WPC  \.h?Ӧ8-pشĘ7u>p7s'g*¦ܷKJ;ڢM{Կr0y1[f+>4=&   .r|h4r:"o$6X< Ǭ&Swzy/%͖N">Ekx3υ`?\R $j*e '&oY'1Z#pb :\Ԗ{q-A1NH4K`m8Q`mOoTwD9K%* 9lpth!MZo0m4 3/ qo7-B`9q&&% HR mH2;ߖo9vA^<ϟA?˙VFkZV&e"p%ٞ+N-_2Dò5I^ʦ^?Y#!UN %M 0:SUNw@4 / > m@ 0UcW UN 1u 1} 1 b 1 18 0w f< a> > > > 1R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R B 0(9 Z6Times New Roman RegularX($USUS.,9 Z6Times New Roman Regular E_E  Xz7:i+003|xU(;3$2#  0  .3  0  (9 Z6Times New Roman Regular##37=CIQYag1.a.i.(1)(a)(i)1)a)( CEMU]emu}AutoList3(a)(a)(a)(a)(a)(a)(a)(a)( CEMU]emu}AutoList2(a)(a)(a)(a)(a)(a)(a)(a)Page - -(EEGOW_gowAutoList21(a)(a)(a)(a)(a)(a)(a)(a)  CEMU]emu}AutoList4(a)(a)(a)(a)(a)(a)(a)(a)(O;$0  2#  a  .3  0` (#(#hTABLE A EEGOW_gowAutoList20(a)(a)(a)(a)(a)(a)(a)(a) d !USUS.,  _ XXXX CXX8XXdd8@_ _ "CHEMISTRY441/541  #XX C_#Y}XX @p p PHYSICALCHEMISTRY:WINTER,2007.  #XXY}!#хXXName:__________________________  SocialSecurityNo.____________ A FINALEXAMINATION h     March19,2007[12:30p.m.2:30  i p.m. #XXх#хXX ]#XXх# CXX `    #XX C# CXX  - } #XX C#&B %XXAnswerallquestionsonthisexaminthespaceprovidedusinganonerasablepen.Inordertoreceivefull A  creditforanyquestionyoumuststateallassumptions,showallequations,showallyourworkandsupplythepropersignandunitsforyouranswer.IfIcannotfollowyourlogic,thenIwillnotassignanypartialcredit.PLEASEBENEAT.  4  #&B % %&B@#Thisexamis 16pages longandisgradedoutofatotalpossiblescoreof200.[therearenobonus   questionsonthisexam]    Allthephysicalconstantsonemightneedinthisexamarelocatedonthefirstpageofthis  exam.Eachofthefollowingfoursectionscarries50points.StudentsareadvisedtoattemptTheUsualSuspectsfirst. Somepossiblyusefulconstants. (x Speedoflight0 ` 0 ` (#` (#0 (# (#2.998x108ms1 Y(#(# _Planck_sconstant0 0 (# (#6.626x1034Js:(#(# Boltzmannconstant0 0 (# (#1.381x1023JsK1(#(# Faradayconstant0 0 (# (#96,485Cmol1(#(# Atomicmassunit0 0 (# (#1.6605x1027kg(#(# AvogadroNumber0 0 (# (#6.022x1023mol1n(#(# MnO4+5e+8H+Mn2++4H2O0 h E0=1.51VOh(#h(# O2(g)+4H++4e2H2O(l)0  0h(#(#E0=1.23V0h(#h(# Br2(l)+eBr0 0 (# (#0h(#(#E0=1.09Vah(#h(# _AgCl_(s)+eAg(s)+Cl(aq)0 h 0h(#h(#E0=0.22VB(#(# __(water)=1.00_cPoise_ # *wXddd Xdd Xdd X(#(#w,<dd ,<dd +   !  Act  !I  Score  !I  One....Dejavu  {#!   {#" Two.....TheFrontNine  $@ #   $@ $ Three....TheUsualSuspects  e&!%   e&!& Four...TheBackNine  '*#'   '*#( HandicapAdjustment  O)$) Zero(everyoneplaysscratchgolf!)  O)$* FinalScorecard(intheclubhouse)  *&+  *&,   +%', #XX %&B# XXXX &B %X X Question10 ` [50points,5pointseach;exceptford,gat10pointseach]....acaseofdejavu? ` (#` (# Rationalizethefollowingobservations.L  (# L  3    3H2 (  a  )3  0    Thestandardpotentialofasimplewateroxidationhalfreaction:O2+4H+(aq)+4e2H2O(l)is N depressedbyabout0.41Vwhenitisruninthehumanbody. 