Physics 30 Lesson 30

Light Spectra & Excitation States

So far in our study of the nature of the atom we have learned about the nuclear model
of the atom and the quantization of light energy. In this lesson we will learn about light
spectra and how they led to our current conception of the atom.

I. Types of spectra
Light spectra are the patterns produced when light is either dispersed through an
equilateral glass prism or is diffracted apart by a diffraction grating i.e. light is
separated into its colours. There are three types of spectra.

Continuous Spectrum
When a solid or a liquid is made white hot white light is emitted. When the light passes
through a prism it is dispersed into its colours. The short wavelengths (violet, blue) are
refracted more by the prism than the longer wavelengths (orange, red). The result is a
continuous spectrum of light from violet to red.

white light
source continuous
spectrum

vib g y o r

Recall from Lesson 28 that a hot solid or liquid acts as a blackbody radiator and that the
light emitted is not affected by the type or kind of solid or liquid being heated.

Emission / Bright-line Spectrum

Gases will also produce light when heated to a high temperature. In 1752 a Scottish
physicist name Thomas Melvill observed the spectra produced by a heated gas.

heated or
electrified gas emission
spectrum

v i b g y o r

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Melvill discovered that gases do not produce a continuous spectrum, rather they
produce a spectrum that is composed of bright colored lines against a black
background. We call this type of spectrum a bright line or emission spectrum (i.e.
the gas emits the light). He also noted that the colors and locations of the bright lines
were different when different gases were used.

By 1823, scientists had found that gases could be induced to glow when excited by
electricity. If the gas was sealed inside a tube with an anode and a cathode, it would
glow when electricity was passed through it. Modern electric signs, for example, are
composed of tubes with neon, argon, and other gases which are exposed to a potential
difference. Each gas gives off its own colours of light.

John Herschel, the British Astronomer, suggested that if each gas had a characteristic
bright line spectrum then elements might be identified by their spectrum. Spectral
analysis was the result of this idea. In 1860, Gustav Kirchoff and Robert Bunsen
discovered two substances with unique emission spectra that did not match any known
spectrum at the time. Using this technique they had isolated two new elements: cesium
and rubidium. Many other elements were discovered using this technique.

Absorption / Dark-line Spectrum

In 1802, British scientist William Wollaston found seven dark lines within the continuous
spectrum produced by light from the sun. In 1814, the German physicist Joseph van
Fraunhofer was able to detect hundreds of these dark lines formed on the continuous
solar spectrum. These lines are now called Fraunhofer Lines in his honour.

In 1859, Gustav Kirchoff was able to produce a dark line (absorption) spectrum by
passing white light through a glass container holding cold sodium gas and then viewing
the emerging light with a prism. The gas in the container absorbed a few discreet
wavelengths or colors of light while the majority of the light passed through the gas.

full spectrum white light source absorption

spectrum

vib g y o r

cool gas

Analysis of the dark Fraunhofer lines of solar spectra indicated that the lines matched
those of many known elements. Thus the atmosphere of the sun contained the same
elements as those on Earth. The chemical composition of the outer region of the sun
and of distant stars and galaxies has been determined by this process. The result
indicates that other things in the universe are made of the same elements and
molecules that we find on Earth.

When spectra were recorded and analyzed from galaxies, it was found that their
spectra were shifted from their normal position. Some were shifted toward the blue end
of the spectrum, while others were shifted toward the red. This shift was interpreted as
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a Doppler shift which was the result of the relative movement between the Earth and
the galaxy red shift indicated the galaxy was moving away, blue shift indicated
movement toward the Earth. There are a few neighbouring galaxies which are slightly
blue-shifted, but the vast majority are red shifted. In fact, the more distant the galaxy,
the greater its red shift. Thus we live in an expanding universe. When this was
discovered, it was not long before the theory of the Big Bang was developed. The
universe is expanding as a result of the original explosion between 15 and 18 billion
years ago. The current best estimate is 13.8 billion years.

Refer to Pearson pages 771 to 773 for a discussion about spectroscopy.

Ask to see the spectra of gases demonstration. In addition, study the

spectrum poster on the wall, and I strongly recommend that you go to the
following website:

http://javalab.uoregon.edu/dcaley/elements/Elements.html

II. Comparison of emission and absorption spectra

When Kirchoff compared the emission spectra with the absorption spectra of sodium
vapor, he noted that the position of the dark lines in the absorption spectra
corresponded exactly with the position of the two bright yellow lines in the emission
spectra.

Emission

Absorption

All other elements were quickly checked and an exact match up resulted for all the
other known elements. Apparently the light energy absorbed by an element from white
light matched exactly the light energy emitted by the excited element. However, a
rather puzzling phenomenon was that there were always more lines in the emission
spectrum than in the absorption spectrum. Why? We will answer this question
below.

