BO GIAO ie WVADAOTAO KY THI CHON HOC SINH GIOI QUOC GIA THPT NAM 2014 BE THI CHiNH TALC Mén: HOA HQC Thai gian: 180 phi (khdng ké thoi gian giao dé) Negay thi ther nhat: 03/01/2014 (Bé thi cé 03 trang, gm 05 edu) 5,5; K = 39; Mn = $5; Cu= 63,54; 1 eV 1,602.10"°3; 8,314 Jamol!.K"' = 0,082 atm.L.mol"K"!; Zco = 27; 1;C= 12; O= 16; Na=23; CI 5,022.10 mot; THK) 44; F = 96500 C.mol'; Cau I (3,0 diém) Nhigt phdn hoan to’n x gam KCIO3 (6 MnO2 xtc tc), Khi thodt ra duge thu qua chau dyng dung dich H,SO, loang (D = 1,15 g/mL) vio éng nghigm dp nguge (nh hinh vé) Cae dit kién thi nghiém: Nhiét d6 17°C; ap sudt khi quyén 752 mm Hg; thé tich khi thu duge trong éng nghiém V = 238 cm*; khoang cach gitta 2 mit thodng h = 27 cm; khdi Iugng ring cua Hg 1a 13,6 g/cm’; dp suat hoi nude trong dng nghiém 1a 13,068 mm Hg. 1. Tinh x 2. Nung néng mot thoi gian hén hop A gdm 10x gam KCIOs (gid tr] x thu duge 6 trén) va y gam KMnO,, thu durge chit rin B va 3,584 lit khi Op (dkte), Cho B tae dung hét véi dung dich HCI die, néng, du, thu duge 6,272 lit khi Cl; (dkte). Viét tét ed ede phuong trinh phan tng c6 thé xay ra va tinh y. Cau HT (4,0 diém) 1, Cho cdc ion sau day: He*, Li?*, Be™* a) Ap dung thie tinh nang lugng: En = -13,6(Z’/n*) (C6 don vi la eV); n 1a sé lugng tr chinh, Z.18 96 din tich hat nhan, hay tinh nang ugng E> theo don vj kI/mol cho méi ion trén (trong dap sé c6 4 chit sé thap phan). b) C6 thé ding tri sé nao trong cae tri sé nang Iugng tinh duge 6 trén dé tinh ning lung ion hoa ca hé tuong ting? Tai ©) G trang thai eo cae ion trén, ion nado bén nhit, ion nao kém bén nhat? Tai sao? 2, Thye nghigm cho biét déng tinh thé c6 khdi lwong riéng D = 8,93 elem’; bin kinh nguyen te dong lé 128 pm. Dang két tinh theo mang tinh thé lap phuong don gidn hay lap phuong tim dign? Tai sao? 3. Dong vi ‘211 ding trong y hoc thutmg duge diéu ché 1g cch bin pha bia chia "Te bing notron trong 13 phin tmg hat nhan. Trong phuong phép nay, trude tién “Te nbn 1 notron chuyén héa thinh "Te, réi déng vi nay phan ra P* tao thanh "31. a) Viét phuong trinh cde phan img hat nan xay ra khi diéu ché '331 b) Trong thoi gian 3 gid, 1 mL dung djch '3\1 ban dau phat ra 1,08.10" hat - Tinh ndng 46 ban dau cia '3}1 trong dung dich theo don vj pmol/L. - Sau bao nhigu ngay, hoat do phong xa riéng cua dung dich '}:1 chi con 10° Bq/mL? Biét chu ki ban ri cia ‘}T 14 8,02 ngiy. trang 1/3Cau III (4,5 diém) 1, Cho phan img: 2A+B>C+D ‘Thy nghigm cho biét phuong trinh ding hoc t5e 46 cia phan img c6 dang nhu sau: (APB {c] Gian dé nang lugng cia phan img c6 dang nhw hinh vé. Thye nghiém cho biét phan img EB xay ra qua 2 giai dogn, mét trong 2 giai dogn dé la thudn nghich. a) Dé xudt co ché cia phan tmg sao cho phi hop ‘y6i phuong trinh ddng hoc va gin 46 nang Iuong a cho. b) Trén co sé co ché phan tmg, hay tim he thie lign he gita hing s6 tdc d6 chung cia phan img v6i cdc hing s6 téc d9 cita cée giai doan. ¢) Tim hé thite lién hé gitta ning lugmg hogt hoa chung (Ea) ciia