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Light and Spectra

INTRODUCTION difference in energy between lower and higher electron


energy levels. When the electrons return to lower energy
Light and color have intrigued humans since antiquity. In
levels, energy is emitted in the form of a photon. Since
this experiment, you will consider several aspects of light
atoms have a number of energy levels available, there are
including:
a number of different energies that can be absorbed and
a. The visible spectrum of colors (red to violet)
released. For example, the visible portion of the spectrum
b. Bright line spectra as emitted by an excited gas or
for mercury contains the following colors:
solid
c. The relationship between color, wavelength, fre‑
COLOR λ , nm COLOR λ , nm
quency and energy.
violet 405 yellow 579
BACKGROUND AND THEORY blue 436 orange 623
green 492 red 689
Light is a form of energy called electromagnetic radiation.
It has wavelength and frequency. Wavelength, λ (lambda),
The energies of the emitted wavelengths can be correlated
is the distance between adjacent wave crests. Visible
with the energies of electron transitions from higher to lower
light has wavelengths in the 400 nm to 700 nm range
energy levels. During an energy high → energy low electronic
(1 nm = 10‑9 m). Frequency, ν (nu), tells how many waves
transition, the greater the difference between the energy
pass by a point in a second. Violet light, with a wavelength
levels, the larger is the energy released, and the shorter is
of 400 nm, has a frequency of 7.5 x 1014 per second, many
the wavelength of the photon emitted. In the energy level
more waves than are shown in the diagram.
diagram of a generic atom shown below, the left-hand arrow
λ λ
represents an electron releasing energy as it drops from the
6th to the 2nd energy level.

n=6

n=5

ν = 2 waves ν = 3 waves
per time line per time line n=4
The energy of electromagnetic radiation varies directly with
the frequency, and inversely with the wavelength. Thus,
violet light is of higher energy than red light, which has n=3
wavelengths in the 650 nm range. White light, such as that
from an ordinary incandescent light bulb, is a mixture of
wavelengths in the visible range. When white light strikes
a prism or diffraction grating, the light is dispersed into a
continuous spectrum of visible colors. A non-continuous n=2
spectrum occurs when an electric current passes through The energy is released in the form of a photon. This photon
a gaseous element in a gas discharge tube or when metal will have more energy (and have a shorter wavelength) than
ions are put into a flame. This type of spectrum, called a the photon given off in the transition represented by the
bright line spectrum, is not continuous but instead contains right-hand arrow. In terms of energy,
only certain colors at particular wavelengths. A bright line (n 6 → n 2 ) > (n 3 → n 2 )
spectrum is due to transitions of electrons between energy The larger energy would be in the violet-blue portion of the
levels in atoms or ions. When an atom or ion absorbs energy, spectrum. The smaller energy would be in the red-orange
such as from a flame or electrical source, it absorbs only portion of the spectrum.
certain discrete amounts of energy. These amounts are the

