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category is a section that treats the effects of instrumental and environmental or all of the manuscript.

l of the manuscript. Included are Professors R. R. Bessette, Southeastern


noise on the precision and accuracy of spectroscopic absorption measurements. Massachusetts University; M. F. Bryant, University of Georgia; J. F. Coetzee,
Also largely new is the development of general chromatographic theory from University of Pittsburgh; P. Dumas, Trenton State College; E. T. Gray, Jr.,
kinetic considerations. The chapter on optical instruments brings together University of Hartford; D. M. King, Western Washington University; P. F. Lott,
information that was formerly found in chapters on infrared, ultraviolet and University of Missouri, Kansas City; C. H. Lochmuller, Duke University;
visible, and atomic absorption spectroscopy; flame and emission spectroscopy; F. W. Smith, Youngstown State University; M. Thompson, University of
and fluorescence and Raman spectroscopy. Toronto; A. Timnick. Michigan State University; W. H. Smith, Texas Tech
Since the publication of the first edition, a host of modifications of well- University; J. E. Byrd, California State College-Stanislaus; A. M. Olivares.
established instrumental methods have emerged and are now included. Among Texas A & I University; and E. J. Billo. Boston College.
these new developments are Fourier transform nuclear magnetic resonance and We also wish to thank Dr. Natalie McClure, now of Syntex Corporation.
infrared methods, infrared photometers for pollutant measurements, laser for preparing problem sets and their solutions for Chapters 8, 14, and 17, and
modifications of spectroscopic measurements, nuclear magnetic resonance Professor Daniel C. Harris. of University of California-Davis. for preparing
measurem<:nts on nuclei other than hydrogen, electron spin resonance problem sets and solutions for Chapters 5. 9-13, 23. and 25.
spectroscOpy, photon counting, inductively coupled plasma sources for emission
spectroscopy, semiconductor detectors for X-rays and gamma rays, energy Stanford, California DoUGLAS A. SKOOG
dispersive: X-ray systems, the electron microprobe, X-ray photoelectric San Jose, California DoNALD M. WEST
spectrometry, chemical, field ionization, and spark sources for mass spectrom- September, 1979
etry, gas electrodes, potentiostatic controls for polarography, differential
pulsed and rapid scan polarography, cyclic and ac voltammetry, high
performance liquid chromatography, new packings for gas-liquid chroma-
tography. interfacing of chromatography with mass. infrared. and fluorescence
detectors, instruments for simultaneous. multielement analysis, and automated
instruments for spectroscopy, electroanalysis. titrimetry, and chromatography.
In addition to the foregoing, the new edition contains, as an appendix, a
brief treatment of the propagation of random errors in analytical measurements.
It is worth noting that selected portions of the material found in this text
have also appeared in the authors' two other titles.· The principal overlap of
the material in this book with that in the earlier two occurs in the chapters
on potentiometry, coulometry, and voltammetry. Duplication willbtl found to
a lesser extent in the chapters on ultraviolet and visible absorption'spectroscopy
and atomic emission spectroscopy.

The authors wish to acknowledge with thanks the considerable contributions


of Professor Alfred R. Armstrong, College of William and Mary. and Dr. James
LuValle, Stanford University, who have read the entire manuscript in detail
and offered many useful suggestions. We are also grateful to Professor R. deLevie
of Georgetown University for his comprehensive review and numerous sug-
gestions for Chapters 2 and 3, to Professor H. S. Mosher of Stanford University
for his helpful comments on the chapter on optical activity. and to Professors
S. R. Crouch of Michigan State University and J. D. Ingle. Jr.. of Oregon State
Universit~ for their detailed criticisms on and suggestions for the section on
precision of spectral measurj:ments. Finally, we offer our thanks to several
others who have taken the time to comment, often in some detail, on portions

'0. A. Skoog and D. M. Wes •• FundamemaL, o(Analrrical Chern;.."r. 3d cd .. 1976. and Ana1l'tical
Chern;.",)'. 3d cd .. 1979. Hok. Rinehan and W'inston: l'ew York. . .
CONTENTS

1 INTRODUCTION
Types of Analytical Methods
Instruments for Analysis

2 ELECTRICITY AND ELECTRIC CIRCUITS


Introduction
Reactance in Electrical Circuits
Simple Electrical Measurements

3 ELEMENTARY ELECTRONICS
Semiconductors
Amplifiers Employing Transistors
Power Supplies and Regulators Employing Transistors
Operational Amplifiers
Noise
Readout Devices
Interfacing of Instruments with Computers

ELECTROMAGNETIC RADIATION AND ITS INTERACTIONS WITH


MATTER 91 (
Properties of Electromagnetic Radiation 92
The Interaction of Radiation with Maller 101
Emission of Radiation 109

5 COMPONENTS OF INSTRUMENTS FOR OPTICAL


SPECTROSCOPY 113
Components and Configurations of Instruments for Optical Spectroscopy 114
Radiation Sources 115
Wavelength Selection; Monochromators 123
Wavelength Selection: Filters 136
Sample Containers 137
Radiation Detection 137
Signal PrOcessors and Readouts 145

6 AN INTRODUCTION TO ABSORPTION SPECTROSCOPY 148


Terms Employed in Absorption Spectroscopy 149
Quantitative Aspects of Absorption Measurements 151
/ APPLICATIONS OF ULTRAVIOLET AND VISIBLE ABSORPTION '1'f. MISCELLANEOUS OPTICAL METHODS 352
MEASUREMENTS 168 V'1fefractometry . .
169 353
Absorbing Species
180
,Polarimetry 357
Some Typical Instruments Optical Rotatory Dispersion and Circul~r Dichroism 370
Application of Absorption Measurement to Qualitative Analysis 187
Quantitative Analysis by Absorption Measurements 188 14 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY 376
Photometric Titrations 197 Theory of Nuclear Magnetic Resonance 377
Automatic Photometric and Spectrophotometric Analysis 199 Experimental Methods of NMR Spectroscopy 386
Photoacoustic Spectroscopy 202 Environmental Effects on Proton NMR Spectra '390
Applications of Proton NMR 404
INFRARED ABSORPTION SPECTROSCOPY 209 Application of Proton NMR to Quantitative Analysis 407
Theory of Infrared Absorption 210 Fourier Transform NMR '409
Infrared Instrument Components 219 Electron Spin Resonance Spectroscopy .412
Some Typical Instruments 221
Sample Handling Techniques 226 \/'15 X-RAY METHODS 426
Qualitative Applications of Infrared Absorption 230 Fundamental Principles ,427
Quantitative Applications 237 Instrument Components 434
Infrared Fourier Transform Spectroscopy 241 X-Ray Fluorescence Methods 444
Hadamard Transform Spectroscopy 254 X-Ray Diffraction Methods 450
The Electron Microprobe Method 452
X-Ray Photoelectron Spectroscopy ,453
RAMAN SPECTROSCOPY 262
Theory of Raman Spectroscopy 263 16 RADIOCHEMICAL METHODS i458
Instrumentation 268 The Radioactive Decay Proa:ss ,459
Applications of Raman Spectroscopy 270 Neutron Activation Analysis 467
Isotopic Dilution Methods 471
\/10 MOLECULAR FLUORESCENCE SPECTROSCOPY 279 Radiometric Methods 473
Theory of Fluorescence 280
Instruments for Fluorescence Analysis 289 vi7 MASS SPECTROMETRY 476
Applications of Fluoremetry 293 The Mass Spectrometer 477
Nephelometry and Turbidimetry 294 Mass Spectra 488
Qualitative Applications of Mass Spectrometry 491
Quantitative Applications of Mass Spectrometry 496
".11 ATOMIC SPECTROSCOPY 301
Theory of Flame Spectroscopy 303 18 AN INTRODUCTION TO ELECTROANALYTICAL CHEMISTRY 500
Flame Characteristics 308 Electrochemical Cells 501
Atomizers for Atomic Spectroscopy 312 Cell Potentials 507
Atomic Absorption Spectroscopy 315 Half-Cell or Electrode Potentials .512
Atomic Emission Spectroscopy 326 Calculation of Cell Potentials from Electrode Potentials ,524
Atomic Fluorescence Spectroscopy 332 Effect of Current on Cell Potentials 527
Reference Electrodes i531
12 EMISSION SPECTROSCOPY 335 Standard Weston Cells '534
Emission Spectra 337
19 POTENTIOMETRIC METHODS - 538
Arc and Spark Sources 337
Argon Plasma Sources Indicator Electrodes 539
340
Instruments for Emission Spectroscopy Instruments for Cell Potential Measurement 554
342
Applications of Emission Spectroscopy Direct Potentiometric Measurements 555
347
Potentiometric Titrations 559
1 580 vAPPENDIX 1 PROPAGATION OF UNCERTAINTIES IN
20 . ELECTROGRAVIMETRIC AND COULOMETRIC METHODS
581 PHYSICAL MEASUREMENTS
Current-Voltage Relationship During an Electrolysis
Electrogravimetric Methods of Analysis 587 APPENDIX 2 SOME STANDARD AND FORMAL ELECTRODE
Coulometric Methods of Analysis 590 POTENTIALS

21 VOLTAMMETRY AND POLAROGRAPHY 605


Polarography 606
Applications of Polarography 617
Voltammetry at Solid Electrodes 622
Polarography with Potentiostatic Control 625
Modified Voltammetric Methods 627
Amperometric Titrations 635
Amperometric Titrations with Two Polarized Microelectrodes 637

22 CONDUCTOMETRIC METHODS 643


Electrolytic Conductance 644
The Measurement of Conductance 647
{::onductometric Titrations 648
Applications of Direct Conductance Measurements 651
Oscillometry 652

THERMAL METHODS 654


Thermogravimetric Methods 655
Differential Thermal Analysis and Differential Scanning Calorimetry 657
Thermometric Titrations 662

AN INTRODUCTION TO CHROMATOGRAPHY 666


A General Description of Chromatography 667
The Rate Theory or Chromatography 671
Separations on Columns 676
Summary of Important Relationships for Chromatography 681
Qualitative and Quantitative Analysis by Chromatography 681

LIQUID CHROMATOGRAP.HY \689


Column Chromatography 690
Planar Chromatography 705
Electrophoresis and ElectrochrOnilatography 709

GAS-LIQUID CHROMATOGRAPHY 715


Principles or Gas-Liquid Chromatography 716
Apparatus 717
Applications or Gas-Liquid Chromatography 722
Gas-Solid Chromatography 731
Examples of Applications of Gas Chromatography 731
PRINCIPLES
OF
INSTRUMENTAL
ANALYSIS
A chemical analysis provides information ductance is to serve as the signal for the separation and resolution of closely related arriving at a decision as to which method to
about the composition of a sample of matter. analysis of one of these species in a sample compounds. Common separation methods in- choose, the chemist must take into account
The results of some analyses are qualitative that also contains the other. clude chromatography, distillation, extrac- the complexity of the materi~ to be
and yield useful clues from which the molecu- tion, ion exchange, fractional crystallization, analyzed, the concentration of the species of
lar or atomic species, the structural features, and selective precipitation. One' of the signals interest, the number of samples to be
or the functional groups in the sample can be TYPES OF listed in Table 1-1 is ordinarily used to com- analyzed, and the accuracy required. His
deduced. Other analyses are quantitative; ANALYTICAL METHODS plete the analysis following the separation choice will then depend upon a knowledge of
here, the results take the form of numerical step. Thus, for example, thermal conductivity, the basic principles underlying the various
data in units such as percent, parts per Table I-I lists most of the common signals volume, refractive index, and electrical con- methods available to him, and thus their
million, or millignlms per liter. In both types that are useful for analytical purposes. Note ductance have all been employed in conjunc- strengths and limitations. The development of
of analysis, the required information is ob- that the first six signals involve either the tion with various chromatographic methods. this type of knowledge represents a major
tained by measurU1g a physical property that emission of radiation or the interaction of This text deals with most of the instrumen- goal of this book.
is characteristically_ related to the component radiation with matter. The next three signals tal methods listed in Table 1-1, as well as with
or components of mterest. are electrical. Finally, five miscellaneous sig- many of the most widely employed separation INSTRUMENTS
It is convenient to describe properties nals are grouped together. Also listed in the procedures. Little space is devoted to the clas- FOR ANALYSIS
which are useful for determining chemical table are the names of analytical methods sical methods, since their use is normally
composition as muilytical signals; examples of which are based on the various signals. treated in elementary analytical courses. In the broadest sense, an instrument for
such signals include emitted or absorbed It is of interest to note that until pCrhaps Table I-I suggests that the chemist faced chemical analysis converts a signal that is
light, conductance, weight, volume, and re- 1920, most analyses were based on the last with an analytical problem may have a bewil- usually not directly detectable and under-
fractive index. None of these signals is unique two signals listed in Table I-I-namely, mass dering array of methods from which to standable by man to a form that is. Thus, an
to a Jiven species. Thus, for example, aU me- and volume. As a consequence, gravimetric choose. The amount of time spent on the instrument can be viewed as a communica-
tallicelements in a Sample will ordinarily emit and volumetric procedures have come to be analytical work and the quality of the results tion device between the system under study
ultraviolet and visible radiation when heated known as classical methods of analysis, in are critically dependent on this choice. In and the scientist.
to a sufficiently hiih temperature in an elec- contrast to the other procedures, which are
tric arc; all charged species conduct electric- known as instrumental methods.
ity; and all of the components in a mixture Beyond the chronology of their develop-
contribute to its refractive index, weight, and ment, few features clearly distinguish in-
volume. Therefore, all analyses require a strumental methods from classical ODes.Some TABLE 1-1 SOME ANALYTICAL SIGNALS
separation. In some instances, the separation instrumental techniques are more sensitive
step involvc:s physical isolation of the individ- than classical techniques, but many are not. Signal Analytical Methods Baed on Maisurement of Signal
ual chemical components in the sample With certain combinations of elements or Emission spectroscopy (X-ray, UV, visible, electron,
prior to signal generation; in others, a signal compounds, an instrumental method may be Augerl; flame phot~metry; fluorescence (X-ray, UV,
IS generated or observed for the entire sample,
more Specific; with others, a gravimetric or a visible ; radiochemical method~ .
following which the desired signal is isolated volumetric approach may be less subject to Spectrop otometry (X-ray, UV: VISible,IR); .
from the others. Some signals are susceptible interference. Generalizations on the basis of colorimetry· atomic absorptiOn, nuclear magnetic
to the latter treatment, while others are not. resonance, ~nd electron spin resonance spectroscopy
accuracy, convenience, or expenditure of time Turbidimetry; nephelometry, Raman spectroscopy
For example, when a sample is heated in an Scattering of radiation
are equally difficult to draw. Nor is it neces- Refraction of radiation Refractometry; interferometry
electric arc, the w~velength distribution for sarily true that instrumental procedures X-Ray and electron diffraction !Deth~s .
Diffraction of radiation
the radiation of each metallic species is employ more sophisticated or more costly Rotation of radiation Polarimetry; optical rotatory dISpersion; Circular
unique to that spj:Cies; separation of the apparatus; indeed, use of a modern automatic dichroism
wavelengths in a s~itable device (a spectro- Electrical potential Potentiometry; chronopotentiometry
balance in a gravimetric analysis involves Polarography; amperometry; coulometry
scope) thus makes possible the identification Electrical current
more complex and refined instrumentation Electrical resistance Conductimetry
of each component without physical separa- than is required for several of the methods Mass spectrometry
Mass-to-char,ge ratio
tion. On the other hand, no general method found in Table 1-1. Rate of reaction Kinetic methods
exists for distinguishing the conductance of Thermal properties Thermal conductivity and enthalpy methods
In addition to the methods listed in the
sodium ions from that of potassium ions. Mass Gravimetric analysis
second column of Table I-I, there exists Volumetric analysis
Here, a physical separation is required if con- Volume
another group of analytical methods for the
CornponenQ sipal to another. An example is a thermo- addition to being amplified,signals are often electronics, because the generation, transduc-
of Inatrulll8l1t8 couple, which converts a radiant heat signal multiplied by a constant smaller than unity tion, amplification,and display of a signal can
into an electrical voltage; the bellows in an (attenuated1 integrated, differentiated,added be rapidly and conveniently accomplished
Regardless of its complexity, an instrument aneroid barometer transduces a pressure or subtracted, or increased exponentially. with electronic circuitry. Numerous trans- .
generally contains nO more than four fun- sipal into a mechanical motion signal. Most Other operations may involve conversion ducers have been developed for the conver- .
damental components. As shown schema- of the transducers that we will encounter con- into an alternating current, rectification to sion of chemical signals to electrical fonn,
tically in Figure 1-1,these components are a vert analytical signals into an electrical give a direct current, comparison of the and enormous amplification of the resulting
signal generator, an input tr~ucer or voltage,current, or resistance, because of the transduced signal with one from a standard, electrical signals is possible.In turn, the eleo- .
detector, a signal processor, and an output ease with which electrical signals can be and transformation from a current to a volt- trical signals are readily presented on meters,
transducer or readout. A general description amplified and modified to drive readout de- age or the converse. on recorders, or in digital form.
of these components follows. vices.Note, however,that the transduced sig- R__ l>efices. Readout devices employ
SipaI Geaerators. Signal generators pro- Owing to the large amount of electronic
nals for the last two instruments in Table 1-2 an output transducer to convert the amplified circuitry in the laboratory, the modem
duce analytical signals from the ,components are nonelectrical. signal from the processor to a signal that chemist is faced with the question of how
of the sample. The generator 'may simply SipaI Processors. The signal processor can be read by the human eye. Readout much knowledge of electronics is needed to
be the sample itself. For example, the signal modifiesthe transduced signal in such a way devices take the form of meters, strip chart make most efficient use of the equipment
for an analytical balance is ~ mass of a as to make it more convenient for operation recorders, oscilloscopes, pointer scales, and available for analysis.We believethat it is not
component of the sample; for a pH meter, the or the readout device. Perhaps the most digital devices. only desirable but feasible for the chemist to
signal is the activity of hydrogen ions in a common modification is that of amplifica- possess a qualitative knowledgeof how elec-
solution. In many other instruments, tion-that is,mUltiplicationof the signal by a tronic circuits work. Thus, Chapters 2 and 3
however, the signal generator is more elabo-
.rate. For example, the signal generator of an
infrared spectrophotometer includes, in addi-
constant greater than unity. In a two-pan
analytical balance, the motion of the beam
is amplified by the pointer, whose displace-
-.d
Electronics
Instrumentation
are largely devoted to a presentation of this
topic; subsequent chapters are concerned
The growth of instrumental analysis has with the application of various instruments to
tion to the sample, a source of infrared radia- ment is significantly greater than that of closely paralleled developmentsin the fieldof the solution of chemical problems.
tion, a monochromator, a beam Chopperand the beam itself. Amplification by a photo-
splitter, a sample holder, and' a radiation graphic film is enormous; here, a single
attenuator. photon may produce as many as 1012 silver
The second column of Table 1-2lists some atoms. Electrical signals can, of course, be
examples of signal generators. readily amplifiedby. factor or 106 or more. TABLE '-2 SOME EXAMPLES OF INSTRUMENT COMPONENTS
•••• T........ ••. Detectors. A trllllS- A variety of other modifications are
ducer is a device that converts one type of commonly carried out on electricalsignals.In SIpaI A..tyticaI IIIpIIt T~ SipaI
1• ...-. GeRenator Signal Tnnsducer Signal ~ Readout

Photometer Tungsten lamp. Attenuated Photocell Electrical None Current meter


glass filter, light beam current
sample

IIT'JI!
s:...-
Atomic emission Flame, UVor Photomultiplier Electrical Amplifier, Chart
sp«:trometer monochromator, visible tube potential demodulator recorder
Electrical chopper, radiation
or sample
mechanical
Coulometer dc source, Cell current Electrodes Electrical Amplifier Chart

-"";';"
_~_;.u_.~_,.:.=;.,
~.-- pH meter

X-Ray powder
diffractometer
sample
Sample

X-Ray tube,
sample
Hydrogen ion
activity
Dilfra(.ted
radiation
Glass-calomel
electrodes
Photographic
film
current
Electrical
potential
Latent
image
Amplifier,
digitalizer
Chemical
developer
recorder
Digital unit

Black images
on film

/112.301
o 0
'I Oi~ital
un,t
Color
comparator
Sunlight,
sample
Color Eye Optic nerve
signal
Brain Visual color
response

Output transducer
or readout
This chapter provides a brief and elementary where Q is the charge. The ampere, A, the unit
review of the laws governing electrical cur- of current, corresponds to a rate of one cou-
rents, the properties of direct and alternating lomb per second.
current circuits, and selected methods for The electrical potential V between two
measuring electrical quantities.! points in space is the work required to move
an electrical charge from one of the points to
the other. When the work is given in joules
and the charge in coulombs, the unit for
potential is the VOII, V. That is, one volt is
An electrical current is the motion of a charge equal to one joule per coulomb.
through a medium. In metallic conductors, The olun, n. is the unit of resistance R to
only electrons are mobile; here, the current current flow and is the resistance through
involves motion of negative charges only. In which a potential of one volt will produce a
media such as ionic solutions and semicon- current of one ampere.
ductors, both negative and positive species Electrical conductance G is the reciprocal
are mobile and participate in the passage of of resistance and has the units of reciprocal
electricity. ' ohms, n- !, or siemens, S.
Electrical power P is the rate of electrical
Electrical Units work in joules per second or watts W. The
The unit of charge or quantity of electricity is power dissipated during passage of electrons
the coulomb,: C, which is the charge required is given by
to convert O;<lOUI800 g of silver ion to silver
metal. Another unit, the faraday, F, corre-
sponds to o;ne equivalent of charge, that is, Substitution of Equation 2-4 yields the power
6.02 x 1023 charged particles. The relation- loss in a resistance of R ohms; that is
ship between the two units is readily cal-
culated from their definitions:
coulombs 107.87 g Ag"/equivalent Ag"
faraday 0.00111800 g Ag"/coulomb
Electrical Currents
I equivalent Ag"
x 1 equivalent of charge If a conducting path exists between two
points with differing potentials, charge will
= 9.649 x 10· flow until the difference in potentials becomes
zero. For example, when the switch is closed
Electric' current 1 is the rate of flow of a
in the direct current circuit shown in Figure
charge. That is,
2-1, a conducting path is provided, through
which charge can flow from one terminal of
the battery to the other. Current will continue
until the potential difference between .4 and B
I Some generai references. which cover these topics. becomes zero-that is, until the battery is
include: A. J.' Diefenderfer. Principles on E1«rronic
Insrrumentation, 2d cd. Philadelphia:' Saunders, 1979; discharged.
J. J. Brophy. Basic Electronics for Scientists. 3d cd. By convention, the direction of a current is
New York: McGraw-Hil~ t977; H. V. Malmstadl, C. G. always from the positive terminal to the nega-
Enke. S. R. Crouch, and G. Hortick, Electronic Measure- tive, regardless of the type of particle that car-
ments for Scientists. Menlo Park, CA: Benjamin, t974; ries the current. Thus. in the external circuit
and R. J. Smith, Circuits, Devices, and Systems, 3d cd. shown in Figure 2-1, current takes the form of
New York: Wiley. 1976.
with sulfuric acid at the expense of the region A to A. The three voltages thuS oppose the volt-
around C. age of the battery V and must be given oppo-
Two electrochemical reactions make pos- site signs.
',1

1
sible the transition from electronic conduc- Substitution of Ohm's 'law into Equation
tion in the metal to conduction by ions in the 2-5 gives
solution. In the first of these two reactions,
hydrogen ions consume electrons from C; in ,.1
the second, water molecules give up electrons
Note that the total resistance R of a series
at D. Thus, three modes of passage of electric- V I" ,.1 circuit is equal to the sum of the resistances of
ity exist in this simple circuit: electronic, +
ionic, and electrochemical. the individual components. That is,
o
R = RI + R2 + R3 (2-7)
Laws of Electricity" '-',v,- '.v.-'.-'.
v- + + v. Applying Ohm's law to the part of the cir-
R- R, + R2 + R2
OIun's Law. Ohm's law takes the form cuit from points B to A gives
Dxygen formation Hydrogen forlTjotion FIGURE 2-2 Resistors in series; a volt-
H.O-to. + 2H' + 2e 2H' + 2e-H.- age divider. VI = IIR. = IRI
Conduction by electrochemicai reaction
where V is the potential in volts between two Dividing by Equation 2-6 yields
points2 in a circuit, R is the resistance be- VI .lR1
tween the two points in ohms, and 1 is the
resulting current in amperes.
Kirchhotl's current law to point D in the 17 = ./(RI + R2 + R3)
circuit, we write
Ohm's law applies to electronic and ionic
motion of electrons e through the metal don- conduction; it is not, however, applicable to
:Iuctors Be and AD. The direction of the Cur- conduction across interfaces such as the elec-
rent I, however, is said to be from A to D to trode surfaces in the cell shown in Figure 2-1.
C to B; that is, current is always treated as if Kircbhofl's Laws. KirchhoJls cu"ent law It is clear that we may also write
it were a ftow of positive charge. states that the algebraic sum of currents
Note that the current out of D must be oppo- Y: = VR2/R
The two platinum electrodes (C and D) around any point in a circuit is zero. Kirch-
hofflJ voltage law states that the algebraic sum site in sign to the input current. Similarly,
md the dilute sulfuric acid solution in which
of the voltages around a closed electrical loop application of the law to point C gives
:hey are immersed represent an electrochemi-
:al cell. The mechanism by which electricity is zero. [3 = [2 Vl = VR3/R
:lasSeSthrough this cell is entirely different The applications of Kirchhotl's and Ohm's Voltage Dividers. Series resistances are
'rom that in the metallic conductor. Here, the laws to simple dc circuits are considered in Thus, it is apparent that the current is the
widely used in electronic circuits to provide
tow involves migration of positive hydrogen the next section. same at all points in a series circuit or
potentials that are variable functions of an
ons toward electrode C, and of negative sul- [=[t=[2=[3=[4 input voltage. Devices of this type are called
ate and hydrogen sulfate ions toward elec- voltage dividers. As shown in Figure 2-38, one
rode D. Note that the excess negative ch~rge Series Circuits Application of the voltage law to the cir- type of voltage divider provides voltages in
hat tends to accumulate around D as a result Consider the simple electrical circuit in cuit yields the equation discrete increments; the second type (Figure
If the anionic migration is exactly offset; by Figure 2-2, which consists of a battery, a 2-3b), called a potentiometer,3 provides a
V-V3-V2-VI=O
he postively charged hydrogen ions switch, and three resistors in series. Applying potential that is continuously variable.
Iroduced by the electrode process; similarly,
he excess hydrogen ions that migrate to elec-
rode C are removed by the electrochemical
2 In Chapten 2 aud 3, the symbol V will be used to 3 The word potentiometer is also used in a different c0n-
,rocess. The consequence is that the solution Note that point D is positive with respect to
denote electrical potential in circuits. In Chapters 18 to text as the name for a complete instrument that emplo}S
emains homogeneous with respect to charge, point C, which in turn is positive with respect a linear voltage divider for the accurate measurement or
22, however, the electrochemical convention will be
'ut the region around electrode D is enriched followed in which electromotive force is designated as E. to point B; finally, B is positive with respect potentials.
B
,.
l, " t -'3'.t -
A

'3 -
when R is the net circuit resistance, then
1 1 1 1
loon

loon
VAS V -

+ +
R,
'. +

'.t
I~ +
R.

-'. +
R.
-=-
R R.
+- +-
R2 R3
In a parallel circuit, in contrast to a series
(2-11)
15VL--=:J1J.Jn
~

circuit, it is the conductances that are additive B


FIGURE 2-4 Resistors in parallel.
rather than the resistances. That is, since
I G = l/R, Here, we have the equivalent of two series
VAS 100 !! I
resistances, and
I
I a . proportionality constant. Similarly, G = G. + G2 + G3 (2-12)
I
I RAIt = kAB. Combination of these relation- Just as series resistances form a voltage R = RI + R2• 3 = 9.0 + 13.3 = 22.3 0
200
loon V= VAS X 500 ships with Equation 2-8, yields divider, parallel resistances create a current From Ohm's law, the current I is given by
divider. The fraction of the total current that
RAC AC is present in R. in Figure 2-4 is
VAC = VA/t- = VA/t- (2-9)
loon RAIt AB
I. VIR. l/R. G. Employing Equation 2·8, the voltage V.
A Parallel Circuits
T= VIR = l/R =G" across RI is
·V = IS x 9.0/(9.0 + 13.3) = 6.0 V
Figure 2-4 depicts a parallel dc circuit. Apply-
ing Kirehho/J's current law to point A, we Similarly, the voltage across resistors R2 and
obtain R3 is
10.0 B
C V2 = V3 = V2.] = IS x 13.3/22.3
EXAMPLE

\
For the accompanying circuit, calculate: = It9s =9.0 V
(a) the total resistance: (b) the current draVl:n
Note that the sum of the two voltag\..'Sis 15 V.
AC from the battery; (c) the current present 10
VAS-
VAC· VAS X Ai as demanded by Kirchho/J's voltage law.
Kirchhoff's voltage law gives three independ- each of the resistors; and (d) the potential
I The current in R. is given by
I ent equations. Thus, we may write, for the drop across each of the resistors.
I
loop that contains the battery and R. II = I =0.67 A
~AC
I
V-/.RI =0 The currents through R2 and R] are found
I
0.0 A I from Ohm's law. Thus.
V= I.R.
/2 =9.0/20 = 0.45 A
lbl For the loop containing V and R2,
FIGURE 2-3 Voltage dividers: (a) selector 1., = 9.0140 = 0.22 A
V = 12R2
type and (b) continuously variable type Note that the two currents add to give the nct
(potentiometer). For the loop containing V and R3, R2 and R] are parallel resistances. Thus; current. as required by Kirchho/J's law.
V=/3R3 the resistance R2•3 between points A and B
will be given by Equation 2-11. That is.
We could write additional equations for the Alternating Current
loop containing R. and R2 as well as the loop 1 1 1
In most potentiometers, such as the one --=- +-- The electrical output from transducers of
containing R2 and R3• However, these equa- R2.] 20 40
shown in Figure 2-3b, the resistance is analytical signals often fluctuate pcriodicall~.
tions are not independent of the foregoing
linear-that is, the resistance between one These fluctuations can be represented (as 10
three. Substitution of the three independent
end, A, and any point, C, is directly propor- Figure 2-5) by a plot of th~ insta~taneous
equations into Equation 2-10 yields R2•3 = 13.30
tional to the length, AC, of that portion of the current or potential as a funct.on of tlJ~e. The
resistor. Then RAC = kAC where AC is ex- V V V V We can now reduce the original circuit to the period, t, for the signal is the time reqUired for
pressed in convenient units of length and k is 1=- =- +- +_ following equivalent circuit. the completion of one cycle.
R R. R2 R3
'-- ---------.1
I
The rCc:ipr()!:&1of the period is the fre- The vector rotates at a rate of 2n radians I
quency,/. of the cycle. That is, in the period t; thus, the angular velocity is I
1== 1/'r (2-14)
given by --------.- I
I
I
2n I I
The unit of frequency is the hertz, Hz, which co == - = 2nl (2-15) " -A I
is defined as one cycle per second. t i i
Sille-Wan Clneals. The sinusoidal wave If the vector quantity .is current or voltage,
(Figure 2-5a) is the most frequently en- the instantaneous current i or instantaneous
countered type of periodic electrical signal. A voltage v at time t is given by4 (see Figure
common example is the alternating current 2-6)
produced by rotation of a coil in a magnetic
fickt (as in an electrical generator). Thus, if j = I, sin cot = I, sin 21ift (2-16)
the instantaneous current or voltage or alternatively
produced by a generator is plotted as a func-
tion of time, a sine wave results. v == V, sin cot = V, sin 2nft (2-17)
A pure sine wave is conveniently repre- where I, and v,.
the maximum or peak cur-
sented as a vector of length I, (or V,1 which rent and voltage, are called the amplitude A of
is rotating counterclockwise at a constant an- the sine wave.
gular velocity co.The relationship between the Figure 2-7 shows two sine waves having
vector representation and the sine-wave plot different amplitudes. The two waves are also
is shown in Figure 2-6. out of phose by 90 deg or n/2 radians. The
phase difference is called the plulSe angle.
i
which arises from one vector leading or lag- sin wt=-
ging a second by this amount. A more gener- '.
i" I" sin wI • Ip sin 2.fr
alized equation for a sine wave, then, is
FIGURE 2-6 Relationship between a sine wave of period t and an,tplitude 1"
j == I, sin(cot + 1/1) = I, sin(21ift + 1/1) (2-18)
and the corresponding vector of length 1" rotating at an angular velocity or OJ or
where 1/1 is the phase angle from some refer- a frequency of 1Hz.
ence sine wave. An analogous equation coukt
be written in terms of voltage.
The current or voltage associated with a
sinusoidal current can be expressed in several
ways. The simplest is the peak amplitude I,
(or v,.), which is the maximum instantaneous
current or voltage during a cycle; the peak-
to-peak value. which is 21, or 2V" is also
employed occasionally. The root mean square
or rms current in an ac circuit will produce
the same heating in a resistor as a direct cur-

• In treating currents that change witb time, it is useful to


symbolize the instantJmeoUl current, voltage. or charII'
Time---~·
witb the lower case Ietten I, v. and q. On tbe other hand,
FIGURE 2-5 Examples of periodic signals: capital Ietten are used for steady current, voltage. or FIGURE 2-7 Sine waves with different amplitudes (1" or V,,)
(a) sinusoidal, (b) square wave, (c) ramp, and charII'. or a specificaUydefined variable quantity such as and out of phase by 90 deg or n/2 radians.
(d) sawtooth. a peak voltage current; tbat is, V,and I,.
rent of the same magnitude. Thus, the rms
cunent is important in power calculations
(Equations 2-2 and 2-3). The rms current is Structurally. capacitors and inductors are
given by quite different. A typical capacitor consists of

1,••••=
m = 0.70711'
,(f
a pair of conductors separated by a thin layer
of a dielectric substanee-that is, by an elec-
trical insulator that contains essentially no
mobile, current-carryin& charged species. The
simplest capacitor consists of two sheets of
metal foil separated by a thin film of a dielec-
tric such as air, oil, plastic, mica, paper, cer-
amic, or metal oxide. Except for air and mica
REACTANCE IN capacitors. the two layers of foil plus the insu- ,,-v-;--
ELECTRICAL CIRCUITS lator are usually folded or rolled into a com- I
pact packase and sealed to prevent
Whenever the current in an electrical qircuit atmospheric deterioration.
is increased or decreased, energy is reciuired In contrast, an in4uctor is ordinarily a coil
to c:harse the electric and magnetic fields as- of insulated wire of relatively large diameter
sociated with the flow of charse. As a to minimize resistance. Some inductors are
consequence, there develops a counterforce or
reactanu which tends to counteract the
change. Two types of reactance can be
recognized. namely. capacitance and i,wuct-
ance. When the rate of change in current is
wound around a soft iron core to enhance
their reactance; otl1ers have an air core. The
latter type is sometimes called a choke.
Capacitors are significantly less bulky than
·inductors and, in addition, can be fabricated
i~Ol'>--
\....
low. the reactance of most of the compOnents as part of printed circuits. Thus. to the extent
in a circuit is sufficiently small to be ne- possible, 'capacitors are employed in prefer- +I I / VL
glected. With rapid changes, on the other ence to inductors in electronic circuit design.
hand, circuit elements such as switches, junc-
tions, and resistors may exhibit a detectable
At high frequencies,-however. the reactance of
capacitors may be too small, and inductors
V
reactance. Ordinarily. this type ofreaetance is are used preferentially.
undesirable. and every effort is made to di- Capacitance. In order to describe the
minish its magnitude. properties of a capacitor. it is useful to con-
FIGURE 2-8 Behavior of (a) a series RC circuit and
Capacitance and inductance are often sider the de circuit shown at the top of Figure
(b) a series RL circuit.
deliberately introduced into a circuit with 2-8•• which contains a battery JIj. a resistor R,
capacitors and inductors. These devices pro- and a capacitor C in series. The capacitor is
vide a means for accomplishing such useful symbolized by a pair of parallel lines. A cir-
functions as converting alternating current to cuit of this kind is frequently called a series
direct or the converse, discriminating among RC circuit.
across the plates and prevents the con- the two plates disappears; here. the capacitor
signals of different frequencies, or sepaiating When the switch S is closed to position I,
tinued flow of electrons. When the current is said to be discharged.
ac and de signals. . electrons flow from the negative terminal of
ceases. the capacitor is said to be charged. A useful property of a capacitor is its abil-
In the section that follows, we shalll con- the battery into the lower conductor or plate
If the switch now is moved from 1 to 2, ity to store an electrical charge for a period
sider the properties of inductors and ~paci- ofthe capacitor. Simultaneously. electrons are
electrons will flow from the negatively of time and then to give up the stored charge
tors. The behavior and uses of these two repelled from the upper plate and flow
charged lower plate of the capacitor through as needed. Thus, if S in Figure 2-8a is first
important circuit components frequently par- toward the positive terminal of the battery.
the resistor R to the positive upper plate. held at I until C is charged and is then
allel one another. Thus. it will be instructive This movement constitutes a momentary
Again, this movement constitutes a current moved to a position between I and 2. the ca-
to note their similarities and differences as the current. which decays to zero. however, owing pacitor will remain in a charged condition for
discussion develops. to the potential difference that builds up which decays to zero as the potential between
electric circuit tend to complement one Note that the product RC that appears in
an extended period. Upon moving S to 2, as a counter-potential v when the current first
another. the last three equations has the units of time;
discharge occurs in the same way as it would begins, and tends to oppOse the flow of elec-
if the change from 1 to 2 had been rapid. trons. On the other hand, when the current in
Rate or C..-ent •••• Poteatial Cbaages in since R = vR/i and C = q/vc,
The quantity of electricity, Q, required to a cOnductor ceases, the magnetic field col- an RC Circuit. The rate at which a capacitor
RC = volts coulombs
charge a capacitor fully depends upon the lapses; this process causes the development of is charged or discharged is ~te. Consider,
coulombs/seconds x volts
area of the plates, their shape, the spacing a momentary potential which acts to continue for example, the circuit shown in Figure 2-8a.
between them, and the dielectric constant for the current. From Kirchhoffs voltage law, we know that = seconds
the material that separates them. In addition, The magnitude of the potential v that at any instant after the switch is moved to
The term RC is called the time constant for
the charge, Q, is directly proportional to the develops during the increase or decrease in position I, the sum of the voltage across C
the circuit.
applied voltage. That is, current is found to be directly proportional to and R (vc and VR) must equal the input volt-
The following example illustrates the use
the rate of current change di/dt. That is, age~. Thus,
Q = CV (2-20) of the three equations that were just derived.
di Y; = Vt + VR (2-24)
When V is the applied potential in volts and v = -L- (2-23) EXAMPLE
dt Because Y; is constant; the increase in Vc that
Q is the quantity of charge in coulombs, the Values for the components in Figure 2-8a
proportionality constant C is the capacitance Here, the negative sign indicates that the accompanies the charging of the capacitor are ~ = 10 V, R = 1000 n.
C = 1.00 pF or
of a capacitor in farads, F. One farad, then, induced potential acts to oppose the change must be exactly offset "y a decrease in VR • 1.00 x 10-6 F. Calculate: (a) the time con-
corresponds to one coulomb of charge per in current. Substitution of Equations 2-4 and 2-20 stant for the circuit; and (b) i, vc, and VR after
applied volt. Most of the capacitors used in The proportionality constant L in Equa- into this equation gives, upon rearrangement, two-time constants (t = 2RC) have elapsed.
electronic circuitry have capacitances in the tion 2-23 is termed the inductance of the (a) Time constant =
RC =
1000 x 1.00 x
microfarad (10-6 F) to picofarad (10-12 F) conductor; it has the units of henrys, H. One Y;=~+iR 10-6 = 1.00 X 10-3 s or 1.00 ms
ranges. henry of inductance produces a counter- (b) Substituting t = 2.00 ens in Equation
Capacitance is important in ac circuits, potential of one volt when the rate of change Differentiating with ~pect to time t yields 2-27 reveals
particularly because a voltage that varies with of current is one ampere per second. Induc-
time gives rise to a time-varying charge-that tors employed in electronic circuits have 0= dq/~t + R ~ . (2-26) . 10.0 -200/100
C dt 1= lOOOe . .
is, a current. This behavior is seen by differen- inductances that range from a few pH
tiating Equation 2-20 to give (microhenry) to several H or more. Here again, we have used lower case letters to = 1.35 X 10-3 or 1.35 mA
Figure 2-8b shows a series RL circuit, represent instantaneous charge and current.
dq = Cdv (2-21) which contains a battery ~,a resistor R, and As noted earlier, dq/dt = i. Substituting - We find from Equation 2-28 that
dt dt an inductor L connected in series. The magni- this expression into Equation 2-26 yields, VR = 10.0e-2.00/1.00 = 1.35 V
By definition (Equation 2-1 ~ the current i is tude of L depends upon the number of turns upon rearrangement,
in the wire coil. and by substituting into Equation 2-29
the rate of change of charge; that is, dq/dt = i. di dt
Thus, As was pointed out earlier, a capacitor -= - RC
V(" = 10.0 (I - e-2.0011.00) = 8.65 V
dv stores energy as an electric field across a
i= C dielectric; an inductor, on the other hand, Integration between the limits of the initial
dt The center illustration in figure 2-8a
stores energy as a magnetic field surrounding current link and i gives
It is important to note that the current in a shows the changes in i, 11K, and Vc that occur
a conductor. The electric field in the capacitor
capacitor is zero when the voltage is time i= linite-·/Rc (2-27) during the charging cycle of an RC circuit.
is proportional to the applied voltage; the
independent-that is, for a direct current. Be- These plots were based upon the data given
magnetic field in the inductor is proportional In order to obtain a relationship between
cause a direct current refers to a steady state, in the example just considered. Note that VR
to the current that exists in the inductor. the instantaneous voltage across the resistor,
the initial transient current that charges the and i assume their maximum values the in-
The difference between a capacitor and an Ohm's law is emplo)led to replace i and lini'
condenser is of no significance in considering stant the switch in Figure 2-8a is moved to 1.
inductor can also be seen by comparing in Equation 2-27. Th~s,
the overall effect of a capacitor on a current At the same instant, on the other hand, the
Equations 2-22 and 2-23. The former indi-
that has a de component. cates that a change in potential across a capac' VR = Y;e-·/RC (2-28) voltage across the capacitor incr~ rapidly
Inductance. It is found experimentally that from zero and ultimately approaches a con-
itor results in a current; the latter shows that Substitution of this expression into Equation
a magnetic field surrounds any conductor as stant value. For practical purpOses, a capaci-
a change in current through an inductor 2-24 yields, upon rearrangement,
it carries an electric current. The work tor is considered to be fully charged after
causes the development of a potential. Thus,
required to establish this field manifests itself Vc = Y;(1 - e-·/RC) (2-29) 5RCs have elapsed. At this point the current
the functions of the two components in an
will have decayed to less than 1 % of its initial It is useful to compare the behavior of RC
value (e-5 = 0.0067 ~ 0.01). and RL circuits during a variation in signaL
When the switch in Figure 2-8a is moved The plots in Figure 2-8 illustrate that the two
to position 2, the battery is removed from the reactances are alike in the sense that both
circuit and the capacitor becomes a source of show a potential change which is out of phase
R "
VR
15kn ~ \, >
current. The flow of charge, however, will be
in the opposite direction from what it was
previously. Thus,
dqldt = -i
with the current. Note again the complemen-
tary behavior of the two; for an inductor, the
voltage leads the current, while for a capaci-
tor, the reverse is the case.
2OV"" v,

-+- Vc
C
O.OO8I'F
~
a
-
0

-0.5
\
1,\
0.75 kHz"
,
"
o E
~

The initial potential will be that of the Response of


battery. That is, Series RC and RL
VC=V; Circuits to Sinusoidal Inputs

Employing these equations and proceeding as In the sections that follow, the response of
series RC and RL circuits to a sinusoidal ac
in the earlier derivation, we find that for the
discharge cycle voltage signal will be considered. The input
signal is described by Equation 2-17; that is,
. Vc' -t/RC
1= -lie (2-30) v. = v" sin cot = V" sin 2nft (2-35)
Voltage, Current, and Phue Relationship
VR = - Vce-t/RC (2-31) for Series RC Circuit. Application of Kirch-
and holrs voltage law to the circuit shown in
Vc = Vce-t/RC
Figure 2-9a leads to the expression
(2-32)
v. = Vc + VR = V" sin cot
The bottom plot of Figure 2-8a shows how
these variables change with time. Substitution of Equations 2-20 and 2-4 yields
It is important to note that in each cycle, FIGURE 2-9 Current, voltage, and phase relationships for an RC circuit:
the change in voltage across the capacitor is v" sin cot = ~ + Ri (a) Circuit, (b) currents at 0.75 and 7.5 kHz, (c) voltages at 0.75 kHz, and
out of phDse with and lags behind that of the (d) voltages at 7.5 kHz.
current and the potential across the resistor. Differentiating and replacing dqldt with
Rate of Current and Potential Change gives
Across an RL Circuit. Equation 2-23 and
techniques similar to those in the previous cov" cos cot = Ci + Rdidi The peak current occurs whenever the cies and capacitance, on the other hand, ep
section can be used to derive a set of expres- sin(wt + ep) is unity. Thus, becomes negligible and, for all practical pur-
sions for the RL circuit shown in Figure 2-8b The solution of the differential equation can poses, the current and input voltage are in
that are analogous to Equations 2-27 through be shown to be5 V phase. Under these circumstances, (llwe) be-
2-32. For example, when the switch is closed
I - I' (2-38)
, - JR2 + (1/coC)2 comes negligible with respect to R and Equa-
to position 1, i= JR 2
+
~
l/coe)
2 sin(cot + ep) (2-36) tion 2-38 reverts to Ohm's law.
VR = V;(1 - e-·R1L) (2-33) A comparison of Equations 2-36 and 2-35
where the phase angle ep is given by reveals that the current in a series RC circuit
1 is often not in phase with the input voltage EXAMPLE
tan ep=-- signaL This condition is likely to prevail AssuUJe the components in the RC circuit
coRC
whenever the frequency (or the capacitance) shown in Figure 2-9a have values of
where LIR is the time constant for the circuit. is small; then, tan ep and thus ep (Equation V" = 20V,R = 1.5 x 104n,and C= 0.OO80pF.
These relationships for a typical RL circuit , J. J. Brophy, Basic Electronics/or Scientists. New York: 2-37) becomes significant with respect to cot (a) Calculate the peak current (1) if
are shown in Figure 2-8b. McGraw-Hil~ 1966. pp. 57-59. in Equation 2-36. At sufficiently high frequen- f = 0.15 kHz, (2) f = 75 kHz, and (3) with the
capacitor removed from the circuit. (b) Calcu- and at 75 kHz
late the phase angles between the voltage and
2.65 x W
the current at the two frequencies. arc tan q, = arc tan 1.5 x 104
(a) (1)
= arc tan 0.0177 = 1.0 deg R
1.1 1 «
E
we = 2~jC = 2n x 0.75 x 103 x 8.0 X 10-9
Figure 2-9b, c, and d shows the instanta- 20V'" v, r::

neous current, voltage, and phase relationships ~


= 2.65 X 104 n U
:>
when the circuit characteristics are the same L
Note that the quantity l/2njC has the dimen- as those employed in the example. The time
sions of ohms. That is, scales on the abscissas differ by a factor of
1 1 100' to accommodate the two frequencies.
jC=s-I·C·V-I From Figure 2-9b and the example, it is evi-
dent that at the lower frequency, the current
But the number of coulombs C is equal to the is significantly smalIer than at the higher be-
product of the current in amperes and the cause of the greater reactance of the capacitor
time in seconds. Thus, at the lower frequency. This larger reactance
is also reflected in the large phase difference
_1_ 1_!_n between the current and the input voltage
jC-s-I·A·s·V-1- A- >
shown in Figure 2-9c (q, = 60.5 deg). At
Employing Equation 2-38, we write 75 kHz, this difference becomes considerably f
-5
0
sm~ler (Figure 2-9d). >
1 20 Figures 2-9c and 2-9d show the relation-
"= J(1.5 x W)2 + (2.65 x 104)2 ship between the input voltages and the volt-
= 6.6 x 10-4 A age· drops across the capacitor and the
resistor. At the lower frequency, the drop ~ ~
(2) across the capacitor is large with respect to FIG UR E 2-10 Current, voltage, and phase relationships in an RL circuit:
that across the resistor. In contrast, at (a) Circuit, (b) currents at 20 and 200 kHz, (c) voltages at 200 kHz, and
1 1
75 kHz, lie is small, indicating little reaction (d) voltages at 20 kHz.
2njC = 2n x 75 x 103 x 8.0 X 10-9
between the current and the capacitor. At
= 2.65 X 102 n frequencies greater than 1 MHz, essentialIy
no interaction would occur, and the arrange-
ment would behave as a purely resistive
1- 20 circuit. in an inductor opposes the current; thus the The peak current occurs where R sin (rot + q,)
" - J(1.5 x W)Z + (2.65 x W? Note also the phase relationships among polarity of Ri and L di/dt must be the same. is equal to unity, or
= 1.33 x 10-3 A t:•• vc, and VR shown in Figure 2-9c. Integration of this equation yields6
I _ V"
(3) In the absence of C
Voltage, Current, and Phase Relationships
for Series RL Circuits. Applying Kirchhoff's
.=
I J R 2 +V" (roL) 2 SID A.)
. (rot + 'I' (2 - 39) ,,- JR 2 + (roL)2

