-:

* -:
:

(Ag+ )1 = C1AgNO3 +AgNO3

(Ag+ )1 = 0.01 0.892
(Ag+ )1 = 0. 00892

* EX -:
) EX = ES ( LX / LS
: EX is the unknown voltage being measured
)ES - Is the voltage of the standard cell (1.019 v
LX - Is the length of resistance wire required to balance the unknown voltage
LS - Is the length of resistance wire required to balance the standard voltage
-: KCl
) EX = ES ( LX1 / LS
) EX = 1.019 ( 25.1 / 69
EX = 0.3707 V
-: KBr
) EX = ES ( LX1 / LS
) EX = 1.019 ( 33.23 / 69
EX = 0.4907 V
-: KI
) EX = ES ( LX1 / LS
) EX = 1.019 (45.5 / 69
EX = 0.672 V

* :
E = RT/ F . Ln(Ag+ )1 / (Ag+)2
:

E0cell = 0
R = 8.3145 J K-1 MOL-1
F = 96485 C MOL-1
T = 25 + 273.15 = 298.15 K
E = Ex
(Ag+ )1 :
(Ag+)2 :

-: KCl
* (Ag+)2 :
0.3707 = 8.3145 298.15 / 96485 . Ln0.00892 / (Ag+)2
0.3707 = 0.02569 . Ln0.00892 / (Ag+)2
Ln0.00892 / (Ag+)2 = 0.3707 / 0.02569
Ln0.00892 Ln (Ag+)2 = 14.429
Ln(Ag+)2 = -4.7195 14.429
Ln(Ag+)2 =-19.1485
(Ag+)2 = e -19.1485
(Ag+)2 = 2.71828183 -19.1485
(Ag+)2 = 4.829 10-9
-: KBr
* (Ag+)2 :

0.4907 = 8.3145 298.15 / 96485 . Ln0.00892 / (Ag+)2

0.4907 = 0.02569 . Ln0.00892 / (Ag+)2
Ln0.00892 / (Ag+)2 = 0.4907 / 0.02569
Ln0.00892 Ln (Ag+)2 = 19.1
Ln(Ag+)2 = -4.7195 19.1
Ln(Ag+)2 = -23.8195
(Ag+)2 =e-23.8195
(Ag+)2 = 2.71828183 -23.8195
(Ag+)2 = 4.522 10-11
-: KI
: ( Ag+)2 *
0.672 = 8.3145 298.15 / 96485 . Ln0.00892 / (Ag+)2
0.672 = 0.02569 . Ln0.00892 / (Ag+)2
Ln0.00892 / (Ag+)2 = 0.672 / 0.02569
Ln0.00892 Ln (Ag+)2 = 26.158
Ln(Ag+)2 = -4.7195 26.158
Ln(Ag+)2 =-30.8775
(Ag+)2 =e-30.8775
(Ag+)2 = 2.71828183 -30.8775
(Ag+)2 =3.891 10-14


* -:
-: Solubility product constants
Ksp =( Ag+)2 . X-

= : X-

Ksp = + CAg+ . - CCl ( ) Ag(s) AgX KX AgX

.

-: KCl
-:
Ksp =( Ag+)2 . Cl (Ag+)2 = 4.829 10-9 -:

Cl--:
Cl- = - Cl- . CClCl- = + KCl . CKCl
Cl- = 0.902 0.01
Cl- = 0.00902
Ksp =( Ag+)2 . ClKsp = 4.829 10-9 0.00902
Ksp = 0.435 10-10 mol2 dm-6

-: KBr
-:
Ksp =( Ag+)2 . Br ( Ag+)2= 4.522 10-11 -:

Br--:
Br- = - Br-. C Br-

 Br- = + KBr . CKBr

Br- = 0.902 0.01
Br- = 0.00902
Ksp =( Ag+)2 . BrKsp = 4.522 10-11 0.00902
Ksp = 4.0788 10-13 mol2 dm-6
-: KI
-:
Ksp =( Ag+)2 . KI ( Ag+)2= 3.891 10-14 -:

KI--:
I- = - I-. C I I- = + KI . CKI
I- = 0.902 0.01
I- = 0.00902
Ksp = 3.891 10-14 0.00902
Ksp = 3.5 10-16 mol2 dm-6

* ) ( S -:
- :Solubility
S= ( KSP )1/2
-: KCl
-:
S =( 0. 435 10-10 )1/2

S= 6.6 10-6 mol dm-3

-: KBr
-:
S =( 4.0788 10-13 )1/2
S= 6.386 10-7 mol dm-3
-: KI
-:
S =( 3.5 10-16 )1/2
S = 1.87 10-8 mol dm-3

* -:

-:
S

KSP

( Ag+)2

x-

EX

)LX(average

AgX

6.610-6

0.43510-10

4.82910-9

0.00902

0.3707

1.52

AgCl

6.38610-7

4.078810-13

4.52210-11

0.00902

0.4907

33513

AgBr

1.8710-8

3.510-16

3.89110-14

0.00902

0.672

5.5.

