THI OLYMPIC HA HC SINH VIN TON QUC NM 2003 Phn Ha i Cng v V C Khi A Thi gian: 90 pht Ngy thi:

23 4 2003 Cu 1: 1) Trnh by cu to ca phn t CO theo phng php VB v phng php MO (v gin nng lng). Cho ZC = 6; ZO = 8. 2) So snh nng lng ion ha gia cc nguyn t C v O, gia phn t CO vi nguyn t O. 3) M t s to thnh lin kt trong cc phc cht Ni(CO)4 v Fe(CO)5 theo phng php VB v cho bit cu trc hnh hc ca chng. Cho bit ZFe = 26, ZNi = 28. 4) Tnh nhit ca ngn la CO chy trong hai trng hp sau: a) Chy trong oxy tinh khit (20% oxy v 80% nit theo th tch) b) Chy trong oxy tinh khit Cho bit lng oxy va cho phn ng, nhit lc u l 25oC. Entanpi chy ca CO 25oC v 1atm l 283kJ.mol-1. Nhit dung mol chun ca cc cht nh sau: Cop (CO2, k) = 30,5 + 2.10-2T Cop (N2, k) = 27,2 + 4,2.10-3T Cu 2: Cho cc s liu sau 298K: Ag+(dd) N3-(dd) K+(dd) AgN3(r) KN3(r) o -1 G tt(kJ.mol ) 77 348 -283 378 77 1) Xc nh chiu xy ra ca cc qa trnh sau: Ag+(dd) + N3-(dd) AgN3(r) K+(dd) + N3-(dd) KN3(r) 2) Tnh tch s tan ca cht in li t tan. 3) Hi phn ng g xy ra khi mui KN3 tc dng vi HCl c. Cu 3: Brom lng tc dng c vi H3PO3 theo phn ng: H3PO3 + Br2 + H2O H3PO4 + 2H+ + 2Br1) Tnh hng s cn bng ca phn ng 298K 2) Tnh th in cc chun Eo(H3PO4/H3PO3) nu bit Eo(Br2/2Br-) = 1,087V 3) Tnh th in cc chun Eo(H3PO3/H3PO2) nu bit Eo(H3PO4/H3PO2) = 1,087V 4) Hy cho mt v d c th v tnh kh mnh ca dung dch H3PO2. 5) Vit cng th cu to ca cc phn t H3PO2, H3PO3 v H3PO4. Cho bit cc s liu sau 298K: H+(dd) H3PO4(dd) Br-(dd) H3PO3(dd) Br2(l) H2O(l) Hott(kJ/mol) 0 -1308 -141 -965 0 -286 o S (J/mol.K) 0 -108 83 167 152 70 Cu 4: Cho bit cc th in cc chun: Eo(Cu2+/Cu) = 0,34V; Eo(Cu2+/Cu+) = 0,15V; Eo(I2/2I-) = 0,54V. 1) Hi ti sao ngi ta c th nh lng Cu2+ trong dung dch nc thng qua dung dch KI? Cho bit thm rng dung dch bo ho ca CuI trong nc nhit thng (25oC) c nng l 10-6M 2) S dng tnh ton xc nh xem Cu c tc dng c vi HI gii phng kh H2 hay khng? 3) Mui Cu2SO4 c bn trong nc hay khng? Gii thch.

Phn Ha Hu c Khi A Thi gian: 90 pht Ngy thi: 24 4 2003 Cu 1: 1) Nh my kh Dinh C x l kh thin nhin thnh hai sn phm: kh ha lng cha trong cc bnh thp v kh cung cp cho khu in - m Ph M. a) Hy cho bit thnh phn ha hc chnh ca mi sn phm . b) V sao khng sn xut ch kh ha lng. 2) Di y cho bit nhit v entanpi ca cc phn ng thun (t tri sang phi) Phn ng H(kJ) 2CH4 CH4 + 2O2 CH4 + 1/2O2 CH4 + H2O CO + H2O a) b) c) d) e)
1500oC 500oC 900oC 900oC 900oC 400oC

C2H2 + 3H2O CO2 + 2H2O CO + 2H2 CO + 3H2 CO2 + H2

+380,4 (1) -890,0 (2) -33,4 (3) +204,8 (4) -46,0 (5)

