I

NDEXOFHYDROGENDEFI
CIENCY

Todeterminethei
ndexofhydrogendef
ici
encyforacompound,appl
ythef oll
owingsteps:
1.
Determinetheformulaforthesaturated,
acycl
ichydrocarboncontai
ningthesamenumber
ofcarbonatomsastheunknownsubstance.

[Link] ementspresenti ntheunknown.A ddone

hydrogenatomforeachGroupVelement( N,P,
As,
Sb,
Bi)
,presentandsubtractonehydrogenatom
foreachGroupVI
Ielement(F,
Cl,
Br,
I)present.

C2H6, C2H7N, C2H8N2,

C2H9N3(GroupV)
C2H6, C2H5F, C2H4F2, C2H3F3(
GroupVI
I)
[Link]
ements(O,S,Se,Te),
nochangei
nthenumberofhydrogensi
srequi
red.
fπbonds
and/
orringsi
nthestructuralformul
aoftheunknownsubstance.
C2H6, C2H6O, C2H6O2,
C2H6O3 (
GroupVI
)

[Link]
sformulawi
ththemolecul
arformul
aoftheunknown.
Determi
nethenumberof
hydrogensbywhi
chthetwoformul
asdiff
er.

5..Dividethedi
fferencei
nthenumberofhydrogensbytwotoobtaintheindexofhydrogen
deficiency.
Thi
sequalsthenumberofπbondsand/orringsi
nthestructuralformul
aofthe
unknownsubstance

2C+2+N-H-X
D
egreeofUnsaturati
on=
2
whereC=numberofcarbonatoms
N=numberofnitrogenatoms
H=numberofhydrogenatoms
X=numberofhalogenatoms
Secondmethod-THERULEOFTHI
RTEEN
Asaf i
rststepi ntheRuleofThirteen,wegenerateabaseformul a,whi
chcontai
nsonlycarbon
[Link] ormulaisf oundbydividi
ngthemol armassMby1
ecul 3(themassof
onecarbonplusonehydrogen) .
Thiscalcul
ationprovidesanumeratornandaremainderr.
M r
=n+
13 1
3
Forexample
Ifthemolecularmassofthesubstancegi venis94amuthen
94 3
=7+
13 13
Heren=7andr=3
Theindexofhydrogendefi ciency(unsaturationindex)Uthatcorrespondstothepreceding
formulaiscalculatedeasi
lybyapplyingtherelati
onship
n-r+2
U=
2

Determi
nethei
ndexofhydrogendef
ici
encyf
oreachofthef
oll
owi
ngcompounds:
(
a)C7H7NO
 2C+2+N-H-X
D
egreeofUnsaturati
on=
2

2x7+2+1
-7
DegreeofUnsaturati
on= =(
17-7)
/2=1
0/2=5
2

Thei ndexofhydrogendefi
ciencygi
vesthenumberof
doubl ebondsor
triplebondsor
ringsinamol ecul
e
Forexampl eC6H6
DegreeofU nsaturati
on=(2x6+2+0-6-0) /2=(14-6)/2=8/2=4
Ifindex=4ormoreexpectabenzeneri ng.
Intheaboveexampl ewecanhavethreedoublebondsandoneri
[Link]
orei
tisabenzene.

I
findex=3thenal
soweexpecttwodoubl
ebondsandoneri
ngl
ike

I
findex=2thenal
soweexpect0nedoubl
ebondsandoneri
ngl
ike

etc
ortwodoubl
ebondswi
thopench
ainstructureoronetri
plebondortwori
ngsf
usedl
ike

Herei
sasummaryofhowthei
ndexofhydrogendef
ici
ency(
IHD)works.
 Adoublebondandri
ngeachcountsasoneI
HD.
 Atripl
ebondcountsastwoIHD.
Cal
cul
atethei
ndexofhydrogendef
ici
ency(
IHD)

Therearetwodoubl ebondsandonering,theIHD=3
(2)C6H10
Sincetheabovef ormulahasonlycarbonandhydrogentheproceduretocal
culateIHDi
s
[Link] ormulasaturatedhydrocarboncorrespondi
ngtothenumberofcarbonatoms
[Link] ormulaisC6H14
[Link] indthedi
fferenceinhydrogenatomsbetweentwof ormul
aeie1
4-10=4
[Link]
erenceby2
Theref oretheIHDintheabovecompoundi s4/2=2
3.CH3C≡CCOCH3
Thereisonetripl
ebondthatisequalI
HDto2andonedoubl
ebondbetweenketogroup.
HencetheIHDofthecompoundis3.

I
NFRAREDSPECTROSCOPY
Cal
culationofVibrationalFrequenci
es
Thestretchingabsorptionfrequencyofabond,
canbecal
cul
atedbyHooke'
slaw

where

Af
teri
nserti
ngtheval
uesofπandc,
theaboveequati
onbecomes
 -2-

Esti
matethefundamentalstretchingvibrati
onofanO–Hbondwhi
ch
5
K=7.
hasaforceconstant, 6×1 0 dynes/cm

Thecarbonylstretchi
ngvi
brati 669cm−1From
onoftrans-2-hexenalappearsat1
thi
sinformation,esti
matetheforceconstantoftheC=Obond.

I
nfraredspectroscopyofhydrocarbons: ALKANES
C-HStretchRegi
on:
TheC-Hstretchingandbendi ngregi
onsaretwoofthemostdi ffi
cul
tregi onsto
i
[Link] requencyoftheabsorptionofC-Hbondsi sa
functi
onmostl yofthetypeofhybri dizati
onthatisattri
[Link]
foll
owingtableil
lustratesthephysi
calconstantsforsp-,sp2-,andsp3-hybri
dized
carbonandtheresulti
ngC-Habsorpti
onvalues.

-3-
Ascanbeseenf romtheabovetable
Thestrengthofsp-C-H>sp2-C-H>[Link] sstrengthresul tsinalargervi
brational
forceconstantandahigherfrequencyofvibrati
[Link]-Habsorption
occursindi
catesthetypeofcarbontowhi chthehydrogenisattached.

Exceptf ortheal dehydehydrogen,anabsorpti onf requencyofl essthan3000cm−1

usual l
yi mpli
es a saturated compound ( only sp3-1s hydrogens).An absorption
−1 −1
frequencyhi gherthan3000cm butnotaboveabout31 50cm usual l
yi mpl
ies
aromati corvinylhydrogens.
Theal dehydeC-Hstretchappearsatl owerf requenci
esthanthesaturatedC-H
absorpti onsandnormal l
yconsi stsoftwoweakabsorpti onsatabout2850and2750
−1
cm .
The2850-cm−1bandusual lyappearsasashoul deronthesaturatedC-Habsorpti on
−1
bands. Thebandat2750cm i sratherweakandmaybemi ssedi nanexaminationofthe
3
spectrum. However, i
tappearsatl owerf requenciesthanaliphaticsp C-Hbands.
Thesp3-hybri dizedC-Hstretchi ngvibrationsformethyl ,methyl ene,andmethineare
showni nthef ol
lowingtable:
 -4-

Stretchingvibrationsandbendi ngvibrati
onsofmethyl enegroup
Conclusion:
Sinceseveralbandsmayappeari ntheC-Hstretchregi on,i
tisprobablyagoodi deato
decideonl ywhethertheabsorpti onsareacetyl eni
c( 3300cm−1),
vinyl
icoraromati c(>
−1 −1 −1
3000 cm ) ,ali
phati
c( < 3000 cm ) ,oral dehydic( 2850 and2750 cm ) .F
urther
interpretati onofC-Hstretchi ngvibrationsmaynotbeworthextendedef [Link]-
Hbendi ngvi brati
onsareoftenmoreusefulfordetermi ningwhethermethylor
methyl enegroupsarepresenti namol ecule.
C-HBendi ngVi brati
onsforMethylandMethyl ene
The presence of methyland methyl ene groups,when not obscured by other
absorptions, maybedetermi nedbyanal yzi
ngtheregi onf rom1465to1375cm−1.
ThebandduetoCH2sci ssoringusual
lyoccursat1 465cm−[Link]
−1
CH3 usuall
yabsorbsstrongl ynear1375cm .Thesetwobandscanof tenbeusedto
detectmethyl eneandmethylgroups,respectively.
Furthermore,the1375-cm−1methylbandisusual l
ysplitintotwopeaksofnearlyequal
intensity(symmetricandasymmetri cmodes) (approximatel yatabout1370and1380
-1
cm )i fagemi naldimethylgroupi [Link] sdoubl etisof tenobservedin
compoundswi thisopropylgroups.

-5-
Atert-butylgroupresul
tsinanevenwiderspli
ttingofthe1375-cm−1bandi
ntotwo
−1 −1
peaks.
The1370-cm bandismorei
ntensethanthe1390-cm one.

I
ncycl i
chydrocarbons,
whichdonothaveattachedmethylgroups,the1375-cm−1band
willbemissi
[Link]
ly,
abandduetorockingofmethylenegroupi
n-planeappearsnear
−1
720cm f orlong-chainalkanesoffourcarbonsormoreandabandat1 250cm-1
appearsdueto out-of -plane(oop)bendi
ng( twisting orwaggi
ng)vi brati
onof
methylenegroup.
I
denti
ficati
onofAl
kanes
Thesebandsoccuri
nal
mostal
lspectraoforgani
ccompounds.
  TheC-Hstretchi ngvi brationalbandsoccurat2940-2855cm-1.
 ThebandduetoCH2sci ssoring(bendingvibrationinpl ane)usual
lyoccursat
−1
1465cm .Oneofthebendi ngmodes( symmetri c)forCH3 usual lyabsorbs
−1
strongl ynear1 375cm .
 Theabovebandi sspl i
ti ntotwowi thequalintensity(1 380and1370cm-1)for
isopropylandforterti arybutylitissplitintounequali ntensi
ties(1390and
-1 -1
1370cm , 1370cm i smorei ntense)
 Abandduetorocki ngofmethyl enegroupi n-planeappearsnear720cm−1for
long-chai nal kanesoffourcarbonsormore.
 Abandat1 250cm-1appearsduetoout-of-pl ane( oop)bending(twistingor
waggi ng)vi brationofmethyl enegroup.
 Skeletalvi
brati
ons,acharacteri
sti
cofbranchedhydrocarbonsoccurat1
250-1
149cm
-1
.
Cycl
ichydrocarbons: Non-branchedcyclicalkanesdonotshow absorpti onsinthe
1385–1365cm−1regi onofthespectrum.f orcyclical kanesthereisaveryslightshi
ft
oftheCH2bendi ngvibrati
ontol owerwavenumber
Problems
[Link] ecularf ormulaofthecompoundi .sC8H18.F romthef ol
lowi
ngIRdataofthe
compound, draw thestructureofthecompoundandassi gnthebandfrequenciesto
stretchingandbendi ngvibrati
onsofCH3andCH2.
IRdata:2971,2865,1470,1
383,725cm-1
[Link] ecul arformul aofthegivencompoundi [Link]
Rdata:2970,2850,1
461.
Fromthedataassi gnthestructureofthecompound.

