Atomic Theory

Engineering Encyclopedia
Saudi Aramco DeskTop Standards
THEORY OF ATOMIC ABSORPTION

AND EMISSION SPECTROSCOPY
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Chapter : Laboratory Science

File Reference: LAB-106.01
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Basic Atomic Absorption and Emission Spectroscopy

Theory of Atomic Absorption
and Emission Spectroscopy
Section
Page
INFORMATION ............................................................................................................... 2
PRINCIPLES OF LIGHT ENERGY: ABSORPTION AND EMISSION ............................. 2
ELECTRON CONFIGURATIONS AND EMISSION PATTERNS .................................... 5
LIGHT ENERGY IN ATOMIC SPECTROSCOPY ........................................................... 8
SUMMARY.................................................................................................................... 11
GLOSSARY .................................................................................................................. 12
LIST OF FIGURES
Figure 1. Atomic Model of Sodium Atom ....................................................................... 2
Figure 2. Atomic Absorption and Emission Process...................................................... 3
Figure 3. Electromagnetic Spectrum ............................................................................. 4
Figure 4. Plancks Constant of Proportionality............................................................... 4
Figure 5. Periodic Table of Elements for Atomic Spectroscopy..................................... 6
Figure 6. Visible Spectrum and element Resonance Lines ........................................... 7
Figure 7. Instruments for Atomic Spectroscopy............................................................. 9

INFORMATION
PRINCIPLES OF LIGHT ENERGY: ABSORPTION AND EMISSION
Atomic absorption and emission spectroscopy use the basic
principles of the quantum theory. The quantum theory was
proposed by Max Planck around 1900 to explain radiation of hot
bodies. Five years later Albert Einstein applied the quantum
principles to the energy emitted by metals exposed to light.
Neils Bohr in 1913 derived a mathematical model of the
hydrogen atom based on the quantum theory.
The atomic model with the electrons in discrete energy levels or
orbitals about the nucleus is shown in Figure 1.
Electron
Nucleus
Energy
Level
Figure 1. Atomic Model of Sodium Atom

This is an illustration of an atom described by the quantum

theory. The discrete energy levels of the electrons are set by
nature. An electron can move up to a higher level by absorbing
a specific quantity of energy. The electron will emit that exact
quantity of energy when the electron returns to the lower level.
This quantum of energy is called a photon.
Figure 2 shows the energy absorption (excitation) process
followed by the emission (relaxation) process. Atoms are at
ground state when all electrons are at their lowest energy levels.
When a photon is absorbed by an atom, an electron undergoes
a transition to a higher energy level. The atom is at an excited
state. Atoms return to the ground state by emitting the photon of
energy.
FLASH
ZAP
Ground
State
Energy
Absorption
(Excitation)
Excited
State
Energy
Emission
(Relaxation)
Figure 2. Atomic Absorption and Emission Process
If enough energy is absorbed, electrons may be completely

removed from an atom to form an ion. An ion is an atom with an
electrical charge. The energy absorbed in the ionization process
is emitted when an electron returns to the atom.

Energy in the form of rays or light is electromagnetic energy.

We are more familiar with thermal energy. It is measured from
hot -high energy - to cold - low energy. The spectrum of
electromagnetic radiation begins with the very high-energy
gamma rays and ends with the low energy radio waves as seen
in Figure 3. Atomic spectroscopy involves a small region of this
spectrum, namely the visible light portion with small overlaps
into the ultraviolet at the high-energy end and into the infrared
on the low energy side. Energy increases as the wavelength
decreases.
Figure 3. Electromagnetic Spectrum

A photon is proportional to the wavelength of electromagnetic
radiation. Plancks constant of proportionality is given in
Figure 4. This principle is the basis of atomic spectroscopy.
E=
hc
= hg
1
The energy of a photon is proportional to the

frequency (or wavelength) of the radiant energy.
E = Photon of Energy
C = Speed of Light
1 = Wavelength
h = Plancks Constant
g = Light Frequency
Figure 4. Plancks Constant of Proportionality

