S GD &T VNH PHC

CHNH THC

K THI HSG LP 12 THPT NM HC 2011 2012

THI MN: HA HC
Dnh cho hc sinh trng Chuyn Vnh Phc
Thi gian lm bi 180 pht khng k thi gian giao
Lu : thi c 02 trang.

Cu 1 (1,0 im). Nghin cu ng hc ca phn ng:

2NO (k) + 2H2 (k) N2 (k) +
2H2O (l)
Ngi ta thu c cc s liu sau:
P(NO), atm
P(H2), atm
Tc phn ng (atm.s1)
0,375
0,500
6,34.10 4
0,375
0,250
3,15.10 4
0,188
0,500
1,56. 10 4
a) Vit biu thc lin h tc phn ng vi p sut cc cht tham gia phn ng.
b) Phn ng c cho l bao gm 3 giai on s cp:

N2O2 nhanh
Giai on 1: 2NO

Giai on 2: N2O2 +
H 2 N2O +
H2O chm
Giai on 3: N2O + H2
N2
+
H2O nhanh
C ch phn ng trn c ph hp vi quy lut ng hc thu c t thc nghim khng?
Cu 2 (1,5 im).
1. 250C, bin thin entropi tiu chun ca phn ng:
3Fe2O3 (r) 2 Fe3O4 (r) + O2 (k)
l 125,4 J.K-1.mol-1
Trong cng iu kin entanpi sinh tiu chun ca Fe2O3 (r) v Fe3O4 (r) ln lt bng -821,4 kJ.mol-1 v
-1116 kJ.mol-1.
a. 250C v di p sut ca O2 l 1atm, oxit st no l bn v mt nhit ng hc?
b. Fe2O3 l thnh phn chnh ca r st. iu ny c phi l bnh thng khng?
2. nhit 1000oK, hng s cn bng ca phn ng:

3FeO (r) + CO2 (k) ; Kp = 1,1

Fe3O4 (r) + CO (k)

Ngi ta cho 100g Fe3O4 v 1 mol CO vo 1 bnh phn ng 10 lit ri nung nng ln 1000oK
a. Tnh thnh phn ca pha kh khi h thng khng din bin na?
b. Tnh p sut ring phn ca mi kh?
Cho bit R = 8,314 J.K-1.mol-1 hoc R = 0,082 atm.l.mol-1.K-1; Fe = 56.
Cu 3 (1,5 im).
1. Tnh tan ca FeS trong dung dch c pH = 3.
Cho:
FeS c pKS = 17,2; H2S c pKa1 = 7,02; pKa2 = 12,90
+
+
-5,92
Fe2+ + H2O
Fe(OH) + H ; = 10
2. tan ca Mg(OH)2 trong nc 180C l 9.10-3 gam/lit cn 1000C l 4.10-2 gam/lit.
a) Tnh tch s tan ca Mg(OH)2 v pH ca cc dung dch bo ho Mg(OH)2 cc nhit .
b) Tnh cc i lng H0, G0 v S0 ca phn ng ho tan, coi H0 v S0 khng thay i
theo nhit .
Cu 4. (2,5 im):
1. Cc hp cht E, F, G, H, I cng c cng thc phn t l C 9H12O khng lm mt mu Br2 trong
CCl4, b oxi ha bi KMnO4 to C6H5COOH v tc dng vi Na to kh khng mu, khng mi.
Lp lun xc nh cng thc cu to cc cht. Bit rng F, G, H, I c th chuyn mu ca Cr 2O72t mu cam sang mu xanh lc, F to c kt ta vng khi tc dng vi I 2/OH-, G khng c tnh
quang hot cn H to sn phm quang hot khi tc dng vi CrO3/piridin.

2. Xc nh cu to cc cht hu c c k hiu A,B.P trong s chuyn ho sau :

Naphtalen

Br2, Fe
1

Mg/ ete
2

CH2 (COOC2H5)/ C2H5ONa

E
F
6
C6H5CHO/ OH
K
L
11

C
KOH, t .

