Nuclear Magnetic Resonance

(NMR) Spectroscopy

Proses Resonansi
Atom: inti dan elektron
Inti mempunyai bil. spin, momen spin
Bil. Spin I= 0, , 1,1 ,2,
I=0 bila proton dan netron ganjil
Inti 1H and 13C, I: +1/2 dan -1/2
Spinning charge, spinning nucleus has a
magnetic moment that coincides with
the axis of rotation.
Under normal circumstances the two
spin states are energetically
equivalent.
Spinning nuclei precesses along axis of
spin in concert with the orientation
with the magnetic field.
refers to angular frequency of
nuclear precession.

Applied
Magnetic
Field

Precessional motion of a
spinning nucleus

Notallelements/isotopesareNMRactive.
Nucleiwithevenmassnumberandevenatomicnumberhave
nuclearspinquantumnumber(I=0)ofzero

Oddmassnumberandeven/oddatomicnumberhave
I=1/2
Evenmassnumberbutoddatomicnumberhaveintegervalues
I=1,2,3,etc
OnlynucleiwithnonzeronuclearspingiveNMRspectra
13C vs. 12C

The natural abundance of 13C is approximately 1%

The natural abundance of 12C is approximately 99%

E'2
E2
E
E1

E'
E'1

H0

H'0

-1/2

Applied
Magnetic
Field

h
+1/2

H0

Keadaan normal (tdk ada medan

magnet) spin inti mempunyai energi yg
sama.
Dlm medan magnet, terjadi dua orientasi
energi
Perbedaan energi tergantung pada
medan magnet yg digunakan
H0 14100 gauss E= 60MHz
H0 23500 gauss E= 100MHz
Pada keafaan ini bila energi dr luar
diberikan spin inti dapat flip. Ini
proses Resonansi
Energi luar (gel radio) harus sama
dengan perbedaan energi yg dibutuhkan.

PeralatanCWNMR

FrequensiVsMedanmagnet
Protonmempunyaifrequensitertentupada
keadaanresonansi
Faktoryangmempengaruhiadalahfaktor
lindungan(shielding)elektronyang
menyelimutiinti
Lindunganditentukanolehinduksidan
momenmagnetyangdisebabkanolehawan
elektron

Chemical Shift
Nuclear Shielding

Nucleiareshieldedby
electrons.
Inducedfieldassociatedwith
orbitingelectrons.
Requirestrongermagneticfield
thanH0.
Increasedshieldingrequires
greaterappliedfieldstrengthto
achieveresonance.

ChemicalShift(,ppm)=

Amoleculemaycontainmultiple
protonsthatexistinunique
electronicenvironments.
Thereforenotallprotonsare
shieldedtothesameextent.
Resonancedifferencesinprotons
areverysmall(ppm).
Measuredifferencesinresonance
energyrelativetoareference.
Tetramethylsilane (CH3)4Si
(TMS) provides highly shielded
reference (set to 0ppm).

ObservedchemicalshiftfromTMS(Hz)
Sptectrometerfrequencey(MHz)

=ppm

NMR Spectra
Representativepeak,
3equivalentprotons

TMS
H
C H
H

12

11 10

0 ,ppm

Increasingmagneticfieldstrength
Increasedsheildingofnuclei
TMSasreference
issetto0ppm

HypotheticalNMRspectra.
ShowsTMSreference.
Chemicalshifts(,ppm)givenrelativetoTMS

Chemically Equivalent
Protonsinthesame
environmentwillhavethe
samechemicalshift.
Protonsindifferent
environmentshave
differentchemicalshifts.
Protonswiththesame
chemicalshiftarereferred
toaschemically
equivalent.
Integratedareaofpeakis
proportionaltothenumber
ofprotons.

H
H

H
H
H

H
H

H
H

Sample Spectra
Thefirstspectraisthat
ofasymmetric
molecule,allprotonsare
equivalent.
Secondspectraisthatof
amoleculecontaining
twotypesofprotons.
Correlationchartfor
protonchemicalshift
hasbeenstudied.

H
H

TMS

12

11 10

C H
H

11 10

TMS

0 ,ppm

12

0 ,ppm

SampleCarbonSpectrum:4methyl2pentanone
chemicalshift=30ppm
chemicalshift=53ppm

CH3

chemicalshift=23ppm

CH3CHCH2CCH3
chemicalshift=25ppm
chemicalshift=209ppm

Shielding:MagneticFields
1. ExternalMagneticField(B0)
2. InducedMagneticFieldCausedbyCirculatingElectrons

Proton Chemical Shifts of Methyl Derivatives

Compound

(CH3)4C

(CH3)3N

(CH3)2O

CH3F

0.9

2.1

3.2

4.1

Compound

(CH3)4Si

(CH3)3P

(CH3)2S

CH3Cl

0.0

0.9

2.1

3.0

Proton Chemical Shifts (ppm)

Cpd./Sub.

