chemsci.kku.ac.thchemsci.kku.ac.th/choosak/Olympic/theory11.pdf · Created Date: 5/24/2016 4:03:12...
19
' d6r{u' L ttfr Tcho zo16 Tho Eloyonlh Thsllsnd ChomlEty OMnpiad K6selslrt t nh.€rslv rriLdmrl ldrd.srnhiw 72n tn i( uqfu um-runs-ununsfndoi *aHzH:::"*' tor^tsaz\re,raZrA n1:[[qJ{qjutnil toatlun:eou?J1ei ni{S 1 1 nruviilurorani uyr?fl urd's mum:orani z finuruu zssg I r?41 8:30 - 13:30 u 9t E{ sodounlnflqufl fluu ao?u. tattJ: v,iroira ou
Transcript of chemsci.kku.ac.thchemsci.kku.ac.th/choosak/Olympic/theory11.pdf · Created Date: 5/24/2016 4:03:12...
' d6r{u'L
ttfr Tcho zo16Tho Eloyonlh Thsllsnd ChomlEty OMnpiad
K6selslrt t nh.€rslv
rriLdmrl ldrd.srnhiw 72n tn i(
uqfuum-runs-ununsfndoi*aHzH:::"*'
tor^tsaz\re,raZrAn1:[[qJ{qjutnil toatlun:eou?J1ei ni{S 1 1
nruviilurorani uyr?fl urd's mum:orani
z finuruu zssgI
r?41 8:30 - 13:30 u
9t E{sodounlnflqufl
fluu ao?u.
tattJ: v,iroira ou
- - ztmtltll,{lun!loallun:Joutm a:{?r ll
.sn1t[[o{n1:6aun1nflqufl
t. rioaounrnmqufifinvuuu:'u 120 nctruu fiorfluSouav 60 tolnvururiruunz. hirinriuun:roaor-rronar:riouadovrtr n1ld
2.1. {oaounlnrqufi t qn o'ruru 13 to 19 r,trir (:rrUnuavnr:rrorn)
2.2. n:corun"rnounrnvrqffi\ qn o"ruru zz urir (:rurJn)
a. rinriuuocarfiorirdoaoukiYoniixnriQraouUrvnrnlfi "a.lfiorir" uacrdoU:vnrn'ir "r,rlonar" lfiu"nriuu unlirdoaouri'ufi uac:ru:run:vorun"rnrurravn:vsum'rnoutiroltiu,tfiourfiu rrruuTfiv
:ohin::unr: t6utoaoubiri uuSou fnGuuS.iovoonornrioraoukiq. li'rfiuunhnourirurJrnnrfrrlrriura6o6o'rvr'o-nrniuutitvirrfu Inurfiuulfin:rniudouavrfiuulun:ord
I -- ! .-rilyunt tyrluu n: tltuu o tl4tJFr?Iltlasttgu 114,l t tnlou v1 a1Jn']uu'lu'laun1ru9l n'llvlnl4lotJottjuu, J.v. , I
ou'tn0u t141t1 lun:vn1un101ulvl'luu
s. Iovrtin'rurruhi'uaoliBrirorrurird'rto.:Iovrd n:fin'roroufi'rtlusi'rrarido'rrirfirfuratrluairn"rgnr*d+ia+uc@i d 4'A ed< . L6. 14'rUUlJtn50{$UU 
Fl_?
-H g
Ep E,{6.{O-=:ZEes-> i
iolr 5_FI E
fr- E
9e
Go.: ^E3,3'5
.E..i .:
E€
R-'E
E.o .E- t-{ € se6 35Ens.! n= !
