ANALYTICAL CHEMISTRY 1

INTRODUCTION
• Course: Analytical Chemistry
- Mid-term test: 03 (5%)
- Dilegence: full attendance at mid-term tests
(5%)
- Lab work: 20%
- Final exam: 90-min open book (3-4
questions) (70%)
 References
• Bộ Y tế (2014), Hóa Phân tích I, Nhà xuất
bản Y học
• D.A. Skoog, D. M. West, F.J. Holler
(2013), Fundamentals of analytical
chemitry, Saunders College Publishing.
 LESSON 1
Learning outcomes:
Appreciate the role of analytical chemistry
Describe the basic terminology in
analytical chemistry
Describe the commonly used tools in
analytical chemistry
Perform basic calculations in analytical
chemistry
 1. The Role of
Analytical Chemistry
 What Is Analytical Science?
Analytical Chemistry is the science of chemical
measurement. Its object is the generation,
treatment and evaluation of signals from which
information is obtained on the composition and
structure of matter.
 Qualitative and Quantitative
Analysis
Qualitative tests may be performed by
selective chemical reactions or with the use
of instrumentation.
A selective reaction or test is one that can
occur with other substances but exhibits a
degree of preference for the substance of
interest.
A specific reaction or test is one that
occurs only with the substance of interest.
For quantitative analysis, the typical sample
composition will often be known or else the
analyst will need to perform a qualitative
test prior to performing the more difficult
quantitative analysis.
Modern chemical measurement systems
often exhibit sufficient selectivity that a
quantitative measurement can also serve
as a qualitative measurement. However,
simple qualitative tests are usually more
rapid and less expensive than quantitative
procedures.
 OBTAINING A REPRESENTATIVE
SAMPLE——WE CAN’T
ANALYZE THE WHOLE THING
The gross sample consists of several
portions of the material to be tested. The
laboratory sample is a small portion of this,
taken after homogenization. The analysis
sample is that actually analyzed
 PREPARING THE SAMPLE FOR
ANALYSIS——IT PROBABLY
NEEDS TO BE ALTERED
Solid samples usually must be put into
solution.
Ashing is the burning of organic matter.
Digestion is the wet oxidation of organic
matter.
The pH of the sample solution will usually
have to be adjusted.
Always run a blank!
A blank theoretically consists of all
chemicals in the unknown and used in an
analysis in the same amounts (including
water), run through the entire analytical
procedure. The blank result is subtracted
from the analytical sample result to arrive
at a net analyte concentration in the
sample solution.
If the blank is appreciable, it may
invalidate the analysis. Oftentimes, it is
impossible to make a perfect blank for an
analysis.
 PERFORMING NECESSARY CHEMICAL
SEPARATIONS
In order to eliminate interferences, to provide
suitable selectivity in the measurement, or to
preconcentrate the analyte for more sensitive
or accurate measurement, the analyst must
often perform one or more separation steps.
It is preferable to separate the analyte away
from the sample matrix, in order to minimize
losses of the analyte.
Separation steps may include precipitation,
extraction into an immiscible solvent,
chromatography, dialysis, and distillation.
PERFORMING THE MEASUREMENT——YOU
DECIDE THE METHOD
A standard operating procedure is “a
detailed written instruction to achieve
uniformity in the performance of a specific
function”
A protocol is a set of guidelines
appropriate to a particular analytical area
or generic group of operations
A standard method consists of a set of
instructions about how to carry out a
method issued by a national standards
body
 A primary method is one having the highest
metrological qualitites, whose operations can be
completely described and understood, and for
which a complete uncertainty statement can be
written down in terms of SI units
A reference method is a method of known
and demonstrated accuracy. It has
undergone a collaborative study using
materials (e.g. certified reference material)
where the amount of the analyte present in
the material and its uncertainty are known.
 INSTRUMENT STANDARDIZATION

Most instrumental methods of analysis are

relative. Instruments register a signal due
to some physical property of the solution

