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WEEK7!
1. OverviewofIRanduvvis Electrochemical
2. Instrumentationfor Spectroscopy
Sensors
spectrophotometrs
3. Interprepting IRanduvvis
spectra
Week 7-8
Infrared and ultraviolet-visible
spectroscopy: Overview
Week 7, Lecture 1
Molar Absorptivity,
X-axis units are wavelength, y-axis units are the amount of light absorbed or transmitted
Electromagnetic
Radiation: X-Axis
Converting EM
Radiation Units
h: plancks constant
c: speed of light
: wavenumber (1/)
Examples of
converting units
You have light incident on a sample for absorption spectroscopy. Its wavelength
is 500 nm. What is the energy of the light in Joules? What kind of spectroscopy is
this? This is uv-vis (I know from the wavelength range)
6.63 10 3.00 10 /
E 3.98 10
500 10
An infrared spectrometer designed to measure ethanol in breath uses two filters at
3.400 microns and 9.500 microns to detect light. What do these filter wavelengths
correspond to in wavenumbers (cm-1)?
1 1 1
2941
3.400 10 100
1 1 1
1052
9.500 10 100
Ultra-Violet Visible:
Electronic Transitions
Molar Absorptivity,
Transmittance
Ranges 0 1
Near 1 not a lot of
absorption
Absorbance
Ranges 0 4
Near 4 a lot of absorption
If too small, hard to detect
P0 is the power incident If too big, not enough light
P is the power after passing through
Beers Law for
Absorbance
One must run a blank!
10 .794
.5 .303
Beers Law In Action
PathL 1 cm
Manga 54.938
PotPerm 158.034
ppm moles/L DeltaA Epsilon
4 7.28E05 0.18 2.47E+03
8 1.46E04 0.33 2.27E+03
12 2.18E04 0.5 2.29E+03
16 2.91E04 0.68 2.33E+03
20 3.64E04 0.85 2.33E+03
Summary of
Quantitative Terms
Place sample in
this compartment
Wikimedia Commons
The Block Diagram:
Absorption Specto(photometer)
Biggest challenge in IR is
typically will not use
solvents need solids
that dont absorb or use
ATR sampling
Light Sources
From www.chem.agilent.com
Constructive Interference:
Key to a Grating
Constructive Destructive
The groves per millimeter govern HOW SPREAD OUT and hence the resolution:
Better resolution in wavelength means fewer photons to detect!
Gratings Help
Disperse the Light
In a FT spectrometer, data is
collected in the time domain and
fourier transformed into frequency:
https://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/Spectrpy/UV-Vis/spectrum.htm
Infrared: Vibrational
Transitions
Interpreting Infrared
Spectra
Some Important
KEY IR Peaks
frequency, cm1 bond functional group
36403610 (s,
OH stretch, free hydroxyl alcohols, phenols
sh)
35003200 (s,b) OH stretch, Hbonded alcohols, phenols
34003250 (m) NH stretch primary, secondary amines, amides
33002500 (m) OH stretch carboxylic acids
C(triple bond)CH: CH
33303270 (n, s) alkynes (terminal)
stretch
31003000 (s) CH stretch aromatics
31003000 (m) =CH stretch alkenes
30002850 (m) CH stretch alkanes
28302695 (m) HC=O: CH stretch aldehydes
The only two Ill 22602210 (v) C(triple bond)N stretch
22602100 (w) C(triple bond)C stretch
nitriles
alkynes
want you to know 17601665 (s C=O stretch
17601690 (s) C=O stretch
carbonyls (general)
carboxylic acids
1.the C-H absorption(s) between 3100 and 2850 cm-1. An absorption above 3000 cm-1 indicates C=C, either alkene or aromatic.
Confirm the aromatic ring by finding peaks at 1600 and 1500 cm-1 and C-H out-of-plane bending to give substitution patterns
below 900 cm-1. Confirm alkenes with an absorption at 1640-1680 cm-1. C-H absorption between 3000 and 2850 cm-1 is due to
aliphatic hydrogens.
2.the carbonyl (C=O) absorption between 1690-1760cm-1; this strong band indicates either an aldehyde, ketone, carboxylic acid,
ester, amide, anhydride or acyl halide. The an aldehyde may be confirmed with C-H absorption from 2840 to 2720 cm-1.
3. the O-H or N-H absorption between 3200 and 3600 cm-1. This indicates either an alcohol, N-H containing amine or amide, or
carboxylic acid. For -NH2 a doublet will be observed.
4. the C-O absorption between 1080 and 1300 cm-1. These peaks are normally rounded like the O-H and N-H peak in 3. and are
prominent. Carboxylic acids, esters, ethers, alcohols and anhydrides all containing this peak.
5. the CC and CN triple bond absorptions at 2100-2260 cm-1 are small but exposed.
6. a methyl group may be identified with C-H absorption at 1380 cm-1. This band is split into a doublet for isopropyl(gem-
dimethyl) groups.
7. structure of aromatic compounds may also be confirmed from the pattern of the weak overtone and combination tone bands
found from 2000 to 1600 cm-1.
http://wwwchem.csustan.edu/Tutorials/quickir.htm
Infrared Spectra:
A Fingerprint
http://www.chemguide.co.uk/analysis/ir/interpret.html
More IR Practice
http://www.chemguide.co.uk/analysis/ir/interpret.html
Case Study 3: Breathalyzers
for Fighting Crime
Week 7, Lecture 7
Last academic year, twenty emergency room visits for alcohol poisoning,
students arrested for drunk driving (state police), one tragic accident
A small percentage of
alcohol is exhaled as gas
through the lungs.
2: (Campus Lawyer) Need a secondary evidentiary method for drivers with high BAC
Keychain
Breathalyzers! Car-GPS
Breathalyzers
IPOD
Breathalyzers!
Coin Operated
Blow
In Bars
breathalyzers
Different Approaches to Breathalyzers
Chromium (VI) is orange and is reduced to the green chromium (III) ion
(Requires sulfuric acid (100 ml) to make the reaction go)
Slow process on the order of about 30 minutes
Labianca, Dominick A. The Chemical Basis of the Breathalyzer: A Critical Analysis, Journal of Chemical
Education. (1990). 67(3). 259-261.
State of the art in breathalyzers
Most commercial handheld devices use
electrochemical fuel cell technology
Fuel cell has two platinum electrodes with a
porous acid electrolyte
As exhaled air goes past, Pt oxidizes any
alcohol into acetic acid, 2 protons and 2
electrons.
Electrons flow through a wire hooked to a
current meter a microprocessor measures the
electrical current which is calibrated to the BAC
Infrared Spectrometer
Uses Infrared spectroscopy to detect ethanol (C-O, O-
H, C-H, C-C bonds)
IR energy passes through sample chamber containing
breath sample and then through narrowband IR filter
Filtered energy focused on photocell detector which
converts it to electrical pulses
Microprocessor interprets pulses and calculates BAC
Microprocessor
Sample Chamber
Photocell
http://www.youtube.com/watch?v=YwlA1ejfC8E
Checking at 3.4 and 9.5
microns
2. Of the various measurement devices what are the most appropriate for each group?