7

(Redox titration)

7.1

Ce4+

Fe2+

3+
ZZ
X
YZ
Z Ce

Fe3+

4+ 3+ (
oxidizing agent) 2+ 3+
( reducing agent)

Ce4+

eFe

2+

3+
ZZ
X
YZ
Z Ce
3+
ZZ
X
YZ
Z Fe

(reduction)
(oxidation)

7.1
Cu Ag
Cu ( anode)
Ag (cathode)

164

Cu

Ag

CuSO4

AgNO3

()

Cu

Ag

CuSO4

AgNO3

()
7.1

() ()

(galvanic cell) (Voltaic
cell)
(electrolytic cell)

165

() ()

||||
7.1
Cu|Cu2+(0.02M)||Ag+(0.02M)|Ag

7.1 7.5

7.1 Al H2

Al H2

2Al(s)

2Al3+(aq) + 6e
6e- + 6H+(aq)
3H2(g)

2Al(s)+6H+(aq)
2Al3+(aq)+3H2(g)
7.2
1)Cu(s) +
2)Zn(s) +
3)H2(g) +
4)2Al(s)+

2Ag+(aq)
Cu2+(aq)
Cu2+(aq)
3Cu2+(aq)

Cu2+(aq) + 2Ag(s)
Zn2+(aq) + Cu(s)
2H+(aq) + Cu(s)
3Cu(s) + 2Al3+(aq)

1)

Cu
Cu

Cu2+ + 2eAg

2)

2Ag+ + 2e-
2Ag
Zn
Zn

Zn2+ + 2eCu
Cu2+ + 2e-
Cu

166

3)

H2
H2

2H+ + 2eCu

4)

Cu2+ + 2e-
Cu
Al
2Al
2Al3+ + 6eCu
3Cu2+ + 6e-
3Cu

7.3 Cu(NO3)2
Fe2+ Cu2+

Cu2+
Fe(s) + Cu2+(aq)
Fe2+(aq) + Cu(s)

Fe(s)

Cu2+(aq) + 2e-

Cu2+

Fe2+(aq) + 2eCu(s)

7.4
Mg(s) + Sn2+(aq)
Mg2+(aq) + Sn(s)

Mg(s)
Mg2+(aq) + 2e-

Sn2+(aq) + 2e-
Sn(s)

Mg|Mg2+||Sn2+|Sn

167

Eocell

Eocathode

Eoanode

7.5 Eocell

Ag+
Cu2+

+
+

e2e-

ZZ
X
YZ
Z
ZZ
X
YZZ

Eo
Eo

Ag
Cu

=
=

0.800 V
0.337 V

Ag+ Cu2+
Ag+ Cu2+
Eocell

Eocathode
0.800
+0.463 V

=
=
=

2Ag+

Cu

ZZ
X
YZ
Z

Eoanode
0.337

Cu2+

2Ag

..1889 (Walther Hermann Nernst)

aA

bB

+ .... +

ne-

ZZ
X
YZ
Z

cC

dD

+ ....

ac aDd
RT
ln aC
nF
aA aBb

Eo -

Eo

V
V
8.314JK-1mol-1

96,485 C

168

25oC(298K)

Eo -

c
d
0.0591
[C][D]
log
a
b
n
[A][B]

7.2

( Y) ( X)

Fe2+ Ce4+
Ce4+

Fe2+ +

Ce4+

ZZ
X
YZ
Z

Fe3+

Ce3+

SCE||Ce4+,Ce3+,Fe3+,Fe2+|Pt

ECe4+ EFe3+

169

7.2.1

7.6 0.0500 M Fe2+ 100.00
0.100M Ce4+ 1.00M H2SO4 Ce4+
1)
2)
3)
4)

0.00
25.00
50.00
60.00

mL

mL
mL
mL
mL

Ce4+ +

e-

Fe3+ +

e-

3+
ZZ
X
YZ
Z Ce
2+
ZZ
X
YZ
Z Fe

Ce4+ +

Fe2+

3+
3+
ZZ
X
YZ
Z Fe + Ce

Eo=1.44V
Eo=0.68V

1M
1M

H2SO4
H2SO4

1) Ce4+

2)Ce4+ 25.00 mL Ce3+

Fe2+ Fe3+ Ce3+
Fe2+-Fe3+
Fe2+
Fe3+

[Fe2+]

