Electrochemistry

Ionic activity, mean activity coefficient

Activity
Activity of a molecule or ion in a solution is referred to as effective
concentration. Recalling the definition of activity from equilibrium
thermodinamics

0
i
m
m
a =
m
0
is the standard concentration, (e.g.: 1 mol kg
-1
,
m
i
the molality of i
th
com!onent of a solution,
is the concentration de!endent activity coefficient. "oth a and have no unit.
#n diluting the solution, i.e.
c $ 0 $1 then a $c
activity becomes equal to the concentration. In very dilute solution interactions
are insignificant and concentration and effective concentration are the same.
%hough, activity and activity coefficient have no unit their magnitude de!end on
the concentration units used. &.g., concentration of the same solution can be
given in units mol'kg
-1
, mol'dm
-(
, molar fraction and so on.
Ion activity
Activities of ionic solutions serve us for calculating
accurate chemical !otentials
accurate equilibrium constants
%aking into account that the activity has a greater im!ortance in ionic solution
than that of non-electrolytes. Intermolecular forces are greater among ions
()oulombic interaction.
Ions in aqueous solution.
Strong electrolytes are the ionic com!ounds that com!letely dissociate into ions
*hen they are dissolved.
+a)l(aq $ +a
,
(aq , )l
-
(aq.
.ean activity /000 1
%he chemical !otentials for the formation of ions,
aq , )l aq , +a
aq +a)l, +
+ =
*hich also im!lies that standard chemical !otentials
0
aq , )l
0
aq , +a
0
aq +a)l, +
+ =
1e also kno* that *e can (must2 *rite
aq +a)l,
0
aq +a)l, aq +a)l,
lna RT + =
1hen *orking *ith ionic solutions *e *ould like to be a little more s!ecific
about the activities of the s!ecies in solution. 3t is customary to use units of
molality, m, for ions and com!ounds in *ater solution. 3f the solutions *ere
ideal *e could *rite for the acticity of i
th
com!onent
0
i
i
m
m
a =
and the chemical !otential *ould be *ritten
0
i
i 0
i i
ln
m
m
RT + =
%*o things must be said about this equation. 4irst, it must be understood that
there is an im!lied m
i
o
dividing the m
i
inside the logarithm, and second, the
standard state is the solution at concentration m
i
= m
i
o
. 5sually we set m
i
o
= 1
mol kg
-1
. 6o*ever, ionic solutions are far from ideal so *e must correct this
e7!ression for chemical !otential for the nonidealities. As usual, *e *ill use an
activity coefficient, 8 , and *rite the activity as
0
i
i
m
m
a
i
i

=
and consistent *ith *hat *e have been doing, *e *ill set m
i
o
to 1 molal and not
*rite it in the equation. %he form of equation indicates that activity and activity
coefficient are dimensionless, i.e. they have no unit.%hus the chemical !otential
*ill be *ritten
i i
m RT ln
0
i i
+ =
.ean activity /000 /
%he standard state for this equation is a hyothetical standard state. %he
standard state is not actually reali9able. 1e are using the so-called 6enry:s la*
standard state in *hich the solution obey:s 6enry:s la* in the limit of infinite
dilution. %hat is,