AgI

-:
-:

) KSP ( AgBr ) > KSP ( AgI

> ) KSP ( AgCl

) S ( AgCl ) > S ( AgBr ) > S ( AgI

* -:
KSP
S AgCl
AgCl Ag+ Cl- 1:1 -:
C Ag+ = C Cl- = S
:
+ = - = +
-:
K = KSP = Ag+ . X-

-:

Ksp = + CAg+ . - CCl S -:

S2

+2

= Ksp

S AgCl + = 1 +
.
1
.
1/2
) S = ( KSP
-:
25 C -:

KSP At . C

KSP at 25 C

AgX

0.43510-10

1.7710-10

AgCl

4.078810-13

5.3510-13

AgBr

3.510-16

110-16

AgI

-: *
-: AgCl
-:

Ag(s) | AgCl ; KCl

c2( 0.01M KCl )

|| AgNO3 aq. c1(0.01M ) | Ag(s)

*The cathode is the electrode where reduction occurs.

Electrode type:- metal insoluble salt electrode:
Ag(s) AgCl (s) KCl(aq) electrode
Electrode reaction (in reduction direction) cathode:-

AgCl (s) + e-

Ag + Cl-(aq)

*The anode is the electrode where oxidation occurs.

Electrode type:- Metal metal-ion electrode

Ag(s)/AgNO3 electrode

Electrode reaction( in Oxidation direction ) (anodic) :Ag+ + e-

Ag
Total interaction:-

Ag+ (aq) + Cl- (aq)

AgCl (s)
AgNO3 + KCl

-:

AgCl + KNO 3

-: AgBr
-:

Ag(s) | AgBr ; KBr c2 ( 0.01M KBr ) || AgNO3 aq . c1(0.01M ) | Ag(s)

*The cathode is the electrode where reduction occurs.
Electrode type:- metal insoluble salt electrode:
Ag(s) AgBr (s) KBr (aq) electrode
Electrode reaction (in reduction direction) cathode:-

AgBr (s) + e-

Ag + Br-(aq)

*The anode is the electrode where oxidation occurs.

Electrode type:- Metal metal-ion electrode
Ag(s)/AgNO3 electrode

Electrode reaction( in Oxidation direction ) (anodic) :Ag

Total interaction:-

Ag+ + e-

Ag+ (aq) + Br- (aq)

AgBr (s)
AgNO3 + KBr

-:

AgBr + KNO 3

-: AgI
-:

Ag(s) | AgI ; KI c2( 0.01M KI ) || AgNO3 aq c1(0.01M ) | Ag(s)

*The cathode is the electrode where reduction occurs.
Electrode type:- metal insoluble salt electrode:
Ag(s) AgI (s) KI (aq) electrode
Electrode reaction (in reduction direction) cathode:-

AgI (s) + e-

Ag + I-(aq)

*The anode is the electrode where oxidation occurs.

Electrode type:- Metal metal-ion electrode
Ag(s)/AgNO3 electrode

Electrode reaction( in Oxidation direction ) (anodic) :Ag

Ag+ + e-

Total interaction:AgI (s)

Ag+ (aq) + I- (aq)

 -:

AgI + KNO3

AgNO3 + KI

-:

AgCl
NO
MEAS.
1
2
3

LX

EX

( Ag+)2

0.3692
0.3722

0.512310-9
4.587210-9

LX

EX

( Ag+)2

33
33
3353

0.487
0.487
0.4977

25
2552

KSP

KSP(average)

S(average)

KSP

KSP(average)

S(average)

KSP

KSP(average)

S(average)

AgBr
NO
MEAS.
1
2
3

5.21810-11
5.21810-11

3.4410-11

AgI
NO
MEAS.
1
2
3

LX
4555
4555
4555

EX
0.672
0.672
0.672

( Ag+)2
3.8910-14