Experimental Determination of Rydberg’s
Constant
Ryan Eagan
Pennsylvania State University
University Park, Pennsylvania 16802
Email: [email protected]
July 25, 2011
Abstract
Discrete emission line spectra of hydrogen is observed and measured
using diffraction grating spectrometry to obtain the respective wavelengths
of the four visible lines in the Balmer series. Using the known corre-
sponding energy levels for the Balmer lines and observed wavelengths
substituted into Rydberg’s formula, an experimental value of Rydberg’s
constant is found Rexp = 1.095 ×107m−1and compared to the accepted
value R= 1.097 ×107m−1. The empirical results are within acceptable
limits with an error difference of 0.26%.
1 Introduction
The earliest beginnings of quantum theory can be attributed to the study of
discrete line spectra throughout the 1800’s. Hydrogen generates the simplest
line spectra of four visible lines: red ( λ= 656.3 nm), green (λ=486.1 nm), blue
(λ=434.1 nm), and violet (λ=410.2 nm)[1]. In 1885 Johann Balmer published
a paper announcing an empirical formula that predicted the the wavelengths of
the four visible lines as given by:
λ(cm) = C2(n2
n2−22)n= 3,4,5, ... (1)
where C2= 3645.6×10−8cm[2]. Balmer’s formula provided no theoretical basis,
though it predicted the wavelengths of other hydrogen spectral series.
The next contribution to Balmer’s work came from Johannes Rydberg in
1889 who recast Balmer’s empirical formula (Eq. 1) into a more generalized form
that could predict the discrete line spectra series for other elements. Rydberg’s
formula is given by 1
λ=R(1
nf2−1
ni2) (2)
1
where R= 1.09737×107m−1is Rydberg’s constant, niand nfare integers called
the principle quantum numbers with ni> nf. The significance of the Rydberg
constant was not understood in its entirety until 1913 when Neils Bohr published
a paper on the structure of the atom[3].
In Bohr’s structural atomic model, the discrete emission spectra are repre-
sentative of electron transitions from higher energy states to lower energy states
that emit photons of a specific wavelength determined by:
1
λ=f
c=ke2
2a0hc(1
nf2−1
ni2) (3)
where k= 8.99 ×109N·m2/C2is Coulombs constant, a0= 0.5292 ×1010mis
the Bohr radius, h= 6.626 ×10−34J·sis Planck’s constant, e= 1.602 ×10−19C
is the magnitude of electron charge and c= 2.998×108m/s the speed of light[4].
The principle quantum numbers now represent the discrete allowed energy levels
for the electrons with n= 1 being the lowest energy or ground state. We now
show the significance of Rydberg’s experimentally determined constant given
as:
R=ke2
2a0hc (4)
by substitution into (3) thus yielding Rydberg’s formula Eq. (2). Bohr showed
in his model that the orbiting electron had a quantized radius ultimately giving
way to the quantization of energy with allowed energy levels:
En=ke2
2a0
(1
n2)n= 1,2,3, ... (5)
where Enis the energy associated with a particular state and for the ground
state (n= 1) the energy is E1= 13.6eV . The final energy state in the Balmer
series is the lowest excited state (n= 2) and has an energy of E2= 3.4eV .
The corresponding initial energy states and respective photon wavelengths are
shown in Figure 1.
Using diffraction grating spectral analysis techniques to obtain the wave-
lengths of the Balmer series from a hydrogen discharge tube, Rydberg’s constant
is measured experimentally by solving (2) for R:
R=4ni2
λ(ni2−4) (6)
The observed hydrogen emission spectra provided only two of the four lines in
the Balmer series, green and red. Despite the lack of the blue and violet lines,
the experimentally determined value for R(1.095 ×107m−1) is well within the
tolerable range of the current accepted value 1.097 ×107m−1.
2
Figure 1: Energy-level transitions for various spectral series including the
Balmer series.
