Aaron Reinicker

Tompall Toone

Nathaly Murillo

CHEM-445 S08

Experiment 3: Effect of Ionic strength on the Solubility of CaSO4

Abstract:

In this experiment the solubility of CaSO4 in pure water and also in NaCl

solutions was measured taking activity coefficients as well as the effects of ion pairs into

consideration. The pKsp° of Calcium Sulfate in water at infinite dilution was found to be

5.798 while the literature data the value was 5.693. This was calculated using ionic

strengths and the Davies equation for activity coefficients. The solubility of CaSO4 in

pure water was bound to be approximately 0.01437M. To measure the effects of ion pairs

on solubility, solutions of NaCl were used instead of pure water. It was observed that as

the concentration of NaCl increases, solubility of CaSO4 increases as well.

Introduction:

To calculate solubility and solubility constants for any electrolyte other than very

slightly soluble 1/1 electrolytes, one must take into consideration the effects of activity

coefficients and ion pairs. In order to measure the solubility of CaSO4 and the change in

solubility with the addition of electrolytes, it is assumed that the non-covalent bonding of

Ca2+ is non-existent as well as assuming that the CaSO4 is completely dissociate in

aqueous solution; Thus:

(1) CaSO4(s) → Ca2+(aq) + SO42-(aq)

(2a) Kspº= [Ca2+]* [ SO42-] γ±²

(2b) Kspº = Ksp{apparent}γ±² = S² γ±²

In equation 2a, Kspº is the solubility constant value at infinite dilution, γ± is the

average activity coefficient for the two ions in equation 1. In equation 2b, Ksp{apparent}

is the product of the ionic concentrations, or the experimental value. S is the solubility of

CaSO4. It is also assumed that the activity coefficient for both ions is the same. The

determination of S{CaSO4} in pure water assumes that there is no ion pairs in solution,

therefore, equation 2b applies.

The calculation of activity coefficient relies on the ionic strength, μ or I. the ionic

strength includes all ions in the solution.

(3)

In this equation Zj is the charge of each ion and mj is the concentration. It is

assumed that there molality is approximately the same as molarity in this equation. Three

ways to calculate activity coefficients are used in this experiment. First used is the

Debye-Hückel Limiting law or DHLL which is accurate mostly at low concentrations.

(4)

Second is the Debye-Hückel-Guggenhein, or DHG, which applies to a wider range of

concentrations.

(5)

Third used is the Davies equation:

(6)

To find the pKspº experimentally, the following equation can be used:

(7) log Kspº =2*log(S) + 2*log (γ) or log(S)= .5log(Kspº) – log(γ)

Solubility can be calculated by:

(8) S = [Ca2+] + [ CaSO4(aq)]

It cannot be assumed that the solubility of CaSO4 depends solely on the concentration of

calcium ions.

Procedure:

First, a 0.015F solution of ethylene diamine tetraacetic acid (EDTA) was required

for all titrations. 5.5860g of EDTA was place into a one liter volumetric flask, one pellet

of NaOH was added, and the flask was filled with distilled water. This solution was

transferred to a one liter plastic container.

To obtain a 0.015M solution of CaSO4, 1.033g of CaSO4 •H2O and approximately

200mL of distilled water were added to an Erlenmeyer flask. This solution was placed

into a constant temperature bath and stirred for 30 minutes. Then the stir bar was

removed and the solution sat in the constant temperature bath for 15 minutes. Next, a

25mL aliquot was placed into a beaker with 50mL of water. Half a micro spatula of

hydroxynaphthol blue was added to the solution. Before titrating, the solution’s pH was

adjusted to 10-11; the pH was manipulated by adding NH3/NH4Cl. The CaSO4 was

titrated with EDTA, while being stirred. This process was repeated for a total of three

trials.

