B GO DUC V O TAO K TH CHON HOC SNH G QUC GA

LP 12 THPT NAM HOC 2000-2001

hng dn chm thi chnh thc
ho hc v c (Bng A)
Cu I (4 im):
1. Phng php sunfat c th iu ch c cht no: HF , HCl , HBr , HI ? Nu
c cht khng iu ch c bng phng php ny, hy gii thch ti sao?
Vit cc phng trnh phn ng v ghi r iu kin (nu c) minh ho.
2. Trong dy oxiaxit ca clo, axit hipoclor l quan trng nht. axit hipoclor c
cc tnh cht: a) Tnh axit rt yu, yu hn axit cacbonic; b) C tnh oxi ho mnh lit;
c) Rt d b phn tch khi c nh sng mt tri, khi un nng. Hy vit cc phng
trnh phn ng minh ho cc tnh cht .
3. C cc dung dch (b mt nhn) : a) BaCl
2
; b) NH
4
Cl ; c) K
2
S ; d) Al
2
(SO
4
)
3
;
e) MgSO
4
; g) KCl ; h) ZnCl
2
. c dng thm dung dch phenolphtalein (khong pH
chuyn mu t 8 - 10) hoc metyl da cam (khong pH chuyn mu t 3,1 - 4,4).
Hy nhn bit mi dung dch trn, vit cc phng trnh ion (nu c) gii
thch.
4. Tm cch loi sch tp cht kh c trong kh khc v vit cc phng trnh
phn ng xy ra: a) CO c trong CO
2
; b) H
2
S c trong HCl ; c) HCl c trong H
2
S ;
d) HCl c trong SO
2
; e) SO
3
c trong SO
2
.
Cch gii
1. Phng php sunfat l cho mui halogenua kim loi tc dng vi axit sunfuric c,
nng iu ch hirohalogenua da vo tnh d bay hi ca hirohalogenua.
Phng php ny ch p dng iu ch HF , HCl, khng iu ch c HBr v HI v
axit H
2
SO
4
l cht oxi ho mnh cn HBr v HI trong dung dch l nhng cht kh
mnh, do p dng phng php sunfat s khng thu c HBr v HI m thu c
Br
2
, I
2
.
Cc phng trnh phn ng:
CaF
2
+ H
2
SO
4
, nng = 2 HF + CaSO
4

NaCl + H
2
SO
4
, nng = HCl + NaHSO
4

2 NaCl + H
2
SO
4
, nng = 2 HCl + Na
2
SO
4

NaBr + H
2
SO
4
, nng = NaHSO
4
+ HBr
2 HBr + H
2
SO
4
, nng = SO
2
+ 2 H
2
O + Br
2

NaI + H
2
SO
4
, nng = NaHSO
4
+ HI
6 HI + H
2
SO
4
, nng = H
2
S + 4 H
2
O + 4 I
2
2. Axit hipoclor :
- Tnh axit rt yu, yu hn axit cacbonic
NaClO + CO
2
+ H
2
O = NaHCO
3
+ HClO
Tnh oxi ho mnh lit, a cht phn ng c s oxi ho cao nht
+6
4 HClO + PbS
-2
= 4 HCl + PbSO
4

- D b phn tch :
a s t
o

1
HClO = HCl + O ; 3 HClO = 2 HCl + HClO
3

3. Dng phenolphtalein nhn ra K
2
S
S
-2
+ H
2
O = HS
-
+ OH
-

pH > 10 dung dch phenolphtalein c mu
Dng K
2
S lm thuc th. Cho K
2
S vo cc dung dch cn li:
t
o

- Vi NH
4
Cl : S
-2
+ NH
4+
= NH
3
+ HS
-

Nhn ra NH
3
nh mi khai, hoc ho giy lc tm phenolphtalein ( v NH
3
c
pH > 9 ).
- Vi Al
2
(SO
4
)
3
: Cho kt ta keo trng Al(OH)
3

Al
3+
+ 3 S
-2
+ 3 H
2
O = Al(OH)
3
+ 3 HS
-

- Vi MgSO
4
: Cho kt ta trng Mg(OH)
2

Mg
2+
+ 2 S
2-
+ 2 H
2
O = Mg(OH)
2
+ 2 HS
-

- Vi ZnCl
2
: Cho kt ta trng ZnS
Zn
2+
+ 2 S
2-
= ZnS
Dng NH
4
Cl nhn ra MgSO
4
: kt ta Mg(OH)
2
tan c trong NH
4
Cl ; trong khi
cc kt ta Al(OH)
3
v ZnS khng tan.
t
o

Mg(OH)
2

+ 2 NH
4+
= Mg
2+
+ 2 NH
3
+ H
2
O
Dng MgSO
4
nhn ra BaCl
2
:
Ba
2+
+ SO
4
2-
= BaSO
4
trng
Dng BaCl
2
nhn ra Al
2
(SO
4
)
3
:


Cn li l KCl. Ba
2+
+ SO
4
2-
= BaSO
4
trng
(Hoc dng metyl da cam lm thuc th:
Nhn ra Al
2
(SO
4
)
3

Al
2
(SO
4
)
3
2 Al
3+
+ 3 SO
4
2-

Al
3+
+ 3 H
2
O = AlOH
2+
+ H
+

Dung dch c phn ng rt axit ( pH < 4 ) lm cho metyl da cam c mu da cam
hoc hng.
Cc dung dch cn li u c pH > 4,4 nn metyl da cam c mu vng. Dng
Al
2
(SO
4
)
3
lm thuc th:
- Vi BaCl
2
cho kt ta trng tinh th Ba
2+
+ SO
4
2-
= BaSO
4
trng
- Vi K
2
S cho kt ta keo trng Al(OH)
3

Al
3+
+ 3 S
-2
+ 3 H
2
O = Al(OH)
3
+ 3 HS
-

Dng K
2
S lm thuc th:
t
o

- Vi NH
4
Cl : S
-2
+ NH
4+
= NH
3
+ HS
-

Nhn ra NH
3
nh mi khai, hoc ho giy lc tm phenolphtalein.
- Vi MgSO
4
: Cho kt ta trng Mg(OH)
2

2
Mg
2+
+ 2 S
2-
+ 2 H
2
O = Mg(OH)
2
+ 2 HS
-

- Vi ZnCl
2
: Cho kt ta trng ZnS
Zn
2+
+ 2 S
2-
= ZnS
- Vi KCl khng c du hiu g.
phn bit MgSO
4
vi ZnCl
2
, cho NH
4
Cl vo 2 kt ta Mg(OH)
2
v ZnS th
ch c kt ta Mg(OH)
2
tan trong NH
4
Cl khi un nng


t
o

Mg(OH)
2

+ 2 NH
4+
= Mg
2+
+ 2 NH
3
+ H
2
O
cn ZnS khng tan.
4. t
o

a) CO + CuO = CO
2
+ Cu
b) H
2
S + CuCl
2
= CuS + 2 HCl
c) HCl + NaHS = NaCl + H
2
S
d) HCl + NaHSO
3
= NaCl + SO
2
+ H
2
O
e) SO
3
+ H
2
SO
4
= H
2
S
2
O
7
(oleum)


Cu II (3,5 im):
1. Hy dng k hiu lng t biu din cc trng hp s lng electron trong
mt obitan nguyn t.
2. Mi phn t XY
3
c tng cc ht proton, ntron, electron bng 196; trong ,
s ht mang in nhiu hn s ht khng mang in l 60, s ht mang in ca X t
hn s ht mang in ca Y l 76.
a) Hy xc nh k hiu ho hc ca X,Y v XY
3
.
b) Vit cu hnh electron ca nguyn t X,Y.
c) Da vo phn ng oxi ho - kh v phn ng trao i, hy vit phng trnh
phn ng (ghi r iu kin, nu c) cc trng hp xy ra to thnh XY
3
.
Cch gii
1. C ba trng hp: hoc
Obitan nguyn t trng c 1 e c 2 e

