roLon nM8 SpecLroscopy: Pow Lo ldenLlfy roLon Lqulvalence

!"#$% '(%")*+",-.
!"#$%&'()* ,-.*.)/0 proLons LhaL are $/012$%"+ ln every way. 1hey have Lhe same magneLlc
envlronmenL, whlch glves Lhem Lhe same spln fllp energy.
1.)("#$%&'()* ,-.*.)/0 proLons LhaL only have Lo dlffer ln a #$13+0 way. 1hese proLons do noL
have Lhe same magneLlc envlronmenL.

45- /( 60 100/ 2( $/012$7- 8,(2(1 09*$:"+01%0 $1 250 7$,#2 8+"%0;
23( )#45(- .6 /$7)&'/ 6.#)8 $) *3( 19: /;(<*-#4 <.--(/;.)8/ *. *3( )#45(- .6 ).)("#$%&'()*
;-.*.) 7-.#;/ $) *3( 4.'(<#'(. knowlng how Lo ldenLlfy proLon equlvalence wlll allow you Lo ldenLlfy
nonequlvalenL proLon groups and ldenLlfy Lhe number of slgnals LhaL wlll show up ln Lhe nM8 specLrum
for Lhe molecule!









Pow Lo deLermlne Lqulvalence:
1here are a few dlfferenL ways of deLermlnlng equlvalence LhaL ofLen need Lo be used LogeLher!

1. ldenLlfy a 4$--.- ;'&)( ln Lhe molecule. lf Lhere ls symmeLry along Lhe mlrror plane Lhen Lhe
proLons are equlvalenL!












2. ldenLlfy an axls of roLaLlon. lf Lhe molecule looks Lhe same upon roLaLlon, Lhen Lhe proLons are
equlvalenL!

Spln lllp Lnergy (hoLon Lnergy)
lnLe
nslLy
of
slgn
al
(ho
Lon
Cual
lLy)
= nM8 Slgnals = = dlfferenL
(nonequlvalenL) proLon seLs
PC C C CP
P
P P
P
1he green proLons and Lhe
red proLons are
symmeLrlcal along Lhe
mlrror plane

Molecular Model Cf:






3. LasLly, you can ldenLlfy whaL aLoms Lhe proLons are connecLed Lo and compare Lhem. lf Lhe
aLom LhaL Lhe proLons are dlrecLly connecLed are Lhe same move on Lo ldenLlfy Lhe addlLlonal
bonded Lo assure Lhere ls no dlfference! lf Lhey dlffer by even one oLher aLom, Lhen Lhey are
nonequlvalenL!

Pere, we already know Lhe hydrogens of Lhe meLhyl group are equlvalenL Lo each oLher, and Lhe
hydrogens of Lhe meLhylene group are equlvalenL Lo each oLher because of symmeLry. Are all Lhe
hydrogens n Lhe molecule equlvalenL Lo each oLher?






8oLaLe
120
8oLaLe
120
Lven Lhough Lhe proLons of Lhe meLhyl
are roLaLlng around Lhe carbon (Lhe
yellow, orange, and plnk Labs help keep
Lrack of Lhe placemenL!), Lhe roLaLlons 8.
).* change Lhe molecule lLself. 23(/(
*3-(( ;-.*.)/ &-( ("#$%&'()*>

P P
P P
CP
Pydrogens of meLhyl
group are dlrecLly
bonded Lo a carbon.
Pydrogens ln
meLhylene are dlrecLly
bonded Lo a carbon.
Pydrogen of Lhe
alcohol ls dlrecLly
bonded Lo oxygen.
1he carbon ls aLLached Lo
oxygen and a carbon.
Carbon ls aLLached Lo
a carbon.
1hree non-equlvalenL
groups= 3 slgnals on Lhe
nM8 specLrum

ln general, hydrogens aLLached wlLh
a slngle bond Lo Lhe same aLom ln an
acycllc molecule are equlvalenL.

!We can lmmedlaLely see LhaL Lhe hydrogen of Lhe alcohol ls 1(1<09*$:"+012 Lo Lhe resL because lL ls
dlrecLly aLLached Lo oxygen whlle Lhe oLher hydrogens are aLLached Lo carbon.

!Slnce Lhe hydrogens of Lhe meLhyl and meLhylene group are boLh aLLached Lo a carbon, we need Lo
look aL Lhe aLoms each carbon ls bonded Lo ln order Lo correcLly ldenLlfy lf Lhey are equlvalenL. 1he
carbon of Lhe meLhyl group ls only aLLached Lo a carbon, buL Lhe carbon of Lhe meLhylene group ls
aLLached Lo a carbon &)8 oxygen. 8ecause Lhey dlffer by Lhe addlLlon of an oxygen aLom, Lhey are 1(1<
09*$:"+012=

Lxample roblems:
ueLermlne Lhe number of slgnals LhaL wlll be found on Lhe nM8 SpecLrum for each molecule.

1.


1he proLons of each meLhyl group are equlvalenL Lo each oLher because of Lhe axls of roLaLlon. 1he
proLons of meLhylene group are equlvalenL because of Lhelr symmeLry. Powever, Lhe meLhyl proLons
and Lhe meLhylene proLons are non-equlvalenL Lo each oLher because Lhe aLoms Lhey are aLLached Lo
are noL ldenLlcal. 1he meLhyl proLons are aLLached Lo a carbon, whlch ls aLLached Lo a carbon wlLh Lhree
addlLlonal carbon bonds. 1he meLhylene proLons are aLLached Lo a carbon LhaL ls aLLached Lo one oLher
carbon and a fluorlne.
?.)<'#/$.)0 2 groups of non-equlvalenL proLons=2 slgnals on Lhe nM8 SpecLrum.

2.


All hydrogens aLLached Lo a benzene rlng are equlvalenL. 1here are Lhree mlrror planes ln Lhls
molecule, and all Lhe hydrogens are symmeLrlcal along each one!
**uon'L leL Lhe alLernaLlng double bonds mess you up. Slnce a benzene rlng ls ln resonance, all
Lhe bonds have parLlal pl bond characLer, and are Lherefore equal!
P
P
CP
3
CP
3
CP
3
l
?.)<'#/$.)0 All hydrogens are equlvalenL= 1 slgnal on Lhe nM8 SpecLrum

3.


1he addlLlon of Lhe fluorlne and chlorlne subsLlLuenLs Lo Lhe chlorlne rlngs desLroys Lhe
symmeLry and ldenLlcal aLom aLLachmenL Lhe molecule had before.
**?ou may be LempLed Lo say LhaL Lhe Lop and boLLom hydrogens are symmeLrlcal and
Lherefore equlvalenL. Powever, lf you look aL Lhe aLoms each hydrogen ls bonded Lo lL ls
apparenL LhaL Lhey are noL ldenLlcal. 1he Lop hydrogen ls bonded Lo a carbon, whlch ls bonded
Lo a carbon wlLh a fluorlne subsLlLuenL. 1he boLLom hydrogen ls bonded Lo a carbon, whlch ls
bonded Lo a carbon wlLh a chlorlne subsLlLuenL. 1he Lwo dlfferenL halogens make Lhe hydrogens
non-equlvalenL.
?.)<'#/$.)0 4 nonequlvalenL hydrogens=4 slgnals on Lhe nM8 SpecLrum


Works ClLed
lmage of benzene rlng from: hLLp://www.davlddarllng.lnfo/encyclopedla/8/benzene.hLml
All oLher lnformaLlon from 1hlnkbook, pages 133-139, and he correspondlng lecLure.
F
Cl