
cross, and as you drag, a gray outline indicates where the panel will
go.
The vertical space and description panels can be Shift-dragged from
any point in them.

Options
The EChem Options dialog box, Figure 63, is opened by the
Preferences/Options command in the Edit menu.

Figure 63
The Echem Options dialog

The Auto Save Data checkbox will cause the EChem le to be saved
immediately after every sweep. It is on by default. You may wish to
turn it off if you want to do a succession of sweeps with the minimum
delay period between each sweep, or if you have set up a series of
macro commands and want to also set up the Save command from
within a macro.
Figure 64
The Display pup-up menu
can be shown (upper) or
hidden (lower).

The Keep Partial Data checkbox is also on by default. It will keep a

partially completed voltammogram if you prematurely halt scanning
by clicking the Stop button in the main display before an experiment
has nished.
The Show Display Control checkbox allows you to show or hide the
Display pop-up menu, Figure 64. So that the user can no longer alter
the display (I vs. E, IE vs. t t, etc.)

Chapter 6 Customizing & Automating EChem

91

Start-Up
When EChem rst starts up, it will use its factory default settings,
taking the whole screen for its display, with the current range on the
lowest sensitivity, and so on. You can alter these defaults so that
EChem will always start with your preferred settings.
Settings are of two sorts: those that affect recording, such as the
technique and channel ranges; and those that affect the way the data
looks, such as the window size, channel areas, display settings, and
menu conguration. To save or clear customized settings, select the
Start-Up submenu command: the Start-Up Settings dialog box
appears (Figure 65).

Figure 65
The Start-Up settings dialog

Clicking the OK button will save all current settings in the EChem
Settings le in the Preference folder in the System folder so that they
are used each time you start up EChem. Clicking the Clear button
will clear any settings currently stored in the EChem Startup le.

Emergency Access!
Note
If you have created startup settings but want start
up EChem with its factory
default settings, on a onetime basis, hold down the
Command key as you open
it (straight after doubleclicking the icon). Release
the key when the alert box
appears, and click the OK
button.

92

Because it is possible to change menu preferences so that vital menu

commands are locked or menus themselves hidden, it is necessary to
be able to have a way to get them back. Emergency access to dialog
boxes is available through the Show Dialog Box dialog box (Figure
66), which appears on typing Command-\ (backslash).
Clicking the Menu Editor button will bring up the Menus dialog
box (Figure 61), allowing you to show hidden menus, and to unlock
menu commands.

EChem Users Guide

Figure 66
The Emergency Access
dialog box

Clicking the Start Up button will bring up the Start-Up Settings

dialog box (Figure 65), allowing you to save the current settings in
the le (including menu layouts and so on) as those EChem will use
when it starts up.
Clicking the Save As button will bring up the Save As dialog box
(Figure 58), which allows you the complete range of options in
saving a EChem le. This is useful to save the le as a Settings le
with the hidden or locked menu items remaining as specied when
the le is saved.

Chapter 6 Customizing & Automating EChem

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Macros
Macros are used to group sets of commands together conveniently,
enabling you to speed up repetitive and tedious tasks, such as
changing the settings for various parts of an experiment, and to
automate recording and analysis. They record the results of your
actions step by step, then reproduce them when played back. If you
nd yourself regularly doing the same series of operations in EChem
macros can automate things considerably.
Macros can record any EChem operation: setting dialog box and
window controls; changing the display format; saving data as a new
le; printing the Zoom window; and so on. There are some
differences involved in recorded and real operations, but in general,
dialog boxes will guide you through your options.
It is important to understand how macros work: they record the
results of your actions, not individual keystrokes and mouse clicks,
and record the simplest possible interpretation of those actions. Even
if you spend some time ddling with control settings during the
recording of a macro, only the nal settings you obtain will be used.
Macros are not able to be edited.
You should keep a written record, in a notebook, HyperCard stack, or
whatever you nd most convenient, of the steps involved in your
macros, and their purpose: it is easy to forget which macro does what
when you havent used them for a few weeks. Noting the steps down
before actually recording will help when constructing complex
macros, since it can prove easy to miss out a step or end a repeated
sequence in the wrong place, with detrimental effects.

Macro Hint
Macros cannot be edited
but they can activate other
macros. It is usually better
to write several small
macros and to use a master
macro to call each of them
in turn. If you make a
mistake then you will only
have to rewrite the macro
the error is in.

94

Macros are saved as part of a normal data le, or can be saved as a

separate le on their own. In either case, any macros currently in
memory are saved to the le. They are loaded into memory whenever
data or settings from the le that contains them are loaded, effectively
adding to the EChem application (this is one reason why they are
stored in as compact a way as possible). Hence if you load three les
in succession, with a different macro in each, then all three macros
will be available until you quit and restart EChem, or delete the
macros. When a le is saved, all currently available macros are saved
with it, becoming part of the le.

EChem Users Guide

Recording a Macro
To record a macro, choose Start Recording from the Macro menu, or
type Command-R (the menu command then changes to Stop
Recording). During the process, a small indicator changes in the
display panel, and the message Recording is displayed to remind
you that your actions are being recorded, not effected. Perform each
action to be recorded, then choose Stop Recording from the Macro
menu, or type Command-R again. Once you stop recording, the Add
Macro to Menu dialog box appears (Figure 67). When a macro is
being recorded, for the most part EChem remembers rather than
executes operations, but operations such as changing current ranges,
for example, are done as you record.
Type here to create a new menu

Figure 67
The Add Macro to Menu
dialog box

Press here to select a menu to which

to add the macro
Type a name for the macro here
Assign a Command-key equivalent here

The pop-up Menu button allows you to select the menu in which
your macro will appear from a list of existing menus. By default, the
macro will be added as a new menu command to the Macro menu.
You can create a new menu by entering its title in the Menu text entry
box: the menu will be added to the right of existing menus in the
menu bar. The name of the macro (up to 20 characters) should be
entered in the Item text entry box.
An optional Command-key equivalent can be assigned to the macro
as well: type a single lower-case letter or number in the text entry box
(letters are automatically capitalized and invalid characters will be
rejected). If you choose a character already in use, an alert box will
warn you of the fact and tell you where it is assigned. If you choose
this character anyway, your choice overrides the previous assignment

Chapter 6 Customizing & Automating EChem

95

and the Command-key equivalent will only work for (and appear
beside) the menu command that you have just created.
The Size indicator tells you the number of steps recorded (useful if
you cant remember which step you are up to in the middle of a
complex macro), and the memory taken by the macro, so far. The
amount of memory used depends on the complexity of the
procedure. Click the Discard button to discard the macro you have
just recorded. Click the Cancel button to continue recording more
steps in the macro. Click the Add button to add the macro to the
bottom of the selected menu; the Add button is only active and
undimmed when the macro is named and a menu is chosen.
Until you save the le, the macro exists only in memory and is not
permanently stored. If you open another le and save that, the macro
(and all other currently available macros) will become part of the new
le. When you quit EChem, you will not be asked to save changes if
you have created new or altered existing macros. So it is a good idea
to save the le each time you create a macro (or save it as various
macro les).

Playing a Macro
Once assigned a name and location, macros act much as if they were
menu commands. Select them from their menu or type their
Command-key equivalent to use them. While a macro plays, the title
of the menu in which it resides is highlighted, and no other functions
can be performed within EChem, nor can one switch to another
application and leave EChem in the background. To stop a macro
playing, hold down the Command key and press Period (.). The
macro will stop at its current step.

Deleting a Macro
To delete existing macros, choose the Delete Macro menu command
in the Macro menu which brings up the Delete Macro dialog box
(Figure 68).
A scrolling list displays the name of the menu that the macro is in, a
colon, and the name of the macro, for all available macros. To delete a
macro, select it and click the Delete button. To delete multiple macros,

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EChem Users Guide

Figure 68
The Delete Macro dialog box

Shift-click or Shift-drag to select contiguous macros, or Commandclick (or Control-click) to select or deselect multiple macros
individually. The dialog box will close and the macro or macros will
be gone. As a shortcut, double-click a macro to delete it and close the
dialog box in one step.
As was mentioned, when a le is saved, all currently available macros
are saved with it. When you delete a macro, you delete it from
memory. If the macro is part of the current le, it is permanently
deleted from that le only when the le is saved. Copies of the same
macro that are part of other les will not be deleted.

Macros That Call Other Macros

Once a macro has been created, it can then be used by other macros
that you create. When constructing multistep procedures it is usually
best to call a series of small macros from a single master macro.
Macros can be nested up to ten deep. An alert box will appear during
the playing of your macros if the combination of macros becomes too
recursive.
If a macro is called by another macro, EChem will warn you if you
attempt to delete it. If you delete it without replacing it then, when
the deleted macro is called, an alert box will tell you that it cannot be
found.

Chapter 6 Customizing & Automating EChem

97

Options When Recording Macros

Operations involving les and dialog boxes can be made to behave in
different ways when playing macros, depending on whether you
want to do the same thing all the time, allow user modication, and
so on.

Changing Dialog Box Settings

Macros can be used to change dialog box settings to the values
specied when you record the macro, or to open a dialog box for the
user to change settings when the macro is played.
If you want a macro that changes the settings in a dialog box, then
select the dialog box as you would normally while recording the
macro. Change the settings, and then click OK in the dialog box. (If
you click Cancel, the changes made in the dialog box will be ignored.)
When playing the macro, the settings are changed without displaying
the dialog box.
If you want a macro that opens a dialog box for the user to change
settings when the macro is played, hold down the Option key when
selecting the command that shows the dialog box while recording the
macro, then click the OK button. Do not make any setting changes.
When you play back the macro, the dialog box is displayed so that its
settings can be changed by the user. Clicking the OK or Cancel
buttons in the dialog box will allow the macro to continue, with the
user-dened settings or the original settings respectively.
When changing control values in dialog boxes, absolute values are
recorded, not relative changes. For example, if you move a scroll bar
that increases potential by 50%, from 1V to 1.5 V, the new potential
(1.5 V) is recorded, not the change in voltage (+0.5 V) or the
percentage change in potential (+50%).

Starting Sampling
Macros can be used to control when sampling starts and stops: you
simply click the Start button when recording the macro, and EChem
will start sampling at the appropriate point when the macro is played.

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EChem Users Guide

Opening Files
A macro can be used to open the same le each time it is played, or to
allow the user to choose which le to open. To open a particular le
with a macro, choose Open from the File menu while the macro is
being recorded: the Macro Open directory dialog box is displayed
(Figure 69).
To allow the user to choose which le is to be opened when the macro
is played, press the Option key when selecting the Open command
while recording the macro. The Open directory dialog box will be
displayed when the macro is played.

Figure 69
The Macro Open dialog box

When opening the same le each time, the full hierarchical le name
(the pathname) of the le, from the disk through any number of
folders, is noted. If the le has been moved (or deleted) since the
macro was recorded, then EChem searches in the most recently used
folder and in the same folder as EChem. If the le is in neither of
these locations, an alert box lets you know that EChem cannot nd
the le, and the Open directory dialog box is displayed to allow you
to nd it yourself. If you choose a different le at this stage, it will be
opened instead and if you click the Cancel button, the macro will
abort.

Chapter 6 Customizing & Automating EChem

99

Saving Files
When playing a macro, you can save data in a le or in a series of
les. Choosing the plain Save command will save a named le (you
might want to do this at specied intervals to minimize data loss in
case of possible power loss; just remember that data is not recorded
during the time it takes to save a le to disk).
You can specify where and in what form you want the data to be
saved by using the Save As command when recording the macro.
The Macro Save As directory dialog box will appear (Figure 610).

Figure 610
The Macro Save As dialog
box

Three checkboxes in the Append le name with section of the

directory dialog box allow you to specify unique le names. If no
checkboxes are selected, then each time you play the macro, the le
will be overwritten, just as it is when saved normally.
If the Unique number checkbox is selected, a different number is
added to the end of the given le name each time the le is saved
during the playing of the macro. Numbers are added in numerical
sequence starting with 1. For example, if the le name is CoolData,
then the next les generated will be CoolData1 and CoolData2.

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EChem Users Guide

Selecting the Time checkbox appends the current time to the le

name. Selecting the Date checkbox appends the current date to the
le name. Both time and date are appended if both boxes are checked.
These checkboxes are dimmed and unavailable if the Unique number
checkbox is selected.

Macro Commands
Control structures for macros are provided in the Macro Commands
submenu in the Macro menu (see Appendix A1). The macro
commands are only available while recording a macro. They allow
you to provide user feedback in the form of dialog boxes or sounds,
set up repeat sequences, and so on.

Update Screen
Normally, when a macro is played, the screen is updated after each
macro step (a tick beside the Update Screen menu command indicates
that it is active). Choosing the command from the menu as the rst
step in a macro causes the macro to play without redrawing the
screen each time the data display is altered in some way (the tick
disappears). Update Screen can be turned off or on at any stage of a
macro (the settings toggle). If Update Screen is off, the screen will be
redrawn only when the macro is nished, or it is turned on again.
This may considerably speed up some macros, for example, those
involving multiple changes to view and display settings: in this case,
the data on screen will still be seen to be selected, but data off screen
will not be scrolled through before selection, as would occur if
Update Screen were off. Since you cannot edit macros, you cannot
change the Update Screen settings once the macro is nalized. You
can, however, record another macro that consists of two steps:
turning update screen off, then calling the original macro.

Wait
Selecting the Wait macro command brings up the Wait dialog box
(Figure 611). A pop-up menu lets you select from Wait For, Wait
Until, and Wait Until the Next, to wait for a set length of time (say, 55
seconds), wait until a certain time (say, 11:20 a.m.), or wait until the
next time division (say, at the next hour) before the macro continues.

Chapter 6 Customizing & Automating EChem

101

Figure 611
The Macro Wait dialog box,
with the three options
selected

The checkbox allows you to choose whether a dialog box with a

progress bar appears during the wait (Figure 612). The dialog box
gives a visual indication of wait progress, and gives you the options
of proceeding immediately to the next step of the macro by clicking
the Skip the Wait button, or aborting the macro by clicking the Stop
Macro button (equivalent to typing Command-period).

Figure 612
The Macro Wait dialog box
during the playing of the Wait
step of a macro

This feature is useful if you want to perform some steps of an

experiment at certain intervals, or to record multiple samples with a
specic interval between samples.

Play Sound
Selecting the Play Sound macro command brings up the Macro
Play Sound dialog box (Figure 612), which allows you to select from
the range of sounds in your Macintosh System to set audible alerts in
macros.
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EChem Users Guide

Figure 613
The Macro Play Sound dialog
box

Note
It helps to notify a user
that something is up if
you precede an alert box
with an audible signal
(using the Play Sound
macro command), since he
or she may not be looking
at the screen when an alert
box appears.

Click the name of a sound in the scrolling list to select it. If you wish
to hear the selected sound, click the Play button. To have it actually
played in the macro, click the OK button. To choose more than one
sound option, Shift-click or Shift-drag to select contiguous sounds in
the list, or Command-click to select or deselect multiple sounds
individually. Sounds appear in the list in the order they were installed
in the system, and are played back in that order. To save time in
creating multiple sounds, you can create a library of sound
combination macros, and simply incorporate one or more of them in
the macro that needs them.
You might wish to have three beeps signal when EChem starts
recording data, or a bell and a whistle at the end of a scan. You can
even record short verbal cues using the Sound control panel (if your
Macintosh has a microphone input) and use these in your macros.
If a macro attempts to play a sound not in the System le (created on
a computer with a different setup, or since removed from the System),
then an ordinary system beep will be substituted for the sound
originally specied.

Message
If you select the Message macro command, the Macro Message
dialog box appears (Figure 612). This allows you to cause alert boxes
requiring user response to appear at certain stages within the macro.

Chapter 6 Customizing & Automating EChem

103

Figure 614
The Macro Message dialog
box

You can type in the message of your choice (up to 255 characters). The
dialog box produced will have an OK button, and if the checkbox at
the top is highlighted, a Cancel button as well (for exiting the macro).
There are four choices of icon: the default shape (a hand) is
highlighted with a heavy border. Click one of the icon buttons to
choose it. You can use the icons to indicate the urgency of an
important message (hand, exclamation mark, and face, in order of
decreasing urgency), and the EChem icon for general messages which
indicate EChems state. Click the OK button when you have chosen
an icon and typed in the message.
Note
The Speak Message
command is only available
on Macintosh systems.

Speak Message
If you select the Speak Message macro command, the Speak
Message dialog box appears (Figure 615). Using it, you can give
spoken messages in macros, if your Macintosh has speech abilities.
Type in the phonetic equivalents to allow non-English words to be
spoken. After the message is spoken, the macro carries out
subsequent steps.
You can type in the message of your choice (up to 255 characters). If
the Macintosh on which the macro plays has no speech abilities then,
if the checkbox is off, a standard system beep will be used in place of
the spoken message. If the checkbox is on, an alert box appears, just
as if the Macro message dialog box were used: this will stop the
macro until its OK button is clicked.

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The volume at which the message is spoken can either be the default
system volume set in the Sound control panel, or can be set
independently to any of the sound levels, from 1 to 7, available in the
Sound control panel, by clicking or pressing the arrow controls.

Figure 615
The Speak Message dialog
box

Begin Repeat
The Begin Repeat macro command brings up the Begin Repeat dialog
box (Figure 616). This is used to repeat groups of steps in a macro.
You may repeat any group of commands up to 100,000 times. This
could be used, for example, to set up sampling at staggered intervals
overnight. For each Begin Repeat you should specify an End Repeat.
If you do not specify enough End Repeats, they are automatically
added when you select Stop Recording, but if you have a complex
macro, the repeated sequences might not end up in the right places.
Writing down the macro before recording it will help avoid such
problems.

Figure 616
The Begin Repeat dialog box

Repeat for Each Page

This macro command allows you to perform some operation on each
overlaid page of data in turn in the EChem le. The blank (last) page,
and pages not in the overlay, will be ignored.

Chapter 6 Customizing & Automating EChem

105

When this macro command plays, it will go through the EChem le

and display each page it operates upon, which may take a while: turn
off the Update Screen command to avoid this. As with the Begin
Repeat macro command, you should specify an End Repeat after the
instructions you want performed in the repeated sequence.

End Repeat
Each Begin Repeat or Repeat for Each Page macro you specify should
be paired with an End Repeat. If you do not specify enough End
Repeats, they are automatically added when you select Stop
Recording, but if you have a complex macro, the repeated
sequences might not end up in the right places. Writing down the
macro before recording it will help avoid such problems.
Note
The AppleScript command
is only available on
Macintosh systems.

AppleScript
This macro command allows you to insert an AppleScript as a macro
step. AppleScript is a scripting language for automating tasks, and
controlling applications and their interactions through Apple events.
To use it, you must have AppleScript installed on your Macintosh. On
selecting the AppleScript macro command, the AppleScript from
Macro dialog box appears. You will also need to be familiar with
using AppleScript.
For more information read the AppleScript section of your Scope
Users Guide. The EChem software has similar capability.

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EChem Users Guide

C H A P T E R

S E V E N

EChem Techniques
This chapter describes each of the items in the EChem Techniques
menu and the experiments that can be performed. Unnecessary
Techniques can be deleted from the menu by use of the Menu Editor
(discussed in Chapter 6).

Commonly performed experiments can be quickly congured with

the technique and exact parameters (scan rate, upper and lower
potential limits, pulse duration etc.) by the use of Settings Files or
Macros (Chapter 6).

In addition, other electrochemical experiments can be performed with

the Chart and Scope software, and these techniques are discussed in
Chapter 8. Chapter 8 also describes the use of EChem for AC
voltammetry and AC cyclic voltammetry.

EChem Users Guide

107

Introduction
EChem software supports a variety of voltammetric and
amperometric techniques:

The EChem Technique

menu

Standard techniques
Linear sweep voltammetry
- potentiodynamic polarization
- polarization resistance
Differential pulse voltammetry
Square wave voltammetry
Normal (and reverse) pulse voltammetry
Stripping techniques
Linear sweep stripping voltammetry
Differential pulse stripping voltammetry
Square wave stripping voltammetry
Normal pulse stripping voltammetry
Special techniques
Cyclic voltammetry
- cyclic potentiodynamic polarization scanning
MultiPulse voltammetry
- non-standard sampling for linear sweep voltammetry
- non-standard sampling for cyclic voltammetry
- cyclic square wave voltammetry
- cyclic differential pulse voltammetry
Pulse Amperometry
- differential pulse amperometry
- double pulse amperometry
- constant potential electrolysis
- differential normal pulse voltammetry
- double pulse voltammetry

The bulleted headings () can be selected from the Techniques menu

in EChem. This will activate the appropriate dialog box so that the
parameters for the experiment (scan rate, upper and lower potential
limits, pulse duration, etc.) can be entered.

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EChem Users Guide

All Stripping and Special techniques include controls that enable a

pre-scan deposition and a post-scan cleaning potential to be applied.
Multi Pulse Voltammetry is a general purpose technique allowing
you to dene any potential waveform that may be constructed from a
combination of a stepped ramp with one or two pulses superimposed
on each step. Up to four current signal sampling periods may be
dened for each step/pulse cycle. This technique can also be used to
set up nonstandard linear sweep, cyclic, square wave and differential
pulse voltammetry experiments where the current signal is sampled
at non standard times. It can also be used to perform cyclic square
wave and cyclic differential pulse voltammetry.
The Pulse Amperometry technique allows a xed potential to be set
with up to two pulses to be performed over a pre-set interval. The
potential/pulse interval can be repeated up to 16000 times, to create a
continuous scan.
Support for polarography experiments with a dropping mercury
electrode is provided by means of synchronized TTL pulse signals
(available on PowerLab S series units only).
Each of these techniques is discussed in greater detail in the following
sections.
Other techniques, which can be performed with Chart and Scope
software, are discussed in Chapter 8.
EChem software can also be used in conjunction with an AC
waveform generator and lock-in amplier to drive a potentiostat for
AC voltammetry and AC cyclic voltammetry (also discussed in
Chapter 8).

Chapter 7 EChem Techniques

109

General Considerations
Voltammetric experiments involve measuring the current signal while
the potential difference between the working and reference electrode
is varied. Results are usually presented as a plot of current versus
potential.
Amperometric techniques use a xed base potential, i.e. they have a
scan rate of 0 V/s. However pulses may be superimposed on the base
potential. The results are usually plotted as current signal versus time.

The Voltammetric Ramp

Figure 71
Typical potential/time profile
of a voltammetric ramp

Potential

Voltammetric techniques require that the potential between the

reference and working electrodes be increased or decreased at a
constant rate. If the potential at the electrode is plotted against time
then the resulting graph has the appearance of a smooth ramp
(Figure 71).

Time

With digital instrumentation, such as the PowerLab system, the ramp

actually consists of a series of discrete steps (and thus is often called a
staircase or stepped ramp) dened by the step width (ts) and step
height (Es) as shown in Figure 72.
The coarseness of this staircase is a function of the step width (ts) and
step height (Es). Step widths should be chosen to keep the step height
to a minimum (generally the step height should be less than 10 mV
with 1 or 2 mV being ideal). Then minimum step width and height
available depend on the potential range and sampling speed selected.

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EChem Users Guide

Staircase ramp
Potential

Figure 72
The digitally generated
staircase ramp

Es
Rest
time

ts

Time

Table 71 Dependence of Step Height resolution

on selected Potential Range. The Step Height at
any range setting must be a multiple of the
resolution.
Potential Range

Step Height resolution

1 V

0.5 mV

2 V

1.0 mV

5 V

2.5 mV

Table 72 Dependence of time base on selected

Sampling Speed. The Step Width, Sampling
Period, and Pulse Width at any speed setting must
be multiples of the time base.

Chapter 7 EChem Techniques

Sampling speed

Time Base

100 Hz

10 ms

400 Hz

2.5 ms

1 kHz

1 ms

4 kHz

0.25 ms

10 kHz

0.1 ms

111

Table 73 Commonly selected scan rates (mV/s) as a function of Step Height and Step Width.
Height, mV

Width, ms
0.5
0.1
0.2
0.25
0.3
0.4
0.5
0.6
0.7
0.75
0.8
0.9
1.0
1.1
1.2
1.25
1.5
1.6
1.8
2.0
2.5
3.0
3.3
4.0
5.0
7.5
8.0
10.0
11.1
12.5
14.3
15.0
16.7
20.0
25.0
30.0
33.3
40.0
50.0
62.5
66.7
80.0
83.3
90.9
100.0
111.1
125.0
142.9
166.7
200.0

112

5000
2500
2000
1666.6667
1250
1000
833.3333
714.2857
666.6667
625
555.5556
500
454.5455
416.6667
400
333.3333
312.5
277.7778
250
200
166.6667
151.5152
125
100
66.6667
62.5
50
45.045
40
34.965
33.3333
29.9401
25
20
16.6667
15.015
12.5
10
8
7.4963
6.25
6.0024
5.5006
5
4.5005
4
3.499
2.9994
2.5

1
10000
5000
4000
3333.3333
2500
2000
1666.6667
1428.5714
1333.3333
1250
1111.1111
1000
909.0909
833.3333
800
666.6667
625
555.5556
500
400
333.3333
303.0303
250
200
133.3333
125
100
90.0901
80
69.9301
66.6667
59.8802
50
40
33.3333
30.03
25
20
16
14.9925
12.5
12.0048
11.0011
10
9.0009
8
6.9979
5.9988
5

EChem Users Guide

1.5
15000
7500
6000
5000
3750
3000
2500
2142.8571
2000
1875
1666.6667
1500
1363.6364
1250
1200
1000
937.5
833.3333
750
600
500
454.5455
375
300
200
187.5
150
135.1351
120
104.8951
100
89.8204
75
60
50
45.045
37.5
30
24
22.4888
18.75
18.0072
16.5017
15
13.5014
12
10.4969
8.9982
7.5

2
20000
10000
8000
6666.6667
5000
4000
3333.3333
2857.1429
2666.6667
2500
2222.2222
2000
1818.1818
1666.6667
1600
1333.3333
1250
1111.1111
1000
800
666.6667
606.0606
500
400
266.6667
250
200
180.1802
160
139.8601
133.3333
119.7605
100
80
66.6667
60.0601
50
40
32
29.985
25
24.0096
22.0022
20
18.0018
16
13.9958
11.9976
10

2.5
25000
12500
10000
8333.3333
6250
5000
4166.6667
3571.4286
3333.3333
3125
2777.7778
2500
2272.7273
2083.3333
2000
1666.6667
1562.5
1388.8889
1250
1000
833.3333
757.5758
625
500
333.3333
312.5
250
225.2252
200
174.8252
166.6667
149.7006
125
100
83.3333
75.0751
62.5
50
40
37.4813
31.25
30.012
27.5028
25
22.5023
20
17.4948
14.997
12.5

Table 73 Commonly selected scan rates (mV/s) as a function of Step Height and Step Width.
Height, mV

Width, ms
0.5
250.0
333.3
500.0
1000.0
1250.0
1500.0
2000.0
3333.3
5000.0
6666.7
10000.0
100000.0

2
1.5002
1
0.5
0.4
0.3333
0.25
0.15
0.1
0.075
0.05
0.005

4
3.0003
2
1
0.8
0.6667
0.5
0.3
0.2
0.15
0.1
0.01

1.5
6
4.5005
3
1.5
1.2
1
0.75
0.45
0.3
0.225
0.15
0.015

2
8
6.0006
4
2
1.6
1.3333
1
0.6
0.4
0.3
0.2
0.02

2.5
10
7.5008
5
2.5
2
1.6667
1.25
0.75
0.5
0.375
0.25
0.025

Scan Rate
The scan rate is determined by the ratio of the step height to the step
width:

E
ScanRate = -----sts
This means that only certain scan rates, albeit a very large number,
can be entered. Table 73 contains a small selection of scan rates for
various combinations of step height and width.
In most techniques the easiest way to enter a legal scan rate is to type
in the desired scan rate, then to alter the Step Width to the nearest
exact multiple of the time base, Table 72. The scan rate will be
automatically updated to a legal value.

Chapter 7 EChem Techniques

113

Pulse Techniques
Pulse techniques require sudden increases in potential to be
superimposed on the staircase for short periods of time. Each pulse is
characterized by a Pulse Width and Pulse Height (Figure 73).
pulse width

Figure 73
Pulse terminology

pulse height

Potential

step width

current sampling per

step height

iod

Time

The Sampling Period

The EChem software samples the current signal at discrete periods
during each step. During these sampling periods data is collected at a
user selected rate of 100 Hz to 10 kHz. Sample periods are dened as
the period over which current readings are taken and then averaged.
The sampling period can be as short as 0.1 ms if sampling at 10 kHz.
There can be up to 4095 individual points in a sampling period which
can be as long as 409.5 ms (in the 10 kHz mode) to 40.95 s (in the 100
Hz mode)
Thus if you have dened a sampling period to be 2 ms long then
EChem can take 20 current measurements (at 0.1, 0.2, ... 1.9, 2.0 ms)
when in the 10 kHz sampling mode. At the end of the period the
current values are averaged to give a single value representative of
the current owing during the sample period.
The slower modes are used for very slow scanning, for example with
corrosion techniques, where very long step widths and sampling
periods are used. If the 100 Hz speed is selected scan rates as slow as
0.00016 mV/s can be used.
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EChem Users Guide

By selecting a sample
period of 20 ms or 16.7 ms
(for 50 or 60 Hz mains)
you can dramatically
remove main noise from
your voltammograms.

When using slower scan rates the sampling period can be set to
minimize mains noise. If you are operating on a mains frequency of
50 Hz (Europe, Australia, Chile, Argentina, and most of Africa, Asia)
then use sampling periods that are a multiple of 1/50 Hz = 20 ms, i.e.
a single mains AC cycle. If you are operating at 60 Hz (North
America, South Korea, Taiwan, most of South America, and parts of
Japan, Peru and Saudi Arabia, etc.) then make your sample period a
multiple of 1/60 Hz 16.7 ms. This will cause the current data to be
sampled over an integral number of mains AC cycles and thus any
noise arising from this source will be effectively ltered out.
With most techniques the sampling period is located at the end of the
pulse or step. But with the more exible MultiPulse Voltammetry and
Amperometry techniques you may set the sample period to be at the
beginning, middle or end of a step or pulse.

The Rest Time

Before data is recorded it is common to bring the working electrode to
the initial potential of the applied potential ramp. The potential is
then held at this value for a short period of time, the rest time,
(usually several seconds or longer) for the current ow to stabilise,
and for the solution to settle after stirring.

Chapter 7 EChem Techniques

115

Linear Sweep Voltammetry

In linear sweep voltammetry (LSV) a linearly increasing (or
decreasing) potential staircase ramp is applied to the working
electrode (Figure 74). The average current owing during the sample
periods (at the end of each step of the potential ramp) is recorded and
plotted against the voltage. Note that the peaks may appear positive
or negative depending on your denition of the direction of current
ow. The invert check box in the Potentiostat/Input Amplier setup
dialog can be used to alter the direction (up or down) of the peaks.
Figure 74
Waveform terminology for the
Linear Sweep technique

Staircase ramp
Potential

step width
step height
Rest
time

sampling per

iod

Time

The position of the current sampling period in LSV is xed by

software at the end of each potential step. At this point the faradaic
component is still signicant whereas the charging current has
decayed. If you require a different position of the sampling period
then you can use the Multi Pulse method to set up your own
customized LSV run.
Since this technique is designed to mimic linear sweep behavior
obtained with analog instruments, the idea is to select parameters
such that the coarseness of the potential staircase ramp is minimized.
To achieve this the step height should be kept as small as possible.
With EChem this places an effective limit on the scan rate of about 50
V/s for a potential range of 1 V. The scan rate can exceed this limit
but close adherence to results obtained from true analog linear sweep
voltammetry is no longer retained. Note that higher scan rates are
achieved with PowerLab/4s, /8s, and /16s models.

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EChem Users Guide

Parameters
When Linear Sweep Voltammetry is chosen from the techniques
menu the Linear Sweep Voltammetry dialog box appears
(Figure 75). This allows the user to adjust the parameters for the
technique. The rst time the technique is chosen the parameters will
be default values.

Figure 75
The Linear Sweep
Voltammetry dialog box

Each parameter is altered by entering a new value in the appropriate

box, selecting a new menu item, or clicking the control arrows.
Changes take effect when the OK button is clicked. Click the Cancel
button to exit without altering the parameters. It is usually best to
adjust the parameters in the following order:

Speed
The data acquisition rate is normally set at 10 kHz in the Speed popup menu. Very slow rates (less than 1 mV/s) may require slower
speeds so that appropriately long step widths can be used.

