Spectroscopy Emission Wavelength

John Freeman
Department of Physics, University of Utah, Salt Lake City, Utah

Spectral emission lines propagate in discrete wavelengths based on the energy lost during
orbital transition. When an electron makes a transition from an excited state to a lower
state, a photon is emitted at a wavelength that is inversely proportional to the change in
ℎ𝑐
energy ∆𝐸 = 𝜆 . The discrete nature of the electronic energy levels thus leads to a
discrete spectrum. In this experiment, we use a spectroscope to observe the emission
wavelength of ionized hydrogen, neon, helium, and mercury.

Introduction
Spectroscopy is a vital technique for determining the elemental composition of an object.
For example, it is commonly used in astronomy to predict the percentage of hydrogen and
helium in a celestial object, and its corresponding metallicity. In 1885, Johann Balmer
1 1 1
revolutionized spectroscopy by discovering a mathematical formula, 𝜆 = 𝑅 (𝑛2 − 𝑛2 ), that
𝑓 𝑖
predicts the 4 emission wavelengths of the hydrogen atom in the visible spectrum. At the time,
the structure of the atom was in debate but one thing was certain; excited elements emitted a
range of discrete wavelengths. Niels Bohr proposed that electrons were in orbital shells, of
naturally determined finite radii, around the nuclei. This model is similar to planetary orbits but
with electromagnetic forces instead of gravitational. However, there were several concerns with
this model such as wondering why doesn’t the electron collapse into the nuclei. It would later be
answered by Louis de Broglie’s proposal of standing wave particle duality.

In this experiment, we will measure the wavelength of orbital transitions of excited gases.
The wavelengths are inversely proportional to the change in energy of the initial and final
ℎ𝑐
“orbital” state. ∆𝐸 = 𝑛ℎ𝑓 = 𝑛 𝜆 . We will compare these wavelengths to the accepted values.
Next, we will use linear least square fitting to calculate the Rydberg constant, 𝑅. Lastly, we will
show that the Balmer series is true in predicting the final state of hydrogen emission, in the
visible spectrum range, is 2.

Experiment
The equipment used was a spectroscope with its accessories: diffraction grating (Replica
Grating: 600 grooves/mm, Grade A, Sargent-Welch Scientific Company), lamp holder with gas
tube lamps, magnifying glass, and collimator (Figure 1). The spectroscope works similar to a
telescope; it magnifies the image. The low-pressure gas tubes are each filled with a different
elemental gas. For this experiment, we used hydrogen, helium, mercury, and neon. A diffraction
grating a transparent material with equally spaced parallel lines called the grating spacing, 𝑑. The
grating separates light of different wavelengths into different directions. The angle can be
measured using a circular scale consisting the main scale and the upper Vernier scale (Figure 2).
The collimator is a device that transforms diverging light into parallel rays.
 Figure 1: The spectrometer and accessories Figure 2: The scale to determine the diffraction
used to conduct the experiment. angle. The larger scale is the main and the
shorter scale is the vernier.

The lamp holder is an electrode that ionizes the gas inside the tube. The spectroscope has
a crosshair that can be centered the focused emission lines as shown in Figure 3-4. The angle of
each line is recorded. The wavelength of the emission can be calculated by Eq 1 where 𝑚 is the
order number, 𝜆 is the wavelength, 𝑅 is the Rydberg constant, and 𝜃 is the diffraction angle. The
measurements can then be applied to Eq 2 where 𝑛 is the quantum principle number of initial and
final states.

