1

THE GEOCHEMISTRY OF
NATURAL WATERS
CHEMICAL EQUILIBRIUM
CHAPTER 2b - Kehew (2001)
2
LEARNING OBJECTIVES
Learn to use some tools of thermodynamics.
Become acquainted with equilibrium and the equilibrium
constant.
Become acquainted with activity and activity coefficients.
Learn to calculate and use IAP and SI.
Learn to calculate variation of the equilibrium
constant with temperature.
See and be able to calculate the effect of activity
coefficients on mineral solubility.
See and be able to calculate the effect of complexation on
mineral solubility.
3
THE ION ACTIVITY PRODUCT
(IAP)
Consider once again the reaction:
CaSO
4
(s) Ca
2+
+ SO
4
2-

The equilibrium constant is expressed in terms of the
activities of the reactants and products at equilibrium:


However, a real solution may or may not be in equilibrium.
The ion activity product (IAP ) or reaction quotient (Q )
has the same form as the equilibrium constant, but
involves the actual activities:
( ) ( )
equil
SO
equil
Ca
a a K
+
=
2
4
2
( ) ( )
actual
SO
actual
Ca
a a Q IAP
+
= =
2
4
2
4
THE SATURATION INDEX
The saturation index (SI) is defined according
to:


If IAP = K
SP
, then SI = 0, and the water is
saturated with respect to the mineral.
If IAP < K
SP
, then SI < 0, and the water is
undersaturated with respect to the mineral.
If IAP > K
SP
, then SI > 0, and the water is
supersaturated with respect to the mineral.
|
|
.
|

\
|
=
SP
K
IAP
SI log
5
APPLICATION
Suppose a groundwater is analyzed to contain 5x10
-2
mol
L
-1
Ca
2+
and 7x10
-3
mol L
-1
SO
4
2-
. Is this water saturated
with respect to anhydrite? (ignore activity coefficients)
K
SP
= 10
-4.24
mol
2
L
-2
IAP = (5x10
-2
)(7x10
-3
) = 3.5x10
-4
= 10
-3.45
mol
2
L
-2





In this case, SI > 0, i.e., IAP > K
SP
, so the solution is
supersaturated and anhydrite should precipitate.


| | | |
79 . 0
10
10
log log log
24 . 4
45 . 3 2
4
2
=
|
|
.
|

\
|
=
|
|
.
|

\
|
=
|
|
.
|

\
|
=

+
SP SP
act act
K
IAP
K
SO Ca
SI
6
A SECOND APPLICATION
A water contains the following: 3.13x10
-4
mol L
-1
Mg
2+
;
8.48x10
-4
mol L
-1
Ca
2+
; and 2x10
-6
mol L
-1
CO
3
2-
. Determine
whether this water is saturated with respect to dolomite
(ignore activity coefficients).
K
SP
= 10
-17.20
mol
2
L
-2
IAP = (8.48x10
-4
)(3.13x10
-4
)(2x10
-6
)
2

= 1.06x10
-18
= 10
-17.97
mol
2
L
-2




Because SI < 0, the solution is undersaturated with respect
to dolomite; the mineral should dissolve.
77 . 0
10
10
log log
20 . 17
97 . 17
=
|
|
.
|

\
|
=
|
|
.
|

\
|
=

SP
K
IAP
SI
7
THIS APPROACH CAN BE APPLIED
TO ALL TYPES OF REACTIONS
Consider the acid-base reaction:
H
2
CO
3
0
HCO
3
-
+ H
+
for which K = 10
-6.35
. Which way should the reaction go if
pH = 7, a
H
2
CO
3
0
= 10
-4
and a
HCO
3
-
= 10
-3
?
First, we must calculate the IAP. To do so, we recall that
pH = -log a
H
+
, so

a
H
+
= 10
-7
. Now



and IAP > K (10
-6
> 10
-6.3
). The reaction will shift to the
left until IAP = K.
( )( )
( )
6
4
7 3
10
10
10 10
0
3 2
3

= = =
+
CO H
H HCO
a
a a
IAP
8
THE DISSOCIATION OF
WATER AND NEUTRAL pH - I
In this case, we have the reaction:
H
2
O(l) H
+
+ OH
-

for which


but because usually a
H
2
O
~ 1,

A
r
G = A
f
G
H
+
+ A
f
G
OH
-
- A
f
G
H
2
O
A
r
G = 0 + (-157.3) - (-237.1) = 79.80 kJ mol
-1

