Determining Saturation Indices: Gypsum (temperature of 20 Celsius)

No. Parameter Concentrati

on
  Kmineral Mineral equilibrium constant
(mmol/L)
1 pH = 8.01
2 HCO3- 0.3
3 Ca2+ 1.4
4 Mg 2+
1.1
5 Na +
2.3
6 K+ 0.1
7 Cl- 2
8 SO4 2-
0.9
9 NO3 -
1.5
10 Al <0.001
11 Fe <0.001
 Methods
 SI = O; mineral is in equilibrium
Analyze water sample for major ions and with solution.
minor ions of interest(Done)  SI < 0; mineral is under saturated
 SI > 0; mineral is supersaturated
Calculate concentrations of
species/complexes (Done)

Calculate Ionic Strength (1)

Calculate Activity Coefficients (2)

Five steps: Saturation Indices (SI)

Calculate Activities of solutes (3)

Calculate Ion Activity Product (IAP) or Q..(Hem)

(4)

Use the equation:

(5)
 1. Ionic Strength (I)

 The ionic strength (I) of a solution is a measure of the strength of the

electrostatic field caused by the ions.
 It is computed from the expression:

Where; m is the concentration of a given ion in moles per liter

z is the charge on that ion.
 1.1 Calculate the Ionic Strength of the Solution, I

Calculations

A. Data
No. Parameter Concentration   Zi Zi2 I= (M* Zi2)*0.5
No. Parameter Concentr (mmol/L) (Moles/L)
ation
1 pH 8.01        
(mmol/L)
2 HCO3- 0.3 0.0003 -1 1 0.00015
1 pH 8.01
2 HCO3- 0.3 3 Ca2+ 1.4 0.0014 2 4 0.0028
3 Ca2+ 1.4 4 Mg2+ 1.1 0.0011 2 4 0.0022
4 Mg2+ 1.1 5 Na+ 2.3 0.0023 1 1 0.00115
5 Na+ 2.3 6 K+ 0.1 0.0001 1 1 0.00005
6 K+ 0.1 7 2 0.002 -1 1
Cl- 0.001
7 Cl- 2.0
8 SO42- 0.9 0.0009 -2 4 0.0018
89 SO42- 0.9
9 NO3- 1.5 0.0015 -1 1 0.00075
10 NO3- 1.5
11 Al <0.001 10 Al <0.001        
12 Fe <0.001 11 Fe <0.001        

Sum 0.0099
 2. Calculation of activity coefficient ( )

For dilute solutions, activity coefficients ( )of single ions can be computed by
means of the Debye-Huckel equation. Various forms of this equation exist.

 But it seems generally agreed that the equation works satisfactorily for solutions
whose total concentration is not much over 0.10 mol/L of univalent salts.

Or if the Ionic strength less than 0.10moles/Kg H2O the Debey- Huckle equation
used is:
2.1 Different formulae to calculate activity coefficient activity coefficient…Cnt’d

Source: Broder J. Merkel · Britta Planer-Friedrich, (2008).Groundwater Geochemistry, A practical guide to

modeling of Natural and Contaminated Aquatic System, 2nd ed. pp (11)
 activity coefficient…Cnt’d
2.2Constants: (At 20 degree Celsius)
Thus, I < 0.10 moles /Liter, we use the following equation :
2.3 Ionic strength Vs Activity at 25 degree Celsius
activity coefficient…Cnt’d
 activity coefficient…Cnt’d
2.4 In to Calculate the Activity Coefficients,( )

We have to Determine the constants: A,B, ai, bi

 A,B temperature-dependent parameters, calculated from the following
empirical equations

Source: Broder J. Merkel · Britta Planer-Friedrich, (2008).Groundwater Geochemistry, A practical guide to

modeling of Natural and Contaminated Aquatic System, 2nd ed. pp (11)
 Calculation activity coefficient…Cnt’d
ai, bi = ion-specific parameters (dependent on the ion radius) (selected
values see Table 4, complete overview in van Gaans (1989) and Kharaka et al. (1988))

Source: Hem
Source: Broder J. Merkel · Britta Planer-Friedrich,
(2008).Groundwater Geochemistry, A practical guide to
modeling of Natural and Contaminated Aquatic System, 2nd
ed. pp (11)
 Calculation activity coefficient…Cnt’d

Tc = 20C0

 d= 0.998234

TK0 = 273.15 + 20
= 293.15K0

ε =2727.586+0.6224107*(293.15-466.9151)*LN(293.15)-(52000.87/293.15)
ε =1935.815

A=(1.82483*10^6*SQRT(0.998234))/(1935.815*293.15)^1.5)