X=Cl

X=Br

X=I

X=OR

X=SR

CH3X

3.0

2.7

2.1

3.1

2.1

CH2X2

5.3

5.0

3.9

4.4

3.7

CHX3

7.3

6.8

4.9

5.0

TabelpergeseranKimia

Nuclear Shielding/Deshielding
Valenceelectrondensity
canshieldnucleusfrom
appliedfield.
(ppm)
Electronegative
substituentscandraw
elecrondensityaway.
Resultsindeshielding.
Anisotropy:electrons
andinducedmagnetic
field.
Resultsinshieldingand
deshieldingzones.

CH3F
4,3

CH2Cl2

CH3Cl
3,1

5,4

CH3OCH3

CH3CH3

3,2

0,9

H0

Spektra1HNMR
SpektraCH3CH2OHbilatidakterjadi
spliting
OHCH2CH3

SpektraC2H6O(terjadipemecahan)

Spin-spin Splitting and n+1 Rule

Each type of proton senses

protons on adjacent carbon atoms.
Spin state of nearby protons
contributes to the proton
evironment and apparent magnetic
field.
General rule is that the signal is
split into n+1 peaks. n = number of
equivalent neighboring protons.

n = 0, singlet

Splitting

+1/2

-1/2

+1

n = 1, doublet

Spacing between component

peaks referred to as coupling
constant (J).
J coupling is representative of the
degree to which protons interact.
J usually 0-18Hz

-1

n = 2, triplet

-1 1/2

+1 1/2
+1/2

Numbers in Italics refer to net spin

-1/2

n = 3, quartet

Two types of protons in 1,1,2-trichloroethane

Cl

Ha

Hb

Cl

Hb

Cl

Cl

Ha

Hb

Cl

Cl

Hb

equivalent
protons behave
as a group

n = 0, singlet

Splitting

+1/2

-1/2

n = 1, doublet

+1

n = 2, triplet

Numbers in Italics refer to net spin

-1
-1 1/2

+1 1/2
+1/2

-1/2

n = 3, quartet

Multiplicity
singlet
Doublet
Triplet
Quartet

Quintet

struktur

struktur

1,1,2trichloroethane
Hb
J

Cl

Ha

Hb

Cl

Hb

Cl
TMS

Ha
JJ

0 ,ppm

NMR spectrum for 1,1,2-trichloroethane

Hb proton signal split into doublet
Ha proton signal split into triplet
J couplings are the same for Ha and Hb signals
Ha integral is 1/2 that of Hb

CouplingconstantJ

MagnitudeofSomeTypicalCouplingConstants
<

Magnetic Equivalence vs.

Chemical Equivalence
NMRdifferentiates
betweennucleibasedon
environment.
Inconstrainedsystems,
twoprotonsonthesame
Catomcanbeindifferent
environments.
Theseprotonscan
demonstratespinspin
splitting.
Geminalcoupling
Jgeminal~5Hz

Br
Ha

Br
H3C

Hb

H3C

Ha

Hc

Hb

Diagram Karplus

IkatanHidrogen

R-O-H + D2O

R-O-D + D-O-H

Higher Field Strengths

Athigherfieldstrengths
differencesinenergy
betweenspinstatesis
increases.
Improvedsignal
resolution.
Couplingconstantsare
independentoffield
strength.

TMS

60 MHz

0 ,ppm

60 MHz

TMS

100 MHz

Chemical Shift (, ppm) =

100 MHz

0 ,ppm

Observed chemical shift from TMS (Hz)

Sptectrometer frequencey (MHz)

= ppm

ChemicalshiftReagent

Pereaksi Pergeseran kimia

Integrasi

TentukanStruktursenyawadarispektraNMRprotonberikut:

C10H14O

Tentukanstrukturdaridataberikut:

RumusmolekulC3H8O

RumusmolekulC6H12

RumusMolekulC5H10O

Carbon-13 NMR

~1.08%ofCatomsarethe13Cisotope.
DonotusuallyseeCCspinspininteractions.
CanseecouplingbetweenCandattachedHs.
Magneticmomentof13Cislow.
Resonancesof13Cnucleiare~6000foldweakerthan1H
resonances.
Thereforemostusefulinformationischemicalshift.
Coversarangeof0200ppm.
Influencechemicalshiftinprotonspectraalsoinfluence
incarbonspectra

SpektraNMRCarbon4bromoacetofenon

Pergeseran kimia atom Karbon

Perbedaan atom karbon dalam 13C NMR

Proton Decoupled
Protoncouplingcan
provideinformation
aboutnumberofprotons.
Oftenusefultodecouple
protons.
Irradiatesamplewith
broadspectrumof
frequencies.
SubstituentsonCcan
enhanceofreducesignal.
Protonsenhancethe13C
signal.

O
H2C

Undecoupled

H2
C

CH3

Decoupled from protons

2,6

TMS

3,5
1

6
5

180

O
H2
C C

2
3

O CH2

CH3

160

140

120

100

80

60

40

20

0 ,ppm

Rumus Molekul C5H7O2N

RumusMolekulC6H8O

RumusMolekulC8H8O