20 -3
voltage law to the circuit in Figure 2-10 gives Figure 2-10 shows the relationships among
I" = 1.5 X 104 = 1.33 x 10 A currents, voltages, and phases for an RL
v. = VR + VL = V" sin rot
circuit. Comparison with Figure 2-9 again
(b) Employing Equation 2-37, we find at SUb~tituting Equations. 2-4 and 2-23 yields roL
tanq,=- reveals the complementary nature of the two
0.75 kHz. R types of reactive components. For inductors,
V, sin rot = Ri + L di/dt
2.65 x W reaction to the current occurs at high
tan q, = 1.5 X 104 = 1.77 The second term on the right-hand side of the frequencies but tends to disappear at low.
equation is positive because the minus sign in Here, the current lags the input potential
• J. J. Brophy. Basic Eleclronicsfor Scientists. New York:
q, = 60.5 deg Equation 2-23 means that the induced voltage McGraw-Hili. 1966. pp. 67-69. rather than leading it.
Capacitative .nd Inductive Reactance; Im- cuits containing capacitive and inductive ele- ----
pedance. An examination of Equations 2-41
and 2-38 shows a similarity to Ohm's law,
with the denominator terms being an expres-
sion of the impedance exerted by the circuit
to the flow of electricity. Note that at high
ments. A convenient way of visualizing these
effects is by means of vector diagrams.
Vector Diagrams for Reactive Circuits.
Because the voltage lags the current by
90 deg in a pure capacitance, it is convenient
XL

0 ~
z
R

Za .JR2+xL2
XL
:
I
I

frequencies, where l/wC ~ R, Equation 2-38 to let q, equal -90 deg for a capacitive reac- ~=ilfCtanR

reverts to Ohm's law; similarly, when tance. The phase angle for a pure inductive
wL ~ R, Equation 2-41 behaves in the same circuit is +90 deg .. For a pure resistive
way. circuit, q, will be equal to 0 deg. The relation-
The term l/wC in the denominator of ship ainong Xc, XL' and R can then be rep-
Equation 2-38 is termed the capacitive reac- resented vectorially as shown in Figure 2-11.
tance Xc, where As indicated in Figure 2-11c, the im-
pedance of a series circuit containing a
resistor, an inductor, and a capacitor is
Similarly, the inductive reactance XL is defined determined by the relationship
as (see Equation 2-41)
Z = JR2 + (XL - Xc>2 (2-46)
XL = wL = 27tjL (2-43) z· .JR' +(XL -Xci'
Because the outputs of the capacitor and (X, - Xci
o :lIE arc tan -R--
The impedance Z of the two circuits under inductor are 180 deg out of phase, their
discussion is a measure of the total effect of combined effect is determined from the differ-
resistance and reactance and is given by the ence of their reactances.
denominators of Equations 2-38 and 2-41. FIGURE 2-11 Vector diagrams for series circuits:
Thus, for the RC circuit EXAMPLE (a) RC circuit, (b) RL circuit, (c) series RLC circuit.
For the following circuit, calculate the
Z=JR2 +X~ peak current and voltage drops across the
and for the RL circuit three components. ring at different times. The sum .of the instan- Since the voltage drop across the resistor is in
Z = JR2 + xl (2-45) taneous voltages, however, would add up to phase with the current,
10V.
Substitution of Equations 2-42 and 2-44 High-Pass .nd Low-Pass Fikers. Series RC
1 = (VI').
, R
into Equation 2-38 yields and RL circuits are often used as filters to
attenuate high-frequency signals while pas- The ratio of the peak output to the peak
1 = V"
, Z sing low-frequency components (a low-pass input voltage is obtained by dividing the first
filter) or, alternatively, to reduce low- equation by the second and rearranging.
A similar result is obtained when Equations frequency components while passing the high Thus,
2-43 and 2-45 are substituted into Equation Z = J(SO)2 + (40 - 2W = 53.8 n (a high-pass filter). Figure 2-12 shows how
2-41.
series RC and RL circuits can be arranged to
In one sense, the capacitive and inductive 1" = 10 V/53.8 n = 0.186 A
give high- and low-pass filters. In each case.
reactances behave in a manner similar to that VR = 0.186 x SO = 9.3 V the input and output are indicated as the volt-
of a resistor in a circuit-that is, they tend to
Vc = 0.186 x 20 = 3.7 V ~es (Vp)i and (Vp) •. A plot of this ratio as a function of frequency
impede the flow of electrons. They differ in ; In order to employ an RC circuit as a
two major ways from resistance, however. is shown in Figure 2-13a; here, a resistance of
VL = 0.186 x 40 = 7.4 V high-pass filter, the' output voltage is taken
First, they are frequency dependent; second, 1.0 x 10· n and a capacitance of 0.10 pF was
across the resistor R. The peak current in this
they cause the current and voltage to differ in Note that the sum of the three voltages employed. Note that frequencies below
circuit is given by Equation 2-38. That is,
phase. As a consequence of the latter, the (20.4) in the example exceeds the source 50 Hz have been largely removed from the
phase angle must always be taken into voltage. This situation is possible because the I _ (Vp); input signal. It should also be noted that be-
account in considering the behavior of cir- voltages are out of phase, with peaks occur- I' - JR2 + (l/wC)2 cause the input and output voltages are out of
resistor -behavior just opposite of that of the energy stored in the magnetic field of the
RC circuit. Curves similar to Figure 2-13 are inductor during the other. Thus, during a
obtaincd for RL filters. one-half cycle, the energy of the capacitor
Low- and high-pass filters are of great im- forces the current through the inductor; in
portance in the design of electronic cirCUits. the other half cycle, the reverse is the case. In
~-----~ principle, a current induced in a closed reso-
Resonant Circuits nant circuit would continue indefinitely except
for the loss resulting from resistance in the
A resonant or RLC circuit consists of a
leads and inductor wire.
resistor, a capacitor, and an inductor ar-
The resonant frequency I. can be readily
ranged in series or parallel, as shown in
calculated from Equations 2-42 and 2-43.
Figure 2-14.
That is, whenf=f., XL = Xc, and
Series Resonant Filters. The impedance of
the resonant circuit shown in Figure 2-14a is 1
given by Equation 2-46. Note that the im- 2nf.C = 2nf.L
pedance of a series inductor and capacitor
is the difference between their reactances and Upon rearrangement, it is found that
that the net reactance of the combination is
1
zero when the two are identical. That is, the
1.= 21tJfC
FIGURE 2-12 Filter circuits: (a) High- The follQwing example will show some of the
pass RC filter, (b) low-pass RC filter, (c) high- 1.0 (bl properties of a series resonant circuit.
pass RL filter, and (d) low-pass RL filter. FIGURE 2-14 Resonant circuits employed i
O.B
as filters: (a) series circuit and (b) parallel EXAMPLE
~ 0.6
~ circuit. Assume the following values for the com-
~
phase, the peak voltages will occur at differ- :: 0." ponents of the circuit in Figure 2-14a: (Vp)i =
15.0 V (peak voltage), L= 100 mH, R = 20 n,
ent times. 0.2
and C = 0200 JLF. (a) Calculate the peak cur-
For the low-pass filter shown in Figure 0.0
only impedance in the circuit is that of the rent at the resonance frequency and at a
2-12b, we may write 1 100
resistor or, in its absence, the resistance of frequency 75 Hz greater than the resonance
Frequency. Hz
(Vp). = IpXc the inductor coil and ·the other wiring. This frequency. (b) Calculate the peak potentials
(al
behavior becomes understandable when it is across the resistor, inductor, and capacitor at
Substituting Equation 2-42 gives
recalled that in a series RC circuit, the poten- the resonant frequency.
(Vp). = Ip/(roC) tials across the capacitor and the inductor are (a) We obtain the resonant frequency with
O.B
180 deg out of phase (see the vector diagrams Equation 2-49. Thus,
Multiplying by Equation 2-38 and rearrang-
ing yields
~ 0.6 in Figure 2-11). Thus, if Xc and XL are alike,
"i
there is no net potential drop across the pair. 1
;0- 0.4
1.;= 2nJl00 x 10 x 0.2 x 10
(Vp)., 1 1 Electricity continues to flow, however; there- 3 6

(VP)i = roCJR2 + (l/roC)2 = j(roCR)2 + 1 fore, the net reactance for the combination is
= 1125 Hz
(2-48) zero. Also, when XL and Xc are not identical,
their net reactance is simply the difference be- By defidition, XL = Xc at!.; therefore, Equa-
Figure 2-13b was obtained with this equation. Frequency. Hz
tween the two. tion 2-46 becomes
As shown in Figure 2-12, RL circuits can (b) The condition for resonance is
also be employed as filters. Note, however, FIGURE 2-13 Frequency response of (a) the
that the high-pass filter employs the potential XL= Xc
high-pass filter shown in Figure 2-118 and (b) the
across the reactive element while the low-pass low-pass filter shown in Figure 2-12b; R = Here, the energy stored in the capacitor
filter employs the potential across the 1.0 X 104 nand C = 0.10 JLF. during one half cycle is exactly equal to the
To calculate I, at 1200 Hz, we substitute ing upon the relationship between the widtp
Equations 2-42 and 2-43 into Equation 2-46. of the pulse and the time constant for the
Thus, circuit. These effects are illustrated in Figure
Z = JR 2 + [27tjL - (1/27tfC)j2 2-17 where the input is a square wave having
a pulse width of 1",' seconds. The second
= J202 + [27t x 1200 x 100 x 10
column shows the variation in capacitor
- 1/(27t x 1200 x 0.200 x lO-ti)j2 potential as a function of time, while the third
column shows the change in resistor potential
= J400 + (754 - 663)2 = 93 0
at the same times. In the top set of plots
and I, = 15.0/93 = 0.16 A. (Figure 2-17a~ the time constant of the circuit
(b) At f. = 1125 Hz, we have found that is much greater than the input pulse width.
I,= 0.75 A. The potentials across the Under these circumstances, the capacitor can
resistor, capacitor, and inductor (V,)Il' (V,)L, become only partially charged during each
and (J-;,)c are pulse. It then discharges as the input potential
returns to zero; a sawtooth output results.
(V')ll = 0.75 x 20 = 15.0 V 1050 1100
The output of the resistor under these circum-
Frequency, Hz . Frequenc:y. Hz
(V,)L = I,XL FIGURE 2-15 Frequency response of a stances rises instantaneously to a maximum
FIGURE 2-16 Ratio of output to input value and then decreases essentially linearly
= 0.75 X 27t x 1125 x 100 x 10-3 series resonant circuit; R = 20Q,L = l00mH, voltage for the series resonant filter; L =
=
C 0.2 IlF, and (J-;,), = 15.0 V. 100 mH, C = 0.20 IlF, and (v,,)i = 15 V.
during the pulse lifetime.
= 530 V The bottom set of graphs (Figure 2-17c)
Since XL = Xc at resonance, illustrates the two outputs when the time con-
stant of the circuit is much shorter than the
f If the output of the circuit shown in Figure filter (Equation 2-46). Note that the im-
pulse width. Here, the charge on the capacitor
2-14a is taken across the inductor or capaci- pedance in the latter circuit is a minimum at
rises rapidly and approaches full charge near
Part (b) of this example shows that, at tor, a potential is obtained which is several resonance, when XL = Xc. In contrast, the the end of the pulse. As a consequence, the
resonance, the peak voltage across the re- times larger than the input potential (see part impedance for the parallel circuit at reso-
potential across the resistor rapidly decreases
sistor is the potential of the source; on the b of the example). Figure 2-16 shows a plot of nance is a maximum and in principle is infinite.
to zero after its initial rise. When V;goes to
other hand, the potentials across the Inductor the ratio of the peak voltage across the induc- Consequently, a maximum voltage drop
zero, the capacitor discharges immediately;
and capacitor are over 35 times greater than tor to the peak input voltage as a function of across (or a minimum current through) the the output across the resistor peaks in a nega-
the input potential. It must be realized, frequency. A similar plot is obtained if the parallel reactance is found at resonance. With
tive direction and then quickly approaches
however, that these peak potentials do not inductor potential is replaced by the capaci- both parallel and series circuits at resonance,
zero.
occur simultaneously. One lags the current by tor potential. a small initial signal causes resonance in These various output wave forms find
90 deg and the other leads it by a similar The upper curve in Figure 2-16 was ob- which electricity is carried back and forth be-
applications in electronic circuitry. The
amount. Thus, the instantaneous potentials tained by substituting a 10-0 resistor for the tween the capacitor and the inductor. But cur- sharply peaked voltage output shown in
across the capacitor and inductor cancel, and 20-0 resistor employed in the example. rent from the source through the reactance is Figure 2-17c is particularly important in
the potential drop across the resistor is then Parallel Resonant Filters. Figure 2-14b minimal. timing and trigger circuits.
equal to the input potential. Clearly, in a cir- shows a typical parallel resonant circuit. The parallel circuit, sometimes called a
cuit of; this type, the capacitor and inductor Again, the condition of resonance is that tank circuit, is widely used as for tuning radio
may have to withstand considerably larger Xc = XL and the resonant frequency is given or television circuits. Tuning is ordinarily ac- SIMPLE
potenti;als than the amplitude of the input by Equation 2-49. complished by adjusting a variable capacitor ELECTRICAL MEASUREMENTS
voltage would seem to indicate. The impedance of the parallel circuit is until resonance is achieved.
Figure 2-15, which was obtained for the given by This section describes selected methods for
circuit shown in the example, demonstrates Behavior of RC
that the output of a series resonant circuit is a Z = JR2 + (XC-XL
XLXC )2 (2-50) Circuits with Pulsed Inputs
the measurement of current, voltage, and
resistance. More sophisticated methods for
narrow band of frequencies, the maximum of measuring these and other electrical proper-
When a pulsed input is applied to an RC
which depends upon the values chosen for L It is of interest to compare this equation with ties will be considered in Chapter 3 as well as
circuit, the voltage outputs across the capaci-
and C. the equation for the impedance of the series in later chapters.
tor and resistor take various forms, depend-
Meter
The Ayrton Shunt. The Ayrton shunt,

f1o-------AJV:J shown in Figure 2-19, is often employed to


vary the range of a galvanometer. The
example that follows demonstrates how the
'"
:\, '-

resistors for a shunt can be chosen.


~
..!!..'Aft
Shunt
EXAMPLE R, R. ·R, R.
3
Assume that the meter in Figure 2-19 reg- 2 4 t '.
isters full scale with a current of SO JlA; its
internal resistance is 3000 n. Derive values
for the four resistors such that the meter
(b) ranges will be 0.1, 1, 10, and 100 mA.
RCO!!T. For each setting of the contact, the circuit
is equivalent to two resistances in parallel. FIGURE 2-19 A current meter with an
One resistance is made up of the meter and Ayrton shunt.
the resistors to the left of the contact in
(el T+l .JnLJnLJnL T+ !7l
J
:Tl iT1
LJ U L T+~' I -, I -, I
Figure 2-19; the other consists of the remain-

t ing resistor to the right of the contact. The


Vi 0 Vc 0
RC~T.
1.. 1.. _ 1.._
V" 0 -
potential across parallel resistances is, of We may also write, from Kirchholfs current
o course, the same. Thus, law
--Time- 0 --T~_ o --Time---"

IM(RM + Rd = IRRR
I", = 1M + IR
FIGURE 2-17 Output signals VR and Vc for pulsed input signal J-l; (a) time constant ~ pulse
width Tp; (b) time constant ~ pulse width; (c) time co~tant <l! pulse width. which can be combined with the first equa-
where RM is the resistance of the meter, R,. is tion to give, after rearrangement,
the resistance of the resistors to the left of the
contact, and RR is the resistance to the right. I", RM + RL + RR R", + Rr
1M = RR RR
G•• vanomet ••.• cause rotation of the coil and deflection of the
attached pointer; the deflection i~directly where Rr is the total resistance of the shunt
The classical methods for measuring direct proportional to the current present in the (RL + RR)'
current, voltage, and resistance employ a coil. Pennlnent With the contact in position 1, RL = 0 and
galvanometer. This device, which was in- Meters with D'Arsonval movements are magnet \ RR = Rr; here, the greatest fraction of the
vented nearly a century ago, still finds wide- generally called ammeters, milliammeters, or current will pass through the meter. There-
spread use in the laboratory. It is based upon microammeters, depending upon the current fore, setting 1 corresponds to the lowest cur-
the current-induced motion of a coil sus- range they have been designed to measure. rent range, where the full meter reading
pended in a fixed magnetic field. This arrange- Their accuracies vary from 0.5 to 3 % of full (/",= SO JlA) should correspond to 0.1 mA
ment is called a D'Arsonval movement or scale, depending upon the quality of the (Ix = 0.1 mAl. Substituting these values into
coil. meter. the derived equation yields
Figure 2-18 shows construction details of a More sensitive galvanometers are obtained 0.1 x 10- 3 A 3000 + 0 + RR
typical D'Arsonval meter. The current to be by suspending the coil between the poles of a SO X 10-6 A RR
measured passes through a rectangular coil ma~et by a fine vertical filament that has
wrapped about a cylindrical soft iron core very; low resistance to rotation. A small RR = Rr = 3000 n
that pivots between a pair of jeweled bear- mirror is attached to the filament; a light
ings; the coil is mounted in the air space be- beam, reflected ofT the mirror to a scale, Substituting this value for Rr in the work-
tween the pole pieces of a permanent magnet. detects and measures the extent of rotation
FIGURE 2-18 Current meter. ing equation gives
The current-dependent magnetic field that (Taken from R. J. Smith, Circuits, De-
during current passage. Galvanometers can
vices, and 51'stems. New York: Wiley, Ix R", + Rr 3000 + 3000
develops in the coil interacts with the per- be constructed that will detect currents as I", = RR RR
manent magnetic field in such a way as to small as 10-10 A. 1976. With permission.)
VAB across the resistor Rz is obtained by con- obtained. Here, it is desired to determine the resistance to total resistance of the remaining
. necting the meter at points A and B. Under current I in the resistor RAB when the switch components in the system .
RR = 6000 x IMII;" these circumstances, is thrown to position 1. Oearly, the error associated with this
From Ohm's law, this current is given by measurement can be minimized by choosing a
6 0.300 VAB = IMRM
= 6000 X 50 X 10- II" = -1-. Jr. Jr.s meter having the lowest possible resistance.
" . where RM is the resistance of the meter (and 1= S Alternatively, the meter can be replaced by a
any resistors placed in series with it) and 1M is R1 + Rz + Rs = Rr small precision resistor; the potential drop
the current measured by the meter. Since RM where Vs is the potential of the source, Rs is across this resistor can then be measured with
is a constant, the meter scale can be cal- its internal resistance, and Rr is the total re- a high resistance meter, and the current can
Setting I" ibrated in volts rather than amperes. sistance of the circuit. be calculated from Ohm's law.
Effect of Meter Resistance on Current In order to measure the current, however, Often, a current meter or a precision re-
1 0.1 X 10-3 3000 = (R, + R2 + R) + R.) Measurements. The coil of a meter or galva- sistor is made a permanent part of an instru-
2 1x 10- 3 300 = (R2 + R) + R.) the meter must be brought into the circuit by
nometer offers resistance to the flo~ of electric- moving the switch from position I to 2. ment; under these circumstances, a somewhat
3 10 x 10- 3 30= (R) + R.)
ity, and this resistance will reduce the Clearly, the measured current 1M will differ smaller current is obtained, but its magnitude
4 100 X 10-3 3 = R.
magnitude of the current being· measured; from I and will be given by is given directly by the meter.
thus, an error is introduced by t~e measure- Effect of Meter Resistauce on Voltage
Thus, R~ = 3 n, R3 = (30 - 3) = 27 n, Rz = ment process itself. This situation is not pecul- Vs Vs Meaurements. As shown in the following
III = ------- ---
(300 - 30) = 2700, and R1 = (3000 - 300) = iar to current measurements. In fact, it is a R1 + Rz + Rs + RM Rr +. RM example, the measurement of voltage by the
27000. simple example of a general limitation to any circuit in Figure 2-20b may also alter the
The relative error associated with the
Meaurement of Current and Voltage. Fi- physical measurement. That is, the process of system in such a way as to create a significant
presence of the meter is given by
gure 2-20 presents circuit diagrams showing measurement inevitably disturbs the system of error.
how a galvanometer can be employed to interest so that the quantity actually reI error = (IM - 1)/1
measure current and voltage in a circuit. Note measured differs from its value ~rior to the EXAMPLE
that the meter is placed in series with the re- measurement. This type of error cim never be Substitution of the relationships for I and 1M The voltage drop VAB across the resistor
mainder of the circuit for a current measure- completely eliminated; often, however, it can yields, upon rearrangement, Rz in Figure 2-20b is to be measured by
ment (Figure 2-208). In contrast, a voltage be reduced to insignificant proportions. means of a meter having a resistance of
measurement is obtained by placing the meter The circuit shown in Figure 2-208 can be
reI error = - RM I(Rr + RM)
50.0 1e0. (a) Calculate the relative error asso-
across or in parallel with the potential to be used to illustrate how a simple measurement The data in Table 2-1 illustrate the magnitude ciated with the measurement. (b) Repeat the
measured. Thus, in Figure 2-20b, the voltage can perturb a system and thus alter the result of the disturbance to the system by the mea- calculations assuming the meter resistance is
surement process for various ratios of meter still 50.0 kn, but that all other resistances

Vs
12.GV l00kn

IIII
Rs.,00n R,
A
TABLE 2-1 EFFECT OF METER RESISTANCE ON CURRENT
MEASUREMENTS·

Meter Resistance, Measured Current,

S 8
R", kn I". mA
2
meter absent 0.00 0.100 o
I om 0.099 -0.8
10 0.08 0.092 -7.6
w ~ 50 0.42 0.071 -29
100 0.83 0.055 -45
FIGURE 2-20 Circuits for measuring (a) current I and
(b) voltage VAS.
have values that are 1/10 that shown in the the second part of the example, however, the to 1 mA in the initial adjustment, we may
figure. resistance of the potential source plays an im- write
(a) With the switch S open so that the portant part in determining the meter resis- 1.5 = 11(RM + Rv) = 1.00 X 1O-3(RM + Rv)
meter is out of the system, the potential drop tance required for a given accuracy. That is, as Device
V.u can be obtained by use of Equation 2-8 the source resistance increases, so also must (RM + Rv) = 1500 n to give
known" V.
(p.9) -. the meter resistance if accuracy is to be main-
tained. This relationship becomes particularly FIGURE 2-22 Block diagram for a com-
V = 12.0 x 20.0 _ parison measurement system.
significant in the determination of pH by Rx= (~- 1)1500
AB 100 + 20.0 + 0.100 - 2.00 V
measurement of the potential of a cell con-
taining a glass electrode. Here, the resistance 3
When the switch is closed, a system of two =(1.00;110- -1)1500 As shown in Figure 2-22, a typical compar-
parallel resistors is created whose net resis- of t~ system may be 100 megohms or more.
Thus; a potential measuring device with an ison instrument consists of three components.
tance RAB can be found by substitution into
eno~ous internal resistance is required. Clearly, the relationship between the One of these is a null detector, which indi-
Equation 2-11 (p. 11). Thus,
Resistance Measurements. Figure 2-21 gives measured current and the resistance is cates the inequality or equality of the two sig-
1 1 1 I 1 a circuit for the measurement of resistance nonlinear. nals. The second component is a reference
-=-+-=-+-
RAB R R 20.0 50.0 standard signal against which the unknown
1 AI with; a D'Arsonval meter. The source is
usually a 1.5-V dry cell. To employ the signal is compared. Finally, the instrument
RAB = 14.3 ill
circuit, the switch is placed in position I and
Comparison M ••••• rementa
contains a device for continuously attenuat-
The potential drop VAl, sensed by the meter, Comparison or Null Measurements. Instru- ing one of the two signals in such a way that
the meter is adjusted to full scale by means of
is now ments based upon comparison of the system the percent reduction is exactly known. In
the v;uiable resistor Rv • From Ohm's law, we
may write of interest with a standard are widely Figure 2-22, attenuation is performed on the
v. = 12.0 x 14.3 _ employed for chemical measurements; such reference signal; often, however, it is the un-
AI 100 + 14.3 + 0.100 - 1.50 V 1.5 = 11(RM + Rv) devices are called null instruments. Null in- known signal that is varied. Furthermore,
Therefore, struments are generally more accurate and attenuation may be performed mechanically
With: the switch moved to position 2, the cur-
precise than direct-reading instruments, in rather than electrically. An example is a var-
1.50 - 2.00 rent decreases to 11 because of the added re-
part because a null measurement generally iable diaphragm that reduces the power of a
re I error = ---- x 100 = -25% sistance of the unknown Rx• Thus,
2.00 causes less disturbance to the system being beam of light used for photometric analysis.
1.5 = 12(RAt + Rv + Rx)- studied. Moreover, the readout devices Potentiometers. The potentiometer is a
(b) Proceeding as in (a~ we find
employed can often be considerably more null instrument that permits accurate measure-
Division of the two equations and rearrange-
V = 12.0 x 2.00 _ rugged and less subject to environmental ment of potentials while drawing a minimum
ment yields
AB 10.0 + 2.00 + 0.0100 - 2.00 V effects than a direct-reading device. current from the source under study. A typi-.

1 1 1 Rx=(~ -1)(RM+Rv)
Ii= 2.0 + 50.0
The value of (RAt + Rv) is determined by
the range of the meter. For example, if the TABLE 2-2 EFFECT OF METER RESISTANCE ON POTENTIAL
R = 1.92 kCl meter range is 0 to I mA and the meter is set MEASUREMENT-
V. = 12.0 x 1.92 _
M 10.0 + 1.92 + 0.0100 - 1.93 V Meter Resistance, Measured Voltage, Relative Error,

I 1.93 - 2.00 RM,kCl VM. V %


re error = 2.00 x 100 = -3.5%
10 0.75 -62
SO 1.50 -25
Table 2-i shows the effect of meter resis- 1.935
500 -32
tance on a potential measurement. Note that, 1 X 103 1.967 -1.6
in contrast to a current measurement the 1 X 104 1.997 -02
accuracy of a potential measuremen~ in- FIGURE 2-21 A circuit for measurement
creases with meter resistance. As shown by of resistance.
callaboratory potentiometer employs a linear V. R The slide wire shown in Figure 2-22 is current of 1 pA (10-6 A), we can readily ~_
voltage divider such as that shown in Figure ·+10--1- ~w.. readily calibrated to read directly in volts, culate from Ohm's law that the minimum
2-3b (p. 10) to attenuate a reference voltage B thus avoiding the necessity of calculating v,. distinguishable voltage difference will be
until a null point is reached. In its simplest each time. Calibration is accomplished by set- 10-6 X 1000 = 10-3 V, or 1 mY. By use of a
0.0 0.5 1.0 1.5 2.0
form, the divider consists of a uniform resis, I, I I I II • I I II I I I II , I .I
ting the slide wire to the voltage of the stand- galvanometer sensitive to 10 - 7 A, a difference
tance wire mounted on a meter stick. A sliding B ard cell. Then, with that cell in the circuit, of 0.1 mV will be detectable. A sensitivity of
contact permits variation of the output
Lineor vollllge the potential across AB is adjusted by means this order is found in an ordinary pointer-
divider
voltage. More conveniently, the divider is a of the variable resistor R until a null is type galvanometer; more refined instruments
precision wire wound resistor formed in a hel- achieved. The slide-wire setting will then give with sensitivities up to 10-10 A are not
ical coil. A continuously variable tap that can V" directly when C is adjusted to the null posi- uncommon.
be moved from one end of the helix to the tion with the unknown voltage. From this discussion, it is clear that the
other gives a variable voltage. Ordinarily, the The need for a working battery B may be sensitivity of a potentiometric measurement
divider is powered by dry cells or mercury questioned. I~ principle, there is nothing to decreases as the electrical resistance of the cell
batteries, which provide a potential somewhat prevent a direct measurement of v,. by replac- increases. As a matter of fact, potentials of
larger than that which is to be measured. ing B with die standard cell V,. It must be cells with resistances much greater than
Figure 2-23 is a sketch of a laboratory remembered, thowever, that current is being 1 Mn cannot be measured accurately with a
potentiometer employed for the measurement continuously drawn from B; a standard cell potentiometer employing a galvanometer as
FIGURE 2-23 Circuit diagram of a lab-
of an unknown potential v,.
by comparing it
oratory potentiometer.
would not maintain a constant potential for the current-sensing device.
with a standard potential V,. The latter is long under such usage. Current Measurements with a NuU In-
ordinarily a Weston standard cell which can The accur!lCY of a. voltage measurement strument. The null method is readily applied
be represented as follows: with a potentiometer equipped with a linear to the determination of current. A small
voltage dividcjr depends upon several factors. precision resistor is placed in series in the cir-
Cd(Hg)"ICdS04 • (8/3)HzO(sat'd~ from the battery B through C and the circuit Thus, it is nel:essary to assume that the volt- cuit and the potential drop across the resistor
containing G and V,. Electrons will flow in
Hg2S04(sat'd) I Hg the opposite direction, of course, if VAC is
age of the working battery B remains con- is measured with a potentiometer.
stant during the time required to balance the Resistance Measurements; the Wheatstone
One of the electrodes is a cadmium amalgam smaller than V,. The position of contact C is BrilIge. The Wheatstone bridge shown in
instrument against the standard cell and to
represented as Cd(Hg),,; the other is mercury. then varied until a null condition is achieved, measure the potential of the unknown cell. Figure 2-24 provides another example of a
The electrolyte is a solution saturated with as indicated by the galvanometer when K Ordinarily, this assumption does not lead to null device, applied here to the measurement
cadmium and mercury sulfates. The half reac- is closed.
appreciable error if B consists of one or two of resistance. The power source S provides an
tions as they occur at the two electrodes are The foregoing process is repeated with S in heavy-duty dry cells (or mercury cells) in
position 2 so that the unknown cell is in the good condition or a lead storage battery. The
Cd(Hg)" ...•Cd2+ + xHg + 2e circuit. Equation 2-9 can then be employed to instrument should be calibrated against the
HgZS04 + 2e ...•2Hg + SO~- calculate v,..
Thus, with S at position 1 standard cell before each voltage measure-
The potential of the Weston cell at 2SoC is ment to compensate for possible changes in
V. = Yo AC.
1.0183 V. • B AB B, however.
A potential measurement with the instru- The linearity of the resistance AB, as well
ment shown in Figure 2-23 requires two null- and at position 2 as the precision with which distances along its
point measurements. Switch P is first closed length can ~ estimated, both contribute to
V. = Yo AC" the accuracy of the potentiometer. Ordinarily,
to provide a current in the slide wire and a " B AB
potential drop across AC. The Weston cell is however, the, ultimate precision of a good-
next placed in the circuit by moving switch S Dividing these equations gives, upon quality instniment is determined by the sensi-
to position 1. When the tapping key K is rearrangement, tivity of the galvanometer relative to the
closed momentarily, a current will be in- resistance of the circuit. Suppose, for example,
that the electrical resistance of the galva-
dicated by the galvanometer G, unless the
output from the standard cell is identical with nometer plus the unknown cell is 1000 n, a
'"s
the potential drop VAC between A and C. If Thus, v,.
is obtained from the potential of the typical figure. Further, if we assume that the FIGURE 2-24 A Wheatstone bridge for
VAC is greater than V" electrons will flow standard cell and the two slide-wire settings. galvanometer is just capable of detecting a resistance measuremet1ts.
Be current at a potential of 6 to 10 V. The To measUre R", the position of C is ad- 4. A voltmeter was employed to measure the potential of a cell having
resistances RAC and Rc" are determined from justed to a minimum as indicated by the null an internal resistance of 750 O. What must the internal resistance of
the total resistances of the linear voltage detector. Application of Equation 2-9 to the the meter be if the relative error in the measurement is to be less than
divider, AB, and the position of C. The upper voltage divider ACB yields (a) -1.0~", (b) -0.10%?
right arm of the bridge contains a series of 5. For the following circuit, calculate
precision resistors that provide a choice of
AC
VAC= VAI/- (a) the potential drop across each of the resistors.
several resistance ranges. The unknown resis- AB (b) the magnitude of each of the currents shown.
tance R" is placed in the upper-left arm of the For the circuit ADB, we may write ·(c) the power dissipated by resistor R) .
bridge. (d) the potential drop between points 3 and 4.
A null detector N D is employed to indicate R"
VAD=VA"-R
,,+ R •
R, 2 3

-" '·1 -
an absence of current between D and C. The
detector often consists of a pair of ordinary
But at nul~ VAC= VAD.Thus, the two equa- +
= R, -loon
'3
earphones; an ac signal of about 1000 Hz is tions can be combined to give, upon 15.0V R. R3 R.· soon
employed, the human ear being sensitive in rearrangement, .!!... R3·200n
this frequency range. Alternatively, the detec-
~ R.-l000n

tor may be a cathode-ray tube or an ac 4 R. 5 6


microammeter.
6. For the circuit shown below, calculate
(a) the power dissipated between points 1 and 2.
1. It was desired to assemble the voltage divider shown below. Two of .(b) the current drawn from the source.
each of the following resistors were available: 50 0. 100 0, and 200 0. :(c) the potential drop across resistor RA•
[(d) the potential drop across resistor RD'
10.0 V
;(e) the potential drop between points 5 and 4.
+ 11-
V.
R, R. R3

R.-
RA- 1.0 kn
2.0 kn
Rc- 4.0 kn
Ro- 2.0 kn
V,-1.0V V.-4.0V V,
3 4 RE- 1.0 kn
2
-1111 +
(a) Describe a suitable combination of the resistors that would give 24 V
the indicated voltages.
(b) What would be the IR drop across R)? 7. Assume that the resistor shown between A and B in Figure 2-23
(c) What current would be drawn from the source? (p. 34) is a linear slide wire exactly 1.00 m in length. With the stand-
(d) What power is dissipated by the circuit? ard Weston cell (1.018 V) in the circuit, a null point was observed
2. Assume that for a circuit similar to that shown in Problem I, when contact C was moved to a position 84.3 cm from point A. When
Rj = 200 0, R2 = SOO0. R) = 1000 0. and V" = 15 V. - the Weston cell was replaced with an unknown voltage, null was
(a) Calculate the voltage V2• , observed at 44.3 cm. Calculate the potential of the unknown.
(b) What would be the power loss in resistor R2 ? 8. , A galvanometer with an internal resistance of 5000 0 shows a full
(c) What fraction of the total power lost by the circuit would be i scale reading with a current of 0.100 mA. Design an Ayrton shunt
dissipated in resistor R2 ? such that the gal\L8nometer will have a range of 0 to 10.0, 25.0, 50.0,
3. For a circuit similar to the one shown in Problem I, Rj = 1.00 ldl, and 100 mA.
R2 = 2.50 ko, R) = 4.00 ldl, and V" = 12.0 V. A voltmeter was 9. Assume that the slide wire in the Wheatstone bridge shown in Figure
placed across contacts 2 and 4. Calculate the relative error in the 2-24 has a resistance of SOOn and that the switch is in position 3.
voltage reading if the internal resistance of the voltmeter was (a) (a) What is the resistance of the unknown R" if a null is found when
5000 0. (b) 50 ill, and (c) 500 kO. contact C is at 62.6% of the full length of the slide wire?
(b) If the source potential S is 15 V and the resistance of the null n
18. A series RL circuit conSisted of a 12 Vsource, a 1000 resistor, and a
detector is 100 n, what is the current in the detector when C is set 2 H inductor.
at 62.7%? (a) Calculate the time constant for the circuit.
(c) If the switch is moved from 3 to 2, with Rx still in the circuit, (b) Calculate the current and the voltage drops across the resistor
where would C have to be moved in order to reach a new null? and inductor for the following times after the current was ini-
10. The current in a circuit is to be determined by measuring the poten- tiated: 0, 1,2, 4, 8, 10 IDS.
tial drop across a precision resistor in series with the circuit. 19. Calculate the capacitive reactance, the impedance, and the phase
(a) What should be the resistance of the resistor in ohms if 1.00 V is angle q, for the following series circuits.
to correspond to SO JlA?
Frequency, Hz R, 0 C,Ilf'
(b) What must be the resistance of the voltage measuring device if the
error in the current measurement is to be less than 1.0% relative? 1 20,000 0.033
11. An electrolysis at a nearly constant current can be performed with the 103 20,000 0.033
following arrangement: 106 20,000 0.033
I 200 0.033
103 200 0.033
106 200 0.033
1 2,000 0.33
103 2,000 0.33
106 2,000 0.33
20. Calculate the inductive reactance, the impedance, and the phase angle
q, for the following series circuits.
The 9O-V source consists of dry cells whose potential can be assumed Frequency, Hz R,O L,mH
to remain constant for short periods. During the electrolysis, the re-
3
sistance of the cell increases from 20 0 to 40 0 due to depletion of 10 2000 SO
ionic species. Calculate the percent change in the current assuming 10· 2000 SO
that the internal resistance of the batteries is zero. 105 2000 SO
12. Repeat the calculations in Problem II assuming that Ys = 9.0 V and 103 200 SO
R = 0.50 kO- 104 200 SO
105 200 SO
13. A 24-V dc potential was applied across a resistor and capacitor in
103 200 5
series. Calculate the current after 0.00, 0.010, 0.10, 1.0, and 10 sec if
104 200 5
the resistance was 10 MO and the capacitance 0.20 JlF.
IOS 200 5
14. How long would it take to discharge a oms JlF capacitor to I % of its
full charge through a resistance of (a) 10 MQ, (b) I MQ, (c) I kO? 21. Calculate the capacitive and inductive reactances and the impedance
IS. Calculate time constants for each of the RC circuits described in of the following series resonant circuits.
Problem 14. L,mH
Frequency, Hz R,O C,IlF
16. A series RC circuit consisted of a 2S-V dc source, a SO kO resistor,
102 2000 0.20 1.2
and a 0.035 IlF capacitor.
104 2000 0.20 1.2
(a) Calculate the time constant for the circuit.
106 2000 0.20 1.2
(b) Calculate the current and potential drops across the capacitor
102 20 0.20 1.2
and the resistor during a charging cycle; employ as times 0, 1,2,3,
104 20 020 1.2
4, 5, and 10 ms.
106 20 0.20 1.2 •
(c) Repeat the calculations in (b) for a discharge cycle.
17. Repeat the calculations in Problem 16 assuming that the potential 22. For the circuits described in Problem 21,
was 15 V, the resistance was 20 MQ, and the capacitance was (a) calculate the frequency at which a current maximum would
0.050 JlF. Employ as times 0, I, 2, 3, 4, 5, and 10 s. appear.
(b) calculate the current at this maximum if the input is a 15-V sinu-
soidal signal.
(c) calculate the potential drop across each of the components if the
input is a 15-V sinusoidal signal.
23. ~rive a frequency response curve for a low-pass RC filter in which
R';' 2.5 X 10' n and C •••0.015 pF. Cover a range of (Yp).!(Yp)/ of
0.01 to 0.99.
24. Derive a frequency response curve for a high-pass RC filter in which
R •••5.0 X 10' nand C •••200 pF (1 pF •••10-12 F). Cover a range of
om
(V,,).!(Yp)/ of to 0.99.
25. Derive a frequency response curve for an RL low-pass filter in which
R ••• 120 nand L ••• 8.0 H. Cover a range of (V,,).!(V,,)/ of 0.01 to 0.99.
Give a circuit design for an RC filter that would have the same
characteristics.
26. Determine the current and the voltage across !=&Chcomponent in a
series resonant circuit in which R'"' 100 n, C •••0.050 pF,
L'"' 225 mH, and (V,,)/'"' 12.0 V
(a) at the current maximum.
(b) at a frequency 10% lower than the maximum.
(c) at a frequency 10% higher than the maxim~m.
27. Calculate the capacitive and inductive reactances and the impedance
for parallel resonant circuits similar to that stfown in Figure 2-14b
assuming the values for f, R, C, and L given in Problem 21.
28. For the circuit shown in Figure 2-14b, calculate
(a) the frequency at which a current minimum would be expected.
(b) the current at a frequency that was 10% less than the minimum.
(c) the current at a frequency that was 10% more than the minimum.
A p-type or positive type semiconductor is p-type semiconductor is inherently less than
The circuit elements and circuits considered crysta~ each of these electrons is immobilized
formed when silicon is doped with a Group that of an n-type.
in Chapter 2 are linear in the sense that their by combination with an electron from
III element which contains only three valence
input and output voltages and currents are another silicon atom to form a covalent bond.
electrons. Here, positive holes are introduced
proportional to one another. Electronic cir- Thus, in principle, no free electrons' should Semiconductor Diodes
when electrons from adjoining. silicon atoms
cuits contain one or more nonlinear devices exist in crystalline silicon, and the material
jump to the vacant orbital associated with the A diode is a device that has greater conduct-
such as transistors, vacuum tubes, gas-filled should be an insulator. In fact, however,
impurity atom. Note that this process imparts ance in one direction than in another. Useful
tubes, and semiconductor diodes.l Histor. sufficient thermal agitation occurs at room
ically, electronic circuits were based upon temperature to liberate an occasional elec- a negative charge to the Group III atoms. diodes are manufactured by forming adjacent
vacuum tubes. Now, however, the vacuum Movement of the holes from silicon atom to 11- and p-type regions within a single germa-
tron, leaving it free to move through the crys-
tube has been almost totally replaced by semi- tal lattice and thus to conduct electricity. silicon atom, as described earlier, constitutes nium or silicon crystal; the interface between
conductor devices. The advantages of the This thermal excitation of an electron leaves a a current in which the majority carrier is these regions is termed a pn junction.
latter include low cost, low power consump- positively charged region, termed a hole, asso- positive. Positive holes are less mobile than ProPerties of. pn JUnctiolL Figure 3-la is
tion, small heat generation, long life, and ciated with the silicon atom. The hole, free electrons; thus, the conductivity of a a cros~ section of one type of pll junction,
small size. Most modern analytical instru- however, is mobile as wel~ and thus also
ments use only semiconductors; we shal~ contributes to the electrical conductance of
therefore, limit our discussion to these
devices.
the crystal. The mechanism of hole movement
is stepwise; a bound electron from a neigh-
,..---1 mm--.,
I I
I I
boring silicon atom jumps to the electron- I rr I
deficient region and thereby leaves a positive I +l l
IWire
hole in its wake. Thus, conduction by a semi- l Metal
I contact p.region
I
A semiconductor is a crystalline material conductor involves motion of thermal elec-
I \ I
having a conductivity between that of a con- trons in one direction and holes in the other.
ductor and an insulator. Many types of semi- The conduction of a silicon or germanium
conducting materials exist, including silicon crystal can be greatly enhanced by doping. a
and germanium. intermetallic compounds process by which a tiny, controlled amount of
(such as silicon carbide~ and a variety of an impurity is introduced into the crystal
organic compounds. Two semiconducting structure. Typically, a silicon semiconductor
materials that find wide application for elec- is doped with a Group V element such as
tronic devices are crystalline silicon and arsenic or antimony or a Group III element
germanium; we shall limit our discussions to such as indium or gallium. When an atom of
these. a Group V element replaces a silicon atom in
the lattice, one unbound electron is in-
Properties of Silicon troduced into the structure; only a small ther-
and Germanium Semiconductors mal energy is needed to free this electron for
Silicon and germanium are Group IV ele- conduction. Note that the resulting positive
ments and thus have four valence electrons Group V ion does not provide a mobile hole
available for bond formation. In a siliCQn inasmuch as there is little tendency for elec-
trons to move from a covalent silicon bond to
this nonbonding position. A semiconductor
I for further infonnation about modern electronics, see:
that has been doped so that it contains non-
A.J. Diefenderfer,Principles of Electronic Instrumentalion,
2d cd., Philadelphia: Saunders, 1979; J. J. Brophy, Basic bonding electrons is termed an n-type (nega-
ElectroniCS for Scientists, 3d cd. New York: McGraw. tive type) because electrons are the majority
Hill, 1977; H. V. Malmstadl, C. G. Enke, S. R. ca"iers of current. Positive holes still exist as (e) (d)
Crouch, and G. Horlick, Eleetronk Measurements for in the undoped crystal (associated with sili-
Screntlsrs.Menlo Park, CA: Benjamin, 1974;R. J. Smith,
con atoms~ but their number is small with FIGURE 3-1 A pn junction diode. (a) Physical appearance of
Circuits, Device3, and Systems. 3d cd. New York: Wiley. one type formed by diffusion of a p-type impurity into an n-type
1976; and B. H. Vassos and G. W. Ewing, Analog and respect to the number of electrons; thus, holes
represent minority carriers in an n-type semiconductor; (b) symbol for; (c) current under forward bias;
Digital Electronics for Scientists. New York: Wiley-
Interscience, 1972. semiconductor. (d) resistance to current under reverse bias.
we shall see, this phenomenon has practical transistors are; (1) small size; (2) heavilY
which is formed by dilTusing an excess of a
application in electronics. doped outer layers, the smaller of which is
p-type impurity such as indium into a minute
silicon chip that has been doped with an called the emitter and .the larger the collector;
n-type impurity such as antimony. A junction Transistors (3) a thin (- 0.02 mm~ lightly doped base
of this kind permits ready flow of positive layer that separates· the emitter and the
The transistor is the basic semiconductor am- collector; and (4) metallic contacts and elec-
charge from the p region through the n region
plifying device and performs the same func- trical leads to each of the three regions.
(or flow of negative charge in the reverse
tion as a vacuum amplifier tube-that is, it An alloy junction imp transistor, such as
direction); it olTers a high resistance to the
provides an output signal that is usually that shown in Figure 3-3a, is often fabricated
flow of positive charge in the other direction
significantly greater than the input. from a chip of n-type germanium. Small pel_
and is .thus a current rectifier.
Bipolar Transistors. Bipolar transistors lets of a Group III metal such as indium are
Figure 3-1b illustrates the symbol employed
consist of two back-to-back semiconductor fixed on both sides of the chip and heated
in circuit diagrams to denote the presence of
diodes. The pnp transistor consists of an until the metal melts and dissolves in the
a diode. The arrow points in the direction of
n-type region sandwiched between two p-type germanium. Upon cooling and crystallization,
low resistance to positive currents.
-I regions; the npn type has the reverse struc- two heavily doped p regions are formed on
Fi&/1re 3-lc shows the mechanism of con-
duction of electricity when the p region is FIGURE 3-2 Current voltage char- ture. Bipolar transistors are constructed in a the tw~ sides of the thin layer of n-doped
made positive with respect to the n region by acteristics of a silicon semiconductor variety of ways, two of which are shown in germanIUm.
application of a potential; this process is diode. Note that, fo~ the sake of Figure 3-3. The general features of all such A typical planar npn transistor, such as
called forward biasing. Here, the positive holes clarity, the small current under reverse
in the:p region and the excess electrons in the bias has been exaggerated.
n region (the majority carriers in both rr.-
gions)imove under the influence of the electric
field toward th~ junction, where they can
combine with and thus annihilate each other.
The negative terminal of the battery injects observed. Under reverse bias, a current on the
new electrons into the n region, which can order of microamperes flows over a consider-
then continue the conduction process; the able voltage range; in this region, conduction
positive terminal, on the other hand, extracts is by the minority carriers. Ordinarily, this
electrons from the p region thus creating new reverse current is of no consequence. As the
holes which are free to migrate toward the pn reverse potential is increased, however, a
junction. breakdown voltage is ultimately reached
When the diode is reverse-biased, as in where the reverse current increases abruptly
Figure 3-ld, the majority carriers in each to very high values. Here, holes and electrons,
region drift away from the junction to leave a formed by the rupture of covalent bonds of
depletion layer that contains few charges. the semiconductor, are accelerated by the
Only the small concentration of minority car- field to produce additional electrons and
riers present in each region drift toward the holes by collision. In addition, quantum p·layer
junction and thus carry a current. Con- mechanical tunneling of electrons through the -O.02mm
thick
sequently, conductance under reverse bias is junction layer contributes to the enhanced
typicalIy 10-6 to 10-8 that of conductance conductance. This conduction, if sufficiently (b) Id)
under forward bias. large, may result in heating and damaging of
Current-Voltage Carves for Semiconductor the diode. The voltage at which the sharp in- FIGURE 3-3 Two types of bipolar resistors. Construction
Diodes. Figure 3-2 shows the behavior of a crease in current occurs under reverse bias is details are shown in (a) for a pnp alloy junction transistor and
typical semiconductor diode under forward called the Zener breakdown voltage. By con- in (b) for an npn planar transistor. Symbols for a pnp and an
and reverse bias. With forward bias, the cur- trolling the thickness and type of the junction npn bipolar transistor are shown in (c) and (d), respectively.
rent increases nearly exponentially with layer, Zener voltages ranging from a few volts Note that aUoy junction transistors may also be fabricated as
voltage; often currents of several amperes are to several hundred volts can be realized. As npn types and planar transistors as pllp.
that shown in Figure 3-3b, is formed from a . After amplification, the dc component can
wafer of n-type silicon which has a surface then be removed by a high-pass filter (p. 23).
coating of silicon dioxide; this layer is The emitter-collector circuit is powered by
deposited by heating the wafer in an oxygen a dc source or. power supply that may consist
atmosphere. To fabricate the p-type base of a series of b~tteries or a rectifier. Typically,
region, a circle is etched in the oxide surface; the power supply will provide a potential be-
the crystal is then heated and exposed to va- tween 9 and 30 V.
porized boron to produce a lightly doped, Note that, as shown by the breadth of the
p-type region by diffusion. The surface film is arrows, the collector or output current Ie is
then reformed by oxidation, following which significantly larger than the base input cur-
a smaller circle is etched within the original rent lB' Furthermore, the magnitude of the
circle. This region is then heavily doped by collector current is directly proportional to
diffusion of phosphorus into the heated crys- the input current. That is,
tal to give an n-type emitter.
The symbols for the pnp and the npn type
of transistor are shown on the right in Figure
3-3. The arrow on the emitter lead indicates where the proportionality constant a is the
the direction of flow of positive charge. Thus, current gain, which measures the current
in the pnp type. positive charge flows from the amplification that has occurred. The collector
emitter to the base; the reverse is true for the current is also proportional to the emit.er
npntype. I current. Thus,
Electrical Charaderistics of a Bipolar
Transistor. The discussion that follows will
focus upon the behavior of a pnp-type bipolar where the proportionality constant C( is called Ie
transistor. It should be appreciated that the
the forward current transfer ratio. Since J;;
Current gain, a ,..
npn type acts analogously except for the
IE == IB + Ie (see Figure 3-4), it is readily FIGURE 3-4 Currents in a common-emitter
direction of the flow of electricity, which is
shown that cir~uit with a pnp transistor. Ordinarily, C( ~ 0.95
opposite.
to 0.995 or C( ~ 20 to 200.
When a transistor is to be used in an elec- C(
a=--
tronic device, one of its terminals is connected l-C(
to the input and the second serves as the
output; the third terminal is connected to Values for a for typical transistors range from
both and is the common terminal. Three 20 to 200. away from the junction, as shown in Figure the n layer. Thus, the holes in this pn junction
configurations are thus possible: a common- Mechanism of Amplification with a Bipolar 3-ld. have a current-carrying capacity that is per-
emitter, a common-collector, and a common- Transistor. It should be noted that the In the forward-biased pn junction il- haps one hundred times greater than that for
base. The common-emitter configuration has emitter-base interface of the transistor ,;hown lustrated in Figure 3-1c, the number of holes the electrons.
the widest application in amplification and is in Figure 3-4 constitutes a forward-biased pn in the p region is about equal to the number Turning again to Figure 3-4, it is apparent
the one we shall consider in detail. junction similar in behavior to that shown in of mobile electrons in the n region. Thus, that holes are formed at the p-type emitter
Figure 3-4 illustrates the current Figure 3-lc, while the base-collector region is except for the small difference in their mobili- junction through abstraction of electrons by
amplification that occurs when a pnp tran- a reverse-biased np junction similar to the cir- ties, conduction through the diode is shared the two dc sources, namely, the input battery
sistor is employed in the common-emitter cuit shown in Figure 3-1d. A current 18 more or less equally between the two types of and the power supply. These holes can then
mode. Here, a small dc input current IB, readily flows through the forward-biased charged bod.ies. Recall, however, that the p move into the very thin n-type base region
which is to be amplified, is introduced in the junction whett an input signal of a few tenths region of a pnp transistor is much more where some will combine with the electrons
emitter-base circuit; this current is labeled as of a volt is applied (see Figure 3-2). In heavily doped than the n region. As a from the input source; the base current IB is
the base current in the figure. As we shall contrast, passage of electricity across the consequence, the concentration of holes in the the result. The majority of the holes wil~
show later, an ac current can also be reverse-biased collector-base junction is in- p region is a hundredfold or more greater however, drift through the narrow base layer
amplified by introducing it in series with lB' hibited by the migration of majority carriers than the concentration of mobile electrons in and be attracted to the negatively charged
Power supply
collector junction, where they can combine the gate, however (as in Figure 3-5c~ the Ve ac. It is important to note that a dry cell (or
with electrons from the power supply; the col- supply of electrons in the channel is depleted other dc source generally) has, for all practi-
lector current Ic is the result. (see Figure 3-1d, p. 43); thus, the resistance of -1111 +
cal purposes, negligible resistance toward an
It is important to appreciate that the mag- the channel increases and the current ac signal; similarly, most ac sources can be
nitude of the collector current is determined decreases. assumed to olTer virtually no resistance
by the number of current-carrying holes
available in the emitter. This number,
A major advantage of the field elTect tran-
sistor arises from the fact that it is normally
, toward a dc current. Thus, the series arrange-
ment shown will produce an ac signal that is
I
however, is a fixed multiple of the number of operated in the reverse-bias mode. As a I superimposed upon the dc current. That is,
1
electrons supplied by the input base current. consequence, the resistance of the gate circuit I the base current is given by (/B + iB) where is '
I
Thus, when the base current doubles, so also is very large, and the current drawn from the Ouqx;t is due to the ac signal.
AC
does the collector current. This relationship input signal small. input f (va+ Va) Typically, an amplifier such as that shown '
leads to the current amplification exhibited
by a bipolar transistor.
~~I~
v. (~+M i
I
I
in Figure 3068 employs a power supply that
has an output potential of IS to 30 V dc'
'

