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SOLUBILITY EQUILIBRIUM OF CALCIUM HYDROXIDE

Y.K. ONG AND E.J.V. REYES


NATIONAL INSTITUTE OF PHYSICS, COLLEGE OF SCIENCE
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY, PHILIPPINES
DATE PERFORMED: OCTOBER 7, 2016
INSTRUCTORS NAME: LIZETTE MELLA
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ABSTRACT
The study aimed to determine the solubility product constant, Ksp, of calcium hydroxide
[Ca(OH)2] through titration using different medias and to inspect the factors affecting the changes
in the Ksp of Ca(OH)2. The suspensions formed by adding Ca(OH)2 to different medias were titrated
with hydrochloric acid (HCl). The titrant volumes, Vtit, were used to calculate the molar solubility of
Ca(OH)2 in various conditions. Diverse ions and polar solvents increased the molar solubility while
the presence of common ions decrease the solubility. The Ksp, H, and S values were obtained
through the use of the vant Hoff equation and linear regression. The experimental Ksp at 298 K is
1.83 x 10-5 with 231.82% percent error. The experimental H and S are -5.45kJ/mol and -109.02
J/ mol K, respectively. Deviation from the literature value of the H is at 67.37% while the percent
error of S is 31.00%. The Ksp value acquired shows the amount of Ca(OH)2 is needed to be dissolved
to form a saturated solution, while the H value illustrates that the dissolution of calcium hydroxide
is an exothermic reaction.
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INTRODUCTION solvent polarity, common ion effect and


diverse ion effect.
Dissolving soluble salts in water
partially dissociates into ions in order to As the Ksp varies with temperature, it
reach equilibrium. this equilibrium is in turns affects the solubility of a compound
attained when the solution becomes which can be seen through the vant Hoff
saturated. The equilibrium obtained when equation:
calcium hydroxide, Ca(OH)2, dissociated into
ions [Ca]2+ and [OH]- is shown by: ln = +
(3)
2+
()2 () () + 2() (1) where H is the enthalpy change of the
reaction, S is the entropy change of the
For soluble compounds in water, the reaction and R is the gas constant, 8.314
equilibrium constant, Keq, can be referred to J/mol-K [1].
as the solubility product constant or Ksp of Polarity of solvents also affects the
the ionic solid. It determines how much solid solubility of compounds as polar solvents
is dissolved to form a saturated solution. The only dissolve polar solutes and nonpolar
Ksp expression of Ca(OH)2 is represented as, solvents only dissolve nonpolar solutes.
2+
= [()
][() ] (2) Stronger polar or nonpolar solvents binds
more strongly to ions than weaker solvents.
where [Ca2+
(aq) ] and [OH(aq) ] are the ionic With the dissolution at equilibrium,
concentrations. the presence of common ions in the solution
A molar solubility of a compound is decreases the solubility of the compound
related to the Ksp and through this due to the Le Chtelier's Principle. Due to
relationship, values for Ksp are influenced by this principle, the precipitation of the
different factors such as temperature, dissolved compound is favored.
On the other hand, the presence of media with different compositions were
diverse ions in the solution increases the prepared. Media A, B, and C were used to
solubility just as it increases the ionic observe the effects of varying temperature
strength of the compound. Equation 4 on the molar solubility and Ksp of Ca(OH)2
shows that as solubility increases with ionic while D and E were done to investigate the
strength. common ion and diverse ion effect. In
1 medium D, the addition of CaCl2 disrupts the
= 2 2 (4) equilibrium of the reaction by adding more
where is the ionic strength of the Ca2+(aq) in the solution. The addition of KCl in
compound, is the molar concentration of i media E increases the ionic strength of the
and zi is the charge number of the ion i [2]. solution. Lastly, media F was used to
compare the solubility of Ca(OH)2 in pure
The objectives of this study are to water (media A) and in a mixture of 10%
determine the Ksp of Ca(OH)2 at different ethanol.
temperatures, to obtain the molar solubility
of Ca(OH)2 and to observe the effects of In determining the concentration of
temperature, polarity of solvents, common calcium hydroxide in the solution, titration
ions and diverse ions on the solubility of of Ca(OH)2 solution with 0.1M HCl was done.
Ca(OH)2. The strong acid-strong base reaction that
occurred is expressed as,
METHODOLOGY
()2 () + 2 () Ca2 () +
To observe the solubility equilibrium
of calcium hydroxide, the media presented in 2 () . (5)
Table 1 of the Appendix were used. The The concentration of Ca(OH)2 can be
following media were prepared in 250 mL related to the molar solubility of the ions
beakers and the temperatures for media A, B present in the compound which in turn can
and C were recorded. be used to determine the Ksp of Ca(OH)2. This
relationship is shown by Equation 2. The
While stirring, calcium hydroxide volume of the titrant (Vtit) obtained when the
[Ca(OH)2] solid were added to each medium titration reached the equivalence point was
until the solution is saturated. The solutions used to compute for the concentration of
were stirred for 5 minutes and were left for Ca(OH)2. The molar concentration is also the
10 minutes so that it would reach its molar solubility of the substance. Table 1
equilibrium. The suspensions were filtered show the calculated molar solubility of
whilst making sure that the receiving flasks Ca(OH)2 in different media.
for the solutions prepared in media B and C
were of the same temperature as the Table 1. Molar solubility (s) of Ca(OH)2 at
suspensions. different media.
Medium s, M
From the supernate, 25 mL of aliquot A 0.019875
was acquired and transferred into a 125 mL B 0.014
Erlenmeyer flask. Three drops of 1% C 0.016025
phenolphthalein were added to the aliquot.
D 0.021519
This solution was titrated using 0.10M
E 0.025667
hydrochloric acid (HCl) until the solution
became colorless. The titrant volume, Vtit, F 0.0172
was recorded. The titration was done at least
twice for each medium. The data gathered The Common Ion Effect states that
were used to calculate the solubility product the solubility of a slightly soluble ionic
constant, Ksp. compound lowers in the presence of
RESULTS AND DISCUSSION common ions in the solution [3]. Based from
the Common Ion Effect, the solubility of
To observe the effects of different Ca(OH)2 decreases when CaCl2 is added to
factors on the molar solubility of Ca(OH)2, six the solution. However, the molar solubility
increased from 0.019875 M to 0.021519 M error from its literature value of 5.50 x 10-6
which differed from the expected trend [1]. The experimental H and S for the

