S GD&T Hi Phng K thi chn Hc Sinh Gii lp 12

Mn: ho hc (bng a)

-------------------

Nm hc 2003 - 2004

--

===============
(Thi gian lm bi: 180 pht)

Bi 1: (3 im)
1-Thc hin cc chuyn ho sau bng phng trnh phn ng:
+B

H O
+O
+H
PBr
CuO , t
(C)
Etilen
(A)
(D)

(E)
(F)

(B)
OH
(G)
+ IBr
(I)

Br

(H)
as
Bit (F) l CH3-CH2-CH2-COOH
2- Thc hin dy chuyn ho sau bng phng trnh phn ng, cc phn
ng din ra theo t l mol 1:1, cc cht sau phn ng u l sn
phm chnh.
KOH
+ Br
C

B
t cao ; P cao
Fe
n-C3H7-C6H5
Br
KOH / C H OH
KOH / H O
Br / H O

D
E
G
(A)
F
as
t
t
0

2
0

Bi 2: (4 im)
1- T toluen vit cc phng trnh phn ng iu ch: C6H5-CH2-COOCH2-CH2-C6H5
2- T axetilen vit s phn ng iu ch H2C=CH-COOH.
3- T But-1-en vit cc phng trnh phn ng iu ch 3metylheptan-3-ol
4- Cho s phn ng:
+ KOH
+ Cl
+ KMnO
H / Pd
C
B
D (C6H10O4)
Ben zen
A
H O
as
t
Xc nh cng thc cu to ca A , B , C , D
2

Bi 3: (5,0 im)
1- Vit cc cng thc cu to ca axit cacboxylic ng vi cng thc phn
t C5H10O2 , gi tn theo danh php IUPAC. So snh tnh axit ca cc
axit.
2- So snh tnh axit ca cc cp cht sau, gii thch.
a)

HOOC
H

COOH
C=C

H
v

COOH
C=C

HOOC
(A)
(B)
b) HOOC-CH2-COOH
v
HOOC-COOH
(C)
(D)
c) C6H5-CH2 -COOH
v
HC C-CH2-COOH
(E)
(F)
3- So snh tnh axit ca cc cht sau, gii thch:

C6H5OH ; p-CH3O-C6H4-OH ; p-NO2-C6H4-OH ; p-CH3-CO-C6H4-OH ; p-CH3C6H4-OH ;

(A)
(B)
(C)
(D)
(E)
4- Hai hp cht thm A v B u c cng thc phn t CnH2n-8O2. Hi B
c khi lng ring 5,447 g/l (ktc). A c kh nng phn ng vi kim loi
Na gii phng H2 v c phn ng trng gng. B phn ng c vi Na2CO3
gii phng kh CO2 .
a) Vit cng thc cu to ca A,B.
b) A c 3 ng phn A1 ; A2 ; A3 , trong A1 l ng phn c
nhit si nh nht. Xc nh cng thc cu to ca A1 , gii thch.
c) Vit s chuyn ho o-crezol thnh A1 ; toluen thnh B.
Bi 4: (3 im)
1- Vit cc phng trnh phn ng thch hp nht iu ch cc kim loi
t cc hp cht sau:
Cr2(SO4)3 ; KHCO3 ; Fe2O3 ; CuSO4 ; MgSO4
2- C cc cht A, B , C, D, E. Tin hnh lm th nghim nh sau:
+ t cc cht trn u cho ngn la mu vng.
+ A + H2O
O2 + ...
+ B + H2O
NH3 + ...
+ C + D
X (kh) + ...
+ C + E
Y (kh)
X,Y l nhng hp cht kh c th gp trong mt s phn ng ho hc,
t khi ca X so vi O2 v Y so vi NH3 u bng 2.
a) Xc nh cng thc ho hc A, B , C, D, E.
b) Vit cc phng trnh phn ng xy ra.
Bi 5: (2,0 im)
1- Tnh pH ca dung dch AlCl3 0,10M bit hng s thu phn ca AlCl3
K (1) = 1,2.10-5
2- Trong iu kin p sut 1 atm, khi lng ring ca nhm clorua ph
thuc nhit nh sau:
Nhit
Khi lng ring
(0C)
(g/dm3)
200
6,9
600
2,7
800
1,5
a) Tnh khi lng phn t nhm clorua ti cc nhit trn
b) Vit cng thc phn t, cng thc cu to ca nhm clorua nhit
2000C v 8000C.
Bi 6(3)
1)Xc nh CTCT ca A , B, C....v hon thnh cc phng trnh phn
ng theo s sau:
1,47g (A) + (K)
(1)
0,01 mol (B) + (C)
600 C
3(B)
(E) : cn xng
(2)
2

