8/28/13 ChemLab - Chemistry 6 - Spectrum of the Hydrogen Atom - Chemistry & Background

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Spectrum of the
Hydrogen Atom
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Chemistry & Background
The line spectra of the elements, like those observed in this
experiment, show that electrons in atoms can only exist with
discrete, quantized energy values. The state of lowest energy is
called the ground electronic state and an electron in this state can
absorb but cannot emit energy. Discrete states of higher energy
are called excited electronic states. An electron in an excited
electronic state can lose energy and change to a state of lower
energy. This change of energy state, or energy level, by an
electron in an atom is called an electronic transition. The energy
lost by the atom, the energy difference between the initial and
final states, is emitted as a photon. Since electrons in atoms can
exist only with particular, quantized energy values, electronic
transitions are also limited to particular energy values. Thus,
transitions between electronic energy levels, observed either as
emission or absorption of light, occur at discrete energies or
wavelengths. In this way, the four visible lines of light emitted by
hydrogen atoms in excited electronic states can be used to
calculate the differences between energy levels of the electron in
a hydrogen atom.
The hydrogen emission spectrum consists of several series of
lines, named for their discoverers. A series of emission lines
consists of those electronic transitions which all terminate at the
same final level. For example, transitions in the Lyman series,
which appear in the UV region of the spectrum, all terminate at
the ground electronic state of the hydrogen atom. The Paschen,
Brackett, and Pfund series of lines are found in the infrared
region. In addition there is a series of lines, first discovered by
Balmer, in the visible region of the electromagnetic spectrum. The
frequencies of the four lines in this series that you will observe can
be fit to the Balmer equation:
where n is an integer equal to or greater than 3. Balmer's equation
was simply an empirical fit to the observed emission frequencies,
without any basis in theory.
The Bohr model of the atom provides a theoretical basis for
explaining the line spectra of hydrogen atoms. Based on a
planetary model of the atom, Bohr hypothesized that an electron
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could only exist in quantized energy levels, with the electron
orbiting the nucleus at a fixed radius. The allowed quantized
energy levels depend on the value of an integer n, called the
principal quantum number, which can take any value in the range
1,2,3, ..., . According to Bohr theory, which accurately predicts
the energy levels for one-electron atoms like H, He
+
, Li
2+
, the
energy of an electron in the nth energy level is given by:
where Z is the nuclear charge, -e is the electron charge, m
e
is the
mass of the electron,
o
is the permittivity of free space, n is the
principal quantum number, and h is Planck's constant. Note that
the allowed energies are negative numbers and that as n
increases, the energy becomes less negative. This means that an
electron in a level with n=1 is more tightly bound to the nucleus
than an electron in a level with n=2. The zero of energy occurs
when n=, and for this value of n the allowed Bohr orbit has an
infinite radius (this is shown in Eq. 15-7 on p. 539 of Oxtoby,
Gillis, and Nachtrieb). Since the zero of energy corresponds to
the electron and the nucleus at infinite separation and both at rest,
it corresponds to the state of ionization. The energy levels
predicted by Bohr theory for the H atom are shown in Figure 1.
Figure 1
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Energy Levels in the Bohr Atom
and Electronic Transitions of the Balmer Series
Clearly, electronic transitions between the quantized energy levels
of the Bohr atom will give rise to discrete line spectra. For the
Balmer series of hydrogen, light is emitted when an electron
makes a transition from energy levels with n 3 to the n = 2
energy level, as shown in Figure 1. The energy of light emitted
corresponds to the energy level difference between the final and
initial levels (note that Z=1 for H):
E = E
photon
= E
final
- E
initial
= h
photon
= hc / (3)
(4)
(5)
Since e, m
e
,
o
, and h are fundamental constants, this equation
expresses the difference between hydrogen atom energy levels
in terms of the principal quantum numbers of those levels. This
energy level difference corresponds to the energy of the light that
is emitted or absorbed when the electron changes its energy.
Note that in an emission process, the atom loses energy. Its
energy becomes more negative and E for the atom is negative.
This is consistent with the above equation since in an emission
process n
final
is less than n
initial
. In an absorption process, the
atom gains energy, n
final
is greater than n
initial
and E for the
atom is positive. You can also see that the equation has the same
form as Balmer's empirical one, with n
final
= 2.
As an example, let's examine the lowest energy line in the Balmer
Series, where the electron makes a transition from the n=3 level
to the n=2 level. For this case,
= (2.178 10
-18
J) ( 1/22 - 1/32)
(6)
= (2.178 10
-18
J) ( 1/4 - 1/9)
= 3.035 10
-19
J
As mentioned above, since this is an emission process, E for the
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atom is negative. Thus, the energy gained by the surroundings, i.e.
the energy of the emitted photon, is given by |E |, and this can
be converted to the wavelength of light emitted using the
relationship between energy and the wavelength of light, E = h c/
:
= h c / | E | (7)
= 6.5452 10
-7
m = 654.52 nm
Thus, the lowest energy line (which is the longest wavelength
line) in the Balmer series appears in the red portion of the visible
spectrum.
