Organic Chemistry, 7th Edition L. G. Wade, Jr.

Chapter 12
Infrared Spectroscop and !ass Spectro"etr

2010, Prentice Hall

Introd#ction
$ Spectroscop is a techni%#e #sed to deter"ine the str#ct#re of a co"po#nd. $ !ost techni%#es are nondestr#cti&e 'it destro s little or no sa"ple(. $ )*sorption spectroscop "eas#res the a"o#nt of li+ht a*sor*ed * the sa"ple as a f#nction of ,a&elen+th.

Chapter 12

. pes of Spectroscop
$ Infrared (IR) spectroscopy "eas#res the *ond &i*ration fre%#encies in a "olec#le and is #sed to deter"ine the f#nctional +ro#p. $ Mass spectrometry (MS) fra+"ents the "olec#le and "eas#res their "ass. !S can +i&e the "olec#lar ,ei+ht of the co"po#nd and f#nctional +ro#ps. $ Nuclear magnetic resonance (NMR) spectroscop anal /es the en&iron"ent of the h dro+ens in a co"po#nd. .his +i&es #sef#l cl#es as to the al0 l and other f#nctional +ro#ps present. $ Ultraviolet (UV) spectroscopy #ses electronic transitions to deter"ine *ondin+ patterns.
Chapter 12 -

Wa&elen+th and 2re%#enc

$ .he fre%#enc of a ,a&e is the n#"*er of co"plete c cles that pass a fi3ed point in a second. $ Wa&elen+th is the distance *et,een an t,o pea0s 'or an t,o tro#+hs( of the ,a&e.
Chapter 12 1

Electro"a+netic Spectr#"
$ 2re%#enc and ,a&elen+th are in&ersel proportional. c 5

5 c6

,here c is the speed of li+ht '- 3 1010 c"6sec(. $ Ener+ of the photon is +i&en * E 5 h ,here h is Planc07s constant '8.82 3 109-7 0J$sec(.
Chapter 12 4

.he Electro"a+netic Spectr#"

Chapter 12

.he I: :e+ion
$ 2ro" ri+ht *elo, the &isi*le re+ion to ;#st a*o&e the hi+hest "icro,a&e and radar fre%#encies . $ Wa&elen+ths are #s#all 2.4 3 1091 to 24 3 1091 c". $ !ore co""on #nits are ,a&en#"*ers, or c"91, the reciprocal of the ,a&elen+th in centi"eters. $ Wa&en#"*ers are proportional to fre%#enc and ener+ .
Chapter 12 7

!olec#lar =i*rations

$ If the *ond is stretched, a restorin+ force p#lls the t,o ato"s to+ether to,ard their e%#ili*ri#" *ond len+th. $ If the *ond is co"pressed, the restorin+ force p#shes the t,o ato"s apart. $ If the *ond is stretched or co"pressed and then released, the ato"s &i*rate.
Chapter 12 <

Stretchin+ 2re%#encies

$ 2re%#enc decreases ,ith increasin+ ato"ic "ass. $ 2re%#enc increases ,ith increasin+ *ond ener+ .
Chapter 12 >

=i*rational !odes

$ ) nonlinear "olec#le ,ith n ato"s has -n 9 8 f#nda"ental &i*rational "odes. $ Water has -'-( 9 8 5 - "odes. .,o of these are stretchin+ "odes, and one is a *endin+ "ode 'scissorin+(.
Chapter 12 10

2in+erprint :e+ion of the Spectr#"

$ ?o t,o "olec#les ,ill +i&e e3actl the sa"e I: spectr#" 'e3cept enantio"ers(. $ 2in+erprint re+ion is *et,een 800@1100 c"91, and has the "ost co"ple3 &i*rations. $ .he re+ion *et,een 1800@-400 c"91 has the "ost co""on &i*rations and ,e can #se it to +et infor"ation a*o#t specific f#nctional +ro#ps in the "olec#le.
Chapter 12 11