C6H5SO3H
12

3 O

C2H4(OH)2

H3O+

P +Br2

H2SO4,t .
8

H2 , xt
13

H3O+

SOCl2
9

AlCl3 khan

10

14

Bit L c cng thc phn t l C21H16O.

Cu 5 (1,0 im).
Nho t t 25 gam dung dich HCl 14,6% vao dung dich cha 11,04 gam K 2CO3, sau o cho
thm vao dung dich 0,04 mol Ba(OH) 2. Tinh tng khi lng mui trong dung dich thu c sau
khi cc phan ng xay ra hoan toan.
Cu 6 (1,5 im). -aminoaxit X cha %C =54,96%; %H = 9,92%; %N = 10,69%; %O =
24,43% v khi lng.
1. Xc nh cng thc phn t ca X bit MX < M axit adipic
2. X c iu ch t axit isocaproic. Xc nh cu to ng ca X.
3. X c pKa ln lt l 2,36 v 9,6. Hy vit gi tr pK a bn cnh nhm chc thch hp v tnh pH I
ca X.
4. Vit cng thc cu to ca X cc pH ln lt l 2,0; 5,98; 10,0.
5. Thu phn hon ton mt mol pentapeptit Y thu c 2 mol Gly, 1mol Ala, 1mol Phe, 1 mol
X. Thy phn khng hon ton Y thu c cc ipeptit Ala Gly v Gly Ala. Y khng thc
hin phn ng thy phn vi enzim cacboxipeptidaza v vi phenylisothioxianat. Xc nh cc
cu trc c th c ca pentapeptit Y.
Cu 7 (1,0 im).
Trong phng th nghim c st nguyn cht v dung dch HNO 3 long. Khng dng thm
bt k ha cht no khc, c th iu ch dung dch Fe(NO 3)3 (khng cha cht tan khc) theo hai
cch khc nhau. Gi s phn ng ch to NO, cc dng c cn thit c . Hy nu cch iu ch
v vit phng trnh phn ng minh ha.
Ht
Cn b coi thi khng gii thch g thm. Th sinh c s dng bng tun hon.
H v tn th sinhSBD..

S GD & T VNH PHC

Cu
Cu 1
(1,0)

2H2 (k) +

2NO (k)

K THI CHN HSG LP 12 THPT NM HC 2011-2012

HDC MN HA HC - CHUYN
Ni dung
im

N2 (k) + 2H2O (k)

a) Biu thc nh lut tc phn ng:

v1 = k.(0,375)a.(0,500)b = 6,34. 104
v2 = k.(0,375)a.(0,250)b = 3,15.104
v3 = k.(0,188)a.(0,500)b = 1,56.104
a = 2, b = 1

v=k.PNOa.PH2 b

0,5

v=k.PNO2.PH2

Thc nghim chng t rng

.
b) Theo bi ra
Giai on 2 chm, 1 v 3 nhanh.
2NO
N2O2
k
N2O2 + H2 N2O +
H2O
k
N2O + H2 N2
+
H2O
Tc phn ng c quyt nh bi (2), nn:

(1)
(2)
(3)

v=k2.PN2O2 .PH2

.
Da vo cn bng (1) rt ra:
PN O = K. PNO2 (5)
Thay (5) vo (4) thu c:
2

nhanh
chm
nhanh

(4)
0,5

v = K.k 2 .PNO 2 .PH2 = k.PNO 2 . PH2 .