1
Frequency and Energy Continuous Spectrum
The relationship between wavelength and frequency is: Find the tall, clear light bulb connected to a variable power
λν = C transformer. Turn the transformer on with the dial set to high.
C, the speed of light, equals 3.00 x 108 m/s. The violet line Hold the diffraction grating as instructed above to observe
with λ = 405 nm from the mercury spectrum would have a the filament in the light bulb. A full spectrum is visible.
frequency calculated as follows: Now t urn off the room lights, and observe the spectrum
C 3.00 x 108 m ⋅ s− 1 as the rheostat is turned down, then back up. Notice how
ν= ν = = 7. 41x1014 s− 1
λ or 405x10− 9 m the blues and greens diminish in intensity more than the
reds diminish as the temperature of the filament decreases,
Notice that λ is written as 405 x 10-9 m, rather than 405
then reappear as the temperature increases. The theory
nm.
available 100 years ago predicted that as the temperature
To find the energy of a photon, the Planck relationship is
increased, the spectrum would completely shift over into
used:
the ultraviolet, with no reds or yellows or greens remaining.
E = hν This inadequate theory had physicists mumbling about the
where h, the Plank constant, = 6.63 x 10-34 J·s. “ultraviolet catastrophe”. Theoretical physicists looked to
develop theories consistent with experimental data. Max
To find the energy of the violet line,
Planck developed a new theory which has held up for close
E = ( 6. 63x10− 34 J ⋅ s) ( 7. 41x1014 s −1 ) = 4. 91x10 −19 J to a century. The equation: E = hν is part of the theory.
This is the energy emitted when an electron in one particu‑ Line spectra
lar energy level in a mercury atom drops down to a lower The conditions used in this part of the experiment, namely,
particular energy level. 4.91 x 10-19 J might seem extraor‑ high voltage through a low pressure sample of an element,
dinarily small, but in terms of a mole of atoms, there would produce a characteristic line spectrum for each element.
be 296 kJ·mol-1. (Can you verify this?). Each element is labeled and set-up properly. Plug in the
high voltage source if necessary.
This is a good time to make a general observation about
quantities. You will hear people say, and perhaps you say, Hydrogen Spectrum: With the lights still out, observe the
“that seems like an awfully small amount”. The response hydrogen spectrum. The closer you get, the clearer it appears.
to this is, “compared to what?”. A mercury atom, one of the Observe the lines and draw them on the chart below.
really heavy atoms, weighs about 3 x 10-22g. Compared to
your weight, a mercury atom weighs “nothing”. Compared
to a neon atom, the mercury atom weighs 10 times as much.
A thousand percent heavier! The moral of the story is:
red yellow green blue violet
Consider everything in perspective.
EXPERIMENT Mercury Spectrum: Observe the lines and draw them on
the chart below. Just as H and Hg differ, so each atom has
Using the diffraction grating:
a unique spectrum.
Diffraction gratings split a light source into its component
wavelengths. To use the grating, hold it so the “MADE IN
U.S.A.” is on the bottom facing you. The right-side card‑
board frame should be between your dominant eye and the
light source, blocking the light source from your eye. The red yellow green blue violet
plastic should be to the left of your eye. You will see the
spectrum by glancing into the plastic. Neon Spectrum: Simply observe. Notice the number of
lines in the red and yellow portion of the spectrum.

The unique spectrum given by each element provides a simple


means of analysis for elements. After exciting a substance
with a spark or in a flame, the position of the spectral lines
produced gives the identity of the elements in the substance,
Light and the intensity of the lines gives the quantity of the ele‑
source ments. Of course, instruments that do this have data bases
Julie built in that allow for the experimental data to be compared
Enriquez with previously compiled data.

2
CALCULATIONS Also, notice that the lines have different widths. This is
typical of spectral lines, and spectroscopists rank lines
Hg Spectrum. The one you observed in the lab is a low
according to their appearance and abundance. Hence the
resolution spectrum. The spectral charts posted on the walls
designations s, p, d, and f for electron orbitals (from sharp,
show higher resolution spectra of a number of substances.
principal, diffuse and fundamental.
Look at a chart and sketch the spectral lines of mercury
roughly to scale in the strip below: (numbers are λ in nm) Hydrogen Spectrum.
The hydrogen atom is the simplest atom and a detailed
study of its spectrum leads to valuable insights. Shown in
Figure 1 below are the energy levels in the hydrogen atom
as calculated from the Schrödinger equation. The numbers
750 700 650 600 550 500 450 400
on the left give the energy of each level in joules. The
number on the right gives the principal quantum number
Notice that the spectrum has three lines shown in the yellow
of each level. The names along the top are the names of the
region. Record the actual wavelengths from the chart, then
scientists who first characterized the spectrum corresponding
calculate the frequency and energy of each of these three
to these transitions. Shown in Figure 2 is a black and white
lines in the mercury spectrum:
representation of the experimentally observed spectrum of
λ ν E
the hydrogen atom. IR is infrared, VIS is visible and UV is
_______ _______ _______
ultraviolet. The wavelength of each line in nanometers is
_______ _______ _______
listed below the line. Figure 2, which is experimental, can
_______ _______ _______
be calculated from Figure 1, which is theoretical.

Figure 1: Energy Levels and Some Possible Transitions for Hydrogen Atoms
0 n = ∞ (13 or 14)
-0.341 Lyman Balmer Paschen n=8
-0.445 Ultraviolet Visible Infrared n=7
-0.606 n=6
-0.872 n=5
-1.36 n=4

-2.42 n=3
7→3 6→3 5→3 4→3
Energy/10-19 Joules

n values
-5.45 n=2
6→2 5→2 4→2 3→2

Each arrow represents an energy


release, ∆E, as an electron goes
from a higher energy level to a
lower one. The energy is given
off as photons. The photons are
in the part of the spectrum
indicated above the arrows.