2 Experimental Methods
Spectral analysis of hydrogen gas was performed by diffraction grating spec-
trophotometry. A PASCO spectrophotometer1configured with a PASCO high
sensitivity light sensor2and rotary motion sensor3provided light intensity with
respect to angular position. The collimated light from the hydrogen discharge
tube was propagated through a diffraction grating with a grating line spacing
of 1673nm. The line spacing of the diffraction grating was determined using
a PASCO red diode laser4with a wavelength of 650nm. Observation of the
first order fringes in the laser diffraction pattern was obtained to determine the
deviation from the central order maximum. Diffraction grating line spacing d
was then calculated using the known wavelength and :
d=sin θ
mλ (7)
where m= 1 to yield 1.673 ×10−6mfor the value of d.
Angular position data was obtained by the rotary motion sensor coupled
with the revolving degree plate used to rotate the light sensor. Angular position
calibration was performed over five trials to obtain the mean ratio (0.0169s−1)
between the degree plate and rotary motion sensor armature, thus the angular
position of spectral data yis given by y=x
59.238 where xis the position reported
by the rotary motion sensor with a sample frequency of 1400 Hz.
1PASCO Spectrophotometer, Model No. OS-8537
2PASCO High Sensitivity Light Sensor, Model No. CI-6604
3PASCO Rotary Motion Sensor, Model No. CI-6538
4PASCO Red Diode Laser, Model No. OS-8525A
3
3 Experimental Results
Spectral data was obtained for four trials using the same hydrogen discharge
tube. The plot of intensity vs. angular position was then analyzed in PASCO’s
DataStudio5software to obtain the deviation (difference between the central
maximum fringe m= 0 and the respective first order fringe m= 1) of the first
order spectral patterns. The corresponding wavelength was then determined by
λ=dsin θ
m(8)
where d= 1.673 ×10−6mis the diffraction grating line spacing and m= 1 for
the first order bright fringes.
Table 1: The exact value of the wavelength for Bαis λ= 656.3nm and Bβis λ=
486.1nm. The observed values, with the exception of Bβin Trial 2, are very close to
the exact values.
Balmer Line Trial λnm Robserved (1 ×107m−1)
1 654.6 1.0999
Bα2 654.8 1.0996
3 656.1 1.0974
4 656.1 1.0974
1 486.4 1.0965
Bβ2 494.0 1.0797
3 488.0 1.0929
4 488.0 1.0929
The observed spectrum produced only the Balmer Alpha (red, ni= 3) and
Balmer Beta (green, ni= 4) lines. The data obtained for both lines in the series
were taken from the right side of the central maximum which proved to be the
more pronounced or brighter side of the spectrum. Figure 2 shows the obtained
spectrum for the fourth trial.
The experimental value of Rwas calculated for each Balmer line over four
trials as listed in Table 1. The mean experimental value for Rwas 1.095 ×
107m−1with a σ= 6.146 ×104. This yielded a percent error of approximately
0.26% as compared the accepted value of 1.097373 ×107m−1[5].
5www.pasco.com
4
Figure 2: Observed spectrum of hydrogen, trial 4. The Beta (green) line is
marginal compared to the Alpha (red) line and was originally overlooked upon
initial analysis.
4 Conclusion
Curiously, the missing two lines of the Balmer series in the obtained spectrum
pose a slight mystery. In initially analyzing the spectral data, the Balmer Alpha
line was only initially visible. Careful inspection of the plot showed the small
fringe of the Balmer Beta line to the left of the Alpha line only after magnifi-
cation. The assumption made regarding the missing Balmer lines is that their
relative intensity was not significant enough for detection by the light sensor.
Two possible solutions are a) increasing the gain of the electronic light sen-
sor and b) increasing the size of the collimating slit to allow for more light to
propagate.
In summary the experimentally determined value of Rydberg’s constant
(R= 1.095 ×107m−1) from the line spectra of hydrogen using a simple diffrac-
tion grating spectrophotometer yields acceptable results (0.26% error) in com-
parison to the current accepted value (R= 1.097373 ×107m−1). Furthermore,
determination of principle quantum numbers and respective energy levels may
deduced from the same methods with similar success. Regarding random error
and measurement uncertainty, total differentials proved to be insignificant with
regard to the the final precision of the experimental value of R.
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