CH3OH -110,8 (6) CO + 2H2 sn xut axetilen theo (1) v sao ngi ta thm mt lng nh oxy vo hn hp phn ng? c cht u cho sn xut metanol theo phn ng (6) ngi ta nhit phn hn hp metan v hi nc theo phn ng (4). V sao trong sn xut ngi ta ly t l mol CH4 : H2O = 1 : 2 m khng phi l 1 : 1? Hn hp sn phm thu c gm nhng kh no? Hy vit phng trnh phn ng ca ankan nhit xp x 900oC vi oxy v vi nc. Theo d n nh my phn m Ph M, hydro c sn xut t kh thin nhin. Trong cc phn ng to ra hydro cho trn, nn s dng nhng phn ng no?. Khng s dng nhng phn ng no?, v sao? C hn hp CO + H2 (sn phm phn ng (3) v (4)). Hy ngh phng php tinh ch H2 c th a vo phn ng vi N2 to kh NH3.

Cu 2: 1) Ngi ta tin hnh cc phn ng sau y xc nh cng thc cu to ca hp cht thm A (C9H10O): Oxy ha mnh cht A vi KMnO4 m c thu c hai axit C7H6O2 v C2H4O2. Cho A phn ng vi metyl magie bromua ri thu phn thu c ancol bc ba (B) c mt nguyn t cacbon bt i. a) Vit cng thc cu to v gi tn A. b) Hy cho bit gc quay mt phng nh sng phn cc ca ancol B bng 0 hay khc 0, v sao? 2) Cho A tc dng vi metyl iodua d trong mi trng baz mnh ngi ta c lp c C (C11H14O). Hy cho bit tn c ch phn ng. Vit cng thc cu to v gi tn C. 3) Cho ancol B phn ng vi H2SO4 c nng thu c sn phm chnh l E (C10H12). Dng cng thc khng gian thch hp biu din c ch phn ng to thnh E v gi tn E.

OLYMPIC HA HC CC TRNG I HC VIT NAM LN TH HAI ,2004 THI PHN C S V HA HC V C, BNG A Thi gian: 180 pht lm bi, khng k thi gian pht Th sinh ch c dng bng HTTH v my tnh c nhn b ti Cu I: 1) Khi chiu nh sng c di sng 205,0nm vo b mt tm bc kim loi, cc electron b bt ra vi tc trung bnh 7,5.105 ms-1. Hy tnh nng lng lin kt theo eV ca electron lp b mt (100) ca mng tinh th bc. Cho me = 9,11.10-28g; h = 6,626.10-34 J.s; c 3.108 ms-1. 2) p dng biu thc gn ng Slater, hy tnh (theo n v eV): a) Nng lng cc electron phn lp, lp v ton nguyn t oxy (Z = 8) b) Cc tr nng lng ion ha c th c ca oxy. Cu II: 1) Vi thnh phn [Cr(H2O)2(NH3)2Br2]+, ion ny c 5 ng phn hnh hc; trong mt ng phn hnh hc li c hai ng phn quang hc; tt c cc dng ng phn trn u c cu to bt din (tm mt) u. a) Hy vit, v cng thc cu to ca mi ng phn trn. b) p dng thuyt lai ho hy gii thch hnh dng . 2) Ion phn t H3+ c J.J.Thomson pht hin t 1912, ti 1978 M.J.Gailard xc nhn H3+ c cu to tam gic u, c vai tr quan trng trong ha hc thin th. p dng phng php gn ng MO Huckel hy: a) Lp nh thc th k cho h H3+ hnh tam gic u. b) V gin nng lng ca h. c) Biu th nng lng lin kt theo tch phn , ca H3; H3+; H32+; H3Cu III: Trong cng nghip NH3 c tng hp theo phn ng sau: N2(k) + 3H2 2NH3(k) 1) Da vo quy tc pha ca Gibbs tnh bc t do( bin ) ca h cn bng trn. Ga tr thu c cho ta nhng thng tin g v h cn bng. 2) Hy cho bit nhng iu kin thc hin phn ng trong cng nghip v chng c ph hp vi nguyn l chuyn dch cn bng Le Chartelier khng? Gii thch. 3) Dng hn hp ban u theo t l s mol N2:H2 = 1 : 3 thc hin phn ng. a) t a = PNH3/P, trong PNH3 l p sut ring phn ca NH3 v P l p sut chung ca hn hp trng thi cn bng. Thit lp cng thc lin h gia a, P v KP. b) Tnh a 500oC v P = 300atm, bit rng nhit ny th KP = 1,5.10-5. T tnh hiu sut chuyn ha ca N2 (hoc H2) thnh NH3 khi cn bng. Nu thc hin phn ng P = 600atm th bng bao nhiu? So snh hai trng hp v gii thch ti sao trong thc t ngi ta ch thc hin phn ng khong 300atm. Cu IV: 1) Cacbon 14 phn r phng x theo phn ng sau: 14 14 0 6 C 7 N + 1 e Thi gian bn r l 5730 nm. Hy tnh tui ca mt mu g kho c c phng x bng 72% phng x ca mu g hin ti 2) Vng l kim loi rt km hot ng, khng b oxy oxy ha nhit cao nhng n li b oxy khng kh oxy ha trong dung dch xianua, chng hn kali xianua ngay nhit thng (phn ng dng trong khai thc vng). Hy vit phng trnh phn ng v bng tnh ton chng minh rng phn ng xy ra c 25oC v pH = 7. Cho bit cc s liu sau 25oC: O2(k) + 4e + 4H+ 2H2O Eo = 1,23V

