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Table of Contents
(Subject Area: Analytical Chemistry)

Pages in the
Article Authors
Encyclopedia

Ulrich J. Krull and Michael


Analytical Chemistry Pages 543-579
Thompson
Atomic Spectrometry Vahid Majidi Pages 765-786
Auger Electron
C. L. Briant Pages 787-792
Spectroscopy
Capillary Zone
Tim Wehr Pages 355-368
Electrophoresis
Electrochemistry Donald T. Sawyer Pages 161-197
Electron Spin
Larry Kevan Pages 331-345
Resonance
Electrophoresis S. P. Spragg Pages 363-378
Elemental Analysis,
T. S. Ma Pages 393-405
Organic Compounds
Gas Chromatography Milos Novotny Pages 455-472

Infrared Spectroscopy Norman B. Colthup Pages 793-816


Liquid
Neil D. Danielson Pages 673-700
Chromatography
Magnetic Resonance in
John F. Schenck Pages 959-981
Medicine
Mass Spectrometry Kenneth L. Busch Pages 145-158
Mass Spectrometry in
Jan Schuberth Pages 159-169
Forensic Science
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Microwave molecular
Robert L. Cook Pages 799-852
spectroscopy
Nuclear Magnetic
Bernard C. Gerstein Pages 701-720
Resonance (NMR)
Organic Chemistry, Raphael Ikan and Bernard
Pages 459-496
Compound Detection Crammer
Photoacoustic Konka Veeranjaneyulu and
Pages 1-13
Spectroscopy Roger M. Leblanc
Photoelectron G. Hohlneicher and A.
Pages 57-90
Spectroscopy Gildenpfennig
R. P. Van Duyne and C. L.
Raman Spectroscopy Pages 845-866
Haynes
Scanning Probe
C. Daniel Frisbie Pages 469-484
Microscopy
Sonoluminescence and
Kenneth S. Suslick Pages 363-376
Sonochemistry
Spectroscopy in
Michael B. Eyring Pages 637-643
Forensic Science
Thermal Analysis David Dollimore Pages 591-612

Tomography Z. H. Cho Pages 843-877


Ultrafast Spectroscopy M. Hayashi, Y. M. Chang, T.
Pages 217-226
and its Applications K. Wang, S. H. Lin and
X-Ray Analysis Ron Jenkins Pages 887-902
X-Ray Photoelectron Charles C. Chusuei and D.
Pages 921-938
Spectroscopy Wayne Goodman
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Analytical Chemistry
Ulrich J. Krull
Michael Thompson
University of Toronto

I. Classical Methods
II. Instrumental Methods
III. Computers in Analytical Chemistry
IV. Future Perspectives

GLOSSARY Quantitative analysis Process of determining the rela-


tive amounts of one or more component(s) in a sample
Accuracy Nearness of a measurement to its accepted of matter.
value. Resolution The ratio given by the average magnitude of
Analyte Species present in a sample of matter about an analytical variable divided by the smallest difference
which chemical information is sought. of values of the analytical variable, where each value
Calibration Process of determining the precise quanti- provides analytical signals that are considered distinct
tative relationship between a known concentration of by statistical techniques.
a chemical species and a physical property of that Selective Method in analytical chemistry that yields a re-
species. sponse for a group of chemical species.
Interferences Elements or chemical compounds that Sensitivity Ratio of the change in the response of an in-
have similar properties to the analyte that prevent its strument with a corresponding change in the concen-
direct measurement. tration of a chemical species.
Limit of detection Concentration of a chemical species Specific Method in analytical chemistry that yields a re-
that produces an analytical signal equal to twice the sponse for a single chemical entity only.
standard deviation of the background signal. Standard Chemical species with well-established physi-
Matrix Matter present in a sample in which the species cal properties that is employed to calibrate an analytical
being determined is dispersed. procedure.
Noise Random fluctuations of analytical signal with time.
Precision Statistical measure of the distribution of a se-
ries of analytical determinations about the average ANALYTICAL CHEMISTRY is concerned with pro-
value of the same analytical determinations. viding qualitative and quantitative information about the
Qualitative analysis Process of identifying one or more chemical and structural composition of a sample of mat-
component(s) in a sample of matter. ter. A huge variety of samples, from high concentrations of

543
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544 Analytical Chemistry

elements in alloy steels to part-per-billion levels of drugs ganic species lies in their chemical and physical behavior.
in biological tissue, are handled by the analyst. The field For example, reagents are used to yield distinct chemical
is founded on the conversion of a measured physical prop- effects such as the production of colored solutions or pre-
erty of the species being examined to a usable signal. It cipitates, the generation of easily observed gases, and the
is generally divided into two categories, classical and in- dissolution of previously insoluble substances. In a typical
strumental, on the basis of its historical development. The analysis, the identification of several species is required,
overall strategy is to prepare a sample correctly, choose and in this circumstance, it is desirable to employ selective
a particular method of analysis, and report the results reactions for each component of the system.
in a meaningful format, which may include a statistical This type of chemistry is incorporated into a strategy
evaluation. that involves the separation of the original mixture into
several parts in order to avoid the buildup of a highly
complex array with a specific sample due to the addition
of a number of reagents. Each part is then subjected to
I. CLASSICAL METHODS an analysis of a small number of species. In summary,
the analysis involves a set of sequenced separations and
A. Semimicro Qualitative Analysis
identifications.
A complete system of qualitative analysis is usually re- The strategy for the separation of cations involves their
stricted to the detection of a complex array of inorganic division into a set of groups by treatment with a particular
cations and anions. In principle, schemes are developed to selective reagent. After solution of the unknown in water,
include less common species such as rhenium and tellurate a reagent is employed to cause all cations of the group to
anions, but more often than not attention is concentrated on precipitate, with all other ions remaining in solution. A
more common cations such as Na+ and Cu2+ and oxy an- typical overall scheme (simplified) is depicted in Fig. 1.

ions such as SO2−
4 and NO3 . The basis for identifying inor-
After separation, the precipitate is reexamined for specific

FIGURE 1 Simplified strategy for separation of cations into groups for qualitative analysis.
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Analytical Chemistry 545

cations. As one example let us consider the silver group. and therefore the error, on reagent precipitation. The fa-
Treatment of the white precipitate of Hg2 Cl2 , AgCl, and cility with which a precipitate is removed from solution
PbCl2 with hot water results in solubilization of the lead is related to the particle size of the solid phase, which in
compound to yield a colorless solution. The presence of turn is governed by the conditions that exist at the time
Pb2+ is confirmed by the addition of K2 CrO4 , which gives of formation of the precipitate. Thought to be important
a yellow precipitate of PbCrO4 . Addition of NH4 OH to are the solubility of the precipitate, temperature, reactant
Hg2 Cl2 and AgCl results in either a gray mixture of mer- concentration, and mixing phenomena. These parameters
cury and HgNH2 Cl, confirming Hg2+ 2 , and/or colorless control the supersaturation that exists in solution at a par-
solutions of Ag(NH3 )+ 2 Cl −
. Acidification of the latter re- ticular time. Although the usual aim is to achieve an eas-
precipitates AgCl, identifying the presence of Ag+ . ily manipulated crystalline precipitate, colloidal particles
The detection of anions in the original sample does not (10−6 to 10−4 mm in size) are sometimes obtained. In
proceed in the same way in that the material is usually sub- these cases, the individual particles must be coagulated
jected to a series of preliminary tests. Moreover, the cation by an experimental procedure such as heating, stirring,
analysis described above can often be assessed to infer the and the addition of auxiliary electrolyte. The mechanism
presence of certain anions. A sample solution is separately of this process lies in the reduction of electrical repulsive
treated with AgNO3 and BaCl2 , and the various precipi- forces on the particles. Purer, more dense precipitates can
tates of silver and barium are used to verify the presence of often be produced by precipitation from homogeneous so-
anionic components. This procedure is then followed by lution, where the reagent is generated in solution. Finally,
the addition of concentrated cold H2 SO4 to the unknown after filtration a gravimetric precipitate is heated until its
solid, which results in the liberation of characteristic gases weight becomes constant. A wide range of temperatures
(e.g., I− gives the odor of H2 S and violet fumes of I2 ), and (110–1200◦ C) are used for this purpose, the most impor-
by a series of confirmatory tests for each anion. tant requirement being weight constancy and unequivocal
On a practical level the whole analysis is performed knowledge of the composition of the precipitate at a par-
at the semimicro level. This means that sample sizes are ticular temperature.
in the range of 10 mg and solutions are of the order of Some examples of inorganic and organic precipitation
1–2 ml in volume. Special equipment is required to han- agents for inorganic analytes are given in Table I.
dle low volumes of reagent solutions and to avoid serious There are also methods available for the precipitation
losses in separative and transfer procedures. The sepa- of organic compounds through the reaction of a partic-
ration of precipitates is performed by centrifugation and ular functional group. For example, compounds with
decantation, and heating is achieved in specially designed carbonyl functional groups can be precipitated with
test tube heating blocks. 2,4-dinitrophenylhydrazine according to the following
reaction:
B. Gravimetric Analysis RCHO + H2 NNHC6 H3 (NO2 )2 →
Here, quantitative analysis is based on the measurement of R—CH NNHC6 H3 (NO2 )2 ↓ + H2 O.
the weight of a substance of precisely known composition
that is chemically related to the analyte. Most often the In summary, the gravimetric method does not require
unknown is precipitated from solution by a reagent and, calibration, as is the case with many other analytical
after separation and drying, is weighed. Less frequently
the species being determined is volatilized, and the weight TABLE I Typical Inorganic and Organic Precipitat-
of the condensed gas or residual solid serves to complete ing Agents
the analysis. The precipitate must be insoluble in water Element precipitated
(or other solvent) in order to minimize obvious losses, be Agent (weighed form)
easily filtered and washed, and be stable after drying or ig-
NH3 Al (Al2 O3 ), Fe (Fe2 O3 )
nition procedures. With respect to the first requirement, an
H2 S Zn (ZnO), Ge (GeO2 )
important quantitative parameter is the solubility product
H2 SO4 Pb (PbSO4 ), Ba (BaSO4 )
of the compound produced from the analyte. For exam-
HCl Ag (AgCl)
ple, for the precipitation of SO2− 2+
4 with Ba , the solubility
(NH4 )2 CO3 Bi (Bi2 O3 )
product (K sp ) for BaSO4 is defined by
  BaCl2 SO2−
4 (BaSO4 )
K sp = [Ba2+ ] SO2−4 = 1.3 × 10−10 MgCl2 , NH4 Cl PO3−
4 (Mg2 P2 O7 )
8-Hydroxyquinoline (HQ) Al (AlQ3 )
for a saturated solution. Clearly, this value can be used
Dimethylglyoxime (DMG) Ni (NiDMG2 )
to compute the loss of analyte (remaining in solution),
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546 Analytical Chemistry

methods (see later). Accordingly, it is still frequently used ion, bases are standardized against potassium hydrogen
as a “standardizing” technique for instrumental methods. phthalate (KHC8 H4 O4 ). The end point in a strong acid–
Gravimetry, however, can be rather time consuming, es- strong base neutralization titration is usually found from
pecially if a large number of samples are involved. the in situ behavior of an added indicator, which is gener-
ally a weak organic acid or base that undergoes chemical
changes exhibiting different colors. For example, we can
C. Titrimetric (Volumetric) Analysis
write for the acid-type indicator HIn
In titrimetric analysis, which is often termed volumetric
H2 O + HIn = H3 O+ + In− ,
analysis, we obtain the volume of a standard reagent re-
quired to consume an analyte completely. On a practical (color 1 in (color 2 in
basis a standard solution of reagent, the concentration of acid solution) basic solution)
which is known accurately, is added by a buret until it is
Thus, it is very important to know the range of hydrogen
decided that the analyte is just used up. This condition is
ion concentration (i.e., pH) in which a change from color
usually called the equivalence point. Since it is difficult
1 to color 2 can be observed. Generally, this occurs within
to observe this point experimentally, it is usually approx-
approximately ±1 pH unit of the pK a of the indicator.
imated by the distinction of an end point, which is asso-
The titration of a strong acid solution by additions of
ciated with detectable physical changes at equivalence. It
a standard strong base solution from a buret would re-
is generally the case that standard solutions are calibrated
sult theoretically in the lower graph shown in Fig. 2 (the
against solutions of a primary standard that is a highly
titration curve). Accordingly, we would require an added
pure and stable reference substance.
indicator to respond to the abrupt approximately 3–10 pH
In the present description we introduce four types of vol-
change. In this case, phenolphthalein would be appropri-
umetric analysis. One involves the neutralization of acid or
ate, since its change from colorless to purple is easily
base, the second is concerned with precipitation, the third
detected by the eye. The titration curve for a weak acid
with complex formation, and the fourth with oxidation–
(with strong base) depends very much on the dissociation
reduction reactions. Before doing this we must consider
constant of the acid. Basically, additions of base set up a
several definitions. The equivalent weight of a substance is
buffer zone as in the set of curves shown in Fig. 2 (upper
generally the weight that combines with a standard amount
curve). The choice of an indicator for this type of titration
of reactant. The parameter is based entirely on the nature
is significantly more limited than for a strong acid, since
of a particular reaction and, therefore, can have no more
there is now no abrupt change in pH. Not surprisingly,
precise meaning at this stage. Titration refers to the pro-
the appropriate curves for polyprotic weak acids are even
cess of gradual addition of standard reagent, whereas the
more complex.
titer of a solution is the weight of a substance that is chem-
Neutralization methods are employed wherever inor-
ically equivalent to 1 ml of the solution. Finally, one often
ganic or organic substances possess acidic or basic groups.
sees the term normality, which expresses the number of
An important application is the conversion of elements
milliequivalents of solute contained in 1 ml of solution.
The end point in titrimetric methods is usually based
on a way of dynamically distinguishing analyte or reagent
concentration. The most widely used method is change in
color due to reagent, analyte, or indicator, but the moni-
toring of electrical potential and current, and turbidity, are
sometimes used.

1. Neutralization Titrations
In this technique the concentration of acid or base is de-
termined through the abrupt change of pH that occurs at
the titration end point. Here, the equivalent weight of the
acid or base is the weight that either contributes or reacts
with 1 mol of hydrogen ion in that specific reaction. The
standard reagents used in the titration are always strong
acids or bases, although the analyte may be a weak acid
or base. A-standard acid solution can be prepared by titra- FIGURE 2 Neutralization titration curves for 50 ml of 0.05M
tion of the acid, say HCl, against a solution containing an strong acid (lower curve) and weak acid (upper curve) with 0.1M
accurately known weight of Na2 CO3 . In a similar fash- NaOH solution.
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Analytical Chemistry 547

in organic or biological systems to acid–base character. of Cl− and Br− is that of Mohr, who used chromate ion
For example, organic nitrogen is converted to NH+
4 in the (CrO2−4 ), the end point being specified by the appearence
Kjedahl method to be determined in a neutralization pro- of Ag2 CrO4 , which is brick red in color. The essence of
cedure as liberated NH3 . the principle here is that the solubility of silver chromate
is much greater than that of silver halide. Accordingly, the
conditions of the titration can be adjusted such that the
2. Precipitation Titrations formation of silver chromate occurs only in the vicinity of
In this method, the reagent solution, added from a buret, the end point. In the Volhard method a standard solution of
is allowed to cause precipitation with the analyte, and the thiocyanate ion (SCN− ) is titrated against Ag+ using Fe3+
end point is associated with an abrupt change in the con- as the indicator. At the initial excess of SCN− , a red color
centration of the reagent species. The equivalent weight of due to red Fe(SCN)2+ is produced. An important applica-
a participant in a precipitation titration is the weight that tion of this method is the “backtitration” procedure for the
reacts with or provides 1 g formula weight of the reacting Cl− ion. Here, an excess of standard silver nitrate solution
cation if it is univalent (0.5 for divalent, etc.). The tech- is added to the unknown Cl− solution and then titrated
nique can be best understood by the example provided by with SCN− with the Volhard indicator in place. Finally,
the long-standing silver ion procedure for the determina- adsorption indicators (Fajans method) are employed that
tion of halide anion, particularly Cl− (sometimes termed are based on the adsorption of a colored organic compound
argentometric titration). Typical titration curves for vari- to the precipitate, only in the vicinity of the end point.
ous halide anions with silver cation are shown in Fig. 3.
Notice that the concentration of the free reagent cation
3. Complexometric Titrations
present at a particular point in the titration is usually ex-
pressed as −log[Ag+ ], that is, pAg, in a fashion analogous Titrimetric methods based on the reaction of metal
to pH for hydronium ion. Before the equivalence point ions with a coordinating species (ligand) are more than
(with abrupt change of pAg), the concentration of Ag+ is 100 years old. If the ligand is attached to the metal by
determined by the solubility product of the silver halide more than one functional group, it is said to be polyden-
concerned. After this point we simply have the concentra- tate and the compound produced is called a chelate. The
tion of excess added reagent, which is not now reacting complexometric reagent that is easily the most widely used
with halide anion. To detect the end point an indicator is for the titration of unknown concentrations of metal ion
required that will respond to the particular range of abrupt is the hexadentate ligand ethylenediaminetetraacetic acid
pAg change shown in Fig. 3. A common method in the case (EDTA), first recognized by Schwarzenbach in 1945. The
structure of the molecule is

HOOC−CH2 CH2 −COOH


\ /
N−CH2 −CH2 −N
/ \
HOOC−CH2 CH2 −COOH

and is usually abbreviated to the shorthand notation H4 Y,


with H representing the carboxylic hydrogen atoms. This
reagent is extremely important because it forms simple
1 : 1 complexes with a metal ion, that is, one metal atom
to one EDTA molecule of very high stability. Note that the
latter is associated with the relatively large number (6) of
points of attachment (4 × COO− + 2 × N) of the ligand
to the metal.
In the now familiar pattern discussed above, the titration
involves the buret addition of EDTA solution to the metal
ion solution, which generates a titration curve with an
abrupt change in −log[Mn+ ] (pM). This is governed by
FIGURE 3 Precipitation titration curves for 25 ml of 0.1M solu- the equilibrium constant for the formation of the metal–
tions of various anions with 0.1M AgNO3 solution. EDTA complex:
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548 Analytical Chemistry


 
MY(n−4)+ TABLE II Common Oxidizing and Reducing Agents Em-
K MY = , ployed as Standard Solutions in Oxidation–Reduction Titra-
[Mn+ ][Y 4− ] tions
Note the analogy of this result with that outlined for Oxidizing Reduction
the effect of solubility product in precipitation titrations Reagent species Product
discussed above. A great many compounds have been
Oxidizing
proposed as indicators for metal ions in EDTA titrations.
Potassium permanganate, KMnO4 MnO− Mn2+
These species are generally organic compounds that form 4
Potassium bromate, KBrO3 BrO− Br−
colored chelates with metal ions in a range of pM that 3
Cerium ammonium nitrate, Ce4+ Ce3+
is characteristic of the cation and dye. One example is
Ce(NO3 )4 2NH4 NO3
Eriochrome black T, which is blue at pH 7 and red when
Potassium dichromate, K2 Cr2 O7 Cr2 O2−
7 Cr3+
complexed with a variety of metal ions.
Potassium, iodate, KlO3 IO−
3 I−
EDTA titrations are still widely used because of their
great versatility with respect to the analysis of a large num- Reducing Oxidation
ber of different metal cations. Furthermore, the technique species product
can be made more selective by adjusting the pH or by Reducing
the use of compounds that effectively remove interfering Sodium thiosulfate, Na2 S2 O3 S2 O2− S4 O2−
3 6
cations from the titration (masking agent). The method is Ferrous ammonium sulfate, Fe2+ Fe3+
inexpensive and reasonably accurate. Fe(NH4 )2 (SO4 )2 ·6H2 O

4. Oxidation–Reduction Titrations
Here, we are dealing with the reaction of an oxidizing derive
3+ + 5E
0 0
(reducing) reagent as titrant with a reducing (oxidizing) E Fe MnO−
species as unknown. The equivalent weight of a partici- E eq = 4

6
pant in this type of system is the weight that directly or  
indirectly produces or consumes 1 mol of electrons. Thus, 0.0591 5 MnO− 2+
4 [Mn ]
− log   .
the equivalent weight for the permanganate ion (MnO− 4)
6 5[Mn2+ ] MnO− + 8
4 [H ]
in its oxidation of oxalate anion in the reaction
Thus,
5C2 O2−
4 + 2MnO−
4 + 16H + 0
E Fe3+ + 5E
0
MnO− 0.0591 1
E eq = 4
− log + 8 .
→ 10CO2 + 2Mn2+ + 8H2 O 6 6 [H ]
is the molecular weight of MnO−
divided by 5.
4
In much the same manner as for the other types of
A great variety of both oxidizing and reducing agents titration described above, it is the electrode potential dur-
have been employed for this type of titration, and some ing the procedure that exhibits an abrupt change on ad-
common compounds are given in Table II. The equivalence dition of reagent. Accordingly, we require indicators that
point of oxidation–reduction titrations can be computed change color during this change (i.e., that show oxidation–
from a knowledge of solution concentrations and electri- reduction behavior themselves). Two examples are 1, 10-
cal potentials. For example, in the titration of ferrous ion phenanthroline–iron (II) complex, which changes from
against KMnO4 according to the following reaction pale blue to red at an electrical potential of +1.11 V (in
1M H2 SO4 ), and diphenylaminesulfonic acid, which
5Fe2+ + MnO− +
4 + 8H → 5Fe
3+
+ Mn2+ + 4H2 O, changes from colorless to violet at 0.85 V.
we can write Nernst electrode potentials for each
oxidation–reduction system:
II. INSTRUMENTAL METHODS
[Fe2+ ]
E = E Fe
0
3+ − 0.0591 log 3+ A. Absorption of Electromagnetic Radiation
[Fe ]
0.0591 [Mn2+ ] Matter interacts with incident electromagnetic radiation
E = E MnO
0
− − log   , by the three distinct processes of transmission, scattering,
4 5 MnO−
4 [H ]
+ 8
or absorption. The nature of any interaction is a function of
At the equivalence point we know that these two poten- the properties of the radiation, such as energy, phase, po-
tials, now called E eq , are equal; therefore, on adding we larization, and the chemical properties of the matter under
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Analytical Chemistry 549

FIGURE 4 Analytical potential for absorption spectroscopy across the electromagnetic spectrum.

investigation. Chemical evaluation is derived from obser- concentration of the analyte, and A represents a value for
vation of the extent of interaction by measurement of the absorption.
energy and intensity of transmitted, scattered, absorbed,
or latently released radiation.
Absorption is said to occur when radiation passes 1. Atomic Absorption
through matter and interacts with the ions, atoms, or The absorption of radiation by a sample of atomic parti-
molecules constituting the sample in such a way that they cles, created by vaporizing the sample, represents a rel-
gain energy and move from a quantized low-energy state atively simple spectral situation that has great practical
to a higher energy state. Analytically, this phenomenon is value for elemental identification and concentration de-
observed as a reduction of the intensity of radiation after termination. The absorption spectrum observed with poly-
passage through a sample of matter. Two distinct param- chromatic light contains only a few areas of reduced in-
eters can be investigated. The reduction of intensity is a tensity occurring at very well-defined frequencies due to
function of the probability of interaction of the radiation the small number of energy states available to the atoms.
with appropriate analyte species and indicates concentra- The natural width of such absorption lines can be less than
tion. Also, the energy of the absorbed radiation indicates 10−4 nm, but broadening often occurs due to collisional
the quantized energy levels in which energy is deposited and Doppler effects in the sample matrix. The quantized
(Fig. 4) and therefore assists in species identification. The energy transitions responsible for atomic absorption are
Beer–Lambert law generally applies to all absorption pro- of electronic origin, indicating that electromagnetic spec-
cesses at low concentrations when monochromatic radia- trum energies from X-rays to ultraviolet–visible rediation
tion is used. It is conventionally written are sufficient to observe this process.
P0 The technique known as atomic absorption spec-
log = εbc = A, troscopy is of particular analytical importance for the de-
P termination of metals due to its sensitivity and potential
where P0 is the initial power of an incident beam of radi- for selectivity by virtue of the narrow atomic absorption
ation, P is the final power (decreased due to absorption), lines. A schematic representation of the spectrophotome-
ε represents a value characteristic of the extent of absorp- ter is shown in Fig. 5. To take advantage of characteristic
tion expected for a certain species at a defined wavelength selectivity, a special radiation source must be provided
in a defined matrix, b is the sample path length, c is the to produce extremely monochromatic radiation with a

FIGURE 5 Representation of the design of a conventional atomic absorption spectrophotometer.


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550 Analytical Chemistry

linewidth less than the absorption bandwidth of the atomic TABLE III Atomic Absorption Detection Limits for Common
sample. In most cases the same element being analyzed is Analytes
also used in the source lamp to provide appropriate emis- Limit of detection (ppm)
Analytical
sion line spectra by stimulation with a plasma discharge. wavelength Flame Nonflame
Common sources are hollow cathode lamps, electrode- Element (nm) absorptiona absorption
less discharge lamps, and gaseous discharge lamps. The
source is often modulated and coupled to a lock-in am- Aluminum 396.2 0.03 0.00001
plifier in order to determine the relative absorbance of Calcium 422.7 0.001 0.00005
the atomic sample as compared with sample emission at Cadmium 326.1 0.0005 0.000003
the same wavelength. Other methods of background cor- Iron 372.0 0.003 0.00002
rection involve monitoring of a nonabsorbed radiation by Lithium 670.8 0.0005 0.0003
the use of distinct spectral lines, continuous sources, or Magnesium 285.2 0.0001 0.000004
the Zeeman effect (separation of degenerate energy states Potassium 766.5 0.005 0.0009
of an atom by application of a powerful magnetic field; a Data for acetylene–air flame.
provides closely spaced energy levels which are sensi-
tive to polarized light). The sample itself is usually pro-
2. Molecular Absorption
duced by volatilization of solutions in a high-temperature
flame or solids and in a graphite furnance. Flame methods The absorption spectrum commonly produced by
generally provide relative errors of approximately 1–2%, molecules is significantly more complex than that
whereas the equivalent furnace methods provide only 5– produced by atoms due to the large number of energy
10%, but sensitivities up to 1000 times greater than those states available for energy deposition. The total energy of
observed for flames. Chemical interferences commonly a molecule that has no translational velocity is given by
originate from the atmosphere supporting the atomic pop-
E total = E electronic + E vibrational + E rotational ,
ulation and from other sample matrix components. The
formation of oxides in flames causes the reduction of the where the electronic levels due to electrons in bonding and
atomic population and can be controlled by the employ- nonbonding orbitals are related to numerous interatomic
ment of appropriate fuel–oxidant ratios and by sampling vibrations and molecular rotations about a center of grav-
appropriate portions of the flame. This problem is avoided ity. The large energy difference of the three energy types
in the furnace by the use of a continuous flowing inert implies that each can be individually studied with radiation
gas atmosphere. Poor volatilization and atomization often from distinctly different portions of the electromagnetic
occur when an analyte binds with anions in the sample spectrum.
matrix. This is overcome by the use of high concentra-
tions of cationic releasing agents, which preferentially Optical polarization. Since the early 1800s it has
couple with the interferent, or by the use of protective been recognized that certain molecules have the capacity
agents such as chelating ligands, which form stable but to rotate plane-polarized light, which has since led to the
volatile species with the analyte of interest. Spectral in- development of a number of techniques suitable for quali-
terferences can also occur, though direct overlap of inter- tative structural determination and quantitative concentra-
ferent and analyte atomic absorption bands is rare. These tion analysis. All these techniques are based on the fact that
interferences include molecular band absorption such as electromagnetic radiation has wavelike properties and can
that experienced from the formation of combustion prod- be represented as a combination of electric vectors. The
ucts, which can often be eliminated by the use of higher electric vector can interact with the electrons of matter
temperatures, and ionization of the atomic population due in an absorption–reemission process taking place over a
to excess temperatures. Since many of the chemical pro- time period of 10−14 to 10−15 sec. Even though this pro-
cesses occurring in certain localized areas of the atomic cess does not change the energy of the radiation, a slowing
atmosphere are approximately in equilibrium, such ion- does occur. If a monochromatic beam of radiation passes
ization can be suppressed by the addition of a radiation through an anisotropic solid sample, the electric vectors
buffer, which selectively ionizes in contrast to the ana- that encounter greater particle density will be slowed more
lyte of interest and therefore increases the probability of than the vectors passing through less dense areas. Plane-
ion–electron recombination to form the required atomic polarized light is represented as the resultant of two inter-
population. Table III presents some of the analytes com- fering electric vectors such that the resultant always lies in
monly investigated by the techniques of atomic absorption a single plane. In the case of plane-polarized monochro-
spectroscopy. matic light with two coherent perpendicular electric vector
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Analytical Chemistry 551

components, the components can pass through the sample thickness of ultrathin films. Circularly or elliptically polar-
and be unequally retarded so that the recombination after ized light is reflected from a surface on which the sample
exiting the sample results in constructive interference with is coated. The reflection through the sample alters the po-
a phase difference from that originally observed. This re- larization, and the degree of alteration provides thickness
sults in a rotation of the plane of polarization and propaga- data to 0.1-nm precision. These instruments have wide ap-
tion of circularly or elliptically polarized light dependent, plicability in the semiconductor industry and as tools for
respectively, on phase separations of multiplies of 0, 14 , 12 , the measurement of organic films of monolayer dimen-
or combinations of these numbers. sions.
Polarimetry is a technique suitable for structural de-
termination and quantitative analysis and simply studies Ultraviolet–visible. This form of electromagnetic
the direction and degree of the rotation of plane-polarized radiation is of sufficient energy to cause electronic ab-
monochromatic radiation of transparent substances. In- sorption transitions from the ground state to an excited
struments generally make use of vapor lamps, which iso- state within molecules. In contrast to sharp atomic elec-
late the sodium D line or mercury line at 546 nm. The light tronic absorptions, molecular spectra show broad bands
is then processed by a Nicol polarizer prism assembly, covering tens of nanometers due to the availability of a
passed through a half-shadow Lippich prism (to assist de- multitude of distinct energy states caused by the overlap
tection of the optical minimum intensity), passed through of the vibrational and rotational energy sublevels with the
a thermostated transparent sample holder, passed through primary electronic level. Only high-resolution spectrom-
a second Nicol prism known as the analyzer, and directed eters can clearly resolve these energy levels.
to an eyepiece or photoelectric detector. Rotation of the The design of a typical double-beam instrument that al-
analyzer allows matching of the split-field bright image. lows for relative background correction is schematically
The instrument is calibrated by analyzing the rotation of shown in Fig. 6 and consists of a radiant source, such as
a standard solution of known concentration and rotatory a hydrogen–deuterium lamp for ultraviolet and a tung-
power and provides precision to 0.001◦ when coupled to sten lamp for visible radiations; a filter, prism, or grating
photoelectric detectors. monochromator for wavelength selection; sample and ref-
Other techniques that find widespread application are erence cells; and a photocathode, usually associated with
optical rotatory dispersion and circular dichroism. These a photomultiplier for detection.
are closely related methods that rely on the wavelength The most important types of electronic transition in-
dependence of refractive index and molar absorptivity, re- volve the following:
spectively, toward the direction (d or l ) of circularly po-
larized radiation. Optical rotatory dispersion experiments 1. n, σ , and π electrons, covalent compounds
provide a measurement of molecular rotations as a func- 2. Charge-transfer electrons
tion of wavelength. Circular dichroism results are pre- 3. Electrons, ligand field strength
sented in a plot of wavelength vs a value [θ ], and [θ ] is 4. f electrons, lanthanide and actinide ions
a corrected value of θ, the molecular ellipticity measured
as the singular difference between the emergent ellipti- Of particular importance are those transitions involving
cal beam and the original incident plane of polarization. bonding electrons, since particular absorption energies are
These techniques have been important tools in the elucida- characteristic of the bonding of certain functional groups,
tion of structural information about complex organic and known as chromophores, providing chemical identifica-
biological systems and metal–ligand complexes. tion and concentration information. A summary of approx-
The use of elliptically polarized light has also found imate electronic energy transitions for bonding and non-
application in the determination of refractive index and bonding electrons is given in Fig. 7. This can be correlated

FIGURE 6 Conventional double-beam ultraviolet–visible absorption spectrophotometer.


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552 Analytical Chemistry

FIGURE 7 Electronic transitions for n, σ , and π electrons caused


by ultraviolet–visible energy absorption.

with the wavelength for maximum absorption of some


typical chromophores listed in Table IV. Molecular struc-
tural information can occasionally be garnered from wave-
length shifts for particular chromophores when they are af-
fected by conjugation or by structural distortion. Although
all covalently bonded electrons can be excited to higher FIGURE 8 Differential absorption methods for quantitative con-
energy levels, the energy associated with single-bond tran- centration analysis. (a) High-absorbance method: A, optical shut-
sitions lies in the vacuum ultraviolet range, which because ter; B, low-transmission reference solution. (b) Low-absorbance
of technical difficulty is usually not exploited. This im- method: A, pure solvent; high-transmission reference solution. (c)
Ultimate precision method: A, B, reference solutions; S, sample.
plies that analyses of unsaturated species and aromatic
compounds are by far the most prevalent.
Due to the broadband nature of the electronic absorp- Infrared. It can be seen from Fig. 4 that infrared
tions, this technique is poor for qualitative information radiation is of an energy suitable for the stimulation of vi-
acquisition but is excellent for accurate quantitative anal- brational absorption that occurs within a single electronic
ysis. Three differential absorption methods are employed level. For gas-phase samples, vibrational bands can be
to maximize the accuracy of the analysis, with the choice divided into a series of closely spaced absorptions asso-
being dependent on the concentration of the absorbing ciated with molecular rotational energy levels; however,
species and the availability of appropriate calibration stan- these are not usually observed. Even so, the infrared ab-
dards. The three methods are outlined in Fig. 8. sorption spectrum for most solid and liquid samples is
complex and contains many sharp maxima and minima
TABLE IV Absorption Characteristics of Common associated with well-defined vibrational energy levels.
Ultraviolet–Visible Chromophores Vibration consists of the periodic fluctuation of atoms
Unconjugated
with respect to relative position, but not all such position
chromophore (n→π ∗ Approximate Approximate changes are associated with radiation absorption. Only
transitions) Solvent λmax (nm)a εmax when a net molecular dipole change is associated with
vibrational or rotational motion can the alternating electric
Aldehyde n-Hexane 293 12 field of the radiation interact with the matter. Absorption
Alkyne n-Heptane 225 160 then leads to a resonant vibrational or rotational amplitude
Amideb Vapor phase 215 600 increase.
Amido Water 214 60 All vibrations can be classified into the two major
Carboxyl Ethanol 204 41 categories of stretching, where bond lengths alternate,
Ketone n-Hexane 280 16 or bending, where angular changes occur between two
Nitrate Dioxane 270 12 bonds. Theoretically and generally, the vibrational modes,
Nitro Isooctane 280 22 amplitudes, and energies can be approximated by classical
a Considering only conventional instruments scanning λ greater than and quantum mechanical treatments of a harmonic oscil-
200 nm. lator at low potential energies. Given that the description
b Amide absorption at this λ ∗
max due to n → σ transition. of any atom in space requires the use of three coordinates
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Analytical Chemistry 553

and 750 cm−1 , which is often called the “fingerprint” re-


gion. Such analyses can be applied to solid-, liquid-, and
gas-phase samples, and a summary of some common ab-
sorption bands useful for chemical identification purposes
is provided in Table V.

Electron spin resonance. In a strong magnetic


field, the degenerate energy levels designated by the elec-
tron spin quantum number ± 12 actually differ in energy.
The difference in energy between these levels is described
FIGURE 9 Conventional double-beam infrared absorption
as E,
spectrophotometer.
E = µβN H0 /I,
where µ is the magnetic moment, βN the Bohr magne-
to locate position and a molecule contains N atoms, then
ton, H0 the external magnetic field strength, and I the
3N coordinates, or “degrees of freedom,” are required to
quantum spin number. The difference in energies between
describe the molecule. Since molecular motion consists
the two distinct states can be equal to that of a photon
of translation, vibration, and rotation and three coordi-
in the microwave region of the electromagnetic spec-
nates are required to describe translation and also rotation,
trum and, for a conventional magnetic field strength of
3N − 6 degrees of freedom remain to describe the num-
3400 G, represents a frequency of 9500 MHz. It is possi-
ber of possible “normal” modes of vibration. The number
ble for energy absorption to occur, promoting an electron
of normal modes of vibration does not necessarily corre-
from the low-energy state to the high-energy state by cap-
spond to the total number of observed vibrational absorp-
ture of photons in the microwave region. The majority of
tions, since some extra vibrational signals can be gained
molecules do not exhibit an absorption spectrum since all
from overtone and combination frequencies, while some
electrons are paired and equal numbers exist in the two
can be lost by being dipole inactive, being outside the in-
spin states. Paramagnetic molecules such as free radicals
strumental analysis range, by overlap, or by having too
are strongly influenced by magnetic fields. The associated
low an intensity.
splitting of energy levels is very evident from the pres-
The design of a typical double-beam infrared spec-
ence of absorption bands, which may be complicated by
trophotometer is schematically illustrated in Fig. 9. Typ-
hyperfine splitting caused by electron spin–nuclear spin
ically, the broadband source consists of a metal wire or
coupling.
ceramic tube heated to incandescence by passage of an
A typical electron spin resonance instrument consists of
electric current. The radiation is first divided into two
a microwave source, known as a klystron tube, which by
beams, which are directed through the sample and refer-
ence cells. A chopper mechanism placed behind the cells
alternately selects transmission of either the sample or ref-
erence beam to the grating monochromator and thermal TABLE V Infrared Absorptions of Common Chromophores
detector. This sets up an alternating current (ac) output Wavelength Vibration
from the detector, which is passed to a synchronous recti- Chromophore range (µm) mode and intensity
fier. A comparison of beam power occurs via the rectifier,
Alcohols 3.1–2.7 O—H stretch (strong)
which is produces a continuous unfluctuating direct cur-
Amines 3.3–2.8 N—H stretch (medium)
rent (dc) if the beams are identical. If the beam powers
C H 3.8–3.0 C—H stretch (strong)
differ, an ac current is output from the rectifier, and after
Cyanides 4.7–4.4 C N stretch (medium)
further amplification, this output signal is used to drive
Alkynes 5.1–4.6 C C stretch (weak)
a synchronous motor. The motor concurrently drives a
Carbonyls 6.5–5.5 C O stretch (strong)
recording pen and an attenuator, until the attenuator causes
Alkenes 6.4–5.9 C C stretch (variable)
the two beams to be of equal power and a signal null is
N O 6.8–6.1 N O stretch (strong)
achieved.
Amides 8.4–6.0 N—H deformation (medium)
Though numerous instruments and measurement meth-
Esters 8.6–7.6 RCOOR (variable)
ods have been devised for quantitative work, the large
Alcohols 10.0–8.5 C—OH stretch (strong)
number and narrow characteristics of infrared absorption
C Cl 15.4–12.5 C—Cl stretch (strong)
bands make them more suitable for qualitative identifica-
C Br 17.9–13.3 C—Br stretch (strong)
tion. This is especially true of the region between 2000
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554 Analytical Chemistry

means of a metallic waveguide transmits the electromag- TABLE VI Common Nuclear Magnetic Resonance Nuclei of
netic radiation to a quartz tube sample holder positioned Quantum Spin 12
between the poles of a permanent magnet. The experi- NMR frequency Natural Relative sensitivity
ment consists of varying the magnetic field strength by Isotope (MHz) at 20 kG abundance (%) per nucleus
means of secondary coils to induce resonance. The result- 1H 85.2 99.98 1.000
ing absorption signal is usually processed and outputed 2H 90.8 0.02 1.21
as a first-derivative curve to increase sensitivity and res- 13 C 21.4 1.11 1.59 × 10−2
olution. Though the technique does not have wide ap- 15 N 8.6 0.37 1.04 × 10−3
plicability, it continues to play an important role in the 19 F 80.1 100 0.834
probing of biological systems for order, viscosity, reactiv- 31 P 34.5 100 6.64 × 10−2
ity with spin-label reagents (since absorption is influenced 195 Pt 18.3 33.7 9.94 × 10−3
by chemical environment), and investigation of chemical
reactions, which include free-radical intermediates.

would equal net emission and no absorption could be ob-


3. Nuclear Absorption
served. Radiationless relaxation processes from high- to
Nuclear magnetic resonance. Certain atomic nu- low-energy states are therefore of fundamental importance
clei have properties of spin and magnetic moment that for the maintenance of an absorption signal. Furthermore,
cause their energies to split into quantized levels when such relaxation mechanisms are dependent on the nuclear
subjected to a powerful magnetic field. Transitions from environment and proximity to other nuclei, so that relax-
a lower energy level to a higher level can be induced by ation rates can provide chemical data.
absorption of electromagnetic radiation in the radiofre- There are two distinct types of relaxation processes.
quency range of 0.1–100 MHz. Such absorption can oc- One is known as spin–lattice or longitudinal relaxation
cur only when the energy provided is equivalent to the en- and results from the interaction of absorbing nuclei with
ergy difference between two magnetically induced states the rest of the sample (lattice), which in the standard liq-
and satisfies the resonance condition. The experiment uid phase is in vigorous vibrational and rotational motion.
that measures the frequencies that satisfy the absorption Due to the large number of random magnetic components
process is known as nuclear magnetic resonance spec- offered by the lattice, there exists a good probability that
troscopy. This technique is related to electron spin reso- the phase and frequency of some of the lattice nuclei match
nance, which has been described previously. the precessional frequency of the high-spin-state nuclei so
For a nucleus of spin quantum number I, a total of 2I + 1 that energy exchange can take place. The spin–lattice re-
discrete energy states exist in a magnetic field. If u repre- laxation time T1 is defined as a measure of the average
sents the magnetic dipole caused by the spin of the charged lifetime of nuclei in the higher energy state. This lifetime
nucleus, the energy difference E between states can be is a function of the lattice mobility and can be used to probe
written generally as microstructures and viscosities. The availability of a para-
magnetic molecule or ion in the lattice provides a strong
E = µβ H0 /I,
fluctuating magnetic field source, which can substantially
where H0 is the magnetic field strength and β is a constant shorten T1 . The second relaxation process is known as
called the nuclear magneton. A term that is characteristic spin–spin or transverse relaxation and is denoted as a value
of a nucleus is known as the magnetogyric ratio γ , T2 . This value is actually a sum of a number of distinct
processes that increase absorption bandwidth by decreas-
γ = µβ/I (h/2π),
ing T2 . Some of these processes include energy transfer
where h is Planck’s constant. This value can be used di- between closely spaced-identical nuclei that exist in high-
rectly to relate the frequency of absorbed radiation v to and low-energy states, so that the lifetime in any one state
the magnetic field strength by the relation is shortened, and also the effects of other magnetic nuclei
whose spins create local magnetic fields, which align with
v = γ H0 /2π,
or against the permanent externally applied field so that a
Some nuclei commonly observed by nuclear magnetic res- range of absorption frequencies exist.
onance are listed with their important physical constants Chemical information can also be derived from the posi-
in Table VI. The difference in the population of nuclei tion of absorption signals measured on an energy basis and
between energy states is usually very small, with lower the fine structure of such absorption signals. The position
states being occupied by only a few excess nuclei per mil- of absorption bands is referred to as the chemical shift and
lion. If the states were equally populated, net absorption is measured relative to a standard substance. The effect is
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Analytical Chemistry 555

due to electrons that circulate in the molecule contain- higher, the resolution of the instrument improves, and
ing the absorbing nucleus. Circulation of charge creates a 600-MHz instruments for proton studies are now avail-
magnetic field, which can reduce or enhance the applied able. A pair of secondary field coils are located paral-
field in a local area so that lel to the high-power magnet faces for the adjustment of
field strength over small ranges. A radiofrequency source
H0 = HA (1 − σ ),
consisting of oscillator coils is mounted perpendicular to
where H0 is the resultant field and is equal to the origi- the magnetic field direction and provides plane-polarized
nal applied field HA corrected for the shielding parameter radiation. The signal produced by nuclei in resonance
σ . A compound is chosen as a standard for calibration is detected by another coil surrounding the sample and
if its shielding value is larger than the values commonly mounted perpendicularly to the radiofrequency source
associated with the nuclei of interest (e.g., tetramethylsi- coil. Samples are usually in liquid form and are placed
lane for proton magnetic resonance studies). Correlation in a narrow glass tube, which is rapidly spun to elimi-
of the chemical shift with structure can provide useful nate the effects of field inhomogeneities. Analysis of solid
group identification. Chemical shift values for protons are samples is possible when a special arrangement is avail-
the most common and are often referred to on a δ or τ scale, able to orient and rapidly spin the sample (>2 kHz) at a
“magic angle” in relation to the magnetic field. This an-
Href − Hsample × 106 gle of 54.7◦ is dictated by geometrical constraints. The
δ∼
=
Href use of Fourier transform methods (see Section III.A.3)
τ = 10 − δ, has provided a means of amplifying the nuclear mag-
netic resonance signal so that many insensitive nuclei are
where Href and Hsample are the field strengths required to now routinely investigated, as shown in Table VI. Samples
produce tetramethylsilane and sample resonance, respec- are irradiated with a broad radiofrequency spectrum for a
tively. A summary of some common proton chemical short period of time. After this pulse of energy is applied,
shift values is given in Table VII. Additional information the excited nuclei relax to the lower energy states, pro-
can be garnered from the fine structure of absorption viding a time-based free induction decay spectrum. This
bands, which is known as spin–spin splitting. This occurs spectrum represents the overlap of the different resonant
when the field about one nucleus is affected by the fields frequencies, producing a characteristic envelope of time-
from neighboring nuclei attached to an adjacent atom. dependent oscillations. The time-domain spectrum can be
The degree of splitting reported as frequency differences collected in seconds, allowing experiment replication to
and the relative areas under each separate absorption occur hundreds of times in a practical time period. These
signal can, therefore, provide quantitative information spectra can be collected and averaged by computers to
about the chemical environment. provide a tremendous signal-to-noise enhancement and
Instrumentation incorporates a high-strength, high- are finally displayed as conventional frequency-domain
quality magnet, which may be permanent, electrically in- spectra. Modern techniques now allow two-dimensional
duced, or superconducting. As the field strength becomes analysis where excitation scans across different frequency
ranges are concurrently analyzed to provide information
about coupling between nuclei.
TABLE VII Correlation of Common Proton Chemical Shifts

Group δ Scale τ Scale Nuclear γ -ray resonance spectroscopy. This


technique is based on the resonance absorption of γ ra-
Tetramethylsilane 0 10.00
diation and is more conventionally known as Mössbauer
H3 C C (saturated) 1.3–0.7 8.7–9.3
spectroscopy. The source of the radiation is a nuclide fixed
CH2 (saturated) 1.5–1.2 8.5–8.8
in a solid crystal lattice held below the Debye tempera-
H3 C C C 1.9–1.6 8.1–8.4
ture. In this condition, γ radiation of energies less than
H2 C C C 2.3–1.8 7.7–8.2
150 keV are emitted with no loss of energy. Such quan-
H3 C Ar 2.5–2.1 7.5–7.9
tized γ photons can undergo resonance absorption by the
H C C (nonconjugated) 2.7–2.4 7.3–7.6
appropriate identical stable nuclide in a solid sample ma-
H C C (conjugated) 3.1–2.8 6.9–7.2
trix. If the chemical environment of the absorbing nu-
H3 C O 4.0–3.3 6.0–6.7
clide is different from the emitter, energy must be added
C CH (cyclic) 5.7–5.2 4.3–4.8
or subtracted from the radiation to establish resonance.
ArH (benzenoid) 8.0–6.6 2.0–3.4
This can be achieved by introducing net motion to the
R CHO 9.8–9.5 0.2–0.5
source or absorber to establish a Doppler motion energy
R COOH 11.5–11.0 −1.5 to −1.0
term.
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556 Analytical Chemistry

Properties of interest for chemical analysis are the so- This technique allows a multitude of species to be de-
called isomer shifts, which represent the displacement of termined concurrently since characteristic lines originate
resonance from zero Doppler velocity, and two types of from all suitable species simultaneously. A schematic rep-
line splitting. Splitting can be induced by interaction of resentation of a simple instrument would be equivalent
the electric field gradient about the nucleus with the elec- to that shown in Fig. 5 if the hollow cathode lamp and
tric moment of the excited nucleus and also by interaction modulation system were removed. A more energetic atom
of the nuclide magnetic dipole moment with internal or source such as an inductively coupled plasma (a zone of
external magnetic fields to produce magnetic hyperfine highly energetic ionized inert gas such as argon, which
structure. Instrumentation is based on the γ -ray source, a provides a high constant operating temperature, a long
Doppler motion device, and an energy-proportional γ -ray sample residence time, and a nonoxidating amosphere) is
detector coupled to a multichannel analyzer. Chemical usually employed. Detection limits are generally in the
information extracted from Mössbauer spectra indicate range observed for atomic absorption methods, though
oxidation states, sample identity with respect to mineral the two techniques are complementary, each surpassing
structure, and quantitative sample mineral compositions. the other in the analysis of certain species.
The technique is employed most often for iron and cobalt,
though over 50 nuclides have demonstrated the Mössbauer Atomic fluorescence spectroscopy. Fluorescence
effect. refers to a process whereby absorption and reemission
of radiation are separated temporally. A pulsed source
of high intensity such as a laser, electrodeless discharge
B. Emission of Electromagnetic Radiation
lamp, gaseous discharge lamp, or specially adapted hol-
Matter can exist in a physically excited energy level and low cathode lamp at the required resonant frequency is
can relax to a lower ground state energy by releasing the used to irradiate an atomic population created usually by
difference in energy. One mechanism of such relaxation a nonflame method. Emission can occur in any direction
can occur by emission of electromagnetic radiation. Con- and is commonly observed by standard atomic absorption
tinuous broadband radiation is observed from a thermally instrumentation set at an angle of 90◦ to the high-intensity
excited continuous solid and results from the complicated source beam. This arrangement has been shown to im-
oscillations originating from the molecules and atoms of prove detection limits over those for atomic absorption or
the sample. If these molecules or atoms emit indepen- emission for up to 10 elements.
dently, then a discontinuous spectrum composed of dis-
tinct bands or lines can be observed. The structure of this X-ray fluorescence spectroscopy. This technique
discontinuous emission is related directly to the quantized is one of the most widely used for qualitative and quan-
electronic energy levels of molecules and atoms as dis- titative elemental determination for elements of atomic
cussed previously, and energy is released in a reversal of number greater than 8. A beam of X-rays is directed from
the absorption process. Though this can be strictly true a source such as a Coolidge tube or radioactive substance
for atomic samples, often radiationless decay either elim- to a sample. Figure 4 indicates that such radiation is suf-
inates or precedes radiative emission from molecular sam- ficient for ionization of the core electronic level in atoms
ples and provides interesting chemical information. of the sample. The process of absorption of X-rays can be
used to provide structural information about atomic po-
sitions in three-dimensional space by a technique known
1. Atomic Emission
as Extended X-ray Absorption Fine Structure (EXAFS).
Emission spectroscopy. Atomic or ionic popula- Relaxation of such excited elements occurs by the shifting
tions can be prepared by the use of high-energy sources of an electron from a higher energy level to fill the elec-
such as flames, electrical discharges, and plasmas. If the tronic vacancy. The difference in energy between the two
energy in these sources is sufficient, electronic excitation electronic levels is released as quantized fluorescence in
occurs by collision processes, and relaxation can take the the X-ray region of the electromagnetic spectrum. A large
form of discrete narrow line emission. Since the wave- number of different X-ray energies can be emitted from a
lengths of such emissions reflect the energy differences single sample simultaneously, necessitating the employ-
in the quantized electronic energy level distributions, the ment of wavelength- and/or energy-dispersive devices in
emission wavelengths are characteristic of the excited el- many cases. Wavelength dispersion is accomplished in a
ement and can be used for identification purposes. The manner analogous to that for grating monochromators,
intensity of emitted lines can be used for quantitative but in this case a collimated beam of fluorescent X-rays
analysis by comparison with calibration standard signals is allowed to impinge on a solid crystal of well-defined
recorded on film or collected by photoelectric detectors. lattice spacing d (e.g., lithium fluoride, sodium chloride,
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Analytical Chemistry 557

FIGURE 10 Schematic representation of an X-ray fluorescence spectrometer employing both wavelength dispersion
and energy dispersion.

topaz) mounted on a goniometer to satisfy Bragg’s nant effect between an incoming photon and the electrons
law, of a chromophore, elevating the valence electronic con-
figuration to a higher energy state. Fluorescence is said to
nλ = 2d sin θ,
occur when the system relaxes to a lower energy state by
where n is an integer, λ is the wavelength, and θ is the the release of radiation within 10−8 sec after absorption
angle at which constructive interference occurs. Energy- in a process that ceases in less than 10−6 sec. Resonance
dispersive systems (see Section II.B.3.b) employing pulse fluorescence occurs when the absorbed radiation is reemit-
height analysis can be used in conjunction with wave- ted at the same wavelength. Polyatomic molecules often
length dispersion to distinguish between two or more en- reemit at wavelengths longer than those absorbed, produc-
ergies of photons appearing at one angle due to differ- ing a spectral feature known as a Stokes shift. This is due
ent values of n, or a multichannel analyzer for discrete to nonradiative energy losses by molecular vibration in the
energy measurement can be independently employed. A electronically excited state. The closely related processes
schematic representation of a combined wavelength- and of fluorescence and phosphorescence are summarized in
energy-dispersive system is shown in Fig. 10. Fig. 11. Phosphorescence occurs from a forbidden excited
triplet state after inter-system crossing and may take a pe-
riod of seconds. This phenomenon is often of very weak
2. Molecular Emission
intensity and is not as common as fluorescence, thereby
Fluorescence spectroscopy. Molecular absorp- limiting its analytical potential. Competition between non-
tion of ultraviolet or visible radiation results from a reso- radiative and fluorescent energy loss occurs, reducing the

FIGURE 11 Energies of fluorescence and phosphorescence processes.


