I.

OLYMPIC HA HC VIT NAM:

OLYMPIC HA HC SINH VIN TON QUC 2003 (Bng A):
Brom lng tc dng c vi H
3
PO
3
theo phn ng:
H
3
PO
3
+ Br
2
+ H
2
O H
3
PO
4
+ 2H
+
+ 2Br
-

1) Tnh hng s cn bng ca phn ng 298K
2) Tnh th in cc chun E
o
(H
3
PO
4
/H
3
PO
3
) nu bit E
o
(Br
2
/2Br
-
) = 1,087V
3) Tnh th in cc chun E
o
(H
3
PO
3
/H
3
PO
2
) nu bit E
o
(H
3
PO
4
/H
3
PO
2
) = 1,087V
Cho bit cc s liu sau 298K:
H
+
(dd) H
3
PO
4
(dd) Br
-
(dd) H
3
PO
3
(dd) Br
2
(l) H
2
O(l)
H
o
tt
(kJ/mol) 0 -1308 -141 -965 0 -286
S
o
(J/mol.K) 0 -108 83 167 152 70
BI GII:
1) H
o
p
= -339kJ
S
o
p
= -331JK
-1
.
G
o
p
= -240,362kJ lgK 42,125 K = 1,33.10
42
.
2) G
o
p
= -nFE
o
p
E
o
p
= 1,245V
E
o
(Br
2
/2Br
-
) - E
o
(H
3
PO
4
/H
3
PO
3
) = E
o
p
= 1,245V
E
o
(H
3
PO
4
/H
3
PO
3
) = -0,158V ~ - 0,16V
3) H
3
PO
4
+ 4H
+
+ 4e H
3
PO
2
+ 2H
2
O E
o
1
= - 0,39V (1)
H
3
PO
4
+ 2H
+
+ 2e H
3
PO
3
+ H
2
O E
o
1
= - 0,16V (2)
Ly phng trnh (1) (2) ta c: H
3
PO
2
+ 2H
+
+ 2e H
3
PO
2
+ H
2
O E
o
3
= ?
G
o
3
= G
o
1
- G
o
2
-2FE
o
3
= -4FE
o
1
(-2FE
o
2
) E
o
3
= -0,62V
OLYMPIC HA HC SINH VIN TON QUC 2003 (Bng A):
Cho bit cc th in cc chun: E
o
(Cu
2+
/Cu) = 0,34V; E
o
(Cu
2+
/Cu
+
) = 0,15V; E
o
(I
2
/2I
-
) =
0,54V.
1) Hi ti sao ngi ta c th nh lng Cu
2+
trong dung dch nc thng qua dung dch KI?
Cho bit thm rng dung dch bo ho ca CuI trong nc nhit thng (25
o
C) c
nng l 10
-6
M
2) S dng tnh ton xc nh xem Cu c tc dng c vi HI gii phng kh H
2
hay
khng?
3) Mui Cu
2
SO
4
c bn trong nc hay khng? Gii thch.
BI GII:
1) Cu
2+
+ e Cu
+
E
o
1
= 0,15V
Cu
2+
+ I
-
+ e CuI E
o
2
= ?

| || |
| |
+
+
+ =
Cu
I Cu
E E
o o
2
1 2
lg 059 , 0
[Cu
2+
] = [I
-
] = 1M | |
| |
M
I
K
Cu
s 12
10

+
= =
E
o
2
= 0,15 + 0,059lg10
12
= 0,86 > E
o
(I
2
/I
-
)
Vy c phn ng: Cu
2+
+ 3I
-
CuI + I
2
.
nh lng I
2
theo phn ng: I
2
+ Na
2
S
2
O
3
Na
2
S
4
O
6
+ 2NaI
2) Cu
2+
+ 2e Cu E
o
1
= 0,34V
Cu
2+
+ e Cu
+
E
o
2
= 0,15V
Cu
+
+ e Cu E
o
3
= 0,34.2 0,15 = 0,53V
CuI + e Cu + I
-
E
o
4
= E
o
3
+ 0,059lg10
-12
= -0,17V
Vy c phn ng: 2Cu + 2HI 2CuI + H
2

3) Cu
+
+ e Cu E
o
1
= 0,53V
Cu
2+
+ e Cu
+
E
o
2
= 0,15V
2Cu
+
Cu + Cu
2+
E
o
= 0,53 0,15 = 0,38V
Vy Cu
2
SO
4
l mui tan trong nc, khng bn trong dung dch:
Cu
2
SO
4
Cu + CuSO
4

OLYMPIC HA HC SINH VIN TON QUC 2005 (Bng A):
loi tr cc ion NO
3
-
trong nc (cc ion NO
3
-
c mt trong nc xut pht t phn
bn) c th kh n thnh NO
2
-
bng cch cho i qua li c cha bt Cd.
1) Vit na phn ng ca hai cp NO
3
-
/HNO
2
v HNO
2
/NO trong mi trng axit. Chng
minh rng HNO
2
b phn hy trong mi trng pH = 0 n 6.
2) pH = 7, nng NO
3
-
l 10
-2
M. Vit phn ng gia Cd v NO
3
-
. Hi NO
3
-
c b kh
hon ton 25
o
C trong iu kin ny khng? Tnh nng NO
3
-
cn li trong nc khi
cn bng.
3) Tnh th kh (th oxy ha - kh) chun ca cp NO
3
-
/NO
2
-
pH = 14 v 25
o
C
Cho bit cc s liu sau 25
o
C: E
o
(NO
3
-
/HNO
2
) = 0,94V; E
o
(HNO
2
/NO) = 0,98V;
E
o
(Cd
2+
/Cd) = -0,40V; K
a
(HNO
2
) = 5.10
-4
; K
s
(Cd(OH)
2
) = 1,2.10
-14
.
BI GII:
1) NO
3
-
+ 3H
+
+ 2e HNO
2
+ H
2
O; E
o
= 0,94V
HNO
2
+ H
+
+ e NO + H
2
O; E
o
= 0,98V
pH = 0 th E
o
(HNO
2
/NO) > E
o
(NO
3
-
/HNO
2
) nn HNO
2
b phn hy theo phn ng:
3HNO
2
NO
3
-
+ 2NO + H
+
+ H
2
O
pH = 6 th:
E
o
(NO
3
-
/HNO
2
) = 0,94 + 0,059/2(lg10
-6
) =
E
o
(HNO
2
/NO) = 0,98 + 0,059lg10
-6
= 0,626V
E
o
(HNO
2
/NO) vn ln hn E
o
(NO
3
-
/HNO
2
) nn HNO
2
vn khng bn
2) Cd + NO
3
-
+ H
2
O Cd
2+
+ NO
2
-
+ 2OH
-

Gi thit phn ng l hon ton th [Cd
2+
] = [NO
3
-
]
b
= 10
-2
M
pH = 7 th [Cd
2+
] = K
s
/[OH
-
]
2
= 1,2M. Nng Cd
2+
sau phn ng nh hn nhiu so vi
1,2M nn khng c kt ta Cd(OH)
2
.
tnh [NO
3
-
] khi cn bng cn tnh hng s cn bng K ca phn ng trn:
Cd + NO
3
-
+ H
2
O + 3H
+

K
Cd
2+
+ NO
2
-
+ 2OH
-
+ 3H
+



Cd
2+
+ HNO
2
+ 2H
2
O
2
K
Cd
2+
+ H
+
+ NO
2
-
+ 2H
2
O
K = K
1
.K
2
.K
3
.
14 2 14 4 45
45
1 1
10 . 325 , 1 ) 10 .( 10 . 5 . 10 . 65 , 2
10 . 65 , 2 42 , 45
059 , 0
) 40 , 0 94 , 0 ( 2
lg
= =
= =
+
=

K
K K

Hng s K rt ln nn phn ng gn nh hon ton. pH = 7 ta c:
Cd + NO
3
-
+ H
2
O Cd
2+
+ NO
2
-
+ 2OH
-
Ncb: (10
-2
x) = c x = 10
-2
x = 10
-2
10
-7

Nh vy ta c:
K1 K1
| | M NO
33
3
2 7 2 2
14
10 . 55 , 7
) 10 .( 10 . 10
10 . 325 , 1


= = = c
c

3) V E
E
K
o
NO NO
o
NO NO
017 , 0
059 , 0
) 40 , 0 ( 2
lg
2 3
2 3
/
/
1
=
+
=



OLYMPIC HA HC SINH VIN TON QUC 2005 (Bng A):
C th ho tan hon ton 100mg bc kim loi trong 100ml dung dch amoniac nng
0,1M khi tip xc vi khng kh c khng?
Cho bit nguyn t khi ca Ag = 107,88; hng s in li baz ca amoniac l K
b
=
1,74.10
-5
; cc hng s bn ca phc [Ag(NH
3
)
i
]
+
tng ng l: lg|
1
= 3,32(i = 1) v lg|
2
= 6,23(i =
2).
Cc th kh (th oxy ha - kh) chun 25
o
C: E
o
(Ag
+
/Ag) = 0,799V; E
o
(O
2
/OH
-
) =
0,401V. p sut ring phn ca oxy trong khng kh l 0,2095atm. Phn ng c thc hin
25
o
C.
BI GII:
N
Ag
= 0,100 : 107,88 = 9,27.10
-4
mol
S mol cc i ca NH
3
cn to phc l: 9,27.10
-4
. 2 = 1,854.10
-3
M ngha l nh hn
nhiu so vi s mol NH
3
c trong dung dch (10
-2
M). Vy NH
3
rt d ho tan lng Ag nu
xy ra phn ng.
Chng ta s kim tra kh nng ho tan theo quan im in ha v nhit ng:
Ag
+
+ e Ag E
1
= E
o
1
+ 0,059lg[Ag
+
]
O
2
+ 4e + H
2
O 4OH
-
| |
4
2 2
2
lg
4
059 , 0

+ =
OH
P
E E
O
o

Khi cn bng E
1
= E
2
. Trong dung dch NH
3
= 0,1M (lng NH
3
phn ng khng ng
k) ta c: [OH
-
] = (K
b
.C)
1/2
= 1,32.10
-3
M
E
2
= 0,5607V.
V E
2
= E
1
nn t tnh ton ta c th suy ra c [Ag
+
] = 9,12.10
-5
M
Nng tng cng ca Ag
+
trong dung dch:
[Ag
+
]
o
= [Ag
+
] + [Ag(NH
3
)
+
] + [Ag(NH
3
)
2
+
]
= [Ag
+
](1 + |
1
[NH
3
] + |
1
|
2
[NH
3
]
2
) = 15,5M
Gi tr ny ln hn nhiu so vi lng Ag dng cho phn ng. V vy cc iu kin in
ha v nhit ng thun li cho vic ho tan 0,100g Ag
OLYMPIC HA HC SINH VIN TON QUC 2005 (Bng B):
1) Trn hai th tch bng nhau ca hai dung dch SnCl
2
0,100M v FeCl
3
0,100M. Xc nh
nng cc ion thic v st khi cn bng 25
o
C. Tnh th ca cc cp oxy ha - kh khi
cn bng.
2) Nhng mt si Ag vo dung dch Fe
2
(SO
4
)
3
2,5.10
-2
M. Xc nh nng ca Fe
3+
; Fe
2+
v
Ag
+
khi cn bng 25
o
C. Tnh th ca cc cp oxy ha - kh khi cn bng.
Cho bit E
o
(Sn
4+
/Sn
2+
) = 0,15V; E
o
(Fe
3+
/Fe
2+
) = 0,77V; E
o
(Ag
+
/Ag) = 0,80V
BI GII:
1) Sn
2+
+ 2Fe
3+
Sn
4+
+ 2Fe
2+