3Hs݌ (#(# Ќ  __  3    3 2 (  b  )3  0    Aconcentrationcellcanbecreatedfromtwohydrogenelectrodes.Makeacrudesketchofthis  cellandgivetherelevantcellreactions.Isthereanydifferencebetweenanelectrolyteandanelectrodeconcentrationcellinvolvingthestandardhydrogenelectrode? 3 5݌ G(#(# Ќ    3    32 (  c  )3  0    Apotentialdifferenceofbetween7085mVismaintainedacrossmostbiologicalcellwalls.  ThesecellsaremorepermeabletoK+ionsthantoNa+andClions.Theconcentrationsof  potassiumionsinthecellwallaregenerally20.3Xthatoutsidethecellwall. 3݌ (#(# Ќ    3    32 (  d  )3  0    Additionof1.00MBrionstopermanganateandacid(bothat1.00M)showsarapidformation c ofabrownishpungentsmellingliquid.AdditionofbromideionstothesamemixtureinabufferthatmaintainsapHof6.00,however,doesnotshowsuchanovertreaction. 3,݌ %u(#(# Ќ    3    32 (  e  )3  0    Forthesamegaseousmolecule,atthesameconditionsoftemperatureandpressure,theproduct  ofitsmeanfreepathanditscollisionfrequencygivesafixedwellknownvalue. 3݌ (#(# Ќ    3    32 (  f  )3  0    Thereisanegativesquarerootofconcentrationtermin_Kohlrausch_slaw!#&B % % &B##XX %&B #ԇ 3݌%u(#(# Ќ   +&* Ї&B %XX  3    3L2 (  g  )3  0    Intermsofionicmobilities,theorderis:K+>Na+>Li+.Doesthislookkoshertoyou? 3Lw݌(#(# Ќ  #XX %&B-#&B %XX  3    32 (  h  )3  0    Mobilityoftheprotonissomuchhigherthanofanyotherionknown. 3 ݌4! (#(# Ќ   +', Ї#XX %&Bì#  &B %XX Question20 [50points;5,5,15,15,10] 0 (# (#G (#(# L  ((L  3    3C 2 (  a  )3  0    Namefivephysicalparametersthatcanbealteredtoeffectarelaxationspectrum. 3C n ݌) y(#(# Ќ    3    3j!2 (  b  )3  0    Whatistheprerequisiteforareactiontodisplayatemperaturejumprelaxationspectrum?Givea w relevantequationthatshowshowthisconstraintquantitativelyaffectstheequilibriumconstant.AssumeaTjumpof5Kforareactionmixtureatequilibriumat298.15K.Evaluatethepercentchangeinequilibriumconstantifthereactionsenthalpychangeis30_kJ_Ԁmol1. 3j!!݌j(#(# Ќ  #XX %&BM# +&* Ї&B %XX  3    3T$2 (  c  )3  0    Considerthereactionofmoleculariodineandiodidetoproduce_triiodide_:I2(aq)+I(_ag_)I3(aq).   Howwouldyouproceedtoexperimentallydeterminetheforwardandreverserateconstantsusingatemperaturejumptechnique?[Youneedtoderivetherelaxationtimefromfirstprinciplesandthendescribehowtherelaxationtimedatawillbeusedtoderivethekineticsconstants]#XX %&B5$# 3T$$݌5 (#(# Ќ  __   f    3   &B %XX 3v'2 (  d  )3  0    Thedecompositionofozone[2O3(g)3O2(g)]inafixedvolumewasfoundtobefirstorderin  theconcentrationofozoneatthebeginningofthereactionbutbecame_autoinhibitory_Ԁasthereactionprogressed.AverycleverChem441student,_Pratik_ԀPatel,devisedthefollowingreactionmechanismforthisdecomposition: 3v''݌ (#(# Ќ     `  O3󀀀O2+O 0  _k1_(forwardreaction);k!1(reversereaction)4(#(#    `  O3+O 2O20  k2(slow,ratedetermining) e(#(#   Can_Pratik_smechanismexplaintheseexperimentalobservations?       3    3+2 (  e  )3  0    ݀Thezerocurrentpotentialofthecell:Pt H2(g) _HCl_(aq) _AgCl_(s) Agis0.277Vat250C.What  isthepHoftheelectrolytesolution? 