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558 Analytical Chemistry

quantum yield, which represents the ratio of energy re-


leased by radiative processes compared with total energy
absorption. Ideally, the quantum yield would have a value
of unity, but molecular interactions such as intermolec-
ular collisions or intramolecular rotations in the sample
matrix can reduce this dramatically. The fluorescent in-
tensity F is therefore a function of the chemical structure
of chromophores and molecular interactions and, for di-
lute solutions with A < 0.05, can be written as
F = 2.3K A P0 ,
where K is dependent on the quantum yield, A is ab-
sorbance, and P0 is the incident radiation power. The in-
strumental components of a spectrofluorimeter are very
similar to those for the molecular absorbance technique
described previously. Observation of fluorescence occurs FIGURE 12 Energetics of the Raman process.
at 90◦ to the angle of source illumination, and an emission
monochromator may precede the detector. These instru- shifts from the source line and include both Stokes and
ments are inherently more sensitive than those based on the generally weaker anti-Stokes lines. These lines rep-
absorbance since at low sample concentrations it is much resent infrared absorption as well as active and inactive
easier to amplify electronically a small radiant signal su- transitions and can be correlated with the latter technique
perimposed on a dark background than measure a small to distinguish between vibrational frequencies related to
difference in intensity due to absorption measured on a dipole moments and induced distortions of electrons from
bright background. These systems can have one to four or- their usual locations in bonds.
ders of magnitude better sensitivities than corresponding The instrumentation used for modern Raman spec-
absorption techniques, though limitations of applicability troscopy consists of an intense source of optical or ul-
occur since many chromophores do not undergo fluores- traviolet radiation, a system for sample illumination, and
cent relaxation. For absorption wavelengths of 250 nm a monochromator-based spectrophotometric system using
or greater, fluorimetry is the method of choice for direct standard photomultiplier detection. The incident light path
molecular quantitation at low concentrations. The tech- is usually perpendicular to the direction of detection, as in
nique has found great application in organic chemistry, the spectrofluorimetric instruments previously described.
natural product chemistry, and fluorimetric reagent anal- Resolution to 0.2 cm−1 is possible with the best instru-
ysis. ments, and the Raman signal is directly proportional to
concentration of the active species. Signal intensity in the
Raman spectroscopy. The Raman effect is based absence of absorption is proportional to the fourth power
on the molecular scattering of incident electromagnetic ra- of the source frequency, though wavelengths shorter than
diation in the ultraviolet or visible wavelength range. The 450 nm are not usually employed because of rapid sample
scattered radiation is quantized due to the interaction with decomposition caused by intense energetic radiation. A
molecular vibrational levels, and therefore, the difference large variety of surfaces can be studied by use of Surface-
between the incident beam energy and scattered radia- Enhanced Raman Spectroscopy (SERS). Local electro-
tion falls within the infrared range. These differences in magnetic effects on certain roughened conductive surfaces
wavelength are dependent on molecular polarization, as (e.g., Ag, Au, Cu) enhance the Raman signal by factors
opposed to the dipole moment changes associated with up to 106 by increasing the incident power at the surface
infrared absorption spectroscopy, making the two tech- and increasing the Raman scattering cross section, making
niques complementary for structure determination. Spec- detection and spectral characterization of even submono-
tral analysis shows vibrational bands at values both above layer coverage straightforward.
and below the wavelength of the monochromatic radiation
used for sample irradiation as governed by the physical
3. Nuclear Emission
processes shown in Fig. 12. Energy is absorbed to promote
a molecule to a quasi-excited state characterized by a dis- Activation analysis. This technique is based on the
torted polarized species. Relaxation occurs after 10−15 to measurement of the radioactivity of a sample after activ-
10−14 sec to the ground state or one of the higher vibra- ity has been induced by irradiation with nuclear particles,
tional levels. Spectra are usually plotted as wave number such as thermal neutrons, or highly energetic γ - or X-rays.
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Analytical Chemistry 559

Four major distinctions can be made between methods of C. Separation Science


activation analysis. They include the type of radiation or
Separation science is a very broad term covering all tech-
particle bombardment used for sample excitation, the type
niques that employ chemical and/or physical methods to
of radiation observed in the final emission process, sample
isolate one or more species from some mixture. These
preparation by isolation of the species of interest, or di-
methods include solvent extraction, distillation, selective
rect sample observation without separation by an energy-
precipitation, crystallization, and chromatography.
discriminating device such as a γ -ray spectrometer.
Neutron activation analysis is the most common tech-
nique employed today, and the activity A induced in a
1. Principles of Chromatography
sample can be related to neutron flux φ and sample half-
life t1/2 as follows: Chromatography is a very specialized, yet widely appli-
cable technique of separation science by which one can
A = N σ φ[1 − exp(−0.693t/t1/2 )], effectively separate chemically similar substances in com-
plex mixtures. There are three distinct physical methods
for attaining separation, yet all are characterized by their
where N is the number of sample nuclei, σ is their neu- common application of a stationary and a mobile phase.
tron capture cross section, and t is the time of sample The stationary phase provides the chemical surface, which
irradiation. From this equation, it can be seen that, after a interacts with the components of the mixture to be sepa-
particular irradiation time, the activity reaches a saturation rated. The difference in the chemistry of these compo-
level where the rate of formation and decay of the active nents results in various degrees of molecular bonding or
species becomes equivalent. At any one neutron flux, the entrapment to the stationary phase. If the mixture is carried
saturation is determined by the characteristic half-life of across a bed of stationary phase by some mobile phase,
the sample, which consequently establishes the analysis the molecules experiencing the least interaction with the
time required to attain maximum sensitivity. stationary phase will tend to advance more quickly than
The most significant analytical feature offered by acti- those retained on the bed by stronger molecular interac-
vation analysis is its inherent sensitivity, which is suitable tions. This results in the separation of similar species as
for trace analysis to values as small as 10−12 g for some influenced by differences in migration rates across the sta-
species. However, such sensitivities are attainable for only tionary bed. The three distinct separation strategies are
some elements, whereas others may require a total mass summarized below and all assume a common stationary
of 10−4 g before being detectable. phase.

γ -Ray spectroscopy. The ability to measure pho-


ton energy accurately at this part of the electromagnetic 1. Frontal chromatography. The mobile phase is the
spectrum is used to great advantage in the identification, sample mixture, and as the sample migrates down the sepa-
discrimination, and quantification of both natural or in- ration bed, the least retained species are concentrated near
duced radioactive species. The principle of operation can the leading edge.
be considered as proceeding in three phases. An energetic 2. Displacement chromatography. A sample mixture is
photon interacts with a scintillation crystal–photocathode applied to one end of a stationary phase, and then a mobile
arrangement or a semiconductor material as the first step phase is introduced. The mobile phase selectively binds
in transduction to an electric signal. This electric signal to the stationary phase competing for the same binding
is amplified by conventional electronics so that the output sites as the sample. Separation is established as a relative
signal energy is proportional to that of the original photon. function of the intermolecular interactions of the sample
The second phase involves analysis of the energy of the and mobile-phase species with the stationary phase.
output signal so that it can be sorted with respect to a pre- 3. Elution chromatography. A sample mixture is ap-
assigned energy resolution into a defined energy level, or plied to one end of a stationary phase, which may already
“channel.” The last phase involves counting and display contain mobile phase. The mobile phase does not inter-
of the signals in any one channel for quantitative anal- act significantly with the stationary phase and only carries
ysis. Both multichannel and single-channel instruments the sample mixture through the stationary bed. The differ-
exist and are selected according to cost and flexibility. ences in selective binding of sample mixture components
Multichannel systems can monitor hundreds of discrete with the stationary phase retards migration of some species
wavelengths simultaneously and are commonly used for so that separation occurs. This is the most analytically use-
multielement analysis in conjunction with techniques such ful form of chromatography due to its tremendous power
as neutron activation analysis. of separation of very similar species.
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560 Analytical Chemistry

Stationary phases can be solid surfaces or surfaces rate at which equilibrium is attained include the volume
coated with liquids, while mobile phases can be liquids or and average thickness of the liquid stationary phase and
gases. Standard forms that stationary phases take are often diffusion coefficients and relative equilibrium concentra-
very fine granular powders spread evenly on planar glass tion ratios of the mobile and stationary phases.
or polymer supports (e.g., thin-layer chromatography) or A feature of fundamental interest for any chromato-
packed in columns. Also common are porous polymeric graphic work is the resolution or separation capability of
solids usually containing a microcoating of water (liquid the technique. One equation useful for quantitative mea-
stationary phase) or capillary tubes whose inside walls are surement of resolution R can be written
coated with a liquid stationary phase.
The theory of chromatography has been reasonably well R = 2 Z /(W1 + W2 ),
established with a “kinetic” or “rate” theory that describes
where W1 and W2 represent the base width of two different
the broadening of the bands or zones of separated com-
peaks in a separation and Z represents the difference in
ponents on a stationary-phase bed, describes their time
elution of the maxima of the two peaks.
of appearance at any particular point, and provides de-
tails of the separation power or resolution of the particular
system employed. Numerous equations describing zone 2. Gas Chromatography
broadening have been proposed, the simplest being the
general form of the van Deemter equation as derived for This technique is one of the cornerstones of chromato-
gas–liquid chromatography, graphic analysis, being suitable for the separation of very
complex organic and inorganic gas samples. The mobile
H = A + B/V + Cv, phase is a carrier gas chosen to maximize separation ef-
where A, B, C represent three kinetically controlled pro- ficiency as per the van Deemter equation, while concur-
cesses known as eddy diffusion, longitudinal diffusion, rently maximizing the sensitivity of the detector. The sta-
and nonequilibrium mass transfer, respectively. The term tionary phase is either a solid or a viscous organic liquid
v represents the mobile-phase flow rate, and H is defined coated on a solid support (hundreds available) or an open
as the height equivalent of a theoretical plate. This ter- tubular capillary column (for very high efficiency separa-
minology derives from the plate theory of distillations, tions).
where a distillation tower can be divided into a number of A schematic representation of a gas chromatograph is
equilibria steps or plates. In the chromatographic sense, shown in Fig. 13, and it indicates that the sample is first
the height equivalent of such a step represents simply the vaporized by injection into a heated port, then passed
length L of the separation bed divided by the number of through a heated separation column, and finally detected.
steps in the separation bed N (determined from efficiency The small sample size that can be passed by capillary
of separation): columns usually necessitates supplementation of special-
ized splitters at the injection port. A splitter accurately and
H = L/N , reproducibly reduces the volume of sample that enters the
The three kinetically controlled factors responsible for column from standard sample injections done by syringe.
zone broadening can be readily analyzed to improve sep- Numerous detection devices exist, and the most common
aration efficiency, which is equivalent to minimizing the are summarized in Table VIII. Separation times of vari-
value of H . Eddy diffusion refers to the torturous path ous species eluting from the column are often controlled
that sample species must take through a packed particle by varying column temperature by a technique known as
stationary-phase bed. The distance traveled by different temperature programming.
molecules as they migrate across the bed must vary since
different paths are highly probable. This results in zone
broadening and is critically dependent on average particle
diameter and size distribution. Longitudinal broadening
refers to the natural diffusion of molecules from a concen-
trated band toward areas of lower concentration on either
side. The most important parameters are those that con-
trol molecular diffusion rates in the stationary phase and
in the mobile phase. Nonequilibrium mass transfer recog-
nizes the fact the mobile phase may move too quickly to
allow concentration equilibrium to be established between FIGURE 13 Schematic representation of a single-column gas
the mobile and stationary phases. Factors that control the chromatograph.
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Analytical Chemistry 561

TABLE VIII Summary of Common Gas Chromatographic TABLE IX Summary of Common High-Performance Liquid
Detector Characteristics Chromatographic Detector Characteristics

Limit of detection Limit of detection


Detector type Selectivity (g sec−1 ) Detector type Selectivity (g ml−1 )

Thermal conductivity None 10−9 Refractive index None 5 × 10−7


Flame ionization Combustibles 10−12 Ultraviolet–visible Chromophore-containing 5 × 10−10
Flame photometric Sulfur, phosphorus 10−12 absorption species
species Fluorescence Fluorophore-containing 10−10
Electron capture Halogenated species 10−13 species
Photoionization None 10−14 Amperometric Electroactive functional 10−12
groups
Conductivity Ionized species 10−8

3. High-Performance Liquid Chromatography


This form of chromatography is very well suited for sep- stationary phases for general laboratory glass column sep-
arations of organic mixtures and often complements gas arations. However, a tremendous advance in this technol-
chromatography, since many organic species cannot be ogy has occurred since the mid-1970s, resulting in the evo-
volatilized readily. Separation efficiency can be similar to lution of high-performance ion chromatographs capable of
that obtained from packed column gas chromatography concurrent separation of monovalent and multivalent inor-
and is usually achieved on an extremely thin stationary ganic and organic ions in periods of minutes. A schematic
phase coated onto small solid particles of micrometer di- diagram of such an instrument is shown in Fig. 15. The in-
ameter. The small size and high degree of regularity of novations of this instrument lie in the development of new
the packing material provide great resistance to solution separation column resins of high efficiency and the devel-
flow, thereby necessitating use of high pressure to force opment of countercurrent fiber-based suppressor columns
the mobile phase through a column. The technique has that eliminate all but analyte ions from the mobile phase.
greater flexibility than gas chromatography since the mo- The elimination of all ions other than the analyte ions is ac-
bile phase can be easily changed with dramatic effects on complished by use of a semipermeable membrane which
resolution. A schematic of such a chromatographic system can only pass ions of one type of charge. A suppressor
is shown in Fig. 14, illustrating the use of fluids as the mo- solution is maintained on the outside of the membrane
bile phase. Solvent programming refers to mobile-phase and functions by exchanging ions with the mobile phase,
solvent changes during the course of one chromatographic maintaining charge balance and resulting in conversion of
elution and in some respects is similar to temperature pro- ions to nonconductive soluble compounds. For example,
gramming. A summary of common detectors is provided sodium ions of 2Na+ /CO2− 3 in the mobile phase can be
in Table IX. exchanged with hydronium ions of 2H3 O+ /SO2− 4 from
the suppressor solution, leaving H2 CO3 as a nonductive
compound in the mobile phase. The conductivity detec-
4. Ion Chromatography
tor senses only the presence of analyte ions without a
Ion chromatography has been known for many years, and large background signal and can therefore provide detec-
ion-exchange resins are perhaps the most commonly used tion limits of 10−10 M concentrations or better.

FIGURE 14 Schematic representation of a solvent-programmed, high-performance liquid chromatograph.


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562 Analytical Chemistry

FIGURE 15 Schematic representation of a high-performance ion chromatograph.

5. Supercritical Fluid Chromatography 6. Chromatographic Methods


in Biochemical Science
Supercritical fluids exist at temperatures and pressures
above the supercritical point of a compound (e.g., where Biochemists address a chemically limited, yet extremely
a gas at STP exists as a fluid). As mobile phases for chro- complex area of organic chemistry. The complexity has re-
matography, supercritical fluids provide properties that are sulted in the evolution of specialized separation techniques
intermediate to liquid and gas chromatography. The sol- suitable for macromolecules that are difficult to determine
vent strength is closely related to density and offers an- by gas and high-performance liquid chromatographic sys-
other operating parameter in the form of pressure–density tems. Though many specialized separation methods are
programming. The low densities and high diffusivities of employed by biochemists, two techniques have found
gases give gas chromatography better resolution per unit of widespread use in many areas of chemistry.
time than liquid or supercritical chromatography, but gas Gel permeation (or size-exclusion) chromatography
chromatography is limited to the analysis of low molecular is a technique based on molecular separation partially
weight, volatile, and thermally stable compounds. High by size rather than chemical interaction with a station-
liquid densities provide liquid chromatography with an ary phase. A water-swollen polymeric gel acts as the
excellent range of solvating power, but this technique is stationary phase and is designed by polymeric cross-
relatively show and is limited by a lack of sensitive univer- linking to contain a certain size distribution of pores
sal detectors. The ability of supercritical fluids to solvate or cavities. As a sample passes through the polymeric
compounds at lower temperatures by controlling the mo- sieve in a water-based mobile phase, smaller molecules
bile phase density makes it possible to readily analyze diffuse into the pores more readily than larger macro-
thermally labile and nonvolatile compounds. The mobile molecules, so that the latter elute first while the progress
phase is pumped as a liquid and heated to above the crit- of the smaller molecules is retarded. The most popu-
ical temperature before passing through the column as a lar polymer for this type of separation is prepared by
supercritical fluid via an injection loop valve. A pressure cross-linking epichlorohydrin with the polysaccharide
restrictor is incorporated after the column to ensure that dextran.
conditions throughout the column remain supercritical. Electrophoresis is a second specialized technique, em-
The technique uses either packed liquid chromatography ploying for analysis the migration of ionic molecules or
columns or open-tubular fused-silica columns, with a va- aggregates in an applied electric field. Commonly, a sta-
riety of nonpolar, polar, or novel chiral-bonded stationary tionary phase such as a water-swollen gel saturated with an
phases. electrolyte is placed between two do high-voltage (hun-
The most commonly used mobile phase in SFC is car- dreds to thousands of volts) electrodes. The sample mi-
bon dioxide (CO2 ) because it has a critical temperature grates through the gel as a function of its charge-to-mass
(Tc ) of 31.05◦ C and a critical pressure (Pc ) of 72.9 atm, ratio, as well as being influenced by all the factors previ-
which are easy to work with; it is nontoxic and non- ously described in Section II.C. Staining of the gel after
flammable; and it is readily available at low cost. Mod- the application of the voltage for a defined time allows vi-
ifiers such as methanol are sometimes added to change sualization of sample species. It is possible to arrange the
solute elution characteristics. instrumentation to use standard high-performance liquid
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Analytical Chemistry 563

chromatographic detectors for sample elution analysis and the oxidized and reduced forms of any species (a ox , ared )
subsequent species collection. by the general form of the Nernst equation,

RT ared
D. Analytical Electrochemistry E = E◦ − ln ,
nF aox
Electroanalytical chemistry includes a broad range of tech-
niques that have as their focus the fact that the analyte par- where E ◦ is the standard electrode potential, R is the molar
ticipates in a galvanic or electrolytic electrochemical cell. gas constant, T is the absolute temperature, n is the charge
All techniques can be classified into one of three major associated with the redox reaction, and F is the faraday.
areas: those that measure electrical properties of the cell,
those that measure cell electrical properties as a function Indicator and reference electrodes. Complete an-
of a chemical reaction in the electrolyte, and those that alytical electrochemical cells are composed of combina-
physically collect the analyte at an electrode for further tions of an indicator and a reference electrode. Each of
analysis. these electrodes contributes half-reaction chemistry; in
combination they provide a complete redox reaction. The
indicator electrode is the analyte activity sensing element
1. Conductimetry
and develops a potential E Ind relative to the reference elec-
When an electrical potential is applied between two elec- trode, which represents a constant known potential E Ref
trodes immersed in an electrolyte solution, ions are accel- independent of the composition of the sample solution.
erated and migrate to electrodes of opposite charge. The The measured cell potential E cell can be written
rate of ion migration is a function of the applied potential
acting as a driving force countered by frictional forces and E cell = E Ind + E Ref + E Junc ,
electrophoretic and relaxation effects in solution. Conduc-
tance is represented as reciprocal resistance and can be where E Junc represents the liquid junction potential origi-
corrected for the cross-sectional area and length of the nating at the interfaces of the electrodes in the sample so-
conduction solution (specific conductance), or it can be lution due to the unequal distribution of ions as a function
stated as the specific conductance of 1 equivalent of so- of their different rates of migration across the interface.
lute (equivalent conductance). A linear relationship exists Ideally, the reference electrode potential is constant, and
between equivalent conductance and the square root of the junction potential is constant or negligible. A number
the concentration of a strong electrolyte. The measure- of reference electrodes are available, the most common
ment of solution conductance is highly sensitive, though being silver/silver chloride, calomel, or hydrogen gas sys-
not selective for any particular species. The device finds tems.
application as a detector for ion chromatographic instru- Indicator electrodes are generally employed for titration
ments, due to its inherent sensitivity. Conductance can be analysis where the cell potential varies as ions are con-
employed as a parameter to follow certain titrations such sumed or produced in a chemical reaction. At least four
as those involving neutralization, precipitation, and com- important types of indicator electrode can be identified.
plexation reactions that consume or generate ionic species. The simplest systems involve a strip of material suitable
The conductance experiment uses an ac source to avoid for the provision or acceptance of electrons, such as gold,
faradaic currents, with oscillation frequencies from 60 to platinum, or carbon, immersed in a solution containing
1000 Hz. A Wheatstone bridge assembly can be used as both the oxidized and reduced forms of some species so
the detection element if the electrochemical cell acts as that a redox potential can be measured. Another situation
one arm of the bridge, though other electronic assemblies involves the use of a metal that is reversible with respect to
are suitable for direct instrumental measurement of con- analyte ions of the metal so that the metal electrode partic-
ductance. The electrochemical cell consists of two large ipates in mass and charge balance rather than only charge
area platinized platinum electrodes placed in fixed orien- balance. A third class of electrodes uses two interfaces, as
tation with defined separation. in the case of the silver/silver chloride reference system,
where the metal is coated with a sparingly soluble salt and
is suitable for titration analysis as well as determination
2. Potentiometry
of the activity of the metal or the anion in the salt coating.
The measurement of the electromotive force between two Another class of electrodes representing a specialized se-
electrodes can provide information about the activity or ries of membrane-based devices designed to monitor the
concentration of an ion in the analyte solution. The poten- activities of certain ions selectively is described in the fol-
tial of any electrode (E) can be related to the activities of lowing two sections.
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564 Analytical Chemistry

an interfering ion of charge Z adjusted for response with a


selectivity factor K 1,2 representing the ratio of selectivity
for ion 1 over ion 2. All selective electrodes suffer from in-
terferences caused by competing species, and these must
be recognized and controlled in any quantitative assay.
It is possible to produce hybrid potentiometric elec-
trodes suitable for the detection and measurement of cer-
tain gases and organic molecules. An ion-selective elec-
trode can be used as a transducer to measure changes in ion
activity caused by enzyme–substrate reactions or dissolu-
tion of gases at small aqueous volumes trapped at the se-
lective electrode surface. For example, an enzyme trapped
in a hydrophilic water-swollen gel can be attached to the
surface of a glass electrode. When placed in a substrate-
containing sample solution, the enzyme–substrate reac-
tion may produce a certain amount of hydronium ion
product, which can be quantitatively detected as a local
FIGURE 16 Construction and hydration properties of an ion- pH alteration by the glass electrode. Further extension of
selective glass electrode. this technology makes use of enzyme-linked immunoas-
say. An antibody that is attached to an enzyme provides
immunochemical selectivity in a competitive binding or
Glass electrodes. Glass electrodes are ion-
sandwich assay strategy, while the enzyme provides the
selective electrodes based on the chemical properties of a
electrochemical signal.
glass membrane of defined chemical composition. Alter-
ation of the glass chemistry to contain variable quantities
of Na2 O, CaO, SiO2 , and Al2 O3 produces chemically 3. Voltammetry and Polarography
active binding sites in the glass that have hydronium,
sodium, or simple cation selectivity. The construction of Voltammetry refers to a broad range of techniques that
a typical electrochemical cell based on a glass electrode compare current–voltage relationships between a work-
is shown in Fig. 16, including a representation of the ing and a reference electrode. The best known of these
physical properties of the sensing membrane. The internal techniques is polarography, which is based on an elec-
solution contains a fixed concentration of the cation of trolytic reduction or oxidation at a microelectrode when
interest and therefore fixes the internal electrode surface the rate of the redox reaction is controlled by analyte dif-
potential, while that in the external solution varies. The fusion to the working electrode surface. Standard work-
electric potential develops only in each hydrated gel ing electrodes are easily polarized microelectrodes such
layer based on an ion-exchange principle that leads to as the mercury drop, rotating platinum, glassy carbon,
a phase boundary potential. The entire glass membrane
is nominally 50–100 µm in thickness, but the hydrated
glass accounts for little of this, being only 5–100 nm TABLE X Common Ion-Selective Electrodes
thick. Conduction within the dry glass is due to the cation Typical
of lowest charge and is not related to penetration by a Membrane type Construction ion selectivity
substantial amount of cations.
Glass Thin, specially formulated H+ , monovalent
glass Group I cations
Ion-selective electrodes. The glass electrode is Solid state Pellets or polymer matrix Cl− , Br− , I− , Cu2+ ,
one example of an ion-selective electrode; three other spe- of insoluble salts Cd2+ , Pb2+
cialized types exist as defined by their membrane con- Single crystal of LaF3 F−
struction. A summary of these is given in Table X. All doped with EuF2
these devices are governed by modifications of the Nernst Liquid ion Hydrophobic charged ion- Ca2+ , Mg2+ , NO−
3,
equation, as shown for the fluoride electrode at 25◦ C, exchange liquid trapped ClO− 4 , Cl

in porous lipophilic
0.059  n/z 
E cell = const − log a1 + K 1,2 a2 , diaphragm
n Neutral carrier Neutral chelating agent in K+ , Na+ , Rb+
where the cell potential E cell is related to a constant in- liquid trapped in porous
cluding internal and external reference electrode poten- diaphragm or supported
in polymer matrix
tials, the activity a1 of the analyte, and the activity a2 of
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Analytical Chemistry 565

and wax-impregnated graphite electrodes. Conventional TABLE XI Common Techniques for Polarographic Analysis
electrochemical cells are designed on the basis of three- Technique Detection limit (M) Resolution (mV)
electrode (working, reference, counter) potentiostatic con-
trol, which allows work in solvents of high resistance. Classical polarography 10−5 200
Polarography applies a continuous or pulsed or oscillat- Rapid-scan polarography 10−7 50
ing potential ramp to the working electrode and observes Cyclic voltammetry 10−7 50
the generation of a redox current as a function of applied Differential pulsed 10−8 50
potential. Three mass transfer processes can control the polarography
rate of analyte deposition at the surface of the working Square wave voltammetry 10−8 50
electrode: convection in the sample solution, migration of Stripping voltammetry 10−10 100
charged ions in the applied electrostatic field, and diffusion
due to a concentration gradient. Experiments are usually
conducted without stirring and in 100-fold concentration lyte diffusion coefficient in square centimeters per second,
excess of an electrochemically inactive electrolyte to elim- C is the analyte concentration in millimoles per liter, m is
inate the first two processes. When the working electrode the rate of mercury mass flow in milligrams per second,
potential reaches a threshold value, dependent on the stan- and t is the drop time in seconds. This equation demon-
dard potential for the half-reaction of interest, oxidation strates that the diffusion-limited current is directly propor-
or reduction of the analyte at the electrode surface be- tional to analyte concentration.
gins. Concentration diffusion begins from bulk solution Numerous procedures for applying electric potential
and eventually reaches a steady state, indicated experi- have been developed to increase the sensitivity of polaro-
mentally as increased but constant redox current (Fig. 17). graphic methods. The most sensitive of these procedures
The potential at the midpoint of the polarographic step is makes use of application of short (millisecond) voltage
known as the half-wave potential E 1/2 and is related to the pulses and sample the current which flows as a func-
applied potential E appl for the half-reaction, the measured tion of the pulse regime. These procedures concentrate
current i, and the diffusion-controlled current id as on maximizing the desired faradaic current while mini-
RT i mizing background signals originating from nonfaradaic
E appl = E 1/2 − log ,
nF id − i processes. A summary of these techniques is presented in
The current, which is diffusion limited, is a function of Table XI to indicate electric potential application methods.
electrode geometry as well as other parameters, as shown The speed of techniques such as square wave voltammetry
in the simple form of the Ilkovic equation for a classical makes such methods preferred for many analytical situa-
dc polarographic experiment using a dropping mercury tions. Polarographic techniques are often used in analyses
electrode, of trace concentrations of toxic metals and are applicable
to almost every element in the periodic table. Analyses of
i d = 607nCD 1/2 m 2/3 t 1/6 , concentration and reaction mechanisms of organic species
where i d is the average diffusion current in microamperes containing certain functional groups are also important.
for each drop, n is the redox electron transfer, D is the ana-
4. Amperometric Titrations
The methods of polarography can be used to follow the
progress of a titration that produces or consumes some
electroactive species. The voltage applied to the work-
ing electrode is constant and sufficient to provide the
diffusion-limited current for the observable analyte. The
current is then recorded as a function of the volume of
titrant added to the sample solution. Since the working
electrode is a microelectrode with an area of only a few
square millimeters, and the current that flows is usually
of the order of microamperes or less, only an insignificant
amount of analyte ion is removed from the sample solu-
tion. This implies that the redox process involved at the
working electrode has a negligible effect on the chemical
FIGURE 17 Electrochemical profile observed in a classic polaro- titration reaction and does not introduce significant error
graphic experiment. in most instances.
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566 Analytical Chemistry

5. Coulometry and Electrogravimetry 1. Ion Sources


These techniques are dependent on an electrolysis that The common features of all ion sources are that they in-
attempts to oxidize or reduce completely all of an elec- corporate techniques for producing ions and giving them
troactive analyte species in a volume of sample solution. kinetic energy (acceleration used for introduction into the
These methods have the distinct advantage of requiring spectrometer). The electron-impact source is the most
no calibration since they are dependent on total electron widely used (Fig. 18). In this device, molecules in the
transfer, which can be quantitatively related to the total gas phase, obtained from the inlet system, are subjected
mass of the analyte. Coulometry refers to the integration to a stream of accelerated electrons (usually at a poten-
of electric current with time as electrolysis proceeds ei- tial of 70 V), and the resulting collisions between the
ther at a constant current or at a constant voltage. The particles cause molecular ionization and fragmentation.
latter parameters are chosen to optimize analysis time and These species are then injected into the spectrometer by
limit interferences. For constant current, the number of the accelerating slits. Another source is based on chemi-
coulombs of electrons consumed or produced, Q, is re- cal ionization. Here, the analyte molecule is ionized by an
lated to the current I and time t by ion–molecule reaction, not directly by electrons as men-
tioned above. A reagent gas is ionized by electrons, for
Q = I t. example, methane,
CH4 + e− → CH+ −
4 + 2e ,
For variable current, the relationship becomes
 with further reactions:
Q= I dt. CH+ +
4 + CH4 → CH5 + CH3

CH+ +
3 + CH4 → C2 H5 + H2 .
Typical electrochemical cell arrangements employ a three-
electrode potentiostat with a platinum working electrode. These particles can react with the sample molecule (MH)
It is possible in many cases to arrange the experiment in a number of ways:
so that the electrolysis deposits the analyte quantitatively
on the working electrode. The mass change of the elec-
CH+ +
5 + MH → CH4 + MH2
trode can be related to the number of coulombs of the
charge associated with the deposition to determine equiv- CH+
3 + MH → CH4 + M
+

alent weight. These techniques have only moderate sensi-


CH+
4 + MH → CH4 + MH
+
tivity but provide accuracy and precision to relative values
of tenths of a percent. The advantages of this technique are that less energy
is transferred to the analyte molecule, causing less frag-
mentation, and the fragmentation can be controlled by the
E. Mass Spectrometry choice of reagent gas.
The field ionization technique uses the effect produced
In mass spectrometry, molecules are both ionized, posi- on molecules by a high electric field (107 –108 V cm−1 ).
tively or negatively depending on the imposed conditions, In an appropriate electrode design, the electric field is
and fragmented. The particles are sorted out into groups high enough to rip electrons from the molecule of interest.
according to their mass-to-charge ratio. A plot of the count
of the ions against the mass of the different types of ions
is called a mass spectrum. This record is valuable analyti-
cally in that it is characteristic of each chemical compound.
The instrument required for this purpose can be divided
into several main components: (1) a device for introducing
the sample or inlet system, (2) an ion source, (3) the spec-
trometer for sorting out ions or ion analyzer, (4) a detector
of ions, (5) a recording system, (6) a vacuum system, and
(7) a complete control system including computer for data
handling and so on. There are a wide variety of such instru-
ments, which can be classified according to the methods
of ionization and/or procedures for ion analysis. Here, we FIGURE 18 Typical electron-impact source for mass spec-
shall concentrate on certain areas. trometry.
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Analytical Chemistry 567

Other sources are field desorption, spark source, thermal are brought to a focus close to where the ion detector is
ionization, fast atom bombardment, and secondary ion located. Thus, the analyzer separates the ions into streams
mass spectrometry (see SIMS, Section G.4, Surface Anal- of different M/e,
ysis).
M/e = H 2r 2 /2V,
where M is the mass of the ion, e is the charge, H is
2. The Spectrometer
the magnetic field, r is the radius of curvature of the an-
The purpose of the spectrometer is to separate the ions alyzer tube, and V is the accelerating potential employed
emanating from the ion source as efficiently as possible. in the ion source. Usually, V is swept to obtain a mass
Quantitatively, this is expressed as the resolving power spectrum. In the time-of-flight mass spectrometer, ions
of the instrument, which is defined as the ratio M/ M, of different mass, which are produced by pulsed electron
where M and M + M are the mass numbers of two beam impact in the ion source, are accelerated to the same
neighboring peaks of equal intensity in the spectrum. kinetic energy. The ions are then allowed to drift in space
The key factor here is the ability to distinguish M and down a tube of particular length before they are detected
M + M; usually, this is said to be achieved when the (Fig. 19b). Because they have different velocity, the transit
“valley” between the two peaks is no more than 10% of time t varies as
the intensity of M or M + M. Resolution is controlled  
M 1 1/2
by a number of instrumental factors, including the method t=L µsec.
of ion separation. e 2V
One widely used system of separation is the magnetic This instrument is useful for the study of fast reactions. An
deflection apparatus. Here, a controllable magnetic field additional spectrometer known as the quadrupole device
causes ions to deflect along curved paths according to their is based on the passage of ions through a region between
mass-to-charge ratio. The instrument is designed such that four, short parallel metal rods of alternating electrical volt-
only those ions that follow the path coinciding with the age and provides low resolving power. This is widely used
arc of the analyzer tube (Fig. 19a) in the magnetic field because of its simplicity, although its physics is very com-
plex.
All the spectrometers described to this point are called
single-focusing systems. These are characterized by low
resolving power, which is due to the variety of kinetic en-
ergies produced in the ion source. In a double-focusing
spectrometer (Fig. 19c), an electrostatic field for ion de-
flection is introduced between the ion source and the mag-
netic deflection device. The electrostatic analyzer ions are
effectively focused into highly defined kinetic energies be-
fore they pass into the magnetic analyzer. The resolving
power of such instruments is on the order of 50,000.
Another relatively new device known as the ion cy-
clotron system, which is not a double-focusing system, can
provide resolution to well over 100,000 and can operate in
a Fourier transform mode, offering speed and sensitivity.

3. Other Components
The sample inlet system for a typical mass spectrometer
is versatile enough to handle gas, liquids, and solids. The
device is usually held at ∼200◦ C and 0.02 torr pressure.
Accordingly, any solids must have a sufficient vapor pres-
sure under these conditions to allow transport to the ion
source as a gas before a spectrum can be recorded. Mod-
ern instruments usually incorporate an electron multiplier
or channel electron multiplier array as a detecting system.
FIGURE 19 Magnetic deflection (a), time-of-flight (b), and Both these devices work on the principle of electrons re-
double-focusing (c) mass spectrometers. leased from a material on ion impact. The electrons are
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568 Analytical Chemistry

then amplified in number before measurement of the cur- for bond breakage, which allow us to predict the original
rent. It goes without saying that nearly the entire mass structure of a particular species. For example, ring com-
spectrometer must be kept under high vacuum with diffu- pounds usually contain mass numbers characteristic of the
sion pumps, backed by rotary oil pumps. If the spectrom- ring (due to its inherent stability). As can be appreciated,
eter is connected to a gas chromatograph, an interface is the whole philosophy behind working out the structure of
inserted between the inlet system and the chromatograph a complete unknown from its mass spectrum is akin to the
to allow sample transport but to remove carrier gas. Effu- development of a solved jigsaw puzzle. This procedure is
sion, membrane, and jet separators are used for this pur- quite different from the use of the computer to match the
pose. Finally, most modern high-resolution instruments mass spectrum of an “unknown” with its memory bank
utilize dedicated computers not only for data handling, but of data, as mentioned above. In this case we are using the
also for total control of the instrument. Many facilities are “fingerprint” approach to identification.
incorporated in these configurations—for example, com-
parison “libraries” of recorded mass spectra of thousands
F. Thermal Methods
of known compounds.
Thermal methods of analysis involve the measurement of
a physical property of a sample as a function of controlled
4. Analytical Use temperature. Equipment is available for detecting transi-
The mass spectrometer is clearly of tremendous impor- tion temperatures, energies of transitions, weight loss, size
tance in the identification of chemical compounds. This changes, elasticity, and changes in solution temperature
is because the ionization of compounds produces unique plotted as a function of added volume of a reagent.
fragmentation patterns. Accordingly, the correlation of
mass spectra with molecular structure provides a beau-
1. Thermogravimetry
tiful foundation for chemical analysis. In identification
procedures at a reasonably low level, we can use the mass In thermogravimetry (TGA), weight change associated
spectrum in two distinct ways. First, the highest mass peak with a transition in the sample as a function of temper-
in the spectrum (Fig. 20) usually is associated with the ature is measured. For example, if water molecules of hy-
molecular weight of the compound, a particularly valu- dration can be removed thermally, they can be detected
able piece of initial information. Furthermore, at masses 1 by apparatus for TGA. Practically, the sample is placed
and 2 larger than this value, we find the effect of naturally in a crucible, which is part of an automatic recording an-
occurring heavier isotopes. This aids us in deciding on a alytical balance. The sample configuration is then intro-
formula for a particular molecular weight when we might duced into a furnace in which the temperature is mea-
have several choices. Second, fragmentation produces a sured accurately (usually room temperature to ∼1200◦ C).
set of characteristic mass peaks for each compound. De- The temperature of the furnace is raised gradually, often
struction of a particular ion occurs because there is enough in the heating range 5–10◦ C/min, and any weight losses
residual energy to cause bond breakage, as well as removal (increases) are recorded. From plots of loss (increase)
of electrons. Fortunately, a number of rules seem to apply in weight vs temperature, information about the gross
structure of the sample components and reaction mech-
anisms can be obtained. The technique is often employed
in conjunction with other thermal methods such as differ-
ential thermal analysis (DTA) and differential scanning
calorimetry (DSC).

2. Differential Thermal Analysis and Differential


Scanning Calorimetry
In DTA, the temperature of a sample is compared with
that of a reference substance, and the liberation or absorp-
tion of energy associated with various sample transitions
can be correlated with the difference in the two temper-
ature values. As in TGA, the temperature of the sample
is raised in a programmed fashion. The results inform the
FIGURE 20 Typical mass spectrum of an organic molecule with analyst as to the occurrence of exothermic or endother-
identified mass peaks. mic reactions. The instrument itself consists of a furnace
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Analytical Chemistry 569

endothermic peaks, which correlate with weight changes,


are caused by the loss of CO to produce CaCO3 and the
loss of CO2 to yield CaO, respectively.
Thermal analysis of polymeric materials can be partic-
ularly fruitful for the analyst. Melting points, phase transi-
tions, pyrolysis, and curing conditions can all be gleaned
not only from the temperature positions in DTA (DSC),
but also from the width of endothermic and exothermic
peaks. In addition, it is often possible to analyze gases
that are liberated from the sample by gas chromatographs
and mass spectrometers.
FIGURE 21 Apparatus for differential thermal analysis. S = sam-
ple pan; R = reference pan. 3. Thermometric Titrations
that incorporates a heating block for sample and reference In this technique, a titration of the sample (enclosed in a
material into different chambers (Fig. 21). The block tem- Dewar container) is performed with an automatic motor-
perature is measured at 5–10◦ C/min, and the difference in driven buret at the same time as the sample solution
temperature is measured by thermocouples, which are in temperature measurement. Temperature changes are very
close contact with the sample and reference material. The small (0.001–0.2◦ C), and therefore temperature measure-
overall temperature of the furnace is also recorded. In a ments must be made with considerable accuracy. The
rather closely related manner, DSC involves the addition method yield heats of reaction for a particular chemical
or substraction of thermal energy in order to maintain both system. Applications of the method include determination
sample and reference materials at the same temperature. of the concentration of an unknown, reaction stoichiom-
The three techniques described above are often corre- etry, and thermodynamic parameters. These can be per-
lated with one another in the thermal analysis of a sample, formed in nonaqueous solvents and fused salts.
since weight changes are often accompanied by the ab-
sorption or release of thermal energy. In DTA or DSC, G. Electron Spectroscopy
when an endothermic change occurs, the sample temper-
ature lags behind the reference temperature; the opposite When a sample is exposed to electromagnetic radiation of
is the case for exothermic processes. Typical TGA and sufficiently short wavelength or an electron beam with par-
DTA plots for an inorganic material, Ca(CH3 COO)2 ·H2 O, ticles of sufficient kinetic energy, an emission of electrons
are shown in Fig. 22. In an argon atmosphere, the first can be observed. In the former case we can ascribe elec-
endothermic signal matching a weight loss is associated tron ejection in terms of a photoionization effect, whereas
with the removal of water. The second and third of the in the latter we have ionization produced by electron im-
pact. Recent years have seen the development of a family
of techniques in which the kinetic energy and number
of ejected electrons are measured. Typically, these meth-
ods are classified as electron spectroscopic techniques.
The overall instrument consists of a sample inlet system,
ionization chamber, source of ionizing particles or radia-
tion, kinetic energy analyzer, electron detector, control and
recording system, and vacuum configuration (Fig. 23). As

FIGURE 22 Thermogravimetric and differential thermal analysis FIGURE 23 General schematic representing the experiment of
profiles for Ca(CH3 COO)2 ·H2 O. electron spectroscopy.
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570 Analytical Chemistry

with the mass spectrometer, an electrostatic field can be


used to focus electrons of certain energy at an exit slit ready
for counting (detection). The experimental plot of number
of electrons vs their kinetic energy is called an electron
energy spectrum. The individual techniques in electron
spectroscopy are classified according to either the method
of inducing ionization or the nature of the process that
accompanies the emission of electrons.

1. Vacuum Ultraviolet
Photoelectron Spectroscopy
In vacuum ultraviolet photoelectron spectroscopy (UPS),
the sample atom or molecule is exposed to radiation in the
vacuum ultraviolet region of the electromagnetic spec-
trum. A readily available source of radiation is the he-
lium discharge lamp, which produces a sharp HeI line at
21.2 eV. Since the energy required for photoionization of
sets of valence electrons is in the vicinity of 6 eV to this
energy, we obtain a polyenergetic emission of electrons
described by the Einstein relation
E n = hν − In ,
where In is the ionization energy of the nth species of
electron and E n is the kinetic energy of the bunch of elec-
trons ejected by a photon of energy hν. Usually, we form
an experimental plot of numbers of electrons vs ioniza-
tion potential (the photoelectron spectrum), since hν is a
known quantity and we wish to know In .
A great deal of work has been carried out by UPS
on gas-phase molecules. In particular, electronic energy FIGURE 24 Typical vacuum ultraviolet photoelectron (a), wide-
scan X-ray photoelectron (b), and narrow-scan X-ray photoelec-
level and vibrational fine structure information can be
tron (c) spectra.
generated. A typical ultraviolet photoelectron spectrum
is shown in Figs. 24a. Ionization of a nonbonding electron
results in little change in the molecular internuclear dis-
tance and sharp peaks are obtained, whereas the removal
2. X-Ray Photoelectron Spectroscopy or Electron
of a bonding electron causes changes in bond length and
Spectroscopy for Chemical Analysis
a distribution of vibrational transitions resulting in broad
peaks. Such vibrational structure has been used to study The development of this technique resulted in the award
vibrational frequencies in ions, to distinguish the nature of of the Nobel Prize in physics to Kai Siegbahn of Sweden.
electron bonding, and to examine the consequences of the Here, the sample is exposed to a beam of X-rays (although
Jahn–Teller theorem. Also found in spectra are the conse- synchrotron radiation has been used), causing ejection of
quences of spin–orbit coupling, which occurs as a result of both valence and more deeply held (core-level) electrons.
the production of a molecular ion in an orbitally degenerate Experimentally, by far the most work has been accom-
state. The hydrogen halide molecules show the expected plished with X-ray sources MgKα at 1253.6 eV and AlKα
progressive increase in splitting of the orbitals of halogen at 1486.6 eV, and most studies have been related to solid
lone-pair character (HF, 0.033 eV; HCl, 0.073 eV; HBr, samples and core-level spectra. A very important feature
0.32 eV; HI, 0.66 eV). In terms of chemical applications, of X-ray photoelectron spectroscopy (XPS) is that it is a
UPS has been employed for “fingerprint” identification surface-sensitive technique. Electrons produced by X-ray
in analytical chemistry, in molecular conformation stud- beam ionization are greatly attenuated by collision with
ies, for examination of the orbital structure of transient sample atoms or molecules according to the expression
species, and in correlation experiments with theoretical
calculations of orbital energies. I (x) = I 0 (x)e(−x/λ) ,
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Analytical Chemistry 571

where I (x) is the electron flux emerging at the surface for


a flux originating at depth x, I 0 (x). The parameter λ is
called the escape depth and is of the order of 20 Å for
electrons of kinetic energy 500 eV. Clearly, only discrete
kinetic energies of electrons will be obtained from the first
few atomic layers.
The binding energies of core electrons are essentially
constant, within narrow limits, and are characteristic of
the atom concerned. Accordingly, a sweep of the binding
energy scale (computed directly from measured kinetic
energy and knowledge of the source energy corrected for
charging) for a particular sample leads to an elemental
identification (Fig. 24b). Furthermore, the precise binding
energy of a core electron varies with the oxidation state
or chemical environment of an element. This is called
the chemical shift effect and manifests for ionizations of
the same atomic orbital from different chemical situations
(Fig. 24c). Observation of this effect is particularly useful
in solving structural problems in an analogous fashion
to that used in nuclear magnetic resonance spectroscopy.
Additional features of core-electron spectra are shake-up
and multiplet structure.
There are many applications of XPS, particularly in the
area of surface analysis. It has been applied in such diverse
areas as polymers, catalysts, textiles, corrosion, biochem- FIGURE 25 Ejection of the Auger electron (a) and typical differ-
ential Auger electron emission spectrum from a solid (b).
istry, environmental science, geochemistry, and archaeo-
logical chemistry. It is usually used for samples of approx-
imately 1 cm2 area but can sample a surface to a lateral
resolution of approximately 150 µm2 (limited by ability tively. The subscripts a, b, and c are subshell indexes, or J
to focus X-rays). Multichannel analysis and long analysis values. For example, we may label an electron as KL1 L 2 ,
times improve spectra, which often must be deconvoluted which means we have ionized a 1s electron, with relax-
by statistical techniques to identify signals associated with ation of a 2s electron (L 1 ), followed by emission from
closely spaced chemical shifts. L 2 . AES compares with XPS in that the kinetic energies
of the Auger electrons are characteristic of their elements
of origin, a feature useful for analysis, and that it is a
3. Auger Electron Spectroscopy
surface-oriented method for similar reasons. Also, there
To describe Auger electron spectroscopy (AES) we must are other observed transitions that have to be taken into
consider the fate of an atom after an electron is ejected account such as shake-up and Coster–Kronig processes.
by either X-ray radiation or electron impact. When a hole These generally produce satellites to the main peaks or
is generated in a core level, the atom must “relax,” and are responsible for the nonobservance of certain peaks,
it does this via electron movement to fill the level with respectively.
vacancy. This process can result in the release of an X-ray On a practical basis, the ionizing system is usually a mo-
photon (fluorescence) or can be responsible for the ejec- noenergetic beam of electrons. This arrangement enhances
tion of a secondary electron (Fig. 25a). The latter is called the sensitivity of the technique through many electron-
an Auger electron after its discoverer in the 1920s, and impact collisions. However, this has the undesirable fea-
it is the counting and measurement of the kinetic energy ture of a large diffuse background of scattered electrons,
of these electrons that constitute AES. As distinct from which makes it difficult to observe the discrete Auger peak
XPS, nomenclature from physics is used to describe the in a simple manner. Accordingly, the spectrum is usually
origin of a particular Auger electron. From elements to- plotted in the differential mode (Fig. 25b) to pick out the
ward the top half of the periodic table, the symbol X a Yb Z c identifiable Auger features. Another valuable experimen-
is used, where X is the original level where primary ion- tal feature, associated with the narrowness of the ioniz-
ization takes place, and Y and Z represent the origins of ing electron beam (∼1 µm), is the ability to carry out a
the “down” electron and ejected Auger electron, respec- full three-dimensional “surface” volume analysis of the
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572 Analytical Chemistry

sample. Here, lateral analysis can be performed by move- 5. Has high sensitivity
ment of the impacting electron beam, and depth studies 6. Has high spatial resolution
can be achieved by removing layers of sample by impinge- 7. Is applicable to a wide range of samples
ment of a sputtering ion beam. 8. Does not discriminate against any component
Not surprisingly, AES has found tremendous use in the 9. Has no influence on surface composition and structure
analysis of surfaces of samples in metallurgy and mate-
rials science. It has been used extensively in alloy analy- As expected, no single technique possesses all these
sis, metal oxidation, segregation, adsorption phenomena, requirements. The battery of methods that are available
catalysis, electrodeposition, corrosion, films and coatings, is outlined in Table XII. From these data it is clear that
tribology, adhesion, and the semiconductor industry. the overall strategy is the study of information carried by
emitted photons, ions, or electrons after perturbation of a
4. Surface Analysis
We now describe briefly the principles of a number
In view of the comments regarding the use of XPS and of important methods. In secondary-ion mass spectrome-
AES in surface analysis, it is appropriate to summarize try (SIMS), solids are bombarded by 1- to 30-keV ions,
this area concisely. An ideal method for surface analysis resulting in the ejection of substrate species as posi-
should possess the following features: tively and negatively charged atomic and molecular par-
ticles (and neutrals). The charged species are subjected
1. Is capable of monolayer examination to mass spectral analysis. The method is used in both
2. Detects elements dynamic and static modes; in the latter the target is
3. Identifies molecular species bombarded “gently,” resulting in a low sputtering rate
4. Elucidates surface topography and a relatively long average lifetime of the monolayer.

