Introduction to

Analytical Chemistry

CHAPTER 1
WHAT IS ANALYTICAL
CHEMISTRY?
1-1 Copyright © 2011 Cengage Learning
 What is Analytical Chemistry?

 Analytical chemistry is a measurement science

consisting of a set of powerful ideas and methods that
are useful in all fields of science and medicine.

1-2 Copyright © 2011 Cengage Learning

 Qualitative Analysis vs.
Quantitative Analysis
 Qualitative analysis reveals the identity of the elements
and compounds in a sample.

 Quantitative analysis indicates the amount of each

substance in a sample.

1-3 Copyright © 2011 Cengage Learning

 1A The Role of Analytical Chemistry
 Analytical chemistry is applied throughout industry,
medicine, and all the sciences.

 Quantitative analytical measurements also play a vital

role in chemistry, biochemistry, biology, geology,
physics, and the other sciences.

 Many scientists devote much time in the laboratory

gathering quantitative information about systems that
are important and interesting to them.

1-4 Copyright © 2011 Cengage Learning

 1A The Role of Analytical
Chemistry

Figure 1-1 The relationship between analytical chemistry, other branches of chemistry, and the other sciences. The
central location of analytical chemistry in the diagram signifies its importance and the breadth of its interactions
with many other disciplines.
1-5 Copyright © 2011 Cengage Learning
 1B Classifying Quantitative
Analytical Methods
 The results of a typical quantitative analysis are
computed from two measurements:

1. One is the mass or the volume of sample to be analyzed.

2. The second is the measurement of some quantity that is

proportional to the amount of analyte in the sample, such
as
mass, volume, intensity of light, or electrical charge, density,
viscosity, refractive index, heat capacity, molar heat capacity,
internal energy, chemical potential, temperature etc.
 Intensive Properties
 Extensive Properties
1-6 Copyright © 2011 Cengage Learning
 1B Classifying Quantitative
Analytical Methods
 We classify analytical methods according to the nature
of this final measurement.

1. Gravimetric methods determine the mass of the analyte or

some compound chemically related to it.

2. Volumetric methods determine the volume of a solution

containing sufficient reagent to react completely with the
analyte.

1-7 Copyright © 2011 Cengage Learning

 1B Classifying Quantitative
Analytical Methods (cont.)
3. Electroanalytical methods involve the measurement of such
electrical properties as voltage, current, resistance, and
quantity of electrical charge.

4. Spectroscopic methods are based on measurement of the

interaction between electromagnetic radiation and analyte
atoms or molecules or on the production of such radiation
by analytes.

1-8 Copyright © 2011 Cengage Learning

 1B Classifying Quantitative
Analytical Methods (cont.)
 Miscellaneous methods:
 mass-to-charge ratio

 rate of radioactive decay

 heat of reaction

 rate of reaction

 sample thermal conductivity

 optical activity

 refractive index

1-9 Copyright © 2011 Cengage Learning

 Flow Diagram Showing the Steps in a
Quantitative Analysis

Figure 1-2 Flow diagram showing the steps in a quantitative analysis. There are a number of possible paths through the steps in a
quantitative analysis. In the simplest example represented by the central vertical pathway, we select a method, acquire and process the
sample, dissolve the sample in a suitable solvent, measure a property of the analyze, calculate the results, and estimate the reliability of
the results. Depending on the complexity of the sample and the chosen method, various other pathways may be necessary.
1-10 Copyright © 2011 Cengage Learning
 1C-1 Picking a Method
 One of the first questions to be considered in the
selection process is the level of accuracy required.
 A second consideration related to economic factors is
the number of samples to be analyzed.
 The complexity of the sample and the number of
components in the sample always influence the choice
of method to some degree.

1-11 Copyright © 2011 Cengage Learning

 1C-2 Acquiring the Sample
 Sampling involves obtaining a small mass of a material
whose composition accurately represents the bulk of
the material being sampled.
 Sampling is frequently the most difficult step in an
analysis and the source of greatest error. The final
results of an analysis will never be any more reliable
than the reliability of the sampling step.

1-12 Copyright © 2011 Cengage Learning

 1C-2 Acquiring the Sample
 A material is heterogeneous if its constituent parts can
be distinguished visually or with the aid of a
microscope.
 An assay is the process of determining how much of a
given sample is the material indicated by its name.
 We analyze samples and we determine substances.

1-13 Copyright © 2011 Cengage Learning

 1C-3 Processing the Sample
 Under certain circumstances, no sample processing is
required prior to the measurement step.
 Under most circumstances, we must process the
sample in any of a variety of different ways.
 The first step in processing the sample is often the
preparation of a laboratory sample.

1-14 Copyright © 2011 Cengage Learning

 1C-3 Processing the Sample
 Preparing a Laboratory Sample
 A solid sample is ground to decrease particle size, mixed to
ensure homogeneity, and stored for various lengths of time
before analysis begins.
 Because any loss or gain of water changes the chemical
composition of solids, it is a good idea to dry samples just
before starting an analysis.
 Alternatively, the moisture content of the sample can be
determined at the time of the analysis in a separate analytical
procedure.