[Fe2+]

[Fe2+] =
=
[Fe2+]

[Fe3+]

=
=

e-

ZZ
X
YZ
Z

Fe2+

[Fe2+] [Fe2+]
0.05 50.00
2.50
=
M
55.00
50.00 + 5.00
[Ce4+]
0.100 5.00
0.500
=
M
55.00
55.00
2.50
0.500
2.00
=
M

55.00
55.00
55.00
[Fe2+]
0.500
M
55.00

170

0.0591
[Fe2+]
log
1
[Fe3 +]
2.00 / 55.00
0.68 0.0591 log
0.500 / 55.00
0.68 0.036
0.64 V
0.68

=
=
=
=

3) Ce4+ 50.00

Fe2+
2
Eeqp

Eeqp

mL

[Fe2+]eqp
EoFe3+ - 0.0591log
[Fe3 +]eqp
[Ce3 +]eqp
o
4+
E Ce - 0.0591log
[Ce4 +]eqp

2Eeqp =

[Ce3 +]eqp[Fe2+]eqp
EoCe4+ + EoFe3+ - 0.0591log
[Ce4 +]eqp[Fe3 +]eqp

[Fe2+] = [Ce4+] = 0
[Fe3+] = [Ce3+]

2Eeqp

[Ce3 +]eqp[Fe2+]eqp
EoCe4+ + EoFe3+ - 0.0591log
[Ce4 +]eqp[Fe3 +]eqp

Eeqp

Eo'Fe2+ + Eo'Ce4+
2
0.68 + 1.44
2
1.06 V

=
=
=

4) Ce4+ 60.00

Fe3+
Ce3+ Ce4+ Ce3+-Ce4+
Ce4+
[Ce3+]
=
[Ce4+]
mL

=
[Ce4+]

=
=
=

0.100 50.00
5.00
=
M
100.00 + 60.00
160.00
[Ce4+] [Ce4+]
0.100 60.00
5.00
100.00 + 60.00
160.00
1.00
M
160.00

171

=
=

=
=
Fe2+

0.0591
[Ce3 +]
log
1
[Ce4 +]
5.00 / 160.00
1.44 0.0591 log
1.00 / 160.00
1.44 0.0413
1.40 V
Ce4+ 7.2(A)
1.44

,V

7.2

, Fe2+

, U4+

0.1000M Ce4+, mL
0.0500M Fe2+ 50.00mL

Ce4+(A) 0.0250M U4+

0.1000M

0.1000M Ce4+(B)

(Skoog,West&Holler,1997,p.348)
7.2.2

Keq
7.3

172

7.3

(Skoog,West&Holler,1997,p.351)
7.3 EoA EoT
1.20,1.00,0.80,0.60
0.40 V
1

A > B > C > D > E

Keq
7.3

2

4

173

1)(self indicator)

KMnO4 KMnO4
0.02 M 5.0 10-6
KMnO4
Fe2+ KMnO4
7.4

()

()

()

7.4
Fe2+ KMnO4 (), Fe2+
(), Fe2+ Fe3+ ()
(Hill&Petrucci,2002)

MnO4-

KMnO4 KMnO4
Mn2+ KMnO4

2)(specific indicator)

(starch) (amylose) I3(triiodide ion)

174

KSCN Fe3+
Ti3+ Fe(SCN)2+ Fe3+ Ti3+
Fe2+
3)(external indicator)

(internal indicator)
Fe(CN)63- Fe2+
Fe(CN)63- Fe2+
3

4)(redox indicator)

Fe2+ Ce4+ H2SO4 1.0 M
7.1 E 1.06 V
1,10-(II)(1,10-phenanthroline
iron(II)complex) (ferroin) 7.1