𝑑𝑠𝑖𝑛(𝜃)
Eq 1 𝜆= 𝑚
1 1 1
Eq 2 = 𝑅 (𝑛2 − 𝑛2 )
𝜆 𝑓 𝑖

It is common to approximate the Rydberg constant by assuming the nucleus is infinitely

large,
𝑚 𝑒4
𝑅∞ = 8𝜖2𝑒ℎ3 𝑐 = 1.09737 ∗ 107 𝑚−1. However, lighter elements such as hydrogen are multiplied
0
𝑚𝑝
by the reduced mass of the electron, 𝑅𝐻 = 𝑅∞ = 𝑚 = 1.09678 ∗ 107 𝑚−1 . Where 𝑒 is the
𝑒 +𝑚𝑝
elementary charge of an electron, 𝜖0 is the permittivity of free space, h is the Planck constant,
and c is the speed of light in vacuum.
 Figure 3: The emission lines of hydrogen seen Figure 4: The emission lines of neon seen
through the scope. through the scope.

Results & Analysis

To calculate the wavelength, we measured the angle of the spectroscope using the main
and vernier scale. The vernier scale increases the accuracy more than the main scale alone. The
vernier scale has 30 marks for every 5° on the main. That gives us the equation 𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑 =
𝑣𝑒𝑟𝑛𝑖𝑒𝑟𝑟𝑒𝑎𝑑𝑖𝑛𝑔 1
𝑚𝑎𝑖𝑛𝑟𝑒𝑎𝑑𝑖𝑛𝑔 + . The uncertainty in the reading is ±1 𝑚𝑎𝑟𝑘𝑠 = °. The diffraction
60 30
𝑔𝑟𝑜𝑣𝑒𝑠
grating was spaced 𝑁 = 600 , and the distance between the lines on the diffraction grating
𝑚𝑚
1
𝑑 = 𝑁 = 1.667 ∗ 10−6 ± 5 ∗ 10 −9
𝑚. The wavelength can be calculated by 𝜆 =
𝑑
sin(𝜃) ± 55 𝑛𝑚. The uncertainty is found using error propagation (Eq 3). The observed
𝑚𝑖
wavelength of each element is given in Table 1-4. The values are compared with the accepted
wavelengths provided by National Institute of Standards and Technology (NIST)1.

2 sin2 (𝜃) 2 cos2(𝜃)

𝛿𝑑 𝑑2 𝛿𝜃
Eq 3 𝛿𝜆 = √ + .
𝑚2 𝑚2
Table 1: The observed wavelength of hydrogen Table 2: The observed wavelength of mercury

Observed ±𝛿𝐻 𝑛𝑚 Accepted Percent Observed ±𝛿𝐻𝑔 𝑛𝑚 Accepted Percent

𝜆𝐻 𝑛𝑚 𝜆𝐻 𝑛𝑚 Error 𝜆𝐻𝑔 𝑛𝑚 𝜆𝐻𝑔 𝑛𝑚 Error
% %
443.94 53.68 434.00 2.29 446.06 53.66 435.80 2.36
495.22 53.18 486.10 1.88 546.45 52.63 546.10 0.06
664.13 51.11 656.20 1.21 584.85 52.17 580.40 0.77
439.18 23.71 434.00 1.19 597.93 52.01 589.60 1.41
490.01 22.58 486.10 0.81 445.44 23.58 435.80 2.21
651.36 17.52 656.20 0.74 564.98 20.56 546.10 3.46
658.14 17.24 656.20 0.30 591.26 19.73 580.40 1.87
349.11 54.45 410.20 14.89 592.29 19.70 589.60 0.46
490.12 53.24 486.10 0.83 432.79 53.78 435.80 0.69
667.69 51.06 656.20 1.75 541.49 52.68 546.10 0.84
443.31 23.62 434.00 2.14 584.71 52.17 580.40 0.74
601.32 19.40 486.10 23.70 584.82 52.17 589.60 0.81
663.04 17.03 656.20 1.04 436.53 23.76 435.80 0.17
670.93 16.69 656.20 2.24 548.03 21.06 546.10 0.35
579.20 20.12 580.40 0.21
580.25 20.09 589.60 1.59

Table 3: The observed wavelength of neon Table 4: The observed wavelength of helium