Range
The range pop-up menu selects the full scale range of the applied
potential. Three ranges are available, 1000 mV giving 0.5 mV
resolution, 2000 mV giving 1 mV resolution, or 5000 mV giving 2.5
mV resolution, Table 71. Usually the 2000 mV range is chosen.

Chapter 7 EChem Techniques

117

(Step) Height
This is the amplitude of each potential step. The minimum step
available depends on the selected range, Table 71. Values from 0.5 to
2.5 mV are ideal for work where accurate peak positions, heights and
areas are required. Values over 5 mV may give insufcient potential
resolution, and also lead to excessively high charging currents at
macro electrodes, for most voltammetric and pulse techniques.

Initial (Potential)
This is a text box that sets the initial or starting potential of the ramp.
This can be chosen anywhere between the limits of the range setting.

Final (Potential)
The potential voltage at which the ramp waveform [Link] can
be chosen anywhere between the limits of the range setting. The nal
potential may be either more negative than the initial potential
(negative scan) or more positive than the initial potential (positive
scan).

Steps
The number of steps in the ramp is derived from the initial and nal
potentials and the step height:
FinalPotential InitialPotential
Steps = -----------------------------------------------------------------------------------------StepHeight

This number must be an integer. If it is not then you will have to

adjust the Upper and/or Lower Limit so that the difference is an
exact multiple of the Step Height.

(Scan) Rate
This sets the rate at which the ramp will be generated. Faster scan
rates lead to a higher background signal unless a microelectrode is
used. This is usually set between 5 and 1000 mV/s for ordinary macro
electrodes. The scan rate is the ratio of the step height to the step

118

EChem Users Guide

width. When the rate is adjusted the step width is also adjusted to
maintain the selected step height.

(Step) Width
The time that the potential is kept constant at each step. The value
must be a multiple of the time base, Table 72. Step width, step height
and scan rate are interrelated:
StepHeight
StepWidth = ----------------------------ScanRate

After you adjust the scan rate, adjust the step width to the nearest
exact multiple of the time base, Table 72. This may alter the scan rate
slightly.

Rest Time
This is the length of time the initial potential is maintained before the
scan is started. A time of around 1 to 60 seconds is usually
appropriate, although much longer times may be necessary for
corrosion experiments (potentiodynamic polarization or polarization
resistance experiments).

Figure 76
Waveform Overview dialog
box for a typical LSV
technique

The View Button

You can get an idea of what effect the present parameters will have on
the waveform by clicking the View button. If the parameters are set
correctly then the Waveform Overview dialog will appear
(Figure 76). This displays a small section of the waveform showing
Chapter 7 EChem Techniques

119

the steps and the sampling period (the thick, red, line segments). If
the parameters are above the maximum limits or do not make sense
then you will see an error dialog describing what is wrong

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EChem Users Guide

Square Wave Voltammetry

In Square Wave Voltammetry (SWV) a square wave cycle is added to
each step of the staircase potential ramp. This technique is also called
Osteryoung Square Wave Voltammetry. A variation where a number
of square wave cycles occur at each step is called Baker Square Wave
Voltammetry and this is not available in EChem.
SWV has the advantage of showing the signals from a reversible
redox reaction while partially suppressing signals of irreversible
processes, and can be a very powerful technique for compound
characterization. It is also extremely useful for high speed, yet
sensitive, stripping analysis
The wave-form used in square wave voltammetry is shown in
Figure 77 Note that the square wave amplitude is dened as half the

step width
amplitude

Potential

Figure 77
Waveform terminology for
Square Wave Voltammetry

sampling
period, i1

Rest
time

step height

sampling
period, i2

Time

peak to trough separation (similar to the denition of the amplitude

of a sine wave). The current is sampled and averaged at the end of the
forward step and again at the end of the reverse step. The two data
points at each step can be described by the potential/current
coordinates (E1, i1) and (E2, i2).
SWV is quite popular for analysis as it combines the speed of linear
sweep techniques with the ability to discriminate against charging
currents (similar to differential pulse voltammetry). The difference
between the current at the forward step, i1, and the current at the
reverse step, i2, is displayed against average potential during the step
width. Thus at each step of the experiment the coordinates of the data
points displayed on the screen are given by:

Chapter 7 EChem Techniques

121

([i1-i2], [E1+E2]/2)
The actual values of the two currents, i1 and i2 are stored in the
arrays of these names and can be viewed separately by choosing
Sampling Display in the Display menu, to present the dialog in
Figure 78.

Figure 78
The Data Selection dialog
box.

The default settings for SWV displays i1i2 (i3 and i4 are not used for
Square Wave Voltammetry). Selecting i2 Minus Nothing would
change the graph on display so that you would see the current values
at the top of each pulse.
You may occasionally nd that a SWV run gives you small peaks and
that on attempting to run the experiment at a slightly higher gain you
nd that much of the signal is off scale. Remember that the default
display is i1i2, i.e. the difference between the current values in i1 and
i2. It is possible that the arrays i1 and i2 contain many large current
values and so need to be recorded on low gain settings to be on scale.
You can check that this is so by using the Sampling Display
command. If corresponding values in i1 and i2 are both large and
nearly equal then the difference, i1i2 will be small but you will not
be able to select higher gains to collect the data.

Parameters
When Square Wave Voltammetry is chosen from the techniques menu
the Square Wave Voltammetry dialog box appears (Figure 79).
Suitable parameters can be entered in the relevant spaces to alter the
technique as needed for the experiment being conducted.
Changes take effect when the OK button is clicked. Click the Cancel
button to exit without saving.

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Figure 79 z
The Square Wave
Voltammetry dialog box.

The Speed Menu

The data acquisition rate is normally set at a speed of 10 kHz.

Range
The range pop-up menu selects the full scale range of the applied
potential. Three ranges are available, 1000 mV giving 0.5 mV
resolution, 2000 mV giving 1 mV resolution, or 5000 mV giving 2.5
mV resolution, Table 71. Usually the 2000 mV range is chosen.

Initial (Potential)
Enter the initial or starting potential of the ramp in this text box. This
can be chosen between anywhere between the extremes of the
selected range. The Initial Potential is the mid point of the rst square
cycle.

Final (Potential)
The potential voltage at which the ramp waveform nishes. This can
be chosen anywhere between the extremes of the selected range. The
nal potential may be either more negative than the initial potential
(negative scan) or more positive than the initial potential (positive
scan). The Final Potential is the mid point of the last square wave
cycle.

Frequency
This is the frequency of the square wave. Frequencies in the range
5 60 Hz usually give good results, but with microelectrodes, or RAM
Chapter 7 EChem Techniques

123

electrodes, frequencies of hundreds (or even thousands) of Hertz may

be employed. With a PowerLab S model, frequencies of up to 5000 Hz
can be used. With PowerLab e, and earlier, models you should not
exceed 500 Hz.
The frequency of the square wave is related to the step width by:
1
StepWidth = ---------------------------Frequency

For square wave voltammetry the step width must be twice some
multiple of the time base, so that not all frequencies are allowed.

(Step) Height
Typical values of 1 2.5 mV are ideal. Values over 10 mV usually give
insufcient potential resolution for precise analytical work. The step
height and frequency are related to the scan rate by:
ScanRate = Frequency StepHeight

Steps
This value is automatically calculated and shows the number of steps
in the ramp according to the formula:
FinalPotential InitialPotential
Steps = -----------------------------------------------------------------------------------------StepHeight

S.W. Ampl. (Square Wave Amplitude)

This is the half-height of the pulses of the square wave. Typical
amplitudes are in the range of 10 50 mV. Use a negative amplitude if
you want the initial square wave cycle to begin in the negative
direction.

S.(ampling ) Period
Current data will be collected and averaged over this period which
occurs at the end of each step (upper and lower). The sampling
period should normally be shorter than the step width
(= 1/Frequency) in order for the charging current to decay. For

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example at a frequency of 25 Hz the step width is 40 ms. Therefore

the sampling period should be set to 40 ms or less (preferably 16.7 or
20 ms to minimize mains 60 Hz or 50 Hz noise interference).

Rest Time
This is the length of time the initial potential is maintained before the
scan is started. A time of around 1 to 60 seconds is usually
appropriate.

The View button

The quickest way to determine if the parameters you have set will
work is to click the view button. If the parameters you have set are
logically consistent then the Waveform overview window will appear
(Figure 710) with a representation of the potential waveform. If for
any reason the values you have set are out of range, or otherwise
inappropriate, you will be prompted by a dialog box telling you what
the problem is.

Figure 710 Waveform

Overview for a typical Square
Wave Voltammetry technique

Chapter 7 EChem Techniques

125

Normal Pulse Voltammetry

In Normal Pulse Voltammetry, a series of pulses of successively larger
potential are applied above a base potential to the working electrode.
Alternatively this can be thought of as an applied ramp interrupted at
regular intervals by a return to the baseline value.
Reverse Pulse Voltammetry is similar except that the base potential is
chosen to electrolyse the electroactive substrate. The pulses that are
then applied cause the reverse reaction to take place. This may be
useful if parallel competing reactions take place when the original
species is electrolysed. The waveform used in normal pulse
voltammetry is depicted in Figure 711. The current is sampled at the
end of each pulse, and plotted against the potential.

step width
current sampling period

Figure 711
Waveform terminology for
Normal Pulse Voltammetry

step height
initial (zero)
pulse
initial (base)
potential

pulse width

Parameters
A Typical dialog box for setting up a normal pulse experiment is
shown in Figure 712. Each parameter is altered by entering a new
value in the appropriate box, selecting a new menu item, or clicking
the control arrows. Changes take effect when the OK button is
clicked. Click the Cancel button to exit without saving.

Speed
The data acquisition rate is normally set at 10 kHz. Very slow rates
(less than 1 mV/s) may require slower speeds so that appropriately
long step widths can be used.

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Figure 712
The Normal Pulse
Voltammetry dialog box

Range
The range pop-up menu selects the full scale range of the applied
potential. Three ranges are available, 1000 mV giving 0.5 mV
resolution, 2000 mV giving 1 mV resolution, or 5000 mV giving 2.5
mV resolution, Table 71. Usually the 2000 mV range is chosen.

Initial (Potential)
This is the initial or starting potential of the ramp. This can be chosen
between 2000 mV if on the 2000 mV range or 5000 mV when on
the 5000 mV range. This value is usually chosen to be a value at
which the electrode reaction of interest does not occur (so that the
current is close to zero). For Reverse Pulse Voltammetry this potential
is chosen to cause complete oxidation (or reduction) of the substrate,
and the pulses then cause the reverse reaction.

Final (Potential)
The potential voltage at which the ramp waveform nishes. This can
be set between 2000 mV if on the 2000mV range or 5000 mV when
on the 5000 mV range. The nal potential may be either more
negative than the initial potential (negative scan) or more positive
than the initial potential (positive scan). This is the height of the last
pulse to be applied. It can be thought of as the height of an imaginary
ramp passing through the tops of the pulses.

(Scan) Rate
This sets the rate at which the ramp will be generated in mV per
second. This is usually set between 5 and 100 mV s-1 for macro

Chapter 7 EChem Techniques

127

electrodes. Generally this parameter is allowed to vary as the Initial

and Final Potentials and the Step Width and Height are set.

(Step) Width
The time that the potential is kept constant at each step. The value
cannot be set less than 0.2 ms. Times of around 2 4 ms are usually
satisfactory. Step Width is related to Step Height and Scan Rate by:
StepHeight
StepWidth = ----------------------------ScanRate

(Step) Height
This denes the increase in height (mV) of successive pulses. The
minimum step available is 1 mV. Typical values of 1 2 mV are ideal.

Steps
This value is automatically calculated and shows the number of steps
in the ramp according to the formula:
FinalPotential InitialPotential
Steps = -----------------------------------------------------------------------------------------StepHeight

Pulse Width
The length of time of the applied pulse. Values between 5 and 100 ms
are commonly used, with a minimum of 0.1 ms possible. The pulse
width should be wide enough to allow the non-faradaic components
of the current to decay before sampling. For a 1 mm2 macro electrode
allow the pulse to be at last several milliseconds longer than the
sample period.

Rest Time
This is the time that the initial potential will be applied to the cell
before the actual ramp is applied. This allows you to leave the cell
electrodes at a preset potential in order for charging currents and
other disturbances to settle. This time is usually in the range of
1 60 seconds. Setting the rest time to zero will start the technique
immediately.
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S.(ampling ) Period
Current data will be collected and averaged over this period which
occurs at the end of each pulse. A suitable sampling width is 20 ms,
or 16.7 ms where mains frequency is 60 Hz. This effectively
discriminates against mains frequency interference.

The View button

The quickest way to determine if the parameters you have set will
work is to click the view button. If the parameters you have set are
OK then the Waveform overview window will appear (Figure 713)
with a representation of the potential waveform. If for any reason the
values you have set are out of range or inappropriate you will be
prompted by a dialog box telling you what the problem is.

Figure 713
The Waveform Overview
dialog box for the Normal
Pulse Voltammetry technique

Chapter 7 EChem Techniques

129

Differential Pulse Voltammetry

Differential Pulse Voltammetry (DPV) uses a series of short, small
amplitude pulses (typically 50 mV) superimposed on a linearly
increasing or decreasing potential ramp (Figure 714). The current is
sampled just prior to each pulse (i1) and at the end of the pulse (i2).
The difference in current (i2i1) is plotted versus the potential at the
base ramp.
step width

amplitude

Figure 714
Waveform terminology for the
Differential Pulse
Voltammetry technique
Rest
time

step height

sampling
period

Time

Remember that you are viewing the difference between two current
signals. The actual values of the two currents, i1 and i2 are stored in
the arrays of these names and can be viewed by choosing Sampling
Display in the Display menu.
Figure 715
The Sampling Display dialog
box

This brings up the Data Selection Dialog (Figure 715) which is set to
display i2 Minus i1 (i3 and i4 are not used for DPV). Selecting i2
Minus Nothing would change the graph on display so that you
would see the current values at the top of each pulse.
You may occasionally nd that a Differential Pulse Voltammetry run
gives you small peaks and that on attempting to run the experiment
at a slightly higher gain you nd that much of the signal is off scale.
Remember that the default display is i2 i1, i.e. the difference

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between the current values in i2 and i1. It is possible that the arrays i1
and i2 contain many large current values and so need to be recorded
on low gain settings to be on scale. You can check that this is so by
using the Sampling Display command to view i1 and i2 separately. If
the values in i1 and i2 are both large and nearly equal then the
difference, i1 i2, will be small but you may not be able to select
higher gains to collect the data because i1 and/or i2 will go off scale.
Increasing the pulse height for DPV experiments may give you larger
peaks but resolution will be decreased.
Note that if you make the Pulse Width exactly half the Step Width
then you will actually have a waveform that is identical to that used
for Square Wave voltammtery. However, there are two important
differences. Firstly the default display of DPV is i2 i1 while for
SWV it is i2 i1. Thus you will need to alter the DPV Sampling
Display appropriately. Secondly DPV results are plotted against the
potential at base of each pulse, whereas in SWV the average potential
over each square wave step is used.

Parameters
When Differential Pulse is chosen from the Techniques menu the
Differential Pulse Voltammetry dialog box appears (Figure 716).

Figure 716
The Differential Pulse
Voltammetry dialog box

Each parameter is altered by entering a new value in the appropriate

box, selecting a new menu item, or clicking the control arrows.
Changes take effect when the OK button is clicked. Click the Cancel
button to exit without saving.

Chapter 7 EChem Techniques

131

The Speed Menu

The data acquisition rate is normally set at 10 kHz. Very slow rates
(less than 1 mV/s) may require slower speeds so that appropriately
long step widths can be used.

Range
The range pop-up menu selects the full scale range of the applied
potential. Three ranges are available, 1000 mV giving 0.5 mV
resolution, 2000 mV giving 1 mV resolution, or 5000 mV giving 2.5
mV resolution, Table 71. Usually the 2000 mV range is chosen.

Initial (Potential)
This is the initial or starting potential of the ramp. This can be chosen
between 2000 mV if on the 2000 mV range or 5000 mV when on
the 5000 mV range.

Final (Potential)
The potential voltage at which the ramp waveform nishes. This can
be set between 2000 mV if on the 2000 mV range or 5000 mV
when on the 5000 mV range. The nal potential may be either more
negative than the initial potential (negative scan) or more positive
than the initial potential (positive scan). The nal potential cannot be
the same as the initial potential.

(Step) Height
This is the amplitude of each voltage step in millivolts. The minimum
step available is 1 mV. Typical values of 110 mV are ideal. Keep this
parameter as small as possible.

(Scan) Rate
This sets the rate at which the ramp will be generated in mV per
second. This is usually set between 1 and 25 mV s-1. Increasing the
scan rate decreases peak resolution. However very slow scan rates
mean inordinately long analysis times.

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(step) Width
The time of each step (including the pulse time). This is also the
period between pulses. This parameter is usually allowed to vary
while the Scan Rate and Step height are set. This parameter is usually
set between 0.5 to 4 s. Step Width is related to Step Height and Scan
Rate by the following relationship.
StepHeight
StepWidth = ----------------------------ScanRate

Steps
This is simply a readout value showing the number of steps in the
ramp according to the initial and nal voltages and the step height set
in these text boxes. The relationship between the number of steps and
the other parameters is:
FinalPotential InitialPotential
Steps = -----------------------------------------------------------------------------------------StepHeight

Pulse Width
The width of the pulse superimposed upon the potential ramp. This
parameter is usually set in the range of 5 to 100 ms. The pulse should
last long enough to allow the non-faradaic components of the current
to decay before sampling. For a standard glassy carbon electrode with
an area of ~1 cm2 where sampling is to be carried out over a wide
enough window to reject mains noise (20 ms @ 50 Hz) then a pulse
width of 50 ms would be appropriate.

Pulse Amplitude
The height of the pulse superimposed upon the potential ramp. This
is usually set in the range of 50 100 mV. Larger values increase
sensitivity (i.e. you get bigger peaks), smaller values improve
resolution.
The Pulse Height must be greater than Step Height, or else the next
step will be higher that the previous pulse!

Chapter 7 EChem Techniques

133

Rest (time)
This is the period between when the deposition potential is applied
and the scan commences. This is usually set to between 1 and 5 s.

S.(ampling ) Period
Current data will be collected and averaged over this period which
occurs just prior to the pulse and at the end of each pulse. Usually
this parameter is set to between 1 and 20 ms. Multiples of 20 ms (at
50 Hz mains) or 16.7 ms (at 60 Hz mains) will discriminate against
mains noise. In general there will be less noise for longer sampling
periods.

The View button

The quickest way to determine if the parameters you have set will
work is to click the view button. If the parameters you have set are
OK then the Waveform overview window (Figure 717) will appear
with a representation of the potential waveform. If for any reason the
values you have set are out of range or inappropriate you will be
prompted by a dialog telling you what the problem is.
The thick line segments just prior to the pulse and at the end of the
pulse represent the sampling period. Note that the waveform
overview dialog box shows a magnied portion of the entire
waveform (upper) as well as the whole ramp (lower).
Figure 717
The Waveform Overview
Dialog box for a typical
Differential Pulse
Voltammetry experiment

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EChem Users Guide

Stripping Techniques
EChem allows you to perform stripping type techniques using any
one of the ve standard methods just described. EChem supports;

Linear sweep stripping voltammetry

Differential pulse stripping voltammetry
Square wave stripping voltammetry
Normal pulse stripping voltammetry

In addition non-standard stripping experiments can also be set up in

the Cyclic and MultiPulse Techniques. Stripping techniques involve
xing the analyte to the working electrode in some way. This has the
advantage of concentrating the analyte at the electrode and giving a
dramatic increase in sensitivity.
The two main methods in this area are cathodic stripping
voltammetry and anodic stripping voltammetry. Both methods make
use of a constant deposition potential applied prior to beginning of
the experiment proper. Similarly after the experiment a constant
cleaning potential can be maintained for a xed time period.

Anodic Stripping Voltammetry

Anodic stripping techniques usually involve the use of mercury as a
working electrode. This may be in the form a hanging mercury drop
electrode (HMDE), or a mercury lm electrode (MFE). The function of
the mercury is to amalgamate with (dissolve) metals that plate out on
the electrode surface when metal ions in solution are reduced. Solid
electrodes can also be used but mercury usually gives superior
performance.
Prior to the experiment a reduction step takes place when a
deposition potential is applied to the mercury working electrode. This
potential is maintained, usually while stirring the solution, so that the
metal ions of interest in the sample are concentrated within the
mercury electrode. The deposition potential should be at least 0.2 V
more reducing than the peak potential of the most electropositive
metal to be detected.

Chapter 7 EChem Techniques

135

The deposition process can involve a concentration increase of many

orders of magnitude and allows the measurement of metal ion
concentrations in extremely dilute (ppb or ppt) solutions. The more
dilute the original sample the larger it should be, and the longer the
deposition step will take. While you will have to work out your own
parameters for any given sample some suggested values to start with
are shown in Table 74.

Table 74 Typical deposition times for analytes of various concentrations.

Concentration mol L-1

Deposition time min

10-7

10-8

20

10-10

60

After the metals have been deposited within the mercury electrode
stirring is stopped and a rest potential is applied for at least 30 s.
Linear sweep voltammetry or one of the standard pulsed techniques
can be applied. At the end of the ramp an oxidizing cleaning potential
is applied to remove any residual metals from the mercury electrode.
This potential should be at least 0.2 V more oxidizing than the peak
potential of the most electronegative metal being measured.
It is not necessary to deposit all the metal ions in solution. It is simply
necessary to repeat the experiment under exactly the same conditions
(deposition time and potential, scan rates and limits etc.) for a series
of standards followed by the unknown(s) so that a useful graph of
concentration versus signal can be prepared. If the concentration of
the metal ion is relatively high then it is important to either dilute the
solution before measuring and/or to ensure that deposition times are
short. This is to ensure that the build up of metal analyte in the
mercury does not change the properties of the amalgam too far from
that of a dilute mixture. A concentrated amalgam may give peaks at
unexpected values or even multiple peaks for a single analyte, or may
give a current that overloads the potentiostat.
Closely overlapping peaks arising from metal ions with a similar
reduction potential can sometimes be separated by the addition of a
complexing agent (such as EDTA, or dimethylglyoxime). The metal is

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EChem Users Guide

then no longer present in solution as an aquated metal ion but as a

complex ion with a different reduction potential.

Cathodic Stripping Voltammetry

Anions can be xed to an electrode as an insoluble metal salt. In the
case of analyzing for halides an oxidizing deposition potential is rst
applied at a silver electrode:
Ag(s) + I-(aq) AgI(s) + eA subsequent scan to reducing potential can be used to detect the
halide(s) present as the silver halide is reduced:
AgI(s) + e- Ag(s) + I-(aq)
Other anions that can be detected include sulde, phosphate,
arsenate, and arsenite. The working electrode is usually made of
mercury, gold or silver.

Setting Parameters
When any of the stripping techniques are chosen from the Technique
menu, a dialog box will appear (Figure 718). The dialog is similar to
the non-stripping technique dialog except that extra controls for
Deposition and Cleaning appear at the bottom of the dialog box. You
can set a potential, and a time period, for both deposition and
cleaning. All the Stripping techniques carry out deposition rst,
followed by the actual technique and then cleaning takes place.
Both the deposition and Clean Time periods can be turned off using
the check boxes next to their titles. By tuning off both the Deposition
and Clean Time periods then only the basic technique will be left. For
example, when using Cyclic Voltammetry you should leave both
check boxes off unless you are attempting an unconventional
experiment.
The ramp and pulse parameters are set up in the same way as for the
corresponding non-stripping technique. Refer to the corresponding
non-stripping technique for information on these parameters.

Chapter 7 EChem Techniques

137

Figure 718
An example of the Stripping
version of the standard Linear
Sweep Voltammetry technique
dialog box

Deposition potential
This potential is applied for a xed period (usually several minutes)
and can be set between extremes of the Range setting.

Deposition Time
This is the time in seconds for which the deposition potential will be
applied. You can enter times from 0.01 seconds up to 9999 seconds
(about 2 h 47 min).

Clean Time Potential

At the end of a scan a cleaning potential can be applied (usually for a
minute or so). This can be set anywhere between the extremes of the
range setting.

Cleaning Time
This is the time in seconds for which the cleaning potential will be
applied. You can enter times from 0.01 seconds up to 9999 seconds
(about 2 h 47 min).

Stirrer & Gas Controls

Use of a stirrer and gas purge is facilitated by the provision of TTL
logic control signals carried by carried by Output 1 and Output 2 of

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EChem Users Guide

CAUTION. Connection
of the PowerLab to an
external stirrer and
purge system should
only be attempted by a
qualied electronics
technician.

TTL logic signals are a

simple means of on/off
communication between
instruments. TTL high
corresponds to a voltage
level of about 5 V, while
TTL low corresponds to
a signal of about 0 V.
These states are
controlled in software by
a single bit variable
which is referred to as
being set on or off.

the PowerLab digital output, page 160. The Stirrer check box controls
digital output 1 and the Gas check box controls digital output 2 of the
PowerLab. Refer to your PowerLab Owners Guide for details of the
digital output signals and how to connect to them. Note that on
PowerLab/200 /400 and the older /2e and /4e units the digital
output signals are provided on the Multiport connector on the rear of
the unit. Other PowerLab models have a dedicated digital output
connector. The digital I/O ports provide 0 5 V at about 1 mA. This is
enough to act as an on/off signal but is not sufcient to power a
stirrer or other equipment.
Checking the Gas and/or Stirrer checkboxes allows you to control the
state of an external stirrer motor or solenoid gas valve during
deposition. These check boxes control two of the digital output (TTL)
lines provided by the PowerLab. Activating these controls (click the
check box) will set the corresponding digital output on at appropriate
times during the experiment. Output 1 is on during the Deposition
and Cleaning periods, while Output 2 is on during the Deposition
time only. A cable can be made to use these signals to turn a stirrer
and solenoid gas valve on and off during the stripping experiment.
You can monitor the state of the digital output lines by displaying the
Digital Output panel, Figure 732.

Chapter 7 EChem Techniques

139

Cyclic Voltammetry
The potential is driven between two limits at a constant rate, similar
to linear sweep voltammetry. When a limit is reached the potential is
swept back again at the same rate. The experiment can start at any
potential (initial potential) between the two limits and usually
nishes at the initial potential so that an integral number of cycles are
performed. This technique is usually used for qualitative purposes
and is valuable in the characterization of new compounds.
The ideal waveform used in cyclic wave voltammetry is depicted in
Figure 719. For computer driven systems like EChem/PowerLab the
ramp is stepped (shown below right) and this method is often called
staircase cyclic voltammetry.

Figure 719
Waveform terminology for
Cyclic Voltammetry

upper limit
initial
potential

final
potential

step width
step height

sampling per

iod

lower limit

Different workers have sampled at 25%, 50%, 75%, or 100% of each

step, depending on the experimental requirements. For qualitative
work this will usually not give signicant differences. The Cyclic
Voltammetry method in EChem always samples current at the end of
each step. Thus a 100 ms step with a sampling period of 25 ms would
be sampled at 75.0 99.9 ms at 0.1 ms intervals (when the 10 kHz
speed mode is used) and the values then averaged. If you require to
sample the current values over different regions, say halfway through
the step, then you can use the Multi Pulse Voltammetry command.
The upper and lower potential limits will often be constrained by the
choice of solvent and electrolyte. Background sweeps (of solvent and
electrolyte) are necessary to determine the window region in which
measurements can be made. Remember to perform these sweeps at
the same gain setting as will be used in your experiment. When using

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EChem Users Guide

non-aqueous solvents ensure that adequate purication and drying

are undertaken. See Appendix E for more information.

Parameters
Choose Cyclic Voltammetry from the Techniques menu. The Staircase
Cyclic Voltammetry dialog will appear (Figure 720).
Figure 720
The Staircase Cyclic
Voltammetry dialog box.

Each parameter is altered by entering a new value in the appropriate

box, selecting a new menu item, or clicking the control arrows.
Changes take effect when the OK button is clicked. Click the Cancel
button to exit without saving.

The Speed Menu

The data acquisition rate is normally set at 10 kHz. Very slow rates
(less than 1 mV/s) may require slower speeds so that appropriately
long step widths can be used.

Range
The range pop-up menu selects the full scale range of the applied
potential. Three ranges are available, 1000 mV giving 0.5 mV
resolution, 2000 mV giving 1 mV resolution, or 5000 mV giving 2.5
mV resolution, Table 71. Usually the 2000 mV range is chosen.

Chapter 7 EChem Techniques

141

Initial (Potential)
This is the initial or starting potential of the ramp. This can be set
anywhere between the Upper and Lower Potential Limits. It is
normally chosen to be a value at which oxidation or reduction of the
substrate does not occur.

Final (Potential)
The potential voltage at which the ramp waveform nishes. It is
automatically set to be the same as the initial potential (so as to
complete a full cycle).

Upper (Potential Limit)

The maximum potential that will be achieved in a cycle and this can
be set anywhere between the extremes of the Range.

Lower (Potential Limit)

The minimum potential that will be achieved in a cycle and this can
be set anywhere between the extremes of the Range. Note that the
difference, UpperLower will be less than 2 V if the 1000mV range
is selected, 4 V if the 2000 mV range is selected, and less than 10 V if
the 5000 mV range is selected.

(Step) Height
Click the arrows to adjust the Step Height, usually 1 or 2 mV is ideal.
More than 10 mV will not give adequate resolution on the potential
axis.

(Scan) Rate
This sets the rate at which the ramp will be generated in units of
mV/s. It is usually set in the range 10 1000 mV/s for normal macro
electrodes (1 mm diameter or greater). Microelectrodes (diameters
from less than 1 m to 100 m) are usually employed for faster scan
rates.

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(Step) Width
This is the time that the potential is kept constant at each step. In
general rst adjust the Step Height, next enter the Scan Rate, then
nally adjust the Step Width to the nearest allowed resolution
increment, Table 72
Step Width is related to Step Height and Scan Rate by the following
relationship.
StepHeight
StepWidth = ----------------------------ScanRate

Steps
The number of Steps in a cycle is determined automatically and is
given by the formula:
Steps =

UpperPotential LowerPotential
2
StepHeight

If Steps is not an integer then EChem will not perform the experiment
and a warning dialog will appear when you click the View or OK
button. In this case you will need to adjust Step Height or the Upper
and Lower Potentials to make Steps an integer.

Rest Time
This is the period after the deposition potential has been applied and
before the scan commences. This is usually set to between 1 and 60s.

(Deposition) Pot(ential)
Not normally used for Cyclic Voltammetry. This is the deposition
potential applied for a xed period prior to the scan. This can be set
anywhere between the extremes of the Range.

(Deposition) Time
Not normally used for Cyclic Voltammetry. This is the time in seconds
for which the deposition potential will be applied. You can enter

Chapter 7 EChem Techniques

143

times from 0.01 to 9999 seconds (about 2h 47 min). This a period

before the Rest Time.

(Cleaning ) Pot(ential)
Not normally used for Cyclic Voltammetry. The potential applied
during the Cleaning Time. The Cleaning Potential can also be set so as
to oxidize (or reduce) any material that has plated out on the working
electrode. This can be set anywhere between the extremes of the
Range.

(Cleaning ) Time
Not normally used for Cyclic Voltammetry. At the end of a scan a
cleaning potential can be applied for a period dened by the Cleaning
Time (usually a few seconds to a minute or so).

Cycles
Enter the number of cycles required in this text box, this number must
be an integer less than 100. You can also choose the initial direction of
the cycle (if the Initial Potential lies between the Upper and Low
Potential Limits) by using the Initial Direction check box.
The maximum number of data points that can be stored during one
experiment is set at 65000. Thus number of cycles that can be
performed in the one experiment is limited by the formula:
Steps Number of Cycles 65000
Usually this will enable you to collect a maximum of between 8 and
100 scans (depending on your parameters). Of course if you require
more cycles you can always start the experiment over again or set a
Macro to repeat the experiment as many times as you like. There will
however be a short interval between each experiment.

The View button

The quickest way to determine if the parameters you have set will
work is to click the view button. If the parameters you have set are
OK then the Waveform Overview window will appear (Figure 721)

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with a representation of the potential waveform. If for any reason the

values you have set are out of range or inappropriate you will be
prompted by a dialog box telling you what the problem is:

Figure 721
The Waveform Overview
dialog box for Cyclic
Voltammetry.

Cyclic Voltammetry with 3rd Party

Potentiostats
The PowerLab Potentiostat will automatically isolate the electrodes
after the scan but if you are using a third party potentiostat you may
wish to set the Cleaning Potential equal to the Final Potential for
some seconds. This will give you time to isolate the electrodes before
the signal from the PowerLab is switched to zero volts. Similarly the
rest time can be extended to give you time to switch the potentiostat
from standby to real mode before the scan commences.

