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Electrochemistry- Physicalchemistry
K1
lg K 1 =
2(0,94 + 0,40)
= 45,42 K 1 = 2,65.10 45
0,059
3)
lg K 1 =
10 2.10 2.(10 7 ) 2
o
2( E NO
/ NO
3
+ 0,40)
0,059
2OH10-7
= NO3 = 7,55.10 33 M
o
E NO
= 0,017V
/ NO
3
Electrochemistry- Physicalchemistry
0,025.(0,05) 2
0,0025
1.10 21 =
= Fe 3+ = 1,58.10 12 M
K=
2
2
0,025.
1,58.10 12
0,059 0,025
= 0,15 +
lg
= 0,15M
0,05
2
0,025
2)
Ag
+
Fe3+
Ag+
+
ncb:
0,05 x
x
lgK = (0,77 0,80)/0,059 = -0,51 K = 0,31
Electrochemistry- Physicalchemistry
Fe2+
x
] [
x2
= 0,31 x = Ag + = Fe 2 + = 4,38.10 2 M
0,05 x
[ Fe ] = 6.10
3+
6.10 3
= 0,80 + 0,059 lg 4,38.10 2 = 0,72V
4,38.10 2
K THI CHN HC SINH GII QUC GIA VIT NAM 2002 (BNG A)
1. Bit th oxi ha-kh tiu chun :
Cho : axit c H 2S pK1 = 7,00, pK2 = 12,90; HSO4- c pK = 2,00; Tch s tan
ca PbS = 10-26 ; PbSO4 = 10-7,8 ; PbI2 = 10-7,6.
Eo Fe3+/Fe2+ = 0,77 V ; Eo S/H2S = 0,14V ; Eo I2/2I- = 0,54V ; Ecal bo ho = 0,244V
BI GII:
1. a) Eo Fe3+/Fe2+ = +0,77 V
>
Eo Fe2+/Fe = -0,44 V nn:
Tnh oxi ho: Fe3+ mnh hn Fe2+
Tnh kh:
Fe mnh hn Fe2+
Do phn ng t pht xy ra gia 2 cp l: 2 Fe3+ + Fe 3 Fe2+
Nh vy Fe tan trong dung dch Fe(SO4)3 to thnh mui FeSO4, lm nht mu vng ( hoc nu)
ca ion Fe3+ v cui cng lm mt mu (hoc to mu xanh nht) dung dch.
b) Eo Cu+/Cu = + 0,52 V > Eo Cu2+/Cu+ = + 0,16 V nn:
Tnh oxi ho: Cu+ mnh hn Cu2+
Tnh kh:
Cu+ mnh hn Cu
Do phn ng t pht xy ra giaa 2 cp l: Cu+ + Cu+ Cu2+ + Cu
Phn ng nghch (Cu2+ phn ng vi Cu to thnh ion Cu+) khng xy ra. Do khi b bt ng
vo dung dch CuSO4 khng xy ra phn ng v quan st khng thy hin tng g.
2. Axit ho dung dch X:
S2- + 2H+ H2S (C H2S = 0,010 < S H2S nn H2S cha bo ho, khng thot ra khi
dung dch)
Phn ng:
+ 2 H+
K=1021
0,1
0,01
0,08
0,02
0,02
3+
2+
2 Fe + 2I 2 Fe
+
I2
K=107,8
0,08
0,06
0,02
0,02
0,08
0,030
3+
Thnh phn trong dung dch: Fe 0,020 ; Fe2+ 0,080 ;I2 0,030M ;H+ 0,02M
Electrochemistry- Physicalchemistry
Khi lng mol ca kim loi: A = n. . V kim loi ny y ng ra khi dung dch nn
ng lng ca Cu:
A1 = 103,6 x 1 = 103,6
A2 = 103,6 x 2 = 207,2
A3 = 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).
= C2H6
C2H6 + CO2.
K THI CHN HC SINH GII QUC GIA VIT NAM 2004 (BNG A)
Dung dch A gm AgNO3 0,050 M v Pb(NO3)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 AgNO3 0,010 M v KSCN 0,040 M.
a) Vit s pin .
b) Tnh sc in ng Epin ti 250C .
c) Vit phng trnh phn ng xy ra khi pin hot ng.
d) Tnh hng s cn bng ca phn ng .
Cho bit : Ag+ + H2O
AgOH + H+ (1) ; K1= 10 11,70
Pb2+ + H2O
PbOH+ + H+ (2) ; K2= 10 7,80
Ch s tch s tan pKs : AgI l 16,0 ; PbI2 l 7,86 ; AgSCN l 12,0 .
RT
0
ln = 0,0592 lg
EAg
;
=
0
,799
V
+
F
/Ag
2. Epin s thay i ra sao nu: a) thm mt lng nh NaOH vo dung dch B ; b) thm mt lng
nh Fe(NO3)3 vo dung dch X?
