1396 PRINCIPLES OF PHYSICAL CHEMISTRY from the position in the spectrum which would correspond fo tier true mass. The position ofthe Peak due. to metastable fon, m’ is related to the mass ofthe precursgr ion (m;) and the mass ofthe product fon (m) by the equation mt = (mim, 24 The eristence of & metastable fon and its lation tom, and m dus coin that the ion m, was, in fct, formed diretly from m;. Thete are theoretically maay possible solutions to tis equation but the actual solution is aocmally obtained by the inspection of the mass spectrum using major peaks, tsualy of similar inessity, as possible values of mm and my. For spectrometers which have an exponential mass scan, thi is a simple operation since the distances between mand my; and my and 1m, willbe identical. Further Remarks on the Molecular Ton : ‘Though the molecular ion i iavaiably represented as M, Le, radical eatlon produced when & neutral molecule loses an electron, we naturally ask : where does the’ electron come from ? For electron bombardment around their ionizational potentials % 15 eV), one can specify the orbitals which are likely to lose electrons in te ease of organic molecules. The HOMOs of aromatle systems and the non-bonding orbitals on oxygen ard nitrogen atoms readily lose an electron. The s-orbitals of. doable and triple bonds ate also vulnerable, At the instant of lanzation in a Frauck-Condon proces, before any structural reatrangement ean oscur, these ioniaatons can then be represented schematically 2s fllows RON aK For bomtardnent of complex mluss aroun 70 eV, any specify in te se of elton tenor st ere The tegen pk Be ace en mad get raza ios. Tes ar equenly wits in ge bcs (yg? 0 (Ca 0 amt bene mie to pest on he preci sacs Recognion ofthe Mole fo. Siete moa oes inary te mos nora iron ered fom ema ssi, ear fo be as cei pos ta lca fon win te mcs caer (ME, M+, MEA, .) as ben coe Wie Wecan apie of texts hich an donne nin te oles ‘Te ion mast bea odo pecs sine he mls ois produced by he sof oe cleton ftom the neal oll cuvese pt tue sine ie may bec dtr et oie tha te cela fo ake pec, aig fom eangenent eas fe eet Composton of te lon can be detuned, nen of bugs eiceny (te sum of pe bonds ad rag sytem) can beeline weer eo tanec on, Te Index ot hydrogen defieny she amber yl of byes sns wich mut be enol ome MASS SPECTROMETRY e 4 1307 Saturated open-chan formula to give the observed molecular formula. For a molecule Wylytl!V,, the index of hydrogen deficiency = x y!2 + 2 ++ I where say monovalent atom, 8 =.0, S or any oer divalent atom, Ul = N, Por any other trivalent atom, WV = C, Si or any other tetravaleat ator, Tavs, for example, thiophene, cats, has an index of drogen defciney =(4~$.1 The index of hydrogen deficiency must be @ whole number for an odd-eleetron ion. For an even ‘leeton ion the value will b non-integral ‘The second test that can be applied isthe nitrogen rue. If a molecule (or ion) contains an odd number of nitrogen atoms, it will have an odd numerical value of the molar mass, whereas if it contains zero or an even numberof nitrogen atoms, it wil have an even-numbered molar mass. The ‘le applies to all compounds containing C, HO, N, S, halogens, P, B, Si. Thus, fora species with 2210 or even number of nitrogen atoms, odd-elecron ions wll have an-even mass number and ever. electron ions will have an odd mast number A third test that anion is, indeed, the molecular ion, ray be obtsined ftom an exeminatio‘af te fragment ion peaks in the vicinity of te ion. Mass losses ranging, between 3 and 15 and between 20 and 26 are highly ualikely. If they are observed, they woyld suggest that the molecular ion i, in fact, a fragment ion ‘Alteration of instrumental conditions may also provide evidence to confirm the resogition ofthe smolealar ia. The use of maximum sensitivity may show up a very weak molecular ion. Alterratively, if the energy of the electron beam is decreased, the intensity of the ftagment ions will decrease Felative to the molecular ion. Ths also apples to fragment ions arising from impurities, Intensity of the Motecular Ton Peak. The lower the energy requited for ionization of the ‘molecile and thé’ more stale the molecular ion, the more intense will be the peak in the mass spectrum. Structural features within the molecule have characteristic values of ionisation energy and hence determine the amount of eneray required wo form the molecular ion, Table 2 gives a general indication of the intensity of molecular ion for several types of compounds. In general, the intensity ofthe molecular ion peak ineceases with unsaturation and with the number of rings but decreases ‘with chain-branching. The presence of heteroatoms with easily fonised outer shell electrons, increases the intensity ofthe molecular io, TABLE 2 Fateosity of Molecular Ion Peak in the Mass Spectrum ‘Se We Weak or woman “ona hgrearons | A, Ae ‘Alpi ol, amine nd ies ‘Ai, ACL AC, Conjugates