Infrared Spectroscopy

Infrared Spectroscopy-IR

Common Applications Identification of compounds by matching spectrum of unknown compound with reference spectrum (fingerprinting) Identification of functional groups in unknown substances Identification of reaction components and kinetic studies of reactions Identification of molecular orientation in polymer films Detection of molecular impurities or additives present in amounts of ! and in some cases as low as "#" ! Identification of polymers$ plastics$ and resins Analysis of formulations such as insecticides and copolymers

Complementary or %elated &echni'ues

(uclear )ass

magnetic resonance provides additional information on detailed molecular structure spectrometry provides molecular mass information and additional structural information spectroscopy provides complementary information on molecular vibration# (Some vibrational modes of motion are I%*inactive but %aman*active and vice versa#)* NOT INCLUDED IN THIS COURSE

%aman

Introduction
Infrared

(I%) spectroscopy is one of the most common spectroscopic techni'ues used by organic and inorganic chemists is the absorption measurement of different I% fre'uencies by a sample positioned in the path of an I% beam# main goal of I% analysis is to determine the chemical functional groups in the sample# functional groups absorb characteristic fre'uencies of I% radiation#

it

&he

Different

I% +re'uency %ange

Region (ear )iddle +ar )ost used

range (m) "#,-*.#/ .#/*/" /"* """ .#/* /

Wave number range, cm-1 .$ """ to 0""" 0""" to ."" ."" to " 0""" to 3,"

Frequency Range 1#-2 " 0* #.2 " 0 #.2 " 0* 3#"2 " . 3#"2 " .* 1#"2 " #.2 " 0* .#"2 " 1

+&*I% Instrument
1. The Source: Infrared energy is emitted from a glowing black*body source# &his beam passes through an aperture which controls the amount of energy presented to the sample (and$ ultimately$ to the detector)# 2. The Interferometer: &he beam enters the interferometer where the 4spectral encoding5 takes place# &he resulting interferogram signal then e2its the interferometer# 3. The Sample: &he beam enters the sample compartment where it is transmitted through or reflected off of the surface of the sample$ depending on the type of analysis being accomplished# &his is where specific fre'uencies of energy$ which are uni'uely characteristic of the sample$ are absorbed# 4. The Detector: &he beam finally passes to the detector for final measurement# &he detectors used are specially designed to measure the special interferogram signal# 5. The Computer: &he measured signal is digiti6ed and sent to the computer where the +ourier transformation takes place# &he final infrared spectrum is then presented to the user for interpretation and any further manipulation#

+&*I% Instrument* Schematic

)ichaelson Interferometer

Stationary mirror

HeNe laser

Beam Splitter

Source Moving mirror PMT Sample

Detector

)ichaelson Interferometer

Interferometers employ a eamspl!tter which takes the incoming infrared beam and divides it into two optical beams# 7ne beam reflects off of a flat mirror which is fi2ed in place# &he other beam reflects off of a flat mirror which is on a mechanism which allows this mirror to move a very short distance (typically a few millimeters) away from the beamsplitter# &he two beams reflect off of their respective mirrors and are recombined when they meet back at the beamsplitter# 8ecause the path that one beam travels is a fi2ed length and the other is constantly changing as its mirror moves$ the signal which e2its the interferometer is the result of these two beams 4interfering5 with each other# &he resulting signal is called an !nterfero"ram which has the uni'ue property that every data point (a function of the moving mirror position) which makes up the signal has information about every infrared fre'uency which comes from the source# &his means that as the interferogram is measured$ all fre'uencies are being measured s!multaneously# &hus$ the use of the interferometer results in e2tremely fast measurements# 8ecause the analyst re'uires a fre#uency spectrum (a plot of the intensity at each individual fre'uency) in order to make an identification$ the measured interferogram signal can not be interpreted directly# A means of 4decoding5 the individual fre'uencies is re'uired# &his can be accomplished via a well*known mathematical techni'ue called the $our!er transformat!on# &his transformation is performed by the computer which then presents the user with the desired spectral information for analysis#

I% Spectrum

I% absorption information is generally presented in the form of a spectrum with wavelength or wavenumber as the 2*a2is and absorption intensity or percent transmittance as the y*a2is

&heory of Infrared
Dipole changes During 9ibrations and %otations

I% absorption * a molecule must undergo a net change in dipole moment due to vibrational or rotational motion# :omonuclear species such as 7.$ (. or Cl. ; no net change in dipole moment occurs during vibration or rotation# <g# &he charge distribution around a molecule of :Cl is not symetric because the Cl has a higher electron density than the hydrogen# :Cl has a significant dipole moment and known as polar molecule Dipole moment= determined by the magnitude of the charge difference and the distance between the two centre of centre of charge# as a :Cl vibrates$ a regular fluctuation in dipole moment occurs$ an a field is established that can interact with the electrical field associated with radiation# If the fre'uency of the radiation e2actly matches a natural vibrational fre'uency of the molecule$ a net transfer of energy takes place that results in a change in the amplitude of the molecular vibration$ absorption of the radiation is the conse'uence# Similarly$ the rotation of asymmetric molecules around their centres of mass result in a periodic dipole fluctuation that can interact with radiation#

