Atomic Models and Spectroscopy

In this activity you will use both a computer simulation and laboratory instruments
to investigate the line emission spectra for different atoms.

Introduction
When light from the Sun or white light is passed through a prism it produces a
“rainbow” of different colors. This has been known for centuries, with Isaac Newton
making significant advances in the area of “Opticks” in the 1700’s by investigating how
light is reflected, refracted, dispersed, etc.

However, something very different occurs when light from a single element is emitted
and passed through a prism. In this case only a small number of discrete lines are
observed. Even more remarkably, the pattern of these lines (the line spectrum) is a
defining characteristic of each element. What happens when light is emitted from an
element like hydrogen? Why is the pattern different for different elements? As you will
see in this investigation, the answering of these question has led to profound insights
into the electronic structure of the atom and, in turn, our modern understanding of
chemistry.

Logistics
This laboratory activity is designed for one 3-hour session for General Chemistry
students working in groups of 2-3. Parts A.1 and A.2 may be completed prior to attending
lab. The PhET sim, if used as a standalone activity in Part A, can be completed in about
60-90 minutes. Prior knowledge regarding the structure of the atom and atomic models
proposed by Dalton, Thomson, and Rutherford is assumed and extended here.
 Part A. Investigate Models of the Hydrogen Atom

Descriptions of different models of the hydrogen atom are scattered throughout your
textbook. Atomic models are conceptual. A weather map is also an example of a
conceptual model. The weather map communicates some (but not all) aspects of the
weather, e.g. the temperature, areas of high and low pressure, precipitation, etc. Models
allow one to make predictions (will it rain in New York tomorrow?) and makes sense of
complex systems. Atomic models are conceptual and serve to communicate different
characteristics and make predictions, even when it is impossible to directly see the parts
of the atom itself.

A.1) Use the sim to collect the line emission spectrum for hydrogen.

Start by playing with the sim “Models of the Hydrogen Atom”

Figure out how to do the following things with the sim:

o Turn on the “gun” to direct light into a box of hydrogen.

o Speed up, slow down, or pause the sim.

o Use a spectrometer to detect photons emitted from the box.

o Direct only green light (photons of “green”) in to the box of hydrogen.

o Direct only ultra-violet (UV) photons in to the box of hydrogen.

o Collect the line emission spectrum using the spectrometer when white light enters
the box. It may be helpful to speed up the sim. After a few minutes sketch the
spectrum in the box below1. Include in your sketch the colors (regions of the
electromagnetic spectrum) and estimated wavelengths.

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Questions in bold should be answered directly into this packet.
 o Also figure out how to take a picture of the spectrum. Save the spectrum on the
screen. This is “experimental data” and can be compared with predicted line
spectra for different atomic models.

For hydrogen, how many emission lines are present in the visible light region, and
which color do you think will be the brightest, i.e. the most intense?

A.2) Investigate the pre-quantum models of the hydrogen atom.

o Figure out how to switch to different atomic models in the sim. This will allow you
to test different models and see the line spectrum they predict.

For the “pre-quantum” models (Dalton’s Billiard Ball model, Thomson’s Plum Pudding
model, and Rutherford’s Classical Solar System model) perform the following tasks:

o In your notebook, describe each model with words and/or a sketch.

o Test the model: Does it produce a line emission spectrum matching the
experimental one?

Dalton’s atomic model was put forward in 1807 and was influential for much of the 19 th
century. It is not uncommon for conceptual models to be replaced, but also retain value if
they are still useful for describing some aspects of nature.
Are there parts of Dalton’s atomic hypothesis still used by chemists today?

Thomson’s model was proposed in the last years of the 19 th century. Scientific ideas are
often described as “concrete and durable”, with strong support from different sources,
but at the same time “tentative”, with ideas being subject to change in light of new
evidence or new interpretations of existing evidence.
What led to Thomson’s model replacing Dalton’s model? Was it new evidence, or a
new interpretation of existing evidence?
Some textbooks suggest that Rutherford’s model was a great success and widely accepted
upon its introduction. This is false, as it took several years before it became accepted as a
plausible model.
Why do you think the Classical Solar System model was not readily accepted?

A.3) Investigate the Bohr and de Broglie models of the hydrogen atom.

First, figure out how to show the electron energy level diagram for these models.
There are now three different representations shown in the sim: the “picture” of the
atom, the electronic energy level diagram, and the predicted emission spectrum. Your
task is to make connections between all three of these domains.

