9/13/2023

Atomic Spectra
Atomic Absorption and Emission
Spectroscopy
Hydrogen Spectral Lines

CHEM 4138

Bohr Model of the Atom

Electrons
nucleus (+)
in Atoms

electron (-)

Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem

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Prism
• White light is made
up of all the colors of
the visible spectrum.
• Passing it through a
prism separates it.

Continuous Spectrum

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If the light is not white

• By heating a gas or
with electricity we
can get it to give off
colors.
• Passing this light
through a prism does
something different.

• These are called

line spectra
• unique to each
element.
• These are
emission spectra
• The light is
emitted given off.

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Atomic Spectrum
• Each element gives
off its own
characteristic colors.
• Can be used to
identify the atom.
• How we know what
stars are made of.

 If the source is a heated gas, such as the neon in an

advertising sign, the spectrum includes only a few
colors in the form of isolated sharp parallel lines.
 A spectrum of sharp parallel lines is called an
emission line spectrum and the lines are called
spectral lines.

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Wavelength (nm)
excited state 410 nm 486 nm 656 nm
434 nm

Slits Prism

ENERGY IN PHOTON OUT

ground state

Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem

• electrons exist only in orbits with specific

amounts of energy called energy levels
• Therefore…
• electrons can only gain or lose certain
amounts of energy
• only certain photons are produced

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Bohr Model

6
5
4
• Energy of photon
3
2
depends on the
1
difference in energy
nucleus levels

• Bohr’s calculated
energies matched the IR,
visible, and UV lines for
the H atom
Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem

 Each element has a unique bright-line

emission spectrum.
i.e. “Atomic Fingerprint”

Helium
Bohr’s calculations only worked for hydrogen! 

Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem

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Kelter, Carr, Scott, Chemistry A Wolrd of Choices 1999, page 76 Animation by Raymond Chang – All rights reserved.

Line spectrum

Line Emission Spectrum of Hydrogen Atoms

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(a) Electronic absorption transition

(b) H2 emission spectrum (top), H2

absorption spectrum (bottom)
Copyright © 2007 Pearson Benjamin Cummings. All rights reserved.

Higher-energy
orbit

Photon e-

Lower-energy
orbit

(a) Electronic absorption transition

(b) H2 emission spectrum (top), H2

absorption spectrum (bottom)
Copyright © 2007 Pearson Benjamin Cummings. All rights reserved.

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continuous spectrum

gas
absorption spectrum
hot source

emission spectrum

Lyman series Balmer series Paschen series

(ultraviolet) (visible) (infrared)
Frequency 1016 1015 1014
(hertz)

n= 765 4 3 2 1

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HYDROGEN SPECTRAL LINES (ultraviolet)

(visible)

(infrared)

Copyright © 2007 Pearson Benjamin Cummings. All rights reserved.

Hydrogen Spectral Lines

Bohr’s model of the atom accounted mathematically for the energy of each of the transitions shown.

ionization

IR
E6
region
E5
656 nm
E4

E3
A B C D

486 nm
Paschen (IR)
E2
A B C D E
Energy

434 nm
Balmer (Visible)

410 nm

UV
region
E1
A B C D E F

Lyman series (UV)

Davis, Metcalfe, Williams, Castka, Modern Chemistry, 1999, page 97

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Line Spectra
 Heated materials emit light and different materials
emit different kinds of light.
 Toaster coils glow red when in operation; match
flames have a yellow color; and the flame from a
gas stove is blue.
 To analyze this light, we can use a prism or a
diffraction grating to separate the various
wavelengths in a beam of light into a spectrum.
 If the light source is a hot solid (such as the filament
of a light bulb) or liquid, the spectrum is
continuous; light of all wavelengths is present.

Why does a given kind of atom emit and absorb only

certain very specific wavelengths?
 Atoms are much smaller than wavelengths of visible
light, so we can not actually see an atom using the
light.
 In the early 1900’s, Thomson believed that if an atom
collided with another atom, as in a heated gas, each
electron would oscillate around its equilibrium position
with a characteristic frequency and emit
electromagnetic radiation with that frequency.
 If the atom were illuminated with light of many
frequencies, each electron would selectively absorb
only light whose frequency matched the electron’s
natural oscillation frequency (resonance).

