TRNG THPT TX NGHIA

L
Ki thi chon
hoc sinh gioi cp
trng
Ngy thi : 15/9/2013

THI HOC
SINH GIOI MN HOA
LP 12
Nm hoc 2013-2014
Thi gian : 180 phut

Cu I (3 im):
1. Phng php sunfat c th iu ch c cht no: HF, HCl, HBr, HI? N u c ch t khng i u
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 ch t: a)
Tnh axit rt yu, yu hn axit cacbonic; b) C tnh oxi ho mnh lit; c) R t 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. Tm cch loi sch tp cht kh c trong kh khc v vit cc phng trnh phn ng xy ra:
a) CO c trong CO2 ; b) H2S c trong HCl ; c) HCl c trong H2S; d) HCl c trong SO2;
Cu II: (4,0 im):
Mt phn t XY3 c tng cc ht proton, ntron, electron bng 196; trong , s ht mang i n
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 XY3.
b) Vit cu hnh electron ca nguyn t X,Y.
c) Xc nh b 4 s lng t ng vi electron cui cung
ca X v Y.
d) 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 XY3
Cu III : (3im)

Cho 1 mol axit axetic vi 1 mol ru etilic vao binh

cu.
Tao iu kin cho xay ra phan ng:
CH3COOH + C2H5OH CH3COOC2H5 + H2O
Khi h at trang
thai cn bng
trong hn
hp co

2
mol CH3COOC2H5. Hoi s mol este CH3COOC2H5
3

thu c luc cn bng

la bao nhiu. Bit rng
s mol ban u
cua CH3COOH la 1 mol/l, C2H5OH la 2 mol/l.
Cu IV: (3 im)

a/ Cho dung dich

CH3COOH 0,1M co = 4,3%. Tinh
nng
ion H+ va pH cua dung dich.

b/ Tnh pH ca dung dch thu c khi trn ln 50,0 ml dung dch NH 4Cl 0,200 M vi 75,0 ml dung
dch NaOH 0,100 M. Bit Kb (NH3) = 1,8.10-5.
Cu V: (3im)

Hai hp cht thm A v B l ng phn c cng thc phn t C nH2n-8O2. Hi B c khi lng
ring 5,447 gam/lt ( ktc). A c kh nng phn ng vi Na gii phng H 2 v c phn ng trng gng.
B phn ng c vi NaHCO3 gii phng kh CO2.
a) Vit cng thc cu to ca A v B.
b) Trong cc cu to ca A, cht A1 c nhit si nh nht. Hy xc nh cng thc cu to ng ca
A1.
c) Vit cc phng trnh phn ng chuyn ha ocrezol thnh A1.
Cu VI: (4,0 im).
1/. Cho 20,80 gam hn hp Fe, FeS, FeS 2, S tc dng vi dung dch HNO3 c nng d thu c V lt
kh NO2 (l sn phm kh duy nht, o ktc) v dung dch A. Cho A tc dng vi dung d ch Ba(OH) 2 d
thu c 91,30 gam kt ta. Tnh V?
2/. Cho m gam hn hp hai kim loi Fe, Cu (trong Fe chi m 30% v kh i l ng) vo 50 ml dung
dch HNO3 nng 63% (d = 1,38 gam/ml) un nng, khuy u hn hp ti cc ph n ng hon ton thu
c rn A cn nng 0,75 m gam, dung dch B v 6,72 lt hn hp kh NO 2 v NO ( ktc). Hi c cn
dung dch B th thu c bao nhiu gam mui khan? (Gi s trong qu trnh un nng HNO 3 bay hi
khng ng k)
( Cho H=1, C=12, N=14, O=16, Na=23, S=32, K =39, Fe=56, Cu=64, Zn=65, Ba =137)
----------------- HT
----------------

( Hoc sinh chi c s dung

bang
tun
hoan)

