Second order reactions. Second order, class I reactions 2A P A + B P. class I. class II. Nov 17, 2010!

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1 Nov 7, ½ Exam 5 Friday /9/ opics & Old Exam problems o sudy (also sudy OWLs & noes): Ligand binding including cooperaiviy HE, 5 HE5 7 E, 8 E, 9 E Cenrifugaion & Elecrophoresis 6 Final abc, 7 E 5 8 E abc, 9 E abc Kineics hrough.7 HE5, 6 Final 7 E abc, 9 E abc Second order reacions Second order, class I reacions A P A + B P A P class I class II

2 A + B P Second order, class II reacions ( ) coninues [P] [B] e ( [B] )k ( ([B] )e [B] )k ( [B] e [B] )k ( [B] e [ A] [ B] )k Zero order Reacion half-life / is he ime a which half of he reacan concenraion is consumed Firs order Second order, class I 5 6 Summary of rae laws order law linear plo half ime unis of rae cons. [ A] k M/sec sec - Deermining reacion order Plo, ln and / vs. Measure v vs. Use iniial reacion velociy (I) k M - sec - [ A] (II) messy M - sec - n(i) n [ A] M -n sec - k n 7 8

3 Example: hypochlorie reducion he iniial velociy of he reacion I- + OCl- OI- + Clin basic soluion was sudied a differen soluion concenraions as shown. Wha are he orders of I-, OCland OH- and he value of he rae consan? [I-] (mm) [OCl-] (mm) [OH-] (M) v (mm/s of iodide) R 8.5 J/K mol.85 [I-] (mm) [OCl-] (mm).5 [OH-] (M) coninues v (mm/s of iodide) Formulas and consans, /5/ L am/k mol.987 cal/k mol kb.8 - J/K J Nm kgm/s.9 cal L am cal/k eu, Pa N/ m am. 5 Pa 76 orr, F 96,5 J/mol V PV nr E nr mu E q + w -.7 Srxn CP d CP,cons ln µ A µ a, µ a, R ln H rxn C p (9 ) P P Grxn V (P P ) dg VdP Sd + µadna + Grxn n gasr ln f asolv, asolv, K A [L] [L] N + K A [L] K D +[L] µa µa + RlnaA agas gaspgas/ am asolven solvenxsolven asolue soluecsolue/ M ; G G + RlnQ H E + PV Srxn CP d CP,cons ln µ A µ a, µ a, R ln H rxn C p ( ) ds G dqrev / n P rxn P Grxn V (P P ) dg VdP Sd + µadna + gas R ln f G G + RlnQ G H S V & dg Gdw v% ( non-pv -R lnk + VdP Sd $ w ' G -nef R lnq ne F G H S dg dwnon-pv + VdP Sd P,,K Rs D( v ) x (b a log M ) v dc/d f(, [B], [C], ) k ln ln k M ln ds dqrev/ G -nef R lnq ne F H vap $ ' P & ) P R % ( Psolven XsolvenPsolven,pure Pgas kxdissolved gas µa µa + RlnaA agas gaspgas/ am asolven solvenxsolven asolue soluecsolue/ M ; asolv, asolv, K A [L] [L] N + K A [L] K D +[L] H E + PV Veff V & v% ( $ w 'P,,K m G -R lnk Formulas and consans, /5/ R 8.5 J/K mol.85 L am/k mol.987 cal/k mol kb.8 - J/K J Nm kgm/s.9 cal L am cal/k eu, Pa N/ m am. 5 Pa 76 orr, F 96,5 J/mol V PV nr E nr mu E q + w cr / Veff m A k Rs D( v ) x (b a log M ) v dc/d f(, [B], [C], ) k ln ln k M H vap $ ' P ln & ) P R % ( Psolven XsolvenPsolven,pure Pgas kxdissolved gas cr / A k