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 Each spectral line corresponds to a definite wavelength and

frequency.
 Each element in its gaseous state has a unique set of wavelengths
in its line spectrum.
 Scientists use the line spectra to identify elements and
compounds. For example: astronomers use line spectra to
identify molecules in interstellar space.
 While a heated gas selectively emits only certain wavelengths, a
cool gas selectively absorbs certain wavelengths.
 If we pass white light (continuous spectrum) light through a gas
and look at the transmitted light, we find a series of dark lines
corresponding to the wavelengths that have been absorbed.
 This is called an absorption line spectrum.
 A given atom or molecule absorbs the same characteristic set of
wavelengths when it Is cool as it emits when heated.
 Scientists use the absorption line spectra to identify substances in
the same way they can use emission line spectra.

 Rutherford suggested that electrons revolve in

orbits around the nucleus, just like the planets
revolve around the Sun.
 As the electrons radiated energy, their angular
speeds would change continuously and they would
emit a continuous spectrum, not the line spectrum
actually observed.
 Rutherford’s model of electrons orbiting the
nucleus, based on Newtonian mechanics and
classical electromagnetic theory, makes three
entirely wrong predictions about atoms:
1. They should emit light continuously.
2. They should be unstable.
3. The light they emit should have a continuous spectrum.

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According to Classical Physics:

 An orbiting electron is accelerating, so it should radiate
electromagnetic waves.
 The waves should carry away energy, so the electron should
lose energy and spiral inward.
 The electron’s angular
speed should increase as
its orbit shrank, so the
frequency of the radiated
waves should increase.
 Classical physics says
that atoms should
collapse within a
fraction of a second and
should emit light with a
continuous spectrum as
they do so.

 Classical electromagnetic theory states that any

accelerating electric charge (either oscillating or revolving)
radiates electromagnetic waves.
 An electron orbiting inside an atom would always have a
centripetal acceleration toward the nucleus, and so should
be emitting radiation at all times.
 The energy of an orbiting electron should therefore
decrease continuously, its orbit should become smaller and
smaller, and it should spiral into the nucleus within a
fraction of a second.
 According to classical theory, the frequency of the
electromagnetic waves emitted should equal the frequency
of revolution.

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Energy Levels and the Bohr Model of the Atom

 Bohr’s hypothesized that the emission line spectrum of
an element tells us that atoms of that element emit
photons with only certain frequencies f and certain
specific energies E = h·f.
 During the emission of a photon, the internal energy of the
atom changes by an amount equal to the energy of the
photon.
 Each atom must be able to exist with only certain specific
values of internal energy.
 Each atom has a set of possible energy levels, but it cannot
have an energy intermediate between two levels.

 All atoms of a given element have the same set of energy

levels, but atoms of different elements have different
sets.
 If an atom is raised, or excited, to a high energy level, the
excited atom can make a transition from one energy level to
a lower energy level by emitting a photon with energy equal
to the energy difference between the initial and final levels.
 If Ei is the initial energy of the atom before a transition, Ef is
the final energy after the transition, and the photon’s
energy is h·f = (h·c)/λ, then conservation of energy gives:

hc
h f   Ei  E f


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 For example: an excited lithium atom emits red light

with wavelength λ = 671 nm. The corresponding photon
energy is:
hc 6.63x1034 J  s  3x108 m
E  s
9
 671x10 m
19
E  2.96 x10 J  1.85 eV

 Emission line spectra show that many different wavelengths

are emitted by each atom.
 Each kind of atom must have a number of energy levels,
with different spacing between each energy level.
 Each wavelength in the spectrum corresponds to a
transition between two specific energy levels of the atom.
 Caution: the lines of an emission line spectrum are not all
produced by a single atom. The spectrum from a gas
shows the light emitted from all the different transitions
that occurred in different atoms of the sample.

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 The observation that atoms are stable means that each

atom has a lowest energy level, called the ground level.
 Levels with energies greater than the ground level are called
excited levels.
 An atom in the excited level, called an excited atom, can
make a transition into the ground level by emitting a
photon.

