In the Laboratory
A Guided-Inquiry Lab for the Analysis of the Balmer
Series of the Hydrogen Atomic Spectrum
A. M. R. P. Bopegedera
Department of Chemistry, The Evergreen State College, Olympia, Washington 98505, United States
bopegedd@evergreen.edu
Analysis of the emission spectrum of atomic hydrogen in
the visible region (Balmer series) is a common experiment in the
general chemistry laboratory (1) and articles on this topic have
been published in this Journal (2-9). In the published labora-
tory manuals used in the general chemistry laboratory courses,
students are given the Rydberg equation and the values of n1 and
n2 for each spectral line they observe,
 
1 1 1
¼ R 2- 2 where n2 > n1 ð1Þ
λ n1 n2
where n1 and n2 are integers and for the Balmer series n1 = 2, n2 =
3, 4, 5, 6, .... Using the recorded wavelengths, λ, the students plot
a linear graph of 1/λ as a function of [1/(n1)2 - 1/(n2)2] to
obtain the value of the Rydberg constant, R, from the slope of
the line.
It is my experience that, even after students complete this
experiment following instructions in the laboratory manual, they
often cannot make a connection between the Rydberg formula
and the Bohr model of the hydrogen atom. This shows a lack
of conceptual understanding of this central chemical concept.
Students seem to have little recognition of the contributions made
by Johann Balmer and Johannes Rydberg toward the analysis of the
hydrogen spectrum or how Neils Bohr used the mathematical
relationship in eq 1 to arrive at his model of the atom.
To solve this problem, I developed a guided-inquiry lab
for studying the visible spectrum of the hydrogen atom. This lab
falls early in the academic year (fall quarter or semester) because
the concept of the structure of the atom is covered early in the
chemistry curriculum. Chatterjee et al. described their use of
a well-designed survey to compare students' attitudes toward
guided- and open-inquiry labs (10). They concluded that stu-
dents have a preference for guided-inquiry labs and responded
more positively to them compared with open-inquiry labs.
Other authors have linked better attitudes with higher achieve-
ment (11, 12). An article exploring the impact of inquiry-based
labs compared with verification labs on students' understanding
of chemistry is currently under review in this Journal (13).
Experiment
Prelab
Prior to the lab, students are given instructions on the Bohr
model of the atom and the Rydberg formula. They learn that the
visible spectrum is observed when n1 = 2 with n2 > n1. As a prelab
assignment, they are asked to read the relevant section in their
textbook (14) and bring a hand-drawn diagram of the Bohr
model of the hydrogen atom showing the five lowest energy
transitions responsible for the visible spectrum (Balmer series)
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r 2010 American Chemical Society and Division of Chemical Education, Inc. pubs.acs.org/jchemeduc Vol. 88 No. 1 January 2011
10.1021/ed1003146 Published on Web 10/28/2010
and the corresponding ladder-type energy diagram (Figures 1
and 2) to the lab. In addition, students are asked to calculate the
value of the Rydberg constant, R, in cm-1, given that quantum
theory predicts that R is related to primary constants as shown in
eq 2 (15).
me4
R ¼ ð2Þ
8ε0 2 ch3
where m is the mass of an electron, e is the charge of an electron,
c is the speed of light, h is the Planck's constant, and ε0 is the
permittivity of a vacuum, all of which could be obtained from
standard table of constants (16).
Instrument Construction
In the laboratory, students, working in groups of three,
construct a homemade spectrophotometer on the lab bench to
record the visible spectrum of atomic hydrogen. There are many
advantages to using a homemade instrument, specially because
this is the first introduction to a spectrophotometer in the
general chemistry laboratory. Students can see all components
of the spectrophotometer and this eliminates the “black box”
syndrome. The spectrophotometer is broken into its bare-
bone functional parts and the students are given instructions
on the function of each part. Later in the year when they use
a commercial spectrophotometer, they receive more in-depth
instructions on how the diffraction grating works. Over the
course of the year, students use spectrophotometers several times.
At each of these times, the components of the homemade
spectrophotometer are revisited providing students with a better
understanding of the instrument with each use. As a result, by the
end of the second quarter, general chemistry students are able to
describe in detail how a spectrophotometer works by referring to
the function of each component of the instrument.
The homemade instrument is easy to build with a small
budget and even high school students taking advanced placement
chemistry can have access to it. The use of a meter ruler as a
measuring device provides an excellent opportunity for a discus-
sion on the accuracy of spectral measurements, an experience that
is lost when commercial instruments are used. Unlike commer-
cial spectrophotometers, the homemade instrument needs to be
calibrated and this calibration is dependent on the configuration
of the components. Because each lab group invariably moves the
components during setup, each group has a unique configuration
and a calibration graph. Therefore, each group must work
independently when analyzing data. At the end of the analysis,
students compare their results (Rydberg constant values) to
find that they are in good agreement despite using a “unique”
spectrophotometer.
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Journal of Chemical Education 77
 In the Laboratory

Figure 3. The block diagram of the homemade spectrophotometer.