xu;qEfl=.?- rEl 9*
.r::gorE
6- =9E'E
soa E oE
^EErE6E
:-.5;fE
+E'E-zats3qE3r- E-P.. E
:.26Gl ,E
.i- E
' t'.r E
+o 5 :z 9dr- E<g 3,) 5- =or 5=x E
+*o E
-E 5 \J9 -roE 8:€a2 :E E
-39^ 3" I:-rnE
qERc).:_(n 3;E
-F !fiE
Ro !"!r .E
359J Er.z
=z E"-t =* E2a t
eeF-a 9-0.E;E3eSiE Eg5
..i E-U€ ie'ii,9sE
pE
6:
Ec.-o = ^!r -E
a,sv-.=oE B
-la B
EE*z E
g6l E
_v E oi .E
a=.iEE
o
t:I
II
ltrFcl., lELIE
Eefi
IEt>IIlol>I
IIFta
L,.=
Btr e
-N.:d_; 3Eo5 Srtr:E
^oE
e = IRU T
5 oaU:<; -< sghD
=
99.- ?- zi 9E E6E
a9tio 5
a.r.i-&z FE
aEEE6oE
Hc) "-rq.g
-E
$E
(.! _Y, ,, 3
P- E
!l 6 2
^-;
eEB -., E
!E
9,.5 SEi{ ,q .:iFa +
9?-6'E
qEno E
;EBEB -s
F:a9boE-(2 3
6E -Z ."e
^CE:;d:
-' E
g." E
5:- .E
^F E Ni!'s
E*E; lr E
e
daE->'Eo'i
;5661 E-Fl tsoj
IJi E
oE6Gr.:re= : oD .;
^a B
o- E
.() *9E
0E sa 5G-
;trE
Fl= -zE-v i9A
EpEe€
g.?.:;" g
srri'gEE
<E
.9b
ee
.= v1Eq,
Fl<
6C@DF@C6
'!F
I.?e
?
cE+rE
(a
n'r:urirdurnfilDe!0n:ysr-utr6 nird u 4
hrdtod 1 (16 ncuuu)
1.1 (5 nr[[uu) nioSiatooou Fe(il) 1u;rJuioiia{auinravrv,loSiay,lurr:n ldrfluurraiuorqpa6nnr:irn:rvdGurru re(il) luar:n"rodr.:rirldlorulfi Fe(r) :?riry! i,to-fluuu1vr:Eu 0n:.rafr,roTrgrJd t ) ldar:rJ:v norrfi ldouf, uordu fi qn: uilu [Fe(c 12HsN2)3]2* o'.!6rn1i
Fe2* + 3 (1,1O-phenanthrotine ) --+ [Fe(1,10-phenanthrotine)3J2.
attn.:au
;rld t qn:Ia:lair{ro.r 1,1o-fl uuulrrAr
J-.. - , ) adiaiinJnar:nrodrlfilrf,uulo5ias'atr{nnavrv'laiiay{urr:orr{ rolo_mDlaluvlnr-or]iuror:
rfiu1on:onfiarfiu1a1o:nao1:r{ (hydroxytamine hydrochtoride) o'riru t.o mr rdoifird re(tD dororJuurl#rflu Fe(tt) u#'lrfiu t,ro-fluuulvr:f,u riruru 4.0 mL nurirunr:rfiua.r:avarufiiryloiailU 2.5 mL ornriuU:-rGrrn:rflu 'sooQ-mt oYofi"otl ro urfi udrrhar:avarun'rodrlyrrlioorrudr
fi) hJinuowofu+u{d,uorar:U:vnouris{oudyr'nrrlurendu soa nm 1nu1,{rn:Jo.ra6Jnlvr:Il[n
firnoitffvirfiu o.soo )\--'-.--.--...-.--- -----..._-_----=riryunrirnouroiuuludrolrnar:acaruurn:mu fle(l) o.1ooo mg/mL illiurn:rirl 1 d,l
rsr:'uutire,i6rdurnTu{rrfr utriaranldtsr:UUfl'tU'JE[nU?nUfl1{mU toi.lan{U o.;*L i ", -r/*L
U3uror:ar:avaru!.rsr:51! Fe( ) (mL) uousoiuuuuri 0-r ^' n''0.00 0.000 1\lLO.5O -' t.",'-- 1 O.l2O ,i.\'. -- r '.:
1.00 'r 0.2501..6 - .L
1.50 0.370 1 '^, , . 1:,' -:
2.50 0.610
1.1.1 o{ai'r'ini11'lrJlflryruornorr:rrrirrsiu Iounr:vrf;oflrilloutoiurruudryunrupil{uloraliavalu rn:E1tl Fe(il) riu mg/L uao{i6ilmi1$r{}t!,llolaGaraiuoriotiiT}nn:rv{uav riru':runrnrrurtlriutor_tg(D falr n"rod)rleD-=r!-
-i-t
