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Review:

1)  What is calibration in chemical analysis? Explain External-

Standard calibration and Standard-Addition methods briefly.

2)  What’s the difference between detector and transducer?

3)  Explain interdomain conversion.

歐亞書局

Chapter 6
An Introduction to
Spectrometric Methods

Spectroscopy (光譜學): science that deals with the

interactions of various types of radiation with matter.

Spectrometry or spectrometric methods (光譜分析

或光譜方法): the measurement of the intensity of radiation
with a photoelectric transducer or other type of electronic
device.

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6B Wave Properties of Electromagnetic Radiation

FIGURE 6-1 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.

歐亞書局 Ch6 An Introduction to Spectrometric Methods P.121

FIGURE 6-2 Change in wavelength as radiation passes from air into a

dense glass and back to air. Note that the wavelength shortens by nearly
200 nm, or more than 30%, as it passes into glass; a reverse change
occurs as the radiation again enters air.

Wavenumber (ν): ν = kν
Power (P): the energy of the beam that reaches a given area per second.

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y = A sin(ωt + φ) ω = 2πν y = A sin(2πνt + φ)

FIGURE 6-3 Regions of the electromagnetic spectrum.

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TABLE 6-1 Common Spectroscopic Methods Based on Electromagnetic

Radiation

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Principle of superposition (重疊原理):

y = A1sin(2πν1t+φ1) + A2sin(2πν2t+φ2) + … + Ansin(2πνnt+φn)

FIGURE 6-4 Superposition of sinusoidal wave: (a) A1<A2, (Φ1- Φ2) = 20˚, v1 =
v2; (b) A1<A2, (Φ1-Φ2) = 200˚, v1 = v2. In each instance, the black curve
results from the combination of the two other curves.

歐亞書局 Ch6 An Introduction to Spectrometric Methods P.124

FIGURE 6-5 Superposition of two waves of different frequencies but identical

amplitudes: (a) wave 1 with a period of 1/v1; (b) wave 2 with a period of 1/v2 (v2 = 1.25
v1); (c) combined wave pattern. Note that superposition of v1 and v2 produces a beat
pattern with a period of 1/Δv where Δv = |v1 – v2|.

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Complex waveform can be broken

down into simple components by a
mathematical operation called the
Fourier transformation.

Square wave-from described by

equation (6-8)

FIGURE 6-6 Superposition of

sine waves to form a square
wave: (a) combination of three
sine waves; (b) combination of
three, as in (a), and nine sine
waves.

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6B-5 Diffraction (繞射) of Radiation

Diffraction: a process in which a parallel beam of radiation is bent
as it passes by a sharp barrier or through a narrow opening.
Diffraction is a consequence of interference (干涉).

FIGURE 6-7 Propagation of waves through a slit: (a) xy »λ; (b) xy =λ.

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Constructive
interference

nλ = CF = BCsinθ
= ΒC.DE/OE
n: order of
interference

FIGURE 6-8 Diffraction of monochromatic radiation by slits.

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6B-7 Transmission of Radiation

Refractive index:

ni = c/νi
νi : velocity of the radiation
in the medium.

Liquid: 1.3-1.8
Solid: 1.3-2.5

Periodic polarization (極化) (Absorption occurs)

of the atomic and molecular
species: deformation of
electron clouds (10-14~10-15
sec), no-absorption and re-
emit.
FIGURE 6-9 A typical dispersion (分散) curve.

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Snell’s law

sinθ1/sinθ2 = n2 /n1 = ν2 /ν1

(n2)vac = (sinθ1)vac /sinθ2

(n2)air = (sinθ1)air /sinθ2

nvac = 1.00027nair

Fraction of reflection:

Ir /Io = (n2-n1)2/(n2+n1)2
FIGURE 6-10 Refraction of light in passing from a
less dense medium M1 into a more dense medium
M2, where its velocity is lower.

