BMB170a_2011_LECTURE2

BMB170a_2011_LECTURE2 - !"!#!$#%&'()*+,-./0$12+...

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T&?+1.+eW+ C! •! 8.G0+$1+>*4/0-$*+ •! 8$=0+4&*$1+ 1.G014@*/5-0+ + CO2- H3N –! !, ", #, $, %, &, '+ #+ "+ !+ %+ $+ &+ kG$1.+ *4$=2+ ,*l0-12+.Q+*G$1.+*4$=+20_50140+4.120-L*<.1+ /.+*+J..=+R-2/+*99-.D$G*<.17+*G$1.+*4$=+2$G$@*-$/?+-0s04/2+2$A0+*1=+9.@*-$/?+ J@5+ 9-.+ *29+ J@?+ *@*+ k+ 20-+ 8+ /&-+ r+ ,+ c+ *21+ V+ J@1+ O+ 2G*@@+ o .5/0-+ K+ b+ %+ 4?2+ e+ $110-+ @*-J0+ "+ G0/+ T:e:+K*?@.-+*%&-./#"%&+0#1%+""27+6)X+E';ZPH+ &$2+ T p+ $@0+ *-J+ a+ q L*@+ @?2+ @05+ 3+ \+ d+ 9&0+ /-9+ /?-+ ,09<=0+>.1=+Q.-G*<.1+ t+ Ca6m+ Ca6m+ t+ %*-@2>0-J+3*>.-*/.-$02+ 3*04(.05.(6+.7'1-. \.51=0=+>?+i:%:+i*4.>201+'ZM(+ 3*>+Q.51=0=+$1+'Z(X+ )2$$.2"#3($/4&$2"145/"6/7404& 8:,:+8u-01201+E9aH+ ,-./0$1+4&0G$2/-?+E';M)2+h+X)2H+ 86+.1*+9+*:. b*n+3$1=0-2/-uGC3*1J+ •! a.S+S0+=024-$>0+9-./0$12+ –! ,-$G*-?+C+*G$1.+*4$=+20_50140+ –! 804.1=*-?C+-0J5@*-+9.@?909<=0+ 4.1Q.-G*<.1+ –! K0-<*-?C+9*4F$1J+/.J0/&0-+.Q+204.1=*-?+ 2/-54/5-0+0@0G01/2+ –! 3$1J5$2<4+*1*@.J$02+C+@0l0-2#S.-=2# 201/01402+ –! ]o5*/0-1*-?`+ \$>0-+=$j-*4<.1+2/5=$02+ •! \$>-.52+9-./0$12+S0-0+ 520=+R-2/+ –! T$@@$*G+k2/>5-?+E300=2H+ •! K&-00+9-0=.G$1*1/+ Q.-G2+ –! B+f+S..@+EF0-*<1H7+G524@0+ –! I+f+2$@F7+2/-0/4&0=+S..@+ –! %.@@*J01+E/01=.12H+ k2/>5-?+k11+e0L+!$.4&0G+E';N;H+Zg''N+ I+E2$@FH+ %.@@*J01+ B+EG?.2$1H+ 8590-+4.1/-*4/0=+ +V-$0=+$125@$1+ 4-?2/*@2+ %-.SQ../+,-.4+e.?+8.4+E';NZH+k'PMgXZ)+ ik%8+E';N;H+P'g'ZP)+ !"#$&'#(21&)#$&8+E';X)H+6)NgN6'CNXP+ 3$152+,*5@$1J+*1=+/&0+9@*1*-+909<=0+>.1=+ E%k3Kc%avH+ O 1.24Å 1.32Å C! C x+ N C! H •! %-?2/*@+2/-54/5-02++ –! =0R10=+-0Q0-0140+>.1=+@01J/&2+ –! 2$1J@0+>.1=+%CO+':M(w++ •! "0/&?@*G$10+C+T:O:+3$924.G>+*1=+c:T:+ a5J&02+E';XNH+k4/*+%-?2/+ –! =.5>@0+>.1=+%Ym++':6)+w+EF0/.10H+ –! +=0G.12/-*/0=+U+9@*1*-$/?+ c=$2.1+O*/+8/-+!$.+E6))'H+Zg6)'+ O + C! C! C! •! 8.G0+s0D$>$@$/?+$1+/&0+909<=0+>.1=+ –! 0L$=0140=+>?+/&0+=$2/-$>5<.1+.Q+(+ –! >*--$0-+$2+6)CN)+F4*@#G.