TABLE XII Example Methods of Surface Analysis


Exit species and information carrier

Excitation or probe Photons Electrons Ions (neutrals)

Photons Laser optical-emission spectroscopy X-ray photoelectron spectroscopy (XPS) Photodesorption (PD)
(LOES)
Light (Raman) scattering spectroscopy Ultraviolet photoelectron spectroscopy
(LS) (UPS)
Fourier transform infrared spectroscopy
(FTIR)
Ellipsometry (E)
Evanescent wave spectrofluorimetry
(EWS)
Electrons Electron microprobe (EMP) Auger electron spectroscopy (AES) Electron-stimulated desorption
Scanning electron microscopy X-ray Scanning electron microscopy (SEM) (ESD)
detection (XSEM) Low-energy electron diffraction (LEED)
Electron-impact energy loss spectroscopy
(EELS)
Ions Ion-induced X-ray spectroscopy (IIX) Ion-neutralization spectroscopy (INS) Secondary-ion mass spectrometry
(SIMS)
Proton-induced X-ray spectroscopy Ion-induced Auger electron spectroscopy Ion-scattering spectroscopy (ISS)
(PIX) (IAES)
Surface composition by analysis of Rutherford backscatter
neutral species and ion-impact spectroscopy (RBS)
radiation (SCANIIR)
Glow-discharge optical spectroscopy
(GDOS)
Electric field — Field electron microscopy (FEM) Atom probe field-ion microscopy
(APFIM)
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Analytical Chemistry 573

In ion-scattering spectroscopy (ISS), low-energy ions manipulators. Finally, in Table XIII we carry out a direct
(0.5–2 keV) bombard the surface to provide energy spectra comparison of the methods outlined in this article with
characteristic of the masses of the scattering centers. Low- respect to such analytical criteria as sensitivity, limit of
energy electron diffraction (LEED) is concerned with the detection, and lateral resolution. An examination of the
impingement of electrons of energy 5–500 eV on a sur- data reveals that each method has its own strengths and
face to provide a study of the surface diffraction process. weaknesses and that surface methods in general are truly
In electron-impact energy loss spectroscopy (EELS), a complementary.
monoenergetic beam of electrons is imposed on a surface,
and the electrons obtained from the surface are exam-
H. Chemical Sensors
ined for discrete energy losses associated with the vibra-
tional frequencies of adsorbed molecules. Direct observa- Since 1975 there has been a movement toward the in situ
tion of individual molecules and atoms has been achieved analysis of specific species in complex mixtures without
by Scanning Tunnelling Microscopy (STM) and Atomic initial application of separation science to simplify the
Force Microscopy (AFM), both of which bring a fine wire problem. The possible applications of such chemically
with a tip of atomic dimensions to the surface and observe selective devices, particularly those designed to quanti-
interactions of the wire with the surface while the wire tatively monitor organic compounds, cover a wide range
is displaced laterally by piezoelectric crystal mechanical of situations, including on-line monitoring and control of

TABLE XIII Performance Criteria for Methods of Surface Analysisa


Characteristic AES XPS SIMS ISS LEED EELS

Excitation beam Electrons X-ray photons Ions Ions Electrons Electrons


Energy (keV) 0.1–5 1–10 0.1–100 0.5–2 0.2–0.5 0.003–0.008
Diameter (µm) 25–100 10 103 103 103 103
→1 raster →1 raster
Information depth (Å) 3–25 10–30 3–20 3–10 0–10 0–10
Monolayers 2–10 3–10 1–4 2 0–2 0–2
Detection capability
Elements Z >2 2 Z >1 All Z >1 Not directly Not directly
Elemental sensitivity 10 10 104 10 — —
range
Isotopes No No Yes Restricated No Restricted
Chemical valence Special cases Yes Indirect No No Yes
Organics No Yes No No No No
Beam damage Small Occasionally Yes, dynamic; Small Small No
uppermost
layer, static
Lateral resolution <1µm possible ∼1.0 mm <1 µm possible 10 µm 2.0 mm 1.0 mm
Detection limits
“Surface” (g cm−2 ) 10−10 10−9 10−13 10−10 10−10 10−10
Bulk (atomic fraction) 10−3 10−3 –10−2 10−3 –10−4 10−2 — —
Advantages Sensitive to Information on Detection of all Outermost Atomic Direct
low-Z chemical elements and atomic layer structure of information on
elements; bonds; no isotopes; good analysis “ordered” interaction of
minimal beam damage detection surface adsorbate
matrix effects; sensitivity;
high lateral high lateral
resolution resolution
Disadvantages Difficult to No lateral Difficult to Low sensitivity, No elemental No elemental
quatify; no resolution; quantify poor lateral analysis pattern; analysis; long
H, He detection slow profiling; matrix effects resolution; often difficult analysis time
no H detection slow profiling to interpret;
long analysis time

aFor definitions of acronyms, see Table XII. [From Thompson, M., Baker, M. D., Christie, A., and Tyson, J. F. (1985).“Auger Electron Spectroscopy,”
Wiley-Interscience, New York.]
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574 Analytical Chemistry

industrial chemical processes, long-term remote environ- selective membrane. The variation of potential of one sur-
mental monitoring, automation of clinical analyses, in vivo face of this membrane can control any electronic current
drug monitoring, and feedback control of artificial organs. through the transistor known as the drain current. A simi-
All chemical sensors employ a basic union between a lar arrangement employing an enzyme–substrate receptor
selective receiving site for ionic or molecular binding and system at the gate also provides for ionic charge control
a transducer that is capable of translating a chemical bind- of transistor electronic current conduction, resulting in a
ing into a useful analytical signal. Transducers can be di- chemically sensitive field effect transistor (CHEMFET).
vided into four categories: semiconductors, conventional Multiple enzyme systems, where one enzyme produces
ion-selective electrodes, optical devices, and piezoelectric an electrochemically inactive product that is consumed as
devices. Other than the ion-selective electrodes described a substrate by another enzyme to form an active prod-
previously, the semiconductor-based gas sensors are the uct, have been successfully used to extend enzyme se-
best known chemical sensors. These devices usually op- lectivity. The selectivity of immunochemical systems has
erate at elevated temperatures, allowing certain gases to been employed by implementation of enzyme-linked as-
interact chemically with the semiconductor surface to alter says. Direct coupling of redox relay centers of enzymes
its electrical characteristics. Such devices may be selective to conductive electrodes has been achieved by a technique
to certain gases such as CO2 and O2 or to certain classes known as molecular wiring and avoids the indirect anal-
of molecules such as hydrocarbons and may take the form ysis of products of enzyme–substrate reactions. This fast
of chemiresistors or thin-film metal oxides. and sensitive technique measures current flow and is com-
Better selectivity can be attained by the use of special- mercially available.
ized chemical receptors. The ion-exchange chemistry of
ion-selective membranes is one manner in which selec-
2. Optical Devices
tivity is enhanced for simple inorganic ions and gases.
Nature provides the materials for the complicated task of In analogy to electrodes, chemically selective optical de-
selectively complexing biochemicals through molecular vices have been termed optrodes. These systems employ
recognition processes. The selectivity of these receptors is absorption and luminescence strategies and make use of
based on the tertiary structure of proteins and polypeptides waveguide fiber-optic and laser technology for miniatur-
and on nucleic acid complementary pairing. Enzyme– ization. Light in the ultraviolet or visible region of the
substrate, antibody–antigen, lectin–saccharide, and hor- electromagnetic spectrum can be passed through an opti-
mone receptor–hormone selective reactions have all been cal fiber to a remote reaction vessel. Detection may de-
employed in conjunction with “building block” construc- pend on observation of light passing through the reaction
tion and a variety of transducers to produce sensitive and zone, or being transmitted toward a detector by another
selective devices. Such selective chemistry has also found fiber, or by the evanescent wave phenomenon encoun-
wide application in techniques such as immunoassay. The tered in techniques such as attenuated total reflection or
development of catalytic antibodies (synzymes) and ge- total internal reflection fluorescence spectroscopy. In con-
netic engineering to express proteins of DNA of inter- trast to electrochemical devices, these systems offer ad-
est for chemical selectivity and the introduction of artifi- vantages such as insensitivity to electrical interference,
cial receptor sites and selective surfaces have substantially elimination of reference electrodes, possibility for change
broadened the commercial potential for long-term devel- of reagent phase, distributed multisensor operation with
opment of a wide range of chemical sensors. the use of one optical detector (spectrophotometer), mul-
tiwavelength analysis, time-resolved analysis, and a com-
plementary range of analytes that may not be electrochem-
1. Electrochemical Devices
ically active. One example is a pH sensor, based on optical
These devices are based on the measurement of either elec- absorption changes of an indicator dye trapped in a gel ma-
trochemical potential or faradaic current associated with trix in a cell at the tip of a fiber-optic system. Ratio meth-
redox reactions at an electrode. They are particularly suit- ods of quantitative analysis and multiwavelength analy-
able for enzyme–substrate receptor systems by virtue of sis for selective observation of two or more species are
the ionic products often produced in such reactions. The preferred for elimination of background drift and interfer-
sensing membranes of the ion-selective electrodes previ- ence problems. A form of evanescent wave spectroscopy
ously described have been combined with semiconductor in which the electromagnetic field is coupled into the con-
devices for miniaturization, low-impedance output, signal duction band of a thin metal film is currently being com-
amplification, and capability of on-chip processing. The mercialized. This technique, known as Surface Plasmon
ion-sensitive field effect transistor (ISFET) is based on re- Resonance Spectroscopy (SPR), is very sensitive to any
placement of the conventional transistor gate with the ion- organic reagents located on the exterior of the metal film
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Analytical Chemistry 575

and can be used to picomolar detection limits for many aging, statistical analysis, integration, and data storage.
immunochemical analyses. Often these functions can be handled by a micro- or mini-
computer with a minimum of 8-bit word lengths, though
greater word length and greater capability of microproces-
3. Piezoelectric Devices
sor addressing allow for increased processing speeds and
It is well known that certain crystalline substances such greater on-line data storage capability. Data acquisition is
as quartz generate an electrical voltage when subjected to usually performed by specialized analog-to-digital circuit
physical compression. Similarly, it is possible to induce packages, which may receive polling requests and timing
a constant frequency of physical oscillation of the crystal signals from the microprocessor. Two common devices
planes when a regular alternating voltage is applied to such for transducing analog instrument measurements into dig-
a crystal. Piezoelectric crystals coated with thin films of ital form are known as counter converters and successive
selective adsorbent have found application as conventional approximation counters. Some instruments acquire com-
gas detectors when employed as physical oscillators. The plicated and extensive data sets at rapid rates. Such data
mass changes caused by the adsorption of gases to the may be difficult to interpret manually, but with the aid of a
crystal cause the oscillation frequency to change, f, in reference library, aspects such as compound identification
proportion to adsorbed mass as can readily be established by computer. Such reference li-
braries are used extensively for infrared and mass spectral
f = −2 f q2 (Pq Vq )m f , analysis.
where f q is the quartz crystal frequency, Pq is the quartz
density, Vq is the velocity of the wave in the quartz, and 2. Microprocessor Control
m f is the mass per unit area for the deposited matter on
Due to its great speed, a computer can often control an in-
the quartz surface. It has been demonstrated that mass
strument more efficiently than is possible by manual oper-
responses and also microviscosity responses associated
ation. Such active instrument control must occur in at least
with surface reactions can be obtained from enzyme–
two steps. The microprocessor must first ascertain the state
substrate and immunochemical complexation on bulk
of some variable, and then action must be taken to activate
acoustic wave piezoelectric quartz crystals. Furthermore,
an instrument control to adjust the value of the variable.
both bulk acoustic and surface acoustic wave devices can
Many instruments employing microprocessor control con-
be used directly in aqueous media in certain configurations
tain more than one processor and can perform a series
for quantitative analysis.
of complicated feedback functions. These processors are
considered to be “dedicated” to a particular series of tasks
and receive their operating commands from a hard-wired
III. COMPUTERS IN
instruction set as well as the instrument operator. The sim-
ANALYTICAL CHEMISTRY
plest microprocessors operate with instruction sets based
on 8-bit word lengths. Memory increments of 256 words
A. Instrument Control and Data Handling
are available for such systems, and often only one or two
Since 1975 there has been a tremendous revolution in ca- of these memory increments are required for instrument
pability and cost of computers and microprocessors, re- control. Control usually takes the form of activating a stan-
sulting in the incorporation of such technology into al- dard electrical relay device (which may drive a motor or
most every modern analytical instrument available today. switch) by toggling an active line connected to the relay
Computers are fundamental to two areas of analytical and controlled by the microprocessor between electrical
chemistry: (1) the applications of mathematics to analysis ground and a standard 5-V high level. More complicated
(chemometrics), encompassing such topics as factor anal- control systems involve more control relays and necessi-
ysis, multiple regression, pattern recognition, optimiza- tate the availability of more control lines and microproces-
tion, and statistics, and (2) interactions with analytical sors. The time-sharing capabilities of a minicomputer are
instruments. The latter can actually be considered to be often used in controlling a number of microcomputers or
either passive or active interaction, as determined by com- microprocessors in complex instruments. Significant ad-
puter control of instrument operation. vances in speed and therefore “real time” complexity of
instrument operation have been achieved as new 16- and
32-bit microprocessors have entered the market. The ad-
1. Data Acquisition and Processing
vantages of speed and increased memory have aided in the
This area usually implies a passive function involving the development of expert systems and parallel processing. A
actual collection of data, simple calculations, data aver- revolution in instrument control and data processing is
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576 Analytical Chemistry

currently developing with the advent of parallel process- processing, resultant conversion, and information organi-
ing and neural networks for interactive “learning.” zation. Software packages for these purposes are commer-
cially available.
3. Fourier Transform Analysis
1. Common Chemometric Methods
One application of high-speed computers to data anal-
ysis is often found in spectrophotometric applications, The three most commonly used chemometric methods are
such as infrared and nuclear magnetic resonance tech- discussed in the following subsections.
niques. Samples can be irradiated with broad ranges of
frequencies from the appropriate regions of the electro- Multiple regression analysis. This is suitable for
magnetic spectrum and will absorb certain discrete fre- data modeling and expresses data as a simple equation.
quencies dependent on sample chemistry. Each indepen- The process begins with experimentation to produce a vec-
dent frequency that can be observed (resolved) in the range tor of measured data known as the “dependent” variables.
of energies employed can be represented as a sinusoidal Then a limited number of “factors” are considered to be
oscillation. The simultaneous superpositioning of all the significant for the determination of data values, and these
available frequencies produces both constructive and de- “independent” variables are used to prepare a model for
structive interference, resulting in a well-defined complex the data. Finally, coefficients, as shown below, are calcu-
waveform pattern. Interaction of the sample with discrete lated by least-squares analysis to represent the significance
frequencies will alter the waveform pattern, which will or weighting of the independent variables. The result is a
then contain the analytical interaction information in the calculation of “regression coefficients” to prepare a math-
form of a time “domain.” This can be converted to a con- ematical model that is suitable for preditions,
ventional frequency-domain spectrum by the fast Fourier d = c 1 i 1 + c2 i 2 + · · · + c n i n ,
transform algorithm, so that individual frequencies that
make up the superimposed waveform can be individually where d represents the dependent variable, c represents
identified and plotted in conventional formats. Data must the regression coefficient, and i represents the independent
be sampled and digitized at a rate at least twice the value of variable.
the ratio of the range of frequencies encountered divided
by the frequency resolution desired. The major advantage Factor analysis. This method is used to interpret
of this technique is that all frequencies are simultaneously underlying factors responsible for data and is one of the
measured, and a complete conventional spectrum can be most versatile chemometric methods. Factor analysis pro-
constructed in seconds for any one measurement. Since vides a purely mathematical model prepared from abstract
these spectra are digitized and contain frequency refer- values, which are related to a data matrix as follows,
ence information, it is possible to sum sequential spectra D = RC,
to improve signal-to-noise ratio. Signals increase linearly
with spectral addition, while noise increases as the square where D represents the data matrix and R and C represent
root of the number of spectra that are combined. factors for each row and column. The factors are math-
ematically transformed so that their significance can be
interpreted with respect to the data. This results in the es-
B. Chemometrics tablishment of the number of significant factors and assists
The term chemometrics describes the interface between in the correlation of data and the application of physical
analytical chemistry and applied mathematics, where significance to the factors.
mathematical and statistical methods are employed to
maximize information quality in a chemical experiment. Pattern recognition. This procedure allows the
Most chemometric methods involve matrix algebra, which classification of a species to be made on the basis of a
is efficiently handled by computer, and numerous pro- series of measurements that establish a pattern. Proce-
grams are presently available. A number of reviews have durally, a matrix describing the patterns of a number of
been written on this broad subject area, which includes species is constructed. Then a decision vector is designed
such topics as statistics, modeling and parameter esti- by the use of standards to divide the patterns into discrete
mation, resolution, calibration, signal processing, image classifications, resulting in a mathematical form,
analysis, factor analysis, pattern recognition, optimization p = V1 d1 + V2 d2 + · · · + Vn dn ,
strategies, and artificial intelligence. Appropriate topics
can be chosen to optimize an analysis at each level of where p represents a set of patterns, V represents com-
experimentation, including sampling, measurement, data ponents of the decision vector, and d represents the data
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Analytical Chemistry 577

for the species of interest. The pattern p is assigned and method originally described must employ steps of fixed
values of d are determined so that a decision vector V can size, which can result in excessive experimentation when
be calculated. When the calculated vector V is mathemat- step size is small or in poor precision for large steps. A
ically combined with a new set of experimental data, a more efficient solution employs variable step size through-
pattern p is calculated for the experimental species and out the entire procedure, allowing expansion (accelera-
can be fitted to previous classifications. tion) of the simplex in favorable directions and contrac-
tion in zones that produce poor results. The distance to be
moved is controlled by constant arbitrarily chosen multi-
2. Optimization by the Simplex Method
plication factors, which are multiplied with the distance of
Numerous mathematical techniques exist for solving a se- movement obtained on reflection. Eventually, the simplex
ries of simultaneous equations given defined boundary contracts as movement to the optimum occurs. The process
constraints in order to maximize or minimize a particu- halts when the distance of movement has dropped below
lar parameter. The general acceptance and implementa- some predetermined value, which is generally governed
tion of techniques such as linear programming attest to by experimental uncertainty or time limitations. Certain
the power of optimization strategies. The simplex method difficulties exist in the application of simplex methods
is an “evolutionary operations” method that has been used when considering error sources:
systematically in many problems. A simplex is a geomet-
ric figure whose vertices are defined by the number of ex- 1. The method cannot be used if discontinuous variables
perimental parameters plus 1. Each point of the simplex are chosen.
represents the actual measured analytical response at a set 2. Movement to a local optimum may occur if numerous
of chosen experimental parameters. Represented in some optima exist.
n-dimensional space, one vertex of the simplex always 3. Parameters must be judiciously selected to ensure that
represents the case of worst response in the experimental. nontrivial analyses occur.
A mirror reflection through a symmetry plane away from 4. As many significant parameters as possible should be
the point of worst response (assuming the response will be included in the simplex so that no important factors
greater at a point opposite to the worst case) generates an- are overlooked. This subsequently increases the
other simplex. An experiment is then performed using the experimental work for each step in the simplex
new parameters to determine which vertex represents the generation.
new worst case response. A reiteration process following
four well-defined rules allows movement along the “re-
sponse surface,” resulting in eventual convergence to the 3. Selectivity vs Specificity
optimal experimental conditions.
The basic rules are as follows: A definition of terminology has been attempted, where the
upper limit of the concept of selectivity implies specificity.
1. Rejection of the point with the worst result is followed A fully selective system can measure one component in the
by replacement with its mirror image across a line or presence of many others, while fully specific implies that
plane generated by the other remaining points. in all situations only one component is measured and other
2. If the new point has the worst response, the previous components in the experiment do not produce any signal.
simplex is regenerated and the process applied in rule A nonselective system produces an analytical signal due to
1 is repeated for the second worst case point. all components in the experiment. For any of these cases,
3. If one point is common to three successive simplexes, the measured signal x is a function of concentration c of
it represents the optimum, provided that the point the available component and is related to the latter by a
represented the best response in each case. If this is normalization parameter γ , where
false, the entire process must be repeated using new
x = γ c.
initial starting points.
4. Boundary conditions are defined so that if a point falls The element γ is determined by the sensitivity parameter
outside accepted bounds, it is assigned an artificially dx/dc, and the sensitivity of the method is numerically
low value, which forces the simplex to move into the determined by the value of γ . This example can readily
useful calculation area. be expanded to consider a multicomponent case, where
x, γ , and c become matrix representations and a partial
A variation of the latter optimization procedure known sensitivity ∂ x/∂c is employed. A mathematical rearrange-
as “modified simplex optimization” has evolved to elimi- ment of the γi j matrix to place the largest γ value in each
nate the limitations imposed by the simplex method. The row on the main diagonal results in a useful “calibration
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578 Analytical Chemistry

TABLE XIV Areas of Future Instrumental Development IV. FUTURE PERSPECTIVES


Area Anticipated development
Naturally, it is difficult to predict the evolution of a dis-
Electroanalytical methods Molecularly designed electrodes, cipline as diverse as analytical chemistry. Table XIV
speciation
indicates a summary of short-term future directions as
Microelectrodes, biological probes
garnered from the present interests and activities of re-
Electrochemical detectors, combination
techniques
searchers in the field. One dramatic, rapid change is the
Chromatographic and Specialization methods for difficult
movement away from sampling technology. Direct in situ
separation methods separations (maximization of measurement technology is being emphasized in many
column efficiency and methodology areas of analytical chemistry and eventually may largely
presently attained developments in supercede the need to define statistically valid samples
supercritical fluid chromatography, from a bulk sample material.
separation of isomers and
chiral species)
Probably the analytical instrumentation of the future
Spectrochemical methods Higher yield ion sources for mass
will become more and more automated, but until artificial
spectrometry intelligence makes its debut in instrumentation, the chem-
Hyphenated techniques, gas or liquid ical knowledge of the analyst will always be of paramount
chromatography with inductively importance. The intelligent application of any analytical
coupled plasma emission spectroscopy technique will continue to require a good understanding
Minimization of sample preparation of basic physical and chemical theory and a knowledge of
Chemometrics Computer-assisted data manipulation practical experimental limitations.
Expert systems and “intelligent”
instruments
Resolution improvement programs for
chromatography to speed analyses
SEE ALSO THE FOLLOWING ARTICLES
Pattern recognition systems
Surface science Angle-resolved electron spectroscopy
ATOMIC SPECTROMETRY • CHROMATOGRAPHY • DISTIL-
LATION • ELECTROCHEMISTRY • ELEMENTAL ANALY-
Molecular information, conformations
SIS, ORGANIC COMPOUNDS • GAS CHROMATOGRAPHY •
Discrete molecular and atomic resolution,
e.g., for direct sequencing of DNA INFRARED SPECTROSCOPY • LIQUID CHROMATOGRAPHY
• MASS SPECTROMETRY • NUCLEAR MAGNETIC RESO-
NANCE • ORGANIC CHEMISTRY, COMPOUND DETECTION

matrix.” If the corresponding “analytical matrix” of x jk is • RAMAN SPECTROSCOPY


considered, the following observations apply:
BIBLIOGRAPHY
1. For a determinant of det(γik ) = 0, no mapping from
the calibration to the analytical matrix exists. Bard, A. J., and Faulkner, L. R. (2001). “Electrochemical Methods,”
2. Selectivity can be given a value θ , where Wiley, New York.
γii Christian, G. D. (1994). “Analytical Chemistry,” 5th ed., Wiley, New
θ = min
k − 1, York.
i=1→n
n=1 γik − γii Dean, J. A. (1995). “Analytical Chemistry Handbook,” McGraw-Hill,
New York.
A system is fully selective when lim θ → ∞, but no Elving, P. J., and Kolthoff, I. M. (eds.) (1978). “Treatise on Analytical
selectivity exists for θ values that are small compared Chemistry,” 2nd ed., Wiley-Interscience, New York.
with zero. Kellneer, R., Mermet, J.-M., Otto, M., and Widmer, H. M. (1998). “An-
alytical Chemistry,” Wiley-VCH, Weinheim.
3. Specificity is a special case of selectivity and Lindon, J. C., Tranter, G. E., and Holmes, J. L., eds., (2000). “Ency-
generates a single nonzero element (in the calibration clopedia of Spectroscopy and Spectrometry,” Academic Press, San
matrix), which lies on the diagonal. Diego.
4. A partial specificity can be defined when only the Meyers, R. A., ed. (1998). “Encyclopedia of Environmental Analysis
diagonal element in one row can practically be and Remediation,” Wiley, New York.
Meyers, R. A., ed. (2000). “Encyclopedia of Analytical Chemistry
considered to have a nonzero value. A grade of Applications, Theory and Instrumentation,” Wiley, Chichester.
specificity is numericaily determined by Skoog, D. A., West, D. M., and Holler, J. F. (1997). “Fundamentals of
γaa Analytical Chemistry,” 7th ed., Saunders, Philadelphia.
θa =
n − 1. Skoog, D. A., Holler, J. F., and Nieman, T. A. (1998). “Principles of
k=1 γkk − γaa Instrumental Analysis,” 5th ed., Harcourt, Philadelphia.
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Analytical Chemistry 579

Sorum, C. H., and Lagowski, J. J. (1991). “Introduction to Semimicro Svehla, G., and Suehla G. (1996). “Vogel’s Qualitative Inorganic
Qualitative Analysis,” 7th ed., Prentice-Hall, Englewood Cliffs, Analysis,” 7th ed., Addison-Wesley, Reading, MA.
NJ. Wilson, I. D., Adlard, T. R., Cooke, M., and Poole, C. F., eds.
Strobel, H. A., and Heineman, W. R. (1989). “Chemical Instrumentation: (2000). “Encyclopedia of Separation Science,” Academic Press, San
A Systematic Approach,” 3rd ed., Wiley, New York. Diego.
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Encyclopedia of Physical Science and Technology en001d42 May 26, 2001 14:55

Atomic Spectrometry
Vahid Majidi
Chemistry Division, Los Alamos National Laboratory

I. Atomic Spectrometric Techniques


II. Optical Detection
III. Atomic Emission Spectrometry
IV. Atomic Absorption Spectrometry
V. Atomic Fluorescence Spectrometry
VI. Detection of Elemental Ions
VII. Comparisons of the Atomic
Spectrometric Techniques

GLOSSARY Standard Sample that contains the analyte at a known


concentration from which a signal can be obtained that
Analyte Element whose concentration is to be deter- can be compared with the signal from a sample of un-
mined in a matrix. known analyte concentration. From this, the concen-
Atom cell Device that provides a sufficiently high tem- tration of the analyte in the unknown sample can be
perature to break down the sample into its constituent determined.
atoms.
Differential pumping Evacuating two chambers, ad-
joined by a conductance limited orifice, with the use ATOMIC SPECTROMETRY is a series of analytical
of either one or two independent vacuum pumps. This techniques that are used to determine the identity and
allows for maintaining two connected chambers at dif- concentration of elements in any sample. While his-
ferent pressures with respect to one another. torically the detection of analytical signals was exclu-
Interference Increase or decrease in the size of the signal sively done through measurement of photons, during
obtained from the analyte as a result of the presence the past two decades atomic spectroscopists have suc-
of some other known or unknown component in the cessfully integrated the measurement of ion current into
matrix. the suite of detection technologies known as atomic
Matrix Components of a sample other than the element spectrometry. Photon-detection-based techniques include
whose concentration is to be determined. atomic emission, atomic absorption, and atomic fluores-
Multi-element Multi-element analysis is the simultane- cence spectrometry. Ion-detection technologies include
ous or rapid sequential determination of the concentra- laser-enhanced ionization and elemental mass spectrom-
tion of several elements in a matrix. etry (MS). Absolute analyte masses at the nanogram

765
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766 Atomic Spectrometry

level (10−9 g) can be determined in samples of a few is initially volatilized and ultimately decomposed into its
micrograms (10−6 g) by electrothermal vaporization constituent atoms (sodium and chlorine) by the heat of
(ETV) atomic absorption. Solution concentrations at the the flame. The thermal energy from the flame excites the
nanogram (10−9 g) per milliliter level can be routinely gas-phase sodium atoms from the ground state (0) to an
measured by most of these techniques. Conversely, us- excited state (1). The efficiency of this excitation depends
ing plasma mass spectrometry, absolute mass detection on the gas-phase temperature (the wavy line in Fig. 1A
limits of a few femtograms (10−15 g by ETV–MS) or represents the thermal excitation processes). The sodium
measuring solution concentrations of parts per quadrillion atom in the excited state then spontaneously decays back
(10−15 g/ml) are not uncommon. All the techniques use the down to the ground state, either by collisional transfer of
phenomenon of electronic excitation. This involves transi- energy to other species or by atomic emission (loss of en-
tions among the outer electrons in the atomic orbitals, with ergy by emission of a photon). This is illustrated by the
accompanying ionization, emission, or absorption of ra- straight line from the excited state down to the ground
diation. In photon-based detection, the intensity of these state in Fig. 1A. The wavelength of this emitted photon
emissions and absorptions can be related directly to the depends on the energy difference between the excited state
concentration of an element in a sample. For ion-based and the ground state.
detection, the obtained electric current is directly propor- The amount of light that is emitted from the analyte
tional to the analyte concentration. is proportional to the number of atoms in the flame or
plasma. Hence, atomic emission spectrometry can be both
a qualitative analytical technique, in which the identity of a
I. ATOMIC SPECTROMETRIC metal is revealed by the observed color (wavelength), and
TECHNIQUES a quantitative analytical technique, in which the intensity
of the light emitted from the analyte is a function of the
There are three traditional analytical atomic spectrometric number of atoms.
techniques: atomic emission spectrometry (AES), atomic The experimental arrangement involved in an AES mea-
absorption spectrometry (AAS), and atomic fluorescence surement is shown in Fig. 1E. The hot analyte environ-
spectrometry (AFS). In all three cases, the analytical sig- ment, which is able to break down and excite atoms, is
nal is generated by photons. More recently, however, the called an atom cell. The atom cell can be a flame, plasma,
detection of resulting ions from an electronic excitation a heated graphite tube, or any other environment where
has led to superbly sensitive detection of elements. It is the analyte is observed in a spatially confined arrange-
possible to distinguish among these techniques by con- ment. In Fig. 1, the detector box is used to represent a
sidering the excitation mechanism and the way the an- detection system, which is able to identify the wavelength
alytical signal is detected. The general schematic rep- and measure the intensity of the emitted radiation. The ex-
resentation for various types of atomic spectrometry is perimental arrangement is the simplest of the three optical
shown in Fig. 1, where two-level electronic systems are atomic spectrometric techniques.
depicted. The ground state is labeled 0, and the excited
state is labeled 1. In general, the transition originat-
B. Atomic Absorption Spectrometry (AAS)
ing from or terminating to the ground state (or another
of the lowest lying excited states) is most commonly Figure 1B illustrates the principle of atomic absorption
used for atomic spectrometric measurements (Ingle and spectrometry. The excitation from the ground state to the
Crouch, 1981). upper state is by the absorption of light energy. An atom
cell (a flame or a heated graphite tube) is used to decom-
pose compounds, but the energy for excitation is drawn
A. Atomic Emission Spectrometry (AES)
primarily from a light source such as a white light source
The most basic measurements in analytical atomic spec- (which emits all wavelengths) or a hollow cathode lamp
trometry can be traced back to Thomas Melville, who in (which emits narrow spectral lines). In AAS, the detection
1752 reported his observations on spectra of mixtures of system looks at the light source directly (Fig. 1F) and sees
alcohol with sea salts (Laitinen and Ewing, 1981). The an intensity of the light source (I0 ) before any atoms are
simplest example of atomic emission is the experiment of present within the atom cell. When atoms are introduced
putting table salt (sodium chloride) into a flame, which into the atom cell, they absorb some of the radiational
generates a yellow color. Although the example is a sim- energy (solid arrow in Fig. 1B) and are excited from the
ple illustration, the actual events that ultimately lead to ground state to the upper state. The detection system sees
the yellow plume are due to a complex series of chemical this absorption as a reduction in the intensity of the light
and physical processes outlined in Fig. 2. Sodium chloride source from I0 to I (Fig. 1F). The ratio I /I0 is called the
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Atomic Spectrometry 767

FIGURE 1 A simple two-level energy diagram representation for excitation and relaxation mechanisms in the atomic
emission process (A), atomic absorption process (B), atomic fluorescence process (C), and ionization process (D).
The resulting analytical signals from the above processes are measured by experimental arrangements depicted in
E, F, G, and H, respectively.

transmittance and is related to the concentration of the to yield excited atoms. The direction of observation of the
absorbing analyte atoms. In short, the greater the amount fluorescence is at right angles to the angle of incidence
of light that is absorbed, the more atoms are present in the of the excitation source on the atom cell to avoid looking
atom cell. directly at the light source. Once again, a higher population
of atoms in the atom cell produces a greater fluorescence
C. Atomic Fluorescence Spectrometry (AFS) signal.

In AFS, the excitation from the ground state to the upper


D. Detection of Elemental Ions
state (Fig. 1C) is accomplished by absorption of a photon,
and the measurement is made by detection of radiation When the deposited energy into an atom cell is suffi-
emitted by the atom as it relaxes back from the excited state ciently high, elemental ions are produced. The atoms ab-
to the ground state. This re-emitted radiation is no differ- sorb enough thermal or radiational energy to promote ex-
ent in character from the radiation emitted in the atomic citation of an electron above the bound state.
emission technique. In AES, the atoms are excited only by In laser-enhanced ionization, laser sources are used to
the collisional energy inherent in the high temperature of selectively produce the ion from a specific element. This
the atom cell, while in AAS and AFS the atoms are excited may be done either through resonance transitions or by
primarily by radiation from an external light source. exciting an electron to a bound state which is then ion-
The experimental arrangement for AFS is illustrated in ized through subsequent collisions. This mode of ioniza-
Fig. 1G. A light source is used to irradiate the atom cell tion will yield a unique ion from an ensemble of different
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768 Atomic Spectrometry

FIGURE 2 Sequence of events that occur in flame during the conversion of crystalline salts into gas-phase atomic
and ionic species for spectrochemical analysis.

elements and as such an undiscriminating detector (e.g., spectrochemical analysis, one must be able to measure
a charge collector) may be used to selectively identify the photon intensity (to extract quantitative information)
a particular element (the selection is done through the and characteristic wavelength (to extract qualitative infor-
unique excitation wavelength). Conversely, in elemental mation). The optical information encoded in any of the
mass spectrometry, thermal sources (e.g., inductively cou- above spectrometric processes must be decoded in terms
pled plasma) are commonly used to ionize most elements of intensity and wavelength.
present within the plasma, to varying degrees. Therefore,
a mass analyzer is needed prior to the detection to provide
quantitative information for a given element without inter- A. Wavelength Selection
ference from all other ions present. Regardless of the mode The light emanating from an atom cell or the light used in
of ionization or detection, the ion current generated from atomic absorption experiments is generally composed of
an atom cell is proportional to the total amount of analyte several different wavelengths. The simplest approach for
initially present. The process of ionization and detection wavelength discrimination is to use an optical filter. But, to
is shown schematically in Figs. 1D and H. distinctly identify elements by their characteristic spectra
and to quantify the amount of analyte present by its signal
intensity, a wavelength-selection device is used. These de-
II. OPTICAL DETECTION vices are known as monochromators or polychromators,
depending on their ability to display a single wavelength
In atomic absorption, emission, and fluorescence spec- or multiple wavelengths at one time. Schematic represen-
trometry, the detection and characterization of photons tations of several different types of monochromators and
are the fundamental measurements that ultimately lead to polychromators are shown in Fig. 3.
the determination of elemental identity or the quantitative Typically, the light from an experiment is focused on
evaluation of a given analyte. Therefore, for a complete the entrance slit of the monochromator. The light on the
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Atomic Spectrometry 769

FIGURE 3 Schematic representation of the most frequently used grating-based monochromators (A, B, C) and
polychromators (D, E, F). A and D are known as Czerny–Turner design. Fastie-Ebert (B) and Littrow (C) have similar
designs in that both use a single reflective mirror. A Rowland circle polychromator is depicted in E, and F represents
an Echelle spectrograph.

slit is then collected by a collimating mirror and converted is the polychromator of choice due to its superb spectral
to parallel light rays that are directed toward a wavelength- resolution.
dispersion element (diffraction grating or prism). The
original light is now separated into discrete wavelengths,
B. Photon Detection
which are imaged by the mirror on the exit plane of the
monochromator. A slit is used to allow for propagation of a Historically, photographic films and plates have been used
unique wavelength out of the monochromator and into the at the exit plane of the monochromators to detect the spec-
detector. In most instances, a monochromator can be con- tral patterns from analytes. The main advantage of this ap-
verted to a polychromator by simply removing the exit slit proach is its inherent multi-wavelength detection ability.
and replacing the traditional detector by an area detector Because photographic films and plates are area detectors
(see next section). On the other hand, any polychromator with fantastic spatial resolution, the entire spectrum from
can be used as a monochromator if only a single output a sample may be recorded on a 30-cm plate, which ulti-
channel is used during an experiment. Although many mately results in simultaneous multi-elemental analysis.
wavelength-selection devices are available commercially, Unfortunately, the dynamic range of photographic emul-
the designs shown in Fig. 3 are among the most popular. sion is limited and the response function is typically non-
The Czerny–Turner monochromator is extremely popular linear. Furthermore, the overall process is extremely time
because of its compact design, while the Echelle system consuming and chemically intensive (need for a darkroom,
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770 Atomic Spectrometry

developing time, and chemicals for the development pro- III. ATOMIC EMISSION SPECTROMETRY
cess). Today, photomultipliers (PMT), photodiodes, and
array detectors completely dominate the photon detection A. Theoretical Background
arena. Schematic representations for a photomultiplier and
a charge injection device (a two-dimensional array detec- In atomic emission spectrometry, the intensity of emis-
tor) are shown in Fig. 4. Photomultipliers and photodiodes sion from the analyte atoms depends on the number of
are used as single-channel detectors with both monochro- atoms that are in the excited state. If the temperature of
mators and polychromators. Array detectors are used for the atom cell is increased, then more atoms undergo en-
simultaneous detection over a given spectral range. ergy exchange collisions with the surrounding hot gases.
In photomultipliers, a photon strikes the photoactive More atoms then possess enough energy to be excited to
material on a photocathode, resulting in ejection of an an upper state and drop back down to the ground state by
electron from the surface. The initial electron is acceler- loss of a photon. The expression that relates the tempera-
ated toward the first dynode, which upon collision releases ture of the atom cell to the number of atoms in the excited
several secondary electrons. This process is repeated by state is the Boltzmann expression. If n 0 is the number of
using several additional dynodes to yield an overall signal atoms in any given state with energy E 0 , then the number
amplification of 106 . Solid-state detectors (photodiodes n ∗ in an excited state with energy E q , is given by
 
and charge injection devices), however, do not intrinsi- n ∗ n 0 = gq g0 e−(Eq −E0 )/kT (1)
cally amplify the signal. In these devices, the initial pho-
ton results in a single charge-hole separation or single where k is the Boltzmann constant, and T is the absolute
charge storage. In all cases, the signal from the detec- temperature. The constants gq and g0 are the statistical
tor is electronically conditioned (e.g., amplified, filtered, weights (degeneracy), which account for the fact that there
time-gated, etc.) and is converted into an analog or digital are often several states with the same energy E q and E 0 ,
format to be used with a display device (e.g., computer, respectively.
analog gauge, digital display, etc.). The Boltzmann expression predicts the number of
atoms in the excited state, relative to the number of atoms
in the ground state. For example, considering the atomic
emission from Cs (852 nm; E q − E 0 = 1.46 eV) and Zn
(213.8 nm; E q − E 0 = 5.8 eV) at 4000 K, the n ∗ /n 0 ra-
tios for these elements are 2.98 × 10−2 (gq /g0 = 2) and
1.48 × 10−6 (gq /g0 = 3), respectively. Another way to use
the above equation is to generate a plot for the Boltzmann
factor (e−(Eq −E0 )/kT ) as a function of the excitation tem-
perature, as shown in Fig. 5. For a given transition (E),
the Boltzmann factor becomes dependent only on the tem-
perature; as a result, higher temperatures within the atom
cell will generate a larger population of the excited species,
which ultimately leads to higher emission intensities.
Flames have temperatures in the 2000–3000 K range,
while atmospheric pressure plasmas are in the 4000–
10,000 K range. In the air–acetylene flame, which has
a temperature of about 2540 K, it is possible to see rela-
tively large amounts of light emitted by sodium, cesium,
calcium, and other metals, but it is very difficult to see zinc
emission in the same flame. If a nitrous oxide–acetylene
flame is used, with its typical temperature of 3150 K,
larger signals from zinc and many other metals can be
seen. In general, flames are not a convenient source for
atomic emission measurements in light of the fact that
in plasmas, most elements can be determined with high
sensitivity by AES.
FIGURE 4 Examples of single-channel (photomultiplier) and two- The primary variable that determines the temperature
dimensional array (charge injection device) detectors for spectro- necessary to excite strong atomic emission signals from a
scopic applications. particular element is the energy difference (E q − E 0 ). The
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Atomic Spectrometry 771

FIGURE 5 The Boltzmann factor as a function of the excitation temperature. Each curve represents a particular E
in the ultraviolet or visible region of the electromagnetic radiation.

larger this difference, the more energy required to cause During the past two decades, plasma spectroscopy has
the element to be excited to the higher state. In general, dominated the analytical market for atomic emission spec-
elements with analytical lines (usually resonance lines) in trometry. Consequently, we will not discuss the use of
the blue or ultraviolet do not give a strong atomic emis- flames for atomic emission, as the industry, in large, has
sion signal in a flame. These trends can be seen in Fig. 5, moved toward plasmas for this application. On some oc-
where the analytes with short analytical wavelengths have casions, flame emission is used for analysis of sodium
a correspondingly low Boltzmann factor. and potassium. Nonetheless, these elements can be easily
In addition to the Boltzmann equation, the following determined by inductively coupled plasma spectrometry.
expression is used to account for other variables that affect
the atomic emission signal at low concentrations:
B. Inductively Coupled Plasma Spectrometry
 = Ahν0 n(gq /g0 )a L(/4π )e−(Eq −E0 ) (2)
1. Instrumentation
where  is the radiant power (in watts) emanating from the
atom cell, and n is the number of atoms in the atom cell A diagram of the inductively coupled plasma (ICP) device
per cm3 . A is the Einstein transition probability, which is shown in Fig. 6. The effective temperature of plasma is
indicates the probability that an excited atom, per unit two to three times higher than those observed in flames
time, will fall into a lower level by spontaneous emission (in the 4000–10,000 K region). Passing argon gas through
of a photon. This is a rate constant for the first-order decay a set of concentric quartz tubes within a strong radio fre-
of the atom from the excited state to the lower state. In the quency (rf) field generates the plasma. Radio-frequency
above equation, a is the area of the atom cell observed by energy at about 27 MHz and 2 kW of power is coupled to
the detector, L is the thickness of the atom cell, and  is the the water-cooled induction coils at the top of the quartz
solid angle (in steradians) over which the emission is being plasma tube. This energy is sufficient to accelerate ion-
observed. There are other losses that are often difficult to ized particles into many collisions which causes further
quantify, such as light losses in the optical components. In ionization and emission of significant background radia-
principle, if there are n ∗ atoms per cm3 in the excited state, tion from the argon gas. The plasma is ignited by seeding
then n ∗ A photons with energy hν0 will be emitted per unit with electrons generated by an electrical discharge. Af-
time and per cm3 . In the case of sodium, which has two ter the onset, the plasma becomes a self-propagating and
excited states of similar energy (589.0 and 589.6 nm) and -sustaining process. The tangentially introduced argon gas
similar A values, the relative emission intensities are the (Fig. 6) spins the plasma into a torroidal shape at the point
same as the ratio of their statistical weights (1 : 2). where the sample is introduced. The sample is injected
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772 Atomic Spectrometry

(HEN) is ideally suited for applications requiring efficient


nebulization at low solution-flow rates. In general, while
the ultrasonic nebulizer is more expensive than HEN and
cross-flow systems, it does provide for a better analytical
detection limit.

2. Instrumentation for Multi-Element Analysis


One of the primary advantages of an ICP is that it provides
good sensitivity for the determination of a wide range of
elements without significant chemical interferences. With
the use of any multichannel detection system, one can
detect the emission coming from many elements simulta-
neously. The spectrometers shown in Fig. 3 are capable

FIGURE 6 Schematic representation of an inductively coupled


plasma torch during operation.

into the center of the plasma where excitation is more effi-


cient. As shown in Fig. 6, the plasma may be divided into
observation zones where atomic or ionic species are more
abundant.
The sample is introduced into the plasma commonly
through a nebulizer. The function of the nebulizer is to
convert the sample solution into a fine aerosol spray. The
nebulizers are often coupled to a spray chamber where
large droplets are preferentially removed from the aerosol
stream. Discrimination against larger droplets facilitates
more stable plasmas and a better measurement precision.
The most frequently used nebulizers are depicted in Fig. 7.
Cross-flow nebulizers are robust aerosol generators suit- FIGURE 7 Three popular nebulizers used for introduction of so-
able for most applications. The high-efficiency nebulizer lutions into an atom cell.
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Atomic Spectrometry 773

of simultaneous interrogation of many spectral lines. The


electronic data-handling system is then able to gather data
from a large number of elements simultaneously. Thirty
elements are typical, and as many as 60 elements are prac-
tical for an optimized analytical run.

3. Sensitivity
Atomic emission signals in the ICP are much larger
than those in the flame for nearly all elements and can
be obtained for a wider range of elements. The high-
temperature, inert-argon environment of the ICP leads to
a more complete atomization and efficient excitation of
analytes, resulting in larger signals.
The copious energy in the ICP causes some atoms to
become completely ionized. For analytes with extensive
ionization, the atomic emission signal is minute, but the
ionic emission signal is quite substantial. The concept of
an ionic emission signal is exactly the same as that of
atomic emission. An ion has a different set of energy lev-
els from the equivalent neutral atom (i.e., ionic emission
signals occur at different wavelengths from the atomic
emission signals). This duality of ICP spectrometry has
led to the use of the name optical emission spectrometry
(OES) for the ICP emission technique rather than atomic
emission spectrometry. Signals from ion transitions are
used just as routinely as atom lines for the determination
of the concentration of an analyte. Furthermore, the ions
FIGURE 8 Atomic emission profile and potential spectral inter-
from an ICP may be extracted into a mass analyzer for ferences. (A) A typical atomic emission line profile intensity as
elemental mass spectrometry (discussed later). a function of wavelength (note the narrow width of the emission
line). (B) Two independent atomic emission profiles emitted from
two different elements that can be resolved with the use of a high-
4. Chemical Interference Effects resolution monochromator. (C) A typical molecular emission band
as a function of wavelength (note the emission coverage over
One of the most important advantages of the ICP over other a wide wavelength range as compared to atomic emission). (D)
atomic emission sources is the near absence of chemical Atomic emission superimposed on a concurrent molecular emis-
interferences. The argon plasma is inert and the tempera- sion (points 1 and 2 represent the background correction regions
ture is so high that nearly all compounds are broken down for the atomic emission signal).
efficiently. Virtually all the analyte is released for excita-
tion and subsequent atomic emission.
width of the spectral line at half-height (the half-width)
is about 5 pm, but it can vary by a factor of ten or more
5. Spectral Interferences
depending upon many fundamental and experimental pa-
Because of the high excitation temperatures attained rameters (e.g., temperature and pressure).
in ICP, the most serious disadvantage of this plasma is Some analytes emit lines that are very close to the lines
the relatively large number of spectral interferences. of other analytes (Fig. 8B). For example, iron emits radia-
Spectral overlap becomes very likely in complex sam- tion at a multitude of lines, any of which might be at almost
ples containing many elements over a wide range of the same wavelength as that emitted by another metal. If
concentrations. The potential spectral overlaps are often the slits on the monochromator are narrow enough and
remedied with the use of high-resolution monochromators if the dispersion of the monochromator is large enough,
(polychromators). spectral lines that are very close to each other will be
The atomic emission signal from a particular element is well separated. The resolution of a monochromator is said
not composed strictly of one wavelength but of a very nar- to be high if it is able to separate close spectral lines.
row range of wavelengths (approximated by Fig. 8). The The highest possible resolution is usually required for
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774 Atomic Spectrometry

TABLE I Elements with Pronounced Spectral Inter- scanning capability of monochromators may be used to
ference for Determination of Be Using 313.042 nm Line correct for these types of interferences. As seen in Table I,
Element Observed changes on Be emissiona (%) the presence of some elements (e.g., presence of Cr, Ta,
and U while measuring the emission from the Be 313.042
Cr −120 line) may cause an over-correction of the background
Ta −20 emission.
U −15 Spectral interferences can be corrected if the magnitude
Ag 0 of the interference is known as a function of the concen-
Gd +30 tration of the interfering element. A correction factor may
Th +75 be calculated and ratioed to the signal size at the ana-
Ti +160 lyte wavelength (concentration ratio method). This is best
a Positive changes in Be emission intensities are due to direct accomplished by making simultaneous measurements of
line or wing overlaps. Negative deviations are due to interference both the signal at the analyte wavelength and the concen-
at a background correction point. tration of the interfering element at another wavelength.
The main requirement is that the concentration of the in-
terfering element can be measured at the other analytical
atomic emission spectrometry, but most of the monochro- wavelengths without any spectral or other interferences.
mators that are commonly used in emission spectrome- Hence, polychromators are ideally suited for this proce-
try cannot resolve two lines that are closer than about dure. It is also assumed that both the interferent signal,
3 pm apart. which causes the spectral interference at the analyte wave-
If two spectral lines from two metals are not satis- length, and the interferent signal at the second wavelength
factorily separated, then a spectral interference occurs. behave in the same way in the plasma. This turns out to
Spectral interferences can still occur even with a large, be an acceptable method of correction for spectral inter-
high-resolution monochromator. The resulting measured ferences due to the lack of chemical interferences within
signal not only represents the element of interest, but also the plasma.
a component of the signal resulting from the interfering An internal standard is frequently used to correct for
element. In general, the signal is larger than it should drift in the signal size as a function of time. An internal
be, which results in an inaccurate measure of the ele- standard is an element of known concentration in a sample
ment concentration. As an example, a list of elements that is present in all examples of the sample. The instru-
with spectral interference for determination of Be is given ment monitors its signal, often simultaneously with the
in Table I. measurements described, and if it drifts in size an appro-
The monochromators that are used for ICP optical emis- priate correction is applied to the analyte signal to com-
sion spectrometry (ICP–OES) often include automatic pensate for the drift. This helps to ensure that the instru-
scanning capability to measure the background at each ment remains accurately calibrated for the duration of the
side of the analytical atom or ion line. The primary ap- analytical run.
proach to discriminating against spectral line interferences
is through the use of a high-resolution monochromator. If
this fails, then one recourse is to find another atomic or
ionic emission line that is sufficiently sensitive but which TABLE II Analytical Wavelengths Used in ICP-AES Analysis
is not affected by a spectral interference. Examples of ac- Primary Alternate Decreased
ceptable alternative emission lines for some elements are analytical analytical sensitivity
presented in Table II. Alternatively, it is possible to re- Analyte wavelength (nm) wavelength (nm) factor
move the element that is causing the spectral interference
Ag 328.068 338.289 2.0
by use of solvent extraction, or another chromatographic
Au 242.795 267.595 1.8
technique, prior to sample introduction.
Be 313.042 234.861 1.2
The atomic emission from inductively coupled plasma
Cd 214.438 228.802 1.1
frequently resides on a substantial background emission.
Cu 324.754 224.700 1.4
The majority of background continuum emission is due
Ga 294.364 417.206 1.4
to bremsstrahlung radiation (deceleration of fast-moving
In 230.606 325.609 1.9
electrons) or an electron-ion recombination process. An-
Ni 221.647 232.003 1.3
other cause of the background radiation is the molecu-
Pb 220.353 216.999 2.1
lar band emission from the OH species originating from
Zn 213.856 202.548 2.2
the aqueous samples (Fig. 8C). As shown in Fig. 8D, the
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Atomic Spectrometry 775

C. Electrical Discharges for Optical 2. dc Plasma


Emission Spectrometry
The dc plasma (DCP) technique is similar to ICP and less
1. dc and ac Arcs and Sparks like the electrical discharges described above. Figure 9
shows the basic arrangement of the three-electrode DCP
Arcs and sparks were the dominating emission techniques
system. The plasma is formed by the discharge of dc cur-
nearly four decades ago and in most arenas they have been
rent at low voltage across graphite electrodes bathed in
replaced by ICP emission spectrometry. Nonetheless, arcs
argon. The main difference between the DCP and the dc
and sparks have escaped complete extinction due to their
arc is that the sample is introduced in liquid form. The
versatility for analysis of solid samples. These techniques
sample is aspirated and converted into small droplets (us-
are still in use in many foundry-based industries and nu-
ing a nebulizer), in a way similar to the ICP systems. The
clear fuel-fabrication laboratories. These types of elec-
premixed droplets and argon are then allowed to flow into
trical discharge are comprised of two electrodes, across
the DCP observation zone. The sensitivity of the plasma
which an electric current is passed. In the case of the dc
for the determination of metals in samples is inferior to
and ac arcs, a low voltage of 10–50 V is used and a current
that of ICP. There are minimal chemical interferences,
of 1–35 A flows between the electrodes. The ac arc is a
and spectral interferences are as serious as with ICP. DCP
series of separate discharges that occur once during each
is also affected by easily ionized element (EIE) interfer-
half-period of the power cycle. The ac spark is based on the
ence, which cause a 30–80% enhancement of the signals
discharge of a capacitor that has been charged to 1–30 kV.
of some elements. DCP instrumentation is, in principle,
The spark occurs 120–1800 times per second. The tem-
similar to that of the ICP, because multi-element analyses
peratures of these discharges are in the same range as the
are possible by use of a spectrometer that has multiple
ICP; hence, many species can be excited, and quantitative
photomultiplier tubes.
and qualitative analyses can be obtained.
The sample is typically placed in a cup in the bottom
electrode, so the discharge occurs between the anode elec-
3. Glow Discharge Plasma
trode and the sample (cathode). The sample can be a con-
ductive solid or it may be crushed and mixed with a con- A direct current glow discharge (GD) plasma is formed
ducting material such as powdered graphite. in a low-pressure, inert buffer gas (e.g., 0.1–10 torr of
The instrumentation for these discharges is essentially Ar). The sample is composed of conductive material,
the same as those used for all emission experiments. The which becomes a part of the electrical circuit (cath-
detection system after the monochromator (also known as ode). The discharge is typically sustained at several hun-
a spectrograph) can be the multiple photomultiplier ar- dred volts at a current of a few mA. GD plasmas have
rangement, the older photographic plate arrangement, or a high charge density and large electric field gradients
a charge injection device. The intensity of the image of (kV/mm) near the cathode surface. Initially, the argon
each line is proportional to the amount of light emitted buffer gas becomes ionized and is accelerated toward
from the discharge at each wavelength, and the concentra- the cathode due to a net electric field. As the fast mov-
tion can thus be interpolated by use of standards of known ing Ar impinges on the cathode surface (sample), the
concentration. sputtering process removes a few layers of material.
Electrical discharges are affected by a number of se- The sputtered material is subsequently excited and ion-
rious matrix interferences associated with the way that ized through a series of complex gas-phase processes.
the sample is vaporized into the discharge as well as var- These include electron impact (A + e− → A∗ , A+ , A∗+ ),
ious chemical and physical interactions within the dis- Penning ionization by the metastable species of the
charges. Spectral interferences are as serious as for ICP– buffer gas (A + Arm → A+∗ + Ar), radiative recombi-
OES. These interferences can be mitigated, in part, by nation (A+ + e− → A∗ + hν), and radiation trapping
the use of internal standards and the concentration ratio (A + hν → A∗ ).
method. However, these approaches are not as successful Two types of glow discharge sources are illustrated
as with the ICP because the latter has fewer interferences in Fig. 10. The hollow cathode GD is often used as a
and better precision. Internal standards have to be cho- line source for many spectroscopic applications (such as
sen with great care because they must behave in the same atomic absorption, which is discussed in the next section).
way as the analyte. This is not trivial because the physico- A potential of up to 400 V is placed between the anode
chemical interference problems that occur in these atom and cathode of the lamp to initiate the plasma. During
cells vary greatly from element to element and sample to operation, an electrical current between 4 and 40 mA at
sample. 150–350 V sustains the plasma in a low pressure of an
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776 Atomic Spectrometry

FIGURE 9 A direct current plasma emission source.

inert gas (argon or neon). The cathode is made of the el- Another popular approach to glow discharge spec-
ement that is to be determined in a sample. Occasionally, troscopy is to use rf power instead of traditional dc power
these plasma sources may be used for determination of sources. The main advantage of rf-GD is its ability to sput-
elements in a solution matrix. In these instances, a few ter nonconductive samples, hence elemental analysis for
microliters of a solution are deposited and dried onto the polymers and ceramics becomes a matter of simple solids
cathode surface. The chamber is then evacuated and back- analysis.
filled with a small amount of Ar gas (1–10 torr). For dried
solutions, the analyte emission is a transient signal that is
4. Other Plasmas
integrated over time and compared to integrated intensities
for a standard solution. Microwave-induced plasmas (MIP) are generated using
The Grimm source is the most popular GD design for the microwave region of electromagnetic radiation (1–
spectrochemical determination of analytes in conductive 3 GHz). The microwave is generated by a magnetron
solids (Fig. 10). The plasma is a restricted discharge on source, and the energy is coupled into an inert gas (e.g.,
the cathode yielding uniform sputtering and well-defined He) containing the sample, using a waveguide and a cav-
craters. The calibration curves are always established with ity. About 50–200 W of power are needed to sustain the
known analyte concentrations in similar matrices. plasma. MIP is an ideal source for analysis of nonmetals
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Atomic Spectrometry 777

FIGURE 10 Two different glow discharge cells based on the hollow cathode and the Grimm-type design.

but it is not the most robust source for analysis of aqueous from the light source is related to the transmittance T ,
solutions. MIP has been successfully, applied to gas chro- where:
matography applications as an atomic emission source.
T = I /I0 (3)
Laser-induced plasma spectroscopy (LIPS), which is
also known as laser-induced breakdown spectroscopy Io and I are the initial intensity of the source and the source
(LIBS), is a versatile tool for elemental analysis. A pulsed intensity after the atom cell, respectively.
laser beam (lasting a few nanoseconds) is focused onto a The path length b in the atom cell (Fig. 1F) needs to be
target at power densities in excess of 100 MW/cm2 . The relatively long to maximize the amount of light absorbed
plasma is formed when the irradiance of the laser beam is by the analyte. The amount of light absorbed depends on
high enough to generate an electric field at the focal vol- the fundamental constant k , the atomic absorption coeffi-
ume that exceeds the breakdown threshold of the target cient. These parameters are related to transmittance in the
medium. Laser plasmas with well-defined spatial resolu- following manner:
tion can be formed in almost any medium. Good analytical
I /I0 = e−k b (4)
results may be obtained for LIBS instruments equipped
with time-resolved detection technology. Laser-induced The absorbance A is the parameter that is usually de-
plasmas can be optimized to yield a detection limit of tens termined with an AAS instrument, where:
of µg/g for certain elements in ideal matrices.
A = −log I /I0 = log 1/T = k b log e = 0.434k b (5)

The constant k prime is proportional to a number of pa-
IV. ATOMIC ABSORPTION rameters, including the number of atoms per unit volume,
SPECTROMETRY the Einstein transition probability for the absorption pro-
cess, and the energy difference (Fig. 1) between levels 0
A. Theoretical Background and 1. The Beer-Lambert law combines these constants
into one constant a to yield the following equation:
Figure 1B illustrates the basic principle of atomic absorp-
tion spectrometry (AAS). The amount of light absorbed A = abc (6)
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778 Atomic Spectrometry

FIGURE 11 A dual-beam flame atomic absorption instrument with the corresponding timing diagram.

