S GIO DC - O TO

THNH PH NNG

K THI HC SINH GII THNH PH

NM HC 2006 - 2007
HNG DN CHM MN HA HC LP 12 - BNG A

Cu 1 (2,0 im)
1. nh sng nhn thy c phn hy c hi Br 2 thnh cc nguyn t khng? Bit nng lng phn ly
lin kt Br2(k) l 190kJ.mol-1; h = 6,63.10-34 J.s; c = 3.108 m.s-1; NA = 6,022.1023 mol-1.
2. Kt qu nghin cu thc nghim cho bit ion Cr2+ to ra ion phc dng bt din [Cr(CN)6]4- c momen
t l 2,8 B. Trnh by cu to ca ion theo thuyt lin kt ha tr.
P N

IM

1. D = h(c/ ).NA = 6,3.10 m

-7

nm trong vng cc tia sng nhn thy nn nh sng nhn thy phn hy c hi
Br2.
2. Cu hnh electron ca ion Cr2+: [Ar]3d4
S phn b electron trn cc obitan trong ion Cr2+ :

3d
4s
4p
4d
Gi n l s electron c thn trong ion [Cr(CN)6]4Ta c: n(n +2) = 2,8
n = 2
Ion [Cr(CN)6]4- c 2 electron c thn nn c s dn electron trong ion Cr 2+ nh sau (do
CN- l phi t trng mnh):

Ion Cr2+ trng thi lai ha d2sp3 (lai ha trong), hnh thnh 6 obitan lai ha d2sp3 trng
c cc trc hng ra 6 nh ca hnh bt din u. Cc obitan lai ha ny to lin kt
cho - nhn vi 6 ion CN-, hnh thnh nn phc cht [Cr(CN) 6]4- c cu trc hnh bt
din u.
Cu 2 (2,5 im)
1. Tnh in li ca CO32 trong dung dch Na2CO3 c pH =11,60; CO2 c pKa1 = 6,35 v pKa2 = 10,33.
2. Brom lng tc dng c vi H3PO3 theo phn ng: H3PO3 + Br2 + H2O H3PO4 + 2H+ + 2Bra) Tnh th in cc chun Eo(H3PO4/H3PO3). Bit Eo(Br2/2Br-) = 1,087V.
b) Tnh th in cc chun Eo(H3PO3/H3PO2). Bit Eo(H3PO4/H3PO2) = - 0,39V
Cho bit cc s liu sau 298K:
H3PO4(dd)
Br-(dd)
H3PO3(dd)
Br2(l)
H2O(l)
o
H (kJ/mol)
-1308
-141
-965
0
-286
So(J/mol.K)
-108
83
167
152
70
P N
1. (1 im)

CO32 + H2O
HCO3 + OH
Kb1 = 10-14/10-10,33 = 10 3,67

HCO3 + H2O
(H2O.CO2) + OH Kb2 = 10-14/10-6.35 = 10 7,65
Kb1 >> Kb2 , cn bng (1) l ch yu.

CO32
+
H2O
HCO3 + OH
Kb1 =10 3,67
C
C

[ ]
C 10 2,4
10 2,4
10 2,4
Kb1 =

(10 )

2, 4 2

C 10

2, 4

IM
(1)
(2)

= 10 3,67 C = 10 2,4 + (10-4,8/10-3,67) = 0,0781 M

1/8

 (CO32-) =

10 2, 4
.100 % = 5,1%
0,0781

2. (1 im)
a) Hop = -339kJ
Sop = -331JK-1.
Gop = -240,362kJ lgK 42,125 K = 1,33.1042.
Gop = -nFEop Eop = 1,245V
Eo(Br2/2Br-) - Eo(H3PO4/H3PO3) = Eop = 1,245V
Eo(H3PO4/H3PO3) = -0,158V - 0,16V
b) H3PO4 + 4H+ + 4e H3PO2 + 2H2O
Eo1 = - 0,39V (1)
H3PO4 + 2H+ + 2e H3PO3 + H2O
Eo1 = - 0,16V (2)
+
Ly phng trnh (1) (2) ta c: H3PO2 + 2H + 2e H3PO2 + H2O
Go3 = Go1 - Go2 -2FEo3 = -4FEo1 (-2FEo2) Eo3 = -0,62V

Eo3 = ?

