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ELECTROCHEMISTR
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R: B REDOX
• B :
1. MO4() + C
() ⇌ M2+() + C2()
2. H2O2() + CO2() ⇌ CO2() + O2()
3. NO2() + C2O72() ⇌ C3+() + NO3()
ELECTROCHEMISTR
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• OR .
– LEORA ( ) – GEROA ( )
C2+ + ⇄⇄⇄⇄ 2+ + C
R: C2+ + 2⇄ C
O: ⇄ 2+ + 2
(H )
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A
• T
– R C2+ C
– O 2+
• T :
R: C()2+ + 2⇄ C()O: ()⇄ ()
2+ + 2
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T (
)
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I E,
E C
( )
(+ )
V/G C
( )
(+ )
+
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T ()C () V/G C
+1.10
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E
C2+() + 2 ⇌ C() F
3+() +
⇌ F2+()C() ACE P() E
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C C
• V/G
• A :M ( )
A .
A ,
, .
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T C C
• C C :
1. A C 1.0 (II) .
2. A 1.0 (II) .
3. A
• T 1.10
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T C C
1.0 M 1.0
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C N
• S .
– C ()
() ()2+ (1.0 ) C()
2+ (1.0 ) C()
R O
D :
S
S :
S :
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T C S C• C :
1. A C 1.0 (II) .
2. A A 1.0 (I) .
3. A .
• T 0.46 .
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T C S C
•
C C CA :
C()C()2+ (1.0 )A()+(1.0 )A()
W
.
()()2+ (1.0 )C()
2+(1.0 )C() C
C
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• T C2+ 2+.
– I C2+ 2+.
• S, A+ C2+.
– B A+ C C 2+.• I ,
:
R
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S E P• P
• T , .
• T S H
E (SHE). – T SHE
0.00000000 V
– T
SHE
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T SHE C
• F :
1. A 1.0 (II) .
2. T S H E.
3. A .
• T 0.763 .
• T S H E. – I H+ H2.
• T .
–
2+
.
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T SHE C
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T CSHE C• T :
1. A C 1.0 (II) .
2. T S H E.
3. A .• T 0.337 .
• I SHE – T C2+ H2 H
+.
• T C .
–
T C2+
C .
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T CSHE C
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S E P
• S ()
.
L (L0 )
( OX
SHE)
F (F20 )
( RED
SHE)
• E
.
• E
.
⇌ .
⇌
.
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U S E P
• S E
• S E
• N:
E = E E I
E = E
+ E
I ,
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S
O
A
S
R
A
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H S E P
1. C
2. W E0 , E0 .
3. W , ..
E
0
.
4. B . D E0 ! (E0 INTENSIVE )
5. A . T E0 , (). I E0 , ().
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• W : P , MO4, (II) (III) , (III) (II) ?
• I S
, ?
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• G E :
2A+() + () ⇌ 2+() + 2A()
MO4
() + 5F2+
() + 8H+
() ⇌ M2+
() + 4H2O() + 5F3+
()
2NO3−(aq) + 8H
+() + 3C() ⇌ 3C2+() + 2NO() + 8H2O()
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G F E, K, E
• F
ΔGΔGΔGΔGoooo nFEnFEnFEnFEoooocellcellcellcell #
F 96 485 J/V (F C)
E
ΔG
G F E
• R E0 E K
ΔGΔGΔGΔG0000
nFEnFEnFEnFEoooo
cellcellcellcell 2.303RTlogK2.303RTlogK2.303RTlogK2.303RTlogKeqeqeqeq∴
.
at 25, .
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kJ/mol302.23-orrxnJ/mol302230-G
V1.5662emoleV
J48596emole2-G
0
-
-0
=∆
+⋅⋅=∆
kJ/mol285.60-orrxnJ/mol285595-G
V0.74emoleV
J48596emole4-G
0
-
-0
=∆
+⋅⋅=∆
D ∆G :
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D K :
.
. .
. . .
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• C . W +E.