.. :
- - !)n1:u1,.!1r!tn!laallun:Jfllllo a5{ri l 1
t.1.2 o{lfiuuemrlnr{a51{ro{ai:!lunour0rdauvirfisrorn re(tt) ri'u t,io-fluuulvr:6u
1.2 (7JU$uu) 6'r1uar:avaruqr'ratjr.:nr6nfirft Fe(u) uav Fe(flt) fiodla,uavarun'rotilrGurfl:i/zs.oo it lr'lylt:nn-r 0.0200 M KMnoq (1un:ns'aflrinr6oorl) il'1i?u€3.45 mL loooll Fe(l)
r'lr,runo_vgnoon0lndtrJrflu re(rD va'rornriurirar:avarulrrirrJfrffiu.rfi'daracflinvf,rdoruduu
re(rD rfirauolrirfl_y-re(tt) ravdlarlavaladtrilrlvrrvr:ouYual:aca1u 0.0200 M Kunoq 1{Gurn:rvirrirZillS mr- -
1.2.1 orqaaunr:aiohJd
Mnoa- + H* + Fe2* --+ Mn2* + Hro + Fe3*
FeY + zn ------) Fe" + zn2*
z-1.2.2 rardrurufia6lua:uta{ooouFeluar:avaru25.oomL (vrnfiuffirur,rr.il)
,11.2.3 vrnmur{uduriiuluariuo{ooou Fe(ll) luar:or''lodrr (vrniuuy'riruuill)
1.2.4 r,rrnlurtudurfl uluarf uorlooou Fe(r u) lualrer'?otj, .i
1.3 (4 nvttuu) drraunrirruanrunr:acalu ro.r Fe(oH)r = 4.5 x 10-37
(vrniuu yi,ohur,rill)
t.3.r ri'rdornr:roriuuar:avarulooou Fe(ttt) luusrhifinruuiudu o.otoo lll loulriu'nynou
1,0.r Fe(OH)3 ovsio.iUiubiar:avarufi pH arantrirfi urvirl:
t.3.2 o.uirurruur pH fivrtrhi'tooou Fe(ilt) luar:avaru ornnvnoulfluruf;nlsfl:onts,i
Fe(oH), odrrauX:n! Goulrifio'jrfilooou Fe (tl) ru6oo{rioun.j1 0.1 mg oioar:ayaru
100 mL)
- - !)nT :u?r{1,!m!t0an nlvnu!10 a:!yl u
lovrtiton' 2 (7 nyuuu)
lurJ:vlynlfioluurr finr:1{ cact, rualdu Nact rtr'aazarufiuvuacrirud.:uunuu nr:irn:rvrirariEurru CaCt, doqlu,uolzuau rinrnfltdrirto.:aralor-.lodrur 2.463 g ararurh uavrfil Narcroo(sodium oxatate) rdonnflvnou cac2o4 oonur ei{a n1:
ca'* * croo'- -----+ cac2oag
ya-rornrfun:o.lstvnou cac2o4 dtnayaruluarracarun:or-ailainlein:q H2c2o4 udrluryr:nri,:ud'riava'ru O.OIOOO M KMnOa vru'jr ldar:avaru KMnOo 1 2t.62 mL
2. 1 ( 1 nv ltuu) otduuuavoaaunr:nr:lvr tvr:nyl'1fi nfi u
2.2 (2 Artuur) oin'rurruu, iouavlouri, r.rrinto.l CaCt2'lutolatau
2.3 (4 nvltuu) tirrovraunrodrru:cnoueiru CaCt2 0.10 g rlav Nact 2.85 g rjrurava.rtr'lurlr
eQ g n.iil11o160nttdrrorar:araruruauf
(rirrauorir t<rro{;h = 1.86 'C mot'1.kg uae van't Hoff factor ljo.i CaCt2 = 3, 1,0{ NaCt = 2)
- - !)n15ll1,ll,um!loauun:Ynui'rlr Ar{?r I l
iovrddod 3 (7 nurruu)
01nrmufl1fl rirar:avaru at'* firjilrn:rfluaaqyirrorar:avaru u'* dorjrioulr,in:vualyhftllla
lflulrar = t zu qrura4fi 25 oc
flu'ir6r:aca1u M2* fin?llr{lduujduuhJ 0.36 mot/L uavn'ntitv,h{r
dinlfrfirirrflu 1.51s v alufi'irnr:ujduuurJarturi{riflrrnfidhirirhirlBuln:rio.!6r:aca1u.J v ).
