Chapter 24

Introduction to Spectrochemical
Methods

Book: Fundamentals of Analytical Chemistry by: Douglas

A. Skoog
• Spectroscopy is the interactions of radiation and matter.
• Spectroscopic analytical methods are based on measuring the
amount of radiation (hν):
1. Produced by molecular or atomic species of interest or
2. Absorbed by molecular or atomic species of interest
• Spectroscopic methods are classified according to the region of the
electromagnetic spectrum used or produced in the measurement.
The (1) γ-ray, (2) X-ray, (3) ultraviolet (UV), (4) visible, (5) infrared
(IR), (6) microwave, and (7) radio-frequency (RF) regions have been
used.
• Spectroscopic methods are used for the elucidation of molecular
structure as well as the quantitative and qualitative determination of
both inorganic and organic compounds.
Properties of Electromagnetic Radiation

• Electromagnetic radiation a form of energy (E) that is transmitted

through space at enormous velocities.

• Electromagnetic radiation can be described as a wave with properties

of (1) wavelength, (2) frequency, (3) velocity, and (4) amplitude.

• In contrast to sound waves, light requires no transmitting medium;

thus, it can travel readily through a vacuum.

• Light also travels nearly a million times faster than sound.

• For these processes, electromagnetic radiation can be treated as

discrete packets of energy or particles called photons or

quanta.

• These dual views of radiation as particles and waves are not

mutually exclusive but complementary.

• In fact, the energy of a photon is directly proportional to its

frequency.

𝒉𝒄
𝑬= = 𝒉𝝂
𝝀

C = 3 x 108 m/s and h 6.63 x 10-34 J.s

Wave Properties

• Electromagnetic radiation is conveniently modelled as waves

consisting of perpendicularly oscillating electric and magnetic

fields, as shown in Figure 24-1a.

• The electric field for a single frequency wave oscillates sinusoidally in

space and time, as shown in Figure 24-1b. The electric field is

represented as a vector whose length is proportional to the field

strength.

• The x-axis in this plot is either time as the radiation passes a fixed

point in space or distance at a fixed time. Note that the direction in

which the field oscillates is perpendicular to the direction in which

the radiation propagates.

Figure 24-1 Wave nature of a beam of single frequency electromagnetic
radiation. In (a), a plane-polarized wave is shown propagating along the x axis.
The electric field oscillates in a plane perpendicular to the magnetic field. If the
radiation were unpolarized, a component of the electric field would be seen in all
planes. In (b), only the electric field oscillations are shown. The amplitude of the
wave is the length of the electric field vector at the wave maximum, while the
wavelength is the distance between successive maxima.
Wave Characteristics

• In Figure 24-1, the amplitude of the sine wave is shown, and the

wavelength is defined.

• The time (s) required for the passage of successive maxima or minima

through a fixed point in space is called the period, p, of the radiation. The

frequency, v, is the number of oscillations of the electric field vector per

unit time and is equal to 1/p.

• The frequency of a light, Figure 24-1b wave or any wave of

electromagnetic radiation is determined by the source that emits it and

remains constant regardless of the medium traversed.

• In contrast, the velocity, v, of the wave front through a medium depends

on both (1) the medium and (2) the frequency.

• The wavelength, λ, is the linear distance between successive

maxima or minima of a wave, as shown in Figure 24-1b.

• The product of the frequency in waves per unit time and the

wavelength in distance per wave is the velocity of the wave in

distance per unit time (cm s-1 or m s-1).

• Both the velocity and the wavelength depend on the medium.

𝒄 = 𝝀𝝂
• Table 24-1 gives the units used to express wavelengths in various

regions of the spectrum.

 General information

The Speed of Light

• In a vacuum, light travels at its maximum velocity. This velocity, which is

given the special symbol c, is 2.99792 x 108 m s-1, c = 3.00 x 108 m s-1.
• In a medium containing matter, light travels with a velocity less than

c because of interaction between the electromagnetic field and

electrons in the atoms or molecules of the medium.

• Since the frequency of the radiation is constant, the wavelength

must decrease as the light passes from a vacuum to a medium

containing matter.

• This effect is illustrated in Figure 24-2 for a beam of visible radiation.

Note that the effect can be quite large.