@+E*2+,*5@$1J+ *1<4$9*/0=H+ - O N H C! N H -02.1*140+2/*>$@$A*<.1+P)gM)+ ,09<=0+>.1=+4$2C/-*12+$2.G0-$A*<.1+ O O C! C! N H NH C! C! 3.2Å 3.8Å O O C! C! N C" C! N C! T0$22+/9&217+O*/5-0+8/-54/+!$.@.J?+E';;ZH+XgP(P+ O.1C9-.@$10+4$2+U+):)My+ ,-.@$107+4$2+U+Py+ ,09<=02+*1=+&?=-.J01+>.1=$1J+ •! a?=-.J01+>.1=2+.445-+>0/S001+*+ ;.1.-+*1=+!4409/.-+ –! VCazzzzzk+S&0-0+V+h+k+*-0+ /?9$4*@@?+O7+m+E8H+ –! !*4F>.10+$1+204.1=*-?+2/-54/5-0+ OCazzzzzzzzmY%+ •! V$2/*140+6:XCN:Xw+kCV+ •! %.1/-$>5/02+UNF4*@#G.@0+EU'))D+ 2G*@@0-+/&*1+*+4.L*@01/+>.1=H+ •! k@@+&?=-.J01+>.1=2+G52/+>0+ 2*<2R0=+E0$/&0-+$1/-*G.@045@*-+.-+ >?+2.@L01/H+ H N C! C O C! N H 2.8Å O C H N C O O C C! N H C! e02/-$4/0=+/.-2$.1+*1J@02++ O Ca C Ca C N H Ca H N ! " O A D AD /.-2$.1+*1J@0+=0R1$<.1+ B C ! 0D/01=0=+9.@?909<=0+4&*$1+), *+Y+'Z){+ B,C ! K.-2$.1+*1J@0+-02/-$4<.12+ A B "6 R12 R ) # R &12 # R & 6 , = E min +"% min ( + 2% min ( . $ R '*$ R ' e+ U ( R) = energy (kJ/mole) 10 8 Q.-+1.1C>.1=0=++ + +%[[[%+J-.592+ cG$1+U):'+C+):Z+Fi#G.@0+ eG$1+U+N:Z+w+ 6 methane 4 argon 2 0 3 4 5 6 7 8 -2 separation (Å) 90-G$22$>@0+),*+L*@502+*-0+010-J0<4*@@?+Q*L.-*>@0+ /.-2$.1+*1J@02+S$/&+>*=+4.1/*4/2+*-0+=$2Q*L.-0=+ e*G*4&*1=-*1+,@./+ *@@.S0=+/.-2$.1+*1J@02+.Q+/&0+ 9.@?909<=0+4&*$1+ + "+ !+ r:O:+e*G*4&*1=-*1+ |||+m3V+%mOqcOKpmO+\me+kOr3c8+ e*G*4&*1=-*1+/9&21+<=>+E';PNH+(7+;XC;+ e*G*4&*1=-*1+ G.-0+-0R10=+ T0+520+/&$2+4.1L01<.1:+ 200+a.+/9&21+?*0(.@AB.E6))NH'6g6X)Z+ e*G*4&*1=-*1+9@./+ O.1Cr@?7,-.+ 92$+ a.+/9&21+?*0(.@AB.E6))NH'6g6X)Z+ r@?+ 9&$+ &l9g##D-*?:>G4:55:20#J0-*-=#259G*/#1.1J@?9-.}-*G9:J$Q+ ,-.+ 8$=0+4&*$1+/.-2$.1+*1J@02+E-./*G0-2H+ ++++'+=024-$>02+-./*<.1+*>.5/+/&0+%!C%"+>.1=+ N H N C! H C" H N H C! C" CO H H C" CO H CO H C! H #1 = +60˚ least pop. g- #1 = 180˚ intermed. trans #1 = -60˚ favored g+ 4*1+*@2.+&*L0+4.59@$1J+.Q+G*$14&*$1#2$=04&*$1+/.-2$.1+*1J@02+ %&*F-*>*-<+h+,*@+,-.J+!$.9&?2+".@+!$.@+E6))'H(Pg'+ k@@.S0=7+-0J5@*-+2/-54/5-02+E204.1=*-?+2/-54/5-02H+ -090*/0=+),*+L*@502+$1+*@@.S0=+-0J$.12+.Q+e*G*4&*1=-*1+9@./+ ,+Y+9$/4&+E-090*/+=$2/*140+*@.1J+&0@$DH+ + =+Y+-$20+90-+-02$=50+*@.1J+&0@$D+ + 1+Y+15G>0-+.Q+-02$=502+$1+.10+&0@$4*@+/5-1+ + (!