tuauul.tua,in1nllaua n1vu9t 1,1,
3.1 (5 nv[[u!) orrirurrurarrirn-ntitriflrtol.fr M uav yrhuru'ir trl 6olaravrfinln
3.2 (2 ailruu) ri'rrirnr:moaolnafiourirrolu uririlduuqrur.r4irflu so 'c inrira-neitylrhki t.sos v
rit,ruorirflndlv'|fl rio'n{ur, or:gruta{aracursrfi od 25 oc (v)
Al"' +3e
Mn- +2e
Zn'' +2e
Cr- +3e
Fe'+2e
cd2* +2e'
Co'' +2e
Ni- +2e
snz'+2e'
Pb'+2e
2H* +2e'
cu2* +2e-
Hg2'' +2e
Ag +e
Au- +3e
------+ Atrrt
-----+ Mn61
--> zryty
---) Cr61
--+ Fe6y
--+ Cd61
-+ Co61
---+ Nic)
-+ sq,l
+ Pbrrt
----J Hagr
--+ Cu6y
------+ 2Hgx;
+ Asat
----+ Au61
-r.66
-1.18
-0.76
-0.74
-0.44
-0.40
-0.28
-0.25
-0.14
-0.13
0.00
0.34
0.79
0.80
1.50
rir Eo."n d 50 oc
ocliJulyirln
7
nliud{r,"urnf, laerfi n:vnlutrfi ni.rn' r r
iovrririon' 4 (4 nrlruu)
uunuflo:'siin Ni-cd ([:un'i1 tticad)'l{lurndolfiovr'nnnravorn rriu lvr:n'nffio6o u!nlnoddfiorunr:l{rruqr aur:nleirJ:v1'[durnfir zooo nfi
uunroro:'drj:rnoud'ru z ndqsaii 6o
Cd(OH)x,t + 2e -+
Cdle + 2OH' (i) El = -0.8t V
NiO(OH)ro + H2O + e ------) Ni(OH)21e + OH- (2) E3 = 0.49 V
do Eo = rird(ntilv,lrhid'n{uurn:oru d 25 oc
4.1 Q.5 ocu,uu) rdaduUrioorJ:v1 (discharge) unorfiu u*unrnoCoqlugttsrqra6oar:rJ:snou
lao:on'[tr{ ru:rvn,tnlo uavfi lrarvirln 6wir'hiuuorrno:'fi n?1!n 0.750 Ah
4.2 (1.5 nclruu) raa-rorn'l{uunrnodouuuuJ:v1udr rirh.fleirJ:voJrari (recharge) Inalfinrvualylfl10.3s0 A oudofl{l':arurun't"rlur rdohi'firJ:vlrvirrfiu uacauu6'jrfid:vf,vrBnrnlunr:lairJ:v1
rfiul gogt
nrrd{!'urnilaAr0nivd'uri ni.rd r r
iond,fla*' 5 (7 nvuuu)
rit,tuoritouri'af,u1n:lluto.inr:rio16o (standard enthatpy of formation, Artto) uav roulm:tjxlniElu (standard
"niropy, So),uolar:oirl1 ri.:nr:rli
' '
a.!uiiala'[o:rourijurfioryr6lyrrl16onfitdiuFr?1u6ulolyri,]vn.l:unlraftrifiufianriuouinaonlsridrflu
iadan1?c1uu::u1n1flrnoiu rilo!fiuufiurJfrfi3urnr:rHrlurftoruf,ao::utrfi rdu iryru (drnrr 1)
CH49 + 20267 --+ CO2q + 2H2O19
nriilAnllflalaloirnuluQnalunt: ldrJfrffiur steam reforming nlnfirylu (aunr: 2) dqtura4fi
700 - 1,100 'c uririrtirfinufla co vrtrdufiu 6rsiolriri'nlnu1{U5mol *u.", cas s# dd;d;2oo - 250 oc (aunr: a) dwi{vitrf,ufianriuoulnoonlrciuavtriufia'toTn:rourfrudusi':u
CHA@ + H2O@ -+
COld + 3Hts1
CO1rl + H2O19 --
COxq + H41
(1)
Q)
(J'
5.1
5.2
(2 ncuuu) drrirvra'wrudldornrJfr63urnr:rarrlyfrolufiafirvruluailnlr 1 ufldli1rJfrffiorlu
