Beruflich Dokumente
Kultur Dokumente
NASA/JPL-Caltech
NASA/JPL-Caltech
Mars Science Laboratory aboard rover Curiosity Curiosity observing Martian landscape from Gale crater, August 2012
Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has
deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.
2 CHAPTER 1 The Nature of Analytical Chemistry
of many elements with no sample preparation. It can determine the identity and amounts
of major, minor, and trace elements and can detect hydrated minerals. The sample analy-
sis package contains a quadrupole mass spectrometer (Chapter 29), a gas chromatograph
(Chapter 32), and a tunable laser spectrometer (Chapter 25). Its goals are to survey carbon
compound sources, search for organic compounds important to life, reveal the chemical and
isotopic states of several elements, determine the composition of the Martian atmosphere,
and search for noble gas and light element isotopes.1
These examples demonstrate that both qualitative and quantitative information are
Qualitative analysis reveals the iden- required in an analysis. Qualitative analysis establishes the chemical identity of the
tity of the elements and compounds in species in the sample. Quantitative analysis determines the relative amounts of these
a sample.
species, or analytes, in numerical terms. The data from the various spectrometers on
Quantitative analysis indicates the the rovers contain both types of information. As is common with many analytical instru-
amount of each substance in a sample.
ments, the gas chromatograph and mass spectrometer incorporate a separation step as
Analytes are the components of a a necessary part of the analytical process. With a few analytical tools, exemplified here
sample that are determined.
by the APXS and LIBS experiments, chemical separation of the various elements con-
tained in the rocks is unnecessary since the methods provide highly selective informa-
tion. In this text, we will explore quantitative methods of analysis, separation methods,
and the principles behind their operation. A qualitative analysis is often an integral part
of the separation step, and determining the identity of the analytes is an essential ad-
junct to quantitative analysis.
1
For details on the Mars Science Laboratory mission and the rover Curiosity, see http://www.nasa.gov.
Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has
deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.
1A The Role of Analytical Chemistry 3
Chemistry
Biochemistry
Inorganic Chemistry
Biology Organic Chemistry
Botany Physical Chemistry Physics
Genetics Astrophysics
Microbiology Astronomy
Molecular Biology Biophysics
Zoology
Geology Engineering
Geophysics Civil
Geochemistry Chemical
Paleontology Electrical
Paleobiology Mechanical
Analytical
Chemistry
Environmental Medicine
Sciences Clinical Chemistry
Ecology Medicinal Chemistry
Meteorology Pharmacy
Oceanography Toxicology
Agriculture
Agronomy Materials Science
Animal Science Metallurgy
Crop Science Polymers
Food Science Solid State
Social Sciences
Horticulture
Archeology
Soil Science
Anthropology
Forensics
Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has
deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.
4 CHAPTER 1 The Nature of Analytical Chemistry
1C-1 Choosing a Method
The essential first step in any quantitative analysis is the selection of a method as
depicted in Figure 1-2. The choice is sometimes difficult and requires experience
as well as intuition. One of the first questions that must be considered in the selec-
tion process is the level of accuracy required. Unfortunately, high reliability nearly
always requires a large investment of time. The selected method usually represents
a compromise between the accuracy required and the time and money available for
the analysis.
Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has
deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.
1C A Typical Quantitative Analysis 5
Select
method
Acquire
sample
Process
sample
Is No Carry out
sample soluble chemical dissolution
?
Yes
Yes
Eliminate
interferences
Figure 1-2 Flow diagram showing
the steps in a quantitative analysis.
There are a number of possible paths
Measure through these steps. In the simplest
property X example represented by the central
vertical pathway, we select a method,
acquire and process the sample,
dissolve the sample in a suitable
Calculate results solvent, measure a property of the
analyte, calculate the results, and
estimate the reliability of the results.
Depending on the complexity of the
Estimate sample and the chosen method,
reliability of results various other pathways may be
necessary.
Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has
deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.
