http://ion.chem.usu.

edu/~sbialkow/Classes/3600/Overheads/C
arbonate/CO2.html
Carbon Dioide ! Carbonic "cid #$uilibrium
Carbonic acid is formed when atmospheric CO
2
is dissolved in water. The chemical
equilibria are
1) Gas dissolution
2) Carbonic acid formation
3) Carbonic acid equilibrium
In an open sstem! the partial pressure of CO
2
"#) is relativel constant at P"CO
2
) $
%.%%%3&& 'tmosphere.
The equilibrium e(pression is the )enr*s +aw equation ", 2& -C)
Thus
.sin# this one ma obtain
Click here to learn more about calculating the p H of water in
equilibrium with air
Dependent Carbonate #$uilibrium
.sin# carbonate mass balance and acid equilibrium e(pressions! the fractional
amounts of all carbonate species can be found as a function of /H
0
1
The pH dependent fractions are

Of interest is the total carbonate as a function of pH.
2emember that /H
2
CO
3
1 is 3fi(ed3 b the atmosphere in an open equilibrium sstem
and
Total carbonate increases with pH.
%olubilit& o' Calcium Carbonate
"' 4stematic Treatment)
Chemistry
Charge Balance
Mass Balance
Equilibrium Equations
This is obviousl a difficult sstem of equations to solve. Thou#h it could be done!
let*s loo5 for the appro(imations "'6'! the eas wa out)
Clic5 here to learn more about sstematic treatment of chemical equilibrium
(olar %olubilit& o' Calcium Carbonate "pproimations
Open system7 The tric5 to solvin# for carbonate equilibria is to first identif the ma8or
species. That is! we should be able to loo5 at all equilibria and determine which
carbonate species are in #reatest abundance.
The ma8or equilibrium process here is
9 e(aminin# the alpha plot! we see that HCO
3
:
is a ma(imum at pH$;.3. This will
help. 4olvin#<
Closed System= The real tric5 here! if there is one! is to find the pH. >ith the pH! we
can easil solve an carbonate problem with the fractional amounts. ?or e(ample! the
calcium carbonate solubilit is a function of the fractional amount of carbonate as
carbonate and the total amount of carbonate. In a closed sstem at fi(ed pH
Use of Acid Distributions in Solubility Problems
?or solutions with controlled pH! the counter ion solubilit effects are easil
accounted for in determinin# the solubilit of a salt producin# a con8u#ate base. 4a
we have a metal@con8u#ate base salt! MA! that ioniAes "dissociates) in solution b
where A
n-
is a con8u#ate base of an acid with equilibria
etc.
'lthou#h the salt dissociates to form M
n
and A
n-
! the A
n-
is basic and B#rabs* protons
from water. 'cidic forms of the A
n-
anion do not form an insoluble salt comple(.
The problem is not intractable. In fact! it is easy i! the pH is "no#n. To find the
solution! we note that for each mole of M
n
dissolved! one mole of A
n-
is initiall
formed. The A
n-
! in turn! is distributed amon# all acid forms.
?rom the
n
definition we 5now that the fraction of acid as A
n-
is
4ubstitution of this into the $
sp
equation #ives a simple result
's a concrete e(ample! consider the molar solubilit of calcium carbonate at pH C.
Calcium carbonate dissociates b
The $
sp
$C.%(1%
D
. Carbonate will be distributed as CO
%
&
! HCO
%
! and H
&
CO
%

where $
a'
$ E.E&(1%
F
and $
a&
$ E.CD(1%
11
. The e(pressions are
To find the molar solubilit we use the table to find the amounts of solution phase
species.
CaCO
%
"s) > Ca
&
"aq) CO
%
&-
"aq)
initial solid % %
change : ( 0 ( 0 (
!inal solid ( (
?or each ( mole of CaCO
%
that dissolves! ( mole of Ca
&
and ( mole of CO
%
&-
are
formed. The CO
%
&-
will be distributed in the different acid forms. 9ut we 5now (
A
and
the concentrations of the various forms are still related to (
A
throu#h the
The $
sp
equation is cast in the form
.sin# the values from the table
where ( is equal to /Ca
&
1! (
A
! and is the molar solubilit of CaCO
%
. To find the molar
solubilit we first determine
2
. 't p) C! /H
%
O

1$1%
C
and
2
$1.EE(1%
&
. The molar
solubilit is
Golar solubilities at other pH*s are #iven in the Table below. Hotice that CaCO
%
is
soluble in acid solution but is insoluble in basic solution. This feature is used b
Geolo#ists to test for carbonate roc5 "calcite). Calcite BfiAAes* when HCl is dropped on
it but has no reaction with )aOH. >h does it BfiAAI*
pH p
2
molar solubilit
2 12.C; 1F%
E ;.C; 1.F%
C E.;E %.%2%
; 2.3E %.%%11
1% %.ED 1.E(1%
:E

12 %.%%D2 F.;(1%
:&

solubilit of CaCO
%
as a function of p)