EXPERIMENT 11: THE

ABSORPTION SPECTRA OF
CONJUGATED DYES AND
THE FEMO THEORY OF
CONJUGATED PI
ELECTRONS

Andrew Fleming, Jordan Haskins,

Gino Moore, Amanda Petty
INTRODUCTION

In our experiment, we measured the

absorbencies and wavelengths of 3 different
conjugated dyes:
 1,1' diethyl-4,4'-cyanine iodide
 1,1' diethyl-4,4'-carbocyanine
 1,1' diethyl-4,4'-dicarbocyanine iodide

This experiment was done in order to test the

FEMO (Free Electron Molecular Orbital) theory
and can be thought of as a particle-in-a-box
problem because of the long, conjugated chains
in the molecules.
MATERIALS AND METHODS

 Spectronic 20 spectrophotometer
 Methanol
 3 disposable pipettes
 A waste beaker
 3 dyes in solid form
 4 Cuvettes (used in spectrophotometer)
MATERIALS AND METHODS
A single crystal of 1,1' diethyl-
4,4'-cyanine iodide was placed in the
cuvette and diluted with methanol.
 The absorption was read, following
directions located with the
spectrophotometer.
 A graph of the absorbance versus the
wavelength was displayed on the
spectrophotometer screen.
 Initially, our absorbance was much
higher than the recommended value of
2.
MATERIALS AND METHODS
 A small amount of solution was taken out
using the pipette and the mixture was further
diluted with methanol.
 Dilution was continued until the absorbance
was less than 2.
 At this point, we printed the graph from the
spectrophotometer.
 These steps were repeated for the other 2
dyes.
RESULTS
1,1'-diethyl-4,4'-cyanine iodide
Absorbance

Wavelength (nm)
RESULTS
1,1'-diethyl-4,4'-carbocyanine iodide
Absorbance

Wavelength (nm)
RESULTS
1,1'-diethyl-4,4'-dicarbocyanine iodide
Absorbance

Wavelength (nm)
RESULTS
Dye Π electrons n (HOMO) n (LUMO)
Cyanine 10 5 6
Carbocyanine 12 6 7
Dicarbocyanine 14 7 8

E=n2h2/8meL2
Dye λmax (m), calc λmax (m), exp Percent Error
Cyanine 5.88E-07 5.90E-07 0.36
Carbocyanine 7.16E-07 7.08E-07 1.16
Dicarbocyanine 8.45E-07 8.14E-07 3.67
DISCUSSION
Our experimental wavelengths of maximum
absorbance were proportional to the lengths
of the dye molecules.
Put simply, as the dye molecule length
increased, the wavelength of maximum
absorbance also increased.
This was predicted by the FEMO theory.
CONCLUSION
When compared to the FEMO predictions, our
data for the actual λmax seem to be accurate.

Since the values for the experimental and

calculated wavelengths of maximum
absorption were similar, this experiment was
a good illustration of the FEMO theory and
the “particle-in-a-box” concept.
Citations

• Clark, Roy W.; Howard, James C. Physical Chemistry

Lab Manual, 4th ed., RonJon Publishing, Denton, TX,
1996.
• Fleming, A.J.; Physical Chemistry Laboratory
Notebook, 2007 p. 15-16.
• Haskins, J.R.; Physical Chemistry Laboratory
Notebook, 2007 p. 21-22.
• Moore, L.G.; Physical Chemistry Laboratory
Notebook, 2007 p. 16-17.
• Petty, A..; Physical Chemistry Laboratory Notebook,
2007 p. 15-16.