6 CHAPTER 1 The Nature of Analytical Chemistry
ScienceCartoonsPlus.com
A material is heterogeneous if its taken. When the bulk is large and heterogeneous, great effort is required to get
constituent parts can be distinguished a representative sample. Consider, for example, a railroad car containing 25 tons
visually or with the aid of a micro-
of silver ore. The buyer and seller of the ore must agree on a price, which will be
scope. Coal, animal tissue, and soil are
heterogeneous. based primarily on the silver content of the shipment. The ore itself is inherently
heterogeneous, consisting of many lumps that vary in size as well as in silver con-
An assay is the process of determin- tent. The assay of this shipment will be performed on a sample that weighs about
ing how much of a given sample is the one gram. For the analysis to have significance, the composition of this small sam-
material by its indicated name. For ple must be representative of the 25 tons (or approximately 22,700,000 g) of ore
example, a zinc alloy is assayed for its
in the shipment. Isolation of one gram of material that accurately represents the
zinc content, and its assay is a particu-
lar numerical value. average composition of the nearly 23,000,000 g of bulk sample is a difficult un-
dertaking that requires a careful, systematic manipulation of the entire shipment.
Sampling is the process of collecting a small mass of a material whose composition
We analyze samples, and we
determine substances. For ❯ accurately represents the bulk of the material being sampled. Sampling is discussed
in more detail in Chapter 8.
example, a blood sample is
analyzed to determine the The collection of specimens from biological sources represents a second type
concentrations of various of sampling problem. Sampling of human blood for the determination of blood
substances such as blood gases gases illustrates the difficulty of acquiring a representative sample from a com-
and glucose. We, therefore, speak plex biological system. The concentration of oxygen and carbon dioxide in blood
of the determination of blood
depends on a variety of physiological and environmental variables. For example,
gases or glucose, not the analysis
of blood gases or glucose. applying a tourniquet incorrectly or hand flexing by the patient may cause the
blood oxygen concentration to fluctuate. Because physicians make life-and-death
decisions based on results of blood gas analyses, strict procedures have been de-
veloped for sampling and transporting specimens to the clinical laboratory. These
procedures ensure that the sample is representative of the patient at the time it is
collected and that its integrity is preserved until the sample can be analyzed.
Many sampling problems are easier to solve than the two just described. Whether
sampling is simple or complex, however, the analyst must be sure that the laboratory
sample is representative of the whole before proceeding. Sampling is frequently the
most difficult step in an analysis and the source of greatest error. The final analytical
result will never be any more reliable than the reliability of the sampling step.
Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has
deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.
1C A Typical Quantitative Analysis 7
Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has
deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.
8 CHAPTER 1 The Nature of Analytical Chemistry
form that is suitable for the measurement step. For example, in the determination of
manganese in steel, the element must be oxidized to MnO42 before the absorbance
of the colored solution is measured (see Chapter 26). At this point in the analysis,
it may be possible to proceed directly to the measurement step, but more often
than not, we must eliminate interferences in the sample before making measure-
ments, as illustrated in the flow diagram.
1C-4 Eliminating Interferences
Once we have the sample in solution and converted the analyte to an appropriate
form for measurement, the next step is to eliminate substances from the sample that
may interfere with measurement (see Figure 1-2). Few chemical or physical proper-
ties of importance in chemical analysis are unique to a single chemical species. In-
stead, the reactions used and the properties measured are characteristic of a group of
elements of compounds. Species other than the analyte that affect the final measure-
An interference or interferent is a ment are called interferences, or interferents. A scheme must be devised to isolate
species that causes an error in an the analytes from interferences before the final measurement is made. No hard and
analysis by enhancing or attenuating fast rules can be given for eliminating interference. This problem can certainly be the
(making smaller) the quantity being
measured. most demanding aspect of an analysis. Chapters 31 through 34 describe separation
methods in detail.
Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has
deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.
1D An Integral Role for Chemical Analysis: Feedback Control Systems 9
Chapters 5, 6, and 7 present detailed methods for carrying out this important final
step in the analytical process. ❮ An analytical result without an
estimate of reliability is of no
value.