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6B-10 Scattering of Radiation (small & large particle)

n  Transmission of radiation in matter: a momentary retention of

the radiation energy by atoms, ions, or molecules followed by
re-emission of the radiation in all directions as the particles
return to their original state. Scattered radiation increases with
particle size.

n  * Rayleigh scattering: scattering by molecules significantly smaller

than the wavelength. Is = k/λ4dp2 (blue color of the sky)

n  * Mie scattering: scattering by large molecules, different in different

directions.

n  * Raman scattering: quantized frequency changes due to vibrational

energy level transitions.

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6-11 Polarization of Radiation

plane-polarized (平面偏振，平面偏極)

FIGURE 6-11 Unpolarized and plane-polarized radiation: (a) cross-sectional view

of a beam of monochromatic radiation, (b) successive end-on view of the
radiation in (a) if it is unpolarized, (c) successive end-on views of the radiation
of (a) if it is plane polarized on the vertical axis.

歐亞書局 Ch6 An Introduction to Spectrometric Methods P.130

FIGURE 6-12 (a) A few of the electric vectors of a beam traveling

perpendicular to the page. (b) The resolution of a vector in a plane XY into
two mutually perpendicular components. (c) The resultant when all vectors
are resolved (not to scale).

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6C Quantum-Mechanical Properties of Radiation

FIGURE 6-13 Apparatus for studying

the photoelectric effect (光電效應).
Photons enter the phototube, strike
the cathode, and eject electrons.
The photoelectrons are attracted to
the anode when it is positive with
respect to the cathode. When the
anode is negative as shown, the
electrons are “stopped”, and no
current passes. The negative
voltage between the anode and the
cathode when the current is zero is
the stopping potential (V0).

KEem = V0e = 1.60 x 10-19V0 joule

1 joule = 6.24 x 1018 eV

歐亞書局 Ch6 An Introduction to Spectrometric Methods P.131

KEm = hν – ω

h: Planck’s constant
= 6.6254 x 10-34 joule-sec.
-ω: work function (功函數)
ω represents the minimum energy
binding electron in the metal.

E = hν = KEm + ω

FIGURE 6-14 Maximum kinetic

energy of photoelectrons emitted
from three metal surfaces as a
function of radiation frequency.
The y-intercepts (-ω) are the work
functions for each metal. If
incident photons do not have
energies of at least hv = ω, no
photoelectrons are emitted from
the photocathode.

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6C-2 Energy States of Chemical Species (atoms,

ions, molecules)
Quantum theory:
1)  Atoms, ions, and molecules can exist only in certain discrete
states, characterized by definite amounts of energy. (quantized)
2)  When atoms, ions, and molecules absorb or emit radiation in
making the transition (躍遷) from one energy state to another, the
frequency or wavelength of the radiation is related to the energy
difference between the states by
E1 - E0 = hν = hc/λ

Atoms or ions: electronic states

Ground state (基態): E0
Molecules: electronic states, Excited states (激發態): E1
vibrational states, rotational states
At room temperature, chemical species are
primarily in their ground state.

歐亞書局 Ch6 An Introduction to Spectrometric Methods P.133

6C-3 Interactions of
Radiation and Matter

FIGURE 6-15(a)
Emission or chemiluminescence processes. In (a), the sample is excited (激發)
by the application of thermal, electrical, or chemical energy. These processes
do not involve radiant energy and are hence called non-radiative processes.

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Excited state

Ground state

FIGURE 6-15(b) In the energy level diagram (b), the dashed lines with
upward-pointing arrows symbolize these non-radiative excitation
processes, while the solid lines with downward-pointing arrows indicate
that the analyte loses its energy by emission of a photon.

歐亞書局 Ch6 An Introduction to Spectrometric Methods P.133

FIGURE 6-15(c) In (c), the resulting spectrum (光譜) is shown as a

measurement of the radiant power emitted PE as a function of
wavelength, λ.
Emission spectroscopy
Chemiluminescence sepctroscopy

Photoluminescence spectroscopy (fluorescence,

phosphorescence spectroscopy)

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Absorption methods

Absorbance (吸收度):
A = log(P0/P)

FIGUREto6-16
Ch6 An Introduction Absorption
Spectrometric methods. Radiation of
Methods incident radiant power P0 can be
P.134
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).