Au+ + e Au Eo = 1,70V [Au(CN)2]- Au+ + 2CN2-1 = 7,04.10-40 (2-1 l hng s in ly tng cng ca ion phc) O2 trong khng kh chim 20% theo th tch, p sut ca khng kh l 1atm. Cu V: chun hm lng Cl2 trong nc sinh hot ngi ta thng dng dung dch iodua, chng hn KI. 1) Tnh Go v hng s cn bng K ca phn ng gia Cl2(k) v 3I- dung dch 25oC. Bit: Cl2(k) + 2e 2ClEo = 1,36V I3 + 2e 3I Eo = 0,54V 2) Khi trong nc c mt cc ion Cu2+ chng cn tr s nh phn. Gii thch bng tnh ton. Cho bit: Cu2+ + e Cu+ Eo = 0,16V -12 Ks(CuI) = 10 3) Thit lp phng trnh: 0 ECu 2 + / CuI = f ( ECu 2 + / CuI , Cu 2 + , I ) 4) Tnh hng s cn bng K ca phn ng gia 2Cu2+ v 5I- 25oC v tnh nng ca cc ion khi phn ng trng thi cn bng, bit rng nng ban u l [Cu2+]o = 10-5M v [I-]o = 1M Cho F = 96500C/mol; R = 8,314J.mol-1.K-1.

][ ]

Mn thi: Ha hc hu c Thi gian lm bi: 180 pht Cu I: 1) Thc hin dy bin ha sau: o + o ,t 2 2-metylpropanal HCN A NH 3 B H 3O C Ac C7 H11O2 N ,t O 2) Hon chnh cc phng trnh phn ng v gi tn sn phm: a) Xiclopentadien + HCl kh: b) Pent-1-en + NBS, a,s c) Hexa-1,3,5-trien + Br2 (1: 1) d) 1-(Brommetyl)-2-metylxiclopenten, un nng trong CH3OH Cu II: Hp cht A(C6H12N2O2) quang hot, khng tan trong axit long v baz long, phn ng vi HNO2 trong nc to thnh B (C6H10O4). Khi un nng B d dng mt nc chuyn thnh C (C6H8O3). Hp cht A phn ng vi dung dch brom v natri hydroxit trong nc to thnh D (C4H12N2), hp cht ny phn ng vi HNO2 khi c mt axit clohydric cho metyletylxeton. 1) Hy xc nh cng thc cu to ca A, B, C, D v gi tn cc hp cht to thnh. 2) Hp cht A c th c cu trc nh th no? Dng cng thc Fis m t. Cu III: 1) Trong khu cng nghip lc ha du tng lai, d kin c c nh my sn xut PVC. a) Hy ngh hai s phn ng lm c s cho vic sn xut vinylclorua t sn phm crackinh du m v NaCl. b) Hy phn tch cc u, nhc im ca mi s , nu cch khc phc v la chn s c li hn. c) Trng hp vinylclorua nh xc tc TiCl4-Al(C2H5)3 s thu c PVC iu ho lp th c bn c nhit cao. Hy cho bit trong mch polime y c trung tm bt i khng?. Vit cng thc lp th mt on mch polime y. 2) T toluen hy vit phng trnh iu ch phlorogluxinol (1,3,5-trihidroxibenzen) 3) Hy tng hp axit glutamic t axit -xetoglutaric. 4) Hy tng hp prolin t axit adipic. Cu IV:

1) Phn ng ca ancol anlylic vi nc clo to ra C3H7ClO2 (A). Phn ng ca anlyl clorua vi nc clo th to ra C3H6Cl2O (B). A v B khi ch ha vi dung dch NaOH u to thnh glixerol nhng A to thm sn phm C3H6O2(D). B to ra sn phm ph C3H5ClO (E). Trn ph hng ngoi ca D v E u khng c vn hp th vng 1500 1800 cm-1, nhng ph ca D c vn hp th mnh v t 3100 3400 cm-1 cn ph ca E th khng c: a) Vit phng trnh phn ng to thnh A, B v cho bit tnh quang hot ca chng. b) A c 2 nhm OH, hydro nhm OH no linh ng hn. c) Xc nh cng thc cu to ca D v E. d) D, E c to thnh t A v B tng ng nh th no, c quang hot khng? 2) T du m, ngi ta tch c cc hydrocacbon A(C10H16); B(C10H18) v C(C10H18). C ba u khng lm mt mu dung dch brom v ch cha C bc hai v ba. T l gia s nguyn t CIII : s nguyn t CII A l 2 : 3; cn B v C l 1 : 4. C ba u ch cha vng 6 cnh dng gh. a) Hy xc nh cng thc cu to v vit cng thc lp th ca A, B v C. b) So snh nhit nng chy ca A, B, C v nu nguyn nhn.

Olympic cc Trng i hc Vit Nam ln th ba, 2005 thi phn Ha c s, Bng A (180 pht lm bi, khng c dng ti liu, c dng bng tun hon v my tnh b ti) Cu I: L thuyt lng t d on c s tn ti ca obitan ng ng vi s lng t ph l = 4 (g l k hiu ca s lng t ph n = 4). 1) Hy cho bit s electron ti a m phn lp ng c th c 2) D on sau phn mc nng lng no th n phn mc ng. 3) Nguyn t c electron u tin phn mc ng ny thuc nguyn t c s th t Z bng bao nhiu? Cu II: 1) Hy cho bit cu hnh hnh hc ca phn t v ion di y, ng thi sp xp cc gc lin kt trong chng theo chiu gim dn. Gii thch. a) NO2; NO2+; NO2-. b) NH3; NF3. 2) So snh momen lng cc gia hai phn t NH3 v NF3. Gii thch. 3) Thc nghm xc nh c mome lng cc ca phn t H2O l 1,85D, gc lin kt HOH l 104,5o, di lin kt O H l 0,0957 nm. Tnh ion ca lin kt O H trong phn t oxy (b qua momen to ra do cc cp electron ha tr khng tham gia lin kt ca oxy) Cho bit s th t Z ca cc nguyn t: 7(N); 8(O); 9(F); 16(S) 1D = 3,33.10-30 C.m in tch ca electron l -1,6.10-19C; 1nm = 10-9m. Cu III: Silic c cu trc tinh th ging kim cng vi thng s mng a = 0,534nm. Tnh bn knh nguyn t cng ha tr ca silic v khi lng ring (g.cm-3) ca n. Cho bit MSi = 28,086g.mol-1. Kim cng c cu trc lp phng tm mt (din), ngoi ra cn c 4 nguyn t nm 4 hc (site) t din ca mng c s. Cu IV: loi tr cc ion NO3- trong nc (cc ion NO3- c mt trong nc xut pht t phn bn) c th kh n thnh NO2- bng cch cho i qua li c cha bt Cd. 1) Vit na phn ng ca hai cp NO3-/HNO2 v HNO2/NO trong mi trng axit. Chng minh rng HNO2 b phn hy trong mi trng pH = 0 n 6. 2) pH = 7, nng NO3- l 10-2M. Vit phn ng gia Cd v NO3-. Hi NO3- c b kh hon ton 25oC trong iu kin ny khng? Tnh nng NO3- cn li trong nc khi cn bng. 3) Tnh th kh (th oxy ha - kh) chun ca cp NO3-/NO2- pH = 14 v 25oC Cho bit cc s liu sau 25oC: Eo(NO3-/HNO2) = 0,94V; Eo(HNO2/NO) = 0,98V; Eo(Cd2+/Cd) = -0,40V; Ka(HNO2) = 5.10-4; Ks(Cd(OH)2) = 1,2.10-14. Cu V: Ion Fe(SCN)2+ c mu nng bng hoc ln hn 10-5M. Hng s in li ca n l 10-2. 1. Mt dung dch cha vt Fe3+. Thm vo dung dch ny mt dung dch KSCN 10-2M (coi th tch khng i). Xc nh nng ti thiu ca Fe3+ dung dch xut hin mu . 2. Mt dung dch cha Ag+ 10-2M v Fe3+ 10-4M. Thm dung dch SCN- vo to kt ta AgCN (coi th tch khng i). Xc nh nng Ag+ cn li trong dung dch khi xut hin mu . Bit TAgSCN = 10-12 3. Thm 20cm3 dung dch AgNO3 5.10-2M vo 10cm3 dung dch NaCl khng bit nng . Lng d Ag+ c chun bng dung dch KSCN vi s c mt ca Fe3+. im tng ng (khi bt u xut hin mu ) c quan st thy khi thm 6cm3 dung dch KSCN 101 M. Tnh nng ca dung dch NaCl. Cu VI:

Cho phn ng: 2NO(k) + O2(k) 2NO2(k) vi tc v = k[NO]2[O2] Hai gi thit ra: 1) Phn ng l n gin. 2) Phn ng c c ch nh sau: 2NO(k) N2O2(k) (a) N2O2(k) + O2(k) 2NO2(k) (b) Thc nghim xc nh rng khi tng nhit th tc phn ng gim. Hi gi thit no ng? Gii thch. Cu VII: C th ho tan hon ton 100mg bc kim loi trong 100ml dung dch amoniac nng 0,1M khi tip xc vi khng kh c khng? Cho bit nguyn t khi ca Ag = 107,88; hng s in li baz ca amoniac l Kb = 1,74.10-5; cc hng s bn ca phc [Ag(NH3)i]+ tng ng l: lg1 = 3,32(i = 1) v lg2 = 6,23(i = 2). Cc th kh (th oxy ha - kh) chun 25oC: Eo(Ag+/Ag) = 0,799V; Eo(O2/OH-) = 0,401V. p sut ring phn ca oxy trong khng kh l 0,2095atm. Phn ng c thc hin 25oC. MN HA HU C. BNG A Thi gian lm bi: 180 pht Cu I: 1. Vit cng thc Newman v cng thc phi cnh (dng nt m, nt chm ca cc hp cht
H H3C HO C C H CH3 OH H Cl Br C C Cl H Br Cl CH3 H H Br CH3 Cl H CH3 CH3

(II) (I) (III) sau): 2. Vit cc ng phn lp th ca 1 metyl 2,3 dicloxiclopropan. 3. Dng cng thc cu to hon thnh s phn ng sau:
Cl 2 , as (1) Cl 2 , Fe ( 2) KOH / EtOH ( 3) Mg / ete ( 4) 1) EtMeCHCHO 2 ) H 3O + (5)

(IV)

H OH

n C3 H 7C6 H 5 B C D E F Cc phn ng u xy ra theo t l 1 : 1, cc cht t B n F u l sn phm chnh. Vit k hu hoc gi tn c ch cc phn ng (1); (2); (3); (5). Vit tn gi hp cht F v cho bit s ng phn lp th ca F. Cu II: 1) Hp cht X (C10H16) c th hp th ba phn t hydro. Ozon phn kh ha X thu c axeton, andehit fomic v 2 oxopentadial. a) Vit cng thc cu to ca X tho mn tnh cht trn. b) Hydrat ha hon ton 2,72g cht X ri ly sn phm cho tc dng vi I2/NaOH thu c 15,76g kt ta mu vng. Dng cng thc cu to ca cc cht X vit cc phng trnh phn ng (ch dng cc sn phm chnh, hiu sut coi nh 100%, C = 12; H = 1; O = 16). 2) T benzen v cc ho cht v c cn thit khc vit s phn ng iu ch naphtalen bng 5 giai on. 3) T 1 amino 1,2 diphenylpropan hy iu ch 1,2 diphenylpropen (c s dng cc ha cht cn thit). Cu III: 1. Hp cht Y (C6H9Obr) phn ng vi metanol trong mi trng axit sinh ra Z (C8H15O2Br). Cho Z phn ng vi Mg trong ete khan sau cho phn ng tip vi andehit