2. a) K hiu s n v in tch ht nhn ca X l Zx , Y l Zy ; s ntron (ht
khng mang in) ca X l Nx , Y l Ny . Vi XY
3
, ta c cc phng trnh:
Tng s ba loi ht: 2 Zx + 6 Zy + Nx + 3 Ny = 196 (1)
2 Zx + 6 Zy Nx 3 Ny = 60 (2)
6 Zy 2 Zx = 76 (3)
Cng (1) vi (2) v nhn (3) vi 2, ta c:
4 Zx + 12 Zy = 256 (a)
12 Zy 4Zx = 152 (b)
Zy = 17 ; Zx = 13
Vy X l nhm, Y l clo. XY
3
l AlCl
3
.
b) Cu hnh electron: Al : 1s
2
2s
2
2p
6
3s
2
3p
1
; Cl : 1s
2
2s
2
2p
6
3s
2
3p
5

Cc phng trnh phn ng to thnh AlCl
3
:
t
o

2Al + 3 Cl
2
= 2 AlCl
3



t
o

3
2Al + 3 CuCl
2
= 2 AlCl
3
+ 3 Cu
Al
2
O
3
+ 6 HCl = 2 AlCl
3
+ 3 H
2
O
Al(OH)
3
+ 3 HCl = AlCl
3
+ 3 H
2
O
Al
2
S
3
+ 6 HCl = 2 AlCl
3
+ 3 H
2
S
NaAlO
2
+ 4 HCl = AlCl
3
+ NaCl + 2 H
2
O
Al
2
(SO
4
)
3
+ 3 BaCl
2
= 2 AlCl
3
+ 3 BaSO
4

Cu III (5 im):
1. Hon thnh phng trnh phn ng a) , b) sau y. Cho bit cc cp oxi ho -
kh lin quan n phn ng v so snh cc gi tr E
o
ca chng.
a) Zn[Hg(SCN)
4
] + IO
3
-
+ Cl
-

ICl + SO
4
2
-
+ HCN + Zn
2+
+ Hg
2+
b) Cu(NH
3
)
m
2+
+ CN
-
+ OH
-
Cu(CN)
2
-
+ CNO
-
+ H
2
O
2. Dung dch X c cht tan l mui M(NO
3
)
2
. Ngi ta dng 200ml dung dch
K
3
PO
4
va phn ng vi 200ml dung dch X, thu c kt ta M
3
(PO
4
)
2
v dung
dch Y. Khi lng kt ta ( c sy kh) khc khi lng M(NO
3
)
2
ban u l
6,825 gam.
in phn 400 ml dung dch X bng dng in I = 2 ampe ti khi thy khi
lng catt khng tng thm na th dng, c dung dch Z. Gi thit s in phn c
hiu sut 100%.
a) Hy tm nng ion ca dung dch X, dung dch Y, dung dch Z. Cho bit
cc gn ng phi chp nhn khi tnh nng dung dch Y, dung dch Z.
b) Tnh thi gian (theo giy) in phn.
c) Tnh th tch kh thu c 27,3
o
C , 1atm trong s in phn.
Cch gii: 1.
a) Zn[Hg(SCN)
4
] + 16 H
2
O Zn
2+
+ Hg
2+
+ 4 HCN + 4 SO
4
2-
+ 24 H
+
+ 24 e
6 IO
3
-
+ Cl
-
+ 6 H
+
+ 4 e ICl + 3 H
2
O
Zn[Hg(SCN)
4
] + 6 IO
3
-
+ 6 Cl
-

+ 8 H
+
Zn
2+
+ Hg
2+
+ 4 HCN + 4 SO
4
2-
+
+ 6 ICl + 2 H
2
O
E
o
IO
3-
/ ICl > E
o
SO
4
2
-
, HCN / Zn[Hg(SCN)
4
]
b) 2 Cu(NH
3
)
m
2+
+ 2 CN
-
+ e Cu(CN)
2
-
+ m NH
3

CN
-
+ 2 OH
-
CNO
-
+ H
2
O + 2 e
2 Cu(NH
3
)
m
2+
+ 5 CN
-
+ 2 OH
-
2 Cu(CN)
2
-
+ 2m NH
3
+ CNO
-
+ H
2
O
E
o
Cu(NH
3
)
m
2+
/

Cu(CN)
2
-

> E
o
CNO
-
/ CN
-

2. a) Phng trnh phn ng:
3 M(NO
3
)
2
+ 2 K
3
PO
4
M
3
(PO
4
)
2
+ 6 KNO
3
(1)
Dung dch Y: dung dch KNO
3
KNO
3
K
+
+ NO
3-
(2)
Theo (1), 6mol NO
3
-
phn ng to ra 2mol PO
4
3-
lm thay i khi lng 372 190 =
182 (g)
x mol NO
3
-
phn ng to ra x/3mol PO
4
3-
lm thay i khi lng 6,825 (g)

) mol ( 1125 , 0
182
825 , 6 x 3
x = = ) l / mol ( 2625 , 0
200
1000 x 115 , 0
Cddx = =

Theo (1), nK
+
= nNO
3
-
= nKNO
3
= 2 nM (NO
3
)
2
= 2 0,1125 = 0,225 (mol).
4
Coi Vdd Y Vdd X + Vdd K
3
PO
4
400 (ml) (3)
0,225 1000
Vy C K
+
= C NO
-
= = 0,5625 (mol/l)
3
400
Dung dch Y c nng : C K
+
= C NO
3
-
= 0,5625 (mol/l)
Cc gn ng chp nhn khi tnh nng dung dch Y:
- B qua s thay i th tch khi tnh (3) v s c mt M
3
(PO
4
)
2

- B qua s tan M
3
(PO
4
)
2
= M
2+
+ PO
4
2-
(4)
- B qua s phn li H
2
O

= H
+
+ OH
-

Xt s in phn, s in phn:
K M(NO
3
)
2
A
H
2
O


M
2+
+ 2 e = M 2 H
2
O - 2 e = 1/2 O
2
+ 2 H
+

Phng trnh in phn:
M(NO
3
)
2
+ H
2
O M + 1/2 O
2
+ 2 HNO
3
(5)
Dung dch Z c cht tan HNO
3
.
Coi Vdd Z Vdd X 400 (ml) (6)
0,5625 400
Theo (5) n HNO = 2 n M(NO
3
)
2
= 2
3
1000
n HNO
3
1000
Vy C H
+
= C NO
-
= = 1,125 (mol/l)
3
400
(hoc theo(6) v (5) nH
+
= nNO
3
-
= 2 C dd x = 1,125)

Cc gn ng chp nhn khi tnh nng dung dch Z:
- Coi Vdd Z Vdd X, b qua s thay i th tch do s in phn gy ra.
- B qua s phn li H
2
O

= H
+
+ OH
-
v Z l dd HNO
3
.
Nng ion dd X: CM
+
= 0,5625 M ; CNO
3
-
= 1,125 M
dd Y: CK
+
= CNO
3
-
= 0,5625 M
dd Z: CH
+
= CNO
3
-
= 1,125 M.
b) Tnh thi gian in phn:
m n
Thay s vo (7) l = M(NO
3
)
2
= 0,5625 0,4 = 0,025 (mol)
A
n = 2 ; I = 2
Vy t = 0,225 96500 = 21.712,5 (giy)
c) Tnh th tch kh thu c 27,3
o
C , 1atm trong s in phn dung dch Y, Z.



