S GIO DC V O TO

K THI CHN HC SINH GII CP TNH

VNH PHC

LP 12 THPT CHUYN NM HC 2012-2013

CHNH THC

Mn: HA HC - THPT CHUYN

Thi gian: 180 pht (khng k thi gian giao )
Ngy thi: 02/11/2012
( thi gm 02 trang)

Cu 1: (1,0 im)
Ho tan hon ton 11,2 gam mt kim loi R bng dung dch H2SO4 c nng thu c SO2, cho
ton b lng kh ny hp th ht vo 350 ml dung dch NaOH 2M. Sau phn ng, c cn dung
dch th thu c 41,8 gam cht rn khan.
1. Tm kim loi R?
2. Ha tan 8,4 gam kim loi R vo 200ml dung dch HCl 2M thu c dung dch A. Cho dung
dch A tc dng vi dung dch AgNO3 d, tnh khi lng kt ta thu c?
Cu 2: (2,0 im)
1. Hy cho bit dng lai ha ca nguyn t trung tm v dng hnh hc theo m hnh VSEPR
ca cc phn t, ion sau: SF4; HClO2; HOCl; ICl 4 ; IF7; BrF5; HNO3; C2H6.
2. Kho st phn ng phn hy NO2 to thnh NO v O2 100C di nh hng ng hc v
nhit ng hc. Bng sau cho bit tc u ca phn ng ph thuc vo cc nng u khc
nhau ca NO2:
[NO2]o ( mol.lit-1)
vo ( mol.lit-1.s-1)

0,010
5,4.10-5

0,012
7,78.10-5

0,014
1,06.10-4

0,016
1,38.10-4

a) Xc nh bc ca phn ng v hng s tc phn ng?

b) Mt cch gn ng, nu xem nh cc i lng nhit ng ca phn ng trn khng ph
thuc nhit . Hy s dng cc gi tr sau tr li cc cu hi: nhit cn t n cn
bng dch chuyn v pha phi l bao nhiu?
0
0
Cho: H s, NO2 =33,2kJ/mol. ; H s, NO =90,3kJ/mol.
S0NO2 =241 J/mol.K; S0NO =211 J/mol.K; SO0 2 =205J/mol.K
Cu 3: (2,0 im)
1. Khi axit ho dung dch hn hp cha [Ag(NH3)2]Cl 0,1M v NH3 1M n khi dung dch thu
c c pH = 6 th c xut hin kt ta khng? ti sao?
+

Cho bit KS (AgCl) = 1,1.10-10; K[Ag(NH 3 ) 2 ] = 6,8.10-8; Kb (NH 3 ) = 2.10-5

2. Cho pin sau : H2(Pt), PH 2 =1atm / H+: 1M // MnO 4 : 1M, Mn2+: 1M, H+: 1M / Pt
Bit rng sc in ng ca pin 250 C l 1,5V.
0
a) Hay cho bit phn ng thc t xy ra trong pin v tinh E MnO-4 /Mn 2+ ?
b) Sc in ng ca pin thay i nh th no khi thm mt it NaHCO3 vo na trai ca pin?
Cu 4: (1,0 im)
un nng hn hp gm 1 mol HCOOH; 1 mol CH 3COOH v 2 mol C2H5OH c H2SO4 c
xc tc toC (trong bnh kn dung tch khng i) n trng thi cn bng th thu c 0,6 mol
HCOOC2H5 v 0,4 mol CH3COOC2H5. Nu un nng hn hp gm 1 mol HCOOH, 3 mol
CH3COOH v a mol C2H5OH iu kin nh trn n trng thi cn bng th thu c 0,8 mol
HCOOC2H5. Tnh a?
Trang 1

Cu 5: (2,5 im)
1. Hy gi tn v gii thch s khc nhau v nhit si cc cht trong dy sau:
N

N
(a)

(b)

(c)

(d)

H
(256 C)

(117 C)

(115 C)

(1870C)

2. V cng thc Fis ca cc hp cht cacbohirat A, E1, E2, F1, F2 v G trong dy chuyn ha sau:
H

OH

HO

CHO

H
H

OH

(A)

tang mach Kiliani - Fisher

E1 + E2

NaBH4

NaBH4

F1 + F2

3. Cho s chuyn ha:

OH
(H3C)2C=CH2
H2SO4

H3C

H2 / Ni
(p sut)

