S GIO DC V O TO GIA LAI CHNH THC

K THI CHN HC SINH GII CP TNH LP 12 THPT, NM HOC 2012 - 2013 Mn: Ha hc - Bng A Thi gian lm bi: 180 pht (khng k thi gian giao ) Ngy thi: 06/12/2012 ( gm 3 trang)

Ghi ch: Hc sinh c php s dng Bng tun hon cc nguyn t ha hc v my tnh cm tay tham kho cc hng s thng dng. Cu 1. (3,00 im) 1. Trong phn t H2O v OF2 nguyn t O u trng thi lai ho sp3. Hy so snh gc lin kt trong phn t ca chng vi nhau v vi gc lai ho, gii thch? 2. a. Vit cu hnh electron ca phn t n cht halogen (X 2). b. Nhit bt u phn hu ca cc n cht: F 2, Cl2, Br2 v I2 ln lt l 450oC, 800oC, 600oC v 400oC. So snh nng lng lin kt trong phn t ca F2, Cl2, Br2 v I2, gii thch? 3. So snh tnh kh ca Fe(II) trong mi trng axit v trong mi trng kim. o o Bit E Fe /Fe = -0,44 V; E Fe /Fe = -0,04 V; tch s tan ca Fe(OH) 2 v ca Fe(OH)3 ln lt l 1,65.10-15 v 3,8.10-38; trong mi trng axit mnh s to phc hidroxo ca Fe(II) v Fe(III) khng ng k. Cu 2. (3,00 im) Dung dch bo ha H2S c nng 0,100 M. Hng s axit ca H2S: K1 = 1,0.107 v K2=1,3.1013. 1. Tnh nng ion sunfua trong dung dch H2S 0,100 M khi iu chnh pH = 2,0. 2. Mt dung dch X cha cation Mn 2+ v Co2+ vi nng ban u ca mi ion u bng 0,010M. Ho tan H2S vo X n bo ho v iu chnh pH = 2,0 th ion no to kt ta? Cho: TMnS = 2,5 1010; TCoS = 4,0 1021. 3. C th tch ring hon ton hai ion Mn2+ v Co2+ trong dung dch trn bng dung dch H 2S bo ho pH = 2,0 c khng? Cu 3. (2,00 im) Lm hai th nghim i vi phn ng: H2O2 + 2HI 2H2O + I2 Th nghim 1: Trn 10,0 cm3 dung dch HI 0,5M vi 10,0 cm3 dung dch H2O2 1,0.10-4M, 40,0 cm3 H2O v 50,0 cm3 H2SO4 1,0M. Bc phn ng c xc nh bng 1. Th nghim 2: Trn 20,0 cm3 HI 0,5M vi 10,0 cm3 H2O2 1,0.10-4M, 30,0 cm3 H2O v 50,0 cm3 H2SO4 1,0M. Bc phn ng xc nh c cng bng 1, nhng tc phn ng gp hai ln so vi th nghim 1. 1. Xc nh bc ring phn v bc chung ca phn ng. 2. Bit phn ng trn xy ra qua hai giai on v c to ra sn phm trung gian HIO. Hy vit cc phng trnh phn ng xy ra v cho bit phn ng no quyt nh tc phn ng? Cu 4. (1,75 im) Xc nh mi quan h v cu trc ca cc hp hu c sau: 1. 2.
2+ 3+

CH 3 HO H H OH CH 2OH

COOH

COOH

H 3C HO H

H
H

OH CH 2OH
H CH 3 Br

Br

Br H

H CH 3

Br

3.
1

4.

OH H H CH2OH HO CH2OH

Br

Br

5.

6.
H3 C

CH3 H 3C

CH 3

H 3C

CH3

7.
OH OH O HO OH H H HO OH OH OH H H H OH OH O

Cu 5. (2,5 im) 1. Trong phng th nghim bng cc phng php ha hc v vt l thch hp hy nhn bit cc cp cht sau: a. 3-deoxy-D-glucoz v 2-deoxy-D-glucoz. b.
CH3
CH2

H3C H 3C

H3 C

v H3C c. Cp cht: CH3CH2CH=C=CH-COOH (1) v CH2=CH-CH(COOH)-CH=CH2 (2). 2. Cho cc cht sau: CH3CH2CHO (1); CH3CH2OH (2); PhCHO (3); PhCH2COCH3 (4); (CH3)3CCOCH3 (5); CH3CH2COCH2CH2COCH3 (6) v PhCH2OH (7). Nhng cht no c th to ra kt ta mu vng khi phn ng vi I2 trong dung dch KOH? 3. Hy tch ring tng cht ra khi hn hp gm 3 aminoaxit l: Histidin (pH I = 7,59); axit aspartic (pHI = 2,77) v arginin (pHI = 10,76) bng phng php in di. Cu 6. (4,00 im) 1. Vit cc phng trnh phn ng chuyn ha D-glucoz thnh: a. 3-deoxy-D-glucoz. b. D-alloz (bit D-alloz l ng phn epime vi D-glucoz nguyn t cacbon th 3). 2. Vit cng thc chiu Fischer v cho bit xyloz thuc dy D hay L? Bit xyloz c cu trc sau:
O OH OH

HO OH

3. Mt metyl -andoz (X) tc dng vi HIO4 sinh ra sn phm hu c duy nht A. Metyl ha metyl glycozit ca X bng CH3I d, tip theo thu phn xc tc axit, ri oxi ha mnh sn phm thu c th to ra i-O-metyl ete ca axit ( S,S)-tactric. Hy bin lun suy ra cng thc Haworth ca X v vit cc phng trnh phn ng xy ra. 4. D-apioz l mt monosaccarit mch nhnh c cng thc chiu Fischer l
CHO H HO OH CH 2 OH CH 2OH

Vit cc cng thc Haworth dng vng furanoz ca D- apioz? Cu 7. (2.00 im) Cho bit cu trc v ha lp th ca cc cht A, B, C v D trong cc phn ng sau: 1. 2.
O Ph Ph O 1.EtONa 2.H 3 O+ OH Br2 CCl4

A
OH

3.

4.
H3 C CH 3

1 BH3

1 O3 2. Me 2S

C
CH 3

2. H 2O 2, OH-

Cu 8. (1,75 im) Bupivacain (C18H28N2O) l amit ca axit 1-butylpiperiin-2-cacboxylic vi 2,6-imetylanilin dng S c dng lm thuc gy t cc b.

(S)-Bupivacain c th tng hp t clorohidrat ca L-lysin nh sau:

Cho rng khi tc dng vi LiOH ch c nhm axit v tr mi xy ra phn ng. Hy v cu trc ca cc cht: A, B, C, D, E, F, G, H, I v J.
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