Figure 1. The Bohr model for the hydrogen atom showing the five lowest Table 1. Mercury Spectral Lines Used for Calibrating the Homemade
energy transitions responsible for the Balmer series. The wavelengths of Spectrophotometer
these transitions range from λ1 to λ5.
Spectral Line Color Ruler Reading/mm λ/nm

Purple 336.0 404.6

Blue 368.0 435.8
Green 478.0 546.0
Yellow 501.5 576.9
Yellow 508.8 579.1
Red 650.0 695.9

Figure 2. The ladder-type energy diagram for the hydrogen atom

showing the five lowest energy transitions in the Balmer series
(wavelengths range from λ1 to λ5).

The power supplies, gas discharge tubes, and diffraction

gratings (at least 600 grooves per mm are required for good
resolution) are commercially purchased.1 A 35 mm slide holder
(without the film) is used as the viewing window. The lab needs
to be completely dark for this experiment and a small flashlight is
used to read the ruler. The block diagram for the homemade
spectrophotometer is given in Figure 3.
Data Collection
Students set up their homemade spectrophotometers with
the mercury discharge tube fitted into the power supply and
adjust the grating to observe a clean spectrum. The various
components of the instrument (power supply, ruler, grating,
viewing window, etc.) are then fixed in place on the table keeping
the configuration of the spectrophotometer constant for the
duration of the experiment. The positions of the mercury lines
on the ruler are read in millimeters with their corresponding
colors and recorded (Table 1). The wavelengths of mercury
lines, obtained from standard tables (14), are used to generate
a calibration graph for the spectrophotometer (Figure 4).
Figure 4. The calibration graph generated using data from Table 1.
This graph was used to obtain the wavelengths of the hydrogen emis-
sion lines from their corresponding meter ruler readings (reported
in Table 2).
The mercury discharge tube is carefully removed from the
power supply and switched with the hydrogen discharge tube
without changing the configuration of the spectrophotometer.
The students then observe four spectral lines that correspond to
the Balmer series of the hydrogen spectrum. The ruler positions
for these lines are recorded in millimeters and converted
to wavelength in nanometers using the calibration graph. These
spectral data are reported in Table 2.

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78 Journal of Chemical Education Vol. 88 No. 1 January 2011 pubs.acs.org/jchemeduc r 2010 American Chemical Society and Division of Chemical Education, Inc.
 In the Laboratory

Table 2. Spectral Data for the Hydrogen Emission Lines and Data Used To Generate Figure 5

Spectral Line Color Ruler Reading/mm Wavelength/nm n2 (1/λ)/nm-1 1/n2 (1/n2)2

Purple 340.0 413.0 6 2.421  10-3 1.667  10-1 2.778  10-2

-3 -1
Blue-purple 364.0 435.8 5 2.295  10 2.000  10 4.000  10-2
-3 -1
Blue-green 419.0 487.9 4 2.050  10 2.500  10 6.250  10-2
Red 600.6 659.9 3 1.515  10-3 3.333  10-1 1.111  10-1

Figure 5. Student generated graphs exploring the relationship between wavelength (λ) and n2.

Guided-Inquiry relationships and justify their choices to each other. It is in these