Cu 3 (2,0 im)
Brommetan phn ng vi OH- theo c ch SN2. Tc ban u ca phn ng v cc nng ban u ca
CH3Br v KOH cho bng di y, tt c cc th nghim u tin hnh 25oC.
[CH3Br] (mol.L-1) [KOH] (mol.L-1) Vo(mol.L-1.s-1)
Th nghim 1
0,100
0,10
2,80.10-6
Th nghim 2
0,100
0,17
4,76.10-6
Th nghim 3
0,033
0,20
1,85.10-6
1. Xc nh bc ring phn ca CH3Br, OH- v bc ca phn ng. Vit phng trnh vn tc phn ng.
Tnh hng s tc ca phn ng.
2. Trong th nghim (1), cn thi gian bao nhiu nng KOH cn li 0,05mol.L-1.
P N

IM

1. Phn ng:
CH3Br + OH- CH3OH + BrBc n1 ca phn ng i vi KOH c xc nh t cc d kin ca th nghim 1 v 2
trong khi nng ca CH3Br gi khng i:
lg 4,76 .10 6 lg 2,8.10 6
=1
lg 0,17 lg 0,10

n1 =

Nh vy, bc ring phn ca KOH l bc 1.

Do , t th nghim 1 nu nng ca KOH l 0,20mol.L-1 th Vo = 2,80.10-6 * 2 =
5,6.10-6mol.L-1.
T cc d kin ca th nghim 3 v Vo khi nng KOH bng 0,20mol.L-1 ta c bc n2
ca phn ng i vi CH3Br nh sau:
n2 =

lg 1,85 .10 6 lg 5,60 .10 6

=1
lg 0,033 lg 0,10

Nh vy, bc ring phn ca CH3Br l bc 1.

Bc tng cng ca phn ng l bc 2.
Phng trnh vn tc phn ng: V = k. C(CH3Br).C(OH-)
2,8.10 6
= 2,8.10 4 L.mol 1 .s 1
k=
0,12

2. Khi trong bnh cn li 0,05mol.L-1 KOH th cng cn li 0,05mol.L-1 CH3Br. Thi gian
phn ng l:

1
1
=
= 35714 s = 9,9h
kC o
2,8.10 4.0,1

2/8

Cu 4 (2,0 im)
Cho cc d kin nhit ng sau:
C2H5OH (l) O2 (k) CO2 (k)
H2O (l)
0,00
-94,05
-68,32
Ho298
(kcal/mol)
So298(cal/mol.K)
32,07
49,00 51,06
16,72
C2H5OH (l) + 3O2 (k) 2CO2(k) + 3H2O (l) H = -326,7 kcal
C (gr) C (k) H = 171,37 kcal/mol
C2H5OH (l) C2H5OH (k) H = 9,4 kcal/mol
H2 (k) 2H (k) H = 103,25 kcal/mol
EC-C = 83,26 kcal/mol; EC-H = 99,5 kcal/mol;
O2 (k) 2O(k) H = 117,00 kcal/mol
EC-O = 79,0 kcal/mol.
1. Tnh hiu ng nhit ng tch phn ng t chy C2H5OH (l), sinh nhit tiu chun ca C2H5OH (l) v
nng lng lin kt O-H trong C2H5OH.
2. Tnh hng s cn bng ca phn ng t chy C2H5OH 298K. T gi tr thu c hy nhn xt v
mc tin trin ca phn ng.
P N
1. Phn ng: C2H5OH + 3O 2 = 2CO2 + 3H2O
p dng cng thc: U = H - nRT v thay cc gi tr vo ta c:
U = -326,107 kcal
T phn ng ta c : Hop = 2 Ho(CO2) + 3 Ho(H2O) - Ho(C2H5OH)
T suy ra: Ho(C2H5OH) = -66,35 kcal/mol
Theo cch lp s lin h gia Hi v Ei ca cc qu trnh bin i ho hc theo cc
s liu bi cho ta tnh c gi tr nng lng lin kt O-H trong C2H5OH l:
EO-H = 108,19 kcal.
2. Sop = 2So(CO2) + 3So(H2O) So(C2H5OH) = -27,42 cal/mol.K
Gop = Ho - T So = 318528,84 cal/mol
Suy ra: lgK = -

