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PHYS 1301

The Hydrogen Spectrum

Introduction

In a previous laboratory experiment on diffraction, you noticed that light from a mercury
discharge tube was composed of only three colors, or three distinct wavelengths of light.
This feature, that an element emits light of specific colors, is an enormously useful probe
of how individual atoms of that element behave. Indeed, the science of spectroscopy was
developed around the discovery that each element of the periodic table emits light with its
own set characteristic wavelengths, or “emission spectrum.” of light. If one has a
collection of several elements, all emitting light, the spectra of the different elements
combine or overlap. By comparing the combined spectra to the known spectra of
individual elements, you can discover which elements are present. It is amusing to note
that the element helium was first discovered in this manner through the spectroscopic
analysis of light from the sun in 1868 and was only later discovered in terrestrial
minerals in 1895.

But why do we see distinct wavelengths in emission spectra? And why are the spectra
different for particular elements? There is nothing distinct about the light from an
incandescent source such as the ordinary light bulb. In an empirical study of the
spectrum of hydrogen, a school teacher Balmer discovered that the precise frequencies
and wavelengths of the visible light produced could be described by a simple equation
involving a constant and an integer. Balmer's equation was then expanded to describe the
entire spectrum of hydrogen, including the ultra-violet and the infrared spectral lines that
are not visible to the human eye . This equation is called the Rydberg equation:

1 1 1
= R(  ),
 n2 2 n12

where R is the “Rydberg” constant, and n1 and n2 are integers.

The presence of integers in this equation created a real problem for physicists until the
development of the quantum theory of the atom by Niels Bohr. Bohr's theory suggested
that the electron orbiting the nucleus could have only certain quantized energies. The
implication of this idea is that the electron can orbit only at certain fixed distances and
velocities around the nucleus. Individual electron orbits are associated with specific
energy levels. Integer numbers uniquely identify these levels and these integers,
“quantum numbers,” are the ones that show up in the Rydberg equation and that are
labeled n1 and n2.

The integers in Rydberg’s equations identify electron orbits of specific radius. In general,
the larger the value of the integer, the larger the size of the orbit. Rydberg’s equation says
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that the wavelength of the light emitted from an atom depends on two electron orbits. The
interpretation is that an electron makes a transition from the initial orbit identified by the
integer n1 to a final orbit identified by the integer n2. Furthermore, since there is a unique
energy associated with each electron orbit, these integers n1 and n2 also identify or tag the
energy of the electron. Hence, a discrete amount of energy is released or absorbed when
an electron makes a transition between two orbits. In the case of the atom, when an
electron makes a transition from one orbit to another with a lesser value of its identifying
integer, energy is released from the atom and takes the form of emitted light of a distinct
wavelength, or equivalently, of distinct frequency.

So the picture we have is that electron transitions between different orbits produce
different wavelengths of light and that the actual wavelength value of the light depends
on the energy difference between the two orbits. Furthermore, since the energies of the
different orbits and the energies of the transitions are determined by the atomic number
(the number of protons in the nucleus), each atom has its own characteristic spectrum.

In this experiment, you will be measure the wavelengths of the spectral lines of hydrogen,
correlating them with their proper quantum numbers, and experimentally determine
Rydberg’s constant.

Equipment
Hydrogen discharge tube, 2 x meter sticks, short ruler, diffraction grating & holder.

Procedure

Set up the same apparatus as you did for the diffraction experiment, but replace the
mercury discharge tube with the hydrogen tube. You should hopefully be able to see the
four lines of the Balmer series:

Red 656.28 nm
Blue-Green 486.13 nm
Blue 434.05 nm
Violet 410.17 nm

1 nm = 1 x 10-9 m. Measure the wavelengths of these four spectral lines using the method
from the diffraction laboratory, recording both color and wavelength. Try to make
independent measurements of each wavelength from both the first (N = 1) and second-
order (N = 2) diffraction of each spectral line. (Note: in this lab, we will use the symbol N
to denote diffraction order, so as not to get it confused with the energy-level integers). So
the diffraction equation is written
N = d sin 

There are 13400 apertures per inch in the grating.

Analysis

The two integer numbers in the Rydberg equation label the orbits, or energy levels, that
an electron jumps between when light is emitted. For emissions in the visible range of
wavelengths, the final state (n2) is always level 2. Substituting this into the Rydberg
equation gives us the equation for the Balmer series of spectral lines that you observe in
this experiment.

1 1 1
= R( 2  2 ) n = 3, 4, 5 ...
 2 n

where the quantum number n is equal to 3, 4, 5..etc.. with each larger integer
corresponding to a more energetic transition and a shorter wavelength of light emitted.
You will have to associate which value of n goes with each particular spectral line. They
should be in order (red=3, blue-green = 4, etc.) but a certain line may be faint and hard to
detect so you have to be careful to associate each integer with the correct color.

Substitute your measured wavelength and the quantum number to get experimental
values for the Rydberg constant. Take caution to get the correct unit for R. First ask
yourself, if you measure wavelengths in nanometers (nm), what will be the unit of R in
the equation above? You should have up to eight R values in all, one for each spectral
line and order of diffraction.
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Results

Note: use the symbol N to denote diffraction order in this lab, so as not to get it confused
with the energy-level integer n.

Color N (order) x y  
 

 
 
 
 
 
 
 
 

Calculate the Rydberg constant from each of the wavelengths and then average .

Wavelength  Initial state n Rydberg constant R

Rave
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Discussion

1. Compare your experimental value for R to the actual value R = 109,677.58 cm-1
(you will need to carefully convert units).

2. How was the hydrogen spectrum different from the mercury spectrum? Be as specific
as possible and say something about the similarity or difference in colors.

3. Which produces a shorter wavelength, a larger or smaller transition?

4. What do you think the absorption spectrum of hydrogen would look like? Imagine a
rainbow of colors is illuminating a hydrogen tube and you are looking back at the
rainbow of colors through the hydrogen lamp. You may want to draw a simple diagram.

5. What are your primary sources of error in determining R? You need to identify these
sources and then explain their significance.

Conclusions