Effect of an Electric 2ield on a Polar Aond

$ $

) *ond ,ith a dipole "o"ent 'as in H2, for e3a"ple( is either stretched or co"pressed * an electric field, dependin+ on the direction of the field. ?otice that the force on the positi&e char+e is in the direction of the electric field 'E( and the force on the ne+ati&e char+e is in the opposite direction.
Chapter 12 12

.he Infrared Spectro"eter

Chapter 12

1-

2.@I: Spectro"eter
$ Has *etter sensiti&it . $ Less ener+ is needed fro" so#rce. $ Co"pletes a scan in 1 to 2 seconds. $ .a0es se&eral scans and a&era+es the". $ Has a laser *ea" that 0eeps the instr#"ent acc#ratel cali*rated.
Chapter 12 11

Car*on9Car*on Aond Stretchin+

$ Stron+er *onds a*sor* at hi+her fre%#encies *eca#se the *ond is diffic#lt to stretchB
CCC C5C CC 1200 c"91 1880 c"91 D 2200 c"91 ',ea0 or a*sent if internal(

$ Con;#+ation lo,ers the fre%#enc B isolated C5C 1810918<0 c"91 con;#+ated C5C 182091810 c"91 aro"atic C5C appro3. 1800 c"91
Chapter 12 14

Car*on@H dro+en Stretchin+

$ $ $

) +reater percent of s character in the h *rid or*itals ,ill "a0e the CCH *ond stron+er. )n sp- h *ridi/ed car*on has a 24E s character, an sp2 has aro#nd --E s character, and an sp car*on has 40E s character. .he CCH *ond of an sp- car*on ,ill *e sli+htl ,ea0er than the CCH of an sp2 or an sp car*on.
Chapter 12 18

I: Spectr#" of )l0anes

$ )n al0ane ,ill sho, stretchin+ and *endin+ fre%#encies for CCH and CCC onl . $ .he CCH stretchin+ is a *road *and *et,een 2<00@-000 c"91, a *and present in &irt#all all or+anic co"po#nds. $ In this e3a"ple, the i"portance lies in ,hat is not seen, i.e., the lac0 of *ands indicates the presence of no other f#nctional +ro#p.
Chapter 12 17

I: Spectr#" of )l0enes

$ .he "ost i"portant a*sorptions in the 19he3ene are the CFC stretch at 1812 c"91, and the #nsat#rated stretch at -0<0 c"91. $ ?otice that the *ands of the al0ane are present in the al0ene.
Chapter 12 1<

I: Spectr#" of )l0 nes

Chapter 12

1>

GCH and ?CH Stretchin+

$ Aoth of these occ#r aro#nd --00 c" 91, *#t the loo0 differentB
)lcohol GCH is *road ,ith ro#nded tip. Secondar a"ine ':2?H( is *road ,ith one sharp spi0e. Pri"ar a"ine ':?H2( is *road ,ith t,o sharp spi0es. ?o si+nal for a tertiar a"ine ':-?( *eca#se there is no h dro+en.
Chapter 12 20

I: Spectr#" of )lcohols

$ .he I: spectr#" of alcohols ,ill sho, a *road, intense GCH stretchin+ a*sorption centered aro#nd --00 c"91. $ .he *road shape is d#e to the di&erse nat#re of the h dro+en *ondin+ interactions of alcohol "olec#les.
Chapter 12 21

I: Spectr#" of )"ines

$ .he I: spectr#" of a"ines sho, a *road ?CH stretchin+ a*sorption centered aro#nd --00 c" 91. $ Hiprop la"ine has onl one h dro+en so it ,ill ha&e onl one spi0e in its spectr#".
Chapter 12 22

Car*on l Stretchin+

$ .he CFG *ond of si"ple 0etones, aldeh des, and car*o3 lic acids a*sor* aro#nd 1710 c"91. $ Is#all the car*on l is the stron+est I: si+nal. $ Car*o3 lic acids ,ill ha&e GCH also. $ )ldeh des ha&e t,o CCH si+nals aro#nd 2700 and 2<00 c"91.
Chapter 12 2-

I: Spectr#" of Jetones

$ .he spectr#" of 29heptanone sho,s a stron+, sharp a*sorption at 171< c" 91 d#e to the CFG stretch.
Chapter 12 21