1-15 Copyright © 2011 Cengage Learning

 1C-3 Processing the Sample
 Preparing a Laboratory Sample (Cont.)
 Liquid samples are subject to solvent evaporation.

 If the analyte is a gas dissolved in a liquid, analyte must be

kept inside a second sealed container to prevent
contamination by atmospheric gases.
 Extraordinary measures, including sample manipulation and
measurement in an inert atmosphere, may be required to
preserve the integrity of the sample.

1-16 Copyright © 2011 Cengage Learning

 1C-3 Processing the Sample
 Defining Replicate Samples
 Replicate samples, or replicates, are 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.
 Replication improves the quality of the results and provides a
measure of their reliability.
 Quantitative measurements on replicates are usually averaged,
and various statistical tests are performed on the results to
establish their reliability.

1-17 Copyright © 2011 Cengage Learning

 1C-3 Processing the Sample
 Preparing Solutions: Physical and Chemical Changes
 Ideally,the solvent should dissolve the entire sample,
including the analyte, rapidly and completely.
 The sample may require heating with aqueous solutions
of strong acids, strong bases, oxidizing agents, reducing
agents, or some combination of such reagents.
 It may be necessary to ignite the sample in air or oxygen
or perform a high-temperature fusion of the sample in
the presence of various fluxes.

1-18 Copyright © 2011 Cengage Learning

 1C-4 Eliminating Interferences
 Few chemical or physical properties of importance in
chemical analysis are unique to a single chemical
species.
 Species other than the analyte that affect the final
measurement are called interferences, or interferents.

1-19 Copyright © 2011 Cengage Learning

 1C-4 Eliminating Interferences
 An interference is a species that causes an error in an
analysis by enhancing or attenuating (making smaller)
the quantity being measured.
 Techniques or reactions that work for only one analyte
are said to be specific. Techniques or reactions that
apply for only a few analytes are selective.
 The matrix, or sample matrix, is all of the components
in the sample containing an analyte.

1-20 Copyright © 2011 Cengage Learning

 Remain Steps of A Typical
Quantitative Analysis
 1C-5 Calibration and Measurement
 Ideally, the measurement of the property is directly
proportional to the concentration.
cA  kX
 where k is a proportionality constant.
 1C-6 Calculating Results
 Computing analyte concentrations are based on the raw
experimental data collected in the measurement step, the
characteristics of the measurement instruments, and the
stoichiometry of the analytical reaction.

1-21 Copyright © 2011 Cengage Learning

 Remain Steps of A Typical
Quantitative Analysis
 1C-7 Evaluating Results by Estimating Their Reliability
 Analytical results are incomplete without an estimate of their
reliability.

1-22 Copyright © 2011 Cengage Learning

 1D An Integral Role For Chemical
Analysis: Feedback Control Systems
 Chemical analysis is the measurement element in all of
these examples and in many other cases.
 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.

1-23 Copyright © 2011 Cengage Learning

 Feedback Control Systems

Figure 1-3 Feedback system flow diagram.

The desired state is determined, the actual
state of the system is measured, and the two
states are compared. The difference between
the two states is used to change a
controllable quantity that results in a change
in the state of the system. Quantitative
measurements are again performed on the
system, and the comparison is repeated. The
new difference between the desired state
and the actual state is again used to change
the state of the system if necessary. The
process provides continuous monitoring and
feedback to maintain the controllable
quantity, and thus the actual state, at the
proper level. The text describes the
monitoring and control of blood glucose as
an example of a feedback control system.

1-24 Copyright © 2011 Cengage Learning

 Accuracy and Precision
25

 Measurement in Science:
 In science, we want measurements to be both
accurate and precise.

 What is the difference between accuracy and

precision?

1-25 Copyright © 2011 Cengage Learning

 Accuracy and Precision
26

 Accuracy
 isa measure of how close a measured value to
the true value (is it the correct value?)

 Precision
 is a measure of the reproducibility of a result (is
it exactly the value?)

1-26 Copyright © 2011 Cengage Learning

 Accuracy and Precision
27

 What sort of measurements do we have?

1-27 Copyright © 2011 Cengage Learning

 Accuracy and Precision
28

 Results may be reproducible, but wrong.

 5.0 grams of sample

 Balance “A” sample

 5.2; 5.4; 5.3; 5.3
Balance “A”
 Balance “B”
 5.0; 4.9; 5.1; 5.0

1-28
Balance “B”
Copyright © 2011 Cengage Learning
 Accuracy and Precision
29

 Systematic errors  Random errors

 are constant and always  produced by any
of the same sign and unpredictable &
thus may not be reduced unknown variations in
by averaging over a lot of the experiment, e.g.
data fluctuations in room
temperature,
fluctuations in power
supply voltage,
mechanical vibrations
etc.
Weighing bottle
1-29 Copyright © 2011 Cengage Learning
 THE END

1-30
1-25 Copyright © 2011 Cengage Learning