B GIO DC V O TO

K THI CHN HC SINH GII QUC GIA

LP 12 THPT NM 2011
P N THI CHNH THC
Mn: HO HC
Ngy thi th nht: 11/01/2011
(Gm 06 trang)

Cu 1

1
(2,0
im)

a) Cng thc cc hp cht XFm:

X l Cl c ClF; ClF3; ClF5 (a); X l Br c BrF; BrF3; BrF5 (b);
X l I c IF; IF3; IF5; IF7 (c).
b) Cc hp cht trn u c lin kt cng ha tr, mi lin kt c to thnh do 2
electron c spin i song song ca 2 nguyn t gp chung.
* F (Z = 9; n = 2) c 4 AO ha tr, v vy cu hnh ch c 1 electron c thn:
* Cl (Z = 17; n = 3), Br (Z = 35; 9n = 4), I (Z = 53; n = 5) ging nhau u c 9 AO
ha tr, c th c:
1 electron c thn:
hoc 3 electron c thn:
5 electron c thn:
7 electron c thn:
- Hp cht ClF7 khng tn ti v th tch nguyn t clo rt nh, lc y ca cc v
nguyn t flo s ph v lin kt trong phn t. Hp cht BrF7 tng t hp cht ClF7
(hp cht BrF7 hin nay cha iu ch c).
- Hp cht IF7 tn ti v th tch nguyn t iot rt ln so vi th tch nguyn t flo, lc
y ca cc v nguyn t flo khng ph v c cc lin kt trong phn t.

2
(1,5

im)

a) Phng trnh phn ng ht nhn iu ch 32P:

v phn r phng x ca 32P:

16

32

15

S + 01n 1532P + 11p

P
1632S + -

32

t/t1/2

A
5.10-1Ci 1 1
t/t1/2 = 2 t = 2.t1/2. Vy thi gian lu gi l 2
=
= =
A0
2Ci
4 2
chu k bn hu.
Tc phn r phng x khng ph thuc vo nng u v nhit , nn sau
thi gian lng 32P ca mu I cng ch cn li 1/4 so vi lc u gim hot
3
phng x trong mu I l: 20 mCi =15 mCi = 15.10-3.3,7.1010 Bq = 15.3,7.107 Bq.
4
S ht nhn bin i phng x l:
A A.t1/2 15.3,7.107 .14,28.24.3600
=
=
= 9,9.1014 nguyn t
N=

ln2
0,693
b)

32.9,9.1014
= 5,3.10-8 (g) = 5,3.10-2 (g)
Khi lng P phn r l: m 32 P =
23
6,02.10
Khi b qua s ht khi ca phn r phng x, khi lng 32S to thnh ng bng
khi lng 32P phn r: m(32S) = 5,3.10-2g.
32

Trang 1/6

Cu 2
1
(1,0
im)

2
(0,75
im)
3
(1,75
im)

Phn ng l bc 1 nn: [X] = [X]0.e-kt (1) v = k[X] = k.[X]0.e-kt

lnv = ln(k[X]0) - kt (2) Hay: lnv = lnv0 - kt (3) (v0 l tc u ca phn
ng) lgv = lgv0 kt/2,303.
v
k = 0 = 4.10-4/2.10-2 = 2.10-2(pht-1) lgv = -3,4 - 8,7.10-3t
[X]0
(t: pht; v: mol.L-1.pht-1).
(Nhng biu thc trong lgv l hm ca mt bin s c lp t u coi l ng).

i vi phn ng bc 1:
ln2
0,693
=
= 34, 7 (pht)
k 2.10-2 (pht) 1
Phn ng 2NO (k) + 2H2 (k) N2 (k) + 2H2O (k) tun theo quy lut ng
hc thc nghim: v = k[NO]2[H2].
C ch 1:
k1
2NO (k)
N2O2 (k)
(nhanh)
(1)
k2
(nhanh)
(2)
N2O2 (k) + H2 (k) 2HON (k)
k3
(chm)
(3)
HON (k) + H2 (k) H2O (k) +HN (k)
t1/2 =