a) b) a) b)

fomic thu c cht L. Thy phn L trong mi trng axit thu c M. Dehydrat ha M thu c 2 vinylxiclopentanon. Hy xc nh cng thc cu to ca Y v vit cc phng trnh phn ng. Nu mun iu ch M i t Y, c nht thit phi qua cc giai on nh trn khng?. V sao? 2. Cho bit cng thc cu to v gii thch s to thnh sn phm trong cc phn ng sau: N axetylalanin + SOCl2 C5H7NO2 + Tos NH CH2COOCOOC2H5 + NaOH C18H18N2O6S2 +

 THI OLYMPIC HA HC SINH VIN TON QUC 2006 THI PHN HA I CNG V C PHN TCH Thi gian lm bi : 180 pht Cu I. Hm sng 1s ca nguyn t hiro nh sau : e 3 a o r l khong cch tnh t ht nhn , ao l bn knh Bohr. Hi : 1. Mt xc sut c mt electron v tr no l ln nht ? 2. Xc sut pht hin electron khong cch r no l ln nht ( xc sut theo bn knh ) Cu II. Fe kt tinh di dng lp phng tm mt vi thng s mng l a : 1. Tnh s hc (l) trng tm mt v bn mt thuc v mt mng c s . 2. Xc nh bn knh R ca Fe , bit rng khi lng ring ca Fe l = 7,87 g.cm-3 3. Gang l hp kim ca Fe cha mt lng nh C . Hi carbon vi bn knh r = 0,077 nm c th chui c vo cc hc 8 mt v 4 mt ca mng Fe nhng khng lm bin dng tinh th Fe khng ? Cu III. 700oC hai phn ng sau xy ra song song : CH 3COOH CH 4 + CO2 CH 3COOH CH 2 = C = O + H 2O 1s = 1
r ao

k1 = 3,5 s 1

k 2 = 4,5 s 1 k l hng s tc CH 3COOH ban u phn hy theo c hai phn ng . 1. Hi cn bao nhiu thi gian 90% 2. Tnh khi lng CH 4 v CH 2 = C = O to thnh t 100 g CH 3COOH ban u . Cu IV. 1. Ion [Mn(CN)6]3- c 2 electron khng cp i . Ion [MnBr4]2- c 5 electron khng cp i. Trong ion [Ni(CN)4]2- tt c cc electron u cp i. Da vo thuyt lin kt ha tr ( thuyt VB ) , hy vit cu hnh electron di dng lng t ca cc ion phc trn , cho bit kiu lai ha v cu hnh hnh hc ca chng . 2. Khi trng phim en - trng , lng d AgBr c loi khi phim m bn bng dung dch Na2S2O3 do to thnh ion phc tan [Ag(S2O3)2]3- . Hy tnh tan ( mol.l-1 ) ca AgBr trong dung dch Na2S2O3 1,0 M . Cho bit ZMn = 25 . ZNi = 28 , tch s tan Ks ca AgBr l 5.10-13 v hng s to phc 2 ca ion [Ag(S2O3)2]3- l 4,7.1013 Cu V. Chun V = 20 ml dung dch FeSO4 nng C mol.l-1 bng dung dch hn hp K2Cr2O7 + H2SO4 vi nng K2Cr2O7 l C = 4,0.10-3 M . im tng ng t c khi dng ht V = 12,0 ml dung dch hn hp trn . 1. Tnh hng s cn bng K 25oC ca phn ng xy ra . 2. Xc nh nng FeSO4 . 3. Gi E l th in cc Pt nhng vo dung dch chun . Biu th E = f(V) vi V l th tch (ml) ca dung dch hn hp K2Cr2O7 + H2SO4 thm vo pH = 0 vi 0 < V < 12,0 ml. Tnh th E ca in cc khi cn bng ( khi V = 12,0 ml ) o o Cho bit : E Fe 2 / Fe3+ = 0,77 V v ECr2O7 2 / Cr 3+ = 1,33 V