Ncb: 0,05- x 0,05 2x x 2x
lgK = 2(0,77 015)/0,059 = 21 K = 10
21
.
K rt ln v nng Fe
3+
cho phn ng nh hn nhiu so vi Sn
2+
phn ng gn nh
hon ton: 2x ~ 0,05
[Fe
2+
] = 0,05M; [Sn
4+
] = 0,025M; [Sn
2+
] = 0,025M; [Fe
3+
] = cM
K = | | M Fe
12 3
2
21
2
2
10 . 58 , 1
0025 , 0
10 . 1
. 025 , 0
) 05 , 0 .( 025 , 0
+
= = = c
c c

Khi cn bng E
cb
= 0,77 + 0,059lg M 15 , 0
025 , 0
025 , 0
lg
2
059 , 0
15 , 0
05 , 0
10 . 58 , 1
12
= + =

2) Ag + Fe
3+
Ag
+
+ Fe
2+

ncb: 0,05 x x x
lgK = (0,77 0,80)/0,059 = -0,51 K = 0,31
Ta c:
| | | |
| | M Fe
M Fe Ag x
x
x
3 3
2 2
2
10 . 6
10 . 38 , 4 31 , 0
05 , 0
+
+ +
=
= = = =

E
cb
= V 72 , 0 10 . 38 , 4 lg 059 , 0 80 , 0
10 . 38 , 4
10 . 6
lg 059 , 0 77 , 0
2
2
3
= + = +

K THI CHN HC SINH GII QUC GIA VIT NAM 2002 (BNG A)
1. Bit th oxi ha-kh tiu chun :
E
o
Cu
2+
/Cu
+
= +0,16V, E
o
Cu
+
/Cu = +0,52V, E
o
Fe
3+
/Fe
2+
= +0,77V, E
o
Fe
2+
/Fe
= -0,44V
Hy cho bit hin tng g xy ra trong cc trng hp sau:
(a) Cho bt st vo dung dch Fe
2
(SO
4
)
3
0,5M.
(b) Cho bt ng vo dung dch CuSO
4
1M.
2. Dung dch X gm Na
2
S 0,010M, KI 0,060M, Na
2
SO
4
0,050M.
Axit ho chm dung dch X n pH = 0. Thm FeCl
3
cho n nng 0,10M.
i Tnh th ca cc platin nhng trong dung dch thu c so vi cc calomen bo
ho (Hg
2
Cl
2
/2Hg,2Cl
-
).
ii Biu din s pin, vit phng trnh phn ng xy ra ti cc in cc v phn
ng tng qut khi pin hot ng.
Cho : axit c H
2
S pK
1
= 7,00, pK
2
= 12,90; HSO
4
-
c pK = 2,00; Tch s tan
ca PbS = 10
-26
; PbSO
4
= 10
-7,8
; PbI
2
= 10
-7,6
.
E
o
Fe
3+
/Fe
2+
= 0,77 V ; E
o
S/H
2
S = 0,14V ; E
o
I
2
/2I
-
= 0,54V ; E
cal bo ho
= 0,244V
BI GII:
1. a) E
o
Fe
3+
/Fe
2+
= +0,77 V > E
o
Fe
2+
/Fe = -0,44 V nn:
Tnh oxi ho: Fe
3+
mnh hn Fe
2+

Tnh kh: Fe mnh hn Fe
2+

Do phn ng t pht xy ra gia 2 cp l: 2 Fe
3+
+ Fe 3 Fe
2+

Nh vy Fe tan trong dung dch Fe(SO
4
)
3
to thnh mui FeSO
4
, lm nht mu vng ( hoc
nu) ca ion Fe
3+
v cui cng lm mt mu (hoc to mu xanh nht) dung dch.
b) E
o
Cu
+
/Cu = + 0,52 V > E
o
Cu
2+
/Cu
+
= + 0,16 V nn:
Tnh oxi ho: Cu
+
mnh hn Cu
2+
Tnh kh: Cu
+
mnh hn Cu
Do phn ng t pht xy ra giaa 2 cp l: Cu
+
+ Cu
+
Cu
2+
+ Cu
Phn ng nghch (Cu
2+
phn ng vi Cu to thnh ion Cu
+
) khng xy ra. Do khi b bt ng
vo dung dch CuSO
4
khng xy ra phn ng v quan st khng thy hin tng g.
2. Axit ho dung dch X:
S
2-
+ 2H
+
H
2
S (C H
2
S = 0,010 < S H
2
S nn H
2
S cha bo ho, khng thot ra
khi dung dch)
Phn ng: 2 Fe
3+
+ H
2
S 2 Fe
2+
+ S + 2 H
+
K=10
21

0,1 0,01
0,08 0,02 0,02
2 Fe
3+
+ 2I
-
2 Fe
2+
+ I
2
K=10
7,8

0,08 0,06 0,02
0,02 0,08 0,030
Thnh phn trong dung dch: Fe
3+
0,020 ; Fe
2+
0,080 ;I
2
0,030M ;H
+
0,02M
E Fe
3+
/Fe
2+
= 0,77 + 0,059 lg 0,02/0,08 = 0,743V (cc dng)
E
cal
= 0,244V ( cc m)
E
pin
= E
+
E

= 0,743 0,244 = 0,499V

S pin:
Hg | Hg
2
Cl
2
| KCl bh || Fe
3+
, Fe
2+
| Pt

Phn ng: 2 Hg + 2 Cl
-
= Hg
2
Cl
2
+ 2 e
+ 2x Fe
3+
+ e = Fe
2+

2 Hg + 2 Fe
3+
+ 2 Cl
-
= Hg
2
Cl
2
|


K THI CHN HC SINH GII QUC GIA VIT NAM 2002 (BNG A)
Cho dng in 0,5A i qua dung dch mui ca mt axit hu c trong 2 gi. Kt qu sau
qu trnh in phn l trn catot to ra 3,865 gam mt kim loi v trn anot c kh etan v kh
cacbonic thot ra.
1. Cho bit mui ca kim loi no b in phn? Bit rng 5,18 gam ca kim loi y c 1,59
gam Cu t dung dch ng sunfat.
2. Cho bit mui ca axit hu c no b in phn?
3. Vit cc phng trnh phn ng xy ra trn cc in cc.
BI GII:
1. in lng Q = It = 0,5 x 2 x 3600 = 3600 coulomb dng to ra 3,865 g kim
loi. T nh lut Faraday, ng lng
Khi lng mol ca kim loi: A = n. . V kim loi ny y ng ra khi dung dch nn
ng lng ca Cu:

Cu
= A/2 = 63,6/2 = 31,8 v t phn ng:
2 + Cu
2+
= Cu

+ 2
+

ta c: : 31,8 = 5,18 : 1,59, suy ra = 103,6
Trong phn ng y Cu, kim loi ch c th c mc oxi ho t 1 n 3, do s chn khi
lng mol nguyn t t 3 kh nng sau:
6 , 103
3600
9650 865 . 3
n
A
=

==
+
A
1
= 103,6 x 1 = 103,6
A
2
= 103,6 x 2 = 207,2
A
3
= 103,6 x 3 = 310,8
V khng c nguyn t vi A > 240 v bng 104 c tnh kim loi v c mc oxi ho l +1.
Do kim loi phi tm ch c th l Pb (A = 207,6).
2. Ti anot khi in phn c C
2
H
6
v CO
2
thot ra l sn phm ca s oxi ho anion
hu c, mui ny c cng thc Pb(RCOO)
2
. S to ra etan.
(CH
3
- CH
3
) v CO
2
t nhm COO
-
chng t mui in phn l
Pb(CH
3
COO)
2
.
R R
3. Cc phn ng xy ra trn cc in cc:
Ti catot: Pb
2+
+ 2 e = Pb
Ti anot: CH
3
COO
-
- e = CH
3
COO
-

CH
3
COO
-
= CH
3
-
+ CO
2

2 CH
3
-
= C
2
H
6

Tng qut: 2 CH
3
COO
-
2e = C
2
H
6
+ CO
2
.
K THI CHN HC SINH GII QUC GIA VIT NAM 2004 (BNG A)
Dung dch A gm AgNO
3
0,050 M v Pb(NO
3
)
2
0,100 M.
1. Tnh pH ca dung dch A.
2. Thm 10,00 ml KI 0,250 M v HNO
3
0,200 M vo 10,00 ml dung dch A. Sau phn ng ngi ta
nhng mt in cc Ag vo dung dch B va thu c v ghp thnh pin (c cu mui tip xc hai
dung dch) vi mt in cc c Ag nhng vo dung dch X gm AgNO
3
0,010 M v KSCN 0,040 M.
a) Vit s pin .
b) Tnh sc in ng E
pin
ti 25
0
C .
c) Vit phng trnh phn ng xy ra khi pin hot ng.
d) Tnh hng s cn bng ca phn ng .
Cho bit : Ag
+
+ H
2
O AgOH + H
+
(1) ; K
1
= 10
11,70

Pb
2+
+ H
2
O PbOH
+
+ H
+
(2) ; K
2
= 10
7,80

Ch s tch s tan pK
s
: AgI l 16,0 ; PbI
2
l 7,86 ; AgSCN l 12,0 .