4
HN (k) + HON (k)
N2 (k) + H2O (k) (nhanh)
(4)
Chp nhn gn ng rng giai on quyt nh tc phn ng l giai on
chm nht.
* Trong c ch cho, giai on 3 chm, quyt nh tc phn ng, nn:
v = k3.[HON][H2]
(5)
Khi nng cc sn phm trung gian t c trng thi dng
d[N 2 O 2 ] 1
k [NO]2
= k1[NO]2 k2[H2][N2O2] = 0 (6) [N2O2] = 1
(7)
2
dt
2k 2 [H 2 ]
d[HON]
= 2k2[H2][N2O2] - k3.[HON][H2] k4[HON][HN] = 0
(8)
dt
d[HN]
= k3.[HON][H2] k4[HON][HN] = 0
(9)
dt
k [N O ]
(10)
Ly (8) tr (9) v bin i n gin, ta c: [HON] = 2 2 2
k3

Thay (7) vo (10) rt ra:

[HON] =

k1[NO]2
2k 3 [H 2 ]

(11)

k1[NO]2
= k[NO]2. Kt qu ny khng ph hp
2
vi inh lut tc thc nghim. C ch 1 l khng c kh nng.
C ch 2:
2NO
N2O2
Kcb
(nhanh)
(12)
k5
(chm)
(13)
N2O2 + H2 N2O + H2O
k6
N2O + H2 N2 + H2O
(nhanh)
(14)
Tc phn ng c quyt nh bi (13), nn: v = k5[N2O2].[H2] (15)
Da vo cn bng 2 NO
N2O2, rt ra: [N2O2] = Kcb.[NO]2
(16)
Thay (16) vo (15) thu c: v = Kcb.k5[NO]2.[H2] = k[NO]2.[H2].
Kt lun: C ch 2 cho php rt ra biu thc ca nh lut tc thc nghim. C
ch ny l c kh nng.
Thay (11) vo (5) thu c: v =

Trang 2/6

Cu 3
1
(0,75
im)

N2 + 3H2

2NH3

(1)

298K, H 0r = - 91,8 kJ.mol-1; S0r = -198,1 J.mol-1.K-1;

G 0r = H 0r 298. S0r = -32,8 (kJ.mol-1);
G 0r = -R.T.lnK lnK = - G 0r (R.T)-1 = 13,24 K = 5,62.105.

2
(1,5
im)

a) Tnh hng s cn bng K ca phn ng T = 773 K:

773K: G 0r (773 K) = H 0r - T. S0r - 91,8 + 773.198,1.10-3 = 61,3 (kJ.mol-1)
lnK = - 61,3.103.(8,314.773)-1 = - 9,54 K = e-9,54 = 7,2.10-5.
b) 298 K, hng s cn bng K >> 1. Phn ng (1) din ra u tin theo chiu thun.
773 K, hng s cn bng K << 1. Phn ng (1) din ra u tin theo chiu nghch.
Mc d nhit cao (773K), phn ng (1) din ra u tin theo chiu nghch,
nhng tc phn ng ln, cn tc phn ng 298 K qu nh. tng tc phn
ng, lm h nhanh t n cn bng, ngi ta buc phi tin hnh phn ng nhit
cao.
tng hiu sut tng hp amoniac trong cng nghip:
- Phn ng (1) gim s mol kh. cn bng chuyn dch theo chiu thun, tng hiu
sut tng hp amoniac cn thc hin phn ng p sut cao.
- Hiu sut to thnh amoniac l cc i khi t l ca kh H2 v kh N2 c ly ng
bng t l cc h s ca chng trong phng trnh phn ng, ngha l H2 : N2 l 3 : 1.

3
(0,5
im)

Tnh bin thin entanpi phn li lin kt H 0b ca mt lin kt N-H trong phn t amoniac:
N2 + 3H2 2NH3
2H1 = 2.(-45,9) kJ.mol-1 (1)
N2
2 Ni
H2 = 945 kJ.mol-1
(2)
-1
3H2
6 Hi
3H3 = 3.436 kJ.mol
(3)
0
T (1), (2), (3), ta c: 2 Ni + 6 Hi 2NH3
6 H (N-H)
6 H 0(N-H) = -2.45,9 945 3.436 = - 2344,8 (kJ.mol-1) H 0b(N-H) = 390,8 kJ.mol-1

4
(0,75
im)

Tnh bin thin entanpi hnh thnh tiu chun H 0f ca gc NH2:

N2 + 3H2 2NH3
2H1 = 2.(-45,9) kJ.mol-1
H2
2 Hi
H3 = 436 kJ.mol-1
2NH3
2 i NH 2 + 2 Hi 2H4 = 2.380 kJ.mol-1
T (1), (3), (4), c: N2 + 2H2 2 i NH 2