AMPLIFIERS l (I. + i.1 j 'lie + IcJ I


I
normally, the current is produced b;:
Field Effect Transistors EMPLOYING TRANSISTORS .J rectification of 1l0-Vac line output. The'
Two other types of transistors, field elTect power supply then serves as the source of the .
The electrical signal from a transducer is or- ':" Ground amplified collector current. Often this current '
transistors (FET) and metal-oxide-semicon-
dinarily so small that it must be amplified, (a) is observed as the output voltage drop
ductor field effect transistors (MOSFET~ are
also encountered. An example of the former
often millions of times, before it is sufficient (vc£ + Vcd across the emitter-eollector ter-
to operate a meter or a recorder and thus be minals of the transistor.
appears in Figure 3-5. Here, the gate is a cylin-
measured. In this section, we will consider the Both the bias current and the signal cur-
drical p-type semiconductor surrounding a
details of a few single-stage, practical rent are, of course, amplified and appear as a
center core of n~oped material called thel
amplifier circuits. It should be appreciated, dc component or the collector current Ie and
channel. As with bipolar transistors, the p- and
however, that a single transistor seldom pro- an ac component ic. Note that the collector
»-semiconductor regions can be reversed. The
vides the amplification needed for most appli- current and the base current combine at the
gate serves the same function as the base in a
cations, and that a satisfactory output can common junction to form an emitter current
bipolar transistor; that is, the bias on the gate
only be achieved by cascading several (if: + If:~ which also has both ac and dc
controls the flow of electrons between the
amplifier stages. character.
source and drain leads of the transistor.
In the absence of a gate bias potentia~ Ground Connections. Electronic circuits
A Simple Amplifier Circuit normally have a low-resistance wire or foil
electrons are free to flow from the power
supply, through the channel and back to the Figure 3-6a is a circuit diagram for a simple (b)
that interconnects one terminal or each signal
power supply; conduction in the channel is amplifier capable or amplirying either an ac source and the power supply; other compo-
FIGURE 3-6 (a) A common-emitter cir- nents or the circuit may also be connected to
by electrons. When a reverse bias is applied to or a dc current by a factor of 100 or more.
cuit for amplification or a small ac signal. this common line, called the ground or the
(b) Shorthand version or (a) wherein all indi- system. The ground provides a common
Power supply cated voltages are assumed to be with respect return ror all currents to their sources. As a
to the common ground.
+ 1111- consequence, all voltages in the circuit are

-=~ ,,,.
atelead
with reference to the common ground. Figure
3-6a shows that the plus terminal or the
- ,p , + power supply is connected directly to the
n n
Source ~ ..,' - Drain - :; - ;>~'j . + With either, the input signal is placed in series ground, which is indicated by the three paral-
lead lead .. (-,. '.'
with a constant base bias VB' and is thus lei lines at the bottom orthe figure. Note that
superimposed on the steady current lB' The a~ide of the input and output signals, as well
Gate bias may be provided by a battery, as shown; as the emitter terminal of the transistor, are
more often, however, the bias is provided by similarly connected and are thus at ground
the amplifier power supply. potential.
In Figure 3-68, the signal is assumed to be Figure 3-6b is a simplified diagram of the
amplifier shown in (a). Here, the lines con- reactance to an alternating current is negli- transistors that are coupled through their
necting the power supply to the grounded gible in the frequency range for which the cir- emitters. As its name implies, this circuit
sides of the output and input have been cuit is intended. Thus, typically, the amplifies the difference between input signals
deleted, it being understood that one side of approximation 1 and 2. If the two load resistors and tran-
v., (VCIl + VcIl1 and Vc is at ground potential.
sistors are perfectly matched, the output of
Note that positive electricity flows from
is valid to 1 to 2 %. Clearly then, the emitter this device will be zero for equal input signals.
ground to the power supply and the signal
follower does not provide any voltage gain. Otherwise, a linear response to signal differ-
sources. ences is obtained.
As with the common-emitter circuit, however,
good current gains are realized. It is also im- The difference amplifier is useful for
An Emitter-Follower Amplifier several reasons. It wil~ for example, reject an
portant to note that Equation 3-4 indicates
Figure 3-7 is a diagram for an emit~er that the output signal will be in phase with unwanted part of a signal that is common to
follower. It differs from the common-emitter the input. both inputs. It is relatively unaffected by tem-
circuit in that the load resistor, RL, is locat-ed The emitter-follower circuit finds wide- perature changes and the passage of time.
between the emitter and the base. For theac spread use because it has a high input im- Finally, it is a useful device for comparing
input, the collector terminal is at ground inas- pedance and thus draws little current. High two signals by the null-point method. Because
much as the dc power supply offers essentially impedance is of importance in measuring of its stability, this circuit is widely used to
no resistance toward the ac current; thus, the electrical properties of devices whose output amplify dc signals.
circuit is a common-collector circuit. is disturbed by current passage. The input re- Amplifiers with Negative Feedback. Often
By applying Kirchhoffs voltage law to the sistance is readily found by assuming that R, it is advantageous to return or feedback a
loop that contains the input, the base, the in Figure 3-7 is so large with respect to RL fraction of the output signal from an amplifier
emitter, and the load resistor RL, we obtaip that essentially all of the input signal passes to the input terminals. The fractional signal
which rearranges to that is returned is called feedback. Figure 3-9
through the latter. Then it is seen that
V••• i.Xc, + V.1l + illRL VB
ill = iB + ic Rio = -;- = (I + a)RL (3-5) shows an amplifier with a feedback loop.
The voltage V.1l across the base-emitter ter- 'B Here, a fraction /I of the output signal is
minal is at most a few tenths of a volt and is Substituting the ac form of Equations 3-1 and where R", is the resistance to an input current sampled by means of a resistor-capacitor
generally insignificant when compared with 3-4 yields of i•.Typically, then, the input resistance of network (shown as the feedback box in the
the JR drop across RL• In addition, the capac- an emitter follower is one hundredfold or diagram); the resulting signal /Iv. is then
itance of C, is made large enough so that its greater than its output resistance, since a returned in such a way that it combines with
often ranges from 100 to 200. the input signal v,, The net input signal then
A Differential Amplifier. Figure 3-8 is a is VA, which is equal to (VI + jlv.). If the
circuit diagram for a difference or differential amplifier gain is a, we may write that

Vc t amplifier. It consists of a pair of matched I'. = aVA = a(v; + /Iv.)


I

t
R, iE: RL
i. I
----- ----.Ij
icl
a
v. = I _ pa Vi (3-6)
feedback system, in contrast t~ the amplifier
itself, can be made quite stable, inasmuch as
the resistors and capacitors it contains are
much leSs subject to temperature fluctuations
C 12V~

Thus, the net gain a' of the amplifier with


feedback is
and aging effects. For that matter, replace-
ment of one or more transistors in an
amplifier with good negative feedback often
r.~ C30V~
. Switch

a'= _a_
1- pa
(3-7)

The feedback ratio p can have either a pos-


has no discernible effect on the overall
amplification of the unit. ~L-:]
115V

Fuse
Primary

itive or negative sign. For example, the


output from the amplifier shown in Figure POWER SUPPLIES
3-9 is out of phase with the input signal. The AND REGULATORS
feedback from this signal, then, would inter- EMPLOYING TRANSISTORS
act destructively with the input, thus reducing
the signal amplitude; here p is negative, and Generally, laboratory instruments require de FIGURE 3-11 Schematicofa typical power
the circuit is said to have negative feedback. power to operate amplifiers and other reac- transformer with multiple secondary windings.
On the other hand, the output signal from the tive components. The most convenient source
amplifier in Figure 3-7 is in phase with the of electrical power, however, is llS-Vac fur-
input; here, the feedback would be positive. nished by public utility companies. As shown
Negative feedback is of great importance in in Figure 3-10,laboratory power supply units
former such as that shown sS:hematically in Filters
electronic circuits; we shall focus almost ex- increase or decrease the potential from the
Figure 3-11. The varying mal!1letic field aris-
clusively on this type of feedback. house supply, rectify the current so that it has The output of each rectifier is also shown in
ing in the primary coil in this device from the
TIle full advantage of negative feedback is a single polarity, and finally, smooth the the plots on the right of Figure 3-12. In order
passage of the IIS-Vac supply current
realized when pa ~ I in Equation 3-7. Then output to give a signal that approximates de. to minimize current fluctuations, the output is
induces currents in the secondary coils; the
Most power supplies also contain a voltage usually filtered by placing a large capacitance
potential across each is given by
regulator which maintains the output voltage in parallel with the load as shown in Figure
a' = - ~ (3-8) at a constant desired level. 3-13. The charge and discharge of the capaci-
tor has the effect of decreasing the variations
Note that under these circumstances, the
Tranefonnera where N 2 and N I are the number of turns in to a relatively small ripple. In some applica-
overall amplification depends only upon the
the secondary and primary coils, respectively. tions, an inductor in series and a capacitor in
properties of the feedback network and not Alternating current is readily increased or de-
Power supplies with multiple taps, as in parallel with the load serve as a filter; this
upon the properties of the amplifier system. The creased in voltage by means of a power trans-
Figure 3-11, are available commercially; type of filter is known as an L section. By
many voltage combinations can be had. Thus, suitable choice of capacitance and inductance,
a single transformer can serve as a power the peak-to-peak ripple can be reduced to the
supply for several components of an millivolt range or lower.
instrument.
The output voltage of a simple transformer
Voltage Regulators
fluctuates only a few percent: even when the
current drawn from the output varies widely. Often. instrument components require de volt-
I
ages that are constant and independent of
the current being drawn. Voltage regulators
Rectifiers
serve this purpose.
Figure 3-12 shows three types of rectifiers and Figure 3-14 illustrates two simple voltage
their output-signal forms. Each uses tran- regulators. Both employ a Zener diode, a pn
FIG U R E 3-10 Diagram showing the components of a power supply sistor diodes (p. 43) to block current flow in junction which has been designed to operate
and their effect on a signal. one direction while permitting it in the other. under breakdown conditions; note the special
""8 e=:
It'"
Holf __
vo~ Time
symbol for this type of diode. In Figure 3-2
(p. 44~ it is seen that at a certain reverse bias
a transistor diode undergoes an abrupt break~
down whereupon the current increases precip- .
itously. For example, under' breakdown
and resistance-the

ments.2
typical signals from the
transducers empioyed for chemical measure-·

General Characteristics
conditions, a current change of 20 to 30 mA of Operational Amplifiers

115V
ac
C
G..
V.

Full-wave
voE Time
may result from a potential change of 0.1 V
or less. Zener diodes with a variety of
specified breakdown voltages are available
commercially.
For voltage regulators, a Zener diode is
Operational amplifiers are a class of differen-
tial amplifiers that find wide application in
instrumentation. The designs of these devices
vary widely. Their performance character-
istics. on the other hand. have a number of
chosen such that it always operates under
co?,mon features which include: (1) large
breakdown conditions; that is, the input volt-

mvil
ItU
age to be regulated is greater than the break-
down voltage.
For the regulator shown in Figure 3-148,
an increase in voltage results in an increase in
gaIns (104 to 106); (2) high input impedances
(orten ~p to 1012 0 or greater); (3) low
output IDlpedances (typically I to 100); and
(4) zero output for zero input.
O~tiOll.1 AmpUfier Design. Operational
current through the diode. Because of the
~phfiers ordinarily contain several amplify-
steepness of the current-voltage curve in the
Ing stages that contain resistors. capacitors,
breakdown region (Figure 3-2), however,
and transistors. Internal negative feedback is
the voltage drop across the diode. and thus
used extensively in their design. Early opera-
the load. is virtually constant.
tional amplifiers employed vacuum tubes and
The regulator circuit shown in Figure
were consequently bulky and expensive. In
3-14b provides the most effective and widely

_., fc :: ~.,
contrast, modern commercial operational
used type of voltage regulator. It serves to
I
,\
reduce the current. and thus the power that
amplifiers are tiny; typically. they are manu-
factured on a single thin silicon chip having
I \ must be dissipated by the diode. Again. the
surface dimensions that are perhaps 0.05 in.
Time
voltage drop across the load is essentially that
on a side. Through integrated-circuit technol-
across the Zener diode.
ogy. resistors, capacitors, and transistors are
FIGURE 3-13 Filtering the current from a rectifier.
formed on the surface of the chip by photo-
lithographic techniques. After leads have bec~
soldered in place, the entire amplifier is
encased in a plastic housing that has dimen-
Regulated sions of a centimeter or less; the package. of
de
course, does not include the power supply.
output Operational amplifiers derive their name
Current-day operational amplifiers, in
from their original applications in analog
addition to being compact, are remarkably re-
computers, where they were employed to per-
liable and inexpensive. Their cost ranges
form such mathematical operations as
typically from less than a dollar to several
summing, multiplying. differentiating, and
dollars. Manufacturers offer a large number
integrating_ These operations also play an im-
Unregulated Regulated of operational amplifiers, each differing in
de de portant part in modern instrumentation; as a
input output consequence. operational amplifiers find
widespread use in instrument design. In addi- 2 For a more complete discussion of applications of
tion to their mathematic role, however, oper- operational amplifiers, see: R. Kalvoda, Opera/joMI
(bl
ational amplifiers find general application in Amplifier .• in Chemical Inslrumenra/ion. New York:
FIGURE 3-14 Voltage regulators. the precise measurement of voltage, current, Halsted Press. 1975.
such properties lIS gain, input and output the differential mode. Here, the difference be- signal input into the inverting terminal yields
impedance, operating voltages, and maximum . tween two input potentials is amplified and an output that is 180 deg out of phDse. The
power. appears as an output with respect to ground. positive input of an amplifier, on the other
Symbols fOl' Operational Amplifiel;oi.In cir- The symbol shown in Figure 3-ISd is often hand, yields an in-phase output signal or a de
cuit diagrams, the operational ampl~er is or- encountered. Unfortunately, it may lead to signal of the same polarity as the -input
dinarily depicted as a triangle having, as a confusion because it is not evident whether
minimum, an input and an output terminal the input is to the inverting or the noninvert- Circuits Employing
(Figure 3-ISd). Often, additional terminals ing terminal; thus, we shall avoid its use. Operetlonal Amplifiers
are indicated, as in (a1 (b1 aild (c) of the Inverting and Noninverting Terminals. It is Operational amplifiers are employed in cir-
figure. A symbol as complete as that in Figure important to realize that the positive and neg- cuit networks that contain various combina-
3-ISa is seldom encountered. Here, the power ative signs show the inverting aniJ noninverting tions of capacitors, resistors, and other
supply leads are shown; ordinarily the power terminals of the amplifier and do not imply electrical components. Under ideal condi- FIGURE 3-16 Inverting circuit with nega-
supply input is deleted, its presence being that they are necessarily to be :connected to tions, the output of the amplifier is tive feedback.
assumed. inputs of the corresponding signs. Thus, if the determined entirely by the nature of the
Figures 3-15a and 3-15b depict the most negative terminal of a battery is connected to network and its components and is independ-
common operational amplifier arrangement, the minus or inverting terminaI,: the output of ent tf tlte operational amplifier itself. Thus, it
in which the noninverting terminal (labeled the amplifier is positive with respect to it; i( is important to examine some of the various tremely high (see criterion (21 p. 55); thus,
+ ) is grounded. The input and output poten- on the other hand, the positive terminal of the networks that employ operational amplifiers. i, <C if and
tials are with respect to ground. Figure 3-ISc battery is connected to the minus input of the BasIc Inverting Circuit. Figure 3-16 is a
shows an operational amplifier being used in amplifier, a negative output results. An ac circuit diagram of an inverting circuit em-
ploying an operational amplifier. The
amplified output v. is 180 deg out of phase
Power supply with the input 1',. Note that part of the output V, - v, v, - v.
Invorting + T vc is fed back through the resistor Rf; because R;-=R;-
terminal I of the phase shift, the feedback is negative.

r
I Substituting the expression for the gain of the
This arrangement is perhaps the most
amplifier into Equation 3-11 and solving for
Input common of all networks associated with
the output voltage gives
operational amplifier circuits.
-:- + Output
I The gain a of the operational amplifier y -_y~_R_f_/R_,}_
_!Vc shown in Figure 3-15a is given by the • 1 + (I + Rf/R,}/a
Noninverting relationship
terminal
Note, however, that a for an operational
(I) v. amplifier is usually larger than 104• Normally,
a=---
1'+ - v_ the resistors R f and R, are chosen such that
Inp~o RJfR, is less than 100. Therefore, under usual
~ Ou~ut Since the plus terminal is grounded, however,
In~PUt conditions, (I + Rf/R,)/a <C I and the fore-
v+ = 0; furthermore, V, = 1'_ . Thus, the gain
going equation becomes
(e) (d) is given by
FIGURE 3-15 Symbols for operational ampli- Rf
fiers. In each case, the output is with respect to
1'.= -V, R,
ground. Inverting circuits with grounded non- The properties of the circuit in Figure 3-16
inverting terminals are shown in (a) and (b). More can be developed with the aid of Kirchhol1's Thus, when a high-gain amplifier is employed
detail than is-usually provided is shown in (a). current law; that is, and when Rf/R, is not too great, the circuit
The circuit in (c) is a differential amplifier in which shown in Figure 3-16 provides a gain which
i,= i,+ if depends only upon Rf/R, and is independent
neither input is grounded. A shorthand representa-
tion of an operational amplifier circuit is shown Recal~ however, that the input impedance of of fluctuations in a, the gain of the amplifier
in (d). an operational amplifier is always made ex- itself.
Light
As we have seen, however, the second term in ~source amplifiers to the measurement of each type of


the denominator is the amplifier gain. Thus, 1\ signal.
Curreat Meuurement The accurate mea-
5 A Open loop gain
Z
,
=~1 +a (3-13) I
I
I
I
surement of small currents is important to
such analytical methods as voltammetry,
4 "SlImPI.
c
Typical values for Rf and a are 10' a and coulometry, photometry, and gas chromatog-
"s,
104• Under these circumstances, the im- + + raphy.
~ 3 As we pointed out in Chapter 2 (p. 30), an
pedance between S and ground would be only
10 a. This property of the circuit, shown in important concern that arises in all physical
Figure 3-16, is of considerable importance in measurements, including that of current, is
current measurement (see p. 30~ whether the measuring process wilI, in itsel~
Frequency Response of the Basic Inverting alter significantly the signal being measured,
Circuit The gain of a typical operational thus leading to aQ error. It is inevitable that
log frequency amplifier decreases rapidly in response to any measuring prOcess will perturb a system
high-frequency input signals. This frequency under study in such a way that the quantity
FIGURE 3-17 Frequency response of a actually measured differs from its original
typical operational amplifier. (a) Without dependence arises from small capacitances FIGURE 3-19 Application of an opera-
that develop at pn junctions. The effect for a tional amplifier to the measurement of a value before the Iheasurement. All that may
negative feedback and (b) with negative
typical amplifier is shown in Figure 3-17, small photocurrent, I". be hoped is that the perturbation can be kept
feedback.
where the curve labeled open-loop gain repre- sufficiently small. For a current measurement,
sents the behavior of the amplifier in the this consideration requires that the internal
absence of the feedback resistor Rf in Figure resistance of the ;measuring device be kept
3-16. Note that both the ordinate and the input is fed into the noninverting termina~ low.
It is important to appreciate that when abscissa are log scales and that the open-loop and a feedback loop is provided which in- A low-resistanet current measuring device
Equation 3-12 applies, the voltage at point S gain for this particular amplifier decreases volves the inverting terminal. The result is an is readily obtained by deleting the resistor R,
with respect to ground is necessarily negli- rapidly at frequencies greater than about amplifier with a gain of approximately unity. in Figure 3-16 arid using the current to be
gible compared with either 1'/ or v•. That t~is 100 Hz. Because the input is not inverted, the output measured as the signal input. An arrangement
statement is correct can be seen by notmg In contrast, an operational amplifier em- potential is the same as the input. The input of this kind is shown in Figure 3-19, where a
that the only cOndition under which Equation ploying external negative feedback, as in impedance is the open-loop impedance for small direct current I" is generated by a pho-
3-12 follows from 3-11 is when v, ~ v. and 1'/. Figure 3-16, has a constant gain or bandwidth the amplifier, which can be very large totube, a transducer that converts radiant
Thus. the potential at point S must approach that extends from dc to over 10' Hz. In this (100 Ma) when a field effect transistor is energy such as IiBht into an electrical current.
ground potential; as a consequence, point S is region, the gain depends only upon Rf/R" as employed. The output impedance, on the When the cathode of the phototube is main-
said to be at virtual ground in the circuit. shown by Equation 3-12. For many purposes, other hand, is low « 1 a). As will be shown tained at a potential of about -90 V, absorp-
It is of interest to determine the effective the frequency independence of the negative later, this impedance transformation is valu- tion of radiation by its surface results in the
impedance Z, between the point Sand feedback inverting circuit is of great impor- able in the measurement of high-impedance ejection of electrons, which are then ac-
ground. This quantity is given by tance and more than offsets the loss in sources with low-impedance measuring celerated to the wire anode; a current results
amplification. devices. that is directly proportional to the power of
Z, = V,/ii the radiant beam.
The Voltage-Follower Circuit Figure 3-18
depicts a voltage follower, a circuit in which Amplification and If the conclusions reached on page 57 are
We have noted, however, that ij ~ if' and applied to this circuit, we may write
from Figure 3-16, we see that Measurement of Transducer Signals
Operational amplifiers find general applica- Ix=',If+I.~If
. . v. - v. ;
li=lf=-R- tion to the amplification and measurement of
f

Combining the two equations gives ,,$ L.. the electrical signals frolD transducers. These
signals, which are often concentration-
dependent, include current, potentia~ and re-
In addition, the point S is at virtual' ground
so that the potential Y" corresponds to the
potential drop across the resistor Rf. There-
fore, from Ohm's law,
Z= v,Rf =~ FIGURE 3-18 Voltage-fol- sistance (or conductance). This section
, v, - v. 1 - v./v, lower circuit. includes simple applications of operational Y,,= -lfRf= -I"Rf
parameter is related to the concentration of 100 Mn or more is often called an ment of conductance or resistance. In (a), the
the species responsible for the absorption. electrometer. conductance of a cell for a conductometric
I" = - V./R, = kV. Photometers are described in detail in Chap- Resistance or Conductance Mea.ements. titration is of interest. Here, an alternating-
Thus, the potential measurement V. gives the ter 7. Electrolytic cells and temperature-responsive current input signal VI of perhaps:5 to 10 V is
current, provided R, is known. By making R, Potencial Meaurements. Potential meas- devices, such as thermistors and bolometers, provided from the secondary of a filament
reasonably large, the accurate measurement urements are used extensively for the measure- are common examples of transducers whose transformer. The output signal is then
of small currents is feasible. For example, if ment of temperature and for the determination electrical resistance or conductance varies in rectified and measured as a potential. The
R, is 100 kCl, a 1-1lA current results in a of the concentration of ions in solution. In the response to a chemical signal. They are em- variable resistance R, provides a means for
potentia} of 0.1 V, a quantity that is readily former application, the transducer is a thermo- ployed for conductometric and thermometric varying the range of conductances that can be
measured with a high degree of accuracy. couple; in the latter, it is a pair of electrodes. titrations, in infrared absorption and emission recorded or read. Calibration is provided by
An important property of the circuit In Chapter 2 (p. 32~ it was demonstrated methods, and for temperature control in a switching the standard resistor R. into the cir-
shown in Figure 3-19 is its low resistance that accurate potential measurements require variety of analytical measurements. cuit in place of the conductivity cell.
toward the tra~ucer, which minimizes the that the resistance of the measuring device be The circuit shown in Figure 3-16 provides Figure 3-21b illustrates how the circuit in
measuring error. Recall from the earlier large with respect to the internal resistance of a convenient means for measurement of the Figure 3-16 can be applied to the measure-
discussion (p. 58) that S is at virtual ground, the voltage source to be measured. The need resistance or conductance of a transducer. ment of a ratio of resistances or conduct-
and the resistance of the measuring device is for a high-resistive measuring device becomes Here, a constant potential source is employed ances. Here, the absorption of radiant energy
thus low. ' particularly acute in the determination of pH for Vi and the transducer is substituted for by a sample is being compared with that for a
with a glass" electrode. For this reason, the either Ri or R, in the circuit. The amplified reference solution. The two photoconduct-
EXAMPLE basic inverting circuit shown in Figure 3-16, output potential V. is then measured with a ance transducers replace R, and RI in Figure
Assume that R, in Figure 3-19 is 200 kCl, which typically has an internal resistance of suitable meter, potentiometer, or recorder. 3-16. A battery serves as the source of power
the internal ~tance of the phototube is perhaps 10' n, is not satisfactory for voltage Thus, if the transducer is substituted for R, in and the output potential M, as seen from
5.0 x 104 Cl, ani! the amplifier gain is measurements. On the other hand, it can be Figure 3-16, the output, as can be seen from Equation 3-12, is
1.0 x 10'. Calcu~te the relative error in the combined with the voltage-follower circuit rearrangement of Equation 3-12, is
current measurement that results from the shown in Figure 3-18 to give a very high- M = k R. = k' p. (3-16)
presence of the measuring ~ircuit. impedance voltage-measuring device. An R P
Here, R••, the resistance of the measuring example of such a circuit is shown in Figure Typically, the resistance of a photoconductive
device, is given by Equation 3-13 3-20. The first stage involves a voltage cell is directly proportional to the radiant
follower, which provides an impedance of as where R" is the resistance to be measured and k
R., = Z. = R,/(I + a) power, P, of the radiation striking it. Thus,
much as 1012 n. An inverting amplifier circuit is a constant which can be calculated if Ri the meter reading M is proportional to the
- 200 x 10'/(1 + 1.0 x 10') = 2.0 n follows, which amplifies the input by R,/~ and V, are known; alternatively, k can be ratio of the power of the two beams.
or 20. An amplifier with a resistance of determined by a calibration wherein R" is Comparison of Transducer Outputs. It is
On page 31, it was demonstrated that the
replaced by a standard resistor. frequently desirable to compare a signal gen-
relative error in a current measurement is
If conductance rather than resistance is of erated by an analyte to a reference signal, as
given by
interest, the transducer conveniently replaces in Figure 3-21b. A difference amplifier, such
R R; in the circuit. Here, from Equation 3-12, it as that shown in Figure 3-22, can also be
reI error = - -_ ••-
RT + R., is found that employed for this purpose. Here, the amplifier
where RT is the resistance of the circuit in the is being employed for a temperature measure-
absence of the resistance of the measuring ..!- = G = _l = k'v (3-15) ment. Note that the two input resistors (Rj)
device R••. Thus; R" " viR, • have equal resistances; similarly, the feedback
resistor and the resistor between the non in-
i 2.0 where G" is the desired conductance. Note verting terminal and ground (both labeled Rt)
re I error = - 5.0 X 104 + 2.0 that in either type of measurement, the value are also alike.
= -4.0 x 10-' or -0.004% of k, and thus the range of the measured Applying Ohm's law to the circuit shown
values, can be readily varied by employing a in Figure 3-22 gives
The instrument shown in Figure 3-19 is a variable resistor R or R,.
j

photometer, which measures the attenuation FIGURE 3-20 A high-impedance circuit Figure 3-21 illustrates two simple applica- V1- V_
11=---
of radiation passing through a solution; this for voltage amplification. tions of operational amplifiers for the measure- Rj
The potential V+ can also be written in terms that meets these qualifications is termed a
of V2 by means of the voltage-divider equa- potentiostat.
tion. Thus, Several reference cells are available to pro-
_ V _ V2Ra: vide an accurately known voltage; one of
these, the Weston cell, was described on
+ - R1+Rt
page 34. None of these sources will, however,
Combining the last two equations gives, upon maintain its potential when a significant cur-
rearrangement, rent is required.
Figure 3-23 illustrates how a Weston cell
or some other reference cell can be employed
to provide a standard voltage source from
Thus,' it is the difference between the two sig- which relatively large currents can be drawn.
nals that is amplified. Note that in both circuits, the standard
Any extraneous potential common to the source appears in the feedback loop of an
two input terminals shown in Figure 3-22 will operational amplifier.
Rodiation be ~celed and not appear in the output. Recall (p. 58) that point S in Figure 3-23a
sou",. Thus, any slow drift in the output of the is 'at virtual ground. For this to be so, it is
A'-••
I
-~ I
transducers or any 6(kycle currents induced necessary that V. = V••••.That is, the current
I I from the laboratory power lines will be eli- through the load must be such that
minated from V.. This useful property I R,. = V..,. It is important to appreciate,
accoUnts for the widespread use of a differen- however, that this current arises from the
tial ~rcuit in the first amplifier stages of power source of the operational amplifier and
instnJments. not tire stalldard cell. Thus, the standard cell
The transducers shown in Figure 3-22 are controls v" without the passage of a
a pair of thermocouple jUllctiolls, one of which significant current through it.
is immersed in the sample and the second in a Figure 3-23b illustrates a modification of
reference solution (often an ice bath) held at the circuit in (a) which permits the output
constant temperature. A temperature-depend- voltage of the potentiostat to be fixed at a
ent contact potential develops at each of the level that is a known multiple of the output
two junctions formed from wires made of voltage of the standard cell.
copper and an alloy called constantan (other
(b)
metal pairs are also employed). The potential
FIGURE 3-21 Two simple circuits developed is roughly 5 mV per loooe temper-
conductance or resistance outputs. ature difference.

Application of
Operational Amplifiers
Figure 3-16 is at virtual ground (p. 58) can to V~ltage and Current Control
V_ - v" be applied to Figure 3-22, where it becomes
1,=--- Operational amplifiers are readily employed
Rt apparent that
to generate constant-potential or constant-
But Equation 3-10 reveals that II and I, are V_ = - V+ curreht signals.
approximately equal. Thus, COMtant-Voltage SoUrce. Several instru-
Substitution of this relationship into the
VI - V_ V_ - v" previous equation yields, upon rearrangement, mental methods require a power source
--R-i-=~ whose potential is precisely known and from
-V _ V1Rt + v"Rj which reasonable currents can be obtained FIGURE 3-22 A circuit for the amplifica-
+-
The argument demonstrating that point S in RI +Rt without alteration of this potential. A circuit tion of differences.
Figure 3-24b is an amperostat which em- evident in Chapter 6, however, it is the loga-
ploys a standard cell (V...,) to maintain a con- rithm of this ratio that is directly related to the
stant current; no significant current is, analyte concentration. Suitable modification
however, drawn from the standard. The non- of the circuit shown in Figure 3-21b permits
inverting booster amplifier permits relatively direct conversion of the outpUt signal to a
large currents to be passed through the cell. logarithmic function.
The outputs of several analytical methods,
Application of for example, chromatography, take the form
Operational Amplifiers
to Mathematical Operations
of a Gaussian-shaped peak in which an elec-
trical signal is plotted as a function of time.
Vo·-R,
. (V,-+-+-+-
V2 V, V.)
R, R2 R, R.
Integration to give the area under the peak is • -Rill, + 12+ I, + 1.1
An important property of the basic inverting
necessary in order to provide a parameter FIGURE 3-25 A summing circuit.
operational amplifier circuit shown in Figure
that is proportional to concentration. Opera-
3-16 is that substitution of various combina-
tional amplifiers can be used to perform the
tions of resistors and capacitors for Rj and R,
integration process and thus give directly a
permit mathematical operations to be per-
concentration-dependent signal.
formed on the input signal. Often, as a
Multiplication and Division by a Con-
consequence, the output is more easily related
to the concentration of the analyte. For
example, we have shown in Figure 3-21b how
stant. We have already seen that the output
of the basic inverting amplifier circuit is given
.=
y.
-R, ( -
VI
RI
+-V2 +-V3 +-V~)
R2 R3 R~
by (3-19)
(bl
the electrical output from a pair of photo-
diodes can be converted to a signal that is R, If the four input resistors and the feCdback
FIGURE 3-23 Constant p0- directly proportional to the ratio of the power v = -v·- resistor are all alike (R, = R == RI = R2 =
tential sources.
• I Rj
of two beams of radiation. As will become R3 == R~~ then the output potential is the
Here, the input signal is being multiplied by a sum of the four input potentials. That is,
constant whose magnitude can be varied by
alteration of the resistance ratio. When this V.=VI+V2+V3+V~

. Constant Current Sources. Constant cur- ratio is less than one, the operation is equiva- Another interesting case arises when
lent to division of the signal by a constant.
rent sources, called amperostats, find applica- RI = R2 = R3 == R~ = R = 4R,
Adclition.nd Subtraction. Figure 3-25 illus-
tion in several analytical instruments. These V,
devices are usually employed to maintain a h-- trates how an operational amplifier can be Here, Equation 3-19 reduces to
Rj
employed to yield an output that is the sum
constant current through an electrochemical
cell. An amperostat reacts to a change in of several input signals. It is important to Y. = _ ~(VI + V2 + V3 + \14)
note again that the point S is at virtual • 4 R R R R
input power or a change in internal resistance
ground. As a consequence, the various input c' (VI + V2 + V3 + V~)
of the cell by altering its output potential in
such a way as to maintain the current at a signals do not interfere with one another; all 4
predetermined level. flow independently to the virtual ground.
Thus, the current at S is simply the sum of the and the output gives the average value for the
Figure 3-24 shows two amperostats. The
individual currents. Because the impedance of four signals. Clearly, a weighted average can
first requires a voltage input V; whose poten-
the amplifier is large, however, be obtained by varying the values of the input
tial is constant in the presence of a current. resistors.
Recall from our earlier discussion that Subtraction becomes possible with the cir-
cuit by reversing the sign of one or more of
the input signals. •
I, = - V./R, Integration. Figure 3-26a shows a useful
Thus, the current will be constant and circuit for integration of a varying-input
independent of the resistance of the cel~ lbl Therefore, signal. Here, a capacitor CI replaces the re-
provided that V; and R remain constant.
j FIGURE 3-24 Constant current sources. V.= -R,(II + 12 + 13 + I~) (3-18) sistance R I in the basic inverting circuit.
3-28a overcomes this problem. Here the
v = --
• R,C
1
f v, dt
'
0
(3-20) introduction· of a small capaci~ C i~ the
feedback circuit and a small resisto: R in
the input circuit filters the high-frequency :olt-
Hold Thus, the output is the time integral of the
ages without significant attenuation of
lWitl:h input voltage. The definite integral is ob-
Vl~ the signal of interest. Figure 3-28b shows
tained by opening the reset switch and closing
the appearance of a typical titration curve v,
the hold switch (Figure 3-26a) at time zero.
and its derivative v•.
Then, when the hold switch is opened at time
t, the integration is stopped, thus holding v.
Generation or Logarithms and Antiloga-
rithms. A number of transducers produce an
at a constant level for measurement. Closing
electrical response which is exponentially
the reset switch then discharges the capacitor
related to concentration. Thus, it is the loga-
so that a new integration can be started.
rithm of the signal that is directly proportional
Figure 3-26b shows a chromatogram
to concentration. Figure 3-29a shows a circuit
(lower curve) and its time integral obtained
t~at will convert an input to its logarithm;
with an operational amplifier circuit. Note
FIgure 3-29b shows a circuit that will provide
that for each peak. there is a corresponding
the antilogarithm of an input. It should be
step in the intepl curve. The height of this
noted that the circuits shown in Figure 3-29
step corresponds to v. in Equation 3-20 and is
Volume, ml ---.. require that the input voltage be of a fixed
ordinarily proportional to the concentration
(bl polarity.
of the species responsible for the peale.
Differentiation. Figure 3-27 is a simple cir- FIGURE 3-28 (a) A practical circuit for
cuit for differentiation. Note that it differs differentiation. (b) Titration curve v, and its
(bl from the integration circuit only in the re- derivative v•.
spect that the positions of C and R have been
FIGURE 3-26 (a) Circuit for integration.
reversed. Here, we may write
(b) A chromatogram and its time integra~
where v. is proportional to the concentration dv, v.
of the species X. C,-== -- where the rate of change in the transducer
dt Rr
signal is low. For example, differentiation is a
useful way to treat the data from a poten-
ilv,
v = -RfC,- tiometric titration; here, the potential change
• dt of interest occl,lrs over a period of a second or
To analyze this circuit, recall that for all The circuit shown in Figure 3-27 is not, in more (f S; 1· Hz). The input signal will,
practical purposes, fact, practical for most chemical applications, however, contain extraneous 60-, 120-, and
2400Hz potentials (see Figure 3-34), which are
ij= ir induced by the ac power supply. In addition,
Because point S is at virtual ground, the signal fluctuations resulting from incomplete
; output v.' is the voltage across the capacitor. mixing of the reagent and analyte solutions
Thus, substituting Equation 2-22 (p. 16) and are often encountered. Unfortunately, the
i Ohm's law into the foregoing equality gives output of the circuit in Figure 3-27 has a
strong frequency dependence; as a
.!i = _Cdv• consequence, the output voltage from the ex-
R, dt traneous signals often becomes as great or
greater than that from the changing trans-
(bl
ducer signa~ even though the magnitude of
FIGURE 3-27 Asimplecircuitfordifferen- the former relative to the latter is small. FIGURE 3-29 Circuits for generating
tiation. The modified circuit shown in Figure (a) logarithms and (b) antilogarithms.
concentration level. At double the analyte
concentration (Figure 3-3Of~ the existence of
The ultimate limitation to the accuracy and the rectangular wave becomes obvious;
Aelative
sensitivity of an analytical method is the accurate determination of the ac amplitude enalyte
presence of extraneous and unwanted signals would, however, be difficult. At the highest conen ANllyte signal Signal + noise SIN

that are superimposed on the analyte signal concentration of analyte, the presence of the

,I ,I
being measured. These extraneous signals are repetitive analytical signal is clearly seen; the
called noise, the terminology being derived relative error associated with the measure- 0 0
"M), .• ~
from radio engineering, where the presence of ment of its amplitude would be significantly ~v VV • \\J
unwanted signals was recognizable to the ear smaller than at the lower concentrations.
0 0
as noise or static. Amplification of a noisy signal provides
(e) (bl
The effect of noise on an analyte signal is little improvement because typically both the
shown in the plots on the right-hand side of noise and the information-bearing signal are

,~""
Figure 3-30. The graphs on the left are the amplified to the same extent; in addition,
theoretical signals in the absence of noise. noise may be added by the amplification
Note that the analytical signal is a rectangu- process. This effect is shown in Figure 3-31,
. Jar wave whose current or voltage amplitude where the noise shown in Figure 3-3Ob has
is directly proportional to analyte concentra-
tion; the signals shown are for relative con-
been doubled and superimposed upon the
pure signal in Figure 3-3Oe. Here, the output
,~
o 0
centrations of 0: I : 2 : 4. The noise assumed is effectively that of Figure 3-3Od after dou-
to be associated with the measurement is bling. Again, visual detection and measurement
shown in Figure 3-3Ob, where the analyte of the analyte signal would be unsatisfactory.
concentration is zero. For the purpose of It is worth noting here that lock-in amplifiers,
illustration, this same noise has simply been
added to the three analyte signals (c, e, and
g~ Thus, the representations in graphs d, (
which are discussed in a later section, do
permit amplification and extraction of a
signal from much of the accompanying noise.
, ,In n n ,~J1I.~
L!h 'VtM- ,
~t
and h are artificial because the fluctuations are It is apparent from these illustrations that
random and would differ from measurement noise becomes increasingly important as its o 0

to measurement unless all four signals were magnitude approaches that of the analyte
observed simultaneously. Furthermore, it has signal; thus, the signal-to-noise tatio SIN is a
been assumed that no significant noise is as- much more useful parameter than the abso-
sociated with the analyte signal itself; such a lute noise level in describing the quality of the
situation is unlikely in real measurements. output from a chemical measurement.
Finally, noise is not necessarily random; it
often has both random and nonrandom com- Signal-to-Noi •• Ratio
ponents. Nevertheless, the illustration is
useful. The signal-to-noise ratio associated with a
measurement is often expressed in terms of a
Examination of the signal plus noise in
ratio of currents, voltages, or power asso-
Figure 3-3Od suggests that the presence of
noise would make detection of the analyte ciated with the signal and the noise. It may ~ 00

signal difficult, or perhaps impossible, at this also be expressed in terms of the decibel; by FIG U R E 3-30 The effect of noise on an ac signal. In each ins1ance, the
definition, noise shown in (a) has been superimposed on the signal from the first column.