-6-
[Link] ecularformul aofthecompoundi sC7H16.TheIRdatais2970,2850,
1470,1380-
-1
1390(twopeakswi thequali ntensity)
,11
75cm .F rom thi
sdataassi gnthepossi bl
e
structureofthecompound.
4..Themol ecularformul aofthecompoundisC9H20.TheIRdatais2970,2850,1380-1390
-1 -1
(thepeakat1 380cm i slessintensewhencomparedwi th1390cm peak) ,175cm-1.
1
Fromthisdataassi gnthepossiblestructureofthecompound.
Problem:[Link].
[Link]
Rdata
ofthecompound, draw thepossibl
estructureofthecompoundandassi gntheband
frequenci
escorrespondingtostretchi
ngandbendi
ngvibrationsofCH3andCH2.
IRdata:2971,
2865,
1470,1 725cm-1
383,

Probl
em [Link]
[Link]
Rdata:2970,
2850,
1461
.Fromthedataassignthepossi
blestructureofthecompound

-7-
ALKENES
C-Hstrecthi ngregi on:
=C-H Stretch f or sp2C-H occurs at val ues greater than 3000 cm−1 but l ess
-1 −1
than3150cm ( 3095–301 0cm ) .Thi sisduetotermi [Link]
tyof
sp2C-Hislessthanthei ntensityofsp3C-Hband.
=C-HOut-of -plane( oop)bendi ngoccursi ntherange1 000–650cm−1.
C=CStretchoccursat1 660–1 600cm−1;conj ugationmovesC=Cstretchtol ower
frequenciesandi ncreasesthei ntensity.
TheC=Cstretchi ngfrequencyusual lyappearsbetween1 670and1 640cm−1forsimple
noncycli
c( acycl ic)al kenes.F orexampl e,simplemonosubsti tutedalkenes ( vi
nyl
group)yieldval uesnear1 640cm−1.
TheC=Cf requenci esincreaseasal kylgroupsareaddedtoadoubl ebond.
Forexampl e,1 ,
1-disubsti tutedal kenesabsorbat about 1 650 cm−1,andtri - and
tetrasubsti tutedal kenesabsorbnear1 670cm−1.
Trans-Disubsti tutedal kenesabsorbathi gherf requencies(1670cm−1 )thanci s-
−1
disubsti
tutedal kenes( 1
658cm ) .
I
ntetrasubsti tutedal kenes,thedoubl ebondabsorpti onmaybesoweakthati ti
snot
observedatal l
.
TheC=Cgrouppeaki ntensityismuchlessweakerthanatypi calC=Ogroup.
Iftheattachedgroupsarearrangedsymmetri call
y,nochangeindipolemomentoccurs
duringstretching,
andhencenoi nfraredabsorptionisobserved.
Cis-Alkenes,whichhavel esssymmetrythantrans-al kenes,generall
yabsorbmore
stronglythanthetrans-al kenesthatisthebandi ntensityforcis-alkenesismore
thanthetrans-al kenes.
Doublebondsi nrings,becausetheyareof tensymmetri cornearl yso,absorbmore
weakl ythanthosenotcontai nedinri
ngs.
Terminal doubl e bonds in monosubsti tuted alkenes general l
y have stronger
absorption.
C-HBendi
ngVi
brati
onsforAl
kenes
Monosubsti
tutedDoubleBonds(Vi
nyl):
Thissubsti
tutionpatterngivesrisetotwostrongbands,(
out-of-pl
ane,oop)one
near990cm−1andtheothernear910cm−1f
oral
kyl
-substi
tutedal
kenes.

+si :
gn Di
recti
onofvi
brati
onoutofthepaperpl
ane
gn:
-Si Di
recti
onofvibrationbehi
ndthepaperplane
F
ig:Out-of-pl
ane( ooP)bendi
ngvi
brationofmonosubsti
tutedal
kenes
-8-

Fi
g:In-planebendingvibrati
onofmonosubstitutedal
kenes
(al
kanesalsoshowCH2sci ssoringvibrationalbandatabout1 450cm-1)
-1
Anovertoneofthe91 0-cm bandusual l
yappearsat1 820cm-1andhel psconfirmthe
presenceofthevinylgroup.
The910-cm−1bandisshi ftedtoal owerf requency,aslow as810cm−1, whenagroup
attachedtothedoubl ebondcanrel easeel ectronsbyaresonanceef fect(Cl,
F,OR).
The910-cm−1groupshi ftstoah igherf requency, ghas960cm−1,
ashi whenthegroup
whenagroupattachedtothedoubl ebondwi thdrawselectronsbyaresonanceef fect
(C=O, C≡N).
The use of the out-of-pl ane vibrati ons (990 and 91 0 cm-1)to confi rm the
monosubsti tutedstructurei sconsideredveryrel iable.
Theabsenceofthesebandsal mostcertai nlyi ndicatesthatthi sstructuralfeature
isnotpresentwi thinthemol ecule.
cis-andtrans-1 ,
2-DisubstitutedDoubl eBonds
−1
Acisarrangementaboutadoubl ebondgi vesonestrongbandnear700cm , whi
lea
−1
transdoubl ebondabsorbsnear970cm .
1,
1-DisubstitutedDoubl eBonds
−1
Onestrongbandnear890cm i sobtai nedf oragem-di alkylsubsti
tuteddoubl ebond.
−1
whenagroupattachedtothedoubl ebondcanrel easeel ectrons,The890-cm bandi s
shiftedtoal owerf [Link] ebondwi thdraws
electrons,The890-cm−1bandi sshif
tedtoahugherf requency.
TrisubstitutedDoubl eBonds
Onemedi um-i ntensi
tybandnear81 5cm−1i sobtai ned.
Tetrasubsti tutedDoubl eBonds
Theseal kenesdonotgi veanyabsorpti oninthi sregi onbecauseoftheabsenceofa
hydrogenatom onthedoubl ebond.I naddi tion,theC=Cstretchi ngvibrationi svery
weak( orabsent)atabout1 670cm−1i nthesehi ghlysubsti tutedsystems.
Conj
ugati
onEffects:
WhenaC=Ci sconj
ugated witheitheracarbonylgrouporanotherdoubl ebondthe
multi
plebondacquiresmoreofsi [Link]
ofthesinglebondcharacter,thef orceconstantofthedoublebondi sloweredand
thusfrequencyofvibrati
oni
salsol owered.

F
orexampl
e,
-9-

Withseveraldoublebonds,thenumberofC=Cabsorpti onsoftencorrespondstothe
numberofconj ugateddoublebonds.
Anexampleofthiscorrespondencei
sf oundi
n1,
3-
pentadi
ene,whereabsorptionsareobservedat1
600and1 650cm−1.
However,butadienegi
vesonlyonepeakat1600cm-1.I
tisanexceptiontotheaboverul
e.
I
fthedoublebondisconj
ugatedwithacarbonylgroup,theC=Cabsorptionshiftstoa
l
owerfrequencyandisal
sointensi
fiedbythestrongdi
poleofthecarbonylgroup.

Thisconjugationi
ncreasesthesi ngl
e-bondcharacteroftheCJ OandCJCbondsinthe
resonancehybridandhencel owerstheirf orceconstants,
resulti
nginaloweringof
thefrequenciesofcarbonylanddouble-bondabsorpti
on.
TheC=Cabsorpti onshi ftsfrom its“ normal”val
ue,about1650cm−1,toal ower-
−1
frequencyvalueofabout1640cm .
Ri
ng-Si
zeEffectswi
thI
nternalDoubl
eBonds-(
endocycl
ic)
:
Theabsorpti
onfrequencyofinternadoublebondsi
ncycl
iccompoundsisverysensiti
ve
toringsi
[Link]
onfrequencydecreasesasthei
nternalangl
edecreases,unti
l
i
treachesami ni
mumat90°i ncyclobutene.

Theabsorpti onf requencydecreasesasthei nternalangledecreases,unti

litreachesa
minimumat90°i ncyclobutene.
Thef requencyi ncreasesagainf orcyclopropenewhentheangl edropsto60° .
Thevari ationinthef requencyofC=Cwi ththeringsizecanbeexpl ai
nedbyconsidering
theC-Csi nglebondstretchi ngvi brati
oncouplingtotheC=Cbond.
-10-
TheC-Csi ngle-bondstretchi ngvi brati
oncanberesol vedintotwocomponents, oneof
whichiscoi ncidentwi ththedirectionoftheC=Cstretch.

WhentheattachedC-CbondsareperpendiculartotheC=Caxis,
asi ncycl
obutene,
thei
r
vibrati
onalmodeisorthogonaltothatoftheC=Cbond(i
.e.
,onadifferentaxi
s)and
doesnotcouple.
Whentheangleisgreaterthan90°(120°i
nthefig,
b),
theC-Csingle-bondstretchi
ng
vibrati
oncanberesolvedintotwocomponents,oneofwhichiscoinci
dentwiththe
di
rectionoftheC=Cstretch.
Si
ncecomponentai sinli
newi ththeC=Cstretchi
ngvector,theC-CandC=Cbondsare
coupl
ed,
leadi
ngtoahi
gherf
requencyofabsorpti
on.
Theeffectofal
kylsubsti
tuti
ononthefrequencyofaC=Cbond
i
naring.
Absorpti
onfrequencyi
ncreasessi
gni
ficantl
ywhenoneormorealkylgroupsareattachedto
thedoublebond.
Thisef
fectismorepronouncedf
orsmallerri
ngs,
especiall
ycyclopropene.

Ring-SizeEffectswithExternalDoubl
eBonds( exocycli
cdoublebonds)
External(exocycli
c)doubl
ebondsgiveanincreaseinabsorpti
onfrequencywi
thdecreasi
ng
ringsize.
-11-

Thi
sremovespcharacterf
romthesi
gmabondofthedoubl
ebondbutgi
vesi
tmores
character,thusstrengtheni
ngandstiffeningthedoubl
ebond.
Thef
orceconstantKi
sthen
increased,
andtheabsorptionfrequencyincreases.

Al
kynes
Thenormalrangef ortheacetyl enic(≡C–H)stretchingvibrationsf orterminaltri
ple
−1
bondsisbetween3320and3280cm .
Thisabsorpti oni
susuallystrongandsharp.
TheC≡Cstretchi ngvibrati onofthetermi naltripl
ebondappearsbetween2260and
−1
2100cm
Ifbothcarbonsofthetri plebondaresubsti tuted,theC≡Cstretchi ngvibrati
onwi l
l
appearbetween221 5and2235cm−1
Symmetri calofnearlysymmetri calalkynesshowl ittl
eornodi pol emomentchange
duringvibration,
consequentl y,theC≡Cstretchingvibrati
oni seitherweakorabsent.
Thespectraoftermi nalal kynesal soexhi
bitbroad≡CHwaggi ngvi brati
onintheregion
−1
between665and625cm .

-1
2-
AROMATI
CRI
NGS
The=C–Hstretchi ngvibrationsofaromati chydrocarbonsoccurbetween31 00and
−1
3000cm
C=CRingstretchabsorpti onsoftenoccuri npai rsat1600cm−1,1500and1475cm−1.
Theout-of -planeC-Hbendi ngvibrati
ons, whichappearbetween900and690cm−1 are
moreusef ul.
Theseextremel yintenseabsorpti ons,resultingf romstrongcoupl i
ngwi thadj acent
hydrogenatoms, canbeusedtoassi gntheposi tionsofsubstituentsonthearomati c
ring.
Theassignmentofstructurebasedontheseout-of -planebendingvibrationsis
mostrel iabl
ef oralkyl-,alkoxy-,halo-,ami no-,orcarbonyl -substi
tutedaromati c
[Link] cnitrocompounds, deri
vati vesofaromati ccarboxyli
caci ds,and
derivati
vesofsul foni
cacidssometimesleadtounsati sfactoryinterpretati
on.
Monosubsti tutedRings.
Thissubstitutionpatternalwaysgivesastrongabsorpti onnear690cm−1.
I
fthi sbandisabsent,[Link]
ly
−1
appearsnear750cm .
Whenthespectrum i stakeni nahal ocarbonsol vent,the690-cm−1bandmaybe
obscuredbythestrongC -Xstretchabsorptions.

ortho-Di
substi
tutedRi
ngs(
1,
2-Di
substi
tutedRi
ngs)
.
Onestrongbandnear750cm−1i
sobtai
ned.
Thi
spatterni
sseeni
nthespectrumofortho
-diethyl
benzene

-1
3-

meta-Di
substi
tutedRi
ngs(
1,
3-Di
substi
tutedRi
ngs)
.
para-Di
substitutedRi
ngs(1
,4-Di
substitutedRi
ngs).
Onestrongbandappearsi
ntheregionfrom 800to850cm−1.