Multielectron Atoms and the Effective Nuclear Charge The
Bohr model of the atom is incorrect in several important ways, for
example, electrons do not move in orbits of fixed radii. However,
the more accurate quantum mechanical theory developed by
Schrdinger confirms the correctness of the Bohr energy level
expression for one-electron atoms: for one-electron atoms the
energy of the electron depends only on the value of the principal
quantum number n:
For multielectron atoms, quantum mechanics shows that energy
levels in such systems are quantized and that the energy of an
electronic level depends on both n and the orbital angular
momentum quantum number, .
To show how this dependence on arises, we compare the case
of the H atom with that of the Na atom. In the H atom, with one
electron and one proton, at any instant the electron always
experiences the same value of the nuclear charge, namely, +1e.
For comparison, consider the ground state Na atom with electron
configuration, 1s
2
2s
2
2p
6
3s
1
. The nuclear charge experienced at
any instant by the 3s valence electron depends on its position
relative to the nucleus compared to the positions of the 10 core
electrons. If the 10 core electrons were always closer to the
nucleus than the 3s valence electron, the 3s electron would
always experience a nuclear charge of +1e, which is the +11e of
the nucleus combined with the 10e charge of the other electrons.
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If this were the case, the 3s valence electron would be perfectly
shielded from the nucleus by the core electrons. However, an
examination of the radial probability distribution plots in Figure 2
reveals that there is, at some instant, a significant probability of
finding the 3s electron closer to the nucleus than some of the core
electrons. At such instants, the 3s electron will experience a
nuclear charge that is greater than +1e. At such instants, the 3s
electron is said to be imperfectly shielded from the full nuclear
charge. Thus, the nuclear charge experienced by the 3s electron
varies from instant to instant, and for such an electron we can only
define an average or effective nuclear charge, (Z
eff
)
3s
.
In the Na atom excited electronic configuration 1s
2
2s
2
2p
6
3p
1
, the
effective nuclear charge experienced by the valence 3p electron
will also vary from instant to instant and, in an analogous fashion,
we can define an effective nuclear charge, (Z
eff
)
3p
, for this
electron. A comparison of the radial probability distribution plots
in Figure 2 for 3s and 3p electrons, shows that there is a greater
probability of finding the 3s electron very close to the nucleus than
there is of finding the 3p electron very close to the nucleus. That
is, the 3s electron can penetrate to the nucleus, and thereby be
closer to the nucleus than some of the core electrons, more
frequently than the 3p electron can penetrate to the nucleus. As a
result, the 3s electron experiences a nuclear charge greater than
+1e more often than does a 3p electron, and (Z
eff
)
3s
(Z
eff
)
3p
.
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Figure 2
At this level of theoretical approximation, the allowed energy
levels for a multielectron atom can be expressed as:
(8)
This equation shows that the dependence of E on arises from
the dependence of Z
eff
on .
Since (Z
eff
)
3s
> (Z
eff
)
3p
, the 3s orbital has a lower energy than
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the 3p orbital. This is clearly consistent with the arguments
presented above; the 3s electron feels a larger effective nuclear
charge, is therefore bound more tightly to the nucleus, and
thereby has a lower (more negative) energy than the less tightly
bound 3p electron.
In the second part of this experiment, you will measure the
spectrum of sodium and determine the wavelength of the emission
line. From this wavelength, the effective nuclear charges of the 3s
and 3p electrons can be calculated.
The sodium emission spectrum has a prominent yellow line, called
the sodium D line. This can be observed in the yellow cast of
low-energy sodium streetlights. This line arises from the transition
of an electron from the excited electronic state in which the
valence electron is in a 3p orbital to the ground electronic state in
which the valence electron is in a 3s orbital. By measuring the
sodium spectrum, you will be able to determine the energy
difference between these two electronic states and thereby the
energy difference between the 3p and 3s orbitals. The existence
of this emission line shows that electrons in the 3s and 3p orbitals
are of different energy and that their energy depends on the , as
well as the n, quantum number.
To determine the absolute energies of the sodium 3s and 3p
orbitals, additional information is required. This is provided by the
ground state ionization energy, which is the energy required to
remove the 3s valence electron from the ground electronic state
of the sodium atom. That is, the ionization energy is the energy of
a transition from the 3s level to the n= level. This is shown
schematically in Figure 3.