 Constant
Not Constant

Figure 24-2 Change in wavelength as radiation passes from air into a dense
glass and back to air.
The wavenumber, ṽ, is another way to describe electromagnetic
radiation. It is defined as the number of waves per centimeter and
is equal to 1/λ. By definition, ṽ has the units of cm -1.

Example 24-1

Calculate the wavenumber of a beam of infrared radiation with a

wavelength of 5.00 μm.

Solution

ṽ = 1/λ = 1/(5.00 µm x 10-4 cm/µm) = 2000 cm-1

Calculate the wavenumber of a beam of infrared radiation

with a wavelength of 5.00 m.

Calculate the wavenumber of a beam of infrared radiation

with a wavelength of 5.00 nm.

Radiant Power and Intensity

• The radiant power, P, in watts (W) is the energy of a beam that

reaches a given area per unit time. The intensity is the radiant

power-per-unit solid angle.

• Both quantities are proportional to the square of the amplitude of

the electric field (see Figure 24-1b).

• Although not strictly correct, radiant power and intensity are

frequently used interchangeably.

General information
The Particle Nature of Light: Photons

• We relate the energy of a single photon to its wavelength, frequency,

and wavenumber by

𝒉𝒄
𝑬= = 𝒉𝝂 = 𝒉 𝝂෤
𝝀

• where h is Planck’s constant (h = 6.63 x 102-34 J.s).

• Note that the wavenumber and frequency in contrast to the

wavelength are directly proportional to the photon energy.

• Wavelength is inversely proportional to energy, E α 1/λ

• The radiant power of a beam of radiation is directly proportional

to the number of photons per second.

 A photon is a particle of electromagnetic radiation having zero mass
and an energy of hν.

Example 24-2

Calculate the energy in joules of one photon of radiation with the

wavelength given in Example 24-1.

Solution

E = hcṽ = 6.63 x 10-34 J.s x 3.00 x 1010 cm/s x 2000 cm-1 = 3.98 x 10-20 J
Calculate the energy in joules of one photon of radiation with the
wavelength given
1. 5 m
2. 5 nm
Interaction of Radiation and Matter

• The most interesting and useful interactions in spectroscopy are those

in which transitions occur between different energy levels of chemical

species. Other interactions, such as (1) reflection, (2) refraction, (3)

elastic scattering, (4) interference, and (5) diffraction, are often

related to the bulk properties of materials rather than to the unique

energy levels of specific molecules or atoms General information.

• Although these bulk interactions are also of interest in spectroscopy,

we will limit our discussion here to those interactions in which energy

level transitions occur.

• The specific types of interactions observed depend strongly on the

energy of the radiation used and the mode of detection.

The Electromagnetic Spectrum

• The electromagnetic spectrum covers an enormous range of

energies and thus wavelengths (or frequencies) (see Table 24-2).

• Useful frequencies vary from > 1019 Hz (γ-ray) to 103 Hz (radio

waves).
• An X-ray photon (v ~ 3 x 1018 Hz, λ ~ 10-10 m), for example, is 10,000

times as energetic as a photon emitted by an ordinary light bulb (v ~

3 x 1014 Hz, λ ~ 10-6 m) and 1015 times as energetic as a

radiofrequency photon (v ~ 3 x 103 Hz λ ~ 105 m) General

information.

• Different types of radiation such as gamma (γ) rays or radio waves

differ from visible light only in the energy (frequency) of their

photons General information.

• Figure 24-3 shows the regions of electromagnetic spectrum that are

used for spectroscopic analyses.

 Energy and frequency increase
Wavelength decreases

• The UV range from 100 to 400 nm

• The visible range from 400 to 800 nm

Figure 24-3 The regions of the electromagnetic spectrum. Interaction of an analyte
with electromagnetic radiation can result in the types of changes shown. Note that
changes in electron distributions occur in the UV/visible region. The wavenumber,
wavelength, frequency, and energy are characteristics that describe
electromagnetic radiation.
• Spectrochemical methods that use visible, ultraviolet and infrared

radiation are often called optical methods (in spite of the fact that the

human eye is not sensitive to UV or IR radiation).

