Analytical Chemistry

introduction

Skoog, West, Holler, and Crouch, Fundamentals of Analytical Chemistry, 10e. © 2022 Cengage. All Rights Reserved. May
not be scanned, copied or duplicated, or posted to a publicly accessible website, in whole or in part.
• Analytical chemistry involves quantitative and qualitative analyses to
determine the components of a substance.
• Qualitative analysis is used to determine the chemical identity of
species in a sample and quantitative analysis is used to determine the
relative amounts of these species (analytes).
• Analytical chemistry is important in other branches of science, including
chemistry, physics, engineering, medicine, materials science, social
sciences, agriculture, environmental sciences, geology, and biology.
• Common quantitative methods include gravimetric, volumetric,
electroanalytical, and spectroscopic methods.
• Typical quantitative analyses involve a series of steps that begins with
selecting a method and ends with calculating the results and estimating
their reliability.
• Samples must be prepared for quantitative analysis, which involves
grinding solids, dissolving liquid samples, and taking steps to
ensure the integrity of both solid and liquid samples.
 The Role of Analytical Chemistry

• Quantitative analysis reveals the identity of the elements and

compounds in a sample.
• Qualitative analysis indicates the amount of each substance in a
sample.
• Analytes are the components of a sample that are determined.
 The Role of Analytical Chemistry

• Analytical chemistry plays a role

in a wide range of scientific
disciplines.
 Quantitative Analytical Methods

• Two measurements are used to compute the results of a typical

quantitative analysis.
▪ Mass or volume of the sample being analyzed.
▪ Some quantity (such as mass, volume, intensity of light, or electrical
charge) proportional to the amount of analyte in the sample.
 Quantitative Analytical Methods

• A variety of analytical methods may be used.

▪ Gravimetric methods determine the mass of the analyte or some
compound chemically related to it.
▪ Volumetric methods measure the volume of a solution containing
sufficient reagent to react completely with the analyte.
▪ Electroanalytical methods measure electrical properties such as
potential, current, resistance, and quantity of electrical charge.
▪ Spectroscopic methods explore the interaction between electromagnetic
radiation and analyte atoms or molecules or the emission of radiation by
analytes.
 Qualitative Analytical Methods

• In chemistry, qualitative analysis is the determination of the chemical

composition of a sample. It encompasses a set of analytical chemistry
techniques that provide nonnumerical information about a specimen.
• Qualitative analysis can tell you whether an atom, ion, functional group, or
compound is present or absent in a sample, but it doesn't provide
information about its quantity.
 Techniques and Tests

• Qualitative analysis involves chemical tests, such as the Kastle-Meyer test for
blood or the iodine test for starch. Another common qualitative test, used in
inorganic chemical analysis, is the flame test.
• Qualitative analysis typically measures changes in color, melting point, odor,
reactivity, radioactivity, boiling point, bubble production, and precipitation.
Methods include distillation, extraction, precipitation, chromatography, and
spectroscopy.
 Chromatography

• a group of laboratory techniques used to separate

the components of a mixture by passing the
mixture through a stationary phase. Typically, the
sample is suspended in the liquid or gas phase
and is separated or identified based on how it
flows through or around a liquid or solid phase.
• The two broad categories of chromatography are
liquid chromatography (LC) and gas
chromatography (GC).
 Spectroscopy

• Spectroscopy is the analysis of the

interaction between matter and any
portion of the electromagnetic spectrum.
Traditionally, spectroscopy involved
the visible spectrum of light, but X-ray,
gamma, and UV spectroscopy also are
valuable analytical techniques.
Spectroscopy can involve any interaction
between light and matter,
including absorption, emission, scattering
 Branches of Qualitative Analysis

• The two main branches of qualitative analysis are organic qualitative analysis
(such as the iodine test) and inorganic qualitative analysis (such as the flame
test).
• Inorganic analysis looks at the elemental and ionic composition of a sample,
usually by examination of ions in aqueous solution. Organic analysis tends to
look at types of molecules, functional groups, and chemical bonds.
Choosing A Method
 Acquiring the Sample

• After selecting a method for analysis, the second step is to acquire 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.
▪ A material is heterogeneous if its constituent parts can be distinguished visually
or with the aid of a microscope.
▪ It is difficult to obtain a representative sample from a heterogenous sample.

• An assay is the process of determining how much of a given sample is the

material by its indicated name.
• Note that we analyze samples and we determine substances.
 Processing the Sample

• Not all samples require processing.