22,4 0,1125 300,3 n
Vo = = 2,772 (lt)
2
273 1
) mol ( 1125 , 0
2
225 , 0
n
2
1
n
2 3 2
) NO ( M O
= = = ( ): 5 Theo
Cu IV (4 im):
5
1. Sunfuryl iclorua SO
2
Cl
2
l ho cht ph bin trong phn ng clo ho. Ti
350
o
C, 2 atm phn ng
SO
2
Cl
2
(kh) = SO
2
(kh) + Cl
2
(kh) (1)
C Kp = 50 .
a) Hy cho bit n v ca tr s v gii thch: hng s cn bng Kp ny phi
c n v nh vy.
b) Tnh phn trm theo th tch SO
2
Cl
2
(kh) cn li khi (1) t ti cn bng
iu kin cho.
c) Ban u dng 150 mol SO
2
Cl
2
(kh), tnh s mol Cl
2
(kh) thu c khi (1) t
ti cn bng.
Cc kh c coi l kh l tng.
2. a) Tnh in li ca dung dch CH
3
NH
2
0,010M.
b) in li thay i ra sao khi
- Pha long dung dch ra 50 ln.
- Khi c mt NaOH 0,0010M.
- Khi c mt CH
3
COOH 0,0010M.
- Khi c mt HCOONa 1,00M.
Bit: CH
3
NH
2
+ H
+
CH
3
NH
3
; K = 10
10,64
CH
3
COOH = CH
3
COO
-
+ H
+
; K = 10
-4,76
Cch gii:
1. a) Gi s mol SO
2
Cl
2
ban u l 1, phn li l , ta c:
SO
2
Cl
2
(kh) = SO
2
(kh) + Cl
2
(kh) (1)
Ban u 1 0 0
Phn li
Cn bng (1 )
pSO (atm) pCl (atm)
2 2
Kp = = 50 atm (2)
pSO
2
Cl
2
(atm)
b) V cc kh u l kh l tng nn pi = P . xi (3)
ni
m xi = (4)
nj
y : nSO
2
= nCl
2
= ; nSO
2
Cl
2
= (1 ) ; cn nj = 1 + (5)
b) T hp (5) v (4) , (3) v (2) ta c:


S mol SO Cl cn l (1 ) 0,0194 (mol)
2 2
0,0194
Do SO Cl cn li chim 100% 0,98%
2 2
1,9804
2
2
1
. P Kp

=
50 2
50
Kp P
Kp
+
=
+
=
9806 , 0 =
y l % theo s mol, cng l % theo th tch. Vy khi (1) t ti cn bng
SO
2
Cl
2
cn li chim 0,98%v s mol hay th tch ca h.
(Hoc SO
2
Cl
2
(kh) = SO
2
(kh) + Cl
2
(kh) Kp = 50 (1)
2 atm
2 - (P + p) p p
0 100 p 100 p 50
p 2 2
p
2
2
= + =

6
p
SO
2
Cl
2
= 2 - 2 0,9902 = 0,0196 (atm)
p
SO
2
Cl
2

= P . n
SO
2
Cl
2

n
SO
2
Cl
2

= 0,0196 : 2 = 0,0098 hay 0,98%
% theo s mol cng l % theo th tch. Vy khi (1) t ti cn bng SO
2
Cl
2
cn
li chim 0,98%v s mol hay th tch ca h.)
c) Ban u dng 150 mol (kh), tnh s mol Cl
2
(kh) thu c khi (1) t ti cn bng:
Theo (1) ta c: nSO
2
= nCl
2
= nSO
2
Cl
2
98,06 = 150 0,9806
nCl
2
= 147,09 mol
2. a) Tnh in li ca dung dch CH
3
NH
2
0,010M:
CH
3
NH
2
+ H
2
O = CH
3
NH
3
+
+ OH
-
10
-14

c c K
b
= = 10
-3,36

[ ] c-x x x 10
-10,64

3 36 , 3
2
b
2
10 . 88 , 1 x 10
x 010 , 0
x
K
x c
x

= =

% 8 , 18 10
10
10 . 88 , 1
2
2
3
= =

b) in li thay i ra sao khi
- Pha long dung dch ra 50 ln:


4
2
NH CH
10 . 2
50
10
C
2 3

= =
4 36 , 3
4
2
10 . 49 , 1 x 10
x 10 2
x

= =

% 5 , 74 10
10 2
10 49 , 1
2
4
4
=

-Khi c mt NaOH 0,0010M:

NaOH = Na
+
+ OH
-

CH
3
NH
2
+ H
2
O = CH
3
NH
3
+
+ OH
-
10
-3,36
(1)
c 0,01 1. 10
-3

[ ] 0,01 - x x 1. 10
-3
+ x
3 36 , 3
3
10 49 , 1 x 10
x 01 , 0
) x 10 (

= =

+ x
% 9 , 14 10
10
10 49 , 1
2
2
3
=

gim v OH
-
ca NaOH lm chuyn dch cn bng (1) sang tri.
- Khi c mt CH
3
COOH 0,0010M:
CH
3
COOH = CH
3
COO
-
+ H
+
; K
a
= 10
-4,76
CH
3
NH
2
+ H
+
= CH
3
NH
3
+
; K
a
-1
= 10
10,64
CH
3
COOH + CH
3
NH
2
= CH
3
NH
3
+
+ CH
3
COO
-
; K = K
a
.K
a
-1
= 10
5,88

K rt ln, phn ng xy ra hon ton
CCH
3
NH
3
+
= CCH
3
COOH = 1,0 10
-3
; CCH
3
NH
2
= 9 10
-3

CH
3
NH
2
+ H
2
O = CH
3
NH
3
+
+ OH
-
; K
b
= 10
-3

c 9.10
-3
1.10
-3

[ ] 9.10
-3
- x 10
-3
+ x x


[CH
3
NH
3
+
] = (1,39 + 1).10
-3
= 2,39 10
-3

3 36 , 3
3
3
10 . 39 , 1 x 10
x 10 . 9
) x 10 (

= =

+ x
% 9 , 23 10
10
10 39 , 2
2
2
3
=

tng v CH
3
NH
2
tng tc vi CH
3
COOH.
- Khi c mt HCOONa 1,00M:
7

HCOONa HCOO
-
+ Na
+
HCOO
-
+ H
2
O

= HCOOH + OH
-
(1)
25 , 10
75 , 3
14
b
,
10
10
10
K

= =
K
a
HCOOH > K
a
CH
3
COOH ( = 10
-4,76
) nn K
,
b
< 10
-14
/ 10
-4,76
= 10
-9,24
<< K
b
(10
-3,36
).
Vy cn bng (2) khng nh hng g n cn bng (1)
CH
3
NH
2
+ H
2
O = CH
3
NH
3
+
+ OH
-
K
b
= 10
-3,36

v do in li ca CH
3
NH
2
khng thay i khi c mt HCOONa.

Cu V(3,5 im): :
Phn ng S
2
O
8
2
-
+ 2 I
-
2 SO
4
2
-
+ I
2
(1)
c kho st bng thc nghim nh sau: Trn dung dch KI vi dung dch h tinh bt,
dung dch S
2
O
3
2-
; sau thm dung dch S
2
O
8
2
-
vo dung dch trn. Cc dung dch u
c nng ban u thch hp.
1. Vit cc phng trnh phn ng xy ra; ti sao dung dch t khng mu
chuyn sang mu xanh lam?
2. Ngi ta thu c s liu sau y:

Thi gian th nghim(theo giy) Nng I
-
(theo mol . l
-1
)
0 1,000
20 0,752
50 0,400
80 0,010

Dng s liu , hy tnh tc trung bnh ca phn ng (1).
Cch gii:
1. Cc phng trnh phn ng xy ra:
S
2
O
8
2-
+ 2 I
-
2 SO
4
2-
+ I
2
(1)
I
2
gii phng ra b S
2
O
3
2-
kh ngay
2 S
2
O
3
2-
+ I
2
S
4
O
6
2-
+ 2 I
-
(2)
Khi ht S
2
O
3
2-
th mt t I
2
gii phng ra t (1) tc dng vi dung dch h tinh
bt lm cho dung dch xut hin mu xanh lam.
1 CI
-