TRNG THPT TX NGHIA

L
Ki thi chon
hoc sinh gioi cp
trng
Ngy thi: 15/9/2013
Cu

HNG DN CHM HOC

SINH GIOI MN HOA
LP
12
Nm hoc 2013-2014
Thi gian : 180 phut

Hng dn chm
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 H2SO4 l cht oxi ho mnh cn HBr v HI trong dung dch l

im
0,25

0,25

nhng cht kh mnh, do p dng phng php sunfat s khng thu c

HBr v HI m thu c Br2, I2.
Cc phng trnh phn ng:
CaF2
+
H2SO4 , nng

NaCl
+
H2SO4 , nng

Cu I:

2NaCl

NaBr

2HBr

NaI

HCl

NaHSO4

2HCl

NaHSO4

0,5

Na2SO4
HBr

SO2

+ 2H2O +
NaHSO4 + HI

Br2

a/s

HCl

3 /. a) CO

CaSO4

H2SO4 , nng
H2SO4 , nng

H2SO4 , nng
H2S + 4H2O + 4I2

2/ . Axit hipoclor :
- Tnh axit rt yu, yu hn axit cacbonic
NaClO
+
CO2 +
H2O
+
HClO
NaHCO3
Tnh oxi ho mnh lit, a cht phn ng c s oxi ho cao nht
-2
+6

4HClO + PbS
4HCl
+
PbSO4
- D b phn tch :
6 HI

HClO

Cu II

H2SO4 , nng
H2SO4 , nng

2HF

+
CuO

to

O ;

3HClO 2HCl
to

CO2

0,25

+ HClO3

0,25

Cu

0,25
0,25
0.25
0,25

b) H2S +
CuCl2
CuS +
2 HCl
c) HCl +
NaHS
NaCl
+
H2S
d) HCl +
NaHSO3
NaCl
+ SO2 + H2O
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 XY3 , ta c cc phng trnh:
Tng s ba loi ht:
2 Zx + 6 Zy + Nx + 3 Ny = 196
2 Zx + 6 Zy
Nx 3 Ny =
60
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

0,5

(1)
(2)

Vy X l nhm, Y l clo. XY3 l AlCl3 .

b) Cu hnh electron:
Al : 1s2 2s2 2p6 3s2 3p1
Cl : 1s2 2s2 2p6 3s2 3p5
1
c) X : n = 3, l = 1, ml = -1, ms = +
2
1
Y : n = 3, l = 1, ml = 0, ms = 2
d) Cc phng trnh phn ng to thnh AlCl3:
Al

to

3Cl2

0,25
0,25
0,5
0,5

2AlCl3

1,5

2Al
+
3CuCl2
2AlCl3 + 3Cu
Al2O3
+
6HCl
2AlCl3
+
3H2O
Al(OH)3
+
3HCl
AlCl3+
3H2O
Al2S3
+
6HCl
2AlCl3 +
3H2S
NaAlO2
+
HCl
AlCl3 +
NaCl + 2H2O
Al2(SO4)3
+ 3BaCl2
2AlCl3 + BaSO4
Phan ng xay ra :
CH3COOH + C2H5OH CH3COOC2H5 + H2O
Ban u :
1
1
0
0
2
3
1
3

Phan ng :
Cu III:

Cn bng
:

2
3
1
3

2
3
2
3

2 2
.
Ta co : K = 3 3 = 4
1 1
.
3 3
Phan ng :
CH3COOH + C2H5OH CH3COOC2H5 + H2O
Ban u :
1
2
Cn bng
:
1-x
2-x
x
x
Hng
s cn bng

:K=

x.x
=4
(1 x )(2 x )

K: x < 1

2
3
2
3

0,5

1
0,5
0,5

3x2 - 12x + 8 = 0

Giai PT bc 2 thu c 2 nghim:

x1 = 0,845; x2 = 3,15 (loai)