Optical methods are spectroscopic methods based

on ultraviolet, visible, and infrared radiation

• This terminology arises from the many common features of

instruments for the three spectral regions and the similarities in the

way we view the interactions of the three types of radiation with matter.
Spectroscopic Measurements

• Spectroscopists use the interactions of radiation with matter to obtain

information about a sample.

• The sample is usually stimulated in some way by applying energy in

the form of heat, electrical energy, light, particles, or a chemical

reaction.

• Prior to applying the stimulus, the analyte is predominately in its

lowest-energy or ground state. The stimulus then causes some of

the analyte species to undergo a transition to a higher-energy or

excited state.
Excited state

E = hν
Ground state
• We acquire information about the analyte by measuring the

electromagnetic radiation emitted as it returns to the ground

state or by measuring the amount of electromagnetic radiation

absorbed as a result of excitation.

• The results of such a measurement are often expressed

graphically by a spectrum, which is a plot of the emitted radiation

as a function of frequency or wavelength.

• Figure 24-4 illustrates the processes that occur in emission and

chemiluminescence spectroscopy. The analyte is stimulated by

applying heat or electrical energy or by a chemical reaction

General information.
• The term emission spectroscopy usually refers to methods in which

the stimulus is heat or electrical energy, while

chemiluminescence spectroscopy refers to excitation of the

analyte by a chemical reaction General information.

• In both cases, measurement of the radiant power emitted as the

analyte returns to the ground state can give information about its

identity and concentration. General information

• When the sample is stimulated by applying an external

electromagnetic radiation source, several processes are possible.

For example, the radiation can be scattered or reflected. General

information
 General information

Figure 24-4 Emission or chemiluminescence processes. In (a), the sample is excited by

applying thermal, electrical, or chemical energy. No radiant energy is used to produce
excited states, and so, these are called non-radiative processes. In the energy level
diagram (b), the dashed lines with upward pointing arrows symbolize these nonradiative
excitation processes, while the solid lines with downward pointing arrows indicate that the
analyte loses its energy by emission of a photon. In (c), the resulting spectrum is shown
as a measurement of the radiant power emitted, PE, as a function of wavelength,λ.
• In absorption spectroscopy, we measure the amount of light

absorbed as a function of wavelength. Absorption measurements

can give both (1) qualitative and (2) quantitative information about

the sample, as shown in Figure 24-5.

• We focus here on absorption spectroscopy in the UV/visible region

of the spectrum because it is so widely used in chemistry, biology,

forensic science, engineering, agriculture, clinical chemistry, and

many other fields.

 Spectrum

Figure 24-5 Absorption methods. In (a), radiation of incident radiant power P0

can be absorbed by the analyte, resulting in a transmitted beam of lower

radiant power P. For absorption to occur the energy of the incident beam must

correspond to one of the energy differences shown in (b). The resulting

absorption spectrum is shown in (c).

• Note that the processes shown in Figures 24-4 through 24-6 can

occur in any region of the electromagnetic spectrum; the

different energy levels can be nuclear levels, electronic levels,

vibrational levels, or spin levels.

• In photoluminescence spectroscopy (see Figure 24-6), the

emission of photons is measured following absorption. The most

important forms of photoluminescence for analytical purposes are

fluorescence and phosphorescence spectroscopy General

information.
Absorption of Radiation

• Every molecular species (analyte) is capable of absorbing its own

characteristic frequencies of electromagnetic radiation, as described in

Figure 24-5.

• This process transfers energy to the molecule and results in a decrease

in the intensity of the incident electromagnetic radiation.

• Absorption of the radiation thus attenuates the beam in accordance

with the absorption law.

Analyte

Incident Transmitted
Radiation (P0) Radiation (P)
Absorption Process

• The absorption law, also known as the Beer-Lambert law or

just Beer’s law, tells us quantitatively how the amount of

attenuation depends on:

(1) The concentration of the absorbing molecules

(2) The path length over which absorption occurs

• As light traverses a medium containing an absorbing

analyte, the intensity decreases as the analyte becomes

excited.
1. For an analyte solution of a given concentration (c in M), the

longer the length of the medium through which the light passes

(path length of light, b in cm), the more absorbers are in the path,

and the greater the attenuation.

2. For a given path length of light (b in cm), the higher the

concentration (c in M) of absorbers, the stronger the attenuation.