ALCOHOLSANDPHENOLS
O—H
Thef reeO—Hstretchi sasharppeakat3650–3600cm−[Link] sbandappearsi n
combinationwiththehydrogen-bondedO—Hpeakwhentheal coholi sdissol
vedina
solvent
Thehydrogen-bondedO—Hbandi sabroadpeakat3400–3300cm−1.
Whenal coholsorphenol saredetermi nedaspure( neat)li
quidf i
lms,abroadO—H
stretchingvibrati
oni sobtainedf ori
ntermolecularhydrogenbondingi ntherange
from3400to3300cm−1.
Phenolsalsoshowthehydrogen-bondedO—H
Astheal coholisdilutedwi thcarbontetrachlori
de,asharp“ free”(non-hydrogen-
bonded)O —Hstretchingbandappearsatabout3600cm−1,totheleftofthebroadband.

-1
4-
Whenthesol utionisfurtherdiluted,thebroadintermolecularhydrogen-bondedband
isreducedconsiderably,l
eavi
ngasthemaj orbandthefreeO—Hstretchi ngabsorpti
on.
Whenal cohol
sorphenol saredeterminedaspure( neat)li
quidfil
ms, abroadO—H
stretchingvibrati
onisobtainedforintermolecularhydrogenbondingintherange
−1
from3400to3300cm .

Asthealcoholi
sdilutedwi thcarbontetrachlori
de,asharp“
free”(
non-hydrogen-
bonded)O
—Hstretchingbandappearsatabout3600cm−1,
tothel
eftofthebroadband.

Whenthesoluti
onisfurtherdil
uted,
thebroadintermolecul
arhydrogen-bondedband
i
sreducedconsi
derabl
y,leavi
ngasthemajorbandthefreeO—Hstretchingabsorpti
on.

I
ntermol
ecularhydrogenbondi
ngweakenstheO—Hbond,
therebyshi
fti
ngthebandto
l
owerfrequency(l
owerenergy).
 -1
5-
C—OStretchingVi
brationsinalcohol
s
ThestrongC—Osingle-bondstretchingvi
brationsareobservedintherangef rom1260
to1000cm−1.
Si
ncetheC—Oabsorpti onsarecoupl edwithth eadjacentC—Cstretchi ngvi
brati
ons,
thepositionofthebandmaybeusedtoassi gnapri mary,secondary,ortertiary
structuretoanalcoholortodetermi newhetheraphenoli
ccompoundi spresent.
 -1
6-

Inadditiontothisband, anO—Hi n-planebendingabsorptionisusual

lyfoundnear1360
cm−1forneatsampl esofphenol [Link] salsofoundi
nalcoholsdetermi
ned
asneat( undil
uted)l iqui
[Link] lyoverlapstheC—Hbendi ngvibrati
onf orthe
methylgroupat1 375cm−1 .
Problems
Givethepossiblestructuref romthef ol
lowingIRdata
1. Themol ecularformul aisC8H10.
TheIRdata:3020,2970, 1
600. 1500,
1430,1474,
1375, and750cm-1
690,
[Link] ecularformul aisC6H14O
TheIRdata:3400, 2970.2840, 1480,
1330,1 720cm-1
060,
[Link] ecularformul aisC3H4O
TheIRdata:3300, 2950,2100,1470and1040cm-1
[Link] ecularf ormulaisC4H6.
Thecompoundshowsλmaxat21 7nmi nUVspectrum
1
IRdata:3020,1620,910and990cm-
EthersandEpoxi
des
EthersexhibitcharacteristicC-0-CStretchi [Link] cmassesofCand0
arefairl
ycomparabl e.
Thus, theirf orceconstantsarecl ose,andsoC-0-CandC-C-C
Stretchi
ngshaveal mostthesamef requency.
Si
ncevibrationsofC-0--Cresul tingreaterdipolemomentchangesthanthatofC-C-
Cduetogreaterel ectronegati vityofoxygen, moreintenseI Rbandsareobservedf
or
ethers.
Ethersshow acharacteri stic,strongbandi ntheregi on1 000cm-1becauseof
300-1
asymmetricalC-0-Cstretchi [Link] calstretchingbandisusual
lyweak.
Alcohol
sandestersal sogi
vestrongC—Oabsorpti
onsinthi
sregion,and
thesepossi bi
li
tiesal
cohol
sandestersmustbeelimi
natedbyobserving
theabsenceofbandsi ntheO—Hstretchregionandi
ntheC—Ostretch
regionrespectivel
y.
 -1
7-
Di
alkylEthers:
TheasymmetricC—O—Cstretchi ngvi
brati
onleadstoasinglestrongabsorptionthat
−1 −1
appearsatabout11
20cm . Thesymmetri
cstretchi
ngbandatabout850cm i susual
ly
veryweak.
TheasymmetricC—O—Cabsorpti onal
sooccursatabout1120cm−1forasix-membered
ri
ngcontaini
ngoxygen.

ArylandVi
nylEthers:
Arylalkylethersgiverisetotwostrongbands:anasymmetricC—O—C
−1 −1
stretchnear1250cm andasymmetri cstretchnear1040cm .
Vi
nylalkylethersal sogivetwobands:onestrongbandassi gnedtoanasymmetri
c
stretchi
ngvibrationatabout1 220cm−1andoneveryweakbandduetoasymmetri c
stretchatabout850cm−1..
Asymmetri
cstretch:
1120cm-1.

Vi
nylethers:Asymmetri
cstretch:
1220cm-1.
-13-

Reason:
Becauseofthei ncreaseddoubl
e-bondcharacter,whi
chstrengthensthebondinvi
nyl
ethers.I
ndialkyletherstheabsorptionoccursat120cm−1.
1 I
nadditi
on,because
resonanceincreasesthepolarcharacteroftheC=Cdoublebond,thebandatabout
1640cm−1i
sconsi derabl
ystrongerthaninnormalC=Cabsorption.

Epoxi
des.
Thesesmall-ri
ngcompoundsgiveaweakring-stretchi
ngbandi ntherange1280–1
230
−1
cm .Thetwostrongri ngdeformati
onbands,onethatappearsbetween950and81 5
−1 −1
cm ( asymmetri
c)andtheotherbetween880and750cm ( symmetri
c)areimportant.

CARBONYLCOMPOUNDS
Thecarbonylgroupi
spresenti
n

Al
dehydes ketones aci
ds
 esters ami
des aci
dchl
ori
des Anhydri
des

Carbonylgroupabsorbsstrongl
yintherangef rom1850to1650cm−1
Thereasonislargechangei
nitsdipol
emoment.
-1
4-
NormalbasevaluesfortheC=Ostretchingvibrati
onsforcarbonylgroups

Factorsaffecti
ngtheabsorpti
onfrequencyofcarbonylgroup
TheC=Ostretchingfrequencydependson
 inducti
veef f
ect
 mesomeri ceffect
 hydrogenbonding
 fieldeff
ect
 stericeffect
 ringstrain

Thesefactorsei therincreaseordecreasethestretchi ngfrequency(byincreasingor

decreasi
ngf orceconstnt)ofboththeal dehydi
candketonicC=Ogroupscomparedto
-1
thenormalval ue1715cm ( Stretchingabsorptionfrequencyofaneatsampl eofa
saturatedaliphaticketone).
Acarbonylcompoundmaybeconsi deredasaresonancehybridofthef ol
lowing
structures:

Anel ectronegativeelementmaytendtodraw i ntheel ectronsbetweenthecarbon

andoxygenatomsthroughi tselectron-wi thdrawingeffect( -I ef
fect),
sothattheC
=Obondbecomessomewhatstronger. Ahigher-frequency( higherforceconstantand
higher-energy)[Link] sconditi
onstructureI i
sfavoured.
IfRandR’ areelectrondonatinggroupsthenstructureI I
isf avouredbecauseel ectron
-releasingef fectweakenstheC=Obondandl owersthef orceconstantandthe
absorptionf [Link] ectronegativethancarbon, thi
sef fect
domi natesinanestertorai setheC=Of requencyabovethatofaketone.
 F
rom
-1 -1
1
715 cm to1
735cm

Inacidchl
ori
des, thehighlyelectronegativehalogenatomstrengthenstheC=Obond
throughanenhancedi nductiveeffectandshi ftsthef requencytoval
uesevenhigher
thanarefoundinesters.
-15-
Anhydri
desarelikewiseshiftedtof requencieshigherthanarefoundi
nestersbecause
ofaconcentrationofel ectronegati
veoxygenatoms.
Resonanceeffect:
Resonanceef fect maybeobservedwhentheunpai redel ectronsonani trogenatom
conj ugatewiththecarbonylgroup,resul
tinginincreasedsi ngl
e-bondcharacteranda
loweri ngoftheC=Oabsorpti [Link] f
ecti sobservedi nanami [Link]
nitrogenislesselectronegati
vethananoxygenatom, itcanmoreeasi lyaccommodate
aposi ti
[Link] ntroducessi ngl e-bond
characteri ntotheC=Ogroupandtherebyl owerstheabsorpti onf requencybel ow
thatofaketone.I namidestheresonanceeffectl owersC=Of requencyf rom1 715cm-1
to1 675cm-1

Hydrogen-Bondi
ngEffects
Hydrogenbondi ngtoacarbonylgroupl engthenstheC= Obondandl owersthe
stretchingf orceconstantK,resulti
nginal oweringoftheabsorptionfrequency.
Exampl es
Acarboxylicaci dexistsinmonomericf orm onlyinverydilutesol
ution,anditabsorbs
atabout1 760cm−1becauseofth eelectron-wi [Link],acidsin
concentratedsol uti
on,intheformofneatl i
quid,orinthesoli
dstate( KBrpelletand
Nujol)tendtodi merizevi
ahydrogenbonding.
Thisdimerizati onweakenstheC=Obondandl owersthestretchingf orceconstantK,
resultingi
nal oweringofthecarbonylfrequencyofsaturatedacidstoabout1 710cm−1.

Inmethylsalicylateanesterth
e C=Of
requencyi
slowereddueto i
ntramol
ecul
ar
hydrogenbonding:
 680cm-1
1

-1
6-
Conj
ugati
onEffects
TheintroductionofaC=Cbondadj acenttoacarbonylgroupresultsindelocal
izati
on
oftheπel ectronsintheC=OandC=[Link]
sconjugati
onincreasesthesingl
e-bond
characteroftheC=OandC=Cbondsi ntheresonancehybridandhencel owerstheir
forceconstants, resulti
nginaloweringofthefrequenci
esofcarbonylanddoubl e-
bondabsorption.
Conjugati
onwi thtriplebondsal
soshowsthiseff
ect.

Generally,thei ntroducti
onofanα,βdoublebondinacarbonylcompoundresul tsina25
−1 -1
-to45-cm l oweringoftheC=Ofrequencyfromthebaseval ue1715cm .
Furtheraddi ti onofunsaturati
on(γ,δ)resultsinaf urthershif
ttol owerf requency,
butonlybyabout1 5cm−1more.
Inaddition,theC=Cabsorpti onshi
ftsf rom its“normal”value,about1 650cm−1,toa
lower-f requencyval ueofabout 1 640 cm−1,andtheC= Cabsorpti oni sgreatly
intensi
fied.
Thef ol
lowi ngexampl esshowtheef fectsofconjugationontheC=Of requency.

α-Substi
tuti
onEffects
Whenthecarbonnexttothecarbonyli
ssubsti
tutedwi thachlori
ne(orotherhalogen)
atom,thecarbonylbandshiftstoahi gherf [Link]-withdrawing
effect removes electrons from the carbon of the C=O [Link] s removalis
compensatedf orbyatighteni
ngoftheπbond( shorteni
ng),whichincreasestheforce
constantandl eadstoanincreasei
ntheabsorpti [Link]
allcarbonylcompounds.