2. Ta c v = (2). Thay s vo (2):
2 t
t
1
: 20

C
1
: 0,348
v
1
: 6,2.10
-3

t
2
: 50 C
2
: 0,600
v
2
: 6,0.10
-3

t
3
: 80 C
3
: 0,990
v
3
: 6,188.10
-3




v 6,129.10
-3
(mol.l
-1
.s
-1
)
3
10 ) 188 , 6 0 , 6 2 , 6 (
v
3
+ +
=
8
B BGO DUC V O TAO K TH CHON HOC SNH G QUC GA
LP 12 THPT NAM HOC 2000-2001

hng dn chm thi chnh thc
ho hc hu c Bng A

Cu I (5 im):
1. Xut pht t brombenzen cha
14
C v tr 1 v cc ho cht v c cn thit
khng cha
14
C, hy iu ch cc hp cht thm cha
14
C v tr 3 : a) Anilin ;
b) Iotbenzen ; c) Axit benzoic.
2. Hon thnh s cc phn ng sau v gi tn cc sn phm t A n F :
Na
2
Cr
2
O
4
2 H
Cl
2
(1 mol) H
2
O C D
Benzen (1 mol) A B
FeCl
3
t
O
, p HNO
3
(1 mol) Fe, HCl
E F
3. Khi oxi ho etylenglicol bng HNO
3
th to thnh mt hn hp 5 cht. Hy
vit cng thc cu to phn t ca 5 cht v sp xp theo trt t gim dn nhit
si ca chng (c gii thch).
Cch gii:
1. Br MgBr COOMgBr COOH
14 14 14 14
Mg CO
2
H
3
O
+

ete
COOH
14 14 14
NaOH/CaO HNO
3
/ H
2
SO
4


NH
2
NO
2
NO
2

0-5
o
C NaNO
2

14 HCl 14 14 14
KI CuCN H
3
O
+


I N
2
(+)
Cl
(-)
CN COOH
a)
Br MgBr MgBr COOMgBr

14
ete khan
14 14 14

+ Mg (1) ; + CO
2
(2)

COOMgBr COOH
14
+ H
3
O
+
+ MgBr
+
+ H
2
O (3)



9
COOH COOH

14
H
2
SO
4
14

+ HNO
3
+ H
2
O (4)
NO
2

COOH COONa

14

14

2 + Na
2
CO
3
2 + H
2
O + CO
2
(5)
NO
2
NO
2

COONa

14


CaO

14

+ NaOH rn + Na
2
CO
3
(6)
NO
2
NO
2


14


14


+ 3 Fe + 7 HCl + 3 FeCl
2
+ 2 H
2
O (7)
NO
2
NH
3
Cl

14


14


+ NaOH + NaCl + H
2
O (8)
NO
2
NH
2

14 14

b) + NaNO
2
+ 2 HCl + NaCl + 2 H
2
O
NH
2
N N Cl


14

14
+ KI + N
2
+ KCl
N N Cl I



14

14
+ CuCN + N
2
+ CuCl
N N Cl C N

14 14

c) 2 + 2 H
2
O + H
+
2 + NH
4
+

C N COOH
O OH
2. Cl OH Na
2
Cr
2
O
4
2 H
Cl
2
(1 mol) H
2
O

FeCl
3
t
O
, p O OH
OH OH OH
NO
2
Fe, HCl
HNO
3


NO
2
NH
3
Cl
10
Cl
FeCl
3

+ Cl
2
+ HCl (1)
A: Clobenzen
Cl OH
t
o
, p
+ H
2
O + HCl (2)
B: Phenol
OH O O OH
[O] 2 H
(3) ; (4)

O O OH
C: p-Benzoquinon D: Hiroquinon
OH

OH + H
2
O (5)

+ HNO
3
NO
2
E: p-Nitrophenol
OH
NO
2

+ H
2
O
OH OH
(6)
+ 3 Fe + 7 HCl F: p-Aminophenol

NO
2
NH
3
Cl
3. (B)
CH
2
OH CHO HOCH
2
- COOH COOH COOH
[O] [O] [O] [O]
CH
2
OH CH
2
OH OHC - CHO CHO COOH
(E) (A) (C) (D) ()
> B > D > A > C
(Gii thch bng hiu ng electron v lin kt hiro).

Cu II (4 im): N
Xinconiin (X) c cng thc cu to :
CH=CH
2
C
9
HOH
l ng phn lp th C
9
ca xinconin (Y). N
1. Hy ghi du vo mi nguyn t cacbon bt i v khoanh vng trn nguyn
t nit c tnh baz mnh nht trong phn t X.
2. Cho t t dung dch HBr vo X nhit phng ri un nng nh, sinh ra cc
sn phm chnh l A (C
19
H
23
BrON
2
) , B (C
19
H
24
Br
2
ON
2
) , C (C
19
H
25
Br
3
ON
2
) , v
D (C
19
H
24
Br
4
N
2
). Ch ho D vi dung dch KOH trong ru 90
o
thu c E (C
19
H
20
N
2
)
11
Hy vit cng thc cu to ca A , B , C , D , E. Ghi du vo mi nguyn t
cacbon bt i trong phn t D v E.
3. Cho C
6
H
5
COCl vo X v Y thu c sn phm u c cng thc C
26
H
26
N
2
O
2

(t l F v G). F v G c ng nht (cng l mt cht) hay khng? Chng c nhit
nng chy ging hay khc nhau? ti sao?
Cch gii: . .
1. N




CH=CH
2

CHOH

N : H
2. N N
(+)
Br
(-)


CH=CH
2
CH=CH
2
CHOH CHOH
Br
(-)(+)
NH Br
(-)(+)
NH
(A) (B)
H H
N
(+)
Br
(-)
N
(+)
Br
(-)


CHBr-CH
3
CHBr-CH
3

CHOH

CHBr

Br
(-) (+)
NH Br
(-) (+)
NH
(C) (D)
3. N N

CH-CH3

CH=CH2

CH= C
6
H
5
COO-
9
CH
(E)
N
(F)
N


F v G l ng phn cu hnh C
9
(tng t X v Y) v phn ng vi
C6H5COCl khng lm t lin kt C
9
-O v vy F v G khng ng nht, chng l
nhng ng phn i quang ca nhau, nn t
nc
ging nhau.

Cu III (4 im):
1.C mt hn hp protit gm pepsin (pH
I
= 1,1), hemoglobin (pH
I
= 6,8) v
prolamin (pH
I
= 12,0). Khi tin hnh in di dung dch protit nu trn pH = 7,0 th thu
c 3 vt cht (xem hnh):
Xut pht

Cc Cc
A B C

Cho bit mi vt cht c trng cho protit no ? Gii thch.