;
RT
ln = 0,0592 lg
F
= 0 ,799 V
E
0
Ag
+
/Ag

2. E
pin
s thay i ra sao nu: a) thm mt lng nh NaOH vo dung dch B ; b) thm mt lng
nh Fe(NO
3
)
3
vo dung dch X?
BI GII:
1. Ag
+
+ H
2
O AgOH + H
+
; K
1
= 10
-11,7

(1)
Pb
2+
+ H
2
O PbOH
+
+ H
+
; K
2
= 10
-7,8

(2)
Do K
2
>> K
1
nn cn bng 2 quyt nh pH ca dung dch
Pb
2+
+ H
2
O PbOH + H
+
; K
2
= 10
-7,8

(2)
C 0,10
| | 0,10 x x x
8 , 7
2
10
x 1 , 0
x

=

x = 10
-4,4
= |H
+
| ; pH = 4,40
2.a) Dung dch B: Thm KI : C
Ag+
= 0,025 M; C
Pb2+
= 0,050
C
I
- = 0,125M ; C
H+
= 0,10M
Ag
+
+ I

AgI |
0,025 0,125
- 0,10
Pb
2+
+ 2 I

PbI
2
|
0,05 0,10
- -
Trong dung dch c ng thi hai kt ta AgI | v PbI
2
|
AgI | Ag
+
+ I

; K
s1
= 1.10
-16
(3)
PbI
2
| Pb
2+
+ 2 I

; K
s2
= 1.10
-7,86
(4)
K
s1
<< K
s2
, vy trong dung dch cn bng (4) l ch yu. S to phc
hidroxo ca Pb
2+
l khng ng k v c H
+
d:



Pb
2+
+ H
2
O PbOH + H
+
; K
2
= 10
-7,8


| |
| |
| | | |
+ +

+
+
<< = =
2 8 , 6
1
8 , 7
2
Pb PbOH 10
10
10
Pb
PbOH

Trong dung dch PbI
2
| Pb
2+
+ 2 I

K
s2
= 1.10
-7,86

x 2 x
(2x)
2
x = 10
-7,86
x = 1,51.10
-3
M 2x = [I

] = 2,302 . 10-
3
M
| |
| |
M 10 . 31 , 3
10 . 02 , 3
10 . 1
I
K
Ag
14
3
16
1 s

+
= = = .
E ca cc Ag trong dung dch A: Ag
+
+ e Ag
| |
V 001 , 0 E
10 . 31 , 3 lg 0592 , 0 799 , 0 Ag lg 0592 , 0 E E
1
14 0
Ag
Ag
1
=
+ = + =
+
+

Dung dch X: Ag
+
+ SCN

AgSCN| ; 10
12,0

0,010 0,040
- 0,030 0,010
AgSCN| Ag
+
+ SCN

; 10
-12,0

0,030
x (0,030 + x)
x0,030 + x) = 10
-12

| |
11
2
12
10 . 33 , 3
10 x 3
10
x Ag

+
= = =
| |
V 179 , 0 E
10 . 33 , 3 lg 0592 , 0 799 , 0 Ag lg 0,0592 0,799 E
2
11
2
=
+ = + =
+

V E
2
> E
1
, ta c pin gm cc Ag trong X l cc + , cc Ag trong B l cc
S pin:
AgI| AgSCN|
PbI
2
| SCN

0,03 M

b) E
pin
= 0,179 0,001 = 0,178V
c) Phng trnh phn ng: Ag + I

AgI| + e
AgSCN + e Ag| + SCN

AgSCN + I

Ag| + SCN

d) K = = = 10
4


3. a) Khi thm lng nh NaOH vo dung dch B , c th xy ra 3 trng hp:
- Lng NaOH qa t khng trung ho HNO
3
: S to phc hidroxo ca Pb
2+
vn
khng ng k, do E
pin
khng thay i.
- Lng NaOH trung ho HNO
3
: C s to phc hidroxo ca Pb
2+
do |Pb
2+
|
gim, Nng I
-
s tng ln, do nng Ag
+
gim xung, E
1
gim ; vy E
pin
tng.
- Lng NaOH d trung ho ht HNO
3
v ho tan PbI
2
to thnh PbO
2

, do |Pb
2+
|
gim v E
pin
tng. PbI
2
+ 4 OH

PbO
2

+ 2 H
2
O + 2 I

b) Thm t Fe
3+
vo dung dch X: Fe
3+
+ SCN

FeSCN
2+

Nng ion SCN

gim, do nng ion Ag

+
tng, E
2
tng E
pin
tng
K THI CHN HC SINH GII QUC GIA VIT NAM 2005 (BNG A)
pH = 0 v 25
o
C th in cc tiu chun E
o
ca mt s cp oxi ha-kh c cho nh
sau:
2IO
4

/I
2
(r) = 1,31V; 2IO
3

/I
2
(r) = 1,19V; 2HIO/I
2
(r) = 1,45V ; I
2
(r)/2I

= 0,54V
(r): ch cht trng thi rn.
1. Vit phng trnh na phn ng oxi ha - kh ca cc cp cho.
2. Tnh E
o
ca cc cp IO
4

/ IO
3

v IO
3

/ HIO
3. V phng din nhit ng hc th cc dng oxi ha-kh no l bn, cc dng no l khng
bn? Ti sao?
4. Thm 0,40 mol KI vo 1 lt dung dch KMnO
4
0,24 M pH = 0
a) Tnh thnh phn ca hn hp sau phn ng.
b) Tnh th ca in cc platin nhng trong hn hp thu c so vi in cc calomen bo
ho.
5. Tnh E
o
ca cp IO
3

/ I
2
(H
2
O).
I
2
(H
2
O) ch iot tan trong nc.
Cho bit: E
o
= 1,51 V ; E ca in cc calomen bo ha bng 0,244 V ;

Ag Ag
Ks
AgSCN
Ks
AgI

10
12

10
16

MnO
4

/ Mn
2+

RT
F
25
o
C, ln = 0,0592 lg ; tan ca iot trong nc bng 5,0.10
4
M.




BI GII:
1. 2 IO
4

+ 16 H
+
+ 14 e I
2
(r) + 8 H
2
O ; E
o
= 1,31 V = E
o
1

2 IO
3

+ 12 H
+
+ 10 e I
2
(r) + 6 H
2
O ; E
o
= 1,19 V = E
o
2

2 HIO + 2 H
+
+ 2 e I
2
(r) + 2 H
2
O ; E
o
= 1,45 V = E
o
3

I
2
(r) + 2 e 2 I

; E
o
= 0,54 V = E
o
4

2. 2 IO
4

+ 16 H
+
+ 14 e I
2
(r) + 8 H
2
O ; K
1

= 10


I
2
(r) + 6 H
2
O 2 IO
3

+ 12 H
+
+ 10 e ; K
2
1
= 10


2 IO
4

+ 4 H
+
+ 4 e 2 IO
3

+ 2 H
2
O ; K
5

= 10


K
5
= K
1
. K
2
1
E
o
5
= E
o
=
4
10 14
2 1
O O
E E
= 1,61 V
2 IO
3

+ 12 H
+
+ 10 e I
2
(r) + 6 H
2
O ; K
2

= 10


I
2
(r) + 2 H
2
O 2 HIO + 2 H
+
+ 2 e ; K
3
1
= 10
2 IO
3

+ 10 H
+
+ 8 e 2 HIO + 4 H
2
O ; K
6
=

K
2
. K
3
1

K
6
= 10 = K
2
. K
3
1

E
o
= E
o
6
=
8
2 10
3 2
O O
E E
= 1,125 (V)
3. V E

<

E
o

nn HIO s t oxi ho - kh
4 2 HIO + 2 H
+
+ 2 e I
2
(r) + 2 H
2
O
2 HIO + 4 H
2
O 2 IO
3

+ 10 H
+
+ 8 e
10 HIO 4 I
2
(r) + 2 IO
3

+ 2 H
+
+ 4 H
2
O

Vy dng km bn nht v mt nhit ng hc l HIO, cc dng khc: IO
4

, IO
3

,
I
2
, I

u bn pH = 0.
4. a)E
o
= 1,51V >> E
o
(E
o
4
nh nht) nn u tin s xy ra phn ng:
2 MnO
4

+ 8 H
+
+ 5 e Mn
2+
+ 4 H
2
O
IO
4
-
/IO
3
-
14E
o
1
/0,0592
-10E
o
2
/0,0592
4E
o
5
/0,0592
10E
o
2
/0,0592
-2E
o
3
/0,0592
8E
o
6
/0,0592
IO
3
-
/HIO
IO
3
-
/HIO HIO/I
2

MnO
4
-
/Mn
2+
I
2
/2I
-
5 2 I



I
2
(r) + 2 e
2 MnO
4

+ 10 I

+ 16 H
+
2 Mn
2+
+ 5 I
2
(r) + 8 H
2
O ; K =

10
163

C
O
0,24 0,4
AC 0,04 2 0,04 10 0,04 2 0,04 5
C 0,16 0 1 0,08 0, 2
MnO
4

cn d s oxi ho tip I
2
thnh IO
3

.
E
o
= 1,51 V > E
o
= 1,19 V

2 MnO
4

+ 8 H
+
+ 5 e Mn
2+
+ 4 H
2
O
I
2
(r) + 6 H
2
O 2 IO
3

+ 12 H
+
+ 10 e
2 MnO
4

+ I
2
(r) + 4 H
+
2 IO
3

+ 2 Mn
2+
+ 2 H
2
O ; K =

10
176

C
O
0,16 0,2 0,08
AC 0,08 2 0,08 0,08 2 0,08 2
C 0 0,12 1 0,16 0, 24
Thnh phn hn hp sau phn ng: IO
3

= 0,16 M; Mn
2+
=0,24 M; I
2
(H
2
O)=5.10
4
M; )
I
2(r)
= 0,12M; pH = 0.
b) Trong hn hp c cp IO
3
-
/I
2
(r) nn:
| | | | V H IO E E
o
r I IO
18 , 1 lg
10
0592 , 0 2 2
3
) ( /
2 3
= + =
+

E so vi in cc calomen bo ho: 1,18 0,244 = 0,936V
5. 2IO
3
-
+ 12H
+
+ 10e I
2
(r) + 6H
2
O : K
2
= 10
10.1,19/0,0592

I
2
(r) I
2
(H
2
O) S = 5.10
-4
M
2IO
3
-
+ 12H
+
+ 10e I
2
(H
2
O) + 6 H
2
O; K
7
=10 =10
10.1,19/0,0592
.S
Suy ra E
7
o
= 1,17V
K THI CHN HC SINH GII QUC GIA VIT NAM 2005 (BNG A)
Mt bnh in phn cha dung dch NaOH (pH=14) v mt bnh in phn khc cha
dung dch H
2
SO
4
(pH = 0) 298K. Khi tng hiu in th t t hai cc mi bnh ngii ta thy
c kh ging nhau thot ra c hai bnh ti cng in th.
1. Gii thch hin tng trn. Vit cc phng trnh phn ng xy ra mi bnh (khng xt s to
thnh H
2
O
2
v H
2
S
2
O
8
).
2. Tnh hiu in th ti thiu phi t vo hai cc mi bnh cho qa trnh in phn xy ra.
3. Ngi ta mun gim pH ca dung dch NaOH xung cn 11. C th dng NH
4
Cl c khng?
Nu c, hy gii thch v tnh khi lng NH
4
Cl phi dng gim pH ca 1 lt dung dch
NaOH t 14 xung cn 11.
4. Khi pH ca dung dch NaOH bng 11, th hiu in th ti thiu phi t vo hai cc ca bnh
in phn cho qa trnh in phn xy ra l bao nhiu?
Cho bit: E
o
= 0,4V; E
o
=1,23 V; pK
b
(NH
3
)

= 4,75.

