CH1

Fundamentals of
Analytical
Chemistry Eighth Edition
CHAPTER
The Nature of Analytical

Chemistry
The Nature of Analytical Chemistry
Analytical Chemistry is a measurement science

consisting of a set of powerful ideas and methods that
are useful in all kinds of science and medicine.
i.e., The mars landscape used the alpha proton X-ray

spectroscopy (APXS) to collected and transferred to
earth for further analysis to determine the identity and
concentrations of the elements.
The example demonstrates that both qualitative information

and quantitative information are required in the analysis.
Qualitative analysis reveals the identity of the elements and

compounds in a sample.
Quantitative analysis indicates the amount of species, or

analytes, in numerical terms.
Analytes are the compoments of a sample that are to be

determined.
The data from the APXS of mars landscape contain both

types of information.
More commonly, a separation step is a necessary part of

the analytical procedure.
The Role of Analytical Chemistry
Analytical Chemistry is applied through industry, medicine,
and all the sciences.
i.e., The concentration of oxygen and of carbon dioxide are

determined in millions of blood samples every day and used
to diagnose and treat illnesses.
i.e., Quantities of nitrogen in foods establishes their proteins

content and thus their nutrition values.
i.e., Analysis if steel during its production permits adjustment

in the concentrations of such element as carbon, nickel, and
chromium to achieve a desired strength, hardness, corrosion
resistance, and ductility.
Amino acid composition of BSA
Ala 48 Cys 35 Asp 41 Glu 58
Phe 30 Gly 17 His 16 Ile 15
Lys 60 Leu 65 Met 5 Asn 14
Pro 28 Gln 21 Arg 26 Ser 32
Thr 34 Val 38 Trp 3 Tyr 21

Alloy
The Role of Analytical Chemistry
Many chemists and biochemists, and medical chemists

devote much time in the laboratory gathering quantitative
information about systems that are important and are
important an interesting to them.
The central role of analytical chemistry is the enterprise and

many others is illustrated in Figure 1.
The interdisciplinary nature of chemical analysis makes it a

vital tool in medical, industrial, government, and academic
laboratories through out the world.
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.
Quantitative Analytical Methods
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.
Gravimetric method determine the mass of the analyte or

some compound chemically related to it.
In volumetric method, the volume of a solution containing

sufficient reagent to react completely with the analyte is
measured.
Quantitative Analytical Methods
Electrocanalytical method involves the measurement of

such electrical properties as potential, current, resistance,
and quantity of electrical charge.
Spectroscopy Method are based on measurement of the

interaction between electromagnetic radiation and analyte
atoms or molecules.
Figure 1-2
Flow diagram showing the steps in a
quantitative analysis. There are a
number of possible 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
analyte, 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.
A Typical Quantitative Method
Choosing a Method
The choice is sometimes difficult and required experience

as well as intuition. High reliability always required a large
investment time. The selective method usually represents
a compromise between the accuracy required and the time
and money available for the analysis
The complexity of the sample and the number of

components in the sample always influence the choice of
method to some degree.
Acquiring the Sample
To produce meaningful information, an analysis must be

performed on a sample that has the same composition as
the bulk material from which it was taken.
When the bulk is large and heterogeneous, great effort is

required to get a representative sample.
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 is frequently the most difficult step and the

source of greatest error.
Processing the sample

Water sample is withdraw from a stream, a lake, or an
ocean, its pH can be measured directly.
Under most circumstances, we must process the sample

in any of a variety of different ways.
Solid sample is ground to decrease the particle size, mixed

to ensure the homogeneity.
Liquid sample: If the samples are allowed to stand in open

containers, the solvent may evaporate and change the
concentration of the analyte => Keeping inside a seal container.

Most chemical analytes are performed on replicate samples
whose masses or volumes have been determined by careful
measurement with an analytical balance or with a precise
volumetric device.
Quantitative measurement on replicates are usually

averaged, and various statistical test are performed on the
results to establish reliability.

The conditions of dissolution should be sufficiently mild so
that loss of analytes can not occur.
But, many materials that must be analyzed are insoluble in

the common solvents.
i.e., silica materials, high-molecular-weight polymers, and

tissue. Therefore need some harsh chemistry treatment.
i.e., in the determination of magnesium in steel, magnesium

must be oxidize to MnO4- before the absorbance of the
colored solution is measured.