G o
= 232 ,367
2,3.RT

IM

K = 10232,36

Hng s K rt ln. iu chng t phn ng xy ra hon ton

Cu 5 (2,0 im)
Ha tan 10,40 gam mt kim loi R trong dung dch HCl va , thu c dung dch X c RCl 2 v thu
c V1 lt kh H2. Chia dung dch X lm 2 phn bng nhau, phn I cho tc dng vi mt lng va
dung dch HNO3 m c, nng thu c V2 lt kh NO2 v dung dch Z (ion clorua khng b oxi ha),
phn II cho tc dng vi mt lng va dung dch H2SO4 m c nng thu c V3 lt kh SO2 (kc)
v dung dch T. C cn dung dch Z nhit thch hp thu c 40,00 gam mt mui A duy nht, c
cn dung dch T nhit thch hp thu c 25,00 gam mui B duy nht. Bit M A < 420 gam.mol-1 , MB
< 520 gam.mol-1. Xc nh R, cng thc ca A, B v tnh V1, V2, V3.
P N
Phng trnh phn ng:
(1) R + 2HCl RCl2 + H2
Phn ng gia dung dch RCl2 v HNO3 m c sinh kh NO2, vi dung dch H2SO4 sinh
kh SO2, iu ny chng t R2+ c tnh kh v b HNO3, H2SO4 m c oxi ha thnh R3+.
(2) RCl2 + 4HNO3 (c) R(NO3)3 + NO2 + 2HCl + H2O
(3) 2RCl2 + 4H2SO4 (c) R2(SO4)3 + SO2 + 2H2O + 4HCl
Gi 2a l s mol R ng vi 10,40 gam R
a l s mol R ng vi 5,20 gam R
Khi c cn dung dch Z, T ta c th thu c mui khan hoc mui ngm nc .
Gi R(NO3)3 . nH2O v R2(SO4)3 .mH2O l cng thc ca A, B vi n, m 0

IM

3/8

T (1) (2) (3) , suy ra :

S mol R(NO3)3. nH2O l a mol, s mol NO2 = a mol
S mol R2(SO4)3. mH2O l a/2 mol, s mol SO2 = a/2 mol
R(NO3)3. nH2O
40,00 gam
R2(SO4)3. mH2O
25,00 gam

R
5,20 gam
R
5,20 gam

M1 = 186 + 18 n
m1 = 34,80
M2 = 144 + 9m
m1 = 19,8

34 ,80
19 ,8
=
178,20 n 156,6 m = 664,2
186 +18 n
144 + 9m
M MA < 400 gam.mol-1 nn n < 11,9 . MB < 520 gam.mol-1 nn m < 11,8
Bin lun theo n hoc m, ta c 2 nghim ph hp l n = 9 , m = 6
Suy ra a = 0.1 v MR = 52 gam.mol-1 .
Vy R chnh l Cr
Cng thc mui A l Cr(NO3)3.9H2O . B : Cr2(SO4)3.6H2O
V1 = 0,1 x 22,4 = 2,24 L
V2 = 0,05 x 22,4 = 1,12L

Suy ra : a =

Cu 6 (2,0 im)
Xc nh D, F v hon thnh chuyn ha di y (mi mi tn ch tng ng vi mt phn ng):

Na2S2O3
(2)

(7)
(4)

(3)

(1)

(8) (11)
(12)

SO2
(6)
(5)

(13)

(14)

(10)

(9)

H2S

P N
(1) S + NaOH c Na2S + Na2SO3 + H2O
(2) Na2SO3 + S t Na2S2O3
(3) SO2 + 2 NaOH Na2SO3 + H2O
(4) Na2SO3 + 2HCl 2NaCl + H2O + SO2
(5) SO2 + 2 H2S 3 S + 2H2O
(6) S + O2 t SO2
(7) 4SO2 + 6 NaOH ( c ) + 2H2S 3 Na2S2O3 + 5H2O
(8) Na2S2O3 + 2HCl (long, ngui) 2NaCl + SO2 + S + H2O
(9) 2H2S+ 3O2 2SO2 + 2H2O
(10) SO2 + 6H H2S + 2H2O
(11) SO2 + Cl2 + 2H2O H2SO4 + 2 HCl
(12) Cu + 2H2SO4 t CuSO4 + SO2 + 2H2O
(13) H2S + 4Cl2 + 5H2O H2SO4 + 8HCl
4 Mg + 5H2SO4 4MgSO4 + H2S + 4H2O

IM

t0

Cu 7 (2,0 im)
Hp cht hu c A c 74,074% C; 8,642% H; cn li l N. Dung dch A trong nc c nng % khi
lng bng 3,138%, si nhit 100,372oC; hng s nghim si ca nc l 1,86oC.
1. Xc nh cng thc phn t ca A.
2. Oxi ha mnh A thu c hn hp sn phm trong c E (axit piridin-3-cacboxilic) v F (Nmetylprolin). Hy xc nh cng thc cu to ca A v cho bit gia E v F cht no c sinh ra
nhiu hn, cht no c tnh axit mnh hn.