phan tng véi cdc gid tri Ea, Bas va Ea. Biét ring, nang lngng hoat héa E phy thude vio hing s6 téc 46 phan img k theo phuong > dink Rv SS 2. Déi voi phan img dé hidro héa et CoHe (kK) = CoH (k) + He (&) @ 6 cae s6 ligu sau: AGS, = 22.39 kJ.mol" va cdc gid tri entropy duge ghi 6 bang dudi day: [ Chat Hy CoHe Coy I Syoox [J-mol.K"] 163,0 319,7 291,7 a) Tinh Ky ciia phan img (1) tai 900K. b) Tinh AHgoo, cita phan img CoHs (Kk) + Ho (k)—> C2Hs (k) ©) Tinh Ky tai 600K cia phan tng (1), gia thiét trong khoang nhiét 46 tir 600K dén 900K thi AH? va AS’ khéng thay di. 3. 6 1396K va dp sudt 1,0133.10° N.m®, dO phan li cia hoi nude thanh hidro va oxi 1a 0,567.10; a6 phan li ciia cacbon dioxit thinh cacbon oxit va oxi la 1,551.10. Hay xée dinh thanh phan hén hop khi (6 trang thai can bang) duge tao thanh theo phan tmg: CO+H;0 = Hy + CO: ‘tr hai thé tich nhu nhau ca cacbon oxit vi hoi nude & diéu kign trén. Cfu IV (4,5 diém) 1. Chat A la hgp chat c6 thanh phan chi gdm nito va hidro. Chat A duge sir dung lam nhién ligu cho tén lita. 6 cing didu kién vé nhiét d6 va dp sudt, m6t thé tich hoi cla A 6 khdi lugng bang khéi long cia cling mét thé tich khi oxi a) Xée dinh céng thie phan tir, cOng thiic cdu tao ciia A va cho biét trang thai lai héa cia nite trong A. b) Dya vio de diém edu tao, hay so sénh tinh bazo va tinh khtr cia A vési NHs. Giai thich. trang 2/3) Ngudi ta thyc hign thi nghiém sau: cho 25,00 mL dung dich A ndng 46 0,025M vao dung. dich Fe,(SO,)s du, dun néng, thu duge dung dich B va mét chit khi X. Chuan d6 1/2 dung dich B trong méi trudng axit, can vira dit 12,40 mL dung dich KMnOg. Biét rang chuan 46 10,00 mL dung dich H2C205 0,05M (trong méi truémg axit HzSOq) can via dit 9,95 mL dung dich KMn0, trén. Xée dinh chat X. 2. Nam 1965, céc nha khoa hoc dai tim ra phuong php c6 dinh nito 6 nhigt d6 phong bing céch din khi nito di qua dung dich pentaaminoaquoruteni(II) (Ai). Khi 46, nito sé thay thé nu6éc trong cdu ni cia Ay tao phire chét méi Ag. Phite chat A cé tinh thudn tir. a) Viét phuong trinh phan img xay ra. b) Ap dung thuyét lign két héa tri (VB), hay mé ta lign két trong phite Az va dy doan cdu tric hinh hoc cia n6. Xéc dinh héa tri va sé oxi héa cia ruteni trong phite chat Ao 3. Trong dung dich OH’ 1,0M cia [Co(NHs)sCI]* tdn tai can bang: [Co(NHs)sCI]* + OH = [Co(NH3)«(NH2)CI}* + 10. 6 25°C, tai thai diém cn bing xéc dinh duge ring it nhdt 95% phite chat tin tai o dang axit [Co(NH3)sCI}?*. Chimg minh [Co(NHs)sCl]*" 1a mét axit rat yéuco K, < 5,26.10" 4. NHb 6 kha ning phan tmg véi nhigu ion kim logi chuyén tigp, Alfred Wemer (duge gidi Nobel héa hoc nim 1913) da phan lap thanh céng mot s6 phite chat gitta CoCl; va NHs, trong 46 c6 phite chit bat dién véi cng thite phan tir 1a CoCl4NHs. Tay thude vao diéu kign tong hop, phite chat nay 6 mau tim ho§c mau xanh. Khi cho lugng du dung dich AgNO; téc dung ‘v6i dung dich chira 1 mol phitc chat nay déu thu duge 1 mol AgCl két tia, Hay xée dinh cdc cong thite cé thé cé etia phite chat néu trén, Cau V (4,0 diém) 1. Tinh hing sé cn bing cita phan img: Cr07 + H,0 2, Tr6n 10,00 mL dung dich KxCr0; 0,80M véi 10,00 ml. dung dich A gbm BaCl, 0,08M va SrCl; 0,08M thu duge hén hop B. Hay cho biét hign tung xay ra va thanh phan hén hop B. 3. Tinh khéi lugng CHyCOONa can cho vao hén hgp B, khi cé mat CsHsCOOH 0,02M dé bat dau cé két tia SrCrO, tach ra (bo qua sy ting thé tich do thém CH3;COONa). 