Instrument response may be linearly or

nonlinearly related to the analyte
concentration.
 Validation of a Method—You Have to
Prove It Works!
Great care must be taken that accurate
results are obtained in an analysis. Two
types of error may occur: random and
systematic. Every measurement has some
imprecision associated with it, which
results in random distribution of results, for
example, a Gaussian distribution.
The best way to validate a method is to
analyze a standard reference material of
known composition.
 Analyze Versus Determine—
They Are Different
a sample is analyzed for part or all of its
constituents.
The process of measuring the analyte is
called a determination.
The constituents in the sample may be
classified as major (>1% of the sample),
minor (0.1 to 1%), or trace (<0.1%). A few
parts per billion or less of a constituent
might be classified as ultratrace.
2. Tools of Analytical
Chemistry
 Selecting and Handling Reagents
and Other Chemicals

Reagent Grade

Primary-Standard Grade
Special-Purpose Reagent Chemicals
 Reference material (RM)
The ISO definition of a Reference material
(RM) is “a material or substance one or
more of whose property values are
sufficiently homogeneous and well
established to be used for the calibration
of an apparatus, the assessment of a
measurement method, or for assigning
values to materials”.
 Certified reference material
(CRM)
“Reference material, accompanied by a
certificate, one or more of whose property
values are certified by a procedure, which
establishes its traceability to an accurate
realization of the unit in which the property
values are expressed, and for which each
certified value is accompanied by an
uncertainty at a stated level of
confidence”.
 Chemical standards
An anytical standard is generally used to
describe a solution or matrix containing a
know amount of analyte, which will be
used to check the performance of a
method/instrument.
A calibration standard is a pure compound
of accurately known concentration used to
calibrate an instrument.
The concentrated analytical standard is
known as the stock solution. The solutions
used to perform the calibration are
described as working standards.
Primary standard is defined as a “standard
that is designed or widely acknowledged
as having the highest metrological
qualities and whose value is accepted
without reference to other standards of the
same quantity.
 Rules for Handling Reagents
and Solutions
1. Select the best grade of chemical available for
analytical work. Whenever possible, pick the
smallest bottle that is sufficient to do the job.
2. Replace the top of every container immediately
after removing reagent. Do not rely on someone
else to do so.
3. Hold the stoppers of reagent bottles between
your fingers. Never set a stopper on a desk top.
4. Unless specifically directed otherwise, never return
any excess reagent to a bottle. The money saved by
returning excesses is seldom worth the risk of
contaminating the entire bottle.
5. Unless directed otherwise, never insert spatulas,
spoons, or knives into a bottle that contains a solid
chemical. Instead, shake the capped bottle vigorously
or tap it gently against a wooden table to break up an
encrustation. Then pour out the desired quantity.
These measures are occasionally ineffective, and in
such cases a clean porcelain spoon should be used.
6. Keep the reagent shelf and the laboratory
balance clean and neat. Clean up any spills
immediately.
7. Follow local regulations concerning the disposal
of surplus reagents and solutions.
 Cleaning and Marking
of Laboratory Ware
Every beaker, flask, or crucible that will contain
the sample must be thoroughly cleaned before
being used. The apparatus should be washed
with a hot detergent solution and then rinsed—
initially with large amounts of tap water and finally
with several small portions of deionized water.
Properly cleaned glassware will be coated with a
uniform and unbroken film of water. It is seldom
necessary to dry the interior surface of glassware
before use. Drying is usually a waste of time and
is always a potential source of contamination.
 Measuring Mass
An analytical balance is an instrument for
determining mass with a maximum capacity that
ranges from 1 g to a few kilograms with a
precision of at least 1 part in 105 at maximum
capacity. The precision and accuracy of many
modern analytical balances exceed 1 part in 106
at full capacity.
 Types of analytical balances
• The most common analytical balances
(macrobalances) have a maximum capacity
ranging between 160 and 200 g. With these
balances, measurements can be made with a
standard deviation of 0.1 mg.
Semimicroanalytical balances have a maximum
loading of 10 to 30 g with a precision of  0.01 mg.
A typical microanalytical balance has a capacity
of 1 to 3 g and a precision of  0.001 mg (1 μg).
 Precautions in Using
an Analytical Balance
1. Center the load on the pan as well as possible.
2. Protect the balance from corrosion. Objects to
be placed on the pan should be limited to
nonreactive metals, nonreactive plastics, and
vitreous, or glasslike, materials.
3. Observe special precautions (see Section 2E-6)
for the weighing of liquids.
4. Consult your instructor if the balance appears to
need adjustment.
5. Keep the balance and its case scrupulously
clean. A camel’s-hair brush is useful for removing
spilled material or dust.
6. Always allow an object that has been heated to
return to room temperature before weighing it.
7. Use tongs, finger pads, or a glassine paper strip
to handle dried objects to prevent transferring
moisture to them.
 Sources of Error in Weighing