aun'r:d 2 rdolfitriuflalslo:rou 1 mol ovfrofl{uf,afiryrud mot
(2 nvrrru) 6'roio'lnr:uffalalorrnui?r#,iuun t kg Inuld I rJ!fiiurirurYu 601{aunr:d r rdo
rjryra"lrruvr*ld1rJrir1firfinrJfrffiurluaunr:d 2 uacriro-o co loiit,fiiliniu{1lailn1:,ir 3 oyfiq c t^ i I J-s
Inan']5uau tnoon !fl oLnotuvr.rl4rfl nfl tan:u
(2 nvuuu) rirldruflaloln:rou t rg dru6nornnruu?unlrlu?io 5.2 rflurdorvrfi.rlurJfrfiiur
rarrtrariovtpina"lqud tt.l uavdrdornr:ldua-.:.lruyr'ryiri'udusfldri, rTufirrarr.dan:Iuranaradu
c,rH, rflurd'aruir uavntruiouornnr:rrurlr.rrirhriudrraraarurvirrYu 48.0 MJlkg oylirhirfioqqtiX)
uRanlSuou looon trritur4{qlnR kg ty5d[fs:'o-\$rdttt\tot - _ itl .. /lt,ru
q
i?ril'., Jr,+.,na,fi ,lYi t',i'.,,,-rn,ru,fl ,,,flu,na.6rlr,iu-!ya.itt?oao ulnn?lnu t1$1vt140rt0
+rnrrarrdmn-r cldlrll
n't CHcs) Hzoot Cor"r Co*t Htt Orgt
Arno (u.mo[l) -74.9 -241.8 -110.5 -393.5 0.00 0.00
so (J'mot-l.Kl) 186 189 198 214 131 205
n,:ttt'{dumibe!0ntvn-uu6 nf.:nr rr 10
Iovrdtavr' 6 (18 ncuuu)
^ o - ta.fi114un [ruflarngnfl tul,onNr ideaI gas
rJ[ffi urnr:aarun-rto.r dinitrogen pe-ntoxiOe (tlzoJ rfluo1ld
2N2Os -+
4NO2 + 02
o"nr lrJA ni u i n 1i aa 1 u ei'rt o.: N2o5 liluo'lal nr :dtruo.l
rate= - --'-'j' - kllUosldt
Ioufidrnrdo"n:r k = 8.62x70'3 min'' dqruv4fi 35.0'c
ruo, drfinduarur:orfinrrJ[fiiur dimerization lriQlhl:':n15'luastihda!ala],fth+ii
2NO2 : NzOq
Inufinirnwlauqa (Kr) rvirnlu 3.68 [aurolyl-af,rolJfrffiur (A,n') rvirn"u -57.2 l/mol
dtirUfrfiiurvirJiuln:n{d Lravqruil{find as.o oc
lne,6tueiulu:vuufirfiul t'tro, 0.200 bar
(1)
(3)
l.(o. r !,n!uuu) olriru':ruraarndltinlunr:aarun-'ltor Np,
t-{6.2 W ' ncuuu) orrirur n?.luriudduqaldo Nro5 aarusY':vun uavrirurruSouavra{ No2 d
rfinrJfr ffi ur dimerization
6.3 (6 nvuuu) oln"rurruqrura4fidrird4odUrtU ruo, rfinrJfrfiiur dimerization kirioulTnl (riou
n'jr s s6 loufu a) ourJ:curoilei'irbirfi orJfr fi 3ur dimerization
T6.4 (5 ncruu) dtirrJfr ffi urlu:vuudGllnrrasqrrr.rftnd hu,iufiunmu6'u:ru,uo.ltvulr = po
iiruruluatol N2O5 = ns uavrirrJf,fiiurdqrura4{iftrirfinrJfrfiEu't dimerization o.ltduuaunr:
ruan{nr1ud'rr:rtrror:ruudnar t 1o1 rdorilauo}i o riJurnuriruluaro.! N2os drfinrJ[fiior
[?a1 1lfl1 uavou{uuaunr:uaornmudlriuii:vu'jr.lo'orrrnr:aaruoYrtol Nro, f-atUort) 6,\ dt/
- -' - ,u, l.99)0fl11n15[Y{ n?1rloul?rJ?]O.ll \dti