V0.83- OH2He2O2H
V0.40 4OHe4O2HO
V1.23 O2H4e4HO
-(aq)2(g)
-(l)2
-
(aq)
-
(l)22(g)
(l)2
-
(aq)2(g)
+→+
→++
→++ +
V2.06 O2H2HO
V0.83 )e2OH2OH22(H
V1.23 O2H4e4HO
(l)2(g)22(g)
-
(l)2
-
(aq)2(g)
(l)2
-
(aq)2(g)
→+
+→+
→++ +
V1.23 O2H2HO
V0.83 )e2OH2OH22(H
V0.40 4OH4eO2HO
(l)2(g)22(g)
-
(l)2
-
(aq)2(g)
-(aq)
-(l)22(g)
→+
+→+
→++
M
,
H+ (
H2 )
L ,
H2O
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V2.06 O2H2HO
V0.83 )e2OH2OH22(H
V1.23 O2H4e4HO
(l)2(g)22(g)
-
(l)2
-
(aq)2(g)
(l)2
-
(aq)2(g)
→+
+→+
→++ +
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L D
• A
I F() , F(III) F(II).
ΔG H L, E0
ΔG0
H L
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T
(L
,
)
T ( )
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I ,
. T
ΔG:
(1) C
(2) T
(3) O
(4) H ( (3))
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L
F E
0 +1 +2F P ( E)
( ).
T E X+/X0
(X+ + → X0). E
(0 ).
X: E (N: E = ∆G/F)
:
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C M:
1 M 2+:
W M0 :
M2+ + 2 → M0 E = 1.18 V
C E:
= 2, ∴ E = −2.36
2 M 3+:
H: M3+ + 3 → M0
D E E
M2+ + 2 → M E = 1.18 V ∆G = 2×F×(−1.18 V) = +2.36F
M3+ + → M2+ E = +1.50 V ∆G = 1×F×(+1.50 V) = −1.50 F
M3+ + 3 → M ∆G= 3×F×(E) = +0.86 F∴ E = −0.287 V
C E:
= 3, ∴ E = −0.86
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A)
T . T
.
,
A. ,
A.
B)
R RA OA
.
, .
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) (
)
S , . T
()
)
I
,
. T
.
)
S
D
D
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W N2 ?
W N2 ?
I 2
I 4
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E C E P
E
T N
.
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T N E• S
N 25
C :
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• F :
T N :
• I C2+ C+ 1.0 , .. , E = E0
.
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• C C2+/C+
250C C+ 1/3 C2+
.
C
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• C
F
3+
/F
2+
F
3+
= 1.0 10
2
M F2+ = 0.10 M S4+/S2+
S4+ = 1.00 M S2+ = 0.100
M. A .
C E
S Q
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• S Q
E.
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CCEA CE
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M E E
AgBr s ⇌ Ag
a q B r
aq E 0.729 V
E 0.0592
1
log Ag Br 0.0592
1
logK
= ?
C:
AgBr s e ⇌ Ag s Br aq 0.071 V
A:
C :
Ag
a q e
⇌ Ags
0.800 V
AgBr s e ⇌ Ag s Br aq E 0.071 V
Ag s ⇌ Ag a q e E 0.800 V
AgBr s ⇌ Ag aq Braq
M E E
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M E E
C :
Au
aq 3e
⇌ Aus
1.520 V
AuCl aq 3e ⇌ Au s 4Cl aq 1.002 V
Au aq 4Claq ⇌ AuCl aq ?
C:
A:
Au aq 3e ⇌ Aus 1.520 V
Au s 4Cl aq ⇌ AuCl 3e aq 1.002 V
Auaq 4Cl aq ⇌ AuClaq 0.518 V
E 0.0592
3
log AuCl
Au
Cl
0.0592
3
logK
• M K
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Ag
0.100 M e
⇌ AgsAg saturated e ⇌ Ags
E E 0.0592
1 log
Agsaturated
Ag 0.100
Ag 0.100 M e ⇌ AgsC:
A: Ag s ⇌ Ag saturated e
Ag 0.100 M ⇌ Ag saturated
E C
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E C• N
• E0
•
ΔG0
ΔG0
= F(E0
)= +
E
( ) S, 212.3
J/
N, 212.3 J/
E C
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E C
• E
• I , ,
• P
o :
o :
• E 1 2
• T :
– E .
– E .
E C 1
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E C: 1
A
.
T
.
A .
T = .E
o P ().
o N ().