BI GII:
1. Ag+ + H2O AgOH + H+ ; K1 = 10-11,7
(1)
2+
+
+
-7,8
Pb + H2O PbOH + H
; K2 = 10
(2)
Do K2 >> K1 nn cn bng 2 quyt nh pH ca dung dch
Pb2+ + H2O PbOH + H+ ; K2 = 10-7,8 (2)
C
0,10
[ ]
0,10 x
x
x
x2
=10 7 ,8
0,1 x
x = 10-4,4 = [H+]
pH = 4,40
K2 = 10-7,8
Electrochemistry- Physicalchemistry
[PbOH ] = 10
[Pb ] 10
+
7 ,8
2+
] [
PbI2 Pb2+ + 2 I
Ks2 = 1.10-7,86
x
2x
-3
x = 1,51.10 M
2x = [I] = 2,302 . 10-3M
.10
[Ag ] = K[I ] = 31,02
.10
+
16
s1
= 3,31.10 14 M .
Ag
Dung dch X:
E 1 = 0,001V
Ag+ +
SCN AgSCN ;
0,010
0,040
0,030
0,010
AgSCN Ag+ + SCN
;
0,030
x
(0,030 + x)
x0,030 + x) = 10-12
10 12
+
[Ag ] = x = 3x10 2 = 3,33.10 11
1012,0
10-12,0
Ag
b)
AgI
PbI2
AgSCN
SCN 0,03 M
Ag
K = KsAgSCN
KsAgI
12
= 10
10
16
= 104
Electrochemistry- Physicalchemistry
RT
BI GII:
1.
2 IO4 + 16 H+ + 14 e
2 IO3 + 12 H+ + 10 e
2 HIO +
I2 (r)
2.
2 H+ + 2 e
+ 2e
2 IO4 + 16 H+ + 14 e
I2 (r)
+ 6 H2O
2 IO4 + 4 H+ + 4 e
I2(r) + 8 H2O ; Eo
I2(r) + 6 H2O ; Eo
I2(r) + 2 H2O ; Eo
2 I
= 1,31 V = Eo1
= 1,19 V = Eo2
; Eo
= 0,54 V = Eo4
o
2 IO3 + 12 H+ + 10 e ; K21 = 10
= 1,45 V = Eo3
-10Eo2/0,0592
Electrochemistry- Physicalchemistry
2 IO3
Eo5 = EoIO4-/IO3+
+ 12 H
I2(r) + 2 H2O
I2(r) + 6 H2O ; K2 = 10
= K2. K31
o EIO
= Eo6 =
3 /HIO
VIOE3-/HIO
3.
= 1,61 V
10Eo2/0,0592
+ 10 e
2 IO3 + 10 H+ + 8 e
8E 6/0,0592
K6 = 10
14 E1O 10 E2O
4
10 E2O 2 E3O
8
< HIO/I
Eo
= 1,125 (V)
nn HIO s t oxi ho - kh
4
2 HIO + 2 H+ + 2 e
2 HIO + 4 H2O
2 IO3 + 10 H+ + 8 e
4 I2(r) + 2 IO3 + 2 H+ + 4 H2O
10 HIO
I2(r) + 2 H2O
5
CO
C
C
2 I
I2(r) + 2 e
2 MnO4 + 10 I + 16 H+
2 Mn2+ + 5 I2(r) + 8 H2O
0,24
0,4
0,04 2 0,04 10
0,04 2
0,04 5
0,16
0
1
0,08
0, 2
MnO4 + 8 H+ + 5 e
I2(r)
CO
C
C
+ 6 H2O
2 MnO4 + I2(r)
0,16
0,2
0,08 2
0,08
0
0,12
; K = 10 163
Mn2+ + 4 H2O
2 IO3 + 12 H+ + 10 e
+ 4 H+
Electrochemistry- Physicalchemistry
/I
3
(r )
0,0592
lg IO3
10
] [H ]
2
+ 2
= 1,18V
BI GII:
1.
Trong th nghim ny, nc b in phn cng mt in th.
a) Dung dch NaOH:
anot:
2 OH
H2O + 1/2 O2 + 2 e
catot:
2 H2O + 2 e
H2 + 2 OH
H2O
b) Dung dch H2SO4:
anot:
H2O
catot:
2 H+ + 2 e
H2 + 1/2 O2
1/2 O2 + 2 H+ + 2 e
H2
H2O
H2 + 1/2 O2
Electrochemistry- Physicalchemistry
10
NH3 + H2O
pOH ca dung dch NaOH thm NH4Cl gim pH ca dung dch NaOH t 14
xung 11 c tnh theo cng
thc:
+
[NH4 ]
pOH = pKb + lg[NH ]
3
3 = 4,75 + lg [NH +]
4
[NH3]
Suy ra [NH4 ] = 0,0178 [NH3]
+
Khi pH ca dung dch NaOH gim t 14 xung 11 th [OH ] ca dung dch gim i: 1 103
= 0,999 mol. y chnh l s mol NH3 hnh thnh. Vy [NH3] = 0,999 mol/L v:
[NH4+] = 0,0178 0,999 0,0178 (mol/L)
S mol NH4Cl phi thm vo 1 lt dung dch:
n= n
1
(103)2
11 2
Electrochemistry- Physicalchemistry
11
[ Au(CN ) ]
=
Kb
[ Au ][CN ]
[ Au(CN ) ] = 99
[ Au ] + [ Au(CN ) ] 100
Electrochemistry- Physicalchemistry
12
][
Electrochemistry- Physicalchemistry
13
BI GII:
1. Cu trc ng thng:
N
Au
2.