BI GII:
1.
Trong th nghim ny, nc b in phn cng mt in th.
E
7
o
/0,0592
H
2
O, 1/2 O
2
/ 2OH

2H
+
, 1/2 O
2
/ H
2
O
a) Dung dch NaOH:
anot: 2 OH

H
2
O + 1/2 O
2
+ 2 e
catot: 2 H
2
O + 2 e H
2
+ 2 OH


H
2
O H
2
+ 1/2 O
2

b) Dung dch H
2
SO
4
:
anot: H
2
O 1/2 O
2
+ 2 H
+
+ 2 e
catot: 2 H
+
+ 2 e H
2

H
2
O H
2
+ 1/2 O
2

Kh thot ra 2 bnh u l hidro v oxi
2.
a) Dung dch NaOH:
E
ant
= 0,4 V
E
catt
= 0 + lg (10
14
)
2
= 0,83 V
U
min
= E
ant
E
catt
= 0,4 + 0,83 = 1,23 V
b) Dung dch H
2
SO
4
:
E
ant
= 1,23 V
E
catt
= 0 V
U
min
= E
ant
E
catt
= 1,23 V
(khi tnh U
min
khng xt n qu th).
3. C th dng NH
4
Cl gim pH ca dung dch NaOH t 14 xung 11.
NH
4
+
+ OH

NH
3
+ H
2
O


pOH ca dung dch NaOH thm

NH
4
Cl

gim pH ca dung dch NaOH t 14
xung 11 c tnh theo cng thc:
pOH = pK
b
+ lg



3 = 4,75 + lg

Suy ra [NH
4
+
] = 0,0178 [NH
3
]
Khi pH ca dung dch NaOH gim t 14 xung 11 th [OH

] ca dung dch gim i: 1

10
3
= 0,999 mol. y chnh l s mol NH
3
hnh thnh. Vy [NH
3
] = 0,999 mol/L v:
[NH
4
+
] = 0,0178 0,999 ~ 0,0178 (mol/L)
S mol NH
4
Cl phi thm vo 1 lt dung dch:
n = n + n = 0,0178 + 0,999 = 1,0168 (mol)
Khi lng NH
4
Cl phi thm vo 1 lt dung dch: 1,0168 53,5 = 54,4 (gam)
2

0,0592

[NH
3
]
[NH
4
+
]
[NH
3
]
[NH
4
+
]
NH
4
+
NH
3

4. Khi pH = 11, dung dch NaOH:
E
anot
= 0,4 V + lg
E
catt
= 0 + lg (10
11
)
2

U
min
= E
anot
E
catot
= 0,4 + 3 0,0592 + 0,0592 11 ~ 1,23 V
II. OLYMPIC HA HC QUC T:
K THI OLYMPIC HA HC QUC T LN TH 30:
Vng kim loi thng c pht hin trong cc loi aluminosilicat v b phn tn
nhuyn trong cc khong cht khc. Vng c th c tch bng cch cho nghin vn tc dng
vi dung dch natri xianua sc khng kh. Trong qa trnh ny vng km loi c chuyn chm
thnh [Au(CN)
2
]
-
tan c trong nc (phn ng (1)).
Sau khi t n cn bng, phn dung dch (pha dung dch) c bm ra v vng kim loi
c thu hi bng cch cho phc vng tc dng vi km, km c chuyn thnh [Zn(CN)
4
]
2-

(phn ng 2).
1) Vit v cn bng cc phng trnh ion ca phn ng (1) v (2).
Vng trong t nhin thng dng hp kim vi bc v bc cng b oxy ho bi dung dch
natri xianua sc khng kh.
2) 500L dung dch cha [Au(CN)
2
]
-
0,0100M v [Ag(CN)
2
]
-
0,0030M c cho bay hi n
ch cn mt phn ba th tch ban u v c x l bng km (40g). Gi thit rng s sai
lch so vi iu kin tiu chun l khng quan trng v cng gi thit l cc phn ng oxy
ha kh xy ra hon ton. Hy tnh cc nng ca [Au(CN)
2
]
-
v [Ag(CN)
2
]
-
sau khi
phn ng kt thc.
Cho bit:
[Zn(CN)
4
]
2-
+ 2e
-
Zn + 4CN
-
E
o
= -1,26V
[Au(CN)
2
]
-
+ e
-
Au + 2CN
-
E
o
= -0,60V
[Ag(CN)
2
]
-
+ e
-
Ag + 2CN
-
E
o
= -0,31V
3) [Au(CN)
2
]
-
l mt phc rt bn trong mt s iu kin nht nh. Nng ca natri xianua
l bao nhiu gi c 99% theo s mol ca vng trong dung dch dng phc xianua?
Bit K
b
([Au(CN)
2
]
-
) = 4.10
28
.
4) c mt s c gng pht trin cc qa trnh tch chit vng khc thay th cch trn.
Ti sao?. Hy chn phng n ng:
a) Dung dch natri xianua n mn cc dng c khai thc m.
b) Natri xianua thot vo nc ngm trong t v to ra hydroxianua rt c vi nhiu
ng vt.
c) Vng thu c t phng php ny khng tinh khit.
BI GII:
1) Phn ng (1): 4Au + 8CN
-
+ O
2
+ 2H
2
O 4[Au(CN)
2
]
-
+ 4OH
-
Phn ng (2): Zn + 2[Au(CN)
2
]
-
[Zn(CN)
4
]
2-
+ 2Au
2) E
o
Ag/Zn
= -0,31 (-1,26) = 0,95V
E
o
Au/Zn
= -0,60 (-1,26) = 0,66V
E
o
Ag/Zn
> E
o
Au/Zn
. V vy phc Ag(I) s b kh trc.
n
Ag(I)
= 1,5mol
n
Au(I)
= 5,0mol
n
Zn
= 0,61mol
1mol Zn s phn ng vi 2 mol Ag(I) hoc Au(I).
0,0592
2
1
(10
3
)
2

0,0592
2
Nn 0,61 mol Zn s tiu th 1,2mol [Ag(CN)
2
]
-

[Ag(CN)
2
]
-
cn li = 1,5 1,2 = 0,3mol
[Au(CN)
2
]
-
khng b kh.
Nng [Au(CN)
2
]
-
khi phn ng kt thc = 0,010.3 = 0,030M
Nng [Ag(CN)
2
]
-
khi phn ng kt thc = 0,3.3/500 = 0,002M
3) Au
+
+ 2CN
-
[Au(CN)
2
]
-
K
b
= 4.10
28
.
| |
| || |
| |
| | | | 100
99
) (
) (
) (
2
2
2
2
=
+
=
+

CN Au Au
CN Au
CN Au
CN Au
K
b

Nn 100[Au(CN)
2
]
-
= 99[Au
+
] + 99{[Au(CN)
2
]
-
}
Do [Au
+
] = [Au(CN)
2
]
-
/99
Thay vo K
b
ta tnh c [CN
-
] = 5.10
-14
M
4) b)
K THI OLYMPIC HA HC QUC T LN TH 32:
n mn kim loi thng i km vi cc phn ng in ha. Vic n mn r st trn b mt
cng theo c ch ny. Phn ng in cc ban u thng l:
(1) Fe
(r)
Fe
2+
(aq)
+ 2e
(2) O
2
+ 2H
2
O + 4e 4OH
-
(aq)

T bo in ha ng vi cc phn ng trn c biu din nh sau (t=25
o
C):
Fe
(r)
Fe
2+
(aq)
OH
-
(aq),
O
2(k)
Pt
(r)
.
Th chun 25
o
C:
Fe
2+
(aq)
+ 2e Fe
(r)
E
o
= 0,44V.
O
2
+ 2H
2
O + 4e 4OH
-
(aq)
E
o
= 0,40V.
Cho bit:
RTln10/F = 0,05916V ( 25
o
C).
F = 96485C.mol
-1
.
1. Tnh E
o
ca phn ng 25
o
C.
2. Vit phn ng xy ra hai na pin v ton b phn ng.
3. Tnh K ca phn ng.
4. Phn ng xy ra trong 24 gi v I = 0,12A. Tnh khi lng Fe chuyn thnh Fe
2+
sau
24 gi. Bit oxy d.

5. Tnh E ca phn ng bit:
[Fe
2+
] = 0,015M; pH
na pin phi
= 9,00, p(O
2
) = 0,700bar.
BI GII:
1. E
o
(pin)
= E
o
phi

- E
o
tri
= 0,40 (-0,44) = 0,84V
2. Phn ng xy ra hai na pin:
Tri: 2Fe 2Fe
2+
+ 4e (nhn 2)
Phi: O
2
+ 2H
2
O + 4e 4OH
-

Ton b phn ng: 2Fe + O
2
+ 2H
2
O 2Fe
2+
+ 4OH
-

3. K = [Fe
2+
][OH
-
]
4
/p(O
2
)
G = -nFE
o
(pin)
= -RTlnK K = 6,2.10
56
(M
6
bar
-1
)
4. Q = It = 10368C.
n(e) = Q/F = 0,1075mol
m(Fe) = 3,00g.
5.
| | | |
) (
Fe
log
05916 , 0
2
4 2
2
) ( ) (
O p
OH
n
E E
o
pin pin
+
=
pH = 9,00 [H
+
] = 10
-9
M v [OH
-
] = 10
-5
M
K THI OLYMPIC HA HC QUC T LN TH 37:
Chiufen, th trn m nm trn i ca min Bc i Loan, l mt ni m bn c th
khm ph ra lch s i Loan. cng l mt trong nhng ni c m vng ln nht chu .
Chnh v vy Chiufen thng c gi l th vng ca chu . KCN thng c dng
chit vng t qung. Vng tan trong dung dch xianua trong s c mt ca khng kh to thnh
Au(CN)
2
-
bn vng trong dung dch nc.
4Au(r) + 8CN
-
(aq) + O
2
(k) + 2H
2
O(l) 4Au(CN)
2
-
(aq) + 4OH
-
(aq)

1. Vit cng thc cu to ca Au(CN)
2
-
, ch ra v tr lp th ca tng nguyn t.
2. Cn bao nhiu gam KCN chit vng t qung?
Nc cng thy, l mt hn hp gm HCl v HNO
3
ly theo t l 3:1 v th tch, c
tm ra v pht trin bi cc nh gi kim thut ho tan vng. Qa trnh ny l mt phn ng oxy
ha - kh xy ra theo phng trnh:
Au(r) + NO
3
-
(aq) + Cl
-
(aq) AuCl
4
-
(aq) + NO
2
(k)

3. Vit hai na phn ng v s dng n cn bng phng trnh trn.
4. Ch ra qa trnh no l oxy ha, qa trnh no l kh.
Vng khng h phn ng vi axit nitric. Tuy nhin vng c th phn ng vi nc cng
thy v to thnh ion phc AuCl
4
-
. Cho bit cc th sau:
Au
3+
(aq) + 3e
-
Au(r) E
o
= +1,50V
AuCl
4
-
(aq) + 3e
-
Au(r) + 4Cl
-
(aq) E
o
= +1,00V
5. Tnh hng s cn bng K = [AuCl
4
-
]/[Au
3+
][Cl
-
]
4
.
6. Vai tr ca HCl l sinh ra Cl
-
. i vi phn ng trn th Cl
-
c vai tr g?
a) Cl
-
l tc nhn oxy ha.
b) Cl
-
l tc nhn kh.
c) Cl
-
l tc nhn to phc.
d) Cl
-
l cht xc tc.




