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I.I,\[PORTANT

NM
bonus

roRvIAL to submit whonoed labgroups F,or

quest!ellg*tgg

to thet:l*gul answe$ include BFBORTplease

IR SpectroscoPY: be used fot utt tinOt pf *!t"t$ffi l. Can IR spectxoscopy

*l

tffilTJff$*ose

in about2 factorsthat can.orrt lbut" to the shielding 2. Discuss

spectroscopv? NMR during fietd amagnetic ofapplying !H-NMR'

5o/c arey/qh13/ffi . ca/cour$_es/3

Info source:httP:l/www,chem'uqal

nfra-Red
r .

ectrosco

of infraredradiation' by absorption the excitationof bond vibrationswithin that molecule Involves md hendingmodes' stretching include Vibrations regions: into two approxlryrate split anIR spechum Usually

from the/rnctional group is obtained that is ur"d to interpretanIR spectrum o Mostof theinformation groups' thefunctionhl represent polarcovalentbonds these molecules ;;i";:iofuanic region, peak..Thetingerprinf every to W t! assign o When anIR spectumawid the temptation analysing specta. aknown with by directcomparison to confirma structwe ci" Ui usefulior-helping however,

>

&okg,s,'LaW
h

G I
--I-

ff
---rr-

mrte
p mr+tQ

f'trtqufnoy

F! m{uarc mtrr

bondto the a vibrating To helpunderstand IR, it is usefulto compare physical canbe spring Thespring system modelof a vibrating system. described given byHooke's Law,asshown in theequation ontheleft. Consider a bond and the connected atomsto be a springwith two masses attached. Using the force constant k (whichreflectsthe stiffrress of the spring) and the twd masses m1 andm2, thenthe equation indicates how the frequency, u, of theabsorption should change astheproperties of the system change.

Consider thefollowingtrends : 1. Fora sbonger bond(larger k value), u increases. Asexamples of this, in orderof increasing bondstrengthcompare: CC bonds: C-C(1000 cm'r), p=C (1600 crn-r; ani'C=C IiZOO cm.r), cn bonds: c-c-H (2900 c0',), c:c-H (:too cm-';andd=c_H cm-r) cg30o

Page L of 4

2. For heavier atoms.attached (larger

u clecreases. Asexampres of this,in orcrer oiiiiunrir{r"rroruiiiirrcomparc: C-H(3000 cm-r) C-C(1000 cm-r)

k value),

C-Ct(S00 cm-r)

fihcuftelre

{qt

i:h

-r

;o

tthlD brnls og.ClC clN

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Iimlro rtil w aDsorpuons ti

Bond

Base Vdtue

I C=O 2 o-H 3 N.H 4 c-o

5 C=C 6 C=C 7 C-TI

t7t5
3600 3500 I 100
I 650 2t50

s, t'finger" s, "broadt'

Strength/ Shape

Comments

m
S

Exactpg.siti_onjepends on typeof carbonyl Hroaddge-toH bond!-ng Also checkfor OH andC:O

Allcene weak due to low polarity Aromatic usually in pairs

w (alkene) nl-s (aromatic) w, sharp

S

3000 2250

8 C=N

m, sharp

abbrgviations ' ffs' = strong, ttnrtt= medium and tt*ir : "'^^;

As hybridisation ofC@ increases Characteristic sincelittle elsearound it

Nuclear Ma
o o

tic Reasonance

ectrosco

Involvesa nuclei in a magneticfield which obsorb andre-emitelectrcmagnetic (EM) energy. Requires stableisotopes that containan ocldnumber of protonsand/orof neutrons with intrinsic magnetic moment andangular (i.e.non-zero momentum spin). oEMradiatiottisrrsedto,|tlip],thealignmentofnuclearspinsfrornthelowenergysP,tl9!i% q'in oppssed . - .. tlu.Jtlgher-enp+gt stet r* - -- - - "
2 of 4 Page

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to the radiofrequency qN etl'v.a\ wt. smatfwrdiorresponds and thereforeso doesthe of the spin states, of-e:rergies field increas* Gyn*utiqn stonger magnetic

-&ss 'etd'Itisusuallv tup-tutasonfrlstren^4lt{^T::fr {A*"etiefr spectrum' EM the of tange

the spin-flip' to cause requiied nequJncy will beabsorbed spinstates thenuclear between difference to the energy equivalent only EM energy
thus the term "Feasonance".

