Chemistry & Background: Getting Started Techniques Procedure FAQ

ChemLab - Chemistry 6 - Spectrum of the Hydrogen Atom - Chemistry & ...
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Spectrum of the
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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 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
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value in the range 1,2,3, ..., . According to Bohr theory,

which accurately predicts the energy levels for one-electron
atoms like H, He+, Li2+, the energy of an electron in the nth
energy level is given by:
where Z is the nuclear charge, -e is the electron charge, me 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
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.
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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 = Ephoton = Efinal - Einitial = hphoton = hc /
(3)
(4)
(5)
Since e, me, 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 nfinal is less than
ninitial. In an absorption process, the atom gains energy, nfinal
is greater than ninitial and E for the atom is positive. You
can also see that the equation has the same form as Balmer's
empirical one, with nfinal = 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 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)
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= 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, 1s22s22p63s1. 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. 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, (Zeff)3s.
In the Na atom excited electronic configuration
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1s22s22p63p1, 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, (Zeff)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 (Zeff)3s (Zeff)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 Zeff on .
Since (Zeff)3s > (Zeff)3p, the 3s orbital has a lower energy
than 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 =Efinal - Einitial =En= - E3s =0 - E3s = -E3s
and
therefore
(9)
ED line = Efinal - Einitial = E3s - E3p
(10)
E3p = E3s - ED 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:
E3p = E3s + | ED line |
(12)
Once the absolute energy of an orbital and its quantum

number n are known, Zeff 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, ED line and calculate the energies and the Zeff values
for the 3s and 3p orbitals.
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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.
Figure 4
Schematic of the Meterstick Spectroscope, seen from
above.
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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, :
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
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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.
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)
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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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