BI GII:
1. Cu trc ng thng:
Au C C N N
-

2.
4Au + 8KCN
-
+ O
2
+ 2H
2
O 4KAu(CN)
2
+ 4KOH

m
KCN
= (20/197).(8/4).65,12 = 13,024g
3. Oxy ha:

+ + e AuCl Cl Au
aq aq r
3 4
) ( 4 ) ( ) (

Kh ha: 3NO
3
-
(aq) + 6H
+
(aq) + 3e
-
3NO
2
(k)

+ 3H
2
O(l)
Au
(r)
+ 3NO
3
-
(aq)
+ 6H
+
(aq)
+ 4Cl
-
(aq)
AuCl
4
-
(aq)
+ 3NO
2(k)
+ 3H
2
O
(l)
.
4. Tc nhn oxy ha: HNO
3

Tc nhn kh: Au
5. Au
3+
(aq) + 3e Au(r) E
o
= +1,50V
Au(r) + 4Cl
-
(aq) AuCl
4
-
(aq) + 3e -E
o
= -1,00V
Au(r) + Au
3+
(aq) + 4Cl
-
(aq) AuCl
4
-
(aq) + Au(r) E
o
= 0,50V
Cch 1: E = E
o
(0,059/n)lgQ
Lc t cn bng: Q = K, E = 0; K = [AuCl
4
-
]/[Au
3+
][Cl
-
]
4

E
o
= (0,059/n)lgK K = 10
25,42
= 2,6.10
25
.
Cch 2: G
o
1
+ G
o
2
= G
o
3

(-nFE
o
1
) + (-nFE
o
2
) = -RTlnK
E = (RT/nF)lnK = (0,059/n)lgK K = 10
25,42
= 2,6.10
25
.
6. a)
III. BI TP CHUN B CHO OLYMPIC HA HC QUC T:
OLYMPIC HA HC QUC T LN TH 32:
K thut in ha hc thng c dng xc nh tnh tan ca cc mui kh tan. Do sc
in ng l hm bc nht theo logarit ca nng cho nn c th xc nh c cc nng d
rt nh.
Bi tp ny s dng mt pin in ha gm hai phn, c ni bng cu mui. Phn bn tri
ca s pin l mt thanh Zn(r) nhng trong dung dch Zn(NO
3
)
2
(aq) 0,200M; cn phn bn phi
l mt thanh Ag(r) nhng trong dung dch AgNO
3
(aq) 0,100M. Mi dung dch c th tch 1,00L ti
25
o
C.
a) V gin pin v vit phng trnh phn ng tng ng ca pin.
b) Hy tnh sc in ng ca pin v vit phng trinh phn ng khi pin phng in.
Gi s pin phng in hon ton v lng Zn c d
c) Hy tnh in lng phng thch trong qa trnh phng in.
Trong mt th nghim khc, KCl(r) c thm vo dung dch AgNO
3
pha bn phi ca
pin ban u. Xy ra s kt ta AgCl(r) v lm thay i sc in ng. Sau khi thm xong, sc in
ng bng 1,04V v [K
+
] = 0,300M.
d) Hy tnh [Ag
+
] ti cn bng.
e) Hy tnh [Cl
-
] ti cn bng v tch s tan ca AgCl.
Th in cc chun ti 25
o
C nh sau:
Zn
2+
(aq)
+ 2e Zn
(r)
E
o
= -0,76V
Ag
+
(aq)
+ e Ag
(r)
E
o
= +0,80V


BI GII:
a) Gin pin: Zn
(r)
Zn
2+
(aq)
Ag
+
(aq)
Ag
(r)
.
Gin pin ny tho quy c ca IUPAC vi qa trnh oxy ha (cho electron) pha bn
tri:
Tri, oxy ha: Zn
(r)
Zn
2+
(aq)
+ 2e
Phi, kh: Ag
+
(aq)
+ e Ag
(r)
(nhn cho 2)
Phn ng ca pin Zn
(r)
+ Ag
+
Zn
2+
(aq)
+ 2Ag
(r)
.
b) E
o
pin
= E
o
(phi)
E
o
(tri)
= 1,56V
Phng trnh Nernst tng ng vi pin nu trn (Cng c th trnh by theo na pin v cc
bn phn ng):
Hot a ca mt cht tan tnh gn ng t nng ca cht y (chia cho nng tiu
chun) v hot ca mt cht rn bng 1
V
a a
a a
n
E E
Zn
Zn
o
pin pin
52 , 1
) 100 , 0 (
200 , 0
lg
2
05916 , 0
56 , 1
) .(
) .(
lg
05916 , 0
2 2
Ag
2
Ag
2
= = + =
+
+ +

Tr s dng ca E
pin
cho thy rng phn ng pin vit nh trn l phn ng c th t xy ra
trong qa trnh phng in.
Phn ng c th t xy ra: Zn
(r)
+ Ag
+
Zn
2+
(aq)
+ 2Ag
(r)
.
c) Khi phng in hon ton, E
pin
= 0 v phn ng trong pin t cn bng
0 = 1,56 0,05916/2.lgK K = 5,5.10
52
; ngha l cn bng ca phn ng pin dch chuyn
hn v bn phi, nn thc t khng cn ion Ag
+
trong dung dch
Lng Ag
+
v electron vn chuyn:
n(Ag
+
) = [Ag
+
].V = 0,100mol v n(e
-
) = n(Ag
+
) = 0,100mol
Hng s Faraday F l s in lng ng vi 1 mol electron
Q = n(e
-
).F = 9648,5C
d) Gi x l nng Ag
+
cui ([Ag
+
])
in cc bn tri khng i, ngha l nng [Zn
2+
] duy tr ti 0,200M
| | M Ag x
10
10 . 3 , 7
2
200 , 0
lg
2
05916 , 0
56 , 1 04 , 1
+
= = =
e) [Cl
-
] = nng thm - nng gim do AgCl kt ta = 0,300 (0,100 - 7,3.10
-10
)
= 0,200M
K
s
(AgCl) = 7,3.10
-10
.0,200 = 1,5.10
-10
M
2
.
OLYMPIC HA HC QUC T LN TH 31:
Ga tr E
o
cho cc bn phn ng ca Fe v Ce nh sau:
Fe
3+
+ e
-
Fe
2+
E
o
= 0,77V
Ce
4+
+ e Ce
3+
E
o
= 1,61V
Th ti im tng ng ca s chun Fe
2+
v Ce
4+
l 1,19V. Hai cht ch th mi
c th s dng xc nh im tng ng:
Di Bolane(dip): In
Ox
+ 2e In
red
E
o
dip
= 0,76V
Tm khng mu
p-nitro-di-bolane(pn): In
Ox
+ 2e In
red
E
o
pn
= 1,01V
Tm khng mu
C hai cht ch th u i mu khi [In
Ox
]/[In
red
] = 10. Vy cht ch th no l thch hp cho
s chun Fe
2+
- Ce
4+
?
BI GII:
Vi di-bolane:
| |
| | red
oxh
E E
o
dip dd
lg
2
059 , 0
+ =
Khi [In
Ox
]/[In
red
] = 10 th:
| |
| |
V
red
oxh
E E
o
dip dd
79 , 0 lg
2
059 , 0
= + =
Ti 0,79V, tnh [Fe
3+
]/[Fe
2+
]
| |
| |
| |
| |
| |
| |
2 , 2 lg 059 , 0 77 , 0 79 , 0
lg
1
059 , 0
2
3
2
3
2
3
= + =
+ =
+
+
+
+
+
+
Fe
Fe
Fe
Fe
Fe
Fe
E E
o
Fe dd

Di-bolane khng phi l cht ch th thch hp v [Fe
3+
] gp 2,2 ln [Fe
2+
]
Vi p-nitro-di-bolane:
| |
| | red
oxh
E E
o
pn dd
lg
2
059 , 0
+ =
Khi [In
Ox
]/[In
red
] = 10 th:
| |
| |
V
red
oxh
E E
o
pn dd
04 , 1 lg
1
059 , 0
= + =
Ti 0,79V, tnh [Fe
3+
]/[Fe
2+
]
| |
| |
| |
| |
| |
| |
4
2
3
2
3
2
3
10 . 80 , 3 lg 059 , 0 77 , 0 04 , 1
lg
1
059 , 0
= + =
+ =
+
+
+
+
+
+
Fe
Fe
Fe
Fe
Fe
Fe
E E
o
Fe dd

Vy cht ch th thch hp l p-nitro-di-bolane
OLYMPIC HA HC QUC T LN TH 30:
Cc bn phn ng sau c lin quan n s hnh thnh urani trong dung dch nc:
U
3+
+ 3e U E
o
= -1,798V
U
4+
+ e U
3+
E
o
= -0,607V
UO
2
2+
+ e UO
2
+
E
o
= +0,062V
UO
2
2+
+ 4H
+
+ 2e U
4+
+ 2H
2
O E
o
= +0,327V
UO
2
2+
+ 4H
+
+ 6e U

+ 2H
2
O E
o
= -1,444V
UO
2
+
+ 4H
+
+ e U
4+
+ 2H
2
O E
o
= +0,620V
a) Xc nh mc oxy ha ca cc tiu phn khc nhau c cha urani xut hin trong cc bn
phn ng trn.
b) Bng cch phn tch cc bn phn ng trn, hy xc nh din tin ha hc ti u ca mt
mu nh urani rn tip xc vi dung dch 1M ca mt axit mnh n chc HX, c mt
hydro di p sut 1atm, tt c ti 25
o
C. Vit cc phng trnh phn ng, cn bng v th
in cc ca tt c cc phn ng (Gi thit rng baz lin hp X
-
khng phn ng ng k
vi urani hoc hp cht ca urani).
c) Tiu phn bn nht ca urani ti pH = 6 l g? (v cc iu kin khc u coi nh chun).
d) Xc nh khong pH ca dung dch hoc axit trung ho m dung dch 1M ca UO
2
+
l bn:
i) Vi cc iu kin khc u chun (nh P(H
2
) = 1, nng ca cc tiu phn c cha urani
= 1.
ii) Vi P(H
2
) = 1,0.10
-6
atm v cc iu kin khc u coi nh chun.
iu kin no l thch hp hn cho s hnh thnh urani trong cc lung nc thin nhin?
BI GII:
a) Urani kim loi c s oxi ha bng khng theo nh ngha. S oxi ha cc tiu phn khc
ca U: U(III) [U
3+
]; U(IV) [U
4+
]; U(V) [UO
2
+
]; U(VI) [UO
2
2+
].
b) Cc iu kin m t l iu kin chun, nn c th dng th kh chun xc nh cc
phn ng t xy ra theo chiu no. Cng cn phi xt cc bc kh:
2H
+
+ 2e H
2
E
o
= 0,000V
C hai bn phn ng to ra U kim loi:
U
3+
+ 3e U
UO
2
2+
+ 4H
+
+ 6e U

