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TUY N 5 HSG THNH PH N NG HO H C 11

S GIO DC V O TO
THNH PH NNG
HNG DN CHM K THI HC SINH GII THNH PH
MN: HA HC LP 11
Thi gian: 150 pht (khng k thi gian giao )
Cu I M (3 im)
1. Hy so snh v gii thch s khc nhau v phn cc phn t, nhit si v mnh tnh
baz gia NH
3
v NF
3
.
2. N
2
O
4
phn li 20,0% thnh NO
2
27
o
C v 1,00 atm. Hy xc nh (a) gi tr K
p
; (b) phn li
ca N
2
O
4
ti 27
o
C v 0,10 atm; (c) phn li ca 69g N
2
O
4
trong bnh 20 L 27
o
C.
3. Tnh pH ca dung dch thu c khi thi ht 224 mL kh CO
2
vo 200 mL dung dch NaOH
0,05M, bit axit cacbonic c
35 , 6 pK
1 a

,
33 , 10 pK
2 a

.
P N IM
1. Cu to:
N
H
H
H
N
F
F
F
- NH
3
phn cc hn NF
3
do trong NH
3
lng cc lin kt v lng cc
electron t do cng chiu, cn trong NF
3
lng cc lin kt v lng cc
electron t do ngc chiu.
- Nhit si ca NH
3
cao hn do NH
3
to c lin kt H lin phn t.
- NH
3
l mt baz cn NF
3
th khng, do trong NF
3
cc nguyn t F ht
electron lm gim mt electron trn nguyn t N.
2. Xt phn ng phn li:
N
2
O
4
2NO
2

n 0
n 2n
n-n 2n
Phn mol:
+

1
1
+

1
2
,
P
1
4
P
P
P
K
2
2
O N
2
NO
O N
2
NO
P
4 2
2
4 2
2


(a)
17 , 0 1
) 2 , 0 ( 1
) 2 , 0 ( 4
P
1
4
K
2
2
2
2
P

(b) %) 6 , 54 ( 546 , 0 17 , 0 10 , 0
1
4
2
2

(c) mol 75 , 0
92
69
n
) 1 ( 9225 , 0
20
300 082 , 0 ) 1 ( 75 , 0
P
4 2
O N



845 , 1
20
300 082 , 0 . 75 , 0 . 2
P
2
NO
17 , 0
) 1 ( 9225 , 0
) 845 , 1 (
K
2
P

%) 27 , 19 ( 1927 , 0
0,75
(0,25

3)
1,50
(0,50

3)
1
TUY N 5 HSG THNH PH N NG HO H C 11
3.
01 , 0 05 , 0 2 , 0 n , mol 01 , 0
4 , 22
224 , 0
n
NaOH CO
2

V s mol CO
2
v NaOH bng nhau nn h ch cha NaHCO
3
. C th tnh pH
ca h lng tnh ny bng cng thc:
( ) 3 , 8 33 , 10 35 , 6
2
1
) pK pK (
2
1
pH
2 1
+ +
0,75
(0,25+0,5)
Cu II (3 im)
1. Vit phng trnh phn ng xy ra khi cho NH
4
Cl tc dng vi CuO v vi ZnO. Cho bit
ng dng thc t ca NH
4
Cl tng ng vi cc phn ng ny.
2. Ha tan 10,00 g hn hp gm Cu
2
S v CuS bng 200,0 mL dung dch MnO
4
-
0,7500 M trong
mi trng axit. Sau khi un si ui ht kh SO
2
sinh ra, lng MnO
4
-
cn d trong dung
dch phn ng va ht vi 175,0 mL dung dch Fe
2+
1,000 M.
(a) Vit cc phng trnh phn ng xy ra (dng phng trnh ion thu gn).
(b) Tnh phn trm khi lng CuS trong hn hp ban u.
P N IM
1. Trong thc t, NH
4
Cl c dng nh sch b mt kim loi trc khi hn:
4CuO + 2NH
4
Cl N
2
+ 3Cu + CuCl
2
+ 4H
2
O
ZnO + 2NH
4
Cl ZnCl
2
+ 2NH
3
+ H
2
O
2. (a) Phng trnh phn ng:
5Cu
2
S + 8MnO
4
-

+ 44H
+
10Cu
2+
+ 5SO
2
+ 8Mn
2+
+ 22H
2
O (1)
5CuS + 6MnO
4
-

+ 28H
+
5Cu
2+
+ 5SO
2
+ 6Mn
2+
+ 14H
2
O (2)
5Fe
2+
+ MnO
4
-
+ 8H
+
5Fe
3+
+ Mn
2+
+ 4H
2
O (3)
(b) Xc nh %
(1)
mol 035 , 0 1 175 , 0
5
1
n
5
1
n
2
4
Fe ) 3 ( MnO

+

mol 115 , 0 035 , 0 75 , 0 2 , 0 n


) 2 , 1 ( MnO
4

t s mol Cu
2
S v CuS ln lt l x v y, ta c:

'

'

+
+
0625 , 0 y
025 , 0 x
115 , 0 y
5
6
x
5
8
10 y 96 x 160

% 60 % 100
10
96 0625 , 0
m %
S Cu

1,50
(0,50

3)
0,75
(0,25

3)
0,75
Cu III (4 im)
1. Ch dng cht ch th phenolphtalein, hy phn bit cc dung dch NaHSO
4
, Na
2
CO
3
, AlCl
3
,
Fe(NO
3
)
3
, NaCl, Ca(NO
3
)
2
. Cc phn ng minh ha vit di dng ion thu gn.
2. Ha tan ht 2,2 g hn hp kim loi A gm st v nhm trong 150 mL dung dch HNO
3
2M
thu c dung dch B v 448 mL (ktc) kh C gm N
2
O v N
2
c t khi so vi khng kh
bng 1,2414. Thm 13,6 g NaOH nguyn cht vo dung dch B thu c kt ta D, lc kt ta
D thu c dung dch nc lc E.
(a) Tnh phn trm khi lng mi kim loi trong hn hp A ban u.
(b) Nung kt ta D n khi lng khng i th thu c bao nhiu gam cht rn khan?
(c) Tnh th tch dung dch HCl 0,5M cn thm vo dung dch E thu c 2,34 g kt ta.
2
TUY N 5 HSG THNH PH N NG HO H C 11
P N IM
1. Trch mu th cho mi ln th nghim:
Cho phenolphtalein vo mi mu th. Mu th c mu hng l dung dch
Na
2
CO
3
, cc mu th cn li khng mu.
CO
3
2-
+ H
2
O HCO
3
-
+ OH
-
Dng Na
2
CO
3
lm thuc th cho vo cc mu th cn li.
Mu th c si bt kh khng mu l NaHSO
4
CO
3
2-
+ 2H
+
H
2
O + CO
2

Mu th to kt ta trng keo v si bt kh khng mu l AlCl


3
2Al
3+
+ 3CO
3
2-
+ 3H
2
O 2Al(OH)
3
+ 3CO
2

Mu th to kt ta nu v si bt kh khng mu l Fe(NO
3
)
3
2Fe
3+
+ 3CO
3
2-
+ 3H
2
O 2Fe(OH)
3
+ 3CO
2

Mu th to kt ta trng l Ca(NO
3
)
2
Ca
2+
+ CO
3
2-
CaCO
3

Mu th khng to hin tng l NaCl.


2. (a) t s mol N
2
O v N
2
ln lt bng a v b, ta c:

'



+
+
01 , 0 b a
36 29 2414 , 1
02 , 0
b 28 a 44
02 , 0
4 , 22
448 , 0
b a
t s mol Fe v Al ln lt bng x v y
Cht kh Cht oxi ha
Fe - 3e Fe
3+
10H
+
+ 2NO
3
-
+ 8e N
2
O + 5H
2
O
3x x 0,10 0,08
Al - 3e Al
3+
12H
+
+ 2NO
3
-
+ 10e N
2
+ 6H
2
O
3y y 0,12 0,10
V
mol 3 , 0 ) bd ( n mol 22 , 0 ) pu ( n
H H
<
+ + nn axit d, phn ng khng to
Fe
2+
.
Ta c:

'

'

+
+
04 , 0 y
02 , 0 x
18 , 0 y 3 x 3
2 , 2 y 27 x 56
Vy
% 9 , 50 % 100
2 , 2
56 02 , 0
m %
Fe

v % 1 , 49 m %
Al

(b) Thm NaOH vo dung dch B [H
+
(0,15.2-0,22 = 0,08 mol), Fe
3+
(x = 0,02
mol), Al
3+
(y = 0,04 mol) v NO
3
-
]
H
+
+ OH
-
H
2
O (1)
Fe
3+
+ 3OH
-
Fe(OH)
3
(2)
Al
3+
+ 3OH
-
Al(OH)
3
(3)
Al(OH)
3
+ OH
-
AlO
2
-
+ 2H
2
O (4)
mol 34 , 0
40
6 , 13
n mol 3 , 0 n 4 n 3 n n
) bd ( OH Al Fe H ) 4 , 3 , 2 , 1 ( OH
3 3
< + +
+ + +
sau (1), (2), (3), (4) vn cn d OH
-
, kt ta D l Fe(OH)
3
(0,02mol)
2Fe(OH)
3
Fe
2
O
3
+ 3H
2
O, m
rn
=
g 6 , 1 160 01 , 0 m
3 2
O Fe

(c) Thm HCl vo dung dch E [Na
+
, OH
-
(0,04 mol), AlO
2
-
(0,04 mol) v NO
3
-
]
OH
-
+ H
+
H
2
O (5)
AlO
2
-
+ H
+
+ H
2
O Al(OH)
3
(6)
Al(OH)
3
+ 3H
+
Al
3+
+ 3H
2
O (7)
1,50
(0,25

6)
1,00
0,50
3
TUY N 5 HSG THNH PH N NG HO H C 11
mol 03 , 0
78
34 , 2
n
3
) OH ( Al

Trng hp 1: Xy ra (5), (6) v AlO
2
-
d
mol 07 , 0 03 , 0 04 , 0 n n n
3
) OH ( Al
OH H
+ +
+ ,
L 14 , 0
5 , 0
07 , 0
V
Trng hp 2: Xy ra (5), (6), (7)
mol 01 , 0 03 , 0 04 , 0 n
) 7 ( ) OH ( Al
3

mol 11 , 0 03 , 0 04 , 0 04 , 0 n 3 n n n
) 7 ( ) OH ( Al
AlO OH H 3
2
+ + + +
+

L 22 , 0
5 , 0
11 , 0
V
1,00
(0,50

2)
Cu IV (3 im)
1. Tnh hiu ng nhit phn ng hidro ha etilen to etan, bit nhit chy ca C
2
H
6
v C
2
H
4
ln
lt bng -368,4 kcal/mol v -337,2 kcal/mol [sn phm chy l CO
2
(k) v H
2
O (l)], nhit
hnh thnh H
2
O (l) l -68,32 kcal/mol.
2. (a) Vit cng thc cu to v gi tn anken t cacbon nht ng thi c ng phn hnh hc v
ng phn quang hc. (b) Vit cc ng phn hnh hc v quang hc ng vi cu to (s
dng cng thc Fisher) v xc nh cu hnh mi ng phn (Z/E v R/S). (b) Vit cu to cc
sn phm chnh hnh thnh khi cho anken trn tc dng vi dung dch nc brom c lng
nh mui natri clorua.
P N IM
1. (1) C
2
H
6
(k) + 7/2O
2
(k) 2CO
2
(k) + 3H
2
O (l)
kcal 4 , 368 H
(2) C
2
H
4
(k) + 3O
2
(k) 2CO
2
(k) + 2H
2
O (l)
kcal 2 , 337 H
(3) H
2
(k) + 1/2O
2
(k) H
2
O (l)
kcal 32 , 68 H
Ly (2) - (1) + (3) ta c:
C
2
H
4
(k) + H
2
(k) C
2
H
6
(k)
kcal 1 , 37 ) 32 , 68 ( ) 4 , 368 ( ) 2 , 337 ( H +
2. (a) Cu to:
CH
3
CH CH C
H
CH
3
C
2
H
5
(4-metylhex-2-en)
(b) Cu hnh:
C
C
CH
3
H
C
2
H
5
C
H
H
CH
3
C
C
H CH
3
C
2
H
5
C
C
CH
3
H
C
2
H
5
C
CH
3
H
H
C
C
H CH
3
C
2
H
5
H
H
C
CH
3
H
CH
3
C
H
(E)(R) (E)(S)
(Z)(R)
(Z)(S)
(c) Cu to cc sn phm:
1,00
0,25
1,00
(0,25