歐亞書局

Photoluminescence methods

FIGURE 6-17

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FIGURE 6-17(a) Photoluminescence (光致發光) methods (fluorescence

and phosphorescence). Fluorescence and phosphorescence result
from absorption of electromagnetic radiation and then dissipation of
the energy emission of radiation (a).

歐亞書局 Ch6 An Introduction to Spectrometric Methods P.134

FIGURE 6-17(b) In (b). the absorption can cause excitation of the analyte
to state 1 or state 2. Once excited, the excess energy ca be lost by
emission of a photon (Iuminescence, shown as solid line) or by non-
radiative processes (dashed lines).

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FIGURE 6-17(c) The emission occurs over all angles, and the wavelengths
emitted (c) correspond to energy differences between levels. The major
distinction between fluorescence and phosphorescence is the time scale
of emission, with fluorescence being prompt and phosphorescence being
delayed.

歐亞書局 Ch6 An Introduction to Spectrometric Methods P.134

Radiation scattering
Elastic scattering: the wavelength of the scattered radiation is the
same as that of the source radiation. (nephelometry 濁度測定法,
turbidimetry 比濁法, particle size)
Inelastic scattering: for Raman spectroscopy (vibrational spectrum).

FIGURE 6-18 Inelastic scattering in Raman spectroscopy.

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FIGURE 6-18(a) As incident radiation of frequency vex impinges on the

sample, molecules of the sample are excited from one of their ground
vibrational states to a higher so-called virtual state, indicated by the
dashed level in (b).

歐亞書局 Ch6 An Introduction to Spectrometric Methods P.135

FIGURE 6-18(b) When the molecule relaxes, it may return to the first
vibrational as indicated and emit a photon of energy E = h(vex – vv) where
vv is the frequency of the vibrational transition. Alternatively, if the
molecule is in the first excited vibrational state, it may absorb a quantum
of the incident radiation, be excited to the virtual state, and relax back to
the ground vibrational state. This process produces an emitted photon of
energy E = h(vex + vv). In both cases, the emitted radiation differs in
frequency from the incident radiation by the vibrational frequency of the
molecule vv.
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FIGURE 6-18(c) The spectrum resulting from the inelastically scattered

radiation shows three peaks: one at vex – vv (Stokes), a second intense
peak at vex for radiation that is scattered without a frequency change, and
a third (anti-Stokes) at vex + vv. The intensities of the Stokes and anti-
Stokes peaks give quantitative information, and the positions of the
peaks give qualitative information about the sample molecule.

歐亞書局 Ch6 An Introduction to Spectrometric Methods P.135

6C-4 Emission (發
射) of Radiation
Excited particles (atoms,
ions, or molecules) relax
to lower energy levels by
giving up excess energy
as photons.

(Excitation means: p. 135)

FIGURE 6-19 Emission spectrum of a brine sample obtained with an oxyhydrogen

flame. The spectrum consists of the superimposed line, band, and continuum
spectra of the constituents of the sample. The characteristic wavelengths of the
species contributing to the spectrum are listed beside each feature.

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Review:

n  1) Explain the difference between emission and

photoluminescence?
n  2) Why molecular absorption and emission spectra are more
complex than atomic ones?

n  3) Explain stopping voltage (V0) and work function briefly.

歐亞書局

10-15 sec (vibrational state)

10-8 sec

FIGURE 6-21 Energy-level diagrams for (a) a sodium atom showing the
source of a line spectrum and (b) a simple molecule showing the source
of a band spectrum.

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Continuum radiation: results

from collisions between the
electrons of the beam and the
atoms of the target material.

FIGURE 6-20 X-ray emission spectrum of molybdenum metal

by bombarding with electron beam.