CrO3

1) CH3MgBr
2) H2O

OH
H+, t0
H2O

1) O3
2) H2O/Zn

Hy vit cu to cc cht t A n E?
Cu 6: (1,5 im)
1. Hp cht (A) c cng thc phn t C10H10O khng to mu vi FeCl3, to sn phm cng
vi NaHSO3. Cho (A) tc dng vi I2/NaOH khng to kt ta, axit ha hn hp sau phn ng
c (B) l C10H10O2, (B) lm mt mu dung dch KMnO4. Cho (B) tc dng vi lng d brom
khi c mt Ag2O/CCl4 thu c (C) l 1,2,3-tribrom-1-phenylpropan.
Mt khc, cho (A) tc dng vi NaBH4 thu c (D) l C10H12O. Hiro ha nh D c xc tc
thu c (E) C10H14O. un nng (E) vi axit H2SO4 long thu c (F) l C10H12. Lp lun xc
nh cng thc cu to ca (A), (B), (D), (E). Vit phn ng to thnh (C) t (B) v gii thch s
to thnh (F) t (E).
2. Vit c ch phn ng sau:
H2SO4

Ht
Th sinh c s dng bng tun hon. Cn b coi thi khng gii thch g thm.

Trang 2

S GIO DC V O TO
VNH PHC

K THI CHN HC SINH GII CP TNH

LP 12 THPT CHUYN NM HC 2012-2013

Mn: HA HC - THPT CHUYN

HNG DN CHM
(Gm 07 trang)
Cu
Ni dung
Cu 1
Ho tan hon ton 11,2 gam mt kim loi R bng dung dch H2SO4 c
(1,0 nng thu c SO2, cho ton b lng kh ny hp th ht vo 350 ml dung
)
dch NaOH 2M. Sau phn ng c cn dung dch th thu c 41,8 gam cht
rn khan.
1) Tm kim loi R?
2) Ha tan 8,4 gam kim loi R vo 200ml dung dch HCl 2M thu c dung
dch A. Cho dung dch A tc dng vi dung dch AgNO3 d, tnh khi lng
kt ta thu c?

im

p n:
- S mol NaOH = 0,35 . 2 = 0,7 mol
- Nhn xt:
* Nu cht rn l Na2SO3 th khi lng l: 0,35 . 126 = 44,1g
* Nu cht rn l NaHSO3 th khi lng l: 0,7. 104 = 72,8g
Cht rn thu c khi c cn dung dch l 41,8g < (44,1 ; 72,8)
=> cht rn thu c gm Na2SO3 v NaOH d
- t s mol ca Na2SO3 l x s mol NaOH d l 0,7-2.x
Ta c: 126.x + (0,7-2x).40 = 41,8 x = 0,3 mol
=> nR =

(0,5)

0, 6
56n
MR =
R l Fe
n
3

- Khi cho Fe tc dng vi dung dch HCl c phn ng:

Fe + 2HCl FeCl2 + H2
=> Dung dch A sau phn ng c: 0,15 mol FeCl2 v 0,1 mol HCl d hay 0,15
mol Fe2+ ; 0,1 mol H+ ; 0,4 mol Cl- Khi cho dung dch AgNO3 d vo dung dch A c cc phn ng:
Ag+ + Cl- AgCl
(1)
2+
+
3+
3Fe + 4H + NO3 3Fe + NO + 2H2O (2)
Fe2+ + Ag+ Fe3+ + Ag
(3)
3
+
4
=> Theo (3) nAg = nFe2+ = 0, 075mol

Theo (2) nFe = nH = 0, 075mol

2+

=> Khi lng kt ta thu c sau phn ng

m = mAgCl + mAg = 0,4.143,5 + 0,075.108 = 65,5 (g)

Trang 3

(0,5)

