netic waves in In infra-red spectroscopy a sample being analysed is irradiated with eleetrom the infra-red 1 sion of the electromagnetic specttum. The machine used is called a wths of infra-red radiation that spectiophotometer. and it detects the intensity of the wavel passes through the sample Ihis analytical technique is particularly useful for organic chemists hecause all organic molecules absorb radiation in the in! ed range of wavelengths. The en corresponds to changes in the vibration of the bonds between atoms. The bonds ean vibrate by stretching. bending and twisting. They have a natural frequency at which they vibrate, If ‘gy absorbed we irradiate the molecules with energy that corresponds to this frequency, it stimulates larger Vibrations and energy is absorbed. This is called the resonance frequency of that vibration Each type of vibration will absorb characteristic wavelengths of infra-red radiation. We cannot be too specific when quoting the characteristic absorption frequency of a bond — the nature of the rest of the molecule shilts the energy absorbed in each particular molecule However, we can say. for example. that the amine group. {-NH;) absorbs in the range 3300 to 3500 cm’. Therefore we can identify the presence (or absence) of different functional groups from the absorbance pattern on an infra-red spectrum Look at the infra-red spectrum of ethylamine in Figure 18.7 7 i Ny Aorbece 8. 8 i No re ‘on sw wo Be aw 800 To SO Waverumbie dm! Figure 18.7 The infra-red spectrum of ethylamine, CHsCH2NHp. Note that the percentage absorbance and the wavenumbers on the axes both get smaller in magnitude along each axis. We can use the characteristic infra-red spectrum of an unknown compound to identify it by ‘fingerprinting’ from a database of known spectra. Some characteristic absorption ranges and appearances of the speaks are shown in Table 18.3. [Parvez Sir] (IR Notes & P-2] [Chemistry , Legends] Scanned with CamScannerC—O alco ethare, 1940-1300 esters C=O aromate 1500-1680, wunless compounds, | conjugated alkenes \ C=0 amides 1640-1690 s ketones and aldehydes 1670-1740 8 esters 1715-1750 5 C=O | alkynes 2150-2250 w unless “iti 2200-2250 | nittiles stkanes.CH,—H | 2850-2950 alkenesiarenes, | 3000-3100 ol NCH amines, amides _ | 3300-3500 wv baced _ O—H | carboxylic acids, | 2500-3000 sand very broad | RCO,—-H | | Webonded alcohol, , 3200-3600 is | RO—H \ 7 % free alcohol, | 3580-3650 | sand sharp i RO—H : : Table 18.3 Some characteristic infra-red absorbance bands and their intensities. These values will usually be given to you. You can see that absorption bands overlap considerably. That is why we need to use a variety of techniques, such as NMR, infra-red spectroscopy and mass spectrometry, to work out the structure of a new organic compound. As well as their wavenumber bands, particular absorbance have characteristic widths (broad or sharp peaks) and intensities (strong or weak) on the infra-red spectrum. For example, the presence of hydrogen bonding makes the absorbance of the O ~ H bonds in alcohols and carbonyl groups has a strong, broad absorbance peak. Look at the infra-red spectra of ethanol, ethanoic acid and ethyle ethanoate shown in Figures 18.8 to 8.10. using the data in Table 18.3, note the broad bands in figures 18.8 and 18.9 arising from the O-H groups involved in hydrogen bonding in the alcohol and in the carboxylic acid. Contrast the width of these peaks with the sharp peak of the carbonyl group in the ester. ethyl ethanoate in Figure 18.10. [Parvez Sir] [IR Notes & P-2} [Chemistry , Legends] Scanned with CamScannerreo} "asoo 3300 3008 28003000500 Figure 18.10 The infra-red spectrum oF ethyl ethanoate, CHsCOOCH3CH. Example: oe atthe two infared spectra below: 6 ry im ce ) wearer! \eentefom! = a. Which one of the infra-red spectra is that of butanone and which one is of butan-2-ol? b. Explain your reasoning in part a. vatkine. v ~e [Parvez Sir} (IR Notes & P-2] {Chemistry , Legends} Scanned with CamScannerUse data from the table below of characteristic infra-red absorptions in organic molecules to the fallowing question. the answet 1090-1360 algenytics. Sector ree 1680-1750, hygragen bonded 2500-2300 tbroai pamary amines 7100-3300 * hycrogen bonded in alcoho!s. phenols 3550 35501-3670 fee One of the three spectra labeled A to C below is produced when ethanol is analysed in in infra-red spectrophozometer: : 5 ve ft inf vl wey TE peepee er 4000 300020091500 1000500 Wevenumber cm" Absorbance! % 2 | one YW | 4909 ea 1500 1000” 50D. Waverumber em’! Absorbance 2000 Siavenumber! 