I: Spectr#" of )ldeh des

$ )ldeh des ha&e the CFG stretch at aro#nd 1710 c" 91. $ .he also ha&e t,o different stretch *ands for the aldeh de CCH *ond at 2720 and 2<20 c"91.
Chapter 12 24

GH Stretch of Car*o3 lic )cids

$ .his GCH a*sor*s *roadl , 2400@-400 c"91, d#e to stron+ h dro+en *ondin+. $ Aoth pea0s need to *e present to identif the co"po#nd as a car*o3 lic acid.
Chapter 12 28

=ariations in Car*on l )*sorption

Chapter 12

27

I: Spectr#" of )"ides

$ )"ides ,ill sho, a stron+ a*sorption for the CFG at 18-0@1880 c"91. $ If there are h dro+ens attached to the nitro+en of the a"ide, there ,ill ?CH a*sorptions at aro#nd --00 c"91.
Chapter 12 2<

Car*onC?itro+en Stretchin+
CC? CF? C ? 1200 c"91 1880 c"91 K 2200 c"91 D 2200 c"91 usually strong

2or co"parison, CC

Chapter 12

2>

I: Spectr#" of ?itriles

$ ) car*on nitro+en triple *ond has an intense and sharp a*sorption, centered at aro#nd 2200 to 2-00 c"91. $ ?itrile *onds are "ore polar than car*on@car*on triple *onds, so nitriles prod#ce stron+er a*sorptions than al0 nes.
Chapter 12

-0

S#""ar of I: )*sorptions

Chapter 12

-1

Chapter 12

-2

Sol&ed Pro*le" 1
Determine the functional group(s) in the compound whose IR spectrum appears here.

Chapter 12

--

Sol&ed Pro*le" 1 'Contin#ed(

Sol#tion
First, look at the spectrum and see what peaks (outside the fingerprint region) dont look like alkane peaks: a weak peak around 3400 cm-1, a strong peak about 1720 cm-1, and an unusual CH stretching region. The CH region has two additional peaks around 2720 and 2820 cm-1. The strong peak at 1725 cm1 must be a C=O and the peaks at 2720 and 2820 cm-1 suggest an aldehyde. The weak peak around 3400 cm-1 might be mistaken for an alcohol OH. From experience, we know alcohols give much stronger OH absorptions. This small peak might be from an impurity of water or from a small amount of the hydrate of the aldehyde (see Chapter 18). Many IR spectra show small, unexplained absorptions in the OH region.

Chapter 12

-1

Stren+ths and Li"itations

$ $ $ $ I: alone cannot deter"ine a str#ct#re. So"e si+nals "a *e a"*i+#o#s. .he f#nctional +ro#p is #s#all indicated. .he absence of a si+nal is definite proof that the f#nctional +ro#p is a*sent. $ Correspondence ,ith a 0no,n sa"ple7s I: spectr#" confir"s the identit of the co"po#nd.
Chapter 12 -4

!ass Spectro"etr
$ !olec#lar ,ei+ht can *e o*tained fro" a &er s"all sa"ple. $ ) *ea" of hi+h9ener+ electrons *rea0s the "olec#le apart. $ Hestr#cti&e techni%#e, the sa"ple cannot *e reco&ered. $ .he "asses of the fra+"ents and their relati&e a*#ndance re&eal infor"ation a*o#t the str#ct#re of the "olec#le.
Chapter 12 -8

:adical Cation 2or"ation

$ When a "olec#le loses one electron, it then has a positi&e char+e and one #npaired electron. .his ion is therefore called a radical cation.
Chapter 12 -7

Electron I"pact Ioni/ation

H H H C C H H H H H e9 + H C C H H H
H H CL H
H H H C CL H H H

H C H H

Gther fra+"ents can *e for"ed ,hen CCC or CCH *onds are *ro0en d#rin+ ioni/ation. Gnl the positi&e fra+"ents can *e detected in !S.
Chapter 12 -<