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145

MultiPulse Voltammetry
The MultiPulse Voltammetry technique allows you to generate your
own waveform. This is constructed by the addition of a staircase
ramp and one or two pulses per step of the ramp. These pulses may
be either positive or negative and may be increased or decreased
throughout the scan. Using this dialog the operator is able to dene
any one of a number of regularly used techniques. There is also the
added exibility of being able to dene an unusual pulse sequence. In
addition up to four current sampling windows can be selected with
their position and duration independently set.
A library of different signals, that can be used at any time, can be
achieved by writing Macros that include the Multi Pulse method or
by storing MultiPulse parameters in Settings les. This will allow you
to automate your experiments.
Note that if you want to set up a non-standard or cyclic Square Wave
voltammetry experiment then you will need to make the Pulse Width
exactly half the Step Width. Remember to adjust the Sampling
Display to i1-i2. Also MultiPulse Voltammetry results the default
display is to plot current against the potential at the base of each
pulse, whereas in the Square Wave Voltammetry technique the
average potential over each step is used.

Parameters
To use the MultiPulse technique, select the Multi Pulse method from
the Techniques menu. The MultiPulse dialog will appear (Figure
722).
Each parameter is altered by entering a new value in the appropriate
box, selecting a new menu item, or clicking the control arrows.
Changes take effect when the OK button is clicked. Click the Cancel
button to exit without saving.

Ramp parameters
First the Ramp parameters are adjusted. These have a similar function
to the parameters used for linear sweep voltammetry.

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Figure 722
The Multi Pulse Voltammetry
Technique dialog box

Speed
The data acquisition rate is normally set at 10 kHz. Very slow rates
(less than 1 mV/s) may require slower speeds so that appropriately
long step widths can be used.

Range
The range pop-up menu selects the full scale range of the applied
potential. Three ranges are available, 1000 mV giving 0.5 mV
resolution, 2000 mV giving 1 mV resolution, or 5000 mV giving 2.5
mV resolution, Table 71. Usually the 2000 mV range is chosen.

Initial (Potential)
This is the initial or starting potential of the ramp. This can be chosen
between 2000 mV if on the 2000 mV range or 5000 mV when on
the 5000 mV range.

Final (Potential)
The potential voltage at which the ramp waveform nishes. This can
be set between 2000 mV if on the 2000 mV range or 5000 mV
when on the 5000 mV range. It must not be the same as the initial
potential. The nal potential may be either more negative than the
initial potential (negative scan) or more positive than the initial
potential (positive scan).

Chapter 7 EChem Techniques

147

(Scan) Rate
This sets the rate at which the ramp will be generated in mV per
second. It is usually set less than 1 mV s-1 for corrosion work or in the
range of 5 to 1000 mV s-1 for other work. Faster scan rates lead to a
higher background signal.

(Step) Width
The time that the potential is kept constant at each step. Step Width is
related to Step Height and Scan Rate by:
StepHeight
StepWidth = ----------------------------ScanRate

(Step) Height
The size of each step. The value of this parameter will depend on the
experiment being performed. But it is usually less than 10 mV.

Steps
This is simply a readout value showing the number of steps in the
ramp according to the initial and nal voltages and the step height set
in these text boxes. The relationship between the number of steps and
the other parameters is:
FinalPotential InitialPotential
Steps = -----------------------------------------------------------------------------------------StepHeight

Rest Time
This is the period between when the deposition potential is applied
and the scan commences. This is usually set to between 1 and 5 s, or
longer for corrosion work.

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Cyclic
Clicking the Cyclic checkbox will activate the Params... button. This
also automatically sets the Final Potential equal to the Initial Potential
(so that the cycle will be complete)

Params...
Clicking the Params... button brings up the Cyclic Parameters dialog
box, Figure 723, so that a cyclic waveform can be set up. You can
enter the Upper and Lower Limits of the scan, the Number of Cycles
to be performed, and the Initial Direction of the scan (if the Initial
Potential lies between the extremes of the Upper and Lower Potential.
See the section on Cyclic Voltammetry for more information on the
operation of these parameters.

Figure 723
The Cyclic Parameters dialog
box

Dening pulses
For each step of the staircase ramp two pulses may be used. Each
pulse is activated by clicking the box in the upper left-hand corner of
the pulse panel, and now the relevant parameters can be entered.

(Pulse) Start
The timing of each pulse is linked to the start of each step in the base
ramp. For example if you enter 20 ms in the Start box it means the
pulse will be activated 20 ms after the beginning of the step. The
pulse can begin at any time during each step and must be less than
the Step Width. If you are using a PowerLab/200, /400, /800 or /2e,
/4e or /8e then try to avoid starting pulses at 0 ms or starting two

Chapter 7 EChem Techniques

149

pulses at the same time when constructing a waveform. There will be

a short delay (a few microseconds) between the beginning of
apparently concurrent events. Often a waveform of the same shape
can be construct by placing the pulse towards the end of the step. The
PowerLab/4s, /4SP, /8s and /16s do not suffer these limitations.

(Pulse) Height
The height of the pulse superimposed upon the potential ramp. Note
that the value for the height of the pulse is added to the potential of
the staircase ramp. If two pulses are made to overlap then the ramp
and pulse potentials are all added together over this period.

Inc(rement)
Pulses on successive steps will be incremented by this amount.

Width
The duration of the pulse must be such that the entire pulse occurs
within one step of the potential ramp.

This is best explained by examples. The dialog box shown in Figure

724 sets up two simple pulses, each 100 ms long, on each 500 ms step
of the ramp. Clicking the View... button Waveform Overview window
displays the appearance of several steps of the ramp, Figure 725.

The Sampling Dialog

By clicking the Sampling... button in the Multi Pulse dialog the
Sampling Time dialog in Figure 726 is activated. This dialog box
allows you to nominate the current sampling periods. This involves
choosing the time and duration of each of up to 4 sampling periods
(i1, i2, i3, and i4).
The dialog box is divided into four panels which control each of the
four sampling periods available.

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EChem Users Guide

Figure 724
An example of settings for the
Multi Pulse dialog box.

Figure 725 the

Waveform Overview dialog
generated by the settings
shown in Figure 724

Figure 726
The Sampling Time dialog
box for Multi Pulse
voltammetric techniques.

Chapter 7 EChem Techniques

151

Each sampling period is activated by clicking the check box in the top
corner of each panel. The Start text box denes the commencement of
each sampling period with respect to the beginning of each step of the
ramp. The relative position of each sample period on the step can be
seen at the bottom of the dialog box (Figure 726).
Figure 727
The sampling period
indicator bar

Note that all sampling periods must be in chronological order. That is

point 1 must precede point 2 and so on. Also it is not possible to
overlap sampling periods.
Sampling periods that are multiples of 20 ms will discriminate
against 50 Hz mains frequency noise (or use a multiple of 16.7 ms for
60 Hz mains).
EChem normally plots the current versus the computed potential of
the base ramp within each step. However it is also possible to actually
measure the potential at any time along the step. To sample the
potential at a specic point use the E sample sub dialog
Select either Calculated (to used the computed potential) or Sampled.
Selecting Sampled then allows you to nominate the position along
each step that the potential is sampled. These sampled potentials are
then used when you display your results in I vs E, E vs I, or IE vs t
modes.

Figure 728
The Sampling Display dialog
box

Displaying Multi Pulse Data

Selecting Sampling Display... in the Display menu brings up the
corresponding dialog, Figure 728, which can be set to display a
graph of the values in i1, i2, i3 or i4, or the difference between any

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EChem Users Guide

two of these. If you require to display more complicated functions

you will need to transfer the data to a spreadsheet or graphing
application.

Chapter 7 EChem Techniques

153

MultiPulse Amperometry
The MultiPulse Amperometry technique allows you to perform
constant potential and pulsed amperometric, and some voltammetric
experiments. The applied waveform is constructed by the addition of
up to two pulses on a base potential. These pulses may be either
positive or negative and may be increased or decreased throughout
the scan for voltammetric work. You are able to dene any one of a
number of regularly used methods. There is also the added exibility
of being able to dene an unusual pulse sequence. In addition up to
four current sampling windows can be selected with their position
and duration independently set.
A library of different signals, that can be used at any time, can be
achieved by writing Macros that record your methods or by storing
parameters in Settings les. This will allow you to automate your
experiments.

Parameters
To use this technique, select the Multi Pulse Amperometry from the
Techniques menu. The dialog shown in Figure 729 will appear.

Figure 729
The Multi Pulse Amperometry
dialog box.

Each parameter is altered by entering a new value in the appropriate

box, or selecting a new menu item. Changes take effect when the OK
button is clicked. Click the Cancel button to exit without saving.

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Base potential
First the base potential is set. This must be within the extreme values
of the Range setting.

Speed
The data acquisition rate is normally set at 10 kHz. Very long
sampling periods may require slower speeds. Up to 4095 samples can
be averaged in one sampling period.

Range
The range pop-up menu selects the full scale range of the applied
potential. Three ranges are available, 1000 mV giving 0.5 mV
resolution, 2000 mV giving 1 mV resolution, and 5000 mV giving
2.5 mV resolution.

Steps
The total number of steps taken during the experiment is entered here
and must be less than or equal to 16000.

Step Width
The time taken for a single step of the experiment (base potential +
pulse 1 + pulse 2) during the experiment:

Duration
The Duration is the total time taken for the experiment and is
automatically calculated:
Duration = Steps StepWidth

Rest Time
This is the period after the deposition potential is applied and the
scan commences. This is usually set to between 1 and 60 s, or longer
for corrosion experiments.

Chapter 7 EChem Techniques

155

Dening pulses
For each step up to two pulses may be applied. Each pulse is
activated by clicking the box in the upper left-hand corner of the
pulse panel, and now the relevant parameters can be entered.

(Pulse) Start
The timing of each pulse is linked to the start of each step. For
example if you enter 100 ms in the Start box it means the pulse will be
activated 100 ms after the beginning of the step. The pulse can begin
at any time during each step but the start time must be less than the
Step Width

(Pulse) Height
The height of the pulse. Make sure that the sum of the base and pulse
potentials does not exceed the Range setting.
Note that the value for the height of the pulse is added to the base
potential. If two pulses are made to overlap then the base and two
pulse potentials are all added together over this period.

Inc(rement)
Pulses on successive steps will be incremented by this amount. If you
enter a non zero value you will probably be doing a pulsed
voltammetric experiment ie the potential will be changing in a ramplike manner during the experiment.

Width
The duration of the pulse must be such that the entire pulse occurs
within one step of the experiment.

This is best explained by examples. The dialog box shown in Figure

730 sets up two simple pulses, each 100 ms long, on each 500 ms step
of the experiment.

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EChem Users Guide

.
Figure 730
Example settings for Multi
Pulse Amperometry
experiment.

Figure 731
Waveform overview for the
settings in Figure 730.

By clicking the View... button the Waveform Overview window

displays the appearance of several steps of the ramp, Figure 731.

The Sampling Dialog

By clicking the Sampling... button in the Multi Pulse dialog the
Sampling Time dialog in Figure 726 is activated. This dialog allows
you to nominate the current sampling periods during each step by
entering the time and duration of each of up to four periods (i1, i2, i3,
and i4).
The dialog box is divided into four panels which control each of the
four sampling periods. Adjust the parameters in the same manner as

Chapter 7 EChem Techniques

157

described for the Sampling Dialog in the MutiPulse Voltammtery

Technique.
Sampling periods that are multiples of 20 ms will discriminate
against 50 Hz mains frequency noise (use a multiple of 16.7 ms if
your main power is at 60 Hz).

Displaying MultiPulse Amperometric Data

For existing data the Sampling Display... command, in the Display
menu, brings up the Data Selection dialog, Figure 728, which is can
be set to display i1, i2, i3 or i4, or the difference between any two of
these. If you require to display more complicated functions you will
need to transfer the data to a spreadsheet or graphing application.

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The Apply Technique... command

An EChem le may contain many different types of experiment that
have employed one or more techniques with different parameters.
You may occasionally want to use the technique and parameters of a
particular page (run) for your next scan. Click on the page button of
the that required to display it. Next go to the Apply Technique...
command in the Techniques menu. This will bring up the parameter
entry dialog with the settings used for that run. You can modify any
of the parameters if desired. When you click OK you are ready to
begin the next scan using these parameters.

Chapter 7 EChem Techniques

159

CAUTION. Connection
of the PowerLab to an
external dropping
mercury electrode should
only be attempted by a
qualied electronics
technician.

TTL logic signals are a

simple means of on/off
communication between
instruments. TTL high
corresponds to a voltage
level of about 5 V, while
TTL low corresponds to
a signal of about 0 V.
These states are
controlled in software by
a bit variable which is
referred to as being set on
or off.

Polarographic Techniques
If you are using a PowerLab S or ST model or PowerLab/800, or
MacLab/8e, then the use of dropping mercury electrode (DME) is
facilitated by the provision of a synchronized TTL pulse signal (of
about 5 V amplitude and 10 ms duration) at the beginning of each
step. This pulse is carried by Output 4 of the TTL digital output lines
accessed at the back of the PowerLab unit. Consult your PowerLab
Owners Guide for pin connection information.
This signal is provided for all EChem techniques all the time.
However, as the duration of the TTL pulse is 10 ms, your technique
must employ a step width of greater than 10 ms so that the signal can
return to its resting state between steps. Thus the drop rate must be
signicantly less than 100 per second. Note that the TTL signal is
provided for timing purposes only, and that there is not enough
current available (about a milliampere) to actually drive a solenoid
drop hammer directly. In such cases you will need to construct a
suitable amplier/power source for your DME.
In addition Output 3 of the digital output (PowerLab S and ST
models and PowerLab/800 or MacLab/8e only) is set on at the
beginning of each scan and turned off at then end of the experiment.
If you want to do a series of sweeps with a hanging mercury drop
electrode (HMDE), with a new drop for each experiment, then this
signal can be used. Outputs 1 and 2 are described on page 138.

Figure 732
The Digital IO panel. Output
3 is shown on, while outputs
1, 2, and 4, are shown off. On
most PowerLab e models
only Outputs 1 and 2 are
shown.

160

You can monitor or manually control the digital output signals by

activating the Controls subcommand in the Preferences command in
the Edit menu (ie Edit/Preferences/Controls), Figure 61, and then
select the Digital IO display panel control. The Digital IO panel,
Figure 732, will now be shown at the right of the screen. When
EChem is scanning the indicators for outputs 1, 2, 3, and 4 will turn
green when they are active. When EChem is not scanning you can
click on the indicators, this will turn on the relevant output and the
indicator will be shown as green. Manual operation of the outputs is
useful for testing you connection cable, but it is overridden by
automatic operation when a scan is commenced. The indicator for
Output 4, (10 ms pulses for drop hammer synchronisation) usually
appears off during a scan because the 10 ms pulses are too short for
the screen display.

EChem Users Guide

C H A P T E R

E I G H T

Additional Techniques
Apart from the EChem software, additional electrochemical
techniques can be performed with PowerLab using the Chart and
Scope software.

Also discussed is the use of the ADInstruments Potentiostat when

congured as a Galvanostat with Chart and Scope software.

EChem Users Guide

161

Introduction
In addition to the EChem techniques, you can also use the Chart and
Scope applications to perform or monitor the following experiments:

162

AC voltammetry use Chart or Scope to monitor, or Echem to

provide a staircase ramp waveform;

Chronoamperometry use Chart or Scope to monitor or to

provide a square wave signal;

Chronocoulometry use Chart or Scope to monitor and

integrate the current signal or to provide a square wave signal;

Chronopotentiometry use Chart or Scope to monitor the

potential signal or to provide square wave signal;

Fast scan techniques use Chart or Scope to monitor, or use

Scope to provide a potential ramp (up to 500 V/s) signal to
potentiostat, and to subtract charging current contributions;

Controlled Potential or Controlled Current Electrolysis and

Electrosynthesis use Chart or Scope to monitor or to provide a
potential signal to the potentiostat;

Rotating Ring Disk Electrodes use Chart to monitor up to two

current and two potential signals with, for example, a
PowerLab/400 or /4SP;

Titrimetry use Chart or Scope to monitor the current signal

from the amperometric or potentiometric sensor. The
ADInstruments Pump can be used as an autoburette;

Quartz Crystal Microbalance experiments use Chart software

to monitor potential current and mass changes;

Amperometric detection (for chromatography) use Chart to

monitor the output from the detector; and

Monitoring of meters for biosensors, pH and ion selective

electrodes, conductivity electrodes and dO2 sensors.

EChem Users Guide

AC Voltammetry
EChem is not specically designed for AC voltammetric studies but
there are several ways to use your PowerLab with this technique. If
your existing potentiostat or waveform generator system can perform
AC voltammetry then you can use your PowerLab with Chart or
Scope to record the results. Your PowerLab now replaces a
conventional chart recorder.
Alternatively EChem can drive such a potentiostat using the Linear
Sweep or Cyclic Voltammetry modes. The potentiostat can be used to
provide an AC waveform. Provided the step width of the staircase
ramp generated by EChem is very much longer than the period of the
AC waveform then you will get good results. For example if your AC
excitation is 20 Hz, with a period of 50 ms, then you should ensure
that the step width is at least 200 ms.
You can also use EChem and a PowerLab connected to a potentiostat,
AC waveform generator and AC lock in amplier. Both the EChem
and the AC waveform can be summed into the potentiostat. Again
make sure that the step width of the staircase ramp is much longer
than the period of the AC waveform.

Fast Scan Techniques

Some techniques using microelectrodes require very fast scan rates.
EChem is designed for electrochemical techniques where very high
speeds are not required. The minimum step width allowed in EChem
is 0.1 ms, Table 71. You will nd that this will allow scan rates of up
to about 80 V/s (with PowerLab s models) or about 30 V/s (with
other PowerLab models) and still maintain adequately small step
heights in the applied potential ramp. If you require faster scan rates
for linear sweep or cyclic voltammetry, then you should use Scope or
Chart. Both Chart and Scope incorporate Stimulator and Output
Voltage commands which can be used to control the analog output of
the PowerLab and to create a waveform suitable for driving a
potentiostat.

Chapter 8 Additional Techniques

163

Chart and Scope can sample up to 40,000 points per second on two
channels or up to 105 points per second on one channel. You can make
use of these features in a number of ways:

if you are using a third party potentiostat capable of fast scan

rates then you can use Scope as a storage oscilloscope for
recording data. Up to 2560 points can be collected on one channel
at a rate of up to 100 kHz, or up to 40 kHz on two channels.

with Chart software you can monitor one channel continuously

up to 200 kHz (PowerLab/4SP, /8SP, or /16SP) or 1 kHz
(PowerLab/200, /400, /800). On the slower models you can also
record in snapshot mode up to 16000 points at up to 100 kHz on a
single channel.

Remember that Chart or Scope data is not averaged from a series of

readings over a nite sampling period, as it is in EChem. Each data
point corresponds to only one sampling of the signal, thus you may
nd that noise is more troublesome when recording at high speeds.
Read the Chart and Scope User Guides for further information on how
to set up your experiment.
The PowerLab/4SP, /8SP, and /16SP models have extended high speed
sampling:

using Chart a single channel can be recorded at 200 kHz

indenitely to hard disk (or 100 kHz if using USB interface).
Similarly 2 channels can be recorded at 100 kHz, 3 or 4 channels
at 40 kHz, and 58 channels at 20 kHz, and 816 channels at 10
kHz, all continuously to hard disk.

in both Chart and Scope the PowerLab stimulator (waveform

generator) can be used at even the fastest sampling rates.

Fast Cyclic Voltammetry

Scope software has a number of features that facilitate Fast Cyclic
Voltammetry (FCV). The base potential is set by using the Constant
Output dialog box while the waveform is generated using the
Stimulators Up & Down or Triangle waveforms (Figure 81). See the
Scope User Guide for further details.
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EChem Users Guide

Figure 81
Setting up the Stimulator in
Scope to perform Fast Cyclic
Voltammetry

The base potential has been set to 1.00 V and a potential ramp has
been set up to go from 1.00 to +1.00 V and back again over a period
of 40 ms using the Up & Down waveform option. This corresponds to
a scan rate of 50 V/s.
Figure 82 shows an example of a positive and negative cyclic
waveform. The base potential has been set to +0.20 V and a potential
ramp has been set up to go from +0.20 to +0.80 V back again to -0.40
V and nally return to +0.20 V, over a period of 20 ms using the
Triangle waveform option. This corresponds to a scan rate of 120 V/s.
The Triangle waveform option always starts a scan in the centre of the
potential limits, while the Up & Down waveform option starts a scan
at one or the other potential limits.
When performing FCV a large background charging current is often
recorded. This can be a hundred times larger than the signal you are
looking for. Fortunately the charging current is highly reproducible
between scans and can be subtracted out: a background scan is
obtained, and then the run repeated on a new page where the
compound of interest (often a neurotransmitter) is present. Make sure

Chapter 8 Additional Techniques

165

Figure 82
Cyclic voltammetry using
Scope and the Stimulators
Triangle waveform option

that the two scans are run at the same gain setting. Select the Scope
page that contains the background scan then use the Set Background
command this will subtract this scan from all other pages in the
le. Use the Don't Subtract Background command to cancel
subtraction, and the Clear Background de-identies the background
page. See the Scope Users Guide for more information.

Low Current Experiments

Some experiments using microelectrodes (especially when used in
organic solvents, or for in vivo studies) require the measurement of
extremely small currents. You can use the PowerLab system to
perform electrochemistry on such systems provided that you have a
suitable potentiostat available.
If you are using microelectrodes the you may need the
ADInstruments Picostat (under development at the time of writing)
This has a thousand times the sensitivity of the ADInstruments
Potentiostat. To minimize interference from noise, try to position the
Picostat as close to the electrodes as possible, and shield the
experiment well (usually by enclosure in a Faraday cage).

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EChem Users Guide

Another suitable instrument for microelectrode work is the BAS Low

Current Module (available from Bioanalytical Systems Inc.). This
system can be supplied with its own Faraday cage (the BAS C2 Cell
Stand) and has current ranges from 10 pA/V to 1 A/V, with a
maximum current of 12 A. The current signal is amplied near the
electrodes inside the Faraday cage. Your ADInstruments dealer can
supply the necessary cables to connect your PowerLab unit to this
system (see Chapter 9). Please note that the Low Current Module is
directly connected to the PowerLab unit no other potentiostat is
required.

Chronoamperometry
These techniques require that a constant potential is maintained for a
dened period while the current is monitored (chronoampero-metry).
If the current signal is integrated with respect to time then the total
charge transferred at the electrode can be calculated (chronocoulometry).
For these techniques Chart and Scope (supplied with the PowerLab
unit) can be used. PowerLab with Chart or Scope will allow you to
perform Single, Double and even Multi-Step Chronoamperometry,
with data collection taking place in milliseconds or over hours or
even days if need be.

Chronoamperometry and Chart

Chart software can be used to output a constant potential (up to
10 V) with a suitable potentiostat equipped with an external input
(or the ADinstruments Potentiostat). The Timed Events (Setup menu)
feature can be used to keep the potential constant for a xed period of
time, or even to drive the reaction backwards after the initial
oxidation/reduction.
To adjust the potential you will rst need to select the range by
choosing the Constant Voltage command in the Setup menu to
activate the Constant Output dialog, Figure 83. You can set the
control voltage sent to the potentiostat by setting the slider bar or
entering a value after clicking the A-button. The slider control, and
the direct text entry available with A-button, both offer 12 bit
resolution (0.024%) within each range (selected by the pull down).
Chapter 8 Additional Techniques

167

This equates to 1 mV resolution if you use the 2 V range, which is

suitable for most experiments employing aqueous solutions.

Output Voltage
control for
PowerLab S series
models)

Figure 83
The Constant Output Dialog
box.

At the time of writing the

control of the Stimulator
with Chart software on
Windows computers was
still under development.
There may be signicant
differences in its use.

Output Voltage
control for
PowerLab e series
models

If you are using a bipotentiostat with a PowerLab S series model then

clicking the Independent radio button, Figure 83, allows you to set
two output voltages which can be sent to the two external inputs of
the bipotentiostat.
The Chart software Stimulator command (in the Setup menu) can also
be used to set up pulses, stepped pulses, and staircase ramp
waveforms which the potentiostat will follow. PowerLab S series
models can also be congured in Chart software to provide
sinusoidal and triangular wavefunctions).
You can also use the Timed Events feature (Setup menu) to adjust the
current at predetermined time intervals after the start of recording.
For example the settings shown in Figure 84 will maintain a
potential of 1.25 V for 30 minutes after which the potential will be
decreased to 0.50 V in order to reverse the reaction, resulting in a
Double Step Chronoamperometric experiment. Any number of steps
at any potential could be set up with this feature.
At the time of writing the
Timed Events feature was
only available for
Macintosh systems.

168

Timed Events can be slightly delayed by up to (0.1 s) depending on

the model of computer and what else is happening. For fast charging
and discharging systems it is better to use the Chart Stimulator.
EChem Users Guide

Figure 84
An example setting for
performing chronoamperometry using Timed
Events in Chart

Using the Stimulator command in the Setup menu it is possible to

send and monitor pulses with a precision better than 1 ms. Pulses up
to 29.9 s may be created by this method. For further details on using
the Stimulator in Chart refer to the Chart Users Guide. An example
using the Chart Stimulator is shown in Figure 84.

Figure 85
An example showing how the
Stimulator in Chart can be
used to generate fast pulse
waveforms.

Chapter 8 Additional Techniques

169

At the time of writing the

Curve Fitting extension is
only available for
Macintosh systems.

Analysis of Chronoamperomograms
The resulting chronoamperomograms obtained from a planar disk
electrode should exhibit a current/time relationship governed by the
Cottrell equation, Appendix D.

nFAD 1 2 C
i = --------------------------------1
1
1000 2 t 2

Curve tting extension icon

You can use the Chart Curve Fitting command (Windows menu) to t
your data with a an idealised curve. This command will only be
present if the Curve Fitting analysis extension is correctly installed in
the Chart Extensions folder (adjacent to the Chart software icon on
your hard disk). For instructions on the use of the extension also see
Application note AN003 which can be downloaded from our web site
at [Link]
It is usually easier to rst simplify the Cottrell equation to:

a
i = --------1 2
t

The Curve Fitting command

is added to the Chart
Windows menu if the Curve
Fitting extension is installed

where a is treated as an empirical constant to be determined. In

addition it is unlikely that the results will decay to exactly zero
current (due to convection currents in the vessel causing non-ideal
diffusion) so a small non-zero constant, b, is added. Finally the
equation is very sensitive to the exact instant when t is zero. This can
be a problem if you have selected data very close to zero time (it is
best to use the t = 0 at start of block option, Figure 87). To get a well
behaved equation when the data selected start at very close to zero
time it is usually best to initially add a small time correction, c, which
will allow for the errors in your estimation of time zero, and the fact
that the potentiostat will take a nite time to stabilise after the change
in potential. Thus the nal form of the equation to be tted is:

a
i = ----------------------- + b
1
(t + c) 2
This must be entered as a New Equation in the Curve Fitting
extension the very rst time you use it, Figure 86.

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EChem Users Guide

Figure 86
Entering an equation suitable
for the Cottrell equation

First lock the value for c, then type in guesses

for a and b until an approximate t is obtained

Figure 87
Fitting a Cottrell equation to
chronoamperometric data

Usually use t=0 at start of block

Iterate by clicking the Fit button, rening a and

b only. If the initial guesses are close enough
then better vales for a and b will be obtained.

Unlock c, and iterate again. A curve

of even better t should be obtained.

Chapter 8 Additional Techniques

171

After the le is saved the equation will be available whenever you

open Chart data le on the computer or even when you transfer the
data le to another computer. Some trial and error will be involved
while you make guesses that are suitable for the initial values to
commence iteration.
Because of the discontinuity that occurs when the denominator is
zero problems can occur if the selected data starts at zero time (or
close to zero time). In this case rst try xing c to a small positive
value, and iterating for better values of a and b. Usually your data
selection should not include data points very close to zero time (the
potentiostat will require some time to settle remember to have the
potentiostat low pass lters turned off otherwise you may only be
measuring the lter response time!), nor points taken at very long
times when convection aided diffusion will produce non-ideal
behaviour. The exact time period that is suitable will depend on the
size of the electrode and the quality of the potentiostat and some trial
and error to determine the best time interval will be required. After
the better estimates for a and b have been determined c can be set free
to rene during the next iteration cycle, Figure 87

Chronoamperometry and Scope

CAUTION
If you are using a high
compliance potentiostat or
galvanostat remember that
dangerous or even lethal
potentials may be
generated across the
electrodes. Read your
potentiostat/ galvanostat
manual carefully to
establish safe working
procedures, and always
isolate the cell before
disconnecting the
electrodes. The potential at
which the potentiostat is
set refers to the potential
between the working and
reference electrodes, the
potential between the
auxiliary and working
electrodes may be many
times greater!

172

For chronoamperometric measurements, where you need to overlay

the results of successive experiments, Scope will generally be the
program of choice.
The total length of the experiment is chosen in the Time Base panel
(128 s is usually sufcient, this is given by the 100 s setting). Up to
2560 data points can be collected in this period. The base potential is
adjusted with the Output Voltage command (Setup menu) and is
similar in function to the corresponding Chart software control
shown in Figure 83.
The potential that will cause the reaction to proceed (and the time
that it will be applied) is set using the Stimulator command in the
Setup menu. In the example shown in Figure 89, after a period of
10 s at the base potential, two 30 s pulses of 0.70 V are to be applied
each followed by a 30 s return to the base potential.
The experiment is usually rst done on a blank solution containing
only electrolyte, followed by a sample solution containing the
EChem Users Guide

Figure 88
The Scope software
Stimulator dialog set up for a
multistep chronoamperometric
experiment.

substrate. The data is collected on separate pages in Scope and the

blank subtracted with the Set Background command then cut and
pasted to a spreadsheet application so that the differences can be
plotted against 1/(t) in a Cottrell graph. For further details on using
Scope refer to the Scope Users Guide.
If you want to t chronoamperomograms, that were collected with
Scope software, to the Cottrell equation the rst import the data to
Chart software (see Application Note AN010 which can be
downloaded from our web site at [Link]
and then use the Curve Fitting extension discussed in the previous
section.

Chronocoulometry
Chart and Scope software have the ability to integrate an incoming
signal both in real time or off line. Since the total charge transferred
(the total number of coulombs, or electrons, transferred) is equal to
the integrated current, the settings used for chronoamperometry can
also be used for chronocoulometry. It is only necessary to set up an
unused channel (usually channel 3 if using Chart software) to be the
integral of the current monitor channel (usually channel 1). Note,
however, that the accuracy of this method is not as good as the results
that can be obtained from a precision coulometer. If you require very
precise results you should record the signal directly from such a
device.

Chapter 8 Additional Techniques

173

In Scope software either of the two input channels can be integrated

by choosing the Computed Functions option (Figure 89) in the
Display menu. The Integrate function is chosen from the functions
pop-up menu. The integrated channel will reset itself automatically if
the integral goes off scale. This works in the same way as an
integrating pen recorder would. Refer to the Scope Users Guide for
more information.

Figure 89
Integrating the current data
with Scope software.

When using Chart software, any one of the unused channels can be
setup to be the integral of the current channel. This is an on-line
function so you need to record to display the integral. To setup
integration you need to choose the Computed Input command from
the Channel pop-up menu which brings up the Computed Inputs
dialog box (Figure 810). Several integration options are available. For
more information refer to the Computed Inputs sections in the Chart
Users Guide.

Figure 810
Setting up on-line integration
in Chart using the Computed
Inputs dialog box

174

EChem Users Guide

At the time of writing the

Integral extension for post
acquisition integration of
data is only available for
Macintosh systems.

For post-acquisition integration of a signal recorded with Chart the

Integral extension can be used. This is particularly useful since the
results can be recalculated from the original current signal at will. The
on-line method will give good results only if the appropriate
sensitivity range has been selected and it is not always possible to
decide on this beforehand.

Chronopotentiometry
This technique requires that a constant current be maintained
between the working and auxiliary (counter) electrodes. The potential
at the working electrode is monitored. For many systems the
potential will remain approximately constant until the electroactive
species is consumed in the region of the electrode.
For this type of experiment it will be necessary to use a specialist
galvanostat or to run your potentiostat in galvanostat mode (check
the potentiostat's manual to see if your potentiostat can be used in
this mode) and use Chart to record the data. The ADinstruments
Potentiostat can be used in galvanostat mode using Chart or Scope
software. If you are using a third party potentiostat/galvanostat you
can set the potential from the front panel of the potentiostat and use
Chart or Scope software to record the current and potential with time.