(1)
(3)
(4)

2 H 0f( i NH 2 )

2 H 0f( i NH 2 ) = - 2.45,9 436 + 2.380 = 232,2 (kJ/mol) H 0f( i NH 2 ) = 116,1 kJ/mol

Cu 4
1
(1,0
im)

Sau khi trn: CMnO- = 0,0040 M; CH 2C2O4 = 0,050 M ; CH + = 0,20 M

4

Mn2+ + 4H2O
2CO2 + 2H+ + 2e
2 MnO-4 + 5H2C2O4 + 6H+ 2Mn2+ + 10CO2 + 8H2O

Phn ng: 2
5

0,0040
-

MnO-4 + 8H+ + 5e
H2C2O4

0,050
0,040

0,20
0,188

0,0040

K = 10337,84

0,020

TPGH: H2C2O4 0,040 M; H+ 0,188 M; CO2 0,020 M (< LCO2 = 0,030 M); Mn2+ 0,0040 M.

Trang 3/6

2
(2,0
im)

Trn dung dch A v dung dch B:

CH 2C2O 4 = 0,020 M; CH + = 0,094 M; CCO2 = 0,010 M; CMn 2+ = 0,0020 M;
CCa 2+ = 0,010 M; CBa 2+ = 0,050 M.

V s phn li ca axit cacbonic (hn hp H2O+CO2) khng ng k trong mi trng

axit, do c th coi [CO2] 0,010 M v kh nng ch xut hin kt ta oxalat (nu c).
Xt th t kt ta:
K s(CaC2O4 )
10-8,75
- c kt ta CaC2O4: C'C O2- (1)
=
= 10-6,75 M
'
2 4
0,01
CCa 2+
- c kt ta BaC2O4: C'C O2- (2)
2

K s(BaC2O4 )
C'Ba 2+

10-6,8
= 10-5,5 M
0,05

V C'C O2- (1) < C'C O2- (2) CaC2O4 s kt ta trc. Do K a1(H 2C2O4 )
2

nng cc cu t c tnh theo cn bng:

H+
H2C2O4
C' 0,020 x

C'H+

= x = 7,15.10 M;

K a1 = 101,25

HC2 O-4

0,094+x

-3

C'HC O2 4

K a2(H2C2O4 ) nn

= 0,1012 M

x
C'C O22 4

= K a2

C'HC O2

C'H+

= 10-5,42 M

C'Ca 2+ . C'C O2- = 0,01.10-5,42 =10-7,42 > 10-8,75 = K s(CaC2O4 ) c CaC2O4 kt ta theo
2

Ca2+ + H2C2O4 CaC2O4 + 2H+

phn ng:

0,010
-

0,020
0,010

K = 103,23

0,094
0,114

nh gi kh nng kt ta BaC2O4 t lng d H2C2O4:

H+ + HC2 O-4
Tng t:
H2C2O4

K a1 = 101,25

C' 0,010 y
0,114+y
y
-3
'
'
CHC O- = y = 3,24.10 M; CH+ = 0,117 M C'C O2- = 10-5,83 M
2

C'Ba 2+
Khi

. C'C O22 4

C'Ca 2+

-5,83

= 0,05.10

K s(CaC2O4 )
C,C O22

'
Kim tra: CCO
2- =
3

-7,13

=10

-6,8

< 10

= K s(BaC2O4 ) khng c BaC2O4 kt ta.

108,75
= 5,83 = 102,92 (M)
10

K 'a1.K 'a2 .[CO 2 ] 1016,68.0, 01

=
= 1,53.10-17 (M)
+ 2
2
[H ]
(0,117)

C'Ca 2+ .C'CO2- < K s(CaCO3 ) ;C'Ba 2+ .C'CO2- < K s(BaCO3 ) khng c CaCO3 v BaCO3 tch ra.
3

Trang 4/6

Cu 5
1
(2,25
im)

a) Tnh E 0

MnO-4 , H 2O/MnO 2

v E 0

MnO-4 /MnO24

MnO-4 + 8H+ + 5e

Mn2+ + 4H2O

K1 = 105.1,51/ 0,0592

Mn2+ + 2H2O

MnO2 + 4H+ + 2e

2.1,23 / 0,0592
K -1
2 = 10

MnO2 + 2H2O

+
MnO 24 + 4H + 2e

K 3-1 = 102.2,26 / 0,0592

MnO-4

MnO 24

+e

K 4 = K1.K -12 .K 3-1 E 0

MnO-4 /MnO24

K 4 = 10

(E 0

MnO-4 /MnO24

) / 0,0592

= 5.1,51 2.(1,23+2,26) = 0,57 (V)