4
)
0,75
4
TUY N 5 HSG THNH PH N NG HO H C 11
CH
3
CH CH CH
CH
3
C
2
H
5
CH
3
CH CH CH
CH
3
C
2
H
5
Br Br
CH
3
CH CH CH
CH
3
C
2
H
5
OH Br
CH
3
CH CH CH
CH
3
C
2
H
5
Cl Br
(0,25

3
)
Cu V (3 im)
1. Hidrocacbon A c khi lng phn t bng 80. Ozon phn A ch to andehit fomic v andehit
oxalic.
C H
O
H C H
O
C
O
H
andehit fomic andehit oxalic
(a) Xc nh cu to v gi tn A.
(b) Dng c ch gii thch cc sn phm hnh thnh khi cng Br
2
vo A theo t l mol 1:1, gi
tn cc sn phm ny.
2. Hp cht A c cng thc phn t C
9
H
8
. A lm mt mu Br
2
trong CCl
4
; hidro ha A trong
iu kin m du to ra C
9
H
10,
cn

trong iu kin nhit v p sut cao th to ra C
9
H
16
; oxi
ha mnh lit A sinh ra axit phtalic [1,2-C
6
H
4
(COOH)
2
]. Lp lun xc nh cu to ca A.
P N IM
1. (a) Cng thc tng qut cho A l C
x
H
y
Ta c

'

'

+
+
8 y
6 x
2 x 2 y
80 y x 12
, cng thc phn t C
6
H
8

) 3 (
T sn phm ozon phn ta thu c cu to ca A:
CH
2
CH CH CH CH CH
2
H
2
C O O
H
C
H
C O O
H
C
H
C O O CH
2
A (hexa-1,3,5-trien)
(b) C ch v sn phm:
0,50
0,50
(0,25

2
)
1,50
(0,50

3
)
5
TUY N 5 HSG THNH PH N NG HO H C 11
CH
2
CH CH CH CH CH
2
Br
2
CH
2
CH CH CH CH CH
2
CH
2
CH CH CH CH CH
2
Br
Br
CH
2
CH CH CH CH CH
2
Br
CH
2
CH CH CH CH CH
2
CH
2
CH CH CH CH CH
2
Br
Br
CH
2
CH CH CH CH CH
2
Br
Br
Br
Br
(X) 5,6-dibromhexa-1,3-dien; (Y) 3,6-dibromhexa-1,4-dien;
(X)
(Y)
(Z)
(Z) 1,6-dibromhexa-2,4-dien
2. A (C
9
H
8
) c bt bo ha 6
A lm mt mu Br
2
v cng m du 1 phn t H
2
cho thy A c 1 lin kt i.
A cng ti a 4 phn t H
2
v khi oxi ha to axit phtalic cho thy A c vng
benzen v ngoi ra cn mt vng 5 cnh na.
Cng thc ca A:
0,50
Cu VI (4 im)
Chia 3,584 L (ktc) hn hp gm mt ankan (A), mt anken (B) v mt ankin (C) thnh 2 phn
bng nhau. Phn 1 cho qua dung dch AgNO
3
d trong NH
3
thy th tch hn hp gim 12,5% v
thu c 1,47g kt ta. Phn 2 cho qua dung dch brom d thy khi lng bnh brom tng 2,22g
v c 13,6g brom tham gia phn ng. t chy hon ton kh ra khi bnh brom ri hp th
sn phm chy vo dung dch Ba(OH)
2
d th thu c 2,955g kt ta.
1. Xc nh cng thc cu to A, B v C.
2. T A vit dy chuyn ha (ghi r iu kin phn ng) iu ch 1,1-dibrompropan v 2,2-
dibrompropan.
3. Vit phng trnh phn ng xy ra khi cho C tc dng vi dung dch KMnO
4
trong (i) mi
trng trung tnh nhit phng v (ii) mi trng axit (H
2
SO
4
) c un nng.
P N IM
1. Trong mt phn, ta c:
mol 08 , 0
4 , 22
584 , 3
2
1
n
C , B , A

. Dung dch AgNO
3
/NH
3
ch
hp th ankin, t cng thc ankin l RCCH (gi s khng phi l C
2
H
2
).
RCCH + AgNO
3
+ NH
3
RCCAg + NH
4
NO
3
(1)
mol 01 , 0 08 , 0
100
5 , 12
n n
ankin
(R + 132)

0,01 = 1,47
R = 15 (CH
3
-), cng thc ca ankin l CH
3
CCH
Dung dch brom hp th anken (C
n
H
2n
) v ankin
C
n
H
2n
+ Br
2
C
n
H
2n
Br
2
(2)
C
3
H
4
+ 2Br
2
C
3
H
4
Br
4
(3)
g 82 , 1 40 01 , 0 22 , 2 m
n 2 n
H C

, mol 065 , 0 2 01 , 0
160
6 , 13
n
) 2 ( Br
2

0,75
0,75
6
TUY N 5 HSG THNH PH N NG HO H C 11
T
065 , 0
1
82 , 1
n 14

n = 2, cng thc ca anken l CH


2
=CH
2
.
Kh ra khi bnh brom l ankan (C
m
H
2m+2
),
mol 005 , 0 065 , 0 01 , 0 08 , 0 n
2 n 2 n
H C

+
C
m
H
2m+2
+
2
O
2
1 n 3

,
_

+
nCO
2
+ (n+1)H
2
O (4)
CO
2
+ Ba(OH)
2
BaCO
3
+ H
2
O (5)
015 , 0
197
955 , 2
n n
3 2
BaCO CO

T (4):
3 n
015 , 0
n
005 , 0
1

, cng thc ankan l CH
3
CH
2
CH
3
.
2. iu ch:
C
3
H
8
C
3
H
7
Cl CH
3
CH=CH
2
CH
3
CHBr-CH
2
Br
CH
3
C CH
CH
3
CH
2
CHBr
2
CH
3
CBr
2
CH
3
Cl
2
,as KOH/ROH
KOH/ROH
Br
2
HBr
HBr
peoxit
3. Phn ng ca C:
+ 2KMnO
4
CH
3
C CH CH
3
C C
O O
+ 2MnO
2
+ KOH OK

5CH
3
CCH + 8KMnO
4
+ 12H
2
SO
4
5CH
3
COOH + 5CO
2

+ 8MnSO
4
+ 4K
2
SO
4
+
12H
2
O
0,50
1,00
(0,50

2)
1,00
(0,50

2)
7
TUY N 5 HSG THNH PH N NG HO H C 11
S GIO DC V O TO
THNH PH NNG
HNG DN CHM K THI HC SINH GII THNH PH
MN: HA HC LP 11
Thi gian: 150 pht (khng k thi gian giao )
Cu VII (4 im)
1. Nu hin tng xy ra v vit phng trnh phn ng minh ha trong cc trng hp sau:
(a) Ha tan t t cho n d dung dch NaOH vo dung dch AlCl
3
, sau thm HCl vo
dung dch thu c n d.
(b) Thm dung dch K
2
CO
3
vo dung dch Fe(NO
3
)
3
2. A l dung dch Na
2
CO
3
0,1M; B l dung dch hn hp Na
2
CO
3
0,1M v KHCO
3
0,1M v C l
dung dch KHCO
3
0,1M.
(a) Tnh th tch kh CO
2
(ktc) thot ra khi cho t t tng git n ht 50 mL dung dch HCl
0,1M vo 100 mL dung dch A v khi cho ht 100 mL dung dch B vo 200 mL dung
dch HCl 0,1M.
(b) Xc nh s mol cc cht c trong dung dch thu c khi thm 100 mL dung dch
Ba(OH)
2
0,1M vo 150 mL dung dch C.
(c) Tnh pH ca cc dung dch A v C, bit axit cacbonic c pK
1
= 6,35 v pK
2
= 10,33.
(d) ngh phng php nhn bit cc anion c trong dung dch B.
P N IM
1. (a) Thm dung dch NaOH vo dung dch AlCl
3
thy xut hin kt ta trng keo,
sau tan li:
Al
3+
+ 3OH
-
Al(OH)
3
Al(OH)
3
+ OH
-

Al(OH)
4
-
Thm HCl vo dung dch thu c li thy xut hin kt ta trng keo,
sau tan li:
Al(OH)
4
-
+ H
+
Al(OH)
3
+ H
2
O
Al(OH)
3
+ 3H
+
Al
3+
+ 3H
2
O
0,50
(b) Thm dung dch K
2
CO
3
vo dung dch Fe(NO
3
)
3
thy xut hin kt ta nu
v si bt kh khng mu: 2Fe
3+
+ 3CO
3
2-
+ 3H
2
O 2Fe(OH)
3
+ 3CO
2
0,25
2. (a) Cho t t tng git n ht 50 mL dung dch HCl 0,1M vo 100 mL dung dch
Na
2
CO
3
0,1M
CO
3
2-

+ H
+
HCO
3
-
0,01 0,005
0,005 0,005
0,005 0
Do CO
3
2-
d nn khng c giai on to CO
2
,
0 V
2
CO

0,50
Cho ht 100 mL dung dch Na
2
CO
3
0,1M v KHCO
3
0,1M vo 200 mL dung
dch HCl 0,1M:
CO
3
2-

+ 2H
+
H
2
O + CO
2
(1)
HCO
3
-
+ H
+
H
2
O + CO
2
(2)
V
+
> +
H HCO CO
n n n 2
3
2
3
nn H
+
phn ng ht.
Gi s (1) xy ra trc th ta c mol 01 , 0 n
2
1
n
H
CO
2

+
Gi s (2) xy ra trc th t (1) v (2) ta c
mol 015 , 0 n
2
CO

1,00
8
TUY N 5 HSG THNH PH N NG HO H C 11
Thc t (1) v (2) ng thi xy ra nn:
L 336 , 0 4 , 22 015 , 0 V 4 , 22 01 , 0 L 224 , 0
2
CO
< <
(b) Thm 100 mL dung dch Ba(OH)
2
0,1M vo 150 mL dung dch KHCO
3
0,1M
HCO
3
-
+ OH
-
CO
3
2-
+ H
2
O
0,015 0,02
0,015 0,015
0 0,005 0,015
Ba
2+
+ CO
3
2-
BaCO
3
0,01 0,015
0,01 0,01
0 0,005
Dung dch cn 0,005 mol KOH v 0,005 mol K
2
CO
3
0,50
(c) Dung dch A c cc cn bng:
CO
3
2-
+ H
2
O HCO
3
-