In your notebook, use words and/or sketches to compare and contrast the Bohr and de
Broglie models in terms of:
a) What the atom “looks like”,
b) The electron energy levels, and
c) The emission spectra.

How is the location of the electron related to the energy level diagram?

What causes the electron to change its position?

What causes a photon to be emitted?

Go to the Help menu, select Transition, and then fill in the missing entries:
Electronic transition Wavelength (nm) UV, visible, or IR?
between n levels (Look at the spectrometer)
12 122 UV

14 97 UV

23 655 Visible

26 410 Visible

34 1876 IR

36 1094

46 IR
56 IR

In General Chemistry, common calculations involve converting between energy,

frequency, and wavelength:

E=h Planck’s relationship for the energy of a photon

c= 1 nm = 1x10-9 m h = 6.63x10-34 Js.
c= 3.00x108 m/s in a vacuum.

You may also be familiar with the concept of “matter waves,” where the wavelength of
any particle is inversely related to the particle’s mass and speed:  = h/mv

Suppose an electron is at the n=2 energy level. It is then struck by light with a
frequency of 4.5770x1014 s-1. What happens to the electron?

In the sim’s representation of de Broglie’s model of the hydrogen, the wave-

character of the electron and the proton appear quite different. Why do you think
this is?
 Suppose the electron is in orbit closest to the nucleus. Complete the table below by
FIRST predicting what will happen if monochromatic radiation is used. AFTER you have
recorded your predictions, test them with the sim. It may help to perform tests after
completing a row.

Wavelength Movement of electron Energy level diagram Emission spectrum

103 nm Prediction: Prediction: Prediction:

97 nm Prediction: Prediction: Prediction:

99 nm Prediction: Prediction: Prediction:

Were your predictions confirmed by the sim?

If so, you have a good understanding of these models.
A.4) Investigate the Schrödinger model of the hydrogen atom.

Erwin Schrödinger began working on wave mechanics in 1925. His interest was sparked by
a footnote in a paper by Albert Einstein. Like de Broglie, he began to think about explaining
the movement of an electron in an atom as a wave. In 1926 he published his work, providing
a theoretical basis for the atomic model that Bohr had proposed. The equation at the heart
of his publication became known as Schrödinger's wave equation.

In your notebook, use words and/or sketches to compare and contrast the Schrö dinger
and the Bohr models in terms of:
a) What the atom “looks like”,
b) The electron energy levels, and
c) The emission spectra.

Notice, as the electron moves in to different orbitals the quantum numbers change. Use
white light and, for three different combinations of quantum number in the sim,
sketch the resulting atomic orbital in the table below.
Quantum Numbers Quantum Numbers Quantum Numbers

Sketch of atomic orbital Sketch of atomic orbital Sketch of atomic orbital

Let the sim run with white light and identify the electronic transitions (i.e. the change
from one orbital to another) that take place. Add your results to the table below. An
example for the absorption of a photon is given (how do you know it’s an absorption?)…
it is not necessary to list the corresponding emission, e.g. from n,l,m = 4, 1, 0 to the
ground state 1, 0, 0 as well.

Electronic Transitions in the Hydrogen Atom

Quantum State Quantum State Does the transition involve
(Initial) (Final) the ground state?
n L m n L m Yes
1 0 0 4 1 0

There are many energy levels and corresponding quantum numbers for the hydrogen
atom, but the electron does not move between every possible combination. In other
words, some transitions “allowed” and others “forbidden”.

Start by looking at information in your table for transitions involving the ground state.
Are there “rules” restricting the transition of the electron involving “n”, or can it
change by any amount?

Are there “rules” involving “l”?

Now look at transitions between excited states.

Do your rules explain why an electron in an excited state might absorb another
photon and moves to a different excited state instead of returning directly to the
ground state?
 Part B. Use a Spectroscope to Observe the Line Spectra for
Hydrogen and Helium

In this activity you will…

o Record scale readings for hydrogen emission lines with a spectroscope.
o Prepare a calibration curve for the spectroscope.
o Record scale readings for helium emission lines with a spectroscope.
o Use the calibration curve to determine the wavelength of the He emission lines.

The line spectrum for hydrogen you will observe is what results when white light enters
the ?-box in the computer simulation (although here the excitations take place with
electricity). As shown in the simulation, photons with many different wavelengths (UV,
visible, IR) are emitted. Photons in the visible light region are observable with our eyes,
but we do not see a line spectrum because our eyes observe all of the photons at the same
time. To produce a line spectrum the photons must be separated. This is accomplished
with a spectroscope.