where a is a constant called the absorptivity and c is the 1. Instrumentation


concentration of the analyte in solution. The hollow cathode lamp: The most important aspect of
The signal in an atomic absorption instrument is the AAS instrumentation is the light source, the most com-
measured reduction in the light intensity from I0 to I . In mon of which is the hollow cathode lamp (HCL). Figure
modern instruments, the logarithm is automatically calcu- 10 illustrates the basic construction details of these lamps.
lated so that the output of the instrument is the absorbance. Other line sources such as electrode-less discharge lamps
Absorbance is a unitless number that varies typically be- are frequently used for determination of nonmetals. In ad-
tween 0.001 and 2, but the number is usually referred to dition to dc operation, hollow cathode lamps may be oper-
as absorbance units. The AAS calibration curve is a plot ated by supplying pulsed current (at about 50–200 Hz) to
of A versus c with a slope of ab. It is best to work at increase the average amount of light that can be obtained
concentrations that give signals in the middle of the ab- from the lamp. Atomic absorption profile is the term used
sorbance range. to describe the range of wavelengths over which it is pos-
sible for an atom to absorb radiation. The amount of light
absorbed is proportional to the atomic absorption coeffi-
B. Flame Atomic Absorption Spectrometry
cient k (Fig. 12A). In most atmospheric pressure atom
Flame AAS may be used to determine the concentration cells, the profile has a typical width at half-maximum of
of most metals by using an acetylene-based flame. An 5 pm or greater and is a function of temperature and the
instrumental arrangement for a flame atomic absorption concentrations of major species in the atom cell. The pri-
spectrometer is presented in Fig. 11. There are virtually mary assumptions of the Beer–Lambert law is that the half-
no spectral interferences that affect AAS. Nonetheless, the width of the light source is narrower than the half-width of
main limit to analysis by AAS is due to physico-chemical the atomic absorption profile. The HCL is almost an ideal
interferences. The proliferation of ICP instruments has source for AAS because of its narrow spectral line profile
significantly reduced the overall application of flame AAS (half-width = 2 pm). Figure 12A shows a representation
in most industrial applications. More than likely, the use of of the overlap of the light source emission profile with the
flame atomic absorption will dwindle to only a few special- atomic absorption profile. If the light source spectral line
ized applications (similar to flame emission instruments). width is significantly broadened (i.e., it is comparable to
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Atomic Spectrometry 779

contrast, ICP, AES, and AFS have linear dynamic ranges


of 3 to 6 orders of magnitude.
The flame: For AAS measurements it is necessary to
break down compounds in the flame into their constituent
elements. Air–acetylene and nitrous oxide–acetylene are
the most frequently used flame gases. Most elements can
be determined by AAS in the air–acetylene flame. The
nitrous oxide–acetylene flame is necessary for 5–15 ele-
ments whose compounds do not break down sufficiently
in the air–acetylene flame. Aluminum, for example, does
not produce a signal in the air–acetylene flame, while cal-
cium gives signals in both flames but a larger signal in the
nitrous-oxide flame. The burner used is usually a slotted
burner (Fig. 11), which allows for the maximum signal
due to the long absorption path length.
Modulation techniques to discriminate against back-
ground signals: The experimental arrangement for optical
modulation is shown in Fig. 11. As depicted in the fig-
ure, the hollow cathode lamp is placed on the optical axis
of the monochromator. In this arrangement, the incident
HCL radiation is split into two parts, one passing through
the flame and the other passing around the flame. A mir-
rored optical chopper is used in front of the HCL so that the
light output is periodically interrupted and rerouted around
the flame. This is called intensity modulation of the light
source output and is used to allow discrimination against
background signals. The two main background signals that
affect AAS (and AFS) measurements are the background
light emitted from the atom cell and the atomic emission
signals from the elements in the sample matrix. Atom
cells always have some inherent background luminosity.
While the background in the flame is due to the emis-
sions that result from the chemical reactions within the
flame, graphite furnace atomizers (see next section) emit
blackbody radiation. All atom cells are hot enough to ex-
FIGURE 12 Influence of line shape on calibration parameters for cite some atomic emission signals. Consequently, absorp-
atomic absorption spectrometry. (A) Comparison of atomic line tion (and fluorescence) signals are always accompanied
widths for a hollow cathode lamp versus the atomic absorption by atomic emission signals from most of the matrix ele-
line width observed in atmospheric pressure atom cells. (B) The
slope and linear dynamic range of the calibration changes from
ments. All background signals must be subtracted to avoid
“I” to “II” as the emission line width of the hollow cathode lamp the spectral interferences associated with the atomic ab-
becomes broader. sorption measurements. Figure 11 helps demonstrate how
modulation subtracts out these background signals and is
the absorption profile), then the slope of the calibration an illustration of the temporal behavior of the signals that
curve changes, as illustrated in Fig. 12B. This change in are observed by the detection system at a particular wave-
the slope results in a loss in sensitivity. Such broadening of length. The flame background emission and the matrix
the light source emission profile occurs in practice as the atomic emission signals are emitted continuously from
HCL ages or if it is run at operating currents that are too the atom cell while the sample is being introduced and are
high. Regardless of the lamp output profile, AAS tends to represented in Fig. 11 as the baseline. The hollow cathode
have calibration curves that have a limited linear dynamic lamp emission is also observed by the detection system,
range (the straight part of the calibration curve) relative but the chopper periodically switches off its signal. While
to the other atomic spectrometric techniques (AES and the lamp is blocked, a measure of the total background
AFS). The AAS linear dynamic range is typically about can be made and then subtracted from the HCL signal plus
two orders of magnitude as a function of concentration. In background signal that is obtained when the HCL is on.
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780 Atomic Spectrometry

Hence, all backgrounds, including any atomic emission and complexing agents such as EDTA (ethylenediaminete-
spectral interferences, are subtracted out automatically. traacetic acid). Releasing agents increase the magnitude
The monochromator and detection system: The mono- of the signal in real samples. They can also change the
chromator for AAS does not need to have the high reso- magnitude of the signal from the standard solutions.
lution necessary for AES, because the selectivity of AAS Spectral interferences: The elegance of atomic absorp-
depends on the line width of the light source as discussed tion lies in the very high selectivity of the technique. The
above. The role of the monochromator is to reject the ma- HCL only emits light that is characteristic of the elements
jority of the background radiation as well as selecting only in the cathode. While in the atom cell there may be many
the pertinent HCL emission line for AAS measurements, elements present, only one element that corresponds to the
thus monochromators for AAS have a moderate resolution cathode material absorbs the light, because only the light
of 0.02–2.0 nm. The detection system is based on a pho- characteristic of that element is emitted by the light source
tomultiplier tube, and the readout electronics are similar and reaches the detector. The HCL acts like a probe to de-
to single-element AES instruments. termine the concentration of only one metal. This means
that virtually no spectral line interferences affect AAS.
The technique is often much simpler to use than AES, and
2. Interference Effects
the instrumentation can be relatively inexpensive while
Physico-chemical interference effects: The flame atom- providing high sensitivity and selectivity.
ization process is affected by chemical interferences that
prevent facile formation of neutral metal species of M.
C. Graphite Furnace Atomic
For example, oxides of many metals are likely to form in
Absorption Spectrometry
the flame environment. Oxygen is abundant in any flame
as a consequence of the oxidant (air, oxygen, or nitrous Graphite furnace AAS, also known as electrothermal
oxide) used in the combustion process. The main con- atomic absorption spectrometry (ETV–AAS), is one of the
cern is whether or not there is enough energy in the flame most sensitive techniques available for routine elemental
to break the bond between the metal and the oxygen to analysis. This technique is capable of the determination
release the metal. If the flame does not have enough en- of picogram (10−12 g) amounts in a few microliters of
ergy, most of the metal oxides remain intact and very little sample.
free metal is available. Phosphates also cause chemical
interference due to formation of a stable compound in the
1. Instrumentation
air-acetylene flame that breaks down slowly to release the
metal atom. This reduces the expected signal size signif- The arrangement for this technique is similar to that for
icantly. In striving to discriminate against chemical inter- flame AAS, except that a graphite furnace replaces the
ferences, the main aim is to obtain some assurance that the flame. The atomizer consists of a graphite tube about 3 cm
signal measured by the detection system does indeed quan- long, with a 6-mm internal diameter and wall thickness of
titatively represent the concentration of the analyte in any about 1 mm. Two different graphite tube designs are shown
particular matrix. We try to calibrate the instrument with in Fig. 13. The tube is fixed between two electrodes and
a known concentration of the analyte in a deionized wa- is subjected to a low-voltage (up to 12 V), high electrical
ter matrix and then compare directly the signal from a real current. The power supply can be programmed to heat the
sample with the calibration curve. The real sample compo- furnace to several pre-selected temperatures. The furnace
nents in the matrix, such as phosphate in a biological ma- has an inert gas passing through and around it to min-
trix during the determination of calcium, cause the signal imize the ingress of oxygen from the air, which would
to be smaller (a depression) or sometimes larger than the lead to rapid oxidative degradation of the furnace tube.
signal obtained from the same concentration of analyte in Five to 100 µl of the sample solution are placed in the
the calibration solution. One way to circumvent chemical furnace and dried at 100◦ C. The sample is then pyrolyzed
interferences is to use releasing agents. Lanthanum chlo- to break down or volatilize the matrix component. The
ride, which is usually added (1% weight/volume) to all pyrolysis temperature is set high enough without uninten-
sample solutions, is a good example of a releasing agent. tionally vaporizing the analyte (about 400–1200◦ C). After
The lanthanum oxide and phosphate compounds are often pyrolysis, the furnace is rapidly heated to the atomization
more stable than the same compounds of other metals. In temperature to volatilize the analyte into the atom cell. The
the flame, the lanthanum oxide or phosphate forms in pref- atomization temperature can be anywhere in the range of
erence to the analyte oxide or phosphate and thus releases a few hundred to about 2700◦ C. The analyte then absorbs
the analyte atom. Other releasing agents that have been light from the hollow cathode lamp to give the atomic ab-
found to work in many situations are strontium chloride sorption. This signal is a transient (Fig. 13E), because the
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Atomic Spectrometry 781

FIGURE 13 Graphite furnace electrothermal atomizers and their corresponding temperature profiles and analytical
signals. (A) and (C) correspond to furnace geometry and the tube temperature profile for transversely heated atomiz-
ers. (B) and (D) correspond to furnace geometry and the tube temperature profile for longitudinally heated atomizers.
The appearance time of the analytical signal for sample atomization from the furnace wall or the platform is highlighted
in (E).

sample is pulse vaporized and the atomic vapor diffuses center of the tube, it may condense at the cooler ends of
rapidly out of the tube. the graphite furnace.
Regardless of the furnace design, the sample is usually
vaporized from a small graphite platform that is placed
2. Tube Design and Heating Characteristics
inside the graphite tube (Fig. 13A and B). The sample is
Figure 13 illustrates two popular tube designs for elec- placed on the platform through a small hole in the top
trothermal vaporization. The transversely heated graphite center of the furnace tube. Figure 13E illustrates the dif-
tube (Fig. 13A), also known as an integrated contact ferent atomization profiles expected when the sample is
cuvette, is heated through the electrical contacts at the vaporized either from the furnace wall or the platform.
side of the atomizer tube. This allows for a more uniform This figure helps to illustrate the function of the platform
heating profile along the length of the graphite tube, as and explain why it is a useful tool. The graphite tube takes
shown in Fig. 13C. In longitudinally heated furnaces a finite time to heat up, as indicated by the tube-wall tem-
(Fig. 13B), the atomizer is heated through the electrical perature versus time plot. The vapor temperature in the
contacts at the ends of the graphite tube. Although simpler furnace follows the tube-wall temperature, and if the sam-
in design, these furnaces tend to have a significant thermal ple is placed on the bottom wall of the tube, it heats up at
gradient along the length of the graphite tube (Fig. 13D). the same rate as the tube. In most cases, the sample is va-
Consequently, because the analyte is vaporized at the porized while the tube is still heating up and results in the
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782 Atomic Spectrometry

appearance of the analyte transient quite early in the heat- centration. Because of the fast heating rates employed in
ing cycle. The main problem in the early appearance of the electrothermal vaporization, the transient from the furnace
atomization profile is with the gas-phase chemistry. The lasts for a very short time and it is necessary to have an
sample is vaporized into a cooler environment, which may instrument with relatively fast (ms time-scale) electronics.
not allow for decomposition of small molecules yielding
a sufficient number of free atoms. But, if the sample is de-
6. Physico-Chemical Interferences
posited on a small graphite platform (inside the graphite
tube), it will be vaporized into the hot environment of The processes that lead to breakdown of the matrix, va-
the furnace later than in the wall atomization case. The porization, and complete release of the analyte as a free
platform heats up later than the tube because of its ther- element vary from analyte to analyte and matrix. These
mal mass and little thermal contact with the tube. As a differing conditions are ultimately responsible for the in-
result, the vaporized sample enters a much hotter envi- terferences experienced by the analyte. These effects are
ronment than in the wall atomization case. The platform well studied and the role of ubiquitous species such as car-
often provides a sufficient delay in vaporization so that bon and oxygen are well documented with regard to the
many samples, upon vaporization, see a constant vapor vaporization process. Even though an attempt is made to
temperature even though each matrix may release the an- maintain an oxygen-free environment, the matrix usually
alyte at slightly different times. One analytical scenario contains oxygen. In addition, oxygen ingress through the
in which the platform vaporization may not be suitable is dosing hole has been observed even during the atomiza-
when refractory elements are to be determined. Refrac- tion stage. Compounds of the analyte, such as oxides or
tory elements have a very high vaporization temperature, halides (formed due to the presence of the matrix) may
and platform atomization will result in premature furnace not break down sufficiently to release all the analyte into
failure due to excessively high temperatures. the source radiation.
In a typical atomization cycle, the sample is vaporized Interference effects can often be minimized by the use
with a heating rate of about 1300–1500 K/s. After reaching of chemicals, which are added to the sample to modify
the desired temperature, the furnace is held at a constant the matrix so that interferences are controlled. A matrix
temperature for 3–4 seconds while the absorption pulse is modifier can both modify the matrix so that the analyte is
measured. vaporized relatively late during the atomization stage and
allow a higher pyrolysis temperature to be used without
3. Pyrolytic Coating of the Graphite Tube premature release of the analyte. Matrix compounds can
then be broken down during the pyrolysis step so that they
Atomic absorption spectrometry furnace tubes are sup- are less likely to cause interference during the atomization
plied with a hard pyrolytic graphite surface. This helps stage. Some typical matrix modifiers are ascorbic acid,
to reduce the porosity of the tube, which minimizes ad- magnesium nitrate, and palladium solutions. Modifiers are
sorption of hot metal vapors and slows down the rate of added in relatively high amounts (about 250 µg).
oxidation of the graphite and the accompanying mechan-
ical degradation of the furnace tube.
7. Background Correction
4. Inert Gas Requirements Small molecules, such as sodium chloride, that are present
An inert gas is used to flush the furnace during analy- during the atomization stage of a furnace analysis are often
sis. This prevents oxidation of the furnace. Usually an able to absorb or scatter radiation from the light source and
argon flow of about 300 cm3 /min. is maintained through cause a spurious absorption signal. This is called spectral
the furnace during the dry and pyrolysis stages of the anal- band interference. In addition, smoke and other particles
ysis. The flow is stopped or reduced during the atomiza- that are present during atomization can cause scatter of the
tion stage to minimize the gas expulsion from the furnace, radiation. This again causes an apparent spurious absorp-
which would reduce the absorbance signal. tion signals. These signals can be corrected effectively by
the use of one of two different methods of background
correction.
5. The Detection System
Deuterium lamp background correction (two-source
The transient signal is usually measured quantitatively by background correction): Two light sources are used in
evaluating the peak area (integrating) rather than by a mea- a deuterium lamp background corrected instrument. The
surement of peak height. While interference may affect first is the usual hollow cathode lamp, and the second is the
position and height of the absorption peak, the area of the deuterium lamp. The latter emits light over a broad range
transient often does not change for a given analyte con- of wavelengths. The deuterium lamp does not normally
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Atomic Spectrometry 783

give a significant atomic absorption signal from the ana- V. ATOMIC FLUORESCENCE
lyte element; however, it does give a scatter signal from SPECTROMETRY
particles within the furnace and an absorption signal from
molecular species. The modulation chopper is mirrored Atomic fluorescence is an extremely sensitive technique
so that, as the chopper spins, it alternatively irradiates the for determination of elements in samples. We should reit-
furnace by using either the HCL or the deuterium lamp. erate that in atomic fluorescence an external light source
Hence, when the HCL is irradiating the furnace, a signal is used to excite the analyte atoms. An ideal light source
is obtained that is composed of the true analyte absorp- for AFS must be much more intense than a hollow cathode
tion signal plus the spurious background signal. When lamp to achieve improvements in sensitivity. As a result,
the deuterium lamp is irradiating the furnace, only the pulsed hollow cathode lamps and lasers are frequently
spurious background signal is obtained. The subtraction used in AFS measurements. Excitation with a light source
of these two signals gives the actual analyte absorption such as a hollow cathode lamp, which only emits radiation
signal. The deuterium lamp works best for elements that specific for the element of interest, makes AFS virtually
have analytical wavelengths in the ultraviolet region of the completely free from spectral interferences. In addition,
spectrum. For background correction in the visible region AFS is like AES in that a multi-element analysis can be
a tungsten–halide lamp may be used. achieved by putting several light sources around the atom
Zeeman background correction: This method of back- cell, as discussed below.
ground correction makes use of the fact that a magnetic
field is able to split the atomic energy levels of an analyte.
A. Theoretical Background
A magnet is placed around the furnace, with the lines of
force of the field perpendicular to the direction of propa- This discussion assumes that the spectral line width of the
gation of the light beam. In this configuration the atomic light source is narrow relative to the absorption profile of
energy levels of an analyte can be split from the normal the analyte atoms, as illustrated in Fig. 12A. The atoms
situation into three energy levels (σ1 , σ2 , and π). The π absorb light from the source, and some of the energy is
energy level absorbs only light of a particular polariza- re-emitted as fluorescence, while various collisional pro-
tion, which is a natural consequence of the splitting of the cesses in the atom cell deplete the remainder of energy.
energy levels. The light source is deliberately polarized The ratio of the amount of light absorbed to that emitted
so that no light can be absorbed by the π energy level. is called the quantum efficiency (Y ) and is ideally equal to
Then two measurements are made. First, the magnetic one. In its simplest form, the equation for fluorescence ra-
field is switched off, and a measurement of signal plus diant power ( f ) resembles general expressions in atomic
background (A) is obtained. In this case, the light-source absorption (because for optically unsaturated systems the
polarization is irrelevant because atoms that are not in a fluorescence signal is a function of the initial source radi-
magnetic field absorb light of any polarization. Second, ant power, 0 ):
the magnetic field is switched on, causing the atoms to
 f = 0 (1 − e−kl ) (7)
split into the various components. When the field is on,
no analyte absorption of light occurs, because the light In the above equation, k is the absorption coefficient and
source is not of the correct depolarization even though l is the optical path length for the atom cell. Therefore,
it clearly is still at the correct wavelength. The σ compo- in AFS the signal size is directly proportional to both the
nents are not involved because they are at the wrong wave- light-source intensity and the atom concentration. Calibra-
length to absorb energy from the light source. Therefore, tion curves for AFS with HCL excitation are linear with
the signal obtained (B) results only from light absorbed or a slope of 1 (on a logarithmic plot) at low concentrations
scattered by background species and particles. The simple and bend back towards the concentration axis with a lim-
subtraction (A–B) then gives the background-free analyte iting slope of –0.5 at high concentrations. The curvature
signal. This method has been proven to give reliable and at high concentration is related to self-absorption in the
accurate background correction for all elements that are atom cell.
normally analyzed by AAS. It is particularly easy to ap-
ply because only one light source is used which removes
1. Light Source
many alignment problems that causes difficulties in a two-
source system. The background measurement is made at The multi-element capability of AFS is realized by use of
exactly the same wavelength as the source and analyte several light sources. The HCLs used for AFS are special
wavelengths. In contrast, two-source correction measures high-intensity versions of the ones used for atomic absorp-
the background over the range of wavelengths that exit the tion and up to 12 of them can be arranged in a practical
monochromator. experimental arrangement. Lasers are also frequently used
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784 Atomic Spectrometry

ground correction, could be mistaken for fluorescence.


When an ICP is used as the atom cell, the scattering inter-
ference is not observed. The ICP is so efficient at breaking
down droplets and particles that very few scatter signals
have been detected in an HCL–ICP instrument.

VI. DETECTION OF ELEMENTAL IONS

The laser-enhanced ionization (LEI) technique or elemen-


tal mass spectrometry may be used to directly measure
elemental ions. In LEI, a laser beam is used to excite the
analyte atoms in either a flame or electrothermal atomizer
cell. These atom cells are selected for LEI experiments be-
cause of their inherently low background ion population
(in contrast to plasma sources, which are rich in ions). The
laser-excited atoms undergo collisional processes that will
FIGURE 14 Laser atomic fluorescence in flame atomizers. The
ultimately lead to ionization of the analyte atoms. The ions
photomultiplier tube (PMT) is equipped with a band-pass filter.
are then collected and measured against a background cur-
rent. Although extremely sensitive, the LEI technique is
for AFS measurements because of their inherently large limited to detection of one analyte at a time in a flame or
radiant intensity. The general diagram for a flame atomic ETV atom cell. There are currently no commercial instru-
fluorescence instrument with laser excitation is shown in ments available for LEI analysis.
Fig. 14. Another approach for detection of elemental ions is to
use ICP sources (which are very rich in ion population)
in tandem with mass spectrometric detection. Under typ-
2. Detection System
ical operating conditions, about half of the elements in
Generally, monochromators are not used in AFS measure- the periodic table are singly ionized with an efficiency of
ments. For hollow cathode excitation, each HCL has a 90% or greater. The schematic diagram for an ICP–MS
paired dedicated photomultiplier tube detector. In front of instrument is shown in Fig. 15.
each photomultiplier tube is a filter, which allows a range Unlike the upright configuration in ICP–AES, in ICP–
of wavelengths to pass through it including the atomic- MS the plasma torch is placed on its side along the axis
fluorescence wavelength of the element excited by the of the mass spectrometric ion collection optics. A water-
HCL. The filter provides discrimination against the back- cooled cone is placed into the tip of the plasma to sample
ground emission from the atom cell. A high-resolution a portion of the ions generated by the ICP. The extracted
monochromator is not used for AFS, because the resolu- ions pass through another orifice, the skimmer, through
tion is provided by the specificity of the light source for the a differentially pumped region of the mass spectrometer.
element of interest. Although a low-resolution monochro- Differential vacuum pumping allows for the transfer of
mator can be, and often is, used for AFS, filters pass ions from plasma at atmospheric pressure into the high
more total light onto the photomultiplier tube and provide vacuum environment of the mass analyzer. The ions are
adequate resolution (in the range 2–10 nm) to discrim- guided through a series of lenses for the optimal signal-
inate against much of the background from the plasma. to-noise ratio at all mass ranges.
The light sources used for AFS measurement are always
modulated to allow discrimination against background
TABLE III Examples of Isobaric Interferences
emission.
Observed in ICP–MS

Analyte Mass Interfering ion


3. Spectral Interferences
Si 28 12 C16 O+ , 14 N+
2
Because of the selectivity of the excitation source, 38 ArH+
K 39
the spectral interferences are almost completely absent. 40 Ar+
Ca 40
Nonetheless, some spectral interference has been reported. 40 Ar35 Cl+
As 75
This interference is caused by scatter of the incident source 40 Ar+
Se 80 2
radiation off large droplets in the flame and, without back-
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Atomic Spectrometry 785

FIGURE 15 Schematic representation of an inductively coupled plasma mass spectrometer.

The linear dynamic range of an ICP–MS instrument is lyzers. Some common isobaric interferences observed in
typically about 4–6 orders of magnitude, while the sensi- ICP–MS are listed in Table III.
tivity is often 3 orders of magnitude better than the ICP–
AES technique. While the detection limits for many el-
ements with ICP–MS are better or comparable to AFS VII. COMPARISONS OF THE ATOMIC
and graphite furnace atomic absorption spectrometry, the SPECTROMETRIC TECHNIQUES
simultaneous multi-elemental detection afforded by ICP–
MS clearly places this technique in the lead for analytical It is unlikely that any one of the above analytical tech-
utility and versatility. niques is capable of replacing all other methodologies.
Interferences in ICP–MS are similar to chemical inter- Some techniques, however, have all but disappeared (e.g.,
ferences observed for ICP–OES. In addition, a number flame atomic emission), and others have been employed
of isobaric interferences caused by molecules with sim- for unique projects (i.e., LEI, for selective isotopic detec-
ilar mass-to-charge ratios of some analyte ions also in- tion). Frequently, a technique is selected based on the spe-
fluence the analytical results. These interferences can be cific analytical needs and instrument availability. A gen-
minimized by judicious use of acids in sample matrices, eral comparison of these techniques is outlined in Table IV.
optimized plasma power settings, use of different sam- The information provided in this table is a gross oversim-
ple introduction schemes, and use of altermate mass ana- plification of many experimental factors and it should be

TABLE IV Comparison of Atomic Spectroscopic Techniques


dc dc GD
ICP–OES arc plasma plasma FAA GF–AA AFS ICP–MS

Number of elements measured E E E E A A E E


Multi-elemental capability E E E E P P A E
Solids analysis P E P E P A P P
Micro samples P A P P P E P A
Qualitative analysis E E E E P P P E
Isotopic information P P P P P P P E
Detection limit A P A A A E E E
Dynamic range E P A A P P A E
Spectral (isobaric) interference A P A E E E E A
Chemical interference E P A A A A A E

Note: ∗ E = excellent, A = acceptable, P = poor.


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786 Atomic Spectrometry

used only as a first approximation to narrow down the BIBLIOGRAPHY


selection criteria.
Holcombe, J. A., Hieftje, G. M., and Majidi, V. (1998). “Focus on Ana-
lytical Spectrometry: A Compendium of Applied Spectroscopy Focal
SEE ALSO THE FOLLOWING ARTICLES Point Articles,” Society for Applied Spectroscopy, MD.
Ingle, J. D., and Crouch, S. R. (1988). “Spectrochemical Analysis,”
Prentice Hall, Englewood Cliffs, NJ.
ANALYTICAL CHEMISTRY • ATOMIC PHYSICS • MASS Laitinen, H. A., and Ewing, G. W. (1981). “A History of Analytical Chem-
SPECTROMETRY istry,” American Chemical Society Maple Press, PA.
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Encyclopedia of Physical Science and Technology en001f-44 May 26, 2001 14:57

Auger Electron Spectroscopy


C. L. Briant
Division of Engineering, Brown University, Providence, RI

I. Introduction
II. The Auger Process and Auger
Electron Spectroscopy
III. Applications in Materials Science
IV. Conclusions

GLOSSARY trons to determine the chemical composition of a solid


surface. Because the electrons that are detected are of very
Auger transition Electronic transition that produces low energy, this spectroscopy probes only the top two to
Auger electrons. It occurs in the following way: and five atom layers of the surface. This type of spectroscopy
electron beam impinges on the surface of a solid and is now routinely used in materials research to obtain in-
knocks out a core electron; an outer shell electron de- formation about the composition of solid surfaces.
cays into the hole and in so doing emits energy; this
energy can then knock another electron, the Auger elec-
tron, out of its orbital, and it can escape from the solid I. INTRODUCTION
into the vacuum if the atom is located near the surface.
Grain boundaries Internal interfaces in solids where two Of all the techniques that have been developed to analyze
single crystal grains meet one another. In most solids, surfaces, Auger electron spectroscopy has had the most
the atomic matching between the interfaces is poor. widespread application. In the field of materials science,
Intermetallic compound A compound made up of two or it has joined such analytical methods as X-ray diffrac-
more metals. The atoms of each metal occupy specific tion and transmission electron microscopy as a staple of
sites on the crystal lattice. The compound is thus said any well-equipped laboratory. It is used in chemistry and
to be ordered. materials science to study the composition of solid sur-
Segregation The process by which the composition of faces and the chemical states of atoms and molecules
a surface or internal interface becomes enriched in a on those surfaces. Chemists and physicists study the ba-
particular atomic species. The element reaches the in- sic Auger transition to help learn about electronic pro-
terface by diffusion through the bulk. cesses in solids. Those interested in developing electronic
equipment have been concerned with providing spec-
trometers with ever-decreasing incident beam diameters
AUGER ELECTRON SPECTROSCOPY is an elec- that will allow the chemical analysis of a surface on a
tron spectroscopy that employs Auger, or secondary, elec- microscopic scale. It is hoped that this article plus the

787
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788 Auger Electron Spectroscopy

bibliography will provide the interested reader with a start


in this field.
An obvious question that must be answered is why
Auger electron spectroscopy has achieved this place in
the surface analytical field. First of all, it is a relatively
straightforward technique to use, and high-quality com-
mercial spectrometers are available. The data are easily
interpretable, at least on a qualitative level, and it is also
possible to use an incident beam that is well under 1 µm
in diameter. This diameter is several orders of magnitude
smaller than what is possible for most other surface an-
alytical techniques, and this fact means that Auger spec-
troscopy can be used to probe changes in composition
across a surface at a microscopic scale. Finally, Auger
electron spectroscopy can detect every element except hy- FIGURE 1 Energy level diagram representing de-excitations by
(a) Auger electron emissions and (b) X-ray fluorescence. In the
drogen and helium, so it useful for studying both light and particular Auger process that is shown, a K-shell hole is first cre-
heavy element. We now wish to consider Auger electron ated and an electron in the LI shell drops down to fill it. In so doing,
spectroscopy and the process on which it is based. it gives off enough energy to knock an electron out of the LIII shell,
which becomes the Auger electron.

II. THE AUGER PROCESS AND AUGER


ELECTRON SPECTROSCOPY solid must come from very near the surface of the solid.
Although the yield of Auger electrons will again depend
When an electron beam impinges on a solid surface, it can on the particular element, it is estimated that most come
knock out inner shell electrons if it is of sufficient energy. from the top two to five atom layers.
The holes that are left behind will then be filled by having It had been recognized for some years after their discov-
outer shell electrons fall into them. This last process occurs ery that Auger electrons might provide a chemical analysis
with the emission of energy, since the outer shell electron of a surface, but it was not until the work of L. A. Harris
is changing from a higher to a lower energy. The energy in 1968 that the technique actually became feasible in the
that is given off can cause one of two events to occur. The laboratory. Prior to Harris’ work, the problem had always
energy can simply escape from the solid as an X-ray; in been that the Auger signal was so small compared with
this case, the process of X-ray fluorescence has occurred. that from other types of emitted electrons that it could not
In the other case, this energy can knock out another outer be adequately detected. Harris applied a phase-sensitive
shell electron. These electrons are the Auger electrons that detection scheme in which a small, regularly oscillating
were named for Pierre Auger who discovered this process voltage was superimposed on a larger, constantly increas-
in 1929. Such processes are usually denoted by the shells ing voltage. By measuring the electrons being collected,
of the electrons that are involved. Thus, a KLL Auger he was able to detect a small perturbation in the number
process means that the first electron that was knocked out of electrons at a given energy level, because the increased
was from the K shell, the hole was filled by an electron yield would be in phase with the frequency of the oscillat-
from an L shell, and the Auger or secondary electron that ing voltage. By electronically differentiating the signal in
was emitted was also from an L shell. this way, he could help bring out these small peaks. With
Figure 1 shows the processes of Auger emission and flu- this advance, the use of Auger electrons to measure sur-
orescence schematically. The frequency with which one face composition became a reality. Today, one can simply
of them will occur relative to the other depends on the obtain differentiated spectra such as those shown in Fig. 2
particular element; but as a rule of thumb, it can be re- and identify the elements present on the surface by com-
membered that elements with low atomic numbers tend to paring the energies of the peaks with those in handbooks
favor the Auger process, whereas those with high atomic of elemental standards.
numbers favor fluorescence. The Auger electrons that are Although Harris’ contribution was pivotal in the devel-
emitted have energies that are characteristic of the element opment of Auger electron spectroscopy, there have been
from which they came. Therefore, if they can be detected other advances since his that have helped Auger electron
they will provide a method of chemical analysis. Further- spectroscopy to become such a useful surface analytical
more, since the electrons that arise from such a process are technique. One of the most important was the development
going to be of low energy, those that do escape from the of the cylindrical mirror analyzer by Palmberg, Bohn, and
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Auger Electron Spectroscopy 789

dependent on such factors as trace contamination, the crys-


tallography of the surface, the roughness of the surface,
and the presence of other alloying elements in the solid
that is being analyzed. Although one can obtain accurate
calibration for a particular system, it is very difficult to
apply a given calibration to a variety of alloys on a rou-
tine analytical basis. Consequently, many researchers fre-
quently rely on relative changes in a normalized signal to
discuss changes in the surface composition. For example,
in the differentiated spectrum shown in Fig. 2, which was
taken from a steel fracture surface, one might choose the
strong iron peak at 703 eV and normalize all other peaks
by it. Then, one could discuss changes in normalized peak
FIGURE 2 Typical differentiated Auger spectra taken from steels.
The upper spectrum was from a nonembrittled (N.E.) steel, and height ratios to describe changes in the composition of this
the fracture surface that was analyzed was transgranular. The surface.
lower spectrum was from an embrittled steel, and the fracture The previous paragraphs give a brief introduction of
surface that was analyzed was intergranular. [From Stein, D. F., the Auger process and the basic way in which surfaces
Joshi, A., and LaForce, R. P. (1969). ASM Trans. Q. 62, 776.]
are analyzed with it. However, the great power of Auger
electron spectroscopy has been broad in its applicability.
We now wish to discuss these applications in the field of
Tracy. This analyzer provided a much higher signal-to-
materials science.
noise ratio and also allowed for much faster acquisition
of data. It is the analyzer on which most modern sys-
tems are based. Another important improvement was in III. APPLICATIONS IN
vacuum systems. When the early work was performed, MATERIALS SCIENCE
it was almost impossible to obtain a clean surface. The
vacuums were poor enough so that carbon and oxygen Auger electron spectroscopy has become one of the most
were adsorbed rapidly onto the surface. For a technique important tools for the investigation of interfaces in the
that only probes the top two to five atom layers, as does field of materials science. In fact, it is probably safe to say
Auger electron spectroscopy, this adsorption presented a that it has found its most widespread application in this
problem. With the development of ions pumps and tur- field. Because it does not give detailed chemical bonding
bomolecular pumps that provide a background pressure information about the species on a surface, other tech-
of less than 1 × 10−10 Torr, a clean surface could be pre- niques such as XPS and UV photoemission are more com-
pared routinely, either through fracture or by sputtering monly used for detailed chemical investigations. However,
with rare gas ions, and kept in this condition for 5 to 10 h. in materials science applications the need is more often to
Finally, new and much brighter filaments were developed detect the presence of elements on the surface of the solid,
that allowed a stronger Auger signal to be generated. In and for this application Auger electron spectroscopy is the
particular, the development of the lanthanum hexaboride preferred technique.
filament, which replaced the standard thermionic tung- The types of studies that have been performed can be
sten filament, offered a great increase in filament current. divided into two categories. One set is concerned with
This increase also meant that smaller areas (<1 µm in studies of the external surface. Segregation to the surface
diameter) on the surface could be analyzed, and it led to can cause its composition to be very different from that of
the development of the scanning Auger spectrometer. In the bulk. There has been great interest in understanding
this spectrometer, the Auger beam is first used to form how this difference in composition can affect such pro-
a secondary electron image of the surface that is being cesses as catalysis, corrosion, and oxidation. Also, one can
analyzed. The beam can then be placed on one particular use the kinetics of segregation to the surface to determine
area to obtain a spectrum from that spot. In the most re- the diffusion coefficient of an element in the solid. The
cent machines, field emission filaments are used that allow other type of study is concerned with internal interfaces,
analysis of a spot size of under 20 A. such as grain boundaries and particle–matrix interfaces.
One problem with Auger electron spectroscopy is the The composition of these interfaces can also be quite dif-
difficulty of converting the signal to accurate values of ferent from that of the bulk, as a result of segregation,
atomic percent. The reason for this difficulty is that be- and consequently, they can control various metallurgical
cause the Auger signal is so surface sensitive, it is very properties.
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790 Auger Electron Spectroscopy

Let us first consider the external surfaces. The most in which results could be misinterpreted. One is that the
common types of experiments that are performed are those surface will be covered with enough oxygen and carbon
in which the surface is cleaned and then heated to allow from the environment to mask the surface species that may
segregation. The heating allows solid state diffusion to oc- have originally caused a problem. The second is that con-
cur, and one finds that with time the composition of the taminants from handling of the material may show up and
surface can be significantly altered as a result of this seg- mislead the researcher in his or her effort to find the root
regation. Figure 3 shows an example of such changes in cause of a problem.
composition. The base material is an Fe-Cr-Ni 304 stain- In contrast, the direct studies of segregation to internal
less steel that has bulk concentrations of phosphorus, sul- interfaces have been extremely important in the solution
fur, and nitrogen that are below 300 ppm. However, as of many engineering problems. The basic segregation pro-
seen in Fig. 3, the concentration of these elements on the cess is similar to that which occurs for surface segregation.
surface can be quite significant. The solid is heated to a sufficiently high temperature and
The most common use of these types of studies has been solid state diffusion begins to occur. However, there is an
to simply detect elements present on the surface during a important difference in the way grain boundary segrega-
surface science experiment or to determine what elements tion is detected compared with the way surface segregation
will tend to segregate to interfaces when the materials are is studied. For the surfaces, the change in the composition
heated. Some investigations have attempted to use surface is simply monitored by impinging the electron beam on
segregation to predict the segregation that will occur to the surface while it is being heated. However, grain bound-
internal interfaces such as grain boundaries, but there are aries are internal interfaces and they must be exposed after
numerous studies which show that the differences between the segregation has occurred. What is done is to take ad-
grain boundary segregation and surface segregation are vantage of the fact that segregation often weakens the grain
great enough that such studies can, at best, give qualitative boundaries. The samples can then be fractured apart along
trends. their grain boundaries in the high-vacuum spectrometer,
One of the concerns of this type of experiment is that it and this fracture surface becomes the one that is analyzed
must be done in high vacuum, whereas most applications by Auger electron spectroscopy. However, the fracture
are in an environment of some type. Thus, one must be may not be completely intergranular, and this application
careful in the application of the results of these experi- is one where the development of scanning Auger electron
ments to situations where aggressive media are the cause spectrometers has provided a great advantage. One can
of the problem, such as would be the case for corrosion obtain an image of the fracture surface and select regions
or high-temperature oxidation. Another word of caution on it that are intergranular and analyze only them. One can
must be given about the analysis of surfaces that have been then compare the compositions of these regions with those
exposed to the atmosphere. Because of the extreme sur- from regions where the fracture goes through the grains.
face sensitivity of Auger spectroscopy, there are two ways The reason why Auger analysis of grain boundaries has
been so important is because the segregation often controls
metallurgical properties. We have already mentioned that
segregation often makes the boundaries preferred fracture
paths, and, in general, intergranular fracture is a very low
energy, undesirable fracture mode. Prior to the develop-
ment of Auger electron spectroscopy, it was suspected
that segregation of impurity elements, such as phospho-
rus, tin, and antimony, caused the embrittlement. Figure 4
shows the change in the ductile to brittle transition temper-
ature of Ni-Cr steel plotted as a function of the amount of
segregation of phosphorus and antimony. This transition
temperature measures the brittleness in steels, and as the
transition temperature increases, the brittleness of the steel
increases. This plot shows that there is a good correlation
between brittleness and segregation.
Another example of the effect of segregation can be
FIGURE 3 The segregation kinetics at 650◦ C for sulfur, phos-
to affect the response of the material to an external envi-
phorus, and nitrogen in a commercial 304 stainless steel alloy. In
this figure, changes in the peak height ratio are used to express ronment. Numerous studies have shown that phosphorus
changes in the composition of the surface. [From Briant, C. L., and segregation to grain boundaries of steel enhances its cor-
Mulford, R. A. (1982). Metall. Trans. A, 13A, 745.] rosion nitrate environments, nitric acid, picric acid, and
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Auger Electron Spectroscopy 791

FIGURE 4 The change in the ductile to brittle transition temper-


ature plotted as a function of the grain boundary concentration of
either phosphorus or antimony. The steels were a Ni-Cr base ma-
terial and were doped with one of these two elements. The grain
boundary concentration was determined by Auger electron spec-
troscopy. [From Mulford, R. A., McMahon, C. J., Jr., Pope, D. P.,
and Feng, H. C. (1976). Metall. Trans. A, 7A, 1269]

caustic solutions. Furthermore, it has been well estab-


lished that segregants that embrittle grain boundaries also
make the material more susceptible to hydrogen embrit- FIGURE 5 Auger spectrum from intergranular fracture surfaces
tlement. of undoped (a), (b), and (c) and boron-doped (d), (e), and (f) Ni3 Al.
Another type of environmental embrittlement that has (a) and (d) are spectra from as-fractured surfaces. All other sam-
received significant attention in recent years has been the ples were exposed to the indicated pressure of water vapor. [From
Lee, K. H., Lukowski, J. T., and White, C. L., (1996). Scripta Metall.
embrittlement of intermetallic compounds when they are 35, 1153.]
exposed to water vapor. In general, it has been found that
the water-molecules decompose on the surface of these sion at the grain boundaries is because it retards hydrogen
compounds and release atomic hydrogen. This hydrogen embrittlement.
then diffuses into the solid and causes embrittlement. Re- These examples are just a few of the many applications
search has also shown that the ease with which the disso- that Auger electron spectroscopy has had in materials sci-
ciation of water vapor occurs depends on the chemistry of ence. The references at the end of the article give many
the surface. more of them. Yet it seems fair to say that the overall theme
As an example of this effect, consider the results re- behind most of these studies is the fact that surfaces and
ported in Fig. 5. The intermetallic compound under in- internal interfaces can have very different compositions
vestigation was Ni3 Al, and the particular issue was to from that of the bulk and that this difference in composi-
determine whether or not the presence of boron on the tion causes them to have different properties. Auger elec-
grain boundaries affected the dissociation of water vapor. tron spectroscopy is used to detect the composition of the
The interest in boron additions stems from the fact that interface and allow correlation between composition and
boron on the grain boundaries of this compound appears properties to be made.
to enhance grain boundary cohesion. For this study, the
measure of dissociation of the water vapor on the sur-
face was the height of the oxygen Auger peak. (Recall IV. CONCLUSIONS
that hydrogen does not have an Auger signal.) To perform
the experiment the sample was fractured and exposed to This article has considered Auger electron spectroscopy.
water vapor. Figure 5 shows two sets of results. Those We have described the basic Auger transition, fundamen-
on the left are for a sample that did not contain boron. tal ways in which Auger electrons are detected, and vari-
Those on the right are for a sample that did contain boron. ous problems that can be encountered in using this spec-
The results clearly show that the presence of boron on the troscopy. We have also considered the application of this
exposed grain boundaries decreased oxygen absorption spectroscopy in materials science. In the early days of
and presumably dissociation of water vapor. Thus, this the development of this technique, it was a specialized
study suggests that one reason why boron enhances cohe- technique that was often the center of a particular study.
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792 Auger Electron Spectroscopy

Today, primarily as a result of the commercial availability BIBLIOGRAPHY


of excellent systems, it is used along with other techniques
to solve complex engineering problems. Briant, C. L., ed. (1999). “Impurities in Engineering Materials,” Dekker,
New York.
Briant, C. L., and Messmer, R. P., eds. (1988). “Auger Electron Spec-
SEE ALSO THE FOLLOWING ARTICLES troscopy,” Academic Press, Boston.
Briggs, D., and Seah, M. P. (1983). “Practical Surface Analysis by Auger
EMBRITTLEMENT, ENGINEERING ALLOYS • INFRARED and X-ray Photoelectron Spectroscopy,” Wiley, New York.
Smith, G. C. (1994). “Surface Analysis by Electron Spectroscopy: Mea-
SPECTROSCOPY • PHOTOACOUSTIC SPECTROSCOPY • surement and Interpretation,” Plenum, New York.
RAMAN SPECTROSCOPY • SURFACE CHEMISTRY • X-RAY Thompson, M., Baker, M. D., Christie, A., and Tyson, J. F. (1985). “Auger
PHOTOELECTRON SPECTROSCOPY Electron Spectroscopy,” Wiley, New York.
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Capillary Zone Electrophoresis


Tim Wehr
LC Resources, Inc.

I. Principles of Capillary Electrophoresis


II. Band Broadening in Capillary Electrophoresis
III. Capillary Electrophoresis Instrumentation
IV. Capillary Electrophoresis Separation Modes
V. Capillary Zone Electrophoresis
VI. Capillary Isoelectric Focusing
VII. Capillary Sieving Techniques
VIII. Isotachophoresis
IX. Micellar Electrokinetic Chromatography
X. Capillary Electrokinetic Chromatography

GLOSSARY an electric field is applied to a capillary carrying fixed


charges on the inner surface.
Anolyte Acidic solution (usually dilute phosphoric acid) Isoelectric point The pH at which an amphoteric species
used to terminate the anodic end of the pH gradient in (such as a polypeptide) has zero net charge and does
isoelectric focusing. not migrate in an electric field.
Carrier ampholytes Synthetic amphoteric compounds Joule heat The heating of a conductive medium as current
containing acidic and basic functions which migrate flows through it.
under the influence of an electric field to form a stable Plate height In chromatography and electrophoresis, the
pH gradient in isoelectric focusing. The composition measure of the amount of dispersion or spreading of a
of the carrier ampholyte mixture defines the extent and zone or peak during the separation process.
shape of the pH gradient.
Catholyte Basic solution (usually dilute sodium hydrox-
ide) used to terminate the cathodic end of the pH gra- CAPILLARY ELECTROPHORESIS (CE) is a rela-
dient in isoelectric focusing. tively new separation technology which combines aspects
Chiral selector Additives used in capillary electrophore- of both gel electrophoresis and high-performance liquid
sis and electrokinetic chromatography which complex chromatography (HPLC). Like gel electrophoresis, the
differentially with enantiomers such that the complexes separation depends upon differential migration in an
migrate at different rates. electrical field. Since its first description in the late 1960s,
Electroosmotic flow Bulk flow of the electrolyte when capillary electrophoretic techniques analogous to most

355
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356 Capillary Zone Electrophoresis

conventional electrophoretic techniques have been dem- with an electrolyte. A schematic of a CE system is pre-
onstrated: zone electrophoresis, isotachophoresis, isoelec- sented in Fig. 1. The capillary ends are immersed in
tric focusing, and sieving separations. Unlike conven- electrolyte-filled reservoirs containing electrodes con-
tional electrophoresis, however, the separations are nected to a high-voltage power supply. A sample is in-
usually performed in free solution without the require- troduced at one end of the capillary (the inlet) and ana-
ment for a casting a gel. As in HPLC, detection is lytes are separated as they migrate through the capillary
accomplished as the separation progresses, with resolved towards the outlet end. As separated components migrate
zones producing an electronic signal as they migrate past through a section at the far end of the capillary, they are
the monitor point of a concentration-sensitive (e.g., ul- sensed by a detector, and an electronic signal is sent to a
traviolet absorbance or fluorescence) detector; therefore, recording device.
the need for staining and destaining is eliminated. Data As in conventional gel electrophoresis, the basis of sep-
presentation and interpretation is also similar to HPLC; arations in capillary electrophoresis is differential migra-
the output (peaks on a baseline) can be displayed as an tion of analytes in an applied electric field. The elec-
electropherogram and integrated to produce quantitative trophoretic migration velocity ν E P (in units of cm/sec)
information in the form of peak area or height. In most will depend upon the magnitude of the electric field, E,
commercial CE instruments, a single sample is injected and electrophoretic mobility, µEP , of the analyte:
at the inlet of the capillary and multiple samples are
νEP = µEP E (1)
analyzed in serial fashion. This contrasts to conventional
electrophoresis in which multiple samples are frequently In a medium of a given pH, mobility of an analyte is given
run in parallel as lanes on the same gel. This limitation by the expression:
of CE in sample throughput is mitigated by the ability
µEP = q/6π ηr (2)
to process samples automatically using an autosampler.
Several multicapillary systems have been introduced to where q is the net charge of the analyte, η is the vis-
increase sample throughput; most of these are designed cosity of the medium, and r is the Stoke’s radius of the
specifically for high-throughput DNA sequencing. analyte. Since the Stoke’s radius is related to molecular
Compared to its elder cousins, CE is characterized mass and therefore to frictional drag, mobility will in-
by high resolving power, sometimes higher than elec- crease inversely with molecular weight and directly with
trophoresis or HPLC. The use of narrow-bore capillar- increasing charge. Mobility in units of cm2 sec−1 V−1 can
ies with excellent heat-dissipation properties enables the be determined from the migration time and field strength
use of very high field strengths (sometimes in excess by:
of 1000 volts/centimeter), which decreases analysis time
µEP = (I /t)(L/V ) (3)
and minimizes band diffusion. When separations are per-
formed in the presence of electroosmotic flow (EOF), the where I is the distance from the inlet to the detection
plug-flow characteristics of EOF also contribute to high point (termed the effective length of the capillary), t is the
efficiency. In contrast, the laminar flow properties of liq- time required for the analyte to reach the detection point
uid chromatography increase resistance to mass transfer, (migration time), L is the total length of the capillary, and
reducing separation efficiency. V is the applied voltage.
Because of its many advantages, CE is finding increas- In contrast to most forms of gel electrophoresis, the ve-
ing use as a tool in analytical chemistry. In some cases it locity of an analyte in capillary electrophoresis will also
may replace HPLC and electrophoresis, but more often it depend upon the rate of electroosmotic flow. This phe-
is used in conjunction with existing techniques, providing nomenon is observed when an electric field is applied to
a different separation selectivity, improved quantitation, a solution contained in a capillary with fixed charges on
or automated analysis. It was the adaptation of CE tech- the capillary wall. Typically, charged sites are created by
nology in the design of 96-channel DNA sequencers that ionization of silanol (SiOH) groups on the inner surface
enabled a draft of the human genome sequence to be com- of the fused silica. Silanols are weakly acidic and ionize
pleted in less than two years. at pH values above about 3. Hydrated cations in solution
associate with ionized SiO− groups to form an electrical
double layer: a static inner Stern layer close to the surface
I. PRINCIPLES OF CAPILLARY and a mobile outer layer known as the Helmholtz plane.
ELECTROPHORESIS Upon application of the field, hydrated cations in the outer
layer move toward the cathode, creating a net flow of the
As the name implies, capillary electrophoresis separates bulk liquid in the capillary in the same direction (Fig. 2).
species within the lumen of a small-bore capillary filled The rate of movement is dependent upon the field strength
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Capillary Zone Electrophoresis 357

FIGURE 1 General schematic of a capillary electrophoresis system. Capillary internal diameters can range from 25
to 150 µm, and capillary lengths can range from 20 cm to over 1 meter. In some cases, sample may be injected at the
capillary outlet, and the short segment between the outlet and the detection window serves as the separation path.