+ OH
-
K
b1
= 10
-3,67
HCO
3
-
+ H
2
O H
2
O + CO
2
+ OH
-
K
b2
= 10
-7,65
H
2
O H
+
+ OH
-
K
N
= 10
-14
V K
b1
>> K
b2
>> K
N
nn cn bng (1) l ch yu:
pH = 14 -
2
1
(pK
b1
+ pC) = 14 -
2
1
(3,67 + 1) = 11,67
Dung dch C l dung dch lng tnh nn:
pH =
2
1
(pK
1
+ pK
2
) =
2
1
(6,35 + 10,33) = 8,34
0,75
(d) Trch mu th, thm BaCl
2
d vo mu th thy xut hin kt ta trng (tan
trong axit), nh vy mu th c CO
3
2-
.
Ba
2+
+ CO
3
2-
BaCO
3
Lc tch kt ta, thm HCl vo dung dch nc lc thy si bt kh khng mu
(lm c nc vi trong), vy dung dch c HCO
3
-
HCO
3
-
+ H
+
H
2
O + CO
2
.
0,50
Cu VIII (4 im)
1. (a) Amoniac c tnh oxi ha hay tnh kh? Vit phng trnh phn ng minh ha. (b) Trong
dung mi amoniac lng, cc hp cht KNH
2
, NH
4
Cl, Al(NH
2
)
3
c tnh axit, baz hay lng
tnh ? Vit cc phng trnh phn ng minh ha.
2. Ha tan 4,8 gam kim loi M bng dung dch HNO
3
c nng d, hay ha tan 2,4 gam mui
sunfua kim loi ny cng trong dung dch HNO
3
c nng, th u cng sinh ra kh NO
2
duy
nht c th tch bng nhau trong cng iu kin.
(a) Vit cc phng trnh phn ng di dng phng trnh ion.
(b) Xc nh kim loi M, cng thc phn t mui sunfua.
(c) Hp th kh sinh ra c hai phn ng trn vo 300 mL dung dch NaOH 1M, ri thm
vo mt t phenolphtalein. Hi dung dch thu c c mu g? Ti sao?
P N IM
1. (a) NH
3
va c tnh oxi ha, va c tnh kh :
Tnh oxi ha: K + NH
3 (l)
KNH
2
+ 1/2H
2
Tnh kh: 2NH
3
+ 3CuO 3Cu + N
2
+ 3H
2
O
0,75
(b) KNH
2
l mt baz, NH
4
Cl l axit v Al(NH
2
)
3
c tnh lng tnh.
Phn ng trung ha: KNH
2
+ NH
4
Cl KCl + 2NH
3
9
TUY N 5 HSG THNH PH N NG HO H C 11
Phn ng ca cht lng tnh vi axit: Al(NH
2
)
3
+ 3NH
4
Cl AlCl
3
+ 6NH
3

Phn ng ca cht lng tnh vi baz: Al(NH
2
)
3
+ KNH
2
K[Al(NH
2
)
4
]
075
2. (a) Phng trnh phn ng:
M + 2mH
+
+ mNO
3
-
M
m+
+ mNO
2
+ mH
2
O
(1)
M
2
S
n
+ 4(m+n)H
+
+ (2m+6n)NO
3
-
2M
m+
+ nSO
4
2-
+ (2m+6n)NO
2

+ 2(m+n)H
2
O (2)
1,00
(b) V s mol NO
2
hai trng hp l bng nhau nn ta c:
) n 6 m 2 (
n 32 M 2
4 , 2
m
M
8 , 4
+
+

'

3 , 2 , 1 m , n
m 2 n 6
mn 64
M
, nghim thch hp l n = 1, m = 2 v M = 64.
Vy M l Cu v cng thc mui l Cu
2
S.
0,75
(c) mol 075 , 0
64
8 , 4
n
Cu

Cu + 4HNO
3
Cu(NO
3
)
2
+ 2NO
2
+ 2H
2
O
NaOH NO
n mol 3 , 0 075 , 0 2 2 n
2

xy ra va phn ng:
2NO
2
+ 2NaOH NaNO
3
+ NaNO
2
+ H
2
O
Dung dch thu c c mu hng do NO
2
-
to mi trng baz:
NO
2
-
+ H
2
O HNO
2
+ OH
-
0,75
Cu IX (4 im)
1. (a) Tnh t l cc sn phm monoclo ha (ti nhit phng) v monobrom ha (ti 127
o
C)
isobutan. Bit t l kh nng phn ng tng i ca nguyn t H trn cacbon bc nht, bc
hai v bc ba trong phn ng clo ha l 1,0 : 3,8 : 5,0 v trong phn ng brom ha l 1 : 82 :
1600.
(b) Da vo kt qu tnh c cu (a), cho nhn xt v cc yu t nh hng n hm lng
cc sn phm ca phn ng halogen ha ankan.
2. Dng c ch phn ng gii thch ti sao khi x l 2,7-imetylocta-2,6-dien vi axit
photphoric th thu c 1,1-imetyl-2-isopropenylxiclopentan.
3. Hiro ha mt hirocacbon A (C
8
H
12
) hot ng quang hc thu c hirocacbon B (C
8
H
18
)
khng hot ng quang hc. A khng tc dng vi Ag(NH
3
)
2
+
v khi tc dng vi H
2
trong s
c mt ca Pd/PbCO
3
to hp cht khng hot ng quang hc C (C
8
H
14
).
1. Lp lun xc nh cu to (c lu cu hnh) v gi tn A, B, C.
2. Oxi ha mnh lit A bng dung dch KMnO
4
trong H
2
SO
4
.Vit phng trnh ho hc.
P N IM
1. (a) T l sn phm:
0,50
10
TUY N 5 HSG THNH PH N NG HO H C 11
CH
3
CH CH
3
+ Cl
2
- HCl
CH
3
CH CH
2
Cl
CH
3
C CH
3
Cl
1-clo-2-metylpropan
2-clo-2-metylpropan
CH
3
CH
3
CH
3
(9x1,0)
(9x1,0) + (1x5,0)
= 64,3%
(1x5,0)
(9x1,0) + (1x5,0)
= 35,7%
CH
3
CH CH
3
+ Br
2
- HCl
CH
3
CH CH
2
Br
CH
3
C CH
3
Br
1-brom-2-metylpropan
2-brom-2-metylpropan
CH
3
CH
3
CH
3
(9x1,0)
(9x1,0) + (1x1600)
= 0,56%
(1x1600)
(9x1,0) + (1x1600)
= 99,44%
0,50
(b) Hm lng sn phm halogen ha ph thuc ba yu t:
Kh nng tham gia phn ng th ca ankan: Phn ng halogen ha u tin th
hidro trn nguyn t cacbon bc cao hn.
Kh nng phn ng ca halogen: Brom tham gia phn ng yu hn so vi clo,
nhng c kh nng chn lc v tr th cao hn so vi clo.
S nguyn t hidro trn cacbon cng bc: Khi s hidro trn cc nguyn t cacbon
cng nhiu th hm lng sn phm cng ln.
0,75
2. C ch:
H
+
-H
+
0,75
3. (a) A c bt bo ha 3
2
12 8 . 2 2

+
, B c 0
2
18 8 . 2 2

+
v C c
2
2
14 8 . 2 2

+
.
V A cng 3 phn t hidro to ra B nn A c cc lin kt bi hoc vng ba
cnh.
A cng 1 phn t H
2
to ra C v A khng tc dng vi Ag(NH
3
)
2
+
nn A c mt
lin kt ba dng -C C-R.
A cng phi cha mt lin kt i dng cis- (Z) v tr i xng vi lin kt ba,
v khi A cng 1 phn t H
2
(xc tc Pd lm cho phn ng chy theo kiu cis-) to
C khng hot ng quang hc.
0,50
11
TUY N 5 HSG THNH PH N NG HO H C 11
Cu to ca A, B, C l:
CH
3
C C
H H
H
C
CH
3
C
*
C CH
3
2Z-4-metylhept-2-en-5-in (A)
CH
3
CH
2
CH
2
CH(CH
3
)CH
2
CH
2
CH
3
4-metylheptan (B)
CH
3
C C
H H
H
C
CH
3
C C CH
3
2Z,5Z-4-metylhepta-2,5-dien (C)
H H
0,75
(b) Phng trnh phn ng:
5CH
3
CH=CHCH(CH
3
)C C-CH
3
+ 14KMnO
4
+ 21H
2
SO
4

10CH
3
COOH + 5CH
3
CH(COOH)
2
+ 14MnSO
4
+ 7K
2
SO
4
+ 16H
2
O
0,25
Cu X(4 im)
1. Limonen (C
10
H
16
) l tecpen c trong v qu cam, chanh v bi. Oxi ha limonen bng
kalipemanganat to cht A.
CH
3
C
O
CH
2
CH
2
CH
CH
2
COOH
C O
H
3
C
(A)
(a) Dng d kin trn v qui tc isopren xc nh cu trc ca limonen.
(b) Vit cng thc cc sn phm chnh hnh thnh khi hidrat ha limonen.
2. iu ch nitrobenzen trong phng th nghim v tnh hiu sut phn ng, ngi ta tin
hnh cc bc sau:
Cho 19,5 ml axit nitric vo mt bnh cu y trn c 200 mL lm lnh bnh v lc, sau
thm t t 15 mL H
2
SO
4
m c, ng thi lc v lm lnh n nhit phng. Lp ng
sinh hn hi lu (nc hay khng kh), cho tip 13,5 mL benzen qua ng sinh hn vi tc
chm v gi nhit khng qu 50
0
C, ng thi lc lin tc (a).
Sau khi cho ht benzen, tip tc un nng bnh phn ng trn bp cch thu trong 30-45 pht
v tip tc lc. Sau lm lnh hn hp phn ng v qua phu chit. Tch ly lp
nitrobenzen trn. Ra nitrobenzen bng nc ri bng dung dch Na
2
CO
3
(b). Tch ly
nitrobenzen cho vo bnh lm kh c cha cht lm kh A th rn (c). Chng ct ly
nitrobenzen bng bnh Vuy-c trn bp cch thu thu ly nitrobenzen sch. Cn lng
nitrobenzen thy c 15 gam (d).
(a) Vit phng trnh ho hc chnh v cc phng trnh th hin c ch ca phn ng. Cho
bit v sao cn phi lc bnh lin tc v gi nhit phn ng 50
0
C? Nu khng dng
H
2
SO
4
m c, phn ng c xy ra khng?
(b) V sao cn phi ra nitrobenzen bng nc, sau bng dung dch Na
2
CO
3
?
(c) A c th l cht no?
(d) Tnh hiu sut phn ng nu khi lng ring ca benzen 0,8g/mL.
P N IM
a. (a) Cu to:
0,75
12
TUY N 5 HSG THNH PH N NG HO H C 11
O + O=C=O
O
O
OH
limonen
(b) Cc sn phm chnh khi hidrat ha:
OH
OH OH
OH
0,75
4. (a) Phn ng:
C
6
H
6
+ HONO
2


4 2
SO H
C
6
H
5
NO
2
+ H
2
O (1)
C ch phn ng:
HO - NO
2
+ H
2
SO
4
H - O - NO
2
+ HSO
4
H
(+)
(-)
H - O - NO
2
+ H
2
SO
4
H
(+)
H
3
O
(+)
+ HSO
4
(-)

+ NO
2
(+)
+ NO
2
(+)
H NO
2
+
NO
2
+ H
(+)
chm nhanh
0,75
Hn hp phn ng h d th nn cn phi lc u hay khuy mnh lin tc
to thnh nh tng, bo m s tip xc tt gia cc tc nhn.
Phi gi 50
0
C v nu nhit cao hn s tng lng sn phm
initrobenzen.
Nu khng dng H
2
SO
4
, phn ng vn xy ra do vn c s hnh thnh NO
2
+
theo phng trnh sau:
HO-NO
2
+ HNO
3
H
2
O
+
-NO
2
+ NO
3
-

H
2
O
+
-NO
2
+ HNO
3
H
3
O
+

+ NO
3
-
+ NO
2
+
(1)
Tuy nhin khi khng c H
2
SO
4
phn ng xy ra chm v hiu sut to NO
2
+
sinh ra trong (1) rt thp. Khi c mt H
2
SO
4
m c, cn bng chuyn di v
pha thun nn phn ng xy ra nhanh hn.
0,75
(c) Cn phi ra bng nc loi axit, sau ra bng dung dch Na
2
CO
3
loi
ht axit d v d kim tra kt qu do phn ng gia axit v Na
2
CO
3
sinh kh.
0,25
(b) A l cht ht nc dng rn, nn A c th l CaCl
2
, ... khan 0,25
(d) Hiu sut phn ng:
0,50
13
TUY N 5 HSG THNH PH N NG HO H C 11
gam 512 , 9
123
78 15
m
) 1 ( H C
6 6