Axi
alchl
ori
neandEquatori
alchl
ori
ne-Fi
eldeffect
I
nketones,twobandsresultfromthesubsti
tutionofanadj acentchl
orineatom.
One
ari
sesf romtheconformati
oninwhichthechlori
neisrotatednexttothecarbonyl ,
andtheotherisduetotheconformati
oninwhichthechlori
neisawayf romthegroup.
Whenthechlorineisnexttothecarbonyl,(
equitori
al)nonbondedelectronsonthe
oxygenatomarerepell
ed,

-17-
resulti
nginastrongerbondandahi gherabsorpti
onfrequency.I
nformationofthi
s
kindcanbeusedtoestabl
ishastructureinrigi
dri
ngsystems,suchasinthefol
lowi
ng
examples:

trans ci
s
Al
dehydes
C=Ostretch:C=Ostretchappearsi
ntherange1 725cm−1f
740–1 ornormalal
iphati
c
aldehydes.

Conj
ugati
onofC=Owi
thα,
βC=C;
1 680cm−1f
700–1 640cm−1f
orC=Oand1 orC=C.

Conj
ugati
onofC=Owi
thphenyl
;1 660cm−1f
700–1 orC=Oand1 450cm−1f
600–1 or
ri
ng.

Longerconj
ugatedsystem;
1680cm−1f
orC=O.
C-HStretch
Aldehydehydrogen(—CHO),consistsofapai rofweakbands, oneat2860–2800cm−1and
−1
theotherat2760–2700cm .I tiseasiertoseethebandatthel owerf requency
becauseitisnotobscuredbytheusualC—Hbandsf rom [Link]-
frequencyaldehydeC—Hstretchi softenburiedintheali
phaticC—Hbands.
−1
TheC—Hstretchi ngvibrati
onsf oundinaldehydes(—CHO)atabout2750and2850cm
areextremel yi
mportantf ordi stingui
shi
ngbetweenketonesandal dehydes.

-1
8-

Ketones
Ketonessh ow averystrongbandf ortheC=Ogroupthatappearsi ntherangeof
−1
1720–1 708cm f orsi
mpl eali
phati
[Link]
ftedtolowerf requencies
withconj ugationtoaC=[Link]α-hal ogenatom wi l
lshiftth eC=O
frequencytoahi [Link]
ngstrainmovestheabsorptiontoahigherf requencyin
cyclicketones.
Bendi ngModes. Amedium-to-strongabsorptionoccursintherangefrom1 300to1 100
−1
cm forcoupl edstretchingandbendingvibrationsi
ntheC—CO—Cgroupofketones.
Ali
phati cketonesabsorbtotheri ghtinthisrange(1220to1100cm−1),asseeninthe
spectrumof3-methyl -2-butanonewhereabandappearsatabout1 180cm−[Link]
ketonesabsorbtothel efti
nthisrange
−1
(1300to1220cm ) ,
asseeni
nthespectrumofacetophenonewhereabandappearsat
−1
.
about1260cm
Amedium-i ntensitybandappearsforamethylgroupadj acenttoacarbonylatabout
−1
1370cm f orthesymmetri cbendi ngvibrati
[Link] th
greaterintensitythanmethylgroupsf oundinhydrocarbons.

-1
9-

Cycl
icKetones(
RingStrai
n)

F
ig:
Ri
ng strai
nusual
ly
i
ncreasestheC=Ostretchi
ngfrequency.
Thescharacteri
ntheC=Ogroupincreasesastheri
ngsizedecreases,
untili
treachesa
maximumvaluethatisfoundi
nthesp-hybridi
zedcarbonylcarboni
nketene.
α-Di
ketones(
1,
2-Di
ketones)
Unconjugateddi
ketonesthathavethetwocarbonylgroupsadj acenttoeachother
−1
show onestrongabsorptionpeakatabout1 71
6cm .I fthetwocarbonylgroupsare
conjugatedwitharomaticrings,
theabsorptioni
sshiftedtoal ower-frequencyvalue,
about1680cm−1.
Inthelattercase,anarrowlyspaceddoubletratherthanasinglepeak
maybeobservedduetosymmetri candasymmetri cabsorpti
ons.

β
-Di
ketones(
1,
3-Di
ketones)
Di
ketoneswi thcarbonylgroupslocated1 ,
3withrespecttoeachothermayyi el
da
morecompl i
catedpatternthanth oseobservedformostketones(Theseβ-di
ketones
oftenexhibi
ttautomerization,whichyiel
dsanequili
bri
um mixtureofenolandketo
[Link]β -di
ketonescontainlargeamountsoftheenolf orm,wemay
observecarbonylpeaksforboththeenolandketotautomers.
-20-

Thecarbonylgroupi ntheenolf orm appeari

ngatabout1 622cm−1issubstanti all
y
shi
ftedandintensifiedi
ncomparisontothenormalketoneval ue,
1 5cm−1.
71 Theshi
ftis
aresultofi [Link],however,alsocontributestothe
loweri
ngofthecarbonylf requencyintheenolf [Link]-
bondcharacterintotheenolform.

Aweak, broadO-Hstretchisobservedf ormat3200–2400cm−1.

ortheenolf Si
ncethe
ketof orm isal
sopresent,adoubletfortheasymmetricandsymmetricstretchi
ng
frequencies i
s observed f
or the two carbonylgroups (
Fig.2.
42)
.The relati
ve
i
ntensiti
esoftheenolandketocarbonylabsorpti onsdependonthepercentages
presentatequi
libri
[Link]-bondedcarbonylgroupsinenolf ormsareoften
m−1
observedi
ntheregion1
640–1570c . Theketoformsgeneral
lyappearasdoubl
etsin
therangefrom1
730to1695cm−1.

α-Hal
oketones
Substitutionofahal ogenatomontheacarbonshiftsthecarbonylabsorptionpeakto
ahigherf [Link]
arshif
tsoccurwithotherelectronwi
thdrawinggroups,such
asanal koxygroup( -O-CH3)
.Forexampl
e,thecarbonylgroupi
nchloroacetoneappears
at1750cm−1, whereasthat

-21
-
−1
i
nmethoxyacetoneappearsat1731cm .
Whenthemoreel ectronegativefluori
neatom
−1
i
sattached,
thefrequencyshi
ftstoanevenhigherval
ue,
1781cm , inf
luoroacetone.
Carboxyl
icAci
ds
Carboxyli
caci dsshowaverystrongbandf ortheC=Ogroupthatappearsi ntherange
−1
of1730–1700cm f orsimpleal i
phati
ccarboxyli
cacidsinthedimeri cform.
Thisbandisshiftedtol owerf requenci
eswithconjugationtoaC=Corphenylgroup.
TheO—Hstretchappearsi nthespectrumasaverybroadbandextendi ngfrom3400to
−1
2400cm .
Thisbroadbandcentersonabout3000cm−1andparti allyobscurestheC—Hstretchi ng
bands.
IfthisverybroadO—Hstretchbandi sseenalongwi thaC=Opeak, i
talmostcertai
nly
indi
catesthecompoundi sacarboxyli
cacid.
C—OStretchoccursi ntherange1 320–1 0cm−1wi
21 thmedi umi ntensity.
−1
O—Hout-of -planebendi ngvibrati
on,appearsatabout930cm .Thi slatterbandis
usuallyoflow-to-medi umintensity.
 -22-
Esters
C=Ostretchappearsi
ntherange1750–1735cm−1f ornormalal
iphati
cesters.
TheC=Obandisshi
ftedtolowerfrequencieswheni tisconj
ugatedtoα,βC=Corphenyl
−1 −1
group.
Thevalueisloweredto1740–171
5cm f orC=Oand1640–1625cm f orC=C(
two
bandsforsomeC=C,ci
sandtrans.

Conj
ugati
onofC=Owi
thphenyl
;1740–1
715cm−1f
orC=Oand1 450cm−1f
600–1 orri
ng.

conjugationofaC=Corphenylgroupwi ththesingl
e-bondedoxygenofanesterleads
-1
toani ncreasedf requencyfrom therangegivenabovethatis1 750–1735cm The
valueisincreasedto1765–1762cm−1f
orC=O.
C—O
Stretchoccursintwoormorebands,onestrongerandbroaderthantheother,
occurs
−1
intherange1300–1
000cm .General
ly,
theC—Ostretchnexttothecarbonylgroup(the
“aci
d”si
de)oftheesteri
soneofthestrongestandbroadestbandsinthespectrum.

-23-
Conjugationwi thaCarbonylGroup(
α,βUnsaturati
onorAryl
Substitution:
TheC=Ostretchingvibrati
onsareshiftedbyabout1 5to25cm−1tolowerf requenci
es
withα,βunsaturati
[Link] ate
andmethylbenzoate show theC=Oabsorpti onshiftfrom theposi
tioni nanormal
ester,
[Link]
cethattheC=Cabsorpti onbandat1630cm−1i nmethyl
methacrylatehasbeenintensi
fiedoverwhati sobtai
nedwithanonconj ugateddouble
bond.

-24-
Conj
ugati
onwi
ththeEsterSi
ngl
e-BondedOxygen:
Conjugati
oni nvolvi
ngthesingle-bondedoxygenshiftstheC=Ovi brati
onstohi gher
frequenci
[Link],
theconj ugati
oninterf
ereswithpossibl
eresonancewiththe
carbonylgroup,leadi
ngtoanincreaseintheabsorpti
onfrequencyfortheC=Oband.
Hydrogen-Bondi
ngEffects
Wheni
ntramolecular(
internal
)hydrogenbondi
ngi
spresent,
theC=Oi
sshi
ftedtoa
l
owerfrequency.

AMI
DES
CarbonylAbsorpti
oni
nAmi
des
Primaryandsecondaryami desinthesol i
dphase( potassiumbromi depell
etorNuj ol
)
−1
havebroadC=Oabsorpti onsi ntherangef rom1700–1640cm .
Forprimaryandsecondaryami des, theN–Hbendingvibrationusuallyoverlapswiththe
carbonylabsorption,resul tinginabroadbandbetween1 695and1 626cm−1
Inverydil
utesolution,thebandappearsatabout1 690cm−1.
Tertiaryamides,whichcannotf ormhydrogenbonds, haveC=Of requenciesthatarenot
infl
uencedbythephysi calstateandabsorbi naboutthesamerangeasdopri maryand
−1
secondaryamides( 1700–1 640cm ) .

-25-
N—HandC—NStretchi ngBandsi namides
N—HStretchi ngBands
Theappearanceandposi tionoftheN–Hstretchi ngvibrationofami desdepend,inpart,
uponstructuralf eaturesoftheami deanditsphysicalstate.
Forinstance,pri maryami desindi lutesolutions,usuallyshow symmetri caland
−1
asymmetri calH–N–Hstretchi ngvi
brationsnear3520and3400cm respecti vely.
Secondaryami desindil
utesol uti
onsshowonl yonebandwhi chappearsnear3333cm−1
Naturall
y,thisabsorptionisabsentinthespectraofterti aryamides.
Inthesoli
dstate( KBrorNuj ol
)theN–Hstretch i
ngvibrationsofpri maryamidesoccur
near3350and31 80cm−1.
Forsecondaryami des, takenasthesol idsampl e,theN–Habsorpti onsusuall
yappearas
−1
mul ti
plebandsnear3330cm .
N—HBendi ngBands
Inthesol idstate, primaryami desgivestrongbendi ngvibrationalbandsintherange
−1
from1 640to1 620cm .
Primaryami desgiveotherbendi ngbandsatabout1 125cm−1andaverybroadbandi nthe
−1
rangef rom750to600cm . Secondaryami desgi verel ati
velystrongbendingbandsat
about1 550cm−1;theseareattri butedtoacombi nationofaC—Nstretchi ngbandandan
N—Hbendi ngband.
C—NStretchi ngBands
−1
C—Nstretchi ngbandappearsatabout1 400cm f orprimaryami des.