Next, the affects of adding NaCl to the CaSO4 solution were determined. Five

solutions were made by adding NaCl to a 250mL volumetric flask and filled with distilled

water. The molarities NaCl ranged in these solutions from 0.0436 to .1990M. Once the

solution was made; it was transfer to an Erlenmeyer flask and stirred in a constant

temperature bath for 30 minutes. Following the stirring, the solution sat in the constant
temperature bath for 15 minutes. A 25mL aliquot was taken and added to a beaker that

contained 50mL of water and half a micro spatula of hydroxynaphthol blue. The solution

was then titrated with EDTA while being stirred. The pH was adjusted for each titration

to be between 10 and 11. Three titrations were preformed on each solution.

Data and Results

Table 1: Solubility of CaSO4 in Pure Water

V{EDTA} (ml) [Ca2+] (M) Ionic Strength Ksp{apparent} pKsp{apparent}

24.03 0.014418 0.028836 0.000207879 3.682189958
23.98 0.014388 0.028776 0.000207015 3.683999142
23.84 0.014304 0.028608 0.000204604 3.689084997
Footnotes: [EDTA] = 0.015M
Volume of Aliquot = 25ml

Table 2: Solubility Values of CaSO4

M {NaCl} V{EDTA} (ml) S{CaSO4, M}

0 24.03 0.014418
0 23.98 0.014388
0 23.84 0.014304
0.0436 29.02 0.017412
0.0436 28.3 0.01698
0.0436 27.53 0.016518
0.0755 34.07 0.020442
0.0755 29.09 0.017454
0.0755 31.11 0.018666
0.1110 36.1 0.02166
0.1110 34.21 0.020526
0.1110 34.96 0.020976
0.1440 36.84 0.022104
0.1440 35.49 0.021294
0.1440 36.25 0.02175
0.1990 37.07 0.022242
0.1990 37.16 0.022296
0.1990 38.13 0.022878
 Figure 1: S{CaSO4, M} vs M{NaCl}
y = -0.1837x 2 + 0.0786x + 0.0142
0.025 R2 = 0.953

0.02
S{CaSO4, M}

0.015
S{CaSO4, M}
Poly. (S{CaSO4, M})
0.01

0.005

0
0 0.05 0.1 0.15 0.2 0.25
M{NaCl}

Footnote: a = -0.1837 + 0.0398

b = 0.0786 + 0.0083

Table 3: Activity Coefficients from DHG and Davies Equations

S{CaSO4, M} Ionic Strength logγ (DHG) logγ (Davies)

0.014418 0.028836 -0.29554889 -0.27793586
0.014388 0.028776 -0.29528587 -0.27770949
0.014304 0.028608 -0.29454752 -0.27707376
0.017412 0.034824 -0.32019047 -0.29891997
0.01698 0.03396 -0.31681544 -0.29607267
0.016518 0.033036 -0.31314315 -0.29296477
0.020442 0.040884 -0.34243527 -0.31746332
0.017454 0.034908 -0.32051565 -0.29919385
0.018666 0.037332 -0.32968541 -0.30688303
0.02166 0.04332 -0.35075727 -0.32429742
0.020526 0.041052 -0.3430197 -0.31794514
0.020976 0.041952 -0.34612364 -0.32049936
0.022104 0.044208 -0.35371266 -0.32671042
0.021294 0.042588 -0.34829029 -0.32227754
0.02175 0.0435 -0.35135961 -0.32478981
0.022242 0.044484 -0.35462308 -0.32745225
0.022296 0.044592 -0.35497829 -0.3277415
0.022878 0.045756 -0.35877036 -0.33082259
 Figure 2 Log(S) vs Log(y)

-1.6
-0.4 -0.3 -0.2 -0.1 0
-1.65 logS vs logy
y = -3.7929x - 2.8942
2
DHG
R = 0.9998
-1.7
logS vs. logy
Davies
logy

-1.75
Linear (logS
-1.8 vs logy DHG)