% 88
mL / g 8 , 0 mL 5 , 13
g 512 , 9
H

Cu XI
A l hidrocacbon khng lm mt mu dung dch brom. t chy hon ton 0,02 mol A v hp thu
sn phm chy vo dung dch cha 0,15 mol Ca(OH)
2
thu c kt ta v khi lng bnh tng
ln 11,32 gam. Cho dung dch Ba(OH)
2
d vo dung dch thu c kt ta li tng ln, tng khi
lng kt tu hai ln l 24,85 gam. A khng vi dung dch KMnO
4
/H
2
SO
4
nng, cn khi monoclo
ha trong iu kin chiu sng th ch to mt sn phm duy nht.
1. Xc nh cng thc cu to v gi tn A.
2. Ngi ta c th iu ch A t phn ng gia benzen v anken tng ng trong axit sunfuric.
Dng c ch phn ng gii thch phn ng ny.
3. Mononitro ha A bng cch cho phn ng vi axit nitric (c mt axit sunfuric c) th sn
phm chnh thu c l g? Ti sao?
P N IM
1. Dung dch Ca(OH)
2
hp th ht sn phm chy ca A cha CO
2
v H
2
O
CO
2
+ Ca(OH)
2
CaCO
3
+ H
2
O (1)
2CO
2
+ Ca(OH)
2
Ca(HCO
3
)
2
(2)
Ca(HCO
3
)
2
+ Ba(OH)
2
CaCO
3
+ BaCO
3
+ 2H
2
O (3)
0,50
t s mol CO
2
tham gia cc phn ng (1) v (2) ln lt l x v y, ta c:
mol 1 , 0 y x
85 , 24
2
y
197
2
y
x 100
15 , 0
2
y
x

'

+
,
_

+
+
,
mol 2 , 0 y x n
2
CO
+
T mol 14 , 0
18
44 . 2 , 0 32 , 11
n g 32 , 11 m m m
O H CO O H
2 2 2

+
0,50
t cng thc tng qut ca A l C
x
H
y
:
C
x
H
y
+ (x+y/4)O
2
xCO
2
+ y/2H
2
O
Ta c
14 y , 10 x
14 , 0 . 2
y
2 , 0
x
02 , 0
1

Cng thc phn t ca A l C
10
H
14
( ) 4
0,50
V A khng lm mt mu dung dch brom (cu trc thm), khng tc dng vi
dung dch KMnO
4
/H
2
SO
4
(ch c mt nhm th) v monoclo ha (nh sng) ch to
mt sn phm duy nht (nhm th c cu trc i xng cao) nn cu to ca A l:
C
CH
3
CH
3
CH
3
(t-butylbenzen)
1,00
2. C ch:
(CH
3
)
2
C=CH
2
+ H
2
SO
4
(CH
3
)
2
C
+
-CH
3
+ HSO
4
-
+
C(CH
3
)
3
H
+ H
(+)
chm nhanh
+ (CH
3
)
3
C
+
C(CH
3
)
3
1,00
3. Nhm ankyl ni chung nh hng th vo cc v tr ortho- v para-. Tuy nhin, do
14
TUY N 5 HSG THNH PH N NG HO H C 11
nhm t-butyl c kch thc ln gy n ng khng gian nn sn phm chnh l sn
phm para-:
C
CH
3
CH
3
CH
3
O
2
N
0,50
S GIO DC V O TO HNG DN CHM THI HC SINH GII THNH PH
15
TUY N 5 HSG THNH PH N NG HO H C 11
THNH PH NNG MN: HA HC LP 11
Thi gian: 150 pht (khng k thi gian giao )
CHNH THC
ny c hai (2) trang
Cu XII (4 im)
1. Tnh pH ca dung dch thu c khi trn ln 50,0 mL dung dch NH
4
Cl 0,200 M vi 75,0 mL
dung dch NaOH 0,100 M. Bit K
b
(NH
3
) = 1,8.10
-5
.
2. Phn l mui sunfat kp ca mt cation ha tr mt (nh K
+
hay NH
4
+
) v mt cation ha tr
ba (nh Al
3+
, Fe
3+
hay Cr
3+
). Phn st amoni c cng thc (NH
4
)
a
Fe(SO
4
)
b
.nH
2
O. Ha tan 1,00
gam mu phn st vo 100 cm
3
H
2
O, ri chia dung dch thu c thnh hai phn bng nhau.
Thm dung dch NaOH d vo phn mt v un si dung dch. Lng NH
3
thot ra phn ng
va vi 10,37 cm
3
dung dch HCl 0,100 M. Dng km kim loi kh ht Fe
3+
phn hai
thnh Fe
2+
. oxi ha ion Fe
2+
thnh ion Fe
3+
tr li, cn 20,74 cm
3
dung dch KMnO
4
0,0100
M trong mi trng axit.
(a) Vit cc phng trnh phn ng dng ion thu gn v xc nh cc gi tr a, b, n.
(b) Ti sao cc phn khi tan trong nc u to mi trng axit ?
P N IM
1. M 08 , 0
L 125 , 0
L . mol 200 , 0 L 050 , 0
C
1
o
Cl NH
4

; M 06 , 0
L 125 , 0
L . mol 100 , 0 L 075 , 0
C
1
o
NaOH

NH
4
Cl + NaOH NaCl + NH
3
+ H
2
O
0,08 0,06
0,06 0,06 0,06
0,02 0 0,06
Xt cn bng :
NH
3
+ H
2
O NH
4
+
+ OH
-
0,06 0,02
x x x
0,06x 0,02+x x
5
3
4
b
10 . 8 , 1
x 06 , 0
x ) x 02 , 0 (
] NH [
] OH ][ NH [
K

+

+

, gn ng
M 10 . 4 , 5
02 , 0
06 , 0
10 . 8 , 1 x
5 5

73 , 9 )] 10 . 4 , 5 lg( [ 14 pH
5


0,50
1,00
2. (a) t s mol ca phn st (NH
4
)
a
Fe(SO
4
)
b
.nH
2
O trong mi phn l x mol.
Phng trnh phn ng phn mt :
NH
4
+
+ OH
-
NH
3
+ H
2
O
ax
0 ax
Fe
3+
+ 3OH
-
Fe(OH)
3
NH
3
+ H
+
NH
4
+
ax ax
Phng trnh phn ng phn hai :
Zn + 2Fe
3+
Zn
2+
+ 2Fe
2+
x
0 x
5Fe
2+
+ MnO
4
-
+ 8H
+
5Fe
3+
+ Mn
2+
+ 4H
2
O
10,25
16
TUY N 5 HSG THNH PH N NG HO H C 11
x x/5
Ta c : mol 10 . 037 , 1 L . mol 100 , 0 L 01037 , 0 ax
3 1

mol 10 . 037 , 1 L . mol 010 , 0 L 02074 , 0 5 x
3 1

a = 1
Cng thc ca phn c vit li l NH
4
+
Fe
3+
(SO
4
2-
)
b
.nH
2
O
b = 2
T M = 18 + 56 + 96.2 + 18n =
mol 10 . 037 , 1
gam 5 , 0
3

n = 12
Cng thc ca phn st amoni l NH
4
Fe(SO
4
)
2
.12H
2
O
(b) Phn tan trong nc to mi trng axit v cc ion NH
4
+
, Al
3+
, Fe
3+
v Cr
3+
u nhng ion axit (cc ion K
+
c tnh trung tnh, cn SO
4
2-
c tnh baz rt yu).
NH
4
+
+ H
2
O NH
3
+ H
3
O
+
M
3+
+ H
2
O M(OH)
2+
+ H
+

Cu XIII (4 im)
1. Vit phng trnh phn ng xy ra khi ln lt cho cc n cht As v Bi tc dng vi dung
dch HNO
3
(gi thit sn phm kh ch l kh NO).
2. So snh (c gii thch) tnh tan trong nc, tnh baz v tnh kh ca hai hp cht vi hidro l
amoniac (NH
3
) v photphin (PH
3
).
3. Mt giai on quan trng trong qu trnh tng hp axit nitric l oxi ha NH
3
trong khng kh,
c mt Pt xc tc.
(a) Xc nh nhit phn ng ca phn ng ny, bit nhit hnh thnh cc cht NH
3
(k), NO
(k) v H
2
O (k) ln lt bng 46 kJ/mol; + 90 kJ/mol v - 242 kJ/mol.
(b) Trong cng nghip, ngi ta s dng nhit v p sut th no qu trnh ny l ti
u ? Ti sao ?
P N IM
1. Phng trnh phn ng :
3As + 5HNO
3
+ 2H
2
O 3H
3
AsO
4
+ 5NO
Bi + 4HNO
3
Bi(NO
3
)
3
+ NO + 2H
2
O
1,00
2. Tnh tan :
NH
3
tan tt hn PH
3
trong nc, do phn t phn cc hn v c kh nng to lin
kt hidro vi nc.
H N
H
H
H O
H
H N
H
H
... ... ... ...
Tnh baz :
NH
3
c tnh baz mnh hn PH
3
, do lin kt N-H phn cc mnh hn lin kt P-
H, lm cho nguyn t N trong phn t NH
3
giu electron hn, d dng nhn
proton hn (mt nguyn nhn na gii thch cho iu ny l ion NH
4
+
bn hn
PH
4
+
).
Tnh kh :
PH
3
c tnh kh mnh hn nhiu so vi NH
3
, do nguyn t P l mt phi kim c
17
TUY N 5 HSG THNH PH N NG HO H C 11
m in nh v phn t PH
3
km bn hn NH
3
.
3. (a) 4NH
3
(k) + 5O
2
(k) 4NO (k) + 6H
2
O (k)
+
3 2
NH O H NO
H 4 H 6 H 4 H
kJ 908 ) kJ 46 ( 4 [ )] kJ 242 ( 6 [ ) kJ 90 4 ( H +
(b) V phn ng l ta nhit, nn tng hiu sut cn gim nhit . Tuy nhin
nu h nhit qu thp s lm gim tc phn ng, nn thc t phn ng ny
c tin hnh 850-900
o
C v c xc tc Pt. V phn ng thun l chiu lm
tng s phn t kh, nn tng hiu sut phn ng cn gim p sut. Tuy nhin,
iu kin p sut gy tng gi thnh cng ngh sn xut, nn ta ch dng p sut
thng (1 atm).
Cu XIV (4 im)
1. Dng hnh v, m t th nghim c tin hnh trong phng th nghim xc nh s c mt
ca cc nguyn t C v H c trong glucoz.
2. Hon thnh cc phn ng di y. Xc nh sn phm chnh ca mi phn ng v dng c
ch gii thch s hnh thnh sn phm chnh .
(a) CH
3
-CH=CH
2
(propilen) + HCl
(b) CH
3
-CH
2
-CH(OH)-CH
3
(ancol s-butylic)

C 180 , SO H
o
4 2
(c) C
6
H
5
CH
3
+ HNO
3


o
4 2
t , SO H
3. Dng s xen ph obitan nguyn t m t cc phn t CH
3
-CH=C=CH-CH
3
(phn t A)
v CH
3
-CH=C=C=CH-CH
3
(phn t B). Cho bit A, B c ng phn hnh hc hay khng ?
Ti sao ?
P N IM
1. Th nghim xc nh s c mt ca cc nguyn t C v H c trong glucoz :
1,5
2. Phn ng v c ch phn ng:
(a) Phn ng :
CH
3
CH CH
2
+ HCl
CH CH
3
CH
3
Cl
CH
2
CH
3
CH
2
Cl
(sn phm chnh)
C ch (cng A
E
) :
0,50
18
TUY N 5 HSG THNH PH N NG HO H C 11
CH
3
CH CH
2
H
+

CH
3
CH CH
3
CH
3
CH
2
CH
2
Cl
-
CH CH
3
CH
3
Cl
(X)
(Y)
Sn phm chnh hnh thnh theo hng to cacbocation trung gian bn vng hn.
D thy rng cacbocation (X) bn hn (Y) (do in tch c gii ta nhiu hn,
vi 6H

), nn sn phm chnh l isopropyl clorua.