• Solid laboratory samples are ground, mixed, and stored.
▪ Drying samples prior to analysis is recommended because loss or gain of
water changes the chemical composition of solids.
▪ Alternatively, a separate analytical procedure can be used to determine the
moisture content of the sample at the time of the analysis.
 Processing the Sample

• Liquid samples can undergo evaporation of the solvent and/or

contamination by atmospheric gases.
• Two approaches can help to preserve the integrity of the liquid
sample:
▪ Keeping the sample container in a second sealed container.
▪ Manipulating and measuring the sample in an inert atmosphere.
 Processing the Sample

• 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 that can be established using statistical
testing.
 Processing the Sample

• Most analyses are performed on solutions of the sample made with a

suitable solvent.
• Consider whether the sample has a property proportional to the analyte
concentration that can be measured.
• If not, convert the analyte to form suitable for the measurement step.
This step may require the use of fluxes to perform the conversion.
▪ A flux is a material, often an alkali metal salt, that is mixed with the sample
and heated to form a fused salt.
• Before proceeding to the measurement step, eliminate interference in
the sample.
 Eliminating Interferences

• An interference or interferent is a species that causes an error in

an analysis by enhancing or attenuating (making smaller) the
quantity being measured.
• Analytes must be isolated from interferents before measurements
are made.
 Calibrating and Measuring Concentration

• Ideally, the final measurement X of a physical or chemical property of

the analyte is directly proportional to the concentration of the analyte.

• The matrix, or sample matrix, is the collection of all the components in the
sample containing an analyte.
• Techniques or reactions that work for only one analyte are specific.
Techniques or reactions that apply to only a few analytes are selective.
• Calibration is the process of determining the proportionality between analyte
concentration and a measured quantity.
 Calculating Results

• After the concentration has been calibrated and measured, it can be

calculated. These computations are based on:
▪ The raw experimental data.
▪ The characteristics of the measurement instruments.
▪ The stoichiometry of the analytical reaction.
 Evaluating Results by Estimating Reliability

• Analytical results are complete only when their reliability has been
estimated.
• An analytical result without an estimate of reliability is of no value.
 Feature 1-1: Deer Kill: A Case Study (1 of 15)

Analytical chemistry is a powerful tool in environmental investigations. This feature

describes a case study in which quantitative analysis was used to determine the agent that
caused deaths in a population of white-tailed deer in a wildlife area of a national
recreational area in Kentucky. We begin with a description of the problem and then show
how the steps illustrated in Figure 1-2 were used to solve the analytical problem. This case
study also shows how chemical analysis is used in a broad context as an integral part of
the feedback control system depicted in Figure 1-3.
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.
 Feature 1-1: Deer Kill: A Case Study (2 of 15)

The 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.
The ranger and the chemist carefully inspected the site where the badly
decomposed carcass of the deer had been found. 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 chemist was summoned to the site of the kill, where the deer was
loaded onto a truck for transport to the veterinary diagnostic laboratory. The
investigators then conducted a careful examination of the surrounding area in an
attempt to find clues to establish the cause of death.
 Feature 1-1: Deer Kill: A Case Study (3 of 15)
The search covered about 2 acres surrounding the pond. The investigators noticed that grass
surrounding nearby power line poles was wilted and discolored. They speculated that a herbicide
might have been used on the grass. A common ingredient in herbicides is arsenic in any one of a
variety of forms, including arsenic trioxide, sodium arsenite, monosodium methanearsenate, and
disodium methanearsenate. The last compound is the disodium salt of methanearsenic acid,
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 (S─H) groups in the amino acid cysteine. When cysteine in plant enzymes reacts with
arsenical compounds, the enzyme function is inhibited, and the plant eventually dies.
Unfortunately, similar chemical effects occur in animals as well. The investigators, therefore,
collected samples of the discolored dead grass for testing along with samples from the organs of
the deer. They planned to analyze the samples to confirm the presence of arsenic and, if present,
to determine its concentration in the samples.
 Feature 1-1: Deer Kill: A Case Study (4 of 15)

Selecting a Method
A scheme for the quantitative determination of arsenic in biological samples is
found in the published methods of the Association of Official Analytical Chemists
(AOAC). In this method, arsenic is distilled as arsine, and is then
determined by colorimetric measurements.

Processing the Sample: Obtaining Representative Samples

Back at the laboratory, the deer were dissected, and the kidneys were removed
for analysis. The kidneys were chosen because the suspected pathogen (arsenic)
is rapidly eliminated from an animal through its urinary tract.
 Feature 1-1: Deer Kill: A Case Study (5 of 15)

Processing the Sample: Preparing a Laboratory Sample

Each kidney was cut into pieces and homogenized in a highspeed blender. This
step served to reduce the size of the pieces of tissue and to homogenize the
resulting laboratory sample.

