Céu I (3,0 diém) HNC (hidro isoxianua) la mt déng phan cla HCN. Chit nay duge tim thy phd bién trong méi trudng gitta cdc vi sao. 1. Viét cing thite c&u tao cia HCN va HNC. Lép lugn dé cho biét céc dign tich thyc -0,47e, va ~0,24e, lan Iugt thudc vé nguyén tr N trong phan tir nao? 2, COng trinh nghién ctw thyc nghiém cua nhém téc gid Chin Fong Pau va Warren J. Hehre (nim 1982) cho biét bién thién ni n&ng cia phan img chuyén HCN thanh HNC Ia 46,9 kI-mol tai nhigt 46 100 K. Dya vao dit kign nay ciing céc gid thiét gin ding hop It, tinh hing s6 can bing X (tai 100 K) cho efn bing: HCN == HNC 3. Trong khong gian gitta céc vi sao, ngudi ta phat hign ra hai phan img quan trong lién quan én su hinh thinh HNC nhu sau: [HNCH]’ +e —> HNC+H [H,NCl. +e —> HNC+H Dé xudt cong thite cdu tao cla [HNCH]* va [H:NCY’, tir dé gidi thich vi sao nguyén tir H bj téch ra khi hai ion nay nhén thém electron. Cho rang khng eé phan img trung gian nao khdc. 4. Phin tir 2,3-diaminomaleonitrin c6 thé duge tao thanh tir HCN. Bing cdc Iép lun hgp li dya NC _N theo edu tric céc chét trung gian thich hop 62 © 4HCN——~ -» ——~ C=C : Fee cies Tah ee va 3 cing céc kién thite vé cdu tao phan ti, lién HAN’ ‘NH ee ta hes se xudt co ché tgo thanh hgp chit 2.3-tiaminomaleonitrin Scanned with CamScannerCau II 3,0 diém) Butan (Mey, = 58,13 g-mol), sit dung lim khi dét 48 cung cp nhigt cho che myc ich dan dung, duge nén 6 ép sult cao trong céc binh thép, m&i binh nhu vay chiza 13 kg butan, Gia thiét 46t chdy hoan toan 13 kg khf butan trong digu kin ding 4p bing V (L) khong khi via ii, 6 nhigt 45 300 K 4é dun mot binh nuéc lén. Lugng nhiét sinh ra tir phan tg (& 300 K) mot phn lm néng céc san phim cila phan img (gia thiét chi ghm COz(k) va H,O(I)) va lugng Nz cb trong V/(L) king kh ln 450 K; mot phn lam nog binh dun va nue trong binhs phan con Ii hao phi do bite xa nhigt ra moi tru’mg xung quanh. Biét lugng nhigt bite xa ra m6i truymg xung quanh bing 1/9 lugng nhigt duge nhgn béi binh dun va nuéc trong binh. 1. Tinh nhigt d6t chay chudn, A. (kd-mol"), cia khi butan 6 300 K. 2. Tinh lugng nhiét (theo kJ) ma binh dun va nuéc trong binh nhgn duge khi dét chéy toin b6 lugng butan cé trong binh thép trong diéu kién 44 cho. trang 2/10 3. Tinh kh6i lugng nurée trong binh c6 thé dun néng duge (trong m6t lin dun) tir 27°C dén 75°C hi ddt chdy hét 13 kg khf butan n6i trén. Gia thiét, muéc trong binh bay hoi khong ding ké trong itu kign 48 cho, Cho ring: + Nhigt hinh thanh ca céc chit: 4, Ha(H,0,1)=—285,83 KI -mmol"; Ay i9(CO, k)=~393,51 KI -mol; Ay Hyy(C,Hp,k) =—126 14 kJ-mol™. + Nhift héa hoi cia nuéc long: A, Hy (H,0,1)= 40,5 kJ-mol. +Nhigt dung: C3(H,0,I)= 75,3 J-mol™-K~; C}(H,0,k)= 33,86 J-mol"*- CHIN, k)= 28, 74 J-mol™-K"; C3(CO, k) = 41,63 J-mol-K"; Cf (binh dun) = 6750 J-K-*. Coi cée gid tri nhigt dung kh6ng