Solubility Equilibrium

TRAINING COURSE ON ISOTOPE AND
GEOCHEMICAL MODELLING
Addis Ababa, Ethiopia 4 - 15 JANUARY 2010
Solubility and chemical

equilibrium
Paula Carreira
Instituto Tecnológico e Nuclear
Sacavém, Portugal
THERMODYNAMICS ACTIVITY AND
EQUILIBRIUM
In solution, ionic species behave as if their concentration

is less than the real.
Activity [ ] of a specie comes to represent the effective

concentration of that specie.
The behavior of a substance in a chemical reaction is

given by the Law of Mass Action. This law can be apply
to processes of dissolution / precipitation, gas solubility.
In reactions like:
[C ]c [ D]d
K a b
aA + bB  cC + dD [ A] [ B]
a, b, c and d --- number of moles of the chemical

constituents A, B, C and D, respectively
Where K is the thermodynamic equilibrium constant

and [ ] represents the activities, expressed as
molality
In a liquid state water undergoes the equilibrium
dissociation:
H2O  H+ + OH-
From the law of mass action, can be expressed as:
[ H ] [OH ]
K
[ H 2O]
H2O <--> H+ + OH- Kw= 10-14,0
CO2(g) + H2O <--> H2CO3 KH=10-1,5
H2CO3 <--> H+ + HCO3- K1= 10-6,3
HCO3- <--> H+ + CO32- K2 = 10 -10,3
The activity coefficient of these samples depends

greatly on the pH and of the partial pressure of CO2 on
the system.
There are cases where concentration is nearly equal
activity.
In the case of the dissolution of fluorite, we can write:
CaF2 <--> Ca2+ + 2F-
so Kfluorite = [Ca2+] · [F-]2 = 10-10.57 at 25ºC
This relationship gives us an idea about the solubility of

the mineral phase and when the ionic concentration of
these species is saturated, unsaturated or
supersaturated with respect to this mineral phase.
Extracting logarithms:
Log Kf = log [Ca2+] + 2 log [F-] = -10.57
This is the equation of a line on a logarithmic scale

that lets us know the saturation
-- unsaturated
-- saturated
--supersaturated
Fields of stability and solubility of fluorite
Similar happens with gypsum (CaSO4 *2H2O)
CaSO4 <--> Ca2+ + SO42-
Kgypsum= [Ca2+] · [SO42-] = 10-4.60 at 25ºC
Gypsum is more soluble than fluorite.
One way to reduce the fluor content present in a

groundwater, can be by precipitation, by adding gypsum to
the system, the fluorite to reach saturation and precipitate.
The fluor is remove from the system.
The amount of gypsum to be added can be calculated by

solving an equation system:
Effect of adding gypsum to a water sample
with high fluor content
When the activity is different from the concentration.
We must speak about the activity coefficient g
[i] = g · mi
The activity coefficients are calculated from the Huckel-

Deybe equation.
The ionic strength I is determined by the relation:
I = 1/2 Σmi · zi2

mi is the molality of species i
zi is the valence, or charge, that the ion carries
The ionic strength I of freshwater is about 0.02, while that

of seawater is 0.7
The activity coefficient of a specific ion can be calculated by the
relation:
- A z2 √m Debye – Hukel equation

Log gi =
1 + B ai √m
This equation can be used up to m ≈ 0.1, to which corresponds a

salt content between 5 to 8 g/L. In freshwater ≈ 0.2 g/L
or
- A z2 √m m ≈ 4 is acceptable
Log gi = - bim
1 - B ai √m
z – ion valence
A and B – characteristics of the dissolvent in water between 0 and 60 ºC
A = 0.49176 + 6.69213 x 10-4 T + 3.5559 x 10-6 T2
B = 0.32486 + 1.47259 x 10-4 T + 1.54486 x 10-7 T2
T = temperature
a and b specific of each ion
Relationship between the activity coefficients
of different ions and ionic strength
SOLUBILITY AND CHEMICAL EQUILIBRIUM
The reactivity of ions in solution is further limited by the presence of
ion pairs or complexes: CaSO4o, CaF+, etc.
The K of these reactions is called the stability constant or dissociation
and its calculation requires the use of programs like WATEQF ,
PHREEQE, etc..
They play an important role in hydrochemistry
Chemical analyses indicate the total concentration of the constituents, but
not the form in which occur in the water.
Complexes forms:
SO42- complexes: CaSO4o