1.06V -
(p-nitrodiphenylamine) -

175

7.1

5-Nitro-1,10-phenanthroline ferrous
sulphate (nitroferroin)
1,10-phenanthroline ferrous
sulphate (ferroin)
5-Methyl-1,10-phenanthroline ferrous
sulphate (methylferroin)
NPhenylanthranilic acid
2,2-Dipyridyl ferrous sulphate
5,6-Dimethylferroin
4,7-Dimethyl-1,10-phenanthroline ferrous
sulphate (4,7-Dimethyl ferroin)
Diphenylaminesulphonic acid
3,3-Dimethylnaphthidine-disulphonic acid
Diphenylbenzidine
Diphenylamine
3,3Dimethylnaphthidine
Starch-I3-, KI
Methylene blue

(Eo) pH=0

Pale blue

Red

1.25

Pale blue

Red

1.06

Pale blue
Purple red
Faint blue
Pale blue

Red
Colouress
Red
Red

1.02
1.08
0.97
0.97

Pale blue
Red-violet

Red
Colouress

0.88
0.85

Reddish purple
Violet
Violet
Purplish red
Blue
Blue

Pale green
Colouress
Colouress
Colouress
Colouress
Colouress

0.80
0.76
0.76
0.71
0.53
0.52

( , 2542, 644)
7.4

7.4.1

1)(KMnO4)

MnO4-

ZZ
X
MnO4- + 8H+ + 5e- YZ
Z

Mn2+ +

4H2O

Eo=1.51V

MnO4-
MnO4- +

ZZ
X
e- YZ
Z

MnO42-

Eo=0.564V

176

(pH 4)
MnO4- MnO2

ZZ
X
YZ
Z

MnO2

2H2O

Eo=1.695V

ZZ
X
MnO4- + 2H2O + 3e- YZ
Z

MnO2

4OH-

Eo=0.588V

MnO4- + 4H+ + 3e-

KMnO4
KMnO4

MnO2
4MnO4-

2H2O

ZZ
X
YZ
Z

4MnO2

3O2

+ 4OH-

MnO4 Mn2+
MnO2 Mn2+ MnO4 MnO4
MnO2

2MnO4- + 3Mn2+ + 6H2O

ZZ
X
YZ
Z

5MnO2 + 4H3O+

KMnO4
KMnO4
MnO2 KMnO4 MnO2

KMnO4 Na2C2O4
As2O3
2+
ZZ
X
2MnO4- + 5C2O42- + 16H+ YZ
Z 2Mn + 10CO2 + 8H2O
2+
ZZ
X
5As2O3 + 4MnO4- + 12H+ YZ
Z 5As2O5 + 4Mn + 6H2O

KMnO4

Fe2O3,Fe2O4
Fe2O3.H2O

177

HCl,H2SO4 HNO3


Na2CO3

+2
KMnO4 SnCl2
Fe2+ KMnO4 Cl( HCl SnCl2) Fe2+
KMnO4 Cl- Cl2
Fe
(Zimmermann-Reinhardt reagent) Fe2+
KMnO4 MnSO4,H3PO4
H2SO4 Mn2+ Eo MnO4-
KMnO4 Cl- H3PO4
H3PO4 Fe3+
Fe(HPO4)+ H2SO4
HCl
Fe2+
ZZ
X
MnO4- + 8H+ + 5Fe2+ YZ
Z

Mn2+ + 4H2O

2) (IV)

(IV)
Ce4+ H2SO4
HClO4 HNO3 Ce4+ H2SO4
Ce4+ Ce4+
Ce4+
Ce4+ H2SO4
Ce3+
Ce4+

e-

ZZ
X
YZ
Z

Ce3+

178

Ce(SO4)2

KMnO4
KMnO4
Ce4+ Cl- Cl-
HCl KMnO4
Ce4+
Na2C2O4
As2O3 ICl
OsO4 (nitroferroin)
Ce4+

KMnO4

Ce4+
Fe2+ Cl-
Ce4+ Cl-
Ce4+
Ce4+ Ce4+
Fe2+
(malic
acid) (malonic
ester)
3) (K2Cr2O7)

KMnO4 K2Cr2O7

K2Cr2O7

3+
ZZ
X
Cr2O72- + 14H+ + 6e- YZ
Z 2Cr + 7H2O

Eo=1.33V

K2Cr2O7
Fe2+ Cl- 1.0 M K2Cr2O7
Cl- K2Cr2O7
K2Cr2O7

179

Cr3+

K2Cr2O7

K2Cr2O7

KMnO4
K2Cr2O7

H3PO4
FeHPO4+ -
5,6-(5,6-dimethylferoin)
H3PO4
Fe2+ K2Cr2O7
3+
3+
ZZ
X
6Fe2+ + Cr2O72- + 14H+ YZ
Z 6Fe + 2Cr + 7H2O