i
$ 1 in the limit *hen m
i
$ 0.
1e *ill sim!lify matters by *riting m
,
, 8
,
and m
-
,8
-
for the molalities and
activity coefficients of the !ositive and negative ionic s!ecies, res!ectively.
1e *ill also refer to the ionic com!ound sim!ly as the ;salt.; 1ith this notation
*e can re*rite former &quations as,
+
+ =
salt
or
+ + +
+ + + = + m RT m RT a RT ln ln ln
0 0
salt
0
salt
.
3n a sim!lified form
+ + +
+ + = + m m RT a RT ln ln
0 0
salt
0
salt
%he sum of standard chemical !otentials is equal to that of the salt
0 0 0
salt +
+ =
%he logarithmic term on the left is identical to the logarithmic term on the right,
+ +
= m m RT a RT ln ln
salt
from *hich *e conclude that
+ +
= m m a
salt
!he activity coefficients, "
#
and "
$
can%t &e measured indeendently
because solutions must be electrically neutral. 3n other *ords, you can't make a
solution which has just positive or just negative ions. <ou can:t calculate the
individual activity coefficients from theory, either. 6o*ever, you can measure a
;geometric mean; activity coefficient and, *ithin limits, you can calculate it
from theory.
=eometric mean.
.ean activity /000 (
=eometric mean. +umbers like x
1
, x
/
,>x
n
form a geometric mean *hich can be
given as,
n / 1
...x x x m
n
=
%he actual form of the geometric mean de!ends on the number of ions !roduced
by the salt. Right no* *e *ill define it for +a)l and then give more e7am!les
later. 4or +a)l *e define,
/
+
= or
( )
+
=
/
1
3t turns from the form of eqution above that
+
=
*hich says that
equal amount of 'activity coefficient roerty( is divided to ositive and
negativ ions.
?o,
/
salt +
= m m a
"ut for a +a)l solution of molality, m, *e have m
,
@ m and m
-
@ m so that
/ /
salt
= m a
Aee! in mind that this is for +a)l, but it is correct for any one-to-one ionic
com!ound.
%ry .g)l
/
,
.g)l
/
$ .g
/,
, / )l
-

+
+ + + = + + +
)l
0
)l .g
0
.g
salt
0
salt
ln / / ln ln / / m RT m RT a RT
/ / 0
)l
0
.g
salt
0
salt
ln / ln /
+ +
+ + = + + m m RT a RT
so
+ +
=
/ /
salt
m m a
"ut for .g)l
/
at molality, m, *e kno* that m
,
@ m and m
-
@ /m. 4urther, *e
define the geometric mean activity coefficient by,
( )
(
1
/
+
=
%hen
.ean activity /000 B
( )
( ( ( /
salt
B /

= = m m m a
#ther ionic com!ounds are done in a similar manner. After some !ractice you
can !robably figure out the e7!ression for a
salt
Cust by looking at the com!ound.
5ntil then, or *hen in doubt, go back to the e7!ressions for chemical !otentials
as *e have done here. (4or !ractice you might *ant to try Al
/
(?#
B

(
..
General formula
Absolute activities of cations and anions can not e !etermine! e7!erimentally.
The defnition of the mean activity coefcient depends on
the number of ions into which a molecule dissociates when it is
dissolved.
3n the laboratory it is im!ossible to study solutions *hich only contain one kind
of ion. 3nstead, solutions *ill have at least one !ositive and one negative ty!e of
ion. 4or the generic electrolytic com!ound dissolving in *ater:
+
+
9 9
y 7
y" 7A " A
*e *ill find terms such as
7
"
7
A
a a
in eqilibrium constant, "
a
and in reaction
quotient, # values. &7!ressing such !roducts in terms of molalities and activity
coefficients, *e first note that for a solution containing y 7
" A
com!onent of
concentration m, the ion concentrations are DAE @ xm and D"E @ ym. %he activity
!roduct then becomes:
( ) ( ) ( ) ( ) ( )
( )
( )
y
$
x
%
y x y x
m y x ym xm m m a a = = =
+ y
"
7
A
y
" "
7
A A
y
"
7
A
1e can define a mean activity coefficient as: ( )
( ) y x+

=
F 1
y
"
7
A
and this allo*s us to re*rite equation as: ( )
( ) ( ) y x y x y x
m y x a a
+

+
=
y
"
7
A
)elationshi &etween K
a
and K
m
%he equilibrium constant given in terms of activities is the thermo!ynamic
equilirium constant&
.ean activity /000 G
5se an e7am!le of dissociation equilibrium of a *eak acid to sho* this
relationshi!H
6A $ 6
,
, A
-
the equilibrium constant of the reaction, (introducing the standard concentration,
m
o
again
o
6A 6A 6A
a
1
m
m
m m
a
a a
"

= =
+ + +

Ano*ing
/
+
=
and m
,
@ m
'
@ m
6A 6A
o
/ /
6A
a

= =
+
m m
m
a
a a
"

" " " =

c a
*here
6A
o
/
c
m m
m
"

