BO GIAO DUC VA DAO TAO KY THI CHON HQC SINH GIOI QUOC GIA, THPT NAM 2012 HUONG DAN CHAM DE THI CHINA THUC Mon: HOA HOC ‘Needy thi thir hai: 12/01/2012 Dy thio Ch 1. (4,0 diém): 1. 1,5 dim; 2 2,5 diém. ‘Viet cong thite edu tao cia cde hop chit hi co A, B,C, D, E, F, GH, 1, J, K, M, N dé hoan thinh cée sor dd chuyén hoa sau: 1 mcr Sp HNOACHCOOH, ONL (CiaH 202) an POC.CH, p MNCCHY _NCHICIIE 2. CHy-CHy-CH,-OH pp AAC g ENGUCIID p ° > a HOS Lets : ; San | mre wo crecr.cHo > 6 Ee wae Oe | Haney Mou (CisHin0) ee 20 Huéng dén chim: 8 es bu a arectto MON. pr-co-cuor-eh EX» mcoden a> me hou cH,COOH I as w @ oO Go Pm» mh | : > phc-con Meo -F ‘OH Is ob 10 6 © 2 PCC, CHL TNCCHY: LIN(CH(CH)3}> Li catpcrsctt-on YS cryyecr.cHo 8 car-criecten-c(cig NM OE cH, CH-CHEN-CICH: D E F o KC on i OO y on at 4°, cu-cucio > nec] Me cen) oe Loo wh ‘on be O- Nigar O- BHO We OY c 0 1b HyC__ On cus Cs ng frac a is ~ (pets io Hic ry wes oS me Scuo 1 oS 7 K it on i oe arycrcrncenys + LJ J Savoy 2 1H * ae cio The peer F K (CH))C-N-I He ce OHC™ ~CHy CA 2. (4,0 diém): 1. 1 diem; 2. 1,5 diém; 3. 1,5 diem.Vist céng thie cau tao cua cée hyp chat hiu co A, B, C, D, E, F, GH, 1, J, K cfc so dé chuyén héa saw PPh ch 1. 1,2-biformytbenzen Pit?" a —t ys (CsHle02) 2. peMetyinaphtalen OP, CHECH-CHECH: 200°C yy IINNINCHONS 5 KiCiOyHS0u (Cutie) v HN-O1 11,80, +G F290 g ENON y LIBS | 4G y K Cidths02) 2Lialn, 3. Viét co ché cia phan img: Br KONTO N.CH3-CHs-COOK 40°C B co thé lisa phim cng 2 Cl: Huéng dan chim: 10 AS t LZ PP Sate Jo oom “bon. Sn *or 2 C(O -O05 — \xY \2 Boa 9 CHs ALE {-Metyinphtaln rd om Hy Hy ote K.COML S04 Se COOH sso, (7 fo HNOM aa coon ~ Hee G Hy Hy CHs oO ZF or ‘NH LiAIH, 110, hove ans oc ae ote: NH So " oy cco cH, 3. Co ché cia phin img:Caw 3. (4,0 dé): 1. 1 dig: 2.1 dim; 3.1 diém: 4, 1 diém 1. Hop chat (A) chuyén hoa thanh hgp chat (A') trong mdi trudng kiém theo so dé bén. Hay ding mai tén On, coon cong dé chi r8 co ché cia phan img 7 OEE Bi (ay a tei a trong phan ti va vb ea can tht; hay viet ce phan img digu che One N-ctyloxindo N-Btyloxindol ci 3. Viet céng thie cau tao cia céc hop chat hitu co B, C, D, E va co ché phiin ting tao thinh B theo so 43 Chun haa: ° WE OH yy Zyewst en a or o fi i ‘oi (2) vi ve cau tne etia 4. Vikt cée td nhin phan img, diéu kign phan sing (néu 6) thay cho du cl cae hgp chit hia eo A, B dé hoan thinh so d6 chuyén hod sau Huing din chim: ; Néu nguyén tir Br thir 2 6 vj tri s 3 cita vong thi khi phan img voi OH" khéng tao ra sin pham A’. Muon tao rt A*, nguyén tir Br dé phat 6 vi tri2 va phan tmg xay ra nur sau2 2 2 To |) cont jy} bam SN Casco, CY te bn e SH wy ABSA sae Ho c00Ne 4 HNO wal oO B HAC cH c D E 4 9 Ne Me oct, yn, fa ioe 7 {OV water CT ir - ¢ HOCH,’ j aan (Giai dogn cubi cing o6 thé ding H Cau 4. (4,0 diém): 1. J diém; 2.1 diém; 3. 1,5 diém; 4. 