The Analytical Process

The Analytical
Process
CHM123 1st SEM 2022-23
Analytical Chemistry deals with methods for
determining the chemical composition of samples.
• Qualitative Analysis (identification) provides information

about the identity of species or functional groups in the
sample (an analyte can be identified).
• Quantitative Analysis provides numerical information of

analyte (quantitate the exact amount or concentration).
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Analytical Methods
▹Classical Methods: Wet ▸ Instrumental Methods: Analytical

chemical methods such as measurements (conductivity,
precipitation, extraction, electrode potential, light
distillation, boiling or melting absorption or emission, mass-
points, gravimetric and to-charge ratio, fluorescence
titrimetric measurements. etc.) are made using
instrumentation.
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Classifying Quantitative Analytical Methods
▸ Gravimetric Methods ▸ Volumetric Methods
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▸ Spectroscopic Methods ▸ Chromatographic Methods
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▸ Electroanalytical Methods
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What is the
Role of
Analytical
Chemistry?
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Classification of Analyses
1. Based on the extent of analysis
a. complete or exact analysis
– the amount of each constituent of the sample is
determined quantitatively.
Ex. blood analysis involves determination of glucose
Na, K, bilirubin etc.
b. ultimate analysis
- amount of each element is determined.
Ex. analysis of gasoline gives %C, %H, %O, %Pb, etc.
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1. Based on the extent of analysis
c. proximate or partial analysis
– the amount of a certain selected constituent in the
sample is determined.
e.g. partial analysis of aspirin tablets gives the amount of
salicylic acid impurity.
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2. Based on the size of the sample available for analysis
Analysis Mass of sample Volume of sample
macro >100 mg >100 μL

semimicro 10 – 100 mg 50 – 100 μL
micro 1 – 10 mg <50 μL
ultramicro <1 mg
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A technique is any chemical
or physical principle that can
be used to study an analyte.
A method is the application of

a technique for the
determination of a specific
analyte in a specific matrix
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A procedure is a set of written
directions detailing how to
apply a method to a particular
sample, including information
on proper sampling, handling
of interferents, and validating
results.
A protocol is a set of
stringent written guidelines
detailing the procedure that
must be followed if the
agency specifying the
protocol is to accept the
results of the analysis.
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Two general classes of analytical techniques:
1. total analysis techniques

A technique in which the signal is proportional to the absolute
amount of analyte; also called “classical” techniques
➢Mass, volume, and charge are the most common signals for total
analysis techniques, and the corresponding techniques are
gravimetry, titrimetry, and coulometry.
2. concentration techniques
A technique in which the signal is proportional to the analyte’s
concentration; also called “instrumental” techniques.
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Stepping through a Typical
Quantitative Analysis
1. Picking a Method: The first step is the

selection of a method. Factors need to be
considered in the selection process are:
a. Accuracy required
b. Precision
c. Sensitivity
d. Selectivity
e. Robustness
f. Ruggedness
g. Scale of Operation
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1. Picking a Method:
Other factors that need to be
considered in the selection process are:
• Cost of analysis (total investment)
• Number of sample to be analyzed
• Time required for analysis
• Skill required
• Complexity of the sample
• Number of components in the sample
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sensitivity
A measure of a method’s ability to distinguish between two
samples; reported as the change in signal per unit change in the
amount of analyte (k).
detection limit
A statistical statement about the smallest amount of analyte that
can be determined with confidence.
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Suppose that for a particular total analysis method the signal
is a measurement of mass using a balance whose smallest
increment is ±0.0001 g. If the method’s sensitivity is 0.200,
then the method can conceivably detect a difference of as
little as
in the absolute amount of analyte in two samples.
Further reading: Harvey, D. Modern Analytical Chemistry. Int’l ed. The McGraw-Hill
Companies, Inc. pp.38-45 18
selectivity
A measure of a method’s freedom from interferences as defined by the method’s selectivity coefficient.
selectivity coefficient
A measure of a method’s sensitivity for an interferent relative to that for the analyte (KA,I).
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Scale of operation for analytical methods
➢ a 1-g sample containing 1% analyte has

the same amount of analyte (0.010 g) as a
100-mg sample containing 10% analyte or
a 10-mg sample containing 100% analyte.
A hypothetical total analysis method for which

the minimum detectable signal requires 100 mg
of analyte, suggests that this method is best
suited for macro samples and major analytes
(see diagonal line representing 100 mg).
Applying the method to a minor analyte with a
concentration of 0.1% w/w requires a sample of
at least 100 g. and working with a sample of this
size is rarely practical.
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2. Acquiring a sample
Sampling is the process of collecting a small

mass of a material whose composition
accurately represents the bulk of the material
from which it was taken.
To produce meaningful information, an analysis

must be performed on a representative sample.
Proper sampling is the most difficult step in an

analysis and the source of greatest error. 21
Gross sample consists of several portions of

the material to be tested.
The laboratory sample is a small portion of the

gross sample, made homogeneous.
The analysis sample is that actually analyzed.
22
Assay - the process of determining how much

of a given material is indicated by its name
Matrix or sample matrix - all of the

components in the sample containing an
analyte
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3. Processing the sample
Sometimes no sample processing is required prior to
the measurement step (e.g. measurement of pH of a
water sample)
sample preparation—transforming a sample into a
state that is suitable for analysis.
1. 2. 3.
Preparing a Defining Preparing

laboratory replicate solutions
sample samples
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Stepping through a Typical Quantitative Analysis
→ a solid laboratory sample is ground to decrease particle size,

mixed to assure homogeneity, and stored for various lengths of time
1. before the analysis begins.
Preparing a → adsorption or desorption of water may occur, so any lost or gain of

laboratory
water changes the chemical composition of the solids, and it is a
sample
good idea to dry the samples before starting the analysis.
→ for liquid samples, different preparation steps may apply; if