• Figure 24-7 depicts the attenuation of a parallel beam of

monochromatic radiation as it passes through an absorbing

solution of thickness b cm and concentration c moles per liter

(M).
 Cell or cuvette

Figure 24-7 Attenuation of a beam of radiation by an absorbing solution.

The larger arrow on the incident beam signifies a higher radiant power P0 than that
transmitted by the solution P. The path length of the absorbing solution is b and the
concentration is c.
• Because of interactions between the photons and absorbing

particles (recall Figure 24-5), the radiant power of the beam

decreases from P0 to P.

• The transmittance (T) of the solution is the fraction of incident

radiation transmitted by the solution, as shown in Equation 24-4.

• Transmittance is often expressed as a percentage and called the

percent transmittance:
𝑷 𝑷
𝑻= 𝑶𝑹 %𝑻 = 𝒙 𝟏𝟎𝟎
𝑷𝟎 𝑷𝟎

• Absorbance (A)
𝑷𝟎
𝑨 = − 𝐥𝐨𝐠 𝑻 = 𝐥𝐨𝐠
𝑷
Calculate the transmission, if an analyte solution has an
absorbance of: (a) 1.000 and (b) 2.000

Answer:
(a) log T = - A = -1.000
T = antilog – (1.000) = 0.100
(a) log T = - A = -2.000
T = antilog – (2.000) = 0.0100
Measuring Transmittance and Absorbance

• Transmittance and absorbance, as defined by Equations

24-4 and 24-5 and depicted in Figure 24-7, usually cannot be

measured as shown because the solution to be studied must

be held in a container: cell or cuvette.

• Reflection and scattering losses can occur at the cell walls,

as shown in Figure 24-9. These losses can be substantial.

• For example, about 8.5% of a beam of yellow light is lost by

reflection when it passes through a glass cell.

• Light can also be scattered in all directions from the surface of large

molecules or particles, such as dust, in the solvent, and this scattering

can cause further attenuation of the beam as it passes through the

solution.

• To compensate for these effects, the power of the beam transmitted

through a cell containing the analyte solution is compared with one

that traverses an identical cell containing only the solvent (a reagent

blank).

• An experimental absorbance that closely approximates the true

absorbance for the solution is thus obtained, that is,

𝑷 𝑷𝒔𝒐𝒍𝒗𝒆𝒏𝒕
𝑨 = 𝐥𝐨𝐠 = 𝐥𝐨𝐠
𝑷𝟎 𝑷𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏
Figure 24-9 Reflection and scattering losses with a solution contained in a typical
glass cell. Losses by reflection can occur at all the boundaries that separate the
different materials. In this example, the light passes through the following
boundaries, called interfaces: air-glass, glass-solution, solution-glass, and glass-air.
• Because of this close approximation, the terms P0 and P will henceforth

refer to the power of a beam that has passed through cells containing

the solvent (or blank) and the analyte solution, respectively.

Beer’s Law

• According to Beer’s law, absorbance is directly proportional to the

concentration of the absorbing species, c, and to the path length, b, of

the absorbing medium as expressed by Equation 24-7.

A = log(P0/P) = abc

• In Equation 24-7, a is a proportionality constant called the absorptivity.

Because absorbance is a unitless quantity, the absorptivity must have

units that cancel the units of b and c.

• If, for example, c has the units of g L-1 and b has the units of cm,

absorptivity has the units of L g-1 cm-1.

• When we express the concentration in Equation 24-7 in moles per

liter and b in cm, the proportionality constant is called the molar

absorptivity and is given the symbol ε.

Thus A = εbc
where ε has the units of L mol-1 cm-1.
Example 24-3

A 7.25 x 10-5 M solution of potassium permanganate has a

transmittance of 44.1% when measured in a 2.10-cm cell at a

wavelength of 525 nm. Calculate (a) the absorbance of this solution and

(b) the molar absorptivity of KMnO4.

Solution

(a) A = -log T = -log 0.441 = -(0.356) = 0.356

(b) From Equation 24-8,ε = A/bc = 0.356/(2.10 cm x 7.25 x 10-5mol L-1)

= 2.34 x 103 L mol-1 cm-1