+ 2H
2
O
T Urani b oxi ha k tip:
2U + 6H
+
2U
3+
+ 3H
2
E
o
pin
= +1,798V
U + 2H
+
+ 2H
2
O UO
2
2+
+ 3H
2
E
o
pin
= +1,444V
Bt k qa trnh no trn y chim u th, khng c sn phm s cp no U
3+
hoc
UO
2
2+
l sn phm chnh.
U(III) t oxy ha chuyn thnh U(IV):
2U
3+
+ 2H
+
2U
4+
+ H
2
E
o
pin
= +0,607V
Trong khi U(VI) li t kh to li U(IV) hoc U(V):
UO
2
2+
+ 2H
+
+ H
2
U
4+
+ 2H
2
O E
o
= +0,327V
UO
2
2+
+ H
2
2UO
2
+
+ 2H
+
E
o
= +0,062V
v U(V) cng t kh thnh U(IV):
2UO
2
+
+ 6H
+
+ H
2
2U
4+
+ 4H
2
O E
o
= +0,620V
V U
4+
l tiu phn duy nht khng th t phn ng vi H
+
hoc H
2
, nn s c nhiu nht
trong dung dch nc iu kin ny.
(B sung: khi vn cn U kim loi, qa trnh: U
4+
+ 3U 4U
3+
E
o
pin
= +1,191V
l thun li, nhng ch c th xy ra n khi ht U, sau U(III) s b oxi ha thnh U(IV) nh
ni trn).
c) Do cc iu kin l tiu chun tr [H
+
] = 1,0.10
-6
M, c th dng dng n gin ca phng
trnh Nernst nh sau cho cc phng trnh c lin quan:
2U + 6H
+
2U
3+
+ 3H
2
E
o
pin
= +1,798V
E
pin
= E
o
pin
(RT/6F)ln([H
+
]
-6
) = +1,444V
U + 2H
+
+ 2H
2
O UO
2
2+
+ 3H
2
E
o
pin
= +1,444V
E
pin
= E
o
pin
(RT/6F)ln([H
+
]
-2
) = +1,326V
2U
3+
+ 2H
+
2U
4+
+ H
2
E
o
pin
= +0,607V
E
pin
= E
o
pin
(RT/2F)ln([H
+
]
-2
) = +0,253V
UO
2
2+
+ 2H
+
+ H
2
U
4+
+ 2H
2
O E
o
pin
= +0,327V
E
pin
= E
o
pin
(RT/2F)ln([H
+
]
-2
) = -0,027V
UO
2
2+
+ H
2
2UO
2
+
+ 2H
+
E
o
pin
= +0,062V
E
pin
= E
o
pin
(RT/2F)ln([H
+
]
2
) = +0,293V
2UO
2
+
+ 6H
+
+ H
2
2U
4+
+ 4H
2
O E
o
pin
= +0,620V
E
pin
= E
o
pin
(RT/2F)ln([H
+
]
-6
) = -0,444V
Ton b cc qa trnh trn c tr s E
o
pin
dng khi xt theo chiu thun, nn tt c u xy
ra c theo chiu ny ti pH = 0. Tri li, U(VI) U(IV) v U(V) U(IV) t xy ra theo chiu
nghch ti pH = 6 (nh cho thy qua tr s m ca E
pin
); nay U(IV) li b oxy ha thnh U(V) hoc
U(VI). Do U(VI) l mc oxy ha duy nht khng t phn ng c vi H
+
hay H
2
trong iu kin
ny nn tiu phn chim s lng ln s l UO
2
2+
.
d) gii cu hi ny, cn xem xt cc phn ng c lin quan n UO
2
+
.
UO
2
2+
+ H
2
2UO
2
+
+ 2H
+
E
o
= +0,062V
E
pin
= E
o
pin
(RT/2F)ln([H
+
]
2
.P(H
2
)
-2
)
2UO
2
+
+ 6H
+
+ H
2
2U
4+
+ 4H
2
O E
o
= +0,620V
E
pin
= E
o
pin
(RT/2F)ln([H
+
]
-6
.P(H
2
)
-2
)
Ti cc iu kin lc u, E
pin
= 0, tng ng vi cc trng hp sau:
| | } {
2 / 1 ) / 2 (
2
.
2
RT FE
H
o
pin
e P H =
+
cho qa trnh U(VI) U(V) v
| | } {
6 / 1 ) / 2 (
2
.
2
RT FE
H
o
pin
e P H

+
=
cho
qa trnh U(IV) U(V)
Cc biu thc trn cho gi tr ban u ca:
i) [H
+
] < 11,2M hay pH > -1 U(V) bn hn U(IV) v [H
+
] < 3,19.10
-4
M hay pH > 3,50
U(V) bn hn U(IV).
ii) [H
+
] < 1,12.10
-5
M hay pH > 4,95 U(V) bn hn U(IV) v [H
+
] < 3,19.10
-2
M hay pH >
1,50 U(V) bn hn U(IV).
Nh vy UO
2
+
bn hn cc mc oxy ha khc trn khong pH 3,5 7 (ta ch ang xt cc
dung dch axit v trung ha) di kh quyn hydro tiu chun, nhng ch bn v khng b oxy ha
thnh U(VI) ti pH c ga tr ln hn 4,95.
p sut ring phn ca H
2
trong kh quyn rt thp, nn iu kin ca cu sau (cu ii) gn
hn vi iu kin thc ca mi trng qa t. UO
2
+
khng thc s bn nh kt qa ca pin cho
thy.
OLYMPIC HA HC QUC T LN TH 32:
Mangan v St trong hu ht t trng an Mch c ngun gc ch yu t cc enzym
trong cc vt liu hu c cht. Trong iu kin axit v kh, cc nguyn t ny c mt di
dng Mn
II
v Fe
II
.
Ti nhng ni m nc ngm trn ra b mt theo cc con sui, cc ion b oxy ha bi oxy
khng kh.
a) Vit phng trnh phn ng oxy ha mangan (II) thnh mangan (IV) oxit vi dioxi (O
2
).
b) Hy tnh G
1
o
ti 25
o
C ca phn ng cu a vi cc s liu cho di y:
2MnO
2(r)
+ 4H
+
(aq)
+ 2e
-
Mn
2+
+ 2 H
2
O
(l)
E
o
2
= 1,21V
3O
2(k)
+ 4H
+
(aq)
+ 4e
-
2H
2
O
(l)
E
o
3
= 1,23V
c) Hy tnh hng s cn bng K
1
ti 25
o
C ca phn ng cu a
Gi thit rng mangan (II) to phc vi vt liu hu c trong mn ca t. Cng gi thit
rng hng s to phc mangan (II) mn l 10
5
M
-1
v nng ca ligand bng 10
-4
M
d) Hy tnh hng s cn bng ca phn ng:
2Mn(mn)
2+
(aq) + O
2
(k) + 2H
2
O(l) 2MnO
2
(r) + 2mn(aq) + 4H
+
(aq)
t trng axit c th c pH bng 5 v t kim c th c pH bng 8
e) T cc s liu l thuyt cho trn hy tnh nng ca Mn(mn)
2+
ln lt ti pH bng 5 v
pH = 8. Bit p(O
2
) = 0,2 bar v t trng c cha lng MnO
2
d.
f) Mangan c cy trng hp th qua trung gian phc mn. Loi t canh tc no gp vn
thiu mangan d c lng ln mangan trong t?
BI GII:
a) 2Mn
2+
(aq) + O
2
(k) + 2H
2
O(l) 2MnO
2
(r) + 4H
+
(aq)
b) G
2
o
= -2FE
2
o
= -233,5kJ.mol
-1

G
3
o
= -2FE
3
o
= -474,7kJ.mol
-1

G
1
o
= -2G
2
o
+ G
3
o
= -7,7kJ.mol
-1

c) G
1
o
= -RTlnK
1
vi K
1
= 22,4M
2
bar
-1

d) Mn
2+
(aq) + mn(aq) Mn(mn)
2+
(aq) | = 10
5
M
-1

2Mn(mn)
2+
(aq) + O
2
(k) + 2H
2
O(l) 2MnO
2
(r) + 2mn(aq) + 4H
+
(aq)
| | | |
| | ( )
1 4 9
2
1
2
2
4
2
10 . 24 , 2
) (

+
+ +
= = = bar M
K
O p mun Mn
H mun
K
|
(*)
e) pH = 5: Thay [H
+
] = 10
-5
M vo biu thc (*) trn ta tnh c [Mn(mn)
2+
] = 4,7.10
-10
M
pH = 8: Thay [H
+
] = 10
-8
M vo biu thc (*) trn ta tnh c [Mn(mn)
2+
] = 4,7.10
-16
M
f) t kim
OLYMPIC HA HC QUC T LN TH 33:
a) Mt dung dch cha ion Sn
2+
c chun in ha bng dung dch Fe
3+
. Th kh tiu chun
ca cp Sn
4+/2+
v Fe
3+/2+

c cho di y:
Sn
4+
+ 2e = Sn
2+
E
o
= 0,154V
Fe
3+
+ e = Fe
2+
E
o
= 0,771V
i) Vit phng trnh phn ng tng qut v tinh nng lng t do ca phn ng.
ii) Xc nh hng s cn bng ca phn ng.
b) Nu 20ml dung dch Sn
2+
0,10M c chun bng dung dch Fe
3+
0,20M. Tnh sc in
ng ca pin trong cc iu kin sau:
i) Khi thm 5mL Fe
3+
.
ii) Ti im tng ng.
iii) Khi thm 30mL dung dch Fe
3+

in cc calomel (E
o
S.C.E
= 0,242V) c s dng lm in cc chun.
c) Mt trong s nhng phng php phn tch quan trng nh lng ion Cu
2+
l php chun
iot. Trong phn ng ny Cu
2+
s b oxy ha v Cu
+
bng I
-
v I
2
t do sinh ra s phn ng
vi dung dch chun Na
2
S
2
O
3
. Phn ng chun Cu
2+
xy ra theo phng trnh:
2Cu
2+
+ 4I
-
2CuI
(r)
+ I
2(aq)