ACI
DCHLORI
DES
C=OStretchoccursi ntherange181 775cm−1i
0–1 nunconj
ugatedchl
ori
des.
Conj
ugati
on
−1
.
lowersthef requencyto1780–1760cm .
C-ClStretchoccursi ntherange730–550cm−1.
-26-

I
nfra-redspectrumofacetylchl
ori
de
Anhydri
des
The characteristi
c pattern f or non-cycli
c and saturated anhydri des is the
appearanceoftwostrongbands, notnecessarilyofequali ntensiti
es,i
ntheregions
from1 830to1800cm−1andfrom1 775to1 740cm−1.
Thetwobandsresul tfromasymmetri candsymmetricstretch.
Fornon-cycl i
canhydrides,
theabsorpti onathigherf requencyisthemorei ntenseof
thetwo.
Conversely,forcycl i
canhydrides,theabsorpti onathi gherf requencyisofl ower
intensity.
Conjugationshi
ftstheabsorptiontoal owerfrequency,whilecycli
zation(ri
ngstrai
n)
shiftstheabsorptiontoahigherf requency.
 -27-
TheC–Ostretchingvibrati
onf orbotharomaticandal iphaticnon-cycli
canhydri
des
appearsbetween1250and1000cm−1.
Forcycli
canhydrides,thisabsorpti
onisshi
ftedto
approxi
mately910cm−1.
Inmostcases,theC–Ostretchingvibrationi
sbroadandstrong.

Ami
nes
Pri
maryami nesarecharacteri zedbyabsorpti onsi nthefoll
owi nggeneralregi ons.
Two weak absorpti ons attri buted to the –NH2 asymmetri caland symmetri cal
stretchingvibrati ons.
Theseabsorpti onsarel ocatednear3390cm−1and3296cm−1respecti vely.
Thenormalrangeoftheasymmetri calstretchingi sbetween3400and3200cm−1
secondaryami nes,therei sonl yoneabsorpti oni ntheregi onsmenti onedandf or
tertiaryami nestherearenone. .
Anaromati csecondaryami negivesastrongerN—Hbandnear3400cm−1.
–NH2scissoringbendi ngvibrati ons:near1615cm−1. Thenormalrangef orthisabsorption
−1
is1600–1630cm . Obviousl y,
thisabsorpti onisabsencei nthespectraofsecondaryand
tertiaryami nes. Inaromati csecondaryami nes, thebandshif tstoal owerf requency
−1
andappearsnear1 500cm .
–NH2waggi ng:between91 0and770cm−1. Thi
sbroadabsorpti oni susuallyfoundi nthe
spectraofsecondaryami nes,buti snotfoundinthespectraofterti aryamines.
The C–N stretchi ng vibration i s usually weaker and more dependent upon the
structuralf eaturesoftheami neasshownbel ow:

TheC—Nstretchingabsorptionoccursi
ntheregi
onf
rom1 000cm−1asamedi
350to1 um
tostrongbandforallamines.
 -28-
The C—N absorption occurs at a hi
gher frequency in aromati
c amines because
resonanceincreasesthedouble-bondcharacterbetweentheri ngandtheattached
nitrogenatom.Aromaticaminesabsorbfrom1350to1 250cm−1.
.

1
.)3300and3380 2.
)1600 3.
)1080 4. )835cm-1
)790 5.
I
nprimaryamines,theN—Hbendi ngmode( sci
ssori
ng)appearsasamedi um-tostrong-
i
ntensi
ty(
broad)bandintherangef rom1
640to1560cm−1..
Theinfraredspectrumofdibutyl
amine(neatl
iqui
d,KBrpl
ates).

-1
1.3280 2.1 11
5 3.738cm
InaliphaticsecondaryaminestheN—Hbendi ngvibrati
onisveryweakandusuallyisnot
observed.
Anoutof -pl
aneN—Hbendingvibrationappearsasabroadbandnear800cm−1f
orpri
maryand
secondaryami nes.
 NoN–Hstretchi
ngandnoN-Hoop 1
.1 090cm-1C-Nstretch
-29-

THEI
NFRAREDSPECTROMETER
Theinstrumentthatdetermi nestheabsorpti onspectrumf oracompoundi scal
l edan
infrared
spectrometeror,morepreci sel
y,[Link] nfrared
spectrometersareincommonuse: di
spersiveandFouriertransform( F
T)instruments.
Bothofthesetypesofi nstrumentsprovi despectraofcompoundsi nthecommon
rangeof4000
to400cm−1.
Althoughthetwoprovi denearlyidenticalspectraf oragivencompound, FTinfrared
spectrometersprovidetheinfraredspectrummuchmorerapi dlythanthedispersive
instruments.
Di
spersi
veI
nfraredSpectrometers
The schemati
c representati
on ofdi
fferent components ofa si
mpl
e di
spersi
ve
i
nfraredspectrometerisshowni
nthefi
gure.
 -30-
Thei nstrumentproducesabeamofi nf raredradi ationf romahotwi [Link]
mirrors, theradiationi sdi videdintotwoparal lelbeamsofequal -intensityradiation.
Thesampl eisplacedi nonebeam, andtheotherbeami susedasaref [Link]
thenpassi ntothemonochromator, whichdi sperseseachi ntoaconti nuousspectrum
off requenciesofinf raredl ight.
Themonochromatorconsi stsofarapi dlyrotati ngsector( beamchopper)thatpasses
thetwobeamsal ternatel ytoadi ffracti ongrating( apri sm i
nol derinstruments) .
Thesl owlyrotati ngdi ff ractiongrati ngvari esthef requencyorwavel engthof
radiationreachingthethermocoupl edetector.
Thedetectorsensestherati obetweenthei ntensitiesoftheref erenceandsampl e
beams. I
nthisway, thedetectordetermi neswh ichfrequenci eshavebeenabsorbedby
thesampl eandwhi chf requenci esareunaf fectedbythel i
ghtpassi ngthroughthe
sampl e.
Afterthesi gnalf rom thedetectori sampl i
fied,therecorderdrawstheresul ting
spectrumofthesampl eonachart.
Itisimportanttoreal izethatthespectrumi srecordedasthef requencyofi nfrared
radiationchangesbyrotati onofthedi ffractiongrati [Link] nstrumentsare
saidtorecordaspectrumi nthefrequencydomai n.
Itiscustomarytopl otf requency( wavenumber, cm−1 )versusl i
ghttransmi tted,not
li
ghtabsorbed. Thisi srecordedaspercenttransmi ttance( %T)becausethedetector
recordstherati oofthei ntensi ti
esofthetwobeams, and

whereIsi
stheintensi
tyofthesampl ebeam, andIristhei ntensi
tyoftheref erence
beam.I
nmanypartsofthespectrum, thetransmi ttanceisnearly100%,
meaningthat
thesamplei
searlytransparenttoradi ati
onofthatf requency(doesnotabsorbi t)
.
Maximumabsorpti
onisthusrepresentedbyami ni
mumonthechart.
Fouri
erTransformSpectrometers
The most modern i
nfrared spectrometers(
spectrophotometers)operate on a
differentpri nci [Link] gnoftheopti calpathwayproducesapatterncal ledan
interferogram.
Thei nterf erogram i sacompl exsi gnal,buti tswave-l ikepatterncontai nsallthe
frequenciesthatmakeupthei nf raredspectrum.
Ani nterferogram i sessenti al l
yapl otofi ntensityversusti me( atime-domai n
spectrum) .
However,apl otofi ntensityversusf requency( afrequency-domai nspectrum)i s
required.
Amathemati caloperati onknownasaFouri ertransform ( FT)canseparatethe
indi
vidualabsorpti onf requenciesf rom thei nterferogram,produci ngaspectrum
virtuallyidenti caltothatobtai nedwi thadi spersivespectrometer.
Thistypeofi nstrumenti sknownasaFouri ertransformi nfraredspectrometer, or
FT-IR.
TheadvantageofanF T-IRinstrumenti sthati tacquiresthei nterf
erogram i
nl ess
thanasecond.I ti sthuspossi bletocol lectdozensofi nterferogramsofthesame
sampl eandaccumul atethemi nth ememoryofacomputer.
When a F ourier transf orm i s perf ormed on the sum of the accumul ated
interferograms, aspectrumwi thabettersi gnal-to-noiserati ocanbeplotted.
-31-
AnF T-IRinstrumenti stheref orecapabl eofgreaterspeedandgreatersensi ti vity
thanadi spersi oni nstrument.
Aschemati cdiagramofanF T-IRisshowni nthef i
gure.

TheF T-IRusesani nterferometertoprocesstheenergysenttothesampl [Link]

i
nterf erometer,thesourceenergypassesthroughabeamspl itter,amirrorplacedat
a45°angl etothei ncomi ngradiati
on,whi
challowsthei ncomingradiationtopass
throughbutseparatesi tintotwoperpendicul
arbeams,oneun-def l
ected,theother
ori
entedata90°angl [Link],theoneori
entedat90°infigure,goestoastationary
or“fi
xed”mi rrorandisreturnedtothebeamspl itter.
Theun-def lectedbeamgoesto
amovi ngmirrorandi sal soreturnedtothebeamspl i
[Link] onofthemi rror
causesth epathlengththatthesecondbeamtraversestovary. Whenthetwobeams
meetatthebeamspl itter,theyrecombi ne,butthepathl engthdifferences(differing
wavel engthcontent)ofthetwobeamscausebothconstructi veanddestructi ve
interf [Link] nedbeam contai ningthesei nterferencepatternsi scalled
thei nterf erogram.
Thisi nterf erogramcontai nsal loftheradi ati
veenergycomi ngfromthesourceand
hasawi derangeofwavel engths.
Thei nterf erogram generatedbycombi ni
ngthetwobeamsi sorientedtowardthe
sampl e by the beam spl i
[Link] i t passes through the sampl e,the sampl e
simul taneousl yabsorbsal lofthewavel engths( f
requenci es)thatarenormal l
yfound
ini ts i nfrared [Link] modi f i
ed i nterferogram si gnalthat reaches the
detectorcontai nsi nf ormationabouttheamountofenergythatwasabsorbedat
everywavel ength( f requency).Thecomputercomparesthemodi fiedinterferogram
toaref erencel aserbeamtohaveastandardofcompari [Link] i
nalinterferogram
contai nsal lofthei nf ormationi nonetime-domai nsignal,asignalthatcannotberead
byahuman.
A mathemati calprocess cal led a Fourier transf orm must be i mpl emented by
computer to extract the i ndivi
dualf requencies that were absorbed and to
reconstructandpl otwhatwerecogni zeasatypi calinfraredspectrum.
1.(a)Intermsoftransi ti
ons,howdoesI Rspectroscopydi fferfromUVspectroscopy?

-32-
(b) Arrange the fol lowi ng transi tions i n order of thei ri ncreasing energy
requirement Vi brational,electroni candrotati onal
Ans:Th evisibleandul travi oletspectraoforgani cmol eculesareassoci atedwi th
transiti
onsbetweenel ectroni cenergyl [Link] onofinf raredradiati
onby
amol eculeoccursduetoquanti zedvi brationalandrotati onalenergychangeswh enit
issubjectedtoi nfraredi rradiati [Link],I Rspectraareof tencal ledvibrational-
rotationalspectra.
[Link]:
(a)Stretchingandbendi ngvi brati ons; (b)Fingerprintregion;(c)Fermi resonance
Ans:Thetwotypes( modes)off undamentalmol ecularvibrationsknownare:( a)
stretchingand( b)bendingvi brations( deformati ons).
(i)StretchingVibrations
Instretchingvibrations,thedi stancebetweentwoatomsi ncreasesordecreases, but
theatomsremai ninthesamebondaxi [Link]:
(a)Symmetri calstretching.I nthi smodeofvi bration,themovementofatomswi th
respecttothecommon( orcentral )atom i ssimul taneouslyinthesamedi rection
alongthesamebondaxi s( Fi
g. ).