ELECTRON CONFIGURATIONS AND EMISSION PATTERNS

The Periodic Table of Elements (Figure 5) is a natural
classification of the elements by their electron configurations.
The inert gases at the far right have the most stable outer level
of electrons. The alkaline earth metals in the first column on the
left have the least stable outer electron level. The alkaline earth
metals require the least energy for excitation.
The element sodium has an atomic number of eleven. Sodium
has eleven electrons. The electrons are in energy levels unique
to sodium (see Figure 1). Each element has its own atomic
number, number of electrons and electron distribution. The
energy required to excite a given electron of sodium is unique.
The same is true for all elements. These unique quantums of
energy are called resonance energies. A wavelength spectrum
of energy emission from an excited element shows each
resonance energy as a line (See the color spectrum, Visible
Spectrum and Element Resonance Lines, Figure 6). Very
narrow wavelength bands of emitted energy generate the lines
of color seen in this figure. The lines are said to be
monochromatic. The resonance lines of sodium are readily seen
in the figure. Note the differences in the spectra of sodium,
hydrogen, calcium, mercury and neon.

IA
IIA
IIA
IVA
VA
VIA VIIA
VIIIA
IB
IIB
IIIB
IVB
VB
NOBLE
VIIB GASES
VIB
He
1.00794
1.00794 4.00260
10
Ne
Li
Be
6.941
9.01218
10.81
12.011
11
12
13
14
15
16
17
18
Na
Mg
Al
Si
Cl
Ar
32.06
35.453
39.948
34
35
36
22.98977 24.305
19
20
14.0067 15.9994 18.99840 20.179
26.98154 28.0855 30.97376
21
22
23
24
25
26
27
28
29
30
31
32
33
Ca
Sc
Ti
Cr
Mn
Fe
Co
Ni
Cu
Zn
Ga
Ge
As
Se
Br
Kr
39.0983
40.08
44.9559
47.88
50.9415
51.996
54.9380
55.847
58.9332
58.69
63.546
65.38
69.72
72.59
74.9216
78.96
79.904
83.80
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
Rb
Sr
Zr
Nb
Mo
Tc
Ru
Rh
Pd
Ag
Cd
In
Sn
Sb
Te
Xe
85.4678
87.62
88.9059
91.22
92.9064
95.94
(98)
114.82
118.69
121.75
55
56
57
72
73
74
75
81
82
83
84
Cs
Ba
La
Hf
Ta
132.9054 137.33 138.9055 178.49 180.9479 183.85
87
Fr
(223)
88
89
104
Ra
Ac
Unq Unp Unh
226.0254 227.0278
(261)
105
(262)
101.07 102.9055 106.42 107.8682 112.41
76
77
Re
Os
Ir
186.207
190.2
192.22
78
79
80
Pt
Au
Hg
195.08 196.9665 200.59
127.60 126.9045 131.29
85
86
Ti
Pb
Bi
Po
At
Rn
204.383
207.2
208.9804
(209)
(210)
(222)
106
(263)
58
59
60
61
62
63
64
65
66
67
68
69
70
71
Ce
Pr
Nd
Pm
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
(145)
150.36
151.96
140.12 140.9077 144.24
96
174.967
90
91
92
93
94
97
98
99
100
101
102
Th
Pa
Np
Pu
Am Cm
Bk
Cf
Es
Fm
Md
No
Lr
(244)
(243)
(247)
(251)
(252)
(257)
(258)
(259)
(260)
232.0381 231.0359 238.0289 237.0482
95
157.25 158.9254 162.50 164.9304 167.26 168.9342 173.04
(247)
103
Figure 5. Periodic Table of Elements for Atomic Spectroscopy
6000
4000A
Ne
Hg
Ca
Na
4000A
H Ca H
5000
5000
Fe
Na
6000
7000
7000