4KAu(CN)2 + 4KOH
4Au + 8KCN- + O2 + 2H2O
mKCN = (20/197).(8/4).65,12 = 13,024g
3.
Electrochemistry- Physicalchemistry
14
Eo = -0,76V
Eo = +0,80V
BI GII:
a) Gin pin: Zn(r) Zn2+(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) Zn2+(aq) + 2e
Phi, kh: Ag+(aq) + e Ag(r) (nhn cho 2)
Phn ng ca pin Zn(r) + Ag+ Zn2+(aq) + 2Ag(r).
b) Eopin = Eo(phi) Eo(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
2
0,05916 a Zn .( a Ag )
0,05916
0,200
o
E pin = E pin +
lg
= 1,56
lg
= 1,52V
2
n
2
a Zn .( a Ag )
(0,100) 2
2+
Tr s dng ca Epin 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+ Zn2+(aq) + 2Ag(r).
c) Khi phng in hon ton, Epin = 0 v phn ng trong pin t cn bng
0 = 1,56 0,05916/2.lgK K = 5,5.1052; 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 [Zn2+] duy tr ti 0,200M
1,04 = 1,56
0,05916 0,200
lg
x = Ag + = 7,3.10 10 M
2
2
e) [Cl-]
Electrochemistry- Physicalchemistry
15
0,059 [ oxh]
lg
[ red ]
2
0,059 [ oxh]
o
lg
= 0,79V
Khi [InOx]/[Inred] = 10 th: E dd = E dip +
[ red ]
2
o
Vi di-bolane: E dd = E dip +
[
[
]
]
[ Fe ] [ Fe ] = 2,2
[ Fe ] [ Fe ]
3+
3+
2+
2+
o
Vi p-nitro-di-bolane: E dd = E pn +
[
[
[ Fe
1,04 = 0,77 + 0,059 lg
[ Fe
]
]
] [ Fe ] = 3,80.10
] [ Fe ]
3+
3+
2+
2+
Electrochemistry- Physicalchemistry
16
Electrochemistry- Physicalchemistry
17
[ H ] = {P
+
2
H2
.e
( 2 FE opin / RT )
{P
2
H2
.e
( 2 FE opin / RT )
} 1 / 6 cho
= 2,24.10 9 M 4 bar 1
(*)
e) pH = 5: Thay [H+] = 10-5M vo biu thc (*) trn ta tnh c [Mn(mn)2+] = 4,7.10-10M
pH = 8: Thay [H+] = 10-8M vo biu thc (*) trn ta tnh c [Mn(mn)2+] = 4,7.10-16M
f) t kim
Electrochemistry- Physicalchemistry
18
lg
4+
/ Sn 2 +
2
Sn 4+
i) Khi thm 5,00mL Fe3+ th lng Sn2+ chuyn sang Sn4+ s l 5,00/20,00.
Nh vy:
Sn 2+
15,0 / 20,0
=
=3
4+
5,0 / 20,0
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:
o
o
2 ESn
+ E Fe
4+
3+
/ Sn 2 +
/ Fe 2 +
E=
= 0,118V
3
iii) Khi thm 30,00mL Fe3+ vo th trong dung dch cn d 10mL Fe3+:
Fe 2+
20,0
=
=2
3+
10,0
Fe
[
[
[
[
[
[
]
]
]
]
]
]
Electrochemistry- Physicalchemistry
19
Electrochemistry- Physicalchemistry
20
RT
ln OH
2F
RT
1
ln
2F
OH
Eoa = -0,809V
nap
phong
2Ni(OH)2(r) + Cd(OH)2(r)
Electrochemistry- Physicalchemistry
21
Electrochemistry- Physicalchemistry
22
][ ]
[ ]
o
1
Khi pH = 1 th E1 = E
[
[
0,059 Ce 4 +
E2 = E +
lg
2
Ce3 +
Eeq = E1 = E2
o
2
[ ]
0,059 [ AsO ]
0,059 +
lg
[ AsO ]
2
0,059 AsO43 H +
E1 = E +
lg
2
AsO33
o
1
]
]
3
4
3
3
]
]
[
[
0,059
0,059 AsO43
+ 2
=E +
lg H +
lg
2
2
AsO33
o
1
3
4
3
3
Electrochemistry- Physicalchemistry
4+
3+
3
3
3
4
23
[ AsO ] = [Ce ] E
im tng ng:
[ AsO ] [Ce ]
3
3
3
4
4+
3+
eq
= 0,90 V
RT
ln a( Ag + ) = 0,681V
F
RT
ln a ( Ag + ) = 0,331V a ( Ag + ) = 1,22.108 M
F
Electrochemistry- Physicalchemistry
24
RT
ln C1 4,81.1013 M TAgBr = 4,81.10 13 M 2
F
Electrochemistry- Physicalchemistry
25