&heory of Infrared
%otational &ransitions

&he energy re'uired to cause a change in rotational is minute (small) and corresponds to radiation of "" cm* or less (> ""?m) %otational levels are 'uanti6ed@ i) Absorption by gases in the far I% region is characteri6ed by discrete$ well*defined line ii) Absorption by li'uids or solids intramolecular collisions and interactions cause broadening of the lines in to a continuum#

9ibrationalA%otational &ransitions

9ibrational energy levels are also 'uanti6ed for most molecules the energy differences between 'uantum states correspond to the mid*I% region# &he I% spectrum of a gas usually consists of closely spaced lines$ because there are several rotational energy state for each vibrational state# 7n the other hand$ rotation is highly restricted in li'uids and solids$ in such sample$ discrete vibrationalArotational lines disappear$ leaving only somewhat broadening vibrational peaks#

&ypes of molecular vibration

i)

Stretching= involves a continues change in the inter atomic distance along the a2is of the bond between two atoms# . types= Symetric stretching and asymetric stretching 8ending= characteri6ed by a change in the angle between two bonds# 0 types of bending vibrations= scissoring(bending)$ rocking$ wagging and twisting#

ii)

Stretching and 8ending

Symmetric

Asymmetric

In plane rocking

In plane scissoring

7ut of plane wagging

7ut of plane twisting

&he I% spectrum ( Dudley Billiams pg 1")

A comple2

molecule*many vibrate modes involve in the whole molecule

:owever$

these molecular vib# are largely associated with the vib# of individual bonds and called locali6ed vibrations# locali6ed vibrations are useful for the identification of functional groups$ such as the stretching vibs of=

&hese

Single bond (7*: C (*:) and all kinds of triple and double bonds$ all of which occur with fre'uency greater than /""cm*
&he

stretching vib# of other single bonds$ most bending vibrations and the soggier vibration of the molecule as a whole give rise to a series of absorption bands at lower energy$ below /""cm* $ the position of which are characteristic of that molecule (+ingerprint region)#

+ull spectrum of cortisone acetate $ pg 1

+ull spectrum of cortisone acetate $ pg 1

Strong absorption from the stretching vibrations above /""cm* $ showing that the presence of each of the functional groups=
7*: 1

group

diff CD7 groups

&he weaker absorption of the CDC double bond

4finger

print region5 below /""cm*

Identification of I% spectrum (organic comp)

&wo step processes=

Determine

what functional groups are present*e2amining the group fre'uency region (13"" ; .""cm* ) comparison of the spectrum of the unknown with the spectra of pure compounds that contain all of the functional groups found in the first step# &he fingerprint region ( .""*3""cm* ) is useful due to small differences in the structure and constitution of a molecule result in significant changes in the appearance and distribution of absorption peaks in this region# Conse'uently$ a close match between two spectra in the fingerprint region (as well as others) constitutes almost certain evidence for the identity of the compound yielding the spectra#

Detailed

&able of group fre'uency for organic group

Bond C*: C*: C*: C*: 7*:

Type of compound Alkanes Alkenes (CDC) Alkynes (CFC) Aromatic ring )onomeric alcohols$ phenols :ydrogen*bonded alcohols$ phenols )onomeric carbo2ylic acids :*bonded carbo2ylic acids Amines$ amides Alkenes Aromatic rings Alkynes Amines$ amides (itriles Alcohols$ ethers$ carbo2ylic acids$ esters Aldehydes$ ketone$*C77:$ esters (itro compounds

Frequency range, cm-1 .-/"*.E," 10"* 0," 1" "*1"E/ 3,/*EE/ 11"" 1" "*1 "" 3E"*E"" 1/E"*13/" 1.""*13"" 1/""*13/" ./""*.,"" 11""*1/"" 3 "* 3-" /""* 3"" . ""*..3" -"* 13" .. "*..-" "/"* 1"" 3E"* ,3" /""* /," 1""* 1,"

In en!i y Strong Strong )edium Strong Strong )edium Strong 9ariable 9ariable (sometimes broad) )edium 8road )edium 9ariable 9ariable 9ariable Strong Strong Strong Strong Strong Strong

(*: CDC CDC CFC C*( CF( C*7 CD7 (7.