CAUTION
If you are using a high
compliance potentiostat or
galvanostat remember that
dangerous or even possible
lethal potentials may be
generated across the
electrodes. Read your
potentiostat/galvanostat
manual carefully to
establish safe working
procedures, and always
isolate the cell before
disconnecting the
electrodes.

Alternatively once the galvanostat is set up, adjust Chart or Scope as

you would for chronoamperometry. Remember, however, that the
PowerLab output voltage will be converted to a current value by the
galvanostat. In most cases this means that only small values should
be used, < 100 mV, which would correspond to < 100 mA if a 1:1
correspondence is maintained by the galvanostat. This is because
most galvanostats will not be able to generate voltages big enough to
pass larger currents.

The ADInstruments Potentiostat

as a Galvanostat
Like many other potentiostats, the ADInstruments Potentiostat can be
congured for galvanostat operation (with Chart or Scope software).
However since it is primarily designed for potentiostatic operation

Chapter 8 Additional Techniques

175

you will need to take some extra care when setting it up as a

galvanostat.
Figure 811
Setting up the ADinstruments
Potentiostat in galvanostat
mode.

At the time of writing the

control of the Potentiostat
with Chart software on
Windows computers was
still under development.

Display area showing

potential signal

First nd the Potentiostat

menu item in the Chart
software Channel menu

At each PowerLab control Output Voltage setting

there are four current range settings available

First switch to the galvanostat mode of operation. Choose the

Potentiostat item in the Channel menu to open the control window
and turn on the Galvanostat and Dummy radio buttons, Figure 811.
The default setting is for zero current on the 100 mA range. It is likely
that there will be a small residual offset at this setting which will
cause the Potentiostat/Galvanostat to go off scale (over 10 V) in
standby mode (as it is connected to the internal 100 k dummy cell).
Try selecting the 1 A or 10 A range, where the offset will be
correspondingly smaller, and the signal should come on screen and
be close to zero volts.
The PowerLab control voltage can be set using the Chart software
Output Voltage command in the Setup menu. You can select a range
of 100 mV to 10 V in [Link] increments on most models, or 200 mV to
10 V on PowerLab /200 and /400 models, Figure 83.
At each of the Output Voltage range settings the ADInstruments
Potentiostat/ Galvanostat offers four current range settings when in
Galvanostat mode, Table 81. The most accurate control is achieved
by using the largest possible Output Voltage range with the smallest
176

EChem Users Guide

possible Galvanostat range setting. The resolution within each range

is 12 bits or 0.024% of the range setting.
You can use the slider bar, or the A-button to adjust the current within
the selected range. The resulting potential signal is shown in the
display area. Remember to set the radio button back to Standby
before you return to the main Chart window.

Table 81 Galvanostat range settings available for each Output Voltage range of the
PowerLab unit, when using the ADInstruments Potentiostat in galvanostat mode.
Output Voltage Range

Galvanostat Range Settings

10 V

1 A

10 A

1 mA

100 mA

5V

500 nA

5 A

500 A

50 mA

2V

200 nA

2 A

200 A

20 mA

1V

100 nA

1 A

100 A

10 mA

500 mV

50 nA

500 nA

50 A

5 mA

200 mV

20 nA

200 nA

20 A

2 mA

100 mV *

10 nA

100 nA

10 A

1 mA

* This setting not available on some PowerLab models (for example PowerLab/200 and /400).

If you are using a PowerLab/200 or /400 with Multiport connection

to the Potentiostat/Galvanostat then when you return to the main
Chart window and begin recording the potential signal will be
shown on channel 2 and the current signal on Channel 1. If you are
not using a Multiport cable then the current and potential signals will
be recorded on the channels you have used to connect the
Potentiostat/Galvanostat. The current channel will automatically
have had Units Conversion applied to it so that the display is
correctly shown in units of nA, A or mA.
You can now control the current passed by the Potentiostat/
Galvanostat by setting the Output Voltage slider bar or entering a
value after clicking the A-button. However you will be adjusting the
PowerLab control voltage which is reinterpreted as a current value by
the galvanostat. For example if you have selected a PowerLab Output
Voltage of 500 mV, and a current range of 50 A you might now wish
Chapter 8 Additional Techniques

177

to do an experiment where the current is held at a constant 35 A (or

35/50 100 = 70% of the range setting). You should now set the slider
control of the Output Voltage control to a value of 70% of 500 mV, that
is to 350 mV. Remember that the use of + and voltages determine
the direction of current ow (into or out of the working electrode).
The Chart software Stimulator command (Setup menu) can also be
used to set up pulses, stepped pulses, and staircase ramp waveforms
which the galvanostat will follow (PowerLab/4SP, /8SP, or /16SP
models can also be congured in Chart software to provide
sinusoidal and triangular wavefunctions). You can also use the Timed
Events feature (Setup menu) to adjust the current at predetermined
time intervals after the start of recording.
Operation of the Potentiostat/Galvanostat with Scope software is
similar but a wider variety of waveforms can be used.
Consult the Chart and Scope Users Guides for more details of the
Output Voltage, Stimulator, and Timed Events features.

Controlled Potential Electrolysis

and Electrosynthesis
These techniques are essentially the same as chronoamperometry. A
constant potential is applied at the working electrode which is
sufcient to oxidize or reduce the substrate. As the electrolysis
continues the substrate is eventually completely consumed and the
current will decrease to a residual value. Both the potential and the
current ow can be monitored with Chart in the same way as for
chronoamperometry. The integrated current (i.e. the total charge
transferred) can also be determined which can be used to determine
the extent of reaction.
A potential should be chosen which is at least 50 200 mV more
oxidizing (or reducing) than the half potential in order to ensure
complete reaction of the substrate. It is important to separate the
auxiliary (counter) electrode from the electrochemical cell by means
of a salt bridge. This is due to the build up of reduction products in
the region of the auxiliary electrode which could react with the
products of oxidation at the working electrode (or conversely

178

EChem Users Guide

products of oxidation will build up around the auxiliary electrode if

reduction is taking place at the working electrode). The working
electrode is constructed to have a large surface area so that a greater
amount of material can be electrolyzed in a small time, thus a plate or
gauze electrode is usually chosen.
It is usual to stir the solution during electrolysis in order to bring a
fresh supply of substrate into contact with the working electrode.
For the conversion of large amounts of substrate (> 100 mg) in
reasonable times relatively high currents must be passed through the
cell. A potentiostat capable of a maximum current of at least 100 mA,
or even 1 A is required. For the electrosynthesis of organic
compounds in highly resistive non-aqueous solvents the addition of a
large amount of electrolyte is necessary to sustain the current ow
(which can sometimes lead to difculties in later separation of the
product), as is the use of a high compliance potentiostat. For studies
using water as the solvent the addition of a small quantity of acid (or
base) can increase the conductivity of the cell greatly, without having
to add large amounts of electrolyte.

Controlled Current Electrolysis

and Electrosynthesis
These techniques are essentially the same as chronopotentiometry
and require the use of a galvanostat (or constant current source and
voltmeter). A constant current is applied between the working and
auxiliary electrodes and the potential at the working electrode is
monitored as the substrate is oxidized or reduced. As the electrolysis
continues the substrate is eventually completely consumed and the
potential will alter as the galvanostat tries to maintain a constant
current. Both the potential and the current ow can be monitored
with Chart software. The integrated current (i.e. the total charge
transferred) can also be determined which can be used to determine
the extent of reaction.
Electrosynthesis reactions are often more quickly carried out under
constant current conditions (especially if there are no competing
redox reactions at nearby potentials) than under constant potential
conditions.

Chapter 8 Additional Techniques

179

It is important to limit the current so that the potential stays within

the compliance voltage of the galvanostat, at least until the reaction of
interest is complete.
Many potentiostats can be used in galvanostat mode consult the
instrument manual to see if this is possible. The use of the
ADInstruments Potentiostat in galvanostat mode is discussed above:
See The ADInstruments Potentiostat as a Galvanostat on page 175.

Rotating Ring Disk Electrodes

A rotating ring disk electrode (RRDE) consists of two electrodes: an
inner circular cross section electrode; and an outer, concentric,
annular electrode. Both the disk and the ring can be controlled
independently by two separate potentiostats or with a bipotentiostat.
Rotation of the electrode causes hydrodynamic ow such that the
solution is moved onto the disk from the bulk solvent then pushed
outwards towards the ring. Thus the RRDE can be used to measure
rates of various redox reactions, using the ring as a detector and the
disk as a generator of various electroactive substances.
Much RRDE work will require at least a four channel PowerLab unit
(for example a PowerLab/400) as the potential and current ows of
both (or either) the ring or disk will need to be monitored.
A typical experiment would use a PowerLab/400 with Chart to
record the results. The current at the ring is held at a constant
oxidizing potential to detect any reduced species formed at the disk.
The disk potential is swept over a range of potentials in order to
generate various reduced species in solution. Because the ring
potential is held constant it does not need to be monitored. But we
will need to plot both the disk and ring currents against the disk
potential so each of these must be recorded. The Chart X-Y Window
command (Windows menu) can be used to plot the results on one
channel versus another.

Amperometric Titrimetry
Titrations can be performed in an electrochemical cell where the
working electrode is held at a constant potential while the current is

180

EChem Users Guide

monitored. As the electroactive species is consumed during the

titration the current decreases.
The ADInstruments Pump, can be used to deliver 50 L aliquots of
titrant to a vessel with a coefcient of variability of 0.3%. It is suitable
(after calibration) for performing titrations on a scale similar to that
used with a conventional 25 or 50 mL burette. Monitoring such a
titration is best achieved with Chart software, plotting volume and
current ow on separate channels. Chart also has the ability to
perform XY plots so that current can be plotted against volume of
titrant added.

Liquid Chromatography
Detectors
Electrochemical detection can be an extremely sensitive technique for
liquid and highpressure liquid chromatography (LC and HPLC).
The method is essentially chronoamperometry on a owing sample.
A owthrough cell must be purchased or constructed.
Chart can be set up to drive the potentiostat at a constant potential for
an indenite period. Alternatively the potentiostat can be set to
provide a xed potential. The potential is chosen such that the
substrate will be oxidised or reduced as it passes through the
electrochemical cell. The current is monitored continuously. As the
substrate passes through the cell an increase in the current occurs, the
current then peaks and subsides as the substrate is pushed out of the
cell by new carrier solution.
Chart can also be used to monitor the outputs of other detectors
connected to other channels of the PowerLab. Thus using a
PowerLab/400 you could monitor output from an electrochemical,
uv-visible, refractive index, and uorescence detector, simultaneously.
In addition four virtual channels of data can be constructed using the
computed functions dialog to monitor the integrated signals (or their
differentials) from each of the detectors. Refer to the Chart User's
Guide for further details.
For more extensive chromatographic use, PowerChrom software is
also available for use with PowerLab units. It can acquire and analyze

Chapter 8 Additional Techniques

181

data, and supports autosamplers and fraction collectors. The

ADinstruments Potentiostat can be used as a low cost electrochemical
detector for chromatography systems when used in conjunction with
Chart or PowerChrom software. Ask your ADInstruments dealer for
more information.

Biosensors
Biosensors are usually of the potentiometric, amperometric or
conductiometric varieties (see the following sections). Usually
ordinary pH meters or high impedance voltmeters can be used for the
potentiometric type. The amperometric variety usually require a
special meter that has an adjustable polarizing potential and a
variable gain ranges suitable for the currents being measured (see
Appendix F). The conductiometric types may work with an ordinary
conductivity meter but may have special requirements in terms of the
frequency of AC excitation or the range of conductances to be
measured. Any biosensor meter with an analog recorder output can
be connected to a PowerLab unit.

Potentiometric sensors
As their name suggests these sensors measure potential, and there
output can always be monitored in units of millivolts or volts. In
some cases it is more convenient to convert this signal to alternative
units such a pH or log[Na] to give a more direct indication of the type
of measurement being carried out. Virtually all these sensors can be
monitored by connection to a pH meter or other high impedance
voltmeter.

pH Electrodes
The impedance of the PowerLab inputs is 106 which is unsuitable
for direct connection to the very high impedance signals produced by
glass pH electrodes. For these electrodes a high impedance
preamplier (a pH or ISE meter with an impedance of >1012 ) must
be used between the electrodes and the PowerLab. The
ADinstruments pH Amp is also suitable for most pH and

182

EChem Users Guide

combination pH electrodes contact your local ADInstruments dealer

for details.
Some pH meters give an output which is directly proportional to the
pH reading on the meter. If this is the case then refer to the meter
manual to nd the relationship between the analog signal (in mV)
and pH. Often the correspondence is 0 mV = pH 0, and
1400 mV = pH 14, in which case the units conversion feature of Chart
can be set up as show in Figure 812

Figure 812
Setting up Units Conversion
for a meter with a known
voltage/pH relationship of
pH 14 = 1400 mV.

If the pH meter outputs a raw millivolt signal (as does the

ADInstruments pH Amp) then you can calibrate the signal with the
specially designed Chart pH extension. See the section entitled pH
and Ion Selective Electrode Calibration, p. 189. This method also has
the advantage of reporting the percentage Nernstian response of the
electrode. If multiple point or non-linear calibration is required then
the Chart MPCalibration extension can be used. See Application
Notes AN006 and AN112 (downloadable in Adobe Acrobat pdf
format from the ADInstruments home page at
[Link]

Ion Selective Electrodes

Ion selective electrodes, like pH electrodes, normally require to be
connected to a high impedance preamplier such as a pH meter or
the ADInstruments pH Amp, which can in turn be connected to the
PowerLab unit. Usually the recorder signal is provided as a raw
millivolt signal which is recorded with Chart software. The Chart pH
extension can be used to calibrate the signal directly in units of pNa,
pCl, etc. If multiple point or non-linear calibration is required then
the Chart MPCalibration extension can be used. See Application
Notes AN006 and AN112 (downloadable in Adobe Acrobat pdf
format from the ADInstruments home page at
[Link]

Chapter 8 Additional Techniques

183

Potentiometric Redox Electrodes

Depending on the design of the electrode it may be possible to
connect a reference and redox electrode directly to the PowerLab
inputs. However, for best quality results it is usually better to use a
high impedance preamplier such as a pH meter or the
ADInstruments pH Amp, which can in turn be connected to the
PowerLab unit. Chart software is usually the best choice to record the
signal.

Dissolved CO2 and NH3 Electrodes

These electrodes measure the pH of an internal solution which is
separated from the bulk solution by a gas permeable membrane. As
CO2 (or NH3) concentration equilibrates on either side of the
membrane, the pH of the internal solution will change. The resulting
signal is usually measured with a conventional pH meter. The
recorder signal of the pH meter can be monitored with Chart software
on a PowerLab unit. The Units Conversion feature of Chart can be
used to perform two point calibration of the signal which is
satisfactory for most uses. If multiple point or non-linear calibration is
required then the Chart MPCalibration extension can be used. See
Application Note AN112 (downloadable in Adobe Acrobat pdf
format from [Link]

Electrode Behaviour
The behaviour of an ideal pH, or ion sensitive, electrode is
characterised by the Nernst equation. This describes the relationship
between observed potential and ion activity.

RT
E = E 0 ------- pY
nF
where
E
E0
R
T
F

184

is the observed potential (in volts)

is the potential when pY is zero
is the gas constant (8.314 J K-1 mol-1)
is the temperature in Kelvin
is the Faraday constant (96487 C mol-1)

EChem Users Guide

is the number of electrons transferred at the electrode

(usually the charge of the ion)
pY = log10[Y] where [Y] is the activity of the ionic species, Y
(for a pH electrode pY = pH)
If pY is plotted against E then a straight line should be obtained of
intercept E0 and a slope of (RT/nF). For pH measurements (n=+1) at
25C and the expression RT/nF has a value of 59.16 mV.
If two solutions of known pY are measured then these values can be
used to construct a graph of a straight line to determine E0 and the
slope. The percentage Nernstian response of the electrode is given by:

100 slope observed

response = ----------------------------------------------slope calculated
where slopeobserved is the observed slope and slopecalculated = (RT/nF)
Such a graph, with the Nernstian response is calculated by the Chart
pH extension.
High quality pH electrodes will have a response in the range 95
102%. Cheaper, older, or poorly maintained, electrodes will most
likely have a response below this range. Ion selective electrodes
exhibit a wider variation which should be taken into account when
characterising electrode types.

Non-Linear Multiple Point Calibration

At the time of writing the

MP Calibration extension
is only available for
Macintosh systems.

Both single and two point calibration assume that the electrode has a
linear response to ion activity. Experimentally there will always be
some deviation from linearity in the response. This is most noticeable
at very high or low concentrations. In these instances a non-linear
calibration technique must be used for accurate work.
If you need to calibrate an electrode directly in terms of ionic
concentration (or log of concentration) rather than activity, a nonlinear calibration is also needed. The Chart Mutipoint calibration
extension can perform this sort of non-linear calibration.

Chapter 8 Additional Techniques

185

The Mutipoint Calibration extension should be installed in the Chart

Extensions Folder (adjacent to the Chart software icon) on the hard
disk of your computer. When the Chart software is next run the
MPCalibration command will appear in each of the channel menus.
Mutipoint calibration
extension icon

The MPCalibration command is

added to each of the Channel
menus if the Mutipoint
calibration extension is installed

In a typical calibration experiment your sensor probe (pH electrode,

biosensor, etc.) might be immersed in a series of solutions of
increasing analyte substrate as you record data, or if you have a ow
system you might make regular injections of the calibration solutions.
The input gain range of the PowerLab channel should be set so as to
accommodate the largest signal you expect to record. If your signals
will cover a very large dynamic range then you can record signals
from different concentration of analyte at different gain ranges.
Recording is continued at each concentration until a steady reading is
obtained or, if a ow injection analysis system is used, until the peak
of interest has passed the sensor. After the calibration solutions have
been recorded the signal will have units of raw millivolts. You can
select a region of data to perform multipoint calibration, Figure 813.
A good idea is to annotate the le with the Chart comments feature
(see your Chart Users Guide) so that each concentration level is
written in the data le.
Choose the MPCalibration command from that channel pop-up
menu. The Multi Point Calibration dialog box, Figure 813, will
appear. Make sure that the correct units (if any) are entered and that
an appropriate number of decimal places is selected.

Figure 813
Selection of data from
potassium selective electrode

Concentrations used can be entered

as comments
Select the data region of interest

186

EChem Users Guide

Comments are marked on the signal

Enter the signal value

Enter the concentration value, or log of concentration

Figure 814
Setting up multiple point
calibration

Set the number of decimal places

Select a region of the signal

that represents a steady signal.
(Clicking would set just one
pint)

Enter the unit name or other identier such as pH or log[K+]

Each calibration solution is

selected and entered separately

Use the arrow buttons to enter

the average of the selected
signal value

Use the Fit button to show the

calibration graph

While in the Multi Point Calibration dialog box select a calibration

level. Enter the mean value in the left hand column (use the arrow
button) and enter the corresponding concentration value in the right
hand column. In most cases the logarithm, base 10, of the
concentration is used if the concentrations are to vary by several
orders of magnitude. Repeat for each calibration level. Next click the
Fit... button to show the calibration graph (Figure 815). Different
functions, can be used to achieve a best t for the data. For difcult
functions use the Point-to-Point function which does linear
interpolation between pairs of points, and extrapolates the rst and
last interval beyond the calibration region. Beware of polynomial
functions which can give unexpected results outside the region of
calibration.

Chapter 8 Additional Techniques

187

Figure 815
Selecting a calibration
function.

The calibration points are shown as a

graph and in spreadsheet format

Choose the
function to t
the calibration
data
Drag the axis tick labels to stretch
and compress the axes
Type in you own title

Check this box if you want

the tted function to pass
through the graph origin
Goodness of t parameters
are reported

The equation of the calibration

function is shown

Copy or Print the results

for a quick report

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EChem Users Guide

The Print button allows printing of the calibration curve for quick
reports, while the Copy... button allows the graph to be copied either
as a picture, or as the text of the calibration data in the small
spreadsheet. Clicking OK returns you to the main Multi Point
Calibration dialog Figure 814.
When the OK button is clicked in the main Multi Point Calibration
dialog, Figure 814, then the calibration calculation will be applied to
the entire channel, Figure 816. You can always revert to the original,
uncalibrated, data by selecting No Calculation in the channel menu.
Figure 816
A view of the calibrated data
in Figure 813.

Also see Application Note AN006. Application Notes can be

downloaded from our web site at [Link]
pH extension icon

pH and Ion Selective Electrode Calibration

If you need to calibrate a pH or electrode then usually a single or two
buffer (single or two point) calibration procedure is used based on the
Nernst equation. The Chart pH extension can perform this sort
calibration. The pH extension should be installed in the Chart
Extensions Folder (adjacent to the Chart software icon) on the hard
disk of your computer. When the Chart software is next run the pH...
command will appear in each of the channel menus.

The pH... command is added to

each of the Channel menus if
the pH extension is installed

If you are using a conventional pH meter with analog outputs,

connect the electrode to the meter input and then connect the meter
output to one of the analog inputs of the PowerLab. The meter should
have a minimum impedance of 1012 and be set to read absolute
millivolts. Any temperature compensation on the meter should be

Chapter 8 Additional Techniques

189

At the time of writing the

pH extension is only
available for Macintosh
systems.

turned off unless you want to use it. If you are using an
ADInstruments pH Amp then follow the instructions in its Owners
Manual to set it up.
Set the PowerLab channel input range to an appropriate range
(usually 500 mV for pH readings in the range pH 0 14). Because
readings from pH and ISE electrodes take several seconds or even
minutes to stop drifting, slow sampling rates in Chart are usually
employed (2 samples per second or less is adequate).
The electrode is placed in a buffer solution of known pH and the
response is recorded using Chart until a steady reading is obtained. If
you are performing two point calibration the electrode is then placed
in a second buffer solution while still recording.

Figure 817
Signal from a pH electrode in
two different calibration buffer
solutions

Select a region of data

to be used for
calibration

A selection of data covering the two pH regions of interest is made in

the Chart window by dragging a selection to include both pH values.
For single point calibration you will only need to record one pH
value. A typical recording of two pH values and an appropriate
selection for use in calibration is shown in Figure 817.
Choose the pH... command from that channel pop-up menu. The
Electrode Calibration dialog box, Figure 818, will appear. Make sure
that the correct units are entered (in this case the units are pH), that
the correct choice for n is made (+1 for pH) and that an appropriate
number of decimal places is selected.
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EChem Users Guide

Figure 818
Setting up electrode
calibration with the pH
extension

Use the arrow button to enter the

average selected signal value

Enter the value of the rst buffer

Select units
Set number od
decimal places
to be displayed
The Eo, slope
and percentage
Nernstian
response are
displayed. For a
single buffer a
100%
Nernstian
response is
assumed.

Select a region of constant signal for the rst buffer

Select value of n

Enter temperature and units

Click the View

Response
button to see
the calibration
graph
Select a region of constant signal for the second buffer

Select an area in the data display region that corresponds to recorded

voltage of one of the pH buffer solutions. Click the arrow icon to the
left of the rst text entry box to put the mean value of the selected
region of the trace into the adjacent box. Now type in the value of the
buffer (in this example a pH of 4.00). The dialog box is updated
assuming the electrode has 100% Nernstian behavior and the Eo value
for the electrode is zero volts. This is equivalent to single point

Chapter 8 Additional Techniques

191

calibration. An example of this process is shown in the top dialog in

Figure 818.
Next select a region of the trace in the data display area which
represents the value of the second buffer. You only need to do this if
you are performing a two point calibration. Click the arrow button to
the left of the second row of boxes to enter the mean value into the
second entry box. Type in the value of the second buffer (pH 10.00).
The slope, Eo value, and percentage Nernstian response of the
electrode is then calculated and displayed. An example of this process
is shown in the bottom dialog in Figure 818.
The calibration data entered will only be applied to the raw millivolt
data in the Chart window when the OK or Apply button is clicked.
Note that this calibration will be applied to all data in the channel,
whether it is pH (or pNa, pCl etc.) data or not. It is therefore
important to remember to use one electrode per channel per data le.
The pH calibration can be turned off at any time by choosing the No
Calculation command from the channel pop-up menu. This allows
you to return to the raw millivolt electrode signal at any time.

Ionic Charge
The n pop-up menu lets you set the value for the number of electrons
transferred at the electrode. This usually corresponds to the charge of
the ion be measured. You can choose a value between 3. For pH
measurements this value should be set to +1. The value of n is used
internally to calculate the response of the electrode using the Nernst
equation.

Calibration Temperature
The temperature of the solutions used for calibration is entered in this
text box. Units of Celsius, Kelvin or Fahrenheit can be selected. The
buffer solutions you use should have accurately known values at the
temperature at which the calibration is performed.

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Viewing the Electrode Response

To conrm the calibration calculation use the View Response...
button. The calibration point(s) will be shown and parameters used in
the Nernst equation are also tabulated. The graph can be printed by
simply clicking the print button. You can also copy either the graph or
the text of the small spreadsheet showing the calibration points. The
graph axes are scalable (drag the axis tick labels, or the area between
the ticks) so that smaller ranges can be plotted, which is particularly
useful for ISE work.
Figure 819 shows two typical electrode responses, one for a single
point calibration, and one for a two point calibration. The default
value for the isopotential point is zero.
Calibration point

Type in your own title

Figure 819
Viewing the response graph

Electrode
parameters are
reported

Calibration point
coordinates are
reported
Print or copy
the calibration

Calibration points
Drag the tick labels
to stretch and
compress the axes

Chapter 8 Additional Techniques

193

The vertical axis of the plot will be automatically scaled to the full
scale range that the data was recorded at. So, for instance, if you were
recording on the 500 mV range then the scale would have a range of
500 mV. If the response does not go anywhere near the current full
scale range you can drag or stretch the vertical axis to obtain a more
detailed plot.
The horizontal axis represents the ionic concentration and is by
default pH. In the case of pH the horizontal scale will be
automatically scaled to be between 0 and 14 pH. This scale can also be
dragged or stretched to view the response plot in more detail. The
small arrow pop-up menu next to the horizontal axis allows you to
use the set scale feature to adjust the axis between two values.
The electrode response dialog can be copied to the Clipboard for
export to a word processor or another application or can be printed
for a permanent record. The title area at the top of the dialog is
editable so that an electrode serial number or other information can
be entered instead of the default title.

Temperature Compensation
There will be times when pH or other ISE measurements will be
made at temperatures other than the temperature under which
calibration was performed. The greater the change in temperature
from the calibration temperature the greater the error in the electrode
reading. Also the further away from the isopotential point the greater
the error. To overcome this problem most pH meters provide a
method for temperature compensation using the Nernst equation as a
basis for compensation.
The pH extension offers both Manual and Automatic Temperature
Compensation (MTC and ATC). Both MTC and ATC corrections can
be turned off so you can return to the uncompensated data.

Manual Temperature Compensation (MTC)

The MTC option is for use when you need to make your
measurements at a temperature other than that at which the electrode
was calibrated. For instance the calibration may have taken place at
25C but you need to record a solution that will be at 65C. MTC will

194

EChem Users Guide

alter the electrode response to suite the new temperature using the
Nernst equation. Note that this mode is not suitable if the
temperature is going to change signicantly during recording. You
should use the ATC mode in this case.
To use MTC make sure that temperature compensation is enabled by
placing a tick mark in the Temp. Compensation check box. Then
select the Manual radio button. The temperature at which recording
will take place or has taken place should be entered in the text entry
box next to the Manual option.
A temperature (other than the calibration temperature) is entered.
When the View Response button is clicked the electrode response
dialog will display two plots: one representing the response at the
calibration temperature; and a second plot showing the response at
the specied temperature, Figure 820.
The calibration response can be identied as the line with one or two
calibration points on it. These are represented as large dots. The
information displayed on the right of the dialog shows the calibration
points and the values used for the Nernst equation.

Response at 65 C

Isopotential point

Figure 820
Electrode response graph
with Manual Temperature
Compensation

Response at 25 C

Chapter 8 Additional Techniques

195

Automatic Temperature Compensation (ATC)

There may be circumstances where the temperature of the solution
being measured cannot be maintained at a constant temperature. In
this case the pH extension provides the necessary functionality to
perform real-time, or automatic, temperature compensation.
Using the Temperature amplier of the pH Amp, or a temperature
signal from a third party temperature measurement device, the
temperature signal can be recorded on a second PowerLab channel.
When the Automatic option is chosen, the pH extension will use
temperature data from one of the Chart channels to correct the pH
channel for variations in temperature. To choose the automatic
temperature compensation option click in the radio button next to the
Automatic option. The channel selection pop-up menu will no longer
be grayed out and you can choose the channel on which temperature
was recorded.

Recording Temperature for ATC

To record and use a temperature channel with the ATC, the channel
must be appropriately calibrated using the Units Conversion feature.
The units must be set to either C, F, or K. If you have not calibrated
the temperature channel you will be warned by the dialog box shown
in Figure 37. This is necessary because the pH extension will look at
the units rst to determine the conversion factor required the Nernst
equation.

Figure 821
Warning dialog if Automatic
Temperature Compensation
is attempted without first
setting up a temperature
channel

Isopotential Point
The isopotential point of the electrode is that potential which remains
constant as the temperature changes. Most pH electrodes are
constructed so that the isopotential point is about 0 mV (which for
most pH electrodes also corresponds to pH 7). But it is usual, even in

196

EChem Users Guide

new pH electrodes, that the isopotential point is actually anywhere

between 50 mV and that this value changes as the electrode ages.
Ion selective electrodes may have an isopotential completely outside
the measuring range of the electrode.
Most pH meters assume an isopotential point of 0 mV (at pH 7) and
then apply either manual or automatic temperature compensation.
The Chart pH extension however allows you to set the isopotential
point to an appropriate value. To calculate the isopotential point, two
calibration runs must be made at two different temperatures, T1 and
T2.
From the Nernst equation:
E = E01 + (slope1) pH
E = E02 + (slope2) pH

or
or

pH = (E E01)/slope1
pH = (E E02)/slope2

where
slope1 = RT1/nF

and

slope2 = RT2/nF

At the isopotential point both potential and pH are constant for both
T1 and T2, that is E = Eip, and pH = pHip. From the above equations
we derive:

( E ip E 01 )
( E ip E 02 )
-------------------------- = -------------------------slope 1
slope 2
which can be solved for Eip:

( E 01 E 02 )
E ip = -------------------------------------slope 1 slope 2
or:

( E 01 E 02 )nF
E ip = ---------------------------------R(T 1 T 2)
For best results ensure that T1 and T2 are at least 20 degrees apart.

Potentiometric Titrimetry
The ADInstruments Pump, can be used to deliver 50 L aliquots of
titrant to a vessel with a coefcient of variability of 0.3%. It is suitable

Chapter 8 Additional Techniques

197

(after calibration) for performing titrations on a scale similar to that

used with a conventional 25 or 50 mL burette. Monitoring such a
titration is best achieved with Chart software, plotting volume and
current ow on separate channels. Chart also has the ability to
perform XY plots so that current can be plotted against volume of
titrant added.

Dissolved Oxygen, dO2, Sensors

Usually the sensor electrode and meter will be purchased from the
same manufacturer because the gain settings of the meter must be
appropriate for the current signal from the electrode. The recorder
output of the dO2 meter can be connected to your PowerLab unit. On
line measurements can be made over periods of less than a second to
weeks if need be. This can be an ideal way to monitor water quality
over a long period of time, or for monitoring of fermentation reactors.
Most oxygen sensors exhibit a slow response time and will take at
least 20 s to stabilize. The Units Conversion feature of Chart can be
used to perform two point calibration of the signal which is
satisfactory for most uses. If multiple point or non-linear calibration is
required then the Chart MPCalibration extension can be used. See
Application Note AN112 (downloadable in Adobe Acrobat pdf
format from [Link]

Conductivity Sensors
Conductivity measurements are usually performed with a pair of
platinum plate electrodes. The conductivity meter provides a small
amplitude AC signal from 50 1000 Hz (to prevent hydrolysis of the
solution) and should provide a recorder type signal that is
proportional to the conductivity of the solution. The Units
Conversion feature of Chart can be used to perform two point
calibration of the signal which is satisfactory for most uses. If
multiple point or non-linear calibration is required then the Chart
MPCalibration extension can be used. See Application Note AN112
(downloadable in Adobe Acrobat pdf format from
[Link]

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EChem Users Guide

Simple Galvanic Cells

WARNING
The connection of multiple
Galvanic cells in series
can lead to the production
of dangerous voltages.
PowerLab units are
designed to accept
voltages up to 10V.
Physical damage to the
units will occur if the
voltage exceeds 35V.