thay 45i theo nhigt 9. + Khéng khi gdm Nz va O; theo ti I¢ thé tich twong img 1&4: 1. Scanned with CamScanner‘Cfu III (3,0 diém) Pin nhién ligu dang duge djc bigt quan tim nghién ctu vi tiém nang sir dung trong tuong lai do cé6 nhiéu wu diém so véi pin Galvani hién nay. Dong dign tao ra trong pin do phin ‘img oxi héa nhién ligu (Hip, CHjOH, CHy,...) bing Op cia khong khi. Uu diém cia pin la sin sinh dong dign véi higu suat cao, céc sin phdm oxi héa la HO, CO; than thign véi mdi trudng. ‘Trong pin hidro — oxi, céc qua trinh oxi héa ~ khit xdy ra nhu sau: (Qué trinh Khir xy ra 6 catot: O2(K) + 2Hz0(1) + 4¢ — 40H (dd) ‘Qué trinh oxi héa xay ra é anot (trong dung dich KOH): Hy(k) +20H (dd) —+ 2H,0(1) +2e 1. Vide phn tg ting cng xdy ra khi pin hidro ~ oxi hogt dng, Tinh site dign dng chudin cia pin 625°C. 2. Mét han ché cia pin hidro — oxi IA strc dign d$ng chudn gidm khi nhiét 46 ting. a) Giai thich (bling Hip Iufin hodc tinh todn) Ii do sire dién dong chuén ca pin gidm khi nhigt 46 ting. b) O nhigt 46 nao thi gid tr ste dign d6ng chudn cia pin gidm di 10% so voi & 25°C? 3. Tinh kh6i lugmg (g) hidro (My, =2,00g-mof) cln six dung trong pin nhién ligu 8 o6 thé cung cp m6t dign long 1a 10500 mAh, gia thiét higu suft céc qué trinh déu bang 100%. Cho biét: Chu tir ApH (kd-mol) Soy (E-K" mol) Oatk) 0,00 205,14 1,00) = 285,83, 69,91 OH (dd) =210,41 10,75 Hak) 0,00 130,68 Gia thiét trong khoang nhiét 4§ nghién citu, Ar” va S® cla cdc clu tr 1a khong d8i. Scanned with CamScannerCau IV (3,0 diém) ‘Duge chét Reumicin (R) duge ding 4é diéu trj ung budu. R téc dung véi chat kiém B, tgo thanh chét trung gian D va sn phdm cudi C theo ca ché sau: Ripe D B+D —2>C Tién hinh m6t thf nghiém trong digu kign dng thdi: [B) rét 1én va [B) >> (R], két qua cho thy d8 thj cia InfR] phy thuge tuyén tinh (48 thj c6 dang duéng thing) vao thai gian ¢. 1. Viét phuong trinh phan img ting cOng dya vio co ché trén. Bac riéng phn cia R trong phin img tng c6ng 6 didu kign néu trén 1a bao nhiéu? 2, Sir dung sy gin ding ndng d6 dimg, viét biéu thic djnh lugt tic 4 cia phan img tang c6r theo ki, k-, fx, [B] va [R] trong trutmg hp téng quat v6i moi ndng 49 cia B va R. Tir 46, i bigu thite dinh lugt tbc 9 cia phan tg cho truing hgp TB) rt len ng hei [B]>> [R] va nit ra biéu thite cita king cgeg- . . 3.Cé thé xéc dinh duge gif tri gan ding cia k, bing céich do hirgctrg © [B] rat lon, dng thoi [B] >> [R]. a) Dua ra biéu thire tinh A; trong truémg hgp nay. b) Dya vio gid trj thye nghiém cia hing cong Cling c6 thé tinh durge ti s6 kp/k-1. Rit ra bidu thie tinh ti sb kf. Scanned with CamScannerCin V (4,0 diém) Cho so 48 chuyén héa nhwr hinh bén. OY Céc hgp chét Al, A2, A3, Ad, AS va AG déu 43 = A4 ~ chita nguyén t6 kim logi A va nguyén t6 oxi; s6 oxi @) * fa cia A ting dn tir +2 dén +7 trong cdc hop chét ) i oe @) » tir Al, A2, A3 dén Ad. Hop cht A2 chi gém 2 ” nguyén t6, phan tram khéi lugng cua oxi trong AZ a1 a2 S———_ as 14 36,78%. 