Chimica Fisica II - Elettrochimica - Sandra Rondinini

Chimica Fisica II - Elettrochimica - Sandra Rondinini
CHIMICA FISICA II - ELETTROCHIMICA

Sandra Rondinini
2
Activity and standard state
f
i
= rational activity coefficient
y
i
= molar activity coefficient
i
= molal activity coefficient
Activity of i
a = f
i
(x
i
/x
0
) = y
i
(c
i
/c
0
) =
i
(m
i
/m
0
)
x
0
= standard state on rational scale
c
0
= standard state on molar scale
m
0
= standard state on molal scale
Activity and standard state:
choice of the more convenient scale and standard state
Solid phase and liquid non-
ionic mixtures: molar
fraction
a = f
i
(x
i
/x
0
)
x
0
= 1, the pure compound
SOLUTIONS: solute and solvent same scale (molar, molal or mole fraction) but
different standard states:
Solvent standard state: THE PURE SOLVENT, i.e. x
0
= 1
Solute standard state: c
0
= infinite dilution (hypothetical c
0
= 1)
m
0
= infinite dilution (hypothetical m
0
= 1)
( ) ( ) ( ) 1 lim ; 1 lim ; 1 lim
0 0 0
= = =
m m c c x x
y f
Activity coefficient: the Debye-Hckel equation
z
+
and z
=ionchargenumbers
I =ionicstrengthof the solution
A and B = D-Hconstants, functionof solvent and temperature
a =closest approachdistanceof ions
b =interactionparameters
( )
( ) I A z z
bI
I aB
I A z z
+
+
=
+
+
=
lg
1
lg
extended equation
limiting law
( )
I aB
I A z z
+
=
+
1
lg
Figure 2.7 The Debye-Hckel model in its limiting version predicts that the mean
ionic activity coefficients of salts depend on (z
+
z
)
2
; according to the red line. The
points show experimental data for potassium fluoride and calcium chloride solutions.
The predictions of the extended law for z
+
z
= 1 cases are shown in green and those

for z
+
z
= 2 are in violet.
(aq) 2Br (aq) Zn (l) Br Zn(s)
(aq) Br 2 2e (l) )Br (
2e (aq) Zn Zn(s) ) (
) Cu( | (l) Br | (aq) ZnBr | n(s) | )Cu (
2
2
2
2
2 2
+

+
+ +
+ +
+
+ Z
Activity coefficient: experimental determination
2
Br Zn
Br Zn
2
2
ln
2
+
+ =
a a
a a
F
RT
E E
o
And the corresponding Nernstian expression is
Nonetheless, the liquid bromine is soluble in water and in excess of bromide ions
forms stable complexes of the type
hence
( )

+ =
+ =
+ =
+ =
+ +
+ +
3
Br Zn
Br
Zn
'
3
Br Zn
Br
Zn
Br
2
Br Zn
Br
Zn
2
Br Zn
Br Zn
2
-
3
2
-
3
2
-
3
2
2
ln
2
ln
2
ln
2
1
ln
2
ln
2
a a
a a
F
RT
E
a a
a a
F
RT
K
F
RT
E E
K a a a
a a
F
RT
E
a a
a a
F
RT
E E
o o
o o
= = +

Br
Br
Br
-
3 2
2
3
(aq); Br (aq) Br (aq) Br
a a
a
K
( )
( ) ( ) [ ]
[ ] [ ]

= =
= =
=
+

m
k
E m
k
E E
m m
k
E m
k
E E
a a
k
E E
3
' 3 3 '
3
2
' 3 3 '
2
Br Zn
'
4 lg
2
3
4 lg
2
2 lg
2
lg
2
lg
2
2
o o
o o
o
In the assumption that
1 and
Zn
Br Br
3
=

a a a
If the standard potential E and K are known, the mean activity coefficient of
zinc bromide can be determined at any m by measuring the open circuit
potential:
Otherwise, the simoultaneous determination of E
and
requires an
extrapolation procedure upon substitution of the
term with the Debye-Hckel

equation:
[ ]
( )
[ ] m
k
E E
ZnBr
3
'
,
4 lg
2 3
lg
2
+
=

o
[ ] [ ] [ ]
[ ]

+
+ =
= =

bI
I aB
I A k
m
k
E E
k
m
k
E m
k
E E
1
2
2
3
4 lg
2
3
lg
2
3
4 lg
2
3
4 lg
2
3
3
'
3
'
3
'
o
o o