Cu 2
1) Hy cho bit dng lai ha ca nguyn t trung tm v dng hnh hc
(2,0 theo m hnh VSEPR ca cc phn t, ion sau: SF4; HClO2; HOCl; ICl 4 ;
)
IF7; BrF5; HNO3; C2H6.
p n:
1) * SF4: (AX4E) lai ha sp3d. Hnh dng ci bp bnh
* HClO2: (AX3E2) lai ha sp3d. Hnh dng ch T
* HClO : (AX2E3) lai ha sp3d. Hnh dng ng thng
* ICl 4 : (AX4E2) lai ha sp3d2 . Hnh dng vung phng
* IF7: (AX7) lai ha sp3d3. Hnh dng lng chp ng gic
* BrF5: (AX5E) lai ha sp3d2 . Hnh dng thp vung
* HNO3: (AX3) lai ha sp2 . Hnh dng tam gic phng
* C2H6: (AX4) lai ha sp3 . Hnh dng 2 t din chung nh

(1,0)

2) Kho st phn ng phn hy NO2 to thnh NO v O2 100C di nh

hng ng hc v nhit ng hc. Bng sau cho bit tc u ca phn
ng ph thuc vo cc nng u khc nhau ca NO2:
[NO2]o ( mol.lit-1)
vo ( mol.lit-1.s-1)

0,010
5,4.10-5

0,012
7,78.10-5

0,014
1,06.10-4

0,016
1,38.10-4

a) Xc nh bc ca phn ng v hng s tc phn ng?

b) Mt cch gn ng, nu xem nh cc i lng nhit ng ca phn
ng trn khng ph thuc nhit . Hy s dng cc gi tr sau tr li
cc cu hi: Nhit nh nht cn t n cn bng dch chuyn v
pha phi l bao nhiu?
0
0
Cho: H s,NO = 33,2 kJ / mol. ; H s , NO = 90,3kJ / mol.
2

0
NO2

0
= 241 J / mol.K ; S NO
= 211 J / mol.K ; S O02 = 205 J / mol.K

p n:
a)
Phn ng : 2NO2 2NO + O2
- Tnh ton : v = k[NO2]a => lgv = lgk + a.lg[NO2]
- p dng : lg5,4.10-5 = lgk + a.lg0,010 v lg1,38.10-4 = lgk + a.lg0,016
v

0,4075 = a.0,0204 a 2 k = [NO ] 2

2
- S dng ln lt cc d kin thc nghim, ta c:
k1 = 5,4.10-5/0,012 = 0,54
k2 = 7,78.10-5/0,0122 = 0,54
k3 = 1,06.10-4/0,0142 = 0,541
k4 = 1,38.10-4/0,0162 = 0,539
=> Kt lun: bc ca phn ng l bc 2, hng s tc phn ng k= 0,54lit/mol.s

Trang 4

(0,5)

H0p = 2 90,3 2 33,2 = 114,2 kJ

Sop = 2 211 + 205 2 241 = 145 J/K
- Mt cch gn ng , v mt nhit ng hc khi phn ng t n cn bng th :
b)

Gp

H o 114,2 1000 J
=
= 787,6 K
= 0 T =
145( J / K )
S o

=> iu kin v nhit cn cn bng dch chuyn v pha phi l:

T > 787,6 K

(0,5)

Cu 3
1) Khi axit ho dung dch hn hp cha [Ag(NH3)2]Cl 0,1M v NH3 1M
(2,0 n khi dung dch thu c c pH = 6 th c xut hin kt ta khng? ti
)
sao?
+