!
N
(decibels)
• For a more detailed discussion of noise see: T. Coor, J.
en. Educ. 45, AS34 (1968)and A. J. Diefenderfer,
Principles of Electronic Instrumentation. Philadelphia, = 20 log signal voltage or current
Saunders. 1979.Chapter 13. noise voltage or current
.~
The random noise for an instrument can Johnson Noise. Johnson noise owes its After amplification,
often be obtained by performing 20 to 30 source to the thermal motion of electrons in
measurements on a blank. The noise then is resistors and other resistive elements of an ",ms = 0.013 x 100 = 1.3 mV
taken as the standard deviation of the set (see electrical circuit. This agitation, which Shot Noise. Shot noise arises wherever a
Appendix 1~ That is, o decreases as temperature is r~uced, imparts current involves the transfer of electrons or
a random motion to the electrons, which in other charged particles across junctions. In
1 (x. -

.rn-n
x)
turn causes inhomogeneities in electron densi- the typical electronic circuit, these junctions
(n - 1) ties throughout the resistor. Thus, momentary are found at p and n interfaces; in photocells
where x. is the observed parameter and x is small voltage differences develop within re- and vacuum tubes, the junction consists of
the mean for the n measurements. The SIN gions of the resistor, and the net voltage drop the evacuated space between the anode and
values shown in the last column in Figure across the resistor fluctuates slightly with the cathode. The currents in both result from
3-30 were based on this definition of N; that o time. Note that Johnson noise will occur even a series of quantized events. namely, the
is, they are ratios of the amplitudes of the ac in the absence of a current. transfer of individual electrons across the
signals to the standard deviation derived from The magnitude of Johnson noise is readily junction. Thus, the current results from a
the blank. As a rule of thumb, visual observa- derived from thermodynamic considerations4 series of random events, the number of which
tion of a signal becomes impossible when SIN and is given by
is subject to fluctuation from instant to
is smaller than from two to three. instant. Because the behavior is random,
. however, the magnitude of the current fluctu-
where "•••••is the root-mean-square noise volt- ation is readily susceptible to statistical treat-
Sources of Nol ••
age lying in a frequency bandwidth of ment using the equation
Noise is associated with each component of M" Hz, k is the Boltzmann constant (1.38 x
an instrument-that is with the source, the 10-23 J/deg~ T is the absolute temperature, = J2Je Af
i,•••• (3-24)
FIGURE 3-31 Effect of
transducer, the signal processor, and the read- and R is resistance in ohms of the resistive where i,ms is the root-mean-square current
amplification of a noisy
out Furthermore, the noise from each of element. fluctuation associated with the average direct
signal. Here, both the noise
these components may be of several types and It is important to note that Johnson noise. current J. e is the charge on the electron
and the signal from Figure
arise from several sources. Thus, the noise while dependent upon the frequency band- (1.6 x 10-19 q and M" is again the band-
3-3Od have been doubled.
that is actually observed is a complex compos- width. is independent of frequency itself; thus. width of frequencies being considered. Like
ite, which usually cannot be fully charac- it is sometimes termed white noise by analogy Johnson noise, shot noise has a •.white ft

terized. Certain kinds of noise are to white light, which contains all visible spectrum.
recognizable, however, and a consideration of frequencies. It is also noteworthy that John- Flicker Noise. Flicker noise is charac-
their properties is useful. example. incomplete mixing of a reagent with son noise is independent of the physical size terized as a noise whose magnitude is in-
Instrumental noise can be divided into an analyte solution during a titration often of the resistor. versely proportional to the frequency of the
four general categories. Two, thermal or John- causes initial fluctuations (or noise) in the signal being observed; it is sometimcs tcrmed
son noise and shot noise, are well understood, potential of an electrode system used to mon- EXAMPLE l/r (olle-over{) noise as a consequence. The
and quantitative statements can be made itor the analyte concentration. Uncontrol- Calculate the Johnson noise at the input causes of flicker noise are not well undcr-
about the magnitude of each. It is clear that lable variations in the temperature of an arc and the output of an amplifier having an stood; its ubiquitous presence. however, is rec-
neither Johnson nor shot noise can be totally source used to excite the atomic spectrum of input resistance of I MO and an amplification ognizable by its frequency dependence.
eliminated from an instrument. an element often cause significant fluctuations , of 100. Assume the bandwidth of the input Flicker noise becomes significant at frequen-
Two other types of noise are also recogniz- in the intensity of the line that is employed as ; signal is 104 Hz. The temperature is 25°C. cies lower than about 100 Hz. The long-term
able, environmental noise and flicker or Ilf a measure of concentration. Noise of this type Employing Equation 3-23. we find drift observed in dc amplifiers, meters, and
noise. Their sources are neither well defined
nor understood. In principle, however, they
is often more significant than instrumental i
noise.
V,ms = J4 x 1.38 x 10-23 x 298 X 106 x 104 galvanometers is considered to be a mani-
festation of flicker noise.
can be eliminated by appropriate instrument _ The sections that follow deal with in- = 1.3 x 10-5 V or 0.013 mV Environmental Noise. Environmental noise
design. strumental noise only. Noise associated with is a composite of noises arising from the sur-
In addition to instrumental noise, the re- the properties of analytes will be dealt with in roundings. Figure 3-32 suggests typical
sults of an analysis are often affected by a the chapters devoted to specific instrumental • For example, see: T. Coor, J. Chem. Edue .• 45, AS33 sources of environmental noise in a university
type of noise related to the analyte itself. For methods. and ASS3 (1968). laboratory.
Gl'OUIIlIi.. and Shielding. Noise ansmg the input signal to a narrow band of frequen-
Power line
60-
from environmenfa1ly generated electromag- cies and employing an amplifier that is tuned
180- netic radiation can often be substantially to this band. It should be appreciated,
reduced by shielding, grounding, and mini- however, that if the signal generated from the
I· Good ·1 mizing the lengths of conductors. Shielding analyte varies with time, the bandwidth must
qUtet
region consists of surrounding a circuit, or Some of be sufficiently great to carry all of the infor-
the wires in a circuit, with a conducting mate- mation provided by the signal.
rial that is attached to earth ground. Electro- Mndulation. Amplification of a low-fre-
magnetic radiation is then absorbed by the quency or dc signal is particularly"troublesome
shield rather than by the enclosed conduc- because of amplifier drift and flicker noise.
tors; noise generation in the instrument cir- Often, this Iffnoise is several times larger than
cuit is thus avoided in principle. the types of noise that predominate at higher
Shielding becomes particularly important frequencies. For this reason, low-frequency or
when the output of a high-impedance trans- dc signals from transducers are often converted
FIGURE 3-32 Some sources of environmental noises in a university ducer, such as the glass electrode, is being to a higher frequency, where Iff"noise is less
laboratory. Note the frequency dependence. [From T. Coor, J. Chern. amplified. Here, even minuscule induced cur- troublesome. This process is call~ modulation.
Educ~ 45,533 (1968). With permission.] rents give rise to relatively large voltage drops After amplification, the modulated signal can
and thus to large voltage fluctuations. be freed from amplifier Iff noise by filtering
Difference Amplifiers. Any noise generated with a high-pass filter; demodulation and
in the transducer circuit is particularly critical filtering with a low-pass filter then produces a
because it appears in an amplified form in the . dc signal suitable for driving a re8dout device.
Much environmental noise occurs because instrument readout. To attenuate this type of Figure 3-34 is a schematic diagram show-
Signat-to-Nol.e Improvement
each conductor in an instrument is poten- noise, most instruments employ a difference ing the flow of a signal thrdugh such a
tially an antenna capable of picking up elec- Many laboratory measurements require only amplifier, such as that shown on page 51, for system. Here, the original dc current is mod-
tromagnetic radiation and converting it to an minimal effort to maintain the signal-to-noise the first stage of amplification. An ac signal ulated to give a narrow-band 4OO-Hz signal
electrical signal. Numerous sources of electro- ratio at an acceptable Ieve~ because the sig- induced in the transducer circuit generally
magnetic radiation exist, including ac power nals are relatively strong and the require- appears in phase at both the inverting and
lines, ignition systems in gasoline engines, ments for precision and accuracy are low. noninverting terminals; cancellation, however,
arcing switches, brushes in electrical motors, Examples include the weight determinations occurs at the output.
lightning, and ionospheric disturbances. Note made in the course of a chemical synthesis or
that some of these sources, such as power the color comparison made in determining
Fllte,. v,~
lines. cause noises with limited-frequency the chlorine content of the water in a swim-
bandwidths. ming pool. For both examples, the signal is High, low, and resonant filters (pages 23 to
It is also noteworthy that the noise spec- large relative to the noise and the require- 27) are often employed to remove noise that
trum shown in Figure 3-32 contains a large, ments for accuracy are minimal. When the differs in frequency from the signal of interest.
continuous noise region at low frequencies.
This noise has the properties of flicker noise;
its sources are unknown. Superimposed upon
the flicker noise are noise peaks associated
with yearly and daily temperature fluctua-
tions and other periodic phenomena asso-
ciated with the use of the laboratory building.
need for sensitivity and accuracy increases,
however, the SIN ratio often becomes the lim-
iting factor of a measurement.
Two general methods exist for overcoming
signal-to-noise limitations. The first entails re-
duction of the noise by appropriate instru-
ment design. The second makes use of some
Figure 3-33 illustrates the use of a low-pass
RC filter for reducing environmental and
Johnson noise from a slowly varying dc
signal. High-pass filters are also useful. Gen-
erally, this type of filter is employed to reduce
drift and other flicker noise from an ac signal.
Resonant filters are also used to attenuate
V~t2
- Time

Finally, two quiet-frequency regions in type of signal averaging to isolate the signal noise in electronic circuits. We have pointed FIGURE 3-33 Use of a
which environmental noises are low are in- from the noise. out that the magnitude of fundamental noise low-pass filter with a large
dicated in Figure 3-32. Often, signals are con- The sections that follow deal briefly with is directly proportional to the frequency time constant to remove
verted to these frequencies to reduce noise some of the methods that are employed to bandwidth of the signal. Thus significant noise from a slowly chang-
during signal processing. overcome the effects of noise. noise reduction can be achieved by restricting ing dc voltage.
that is amplified by a factor of 105• As shown, their surroundings; that is, they suffer from Signal form.

b
however, amplification introduces Iff and serious environmental noise effects. e
power line noise; most of this noise can be In order to minimize these noise problems,
removed with the aid of a suitable filter the beams from infrared sources are generally
before demodulation. chopped by imposition of a slotted rotating I I III I I I
nnnn
Sipal Chopping; the Chopper Amplifier.
The chopper amplifier provides one means for
disk in the beam path. The rotation of this
chopper produces a radiant signal that fluctu-
t I I II I I I

I~vo --- 1.5V

accomplishing the signal flow shown in Figure ates periodically between zero and some max-
3-34. In this device, the input signal is con- imum intensity. After interaction with the Circuit
verted to a rectangular wave form by an sample, the signal is converted by the trans- A B

1
ducer to an ac electrical signal whose Vi
electronic or mechanical chopp~. Chopping V.
can be performed either on the ~source itself frequency depends upon the size of the slots
or on the electrical signal from t~ transducer. and the rate at which the disk rotates. Envi-

1~
In genera~ it is desirable to chop the signal as ronmental noise associated with infrared
close to its source as possible because it is only measurement is generally dc or low-frequency
the noise arising after chopping that is removed
by the process.
Infrared spectroscopy provides an example
of the use of a mechanical chopper for signal
. modulation. Noise is a major. concern in
detecting and measuring infran:d radiation
ac; it can be largely eliminated by use of a
high-pass filter prior to amplification of the
electrical signal. .
Another example of the use of a chopper is
shown in Figure 3-35. This device is a chopper
amplifier, which employs an ac-driven
FIGURE 3-35 A chopper amplifier. The signal forms are idealized wave
forms at the various indicated points in the circuit.
I
"='

because both source intensity ~nd detector electromagnet to operate a switch that, in its
sensitivity are low in this regio~ of the spec- closed position, shorts the input or the output
trum. As a consequence, the electrical signal signal to ground. The appearance of the
approximately rectangular wave signal with ship to the latter. Figure 3-36a shows a
from an infrared transducer is generally small signal at various stages is shown above the
an amplitude of 6 mV (B). Amplification pro- system which employs an optical chopper to
and requires large amplification. Further- circuit diagram. The transducer input is
duces an ac signal with an amplitude of 6 V provide coherent analytical and reference sig-
more, infrared transducers, which are heat assumed to. be a 6-mV dc signal (A). The
(C), which, however, is shorted to ground per- nals. The reference signal is provided by a
detectors, respond to thermal radiation from vibrating sWitch has the effect of forming an
iodically; as shown in (D), shorting also re- lamp and can be quite intense, thus freeing it
duces the amplitude of the signal to 3 V. from potential interferences. The reference
Finally, the RC filter serves to smooth the and signal beams are chopped synchronously
signal and produce a 1.5-V dc output. The by the rotating slotted wheel, thus providing
synchronous demodulation process has signals that are identical in frequency and
Demodulation to de the effect of rejecting the noise generated have a fixed phase angle to one another.
.lter filtering within the amplifier. The synchronous demodulator acts in a

\ Lock-in Amplifiers.5 Lock-in amplifiers


permit the recovery of small signals even
when SIN is unity or less. Generally, a lock-in
amplifier requires a reference signal that is
manner analogous to the double poleo(fouble
throw switch shown in Figure 3-36b. Here,
the reference signal controls the switching so
that the polarity of the analytical signal is
coherent with the signal to be amplified. That reversed periodically to provide a rectified dc
is, the reference signal must be of the same signal, as shown to the right in Figure 3-36c.
frequency as the analytical signal and, equally The ac noise is then removed by a low-pass
important, must bear a fixed phase relation- filtering system.
A lock-in amplifier is generally relatively
o
1.0 free of noise because only those signals that
Frequency, Hz Frequency, Hz Frequency, Hz
are "locked-in" to the reference signal are
• See. T. C. O'H.ver. J. Chem. Educ., 49, A131. A211 amplified; that is, those that are coherent. AU
FIGURE 3-34 Amplification of a dc signal with a chopper amplifier.
(1972~ other frequencies are rejected by the system.
PRINCIPLES OF INSTRUMENTAL ANALYSIS

with computers in order to facilitate signal appears as a small bright dot in the center of
I
Monochromotor
Synchronous averaging. Here, the measuring process is the screen.
SIm_PIe ~SignaIor demodulator triggered repetitively, and the signal is accu- Input signals are applied to two sets of
mulated in one or more memory channels. plates, one of which deflects the beam hori-
.J V.
v. After a suitable number of sweepS or measure- zontally and the other vertically. Thus, x-y
ments, an average for the signal is computed. plotting of two related signals becomes
v, The effect of averaging is shown in Figure possible. Because the screen is phosphores-
_-0'-v, l
_ 3-37; the signal· is part of the output from an
NMR spectrometer. With a single scan, only
cent, the movement of the dot appears as a
lighted continuous trace that fades after a
Refenmce
detector a few of the peaks are discernible because brief period.
they are roughly the same size as the random The most common way of operating the
noise. After averaging the data from 50 scans, cathode tube is to cause the dot to be swept
the peaks begin to emerge; averaging 200 periodically across the horizontal axis of the
scans provides an even better spectrum. tube. For this purpose, a sawtooth sweep
Double-throw switch signal (p. 12) is employed. The signal to be
opel'llted in p"-
with v"" measured is then applied across the vertical
plates. If the signal is dc, it will simply
displace the horizontal line to a position
A variety of devices are employed for convert- above or below the central horizontal axis.
ing the output from a signal processor to a In order to have a repetitive signal, such as
(bl form that can:be read and interpreted by a sine wave, displayed on the screen, it is
man. We have:already considered some of essential that each sweep begin at an identical
these in thesedtion of Chapter 2 devoted to place on the wave; that is, for example, at a
.,~ meters. We hav~ also seen how the position of
a sliding contact on a linear resistor can be
maximum, a minimum, or a zero crossing.
Synchronization is usually realized by mixing
employed to provide voltage data (p. 34) or a portion of the test signal with the sweep

'.'LEft
resistance data (p. 35). _ signal in such a way as to produce a voltage
In this section, we consider two more so- . spike for, say, each maximum or some mul-
phisticated readout devices, namely, the tiple thereof. This spike then serves to trigger
cathode-ray tube and the laboratory recorder. the sweep. Thus, the wave form can be ob-
served as a continuous image on the screen.
The Cathode-Ray Tube
(e)
The oscilloscope is a most useful and versatile Recorders'
FIGURE 3-36 Alock_inamplifiersystem:(a)s~stemfora
laboratory instrument that employs a
spectrophotometer, (b) synchronous demodulation (sche- The typical laboratory recorder is an example
cathode-ray tube as a readout device. Figure
matic), and (c) signal form. of a servosystem, a null device that compares
3-38 is a schematic drawing showing the main
two signals and then makes a mechanical
components of the tube. Here, the display is
adjustment that reduces their difference to
formed by the ;interaction of electrons in a
numerous measurements of its magnitude can zero; that is, a servosystem continuously
Signal Avereglng6 focused beam with a phosphorescent coating
be performed. If the measurements can all be seeks the null condition.
on the interior pf the large curved surface of In the laboratory recorder, shown schemat-
Signal averaging provides a powerful tool for made in exactly the same way~the signals.wi~1 the tube. Electtions are formed at a heated ically in Figure 3-39, the signal to .be
extracting a small signal fro~ larg~ ~ounts be additive, but the noise, Insofar as It IS
cathode, which is maintained at ground recorded, v,., is continuously compared With
of noise. To apply this techmque, It IS neces- random and tends to cancel, adds. as the
potential; an anode with a potential of the the output from a potentiometer powered by
sary that the signal be repeatable, so that square root of the number of measurements n.
order of kilovolts accelerates the electrons
Thus, the SIN ratio is improved by a factor of through a control grid and a second anode
~. . that serves to focus the beam on the screen. , For a good discussion of laboratory recorders, see:
Many modern instruments are Interfaced In the absence of input signals, the beam G. W. Ewing, J. Chem. £due .• 53. A361. A407 (1976).
IntensitY
control Focusing Accelerating
grid: •• ode anode

fereooe signal can be caused to drive the ser- INTERFACING OF


vomechanism to the null state from either INSTRUMENTS WITH COMPUTERS
direction.
In most laboratory recorders, the paper is Undoubtedly, one of the major developments
moved at a fixed speed. Thus, a plot of signal in analytical chemistry during the last decade
FIGURE 3-37 Effect of signal averaging. Note that the intensity as a function of time is obtained. has been the interfacing of digital computers
vertical scale is smaller as the number of scans increases. A good-quality laboratory recorder will with the various instruments listed in Table
That is, the noise grows in absolute value with increased provide a record of voltages that is accurate I-I. At least two reasons exist for connecting
number of scans; its value relative to the analytical signal to a few microvolts. a computer to an analytical instrument. The
decreases, however.

a reference signal, v".,. The latter may be one To understand the directional control of
or more mercury cells, the potential of which the motor, it is important to note that a
remains constant throughout the lifetime of reversible ac motor has two sets of coils, one
the battery; alternatively, a rectified ac signal, of which is fixed (the stator) and the other of
stabilized by a Zener diode (p. 53) serves as which rotates (the rotor). One of these, say,
the reference. Any difference in potential be- the rotor, is powered from the no-v house
tween the potentiometer output and Vx is line and thus has a continuously fluctuating
converted to a 6O-cycle ac current by a magnetic field associated with it. The output c,
mechanical chopper; the resulting signal is from the ac amplifier, on the other hand, is
then amplified sufficiently to activate a small fed to the coils of the stator. The magnetic .~_ c.
phase-sensitive electrical motor that is me- field induced here interacts with the rotor ,Qac +
chanically geared or linked (by a pulley
arrangement in Figure 3-39) to both a record-
field and causes the rotor to turn. The direc-
tion of motion depends upon the phase of the
] _
-
-
Chopper
amplifier
er pen and the sliding contact of the poten-
tiometer. The direction of rotation of the
motor is such that the potential difference be-
stator current with respect to that of the
rotor; the phase of the stator current,
however, differs by 180 deg, depending upon
,r
V.

tween the potentiometer and v.: is decreased whether Vx is greater or smaller than FIG U R E 3-39 Schematic diagram of a self-balancing recording
to zero, whereupon the motor stops. the signal fro~ v".,. Thus, the amplified dif- potentiometer.
first is that partial or complete automation of Binary Number Syoem (b) 19 10011
.measurements becomes possible. Ordinarily, +6 110
The programs, instructions, mathematical 1011000110
automation leads to more rapid data acquisi- operations, and memories of a digital com-
tion and shortens the time required for an 29 - 27 26 - - - 22 21 -
25 11001
puter are all based upon the binary system of
analysis or increaSes its precision by provid- (c) 7
numbers rather than on the more familiar deci- 111
ing time for additional replicate measure- Arithmetic with binary numbers is similar x3
mal system. The decimal system is, of course, 11
ments to be made. Automation, moreover, based on ten digits; the binary system uses to, but simpler than, decimal arithmetic. For
frequently provides better control over exper- addition, only four combinations are possible. 111
but two, 0 and 1.
imental variabl~ than a human operator can 111
Table 3-1 illustrates the relationship be-
achieve; more precise and accurate data are
tween some decimal and binary numbers. The 10101
the result.
example thaf follows illustrates methods for
A second reason for attaching computers (d) 22
binary-to-decimal conversion and the reverse. 10110
to instruments is to take advantage of their
x5 101
tremendous computational and data-handling
capabilities. These capabilities make possible 10110
EXAMPLE
the routine use of techniques that would or- (a) Convett 101011 to a decimal number. 0‫סס‬oo
dinarily be impractical because of their exces- 10110
(b) Convert 710 to a binary number.
sive computational time requirements.
(a) To understand how this conversio~ 1101110
Notable among such applications is the use of
can be made, it is useful to realize that a decJ-
Fourier transform calculations in spectros-
mal number can be readily broken down into The following example illustrates the use of
copy to extract small analytical signals from Bits. The binary digits 0 and 1 are often
integer multi~1es of powers of ~O. For exam- these operations.
noisy environments. referred to as bits. Thus, the decimal number
ple, the numljer 4753 can be wntten as
The interfacing of computers with analyti- EXAMPLE 110 in part (d) of the example is called a
cal instruments is too large and complex a 4753 = three-digit number in the decimal system; the
Perform the following calculations with
field to be treated in detail here.8 Thus, the binary arithmetic. (a) 7 + 3, (b) 19 + 6, (c) binary equivalent 1101110 is a seven-bit
4 x 103 + 7 X 102 + 5 X 101 + 3 x 10°
discussion that follows is limited to a general number.
7 x 3, (d) 22 x 2.
summary of the properties possessed by com- 4000 +700 + 50 + 3 Words. A word consists of one or more
puters and the advantages gained by interfac- By analogy, binary numbers can be expressed (a) 7 111 bits that are associated with one another. The
ing them with analytical instruments. in terms of base 2. Thus, +3 +11 number of bits per word depends upon the
For many purposes, it is convenient to size of the computer; some common sizes in-
categorize computers on the basis of size. 101011 = 1 x 2' + 0 X 24 + 1 X 23 10 1010 clude 8, 12, 16, 24, and 64. Minicomputers
Here; size refers not only to physical dimen- 32 + 0 + 8
sions but more importantly to the quantity of
+ 0 X 22 + 1 X 21 + 1 x 2°
information and instructions that can be
stored. This discussion will focus on so-called + 0 + 2 + 1 = 43
minicomputers and microcomputers rather (b) As a first step, we determine the largest TABLE 3-1 RELATIONSHIP BETWEEN SOME
than on the large, centralized, general-purpose power of 2 that is less than 710. Thus, since DECIMAL AND BINARY NUMBERS
device. 21o = 1024, ;
Decimal Binary Decimal Binary
29 = 512 and 710 - 512 = 198 Number Representation Number Representation
The process Is repeated for 198 o
• For monographs on compuler interfacing, see: Com- o 8 1000
purtrs for SpectroJcoputJ,ed. R. A. G. Carrington. New 27 = 128 and 198 - 128 = 70 1 1 9 1001
York: Wiley, 1974; J.• Finkel, Computer-Aided Exper- 2 10 10 1010
imentation. New York: Wiley-Interscience, 1974; J. S. Continuing, we find 3 11 12 1100
MatlJoD, H. B. Mark, Jr, and H. C. MacDonald, Jr, 4 100 15 1111
Chemu/$. New York: Marcel 26 = 64 and 70-64=6
Computer Fundamentabfor 5 101 16 1‫סס‬oo
Dekker, 1973; and A. J. Diefenderfer, PrincipleJ of Elec- 2
2 = 4 and 6- 4=2 6 110 32 10‫סס‬oo
tronic Instrumentation, 2d ed. Philadelphia: Saunders, 7 111 64 1000ooo
1979,Chapters 10-12. 21 = 2 and 2- 2=0
logic to perform the various functions of the Tiny single chips containing 1024 to 4096 of
often employ 16-bit words and microcom- Major Components of a Computer computer; generally, the switches control volt- these elements are employed. Binary storage
puters 8. Computer memories are described Figure 3-40 is a block diagram showing the ages that range from 0 ± 0.5 V for the off or . and retrieval depends upon which half of the
in terms of the number of words they can arrangement of the major components of a o position and 5 ± 2 V in the on or I posi- circuit is conducting at any time. An
retain. Thus, an 8K memory has space for digital computer. tion. The band between 0.5 and 3.0 V is integrated-circuit memory has the disadvan-
approximately 8000 words. The Central Proceaiag Unit. The heart of sufficiently large to prevent interference by tage of being volatile; that is, loss of electric
A single word contains a pattern of bits a computer is the central processing unit, random noise. power results in loss of the stored
that cause the computer to take a specific which contains a control unit and an arith- Memory. Storage of data and instructions information.
action. Generally, a word contains a datum for a computer take two forms. One makes Input-Output Systems. Input-output devices
metic unit. The former controls the overall
or a command and an address, both written use of magnetic tapes or disks. Access to these provide the means by which the user (or
sequence of operations by means of a
in binary notation. The latter gives the loca- program, which is stored in the memory unit is relatively slow, and they are used primarily his instrument) communicates with the com-
tion of an instruction or a datum word in the The control unit ~receives instructions from for storage of programs and data for future puter. Familiar input devices include the
memory. For example, for a computer em- use. electric typewriter, punch cards or tapes,
the input device, fetches instructions and data
ploying 12-bit words, a word might take the from the memory: unit, transmits instructions The main memory of computers is either a magnetic tapes or disks, and the electrical or
form to the arithmetic. unit for computation, and magnetic-core type or an integrated-circuit mechanical signals from analytical instru-
transmits the results of these computations to type. In both, instructions or data are stored ments. Output devices include recorders, elec-
the output and often to memory as well in binary form with a separate core or circuit tric typewriters, cathode-ray screens, and
Here, the first three bits could be the code for The program, the instructions, the math- being required for each bit. Generally, the meters. It is important to appreciate that
a command such as add, subtract, multiply, ematical operations, and the memory of a dig- individual cores or circuits are arranged in most of these devices provide or use an
or store. The next two, in this example, are ital computer are all based upon the binary square arrays of 32 x 32 or 1024 storage posi- alUllog signal while, as we have pointed out,
not used. The last seven bits give the location system made up of just two states, on and 00; tions. For a computer employing words made the computer can respond only to digital sig-
of the number upon which the command is to or 0 and 1. The \:cntral processing unit of a up of 16 bits; one of these arrays would corre- nals. Thus, an important part of the input-
be exercised. For example, the word just computer contaiJls a vast array of transis- spond to 64 words. The minimum memory output system is an analog-to-digital converter
shown might command the computer to add torized switches, ~ach of which has only two capacity required for most computational (ADC) for inputting data, which the com-
the number stored in the indicated location settings, 0 or I, corresponding to on or 01T. applications is 4096 words (a 4K memory). puter can use, and a digital-ta-analog counter
(storage number 74) to another number. These switches are employed using binary Thus, the number of individual binary cores (DAC) for converting the output from the
or circuits is enormous. computer to a usable signal.
The individual storage unit or core in a By definition, an analog signal is one that
magnetic-core memory is made of a ferrite varies continuously, whereas a digital signal is
ceramic, shaped in the form of a doughnut. one that varies in discrete increments. An
The inside and outside diameters of the ring example of an analog signal is the voltage
are 0.013 and 0.020 in~ respectively. When an output of a glass electrode, which varies con-
electrical signal passes through a wire that is tinuously from about 0 to about 1.0 V
threaded through the ring, magnetization of depending upon the pH of the solution in
the ferrite material occurs; the direction of which it is immersed. Most, but not al~ analyt-
magnetization (clockwise or counter clock- ical instruments are analog; examples of ex-
wise) depends upon the direction of the ceptions include the output from the decay of
current and remains fixed after the current a radioactive species or from a Geiger tube
ceases. Thus, the core has two stable states when it is employed to measure the intensity
and can store binary information. A sensing of an X-ray beam.

•• wire running through the ring is then Most output devices such as recorders,
employed to sense the direction of magnetiza- plotters, and meters require analog rather
tion and thus retrieve the information stored than digital signals.


in the element. Where the analog signal is the rotary
An integrated-circuit memory element gen- motion of a shaft, a digital signal is readily
erally consists of a circuit containing four produced by means of a mechanical turn
transistors, two capacitors, and two switches. counter. One method of achieving a digital
signal is to mount on the shaft a circular disk to errors. For this reason, assembly languages
used in more than one way and by more than the user is required to obtain automated in-
that is notched to give opaque and transparent have been developed in which the switch-
one user at the same time without interfer- strument control.
slots. An array of light beams and pho- setting steps are. assembled into groups which
ences. A single minicomputer is frequently Microcomputer memories tend to be small-
tocells then produces a series of digital electri- can be designated by code word. For exam-
used to control several instruments in one er than those employed in minicomputers.
cal pulses as the disk rotates. Such a device ple, the abbreviation for subtract might be
laboratory. Memory increments of 256 words are avail-
might be employed to monitor the SUB and might correspond to 101 in machine
MiniComputers can usually be pro- able; typically, eight of these are employed to
wavelength setting of a monochromator or language. Clearly, SUB is a good deal easier
grammed in one or more high-level lan- provide a capacity of 2048 words. Only one
the null point of a potentiometer. for the programmer to remember than 101.
guages. Often, however, interfacing them with or two of the memory increments is required
More commonly, analog-to-digital convert- Assembly programming, while simpler
instrument signals may require the user to for the control of many instruments. Word
ers are electronic and are based upon count- than machine programming, is still difficult
construct subroutines in assembly language. lengths for microcomputers are commonly
ing square-wave pulses from a generator. and tedious. As a consequence. a number of
The central processing unit in a mini- eight bits.
Here, the number of pulses or their frequency high-level languages, such as FORTRAN and
computer generally ranges in cost from 51000 'Microcomputers, quite adequate for the
is determined by the analytical signal. Alter- Basic, have been developed. These languages,
to 510,000. The addition of storage, input and control of a single instrument and with data-
natively, the time required for a ramp voltage which are easily learned, have been designed
output devices, and other peripherals usually acituisition speeds of 1000 to 3000 words per
to change from zero to a chosen level may be to make communication with the computer
doubles these costs at a minimum and may second, are available for 51000 or less.
measured. relatively straightforward. Here, instructions
multiply them by a factor as great as five to tIn more complex instruments, one or more
Digital-to-analog converters are electronic in Basic or FORTRAN are translated by a
ten. microcomputers may be controlled by a
devices that convert a digital number into a computer program (called a compiler) into
minicomputer. The slave microcomputer then
voltage proportional to the number. The volt- machine language which can then control the
Microcomput •••• performs one or more control functions at the
age can then be employed to drive a record- computer for computations. Unfortunately,
command of the minicomputer.
er, meter, or other output device. loss of efficiency accompanies the use of The heart of a microcomputer is the micro-
higher-level languages. processor, a device that first appeared on the
Figure 3-41 illustrates the application of market in about 1973; the applications of
Computer Programming .A~Plicetiona of Compute •••
the three languages for obtaining a sum. microprocessors have grown exponentially
Communication with a computer entails set- since that time.9 A microprocessor is a com- Computer interactions with analytical instru-
ting an enormous aggregation of switches to plete central processing unit, which has been ments are of two types, passive and active.tO
Minicomput ••.•
appropriate off or on positions. A program miniaturized and formed on a single In passive applications, the computer does
consists of a set of instructions as to how A minicomputer is sufficiently small and inex- integratcd-circuit chip having an area of a few not participate in the control or the experi-
these switches are to be set for each step in an pensive that its use can be limited to one lab- square millimeters. Combination of a micro- ment but is used only for data handling,
instruction or a computation. Each of these oratory or even to a single instrument. A processor with a memory and an input- processing, storing, file searching, or display.
instructions must be written in a form to minicomputer will have at least 4K or output device. leads to a remarkably In an active interaction, the computer is
which the computer can respond-that is, a memory and often considerably more. inexpensive microcomputer, which can be significantly involved in the control of the
binary mJJChine code. Machine coding is te- Usually, it can be used on a time-shtJred basis. conveniently employed in conjunction with a experiment. Instruments with computer con-
dious and time consuming and is often prone That is, its capabilities are such that it can be single instrument; such a computer is said to trol are said to be automated.
be dedicated. Most new analytical instruments Passive Applications. Data processing by a
are being sold with one or more programmed computer may involve relatively simple math-
microprocessors as an integral part of the ematical operations such as calculation of
equipment. With these, no programming by ~ncentrations, data averaging, least-square
analysis, statistical analysis, and integration
o 110001 100 100 001 LOA Z
to obtain peak areas; as we have seen. several
0100 001100 100010 Assembler ADA B

0100 001 100 100 011 AOAC


• For a summary of the construction and applications of
o 111 001 100 100 100 STA 0
microprocessors and minicomputers. see: R. E. Dessy. P.
Janse·Van. Vuuren, and J. A. Titus. AMI. Chem. 46 (11~
917A (1974); 46 (12~ 10SSA (1974); B. Soucek. Micro- 10 This c1assification has been IUgated by Perone in his
FIGURE 3-41 Relationships among machine, as- procnson and Microcompuler<. New York: Wiley. 1976; summary or computer applicatioDl. See: S. P. Perone
sembly, and a high-level language. (From S. Perone, and An Introduclion 10 Microcompulers. Adam Osborne and D. O. Jones. Digital Compuler III ScinIlific
and Associates. P.O. Box 2036. Berkeley. CA 94710. 1977. llUll'lUMntation. New York: McGraw·Hill, 1973. Chapter
J. Chromatog, Sci., 7, 715 (1969). With permission.)
vol O. I. and 2. 12.
of these operations can also be performed the computer exercises at least some and 1. Design a circuit whose output V. is given by
with operational amplifiers. More complex sometimes all of the control of an instrument
during an analysis. Most modem instruments
- V. = 2V, + 4V2 + 1V3 + 3V4
calculations may involve solution of several
simultaneous equations, curve fitting, and contain one or more microcomputers that 2. Design a circuit for calculating an average value for three voltage
Fourier transformations. perform such functions. Examples would in- inputs multiplied by 100.
Data storage is another important passive clude control of the slit width and wavelength 3. Design a circuit for performing the following calculation:
function of computers. For example, a power- setting ora monochromator, the temperature
ful tool for the analysis of complex mixtures of a chromatographic column, the potential y = !(2x, + 3X2)
is obtained by linking gas-liquid chromatog- applied to an electrode, the rate of addition of
raphy (GLe) with mass spectrometry (MS). a reagent, and the time at which the integra-
The former is capable of separating mixtures tion of a peak is to begin. Referring again to
on the basis of the time required for the indi- the GLCjMS instrument considered in the R" Rf2
vidual components to appear at the end of last section, a computer is often used to ini-
suitably packed columns. Mass spectrometry tiate collection of mass spectral data each R,
permits identification of each co~ponent time a compound is sensed at the end of the V,
according to the mass of the fragments chromatographic column. R.
V.
formed when the compound is bombarded Computer control can be relatively simple,
with a beam of electrons. GLCjMS equip- as in the examples just cited, or more .".
ment may produce as many as 100 spectra in complex. For example, the determination of R3
V3
less than an hour, with each spectrum being the concentration of elements by atomic emis-
made up of tens to hundreds of peaks. Con- sion involves the measurement of the heights
version of these data to an interpretable form of emission peaks that occur at wavelengths
is time consuming; thus, the data must be characteristic for each element. Here, the I
(a) write an expression giving the output voltage in terms of the three
stored in digital form for subsequent printing. computer can cause a monochromator to
input voltages and the various resistances. .
Identification of a species from its mass sweep a range of wavelengths until a peak is
(b) indicate the mathematical operation performed by the circuit
spectrum involves a search of files of spectra located, and can then seek the exact
when R1 = Rfl = 100 kn; R4 = Rf2 = SOkn; R2 = 2S kn;
for pure compounds until a match is found; wavelength at which the maximum output
R3 = 10 kn.
this process is also time consuming, but can signal is obtained. Measurements are made at
be accomplished quickly by using a this point until an average is obtained that S. Show the algebraic relationship between the voltage input and output
computer. Here, a magnetic disc or magnetic will give a suitable signal-to-noise ratio. The for the following circuit:
tape file storage is required. For example, computer then causes the instrument to
programs have been described which permit repeat this operation for each peak of interest
the search of several thousands of spectra in a in the spectrum. Finally, the computer
minute or less. Such a search will frequently processes the data and prints out the concen-
produce several possible compounds. Further tration of the elements present. 3kU
comparison of spectra by the scientist usually Because of its great speed, a computer can v,
makes identification possible. often control variables more efficiently than SkU
v,
Another important passive application uti- can a human operator. Furthermore, with 4kU
lizes the high-speed data fetching and cor- some experiments, a computer can be pro- V3
relating capabilities of the computer. Thus, grammed to alter the way in which the mea- 6kU
V.
for example, the computer can be called upon surement is being made, according to the
to display on a cathode-ray screen the spec- nature of the initial data. Here, a feedback
trum of anyone of the components after it loop is employed in which the signal output is
has exited from a gas chromatographic fed back through the computer and serves to 6. What would be the output voltage of the circuit shown in Figure
column. control and optimize the way in which addi- 3-26a after 30 s, if the input voltage is 2S mY, the resistor is 200 kQ,
Active Applicatiol& In active applications, tional measurements are made. and the capacitor is 0.26 JlF?
12. The linear slide wire AB has a length of 100 an. Where along its
length should contact C be placed in order to provide a potential of
exactly 2.50 V?

8. Show that when the four resistances are equal. the following circuit
becomes a subtracting circuit.

13. Design a circuit that will produce the following output:

V. =2 .f VJ dt +3 f V2 dt

14. Design a circuit that will produce the following output:

V. =3 f VI dt - 4(V2 + V3)
9. Derive a relationship between v..
I't. and ~ for the circuit shown in 15. The following data were obtained for repetitive weighings ofa 12S4-g
Problem 8 when Ru = Ru and RJ = R2• object with a top-loading balance. Calculate the signal-to-noise ratio
10. Derive a relationship between V. and l'/ for the following circuit: for the measurements, assuming the noise to be random.
1253 g 12S6g
1256 1.252
1.257 1.254
1.254 1.255
16. How many measurements would have to be averaged to increase SIN
in Problem 15 to l000?
17. The following data were obtained for a current measurement on a
noisy system. What is the signal-to-noise ratio. assuming that the
noise is random?
1.34 flA 1.10 flA
1.76 1.63
121 1.77
1.35 1.19

18. How many measurements would have to be averaged to obtain a


~v. signal-to-noise ratio of 10 for the mean in Problem 16; to obtain a
ratio of l00?
19. The resistance of a dc circuit is 1500 0. What is the maximum resist-
ance that a current-measuring device can havc if thc current in this
circuit is to be measured with a relativc error of less than 2 %? Thc
cxpected current range is 0 to 20 pA.
20. Devise an operational amplifier circuit employing a 0 to 10 mV mctcr
that will meet the requirements specified in Problem 20.
21. Thc resistance of a dc circuit is 200 0. What is thc maximum resist-
ance that a current-measuring device can havc if thc current in this.
circuit is to be measured with a relative error of less than 5 %? The
expected current range is 0 to 50 pA.
22. Devise an operational amplifier circuit employing a 0 to 10 mV meter:
that will meet the requiremcnts specified in Problem 21. .
the zero axis. Normally, only' the electrical maximum. This velocity, given the symbol c,
This chapter reviews several topics concerned as particles and waves are not mutually exclu- vector is employed because it is the electriclJl has been accurately determined to be
with electromagnetic radiation, including the sive. Indeed, the duality is found to apply to force that is responsible for such phenomena 2.99792 X 1010 em/s. Thus, for a vacuum,
fundamental properties of this radiation and the behavior of streams of electr~ns or. other as transmission, reflection, refraction, and
the mechanism of its interactions with matter. elementary particles as well and IS readdy ra- absorption of radiation. . . c = vl ~ 3 x 1010 emls (4-2)
The material will serve as a general introduc- tionalized by wave mechanics. Figure 4-1 is a plot ofthe electr.ical vector
In any other medium, the rate of propagation
tion to the various instrumental methods dis- of monochromatic plane-polarized radiation, is less because of interactions between the
cussed in Chapters 5 through 14} Wave Properties the simplest type. The first term indicates that electromagnetic field of the radiation and the
For many purposes, electromagnetic. ~ia- the radiation has a single. frequency; the bound electrons in the atoms or molecules
tion is conveniently treated as an OSCIllatmg second implies that it oscillates in but a single making up the medium. Since the radiant
PROPERTIES OF electrical force field in space; associated ~~ plane in space.
frequency is invariant and fixed by the ~u~ce,
ELECTROMAGNETIC RADIATION Wave Parameters. The time required for
the electrical field, and at right angles to It, IS the wavelength must decrease as radiatIon
a magnetic force field. . the passage of successive maxima through a passes from a vacuum to a me<!ium con~ai?-
Electromagnetic radiation is a type of energy fixed point in space is called the period p of
The electrical and magnetic fields ass0- ing matter (Equation 4-1). ThiS effect IS il-
that is transmitted through space at enor- the radiation. The frequency v is the number
ciated with radiation are vector quantities; at lustrated in Figure 4-2.
mous velocities. It takes numerous forms, the of oscillations of the field that occurs per
any instant, they can be represented by an It should be noted that th~ velocity of ra-
most easily recognizable being light and ra- second2 and is equal to lip. It is important to
arrow whose length is proportio~ t~ t~ diation in air differs only slightly from c (about
~iant beat. Less obvious manifestations include realize that the frequency is determined by the
magnitude of the force and whose direction IS 0.03% less); thus, Equation 4-2 is usually
X-ray, ultraviolet, microwave, and radio source and remaillS invariant regardless of the
parallel to that of the force. A ~phical rep- applicable to air as well as to a vacuum.
radiations. . media traversed by the radiation. In contrast,
resentation of a beam of radiation can be The wavenumber (1 is defined as the
Many of the properties of electromagnetIC the velocity of propagation v,, the rate at'
obtained by plotting one of these vect.or number of waves per centimeter and is yet
radiation are conveniently described by which the wave front moves through a
quantities as a function. of ~ime as the radia- another way of describing ielectromagnet~c
means of a classical wave model which em- medium, is dependent upon both the medium
tion passes a fixed potnt tn space. Alterna- radiation. When the wavelength in vacuo IS
ploys such parameters ~ wavelength, fre- and the frequency; the subscript i is employed
tively, the vector can be plotted as a function expressed in centimeters, the' wavenumber is
quency, velocity, and amplItude. In contrast to to indicate this frequency dependence.
other wave phenomena, such as sound,
of distance, with time held constant. equal to Iii..,",,"", ')
In Figure 4-1, the electrical vector .serves as Another parameter of interest is the wave- Radiant Power or Intensity. The power P
electromagnetic radiation req~ir~ no suI: length Ai' which is the linear distance between
the ordinate; a plot of the magnetIC vector of radiation is the energy of the beam that
porting medium for its transmIssIon; thus, It successive maxima or minima of a wave.J
would be identical in every regard except that -' reaches a given area per second; the intellSity
readily passes through a vacuum. Multiplication of the frequency in cycles per
the ordinate would be rotated 90 deg around '- 1 is the power per unit solid angle. These
The wave model fails to account for phe- second by the wavelength in centimet~ ~ quantities are related to the square of ~h~am-
nomena associated with the absorption or cycle gives the velocity of propagatton .m plitude A (see Figure 4-1). Although .It IS ~ot
emission of radiant energy; for these centimeters per second; that is, strictly correct to do so, power and mtenslty
processes, it is necessary to view e~ectro-
Vi = VA; (4-1) are often used synonymously.
magnetic radiation as a stream of dISCrete I
A---., •
_Wavelength. Mathematical Description of a Wave. With
particles of energy called photons. The energy I
I
I
, In a vacuum the velocity of radiation be-
I time as a variable, the wave in Figure 4-1 can
of a photon is proportional ~o the freq~e~cy comes independent of frequency and is at its be described by the equation (see Equation
of the radiation. These dual vIews of radtatlon
2-18, p. 12)
y = A sin(wt +< I/J) (4-3)
z The common unit of frequency is the hertz Hz, which is
I For a further review of these topics, see: E. J. Bair,
equal to one cycle per second. where y is the electric force, -1 is the amplitude
Introtlucrwn ro Chemical I ••.•,rumen,a,ion. New York:
or maximum value for y, t ~s time, and I/J is
McGraw-HilI, 1962, ChapletS 1-2; E, J. Bowen, The 3 The units commonly used for describing wavelength
Chemical hpecl!l of Light, 2d ed. Oxford: The Clarendon differ considerably in the various spectral regions. For
the phase angle, a term which has ~n
Press, 1946; E. J. Meehan, Treatise on Analytical Chem- example, the AngstrOm unit, A (10· I.m), is eonvenient for defined earlier (p. 12). The angular velOCIty
islry, eels. I. M. Kolthofl' and P. J. Elving, Part I, vol. ~,
FIGURE 4-1 Representation of a beam X-ray and short ultraviolet radiation; the nan~meter, ~ of the vector, w, is related to the frequency of
New York: Wiley, 1964, Chapter 53; and. F. Grum m
of monochromatic, plane-polarized radia-
(10·' m), is employed with visible ~nd ultraVlolet ~adla- the radiation v by the equation
Physical Me/hods of Chemistry, eels. A. WeJSSberger and tion; the micrometer,/lm (10·' m), IS useful for the mfra-
B. W. Rossiter. New York: Wiley-Interscience, 1912, Vol. tion. The arrows represent the electrical red region. w = 2ltv
I, Part III B, pp. 214-305. vector.
or cosine terms such as those shown in Equa- approximate the shape of a square wave. As
tion 4-5. For example, the square wave form shown by the solid line in Figure 4-4b, the
often employed in electronics can be repre- resultant more closely approaches a square
sented by an equation having the form wave when nine waves are incorporated. .
Mathematically, resolution of a complex
y = A (sin 2nvt + i sin 67tvt wave form into its sine or cosine components .t
(4-6) is tedious and time consuming; modern com-
puters, however, have made it practical to ex-
+! sin to nvt + ... + ~ sin 2n7tvt) ploit the power of the Fourier transformation
on a routine basis. The application of this
A graphical representation of the summation
Distance
technique will be considered in the discussion
process is shown in Figure 4-4. The solid line
of several types of spectroscopy.
FIGURE 4-2 Effect of change of medium on a monochromatic beam of in Figure 4-4a is the sum of three sine waves
Ditrraction. Figure _4-5 is a schematic rep-
radiation. differing in amplitude in the ratio of S : 3 : I
resentation of diffraction, which occurs
and in frequency in the ratio of 1 : 3 : S. Note
whenever waves of any type pass by a sharp
that the resultant is already beginning to
barrier or through a narrow opening. Diffrac-