3008 Which infra-red spectrum is most likely to be produce by ethanol? Give three reasons for our choice. your choice od buko 7 me ¢ 44 vote 4 -¢-¢-0-H yt HOH [Parvez Sir] {IR Notes & P-2] [Chemistry , Legends] Scanned with CamScannerQl 5 Arwaction sequence is shown . reaction 4 tion 2 Hc—cH,—Br SE cco — on aon? bromosthane propanenitile reaction reaction propanoie acid 4 5 H,C—CH,—OH —H,C=CH, UALH, | reaction 3 ethanol ethene hi {a} Complete the diagram to show the mechanism of reaction 1. Include all necessary charges, partial charges, lone pairs and curly arrows. HC—C—Br ——* Hc—c—cn + 4 H “CN ry (b) ()) Give the name of the type of reaction involved in reaction 3, se cosmic {MY ‘The infra-red spectrum of the propancic acid produced by reaction 2 is shown, 100: transmittance Qn, CH? wavenumber/em-" (il) Deseribe and explain the main difference between the infra-red spectrum of W and that propanoie acid. Aip..W2...290.. Peak. “no Her.CO..qnoup. z - 2) [Parvez Sir} (IR Notes & P-2} [Chemistry , Legends] Scanned with CamScannerQ2. a gre ee BO (d) Hand | are isomers with molecular formula C-H,0,. The infra. pram ea spectra of isomers H and | percentage | transmittance 50 on Bos 8 g he catz-0-0-H ve yor wd © ~ 52 R 7 4000 3000 2000 1500 1000 wavenumber/cm7 CyHten 02 ' 100 percentage transmittance 0 \t 0 < 4000 ‘3000 2000 1800 4000 wavenumber/om io \dentify the bonds responsible for the principal peaks above 1500cm™” in each spectrum O=H. (ii), Name H and |, H non PROC COMA nae Methyl mothonoade...... a [Parvez Sir] [IR Notes & P-2] {Chemistry Legend] ee ee Scanned with CamScannera3, 2B Cora) ah 4118 a branched-chain aoa, G4\.0 is hated unr enflve wth an oxcoas of C0 ne turie reaction oecuisAn SABE compound K ls formed in good Yt Qc o~ The inra-res spettium 9! ie shawn, 1007 transmittance 50) 4000 ‘3000 2000 1800 1000 500 wavenumberlenr” ‘What are the structures of the branched-chain alcohol J and compound K? Cis. 22" aacctol Kuster CHCHICHICH.CHON | CH.CHICHCH:CHO B | CHICHCHIOHICH.CH, CHICH;COCH.CH, CHICHICHICHOHICH, | — CH,CHICHSICOCH, CH.CHICHICH.CH.OK | CH CH(CH,ICH,COoH. as. The infra-ted spectrum of compound Lis shown, pe sro 100 transmitance ‘ % 50: o4 4000 3000 2000 11800 000 500 wavenumber/em! What could be the stucture of ‘A HOCH,COCH,OH B_ HOCH.CHIOHICHO ©rocrscHromerson 1D HOCH,CH.COOH [Parver Sir] [IR Notes & P-2) [Chemistry , Legends} Scanned with CamScanner14 cu I= lene pair on of CR ANDeurly omow fomlene par to of C—Br 2 = correct disco on C—Br curly sow rom C—Br bond to Br AND Br o i ma redcian [om a esappoaronce a peak asp /¥ough absorption at 1680-1730 oato this of C=0 oR peak 91 5200-3650 ue to (aeoholy O—H ileematont 1 o n a a oa ‘Sodumpotsssiun hyerone aquzous 1 ti) ea [Parvez Sir] [IR Notes & P-2] [Chemistry , Legends] —— Scanned with CamScannerQs. Compound X contains three carbon atoms. Part of a simplified infra-red spectrum of eer x is shown, 300 $$ $$. y transmittance 50 0. 4000 2000 100 1000 500 wavenumber/cm* Which compound could be x? A CHCH,CHO B CH;CH,COM CH.CH:CH.OH D CHsCO.CH.« Qs The infra-red spectrum of an organic compound is shown, 100: transmittance * 80 4000 2000 1500 1000 500 ‘wavenumberlem* Which compound could give this spectrum? A CHyCH:CO:H B CH;CH(OH)CH; > © cacocns D_ CH3;COCH20H (Parvez Sir] (UR Notes & P-2) [Chemistry , Legends] —— Scanned with CamScannerae. (d) When glycotic acid is he C.H.0,, 1s formed The equation for tne reaction is given ealed in the presence of a sulfuric acid catalyst, a new ‘compound, Y. 2CHOH)CO.H - C.H.0, + 2H,0 glycolic acid Y (i) The infra-red spectrum of ¥ is shown. 