Bored iain compounds ‘Ai ‘Benya beryl compounds Smartt eycc compounds | Ally aes, ees, sig cin kanes | io compounts, | nd atte, ais, ee amie Molar Mass Determination by Mas Spectrometry Deternsaton of molar mass requires meiads that wil produce the parent jon peak. Fig. 5 stows the spectra of glutamic aid, HO,C—CH(NI,JCH,CH,CO,R, obtained by Tel iaizaton (Ft) 2d fls desorption (FD) methods. Very Hine fagnetatin overs with Net desorption. Ether method is adequate for the molar mass deermiation PAB is the most tequextly sed mettod for ‘olor mass determination of nonvolatile natal vag the davainant (M +11" and (M-H)* ions for ganic materials. With organic materials and organomalie compounds, significant fragment ionPRINCIPLES OF PHYSICAL CHEMISTRY 1298 ifomation is bined providing srt informatie. = wana wa ey Qn 2 wo 2 Ww. é . 2 Bo 4 4 Sa Ee we Ee § mo] coow* gevtnt Ea mo 130" 160 OTe ey ho eo ova" wo 8) oo Fig 5: as psf gt (Fe ion Fa eon ten a rn aptiation, a eto igri Apo fas pst, Fe Sg pa con auevt nly employed st els eee st Te eseraing poi ee {eS pao at pment So pate pres ana ove | SES en sa ue of jas epee cng, he te Coserved te wel fora ngs splaon coy em gen med Saeptan of he pram nit, gt pen, te aoe he pe, Bet Accordugh, Et etos ave ped pct tees fr EI a 70 e¥ ae rail ia inp forming kon spa kam one est © mk congo of the spsrum oft wakoown conpopnd wih tat of & Known sample on the 6 Pace eren eters .. ye cing Remar. Masonry lc rie easing el pep: Te sn Sey mesg et Ser cee ideo por eps be moa, on ar ee 2 eee cero eimeilgene Fel bane esis sre AB0 ha aes ibination of mass spectrometry with gas-liquid chromatography (GLC) provides om ix met or nas of ites, Very sl amo of aera are sete The mat spoarometar ised as the GLC detector and numerous mass spectra may poets Erp componsn emerges (om he spectrum, A prallyresaved GLC peak is red. detected by the change la mass spcta ofthe pea ih tine uation forthe ft (0 steps Froblan 1 Us R$. ar he pla gered compo it fe eas ‘mass spectral analyse, Lent Ee steps and exch met in the eq tet - a RS* + 26 Getto ner | Supe RS eH RSt + eon “ ee eet High omy es: we (Cagpenations) sen ass Radice Cailoas Fragmectaton can ave release a emailer nal exon and x ora! ralgule = RSH RES or RES MASS SPECTROMETRY 1398 Froion 2 Aer iization ard trcgmentatchsocur, what des the mae spctroweter do to erode 2 sms spetram sen) (Wh ca the mi alas be tle a the ac ws ofthe eon fa mos cates?) How arene Ue mas a compotod be dete by mass ca aay? () Way & lens tae | oo pes aid Be anon ste for sans?) Why do several signals appease ‘Speuren 1 (0) Which feapment cations ate the most abundant ? () How ae reat’ teases ces Anos: (0) a mot eas he chars on the ele fe veo 2) 6 +1, making mt = 10 a fe pret (acleua) cao: do nt fagent (he spiel sain), ebe tare vale can be ‘sige ashe roars ofthe pare cation aed hens Be put ele (0A scativey sma mamber of molecles ae wen in Serves fagnens. Combicaton of fagmens ight ew lms wit ap wad bese eoaag, {GT rca con fgets ye and eich ein fagment can fer fasten pid sar A, Me Rest sbvadut cations are te most sable ones. Hence, «good undecstnding of cation stilts i ‘Steal for iter fagmeenon pavers ces) erste doesent io ot iene pk, clled the bse pati abralyasiged a vale of 1005. The eal peat TEMG ME mesured ant divided oy the base pk height w ive lr ave pesenag® soendneee Fae ‘ani, peak with 23 Neigh of the tase pr ts lathe ibanone af oP Problem 4 (a) Give mulesar formals of hydrocarbon cos with me vas of ()29 UD $9 © Cive a combination of C,H sad N to aco fr mi vals af G29) £7, ‘nove: () Dive te eve vas by 120 gt the ube fC he emer the mass du we Motta fre at: (0 HS Ca) Cy, 12) OE coe N is pre, sabrsing 14 faves 2 mas Of 1S, xh for ear € and the Hs. The form i ‘SONY: One, tor thes Ns ca be prestige ios: GFRNT, CANT or CHAN § (0) De patent (molecule ions, RSs of hydrocarbons ever have odd mv values? (if Wy GM and O; aay ts mi value be eer oid ferent (0) an RS" cota vay, ert mE ale beer od or ees? Way conan on m= 3, mat be GUS 7 What ithe? ‘i Problem RS contains aad Ny eke 0, Ne: Hysrrctone and i are os mas havea een ube of Hs: Callies. Ca Mets Calas ec. Since the somie mas of Cis eve (2). te mises ne be (ir ase bes of © i Grae dos oat change he ai of Cw B. Since mas of 0 is even (6), te ass of RS* wih C, H and O mut be een, ) reuesaaadaeal H Clg, CaN, Cathe). Three, bes of Hs and ano av abe real An even tune of Né reyes ‘These seme ply ony pares fons, mr 8 fngment ont @ Te lngstmanber of Hs fortwo Cs six (Ci Some posites ce CHyO* and CAN”, Pela &. Mich sleceon is most ley tobe los in ienzton df the falling campownds 1 Write ua stesronk ruta for RS* (e) CH,” CHSCH (@) HyC=Clly td CHCl code OSE Nm cen inte HOMO is mo ily eta, te dering ode finely i Tat re 9 NMR 2 42: & electrons ae preset te ost een me kel comes fom We ghey 2 ‘Te + in each formula below showy the Cheat te ming ee H (1s he charge due w the mig este)