(E) + Cl2
(F) + (K)
(3)
askt

(F) + NaOH
(G) + NaCl
(4)

(G) + CuO
(H) + Cu + (D)
(5)

(H + AgNO3 + NH3 + H2O

(6)
(M) + Ag + ...
(M) + H2SO4
(7)

(N) + ...
(E ) + KMnO4 + H2SO4
(8)
(N) + ...
2/ - Cho bit A, B, C, D, E l cc hp cht ca Natri cho A ln lt tc dng
vi cc dung dch B, C thu c cc kh tng ng X, Y. Cho D, E ln lt tc
dng vi nc thu c cc kh tng ng Z, T. Bit X, Y, Z, T l cc kh
thng thng chng tc dng vi nhau tng i mt. T khi ca X so vi
Z bng 2 v t khi ca Y so vi T cng bng 2. Vit tt c cc phng
trnh phn ng xy ra.
HT

S GD&T Hi
Phng
--------------------

hng dn chm thi Hc Sinh Gii lp 12

Mn: ho hc (Bng A )

Nm hc 2003 - 2004
===============

Bi 1: (3 im)
1- (2 im) . Mi phng trnh phn ng cho 0,2 im
Thc hin cc chuyn ho :
H
CH2=CH2 + HOH
CH3-CH2OH
+ CuO ,t
CH3-CH2OH
CH3-CH=O
OH
2CH3-CH=O

CH3-CH(OH)-CH2-CH=O
H O
CH3-CH(OH)-CH2-CH=O
CH3-CH=CH-CH=O
O
CH3-CH=CH-CH=O CH3-CH=CH-COOH
+H
CH3-CH=CH-COOH
CH3-CH2-CH2-COOH
PBr
CH3-CH2-CH2-COOH
CH3-CH2-CHBr-COOH
Br
CH3-CHBr-CH2-COOH
CH3-CH2-CH2-COOH
as
IBr
CH3-CH=CH-COOH
CH3-CHBr-CHI-COOH

(A)

(B)
(C)
(D)

(E)
(F)
(G)
(H)
(I)

2- (1 im) . Mi phng trnh phn ng cho 0,2 im

Cc phng trnh phn ng :
as
C6H5-CH2-CH2-CH3 + Br2
C6H5-CHBr-CH2-CH3 + HBr
(A)
(D)
C H OH
C6H5-CH=CH-CH3 + KBr + H2O
C6H5-CHBr-CH2-CH3 + KOH
t
(D)
(E)
C6H5-CH=CH-CH3 + Br2
C6H5-CHBr - CHBr-CH3
(E)
(F)
2

5
0

C6H5-CHBr - CHBr-CH3 + KOH

C6H5-CH(OH) - CHBr-CH3 + KBr
(F)
(G)
Fe
-CH2-CH2-CH3 + Br2
Br- -CH2-CH2-CH3 + HBr

(A)
(B)
HOBr -CH2-CH2-CH3 + KOH
- -CH2-CH2-CH3 + KBr
t cao ; P cao
(B)
(C)
0

Bi 2:(4 im)
1-( 1,5 im) . Mi phng trnh phn ng cho 0,2 im)
T toluen vit cc phng trnh phn ng iu ch: C6H5-CH2-COOCH2-CH2-C6H5
+ KCN
C6H5-CH2Cl
C6H5-CH2-C N
H
C6H5-CH2-C N
C6H5-CH2-COOH
+ Cl ( as )
C6H5-CH3
C6H5-CH2Cl
+ Mg
C6H5-CH2Cl
C6H5-CH2MgCl
+ HCHO
C6H5-CH2MgCl

