B GIO DC V O TO

THI CHNH THC

K THI CHN HC SINH GII QUC GIA THPT

NM 2013
Mn: HA HC

Thi gian lm bi: 180 pht (khng k thi gian giao ) Ngy thi thc nht: 11/01/2013

Cu 1. (4,5 im) 1. Kt qu tnh Hoa hc lng t cho bit ion Li2+ c nng lng electron cc mc En (n l s lng t chnh) nh sau: E1 = -122,400eV; E2 = -30,600eV; E3 = -13,600eV; E4 = 7,650eV. a) Tnh cc gi tr nng lng trn theo kJ/mol (c trnh by chi tit n v) b) Hy gii thch s tng dn nng lng t E1 n E4 ca ion Li2+. c) Tnh nng lng ion ha ion Li2+ (theo eV) v gii thch. 2. Chuyn ng ca electron dc theo mch cacbon ca mt h lin hp mch h c coi l chuyn ng t do ca v ht trong hp th mt chiu. Nng lng ca vi ht trong hp th mt chiu c tnh theo h thc: En =
-31

, trong n = 1, 2, 3; h l hng s Planck; m l

khi lng ca electron, m = 9,1.10 kg; a l chiu di hp th. i vi h lin hp, a l chiu di mch C v c tnh theo cng thc: a = (N+1).lC-C, y N l s lng t C; lC-C l di trong bnh ca lin kt C-C. ng vi mi nng lng En nu trn, ngi ta xc nh c mt obitan phn t (vit tt MO-) tng ng, duy nht. S phn b electron vo cc MO- cng tun theo cc nguyn l v quy tc nh s phn b electron vo cc obitan trong nguyn t. S dng m hnh vi ht chuyn ng t do trong hp th mt chiu cho h electron ca phn t lin hp Octatetraen, hy: a) Tnh cc gi tr nng lng En (n= 15) theo J. Biu din s phn b cc electron trn cc MO- ca gin nng lng v tnh tng nng lng ca cc electron thuc Octatetraen theo kJ/mol. Cho bit Octatetraen c lC-C = 1,4A0. b) Tnh s sng (cm-1) ca nh sng cn thit kch thch 1 electron t mc nng lng cao nht c electron (HOMO) ln mc nng lng thp nht khng c electron (LUMO). Cu 2: (4,0 im) 1. Bng tun hon c 118 nguyn t. Nguyn t X (Z = 118) c hnh thnh khi bn ph ht nhn Californi ( ) bng ht nhn Canxi ( ). Bit nguyn t X phn r v c s khi l A = 249. a) Vit phng trnh phn ng tng hp v phn r ca nguyn t X. b) Vit cu hnh electron nguyn t ca nguyn t X. T suy ra v tr ca X trong bng tun hon cc nguyn t ha hc. 2. Cho M l mt kim loi hot ng. Oxit ca M c cu trc mng li lp phng vi cnh ca c s l a = 5,555A0. Tnh s mng c s, ion O2- chim nh v tm cc mt ca hnh lp phng, cn ion kim loi chim cc hc t din (tm ca cc hnh lp phng con vi cnh l a/2 trong mng). Khi lng ring ca oxit l 2,400g/cm3. a) Tnh s ion kim loi v O2- trong mt c s. b) Xc nh kim loi M v cng thc oxit ca M.