Vy
tai thi im
luc cn bng
co 0,845 mol este
Cu IV:

a/ Ta co: C = C0. =

0,1.4,3
= 4,3.10-3 M
100

Cn bng
xay
ra :
CH3COOH CH3COO- + H+
4,3.10-3
4,3.10-3 4,3.10-3
[H+] = 4,3.10-3 pH = 2,34
0, 050 0, 200
0, 075 0,100
o
o
= 0, 08M ; C NaOH
=
= 0, 06 M
b/ CNH 4Cl =
0,125
0,125
NH4Cl + NaOH NaCl + NH3 + H2O

0,08
0,06
0,06
0,06
0,06
0,02
0
0,06
Xt cn bng :
NH3 + H2O NH4+ + OH-

0,5
0,25
0,25
0,5
0,25
0,25
0,25

0,06
x
0,06x

0,25

0,02
x
0,02+ x

x
x

[ NH +4 ][OH ] (0,02 + x ) x
Kb =
=
= 1,8.10 5 ,
[ NH 3 ]
0,06 x
x =1,8.10 5

0,25

gn ng
0,25

0,06
= 5,4.10 5 M
0,02

pH =14 [ lg(5,4.10 5 )] =9,73

a) MB = 5,447.22,4 = 122 (gam/mol) 14n + 24 = 122 n = 7. Vy cng

thc phn t ca A v B l C7H6O2
A + Na H2
A tp chc c 1 nhm OH v 1 nhm CHO
A + AgNO3/NH3
A c ba cng thc
cu
to :

CHO

CHO

CHO

0,25
0,25
0,5
0,25
0,25

OH
0,5

OH
Cu V

OH
B + NaHCO3 CO2 Vy B c cng thc cu to :

COOH

0,25

3
b)

CHO

A1 l

OH

v A1 c lin kt H ni phn t, nn nhit si thp hn so vi 2 ng phn

cn li
a) Phng trnh chuyn ha o-cresol thnh A1
1:1
o-HO-C6H4-CH3 + Cl2 as,
o-HO-C6H4-CH2Cl + HCl
o-HO-C6H5-CH2Cl + 2NaOH t o-NaO-C6H5-CH2OH + 2NaCl +H2O
o-NaO-C6H5-CH2OH + CuO t o-NaO-C6H5-CHO + H2O + Cu
o-NaO-C6H5-CHO + HCl t o-HO-C6H5-CHO + NaCl

0,25
0,25

Cu VI

1/ Do sn phm cui cng khi cho hn hp tc dng vi HNO3 c nng c

Fe3+, SO42- nn c th coi hn hp ban u l Fe v S. Gi x v y l s mol ca
Fe v S, s mol ca NO2 l a
Fe Fe+3 + 3e
x
x
3x
S S+6 + 6e
y
y
6y
+5
+4
N + e N
a
a
a
A tc dng vi Ba(OH)2

0,25
0,25
0,25
0,5

0,5

Fe3+ + 3OH- Fe(OH)3

Ba2+ + SO42- BaSO4
x =0,2
56x +32 y =20,8
Ta c h phng trnh
Gii ra
107x +233y =91,3
y =0,3
Theo nh lut bo ton electron : 3x + 6y = a = 3.0,2 + 6.0,3 = 2,4
V = 2,4.22,4 = 53,76 (lt)
2/ Khi lng Fe = 0,3m (g); khi lng rn A = 0,75 m(g). Suy ra lng Fe
phn ng = 0,25 m Fe d ; Cu cha phn ng. Dung dch B cha Fe(NO3)2,
khng c Fe(NO3)3 v Cu(NO3)2
nhn hpkh = 6,72/22,4= 0,3 mol
S mol HNO3 =

50.1,38.63
= 0,69 (mol)
100.63

Fe Fe+2 + 2e
NO3- + 3e NO
NO3- + e NO2
S mol NO3- to mui = 0,69 0,3 = 0,39 (mol)
1
Khi lng Fe(NO3)2 = .0,39(56 + 62.2) = 35,1( g ) (gam)
2

----------------------------Ht ------------------------------------------- Hc sinh lm cch khc ng vn cho im ti a

- Vit thiu hc khng iu kin th cho s im

0,5
0,5
0,5
0,5

1,0