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Atomic Absorption
 Collisions are not the only way that an atom’s energy can be
raised from one level to a higher level.
 If an atom initially in the lower energy level is struck by a
photon with just the right amount of energy, the photon can
be absorbed and the atom will end up in the higher level.
 In a previous example, we mentioned two levels in the
lithium atom with an energy difference of 1.85 eV. Therefore
– For a photon to be absorbed and excite the atom from the lower
level to the higher one, the photon must have an energy of 1.85 eV
and a wavelength of 671 nm.
– An atom absorbs the same wavelengths that it emits.

 This explains the correspondence between an element’s

emission line spectrum and its absorption line spectrum.
 A lithium atom cannot absorb a photon of wavelength 670
nm or 672 nm, its all or nothing, which explains why
absorption line spectra have distinct dark lines.
 Atoms can only absorb photons with specific wavelengths.
 An atom that has been excited into a high energy level does
not stay there long.
 After a short time, called the lifetime of the level (about 10-8
s), the excited atom will emit a photon and make the
transition into a lower excited level or the ground level.

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 To keep a gas of atoms glowing, energy must continually be

provided to re-excite atoms so tht they can emit more
photons.
Example: Emission and Absorption Spectra
 A hypothetical atom has energy levels at 0.0 eV (ground
level), 1.0 eV, and 3.0 eV. What are the frequencies and
wavelengths of the spectral lines this atom can emit when
excited?

E 1.0 eV
f   15
 2.42 x1014 Hz
h 4.136 x10 eV  s
E 2.0 eV
f   15
 4.84 x1014 Hz
h 4.136 x10 eV  s
E 3.0 eV
f   15
 7.25 x1014 Hz
h 4.136 x10 eV  s

c 3x108 m
  s  1.24 x10 6 m
14
f 2.42 x10 Hz

c 3x108 m
  s  6.2 x10 6 m
f 4.84 x1014 Hz

c 3x108 m
  s  4.14 x10 6 m
14
f 7.25 x10 Hz

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 What wavelengths can this atom absorb if it is in

its ground level?
– From the ground level, only a 1 eV or 3 eV photon can be
absorbed.
– A 2 eV photon cannot be absorbed because the atom has
no energy level 2 eV above the ground level.
– Passing light from a hot solid through a gas of these
hypothetical atoms (almost all of which would be in the
ground state if the gas were cool) would yield a
continuous spectrum with dark absorption lines at 1240
nm and 414 nm.
– If a gas of these atoms were at a sufficiently high
temperature, collisions would excite a number of atoms
into the 1 eV energy level and these excited atoms can
absorb 2 eV photons and an absorption line at 620 nm
would appear in the spectrum.

 Suppose we take our hypothetical gas and illuminate it

with violet light of wavelength 414 nm.
– Atoms in the ground level can absorb this photon and
make a transition to the 3.0 eV level.
– Some of these atoms will make a transition back to the
ground level by emitting a 414 nm photon.
– Other atoms will return to the ground level in two steps,
first emitting a 620 nm photon to transition to the 1.0 eV
level, then a 1240 nm photon to transition back to the
ground level.
– Thus this gas will emit longer-wavelength radiation than
it absorbs, a phenomenon called fluorescence.

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Are Energy Levels Real?

 Franck and Hertz Experiment: Franck and Hertz
studied the motion of electrons through mercury
vapor under the action of an electric field.
 They found that when the electron kinetic energy
was 4.9 eV or greater, the vapor emitted ultraviolet
light of wavelength 250 nm.
 Suppose mercury atoms have an excited energy
level 4.9eV above the ground level.
 An atom can be raised to this level by collision with
an electron; it later decays back to the ground level
by emitting a photon.

 The wavelength of the photon should be:

15 8 m
h  c 4.136 x10 eV  s  3x10 s
   2.5 x107 m  250 nm
E 4.9 eV
 This is equal to the wavelength Franck & Hertz
measured, which demonstrates that this energy
level actually exists in the mercury atom.

Electron Waves and the Bohr Model of Hydrogen

 Bohr’s hypothesis established the relationship
between atomic spectra and energy levels.
 It did not provide general principles for predicting
the energy levels of a particular atom.

