Chapter 1: Classification of Analytical
Methods
Naaimat Muhammed
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Instrumental Analysis
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Introduction:
Analytical Chemistry deals with methods for determining the chemical
composition of samples of matter. A qualitative method yields
information about the identity of atomic or molecular species or the
functional groups in the sample; a quantitative method, in contrast,
provides numerical information as to the relative amount of one or
more of these components.
Analytical methods are often classified as being either classical
or instrumental. This classification is largely historical with classical
methods, sometimes called wet-chemical methods, preceding
instrumental methods by a century or more.
Classical Methods:
Separation of analytes by precipitation, extraction, or distillation.
Qualitative analysis by reaction of analytes with reagents that
yielded products that could be recognized by their colors, boiling or
melting points, solubilities, optical activities, or refractive indexes.
Quantitative analysis by gravimetric or by titrimetric techniques.
In the early years of chemistry, most analyses were carried out by
separating components of interest in a sample by precipitation,
extraction, or distillation. For quantitative analyses, the separated
components were then treated with reagents that yielded products
that could be recognized by their colors, boiling points or melting
points, their solubility in a series of solvents, their odors, their optical
activities, or their refractive indexes. For quantitative analyses, the
amount of analyte was determined by gravimetric or by titrimetric
measurement.
Gravimetric Methods the mass of the analyte or some compound
produced from the analyte was determined.
Titrimetric Methods the volume or mass of a standard reagent
required to react completely with the analyte was measured.
Instrumental Methods:
Measurements of physical properties of analytes, such as conductivity,
electrode potential, light absorption, or emission, mass to charge ratio,
and fluorescence, began to be used for quantitative analysis of a
variety of inorganic, organic, and biochemical analyte. Highly efficient
chromatographic and electrophoretic techniques began to replace
distillation, extraction, and precipitation for the separation of
components of complex mixtures prior to their qualitative or
quantitative determination. These newer methods for separating and
determining chemical species are known collectively as instrumental
methods of analysis.
Instrumentation can be divided into two categories: detection and
quantitation.
Measurement of physical properties of analytes - such as
conductivity, electrode potential, light absorption or emission, massto-charge ratio, and fluorescence-began to be employed for
quantitative analysis of inorganic, organic, and biochemical
analytes.
Efficient chromatographic separation techniques are used for
the separation of components of complex mixtures.
Instrumental Methods of analysis (collective name for newer
methods for separation and determination of chemical species.)
Define The Problem
In order to select an analytical method intelligently, it is essential to
define clearly the nature of the analytical problem. Such a definition
requires answers to the following questions.
1. What accuracy and precision are required?
2. How many samples are available?
3. What is the concentration range of the analyte?
4. What components of the sample will cause interference? /What else
is present?
5. Where is the origin of the sample?
6. What are the physical and chemical properties of the sample matrix?
7. When was it released or discharged?
8. How/ under what circumstances will certain reactions occur?
Instrumentation is necessary to decipher these values. The challenge
for the instrumental scientist is to mimic the 5 senses. Substances
have physical and chemical fingerprints with unique thresholds. The
object is to detect a chemical substance within a matrix and selectively
perturb the substance of interest. Signals must be readable (in a
voltage or electrical signal).
Signals Employed in Instrumental Methods
Table 1-1
The table below lists the names of instrumental methods that are
based upon various analytical signals.
Signal
Emission of radiation
Absorption of radiation
Scattering of radiation
Refraction of radiation
Diffraction of radiation
Rotation of radiation
Electrical potential
Electrical charge
Electrical current
Electrical resistance
Mass-to-charge ratio
Rate of reaction
Instrumental Methods
Emission spectroscopy (X-ray, UV,
visible,
electron, Auger); fluorescence,
phosphorescence, and
luminesc
ence
(X-ray, UV, and visible)
Spectrophotometry and
photometry (X-ray, UV, visible, IR);
photoacoustic spectroscopy;
nuclear magnetic resonance and
electron spin resonance
spectroscopy
Turbidimetry; nephelometry;
Raman spectroscopy
Refractometry; interferometry
X-Ray and electron diffraction
methods
Polarimetry; optical rotary
dispersion; circular dichroism
Potentiometry;
chronopotentiometry
Coulometry
Polarography; amperometry
Conductometry
Mass spectrometry
Kinetic methods
Thermal properties
Radioactivity
Thermal conductivity and enthalpy
Activation and isotope dilution
methods
Analytical Signals
Data Domain information
encoded
Non-electrical Domains
(scale, number, chemical)
Electrical Domains (volts,
current, charge)
Analog Domains
continuous quantities (volts,
current)
Time Domains (pulses,
slopes)
Digital Domains (Off/On or
Hi/Lo)
Selecting an
Analytical Method
Required Accuracy
Amount of sample
Concentration range(s)
of analyte(s)
Possible interferences
Chemical and physical
properties of matrix
Number of samples
Desirable
Characteristics for
an
Analytical Method
Speed
Ease and Convenience
Skill required of operator
Cost and availability of
equipment
Per-samples cost
Numerical Criteria
for
Selecting an
Analytical Method
Precision
Absolute standard deviation
Relative standard deviation
Coefficient of variation
Variance
Bias
Absolute systematic error
Relative systematic error
Sensitivity
Calibration
Analytical
Detection Limit
Blank plus three times Std.