Processing the Sample: Defining Replicate Samples

Three 10-g samples of the homogenized tissue from each deer were placed in
porcelain crucibles. These served as replicates for the analysis.
 Feature 1-1: Deer Kill: A Case Study (6 of 15)

Doing Chemistry: Dissolving the Samples

To obtain an aqueous solution of for analysis, it was necessary to convert its
organic matrix to carbon dioxide and water by the process of dry ashing. This
process involved heating each crucible and sample cautiously over an open flame
until the sample stopped smoking. The crucible was then placed in a furnace and
heated 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 crucible
was then dissolved in dilute HCl, which converted the to soluble
 Feature 1-1: Deer Kill: A Case Study (7 of 15)

Eliminating Interferences
Arsenic can be separated from other substances that might interfere in the
analysis by converting it to arsine, a toxic, colorless gas that is evolved when
a solution of is treated with zinc. The solutions resulting from the deer
and grass samples were combined with and a small amount of iodide ion
was added to catalyze the reduction of according to the following
reaction:

The was then converted to by the addition of zinc metal as follows:

 Feature 1-1: Deer Kill: A Case Study (8 of 15)

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 as shown in Figure 1F-1.
The arrangement ensured that
interferences were left in the reaction
flask and that only arsine was
collected in the absorber in special
transparent containers called
cuvettes. FIGURE 1F-1 An easily constructed
apparatus for generating arsine, AsH3.
Feature 1-1: Deer Kill: A Case Study (9 of 15)
Arsine bubbled into the solution in the cuvette reacts with silver
diethyldithiocarbamate to form a colored complex compound according to
Equation 1F-1.
Feature 1-1: Deer Kill: A Case Study (10 of 15)

Measuring the Amount of the Analyte

The amount of arsenic in each sample was determined by measuring the intensity
of the red color formed in the cuvettes with an instrument called a
spectrophotometer. 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. To use absorbance for
analytical purposes, a calibration curve must be generated by measuring the
absorbance of several solutions that contain known concentrations of analyte. The
upper part of Figure 1F-2 shows that the color becomes more intense as the
arsenic content of the standards increases from 0 to 25 parts per million (ppm).
Feature 1-1: Deer Kill: A Case Study (11 of 15)

FIGURE 1F-2 Constructing and using a

calibration curve to determine the concentration
of arsenic. The absorbances 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 arrows.
 Feature 1-1: Deer Kill: A Case Study (12 of 15)

Calculating the Concentration

The absorbances for the standard solutions containing known concentrations of arsenic are plotted
to produce a calibration curve, shown in the lower part of Figure 1F-2. Each vertical line between the
upper and lower parts of Figure 1F-2 ties a solution to its corresponding point on the plot. The color
intensity of each solution is represented by its absorbance, which is plotted on the vertical axis of
the calibration curve. Note that the absorbance increases from 0 to about 0.72 as the concentration
of arsenic increases from 0 to 25 parts per million. The concentration of arsenic in each standard
solution corresponds to the vertical grid lines of the calibration curve as shown. This curve is then
used to determine the concentration of the two unknown solutions shown on the right. First, find the
absorbances of the unknowns on the absorbance axis of the plot, and then read the corresponding
concentrations on the concentration axis. The lines leading from the cuvettes to the calibration curve
show that the concentrations of arsenic in the two deer samples were 16 ppm and 22 ppm,
respectively.
Feature 1-1: Deer Kill: A Case Study (13 of 15)

Arsenic in kidney tissue of an animal is toxic at levels above about 10 ppm, so it

was probable that the deer were killed by ingesting an arsenic compound. The tests
also showed that the samples of grass contained about 600 ppm arsenic. This very
high level of arsenic suggested that the grass had been sprayed with an arsenical
herbicide. The investigators concluded that the deer had probably died as a result
of eating the poisoned grass.
Feature 1-1: Deer Kill: A Case Study (14 of 15)

Estimating the Reliability of the Data

The data from these experiments were analyzed using the statistical methods
described in Chapters 3–6. 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.
Feature 1-1: Deer Kill: A Case Study (15 of 15)

Conclusion
In this analysis, the formation of the highly colored product of the reaction served
both to confirm the probable presence of arsenic and to provide a reliable
estimate of its concentration in the deer and in the grass. Based on their results,
the investigators recommended that the use of arsenical herbicides be suspended
in the wildlife area to protect the deer and other animals that might eat plants
there.
 Key Terms Activity
• Analyte • Fusion
• Assay • Gravimetric method
• Calibration • Interferent
• Calibration curve • Matrix
• Dry ashing • Replicate samples
• Electroanalytical method • Sampling
• Feedback loop • Spectroscopic method
• Feedback system • Volumetric method
• Flux