12
2. Khi thu phn hon ton 1 mol tripeptit X thu c 2 mol axit glutamic
( HOOC(CH
2
)
2
CH(NH
2
)COOH ), 1 mol alanin ( CH
3
CH(NH
2
)COOH ) v 1 mol NH
3
.
X khng phn ng vi 2,4-initroflobenzen v X ch c mt nhm cacboxyl t do.
Thu phn X nh enzim cacboxipeptiaza thu c alanin v mt ipeptit Y.
Vit cng thc cu to ca X , Y v gi tn chng.
Cch gii:
1. Vt A: Pepsin, v Pepsin l protit c tnh axit mnh (pH
I
= 1,1) nn tn ti dng
anion, do chuyn v cc dng.
Vt B: Hemoglobin (pH
I
= 6,8), hu nh dng ion lng cc.
Vt C: prolamin (pH
I
= 12,0), v l protit c tnh baz mnh nn dng cation, do
chuyn v cc m.
2. Tripeptit X c cu to theo trt t Glu-Glu-Ala. V theo d kin u bi aminoaxit
ui (ui C) l Ala, nhm -NH
2
ca aminoaxit u (u N) to thnh lactam vi
nhm -COOH ca n v Glu th nht, nhm -COOH ca n v th Glu hai dng
chc amit -CONH
2
(do thu phnto ra NH
3
). Vy:
O O
X: NH - CH - C - NH - CH - C - NH - CH - COOH ;
O=C (CH
2
)
2
-CONH
2
CH
3

CH
2
- CH
2
-Glutamolactam--ylglutaminylalanin
O
Y: NH - CH - C - NH - CH - COOH
O=C (CH
2
)
2
-CONH
2

CH
2
- CH
2
-Glutamolactam--ylglutamin

Cu IV (4,5 im):
Melexitoz (C
18
H
32
O
16
) l ng khng kh, c trong mt ong. Khi thu phn
hon ton 1 mol melexitoz bng axit s nhn c 2 mol D-glucoz v 1 mol D-
fructoz. Khi thu phn khng hon ton s nhn c D-glucoz v isaccarit
turanoz. Khi thu phn nh enzim mantaza s to thnh D-glucoz v D-fructoz, cn
khi thu phn nh enzim khc s nhn c saccaroz.
Metyl ho 1 mol melexitoz ri thu phn s nhn c 1 mol 1,4,6-tri-O-metyl-
D-fructoz v 2 mol 2,3,4,6-tetra-O-metyl-D-glucoz.
1. Hy vit cng thc cu trc ca melexitoz. Vit cng thc cu trc v gi tn
h thng ca turanoz.
2. Hy ch ra rng, vic khng hnh thnh fomanehit trong sn phm oxi ho
bng HIO
4
chng t c cu trc furanoz hoc piranoz i vi mt xch fructoz v
piranoz hoc heptanoz (vng 7 cnh) i vi mt xch glucoz.
3. Cn bao nhiu mol HIO
4
phn hu hai mt xch glucoz c cu trc
heptanoz v s nhn c bao nhiu mol axit fomic?
Cch gii:
1. T cc d kin u bi suy ra melexitoz:
- Khng cn -OH semiaxetan
- L trisaccarit c cu thnh t 2 dn v D-glucoz v 1 n v D-fructoz,
trong 1 n v D-glucoz lin kt vi D-fructoz to thnh isaccarit turanoz, n
v D-glucoz th hai cng lin kt vi D-fructoz to thnh isaccarit saccaroz.
- Thu phn 1 mol sn phm metyl ho melexitoz thu c:
13
1
1 mol CH
3
OCH
2
H v 2 mol
6
CH
3
OCH
2

2 5 H H
HO
3

4
CH
2
OCH
3
4 1
OH H CH
3
O 3 2 OH
H OCH
3

T suy ra n v D-fructoz dng furanorit, 2 n v D-glucoz u dng
piranorit; 2 n v D-glucoz u to ra lin kt glicorit vi C2 v C3 ca D-fructo
furanozit.
Cu trc: 4 H
2
6
COH
O

1
CH
2
OH HO
HO 5
O
H
HO
3

2
1
2

5

OH O H
4

6
CH
2
OH
4 H
2
COH O
3
H
HO 5
HO
3

2

1 H

H
O

Melexitoz (C
18
H
32
O
16
)
H
4 H
2
6
COH O H
2
1
COH
O
H
HO 5 2
5

HO
3

2

1
H
HO
H HO

6
CH
2
OH
H OH
3

4
H
O
3-O-(-D-glucopiranozyl)-D-fructofuranoz
(Turanoz)
hoc: 4
6
C H
2
OH
O

HO 5 H
HO
3

2
1

H
OH O H


4 H
2
COH O
HO 5 H
3

4
OH
HO
3

2
OH

1
H

2

O

5

6
CH
2
OH


H


1
CH
2
OH
H

Melexitoz (C
18
H
32
O
16
)
4 H
2
6
COH O
HO
5
H
HO
2
1 4
H

3
HO O 3 OH



H H

6
CH
2
OH
HO
2


5
H (Turanoz)



1
CH
2
OH 3-O-(-D-glucopiranozyl)-D-fructofuranoz
14
2. Mt xch fructoz Mt xch glucoz
7 7
CH
2
OH CH
2
OH O - CH O-CH
O - C O - C CHOH CHOH
O - CH O - CH O CHOH O CHOH O
CHOH O CHOH CHOH CHOH
CHOH CH CHOH CH
CH
2
CH
2
OH CH
2
CH
2
OH
Piranoz Furanoz Heptanoz Piranoz
khng c HCHO khng c HCHO khng c HCHO khng c HCHO
T fructoz T glucoz
V V
(do khng c nhm 1,2-itol kiu -CHOH-CH
2
OH)
3.
O - CH O - CH
CHOH O=CH
2 CHOH
O
+ 6 HIO
4
2 O + 4 HCOOH
CHOH + 6 HIO
3

CHOH O=CH + 2 H
2
O
CH
2
CH
2

Cu V (2,5 im):
1. Clorofom tip xc vi khng kh ngoi nh sng s b oxi ha thnh photgen
rt c. nga c ngi ta bo qun clorofom bng cch cho thm mt lng nh
ancol etylic chuyn photgen thnh cht khng c.
Vit phng trnh phn ng oxi ha clorofom bng oxi khng kh thnh
photgen, phn ng ca photgen vi ancol etylic v gi tn sn phm.
2. un nng vi git clorofom vi lng d dung dch NaOH, sau nh thm
vi git dung dch KMnO
4
thy hn hp xut hin mu xanh. Vit cc phng trnh
phn ng v gii thch s xut hin mu xanh.
3. Khi tin hnh iu ch axit lactic t anehit axetic v axit xianhiric, ngoi
sn phm mong mun ta cn thu c hp cht X (C
6
H
8
O
4
). Vit cng thc cu to ca
X v cc phng trnh phn ng xy ra.
Cch gii: as
1. 2 CHCl
3
+ O
2
2 COCl
2
+ 2 HCl
COCl
2
+ 2 C
2
H
5
OH O=C(OC
2
H
5
)
2
+ 2 HCl
ietyl cacbonat
t
o

2. CHCl
3
+ 4 NaOH HCOONa + 3 NaCl + 2 HOH
HCOONa + 2 KMnO
4
+ 3 NaOH Na
2
CO
3
+ K
2
MnO
4
+ Na
2
MnO
4
+ 2 HOH
Anion MnO
4
2-
cho mu xanh.
15
3. Axit lactic l -hiroxiaxit, trong iu kin tin hnh phn ng D chuyn thnh
lactit X:
OH
CH
3
CH=O + HCN CH
3
CH

CN

OH t
o
OH
2 CH
3
CH + 2 HOH + H
+
CH
3
CH + NH
4
+

CN COOH
OH H
+
,t
o
COO
2 CH
3
CH CH
3
CH CHCH
3
+ 2 HOH
COOH OOC
lactit X

Cu IV (4,5 im): (thay cu IVbng A, dng cho bng B)
1. Vit phng trnh phn ng iu ch D-fructoz t D-glucoz, bit rng
D-glucozazon khi tc dng vi benzanehit to thnh ozon ca D-glucoz
(HOCH
2
(CHOH)
3
COCHO).
2. Chitin (tch t v tm, cua...) c coi nh l dn xut ca xenluloz,
trong cc nhm hiroxyl cc nguyn t C2 c thay th bng cc nhm
axetylamino ( -NH-CO-CH
3
).
a) Vit cng thc cu to mt on mch ca phn t chitin.
b) Gi tn mt mt xch ca chitin.
c) Vit phng trnh phn ng xy ra khi un nng chitin vi dung dch HCl
c (d), un nng chitin vi dung dch NaOH c (d).
Cch gii:
1. CH=O CH=N-NHC
6
H
5