4 C S rxn P d CP,cons ln H rxn C p ( ) µ A µ a, µ a, R ln a solv, a solv, ln µa µ a, µ a, R ln a solv, a solv, G rxn n gas R ln P P G rxn V (P P ) dg VdP Sd + µadna + µa µ A + RlnaA agas gaspgas/ am asolven solvenxsolven asolue soluecsolue/ M f N K A[L] + K A [L] [L] K D +[L] f N K A[L] + K A [L] [L] K D +[L] G G + RlnQ G -R lnk v V & % ( $ w ' P,,K V eff m G -nef R ds dqrev/ n e F lnq Rs M D( v ) ln P H x (b a log M ) $ vap ' & ) v dc/d f(, [B], [C], ) P R % ( k Psolven XsolvenPsolven,pure ln ln k v % V & ( V Pgas kxdissolved gas eff $ w ' P,,K m G H S cr / A k dg dwnon-pv + VdP Sd Chem/Biochem 7 Half Exam /5/ Page of Name:. Suppose you are sudying a proein (P) wih binding sies for is ligand (L). You perform an equilibrium dialysis experimen wih $% &'inside he dialysis bag, placed in a beaker conaining a()*+,-).)/., )9(,):+-*-5;-+9<,;-( $% & )+,(-6,5>7>.6>,),>*)/?@ $% &-.(-6,5>7Assume he emperaure is 5 C and ha P canno cross he dialysis membrane. a) >,-(,8).8.,;>,-).)/,>,-(5)+.6,)'-.,5>7AB)CD)+;;>().-.7 5E>,-(,)(9),-8F;((+;>8;)((,995;>.A c) If he binding sies are idenical and independen, wha is he dissociaion consan for L binding o a single sie on P? $%&'()*+,-*./*/$*+* -565+* $%&'() 7/$ * *+%,%-./+%.+'++-$%, * 6:56%%78%('.8+%.69.'('+%,6%,%%8-+',:569.'+,/,'('.8.;'< /.'$%;'9;%%%%.69.'('+%9('.8%>56%%78%6,('?.;/9/$,/%,('. CD E F <C */(?/,.%/+?9%9+/G% ;/'6%8/,,+/G%'9'99''/%./6%6'6%.H6'%./''(:5/++ 6+('(6%%78%,/%,;%'?-/%9;:5I ;@(6%('?.:5;/9/$,/%,.%-',//J%+''-%./J%/6K/++'%((//%'(&>LH6 '%./''(:5/++6+('(6%%78%,/%,;%'?-/%9;:5I M6%$.-6;%+'H-+'6%(./''(%78%,/%,;'?9J%.,?,N:5O('.6%,%',%,> P%,?.%'+;%+6%Q%,/6--.'-./%?8;%.,> (./';'?9 d) Again assuming he sies are idenical and independen, >,C>,8).8.,;>,-).)/C-**>*/ )/,F;),-.(-,(5)88+F-65DA 5 N:5O 6

5 Chem/Biochem 7 Exam /5/9 $%&'() Name: *+%,%-./+%.+'++-$%,.56%///+7%+'/'(6%$,8-6,%.%/' P:9*H P<*H va*hr,'(<9 k ACASA ACA9 9CU SA 8V 9:9;9< 9:9;<9 ACAA ACA9 SC9 SA 8V >,,?@/%@)AA BCD/6%E+%./$6 ACASA ACAS9 ACVA SA 8V,6'>,6%///+.%'(.%/'?@%.@/((%.%.%/''%./''@//',C F6/,6%'.@%.'(6/,.%/'('.P<G EF./%@'>6%.%+>('.6/,.%/'C*56/,/,('.H?+C HL%?-6%-.'-',%@H%6/,H('.6/,.%/'C k F6/,6%7+?%'(6%.%',/-.E/%.H, H + NO N + HO + O, slow '(6%%M?/+/E./?H@.%',,/6%%+%H%. k.%/',g*56/,/,('.h?+c O + H HO, fas k- 7