C ch a ra ph hp vi kt qu thc nghim
Cu 2
(1,5)

0
0
0
1
1. a) Hp = 2Hs (Fe3O4 ) 3Hs (Fe2O3) = +232,2kJ.mol

G0p = H0p TS0p = 194, 8kJ

i vi mt phn ng c thc hin cc iu kin tiu chun t din bin

0
l Gp < 0 . Nh vy bin i Fe2O3 thnh Fe3O4 l khng th thc hin c v
mt nhit ng hc cc iu kin ny.
b) Theo kt qu phn a ta thy Fe2O3 l bn hn v s c mt ca n trong r st
l bnh thng
2. a/ Gi s trong bnh p c cn bng:

3FeO (r) + CO2 (k)

Fe3O4 (r) + CO (k)

0,25
0,25
0,25

PCO2

PCO = K = 1,1 (1)

p sut tng qut: PTQ =

3

v PCO2 + PCO = PTQ (2)

nTQ .R.T
V

= 1 mol. 8,314 J.K-1. mol-1. 1000K: 10.10-3

m = 8,2 atm
T (1) v (2) PCO2 = 4,3 atm; PCO = 3,9 atm nCO = 0,48 mol ; n CO2 =
0,52 mol
iu ny khng hp l v ta ch cho vo bnh 0,43 mol Fe3O4 . Phn ng
ngng li trc khi h t ti TTCB do thiu Fe3O4:
nFe O = 0 mol;
n(CO) = 0,57 mol;
nFeO = 3.0,43 = 1,29 mol
n (CO2) = 0,43 mol
3 4

0,5

b/ PCO = 4,674 atm; PCO2 = 3,526 atm

0,25
Cu 3
(1,5)

1. Cc cn bng in li trong dung dch:

2+
2
FeS
KS=1017,2

Fe + S
Fe2+ + H2O
FeOH+ + H+ = 10-5,92

S2 + H+
HS
Ka2-1 = (1012,9)1

HS + H+
Ka1-1 = (107,02)1

H2S
Gi tan ca FeS l s:
s = CFe = [Fe2+] + [FeOH+]
= [Fe2+] + [Fe2+][H+]-1
= [Fe2+] .(1 + [H+]-1)
(1)
2

s = CS = [S ] + [HS ] + [H2S]
= [S2] + Ka2-1 [S2][H+] + ( Ka1Ka2)1 [S2][H+]2
= [S2] [1 + Ka21[H+] + (Ka1Ka2)1[H+]2]
(2)
2+
2
[Fe ] [S ] = KFeS
(3)
-2
T hp cc cn bng (1), (2) v (3), ta c: s = 2,29.10 M
2.
2+
2+
- 2
3
a) Mg(OH)2
Mg + 2OH T = [Mg ].[OH ] = 4s
s
2s

0,25

2+

0,25
0,5

9.103
-4 3
-11
291K: T291 = 4.
= 4.(1,552.10 ) = 1,495.10 .
58

pH = 14 pOH = 14 + lg(2.1,552.10-4) = 10,49

3

4.102
-9
373K: T373 = 4.
= 1,312.10
58

pH = 14 pOH = 14 + lg(2.6,897.10-4) = 11,14

b)

0,5

RT2T1
T
8,314.373.291 1,312.109
.ln 373 =
.ln
H =
= 49243,8 J.mol-1
T2 T1
T291
373 291
1,495.1011
0

Tnh tan ca Mg(OH)2 298K:

ln

Cu 4
(2,5)

T298
H0 1
1
49243,8 1
1
=
.

=
.

T291
R 298 291
8,314 298 291

Suy ra T298 = 2,41.10-11.

T biu thc:
0
G 298 = -RTlnT298 = -8,314.298.ln2,41.10-11 = 60573,7 J.mol-1 = 60,5737 KJ.mol-1
0
G 298 = H0 298. S0 Suy ra S0 = -38,02 J.mol-1.K-1
1. Xc nh ng cng thc cu to ca mi cht c 0,25
V C9H12O (k = 4) khng lm mt mu Br 2 trong CCl4, b oxi ha bi KMnO4 to
C6H5COOH v tc dng c vi Na nn E, F, G, H, I l cc ancol thm. Cc cu
to ancol thm c th c:
OH
CH2OH
OH
I