Figure 6. Visible Spectrum and element Resonance Lines

LIGHT ENERGY IN ATOMIC SPECTROSCOPY

Analytical spectroscopic methods utilize instruments designed to
measure light intensity and energy. Atomic spectroscopy
involves the light absorption or emission by electron transitions
in the atoms of a sample introduced into an atomic vapor
medium. Three types of instruments for atomic spectroscopy
are shown in Figure 7.
Atomic absorption spectroscopy (AAS), part 1 of Figure 7,
measures the intensity of light energy absorbed by the ground
state atoms of an element in an atomized sample. The energy is
measured at the specific wavelength region of the light
spectrum corresponding to one of the elements resonance
lines. The absorbed energy is specific to the element and
proportional to the number of atoms present. Absorption is
measured as the decrease in intensity of a light source passing
through the atomized sample.
Atomic emission spectroscopy (AES), part 2 of Figure 7,
measures light intensity and wavelength emitted by atoms that
have been excited by a thermal energy source. The light
intensity measured for a specific resonance line is proportional
to the number of atoms present. The resonance line identifies
the element.
Atomic fluorescence spectroscopy, part 3 of Figure 7, measures
the light intensity emitted by atoms that have been excited by
light energy of a specific wavelength. The intensity is a measure
of the number of atoms present. The excitation wavelength
identifies the element by resonance lines.
Instrument technology favors AAS and AES over atomic
fluorescence. AAS and AES are widely used techniques and are
very important tools in the analytical laboratory. All of the
elements that are not shaded in Figure 5 can be determined by
either AAS or AES techniques.

Instruments for Atomic Spectroscopy
Light
Source
Medium
for Atomic
Vapor
Monochromator
Detector
Part 1: AAS
Energy Source
and Medium for
Atomic Vapor
Monochromator
Detector
Part 2: AES
Monochromator
Part 3:
Detector
Atomic Fluorescence Spectroscopy
Figure 7. Instruments for Atomic Spectroscopy

AES has historically been a method to qualitatively identify

elements in samples. The emission spectrograph is used to
detect resonance lines in a spectrum generated by thermal
excitation of a sample. The spectral lines can be resolved into
patterns that are characteristic of the elements present in the
sample.
Analytical quantitative spectroscopy is accomplished by
comparing standard or known samples to unknown samples
using the same instrument conditions. For example quantitative
AAS is generally carried out in the laboratory as follows:
1. The instrument monochromator is set to measure light
intensity at the resonance wavelength of the element to be
determined.
2. A light source for the resonance wavelength is passed
through the atomic vapor medium containing a sample
blank. The light measured by the detector is set as zero
concentration on the instrument meter.
3. A standard sample of known concentration (Cstd) of the
element to be determined is placed in the atomic vapor, and
the light measured (Istd). The reading is the amount of light
absorbed by the atoms in the atomic vapor. It is directly
proportional to the standard sample concentration.
4. A sample of unknown concentration (Cunk) is placed in the
atomic vapor and the light intensity again measured (Iunk).
The measurement is proportional to the unknown
concentration.
By ratio and proportion the standard concentration and two
light readings are used to calculate the unknown
concentration.
Cunk C std
=
Iunk
Istd
Cunk =
C std Iunk
Istd
For quantitative AES and atomic fluorescence, emitted light

from the excited state atoms in the atomic vapor is measured
directly. The above standardization procedure is the basis for all
spectroscopic quantitative methods.
10

SUMMARY
Atomic absorption and atomic emission spectroscopy are based
on these principles of quantum theory and light energy:
Each element has a unique electron energy level distribution

for its atoms.
An atom is at ground state when its electrons are in their

lowest energy levels.
An atom is at an excited state when energy has been

absorbed and electrons move to higher energy levels.
An excited atom will return to the ground state by emitting

energy in the form of photons or light.
The energy of a photon is proportional to the wavelength of

the light.
Resonance energy is the energy absorbed or emitted for a

given electron transition of an element.
Each element has unique resonance energies.
Atomic absorption spectroscopy measures the light energy

absorbed by the atoms of a given element in a sample. The
absorbed energy is proportional to the concentration of the
element in the sample.
Atomic emission spectroscopy measures the light energy
emitted by excited state atoms of a given element in a sample
that has been subjected to an energy source. The light energy
emitted is proportional to the concentration of the element in the
sample.
11