B. PHN HO HU C ( Bng A ) Cu 6. ( 2.5 im ) Cho s chuyn ho sau :

Vit cng thc cu to ca cc cht A, B, C, D, E, F, G, H, X, Y. Vit c ch ca phn ng to ra X t E . Cu 7. ( 2.5 im ) Vit cng thc cc ng phn khng gian ( coi vng nh mt a gic phng ) ca : a) 1,3 icloxiclopentan ( c ghi cu hnh ca C* trn cng thc ) . b) 1 metyl 2,3 icloxiclopropan . Cu 8 . ( 2.5 im ) T cc cht u l xiclohexanol , metanol , metyl ioua , etylenglicol v cc cht v c cn thit khc , hy lp s iu ch hp cht 2 amino 2 metylxiclopentanon . Cu 9 . ( 2.5 im ) Cht lng A1 quang hot c cng thc C5H11O2N khng tan trong nc v trong axit long nhng tan trong dung dch NaOH to ra dung dch B1 . Axit ho dung dch B1 to ra bin th rexemic ca A1 . Hiro ho xc tc Ni cht A1 quang hot to ra C1 ( C5H11N ) quang hot , cht ny phn ng vi HNO2 to ra ancol D1 quang hot v mt lng nh ancol t amylic . Lp lun ngn gn xc nh cng thc cu to ca A1, C1, D1 . Vit cc phng trnh phn ng . Gii thch s to thnh bin th raxemic A1 v ancol t amylic k trn .

 THI OLYMPIC HA HC SINH VIN TON QUC LN TH V (Nm 2008) (Thi gian lm bi 180 pht) BNG A A. Phn Ha hc i cng V c Phn tch Cu I (2,50 im) 1. Nhng nguyn t hydro trng thi c bn b kch thch bi tia UV c = 97,35 nm. S lng t chnh ca trng thi kch thch ny l bao nhiu ? Khi nhng nguyn t hydro b kh trng thi kch thch th chug c th pht ra nhng bc x c bc sng (tnh bng nm) l bao nhiu ? 2. V gin nng lng cc MO ca cc phn t HCl c to thnh t cc nguyn t hydro v clo theo thuyt MO LCAO. T vit cu hnh electron v tnh ch s ( bi, bc) lin kt ca phn t HCl 3. Trong phn t HCl th 38% thi gian electron lin kt chuyn ng pha nguyn t hydro, cn 62% thi gian electron chuyn ng pha nguyn t clo. Tnh cc h s C1 v C2 trong biu thc MO lin kt = C1 1sH + C2 3pCl ca phn t HCl Cu II (3,00 im) Trong cng nghip ngi ta thng iu ch Zr bng phng php Kroll theo phn ng sau: ZrCl4 (k) + 2Mg (l) 2MgCl2 (l) + Zr (r) Phn ng c thc hin 800oC trong mi trng kh agon (Ar) p sut 1,0 atm. Cc pha trong phn ng khng ha ln vo nhau: 1. Thit lp phng trnh Go = f(T) cho phn ng 2. Chng minh rng phn ng l t pht trong iu kin cng nghip 800oC v p sut ca ZrCl4 l 0,10 atm. Cho bit cc s liu entanpi to thnh Hos, entanpi thng hoa Hoth, entanpi nng chy Honc (tnh bng kJ.mol-1) v entropy So (n v l J.K-1.mol-1) bng sau Cht Hos Hoth Tnc (K) Tth (K) So Honc Zr (r) 0 39,0 ZnCl4 (r) -980 106 604 181 Mg (r) 0 923 32,68 9 MgCl2 (r) -641 981 89,59 43 Coi Ho v So ca phn ng l hng s trong khong nhit kho st Cu III (3,50 im) 1. Cn bng sau xy ra trong dung dch nc 25oC: 2Cu+ Cu2+ + Cu (r) (1) a. Tnh hng s cn bng K1 ca phn ng (1) b. Mt dung dch cha CuSO4 0,10M v Cu (r) rt d. Tnh nng Cu+ trng thi cn bng 2. Tnh cc hng s can bg ca cc phn ng sau 25oC a. I3- + 2Cu+ 2Cu2+ + 3IK2 = ? 2+ b. I3 + 2CuI (r) 2Cu + 5I K3 = ? 2+ c. Cl2 (k) + 2CuCl (r) 2Cu + 4Cl K4 = ?