• / • E
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• / o C (+): M P
E0o A (): M N
E0o T MOST E0
• E o C (): L N
E0o A (+): L P
E0o T LEAST E0
, EDC CADE, DA ADE
(EDCA, A)
V0.83- OH2He2O2H
V0.40 4OHe4O2HO
V1.23 O2H4e4HO
-
(aq)2(g)
-
(l)2
-(aq)
-(l)22(g)
(l)2
-
(aq)2(g)
+→+
→++
→++ +
V2.06 O2H2HO
V0.83 )e2OH2OH22(H
V1.23 O2H4e4HO
(i)2(g)22(g)
-
(l)2
-
(aq)2(g)
(l)2-(aq)2(g)
→+
+→+→++
+
V1.23- 2HOO2H
V0.83- )2OHH2eO2(2H
V0.40- 4eO2HO4OH
(g)22(g)(i)2
-
(aq)2(g)
-
(l)2
-(l)22(g)-(aq)
+→
+→+++→
E V/G
E C: E A KI
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+ () + () 2.924
22 + 2 22 () + 0.828
2() + 2 2 () +0.535
2 () + 4+ +4 22 +1.229
C :
E1 = E(K+/K) E(I2/I) = (2.924 V) (+0.535 V)= 3.459V
E2 = E(H2O/H2,OH) E(I/I2) = (0.828V) (0.535 V)
= 1.363V
E3 = E(H2O/H2,OH) E(H2O/O2, H+)=(0.828V) (1.229)
= 2.057
2 ,
.
E C: E A NC
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E C: E A NC
N+ () + N() 2.714 V
2H2O + 2 2H2 () + OH 0.828 V
C2() + 2 C () +1.360 V
O2 () + 4H+ +4 2H2O +1.229 V
C :
E1 = E(N+/N) E(C/C2)= (2.714 V) (+1.360 V) = 4.074 V
E2 = E(H2O/H2,OH) E(C2/C)
= (0.828V) (1.360 V) = 2.188 VE3 = E(H2O/H2,OH) E(H2O/O2, H+)
=(0.828V) (1.229) = 2.057
E = E E
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• T V
O2() C2().
• H, (O2) .
•
T .
E2 = E(H2O/H2,OH) E(C/C2)= (0.828V) (1.360 V) = 2.188 V
E3 = E(H2O/H2,OH) E(H2O/O2, H+)=(0.828V) (1.229) = 2.057
OVERPOTENTIAL
C E: F E
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C F
• F L , (96,487 ) , ,
.
• A
.
M+ + M0 A0 A + • T M A
1 = 6.022 ×××× 1023
1 = 96485
C E F L E
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C E: F L E
Mass of substance oxidized or reduced
I ,
.
•
A (A) .
• Q () =
• 1 = 1 /
• I () =
• 1 = 1 /
• C (II) 3 20
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(II) 3.20
(II) 30.0.
: 2+ + 2 0
∴∴∴∴ = 2
A = 106.42
: 30
Mass of Pd 3.20
30 min
60 106.42
2
96485 C
mol e
= 3.18 P
• C ( STP)
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2.0 5.0
:
2 2 2() + 4+ + 4
∴∴∴∴ = 4
1 2 = 22.4
: 5
Vol 2.0
5 min
60 22.4
4
96485
C
mol e
= 0.0348 L 34.8 L
C A E C
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E E
• I ≈ 100% C. – T
: A, A, P.
• T CSO4 H2SO4
• T C C2+.
•
T C2+
C .
E C:
E NC
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E NC
• R () NC – C N+ C .
• I ( 3.852 V) ( )
NC, : – P (C2)
.
– M, N . T N
NC.
A
C
D C I
N()
C
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• M
CO2, O2, H2O.
( )
points.exposedatrapidlyoccursreactionThe
reactionoverallOFe2O3+Fe4 320
2
0 →
O2 + 4 + 2 H2O → 4 OH
F → F2+ + 2 −
4 F2+ + O2 → 4 F3+ + 2 O2−
2 + O2 + 2H2O → 4OH
F3+ + 3 H2O ⇌ F(OH)3 + 3 H+
F(OH)3 ⇌ FO(OH) + H2O
2FO(OH) ⇌ F2O3 + H2O
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C P• S .
1. P (
) .
2. C ,
.
C P
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3. A .
4 G, , .
C P
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C P
5. P
.
ceramic.withcoatedare bathtubsSteel
B
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B
• P ,
( )
• S ,
(
)
• F
,
V G
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C• E
• H ( )
.
• E : – A
– F
– B
– L+
P C
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L
S
:
A
:
L (
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)
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A B
L I
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