:

Cu
1/2 O2 + 2H+ + 2e-

Cu +2 + 2 eH2O

VTotal = (Ea + Wa ) (Ec +Wc ) + IR

Ea Ec
Wa Wc
.
: IR .
Ea Ec E


.







.

-:
.. . ..
154

:







.
1/2 Cl -

Cl2 + eAgCl + e-

Cl - + Ag

Ag+ + Cl-

AgCl + e-

AgCl
Cl2
Ag + Cl2

Ag

AgCl + 2e-

Control potential electrolysis

:
VTotal = (Ea + Wa ) (Ec +Wc ) + IR

SEC :

) Vcathod = ESCE - ( EC + Wc
-:
.. . ..
155

Qulomtry


:
W = QM/nF
:
: W
: M Q
: M/n
: F
Q=i.t

%100

:
:
.
:
.
:
Q = i . t = i . dt

.
.

.
-:
.. . ..
156

) H+ , OH (


( )
H + :
H2O

2H2O + 2 e-

1/2 O2 + 2H + 2 eH2 + 2OH

:
-1
.

-:
.. . ..
157

-2
.
-3 EDTA

:
-1 .
-2 .
-3
100-10.
-4
.

Conductometric titration

.

.

.

) (Electromotive force

( ).

).(1

e.m.f :

-:
.. . ..
158

I = E/R

-1 I/R
)L ( Conductance ( )1/R
I :
ohm-1 :

)..(2
)...(3

L= 1/R
I = E.L

-2 R l a :
).(4

R l/a

L R:
)..(5

L a/l

:
) ..............) 6

L = K . a/ l

) Kappa
( K
) (Specific conductance . ) (6
L=1, a=1

:
)(6

)..(7

L =K
K=I/R.l/a

ohm -1 . cm-1 mho K

mho 1 2
3 .

Equivalent conductance

. :
)..(8
-:
.. . ..
159

^ = 1000 . K / C

)(9

^ =K.V

: C .
: V .

Interionic effect
.

^ ^
.
Kohlraush





. :

= + + -

)(10

.
: 0.1 N 8.269X 10-3 mho/cm

:
= 1000 . K / C
= 1000 x 8.269 x 10-3 / 0.1
= 82.69 mho . cm2
-:
.. . ..
160

Principles of conductometric titrations

HCl

.NaOH
) (H+ + Cl- ) + (Na + + OH -

( Na + + Cl - ) + H2O

Ideal case
. HCl HCl
( ) :
= 349.82 + 76.34

H+ + Cl-

= 426.16 mho.cm2
HCl NaOH
NaCl
( )
:
Na+ + Cl- = 50.11 +76.34
= 126.43 mho. Cm2
NaOH

NaOH + NaCl :
Na+ + Cl- + Na+ + Cl- = 50.11+ 76.34 + 50.11 + 198
= 374.56 mhos. Cm2

:

NaOH

-:
.. . ..
161

AO .
OB .
.


,
.

-:
.. . ..
162