(b) Phn ng :
CH
3
CH
2
H
2
SO
4
(sn phm chnh)
CH CH
3
OH
CH
3
CH CH CH
3
+ H
2
O
CH
2
CH CH
2
CH
3
+ H
2
O
C ch (tch E1) :
CH
3
CH
2
CH CH
3
OH
CH
3
CH CH CH
3
CH
2
CH CH
2
CH
3
H
+
CH
3
CH
2
CH CH
3
+
OH
2
-H
2
O
(X)
(Y)
Sn phm chnh c hnh thnh theo hng to sn phm bn hn. y, (X)
bn hn (Y) do c s nguyn t H

tham gia lin hp, lm bn ha lin kt


nhiu hn.
0,50
(c) Phn ng :
+ HONO
2
H
2
SO
4
+ H
2
O
CH
3
CH
3
NO
2
+ H
2
O
CH
3
NO
2
C ch (th S
E
2Ar) : HONO
2
+ H
2
SO
4
HSO
4
-
+ H
2
O +
+
NO
2

+
NO
2
+
NO
2
-H
+
CH
3
CH
3
CH
3
CH
3
-H
+
CH
3
CH
3
H
NO
2
H
NO
2
NO
2
NO
2
Phn ng dnh hng th vo v tr meta-, do mt electron v tr ny trong
phn t toluen giu hn cc v tr ortho-, para-. ng thi phn ng th vo v tr
ny to s gii ta in tch tt nht phc .
0,50
3. M hnh phn t :
19
TUY N 5 HSG THNH PH N NG HO H C 11
H
CH
3
H
CH
3
Trong trung hp ny, cc nhm th khng ng phng, nn phn t khng xut hin
hin tng ng phn hnh hc.
H
CH
3
H
CH
3
Trong trng hp ny, cc nhm th ng phng, nn phn t xut hin hin tng
ng phn hnh hc.
1,00
Cu XV (4 im)
1. Thi 672 mL (ktc) hn hp kh A gm mt ankan, mt anken v mt ankin (u c s
nguyn t cacbon trong phn t bng nhau) qua dung dch AgNO
3
/NH
3
, th thy c 3,4
AgNO
3
tham gia phn ng. Cng lng hn hp kh A trn lm mt mu va ht 200 mL
dung dch Br
2
0,15 M.
(a) Xc nh thnh phn nh tnh v nh lng cc cht trong A
(b) ngh phng php tch ring tng cht ra khi hn hp A.
2. Oxi ha m gam hp cht hu c A bng CuO ri cho sn phm sinh ra gm CO
2
v hi H
2
O
ln lt i qua bnh 1 ng Mg(ClO
4
)
2
v bnh 2 ng 2 lt Ca(OH)
2
0,0 2 M th thu c 2
gam kt ta. Khi lng bnh 1 tng 1,08 gam v khi lng CuO gim 3,2 gam, M
A
< 100.
Oxi ha mnh lit A, thu c hai hp cht hu c l CH
3
COOH v CH
3
COCOOH.
(a) Xc nh cng thc cu to v gi tn A.
(b) Vit cc dng ng phn hnh hc tng ng ca A.
(c) Khi cho A tc dng vi Br
2
theo t l mol 1:1, th to c nhng sn phm no ? Gii
thch.
P N I
M
1. (a) Nu ankin c dng RC CH :
RC CH + AgNO
3
+ NH
3
RC CAg + NH
4
NO
3

mol 02 , 0
mol / gam 170
gam 4 , 3
) ankin ( n
v
mol 04 , 0 ) ankin ( n 2 n
2
Br

iu ny tri gi thit, v s mol Br
2
ch bng
mol 03 , 0 L / mol 15 , 0 L 2 , 0
Vy ankin phi l C
2
H
2
v nh vy ankan l C
2
H
6
, anken l C
2
H
4
.
T phn ng :
C
2
H
2
+ 2AgNO
3
+ 2NH
3
C
2
Ag
2
+ 2NH
4
NO
3
n(C
2
H
2
) = 1/2n(AgNO
3
) = 0,01 mol
T cc phn ng :
C
2
H
2
+ 2Br
2
C
2
H
2
Br
4
C
2
H
4
+ Br
2
C
2
H
4
Br
2
n(C
2
H
4
)

= 0,01 mol
n(C
2
H
6
) =
mol 01 , 0 mol 01 , 0
mol / L 4 , 22
L 672 , 0
0,01 mol
0,50
(b) Thi hn hp qua binh cha dung dch AgNO
3
/NH
3
d. Lc tch kt ta, ha tan
kt ta trong dung dch HCl d thu c kh C
2
H
2
.
C
2
H
2
+ 2AgNO
3
+ 2NH
3
C
2
Ag
2
+ 2NH
4
NO
3
20
TUY N 5 HSG THNH PH N NG HO H C 11
C
2
Ag
2
+ 2HCl C
2
H
2
+ 2AgCl
Kh ra khi bnh cha dung dch AgNO
3
/NH
3
, thi tip qua dung dch nc brom d.
Chit ly sn phm v un nng vi bt Zn (trong CH
3
COOH) thu c C
2
H
4
:
C
2
H
4
+ Br
2
C
2
H
4
Br
2
C
2
H
4
Br
2
+ Zn C
2
H
4
+ ZnBr
2
Kh ra khi bnh cha dung dch brom l kh C
2
H
6
1,00
2. (a) n(H
2
O) = 0,06 mol n(H) = 0,12 mol
T cc phn ng :
CO
2
+ Ca(OH)
2
CaCO
3
+ H
2
O
2CO
2
+ Ca(OH)
2
Ca(HCO
3
)
2
vi
mol 045 , 0 n
2
) OH ( Ca

v
mol 02 , 0 n
3
CaCO

n(CO
2
) bng 0,02 mol hoc 0,07 mol.
n(O) tham gia phn ng bng
mol 2 , 0
mol / gam 16
gam 2 , 3

Vy s mol O trong A bng :


n(O) = 0,02mol 2 + 0,06 mol 0,2 mol < 0 (loi)
n(O) = 0,07mol 2 + 0,06 mol 0,2 mol = 0 mol
A l hidrocacbon c cng thc n gin C
7
H
12
V M
A
< 100, nn cng thc phn t ca A chnh l C
7
H
12
( 2 )
Cu to ca A ph hp vi gi thit l:
CH CH
3
C
CH
3
CH CH CH
3
(3-metylhexa-2,4-dien)
1,00
0,50
(b) Cc dng ng phn hnh hc :
CH
3
C C
CH
3
C C
CH
3
H H
H
H
3
C
C C
CH
3
C C
H
CH
3
H
H
H
C C
CH
3
C C
CH
3
H H
CH
3
H
C C
CH
3
C C
H
CH
3
H
CH
3
cis-cis cis-trans trans-cis trans-trans
0,50
(c) Tc dng vi brom theo t l mol 1:1 th to c cc sn phm :
CH CH
3
C
CH
3
CH CH CH
3
+ Br
2
- Br
-
CH CH
3
C
CH
3
H
C CHBr CH
3
H
C CH
3
C
CH
3
CH CHBr
H
C CH
3
C
CH
3
CH CH CH
3
CH
3
Br
+ Br
-
CH
3
CH=C(CH
3
)-CHBr-CHBr-CH
3
CH
3
-CHBr-C(CH
3
)=CH-CHBr-CH
3
CH
3
-CHBr-CBr(CH
3
)-CH=CH-CH
3
0,50
21
TUY N 5 HSG THNH PH N NG HO H C 11
Cu XVI ( 4 im)
1. Trnh by phng php phn bit mi cp cht di y (mi trng hp ch dng mt thuc
th n gin, c vit phn ng minh ha) :
(a) m-bromtoluen v benzylbromua
(b) phenylaxetilen v styren
2. T benzen v cc cht v c, xc tc cn thit khc c , vit cc phng trnh phn ng ha
hc iu ch :
(a) meta-clonitrobenzen
(b) ortho-clonitrobenzen
(c) axit meta-brombenzoic
(d) axit ortho-brombenzoic
3. Hidrocacbon X c phn t khi bng 128, khng lm nht mu dung dch Br
2
. X tc dng vi
H
2
(xc tc Ni, t) to cc sn phm Y v Z. Oxi ha mnh lit Y to sn phm l axit o-
phtalic, o-C
6
H
4
(COOH)
2
.
(a) Xc nh cu to v gi tn X, Y, Z.
(b) Vit phn ng to ra sn phm chnh, khi cho X ln lt tc dng vi dung dch HNO
3
c (H
2
SO
4
c xc tc) v Br
2
(xc tc bt st). Bit mi phn ng, t l mol cc cht
tham gia phn ng l 1:1.
P N I
M
1. Phn bit cc cht :
(a) Dng AgNO
3
, benzyl bromua cho kt ta vng :
C
6
H
5
CH
2
Br + AgNO
3
+ H
2
O C
6
H
5
CH
2
OH + AgBr + HNO
3
(b) Dng dung dch AgNO
3
/NH
3
, phenylaxetilen cho kt ta vng xm :
C
6
H
5
C CH + AgNO
3
+ NH
3
C
6
H
5
C CAg + NH
4
NO
3
1,00
2. iu ch :
NO
2
+ HONO
2
H
2
SO
4
+ Cl
2
Fe
NO
2
Cl
(a)
Cl
+ HONO
2
H
2
SO
4
+ Cl
2
Fe
Cl
(b)
+H
2
SO
4
SO
3
H
Cl
SO
3
H
t
Cl
NO
2
NO
2
CH
3
+ CH
3
Cl
AlCl
3
+ Br
2
Fe
COOH
(c)
+ KMnO
4
COOH
Br
0,25
0,50
0,25
22
TUY N 5 HSG THNH PH N NG HO H C 11
CH
3
+ Br
2
Fe
+CH
3
Cl
AlCl
3
CH
3
(d)
+H
2
SO
4
SO
3
H
CH
3
SO
3
H
t
CH
3
Br
Br
+ KMnO
4
COOH
Br
0,50
3. (a) X (C
x
H
y
), c 12x + y = 128 (y 2x + 2) c hai nghim thch hp l C
10
H
8
v
C
9
H
20
. Tuy nhin, v X tc dng c vi hidro, nn cng thc ng l C
10
H
8
(
7 ).
V X khng lm nht mu nc brom nn cu to thch hp ca X l naphtalen v
ph hp vi gi thit th Y l tetralin v Z l decalin :
(naphtalen)
(tetralin) (decalin)
1,00
(b) Phn ng :
+ HONO
2
H
2
SO
4
+ H
2
O
NO
2
+ Br
2
Fe
+ HBr
Fe
0,50
23
TUY N 5 HSG THNH PH N NG HO H C 11
S GIO DC V O TO
THNH PH NNG
HNG DN CHM THI HC SINH GII THNH PH
MN: HA HC LP 11
Thi gian: 150 pht (khng k thi gian giao )
CHNH THC
ny c hai (2) trang
Cu XVII (4 im)
3. Tnh pH ca dung dch thu c khi trn ln 50,0 mL dung dch NH
4
Cl 0,200 M vi 75,0 mL
dung dch NaOH 0,100 M. Bit K
b
(NH
3
) = 1,8.10
-5
.
4. Phn l mui sunfat kp ca mt cation ha tr mt (nh K
+
hay NH
4
+
) v mt cation ha tr
ba (nh Al
3+
, Fe
3+
hay Cr
3+
). Phn st amoni c cng thc (NH
4
)
a
Fe(SO
4
)
b
.nH
2
O. Ha tan 1,00
gam mu phn st vo 100 cm
3
H
2
O, ri chia dung dch thu c thnh hai phn bng nhau.
Thm dung dch NaOH d vo phn mt v un si dung dch. Lng NH
3
thot ra phn ng
va vi 10,37 cm
3
dung dch HCl 0,100 M. Dng km kim loi kh ht Fe
3+
phn hai
thnh Fe
2+
. oxi ha ion Fe
2+
thnh ion Fe
3+
tr li, cn 20,74 cm
3
dung dch KMnO
4
0,0100
M trong mi trng axit.
(a) Vit cc phng trnh phn ng dng ion thu gn v xc nh cc gi tr a, b, n.
(b) Ti sao cc phn khi tan trong nc u to mi trng axit ?
P N IM
1. M 08 , 0
L 125 , 0
L . mol 200 , 0 L 050 , 0
C
1
o
Cl NH
4