Substitution of this relationship into Equa- waves. Figure 4-3b differs from 4-3a in that
tion 4-3 yields the difference in phase angle is greater; here,
the resultant amplitude is smaller than those
y = A sin(2nvt ~ tfJ) (4-4)
of the component waves. Clearly, a maximum
Superposition of Wa,ts. fhe principle of amplitude for the resultant will occur when
superposition states that when two or more the two waves are completely in phase; this
waves traverse the same space, a displacement situation prevails whenever the phase differ-
occurs which is the sum of the displacements ence between waves (tfJI - 4>2) is 0 deg, 360
caused by the individual waves. This principle deg, or an integer multiple of 360 deg. Under
applies to electromagnetic waves, where the these circumstances, maximum constructive
displacements involve an electrical force field, interference is said to occur. A maximum de-
as well as to several other types of waves, structive interference occurs when (tfJI - tfJ2) is
where atoms or molecules are displaced. For equal to 180 deg or 180 deg plus an integer ----Time---~ ----Time,----
example, when n electromagnetic waves of the multiple of 360 deg. The property of interfer-
(al (b)
same frequency but differing amplitudes and ence plays an important role in many in-
phase angles pass some point in space simul- strumental methods based on electromagnetic
taneously, the principle of superposition and radiation.
Equation 4-4 permits us to write Figure 4-3c depicts the superposition of
two waves with the same amplitude but dif-
y = Al sin(2nvt + tfJd ferent frequency. The resulting wave is no
+ A'2 sin(2nvt t 4>2) + ... (4-S) longer sinusoidal. It does, however, exhibit a
periodicity. Thus, the wave from 0 to B in the
+ A. sin(2nvt + 4>.) figure is identical to that from B to C.
. i
where y IS the resultant for~ field. An important aspect of superposition is
The solid line in Figure 4-3a shows the that the process can be reversed by a math-
application of Equation 4-S to two waves of ematical operation called a Fourier transfor-
identical frequency but somewhat different mation. Jean Fourier, an early French (el
amplitude and phase angle. Note that the re- mathematician (1768-1830~ demonstrated FIGURE 4-3 Superposition of sinusoidal waves: (a) Al < A2, (tfJI - tfJ2) = -20°,
sultant is a sine wave with the same frequency that any wave motion, regardless of complex- VI = V2; (b) Al < A2, (4)1 - 4>2) = -200°, VI = V2; (c) Al = A2, 4>1 = 4>2' VI = I.S V2' In
but different amplitude from the component ity, can be described by a sum of simple sine each instance, the solid curve is the resultant from combination of the two dashed curves.
lion is readily observed by generating waves
of constant frequency in a tank of water and
observing the wave crests before and after
Superposition of 3 .ine _ they pass through a rectangular opening or
y - Al.in 2m. t sin 81M. t sin 1000l slit. When the slit is wide relative to the wave-
length of the motion (Figure 4-Sa~ diffraction
is slight and difficult to detect. On the other
hand, when the wavelength and the slit open-
ing are of the same order of magnitude, as in
Figure 4-Sb, diffraction becomes pronounced.
Here, the slit or opening behaves as a new
source from which waves radiate in a series of
nearly 180-deg arcs. Thus, the direction of the
wave front appears to bend as a consequence
of passin.s the two edges of the slit.
- Diff~ion is a consequence of interfer-
ence. This relationship is most easily under-
stood by considering an experiment, per-
formed first by Thomas Young in 1800, by
which the wave nature of light was unambig-
uously d~monstrated. As shown in Figure 4-6,
a paralI4I beam of radiation is allowed to
pass through a na~row slit A (or in Young's
/ "\ experiment, a pinhole) whereupon it is dif- lbl
'V' \
\ Su-,tion of 9 .ine_
fracted and illuminates more or less equally FIGURE 4-5 Propagation
two closely spaced slits or pinholes Band C; of waves through a slit.
, \ - y-Ahin2lh't.tsin8""t ••..• ;!; sin 34,,,,,) the radiation emerging from these slits is then (a) x)' ~ l; (b) x)';:: l.
,""'-
, Superposition of 3 sine _
\
\
observed on the screen lying in a plane XY.1f
the radiation is monochromatic, a series of
, y - Alsin 2•.vr • t .in 8•.vr • t sin 10,M) darlc and light images perpendicular to the
plane of the page is observed. in the other light bands, are readily derived.
Figure 4-6b shows the intensities of the The angle of diffraction (J is the angle from
various bands reaching the screen. If, as in the normal formed by the dotted line extend-
this diagram, the slit widths approach the ing from a point, 0, halfway between the slits,
wavelength of radiation, the band intensities to the point of maximum intensity, D. The
decrease only gradually with increasing dis- solid lines BD and CD represent the light
tances from the central band. With wider slits, paths from the slits B an<!..f to this point.
the decrC'ase is much more pronounced. Ordinarily, the distance OE is enormous
The existence of the central band E, which compared to the distance between the slits
lies in tht shadow of the opaque material se- BC; as a consequence, the lines BD, OD, and
parating the two slits, is readily explained by CD are, for all practical purposes, paralleL
noting that the paths from B to E and C to E Line BF is perpendicular to CD and forms
lb)
are identical. Thus, constructive interference the triangle BCF, which is, to a close approxi-
of the diffracted rays from the two slits mation, similar to DOE; consequently, the
FIGURE 4-4 Superposition of sine waves to form a square wave:
occurs, and an intense band is observed. With angle CBF is equal to the angle of diffraction
(a) combination of three sine waves, and (b) combination of three, as in
(a), and nine sine waves. the aid of Figure 4-6c, the conditions for max- 9. We may then write
imum constructive interference, which result CF= BCsin (J
Substitution into Equation 4-7 gives vidual events, each of which lasts on the order
of 10-1 second. Thus, a beam of radiation
n.l. - ~ ;;;:~ (4-8) Crom this type of source is not continuous, as
DD DE . is the case in microwave or laser radiation;
).
/ Equation 4-8 permits the calculation of.~ instead, it is composed of a series of wave
I- wavelength Crom the three measurable trains that arc a few meters in length at most
quantities. Because the processes that produce a train
are random, the phase differences among the
EXAMPLE
Suppose that the screen in Figure 4-6 is trains must also be variable. A wave train
2.00 m Crom the plane of the slits and that the from slit B may arrive at a point on the
slit spacing is 0.300 mm. What is the wave- screen in phase with a wave train from C, and
length of radiation if the fourth band is constructive interference will occur; an in-
located 15.4 mm from the central band? stant later, the trains may be totally out of
DiffrllCtion Substituting into Equation 4-8 gives phase at the same point, and destructive inter-
byl ference will occur. Thus, the radiation at all
slngllsfit
' _ 0.300 )( 15.4 points on the screen is governed: by the
4
A 2)( 1000 mm random phase variations lU1,1ongthe wave
.l.- 5.78 )( 10-· mm or 578 mn trains; uniform illumination, which represents
an average for the trains, is the result.
Coherent Wiatioa. In order to produce a Sources do exist which produce- electro-
diffraction pattern such as that shown in magnetic radiation in the form of tr~ins with
Figure 4-6a, it is ncccssary that the clcctro- essentially infinite length and consfant fre-

f I Ii n n
magnetic waves traveling from slits B and C quency. Examples include radio frequency
to any given point on the screen (such as D or oscillators, microwave sources, optical lasers,
E) have sharply defined phase differences that and various mechanical sources such as a

~olLVJJJlliL
X-Diltlncl-Y
remain entirely constant with time; that is,
the radiation from slits Band C must be
coherent. The conditions for cohcrcncc are:
two-pronged vibrating tapper in a riffle tank.
When two of these are employed as sources
for the experiment shown in Figure 4-6, a reg-
(bl (el (1) the two sources of radiation must have ular diffraction pattern is observed.
FIGURE 4-6 Diffraction of monochromatic radiation by identical frequency and wavelength (or sets of Diffraction patterns can be obtained from
slits. frequencies and wavelengths); and (2) the 'random sources, such as a tungsten filament,
phase relationships between the two beams provided that an arrangement similar to that
must remain constant with time. The neces- shown in Figure 4-6a is employed. Here, the
sity for these requirements can be demon- very narrow slit A assures that the radiation
strated by illuminating the two slits in reaching Band C emanates from the same
Because BC is so very small compared to DE, for the light bands surrounding the central Figure 4-6a with individual filament lamps. small region of the source. Under these cir-
FD closely approximates BD, and the dis- band is Under these circumstances, the well-defined cumstances, the various wave trail1$ exiting
tance IT is a good measure of the difference n.l.= BC sin 8 (4-7) light and dark patterns disappear and are from slits Band C have a constant set of
in path lengths of beams BD and CD. For the replaced by a more or less uniform illumina- frequencies and phase relationships to one
two beams to be in phase at D, it is necessary where D is an integer called the order of
interference. tion of the screen. This behavior is a con- another and are thus coherent. If the slit at A
that CF correspond to the wavelength of the sequence of the incoherent character of is widened so that a larger part of the source
radiation; that is, The linear displacement DE of the dif-
fracted beam along the plane of the screen is filament sources (many other sources of is sampled, the diffraction pattern becomes
.l.z= CF z= BC sin 8 a function of the distance DE between the electromagnetic radiation are incoherent" as less pronounced because the two beams arc
screen and the plane ofthe slits, as well as the well). only partially coherent. If slit A is made
Reinforcement would also occur when the In incoherent sources, light is emitted by sufficiently wide, the incoherence may become
additional path length corresponds to 2)., 3)., spacing between the slits BC; that is,
individual atoms or molecules, and the result- great enough to produce only a constant illu-
and so forth. Thus, a more general expression DE= OD sin 8 ing beam is the summation of countless indi- mination across the screen.
ELECTROMAGNETIC RADIATION 101

Wavenumber. W••••• ngth. Frequency.


PlU1:icleProperti •• of R_iation beam front, but rather is concentrated at cer- Energy

Energy of EIedromagnetic Radiation. An
tain points or in particles of energy. Electron
volts.
a
--- A
Type
rad. Type Type
The work w required to cause emission of kCII/moi .V em-' em Hz tion IpeCtroIcopy
understanding of certain interactions between quantum transition
electrons is characteristic of the metal. The
radiation and matter requires that the radia-
alkali metals possess low work functions and 9.4 X 10' 4.1 X loa 3.3 X 10'· 3 X 10-11 1021
t
tion be treated as packets of energy called
photons or quanta. The energy of a photon
emit electrons when exposed to radiation in
the visible region. Metals to the right of the
Gemma
I'IY G"""""roy
emission
t
Nucl.lr
depends upon the freql,lency of the radiation,
and is given by
alkali metals in the periodic chart have larger
work functions and require the more ener-
getic ultraviolet radiation to exhibit the
9.4 X 10' 4.1 X 10' 3.3 X 10· 3 X 10-" 10'·
~ f
X..-oy
Ibsorption
omission
l r
Electronic
(inner sh.lI)
photoelectric effect. As we shall note in later
where h is Planck's cOnstant (6.63 x 10-27
erg see). In terms of w~velength,
chapters, the photoelectric effect has great
9.4 X 10" 4.1 X 10" 3.3 X loa 3 X 10-' 10"
1 1
practical importance in the detection of radia-
he tion using phototubes.
E=- Energy Units. The energy of a photon that
;1
is absorbed or emitted by a sample of matter 9.4 X 10' 4.1 X 100 3.3 X 10' 3 X 10-5 10'"
V VK
UV. absorption t
EllCtronic
Thus, an X-ray photon (1- 10-8 em) has ap- can be related to an energy difference between

fl'::'r
(outer sh.lI)
U\ }~ion
proximately 10,000 times the energy of a two molecular or atomic states, or to the
photon emitted by a hot tungsten wire frequency of a molecular motion of a constit- Yr· !
(1- 10-4 em~ uent of the matter. For this reason, it is often It absorption.
TIle Photoelectric ~ffed. The need for a convenient to describe radiation in energy
9.4 X 10-' 4.1 X 10-2 3.3 X 102 3 X 10-' 10"
1 1m1n Molecullr
vibration
particle model to de¢ribe the behavior of units, or alternatively in terms of frequency
electromagnetic radiation can be seen by con- (Hz) or wavenumber (cm -1), which are
1 f
Molecular
sideration of the photoelectric ~fJect. When directly proportional to energy. On the other t

- n:_I~
9.4 X 10-' 4.1 X 10-4 3.3 X 10· 3 X 10-' 10" rotation
Microwave
sufficiently energetic radiation impinges on a hand, the experimental measurement of radia- Micro-

metallic surface, electrons are emitted. The tion is most often expressed in terms of the
energy of the emitted electrons is found to be reciprocally related wavelength units such as
9.4 X 10-1 4.1 X 10'" 3.3 X 10-2 3 X 10' porlmlQnellC
related to the frequency of the incident radia- centimeters, micrometers, or nanometers. The 10·
resonence Magnetically
tion by the equation chemist must become adept at interconver-
E = hv - w (4-11)
sion of the various units employed in spec-
troscopy. Conversion factors commonly
9.4 X 10-'
Radio
J•
Nuclear magnetic
resonenc.
1 ~
--
spin states

4.1 X 10-· 3.3 X 10" 3 X 10' 10'


where w, the work function, is the work encountered for transformations are found
required to remove the electron from the FIGURE 4-7 Spectral properties, applications, and interactions of electromagnetic
inside of the front cover of this text.
radiation.
metal to a vacuum. While E is directly depend- The electron volt (eV) is the unit ordinarily
ent upon the frequency, it is found to be employed to describe the more energetic
totally independent of the intensity of the X-ray or ultraviolet radiation. The electron
beam; an increase in intensity merely causes volt is the energy acquired by an electron in sions. A logarithmic scale has been employed molecular or atomic transitions r~ponsible
an increase in the number of electrons emitted falling through a potential of one volt. Ra- in this representation; note that the portion for absorption or emission of radiation in
with energy E. diant energy can also be expressed in terms of to which the human eye is perceptive is very each region are also indicated.
Calculations indicate that no single elec- energy per mole of photons (that is, Avoga- small. Such diverse radiations as gamma rays
tron could acquire sufficient energy for ejec- dro's number of photons). For this purpose, and radio waves are also electromagnetic ra-
tion if the radiation striking the metal were units of kcal/mol or cal/mol are convenient. diations, differing from visible light only in the THE INTERACTION OF
uniformly distributed over the surface; nor matter of frequency, and hence energy. RADIATION WITH MATTER
could any electron accumulate enough energy The Electromegnetlc Spectrum Figure 4-7 shows the regions of the spec-
for its removal in a reasonable length of time. The electromagnetic spectrum covers an im- trum that are useful for analytical purposes As radiation passes from a vacuum through
Thus, it is necessary to assume that the mense range of wavelengths or energies. and the names of the spectroscopic methods the surface of a portion of matter, the electri-
energy is not uniformly distributed over the Figure 4-7 depicts qualitatively its major divi- I associated with these applications. The cal vector of the radiation interacts with the

_1_-
atoms and molecules of the medium. The Iating atoms, ions, or molecules as inter- normal dispersion region, there: is a gradual
nature of the interaction depends upon mediates .. increase in refractive index with increasing
the properties of the matter and may lead to One would expect the radiation from each frequency (or decreasing wavelength). Anoma-
transmission, absorption, or scattering of the polarized particle in a medium to be emitted lous dispersion regions are those frequency
radiation.· 'in all directions. If the particles are smal~ ranges in which a sharp change in refractive
however, it can be shown that destructive index is observed. Anomalous dispersion
Transmlulon of Rlldietlon interference prevents the propagation of always occurs at frequencies that correspond
significant amounts in any direction other. to the natural harmonic frequency associated
It is observed experimentally that the rate at with some part of the molecule, atom, or ion
than that of the original light path. On the
which radiation is propagated through a trans- . of the substance. At such a frequency, per-
other hand, if the medium contains large par-
parent substance is less than its velocity in a manent energy transfer from the radiation to
ticles (such as polymer molecules or colloidal.
vacuum; furthermore, the rate depends upon particles 1this destructive effect is incomplete: the substance occurs and absorption of the
the kinds and concentrations of atoms, ions, and a portion of the beam is scattered as a. beam is observed. Absorption is discussed in
or molecules in the medium. It follows from consequence of the interaction step. Scatter-' a later section.
these observations that the radiation must ing is considered in a later section of this' Dispersion curves are important in the FIGURE 4-9 Refraction
interact in some way with the matter. Because choice of materials for the optical compo- of light in passing from a
chapter.
a frequency change is not observed, however, Dispersion. As we have noted, the velocity' nents ofinstruments. A substance that exhibits less dense medium M1 into
the interaction CQllIIOt involve a permanent of radiation in matter is frequency-dependent; normal dispersion over the wavelength region a more dense medium M2,
energy transfer. since c in Equation 4-12 is independent of this of interest is most suitable for the manufac- where its velocity is lower.
The refractive index of a medium is a
parameter, the refractive index of a substance ture of lenses, for which a high and relatively
measure of its interaction with radiation and must also change with frequency. The varia'; constant refractive index is desirable. Chro-
is defined by
tion in refractive index of a substance with' matic aberration is minimized through the
frequency or wavelength is called its disper- i choice of such a material. In contrast, a sub- Reflection and
sion. The dispersion of a typical substance is: stance with a refractive index that is not only Scattering of Rlldletlon
shown in Figure 4-8. Clearly, the relationship' large but also highly frequency-dependent is
selected for the fabrication of prisms. The RellectioL When radiation crosses an
where IIj is the refractive index at a specified is complex; generally, however, dispersion
frequency i, Vi is the velocity of the radiation plots exhibit two types of regions. In the applicable wavelength region for the prism interface between media with differing refrac-
tive indexes, reftection occurs. The fraction
in the medium, and c is its velocity in vacuo. thus approaches the anomalous dispersion
region for the material from which it was reflected becomes larger with increasing dif-
The interaction involved in the transmis-
fabricated. ferences in refractive index; for a beam travel-
sion process can be ascribed to the alternat-
Refraction of Radiation. When radiation ing normally to the interface, the fraction
ing electrical field of the radiation, which
reflected is given by
causes the bound electrons of the particles passes from one medium to another of differ-
contained in the medium to oscillate with re- ing physical density, an abrupt change in di-
rection of the beam is observed as a
I, (n2 - nd2
spect to their heavy (and essentially fixed) - = ~-~ (4-14)
nuclei; periodic polarization of the particles consequence of differences in the velocity of 10 (n2 + nd2
thus results. Provided the radiation is not ab- . the radiation in the two media. This refraction
where 10 is the intensity of the incident beam
sorbed, the energy required for polarization is of a beam is illustrated in Figure 4-9. The
and I, is the reflected intensity; nl and "2 are
only momentarily retained (10-14 to 10-15 s) extent of refraction is given by the
the refractive indexes of the two media.
by the species and is reemitted without altera- relationship
tion as the substance returns to its original
state. Since there is no net energy change in EXAMPLE
this process, the frequency of the emitted ra- Calculate the percent loss of intensity due
diation is unchanged, but the rate of its propa- to reflection of a perpendicular beam of
gation has been slowed by the time required If the medium M1 is vacuum, VI becomes c yellow light as it passes through a glass cell
for retention and reemission to occur. Thus, and nl is unity (Equation 4-12); thus, the re- containing water. Assume that for yellow ra-
Frequency, Hz
transmission through a medium can be fractive index n2 of M2 is simply the ratio of diation the refractive index of glass is 1.5, of
viewed as a stepwise process involving oscil- FIGURE 4-8 Typical dispersion curve. the sines of the two angles. water is 1.33, and of air is 1.00.
In passing from air to glass, we find intense to be seen by the naked eye (the Tyn-
dall effect~ components of AB. A polarizing sheet, re-
!.!. = (1.50 -1.00f = 0.040 or 4.0% Scattering by molecules or aggregates of gardless of orientation, removes approxi-
10 (1.50 + l.00f molecules with dimensions significantly small- mately half of the radiation from an
er than the wavelength of the radiation is unpolarized beam, and transmits the other
In passing from glass to water, we find the
caIIcd Rayleigh scattering; its intensity is half as a plane-polarized beam. The plane of
loss to be
readily related to wavelength (an inverse polarization of the transmitted beam is
1, (1.50 - 1.33)2 0004 4. fourth-power effect~ the dimensions of the dependent upon the orien~ation of the sheet
10 = (1.50 + 1.33)2 =. or O. % scattering particles, and their polarizability. with respect to the incident beam. When two
An everyday manifestation of scattering is the polarizing sheets, oriented at 90 deg to one
The same losses would occur as the beam blueness of the sky, which results from another, are placed perpendicular to the
passes from the water and through the glass. the greater scattering of the shorter wave- beam path, essentially no ~radiation is trans-
Thus, lengths of the visible spectrum. mitted. Rotation of one results in a contin-
Scattering by larger particles, as in a col- FIGURE 4-10 (a) A few of the electrical uous increase in transmission until a
total percent loss = 2(4.0 + 0.4) = 8.8 loidal suspension, is much more difficult to vectors of a beam traveling perpendicular to maximum is reached when molecules of the
treat theoretically; the intensity varies roughly the page. (b) The resolution of a vector in two sheets have the same ltlignment.
It will become evident in later chapters as the inverse square of wavelength. plane XY into two mutually perpendicular The way in which radIation is reflected,
that losses such as those shown in this Measurements of scattered radiation can components. (c) The resultant when all vectors scattered, transmitted, and refracted by cer-
example are of considerable significance in be used to determine the size and shape of are resolved (not to scale). tain substances is also dependent upon direc-
various optical instruments. polymer molecules and colloidal particles. tion of polarization. As a consequence, a
Reftective losses at a polished glass or The phenomenon is also I1tilized in nephelom- group of analytical methods have been
quartz surface increase only slightly as the etry, an analytical method considered in developed whose selectivity. is based upon the
angle of the incident beam increases up to Chapter 10. different scale from Figure 4-lOa or 4-lOb to interaction of these substances with light of a
about 60 deg. Beyond this figure, however, Raman Scattering. The Raman effect dif- keep its size within reason. particular polarization. These methods are
the percentage of radiation that is reflected fers from ordinary scattering in that part of Removal of one of the two resultant planes considered in detail in Chapter 13.
increases rapidly and approaches 100% at 90 the scattered radiation suffers quantized of vibration in Figure 4-IOc produces a beam
deg. frequency changes. These changes are the that is plane polarized. The vibration of the
Scattering. As noted earlier, the transmis- result of vibrational energy level transitions electrical vector of a plane-polarized beam, Absorption of Radiation
sion of radiation in matter can be pictured as occurring in the molecule as a consequence of then, occupies a single plane in space. When radiation passes through a transparent
a momentary retention of the radiant energy, the polarization process. Raman spectroscopy Plane-polarized electromagnetic radiation layer of a solid, liquid, or gas, certain frequen-
which causes a brief polarization of the ions, is discussed in Chapter 9. is produced by certain radiant energy sources. cies may be selectively removed by the
atoms, or molecules present. Polarization is For example. the radio waves emanating from process of absorption. Here. electromagnetic
followed by reemission of radiation in all di- an antenna commonly have this character- energy is transferred to the atoms or
Polarization of Radiation
rections as the particles return to their original istic. Presumably, the radiation from a single molecules constituting the sample; as a result,
state. When the particles are small with re- Plane PoiarizatiolL Ordinary radiation can atom or molecule is also polarized; however, these particles are promoted from a lower-
spect to the wavelength of the radiation, de- be visualized as a bundle of electromagnetic since common light sources contain large energy state to higher-energy states, or
structive interference removes nearly all of the waves in which the amplitude of vibrations is numbers of these particles in all orientations, excited states. At room temperature, most
reemitted radiation except that which travels equally distributed among a series of planes the resultant is a beam that vibrates equally substances are in thei~ lowest energy
in the original direction of the beam; the path centered along the path of the beam. Viewed in all directions around the axis of travel. or ground state. Absorption then ordinarily
of the beam appears to be unaltered as a con- end-on, the electrical vectors would then The absorption of radiation by certain involves a transition from the ground state to
sequence of the interaction. Careful observa- appear as shown in Figure 4-lOa. The vector types of matter is dependent upon the plane higher-energy states. 1
tion, however, reveals that a very small in anyone plane, say X Y, can be resolved of polarization of the radiation. For example. Atoms, molecules, or ions have only a .
fraction of the radiation is transmitted at all into two mutually perpendicular components when properly oriented to a beam, aniso- limited number of discrete, quantized energy
angles from the original path and that the AB and CD as shown in Figure 4-10b. If the tropic crystals selectively absorb radiations levels; for absorption of radiation to occur,
intensity of this scattered radiation increases two components for each plane are combined, vibrating in one plane but not the other. the energy of the exciting photon must
with particle size. With particles of colloidal the resultant has the appearance shown in Thus, a layer of anisotropic crystals absorbs exactly match the energy difference between
dimensions, scattering becomes sufficiently Figure 4-1Oc. Note that Figure 4-1Oc has a all of the components of, say, CD in Figure the ground state and one of the excited states
4-IOc and transmits nearly completely the of the absorbing species. Since these energy
a molecule is given by
the number of possible energy levels for a
difTerences arc unique for each species, a
1. + Eribra'lanal
E - £.••••••••• + E"""IIOIIoI . (4-15) molecule Is much greater than for an atomic
study of the frequencies of absorbed radiation particle.
provides a means of characterizing the constit- where E•••et •••••l• describes the electronic
Figure 4-12 is a graphical representation of
uents of a sample of matter. For this energy of the molecule, and EribraiiOlUlI refers to the energies associated with Ii few of the elec-
purpose, a plot of absorbance as a function of the energy of the molecule resulting from var- tronic and vibrational states"'of a molecule.
wavelength or frequency is experimentally ious atomic vibrations. The third term in The heavy line labeled Eo represents the elec-
derived (absorbance, a measure of the Equation 4-15 accounts for the energy asso- tronic energy of the molecule in its ground
decrease in radiant power, is defined on ciated with the rotation of the molecule state (its state of lowest electronic energy);
p. 149). Typical plots of this kind, called around its center of gravity. For each elec- the lines labeled E1 and Ez represent the
absorption spectra, arc shown in Figure 4-11. tronic energy state of the molecule, there energies of two excited electronic states.
The general appearance of an absorption normally exist several possible vibrational Several vibrational energy levels (eo, eh .,.,
spectrum will depend upon the complexity, states, and for each of these, in turn, e.) are shown for each of these electronic
the physical state, and the environment of the numerous rotational states, As a consequence, states.
absorbing species. It is convenient to recog-
nize two types of spectra, namely, those asso-
ciated with atomic absorption and those
resulting from molecular absorption.
Atomic Absorptia The passage of poly-
chromatic ultraviolet or visible radiation
through a medium consisting of monatomic
t
I
particles, such as gaseous mercury or sodium,
results in the absorption of but a few well-
,
i
Excited
defined frequencies (see Figure 4-11d ~ The rel- £, electronic
ative simplicity of such spectra is due to the state 2

small number of possible energy states for the


particles. Excitation can occur only by an
electronic process in which one or more of
the electrons of the atom is raised to a higher-
o
220 240 260 280 300 ·3
.
~r"'"---~t -
Wovelength, nm •• L ~
CDerIYlevel. Thus, with sodium, excitation or
Cd)
the 35 electron to the 3p state requires energy
corresponding to a wavenumber of 1.697 x FIGURE 4-11 Some typical ultra- 1 .") J
eo' I E,
Excited
electronic
1()4em - I. As a result, sodium vapor exhibits violet absorption spectra. state t

a sharp absorption peak at 589.3 nm

f~:ae:'::.<--- - -
I
(yellow light). Several other narrow absorp-
tion lines, corresponding to other permitted Vi.lbl. energy
V ibrational :

~j _
-f-
electronic transitions, are also observed (see
Figure 4-11d). Regardless of the wavelength region in-
Ultraviolet and visible radiation have
sufficient energy to cause transitions of the
volved, atomic absorption spectra typically
consist of a limited number of narrow peaks. ..,_)1'
outermost or bonding electrons only. X-ray Spectra of this type are discussed in connec- •J -'~I----
frequencies, on the other hand, are several tion with X-ray absorption (Chapter 15) and
1 • 2 'I I
orders of magnitude more energetic and are atomic absorption spectroscopy (Chapter 11).
f I • " '
capable of interacting with electrons closest Molecular Absorption. Absorption by poly- • l il Eo
Gtound
electronic
to the nuclei of atoms. Absorption peaks cor- atomic molecules, particularly in the con- state
responding to electronic transitions of these densed state, is a considerably more complex fa) (bl (el
innermost electrons are thus observed in the process because the number of energy states
FIGURE 4-12 Partial energy level diagram for a fluorescent organic molecule.
X-ray region. is greatly enhanced. Here, the total energy of
As can be seen in Figure 4-12, the energy we have mentioned, many rotational energy resonance (NMR) and electron spin resonance complicated molecules possessing many
levels are associated with each vibrational (ESR) techniques, respectively; these methods closely related energy states. Continuous
difference between the ground state and an
state .. As a consequence, the spectrum for a are considered in Chapter 14. spectra also arise when the energy changes
electronically excited state is large relative to
molecule ordinarily consists of a series of Relaxation Processes. Ordinarily, the involve particles with unquantized kinetic
the energy differences be~een vibrational
closely spaced absorption bands, such as lifetime of an atom or molecule excited by energies.
levels in a given electronic s~te (typically, the
that shown for benzene vapor in Figure absorption of radiation is brief because Both continuous spectra and line spectra
two differ by a factor of 10 to 100).
4-11c. Unless a high-resolution instrument is several relaxation processes exist which are of importance in analytical chemistry. The
Figure 4-118 depicts with arrows some. of
employed, the individual bands may not be permit its return to the ground state. As former are frequently employed in methods
the transitions which result from absorption
detected, and the spectra will appear as shown in Figure 4-12b, nonradiative relaxa- based on the interaction of radiation with
of radiation. Visible radiation causes excita-
smooth curves. Finally, in the condensed tion involves the loss of energy in a series of matter, such as spectrophotometry. Line spec-
tion of an electron from Eo to any of the
state and in the presence of solvent small steps, the excitation energy being con- tra, on the other hand, are important because
vibrational levels associated with E I' The
molc:eules, the individual bands tend to verted to kinetic energy by collision with they permit the identification and determina-
frequencies absorbed would be given by
broaden to give spectra such as those shown other molecules. A minute increase in the tion of the emitting species.
in Figure 4-11a and b. Solvent effects are con- temperature of the system results.
v. = ~(E1 + e~ - Eo) (4-16)
As shown in Figure 4-12c, relaxation can
sidered in later chapters.
Pure vibrational alpsorption can be ob-
Thermel Radiation
also occur by emission of ftuorescent radia-
Similarly, the frequencies of absorbed ultra- served in the infrared region. where the tion. Still other relaxation processes are dis- When solids are heated to incandescence, the
violet radiation would be given by energy of radiation is insufficient to ca~ cussed in Chapters 10 and' 14. continuous radiation that is emitted is more
electronic transitions. Here, spectra exhibit characteristic of the temperature of the emit-
v. = ~ (E2 + e: - Eo) (4-17) narrow, closely spaced absorption peaks re- ting surface than of the material of which that
sulting from transitioBs among the various surface is composed. Radiation of this kind
Finally, the less energetic near- and mid- vibrational quantum Jeivels(see the bottom of (called black-body radiation) is produced by
infrared radiation can only bring about tran- Figure 4-118). Variatidns in rotational levels Electromagnetic radiation is often produced the innumerable atomic and molecular oscil-
sition among the vibrational levels of the may give rise to a seiies of peaks for each when excited particles (ions, atoms, or lations excited in the condensed solid by the
ground state. vibrational state. However, rotation is often molecules) return to lower-energy levels or to thermal energy. Theoretical treatment of
hindered or prevented in liquid or solid their ground states. Excitation can be brought black-body radiation leads to the following
samples; thus, the effects of these small energy about by a variety of means, including bom- conclusions: (I) the radiation exhibits a maxi-
differences are not ordinarily detected in such bardment with electrons or other elementary mum emission at a wavelength that varies in-
Although they are not shown, several rota- samples. particles, exposure to a high-potential alter- versely with the absolute temperature; (2) the
tional energy levels are associated with each Pure rotational spectra for gases can be nating current spark, heat treatment in an arc total energy emitted by a blade body (per unit
vibrational level. The energy difference be- observed in the microwave region. or a ftame, or absorption of electromagnetic of time and area) varies as the fourth power
Absorption Induced by a Magnetic Field. radiation. of temperature; and (3) the emissive power at
tween these is small relative to the energy dif-
When electrons or the nuclei of certain ele- Radiating particles that are well separated a given temperature varies inversely as the
ference between vibrational levels; transition
to excited rotational states is brought about ments are subjected to a strong magnetic from one another, as in the gaseous state, fifth power of wavelength. These relationships
by radiation in the 500- to 1QO-cm- 1 range. field additional quantized energy levels are behave as independent bodies and often pro- are reflected in the behavior of several exper-
In contrast to atomic absorption spectra, produced as a consequence of .magnetic duce radiation containing relatively few imental radiation sources shown in Figure
which consist of a series of sharp, well-defined properties of these elementary partiCles. The specific wavelengths. The resulting spectrum 4-13; the emission from these sources
lines, molecular spectra in the ultraviolet and· difference in energy' between the induced is then discontinuous and is termed a line spec- approaches that of the ideal black body. Note
visible regions are ordinarily characterized by states is small, and transitions between the trum. A continuous spectrum, on the other that the energy peaks in Figure 4-13 shift to
absorption bands that often encompass a sub- states are brought abput only by absorption hand, is one in which all wavelengths are rep- shorter wavelengths with increasing tempera-
stantial wavelength range (see Figure 4-11a, of long-wavelength (<lr low-frequency) radia- resented over an appreciable range, or one ture. It is clear that very high temperatures
b, c). Molecular absorption also involvc:selec- tion. With nucle~ radio waves ranging from in which the individual wavelengths are so are needed to cause a thermally excited
tronic transitions. As shown by Equations 4- 10 to 200 MHz are generally employed, while closely spaced that resolution is not feasible source to emit a substantial fraction of its
16 and 4-17, however, several closely spaced for electrons, microwaves with frequencies of by ordinary means. Continuous spectra result energy as ultraviolet radiation.
1000 to 25,000 MHz are absorbed. from excitation of: (1) solids or liquids, in Heated solids are used to produce infrared,
absorption lines will be associated with each
Absorption by nuclei or by electrons in which the atoms are so closely packed as to visible, and longer-wavelength ultraviolet ra-
electronic transition, owing to the existence of
numerous vibrational states. Furthermore, as magnetic fields is studied by nuclear magnetic be incapable of independent behavior; or (2) diation for analytical instruments.
Resonance fluorescence describes a process as a result of collision with other molecules.
the excited hydrogen atom, while £Ht and £H2
in which the emitted radiation is identical in Morc often than not, the energy of the ab-
represent the kinetic energies of the 'atoms.
frequency to the radiation employed for exci- sorbed radiation is greater than that of the
The sum of the latter can vary continuously
tation. The lines labeled 1 and 2 in Figure emitted radiation. Thus, for the absorption
from zero to EH•• Thus, the frequency of ~-
4-12a and 4-12c illustrate this type of fluores- labeled 3 in Figure 4-128, the absorbed
diation hv can also vary continuously" over thIS
cence. Here, the species is excited to the energy would be equal to (E2 - Eo +
range. The conseqUet1QCis a continuous s~-
trum from about 400 to 200 om that 15 a
energy states EI or E2 by radiation having an e: - eo); the energy of the fluorescent radia-
energy of (Et - Eo) or (E2 - Eo). After a tion, on the other hand, would again be given
useful source for absorption spectropho-
brief period, emission of radiation of identical by -(E2 - Eo); the emitted radiation would
tometry. energy" occurs, as depicted in Figure 4-12c. necessarily have a lower frequency or greater
Resonance fluorescence is most commonly wavelength than the radiation that excited
Emluion of X-ray Radiation
500 1000
produced by atoms in the gaseous state which the 'fluorescence. (This shift in wavelength to
Wavelength, om Radiation in the X-ray region is normally do not have vibrational energy states super- lower frequencies is sometimes called the
generated by the bomba~ment of a metal imposed on electronic energy levels. Stokes shift.) Clearly, both resonance and
target with a stream of htgh-speed electrons. Nonresonance fluorescence is brought nonresonance radiation can accompany fluo-
The electron beam causes the innermost elec- about by irradiation of molecules in solution resqence of molecules; the latter tends to pre-
trons in the atoms of the target material to be or in the gaseous state. As shown in Figure dominate,however, because of the much larger
raised to higher energy levels or to be ejected 4-128, absorption of radiation promotes the number of vibrationally excited states.
Emission of G••••
entirely, The excited atoms o~ ions th~ molecules into any of the several vibrational Phosphorescence occurs when an excited
Atoms, ions. or molecules in the gaseous state return to the ground state by vanous stepw,* levels associated with the two excited elec- molecule relaxes to a metastable excited elec-
can often be excited, by electrical discharge or electronic transitions that are accompanted tronic levels. The lifetimes of the excited troaic state which has an average lifetime of
by heat, to produce radiation in the ult~a- by the emission of photons, each having. an vibrational states are momentary, however greiter than about 10-, s. The nature of this
violet and visible regions. The process 10- energy hv. The consequeooe is the production (- 10-15 s~ and, as shown in Figure 4-12b, typtl of excited state is discussed in Chapter
volves promotion of the outerm~t electrons of an X-ray spectrum consisting of a ~ries ~f relaxation to the lowest vibrational level (eo 10. '
of a species to an excited electron~ state; ~a- lines characteristic of the target matenal. ThIS and e~) of a given electronic state takes place
diation is then emitted as the excited Species discrete spectrum is superimposed on a con-
returns to the ground state. Atomic emission tinuum of nonquantized radiation given off
spectra consist of a series of discrete Iin~ when some of the high-speed electrons are
1. Calculate the frequency in hertz and the wavenumber for
whose energies correspond to the energy dif- partially decelerated as they pass through the (a) an X-ray beam with a wavelength 4.2 A.
ferences between the various electronic states. target material. (b) an emission line for Cu at 211.0 nm.
For molecules, emission spectra are usua~ly
(c) the line at 694.3 nm produced by a ruby laser.
more complicated because there can eXISt Fluorescence and Phosphorescence
(d) the output of a CO2 gas laser at 10.6 Jim.
several vibrational and rotational states for
Fluorescence and phosphorescence are analyt- (e) an infrared absorption peak at 34.1 jJTll.
each possible electronic energy ~vel; in~t~
ically important emission processes in wh.ich (f) a microwave beam of wavelength 0.250 em.
of a single line for each electrOniC translu~n,
atoms or molecules are excited by absorption 2. Calculate the wavelength in centimeters for
numerous closely spaced lines form an emis-
of a beam of electromagnetic radiation; radiant (a) the radio frequency of an airport tower at 118.6 MHz.
sion band. .' emission then occurs as the excited species
A true continuous spectrum IS sometimes (b) a radio navigation beam !laving a frequency of 315.3 kHz.
produced from the excitation of gaseous return to the ground state. (c) an NMR signal at 42.6 MHz.
Fluorescence occurs much more rapidly (d) an EPR signal at 12,000 MHz.
molecules. For example, when hydrogen at
than phosphorescence and is generally com- 3. Calculate the energy of each bf the radiations in Problem 1 in
low pressure is subjected t~ an electric
plete after about 10-' s (or I~) from the (a) ergs/photon, (b) kcal/mol. and (c) eV. .
discharge, an excited molecule IS formed that
time of excitation; it is most easily observed
dissociates to give two hydrogen atoms and 4. Calculate the energy of each of the radiations in Problem 2 in
an ultraviolet photon. The energetics of this at a 9<k1eg angle to the excitation beam. P~-
(a) ergs/photon, (b) kcal/mol, and (c) eV.
phorescence emission takes place ove~ pen·
process is described by the equation 5. Calculate the velocity, wavelength, and frequency of the sodium D line
ods longer than 10-' s, and may lO~ecd
EH• = £HI + £H2+ hv (l = 5890 A in a vacuum) in
continue for minutes or even hours after Irra-
(a) acetone vapor (nD = l.()() 11).
Here, EH• represents the quantized energy of diation has ceased.
(b) carbon bisulfide (110 •• 1.622~
(c) a flint glass (110 •• 1.6S~
(d) fused silica (110 •• 1.44).
6. Calculate the reflective loss when a S89-nm beam of radiation
(a) passes through a piece of dense flint glass ("0" 1.63~
(b) passes through a cell having glass windows ("0" 1.46) and con-
taining an alcohol solution with a refractive index of 1.37.
COMPONENTS OF INSTRUMENTS FOR OPTICAL SPECTROSCOPY

The term spectroscopy was originally used to whether they are applied to the ultraviolet,
describe a branch of tcience based upon the visible, or infrared portion of the Spectrum.l
resolution of visible radiation into its com- Spectroscopic instruments contain five
ponent wavelengths. With the passage of components, including: (1) a stable source of
time, the meaning of the term has been ex- radiant energy; (2) a device that permits em-
panded to iitclude studies encompassing the ployment of a restricted wavelength region;
entire electromagnetic spectrum (Figure 4-7~ (3) a transparent container for holding the
The first spectroscopic instruments were sample; (4) a radiation detector or transducer
developed for use in the visible region and that cOnverts radiant energy to a usable
were thus called optical instruments. This term signal (usually electrical); and (5) a signal
has now been extended to include instru- processor and readout. Figure 5-1 shows the
ments designed for use in the ultraviolet and arrangement of these components for the four
infrared regions as well; while not strictly common types of spectroscopic measure-
correct, the terminology is nevertheless useful ments :mentioned earlier. As can be seen in
in that it emphasizes the many features that the figure, the configuration of components
are common to the instruments used for stud- (4) and (5) is the same for each type of
ies in these three important spectral regions. instruinent.
The purpose of this chapter is to describe Emission spectroscopy ditTers from the
the nature and properties of components of other three types in the respect that no exter-
instruments employed. for optical spectros- nal radiation source is required; the sample
copy. The seven chapters that follow will itself ~ the emitter. Here, the sample con-
provide details showing how the various c0m- tainer; is an arc, a spark, or a flame, which
ponents are assembled to produce optical in- both holds the sample and causes it to emit
struments, and how these instruments in turn characteristic radiation.
provide useful information. The instruments Absorption as well as fluorescence and
and techniques for spectroscopic studies in re- scattering spectroscopy require an external
sions more energetic than the ultraviolet and source of radiant energy. In the former. the
less energetic than the infrared have charac- beam from the source passes through the
teristics that dill'er substantially from optical sample after leaving the wavelength selector. Ie)
iDstrumcnts and are considered separately in In the latter two, the source iDduces
Chapters 14 and IS. the sample, held in a container, to emit char- FI~URE 6-1 Components for various types of instruments for
acteristic fluorescent or scattered radiation, ~Ptlcal spectroscopy: (a) emission spectroscopy, (b) absorption
which is measured at an angle (usually 90 pectroscopy, and (c) fluorescence and scattering Spectroscopy.
deg) with respect to the source.
Figure 5-2 summarizes the characteristics
COMPONENTS AND
of the first four components shown in Figure
CONFIGURATIONS OF
5-1. It is clear that instrument components
INSTRUMENTS FOR differ in detail, depending upon the wave-
OPTICAL SPECTROSCOPY length region within which they are to be
used. Their des~gn also depends on the pri-
~n order to be suitable for spectroscopic stud-
Spectroscopic methods are based upon the ~ use of the Instrument; that is, whether il
I For ~ more complcae discuuion of the components of I~, a s.ource must generate a beam of radia-
~ to be e~ployed for qualitative or quantita-
phenomena of emission, absorption, fluores- optical instruments, see: R. P. Bauman, Absorption Spec. tion With sufficient power for ready detection
tive ~nalyslS and whether it is to be applied to
cence, or ~cattering. While the instruments lrOICOpy. New York: Wiley. 1962, Chapten 2 and 3; E. J. and measurement. In addition, its output
Meehan, in TfflItiM 011 AlI4lytlcGl Clwmlltry, eds. I. M. atolDJC or molecular spectroscopy. Never-
for each dill'er somewhat in configuration, should be stabl~. Typically, the radiant power
Koltholl' and P. J. Elvin•. New York: Intcncicncc, 1964, thele;u, the general function and performance
their basic components are remarkably simi- Part I, yo\. 5, Chapter 55; and Pltyslc4l Mtfltob ofCIwm- o~ a source vanes exponentially with the elec-
r~~lrements of each type of component are
lar. Furthermore, the general properties of IItry. eds. A. Wciubcracr and B. W. Rouiter. New York: tncal power supplied to it. Thus, a regulated
slml~ar, .regardless of wavelength region and
their components are the same regardless of Wiley·lntcnciencc, 1912, Part IIIB, Yo\. I, Chapters 1-5. apphcatlon. power supply. is often needed to provide the
required stability. Alternatively, in some in-
-
struments. the output of the source is split An important feature of hydrogen discharge
into. a reference beam and a sample beam. lamps is the shape of the aperture between
.nm The first passes directly to a transduc:er while the two electrodes, which constricts the dis-
Spectral region VACUV UV ,I VISIBLE NEAR'IR IR • , FARIR the second interacts with the sample and is charge to a narrow path. As a consequence.
then focused on a matched transducer. (Some an intense ball of radiation about 1 to 1.5 mm
(.1 Sources
~limp I instruments employ a single transducer which in diameter is produced. Replacement of
Xenon limp
is irradiated alternately by the sample and hydrogen by deuterium results in a somewhat
'I H20rD2 1 reference beams.) The ratio of the outputs of
lamp Tungsten lamp
larger light ball.
Continuous r the two transducers serves as the analYtical Both high- and low-voltage lamps produce
Nern.t glower IZrD2 +Y20,)
parameter. The effect of fluctuations in the a continuous spectrum in the region of 160 to
Nichrome wire (Ni + Cr) ,
source output is largely canceled by. this 375 nm. Quartz windows must be employed
GlobIr (SiC!
means. in the tubes, since glass absorbs strongly in
Hollow cathode
Di1continuou. {
, Both continuous and line sources are used this wavelength region.
lamps
in optical spectroscopy. The former ;finds Tungsten Filament Lamps. The most
wide application in molecular absorption
lb) W_ength
selectors :~ prism '-.,
Fused .
.11..,. or qUlrtz prosm methods. The latter is employed in ftqores-
common source of visible and near-infrared
radiation is the tungsten filament lamp. The
GllSlprism . cence and atomic absorption spectroscopy. energy distribution of this source approxi-
Continuous

3000 Iineslmm
I I
Grltings with various number
i~~
of lineslmm
KBr pritm
50lineslmm
Figure 5-la lists the most widely used
spectroscopic sources.
mates that of a black body and is thus
temperature dependent. Figure 4-13 illus-
trates the behavior of the tungsten filament
I Interference wedges
lamp at 3OOOoK.In most absorption instru-
Interforence filters
Continuous Sources of Ultraviohtt. ments, the operating filament temperature is
OilContinuous {
GllSlabsorption
Visible, and Near-Infrared Radiat)on about 2870oK; the bulk of the energy is thus
filters .emitted in the infrared region. A tungsten
LiF
(e) M.terill. for filament lamp is useful for the wavelength
cell •• windows, qUIrtz
& lenses
Fused silica or Continuous sources provide radiation whose region between 320 and 2500 nm.
,
Corexglass! power does not change sharply among adja- In the visible region. the energy output of a
Silicate gtlSl cent wavelengths. tungsten lamp varies approximately as the
NaCI Hydrogen or Deuterium Lamps. As noted fourth power of the operating voltage. As a
K8r in Chapter 4 (p. 110~ a continuous spectrum consequence. close voltage control is required
TIBr-TII in .the ultraviolet region is conveniently for a stable radiation source. Constant volt-
produced by the electrical excitation of age transformers or electronic voltage regu-
ldl TWItducers Photornu tiplier hydrogen or deuterium at low pressure. lators are often employed for this purpose. As
Two types of hydrogen lamps are en-

{
Photon Phototube an alternative, the lamp can be operated from
detectors
, 7:otocefl countered. The high-voltage variety employs a 6-V storage battery, which provides a
Silicon diode
potentials of 2000 to 6000 V to cause a remarkably stable voltage source if it is main-
Semiconductor
discharge between aluminum electrodes; tained in good condition.
Thermocouple (volts) or Bolometer (ohms'
water cooling of the lamp is required if-high Xenon Arc Lamps. This lamp produces
Heat
detectors { I
I
I Gol.y
Pyrcetectric
pneumltic cell
cell (capocitonce)
I radiation intensities are to be produee<i. In
low-voltage lamps. an arc is formed between
intense radiation by the passage of current
through an atmosphere of xenon. The spec-
a heated, oxide-coated filament and a rhetal trum is continuous over the range between
FIGURE 5-2 Components and materials for spectroscopic instruments ..(Adapt~ ~rom
a figure by Professor A. R. Armstrong, College of William and Mary. With permission.) electrode. The heated filament provides 'elec- about 25;0 and 600 nm, with the peak inten-
trons to maintain a dc current when a voltage sity occurring at about 500 nm (see Figure
of about 40 V is applied; a regulated power 4-13, p. 110). In some instruments, the lamp is
supply (p. 53) is required for constant operated intermittently by regular discharges
intensities. from a capacitor; high intensities are obtained.
Continuous Sources age of current. A rhodium wire heater sealed
~ Nonparallel radiation •
of Infr••.••• Rlldlation in a ceramic cylinder has similar properties as
..•.._ .•..,._A'
a source.
t----i: '..>.-;""'"

'X-i- ~
The common infrared source is an inert solid
heated electrically to temperatures between
lSOO and 2OQOoK. Continuous radiation
approximating that of a black body results
(see Figure 4-13). The maximum radiant
intensity at these temperatures occurs be-
tween 1.7 and 2 #Ll11 (6000 to SOOOem -I). At
Line Sources
Sources that emit a few discrete lines find use
in atomic absorption spectroscopy, Raman
spectroscopy, refractometry, and polarimetry.
Metal Vapor Lamps. Two of the most
Mirror

Pumping
SOurce
JZ:"
Radiation ----- ~

g£~
. ".
t -.
''.i'~lv
=s --.
Active I~ing mediu'!'