For chemical or physical properties of chemical analysis are
unique to a single chemical species.
Species other than the analyte that affect the final

measurement are called interferences.
A scheme must be devised to isolate the analyte from the

interferences before the final measurement is made.
Calibration and Measureing Concentration
Ideally, the measurement of the property is directly proportional

to the concentration.
cA = kX
k is the proportionality constant. The process of determining k,

an important step in most analytes, is termed a calibration.
Evaluating Results by Estimating their Reliability
The experiment must provide some measure of the

uncertainties associated with computed results if the data
are to have any value.
Feedback Control System
Analytical chemistry is usually not an end in itself, but is a

part of a bigger picture in which we may use analytical results
to help maintain or improve a patients health.
i.e., Patients with insulin-dependent diabetes mellitus develop

hyperglycemia, which manifests itself as a blood glucose
concentration above the normal value of 60 to 95 mg/dL.
Many patients must monitor their blood glucose levels by
periodically submitting samples to a clinical laboratory for
analysis or by measuring the levels themselves using a
handheld electronic glucose monitor.
Feedback Control System
If the measured blood glucose level is above 95 mg/dL, the
patient's insulin level, which is a controllable quantity, is
increased by injection or oral administration. After a delay to
allow the insulin time to take effect, the glucose level is
measured again to determine if the desired state has been
achieved.
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. These ideas find wide application in biological and
biomedical systems, mechanical systems, and electronics.
Chemical analysis plays a central role in a broad range

of 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 if 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 concentration as an example of a feedback
control system.
Deer Kill: A Case Study Illustrating the Use of Analytical
Chemistry to Solve a Problem in Toxicology
The tools of modern analytical chemistry are widely

applied in environmental investigations.
We describe a case study in which quantitative analysis

was used to determine the agent that caused deaths in a
population of white-tailed deer inhabiting a wildlife
preserve in Kentucky.
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.
Because of the advanced state of decomposition, no fresh

organ tissue samples could be gathered.
A few days after the original inquiry, the ranger found two
more dead deer near the same location.
The investigators noticed that grass surrounding nearby power

line poles was wilted and discolored.
White-tailed deer have proliferated in many
parts of the country.
The investigators speculated that a herbicide might have

been used on the grass.
The compound of the disodium salt of methanearsenic acid,

CH3AsO(OH)2 which is very soluble in water and thus finds
use as the active ingredient in many herbicides.
The herbicidal activity of disodium methanearsenate is due

to its reactivity with the sulfhydryl (SH) groups in the amino
acid cysteine.
Throughout this text, we
will present models of
molecules that are
important in analytical
chemistry. Here we show
arsine, AsH3. arsine is an
extremely toxic, colorless
gas with a noxious garlic
odor. Analytical methods
involving the generation
of arsine must be carried
out with caution and
proper ventilation.
When cysteine in plant enzymes reacts with arsenical

compounds, the enzyme function is inhibited and the plant
eventually dies. Similar chemical effects occur in animals as
well.
The investigators planned to analyze the samples to confirm

the presence of arsenic and, if present, to determine its
concentration in the samples.
Selecting a Method
Quantitative determination of arsenic in biological samples is

found in the published methods of the Association of Official
Analytical Chemists (AOAC). This method involves the
distillation of arsenic as arsine, which is then determined by
colorimetric measurements.
Processing the Sample

In the laboratory, the deer were dissected and the kidneys were
removed for analysis.
Doing Chemistry
To obtain an aqueous solution of the analyte for analysis,
heating sample at 555 C for 2 hours. Dry ashing served to
free the analyte from organic material and convert it to arsenic
pentoxide. The dry solid in each sample was then dissolved
in dilute HCl, which converted the As2O5 to soluble H3AsO4.
Eliminating Interferences
Arsenic can be separated from other substances that might

interfere in the analysis by converting it to arsine, AsH3
H3AsO4 + SnCl2 + 2HCl H3AsO3 + SnCl4 + H2O
H3AsO3 + 3Zn + 6HCl AsH3(g) + 3ZnCl2 + 3H2O

Figure 1F-1
An easily constructed
apparatus for generating
arsine, AsH3. The entire
reaction was carried out
in flasks equipped with
a stopper and delivery
tube so that the arsine
could be collected in the
absorber solution.
Molecular model of
diethyldithiocarbamate.
This compound is an
analytical reagent used
in determining arsenic.
Red Complex
Measure the Amount of Analyte