A buoyancy error will affect data if the

density of the object being weighed differs
significantly from that of the standard
masses. This error has its origin in the
difference in buoyant force exerted by the
medium (air) on the object and on the
masses.
W1 is the corrected mass of the object, W2
is the mass of the standard masses, dobj is
the density of the object, dwts is the density
of the masses, and dair is the density of the
air displaced by masses and object. The
value of dair is 0.0012 g/cm3
 Temperature Effects
Attempts to weigh an object whose temperature is
different from that of its surroundings will result in
a significant error. Failure to allow sufficient time
for a heated object to return to room temperature
is the most common source of this problem. Errors
due to a difference in temperature have two
sources. First, convection currents within the
balance case exert a buoyant effect on the pan
and object. Second, warm air trapped in a closed
container weighs less than the same volume at a
lower temperature. Both effects cause the
apparent mass of the object to be low.
 Equipment and manipulations
associated with weighing

weighing bottles.
desiccator containing weighing
bottles with dry solids
 Quantitative transfer of
Arrangement for the solid sample. Note the use
drying of samples of tongs to hold the
weighing bottle and a paper
strip to hold the cap to
avoid contact between
glass and skin.
Filtering and Washing Precipitates

Washing by Transferring the precipitate

decantation
 Measuring Volume

The coefficient of expansion for dilute

aqueous solutions (approximately
0.025%/°C) is such that a 5°C change has
a measurable effect on the reliability of
ordinary volumetric measurements
Apparatus for Precisely
Measuring Volume
Avoiding Parallax
CALIBRATING VOLUMETRIC
GLASSWARE
 The Laboratory Notebook

 You must carefully

record experimental
observations in your
notebook as soon as
they occur.
 An entry in a laboratory
notebook should never
be erased but should be
crossed out instead.
 Safety in the laboratory

• Wear eye protection at all times.

 3. Calculations Used
in Analytical Chemistry
 Some Important Units of Measurement

SI Units
The Distinction Between Mass and Weight ?

The mole (abbreviated mol) is the SI unit for

the amount of a chemical substance
 Solutions and Their Concentrations

Molar analytical concentration

Molar equilibrium concentration
 An electrolyte is a substance that dissociates
into ions in solution. In general, electrolytes are
more dissociated in water than in other solvents.

 Sometimes the molarity of a strong electrolyte is

called the formal concentration (F), to
emphasize that the substance is really converted
into other species in solution
Molality (m) is concentration expressed as
moles of substance per kilogram of solvent (not
total solution). Molality is independent of
temperature. Molarity changes with temperature
because the volume of a solution usually
increases when it is heated.
 Normality

• A one-normal solution contains one

equivalent per liter. An equivalent
represents the mass of material providing
Avogadro’s number of reacting units.
at the equivalence point in any titration,
 Titer

The titer is the weight of analyte that is

chemically equivalent to 1mL of the titrant,
usually expressed in milligrams
Percent Concentration
Parts per Million and Parts per Billion
p-Functions
 Chemical Stoichiometry

Stoichiometry is the quantitative relationship

among the amounts of reacting chemical species.