After collecting spectral data, students work in groups to
discover the relationship between their data and the theoretical
model to fit their data (their prelab work on the Bohr model, the
ladder-type energy diagram, and the Rydberg formula). At this
time, I move among student groups following their discussions,
asking, and answering questions, but the responsibility of making
the connection between their lab data and the theoretical model
is left to each individual group. After some time, I ask student
groups to share their findings. It does not take long for the class to
come to a consensus that the values of n2 in the Rydberg formula
change as the wavelengths (and color) of the spectral lines
change. This is a great “aha” moment for many students who
before this experience could not appreciate the connection
between the Bohr model, the Rydberg formula, and spectral data.
At this point, it is useful to generate a discussion on
independent and dependent variables and invite student groups
to identify these in relation to their data. From their Bohr model
diagram, students quickly conclude that the independent vari-
able is n2 and the dependent variable is the wavelength, λ,
although the relationship between these variables is not apparent
to them at once. It is vital that the instructor exercise patience at
this time and refrain from directing students to the answer.
Instead he or she should ask questions and encourage students to
work in their groups to find the solution. Some student groups
refer to their chemistry textbook at this time looking for help
to solve their problem. Others have discussions about possible
interactions (with the textbook and with peers) that real learning
takes place. I provide words of encouragement but never the
solution. I may direct the groups to try out some graphs to find
out the relationship between λ and n2. Students have access to
computers in the laboratory and use Microsoft Excel to plot
graphs. Whereas some groups follow this course of action, others
find the answer by analyzing the information in their prelab
assignment (Bohr model, the ladder-type energy diagram, and
the Rydberg formula). A collection of graphs typically generated
by students is given in Figure 5.
Hazards
There are no hazardous materials associated with this
laboratory. Caution should be used when changing the gas
discharge tubes in the power supply. The power supply must
be turned off and unplugged before changing gas discharge tubes.
Discussion
Over the course of this exercise, students recognize that 1/λ
is directly proportional to 1/(n2)2, some groups reaching this
conclusion before others, providing an opportunity for peer
teaching and learning. Once they reach this stage, the connections
between the Bohr model, the Rydberg formula, and their spectral
data become clear. They deduce that a graph of 1/λ versus 1/(n2)2
is linear because the Rydberg formula has y = -mx þ b type of a

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 In the Laboratory
relationship [y = 1/λ, m = R, x = 1/(n2)2, and b = R/4 since n1 = 2
for the Balmer series].
At this point, I ask students if they think their spectral lines
have been assigned correctly. Students are surprised at this
question because their data seem to fit eq 1 and they do not
understand what is meant by “a correct spectral assignment” or
how one could make a “wrong spectral assignment”. I suggest that
they change their n2 value for the lowest energy spectral line and
for the other lines accordingly and replot their graphs. The
results are shown in Figure 6. It becomes clear from this exercise
that the graph of 1/λ versus 1/(n2)2 is linear only when the
spectral lines are assigned with the correct quantum numbers.
Figure 6 is definite evidence that it is very important to
check the accuracy of the spectral assignment before proceeding
to do calculations or draw conclusions. Students determine the
value of the Rydberg constant in cm-1 units using the slope of
the line in Figure 5, graph E. They are asked to find another way
to determine R [R = 1/4(intercept) in Figure 5, Graph E],
compare these two values, and use the average as their experi-
mental value for the Rydberg constant. Then they compare their
experimental value with their calculated value from the prelab
assignment and perform an error calculation (Table 3). They are
also asked to calculate the ionization energy of hydrogen from
their data (by substituting n1 = 1 and n2 = ¥ into the Rydberg
formula) and compare with the published value.
These calculations provide an excellent opportunity to have
a discussion on significant figures. The theoretical value of the
Rydberg constant can be calculated to seven significant figures,
whereas the experiential data are limited by the accuracy of their
measuring device, which is a ruler. Although students have used
other instruments earlier in the year to compare how accurately
measurements could be made (top loading balance versus the
analytical balance for example), it is important to visit this
concept as many times as possible in the laboratory to drive it
home. It is wonderful that using such simple equipment students
Figure 6. Determining the correct n2 assignment for the hydrogen
emission lines.
Table 3. Error in the Rydberg Constant and Ionization Energy
Parameter Experimental Value
Rydberg constant/m-1 1.090  107
b
Ionization energy/eV 13.52
a b
Calculated using eq 2. Calculation is given in supporting information. Literature value from ref 14.
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80 Journal of Chemical Education Vol. 88 No. 1 January 2011
can obtain high quality data as evidenced by the low percent
errors.
Other Logistics in the Laboratory
Enough equipment was available to set up six homemade
spectrophotometers; hence, 18 students (six groups of three
students) could work on the spectrophotometers at a time. Those
waiting for their turn on a spectrophotometer were engaged in
recording emission spectra of other gas discharge tubes (nitrogen,
argon, krypton, neon, etc.) and Fraunhofer lines (if it was a
sunny day) using hand-held spectrophotometers.2
Some Student Comments
Overall, students responded well to the inquiry approach to
this lab. Compared with previous years where the inquiry
approach was not used, students retained what they learned
in this lab for the duration of the course as demonstrated in
subsequent exams and based on the following responses.
• At first I could not see any connection between λ and n2
although I kept referring to my prelab for help. I was hoping for
some help from my instructor but it became clear that I would
have to do this myself. My group mates and I spent a long time
discussing the Rydberg formula when we finally realized that it
represents a linear relationship. I will never forget that moment!
If I were taught this by my instructor, the learning experience
would not be so powerful (or painfully powerful!)
• Our group simply could not get it. We kept hearing “we got it”
from other students around us and they seemed really excited
that I felt envious. Finally we asked another group for help.
I think I now understand the power of peer teaching. I hope I get
to teach someone else in the future
• It was the graphs that helped our group. We kept generating
graphs until we found that 1/λ and 1/n22 has a linear relation-
ship. Then our instructor told us to try to relate that to the
Rydberg formula. It was like a light bulb going on at that
moment. I understood how the lab and the prelab were
connected
• I don't like prelab assignments. I do them only because I have to.
After this lab however, I have a different view of the pre-lab!
Possible Extension of This Laboratory
Half of the class could record the spectrum of hydrogen and
the other half could record the spectrum of deuterium. They
could pool their data and calculate the Rydberg constants for
hydrogen and deuterium. This generates interesting discussions
in class. How can the Rydberg “constant” be a constant if it is
different from hydrogen to deuterium? Students are convinced
that the two constants will be the same even before they attempt
the analysis. The spectral data and analysis completed by a single
Calculated or Literature Value Percent Error
1.097373  107a 0.64%
13.598c 0.57%
c
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pubs.acs.org/jchemeduc r 2010 American Chemical Society and Division of Chemical Education, Inc.

