1049 PRINCIPLES OF PHYSICAL CHEMISTRY He (Tbe CHC bond is wee than be C-H bond) ai (6 Maca Hy” - ¢Eteton comes Ho the bat) @ WCC: — ann eeern is as) @ H+ OF (Ann doema is ea) Problem 7. Give the structre of a compouod Cylly0, whos mass spectra shows m/z values of 15,43, 57, 91, 105 aod 18. Answer + A peak a mit = 15 svgpests # CH roe. Bosme 43 ~ 15 2 28, the mats of C=O, the mit value of 43 may be doe © an aceyl, CH\CO, group inthe coepound. The highest peak gives the malar mas {lewving an sony! group (wit = 43) from 148 ges 105, whch an observed pene. Next below 108 fs 9, Aieense of Las the sggets a CH, grep abe! 1 CHGCO. So fr we have CH,COCH, adding wp 57 teving 18 ~ 57 = 91 ta be acouned fer. Tepes iy 1 be (CI, whose preeso xte able sy sn, GACH, Pach weet al ws arsenate ECM CHC, Problem 8. Eyplala the appearance af w/t = 4a he mass specrum of CHCH,CHCH “0. Answer: Tae value of w/t (2) of th mesa on, minus 4 equal 28, the molar mas of te ost uncured roel. High resolution mass spectrometry shows tht he lst melee is H,C=CHy and the Gagment exon 1H,C= CHOHI*, Tse specie ae rom the MeL reeragenent of the pant extn, as own below ERO af may! KH H Kt | DOK mS, c™ i oy = een mat = 29° (not Problem 9. Summarae the Kind of information provide by the fig spiral ecoiques : (2) UV) IR (@ PMT (A}¥C NOM and () Mass Spetomety OM. ‘answer + (a) Conugstion (8) furtionlgrowpe (© evitoeat of Hsin a molecule and consequent moteclar skeleton incting the Hs (2) cab steeon and (molar mast of the parent and major svt exes from the (rgmenttin pater ‘Problem 10. Write equations iol the eleron-st formals for each fragmentation wsed to explain the folowing : (a) Iabutane, + typleal Branched-tala alkane, has a lower-intensty RS” peak than does 1 os c cation at mlz = 31. (@) All CQ,CHGR-ype bydrourboas have prominent fragment cation a mit = 91 (@_ Alkane of the type H:C=CHCHR have 4 prominent fragment cation at alt = 41. (0) Aldehydes, RCH=0, show intense peak at wit 29. Answer: (a) The weaker CC bos clea moe easly tan te stronger CH boo. Fragmentation of the part eat of bua, ean, — cg + om ih ti sires 2 2°R* tas move sable thane RY fom aber, HH 4 + He ° + ctor lel Rycclc en, rt ha * (MASS SPECTROMETRY 5 141 Hence, RS* of isobutane undrgocs fragmentation more really than doce RS* of nbuase, ant fever RS* ‘ations of obuane survive. As 8 rest, bane his « Inerieasty RS" peak than ane. = 8 I ® gene we A AC* net fo an © is sbiling by exenedsontng(esnance). The RS* species of aeoals getely undergo cleuage of he toed» C4.6-O1L © causdtn ms cai: by (sole bea RY) (4 ror sable aromatic: otoheptaieyl cation, w/e Hye né-cieay + ok (ea ae exon’ a=) sabe aii oa mi2=29) Rca © ced: Fron Fig 6 sows the mas spr of ne As the spc um Lhe appre compen ‘by analyzing the fragmentation pattern with the aid of equations. = 238 sueessy oy a on aT 2 Fig 6. Mass stam of sone Answers The spectrum in Fi. 6. hus «pute pak wt = 18. The sex lover one at m= 99 indies 8 loss of 29 (128 = 99) mas units coresaeding wo CHC From tis pot the prominent peaks are rom 2 ‘sequel los of CHs. This Fapmentatn pases i pea or sagt cba alkares,1342 PRINCIPLES OF PHYSICAL CHEMISTRY Problem 12, (i) What information canbe obtained rom the mass spectrum is Fg. 7 about the strcare sf am arumati hydrocarboa? (8) Wha other spectros cold help penpelat the compound ? 