Absorption spectrum

Emission spectrum

(Sodium vapour)

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III. The Franck Hertz experiment
Earlier studies of emission and absorption spectra had revealed that atoms emit and
absorb light energy only at discrete, characteristic wavelengths or energies, but there
was no theory that could explain how they worked. A significant contribution to our
understanding of atomic structure was provided by a team of two German physicists,
James Franck and Gustav Hertz, in 1914. Franck and Hertz devised an experiment to
investigate how atoms absorb energy in collisions with fast-moving electrons.

Using an apparatus similar to that shown,

free electrons emitted from the cathode
were accelerated through low pressure
mercury vapour by a voltage applied to the
wire screen anode. (An electron
accelerated by a potential difference of 5.0
V, for example, acquires a kinetic energy
of 5.0 eV.) Most of the electrons went
through the screen and were collected by
the anode plate beyond the screen. This
flow of electrons constituted an electric current, which was measured by a
microammeter.

The experiment consisted of gradually increasing the accelerating voltage and, for each
value, measuring the electric current passing through the mercury vapour and collected
by the plate. Franck and Hertz found the following results:
As the accelerating voltage was increased slowly from zero, the current gradually
increased as well.
1 Then, at a voltage of 4.89 V, the
current dropped dramatically.
As the voltage was increased further,
the current once again began to
increase.
Similar minor decreases in current
2
also occurred at voltages of 6.67 V
and 8.84 V.
Another significant decrease in current
3
occurred at a voltage of 9.8 V.

The results indicated that for certain values of bombarding electron energy (4.89 eV,
6.67 eV, 8.84 eV, 9.8 eV, . . . ) the electrons do not "make it" through the mercury
vapour. Their energy is lost because of collisions with mercury vapour atoms. The
proposed explanation was simple, yet elegant:
Whenever the energy of the incident electrons was less 4.0 eV
than 4.9 eV, they simply bounced off any mercury
4.0 eV
atoms they encountered with no loss of energy and electron
continued on as part of the current.
mercury atom

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 Those electrons with an energy of 4.9 eV that collided 0 eV
with a mercury atom transferred all of their energy to
the mercury atom and, therefore, with no energy 4.9 eV
remaining, did not reach the plate. electron

At energies greater than 4.9 eV, electrons colliding with mercury atom
mercury atoms can give up 4.9 eV in the collision and
still move off with the remaining energy and reach the
plate. 1.1 eV

At electron energies of 6.7 eV and 8.8 eV, collisions

6.0 eV
once again rob the bombarding electrons of all their electron
energy, but these collisions are less likely to occur than
those at 4.9 eV, (i.e. mercury atoms prefer to absorb mercury atom
4.9 eV of energy) so that the effect on the current is
less severe.
At 9.8 eV, electrons are able to make a collision, losing 4.9 eV of energy, and then
go on to make a second similar collision with another mercury atom, losing another
4.9 eV of energy. Since these collisions are more probable, a sharper decrease in
current occurs.
The significant result of the Franck-Hertz experiment is that atoms can change their
internal energy as a result of collisions with electrons, but only by specific, discrete
quanta or amounts of energy. Their
interpretation was that the electrons within 10.4 eV ionization level
the atoms normally exist in a ground state many other excitation
levels exist in this region rd
(0 eV). When they are given enough 3 excitation level
energy, they jump up to an excited 8.84 eV
energy state. Only certain excitation nd
2 excitation level
levels are allowed i.e. electrons can only 6.67 eV
absorb specific amounts of energy. The st
1 excitation level
diagram on the right is a representation of 4.89 eV
the energy states of a mercury atom.
Energy diagrams for other elements would
look similar, but they would have different
excitation energies. The ionization level ground state
is when one of mercurys electrons is 0 eV
given enough energy that it leaves the
atom resulting in a positive mercury ion.