GLOSSARY
atomic absorption
spectroscopy (AAS)
The technology or science of measuring the absorption of

light energy by atoms. Refers to the use of an analytical
laboratory instrument to determine amounts of specific
elements in samples.
atomic emission
spectroscopy (AES)
The technology or science of measuring the emission of

light energy by atoms. Refers to the use of an analytical
laboratory instrument to determine amounts of specific
elements in samples. Most modern AES instruments are
plasma instruments and are known as ICP (inductively
coupled plasma).
electromagnetic energy
Energy in the form of rays or light.
excited state
The state of an atom that has absorbed energy and one

or more of its electrons has moved to a higher energy
level.
ground state
The state of an atom with all of its electrons in their

lowest energy levels. The atom has no absorbed energy.
Monochromatic
Light energy of one wavelength.
Photon
An exact amount of electromagnetic energy associated

with the movement of an electron from one energy level
to another.
Plasma
A form of matter containing a significant amount of free

electrons and positive ions. A highly energized ionized
gas.
quantum
See Quantum Theory.
quantum theory
An explanation of how energy is absorbed and emitted in

stepwise amounts or quanta by materials. The
explanation involves an atomic structure consisting of a
nucleus surrounded by electrons in prescribed energy
levels. The movement of an electron from one level to
another results in the emission or absorption of a
quantum.
resonance line
A line formed on a spectrum at a specific wavelength that

is characteristic for a particular element and electron
energy level change. May be called a resonance
wavelength.
12

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Engineering Encyclopedia

Saudi Aramco DeskTop Standards

THEORY OF ATOMIC ABSORPTION

Chapter : Laboratory Science

For additional information on this subject, contact

Basic Atomic Absorption and Emission Spectroscopy

Saudi Aramco DeskTop Standards

Basic Atomic Absorption and Emission Spectroscopy

Figure 1. Atomic Model of Sodium Atom

Saudi Aramco DeskTop Standards

Basic Atomic Absorption and Emission Spectroscopy

This is an illustration of an atom described by the quantum

Figure 2. Atomic Absorption and Emission Process

If enough energy is absorbed, electrons may be completely

Saudi Aramco DeskTop Standards

Basic Atomic Absorption and Emission Spectroscopy

Energy in the form of rays or light is electromagnetic energy.

Figure 3. Electromagnetic Spectrum

The energy of a photon is proportional to the

Saudi Aramco DeskTop Standards

Basic Atomic Absorption and Emission Spectroscopy

ELECTRON CONFIGURATIONS AND EMISSION PATTERNS

Saudi Aramco DeskTop Standards

Basic Atomic Absorption and Emission Spectroscopy

14.0067 15.9994 18.99840 20.179

26.98154 28.0855 30.97376

132.9054 137.33 138.9055 178.49 180.9479 183.85

Unq Unp Unh

101.07 102.9055 106.42 107.8682 112.41

195.08 196.9665 200.59

127.60 126.9045 131.29

140.12 140.9077 144.24

232.0381 231.0359 238.0289 237.0482

157.25 158.9254 162.50 164.9304 167.26 168.9342 173.04

Figure 5. Periodic Table of Elements for Atomic Spectroscopy

Saudi Aramco DeskTop Standards

Basic Atomic Absorption and Emission Spectroscopy

Theory of Atomic Absorption

Figure 6. Visible Spectrum and element Resonance Lines

Saudi Aramco DeskTop Standards

Basic Atomic Absorption and Emission Spectroscopy

LIGHT ENERGY IN ATOMIC SPECTROSCOPY

Saudi Aramco DeskTop Standards

Basic Atomic Absorption and Emission Spectroscopy

Instruments for Atomic Spectroscopy

Atomic Fluorescence Spectroscopy

Figure 7. Instruments for Atomic Spectroscopy

Saudi Aramco DeskTop Standards

Basic Atomic Absorption and Emission Spectroscopy

AES has historically been a method to qualitatively identify

For quantitative AES and atomic fluorescence, emitted light

Saudi Aramco DeskTop Standards

Basic Atomic Absorption and Emission Spectroscopy

Each element has a unique electron energy level distribution

An atom is at ground state when its electrons are in their

An atom is at an excited state when energy has been

An excited atom will return to the ground state by emitting

The energy of a photon is proportional to the wavelength of

Resonance energy is the energy absorbed or emitted for a

Each element has unique resonance energies.

Atomic absorption spectroscopy measures the light energy

Saudi Aramco DeskTop Standards

Basic Atomic Absorption and Emission Spectroscopy

The technology or science of measuring the absorption of