FIGURE 2 Electroosmotic flow in an uncoated fused silica capillary. The negative charges represent ionized silanol
groups on the silica surface, and the positive charges represent hydrated electrolyte cations.
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358 Capillary Zone Electrophoresis

the capillary wall remain constant from run to run. Com-


pounds such as polypeptides and organic amines are no-
torious for interacting with silica surfaces and changing
the level of EOF. A great variety of capillary surface treat-
ments and buffer additives have been developed for reduc-
ing adsorption and controlling EOF, and this continues to
be an active area of research in capillary electrophoresis.
Separation efficiency N in capillary electrophoresis is
given by the following expression:
N = µAPP V /2D (8)
where D is the diffusion coeffcient of the analyte in the
separation medium. This predicts that efficiency is only
diffusion limited and increases directly with field strength.
Note that V = E/L, so increasing capillary length will in-
crease the diffusion time, decreasing efficiency. Capillary
FIGURE 3 Magnitude of electroosmotic flow as a function of pH.
electrophoresis separations are usually characterized by
very high effiency, often as high as several hundred thou-
and charge density of the capillary wall. The population of sand plates. Efficiency in CE is much higher than in HPLC
charged silanols is a function of the pH of the medium, so because there is no requirement for mass transfer between
the magnitude of EOF increases directly with pH until all phases and because the flow profile in EOF-driven systems
available silanols are fully ionized (Fig. 3). The velocity is flat (approximating plug flow) in contrast to the laminar-
νEOF , of electroosmotic flow can be expressed as: flow profiles characteristic of pressure-driven flow in chro-
matography columns. Resolution, R, in CE is defined as:
νEOF = µEOF E (4)    
R = 1 4
µEP N 1/2 µEP + µEOF (9)
where µEOF is the electroosmotic mobility, defined as:
This implies that resolution will be greatest when µEP
µEOF = εξw /η (5) and µEOF are of similar magnitude but of opposite sign;
however, high resolution will be at the expense of analysis
where ε is the dielectric constant, ξw is the zeta poten-
time. It is also evident from Eq. (9) that, although Eq. (8)
tial of the capillary wall, and η is the viscosity of the
suggests that use of higher field strengths is the most direct
medium. Electroosmotic mobility can be determined ex-
route to high efficiency, a doubling of voltage yields only
perimentally by injecting a neutral species and measuring
a 1.4-fold increase in resolution, at the expense of Joule
the time, tEOF , when it appears at the detection point:
heat. The most direct route to optimize resolution is to
µEOF = (I/tEOF )(L/V) (6) increase
µ.
The apparent velocity, νAPP , of an analyte in an elec-
tric field will therefore be the combination of its elec-
II. BAND BROADENING IN CAPILLARY
trophoretic velocity and its movement in response to EOF:
ELECTROPHORESIS
νAPP = νEP + νEOF = (µEP + µEOF )E (7)
Band broadening and the resultant reduction in resolution
In the presence of electroosmotic flow, analytes which pos- can arise from several contributing factors. If the total band
sess net positive charge will migrate faster than the rate of broadening is expressed as plate height H , the contribu-
EOF, analytes which have zero net charge will be carried tions to band broadening due to initial zone width, diffu-
toward the cathode at the rate of EOF, and anionic analytes sion and electrodispersion, Joule heating, and adsorption
will migrate towards the cathode at a rate which is the dif- can be expressed qualitatively as:
ference between their electrophoretic velocity and νEOF .
If the magnitude of EOF is sufficiently great, all analytes H = h inj + h diff+cond + h joule + h ads (10)
regardless of their charge state will migrate past the de-
tection point. In this regard, performing separations in the
A. Initial Zone Width (hinj )
presence of EOF is highly desirable. However, achieving
reproducible separations requires that EOF be constant, Best resolution will always be obtained by keeping the
and this in turn requires that the surface characteristics of initial sample zone as small as possible. The starting zone
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Capillary Zone Electrophoresis 359

length should not exceed 5% of the total capillary length. The small internal diameters of fused silica capillar-
Sample zone sharpening can be achieved by preparing ies have been the key to high-resolution CE separations.
the sample in an electrolyte of lower conductivity than The smaller the capillary bore, the greater the surface-to-
the analysis buffer. Under these conditions, there is a dis- volume ratio and the more efficiently heat is removed from
continuity in field strength at the sample:buffer boundary the tube. The optimal capillary inside diameter (i.d.) for
such that ions migrating rapidly from a region of higher most applications is 50 to 75 µm. Capillaries with smaller
field strength become focused at the boundary. This fo- diameters are subject to plugging, and the high surface-
cusing or stacking effect not only produces narrow zones to-volume ratio increases the risk of adsorption. Capillar-
for increased resolution, but also increases zone concen- ies with larger internal diameters may exhibit significant
tration for enhanced sensitivity. Sensitivity enhancement loss in resolution due to thermal effects, and may require
is directly proportional to the ratio of sample to buffer operation at low field strengths or with low-conductivity
conductivity. Sample zone sharpening can also be accom- buffers.
plished by transient isotachophoretic preconcentration, as
discussed below.
D. Adsorption (hads )

B. Diffusion and Electrodispersion (hdiff +cond ) Wall interactions have been the greatest obstacle to achiev-
ing satisfactory resolution and reproducibility in capillary
Band broadening due to axial diffusion should be reduced electrophoresis, particularly in zone electrophoresis and
by shortening analysis time (i.e., by operating at high field isoelectric focusing. Approaches to minimizing or elimi-
strengths with short capillaries). On the other hand, higher nating adsorption include use of buffer additives and dy-
field strengths will generate more Joule heat, which in- namic or covalently-coupled capillary coatings.
creases diffusion rates. Electrodispersive band broaden-
ing arises from conductivity differences between the zone
and the background electrolyte. If this difference is large,
diffusion at one boundary of the zone is neglible due to III. CAPILLARY ELECTROPHORESIS
the zone-sharpening effect caused by the discontinuity in INSTRUMENTATION
field strength. In this case, the peak will be asymmetric;
that is, it will exhibit fronting or tailing depending on A variety of commercial CE instruments are available,
whether conductivity of the zone is greater or less than from simple modular systems consisting of a power sup-
that of the background electrolyte. This phenomenon is ply, detector, and injection device to fully integrated au-
readily observable when analyzing highly charged small tomated systems under computer control. This discussion
molecules such as inorganic ions, and satisfactory peak will focus on the features of automated CE instrumenta-
shapes can only be obtained by carefully matching sam- tion.
ple and electrolyte conductivities. The effect is much less
noticeable in other CE separations, except at high sample
A. Power Supply
concentrations.
Power supplies capable of delivering constant voltage with
high precision up to 30 kV are standard throughout the
C. Joule Heating (hjoule )
industry. Most systems offer, in addition, constant cur-
When an electric field is applied to a capillary containing rent operation at up to 300 µA; constant current operation
an electrolyte, Joule heat is generated uniformly across may be desirable in systems without adequate tempera-
the circumference of the tube. Since heat can only be re- ture control. High voltage is applied at the capillary inlet,
moved at the margin of the tube, a temperature gradient with the outlet (detector) at ground potential. When sepa-
exists across the radius of the tube. As noted in Eq. (2), rations are performed in uncoated fused silica capillaries
mobility is inversely related to viscosity, which decreases in the presence of EOF, the inlet (high-voltage) electrode
with temperature. Mobility increases approximately 2.5% is the anode and EOF carries analytes towards the cathode
for each degree rise in temperature. Therefore, the temper- (“normal” polarity). Separations performed in coated cap-
ature gradient creates a mobility gradient across the tube illaries without EOF may require “reversed” polarity. In
radius which contributes to band broadening. It should some separations, the direction of EOF may be reversed
also be noted that, in addition to this mobility gradient, by using capillaries coated with positively charged poly-
Joule heat can compromise resolution by increasing dif- mers or by using osmotic flow-modifying additives in the
fusion and convection; these are minimized by the use of background electrolyte. In these cases, reversed polarity
viscous buffers. is also used.
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360 Capillary Zone Electrophoresis

B. Injection injection) or application of hydrostatic pressure by ele-


vating the capillary inlet relative to the capillary outlet
Sample injection in CE requires the introduction of very
(gravity injection). Gravity injection has been reported to
small amounts of analyte at the capillary inlet with high
provide reproducible injection of very small sample zones.
precision. All commercial instruments offer electromi-
On the other hand, pressure injection can allow the flex-
gration injection and at least one type of displacement
ibility of introducing larger sample zones; this can be an
injection.
advantage when using injection pneumatics to introduce
Electromigration is the simplest injection method in
a chiral selector or to perform on-column concentration.
CE; the capillary inlet is immersed in the sample solu-
Moderate injection pressures can be an advantage when in-
tion and high voltage is applied for a brief period (typi-
jecting samples into capillaries containing analysis buffers
cally a few seconds). If no electroosmotic flow is present,
with viscous agents such as sieving polymers.
sample ions enter the capillary by electophoretic mobility
alone; this mode of sample introduction is termed elec-
trophoretic injection. If EOF is present, sample ions will C. Capillary Temperature Control
be introduced by a combination of electrophoretic mobil- Temperature control of the capillary environment is essen-
ity and electroosmotic flow; this mode is generally termed tial for attaining satisfactory reproducibility. Inadequate
electrokinetic injection. temperature control results in variable migration times. In
Electrophoretic injection offers two advantages. First, CE, peak area depends upon the residence time of the com-
if electrophoretic injection is performed in the absence of ponent in the detector light path and therefore is dependent
EOF, only species of like charge will enter the capillary. upon migration velocity. If migration times vary because
This enables discrimination against compounds of oppo- of inadequate temperature control, peak area precision will
site charge, simplifying the separation problem. Second, be poor. Control of capillary temperature above ambient
zone sharpening can be achieved using the stacking princi- temperature may be desirable in special applications—
ple described above. Unfortunately, these advantages are for example, in performing kinetic studies or on-column
countered by two major limitations. Since sample ions en- enzyme assays, in the study of protein folding, or for mu-
ter the capillary based on mobility, low-mobility ions will tation detection in amplified gene sequences. Operation
be loaded to a lesser extent than high-mobility ions. More at higher temperatures in capillary zone electrophoresis
importantly, presence of non-analyte ions in the sample will decrease analysis time and may improve peak shape.
will reduce injection efficiency, so electrophoretic injec- Operation at lower temperatures generally has little ad-
tion is very sensitive to the presence of salts or buffers in vantage in most modes of capillary electrophoresis.
the sample matrix. The disadvantages of electrophoretic Capillary temperature control can be achieved by forced
injection argue against its use in routine analysis except in air or nitrogen convection or by a circulating liquid cool-
cases where displacement injection is not possible (e.g., in ant. Forced air control permits the use of free-hanging cap-
capillary gel electrophoresis, CGE). Electrokinetic injec- illaries but is less efficient. Liquid cooling requires that the
tion suffers from the further disadvantage that many sam- capillary be enclosed in a sealed cartridge, but the cartridge
ple matrices contain components such as proteins which format provides for automatic alignment of the capillary
adsorb to the capillary wall and change the magnitude of in the detector light path and reduces time required for
EOF. capillary installation when changing methods.
Displacement or hydrodynamic injection is usually the
preferred method since analyte ions are present in the sam-
ple zone in proportion to their concentration in the bulk D. Detectors
sample, and injection efficiency is less sensitive to varia- Most of the detection modes used in HPLC have been
tions in sample ionic strength. However, it should be noted demonstrated for capillary electrophoresis (absorbance,
that the presence of high salt can affect detector response fluorescence, conductivity, electrochemical, radioactiv-
with displacement injection, and variations in the sample ity, mass spectrometry, postcolumn reaction). However,
viscosity (due to temperature variations or the presence of of these, only absorbance, fluorescence, conductivity,
viscosity-modifying components) can affect displacement and mass spectrometry are available for automated CE
injection efficiency. systems.
Two modes of displacement injection have been em-
ployed in commercial CE instruments: application of pos-
1. Absorbance
itive pressure at the capillary inlet and application of vac-
uum at the capillary outlet. The former method can employ As in HPLC, absorbance detection is used in the vast ma-
pressurization of the sample headspace by gas (pressure jority of CE applications, and all commercial CE systems
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Capillary Zone Electrophoresis 361

employ UV or UV–Vis absorbance as the primary mode of through the capillary is dispersed by a grating onto an array
detection. The simplest approach is the use of line-source of photodiodes, each of which samples a narrow spectral
lamps or continuum-source lamps with wavelength selec- range. In fast-scanning detectors, monochromatic light is
tion by filters. Better flexibility is obtained using a con- collected from the source using a movable grating and slit
tinuum (e.g., deuterium lamp) source with wavelength se- assembly and directed to the capillary; light transmitted by
lection by a grating monochromator. the capillary is detected by a single photodiode. Scanning
All commercial CE absorbance detectors employ on- is accomplished by rapidly rotating the grating through an
tube detection, in which a section of the capillary itself angle to “slew” across the desired spectral range. Photodi-
is used as the detection cell. This permits detection of ode array detectors are more sensitive in full-scan mode,
separated zones with no loss in resolution. Most capil- but the high light intensity can damage coated or gel-filled
laries used for CE are coated with with a polymer (usu- capillaries.
ally polyimide) which protects the fused silica capillary
and provides it with mechanical stability. Since the poly-
2. Fluorescence
mer is not optically transparent, it must be removed from
the detection segment to form a “window,” and this win- Fluorescence detection offers the possibility of high sen-
dow must be accurately positioned in the optical path to sitivity and, in the case of complex samples, improved
achieve good sensitivity. This segment of bare capillary selectivity. However, this mode of detection requires that
is very fragile and is subject to breakage during manipu- the analyte exhibit native fluorescence or contain a group
lation and installation of the capillary. Capillaries with a to which a fluorophore can be attached by chemical deriva-
UV-transparent coating are commercially available which tization. The number of compounds that fall into the for-
eliminate this problem; however, the coating is not resis- mer category are small, and while many analytes contain
tant to some coolants (e.g., fluorinated hydrocarbons) used derivatizable groups (e.g., amino, carboxyl, hydroxyl),
in liquid-cooled CE systems. most derivatization chemistries are limited by one or more
In on-tube detection, the internal diameter of the cap- disadvantages (slow reaction kinetics, complicated reac-
illary forms the detection light path. In accordance with tion or cleanup conditions, poor yields, interference by
Beer’s law, the sensitivity of a concentration-sensitive de- matrix components, derivative instability, interference by
tector is a direct function of the length of the light path. reaction side products or unreacted derivatizing agent).
Therefore, in comparison to an HPLC detector with a When compared to fluorescence detectors for HPLC,
1-cm path length, detector signal strength should be re- the design of a fluorescence detector for CE presents some
duced 200-fold in a CE system equipped with a 50-µm- technical problems. In order to obtain acceptable sensitiv-
i.d. capillary. Concentration sensitivity can be improved ity, it is necessary to focus sufficient excitation light on the
by employing focusing lenses to collect light at the capil- capillary lumen. This is difficult to achieve with a conven-
lary lumen, by detecting at low wavelengths (where most tional light source, but is easily accomplished using a laser.
analytes have greater absorbance), and by using sample- The most popular sources for laser-induced fluorescence
focusing techniques during the injection process. How- (LIF) detection are the argon ion and helium–neon lasers,
ever, even under ideal conditions, the concentration limit which are stable and relatively inexpensive. These lasers
of detection (CLOD) is about 10−6 M. Sensitivity in op- produce emission lines close to the excitation wavelengths
tical detectors can be improved by the use of extended- for several common fluorophores. The CLOD for a laser-
pathlength capillaries. These include capillaries with in- based fluorescence detector can be as low as 10−12 M.
creased diameters in the window segment (“bubble cell” The most successful applications of CE–LIF detection
capillaries) or in-line cells with a section of capillary po- have been in the analysis of carbohydrates and nucleic
sitioned axially along the light path (“Z-cells”). acids. Carbohydrates can be derivatized with agents such
Several commercial CE systems incorporate scanning as aminopyrene trisulfonic acid, which introduces a flu-
absorbance detectors. Scanning detection enables on-the- orophore and also confers electrophoretic mobility to the
fly acquisition of spectra as analytes migrate through the analyte. Double-stranded nucleic acids can be detected
detection point; this information can assist in the identi- using intercalating dyes and by covalent attachment of
fication of peaks based on spectral patterns, in detection nucleotides carrying fluorophores. The fluorescently la-
of peak impurities by variation in spectral profiles across beled primers or chain terminating nucleotides which are
a peak, or in determation of the absorbance maximum of widely used in automated slab gel-based DNA sequencers
an unknown compound. Two different designs are used are also used in capillary-based sequencers. In one multi-
to accomplish scanning detection in CE instruments. In capillary sequencer, a novel sheath flow system is used for
photodiode array (PDA) detectors, the capillary is illu- LIF excitation of separated bands with imaging of emitted
minated with full-spectrum source light; the light passing fluorescence on a charge-coupled device (CCD) detector.
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362 Capillary Zone Electrophoresis

3. Mass Spectrometry IV. CAPILLARY ELECTROPHORESIS


On-line coupling of a capillary electrophoresis system to a
SEPARATION MODES
mass spectrometer (CE–MS) enables mass and structural
One of the major advantages of CE as a separation tech-
information to be obtained for separated components. The
nique is the wide variety of separation modes available.
most common configuration is introduction of the capil-
Analytes can be separated on the basis of charge, molecu-
lary outlet into an electrospray ionization (ESI) interface.
lar size or shape, isoelectric point, or hydrophobicity. The
In this configuration, the outlet electrode of the CE is
same CE instrument can be used for zone electrophoresis,
eliminated and the MS becomes the ground. Two types
isoelectric focusing, sieving separations, isotachophore-
of CE–ESI interfaces have been employed. For conven-
sis, and chromatographic techniques such as micellar
tional capillaries of 50- to 100-µm i.d., a makeup flow
electrokinetic chromatography and capillary electroki-
is introduced via a coaxial sheath flow or liquid junction
netic chromatography. The following sections provide a
coupling to transport the capillary eluant into the ioniza-
brief description of each separation mode and typical
tion source and produce a stable electrospray. In these de-
applications.
signs, the concentric stainless steel capillary serves as the
electrical connection for the electrospray voltage. An al-
ternative design, termed microspray or nanospray, permits
direct introduction of the CE eluant without makeup flow.
V. CAPILLARY ZONE ELECTROPHORESIS
Small diameter capillaries are used, with the outlet tip ta-
In capillary zone electrophoresis (CZE), the capillary, inlet
pered and metal-coated to establish the ESI high-voltage
reservoir, and outlet reservoir are filled with the same elec-
connection. The major limitation of CE–ESI/MS is the re-
trolyte solution. This solution is variously termed “back-
quirement for volatile buffers, which narrows the choice of
ground electrolyte,” “analysis buffer,” or “run buffer.” In
CE separation modes and resolving power. However, this
CZE, the sample is injected as a plug at the inlet end of
constraint may be relaxed to a degree by the recent intro-
the capillary, and sample components are resolved into
duction of orthogonal or “Z-spray” ESI designs. In some
separated zones according to their mass-to-charge ratio as
studies, an in-line, hollow-fiber dialysis tube has been used
they migrate towards the detection point. It is the simplest
between the separation capillary and the ESI interface.
form of CE and the most widely used.
This technique has been used to remove ampholytes in the
performance of capillary isoelectric focusing–ESI–MS of
proteins.
A. Separation Conditions for Capillary
Zone Electrophoresis
E. Preparative Capillary Electrophoresis
Capillary zone electrophoresis may be performed in the
Because of its high resolving power, CE is often con- presence or absence of EOF. Separations carried out in
sidered for micropreparative isolation. Many of the com- the presence of EOF permit the analysis of cations and
mercially available CE systems have the capability for anions in the same analysis, and the resolution of analytes
automatic fraction collection; however, the desirability of moving counter to EOF can be enhanced. Uncoated fused
using CE as a preparative tool has to be carefully weighed silica capillaries exhibit electroosmotic flow toward the
against the problems encountered in fraction collection. cathode, and the magnitude of EOF increases with pH.
When using narrow-bore capillaries, the volume injected Capillaries coated with an adsorbed or covalent positively
into the capillary is quite small (typically a few nanoliters). charged coating exhibit reversed electroosmotic flow to-
Unless the analyte is in very high concentration, recov- ward the anode. Reversed-charge CZE can be used for
ery of sufficient material requires repetitive injections of analysis of cationic analytes which would adsorb to bare
the same sample. In this case, the run-to-run migration silica capillaries, and for analysis of high-mobility anions
times must be highly reproducible to ensure accurate col- which would not be resolved with normal EOF flow. A dis-
lection of the analyte peak. Also, the recovered analyte advantage of performing CZE in the presence of EOF is
must be stable under the collection conditions for the time variation in the magnitude of EOF, which can compromise
required to collect the desired amount of material (of- migration time and peak area reproducibility. Electroos-
ten several hours). An alternative strategy is the use of motic flow can be controlled or eliminated by coating the
larger diameter capillaries (≥75 µm). However, thermal capillary with an adsorbed or covalent neutral material,
effects may compromise resolution, and low voltages or usually a hydrophilic polymer. Coated capillaries are of-
low-conductivity buffers may be necessary to prevent ex- ten used when analyzing species that have strong affinities
cessive heating. for silica, such as proteins.
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Capillary Zone Electrophoresis 363

Mobility and selectivity in CZE are most profoundly af- ity monitoring of protein therapeutics; clinical analysis of
fected by analyte charge, and selection of the electrolyte serum proteins; and quality control of wines. The CZE
pH is the most effective method of controlling a CZE sep- separation of peptides originating from tryptic digestion
aration. A wide variety of buffers have been employed of cytochrome C is shown in Fig. 4. In addition to these
in CZE, and a buffer is selected to provide good buffer- applications, three important variations of CZE are of par-
ing capacity at the desired pH, low UV absorbance, and ticular note.
low conductivity. In addition to the buffer, other compo-
nents may be added to the electrolyte to control EOF,
1. Capillary Ion Analysis
reduce solute–wall interactions, or to modulate the mo-
bility or solubility of an analyte. Additives for CZE in- Inorganic ions are a particular challenge for CZE because
clude neutral salts, organic amines, surfactants, organic of their high mobilities and lack of UV absorbance. Inor-
solvents, and chiral selectors. Secondary equilibria intro- ganic ions can be detected in the UV region using indi-
duced by additive–analyte interactions are very important rect detection. In this technique, a UV-absorbing species
for achieving resolution in CZE. is used as the background electrolyte, and analytes are
detected as negative peaks. High-mobility anions are an-
alyzed using reversed-charge CZE. Capillary ion analysis
B. Applications of Capillary is routinely used in the analysis of environmental samples,
Zone Electrophoresis industrial brines, and food products.
The great flexibility of CZE has enabled its successful
application to a wide variety of analytes ranging from in-
2. Affinity Capillary Electrophoresis
organic ions to macromolecules. A very incomplete listing
of these includes analysis of ionic drugs and metabolites Affinity capillary electrophoresis (ACE) is used to char-
in pharmaceutical formulations and body fluids; analysis acterize receptor–ligand interactions. The technique de-
of foods, food supplements, and nutriceuticals; analysis pends upon a shift in the electrophoretic mobility of the
of milk and cereal proteins; quality control and stabil- receptor upon complexation with a charged ligand. The

FIGURE 4 Separation of a tryptic digest of cytochrome C by capillary zone electrophoresis. Separation was performed
in a neutral-coated capillary using 100-mM sodium phosphate (pH 2.5).
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364 Capillary Zone Electrophoresis

FIGURE 5 Separation of enantiomers of epinephrine and norepinephrine. Separation was performed in a neutral-
coated capillary using 100-mM sodium phosphate (pH 2.5) and β-cyclodextrin.

distribution of bound vs. free receptor at various ligand and an acidic anolyte solution. The technique is almost
concentrations can be used to determine binding kinetics. universally applied to separation of proteins, which are
Applications of ACE include determination of enzyme– resolved according to their isoelectric points. Capillary
effector binding, antibody–antigen binding, and DNA– isoelectric focusing (CIEF) is similar in concept to con-
carcinogen interactions. ventional gel IEF; carrier ampholytes form a pH gradient
under the influence of an electric field and proteins migrate
electrophoretically to the point in the gradient at which
3. Chiral Analysis
they are isoelectric. In both IEF formats, very high resolu-
Enantiomers can be resolved by incorporating a chi- tion is achieved due to the electrophoretic focusing effect,
ral selector in the background electrolyte. Typical chi- which counters protein diffusion away from the zone at
ral selectors are cyclodextrins, proteins such as α1 -acid equilibrium. In contrast to gel IEF (in which focused pro-
glycoprotein, and macrocyclic antibiotics such as van- teins are fixed and detected by staining in situ within the
comycin. Charged enantiomers may be separated by dif- gel), capillary IEF with on-tube detection requires mobi-
ferential formation of inclusion complexes with neutral lization of focused protein zones past the detection point.
cyclodextrins, while uncharged enantiomers may be re-
solved using a charged cyclodextrin such as cyclodextrin-
A. Separation Conditions for Capillary
sulfobuytlether. Separation of enantiomers of epinephrine
Isoelectric Focusing
and norepinephrine using a cyclodextrin chiral selector is
shown in Fig. 5. Capillary IEF can be carried out as a single- or two-step
process. In single-step CIEF, a mixture of sample proteins
and ampholytes is introduced as a plug at the capillary
VI. CAPILLARY ISOELECTRIC FOCUSING inlet, and an electric field and a mobilizing force are ap-
plied simultaneously. Formation of the pH gradient and
Isoelectric focusing (IEF) is an equilibrium technique in protein focusing occur while the zone is in transit from
which amphoteric compounds are focused in a stable pH the capillary inlet to the detection point. The mobilizing
gradient at the point where they have no net charge. The pH force can be pressure, vacuum, gravity, or electroosmotic.
gradient is contained between a basic catholyte solution Although single-step CIEF is simple in concept, achieving
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Capillary Zone Electrophoresis 365

reproducible migration patterns can be difficult, particu- pholyte blends are used which generate gradients of over
larly when using electroosmotic mobilization. 8 pH units (e.g., pH 3–10); for high-resolution separation
In two-step CIEF, focusing and mobilization are per- of a few proteins, narrow-range ampholyte blends are used
formed separately. Initially, the entire capillary is filled to generate gradients of 1 to 2 pH units.
with a mixture of sample and ampholytes, high voltage
is applied, and the focusing progress is monitored by the B. Applications of Capillary
decrease in operating current. Once equilibrium has been Isoelectric Focusing
established, the mobilization step is begun. The mobilizing
force may be pressure, vacuum, gravity, or electrophoretic. The high resolving power of CIEF enables separation of
In all cases, the electric field is maintained to prevent defo- protein species with small differences in isoelectric points.
cusing of zones during mobilization. Electrophoretic mo- Capillary IEF has been applied to the analysis of protein
bilization is accomplished by changing the composition of glycoforms, protein clips, and deamidation products. The
the anolyte or catholyte, usually by the addition of a salt, technique has also been used for analysis of hemoglobin
buffer, or zwitterion solution. This change in composi- variants and glycated hemoglobins. It provides a rapid and
tion produces a progressive shift in pH down the capillary, convenient method for estimating the isoelectric point of
causing electrophoretic migration of focused proteins past an unknown protein. On-line CIEF–MS is being inves-
the detection point (Fig. 6). In two-step CIEF, the presence tigated as an instrumental counterpart to analytical two-
of EOF disrupts the CIEF process, resulting in loss of reso- dimensional gel electrophoresis in proteomic studies.
lution and reproducibility. For this reason, two-step CIEF
is performed in capillaries coated to reduce or eliminate VII. CAPILLARY SIEVING TECHNIQUES
EOF. Because the entire capillary is filled with sample in
two-step CIEF, zone concentrations at equilibrium will be Sieving techniques are required for separation of species
higher and detection sensitivity will be greater compared which have no differences in mass-to-charge ratio such as
to single-step CIEF. nucleic acids and sodium dodecylsulfate (SDS)–protein
Resolution in CIEF is governed primarily by the com- complexes. Sieving systems include cross-linked or linear
position of the ampholyte mixture. For screening and for polymeric gels cast in the capillary or replaceable polymer
analysis of complex mixtures of proteins, wide-range am- solutions.

FIGURE 6 Separation of proteins by two-step CIEF using electrophoretic mobilization. The ampholytes generated
a gradient from pH 3 to 10 after a focusing time of 300 sec in a neutral-coated capillary. Cathodic mobilization was
initiated by replacing the catholyte (40-mM NaOH) with an alkaline zwitterion solution. pI, Isoelectric point.
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366 Capillary Zone Electrophoresis

FIGURE 7 Separation of SDS–protein complexes by polymer-sieving CE. Separation was obtained in an uncoated
capillary using a commercial polymer-sieving applications kit developed for analysis of SDS–protein complexes (Bio-
Rad Laboratories; Hercules, CA).

A. Capillary Gel Electrophoresis is the ability to closely control the porosity by changing
the ratio of monomer to cross-linker. Polyacrylamide gel-
Polyacrylamide gels can be cast within a capillary using
filled capillaries are incompatible with absorbance detec-
the same chemistry employed for casting conventional
tion at short UV wavelengths. Capillary gel electrophore-
polyacrylamide gels. However, preparation and use of
sis (CGE) has been used for high resolution of synthetic
gel-filled capillaries is complicated by bubble formation
antisense nucleotides such as phosphothioate nucleotides.
caused by volume changes during polymerization, and by
extrusion of the gel from the capillary. To circumvent this,
gels are covalently attached to the capillary wall and poly-
B. Replaceable Polymer Solutions
merized in a segmental fashion. Care must be exercised
in their use to avoid bubble formation and contamina- Sieving separations can be accomplished using solu-
tion of the gel bed. An advantage of gel-filled capillaries tions of linear or branched hydrophilic polymers. These
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Capillary Zone Electrophoresis 367

FIGURE 8 Separation of synthetic oligonucleotides by polymer-sieving CE. Separation was obtained in a neutral-
coated capillary uisng a commercial polymer-sieving applications kit developed for analysis of oligonucleotides (Bio-
Rad Laboratories; Hercules, CA).

polymers have low UV absorbance at short wavelengths, ity toward the detection point where they are detected
and can be replenished between analyses by pressure. as steps with zone length proportional to concentration.
Polymer solutions act by forming entangled networks When UV-transparent spacers are added to the sample, ITP
above a certain polymer concentration, which mimics the zones may appear as isolated peaks and the detector trace
sieving properties of cross-linked gels. Polymers used for will resemble a CZE electropherogram. Isotachophoresis
sieving separations include alkylated celluloses, polyethy- is rarely used as a separation method but is occasionally
lene oxide, and dextrans. Replaceable polymer systems used transiently as an on-line preconcentration technique
have been developed for separation of SDS–protein com- prior to CZE separation.
plexes ranging form 10 to 200 kDa (Fig. 7). Replaceable
polymer solutions have found wide use in nucleic acid sep-
arations, with applications including purity determination IX. MICELLAR ELECTROKINETIC
of synthetic oligonucleotides (Fig. 8), separation of DNA CHROMATOGRAPHY
restriction fragments, DNA typing using microsatellite or
short tandem repeat (STR) sequences, mutation analysis of As the name implies, micellar electrokinetic chromatog-
amplified genetic sequences, and, most importantly, DNA raphy (MEKC) is a chromatographic technique in which
sequence analysis. Because of their excellent precision, samples are separated by differential partitioning between
ease of use, and high resolution, polymer sieving systems two phases (Fig. 9). The technique is usually performed in
have virtually replaced gel-filled capillaries for size-based uncoated capillaries under alkaline conditions to generate
separations by capillary electrophoresis. a high electroosmotic flow. The background electrolyte
contains a surfactant at a concentration above its critical

VIII. ISOTACHOPHORESIS

As a separation techique, isotachophoresis (ITP; also


known as displacement electrophoresis) resolves analytes
as contiguous zones which migrate in order of mobil-
ity. The sample is injected into the capillary between a
leading buffer (with ion mobility greater than that of all
analytes) and a terminating buffer (with ion mobility less FIGURE 9 Schematic of an MEKC separation. Sample mole-
than that of all analytes). Zones migrate at equal veloc- cules are labeled “S.”
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368 Capillary Zone Electrophoresis

micelle concentration (CMC); surfactant monomers are in flow when a voltage is applied to the system, pumping
equilibrium with micelles. The most widely used MEKC mobile phase through the column. Since EOF is plug-like
system employs sodium dodecylsulfate (SDS) as the sur- rather than laminar in nature, efficiencies in CEC can be
factant. The sulfate groups of SDS are anionic, so both sur- much higher than in HPLC. In contrast to pressure-driven
factant monomers and micelles have electrophoretic mo- capillary liquid chromatography, which requires pressures
bility counter to the direction of EOF. Sample molecules of several thousand psi to pump mobile phase through
will be distributed between the bulk aqueous phase and the the column, CEC generates no column backpressure. Like
micellar phase, depending upon their hydrophobic char- MEKC, CEC is used primarily for small molecules.
acter. Hydrophilic neutral species with no affinity for the
micelle will remain in the aqueous phase and reach the
detector in the time required for EOF to travel the effec- SEE ALSO THE FOLLOWING ARTICLES
tive length of the column. Hydrophobic neutral species
will spend varying amounts of time in the micellar phase ELECTROPHORESIS • LIQUID CHROMATOGRAPHY • MASS
depending on their hydrophobicity, and their migration SPECTROMETRY
will therefore be retarded by the anodically moving mi-
celles. Charged species will display more complex behav-
ior, and their migration will include contributions from BIBLIOGRAPHY
electrophoretic mobility and electrostatic interaction with
the micelles in addition to hydrophobic partitioning. The Camilleri, P., ed. (1993). “Capillary Electrophoresis: Theory and Prac-
selectivity of MEKC can be expanded with the introduc- tice,” CRC Press, Boca Raton, FL.
Deyl, Z., and Struzinsky, R. (1991). J. Chromatogr. 569, 63.
tion of chiral selectors to the system. MEKC is used al- Grossman, P. D., and Colburn, J. C., eds. (1992). “Capillary Elec-
most exclusively for small molecules such as drugs and trophoresis: Theory and Practice,” Academic Press, San Diego, CA.
metabolites, pesticides, herbicides, vitamins, etc. Guzman, N. A. (1993). “Capillary Electrophoresis Technology,” Dekker,
New York.
Kuhr, W. G. (1990). Anal. Chem. 62, 403R.
Kuhr, W. G., and Monnig, C. A. (1992). Anal. Chem. 64, 389R.
X. CAPILLARY ELECTROKINETIC Landers, J. P., ed. (1996). “Handbook of Capillary Electrophoresis,” 2nd
CHROMATOGRAPHY ed., CRC Press, Boca Raton, FL.
Li, S. F. Y. (1992). “Capillary Electrophoresis: Principles, Practice, and
Like MEKC, capillary electrokinetic chromatography Applications,” Vol. 52, Elsevier Science, Amsterdam.
Lunte, S. M., and Radzik, D. M., eds. (1996). “Pharmaceutical and
(CEC) is a chromatographic technique performed with CE
Biomedical Applications of Capillary Electrophoresis: Progress in
instrumentation. It employs fused silica capillaries packed Pharmaceutical and Biomedical Analysis,” Vol., Elsevier Science,
with 1.5- to 5-µm microparticulate porous silica beads, Oxford.
usually derivatized with a hydrophobic ligand such as C18. Monnig, C. A., and Kennedy, R. T. (1994). Anal. Chem. 66, 280R.
Mobile phases are similar to those used for conventional Wehr, T., Rodriguez-Dı́az, R., and Zhu, M. (1998). “Capillary Elec-
reversed-phase HPLC (e.g., mixtures of aqueous buffers trophoresis of Proteins,” Dekker, New York.
Weinberger, R. (1992). “Practical Capillary Electrophoresis,” Academic
and an organic modifier such as acetonitrile). The silica Press, Boston, MA.
surface of the derivatized beads has sufficient densities of Vindevogel, V. (1992). “Introduction to Micellar Electrokinetic Chro-
ionized silanol groups to generate a high electroosmotic matography,” Hüthig, Heidelberg.
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Electrochemistry
Donald T. Sawyer
Texas A&M University

I. Fundamentals
II. Electrode Potentials and Potentiometry
III. Controlled-Potential Electrolysis
and Voltammetry
IV. Electron-Transfer Processes
V. Electrochemical Characterization of Molecules
VI. Industrial Electrosynthesis
VII. Batteries and Fuel Cells
VIII. Corrosion; Cathodic Protection

GLOSSARY Electrode Conducting material (usually metal or carbon)


that is immersed in an electrolyte solution and is a
Anode Electrode at which a chemical oxidation occurs source or sink for electrons.
with removal of electrons; the negative terminal for Electrolysis Passage of ionic current through an elec-
spontaneous cell reactions (batteries, galvanic cells, trolyte solution with reduction of an electroactive
and fuel cells); the positive terminal for imposed cell species at the cathode and oxidation of an electroac-
reactions (electrolysis cells and voltammetric cells). tive species at the anode.
Cathode Electrode at which a chemical reduction occurs Electrolyte Solution that conducts ionic current via ionic
via introduction of electrons; the positive terminal for transport (ions of dissolved salts, mineral acids, or
spontaneous cell reactions (batteries, galvanic cells, strong bases).
and fuel cells); the negative terminal for imposed cell Indicator electrode Electrode that responds to the ac-
reactions (electrolysis cells and voltammetric cells). tivity (thermodynamic effective concentration) of a
Cell Container that includes the electrodes (anode and solution species in potentiometric and voltammetric
cathode) connected via an electrolyte solution. Physical measurements.
contact between the anode and the cathode and mixing Reference electrode An electrochemical half-cell with
of electrolysis products from the two electrodes often a stable and known potential. The most common is
is prevented by the use of separators (membranes or the saturated calomel electrode (SCE, +0.242 V vs
inert materials). NHE). The primary standard reference electrode is
Electroactive species Molecules that are transformed at the normal hydrogen electrode (NHE, 0.0000 V by
the anode and cathode. definition).

161
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162 Electrochemistry

THE TECHNOLOGY for the interconversion of chem- tween the anode and the cathode), which is the defining
ical energy and electrical energy has been utilized since difference for electrochemistry and electronics, is due to
the mid-19th century. This conversion is accomplished by the incompatibility of electrons and electrolyte solutions.
ionic-current flow in an electrolyte solution between two During the past four decades, the dynamics and mech-
electrodes connected to each other via an external circuit anisms of electron-transfer processes have been studied
with an electrical load or current source. Batteries, fuel via the application of transition-state theory to the kinet-
cells, and corrosion processes convert the energy of chem- ics for electrochemical processes. As a result, the kinetics
ical reactions into electrical energy. Electrolysis, electro- of both the electron-transfer processes (from solid elec-
plating, and some forms of electroanalysis reverse the trode to the solution species) as well as the pre- and post-
direction of conversion, using electrical energy to produce electron-transfer homogeneous processes can be charac-
a net chemical change. The basic principles and quanti- terized quantitatively.
tative relationships (voltage, current, charge conductance, By the use of various transient methods, electrochem-
capacitance, and concentration) for electrochemical phe- istry has found extensive new applications for the study
nomena were empirically elucidated by Michael Faraday of chemical reactions and adsorption phenomena. Thus,
and other European scientists before the discovery of the a combination of thermodynamic and kinetic measure-
electron (J. J. Thompson, 1893) and the development of ments can be utilized to characterize the chemistry of het-
chemical thermodynamics (G. N. Lewis, 1923). Building erogeneous electron-transfer reactions. Furthermore, het-
on this foundation, the utilization of electrochemical phe- erogeneous adsorption processes (liquid-solid) have been
nomena for thermodynamic characterization and analysis the subject of intense investigations. The mechanisms of
of molecules and ions (electroanalytical chemistry) be- metal-ion complexation reactions also have been ascer-
gan at the beginning of this century [potentiometry (1920) tained through the use of various electrochemical impulse
and polarography (1930)]. Relationships that describe the techniques.
techniques of potentiometry and polarography derive di- The so-called Renaissance of electrochemistry has
rectly from solution thermodynamics. In the case of po- come about through a combination of modern electronic
larography, there is a further dependence on the diffusion instrumentation and the development of a more molecular-
of ionic species in solution. The latter is the basis of con- based theory implemented with the data processing and
ductivity measurements, another area that traces its ori- computational power of computers. Within the area of
gin to the 19th century. These quantitative relationships physical chemistry, numerous thermodynamic studies of
make it possible to apply electrochemistry to the detailed unstable reaction intermediates have made use of mod-
characterization of chemical species and processes in the ern electrochemistry. In addition, extensive studies of the
solution phase. kinetics of electron-transfer processes in aqueous and
Electrochemistry is the science of electron transfer nonaqueous media have been accomplished. The electro-
across a solution/electrode interface. At the cathode, chemical characterization of adsorption phenomena has
electrons (from the electrode) are transformed within the been of immense benefit to the understanding of catalytic
interface via reaction with ions or molecules to produce processes.
reduced molecules or ions (e.g., H+ −
3 O + e → H· + H2 O; Some of the most exciting applications of electrochem-
− − − −
H2 O + e → H· + HO ; · O2 · + e → O2 ·; CuII (bpy)2+ 2 istry have occurred in the areas of organic and inorganic
+ e− → CuI (bpy)+ − II −
2 ; Fe Cl3 + e → Fe Cl3 ). [Note: Al-
III
chemistry and of biochemistry. The applications have
though the traditional formulation of the hydro- ranged from mechanistic studies to the synthesis of un-
nium ion (H3 O+ ) is pervasive in the chemical literature, stable or exotic species. The control of an oxidation or
the positive charge is equally distributed among the reduction process through electrochemistry is much more
three hydrogens, which prompts the formulation used precise than is possible with chemical reactants. Within the
here (H+ 3 O).] At the anode, molecules or ions (from the area of inorganic chemistry, electrochemistry has been es-
solution) are transformed within the interface to pro- pecially useful for the determination of formulas of coordi-
duce electrons (at the electrode surface) and oxidized nation complexes and the electron-transfer stoichiometry
ions and molecules (e.g., 2 H2 O → H+ −
3 O + HO· + e ; of new organometallic compounds. Electrochemical syn-
II − −
Fe Cl3 → Fe Cl3 + e ). The resultant electrons move
III
thesis is increasingly important to the field of organometal-
from the anode through the wires of the external circuit to lic chemistry.
the cathode as electronic current (amperes; coulombs per During the past 50 years, numerous exciting extensions
second). Within the solution phase the current is carried of electrochemistry to the field of analytical chemistry
by the ions of the supporting electrolyte (positive ions have occurred. A series of selective-ion potentiometric
toward the cathode and negative ions toward the anode). electrodes have been developed, such that most of the
The limitation of ionic current in the solution phase (be- common ionic species can be quantitatively monitored in
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Electrochemistry 163

aqueous solution. A highly effective electrolytic moisture The flux of ox that is reduced at the electrode (vc ) has
analyzer provides continuous online assays for water in the dimensions of moles per unit area (cm2 ) per second,
gases. Another practical development has been the voltam- and
metric membrane electrode for dioxygen (·O2 ·), which re- vc = d(Cox )o /A dt = kc (Cox )o = jc /n F), (7)
sponds linearly to the partial pressure of ·O2 ·, either in the
gas phase or in solution. The use of an immobilized en- where (Cox )o is concentration (mol/cm3 ) at the electrode
zyme (glucose oxidase) on an electrode sensor to assay surface, A is area of the electrode (cm2 ), and jc is net
glucose in blood is another extension of electrochemistry cathodic (reductive) current density (A/cm2 ).
to practical analysis. At equilibrium (E = 0),
    
(vc )E=0 = (Cox )o [κkT / h] exp − G ‡c E=0 RT ,
(8)
I. FUNDAMENTALS
where κ is the transmission coefficient within the Ac-
Reductive electrochemistry involves the transfer of elec- tivated Complex Theory, k is the Boltzmann constant,
trons from the electrode surface (cathode) into the double- and h is the Planck constant, which, in combination
layer interface. Within the latter, the electrons react with with Eq. (7), gives an expression for the heterogeneous
the most electrophilic component of the interface; e.g., electron-transfer rate constant when E is zero,
H+     
3 O(aq) in acidic aqueous solutions and H2 O(aq) in basic (kc )E=0 = [κkT / h] exp − G ‡c E=0 RT . (9)
aqueous solutions. From electrochemistry the respective
standard reduction potentials in water are In turn, combination of these equations gives expressions
for the flux of ox reduction (vc ) and cathodic current den-
e − + H+
3O [H·] + H2 O E ◦ , −2.10 V vs NHE (1) sity ( jc ) for a potential difference E.

e + H2 O [H·] + HO − ◦
E , −2.93 V vs NHE (2)     
vc = (Cox )o [κkT / h] exp − G ‡c E=0 RT
and in acetonitrile are × exp(−αn a EF/RT )
e −
+ H+
3O [H·] + H2 O ◦
E , −1.58 V vs NHE (3) = (Cox )o (kc )E=0 exp(−αn a EF/RT ); (10)
− − ◦
e + H2 O [H·] + HO E , −3.90 V vs NHE. (4) jc = (Cox )o n F(kc )E=0 exp(−αn a EF/RT ). (11)
The expressions for the reverse anodic process (oxida-
A. Electron-Transfer Dynamics (Kinetics tion) of Eq. (5) (red → ox + n e− ; ka ) follow from similar
and Thermodynamics) arguments:
The rate of electron transfer at an electrode/solution in- va = (Cred )o (ka )E=0 exp[(1 − α)n a EF/RT ], (12)
terface for the direct reduction of an oxidized species
− ja = (Cred )o n F(ka )E=0 exp[(1 − α)n a EF/RT ]. (13)
2 +e →
(ox) to its reduced state (red ) [e.g., CuII (bpy)2+
I +
Cu (bpy)2 ], When the cathodic current density ( jc ) is equal to the an-
kc odic current density ( ja ), the net current flow across the
ox + ne− ka
red, (5) electrode/solution interface is zero and the net flux of ox
is a function of the concentration of the oxidized species and red is zero. For this unique condition (zero net current)
and its heterogeneous electron-transfer rate constant (kc ; the current densities represent the equilibrium exchange
cathodic process). The latter is a function of the potential current density ( jo ),
difference across the electrode/solution interface (E), jc = ja = jo , (14)
which is directly proportional to the activation energy which is associated with the equilibrium potential differ-
for reduction (−G ‡c ). Only a fraction of E is effec- ence, E e . Thus,
tive for accelerating the rate of reduction, which is repre-
sented by a symmetry parameter, α [transfer coefficient, jo = jc = (Cox )o n F(kc )E=0 exp(−αE e F/RT ) (15)
0.0 < α < 1.0 (usually about 0.5)], jo = ja = (Cred )o n F(ka )E=0 exp[(1 − α)E e F/RT ].
     
G ‡c total = G ‡c E=0 + G ‡c E (16)
 
= G ‡c E=0 + αn a EF, (6) The difference between E and E e is the activation
overpotential (η),
where n a = number of electrons in the rate limiting step;
usually one. η = E − E e . (17)
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164 Electrochemistry

These relationships can be combined to give an expres- Marcus/Hush/Gerischer type) are discussed in Bard and
sion for the net current density ( j), which by definition Faulkner (2001).
is equal to ja − jc in terms of the activation overpoten-
tial (substitute η + E e = E), which is referred to as the
Butler-Volmer equation II. ELECTRODE POTENTIALS
AND POTENTIOMETRY
j = ja − jc = jo {exp[(1 − α)n a Fη/RT ]
− exp[−αn a Fη/RT ]}. (18) Use of the potential of a galvanic cell to measure the con-
centration of an electroactive species developed later than
Both kc and ka vary exponentially with potential a number of other electrochemical methods. In part, this
difference: was because a rational relation between electrode potential
kc = (kc )E=0 exp[−αn a EF/RT ], (19) and the concentration of an electroactive species required
the development of thermodynamics, and, in particular, its
ka = (ka )E=0 exp[(1 − α)n a EF/RT ]. (20) application to electrochemical phenomena. The work of
At equilibrium ( j = 0) and for the special case when J. Willard Gibbs in the 1870s provided the foundation for
(Cox )o = (Cred )o , the Nernst equation. The latter provides a quantitative re-
lationship between potential and the ratio of effective ther-
(kc )E=0 = (ka )E=0 = ks . (21) modynamic concentrations [activities] for a redox couple
This simple rate constant (ks ) is the defined value of kc ([ox]/[red]) and is the basis for potentiometry and poten-
and ka at the formal potential, E ◦ . Then, tiometric titrations. The utility of potentiometric measure-
ments for the characterization of ionic solutions was es-
(kc )E=0 = ks exp[−αn a F(E − E ◦ )/RT ] (22) tablished with the invention of the glass electrode in 1909
◦
(ka )E=0 = ks exp[(1 − α)n a F(E − E )/RT ] (23) for a selective potentiometric response to hydronium-ion
concentrations. Another milestone in the development of
j = n Fks {(Cred )o exp[(1 − α)n a F potentiometric measurements was the introduction of the
× (E − E ◦ )/RT ] hydrogen electrode for the measurement of hydronium-
ion concentrations; one of many important contributions
− (Cox )o exp[−αn a F(E − E ◦ )/RT ]}. by Professor Joel Hildebrand. Subsequent development
(24) of special glass formulations has made possible electrodes
that are selective to different monovalent cations. The idea
Redox couples in aqueous solutions at room temperature
is so attractive that intense effort has led to the develop-
have ks values that range from about 1.0 cm s−1 down to
ment of electrodes that are selective for many cations and
essentially zero (<10−10 cm s−1 ); e.g., ks = 0.1 cm s−1
anions, as well as several gas- and bioselective electrodes.
6 /Fe (CN)6
for FeIII (CN)3− II 4−
and 10−5 cm s−1 for
The use of these electrodes and the potentiometric mea-
Cr (OH2 )6 /Cr (OH2 )6 .
III 3+ II 2+
surement of pH continue to be among the most important
At the equilibrium potential, E = E e , j = 0, Coxo
=
applications of electrochemistry.
Cox , and Cred = Cred , where C denotes the concentration
b o b o

of a species at the electrode surface, whereas C b its bulk


concentration. Then A. Principles and Fundamental Relations
b
Cbx Potentiometric measurements are based on thermody-
b
= exp[−n F(E − E ◦ )/RT ] (25)
Cred namic relationships and, more particularly, the Nernst
and equation which relates potential to the concentration of
b
electroactive species. For our purposes, it is most conve-
Cox
E e = E ◦ + (RT /n F) ln b
nient to consider the redox process that occurs at a single
Cred electrode, although two electrodes are always essential
= E ◦ + (0.05915/n) log ([ox]/[red ]) (26) for an electrochemical cell. However, by considering each
electrode individually, the two electrode processes are eas-
(Nernst equation for a half reaction). ily combined to obtain the entire cell process. Further-
Also, at the equilibrium potential (E e ), more, confusion can be minimized if the half reactions
 b (1−α)  b α for electrode processes are written in a consistent man-
jo = n Fks Cox Cred
(27) ner. Here, these are always reduction processes with the
= n Fks C (when Cox = Cred ). oxidized species reduced by n electrons to give a reduced
More modern models and treatments for the dy- species,
namics of electrochemical electrontransfer (of the ox + ne− red. (28)
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Electrochemistry 165

For such a half reaction the free energy is given by the More rigorous methods for the calculation of aqueous ac-
relation tivity coefficients are available.
[red ] The reaction of an electrochemical cell always involves
G = G ◦ + RT ln , (29) a combination of two redox half reactions such that one
[ox]
species oxidizes a second species to give the respective
where −G indicates the tendency for the reaction to go to redox products. Thus, the overall cell reaction can be ex-
the right; R is the gas constant and in the units appropriate pressed by a balanced chemical equation
for electrochemistry has a value of 8.317 J mol−1 K−1 ; T
is the temperature of the system in K; and the logarithmic a ox1 + b red2 c red1 + d ox2 , K equil . (36)
terms in the bracketed expression represent the activities
(effective concentrations) of the electroactive pair at the However, electrochemical cells are most conveniently
electrode surface. The free energy of this half reaction is considered as two individual half reactions, whereby each
related to the electrode potential, E, by the expression is written as a reduction in the form indicated by Eqs. (28)–
(32). When this is done and values of the appropriate
−G = n FE; −G ◦ = n FE ◦ . (30) quantities are inserted, a potential can be calculated for
each half-cell electrode system. Then that half-cell reac-
The quantity G ◦ is the free energy of the half reaction tion with the more positive potential will be the positive
when the activities of the reactant and product have values terminal in a galvanic cell, and the electromotive force of
of unity and is directly proportional to the standard half- that cell will be represented by the algebraic difference
cell potential for the reaction as written. It also is a measure between the potential of the more positive half-cell and
of the equilibrium constant for the half reaction, assuming the potential of the less positive half-cell,
the activity of electrons is unity,
E cell = E (more positive) − E (less positive) = E 1 − E 2 . (37)
−G ◦ = RT ln K . (31)
Insertion of the appropriate forms of Eq. (32) into Eq. (37)
An extensive summary of E ◦ values is presented in the
gives an overall expression for the cell potential,
compilation by Bard, Parsons, and Jordan (1985); the
most important are tabulated in Sawyer, Sobkowiak, and RT [ox1 ]a [red2 ]b
Roberts (1995). Standard potentials are thermodynamic E cell = E 1◦ − E 2◦ + ln . (38)
nF [ox2 ]d [red1 ]c
quantities that usually are evaluated via caloriometry
for a cell reaction (e.g., 2 H2 + ·O2 · → 2H2 O; E cell◦
= The equilibrium constant for the chemical reaction ex-
◦ ◦
[E O2 − E H+ /H2 ]) and the relationship of Eq. (30). pressed by Eq. (36) is related to the difference of the stan-
When Eqs. (29) and (30) are combined, the resulting dard half-cell potentials by the relation
Nernst expression relates the half-cell potential to the ef- ln K equil = (n F/RT )(E 1◦ − E 2◦ ). (39)
fective concentrations (activities) of the redox couple,
To apply potentiometric measurements to the determi-
RT [red ] RT [ox]
E = E◦ − ln = E◦ + ln . (32) nation of the concentration of electroactive species, a num-
nF [ox] nF [red] ber of conditions have to be met. The basic measurement
The activity of a species is indicated as the symbol of system must include an indicator electrode, which is capa-
the species enclosed in a bracket. This quantity is equal ble of monitoring the activity of the species of interest, and
to the concentration of the species times a mean activity a reference electrode, which gives a constant, known half-
coefficient, cell potential to which the indicator electrode potential
can be referred. The voltage resulting from the combina-
[M a+ ] = a M a+ = γ± C M a+ . (33) tion of these two electrodes must be measured in a man-
Although there is no straightforward and convenient ner that minimizes the amount of current drawn by the
method for evaluating activity coefficients for individual measuring system. For low-impedance electrode systems,
ions, the Debye-Huckel relationship permits an evalua- a conventional potentiometer is satisfactory. However,
tion of the mean activity coefficient (γ± ) for ions at low electrochemical measurements with high-impedance elec-
concentrations (usually below 0.01 M), trode systems, and in particular the glass-membrane elec-
√ trode, require the use of an exceedingly high-input-
µ impedance measuring instrument (usually an electrometer
log γ± = −0.509z 2 √ , (34)
1+ µ amplifier with a current drain of less than 10−12 A). Be-
cause of the logarithmic nature of the Nernst equation, the
where z is the charge on the ion and µ is the ionic strength
  measuring instrumentation must have considerable sensi-
1 tivity. For example, a one-electron half reaction of 25◦ C
µ= Ci z i2 . (35)
2 gives a voltage change of 59.1 mV for a 10-fold change
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166 Electrochemistry

in the concentration of the electroactive species. Another metal as a surface. However, during the past 50 years, it
important point is that the potential response is directly has become evident that platinum electrodes are not as in-
dependent on the temperature of the measuring system. ert as long believed and that their potentiometric response
Thus, if the correct temperature is not used in the Nernst is frequently dependent on the history of the surface and
expression, large absolute errors can be introduced in the the extent of its activation. The evidence is convincing that
measurement of the activity for an electroactive species. platinum electrodes, and, in fact, all metal electrodes, are
covered with an oxide film that changes its characteristics
with time. Nonetheless, the platinum electrode continues
B. Electrode Systems to enjoy wide popularity as an “inert” indicator of redox
The indicator electrodes for potentiometric measurements reactions and of the activities of the ions involved in such
traditionally have been categorized into four separate reactions.
classes. “First-class” electrodes consist of a metal im- For those redox couples that involve a metal ion plus
mersed in a solution that contains the metal ion. These the metal, the logical electrode system is the metal itself.
electrode systems provide a direct response to the ion or In other words, if the measured quantity is to be cupric
species to be measured, ion [copper (II)], a practical indicator electrode is a piece
of copper metal. All second-class electrodes involve an
RT active metal in combination with an insoluble compound
E = E◦ + ln [M n+ ]; M n+ + ne− M (s).
nF or salt. Thus, the silver/silver-chloride electrode actually
(40) is a silver/silver-ion electrode system that incorporates the
Therefore, the primary electrode reaction includes the means to control the silver-ion concentration through the
sensed species. Such electrodes give a direct response ac- chloride-ion concentration [Eq. (41)].
cording to the Nernst equation for the logarithm of the A number of the most common potentiometric electrode
activity of the species. systems and their applications are summarized in Table I.
Electrodes classified as “second-class” electrode sys- One of the most important and extensively used indicator
tems are those in which the electrode is in direct contact electrode systems is the glass-membrane electrode that is
with a slightly soluble salt of the electroactive species used to monitor hydronium-ion activity. Although devel-
such that the potentiometric response is indicative of the oped in 1909, it did not become popular until reliable elec-
concentration of the inactive anion species. Thus, the trometer amplifiers were developed in the 1930s (modern
silver/silver-chloride electrode system, which is represen- pH meters use high-input-impedance digital voltmeters).
tative of this class of electrodes, gives a potential response Figure 1 gives a schematic representation of this elec-
that is directly related to the logarithm of the chloride ion trode and indicates that the primary electrode system is
activity, a silver/silver-chloride (or mercury/mercurous-chloride)
RT electrode in contact with a known and fixed concentra-
E = E◦ − ln [Cl− ]; AgCl (s) + e− Ag (s) + Cl− , tion of hydrochloric acid (usually about 0.1 M). When
nF
(41)
even though it is not the electroactive species. This is true
because the chloride-ion concentration, through the solu- TABLE I Redox Potentials (E ◦ ) for the MI (OH2 )+
2 /M and
bility product, controls the activity of the silver ion, which MI OH/M, HO− Couples of Cu, Ag, and Au in H2 O and in MeCN
(0.1 M Tetraethylammonium Perchlorate)
is measured directly by the potentiometric silver-electrode
system. E ◦ , V vs NHEa
Because any potentiometric electrode system ultimately M MI (solv)+
n /M MI OH/M, HO−
must have a redox couple (or an ion-exchange process
in the case of membrane electrodes) for a meaning- A. H2 O Cu +0.52 −0.36
ful response, the most common form of potentiometric Ag +0.80 +0.34
electrode systems involves oxidation-reduction processes. Au +1.7
Hence, to monitor the activity of ferric ion [iron(III)], an H+
2 O·/H2 O;
HO·/HO− (GC) +2.72 +1.89
excess of ferrous ion [iron(II)] is added such that the con-
B. MeCN Cu +0.19 −0.79
centration of this species remains constant to give a di-
Ag +0.54 −0.30
rect Nernstian response for the activity of iron(III). For
Au +1.58 −0.19
such redox couples the most common electrode system
H+
2 O·(MeCN)/H2 O;
has been the platinum electrode. This tradition has come
HO·/HO− (GC) +3.2 +0.92
about primarily because of the historic belief that the plat-
inum electrode is totally inert and involves only the pure a SCE = +0.24 V vs NHE.
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Electrochemistry 167

exchange membranes (prepared from organic, polymer-


based, ion-exchange resins) that give a selective response
to specific cations and anions. The main advantages of the
membranes are resistance to high acid and alkali concen-
trations and high conductivity. The membranes, however,
show little selectivity between ions. A related form of the
membrane electrode is the inorganic-crystal electrode. An
example is the lanthanum-fluoride (LaF3 ) electrode that
senses fluoride-ion concentrations, which has become the
standard sensor for fluoride determinations in water anal-
ysis. It represents a combination of a membrane electrode
with ion-exchange characteristics and an incomplete form
of a second-class electrode in which lanthanum fluoride
is the insoluble material that responds to the free fluoride-
ion concentration in the test sample. Other examples of
this form of electrode include AgX /Ag2 S and MS/Ag2 S
electrodes, which give response to monovalent anions and
divalent cations, respectively.
In contrast to solid-membrane electrodes, liquid-
membrane electrodes can extract counterions from the so-
lution phase into the membrane phase. Selectivity is pro-
vided by the charged nature of the membrane carriers and
arises from the competitive degree of extractability of var-
ious counterions. Totally liquid systems can be employed
FIGURE 1 Glass electrode (a) and its cell schematic (b) in asso- but are impractical. Instead, a porous support or an inert
ciation with a reference electrode. polymer support is used in most commercial electrodes.
Gas-selective electrodes are a particularly important ap-
plication of the glass electrode. For example, the carbon-
the outside surface of the glass membrane is exposed to dioxide electrode is a self-contained system with a glass
an ionic solution, a response for the hydronium-ion ac- electrode and a concentric silver/silver-chloride electrode
tivity [H+3 O] is obtained that follows the Nernst expres- enclosed by a CO2 permeable membrane. The latter holds
sion. Although there has been considerable debate about a thin film of bicarbonate solution in contact with the glass
the mechanism of response for the glass electrode, the membrane, which provides a junction to the silver/silver-
current thinking invokes an ion-exchange process that in- chloride reference electrode. The electrode has found ex-
volves the hydroxyl groups on the surface of the glass. tensive application in monitoring CO2 levels in blood and
Thus, the population of protons on the outside surface of probably will find increasing application in other systems
the membrane affects the population on the inside of the that require continuous measurement of CO2 partial pres-
membrane, which generates a membrane potential that is sures. The electrode response is based on the reaction
indicated by the silver/silver chloride. At one time there
CO2 + 2 H2 O H+
3 O + HOC(O)O