As the experiment progressed Franck and Hertz also noted that the mercury vapour
began to emit light. The next step in their experiment was to measure the wavelength
of the light emitted by the excited mercury atoms. When the input electron had energy
of 9.00 eV, the mercury vapour released photons that produced spectral lines at 686.8
nm, 572.9 nm, 312.3 nm, 254.2 nm, 186.4 nm and 140.6 nm. Using Plancks equation,
the energies of each of these wavelengths could be calculated. For example, for the
254.2 nm light
hc 4.14 10 15 eV s(3.00 108 m s )
E = 4.89 eV
254 10 9 m

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A complete list of the corresponding energies of the photons yields:

140.6 nm little bump 8.84 eV Note that these wavelength/energy pairs
186.4 nm little bump 6.67 eV correspond to the excitation levels of mercury
254.0 nm 4.89 eV vapour.
312.3 nm 3.98 eV
572.9 nm 2.17 eV What about these wavelength/energy pairs?
686.8 nm 1.81 eV

Franck and Hertz interpreted the energies and wavelengths as the result of jumps of
mercury atom electrons falling from excitation states down toward the ground state. As
the electron falls or de-excites back toward the ground state, it releases its energy in
the form of a photon. In general, the photons energy is determined by the difference
in the initial (higher) and final (lower) energy levels.
Ephoton Ei E f
The wavelength or frequency of the photon may be calculated using Plancks equation.

The diagram on the right illustrates the

10.4 eV
emission of photons when electrons fall back
from an excitation state directly to the
ground state. 8.84 eV
186.4 nm photon
(6.67 eV)
The remaining wavelength/energy pairs above 6.67 eV
can be explained by intermediate jumps to
lower energy states. For example, an 4.89 eV
electron in the third excitation state could fall
to the second level before falling to the 140.6 nm photon
ground state. The energy of the photon for (8.84 eV) 254.0 nm photon
the jump from E3 to E2 would be the (4.89 eV)
difference in their energies 8.84 eV 6.67 eV 0 eV
= 2.17 eV. The 2.17 eV photon has a
wavelength of
hc hc
= 572.9 nm.
E 2.17eV
which corresponds to one of the observed wavelengths emitted by mercury. The
diagram on the right illustrates the
emission of photons when electrons
10.4 eV
fall back from a high excitation state
312.3 nm photon
to another intermediate excitation (3.98 eV)
state. 8.84 eV
579.2 nm photon
(2.17 eV)
Thus the emission spectrum of an 6.67 eV
element is explained by a
combination of de-excitations to the 4.89 eV
686.8 nm photon
ground state and de-excitations to (1.81 eV)
intermediate excitation states.

0 eV

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IV. Summary of spectra and excitation states

Absorption of energy
Atoms can absorb energy in two ways:
1. By collisions with high energy electrons. In these collisions the electron in the
atom absorbs only the amount of energy corresponding to a jump from the ground
state to an excitation state. The incoming electron continues on with the remaining
energy. For example, a 6.00 eV incoming electron colliding with a mercury atom
will lose 4.89 eV to the atom and then continue on with an energy of 1.11 eV. Note,
for this type of energy absorption, the incoming particle need only have an energy
greater than the first excitation energy.

10.4 eV

8.84 eV

6.67 eV
mercury atom electron
1.11 eV 4.89 eV jumps to first excitation
level

6.00 eV
electron
0 eV

2. By absorbing a photon. In this case, the atom will absorb only those photons that
have energies that exactly match the excitation state energies. Since electrons
normally reside in the ground state, this means that it will absorb only those
photons that match its excitation states from the ground level. Therefore, when full
spectrum white light is sent through a gas, only those wavelengths of light that
correspond to the excitation states of the gas are absorbed by the gas. The
remaining wavelengths simply pass through the gas. This explains the dark lines
for absorption spectra.

10.4 eV
207 nm photon 207 nm photon
(6.00 eV) (6.00 eV)
8.84 eV
186 nm photon
incoming (6.67 eV) 6.67 eV outgoing
photons photons
4.89 eV

177 nm photon 177 nm photon

(7.00 eV) (7.00 eV)

0 eV

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Release of energy
Once atoms have been excited they will eventually fall back to the ground state. Some
atoms, for example hydrogen, will return to the ground state immediately after being
excited. Other atoms, like phosphorous, can stay in an excited state for hours before
returning to the ground state. This is why divers watches have phosphorous paint
numbers they will continue to emit light for hours.

Atoms can fall back to the ground state in one of two ways:
The atom can fall straight back to the ground state from the excitation state. In
this case, one high energy photon is emitted.
The atom can fall through a series of intermediate excitation states to the ground
state. In this case, several lower energy photons will be emitted.

10.4 eV

572.9 nm photon
8.84 eV (2.17 eV)
312.3 nm photon
6.67 eV (3.98 eV)

4.89 eV
140.6 nm photon 254.2 nm photon
(8.84 eV) or or (4.89 eV)

0 eV
186.4 nm photon
(6.67 eV)
The emission of photons when atoms fall back toward the ground state explains two
things about emission spectra:
1. Bright lines of emission spectra correspond with the dark lines of absorption spectra
for the same element or molecule.
2. The presence of more lines in emission spectra compared to absorption spectra
can be explained by the intermediate jumps that can occur when atoms fall toward
their ground state.

