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This photograph is by courtesy of Dr Rod Nave of the Department of Physics and Astronomy at Georgia State University,
Atlanta.
The frequency scale is marked in PHz—petaHertz. Peta means "1015 times". The value 3 PHz is equal to 3 × 1015 Hz. The
quantity "hertz" indicates "cycles per second".
The Lyman series is a series of lines in the ultraviolet region. The lines grow closer and closer together as the frequency
increases. Eventually, they are so close together that it becomes impossible to see them as anything other than a
continuous spectrum. This is suggested by the shaded part on the right end of the series. At one particular point, known as
the series limit, the series ends.
In Balmer series or the Paschen series, the pattern is the same, but the series are more compact. In the Balmer series,
notice the position of the three visible lines from the photograph further up the page.
or
c
ν = (12.3.2)
λ
There is an inverse relationship between the two variables—a high frequency means a low wavelength and vice versa.
When juxtaposed, the two plots form a confusing picture. The remainder of the article employs the spectrum
plotted against frequency, because in this spectrum it is much easier visualize what is occurring in the atom.
1 1 1
= RH ( − ) (12.3.3)
2 2
λ n n
1 2
where
RH is the Rydberg constant.
n1 and n are integers (whole numbers). n is always greater than n . In other words, if n is, say, 2 then n can be
2 2 1 1 2
The higher the frequency, the higher the energy of the light. If an electron falls from the 3-level to the 2-level, red light is
seen. This is the origin of the red line in the hydrogen spectrum. From the frequency of the red light, its energy can be
calculated. That energy must be exactly the same as the energy gap between the 3-level and the 2-level in the hydrogen
atom.
The last equation can therefore be rewritten as a measure of the energy gap between two electron levels:
If an electron falls from the 6-level, the difference is slightly less than before, and so the frequency is slightly lower
(because of the scale of the diagram, it is impossible to depict the levels beyond 7).
All other possible jumps to the first level make up the whole Lyman series. The spacings between the lines in the
spectrum reflect the changes in spacings between the energy levels.
The Paschen series is made up of the transitions to the 3-level, but they are omitted to avoid cluttering the diagram.
As the lines become closer together, the increase in frequency is lessened. At the series limit, the gap between the lines is
zero. Consequently, if the increase in frequency is plotted against the actual frequency, the curve can be extrapolated to the
point at which the increase becomes zero, the frequency of the series limit.
In fact, two graphs can be plotted from the data in the table above. The frequency difference is related to two frequencies.
For example, the figure of 0.457 is found by subtracting 2.467 from 2.924. Which of the two values should be plotted
against 0.457 does not matter, as long as consistency is maintained—the difference must always be plotted against either
the higher or the lower figure. At the limit, the two frequency numbers are the same.
As illustrated in the graph below, plotting both of the possible curves on the same graph makes it easier to decide exactly
how to extrapolate the curves. Because these are curves, they are much more difficult to extrapolate than straight lines.
ΔE = hν (12.3.4)
−34 15
= (6.626 × 10 )(3.28 × 10 ) (12.3.5)
−18
= 2.173 × 10 J (12.3.6)
This is the ionization energy for a single atom. To find the normally quoted ionization energy, this value is multiplied by
the number of atoms in a mole of hydrogen atoms (the Avogadro constant) and then dividing by 1000 to convert joules to
kilojoules.
−18 23
1
I onization energy = (2.173 × 10 )(6.022 × 10 )( ) (12.3.7)
1000
−1
= 1310 kJ mol (12.3.8)
This compares well with the normally quoted value for hydrogen's ionization energy of 1312 kJ mol-1.
Contributors
Jim Clark (Chemguide.co.uk)