exhibited by the Common Ion Effect. dissolution reaction were determined to be -


5.45 kJ/mol and -109.02 J/ mol K through
The solubility of calcium hydroxide the use of linear regression. The H and S
in media E which contains 0.50 M KCl was values obtained show a 67.37% and 31.00%
found to be 0.025667 M. The molar solubility error from it literature values of -16.7
is higher compared to the solubility in pure kJ/mol and -157.99 J/ mol K, respectively.
water (s = 0.019875 M). The Diverse Ion Data analysis showed that the dissolution of
Effect was observed wherein the presence of calcium hydroxide as an exothermic reaction.
K+ and Cl- ions increase the ionic strength of Discrepancies from the theoretical values
the solution through Equation 4. The can be ascribed to varying temperatures
presence of these ions prevents the Ca2+ and during titration.
OH- ions from reacting to form Ca(OH)2 solid.
CONCLUSION AND RECOMMENDATION
Table 1 also shows that the solubility
of Ca(OH)2 in 10% ethanol decreased to The effects of diverse ions, polarity
0.0172 M when compared to its solubility in of solvents and temperature on the solubility
pure water (s = 0.019875 M). The decrease of calcium hydroxide were successfully
in molar solubility of calcium hydroxide can discerned while the Common Ion Effect was
be attributed to the decrease in polarity not observed and the experimental Ksp value
between pure water and 10% ethanol of Ca(OH)2 differed significantly from the
solvent. literature value. From the plot ln(Ksp) vs 1/T
(in K), the equation of the line obtained was
Lastly, the effect of temperature was y = 656.1x 13.113 with a R of 0.1388 The
observed through Ksp values of Ca(OH)2 Ksp at 298 K show a percentage error of
calculated at varying temperatures. The Ksp 231.82%. The enthalpy and entropy changes
in terms of molar solubility is expressed as, were found to have a 67.31% and 20.05%
= ()(2)2 = 4 3 (6) error, respectively. Since the H value is
negative, it implies that the dissolution of
where [Ca2+] = s and [OH-] = 2s. calcium hydroxide is an exothermic reaction.