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 Bohr postulated that each energy level of a hydrogen

atom corresponds to a specific stable circular orbit of
the electron around the nucleus.
 Bohr postulated that an electron in such an orbit does
not radiate (a break from electromagnetic theory).
 Instead, an atom radiates energy only when an electron
makes a transition from an orbit of energy Ei to a
different orbit with lower energy Ef, emitting a photon
of energy hf = Ei – Ef.
 Relating angular frequency of the light emitted to the
angular speed of the electron in highly excited energy
levels, Bohr found that the electron’s angular
momentum is quantized.

 The angular momentum of an electron is an

integral multiple of h .
2

 Number the orbits by integer n, where n = 1, 2, 3, …

and call the radius of orbit n rn and the speed of the
electron in that orbit vn.
 The value of n for each orbit is called the principal
quantum number for the orbit.
 The angular momentum of an electron of mass m in
such an orbit is h
Ln  m  vn  rn  n 
2

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 deBroglie’s picture of electron waves

can be used to justify Bohr’s equation.
 Instead of visualizing the orbiting
electron as a particle moving around
the nucleus in a circular path, think of
the orbiting electron as a sinusoidal
standing wave with wavelength λ that
extends around the circle.
 A standing wave on a string transmits
no energy, and electrons in Bohr’s orbit
radiate no energy.
 For the wave to come out even and join
onto itself smoothly, the circumference
of this circle must include a whole
number of wavelengths as shown.

 For an orbit of radius rn and

circumference 2·λ·rn, we must have
2·λ·rn = n·λ, where n is the wavelength
and n = 1, 2, 3, …
 From the deBroglie wavelength
equation, the wavelength of a particle
with mass m moving with speed vn is
h
n 
m  vn
 Substituting into the circumference
equation: h
2    rn  n 
m  vn

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 This matched Bohr’s results; a wave picture of the

atom also leads to the quantization of the
electron’s angular momentum.
 Consider the hydrogen atom consisting of a single
electron with mass m and charge –e in a circular
orbit around a single proton with charge +e.
 The centripetal acceleration of the electron about
the proton is vn 2 and the centripetal force needed
rn vn 2
F m
to produce this acceleration is: c rn
 The electrical attraction between the proton and
the electron provides the centripetal force on the
electron.

k  e 2 m  vn 2 n h
 m  vn  rn 
rn 2 rn 2
n h 2 k  e 2  rn
vn  vn 
2    m  rn m  rn 2
substitute vn into vn 2
2
 n h  k  e2
  
 2    m  rn  m  rn
n2 h2 k  e2

4   2  m 2  rn 2 m  rn

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
n2 h2 k e2
 an m and rn cancel
4   2  m 2  rn 2 m  rn
n2 h2
2
 k  e2
4    m  rn

 The orbital radii in the Bohr model):

n2 h2
rn 
4   2 k m  e2

 Orbital speeds in the Bohr model:

e2
vn 
2  o  n  h
 The orbital radius rn is proportional to n2, so the
smallest orbital radius corresponds to n = 1.
 This minimum radius is called the Bohr radius, ao:
h2
ao   o 
  m  e2
 The orbital radius in the Bohr model can be
rewritten as: 2
rn  n  ao
 Permitted orbits have radii ao, 4·ao, 9·ao, …

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 The radius ao of the smallest Bohr orbit is:

2 2
8.854x10 12 C 
 6.626x10 34 J  s 
ao  N  m2
2

  9.11x10 31kg  1.602x10 19C 
11
ao  5.29x10 m

 Orbital speed vn is proportional to 1/n.

– The greater the value of n, the larger the orbital radius of
the electron and the slower its orbital speed.
– The greatest possible speed of the electron in the
hydrogen atom occurs for n = 1.
Hydrogen Energy Levels in the Bohr Model
 The equations for the kinetic and potential energies
when the electron is in the orbit with quantum
number n:

1 2 m e4
Kn   m v 
2 8  o 2  n 2  h 2
k e4 m  e4
Un   
rn 4  o 2  n 2  h 2
 Potential energy has a negative sign because we
have taken the electric potential energy to be zero
when the electron is infinitely far from the nucleus.
 We are interested only in the differences in energy
between orbits, so the reference position doesn’t
matter.
 The total energy En is the sum of the kinetic and
potential energies:

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m  e4
En  K n  U n 
8  o  n 2  h 2
 Since En has a different
value for each n, this
equation gives the
energy levels of the
hydrogen atom in the
Bohr model.
 Each distinct orbit
corresponds to a
distinct energy level.
 The figure depicts the
orbits and energy
levels.

