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Chapter 10 Spectroscopic Methods of Analysis 369

10A Overview of Spectroscopy

The focus of this chapter is photon spectroscopy, using ultraviolet, visible, and in-
frared radiation. Because these techniques use a common set of optical devices for
dispersing and focusing the radiation, they often are identified as optical spectros-
copies. For convenience we will usually use the simpler term spectroscopy in
place of photon spectroscopy or optical spectroscopy; however, it should be under-
stood that we are considering only a limited part of a much broader area of analyti-
cal methods. Before we examine specific spectroscopic methods, however, we first
review the properties of electromagnetic radiation.

10A.1 What Is Electromagnetic Radiation

Electromagnetic radiation, or light, is a form of energy whose behavior is described
by the properties of both waves and particles. The optical properties of electromag-
netic radiation, such as diffraction, are explained best by describing light as a wave.
Many of the interactions between electromagnetic radiation and matter, such as ab-
sorption and emission, however, are better described by treating light as a particle,
or photon. The exact nature of electromagnetic radiation remains unclear, as it has
since the development of quantum mechanics in the first quarter of the twentieth
century.3 Nevertheless, the dual models of wave and particle behavior provide a use-
ful description for electromagnetic radiation.

Wave Properties of Electromagnetic Radiation Electromagnetic radiation consists

of oscillating electric and magnetic fields that propagate through space along a lin-
ear path and with a constant velocity (Figure 10.1). In a vacuum, electromagnetic
radiation travels at the speed of light, c, which is 2.99792 108 m/s. Electromagnetic
radiation moves through a medium other than a vacuum with a velocity, v, less than
that of the speed of light in a vacuum. The difference between v and c is small
enough (< 0.1%) that the speed of light to three significant figures, 3.00 108 m/s,
is sufficiently accurate for most purposes.
Oscillations in the electric and magnetic fields are perpendicular to each other,
and to the direction of the waves propagation. Figure 10.1 shows an example of
plane-polarized electromagnetic radiation consisting of an oscillating electric field
and an oscillating magnetic field, each of which is constrained to a single plane.
Normally, electromagnetic radiation is unpolarized, with oscillating electric and

Electric field

Magnetic field

Direction
of
propagation

Figure 10.1
Plane-polarized electromagnetic radiation
showing the electric field, the magnetic
field, and the direction of propagation.
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370 Modern Analytical Chemistry
Figure 10.2
Electric field component of plane-polarized
electromagnetic radiation.
frequency
The number of oscillations of an
electromagnetic wave per second ().
wavelength
The distance between any two
consecutive maxima or minima of an
electromagnetic wave ().
wavenumber
The reciprocal of wavelength ().
Electric field strength
Ae
Time or distance
magnetic fields in all possible planes oriented perpendicular to the direction of
propagation.
The interaction of electromagnetic radiation with matter can be explained
using either the electric field or the magnetic field. For this reason, only the electric
field component is shown in Figure 10.2. The oscillating electric field is described by
a sine wave of the form
E = Ae sin(2t + )
where E is the magnitude of the electric field at time t, Ae is the electric fields maxi-
mum amplitude, is the frequency, or the number of oscillations in the electric
field per unit time, and is a phase angle accounting for the fact that the electric
fields magnitude need not be zero at t = 0. An identical equation can be written for
the magnetic field, M
M = Am sin(2t + )
where Am is the magnetic fields maximum amplitude.
An electromagnetic wave, therefore, is characterized by several fundamental
properties, including its velocity, amplitude, frequency, phase angle, polarization,
and direction of propagation.4 Other properties, which are based on these funda-
mental properties, also are useful for characterizing the wave behavior of electro-
magnetic radiation. The wavelength of an electromagnetic wave, , is defined as the
distance between successive maxima, or successive minima (see Figure 10.2). For
ultraviolet and visible electromagnetic radiation the wavelength is usually expressed
in nanometers (nm, 109 m), and the wavelength for infrared radiation is given in
microns (m, 106 m). Unlike frequency, wavelength depends on the electromag-
netic waves velocity, where
v c
= = (in vacuum)
Thus, for electromagnetic radiation of frequency, , the wavelength in vacuum is
longer than in other media. Another unit used to describe the wave properties of
electromagnetic radiation is the wavenumber, , which is the reciprocal of wave-
length
1
=
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Chapter 10 Spectroscopic Methods of Analysis 371

Wavenumbers are frequently used to characterize infrared radiation, with the units
given in reciprocal centimeter (cm1).

EXAMPLE 10.1
In 1817, Josef Fraunhofer (17871826) studied the spectrum of solar radiation,
observing a continuous spectrum with numerous dark lines. Fraunhofer
labeled the most prominent of the dark lines with letters. In 1859, Gustav
Kirchhoff (18241887) showed that the D line in the solar spectrum was due
to the absorption of solar radiation by sodium atoms. The wavelength of the
sodium D line is 589 nm. What are the frequency and the wavenumber for this
line?
SOLUTION
The frequency and wavenumber of the sodium D line are
c 3.00 108 m/s
= = = 5.09 1014 s 1
589 10 9 m

1 1 1m
= = = 1.70 104 cm 1

589 10 m 100 cm
9

Two additional wave properties are power, P, and intensity, I, which give the flux power
of energy from a source of electromagnetic radiation. The flux of energy per unit time (P).
intensity
Particle Properties of Electromagnetic Radiation When a sample absorbs electro- The flux of energy per unit time per area
magnetic radiation it undergoes a change in energy. The interaction between the (I).
sample and the electromagnetic radiation is easiest to understand if we assume that
electromagnetic radiation consists of a beam of energetic particles called photons. photon
When a photon is absorbed by a sample, it is destroyed, and its energy acquired A particle of light carrying an amount of
energy equal to h.
by the sample.5 The energy of a photon, in joules, is related to its frequency, wave-
length, or wavenumber by the following equations
E = h

hc
=

= hc
where h is Plancks constant, which has a value of 6.626 1034 J s.

