Important Concepts in UV-Vis and IR Spectros

BASIC SPECTROSCOPIC
TECHNIQUES: UV-Vis and IR

(Part 1)
Introduction to Spectroscopy
• Spectroscopy involves an
interaction between
matter and light
(electromagnetic
radiation).
• Light can be thought of as
waves of energy or packets
(particles) of energy called
photons.
• Properties of light waves
include wavelength and
frequency.
Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e 15-2
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15.1 Introduction to Spectroscopy
• There are many wavelengths of light that cannot be
observed with your eyes.

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Types of Electromagnetic radiation
Type of Quantum
Type Wavelength Interaction
Transition
Nuclear (Bond
 <10 nm Nuclear emission breaking or
ionization)
X-ray <10 nm Atomic ionization Inner Electron
uv 10 – 380 nm Electronic transition Bonding electron
vis 380 – 800 nm Electronic transition Bonding electron
IR 800nm - 100m Bond interaction Rotation/Vibration
Radio meters Nuclear absorption Rotation

4
Introduction to Spectrochemical Methods
15.1 Introduction to Spectroscopy
• When light interacts with molecules, the effect depends
on the wavelength of light used.

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Qualitative and Quantitative
Analysis using UV-Vis
Qualitative Analysis
• What is present/absent in the sample?
Quantitative Analysis
• How much of that analyte is present in the
sample
17.1 Classes of Dienes
• There are three categories for dienes:
– Cumulated: pi bonds are adjacent.

– Conjugated: pi bonds are separated by exactly ONE single bond.
– Isolated: pi bonds are separated by any distance greater than ONE single bond.

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UV-Vis Spectroscopy
• If light with the NECESSARY ENERGY strikes a compound
with pi bonds, an electron will be excited from the
HOMO to the LUMO.
• Light energy is converted into potential energy.

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UV-Vis Spectroscopy
• UV-Visible (UV-Vis) spectroscopy gives structural
information about molecules:
– A beam of light (200-800 nm) is split in two.
– Half of the beam travels through a cuvette with the analyte in
solution.
– The other half of the beam travels through a cuvette with just
the solvent (used as a negative control).
– The intensities of light that pass through the cuvettes are
compared to determine how much light is absorbed by the
analyte.

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How Do UV spectrometers work?
Rotates, to achieve
scan Matched quartz cuvettes
Sample in solution at ca. 10-5
M.
System protects PM tube
from stray light
D2 lamp-UV
Tungsten lamp-Vis
Two photomultiplier Double Beam makes it a

inputs, differential difference technique
voltage drives
amplifier.
• in space
• In time
instrument arrangement
Common arrangement for uv/vis
 Source radiation of the selected wavelength

is sent through the sample
Instruments for Optical
11
Spectrometry
SAMPLE CELLS or containers
Typical
examples of
commercially
available
cells for
uv/visible
region

12
Spectrometry
The Quantitative Picture
• Transmittance:
P0 P
T = P/P0 (power in) (power out)
• Absorbance:
A = -log10 T = log10 P0/P B(path through sample)
• The Beer-Lambert Law (a.k.a. Beer’s Law):

A = bc
Where the absorbance A has no units, since A = log 10 P0 / P
 is the molar absorbtivity with units of L mol -1 cm-1
b is the path length of the sample in cm
c is the concentration of the compound in solution, expressed in mol L -1 (or M, molarity)
Absorbance vs. transmitance
As the absorbance of the solution increases,

the transmittance decreases
14
Introduction to Spectrochemical Methods
UV-Vis Spectroscopy
• UV-Visible (UV-Vis) spectroscopy gives structural
information about molecules:
– The resulting data
is plotted to give a
UV-Vis absorption
spectrum.
– Compounds
require specific
wavelengths of
energy to excite.
WHY?

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UV-Vis Spectroscopy
• More conjugation gives a smaller π  π* energy gap.
• The smaller the energy gap, the greater the lambda max
(λmax).
217 258 290

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Color
• The visible region of the spectrum (400-700 nm) is
lower energy than UV radiation.
• Lycopene is responsible for the red color of tomatoes.
• β-carotene is responsible for the orange color of carrots.

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Color
• The color observed by your eyes will be the opposite of
what is required to cause the π  π* excitation.

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Color
A color wheel shows the observed color when a single color is
absorbed (only 1 λmax observed).
(or vice versa)
λmax = 510 nm
solution color
17.12 Color
• Bleaching agents
generally work by
breaking up conjugation
through an addition
reaction.
• Destroying long range
conjugation destroys the
ability to absorb colored
light. WHY?
• Does bleach actually
remove stains?
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17.11 UV-Vis Spectroscopy
• The group of atoms responsible
for absorbing UV-Vis light is
known as the chromophore.
• Woodward and Fieser developed rules to predict λmax for

chromophore starting with butadiene as the base.

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• Woodward and Fieser developed rules to predict λmax for
chromophore starting with butadiene as the base.
• The Woodward-Fieser rules are a guide to ESTIMATE λmax.

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• Practice with SKILLBUILDER 17.4.

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15.2 IR Spectroscopy
• Molecular bonds can vibrate by stretching or by bending
in a number of ways.