Simple galvanic cells used in undergraduate and high school

experiments, for example a Zn | 1 M ZnSO4 || 1 M CuSO4 | Cu
system set up in two beakers joined by a salt bridge can be connected
by wiring the electrodes (anode and cathode) directly to the
PowerLab inputs. There are two ways to do this for a galvanic cell:

connect one electrode to the centre wire of a shielded cable with a

BNC connector at the other end. The second electrode should be
connected to the shield of the cable. The BNC connector of the
cable can now be plugged into the Channel 1 (or Channel 2 etc.)
of a PowerLab unit.

connect one electrode to the centre wire of a shielded cable with a

BNC connector at the other end, and plug this into Channel 1+ of
two or four channel PowerLab unit (these units feature
differential inputs). Connect the second electrode to the centre
wire of a second cable and plug this into Channel 1 of the
PowerLab. Make sure that the + and checkboxes are both
checked in the Input Amplier window to enable differential
input.

The second conguration is the one to be preferred as it allows easy

reversal of the polarity of the system and allows maximum shielding
of the wiring which may be important where small potentials are
being measured.
However, for highest precision work for small potentials, or if your
cell has a high internal resistance, then your electrodes should be
connected to a ADInstruments GP Amp (input impedance 108 , 200
mV maximum), or to a pH meter, or to an ADinstruments pH Amp
(2 V maximum, input impedance 3 1012 ), which in turn is
connected to the PowerLab. If in doubt always use a pH meter or the
ADInstruments pH Amp.

Chapter 8 Additional Techniques

199

Quartz Crystal Microbalance

The use of a potentiostat to control the potential of an electrode which
is also the sensor of a Quartz Crystal Microbalance (QCM) allows
mass changes to be detected during a voltammetric experiment.
You will need a QCM with analog recorder output. A PowerLab (with
at least four channels) with Chart software to monitor current,
potential and mass signals is also required. If you want to control the
potentiostat then a PowerLab/4SP, /8SP, or /16SP is recommended as
these units can be congured with Chart software to provide a
triangular waveform (sent to the potentiostat for a cyclic
voltammetric experiment) while recording on all channels. EChem
software can only record current and potential and is not suitable for
QCM use.

Electrochemical Noise Experiments

PowerLab units with Chart software can be used to measure the
current and/or potential signals from potentiostats, galvanostats and
potential meters. If you are measuring the noise associated with these
signals then you should consult Application Notes AN002 and AN007
which discuss the determination of RMS (root mean square) and
Noise (the standard deviation) functions of a signal, and the
application of digital ltering of a signal. Also of interest is the
Spectrum command in Chart (Windows menu) which can be used for
frequency (FFT) analysis of the signal. This can be us use in
determining if the noise seen is actually a high frequency
interference. Make sure that you are recording at a rate at least twice
as fast as the highest frequency component that you need to detect.
At the time of writing these features are only available on Macintosh
systems.
Application notes can be downloaded from our web site at
[Link]

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EChem Users Guide

Corrosion Measurements
EChem can be used to drive a potentiostat to perform simple
electrochemical corrosion experiments. Because very slow scan rates
are employed make sure that you are running EChem in slower speed
mode (100 Hz, 400 Hz, or 1000 Hz) when attempting these
experiments or you are likely to encounter warning messages saying
that the sampling periods are too long.
In addition PowerLab with Chart and Scope software can be used to
monitor potentiostat systems replacing existing XYT plotters and
chart recorders. In general Chart will be more useful than Scope for
these techniques as the slowest Scope can be run at is 2 Hz for 2560
points, a total of 20 minutes per scan. Chart can be run as slow as 12
points per hour for an indenite period.

Choice of Potentiostat
The American Society for Testing and Materials (ASTM) has put
forward several standard protocols performing corrosion
experiments. The ADinstruments Potentiostat meets the
requirements of ASTM G587 for potentiostatic and potentiodynamic
polarization measurements ASTM G6186 for cyclic potentiodynamic
polarization measurements, and ASTM G5991 for polarization
resistance measurements. However you should note that this requires
that the potentiostat have a maximum current rating of only 100 mA.
If you require a potentiostat with greater capability then consult
Chapter 9 for a suitable instrument that will be compatible with
PowerLab. Also the ADinstruments Potentiostat provides a signal
that is proportional to current. Some third party potentiostats have an
option so that a recorder signal proportional to log of the absolute
current can be obtained. By using such a potentiostat with EChem,
Chart, or Scope, the PowerLab system will be able to present data as
log of current versus potential.
See ASTM Designation G15 90a for standard terminology relating to
corrosion experiments, and also ASTM G3: Practice for Conventions
Applicable to Electrochemical Measurements in Corrosion Testing.
For most experiments the value of Ecorr must rst be determined by
measuring the resting potential of your system. This is usually done
Chapter 8 Additional Techniques

201

by connecting a high impedance digital voltmeter (or pH meter in

millivolt mode) across the working and reference electrodes before
the potentiostat is connected. You may have to wait a few minutes for
the reading to stabilize.

Potentiodynamic Polarization
This is essentially Linear Sweep Voltammetry at very slow scan rates,
typically 0.6 V/hour 0.16667 mV/s, over a potential range that is up
to Ecorr 500 mV.
The potential range should be limited so that extensive water
hydrolysis does not occur as this is likely to produce large currents
that may overload the potentiostat, while bubbles on the working
electrode may alter the rate and type of corrosion taking place, as well
as interrupting current ow and causing a noisy signal. Also the use
of larger potentials than necessary may also accelerate corrosion to
the extent that the surface of the working electrode is altered
sufciently so that results cannot be reproduced.
This type of scan can also be set up using the Multi Pulse technique.
EChem should be run at slower speeds (100 Hz 1 kHz mode) for
these types of experiment to enable longer step widths and data
sampling periods to be used.
The output from EChem is displayed as current versus the potential.
If you wish to display the results as the log of current density versus
potential then the data should be transferred to a third party
graphing program, for example IGOR Pro. A set of macros for IGOR
Pro are available from your ADInstruments dealer to facilitate
plotting of the data in this format.
If you are used to performing this type of experiment with analog
potentiostats then you may wish to do several comparison runs with
known materials to compare results. EChem generates a staircase
ramp and samples the current over a xed period of time at a
constant potential then averages the current value at each potential.
This may lead to smoother graphs and more reproducible results than
you are accustomed to. Make the sampling period a multiple of 20 ms
(if you use 50 Hz mains) or 16.7 ms (if you use 60 Hz mains) to
eliminate noise due to mains hum.

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EChem Users Guide

Cyclic Potentiodynamic Polarization

See ASTM Designation G61 86 for a description of the standard test
method. This experiment can be set up with the Cyclic Voltammetry
in EChem using very slow scan rates typically 0.6 V/hour
(0.1667 mV/s). EChem should be run at slower speeds (100 Hz 1
kHz mode) for these types of experiments. If the results need to be
plotted as the log of current density versus potential then the data
will need to be transferred to a specialist graphing program, or you
will need to employ a third party potentiostat with a recorder output
proportional to the log of current ow.
If you require more control over the sampling period use the Multi
Pulse technique with the Cyclic Parameters setting to dene your
own forward and reverse scan procedures.

Polarization Resistance
See ASTM Designation G59 91 for a description of the standard
practice. This experiment is simply Linear Sweep (or Cyclic)
Voltammetry over a restricted potential range (usually Ecorr 30 mV)
at slow scan rates, typically 0.6 V/hour. This can be performed using
EChem software after rst determining Ecorr with a potentiodynamic
polarization scan, or with a high impedance voltmeter.
Make sure that EChem is running in a slower mode (100Hz 1kHz)
when performing these experiments. This technique can also be set
up in the Multi Pulse technique. Results are usually plotted as current
versus potential.

Chapter 8 Additional Techniques

203

204

EChem Users Guide

C H A P T E R

T W E L V E

Using 3rd Party

Equipment
You may wish to use you PowerLab with a potentiostat other than the
ADInstruments Potentiostat. This is necessary for:

very low current situations; or for

high current/ high power situations.

or you may have existing potentiostats in your laboratory that

you want to use with a computer.

This chapter takes a look at some of the third party equipment that is
compatible with a PowerLab unit using EChem, Chart, or Scope
software. PowerLab units can also be used with many patch, voltage,
or current clamps such as those made by Axon, Warner, or WPI.

Connection of third party potentiostats to your PowerLab unit is

discussed in Chapter 3.

For very low current (picoampere range) work look for the release of
our special low current Picostat (under development at time of
writing).

EChem Users Guide

205

Introduction
There is an extensive range of potentiostats manufactured by third
parties that are compatible with PowerLab. In most cases all that is
required is a simple cable connection to the PowerLab.
A range of adaptor cables can also be purchased from your
ADInstruments dealer.

EG&G PARC
Many of the potentiostat models made by EG&G Princeton Applied
Research (PAR) are suitable for connection to PowerLab systems. A
brief summary of the different PAR models that can be connected to
PowerLab is given in Table 71 at the end of this section. More
information can be found at [Link]

Model 170 potentiostat

This model has been superseded but if you already own one it can be
connected to a PowerLab system using Chart and Scope for plotting,
or using EChem to drive the potentiostat and plot the data. The 170
has a very high compliance (100 V) and due caution should be taken
in its use. The 170 allows AC polarography/voltammetry. Your
electronics workshop can construct a cable to enable EChem to drive
the 173, otherwise an MLC01 Cable Kit can be used to record data
with Chart and Scope.
CAUTION
Please remember that
many of these
potentiostats are high
power models capable of
producing dangerous
voltages. They should only
be used after reading the
manufacturer's
instruction manuals and
becoming thoroughly
acquainted with the
hazards.

206

Model 173 potentiostat

This model has been superseded but if you already own one it can be
connected to a PowerLab system using Chart or Scope for plotting, or
using EChem to drive the potentiostat and plot the data. The 173
potentiostat has a very high compliance (100 V) and due caution
should be taken in its use. Your electronics workshop can construct a
cable to enable EChem to drive the 173, otherwise an MLC-01 Cable
Kit can be used to record data with Chart and Scope.

EChem Users Guide

Model 174 potentiostat

This model has been superseded but if you already own one it can be
connected to a PowerLab system using Chart and Scope for plotting,
or using EChem to drive the potentiostat and plot the data. The 174
has a very high compliance and due caution should be taken in it use.
If you have a 174/51 dual cell differential operation is possible. The
174/50 conguration allows AC polarography.

Model 175 Universal Programmer

The 175 is essentially a waveform generator capable of outputting
pulses or a potential ramp. It can be used to drive potentiostats
capable of accepting a waveform input. It would normally be used
with a potentiostat and the PowerLab system could be used with
Chart or Scope to replace an XY plotter or oscilloscope. The MLC-01
Cable Kit is available to connect your PowerLab to this instrument.
The use of a PowerLab unit as a waveform generator with EChem,
Chart or Scope software renders the Model 175 largely redundant but
it is still useful if you require true analog ramps.

Models 263, 273, and 273A potentiostats

CAUTION
The 273 potentiostats have
a very high compliance
(100 V). Read the
manufacturers manual
and make sure you observe
the correct safety
procedures.

The 263, and 273 series of potentiostats would normally used with
PAR's own programs via their inbuilt GPIB IEEE interfaces and an
IBM clone computer. However, they can also be used with a
Macintosh computer and a PowerLab. You may prefer to use the
potentiostat in its stand alone mode and use the combination of
Scope/Chart and a PowerLab for plotting your data rather than a
standard XY plotter, or you can control the potentiostat by generating
stepped and pulsed waveforms with EChem. The MLC01 Cable Kit
is available to connect your PowerLab to this instrument.

Model 264A potentiostat

The 264A Polarographic Analyser/Stripping Voltammeter can benet
by using a PowerLab/200 with Scope or Chart in place of its standard
XY plotter. Alternatively it can be used with EChem to drive it and
replace its inbuilt techniques. The MLC01 Cable Kit is available from
to connect your PowerLab to this instrument.

Chapter 9 Using 3rd Party Equipment

207

Model 363 potentiostat

The 363 is a nonscanning potentiostat/galvanostat with a maximum
current rating of 1 A and 30 V compliance making it ideal for
corrosion and plating studies, and electrosynthesis. Combining this
potentiostat with a PowerLab/EChem system will enable it to
become a scanning instrument. All the techniques offered by EChem
will then be available with this potentiostat. Newer models of the 363
have inbuilt positive feedback iR compensation. The MLC02 Cable
Kit is available to connect your PowerLab to this instrument.

Model 362 potentiostat

This model has similar specications to the 362 potentiostat with the
added advantage that it can provide its own analog ramp. This means
that techniques that require a true analog ramp can be monitored
with a PowerLab controlled with Chart or Scope. The 362 comes
equipped with positive feedback iR compensation. The MLC02
Cable Kit is available to connect your PowerLab to this instrument.

Model 366 Bipotentiostat

Ring /disk work requires a bipotentiostat (or two single
potentiostats). The model 366 bipotentiostat can be used with a
PowerLab in several ways, including:

a PowerLab/200 or /400 could be used to drive the ring or disk

electrode with EChem (via the external input) while a constant
potential is applied to the disk (or ring) with the other half of the
bipotentiostat. When using EChem only two channels of data can
be recorded.

a PowerLab/400 and Chart could monitor current and potential

at the ring as the ring potential is ramped, while simultaneously
monitoring current at the disk as it is held at constant potential. A
total of three channels of data would be recorded.

For maximum recording exibility with this instrument a four (or

more) channel PowerLab unit is recommend. The MLC03 Cable Kit
is available to connect your PowerLab to this instrument.

208

EChem Users Guide

Model 400 electrochemical detector

The Model 400 electrochemical detector is designed for liquid
chromatography. Both outputs on the Model 400 can conveniently be
monitored with a PowerLab/200 and Chart. With a PowerLab/400
the signals from two Model 400's could be monitored. The MLC01
Cable Kit is available to connect your PowerLab to this instrument.
If you are using a Model 400 detector and a UV-visible or uorescence
detector you can monitor the outputs of any two detectors
simultaneously with Chart and a PowerLab/200. With a
PowerLab/400 you can monitor the output of up to four detectors.
Extra virtual channels are provided which can be used for on-line
integration of the incoming signals (using the Computed Input
feature).
The Model 400 is also suitable for connection to our PowerChrom
system which offers many more features suitable for
chromatographic data analysis.

Model 303A Static Mercury Drop Electrode

The PAR 303A Static Mercury Drop Electrode (SMDE) can also be
used as a Hanging Mercury Drop Electrode or Dropping Mercury
Electrode (HMDE or DME). It can be used with a PowerLab/EChem
system, either with a third party potentiostat, or with a
ADInstruments Potentiostat.

Chapter 9 Using 3rd Party Equipment

209

Chapter 9 Using 3rd Party Equipment

210

yes
10 V
30 V
1 A to
1A
feedback

Inbuilt scan rate

External input
Voltage range
Compliance
Current ranges (full
scale)
iR compensation

feedback

1 A to
1A

30 V

10V

yes

0.1 mV/s
to 5 V/s

yes

yes

yes

362

none

1 A to
1A

10 V

2 V

yes

0 to
1 V/s

yes

yes

yes

366

feedback/
current
interrupt

100 nA to
100 mA

20 V

8 V

yes

Processor
controlled

yes

yes

yes

263

current
interrupt

1 A to
250 mA

20 V

10 V

yes

Processor
controlled

yes

yes

yes

VersaStat

feedback

1 nA to
5A

100 V

5 V

yes

0.1 mV/s
to
500 mV/s

feedback

100 A
to 1 A

100 V

5 V

yes

no

yes

yes

yes

yes2.

173

yes

170

feedback
with /50
option

20 nA to
10 mA

80 V

5 V

yes

0.1 mV/s
to
500 mV/s

yes

yes

yes

174

feedback/
current
interrupt

100 nA to
100 mA3.

100 V

10 V

yes

Processor
controlled

yes

yes

yes

273 &
273A

none

100 nA
to 5 mA

10 V

10 V

yes

1 mV/s
to 10 V/s

yes

yes

yes

264A

none

100 nA
to 100 A

10 V

2 V

no

1 mV/s to
100 mV/s

no

no

yes

400 LC
Detector

Notes: 1. These specications should be veried by the manufacturer, specications may change at short notice; 2. The external input should be modied to accept DC signals as
described in section III, pages 1 & 2 of the PAR 170 instruction manual; 3. Ranges of 10 A and 1 nA can be selected if the instrument is controlled by PARs own software.

no

yes

PowerLab as
waveform generator
Inbuilt scanning

yes

363
PowerLab as plotter

Feature

Model

Table 101
Comparison table for EG & G
PARC equipment. 1

BAS Equipment
Refer to Table 92 at the end of this section for a table of equipment
made by Bioanalytical Systems Inc. (BAS) at its compatibility with
PowerLab. Also see [Link]

Model CV-1B potentiostat

CAUTION.
Please remember that
these potentiostats should
only be used after reading
the manufacturer's
instruction manuals and
becoming thoroughly
acquainted with any
hazards.

The CV1B is BAS's most basic unit and is widely used in teaching
laboratories. It is greatly enhanced by connecting its recorder outputs
to a PowerLab and recording data with Chart or Scope software. It is
not suitable for control with EChem. The MLC06 Cable Kit is
available to connect your PowerLab to this instrument.
To set up scan limits, connect the CV1B to the PowerLab, I output to
Channel 1 and E output to Channel 2. Now open the Input Amplier
on Channel 2. Adjust the scan limits of the CV-1B while using the
Input Amplier window to monitor the value of the potential.

Models CV-27 and CV-37 potentiostats

The CV-27 and CV-37 can both be connected to a PowerLab, with
Chart and Scope, to replace a conventional XY plotter. These units can
also be controlled with EChem and a PowerLab, allowing full use of
stepped ramp and pulse techniques. The MLC-06 Cable Kit is
available to connect your PowerLab to these instruments.

Model PWR-3 Power Module potentiostat

The PWR-3 Power Module can be used directly with a PowerLab and
EChem or Chart or Scope, or you may use it with one of BASs other
potentiostats in combination with PowerLab. Remember that this
instrument can produce dangerous voltages and should only be used
after thoroughly reading its instruction manual. The MLC-06 Cable
Kit is available to connect your PowerLab to this instrument.

Low Current Module potentiostat

The BAS Low Current Module is designed to be used with a
waveform generator. This module can be directly attached to a

Chapter 9 Using 3rd Party Equipment

211

PowerLab unit, and with EChem, Chart, or Scope, software you can
perform very low current (sub nA) work with microelectrodes. Note
that you do not need to purchase a separate potentiostat! Low current
work generally requires the use of a Faraday cage and the low current
module is designed to be compatible with BAS's C2 Cell Stand. The
MLC04 Cable Kit is available to connect your PowerLab to this
instrument.

Models 100A and 100B potentiostat workstations

The BAS 100A, and 100B are both equipped with analog recorder
outputs which can be connected directly to a PowerLab and the data
recorded with Chart or Scope. In addition an analog input is provided
so that control of the instrument is possible with a Macintosh
computer using a PowerLab and EChem. The MLC06 Cable Kit is
available to connect your PowerLab to these instruments.

Model LC-44
The LC44 electrochemical detector is designed for liquid
chromatography. Both generator and detector current outputs can be
monitored with a PowerLab/200 and Chart, or the detector outputs
from two LC44's. With a PowerLab/400 the generator and detector
currents from two LC44's could be monitored. The MLC07 Cable
Kit is available to connect your PowerLab to this instrument.
If you are using an LC44 detector and a UV-visible or uorescence
detector you can monitor the outputs of any two detectors
simultaneously with Chart and a PowerLab/200. With a
PowerLab/400 you can monitor the output of up to four detectors.
Extra virtual channels are provided which can be used for on-line
integration of the incoming signals (using the Computed Input
feature).

Model RDE-1
The BAS Rotating Disk Electrode can be used with most potentiostats.
If your potentiostat is being used with a PowerLab/EChem system
then you can connect the RDE1 to the potentiostat and you will be
able to drive the RDE1 with EChem.

212

EChem Users Guide

Chapter 9 Using 3rd Party Equipment

213
yes
0 to 10 V/s
no
3.75 V

0.5 A to
500 A
none

Inbuilt scanning
Inbuilt scan rate
External Input
Voltage range
Compliance
Current ranges
(full scale)
iR compensation

none

2 A to
120 mA

12 V

5 V

yes

0.1 mV/s
to 4 V/s

yes

yes

yes

CV-27

none

0.2 nA to
12 A

10 V

5 V

yes

0.1 mV/s to
400 mV/s

yes

yes

yes

CV-37

none

10 mA to
1A

85 V

10 V

yes

no

yes

yes

PWR-3

Notes: 1. These specications should be veried. Specications may change at short notice.

no

yes

CV-1B

PowerLab as waveform
generator

PowerLab as plotter

Feature

none

10 pA to
12 A

12 V

yes

no

yes

yes

Low
Current
Module

Model

feedback

100 nA to
100 mA

10 V

3.276 V

no

Processor
controlled

yes

no

no

50W

no

Processor
controlled

yes

no

no

100

feedback

100 nA to
100 mA

12 V

3.276 V

yes

1 mV/s to
10 V/s

yes

yes

yes

100A & B

none

0.1 nA to
50 A

2 V

yes

no

yes

yes

LC-44
LC
Detector

Table 102
Comparison table for BAS
equipment. 1

PINE Equipment
Table 93 provides a comparison of different potentiostats offered by
the PINE Instrument Company, [Link]

Model AFCBP1 bipotentiostat

This model operates on 110 V/60 Hz (the AFCBP1E is the
corresponding 220 V/50 Hz model). It is a true analog bipotentiostat
suitable for cyclic voltammetry and dual electrode hydrodynamic
studies. It is capable of being interfaced to an IBM type computer and
controlled with PINE's own software. It is equipped with analog
outputs and can be used with a PowerLab to replace an XY plotter or
chart recorder. It also has an external waveform input and can be
used with EChem. The MLC-01 Cable Kit is available to connect your
PowerLab to this instrument.

Model AFRDE5 bipotentiostat

This model operates on 110 V /60 Hz (the AFRDE5E is the
corresponding 220 V/50 Hz model). It is a true analog bipotentiostat
similar to the AFCBP1 in features but without the option of
connecting to an IBM computer. It can be used with PowerLab and
Chart, Scope, and EChem. The MLC-01 Cable Kit is available to
connect your PowerLab to this instrument.

Table 93
Comparison table for PINE
equipment

AFCBP1 &
AFCBP1E

Feature

AFRDE5 &
ARFDE5E

PowerLab as plotter

yes

yes

PowerLab as waveform generator

yes

yes

inbuilt scanning

yes

yes

inbuilt scan rate

0 to 1 V /s

0.01 to 10 V /s

external input

yes

yes

voltage range

10 V

10 V

current ranges (full scale)

100 nA to 1 A

100 nA to 1 A

iR compensation

no

no

Note: These specications should be veried. Specications may change at short notice.

214

EChem Users Guide

While many experiments can be performed with a PowerLab/200, for

maximum exibility these PINE bipotentiostats should be used with
a PowerLab/400. PINE also makes a variety of rotators, and disk and
ring disk electrodes. these are also compatible for use with PowerLab
systems.

Metrohm Equipment
CAUTION
Some of these
combinations have
compliance voltages up to
90 V and are a shock
hazard. They should be
used only after thoroughly
reading the instruction
manual and being
thoroughly acquainted
with the possible hazards.

Model 506 Polarecord with 663 VA Stand

The Metrohm 506 Polarecord is found in many analytical
laboratories using polarography for trace analysis. It has provision for
attachment to an external XY recorder and so Scope or Chart can be
used with PowerLab to record data directly to a Macintosh.
It is also possible to use EChem to drive a Polarecord but the pilot
voltage connection on the Polarecord has an attenuation of 1:10. Thus
the maximum potential range that EChem is capable of (5 V) will be
interpreted as 0.5 V. To overcome this you can use a 1:10 amplier to
boost the signal before feeding it into the Polarecord, or, if your
experiment can be run in a 0.5 V range, put up with the
X-axis being out by a factor of 10.

Model 690 Ion Chromatograph

The Metrohm 690 is a conductivity detector system for ion
chromatography. It is ideal for use with PowerLab and Chart to
replace a conventional strip chart recorder. The program Peaks can
then be used to analyse the data and extract peak heights and areas.
For more advanced chromatography our PowerChrom system is
available.

Chapter 9 Using 3rd Party Equipment

215

Schlumberger Equipment
Model 1186 potentiostat
Schlumberger potentiostats (such as the 1186) are compatible with
PowerLab and EChem. The MLC-01 Cable Kit is available from your
ADinstruments representative to help you connect your PowerLab to
these systems.

Radiometer Equipment
Model PGP201 potentiostat
This instrument is a potentiostat/galvanostat which can be used with
Chart, Scope, and EChem. The MLC-01 Cable Kit is available from
your ADinstruments representative to help you connect your
PowerLab to these systems.

Table 94
Features of the Radiometer
PGP201
potentiostat/galvanostat

Feature

PGP201

PowerLab as plotter

yes

PowerLab as waveform generator

yes

inbuilt scanning

yes

inbuilt scan rate

25 V/s to 2.5 V/s

external input

yes

voltage range

4.095 V

compliance

20 V

current ranges (full scale)

1 A to 1 A

iR compensation

none

Note: These specications should be veried. Specications may change at short notice

216

EChem Users Guide

HEKA Equipment
Models PG28.. series potentiostats
The HEKA potentiostats in the PG28 system are all compatible with
PowerLab and Chart and Scope for data collection. In addition they
can also be used with a PowerLab and EChem so that you can use
them as part of a computer controlled system. The MLC-01 Cable Kit
is available from your ADinstruments representative to help you
connect your PowerLab to these Heka systems.
The basic system comprises modules from the series 100 control
ampliers and the series 200 current ampliers. In addition the 300
series modules, trigger pulse and scan generators; 400 series modules,
current integrators; and 500 series module, digital display; can also be
added. Consult [Link] more details.

Table 95
Features of HEKA
potentiostats

Feature

PG28

PG28../5A

PG28.B

PG284

PG285

PG287

PowerLab as plotter

yes

yes

yes

yes

yes

yes

PowerLab as waveform
generator

yes

yes

yes

yes

yes

yes

Inbuilt scanning

no

no

no

yes

yes

yes

Inbuilt scan rate

1 mV/s to
1 kV/s

1 mV/s to 1
kV/s

1 mV/s to
1 kV/s

External Input

yes

yes

yes

yes

yes

no

Voltage Range

10 V

5 V

2 V

10 V

90 V

10 V

Current Ranges (full

scale)

1 A to
2A

1 A to
2A

1 A to
200 mA

1 A to
1A

1 A to
1A

1 A to
1A

iR Compensation

feedback

feedback

feedback

feedback

feedback

feedback

Note: These specications should be veried. Specications may change at short notice.

Chapter 9 Using 3rd Party Equipment

217

Cypress Systems Equipment

Cypress Systems make a variety of potentiostats and related
information. Latest information can be found at
[Link]

Omni 90 Potentiostat
The Omni 90 is a simple potentiostat with inbuilt analog scanning
and also able to accept an external input. It can be used with
PowerLab replacing the XY plotter or chart recorder with Scope and
Chart software, or can be used with EChem software so that stepped
ramp and pulse voltammetry can be performed. The MLC-01 Cable
Kit is available to connect your PowerLab to this instrument.

Omni 101 Potentiostat

The Omni 101 is a stand alone microprocessor controlled analog
potentiostat with inbuilt analog scanning and also able to accept an
external input. It can be used with PowerLab replacing the XY plotter
or chart recorder with Scope and Chart software, or can be used with
EChem software so that stepped ramp and pulse voltammetry can be
performed. The MLC-01 Cable Kit is available to connect your
PowerLab to this instrument.

CS 1000 Galvanostat/Coulometer
The CS1000 can be used with PowerLab replacing the chart recorder
with Chart software.

EI 400 Bipotentiostat
The EI 400 is an analog bipotentiostat (which can also be used as a
single potentiostat) with inbuilt analog scanning and also able to
accept an external input. It can be used with PowerLab replacing the
XY plotter or chart recorder with Scope and Chart software, or can be
used with EChem software so that stepped ramp and pulse
voltammetry can be performed. It is also suitable for use with
microelectrodes.

218

EChem Users Guide

Table 96
Features of Cypress
Systems instruments.

Model
Feature
Omni 90

Omni 101

CS 1000

EI 400

PowerLab as plotter

yes

yes

yes

yes

PowerLab as waveform
generator

yes

yes

no

yes

Inbuilt scanning

yes

yes

no

yes

<100 mV/s to
1000 V/s

no

yes

Inbuilt scan rate

External Input

yes

yes

Voltage range

2.5 V

2 V

Compliance

10 V

15 V

18 V

10 V

Current ranges

0.01A to 100mA

100nA/V to
100mA/V

100 A/V to 1 A

100 pA/V to 100

nA/V

iR Compensation

no

no

no

no

10 V

Note: These specications should be veried. Specications may change at short notice.

Chapter 9 Using 3rd Party Equipment

219

AMEL Equipment
Latest information on AMEL potentiostats can be found at
[Link]

Model 2049 Potentiostat

The 2049 has an external input and can be used with PowerLab
replacing the XY plotter or chart recorder with Scope and Chart
software, or can be used with EChem software so that stepped ramp
and pulse voltammetry can be performed. The MLC-01 Cable Kit is
available to connect your PowerLab to this instrument.

Model 2051 Potentiostat/Galvanostat

The 2051 has an external input and can be used with PowerLab
replacing the XY plotter or chart recorder with Scope and Chart
software, or can be used with EChem software so that stepped ramp
and pulse voltammetry can be performed. The MLC-01 Cable Kit is
available to connect your PowerLab to this instrument.

Model 2053 Potentiostat/Galvanostat

The 2053 has an external input and can be used with PowerLab
replacing the XY plotter or chart recorder with Scope and Chart
software, or can be used with EChem software so that stepped ramp
and pulse voltammetry can be performed. The MLC-01 Cable Kit is
available to connect your PowerLab to this instrument.

Model 2053 High Current Potentiostat

The Omni 101 is a high current (up to 12 A) potentiostat/galvanostst
able to accept an external input. It can be used with PowerLab
replacing the XY plotter or chart recorder with Scope and Chart
software, or can be used with EChem software so that stepped ramp
and pulse voltammetry can be performed. The MLC-01 Cable Kit is
available to connect your PowerLab to this instrument.

220

EChem Users Guide

Table 97
Features of AMEL
instruments.

Model
Feature
2049

2051

2053

2055

PowerLab as plotter

yes

yes

yes

yes

PowerLab as waveform
generator

yes

yes

yes

yes

Inbuilt scanning

no

no

no

no

External Input

yes

yes

yes

yes

Voltage range

5 V

5 V

5 V

Compliance

22 V

27 V

50 V

30 V

Current ranges

1A to 1 A

1A to 1 A

1A to 1 A

100 A to 10 A

iR Compensation

no

no

yes

no

Note: These specications should be veried. Specications may change at short notice.

Chapter 9 Using 3rd Party Equipment

221

222

EChem Users Guide

A P P E N D I X

Menus & Commands

Menus
The menus shown here are similar to how they will appear when you
rst use EChem. If your copy of EChem has previously been used by
someone else it may appear differently if the EChem menus have
been customized. EChem has six standard menus: File, Edit,
Technique, Display, Windows, and Macro. Some of the menu
commands shown will change or be disabled depending on the active
window and what, if anything, is selected. An ellipsis, three dots (),
after a menu command indicates that it brings up a dialog box; a tick
to the left of the command indicates that it is currently active; and a
keyboard equivalent, if there is one, is shown to the right.
Figure A1
The File menu

Create a new EChem le

Open an existing le
Close the current le
Save the current le
Save the le with a new name, elsewhere, or in various forms
Set up page size and so on to suit the printer
Print one or more pages of data
Quit EChem

EChem Users Guide

223

Figure A2
The Edit menu

Undo previous action (if possible)

Cut page or selected data to the Clipboard
Copy page or selected data to the Clipboard
Paste page or selection
Clear page or selection
Copy text or graphics to the Clipboard
Customise EChem options (see Figure A3)
Show contents of Clipboard

Modify various EChem settings

Modify EChem menus
Modify appearance of control panels
Save current settings as default settings

Figure A3
The Preferences submenu

Figure A4
The Technique menu

Command- E (or Control-E) signies the active

technique

Apply Technique makes uses old parameters

for the next page

224

EChem Users Guide

Modify display colours, grids, lines, and so on

Go to a particular page of a le quickly

Figure A5
The Display menu

Show or hide an overlaid page

Turns all overlays on
Turns all overlays off
Modify the way overlaid waveforms are displayed
Sets the current sampling display method
Keep selected background but dont subtract
Select a scan to be background
Deselect background scan

Figure A6
The Windows menu

Display Notebook window. Write general notes on the le

Return to, or open the main EChem window
Display a selection in the Zoom window
Dene selection area
Dene marker position
Bring up Data Pad window
Log results to Data Pad

Figure A7
The Macro menu

Start or stop recording a macro

Delete a macro from the current list of macros
Choose macro control actions (see Figure A8)
Redraw the screen during the playing of a macro

Figure A8
The Macro Commands
submenu. The Speak
Message and AppleScript
commands are available only
on Macintosh systems.