Dry ashing – combustion in allowed to stand in open containers, solvent may evaporate and
a furnace at 400 -700 C change concentration of analyte; if the analyte is a gas dissolved in
a liquid, sample container must be kept inside a second sealed
Wet digestion – heating
container.
with oxidizing acids
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→most analyses are performed on replicate samples whose masses

or volumes have been determined by careful measurements with
analytical balance or with a precise volumetric device.
2.
→replication improves the quality of the results and provides a
Defining
measure of their reliability.
replicate
samples
→quantitative measurements in replicates are usually averaged and
statistical results are performed
replicates – portions of a material of

approximately the same size that are carried
through an analytical procedure at the same time
and in the same way
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→most analyses are performed in solutions of the sample
3.
→ideally, a solvent should dissolve the entire sample (not
Preparing just the analyte) rapidly and completely.
solutions
→conditions of the dissolution should be sufficiently mild to

avoid loss of the analyte.
→may require heating with aqueous solutions of strong acids,

strong bases, oxidizing agents, reducing agents or
combination of these reagents
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4. Eliminating Interferences
interference or interferents – a species that causes

error in an analysis by enhancing or attenuating (making
smaller) the quantity being measured
masking – the transformation of an interfering species

into a form that is not detected
blank – consists of all chemicals in the unknown, used

in an analysis in the same amounts, run through the
entire analytical procedure
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specific – techniques or reactions that work for only one analyte
selective - techniques or reactions that work for only a few

analytes
30
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32
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5. Calibration and Measurement

Calibration – the process of ensuring that the
signal measured by a piece of equipment or an
instrument is correct
Standardization – the process of establishing

the relationship between the amount of analyte
and a method’s signal
Method of standard additions – used to

overcome matrix effects.
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Calibration curve for the spectrometric determination of iron using method of standard addition.
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6. Calculating Results
Analyte concentrations from experimental data

need to be calculated. These computations are
based on the raw experimental data collected in
the measurement steps, the characteristics of
the measurement instruments and the
stoichiometry of the analytical reaction.
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7. Evaluating Results by Estimating their

Reliability
Analytical results are incomplete without an

estimate of their reliability. Some measure of the
uncertainties associated with computed results
need to be provided.
Validation – the process verifying that a procedure

yields acceptable results
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An integral Role for Chemical Analysis: Feedback Control Systems
The process of continuous
measurement and control is
often referred to as a feedback
system, and the cycle of
measurement, comparison,
and control is called a feedback
loop.
38
References
1. Christian, G.D. Analytical Chemistry. 6th ed John Wiley & Sons, Inc.
2. Harris, D.C. and Lucy, C.A. Quantitative Chemical Analysis. 9th ed. W.H.
Freeman and Company.
3. Harvey, D. Modern Analytical Chemistry. Int’l ed. The McGraw-Hill
Companies, Inc.
4. Skoog, D.A., West, D.M., Holler, F.J., and Crouch, S.R. Fundamentals of
Analytical Chemistry. 9th ed. Brooks/Cole.
39
THANKS!
Any questions?
You can reach me via email:
ahsanna.inkiran@msumain.edu.ph
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The Analytical Process

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The Analytical Process

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The Analytical

• Qualitative Analysis (identification) provides information

• Quantitative Analysis provides numerical information of

▹Classical Methods: Wet ▸ Instrumental Methods: Analytical

▸ Gravimetric Methods ▸ Volumetric Methods

▸ Spectroscopic Methods ▸ Chromatographic Methods

Analysis Mass of sample Volume of sample

macro >100 mg >100 μL

A method is the application of

1. total analysis techniques

1. Picking a Method: The first step is the

in the absolute amount of analyte in two samples.

➢ a 1-g sample containing 1% analyte has

A hypothetical total analysis method for which

Sampling is the process of collecting a small

To produce meaningful information, an analysis

Proper sampling is the most difficult step in an

Gross sample consists of several portions of

The laboratory sample is a small portion of the

The analysis sample is that actually analyzed.

Assay - the process of determining how much

Matrix or sample matrix - all of the

Preparing a Defining Preparing

→ a solid laboratory sample is ground to decrease particle size,

Preparing a → adsorption or desorption of water may occur, so any lost or gain of

→ for liquid samples, different preparation steps may apply; if

→most analyses are performed on replicate samples whose masses

replicates – portions of a material of

→most analyses are performed in solutions of the sample

→conditions of the dissolution should be sufficiently mild to

→may require heating with aqueous solutions of strong acids,

interference or interferents – a species that causes

masking – the transformation of an interfering species

blank – consists of all chemicals in the unknown, used

specific – techniques or reactions that work for only one analyte

selective - techniques or reactions that work for only a few

5. Calibration and Measurement

Standardization – the process of establishing

Method of standard additions – used to

Analyte concentrations from experimental data

7. Evaluating Results by Estimating their

Analytical results are incomplete without an

Validation – the process verifying that a procedure

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