EXAMPLE 10.2
What is the energy per photon of the sodium D line ( = 589 nm)?
SOLUTION
The energy of the sodium D line is
hc (6.626 10 34 J s) (3.00 108 m /s)
E = = = 3.37 10 19 J
589 10 9 m
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372 Modern Analytical Chemistry

Wavelength (m) 1014 1012 1010 108 106 104 102 100 102

Frequency (s1) 1022 1020 1018 1016 1014 1012 1010 108

Type of Molecular
Core-level Valence Molecular Nuclear
transition Nuclear rotations;
electrons electrons vibrations spin
electron spin

Spectral
-ray X-ray UV IR Microwave Radio wave
region

Visible

Wavelength (nm) 380 480 580 680 780

Violet Blue Green Yellow Orange Red
Figure 10.3
The electromagnetic spectrum showing the
colors of the visible spectrum.

Colorplate 9 shows the spectrum of visible The energy of a photon provides an additional characteristic property of electro-
light. magnetic radiation.

The Electromagnetic Spectrum The frequency and wavelength of electromagnetic

radiation vary over many orders of magnitude. For convenience, electromagnetic
radiation is divided into different regions based on the type of atomic or molecular
transition that gives rise to the absorption or emission of photons (Figure 10.3).
electromagnetic spectrum The boundaries describing the electromagnetic spectrum are not rigid, and an
The division of electromagnetic overlap between spectral regions is possible.
radiation on the basis of a photons
energy.
10A.2 Measuring Photons as a Signal
In the previous section we defined several characteristic properties of electromag-
netic radiation, including its energy, velocity, amplitude, frequency, phase angle,
E2 polarization, and direction of propagation. Spectroscopy is possible only if the pho-
tons interaction with the sample leads to a change in one or more of these charac-
teristic properties.
E1
Spectroscopy is conveniently divided into two broad classes. In one class of
techniques, energy is transferred between a photon of electromagnetic radiation and
the analyte (Table 10.1). In absorption spectroscopy the energy carried by a photon
is absorbed by the analyte, promoting the analyte from a lower-energy state to a
higher-energy, or excited, state (Figure 10.4). The source of the energetic state de-
pends on the photons energy. The electromagnetic spectrum in Figure 10.3, for ex-
E0
ample, shows that absorbing a photon of visible light causes a valence electron in
Figure 10.4 the analyte to move to a higher-energy level. When an analyte absorbs infrared radi-
Simplified energy level diagram showing ation, on the other hand, one of its chemical bonds experiences a change in vibra-
absorption of a photon. tional energy.
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Chapter 10 Spectroscopic Methods of Analysis 373

Table 10.1 Representative Spectroscopies Involving an Exchange of Energy

Type of Energy Transfer Region of the Electromagnetic Spectrum Spectroscopic Technique

absorption -ray Mossbauer spectroscopy

X-ray X-ray absorption spectroscopy
UV/Visa UV/Vis spectroscopyb
atomic absorption spectroscopyb
infrared infrared spectroscopyb
raman spectroscopy
microwave microwave spectroscopy
electron spin resonance spectroscopy
radio waves nuclear magnetic resonance spectroscopy
emission (thermal excitation) UV/Vis atomic emission spectroscopyb
photoluminescence X-ray X-ray fluorescence
UV/Vis fluorescence spectroscopyb
phosphorescence spectroscopyb
atomic fluorescence spectroscopy

aUV/Vis: ultraviolet and visible ranges.

bTechniques discussed in this text.

The intensity of photons passing through a sample containing the analyte is at-
tenuated because of absorption. The measurement of this attenuation, which we call
absorbance, serves as our signal. Note that the energy levels in Figure 10.4 have absorbance
well-defined values (i.e., they are quantized). Absorption only occurs when the pho- The attenuation of photons as they pass
tons energy matches the difference in energy, E, between two energy levels. A plot through a sample (A).

of absorbance as a function of the photons energy is called an absorbance spec-

absorbance spectrum
trum (Figure 10.5). A graph of a samples absorbance of
Emission of a photon occurs when an analyte in a higher-energy state returns electromagnetic radiation versus
to a lower-energy state (Figure 10.6). The higher-energy state can be achieved in wavelength (or frequency or
several ways, including thermal energy, radiant energy from a photon, or by a wavenumber).

emission
The release of a photon when an analyte
returns to a lower-energy state from a
1.000 higher-energy state.

0.800
Absorbance

0.600

0.400

0.300

0.00
Figure 10.5
350.0 430.0 510.0 590.0 670.0 750.0
Ultraviolet/visible absorption spectrum for
Wavelength (nm) bromothymol blue.