Pause the macro for a set time

Set an audible alert using the System sounds
Display a message dialog box (requiring user action)
Speak a written message (if the computer can do this)
Add an AppleScript as a macro step
Select each page of data to perform some action to
Start a repeat sequence
Finish a repeat sequence

Appendix A Menus & Commands

225

Keyboard Shortcuts
The Command-key ( or ) on Macintosh, or the Control-key on
Windows PC, menu command equivalents are shown in Table A1.
Your copy of EChem may be set up differently if it has been
customized. Some of the Command-key equivalents will also change
or be disabled depending on the active window and what, if
anything, is selected. Their functions are discussed elsewhere in this
users guide.
Table A1
EChem keyboard short-cuts
for Macintosh. Use the
Control key on a Windows
PC, or the - or -key on
a Macintosh. The list is
alphabetical so that you can
see at a glance which keys
have been used for menu
commands

Keystrokes

Function

CommandA

Overlay all

CommandB

Clear data

CommandC

Copy to Clipboard

CommandE

Edit active technique

CommandH

Overlay none

CommandN

New

CommandO

Open

CommandP

Print

CommandQ

Quit EChem

CommandR

Start/stop macro recording

CommandS

Save file

CommandV

Paste

CommandW

Close active window

CommandX

Cut page

CommandZ

Undo/redo (if possible)

Command\

Access to dialog boxes (Menu, Save As, Start-up)

CommandPeriod (.)

Stop sampling, stop macro recording or playing

CommandSpacebar

Start/stop sampling

CommandRight arrow

Go to last page

CommandLeft arrow

Go to first page

Standard keyboard short-cuts for dialog boxes also apply: Tab moves
the insertion point to next text entry box; Enter or Return is the same
as clicking the OK button; and Esc or Command-period (.) or Controlperiod, is the same as clicking the Cancel button.

226

EChem Users Guide

A P P E N D I X

Troubleshooting
Technical Support
EChem has been extensively tested to make sure that it runs smoothly
and without difculties. Occasionally, however, problems may arise
or something unexpected may occur. The second part of this
appendix gives a list of possible problems and likely solutions: you
should look there rst to see if your needs are addressed specically.
If you are experiencing difculties with EChem that are not covered
in this users guide, or you need technical assistance with your
system, then ADInstruments and its authorised distributors are glad
to help. The About EChem dialog box provides dealer and distributor
addresses and the required system conguration information. To
access this information, select the About EChem command from
the Apple () menu on a Macintosh, or go to the Help menu on a
Windows computer (click the dialog box when you have nished to
make it go away).

Figure B1
The About EChem dialog box

Release date

Click this button for

information on dealer
contacts

EChem Users Guide

227

Click this button for

information on
hardware conguration

Dealer and Distributor Information

If you need help or information from an authorised PowerLab
distributor, click the Telephone button, Figure B1, to bring up the
PowerLab Dealer and Distributor Addresses dialog box. Click in the
scrolling list on the right of the dialog box to select your country, or
the nearest one to it, and contact information will appear to the left.
Feel free to contact your PowerLab dealer to discuss hardware and
software requirements generally, and nd out more about the latest
releases, upgrades, and software maintenance information.

Figure B2
The ADInstruments Distributor
Addresses dialog box

System Conguration Information

In general, you will need to provide specic information about your
hardware and software to help to isolate and to solve problems
effectively. Since this type of information can be tedious to collate,
EChem does it all for you. Click the computer icon-shaped button,
Figure B1,to activate the About This Computer dialog box. There
will be a short delay while it gleans the required information from
your system.
The dialog box gives information on which version of EChem is
running, together with a list of system extensions and inits. Also
provided is a detailed description of your Macintosh, your PowerLab
and how it is connected, special hardware congurations, and other
peripheral devices connected to the computer.
Click the Print button to print the picture (it brings up the Print
dialog box), or the Copy to Clipboard button to copy the picture for
pasting into a letter or fax to your PowerLab dealer.

228

EChem Users Guide

Model of
PowerLab (if
connected)

Figure B3
The About This Computer
dialog box

Information about
computer

List of system
extensions
(Macintosh only)

Click to copy
information
Click to print
information

General
We welcome customer comment. You dont have to wait until you can
send a software problem report or return damaged hardware! If you
have comments or suggestions you would like to make about the
EChem application or this users guide, please feel free to write to us
directly in Australia or New Zealand, or through your local
PowerLab dealer. We value your responses, and they are taken into
account when future releases are being worked on.

Solutions to Common Problems

EChem has an extensive array of dialog and alert boxes, and these
will probably appear in most cases where problems arise. Very often
they will suggest appropriate courses of action. Where they do not, or
where the actions they suggest fail to alleviate the problem, this
section of the guide should prove useful.

Starting Up
Start-up errors are mostly hardware problems, and are dealt with in
detail in your PowerLab Owners Guide, but are briey covered here.

Appendix B Troubleshooting

229

The computer cant nd the PowerLab unit

The PowerLab is off or the power is switched off at the wall, the
power cable is not connected rmly, or a fuse has blown.

Check switches, power connections, and fuses.

Poor cable connection between the PowerLab and the computer, or a

bad cable.

Ensure that the cable is rmly attached at both ends and try
again. If there is still a problem, try a new cable.

The PowerLab has an internal problem or has hung

Turn off the computer and PowerLab (and any other devices in
the SCSI chain), and then turn the PowerLab back on again after
at least ten seconds. Turn on the computer and try using EChem
again.

SCSI problems: two SCSI devices on the bus have the same SCSI ID,
or termination is incorrect.

Check that each device has a unique ID number and that the SCSI
chain is terminated correctly.

EChem hangs or gives an alert on start-up

SCSI problems: two SCSI devices on the bus have the same SCSI ID,
or termination is incorrect.

Check that each device has a unique ID number and that the SCSI
chain is terminated correctly.

It may be that the application has become damaged in some way.

Try reinstalling EChem from the original CD

EChem starts up with strange settings and macros

You started EChem by opening a data le with custom settings or a
settings le, or the start-up settings have been customised.

230

EChem Users Guide

Start up again from the application itself. To start up EChem with

its default settings, hold down the Command key as you open the
application (straight after double-clicking it). Release the key
when an alert box appears.

To revert to the default start-up settings, choose the Start-Up

submenu command from the Preferences submenu of the Edit menu
and click Clear in the dialog box that appears. The next time EChem
starts up, it will open with the default settings.

Interface Problems
Some data display areas show gray
The Zoom window needs a selection (at least four data points) in the
EChem window before it can display anything. Zooming within the
Zoom window changes the selection in the EChem window, and may
reduce the selection too far.

Select data in the EChem window if there is no selection or

change the extent of the selection if the Zoom window is gray.

Dened units display incorrectly

EChem will deal with a unit prex correctly only if it is chosen from
the Prex pop-up menu in the dialog box for dening units: if dened
as part of a unit, it is ignored. For example to dene a milliampere
if you type in mA as one word with no prex, then EChem will
display a signal of a microampere in units of mmA
(millimillliampere). If the prex m were chosen, and the units as A,
EChem would scale the unit prex properly, to give the correct units
of A.
The indented position of dened units in the Units pop-up menu in
the Units Conversion dialog box will show if a prex has been used
properly.

Appendix B Troubleshooting

231

Commands seem to have no effect, or a strange one

Macro recording might have been turned on, so that you record what
you are doing rather than actually doing it. If so, then an indicator
will be turning in the title panel, with the word Recording beside
it.

Choose Stop Recording from the Macro menu, and discard the
macro, since it will likely be of little use.

Command-key equivalents dont work, or do strange things

Menu commands may have been deleted, or reassigned to other
menu commands or macros.

Look at the menus and compare them with Table A1. See below
for resetting procedures.

Menus, controls, or settings dont resemble those in this guide

If you started EChem by opening a data le with custom settings or a
settings le, or the copy of EChem you are using has been extensively
customised, and the settings saved as start-up settings. (Some menu
commands may be disabled, or have disappeared altogether, some or
all may be replaced by macros.)

Start up again from the application itself. To start up EChem with

its default settings, hold down the Command key as you open the
application (straight after double-clicking it). Release the key
when an alert box appears.

To revert to the default start-up settings, choose the Start-Up

submenu command from the Preferences submenu of the Edit menu
and click Clear in the dialog box that appears.
Ive altered menus and locked myself out, cant save, and so on

232

Type Command-/ to bring up a dialog box that allows emergency

access to the menu settings, start-up settings, and saving options.

EChem Users Guide

Dialog boxes dont appear where I want them

EChem dialog boxes usually appear on the main monitor (the one
with the menu bar). There are times, however, when you want one to
appear on a secondary monitor, for instance, if that monitor is colour
and you are changing display colours.

EChem in fact brings up dialog boxes on the monitor where the

pointer is positioned. To make a dialog box appear on a
secondary monitor, place the pointer there and use a Commandkey equivalent to bring up the dialog box (or if there is no
keyboard equivalent, dene a macro with one to do it).

The computer hangs while recording, or there is data loss

There may be a poor cable connection between the PowerLab unit
and the computer, or a bad cable, or incorrect SCSI termination.
Network connection problems or a strange system extension could
also be causing the problem.

Ensure that the cable is rmly attached at both ends and try
again. If there is still a problem, try a new cable.

If you are using a SCSI interface ensure that the SCSI chain is
terminated correctly.

Check your network connections, if you are on a network.

Check for strange system extensions, or software, especially

obscure ShareWare or FreeWare.

I keep running out of memory

EChem records to RAM. If you increase its memory allocation
(Macintosh only), you will have more of the RAM in your System
available to record data.

Appendix B Troubleshooting

To increase available memory (Macintosh only), quit EChem,

select the EChem icon in the Finder and choose Get Info in the
File menu (or type Command-I). Type in a new value in the
Preferred size box.

233

If the Macintosh has little free RAM space, you might want to
turn off unused applications, reduce the size of the RAM cache or
remove non-standard extensions or inits from the system. See
your computers Users Guide for more details.

If the Windows computer is running more than one piece of

software turn off these other programs while EChem is running.

When multiple sweeps are taken, data compression is only done after
all the pages have been sampled. EChem uses a reasonable amount of
memory for an off-screen buffer: if the EChem window is large and
the display is grayscale or color, more memory is used, especially if
thousands or millions of colors (16 bit or more) are selected for
display.

Shrink the EChem window and change the display from colour or
grayscale to black and white, or at least reduce the colour depth.

Printing Problems
Only one page printed, although a page range was specied
EChem adds to the bottom of the Print dialog box a dividing line and
the Print Current Page Only checkbox, which is on by default. When
the checkbox is on, the active page prints regardless of the range, if
any, specied in the dialog box.

To print a range of pages, turn off the Print Current Page Only
checkbox, and enter the numbers as usual.

Printing is slow
If getting a hard copy of your EChem pages quickly is important,
there are a number of things you can do.

234

First, work in black and white, not gray-scale or color, and use the
Waveform Print Layout buttons to minimize the number of sheets
of paper to printed. On Macintosh turn off Background Printing
in the Chooser: although it is useful to print in the background,
spooling the document takes time. Ensure that you are using the
latest printer driver (the LaserWriter 8 software, for instance, is
considerably faster than the LaserWriter 7 software).

EChem Users Guide

The Page Setup options affect printing speed. For a PostScript

laser printer, Faster Printing should be on, and Color and HighResolution Printing off. If you have another type of printer, you
should experiment with the Page Setup options to see which give
greatest speed. (Remember that the Faster Printing option in the
EChem Page Setup dialog box is not necessarily a panacea, in fact,
depending on your particular setup, it is possible that it could
make printing slower.) If using the LaserWriter 8 software, leave
the Layout option in the Page Setup dialog box at 1 Up (printing
one page per sheet) rescaling is quite slow.

The quality of printed work using these settings should be sufcient

for most routine purposes, although, for publication quality
diagrams, you may want to transfer data to a specialist graphing
program such as IGOR Pro.
Printing speed depends on hardware as well: the faster the computer
and printer, the faster that material can be printed.
Graphs are shrunk or comments truncated when printed
The le title, page number, and any page comments are included in
the printed EChem page. Long comments mean the area used for the
drawing is reduced; very long comments will be truncated.

You cannot prevent page comments from printing, so keep them

short (300 characters at most). Transfer longer comments as text to
a word-processing program.

Macro Problems
Macros behave unexpectedly

Make sure that you have the right macro, not a different one of
the same name (in the case of name conicts, the latest macro
loaded into memory is used).

Check that you have the steps and effects recorded somewhere,
and that you havent remembered them incorrectlyit is very easy
to do.

Appendix B Troubleshooting

235

If the macro is a new one, it is possible that a step was not

recorded correctly, and in particular, that a repeated sequence was
ended in the wrong place. Try recording the macro again.

I have macros in les where I dont want them

A macro, once created, oats around in memory until you save a le,
whereupon a copy is saved with the le (not necessarily the original
le where it was created). If you have opened many les with macros
in them, you will likely have a lot in memory.

Delete unwanted macros from a le using the Delete Macro

menu command and then save the le. (Delete Macro removes
the macros from memory the changes do not permanently take
effect until the le is saved.)

I created a macro, but lost it on quitting EChem

As mentioned above, macros oat around in memory until a le is
saved. Your macro may have been attached to another le, or lost if
you saved no les before quitting EChem.

Save a le where you want macros stored before quitting EChem.

Crashes
Note
EChem checks itself on
start-up for damage or
virus infection, and will
present an appropriate
alert box if it detects a
problem. (Files are not
checked, though.)

EChem quits unexpectedly, crashes, or freezes

If EChem quits unexpectedly or crashes (you get a dialog box with a
bomb in it), or the pointer freezes, then there may be a operating
system problem. If the behaviour is repeated, then the problem may
be coming from other software on you hard disk.

Turn off screen savers. On a Macintosh try also turning off system
extensions to see if this xes the problem. See your computers
manual for more details on this problem and how to deal with it.

The data or settings le you are using may have become corrupted,
possibly through disk damage, especially if it is on a oppy disk.

236

Use disk-checking software to nd and attempt to x any

problems in this area.

EChem Users Guide

It may be that the EChem software itself has become damaged in

some way.

Try reinstalling EChem from the original CD.

It could be that a computer virus is causing the problems.

Check your disk with anti-viral software. If you nd a virus, you

should check all potentially affected computers, disks, and
backups, and eliminate the infection. See if you can nd the cause
of the outbreak (poor network security or student copying of
software onto lab machines, for example) and try to prevent
future occurrences.

Noise
The detection of small current signals can be hampered by a relatively
large amount of noise. The determination of the source(s) of the noise
and its elimination can be a time consuming task. The following
advice is meant only as a guide to the likely sources of noise and is by
no means a comprehensive list.
If you are using the ADInstruments Potentiostat, much high
frequency noise can be effectively removed by setting the 10 Hz lter
setting. Remember, however, that this lter will affect results from
experiments that use short pulses (< 0.1 s), or fast scan times and
should not be used under such conditions.
EChem voltammograms show unexpected oscillations
The noise on the raw signal is probably large. Check by opening the
Input Amplier or Potentiostat dialog and examining the raw signal
at the same gain range as your experiment.
If the noise is 50 Hz or 60 Hz mains interference then the regular
sampling periods of EChem can cause an aliasing effect which may
produce low frequency oscillations in the voltammogram. In this case:

Appendix B Troubleshooting

Set the sampling period to an exact multiple of 20 ms (if using 50

Hz mains power) or 16.7 ms (if using 60 Hz mains power). The
mains induced noise will be eliminated when the signal is
averaged over each sampling period; or

237

Adjust the lter setting on your potentiostat to less than 50 Hz so

that the noise is reduced to an acceptable level. This will only be
possible at slower scan rates as ltering will distort peak shapes
at faster scan rates. A 10 Hz lter setting can be used even for
quantitative linear sweep or cyclic voltammetry up to about 100
mV/s and for qualitative work up to about 500 mV/s. For pulse
techniques the pulse widths should be longer than about 100 ms
if a 10 Hz lter setting is employed.

Make sure that power cables are positioned well away from your
experiment and the electrodes.

Other high frequency noise

Other high frequency noise may come from uorescent lighting, air
conditioners, electric motors (in laboratories these are found in
hotplate-stirrers, water bath thermostat-stirrers, and refrigerators).
Occasionally equipment in adjacent rooms may be the cause of the
problem.

Turn off lights, and nearby equipment, one at a time to locate

noise source(s) by trial and error

The computer itself, or other nearby computers, are likely sources of

high frequency noise. The computer monitor and the oppy and hard
disk drives are the most common origins.

Reposition the potentiostat and reaction vessel as far from the

computer as possible. Especially avoid having the electrodes in
front of the computer monitor.

Occasional spikes or intermittent noise

Occasional spikes or intermittent noise are more likely to be caused
by nearby electrical instrumentation being turned on or off.
Remember that many instruments have internal relays that may be
switching on and off during normal operation. The computer hard
disk and oppy disk drives may also give rise to this type of noise.

238

Install a surge suppressor/line lter power board on your power

socket and plug the computer, MacLab/PowerLab and

EChem Users Guide

potentiostat all into this one board. Try running your experiment
with nearby equipment switched off.
Noise with no apparent cure
Aluminium foil wrapped around the electrochemical cell and
grounded at a single common place may help. Placing the
experiment, potentiostat, MacLab or PowerLab, and even the
computer on a single large grounded copper sheet may reduce noise
levels markedly. In very low current or very noisy situations you may
have no alternative but to enclose your experiment in a Faraday cage.
Commercial cages are available but they will work no better than one
made by a local tradesperson from sheet metal or copper mesh. It
may also be useful to position the potentiostat within the cage. In a
large laboratory a small garden shed could be used as a walk-in cage.

Appendix B Troubleshooting

239

240

EChem Users Guide

A P P E N D I X

Technique Summary
This Appendix provides a quick reference to the techniques provided
in then EChem Technique menu. It is not a replacement for the detail
given in Chapter 7. If you need more detail please refer to the
appropriate technique in Chapter 7.

This Appendix does not cover the additional techniques described in

Chapter 8.

EChem Users Guide

241

Linear Sweep Voltammetry

In linear sweep voltammetry (LSV) a linearly increasing (or
decreasing) potential staircase ramp is applied to the working
electrode (Figure C1). The average current owing during the
sample periods (at the end of each step) in the potential ramp is
recorded and plotted against the voltage.
The current is usually sampled at the end of each potential step. If
you use the Multi Pulse Technique to set up a linear sweep run then
you can alter the position of the sampling period.
Table C1
Linear Sweep Voltammetry
parameter reference

Parameter

Values

Comments

Range

1000, 2000 or 5000 mV

full scale

Initial Potential

between 1, 2 or 5 V

Final Potential

between 1, 2 or 5 V

Must not be the same as the initial potential. It can be more negative or
positive than the initial potential.

Scan Rate

usually 51000 mV/s

Faster scan rates lead to a higher background signals unless

microelectrodes are employed.

Step Width

0.1 ms

The time that the potential is kept constant at each step

Step Height

1-2 mV is ideal

Values over 10 mV give insufficient potential resolution and lead to

excessively high charging currents

Samplig Period

0.1 ms

Use 20 ms at 50 Hz power, or 16.7 ms at 60 Hz power, to minimise mains

hum interference (visible as oscillations on voltammogram)

Steps

automatically set

Rest Time

15 s is usual

242

The 2000 mV range is typical

The length of time the potential is kept at the initial potential before the
scan is started.

EChem Users Guide

Square Wave Voltammetry

In Square Wave Voltammetry a square wave is superimposed upon a
staircase potential ramp so that one square wave cycle occurs on each
step. The Square Wave technique in EChem uses this method which is
sometimes called Osteryoung Square Wave Voltammetry.
The current is sampled at the end of the forward step and again at the
end of the reverse step.
Table C2
Square Wave Voltammetry
parameter reference
Parameter

Values

Comments

Range

1000, 2000 or 5000 mV

2000 mV is typical

Initial Potential

between 1, 2 or 5 V

This potential is usually chosen so as to not oxidise or reduce the

substrate

Final Potential

between 1, 2 or 5 V

must be different to the initial potential

Frequency

1060 Hz is typical

frequency of the square wave

Step Height

1 mV

This is the height by which the staircase base ramp increments

Steps

automatically set

SW Ampl.

1050 mV is typical

This is the half-height of the pulses of the square wave

Sampling Period

0.1 ms

Current data will be collected and averaged over this period which
occurs at the end of each step (upper and lower). The sampling
period should be significantly shorter than the step width in order for
the charging current to decay. Use 20 ms at 50 Hz power, or 16.7 ms
at 60 Hz power, to minimise mains hum interference (visible as
oscillations on voltammogram).

Rest Time

15 s is typical

Appendix C Technique Summary

243

Normal & Reverse Pulse

Voltammetry

Table C3
Pulse Voltammetry parameter
reference
Parameter

In Normal Pulse Voltammetry, a series of pulses of successively larger

potential are applied above a base potential to the working electrode.
Reverse Pulse Voltammetry is similar except that the base potential is
chosen to electrolyse the electroactive substrate. The pulses that are
then applied cause the reverse reaction to take place. The current is
sampled at the end of each pulse, and plotted against the potential.
Values

Comments

Range

1000, 2000 or 5000 mV

2000 mV is typical

Initial Potential

between 1, 2 V or 5 V

Usually chosen to be a value at which the electrode reaction of interest

does not occur. For Reverse Pulse Voltammetry this potential is chosen to
cause complete oxidation (or reduction) of the substrate, and the pulses
then cause the reverse reaction.

Final Potential

between 1, 2 or 5 V

This is the height of the last pulse to be applied. It can be thought of as the
height of an imaginary ramp passing through the tops of the pulses.

Scan Rate

usually 5100 mV/s

Usually this parameter is allowed to vary as the Step Width and Step Height
are set.

Step Width

24 s is typical

This is the period of a single step (including the pulse time). Much shorter
times can be used with microelectrodes.

Step Height

10 mV is typical

This defines the increase in height (mV) of successive pulses. The

minimum increment available is 1 mV

Steps

automatically set

Pulse Width

5100 ms is typical

Should be wide enough to allow the non-faradaic components of the

current to decay before sampling. Much shorter times can be used with
microelectrodes.

Rest Time

several seconds

This is the period between when the deposition potential is applied and the
scan commences. It allows the solution to come to equilibrium after the
initial potential is applied.

Sampling Period

0.1 ms

The current is always sampled at the end of the pulse. Use 20 ms at 50 Hz

power, or 16.7 ms at 60 Hz power, to minimise mains hum interference
(visible as oscillations on voltammogram)

244

EChem Users Guide

Differential Pulse Voltammetry

Table C4
Differential Pulse
Voltammetry parameters
Parameter

Differential pulse voltammetry uses a series of short, small amplitude

pulses (typically 50 mV) superimposed on a linearly increasing or
decreasing potential ramp (Figure 714). The current is sampled just
prior to each pulse (i1) and at the end of the pulse (i2). The difference
in current (i2i1) is plotted versus the potential at the base ramp.
Values

Comments

Range

1000, 2000 or 5000 mV

Initial Potential

between 1, 2 or 5 V

Final Potential

between 1, 2 V or 5 V

Must not be the same as the initial potential

Scan Rate

125 mV/s is typical

Increasing the scan rate decreases peak resolution. However very slow
scan rates mean inordinately long analysis times

Step Width

0.54 s is typical

The time of each step (including pulse time). This is also the period
between pulses. This parameter is usually allowed to vary while the Scan
Rate and Step Height are set. Much horter times can be used with
microelectrodes.

Step Height

110 mV is typical

keep as small as possible

Steps

automatically set

Pulse Height

50100 mV is typical

The height of the pulse superimposed upon the potential ramp. A positive
peak height indicates a pulse in the direction of the applied ramp. Larger
values increase sensitivity (bigger peaks). Smaller values improve
resolution. The Pulse Height must be greater than the Step Height or the
next step will be bigger than the previous pulse.

Pulse Width

20100 ms is typical

The pulse should last long enough to allow the non-faradaic components
of the current to decay before sampling, this usually requires that the
Pulse Width is at least 5 ms longer than the sampling period - the larger
the area of the electrode the longer this will need to be. For a standard
glassy carbon electrode with an area of ~1 mm the pulse should be at
least 20 ms wide. Much shorther times can be used with microelectrodes.

Rest Time

15 s

The period before the scan commences when the initial potential is
applied.

Sampling Period

120 ms typically

Use 20 ms at 50 Hz power, or 16.7 ms at 60 Hz power, to minimise

mains hum interference (visible as oscillations on voltammogram).

Appendix C Technique Summary

2000 mV is typical

245

Cyclic Voltammetry
The potential is driven between two limits at a constant rate, similar
to linear sweep voltammetry. When a limit is reached the potential is
swept back again at the same rate. The experiment can start at any
potential (initial potential) between the two limits. The current is
sampled at the end of each potential step.

Table C5
Cyclic Voltammetry
parameter reference
Parameter

Values

Comments

Range

1000, 2000 or 5000 mV

2000 mV is typical

Initial Potential

between 1, 2 or 5 V

Chosen to be a value at which oxidation or reduction of the substrate does

not occur. The potential might correspond to either the Upper or Lower
potential or be somewhere in this range.

Final Potential

must be the same as the initial potential (to complete a cycle).

Upper (Potential
Limit)

between 1, 2 or 5 V

maximum potential that will be achieved in a cycle and can be any value

Lower (Potential
Limit)

between 1, 2 or 5 V

minimum potential that will be achieved in a cycle. Note that the difference,
Upper-Lower potential, must be less than 4 V if the 2000 mV range is
selected, and less than 10 V if the 5000 mV range is selected.

Scan Rate

101000 mV/s

Faster scan rates can be selected but (depending on the scan width) you
may find that the step height is unacceptably high.

Step Height

1 mV

the step height to a minimum (between 1 or 2 mV is ideal. More than 10 mV

will not give adequate potential resolution.

Step Width

2 ms

The time that the potential is kept constant at each step.

Samplig Period

0.1 ms

Use 20 ms at 50 Hz power, or 16.7 ms at 60 Hz power, to minimise mains

hum interference (visible as oscillations on voltammogram)

Rest Time

1s

Period between when the Potential is applied and the scan commences.

Deposition
Potential

not normally used

potential applied during the deposition time.

Deposition Time

not normally used

This is a period before the Rest Time. Can be used for stripping methods.

Cleaning Potential

not normally used

The Cleaning Potential can also be set to a value to oxidise (or reduce) any
material that has plated out on the working electrode. The potential applied
during the Cleaning Time.

Cleaning Time

not normally used

This is a period after the Final Potential has been reached. Can be used for
stripping methods.

246

EChem Users Guide

Multi Pulse Voltammetry

Table C6
Multi Pulse Ramp parameter
reference
Ramp Parameter

The Multi Pulse Voltammetry technique allows you to generate your

own waveform. This is constructed by the addition of a staircase
ramp and one or two pulses per step of the ramp. In addition up to
four current sampling windows can be selected with their position
and duration independently set.
Values

Comment

Range

1000, 2000 or 5000 mV

Initial Potential

between 1, 2 or 5 V

Final Potential

between 1, 2 or 5 V

Must not be the same as the initial potential. The final potential may
be either more negative than the initial potential (negative scan) or
more positive than the initial potential (positive scan).

Scan Rate

< 1 mV/s for corrosion work

otherwise 51000 mV/s

Faster scan rates lead to a higher background signal.

Step Width

2 ms

The time that the potential is kept constant at each step.

Step Height

dependent on experiment

Steps

automatically set

Rest Time

15 s is typical, longer for

corrosion work

Table C7
Multi Pulse parameter
reference for defining pulses
Pulse Parameters
Pulse Start

Usually the 2000 mV range is chosen.

the length of time the potential is kept at the initial potential before
the scan is started

Dening Pulses
Values

< Step Width (ms)

Comments
The timing of each pulse is linked to the start of each step in the
base ramp. For example if you enter 20 ms in the Start box it
means the pulse will be activated 20 ms after the beginning of the
step. The pulse can begin at any time during each step

Pulse Height

this is the height of the pulse above (or below) the step.

Increment

pulses on successive steps will be incremented by this amount

Duration

< (Step Width Pulse Start)

Appendix C Technique Summary

the duration of the pulse must be such that the entire pulse occurs
within one step of the potential ramp

247

248

EChem Users Guide

A P P E N D I X

Electrochemical
Equations
Linear Sweep and Cyclic Voltammetry
The Randles-Sevcik Equation
For a substrate with a reversible redox reaction, at a planar disk
electrode, in an unstirred solution, the peak current during linear
sweep, or cyclic voltammetry, is given by the RandlesSevcik
equation:
3/
1/
1/
ipa = 269 n 2 AD 2 Cv 2

for an oxidation (anodic scan)

3/
1/
1/
ipc = 269 n 2 AD 2 Cv 2

for a reduction (cathodic scan)

The potential where this occurs is given by:

0.0285
Epc = E 1/2 ---------------n

0.0285
E pa = E 1/2 + ---------------n

where
ipa = current peak during anodic scan (A)
ipc = current peak during cathodic scan (A)
E pa = potential at current peak for anodic scan (V)
Epc = potential at current peak for cathodic scan (V)
E 1/2 = half potential as determined by cyclic voltammetry (V)

n = the number of electrons transferred to (or from) the substrate

molecule

EChem Users Guide

249

A = area of the exposed surface of the electrode (cm2)

D = diffusion coefcient of the substrate molecule (cm2 s-1).
C = concentration of the substrate molecule (mol L-1)
= the scan rate (V s-1)
The factor of 269 is a parameter that derives from using a planar
electrode at a temperature of 298 K
Thus a truly reversible reaction can be identied by examining the
adherence of the system to the following functions:

ip v

Ep independence of the san rate,

In addition cyclic voltammograms will exhibit:

57
E pa Epc = -----n
ipa
------ = 1
ipc

mV (at 298 K)

When working in highly resistive solutions, which is often the case

when using organic solvents for cyclic voltammetry, the reference
electrode should be kept as close as possible to the working electrode
to minimise iR drop. Nonetheless there may still be an appreciable
uncompensated resistance which will cause | Epc - Epa| to become
larger than predicted, the peaks will be broader and the peak currents
smaller.

250

EChem Users Guide

Differential Pulse Techniques

The Parry-Osteryoung Equation
Differential pulse techniques require that the sampling periods be
chosen so that the current is only due to a Faradaic component (i.e.
only due to a redox reaction and not the charging current which
dominates immediately after the application of a pulse)
The observed potential of the peak when studying a reversible system
is given by:
h
Ep = E 1/2 -----p2

where
Ep = potential at which the peak occurs
E 1/2 = the half wave potential (as might determined by cyclic
voltammetry)
hp = the height of the pulse.

The peak current is given by the Parry-Osteryoung equation:

1

nFAD 2 C ( 1 )
i p = --------------------------------------------------------------1
1
1000 2 ( t ) 2 ( 1 + )
where
t = time at which the current is rst sampled in each cycle
= time at which the current is sampled second in each cycle
( nFAh p )
-----------------------

= e 2 RT
n = the number of electrons transferred to (or from) the substrate
molecule
F = Faraday's constant, 96485 C mol-1
A = area of the exposed surface of the electrode (cm2)
D = diffusion coefcient of the substrate molecule (cm2 s-1).
C = concentration of the substrate molecule (mol L-1)
R = the gas constant, 8.314 J K-1 mol
T = the temperature (K)

Appendix D Electrochemical Equations

251

Chronoamperometry
The Cottrell Equation
When chronoamperometry is performed on an unstirred solution at a
planar electrode the faradaic current response is described by the
Cottrell equation
1

nFAD 2 C
i = ------------------------------1 1
1000 2 t 2
where
n = the number of electrons transferred to (or from) the substrate
molecule
F = Faraday's constant, 96485 C mol-1
A = area of the exposed surface of the electrode (cm2)
D = diffusion coefcient of the substrate molecule (cm2 s-1).
C = concentration of the substrate molecule (mol L-1)
t = time (s)
The factor of 1000 is to bring both cm and dm (1 L = 1 dm3) in the
equation to common units.
In aqueous solution the coefcient of diffusion usually has a value of
between 10-5 and 10-6 cm2 s-1.