+Y+-./*<.1+*1J@0+90-+-02$=50+*@.1J+&0@$D+ +++++E1./0g+/&$2+(+$2+=$j0-01/+/&*1+/&0++ ++++++909<=0+>.1=+9@*1*-$/?+/.-2$.1+*1J@0H+ + ,+Y+=[1+ (!Y+NP){#1+ V$4F0-2.1+h+r0$27+)9":$9:"/&27;&8$<#7&#=&!"#9/074&E';P;H+ C"%$. $. e0@*<.12&$9+>0/S001+), *+*1=+=71+ #" & #) + * & #) +* & cos% ( = +0.817sin% ( + 0.045sin% ( $2' $2' $2' #" & #) + * & #) +* & d sin% ( = +2.967cos% + 0.664 cos% ( ( $2' $2' $2' D"%$. " = 360˚/ n D"%$. V$4F0-2.1+h+r0$27+)9":$9:"/&27;& 8$<#7&#=&!"#9/074&E';P;H+ $. C"%$. !$.@.J$4*@+&0@$402+ K&0+!C&0@$D+ ,Ok8+E';X'H+N(g6)XC6''+ ,*5@$1J+*1=+ %.-0?+%,b+ •! -$J&/+L2+@0~+ &*1=0=W+ •! 2$=0+4&*$1+ 9.2$<.1W+ & E!. G. E. F ,*5@$1J2+&0@$D+ e $ 4 & * - =+ " * - 2 & 7+ . 1 0+ . Q+ / & 0+ Q0S+ 2 5 -L $ L $ 1 J+ 4-?2/*@@.J-*9&0-2+ Q-.G+ /&*/+ r.@=01+ kJ0+ $1+ 2/-54/5-*@+ 4&0G$2/-?+ */+ %*@/04&7+ &*2+ 0D9@*$10=+ /.+ G0+ /&*/+ */+ /&*/+ <G0+ /&0+ %*@/04&+ J-.59+ S0-0+ $1/0-02/0=+ $1+ =0/*$@2+ .Q+ G.@045@*-+ 2/-54/5-07+ $1+ >.1=+ @01J/&2+ *1=+ >.1=+ *1J@027+ $1+ $1/0-*/.G$4+ =$2/*14027+ $1+ Q0*/5-02+ /&*/+ S0-0+ n52/+ *2+ -0@0L*1/+ $1+ *+ @0~C&*1=0=+ S.-@=+ *2+ $1+ *+ -$J&/C&*1=0=+ .10:+ p/+ S*2+ $1=00=+ /&0+ 4@.20+ *l01<.1+ /.+ 254&+ =0/*$@2+ /&*/+*@@.S0=+,*5@$1J+$1+/&0+R-2/+9@*40+/.+>5$@=+G.=0@2+.Q+ 9.@?909<=0+ 4&*$12+ /&*/+ S.5@=+ 2*<2Q?+ /&0+ 2/-$4/+ 2/-54/5-*@+ -0_5$-0G01/2+ /&*/+ &*=+ 0G0-J0=+ Q-.G+ 254&+ 2/5=$02:+ ,-.>@0G2+ .Q+ *>2.@5/0+ 4.1RJ5-*<.1+ -040$L0=+ @$l@0+ .-+ 1.+ *l01<.1+ >04*520+ /&0-0+ 200G0=+ /.+ >0+ 1.+ 100=+Q.-+/&0G+/&01:+,0-&*92+/&0?+S0-0+0L01+-0J*-=0=+ *2+ *+ =$2/-*4<.1+ Q-.G+ /&0+ /*2F+ */+ &*1=:+ 8.G0<G02+ .10+ 4*1+Q.452+G.-0+4@0*-@?+>?+4@.2$1J+.10+0?0:`+,*5@$1J2+30~Ca*1=0=+a0@$D`++ iV+V51$/A+876/>%&,./3%&?791%&/;:+E6))'H+M)gM'P(+ ,-..Q+/&0?+S0-0+-$J&/+f+"*D+,0-5/A+ •! K&0+,*5@$1J+G.=0@+ 9-0=$4/0=+*+':Xw+ -0s04<.1+ •! 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This note was uploaded on 01/03/2012 for the course BI 170a taught by Professor List during the Fall '09 term at Caltech.

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