!ass Spectro"eter

Chapter 12

->

Separation of Ions
$ ) *ea" of electrons ca#ses "olec#les to ioni/e and fra+"ent. $ .he "i3t#re of ions is accelerated and passes thro#+h a "a+netic field, ,here the paths of li+hter ions are *ent "ore than those of hea&ier ato"s. $ A &ar in+ the "a+netic field, the spectro"eter plots the a*#ndance of ions of each "ass. $ .he e3act radi#s of c#r&at#re of an ionMs path depends on its "ass9to9char+e ratio, s "*oli/ed * m6z. In this e3pression, m is the "ass of the ion 'in a"#( and z is its char+e. $ .he &ast "a;orit of ions ha&e a L1 char+e, so ,e consider their path to *e c#r&ed * an a"o#nt that depends onl on their "ass.
Chapter 12 10

.he !ass Spectr#"

$ In the spectr#", the tallest pea0 is called the *ase pea0 and it is assi+ned an a*#ndance of 100E. .he E a*#ndance of all other pea0s are +i&en relati&e to the *ase pea0. $ .he "olec#lar ion '!L( corresponds to the "ass of the ori+inal "olec#le.
Chapter 12 11

Gas Chro"ato+raph @!ass Spectro"etr 'GC@!S(

$ .he +as chro"ato+raph col#"n separates the "i3t#re into its co"ponents. $ .he "ass spectro"eter scans "ass spectra of the co"ponents as the lea&e the col#"n.
Chapter 12 12

Hi+h :esol#tion !S
$ !asses "eas#red to 1 part in 20,000. $ ) "olec#le ,ith "ass of 11 co#ld *e C-H<, C2H1G, CG2, or C?2H1. $ Isin+ a "ass ,ith "ore si+nificant fi+#res ,o#ld help identif the correct for"#la. $ 2or e3a"ple, let7s sa the co"po#nd ,e are loo0in+ for has "ass of 11.02>, pic0 the correct str#ct#re fro" the ta*leB

Chapter 12

1-

!olec#les ,ith Heteroato"s

$ Isotopes are present in their #s#al a*#ndance. $ Car*on has a 1-C isotope present in 1.1E a*#ndance. .he spectr#" ,ill sho, the nor"al !L and s"all !L1 pea0. $ Aro"ine has t,o isotopesB 7>Ar '40.4E( and <1 Ar '1>.4E(. Since the a*#ndances are al"ost e%#al, there ,ill *e an !L pea0 and and !L2 pea0 of e%#al hei+ht.
Chapter 12 11

Isotopic )*#ndance

Chapter 12

14

!ass Spectr#" ,ith Aro"ine

$ Aro"ine is a "i3t#re of 40.4E 7>Ar and 1>.4E <1 Ar. .he "olec#lar ion pea0 !L has 7>Ar *e as tall as the !L2 pea0 that has <1Ar.
Chapter 12 18

!ass Spectr#" ,ith Chlorine

$ Chlorine is a "i3t#re of 74.4E -4Cl and 21.4E -7 Cl. .he "olec#lar ion pea0 !L is - ti"es hi+her than the !L2 pea0.
Chapter 12 17

!ass Spectr#" ,ith S#lf#r

$ S#lf#r has three isotopesB -2S '>4E(, --S '0.<E(, and -1 S '1.2E(. $ .he !L pea0 of eth l "eth l s#lfide has an !L2 pea0 that is lar+er than #s#al 'a*o#t 1E of !L(.
Chapter 12 1<

2ra+"entation of the He3ane :adical Cation

Chapter 12

1>

!ass Spectr#" of n9He3ane

$ Gro#ps of ions correspond to loss of one9, t,o9, three9, and fo#r9car*on fra+"ents.
Chapter 12 40

2ra+"entation of Aranched )l0anes

$ .he "ost sta*le car*ocation fra+"ents for" in +reater a"o#nts.

Chapter 12 41

!ass Spectra of )l0anes

Chapter 12

42

!ass Spectra of )l0enes

:esonance9sta*ili/ed cations fa&ored.

Chapter 12

4-

!ass Spectra of )lcohols

Chapter 12

41