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 For each value of n there is a corresponding

value for the orbital radius rn, orbital speed vn,
angular momentum n  h , and total
energy En. L 
2

 The energy of the atom is least when n = 1 and En

has its most negative value (the ground level of
the hydrogen atom with radius ao).
 For n = 2, 3, 4, … the absolute value of En is
smaller and the energy is progressively larger
(less negative).
 The figure on the next slide shows some of the
possible transitions from one electron orbit to an
orbit of lower energy.

 Transition
from orbit nU
(upper) to nL
(lower)
results in the
energy
h c
E

of the
emitted
photon of
wavelength λ
equal to
EnU - EnL

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 From the energy equation:

m  e4
En  K n  U n 
8  o  n 2  h 2
 We rewrite the equation:
h c  R m e4
En   where R
n2 8  o 2  h 3  c

 R is the Rydberg constant; R = 1.097 x 107/m.

 Equation for the hydrogen wavelengths in the Bohr
model, nL < nU:
1  1 1 
 R  2  2 
  nL nU 

 When a hydrogen atom absorbs a photon, an

electron makes a transition from a level nL to a
higher level nU.
– This can happen only if the photon energy is equal to
EnU – EnL.
– The wavelength equation also predicts the wavelengths
found in the absorption line spectrum of hydrogen.
 the Bohr model predicts the values of the observed
wavelengths for electron transitions within the
hydrogen atom.
– Lyman series involves electron transitions from nU = 2, 3,
4, … to nL = 1.
– Balmer series involves electron transitions from nU = 3, 4,
5, … to nL = 2.

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 Paschen series involves electron

transitions from nU = 4, 5, 6, 7 to nL = 3.
 Brackett series involves electron
transitions from nU = 5, 6, 7 to nL = 4.
 Pfund series involves electron transitions
from nU = 6, 7 to nL = 5.
 The figure shows only transitions in which
a hydrogen atom loses energy and a
photon is emitted.

 The wavelengths of those photons that an atom

can absorb are the same as those that it can emit.
 The Bohr model also predicted the value of the
ionization energy of the hydrogen atom.
– Ionization energy is the energy required to remove the
electron completely from the atom.
– Ionization corresponds to the transition from the ground
level (n = 1) to an infinitely large orbit (n = ), so the
energy that must be added to the atom is E - E1 = 0- E1 =
-E1 = -(-13.6 eV) = 13.6 eV.

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 Example: Exploring the Bohr Model

 Find the kinetic energy, potential energy, and total
energies of the hydrogen atom in the first excited
level.
m  e4 m e4
Kn  but h c  R 
8  o 2  n 2  h 2 8  o 2  h 2
h c  R
Kn 
n2

m  e4 m e4
Un   but h c  R 
4  o 2  n 2  h 2 8  o 2  h 2
2h c  R
Un  
n2

m e4 m e4
En   but h c  R 
8  o 2  n 2  h 2 8  o 2  h 2
h c  R
En  
n2
h  c  R  6.626x1034 J  s  3x108 m  1.097x107 / m
s
18
h  c  R  2.179x10 J  13.6 eV

 For the first excited energy level (n = 2), and

expressed in terms of h·c·R:
13.6ev 13.6ev
Kn    3.4eV
n2 22
2  13.6ev 2  13.6ev
Un    6.8eV
n2 22
13.6ev 13.6ev
En    3.4eV
n2 22

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 Find the wavelength of the photon emitted in a

transition from n = 2 to the ground level.
– The energy of the emitted photon is E2 – E1.

h c 4.136x10 15 eV  s  3x108 m

  s
E 2  E1 3.4eV   13.6eV 
  1.22x107 m  122 nm

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