(42)
was a belief that hydronium ions actually penetrated the
glass membrane from the outside to the inside. However, such that changes in the partial pressure of carbon dioxide
experiments with labeled systems establish that this is not cause an attendant change in the concentration of hydro-
true. Further support for the ion-exchange mechanism is nium ion. [Note: Although the coventional formulation of
provided by the realization that glass electrodes are not bicarbonate ion (HCO− 3 ) is common, the formulation used
specific for hydronium ions, but only give a selective re- here (HOC(O)O− ) provides a better sense of its structure
sponse. In other words, other metal ions, in particular those and chemistry.] Thus, with a fixed concentration of bi-
of sodium and lithium, cause a response from glass elec- carbonate the electrode provides a direct potentiometric
trodes through an equivalent ion-exchange process. response to the partial pressure of carbon dioxide. Other
The unwanted response of glass electrodes to metal gas-monitoring electrode systems should be possible that
ions, particularly alkali metal ions, has prompted the de- are based on similar processes. For example, an ammo-
velopment of specialized glass membranes that have an nia (NH3 ) electrode might well be developed with the
enhanced selective response for monovalent cations. A converse of the reactions indicated for the CO2 electrode.
parallel approach has been used in the development of ion- Thus, an ammonium-ion (NH+ 4 ) electrolyte would be used
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168 Electrochemistry

such that changes in pH would be proportional to changes ence potentials that do not vary more than a few millivolts.
in the partial pressure of NH3 . These electrodes as well as The silver/silver chloride electrode also finds application
SOx -, NOx -, HF-, H2 S-, and HCN-sensing electrodes are in nonaqueous titrations, although some solvents cause
commercially available. the silver-chloride film to become soluble. Aqueous refer-
The gas-sensing electrodes also are used for the poten- ence electrodes are as convenient for nonaqueous systems
tiometric measurement of biologically important species. as any of the prototypes that have been developed to date.
An enzyme is immobilized at or near the gas probe. The When there is a need to rigorously exclude water, double-
gas sensor measures the amount of characteristic gas pro- salt bridges (aqueous/nonaqueous) are a convenient
duced by the reaction of the analyzed substance with solution.
the enzyme. For example, an enzyme electrode for urea For measurement of redox couples, a frequently over-
[NH2 C(O)NH2 ] determination is constructed by the im- looked but convenient reference electrode is a conven-
mobilization of urease onto the surface of an ammonia- tional glass pH electrode (assuming the sample solution
selective electrode. When the electrode is inserted into a system contains a constant level of acidity). Such an elec-
solution that contains urea, the enzyme catalyzes its con- trode provides an extremely inert and stable reference po-
version to ammonia, tential that is completely indifferent to most redox species.
urease However, the glass electrode requires the use of an elec-
NH2 C(O)NH2 + H2 O 2 NH3 + CO2 . (43)
trometer amplifier such as that contained in pH meters.
The generated ammonia diffuses through the gas-
permeable membrane and is detected by the probe of the
C. Applications of Potentiometry
electrode. A steady-state signal is reached when the rate
of NH3 diffusion from the electrode equals the rate of its Although all potentiometric measurements (except those
generation. involving membrane electrodes) ultimately are based on a
In general, a necessary part of a potentiometric mea- redox couple, the method can be applied to oxidation-
surement is the coupling of a reference electrode to the reduction processes, acid-base processes, precipitation
indicating electrode. The ideal reference electrode has a processes, and metal-ion complexation processes. Mea-
number of important characteristics: (1) a reproducible surements that involve a component of a redox couple
potential, (2) a low-temperature coefficient, (3) the capac- require that either the oxidized or reduced conjugate of
ity to remain unpolarized when small currents are drawn, the species to be measured be maintained at a constant
and (4) inertness to the sample solution. If the reference and known activity at the electrode. If the goal is to mea-
electrode must be prepared in the laboratory, a convenient sure the activity of silver ion in a solution, then a silver
and reproducible system is desirable. wire coupled to the appropriate reference electrodes makes
Although the standard half-cell reactions are all refer- an ideal potentiometric system. Likewise, if the goal is
enced to the standard hydrogen electrode (NHE or SHE), to monitor iron(III) concentrations with a platinum elec-
this is an exceedingly awkward reference electrode. It has trode, a known concentration of iron(II) must be present
been selected because its potential falls in the middle of in the sample solution such that potential changes are only
those for the most common half reactions in water and dependent on the iron(II) concentration.
because with rigorous care highly reproducible potentials Table I summarizes a number of redox couples that are
can be duplicated by equally careful workers in other lab- well behaved in aqueous solutions and provide a means for
oratories. Furthermore, because it consists of a platinized monitoring the indicated species by potentiometric mea-
platinum electrode over which hydrogen gas is passed in surements. This can be either in the form of monitoring
combination with a known activity of hydronium ion, it a titration or as a direct absolute measurement of activity.
can be combined in a number of cases with other half-cells Although the tabulations of standard potentials infer that
without a liquid junction. These three factors undoubtedly the listing should be much more comprehensive, most of
justify its selection as the ultimate reference electrode for the couples tabulated are not well behaved in an electro-
fundamental measurements. The electrode reaction is a chemical sense and do not provide a Nerstian response
typical redox half reaction which includes the oxidized under normal laboratory conditions. The vast majority of
and reduced forms of hydrogen. By controlling the hy- the data tabulated is based on calorimetric data.
drogen partial pressure at a fixed level, this becomes an The major application of the potentiometric method
indicating electrode for hydronium-ion activity. is for acid-base measurements in both aqueous and non-
For most potentiometric measurements, either the sat- aqueous solvent systems. Although the glass electrode is
urated calomel reference electrode or the silver/silver- universally the most common indicating electrode sys-
chloride reference electrode is used. These electrodes can tem for such measurements, many other electrodes have
be made compact, are easily produced, and provide refer- been developed. However, except in extremely specialized
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Electrochemistry 169

circumstances, none of these provides the reliability and sure of metal-ion activity. If one is concerned purely with
precision that is afforded by the glass electrode. In the ab- the actual activity of free metal ion, these measurements
sence of interfering substances, the quinhydrone electrode are meaningful. However, if the measurement is taken to
(an equimolar combination of quinone and hydroquinone represent the total metal-ion content of the solution, both
with a gold-foil electrode) provides a simple monitoring as a free solvated ion and as its various complexes, then
system for measurements up to pH 8. However, the pres- highly erroneous conclusions can be made. Thus, the abil-
ence of oxidizing or strongly reducing ions in the sample ity to monitor the concentration of ligands should be rec-
system will interfere, as is true for the hydrogen gas elec- ognized as a pitfall if one does not take account of this in
trode and most other systems that are an alternative to the the use of potential measurements to monitor metal-ion
glass electrode. concentrations.
Potentiometric redox measurements are often per- A recent and rapidly developing extension of poten-
formed in nonaqueous or mixed-solvent media. For such tiometry is in the area of membrane-type indicator elec-
solvents, various potentiometric sensors have been devel- trodes. These include (1) specialized glass electrodes that
oped, which, under rigorously controlled conditions, give respond to ions other than the hydronium ion, (2) ion-
a Nernstian response over a wide ranges of activities (par- exchange membranes, and (3) single-inorganic-crystal
ticularly in buffered solutions). There are some experi- membranes. Each year the selectivity and reliability are
mental limitations, e.g., solvent purification and handling improved for this important class of electrode. In partic-
or use of a reference electrode without salt bridges, but ular, the development of ion-exchange membranes that
there are important advantages. Solutes may be more sol- provide selective response for a number of anions has
uble in such media, and redox properties of the species made new areas of analysis amenable to potentiometric
may be altered in comparison with aqueous solutions. measurements. This has been particularly important for
Measurements of pH in nonaqueous solvents almost with- the biomedical field where nondestructive, highly specific
out exception use the glass electrode in combination poteniometric measurements are desirable. Furthermore,
with an appropriate reference electrode, frequently the the potentiometric method, because of its continuous na-
silver/silver-chloride electrode. In general, the response ture, is particularly attractive to those concerned with in
of the glass electrode follows the Nernst expression in vivo monitoring of biological substances.
nonaqueous solvents and is an accurate representation of Because potentiometry (through the Nernst equation)
the changes in activity of hydronium ion. Unfortunately, gives a response that is proportional to the logarithm of
few, if any, standard buffers are available to calibrate pH the activity of the electroactive ion, the accuracy and pre-
meters for nonaqueous measurements. Thus, nonaqueous cision are more limited than for many methods that give
pH measurements are only meaningful for monitoring the a direct proportional response. Thus, for a one-electron
course of an acid-base titration or relative to some refer- redox process, an order of magnitude change in activity
ence measurement made within the individual laboratory. gives a potential change of 59.1 mV (at room temperature),
Little, if any, confidence can be attached to absolute pH a 10% change in activity gives a change of 2.5 mV, and a
measurements in nonaqueous systems. The application of l% change in activity gives only a change of 0.25 mV.
ion-selective electrodes in nonaqueous media has been Potentiometry has found extensive application over the
limited, but the response for several cations and anions past 50 years as a means to evaluate various thermody-
is usable, especially when 10–20% of water is added to namic parameters. Although this is not the major appli-
pure nonaqueous solvent. Limited use of liquid-membrane cation of the technique today, it still provides one of the
electrodes in such media arises from the solubility of most convenient and reliable approaches to the evalua-
electrode-system components in organic media. tion of thermodynamic quantities. In particular, the ac-
Second-class electrodes, that is those whose response tivity coefficients of electroactive species can be evalu-
is dependent on the change in concentration of an anion ated directly through the use of the Nernst equation (for
which gives an insoluble salt with the metal ion of the species that give a reversible electrochemical response).
indicator electrode, provide a general means for moni- Thus, if an electrochemical system is used without a junc-
toring the concentrations of anions. Some of those half tion potential and with a reference electrode that has a
reactions, which are well behaved electrochemically and well-established potential, then potentiometric measure-
provide means for the potentiometric monitoring of anion ment of the constituent species at a known concentration
species, are summarized in Table I. This table also includes provides a direct measure of its activity. This provides a
a tabulation of redox reactions that are useful to moni- direct means to evaluate the activity coefficient (assuming
tor the concentration of ligands that can complex metal the standard potential is known accurately for the con-
ions. Consideration of these indicates one of the difficul- stituent half reaction). If the standard half-reaction poten-
ties with absolute potentiometric measurements as a mea- tial is not available, it must be evaluated under conditions
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170 Electrochemistry

where the activity coefficient can be determined by the at the half-equivalence point; the half-reaction potential,
Debye-Huckel equation. assuming activities are equal to concentrations, is given
Another important application is the use of potentio- directly by the potential of the indicator electrode relative
metric measurements for the evaluation of thermodynamic to the reference electrode. If the latter is a standard hydro-
equilibrium constants. In particular, the dissociation con- gen electrode, the measured potential is equal to the E ◦ for
6 /Fe (OH2 )6 couple. The evaluation of
the FeIII (OH2 )3+ II 2+
stants for weak acids and weak bases in a variety of sol-

vents are evaluated conveniently with a pH electrode mea- the E for a half reaction provides a direct measure of the
suring system. The most precise approach is to perform free energy for the half reaction relative to the free energy
an acid-base titration such that the titration curve can be for the reduction of hydronium ion to hydrogen gas. Like-
recorded. Obviously, one could measure the pH of a known wise, a combination of any pair of E ◦ values or of the free
concentration of a weak acid and obtain a value of its energy values permits the evaluation of the equilibrium
hydronium-ion activity which would permit a direct eval- constant and the standard free energy for a redox reaction.
uation of its dissociation constant. However, this would From a practical standpoint it is often useful to have the
be a one-point evaluation and subject to greater errors observed potential in the medium of measurement for the
than by titrating the acid halfway to the equivalence point. condition of equal concentrations of the oxidized and re-
The latter approach uses a well-buffered region where the duced species of a half reaction. Such potentials are known
pH measurement represents the average of a large num- as formal potentials, E ◦ , rather than standard potentials
ber of data points. Similar arguments can be made for the and are not purely thermodynamic quantities. The term
evaluation of solubility products and stability constants of “formal potential” comes from the tradition of having the
complex ions. supporting electrolyte at a one formal concentration. How-
In the use of potentiometry for the evaluation of stability ever, other stated solution conditions also are included in
constants for complex ions, the expressions can become many listings. Thus, the indicated potential is what one
extremely complicated if multi-equilibria are present. For would expect at the half-equivalence point under actual
a simple one-to-one complex, a direct potentiometric titra- titration conditions. In other words, activity corrections
tion curve again provides the most satisfactory route to an have not been made.
accurate evaluation of the constant. The curve looks sim-
ilar to that for an acid-base titration, and the appropriate
III. CONTROLLED-POTENTIAL
point to pick is the half-equivalence point. If the complex is
ELECTROLYSIS AND VOLTAMMETRY
extremely stable, then the amount of free metal ion at this
point on the titration curve (ligand titrated with metal ion)
For chemists, the second important application of elec-
is sufficiently low that it can be disregarded. Assuming it
trochemistry (beyond potentimetry) is the measurement
is a stable complex, at the first half-equivalence point the
of species-specific [e.g., iron(III) and iron(II)] concentra-
concentration of complexed metal ion will be equivalent to
tions. This is accomplished by an experiment whereby the
that of the free ligand. The potential will give a direct mea-
electrolysis current for a specific species is independent of
sure of the free metal ion and allow the stability constant
applied potential (within narrow limits) and controlled by
for the complex to be evaluated at the half-equivalence
mass transfer across a concentration gradient, such that
point, e.g.,
it is directly proportional to concentration (i = kC). Al-
[AgI (en)+ ] though the contemporary methodology of choice is cyclic
Kf =   . (44)
AgI (OH2 )+
2 [en]
voltammetry, the foundation for all voltammetric tech-
niques is polarography (discovered in 1922 by Professor
Potentiometry also is a direct means to evaluate the
Jaroslov Heyrovsky; awarded the Nobel Prize for Chem-
standard potential for half reactions (E ◦ ) and has been ap-
istry in 1959). Hence, a historical approach is used with
plied for appropriate reversible systems. Such measure-
a recognition that cyclic voltammetry will be the primary
ments require corrections for activity coefficients or ex-
methodology for most chemists.
trapolation of the data to infinite dilution. Again, direct
measurements in which equal molar concentrations of the
oxidized or reduced species are introduced into the sys- A. Principles and Fundamental Relations
tem provide a simple approach to such evaluations and
1. Diffusion to a Planar Electrode
are as precise as those obtained by less direct methods.
However, E ◦ values also can be extracted from poten- The basic approach in controlled-potential methods of
tiometric titration data. For example, in the titration of electrochemistry is to control in some manner the poten-
FeII (OH2 )2+ IV 4+ III
6 ion with Ce (OH2 )n ion, the Fe (OH2 )6
3+
tial of the working electrode while measuring the resultant
II 2+
ion concentration equals the Fe (OH2 )6 concentration current, usually as a function of time. When a potential
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Electrochemistry 171

sufficient to electrolyze the electroactive species com- This relationship holds for any electrochemical process
pletely is applied to the electrode at (t = 0), the concen- that involves semi-infinite linear diffusion and is the basis
tration at the electrode surface is reduced to zero and an for a variety of electrochemical methods (e.g., polarogra-
electrode process occurs, for example, phy, voltammetry, and controlled-potential electrolysis).
Equation (50) is the basic relationship used for solid-
ox + ne− red, (45)
electrode voltammetry with a preset initial potential on
where ox and red represent an oxidized and reduced form a plateau region of the current-voltage curve. Its applica-
of an electroactive species. Passage of current requires tion requires that the electrode configuration be such that
material to be transported to the electrode surface as well semi-infinite linear diffusion is the controlling condition
as away from it. Thus, relationships must be developed for the mass-transfer process.
which involve the flux and diffusion of materials; this is
appropriately accomplished by starting with Fick’s second
law of diffusion, B. Voltammetry
∂C(x,t) D∂C(x,t)
= , (46) 1. Polarography
∂t ∂x2
where D represents the diffusion coefficient, C represents The most extensively studied form of voltammetry has
the concentration of the electroactive species at a dis- been polarography (first described by Heyrovsky in 1922,
tance x from the electrode surface, and t represents the with the quantitative relationships of current, potential,
amount of time that the concentration gradient has ex- and time completed by the early 1930s with the assistance
isted. Through the use of Laplace transforms with initial of associates such as Ilkovic). The potential-time depen-
and boundary conditions; dence that is used for polarographic measurements is pre-
sented in Fig. 2 (solid line). The potential is scanned from
for t = 0 and x ≥ 0 C = C b, E 1 to E 2 to obtain a current response that qualitatively
for t ≥ 0 and x → 0 C → C b, and quantitatively characterizes the electroactive species
present. The vast body of data from polarographic mea-
for t > 0 and x = 0 C = 0. surements can be adopted by other electroanalytical meth-
Equation (46) can be solved to give a relationship for con- ods. Moreover, pulse polarographic methods and anodic
centration in terms of parameters x and t, stripping analysis, which are still used for determination
x of trace amounts of metal ions, are closely related to po-
C(x,t) = C b erf 1/2 1/2 , (47) larography. The unique characteristic of polarography is
2D t
its use of a dropping mercury electrode, such that the elec-
where C b is the bulk concentration of the electroactive trode surface is continuously renewed in a well-defined
species. and regulated manner to give reproducible effective elec-
By taking the derivative of Eq. (47) for the proper trode areas as a function of time. The diffusion cur-
boundary condition, namely at the electrode surface rent equation [Eq. (50)] can be extended to include a
(x = 0), the diffusion gradient at the electrode surface is dropping mercury electrode by appropriate substitution
expressed by the relation for the area of the electrode. Thus, the volume of the
 
∂C Cb drop for a dropping mercury electrode is given by the
= 1/2 1/2 1/2 . (48) relationship
∂ x (0,t) π D t
This flux of material crossing the electrode boundary can 4 3 mt
be converted to current by the expression V= πr = , (51)
3 d
∂C(0,t)
i = n FAD , (49) where r is the radius of the drop of mercury, m is the mass
∂x
flow rate of mercury from the orifice of the capillary, t is
where n is the number of electrons involved in the elec-
the life of the drop, and d is the density of mercury under
trode reaction, F is the faraday, and A is the area of the
the experimental conditions. When this equation is solved
electrode. When Eq. (48) is substituted into this relation a
for r and the latter is substituted into the equation for the
complete expression for the current that results from semi-
area of a sphere, an expression for the area of the dropping
infinite linear diffusion is obtained (the Cottrell equation
mercury electrode drop as a function of the experimental
for a planar electrode),
parameters is obtained,
n FAC b D 1/2
i= . (50)
π 1/2 t 1/2 A = (4π )1/3 32/3 m 2/3 t 2/3 d −2/3 . (52)
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172 Electrochemistry

FIGURE 2 Potential-time profile that is used for polarography and linear-sweep voltammetry (solid line) and cyclic
voltammetry (both solid and dashed lines).

This then can be substituted into Eq. (50) to give a calcu- rial produced by the electrolysis reaction, these quantities
lated diffusion current for the dropping mercury electrode, can be directly related to the concentration of the species
at the electrode surface. For a generic reduction process
(i t )calc = 462nC b D 1/2 m 2/3 t 1/6 . (53)
[Eq. (45)], the potential of the electrode is given by the
Actually, experimental results indicate √that the constant Nernst equation
in Eq. (53) is too small by a factor of 7/3, due to the
growth of the mercury drop into the solution away from RT Cox(0,t)
E = E◦ + ln . (56)
the capillary orifice. Thus, the correct diffusion current nF Cred(0,t)
expression for a dropping mercury electrode is
Initially, the solution contains only ox (concentration,
i = 706nC b D 1/2 m 2/3 t 1/6 , (54) b
Cox ). When a potenital is applied and reductive current
which gives the current at any time up to the lifetime of the flows, the oxidized form of the electroactive species dif-
drop. If the drop time, td , is substituted, the well-known fuses toward the electrode. From Eq. (63) it follows that
Ilkovic equation results,  b  1/2 2/3 1/6
1/6 i = 706n Cox − Cox(0,t) Dox m td
i d = 706nC D b 1/2
m 2/3 td , (55)
1/6
= i d − 706nCox(0,t) Dox m td .
1/2 2/3
(57)
where i d is in A if D is in cm2 s−1 , C b is in mol cm−3 , m
in mg s−1 , and t is in s. Alternatively, i d is in µA when
Hence,
C b is in mM.
The polarographic current-potential wave that is illus- id − i
Cox(0,t) = 1/2
. (58)
trated by Fig. 3 conforms to the Nernst equation for re- 706n Dox m 2/3 t 1/6
versible electrochemical processes. However, it is more
convenient to express the concentrations at the electrode After reduction of ox, its reduced form (red ) diffuses either
surface in terms of the current, i, and diffusion current, into the bulk of solution or into the mercury to form an
i d . Because i d is directly proportional to the concentra- amalgam. In either case,
tion of the electroactive species in the bulk and i at any   1/2 2/3 1/6
point on the curve is proportional to the amount of mate- i = 706n Cred(0,t) − Cred
b
Dred m td . (59)
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Electrochemistry 173

FIGURE 3 Polarograms for (a) 0.5 mM CdII (OH2 )2+


6 in 1 M HCl and (b) 1 M HCl.

But the reduced form of the electroactive species was 2. Linear Sweep and Cyclic Voltammetry
not present in the solution before electrolysis, therefore,
The potential-time relation for voltammetric measure-
b
Cred = 0 and
ments is presented in Fig. 2. With linear-sweep voltamme-
i try, the potential is linearly increased between potentials
Cred(0,t) = 1/2
. (60)
706n Dred m 2/3 t 1/6 E 1 and E 2 . Cyclic voltammentry is an extension of linear-
sweep voltammetry with the voltage scan reversed after
Substitution of Eqs. (58) and (60) into Eq. (56) gives the current maximum (peak) of the reduction process has
  been passed. The voltage is scanned negatively beyond the
RT Dred 1/2 RT i d − i
E = E◦ + ln + ln . (61) peak and then reversed in a linear positive sweep. Such a
nF Dox nF i
technique provides even more information about the prop-
At the half-height of a polarographic wave (i = i d /2), the erties and characteristics of the electrochemical process
corresponding potential is defined as the half-wave poten- and also gives insight into any complicating side processes
tial (E 1/2 ). Therefore, Eq. (61) takes the form such as pre- and post-electron-transfer reactions as well
RT id − i as kinetic considerations. Whereas in classical polarog-
E = E 1/2 +ln . (62) raphy the voltage-scan rate is about 1 V min−1 , linear-
nF i
sweep voltammetry uses scan rates up to 100 V s−1 for
For the reduction of a simple solvated metal ion to its conventional microelectrodes (and up to 10,000 V s−1 for
amalgam, E 1/2 is given by ultra-microelectrodes; 10−6 m diameter).
RT γion Da
1/2 Figure 4 illustrates the shape of a cyclic voltammo-
E 1/2 = E ◦ + ln 1/2
, (63) gram with an electrode of fixed area. The voltammogram
nF γa Dion is characterized by a peak potential, E p , at which the cur-
where γion is the activity coefficient for the ion and γa is rent reaches a maximum value, and by value of the peak
the activity coefficient for the amalgamated species. The current, i p . When the reduction process is reversible the
diffusion coefficients for the amalgam and ionic species peak current is given by the relation
also are a part of this expression. The standard reduction i p = 0.4463n FA(Da)1/2 C b (64)
potential is for reduction of the ion to the amalgamated
species. These expressions also hold for the reduction of with
an ion to a lower oxidation state, but require that the ap- n Fν nν
a= = at 25◦ C, (65)
propriate value be used. RT 0.026
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174 Electrochemistry

For a reversible process the peak potential can be re-


lated to the polarographic half-wave potential, E 1/2 , by
the expression

RT 0.0285
E p = E 1/2 − 1.11 = E 1/2 − at 25◦ C
nF n
(69)
Another useful parameter of the voltammetric curves is the
half-peak potential, E p/2 , which is the potential at which
the registered current reaches half its maximum value and
is used to characterize a voltammogram. For a reversible
process, E 1/2 is located halfway in between E p and E p/2 .
The ratio of the peak current for the cathodic process
relative to the peak current for the anodic process is equal
to unity (i p,c /i p,a = 1) for a reversible electrode process.
To measure the peak current for the anodic process the ex-
trapolated baseline going from the foot of the cathodic
wave to the extension of this cathodic current beyond
the peak must be used as a reference, as illustrated by
Fig. 4.
For the condition
0.141
|E λ − E p/2 | ≥ , (70)
n
where E λ is the extent of the voltage sweep, the differ-
FIGURE 4 Linear voltage-sweep voltammogram with reversal of
sweep direction to give a cyclic voltammogram. The initial sweep ence in the peak potentials between the anodic and ca-
direction is to more negative potential. thodic processes of the reversible reaction is given by the
relationship

0.059
where ν is the scan rate in volts per second. This relation |E p | = |E p,a − E p,c | = at 25◦ C, (71)
results from the set of differential equations for Fick’s n
second law of diffusion (with the appropriate initial and which provides a rapid and convenient means to determine
boundary conditions for ox and red ). Thus, in terms of the number of electrons involved in the electrochemical
the adjustable parameters the peak current is given by the reaction. For a reversible system, i p is a linear function of
Randles-Sevcik equation √
ν, and E p is independent of ν.
i p = 2.69 × 105 n 3/2 AD 1/2 C b ν 1/2 at 25◦ C, (66)
where i p is in A, A is in cm2 , D is in cm2 s−1 , C b is in mol C. Controlled-Potential Bulk Electrolysis
cm−3 , and ν is in V s−1 .
Because of the extensive amount of data available from the
Nicholson and Shain revolutionized the voltammetric
polarographic and voltammetric literature, the optimum
experiment with their elegant development and demon-
conditions for macroscopic electrolyses often are estab-
stration of linear-sweep and cyclic voltammetry. In their
lished. In particular, controlled-potential electrolysis at a
approach, the current-potential curve is presented as
mercury pool can be approached with predictable success
i = n FAC b (πDa)1/2 χ (at). (67) on the basis of available polarographic information for
the system of interest. An electrolysis can be accelerated
From tabulations for the relation between π 1/2 χ ( at) and by maximizing the electrode surface area and minimizing
n(E − E 1/2 ) and converting the term π 1/2 χ (at) to χrev , the thickness of the diffusion layer. However, the same
Eq. (67) takes the form electrode material must be used as in polarography. Thus,
i = n FAC b (Da)1/2 χrev . (68) a conventional approach in controlled-potential electrol-
ysis is the use of a mercury pool stirred as vigorously as
For a given potential (E) the value of χrev is obtained from possible with a magnetic stirring bar to minimize the con-
tabulations. centration gradient. Under such conditions the decay of
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Electrochemistry 175

the current as well as the decay of the concentration of the in the electrode reaction be known, and the concentration
electroactive species is given by the relation of the electroactive species and the area of electrodes be

  known. With these conditions satisfied, diffusion coeffi-
it Ct −D A
= = exp t , (72) cients can be evaluated rapidly over a range of tempera-
i t=0 Ct=0 Vx tures and solution conditions.
where V is the volume of the solution to be electrolyzed Voltammetric methods also provide a convenient ap-
and x is the thickness of the concentration gradient. proach to establish the thermodynamic reversibility of an
Thus, the current and concentration decay exponentially. electrode reaction and for the evaluation of the electron
Under idealized conditions, 90% of the electroactive stoichiometry for the electrode reaction. As outlined in
species will be electrolyzed in approximately 20 min. In- earlier sections, the standard electrode potential, the dis-
creases in the temperature as well as in the electrode area sociation constants of weak acids and bases, solubility
relative to the solution volume will accelerate the rate of products, and the formation constants of complex ions can
electrolysis. The fundamentals of the controlled-potential be evaluated from polarographic half-wave potentials, if
bulk electrolysis are discussed in recent monographs (see the electrode process is reversible. Furthermore, studies of
Bibliography). half-wave potentials as a function of ligand concentration
provide the means to determine the formula of a metal
complex.
D. Applications of Controlled-Potential Methods
The techniques of voltage sweep and cyclic voltamme-
To date, the most extensive application of electrochemical try provide the analytical and physical chemical capabili-
methods with controlled potential has been in the area of ties of classical voltammetry and, in addition, provide the
qualitative and quantitative analysis. Because a number of means to perform these measurements much more rapidly
monographs have more than adequately reviewed the liter- for a broader range of conditions. Cyclic voltammetry is
ature and outlined the conditions for specific applications, particularly useful for the rapid assessment of thermody-
this material is not covered here. In particular, inorganic namic reversibility and for the evaluation of the stoichiom-
applications of polarography and voltammetry have been etry for the electrode reaction.
discussed in great detail in the classic treatise by Kolthoff
and Lingane.
An important specialized type of voltammetric system IV. ELECTRON-TRANSFER PROCESSES
is a self-contained cell for the determination of ·O2 · in the
gas or solution phases. This is the so-called Clark elec- In electrochemical cells, electron transfer occurs within
trode, which consists of a platinum or gold electrode in the the electrode/solution interface, with electron removal
end of a support rod that is covered by an ·O2 ·-permeable (oxidation) at the anode and electron introduction (reduc-
membrane (polyethylene or Teflon) such that a thin film tion) at the cathode. The current through the solution is
of electrolyte is contained between the electrode surface carried by the ions of the electrolyte, and the voltage limits
and the membrane. A concentric tube provides the support are those for electron removal from and electron insertion
for the membrane and the means to contain an electrolyte into the solvent/electrolyte {e.g., H2 O/(H+ −
3 Oaq )(ClO4aq );
I + −
solution in contact with a silver-silver chloride reference [Na (OH2 )6 ](Claq )}
electrode. The Clark device has found extensive applica- −e−  
tion to monitor ·O2 · partial pressure in blood, in the atmo- 2 H2 O H2 O(H2 O·)+ H+
3O
sphere, and in sewage plants. By appropriate adjustment
of the applied potential, it gives a voltammetric current +[HO·](E ◦ )pH 0 , + 2.72 V vs NHE
plateau that is directly proportional to the ·O2 · partial pres- (E ◦ )pH 7 , +2.31 V (73)
sure. The membrane material prevents interference from −e −
electroactive ions as well as from surface-contaminating HO− [HO·] (E ◦ )pH 14 , +1.89 V (74)
biological materials. −e −

In addition to the analytical applications discussed Cl− Cl· E ◦ , +2.41 V


above, controlled-potential methods are used for the eval-
E ◦
MeCN , +2.24 V. (75)
uation of thermodynamic data and diffusion coefficients in
both aqueous and nonaqueous solvents. Polarographic and In the gas phase, electron removal from atoms is limited
voltammetric methods provide a convenient and straight- by their ionization potential (e.g., H·, 13.6 eV; K·, 4.3 eV;
forward means to the evaluation of the diffusion coeffi- Na·, 5.1 eV; Cu·, 7.7 and 20.3 eV; Ag, 7.6 eV; Fe, 7.9, 16.2,
cients in a variety of media. The requirements are that the and 30.7 eV). However, in the solution phase, electron
current be diffusion controlled, the number of electrons removal (oxidation) from the solvent may be facilitated
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176 Electrochemistry

by the presence of substrate atoms (rather than be from at much lower potentials [Eq. (73); at pH 0, +2.72 V vs
them). NHE]. At a silver electrode, water oxidation is facilitated
For example, with water at pH 0 the process of Eq. (73) via formation of an AgI –OH+2 bond; the shift in oxidation
is shifted −4.82 V when hydrogen atoms are present, potential from +2.72 to +0.80 V is a measure of the bond-
−e−   formation energy (−G BF ),
[H·] + 2 H2 O (H2 O)H+
3O H+
3 O + H2 O −G BF = (+2.72 − 0.80) 23.1 = 44.4 kcal mol−1 . (78)

E , −2.10 V. (76) −
At pH 14 the anodic process is the oxidation of HO ,
e−
A. Oxidative Electrochemistry: Metals, HO− HO· E ◦ , +1.89 V
Metal Complexes, Lewis Bases (E ◦ )pH 7 , +2.30 V, (79)
1. Metals I
which is facilitated via formation of an Ag –OH bond
The transformation of metal electrode surfaces via ele- [−G BF = (1.89 − 0.34) 23.1 = 35.8 kcal mol−1 ]
ctrooxidation to their metallo-oxides, solvated ions, and −e−
Ag (s) + HO− AgI −OH (s)
metal complexes is fundamental to most anodic elec-
trochemical processes (batteries, electrorefining, anodic E◦ , +0.34 V
stripping analysis, and reference electrodes). Although (E ◦ )pH 7 , +0.75 V. (80)
this is traditionally represented as the removal of one (or
more) valence electron from a metal atom at the electrode The data of Eqs. (77) and (79) can be combined to give a
surface to give a metal ion [e.g., Ag (s) − e− → Ag+ ; E ◦ , value for the solubility product (K sp ) for Ag–OH (s),
+0.80 V vs NHE], the gas-phase ionization potential [e.g., AgI (OH2 )+ −
2 + HO AgI −OH (s) + 2 H2 O
Ag · (g) − e− → Ag+ (g); IP, 7.6 eV] is far greater than the  I 
observed oxidation potential. The difference is attributed Ag (OH2 )+ −
2 [HO ] = K sp ;
to the solvation energy for the metal ion [e.g., Ag+ + log K sp = (0.34 − 0.80)/0.059 = −7.8.
nH2 O → Ag+ (aq); −G(aq) ≈ 70–100 kcal mol−1 ].
(81)
However, such a sequential path would not obviate the
7.6-V energy barrier for the initial step and is in conflict In the presence of chloride ion, metal electrodes facil-
with the observed thermodynamic reversibility for many itate its oxidation [Eq. (75); E ◦ , +2.41 V vs NHE] via
metal/solvated-metal-ion redox couples. formation of metal-chlorine covalent bonds, e.g.,
All reactions, and particularly redox processes, occur −e−
via the easiest and lowest energy pathway that is avail- Ag (s) + Cl− Ag−Cl (s) E ◦ , +0.22 V. (82)
able (mechanistically feasible) to the system. In the case Hence, the differential bond-formation energy
of a metal electrode/electrolyte interface undergoing an- [(−G BF )] [Ag–Cl bond energy, minus the energy
odic transformations, the electrons can come from (a) sur- required to break an Ag–Ag bond at the Ag (s) surface)] is
face metal atoms (energy limit; first ionization potential), given by the difference in oxidation potentials [Eqs. (75)
(b) solvent molecules (energy limit; oxidation potential and (82)],
of solvent), (c) electrolyte anions (energy limit; oxidation
potential of anions), and (d) base ligands (energy limit; ox- (−G BF ) = (2.41 − 0.22) 23.1 = 50.6 kcal mol−1 .
idation potential of ligand). All metal electrodes are elec- (83)
trochemically transformed via path b, c, or d and never
Because the escape energy for an Ag· atom from Ag (s) is
via path a. This general conclusion is illustrated for silver
68 kcal mol−1 , a reasonable approximation for the break-
and copper electrodes in aqueous and acetonitrile (MeCN)
age of a single bond is 22.6 kcal mol−1 [(1/3) 68]. When
solutions that contain inert electrolyte, chloride ion (Cl− ),
combined with Eq. (83), this gives a reasonable value for
or bipyridine (bpy).
−G BF ,
In aqueous solutions at pH 0, the silver electrode facil-
itates oxidation of water Ag· + Cl· Ag–Cl −GBF = 50.6 + 22.6
−e− = 73.2 kcal mol−1 .
Ag (s) + 2 H2 O AgI (OH2 )+
2
(84)
E ◦ , +0.80 V vs NHE. (77)
The literature value for the dissociative bond energy
The gas-phase ionization potential for a silver atom is (HDBE ) of Ag–Cl (g) is 81.6 kcal mol−1 , which is equiv-
7.6 eV. In contrast, water is oxidized (gives up an electron) alent to an estimated −G BF value of 73.8 kcal mol−1
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Electrochemistry 177

[−G BF = HDBE − TS = 81.6 − 7.8 (est) = 73.8 kcal and CeIII (OH2 )3+ +
6 , each with one, two, and three M–OH2
mol−1 ]. Thus, the proposition that metal electrode ox- covalent bonds, respectively],
idations are solvent or ligand centered with potentials
−e−   II
that reflect the metal-solvent/ligand bond-formation free CuI (OH2 )+
6 + H2 O (H2 O)+
5 Cu
(E ◦ )pH 0 ,+0.16 V
energies (−G BF ) is supported by independent bond-
energy data. The data of Eqs. (77) and (82) provide a meas- − OH+
2 (OH2 ) (H2 O)+
5 Cu −OH + H3 O
II +

ure of the solubility product for AgCl (s).  


−G BF , 59 kcal mol−1 (90)
AgI (OH2 )+
2 + Cl

AgI −Cl (s) + 2 H2 O
 I −e−   III
+
Ag (OH2 )2 [Cl− ] = K sp ; 6 + H2 O
FeII (OH2 )2+ ◦
(E )pH 0 ,+0.77 V
(H2 O)2+
5 Fe

log K sp = (0.22 − 0.80)/0.059 = −9.8. (85) − OH+ +


5 Fe −OH + H3 O
(H2 O)2+ III
2 (OH2 )
Another important example is the oxidation of Cl− at a  
−GBF , 45 kcal mol−1 (91)
mercury electrode [Hg2 (l)] to form calomel [mercurous
chloride, Hg2 Cl2 (s), Cl–HgII –HgII –Cl (s)]. −e−  IV
6 + H2 O
CeIII (OH2 )3+ ◦
(E )pH 0 ,+1.60 V
(H2 O)3+
5 Ce
−e−
Hg2 (l) + Cl− [Cl−Hg−Hg·] 
− OH+
2 (OH2 ) 5 Ce −OH + H3 O
(H2 O)3+ IV +
−e −
 
Cl−
Cl−Hg−Hg−Cl (s) E◦ , +0.27 V. (86) −GBF , 25 kcal mol−1 . (92)
The potential shift for the Cl− /Cl· couple from +2.41 In none of these examples has the potential for removal
[Eq. (75)] to +0.27 V in the presence of Hg2 (l) is a mea- of an electron approached the ionization potentials of the
sure of the [Cl–HgHg] bond energy [−G BF = (2.41 − metals. Although traditional treatments attribute the po-
0.27) 23.1 = 49.4 kcal mol−1 ]. tentials of Eqs. (77), (87), and (89)–(92) to the removal of
Similar metal-facilitated oxidations of H2 O and of Cl− electrons from the metals, coupled with large ionic solva-
occur for all metal electrodes. The respective potentials tion energies, this requires a pathway with the ionization
for the oxidation of each at a copper electrode are potential as a kinetic barrier. Furthermore, the spontaneous
−e− reaction of iron with acidified water is driven by the for-
Cu (s) + 2 H2 O (H2 O)CuI −OH+
2 (E◦ )pH 0 , +0.52 V mation of Fe–OH+ 2 and H–H covalent bonds that facilitate
  hydrogen-atom transfer from water (rather than electron
−G BF , 46 kcal mol−1 (87)
transfer from iron),
and H2 O
−e− Fe (s) + 2 H+
3O 2 + H2 (93)
(H2 O)4 FeII (OH2 )2+
Cu (s) + Cl− CuI −Cl E◦ , +0.14 V
  −3e−
−G BF , 52 kcal mol−1 . (88) {Note: To ionize a gas-phase iron atom (Fe Fe3+ )
−1
requires 54.8 eV (1266 kcal mol ); in turn, this species
Additional redox data for oxidations of H2 O/HO− at Cu, reacts upon dissolution into liquid water {Fe3+ (g) +
+
Ag, and Au electrodes in aqueous and acetonitrile (MeCN) 7H2 O(l) → [(H2 O)2+ 5 ]Fe –OH + H3 O, − H ≈ 1000
III
−1
solutions are summarized in Table I. At pH 0 with an iron kcal mol (1266 − 266)}; the net energy change often
electrode the water oxidation of Eq. (73) is shifted by is ascribed as the solvation energy for Fe3+ (g) (heat of
−3.12 V, hydration)}.
−2e−  2+ Within an aprotic solvent (e.g., acetonitrile, MeCN)
Fe (s) + 6 H2 O (H2 O)4 FeII (OH2 )2 oxidation of metals and metal complexes also is ligand
(E◦ )pH 0 , −0.40 V, (89) centered with the potential determined by the oxidation
potential of the ligand and the metal-ligand covalent bond-
which indicates that the [H2 O(H2 O·)+ ] species is sta- formation free energy (−G BF ). For example, the free bpy
bilized by a strong [(H2 O)4 (H2 O)+ ]FeII –OH+
2 covalent ligand in acetonitrile is oxidized near the solvent limit at
bond (−G BF , ∼71 kcal mol−1 ). a glassy-carbon electrode (GC) (Fig. 5),
(bpy) MeCN
bpy+ · E◦ , +2.32 V vs NHE, (94)
2. Metal Complexes
but at a copper electrode the oxidation occurs at a negative
In an analogous fashion, the removal of an electron (ox- potential,
idation) from water via Eq. (73) is aided by the presence
−e−
of transition-metal ions [e.g., CuI (OH2 )+ II 2+
6 , Fe (OH2 )6 , Cu (s) + 2 bpy CuI (bpy)+
2 E◦ , −0.16 V. (95)
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178 Electrochemistry

TABLE II Oxidation Potentials for Ligands (L) and Their ML3


Complexes with Zn(II), Mn(II), Fe(II), and Co(II) in MeCN (0.1 M
Tetraethylammonium Perchlorate)

E b1/2 , V vs NHEc
Ligand
(L or L− )a L/L+ · (L− /L·) ZnII L3 MnII L3 FeII L3 CoII L3

H2 O +2.8 +2.8 +2.8 +1.84 +2.8


bpy +2.32 >+2.5 +1.55 +1.30 +0.58
PA− +1.50 +1.54 +0.60 +0.20 +0.04
acac− +0.55 +0.58 +0.18 −0.42 −0.35
8-Q− +0.21 +0.22 −0.06 −0.41 −0.57
a Key: bpy, 2,2 -bipyridine; PA− , picolinate (2-carboxylate pyridine);

acac− , acetylacetonate; 8-Q− , 8-quinolinate.


1/2 taken as (E p,a + E p,c )/2 for reversible couples of Mn L 3 and
b E II

FeII L 3 complexes; as E p,a/2 + 0.03 V for L (or L − ) and ZnII L 3 ; and


as E p,c/2 − 0.03 V for the CoII L 3 complex that exhibits separated redox
couples.
c SCE vs NHE; +0.242 V.

Table II summarizes the oxidation potentials for lig-


ands (L) and their M II L 3 complexes with zinc(II), man-
ganese(II), iron(II), and cobalt(II). The difference in the
potentials for the free and complexed ligands is a measure
of the metal(III)-ligand covalent-bond-formation energies
(−G BF ); these are summarized in Table III. All of the
data are consistent with ligand-centered redox processes.

FIGURE 5 Cyclic voltammograms of 3 mM solution in MeCN B. Reductive Electrochemistry


(0.1 M tetraethylammonium perchlorate [TEAP]): (a) bpy; (b)
FeII (bpy)2+ II 2+ II 2+
3 ; (c) Co (bpy)3 ; (d) Zn (bpy)3 . Conditions: scan rate,
1. Free Electron (e− ); Ultimate Base and
−1 ◦
0.1 V s ; 25 C; glassy-carbon working electrode (0.09 cm2 ); SCE One-Electron Reductant in Any Matrix
vs NHE, +0.244 V.
The free electron interacts with all atoms and molecules
Figure 5 illustrates that the oxidation of the Fe II
(bpy)2+ that have finite electron affinities to produce anions and,
3
complex is reversible and ligand centered, thus, is unstable in all but the most inert liquids. Elec-
trochemistry attests to this general axiom and provides a
−e−
FeII (bpy)2+
3 FeIII (bpy)3+
3 E◦ , +1.30 V. (96) convenient means to evaluate the energetics for the ad-
MeCN
6 5 2 dition of an electron to solvent molecules and to species
d sp d sp
within a solution, e.g.,
(Noteworthy are the three reversible one-electron reduc-
tions for this complex.) The electron that is removed e  H2O(aq) [H] HO(aq)
from the FeII (bpy)2+3 complex comes from the ligands
to give bpy+ ·, which couples with one of the four un- E °, 2.93 V vs NHE (97)
paired electrons of the iron(II) center (d6 sp) to give a
3 , d sp ; S = 5/2]. The
third covalent bond [FeIII (bpy)3+ 5 2 O O
difference in oxidation potentials for FeII (bpy)2+
3 and free e  CO2 (MeCN) C C
bpy [Eq. (94)] is a measure of the FeIII –bpy+ bond en-
ergy [−G BF = (2.32 − 1.30) 23.1 = 23.6 kcal mol−1 ]. O O
The potential that would be required to remove an elec-
tron from the d6 sp manifold of the iron(II) center of E °, 1.86 V vs NHE (98)
FeII (OH2 )2+ II 2+
6 or Fe (bpy)3 would be greater than the first
ionization potential of atomic iron (7.9 eV). e  Me2S(O) H2C S(O)Me  [H] (99)
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Electrochemistry 179

TABLE III Apparent Metal-Ligand Covalent-Bond- The electrochemical reduction of permanganic acid
Formation Free Energies (−∆G BF ) for Several Man- [HOMnVII (O)3 ], which is traditionally represented as a
ganese, Iron, and Cobalt Complexes
metal-centered electron transfer to change Mn7+ to Mn6+ ,
a
Complex −∆G BF , kcal mol−1 is another example of a ligand-centered process,
A. Manganese
(O)3 MnVII –OH + H+
3O+e

MnVI (O)3 + 2 H2 O
(8Q)2 MnIII –8Q 6
(acac)2 MnIII –acac 9 −GBF = 28 kcal mol−1 (pH 1). E◦ , +1.45 V (106)
(PA)2 MnIII –PA 22
[(bpy)2 MnIII –bpy]3+ >23b Comparison of this with the reduction of free hy-
B. Iron droxyl radical (HO·) [Eq. (104)] provides a measure
(8Q)2 FeIII –8Q 15 of the HO–MnVII (O)3 bond energy [−G BF = (2.66 −
(acac)2 FeIII –acac 23 1.45) 23.1 = 28 kcal mol−1 ]. The other strong oxidants
3+
(PA)2 FeIII –PA 31 [(HO)2 CrVI IV
2 (O)5 and HOCe (OH2 )5 ] that are used for
[(bpy)2 FeIII –bpy]3+ >29b aqueous redox titrations are reduced by a similar path,
[(Ph3 PO)3 FeIII –OPPh3 ]3+ >30b
[(MeCN)4 FeIII –OH2 ]3+ 23 HO–CrVI (O)2 OCrVI (O)2 OH + H+
3O+e

C. Cobalt
+1.30 V (O)2 CrV OCrVI (O)2 OH + 2 H2 O
(8Q)2 CoIII –8Q 16
(acac)2 CoIII –acac 21 −G BF , 31 kcal mol−1 (pH 1) (107)
(PA)2 CoIII –PA 35 + −
[(bpy)2 CoIII –bpy]3+ >46b 5 + H3 O + e
HO–CeIV (OH2 )3+
a (−G BF ) = [E 1/2[ZnL − /ZnL 2 (L·)] − E 1/2(M L − /M(·L)L 2 ) ] +1.66 V 6 + H2 O
CeIII (OH2 )3+
3 3
× 23.1 kcal mol−1 . −GBF , 23 kcal mol−1 (pH 1). (108)
b (−G ) = [E
BF p,a (ZnL/ZnL + ·) − E p,a(M L/M−L + ) ] × 23.1 kcal
mol−1 ; L = (bpy)3 or (Ph3 PO)4 .
An important point in these electron-transfer reductions
is that the primary electron acceptor is the hydronium ion
e    (H+ 3 O), which is transformed to a hydrogen atom (H·) that
reacts with HO· (either free or bound via a covalent bond
to the metal center). Thus, in the reactions of Eqs. (103),
(104), and (106)–(108), the oxidant in each is the hydro-
nium ion (H+
H2O
 H  HO 3 O) and the reduction potential is determined
by the H–OH bond energy (−G BF ) of the product H2 O,
(100)
minus the metal–OH bond energy [Eqs. (106)–(108)].
Hence, reductive electrochemistry converts electrons (e− ) Under alkaline conditions MnVII O− 4 is reduced via di-
via the solution matrix at the interface to atoms and an- rect electron addition to one of the bound oxygen atoms,
ions. The solution outside the inner double layer never

is exposed to an electron. Some examples of such inner- OMnVII (O)3 + e− −
OMnVI (O)2 O−
double-layer electron transfer include
E ◦ , +0.55 V vs NHE. (109)
− − ◦
H2 O + e [H·] + HO E , −2.93 V vs NHE
(101) The extent of the stabilization of the oxygen atom in
H+ +e −
[H·] + H2 O ◦
E , −2.10 V MnVII O−
4 is indicated by the reduction potential for a free
3O (102)
·O· atom,
(H2 O)25 + FeIII –OH + H+
3O+e

[·O·] + e− ·O− (E◦ )pH 14 , +1.43 V. (110)
pH 1 ◦
Fe II
(OH2 )2+ + H2 O E , +0.71 V (103)
H2 O 6
In summary, the electron-transfer reactions for metals
pH 1
[HO·] + H+
3O+e

H2 O
2 H2 O E◦ , +2.66 V (104) and metal complexes are ligand centered (or solvent cen-
tered). In each case the potential for the oxidation of free
  ligand is decreased in the presence of metal or reduced-
−GBF (H2 O)2+
5 Fe –OH = [2.66 − 0.71] × 23.1
III
metal complex by an amount that is proportional to the
= 45 kcal mol−1 (105) metal-ligand bond energy (−G BF ).
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180 Electrochemistry

2. Electro-Induced Hydrogenation Often, the first step in the electrochemical characteriza-


tion of a compound is to ascertain its oxidation-reduction
Reductive electron transfer in an electrochemical cell oc-
reversibility. Cyclic voltammetry usually is the most con-
curs by insertion of an electron from the electrode (cath-
venient and reliable technique for this and related quali-
ode) into the solution matrix within the double layer of
tative characterizations of a new system. The discussion
the electrode/solution interface {e.g., H2 O/(H+ −
3 O)(ClO4 );
I + − in earlier sections outlines the specific procedures and re-
[Na (OH2 )6 ](ClO4 )}.
lationships. The next step in the characterization usually
e− is the determination of the electron stoichiometry of the
H+
3O [H·] + H2 O (E◦ )pH 0 , −2.10 V vs NHE
oxidation-reduction steps of the compound. Controlled-
(E ◦ )pH 7 , −2.51 V. (111) potential coulometry provides a rigorously quantitative
means to such evaluations.
The reductive processes of Eq. (111) may be facilitated by The electrochemical characterization of the oxida-
the presence of substrates to stabilize the H-atom product. tion/reduction chemistry of metals, metal ions, and metal
For example, in pH 0 water, the reduction process is shifted complexes has been discussed in Section III. In the follow-
by +4.82 V when hydroxyl radicals (HO·) are present, ing paragraphs, the use of electrochemistry for molecular
e− characterization is further illustrated.
H+
3 O + [HO·] HO–H + H2 O E◦ , +2.72 V
 
−G BF , 111 kcal mol−1 (112) A. Hydronium Ions, Brønsted Acids,
and Molecular Hydrogen
and by +2.10 V at a platinum electrode,
e− The most fundamental redox process in electrochem-
H+
3 O + Pt Pt–H + H2 O E◦ , 0.00 V istry is the reductive transformation of hydronium ion
  [H+
−G BF , 48 kcal mol−1 (113) 3 O(aq)] at a platinum electrode to molecular hydrogen
[H2 (g)],
In the presence of benzoquinone (Q), the shift is +2.80 V, Pt
2 H+
3 O(aq) + 2e

H2 (g) E◦ , 0.0000 V vs NHE.
O H
(115)
2e
2H3O  Q (E°) pH 0, 0.70 V
When properly engineered and with [H+ 3 O(aq)] at unit ac-
O H (∆GBF, 65 kcal mol1 ). tivity and PH2 at unit fugacity, this electrode system is the
(114) thermodynamic reference standard for measurements of
electrochemical potentials and is referred to as the Normal
Hydrogen Electrode (NHE), which is alternatively called
V. ELECTROCHEMICAL the Standard Hydrogen Electrode (SHE),
CHARACTERIZATION OF MOLECULES
 2 

E = E NHE + 2.30 RT/2F log H+ 3 O(aq) PH2
An increasing number of chemists use electrochem- ◦
istry as a characterization technique in a fashion anal- (E NHE ≡ 0.0000 V at all temperatures, 0–100◦ C)
ogous to their use of infrared, UV-visible, NMR, and [2.30RT/2F = 0.05915/2 at 25◦ C]. (116)
ESR spectroscopy. Some of the chemical questions
that are amenable to treatment by electrochemistry in- The latter equation for the NHE also is the defining ba-
clude (1) the standard potentials (E ◦ ) of the com- sis for the potentiometric measurement of hydronium-ion
pound’s oxidation-reduction reactions, (2) evaluation of activity [H+3 O] and molecular hydrogen fugacity (PH2 ),
the solution thermodynamics of the compound, (3) de-  
pHa ≡ −log H+ ◦
3 O = [(E NHE − E ind )/0.059]
termination of the electron stoichiometry of the com-   ◦
pound’s oxidation-reduction reactions, (4) preparation − log PH2 = −E ind /0.059 (E NHE = 0.000 V;
and study of unstable intermediates, (5) evaluation of
PH2 = 1.00 atm) (117)
the valence of the metal in new compounds, (6) de-
termination of the formulas and stability constants of    2
metal complexes, (7) evaluation of M–X , H–X , and ◦
log PH2 = [(E NHE − E ind ) 2/0.059] + log H+3O
O–Y covalent-bond-formation energies (−G BF ), and ◦  
= −E ind (2/0.059) E NHE = 0.000 V; H+ 3O
(8) studies of the effects of solvent, supporting electrolyte,
and solution acidity upon oxidation-reduction reactions. = 1.000 . (118)
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Electrochemistry 181