; M 06 , 0
L 125 , 0
L . mol 100 , 0 L 075 , 0
C
1
o
NaOH

NH
4
Cl + NaOH NaCl + NH
3
+ H
2
O
0,08 0,06
0,06 0,06 0,06
0,02 0 0,06
Xt cn bng :
NH
3
+ H
2
O NH
4
+
+ OH
-
0,06 0,02
x x x
0,06x 0,02+x x
5
3
4
b
10 . 8 , 1
x 06 , 0
x ) x 02 , 0 (
] NH [
] OH ][ NH [
K

+

+

, gn ng
M 10 . 4 , 5
02 , 0
06 , 0
10 . 8 , 1 x
5 5

73 , 9 )] 10 . 4 , 5 lg( [ 14 pH
5


0,50
1,00
2. (a) t s mol ca phn st (NH
4
)
a
Fe(SO
4
)
b
.nH
2
O trong mi phn l x mol.
Phng trnh phn ng phn mt :
NH
4
+
+ OH
-
NH
3
+ H
2
O
ax
1 ax
Fe
3+
+ 3OH
-
Fe(OH)
3
NH
3
+ H
+
NH
4
+
ax ax
Phng trnh phn ng phn hai :
Zn + 2Fe
3+
Zn
2+
+ 2Fe
2+
x
0 x
10,25
24
TUY N 5 HSG THNH PH N NG HO H C 11
5Fe
2+
+ MnO
4
-
+ 8H
+
5Fe
3+
+ Mn
2+
+ 4H
2
O
x x/5
Ta c : mol 10 . 037 , 1 L . mol 100 , 0 L 01037 , 0 ax
3 1

mol 10 . 037 , 1 L . mol 010 , 0 L 02074 , 0 5 x
3 1

a = 1
Cng thc ca phn c vit li l NH
4
+
Fe
3+
(SO
4
2-
)
b
.nH
2
O
b = 2
T M = 18 + 56 + 96.2 + 18n =
mol 10 . 037 , 1
gam 5 , 0
3

n = 12
Cng thc ca phn st amoni l NH
4
Fe(SO
4
)
2
.12H
2
O
(b) Phn tan trong nc to mi trng axit v cc ion NH
4
+
, Al
3+
, Fe
3+
v Cr
3+
u nhng ion axit (cc ion K
+
c tnh trung tnh, cn SO
4
2-
c tnh baz rt yu).
NH
4
+
+ H
2
O NH
3
+ H
3
O
+
M
3+
+ H
2
O M(OH)
2+
+ H
+

Cu XVIII (4 im)
4. Vit phng trnh phn ng xy ra khi ln lt cho cc n cht As v Bi tc dng vi dung
dch HNO
3
(gi thit sn phm kh ch l kh NO).
5. So snh (c gii thch) tnh tan trong nc, tnh baz v tnh kh ca hai hp cht vi hidro l
amoniac (NH
3
) v photphin (PH
3
).
6. Mt giai on quan trng trong qu trnh tng hp axit nitric l oxi ha NH
3
trong khng kh,
c mt Pt xc tc.
(a) Xc nh nhit phn ng ca phn ng ny, bit nhit hnh thnh cc cht NH
3
(k), NO
(k) v H
2
O (k) ln lt bng 46 kJ/mol; + 90 kJ/mol v - 242 kJ/mol.
(b) Trong cng nghip, ngi ta s dng nhit v p sut th no qu trnh ny l ti
u ? Ti sao ?
P N IM
1. Phng trnh phn ng :
3As + 5HNO
3
+ 2H
2
O 3H
3
AsO
4
+ 5NO
Bi + 4HNO
3
Bi(NO
3
)
3
+ NO + 2H
2
O
1,00
2. Tnh tan :
NH
3
tan tt hn PH
3
trong nc, do phn t phn cc hn v c kh nng to lin
kt hidro vi nc.
H N
H
H
H O
H
H N
H
H
... ... ... ...
Tnh baz :
NH
3
c tnh baz mnh hn PH
3
, do lin kt N-H phn cc mnh hn lin kt P-
H, lm cho nguyn t N trong phn t NH
3
giu electron hn, d dng nhn
proton hn (mt nguyn nhn na gii thch cho iu ny l ion NH
4
+
bn hn
PH
4
+
).
Tnh kh :
25
TUY N 5 HSG THNH PH N NG HO H C 11
PH
3
c tnh kh mnh hn nhiu so vi NH
3
, do nguyn t P l mt phi kim c
m in nh v phn t PH
3
km bn hn NH
3
.
3. (a) 4NH
3
(k) + 5O
2
(k) 4NO (k) + 6H
2
O (k)
+
3 2
NH O H NO
H 4 H 6 H 4 H
kJ 908 ) kJ 46 ( 4 [ )] kJ 242 ( 6 [ ) kJ 90 4 ( H +
(b) V phn ng l ta nhit, nn tng hiu sut cn gim nhit . Tuy nhin
nu h nhit qu thp s lm gim tc phn ng, nn thc t phn ng ny
c tin hnh 850-900
o
C v c xc tc Pt. V phn ng thun l chiu lm
tng s phn t kh, nn tng hiu sut phn ng cn gim p sut. Tuy nhin,
iu kin p sut gy tng gi thnh cng ngh sn xut, nn ta ch dng p sut
thng (1 atm).
Cu XIX (4 im)
4. Dng hnh v, m t th nghim c tin hnh trong phng th nghim xc nh s c mt
ca cc nguyn t C v H c trong glucoz.
5. Hon thnh cc phn ng di y. Xc nh sn phm chnh ca mi phn ng v dng c
ch gii thch s hnh thnh sn phm chnh .
(a) CH
3
-CH=CH
2
(propilen) + HCl
(b) CH
3
-CH
2
-CH(OH)-CH
3
(ancol s-butylic)

C 180 , SO H
o
4 2
(c) C
6
H
5
CH
3
+ HNO
3


o
4 2
t , SO H
6. Dng s xen ph obitan nguyn t m t cc phn t CH
3
-CH=C=CH-CH
3
(phn t A)
v CH
3
-CH=C=C=CH-CH
3
(phn t B). Cho bit A, B c ng phn hnh hc hay khng ?
Ti sao ?
P N IM
4. Th nghim xc nh s c mt ca cc nguyn t C v H c trong glucoz :
1,5
5. Phn ng v c ch phn ng:
(a) Phn ng :
CH
3
CH CH
2
+ HCl
CH CH
3
CH
3
Cl
CH
2
CH
3
CH
2
Cl
(sn phm chnh)
C ch (cng A
E
) :
0,50
26
TUY N 5 HSG THNH PH N NG HO H C 11
CH
3
CH CH
2
H
+

CH
3
CH CH
3
CH
3
CH
2
CH
2
Cl
-
CH CH
3
CH
3
Cl
(X)
(Y)
Sn phm chnh hnh thnh theo hng to cacbocation trung gian bn vng hn.
D thy rng cacbocation (X) bn hn (Y) (do in tch c gii ta nhiu hn,
vi 6H

), nn sn phm chnh l isopropyl clorua.


(b) Phn ng :
CH
3
CH
2
H
2
SO
4
(sn phm chnh)
CH CH
3
OH
CH
3
CH CH CH
3
+ H
2
O
CH
2
CH CH
2
CH
3
+ H
2
O
C ch (tch E1) :
CH
3
CH
2
CH CH
3
OH
CH
3
CH CH CH
3
CH
2
CH CH
2
CH
3
H
+
CH
3
CH
2
CH CH
3
+
OH
2
-H
2
O
(X)
(Y)
Sn phm chnh c hnh thnh theo hng to sn phm bn hn. y, (X)
bn hn (Y) do c s nguyn t H

tham gia lin hp, lm bn ha lin kt


nhiu hn.
0,50
(c) Phn ng :
+ HONO
2
H
2
SO
4
+ H
2
O
CH
3
CH
3
NO
2
+ H
2
O
CH
3
NO
2
C ch (th S
E
2Ar) : HONO
2
+ H
2
SO
4
HSO
4
-
+ H
2
O +
+
NO
2

+
NO
2
+
NO
2
-H
+
CH
3
CH
3
CH
3
CH
3
-H
+
CH
3
CH
3
H
NO
2
H
NO
2
NO
2
NO
2
Phn ng dnh hng th vo v tr meta-, do mt electron v tr ny trong
phn t toluen giu hn cc v tr ortho-, para-. ng thi phn ng th vo v tr
ny to s gii ta in tch tt nht phc .
0,50
6. M hnh phn t :
27
TUY N 5 HSG THNH PH N NG HO H C 11
H
CH
3
H
CH
3
Trong trung hp ny, cc nhm th khng ng phng, nn phn t khng xut hin
hin tng ng phn hnh hc.
H
CH
3
H
CH
3
Trong trng hp ny, cc nhm th ng phng, nn phn t xut hin hin tng
ng phn hnh hc.
1,00
Cu XX (4 im)
3. Thi 672 mL (ktc) hn hp kh A gm mt ankan, mt anken v mt ankin (u c s
nguyn t cacbon trong phn t bng nhau) qua dung dch AgNO
3
/NH
3
, th thy c 3,4
AgNO
3
tham gia phn ng. Cng lng hn hp kh A trn lm mt mu va ht 200 mL
dung dch Br
2
0,15 M.
(c) Xc nh thnh phn nh tnh v nh lng cc cht trong A
(d) ngh phng php tch ring tng cht ra khi hn hp A.
4. Oxi ha m gam hp cht hu c A bng CuO ri cho sn phm sinh ra gm CO
2
v hi H
2
O
ln lt i qua bnh 1 ng Mg(ClO
4
)
2
v bnh 2 ng 2 lt Ca(OH)
2
0,0 2 M th thu c 2
gam kt ta. Khi lng bnh 1 tng 1,08 gam v khi lng CuO gim 3,2 gam, M
A
< 100.
Oxi ha mnh lit A, thu c hai hp cht hu c l CH
3
COOH v CH
3
COCOOH.
(a) Xc nh cng thc cu to v gi tn A.
(b) Vit cc dng ng phn hnh hc tng ng ca A.
(c) Khi cho A tc dng vi Br
2
theo t l mol 1:1, th to c nhng sn phm no ? Gii
thch.
P N I
M
1. (a) Nu ankin c dng RC CH :
RC CH + AgNO
3
+ NH
3
RC CAg + NH
4
NO
3

mol 02 , 0
mol / gam 170
gam 4 , 3
) ankin ( n
v
mol 04 , 0 ) ankin ( n 2 n
2
Br

iu ny tri gi thit, v s mol Br
2
ch bng
mol 03 , 0 L / mol 15 , 0 L 2 , 0
Vy ankin phi l C
2
H
2
v nh vy ankan l C
2
H
6
, anken l C
2
H
4
.
T phn ng :
C
2
H
2
+ 2AgNO
3
+ 2NH
3
C
2
Ag
2
+ 2NH
4
NO
3
n(C
2
H
2
) = 1/2n(AgNO
3
) = 0,01 mol
T cc phn ng :
C
2
H
2
+ 2Br
2
C
2
H
2
Br
4
C
2
H
4
+ Br
2
C
2
H
4
Br
2
n(C
2
H
4
)