4. Tinh khoang pH can thiét lap dé c6 thé tach hoan toan ion Ba” ra khdi ion Sr* bing K:CrO; Khi trn 10,00 mL. dung dich K,Cr0; 0,80M véi 10,00 mL dung dich A (coi Ba duge tach hoan toan khi ndng 46 cén lai cia Ba”* trong dung dich nhé hon hode bang 1,0.10°M). Cho: CrO*+H,0 = HCrOs +OH Ky= 1075 C07 +H,O = 2HCrOs K=10' pK,(CH;COOH) = 4,76; pK,(CoHsCOOH) = 4,20; pKy(F20) = 14,0; pKs(BaCrO,) pK,(S1Cr0,) = 4,65. 2C10"" + 2H" os * Thi sinh khong duoe sie dung tai ligu; + Gidm thi khing gidi thich gi them trang 3/3BQ GIAO DUC VA DAO TAO KY THI CHON HQC SINH GIOI QUOC GIA THPT DE THI CHiNH THUC NAM 2014 Mén: HOA HQC ee ee ‘Thai gian: 180 phat (khong ké thoi gian giao dé) Rf : Negay thi thir hai: 04/01/2014 + (Dé thi c6 03 trang, gom 0S céu) (Chi ¥ m@t s6 ki higu viét tit: Me: metyl, Et: etyl, Pr: isopropyl, Ph: phenyl, Ar: aryl, Ac: axetyl, m-CPBA: axit m-clopeoxibenzoic) Ciiu I (4,0 diém) 1. Cho cae hgp chat sau: ° 9 9 9 ° i i i i i 1 I 4 5 AOQoaeonogp o a an ay) ”) wp any win ax) a) So sdnh kha ning enol héa ciia cdc hgp chat trén. Giai thich ngéin gon. b) Hop chat (V) dé chuyén héa thanh hop chat T c6 cOng thtte CigHsO2. Hay cho biét céng thite cu tao cia T va gid thich, €) Hap chat (VEID) tgo duge oxim khi phan img v6i hidroxylamin, hop chat (VI) thi khong. Gi thich. 2. Cho cae hop chat X va Y c6 cng thire nhur hinh vé, So sinh (c6 giai thich) momen Iuéng eye cia cde hop chat X va. 3. Vé c6ng thire phéi cénh va cong thic chiéu Niumen cia hgp chat 7,7-dimetylbixiclo[2.2. 1 ]heptan. 4, Hop chit A (CH:N2) c6 momen lung cue 1a 4,52 D” (Cho biét momen ludmg cue cia fomandehit li 2,33 D). x Chit A phn img véi amoniac cho hop chat B (CHN:). 6 nhigt 46 thuémg A chuyén hoa tinh hop chat € (CoHANe) ndng chay 6 210°C. 6 nhigt 49 cao A chuyén héa think hop chit E (CaHkNe) nong ehiy 6 350°C. ‘a) Hay viét (cé gidi thich ngin gon) cong thite cdu tao cita cdc hop chat A, B,C va E. b) Viet co ché ctia phan img tgo thanh B, C va E. ©) So sénh (cé giti thich) lye bazo cia A, B, C va E. 4) Ding céng thite cdu tgo, viét phurong trinh phan tig cia A véi MeOH, HS, dung dich NaOH die va ‘v6i AGNOs tao két tha AgsCN>. CA II (4,0 diém) 1. Xéc dinh cdu tao cia cdc hop chat chua biét trong so dé sau: oO Maes 5 v Nc io ee ee ee wei _ >G a oe NHAc H,SO44, © m-CPBA Hj0° Ac, Qmol) 1) NaOH (1 mol) ee OE ESL ee a WC uthyNo) 2) Me,SOyNeOH. 