Cho bit KS (AgCl) = 1,1.10-10; K[Ag(NH 3 ) 2 ] = 6,8.10-8; Kb(NH 3 ) = 2.10-5

p n:
1. C xut hin kt ta
* Gii thch:
- Dung dch thu c c pH = 6 < 7 => c th coi ton b NH3 trong dung dch
chuyn ho thnh mui NH4+ => [NH4+] = 1M
- Trong dung dch c cc cn bng sau:
[Ag(NH 3 )2] + + Cl[Ag(NH3)2]Cl
[Ag(NH 3 )2] +
Ag+ + 2NH3
K1 = 6,8.10-8
NH3 + H2O
NH4+ + OHK2 = 2.10-5
- Thay gi tr [NH4+] = 1; [OH-] = 10-8 (v pOH = 8) vo biu thc tnh hng s K2
ta c [NH3] = 5.10-4M
(3)
- Theo nh lut bo ton nng ta c
[Ag(NH 3 )2] + = 0,1 - [Ag+] (4)
Thay (3) ; (4) vo biu thc tnh hng s K1 ta c [Ag+] = 2,1.10-2
=> [Ag+][Cl-] = 2,1.10-2. 0,1 > KS (AgCl) =1,1.10-10
2) Cho pin sau :
H2(Pt), PH = 1atm / H+: 1M // MnO 4 : 1M, Mn2+: 1M, H+: 1M / Pt
2

Bit rng sc in ng ca pin 250 C l 1,5V.

0
a) Hay cho bit phn ng thc t xy ra trong pin v tinh E MnO / Mn ?
b) Sc in ng ca pin thay i nh th no khi thm mt it NaHCO 3 vo
na trai ca pin.

2+

p n:
1. Phn ng thc t xy ra trong pin:
Do Epin = 1,5 V > 0 nn cc Pt - (phi) l catot, cc hiro - (tri) l anot do
phn ng thc t xy ra trong pin s trng vi phn ng qui c:
- Catot:
MnO 4 + 8H+ + 5e
Mn2+ + 4H2O
- Anot:
H2
2H+ + 2e
=> phn ng trong pin:
2MnO 4 + 6H+ + 5H2
2Mn2+ + 8H2O
* E

= E MnO

pin
0

/ Mn 2 +

- E 2H

/ H2

= 1,5 V

E MnO / Mn = 1,5 V
2. *) Nu thm mt t NaHCO3 vo na tri ca pin s xy ra p:
HCO3- + H+ H2O + CO2
Trang 5

2+

(1,0)

 [H

[ ]

0,059
H+
gim nn E 2 H + / H 2 = 2 . lg P gim , do :
H2

Epin = (E MnO

/ Mn 2 +

- E 2H

/ H2

(1,0)

) s tng

Cu 4 un nng hn hp gm 1 mol HCOOH; 1 mol CH COOH v 2 mol C H OH

3
2 5
(1,0 c H SO c xc tc toC (trong bnh kn dung tch khng i) n trng
2
4
)
thi cn bng th thu c 0,6 mol HCOOC2H5 v 0,4 mol CH3COOC2H5.
Nu un nng hn hp gm 1 mol HCOOH, 3 mol CH 3COOH v a mol
C2H5OH iu kin nh trn n trng thi cn bng th thu c 0,8 mol
HCOOC2H5. Tnh a.
p n:
- Cc phng trnh phn ng:
xt,t

HCOOC2H5 + H2O
HCOOH + C2H5OH

[]
0,4
1
0,6
1 (mol)
=> K1 = 1,5
xt,t

CH3COOC2H5 + H2O
CH3COOH + C2H5OH

[]

0,6

0,4

K1

K2

1 (mol)

=> K2 = 2/3
- Gi s mol ca CH3COOC2H5 l b mol. Ta c:
0

(0,5)

xt,t

HCOOC2H5 +
HCOOH + C2H5OH

[ ]: 0,2
a-0,8-b
0,8
xt,t

CH3COOC2H5
CH3COOH + C2H5OH

[ ]: 3-b
a-0,8-b
b
0

H2O
0,8+b
+ H2 O
0,8+b

0,8.(0,8 + b)
b.(0,8 + b)
; K2 =
0, 2.(a 0,8 b)
(3 b).(a 0,8 b)

=>

K1 =

=>

K1 0,8.(3 b) 9
=
=
K2
0, 2.b
4

(mol)
(mol)

b = 1,92 a = 9,97 mol

(0,5)

Cu 5 1) Hy gi tn v gii thch s khc nhau v nhit si cc cht trong dy sau:

(2,5
N
N
)
(a)
(b)
(c)
N
(d)
N

N
H

(115 C)

(117 C)

(256 C)

H
(1870C)

p n:
1) * Tn gi
(a) Piridin ; (b) Thiazol ; (c) 1,3Diazol hay Imidazol; (d) 1,2Diazol hay Pirazol

Trang 6

(0,5)

* So snh nhit si:

- (a) v (b) khng to c lin kt hidro lin phn t nn nhit
si thp hn, trong PTK(a) = 79 < PTK(b) = 85 nn nhit si
(a) < (b).
(c) v (d) c nhit si cao hn do u to lin kt hidro lin
phn t, nhng (d) cn to lin kt hidro dng dime cn tr s hnh
thnh lin kt lin phn t nn nhit si ca (d) < (c).