Observed ±𝛿𝑁𝑒 𝑛𝑚 Accepted Percent Observed ±𝛿𝐻𝑒 𝑛𝑚 Accepted Percent

𝜆𝑁𝑒 𝑛𝑚 𝜆𝑁𝑒 𝑛𝑚 Error 𝜆𝐻𝑒 𝑛𝑚 𝜆𝐻𝑒 𝑛𝑚 Error
% %
584.82 52.17 585.20 0.07 459.75 53.53 447.10 2.83
585.39 52.16 585.20 0.03 487.70 53.26 471.00 3.55
598.20 52.00 603.00 0.80 501.62 53.12 492.20 1.91
598.75 52.00 603.00 0.71 515.50 52.97 515.60 0.02
598.88 52.00 603.00 0.68 601.19 51.97 587.60 2.31
611.81 51.83 618.20 1.03 692.01 50.70 667.80 3.62
612.19 51.82 618.20 0.97 446.85 53.65 447.10 0.06
612.60 51.82 618.20 0.91 474.86 53.39 471.00 0.82
625.30 51.65 626.70 0.22 488.82 53.25 492.20 0.69
625.65 51.65 626.70 0.17 502.73 53.11 515.60 2.50
625.97 51.64 626.70 0.12 585.39 52.16 587.60 0.38
638.92 51.47 640.20 0.20 666.45 51.08 667.80 0.20
639.22 51.46 640.20 0.15
639.24 51.46 640.20 0.15
639.62 51.46 640.20 0.09
652.31 51.28 650.70 0.25
 The Rydberg constant can be measured by applying the linear least square fit to Eq 2, and
calculating the slope (Figure 5). Our calculated slope was 101.27 ± 22.836 𝑛𝑚 with an r-
squared value of . 981. The accepted Rydberg constant is 109.68 nm which gives us an
experimental percent error of . 4%.

y = 1.013E+07x
Rydberg Constant R² = 9.817E-01
3500000

3000000

2500000
1/lambda 1/m

2000000

1500000

1000000

500000

0
0 0.05 0.1 0.15 0.2 0.25
(1/n_f^2 -1/n_i^2)

Figure 5: Linear least square fit to calculate the Rydberg constant. Error bars
are the standard error (standard deviation of the mean).

Figure 6: Residual graph for verifying correlation. Error bars are Root Mean
Square Error.
 To show that 𝑛𝑓 = 2 for the Balmer lines based on our measurements, we perform
algebra on Eq 2 to obtain Eq 4, and take the average of our results. Using our experimental
Rydberg constant and our measured wavelengths we found 𝑛𝑓𝑎𝑣𝑔 = 2.07 (Table 5).
𝐻 𝑅 𝜆
Eq 4 𝑛𝑓 = 𝑛𝑖 √𝑛2 +𝑅
𝑖 𝐻𝜆

Table 5: Trials of calculated final state of electrons based on emitted wavelengths.

𝑛𝑓 6 4 3 6 5 4 3
Trials 2.069186 2.012209 2.005343 2.05937 2.101488 2.220819 2.000314
1.858686 2.004428 2.00831 2.067874 2.282618 2.234481 2.010991

Mean 2.066866

Conclusion
Some of our samples weren’t entirely pure as we had several observed wavelengths
corresponding to one emission line. Furthermore, our hydrogen sample showed 4 emission lines
when it was in second order, but only 3 emission lines in first order. Better results could be
obtained by using fresh samples, and by using a spectrometer instead a spectroscope. We have
verified the Rydberg constant to a 4% error using linear least square fitting. We have also shown
that the final orbital state of the Balmer Series, in the visible spectrum, is 2.

Acknowledgements

This research was supported in part by the University of Utah Physics Department under
the supervision of Dr. Orest Symko. Luis Rufino and Dalton Rasmussen participated in data
recording and resulting analysis.

References

1] Kramida, A., Ralchenko, Yu., Reader, J., and NIST ASD Team (2021). NIST Atomic Spectra
Database (ver. 5.9), [Online]. Available: https://physics.nist.gov/asd [2021, November 23].
National Institute of Standards and Technology, Gaithersburg, MD. DOI:
https://doi.org/10.18434/T4W30F