C=N-NHC
6
H
5
+ C
6
H
5
NHNH
2
+ NH
3

+ 3 C
6
H
5
NHNH
2
(CH
3
OH)
CH
2
OH D-Glucozazon
CH
2
OH
CH=N-NHC
6
H
5
H
+
CH=O
C=N-NHC
6
H
5
+ 2 H
2
O CH=O + 2 C
6
H
5
NHNH
2

(CH
3
OH) (CH
3
OH)
CH
2
OH CH
2
OH

CH=O CH
2
OH (nhm -CH=O d b kh
CH=O + 2 [H]

C=O

hn nhm C=O )
(CH
3
OH)
CH
2
OH
CH
2
OH D-Fructoz

16
Cu III (5 im): (thay cu III bng A, dng cho bng B)
1. Cho hn hp ng phn t gm axit benzoic v axit p-metoxibenzoic tc dng
vi hn hp HNO
3
c v H
2
SO
4
c.
Vit cng thc cu to hai sn phm mononitro chnh v cho bit cht no to
thnh vi s mol nhiu hn? Hy so snh tnh axit ca cc cht gm hai axit u v hai
sn phm, gii thch.
2. C cc hp cht sau: H
3
NCH
2
COO

(A) , H
2
NCH
2
CONH
2
(B) ,
H
2
N-CO-NH
2
(C) , CH
3
CHOHCOOH (D). Cho bit tng hp cht trn thuc loi
hp cht c chc hu c no? Vit phng trnh phn ng ca tng hp cht trn vi:
a) Dung dch HCl (d, nng) ; b) Dung dch NaOH (d, nng).
Cch gii:
1. HNO
3

COOH + CH
3
O COOH COOH + CH
3
O COOH
H
2
SO
4

(A) (B) O
2
N (C) O
2
N (D)
- S mol D nhiu hn s mol C , v B c nhm CH
3
O- y electron lm nhn
thm giu electron hn.
- Tnh axit gim dn theo chiu : C > D > A > B .
(gii thch bng hi ng electron ca cc nhm th)
2. A l aminoaxit c nhm chc cacboxyl v nhm chc amino
B l dn xut ca aminoaxit c nhm chc amit v nhm chc amino
C l dn xut ca axit cacbonic c nhm chc amit (iamit)
D l - hiroxiaxit c nhm chc cacboxyl v nhm chc hiroxyl

t
o

a) H
3
NCH
2
COO + HCl [ H
3
NCH
2
COOH]Cl
t
o

H
2
NCH
2
CONH
2
+ HCl + H
2
O Cl[ H
3
NCH
2
COOH] + NH
4
Cl
t
o

H
2
N-CO-NH
2
+ 2 HCl + H
2
O 2 NH
4
Cl + CO
2

H
+

CH
3
CHCOOH + HCl CH
3
CHCOOH + H
2
O
OH Cl
t
o

b) H
3
NCH
2
COO + NaOH H
2
NCH
2
COONa + H
2
O
t
o

H
2
NCH
2
CONH
2
+ NaOH H
2
NCH
2
COONa + NH
3

t
o

H
2
N-CO-NH
2
+ 2 NaOH Na
2
CO
3
+ 2 NH
3

CH
3
CHCOOH + NaOH CH
3
CHCOOH + H
2
O
OH Cl

17
B GO DUC V O TAO K TH CHON HOC SNH G QUC GA
LP 12 THPT NAM HOC 2000-2001
thi chnh thc
Mn : ho hc Bng B
Thi gian : 180 pht ( khng k thi gian giao )
Ngy thi : 13 / 3 / 2001

Cu I (5 im):
1. Xut pht t brombenzen cha
14
C v tr 1 v cc ho cht v c cn thit
khng cha
14
C, hy iu ch cc hp cht thm cha
14
C v tr 3 : a) Anilin ;
b) Iotbenzen ; c) Axit benzoic.
2. Hon thnh s cc phn ng sau v gi tn cc sn phm t A n F :
Na
2
Cr
2
O
4
2 H
Cl
2
(1 mol) H
2
O C D
Benzen (1 mol) A B
FeCl
3
t
O
, p HNO
3
(1 mol) Fe, HCl
E F
3. Khi oxi ho etylenglicol bng HNO
3
th to thnh mt hn hp 5 cht. Hy
vit cng thc cu to phn t ca 5 cht v sp xp theo trt t gim dn nhit
si ca chng (c gii thch).

Cu II (3,5 im): N
Xinconiin (X) c cng thc cu to :
CH=CH
2
C
9
HOH
l ng phn lp th C
9
ca xinconin (Y). N
1. Hy ghi du vo mi nguyn t cacbon bt i v khoanh vng trn nguyn
t nit c tnh baz mnh nht trong phn t X.
2. Cho t t dung dch HBr vo X nhit phng ri un nng nh, sinh ra cc
sn phm chnh l A (C
19
H
23
BrON
2
) , B (C
19
H
24
Br
2
ON
2
) , C (C
19
H
25
Br
3
ON
2
) , v
D (C
19
H
24
Br
4
N
2
). Ch ho D vi dung dch KOH trong ru 90
o
thu c E (C
19
H
20
N
2
)
Hy vit cng thc cu to ca A , B , C , D , E. Ghi du vo mi nguyn t
cacbon bt i trong phn t D v E.

Cu III (5 im):
1. Cho hn hp ng phn t gm axit benzoic v axit p-metoxibenzoic tc dng
vi hn hp HNO
3
c v H
2
SO
4
c.
Vit cng thc cu to hai sn phm mononitro chnh v cho bit cht no to
thnh vi s mol nhiu hn? Hy so snh tnh axit ca cc cht gm hai axit u v hai
sn phm, gii thch.
2. C cc hp cht sau: H
3
NCH
2
COO

(A) , H
2
NCH
2
CONH
2
(B) ,
H
2
N-CO-NH
2
(C) , CH
3
CHOHCOOH (D). Cho bit tng hp cht trn thuc loi hp
cht c chc hu c no? Vit phng trnh phn ng ca tng hp cht trn vi :
a) Dung dch HCl (d, nng) ; b) Dung dch NaOH (d, nng).


18

Cu IV (4,5 im):
1. Vit phng trnh phn ng iu ch D-fructoz t D-glucoz, bit rng
D-glucozazon khi tc dng vi benzanehit to thnh ozon ca D-glucoz
(HOCH
2
(CHOH)
3
COCHO).
2. Chitin (tch t v tm, cua...) c coi nh l dn xut ca xenluloz, trong
cc nhm hiroxyl cc nguyn t C2 c thay th bng cc nhm axetylamino
( -NH-CO-CH
3
).
c) Vit cng thc cu to mt on mch ca phn t chitin.
d) Gi tn mt mt xch ca chitin.
c) Vit phng trnh phn ng xy ra khi un nng chitin vi dung dch HCl
c (d), un nng chitin vi dung dch NaOH c (d).
Cu V (2 im):
1. Clorofom tip xc vi khng kh ngoi nh sng s b oxi ha thnh photgen
rt c. nga c ngi ta bo qun clorofom bng cch cho thm mt lng nh
ancol etylic chuyn photgen thnh cht khng c.
Vit phng trnh phn ng oxi ha clorofom bng oxi khng kh thnh
photgen, phn ng ca photgen vi ancol etylic v gi tn sn phm.
2. un nng vi git clorofom vi lng d dung dch NaOH, sau nh thm
vi git dung dch KMnO
4
thy hn hp xut hin mu xanh. Vit cc phng trnh
phn ng v gii thch s xut hin mu xanh.