As you might infer from the image below, spectroscopes have been around for a long
time. They make use of the phenomena of refraction; by simply passing light through a
prism, the photons of different energy may be separated.

As shown by visible light passing through a prism, the extent of the refraction (the change
in direction) is affected by the wavelength.

Are high-energy photons refracted more or less than low energy photons?

With a spectroscope you observe the “screen” following the dispersion of the light.
Would the line spectrum you see change in any way if the distance between the
prism and the screen changed?
Based on the sim, how many lines do you expect to see for a hydrogen discharge lamp?
For each line, predict the color, the wavelength, and whether it will be “bright” or “dim”.
Base your predictions on what you observed using the sim and record the information in
your notebook.

Color Wavelength Intensity Scale reading

(nm) (bright of dim)

AFTER RECORDING YOUR PREDICTIONS, use the spectroscope and write the scale
readings in your notebook for the lines you observe (see cautions below). These are the
emission lines appearing on the “screen” of the spectroscope.
When using the spectroscope you will see a bright yellow line. This is from the element
sodium, which is in the glass. It has an emission line at 589 nm. Add this value to your
table as well.

Cautions and Procedure

 The 5000 V step-up transformer and contacts for tubes on boards are an electrical
hazard.

 Always wear your lab goggles since they will block out almost all-harmful UV
radiation.

 Make sure the overhead lights in the balance room are off during observations.

 The TA will assist you with setting up the spectroscope.

Data Analysis for Hydrogen: Calibration of Spectroscope

The spectroscope separated the photons of light emitted from the hydrogen discharge
lamp based on their energy. Since you already know the wavelength values for the
different emission lines you can calibrate the instrument by finding a relationship
between wavelength and the scale readings. Plotting and then fitting the data with a
program like Excel is a useful way to determine this relationship. Complete this task and
record the calibration information in your notebook.

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Helium Emission Line Spectrum
A helium discharge lamp is also available in lab. For this element you do not know in
advance the number of emission lines or their wavelength. Fortunately, after your
analysis of the hydrogen emission lines you do have a calibrated spectroscope. Use the
spectroscope to identify the emission lines for helium and the accompanying scale
readings. Then, use your calibration data to convert these scale readings to wavelengths.
Record your data, calculations, etc., in your notebook.

Now make a sketch of the line emission spectrum for helium in the box below.
Notice the x-axis has units of wavelength.

He line spectrum: Data from a spectroscope

Wavelength (nm)

Part C. Using a Spectrometer2 to Observe the Line Spectra

Although simple, inexpensive, and historically interesting, spectroscopes are not

frequently used by chemists. In contrast, spectrometers are extremely important. In
fact, it is difficult to imagine modern scientific laboratories without numerous
spectrometers. You will use several kinds of spectrometers this semester. How are they
different from spectroscopes? To answer this question, use a spectrometer to record the
emission from a helium discharge lamps and sketch it in the box below.

He line spectrum: Data from a spectrometer.

Wavelength (nm)

Why might a chemist favor a spectrometer over a spectroscope?

Report Questions
2
A Vernier spectrometer and gas discharge lamps are used.

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The report questions are very important in this laboratory report. Convince the
reader you understand the concepts investigated with the computer simulation
and/or the experimental data, as applicable.

1. The computer simulation includes pre-quantum models (Billiard Ball, Plum Pudding,
etc.). It was not possible to “test” these models and actually collect emission spectra in
the lab. How did the computer programmers (in consultation with expert physicists)
decide on the correct output? In other words, communicate your understanding of each
of the pre-quantum models and discuss how each model’s attributes led the
programmers to predict their emission spectra. Information from Part A, and from your
textbook or other sources, may be helpful.

2. In this experiment you calibrated a spectroscope. Suppose you analyzed the emission
spectra for a second row element (Li, Be, B, etc.) in the visible light region using the
same set-up. What would be the scale readings? Express your findings in a table that
includes both the reported wavelengths and your converted scale readings. There are
several web-sites listed emission data (see the link below).
http://concave.stc.arizona.edu/thepoint/Interactive/spectraline.html

3. Examine line spectra data for other elements (the web site in question 2 is useful). Do
the emission spectra for the second row elements follow a periodic trend in terms of
number of emission lines, or perhaps their energy?

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