The Nature of Analytical Chemistry

Skoog, D.A., West, D.M., Holler, F.J., and Crouch, S.R. (2004).
Fundamentals of Analytical Chemistry
8th Ed. Brooks/Cole, U.S.A.
 The nature of analytical chemistry

 Measurement science
 A set of powerful ideas and methods that are
useful in science and medicine

Analytical chemistry

Qualitative analysis Quantitative analysis

(establishes the chemical identity of the (determines the relative amounts of these
species in the sample) species or analytes in a sample)

 Analytes are the components of a sample that are to be

determined
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The role of analytical chemistry

 Interdisciplinary
 Vital tool in medical,
industrial,
government, and
academe
 The relationship between
analytical chemistry,
other branches of
chemistry, and the other
sciences
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Quantitative analytical methods

 Measurement of mass
 Measurement of volume
 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

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Quantitative analytical methods

 Gravimetric methods–determine the mass of the

analyte or some compound related to it
 Volumetric methods–the volume of solution
containing sufficient reagent to react completely with
the analyte is measured
 Electroanalytical methods–involve the measurement
of electrical properties (potential, current, resistance,
quantity of electrical charge)
 Spectroscopic methods–are based on the
measurement of the interaction between
electromagnetic radiation and analyte atoms or
molecules or on the production of such radiation by
analytes
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Miscellaneous methods

 Measurement of mass-to-charge ratio by

mass spectrometry
 Rate of radioactive decay
 Heat of reaction
 Rate of reaction
 Thermal conductivity
 Optical activity
 Refractive index
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Steps in a
quantitativ
e analysis

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STEP 1. Choosing a method

 What is the level of accuracy required?

 High reliability = time
 How many samples should be analyzed?
 Large no. of samples = time
 Assemble and calibrate instruments
 Prepare standard solutions
 What is the nature of and how many
components are there in the sample?
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STEP 2. Acquiring the sample

 An analysis must be performed on a sample

that has the same composition as the bulk of
the material from which it was taken
 Large and heterogeneous bulk = great

effort to get a representative sample

 A material is heterogeneous if its

constituent parts can be distinguished

visually or with the aid of a microscope
 Coal, animal tissue, soil
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STEP 2. Acquiring the sample

 How do you get a sample from a

railroad car containing 25 tons of silver
ore?
 The buyer and seller must agree on the
price based on the silver content of the
shipment
 The ore is heterogeneous, consisting of
many lumps that vary in size and silver
content
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STEP 2. Acquiring the sample

 The assay of the silver ore shipment will

be performed on a sample that weighs
about 1 gram
 An assay is the process of determining
how much of a given sample is the
material indicated by its name
 A zinc alloy is assayed for its zinc content

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STEP 2. Acquiring the sample

 Sampling is the process of collecting a

small mass of a material whose
composition accurately represents the
bulk of the material being sampled
 Sampling from a heterogeneous material
 Sampling from a complex biological system
 Reliability of final results  reliability of
the sampling step

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STEP 3. Processing the sample

 Preparing laboratory samples

 Solid samples
 Decrease particle size
 Homogenize
 Store before analysis
 Absorption/desorption of water (loss/gain of
moisture)
 Dry the samples before analysis
 Determine moisture in a separate procedure

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STEP 3. Processing the sample

 Preparing laboratory samples

 Liquid samples
 Evaporation = change in concentration
 Keep samples in sealed containers perhaps
during the entire analytical procedure
 Manipulate and measure in an inert
atmosphere to preserve the integrity of the
sample

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STEP 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 reliability

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STEP 3. Processing the sample

 Preparing solutions: physical and chemical

changes
 Most analyses are performed on solutions of the
samples made with a suitable solvent
 Solvent should dissolve the entire sample,
including the analyte, rapidly and completely
 Conditions of dissolution should be sufficiently
mild to prevent loss of analyte

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STEP 3. Processing the sample

 Many materials that must be analyzed

are insoluble in common solvents
 Silicate minerals
 High-molecular-weight polymers
 Specimens of animal tissue

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STEP 3. Processing the sample

 Conversion of analyte in insoluble

samples into soluble form
 Heating with aqueous solutions of strong
acids, strong bases, oxidizing agents,
reducing agents, or their combinations
 Ignite the sample in air or oxygen
 High temperature fusion of the sample in
the presence of fluxes

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STEP 3. Processing the sample

 Does the soluble form of the sample

have a property that is proportional to
the analyte concentration that is
measurable?
 In the determination of Mn in steel, Mn
must be oxidized to MnO4 before the
absorbance of the colored solution is
measured

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STEP 4. Eliminating interferences

 Interference or interferent is a species other than the

analyte that causes an error in the analysis by
enhancing or attenuating (making smaller) the
quantity being measured
 Techniques or reactions that work for only one
analyte are specific
 Techniques or reactions that apply for only a few
analytes are selective
 Matrix or sample matrix is all of the components in
the sample containing the analyte

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STEP 5. Calibrating and measuring
concentration

 All analytical results depend on the final

measurement X of a physical or chemical
property of the analyte
 This property must vary in a known and
reproducible way with the concentration cA of
the analyte
 The measurement of the property is directly
proportional to the concentration

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STEP 5. Calibrating and measuring
concentration

 k = a proportionality constant
 With two exceptions, analytical methods
require the empirical determination of k
with chemical standards for which cA is
known
 The process of determining k, is called
calibration

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STEP 6. Calculating results

 Raw experimental data collected in the

measurement step
 Characteristics of the measurement
instruments
 Stoichiometry of the analytical reaction

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 STEP 7. Evaluating results by
estimating their reliability

 Errors in chemical analysis

 Random errors in chemical analysis
 Statistical data treatment and
evaluation

An analytical result without an estimate of reliability

has NO VALUE.
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An integral role for chemical analysis:
feedback control systems

 Chemical analysis is the measurement

element in many real life situations like
 Maintaining or improving a patient’s health
 Control the amount of mercury in fish
 Regulate the quality of a product
 Determine the status of a synthesis
 Find out whether there is life on Mars

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Feedback system flow diagram

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Feedback system flow diagram

 Determine the desired state

 Measure the actual state
 Compare the desired and actual states
 Use the difference in the two states to
change a controllable quantity that
should result in the state of the system
 Repeat the quantitative measurements
on the system and compare again
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 Example: monitoring and control of
blood glucose concentration
 Patients with insulin-dependent diabetes mellitus
develop hyperglycemia (blood glucose concentration >
60–95 mg/dL)
 Desired state: blood glucose concentration < 95 mg/dL
 Actual state: collect blood sample from patient and
measure the blood glucose level
 Compare the desired and actual states
 If the actual blood glucose level > 95 mg/dL, the
patient’s insulin level (controllable quantity) is increased
by injection or oral administration
 After a delay to allow insulin time to take effect, the
glucose level is measured again to determine if desired
state = actual state
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 Feedback system–the process of
continuous measurement and control
 Feedback loop–the cycle of
measurement, comparison, and control

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Applications

 Biological and  Measuring and controlling

biomedical the concentration of
 Mechanical manganese in steel
 Electronics  Maintaining the proper
level of chlorine in a
swimming pool

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 Deer Kill: A Case Study Illustrating
the Use of Analytical Chemistry to
Solve a Problem in Toxicology
 The Problem
The incident began when a park
ranger found a dead white-tailed
deer near a pond in the land
between the Lakes National
Recreation Area in western
Kentucky. The park ranger enlisted
the help of a chemist from the
state veterinary diagnostic
laboratory to find the cause of
death so that further deer kills
might be prevented.
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 Read the case study on page 12-16 of
the reference book.

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