The amount of arsenic in each sample was determined by
using an instrument called a spectrophotometer, to measure
the intensity of the red color formed in the cuvettes.
A spectrophotometer provides a number called absorbance

that is directly proportional to the color intensity, which is also
proportional to the concentration of the species responsible
for the color.
Figure 1F-2
Constructing and using a
calibration curve to determine the
concentration of arsenic. The
absorbance of the solutions in the
cuvettes are measured using a
spectrophotometer. The
absorbance values are then
plotted against the concentrations
of the solutions in the cuvettes, as
illustrated in the graph. Finally,
the concentrations of the
unknown solutions are read from
the plot, as shown by the dark
arrow.
Calculating the Concentration
The absorbance for the standard solutions containing known

concentrations of arsenic are plotted to produce a calibration
curve.
This curve is then used to determine the concentration of the

Two unknown solutions above about 10 ppm, the samples of
grass contained about 600ppm arsenic!
The investigators concluded that the deer had probably died

as a result of eating the poisoned grass.
Estimating the Reliability of the Data
For each of the standard arsenic solutions and the deer

samples, the average of the three absorbance measurements
was calculated. The average absorbance for the replicates is
a more reliable measure of the concentration of arsenic than
a single measurement.
Least-squares analysis of the standard data was used to find

the best straight line among the points and to calculate the
concentrations of the unknown samples along with their
statistical uncertainties and confidence limits.
Conclusions and Remarks
Many of the methods and instruments of analytical

chemistry are used routinely to provide vital information in
environmental and toxicological studies of this type. The
system flow diagram of Figure 1-3 may be applied to this
case study.

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Fundamentals of

The Nature of Analytical

Analytical Chemistry is a measurement science

i.e., The mars landscape used the alpha proton X-ray

The example demonstrates that both qualitative information

Qualitative analysis reveals the identity of the elements and

Quantitative analysis indicates the amount of species, or

Analytes are the compoments of a sample that are to be

The data from the APXS of mars landscape contain both

More commonly, a separation step is a necessary part of

i.e., The concentration of oxygen and of carbon dioxide are

i.e., Quantities of nitrogen in foods establishes their proteins

i.e., Analysis if steel during its production permits adjustment

Ala 48 Cys 35 Asp 41 Glu 58

Phe 30 Gly 17 His 16 Ile 15

Lys 60 Leu 65 Met 5 Asn 14

Pro 28 Gln 21 Arg 26 Ser 32

Thr 34 Val 38 Trp 3 Tyr 21

Many chemists and biochemists, and medical chemists

The central role of analytical chemistry is the enterprise and

The interdisciplinary nature of chemical analysis makes it a

Gravimetric method determine the mass of the analyte or

In volumetric method, the volume of a solution containing

Electrocanalytical method involves the measurement of

Spectroscopy Method are based on measurement of the

The choice is sometimes difficult and required experience

The complexity of the sample and the number of

Acquiring the Sample

To produce meaningful information, an analysis must be

When the bulk is large and heterogeneous, great effort is

Acquiring the Sample

Sampling is frequently the most difficult step and the

Processing the sample

Under most circumstances, we must process the sample

Solid sample is ground to decrease the particle size, mixed

Liquid sample: If the samples are allowed to stand in open

Processing the sample

Quantitative measurement on replicates are usually

Processing the sample

But, many materials that must be analyzed are insoluble in

i.e., silica materials, high-molecular-weight polymers, and

i.e., in the determination of magnesium in steel, magnesium

Processing the sample

Species other than the analyte that affect the final

A scheme must be devised to isolate the analyte from the

Calibration and Measureing Concentration

Ideally, the measurement of the property is directly proportional

k is the proportionality constant. The process of determining k,

Evaluating Results by Estimating their Reliability

The experiment must provide some measure of the

Analytical chemistry is usually not an end in itself, but is a

i.e., Patients with insulin-dependent diabetes mellitus develop

The process of continuous measurement and control is often

Chemical analysis plays a central role in a broad range

The tools of modern analytical chemistry are widely

We describe a case study in which quantitative analysis

Because of the advanced state of decomposition, no fresh

The investigators noticed that grass surrounding nearby power

The investigators speculated that a herbicide might have

The compound of the disodium salt of methanearsenic acid,

The herbicidal activity of disodium methanearsenate is due

When cysteine in plant enzymes reacts with arsenical

The investigators planned to analyze the samples to confirm

Quantitative determination of arsenic in biological samples is