09 : CD Ta ea oo Fig. 7. Mass perm of an rma recon, ‘Answer. () Peaks fr pret eo faa compounds ely aps a mas pein. Te prec a 8 float of 5 and» molt frm 0f Cp Te ne pakat St aly doo GAC sag thc th conae: 2 ocd are 2 Ci gin wal eg. Two coop, LCCC, and CCH,CH Caen ie agen, (0) A BC ame scram weld ep at ebezene wold Ee fi Sg, er! Hugtezte woul ge seen pl A po spe woud show We cancers ape or on a ter tating, ee to MeLafny FW, Imepreaion f Mas Sera, Uae Stee Boks, 180 Mil, LC. larodacion to Mase Spry. 2 Lemon, 172 Biena, Mas Spcronry# Oise hoi! Aptis, Meee 1962 ove. 1, DH. Wilns, nd RD. Boe, Pcl of Og Mas Secromay, 2 cn. Lan, 12 Nelatens.F.W., and aR. Soufi, Reply of Mas Sa Da, Wry, 199. Divi R. abd M, Freon Mat Scrat, Wily, 198 Chriss. 6.0. Aid Cena, 66 en, Wy, 2 Medaser. NLC afd C. Metfaser. GOMS A Prac! Ur Gi, Wey, 198. btn, H.3, Hobos of GCS, Wey, 20 [I Review Questions } 1, isos the sie insrumeston ofa high eslaton double fomning mas spesomter an derive an expression forthe mi in he mas spec, 2 Draw schematically the mass specrum of 2-nethylpnsne (Cl) showing Row the cain can ben Un sve oss. Discus briefly te frapmenttan pattern obeve, ‘Ovatinebriey the dyeanics of elecron- moked colisns i mae spectomety. mune and dics he fos which ifltce(ageaton of rane compounds ia mass spiro. How ce appearance poets and onan poe eee from mass spectrometry ? How i mas pectomeny use to determing the mur mas of vl ognic compound ? * CCasicat thermodyramics deals primarily with the study of systems which are in a sae of qulbrium. Jt adequately deals with processes which begin and end with equilibrium states thoush the inervening ‘sates of a given process may be nonenuliam. ‘An equiibium state, infact, is oily an oversimpliication of the ceal state of a system as it gat be realized only partially inthe man-made systems dealt with in laboratory. Natural processes, on the other hand, are ireversible processes taking place in open systems. AS 2 consequence of severl dissipative processes occurring therein, tne time-invariant ofthese iteversibie processes is a steady sate and sot an equilibrium state. The steady state, in fct, is. more comprehensive than the cequitvium state, which is merely a limiting case ofthe fogmer when the “fluxes” (vz. flow of heat, mass, electricity, ete.) arising from the environment cease to exist. Irreversible thermodynamics i= also known as non-equilibrium thermodyeamics. Phenomenological Laws and Onsagers Reciprocal Relations The ieversibleprocestes involve te tansport of one or more ofthe quate such a8 heat, mass, momentum and-electric charge. In all these cases, a quantity called the flux is transported as 2 result Of a dving force ‘whichis derived fiom the gratiem of some physiel propery of the system. Thus, te diving force fr abet ux i the tenperaure gradient; that fof te Bux is the concestration gradient ad that for an electric cute ithe potential gradient. In al these can the magnitude of the Aux (or flow) i dreey proportional tothe diving force. In generale the umaspoet phenomenon fot 2 one-iensoal stm i wien ss, J=IX (i sihere J is the flux (flow per unit area) of the quantity transported along a given ditetion: X isthe Ariving foree (or the gradient) which causes the flow in that direction and Lis the proportionality cows called the transport coefMeient, For tue various transport (transfer) process, we can now write the following relations a i Heat Transfer: Jg = ~« Fours tw) 0 eee © 3 Momentum Transfer : Jy, (ewon’s aw) “ (Ohm's iw) o Here the Jjs are the corresponding fuxes = Je isthe heat flux ; Sqn the mass flux : Jigs the 1343 4. Flow of electricity : Je