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V. Practice problems
A Frank-Hertz experiment was carried out with on Lichtium vapour in a chamber. The
energies of the electrons sent into the chamber (Einput) and those coming out of the
chamber (Eouput) were measured and the data is given below. What can be inferred
about the possible energy levels within this fictitious atom? Assume that the ground
state energy is zero.

Einput (eV) Eoutput (eV)

4.0 4.0
5.0 0.0
5.5 0.5
6.0 1.0
6.5 1.5
7.0 0.0 or 2.0
7.5 0.5 or 2.5
8.0 0.0 or 1.0 or 3.0
8.5 0.5 or 1.5 or 3.5

1. Draw an energy level diagram for Lichtium.

2. What wavelengths of light would you expect Lichtium to absorb? (248 nm, 177
nm, 155 nm)

3. What wavelengths of light would you expect Lichtium to emit? (total of six
wavelengths)

4. If an atom was excited to the fourth excitation state, how many possible
wavelengths of light would be emitted when the atom fell to its ground state? (10)

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VI. Hand- in assignment
1. When a solid, liquid or very dense gas is heated until it gives off light and the light
is passed through a prism, a(n) _______________ spectrum is produced.

2. When a rarefied gas is excited with electrical energy until it gives off light which is
passed through a prism, a(n) _______________ spectrum is produced.

3. Why can an emission spectrum be used to positively identify different elements or

molecules in their gaseous states?

4. When white light is passed through a gas and then allowed to go through a prism,
it will produce a(n) _______________ spectrum.

5. What is the significance of the results of the Frank-Hertz experiment?

6. What is meant by the following terms:

A. An atom's ground state?
B. An atom's excitation states?
C. An atom's ionization energy?

7. An electron of energy 4.7 eV collided with an atom called Chekleyium and was
reflected with an energy of 1.4 eV. Immediately after the atom emitted a photon.
What is the frequency of the photon? (8.0 x 1014 Hz)

8. A mercury atom has stationary energy states of 4.9 eV, 6.7 eV and 8.8 eV above
the ground state.
A. An electron with an energy of 3.6 eV collides with an unexcited atom.
Estimate the energy of the reflected electron.
B. Another electron with an energy of 6.8 eV is incident on the atom. What is
(are) the possible energy(ies) of the reflected electron?

9. A Frank-Hertz experiment was carried out with a fictitious gas in a chamber. The
energies of the electrons sent into the chamber (E1) and those coming out of the
chamber (E2) were measured and the data is given below. What can be inferred
about the possible energy levels within this fictitious atom? Assume that the
ground state energy is zero.
Einput (eV) Eoutput (eV)
6.4 6.4
6.7 6.7
6.8 0.0
7.8 1.0
8.7 0.0 or 1.9
8.9 0.2 or 2.1
9.1 0.4 or 2.3
9.3 0.0 or 0.6 or 2.5
9.5 0.2 or 0.8 or 2.7

10. What happens to a mercury atom that has been raised to its first excitation level
by a collision with an electron?

11. What is the explanation for the absorption spectrum of an element?

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12. Why are most gases invisible to the human eye?

13. Why does an emission spectrum contain more lines than an absorption spectrum?

14. What will happen when an electron of energy 5.0 eV collides with a mercury
atom? What will happen when a photon of energy 5.0 eV hits a mercury atom?

15. A spectroscope is used to examine the white light that has been passed through a
sample of mercury vapour. Dark lines, characteristic of the absorption spectrum
of mercury, are observed.
A. What eventually happens to the energy the mercury vapour absorbs from the
white light?
B. Why, then, are the absorption lines dark?

16. The emission spectrum of an unknown substance contains lines with the following
wavelengths: 172 nm, 194 nm, and 258 nm. If these all represent transitions to
the ground state (a) calculate the energies of the first three excitation states, and
(b) determine the wavelengths of three other lines in the substances emission
spectrum. (4.82 eV, 6.41 eV, 7.23 eV; 516 nm, 782 nm, 1517 nm)

17. What is the energy difference between the two energy levels in a sodium atom
that give rise to the emission of a 589 nm photon? (2.1 eV)

18. An electron whose kinetic energy is 3.0 eV collides with a free mercury atom.
What will be the kinetic energy of the electron after the collision? (3.0 eV)

19. Electrons are accelerated in a Franck-Hertz experiment through mercury vapour

with a potential difference of 7.0 V. What are the energies of all the photons that
may be emitted by the mercury vapour? (4.9 eV, 6.7 eV, 1.8 eV)

20. If an atom emits a photon of wavelength 684 nm, how much energy dos the atom
lose? (1.82 eV)

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