= 0,01 mol
n(C
2
H
6
) =
mol 01 , 0 mol 01 , 0
mol / L 4 , 22
L 672 , 0
0,01 mol
0,50
(b) Thi hn hp qua binh cha dung dch AgNO
3
/NH
3
d. Lc tch kt ta, ha tan
kt ta trong dung dch HCl d thu c kh C
2
H
2
.
C
2
H
2
+ 2AgNO
3
+ 2NH
3
C
2
Ag
2
+ 2NH
4
NO
3
28
TUY N 5 HSG THNH PH N NG HO H C 11
C
2
Ag
2
+ 2HCl C
2
H
2
+ 2AgCl
Kh ra khi bnh cha dung dch AgNO
3
/NH
3
, thi tip qua dung dch nc brom d.
Chit ly sn phm v un nng vi bt Zn (trong CH
3
COOH) thu c C
2
H
4
:
C
2
H
4
+ Br
2
C
2
H
4
Br
2
C
2
H
4
Br
2
+ Zn C
2
H
4
+ ZnBr
2
Kh ra khi bnh cha dung dch brom l kh C
2
H
6
1,00
2. (a) n(H
2
O) = 0,06 mol n(H) = 0,12 mol
T cc phn ng :
CO
2
+ Ca(OH)
2
CaCO
3
+ H
2
O
2CO
2
+ Ca(OH)
2
Ca(HCO
3
)
2
vi
mol 045 , 0 n
2
) OH ( Ca

v
mol 02 , 0 n
3
CaCO

n(CO
2
) bng 0,02 mol hoc 0,07 mol.
n(O) tham gia phn ng bng
mol 2 , 0
mol / gam 16
gam 2 , 3

Vy s mol O trong A bng :


n(O) = 0,02mol 2 + 0,06 mol 0,2 mol < 0 (loi)
n(O) = 0,07mol 2 + 0,06 mol 0,2 mol = 0 mol
A l hidrocacbon c cng thc n gin C
7
H
12
V M
A
< 100, nn cng thc phn t ca A chnh l C
7
H
12
( 2 )
Cu to ca A ph hp vi gi thit l:
CH CH
3
C
CH
3
CH CH CH
3
(3-metylhexa-2,4-dien)
1,00
0,50
(b) Cc dng ng phn hnh hc :
CH
3
C C
CH
3
C C
CH
3
H H
H
H
3
C
C C
CH
3
C C
H
CH
3
H
H
H
C C
CH
3
C C
CH
3
H H
CH
3
H
C C
CH
3
C C
H
CH
3
H
CH
3
cis-cis cis-trans trans-cis trans-trans
0,50
(c) Tc dng vi brom theo t l mol 1:1 th to c cc sn phm :
CH CH
3
C
CH
3
CH CH CH
3
+ Br
2
- Br
-
CH CH
3
C
CH
3
H
C CHBr CH
3
H
C CH
3
C
CH
3
CH CHBr
H
C CH
3
C
CH
3
CH CH CH
3
CH
3
Br
+ Br
-
CH
3
CH=C(CH
3
)-CHBr-CHBr-CH
3
CH
3
-CHBr-C(CH
3
)=CH-CHBr-CH
3
CH
3
-CHBr-CBr(CH
3
)-CH=CH-CH
3
0,50
29
TUY N 5 HSG THNH PH N NG HO H C 11
Cu XXI ( 4 im)
4. Trnh by phng php phn bit mi cp cht di y (mi trng hp ch dng mt thuc
th n gin, c vit phn ng minh ha) :
(a) m-bromtoluen v benzylbromua
(b) phenylaxetilen v styren
5. T benzen v cc cht v c, xc tc cn thit khc c , vit cc phng trnh phn ng ha
hc iu ch :
(a) meta-clonitrobenzen
(b) ortho-clonitrobenzen
(c) axit meta-brombenzoic
(d) axit ortho-brombenzoic
6. Hidrocacbon X c phn t khi bng 128, khng lm nht mu dung dch Br
2
. X tc dng vi
H
2
(xc tc Ni, t) to cc sn phm Y v Z. Oxi ha mnh lit Y to sn phm l axit o-
phtalic, o-C
6
H
4
(COOH)
2
.
(a) Xc nh cu to v gi tn X, Y, Z.
(b) Vit phn ng to ra sn phm chnh, khi cho X ln lt tc dng vi dung dch HNO
3
c (H
2
SO
4
c xc tc) v Br
2
(xc tc bt st). Bit mi phn ng, t l mol cc cht
tham gia phn ng l 1:1.
P N I
M
1. Phn bit cc cht :
(a) Dng AgNO
3
, benzyl bromua cho kt ta vng :
C
6
H
5
CH
2
Br + AgNO
3
+ H
2
O C
6
H
5
CH
2
OH + AgBr + HNO
3
(b) Dng dung dch AgNO
3
/NH
3
, phenylaxetilen cho kt ta vng xm :
C
6
H
5
C CH + AgNO
3
+ NH
3
C
6
H
5
C CAg + NH
4
NO
3
1,00
2. iu ch :
NO
2
+ HONO
2
H
2
SO
4
+ Cl
2
Fe
NO
2
Cl
(a)
Cl
+ HONO
2
H
2
SO
4
+ Cl
2
Fe
Cl
(b)
+H
2
SO
4
SO
3
H
Cl
SO
3
H
t
Cl
NO
2
NO
2
CH
3
+ CH
3
Cl
AlCl
3
+ Br
2
Fe
COOH
(c)
+ KMnO
4
COOH
Br
0,25
0,50
0,25
30
TUY N 5 HSG THNH PH N NG HO H C 11
CH
3
+ Br
2
Fe
+CH
3
Cl
AlCl
3
CH
3
(d)
+H
2
SO
4
SO
3
H
CH
3
SO
3
H
t
CH
3
Br
Br
+ KMnO
4
COOH
Br
0,50
3. (a) X (C
x
H
y
), c 12x + y = 128 (y 2x + 2) c hai nghim thch hp l C
10
H
8
v
C
9
H
20
. Tuy nhin, v X tc dng c vi hidro, nn cng thc ng l C
10
H
8
(
7 ).
V X khng lm nht mu nc brom nn cu to thch hp ca X l naphtalen v
ph hp vi gi thit th Y l tetralin v Z l decalin :
(naphtalen)
(tetralin) (decalin)
1,00
(b) Phn ng :
+ HONO
2
H
2
SO
4
+ H
2
O
NO
2
+ Br
2
Fe
+ HBr
Fe
0,50
31
TUY N 5 HSG THNH PH N NG HO H C 11
S GIO DC V O TO
THNH PH NNG
HNG DN CHM THI HC SINH GII THNH PH
MN: HA HC LP 11
Thi gian: 150 pht (khng k thi gian giao )
Cu XXII (4 im)
1. Xt hp cht vi hidro ca cc nguyn t nhm VA. Gc lin kt HXH (X l k hiu nguyn
t nhm VA) v nhit si c cho trong bng di y.
c im NH
3
PH
3
AsH
3
SbH
3
Gc HXH 107
o
93
o
92
o
91
o
Nhit si (
o
C) -
33,0
-
87,7
-62,0 -18,0
So snh v gii thch s khc bit gi tr gc lin kt v nhit si ca cc cht ny.
2. Khi cho NH
3
vo dung dch AgNO
3
th thy c vn c mu trng tan li ngay trong NH
3
d,
nhng khi thm AsH
3
vo dung dch AgNO
3
th li thy xut hin kt ta Ag v dung dch thu
c c cha axit asen. Vit phng trnh phn ng v gii thch ti sao c s khc bit ny.
3. Xt phn ng tng hp amoniac : N
2
(k) + 3H
2
(k) 2NH
3
(k)
450
o
C hng s cn bng ca phn ng ny l K
P
= 1,5.10
-5
. Tnh hiu sut phn ng tng
hp NH
3
nu ban u trn N
2
v H
2
theo t l 1:3 v th tch v p sut h bng 500 atm.
P N IM
1. T N n Sb bn knh nguyn t tng dn, c trng lai ha sp
3
ca nguyn t X
trong phn t XH
3
gim dn, nn gc lin kt tr v gn vi gc gia hai obitan
p thun khit. (Cng c th gii thch l t Sb n N m in ca nguyn t
trung tm tng dn, bn knh nguyn t gim dn, lm khong cch gia cc cp
electron lin kt gim, lc y gia chng tng, nn gc lin kt tng).
0,50
NH
3
to c lin kt H lin phn t, cn PH
3
th khng, do vy t NH
3
n PH
3
nhit si gim. T PH
3
n SbH
3
nhit si tng do phn t khi tng.
N
H
H
H N
H
H
H
... ... ...
1,00
(0,50

2)
2. Phng trnh phn ng :
AgNO
3
+ NH
3
+ H
2
O AgOH + NH
4
NO
3
AgOH + 2NH
3
Ag(NH
3
)
2
OH
3
0
3
3
3 2 3
1
3
3
HNO 6 Ag 6 O As H O H 3 NO Ag 6 H As + + + +
+ +
NH
3
c tnh baz mnh hn AsH
3
, nhng ngc li AsH
3
c tnh kh mnh hn
NH
3
.
1,50
(0,50

3)
3. Gi x v h ln lt l s mol ban u ca N
2
v hiu sut phn ng.
N
2
(k) + 3H
2
(k) 2NH
3
(k)
n
o
x 3x 0
n hx 3hx 2hx
x(1-h) 3x(1-h) 2hx n = x(4-2h)
3
2
3
H N
2
NH
P
P
) h 2 4 ( x
) h 1 ( x 3
P
) h 2 4 ( x
) h 1 ( x
P
) h 2 4 ( x
xh 2
P . P
P
K
2 2
3

,
_

,
_

,
_


K P
) h 1 ( 2 , 5
) h 2 4 ( h 2
2

0 1 , 10 h 2 , 28 h 1 , 14
2
+ vi 1 h
1,00
(0,50

2)
32
TUY N 5 HSG THNH PH N NG HO H C 11
467 , 0 h
, vy hiu sut phn ng bng 46,7%
Cu XXIII (4 im)
1. Trn ln 7 mL dung dch NH
3
1M v 3 mL dung dch HCl 1M thu c dung dch A. Thm
0,001 mol NaOH vo dung dch A thu c dung dch B.
(a) Xc nh pH ca cc dung dch A v B, bit
5
NH
10 . 8 , 1 K
3

.
(b) So vi dung dch A, gi tr pH ca dung dch B c s thay i ln hay nh ? Nguyn
nhn ca s bin i ln hay nh l g ?
2. Tnh th tch dung dch Ba(OH)
2
0,01M cn thm vo 100 mL dung dch Al
2
(SO
4
)
3
0,1M
thu c 4,275 gam kt ta.
P N IM
1. (a) Xt phn ng ca dung dch NH
3
v dung dch HCl :
NH
3
+ H
+
NH
4
+
C
o
0,7M 0,3M
C 0,3M 0,3M
[C] 0,4M 0 0,3M
Vy dung dch A gm cc cu t chnh l NH
3
0,4M, NH
4
+
0,3M v Cl
-
.
0,50
NH
3
+ H
2
O NH
4
+
+ OH
-
K
b
C
o
0,4M 0,3M
C xM xM xM
[C] (0,4-x)M (0,3+x)M xM
5 5
10 . 4 , 2 x 10 . 8 , 1
) x 4 , 0 (
x ). x 3 , 0 (
K