- - t)nTlultwrautonlJun:vnuiln a:{r lr
lovrridoyr' 7 (17 nvuuu)
cLvie6Gu (cerraf ra6o cerium(tV) oxide (Ceo2) ttuzultt:rfin drvf,or6n rirhJl{rj:clwdtdlaaruriru uju
rflu catatyst lflu antioxidant uavHallunirfi'uunorfludu tdororn ceo2 rflusl-rdloon0rou'looou'xdfi
(high oxygen ion conductor) 6lfin'nunrvrlunr:tdrfluar:6r6nlvr:lasfllurtaiir{our6rtoru{r (sotid
fuet cel.t) HlfiGurniuilpiornnl:lru1 cerium oxatate ui'o cerium hydroxide
* .ic, ^ i - a JlourlrltJaurifrvrrrnlunlfl'tio{ {ttl'rfrnfrudun:curunr:tn5uriilovrilatariouqfin::utolar: flo1t"uir
finr:r{olurnrrrniuur.r.ir{:lilnaln arnvarui6 nr:aarud'rtorar:rJ:cnout€ldoutaGriuurtui6r,tdld.,t
tfl mlurHwrsu rtuu0nlu'nJ1{41{u
CeCt3'7H2o + triethanotamine +HYl. cerium triethanotamine comptex00ngtntu
11
"."/*\\q",l' ?n, IHzC cH, 9Hz
HJ 4,. J,triethanotamine (TEA)
J *', uoo'., rn
CeO2
7.1 (11 nuuuu) rirar:tirdou cerium triethanol.amine lilfirJ:v1 $acfi conformationaI isomer
aranl:irn:rc# rororordrj:vnouluar:tirdouuaoro'rnr:rr (airudrv6orfluoonitou)
51u Ce C H N CI
%?a 43.56 22.39 3.73 4.35 11.04
I .t.l olufiuunr:o'or5ur6t6nn:ouuuutjo (abbreviated etectron configuration) tlolfitiurlooouluar: Gufru (cecLs.7 Hzo) dl{rniuuar:rJ:v nou[fi .idou
7.1.2 o{L[an.ln']l]1'r{'l{rJraqalo{61:rt{doud
7.1.3 ar:rfildoufiir'or:rai'ru ce : tigand rflurvirln
7.1.4 olrduuln:.rair.lto.l tER rdom'rrarirdrfluiunur{ uavtt'uu':rnardou:ousiruu rto.lcoordinatins atom ufoiluao$:vo.up?Blpj
l,flfl rq ," p/r,*4 ) |F.-
7.t.5 uatoonfi rntiuuavra'uInooifi rut'uro16riuuluar:rildolrfl urvirln
7.t.6 o{Rao{ conformationaI isomer dnrn'irtafiu:uasrflutrflrimlvuoto.i61:t8.rdou
cerium triethanotamine nSou:vudo: Ti{t:$''rnnfn
7.t.7 6tiuil nr:tdtsu5ooaiir'auuu'tolun1iai1!fi!6crYuAunuri uavfialrifiruiry6nuuulo
nl:ud{!-umfilo6! n:vn"utr6 aird rr
7.2 (6 nvruu) rfiorzurar:rfirdouso{firiurJ ovr{duulurflu ceo, rdolorn6unuriaalueiil{ilrrnar:U:cnou CeO, fiurjrurrad (unit cett) d'luao.l
drraunirfitooou
rce4+ = 0.97 A
td2- = 132Anrruvuru utal ceo, = 7.65 g.^t
7.2.1 orriru'lruylJ:vfiyBnrunr:u::oovnouluyilrurgad (packing efficienry) ro.t Ce02
z.z.z lu1n:rafr{tor Ceo2 rarlnooifirudutron ce uac o rflurvirln
7.2.3 udorio Gd3*, sm3* uia zr2* rJiurrurdnfouaflun:curunr:rniul ceo, ovld
MxCel-yO2-6 (M = Gd3*, Sm3* uio Zr'.*); a d dd Jh
' .