2. Ba hgp chit P, Q va S cé cling c6ng thite phan tir CsHysO3, Nguoi ta thyc hign qué trinh chu P theo so dé sau: oe 1) NaEVOH 1) (P10),AV/-PrOH 1)05 Sees FeO) a P2(CiH4203) = P3(Cithe) > Ps 2) HO" 2) HySO«d, ° ) a) Biét P4 c6 cOng thite O=CH-CH-CH;-CO-CH3-CH=0, hay xc dinh céng thie cdu tao cia P, Pl, P2 va P3 trong so dé trén. Trang 1/3b) Khi xir li cae chat Q hode $ bing E1ON@/EtOH déu tgo ra P. Xée dinh céng thite cdu tao cia Q va S. Giai thich ngén gon sy chuyén héa Q va $ thanh P. 3, Pirimidin va dan xuat ciia né 6 khé nhiéu hoat tinh sinh hoe nhu khéng khuan, khang ném, chéng st rét, khang virus HIV... So dd dudi day ding dé téng hop 2-amino-6-aryl-4-(5-hidroxi-4- metyleumarin-6 6- -yDpirimiin (chat Z). ou fe exscocngcogtt —arCHO HEN HE x vt AICI, khan, ¢° e Hay cho biét céng thite edu tgo otia cde chat T, X, Y va Z trong so dé trén. Céu THT (4,0 diém) 1, M@t monosaccarit A khéng quang hoat c6 cOng thite phan tir CsHioQs. Chat A c6 phan img véi thuéc thir Feling nhung khéng phan ting véi nude brom. Khir A bing NaBH), tao thanh cde hgp cl va C c6 ciing céng thite phin tir C> Kg= 107?! >> Ky= 10°" nén c6 thé xe dinh néng 4 H,SO, va HPO, trong hén hop bang cach chudn d@ bang dung dich chuan NaOH vi 2 chat chi thi 1a phenolphtalein va bromocrezol xanh.Khi chuan 46 hén hgp bing dung dich chudn NaOH véi chi thi bromocrezol xanh, H,SO, bj trung héa thinh Na,SO,, HPO, bj trung héa thanh NaH,PO,: H,SO, + 2NaOH — Na,SO, + 2H,0 (1) HsPO,+NaOH = NaH;PO,+H;0 (2) Khi chudn 49 hén hop bang dung dich chudn NaOH véi chi thi phenolphtalein, H,SO, bj trung héa thanh NaySO,, HjPO, bi trung héa thanh Na,HPO,: H,SO,+2NaOH — Na,SO, + 2H,0 (1) HPO, +2NaOH — Na;sHPO,+2H;,0 (3) Két hop 2 phép chuan d9 sé tinh duoc néng dé H;SO, va H;PO, trong dung dich phan tich. 3. Cach tién hanh 1) Chuyén dung dich chuan NaOH lén buret va digu chinh dén diém khéng. Ding Pipet, lay 10,00 ml dung dich mau cn phan tich (trong 19 dymg mau), chuyén vao binh dinh mite dung tich 100,0 ml. Thém nude edt vao binh dén vach mite, lc déu durge dung dich A. 2) Ding pipet lay 10,00ml dung dich A cho vao binh tam giéc co 250ml, thém vao Khoang 10ml nuéc cét, thém 2 giot chat chi thj bromocrezol xanh, dung dich cé mau vang.Tir buret nhé tir tir dung dich chuan NaOH 0,05100 M dén khi mau dung dich trong binh tam giae chuyén sang xanh (bén trong 30 sidy) thi dimg lai. Ghi thé tich dung dich NaOH di ding (ki higu 1a V; ml), ldy dén hai chit sé sau ddu phy. 3) Diing pipet lay 10,00 ml dung dich A cho vao binh tam gide c& 250ml, thém vao khong 10ml nude cét, thém 2 giot chat chi thj phenolphtalein, dung dich khong mau. Chuan d6 dung dich trong binh tam giéc bing dung dich chudn NaOH 0,05100 M cho dén khi dung dich trong binh tam gide c6 mau héng (bén trong 30 gidy) thi dimg Iai. Ghi thé tich dung dich NaOH df ding (ki higu 1a V> ml), Idy dén hai chit sé sau ddu phay. Lap lai cdc phép chuan 46 6 bude 2 va bude 3 it nhat 1 lan dé Idy két qua trung binh. (Thi sinh ne thiét ldp cng thiic va tinh néng dé timg chat trong dung dich m&u ban diw) Thi sinh bao c4o két qua thi nghigm vao phiéu danh gid két qua kém theo. Ghi cui: Cén b6 coi thi khong giai thich gi them