K2Cr2O7
Fe2+ Fe2+
Fe2+ K2Cr2O7
Fe2+
K2Cr2O7
Fe2+
NO3-,ClO3-,MnO4-,(organic
peroxide)
4) (KBrO3)

KBrO3
BrO3- Br-
ZZ
X
BrO3- + 6H+ + 6e- YZ
Z Br + 3H2O

Eo=1.44V

Br-
Br- Br2

180

2-3
KBrO3
KBrO3 Br-
Br2 Br2

As Sb KBrO3
3As3+ + BrO3- + 9H2O
3Sb3+ + BrO3- + 9H2O

+
ZZ
X
YZ
Z 3H3AsO4 + Br + 9H
+
ZZ
X
YZ
Z 3H3SbO4 + Br + 9H

Mg2+ Cd2+ Co2+ Ni2+ TiO2+

Zn2+ Br2
KBrO3
5) (KIO3)

KI

ZZ
X
IO3- + 6H+ + 5I- YZ
Z 3I2 + 3H2O

I2 I2
Na2S2O3
2ZZ
X
I2 + 2S2O32- YZ
Z 2I + S4O6

1molIO3-

3molI2

6molS2O32-

(CCl4)
(CHCl3) I2 ICl2-

181

KIO3 KI
KI HCl CCl4
CHCl3 KIO3
KIO3 CCl4 CHCl3 I2
KIO3 ICl2-
KI
ZZ
X
2I- + IO3- + 6H+ + 6Cl- YZ
Z 3ICl2 + 3H2O

KIO3
(I2) (As3+) (Sb3+) (Cu2+) (Hg22+)
(Sn2+)
6)(I2)

I- NaI KI (I3-)

ZZ
X
I2 + I- YZ
Z I3

KI
Na2S2O3 BaS2O3.H2O ( As2O3
I2 )
I2

I2

I2 2
6.1)(iodimetry)

I2



I2 7.2

182

7.2

I2
ZZ
X
YZ
Z SO42- + 2H+ + 2I-

SO32-

I2 + SO32- + H2O

As3+

ZZ
X
YZ
Z As5+ + 2IZZ
X
I2 + H2S YZ
Z S + 2I- + 2H+
ZZ
X
I2 + Sn2+ YZ
Z Sn4+ + 2IZZ
X
I2 + 2S2O32- YZ
Z S4O62- + 2II2 + As3+

H2S
Sn2+
S2O32-

I- O2

ZZ
X
4I- + O2 + 4H+ YZ
Z 2I2 + 2H2O

I2 pH
O2 CO2 O2

I2

6.2) (iodometry)

I2

Na2S2O3

Aox

I-()
2S2O32- +

I2

ZZ
X
YZ
Z
ZZ
X
YZ
Z

Ared

S4O62- +

I2
2I-

183

KI NaI
(Aox) I2 I2
I2
Na2S2O3
I2 Na2S2O3
I2
I2
I2
7.3
I2 I2 S2O32-

I-

7.3

I-

Cr2O72-

Cr2O72- + 6I- + 14H+

Cl2

ZZ
X
YZ
Z 2Cl- +
ZZ
X
Br2 + 2I- YZ
Z 2Br- +
ZZ
X
ClO- + 2I- + 2H+ YZ
Z
+ ZZ
X
IO3 + 5I + 6H YZ
Z
2+
- ZZ
X
2Cu + 4I YZ
Z 2CuI

Br2
ClOIO3Cu2+

I2

ZZ
X
YZ
Z 2Cr3+ + 3I2 + 7H2O

Cl2 + 2I-

I2
I2
Cl- + I2 + H2O
3I2 + 3H2O
+ I2

O2 I-

ZZ
X
O2 + 4I- + 4H+ YZ
Z

2I2 + 2H2O

CO2() NaHCO3

7.4.2

Na2S2O3,
FeSO4 Ti2(SO4)3
( Na2S2O3)
O2

184

K2Cr2O7,KIO3 KBrO3
1)