1. X4c inh céng thie phin ti cia cdc chét tr Al ao) @) én A6. Viét phuong trinh héa hoc cla cdc phan ng xay ra trong so 46 trén. AG trang 6/10 2. Trong phing thi nghigm, dung dich cia A4 thug duge si dung trong céc phép chudn 4 oxi — h6a khi. Gii thich (bing cdc phuong trinh héa hoc) tai sao: a) Khi thye hign phép chuan 49 nay, ngudi ta cho dung djch cla Ad vao buret, chit khir vio binh tam giée ma khdng lam ngugc lai. b) Dung dich cia A4 duge bao quin trong céc binh t6i mau. 3. Cho dung dich cia Ad téc dung véi AgNOs, thu durge két tha mau 45 X1. Cho BaCk (vita di) vio dung djch bio hda cla X1, thu duge két tia tring X2 va dung dich eva X3. Khi cho HaSO, (long) vao dung djch cla X3, thu dugc két ta tring X4 va dung dich cila XS. Bun néng dung dich iia X5 thi thu duge két tha A2. Con néu cho Ad tic dung véi H;SO, 44m dic thi thu duge oxit X6 la mét chit oxi héa rét manh. Xéc djnh céng thite phan tir cdc chft tir X1 dén X6 va viét phuong trinh hoa ge cha cdc phan tg xdy ra trong céc thi nghiém trén. Biét céc hop chét X1, X3, X5 va X6 déu chia nguyén t6 kim loai A. Scanned with CamScannerfu VI (4,0 diém) id thiét c6 dung dich A gdm H3PO« néng d) a M va CeHsCOOH 0,030 M. Dung dich ‘Acb pH bing 1,56. 1. Tinh a (ghi két qua véi 3 chit s6 sau du phay). 2. Tinh 46 dign li cla CsHsCOOH trong dung djch A. 3.06 két tha tdch ra khOng khi tr6n 1,00 mL dung dich A vi 2,00 mL dung dich CaCh 0,066 M? Giai thich bing tinh todn. 4. TrOn 2,00 mL dung dich A v6i 3,00 mL dung djch NaOH 0,290 M, thu duge dung dich B. Thém tirtirtimg gigt CaCl, 0,066 M vio 1,00 mL dung dich B cho t6i du, Bing tinh todn cho biét: Cé két ta teh ra khng? NB, cho bit két tia gdm ning chat gi? Gia sir khOng cé sy dng két tha (cOng ket). Cho biét: pX,,(H,PO,) = 2,15; 7,21; 12,32; pK, (C,H,COOH) = 4,20; pK, (H,0) = 14,00. pK,(Ca3(PO,),) = 28,92; pK, (CaHPO,) = 6,58. Scanned with CamScannercaw r(3,vaem) 1. Cho cdc chit sau day: NH ° 1 yn 0 Bo we wo ms ak B2 NH, B3 X a) Gitta Al va A2, chdt ndo dé tham gia phan img hon v6i Br, theo co ché cfng electrophin (vio lién két 461 C=C)? Gisi thich. b) So sénh lye axit gitta A2 va A3. Gidi thich. ) Trong s6 cdc chét: B1, B2 va B3, chit ndo c6 lye bazo Ién nhit? Giai thich. 4) DE xult so dd tng hop A2 ti Al. €) Cho so 48 chuyén héa A2 nhu sau: 2 20% a rene CHO | eg tO” gg GUO og PHCHO Molete KOH, Cost a a VE (khong cin giai thich) cng thie cdu tao ca céc chét C1, C2, C3, C4, C5, C6 va C7. 