(
b)Asymmetri
calStretchi
ng.
Inthi
svi
brati
on,
oneatomapproachesthecommonatom
whi
letheotherdepartsf
romi
t(F
ig.
).

i
(i)Bendi
ngVi
brati
ons(
Deformati
ons)
I
nsuchvi brations,theposi tionsoftheatomschangewi threspecttotheiroriginal
[Link] ngvi brationsareoff ourtypes:
(a)[Link] smodeofvi brati
on,themovementofatomsi sintheopposi te
directionwi thchangei ntheirbondaxesaswel lasinthebondangletheyformwi ththe
centralatom( Fig.(a)).
(b)[Link] bration,themovementofatomstakespl acei
nthesamedi rection
wi thchangei ntheirbondaxes( F
ig.(b))
.Scissori
ngandrockingarein-pl
anebendings.
(c)Waggi [Link] svi bration,twoatomssi multaneousl
ymoveaboveandbel ow the
planewi threspecttothecommonatom( Fig.
(c)).
(d)Twi [Link] bration,oneoftheatommovesupandtheothermoves
downthepl anewi threspecttothecommonatom( Fig.
(d)
).
-33-

Fingerpri
ntregi
on:
Itisnotpossibl
ef oranytwodifferentcompounds(exceptenanti
omers)tohave
exactlythesameIRspectrum.
Therefore,
theI
Rspectrumofacompoundi scal
ledi
ts
fingerpri [Link] onbel ow 1500cm-1i scal ledf ingerpri ntregi onbecauseevery
compoundhasuni queabsorpti onpatterni nthi sregi on. Thef ingerpri nt region
contai nsmanyabsorpti onbandscausedbybendi ngvi brati onsaswel lasabsorpti on
bandscausedbyC-C, C-0l i
kei nal cohols,ethers, esters, [Link]-N( e.g.i nami nes,
ami noaci ds,amides,etc. )Stretchi [Link] ngvi brations
inamol ecul eismuchgreaterthani tsStretchi ngvibrati ons, thef ingerpri ntregi onis
richinabsorpti onbandsandshoul [Link], thesuperi mposabi lityofI Rbandsofthe
spectraofanytwodi fferentcompoundsbecomesi mpossi blei nthi sregi on. However,
-1
simi l
arcompoundsmayshowverysi mil
arspectraabove1 500cm .
Fermi resonance
Ans:F ermiresonanceresul tsi nthespl ittingoftwovi brationalbandsthathave
nearl ythesameenergyandsymmetryi nbothI RandRamanspectroscopi ctechni ques.
Thetwobandsareusual lyaf undamentalvi brati onandei theranovertoneor
combi nati onband. Thewavef uncti onsforthetworesonantvi brati onsmi xaccordi ng
totheharmoni cosci l
latorapproxi mation, andtheresul ti sashi f tinf requencyanda
changei nintensityi [Link] t,twostrongbandsareobservedi nthe
spectrum,i nstead ofthe expected strong and weak bands. I fthe symmetry
requi rementsaref ulfill
edandtheenergi esofthetwostatesaresi mi lar,mixing
occurs, andtheresul tingmodescanbedescri bedbyal i
nearcombi nationofth etwo
interacti [Link] fectofthi si
nteracti onistoi ncreasethespl ittingbetween
theenergyl [Link] ittingwi llbelargeri ftheori ginalenergydi fferencei ssmal l
andthe
-34-
coupl ingenergyi [Link] xingofthetwostatesal soequal izedthei ntensities
ofthevi brationswhi chal lowsaweakovertoneorcombi nati onbandtoshow
significanti ntensityf rom thef undamentalwi thwhi chi thasF ermiresonancewi th.
Fermi resonancegi veri setoapai roftransi ti
onsofal mostequali ntensi ty, andsothe
resul ti ngabsorpti onbandsusual lyappearasadoubl et.

Thetopbandsrepresenttwof undamentalvibrationswi thoutFermiresonance,and

thebottombandsshowthechangei nbandsasaresul tofF [Link]
energylevelsarespi ltsuchthatonei ncreasesandtheotherdecreasesi nenergy,
knownasa“ Fermi doublet,
”andth eymoveawayf romeachother.
[Link] lowing:
(a)Whydoeshydrogenbondi nglowertheabsorpti onfrequency?
Ans:Letustaketheexampl eofh ydroxycompounds. Onhydrogenbondi
ng,theorigi
nal0
-Hbondi sl engthened(weakened)duetoel ectrostaticattractionbetweenthe
hydrogenatomsofonemol eculeandoxygenatom oftheother,andthusthef orce
constant ofthe0-Hbondi sreducedresul tingi nadecreasei ni tsstretching
frequency.
Distinctionbetweeni nter-andi ntramol ecul arhydrogenbondi ngs
Inverydi lutesol utions( innon-pol arsol vents) ,intermol eculardi stancesaretoo
largetof ormi ntermol ecul arhydrogenbonds. Ontheotherhand, i
npurel i
quids,soI i
ds
and concentrated sol uti ons,the mol ecul es are cl oser to f orm intermolecul ar
hydrogenbond. Thus, intermol ecul arhydrogenbondi ngisconcentrati ondependent. On
dilutionwi thnon-pol arsol vents,i ntermol ecul [Link],
there i s decrease i ni ntensi ty or di sappearance of the hydrogen-bonded 0-H
stretchi ngbandandi ncreasei ni ntensi tyorappearanceoff ree0-Hstretchi ng
absorpti [Link], i
nverydi lutesol utions( innon-pol arsol vents,concentrati on<-0. 01
M) ,the 0-HStretchi ng f requency i s shi f ted to ahi gherf requency in case of
intermol ecularhydrogenbondi ng.
Intramol ecularhydrogenbondi ngi swi thinthesamemol ecule,hencei tisnotaf f ected
bychangei ni ntermol ecul ardi [Link],i ntramol ecularhydrogenbondsare
unaf fectedbydi lution, andsotheabsorpti onbandi salsounaf fected. I
ntramol ecular
hydrogenbondi ng( chel ation)i sverystrongi nenol sandcompoundsl ikemethyl
salicylateetc.,duetoresonancestabi li
zati onofthechel atering. Forexampl e,i
nenol s,
the0-Hgroupi nvolvedi nchel ationshowsbroadabsorpti onbandi ntherange2500-
3200cm-1, whereastheC=Ostretchi ngbandi nenol icformoccursat1 630cm-1andthat
-1
intheketof orm at1 725cm .F rom therel ativei ntensi ti
esofthetwobands, itis
possibletodetermi nerati ooftheketoandenolf orms.

-35-
 -1
νC=O=1 680cm
(b)Ethanolandmethanolaregoodsol ventsforrecordi ngUVspectrabutnotforI R
spectra.
(c)νc=0frequencyforethylacryl ateisl owerthanthatforethylpropi onate.
([Link] ugation.)
[Link] undamentalvi brationsi rithef ollowingmol ecul
es:
(i)Methane( ii
)Ethanol( ii
i)Acetyl ene( i
v)Ethyl ene( v)Oxygen
[Link] ol l
owi ngI Rabsorpti onbandstoaparti cularcarboxyl icacidderivativei
n
eachcase:
(i)1715-1750cm-1( ii
)1 750-1 81
5cm-1( iii)1630-1690cm-1
(iv)1740-1790and1 800-1 850( twobands)
[Link] ai
nthef ollowi ng:
(a)Concentratedsol utionsofal cohol si nCC14haveanI Rabsorpti onbandatabout3300
cm-1butthi sbandi sshiftedtoah i
gherf requencyondi l
ution.
(b)I Rspectrahavea! argenumberofabsorpti onbandsascomparedtoUVspectra.
([Link] argenumberofstretchi ngandbendi ngvibrati onsinthemol ecule.)
(c)o-Ni trophenolshowsνO-Hbandat3200cm-1i nKBrpel letaswel lasinCHC13s oluti
on,
whereasth eparai somershowsthi sbandatdi fferentf requenci esinthetwomedi a(i
n
-1 3
pelletat3330cm andi nCHC1 sol utionat3520cm-1 .
)( Hi
nt.The0-Hgroupofo-
nitrophenolisi ntramol ecularlyhydrogenbonded. Henceitsf requencyisnotaf f
ected
by the medi um or change of concentrati on,whereas the para i somer i s
intermol ecularlyhydrogenbondedi n

-36-
pelletandthehydrogenbondi ngdi mini
shesinCHC1
3s oluti
onduetorel ativedi
lution
-1
resultingintheshi ftofVo.-Hbandtohi gherf
requency,3520cm .)
[Link] wi llyoudi stingui
shthetwomembersofeachofthef oll
owi ngpairsof
compoundsusi ngIRspectroscopy:
(a)CH3COOHandHCOOCH3
(b)ß-propi olactoneandy-butyrol actone
(c)ClCH2CH2CH2COOHandCH30CH2CH2COC1
(d)CH3CH2CHOandCH2=CH-CH20H
[Link] RandUVspectroscopybeusedtodetermi newhenthef ol
lowingreactionis
compl eted?
(Hi
nt. TheUVspectrumofthestarti ngmateri alwillshowAmaxat237and31 0nmdue
toconj ugatedC=CandC=0groupsrespecti [Link] lldisappearon
compl etionofthereacti [Link]
mi larly,theIRabsorptionbandintheregi on1665-1685cm
-1duetoconj ugatedC=0group( presentinthestarti ngmaterial)wi lldi
sappearon
compl etionofthereacti [Link] tion,anew IRabsorptionbandwi llappeararound
3330cm-1duetohydrogen-bonded0-H
group. )
[Link] ollowingcompoundsi norderofincreasingwavenumber
ofcarbonylabsorpti oni ntheirI Rspectra:
(a)Acetophenone, p-nitroacetophenoneandp-arni noacetophenone.(Hint.A
groupwi th+M ef fectwi l
ldecreaseandthatwi th-M ef fectwillincreasethebond
orderofC=Obond. )
(b)Cycl obutanone,cyclohexanoneandcycl opentanone.
[Link] actorswhi chaf fecttheI Rabsorptionfrequencyofaf unctionalgroup.
11.
Expl ainwhyestersofo-chl orobenzoi cacidshowtwoC=0Stretchi ng
absorpti ons?