N
N

N
N

(0,5)

2) V cng thc Fis ca cc hp cht cacbohirat A, E1, E2, F1, F2 v G

trong dy chuyn ha sau:
H

OH

HO

CHO

H
H

OH

tang mach Kiliani - Fisher

E1 + E2

(A)

NaBH4

NaBH4

F1 + F2

p n:
CH2OH

CHO

CHO

CHO

CH2OH

NaBH4

NaBH4

Tng m ch Kiliani-Fisher

CH2OH

CH2OH

CH2OH

CH2OH

CH2OH

CH2OH

CH2OH

E1

E2

F1

F2

(0,5)

3) Cho s chuyn ha:

OH
(H3C)2C= CH2
H2SO4

H3C

H2 / Ni
(p sut)

CrO3

1) CH3MgBr

OH
H+, t0

2) H2O

H2O

1) O3
2) H2O/Zn

Hy vit cu to cc cht t A n E?
p n:
Cc cht trong s trn l:
(A)

(B)
OH

(C)
OH

(D)

(E)
CH3

CH3
O
O

H3C

CH3
CH3

H3C

CH3
CH3

H3C

CH3
CH3

Trang 7

H3C

CH3
CH3

H3C

CH3
CH3

(1,0)

Cu 6
(1,5 1) Hp cht (A) c cng thc phn t C10H10O khng to mu vi FeCl3, to
)
sn phm cng vi NaHSO3. Cho (A) tc dng vi I2/NaOH khng to kt
ta, axit ha hn hp sau phn ng c (B) l C10H10O2, (B) lm mt mu
dung dch KMnO4. Cho (B) tc dng vi lng d brom khi c mt Ag2O/CCl4 thu c (C) l 1,2,3-tribrom-1-phenylpropan.
Mt khc, cho (A) tc dng vi NaBH4 thu c (D) l C10H12O. Hiro ha
nh D c xc tc thu c (E) C10H14O. un nng (E) vi axit H2SO4 long
thu c (F) l C10H12. Lp lun xc nh cng thc cu to ca (A), (B),
(D), (E). Vit phn ng to thnh (C) t (B) v gii thch s to thnh (F) t
(E)?
p n:
* A: C10H10O ( = 6 ), c 1 nguyn t O A c th l hp cht ancol, phenol, ete,
andehit, xeton.
- A khng to mu vi FeCl3 A khng phi hp cht phenol.
A to sn phm cng vi NaHSO3 A l andehit hoc xeton
A khng to kt ta vi I2/NaOH khng phi dng metylxeton
1.I /NaOH
B(C10H10O2), y l phn ng oxi ha nhm
- Mt khc, A(C10H10O)
2.H
CHO thnh nhm COOH.
A cha nhm CHO.
* Do B lm mt mu dung dch KMnO4 B cha vng benzen, nhnh khng no. (0,25)
2

CH=CH 2CH2-CHO

CH=CH 2CH2-COOH

CH=CH 2CH2-CH2OH

CH2CH2CH2-CH2OH

(0,5)

* Phn ng to thnh (C) t (B)

2C6H5-CH=CH2CH2COOH + 4Br2 + Ag2O CCl

2C6H5-CHBr-CH2BrCH2Br + 2CO2 + H2O + 2AgBr

4

(0,25)

* Gii thch: D E
CH2CH2CH2-CH2OH

xt H

CH2CH2CH2CH2

-H2O
E

SE(Ar): ong vong

(0,25)
F

Trang 8

2) C ch phn ng:
H2SO4

p n:
H+

Ch. vi

H+

+
+

CH2

CH2

( Lu : cc cch lm khc p n nhng ng, vn c im ti a)

Ht

Trang 9

(0,25)