Electrochemical measurement of pHa via Eq. (116) senses Substitution of Eq. (122) into Eq. (116) gives
hydronium-ion activity rather than its concentration.
E Pt = 0.059 log (K a )sol + 0.059 log [HA(sol)]/[A− (sol)]
Hence, electrochemical evaluations of dissociation con-
stants (K HA ) yield thermodynamic quantities − (0.059/2) log PH2 . (124)

HA + H2 O H+
3O+A K HA This equation in conjunction with voltammetric measure-
 +  − ments of half-wave potentials (E 1/2 ) for the reduction of
K HA = H3 O [A ]/[HA]. (119)
Bronsted acids at a platinum electrode in any solvent per-
mits the evaluation of (K a ) sol [pK a (sol)],
1. Hydronium-Ion (H+   
3 O) Reduction E 1/2 = 0.059 log (K a )sol + 0.059 log κ A− κH2 κHA
Although the NHE is fundamental to electrochemistry,
= −0.059 pK a + ε, (125)
it does not represent the primary electron-transfer step
for hydronium-ion reduction at an inert (glassy-carbon) where κ A− , κH2 , and κHA are parameters that relate to diffu-
electrode, sion coefficients, activity coefficients, and PH2 for a given
GC experimental system. Because solvent has such a major
H+
3 O(aq) + e

H·(aq) E◦ , −2.10 V vs NHE, and selective effect on the activity of H+ 3 O(aq), the differ-
(120) ences between concentration-based dissociation constants
(pK ) and activity-based constants (pK a ) are dramatic. For
where GC means a glassy-carbon electrode. The −2.10-V example, phenol in MeCN (pK , 26.6; pK a , 16.0) and in
difference in standard potential (E ◦ ) between the latter Me2 SO (pK , 16.4; pK a , 20.8) exhibits a reversal; it disso-
and that for the NHE [Eq. (115)] is due to the platinum ciates more in Me2 SO than in MeCN, but is more acidic
electrode, which stabilizes the hydrogen atom (H·) via [greater H+ 3 O(aq) activity] in MeCN. Other examples in-
formation of a Pt–H covalent bond, clude (Et3 NH)Cl in MeCN (pK , 18.5; pK a , 10.0) and in
H+
3 O(aq) + Pt (s) + e

Pt–H (s) E◦ , 0.000 V Me2 SO (pK , 10.5; pK a , 12.7) (again, greater dissociation
in Me2 SO and greater acidity in MeCN); PhC(O)OH in
(−G BF ) = [0.00 − (−2.10)] 96.48 kJ mol−1 (eV)−1 MeCN (pK , 20.7; pK a , 7.9), in Me2 SO (pK , 11.1; pK a
= 203 kJ mol−1 = 48 kcal mol−1 , (121) 13.6), in DMF (pK , 11.6; pK a , 11.5), and in H2 O (pK , 4.2;
pK a , 3.2); and H2 O in MeCN (pK a , 30.4) and in Me2 SO
where −G BF is the free energy of bond formation. (pK , 31.4; pK a , 36.7).
In this system the platinum electrode surface does not
consist of free platinum atoms, but must undergo ho- 3. Oxidation of Dissolved Dihydrogen (H2 )
molytic Pt–Pt bond breakage [HDBE , 24 kcal mol−1
per Pt· (est)] before a Pt–H bond is formed. Thus, the Molecular hydrogen (H2 ; HDBE , 104 kcal mol−1 ) is re-
Pt–H bond-formation energy (−G BF ) is estimated to be sistant to electrochemical oxidation at inert electrodes
72 kcal mol−1 on the basis of the electrochemical data [for (glassy carbon or passivated metals; Ni, Au, Hg, Cu). At
the gas-phase Pt–H molecule, HDBE ≤ 80 kcal mol−1 or passivated Pt and Pd, dissolved H2 only exhibits broad, dif-
(−G BF ≈ 72 kcal mol−1 )]. Determination of the reduc- fuse, anodic voltammetric peaks with irreproducible peak
tion potential for H+
3 O(aq) at other metal electrodes (M)
currents that are not proportional to the partial pressure of
provides a convenient means to estimate M–H bond ener- dissolved H2 (PH2 ). However, with freshly preanodized Pt
gies [(−G BF )]. and Pd electrodes, well-defined oxidation peaks for H2 are
obtained, which have peak currents that are proportional
to PH2 . The surface conditioning produces a fresh reactive
2. Brønsted-Acid (HA) Reduction and Evaluation
metal-oxide surface [PtII (OH)2 (s)], which upon exposure
of pK a(sol)
to H2 becomes an oxide-free metal surface (Pt∗ ). In turn,
Brønsted acids (HA) undergo dissociation in any solvent the clean surface reacts with a second H2 to form two Pt–H
to yield the solvated aqua-hydronium ion [(sol)n H+3 O(aq)] bonds,
{from residual H2 O; or [(sol)n Hsol+ ] for basic solvents},   fast
2 Pt∗ (s) + H2 PH2 2 Pt–H (s) Keq , ∼1 atm−1 .
which further dissociates to H+ 3 O(aq) and the solvated
conjugate base [A− (sol)n ] (126)
HA (sol) + H2 O H+ −
3 O(aq) + A (sol) (Ka )sol The value of K eq is estimated on the basis of the Pt–H
(122) bond-formation energy from metallic platinum
and [(−G BF ), 48 kcal mol−1 ] and the dissociative
H+ −
3 O(aq) = (Ka )sol [HA (sol)]/[A (sol)]. (123) bond energy for H2 (G DBE , ∼96 kcal mol−1 ).
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182 Electrochemistry

This activated platinum electrode system is the equiv- sensors for ·O2 · are the most common analytical method-
alent of an NHE and, therefore, conforms to the Nernst ology for its assay in blood, gas streams, biotreaters, and
expression of Eq. (116). Rearrangement gives process streams.
 2
log PH2 = −E Pt (2/0.059) + log H+
3 O(aq) , (127)
1. Molecular Oxygen
which responds to the overall reaction 
The ground state of molecular oxygen (·O2 ·, 3 − g ) has
  K eq two unpaired electrons in degenerate 2πg orbitals and is re-
H2 PH2 + 2 Pt∗ (s) 2 Pt–H (s) ferred to as dioxygen by most contemporary biologists and
−2e − biochemists. When dioxygen is reduced by electron trans-
2 H+
3 O(aq) + 2 Pt (s). (128) fer, a series of intermediate basic dioxygen and monooxy-
H2 O
gen species are produced that may take up one or two hy-
Although there is a long-standing tradition to write an dronium ions (H+ −
3 O) from the media (O2 ·, HOO·, HOO ,

− −
electron-transfer sequence with electron removal (ioniza- HOOH, ·O , HO·, HO , and H2 O). The thermodynamics
tion) from the hydrogen atom to produce a proton [Pt–H (s) for the various reduction steps in aqueous solutions have
→ Pt + H+ + e− ] followed by hydration to give the ob- been evaluated by numerous techniques, but all are fun-
served hydronium ion [H+ + H2 O → H+ 3 O(aq)], the ion- damentally based on the calorimetry associated with the
ization potential for a free hydrogen atom (H·) is 13.6 eV reaction
and even greater for bound hydrogen [Pt–H (s)]. Electron
removal from an aqueous solution at pH 0 with a GCE ·O2 · (g) + 2 H2 (g) 2 H2 O (l) −G◦ = nE◦cell F.
(free of H2 and Pt–H) occurs via the lowest energy path, (131)
which is oxidation of the solvent
If redox potentials are relative to the normal hydrogen
−e−   H2 O
H2 O H+
2 O· H+
3 O + HO·
electrode,
E ◦ , +2.72 V vs NHE. (129) 2 H+
3 O + 2e

H2 (g) E◦H+ O/H2≡0.000, (132)
3

In the presence of Pt–H (s) (and H2 ), this process is facil- then the standard redox potential for the four-electron re-
itated via direct formation of an H–OH bond, duction of dioxygen (E O◦ 2 /H2 O ) can be calculated from
−e− the calorimetric data for the reaction of Eq. (131) under
H2 O + Pt–H (s) Pt (s) + H+
3 O + HO–H E ◦ , 0.00 V standard-state conditions,
H2 O

(−G BF ) = (2.72 − 0.00) 23.1 kcal (eV)−1 ·O2 · (g) + 4 H+


3 O(aq) + 4e

2 H2 O (l)
= 63 kcal mol−1 (130) E◦O2 /H2 O = E◦cell − E◦H+ O/H2 = +1.229 V vs NHE.
3

Addition of the Pt–H (s) bond energy [(−G BF ) = (133)


48 kcal mol−1 ] to the differential bond-formation energy
The reduction potentials for ·O2 · and various interme-
for H–OH gives an electrochemical measure of the HO–H
diate species in H2 O at pH 0, 7, and 14 are summarized
bond energy [−G BF = 111 kcal mol−1 (literature value,
in Table IV; similar data for ·O2 · in MeCN at pH −8.8,
111 kcal mol−1 )].
10.0, and 30.4 are presented in Table V. For those couples
that involve dioxygen itself, formal potentials are given
in parentheses for ·O2 · at unit molarity (∼103 atm; [·O2 ·]
B. Dioxygen Species (·O2 ·, HOO·/O−
2 ·, HOOH) ≈1 mM at 1 atm partial pressure). The reduction manifolds
Although the electrochemistry of hydronium ion and for ·O2 · (Tables IV and V) indicate that the limiting step (in
molecular hydrogen is fundamental, the electrochemi- terms of reduction potential) is the first electron transfer
cal characterization of oxygen species (·O2 ·, HOO·, O− 2 ·, to ·O2 · and that an electron source adequate for the reduc-
HOOH, HOO− , ·O·, HO·, O− ·, H2 O, HO− , O3 , O− 3 ·) and tion of ·O2 · will produce all of the other reduced forms of
of the oxygen component of molecules (e.g., Mx O y , oxy dioxygen (O− −
2 ·, HOO·, HOOH, HOO , HO·, H2 O, HO )

anions and radicals, quinones) is its most important and via reduction, hydrolysis, and disproportionation steps.
unique application. In general, electrochemical measure- Thus, the most effective means to activate ·O2 · is the addi-
ments provide the only direct means for the evaluation of tion of an electron (or hydrogen atom; H+ −
3 O + e → H·),
the electron-transfer thermodynamics of oxygen species which results in significant fluxes of several reactive oxy-
and oxygen-containing molecules. Also, amperometric gen species.
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Electrochemistry 183

TABLE IV Standard Reduction Potentials for Dioxygen Species in Water [O2 , 1 atm (1 mM)] (Formal Potentials for 1 M O2 )

1.66 V vs NHE
pH 0 (1 M H3O)
1.13

0.05 (0.12) 1.44 0.80 2.72


O2 HOO HOOH H2O  HO 2 H2O

0.695 (0.78) 1.763

0.73 (0.79)

1.229 (1.27)

1.20
pH 7
0.64

0.33 (0.16) 0.89 0.38 2.31


O2 O
2 HOOH H2O  HO 2 H2O

0.281 (0.36) 1.349

0.31 (0.37)

0.815 (0.86)

0.65
pH 14 (1 M HO)
0.09

0.33 (0.16) 0.20 0.03 1.77


O2 O2 HOO H2O  OH 4 H2O

0.065 (0.02) 0.867

0.03 (0.01)

0.401 (0.44)

2. Aprotic Media dia decrease. The heat of hydration (−Haq ) for gaseous
O− −1
2 · is 100 kcal mol , which is consistent with the unique
In the absence of proton sources dioxygen is reversibly
strong solvation of anions by water. Hence, if the E O◦ /O− ·
reduced to superoxide ion,
values for the ·O2 ·/O−
2
2 · couple are affected primarily by
2


·O2 · + e− O−
2· E◦ , −0.64 V vs NHE. (134) the degree of solvation of O2 · (that is, the solvation en-
The second reduction is an irreversible one-electron ergy for ·O2 · is assumed to be small and about the same
process, for different solvents), then the relative solvation energies
H2 O
for O− 2 · are H2 O  Me2 SO > DMF > py ∼ MeCN.
O−
2·+e

HOO− + HO− Ep,c , −1.8 V (135)
− − −
HO + HOO + ·O2 · 2 O 2 · + H2 O 3. Hydrogen Peroxide (HOOH, H2 O2 )
−9 −1 −1
K , 10 M atm . (136)
The electrochemical reduction of HOOH in pyridine
The reduction potential for the ·O2 ·/O−2 · couple shifts to yields a superoxide ion. That a reduction process gen-
more negative values as the solvating properties of the me- erates a species with a higher oxidation state than HOOH
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184 Electrochemistry

TABLE V Formal Reduction Potentials for 1 M Dioxygen Species in Acetonitrile [O2 at 1 atm (8.1 mM)]

2.17 V vs NHE
pH 8.8
1.64 [1 M (H3O)ClO4]

0.64 1.96 1.32 3.24


O2 HOO HOOH H2O  HO 2 H2O

1.30 2.28

1.31

1.79

1.06
pH 10.0
[1:1 (Et3NH)Cl/Et3N]
0.64

0.47 0.85 0.21 2.13


O2 HOO HOOH H2O  HO 2 H2O

0.19 1.17

0.20

0.68

0.50
pH 30.4
[1 M (Bu4N)OH]
1.04

0.63 1.27∗ 1.02∗∗ 0.80∗∗∗


O2 O
2 HOO HO  O 4 HO

0.95 0.11

0.90

0.53

∗(O  1.51 V HOOH ).


2

∗∗(HOOH 0.90 V HO  HO).


∗∗∗(HO 0.92 V
 HO ).

is surprising. The cyclic voltammogram for the reduc- oxide ion. The products and the observed electron stoi-
tion of HOOH in pyridine at a platinum working elec- chiometries for the electrochemical reduction of HOOH
trode exhibits a broad cathodic peak at −0.95 V vs NHE are consistent with a mechanism in which the primary step
and anodic peaks for the reverse scan at −0.50 and is a one-electron transfer,
−0.15 V vs NHE. The latter is characteristic of elec-
trolytically generated H2 . Controlled-potential reduction HOOH + e− HOO− + 1/2 H2
of HOOH in pyridine at −1.0 V vs NHE (with argon de- E◦ , −1.0 V vs NHE (137)
gassing) results in a solution that exhibits an anodic cyclic
voltammogram that is characteristic of O− 2 ·. ESR studies followed by a chemical reaction with another hydrogen
of the reduced solution confirm the presence of a super- peroxide molecule.
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Electrochemistry 185

HOOH + HOO− [HOOOH] + HO− Some of the considerations for electron-transfer pro-
py cesses that have been discussed are fundamental to
k,3 × 109 M−1 s−1
1/n [·pyOH]n + H2 O + O−
2· (138) the electrochemistry of these examples. Thus, reduc-
tive processes always involve the most electrophilic
The resultant HO· is trapped by the pyridine solvent to
(acidic, positive-charge density) center (substrate or sub-
yield a stable solution of O− 2 ·. strate/matrix combination) that produces the least basic
In acetonitrile there is no evidence of a superoxide ion,
(nucleophilic) product. Under acidic conditions the pri-
either by ESR or by cyclic voltammetry, from the elec-
mary reactant often is the hydronium ion (H+ 3 O) to give a
trochemical reduction of HOOH. This can be explained
hydrogen atom that couples with the substrate via covalent
by the slow rate of reaction of HO· with CH3 CN (k, 4 ×
bond formation, e.g.,
106 M−1 s−1 ), which favors direct disproportionation.
[HOOOH] + HO− H2 O + [HOOO− ] PhN NPh + 2 H+
3 O + 2e

HO− + ·O2 · PhNHNHPh + 2 H2 O Ep,c , −0.5 V vs SCE.


Me2 SO
(139) (144)
The reduction of hydrogen peroxide in aqueous solution In contrast, oxidations always involve the most nucle-
appears to be analogous to that in CH3 CN, with the mech- ophilic (basic, negative-charge density) center (substrate
anism represented by the reaction of Eq. (137) followed or substrate/base combination) that produces the least
by the reactions of Eqs. (138) and (139). Thus, the re- acidic (electrophilic) product. Under basic conditions (or
duction of HOOH yields H2 and HOO− , initially, in a neutral aqueous solutions) the primary reactant often is
one-electron step. The final products are the result of the the base [B − ; HO− , HOC(O)O− , AcO− , PhO− ] to give
reaction of HOO− and HOOH and are analogous to those an oxyl radical (e.g., HO·) that adds to the substrate or,
for the base-induced decomposition of HOOH. more often, abstracts a hydrogen atom, e.g.,
In acetonitrile HOOH is oxidized to ·O2 · via an electron-
−2e−
transfer/chemical/electron-transfer (ECE) mechanism, PhNHNHPh + 2HO− PhN NPh + 2 H2 O
MeCN
−e−
[HOOH]+ · HOO· +H+ E p,a , −1.1 V vs SCE.
H2 O
HOOH 3O
(145)
◦
E , +2.0 V vs NHE (140) 1. Elemental Sulfur (S8 )

−e
HOO · ·O2 · + H+
3O
◦
E , +0.6 V vs NHE. (141) Although the cyclic voltammogram of S8 (in dimethyl sul-
H2 O
foxide at a gold electrode) appears to be a simple sequence
Although HOO− reacts rapidly with most organic sol- of two two-electron-per-S8 , pseudo-reversible reductions,
vents, it persists long enough in pyridine to permit its controlled-potential coulometry at −0.7 V vs SCE indi-
electrochemical oxidation via a similar ECE mechanism. cates that 2.7 electrons per S8 are consumed to give S2− 6 .
−e− HO− Controlled-potential coulometry at −1.5 V vs SCE con-
HOO− [HOO·] H2 O + O−
2· sumes 4.0 electrons per S8 to produce two S2− 4 ions. On the
E ◦ , −0.37 V vs NHE (142) basis of these results and associated spectroscopic studies,
the reduction sequence in Me2 SO involves two ECE steps
−e−
O−
2· ·O2 · E ◦ , −0.66 V vs NHE (143) with ring opening and chain breaking the two chemical
steps,
C. Nonmetals e
c-S8  e S
8
Although hydronium ion (H+
Ep,c,0.60 V vs SCE
3 O) and dioxygen (·O2 ·) are
the most studied of the molecules and ions without metal S e
atoms, several of the molecules that contain sulfur, ni- 8 S42 S
4
Ep,c, 1.29 V
trogen, or carbon also are electroactive. The results for
representative examples illustrate the utility of electro- e

chemical measurements for the evaluation of the redox


thermodynamics and bond energies for nonmetals. In 2
S4
particular, the electrochemistry for several sulfur com-
(146)
pounds [S8 , SO2 ], nitrogen compounds [·NO, hydrazines
(RNHNHR  )], and carbon compounds (CO2 , CO) is sum- The appearance of the bright blue solution (S−
3 ·) during
marized and interpreted. the course of electrolysis is dramatic;
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186 Electrochemistry

0.6 V vs SCE 4. Hydrazines and Amines


3S8  8e 8S
3
These substrates are directly oxidized in a base-free
KD, 1.1  102 M1 matrix (Me2 SO or MeCN) at platinum or glassy-carbon
electrodes with the potential primarily determined by the
2 RN-H bond energy and secondarily by the basicity of the
4S6 (147) substrate,

e
2. Sulfur Dioxide (SO2 ) 2 PhNHNHPh PhNNHPh  R NH2
(R NH) Ep,a, 0.6 V vs SCE

In aprotic solvents SO2 undergoes a reversible one- e


PhN NPh  R NH2
R NH
electron reduction,
(152)
SO2 + e− SO−
2· E1/2 , −0.75 V vs SCE. (148) 
DMF e
2 PhNH2 PhNH  PhNH3
Ep,a, 0.9 V vs SCE
However, the product species interacts with excess SO2 to 2 PhNH2
give a blue complex that is significantly more difficult to e
PhNHNHPh  PhNH
3
oxidize.
2e 2 PhNH2
SO
2  2 SO2 (SO2)2 S(O)O
PhN NPh  2 PhNH
3.
e Ep,a , 0.25 V vs SCE
(153)
In contrast, when a hydroxide ion HO− is present it
3SO2 (149)
is more easily oxidized than the amine substrates. In
Complete electrolysis yields SO− MeCN, in the absence of substrate, HO− is oxidized
2 ·, which dimerizes to
dithionite ion (colorless), at +0.7−0.9 V vs SCE. However, with hydrazines and
amines present, the N H bonds are homolytically cleaved
2SO−


O2 SSO−
2 K D , 2.4 × 101 M−1 . (150) by the HO· product of HO− oxidation. The latter’s oxida-
DMF
tion potential is shifted by the difference in the HO H
Because SO2 is electrophilic (acidic), it is extremely and RN H bond energies (−G BF ). Thus, the oxidation
resistant to direct electron-transfer oxidation. However, in of PhNHNHPh is shifted by −1.7 V when HO− becomes
aqueous solutions at pH 1, SO2 facilitates the oxidation of the electron-transfer mediator; with PhNH2 the shift is by
H2 O [2 H2 O → HO· + H+ − ◦
3 O + e ; E , +2.42 V vs SCE −1.1 V.
(pH 1)] at gold electrodes via covalent-bond formation to
give sulfuric acid [(HO)2 S(O)2 ] in an ECE process. The e
PhNHNHPh  HO E 1.1 V vs SCE
PhNHNHPh  H2O
p,a,
peak current is proportional to the SO2 concentration and
e
its diffusion coefficient, which makes this anodic process PhN NPh  H2O
HO
suitable as a voltammetric monitor for dissolved SO2 or (154)
gas-phase SO2 via a gas-permeable membrane.
e
PhNH2  HO PhNH  H2O
3. Nitric Oxide (·NO) 0.2 V vs SCE
HO, PhNH2
Reduction of the oxides of nitrogen (·NO, ·NO2 , and N2 O) e
PhNHNHPh  H2O
usually involves the addition of hydrogen atoms that are
(155)
electrogenerated. The use of a mercury electrode inhibits
the reduction of H+ ◦
3 O to H2 (E , −2.2 V vs SCE at pH 5),
but allows formation of H· when it couples with a substrate
via covalent-bond formation, 5. Carbon Dioxide (CO2 )

O  H  E1/2, 0.9 V vs SCE


Whereas the reduction of CO2 at a gold electrode is a one-
N 3 O (pH 5.0)  e [NO H]
electron per CO2 process on a voltammetric time scale,
2X
at mercury it is a sequential two-electron process. In both
[HON NOH] N N O  H2O cases the overall reduction is two electrons per CO2 . The
(N2O) products for anhydrous conditions are CO2− 3 and CO and,
(151) with H2 O present, HOC(O)O− and HC(O)O− ,
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Electrochemistry 187

O acids HA] react with the ultimate nucleophile (the elec-


CO2  Au(s)  e AuI C (s) Ep,c, 2.1 V vs SCE tron) directly or via its reaction product with hydronium
CO2
O ion (H+ 3 O) or Brønsted acids (HA).
For those electrophiles (El) that undergo direct electron-
e
Au(s)  HC(O)O  HOC(O)O AuI C(O)OC(O)O(s) transfer reduction at an inert electrode (glassy carbon)
H 2O
e [with the electron occupying the Lowest-Unoccupied-
Au(s)  CO  OC(O)O Molecular-Orbital (LUMO)], the reduction potential
(156) (E red ) is a measure of their electron affinity and elec-
trophilicity [relative to that for H+3 O (−2.10 V vs NHE
CO2  Hg2(l)  e HgI HgII C(O)O(s) Ep,c, 2.3 V in aqueous media)] (the more positive the potential, the
more electrophilic the molecule).
e H2O e, 2.5 V

El + e− El − ·
CO2
Hg2(l)  HC(O)O HO
E red (159)
[O(O)C HgII HgII C(O)O(s)] CO2 Often, the solution matrix contains Lewis acids (e.g.,
HOC(O)O
H+
3 O) that are more electrophilic than the substrate
Hg2(l)  CO  CO 3
2 molecule and, in combination, are even more electrophilic,
(157) e, H3O
El  H3O  e [HEl] HE lH (Ered)EC.

6. Carbon Monoxide (CO) H2O H2O


(160)
At an activated gold electrode in alkaline (0.01 M NaOH)

aqueous solution CO is oxidized to CO2− 3 via a HO -cen-
The first-formed intermediate (with an unpaired electron)
tered ECE process, in combination with a second Lewis acid molecule has
even greater electron affinity and is reduced at a more
e, Au e
CO  HO [AuI C(O)OH] (HO)2C(O) positive potential to give a voltammogram that appears
E1/2, 0.55 V vs SCE HO

2 HO
to be the result of an irreversible two-electron reduction
process. In most cases it is an ECEC process in which each
2
CO3  2 H 2O. electron transfer (E part of the ECEC mechanism) to the
Lewis acid (H+ 3 O) is reversible to give a product (H·) that
(158)
forms a covalent bond with the substrate (H–El) (the C
Again, the activated gold surface stabilizes the carbon part of the mechanism).
radical intermediate [·C(O)OH] and facilitates the second Conversely, nucleophilic molecules (Nu) [Lewis bases;
electron-transfer oxidation of HO− to HO· via coupling e.g., catechols, hydroquinones, phenols, alcohols, and thi-
to the carbon radical. ols (and their anions); aromatic hydrocarbons and amines
(benzene, toluene, pyridine, bipyridine, etc.)] can be oxi-
dized (1) by direct electron-transfer oxidation [Eq. (161)]
D. Organic Molecules [with the electron coming from the Highest-Occupied-
Most organic reactions are Lewis acid/base processes that Molecular-Orbital (HOMO)] or (2) by coupling with the
involve the interaction of a nucleophilic center with an oxidation product of H2 O (or HO− ), hydroxyl radical
electrophilic center. Because electrochemistry provides (HO·) [Eq. (162)].
the ultimate nucleophile via the electrons at the cathode
−e−
surface and the ultimate electrophile via the electron holes Nu: Nu+ · E ox (161)
at the anode surface, it is the ideal methodology for the
characterization of the electrophilicity and nucleophilic- The potential (E ox ) for those nucleophiles that undergo
ity of molecules. Thus, the carbon centers of saturated direct electron-transfer oxidation at an inert electrode is
hydrocarbons (e.g., CH4 ) are resistant to electrochem- a quantitative measure of their nucleophilicity (the more
ical reduction and oxidation because of their inert na- negative the potential the more nucleophilic the molecule;
ture (all valence electrons are stabilized in sigma bonds; see Table VI for representative values). In many cases wa-
an absence of any Lewis acid/base character). However, ter in the solvent matrix (or as the solvent) is more nucle-
organic molecules with electrophilic components [e.g., ophilic than the substrate molecule and, in combination,
alkyl-, aryl-, and acyl- halides; carbonyl groups; unsatu- is even easier to oxidize, which often results in an ECEC
rated and aromatic hydrocarbons; nitro groups; Brønsted oxidation process.
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188 Electrochemistry

TABLE VI Nucleophilicity and Electrophilicity of Molecules and Ions (Strongest or Most


Reactive at Top of Listing)
(E 1/2 )ox , V vs NHE (E 1/2 )red , V vs NHE

Nucleophile (MeCN) (H2 O) Electrophile (MeCN) (H2 O)


eaq −3.9 −2.9 H2 O+ · +3.2 +2.7
K· −2.9 −2.9 Ph+ ·CH2 OH +2.2
Na· −2.1 −2.7 AuI (OH2 )+
6 +1.6 +1.8
(Cl8 TPP+ ·)FeIV O +1.5
(Compound I)
Li· −2.0 FeIII (bpy)3+
3 +1.3 +1.1
(TPP− ·)Co− −1.7 HO· +0.9 +1.9
H· −1.6 −2.1 FeIII (PA)3 +0.4
(TPP− ·)Fe− −1.4 (TPP)FeIII (py)+
2 +0.4
(TPP)Fe− −0.8 (TPP)FeIII Cl +0.2
(TPP)Co− −0.6 MV2+ −0.2
O−
2· −0.7 −0.2 (Cl8 TPP)FeIV O −0.3
(Compound II)
PhCH2 S− 0.0 AQ (Anthraquinone) −0.6
HOO− 0.0 +0.7 O2 −0.7 −0.2
PhO− +0.3 CCl4 −0.9
Me3 N +0.7 PhCH2 Br −1.4
HO− +0.9 +1.9 PhCl6 −1.4
MeC(O)O− +1.5 t-BuI −1.5
PhOH +1.7 H3 O+ −1.6 −2.1
pyridine +2.0 PhCH2 Cl −1.7
Cl− +2.2 +2.4 n-BuI −1.9
HOOH +2.3 +1.0 c-C6 H11 Br −1.9
H2 O +3.0 +2.3 t-BuBr −2.0
n-BuBr −2.2
n-BuCl −2.5
PhCl −2.6
H2 O −3.9 −2.9

e e, 2 H2O substrate and coupling (R–R) or (b) to a Brønsted acid
Nu:  2 H2O [HO Nu] Nu(OH)2 (Eox)EC
H3O H3O (HA; H2 O) to replace the C–X bond with a C–H bond.
For example,
(162)
1. Alkyl- and Aryl-Halides
Because the halo-groups of organic molecules have large
electronegativities and electron affinities, all halo-carbon n-BuI  e [n-BuI] Ep,c, 2.05 V vs SCE
(a) e
molecules are electrophilic. Their electrochemical re- n-BuI,
n-Bu–Bu-n  2 I
duction potential is a measure of their electrophilicity (b) H2O, e
n-BuH  I  HO
(and electron affinity), which is illustrated in Fig. 6 for
(163)
hexachlorobenzene (C6 Cl6 ), 1,2,3,4-tetrachlorobenzene
(1,2,3,4-C6 H2 Cl4 ), and n-butyl iodide (n-BuI). Table VII In both cases the overall process is an irreversible two-
summarizes the reduction potentials for several alkyl- electron reduction via either (a) an EE path or (b) an ECEC
halides and aryl-chlorides. path; the first electron transfer is the most difficult and
In the absence of other Lewis acids, alkyl-halides un- depends on the substrates electrophilicity. In the presence
dergo direct electron addition at the electrode surface with of an hydronium ion, the primary electron transfer will be
subsequent stimulated electron transfer (a) to a second to the most electrophilic center, e.g.,
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Electrochemistry 189

PhCl6  e [PhCl
6]

e, H2O
HPhCl5  Cl  HO
(165)

Hence, the PhCl6 exhibits six irreversible two-electron


reductions (each product species less electrophilic than its
precursor) to yield at −2.8 V vs SCE benzene (PhH); an
overall 12-electron process.
PhCl6 + 6 H2 O + 12e− PhH + 6 Cl− + 6 HO−
(166)
Although such electrolyses are done in aprotic solvents
(e.g., DMF, DMSO, MeCN), even the most rigorously
dried solvent contains 3–20 mM H2 O (50–350 ppm). If
the solvent has a degree of Brønsted acidity (e.g., alcohols
and ketones), then it can serve as a source of hydrogen
atoms.

TABLE VII Redox Potential for Alkyl Halides (RX ) and Aryl
Chlorides (Ar Clx in Dimethyl Formamide at a Glassy Carbon
Electrodea

Alkyl halides

E p,c ,b V vs SCEc

RX I Br Cl

CH3− −2.10
n-C4 H9− −2.05 −2.41
sec-C4 H9− −1.92 −2.35
t-C4 H9− −1.78 −2.25
c-C6 H11− −2.03 −2.48
PhCH2− −1.68 −1.90
ClH2 C− −2.05
Cl2 HC− −1.99
FIGURE 6 Cyclic voltammograms for chlorinated aromatic
molecules and n-butyl iodide in dimethylformamide (0.1 M TEAP) Cl3 C− −1.13
at a glassy-carbon electrode (area, 0.062 cm2 ): (a) 1.1 mM hex- FCl2 C− −1.71
achlorobenzene (C6 Cl6 ); (b) 2.3 mM 1,2,3,4-C6 H2 Cl4 ; (c) 20 mM (F3 C)Cl2 C− −1.31
n-BuI. PhCl2 C− −1.47
[( p-ClPh)2 HC]Cl2 C− (DDT) −1.50
[( p-ClPh)2 FC]Cl2 C− (F-DDT) −1.44
H3O  n-BuI  e [n-BuIH ]
Alkyl halides
H2O H3O, e
n-BuH  HI .
E p,c , V E p,c , V
H2O Ar Clx vs SCE Ar Clx vs SCE
(164) PhCl(C6 H5 Cl) −2.7 PhCl5 −1.6
Thus, the reduction of n-BuI is the equivalent of the addi- 1,2-PhCl2 −2.5 PhCl6 −1.4
tion of two hydrogen atoms [H·] (generated via the elec- 1,2,3-PhCl3 −2.2 Cl5 Ph-PhCl5 −1.5
trochemical reduction of the two hydronium ions). 1,2,3,4-PhCl4 −1.9
With aryl-chlorides (e.g., PhCl6 ) a similar EEC process a mM solutions in DMF [0.1 M (Et4 N)ClO4 ].
occurs as each chlorine atom is replaced with a hydrogen b E p,c, the reduction-peak potential.
atom (Fig. 6 and Table VII). c Saturated calomel electrode (SCE) vs NHE, +2.44 V.
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190 Electrochemistry

2. Quinones, Semiquinones, and Catechols Neutral catechols (H2 Cat) and hydroquinones (H2 Q) are
much more resistant to electron removal because of their
All molecules with unsaturated bonds (olefins, acetylenes,
release of a proton via the solvent matrix; the more basic
aromatics, carbonyls, quinones, etc.) have a degree of
the solvent, the less positive the oxidation potential.
electrophilicity and electron affinity. Within a class, the
extent of conjugation increases the electron affinity (re-
e e
duction of benzene occurs at a less negative potential H2Cat [HSQ] Q (Ep,a)DMF, 0.97 V
sol sol
than 1-butene), and the presence of unsaturated carbon-
Hsol 
Hsol  (Ep,a)AN, 1.19 V
oxygen (carbonyl) functions within a conjugated system
(e.g., quinones; O ) also enhances the electron affinity
O
(173)
of the molecule. In acetonitrile, the residual H2 O is the stronger base, which
The cyclic voltammogram for 3,5-di-tert-butyl-o- results in the formation of H+ 3 O.
quinone (3,5-DBTQ) has a first reduction that is a re- The electrochemistry of quinones is surprisingly sim-
versible one-electron process, followed by a second one- ilar to that of dioxygen. It is as if a conjugated carbon
electron reduction, which can be reversible in rigorously link is inserted between two oxygen atoms (Q → SQ− · →
anhydrous media to give catechol dianion (3,5-DTBC2− ). HCat− vs ·O2 · → O− −
2 · → HOO ; Q → H2 Cat vs ·O2 · →
HOOH).
e−
3,5-DTBQ + e− 3,5-DTBSQ− . 3,5-DTBC2−
(167)
3. Carbonyl Groups, Olefins,
Although DTBC2− is a strong base that is hydrolyzed by and Aromatic Hydrocarbons
residual H2 O,
Unsaturated carbon centers possess a limited degree of
− − electrophilicity and will accept an electron at potentials
DTBC 2−
+ H2 O DTBCH + HO , (168)
significantly more negative than their chloro derivatives
it is also a strong reductant that can reduce H2 O in DMF. (usually at least −2.5 V vs SCE in rigorously anhydrous
solvents). When water is present, its reduction is syner-
DTBC2− + H2 O DTBSQ− · + 1/2 H2 + HO− gistically facilitated via unsaturated carbon. For example,
(169) in acetonitrile at a glassy-carbon electrode,
In many cases, the second reduction step of quinones
[Eq. (167)] is irreversible and due to the facilitated reduc- H2O  e [H]  HO Ep,c, –3.9 V vs SCE
tion of residual H2 O.
(174)
3,5-DTBSQ− · + H2 O + e− 3,5-DTBCH− + HO−
(170)  e NP Ep,c, 2.6 V vs SCE
+
In the presence of hydronium ions (H3 O), the reduction
of the quinones is an irreversible two-electron process (175)
(ECEC), with the first step being the more difficult (re-
e
quiring the more negative potential). NP  H2O  e [HNP] H2O H2NP

3,5-DTBQ  H 3 O  e [ 3,5-DTBSQH ] HO HO
e, H3O
H2O 3,5-DTBCH2 Ep,c, ~ 2.0 V vs SCE (176)
H2O

(171) Similar synergism is observed for other Brønsted acids


The oxidation potentials for the fully reduced forms of (HA) in the presence of unsaturated carbon centers.
quinones (catechols; H2 Cat, HCat− , and hydroquinones;
e
H2 Q, HQ− ) indicate that the first electron removal is the PhCH(O)  HA  e [ PhCHOH ]
HA
PhCH2OH
most difficult [e.g., 3,5-DTBCH− in DMF] in an irre- A A 
versible two-electron oxidation via an ECE mechanism.
(177)
− −e
− −e− For aromatic hydrocarbons, the more extensive the conju-
HCat HSQ· HCat−
Q + H2 Cat
gation is, the lower the LUMO and the less negative the
E p,a , +0.14 V vs SCE (172) potential for direct electron transfer
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Electrochemistry 191

electron-donating substituents reduce the potential by as


much as 0.7 V. Although a rigorously base-free solvent
, 2.6 V vs SCE; , 2.1 V; , 1.9 V; matrix should result in a reversible oxidation of benzene,
the resulting cation radical (PhH+ ·) is a strong electrophile
and Lewis acid that will react with water (complete sepa-
ration of water from benzene is difficult; 18 ppm H2 O is
a 1-mM concentration) to give PhOH and H+ 3 O in a CEC
, 1.8 V
process.

E. Organometallic Molecules

4. Brønsted Acids The defining characteristic of organometallic molecules is


the presence of one or more metal-carbon bonds. In con-
Carboxylic acids, phenols, and alcohols are electrochem- trast to the acid/base character of coordination complexes
ically reduced via their Brønsted acidity at a reduction of metal ions (with their ligand-centered redox chemistry,
potential that is a direct measure of their acidity (pK a ) in see Section II), the metal-carbon center is highly covalent
a given solvent. with limited polarity (similar to carbon-carbon, carbon-
nitrogen, or carbon-oxygen centers). As a result, the elec-
HA + e− 1/2 H2 + A−
trochemistry of organometallic molecules is more clos-
(E 1/2 )Pt ≈ −0.059 (pK a ) V vs NHE. (178) edly related to that of organic molecules than inorganic
coordination complexes.
The “foundation stone” of organometallic chemistry is
5. Oxidation of Nucleophilic Substrates bis(cyclopendienyl) iron(II) [ferrocene, (Cp)FeII (Cp)], an
and Lewis Bases iron atom sandwiched between two five-membered carbon
All molecules with nonbonding electron pairs (e.g., H2 O, rings [Cp, C5 H5 ·; each carbon with a p electron to give (1)
ROH, ROR, RNH2 , RSH, RSR, etc.) are, by defini- two pi-bonds delocalized around the carbon ring and (2) an
tion, Lewis bases with a degree of nucleophilicity. Their unpaired electron to give a covalent bond that is shared by
electrochemical oxidation potential is a measure (1) of the five carbons of the ring]. Thus, the FeII (Cp)2 molecule
the ease of removal for one of the electron pair of elec- has the iron on a line that connects the centers of two
trons and (2) of relative nucleophilicity (the less positive parallel planar Cp. groups to give an “iron sandwich.”
the potential, the more nucleophilic). Aromatic molecules Figure 7 illustrates the electrochemial redox chem-
with Lewis-base substituents are easier to oxidize than the istry in acetronitrile for several coordination com-
aliphatic forms of the substituents (e.g., PhOMe, +1.75 V plexes of iron [FeII (MeCN)2+ III III
4 , Fe Cl3 , and Fe (acac)3
vs SCE; MeOH, +2.5 V vs SCE) because the aromatic (acac = acetylacetonate)] in relation to that for two
ring provides a means to delocalize the positive charge iron organometallics [FeII (Cp)2 and FeVIII (CO)5 (iron-
and electron spin that would result from electron removal pentacarbonyl); both stable 18-electron systems]. In
(in the case of PhOMe, there are five additional hydro- MeCN, FeII (MeCN)2+ 4 is the only charged species of the
gen atoms to share the positive charge and six unsaturated group. It is reversibly oxidized (II/III couple; E1/2 , +1.6 V
carbon centers to share the spin density). Within this con- vs SCE). The uncharged FeIII Cl3 molecule is reversibly re-
text, the water molecule in a nonbasic solvent matrix is duced (III/II couple; E 1/2 , +0.2 V vs SCE) to give FeII Cl−
3,
the most resistant to electron removal, which is reduced by an irreversible two-electron process
  to iron metal (E p,c , −1.5 V vs SCE). The more basic
2 H2 O − e− (H2 O)H+2 O· HO· + H+ 3 O. (179) FeIII (acac)3 molecule is reversibly reduced (III/II couple;
Because aliphatic alcohols can be viewed as “organic wa- E 1/2 , −0.7 V vs SCE), but does not exhibit a second re-
ter” (but with a greater basicity and a weaker O H bond), duction peak. The III/II reduction potentials for these three
they are almost as difficult to oxidize [MeOH(H2 O) → coordination complexes are a measure of their relative
MeO· + H+ − electrophilicity (Lewis acidity).
3 O + e ; E p,a , +2.5 V vs SCE]. Other aliphatic
bases (amines and thiols) are oxidized by similar
pathways.
1. Ferrocene
The pi-electron cloud of the aromatic ring is much more
susceptable to electron removal than a saturated hydro- The FeII (Cp)2 molecule is resistant to reduction, but ex-
carbon. Thus, benzene is oxidized at +2.45 V vs SCE; hibits a highly reversible one-electron oxidation,
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192 Electrochemistry

FIGURE 7 Cyclic voltammograms: (a) 3 mM [FeII (MeCN)4 ](ClO4 )2 ; (b) 3 mM FeIII Cl3 ; (c) 3 mM FeIII (acac)3 ; (d)
3 mM FeII (Cp)2 ; (e) 3 mM FeVIII (CO)5 in MeCN (0.1 M tetraethylammonium perchlorate [TEAP]). Conditions: scan
rate, 0.1 V s−1 ; ambient temperature; glassy-carbon working electrode (area, 0.09 cm2 ); saturated calomel electrode
(SCE) vs NHE, +0.244 V.

−e− DMF, +0.72 V; py, +0.76 V; Me2 SO, +0.68 V; H2 O,


FeII (Cp)2 MeCN
FeIII (Cp)+
2 E 1/2 , +0.45 V vs SCE +0.40 V.
S=0 S = 1/2 (180)
with the single positive charge delocalized over the 10
equivalent (Cp)2 hydrogens (+0.1 each). For a time there 2. Iron-Pentacarbonyl
was a belief that the FeII (Cp)2 /FeIII (Cp)+
2 couple’s poten- The Fe(CO)5 molecule is equally fundamental to
tial was independent of solvent and, thus, an ideal refer- organometallic chemistry and electrochemistry and, like
ence electrode with which to measure solvent effects for FeII (Cp)2 , is a diamagnetic 18-electron system. It exhibits
other redox couples. However, subsequent measurements an irreversible two-electron reduction via residual H2 O
have shown that the FeIII (Cp)+2 ion possesses considerable (Fig. 7e).
acidity, which causes some solvent effects. The more seri-
ous problem is the limited solubility of FeII (Cp)2 in H2 O.
Fe(CO)5 + 2e− + 2 H2 O Fe (s) + H2 C(O)
The respective E ◦ values for the FeIII (Cp)+ II
2 /Fe (Cp)2 cou-
ple are MeCN, +0.69 V vs NHE (+0.45 V vs SCE); + 4 CO + 2 HO− E p,c , −1.8 V vs SCE. (181)
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Electrochemistry 193

By an anologous process the CO adduct of an iron(II) B. Aluminum Production


porphyrin [(Cl8 TPP)FeIV (CO)] is reduced to H2 C(O) at
The Hall process for the electrolytic production of alu-
−0.87 V. The oxidation of Fe(CO)5 in MeCN yields
minum utilizes an iron container that is lined with carbon,
FeII (MeCN)2+ in a two-electron process (Fig. 7e),
which serves as the cathode. The electrolyte within this
−2e−
container is molten cryolite (Na3 AlF6 ), which dissolves
Fe(CO)5 + 4 MeCN 4 + 5 CO
FeII (MeCN)2+ the aluminum oxide (Al2 O3 ) that is the raw material for
the process,
E p,a , +0.97 V vs SCE. (182)
Na3 AlF6 (l) + Al2 O3 (s) 3 NaAlOF2 . (185)
II 4+
On the basis that Fe (s) is oxidized to Fe (MeCN) A series of carbon anodes are immersed into the molten
at ∼0.0 V (Fig. 7a), the carbonyls of Fe(CO)5 stabi- solution. Electrolysis produces elemental alumium at the
lize the iron against oxidation by about 22 kcal mol−1 cathode (liquid metal at the operating temperature),
[E × 23.06 kcal mol−1 (eV)−1 ; 0.97 × 23.06]. The
(Cl8 TPP)FeIV (CO) molecule is oxidized at +0.75 V vs Cathode: Na3 AlF6 (l) + 3 e− Al (l) + 3 NaF−
2 , (186)
+0.32 V for (Cl8 TPP)FeII ; a stablization by the CO of and molecular oxygen at the anode,
about 10 kcal mol−1 .
These examples of the electrochemical character of Anode: NaAlOF2 + 2 NaF−
2 Na3 AlF6 (l)
organometallics are limited, but illustrate that their oxi- + 1/2 ·O2 · + 2e− . (187)
dation and reduction is closely similar to that for organic
molecules. Thus, the electron transfer is never carbon cen- Hence, the electrolytic cell reaction only consumes Al2 O3
tered and often involves residual water [H-atom addition to produce Al (l) and ·O2 · (g),
via reduction and (HO·) addition or H-atom abstractron Cell: 2 Na3 AlF6 + 3 NaAlOF2 2 Al + 3 Na3 AlF6
via oxidation] or solvent components.
+ 3/2 ·O2 · (Na3 AlF6 + Al2 O3 )
Net: Al2 O3 Al + 3/2 ·O2 ·. (188)
As the Al2 O3 is consumed by electrolysis, more of it is
VI. INDUSTRIAL ELECTROSYNTHESIS
continuously added, and liquid aluminum metal is period-
ically drained from the bottom of the cell.
A. Electroplating and Electrorefining
1. Copper Refining C. Chloro-Alkali Production
Although metallic copper is produced via the smelting of The industrial production of chlorine (Cl2 ) and sodium
copper ores, it contains enough impurities (and the atten- hydroxide (NaOH) involves the electrolysis of molten
dant increase in electrical resistance) to preclude its use as sodium chloride or of brine solutions. With the molten
an electrical conductor. Hence, all copper for use in elec- salt the metallic sodium that is produced at the carbon
trical wire and cable must be purified via electrorefining cathode is vaporized and collected in a condenser as the
with an impure copper plate as the anode, a pure copper solid metal. A common system for brine uses a cell with
sheet as the cathode, and copper sulfate/sulfuric acid as a liquid mercury cathode that flows in one direction along
the electrolyte: the floor with the brine flowing in the opposite direction
past a series of graphite anodes. The electrolysis reactions
Anode: Cu (s) (impure) + 6 H2 O produce chlorine gas at the anode, which is collected,

6 + 2e ,
CuII (OH2 )2+ (183) Anode: 2 Cl− (aq) Cl2 (g) + 2e− , (189)

Cathode: Cu II
(OH2 )2+
6 + 2e and sodium amalgam [Na2 (Hg)] at the cathode,
Cu (s) (pure) + 6 H2 O. (184) Cathode: 2 Na(OH2 )+
6 + Hg (l) + 2e

Na2 (Hg) (l) + 6 H2 O, (190)


Because most copper ores contain traces of gold and silver
(which become a part of the impure smelted copper), the which flows from the cell and is reacted with water to give
sediment that builds up in the bottom of the electrolysis a concentrated sodium hydroxide solution,
cell concentrates these valuble metals. The periodic refin-
Na2 (Hg) (l) + 14 H2 O 2 Na(OH2 )+
6
ing of the sediment often yields sufficient material to pay
for the entire purification process. + 2 HO− (aq) + H2 (g). (191)
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194 Electrochemistry

D. Organic Molecules and Polymers VII. BATTERIES AND FUEL CELLS


(e.g., Adiponitrile)
Batteries are galvanic cells whereby the chemical energy
The production of adiponitrile (intermediate in the pro-
of the components of the cathode (positive terminal) and
duction of nylon 66) via electrosynthesis is an important
the anode (negative terminal) is converted to electrical en-
industrial process. It also is a good example of how elec-
ergy via the cell reaction. Fuel cells are galvanic cells in
trogenerated hydrogen atoms [H·] induce the dimerization
which the active components of the two electrodes are con-
and oligerimization of terminal olefins. In this process a
tinuously replenished and the products of the cell reaction
solution that contains acrylonitrile and a quaternary am-
are continuously removed.
monium salt is circulated through a cathode compartment
with a lead electrode. A dilute solution of sulfuric acid
is circulated through an anode compartment with a lead- A. Lead-Acid Battery
alloy electrode. An ion-exchange membrane separates the
two compartments: The lead-acid battery, which is the electrical-power source
for motor vehicles, has exceptional capacity to deliver the
Cathode: 4 H2 C CHCN + 4 H2 O + 4e− large currents necessary to start internal combustion en-
gines. It has a lead dioxide (PbIV O2 ) cathode and a metallic
acrylonitrile
lead anode that are immersed in an aqueous sulfuric-acid
2 NC(CH2 )4 CN + 4 HO− . (192) solution (35% H2 SO4 by weight).
adiponitrile
Cathode (+ terminal): PbIV O2 (s) + 3 H+
3O
Anode: 6 H2 O 4 H+
3O

+ ·O2 · + 4e . (193)
+ HOS(O)2 O− + 2e− PbII SO4 (s) + 5 H2 O
A portion of the circulating solution from the cathode com- [HSO−
4] (197)
partment is continuously withdrawn to an extraction sys-
Anode (−terminal): Pb (s) + HOS(O)2 O− + H2 O
tem for removal of adiponitrile.
PbII SO4 (s) + H+
3 O + 2e

(198)
Cell: PbIV O2 (s) + Pb (s) + 2 H+
3 O + 2 HOS(O)2 O

E. Molecular Hydrogen and Hydrogen Peroxide


2 PbII SO4 (s) + 4 H2 O (199)
Through the use of sulfuric-acid electrolyte solutions, ex-
tremely pure molecular hydrogen (H2 ) can be electrosyn- When current is drawn from the cell via the two electrode
thesized at a platinum cathode. The cathode compart- reactions, sulfuric acid is consumed in accord with the cell
ment must be completely free of dioxygen and protected reaction and its concentration decreases. Because the den-
from migration of dioxygen from the anode compartment sity of H2 SO4 (l) is almost twice that of water, the state of
[Eq. (196)]. charge of the battery can be determined by a measurement
of the electrolyte density. The initial voltage of a cell is
Cathode: 4 H+
3 O + 4e

2 H2 (g) + 4 H2 O (194) a little greater than 2.0 V. Hence, the conventional 12-V
automobile battery has six cells connected in series. A dis-
If the cathode compartment is saturated with dioxygen (or charged battery is recharged by a generator that causes a
air) and a graphite cathode is used, then extremely pure so- current to flow in the opposite direction [Eqs. (197), (198),
lutions of hydrogen peroxide (HOOH) can be electrosyn- and (199) each are reversed], which releases H2 SO4 from
thesized, the electrodes and increases the density of the electrolyte
solution.
Cathode: 4 H+
3 O + 2 ·O2 · (g) + 4e

2 HOOH +4 H2 O, (195) B. Edison Battery


The Edison battery is another rechargable high-energy-
density system that has superior cycle life relative to the
Anode: 6 H2 O 4 H+ −
3 O + ·O2 · + 4e . (196) lead-acid battery. Prior to the advent of nuclear power
for submarines, large banks of Edison batteries in a se-
With both of these processes the ultimate source of hy- ries/parallel configuration provided the electric power for
drogen atoms is water. The anodic reaction replaces underwater propulsion. Relative to the lead-acid battery,
the hydronium ions that are removed by the cathodic the Edison battery has (1) more energy per unit mass (but
reactions. less energy per unit volume), (2) a smaller cell voltage
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Electrochemistry 195

(1.3 vs 2.0 V), (3) a constant cell voltage during discharge, The alkaline cell has lower internal resistance, longer shelf
and (4) almost unlimited life. In contrast to the sulfuric- life, and a larger open-circuit voltage (about 1.9 V) than
acid electrolyte of the lead-acid battery, the Edison battery the dry cell.
uses concentrated potassium hydroxide (KOH) as the elec-
troyte. The cathode is nickel dioxide [NiIV O2 (s)] and the D. High-Performance Batteries
anode is metallic iron. As the cell reaction confirms, the (Nickel/Cadmium, Silver/Zinc, Lithium)
KOH concentration remains constant during discharge,
which accounts for the constant cell voltage during dis- 1. Nickel/Cadmium
charge (only water is consumed during discharge and re- This is the most common of the rechargable batteries and
stored during recharge). has extensive use in “cordless” power tools, electric razors,
Cathode (+ terminal): NiIV O2 (s) + 2 H2 O + 2e− and electronics. It has similarities to the Edison cell, but
better performance in its areas of application.
NiII (OH)2 (s) + 2 HO− (200)
Cathode: NiIV O2 (s) + 2 H2 O + 2e−
Anode (−terminal): Fe (s) + 2 HO−
NiII (OH)2 (s) + 2 HO− (209)
FeII (OH)2 (s) + 2e− (201)
Anode: Cd (s) + 2 HO− CdII (OH)2 (s) + 2e− (210)
Cell: NiIV O2 (s) + Fe (s) + 2 H2 O
Cell: NiIV O2 (s) + Cd (s) + 2 H2 O
NiII (OH)2 (s) + FeII (OH)2 (s) (202)
NiII (OH)2 (s) + CdII (OH)2 (s) (211)
C. “Dry-Cell” Batteries The main problem with Ni/Cd batteries is their reduced
charge capacity if they are not fully discharged before
1. LeClanché Cell
recharging. Because of the toxicity of cadmium, responsi-
This traditional dry cell consists of a carbon-rod cathode ble disposal of worn-out batteries is important (but often
(positive terminal) immersed in a moist paste of MnIV O2 , ignored).
ZnII Cl2 , NH4 Cl, and powdered carbon, which is contained
in a metallic zinc-can anode (negative terminal). The volt- 2. Silver/Zinc
age (without load) of these cells is about 1.6 V, which have
limited shelf life because of corrosion of the zinc can and Forms of this battery type range from those used in hear-
increased internal resistance. ing aids, watches, and cameras to those used as portable
power sources in space vehicles. The cathode/anode and
Cathode: 2 MnIV O2 (s) + H2 O+2e−
electrolyte system is similar to that for the alkaline cell,

2 O3 (s) + 2 HO
MnIII (203) except the MnIV O2 cathode material is replaced with much
− more expensive silver oxide (AgI2 O). However, it has high
Anode: Zn (s) + 2 NH4 Cl + 2 HO
stability, a long shelf life, and a large charge density with
ZnII (NH3 )2 Cl2 + 2 H2 O+2e− (204) a stable voltage (about 1.8 V).
Cell: 2 Mn O2 (s) + Zn (s) + 2 NH4 Cl
IV Cathode: AgI2 O (s) + H2 O + 2e− 2 Ag (s) + 2 HO−

2 O3 (s) + Zn (NH3 )2 Cl2 + H2 O


MnIII II (212)
(205)
Anode: Zn (s) + 2 HO− ZnII (OH)2 (s) + 2e− (213)
2. Alkaline Cell Cell: AgI2 O (s) + Zn (s) + H2 O
This modern replacement for the dry cell uses sodium 2 Ag (s) + ZnII (OH)2 (s) (214)
or potassium hydroxide as the electrolyte (in place of the
acidic ZnII Cl2 /NH4 Cl electrolyte of the dry cell). Its cath-
ode and anode are essentially the same as the dry cell. 3. Lithium
Cathode: 2 MnIV O2 (s) + H2 O + 2e− The development of the lithium/managanese dioxide bat-
− tery has revolutioned the performance of modern cameras
MnIII
2 O3 (s) + 2 HO (206)
and electronic devices. Because of the use of a dry sol-
Anode: Zn (s) + 2 HO− ZnII (OH)2 (s) + 2e− (207) vent/electrolyte system (e.g., acetronitrile/LiX), these bat-
teries have operating lifetimes of at least five years, high
Cell: 2 MnIV O2 (s) + Zn (s) + H2 O
current capacity, and stable voltages (about 2.5 V) under
2 O3 (s) + Zn (OH)2 (s)
MnIII II
(208) load and can be used at temperatures as low as −40◦ C.
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196 Electrochemistry

Cathode: MnIV O2 (s) + LiX + e− modynamically favored reactions are accelerated by the
presence of salts and acids to cause rapid corrosion:
MnIII (O)OLi (s) + X− (215)
Fe (s) + 2 H2 O/CO2 6 + H2
FeII (OH2)2+
Anode: Li (s) + X− LiX + e− (216)
+ 2 HO(O)O− , (221)
Cell: MnIV O2 (s) + Li (s) MnIII (O)OLi (s) (217)
2 Fe (s) + ·O2 · + 4 H2 O/CO2 + 10 H2 O 2 Fe (OH2)2+
II
6

E. Fuel Cells + 4 HO(O)O− . (222)


The hydrogen (H2 )/oxygen (·O2 ·) anode/cathode combi- This problem has been solved through the use of a sacrafi-
nation is the most highly developed fuel cell. It continues cial metal (usually aluminum) that is attached to the steel
to be an essential power source for manned space missions, structure. The combination constitutes a Galvanic cell
which accounts for its advanced state of development. Be- with the iron as the cathode (+terminal), the aluminum
yond the practical problem of a gaseous fuel (H2 ), both as the anode (−terminal), and the seawater as the elec-
electrode reactions require precious-metal catalysts (usu- trolyte. The relevant half reactions and formal potentials
ally platinum supported on porous carbon electrodes). As [Eqs. (223) and (224)] allow formulation of the cell, its
indicated in earlier sections, electrochemistry is limited voltage, and the equilibrium constant, K , for the cell re-
to pathways that involve one electron steps. Hence, the action [Eqs. (225)–(227)].
essential function of the electrocatalysts for H2 oxidation −
and ·O2 · reduction is to provide such pathways for these 6 + 2e
FeII (OH2 )2+ Fe (s) + 6 H2 O
multi-electron transformations. E ◦ = −0.44 V vs NHE (223)
Cathode: ·O2 · (g) + 2 H2 O + 2 Pt (s) II −
5 Al OH + CO2 + 3e
(H2 O)2+
2 Pt (OH)2 (s); III

2 PtII (OH)2 (s) + 4 H+


3 O + 4e

2 Pt (s) + 6 H2 O Al (s) +HOC(O)O− + 5 H2 O
(218) E ◦ = −1.83 V vs HE (224)
Anode: 2 H2 (g) + 4 Pt (s) −
4 PtH (s); Cathode (of battery): Fe II
(OH2 )2+
6 + 2e
4 PtH (s) + 4 H2 O 4 Pt (s) + 4 H+
3O + 4e −
(219) Fe (s) + 6 H2 O. (225)
Cell: ·O2 · (g) + 2 H2 (g) −
2 H2 O (220) Anode: Al (s) + HOC(O)O + 5 H2 O

5 Al OH + CO2 + 3e
(H2 O)2+ III
(226)
VIII. CORROSION; CATHODIC Cell reaction: 3 Fe II
(OH2 )2+
6 + 2 Al (s) + 2 HOC(O)O−
PROTECTION 3 Fe (s) + 2 (H2 O)2+
5 Al OH + 8 H2 O
III

All metals (M) react with atmospheric oxygen (·O2 ·) to + 2 H2 O/CO2 K (227)
form surface films of metal oxides (MOx ). When this film ◦
 ◦ ◦

E cell = E Fe(II)/Fe − E Al(III)/Al
is formed under controlled conditions, it produces an in-
ert ( passivated ) surface that precludes further reaction = −0.44 V − (−1.83 V) = 1.39 V
and corrosion. However, the oxide films on copper alloys ◦
E cell = [0.05915/n] log K
and structural steel undergo dissolution when exposed
to aqueous media that contain ·O2 · and salts, acids, or log K = [6/0.05915]1.39 = 141; K = 10141
bases, and the surface no longer is protected and corrodes
Hence, the steel structure is protected until the aluminum
(dissolves).
anodes are consumed.

