1

THE GEOCHEMISTRY OF
NATURAL WATERS
ACID-BASE REACTIONS
AND THE CARBONATE SYSTEM
CHAPTER 3b - Kehew (2001)
2
LEARNING OBJECTIVES
Define acids and bases.
Learn to express the strength of an acid in
terms of the dissociation constant (pK
a
).
Understand acid-base equilibria in the
carbonate system.
Define and be able to sketch a Bjerrum
plot.
3
THE CO
2
-H
2
O SYSTEM - I
Carbonic acid is a weak acid of great importance in natural
waters. The first step in its formation is the dissolution
of CO
2
(g) in water according to:
CO
2
(g) CO
2
(aq)
At equilibrium we have:


Once in solution, CO
2
(aq) reacts with water to form
carbonic acid:
CO
2
(aq) + H
2
O(l) H
2
CO
3
0

2
2
2
CO
CO
CO
p
a
K =
4
THE CO
2
-H
2
O SYSTEM - II
In practice, CO
2
(aq) and H
2
CO
3
0
are combined and this
combination is denoted as H
2
CO
3
*. Its formation is
dictated by the reaction:
CO
2
(g) + H
2
O(l) H
2
CO
3
*
For which the equilibrium constant at 25C is:


Most of the dissolved CO
2
is actually present as CO
2
(aq);
only a small amount is actually present as true carbonic
acid H
2
CO
3
0
.
46 . 1
*
10
2
3 2
2

= =
CO
CO H
CO
p
a
K
5
THE CO
2
-H
2
O SYSTEM - III
Carbonic acid (H
2
CO
3
*) is a weak acid that dissociates
according to:
H
2
CO
3
* HCO
3
-
+ H
+
For which the dissociation constant at 25C and 1 bar is:



Bicarbonate then dissociates according to:
HCO
3
-
CO
3
2-
+ H
+

35 . 6
*
1
10
3 2
3

= =
+
CO H
H HCO
a
a a
K
33 . 10
2
10
3
2
3

= =

+
HCO
H CO
a
a a
K
6
THE RELATIONSHIP BETWEEN
H
2
CO
3
* AND HCO
3
-

We can rearrange the expression for K
1
to obtain:


This equation shows that, when pH = pK
1
, the activities of
carbonic acid and bicarbonate are equal.
We can also rearrange the expression for K
2
to obtain:



This equation shows that, when pH = pK
2
, the activities of
bicarbonate and carbonate ion are equal.
*
1
3 2
3
CO H
HCO
H
a
a
a
K

+
=

+
=
3
2
3 2
HCO
CO
H
a
a
a
K
7
BJERRUM PLOTS
These are used for closed systems with a specified total
carbonate concentration. They plot the log of the
concentrations of various species in the system as a
function of pH.
The species in the CO
2
-H
2
O system: H
2
CO
3
*, HCO
3
-
, CO
3
2-
,
H
+
, and OH
-
.
At each pK value, conjugate acid-base pairs have equal
concentrations.
At pH < pK
1
, H
2
CO
3
* is predominant, and accounts for
nearly 100% of total carbonate.
At pK
1
< pH < pK
2
, HCO
3
-
is predominant, and accounts
for nearly 100% of total carbonate.
At pH > pK
2
, CO
3
2-
is predominant.
8
pH
0 2 4 6 8 10 12 14
l
o
g

a
i
-8
-7
-6
-5
-4
-3
-2
6.35
10.33
H
2
CO
3
* HCO
3
-
CO
3
2-
H
+
OH
-
Common pH
range in nature
Bjerrum plot showing the activities of inorganic carbon species as a
function of pH for a value of total inorganic carbon of 10
-3
mol L
-1
.
In most natural waters, bicarbonate is the dominant carbonate species!
9
pH
0 2 4 6 8 10 12 14
l
o
g

a
i
-12
-10
-8
-6
-4
-2
H
2
S
0
HS
-
S
2-
H
+
OH
-
7.0 13.0
Bjerrum plot showing the activities of reduced sulfur species as a
function of pH for a value of total reduced sulfur of 10
-3
mol L
-1
.
10
SPECIATION IN OPEN CO
2
-H
2
O
SYSTEMS - I
In an open system, the system is in contact with its
surroundings and components such as CO
2
can migrate
in and out of the system. Therefore, the total carbonate
concentration will not be constant.
Let us consider a natural water open to the atmosphere,
for which p
CO
2
= 10
-3.5
atm. We can calculate the
concentration of H
2
CO
3
* directly from K
CO
2
:




Note that M
H
2
CO
3
*
is independent of pH!
2
3 2
2
*
CO
CO H
CO
p
M
K =
2 2 3 2
* CO CO CO H
K p M =
2 2 3 2
log log log
* CO CO CO H
K p M + =
11
SPECIATION IN OPEN CO
2
-H
2
O
SYSTEMS - II
The concentration of HCO
3
-
as a function of pH is next
calculated from K
1
:



but we have already calculated M
H
2
CO
3
*
:

so
2 2 3 2
* CO CO CO H
K p M =
*
1
3 2
3
CO H
H HCO
M
a M
K
+
=
+

=
H
CO H
HCO
a
M K
M
* 1
3 2
3
+

=
H
CO CO
HCO
a
p K K
M
2 2
3
1
( ) pH p K K M
CO CO
HCO
+ =

2 2
3
1
log log
12
SPECIATION IN OPEN CO
2
-H
2
O
SYSTEMS - III
The concentration of CO
3
2-
as a function of pH is next
calculated from K
2
:



but we have already calculated M
HCO
3
-
so:

and
+

=
H
CO CO
HCO
a
p K K
M
2 2
3
1

+
=
3
2
3
2
HCO
H CO
M
a M
K
+

=
H
HCO
CO
a
M K
M
3
2
3
2
2
1 2
2 2
2
3
+

=
H
CO CO
CO
a
p K K K
M
( ) pH p K K K M
CO CO
CO
2 log log
2 2
2
3
1 2
+ =

13
SPECIATION IN OPEN CO
2
-H
2
O
SYSTEMS - IV
The total concentration of carbonate C
T
is obtained by
summing:

+ + =
2
3 3
3 2
*
CO HCO
CO H T
M M M C
2
2 1 1
2 2 2 2
2 2
+ +
+ + =
H
CO CO
H
CO CO
CO CO T
a
K p K K
a
K p K
K p C
(
(

|
|
.
|

\
|
+ + =
+ +
2
2 1 1
1 log log
2 2
H H
CO CO T
a
K K
a
K
K p C
14
pH
2 3 4 5 6 7 8 9 10 11 12
l
o
g

c
o
n
c
e
n
t
r
a
t
i
o
n

(
m
o
l
a
r
)
-8
-6
-4
-2
0
C
T
H
+
OH
-
H
2
CO
3
*
HCO
3
-
CO
3
2-
pK
1
pK
2
Plot of log concentrations of inorganic carbon species H
+
and OH
-
,
for open-system conditions with a fixed p
CO
2
= 10
-3.5
atm.
15
pH
2 3 4 5 6 7 8 9 10 11 12
l
o
g

c
o
n
c
e
n
t
r
a
t
i
o
n

(
m
o
l
a
r
)
-8
-6
-4
-2
0
C
T
H
+
OH
-
H
2
CO
3
*
HCO
3
-
CO
3
2-
pK
1
pK
2
Plot of log concentrations of inorganic carbon species H
+
and OH
-
,
for open-system conditions with a fixed p
CO
2
= 10
-2.0
atm.