t.: tuu r.ra nt t: uYt tI auu: ru
(rfiosr'rfii - crystat defect) dululn:lair.: rirl# Mrce,-xo2-6 rflusYrrir o2- looouldd
ii.rdu 6uirtrJri:rqndrf,u6r6nlvr:larilurrarir{ornfi.rki dr cd3* uiruvrudn'rurad.l
Lranfi{ (tattice site) ro.: ce4* luln:la5r.: ceo2 4 st"tul,rill ovrfin o4ygen ur..n.y d,doir uyrjfl uIn:lair.r uanfi rto.r ce02
72
n'r:uri!ilurafia6!0n:vri'wr6 nfid r r t3
iovrridovi 8 (7 acuuu)
,o" )
tlro[H1lauv M
19.98% Iourr?a
1J1? O{Unn5U1- 9.''6
r! {r I
kiar:r.raluo$arava_onlrriuaclauvujoiooqlrr{ lnufiIa1y!lo:iosdrgizuauoqjdrar:arauriruru 1.00 nir 1 rA allava,ru nin n duifn: nuriardryo,)d'rrnau
Iar,lcoonltri + allasalun:n A ------) nvnourl? + H20gqo 1
Iar,tynJoioonlse{ + aliavalun:o A ------) nvnour.'l? + 1H2o2 ,\__-/
u,'on:orr,rnouoonudlrfilar:avaru xt (un:o) durnrfiuno ovrfio t, du o-.:rJfrffiur
2 l-1*2 excess + H2O21oo1 + 2 H* bq) ------+ il4*1. + Z tlrO1,1,.._ _,
a- l elvrry:nrarUiurru t, firfinfiuoieuar:avaru Na2S2o3 tdldu 0.10 u l{tEurn: 23.60 mL
r, @or'- -r Sqo62- + 2t
8.1 (3 nv[[ut.l) rirdrurulua,uo.l Hro,.----E--
0{n'tu?fu1,l'1u?aoun0ut0{tauY M
driordutualnr: (2 MrrYruihu'luluaro{ar.ryujoioontrsi
(1)
Q)
(3)
(4)
\.E(?ar,*uu) t'l fio Taravrinln r{r6uuenirollar,rvoants0irtaclal,rvuJoioontsei?al n,tInul{a'rya'nrgitolor qlunr :rr or n uyular,lv M
c-.\(fiv*yy) nc nourr:drfi oduluaun'r: (1 ) uav (2) 6oa1:1n uavfi #rylndrurudn:-u
m:[ti!r,1]rnfi oe!0n:crYutr6 n:ir:' r r t4
Iovrtidont 9 (6 ayuuu)
rirorq z tiodlJfr ffi urrnfi u'':trJ ovblna-r.lrurioun.jtJ!fiSurfi:rndaSurn
luju 6rfi ulriulalo:rourfi nrJfr fiiulnfi rild
Li + VzH2 -)
LiH + 90.4 k/mot Li
c. .A.. a - -truuu0n:u'ru?[naul0vtnnn{u
ILi + lH ----) 21He
9.1 (4 nvruu) n{u1'jrov0iol'W Li dfiIanillililAffiurnTt n, udrkina'l.lruryirrYunr:'l{ ri r luatu
(1)
tl0tttJ0
nr:rfin{frfiiuritn6ui
dryun uraro.rounT noirll (r,trjru amu) ri'.ld
]Li =7.01600 lH =1.00728 ! He = 4.00260
lou t tr,tev = 7.602x lo-13 J !!av 1 amu = 931 Mev
*5 " h'#ur "rldg.2 (2Fwrw) rdo0.r !!cr oiru:Tra'uoarir/o'ld
X + Y +lH + 7ln
!!v o+fiuufrrga"nunlii'rrnduitororq x uac y Ioul{drga"nuniro.roronrumr:r{orn
rJY+J-,P--1/Jt / 't tt, v
rL' X sz." it
2llcr + 2!He
x- r * "l
Q)
?uo1E Y r?ilnjli.idfifrr z orlnrn udrujduuriju
n1:ud{tiurf,filoe! n:vo'utr6 aild rr
Probtem 10 (11 points)
The Robinson annutation conslsts of two steps, which are the Michael addition and the
atdol condensation. These two steps can be performed under either acidic or basic
condition. The Robinson annutation can be used to synthesize the wetand-Miescher ketone
from methyL vinyl ketone (1) and 2-methyt-1,3-ryctohexanedione (2). This weland-Miescher
ketone is used in the syntheses of many steroids possessing important biotogical properties
and its enantiopure compound can be prepared using L-protine (4) as a chirat catatyst as
shown betow.