Na2S2O3
I2,K2Cr2O7,
KIO3,KBrO3 K3Fe(CN)6
Na2S2O3
I2 KI I2
I2 Na2S2O3

+
I2

I-

2S2O32-

ZZ
X
YZ
Z
ZZ
X
YZ
Z

I2

2I-

S4O62-

Na2S2O3
Na2S2O3
S2O32- S
pH 9-10 Na2CO3
pH S2O32-
S2O32-
HgI2
2) (III)

(III) Ti3+
Ti3+ Fe3+
Ti3+ TiCl3(20% HCl) Fe3+
HCl Cl2
Cl2 Ti3+ Cu2+,
(nitroso),

185

3)

(II)

(II) Cr2+(chromous ion)

Cr2+ Cr3+

Cr2+ Fe3+(
Fe3+ Ti3+) Cr2+
Cr2+ O2
Cr2+
Cr2+ (azo compound)
4)

(C6H8O6)
O2

KIO3 I2 ,


2Ag+ + C6H8O6

ZZ
X
YZ
Z

2Ag

C 6 H6 O6

2H+

5) (As2O3)

As2O3 As2O3
KMnO4 I2
As2O3 As2O3 NaOH
HCl As2O3
KMnO4
2+
ZZ
X
5As2O3 + 4MnO4- + 12H+ YZ
Z 5As2O5 + 4Mn + 6H2O

6) (II)

(II) Fe2+

(II)
(ammonium iron(II)sulfate) FeSO4.(NH4)2SO4.6H2O
Fe2+
Ce4+

186

Fe2+
Fe2+
Fe2+
MnO4-,Ce4+, Cr2O72- -

7.5

2
2

7.5.1

1)(O3)

Mn2+ MnO4-

O3 N2
2)(Br2)(Cl2) I- IO3-
Br2 Cl2
3) (K2S2O8) Ag+
S2O82-
Ce3+ Ce4+,V4+ V5+,Mn2+ MnO4 K2S2O8 S2O82- SO42-

2S2O82-

2H2O

ZZ
X
YZ
Z

4SO42-

O2

4H+

4) (NaBiO3) Mn2+

Mn7+,Cr2+ Cr6+

187

NaBiO3

5)(KIO4) Mn2+ MnO4-

+
ZZ
X
2Mn2+ + 5IO4- + 3H2O YZ
Z 2MnO4 + 5IO3 + 6H

IO3- Hg2+

6)(HClO4) HClO4

Cr Cr2O72-,Ce Ce4+
HClO4 HClO4
Cl2
7)(H2O2) Fe2+
Fe3+ Sn2+ Sn4+ Mn2+ Mn4+
H2O2 H2O2 O2
IO4-

2H2O2
7.5.2

ZZ
X
YZ
Z

2H2O

O2

1)(SO2) SO32-
Fe3+ Fe2+,V5+ V4+
2)(II)(SnCl2) Fe3+ Fe2+
HCl SnCl2
Fe3+

HgCl2
ZZ
X
Sn2+ + 2HgCl2 YZ
Z

Hg2Cl2 + Sn4+ + 2Cl-

KSP Fe2+
KMnO4 SnCl2

Hg2Cl2

188

Sn2+ + Hg2Cl2

ZZ
X
YZ
Z

2Hg

Sn4+

2Cl-

3) (N2H4) As5+

N2

As3+ HgI42- Hg

H2SO4
4)

Al,Zn,Cd,Pb
Ni,Cu Ag Zn Ag

(Jones reductor)
(Walden reductor)
(zinc reductor)
(amalgamated
zinc)
2 cm 40-50cm
Hg Zn Zn
Zn Hg(NO3)2
H2SO4
Zn Zn
H2