4/8

3. A c 1 ng phn cu to l B; khi oxi ha mnh B cng sinh ra 1 hn hp sn phm trong c E v

axit piperidin-2-cacboxilic. Xc nh cng thc cu to ca B.
4. Cho A v B tc dng vi HCl theo t l mol 1:1, cht no phn ng d hn? Vit cng thc cu to
ca cc sn phm.
P N
IM

1. C : H : N =
M=

74 ,074 8,642 17 ,284

:
:
= 5 : 7 : 1 (C5H7N)n
12
1
14

k.m
3,138
1
=1,86
100
=162 g / mol
t
96 ,862
0,372

81n = 162 n = 2; CTPT: C10H14N2

2.
E

COOH

COOH
N
CH3

N
CH3

E sinh ra nhiu hn F

3.

Axit piperidin -2-cacboxilic:

N
H

B
N
H

COOH

N
anabazin

4.
N
N H3C

ClN

N Cl

Cu 8 (2,0 im)
1. Hy thc hin cc chuyn ha sau:

(a)

O
CH3

O
CH2OH
CH3

(b)

O
COOH
CH3

2. T 3,4-dihidroxibenzandehit hy iu ch cht di y:

COCH3
CH3

CH3O
P N

OCH3
IM

1. (a)

5/8

O
+ HCl

Cl
CH3

CH3

Mg

O
1. CH

2
MgCl
2. H+
CH3

CH2OH
CH3

(b)
O

Mg

+ HCl

CH3Cl

O
Mg

+ Cl2, a.s

CH3

MgCl

Cl
O
Cl
CH3

O
1.CO2

MgCl
2. H+
CH3

COOH
CH3

2.
CH O

CH O
CH3Cl,OH-

OH
OH

OCH3
OCH3

CH3
Zn(Hg)
HCl

CH3COCl,AlCl3

OCH3
OCH3 CH CO
3

CH3

OCH3
OCH3
Cu 9 (2,0 im)
1. (a) Vit phng trnh ha hc minh ha phn ng polime ha caprolactam trong mi trng kim iu
ch t nilon-6,6. (b) Trnh by c ch phn ng ny.
2. Vit s minh ho qu trnh iu ch hn hp raxemic 3,4-dihidroxiphenylalanin t vanilin.

CH3O

CH3

CH=O (vanilin)

P N
1. (a) Phn ng:
O
C
n
NH[CH2]5CO
N
H
(b) Phn ng th dy chuyn nucleophin:

Bazo

C NH
O

IM

Bazo-CO[CH2]5NH-

6/8

Bazo-CO[CH2]5NH-

Bazo-CO[CH2]5NHCO[CH2]5NH-

C NH
O

...

2. S minh ho:
MeO

HO

H
Me2SO4
C O
OH

MeO

H
Ac2O
C O

MeO

NaOAc

Vanilin
MeO

MeO

MeO

CH CHCOOH

H2/ Pd

MeO

MeO

CH2CH2COOH

1.Br2/P
2.NH3

HO
CH2CH COONH3+

MeO

HI

CH2CH COONH3+
D,L-dopa

HO

Cu 10 (2,0 im)
1. V cu dng gh bn v km bn cho:
(a) -D-manopyranoz
(b) -L-glucopyranoz
2. Lp lun xc nh cu to ca lactoz, mt disacacrit c trong sa, bit: (i) Thy phn trong emulsin
to ra D-glucoz v D-galactoz, (ii) l mt ng kh c kh nng nghch chuyn. (iii) Khi thy
phn osazon ca n thu c D-glucosazon v D-galactoz, (iv) Oxi ha nh nhng, sau metyl ha
ri cui cng thy phn to cc sn phm tng t nh sn phm thu c t mantoz.
P N

IM

1. Trong cu dng bn hn, nhm -CH2OH v ba nhm -OH khc v tr bin.

OH

H OH
HO
HO

(a)

OH
O
H

H
O

OH
H

(b)

H
H

OH

O
OH

H
OH

(bn hn)

HO
HO
H

OH

(bn hn)

(km bn hn)
OH

OH
H

O
H

OH
OH

OH

OH

H
OH

H
OH

(km bn hn)

2. (i) suy ra lactoz l mt -glucosit cu thnh t D-glucoz v D-galactoz. (ii) cho

bit lactoz c nhm OH-anome t do. (iii) cho bit cu t glucoz l aglycon do n to

7/8

c osazon v galactoz l mt -galactosit. (iv) cho bit c hai cu t u dng

pyranoz v lin kt vi nhau qua C4-OH ca cu t glucoz.
OH

OH

OH 1

O
HO

HO
b

OH
(B) D-galactoz

OH
O
OH
(A) D-glucoz

8/8