15
oAon(catalvst)
solvent, O72-750C,1 i
Michael addition
\*AcorHH4(catalyst)
>solvent, rl,
120 h
aldol condensation
10.2
10.3
enantiopure VVieland-Miescher ketone
56.8% (on a 100 g scale)
10.1 (1 point) From the synthesis shown above, write structural formuta of the nucteophite'
which is derived from 2, in the Michael addition'
(1 point) Assign the absotute configuration at positions a and b of intermediate 5'
(lpoint)WhatwoutdbethefinalRobinsonproductfromthereactionshownbelow?
Draw both stereoisomers A and B'
NaOEt, EIOH KOH, H2O , A + B100 0c
Michaeladdition aldolcondensation
10.4 (2 points) Draw the mechanism of the Michaet addition in question 10'3
10.5(lpoint)Fromquestionl0.3,whatwouldbethefina|.RobinsonproductifcompoundT
is treated with lithium diisopropytamide (LDA) in THF at -78 oC instead of NaoEt in
EtOH?
["4 l-"d5
a+oA
o'..--\U
7
(oA
I
nrldidumilo6!0n:vn"urfi nirr' r r
10.6 (2 points) when a mixture of compounds A and B is treated with NH2NH2 fo(.owed byKoH (heat), compounds D and E are obtained. These products can then undergo ahydrogenation reaction. Draw at[ possibte stereoisomers resutting from thehydrogenation of compounds D and E
10.7 (2 points) Draw chair conformers of att products from question 10.6. lndicate1,3-diaxiat interactions of the methyl. group in each conformer.
10.8 (1 point) What are the stereochemical retations (identicat, enantiomers, diastereomers)of the fottowing compounds?
10.8.1 A and B
10.8.2 Products from question 10.6
t6
att
n'Furi{n"urn!'b6ri0n:vniutr6 aird r r
Problem 11 (12 points)
Give the most possibte structures of compounds A - H in the boxes provided in the schemebetow, and suggest an exampte or name of reagents W - Z.
(Note : 2,4-DNP = 2,4-dinitrophenythydrazine, MW = moLecutar weight)
17
A
excess I pd-CH2 I
x
ceHrz
Baeyer's test
brown precipitate
I
2,4-DNP I
+yellow precipitate
AgNo3 pale yellow- EIOH- PreciPitate
(MW = 100)
t,
1)
2)
PPh3 ,/-rt/
Co- prrJc
G
ab.xon l
reflux I
Brz
+ OPPhs
6^pn)eA
heat
c
o
:l
n1fl n;w1J miiloarrtn:cri'utrfi ni.rd r r
Probtem 12 (5 points)
vancomycin is the gl.ycopeptide antibiotic, which is onty given to patients when atl othertreatments fai[. This compound is biosynthesized via the intermediate shown betow.
OH
18
12.1 (3 points) oral circte
An intermediate of Vancomvcin i . )ro 1r^r q crr;, (X) \o i-),ra\<, a:u (f nu4 6("d
'l \aror'rrL
'rin the above structure. How many
kinds of amino acids are there in the above structure with consideringstereochemistry?
F\schr/12.2 (2 points) From the above structure, draw fisher projections with correct configurations
of a[[ amino acids containing on[y two chira[ carbons.
HOo"
Probtem 13 (3 points)
Vancomycin inhibits the biosynthesis of ce[[ watl by binding to theN-aryl-o-Ata-o-Ata termini of peptidoglycan afd its precursor Lipid [. This binding occursthrough five hydrogen bonds as dash lines {6 shown betow currentty, the emergence ofvancomycin resistance is observed due to the biosynthesis of the /V-ocyl-o-Ala-D_Lactateinstead of the N-oqrzl-o-Ala-o-Ata.
o
te-
(2 points) From the given information, what happens to the hydrogen bonds when theterminus of peptidogtycan is reptaced with;.LactatgJ
(1 point) ls the position indicated by the anow acidic or basic? Give a reason?
o
-r,,(tOH
DJactate Vancomycin
OH
t3.1
I
nr:lirn"umfi air0n:co"wr6 ailyt r r