student for both hydrogen and deuterium are provided in
the supporting information. These data clearly show that the
Rydberg constants for the two isotopes of hydrogen are different.
Although students in general chemistry do not have the necessary
knowledge in quantum chemistry to fully appreciate why there is
a difference, it gets students thinking about what they may
be able to learn if they choose to study physical chemistry in later
years and provides the instructor and opportunity to encourage
students to pursue further studies in chemistry. Some students
point out that the Rydberg constants of the two isotopes are
not “very different” and want to know if the differences are
significant enough. This can lead to an excellent conversation
on significant figure when using instrumentation. Complete
instructions given to students to conduct this laboratory are
provided in the supporting information.
Conclusion
This guided-inquiry lab enables students to recognize that
theory (Rydberg formula and Bohr model) develops from
experimental data, although in their textbook it appears as if
the theory came first! They also gain an appreciation for the work
done by physicists of the early 20th century to arrive at the
structure of the atom. Students could be asked to find informa-
tion on Neils Bohr, Johann Balmer, and Johannes Rydberg as
part of their prelab or postlab exercise that will provide historical
context to this lab, enriching their experience. This enables
students to recognize the many contributions made to chemistry
by physicists and mathematicians, thus, emphasizing the inter-
disciplinary nature of science.
Acknowledgment
The spectral data presented in the article were collected by
James Stroh, a faculty colleague at The Evergreen State College.
The student aide in the general chemistry laboratory, Aubrey
Ernst, recorded the spectral data for hydrogen and deuterium
that is provided in the supporting information.
Notes
1. The power supplies ($170 each) and the gas discharge tubes
($18 each) were purchased from Cynmar Corporation (17).
The diffraction gratings with 600 lines per mm were purchased
from Paton Hawksley Education Limited (18).
2. The hand-held spectrophotometers (Project STAR Spectrom-
eters at $38 per piece) were purchased from Wards Natural
Science (19).
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r 2010 American Chemical Society and Division of Chemical Education, Inc.
In the Laboratory
Literature Cited
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13. Bopegedera, A. M. R. P.; Putting the Laboratory at the Center of
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14. Zumdahl, S. S.; Zumdahl, S. A. Chemistry, 8th ed.; Brooks/Cole
Cengage Learning: Belmont, CA, 2010 and other comparable
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15. Alberty, R. A.; Silbey, R. J.; Bawendi, M. G. Physical Chemistry,
4th ed.; John Wiley and Sons, Inc: Hoboken, NJ, 2005.
16. CRC Handbook of Chemistry and Physics, 60th ed.; Weast, R. C.,
Ed.; The Chemical Rubber Co.: Boca Raton, FL, 1979.
17. Cynmar Corporation Home Page. http://www.cynmar.com/home.
aspx (accessed Oct 2010).
18. Paton Hawksley Education Limited Home Page. http://www.
patonhawksley.co.uk/ (accessed Oct 2010).
19. Wards Natural Science Home Page. http://wardsci.com/ (accessed
Oct 2010).
Supporting Information Available
The analysis of the visible spectrum of hydrogen and deuterium
and the Rydberg constants for the two isotopes obtained from spectral
data recorded by a single student; complete instructions given to
students; instructions on how to build the homemade spectropho-
tometer; calculation of the ionization energy of hydrogen from lab data.
This material is available via the Internet at http://pubs.acs.org.
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pubs.acs.org/jchemeduc Vol. 88 No. 1 January 2011 Journal of Chemical Education 81