c) Tnh bn knh ion kim loi M (theo nm) bit bn knh ca ion O2- l 0,140 nm. d) Nu cch iu ch oxit M. Cu 3. (3,5 im) 1. Nu hin tng v vit phng trnh ha hc ca phn ng xy ra trong cc th nghim sau: a) Sc t t kh clo (n d) vo dung dch NaBr. b) Cho mt t bt MnO2 vo dung dch H2O2. c) Cho dung dch SnCl2 vo dung dch FeCl3, sau cho thm K3[Fe(CN)6]. d) Cho dung dch KI vo dung dch FeCl3. 2. Canxi xyanamit c iu ch theo phn ng (1) v (2), n phn ng vi nc v axit sunfuric theo phn ng (3) v (4) di y: CaO + 3C CaC2 + CO (1) CaC2 + N2 CaCN2 + C (2) CaCN2 + 3H2O CaCO3 + 2NH3 (3) CaCN2 + H2SO4 CaSO4 + H2N-CN (4) a) Hy trnh by ngn gn v nh hng ca p sut v nhit n chiu din bin ca phn ng (1) v (2). b) Da vo cc phn ng cho, hy gii thch v vit cu to ha hc (c ghi y cc electron ha tr) ca CaCN2. c) Hy vit c ch phn ng gii thch s to thnh NH3 phn ng (3) v H2N-CN (xyanamit) phn ng (4). d) Vit cng thc Liuyt ca cc ng phn ng vi phn t CH2N2. Cu 4. (4,0 im) 1. xc nh hm lng oxi trong nc song, ngi ta s dng phng php Winkler bng cch dng Mn2+ c nh oxi di dng hp cht ca Mn(IV) trong dung dch kim. Sau , dng KI kh Mn(IV) trong mi trng axit v chun hn hp bng dung dch Na2S2O3. C th: Ht 150,00 ml nc sng vo chai c nh oxi. Thm MnSO4 d, sau thm tip dung dch kim iodua (gm NaOH v KI d), y nt bnh cn thn trnh bt kh v yn cho kt ta lng xung. Axit ha hn hp bng H2SO4 c. y nt chai v lc k cho n khi kt ta tan hon ton. Chun ngay dung dch thu c bng dung dch Na2S2O3 8,0.10-3M ht 20,50 ml Na2S2O3. a) Vit phng trnh ha hc cc phn ng xy ra trong th nghim trn. b) Tnh ; . ( ) c) Gii thch ti sao: - Giai on c nh oxi phi thc hin trong mi trng kim. - kh Mn(IV) bng KI phi tin hnh trong mi trng axit. - Sau khi axit ha dung dch cn chun ngay. d) Tnh hm lng oxi trong nc theo mg/l. Cho:
( )=

10-14; 250C:

= 0,0592 =1,23V; =0,5355V

=1,23V;

2. Cn 0,432 gam axit yu HA, pha thnh 50,00 ml dung dch A. Tin hnh chun dung dch A bng dung dch chun NaOH 0,100M. Khi thm 50,77 ml dung dch NaOH vo A thi

dung dch thu c c pH = 5,0. Cn khi thm 60,00 ml dung dch NaOH vo A th t n im tng ng. a) Tnh khi lng mol ca axit HA. b) Tm hng s Ka ca axit HA. Cu 5. (4,0 im) 1. Nghin cu ng hc ca phn ng oxi ha kh trong dung dch nc: 2Fe3+(aq) + Sn2+(aq) 2Fe2+(aq) + Sn4+(aq) (1) 2+ 3+ Khi nng ca ion Fe rt ln so vi nng ca ion Fe , thc nghim xc nh c biu thc tnh tc phn ng nh sau: V = k.[Fe3+]2.[Sn2+]/[Fe3+]2 (2) a) Chng minh rng c ch phn ng di y l ph hp vi thc nghim: Fe3+ + Sn2+ Fe3+ + Sn3+
K1 2+ Fe + Sn3+ K-1 K2Fe2+ + Sn4+ (3) (4)

Gi nh rng gi tr ca hng s tc k2 l rt nh. b) C th tnh c k2 theo k(thc nghim) v hng s K ca phn ng (3) khng? 2. Xt qu trnh bay hi ca 1 mol nc lng 250C v 1atm. Cho bit nhit ha hi ca nc, nhit dung ng p ca hi nc v ca nc lng ln lt l: Hhh(1000C,1atm) = 40,668kJ/mol; Cp,H2O(l) = 75,31J.K-1.mol-1; Cp,H2O(k) = 33,47J.K-1.mol-1. Cc d kin trn coi nh c gi tr khng i trong khong nhit kho st. a) Tnh H, S, G ca h trong qu trnh ha hi ni trn? b) Da vo kt qu thu c, hy cho bit qu trnh ha hi ca nc c th t din ra hay khng? V sao? Cho bit, i vi qu trnh ng p c nhit bin i t T1 n T2, bin thin entropy c tnh theo h thc: S = Cp. . Ht