Th chun ca cc qa trnh oxy ha - kh s l:
Cu
2+
+ e = Cu
+
E
o

= 0,153V
I
2
+ 2e = 2I
-
E
o

= 0,535V
Da vo th chun th phn ng trn khng th xy ra c. Tuy nhin phn ng ny vn
xy ra mt cch nh lng. Chng ta hy tm hiu l do thng qua cc d kin sau:
i) trong dung dch nc th CuI c tch s tan b vi K
sp
= 1,1.10
-12
. Tnh th kh chun
biu kin ca qa trnh CuI
(r)
= Cu
+
+ I
-
.
ii) S dng kt qa cu i), tnh th kh chun biu kin ca phn ng v hy da vo cho
bit chiu phn ng.
iii) Tnh hng s cn bng ca phn ng t cc d kin cho cu ii).
BI GII:
a) i) Phn ng xy ra theo phng trnh:
Sn
2+
+ 2Fe
3+
= 2Fe
2+
+ Sn
4+
E
o
= 0,617V
G = -nFE = -119kJ
ii) 0,0592/n(lgK) K = 6,92.10
20
.
b) Trc im tng ng, E ca phn ng c tnh bi phng trnh:

| |
| |
+
+
+ =
+ +
4
2
/
. .
lg
2
0592 , 0
2 4
Sn
Sn
E E E
o
Sn Sn
kh
o
E C S ox pin

i) Khi thm 5,00mL Fe
3+
th lng Sn
2+
chuyn sang Sn
4+
s l 5,00/20,00.
Nh vy:

| |
| |
3
0 , 20 / 0 , 5
0 , 20 / 0 , 15
4
2
= =
+
+
Sn
Sn

Thay vo biu thc tnh E ta thu c kt qa E = -0,102V
ii) Ti im tng ng ta tnh E theo cng thc:
V
E E
E
o
Fe
o
Sn
118 , 0
3
2
2 3 2 4
/ Fe / Sn
=
+
=
+ + + +

iii) Khi thm 30,00mL Fe
3+
vo th trong dung dch cn d 10mL Fe
3+
:
| |
| |
2
0 , 10
0 , 20
3
2
= =
+
+
Fe
Fe

Thay vo biu thc tnh E ta c: E = 0,511V
c) i) G = -RTlnK
sp
= 68,72kJ
Mt khc ta c: G = -nFE E
o
= -0,707V
ii) Cu
+
+ I
-
= CuI E
o

= 0,707V
Cu
2+
+ e = Cu
+
E
o

= 0,153V
Phn ng kh Cu
2+
bng I
-
xy ra theo phng trnh:
Cu
2+
+ I
-
+ e = CuI
(r)
E
o
= 0,86V
T y ta tnh c ga tr E
o
ca phn ng:
2Cu
2+
+ 4I
-
2CuI
(r)
+ I
2(aq)
E
o
= 0,325V.
E
o
c ga tr dng cho bit rng phn ng xy ra theo chiu thun. iu ny c th c
gii thch do I
-
va ng vai tr cht kh va ng vai tr tc nhn to kt ta. S to thnh kt ta
CuI l bc chnh ca phn ng, s to kt ta CuI lm cho ion Cu
+
b tch ra khi dung dch v
a phn ng din ra theo chiu thun.
iii) G
o
= -nFE
o
= -31,3kJ
Mt khc G
o
= -RTlnK K = 2,9.10
5
.
OLYMPIC HA HC QUC T LN TH 34:
ng c l mt phn quan trng trong cuc sng hin i. Cc xe hi chy in ang c
pht trin bo m s vn chuyn trong tng lai. Mt trong s nhng phng php chnh cho
cc phng tin chy bng in l s dng cc ngun nng lng in thch hp. Acquy th cn
phi sc li khi ht in nn n khng th s dng lin tc. S dng phng php in situ tng qut
to ra in trong cc pin nhin liu l mt phng php rt hp dn. Pin nhin liu l mt t bo
in ha m trong cc phn ng ha hc din ra lin tc. Pin nhin liu s dng cc phn ng
chy sinh ra in. Cc bn phn ng cng din ra cc in cc v electron c chuyn ha
thng qua mt mch in kn. Cc electron c phn lp bi mi trng ion cha dung dch hoc
cht rn trng thi nng chy (u c tnh dn in). Cc phn ng din ra cc in cc ca pin
nhin liu hydro oxy vi cht in ly l dung dch KOH l:
O
2(k)
+ 2H
2
O + 4e

= 4OH
-
(aq)
(1)

H
2(k)
+ 2OH
-
(aq)
= 2H
2
O + 2e (2)
Phn ng tng qut s l: 2H
2
+ O
2
= 2H
2
O (3)
Sn phm ca phn ng l nc v hiu sut l t 50 60%
1) Vit phn ng xy ra catot
2) Vit phn ng xy ra anot
3) Nu cht in ly l axit photphoric th phn ng s xy ra nh th no?
S thay i ca nng lng Gibbs G
o
l thc o s chuyn dch chiu ca phn ng. S
chuyn i nng lng c cho bi h thc G
o
= -nFE
o
. n l s electron vn chuyn trong phn
ng v F l hng s Faraday (F = 96487C). Th in cc chun ca O
2(k)
25
o
C l +1,23V.
4) Hy tnh G
o
ca pin nhin liu trong mi trng axit (cu 3)
Qa trnh sinh ra nng lng do s t chy nhin liu l kh kim sot. H Lan, kh
thin nhin l mt ngun nng lng hp dn do n lun c sn. Cc nh my in hin i c th
chuyn ha c 35 40% ngun nng lng sinh ra do t chy kh thin nhin. Phn ng chy
ta nhit ca kh thin nhin (metan) c biu din bi phng trnh:
CH
4(k)
+ 2O
2(k)
CO
2(k)
+ 2H
2
O
(k)
+ nng lng
Nng lng sinh ra thng c s dng mt cch gin tip si m cn nh hay
chy cc my mc. Tuy nhin, trong nhng loi ximng chu nhit cha cc oxit kim loi trng
thi rn (tn ti trng thi ion) lm nhng cht dn in th kh thin nhin c th c s dng
mt cch trc tip, khng cn xc tc v hiu sut chuyn ha cao hn hn (75%). Phn ng trong
loi pin nhin liu ny l:
CH
4(k)
+ 2O
2(k)
CO
2(k)
+ 2H
2
O
(k)

5) Vit cc phn ng catot v anot.
Mt loi pin chu nhit khc tn dng cacbonat nng chy nh l cht dn in. Hydro
c s dng lm nhin liu, oxy c trn vi CO
2

6) Vit phn ng catot v anot v phn ng xy ra.
BI GII:
1) catot oxy b kh v ion hydroxit (phn ng 1)
2) anot hydro b oxy ha thnh nc (phn ng 2)
3) Anot: 2H
2
4e + 4H
+

Catot: 4e + 4H
+
+ O
2(k)
2H
2
O
(k)

Phn ng chung: 2H
2(k)
+ O
2(k)
2H
2
O
(k)

4) Th kh chun ca phn ng xy ra catot: 0V
Th kh chun ca phn ng xy ra anot: +1,23V
S electron vn chuyn: 4e
G
o
= -nFE
o
= -474716J
5) CH
4(k)
+ 2(O
2-
, cht dn in) CO
2(k)
+ 2H
2
O
(k)

+ 4e
O
2(k)
+ 4e

2O
2-
(cht dn in)
CH
4(k)
+ 2O
2(k)
CO
2(k)
+ 2H
2
O
(k)

6) Anot: 2H
2(k)
+ 2CO
3
2-
(l)
2CO
2(k)
+ 2H
2
O
(k)

+ 4e
Catot: O
2(k)
+ 2CO
2(k)
+ 4e 2CO
3
2-
(l)

Phn ng chung: 2H
2
+ O
2
= 2H
2
O
OLYMPIC HA HC QUC T LN TH 35:
Pin Ni Cd (Nicad) c s dng rng ri trong cc loi thit b b tn nh in thoi di
ng, my quay phim xch tay, laptop, v.v Pin Ni Cd c ga va phi v c chu trnh sng cao
ng thi c th hot ng c nhit rt thp hay rt cao. N khng cn phi c bo
dng v c th c np in 2000 ln.. Mt t bo ca pin Ni Cd thc hin hai na phn ng
sau:
Cd(OH)
2(r)
+ 2e Cd
(r)
+ 2OH
-
E
o
1
= -0,809V
2NiO(OH) + 2H
2
O + 2e 2Ni(OH)
2(r)
+ 2OH
-
E
o
2
= -0,490V
E
o
1
; E
o
2
l th kh chun 25
o-
C.
1) Phn ng no xy ra catot? Vit phng trnh Nernst.
2) Phn ng no xy ra anot? Vit phng trnh Nernst.
3) Vit phn ng chung.
4) Tnh E ca phn ng 25
o
C.
5) Tnh khi lng Cd cha trong 1 chic in thoi di ng c s dng pin Ni Cd. Bit
cng sut thng thng ca pin l 700mAh.
BI GII:
2NiO(OH) + 2H
2
O + 2e 2Ni(OH)
2(r)
+ 2OH
-
E
o
c
= -0,490V
| |
2
ln
2

= OH
F
RT
E E
o
c c

Cd
(r)
+ 2OH
-
Cd(OH)
2(r)
+ 2e E
o
a
= -0,809V
| |
2
1
ln
2

=
OH
F
RT
E E
o
a a

Cd
(r)
+ 2NiO(OH)
(r)
+ 2H
2
O 2Ni(OH)
2(r)
+ Cd(OH)
2(r)
nap
phong

E = E
o
a
E
o
c
= 1,299V
700mAh = 0,700A . 3600s = 2520C
n
Cd
= 2520/2.96485 = 0,013mol m
Cd
= 0,013.112,4 = 1,47g
OLYMPIC HA HC QUC T LN TH 37:
Mt s hp cht v c c s bin i s oxy ha, chng hn nhiu hp cht ca Mn c
phm vi s oxy ha t 0 n +7. Th kh tiu chun ca mt na phn ng c o da vo in
cc hydro. Trong bi tp ny, s kh Mn
2+
+ 2e Mn c th c vit l: Mn
2+
(1,5)Mn. Mn
trong dung dch axit xy ra mt lot s kh: Mn
3+
Mn
2+
Mn c th c vit nh sau:
Mn
3+
(1,5)Mn
2+
(-1,18)Mn.
S kh t xy ra nu nh th kh l dng. S Frost v nE
o
(n l s electron them
gia vo na phn ng) ca cp X(N)/X(O) theo s oxy ho N ca nguyn t, c dng ch ra
cc vi ht bn nht ca cc hp cht c cc s oxy ha khc nhau. Hnh di l s Frost ca
Mn
3+
/Mn
2+
/Mn.