0,5 diém. Apiin [i mt lavon-glycozit ob rong cay ean tly, moi téy. Thiy phin ou apiin exc ta enzim Belycosidaza, thu due A (apigenin, cong thie HO, C ry LY phan tir Ia CisHgO3), B (CaFi20s) va C (CHO). Metyl héa hoan {oan apiin boi CHaV/Ag0, sau d thuy phan sn pha thi thu dure é D (CpHsOs), E (CoHlixOe) va F (CaH6O3). Oxi ha E being, COVH2SOs, OH OA (Apigenin) ‘due sin phim chinh li axit (2S)(3S)-dimetoxisuexinie. Khi cat mach Rugf Chi thu duge G (CARO). Mit knic, C chuyén héa duge theo sod dui day: MOM’ C, NOK C, NM GC, HE OL + Cs 1, Xac dinh cu tric cita B. 2. Ve cong thite Havooe cui cée ding phan c6 t 3. Ve edu tric etia C1, Ca, Cay Ca i Cs 4, Ve cau tric cia apiin, bist phan disaccarit lién két voi nguyén tir cacbon 6 vi tri s6 7 cia A. ‘Cho: Kv F la ce monosaccaritthuge day D, o6 thé tin tai 6 dang hn hop céc ding phin anome: Khi B 6 dang o-piranozo vi C 6 dang B-furanozo thi du phan mg duge voi | duong, Ingng (CHs):CO/H2SOx, : C tinh quang host, cin G khong c6 tinh quang hoat; C vi G déu tham gia phan img Tolenxo. fn tai cia C khi é dang furanozo. Haring din chim: 1. Tir cdc din xudt metyl, E va F, suy duge thir ty lién két cua cic monosaccrit: C-B-Apigenin.Xéc dinh B. kK hop digu kign B 6 dang a-piranozo phan img duge véi 1 duong long axeton vi sin phim oxi héa E Ia axit 28),38)-timetoxisuexinic, suy ra B c6 thé 1 D- glucoza, D-sorbozo,.. nH Ho} nt Gon D-servose Khi B la D-glucoza: Hai nhom cacboxyl duge tao thinh do oxi héa nhém OH & C2 va OH 6 C5 etia E. Do vay, C lign két véi B qua vi tri. Meo. Ho, ae non HA OF Meo He Meo Kone owe OMe MeO on Hon F Hoon HOH byome coon e-D-Glucopiranose F (a-anome) Axit 25),(28)Dimewoxisucinie 2. Xac dinh dudng C. Theo dau bai C 14 monosacearit day D, 6 tinh quang hogt, khi ct mach Ruff cho G khdng quang hoat, suy ra C 1a mot D-andotetrozo, dang B c6 nhanh CH:OH (apioz0).. cHo H—2-on —Thotiprannye SHO Ho—*—cH.04 Ho—}—cH.0H choH cH,0H © 6) Nh6m CHO cé thé néi véi mdi nhém CH2OH, cho 2 dang ving furanozo. Mbi dang lai cé 2 ding phan: a- va B-anome, Nhu vay, ve mit Ii thuyét khi & dang furanoza, C o6 thé tn tai 4 dng phan nh sau (Day OH 6 C2 nim ben phai 6 cong thie Fiso, vA nam chad mt phing ving & cng thie Haworth): ON oat oO. 9H o 2) (3) (4) Trong sé 4 dang trén chi e6 2 dang (1) va (2) ¢6 nhém CH;OH 6 phia trén cia vong la dam bao dit kign iia dé bai. 3. Cong thite cua C, C1, C2, C3, C4 va C3. ye oct 0 Os oct, ear ~ ~ ea i HOCH»-COOH \cion ee on) wo, \io 7% \ wey ce EY dio any A on on on {011 onc-cno Pane “ G & .4, Khi B la D-glucozo thi cOng thie cia Apiin la Te Oo AO. i 9 TD Goon? eo? oT on OH Ain Khi B la D-sorbozo thi “apiin” o6 cOng thire sau (mae dit chura tim thy cht nay tén tai & dang glycozit trong thién nhién), 8 HoT aS aat Oy on no OND Gon wy ‘pu on on afar Cau 5. (4,0 diém): 1. 1,5 diém; 2. 1,5 diém; 3. 1,0 diém. 1. Thye nghigm cho bit ning lugmg lin kt, ki hig la E, (theo kd.) ca mat s6 lin kt nhur sau: Lign két_| 0-H (ancol) | C=0 (RCHO) | CH (ankan) [CC (ankan) E 437.6 705.2 412.6 3315 Lién két_| C-0 (ancol) | C-C (RCHO)_| CH (RCHO) HH E 3328 3503 4155 430,5 a) Tinh nhigt phan ting (AH%,,) cia phan img: CHs(CHO)> + 2Hs > CHx(CH:OH)2 (1) b) AH, tinh dirge 6 trén ign hg nur thé no wéi d6 ben cin ign két héa hoe trong chit tham gia va sin phim cia phan émg (1)? 2. Cho phan img: CuCOs (rin) CuO (rin) + COs (ki) Q) ‘Thye nghiém cho biét lién hé gitra nhigt d6 T (theo Kenvin) véi hing s6 can bing héa hoc Ky nur sau: (TR) 400, 500 600, ik, 2.10.10 151.107 | 2.61 a) Khéng can tinh, hay chi rd anh huong cua nhié¢t 46 T dén can bang héa hge cia phan tng (2). b) Tinh nhigt phan mg (AH®,,.) va bién thién nang Inong tw do Gipxo tiéu chuan (AG°,,) ciia phan img (2), Hay nhin xét ur bién thién theo nhigt dO cia AH" v8 AG". 