-21.8 5→1 4→1 3→1 2→1


n=1

Figure 2: H Atom Spectrum


Far IR IR Visible UV
410
397
389
4052

1876

1282

1094

1005

955

656

486
434

122
103
97.3

λ in nanometers
3
Hydrogen Spectrum Calculations To give consistency to the appearance of the energies calcu‑
lated, all energies will be shown with 10-19 as the exponent.
According to spectral theory, each line in the spectrum
Then the energy of the 97.3 nm line is 20.4 x 10‑19 J. This is
comes as an electron drops from a higher to a lower energy
level. In Figure 1 on page 57, the various vertical arrows very close to the absolute value of the ∆E for the n 5 → n1
show a number of such possible transitions. The energy of transition previously calculated, which was 20.9 x 10-19 J.
a transition, for example, the one indicated by the left hand Upon close inspection of the left and right y-axis coordi‑
vertical arrow in Figure 1, can be calculated by subtracting nates of Figure 1, it is seen that for the n 4 → n 1 transition,
the energy of the initial state from the energy of the final represented by the second from the left vertical arrow:
state (found on the left of the diagram):
∆E = ( −21. 8x10− 19 J ) − ( −1. 36x10 −19 J)
∆E = E final − Einitial = 20. 4 x10 − 19 J

= ( −21. 8x10 J ) − ( −0.872 x10 J)
− 19 − 19
This is exactly the same value as the Planck calculation for
= ( −20. 9x10− 19 J) the λ = 97.3 nm given just above. So we can conclude that
the spectral line at 97.3 nm is caused by an electron drop‑
(The negative value indicates energy released.) ping from n = 4 to n = 1 in the hydrogen atom.
This ∆E is for an n 5 → n1 transition (see the right side of
Figure 1 for n values). Your understanding of the calculations and discussion on
Each line in the hydrogen spectrum shown in Figure 2 has this page are crucial for the completion of the calculation
an energy which can be calculated using the Planck relation‑ table below. If you have difficulty with the calculations,
ship. The far right hand line has λ = 97.3 nm, or 97.3 x 10-9 reread this section. If the difficulties continue, see the
m. To calculate the energy, first find the ν of the line: instructor.

3.00 x108 m ⋅ s− 1 The calculations just performed are summarized in the first
ν= = 3. 08x1015 s− 1 line of the table below. Continuing with the wavelengths
97.3x10 −9 m
from Figure 2, complete the first three columns in the table.
Then By analyzing the energy levels in Figure 1, find which
(
E = ( 6. 63x10− 34 J ⋅ s) 3. 08x1015 s −1 ) transition is responsible for each spectral line, and indicate
= 2.04 x10− 18 J the transition in the last column.

CALCULATION TABLE
λ in nm ν in seconds ‑1 ∆E in Joules n high → n low

1 97.3 3.08 x 10 15 20.4 x 10 ‑19 4 →1

2 103

3 122

4 389

5 397

6 410

7 434

8 486

9 656

10 955

11 1005

12 1094

13 1282

14 1876

15 4052

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Name_________________________________________ Grade___________ Date ___________

The Rydberg equation is a famous relationship that first showed the order of the hydrogen spectrum. To calculate the fre‑
quency, the equation has the form:
 1 1
ν = RH 2 − 2 
 n1 n2 
In this equation, n1 is the same as nlow in the table, and n2 is the same as nhigh in the table. Use the values for ν, nlow and
nhigh from the first entry in the calculation table on the previous page, and solve this equation for RH (3 significant digits).
Use the values of ν, nlow and nhigh from the 5th entry and again calculate RH.

RH (from 1) = ________________s-1 RH (from 5) = ________________s-1



Now use this value of RH (averaged if they differ) and the values of n1 and n2 in the 10th entry to calculate ν for the 10th
data.

ν (calculated) = ________________s-1

Compare this calculated value to the value of the observed ν in the second column of the 10th entry.

ν (experimental) = ________________s-1

Does the calculated value agree with the observed value?______ If not, repeat your calculations.


QUESTION

When the Sun’s spectrum is carefully observed, a great number of spectral lines are apparent. If the lines are viewed in
groups, various elements are identified to cause specific groups of lines. For example, each of the lines seen in the mercury
spectrum occurs in the Sun’s spectrum.

Helium is named after Helios, the Greek name for the Sun, because evidence for its existence was observed in 1868 by
examining the sun’s spectrum. Since helium was not found on earth until 1895, how do you suppose observers knew they
had found a new element in 1868?