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Figure 3
Schematic of Sodium Atom Energy Levels
The ionization energy of gaseous sodium atoms is 496 kJ mol
-1
,
or 8.32 10
-19
J for a single sodium atom. This value can be
used with the wavelength of the sodium D line to determine
absolute energy values for the 3s and 3p levels. The wavelength
of emitted light corresponds to the difference between the 3s and
3p orbital energies. The ground state ionization energy (IE) is the
energy required to transfer the valence electron from the 3s
energy level to the n= level, which is defined as the zero of
energy. Thus,
IE =E
final
- E
initial
=E
n=
- E
3s
=0 - E
3s
= -E
3s
(9)
and E
D line
= E
final
- E
initial
= E
3s
- E
3p
(10)
therefore E
3p
= E
3s
- E
D line
(11)
Recall, that for an emission process, E is negative, since the
atom loses energy. Thus, the above equation can be written in the
alternate form:
E
3p
= E
3s
+ | E
D line
| (12)
Once the absolute energy of an orbital and its quantum number n
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are known, Z
eff
can be calculated using equation (8). For the
sodium portion of this experiment, you will determine the
wavelength of the D line, convert this into an energy, E
D line
and
calculate the energies and the Z
eff
values for the 3s and 3p
orbitals.
The Meterstick Spectroscope and the Diffraction Equation
In this experiment, a simple spectroscope made from metersticks
will be used to observe atomic spectra. The light is supplied by a
gas discharge tube, which works like a neon sign. A sample of
gas is sealed inside a glass envelope, with electrodes in it. A high
voltage is applied across the electrodes and a plasma is formed,
with free, accelerated electrons dissociating the hydrogen
molecules into excited atoms. These excited atoms emit light, as
electrons in excited electronic states make transitions to electronic
levels of lower energy. A diffraction grating is used to separate
the emitted light into its component wavelengths and a meterstick
is used to measure the positions of the emitted lines of light.
A schematic diagram of the meterstick spectroscope is shown in
Figure 4. Light from the discharge tube passes through a
collimating slit and the incident beam is transmitted through a
diffraction grating. A transmission diffraction grating is made by
cutting equally spaced parallel grooves (also called rulings) in a
glass plate. The incident beam of light is diffracted by the rulings
on the grating and emission lines can be viewed along the
meterstick, on either side of the incident beam, as indicated by
observers 1 and 2 in Figure 4. Emission lines of different
wavelengths are diffracted at different angles, , and appear at
different positions on meterstick a. This is shown by the three
different arrows for observer 2. Each of the three emission lines
shown on the left side of the slit was diffracted a different angle
and each has a different wavelength. The diffraction equation
discussed in lecture and reproduced below can be used, with the
distances from the slit to the observed line and from the slit to the
grating to determine the wavelengths of the observed lines of light.
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Figure 4
Schematic of the Meterstick Spectroscope, seen from above.
Arrows indicate the path of light.
A derivation of the fundamental diffraction equation required for
analysis of the spectral data was given in lecture and is
reproduced here. In order for constructive interference to occur
at the angle , waves from the upper ruling on the diffraction
grating must be in phase with waves from the lower ruling, as
shown in Figure 5.
Figure 5
A beam of light from the discharge tube is collimated by the slit
and strikes the diffraction grating.
Figure 6 shows that this is possible if the path difference TS
corresponds to an integral number of wavelengths, :
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Figure 6
Close-up of the diffraction of light by one ruling on the grating.
The path difference is TS.
That is,
TS = m where m = 0, 1, 2, 3,... (13)
A consideration of the right-angle triangle RST shows that
sin = TS/d (14)
where d is the spacing between centers of adjacent rulings on the
diffraction grating. Thus for constructive interference
m = d sin where m = 0, 1, 2, 3,... (15)
Here m is an integer called the order of diffraction, d is the
spacing between centers of adjacent rulings on the diffraction
grating, and is the angle, relative to the direction of the incident
beam, at which constructive interference occurs.
In this experiment, you will observe the first-order diffraction
pattern, so that m is always equal to 1. Thus, the diffraction
condition reduces to = d sin . From this equation it should be
clear that for a given value of d (i.e. for a given diffraction
grating), the angle at which constructive interference occurs will
depend on the wavelength, , of the emitted radiation.
Conversely, this equation shows that the measurement of the
angle leads directly to a calculation of the wavelength, . This
diffraction angle, , can be determined from the position of the
diffracted emission lines on the meterstick, as shown in Figure 7.
You may wish to convince yourself of this geometry.
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Figure 7
Geometry of the Meterstick Spectroscope
For the observation of an emission line at distance a on the
meterstick,
= arctan (a/b) (16)
To determine the wavelength, , of the observed line, this is
combined with the first-order diffraction condition to give
= d sin (17)
= d sin (arctan a/b)
Thus, from measurements of a and b and the spacing (d) between
adjacent rulings on the diffraction grating, the wavelength of
emission lines can be calculated.
How Does a Fluorescent Light Work?
A fluorescent light operates like a discharge tube, but has been
optimized to give diffuse, white light in order to be easier on the
eyes. The tube of a fluorescent light bulb contains a low pressure
of gas, which emits visible and UV light when a voltage is applied
across the tube's electrodes. The inside of the tube is coated with
a phosphorescent material that re-emits this light at wavelengths
throughout the visible region, making the light from the lamp
appear white. In the final part of this experiment, you will
compare the spectrum of a fluorescent light to that of several
elements, to determine what gas is inside the fluorescent tube.
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