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The EM Spectrum

Ch. 18 Fundamentals of
Spectrophotometry

E = hcυ~ υ~ = 1 / λ (wavenumber)

Definitions Absorption Process


• Spectrophotometry (spectroscopy) is any
analytical method that uses light for
measurement of chemical concentrations
Real-time monitoring of Absorption spectrum of O3
gases in the human airway
with spectroscopy

A molecule that absorbs light photons will end up with increased energy. The
molecule will be promoted to an excited state. Microwave energy will cause
rotation of compounds. IR energy is high enough to promote bond stretching.
UV/Vis energy promotes electrons into higher orbitals. Short-λ UV and X-rays
can ionize molecules or even break bonds.

Properties of Light Energy Example


• Light can be thought of as a wave or particle. • How much is the energy of CO2 increased per
– The wavelength, λ, is the distance between crests mole when it absorbs IR at 4700 cm-1?
of a wave (m)
– The frequency, υ, is the number of oscillations per E = hcυ~
second (Hz) = (6.626 × 10 -34
J ⋅ s)(2.998 × 108 m/s)(4700 cm -1 )(100 cm/m) = 9.33 × 10 -20 J
υ×λ = c c = 2.998 × 10 m/s
8
= (9.33 × 10 - 20
J)(6.022 ×10 23 ) = 56 kJ/mol
E = hυ υ = 6.626 ×10 −34 J ⋅ s

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Spectrometer Experiment Wavelengths and Color

Irradiance in Irradiance out


Irradiance, P, is measured in W·m-2
T = P / P0 Pathlength
Transmittance, T, is the fraction of
original light not absorbed by the
sample, or

A light source can be a lamp, laser, or even a light bulb. A monochromator


(“one color”) is used to select a particular wavelength. This is typically a grating,
but can be a prism or filter. The light then passes through the sample, containing
the analyte. Afterwards, the light is detected.

Absorbance and Beer’s Law Cells for Spectrophotometry


• Absorbance, A, the amount light absorbed by
the sample is related to transmittance:
P 
A = log 0  = − log T
P
• Beer’s law relates the absorbance of a chemical
to its concentration:
Aλ = ε λ bc
b is the pathlength, typically in cm, and c is the
concentration of the chemical species in M
ε is the molar absorptivity, the unit that tells how
much light is absorbed for a given wavelength. ε
has units of M-1 cm-1

Beer’s Law Example Errors in Spectroscopy Measurements


• Find the absorbance of a 0.0220 M solution
with a molar absorptivity of 15.5 M-1 cm-1 in a There can be many sources
2.00 cm pathlength cell of error with a spectroscopic
method. Electronic noise in
Aλ = ε λ bc = (15.5 M -1cm -1 )(2.00 cm)(0.0220 M) = 0.68 the detector is the most
common. Mistakes with the
cuvet can also be important--
• If you wanted to find transmittance: improper positioning,
touching with fingers or
log T = − A = 10 −0.68 = 0.21 allowing dust on the cell all
could introduce error.
• 21% of the irradiated light emerges from the
analyte sample

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Beer’s Law and Calibration Absorption vs. Emission Spectra
Molecules always emit
radiation at longer
wavelengths than they absorb
at.

The absorbance and emission


spectra usually resemble a
mirror image when viewed
together.
Iron can be analyzed spectroscopically as an iron-
ferrozine complex. However, some metals, especially
copper can interfere with the complexation reaction.
If copper is masked, then the analysis can be done.
Theoretically, the y-intercept should be at 0, but as
you’ve probably seen in lab, error can cause an
absorbance reading at 0 concentration.

Emission Spectroscopy
The Effects of Absorbing Light Experimental Setup
UV-Vis promotes
electrons into higher
orbitals

IR promotes bending Pretty similar to the absorbance measurements,


and stretching of except that you add in an extra monochromator
bonds after the sample and before the detector.

We typically hold the excitation (absorption)


wavelength constant and measure the emission
spectrum resulting from it.

Emission of Light Chemiluminescence


• When a chemical reaction makes a product
that emits light, it is chemiluminescence

• This is the type of chemistry that takes


place when a firefly gives off light or when
you have a glow stick

• Some biochemical reactions also


Fluorescence occurs at lower wavelengths (higher energy) than
chemiluminesce
phosphorescence. Spectroscopy using emission of light is considerably more
sensitive than absorption of light due to inherently lower background.

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Chemiluminescence for Air Quality
• Chemiluminescence is used routinely for air
quality measurements of O3 or NOx

• Anytime you hear ozone or nitrogen oxide


concentrations reported, it’s from this
analytical technique

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