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19
B GO DUC V O TAO K TH CHON HOC SNH G QUC GA
LP 12 THPT NAM HOC 2000-2001
thi d b Mn : ho hc Bng A
Thi gian : 180 pht ( khng k thi gian giao )
NGY TH TH NHT : ( theo quyt nh v thng bo ca B)

Cu I :
1. Vit cc phng trnh ho hc t Na
2
Cr
2
O
7
, C (than ), Al (bt nhm) v
cc iu kin cn thit thu c Cr.
2. CrO
2
Cl
2
(cromyl clorua) l mt ho cht quan trng. Hy vit cc phng
trnh ho hc to ra CrO
2
Cl
2
t:
a) CrO
3
tc dng vi axit HCl.
b) Cho K
2
Cr
2
O
7
tc dng vi KCl tronh H
2
SO
4
c, nng.
3. Thm cht thch hp v hon thnh phng trnh ho hc sau:
a) KNO
2
+ KNO
3
+ ? K
2
CrO
4
+ NO
b) NaNO
2
+ ? + NaI I
2
+ NaHSO
4
+ NO + H
2
O
c) HNO
3
+ P
2
O
5
? + N
2
O
5
Cu II :
1. Vn dng l thuyt Bronstet v axit baz hy gii thch tnh axit baz trong
dung dch nc ca cc cht sau:
a) BaCl
2
; b) K
2
S ; c) NH
4
HS ; d) NaHSO
3

2. Hy trnh by 3 th nghim minh ho tnh cht axit baz trong mi dung
dch : a) NH
4
HSO
4
; b) Na
2
CO
3
(m t cch th nghim v gii thch).
3. Cho NaOH (d) vo hn hp X gm c Zn
2+
; Pb
2+
; Fe
3+
; Cu
2+
;
Mg
2+
; NO
3-
s c kt ta A v dung dch B.
Hy nu phng php ho hc xc nhn cc cht c mt trong kt ta A v
dung dch B(nu r nhn bit) Vit phng trnh ion ca cc phn ng xy ra.
Cu III :
1. Thm dn dung dch NaOH vo dung dch cha H
+
0,100M ; Fe
3+
1,0.10
-3
M
v Mg
2+
0,100M cho n d. Cho bit c hin tng g xy ra?
2. Gi s tng nng NaOH cho vo l 0,2030 M. Hy tnh nng cc ion
trong dung dch (khi tnh khng k s to phc hiroxo ca cc ion kim loi).
Cho: Tch s tan Mg(OH)
2
: 10
10,95
Fe(OH)
3
: 10
37,5
.
Cu IV :
1. Hai mui ca cng mt axit lm i mu khc nhau i vi giy qu tm, to
kt ta trng vi nc vi trong v to kt ta vng vi dung dch AgNO
3
l nhng
mui no? Vit cc phng trnh phn ng chng minh.
2. a) Nu dn chng c th cho thy Cu
2
O bn vi nhit hn CuO v CuCl bn
vi nhit hn CuCl
2
, gii thch nguyn nhn.
b) Nu dn chng c th cho thy trong nc CuCl km bn hn CuCl
2
, gii
thch nguyn nhn.
c) Th in cc chun ca cp Cu
2+
/ Cu
+
l 0,15V, ca cp I
2
/ 2I
-
l 0,54V nhng
ti sao ngi ta c th nh lng ion Cu
2+
trong dung dch nc thng qua tc dng
ca ion vi dung dch KI? Cho bit dung dch bo ho ca CuI trong nc nhit
thng c nng l10
-6
M.

20

Cu V :
1. Hy thit lp s pin sao cho khi pin phng in th xy ra phn ng kh ion
Fe
3+
bi Cu . Vit phng trnh cc na phn ng xy ra ti cc in cc.
2. Tnh sc in ng tiu chun ca pin (E
o
pin) khi pin mi bt u hot ng.
3. Tnh nng cc cht cn li trong cc dung dch khi pin phng in hon
ton (gi s nng cc cht trc phn ng u bng 0,010M).
4. Sc in ng ca pin s tng hay gim nu:
- Thm mt t KI
- Thm t NH
3
vo dung dch cc ng (dung dch A).
- Thm mt t KMnO
4
(mi trng axit)
- Thm t NaF
- Thm t NaOH
vo dung dch ca cc cha Fe
3+
(dung dch B).
Cho E
o
Cu
2+
/ Cu
+
= 0,34V ; E
o
Cu
+
/ Cu = 0,52V
E
o
Fe
3+
/ Fe
2+
= 0,77V ; E
o
Fe
2+
/ Fe = - 0,40V

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21
B GO DUC V O TAO K TH CHON HOC SNH G QUC GA
LP 12 THPT NAM HOC 2000-2001
thi d b Mn : ho hc Bng B
Thi gian : 180 pht ( khng k thi gian giao )
NGY TH TH NHT : ( theo quyt nh v thng bo ca B)
Cu I :
1. Vit cc phng trnh ho hc t Na
2
Cr
2
O
7
, C (than ), Al (bt nhm) v
cc iu kin cn thit thu c Cr.
2. CrO
2
Cl
2
(cromyl clorua) l mt ho cht quan trng. Hy vit cc phng
trnh ho hc to ra CrO
2
Cl
2
t:
a) CrO
3
tc dng vi axit HCl.
b) Cho K
2
Cr
2
O
7
tc dng vi KCl tronh H
2
SO
4
c, nng.
3. Thm cht thch hp v hon thnh phng trnh ho hc sau:
a) KNO
2
+ KNO
3
+ ? K
2
CrO
4
+ NO
b) NaNO
2
+ ? + NaI I
2
+ NaHSO
4
+ NO + H
2
O
c) HNO
3
+ P
2
O
5
? + N
2
O
5
Cu II :
1. Vn dng l thuyt Bronstet v axit-baz hy gii thch tnh axit-baz trong
dung dch nc ca cc cht sau:
a) BaCl
2
; b) K
2
S ; c) NH
4
HS ; d) NaHSO
3

2. Hy trnh by 3 th nghim minh ho tnh cht axit baz trong mi dung
dch : a) NH
4
HSO
4
; b) Na
2
CO
3
(m t cch th nghim v gii thch).
3. Cho NaOH (d) vo hn hp X gm c Zn
2+
; Pb
2+
; Fe
3+
; Cu
2+
;
Mg
2+
; NO
3-
s c kt ta A v dung dch B.
Hy nu phng php ho hc xc nhn cc cht c mt trong kt ta A v
dung dch B(nu r nhn bit) Vit phng trnh ion ca cc phn ng xy ra.
Cu III :
1. Thm dn dung dch NaOH vo dung dch cha H
+
0,100M ; Fe
3+
1,0.10
-3
M
v Mg
2+
0,100M cho n d. Cho bit c hin tng g xy ra?
2. Gi s tng nng NaOH cho vo l 0,2030 M. Hy tnh nng cc ion
trong dung dch (khi tnh khng k s to phc hiroxo ca cc ion kim loi).
Cho: Tch s tan Mg(OH)
2
: 10
10,95
Fe(OH)
3
: 10
37,5
.
Cu IV :
1. Hai mui ca cng mt axit lm i mu khc nhau i vi giy qu tm, to
kt ta trng vi nc vi trong v to kt ta vng vi dung dch AgNO
3
l nhng
mui no? Vit cc phng trnh phn ng chng minh.
2. a) Nu dn chng c th cho thy Cu
2
O bn vi nhit hn CuO v CuCl bn
vi nhit hn CuCl
2
, gii thch nguyn nhn.
b) Nu dn chng c th cho thy trong nc CuCl km bn hn CuCl
2
, gii
thch nguyn nhn.
c) Th in cc chun ca cp Cu
2+
/ Cu
+
l 0,15V, ca cp I
2
/ 2I
-
l 0,54V nhng
ti sao ngi ta c th nh lng ion Cu
2+
trong dung dch nc thng qua tc dng
ca ion vi dung dch KI? Cho bit dung dch bo ho ca CuI trong nc nhit
thng c nng l10
-6
M.
B GO DUC V O TAO K TH CHON HOC SNH G QUC GA
22
LP 12 THPT NAM HOC 2000-2001
thi d b Mn : ho hc Bng A
Thi gian : 180 pht ( khng k thi gian giao )
NGY TH TH HA : ( theo quyt nh v thng bo ca B)