. .
transmitting
mirror

common line sources are the familiar mercury FIGURE 5-3 Schematic representation of a typical
longer wavelengths, the intensity falls off co~- laser source.
and sodium vapor lamps. A vapor lamp con-
tinuously until it is about I % of the maxI-
sists of a transparent envelope containing a
mum at 151lm (667 em-I). On the short
gaseous element at low pressure. Excitation of
wavelength side, the decrease is much more
the characteristic line spectrum of the element processes with lifetimes in the range of 10-9 narrow band of radiation at any chosen
rapid , and a similar reduction in intensity is
I occurs when a potential is applied across a to 10-12 s, the detection and determination wavelength within the range of the source.
observed at about 111m (10,000 em- ).
pair of electrodes fixed in the envelope. Con- of extremely small concentrations of species Figure 5-3 is a schematic representation
TIle Nerast Glower. The Nemst glower is
duction occurs as a consequence of electrons in the atmosphere, and the induction of is0- showing the components of a typical laser
composed of rare earth oxides formed into a
and ions formed by ionization of the metaL topically selective reactions.3 In addition, laser source. The heart of the device is a lasing
cylinder having a diameter of I to 2 mm and
Ordinarily, initial heating is required to pro- sources have become important in several
a length of perhaps 20 Mm. Platinum leads medium. It may be a solid crystal, such as
duce sufficient metal vapor; once started, routine analytical methods, including Raman
are sealed to the ends of the cylinder to ruby, a semiconductor such as gallium arse-
however, the current is self-sustaining. spectroscopy (Chapter 91 emission spectros-
permit passage of current. This device has a nide. a solution of an organic dye, or a gas.
The mercury lamp produces a series of copy (Chapter 12), and Fourier transform The lasing material can be activated or
large negative temperature coefficient of elec-
lines ranging in wavelength from 254 to infrared spectroscopy (Chapter 8).
trical resistance, and it must be heated ex- pumped by radiation from an external source
734 nm. With the sodium lamp. the pair of The term laser is an acronym for light
ternally to a dull red heat before a sufficient so that a few photons of proper energy will
lines at 589.0 and 589.6 nm predominate. amplification by stimulated emission of radia- trigger the formation of a cascade of photons
current passes to maintain the desired
Hollow CathcMle Lamps. Hollow cathode tion. As a consequence of their light- of the same energy. Pumping can also be
temperature. Because the resistance decreases
lamps provide line spectra for a large number amplifying properties, lasers produce spatially carried out by an electrical current or by an
with increasing temperature, the source cir-
of elements. Their use has been confined to narrow, extremely intense beams of radiation. electrical discharge. Thus, gas lasers usually
cuit must be designed to limit the current;
atomic absorption and atomic fluorescence The process of stimulated emission produces do not have the external radiation source
othe(Wise the glower rapidly becomes so hot
spectroscopy. Discussion of this type of a beam of highly monochromatic (band- shown in Figure 5-3; instead, the power
that it is destroyed.
source is deferred to Chapter II. widths of 0.01 nm or less) and remarkably supply is connected to a pair of electrodes
The Globar Source. A Globar is a silicon
coherent (p. 99) radiation. Because of these contained in a cell filled with the gas.
carbide rod, usually about 50 mm in length
Lase,. unique properties, lasers have become impor- A laser normally functions as an oscillator,
and 5 mm in diameter. It also is electrically
heated and has the advantage of a positive tant sources for use in the ultraviolet, visible, in the sense that the radiation produced from
The first laser was constructed in 1960.2 Since
coefficient of resistance. On the other hand, and infrared regions of the spectrum. A limi- the laser mechanism is caused to pass back
that time, chemists have found numerous
water cooling of the electrical contacts is tation of early lasers was that the radiation and forth through the medium numerous
useful applications for these sources in high-
required to prevent arcing. Spectral energies from a given source was restricted to a rela- times by means of a pair of mirrors as shown
resolution spectroscopy, kinetic studies of
of the Globar and the Nernst glower are com- tively few discrete wavelengths or lines. Re- in Figure 5-3. Additional photons are gen-
cently, however, dye lasers have become erated with each passage, thus leading to
parable except in the region below 5 #Ll11
(2000 em -I), where the Globar provides a available; tuning of these sources provides a enormous amplification. The repeated pass-
significantly greater output. 1 For a more complete discussion or lasers. see: B. A. age also produces a beam that is highly par-
Inl:andeseeat Wire Source. A source of Lengye~ lAsers. New York: Wiley, 1971; S. R. Leone allel because nonparallel radiation escapes
and C. B. Moore, Chemical allll Biological A.pplications of from the sides of the medium after being
somewhat lower intensity but longer life than lAsers, eel. C. E. Moore. New York: Academic Press,
the Globar or Nernst glower is a tightly reflected a few times (see Figure 5-3~
1974; and A.nalytical lAser Spectroscopy. eel. N. Omen-
wound spiral of nichrome wire heated by pass- etlo. New York: Wiley, 1979. • For a review or some or Ihese applicalions. see: S. R. In order to obtain a usable laser beam, one
Leone, J. Chem. Educ.,53, 13 (1976~ of the mirrors is coated with a sufficiently
thin layer of reflecting material so that a frac- diagrams shown in Figure 5-4b. Note that the
tion of the beam is trilnsmitted rather than wavelength of the fluorescent radiation is
(1)
reflected (see Figure 5-3). directly related to the energy difference be-
-_ EM
. Laser action can be understood by con-
sidering the four processes depicted in Figure
tween the two electronic states, E, - Ex. It is
also important to note that the instant at
=+=~.
.,- -r· E•
:±: ~ Heat

5-4, namely, (a) pumping, (b) spontaneous which the photon is emitted, and its direction, Pumping I I
energy I I
emission (fluorescence1 (c) stimulated emis-
sion, and (d) absorption. For purposes of
will vary from excited electron to excited elec-
tron. That is, spontaneous emission is a
-+- +E.
illustration, we will focus on just .two of random process; thus, as shown in Figure 5-4,
several electronic energy levels that wil( exist the fluorescent radiation produced by one of
in the atoms, ions, or molecules making up the particles in diagram b-I differs in direc-
the laser material; as shown in the figure, the tion and phase from that produced by the
two electronic levels have energies E, and Ex. second particle (diagram b-2). Spon.taneous
Note that the higher electronic state is shown emission, therefore, yields incoherent radiation.
as having several slightly different vibrational Stimulated Emission. Stimulated emission,
energy levels, E" E~, E;, and so forth. We which is the basis of laser behavior, is
have not shown additional levels for the depicted in Figure 5-4c. Here, the' excited
lower electronic state, although such often laser particles are struck by externally
exist. produced photons having precisely the same
Pumping. Pumping, which is necessary for energies (E,- Ex) as the photons produced
laser action, is a process by which the active by'spontaneous emission. Collisions; of this
species of a laser is excited by means of an type cause the excited species to r~lax im-
electrical discharge, passage of an electrical mediately to the lower energy statei and to
current, exposure to an intense radiant emit simultaneously a photon of exactly the ---
--- ----
source, or interaction with a chemical species.
During pumping, several of the higher elec-
tronic and vibrational energy levels of the
active species will be populated. In diagram
same energy as the photon that stimulated
the process. More important, and more
remarkable, the emitted photon is precisely in
phase with the photon that triggered the event.
~~ __=cvu-
a-I of Figure 5-4, one atom or molecule is That is, the stimulated emission is totally
shown as being promoted to an energy state coherent with the incoming radiation.
E;; the second is excited to the slightly higher . Absorption. The absorption process, which
vibrational level E;. The lifetime of excited competes with stimulated emission. is
vibrational states is brief, however; after depicted in Figure 5-4d. Here, two photons
10-13 to 10-14 S, relaxation to the lowest with energies exactly equal to E, - Ex are ab-
excited vibrational level (E, in diagram a-3) sorbed to produce the metastable excited
occurs with the production of an undetectable state shown in diagram d-3; note that the
quantity of heat. Some excited electronic state shown in diagram d-3 is identical to that
states of laser materials have lifetimes con- attained by pumping diagram a-3. FIGURE 5-4 Four processes important in laser action: (a) pumping
siderably longer (often I ms or more) than Population Inversion a'" Light Amplifica- (excitation by electrical. radiant. or chemical energy). (b) spontaneous
their excited vibrational counterparts; long- tion. In order to have light amplification in a emission. (c) stimulated emission. and (d) absorption.
lived states are sometimes termed metastable laser, it is necessary that the number of~hotons
as a consequence. produced by stimulated emission exceed the
Spontaneous Emission. As was pointed QUt number lost by absorption. This condition will
in the discussion of fluorescence, a species in prevail only when the number of particles in the
an excited electronic state may lose all or part higher energy state exceeds the number in the
of its excess energy by spontaneous emission lower; that is, a population inversion from the
of radiation. This process is depicted in the normal distribution of energy states must exist.
Population inversions are brought about by system. In contrast, it is only necessary to E. E.

:rE~
pumping. Figure 5-5 contrasts the effect of pump sufficiently to make the number of par- " ____ •FISttransition
nonradiative
incoming radiation on a noninverted popula- ticles in the E, energy level exceed the number
tion with an inverted one. in Ex of a four-level system. The lifetime of a Ey

11Iree- •••• Four-Level LIser Systems. Fig- particle in the Ex state is brief, however, be-
ure 5-6 shows simplified energy diagrams for
the two common types of laser systems. In the
three-level system, the transition responsible
cause the transition to Eo is fast; thus, the
number in the Ex state will generally be negli-
gible with respect to Eo and also (with a
1E,/-- Fast transition

for laser radiation is between an excited state modest input of pumping energy) with respect
E, and the ground state Eo; in a four-level to E,. That is, the four-level laser usually
FIGURE 6-6 Energy level diagrams for two types
system, on the other hand, radiation is gen- achieves a population inversion with a smaller
of laser systems.
erated by a transition from E, to a state Ex expenditure of pumping energy.
that has a greater energy than the ground Some Examples of Useful Lasers. The first
state. Furthermore, it is necessary that transi- successful laser, and one that still finds wide-
tions between Ex and the ground state be spread use, was a three-level device in which a laser, which produces intense lines in the Tuning of dye lasers can be readily accom-
rapid. ruby crystal was the active medium. The ruby green (514.5 om) and blue (488.0 nm) regions. plished by replacing the nontransmitting
The advantage of the four-level system is was machined into a rod about 4 em in This laser is a four-level device in which mirror shown in Figure 5-3 with a monochrom-
that the population inversions necessary for length and 0.5 em in diameter. A ftash tube argon ions are formed by an electrical or ator equipped with a reftection grating or a
laser action are more readily achieved. To was coiled around the cylinder to produce radio frequency discharge. The input energy Littrow-type prism (p. 126) which will reftect
understand this, note that at room tempera- intense ftashes of light. Because the pumping is sufficient to excite the ions from their only a narrow bandwidth of radiation into
ture a large majority of the laser particles will was discontinuous, a pulsed laser beam was ground state, with a principal Quantum the laser medium; the peak wavelength can
be in the ground-state energy level Eo'in both produced. Continuous wave ruby sources are number of 3, to various 4p states. Laser activ- be varied by rotatioQ of the grating or prism.
systems. Sufficient energy must thus be now available. ity then involves transitions to the 4s state. Emission is then stirllulated for only part of
provided to convert more than 50% of the A variety of gas lasers are sold commer- Dye lasers4 have become important radia- the fluorescent spec(rum, namely. the wave-
lasing species to the E, level of a three-level cially. An important example is the argon ion tion sources in chemistry because they are length reflected from the monochromator.
tunable over a range of 20 to 50 nm; that is,
dye lasers provide bands of radiation of a
chosen wavelength with widths of a few hun- WAVELENGTH
dredths of a nanometer or less. SELECTION; MONOCHROMATORS
The active materials in dye lasers are solu-
AbIofption "', Ey tions of organic compounds capable.()fftuores- With few minor exceptions, the analytical
cing in the ultraviolet. visible. or infrared methods considered in the following seven
rv\ri I
rvv- regions. In contrast to ruby or gas lasers. chapters require dispersal of polychromatic
however, the lower energy level for laser radiation into bands that encompass a re-
E, action (Ex in Figure 5-6) is not a single energy stricted wavelength region. The most common
but a band of energies arising from the super- way of producing such bands is with a device
lal
position of a large number of small vibra- called a monochromator.'
Ey tional and rotational energy states upon the

'Ulr
base electronic energy state. Electrons in E).
V\r Light amplification
by stimulated
emission
may then undergo transitions to any of these
states, thus producing photons of slightly dif-
j
• For a more complete d~ussion or monochromators,
see: R. A. Bauman, AbJO,ption Spect,OM:OPY.New York:
Stimulated / E, ferent energies.
emission
Wiley, 1962; F. A. Jenkins and H. E. White, FUMamen-
tats of Optia. 3d ed. New York: McGraw-HiI~ 1957;
E. J. Meehan, in T,etIliM 011 A""lytiClJI CMmUt'Y. cds.
(b)
I. M. KolthofTand P. J. Elving. New York: Wiley, 1964.
FIGURE 6-6 Passage of radiation through (a) a noninverted • For rurther inrormation, see: R. B. Green, - Dye Laser Part t, vol. 5. Chapter 55: and J. F. James and R. S.
Instrumentation," J. Chem. Educ.• 54 (9) A365, (10) A407, Sternberg, The Design of Optical Spectromners. London:
population and (b) an inverted population. Chapman and Hall. 1969,
(1977~
grating, angular dispersion results. from Construedoa ~terials. Clearly, the mate-
diffraction, which occurs at the reflective rials employed for fabricating the windows
Focal
surface. In both ~esigns, the dispersed radia- lenses, and prisms of a monochromator must

~~7B
••••... A

A2/Exit
plane
tion is focused on the focal plane AB where it
appears as two "images of the entrance slit
(one for each wavelength).
transmit radiation in the frequency range of
interest •. ideally, the transmittance should
approach tOO%, although it is sometimes
/ sfit necessary to use substances with transmit-
A Types of Instruments tances as low as 20%. The refractive index of
Employing Monochromators materials used in the construction of windows
The method of detecting the radiation dis- and prisms should be low in order to reduce
persed by a monochromator varies. In a reflective losses (see Equation 4-14, p. 103).
spectroscope, detection is accomplished vis- However, for lenses which function by bend-
ually with a movable eyepiece located along ing rays of radiation, a material with a high
the focal plane. The wavelength is then refractive index is desirable in order to reduce
determined by measurement of the angle be- focal lengths. Ideal construction materials for
tween the incident and dispersed beams. In a both lenses and windows should exhibit little
spectrograph, a photographic film or plate is change in refractive index with frequency,
mounted along the focal plane; the series of thus reducing chromatic aberrations. In
darkened images of the slit along the length contrast, just the opposite property is sought
of the developed film or plate is called a for prisms, where1he extent of dispersion
spectrogram. depends upon the rate of change of refractive
The monochromators shown in Figure 5-7 index with frequency. In addition to the fore-
(bl are also utilized for dispersing elements in going optical properties, it is desirable that
spectr~ters. Such instruments have a fixed monochromator components be resistant to
FIGURE 5-7 Two types of monochromators: (a) Bunsen mechanical abrasion and attack by atmos-
prism monochromator, and (b) Czerney-Tumer grating mono- exit slit located in the focal plane. With a
continuous source, the wavelength emitted pheric components and laboratory fumes.
chromator. (In both instances, 11 > 12,) Needless to say, no single substance meets
from this slit can be varied continuously by
rotation of the dispersing element. all of these criteria and trade-offs are thus
We need to define two other types of in- required in monochromator design. The
Mooochromators for ultraviolet, visible, which projects a series of rectangular images choices here depend strongly upon the wave-
struments to complete this discussion. A
and infrared radiation are all similar in of the entrance slit upon a plane surface (the length region to be used.
spectrophotometer is a spectrometer which
mechanical construction in the sense that focal plane). In addition, most monochroma- contains a photoelectric device for determin- Table 5-1 lists the properties of the
they employ slits, lenses, mirrors, windows, tors have entrance and exit windows, which ing the power of the radiation exiting from common substances employed for fabricating
and prisms or gratings. To be sure, the mate- are designed to protect the components from the slit. A photometer also employs a photo- monochromator components. Clearly, no
rials from which these components are fabri- dust and corrosive laboratory fumes. electric detector but contains no monochro- single material is suitable for the entire wave-
cated will depend upon the wavelength region Figure 5-7 shows the optical design of two mator; instead, filters are used to provide length region. For the ultraviolet, visible, and
of intended use (see Figure 5-2b and c). typical monochromators, one employing a near-infrared regions (up to about 3000 nm~
radiation bands encompassing limited
prism for dispersal of radiation and the other a quartz prism is often employed; it should be
wavelength regions. A photometer is inca-
Components of • Monochromator a grating. A source of radiation containing noted, however, that glass provides better res-
pable of providing a continuously variable
but two wavelengths, 11 and 12, is shown for olution for the same size prism for wave-
All monochromators contain an entrance slit, band of radiation.
purposes of illustration. This radiation enters lengths between 350 and 2000 nm. As shown
a collimating lens or mirror to produce a par-
the monochromators via a narrow rectangu- Prism Monochromators in column 5 of Table 5-1, several prisms are
allel beam of radiation, a prism or grating as
lar opening or slit, is collimated, and then required fo cover the entire infrared region.
a dispersing element, 6 and a focusing element
Prisms can be used to disperse ultraviolet, Types of Prisms and Prism Monochroma-
strikes the surface of the dispersing element at
an angle. In the prism monochromator, re- visible, and infrared radiation. The material tors. Figure 5-8 shows the two most common
fraction at the two faces results in angular used for their construction will differ depend- types of prism configurations. The first is a
• Much less gencraIIy employed are interference wedges.
ing upon the wavelength region. 6O-deg design, which is ordinarily fabricated
These devices are described in the next section (p. 136). dispersal of the radiation, as shown; for the
somewhat more compact monochromator rise in the refractive index for glass below 400
designs. In addition, when quartz is Dm corresponds to the sharp increase in
employed, polarization is canceled by the absorption that prevents the use of this mate-
reversal of the radiation path. A typical rial below 350 Dm. in the region of 350 to
Littrow-type monochromator' is shown in 2000 DID, however, glass is greatly superior to
Figure 7-10. quartz for prism fabrication because of its
Angular DispersioR of ~ The angular larger change in refractive index with wave-
dispersion of a prism is the rate of change of length (dll/d).).
FIGURE 5-8 Dispersion by a prism: (a) quartz Cornu type,
the angle 8 in Figure 5-8 as a function of Focal-Plane DiSpersion of Prism Mono-
and (b) Littrow type.
wavelength; that is, d8/dl. The spectral purity chromators. The focal-plane dispersion of a
of the radiation exiting from a prism mono- monochromator refers to the variation in
chromator is dependent upon this quantity. wavelength as a function of y, the linear dis-
The angular dispersion of a prism can be tance along the line AB of the focal plane of
from a single block of material. When crystal- called a Cornu prism. Figure 5-7a shows a
resolved into two parts the instrument (see Figure 5-7). That is, the
line (but not fused) quartz is employed, Bunsen monochromator, which employs a
however, the prism is usually formed by 6O-deg prism, likewise often made of quartz. d8 d8 dn focal-plane dispersion is given by dy/d)'.
cementing two 3().deg prisms together, as Figure 5-8b depicts a Littrow prism, which d)' = dn . d)' (5-1) Figure 5-10 shows the focal-plane disper-
shown in Figure 5-8a; one is constructed is a 3().deg prism with a mirrored back. It is sion of two prism monochromators and one
from right-handed quartz and the second seen that refraction occurs twice at the same where d8/dn represents the change in 8 as a grating instrument. Note that the dispersion
interface; the performance characteristics of function of the refractive index n of the prism for the two prism monochromators is highly
from left-handed quartz. In this way, the optic-
aUyactive quartz causes no net polarization of the Littrow prism are thus similar to those of material and dn/d)' expresses the variation of nonlinear, the longer wavelengths being
the emitted radiation; this type of prism is the 6O-deg prism. The Littrow prism permits the refractive index with wavelength (that is, bunched together over a relatively small dis-
the dispersion of the substance from which tance. The two prism monochromators were
the prism is fabricated). Littrow types. cach having a height of 57 mm.
The magnitude of dO/dn is determined by Notc the much largcr dispersion exhibited by
the geometry of the prism and the angle of the monochromator with a glass prism, in the
incidence i (Figure 5-Sa~ In order to avoid region of 350 to 800 nm.
TABLE 1·1 CONSTRUCTION MATERIAL FOR SPECTROPHOTOMETER
problems of astigmatism (double images), this
OPTICS

=w
angle should be such that the path of the
Uleful HarUelsDd beam through the prism is within a few
Tl'lIDSIIlittance Refractive 1tuIe fer CIIemicaI degrees of being parallel to the base of the
Material Range, pm Index Prisms, IJI11 Resistance
prism. Under these circumstances. dO/dll
Fused silica 0.18-3.3 1.46 0.52 x 10-4 0.18-2.7 Excellent depends only upon the prism angle ClC (Figure
Quartz 0.20-3.3 1.54 0.63 x 10-4 0.20-2.7 Excellent 5-Sa) and increases rapidly with this quantity.
Flint glass 0.35-2.2 1.66 1.70 x 10-4 0.35-2 Excellent Reflection losses, however. impose an upper K 1.60
Calcium 0.12-12 1.43 0.33 x 10-4 5-9.4 Good ~
limit of about 60 deg for IX. For a prism in
fluoride .S

~fluorite)
Lit ium
fluoride
0.12-6 1.39 0.29 x 10-4 2.7-5.5 Poor
which ClC = 60 deg, it can be shown that
2
dO/dn = (I - n /4,-t (5-2)
.~
~ -----------
~OCk salt .

~ 1.50
Sodium 0.3-17 1.54 0.94 x 10-4 8-16 Poor The term dll/d)' in Equation 5-1 is related
chloride to the dispersion of the substance from which
Potassium 0.3-29 1.56 1.45 x 10-4 15-28 Poor
bromide the prism is constructed. We have noted
Cesium 0.3-70 1.79 15-55 Poor (p. 102) that the greatest dispersion for a
iodide given material is near its anomalous disper- 1.40
KRS-5 1-40 2.63 24-40 Good sion region, which in turn is close to a region o 200 400 600 800 1000 1200
(TlBr-TlI) of absorption. The dispersion of some sub-
Wavelength. nm

stances employed for construction of prisms FIGURE 5-9 Dispersion of several optical
• Radians/ l'1li at 0.589 pm is shown in Figure 5-9. Note that the rapid materials.
Figure 5-10 illustrates one ofthe important reflection from a reflection grating. A trans-
advantages of grating mopochromators- mission grating consists of a series of parallel
linear dispersion along the focal plane. and closely spaced grooves ruled on a piece of
Monochromatic
Resolving Power of Prism Monocbroma- glass or other transparent material. A grating beam It incident
tors. The resolving .power R of a prism gives suitable for use in the ultraviolet and visible ongtel .
the limit of its ability to separate adjacent region has between 2000 and 6000 lines per
images having slightly different wavelengths. millimeter. An infrared grating requires con-
Mathematically, this quantity is defined as siderably fewer lines; thus, for the far infrared
region, gratingS with 20 to 30 lines per milli-
meter may suffice. It is vital that these lines be
where dl represents the wavelength difference equally spaced. throughout the several centi-
that can just be resolved and l is the average meters in length of the typical grating. Such
wavelength of the two images. It can be gratings require elaborate apparatus for their
shown that the resolving power of a prism is production and are consequently expensive.
directly proportional to the length of the Replica gratings are less costly. They are
prism base b (Figure 5-8) and the dispersion manufactured I;>yemploying a master grating
of its construction material. That is, as a mold for' the production of numerous
plastic replicas; the products of this process, . FIGURE 6-11 Schematic diagram illustrating the mechan-
while inferior in performance to an original ism of diffraction from an echellette-type grating. (From R. P.
grating, are adequate for many applications. Bauman, Absorption Spectroscopy. New York, Wiley, 1962,
When a transmission grating is illuminated p. 65. With permission.)
from a slit, ~ch groove scatters radiation
Gl'IIting Monochromatora
and thus effedtively becomes opaque. The
for Wavelength Selection
nonruled portions then behave as a series of
Dispersion of ultraviolet, visible, and infrared closely spaced slits, each of which acts as a the radiation as shown in Figure 4-00 reflected beams 1,2, and 3 can occur. In order
radiation can be brought about by passage of new radiation source; interference among the (p. 98). The angle of diffraction, of course, for constructive interference to occur between
a beam through a transmission grating or by multitude of beams results in diffraction of depends upon the wavelength. adjacent beams, it is necessary that their path
Reflection gratings are used more exten- lengths differ by an integral multiple n of the
sively in instrument construction than their wavelength l of the incident beam.
Gl'lting
transmitting counterparts. Such gratings are In Figure 5-11, parallel beams of mono-
200 . 300 500 made by ruling a polished metal surface or by chromatic radiation 1 and 2 are shown strik-
~. om I I I evaporating a thin film of aluminum onto the ing the grating at an incident angle i to the
surface of a replica grating. As shown in grating normal. Maximum constructive inter-
figure 5-11, the incident radiation is reflected ference is shown as occurring at the reflected
Glass prism
200 350 400 450 500 600 800 from one of the faces of the groove, which angle r. It is evident that beam 2 travels a
X,om A-,j\il9£~;;; -.-, I I I I I II then acts as a new radiation source. Interfer- greater distance than beam 1 and that this
ence results in radiation of differing wave- difference is equal to (CD - AB). For con-
Quartz prism
lengths being reflected at different angles r. structive interference to occur, this difference

A,nm
200
I
250
I
300
I
350 400
I
'! I ,
500600800
II
Diffraction by a Grating. figure 5-11 is a
schematic representation of an echellette-type
must equal n).. That is,

M = (CD - AB)
A 8 grating, which is grooved or blazed such that
I it has relatively broad faces from which Note, however, that angle CAD is equal to
0 5.0 10.0 15.0 20.0 25.0 reflection occurs and narrow unused faces.
Diltance y along focal plane, em angle i and that angle BDA is identical with
This geometry provides highly efficient dif- angle r. Therefore, from simple trigonometry,
FIGURE 6-10 Dispersion for three types ofmonochromators. fraction of radiation. Each of the broad faces
The points A and B on the scale correspond to the points we may write
can be considered to be a point source of
shown in Figure 5-7. radiation; thus interference among the
where d is the spacing between the reflecting and the wavelengths for the first-, secondo, RfIOIviDg Power of a Gntiac- It can be For the grating, we employ Equation 5-7
surfaces. It is also seen that and thUd-order reflections are 543, 271, and shown 7 that the resolving power R of a grat- .t
181 nm, respectively. ing is given by the very simple expression -=aN
.u
AB= -dsin r
Similarly, when r = -10 deg (here r lies to .t For the first-order spectrum (D = I)
The minus sign, by convention, indicates that the right of the grating n0"ttal) R = .u = aN (5-7)
reflection has occurred. The angle r, then, is N 460.25 460 3'
negative when it lies on the opposite side of where n is the diffraction order and N is the = 0.10 x I =. x 10 hnes
.t = SOO[sin 48 + sine-10)] = 284.7
the grating normal from the angle i (as in n n number of lines illuminated by the radiation · I h 4.6 X 103 lines 0.1 em
Figure 5-1I~ and is positive when it is on the from the entrance slit. Thus, as with a prism gra t 109 engt = 2000 Ii x --
same side. Substitution of the last two expres- nes/mm mm
(Equation 5-4~ the resolving power depends
sions into the first gives the condition for con- upon the physical size of the dispersing •••0.23 em
structive interference. Thus, Wavelength (nm) for element.
Thus, in theory, the separation can be
III = d(sin i + sin r) (5-5) accomplished with a silica prism with a base
r n=1 n=2 n=3
EXAMPLE of 3.5 em, a glass prism with a base of 1.3 em,
Equation 5-5 suggests that several values 20 543 271 181 ~mpare the size of (I) a 6O-deg fused or 0.23 em of grating.
of.t exist for a given diffraction angle r. Thus, 10 458 229 153 silica' prism; (2) a 6O-deg glass prism; and
if a first-order line (D = I) of 800 nm is found 0 372 186 124
at r, second-order (400 nm) and third-order -10 285 142 95 (3) a grating with 2000 lines/mm, that would Gntinp versus Priims. Gratings offer
(267 nm) lines also appear at this angle. Or- be required to resolve two lithium emission several advantages over prisms as dispersing
lines at 460.20 and 460.30 nm. Average values elements. One of these is that the dispersion is
dinarily, the first-order line is the most
intense; indeed, it is possible to design grat- A concave grating can be produced by for tlje dispersion (dn/d.t) of fused silica and nearly constant with wavelength; this
ings that concentrate as much as 90% of the ruling a spherical reflecting surface. Such a glass ~n the region of interest are 1.3 x 10- 4 property makes the design of monochroma-
incident intensity in this order. The higher- diffracting element serves also to focus the and 3.6 x 10-4 nm-I, respectively. tors considerably more simple. A second
order lines can generally be removed by radiation on the exit slit and eliminates the For the two prisms, we employ Equation 5-4 advantage can be seen from the foregoing
filters. For example, glass, which absorbs ra- need for a lens. .t dn example, namely, that better dispersion can
R=-
diation below 350 nm, eliminates the higher- Dispersion fJl GntiDp. The angular dis- .u =b-d)' be expected for the same size of dispersing
element. In addition, reflection gratings pro-
order spectra associated with first-order persion of a grating can be obtained by
radiation in most of the visible region. The differentiating Equation 5-5 while holding i vide a means of dispersing radiation in the
example which follows illustrates these points. constant; thus, at any given angle of incidence far ultraviolet and far infrared regions where
.t I 460.25 I
b-- x-- ------ x-- absorption prevents the use or prisms.
EXAMPLE dr D
.u dn/d.t 460.30 - 460.20 dn/d)' Gratings have the disadvantage of produc-
An echellette grating containing 2000 -=-- (5-6) For fused silica, ing somewhat greater amounts of stray radia-
d)' dcosr
blazes per millimeter was irradiated with a tion as well as higher-order spectra. These
polychromatic beam at an incident angle 48 b = 460.25 nm x I x 10-7 em disadvantages are ordinarily not serious be-
Note that the dispersion increases as the dis-
deg to the grating normal. Calculate the 0.10 nm 1.3 x 10-4 nm-I om cause the extraneous radiation can be mini-
tance d between rulings decreases or as the
wavelengths of radiation that would appear number of lines per millimeter increases. Over mized through the use of filters and by proper
= 3.5 em
at an angle of reflection of +20, + 10,0, and short wavelength ranges, cos r does not instrument design.
-10 deg (angle r, Figure 5-11). change greatly with .t, so that the dispersion of and f<?rglass, For a number of years, high-quality grat-
To obtain d in Equation 5-5, we write a grating is nearly linear. By proper design of ings were more expensive than good prisms.
the optics of a grating monochromator, it is
b = 460.25 1 x 10-7 = 1.3 em This disadvantage has now largely disap-
Imm nm nm 10.10 x 3.6 x 10-4
d=---- x 106- =500-- possible to produce an instrument that for all peared.
2000 blazes mm blaze
practical purposes has a linear dispersion of
radiation along the focal plane of the exit slit. Monochromator Slits
When r in Figure 5-11 equals + 20 deg
Figure 5-10 shows the contrast between a The slits of a monochromator play an impor-
, SOO(. 48 . 2) 542.6 grating and a prism monochromator in this 1 R. A. Sawyer. Experimental SpeClroscoPY. 2d cd. New tant part in determining its quality. Slit jaws
A=- sm +sm 0 =--
D n regard. Jersey: Prentic:e-Hal~ 1951. p. 130. are formed by carefully machining two pieces
Monochromator A peak power. Figure 5-14 illustrates the .rela-
of metal to give sharp edges, as shown in setting ..l Movement of the .monochromator in either
Figure 5-12. Care is taken to assure that the I tionship between the effective bandwidth of direction diminishes the transmitted intensity
edges of the slit are exactly parallel to one I an instrument and. its effectiveness in resolv- of A2' but increases the intensity of one of the
I ing spectral peaks. Here, the exit slit of a
another and that they lie on the same plane. other lines by an equivalent amount. As
I monochromator is illuminated with a beam
In some monochromators, the openings of I shown bJl the solid line in the plot to the
the two slits are fixed; more commonly, the composed of just three wavelengths, AI> A2' right, no spectral resolution of the three wave-
spacing can be adjusted with a micrometer and A); each beam has the same intensity. In lengths is achieved.
mechanism. I the top figure, the effective bandwidth of the In the middle drawing of Figure 5-14, the
The entrance slit (see Figure 5-7) serves as I instrument is exactly equal to the difference in effective bandwidth of the instrument has
I wavelength between AI and AZ or AZ and A).
a radiation source; its image is focused on the I been reduced by narrowing the openings of
surface containing the exit slit. If the radia- I When the monochromator is set at AZ , radia- the exit and entrance slits to three-quarters
tion source consists of a few discrete I tion of this wavelength just fills the slit. that of their original dimensions. The solid
wavelengths, a series of rectangular images I
appears on this surface as bright lines, each I Effective bandwidth
corresponding to a given wavelength. A partic-
ular line can be brought to focus on the exit Radiant Monochromator
power sening
slit by rotating the dispersing element. If the p
entrance and exit slits are of the same size (as A, A. A"

is usually the case ~ the image of the entrance Relative


A, A. A3 slit
slit will in theory just fill the exit -slit opening width
I--Bandwidth--t
when the setting of the monochromator cor-
Monochromator
responds to the wavelength of the radiation. setting. A
Movement of the monochromator mount in
one direction or the other results in a contin- FIGURE 5-13 Illumination of an exit slit A, A2 A3
uous decrease in emitted intensity, zero being by monochromatic radiation AZ at various ;;

reached when the entrance-slit image has monochromator settings. Exit and entrance •.
'j( Effective
bandwidth
been displaced by its full width. slits are identical. g
Figure 5-13 illustrates the situation in
which monochromatic radiation of wave-
~
1p
length A2 strikes the exit slit. Here, the mono- Cl.:
chromator is set for A2 and the two slits are suits in the image being moved completely ~
0
identical in width. The image of the entrance out of the slit. The lower half of the figure Q. A, A. A3
slit just fills the exit slit. Movement of the shows a plot of the radiant power emitted as i
ia: Effectiv.

,4l
monochromator to a setting of AI or A) re- a function of monochromator setting. Note A, A. A3 bandwidth
that the bandwidth is defined as the span of

'1JJIfJl
monochromator settings (in units of wave-
length) needed to move the image of the
C entrance slit across the exit slit. If polychro-
I
I matic radiation were employed, it would also
I
represent the span of wavelengths emitted A, A2 A3
A-~.i..._':'/ +~.-"""';-""--B from the exit slit for a given monochromator Monochromator
~:~ I setting. setting A

o The effective bandwidth for a monochroma- FIGURE 5-14 The effect of the slit wiath on spectra.
The entrance slit is illuminated with AI> AZ' and A) only.
A-IIa-"'-B tor is also defined in Figure 5-13 as one-half
the wavelength range transmitted by the in- Entrance and exit slits are identical. Plots on the right show
FIGURE 5-12 Construc- strument at a given wavelength setting, or the changes in emitted power as the setting of monochromator
tion of slits. range of wavelengths encompassed at half is varied.
line in the plot on the right shows that partial if one of the elements is a gratin& higher-order zero so that the equation accompanying
resolution of the three lines results. When the wavelengths are removed by the second Figure 5-16 simplifies to
effective bandwidth is decreased to one-half element.
!lA' = 2t (5-8)
the difference in wavelengths of the three
beams, complete resolution is obtained, as where l' is the wavelength of radiation in the
shown in the bottom drawing. 0.2 WAVELENGTH dielectric and t is the thickness of the dielec-
The effective bandwidth of a monochroma- E SELECTION; FILTERS tric. The corresponding wavelength in air is
E given by
tor depends upon both the dispersion of the .<:'
prism or grating as weIl as the width of the
entrance and exit slits. Most monochroma- "
·i Absorption and interference filters are
employed for wavelength selection. The
l=l'n
tors are equipped with variable slits so that fonner are restricted to the visible region of where n is the refractive index of the dielectric
the effective bandWidth can be changed. the spectrum. Interference filters, on the other medium. Thus, the wavelengths of radiation
The use of minimal. slit widths is desirable hand, are available for ultraviolet, visible, and transmitted by the filter are
where the resolution of narrow absorption or infrared radiation.
emission bands is needed. On the other hand, 1 = Un
there is a marked ~ease in the available D

