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Solutions 12

1. Spectrophotometry measures how light is absorbed by a sample at different wavelengths. Different wavelengths correspond to different molecular excitations like rotation, vibration, or electronic transitions. 2. Absorbance is directly proportional to concentration and is related to transmittance. Molar absorptivity is a measure of how likely a wavelength is to be absorbed. 3. A spectrophotometer directs light of different wavelengths at a sample and measures the transmittance or absorbance to obtain an absorption spectrum, which is a graph of absorbance versus wavelength.

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41 views3 pages

Solutions 12

1. Spectrophotometry measures how light is absorbed by a sample at different wavelengths. Different wavelengths correspond to different molecular excitations like rotation, vibration, or electronic transitions. 2. Absorbance is directly proportional to concentration and is related to transmittance. Molar absorptivity is a measure of how likely a wavelength is to be absorbed. 3. A spectrophotometer directs light of different wavelengths at a sample and measures the transmittance or absorbance to obtain an absorption spectrum, which is a graph of absorbance versus wavelength.

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Chan Pheng
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Solutions for Spectrophotometry Exercises

1. a) Doubling the frequency doubles the energy.

b) Doubling the wavelength halves the energy.

2. Microwave energies correspond to molecular rotation energies. Infrared


wavelengths can produce vibrational excitation. Visible light can promote
electrons to excited states (in colored compounds). Ultraviolet radiation can
electronically excite and ionize compounds and break chemical bonds.

3. Transmittance (T) is the fraction of incident light that passes through a sample. T
= P/Po, where Po is the incident radiant power and P is the transmitted power.

Absorbance (A) is logarithmically related to transmitance, A = -logT. When all


light is transmitted, absorbance is zero. When no light is transmitted,
absorbance is infinite.

Molar absorptivity (ε) is a measure of how likely a particular wavelength will be


absorbed.

Absorbance is proportional to concentration, A = εlc.

Transmittance, absorbance and molar absorptivity all depend on the wavelength


at which they are measured.

4. An absorption spectrum is a graph of absorbance versus wavelength.

5. Absorption of wavelngths in the 400-550 nm range means that only the red end
(yellow-orange-red) of the visible light spectrum is not absorbed so the sample
appears to be red-orange.

6.
Solutions for Spectrophotometry Exercises

7. Since absorbance is directly proportional to concentration, the absorbance will


double as the concentration doubles. From Prob. 6, it was noted that if T =
0.450, then A = 0.347. Thus, for the 0.0200 M solution A = 0.694 and

8. Beer’s law only applies to very dilute solutions and to the use of monochromatic
radiation.

9. The concentration of the diluted standard is

Assuming Beer’s law behavior,

Using data for the diluted standard,

10. Basic components of a single-beam spectrophotometer

light source
monochromator
sample holder
detector
Solutions for Spectrophotometry Exercises

11. Continuous radiation from the light source enters the monochromator through a
slit and the radiation reflects off a diffraction grating where it is dispersed (spread
out). After focusing, only a small band of radiation emerges from the exit slit of
the monochromator. By varying the orientation of the diffraction grating with
respect to the incoming radiation, a different wavelength can be selected for
passage through the monochromator.

12. In a single-beam instrument only a narrow band of wavelengths passes through


the sample and its intensity is detected. In a diode array spectrophotometer all
wavelengths emitted from the light source pass through the sample and are
dispersed by a diffraction grating onto an array of detectors (photodiodes). Thus
the intensity of the transmitted light at all wavelengths is measured
simultaneously.

13. Radiation reaching the PMT first strikes a surface called the photocathode where
electrons are ejected by the incident photons. These ejected electrons are
drawn to another surface (dynode) maintained at a slightly more positive
potential, where each incident electron ejects 2 or more electrons. This process
is repeated with a total of 8-10 dynode surfaces and results in a significant
number of electrons being collected as the electrical signal.

14. In order to obtain the sample absorbance, the intensity of light that passes
through a blank solution is first measured (Pblank). Then the intensity of light that
passes through the sample (Psample) is measured. The instrument then computes
the sample absorbance from -log (Psample/Pblank).

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