2. Gian 43 nang lugng orbital (obitan) phn ti (MO) cia nhém cacbony! durgc cho & hinh bén. Gid trj ning lugng HOMO (orbital phan eon tir bj chiém o6 mite niing Iugng cao nhét) va LUMO (orbital phan tir khong bj chiém c6 mite ning Iugng thip nhét) cla CHsCH=0, ‘ning Iugng cila AO 1s cla H duge cho trong bang sau: oh 204 [_____[criscrvo | [cx,cH-ony [Romoreny| ie ~1408 | reat =Ba7 Biét ring HOMO cia phn tir (hoc ion) nay c6 thé tuong tic voi Sco YP LUMO cia phan tir (hoc ion) kia. Khong céch n&ng lugng HOMO-LUMO cang gan thi tuong t4c cang manh. a) Dya vio céc dit kign cho biét 6 trén, giai thich vi sao trong phan img cng gitta HCN va CHsCH=0 thi co ché cia phan img ld An (nhém CN" tin cng tnréc) ma khong phai ld Ag (H* thn cong tnréc). b) Dua ra minh chimg vé m§t nding Iugng 48 gidi thich tai sao khi CH;CH=O duge hogt héa bing axit thi phan tmg c6ng véi CN" xay ra thufin Igi hon. Trang 1/10 Scanned with CamScannerCau I (3,0 diém) 1, Cho cis-2-aminoxiclohexanol phan img v6i dung dich NaNO,/HCI, thu duge chit A va chét B déu cd céng thite phan tt CeHio0. Cho srans-2-aminoxiclohexanol phan img véi dung djch NaNO2/HCI, thu duge chét A. Ca A va B déu phan tmg véi thudc thir 2,4-dinitrophenylhidrazin. Xéc djnh cOng thie cdu tao cla A va B. Dé xufit co: a gidi thich sy tao thanh A va B. 2. Phin img da téc nhan la mt phuong phép dé ting ® ae ° 9 hgp cdc dj vong, Dj ving X dugc ditu ché theo phan tmg 6 cty SK smow ee hinh bén. Be xudt co ché dé gidi thich sy tao thanh X. oN OX 3. Papaverin (hinh bén) 1a host chit ding 48 bao ché M thube ching co thit, Dé xudt so 3 tng hop papaverin tir 1,2-dimetoxibenzen VA yo céc hgp chat hitu co chita kh6ng qué 2 nguyén tir cacbon. ae 4. Quercetin (cht chéng oxi héa va lam bén thanh mach mau) c6 thé duge tng Papaverin ome hop tir 1,2-dimetoxibenzen theo so 48 sau ‘MeO. OH oe on Med. cH > HO. le 0 ICl/KOH Oued HeS804 g CettyONO yy 1. HO T eo Cats KOM CrctOs CigHonOs ——_CygHyp NO, 2 on : . OHO Quercetin Vé (khong cn gidi thich) cng thite cdu tgo cita cdc chit E, F, G va H. Scanned with CamScannerChu O11 (3,0 diém) 1. Metylarbutin (CisHisO7) duge tim thdy trong qua Ié, khéng phan img véi thuéc thit Tollens (Tolen). Khi thdy phén metylarbutin bing enzim f-glucozidaza, thu dugc D-glucozo va hgp chét thom A (CrH0;). Cho A phan tg véi HI, thu duge chét B (CeH¢02) kh6ng mau, phan tt khéng phan cy, c6 tinh axit va phan tng duge voi nudc brom. Khi dé lau trong khong khi, chat B bj oxi héa tao thanh sin phdm cé mau da cam. Cho metylarbutin phan tmg véi lugng dur dimetyl sunfat trong m6i trudng kiém, thu duge cht C. Thily phan C bing dung djch HCl long, thu duge 2,3,4,6-tetra-O-metylglucozo va chat A. a) Xéc dinh (c6 gidi thich) cong thirc cdu tgo cia A, B va cdu triic cia metylarbutin. b) Metylarbutin durge tng hop theo so 48 sau: H .OH O H 420. py HBr og A F 8 Metylarbutin YT NOHO CithnOn Cub B0, ABP City + V& (khéng clin giai thich) cu tric cla cdc chét D, Eva F. + Ba xudt co ché dé giai thich sy hinh thanh E va F. 2, Thiy phn hoan toan mOt axit X (CicHiO;NsP), thu duge adenine (hinh