Dev. of blank
Concentration Range
Limit of Quantitation
(LOQ)
Limit of Linearity (LOL)
Selectivity
Effects of interferences
Coefficient of Selectivity
Examples of Instrumental Components
Table 1-2
The table below lists most of the analytical signals that are currently
used for instrumental analysis.
Signal
Transduced Signal
Readout
Instrument
Generator
Transducer
Signal
Photometer
Tungsten lamp,
Photocell
Electrical
glass filter,
current
meter
sample
Analytical
Input
Signal
Attenuated light
None
Current
beam
Atomic emission
Electrical
spectrometer chromator,
demodulator
Flame, mono- UV or visible Photomultiplier
Amplifier,
Chart
radiation
tube
potential
recorder
chopper, sample
Coulometer
Cell current
Chart
sample
DC source,
Amplifier
current
pH meter
Sample
Electrical
Electrodes
Electrical
recorder
Hydrogen ion Glass-calomel
Amplifier, Digital unit
activity
electrodes potential
digitizer
X-Ray powder X-Ray tube,
Latent
diffractometersample
developer
Diffracted
Chemical
radiation
images
Photographic
Black
film
image
Color
Visual
Eye
on film
Color
comparator
Sunlight,
Brain
sample
color re-
Optic nerve
signal
sponse
Numerical Criteria for selecting Analytical Methods
The table below lists quantitative performance criteria of instruments,
criteria that can be used to decide whether or not a given instrumental
method is suitable for attacking an analytical problem. These
characteristics are expressed in numerical terms that are called figures
of merit. Figures of merit permit the chemist to narrow the choice of
instruments for a given analytical problem to a relatively few.
Selection among these few can then be based upon qualitative
performance criteria such as speed, ease of convenience, skill required
of operator, cost and availability of equiptment, per sample cost.
1.
Criteria
Precision
2.
Bias
3.
Sensitivity
4.
Detection limit
5.
Concentration Range
6.
Selectivity
Figure of Merit
Absolute standard
deviation,
relative standard deviation,
coefficient of variation,
variance
Absolute systematic error,
relative systematic error
Calibration sensitivity,
analytical sensitivity
Blank plus three times
standard deviation of a blank
Concentration limit of quantitation (LOQ) to concentration limit of linearity (LOL)
Coefficient of selectivity
Precision
Precision of analytical data is the degree of mutual agreement among
data that
have been obtained in the same way. Precision provides a measure of
the
random, or indeterminate,, error of an analysis. Figures of merit for
precision
include: absolute standard deviation, relative standard deviation,
standard
deviation of the mean, coefficient of variation, and variance.
Bias
Bias provides a measure of the systematic, or determinate, error of an
analytical method.
bias = g xt
Where: g is the population mean for the concentration of analyte in a sample
that has a true concentration of xt
Sensitivity
Ability to discriminate between small differences is analyte
concentration.
calibration sensitivity
S = MC + Sbl
S=
measured signal
c =
concentration of analyte
Sbi = instrument signal for a blank
M=
the straight line
slope of
Analytical Sensitivity
= m / Ss
= analytical sensitivity
m = slope of straight line
Ss = standard deviation of the signals
Detection Limit
The minimum concentration or weight of analyte that can be
detected at a known confidence level.
The useful range of an analytical method ranges from the lowest
concentration at which quantitative measurements can be made
(LOQ) to the concentration at which the calibration curve departs
from linearity (LOL).
Cm =
Cm =
Sm =
Sbl =
M=
Sm Sbl
m
detection limit
minimum distinquishable analytical signal
mean signal of blank
slope of calibration curve
Selectivity
The degree to which it is free from interference by other
species contained in the sample matrix.
Other Characteristics to Be Considered in Method Choice
1. Speed
2. Ease and convenience
3. Skill required of operator
4. Cost and availability of equipment
5. Per-sample cost
Applicable Concentration Range
The figure below illustrates the definition of the useful range of an
analytical method, which is from the lowest concentration at which the
quantitative measurements can be made (limit of quantitation LOQ) to
the concentration at which the calibration curve departs from linearity
(limit of linearity LOL)
Useful Websites Dealing With Instrumental Analysis
American Chemical Society:
http://www.acs.org
Chemical Abstracts Service:
http://www.cas.org
Chemical Center Home Page: (maintained by ACS)
http://www.chemcenter/org
Science Magazine:
http://www.sciencemag.org
Journal of Chemistry and Spectroscopy:
http://www.kerouac.pharm.uky.edu/asrg/wave/wavehp.html