C6H5-CH2-OH
H SO ( d )

C6H5-CH2-COO-CH2-CH2-C6H5 +
C6H5-CH2-COOH +C6H5-CH2-OH

H2O
2- ( 0,5 im)
T axetilen vit s phn ng iu ch H2C=CH-COOH:
Cch 1:
+ CO
+ HBr
+ Mg
C2H2
CH2=CHBr
CH2=CHMgBr
H2C=CH-COOH.
Cch 2:
+ HCl , H O
+ HCl
+ KCN
C2H2
CH2=CHCl
CH2=CH-CN
H2C=CH-COOH.
3- (1 im) . Mi phng trnh phn ng cho 0,25 im
H
CH2=CH-CH2-CH3 + H2O
CH3 -CH(OH) -CH2-CH3
as
CH3 -CH(OH) -CH2-CH3 + Cl2
CH3-C(OH)-CH2-CH3 + HCl
Cl
OH
CH3-C(OH)-CH2-CH3 + Mg
CH3-C-CH2-CH3
Cl
MgCl
+

Peoxit
CH2=CH-CH2-CH3 + HCl
CH3-CH2-CH2-CH2-Cl + HCl
OH
CH 3
CH3-C-CH2-CH3 + CH3-CH2-CH2-CH2-Cl
CH
-CH
-C-CH
-CH

3
2
2
2-CH2-CH3
MgCl
OH
+
MgCl2

4- (1,0 im)
S chuyn ho:
+ KOH
+ Cl
+ KMnO
H / Pd
C6H10
C6H11Cl
HOOC-(CH2)4-COOH
C6H6
C6H12
H O
as
t
(A)
(B)
(C)
(D)
Cng thc cu to:
Cl
HOOC-(CH2)4-COOH
2

(A)

(B)

(C)

(D)

Bi 3: (5,0 im)
4

1- (1,2 im) . Mi cng thc ng, gi tn ng cho 0,2 im)

Cc cng thc cu to:
CH3 - CH2 - CH2 -CH2 - COOH (A) : axit pentanoic
CH3 - CH - CH2 - COOH (B)
: axit 3-metylbutanoic
CH3
CH3 - CH2 - CH - COOH (C)
: axit 2-metylbutanoic
CH3
CH3
CH3- C - COOH (D)
: axit 2,2-imetylpropanoic.
CH3
So snh tnh axit: (D) < (C) < (B) < (A)
(0,4 im)
2- ( 0,6 im)
So snh tnh axit ca cc cp cht:
a) (A) c tnh axit mnh hn (B) v (B) phn cc phn t bng
0
b) (D) c tnh axit mnh hn (C) v (C) c mch C di hn nh hng
lc ht gia 2 nhm -COOH yu hn (D).
c) (F) c tnh axit mnh hn (E) v nhm -C CH ht e mnh hn
nhm -C6H5.
3- ( 1,0 im)
-Tnh axit tng theo chiu: (B) < (E) < (A) < (D) < (C)
- Gii thch:
+ (B) tnh axit yu nht v (B) c nhm CH3-O - y e mnh hn
nhm - CH3 lm gim phn cc ca lin kt O-H : (E)> (B) .
+ Cc nhm cn li u l nhm ht e: nhm -NO2 ht e mnh
nht sau n nhm CH3-C =O ri n nhm -C6H5 v vy tnh axit c xp nh trn.
4- (2,2 im)
MB = 5,447.22,4 = 122 (g) => CTPT ca A,B: C7H6O2
A + Na
H2 => A c nhm -OH.
NH
A + AgNO3
Ag => A c nhm -CH=O
a)CTCT ca A:
CH=O
CH=O
CH=O
OH
3