radiant power as the slits are narrowed, and Interf ••.• nce Filters The integer n is the order of interference. The
300 400 500
ac:c:urate measurement of this power becomes glass layers of the filter are often selected to
wavelength. nm
more difficult. Thus, wider slit widths may be As the name implies, interference filters rely absorb all but one of the reinforced bands;
used for quantitative analysis than for quali- FIGURE 5-15 The slit width needed to on optical interference to provide relatively transmission is thus restricted to a single
tative work, where spc;etral detail is important. maintain a constant eft'ective bandwidth of narrow bands of radiation (see Figure 5-17). order.
As noted previo~ly, the dispersion of a 1 nm from a quartz Littrow prism mono- An interference filter consists of a transparent Figure 5-17 illustrates the performance
prism is not linear (see Figure 5-10). Much chromator. dielectric (frequently calcium fluoride or mag-
characteristics of typical interference filters.
narrower slits muSt, therefore, be employed at nesium fluoride) that occupies the space be-
long wavelengths than at short in order to tween two semitransparent metalIic films
obtain radiation of a given effective band- coated on the inside surfaces of two glass
width. The slit width in millimeters required parts also causes stray radiation to reach the plates. The thickness of the dielectric layer is
to maintain an effective bandwidth of one cdt slit. Generally, the efl'ects of spurious ra- carefully controlled and determines the wave-
nanometer for a monochromator equipped diation are minimimJ by introducing bafJles in length of the transmitted radiation. When a
with. Littrow prism is shown in Figure 5-15. appropriate spots in the monochromator and perpendicular beam of collimated radiation
One of the advantages of a grating mono- by coating interior surfaces with flat black strikes this array, a fraction passes through
chromator is that a fixed slit width produces paint. In addition, the monochromator is the first metallic layer while the remainder is
radiation of nearly constant bandwidth, re- sealed with windows over the slits to prevent reflected. The portion that is passed under-
gardless of wavelength. entrance of dust and fumes. Despite these goes a similar partition upon striking the
precautions, however, some spurious radia- second metallic film. If the reflected portion
tion is still emitted; we shaIl find that its from this second interaction is of the proper FIGURE 5-16 The interference filter. At
presence can have serious effects on absorp- wavelength, it is partiaIly reflected from the point), light strikes the semitransparent film
tion measurements under certain conditions. inner side of the first layer in phase with in- at an angle 8 from the perpendicular, is
The exit beam of a monochromator is usuaIly coming light of the same wavelength. partiaIly reflected, partiaIly passed. The same
contaminated with smaIl amounts of radia- The result is that this particular wavelength is process occurs at I', 2, 2', and so forth.
Double Monochromator.
tion having wavele~hs far different from reinforced, while most other wavelengths, For reinforcement to occur at point 2, the
that of the instrument setting. There. are Many modern monochromators contain two being out of phase, suffer destructive distance traveled by the beam reflected at l'
several sources of this unwanted radiation. dispersing elements; that is, two prisms, two interference. must be some multiple of its wavelength in
Reflections of the beam from various optical gratings, or a prism and a grating. This ar- Figure 5-16 illustrates an interference filter. the medium 1'. Since the path length between
parts and the monochromator housing con- rangement markedly reduces the amount of For purposes of clarity, the incident beam is surfaces can be expressed as tlcos 8, the
tribute to it. Scattering by dust particles in stray radiation and also provides greater dis- shown as arriving at an angle 8 from the condition for reinforcement is that !lA' =
the atmosphere or on the surfaces of optical persion and spectral resolution. Furthermore, perpendicular. In ordinary use, 8 approaches 2tlcos 8 where n is a small whole number.
the wedge, one can isolate a bandwidth of ing certain portions of the spectra. The most stance employed for cell windows in the infra-
about '20 nm. common type consists of colored glass or of a red region; the other infrared transparent
Interference wedges are available for the dye suspended in gelatin and sandwiched be- materials listed in Table 5-1 (p. 126) may also
visible region (400 to 700 om~ the near-infra- tween glass plates. The former have the be used for this purpose.
red region (1000 to 2000 nm~ and for several advantage of greater thermal stability. The best cells have windows that are per-
parts of the infrared region (2.5 to 14.5 JlI11). Absorption filters have effective band- fectly normal to the direction of the beam in
widths that range from perhaps 30 to 250 om order to minimize reflection losses. The most
Absorption Filters (see Figure 5-18). Filters that provide the nar- common cell length for studies in the ultra-
rowest bandwidths also absorb a significant violet and visible regions is I em; matched,
Absorption filters, which are generally less ex-
fraction of the desired radiation, and may calibrated cells of this size are available from
pensive than interference filters, have been
lu(ve a transmittance of 0.1 or less at their several commercial sources. Other path
widely used for band selection in the visible
band peaks. Glass filters with transmittance lengths, from 0.1 em (and shorter) to 10 em,
region. These filters limit radiation by absorb-
maxima throughout the entire visible region can also be purchased. Transparent spacers
are available commercially. for shortening the path length of l-em cells to
.Cut-off filters have transmittances of nearly 0.1 em are also available.
100% over a portion of the visible spectrum, Cells for infrared studies of liquids and so-
5110 6215 6225 6940 6960
Wavelength, A but then rapidly decrease to zero transmit- lutions generally have path lengths of less than
tance over the remainder, A narrow spectral Imm.
FIGURE 5-17 Transmission character- Interle<wnc:e
band can be isolated by coupling a cut-off For reasons of economy, cylindrical cells
istics of typical interference filters, filler
Iso filter with a second filter (see Figure 5-18b).
;It is apparent from Figure 5-18a that the
are sometimes employed in the ultraviolet
and visible regions. Care must be taken to
1 pejformance characteristics of absorption duplicate the position of the cell with respect
Ordinarily, filters are characterized, as shown, S a.ndwidth
-8nm fil~rs are significantly inferior to those of to the beam; otherwise, variations in path
by the wavelength of their transmittance i interference-type filters. Not only are their length and reflection losses at the curved sur-
peaks, the percentage of incident radiation ~25
CL bandwidths greater, but the fraction of light faces can cause significant errors.
transmitted at the peak (their percent trallS-
AbsorPtion filter transmitted is also less. Nevertheless, absorp- The quality of absorbance data is critically
mitumee, p. 149~ and their bandwidths at a tion filters are totally adequate. for many dependent upon the way the matched cells
transmittance equal to one-half the maximum
applications. are used and maintained. Fingerprints, grease,
(the effective bandwidth). or other deposits on the walls alter the trans-
0
Interference filters are available through- 400 500 600
mission characteristics of a cell markedly.
out the ultraviolet and visible regions and up W-'engttI,nm
(I)
Thus, thorough cleaning before and after use
to about 141llf1in the infrared. Typically, half
Sample containers arc required for all spec- is imperative; the surface of the windows
bandwidths are about 1,5% of the wavelength 100
Absorption
troscopic studies except emission spectros- must not be touched during the handling.
at peak transmittance, although this figure is
copy. In common with the optical elements Matched cells should never be dried by heat-
reduced to 0.15% in some narrow-band •.l! filter> Orlnge
cut .••"
filter of monochromators, the cells or cuvettes that ing in an oven or over a flame-such treat-
filters; these have maximum transmittances of
!! hold the samples must be made of material ment may cause physical damage or a change
about 10%. .~ in path length. The cells should be calibrated
c: SO tha.t passes radiation in the spectral region of
S interest. Thus, as shown in Figure 5-2, quartz against each other regularly with an absorb-
Interference Wedges
•.~•.
'C or fused silica is required for work in the ing solution .
An interference wedge consists of a pair of CL ult~aviolet region (below 350 nm); both of
mirrored, partially transparent plates sepa- theSe substances are transparent in the visible
rated by a wedge-shaped layer of a dielectric 0 region and to about' 3 Ilm in the infrared
400 500 600 700
materiaL The length of the plates ranges from Wavelength, nm
region as well. Silicate glasses can be
about 50 to 200 mm. The radiation trans- lbl
employed in the region between 350 and 2000
mitted varies continuously from one end to the nm. Plastic containers have also found appli- Early instruments for the measurement of
other' as the thickness of the wedge varies. FIGURE 5-18 Comparison of various cation in the visible region. Crystalline emission and absorption of radiation required
By choosing the proper linear position along types of filters for visible radiation. sodium chloride is the most common sub- visual or photographic methods for detection.
Glass ThinI.yerof liI_
choice of exper,imental conditions minimize
These detectors have been largely supplanted ual events (absorption of one photon). the this effect.
by transducers which convert radiant energy
into an electrical signal; our discussion will
be confined to detectors of this kind. Brief
probability of which can be described by the
use of statistics. In contrast. heat transducers,
which are required for the detection of infra-
~:~~~. Barrier-type cells are widely used in
simple, portable. instruments where rug-
gedIlCSljand low cost are important. For rou-
red radiation, are nonquantized sensors. tine analyses. these instruments often provide
consideration of photographic detection will
As will be shown in Chapter 6. the distinc-
~
be found in Chapter 12. perfectly reliable analytical data.
tion between photon and heat detectors is im- FIGURE 6-19 Schematic of a typical Phototubes. A second type of photoelectric
Properties of Photoelectric Detectors. To
portant because shot noise (p. 7!) often barrier-layer cell. device is the phototube. which consists of a
be usefu~ the detector must respond to ra-
diant energy over a broad wavelength range. It limits the behavior of the former whIle John- semicylindrical cathode and a wire anode
should, in addition. be sensitive to low levels son noise may limit the latter. As a sealed inside an evacuated transparent
consequence. indeterminate errors associated envelope. The concave surface of the elec-
of radiant power. respond rapidly to the
radiation, produce an electrical signal that with the two types of detectors are different. the entire array is protected by a transparent trode supports a layer of photoemissive mate-
can be readily amplified, and have a relatively envelope. When radiation of sufficient energy rial (p. 100) that tends to emit electrons upon
low noise level (for stability). Finally, it is reaches the semiconductor. covalent bonds being irradiated. When a potential is applied
Photon Detectors are broken, with the result that conduction
essential that the signal produced be directly across the electrodes, the emitted electrons
proportional to the beam power P; that is, Several types of photon detectors are avail- electrons and holes are formed. The electrons Oow to the wire anode, generating a photo-
able. including: (1) photoooltaic cells. in then migrate toward the metallic film and the current. The currents produced are generally
G = KP. + K' (5-10) which the radiant energy generates a current holes toward the base upon which the semi- about one-tenth as great as those from a
where G is the electrical response of the detec- at the interface of a semiconductor layer and conductor is deposited. The liberated elec- photovoltaic cell fot a given radiant intensity.
tor in units of current. resistance, or emf. The a metal; (2) phototubes. in which radiation trons are free to migrate through the external In contrast, however, amplification is easily
constant K measures the sensitivity of the causes emission of electrons from a photo- circuit to interact with these holes. The result accomplished since the phototube has a high
detector in terms of electrical response per sensitive solid surface; (3) photomultiplier is an electrical current whose magnitude is electrical resistance. Figure 3-19 (p. 59) is
unit of radiant power. Many detectors exhibit tubes, which contain a photoemissive surface proportional to the number of photons strik- a schematic diagram of a typical phololube
a small constant response. known as a dark as well as several additional surfaces that emit ing the semiconductor surface. Ordinarily. the arrangement.
currenl K'. even when no radiation impinges a cascade of electrons when struck by elec- currents produced by a photovoltaic cell are The number of electrons ejected from a
on their surfaces. Instruments with detectors trons from the photosensitive area; (4) semi- large enough to be measured with a galva- photoemissive surface is directly proportional
that have a dark-eurrent response are or- conductor detectors. in which absorption of nometer or microammeter; if the resistance of to the radiant power of the beam striking that
dinarily equipped with a compensating circuit radiation produces electrons and holes, thus the external circuit is kept small, the magni- surface. As the potential applied across the
that permits application of a countersignal to leading to enhanced conductivity; and (5) sili- tude of the photocurrent is directly propor- two electrodes of the tube is increased, the
reduce K' to zero. Thus. under ordinary cir- con diodes. in which photons increase the con- tional to the power of the radiation striking fraction of the emitted electrons reaching
cumstances. we may write ductance across a reverse biased pn junction. the cell. Currents on the order of 10 to 100 the anode rapidly increases; when the satura-
Photovoltak: or Barrier-Layer Cells. The pA are typical. tion potential is achieved, essentially all of
photovoltaic cell is used primarily to detect The barrier-layer cell constitutes a rugged, the electrons are collected at the anode.
Types of Photoelectric Detectors. As in- and measure radiation in the visible region. low-eost means for measuring radiant power. The current then becomes independent of
dicated in Figure 5-2, two general types of The typical cell has a maximum sensitivity at No external source of electrical energy is potential and directly proportional to the ra-
radiation transducers are employed; one re- about SSO nm; the response falls off to per- required. On the other hand. the low internal diant power (see Figure 5-20). Phototubes are
sponds to photons, the other to heat. All haps 10"10 of the maximum at 350 and 750 resistance of the cell makes the amplification usually operated at a potential of about 90 V,
photon detectors are based upon interaction nm. Its range approximates that of the human of its output less convenient. Thus, although which is well within the saturation region.
of radiation with a reactive surface to pro- eye. the barrier-layer cell provides a readily A variety of photoemissive surfaces are
duce electrons (photoemission) or to promote The photovoltaic cell consists of a flat measured response at high levels of illumina- used in commercial phototubes. Some consist
electrons to energy states in which they can copper or iron electrode upon which is tion, it suffers from lack of sensitivity at low of one or more of the alkali metals intermixed
conduct electricity (photoconduction). Only deposited a layer of semiconducting material, levels. with alkali metal oxides and silver oxide. This
ultraviolet, visible, and near-infrared radia- such as selenium or copper(l) oxide (see Another disadvantage of the barrier-type mixture is formed on the surface of the cath-
tion have sufficient energy to cause these Figure 5-19). The outer surface of the semi- cell is that it exhibits fatigue; that is, its cur- ode. Other surfaces contain such semi-
processes to occur. Photoelectric detectors conductor is coated with a thin transparent rent output decreases gradually during con- conductors as Cs3Sb or Na2KSb mixed with
also differ from heat detectors in that their metallic film of gold, silver, or lead. which tinual illumination; proper circuit design and small amounts of the alkali metals. Some
electrical signal results from a series of individ- serves as the second or collector electrode;
electrons are accelerated toward it as a Several electrons
consequence. Upon striking the dynode, each for -" incident
electron
photoelectron causes emission of several
additional electrons; these, in turn, are ac-
celerated toward dynode 2, which is 90 V
more positive than dynode 1. Again, several
electrons are emitted for each electron strik-
ing the surface. By the time this process has
been repeated nine times, 106 to 107 electrons
have been formed for each photon; this
cascade is finally collected at the anode. The
resulting current is then electronically ampli-
FIGURE 5-20 Variation of photo- fied and measured. Anode. - 10'
tube response with the applied potential Semiconductor Detecton. The most sensi- electrons for each
photon
at three levels of iIlumination. The tive detectors for monitoring radiation in the
shaded portion indicates the saturation near-infrared region of about 0.75 to 3 JlM are
region. Note the linearity of response at photoconductors whose resistances decrease
the higher applied potentials. 900 V de
when radiation within this range is absorbed.
Crystalline semiconductors are formed
from the sulfides, selenides, and stibnides of
such metals as lead, cadmium, gallium, and
cathodes are semitransparent, with the indium. Absorption of radiation by these
photoemissive material being present on the
surface opposite that which faces the radiation. ~ Cathode
As shown in Figure 5-21, the photo- Anode \
emissive coating on the cathode determines To numbered dynodes
the spectral response of a phototube. When shown above

sensitivity to radiation below 350 nm is


required, the tube must be supplied with an
envelope or window of quartz. Phototubes
are available for various ranges within the
J~t To

Ibl
region between 180 and 1()()()nm. >
Phototubes frequently produce a small .~ 0.6 FIGURE 5-22 Photomultiplier tube: (a) cross section of the
current in the absence of radiation; this dark .~ tube; (b) electrical circuit.
~
current (see Equation 5-10) results from .~
thermally induced electron emission. ~ 0.4
Photomultiplier Tubes. For the measure- a:

ment of low radiant power, the photomulti- materials promotes some of their bound elec- the region between 0.8 and 2 JlM (12,500 to
plier tube offers advantages over the ordinary trons into an energy state in which they are 5000 em - 1). A thin layer of this compound is
phototube. Figure 5-22 is a schematic dia- free to conduct electricity. The resulting deposited on glass or quartz plates to form
gram of such a device. The cathode surface is change in conductivity can then be measured the cell. The entire assembly is then sealed in
similar in composition to that of a photo tube, with a Wheatstone bridge arrangement an evacuated container to protect the semi-
electrons being 'emitted upon exposure to o (Figure 2-24, p. 35) or, alternatively, with a conductor from reaction with the atmosphere.
200 400 600 circuit such as that shown in Figure 3-21b Silicon Diode Detecton. A silicon diode
radiation. The tube also contains additional
Wavelength, om
electrodes (nine in Figure 5-22) called (p.62). detector consists of a reverse-biased pn junc-
dynodes. Dynode 1 is maintained at a poten- FIGURE 5-21 Spectral responses of some The most widely used photoconductive tion formed on a silicon chip. As shown in
tial 90 V more positive than the cathode, and photoemissive surfaces. material is lead sulfide, which is sensitive in Figure 3-1d (p. 43), the reverse bias creates a
depletion layer which reduces the conduct- n-type surface opposite to it. Then, holes are TII'JIOt
ance of the junction to nearly zero: If radia- created which diffuse toward the other surface wray of
•••• Iconductor
tion is allowed to impinge on the n region, and discharge several of the capacitors that diodas
however, holeS and electrons are formed. The lie along the extension of the path of the inci-
former can diffuse through the depletion layer denr beam. The electron beam then recharges
to the p region where they are annihilated; an these- capacitors when it again reaches them
increase in conductance, which is propor- in the course of its sweeps (see the end view,
tional to radiant power, is the consequence. Figure S-23b). This charging current is then
A silicon diode detector is not so sensitive amplified and serves as the signal.
as a photomultiplier tube. It has, however, The width of the electron beams is such
become important because arrays of these ( - 20 JIm) that the surface of the target is
detectors can be formed on the surface of a effectively divided into SOOlines or channels.
single silicon chip. These chips are an impor- The signal from each of these channels can be
tant component of vidicon tubes.s stored separately in a computer memory.
Figure 5-23a is a schematic diagram of a Thus, if the vidicon tube is placed at the focal 5i02
vidicon tube. It is similar in construction to a plane of a monochromator, the signal from Face insulating 8"m
pl.1ll rwgIon i02
television tube in which a stream of electrons each channel corresponds to radiation of a
is employed to scan a target area with a series different wavelength. It therefore becomes . p region
of successive horizontal sweeps. The target in possible to obtain a spectrum without move-
Figure 5-23 is a silicon diode array with a ment of the monochromator. That is, scan-
diameter of 16 mm and containing over ning is accomplished electronically rather + \ Depletion
layer ~ ~ Electron
15,000 photodiodes per square millimeter. than optically, and channel numbers rather ocan beam
Figure 5-23b is a magnified cross section than monochromator settings serve as a
and end view of a part of the target array of measure of wavelength for spectra.
lb)
photodiodes. Each photodiode consists of a An instrument consisling of a monochrom-
cylindrical section of p-type silicon sur- ator, vidicon tube, and computer, such as FIGURE 5-23 A vidicon tube detector: (a) vidicon tube
rounded by an insulating layer of silicon diox- that just described, is called an optical multi- and (b) target array of silicon diodes.
ide. Each diode is thus electrically independent channel analyzer. It is of considerable impor-
of neighboring diodes; all are connected to the tance because it allows a portion or all of a
common II-type layer. It should be emphasized spectrum to be recorded essentially simultan-
that the schematic has been greatly magnified; and 307 nm. By sacrificing resolution, a much
eously. A disadvantage is that the physical positions. 11 A spectral resolution of about 1
indeed, the distances between centers of the p larger wavelength range can be covered.
size of the detector places a limit on either the nm is achieved over the range from 200 to
regions is only about 8 Jim. Thus, a compact multichannel spectrometer 800 nm.
wavelength range or the resolution of such an
When the surface of the target is swept by for field use has been designed that covers a
analyzer. For example. when a vidicon tube
the electron beam, each of the p-type cylin- 650 nm wavelength rangelO; its resolution,
was mounted at the focal plane of a typical Heat Detectors
ders becomes successively charged to the however, is only 10 nm. Instruments have
. grating monochromator, the face of the tube
potential of the beam and acts as a small also been designed to provide a two dimen- The measurement of infrared radiation is
corresponded to only about 27.0 nm for any
charged capacitor, which remains charged sional display of spectra on the surface of a difficult as a result of the low intensity of
given wavelength setting.9 The resolution,
(except for leakage) until a photon strikes the vidicon tube. In one of these, an optical ~vailable sources and the low energy of the
however, was better than I nm and allowed
system is employed which divides the ultra- mfrared photon. As a consequence of these
the simultaneous determination of lead, tin,
violet-visible spectrum into six 100 nm seg- properties, the eleclrical signal from an infra-
nickel, and iron in a brass, based upon the
ments which are displayed along the red detector is small, and its measurement re-
emission lines of these elements between 280
• For a discussion of vidicon tubes and other analogous horizontal axis of the tube at different vertical quires large amplification. It is usually the
devices, see: Y. Talmi, Anal. Chem. ~, 697A, 658A
(1975); and G. Horlick and E. G. Codding, in Conrem-
porary Topics in Analytical and Clinical Chemistry, cds.
D. M. Hercules. G. M. Hicftjc, L. R. Snyder, and M. A. • E. G. Codding and G. Horlick, Spectrosc. Lett., 7 (I~ 10 G. A. H. Walker, et al., Rev. Sci. Instrum. 45. 1349
Evenson.New York: Plenum Press. 1977,vol. I, Chapter 4. IIR. M. Hoffman and H. L. Pardue. Anal. Chem. 51,
33 (1974). (1974~ 1267 (1979).
COMPONENTS OF INSTRUMENTS FOR OPTICAL SPECTROSCOPY

detector system that limits the sensitivity and Thermocouples. In its simplest form, a Spectrophotometer
the precision of an infrared instrument.12
The convenient phototubes discussed ear-
thermocouple consists of the junctions
formed when two pieces of a given metal are
-,-
II
slit

Thermocouple
lier are generally not applicable in the infra-
red because the photons in this region lade
fused to either end of a dissimilar metal or a
semiconducting metal alloy. A potential
tt junction

the energy to cause photoemission of elec-


trons. Thus, thermal detectors and detection
develops between the two thermocouple junc-
tions which varies with the temperature differ-
~---- -;:]
based upon photoconduction are required. ence between the two junctions. For most
Neither of these is as satisfactory as the applications, one of the junctions (the refer-
photocell. ence junction) is held at a constant tempera-
Thermal detectors, whose responses ture (often in an ice bath) and the second
depend upon the heating effect of the radia- junction serves as the temperature-sensitive
tion, can be employed for detection of all but detector.
the shortest infrared wavelengths. With these The junction for infrared detection is
devices, the radiation is absorbed by a small formed from very fine wires of such metals as
black body and the resultant temperature in-
crease is measured. The radiant power level
platinum and silver or antimony and
bismuth. Alternatively, the detector junction
'=" -15V I
from a spectrophotometer beam is minute may be constructed by evaporating the metals FIGURE.5-24 Thermocouple and preamplifier. (Ad~Pted from
(10-7 to 10-9 W~ so that the heat capacity of onto a nonconducting support. lit either case. G. W. Ewmg, J. Chern. Educ., 48(9), A52l, (1971). With permission.)
the absorbing element must be as small as the junction is usually blackened (to improve
possible if a detectable temperature rise is to its heat absorbing capacity) and sealed in an
be produced. Every effort is made to mini- evacuated chamber with a window that is
mize the size and thickness of the absorbing transparent to infrared radiation. absorb the radiant heat. Bolometers are not
beam that strikes the active sur/ace of the
element and to concentrate the entire infra- The reference junction is designed to have so extensively used as other infrared detectors
phototube is changed; a change in' photocur:
red beam on its surface. Under the best of a relatively large heat capacity and is care- Pyr~r~ Detectors. Certain crystals:
rent results, which can be related to the
circumstances, temperature changes are fully shielded from the incident radiation. such as lithtum tantalate, barium titanate
power of the infrared beam.
confined to a few thousandths of a degree Because the analyte signal is chopped, only and triglycine sulfate, possess temperature~
sensitive dipole moments. When placed be- The Golay cell is more expensive than
Celsius. the difference in temperature between the two other heat detectors and no more sensitive to
The problem of measuring infrared radia- junctions is important; therefore, the refer- tween metal plates, a temperature-sensitive
near- and mid-infrared radiation; thus, it is
tion by thermal means is compounded by eoce junction does not need to be maintained capacitor ~ formed which can be employed
seldom employed for these spectral regions.
thermal effects from the surroundings. The at constant temperature. for rneasunng the power of infrared radiation.
. <?n .the other hand, the Golay detector is
absorbing element is housed in a vacuum and A well-designed thermocouple detector is Here, the transduced signal is capacitance.
slgmficantly superior for radiation with wave-
is carefully shielded from thermal radiation capable of responding to temperature differ- ~ Golay Detector. The Golay detector is
lengths greater t~an. SO Ilm (200 em - I); it
emitted by other nearby objects. In order to ences of 10-hC. This figure corresponds to a essentially a sensitive gas thermometer in
finds g~neral use m mstruments designed for
minimize the effects of extraneous heat potential difference of about 6 to 8 pV/pW. which xenon is contained in a small cylindri- the far-mfrared region.
sources, a chopped beam is always employed The thermocouple of an infrared detector is a cal chamber, which contains a blackened
in infrared measurements. Thus, the analyte low-impedance device; it is frequently con- membrane. One end of the cylinder is sealed
signal, after transduction, has the frequency of nected to a high-impedance preamplifier such with an infrared window; the other consists of
the chopper; with appropriate circuitry, this as that shown in Figure 5-24. a flexible diaphragm which is silvered on the SIGNAL
signal is readily separated from extraneous Bolometers. A bolometer is a type of re- outside. A light beam is reflected from this PROCESSORS AND READOUTS
silvered surface to the cathode of a vacuum
radiation signals, which ordinarily vary only sistance thermometer constructed of strips of
phototube. When infrared radiation enters
!
slowly with time. metals such as platinum or nickel, or from a
the cell, the blackened membrane is warmed The. signal. processor is ordinarily an elec-
semiconductor; the latter devices are some- tromc deVice that amplifies the electrical
times called thermistors. These materials ex- which in turn heats the xenon by conduction:
signal from the detector; in addition, it may
12 For further information on infrared deteaors, see:
hibit a relatively large change in resistance The resulting increase in pressure causes dis-
alter the signal from dc to ac (or the reverse~
G. W. Ewing, J. CMm. Educ ••• (9~ AS21 (1971);and H. as a function of temperature. The responsive tortion of the silvered diaphragm. As a
change the ph~ of the signal, and filter it to
Levinstein, Anal. CMm. 41 (14~ 81A (1969~ element is kept small and blackened to consequence, the fraction of the reflected light
remove unwanted components. Furthermore,
the signal processor may be called upon to decay of radioactive species (these techniques order for the first-order diffraction line for 1 - 500 nm to be observed
perform such mathematical operations on the are considered in detail in Chapter 15~ Only at a reftection angle of -40 deg when the angle of incidence is 60 deg?
signal as differentiation, integration, or con- recently, however, has photon counting been
version to a logarithm. 6. Consider an infrared grating with 72.0 lines per millimeter and
applied to ultraviolet and visible radiation. 13
Several types of the readout devices 5.00 mm of illuminated area. Calculate the first-order resolution (l/Al)
Here, the output of a photomultiplier tube is
described in Chapters 2 and 3 are found in of this- grating. How far apart (in an -I) must two lines centered at
employed. In the previous section, it was in-
modern instruments. Some of these include dicated that a single photon striking the cath- 1000 an-I be if they are to be resolved?
the d'Arsonval meter, digital meters, the ode of a photomultiplier ultimately leads to a 7. Calculate the angular dispersion (d8/d1) at 500 nm for a Cornu type
scales of potentiometers, recorders, and cascade of 106 to 10' electrons or a pulse of prism having a prism angle IX of 60 deg em -1 assuming the material of
cathode-ray tubes. current which can be amplified and counted. construction is
Generally, the equipment for photon (a) a dense flint glass.
Photon Counting counting includes a pulse-height discrimina- (b) fused quartz.
Ordinarily, the output from the p]1otoelectric tor (see Figure 15-13~ which rejects pulses 8. Use the curves in Figure 5-9 to estimate dn/dl and n at 500 nm for
detectors described in the previous section unless they exceed some predetermined mini- prisms constructed from the materials in Problem 7.
is processed and displayed by analog mum voltage. Such a device is useful because 9. A common infrared source consists of an inert solid that behaves as a
techni~ues. That is, the aver. current, dar1c current and instrument noise are often black-body radiator when electrically heated. The energy density of
potential, or conductance associated with the significantly smaller than the signal pulse and black-body radiation is given by the equation
detector is amplified and recorded or fed into are thus not counted; an improved signal-ta-
a suitable meter. As was indicated in Chapter noise ratio results. enelJY density at wavelength 1- 8;h (e<6'.IlT -1)-1
3 (p. 83~ analog signals such as these vary Photon counting has a number of advan-
Continuously; in' spectroscopy, th~ are gen- tages over analog signal processing, including where c is the speed of light, h is Planck'. constant, Ie is Boltzmann's
erally proportional to the aver.ge radiant improved signal-ta-noise ratio, sensitivity to constant, and T is temperature in OK. The total amount of radiant
power of the incident beam. I low radiation levels, improved precision for a energy per second per square centimeter of surface of a black body is
In some instances, it is possible 'and advan- given measurement time, and lowered sensitiv- given by E= (5.70 X 10-5 ergan-Z s-loK-4)'f4, where Tis tempera-
tageous to employ direct digital' techniques ity to voltage and temperature changes. The ture. The wavelength of maximum emission energy is given by
wherein electrical pulses produced by individ- required equipment is, however, more com- l..x - 0.289 an °K/T OK.A graph of black-body radiation intensity is
ual photons are counted. Here, radiant
power is proportional to the number of pulses
rather than to an average current or
plex and expensive; the technique has not yet
been widely applied for routine measurements
in the ultraviolet and visible regions.
(a) Calculate l...
shown in Figure 4-13.
for black body radiators at l500 K and at 1000oK.
0

(b) Calculate the ratio of energy density at 1500 an-I compared to


potential that at 1-. for black bodies at lSOO"Kand at l000"K.
Counting techniques have been used for (c) The center of a typical infrared spectrum is at a wavenumber near
IS For a review or photon countill& see: H. V. Malm-
many years for measuring the power of X-ray stadt, M. L. Franklin, and G. Horlick. Allal. CMm., •••• 1500 em-I. Why is it advantageous in infrared spectroscopy for
beams and of radiation produced by the (8~ 63A (1972~ the source to be heated to 1500 K instead of looo K?
0 0

I. State the differences between and the relative advantages of Littrow


and Bunsen prism monochromators. _
2. W~at ar~ the relative advantages and disadvantages of gratings and
pnsms for dispersion of light?
3. Why m4st the slit width of a prism monochromator be varied to
provide constant resolution. whereas a nearly constant slit width may
be used with a grating monochromator?
4. Why do quantitative and qualitative analyses often require different
monochromator slit widths?
5. For a grating, how many lines per centimeter would be required in
This chapter provides introductory material
which is applicable to ultraviolet-visible,
infrared, and atomic absorption spectroscopy. 1
Detailed discussion of these methods appears
in later chapters.
Po ,--I -I'------~
Absorbing
solution of
P
T =!...

A -log
Po
Po
Ii"

concentration c
TERMS EMPLOYED IN FIGURE 6-' Attenuation of a beam of
ABSORPTION SPECTROSCOPY radiation by an absorbing solution.

Table 6-1 lists the common terms and sym-


bols employed in absorption spectroscopy. In
recent years, a consi~erable effort has been of incident radiation transmitted by the solu-
made by the American Society for Testing tion. That is,
Materials to develop a standard nomencla-
ture; the terms and symbols listed in the first T = PIPo (6-1)
two columns of Table 6-1 are based on Transmittance is often expressed as a
ASTM recommendations. Column 3 contains percentage.
alternative symbols that will be found in the
older literature. A standard nomenclature
seems most worthwhile in order to avoid am-
biguities; the reader, is, therefore, urged to
learn and use the ri:commended terms and The absorbance of a solution is defined by the
equation
symbols.
Po
A = - Ioglo Toc log-
P
Transmittance
Note that, in contrast to transmittance, the
Figure 6-1 depicts a beam of parallel radia- absorbance of a solution increases as the
tion before and after it has passed through a attenuation of the beam becomes larger.
layer of solution with a thickness of b em and
a concentration of c of an absorbing species.
As a consequence of interactions between the Absorptivity and Molar Absorptivity
photons and absorbing particles, the power of
the beam is attenuated from Po to P. The As will be shown presently, absorbance is
transmittance T of the solution is the fraction directly proportional to the path length
through the solution and the concentration of
the absorbing species. That is,

1 For more detailed trelitment or absorption spectros-


A = abc (6-3)
copy. see: R. P. Bauman, Absorption Sp"ctroscopy. New where a is a proportionality constant called
York: Wiley, 1962; J. Ri Edisbury, Practical Hints on
Absorption Sp"ctrometryi New York: Plenum Press, the absorptivity. The magnitude of a will
1968;F. Grum, in Physical Methods o/Chemistry,eds. A. clearly depend upon the units used for b and
Weissberger and B. W. Roositer. New York: Wiley- c. When the concentration is expressed in
Interscience, 1972, Vol. I, Part III B, Chapter 3; G. F. moles per liter and the cell length is in cen-
Lothian, Absorption Sp"ctrophotometry, 3d ed. London: timeters, the absorptivity is called the molar
Adam Hilger Ltd., 1%9; and J. E. Crooks, The Sp"ctrum
absorptivity and given the special symbol e.
in ChemLstry. London: Academic Press, 1978.
Thus, when b is in centimeters and c is in by large molecules or inhomogeneities. Reflec- radiation after it has passed through a cell The meter is thus made direct reading in per-
moles per liter, tion losses can be appreciable; for example, containing the solvent or the solution of the cent transmittance. Obviously, an absorbance
about 4% of a beam is reflected upon vertical anaIyte. scale can also be scribed on the meter face.
passage of visible radiation across an air-to-
glass or glass-to-air interface (see example, M••••• rement of
Experimental p. 103). Trllll8lltlttance and Absorbance QUANTITATIVE ASPECTS OF
M••••• rement of P and Po In order to compensate for these effects, ABSORPTION MEASUREMENTS
Transmittance (or absorbance) measurements
the power of the beam transmitted through
The relationship given by Equation 6-1 or 6-2 are made with instruments having· the com-
the absorbing solution is generally compared The remainder of this chapter is devoted to
is not directly applicable to chemical analysis. ponents arranged as shown in Figure S-Ib
with that which passes through an identical an examination of Equation 6-4 (A = ebc~
Neither P nor Po, as defined, can be conven- (p. 115). The electrical output G of the detec-
cell containing the solvent for the sample. An with particular attention to causes of devia-
iently measured in the laboratory because the tor of such an instrument is given by (see
experimental absorbance that closely approx- tions from this relationship. In addition, con-
solution to be studied must be held in some p. 138).
imates the true absorbance of the solution sideration is given to the effects that
sort of container. Interaction between the ra-
diation and the walls is inevitable leading to a
can then be obtained; that is, G = KP + K' (6-5) uncertainties in the measurement of P and Po
have on absorbance (and thus concentration~
loss by reflection at each interface; moreover, p •••_. Po where K' is the dark current that often exists
significant absorption may occur within the A = Iog-- =Iog- when no radiation strikes the transducer and
p•••
8liea P Bee". Law
walls themselves. Finally, the beam may suffer K is a proportionality constant.
a diminution in power during its passage The terms Po and P, when used hence- In many instruments, the readout device Equations 6-3 and 6-4 are statements of
through the solution as a result of scattering forth, refer to the power of a beam or will consist of a linear scale calibrated in units Beer's law. These relationships can be ration-
of 0 to 100% T. A transmittance measure- alized as follows.2 Consider the block of
ment with such an instrument requires three absorbing matter (solid, liquid, or gas) shown
steps. First, with the light beam blocked from in Figure 6-2. A beam of parallel monochro-
the transducer by means of a shutter, an elec- matic radiation with power Po strikes the
TABLE &-1 IMPORTANT TERMS AND SYMBOLS EMPLOYED IN
trical adjustment is made until the pointer of block perpendicular to a surface; after pass-
ABSORPTION MEASUREMENT
the readout device is at exactly zero; this step ing through a length b of the material, which
Term ••• Symbol" Definition Akerutin Name and Symbol is called the dark current or 0% T adjustment.
A 100% T adjustment is then carried out with
Radiant power, P, Po Energy ofradiation (in ergs) Radiation intensity, I, 10 the shutter open and the solvent in the light
impinging on a l-an2 area
of a detector per second path. This adjustment may involve increasing
or decreasing the power output or the source
P electrically; alternatively, the power of the
Absorbance, A log~ Optical density, D; extinction, E
P beam may be varied with an adjustable
P diaphragm or by appropriate positioning of a
Transmittance, T Transmission, T comb or optical wedge. After this step, we
Po
may write Equation 6-5 in the form
Path lent!th of I,d
radiation, in em b Go = 100 = KPo + 0.00
A In the final step of the measurement, the FIGURE 6-2 Attenuation of radiation
AbsorptivitY,b a Extinction ~fficient, k with initial power Po by a solution con-
be solvent cell is replaced by the sample. The
meter reading is then given by taining c moles per liter of absorbing solute
A with a path length of b ern. P < Po·
Molar absorptivity,' £ Molar extinction coefficient
be G = KP +0.00
Dividing this equation by the previous one
• TerminololY recommended by the American Chemical Society. Reprinted with permission from AMI. CItmt., 24, 1349 yields 2 The discussion that follows is based on a paper by
(1952); •••• 2298 (1976~ Copyrisht by the American Chemiall Society. F. C. Strong. AMI. Ch"",. 24. 338 (t952). For a rigorous
• e may be expressed in g/liter or other specified concentration units; b may be expressed in em or in other units or length. P derivation of tbe law, see: D. J. Swinehart. J. Chem.
, e is expressed in units or mol/liter. G = - x 100 = T x 100
Po Edue.• 39. 333 (1972~
contains n absorbing particles (atoms, ions, or Upon converting to base lO logarithms and among the various species, the total absorb- absorber alters the molar absorptivity of the
molecules ~ its power is decreased tp P as a inverting the fraction to change the sign, we ance for a multicomponent system is given latter by electrostatic interactions; the effect is
result of absorption. Consider now a cross obtain by lessened by dilution.
section of the block having an area S and an Po an While the effect of molecular interactions
infinitesimal thickness dx. Within this section log Ii = 2.303S (6-8) A._I = Al+ A2 + ... + A. . (6-11) is ordinarily not significant at concentrations
there are dn absorbing particles; associated = £Ibel + £2be2 + ... + £.bc. below O.OlM, some exceptions are en-
with each particle, we can imagine a surface where n is the total number of particles within countered among certain large organic ions
at which photon capture will occur. That is, if the block shown in Figure 6-2. The cross- where the subscripts refer to absorbing com- or molecules. For example, the molar absorp-
a photon reaches one of these areas by sectional area S can be expressed in terms of ponents I, 2, ... , n. tivity at 436 nm for the cation of methylene
chance, absorption will follow immediately. the volume of the block V and its length b. blue is reported to increase by 88% as the dye
The total projected area of these capture sur- Thus, Limitation. to the concentration is increased from 10-5 to
faces within the section is designated as dS; Applicability of B•••.•• Law lO-2M; even below 10-6M, strict adherence
V
the ratio of the capture area to the total area, S=-cm2 to Beer's law is not observed.
b The linear relationship between absorbance
then, is dS/S. On a statistical average, this and path length at a fixed concentration of Deviations from Beer's law also arise be-
ratio represents the probability for the cap- Substitution of this quantity into Equation absorbing substances is a generalization for cause £ is dependent upon the refractive index
ture of photons within the section. 6-8 yields of the solution.3 Thus, if concentration
which no exceptions are known. On the other
The power of the beam entering the Po' anb hand, deviations from the direct proportional- changes cause significant alterations in the re-
section, P", is proportional to the number of log Ii = 2.303V (6-9) ity between the measured absorbance and fractive index n of a solution, departures from
photons per square centimeter per second, concentration when b is constant are fre- Beer's law are observed. A correction for this
and dP" represents the quantity removed per Note that n/V has the units of concentration quently encountered. Some of these devia- effect can be made by substitution of the
second within the section; the fraction ab- (that is, number of ~icles per cubic centi- tions are fundamental and represent reallimi- quantity en/(n2 + 2)2 for £ in Equation 6-10.
sorbed is then -dP"/P,,, and this ratio also meter); we can readily convert n/V to moles tations of the law. Others occur as a In general, this correction is never very large
equals the average probability for capture. per liter. Thus, i consequence of the manner in which the and is rarely significant at concentrations less
The term is given a minus sign to indicate absorbance measurements are made or as a than O.OlM.
that P undergoes a decrease. Thus, n particles .
c = --------- result of chemical changes associated with Chemical Deviatiol& Apparent deviations
6.02 )( lO23 particles/mol from Beer's law are frequently encountered as
concentration changes; the latter two are
dP" dS
-p;=S 1000 cm3/liter lOOOn . sometimes known, respectively, as instrumen- a consequence of association, dissociation, or
x Vem3 = 6.02 )( lO23V mol/llter tal deviations and chemical deviations. reaction of the absorbing species with the
Real Limitations to Beer's La". Beer's law solvent. A classic example of a chemical de-
Recall, now, that dS is the sum of the cap-
Combining this relationship with Equation is successful in describing the absorption be- viation occurs in unbuffered potassium dichro-
ture areas for particles within the section; it
6-9 yields havior of dilute solution only; in this sense, it mate solutions, in which the following
must therefore be proportional to the number
of particles, or is a limiting law. At high concentrations equilibria exist:
I Po 6.02 x lO23abe
(usually > O.OlM~ the average distance be- + H20
og Ii = 2.303 x 1000 Cr20~-
tween the species responsible for absorption
Finally, the constants in this equation can be is diminished to the point where each affects ~2HCr04 ~2H+ + 2CrO~-
where tin is the number of particles and a is a
proportionality constant, which can be called collected into a single term £ to give the charge distribution of its neighbors. This At most wavelengths, the molar absorptivities
the capture cross section. Combining Equa- interaction, in turn, can alter their ability to of the dichromate ion and the two chromate
Po .
tions 6-6 and 6-7 and summing over the inter- log Ii =;ebc = A (6-10) absorb a given wavelength of radiation. Be- species are quite different. Thus, the total
val between zero and n, we obtain cause the extent of interaction depends upon absorbance of any solution depends upon the
concentration, the occurrence of this phe- concentration ratio between the dimeric and
_ (dP" = (adn nomenon causes deviations from the linear re-
lationship between absorbance and concen-
the monomeric forms. This ratio, however,
·"0 P" ·0 S Application of changes markedly with dilution, and causes a
B•••.•• Law to Mixtu •••• tration. A similar effect is sometimes
which, upon integration, giv~ encountered in solutions containing low
Beer's law also applies to a solution contain- absorber concentrations and high concentra-
P an ing more than one kind of absorbing
-In-=- tions of other species, particularly elec- • G. Kortum and M. Seiler. Allgew. C"""'" 51, 687
Po S substance. Provided there is no interaction trolytes. The close proximity of ions to the (1939~
We are now able to calculate the absorbance ually, we may write for radiation A'
pronounced deviation from linearity between into the expression for K. makes it apparent
the absorbance and the total concentration of that, in the presence of strong base, essentially at the two wavelengths. Thus, , I P'o 'be
A=og-=e
chromium(VI). Nevertheless, the absorbance all of the indicator is dissociated to In ~ ; there- A430 = e1nb[In-] + t:Hlnb[HIn] P'
due to the dichromate ion remains directly fore,
= 2.06 x 104 x 1.00 x 1.12 X 10-5
proportional to its molar concentration; the
[In-] ~ (1.02 x 10-4)/2 = 5.10 x 10-5
same is true for the chromate ions. This fact is .+ 6.3 x 10 2 X 1.00 x 0.88 X 10-5 P'o = 10"'"
easily demonstrated by measuring the absorb- Similarly, in the strong acid [HIn] ~ 5.10 x P'
ance of chromium(VI) solutions in strongly 10-5. The molar absorptivities for the two = 0.236
acidic solution, where dichromate is the prin- species can thus be determined. At 430 nm, A570 .: 9.6 x 102 x 1.12 X 10-5
cipal species, and in strongly alkaline solu-
tion, where chromate predominat:s. Thus, ,A 1.051 + 7.12 X 103 x 0.88 X 10-5
deviations in the absorbance of this system £in= be = 1.00 x 5.10 X 10-5
=0.073
from Beer's law are more apparent than real = 2.06 X 104
because they result from shifts in chemical The accompanying data were obtained simi-
equilibria. These deviations can, in fact, be , _ 0.032 _ 2 larly.
readily predicted from the equilibrium con- tHin- 5.10 X 10-5 - 6.3 x 10 [lIt-] A430 A570
FH1n [HIn]
stants for the reactions and the molar absorp-
and at 570 nm, 2.00 X 10-5 0.88 X 10-5 1.12 X 10-5 0.236 0.073
tivities of the dichromate and chromate ions. 10-5 0.175
4.00 x 10-5 2.22 X 10-5 1.78 X 0.381
M 0.049 ,,2 8.00 x 10-5 5.27 X 10-5 2.73 X 10-5 0.596 0.401
EXAMPLE £k,= 5.10 X 10-5 = 9.6 x hr
12.00 x 10-5 10-5 10-5 0.771 0.640
Two solutions of the acid-base indicator
HIn were prepared by diluting 1.02 x 1O-4F M 0.363
_ _ 3
16.00 x 10-5
8.52 X
11.9 X 10-5
3.48 X
4.11 * 10-5 0.922 0.887

£Hln- 5.10 X 10-5 - 7.12 x 10


solutions of HIn (K. = 1.42 x 10-5) with
equal volumes of: (a) O.2F NaOH; and (b) Figure 6-3 is a plot of the data derived in
Let us calculate the concentration of HIn the foregoing example and illustrates the kind
O.2F HCI. When measured in a 1.0Q.an cel~
and In- in an unbuffered 2.00 x 1O-5F of departures from Beer's law that arises
the following absorbance' data were obtained
solution of HIn. From the equation for the when the absorbing system is capable of
at 430 and 570 nm:
dissociation reaction, we see that undergoing dissociation or association. Note
SohIrioB Dilutell With that the direction of curvature is opposite for
the two wavelengths.
0.2FNaOH 1.051 0.049 Furthermore, Instrumental DeYiations with Polychromatic ~ 0.600
O.2F HCI 0.032 0.363 Radiation. Strict adherence to Beer's law ?!
[In-] + [HIn] = 2.00 x 10-5 1:
is observed only when the radiation employed j
Derive absorbance data at the two wavelengths Substitution of these relationships into the is truly monochromatic; this observation is <l: 0.400
for unbuffered solutions having indicator con- expression for K. gives yet another manifestation of the limiting
centrations in the range of 2 x 10-5 to [In-]2 _ -5 character of the law. Unfortunately, the use of
16 X 10-5 F. Plot the data. 2.00 X 10-5 _ [In-] - 1.42 x 10 radiation that is restricted to a single wave-
The absorbance of the various solutions length is seldom practical; devices that isolate
depends upon the equilibrium Rearrangement yields the quadratic expression portions of the output from a continuous
[In -]2 + 1.42 x 10- 5[In-] source produce a more or less symmetric
HIN~H+ + In- band of wavelengths around the desired one
i
O.QOO
0.00 4.00 8.00 12.00
- 2.84 X 10-10 = 0 (see Figures 5-14 and 5-17, for example). Indicator conCentration. F X 105
which gives The following derivation shows the effect
K = 1.42 X 10-5 = [H+][In-] [In-] = 1.12 x 10-5 of polychromatic radiation on Beer's law. FIGURE 6-3 Chemical deviations from
• [HI~ Beer's law for unbuffered solutions of the
Consider a beam comprising of just two
[HIn] = 2.00 x 10-5 - 1.12 X 10-5 wavelengths A' and AM. Assuming that Beer's indicator HIn. For data, see example on this
Substitution of the hydrogen ion concen-
law applies strictly for each of these individ- page.
tration of the strong acid or base solutions = 0.88 X 10-5
When an absorbance measurement is made It is an txperimental fact that deviations tration for various levels of p. as compared to !!.. x 100
with radiation composed of both wave- from Beer's law resulting from the use of a Po'
lengths, the power of the beam emerging from Po·
polychromatic beam are not appreciable, Note that the instrumental deviations il-
the solution is given by (P' + P") and that of provided the radiation used does not en- lustrated in Figures 6-4 and 6-5 result in
the beam from the solvent by (PO + PO). compass a spectral region in which the absorb- absorbanees that are smaller than theoretical.
Therefore, the measured absorbance is er exhibits large changes in absorbance as a It can be shown that instrumental deviations
function of wavelength. This observation is always lead to negative absorbance errors.4
A _ I (P'o + PO)
101 - og (P' + P") illustrated in Figure 6-4.
Instrumental Deviations in the Presence of "~
which· can be rewritten as
.e 1.0
Stray Radiation. We have noted earlier
(Chapter 5) that the radiation exiting from a
B
«
The Effect of
monochromator is ordinarily contaminated Instrumental Noise on the Precision
with small amounts of scattered or stray ra- of Spectrophotometric Analy••• S
diation which reaches the exit slit owing to
AM = 10g(P o + PO) reflections from various internal surfaces. The accuracy and precision of spectropho-
tometric analyses are often limited by the un-
- 10g(P'olO-"" + POIO-'-") Stray radiation often differs greatly in wave-
certainties or noise associated with the
length from that of the principal radiation 2.5 5.0 7.5
Now, when t = t', this equation simplifies to and, in addition, may' not have passed instrument. A general discussion of in- Concentrotion. M X 103
through the sample. strumental noise and signal-to-noise optimi-
AM = e'bc FIGURE &-5 Apparent deviation from
When measurements are made in the zation is found in Chapter 3; the reader may
and ~r's law is followed. If the two molar find it helpful to review this material before Beer's law brought about by various amounts
presence of stray radiation, the observed
absofP;livities differ, however, the relationship absorbance is given by undertaking a detailed study of the effect of of stray radiation.
betw~n AM and concentration will no longer instrumental noise on the precision of spec-
be linear; moreover, greater departures from Po + p. trophotometric measurements. In addition, a
linearity can be expected with increasing dif- A' = Iog--- review of the contents of Appendix 1 on the
P+P. uncertainty in concentration can be derived
ferences between e' and t'. This derivation use of standard deviation as a measure of
can be expanded to include additional wave- where p. is the power of the stray radiation. precision may also prove worthwhile. by writing Beer's law in the form
lengths; the relationships remain the ~e. Figure 6-5 shows a plot of A' versus concen- As was pointed out earlier, a spectro- 1 -0.434
photometric measurement entails three steps: C = -£b log T= --e;;-In T
a 0% T adjustment, a 100% T adjustment,
and a measurement of % T with the sample The partial derivative of this equation, hold-
in the radiation path. The noise associated ing band c constant, is given by
with each of these steps combines to give a
net uncertainty for the final value obtained oc = -0.434 iJT
for T. The relationship between the noise en- rbT
countered in the measurement of T and the where oc is the variation in c that results from
the noise or uncertainty oT in T. Dividing by
the first equation yields

~ = 0.434 x oT (6-12)
• I. M. Kolthoff and P. J. Elving. eds, Treatise on Anal.l·t- c 10gT T
ical Chemistry. New York: Interscience Publishe ••• 1964.
Part I. vol. S, pp. 2767-2773. Here, oT/T is the net relative uncertainty or
FIGURE &-4 The effect of polychromatic radiation upon • See: L. D. Rothman, S. R. Crouch, and J. D. Ingle, Jr. noise in T that arises from the three measure-
the Beer's law relationship, Band A shows little deviation Anal. Chem. 47. 1226 (197S); J. D. Ingle, Jr. and S. R. ment steps and oc/c is the resulting relative
since e does not change greatly throughout the band. Band B Crouch, Anal. Chem., 44, 137S (1972); J. O. Erickson and
uncertainty in concentration.
T. Surles, American Laboratory, g (6~ 41 (1976); OplilflJJm
shows marked deviations since e undergoes significant changes The best and most useful measure of the
Parameters for Spectrophotometry. Varian Instrument
in this region.
Division, Palo Alto, CA. noise oT is the standard deviation ST, which
for a series of replicate measurements is given creases or decreases the average number of lation for 20 or 30 independent transmittance
by (see Appendix 1Y' 6.0
electrons moving in a given direction in the measurements oTan absorbing solution.