Linear (logS
-1.85
y = -3.1748x - 2.7776 vs. logy
2
R = 0.9996 Davies)
-1.9
logS

Footnotes: For Davies Equation: slope = -3.7929 + 0.0123

Intercept (-pKsp°/2) = -2.7776 + 0.0038
For DHG Equation: slope = -3.1748 + 0.0163
Intercept (-pKsp°/2) = -2.8942 + 0.0055

Table 4: pKsp° Values

pKsp° from DHG pKsp° from Davies pKsp° corrected pKsp° Literature
Figure 2 (Figure2) from Value1
Figure 3
5.5552 5.7884 5.7976 5.693
 Figure 3 log[Ca2+] vs log(y)
y = -3.8081x - 2.8988
2
-1.6 R = 0.9998
-0.34 -0.32 -0.3 -0.28 -0.26
-1.65

-1.7
Log[Ca2+]

log(y) Davies
Corrected
-1.75
Linear (log(y) Davies
Corrected)
-1.8

-1.85

-1.9
Log(y) Davies Equation Corrected

Footnote: slope: -3.8081 + 0.0127

Intercept (-pKsp°/2) = -2.8988 + 0.0039

Discussion:

Table 1 contains the volume of EDTA needed to titrate each calcium sulfate

solution in pure water and the concentration of calcium sulfate in pure water. The ionic

strength, as calculated by its definition, the apparent solubility, Ksp, which equals the

product of the Ca2+ and SO4- concentrations, and the pKsp. Table 2 contains the volume of

EDTA needed to titrate each solution, the concentration of NaCl in each solution, and the

solubility of CaSO4. Figure 1 was produced by plotting the solubility of CaSO4 verses the

concentration of NaCl. This relationship shows the accuracy and precision of the trials. A

reasonable fit was obtained.

With the information contained in Table 1 and Table 2, the ionic strength could be

calculated as well as the activity coefficient for the mixture. The activity coefficients

were calculated using two methods: the Debye-Huckel-Guggenheim (DHG) equation and
the Davies equation. The results of all these calculations were tabulated in Table 3.

Plotting the log (base 10) of the Solubility and the log (base10) of each activity

coefficient produces Figure 2. The y-intercept of the resulting liner graph is half of log

(base10) of the apparent true solubility, Kspo. Table 4 provides the pKspo values found from

Figure 2 as well as the literature value for pKspo.

Finally, ion paring was taken into account. This means that the solubility of Ca2+

no longer equals the concentration of Ca2+. The molarity of CaSO4 (aq), the ion pair, was

now included in the analysis, now the concentration of Ca2+ is unknown. It can be shown

that the concentration of Ca2+ is equal to thee solubility minus the ratio of Kspo (from the

Davies equation) and the dissociation equilibrium constant. The dissociation equilibrium

constant2 was assumed to be 5.0*10-3. With these new concentrations the ionic strength

was found. Then Figure 3 was created; Figure 3 displays the log of [Ca2+] vs. the log of

the Davies activity coefficient. The Kspo was found the same way and recorded in Table 4.

As can be seen from the values in Table 4, the Davies equation, not corrected for ion

pairing, provides the most accurate results as compared to the literature value.

Conclusion

The closest approximation from our data for pKsp° of Calcium Sulfate in water at

infinite dilution was 5.798 while for the literature data the value was 5.693. There were

several potential sources of error in this experiment. The first possible source of error was

in reading the exact equivalence point during the titration of Calcium Sulfate solution

with EDTA. It was very difficult to tell the exact concentration at which the solution

turned blue because the solution would turn several shades of blue making it near

impossible to tell at which time the true equivalence point was reached. Another problem
we had was with keeping the pH meter above 10 throughout the entire titration process.

We had to keep adding buffer to the system which could have significantly altered several

of the titrations.

Reference

1) "Solubility Product Constants." Faculty of Chemistry and Technology. Eni Generalic.

March 22 2003. University of Croatia. May 14 2008< http://www.ktf-
split.hr/periodni/en/abc/kpt.html>.

2) R. G. Ainsworth, J. Chem. Soc. Farad, 69, 1028 (1973).