3. Hi hng s phn ly tng Kd ca ion phc [Cu(NH3)2]+ trong dung dch phi b hn gi tr xc
nh no, bit rng 0,10 mol CuCl (r) ha tan hon ton c trong dung dch NH3 0,20M ? Tnh gi tr 4. Kd ca ion phc [Cu(NH3)2]+ l 1,0.10-16. Hi dung dch NH3 0,20M c ha tan hon ton c 0,10 mol CuI (r) khng ? Cho bit cc s liu sau 25oC: Eo(Cu+/Cu) = +0,522V ; Eo(Cu2+/Cu) = +0,34V ; Eo(I3-/I-) = +0,54V Eo(Cl2(k)/Cl-) = +1,36V ; Tch s tan Ks (CuCl, r) = 1,0.10-16 -12 Ks(CuI, r) = 5,0.10 Cu IV (1,00 im) Ly vo bnh nn V1 = 10,0 mL dung dch NaCl nng C1 mol.L-1 v V = 0,50 mL dung dch K2CrO4 nng C = 0,050M. Kt ta gch bt u xut hin khi thm vo V2 = 7,8 mL dung dch AgNO3 nng C2 = 1,0.10-2M: 1. Tnh nng C1 ca cc ion Cl- trong dung dch NaCl ban u 2. Tnh nng Ag+ v Cl- trong bnh nn khi bt u xut hin kt ta gch. T tnh phn trm ion Cl- cn li trong dung dch lc ny Cho bit tch s tan: Ks(AgCl, r) = 2,0.10-10 v Ks (Ag2CrO4, r) = 1,6.10-12 Ghi ch: Ga tr cc hng s dng cho cc php tnh h = 6,63.10-34 J.s ; c = 3,00.108 m.s-1 ; 1eV = 1,602.10-19 J ; 1mn = 10-9m o T = (t C + 273)K ; R = 8,314 J.K-1.mol-1 ; F = 96,5.103 C. mol-1 B. Phn Ha Hu c Cu I (5 im): Hon thnh cc phng trnh phn ng theo tng dy bin ha di y, vit cng thc cu to cc cht tng ng vi cc ch ci trong tng s . Vit c ch hnh thnh A, B
1. Metyl xiclopropyl xeton (X) 1. CH 3M gBr 2. H2 O HBr A B 1. Mg, ete 2. X HBr C D 1. Mg, ete , -78 C O CHO O EtO
o

H 3C N 2.

EtOH G H

KMnO 4

HCl dac I K

- CO2

OH -

NaBH4

HI, to P Nicotin 1) C 2 H4 (OH)2 , H + 2) KMnO4 loang R 1) H 3 O+ 2) HCN S 1) H 3 O+ 2) Na - Hg T

H 2SO4 d, FeSO4, 3. Glixerin Q

Cu II (2 im): T benzen, metanol, anhydrit axetic, anhydrit - metylsucxinic, xiclopentadien, etylacrylat v cc ha cht v c cn thit khc vit s phn ng iu ch: 1. 2-phenylpropan-1-ol 2. 2-metylnaphtalen 3.
Br

O O

Cu III (2 im): Hp cht A phn ng vi PCl3 cho B, kh ha B bng H2/Pd nhn c benzandehit. Mt khc cho B tng tc vi NH3 thu c C, x l C vi brom trong mi trng kim th c D. T B c th nhn c E bng cc cho phn ng vi benzen v xc tc AlCl3. E chuyn thnh F khi x l vi hydroxylamin, trong mi trng axit hp cht F chuyn thnh G. Hy xc nh cng thc cu trc cc hp cht t A n G, bit rng G cng c th nhn c khi cho B phn ng vi D Cu IV (1 im): Khi cho nitrozyl clorua phn ng vi xiclohexan s nhn c dn xut mononitroso, sau chuyn thnh oxim A. X l A vi axit s nhn c caprolactam B 1. Vit c ch hnh thnh dn xut mononitroso 2. Vit c ch to thnh lactam v nilon-6 ________________________________ Cn b coi thi khng cn gii thch g thm