ST-
_ aT - f'i]••N-l
-...;-
(7; - T)2 (6-13)
5.0
resistor element. Johnson noise does not
depend on the magnitude of the current;
Column 3 of Table 6-3 shows the relative
error in concentration that would be en-
~ indeed, it occurs even in the' absence of a count~red with a spectrophotometer for
In this expression, 7; represents the individual x current. which 'the performance was limited by John-
values of T obtained for a set of N replicate .:~4.0 Johnson noise exists in all transducers and son or 0% T noise. Here. an absolute uncer-
measurements, and t is the average or mean 1/1
electronic comPonents of photometers and tainty ST in transmittance of ±0.OO3, or
for the set. From Equation 6-12, the relative g'•. 3.0 spectrophotometers. With one important ±OJ% T, was assumed. These data are
standard deviation in terms of concentration •... exception. however, its magnitude is so small plotted in Figure 6-6, curve A, where it is seen
(s.Ie) is then i 2.0 relative to other sources of noise that for all that the relative standard deviation of c reaches
II:
practical purposes it can be neglected. The a minimum at an absorbance of about 0.4. (By
~ = 0.434 x ~ (6-14) exception is for the thermal detectors for setting the derivative of Equation 6-14 equal
c 10gT T 1.0
infrared radiation. With such detectors, John- to zero, it can be shown that this minimum
Experimentally. ST can be evaluated by son noise may predominate and limit the occurs at a transmittance of 0.368 or an
C
malting, say. 20 replicate measurements precision of spectral measurements. This situ- absorbance of 0.434.)
1.0 2,0 3.0
(N •• 20) of the transmittance of a solution in Absorbonee ation is in distinct contrast to the ultraviolet The standard deviation in transmittance
exactly the same way and substituting the and visible regions. where Johnson noise in measurements for most commercial spectro-
data into Equation 6-1l FIGURE 6-6 Error curves (or various in- phototubes. photomultiplier tubes. and photometers will range from ± 0.000 1 to
It is clear from an examination of Equa- strumental uncertainties. Data from Table 6-3, amplifiers is inconsequential. ±O.OI (T = 0.01 to 1%); the lower figure is
tion 6-14 that the uncertainty in a photomet- Curve A: 0 % T and Johnson noise. Curve Elects or 0"10T and Johnson Noise. As we found in high-quality ultraviolet-visible in-
ric concentration measurement varies in a B: Signal shot noise. Curve C: Flicker noise. have noted. the magnitude of Johnson noise struments, whereas the upper figure might be
complex way with the magnitude of the trans- and 0% T noise is independent of the trans- expected in a low-cost infrared instrument.
mittance, The situation is even more com- mittance. Thus. ST in Equation 6-14 is The figure of ±0.OO3 in Table 6-3 is perhaps
plicated than is suggested by Equation 6-14. method thus requires an understanding of the independent of T and can be assumed to be typical for medium quality O/'o T or Johnson
however. because the uncertainty ST is, under likely type (or types) that predominate in a constant in determining the effect of ST on s•. noise-limited instruments; concentration er-
many circumstances, also dependent upon T. given set of circumstances, For a given instrument, a good estimate of ST rors of about 1 to 2% relative are thus in-
In a detailed theoretical and experimental 0"10 T Uacertaiaties. As shown in Table can be derived by a standard deviation calcu- herent when measured absorbanees lie in the
study, Rothman. Crouch and Ingle have 6-2, 0% T noise includes three types of noise
described several sources of instrumental un- associated with transducers and amplifiers; as
certainties and shown their net effect on the the name implies all are associated with the
precision of absorbance or transmittance uncertainties in making the 0% T adjustment.
measurements. These uncertainties fall into Sources would include light leaks around the
three categories: those for which the magni- shutter that screens the radiation from TABLE 6-2 SOURCES OF UNCERTAINTY IN A SPECTROPHOTOMETRIC
tude of ST is~portional to T. (2) propor- the detector, vibrational effects associated MEASUREMENT
tional to .jT2 + T. and (3) independent of T. with movement of the shutter. and tempera-
Table 6-2 summarizes information about ture fluctuations in the transducer and
ST Independent of T sT=k'JT!+T ST = k"T

these sources of uncertainty. Clearly, each amplifier systems. In modem spectropho- 0% TNoise Detector shot noise Source nicker noise
type of source has a different effect upon the tometers, 0% T noise is seldom important (photon detectors only)
magnitude of the concentration error. An except at the wavelength extremes of the Dark current shot noise
Dark current excess noise
error analysis for a given spectrophotometric instrument. where K' in Equation 6-S may
Amplifier excess noise
approach KP and KPo. Note that 0% T
noise is independent of the magnitude of T. Detector Johnson noise
JoblBOll Noise. As noted in Chapter 3
(thermal detectors only)
• For a discussion of the standard deviation as a measu",
of experimental uncertainties, see: D. A. Skoog and D. M. (p, 71). Johnson noise results from thermally Limited readout resolution
Wesl, FundamentaLs of Analytical Chemistry, 3d ed. New induced motion of electrons in resistive cir- Amplifier shot noise
York: Holl, Rinehart and Winston, 1976, Chapter 4. cuit elements. This motion momentarily in-
range of 0.15 to 1.0. The higher error ass0- thus, its effect on the relative error in concen- around a mean value. Here, the magnitude of Ordinarily, Po will not change greatly during
ciated with more strongly absorbing samples tration will be similar to 0% T and Johnson the current fluctuationS is proportional to the a series of measurements of T. When this situ-
can usually be avoided by suitable dilution noise and will be described by Equation 6-14. square root of current (see Equation 3-24, ation prevails, we may write
prior to measurement. Relative errors greater Substitution of 0.005 into this equation p. 71~
than 2"/0 are inevitable, however, when absorb- reveals that such an instrument will yield con- In contrast to the types of ·noise we &ave
ST= Tk'J~+ 1 = k'~ (6-15)
ances are less than 0.1. centration data that are uncertain to the thus far considered, shot noise increasei in
It is important to emphasize that the con- extent of 1.5 to 3 % relative, provided percent magnitude with increases in the size of the
clusions just described are based on the transmittances are limited to a range of 10 to quantity being measured. As a consequence, where k' = k..jP;. Substitution of Equation
assumption that the limiting uncertainty in an 80%. ST in Equation 6-14 varies as a function of T. 6-15 into 6-14 yields
analysis is a constant indeterminate error ST
that is independent of transmittance; this type
Signal Shot Noise. As was pointed out ear-
lier (p. 71~ shot noise must be expected
The effect of shot noise on ST and S. is readily
derived, as shown in the following example. ~=
clog
0.434 x k'~
T T
= 0.434k' J.!. +
log T ~ T
1
of uncertainty is most commonly encountered whenever the passage of electricity involves
in instruments employing thermal detectors. transfer of charge across a junction, such as EXAMPLE : (6-16)
Limited Readout Resolution. The precision the movement of electrons from the cathode Derive an expression relating ST and s. to
of some commercial spectrophotometers is shot noise. The data in column 4 of Table 6-3 were
to the anode of a photomultiplier tube or
limited by the resolution of their readout de- across the junction of a barrier-type pho- Shot noise is associated with each of the obtained with the aid of Equati~n 6-16.
vices. For example, an instrument with a meter tocell Here, the current results from a series of three steps required for measuring transmit- Figure 6-6, curve B is a plot of such data. Note
readable to ±O.s% full scale will have an un- discrete events (emission of electrons from a tance or absorbance. Generally, however, the the much larger range of absorbances that can
certainty (ST) of ±0.005T due to this source. cathode); the number of these events per noise associated with the 0% T adjustment is be encompassed without serious loss of ac-
This uncertainty is also independent of T; unit time is distributed in a random way small relative to the measurement of P and curacy when shot noise, rather than Johnson or
Po because the magnitude of the noise in- 0% T noise, limits the precision. This increased
creases as the square root of the signal range represents a major advantage 4f photon
(p. 71). Thus, the uncertainty in T is gen- type detectors over thermal types.· As with
erally determined largely by noise associated Johnson or O'i~T noise-limited instruments,
TABLE &-3 RELATIVE CONCENTRATION ERROR AS A FUNCTION OF with the measurement of P and Po. Since T is shot-limited instruments do not give very re-
TRANSMITTANCE AND ABSORBANCE FOR VARIOUS SOURCES OF the quotient of these two numbers, its relative liable concentration data at transmittances
UNCERTAINTY standard deviation can be obtained from the greater than 95% (or A < 0.02).
relative standard deviation of P and Po Signal shot noise sometimes limits the
Relative Error, ~ x 100 (Appendix I). Thus, accuracy of transmittance and absorbance
c measurements with ultraviolet and visible
For Measurements Limited by: . photometers and spectrophotome1ers. It is
Absorbance, usually of little importance with infrared
Transmittance, 0% T or Signal Flicker
T A Johnson Noise" Shot Noise" Noise' But shot noise is proportional to the square instruments.
root of the measured quantity (p. 71). Thus, Flicker Noise. Flicker noise in photom-
0.95 0.022 ± 6.2 ±8.4 ±5.8 eters and spectrophotometers is largely as-
0.90 0.046 ± 3.2 ±4.1 ±2.8 s,.=kjP sociated with the radiation source. As was
0.80 0.097 ± 1.7 ±2.0 ±1.3
0.60 0.222 ± 0.98 ±0.96 ±0.s9 where k is a proportionality constant. Also, pointed out in Chapter 3, the magnitude of
0.40 0.398 ± 0.82 ±0.61 ±0.33 flicker noise cannot be predicted frotn theory.
0.20 0.699 ± 0.93 ±0.46 ±0.18
s,.o=k~ It has been shown. however.7 that uncertain-
0.10 1.00 ±1.3 ±0.43 ±0.13 ties from the source can be described by the
Substitution of these quantities into the first
0.032 1.50 ± 2.7 ±0.50 ±0.09 equation and rearrangement gives relationship ,
0.010 2.00 ± 6.5 ±0.65 ±0.06
0.0032
0.0010
2.50
3.00
±16.3
±43.4
±0.92
±1.4
±0.05
±0.04 (~)2
T
('!' +~)
= k2
P Po
2
= k (Po
Po P
+ I) _
• From Equation 6-14 employing IT - ±O.OO3.
• From Equation 6-16 employing k' - ±O.OO3. 7 See: L. D. Rothman. S. R. Crouch. and J. D. Ingle, Jr.
, From Equation 6-18 employing k- - ±O.OO3. Anal. Ch""" 47. 1226 (197S~
and Equation 6-14 becomes ent sections of the cell are exposed to the resulted from this source. Indeed, it seems of random error is probably cell-positioning
source; corresponding variations in measured probable that imprecision in cell positioning uncertainty. It is evident· that the fullest
~ = _ 0.434 k N (6-18)
C 10gT transmittances must then be expected. For is often the most important limitation to the potential of such instruments can only be
high-quality cells, such imperfections will be accuracy of spectrophotometric measure- realizea by filling and rinsing the cells in
As shown by the data in column 5 of Table minimal. If cells become scratched or dirty, ments. One method of reducing the effect of place; ·even with this precaution, cell uncer-
6-3 and by Figure 6-6, curve C, the concentra- however, the dependence of transmittance cell positioning is to leave cells in place tainty often appears to limit the performance
tion error due to flicker noise decreases rapidly upon cell position may become significant. during calibration and analysis; new stand- of these instruments.
and approaches zero at high absorbances. Rothman, Crouch, and Ingle have shown ards and samples are introduced after wash- The performance of inexpensive spectro-
The overall uncertainty in a spectro- that uncertainties due to cell positioning var- ing and rinsing the cell in place with a photometers tends to be limited, at least in
photometric measurement at low absorbance iations behave in the same way as source syringe. Care must be taken to avoid touch- part, by their readout devices; it has been
frequently results from a combination of flicker noise; that is, ST is proportional to ing or jarring the cells during this process. shown that significant improvements can be
flicker noise and the other types mentioned transmittance and the concentration uncer- Stmmary. It is apparent that the random achieved by replacing these components with
earlier; occasionally, all three may contribute. tainty is given by Equation 6-18. Figure 6-7A errors associated with a spectrophotometric more sensitive ones.8
CeO Positioning Uncertainty. All cells have is a plot of some of their data. Even though analysis depend upon several variables, in-
minor imperfections. As a consequence, painstaking care was followed in cleaning cluding instrument design, the wavelength
reflection and scattering losses vary as differ- and positioning the cells, significant errors region, the source intensity and stability, the Effect of Slit Width
sensitivity of the transducer, the slit widths, on Abaorptlon M ••••• nments
and the concentration of the analyte. The sit-
The ability of a spectrophotometer to resolve
uation is made even more complicated with a pair of adjacent absorption peaks depends
5.0
recording instruments, where several of these
upon the slit width employed (p. 133). Narrow
/8 variables may change as the spectrum is
slits are required to obtain the maximum
I recorded.
I detail from a complex spectrum.9 Figure 6-8
Infrared instruments are most commonly
4.0 I illustrates the loss of spectral detail that ac-
limited by the Johnson noise associated with
I companies the use of wider slits. In this
the detector and by the cell position uncer-
I example, the transmittance spectrum of a
~ I
tainty. The latter is due to the fact that
didymium glass was obtained at slit settings
x 3.0 narrow cells must often be used and the width
~':lu I that provided bandwidths of 0.5, 9, and 20

-
~.
, /
I
I
of the windows, and thus the relative sample
thickness undoubtedly fluctuates considerably
from one part of the cell to another. Further-
om. The progressive loss of spectral detail is
clear. For qualitative studies, such losses
often loom important.
..
.~ 2.0
/ more, infrared windows are readily scratched,
Figure 6-9 illustrates another elTect of slit
11
a:
'---_/ abraded, and attacked by the atmosphere;
width on spectra. Here, the spectrum of a
transmission is thus highly variable across
praseodymium chloride solution was ob-
their surfaces. Source flicker may also con- tained at slit settings of 1.0, 0.5, and 0.1 mm.
tribute to the uncertainty of infrared measure-
Note that the peak absorbance values. in-
ments, but is probably less important than
crease significantly (by as much as 70% in
Johnson noise and cell uncertainty. Figure
one instance) as the slit width decreases. At
6-7, curve B is an error plot assuming the
slit settings less than about 0.14 mm, absorb-
same cell positioning uncertainty as in Figure
ances were found to become independent of
6-7, curve A and a Johnson noise uncertainty
FIGURE 6-7 Curve A: Uncertainty due to un- equal to that in Figure 6-6, curve A. For most
certainties in cell positioning. (Data adapted. Re- infrared measurements, the errors would prob-
printed with permission from L. D. Rothman, S. R. • For example, see: J. D. Inlle. Jr~ AII/IL Clam. Actll, •••
ably be larger than those indicated by the plot. 131 (1977~
Crouch, and J. D. Ingle, Jr .• AruJL Chern., 47, 1231 Considerably greater variation in behavior • For • discussion ol the ell"ectsof slit width on .pec:t•.••
(1975~ Copyright by the American Chemical is encountered among ultraviolet and visible see: OptimumSp«trophotometer P-en. Applictllion
Society.) Curve B: Combined effect of cell position- photometers and spectrophotometers. For the Report AR •.•.•1, Monrovia, CA: Cary Instruments; and
ing uncertainty and Johnson noise. best quality instruments, the limiting source F. C. Strons III, AnDl. CMm.,48, 2155 (1976~
100 slit width. Careful inspection of Figure 6-8
90 reveals the same type of effect. In both sets of
spectra, the areas under the individual peaks
80
are the same, but wide slit widths result in
i 70 broader, lower peaks.
';60
~
~ 60

i40
It is evident from both of these illustra-
tions that quantitative measurement of
narrow absorption bands demands the use of
1
<
04
.
0.3
narrow slit widths or, alternatively, very re-
.f3O
producible slit-width settings.
Bandwidth· 0.5 nm
20 Unfortunately, a decrease in slit width is
accompanied by a second-order power reduc-
10
tion in the e~itted radiant energy; at very
100
narrow settings, spectral detail may be lost
90 owing to an increase in the signal-to-noise
4600 6000 4200 4600 6000 4200 4600
80 ratio. The situation becomes particularly ser·
WIY8Iength. It. WIYeI8ngth. It. WIY8Iength. It.
ious in spectnU regions where the output of
I 70 the source or the sensitivity of the detector is FIGURE 8-9. Effect of slit width and bandwidth on peak heights. Here, the sample was
solution of praseodymium chloride. (From Optimum Spectrophotometer Parameters, Applica-
a
"'60 low. Under such circumstances, noise in
either of these components or their associated tion Report AR 14-2, Monrovia, California. Cary Instruments. With permission.)
160
electronic cinoUits may result in partial or
i40
total loss of spectral fine structure.
.•.~ 30 In general, lit is good practice to narrow
20

10
slits no more than is necessary for resolution
of the spectrum at hand. With a variable slit
1.00
,
spectrophotometer, proper slit adjustment \ 8
100
can be determined by obtaining spectra at \
90 progressively narrower slits until peak heights- 0.75 \
80
become constant. \

~ 70
Effect of Scattered ..
.Ii 60
Radiation at Wavelength .e~ 0.50
!i 60

40
Extremes of a Spectrophotometer ~
<
We have already noted that scattered radia-
.•.~ 30 Bandwidth· 20 nm tion may cause instrumental deviations from
0.25
20 Beer's law. When measurements are at-
10
tempted at the wavelength extremes of an
instrument, the effects of stray radiation may
0
300 360 400 460 500 550 600 650 be even more serious, and on occasion lead to
Wavelength, om the appearanee! of false absorption peaks. For 380
example, consider a spectrophotpmeter for Wavelength, nm
FIGURE 6-8 Effect of band width on the visible region equipped with glass optics, FIGURE 6-10 Spectra of cerium (IV)
spectral detail. The sample was a didymium a tungsten source, and a photocell detector. obtained with a spectrophotometer
glass. [Spectra provided through the courtesy At wavelengths below about 380 nm, the win- having glass optics (A) and quartz optics
of Amsco Instrument Company (formerly dows, cells, and prism begin to absorb radia- (B). The false peak in A arises from
Turner Associates) Carpinteria, California.] tion, thus reducing the radiant energy transmission of stray radiation of longer
wavelengths.
reaching the transducer. The output of the the wavelength extremes of a visible-region (a) the absorbance of a 3.77 x 10-4M solution of the complex at 580
source falls off rapidly in this region as well; spectrophotometer is shown in Figure 6-10. nm when measured in a 0.75O-an ceIL
so also does the sensitivity of the photo- The spectrum of a solution of cerium(IV) ob- (b) the transmittance of a 2.85 x 1O-4M solution employing the SlPIle
electric device. Thus, the radiant power for tained with an ultraviolet-visible spectro- cell as in (a).
the 100% T adjustment may be as low as 1 to photometer, sensitive in the region of 200 to (c) the absorbance (0.75O-cm cell) of a solution that has half the trans-
2% of that in the region between SOOand 650 750 DID, is shown by curve B. Curve A is a mittance of that described in (a~
nm. spectrum of the same solution obtained with 5. A solution containing the thiourea complex of bismuth(III) has a
The scattered radiation, however, is often a simple visible spectrophotometer. The ap- molar absorptivity of 9.3 x 103 liter em-I mol-I at 470 nm.
made up of wavelengths to which the instru- parent maximum shown in curve A arises (a) What will be the absorbance of a 5.0 x lO-sM solution of the
ment is highly sensitive. Thus, its effects can from the instrument responding to stray complex when measured in a 0.5OO-cmcell?
be enormously magnified. Indeed, in some in- wavelengths longer than 400 nm, which (as (b) What will be the percent transmittance of the solution described in
stances the output signal: produced by the can be seen from the spectra) are not ab- (a)?
stray radiation may exceed that from the sorbed by the cerium(IV) ions. (c) What concentration of bismuth could be determined by means of
monochromator beam; uDder these circum- This same effect is sometimes observed this complex if 1.00-cm cells are to be used and the absorbance is
stances, the measured absorbance is as much with ultraviolet-visible instruments when to be kept between 0.100 and 1.500?
that for the stray radiatioq as for the radia- attempts are made to measure absorbances at 6. In ethanol, acetone has a molar absorptivity of 2.75 x 103 liter em - I
tion to which the instrument is set. wavelengths lower than about 200 nm. mol-1 at 366 nm. What range of acetone concentrations could· be
An example of a false peak appearing at determined if the percent transmittances of the solutions are to be
limited to a range of 10 to 90% and a 1.().cm cell is to be used?
7. In neutral aqueous solution, it is found that log t for phenol at 211 nm
1. Use the data provided to evaluate the missing quantities. Wherever
is 3.79. What range of phenol concentration could be determined spec-
n~ry, assume that the molecular weight of the absorbing species is
trophotometrically if absorbance values in a 2.00-cm cell are to be
2~0.
limited to a range of 0.100 to 1.50?
8. The equilibrium constant for the reaction
A %T t b, em c,M C

2CrO~- + 2W ~ Cr10~- + H10


(a) 0.2% 2.50 4.41 x 10- 4 mg,lliter
(b) 19.6 -1.50 6.91 x 10-3 ppm 14
has a value of 4.2 x 10 . The molar absorptivities for the two princi-
(e) 0.877 0.500 g,IIiter pal species in a solution of K1Cr10, are
(d) 84.2 7.85 x 102 3.00 X 10-4 II1II100 ml
(e) US x 104 1.25 3.33 ppm
(f) 6.42 x 103 1.10 7.84 X 10-5 mg,lliter
(g) 43.2 0.100 4.11 ppm
(h) 1.025 2.86 x 103 1.00 g,IIiter 1.84 X 103 10.7 X 101
(i) 87.2 0.980 mg,lliter 4.81 X 103 7.28 X 101
(j) 6.74 9.16 x 102 1.86 X 10-4 mg,lliter 1.88 X 103 1.89 X 102

2. A,solution that was 1.54 x 1O-4M in X had a transmittance of 0.0874 Four solutions were prepared by dissolving the following number of
when measured in a 2.00-cm cell. What concentration of X would be moles of K1Cr107 in water and diluting to 1.00 liter with a pH 5.40
required for the transmittance to be increased by a factor of 3 when a buffer: 4.00 x 10-4,3.00 X 10-4,2.00 X 10-4, and 1.00 x 10-4• Derive
1.@O-cmcell was used? theoretical absorbance values (1.00-cm cells) for each and plot the data
3. A 'compound had a molar absorptivity of 6.74 x 103 liter em-I mol-I. for (a) 345 nm, (b) 370 nm, (c) 400 nm.
What concentration of the compound would be required to produce a 9. A species Y has a molar absorptivity of 2400. Derive absorbance data
solution having a transmittance of 7.77% in a 2.5O-an cell? (1.QO-cm cells) for solutions of Y that are 10 x 10-4, 6.00 X 10'4,
4. At 580 nm, the wavelength of its maximum absorption, the complex 3.00 X 10-4, and 1.00 x 1O-4M in Y, assuming that the radiation
FeSCN2+ has a molar absorptivity of 7.00 x 103 liter em-I mol-I. employed was contaminated with the following percent of nonad-
Calculate sorbed radiation: (a) 0.000; (b) 0.300; (c) 2.00; (d) 6.00. Plot the data.
Absorption measurements employing ultra- more, the amount of thermal energy evolved
violet or visible radiation find widespread is usually not detectable. Thus, absorption
application to quantitative and qualitative measurements have the advantage of creating
analysis. Some of these applications are con- minimal disturbance of the system under
sidered in this chapter} study (except when photochemical de-
composition occurs ~
The absorption of ultraviolet or visible
radiation generally results from excitation of
bonding electrons; as a consequence, the
The absorPtion of ultraviolet or visible radia- wavelengths of absorption peaks can be cor-
tion by some species M can be considered to related with the types of bonds that exist in
be a two-siep process, the first of which in- the species under study. Absorption spectros-
volves excitation as shown by the equation copy is, therefore, valuable for identifying
functional groups in a molecule; it also pro-
M + hv --+ M· vides a somewhat selective method of quanti-
where M· represents the atomic or molecular tative analysis for compounds containing
particle in the electronically excited state re- absorbing bonds.
sulting from absorption of the photon h,•.The For purposes of this discussion, it is useful
lifetime of the excited state is brief (10-1 to to recognize three types of electronic transi-
10-9 s~ its existence being terminated by any tions and to categorize absorbing species on
of several relaxation processes (p. 1(9). The this basis. The three include transitions,
most common type of relaxation involves involving: (1) n, CT, and n electrons, (2) d and!
conversion! of the excitation energy to heat; electrons, and (3) charge-transfer electrons.
that is,
(M· ...•M + heat Absorbing Species
Containing n, CT, and n Electrons
Relaxation may also occur by decomposition
of M· to form new species; such a proceSs is Absorbing species of this type include organic
called a photochemical reaction. Alternatively, molecules and ions as well as a number of
relaxation may involve fluorescent or phos- inorganic anions, Our discussion will deal
phorescent reemission of radiation. It is im- largely with the former. although brief men-
portant to note that the lifetime of M* is tion will be made of absorption by certain
usually so very short that its concentration at inorganic systems as well.
any instant is ordinarily negligible. Further- All organic compounds are capable of
absorbing electromagnetic radiation because
all contain valence electrons that can be
excited to higher energy levels. The excitation
I Some useful references on absorl'lion methods include: energies associated with electrons forming
R. P. Baum.tn. Ahsorption Spectroscop)". New York: most single bonds are sufficiently high that
Wiley. 1962: J. R. Edisbury. Practical Hints on Ahsorp- absorption by them is restricted to the so-
tion Spectr0rlletr}". Nc"W York: Plenum Press. I96X: F.
Grum. Physisal Methods of Chemistry. eds. A. Wcissber-
called vacuum ultraviolet region (A. < 185 nm),
ger and B. W. Rossiter. New York:. Wiley-Interscience, where components of the atmosphere also
1972, Volume I, Part 111 B. Chapter 3; H. H. Jaffe and absorb strongly. The experimental difficulties
M. Orchin, TMory and Applictltions of Vltrariole! associated with the vacuum ultraviolet are
Spectroscopy. New York: Wiley, t962; G. F. Lothian, formidable; as a result, most spectrophoto-
Absorplion SpectropMt"""'try, 3d cd. London: Adam
metric investigations of organic compounds
Hilger Ltd, 1969; and J. E. Crooks, The Sptrtrum in
Ch •••••istry. London: Academic Press. 1978.
have involved the wavelength region greater
than 185 om. Absorption oflonger-wavelength
ultraviolet and visible radiation is restricted to
molecule occupy th~ former in the ground
state.
In addition to a and Jr electrons, many
organic compounds contain nonbonding elec-
~.
·c xx
• ••
00
00
0
.-a
x_.
a limited number of functional groups (called The molecular orbitals associated with
trons. These unshared electrons are designated 1-. O-n
chromophores) that contain valena: electrons . single bonds in organic molecules are desig- by the symbol n. An example showing the three
with relatively low excitation energies. . nated as sigma (0-) orbitals, and the' cor- FIGURE 7-2 Types of
types of electrons in a simple organic molecule
The electronic spectra of organic molecules responding electrons are a electrons: As molecular orbitals in form-
is shown in Figure 7-2.
containing chromophores are usually complex, sbown in Figure 7-1a, the distribution of aldehyde.
As shown in Figure 7-3, the energies for
because the superposition of vibrational transi- charge density of a 'sigma orbital is rota- the various types of molecular orbitals differ
tions on the electronic transitions leads to an tionally symmetric around the axis. of the significantly. Quite .generally, the energy level
intricate combination of overlapping lines; the bond. Here, the average negative charge den- of a non bonding electron lies between those
result is a broad band of continuous absorp- sity arising from the motion of tbe two elec- of the bonding and the antibonding Jr and a and can be brought about by radiation in the
tion. The complex nature of the spectra makes trons around the two positive nuclei is orbitals. region of between 150 and 250 nm, with most
detailed theoretical analysis difficult or im- indicated by the degree of shading. Electronic transitions among certain of the absorption peaks appearing below 200 nm.
possible. Nevertheless, qualitative or semi- The double bond in an organic molecule energy levels can be brought about by the Table 7-1 shows absorption data for some
quantitative statements cona:ming the types rontains two types of molecular orbitals: a absorption of radiation. As shown in Figure typical n -+ cr* transitions. It will be seen that
of electronic transitions responsible for a given sigma (a) orbital corresponding to one pair of 7-3, there are four: of these: a ....•a*, n -+ a*, the energy requirements for such transitions
absorption spectrum can be deduced from tbe bonding electrons; and a pi (Jr) molecular n ....•Jr*, and It -+ Jr•. depend primarily upon the kind of ~tomic
molecular orbital considerations. orbital associated with the other pair. Pi orbi- a ....•cr* Transitions. Here, an electron in a bond and to a lesser extent upon the structure
Types of AlIIorbing Electroas.1 The elec- tals are formed by the parallel overlap of
bonding a orbital of a molecule is excited to of the molecule. The molar absorptivities (e)
trons that contribute to absorption by an atomic p orbitals. Their charge distribution is associated with this type of absorption are
the corresponding antibonding orbital by the
organic molecule are: (1) tbose that partici- characterized by a nodal plane (a region of
absorption of radia~ion. The molecule is then intermediate in magnitude and usually range
pate directly in bond formation between low-charge density) along the axis of the
described as being Iin the a,a· excited state. between 100 and 3000 liter em -I mol- I.
atoms and are thus associated witb more than bond and a maximum density in regions
Relative to other; possible transitions, the Absorption maxima for formation of the
one atom; (2) nonbonding or unshared outer above and below the plane (see Figure 7-1b).
energy required to induce a (T'....•(T. transition n,(T· state tend to shift to shorter wavelengths
electrons that are largely localized about such Also shown in Figure 7-1c and 7-1d are the in the presence of polar solvents such as
is large (see Figure 7-3), corresponding to
atoms as oxygen, the halogens, sulfur, and charge-density distributions for antibonding
radiant frequencies in the vacuum ultraviolet water or ethanol. The number of organic
nitrogen. sigma and pi orbitals; these orbitals are _functional groups with n ....•cr* peaks in the
region. Methane, for example, which contains
Covalent bonding occurs because the elec- designated by cr* and Jr•.
only single C-H bonds and can thus readily accessible ultraviolet region is rela-
trons forming the bond move in the field
undergo only a -+ a· transitions, exhibits an tively small.
about two atomic centers in such a manner as
absorption maximum at 125 nm. Ethane has

,/-a,.....
to minimize the repulsive coulombic forces
between these centers. The nonlocalized fields ~;,.",.........
,~.. an absorption peak at 135 nm, which must
also arise from the same type of transition,
between atoms that are occupied by bonding
electrons are called molecular orbitals and can ( but here, electrons of the C-C bond appear
to be involved. Because the strength of the
be considered to result from the overlap of r
C-C bond is less than that of the C-H
atomic orbitals. When two atomic orbitals
combine, either a low-energy bonding molecu-
bond, less energy is required for excitation;
thus, the absorptioJl peak occurs at a longer '0 .~ .~'0

lar orbital or a high-energy antibonding


molecular orbital results. The electrons of a
~

c:
. .
;>
.o wavelength.
Absorption maxima due to a"'" a* transi-
tions are never dbserved in the ordinary,
f
0
1t
~~ f
~

\J accessible ultraviolet region; for this reason,


they will not be considered further. .
n -+ a· Transitions. Saturated compounds
2 For funher details, see: C. N. R. Rao, Ultra-Viol~t and containing atoms with unshared electron
Visib/~ Spectroscopy, 3d ed. London: Butlerwonhs, 1975; pairs (nonbonding electrons) are capable of
and R. P. Bauman, Absorption Spectroscopy. New York: FIGURE 7-1 Electron distribution in FIGURE 7-3 Electronic molecular
n ....•a· transitions. In general, these transi-
Wiley, 1962. Chapters 6 and 8. sigma and pi molecular orbitals. energy levels.
tions require less energy than the a ....•a* type
/I •...• n· and n ....•

Transitions. Most alcohols, in which hydrogen-bond formation groups, since the positions of maxima are also absorptions of multichromophores in a single
applications of absorption spectroscopy to between the solvent protons and the non- affected by solvent and structural details. organic molecule are approximately additive,
organic compounds are based upon transi~ bonded electron pair is extensive. Here, the Furthermore, the peaks are ordinarily broad provided the chromophores are separated
tions for /I or n electrons to the n· excited energy of the n orbital is lowered by an because of vibrational effects; the precise from one another by more than one single
state, because the energies required for these amount approximately equal to the energy of determination of the position of a-maximum bond. Conjugation of chromophores, how-
processes bring the absorption peaks into an the hydrogen bond. When an n ....•7t. transi- is thus difficult. ever, has a profound effect·on spectral proper-
experimentally convenient spectral region tion occurs, however, the remaining single n Effect of Conjugation of Chromopbores. In ties. For example, it is seen in Table 7-3
(200 to 700 nm). Both transitions require the electron cannot maintain the hydrogen bond; the molecular-orbital treatment, n electrons that 1,3-butadiene, CH -eHCH -=CH2, has
presence of an unsaturated functional group thus, the energy ofthe n,n· excited state is not are considered to be further delocalized by a strong absorption band that is displaced
to provide the n orbitals. Strictly speaking, it affected by this type of solvent interaction. A the conjugation process; the orbitals thus in- to a longer wavelength by 20 nm as compared
is to these unsaturated absorbing centers that blue shift, also roughly corresponding to the volve four (or more) atomic centers. The with the corresponding peak for an uncon-
the term chromophore applies. energy of the hydrogen bond, is therefore effect of this delocalization is to lower the jugated diene. When three double bonds are
The molar absorptivities for peaks asso- observed. energy level of the n· orbital and give it less conjugated. the bathochromic effect is even
ciated with excitation to the n,n· state are A second solvent effect that undoubtedly antibonding character. Absorption maxima larger.
generally low and ordinarily range from 10 to influences both 7t •...• ~ and n ....•n· transitions are shifted to longer wavelengths as a Conjugation between the doubly bonded
100 liter em - 1 mol-I; values for n ....•n· tran- leads to a bathochromic shift with increased consequence. oxygen of aldehydes, ketones, and carboxylic
sitions, on the other hand, normally fall in the solvent polarity. This effect is small (usually . As seen from the data in Table 7-3, the acids and an olefinic double bond gives rise
range between 1000 and 10,000. Another less than 5 nm~ and as a result is completely
characteristic difference between the two overshadowed in n ....•n· transitions by the
types of absorption is the effect exerted by the hypsochromic effect just discussed. Here,
solvent on the wavelength of the peaks. Peaks attractive polarization forces between the sol- TABLE 7-2 ABSORPTION CHARACTERISTICS OF SOME COMMON
associated with n ....•7t. transitions are gen- vent and the absorber tend to lower the CHROMOPHORES
erally shifted to shorter wavelengths (a hyp- energy levels of both the unexcited and
sochromic or blue shift) with increasing the excited states. The effect on the excited Type of
polarity of the solvent. Usually, but not state is greater, however, and the energy dif- Chromophore Example Solvent ).••••(nm) e..... transition
always, the reverse trend (a bathochromic or ferences thus become smaller with increased Alkene C6HI3CH-eH2 n-Heptane 177 13,000 n ....•n·
red shift) is observed for n ....•n· transitions. solvent polarity; small bathochromic shifts CSH11CI!iEC-CH3 n ....•n·
Alkyne n-Heptane 178 10,000
The hypsochromic effect apparently arises result. 196 2000
from the increased solvation of the unbonded Orpnic CIIromophores. Table 7-2 lists 225 160
electron pair, which lowers the energy of the n common organic chromophores and the 0
orbital. The most dramatic effects of this kind approximate location of their absorption I
Qubonyl CH3CCH3 n-Hexane 186 1000 n ....•u·
(blue shifts of 30 nm or more) are seen with maxima. These data can serve only as rough n ....•n-
280 16
polar hydrolytic solvents, such as water or guides for the identification of functional
°
CH3CH
I
n-Hexane 180 large n ....•u·
293 12 n ....•n·
TABLE 7-1 SOME EXAMPLES OF ABSORPTION DUE TO
n ....•
u· TRANSITIONS- Carboxyl
°I
CH3COH Ethanol 204 41 /I •..•• n·

Compound
H2O
J.",•• (nm)
167
em••

1480
Compound J.",..( nm)
229
Em..

140 Amido
°•
CH3CNH2 Water 214 60 n -+ 7[*

CH30H 184 ~H3~2Sb Azo CH3N=NCH3 Ethanol 339 5 n ....•n·


150 CH320 184 2520
CH3Q 173 200 H3NH2 215 600 Nitro CH3N02 Isooctane 280 -22 n ....•n·
CH3I 258 365 (CH3hN 227 900 Nitroso C4H9NO Ethyl ether 300 100
665 20 n ....•n·
• Samples in vapor state. Nitrate C2HsON02 Dioxane 270 12 n ....•n·
• In ethanol solvent.
to similar behavior (see Table 7-3). Analo- Absorption by Aromatic Systems. The tional group that does not itself absorb in the carbonate (217 om), nitrite (360 and 280 om~
gous effects are also observed when two car- ultraviolet spectra of aromatic hydrocarbons ultraviolet region, but has the effect of shifting azido (230 nm), and trithiocarbonate (500 nm)
bonyl or carboxylate groups are conjugated are characterized by three sets of bands that chromophore peaks to longer wavelengths as ions. .
with one another. For «-p unsaturated originate from n ...•7t* transitions. For exam- well as increasing their intensities. It is seen in
aldehydes and ketones,· the weak absorption ple, benzene has a strong absorption peak at Table 7-4 that -oH and -NH2 have an Absorption
peak due to n ...• 1!* transitions is shifted to 184 om (e.- - 60,(00); a weaker band, called auxochromic effect on the benzene chromo- Involving d and f Electrons
longer wavelengths by 40 nm or more. In the E2 band, at 204 om (e.- = 79(0); and a phore, particularly with respect to the B Most transition-metal ions absorb in the
addition, a strong absorption peak corre- still weaker peak, termed the B band, at band. Auxochromic substituents have at least ultraviolet or visible region of the spectrum.
sponding to a II:.•.•1'. transition appears. This 256 nm (t",.. = 2(0). The long-wavelength one pair of n electrons capable of interacting For the lanthanide and actinide series, the
latter peak occurs only in the vacuum ultra- band of benzene, and many other aromatics, with the II: electrons of the ring. This interac- absorption process results from electronic
violet if the carbonyl group is not conjugated. contains a series Qf sharp peaks (see Figure tion apparently has the effect of stabilizing transitions of 4f and Sf electrons; for elements
The wavelengths of absorption peaks for 4-11b, p. 106) due to the superposition of the n· state, thereby lowering its energy; a of the first and second transition-metal series,
conjugated systems are sensitive to the types vibrational transitions upon the basic elec- bathochromic shift results. Note that the the 3d and 4d electrons are responsible for
of groups attached to the doubly bonded tronic transitions. Polar solvents tend to elim- auxochromic effect is more pronounced for absorption.
atoms. Various empirical rules have been inate this fine structure, as do certain types the phenolate anion than for phenol itself, Absorption by Lanthanide and Actinide
developed for predicting the effect of such of substitution. ; probably because the anion has an extra pair Ions. The ions of most lanthanide and acti-
substitutions upon absorption maxima and All three of the characteristic bands for of unshared electrons to contribute to the nide elements absorb in the ultraviolet and vis-
have proved useful for structural determina- benzene are strongly affected by ring substitu- interaction. With aniline, on the other hand, ible regions. In distinct contrast to the
tions.3 tion; the effects on the two longer-wavelength the nonbonding electrons are lost by forma- behavior of most inorganic and organic
bands are of particular interest because they tion of the anilinium cation, and the auxo- absorbers, their spectra consist of narrow,
can be readily stlK\ied with ordinary spectro- chromic effect disappears as a consequence. well-defined, and characteristic absorption
I For a summary or these rules, see: R. M. SilveRtein,
G. C. Bassler, and T. C. Morrill, Sp«tromerrlc Idmtljica- photometric equipment. Table 7-4 illustrates Absorption by Inorganic Anions. A number peaks, which are little affected by the type of
tiottofOr(lllllic COffIpowllds, 3d ed. New York: Wiley, 1974, the effects of some k:ommon ring substituents. of inorganic anions exhibit ultraviolet absorp- ligand associated with·the metal ion. Portions
pp. 241-255. By definition, an auxochrome is a fune- tion peaks that are a consequence of " ...•11:. of a typical spectrum are shown in Figure 7-4.
transitions. Examples include nitrate (313 nm), The transitions responsible for absorption

TABLE 7-3 EFFECT OF MULTICHROMOPHORES ON ABSORPTION

Compounll TABLE 7-4 ABSORPTION CHARACTERISTICS OF AROMATIC


Type )-Jnm) tmu
COMPOUNDS
CH3CH2CH2CH=CH2 Olefin 184 - 10,000
CH2 -eHCH2CH2CH==CH2 Diolefin (unconjugated) E2 Band B Band
185 - 20,000
H2C-eHCH-eH2 Diolefin (conjugated) 217 21,000 Compound ;""'.(nm) f"maX ;""'.(nm) & ••••
H2C-eHCH-eHCH==CH2 Triolefin (conjugated) 250
Benzene C6H6 204 7900 256 200
0
I Toluene C6HsCH3 207 7000 261 300
CH3CH2CH2CH2CCH3 Ketone ~82 27 m-Xylene C6H4(CH3h 263 300
Chlorobenzene C6HsCI 210 7600 265 240

CH2 =CHCH2CH2CCH3
°I Unsaturated ketone !78
;
30
Phenol
Phenolate ion
C6HsOH
C6HsO-
211
235
6200
9400
270
287
1450
2600
(unconjugated ) Aniline C6HsNH2 230 8600 280 1430
0
I Anilinium ion C6HsNHj 203 7500 254 160
CH2-eHCCH3 Unsaturated ketone 324 24 Thiophenol C6HsSH 236 10,000 269 700
(conjugated) Naphthalene C10He 286 9300 312 289
219 3600 Styrene C6HsCH==CH2 244 12,000 282 450
~y elements of the lanthanide series appear to
mvolve the various energy levels of 4f elec-
trons, while it is the Sf electrons of the acti-
nide teries that interact with radiation. These
inner orbitals are largely screened from exter- .
nal influences by electrons occupying orbitals ".
with higher principal quantum numbers. As a
consequence, the bands are narrow and rela-
tively unaffected by the nature of the solvent
or the species bonded by the outer electrons".
Absorption by Elements of tile First lUIlI
Second TraJlSition-Metal Series. The ions and
complexes of the 18 elements in the first two
transition series tend to absorb visible radia-
tion in one if not all of their oxidation states.
In contrast to the lanthanide and actinide ele- WlM!length. nm
ments, however, the absorption bands are
FIGURE 7-5 Absorption spectra of ~me d.2_.'- dil
?ften broad (Figu~ 7-S) and are strongly
transition-metal ions. FIGURE 7-6 Electron density distribution in various d orbitals.
mfluenced by chemlClll environmental factors.
An example of the environmental effect is
found in the pale blue color of the aquo
copper(II) ion and the much darker blue of
the copper complex with ammonia. i Both theories are based upon the premise except for their spatial orientation. Note that
Metals of the transition series are charac- that the energies of d orbitals of the these orbitals occupy spaces between the three
terized by having five partially occupied d transition-metal ions in solution are not iden- axes; consequently, they have minimum elec-
orbitals (3d in the first series and 4d in the tical, and that absorption involves the transi- tron densities along the axes and maximum
second~ each capable of accommodating a tion of electrons from a d orbital of lower densities on the diagonals between axes. In
pair of electrons. The electrons in these orbit- energy to one of higher energy. In the absence contrast, the electron densities of the d x' -"
als do not aenerally participate in bond of an external electric or magnetic field (as in and the d.. orbitals are directed along the
formation; nevertheless, it is clear that the the dilute gaseous state~ the energies of the axes .
.s.. 0.04
sJ'CC!raicharacteristics of transition metals in-
~olve electronic transitions among the var-
five d orbitals are identical, and absorption of
radiation is not required for an electron to
Let us now consider a transition-metal ion
that is coordinated to six molecules of water
IOUSenergy levels of these d orbitals. move from one orbital to another. On the (or some other ligand). These ligand
Two theories have been advanced to ra- other hand, complex formation in solution molecules or ions can be imagined as being
tionalize the colors of transition-metal ions occurs between the metal ion and water or symmetrically distributed around the central
and the profound influence of chemical envi- some other ligand. Splitting of the d-orbital atom, one ligand being located at each end of
ronment ~ these colors. The crystal-field' energies then results, owing to the differential the three axes shown in Figure 7-6; the result-
t~eory, which we shall discuss briefly, is. the forces of electrostatic repulsion between the ing octahedral structure is the most common
~lm~ler of the two and is adequate for a qual- electron pair of the donor and the electrons in orientation for transition-metal complexes.
Wavelength. nm Itative understanding. The more complex the various d orbitals of the central metal ion. The negative ends of the water dipoles are
FIGURE 7-4 The absorption spec- ~olecular-orbital treatment, however, pro- In order to understand this effect, we must pointed toward the metal ion, and the electri-
trum of a praseodymium chloride solu- vides a better quantitative treatment of; the first consider the spatial distribution of elec- cal fields from these dipoles tend to exert a
tion; a = absorptivity in liter em -, g - '. phenomenon.4 repulsive effect on all of the d orbitals, thus
trons in the various d orbitals.
(Reprinted with permission from T. The electron-density distribution of the increasing their energy; the orbitals are then
Moeller and J. C. Brantley, Anal. Chern., five d orbitals around the nucleus is shown in said to have become destabilized. The maxi-
• For a DOnmathemalicaldiscussion of these theories,
22,433 (1950). Copyright by the Ameri- Figure 7-6. Three of the orbitals, termed d"" mum charge density of the dx• orbital lies
see: L. E. Orgel, An Introduction 10 Traruition Metal
can Chemical Society.) Chemistry, Ligand-FiLld Theory. New York: Wiley, 1960.
along the bonding axis. The negative field of a
dx.' and dr-' are similar in every regard
---------------'1,--;--------
countered: the tetrahedral, in which the four ~ansier rq,tion· and are therefore called,
groups are symmetrically distributed around charge-transfer complexes. Common examples
the metal ion; and the square planar, in which of such complexes include the thiocyanate
dz2. d.2_r' dK2_~2
the four ligands and the metal ion lie in a and phenolic complexes of iron(I1I), the
, ,,
II
d.y, dllz. dY1
single plane. Unique d-orbital. splitting pat- o-phenanthroline complex of iron(II), the
, I
I,
d•• terns for each configuration can be deduced
by arguments similar to those used for the
iodide complex of molecular iodine, and the
ferro-ferricyanide complex responsible for
~ I 6- I II
!! I octahedral structure. the color of Prussian blue.

/~
dlfl,dY1
w Iii
I
I 11/ The magnitude of 11 (Figure 7-7) depends In order for a complex to exhibit a charge-
d,2
/II, upon a number of factors, including the transfer spectrum, it is necessary for one of its
I, I 'd z2••d 2_r'
11/1 valence state of the metal ion and the position components to have electron-donor charac-
I / d.y, d." dyz II
II ,II
,I of the parent element in the periodic table. An teristics and for the other component to have
1/ /I tI
dley, dill, dY1 ( -J --.1 important variable attributable to the ligand electron-acceptor properties. Absorption of
dz2, d.2_y2 is the ligand .field strength, which is a measure radiation then involves transfer of an electron
No Octahedral
of the extent to which a complexing group from the donor to an orbital that is largely
T etrlhedral Square planar
ligand ligand ligand ligand will split the energies of the d electrons; that associated with the acceptor. As a conse-
field foeld foeld field is, a complexing agent with a high ligand field quence, the excited state is the product of an
FIGURE 7-7 Effect of ligand field on d-orbital energies. strength will cause 11 to be large. internal oxidation-reduction process. This be-
It is possible to arrange the common lig- havior differs from that of an organic chromo-
ands in the order