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instrument arrangement
Common arrangement for IR
 Source radiation of the selected wavelength

is sent through the sample

28 kadecastro
Spectrometry
15.2 IR Spectroscopy
• An IR • Most commonly,
spectrophotometer samples are deposited
irradiates a sample with NEAT on a salt (NaCl)
all frequencies of IR plate.
light.
• The frequencies that • Alternatively, the
are absorbed by the compound may be
sample tell us the types dissolved in a solvent or
of bonds (functional embedded in a KBr
groups) that are pellet.
present.
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DR – Diffuse Reflectance
Klein, Organic Chemistry 1e 7 -30
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ATR – Attenuated Total Reflectance
Transmission Accessory
IR Spectroscopy
• A signal on the IR spectrum has three important
characteristics: WAVENUMBER, INTENSITY, and SHAPE.

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15.3 IR Signal Wavenumber
• Rationalize the trends below using the wavenumber
formula:
1.
2.
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15.3 IR Signal Wavenumber
• The wavenumber formula and empirical observations allow us to designate
regions as representing specific types of bonds.

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15.4 IR Signal Strength
• The strength of IR signals can vary.

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• The more polar the bond, the greater the opportunity
for interaction between the waves of the electrical field
and the IR radiation.
• Greater bond polarity = stronger IR signals.

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• Note the general strength
of the C=O stretching signal
vs. the C=C stretching
signal.
• Imagine a symmetrical
molecule with a completely
nonpolar C=C bond: 2,3-
dimethyl-2-butene.
• 2,3-dimethyl-2-butene does
not give an IR signal in the
1500–2000 cm-1 region.
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15.5 IR Signal Shape
• Some IR signals are broad, while others are very narrow.
• O–H stretching signals are often quite broad.

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• When possible, O–H bonds
form hydrogen bonds (H-bonds)
that weaken the O–H bond
strength.
• WHY does H-bonding affect
the O–H bond strength?
• The H-bonds are transient, so the sample will contain
molecules with varying O–H bond strengths.
• Why does that cause the O–H stretch signal to be broad?
• The O–H stretch signal will be narrow if a dilute solution of an
alcohol is prepared in a solvent INCAPABLE of
H-bonding.
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• In a sample with an intermediate concentration, both
narrow and broad signals are observed.

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• Consider how broad the O-H stretch is for a carboxylic
acid and how its wavenumber is around 3000 cm-1
rather than 3400 cm-1 for a typical O-H stretch.

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• H-bonding is often more pronounced in
carboxylic acids, because they can forms
H-bonding dimers.

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• Primary and secondary amines exhibit N–H stretching
signals. WHY not tertiary amines?
• Because N–H bonds are capable of H-bonding, their

stretching signals are often broadened.
• Which is generally more polar, an O–H or an N–H bond?
• Do you expect N–H stretches to be strong or weak

signals?

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SUMMARY of Regions of the
Infrared Spectrum
• 4000-2500 cm-1 N-H, • 2000-1500 cm-1 double
C-H, O-H (stretching)
– 3300-3600 N-H, O-H bonds (stretching)
– 3000 C-H – C=O 1680-1750
• 2500-2000 cm-1 CC and C  N – C=C 1640-1680 cm-1
(stretching)
• Below 1500 cm-1
“fingerprint” region
47
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Important Concepts in UV-Vis and IR Spectros

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BASIC SPECTROSCOPIC

TECHNIQUES: UV-Vis and IR

Copyright 2012 John Wiley &

Copyright 2012 John Wiley &

uv 10 – 380 nm Electronic transition Bonding electron

vis 380 – 800 nm Electronic transition Bonding electron

IR 800nm - 100m Bond interaction Rotation/Vibration

Radio meters Nuclear absorption Rotation

Copyright 2012 John Wiley &

– Cumulated: pi bonds are adjacent.

Copyright 2012 John Wiley &

Copyright 2012 John Wiley &

Copyright 2012 John Wiley &

Two photomultiplier Double Beam makes it a

Common arrangement for uv/vis

 Source radiation of the selected wavelength

Instruments for Optical

• The Beer-Lambert Law (a.k.a. Beer’s Law):

As the absorbance of the solution increases,

Copyright 2012 John Wiley &

Copyright 2012 John Wiley &

• β-carotene is responsible for the orange color of carrots.

Copyright 2012 John Wiley &

Copyright 2012 John Wiley &

• Woodward and Fieser developed rules to predict λmax for

Copyright 2012 John Wiley &

• The Woodward-Fieser rules are a guide to ESTIMATE λmax.

Copyright 2012 John Wiley &

Copyright 2012 John Wiley &

Common arrangement for IR

 Source radiation of the selected wavelength

Instruments for Optical

Copyright 2012 John Wiley &

Copyright 2012 John Wiley &

Copyright 2012 John Wiley &

• Greater bond polarity = stronger IR signals.

• O–H stretching signals are often quite broad.

Copyright 2012 John Wiley &

Copyright 2012 John Wiley &

Copyright 2012 John Wiley &

• Because N–H bonds are capable of H-bonding, their

• Do you expect N–H stretches to be strong or weak

Copyright 2012 John Wiley &

Copyright 2012 John Wiley &

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