The Ksp values acquired were To further improve the experiment,


plugged into Equation 3 at varying it is recommended to solve the Ksp more
temperatures to create a plot showing the accurately by using the activities (effective
relationship between the Ksp and concentrations) of the ions. Temperature
temperature. The plot obtained is shown must also be controlled during the
below: experiment so that the calculation of the Ksp
would not be greatly affected.
-12
REFERENCES
0 0.001 0.002 0.003 0.004
-12.5
[1] Petrucci, R. H.; Hardwood, W.S.; Herring,
ln(Ksp)

-13 G.F. General Chemistry: Principles and


Modern Applications, 10th ed.;
-13.5 Pearson, Canada, Inc.: Toronto,
Ontario.
-14
1/(T/K) [2] Atkins, Peter W., and Julio De Paula.
Atkins' Physical Chemistry. Oxford:
Figure 1. Plot of ln(Ksp) vs 1/T (in K) Oxford UP, 2006. Print
(y = 656.1x 13.113, R = 0.1388) [3] Lide, David R., and William M. Haynes.
CRC Handbook of Chemistry and
Using the equation of the line, the Physics: A Ready reference Book of
experimental Ksp at 298K was calculated to Chemical and Physical Data. Boca
be 1.83 x 10-5. The Ksp value exhibits a 231.82% Raton: CRC, 2009. Print.
APPENDIX A
Table 1. The different medias used in the determination of molar solubility of calcium hydroxide
in various conditions.

Media Composition Temperature (C)


A 50 mL distilled water 28.5
B 50 mL distilled water 58
C 50 mL distilled water 3
D 50 mL 0.10M CaCl2 28.5
E 50 mL 0.50M KCl 28.5
F 45 mL distilled water + 5 mL 95% 28.5
ethanol

Table 2. Volume of 0.10 M HCl used (Vtit) to titrate dissolved Ca(OH)2 at different volumes in
different media.
Medium Vtit, mL Vanalyte, mL
Trial 1 Trial 2 Trial 1 Trial 2
A 10.5 7.5 25 20
B 7 - 25 -
C 10.9 4.1 25 20
D 13.9 6.4 25 21
E 22.8 13 45 25
F 8.5 8.7 25 25

Computation of the molar solubility (s) of Ca(OH)2


Ca(OH)2 (s) + 2 HCl (aq) CaCl2 (aq) +H2O(l)
1
= ()2
2
1
= ()2 ()2
2
Translating this into
1
= ()
2

=
2

Table 3. Molar solubility (s) of Ca(OH)2 at different media.

Medium s, M
A 0.019875
B 0.014
C 0.016025
D 0.021519
E 0.025667
F 0.0172
Table 4. Ksp of Ca(OH)2 at different temperatures.
Medium Ksp Temperature (K)
A 3.14 x 10-05 301.5
B 1.10 x 10-05 331
C 1.65 x 10-05 276

Computing for the Ksp of Ca(OH)2


The vant Hoff equation was utilized to compute for the Ksp.

ln = +

-10.2
0 0.0005 0.001 0.0015 0.002 0.0025 0.003 0.0035 0.004
-10.4

-10.6

-10.8
ln(Ksp)

-11

-11.2

-11.4

-11.6
1/(T/K)

Figure 1. Plot of ln(Ksp) vs 1/T (in K): y = 656.1x - 13.113, R = 0.1388



= = 656.1


= = 13.113

The Ksp of Ca(OH)2 at 25C was calculated to be 1.83 x 10-5. The experimental H and S
for the reaction Ca(OH)2(s) Ca2+(aq) + 2 OH-(aq) are -5.45kJ/mol and -109.02 J/ mol K, respectively.
Table 5. Standard enthalphy changes (Hf) and entropy (S) values for the dissolution of
Ca(OH)2.
Compound Hf, kJ mol-1 S, J mol-1 K-1
Ca2+(aq) -542.8 -53.1
OH (aq)
- -230.0 -10.75
Ca(OH)2(s) -986.1 83.39

Standard enthalpy change of the dissolution of Ca(OH)2:

= () () (9)
2+
= ( (() ) + 2 (() )) ( (()2 () ) )


= ( 542.8 + 2 (230.0 )) (986.1 )


= 16. 7

Standard entropy change of the same reaction:

= () () (10)

= ( 2+

+ 2 (() )

) (()2 () )
(() )


= (53.1 + 2 (10.75 )) 83.39


= 157.99

% Error of Experimental Value
|(1.83 105 )( 5.50 x 106 )|
Ksp: % = 100% = 231.82% error
|( 5.50 x 106 )|

|(5.45)(16.7 )|
% = 100% = 67.37% error
|( 16.7 )|

|(109.02)( 157.99 )|
% = 100% = 31.00% error
|(157.99 )|