IR Spectroscopy Tutor!al: %o& to analy'e IR spectra

&he distinctive bands of the common functional bands=

3500-3300 cm-1

NH stretch

amines alcohols, a broad, strong band alkenes alkanes ketones, aldeh"des, esters alkenes

3500-3200 cm-1

OH stretch

3100-3000 cm-1 3000-2850 cm-1 17 0-1 5 cm-1

CH stretch CH stretch C!O stretch C!C stretch

1 80-1 #0 cm-1

i) 8egin by looking in the region from 0"""* 1""# Gook at the C;: stretching bands around 1"""=

Indicates: )re an" or all to the right o* 3000& )re an" or all to the le*t o* 3000& alk"l gro(%s ,%resent in most organic molec(lesa C!C bond or aromatic gro(% in the molec(le

ii) Gook for a carbonyl in the region ,3"* 3E"# If there is such a band=
Indicates: $s an OH band also %resent& $s a CO band also %resent& $s an aldeh"dic CH band also %resent& $s an NH band also %resent& )re none o* the abo+e %resent& a carbo'"lic acid gro(% an ester an aldeh"de an amide a ketone

Gook for a broad 7;: band in the region 1/""*1."" cm* # If there is such a band=

Indicates:
$s an OH band %resent&

an alcohol or %henol

Gook for a single or double sharp (;: band in the region 10""*1./" cm* # If there is such a band= Indicates: )re there t.o bands& $s there onl" one band& a %rimar" amine a secondar" amine

7ther structural features to check for= Indicates: )re there CO stretches& $s there a C!C stretching band& )re there aromatic stretching bands& $s there a C/C band& )re there -NO2 bands& an ether ,or an ester i* there is a carbon"l band tooan alkene an aromatic an alk"ne a nitro com%o(nd

IR Spectroscopy Tutor!al: (l)anes

&he spectra of simple alkanes are characteri6ed by absorptions due to C;: stretching and bending (the C;C stretching and bending bands are either too weak or of too low a fre'uency to be detected in I% spectroscopy)# In simple alkanes$ which have very few bands$ each band in the spectrum can be assigned# C;: stretch from 1""";.-/" cm* C;: bend or scissoring from 0,"* 0/" cm* C;: rock$ methyl from 1,"* 1/" cm* C;: rock$ methyl$ seen only in long chain alkanes$ from ,./*,." cm*

IR Spectroscopy Tutor!al: (l)enes

Alkenes are compounds that have a carbon*carbon double bond$ ;CDC;# &he stretching vibration of the CDC bond usually gives rise to a moderate band in the region 3-"* 30" cm* # Stretching vibrations of the ;CDC;: bond are of higher fre'uency (higher wavenumber) than those of the ;C;C;: bond in alkanes#

CDC stretch from 3-"* 30" cm* DC;: stretch from 1 ""*1""" cm* DC;: bend from """*3/" cm*

IR Spectroscopy Tutor!al: (romat!cs

&he DC;: stretch in aromatics is observed at 1 ""*1""" cm* # (ote that this is at slightly higher fre'uency than is the ;C;: stretch in alkanes# Aromatic hydrocarbons show absorptions in the regions 3""* /-/ cm* and /""* 0"" cm* due to carbon*carbon stretching vibrations in the aromatic ring#

C;: stretch from 1 ""*1""" cm* overtones$ weak$ from ."""* 33/ cm* C;C stretch (in*ring) from 3""* /-/ cm* C;C stretch (in*ring) from /""* 0"" cm*

IR Spectroscopy Tutor!al: (lcohols

Alcohols have characteristic I% absorptions associated with both the 7*: and the C*7 stretching vibrations#

7;: stretch$ hydrogen bonded 1/""*1."" cm* C;7 stretch .3"* "/" cm* (s)

IR Spectroscopy Tutor!al: *etones

&he carbonyl stretching vibration band CD7 of saturated aliphatic ketones appears at , / cm* # ConHugation of the carbonyl group with carbon*carbon double bonds or phenyl groups$ as in alpha$ beta*unsaturated aldehydes and ben6aldehyde$ shifts this band to lower wave numbers$ 3-/* 333 cm*

CD7 stretch= aliphatic ketones , / cm* I$ J*unsaturated ketones 3-/* 333 cm*

IR Spectroscopy Tutor!al: (ldehydes

&he carbonyl stretch CD7 of saturated aliphatic aldehydes appears from ,0"* ,." cm* # As in ketones$ if the carbons adHacent to the aldehyde group are unsaturated$ this vibration is shifted to lower wavenumbers$ , "* 3-/ cm*

:;CD7 stretch .-1"*.3E/ cm* CD7 stretch= aliphatic aldehydes ,0"* ,." cm* alpha$ beta*unsaturated aldehydes , "* 3-/ cm*