du6i), cacbohidrat Y (CsHioOs) va axit photphoric theo ti Ig I:1:1 vé s6 mol. Axit X khéng phan img v6i thude thir Tollens (Tolen). Y tham gia phan img trang guong; oxi héa ¥ bing nuéc brom, thu durge axit CsHioOs quang hoat; oxi héa ¥ bang HNOs, thu duge axit CsHyO7 khong quang host. ¥ va cacbohidrat X1 (chét so sinh) cé cdu hinh thugc day D va cing tao thanh mét osazon. Thosi phin Wohl X1, sau 46 oxi héa sin phim tao thanh, thu dugc hgp chit C,HsO¢ khéng quang host. Thiy phan khéng hodn ton X, thu duge adenine va X2 (CsH1,OrP). Khir héa X2 bing Hy/Pd, thu duge chét X3 (CHOP) khong quang hogt. Thiy phan X bing dung djch NH lodng, thu dugc mudi amoni cla H;PO, va adenosine. Xtr If adenosine bing Me,SO,/NaOH, thu duge chat X4. Thy phn X4 trong axit, thu durge chét X5 (CxHisOs). Khi oxi hoa manh XS, thu duge axit 2,3-dimetoxibutandioic khong quang hogt. ‘Xéc dinh (c6 giai thich) edu tric cba X, ¥, X1, X2, XS va adenosine, trong 46 hyp phn cacbohidrat ¥ uge biéu din duréi dang cng thie Haworth (Havoc). Biét nguyén ti C1 cia hgp phin cacbohidrat trong axit X cé cdu hinh £ va adenine tao lién két tai vj tri nguyén tr N cé lye bazo yéu nhdt, Ma Scanned with CamScannerCaw IV G,0diém) 1. Attopin (CirH:3NO;) la ancalot thin nhién 6 de tinh, ¢6 te dung ne. gitn oo. Thly phan atropin, thu duge tropin, axit atropic (hinh bén) vi Ho Hey, anit CcHsCH(CH,OH)COOH. Tropin ld ancol khéng quang hoat. Khi [ dehidrat a tropin, thu duge tropiden (hinh bén). 4 , 4) Ve (Khong cha pi thich)cbg thc chu to oda tropin va atropin. Act atopic Tropiden b) Be xudt so d8 tng hop tropin tir MeNH2 va chat X (hinh bén).. F008 C €) Tropin phin ting véi ¥ (inh bén), thu dugc benztropin la hoat chit ooEt ding 48 bio ché thude chia tri bénh Parkinson. V& (khéng cdn gidi "x bY thich) céng thitc cdu tao ca benztropin. 2. Vitamin B6 (ki higu la K,, chita dj vong piridin) duge t8ng hgp theo so 48 sau: OEt ce: oN on HNO, Poe s Hypa 4, Hovie0’¢ =» NaNOwHCL 90°C 0 HNO GaettyaNaO2 CyoHtgCIN3O, CygHyyNyO Cay gN30 CoHnsNOs Vé (khéng cdn giai thich) cng thitc cdu tao cia cdc chit E, F, G, H, Iva K. 3, Murrayafolin (T) la ancaloit duge phan Ifp tir thye vét. Trong phdng thi nghigm, murrayafolin durge. téng hop theo so 48 sau: OP op opened o me omen Ch MOL? 5 pce g MONS <= | Mts a ° Pp Q AR Pe 4 a) Vé (khéng cn giai thich) cOng thitc cu tao cia cdc chét O, P viQ. b) Dé xudt co ché cia phan tmg chuyén héa L think M. Scanned with CamScannerCiu V (4,0 aiém 1. Hop chat thom vanillin f& tién chat trong tng hop héa hoe va sinh ting hop. ) Con during sinh tng hop vanillin ttyrosin theo so 48 sau: 1)E3 MeO, HO Se A a ME 0 EE ba Tyrosin Cae CoH CoHsOs CrHeOn Biét ring, pyridoxal 14 enzim deaminaza, NADPH c6 tinh khit tuong ty nhu NaBHs, El la enzim chidrat héa, E2 la enzim hidrat héa, E3 14 enzim, SAM Ia téc nh&n metyl héa tuong ty nhu Mel/Ag:O. + Vai tr cba enzim E3 1a gi? + VE (khéng cn gidi thich) cOng thie cdu tgo cla cdc chit A, B,C va D. b) Vanillin chuyén héa thanh dihidroxiphenylalanin theo so 48 sau: 1 Me,SOg ‘Ac0 HPA. | 4, Bralphotpho HHO. COOH Vanitlin ———",- | —— ~¢ = L SEPP yy" KOH AcONa « 2. NHy Road Vé (khéng clin giai thich) cng thite cfu tgo cdc chit I, K, L va M. . 