3+,݌ (#(# Ќ  ___  __ ` __ __  __ h __  __  __ p __  __  _       &B % %&BQuestion30 ` [5pointseach] ` (#` (#    ` Define,asbestasyoucan(useequationsaswellwhereappropriate)thefollowing:L E((L  3      3=12E(  a  )3  0 `   coefficientofthermalconductivity(explainalltermsthatappearinthisequation) 3=1t1݌5` (#` (# Ќ      3      322E(  b  )3  0 `   Theextendedlimiting_Debye_Ԅ_Huckel_ԀLaw 322݌d` (#` (# Ќ     `     3      332E(  c  )3  0 `   _Fick_sfirstlaw 33'4݌!!` (#` (# Ќ   ]+&,     3      3'52E(  d  )3  0 `   anelementaryreaction 3'5^5݌ e` (#` (# Ќ      3      3(62E(  e  )3  0 `   The_Nernst_Ԁequation 3(6_6݌` (#` (# Ќ      3      3D72E(  f  )3  0 `   Thehalflifeofafirstorderreaction 3D7{7݌k` (#` (# Ќ      3      3t82E(  g  )3  0 `   TheEinsteinRelationshipforthediffusioncoefficient 3t88݌&f!&` (#` (# Ќ   =,'- Ї  r   3    392E(  h  )3  0    HowtheEinsteinRelationshipisusedtolinkmolarconductivitieswithdiffusioncoefficients 399݌(#(# Ќ    3      3:2E(  i  )3  0 `   Thethreebasicpostulatesofthekinetictheoryofgases. 3:;݌` (#` (# Ќ    3      3<2E(  j  )3  0 `   _linearization_Ԁasusedinrelaxationkinetics. 3<;<݌  ` (#` (# Ќ    #&B % % &B/#0  {*%+(#(#  Question40 ` [50points;15,10,5,5,15] ` (#` (#  L E(( L  3    3L>2E(  a  )3  0    Ithasalwaysbeendifficulttojustifyfirstorderkineticsbeingderivedfrombimolecularactivation.  The_Lindemann_Ԅ_Hinchelwood_Ԁmechanismwasusedsuccessfullytojustify_unimolecular_Ԁkinetics.Derivetheratelawthatisderivedfromthistreatment.Forgasphasereactions,specificallyunderwhatconditionscanoneunambiguouslyobtainfirstorderkinetics? 3L>w>݌ (#(# Ќ    f   3    3 A2E(  b  )3  0    ݀Acidhydrolysisofsucrosehasanactivationenergyof107_kJ_.Additionoftheenzyme  _saccharase_Ԁreducestheactivationenergyto36_kJ_.Mowmuchfasteristheenzymecatalyzedreactionoverthe_uncatalyzed_Ԁone? 3 A8A݌ (#(# Ќ   S   3    3LC2E(  c  )3  0    Asimpleexperimentwithgreaseandaheaterwillconvinceonethatastemperatureisincreased,  theviscosityofgreasewilldecrease,makingitwatery.Isittruethatthestandardequationgoverningviscositydoesnotsupportthissimpleexperimentaldatum?Whoiswrong? 3LCwC݌ (#(# Ќ    3    3HE2E(  d  )3  0    IfthestandardredoxpotentialsfortheFe3+/Fe2+andFe2+/Fe0are0.77Vand0.44V  respectively;usingthese,evaluatethestandardpotentialfortheFe3+/Fe0 3HEsE݌(#(# Ќ      3    3F2E(  e  )3  0    TheMichaelis_Menten_Ԁschemeisthesimplestandmostcommonlyusedtreatmentforenzyme  kinetics: 3F*G݌ (#(# Ќ     ` E+SES;0  0h(#(#_k1_,k1rh(#h(#    ` ESE+Products0 h k2Sh(#h(# 0  whereSisthesubstrateandESisacomplexcomprisingoftheboundenzymeontothesubstrate.Assume[E]0istheinitialenzymeconcentration. e(#(#   Provethattherateofreactionisgivenby:   `  v=(k1k2[E]0[S])/(k1+k2+k1[S])  ' 0  0` (#(#Next,rewritetheequationabovetoshowhowthe_Michelis_Ԅ_Menten_Ԁconstantisutilizedintheequation.   h     ` (#` (# ___  __ ` __ __  __ h __  __  __ p __  __  __ x __ _