4 , 9 )] 10 . 4 , 2 lg( [ 14 pH
5
A


0,50
Khi thm 0,001 mol NaOH vo dung dch A c phn ng :
NH
4
+
+ OH
-
NH
3
+ H
2
O
C
o
0,3M 0,1M 0,4M
C 0,1M 0,1M 0,1M
[C] 0,2M 0 0,5M
Vy dung dch B gm cc cu t chnh l NH
3
0,5M, NH
4
+
0,2M v Cl
-
.
0,50
NH
3
+ H
2
O NH
4
+
+ OH
-
K
b
C
o
0,5M 0,2M
C xM xM xM
[C] (0,5-x)M (0,2+x)M xM
5 5
10 . 5 , 4 x 10 . 8 , 1
) x 5 , 0 (
x ). x 2 , 0 (
K

7 , 9 )] 10 . 5 , 4 lg( [ 14 pH
5
B


0,50
(b) S khc bit gi tr pH ca dung dch B so vi dung dch A l khng ln, do
trong dch A tn ti mt cn bng axit baz, cn bng ny c kh nng lm
gim (chng li) tc ng thay i nng axit (H
+
) hoc baz (OH
-
).
0,50
2. Theo gi thit
mol 02 , 0 n
3
Al

+ v
mol 03 , 0 n
2
4
SO

. Gi x l s mol Ba(OH)
2
cn thm vo, nh vy
mol x n
2
Ba

+ v
mol x 2 n
OH

.
Ba
2+
+ SO
4
2-
BaSO
4
(1)
n
o
x (mol) 0,03 (mol)
Al
3+
+ 3OH
-
Al(OH)
3
(2)
n
o
0,02 (mol) 2x (mol)
0,50
33
TUY N 5 HSG THNH PH N NG HO H C 11
Al(OH)
3
+ OH
-
Al(OH)
4
-
(3)
Xt trng hp ch xy ra phn ng (1) v (2). Trong trng hp ny Al
3+
tham
gia phn ng va hoc d : ) mol ( 03 , 0 x 02 , 0
3
x 2
, v nh vy Ba
2+
phn ng ht phn ng (1).
Ta c : m(kt ta) = ) mol ( 015 , 0 x 275 , 4
3
x 2
. 78 x . 233 +
Vy th tch dung dch Ba(OH)
2
s dng l
L 5 , 1
L / mol 01 , 0
mol 015 , 0

0,50
Nu xy ra cc phn ng (1), (2) v (3) th
) mol ( 03 , 0 x >
gam 275 , 4 gam 99 , 6 mol / gam 233 mol 03 , 0 m
4
BaSO
>
(loi).
0,50
Cu XXIV (4 im)
1. Chn cht ph hp, vit phng trnh (ghi r iu kin phn ng) thc hin bin i sau :
N
0
N
-3
N
+2
N
+4
N
+5
N
0
N
+2
N
+3
N
+5 (1) (2) (3)
(5) (6)
(8)
(4)
(7)
2. Dung dch A gm 0,4 mol HCl v 0,05 mol Cu(NO
3
)
2
. Cho m gam bt Fe vo dung dch
khuy u cho n khi phn ng kt thc thu c cht rn X gm hai kim loi, c khi
lng 0,8m gam. Tnh m. Gi thit sn phm kh HNO
3
duy nht ch c NO.
P N IM
1. Cc phng trnh phn ng :
(1) N
2
+ 3H
2

atm 300 , 500
Fe
o

2NH
3
(2) 4NH
3
+ 5O
2


C 900 850 , Pt
o
4NO + 6H
2
O
(3) 2NO + O
2
2NO
2

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

(5) 5Mg + 12 HNO
3
5Mg(NO
3
)
2
+ N
2
+ 6H
2
O
(6) N
2
+ O
2


C 2000
o
2NO
(7) 2NO
2
+ 2KOH KNO
2
+ KNO
3
+ H
2
O
(8) 5KNO
2
+ 2KMnO
4
+ 3H
2
SO
4
5KNO
3
+ K
2
SO
4
+ 2MnSO
4
+ 3H
2
O
2,00
(0,25

8)
2. Trong dung dch A :
Dung dch A c 0,4 mol H
+
, 0,05 mol Cu
2+
, 0,4 mol Cl
-
, 0,1 mol NO
3
-

Khi cho Fe vo dung dch A xy ra cc phn ng :
(1) Fe

+ 4H
+
+ NO
3
-
Fe
3+
+ NO + 2H
2
O
0,4 0,1
0,1 0,4 0,1 0,1
0 0 0,1
(2) Fe + 2Fe
3+
3Fe
2+
0,05 0,1
(3) Fe + Cu
2+
Fe
2+
+ Cu
0,16 0,05 0,05
1,00
34
TUY N 5 HSG THNH PH N NG HO H C 11
S mol Fe tham gia cc phn ng t (1) n (3) l 0,1+ 0,05 + 0,05 = 0,2
(mol)
Hn hp 2 kim loi sau phn ng gm Fe d Cu, (m - 56 0,2) + 0,05 64 =
0,8 m
m = 40 (gam)
1,00
Cu XXV (4 im)
1. Di y l cc gi tr nhit nng chy v nhit si ca n-pentan v neopentan. Gii
thch s khc bit nhit nng chy v nhit si gia cc cht ny.
n-Pentan Neopentan
Nhit si (
o
C) 36 9,5
Nhit nng chy (
o
C) -130 -17
2. X, Y, Z ln lt l ankan, ankadien lin hp v ankin, iu kin thng tn ti th kh. t
chy 2,45 L hn hp ba cht ny cn 14,7 L kh O
2
, thu c CO
2
v H
2
O c s mol bng
nhau. Cc th tch kh u o 25
o
C v 1 atm.
(a) Xc nh cng thc phn t ca X, Y v Z.
(b) Y cng Br
2
theo t l mol 1:1 to ba sn phm ng phn. Dng c ch phn ng gii
thch s hnh thnh cc sn phm ny.
3. Hon thnh cc phng trnh phn ng :
+HCHO
A
(1)
(2) (3)
(5)
(6)
(4)
(7)
Etyl bromua
+Mg/ete
+CH
3
COCH
3
+CO
2
X
1
Y
1
Z
1
H
2
O
X
1
Y
1
Z
1
H
2
O
H
2
O
P N IM
1. Nhit si ca neopentan thp hn n-pentan v khi phn t c cng nhiu nhnh,
tnh i xng cu ca phn t cng tng, din tch b mt phn t cng gim, lm
cho bn tng tc lin phn t gim v nhit si tr nn thp hn.
0,50
Tri li, tnh i xng cu li lm cho mng tinh th cht rn tr nn c kht hn v
bn vng hn, nn nhit nng chy cao hn. 0,25
2. (a) Gi cng thc trung bnh ca X, Y, Z l
n 2 n
H C
(do s mol CO
2
v H
2
O bng
nhau).
O H n CO n O
2
n 3
H C
2 2 2
n 2 n
+ + , ta c : 4 n
45 , 2
7 , 14
1
2 / n 3

V X, Y, Z iu kin thng u tn ti th kh (trong phn t, s nguyn t C
4), nn cng thc phn t ca X l C
4
H
10
v Y, Z l C
4
H
6
.
0,75
(0,25

3)
(b) C ch phn ng :
CH
2
CH CH CH
2
Br-Br

CH
2
CH CH CH
2
Br
CH
2
CH CH CH
2
Br
- Y
-
0,75
(0,50+0,25)
35
TUY N 5 HSG THNH PH N NG HO H C 11
+ Br
-
CH
2
CH CHBr CH
2
Br
C C
CH
2
Br BrH
2
C
H H
C C
H BrH
2
C
H CH
2
Br
3. Cc phng trnh phn ng :
CH
3
CH
2
Br + Mg

ete
CH
3
CH
2
MgBr
CH
3
CH
2
MgBr C
O
H H
+

CH
3
CH
2
CH
2
OMgBr
CH
3
CH
2
CH
2
OMgBr + H
2
O
CH
3
CH
2
CH
2
OH + Mg(OH)Br
CH
3
CH
2
MgBr + C
O
CH
3
CH
3
+

CH
3
CH
2
C
CH
3
OMgBr
CH
3
CH
3
CH
2
C CH
3
+ H
2
O CH
3
CH
2
C CH
3
+ Mg(OH)Br
CH
3
OMgBr
CH
3
OH
CH
3
CH
2
MgBr C
O
+

CH
3
CH
2
C OMgBr
O
O
CH
3
CH
2
C OMgBr + H
2
O
O
CH
3
CH
2
C OH + Mg(OH)Br
O
1,75
(0,25

7)
Cu XXVI ( 4 im)
1. Cht X c cng thc phn t C
7
H
6
O
3
. X c kh nng tc dng vi dung dch NaHCO
3
to
cht Y c cng thc C
7
H
5
O
3
Na. Cho X tc dng vi anhirit axetic to cht Z (C
9
H
8
O
4
) cng
tc dng c vi NaHCO
3
, nhng khi cho X tc dng vi metanol (c H
2
SO
4
c xc tc)
th to cht T (C
8
H
8
O
3
) khng tc dng vi NaHCO
3
m ch tc dng c vi Na
2
CO
3
.
(a) Xc nh cu to cc cht X, Y, Z, T v vit cc phng trnh phn ng xy ra. Bit cht
X c kh nng to lin kt H ni phn t.
(b) Cho bit ng dng ca cc cht Y, Z v T
2. t chy hon ton 10,08 L hn hp kh gm hai ankanal A v B thu c 16,8 L kh CO
2
.
Nu ly cng lng hn hp ny tc dng hon ton vi lng d dung dch AgNO
3
trong
NH
3
th thu c 108 gam Ag kim loi.
(a) Xc nh A v B, bit cc kh u o 136,5
o
C v 1 atm.
(b) Tin hnh phn ng canizaro gia A v B. Cho bit sn phm to thnh v gii thch.
P N IM
1. (a) Cu to cc cht :
1,00
36
TUY N 5 HSG THNH PH N NG HO H C 11
COOH
OH
COONa
OH
COOH
OOCCH
3
COOCH
3
OH
X Y Z T
(0,25

4)
Phng trnh phn ng :
HOC
6
H
4
COOH + NaHCO
3
HOC
6
H
4
COONa + H
2
O + CO
2
HOC
6
H
4
COOH + CH
3
OH

4 2
SO H
HOC
6
H
4
COOCH
3
+ H
2
O
HOC
6
H
4
COOH + (CH
3
CO)
2
O

4 2
SO H
CH
3
COOC
6
H
4
COOH + CH
3
COOH
0,75
(0,25

3)
(b) Y vi hm lng rt nh c s dng lm cht bo qun thc phm v pha ch
nc xc ming (c tc dng dit khun); Z c s dng ch to dc phm
aspirin v T l thnh phn chnh ca du gi xanh.
0,75
(0,25

3)
2. (a) Xc nh A v B.
) mol ( 3 , 0
5 , 1 273 ) 273 / 4 , 22 (
1 08 , 10
n
B , A

;
) mol ( 5 , 0
5 , 1 273 ) 273 / 4 , 22 (
1 8 , 16
n
2
CO

v ) mol ( 1
108
108
n
Ag

67 , 1
3 , 0
5 , 0
C
A l HCHO
0,50
Gi cng thc ca B l RCHO (hay C
n
H
2n
O) v s mol ca A, B ln lt l a, b.
HCHO

+
3 3
NH / AgNO
4Ag
RCHO

+
3 3
NH / AgNO
2Ag
Ta c :

'


+
+
+
3 n ; 1 , 0 b ; 2 , 0 a
1 b 2 a 4
5 , 0 nb a
3 , 0 b a
Vy B l CH
3
CH
2
CHO
0,50
(b) Phn ng canizaro :
HCHO + CH
3
CH
2
CHO + OH
-
HCOO
-
+ CH
3
CH
2
CH
2
OH
Hp cht d tham gia phn ng cng A
N
hn (nguyn t cacbon trong nhm
cacbonyl dng in hn) v c nhiu H lin kt vi nhm cacbonyl hn, c xu
hng chuyn thnh ion cacboxilat.
0,50
(0,25

2)
37

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