II

III

CH2OH

OH

IV

- E khng b oxi ha bi KMnO4 nn E l ancol bc 3 (V)

- F to kt ta vng khi cho phn ng vi I 2/OH- nn F cha nhm
metylcacbinol cn H (II)
- G khng c tnh quang hot nn G l (I)
- H to sn phm c tnh quang hot khi tc dng vi CrO 3/piridin nn H l
(IV)
- Vy I l (III)
2. 1,25 im. Xc nh ng 3 cht c 0,25 im

CH2-C6H5

CH2-C6H5

O
(N)

Cu 5
(1,0 )

(P)

n H+ = n Cl- = 0,1 mol ; n CO2- = 0,08 mol ; n K + = 0,16 mol

3

n Ba 2+ = 0,04 mol ; n OH- = 0,08 mol

H+

0,08
H

Xet tng qua trinh :

CO 32-

0,08

0,02

HCO

HCO + OH
0,06
Ba

2+

0,04

0,25

CO 2 + H 2O (2)
0,02

CO 32- + H 2O (3)

0,06
+

HCO 3- (1)
0,08

0,02
3

0,06

CO

BaCO 3 (4)

0,04

0,04

23

0,25

2
Trong dd sau phan ng con: 0,1 mol Cl- ; 0,16 mol K+ ; 0,02 mol OH- va 0,02 mol CO3 .
Khi lng mui = (0,1.35,5) + (0,14.39) + (0,02.60) = 10,21 gam

Cu 6
(1,5)

1. x : y : z : t = 6 : 13 : 2 : 1
CT nguyn ca X: (C6H13O2N)n
MX < MC4H8(COOH)2 = 146 CTPT ca X: C6H13O2N
2.
CH3 CH CH2 CH2 COOH

Br2; PBr3

CH3

0,25

0,25

CH3 CH CH2 CH COOH

CH3

0,25

Br

0,25

NH3
CH3 CH CH2 CH COOH
CH3

NH2

3.
CH3 CH CH2 CH COOH copK a =2,36
CH3
NH3+ copK a =9,6

pHI =
+
H3N CH COOH

2,36 + 9, 6
= 5,98
2

-H+ +
H3N CH COO

-H+

0,25

H2N CH COO

V
i R -: (CH3)2CH - CH2 pH =2:

+
H3N CH COOH
R

pH =5,98:

+H N CH COO3
R

pH =10:

H2N CH COO
R

4.
+ T sn phm thy phn Y phi c phn Gly Ala Gly
+ Y khng thc hin phn ng thy phn vi men cacboxipeptidaza v vi
phenylisothioxianat Y khng c nhm NH2 v COOH
Y l peptit vng Phe v Leu lin kt vi nhau cho hai cu trc:
Gly

Cu 7
(1,0)

Ala

Gly

Phe

Leu

va Gly

Ala

Gly

Leu

Phe

0,25
0,5

Cch 1: Cho bt Fe vo dung dch HNO3, i Fe tan ht. C cn dung dch (c th

c mt trong hai hoc c hai mui Fe(NO3)2 v Fe(NO3)3. Nhit phn c Fe2O3,
ly lng d Fe2O3 cho vo HNO3, lc b Fe2O3 d sau phn ng cn li dung dch 0,5
Fe(NO3)3.
Fe (Fe(NO3)3+Fe(NO3)2) Fe2O3 Fe(NO3)3
Cch 2: Cho bt st d vo 2V ml dung dch HNO3 long. Gn b Fe d. Cho thm
V ml dung dch HNO3 ban u s c dung dch Fe(NO3)3 khng ln Fe(NO3)2 v 0,5
HNO3.
3Fe(d) + 8 HNO3 3Fe(NO3)2 + 2NO + 4H2O
3Fe(NO3)2 + 4HNO3 3Fe(NO3)3 + NO + 2H2O
Ghi ch: Th sinh lm cch khc ng vn cho im ti a.