The extrapolation function is obtained in the assumption that the ion-size
parameter a = 0.39 nm.
By measuring E at various ZnBr
2
molalities, and plotting vs I, one obtains a
straight line, the intercept corresponding to E and the slope to the -3kb/2,
from which the of b can be derived.
Simoultaneous determination of
standard potential and activity coefficent
[ ] bI
k
E
I aB
I A k
m
k
E
2
3
1
2
2
3
4 lg
2
3
'
3
=
+
+ =
o
,

V
I , mol kg
-1
E
The measure of the standard potential of a cell is at the basis
of the electrochemical series of the semi-elements
+ =
+ + +
+ + +
+
+
+
+
+

+
Cl H
Ag
AgCl
2 1
0
H
0
/H H
0
AgCl/Ag/Cl
2
2
2 2
2
2
ln
(aq) Cl (aq) H Ag(s) AgCl(s) (g) H
2
1
(aq) Cl Ag(s) AgCl(s) ) (
(aq) H (g) H
2
1
) (
) Pt( | Ag(s) | AgCl(s) | O H in , HCl | (g) H | Pt ) (
a a a
a
p
p
F
RT
E E E
e
e
m
Under standard conditions, i.e. at unit activities of all species
Assuming that the standard potential of the H
+
/H
2
couple is
equal to ZERO at all temperatures and in all solvents,
one gets
0
/H H
0
AgCl/Ag/Cl
0
2
+
= E E E
0
AgCl/Ag/Cl
0
/H H
0
AgCl/Ag/Cl
0
2
+
= = E E E E
By combining the AgCl/Ag/Cl
electrode with another

semielement, e.g. Hg
2
Cl
2
/Hg/Cl
, one obtains the standard

potential of the latter semielement:
Hg(s) AgCl(s) Ag(s) (s) Cl Hg
2
1
(aq) Cl Hg(s) (s) Cl Hg
2
1
) (
AgCl(s) (aq) Cl Ag(s) ) (
) Pt( | Hg(l) | (s) Cl Hg | O H in , KCl | AgCl(s) | Ag(s) | Pt ) (
2 2
2 2
2 2 2
+ +
+ + +
+ +
+

e
e
m
0
AgCl/Ag/Cl
0
/Hg/Cl Cl Hg
0
2 2

= E E E
0,2223 AgCl(s) + e
= Ag(s) + Cl
0,342 Cu
2+
+ 2 e
= Cu(s)
0,771 Fe
3+
+ e
= Fe
2+
0,7996 Ag
+
+ e
= Ag(s)
1,066 Br
2
(l) + 2 e
= 2 Br
1,229 O
2
(g) + 4 H
+
+ 4 e
= 2 H
2
O
1,358 Cl
2
(g) + 2 e
= 2 Cl
1,69 Au
+
+ e
= Au(s)
1,776 H
2
O
2
+ 2 H
+
+ 2 e
= 2H
2
O
2,866 F
2
(g) + 2 e = 2 F
3,040 Li
+
+ e
= Li(s)
2,925 K
+
+ e
= K(s)
2,84 Ca
2+
+ 2 e
= Ca(s)
2,356 Mg
2+
+ 2 e
= Mg(s)
1,662 Al
3+
+ 3 e
= Al(s)
0,762 Zn
2+
+ 2 e
= Zn(s)
0,447 Fe
2+
+ 2 e
= Fe(s)
0,4030 Cd
2+
+ 2 e
= Cd(s)
0,0000 2 H
+
+ 2 e
= H
2
(g)
Redox Standard Potentials
Redox Standard Potentials
Ox + n e
Red
Figure 6.6 Combined Pourbaix diagrams for oxygen and hydrogen, showing the zone of thermodynamic stability of
water. Full and dashed lines respectively represent ionic activities of unity and 0.001.
Figure 6.5 Pourbaix diagramfor the element zinc. Full and dashed lines respectively
represent ionic activities of unity and 0.001.
Different Potential Scales

Chimica Fisica II - Elettrochimica - Sandra Rondinini

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Chimica Fisica II - Elettrochimica - Sandra Rondinini

CHIMICA FISICA II - ELETTROCHIMICA

= 1 cases are shown in green and those

term with the Debye-Hckel

electrode with another

, one obtains the standard

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