252

EChem Users Guide

Chronocoulometry
The Integrated Cottrell Equation
The current response equation at a planar electrode for a
chronocoulometric experiment is the time integrated form of the
Cottrell equation:
Q =

2nFAD 2 Ct 2
-+k
i dt = --------------------------------------1
0
1000 2

where
Q = the number coulombs transferred
n = the number of electrons transferred to (or from) the substrate
molecule
A = area of the exposed surface of the electrode (cm2)
D = diffusion coefcient of the substrate molecule (cm2 s-1).
C = concentration of the substrate molecule (mol L-1)
t = time (s)
k = a constant.
Thus a plot of Q versus t1/2 should produce a straight line with an
intercept of k.
The constant k can be dened as:

k = nFA + Qdl

where

= surface concentration of adsorbed substrate (mol cm-2)

Qdl = double layer charging.

Appendix D Electrochemical Equations

253

254

EChem Users Guide

E
WARNING
All organic solvents are, to
a lesser or greater degree,
toxic, and many are
ammable. General safety
procedures include working
in a well ventilated area (a
fume hood is necessary for
all but the most benign
solvents), with hand and
eye protection (usually
rubber gloves and safety
glasses). Even if the solvent
is relatively harmless most
organic solvents can
penetrate the skin easily
carrying potentially toxic
solutes with them.
Similarly most electrolytes
used with organic solvents
are toxic and/or skin
irritants. Always
familiarize yourself with
the potential hazards by
reading the Materials
Safety Data Sheets
available from the suppliers
of solvents and electrolytes.
Always assume that new
compounds (for which no
safety data may be
available) are toxic and
handle them with due care.

EChem Users Guide

A P P E N D I X

Cyclic Voltammetry,
Solvents & Electrolytes
Common organic solvents for cyclic voltammetry include methanol,
ethanol, propylene carbonate, 1,2-dimethoxyethane, acetonitrile,
acetone, dimethylsulfoxide (dmso), dichloromethane, dichloroethane,
and toluene. Polar and protic solvents exhibit lower resistivities than
non-polar and/or aprotic solvents. Unfortunately it is the more
resistive solvents in which common electrolytes are least soluble.
Remember that many of the constituent ions (both cations and
anions) of electrolytes are toxic and that when dissolved in organic
solvents they can be carried across the skin. Similar aqueous solutions
are usually much less of a hazard if skin contact occurs. However, in
all cases of accidental spillage where you do not know the specic
treatment, all contaminated skin areas should be continuously
ushed with copious amounts of water for at least several minutes.
For a a good general introduction to the use of non-aqueous solvents
see the Chapter 7, Solvents and Electrolytes in Electrochemistry for
Chemists, 2nd edition, D. T. Sawyer, A. Sobkowiak, and J. L. Roberts,
Wiley-Interscience New York, 1995.

Solubility Rules
Some generalised rules for solubility of electrolytes in organic
solvents are:

perchlorates (care! explosion hazard), chlorides, nitrates, and

tosylates are most soluble in alcohols;

255

perchlorate in the presence of potassium ions will give a

precipitate of KClO4;

electrolytes comprising large cations and anions will be more

soluble in non-polar solvents and less soluble in polar solvents;

dimethylsulfoxide is a very good solvent for most electrolytes;

uoroborate and hexauorophosphate salts exhibit particularly

good solubility in acetone and acetonitrile;

dichloromethane and similar solvents usually require tetra-nbutylammonium hexauorophosphate.

electrochemistry in toluene an be performed using liquid

tetrabutylammonium tetrauoroborate toluene solvate. See
J. Chem. Soc. Chem. Commun, 323 (1985).

Solvent Stability
Amides, esters, nitriles, strained ethers, etc. are subject to hydrolysis
especially if traces of acid or base are present. Hydrolysis reactions
can be very slow (hours or days) and often manifest themselves as an
increase in background currents or a reduced redox stability window.
Remember that only a small fraction of the solvent need hydrolyze to
generate impurities that can be detected electrochemically but which
will remain unseen by nmr or infrared spectroscopy.

Use of Large Ions as Electrolytes

A wide variety of large cations and anions are available so that in
practice it is nearly always possible to nd an electrolyte that will be
suitable for a given solvent. Common electrolytes are commercially
available but others will need to be prepared by the user. Purity of
both commercial and home made electrolytes should be checked by
performing a blank run at the same sensitivity setting of the
potentiostat that is used when the analyte is present. Remember that
purity is a relative term electrolyte and solvent that has been used
satisfactorily with high concentrations of analyte at low sensitivity
settings may prove to hopelessly contaminated when used with much
lower concentrations of analyte at very high sensitivity settings.

256

EChem Users Guide

Cations
Complex cations are typically subject to reduction at sufciently large
potential, oxidation is usually less of a problem. Remember that only
a small proportion of the electrolyte needs to be electrolyzed to
produce a signal that will interfere with the analyte's signal. Some
large cations that can be employed are shown in Table E1.
Tetraalkylammonium salts are the most commonly used for organic
solvent work because of their relatively low cost and because they are
fairly resistant to reduction.
Table E1
Complex cations used in
background electrolytes

Cation

Formula

Mr

tetramethylammonium

[N(CH3)4]+

74.15

tetraethylammonium

[N(CH2CH3)4]+

130.3

tetra-n-butylammonium

[N(CH2CH2CH2CH3)4]+

242.5

PF6 salt used in

dichloromethane.

tetraphenylphosphonium

[P(C6H5)4]+

339.4

Easily reduced.
Hydrolyzed by hydroxide.

benzyltriphenylphosphonium

[P(CH2C6H5)(C6H5)3]+

353.4

Easily reduced.
Hydrolyzed by hydroxide.

bis(triphenylphosphino)imminium

[(C6H5)3P=N=P(C6H5)3]+

538.6

tetraphenylarsonium

[As(C6H5)4]+

383.3

(18-crown-6)potassium

[K(C12H24O6)]+

303.4

Can be prepared in situ from

potassium salts.

(dibenzo-18-crown-6)potassium

[K(C20H24O6)]+

399.5

Can be prepared in situ from

potassium salts. Soluble in
benzene, toluene etc.

Appendix E- Organic Solvents

257

Comments

WARNING
Perchlorates are a known
explosion hazard and their
use should be avoided
wherever possible.
Especially avoid
evaporation of perchlorate
containing solutions and
clean up all spills
immediately.

Anions
Large anions may be subject to reduction or oxidation. Some anions
that can be employed as shown in Table E2. Perchlorate salts are a
known explosion hazard and should be avoided wherever possible.
Note that while nitrate is often considered safe to use, it is an
oxidizing agent. Its use as an electrolyte (at relatively high
concentrations) in organic solvents is a potential explosion/re
hazard, especially if traces of acid are present, or if the solution is left
to evaporate.

Table E2
Complex anions used in
background electrolytes

258

Anion

Formula

Mr

Comments

nitrate

NO3

62.00

Potential explosion hazard.

perchlorate

ClO4

99.45

Explosion hazard, easily reduced.

triflate

CF3SO3

149.1

methanesulfonate

CH3SO3

95.09

tosylate

CH3C6H4SO3

171.2

trifluoroacetate

CF3COO

113.0

tetrafluoroborate

BF4

86.80

tetraphenylborate

B(C6H5)4

319.2

hexafluorophosphate

PF6

145.0

EChem Users Guide

May hydrolyze to HF.

May hydrolyze to HF.

Electrode and Cell Design for

Organic Solvents
Cyclic voltammetry can be carried out in ordinary sample tubes
(2.5 5 cm) with the electrodes placed through holes in the plastic
cap. Air can be excluded with an argon or nitrogen purge. Argon is
more expensive but because of its greater density tends to blanket the
sample more efciently.
The purity of the solvent and the electrolyte can be established by
looking for spurious signals in the cyclic voltammogram but make
sure that you run at the same gain range you will be using for your
samples. In many cases both the solvent and electrolyte will need to
be thoroughly dried as traces of water may limit the scan range or
react with the substrate or electrolysis products.
Electrochemistry in dichloromethane or 1,2-dichloroethane (less
volatile) can be performed using a 0.10 mol L-1 solution of tetra-nbutylammonium hexauorophosphate. Other common combinations
are 0.1 mol L-1 tetra-n-butylammonium tetrauoroborate in
acetonitrile, or benzonitrile; or 0.1 mol L-1 tetraethylammonium
perchlorate in propylenecarbonate, tetrahydrofuran, or dimethyl
formamide. Where possible perchlorates (explosion hazard) should
be substituted with salts containing non-oxidizing anions.
While many workers go to great length to dry their solvents this is
really only necessary if the compound or its redox products are water
sensitive or if you wish to explore outside the redox inactive region of
water. There is nothing inherently wrong in using mixed
aqueous/organic solvent mixtures if this is convenient. However,
remember that many molecules, or their redox products, are acids or
bases and, that if your aqueous solutions are not adequately buffered,
you may have difculty in getting reproducible results. The addition
of a small amount of acid or base to an aqueous solvent mixture can
both serve to buffer the solution and to act as a background
electrolyte.
Many studies require only a simple determination of E1/2 values for
compound characterisation. In these cases some liberties can be taken
with electrode design. A 0.5 mm diameter platinum wire can be used

Appendix E- Organic Solvents

259

as the working electrode. The wire should be embedded in a soft

(soda) glass rod which can be polished at its end. Soda glass matches
the thermal coefcient of platinum more closely than borosilicate if
the platinum wire and glass rod separate in the working electrode
solution may seep into the electrode and give old signals. Allowing
the wire to protrude by as much as 13 mm will increase the current
but this is usually not necessary.
The auxiliary (counter) electrode is usually a simple platinum wire.
The reference Ag/AgCl electrode can be as simple as a silver wire
previously anodized in 1 M hydrochloric acid, rinsed with water, then
allowed to dry. The wire is then immersed in electrolyte solution in a
thin glass or Teon tube with a sintered frit at the bottom which acts
as a small salt bridge.
If there is any doubt about the stability of the reference then the
ferrocene/ferrocinium (Fc/Fc+) couple can be used as reference
potential to calibrate the reference electrode: a small amount of
ferrocene is added to the reaction mixture after the experiment is
nished (the peak to peak separation is usually about 70 mV).
Alternatively the electrode can be calibrated at the beginning of each
day by measuring the Fc/Fc+ couple in fresh electrolyte. Cleaning
and re-anodizing of the silver wire will be necessary from time to
time. It is not uncommon for inorganic and organic chemists to report
redox potentials relative to ferrocene.
The reference electrode should be placed as close as possible to the
working electrode. Distances between the working and auxiliary
electrodes should also be kept to a minimum to keep the required
compliance voltage small (see Appendix F).

260

EChem Users Guide

Synthesis of Selected Electrolytes

WARNING
Concentrating perchloric
acid solutions can result
in serious explosion
especially if organic
matter is present! Under
no circumstances should
concentrated perchloric
acid (> 1.0 M) be used in
these preparations. No
product (nal or
intermediate) should be
taken to dryness unless a
representative sample
dissolved in a small
quantity of water shows
that no acid is present (use
a narrow range indicator
paper). All ltrates and
washings should be
immediately discarded by
ushing down the sink
with tap water.

Tetraethylammonium perchlorate,
[(CH3CH2)4N]ClO4, Mr = 229.7
Acid-Bromide method
Tetraethylammonium bromide, Mr = 210.2, (100 g, 0.48 mol) is
dissolved in water (100 mL) with slight warming, then 1.0 M
perchloric acid (600 mL, 0.60 mol) is added. White crystals form
immediately and are ltered off after cooling the mixture to below
5 C. The crude product is washed with ice cold 1.0 M perchloric acid
(100 mL) then recrystallised from 1.0 M perchloric acid (300 mL). The
product is ltered off, washed rst with ice cold 1.0 M perchloric acid
(100 mL), then ice cold ethanol (200 mL). Recrystallisation from
boiling ethanol (300 mL) with sufcient water to ensure complete
dissolution (about 30 mL) gives the nal product which is washed
with ice cold ethanol (200 mL). The product can be checked for purity
by dissolving about 0.5 g in warm water (2 mL) and testing the pH of
the solution, and for any reaction with silver nitrate. A further
recrystallisation from ethanol may be necessary. The product is dried
under vacuum (0.1 mm Hg), to yield 70.3 g (64%) of white needles.
The solid compound should be treated as an oxidising agent and
stored away from reducing (organic) materials.

Acid-Base method
Aqueous 1 M perchloric acid (250 mL, 0.25 mol) is added to a solution
of 1 M tetraethylammonium hydroxide (250 mL, 0.25 mol). The
mixture is adjusted to pH 7 (use a narrow range pH indicator paper,
not litmus paper) by the addition of more acid or base solution as
required, and stirred while cooling in an ice [Link] resulting
precipitate is removed from the cold suspension by suction ltration
and washed with cold water. The crude product can be recystallised
from water and dried at 100C for 24 h in vacuo. M.p. 351352.5C
with decomposition. The solid compound should be treated as an
oxidising agent and stored away from reducing (organic) materials.
The purity of the product should be checked by cyclic voltammetry.

Appendix E- Organic Solvents

261

WARNING
Hexauorophosphoric acid
is extremely corrosive, it
may also contain traces of
hydrouoric acid! Handle
with gloves in a fume
cupboard.
Hexauorophosphate salts
can very slowly hydrolyze
releasing hydrogen
uoride, thus they should
be stored dry, in plastic
containers.

Tetra-n-butylammonium hexauorophosphate, [n-Bu4N]PF6

Bromide method
A solution of tetra-n-butylammonium bromide (100 g, 0.31 mol) in
acetone (250 mL) is mixed with a solution of ammonium
hexauorophosphate (50 g, 0.4 mol) in acetone (350 mL). The
resulting precipitate of ammonium bromide is removed by suction
ltration. The ltrate is concentrated, with a rotary evaporator, to
approximately 200 mL. Water is added to the acetone solution to
precipitate tetra-n-butylammonium hexauorophosphate (nal
volume approximately 2 L). The precipitate is removed by suction
ltration, washed with water, and then redissolved in a solution of
ammonium hexauorophosphate (5 g, 0.04 mol) in acetone (200 mL)
more acetone can be added to complete dissolution if required.
Addition of water (nal volume approximately 2 L) causes the
precipitation of the crude product which is removed by suction
ltration and washed with water.

Acid-base method
An aqueous solution of 0.5 M hexauorophosphoric acid (600 mL, 0.3
mol) is added to an aqueous 0.5 M solution of tetra-nbutylammonium hydroxide (600 mL, 0.3 mol). The mixture is
adjusted to pH 7 (use a narrow range pH indicator paper, not litmus
paper) by the addition of more acid or base solution as required. The
crude product is removed from the cooled mixture by suction
ltration and washed with water.

Recrystallisation
The crude product, produced by either the bromide or acid-base
method, is recrystallized three or four times from a 3:1 mixture of
ethanol/water and then dried for at least 24 h at 100C in a vacuum
oven. The yield is usually about 95 g.
The purity of the product should be checked by cyclic voltammetry.

262

EChem Users Guide

WARNING
Fluoroboric acid is
extremely corrosive, it
may also contain traces of
hydrouoric acid! Handle
with gloves in a fume
cupboard.
Fluoroboric salts can very
slowly hydrolyze releasing
hydrogen uoride, thus
they should be stored dry,
in plastic containers.

Tetra-n-butylammonium tetrauoroborate,
[n-Bu4N]BF4, Mr = 391.5
Acid-Bromide method
Aqueous uoroboric acid (48%, 36 mL) is added to a solution of tetran-butylammonium bromide (84 g, 0.25 mol) in water (180 mL) and
the mixture stirred for 1 minute. The resulting precipitate is removed
by suction ltration and washed with water until the washings are no
longer acid (use a narrow range pH paper). The crude product can be
recystallised from ethyl acetate/cyclohexane. M.p. 162162.5C.
The purity of the product should be checked by cyclic voltammetry.

Tetra-n-butylammonium uoroborate
toluene solvate, [n-Bu4N]BF4.3(C6H5CH3)
Tetrabutylammonium uoroborate is stirred in toluene between
2225C. A two phase mixture results. The lower layer has an
approximate formula of [n-Bu4N]BF4.3(C6H5CH3). (Below 22C the
solvent-free uoroborate salt crystallises.) This layer an be separated
and used, without further purication, as the solvent for
electrohemical work. Reference: J. Chem. Soc. Chem. Commun, 323 1985.
WARNING
Triic acid is volatile and
extremely corrosive!
Handle with gloves in a
fume cupboard. Tetra-nbutylammonium triate is
hygroscopic.

Tetra-n-butylammonium triate
[n-Bu4N]CF3SO3, Mr = 391.5
Triic acid (triuoromethanesulfonic acid), Mr = 150.1, (600 mL,
0.15 mol) is slowly added, with stirring, and cooling, to a
commercially available 40% solution of tetrabutylammonium
hydroxide (Mr = 259.5) (100 mL 0.15 mol) until the pH drops to 6.5
(use a narrow range indicator paper). Water is added if necessary to
allow adequate stirring. The crude product is suspended in ice cold
water and ltered 5 times to wash it, then dried and recrystallised
from a mixture of dichloromethane and diethyl ether. Reference: J.
Org. Chem., 37, 3968, 1972.
The purity of the product should be checked by cyclic voltammetry.

Appendix E- Organic Solvents

263

CAUTION
Purication and
distillation of solvents
should only be undertaken
by an experienced chemist
or laboratory technician.
Incorrect procedures could
lead to explosion or re.
Appropriate care should be
exercised in the handling
and disposal of reactive
drying agents such as
metal hydrides,
phosphorous pentoxide
(P2O5), and sodium wire.
Adequate ventilation must
be ensured about the
distillation apparatus to
prevent the buildup of
ammable and toxic
solvent vapours.

Purication of solvents
For guidelines on the purication of many solvents see Purication
of Laboratory Chemicals, 4th edition, W. L. F. Armarego and D. D.
Perrin, Butterworth-Heinemann, 1997, ISBN 0750637617.
Solvents should be of at least AR (analytical reagent) grade otherwise
they may be grossly wet or otherwise need a preliminary purication
step. Further drying and purication is then usually necessary before
the solvent can be used for cyclic voltammetry or other
electroanalytical techniques.
Distillation of solvents should always take place using a short
fractionating column lled with glass rings to prevent an aerosol of
the boiling solvent being carried through the condensor. A dedicated
still for each solvent is ideal.
Ethers (including tetrahydrofuran, diethyl ether, 1,4-dioxan, and 1,2dimethoxyethane), as well as aromatic hydrocarbons (benzene,
toluene, xylenes) can be rst dried over sodium wire then distilled
from freshly drawn sodium wire with a little benzophenone added to
the distillation pot. A dark blue or purple color should develop and
persist during reux, for at least 10 minutes, which signals the
presence of sodium benzophenone ketyl (a radical anion). The ketyl
can only exist in the absence of water. The anhydrous solvent can
then be distilled. Excess sodium wire is destroyed by allowing the
distillation pot to cool and cautiously adding absolute ethanol.
Dichloromethane, 1,2-dichloroethane, cyclohexane, or hexane, can be
dried by distillation from either P2O5 or from CaH2.
Acetonitrile should be predried using a molecular sieve with a pore
size of not greater than 4 . Distillation can take place after reux
with a small quantity of P2O5 (about 0.5% w/v) to remove the
residual water. Avoid using too much P2O5 to prevent excessive
formation of an orange polymeric material.
Dimethyl sulfoxide or dimethylformamide should be predried using
a molecular sieve with a pore size of not greater than 4 , followed by
distillation at reduced pressure (10 20 mmHg).

264

EChem Users Guide

Supercritical Fluids
The use of supercritical uids as solvents for cyclic voltammetry has
also been investigated. For an example of a recent paper see
Electrochemical investigations in liquid and supercritical 1,1,1,2tetrauoroethane (HFC 134a) and diuoromethane (HFC 32),
Andrew P. Abbott, Christopher A. Eardley, John C. Harper, and Eric
G. Hope, Journal of Electroanalytical Chemistry, 457, 14, 1998. In
particular HFC 134a, with tetra-n-butyl ammonium tetrauoroborate
as electrolyte, was shown to be have an extraordinarily wide redox
stability window of 9 volts.

The Mercury Electrode

WARNING
Elemental mercury and its
salts and their solutions
are highly toxic. Only an
experienced chemist or
laboratory technician.
aware of the correct
handling and disposal
procedures should
undertake work with
mercury.

At times it may be of use to perform cyclic voltammetry experiments

in organic solvents using a mercury working electrode. Mercury
dropping electrodes (MDEs) can be used but commercial models are
expensive, cumbersome to set up, require periodic cleaning and
maintenance, and require the use of relatively large amounts of
elemental mercury. However they do have the advantage of being
able to provide a clean mercury electrode by dislodgment of the old
mercury drop and allowing a new drop to form, all at the press of a
button, in any solvent you require.
Mercury lm electrodes (MFEs) use much less mercury (often much
less than 1%) than a MDE, and are relatively low cost. The mercury is
usually electrodeposited as a thin lm on a glassy carbon, or
carbonber, support electrode. However the mercury coating must
be removed and replated if it is fouled or oxidised. Some workers
prepare the MFE by electrodeposition from aqueous mercuric ion
solutions and then wash the electrode to replace the solvent.
However it is also possible to electrodeposit mercury directly in
suitable organic solvents: G. Alarnes-Varela, A.L. Surez-Fernndez,
A. Costa-Garca, Electrochimica Acta, 44, 763772, 1998.

Appendix E- Organic Solvents

265

266

EChem Users Guide

A P P E N D I X

Potentiostat Designs
Potentiostats are designed to maintain a known potential difference
across a pair of electrodes while measuring the resulting current ow.
While this sounds simple in theory, the practice of electrochemistry
has demanded a variety of designs to cope with different types of
experiment.

Two electrode systems

The simplest potentiostat is a two-electrode unit that connects to a
working and reference electrode. A battery connected to two
electrodes with an ammeter in series could be considered as a very
simple example.
However, to maintain a known potential at the working electrode the
reference electrode must exhibit a steady response. This is not easy as
the current passing through the electrode will electrolyze (reduce or
oxidize) either the electrode material itself or material around the
electrode, which in turn will alter the half cell potential. In days gone
by the effects of this were usually minimized by making a very large
reference electrode which would not be signicantly disturbed by the
currents owing through it.
Today two electrode potentiostats masquerade under a variety of
different names, such as:

EChem Users Guide

dissolved oxygen meters which measure the current that passes

between a gold or platinum working electrode (at which a preset
reducing potential is maintained, usually about 0.8 V, which is

267

called the polarizing voltage) with respect to a silver counter

electrode. This is the classic Clarke type cell;

nitric oxide meters, which are very similar to oxygen meters, but
which reduce NO.

amperometric biosensor meters, which are very similar to the

previous two types of meter but which can usually have their
polarizing voltages adjusted to suit the system being measured.

voltage clamps, which are used by neurophysiologists to study

inter- and intracellular processes. These are usually exceptionally
high gain instruments employing head stage amplication,
capacitive compensation, and exhibiting very fast response times.

The common feature amongst all these devices is that they are used
for experiments in which the current owing through the (relatively
large) reference electrode is usually measured in nanoamperes or less.
These tiny currents are not sufcient to cause enough electrolysis to
seriously disrupt the environment around the reference electrode.
Some of these potentiostats will also have an external input so that
they can except an external voltage signal to alter the electrode
potential.

Three electrode systems

Most voltammetric experiments for analytical chemistry involve
currents of microamperes or greater and make use of a three electrode
instrument. The ADinstruments Potentiostat is of this type.
The electrodes are identied as the:

268

working electrode, where the redox reaction of interest takes

place;

reference electrode, at which a constant potential is provided by a

known half reaction. Virtually no current ows through this
electrode because it is connected to the working electrode across a
very large resistance (typically greater than 1012 ). This ensures

EChem Users Guide

that concentrations around (and the potential of) the reference

electrode is constant throughout the experiment; and an

auxiliary (or counter) electrode, where a counter reaction takes

place to maintain the electroneutrality of the solution. Thus if
reduction occurs at the working electrode then oxidation must
occur at the auxiliary electrode.

Compliance voltage
For most experiments involving such a potentiostat, at any given
instant the potential between the working and reference electrodes is
being held at a predetermined value while current ow is measured
across the working and auxiliary electrodes. These are the current and
potential values that are actually plotted.
But to do this some other potential must be maintained between the
auxiliary and working electrodes. This potential is called the
compliance voltage and, depending on the internal resistance of the
cell (which in turn depends on type of solvent, total electrolyte
concentration, distance between the electrodes, porosity and size of
frits used to separate cell compartments, etc.) may be much greater
than the observed potential of the working electrode. During an
experiment it may happen that the potentiostat is unable to provide a
sufciently large voltage across the auxiliary and working electrodes
to achieve the desired potential across the reference and working
electrodes. In this situation the potentiostat is said to be out of
compliance (or overloaded) and the results from such an experiment
will be meaningless in the non-compliance region. The
ADInstruments Potentiostat has a non-compliance light on its front
panel which will illuminate if this occurs.
High compliance
potentiostats are an
electrical shock hazard
unless used strictly in
accordance with the
correct procedure. Read
the manufacturers
manual!

The greater the compliance voltage of a potentiostat the greater the

number of cell designs with which it will be able to cope. Also,
because this voltage can actually occur across the working and
auxiliary electrodes, the greater the hazard from electric shock if the
instrument is not used in accordance with the correct safety
procedure. Most standard electronic componentry can handle 10 V
as a matter of course, and most potentiostats will exhibit a
compliance voltage within this range. Greater compliance voltages
will require the use of more specialist componentry, and such
instruments will necessarily command a higher price.

Appendix F Types of Potentiostat

269

It may also occur that the current owing between the auxiliary and
working electrodes is greater than the potentiostat is capable of
delivering and/or measuring. This is a current overload condition.
Currents can be decreased by using electrodes with a smaller surface
area, using lower concentrations of analyte, or (for stripping
methods) using a shorter deposition period. If EChem is being used
with an ADinstruments Potentiostat and the current capability of the
potentiostat (100 mA) is exceeded then an overload message appears
in the Cursor Panel.
By connecting the reference and auxiliary electrode leads together
most three electrode potentiostats can also be used as a two electrode
system. Check with the potentiostat manufacturer if you are unsure
whether your instrument can be used the way. The ADinstruments
Potentiostat can be used in this way
Many manufacturers make three electrode potentiostats such as
EG&G PAR, BAS, Radiometer, Solartron, AMEL, Metrohm, HEKA,
Cypress, Sycopel, and ADInstruments.

Four electrode systems

The most common four electrode potentiostat is the bipotentiostat.
This is designed to work with two working electrodes and a common
reference and auxiliary electrode, and can be considered a simple
variant of the three electrode design. Advanced bipotentiostats can
sweep the potential at each working electrode independently of one
another while simpler units only allow the working electrode
potentials to be adjusted independently and then held steady.
The bipotentiostat is used with a rotating ring disk electrode where
the potentials of the ring and disk electrodes need to independently
controlled. The most widely known manufacturer of these devices is
PINE Instruments.
Another type of four electrode design makes use of two reference and
two counter electrodes. These instruments can be employed to control
the potential across a membrane or interface and to measure the
resulting current ow. This type of potentiostat is not readily
commercially available but a good design has been published: T. J.
VanderNoot and D. J. Schiffrin, Design and Evaluation of a Four-

270

EChem Users Guide

Electrode Potentiostat/ Voltage Clamp Suitable for AC Impedance

Measurements at the Interface of Immiscible Electrolytes, Journal of
Electroanalytical Chemistry, 278, 137 150 (1990), and M. C. Wiles, D. J.
Schiffrin, and T. J. VanderNoot, Experimental Artifacts Associated
with Impedance Measurements at LiquidLiquid Interfaces, Journal
of Electroanalytical Chemistry, 278, 151 159 (1990).

Appendix F Types of Potentiostat

271

272

EChem Users Guide

Bibliography
Electrochemistry is a large eld and there are many specialised and
general texts available, as well as journals and on line information.
The following list is meant as only as a general introduction to the
literature.

The Internet
Much useful information can be obtained from various internet web
sites such as:

[Link] The Electrochemistry Society, Inc.

[Link] The Society for Electroanalytical Chemistry
[Link] Electrochemical Science and Technology Information
Resource. Lists of text books, journals,hand books, graduate schools, societies, meetings, etc
[Link] The Electrochemistry Gateway
[Link] Yahoo search engine
[Link] The Analytical Chemistry Springboard
[Link] Electrochemistry Online Services (ECOS) from Elsevier. Includes
liks to Elseviers electrochemistry journals.
[Link] NACE Internaional ( National Association of Corrosion Engineers)

EChem Users Guide

273

Text Books
For an extensive listing of text books, from 1950 to present, consult
the Electrochemical Science and Technology Information Resource
(ESTIR) web site at [Link]
Many other monographs and proceedings are available from the
Electrochemical Society.
Surface chemistry and electrochemistry of membranes. T. S.
Sorensen (Ed). Dekker, NY 1999.
Pocket handbook of electroanalytical instrumental techniques for
analytical chemistry. J. Osteryoung, Prentice Hall, Englewood Cliffs,
NJ 1998.
Biosensors: An Introduction. Brian R. Eggins. Wiley, 1998.
Environmental electrochemistry: fundamentals and applications in
pollution abatement. K. Rajeshwar and J.G. Ibanez. Academic, NY
1997.
Green functions in electrochemistry. S. Romanowski and L.
Wojtczak (Ed). Kluwer, Dordrecht, Netherlands 1997.
Modern Techniques in Electroanalysis. P. Vanysek (Ed), Wiley, NY
1996.
Laboratory techniques in electroanalytical chemistry (2nd edition).
P.T. Kissinger and W.R. Heineman (Ed), Dekker, NY 1996.
Experimental Techniques in Bioelectrochemistry. V. Brabec, D. Walz
and G. Milazzo (Ed.), Birkhauser, Basel 1996.
Reference electrodes, theory and practice. Reprint of the original
1961 edition - see below. D.J.G. Ives and G.J. Janz (Ed), NACE
International, Houston, TX 1996.
Electrochemistry for Chemists (2nd edition). D.T. Sawyer, A.
Sobkowiak, and J.L. Roberts, Wiley, New York, 1995.

274

EChem Users Guide

Voltammetric Methods in Brain Systems. A.A. Boulton, G.B. Baker,

and R.N. Adams (Eds), Humana, Totowa, NJ 1995.
Single-Channel Recording (2nd Edition). Bert Sakmann and Erwin
Neher (Eds), Plenum Press, New York 1995. An excellent overview of
patch clamping and related techniques.
Analytical Electrochemistry. Joseph Wang. VCH Publishers, New
York, 1994.
Electrochemistry in Organic Synthesis. J. Volke and F. Liska,
Springer, New York, 1994.
Fundamentals of Electrochemical Analysis (2nd edition). Z. Galus,
Wiley, New York, 1994.
Electrochemistry. Principles, Methods, and Applications.
Christopher M. A. Brett and Anna Maria Oliveira Brett. Oxford
University Press, 1993.
Introduction to Electrochemistry. D. Brynn Hibbert. Macmillian,
London, 1993.
Industrial Electrochemistry. Derek Pletcher and Frank C. Walsh.
Chapman and Hall, London, 1993.
Electrochemical Engineering. Frank C. Walsh. The Electrochemical
Consultancy Ltd, 16 Queens Close, Romsey, SO51 8EG, England,
1993. (FAX: +44 703 676 960).
Electrode Processes. Derek Pletcher. The Electrochemical
Consultancy Ltd, 16 Queens Close, Romsey, SO51 8EG, England,
1993. (FAX: +44 703 676 960).
The Materials Science of Microelectrodes. K. J. Backmann. SpringerVerlag, 1993.
Monitoring Neuronal Activity, J. A. Stamford. IRL Press (at Oxford
University Press), 1992. Includes descriptions of the construction of
microelectrodes, and coated microelectrodes.