Electronic transitions in innermost orbitals: independent of

environment.

歐亞書局 Ch6 An Introduction to Spectrometric Methods P.136

FIGURE 6-22 Blackbody radiation curves.

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6C-5 Absorption of Radiation

When radiation passes through a layer
of solid, liquid, or gas, certain
frequencies may be be selectively
removed by absorption.

Absorbance (吸收度):
A = log(Po/P) = -log(P/Po) = -logT

Absorption spectra: influenced by the

complexity, the physical state, and the
environment of the absorbing species.

FIGURE 6-23 Some typical ultraviolet

absorption spectra.

歐亞書局 Ch6 An Introduction to Spectrometric Methods P.138

Quantum theory: atoms, molecules, and ions have only a limited

number of discrete energy levels; for absorption to occur, the energy
of the exciting photon must exactly match the energy difference
between the ground state and one of the excited states of the
absorbing species.

* Atomic absorption: a few well-defined sharp peak.

UV/Visible radiation for outermost or bonding electrons; X-ray
for innermost electrons.
* Molecular absorption:
E = Eelectronic + Evibrational + Erotational

* Absorption induced by Magnetic Field

nuclear magnetic resonance (NMR)
electron spin resonance (ESR)

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Absorptions (electronic
transitions):
νi = (E1 + ei’ - Eo)/h
i = 1, 2, 3,…., n

Vibrational transitions:
ν = (ei – eo)/h
i = 1, 2, 3, …, k

FIGURE 6-24
Partial energy-level
diagrams for a
fluorescent organic
molecule.

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6C-6 Relaxation Processes

Non-radiative Relaxation: Fig. 6-24(b)

Fluorescence and Phosphorescence Relaxation:

Fluorescence Lifetimes (singlet):
excited electronic states: 10-8 sec
excited vibrational states: 10-15 sec
Vibrational relaxation occurs before electronic relaxation.

Stokes shift: the emitted wavelength has a lower frequency, or

longer wavelength, than the radiation that excited the
fluorescence.

Lifetime of triplet state: > 10-5 sec (Phosphorescence)

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6C-7 The Uncertainty Principle

Derived from principle of
superposition:

Δt ≥ 1/Δν or ΔtΔν ≥ 1

Δt .ΔE = h

If the energy E of a particle

or system of particles is
measurable for an exactly
known period of time Δt,
then this energy is
uncertain by at least h/Δt.

FIGURE 6-5 Superposition of two waves of different frequencies but identical

amplitudes: (a) wave 1 with a period of 1/v1; (b) wave 2 with a period of 1/v2 (v2 = 1.25
v1); (c) combined wave pattern. Note that superposition of v1 and v2 produces a beat
pattern with a period of 1/Δv where Δv = |v1 – v2|.

歐亞書局 Ch6 An Introduction to Spectrometric Methods P.137

6D Quantitative Aspects of Spectrochemical

Measurements
S = kP S: electrical signal
S = kP + kd kd: dark current

S= k’c (Pe = kc)

TABLE 6-2 Major Classes of Spectrochemical Methods

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Beer’s law:
A = abc a: absorptivity (L/g-cm) 吸光係數
A = εbc ε: molar absorptivity (L/mol-cm)

FIGURE 6-25 Attenuation of a beam of radiation by an absorbing solution.

The larger arrow on the incident beam signifies a higher radiant power than
is transmitted by the solution. The path length of the absorbing solution is b,
and the concentration is c.

歐亞書局 Ch6 An Introduction to Spectrometric Methods P.142

Measurement of Transmittance and Absorbance

FIGURE 6-26 Single-beam photometer (光度計) for absorption

measurements in the visible region.

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Absorbance: A = log(Po/P) = -log(P/Po) = -logT

FIGURE 6-27 Readout for an inexpensive photometer. Most modern

photometers convert the results directly to absorbance in hardware or
software.

歐亞書局 Ch6 An Introduction to Spectrometric Methods P.159

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