MgSO4o
NaSO4-
NaSO4o
KSO4-
HCO3- complexes: CaHCO3-

MgHCO3-
NaHCO3o
CO32- complexes: CaCO3o

MgCO3o
NaCO3-
The total amount of an ion in
solution is the sum of the ionic forms
and complex forms:
ΣCa2+ = mCa2+ + mCaF- + MCaSO4º
To calculate what happens in the

solution is required by computing a
sequence of iterations until
convergence is obtained, as shown
at right.
Solubility of gypsum in water: Importance of
the complexes
Saturation Index
They tell us if the solution is in equilibrium with a mineral

phase.
If we reach saturation, we can not dissolve, but if it is

over saturated the solution can continue the mineral
dissolution.
When saturated, the tendency is to precipitate
Knowing the solubility product of the mineral phase.
K gypsum = [Ca2+] · [SO42-] = 10-4.60 at 25ºC
We can calculate the ionic activity product (IAP)

Saturation index (cont.)
the ionic activity product (IAP):
IAP gypsum = [Ca2+] · [SO42-]
if
When Ω= IAP/K = 1  equilibrium conditions
when > 1 supersaturated, and <1 unsaturated.
The saturation index is defined as SI = log (IAP / K), and

therefore SI is < 0 or > 0 is used to define if one water is
unsaturated or supersaturated.
In an aquifer we can differentiate sectors subsaturated
or oversaturated water for the various mineral phases,
showing different geochemical conditions.
For this we use programs such WATEQF, PHREEQE
This analysis can also be performed along flow lines

and study what reactions take place, and to what
extent.
It is possible to quantify the magnitude of the reactions

that take place within the aquifer.
Saturation index of calcite and dolomite in samples
along a flow line from the previous case
Saturation index of gypsum in samples along a
flow line from the previous case
Palaeotemperature determination by noble gas
solubility in water

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TRAINING COURSE ON ISOTOPE AND

Solubility and chemical

In solution, ionic species behave as if their concentration

Activity [ ] of a specie comes to represent the effective

The behavior of a substance in a chemical reaction is

a, b, c and d --- number of moles of the chemical

Where K is the thermodynamic equilibrium constant

From the law of mass action, can be expressed as:

The activity coefficient of these samples depends

CaF2 <--> Ca2+ + 2F-

so Kfluorite = [Ca2+] · [F-]2 = 10-10.57 at 25ºC

This relationship gives us an idea about the solubility of

Log Kf = log [Ca2+] + 2 log [F-] = -10.57

This is the equation of a line on a logarithmic scale

CaSO4 <--> Ca2+ + SO42-

Kgypsum= [Ca2+] · [SO42-] = 10-4.60 at 25ºC

Gypsum is more soluble than fluorite.

One way to reduce the fluor content present in a

The amount of gypsum to be added can be calculated by

We must speak about the activity coefficient g

The activity coefficients are calculated from the Huckel-

The ionic strength I is determined by the relation:

I = 1/2 Σmi · zi2

The ionic strength I of freshwater is about 0.02, while that

- A z2 √m Debye – Hukel equation

This equation can be used up to m ≈ 0.1, to which corresponds a

SO42- complexes: CaSO4o

HCO3- complexes: CaHCO3-

CO32- complexes: CaCO3o

ΣCa2+ = mCa2+ + mCaF- + MCaSO4º

To calculate what happens in the

They tell us if the solution is in equilibrium with a mineral

If we reach saturation, we can not dissolve, but if it is

When saturated, the tendency is to precipitate

Knowing the solubility product of the mineral phase.

K gypsum = [Ca2+] · [SO42-] = 10-4.60 at 25ºC

We can calculate the ionic activity product (IAP)

the ionic activity product (IAP):

IAP gypsum = [Ca2+] · [SO42-]

When Ω= IAP/K = 1  equilibrium conditions

when > 1 supersaturated, and <1 unsaturated.

The saturation index is defined as SI = log (IAP / K), and

For this we use programs such WATEQF, PHREEQE

This analysis can also be performed along flow lines

It is possible to quantify the magnitude of the reactions

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