Bibliography

275

Potentiometric Water Analysis (2nd edition). Derek Midgley and

Kenneth Torrance. Wiley, Chichester, 1991. Includes very
comprehensive descriptions of the uses of ion selective electrodes.
Biosensors, A. E. G. Cass. IRL Press (at Oxford University Press),
1990.
Microelectrodes: A Special Issue of Electroanalysis, Electroanalysis, 2,
175262, 1990.
Immobilized cells and enzymes, J. Woodward. IRL Press (at Oxford
University Press).
Electroanalytical Techniques in Clinical Chemistry and Laboratory
Medicine. Joseph Wang, VCH, New York, 1988.
Handbook of Inorganic Electrochemistry. Louis Meites and Petr
Zuman. CRC Press, Boca Raton, 1988. [Link]
Polarography and Other Voltammetric Methods. Tom Riley and
Arthur Watson. J. Wiley and Sons, Chichester, 1987.
Stripping Analysis. Joseph Wang, VCH, New York, 1985.
Electroanalytical Chemistry. J. J. Lingane. Wiley, New York, 1985.
Voltage and Patch Clamping with Microelectrodes, Thomas G. Smith
Jr., Harold Lecar, Stevaen J. Redman, and Peter W. Gage. American
Physiological Society, 1985. Describes many useful circuits for use
with microelectrodes.
Potentiometry and Potentiometric Titrations. E. P. Serjeant. Wiley,
New York, 1984.
Electroanalytical Chemistry. Basil H. Vassos and Galen W. Ewing.
Wiley, New York, 1983.
Modern Polarographic Methods in Analytical Chemistry. Alan Bond.
Dekker, 1980.
Electrochemical Methods. Fundamentals and Applications. Allen J.
Bard and Larry R. Faulkener. J. Wiley and Sons, New York, 1980.

276

EChem Users Guide

Interfacial Electrochemistry. E. Gileadi, E. Kirowa-Eisner, and J.

Penciner. VCH, Weinheim, 1981.
Comprehensive Treatise on Electrochemistry. 10 volumes. Plenum
Press, New York, 19801985.
Experimental Approach to Electrochemistry. Nicholas J. Selley.
Edward Arnold, London, 1977.
Transient Techniques in Electrochemistry. D. D. Macdonald. Plenum,
New York, 1977.
Fundamentals of Electrochemical Analysis. Z. Galus. Ellis Horwood,
Chichester, 1976.
Stripping Voltammetry in Chemical Analysis. K. Z. Brainina. Wiley,
London, 1974.
Priciples and Applications of Electrochemistry. D. R. Crow.
Chapman and Hall, London, 1974.
Organic Electrochemistry. R. M. Baizer. Dekker, New York, 1973.
Determination of pH: Theory and Practice (2nd edition). R.G. Bates,
Wiley, New York, 1973.
Synthetic Organic Electrochemistry. Albert J. Fry. Harper and Row,
New York, 1972.
Electrochemical Reactions in Non-Aqueous Systems. Charles K.
Mann and Karen K. Barnes. Marcel Dekker, New York, 1970.
Topics in Organic Polarography. P. Zuman. Plenum, London, 1970.
Organic Polarography. P. Zuman and C. I. Perrin. Interscience, New
York, 1969.
Electrochemistry at Solid Electrodes. R. N. Adams. Dekker, New
York, 1969.
Electrochemical Techniques for Inorganic Chemists. J. B. Headridge.
Academic Press, London, 1969.

Bibliography

277

Coulometry in Analytical Chemistry. G. W. C. Milner and G.

Phillips. Pergamon Press, Oxford, 1967.
Substituent Effects in Organic Polarography. P. Zuman. Plenum,
London, 1967.
Principles of Polarography. J. Heyrovsky and J. Kuta. Academic
Press, New York, 1966.
Amperometric Titrations. John T. Stock. Interscience, New York,
1965.
Polarographic Techniques. L. Meites. Interscience, New York, 1965.
Alternating Current Polarography and Tensammetry. B. Breyer and
H. H. Bauer. Interscience, New York, 1963.
Electroanalytical Principles. R. W. Murray and C. N. Reilley.
Interscience, New York, 1963.
Controlled Potential Analysis. Garry A. Rechnitz. Pergamon,
Oxford, 1962.
Electrochemical Reactions. G. Charlat, J. Badoz-Lambling, and B.
Trmillon. Elsevier, Amsterdam, 1962.
Ionization Constants of Acids and Bases. Adrien Albert and E. P.
Serjeant. Methuen and Co., London, 1962.
The Principles of Electrochemistry. Duncan A. McInnes. Dover, New
York, 1961.
Reference Electrodes. D. J. G. Ives and G. J. Janz. Academic Press,
New York, 1961. Reprinted in 1996 see above.
Electrolyte Solutions. R. A. Robinson, and R. H. Stokes.
Butterworths, London, 1959.
Electrolytic Preparations. Karl Elbs. Edward Arnold, London,1903.
Electrolytic Methods of Analysis. Berhard Neumann. Wittaker and
Co., London, 1898.

278

EChem Users Guide

Journals
Bioelectrochemistry and Bioenergetics. Elsevier.
[Link]
Biosensors and Bioelectronics, Elsevier.
[Link]
Electroanalysis, WileyVCH.
[Link]
Electrochimica Acta. Elsevier.
[Link]
Interface. The Electrochemistry Society.
[Link]
Journal of Applied Electrochemistry. Kluwer.
[Link]
Journal of Electroanalytical Chemistry. Elsevier.
[Link]
Journal of Electroanalytical Chemistry and Interfacial
Electrochemistry. Elsevier.
[Link]
Journal of Solid State Electrochemistry. Springer-Verlag.
[Link]
Journal of The Electrochemical Society.
[Link]
Journal of the Electrochemical Society of Japan, Overseas Edition (in
English).
Russian Journal of Electrochemistry. Kluwer/Plenum.
[Link]

Bibliography

279

280

EChem Users Guide

Glossary
amperometric titrimetry. A titration
technique where a constant potential is held
at the working electrode and the resulting
current measured during a titration.

cathode. Electrode at which reduction takes

place.
compliance. The compliance (or compliance
voltage) of a potentiostat is the potential it is
capable of generating across the working and
auxiliary (counter) electrodes. This may be
much greater than the potential across the
working and reference electrodes.

amperometry. Techniques that monitor the

current signal versus time. The potential is
held constant, or pulses are applied on a base
potential.
amperomogram. Graph of current signal
(usually on the Y axis) versus time (usually
on the X axis).

controlled potential electrolysis. Technique

where a constant potential is held at the
working electrode in order to completely
electrolyse a substance in solution. Usually
the solution is stirred and either the resulting
current, or total charge transferred, is
measured in order to determine the extent of
reaction.

analyte. Substance that an analytical

procedure is trying to detect.
anion. Negatively charged ion.
anode. Electrode at which oxidation takes
place.

chronoamperometry. Technique where a

constant potential is held at the working
electrode and the resulting current measured.

charging (or capacitive) current. Current that

ows due to charging of the electrode and the
interfacial region.

chronocoulometry. Technique where a

constant potential is held at the working
electrode and the resulting transferred charge
measured. It is equivalent to integrating a
chronoamperometric trace.

cation. Positively charged ion.

EChem Users Guide

281

current sampling. With digital techniques the

current ow is sampled (and averaged) for
discrete intervals at exact times. This can
greatly reduce noise.
deposition potential. For stripping
techniques an initial deposition potential is
applied to a mercury lm or hanging drop
electrode. This potential must be sufciently
reducing to ensure that the metal ions of
interest are deposited from solution as metal
atoms which then dissolve in the mercury
electrode.

measured, or at which an electrochemical

reaction takes place.
electrolyse. Chemical reaction (oxidation or
reduction) induced by the passage of an
electric current
electrolyte. substance which forms cations
and anions when dissolved. Also a solution
containing cations and anions.
electronegative. Tending to be reduced
electropositive. Tending to be oxidised

double step chronoamperometry. Technique

where a constant potential is held at the
working electrode and the resulting current
measured. This is followed by switching the
potential to a new value (usually to reverse
the reaction) and the current is again
monitored at the new potential value. The
potential switching may be repeated a
number of times.

electrosynthesis. Synthesis using the passage

of electric current through a solution
emf. Electromotive force (often used
interchangeably but incorrectly with the
terms potential and voltage). The emf of a
cell is determined by a potentiometer with
zero current drain.

electroactive. Capable of undergoing

reduction or oxidation

faradaic current. Current that ows due to

the occurrence of a redox reaction.

electrolytic cell. An electrochemical cell in

which an applied potential causes a chemical
reaction.

frit. Porous disk, usually made of sintered

glass, used to partially separate two solutions.

electrochemistry. A rather general term

covering just about all techniques where
electrodes of any description are used.
Usually current, potential, charge,
conductivity, (or some combination of these)
is measured as a function of one of the others,
or of time, or of addition of titrant etc.
electrode. Solid or liquid (usually of
mercury) material at which a potential is

282

galvanic cell (also a voltaic cell). An

electrochemical cell in which electricity is
produced by a spontaneous redox reaction.
galvanostat. Device to maintain a known
current owing between two electrodes.
half-wave potential (E1/2). The potential
which produces half the diffusion limited
polarographic current. For a reversible redox
reaction, maintaining the working electrode
at E1/2 will ultimately result in equal

EChem Users Guide

voltammetry. Techniques involving the

control potential and measuring the resulting
current ows.

concentrations of the oxidised and reduced

forms of the analyte.
iR compensation. Methods which attempt to
correct for the 'uncompensated resistance' in
an electrochemical cell. This may be useful
when highly resistive cells are being used.
The most common techniques are positive
feedback (offered on many brands of
potentiostat) and current interrupt (offered
with some EG&G PAR potentiostats).
However iR compensation is no substitute for
careful cell design and electrode placement!

voltammogram. Graph of current (usually on

the Y axis) versus potential (on the X axis).

polarography. Electrochemical techniques

involving the use of a dropping mercury
electrode.
potential. The potential energy difference
between two electrodes.
potentiometer. Device or component for
measuring the potential between two points
with zero current drain.
potentiostat. Device for maintaining a known
potential between two electrodes.
salt bridge. Often a tube containing an
electrolyte solution sealed at either end with
a sintered glass frit. (Sometimes a rolled lter
paper soaked in electrolyte solution is used).
A salt bridge connects the solutions in two
separate containers in which the anode and
cathode are placed.
stripping voltammetry. Technique whereby
the analyte is rst concentrated by deposition
on the working electrode. A subsequent
voltametric scan then measures the oxidation
(or reduction) of the deposited material.

Glossary

283

284

EChem Users Guide

Index
compatibility 5
applied potential control 30, 34
Apply Technique 159
Auto Save Data 91
Automatic temperature compensation 196
recording temperature 196
automating EChem 94
auxiliary electrode 269
axes 16

A
About EChem command 20, 227
About This Computer dialog box 228
AC cyclic voltammetry 109
AC Voltammetry 109, 163
active page 44
Add 62
Add Macro to Menu dialog box 95
Add to Data Pad command 57
adding data to the Data Pad 57
ADInstruments Potentiostat 31
applied potential control 30, 34
cell controls 33
dialog box 31
dummy mode 34
ltering 33
real mode 34
settings 31
setting the current range 33
standby mode 34
AMEL 220
amperometric titrimetry 180, 281
amperometry 281
Amplitude axis 17, 48
analysis 11, 37
analysis mode 12
analyte 281
anion 281
Anodic Stripping Voltammetry 135
appending data les 77
Apple menu
About EChem command 20, 227
AppleScript 106
application

EChem Users Guide

B
background
buttons 43
page 54
recording 19, 20
subtraction 54
Baker square wave voltammetry 121
BAS 211
C2 Cell Stand 167
Low Current Module 167
baseline 51, 73
non-linear 54
Begin Repeat 105
biosensors 182
bipolar display 40, 41

C
Cathodic Stripping Voltammetry 137
Cell button 56
Cell Control 33
channel separator 18, 39, 48
checkboxes 12
Chronoamperometry 167
and Chart 167

285

and Scope 172

chronocoulometry 173
chronopotentiometry 175
clean time potential 140
cleaning time 138
Clear Background command 55
Clear command 68
clipboard 69, 71
window 71
close box 15
Close command 14
closing an EChem le 14
colour depth 233
colour display 21, 232
Colour pop-up menu 43
colour printing 82
Command-key equivalents 226
macros 95
comments 65
compatibility with
BAS products 211
EG&G PARC products 206
HEKA products 217
Metrohm products 215
PINE products 214
Radiometer products 216
Schlumberger products 216
complex anions 258
complex cations 257
compliance voltage 267, 269
computed functions 41, 59
Add 62
Differentiate 64
Divide 62
Integrate 63
Invert 62
Multiply 62
Reciprocal 63
sampling speed 60
Shift 62
Smooth 61
Square 63
Subtract 62
Computed Functions command 60
computer requirements 3
connecting to PowerLab24
connection conventions 24
Control Options dialog box 90
control panel
Cursor 18

286

Sample 19
Control Panels 90
control panels 16
hiding 90
moving 91
position 90
controlled current electrolysis 179
controlled potential electrolysis 178
Controls command 90
Copy command 68
Copy Special 76
command 70
Copy to Cliboard dialog box 70
copying data
as picture 70
as text 70
corrosion 201
corrosion techniques 114
Cottrell equation 170, 173, 252
counter electrode 269
crashes 236
current
axis 17
overload 270
range 17
range adjustment 25
scale 17
current sampling
in Differential Pulse Voltammetry 130
in Square Wave Voltammetry 121
Linear Sweep Voltammetry 116
Normal & Reverse Pulse Voltammetry 126
Square Wave Voltammetry technique 121
Cursor panel 18
curve tting 170
customer comment 229
customising EChem 11, 87
Cut command 68
cycles
in Cyclic Voltammetry 144
Cyclic Potentiodynamic Polarization 203
Cyclic Square Wave Voltammetry 146
Cyclic Voltammetry 140
cleaning potential 144
cleaning time 144
common organic solvents 255
deposition potential 143
deposition time 143
dialog box 141
Fast (using Chart and Scope) 164

EChem Users Guide

nal potential 142

initial potential 142
lower potential limit 142
number of cycles 144
potential limits 140
quick reference 246
Range pop-up menu 141
rest time 143
scan rate 142
setting parameters 141
step height 143
step width 143
upper potential limit 142
View button 144
Waveform Overview dialog box 145
waveform terminology 140
with 3rd party potentiostats 145
Cypress Systems 218

pulse amplitude 133

pulse width 133
quick reference 245
Range pop-up menu 132
rest time 134
sampling period 134
scan rate 132
setting parameters 131
step height 132
step width 133
View button 134
waveform terminology 130
Differentiate 64
digital output 139, 160
display and expectations 49
Display Control 10
Display menu 225
Clear Background command 55
Computed Functions command 60
Display Settings command 43
Go To Page command 16, 45
Overlay All command 45
Overlay Display Settings command 44
Overlay None command 45
Set Background command 54
Show Overlay command 45
Subtract Background command 55
display mode 38
display mode pop-up menu 38
Display pop-up menu 91
Display Settings 43, 49
dialog box 43
command 43
Dissolved Oxygen electrode 198
Divide 62
DME 160
DoseResponse software 5
dO2 198
dropping mercury electrode (DME) 160
dummy mode 32
duplicate Marker 52, 73

D
data compression 21
data display area 18, 38
data le 75
data loss 233
Data Pad 5559
adding data 57
functions 58
limits 55
printing 59
setting up 57
Data Pad command 55
Data Pad Miniwindow 59
data resolution 49
Data Selection dialog box 122
dealer and distributor information 228
default settings 13
Delete Macro command 96
Delete Macros dialog box 97
deposition potential
in Cyclic Voltammetry 143
in Stripping Voltammetry 138
deposition time
in Cyclic Voltammetry 143
in Stripping Voltammetry 138
dialog box placement 232
Differential Pulse Voltammetry 130
current sampling 130
dialog box 131
nal potential 132
initial potential 132

Index

E
E vs I 38
EChem desktop icons 12
EChem Options 91
Edit menu 224
Clear command 68
Copy command 68
Copy Special command 70

287

Cut command 68
Paste command 68
Show Clipboard command 71
Undo command 69
editing data 68
EG&G PARC product compatibility 206
electric shock 269
Electrochemical Noise 200
electrode
auxiliary (AE) 269
counter (CE) 269
for organic solvents 259
hanging mercury drop (HMDE) 135, 160
mercury drop (MDE) 135
mercury lm (MFE) 135
potentiometric redox 184
reference (RE) 268
rotating ring disk (RRDE) 180
working (WE) 268
electrode response 194
electrosynthesis 178
emergency access 92
Emergency Access dialog box 93
End Repeat command 106

F
Faraday cage 167, 238
Faraday's constant 252
Fast Cyclic Voltammetry 164
Fast Scan Techniques 163
faster printing 81, 234
le limits 20
File menu 223
Close command 14
New command 12
Open command 12, 77
Page Setup command 80
Print command 79
Quit command 14
Save As command 69, 74
Save command 74
le types
data 75
macro 77
settings 75
text 75
nal potential
in Cyclic Voltammetry 142
in Differential Pulse Voltammetry 132
in Linear Sweep Voltammetry 118

288

in Multi Pulse 147

in Normal & Reverse Pulse Voltammetry 127
in Square Wave Voltammetry 123
frequency setting
in Square Wave Voltammetry 123

G
Galvanic Cells 199
galvanostat 175
gas & stirrer controls 138
Go To Page command 16, 45
Graticule buttons 43

H
half wave potential 251
hanging mercury drop electrode (HMDE) 135, 160
HEKA product compatibility 217
high-resolution printing 49, 81

I
i vs E display mode 38, 68
I vs t display mode 38
icons 12
iE vs t display mode 38, 68
initial potential
in Differential Pulse Voltammetry 132
in Cyclic Voltammetry 142
in Multi Pulse 147, 155
in Linear Sweep Voltammetry 118
in Normal & Reverse Pulse Voltammetry 127
in Square Wave Voltammetry 123
Input Amplier
controls 26
dialog box 27
button 17, 26
installing EChem 6
Integrate 63
Integrated Cottrell equation 253
internet 273
interruptions while recording 20
Invert 62
Invert Axis 41
ion selective electrodes 183
Calibration 189
isopotential point 197

J
journals 279

EChem Users Guide

Command-key equivalents 95
commands 101
deleting 96
keeping records 94
loading 94
nesting 97
opening les 99
playing 96
problems 235
recording 95
sampling 98
saving 94
saving les 100
stopping 96
Main EChem Window 14, 38
manual temperature compensation 194
Marker 18, 48, 50, 72
independent 51, 72
lair 50
locked to waveform 51, 72
Miniwindow 52
Marker command 52
measurement
direct 71
relative 50, 72
memory 20
allocation 20
problems 233
requirements for EChem 3
memory indicator bar 21
menus 223
altering 88
hiding 89
locking 89
Menus command 88
dialog box 88
mercury drop electrode (MDE) 135
mercury lm electrode (MFE) 135
Message command 103
Metrohm product compatibility 215
Miniwindow 52, 59
Multi Pulse technique 146
dening pulses 149, 156
dialog box 147
nal potential 147
initial potential 147, 155
pulse duration 151, 157
pulse height 150, 156
pulse increment 150, 157
pulse start time 149, 156

K
Keep Partial Data 20, 91
keyboard shortcuts 16, 44, 226

L
Line Type buttons 43
Linear Sweep Voltammetry 116
current sampling 116
dialog box 117
nal potential 118
initial potential 118
quick reference 242
rest time 117, 119, 123, 132, 141, 147
scan rate 118
setting parameters 117
step height 119
step width 119
View button 119
Waveform Overview dialog box 119
waveform terminology 116
liquid chromatography 181
low current experiments 166
lower potential limit
in Cyclic Voltammetry 142

M
Macintosh 104
macro commands 101
AppleScript... command106
Begin Repeat command 105
Delete Macro command 96
End Repeat command 106
Message command 103
Message dialog box 104, 105
Open dialog box 99
Play Sound command 102
Play Sound dialog box 103
Repeat for Each Page command 105
Save As dialog box 100
Speak Message command 104
Start Recording command 95
Update Screen command 101
Wait command 101
Wait dialog box 102
macro le 77
Macro menu 225
macros 94
called by other macros 97
changing dialog box settings 98

Index

289

quick reference 247

ramp parameters 146, 155
Range pop-up menu 155
rest time 148, 149, 155
sampling period 152, 158
Sampling Time dialog box 150, 157
Sampling... button 150, 157
scan rate 148
setting parameters 146, 154
step height 148, 155
step width 148, 155
Multiply 62

N
navigating 16, 44
Nernst equation 184, 192
Nernstian response 185, 195
New command 12
noise 237
non-linear baseline 54
Normal & Reverse Pulse Voltammetry 126
current sampling 126
dialog box 127
nal potential 127
initial potential 127
pulse width 128
quick reference 244
rest time 128
sampling period 129
scan rate 127
setting parameters 126
step height 128
step width 128
View button 129
Waveform Overview dialog box 129
waveform terminology 126
Notebook 64
printing 65, 84
Notebook command 64

O
off-screen buffer 21, 233
Open dialog box 78
Open directory dialog box 13
opening a EChem le 12
Open command 12, 77
organic solvents 255
Osteryoung square wave voltammetry 121
out of compliance 269

290

Overlay All command 45

Overlay Display Settings command 44
Overlay None command 45
overlaying
channels 39
display settings 44
pages 45
overview of EChem 10

P
Page buttons 16, 44, 46, 54
pop-up menu 46
Page Comment 65
button 18, 49, 65
window 65
page comments 65
editing 65
printing 66
Page Corner controls 16, 44
page denition 16, 44
Page Layout dialog box 84
page limit 20
Page Setup command 80
dialog box 80
Parry-Osteryoung equation 251
Paste command 68
pasting in text 79
Pause button 28
pH Amp 182
pH electrode 182
calibration 189
isopotential point 197
pH extension 189
Picostat 166
PINE product compatibility 214
Play Sound command 102
pointer 19
arrow-headed cross 91
cross 72
double-headed arrow 72
dragging 42
heavy cross 56
I-beam 19, 56
resizing 57
stretching 42
Polarity 34
polarization resistance 203
Polarographic Techniques 140, 160
polarography 109
potential axis 17, 42
EChem Users Guide

in Differential Pulse Voltammetry 133

in Normal & Reverse Pulse Voltammetry 128

potential limits
in Cyclic Voltammetry 140
potential monitoring 25
potentiodynamic polarization 202
potentiometric
redox electrode 184
sensors 182
potentiostat
current output 25
potential output 25
Potentiostat, see ADInstruments Potentiostat
Potentiostat dialog box 31, 32
potentiostats
third party input range adjustment 25
PowerChrom software 5
PowerLab
e and S models 5
digital (TTL) outputs 139, 160
PowerLab Unavailable dialog box 7
Preferences 88
submenu 88, 224
Controls command 90
Menus command 88
Options command 91
Start-Up command 92
Print
Current Page Only checkbox 83, 234
Sweep Description 83
Printers 3, 4
printing 79
colour 82
Data Pad 59
EChem pages per sheet 81
faster 81
high-resolution 49, 81
Notebook 65
page comments 66
problems 234
Zoom window 49
Print command 79
problems and solutions 229
Progress Indicator display 21
pulse amplitude
in Differential Pulse Voltammetry 133
pulse height
denition 114
Pulse Techniques 114
pulse terminology 114
pulse width
denition 114

Index

Q
Quartz Crystal Microbalance 200
Quit command 14
quitting EChem 8, 14

R
radio buttons 12
Radiometer product compatibility 216
RAM memory requirements 3, 4
ramp
digitally generated 110
staircase 110, 116, 121
Randles-Sevcik Equation 249
range 28
Range pop-up menu 17, 28
in Cyclic Voltammetry 141
in Differential Pulse Voltammetry 132
in Multi Pulse techniques 155
in Square Wave Voltammetry 123
Read Text Options dialog box 79
real mode 32
Reciprocal 63
recording 19
display during 20
delity 15, 49
length 20
memory 20
problems 233
reference electrode 268
Repeat for Each Page command 105
rest time 115
in Cyclic Voltammetry 143
in Differential Pulse Voltammetry 134
in Linear Sweep Voltammetry 117, 119, 123,
132, 141, 147
in Multi Pulse 148, 149, 155
in Normal & Reverse Pulse Voltammetry 128
in Square Wave Voltammetry 125
Reverse Polarity 34
Reverse Pulse Voltammetry 126
rotating ring disk electrode 180
Row button 56

S
Sample panel 19
Sampling dialog box 32

291

Sampling Display 122

sampling period 76, 78
denition 114
duration 114
in Differential Pulse Voltammetry 134
in Multi Pulse techniques 152, 158
in Square Wave Voltammetry 124
inNormal & Reverse Pulse Voltammetry 129
sampling speeds
computed functions 60
Sampling Time dialog box 150, 157
Sampling... button 150, 157
Save As command 69, 74
Text dialog box 74, 76
Save command 74
scale
moving 42
overlaid pages 46
setting 42
stretching 42
Scale pop-up menu 17, 28
Scan Rate 113
scan rate
in Cyclic Voltammetry 142
in Differential Pulse Voltammetry 132
in Linear Sweep Voltammetry 118
in Multi Pulse 148
in Normal & Reverse Pulse Voltammetry 127
Schlumberger product compatibility 216
Scrolling button 16, 44
selecting data 68
selection information 58
Set Background command 54
Set Scale 41
Setting a baseline 74
settings 75, 92
Shift 62
Show Clipboard command 71
Show Display Control 91
Show Overlay command 45
signal inversion 29
single-sided display 40
size box 15
slope 58
Smooth 61
smoothing waveforms 62
Solubility Rules 255
solvent stability 256
Speak Message command 104
dialog box 105

292

square 63
square wave amplitude
in Square Wave Voltammetry 124
Square Wave Voltammetry 121
current sampling 121
dialog box 123
nal potential 123
frequency 123
initial potential 123
quick reference 243
range pop-up menu 123
rest time 125
sampling period 124
setting parameters 122
square wave amplitude 124
step height 124
View button 125
Waveform Overview dialog box 125
waveform terminology 121
staircase ramp 110, 116, 121
Standby mode 34
Start button 19
Start Recording command 95
Start-up problems 229
Start-Up command 92
Settings dialog box 92
statistics 58
step height
denition 110
in Cyclic Voltammetry 143
in Differential Pulse Voltammetry 132
in Linear Sweep Voltammetry 119
in Multi Pulse 148, 155
in Normal & Reverse Pulse Voltammetry 128
in Square Wave Voltammetry 124
step width
denition 110
in Cyclic Voltammetry 143
in Differential Pulse Voltammetry 133
in Linear Sweep Voltammetry 119
in Multi Pulse 148, 155
in Normal & Reverse Pulse Voltammetry 128
stirrer & gas controls 138
Stripping Voltammetry 135
clean time potential 140
cleaning time 138
deposition potential 138
deposition time 138
setting parameters 137
stirrer & gas controls 138

EChem Users Guide

Subtract 62
Subtract Background command 55
system conguration information 228

three electrode cells 267

Time axis 16
Timed Events 168, 178
title bar 15
titrimetry
amperometric 180
potentiometric 197
Trace Indicator 20
transferring data 69

T
technical support 227
technique description 17
Technique menu 224
techniques 11
AC voltammetry 163
additional to EChem 162
anodic stripping voltammetry 135
cathodic stripping voltammetry 137
chronoamperometry 167
chronocoulometry 173
chronopotentiometry 175
controlled Potential Electrolysis 178
corrosion 114
cyclic potentiodynamic polarization 203
Cyclic Voltammetry 140
Differential Pulse Voltammetry 130
electrosynthesis 178
Linear Sweep Voltammetry 116
list of, 108
low current experiments 166
Multi Pulse 146
Normal & Reverse Pulse Voltammetry 126
polarization resistance 203
potentiodynamic polarization 202
Square Wave Voltammetry 121
stripping voltammetry 135
temperature compensation
automatic 196
manual 194
Text Books 274
text le 75
pasting in from Scope 79
reading 78
third party equipment
BAS 211
EG&G PARC 206
HEKA 217
Metrohm 215
PINE 214
Radiometer 216
Schlumberger 216
third party potentiostats
adjusting the input range 25
applying units conversion 29
performing Cyclic Voltammetry 145

Index

U
Undo command 69
Units Conversion 29, 40, 41, 232
dialog box 29, 32
Update Screen command 101
upper potential limit
in Cyclic Voltammetry 142
using this guide 2

V
View button
in Differential Pulse Voltammetry 134
in Cyclic Voltammetry 144
in Linear Sweep Voltammetry 119
in Normal & Reverse Pulse Voltammetry 129
in Square Wave Voltammetry 125
voltammetric ramp 110
voltammetry 109
AC 109, 163
anodic stripping 135
Baker square wave 121
cathodic Ssripping 137
Cyclic 140
Differential Pulse 130
Fast Cyclic 164
Linear Sweep 116
Normal & Reverse Pulse 126
Osteryoung square wave 121
Square Wave 121
stripping 135

W
Wait command 101
Waveform Cursor 71, 72, 73
waveform cursor display 18
Waveform Overview dialog box
in Cyclic Voltammetry 145
in Linear Sweep Voltammetry 119
in Normal & Reverse Pulse Voltammetry 129

293

in Square Wave Voltammetry 125

Waveform Print Layout buttons 81, 234
window
Clipboard 71
controls 15
Main 14
Page Comment 65
Zoom 47
Windows menu 225
Add to Data Pad command 57
Data Pad command 55
Marker command 52
Notebook command 64
Zoom Window command 47
working electrode 268

XYZ
zero reference point 50, 72
zoom box 16, 55
Zoom window 47, 69
Zoom Window command 47

294

EChem Users Guide

Licensing & Warranty Agreement

If problems arise with an ADI product, ADI will

make all reasonable efforts to x them. This service
may incur a charge, depending on the nature of
the problems, and is subject to the other conditions
in this Agreement.

Extent
This Agreement is between ADInstruments Pty
Ltd [ADI] and the purchaser [the Purchaser] of
any ADI product software, hardware, or both
and covers all obligations and liabilities on the
part of ADI, the Purchaser, and other users of the
product. The Purchaser (or any user) accepts the
terms of this Agreement by using the product. Any
changes to this Agreement must be recorded in
writing and have ADIs and the Purchasers
consent.

Limitations
Since ADI products could be affected by external
factors (for instance, the computer system on
which they run), absolute performance and
reliability cannot be guaranteed. No warranty,
either express or implied or statutory, other than
that contained in this Agreement, is made in
respect to ADI products. The Purchaser therefore
assumes all risks as to the performance and
reliability of the products, and the results gained
using them.

Copyright and Trademarks

ADI develops proprietary computer software and
hardware, including PowerLab units. All ADI
software, hardware, and documentation is
protected by copyright, and may not be
reproduced or altered in any way, nor may
products be derived from or based on it. ADI
retains the exclusive ownership of the trademarks
and registered trademarks represented by its
company name, logo, and product names.

No claim for damages of any sort arising from the

use or misuse of ADI products can be made
against ADI or its agents or employees.
Nevertheless, ADI products are produced to high
standards, and should perform substantially as
described in the supplied documentation. There is
a limited hardware warranty, and technical
support is provided for all products.

Responsibilities
The Purchaser and any others using any ADI
product agree to use it in a sensible manner for
purposes for which it is suited, and agree to take
responsibility for their actions and the results of
their actions.

EChem Users Guide

295

Hardware Warranty

Technical Support

ADI warrants that the hardware purchased by the

Purchaser shall be free of defects in material and
workmanship for one year from its date of
purchase. If there is such a defect, ADI will repair
or replace the equipment as appropriate, and the
duration of the warranty shall be extended by the
length of time needed for repair or replacement.
The Purchaser should contact ADI for return
authorisation before sending back defective
products.

Once a customer registration form has been lled

out and sent in, the Purchaser is entitled to free
technical support for any ADI product for one year
from its date of purchase. (A customer registration
form is included with each product: if for some
reason you cannot nd one, contact ADI for
another.) This involves help and advice concerning
installation, operation, particular uses, and
problems that may arise in the use of ADI
products.

This warranty applies only to hardware used

normally and within its operating specications. It
does not cover hardware modied in any way,
subjected to unusual physical, electrical, or
environmental stress, used with incorrectly wired
or substandard connectors or cables, or with the
original identication marks altered.

Jurisdiction
This Agreement shall be governed by the laws of
New South Wales in Australia, and any
proceedings concerning it shall be heard and
resolved by the Supreme Court of New South
Wales in Australia.

Software License
The Purchaser has the non-exclusive right to use
the supplied ADI software. (The Purchasers
employees or students, for instance, are entitled to
use it, provided they adhere to this Agreement.)
The Purchaser can make as many backup copies of
ADI software as is reasonable. Each separate
purchase of a software program, however, licenses
it to be used on only one computer at any given
time. Although multiple copies of a purchased
program may exist, two or more copies must not
be used simultaneously. Site licenses (multipleuser licenses) are treated as if ve copies of a
program were purchased separately, even if only
one set of disks is provided.

296

EChem Users Guide