3. Tha mot vign nude da c6 khdi Iugng 20 gam 6 -25 °C vio 200 ml rugu Vodka-Ha Noi 39,5° (gia thidt chi chita nude va rugu) dé 6 nhiét d9 25 °C. Tinh bién thién entropi cila qué trinh tha vién nude dit vao rou trén dén khi hé dat cdin bang. Coi he duge xét la 06 lap. (Cho: R= 8,314 L.mof'.K"!; khdi lngng riéng tia made 1a 1g.mf" va eta rugu 14 0,8 gat"; nhigt dung dang ap ciia nude dé la 37,66 J.mol'.K", ciia nude long la 75,31 Jamol'.K'! va cca rugu fa 113,00 Jamol'.K'', Nhigt néng chay cita nude da Ia 6,009 ki.mol”. Huing dan chém:1, a) Phuong trinh phan ting ° i i H zZ pe - cH cS + 2H-H ——» H-O-C-CH;-C-0-H ay 0 4 i I H i ait = Sve, - Sve, két i ili ign kd thie trong chit iu; v, fi s6 mol fi j la lién két thet j trong chat cudis v, ka sé mol lign két j Vay AH pe = (2Ec-0 + 2Biux + 2Benacioy + 2Ec.n (anny * 2Ecc weno) QEco + 2Eou + 6Eca stan + 2ECc ann) = (2. 105,2 +2. 430,5 +2. 4155 +2. 412.6 +2. 350,3) ~(2. 332,8 +2. 437,6 + 6. 412,6 +2. 331.5) = 2(105,2 + 430,5 + 415,5 + 3503) ~ 2 (332,8 + 437,6 +2. 412,64 331,5)=- 512K) b) Phan img toa nbigt vi tong nang lugng can thiét dé pha huy cdc lign Két & cde phin tir ehét du nho hhom tng nang ligne t6a ra khi hinh thinh eée lign két & phan tie chit cudi 2. a) Theo bai ra, khi nhigt 46 T tang, gid tri Ky ting. Vay phan img (2) thu nhigt, AH" > 0. Nhu vay Ki T ting, cn bing héa hoe chuyén dich sang pha. kK, ROTI » AH. = % Voi T) = 400, T2= 5 1,08 (kJ.mol) Voi T; = 500, T2= 600 > AH’, = 71,06 (kl.mol) Vay AH’ = 71,07 (kd/mo), AG'yy =~ RTINK, Voi; = 400; Kyi = 2,10.10° > AG)=+ 20,51 (ki.mor) Voi Ty = 500; Kyo = 151.10! AG!= + 7,86 (kJ.mol") V6iT) = 600; Kys = 2,61 AG}=- 4,78 (kL.mot') Nhin xét: theo chidu ting cia nhigt d6 thi AHYyy hu nhu khéng thay di, ahung AG? gid. 3. Thanh phan cia rugu va mr6e trong rugu 39,5 li Veo = 225200 = 29 (mt) Vyy = 200-79 = 121 (el) 100 : > mejuou =79 0,863.2 (g) vA Myo = 121-1 = 121 Khi tha vién nude dé vao hn hop ru, nhigt toa ra ciia hén hop row bing ding nhige thu vao cua vién nude da thi hé dat cén bing. Goi mhigt 46 cia hé khi h dat cin bing li tes (°C). ‘Qué trinh thu nhigt g6m 3 gia doan H,0 (F) > H,0 ()—*> 4,0 ()—*> H,0() 225°C orc orc to°C Qa =Q: +Q:+Q: +f 37.66 o-a+% 6,009.10 + 7531 (ta-0) > Qin = 7722,78 + 83,68. toy MAt khéc nhigt toa ra ctia qua trink:121 62 Qn = Quiet aie * Quierta = Fy» 75.31 Sty) + SE 113,00. > Qa = 661,50. (25—ts) Do Qua = Qu nen ta e6: 7722, 78+ 83,68. tes = 661,50 Bign thién entropi ctia hé (AS q) bing téng bin thign entropi vién mide di tie -25 °C Ken 11,83 °C (AS na) va bién thién entropi hn hep rugu nuée tit 25 °C xubng 11,83 °C (AS wo) Bién thign entropi cua nude da ting ti 25 °C dén 11,83 °C gém 3 thanh phi H,0 (F) —S> H,0()—S> H,0()—*> 1,0 es) > tes = 11,83 (°C). 25°C orc orc tC Vay ASqa= AS, + AS, + AS, 3 AS .= 22 , 37,66, n 2 5 20 6008.10 5 20 95.55 jy 273883 _ 59.03 GK) 18 273-25 18273 «AB 2B Bign thién enropi hn hop mag me gdm ti 25 °C xubng 11,83 °C gm 2 thinh phn: AS tine = AS nade + AS re aS E7531 an 2EHAS 68.2 115 99 27RE HLA 18 298 46 298 Vay AS ng = 32,03 - 29,9 = 2,13 (.K") 29,9 (LK). (Néu th sin Kam theo cach Kc mes ing vin cho di dé theo bid diém)