100: rN ~ Wit, Mh {fi Mit transmittance iN 50 ' I | { 0. | 4000 3000 2000 1800 1000 500 wavenumber/cm-' | State how this spectrum differs from an infra-red spectrum of glycolic acid. Explain your answer with particular reference to the peaks within the range 1500-4000cm-"" ira) (i) Suggest a structure for ¥ 2] [Total: 17] Legends] [Parvez Sir] (IR Notes & P-2] (Chemistry , Legs —— Scanned with CamScanner(°) Rests as 4 Pal Of stereoisomers Identity 4 he type Of sterecisomerism Shown by “onl Schecter, 'YPe of sterecisomerisrn —_ stereoisomer of R 7 (4) The infra-red Spectrum shown corresponds toone of P.QorR 100 transmittance SO 0. 4000 3000 2000 1500 wavenumber /om- Deduce which of the compounds, In your answer, identify an: correspond to these absorptions in the reg Ptions in the infra-red spectrum and the bonds that ion above 1500cm-", ‘compound explanation ... 8) i Is [IR Notes & P-2] [Chemistry , Legends] (Parvez Sir] Scanned with CamScanneru a9. P, Qand Rall contain five carbon atoms, P Q R ° ll C. H.C cH,CH,CH, ‘Asludent carries out several tests to distinguish between P, Q and R (a) Complete the table, identifying any observations for the rea x ction of each reagent with P, Qand If no reaction occurs, write ‘no reaction’. observations with reagent Pe a R Nats) 2,4-DNPH no reaction acidified K,Cr,0,(aq) | __no reaction 3) (b) Qis reduced by NaBH, Write an equation for the reaction of Q with NaBH,. In your answer, use [H] to represent NaBH, CiH,,0 + lParver sir) [chemistry , Legends] {IR Notes & P-2) Scanned with CamScannera7. Aaferent rhalomethane, CHCT,, rencis with ©, ta produce carbonyl dichioride, HCI(g)is also released as a product of this reaction. s als ° £. a cr Soi carbonyl dichloride (i) Write an equation for this reaction of CHCI, with O., a (i) The conversion of CHCL, to carbonyl dichloride can be monitored by infra-red spectroscopy. The infra-red spectrum of carbonyl dichloride is shown. 100: nsmittance 50 0. 7, 4000 3000 2000 1500 1000 700 wavenumber/cm~* On the infra-red spectrum of carbonyl dichloride identify with an X the absorption that would not be present in an infra-red spectrum of CHCI,. Explain your answer. a ii) "Suggest another difference between the infra-red spectra of CHCI, and carbonyl dichloride. 1) C ends] [Parver si) [IR Notes & P-2] [Chemistry , Lee ee Scanned with CamScannerT a | ges ‘eo srayhl ain 195 38 MOSHE oe Trecouse A /evaight ChON NOS DIDI (suace} area move ip: oa (gay mere energy requiren to forces ora Sgigw | CHCHCHCH) OR CHC? Jraver | Norolaton resticted imted -ataton ot O=C.+carson) aoune ond ‘one (of the two} methyl groune fone rot | HE, “49H WA on Kays 06 iz a = KR we ky amrew trom the C=C coubie bond craw to ie bromins ‘pte on Be; comect onentaton AND anew ory the BC-Br bend to he Br conedt carvocatin /bromenur: on trem the sxueture wah C=C erawn [BC wet one par, negative cho-D= 402) arton: rom lone par to ne carbon atom of miermeaaie oR Using bon anton shown yin atemarwe eagram) anv) | elecrons in pr bond inquce & ene pote} OR {hgh econ deny pond dovtve bona C=C repels eeetons (away fom nearest Bry oR Polarsed by (high) electron densty in p! oon /ooute bond / C=C. AM) | C= (2ametnyieropan.2-017;CH4:3:C08 any unambs uous sincere B= Qamenyoropan-t.01/ (C4, CHCH;OM /any unamiguens srueture E= (2-ymetnyipropanore 3080 ACHs):CHCOM | any unambiguous savctune oH, CL oe oH. ‘ fy wero © ° c ANH) | 2CWHyO, + NALCO: — 264-03 19+ HO + CO: MEK) | twodometnane. stomn | F= ucHor.cosy B® CHCHICHAICHO SA) | 9 evaneoray atom wen four cterent groups aioms /sunstuens atochea 2 carbon (atom) wen four cferent groups /atoms/ sussttvents attached tax) |W C=0 (group bona) AND OHH (group/ bond) c C=O (group bona) AND C+ (group bend) 4 sta) [a= emanacoce 7 |= met memanoste ‘ Parver si [Chemistry , Legends] (IR Notes & P-2] Scanned with CamScanner