([Link] onali somer( a)ofo-chlorobenzoicester,Cli

sneartheC=0group
andi tsnegati vefiel drepel sthenon-bondingelectronsofthecarbonyloxygen( field
eff ect) .
Thus, thef orceconstantofC=0bondi sincreasedresultingi
nshiftingofthe
Vc=0bandtoahi gherf [Link] ntheisomer( b).
Normal l
y,
boththei somersarepresent, thustwoVc=Oabsorpti onsareobserved.)
[Link] someri ccompounds( A)and(B)havingmolecularformul a
C3H60andthef oll
owi ngIRspectraldata:
-1
(A)1 71
0cm ( B)-3300cm-1and1 640cm-1
-37-
[Link] wi llyoudi stinguishthef oll
owingpai rsofcompoundsonthebasi sofI R
spectroscopy?
(a)CH3CH2COC1andCl CH2COCH3
(b)ß-propi olactamandy. butyrolactam
(c)Benzeneandcycl ohexane
(d)Sal icyli
caci dandm-hydroxybenzoi caci
d
[Link] ollowi ngcompoundsdoyouexpecttohavehi gherVo.-Hfrequencyindil
.
CHC1 3solutionandwhy?
(Hi
nt.I
n(a)intramolecul
arhydrogenbondi
ngwil
ldecreaseva-Hf
requency.
)
15.
Givi
ngreasonsarrangethef ol
lowingcompoundsinorderofi
ncreasi
ngwavel
ength
ofcarbonylabsorpti
oninthei
rIRspectra:

[Link] ccompound( A)havingmol ecularformul aC3H7NOshowsI Rabsorpti onbands

at341 3( m),3236( m),2899-3030( m) ,1667( s) ,1
634( s)and1 460cm-1( s) .Gi
vethe
probabl estructureof( A).
[Link] vingexampl esdi scusshow i nducti veandmesomeri cef fectsinf l
uencethe
carbonylabsorpti onfrequency?
[Link] ainwhyacompoundi nthevapourstatehashi gherStretchingfrequencythan
thati nthel iqui
dorsol idstate?( [Link] ntermol ecularinteracti
ons, especial1
y
whenpol argroupscapab1 eofhydrogenbondi ngarepresent, thef orceconstantsof
bondsaredecreased. )
[Link] ollowi nginincreasi ngorderofthei rvD-Hf requency:
ethanol ,tri
chloroaceticacid,aceticaci dandchl oroaceticacid.
20. TheI Rspectrumofmethylsal icyl ateshowsabsorpti onbandsat3300, 3050, 2990,
-1
1700, 1590and1 540cm .Whi chofthesebandsareduetowhi chofthef oll
owi nggroups?
C=O, CH3,0-Handaromati cring
[Link] acetateshowsVc=oabsorpti onat1 735cm-1 ,whereasphenylacetateat1 770
cm-1. Expl ai
n.
[Link] ol
lowi ngcompoundsi norderofi ncreasingabsorptionf requencyof
thei rcarbonylgroups. Givereasonf oryouranswer.

-38-
[Link], howwi llyoudistinguish:
(a)Intermol ecularandintramolecul arhydrogenbondi ng
(b)cis-cinnarnicacidandtrans-ci nnamicaci d
(c)Axialandequatori al0-Hgroup. (Hi
nt.Dueto1 ,
3-diaxi
alinteracti
on,theStretching
vibrationoftheaxi al0-Hgroupi shinderedandthusi tsabsorptionfrequencyisrai
sed.
)
27.2-hydroxy-3-ni troacetophenoneshowstwoVc=Obandsat1 692and1 658cm-1.
Explain.
(Hint.I
nsomemol ecules,thereisintramolecularhydrogenbondingbetweenOHandC=0
,whi l
einotherbetweenOHandN02group. )
[Link]=Of requencyf orm-chl orobenzoicacidishigherthanthatf orp-
chlorobenzoicaci
d?( Hi
nt. Dueto+Mef fect,Cldecreasesthef orceconstantofC=0
bondf romtheparaposi tionbutnotf romthemetaposi ti
on.)
[Link] thmol ecul
arf ormulaC7H80gi vesthef ol
lowingIRspectraldata.
Deduceth estructureofthecompound.
IRbandsat-3300( s)
,-3040( m) ,
2800-2950( w),
1606( m),1
582( m),1
500(m) ,
1450(w),
-1
1380( w),
1185(s)780(s)and692cm ( s)
.
Probl
ems
1
.UsingIRspectroscopy, howwi
llyoudi
sti
ngui
shthef
oll
owi
ngi
someri
ccompounds:
(
i)CH3CH2C≡CHandCH3C≡CCH3
(
ii
)CH3CH20HandCH30CH3
(
ii
i)(CH3)3NandCH3CH2NHCH3
Sol
uti
on.(i
)CH3CH2C≡CHwi
llsh onbandsat-3300cm-1dueto≡C-
owstrongabsorpti
H,2100cm-1duetoC≡Cstretchi ngand625cm-1dueto≡C-Hbendi ngvibrati
[Link]
bandswi llbeabsentintheI RspectrumofCH3C≡CCH3. ItshouldbenotedthatνC≡Cband
wi l
lal so be absent in the IRspectrum ofCH3C≡CCH3 because the symmetri cal
SubstitutionmakestheC≡Cstretchi ngf requencyI
Rinactive.I
nboththecasesth eIHD
is2.
(ii
)CH3CH20Hwi l
lshowabsorptionbandsi ntheregion3200-3600cm-1duetoStretchi ng
vibrati
onofi ntermolecularlyhydrogen-bonded0-Hgroupandat-1 050cm-1duetoC-O
stretching·Thesebandswi l
lbeabsenti ntheI RspectrumofCH30CH3.l twillshowan
-1
absorptionbandaround1 100cm duetoC-0-Cstretchi ng.
(ii
i)CH3CH2NHCH3 wi
llshow amedi um bandi ntheregion331 0-3550cm-1duetoN-H
[Link]( CH3)3N.
Probl
em2
How wi l
l you di sti
ngui
sh o-hydroxybenzaldehyde (
sal
icyl
aldehyde) and m-
hydroxybenzal
dehydeonthebasi
sofIRspectroscopy?
Sol
uti
on.
Insal
icyl
aldehyde,
duetoi
ntramol
ecul
arhydrogenbondi νO-Handνc=o
ng,
bandsareshi ftedtol [Link] ncei ti sintramol
ecular,changei n
concentrationdoesnotcauseanyshiftinνO-Handνc=oabsorpti
onbands.
I
ncaseofm-hydroxybenzal dehyde,νO-Hand νc=o bandsoccuratasti lllower
wavenumberduetoi ntermolecularhydrogenbondi [Link] νO-Handνc=obands
scase,
shi
fttohi gherwavenumbersondilutionwithanonpol arsolvent.

-39-
Probl
[Link]
ning1
0%hydrogenshowsthef
oll
owi
ngbandsi
nits
I
Rspectrum:
(
i)3295cm-1(
ii 30cm-1(
)21 ii
i)[Link].
Sol
uti
on.
Amongvari
oushydrocarbons,
onl kynesshowabandaround3300cm-1
yal
dueto≡[Link],theappearanceofabandat3295cm-1cl earlyshowsthe
presenceof≡C-Hgroupinthehydrocarbon. Thepresenceofabandat21 30cm-1dueto
ngandanotherbandat625cm-1
C≡CStretchi
dueto≡C-Hbendingconf i
rmthatthehydrocarboni sanal kyne.
10%hydrogencontent
showsthatitispropyne(CH3C≡CH).
Probl
[Link]:
(a)StretchingfrequenciesofC-C,C=CandC≡Cfal
lintheregi ons
whicharei nincreasingorder800-1 200cm-1,1650-1670cm-1 and21 00-2260cm-1,
respectively.
(b)TheνO-Hbandappearsnear3570cm-1,whereastheνO-Dbandappearsnear2630cm-1.
-1 -1
(c)2-t-butyl phenolhastwoνO-Hbands-oneat3608cm andtheotherat3643cm ,
-1
whereas2, 6-di
-t-butylphenolhasonlyoneandat3642cm .

Sol
uti
on.(a)Accordi
ngtoHooke'
slawthestretchi
ngf
requencyofabondi
ncreases
withani ncreasei nthef orceconstant,i .
e.,[Link],thestretchi ng
frequenciesofcarbon-carbonsi ngl e,doubleandtri pl
ebondsincreaseintheorderof
theiri
ncreasi ngbondstrengths,i
.[Link] ncreasingorderofstretchingfrequenciesi
s
C-C<C=C<C≡C
(b)AccordingtoHooke' slaw thestretchi ngf requencyofabondi ncreasesasthe
reducedmassofthebondedatomsdecreases. Sincehydrogenhaslesseratomi cmass
-1
thandeuteri um,the0-HStretchi ngf requency( near3570cm )ishigherthanthe0-D
-1
stretchingfrequency( near2630cm ) .
(c)In2-t-butyl phenol,twobandsarepresentat3608and3643cm-1showi ngthat
somemol eculesareintermol ecularlyhydrogenbonded,whereasi nothersOHi snot
hydrogenbondedduetosteri chi
ndrancebythebul ky-t-butylgroup.

I
n2,6-di-t-butyl phenol,becauseofthepresenceoftwobul ky-t-butylgroupsi
nthe
orthopositionoftheOHgroup, theOHgroupsoftwodifferentmoleculesarenotabl
e
toapproachcl oseenoughtof ormintermolecul
arhydrogenbond.
Thus,2,
6-di-t-butyl phenolshowsonl yoneνO-Hbandat3642cm-1duetononhydrogen
-bondedOHgroup.

-40-
em5.
Probl Gi
vingreasonsarrangethef
oll
owi
ngcompoundsi
norderofdecreasi
ng
f
requencyofcarbonylabsorpti
oni
nthei
rIRspectra:

Sol
uti
on:
.Thef
oll
owi
ngi
sdecreasi
ngorderoff
requencyofcarbonylabsorpti
on
(c)>(a)>( b)
Cyclohexanecarboxal dehyde(c)isasaturatedal dehyde,
hencewi llabsorbaround1 730
-1
cm . Duetoconj ugationoftheC=0groupwi ththedoubl ebondsofthebenzeneri ng,
theνC=Oabsorpti onofbenzal dehyde(a)willbeshiftedtolowerf requency( -1700cm-1).
InSal icyl
aldehyde( b),thel oweringisduetoconj ugati
onaswei lasi ntramolecular
hydrogenbondi ng( chelation)thustheνc=oabsorpti
, onfrequencyisf urtherlowered( -
-1
1665cm ) .
Probl
em6.
Howwi
llyoudi
sti
ngui
shthetwomembersofeachofthef
oll
owi
ngpai
rs
ofcompoundbythei rIRspectra:
(a)CH3CH2C=CHandCH3CH2C=N(b)RNH2andRCONH2(c)CH3COCH3andCH3CH=CHCH20H
(d)CH2=CH-O-CH3andCH3CH2CHO ( e)CH3CH2CHOandCH3COCH3
Sol on.
uti (a)CH3CH2C≡CHwi
l onbandat-3300and625cm-1
lshowstrongabsorpti
dueto≡C-Hstretchi ngandbendi ngvi brations,[Link] llbe
absentintheI RspectrumofCH3CH2C≡N.
(b)RCONH2wi l
lshowastrongνc=obandaround1 690cm-1( i
ndilutesoluti
on)whichwi l
lbe
absentintheI RspectrumofRNH2.
(c)CH3COCH3 willshow astrongνc=obandat-1 [Link] llbeabsenti n
CH3CH=CHCH20H.CompoundCH3CH=CHCH20Hwi llshowastrongνO-Hbandi ntheregi
on3200-
-1 -1
3650cm andanothermedi umνc=cbandintheregi on1620-1680cm .
(d)CH3CH2CHOwi l
lshow astrongνC=O bandnear1 730cm-1 andanotherweakband
(generallyappearingasadoubl etduetoF ermi resonance)intheregion2700-2900cm-
1
duetoal dehydicνC-H·
CH2=CH-O-CH3willshowastrongbandi ntherange1020-1075cm-1
duetoC-0-Cstretchi ngandanother
medi umbandnear1 650cm-1duetoC=Cstretchi ng.
(e)Acetonewi llshowastrongνc=obandat-1 715cm-1,
whereasthi sbandappearsat-
1730cm-1i npropionaldehyde.I
naddition,CH3CH2CHOwi l
lshowabandi ntherange2700-
-1
2900cm duetoal dehydicC-Hstretching. Thi
sbandgeneral lyappearsasadoubl etdue
toF ermiresonance.
[Link]
llyoudi
sti
ngui
shmal
eicaci
dandf
umari
caci
dbythei
rIRspectra.
Solution

-41
-
I
nmal eicacid,thebulkyCOOHgroupsareonthesamesi deofthedoubl
ebond,hencedue
torepulsiveinteractionstheC=Ogroupisforcedoutofthepl
aneoftheC=[Link],
theconj ugationisdi mini
shedresulti
ngintheappearanceofνc=o bandatahi gher
frequencyascomparedtothati nfumaricacidwheretheC=Ogroupisinconjugation
withtheC=Cbond.
Probl
em8.
Acompoundhavi
ngmol
ecul
arf
ormul
aC3H60gavethef
oll
owi
ngspectral
data:
(i)UV:
λmax292nm,εmax21
-1
(i
i)IR:
2720cm-1(w)and1 738cm ( s)
Deducethestructureofthecompound.
Sol
uti
on.
TheI
HDofthecompoundi
[Link]
ncethemol
ecul
arf
ormul
acontai
nsone
oxygenatom, thecompoundmaybeanunsaturatedal cohol,
saturatedal dehydeora
-
[Link] eabsenceofapeakat3600-3200cm 1showsthatthecompoundi snot
[Link]λmax292nm wi thε max 21i
ndicatingt hatiti
se itheran
aldehydeorketoneandthi sbandhasarisenfrom n→ π*transi tionofitsC=0group.
-1
TheappearanceofastrongI Rabsorpti
onbandat1 738cm i sindicati
veofanal dehydi
c
carbonylgroupwhichisconfirmedbythepresenceofanotherbandat2720cm-1dueto
aldehydicC-Hstretchi
[Link],th
ecompoundisCH3CH2CHO.