Cu I :
1.Vit cc phng trnh phn ng (nu c) ca:
a) Axit axetic (pKa = 4,76) , phenol (pKa = 10) vi :
- Dung dch NaHCO
3

- Dung dch Na
2
CO
3

Bit H
2
CO
3
c pKa
1
= 6,4 v pKa
2
= 10,3
b) Dung dch CH
3
COONa , dung dch C
6
H
5
ONa vi CO
2
2. Hon thnh cc phng trnh phn ng (cc sn phm vit dng cng thc
cu to) theo cc s chuyn ho sau:
CH
3
OH(dung mi)
a) C
6
H
5
CH=CH
2
+ Br
2
A + B
H
2
SO
4
, t
o
b) C
6
H
5
CH=CH
2
C(C
16
H
16
)
Nu tn cc c ch ca phn ng a) v b).
COOH
CO
2
H
+
(CH
3
CO)
2
O OCOCH
3
e) C
6
H
5
ONa M N
6 at, 125
o
C
(Aspirin)
Cu II :
Hp cht thin nhin X cha 66,67% cacbon; 6,67% hiro; cn li l oxi. Bit
phn t khi ca X l 180.
X tc dng vi (CH
3
CO)
2
O cho A(C
14
H
16
O
5
), vi HBr lnh cho B (C
10
H
11
BrO
2
,
gm hai ng phn c to B1 v B2), vi CH
3
I (c mt baz) cho D (C
11
H
14
O
3
), vi HI
nng cho CH
3
I , v vi O
3
ri Zn / HCl (dung dch) cho E (C
8
H
8
O
3
).
E tc dng vi HI nng cng cho CH
3
I, ngoi ra E cn kh c AgNO
3
. X , B ,
v E tan trong dung dch NaOH nhng khng tan trong dung dch NaHCO
3
.
A v D khng tan trong dung dch NaOH nhng d lm mt mu KMnO
4
long
ngui v brom long.
1. Xc nh cng thc phn t v cc nhm chc c trong phn t X.
2. Xc nh cng thc cu to ca X , A , B , D v E ; bit rng E l ng phn
c pKa gn thp nht.
3. Dng cc cng thc cu to thu gn vit cc phng trnh phn ng xy ra.
Gii thch ti sao sinh ra hai ng phn ca B.
4. Gi tn X , B1 , E.
Cu III :
1. Vit phng trnh phn ng monoclo ho sec-butyl clorua, gi tn cc sn
phm to thnh.
2. Nu xut pht t (S)-sec-butyl clorua th s nhn c bao nhiu hp cht
quang hot? Vit cng thc cu to v gi tn theo danh php R , S.


23
3. Hon thnh s cc phn ng sau v gi tn cc sn phm :
Cl
2
(1 mol) HNO
3
(1 mol) HN(C
2
H
5
)
2
Fe, HCl
a) Benzen (1 mol) A B C D
AlCl
3
H
2
SO
4

CH
3
I (1 mol)
HNO
3
(1 mol) Fe, HCl G
b) Phenol (1 mol) E F
ClCH
2
COOH
H
Cu IV :
Thnh phn chnh ca tinh du hi l anetol (C
10
H
12
O). Cho anetol phn ng vi
dung dch KMnO
4
trong nc th to thnh kali axetat, kali p-metoxi benzoat v MnO
2
.
1. Xc nh cng thc cu to ca anetol, vit cng thc cu trc cc ng phn
khng gian c th c v gi tn IUPAC ca chng.
2. Vit cc phng trnh phn ng xy ra v ngh cch tch ly axit p-metoxi
benzoic t hn hp sau phn ng.
3. Dng cng thc cu to, hy vit cc phng trnh phn ng ca anetol vi: a)
Br
2
/ CCl
4
; b) HCl ; c) Cl
2
+ H
2
O
4. Khi un nng vi xc tc, anetol thng b ho nha. Hy gii thch.

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























24
B GO DUC V O TAO K TH CHON HOC SNH G QUC GA
LP 12 THPT NAM HOC 2000-2001
thi d b Mn : ho hc Bng B
Thi gian : 180 pht ( khng k thi gian giao )
NGY TH TH HA : ( theo quyt nh v thng bo ca B)

Cu I :
1.Vit cc phng trnh phn ng (nu c) ca:
a) Axit axetic (pKa = 4,76) , phenol (pKa = 10) vi :
- Dung dch NaHCO
3

- Dung dch Na
2
CO
3

Bit H
2
CO
3
c pKa
1
= 6,4 v pKa
2
= 10,3
b) Dung dch CH
3
COONa , dung dch C
6
H
5
ONa vi CO
2
2. Hon thnh cc phng trnh phn ng (cc sn phm vit dng cng thc
cu to) theo cc s chuyn ho sau:
CH
3
OH(dung mi)
a) C
6
H
5
CH=CH
2
+ Br
2
A + B
H
2
SO
4
, t
o
b) C
6
H
5
CH=CH
2
C(C
16
H
16
)
Nu tn cc c ch ca phn ng a) v b).
COOH
CO
2
H
+
(CH
3
CO)
2
O OCOCH
3
f) C
6
H
5
ONa M N
6 at, 125
o
C
(Aspirin)
Cu II :
Hp cht thin nhin X cha 66,67% cacbon; 6,67% hiro; cn li l oxi. Bit
phn t khi ca X l 180.
X tc dng vi (CH
3
CO)
2
O cho A(C
14
H
16
O
5
), vi HBr lnh cho B (C
10
H
11
BrO
2
,
gm hai ng phn c to B1 v B2), vi CH
3
I (c mt baz) cho D (C
11
H
14
O
3
),vi HI
nng cho CH
3
I , v vi O
3
ri Zn / HCl (dung dch) cho E (C
8
H
8
O
3
).
E tc dng vi HI nng cng cho CH
3
I, ngoi ra E cn kh c AgNO
3
. X , B ,
v E tan trong dung dch NaOH nhng khng tan trong dung dch NaHCO
3
.
A v D khng tan trong dung dch NaOH nhng d lm mt mu KMnO
4
long
ngui v bom long.
1. Xc nh cng thc phn t v cc nhm chc c trong phn t X.
2. Xc nh cng thc cu to ca X , A , B , D v E ; bit rng E l ng phn
c pKa gn thp nht.
Cu III :
1. Vit phng trnh phn ng monoclo ho sec-butyl clorua, gi tn cc sn
phm to thnh.
2. Hon thnh s cc phn ng sau v gi tn cc sn phm :
Cl
2
(1 mol) HNO
3
(1 mol) HN(C
2
H
5
)
2
Fe, HCl
a) Benzen (1 mol) A B C D
AlCl
3
H
2
SO
4



25

CH
3
I (1 mol)
HNO
3
(1 mol) Fe, HCl G
b) Phenol (1 mol) E F
ClCH
2
COOH
H
Cu IV :
Thnh phn chnh ca tinh du hi l anetol (C
10
H
12
O). Cho anetol phn ng vi
dung dch KMnO
4
trong nc th to thnh kali axetat, kali p-metoxi benzoat v MnO
2
.
1. Xc nh cng thc cu to ca anetol, vit cng thc cu trc cc ng phn
khng gian c th c v gi tn IUPAC ca chng.
2. Vit cc phng trnh phn ng xy ra v ngh cch tch ly axit p-metoxi
benzoic t hn hp sau phn ng.
3. Dng cng thc cu to, hy vit cc phng trnh phn ng ca anetol vi: a)
Br
2
/ CCl
4
; b) HCl ; c) Cl
2
+ H
2
O
4. Khi un nng vi xc tc, anetol thng b ho nha. Hy gii thch.

____________________________

26