A. Structural Steel/Aluminum Anodes


Structual steel in aqueous environments (e.g., oil- SEE ALSO THE FOLLOWING ARTICLES
production platforms in the Gulf of Mexico) undergoes
corrosive dissolution via a number of chemical reactions. ALUMINUM • BATTERIES • CHEMICAL THERMODY-
The protective oxide coating [Fe2 O3 ] is especially suscep- NAMICS • CORROSION • ELECTROCHEMICAL ENGINEER-
tible to removal by the acids, salts, and organic matter in ING • ELECTROLYTE SOLUTIONS, THERMODYNAMICS •
seawater, which leaves an exposed iron surface. Two ther- ELECTROLYTE SOLUTIONS, TRANSPORT PROPERTIES •
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Electrochemistry 197

ELECTRON TRANSFER REACTIONS • FUEL CELLS, APPLI- Bard, A. J., Parsons, R., and Jordan, J., eds. (1985). “Standard Potentials
STATIONARY POWER SYSTEMS
CATIONS IN in Aqueous Solution,” Dekker, New York.
Dryhurst, G., Kadish, K. M., Scheller, F., and Renneberg, R. (1982).
“Biological Electrochemistry,” Vol. 1, Academic Press, New York.
Kissinger, P. T., and Heineman, W. R., eds. (1996). “Laboratory Tech-
niques in Electroanalytical Chemistry,” 2nd ed., Dekker, New York.
BIBLIOGRAPHY Kolthoff, I. M., and Lingane, J. J. (1952). “Polarography,” 2nd ed., In-
terscience, New York.
Baizer, M. M., and Lund, H., eds. (1991). “Organic Electrochemistry,” Sawyer, D. T., Sobkowiak, A., and Roberts, J. L., Jr. (1995). “Electro-
3rd ed., Dekker, New York. chemistry for Chemists,” 2nd ed., Wiley-Interscience, New York.
Bard, A. J., and Faulkner, L. R. (2001). “Electrochemical Methods,” Weinberg, N. L., ed. (1974, 1982). “Technique of Electroorganic Syn-
2nd ed., Wiley, New York. thesis,” Parts I, II, and III, Wiley-Interscience, New York.
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Electron Spin Resonance


Larry Kevan
University of Houston

I. Basic Principles
II. Experimental Aspects
III. Isotropic Hyperfine Analysis
IV. Relation of Hyperfine Constants
to Spin Densities
V. Second-Order Hyperfine Effects
VI. Anisotropic Hyperfine Interaction
VII. g Anisotropy
VIII. Spin Relaxation
IX. Double-Resonance and Time-Domain ESR
X. Applications
XI. New Developments

GLOSSARY Spin density Fraction of unpaired electron spin probabil-


ity at a given nucleus in a molecular system.
Dot product Mathematical multiplication operation for Spin Hamiltonian Mathematical operator that operates
two vectors. or acts on spin wave functions of a paramagnetic system
ENDOR Abbreviation for the double-resonance tech- to give the energy levels of the system.
nique of electron nuclear double resonance. Wave function State function that can be used to calcu-
ESE Abbreviation for the time-domain electron spin res- late any property, typically energy levels, of a natural
onance technique of electron spin-echo spectroscopy. system, typically a molecule.
g Factor Constant characterizing the magnitude of the Waveguide Rectangular pipe of appropriate dimensions
spin angular momentum of an electron or a nucleus. to propagate microwaves in a given frequency range.
Hyperfine coupling Interaction energy or coupling be- Zeeman interaction Interaction energy of a magnetic
tween electron and nuclear spins. field with the spin angular momentum of a particle.
Perturbation theory Mathematical approximation me-
thod used to simplify the calculation of energy levels
from a Hamiltonian operator acting on a wave function ELECTRON SPIN RESONANCE is a type of magnetic
for a system. resonance spectroscopy dealing with transitions between

331
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332 Electron Spin Resonance

magnetic energy levels associated with different orienta-


tions of an electron spin in an atom or a molecule, gen-
erally in an external magnetic field. Measurement of the
allowed transitions between the electron magnetic energy
levels produces a spectrum of an atomic or molecular sys-
tem with net electron spin angular momentum. Generally
FIGURE 1 Energy-level diagram for ESR.
such systems are defined as those having one or more
unpaired electrons. Analysis of the electron spin reso-
nance spectrum can give information about the identifica- value of 9.27 × 10−24 J/T. This spin Hamiltonian operates
tion of the species, the geometric structure, the electronic only on spin wave functions and not on orbital wave func-
structure, and the internal or overall rotational or transla- tions that are commonly associated with electronic energy
tional motion of the species. The most common types of levels. For an electron there are two spin wave functions,
systems studied are free radicals, which can be regarded typically denoted by α and β, which are characterized by
as atoms or molecules containing one unpaired electron, + 12 h and − 12 h where h is Planck’s constant divided by 2π
✥ ✥ ✥

and transition-metal and rare-earth ions. The specificity and gives the unit of spin angular momentum. The two en-
of electron spin resonance spectroscopy for only species ergy levels associated with an electron in a magnetic field
containing unpaired electrons is particularly valuable for are thus given by + 12 gβH and − 12 gβH . The difference
the study of chemical reaction intermediates. between these two energy levels is gβH , so that the tran-
sition energy is given by h ν = gβH . This basic electron
spin resonance transition is illustrated in Fig. 1.
I. BASIC PRINCIPLES Typically, electron magnetic resonance is carried out in
a magnetic field of about 3000 G (gauss) or 0.3 T (tesla).
In general, the energy of a system or, more specifically, This corresponds to an energy absorption frequency of
of a molecule depends on momentum. The kinetic energy about 9 GHz. This frequency is in the microwave range.
of a molecule is proportional to the square of the linear As for any spectral transition, the number of systems or
momentum, and the rotational energy of the molecule is electrons in the upper and lower energy states at thermal
proportional to the square of the rotational or angular mo- equilibrium is given by a Boltzmann distribution.
mentum. An isolated electron can be regarded as a point
particle that has no classical angular momentum. How-
ever, experimentally it is found that isolated electrons in II. EXPERIMENTAL ASPECTS
a magnetic field do absorb a quantitized amount of en-
ergy, which means that they must have at least two energy Figure 2 shows a block diagram of a typical electron spin
levels. These are not translational energy levels, because resonance (ESR) spectrometer. It can be seen that this
the amount of energy absorbed does not depend on the diagram is analogous to that for an optical absorption
kinetic energy of the electron. However, the magnitude spectrometer, consisting of a source of electromagnetic
of the energy absorbed does depend on the magnitude of optical radiation, a sample cavity, and a detector of the op-
the magnetic field to which the electrons are exposed. As tical radiation intensity. In the block diagram of the ESR
an explanation of the existence of these magnetic energy spectrometer, the microwave irradiation is produced by a
levels, it is postulated that an electron has an intrinsic angu- special microwave tube called a klystron or a solid-state
lar momentum called spin angular momentum. When this device called a Gunn diode. The microwaves are transmit-
spin angular momentum interacts with a magnetic field, ted through a rectangular waveguide or through a special
two different energy levels are produced whose difference coaxial cable to an isolator, which is a ferrite device al-
accounts for the absorption of energy by the unpaired elec- lowing microwaves to travel in only one direction. This
tron system. component is used so as to prevent reflection of the mi-
The Hamiltonian energy operator for the electron spin crowaves back into the klystron tube or Gunn diode. The
transition we have just discussed is given by microwaves then pass through a device called an attenua-
tor, which simply controls the intensity of the microwaves
spin = gβS · H, (1)
and consists of a resistive but electrically conducting ele-
where spin is the spin Hamiltonian energy operator; S ment that penetrates to different extents into a waveguide.
is the spin angular momentum; H is the magnetic field; Although not shown, there also are devices available to
gβ is a proportionality constant, where g = 2.0023 and is shift the phase of the microwaves if that is necessary. The
called the g factor or spectroscopic splitting factor, which microwaves then pass into a circulator, which is a ferrite
is dimensionless; and β is the Bohr magneton, which has a device that routes the microwaves in one port and out an
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Electron Spin Resonance 333

FIGURE 2 Block diagram of a typical ESR spectrometer. KLY, klystron or Gunn diode source of microwaves; ISOL,
isolator; ATTEN, attenuator; Circ, three-port circulator; CAV, resonant cavity; M, magnetic field modulation coils;
XL, detector crystal; PSD, phase-sensitive detector; and OSC, oscillator. The double lines represent a waveguide
connecting the microwave components, and the single line represents a cable connecting the electronic components.

adjacent port in a unidirectional fashion. This component signal is then passed into the signal channel of the phase-
is particularly useful for a resonance-type experiment in sensitive detector, and this device compares the coding of
which all of the microwaves are absorbed in the sample the signal with that of the reference and passes only signals
cavity. When this equilibrium situation is upset by a sam- coded at the same frequency. This has the effect of greatly
ple absorbing some of the microwaves in the cavity, an im- increasing the signal-to-noise ratio, since noise generated
balance is set up and some microwaves are reflected from in the system is not coded at the magnetic field modula-
the cavity out through the circulator in a unidirectional tion frequency. The phase-sensitive detection procedure
fashion to the detector crystal. In the diagram the ESR also has the effect of differentiating the ESR signal and
cavity shown is a reflection type, which is typically more producing a first-derivative curve instead of an absorption
sensitive than a transmission type, which would be more curve. The signal from the phase-sensitive detector then
analogous to the sample cell of an optical spectrometer. goes to a recorder or another readout device and is usually
The microwaves are detected by a semiconducting crys- referenced to a swept magnetic field so that one obtains
tal diode rectifier mounted in a waveguide. This crystal ESR intensity as a function of magnetic field.
converts the high-frequency microwave electromagnetic
radiation to a direct current voltage, which can then be III. ISOTROPIC HYPERFINE ANALYSIS
amplified and treated by ordinary electronics. For opti-
mum sensitivity, the detector crystal is biased with a little The real power of electron spin resonance spectroscopy
reflected microwave power controlled by the size of the for structural studies is due to interaction of the unpaired
iris, which is the coupling hole allowing the microwaves electron spin with nuclear spins in molecular species. This
to enter the cavity. The size of this coupling hole can be gives rise to a splitting of the energy levels and gener-
simply changed with a screw tip. ally allows the determination of the atomic or molecular
So that the signal-to-noise ratio can be increased greatly, structure of the radical species. In this situation the spin
by approximately a factor of a thousand, magnetic field Hamiltonian of Eq. (1) involves additional terms corre-
modulation is used. This is accomplished with small coils sponding to the nuclear spin interacting with the magnetic
mounted on each side of the sample cavity through which field, to the nuclear spin interacting with the electron spin,
radiofrequency radiation, typically 100 kHz, is passed. and, if the nuclear spin is ≥1, to a nuclear quadrupole in-
This produces a modulation of the static magnetic field, teraction. This more complete spin Hamiltonian may be
which codes the ESR signal at this modulation frequency. written as
Then a device known as a phase-sensitive detector is used,  
which is referenced to this magnetic field modulation fre- spin = βH · g · S + hS · An · In − gn βn H · In
n n
quency. The microwave signal is coded at this modulation 
frequency, and the crystal detector converts the signal into +h In · Qn · In . (2)
a pulsating dc voltage at this modulation frequency. This n
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334 Electron Spin Resonance

In Eq. (2) the summations are taken over all the nuclei
in the molecular species. The new symbols in Eq. (2) are
defined as follows: gn is the nuclear g factor, which is di-
mensionless; βn is the nuclear magneton, having units of
joules per gauss or per tesla; the nuclear spin angular mo-
mentum operator In ; the electron–nucleus hyperfine ten-
sor An ; the quadrupole interaction tensor Qn ; and Planck’s
constant h.
Note that the nuclear Zeeman term involving the inter-
action of the magnetic field with the nuclear spin angular
momentum operator has a negative sign. This is essen-
tially due to the difference in charge between electrons
and nuclei. Also note that the nuclear g factor can be either
FIGURE 3 Schematic of the first-order spin energy levels of a hy-
positive or negative, while the electron g factor is taken drogen atom, showing successive interactions in the spin Hamil-
as intrinsically positive. In Eq. (2) the electron g factor tonian, the allowed ESR transitions, and the spin wave functions.
has been written in tensor form involving a 3 × 3 matrix
that connects the magnetic field vector and the electron energy levels given in Eq. (5), where mS and mI refer to
spin angular momentum vector. Similarly, the hyperfine the electron and nuclear spin angular momentum quantum
interaction is written in tensor form connecting the elec- numbers:
tron spin and nuclear spin angular momentum vectors. The  
E n = gβ H m S − gn βn H m I n + m S h An m I n .
quadrupole interaction is also written in tensor form. n n
First consider the special case of isotropic hyperfine (5)
interaction in which the hyperfine interaction becomes a The wave functions correct to first-order perturbation the-
scalar and can be written in front of the dot product of the ory are just the product functions of the respective electron
nuclear and electron spin angular momentum vectors. For and nuclear spin combinations. The hyperfine interaction
simplicity the electron g factor will also be considered to term involves only the z-components of the electron and
be isotropic and to be a scalar. This simplification typically nuclear spin angular momentum operators when treated
applies to most organic and some inorganic free radicals by first-order perturbation theory.
in liquids and also to a few cases in solids. This occurs This simplified treatment can be applied exactly to a
because rapid tumbling of the molecular species averages hydrogen atom with S = 12 and I = 12 where the corre-
out the anisotropic interactions. Also, since the quadrupole sponding mS and mI values are both ± 12 . The spin wave
interaction is typically small and can only be experimen- functions such as αe βn and the spin energy levels for a
tally resolved in special cases, it will be left out of the hydrogen atom in a magnetic field are shown in Fig. 3.
simplified spin Hamiltonian. The resulting simplified spin The transition probabilities between the first-order spin
Hamiltonian becomes energy levels can be calculated from time-dependent per-
 
spin = gβH · S − gn βn H · In + h An S · In . (3) turbation theory by standard methods in which the mag-
n n netic dipole moment operator is used. It is found that the
The external magnetic field is unidirectional, and by con- transition moment is only finite for a magnetic dipole mo-
vention it is taken to be in the z-direction. ment operator oriented perpendicular to the magnetic field
Then the energy levels of the spin system are given by direction. This means that in the design of an electron spin
 resonance cavity into which the sample is placed, the mi-
E n = n∗ spin n dτ, (4) crowave magnetic field must be arranged to be perpendic-
ular to the external static magnetic field. The second point
where  represents the spin wave functions. The spin wave of interest is that transition moments that determine the se-
functions can be taken as products of the electronic and lection rules for magnetic resonance are finite for electron
nuclear spin wave functions. These product functions are spin transitions corresponding to a change in the electron
not exact wave functions for the spin Hamiltonian includ- spin orientation but are zero for nuclear spin transitions.
ing the hyperfine interaction term, but they serve as good These selection rules can be compactly written as
first approximations. The correct treatment of the prob-
lem usually involves some approximation method, and a
mS = ±1 (6)
common one is perturbation theory, which is a standard
and
quantum-mechanical method. Applying first-order pertur-
bation theory to the spin Hamiltonian in Eq. (3) gives the
mI = 0, (7)
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Electron Spin Resonance 335

where m S and m I refer to the electron and nuclear spin


quantum numbers, respectively.
If we examine Fig. 3 we see that only two of the four
possible transitions are allowed, namely, those in which
the nuclear spin does not change its orientation. The en-
ergy difference between these two transitions is defined as
the hyperfine constant, usually symbolized by A in units of
megahertz (MHz) or gauss (G). Since
m I = 0, the effect
of the nuclear Zeeman term in the spin Hamiltonian will
always cancel out for first-order spectral transitions. Thus,
this term can be neglected in the Hamiltonian when one is
considering only first-order spectra. However, it should be
cautioned that if one considers spectra in which the per-
turbation theory approach must be carried out to second
order or if one considers spin relaxation, which will be
discussed later, the full spin Hamiltonian must be used.
Figure 4 shows the energy-level diagram based on
Eq. (8) for a hypothetical NH+ species where AN and
AH are assumed to be positive and AN > AH . Any sub-
script refers to the location of the nucleus in the molecule.
Figure 4 shows the energy levels of the spin system and FIGURE 5 Stick diagram for an ESR spectrum of hypothetical
the allowed transitions between sets of two energy levels. NH+ .

So that the actual ESR spectrum can be represented in a


simple way, a stick diagram is often used. Figure 5 shows
a stick diagram for hypothetical NH+ . Each line repre-
sents an observed ESR line. The stick diagram, looks like
half of the energy-level diagram, except that the separation
between lines in the actual spectrum is equal to the hyper-
fine constant rather than to some fraction of it. If no lines
overlap, the total number of lines is given by n (2In + 1).
A slightly more complicated situation for hyperfine cou-
pling exists when several nuclei have the same coupling
constants. Such nuclei are called equivalent. Consider CH3
and CD3 as examples; stick diagrams are shown in Figs. 6

FIGURE 4 First-order hyperfine energy levels and allowed tran-


sitions for a hypothetical NH+ radical with AN > AH > 0. FIGURE 6 Stick diagram for an ESR spectrum of the CH3 radical.
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336 Electron Spin Resonance

The assignment of an experimental coupling constant to


a given set of nuclei is sometimes not unique. Assignments
are usually made on the basis of theoretical calculations
or chemical substitutions. The spin density at a particular
proton is directly related to its coupling constant. Approx-
imate spin densities can be calculated by a simple Hückel
molecular orbital approach. They give a guide to the cou-
pling constant to be expected for a particular position. It
is more desirable if the experimental coupling constants
can be used to check the accuracy of the theoretical cal-
culation. Hence, assignments based on theoretical spin
densities should be used only when no direct information
can be obtained. Chemical substitutions can lead to an
unambiguous assignment. For example, deuterium can be
substituted for a given proton or set of equivalent protons.
Deuterium has a spin of 1 and a magnetic moment that
is 3.26 times smaller than that of H. Thus deuterium will
give a 6.5 times smaller splitting, which is sometimes not
even resolved. Methyl groups and Cl can also be substi-
tuted for certain protons to delineate the proper coupling
assignment.

FIGURE 7 Stick diagram for an ESR spectrum of the CD3


radical.
IV. RELATION OF HYPERFINE CONSTANTS
TO SPIN DENSITIES

and 7. After the hyperfine interaction of one nucleus is In spectral analysis, the hyperfine coupling constant A has
considered, all the individual lines are no longer sepa- been treated as an experimental parameter with units of
rated. The superposition leads to fewer lines and a vari- megahertz. The theoretical expression relating the hyper-
able intensity distribution. The splitting between all the fine coupling constant for atoms is given by
lines in the observed spectrum is identical and is equal
h A = 83 πgβg N β N |ψ(0)|2 , (8)
to the coupling constant. The resulting intensity distribu-
tions are characteristic for sets of equivalent nuclei and where the units are joules on both sides of the equation
often simplify analysis. For protons or any nucleus with and |ψ(0)|2 is the probability density of the electron’s be-
spin 12 , n equivalent nuclei give n + 1 lines with a bino- ing at the nucleus. From a quantum-mechanical point of
mial intensity distribution. In the general case the number view, the electron is in contact with the nucleus, and hence
of lines arising from n equivalent nuclei of spin I is given the isotropic hyperfine coupling is called a “contact” in-
by 2nI + 1. teraction. Only s orbitals have finite electron density at
The equivalence of all magnetic nuclei greatly simpli- a nucleus; p, d, and f orbitals have nodes at the nucleus.
fies the spectrum. For several sets of equivalent nuclei, Thus, contact interaction depends on the s-electron charac-
interpretation is simple only if the difference in coupling ter of the unpaired electron, and the hyperfine constant for
constants is large enough to separate the groups. If a radical a given nucleus provides a measure of the contributions
has two groups of three equivalent protons, the spectrum of the s orbitals on the corresponding atom to the total
will be split into four lines by the first group, and each many-electron wave function of the atom or molecule.
of the four lines will be split again into a quartet by the For molecules, Eq. (8) can be rewritten as
second group. If the two coupling constants differ enough,
h A = 83 πgβg N β N ρ̄ N , (9)
the spectrum will appear as four separated quartets. More
often the groups (quartets in our example) will overlap. If where ρ̄ N is the unpaired spin density, usually just called
all the lines are still separated, analysis is tedious but not spin density, at nucleus N with units of reciprocal vol-
too complex. Real difficulty arises when the linewidth of ume. The spin density ρ̄ N is evaluated from the total
the hyperfine lines interferes with their resolution. Unfor- electron wave function and represents the difference be-
tunately, this often occurs when the number of interacting tween the average number of electrons at the nucleus with
protons becomes large. α spin (m s = + 12 ) and the average number with β spin
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Electron Spin Resonance 337

(m s = − 12 ). By convention, the unpaired electron of a free The spin polarization mechanism generates observable
radical is taken to be an α spin; hence spin densities are hyperfine coupling to protons on the carbon containing the
usually positive. However, a particular nucleus may be in p orbital; such protons are called α protons. The two elec-
a region of excess β spin, in which case the spin density trons in the C—Hα sigma bond are spin polarized such that
at that nucleus is negative. the electron nearest the carbon has the same spin as that of
For example, in the benzyl radical the spin density at the unpaired electron, namely, an α spin. This occurs be-
the meta positions is negative while the spin density at cause the exchange interaction between two parallel spins
the other ring positions is positive. The sign of the spin near the carbon nucleus slightly lowers the energy. This
density corresponds to the sign of the hyperfine coupling spin polarization causes the spin orientation of the un-
constant. In the typical ESR spectrum, no sign information paired electron in the p orbital on carbon to be opposite
on the coupling constants is obtained. Nuclear magnetic the spin orientation of the bonding electron largely in the
resonance (NMR) measurements or, under certain condi- hydrogen 1s orbital. Thus the spin density at the proton is
tions, second-order effects in the ESR spectrum are used negative and the hyperfine coupling constant is negative.
to determine signs. Quantitative calculations for one electron in the 2pz

By convention, the spin density ρ̄ N , which has units of carbon orbital in a ✟ Ċ—H fragment show that a negative
reciprocal volume, is usually normalized by division by spin density of −0.05 is induced at each α proton. This
|ψ N (0)|2 to obtain a dimensionless fractional spin density corresponds to −0.05 (507 G) ≈ −25 G, where 507 G is
ρ N , also usually just called spin density. The number ρ N the value for unit spin density on a proton, which compares
represents the fraction of unpaired spin on an atom N . well with −23.0 G observed for the methyl radical and
A proton hyperfine coupling constant of 142 MHz cor- −22.4 G observed for the ethyl radical. The negative sign
responds to a spin density (ρ N ) of 142/1420 = 0.1 at the is confirmed by NMR measurements.
proton where 1420 MHz is |ψ N (0)| In the ethyl radical the β protons on the carbon adja-
 . The spin density ρ N1
2

may be positive or negative, but N ρ N = 1 for all spin- 2 cent to the one with the unpaired electron also produce a
radicals. hyperfine coupling that is the same order of magnitude as
Since the isotropic hyperfine coupling constant is di- that of the α-proton coupling. A spin polarization mech-
rectly proportional to the s-electron spin density, it can be anism would have to pass through two bonds to reach the
used to determine orbital hybridization and consequently β protons and would be expected to be weaker than for
radical structures. To apply this, one must know what the α protons. Therefore, an alternative mechanism involving
hyperfine coupling constant is for a 100% s electron on an hyperconjugations seems probable. This mechanism can
atom. Only for H atoms is this known exactly. For other be pictured qualitatively as follows. The unpaired electron
atoms, the best available Hartree-Fock wave functions are is envisioned as occupying a molecular orbital consist-
used to calculate |ψns (0)|2 . Values have been tabulated that ing of contributions from the two pz carbon orbitals. This
are good to ±10% or much better for the lighter elements. molecular orbital will overlap H-atom 1s orbitals that are
As an example, consider the trifluoromethyl radical not in the nodal plane of the pz orbitals and therefore will
CF3 . To determine the s-electron spin density on the car- overlap with the β protons in the ethyl radical. The hy-
bon, one must measure the 13 C hyperfine coupling con- perconjugation mechanism allows some of the unpaired
stant experimentally. This is found to be 271.6 G, which is α-spin density to directly overlap into the β-proton 1s or-
∼24% of a full 2s electron on the carbon. This implies near bitals and thus predicts a positive coupling constant. A
SP3 bonding in the radical and indicates that CF3 is tetrahe- positive sign is observed by NMR. It should be noted that
dral and not planar. In contrast, the 13 C hyperfine coupling a positive sign at the β protons is also predicted by the
constant for the methyl radical CH3 is 38 G, which indi- spin polarization mechanism, but the magnitude from this
cates only ∼3% s character. This is consistent with a near- mechanism is expected to be smaller.
planar structure for CH3 . In fact, the time-average structure In aromatic radicals the unpaired electron is delocal-
of CH3 is planar, but a small amount of s hybridization can ized over the pz carbon orbitals, so that the spin density
arise from out-of-plane vibrations of the H atoms. in any one pz orbital is less than it is on a methyl radical.
Equation (9) shows a direct proportionality between The protons are in the nodal plane of the pz orbitals and
the hyperfine coupling constant and the s-electron spin exhibit hyperfine coupling through the spin polarization
density. Many radicals have the unpaired electron largely mechanism. The proton splitting is directly proportional
localized in a p orbital, but direct or indirect interaction to the pz or molecular π -orbital spin density on the car-
with orbitals of partial s character can lead to a net spin bon to which the proton is attached, as represented by
density at the nuclei. The ethyl radical ·CH2 CH3 illustrates Eq. (10):
two types of mechanisms that lead to hyperfine coupling
with all its protons. AH = Q H ρCπ , (10)
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338 Electron Spin Resonance

where Q H is a constant with a value of about −25 G. Equa- The difference between the allowed transitions shown
tion (10) applies to protons bonded to any atom, except in Fig. 8 is not changed from the first-order situation at
that Q H is dependent on the atom. It has been most exten- constant magnetic field. However, in an actual ESR spec-
sively tested for protons bonded to carbon and to a lesser trometer the magnetic field is swept, and since the second-
extent for protons bonded to nitrogen. order correction term depends on the magnetic field, the
Although proton hyperfine interactions are by far the “apparent” splitting will change in second order. This ob-
most common in aromatic radicals, a great deal of in- served apparent splitting will be larger than the actual hy-
formation about spin densities can also be derived from perfine splitting, and for the case of hydrogen atoms this
hyperfine interactions with 13 C, 14 N, 19 F, 17 O, and so forth. difference is about 2 G.
The simple relation of Eq. (10) for protons does not gen- The second-order effect on the hydrogen-atom spec-
erally apply to these nuclei because the interactions of the trum is a subtle one, in the sense that the nominal appear-
unpaired spin with spin density on adjacent nuclei and ance of the spectrum does not change. Generally in more
with lone-pair π electrons must be considered. complex paramagnetic systems additional lines in the ESR
spectrum appear that are due to second-order effects in the
energy-level diagram. These types of transitions must be
V. SECOND-ORDER HYPERFINE EFFECTS identified in order to interpret a spectrum well enough to
assign the structure of a radical. The “extra” lines that
When the hyperfine coupling constants are large and the commonly occur due to second-order hyperfine effects
linewidth is small, second-order hyperfine effects must be can be divided into two classes. One class arises from the
considered to explain the observed spectra in many cases. splitting of some of the degeneracies of the inner lines
A simple example is the spectrum of a hydrogen atom. of a hyperfine pattern involving several equivalent nuclei.
The second-order effects in the hydrogen spectrum cause The second class involves forbidden transitions where the
a shift of the center of the spectrum to lower field and nuclear spin selection rule is violated and transitions cor-
cause the observed hyperfine splitting to be larger than responding to
m I = ±1 are observed.
the actual value for a field-swept spectrum. Second-order In general, extra spectral lines due to the splitting of
analysis is required because the hyperfine splitting of 507 the degeneracies of equivalent nuclei occur when the
G is a significant fraction of the typical 3300-G magnetic second-order hyperfine correction magnitude is greater
field used to observe the spectrum. The second-order per- than the linewidth. This has been observed only in liquid-
turbation theory correction factor to the energy levels is phase spectra. To second order, the transition energies for
proportional to the square of the hyperfine coupling con- a system with one unpaired electron and one type of de-
stant divided by the observing field. This causes a second- generate nuclei of nuclear spin I is given by
order shift in two of the four hydrogen-atom energy levels,
1 A2  
as shown in Fig. 8. The two transition energies are in- E n = gβH + AM I + I (I + 1) − M I2 , (11)
creased, so the entire spectrum is shifted to lower field due 2 gβH
to this effect. For hydrogen atoms the shift is about 18 G, where M I is the total nuclear spin quantum number for the
which corresponds to a change in the apparent g factor of set of equivalent nuclei. For n equivalent nuclei in general
0.0108. I 2 = M I2 , so from Eq. (11) one can see that some splitting
of the first-order degeneracy will result. An example of this
situation occurs for the trifluoromethyl radical in solution,
where the first-order spectrum would predict four equally
spaced lines with relative intensities of 1 : 3 : 3 : 1. Since
Aiso for 19 F is 145 G, which is a large value, second-
order effects are observable. In the actual spectrum at suffi-
ciently high resolution six lines are observed with relative
intensities 1 : (1 : 2) : (1 : 2) : 1, where the (1 : 2) lines are
two closely spaced lines whose splitting is due to second-
order shifts. All lines are shifted slightly to low field, but
different energy levels are shifted by different amounts,
which leads to the additional splitting of about 9 G in this
case.
The other result of second-order hyperfine effects is to
FIGURE 8 Schematic of the first- and second-order energy lev-
els of a hydrogen atom, the first-order allowed ESR transitions, mix the first-order wave functions as shown in Fig. 8 so
and the first- and second-order spin wave functions. The magni- as to partially allow some forbidden transitions that in-
tude of the second-order shift is A2 [4(g β H + gN β N H )]−1 . volve flipping of nuclear spins. When the first-order wave
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Electron Spin Resonance 339

functions are mixed, the normally forbidden transitions diagonal elements of a diagonalized hyperfine tensor are
become weakly allowed, due to components of the oscil- called the principal values.
lating microwave magnetic field parallel to the direction of To determine the anisotropic hyperfine tensor experi-
the external magnetic field, instead of perpendicular to the mentally, one must usually use a single crystal, although
external magnetic field as is the case for ordinary allowed if there is only one interacting nucleus or possibly more
ESR transitions. In the practical situation there is usually with sufficiently large anisotropy, it is sometimes possible
a small component of the applied microwave magnetic to determine the tensor from powder spectra. For single
field in the direction parallel to the external magnetic field, crystals it is necessary to measure the angularly dependent
which can bring about such nominally forbidden transi- hyperfine splitting in three mutually perpendicular planes
tions. These types of transitions are seldom seen in liquids with respect to the external magnetic field. From this data
but are relatively common in solids. there are well-known procedures to obtain the hyperfine
tensor in the axis system chosen for measurement. Then,
VI. ANISOTROPIC HYPERFINE as outlined above, this tensor may be diagonalized and the
INTERACTION principal values with their associated direction cosines
may be determined.
The general spin Hamiltonian was given by Eq. (2), in The physical interpretation of the anisotropic hyperfine
which the interaction parameters were written in the gen- principal values is given by the classical magnetic dipolar
eral tensor form. The total hyperfine tensor A can be rep- interaction between the electron and nuclear spin angular
resented by a 3 × 3 matrix that connects the three com- momenta. This interaction energy is given by

ponents each of the electron spin angular momentum and 1 − 3(cos2 φ)
the nuclear spin angular momentum. The hyperfine tensor aniso = −gβg N β N I · S, (15)
r3
is a real matrix and can always be diagonalized. Thus a
general tensor referenced to an x–y–z axis system can be where r is the vector between the unpaired electron and
written as
  the nucleus with which the interaction occurs and φ is the
 Ax x Ax y Ax z  angle between r and the electron spin angular momentum
 
  vector S, which is in the direction of the external magnetic
A ≡  A yx A yy A yz  . (12)
  field. The A principal values are given by
 A zx A zy A zz 


−1 1 − 3(cos φ)
2
This general tensor can be transformed to another axis 
A = −gβg N β N h , (16)
system in which the new tensor is diagonal. This requires r3
av
finding the proper transformation matrix L, which diago-
where av denotes a spatial average over the electronic or-
nalizes the A tensor as
bital of the unpaired electron. The three components of A
L · Ax yz · LT = dAαβγ , (13) are given by three different values of cos φ corresponding
where LT is the transpose of L. The diagonalized tensor d A to rotation in three mutually perpendicular planes of the
is diagonal in the α–β–γ axis system, and the components principal axis system.
of L are the three sets of direction cosines that relate the The dipolar function 1 − 3(cos2 φ)/r 3 )av can be evalu-
x–y–z axis system to the α–β–γ axis system. ated from known wave functions of electrons in s, p, d, and
The components of the diagonalized hyperfine tensor other orbitals on different atoms. For s orbitals the dipolar
consist of an isotropic part A0 and a purely anisotropic function is zero because of spherical symmetry. The cylin-
part A , whose orientational average is zero. This decom- drical symmetry of p orbitals gives three components, A ,
position is shown in Eq. (14): A⊥ , and A⊥ , which are related by A = −2A⊥ . Note that
    the dipolar angular function changes sign at φ = 54◦ 44 .
 Aαα 0 0   A0 0 0 
  Thus, the space around a nucleus can be divided into four
 
d
A= 0 Aββ 0  =  0 A0 0  regions alternating in sign. In the determination of the hy-
 
 0 0 A  0 γγ 0 A0  perfine tensor, a set of signs of the components will be
  (14) obtained so that the sum of the diagonal principal values
 A 0 0  is zero.
 αα
  The A components from Eq. (16) have been evaluated
= 0 Aββ 0 .
  theoretically for unit spin density in atomic radial wave
 0 0 Aγ γ 
functions for p orbitals. Thus the experimental anisotropic
Thus the sum of the diagonal elements of d A gives 3A0 , hyperfine components can be used to estimate the amount
and the sum of the diagonal elements of A is zero. The of spin density in p orbitals. This complements the use
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340 Electron Spin Resonance

of isotropic hyperfine values to obtain the amount of spin lated and compared with experimental data. The difficulty
density in s orbitals. is that information about the excited-state energy levels
needs to be known to properly calculate the g tensor and
this is generally known only for simple molecular systems.
VII. g ANISOTROPY In a few cases, such as for the CO− 2 radical ion, detailed
calculations have been carried out and the experimental
In the general spin Hamiltonian given by Eq. (2), the g fac- g anisotropy has given information about the molecular
tor given in the electron Zeeman energy term is written as wave function.
a tensor connecting the electron spin angular momentum Organic radicals generally have the unpaired electron
operator S and the magnetic field vector H. A free elec- in a p orbital, which has orbital angular momentum. How-
tron has only spin angular momentum, and its orientation ever, the weak molecular electrostatic field splits the M L
in a magnetic field is determined only by this physical components and gives M L = 0 as the lowest state. In this
property. However, in general, in atomic and molecular case g  ge . Nevertheless, small deviations from ge do
systems there will be some contribution from orbital an- occur and can be readily measured, particularly in single
gular momentum to the total unpaired electron wave func- crystals, since at a typical 3300-G field, g = 0.0006 for a
tion. In this case the orbital and spin angular momentum 1-G shift.
vectors interact, and by convention this interaction is in- When an organic radical contains an atom with a large
corporated into an “effective” anisotropy in the g factor. In spin–orbit coupling constant, such as oxygen, sulfur, or
this representation the spin angular momentum vector S halogens, the g anisotropy becomes significantly greater
no longer represents “the true spin” because the true spin and the average g value generally shifts to larger values.
has only spin angular momentum and is associated with This serves as a diagnostic tool for radicals in solution and
an isotropic g value. Instead, when g is written as a tensor in solids. One particular example involves peroxy radicals
the spin angular momentum vector represents an effective in which the unpaired spin is localized largely on the oxy-
spin, which instead of being oriented along the magnetic gen and for which the average g equals 2.015 in a wide
field direction is oriented along the vector H · g. For most variety of environments. Sulfur-containing radicals also
purposes this nuance will not affect our utilization of the often show large g anisotropy. This can be used as a diag-
g tensor formulation. nostic test for the localization of the radical site in some
The experimental determination of the g tensor is car- biological molecules that contain sulfur.
ried out by a procedure completely analogous to that for The largest g anisotropy occurs for transition-metal
determination of the anisotropic hyperfine tensor. Mea- ions, where the g anisotropy is very useful for discrim-
surements are required as a function of angle in three inating between transition-metal ions in different types of
mutually perpendicular planes. From this data, a general environments. The range of g anisotropy can be rather
g tensor is obtained, which is diagonalized to find the prin- large. Typical values for axial g anisotropy range from
cipal values. The principal axes of the g tensor are often the g⊥ = 2.04 and g = 2.17 for copper complexes to g⊥ = 6
same as for the hyperfine tensor, but they do not have to be. and g = 2 for some ferric complexes.
The interpretation of the principal value of the g tensor
can be conveniently discussed by Eq. (17):
VIII. SPIN RELAXATION

gobs = ge + . (17)

E The energy between the magnetic energy levels at 3000 G,
In this expression, ge is the g factor for an isolated spin gβH , is only 10−3 of kT at 300 K. At thermal equilibrium
(2.0023), λ is the spin–orbit coupling constant, C is a pro- the Boltzmann factor, exp(−gβH/kt), gives the popula-
portionality constant calculated from the electronic wave tion ratio of the two levels, so the levels are almost equally
functions, and
E is the energy difference between the populated. The application of microwave energy causes
ground state and the first excited state. Values of λ have transitions between the magnetic levels. The microwave
been obtained for a number of atoms and ions from atomic field stimulates transitions in both directions with a prob-
spectra, but the particular value to be used in a molecular ability that depends on the microwave power and on the
system can only be approximated by this. In general, λ number of spins in each level. Transitions from the lower
values increase with atomic number. The values of
E to upper levels absorb energy, while upper- to lower-level
can sometimes be deduced from electronic spectra. Thus transitions emit energy. Since the population is slightly
the g anisotropy is related to the electronic wave function, greater in the lower level there will be a net absorption of
and if sufficient information is known about the electronic microwave energy; this provides the observed ESR signal.
wave function the principal g components can be calcu- Under steady application of the microwave field with no
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Electron Spin Resonance 341

other interactions, the populations in the magnetic energy spin states are equalized, Mz = 0, and the resonance ab-
levels would soon become equal; there would then be no sorption disappears. After the pulse, the recovery of Mz
net absorption of microwave energy and no ESR signal. toward M0 with a time constant T1 can be observed by the
However, the spin system is subject to other interac- growth of the resonance line. The term T1 is also called the
tions, the very interactions that bring about thermal equi- longitudinal relaxation time, because it refers to relaxation
librium. These interactions can be collectively called spin– along the magnetic-field axis.
lattice interactions. They comprise radiationless interac- The Mx and M y components of M are not changed by
tions between the spin system and the thermal motion of a spin flip. The m x and m y components of each individual
the “lattice” or surroundings. The inverse of the rate of spin are randomly oriented before and after the magnetic
spin–lattice induced transitions is described by a charac- field Hz is applied. However, application of H1 in the x–y
teristic time called the spin–lattice relaxation time and is plane can produce a net phase alignment of the m x and m y
denoted by the symbol T1 . components to give Mx and M y . When H1 is removed, the
At sufficiently low microwave powers, the spin–lattice phase coherence of the spins decays by 63% in time T2 .
relaxation processes are fast enough to maintain a thermal The term T2 is also called the transverse relaxation time
equilibrium population between magnetic energy levels. because it refers to relaxation of magnetization compo-
As the microwave power is increased the net upward rate nents transverse to the external magnetic field.
of microwave-induced spin transitions from the lower to An ESR line is not infinitely sharp; it has a shape and
upper states is increased and eventually competes with width due to spin relaxation. The equations of motion
the spin–lattice induced net downward rate. The spin pop- for Mx , M y , and Mz in the presence of an applied field
ulations in the two magnetic states become more equal H0 and including the spin relaxation processes discussed
and the ESR signal intensity decreases; this is known as above are called the Bloch equations. The solution to these
power saturation. Normally, one wants to use low enough equations predicts a Lorentzian line with a halfwidth at
microwave power to avoid power saturation. halfheight of T2−1 . Lorentzian lineshapes are indeed of-
In addition to spin–lattice relaxation, in which energy ten found for free radicals in liquids. In this case T2 can
is transferred from the spin system to the lattice, there be determined from the linewidth. The Bloch equations
exist spin–spin relaxation mechanisms, in which energy is also predict how the ESR signal intensity will vary with
redistributed within the spin system. One may think of this increasing microwave power. The ESR signal increases,
redistribution as a modulation of the spin energy levels. In reaches a maximum, and then decreases with increasing
both fluid and solid phases, the net local magnetic fields are microwave power; this behavior is called power satura-
rapidly varying due to different types of molecular motion, tion. From an analysis of the power saturation curve of
and a given spin level at m S gβ H is therefore modulated. ESR intensity versus microwave power, it is possible to
At high spin concentrations, direct spin–spin exchange determine T1 .
and dipolar interaction can also occur. The characteristic In solids, typical ESR lineshapes are Gaussian in-
time for spin–spin relaxation within a single spin system stead of Lorentzian. One common interpretation of the
is symbolized by T2 . Gaussian lineshape is that it is composed of a distribution
In a single spin system the spin–lattice (T1 ) and spin– of Lorentzian lineshapes, each of which corresponds to a
spin (T2 ) relaxation times can be given a precise classi- group of spins forming a “spin packet” which “see” the
cal and quantum-mechanical description. A collection of same local magnetic environment. If these spin packets are
spins has a magnetic moment vector M, which can be randomly distributed in intensity they will superimpose to
resolved into three components, Mx , M y , and Mz . Be- give a Gaussian lineshape. Note that for Gaussian lines T2
fore a magnetic field is applied, the number of spins in cannot be determined from the linewidth. Gaussian lines
the two magnetic energy states is equal; after the field is still undergo microwave power saturation, but very care-
applied, some of the spins begin flipping to achieve a ther- ful and sometimes complex analysis is required to extract
mal equilibrium distribution between the two states. For values of T1 and T2 .
an applied magnetic field in the z-direction the spin flips A more direct method to obtain values of the spin–lattice
cause Mz to change toward a steady value M0 , which is and spin–spin relaxation times is to use time-domain ESR
proportional to the measured static magnetic susceptibil- methods, which are briefly described next.
ity. Mz approaches M0 with a time constant T1 such that
Mz = e−1 M0 = 63%M0 in time T1 . So that resonance can IX. DOUBLE-RESONANCE
be observed, the microwave magnetic field H1 is applied AND TIME-DOMAIN ESR
perpendicular to Hz . If the intensity of H1 is increased
greatly with a pulse of microwaves, the spin system satu- Double-resonance experiments are usually carried out in
rates. This means the populations in the upper and lower spectroscopy to increase spectral resolution. There are
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342 Electron Spin Resonance

several different kinds of double-resonance experiments the total number of lines is additive for different types
that can be done in ESR. The technique that appears to of coupled nuclei, whereas in ESR the number of lines
be the most useful currently and one that is becoming is multiplicative. A specific example can be considered
more widespread is electron nuclear double resonance, for the triphenylmethyl radical. In the ESR spectrum the
abbreviated ENDOR. Essentially, ENDOR is the obser- total number of lines is 196, spread over a 30-G range.
vation of the effect of applying a second frequency, which By ENDOR there are only 6 lines, which can be easily
induces nuclear spin flips, simultaneously with the mi- resolved because you see only one pair of ENDOR lines
crowave frequency that induces electron spin flips. The for each group of equivalent nuclei. In the triphenylmethyl
observation of ENDOR depends on partial saturation of radical there are three different types of protons—namely,
an ESR transition. In simple terms, the ENDOR effect is meta, ortho, and para protons—each of which have differ-
simply the change of the ESR intensity when a second ent hyperfine couplings. Thus this spectral simplification
radio frequency field is applied to the system. leads to effectively increased resolution for liquid-phase
Experimentally, ENDOR is carried out by fixing the spectra.
external magnetic field at an ESR hyperfine line and then 4. ENDOR is also very useful for studying details of
sweeping the radio frequency from perhaps 1 to 20 MHz. spin relaxation mechanisms. The effect of molecular mo-
ENDOR lines will be observed corresponding to differ- tions on relaxation processes can be studied. Solvation
ently coupled nuclei in the paramagnetic system. For and temperature effects on both electron and nuclear re-
weak hyperfine interactions, the ENDOR lines for each laxation mechanisms can also be investigated.
type of spin- 12 nucleus are given by ν N ± A/2 where
ν N = g N β N H/ h. For protons, νH ≈ 14 MHz at 3300 G. Time-domain ESR methods have become quite impor-
Thus a pair of lines is observed in the ENDOR spectrum tant for modern applications of ESR. In a time-domain
for each type of coupled protons. The hyperfine constant experiment one uses microwave pulses rather than steady-
A can be measured more accurately with ENDOR than state microwaves. It is possible to use pulses as short as
by ESR, because one is measuring megahertz instead of a few nanoseconds, which makes fast kinetic processes
gigahertz. Also, the hyperfine nucleus can be identified involving paramagnetic species observable and allows the
from the value of g N , since these values are characteristic direct measurement of relaxation times. In addition, time-
for different nuclei. domain ESR methods have been useful for more direct
The practical advantages of ENDOR experiments can determination and study of relaxation mechanisms and
be summarized as follows: for developing new methods for obtaining structural in-
formation in disordered systems.
1. Increased resolution can be obtained, which is par- Two methods of time-domain ESR will be briefly dis-
ticularly important for inhomogeneously broadened lines cussed. The oldest method is that of saturation recovery,
typically observed in solids where the hyperfine struc- which is a direct method to determine spin–lattice relax-
ture is unresolved. A typical ESR linewidth in solids ation times. The idea is to perturb the steady-state pop-
is 10 G, whereas a typical ENDOR linewidth is about ulation of spins with a partially saturating pulse of mi-
0.03 G. A classic example is that of a trapped electron crowaves and then to observe with a very weak microwave
or of trapped hydrogen atoms in potassium chloride crys- field the recovery of the perturbed spin population to equi-
tals. In these paramagnetic systems, ENDOR couplings librium. In the absence of complications, the recovery pro-
to different shells of magnetic nuclei are resolved, and a cess is exponential and can be related to the time constant
detailed picture of the electron and hydrogen-atom wave for spin–lattice relaxation. Exponential recoveries are gen-
functions can be obtained. By ordinary ESR, only a broad erally observed in liquids and in some cases in solids. If
line is observed, in which the hyperfine information for the spin–lattice relaxation time is not much longer than
the different magnetic nuclei in the solid is not resolved. the spin–spin relaxation time, which is atypical in param-
2. Hyperfine constants can be measured more accu- agnetic systems, the interpretation of saturation recovery
rately by ENDOR than by ESR. This is particularly impor- data becomes more complex.
tant for measuring very small hyperfine couplings. Also, The second type of time-domain method that will be
very small changes in the hyperfine couplings due to tem- discussed is electron spin-echo spectroscopy, abbreviated
perature and so forth are most accurately measured by ESE. Figure 9 gives an illustration of a two-pulse electron
ENDOR. spin-echo response. Two resonant microwave pulses are
3. ENDOR can lead to significant spectral simplifica- applied to the system with typical pulse lengths of 10–
tion, which is particularly important in looking at radicals 100 nsec and pulse powers corresponding to several hun-
in liquids. This is because the total number of spectral dred watts. The first pulse (1) essentially starts a clock and
lines is much less in ENDOR than in ESR. In ENDOR flips the spins from the external magnetic field direction
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Encyclopedia of Physical Science and Technology EN005E-212 June 15, 2001 20:32

Electron Spin Resonance 343

T is swept to produce the echo modulation pattern. This


can simplify analysis of the pattern. Also, the echo decay
becomes slower since it is usually dominated by the spin–
lattice relaxation time T1 . This results in more detectable
FIGURE 9 Illustration of a two-pulse electron spin-echo signal. modulation periods and hence more accurate analysis. A
Microwave pulses 1 and 2 separated by time τ produce the echo
signal V at a second time τ after pulse 2. As τ is increased the
four-pulse sequence in which an additional 180◦ pulse
echo amplitude generally decreases, and in solids the amplitude is introduced in the middle of the T period for a three-
may be modulated as shown here. The decrease in echo ampli- pulse sequence is also useful for measuring combination
tude is related to transverse magnetic relaxation times, and the frequencies.
modulation is related to weak anisotropic hyperfine coupling to Pulsed ENDOR has also become a more common tech-
nearby magnetic nuclei.
nique. This is achieved by adding a radio frequency pulse
within a spin-echo pulse sequence. Then, by detecting the
along the z axis to the x–y plane. During time τ between echo intensity while the radio frequency is swept, one can
the pulses the spins precess in the x–y plane. After time obtain a pulsed ENDOR spectrum which directly reveals
τ a second pulse (2) is applied, which is a 180◦ pulse and electron–nuclear hyperfine frequencies.
which flips the spins into the other direction in the x–y
plane. The spins then precess back together, and at a sec-
ond time τ after the second pulse they coalesce and form X. APPLICATIONS
a bu