Cr3+ Cr2+,Cu2+ Cu Fe3+ Fe2+

2Fe3+ +

ZZ
X
Zn(Hg) YZ
Z

2Fe2+

Zn2+

(silver reductor)
Ag
HCl Fe3+ Fe2+
Fe3+ + Ag(s) + HCl

7.6

ZZ
X
YZ
Z

Fe2+

AgCl(s) + H+

189

7.7 Na2S2O3 KIO3 0.245g

KI HCl I2
Na2S2O3 Na2S2O3 50.50 mL Na2S2O3

ZZ
X
YZ
Z
ZZ
X
YZ
Z

IO3- + 5I- + 6H+

3I2 + 6S2O32mmolNa2S2O3
mmolKIO3
mmolNa2S2O3

3I2 + 3H2O
6I- + 3S4O62=
=
=
=

Na2S2O3

=
=

7.8 H2O2
KMnO4 0.750M KMnO4

6
1
6 x mmolKIO3
0.245g 103 mg / g
6
fwKIO3

0.245 103 mg
214mg / mmol
=
6.869 mmol
6.869mmol
50.50mL
0.136 M
6

3%(w/w)
24.50 mL

H2O2

2+
ZZ
X
5H2O2 + 2MnO4- + 6H+ YZ
Z 5O2 + 2Mn + 8H2O

mmolH2O2
mmolKMnO4

mmolH2O2

=
=

H2O2
H2O2

=
=
=
=
=

5
2
5
mmolKMnO4
2
5
0.750mmol/mL24.5mL
2
45.94 mmol
45.94mmol34.02mg/mmol
1562.88mg
1562.88mg 100g

1000mg / g
3g
52.1g

190

7.9 S 8.00g H2S H2S

I2 0.050M 3.50 mL S

ZZ
X
H2S + I2 YZ
Z S + 2I
mmolS
=
mmolI2
mmolS
=
=
S
=

=
=

7.7

+ 2H+
1
1
mmolI2
0.050mmol/mL 3.50mL
0.0503.50mmol32.064mg/mmol
0.050 3.50 32.064 100
8.00 1000
0.070%

Ecell 0.5V

2

KMnO4
I3-

191

7.8
1.

1)
2)
3)
4)

2.

Fe(s)
Fe3+(aq) + 3eZn(s) + Mg2+(aq)
Zn2+(aq) + Mg(s)
Ca(s) + FeCl2(aq)
CaCl2(aq) + Fe(s)
2Mg(s) + O2(g)
2MgO(s)

1)Cu(s) + Fe3+(aq)
Cu2+(aq) + Fe2+(aq)
2)Sn2+(aq)+Cr2O72-(aq)
Sn4+(aq)+Cr3+(aq)+H2O

3.

1)Sn(s)|Sn2+(aq)||Zn2+(aq)|Zn(s)
2)Pt|O2(g,1atm)|H2O2(aq)||Ag+(aq)|Ag(s)

5.
1)
2)
3)
4)
6.
1) Fe2+ Br2
2) Fe3+ Sn2+
3) Ce4+ Fe(CN)64
7. Fe2+ 0.1600 M 50.00mL
Ce4+ H2SO4 1.0M (
) Ce4+
3.20mmol,8.00mmol 16.00mmol
8. 0.1 M Fe2+ 50.00 mL
0.1 M KMnO4 pH = 4.0
9. Na2C2O4
4.

0.020M KMnO4 35mL

10. 0.5359g

KMnO4 43.01mL ( KMnO4 2.054g

500.00mL) Fe

192

11. Ti3+ Ti4+

0.0232M
2.468g

KMnO4 KMnO4
43.96mL Ti

12. KMnO4

38.00mL KMnO4
0.200g As2O3 KMnO4
13. KI Fe3+ 30.00mL I2
Na2S2O3 0.1112M 24.35mL
Fe3+

193

.(2533). 1. :
.
.(2526). .:
.
. 2. :

.
.(2546). - -
. :.
.(2543). . .
.
.(2542). .:
.
.(2536). 1. :
.
Christian,G.D.(2004).Analytical Chemistry.(6th ed.).
United States of America:John Wiley & Sons,Inc.
Harris,D.C.(1999).Quantitative Chemical Analysis.
(5th ed.).New York:W.H.Freeman & company.
Hill&Petrucci.(2002).General Chemistry.(3rd ed.).Available
HTTP://cwx.prenhall.com/bookbind/pubbooks/hillchem3/
medialib/media_portfolio/04.html
Skoog,D.A.,West D.M.,& James F.H.(1997).Fundamentals of
Analytical Chemistry.(7th ed.).Fort Worth:Harcourt
College Publishers.