A
n Integral Role for Chemical Analysis:
1D Feedback Control Systems
Analytical chemistry is usually not an end in itself but is part of a bigger picture in
which the analytical results may be used to help control a patient’s health, to control
the amount of mercury in fish, to control the quality of a product, to determine the
status of a synthesis, or to find out whether there is life on Mars. Chemical analysis is
the measurement element in all of these examples and in many other cases. Consider
the role of quantitative analysis in the determination and control of the concentration
of glucose in blood. The system flow diagram of Figure 1-3 illustrates the process.
Patients suffering from insulin-dependent diabetes mellitus develop hyperglycemia,
which manifests itself in a blood glucose concentration above the normal concentration
range of 65 to 100 mg/dL. We begin our example by determining that the desired state
is a blood glucose level below 100 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.
The first step in the monitoring process is to determine the actual state by col-
lecting a blood sample from the patient and measuring the blood glucose level. The
results are displayed, and then the actual state is compared to the desired state, as
shown in Figure 1-3. If the measured blood glucose level is above 100 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. If the
level is below the threshold, the insulin level has been maintained, so no insulin is
required. After a suitable delay time, the blood glucose level is measured again, and
the cycle is repeated. In this way, the insulin level in the patient’s blood, and thus the
Start control
system Figure 1-3 Feedback system flow
diagram. The desired system state is
defined, the actual state of the system
is measured, and the two states are
Determine
desired state compared. The difference between the
two states is used to change a control-
lable quantity that results in a change
in the state of the system. Quantitative
Change control Measure measurements are again performed
Delay
quantity actual state 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
Display
the system if necessary. The process
results
provides continuous monitoring and
feedback to maintain the controllable
quantity, and thus the actual state, at
Does the proper level. The text describes
No Yes
desired state 5 the monitoring and control of blood
actual? glucose as an example of a feedback
control system.
Unless otherwise noted, all content on this page is © Cengage Learning.
Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has
deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.
10 CHAPTER 1 The Nature of Analytical Chemistry
blood glucose level, is maintained at or below the critical threshold, which keeps the
metabolism of the patient under control.
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 are widely applied in biological and biomedi-
cal systems, mechanical systems, and electronics. From the measurement and con-
trol of the concentration of manganese in steel to maintaining the proper level
of chlorine in a swimming pool, chemical analysis plays a central role in a broad
range of systems.
Feature 1-1
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 Na- White-tailed deer have proliferated in many parts of the country.
tional Recreation Area in western Kentucky. The ranger
enlisted the help of a chemist from the state veterinary diag- CH3AsO(OH)2, which is very soluble in water and thus finds
nostic laboratory to find the cause of death so that further deer use as the active ingredient in many herbicides. The herbicidal
kills might be prevented. activity of disodium methanearsenate is due to its reactivity
The ranger and the chemist carefully inspected the site with the sulfhydryl (S3H) groups in the amino acid cyste-
where the badly decomposed carcass of the deer had been ine. When cysteine in plant enzymes reacts with arsenical
found. Because of the advanced state of decomposition, no compounds, the enzyme function is inhibited, and the plant
fresh organ tissue samples could be gathered. A few days after eventually dies. Unfortunately, similar chemical effects oc-
the original inquiry, the ranger found two more dead deer near cur in animals as well. The investigators, therefore, collected
the same location. The chemist was summoned to the site of samples of the discolored dead grass for testing along with
the kill, where he and the ranger loaded the deer onto a truck samples from the organs of the deer. They planned to analyze
for transport to the veterinary diagnostic laboratory. The in- the samples to confirm the presence of arsenic and, if present,
vestigators then conducted a careful examination of the sur- to determine its concentration in the samples.
rounding area in an attempt to find clues to establish the cause
of death. Selecting a Method
The search covered about 2 acres surrounding the pond. A scheme for the quantitative determination of arsenic in
The investigators noticed that grass surrounding nearby power biological samples is found in the published methods of the
line poles was wilted and discolored. They speculated that a Association of Official Analytical Chemists (AOAC).3 In this
herbicide might have been used on the grass. A common method, arsenic is distilled as arsine, AsH3, and is then deter-
ingredient in herbicides is arsenic in any one of a variety of mined by colorimetric measurements.
forms, including arsenic trioxide, sodium arsenite, monoso-
dium methanearsenate, and disodium methanearsenate. The 3
Official Methods of Analysis, 18th ed., Method 973.78 , Washington,
last compound is the disodium salt of methanearsenic acid, DC: Association of Official Analytical Chemists, 2005.
Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has
deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.
1D An Integral Role for Chemical Analysis: Feedback Control Systems 11
Eliminating Interferences
Arsenic can be separated from other substances that might
interfere in the analysis by converting it to arsine, AsH3, a
toxic, colorless gas that is evolved when a solution of H3AsO3
is treated with zinc. The solutions resulting from the deer
and grass samples were combined with Sn2+, and a small
amount of iodide ion was added to catalyze the reduction of
H3AsO4 to H3AsO3 according to the following reaction: Absorbent
solution
(continued)
Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has
deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.
12 CHAPTER 1 The Nature of Analytical Chemistry
Arsine bubbled into the solution in the cuvette reacts with Note that the absorbance increases from 0 to about 0.72 as
silver diethyldithiocarbamate to form a colored complex com- the concentration of arsenic increases from 0 to 25 parts per
pound according to the following equation: million. The concentration of arsenic in each standard solu-
tion 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. We 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 con-
centrations of arsenic in the two deer samples were 16 ppm
and 22 ppm, respectively.
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
Molecular model of diethyldithiocarbamate. This compound is
an analytical reagent used in determining arsenic.
very high level of arsenic suggested that the grass had been
2
C2H5 S
AsH3 1 6Ag1 1 3 N C
C2H5 S
C2H5 S
As N C 1 6Ag 1 3H1
C2H5 S 3
Measuring the Amount of the Analyte sprayed with an arsenical herbicide. The investigators con-
The amount of arsenic in each sample was determined by cluded that the deer had probably died as a result of eating
measuring the intensity of the red color formed in the cu- the poisoned grass.
vettes with an instrument called a spectrophotometer. As Estimating the Reliability of the Data
shown in Chapter 26, a spectrophotometer provides a num-
The data from these experiments were analyzed using the sta-
ber called absorbance that is directly proportional to the
tistical methods described in Chapters 5- 8. For each of the
color intensity, which is also proportional to the concentra-
standard arsenic solutions and the deer samples, the average of
tion of the species responsible for the color. To use absor-
the three absorbance measurements was calculated. The aver-
bance for analytical purposes, a calibration curve must be
age absorbance for the replicates is a more reliable measure of
generated by measuring the absorbance of several solutions
the concentration of arsenic than a single measurement. Least-
that contain known concentrations of analyte. The upper
squares analysis of the standard data (see Section 8D) was used
part of Figure 1F-2 shows that the color becomes more in-
to find the best straight line among the points and to calculate
tense as the arsenic content of the standards increases from 0
the concentrations of the unknown samples along with their
to 25 parts per million (ppm).
statistical uncertainties and confidence limits.
Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has
deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.
1D An Integral Role for Chemical Analysis: Feedback Control Systems 13
Standards Samples
0.8
0.6
Absorbance
0.4
0.2
0
0 5 10 15 20 25
Concentration, ppm
The case study of Feature 1-1 illustrates how chemical analysis is used in the iden-
tification and determination of quantities of hazardous chemicals in the environment.
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. The desired state
is a concentration of arsenic that is below the toxic level. Chemical analysis is used to
determine the actual state, or the concentration of arsenic in the environment, and this
value is compared to the desired concentration. The difference is then used to determine
appropriate actions (such as decreased use of arsenical pesticides) to ensure that deer are
not poisoned by excessive amounts of arsenic in the environment, which in this exam-
ple is the controlled system. Many other examples are given in the text and in features
throughout this book.
Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has
deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.
Tools of Analytical
PA RT I
Chemistry
Chapter 2
Chemicals, Apparatus, and Unit Operations
of Analytical Chemistry
Chapter 3
Using Spreadsheets in Analytical Chemistry
Chapter 4
Calculations Used in Analytical Chemistry
Chapter 5
Errors in Chemical Analysis
Chapter 6
Random Errors in Chemical Analysis
Chapter 7
Statistical Analysis Data Treatment and Evaluation
Chapter 8
Sampling, Standardization, and Calibration
Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has
deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.