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    File 341

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    1992 PRINCIPLES OF PHYSICAL CHEMISTRY einen comerions ait wit rans cmray taster, Ii celvat 0 conga he ‘ime seales for some of the processes listed above. The time for a bond vibration is 10" s+ the ‘maximum lifetime of an excited state ion is ~10" 5 and the time an ion spends in the mass ‘spectrometer ion chamber is 10° to 10 s, We see that there is ample time for the excess estronie energy: in anion to $8 converted into an xeess of vibcational energy in i lower lectronially excited state. Thos, molecular ios in the ionization chamber are produced in different nergy ates which further undergo rapid intemal energy conversions to give rise to ions, wilt ‘Yarying amounts of energy. Thus, all Uk above processes of fragmentation of the ion BCDE* are reflected in the mass spectrum. Factors Influencing Fragmentation. We sall briefly list some factors that involve feagmentation of organic compounds + ‘a. Functional groups. Some functional groups may iret the course of fragmentation profoundly while other functional groups may have litle effect. . Thermal decomposition. Thermal decompasiions of thermolabile compounds may occur in the ion source leading to difficulty in inerpredng mass spectra. For instance, alcohols may undergo ehyération before ionization. If chenmal decomposition is suspected, the compound nay be ionized in 8 cooled ion source so that electron bombartmeat ofthe whole molecule takes place, ©. Bombardment energies. Orgiic mass sectra are reuinely recorded at about 70 eV electro energy. It may be noted that even with these high ereges, the molecular ions possess maximum of about 6 eV energy in excess of their ionization poteatials and there is litle change. In the fragmentation patter if this 70 eV energy is reduced to shout 20 eV. However, the on fed (Le the effcieney of ionization) is reduced andthe spectra are weaker in intensity overall. From about 20 eV down tothe ionization potential of the molecule, the mass spectrum becomes progressively simpler since only the most favoured fragmentations are occurring. Thus, recording low-energy specta isa uselul method for bond-energy tues, 4. Relative rates of fragmentation processes, These are also helpful in dictating reiive abuadances Thus, inthe simple case of A? changing eter 19 B* and,C oc to BF and C, te equilibrium abundances of .A?, B* ind -BY depend on the relative rte “constass, for the two ‘commpeting rections. These rate constits may, in tum, depend on the excitation energy possessed by ‘AY and will also depend on the heats of formation of lf Ue products valuation of Heats of Sublimation of Solids ‘The exass spectroscopic tectnique enables the evaluation of the heats of sublimation of solids having high melting poims. The principle is based on the fact thatthe intensity of peaks in the specteum is directly proportional to the pressure of te sample in the ion source. The sample is Placed in @ reservoir containing avery small pinhole (a Knudsen cell) which is connected tote lon Source; the sample enters the soutee by diffusion though the hole. Enough sample is placed in the ‘thermostated cel ; the solid phase i present in the cell, The change in peak intensity, which is ‘elated to the vapour pressure, is followed as 2 fuictioa of temperature. From this te heat of Sublimation is calculated, Although a soall amount of the sample diffuses into the ion beam, it does ot alter the equilibrium in the cell. It has been found tht monomers, dimers and trimers are resent in the vapour of alkali metal chlorides, Caleulation of Appearance Potentials and Toaizaion Potentials ‘AS we have stated earlier, when an electron with energy equal t, or greater than the ionization ‘nergy of the molecule, collides withthe molecule, a moleeaar ion is produced. Fig. 4 shows the ‘onication efficiency curve which iste curve of relative intensity of a peak (Le, she