A= 0.004265
 Calculation activity coefficient…Cnt’d

B = (50.2916*SQRT(0.998234))/SQRT(1935.815*293.15)

B = 0.066701
 Calculation activity coefficient…Cnt’d

Activity coefficient

Para (Zi)2 SQRt(I)   ai      

meter Moles/L
HCO3- 0.0003 1 0.099498744 0.000424362 4 1.026546663 0.000413388 0.999048592
Ca2+ 0.0014 4   0.001697449 6 1.039819994 0.001632445 0.996248213
Mg 2+
0.0011 4   0.001697449 8 1.053093326 0.001611869 0.996295413
Na+ 0.0023 1   0.000424362 4 1.026546663 0.000413388 0.999048592
K +
0.0001 1   0.000424362 3 1.019909997 0.000416078 0.999042404
Cl- 0.002 1   0.000424362 3 1.019909997 0.000416078 0.999042404
SO4 2-
0.0009 4   0.001697449 4 1.026546663 0.001653552 0.996199794
NO3- 0.0015 1   0.000424362 3 1.019909997 0.000416078 0.999042404
 4. Determining Ion Activity, ( )

 The activities of solid species participating in a reaction are, by definition, unity.

 In dilute solution, H2O,the solvent, has Ion activity of unity
 In systems that include a gas phase, the activity of
gaseous components is represented by their partial pressures:

For solute species it is convenient to define activity ( )as the product of the
measured concentration and a correction factor called the “activity coefficient”, :

Where, αi is activity of ionic species

Ci concentration in moles/ Kg of H2o(molal) Or
moles/l( molar)

= Activity coefficient
For practical purposes, the activities of dissolved species will be
considered to represent moles per liter.
 Ion Activity ….cont’d

Parameter Moles/L    
HCO3- 0.0003
0.999049 0.000299715
Ca 2+
0.0014
0.996248 0.001394747
Mg 2+
0.0011
0.996295 0.001095925
Na +
0.0023
0.999049 0.002297812
K +
0.0001
0.999042 9.99042E-05
Cl- 0.002
0.999042 0.001998085
SO4 2-
0.0009
0.9962 0.00089658
NO 3
-
0.0015
0.999042 0.001498564
 5. Determining Saturation Indices, SI
 Write appropriate equation so that IAP can easily be calculated

Gypsum:
CaSO4 .2H2O ↔ Ca2+ + SO42- + 2H2O
1
IAP=(αCa*αSO4*(αH2O)2/αCaSo4.2H2O Keq (solubility) = 10-4.6= 2.51189E-05 ; ( Source; C.A.J. Appelo,2005)

1
IAP gyp = αCa* α SO4 * (αH2O)2

IAP gyp = 0.001394747 * 0.00089658 * 1

SI=Log(1.2505E-06/2.51189E-05)
IAP gyp = 1.2505E-06
SI =-1.302916921
SI < 0

Therefore, the Gypsum-water system is in disequilibrium condition with

respect to gypsum

The water is under saturated with respect to Gypsum

The reaction goes to the right, more gypsum can be dissolved to release Ca
and SO4 ions to gw.
Thank You !
 Saturation Index, SI

CaSO4 .2H2O ↔ Ca2+ + SO42- + 2H2O

1
IAP gyp = αCa* α SO4 * (αH2O)2

IAP gyp = 0.001394747 * 0.00089658 * 1

IAP gyp = 1.2505E-06
 Calcite:
In complete activity of CO3- missing
We have tried to calculate from relation: HCO3-↔CO3-2 +H+
pH= 8.01=

pH= -log K=[CO3]*[H+]/[HCO3]-

[H+]= 10-pH
[H+]= 10-8.01 =
0.001198056 [CO3]= K*[HCO3]-/ [H+]
activity CO3 = 1.43534E-06

 CaCO3(s) ↔ Ca2+ +CO32- Kmineral Mineral equilibrium constant

IAP calc = αCa* αCO3

IAP calc = 0.001394747*1.43534E-06

IAPcalc =2.00194E-09
Keq= 10^-8.45

IAP= -0.24855
Log(2.00194E-09/ 10^-8.45)
 Halite

NaCl ↔Na+ + Cl-

IAP Hal = αNa* α Cl = 0.002297812 * 0.001998085

IAP Hal = 4.59122E-06