B + Na2CO3
CO2
b) A1 l:

CH=O
OH

OH
COOH
=> B l axit:

OH

v A1 c lin kt hiro ni phn t ln gim

nhit si.
Tnh axit ca B mnh hn axit CH3-COOH v nhm -C6H5 l nhm ht e.
c) S phn ng t o-crezol thnh A1:
5

CH3
OH
+ Cl2

as

CH2Cl
OH

CH2OH
OH

+ NaOH

t0

CH=O
OH

+ CuO

t0

T toluen
B: CH3

COOH
0

+ KMnO4 ( t )

Bi 4: (3 im)
1- (1,0 im)
Cc phng trnh phn ng iu ch kim loi:
dp
iu ch Cr:
Cr2(SO4)3 + 3H2O
2Cr + 3H2SO4 + 3/2O2
iu ch K:
KHCO3 + HCl
KCl + H2O + CO2
dp
KCl (nc) K + 1/2Cl2
t
iu ch Fe:
3CO + Fe2O3
2Fe + 3CO2
iu ch Cu:
CuSO4 + Fe
Cu + FeSO4
iu ch Mg:
MgSO4 + 2NaOH
Mg(OH)2 + Na2SO4
Mg(OH)2 + 2HCl
MgCl2 + 2H2O
dp
MgCl2 (nc) Mg + Cl2
2- (2 im)
a) Xc nh cng thc : (1 im)
+ t cc cht trn u cho ngn la mu vng => u l hp cht
ca Na.
+ A + H2O
O2 + ... => A l Na2O2.
+ B + H2O
NH3 + ... => B l Na3N
+ Phn t khi ca X = 64 ; ca Y = 34, X,Y l cc hp cht kh => X l
SO2 ; Y l H2S
+ C l NaHSO4 ; D l NaHSO3 ( hoc Na2SO3)
+ E l NaHS ( hoc Na2S).
b) Cc phng trnh phn ng : (1,0 im)
2Na2O2 + 2H2O
4NaOH + O2
Na3N + 3H2O
3NaOH + NH3
NaHSO4 + NaHSO3
Na2SO4 + H2O + SO2
NaHSO4 + NaHS
Na2SO4 + H2S
0

Bi 5: (2,0 im)
1- (1,0 im)
AlCl3
Al3+ + 3Cl
Al(OH)2+ + H+ K(1) = 1,2.10-5
Al3+ + H2O

B:
0,10
0
0
Cb:
(0,10 -x)
x
x
K(1) =

x2
= 1,2.10-5 => x2 -1,2.10-6 + 1,2.10-5x.
(0,10 x )

+
Gii c x= 1,08.10-3 => H = 1,08.10-3 => pH =2,97.
2- (1,0 im)

a)Dng cng thc : V =

nRT
tnh c th tch 1 mol phn t nhm
P

clorua cc nhit :
V(2000C) = 0,082.473 = 38,78 (l)
V(6000C) = 0,082.873 = 71,58 (l)
V(8000C) = 0,082.1073 = 87,98 (l)
Khi lng phn t ca nhm clorua cc nhit :
M(2000C) = 38,78l x 6,9 g/l = 267,62 => KLPT = 267,62 dvC
M(6000C) = 71,58l x 2,7 g/l = 193,27 => KLPT = 193,27 dvC
M(8000C) = 87,98l x 1,5 g/l = 131,87 => KLPT = 131,87 dvC
b) Cng thc phn t nhm clorua c dng (AlCl3)n
nhit 2000C : n=
CTCT:

267, 62
2 => CTPT: Al2Cl6
133,5

Cl

Cl

Cl

Al

Al

Cl
Cl
Cl
nhit 800 C n = 1 => CTPT: AlCl3
CTCT:
Cl
0

Al
Cl

Cl

Bi 6 (3): Mi pt 0,2