1) Th kh ph thuc nng ca vi ht trong mt dung dch. MnCO
3
c tch s tan
K
sp
=1,8.10
-11
. Hy dng phng trnh Nernst tnh th ti 25
o
C ca mch in ha gm:
Mn
(r)
Mn
2+
(aq)
Mn
2+
(aq)
/MnCO
3
Mn
(r)
nu nng Mn
2+
in cc bn phi l
1,0.10
-8
M.
2) i vi oxy, th kh tiu chun trong dung dch axit nh sau: O
2
(0,7)H
2
O
2
(1,76)H
2
O. Tnh
th kh ca na phn ng kh O
2
thnh H
2
O. H
2
O
2
c th t phn hy c khng?
Xenon diflorua c th c to ra khi t mt bnh sy kh cha kh xenon v kh flo
di nh sng mt tri. Na phn ng kh XeF
2
xy ra nh sau:
XeF
2(aq)
+ 2H
+
(aq)
+ 2e Xe
(k)
+ 2HF
(aq)
E
o

= 2,32V
3) Hy dng m hnh VSEPR d on s cp electron v hnh dng phn t ca XeF
2
. Hy
chng t rng trong dung dch nc, XeF
2
phn hy to ra O
2
, tnh E
o

ca phn ng ny.
Liu s phn hy c xy ra thun li trong mt dung dch c tnh axit hay tnh baz?
Hy gii thch bit 2H
2
O O
2
+ 4H
+
+ 4e c E
o
= -1,23V.
BI GII:
1) E
pin
= E
o
(0,0592/2)lg([Mn
2+
]
phi
/[Mn
2+
]
tri
)
K
sp
= [Mn
2+
][CO
3
2-
] = 1,8.10
-11

[Mn
2+
]
phi
= 1,0.10
-8
M v [Mn
2+
]
tri
= 1,0M; E
o
= 0,00V (do tt c u ca Mn)
Vy E
pin
= 0,237V
2) Phn ng kh oxy thnh nc c E
o
= (0,70 + 1,76)/2 = 1,23V
Qa trnh O
2
+ 4H
+
+ 4e 2H
2
O E
o
= 1,23V
Nh vy qa trnh 2H
2
O
2
2H
2
O + O
2
c E
o
= 1,06V > 0,00V
Vy phn ng xy ra theo chiu thun.
3) S cp electron l 5 (lng thp tam gic) nhng c 3 cp electron cc mt phng bin
nn cu to hnh hc ca XeF
2
l ng thng.
2H
2
O O
2
+ 4H
+
+ 4e E
o
= -1,23V
XeF
2(aq)
+ 2H
+
(aq)
+ 2e Xe
(k)
+ 2HF
(aq)
E
o

= 2,32V
2XeF
2(aq)
+ 2H
+
(aq)
+ 2H
2
O Xe
(k)
+ O
2(k)
+ 4HF
(aq)
E
o
= 1,09V
Vy phn ng ny din ra d dng trong mi trng axit.
IV . OLYMPIC HA HC CC NC TRN TH GII:
OLYMPIC HA HC C 2004:
Th in cc chun ca bc v niken ln lt l E
o
(Ag
+
/Ag) = +0,80V v E
o
(Ni
2+
/Ni) = -
0,23V. Mnh no sau y l ng?
a) Ag
+
l tc nhn oxy ha cn Ni
2+
l tc nhn kh.
b) Ag
+
l tc nhn oxy ha mnh hn Ni
2+
v Ag l cht kh mnh hn Ni.
c) Ni
2+
c th b kh bi bc kim loi.
d) Ag
+
l tc nhn oxy ha mnh hn Ni
2+
v Ni l cht kh mnh hn Ag.
e) Ni
2+
l tc nhn oxy ha mnh hn Ag
+
v Ag l cht kh mnh hn Ni.
BI GII: Cu d
OLYMPIC HA HC ITALY 1999:
Cch biu din ng ca pin Daniell l:
a) Cu
2+
(aq)
Cu
(r)
Zn
(r)
Zn
2+
(aq)
.
b) Zn
2+
(aq)
Zn
(r)
Cu
(r)
Cu
2+
(aq)
.
c) Zn
(r)
Zn
2+
(aq)
Cu
2+
(aq)
Cu
(r)
.
d) Cu
(r)
Cu
2+
(aq)
Zn
2+
(aq)
Zn
(r)
.
BI GII: Cu c
OLYMPIC HA HC ITALY 1999:
in phn mt dung dch CuSO
4
(100mL; 0,150M) vi cng 1,25A cho ti khi ton b
Cu thot ra th thi gian cn thit l:
a) 77,2 pht
b) 60,3 pht
c) 19,3 pht
d) 38,6 pht
BI GII: Cu d
OLYMPIC HA HC O 1999:
Trong php phn tch ny tc nhn oxy ha l ion Ce
4+
, n d b kh thnh ion Ce
3+
. Ga tr
ca th oxy ha - kh ca nhng ion ny ph thuc vo nhng anion c mt. Cht chnh oxy
ha dung dch Ce
4+
l As
2
O
3
. Cho As
2
O
3
tc dng vi NaOH ri axit ha thu c asenit (AsO
3
3-
),
ion ny b Ce
4+
oxy ha thnh asenat (AsO
4
3-
), xc tc l mt lng nh OsO
4
, cht ch th oxy ha
- kh l feroin.
Vit phng trnh ion ca phn ng chun asenit bng Ce
4+
v tnh th im tng
ng (E
eq
) khi lm vic vi pH = 1.
E
o
1
(AsO
4
3-
/AsO
3
3-
) = 0,56V
E
o
2
(Ce
4+
/Ce
3+
; HClO
4
) = 1,70V
BI GII:
AsO
3
3-
+ 2Ce
4+
+ H
2
O 2Ce
3+
+ AsO
4
3-
+ 2H
+

| || |
| |
| |
| |
| |

+
+ + = + =
3
3
3
4
2
1
3
3
2
3
4
1 1
lg
2
059 , 0
lg
2
059 , 0
lg
2
059 , 0
AsO
AsO
H E
AsO
H AsO
E E
o o

Khi pH = 1 th E
1
=
| |
| |

+
3
3
3
4
1
lg
2
059 , 0
059 , 0
AsO
AsO
E
o

| |
| |
| |
| |
| |
| |
| |
| |
| |
| |

+
+

+
+
+
+
+ = =
= =
+ =
3
4
3
3
3
4
3
3
3
4
3
4
2 1
2 1
3
4
2 2
lg
2
059 , 0
lg 059 , 0 lg
2
059 , 0
lg 059 , 0 059 , 0
lg
2
059 , 0
AsO
AsO
Ce
Ce
AsO
AsO
Ce
Ce
E E
E E E
Ce
Ce
E E
o o
eq
o

im tng ng:
| |
| |
| |
| |
90 , 0
3
4
3
4
3
3
= =
+
+

eq
E
Ce
Ce
AsO
AsO
V
OLYMPIC HA HC C 1999 (Vng 2):
Cho ba t bo in ha vi cc hiu in th tng ng 298K:
1) Hg/HgCl
2
, KCl (bo ho)//Ag
+
( a = 0,0100mol/L)/Ag E = 0,439V
2) Hg/HgCl
2
, KCl (bo ho) = AgI (bo ho)/Ag E = 0,089V
3) Ag/AgI (bo ho), PbI
2
(bo ho) // HgCl
2
, KCl (bo ho)/Hg E = 0,230V
a) Hy trnh by khi nim hot ngha l g v n c ng dng u trong in ha
hc?
b) Tnh T
AgI
.
c) Tnh T ca PbI
2

Bit E
o
(Ag
+
/Ag) = 0,799V; R = 8,314J/K.mol; F = 96487C.
BI GII:
a) Do tc ng tng h ca cc ion vi nhau m nhiu khi cc dung dch vi nhng nng
C > 0,01M khng cn x s nh nhng dung dch l tng na. Khi ngi ta tnh ton
bng nng hu hiu v gi l hot . nhng nng thp th hot bng nng
.
T in p ca t bo 1 ngi ta c th tnh c in th ca in cc calomen
[Hg/Hg
2
Cl
2
, KCl (bo ho)].
Sau c th tnh c nng ion bc trong t bo 2. V rng y nng ion iodua
bng nng ion bc, cho nn kt qa l tch s ho tan ca bc iodua T = [Ag
+
]
2
.
Cng t hiu in th ca t bo 3 ngi ta c th tnh c nng ion bc ri t s
dng tch s ho tan va tnh c trn c th tnh c nng ion iodua trong t bo
ny. Nng iodua ny ln hn nhiu so vi nng ion bc. Lng d ion iodua phi
hnh thnh do s ho tan ch iodua, mt na lng d cho bit nng ion ch. Bng
cch c th tnh c tch s ho tan ca PbI
2
.
b) Tnh in th ca in cc calomen: E
1
= E(Ag
+
/Ag) E
calomen

Vi V Ag a
F
RT
E Ag Ag E
o
681 , 0 ) ( ln ) / ( = + =
+ +

Tnh nng ion bc:
E
2
= E(AgI (bo ha)/Ag//Ag) E
calomen
E(AgI (bo ha)/Ag//Ag) = 0,331V
Mt khc ta c:
E(AgI (bo ha)/Ag//Ag) = M Ag a V Ag a
F
RT
E
o 8
10 . 22 , 1 ) ( 331 , 0 ) ( ln
+ +
= = +
Vi i lng ny th [Ag
+
] = a(Ag
+
)
T
AgI
= 1,48.10
-16
.
c) E
3
= E
calomen
E(AgI (bo ho), PbI
2
(bo ho)/Ag)
E(AgI (bo ho), PbI
2
(bo ho)/Ag) = 0,012V
Tng t nh phn b, kt qa thu c y l [Ag
+
] = 4,89.10
-14
M
Phn nng ion iodua sinh ra t AgI cng bng nh vy.
S dng tch s ho tan i vi AgI tnh c phn b ta c:
[I
-
] = 3,02.10
-3
M
Phn nng in iodua sinh ra t AgI l khng ng k so vi ga tr ny. Nh vy nng
ion ch s l 0,5[I
-
].
T(PbI
2
) = 0,5[I
-
]
3
= 1,38.10
-8
M
3
.
OLYMPIC HA HC C 1999 (Vng 3):
Cho cc th chun sau y:
AgBr
(r)
+ e Ag + Br
-
E
o
1
= 0,0713V
Ag
+
+ e Ag E
o
2
= 0,7996V
a) Trn c s hy tnh T
AgBr
25
o
C.
b) T hy tnh G
o
i vi qa trnh: AgCl
(r)
Ag
+
(aq)
+ Cl
-
(aq)
. Bit S
AgCl
(25
o
C) =
1,274.10
-5
M.
BI GII:
a) E
o
1
c lin quan n mt bn t bo, trong trn mt lp kt ta bc bromua nng
ion bromua l 1,00M. Nh c E
o
2
ngi ta c th theo phng trnh Nernst tnh c nng
ion bc trong t bo v t nh c [Br
-
] = 1,00M c th tnh c tch s ho tan.
2 13 13
1 2 1
10 . 81 , 4 10 . 81 , 4 ln M T M C
F
RT
E E
AgBr
o o
= + =
b) T ho tan ta c: [Ag
+
] = [Cl
-
] = 1,274.10
-5
M v nh vy l tch s ho tan T =
(1,274.10
-5
)
2
. T cng l hng s cn bng K
C
i vi phn ng: AgCl
(r)
Ag
+
(aq)
+ Cl
-
(aq)

K
C
ngoi ra cng l hng s cn bng nhit ng lc hc. iu ny c ngha l:
G
o
= -RTlnT = 55,8kJ/mol.