MnO-4 + 8H+ + 5e

Mn2+ + 4H2O

K1 = 105.1,51/ 0,0592

Mn2+ + 2H2O

MnO2 + 4H+ + 2e

2.1,23 / 0,0592
K -1
2 = 10

OH- + H+

K w = 1014

4 H2O
MnO-4

+ 2H2O + 3e

K 5 = K1.K -12 .K 4w E 0

MnO-4 , H 2O/MnO 2

b) E 0

MnO-4 , H + /Mn 2+

K 5 = 10

MnO2 + 4OH

> E0

MnO-4 , H 2O/MnO 2

(3E 0

MnO-4 /MnO 2

) / 0,0592

5.1,51 2.1, 23 14.4.0, 0592

= 0,59 (V)
3

> E0

MnO-4 /MnO24

kh nng oxi ha ca

MnO-4 mnh nht trong mi trng axit v yu nht trong mi trng baz, bi v:

MnO-4 , H + /Mn 2+

= E

MnO-4 , H + /Mn 2+

0,0592 [MnO-4 ][H + ]8

lg
5
[Mn 2+ ]

do khi pH tng, [H+] gim, tnh oxi ha ca MnO-4 gim.

2
(0,75
im)

Cc phn ng minh ha kh nng oxi ha ca ion pemanganat ph thuc vo pH

ca mi trng:
MnO-4 + 5Fe2+ + 8H+
Mn2+ + 5Fe3+ + 4H2O
2 MnO-4 + 3 Mn 2+ + 2H2O
5MnO2 + 4H+
t

2 MnO-4 + SO32- + 2OHCu 6

1
(2,25
im)

22 MnO 24 + SO 4 + H2O

t
Cr2O3 + 3Na2O2 + H2O
2 CrO24 + 2OH- + 6Na+ (1)
t
O2 + 4OH- + 4Na+
2Na2O2 + 2H2O
+
OH
+ H
H2O
+
2
2 CrO4 + 2H
Cr2 O27 + H2O
Fe2O3 + 6H+ 2Fe3+ + 3H2O
Cr2 O27 + 9I- + 4 H+ 2 Cr3+ + 3 I3- + 7H2O

2Fe3+

3I-

2 S 2 O32 + I3Fe3+ + 3F2

(0,25
im)

(2)
(3)
(4)
(5)
(6)

2Fe2+ + I3-

(7)

S 4 O62 + 3IFeF3

(8)
(9)

Vai tr ca dung dch NaF: F- c mt trong dung dch to phc bn, khng mu vi
Fe3+, dng che Fe3+.

Trang 5/6

3
(1,0
im)

t s mol ca Cr2O3 v Fe2O3 trong 1,98 gam mu ln lt l n Cr2O3 = x; n Fe2O3 = y

T (1), (4) v (5) trong 10,00 mL dung dch A s mol ca Cr2 O27 l n Cr O2- = 0,1x;
2

3+

s mol ca Fe l n Fe3+ = 0,2y.

Trng hp NaF khng c mt trong dung dch A, c Cr2 O72 v Fe3+ u b kh bi I-.
Theo (6) v (7) ta c: n I- (1) = 3 n Cr O2- + 0,5 n Fe3+ = 3.0,1x + 0,5.0,2y = 0,3x + 0,1y
3

T (8): n S O2- (1) = 2 n I- (1) 0,40.10,50.10-3 = 2.(0,1y + 0,3x)

2

Trng hp NaF c mt trong dung dch A, ch c Cr2 O27 b kh:

n I- (2) = 3 n Cr O2- = 0,3x 0,40.7,50.10-3 = n S O2- (2) = 2 n I- (2) = 0,6x
3

(10)
(11)

T (11) v (10) x = 0,005 (mol) v y = 0,006 (mol).

52.0, 01
.100 = 26,26%
1,98
56.0, 012
.100 = 33,94%.
n Fe = 2 n Fe2O3 = 2.0,006 = 0,012 (mol) %Fe trong mu l:
1,98
n Cr = 2 n Cr2O3 = 2.0,005 = 0,01 (mol) %Cr trong mu l:

--------------------------HT--------------------------

Trang 6/6