number of ion fragments of a particular type) versus te incident electon energy. At electron energies below the iowlation energy no ions are produced. As the energy of the eleccon beam equals the ionization 1933 Mass SPECTROMETRY © ow intensity soba exer), pak of er ow ye a SB. easly oral te ena 9 “entrar oe me Oe Seer a ation ve eal Howe atmene cen ey, te roe ee lo ees ee ee lo Ro, sine tn more intense peak unl plteal ‘leurs da the curve. The curve shows a tall at eu args tect of vari i en cee oe bombing secon wee anno sce lara 2 SE tn ts em cre. a chee ee ecepalion ofthe reo ficiency env ges onan ee When, however, the observed peak is that of the frage replat of Se eee eae fields the appearance potential of the fragment. If, for instanc 4 the nization ficiency eo pe amen Rm the moles R-X, the appearance pt Mae btines by te exrapolaion oe efiy ee peak ol : Aye = Dex t In + Bint anf P ti t-) ad ; fy is the ionization : fhe RK band fa sg 2, Dax: te sp ton eyo RO bon he en te ONE de tne ery of pails aed ad, i the eatin en) of Sree ent, fet the electonc, vibrational and rotational energy If the Frage eo ee pee gna al ey canbe nee, ng hye = Da he : cant ested fom te pence sjen fy obecwise X° gts sociated THEIDENT ELECTRON ENERGY) —> Fi. 4. A typ ionization fin cue. 03) emial data using Bg, 23.1 sould Saeed fe ‘of electronically excited. be noted that Jy mst be ess than Fragmentation Processes “There are two important factors spect, te say ofthe on tke reactions feaing ote fon. Tovah ions i he mass which detcine the intensities of the fragment arc nce he fd ren nd ome! ch experi coon the mas peso (ty sine esti) ier eal fom tose rormally excused in ogni Fa cnt) can be wed (ornate the aparece Of te Fe ‘tectum Thus, the fllowing fragmentations prodce stable carbocations es cH y e R-G—CHy) 4 Re + CHE @ z i S = > secondary > of saturated carbocations decreases inthe order: tetany ‘The order of stability a eaion i ommed inary > ety Ths, 8 sable te ; mt) scum of masa afi exon . » - ; ge-Ctiy-Ch-Cihy + RY + EC CH, «—> CH = CCH (6 Formation ofa seven-membered cyte topyium fn, CoBly [oatts-cty-eft > ® + 1394 PRINCIPLES OF PHYSICAL CiEMISTRY ete exbocation is stabilises by deloaisation of the lone-pai electrons on the adjacent ROCHE AR — sch eRe Sih, (0 Fornaio of he resonance sie yan oo ap Nac da te naa ini ora by revo dros of te Loe Snipa from the mc The emery teu snes ae oe et iompae < sniped < mewn x < @ ‘saa ion sts formed which may fone in vary of eye, Spl bond cleage may occur to give @ neutral and anionic fragment. Alternatively, several rearangemeris may coca hich are. then followed by bond cleavage reactions. We shall give belew some examples of fragmentations and recrangement. Fragmentation by Movement of One Electron. Bonds are broken by movement of one elecro0, reptesented by a fishshok azrow ((), (2) eceaage gna clenage oe ° . noe RAR ition ress inh removal of cron ad the e-na hen breaks peel to give i carbocation with the ejection ofthe largest possible group as the sadicat” 1 ecdeouge pha ceoage) RRR 9 - ° tROCHMOR 5 Rs CHOIR ec : 2 2” hh —> Re R—CH=NH 2 . 2 RCH CH=CH, ~—> R+ct=CH—G all these processes an uncharged alfy! rafal is lost enabling the sesdual electron to pair with dat associated with the original radical ion to form an even-electron ionic species. Fragmentation by Movement of an Flectron Pair. In this process ‘bonds are: broken by overeat of an electron pair (two eletrons) towards the positive charge represeried by 2 nocral “eutly tow! (AY), IR alee (Cored fom eclenrge of meddle oa} e e Cy, —» Remo In all of these processes an electron pair is donated to the charge site, The electron pair may come from the bond adjacent tothe charge st, ® 1995 secre a ly re electron ions which are aormally recognize in arrangement. Rearrange ma yield keto fons which ae svn) tea trum They are useful ads i the interpret SS re eee alle inte fon sours, earangeent ae exenely

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