2. Glicozit thién nhién X chita hgp phan quercetin (xem céng thie & Cau 11.4), Thiy phan X bing enzim arglcoritazs, thu dure chdt X1 (CoHi20s) va chdt X2. Thay phin X2 biing enzim f-glucozidaza, thu duge t X3 (CeHy20¢) va quercetin. Metyl héa hoin toin X rdi thy phin sin phim c6 xic te axit, thu duge chit X4 (CoHi10s), ‘cht XS (CsHix0s) va chét X6. Oxi héa X4 bing HNOs, thu duge chit yéu 1a axit (2R,4R}-2,3,4-trimetoxipentandioic, axit meso-2,3-dimetoxibutandioic va axit axetic. Oxi héa XS bing HNOs tao thinh axit meso-2,3,4-trimetoxipentandioic. Cho biét, X1 c6 edu hinh L, X3 ¢6 edu hinh D va X6 tn tai & m6t cn bing xeto - enol. Xéc dinh (c6 gidi thich) cdu tnic cla cde chit X1, X2, X3, X4, XS va X, trong 46 céc hop phiin cacbohidrat duge biéu didn dui dang cng thite Haworth (Havoos). 3. Peptit ty nhién Y c6 cfu tric 'Peptit-Asn-Gly-Peptit? 4é Iau trong mdi trudng kiém nhe thi cé sy gidi phéng amoniac tir Goan mach Asn-Gly. Néu dé ldu thém mot thdi gian nffa trong didu kign nay thi conte peptit ¥ chuyén héa thanh hai peptit méi Y1 va Y2 1A ddng phin cla nhau. Xée dinh edu 2 tric eda cdc peptit Y1 va Y2. Giti thich guétrinh chuyén héa Y thinh Y1 va Y2. Biét ede yy doan mach 'Peptit va Peptit” khong bj bién di trong digu kin trén, Aspargin (sn in Scanned with CamScannerC4u VI (4,0 diém) 1, Cho céc hé lurgng tt X: H, Li*, B®. Ki higu ning lugng electron cla méi hé la E,[X] (don vj eV); 7 1a sb lgng tir chinh. Két hgp Ii thuyét véi thye nghiém, ngudi ta thu duge day gid tri ning Iugng cho méi hé nhu sau: f =340,0 | =1360 _{ -340_] Bee c a) Chi ra quy lugt lién hé (dang. wi thie) gitta E,[X] véi s6 lrgng tir chinh n trong mdi day trén. Tinh E«{X] cho méi day. by Dy vio bang trén, xic djnh gid tr nBng lugmg ion héa cia m6i he. Giai thich. 2. Cho so d8 chuyén héa sau: Ph NadHése,du.f x4 COr yo ddNaOCl ya (CH,COOH loang, r re CH; i 02° 4 enh x5 +X6 Xp — noe xg OE pho, 8 CH,COOH | yg HNO, @beandng Io leoh a long, xe) meteled x7 x9 +X3 Céc chit tir X1 dén X9 déu 14 hop cht ciia chi. Phan tmg nhiét phan X2 tién hinh trong binh kin khong chita khéng ht. a) Xée dinh céng thite phan ti eta céc chat tir X1 dén X9 va viét phurong trinh héa hoc cla cdc phan img xdy ra. b) Héa tan hodn toan 0,5 gam Pb;Oy (Myo, = 685 g-mol”) trong dung dich HI dc, dur. Bidu chinh pH cia dung djch sau phin img vé khong 4 + 5 ri chuén 49 ngay dung djch thu duge bing dung dich NavSaQh 0.10 M thi hét Ym1. Tinh 7 Scanned with CamScanner