O H
OH H
w
a
a a
K
2
+
=
+
=
OH H
w
a a K
9
THE DISSOCIATION OF
WATER AND NEUTRAL pH - II
If this reaction were occuring in pure water with no other
solutes, then it would have to be true that at equilibrium:

Thus

98 . 13
) K )(298.15 mol K J 314 . 8 ( 303 . 2
mol J 79800
log
1 1
1
=

w
K
98 . 13
10

= =
+
OH H
w
a a K
+
=
OH H
a a
98 . 13 2
10

=
+
H
a
7 98 . 13
10 10

= =
+
H
a
10
THE DISSOCIATION OF
WATER AND NEUTRAL pH - III
When the solution is said to be
neutral. Hence, neutral pH at 25C is pH = 7.
Note that, a pH of 7 is only neutral at 25C and
1 bar, because K
w
is a function of both pressure
and temperature.
For example, at 0C neutral pH is 7.47 and at
50C neutral pH is 6.63. By 300C, neutral pH is
~5.7!
+
=
OH H
a a
11
DISSOCIATION CONSTANT OF WATER
AT VARIOUS TEMPERATURES (FROM
FAURE, 1997)
T(C) - log K
w
T(C) - log K
w
0 14.9435 30 13.8330
5 14.7338 35 13.6801
10 14.5346 40 13.5348
15 14.3463 45 13.3960
20 14.1669 50 13.2617
24 14.0000 55 13.1369
25 13.9965 60 13.0171
25
12
THE DISSOCIATION OF
WATER AND NEUTRAL pH - IV
Finally, is a solution with and
in equilibrium at 25C?
To answer this we need to calculate the IAP:


Because IAP > K
w
, the solution is not in
equilibrium. Some OH
-
and H
+
need to be
consumed to bring the reaction back to
equilibrium.
3 . 13 14 8 6
10 10 5 ) 10 5 )( 10 (

= = = =
+
OH H
a a IAP
6
10

=
+
H
a
8
10 5

=

OH
a
13
VARIATION OF LOG K WITH
TEMPERATURE
The following is a generally valid relationship:
A
r
G = A
r
H - TA
r
S
If we assume that A
r
H and A
r
S are
approximately constant (true over a limited
temperature range), then because:


we can write
RT
G
K
o
r
303 . 2
log
A
=
RT
S T H
K
o
r
o
r
303 . 2
log
A + A
=
14
THE VANT HOFF EQUATION
If we assume again that A
r
H is approximately
constant, we can write the expression:



We can calculate A
r
H and A
r
S according to:
|
|
.
|

\
|

A
+ =
2 1
1 1
303 . 2
log log
1 2
T T R
H
K K
o
r
T T

A A = A
reactants
o
f
products
o
f
o
r
H H H

= A
reactants
o
products
o o
r
S S S
15
APPLICATION
Calculate the solubility product of anhydrite at 60C.
CaSO
4
(s) Ca
2+
+ SO
4
2-
First, we calculate A
r
H and A
r
S:
A
r
H = A
f
H
Ca
2+
+ A
f
H
SO
4
2-
- A
f
H
CaSO
4
(s)
A
r
H = -543.0 + (-909.3) - (-1434.4) = -17.90 kJ mol
-1

A
r
S = S
Ca
2+
+ S
SO
4
2-
- S
CaSO
4
(s)
A
r
S = -56.2 + 18.5 - 107.4 = -145.1 J K
-1
mol
-1
Method 1:


77 . 4
) K 15 . 333 )( mol K J 4 2.303(8.31
) mol K J 1 . 145 )( K 15 . 333 ( ) mol J 900 , 17 (
303 . 2
log
1 1
1 1 1
=
+
=
A + A
=


RT
S T H
K
o
r
o
r
16
APPLICATION (CONTINUED)
Method 2:






The differences in the results of these two methods are
due to slight inconsistencies in the thermodynamic data.
57 . 4
15 . 333
1
15 . 298
1
) mol K J 314 . 8 ( 303 . 2
mol J 900 , 17
24 . 4
1 1
303 . 2
log log
1 1
1
2 1
1 2
=
|
.
|

\
|

+ =
|
|
.
|

\
|

A
+ =

T T RT
H
K K
o
r
T T