=
6A
/

= "
%he equilibrium constants given in terms of molality and activity coefficient.
"
a
@ f(T,p but inde!endent of molalities.
*e&ye-+,ckel -imiting -aw.
%heoretical calculation of 8
I
.
%he Jebye 6Kckel limiting la* gives the 8
I
in terms of the ionic
strength, (, defined as,.
.ean activity /000 L

=
i
i i
) m (
/
/
1
*here )
i
is the charge on ion i, and m
i
is the molality of ion i and %he
ionic strength, ( em!hasi9es the charges of ions because the charge
numbers occur as their squares.
&7am!les
a. 1hat is the value of ionic strength of 6)l solution *ith molality
0.010:
m
6,
@ m
)l-
@ 0.01 molFkg,
1
/
)l
/
6
= =
+
) )
( ) ( ) ( )
1 - / /
kg mol 01 . 0 1 01 . 0 1 01 . 0
/
1
= + + = (
b. the ionic strength of 0.10 molal +a
/
?#
B

1e must include all ions in the solution. !he ionic strength is a
measure of the total concentration of charge in the solution. +otice
that it includes contributions from both the number of ions in the
solution and the charges on the individual ions.
Mean activity coefcient determination via
calculation: Debye-Hckel theory
%he chemical !otential or activity of ions cannot be determined on a
!urely thermo!ynamic asis. %his is due to the fact that the effects of
an ion cannot be se!arated from the effects of the accom!anying
counter-ion, or in other terms, the electrochemical !otential of the ion
cannot be se!arated into the chemical and the electrical com!onent.
?uch a se!aration must necessarily be based on a non-thermodynamic
convention.
.ean activity /000 M
%he mean activity coefficient can be calculated at very low
concentrations by the Debye-Hckel Limiting Law
/ F 1
lg ( ) ) % =
+

where A = 0.509 / (mol kg

!
"
!/#
for an a$ueous solution
at #5
o
%& in general& A depends on the relative
permittivit' of solvent and the temperature.
The log
!0
of mean activit' coe(cient also depends on
the product of
+
) )
the absolute value of cation and anion charge number.
)hen the ionic strength of the solution is too high for
the limiting law to be valid& it is found that the activit'
coe(cient ma' be estimated from the extended
Debye-Hckel law.
/ F 1
/ F 1
1
G11 . 0
lg
(
( ) )
+

=
+

1here is a measure of distance bet*een ions.

*n the limit of small concentration I
!/#
++ !& and in the
denominator of &q. I
1/#
can be neglected, therefore *e receive
Debye-Hckel Limiting Law again.
NetOs try to make sense of our equation for the mean activity
coefficient by taking it a!art
$ %

=
G11 . 0
10
, *here +
= ) ) %
H
/ F 1
/ F 1
1 (
(
$
+
=
% =reater charges !roduce more negative the argument for the
e7!onential,

is farther a*ay from 1, its ideal value.

.ean activity /000 P
$ %he term $ varies bet*een 0 and 1. 1hen ( is small $ Q 0, and

Q 1.
&7am!le: for % @ 1, $ @ 0.001, the argument for the e7!onential is
-0.000G11, and
00PP . 0 10
000G11 . 0
= =

.alculating ionic strength

)alculate ( for a solution that is 0.( molal in A)l and 0.G molal in
A
/
)r
/
#
M
.
( ) ( ) ( )
( ) P . 1 / ( . 0 ( . 1 G . 0
/
/ 1 1
/
1
M / /
M /
# )r A A)l
A
/
# )r
/
)l
/
A
= + + =
+ =
+ + =
+
+

(
m m m
m m m (
molFkg

(A)l
/0/P . 0
P . 1 1
P . 1 1 G11 . 0
lg
/ F 1
/ F 1
=
+

=

G00L . 0 =

(A
/
)r
/
#
M

GPGG . 0
P . 1 1
P . 1 / G11 . 0
lg
/ F 1
/ F 1
=
+

=

/L . 0 =

Therefore ionic activities are clearl' dependent on

the overall composition of the solution.
.ean activity /000 0