Ipterp,retting .IH'NMR SI ectrq

IIow manytypesof H ? What typesof H ?

therearein thespecha of signals by howmanygroups Indicated group shift (6)ot each by thechemical Indicated by the integration(relativearea)of the signalfor each Indicate<i Look at the couplingpatterns.This tells you what is nextto each group

To*

manyH of eachtYPeare there? group. i -

? What is the connectivitY

Chemlcalshift o The chemical shift is the fosition on the 6 scale(in ppm) wherethe peakoccurs' atoms of H atomby neighbouring r lnfluencebyshielding/deshielding -OH .NH

CHz-[r cHfH cH2-N RCOfI RCHO Sr-H C=C.H cH2-o

cHfs
:-H

CH, CH,

CHrC=O CH CHzC=C

by a singlegroup,In being influenced Note: that the figure showsthe typical chemicals hiftsfor protons cases whEtg-a ro
aa

Integration
3 of 4 Page

c o

Tlteareaof o peak isproportion al to thenwnbe, of E tbatthepeakrepresenrs Theintegralmeasures theareaof thepeakand giuo trr. rehtivi rotioif thenumber of

H for eachpeak

Coupling

e.sbessfpns,.sssssgthe-nsrelxg-b ##ffi:T.!t- "o!-pJ!9t:i!:-g.sletu-ep.!elslbessrs"

Also knownas signal multiplicity or splitting.

--.- 4le*pls

fntegration

0 ppm Based on theoutlinegiven abovethe fbur setsof informationwe get are: ' r J basic tlpesof H present in theratioof 5 :2 : 2 :2 :3. o A 5H "sinllet" (ArH), two 2H triplets,a 2H quartetanda 3H triplet. o Eachtriplet indicates thereare 2H in the acljacent position. quartet A indicates therqare3H adjacent. 1 (Thinkof it asthelines you see,L = n i l, wheren numberof equivalent adjacent H) I s9 thepeaks at 4.4 and2.8 ppm must be connected asa cHzcHz unit.

Usingthechemical shift chails,the H canbe assigned to the peaksasbelow: 7,Zppm(5H)= ArfI; 4.4ppm (2H): CH1O; 2.8ppm (2I{): Ar-CH2; zJpprn (2H) : O=CCHzCH3 and 0.9ppm (3H): CIIzCHT

4 of 4 Page

acefyl'sali,cYlate

22

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t

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Acid
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1H NMR
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f-

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C u r r e n t D a ta Pa r a m e te r s N AI,{E Sa l i cyl i c Aci d EXPN O 44 PROCNO 2 F2 Acq u i si ti o n Pa r a m e te r s D a te 2005082 4 Ti m e 11- 33 IN STR U M sp e ct PROBHD 5 mm PABBO BBPU L PR OG zg 3 0 TD 65536 SOL VEN T C D C I3 N S1 D SO St{H 6 1 72 .8 3 9 H z FID R ES 0 .0 9 4 1 9 0 H z AQ 5 .3 0 8 4 6 6 4 se c RG 256 DW 8 1 .0 0 0 u se c DE 6 .0 0 u se c TE 2 9 6 .5 K Dl 1 .0 0 0 0 0 0 0 0 se c TD O 1

:=:=,====C H AN N ELf1
NUC 1 P1 PL l S FOl

=:====:: 1H 8 .5 0 u se c - 3 .0 0 d B 3 0 0 .1 "3 1 8 5 3 4 M H z p a r a m e te r s 327 68 300. 1300000 MHz no 0 0 .0 0 H z 0 i .0 0

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CBE, 2ndyear Synthesis and chara ctertzation of aspirin

roH

\,OH
l _^,!

Thereaction:
$aficyllc asid

qi9,*l.9 ?tlLYqrl$P >,

p\fo*r'$Hu

V8
scid acetylsalricyli,c

Figure1:NMR of salicylic Spectra acid,aspirinanda student representative ' product

Figure2: FTIR of salicylic Spectra acidandaspirin

AcH $nlir-trtlic.

{iS

SrS $nS n"S

f,,$

1'"S

t"il

I {1oscrn-1 Ene'rgy I
References: Journal of ChemicalEducation. 144,Vol. 80 No. 2 October2003 ' Education.1261,Vol.75 No. 10 October1998' Journalof Chemical

#,
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122

Nuclear Magrletic ResonanceSpectroscopy

Part One: Basic Concepts

T A B LE 3.4
APPROXIMATE CHEMICAT SHIFTRANCES (PPM) FORSETECTED TYPES OF PROTONSA

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0.7- L.3 1.2 - 1.4 1.4 - 7.7

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if tnut r,ydrogen is part of a mcthyl group (CH.r) the shift is generaily at rhe low end of the range given, if the hydrogen is in d methylene group (-CH2- ) the shift is inrcrmediate, and if the hydrogen is in a methine group (-gJ-), the shift is typically at the high end of the rangegiven. b Tie chemical shift of thesc groups is yariable. dependingnot onty orr the chemical environment in the molecule. but also on concentration, tenrperature,and .solvent.
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