Probl
em9
Themol ecularf ormulaofthecompoundi sC8H80. Deducethestructureofthe
compoundf romthef oll
owingIRdata:
301
0,1690,1600,
1580,1450,762and692cm-1
[Link] onaround301 0cm-1 i
ndicati
ngthe
presenceofa=[Link] eusisshownbytheabsorption
- -1
bandsat1 600,1
580and1450cm 1 .Theappearanceofastrongbandat1 690cm shows
thatthecompoundi sanaromati [Link]-of -planebendi
ng
absorpti
onsat762and692cm-1i ndi
catesamonosubstitutedbenzenering.
Si
ncemol ecularformul
aisC8H80,thecompoundisacetophenone.

Howtodi
sti
ngui
shbetween-C=C-andaromati
c-C=C-stretchi
ngvi
brati
ons?
Probl
em1
0
Wri
tethevari
ousi
nfra-redbandsi
nthecaseoftol
uene.
Sol
uti
on:

i
) Ar-Hstr- ~3030cm-1 i
i) C-Hstr-i
nCH3-~2850-2960 cm-
1

i
ii
) C=Cstr ~1 600,
1580,1460cm-1
i
v)C-Hbendi
ngf
ormonosubstitutedbenzene-~730-770cm-1

-42-
Probl
em1
1
Descri
bethevari
ousi
nfra-redbandsi
ncaseofhexyne.
Sol
uti
on:
Thestructureofhexynei sH3C-CH
2-CH2-CH2-C≡CH
-1
i
)≡C-Hstr-~3300cm i i
)C-Hstretchi nCH2-andCH3-i
s~2860-2950cm-1
-1 -1
i
ii
)C≡Cstr-~21 00cm i v)C-Hbending~1 465cm
Probl
em1
2
Descri
bethevari
ousi
nfra-redbandsi
ncaseof2-Hexene.
Sol
uti
on:
Thestructureofhexynei sH3C-CH
2-CH2-CH=CHCH3
-1
i
)=C-Hstr-~3050cm i i
)C-Hstretchi s~2860-2950cm-1
nCH2-andCH3-i
i
ii
)C=Cstr-~1 680cm-1i v)C-Hbending~1 465cm-1
v)-CH=CH2(forcis,trans)700-970cm-1
Probl
em1
3
Comparethestretchi ngfrequencyofcarbonylabsorptioninthef oll
owingcompounds:
I)CH3CHO II)CH2=CH-CHO II
I)CH2=C-CHO
|
CH3
1745cm-1 723cm-1
1 1702cm-1
IncompoundI thereisnoconj ugation.I
ncompoundIItheC=Oi sinconjugati
onwi ththe
doublebondandhenceabsorpti onoccursatl [Link]
inadditi
on
to the conjugation +Ief fect ofmethylgroup l owers f urtherthe absorption
frequency.

Probl
em1
4
Anorganiccompound( A)wi thmol ecularf ormulaC3H9Nshowsthef ol
lowingpeaksinthe
inf
ra-redspectrum:
i)3012cm-1i )3423cm-1i
i i
i)3236cm-1i v)1 5cm-1
61
WhenthecompoundAi streatedwi thnitrousacidwegetacompoundBwhi chshowsa
-1
strongpeakat3430cm .WhatareAandBandexpl ai
nthereactionsinvol
ved.
TheIHDiszero
Thetwobandsat3423cm-1and 3236cm-1areduetosymmetri calandasymmetrical
[Link] nsNH2group
-1
Thepeakat301 2cm i sduetoC_Hstretchi ng.Thebandat1 615cm-1isduetoN-H
bendingvibration.
Theprobabl estructureofAi sCH3CH2CH2NH2
WhencompoundAi streatedwi thni trousaci d-NH2i sconvertedtoOHgroupwhi ch
[Link] oni
nvol
vedi
s
CH3CH2CH2NH2 +HONO → CH3CH2CH2OH+N2 +H2O
Probl
em1
5
How wi l
lyoudi
fferenti
atebetweenthef
oll
owi
ngpai
rsofcompoundsusi
ngI
R
spectrum:

-43-

a) b)CH3CH2CHOandCH2=CH-CH2OH

Sol
uti
on
a)o-hydroxybezoi cacidandm-hydroxybenzoi cacidshowasi mil
arbroadbanddueto-
-1
OHstretchi ngi n-COOHbetween3000-2500cm .However, inorthohydroxybenzoic
acidintramol ecularhydrogenbondi ngtakespl [Link] ore,theO-Hstretching
vibrati
ontakespl aceatl owerf requencyandchangei nconcentrationdoesnotcause
anyshifti nO-Hstretchi ngabsorptionf [Link]-hydroxybenzoi cacid
duetoi ntermol ecul
arhydrogenbondi ng,the-OHstretchi ngf requencyoccursata
stilll
owerf requencyandtheposi tionofabsorpti onbandshif
tswi thdil
ution.
o-hydroxybenzoi cacidshowsonebandatabout735-700cm-1whi l
em-hydroxy
benzoicacidshowstwobandsatabout690-71 0and730-770cm-1
b)CH3CH2CHOandCH2=CH-CH2OH
CH3CH2CHOshows-C=Ostrfrequencyat1
[Link]-Hstrinal sat2720cm-1.
dehydei
-1
TheC-Cstroccursat1400-1000cm
CH2=CH-CH2OHshows-O-Hstrat3300-3600cm-1.-C=Cstroccursat1
650cm-1
Probl
em1
5
Howwoul
dthei
nfra-redspectrumofC6H5CH2NH2andCH3-CO-N(
CH3)
2di
ffer?
Sol
uti
onC6H5CH2NH2,
benz;
ylami
neshowsthef
oll
owi
ngcharacteri
sti
cpeaks
i) characteristicvN-Habsorptionintheregi on3300-3500cm-1.I ndilutesoluti
on,
primaryami nesexhibit twosharpbandsduetosymmetri calandasymmetri cal
Stretchings.
ii
)Aromati cC-Hstretch, around3050cm-1.
-1
ii
i)N-Hbending,1620cm .
iv)C=Cringstretching,1600,1500and1468cm-1
v)C-Nstretchi ng,1
280and1 175cm-1
InCH3-CO-N( CH3)2theC=Ostr, frequencyoccursat1 [Link]
−1
relati
velystrongN-Hbendi ngbandsatabout1 550cm
Probl
em1
6TheI
Rspectrumofanorgani
ccompoundC8H7Nshowsthefol
lowi
ngbands:
3030(
w);
2920(
w);
221
7(s)
;1607(
m);
1607(
m);
1508(
m);
817(
s)
Sol
uti
on:Theformulaofthecompoundi
[Link]
HDi
[Link]
ythecompoundmay
beanaromati
c.I
tisconf
irmedbythepeaksat3030(
w);
);1
607(
m);
1508(
m).Thepeakat
221
7(s)i
sdueto-C≡Nstretchandthei
ndexofthe-C≡Ni 7cm-1i
s2.Thepeakat81 sdue
toparasubsti
tutiononthebenzeneri
ng.Thepeakat2920(w)indi
catesf
ewernumber
ofmethylgroupssincethepeaki
[Link]
s

p-toluoni
tri
le
-44-
Probl
em1
7Identi
fythestructureofthecompoundC8H8Owhosespectrumcontai
ns
thefoll
owingabsorpti
onbands:
1680(
s),1
600(m),1
580(m),
1450(m),
1430(
s),
1360(
s),
1265(
s),
755(
s), s)cm-I.
690(
Sol
uti
on TheI
HDofC8H8Oi
[Link]
c.
Themonosubstitutedbenzeneringhasthecharacteri
sti
cbandsat1600,
1580,
1450,750
-I
and690cm .
Thecharacteristi
cbandsf orthearomati cketoneareat1 680(forC=O) and1 275
-I
bendi
ngmodesof( C-CO-C)cm ,andthoseforthemethylgroupareat1430and1360cm
-I
. Thestructureofth ecompoundi
s

Probl
em1
8:Deducethestructure:
C8H18I cm-I) 2960;
Rbands( 2860;
1460; 1 395;1
385; 1 375;1365
TheI [Link]
sasaturatedcompound.
2960and 2860i catesp3 -C-Hstrvi
ndi brati
ons.1 460cm-1showsthepresenceof
methylgroup.1 395and1385cm-1:I
tisdoubleti
ndicatesi sopropylgroup.
1375and1 365cm-1i
ndi
catesthepresenceoft-butylgroup

Probl
em:
19 Supposethatyouarei
nvesti
gati
ngacompoundwi
ththemol
ecul
ar
[Link] i
ndthati tcontai
[Link]
determinethisonthebasisofthef ol
lowingbandsintheIRspectrumofaCCI 4solution
-I -I -I
ofthecompound.3030cm ( weak),1
765cm ( strong),1649cm ( strong)
,1225cm-I
(strong)and 1 40 cm-I (
1 strong)
.Identify these bands,write al lthe possible
structureswhichincl
udethesetwogroups.
Sol
uti
on:TheI
HDi
s2.
C-Hstretchingat3030cm-1:canbeduetoaromaticor=C-Hstretchi
[Link]
tis
clearthatitisnotanaromati [Link]
ebondterminal
.Thepeakat
1765cm-1isduetoC=Ogroup.1649cm-1showsthe-C=Cstretchi
ng.
-I
1225cm C-O-Cstr. (
asym.)
140cm-IC-O-Cstr.
1 (sym.
)
Estersgeneral
lyshowtwopeaksi
nthi
srange.
Thepossibl
estructuresare:

-45-
Ali
phaticethersshow acharacteri stic,strongbandi ntheregion1 060-1150cm-1
becauseofasymmetri calC-0-Cstretchi [Link] calstretchingbandi s
usuallyweak.
Saturatedal iphaticesters( exceptf ormates)show vc=oabsorptionbandsi nthe
-1
region1735-1750cm .
WhenaC=Coranaromati cringisattachedtotheoxygenoftheC-0groupofanester
orIactone,therei samarkedi ncreaseinthecarbonylfrequency.
TheC=Ostretchi ngvibrationsareshiftedbyabout1 5to25cm−1tol owerf requenci
es
withα, βunsaturationorarylsubsti tution.
Si
ncethestretchi ngf requencyof C=Oi s1765cm-1,
thedoublebondisattachedtothe
[Link] s