CHEMISTRY Journal Nathan 11A

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CHEMISTRY
Temperature Effect on Cobalt(II)-Chloride Complex Equilibrium in Aqueous Solution
ABSTRACT
The equilibrium system of cobalt(II) chloride in hydrochloric acid, a simple experiment is
conducted to discuss on the equilibrium shift depending on the temperature. With a simple
experiment of measuring the color change temperatures for a series of cobalt(II) chloride
solutions with different concentrations of hydrochloric acid, We can conclude that the
equilibrium constant at the temperature of the color change between the pink octahedral complex
and deep-blue tetrahedral complex can be expressed as a function for the concentration of
hydrochloric acid. Using the data collected for conditions for the series of sample solutions and
the typical measured values of td for the sample solutions and the calculated Values of [Cl–]0–1.
constants at those temperatures, the standard enthalpy change Hº is evaluated by a graph called
the van’t Hoff plot.
INTRODUCTION
A simple experiment for determining K can be used to discuss the complex equilibrium in terms
of K, as has been proposed for various equilibrium on how it involves with how the temperature,
and pressure can also effect the solubility of solids liquid and gases. One such experiment is
conducted for the present system for the measurement of [Co(H2O)6]2+ and [CoCl4]2–
concentrations by means of spectrophotometric methods, where the values for the ratio of
[[CoCl4]2–]/[[Co(H2O)6]2+] were used instead of K for discussing the effects of [H2O] and
[Cl–] on the equilibrium shift.
In this journal, an experiment is conducted for illustrating the temperature dependence of K
through an experiment that measures the color change temperatures of several cobalt(II) chloride
solutions with different chloride concentrations and a constant total cobalt(II) concentration. This
simple experimental procedure. Because the acceptable value of the standard enthalpy change
Hº can be evaluated by analyzing the temperature dependence of the equilibrium constant
determined by the experiment, this can also be applicable to chemistry subjects at colleges as an
introductory experiment for people who want to study about chemical thermodynamics.
LITERATURE
The complex equilibrium of cobalt(II) ions in hydrochloric acid solution,
[Co(H2O)6]2+ (pink) + 4Cl– ⇄ [CoCl4]2– (deep blue) + 6H2O
Using the LeChatelier’s principle , we can deduce that because the equilibrium shift due to the
effects of concentrations of related species and of temperature. According to Le Chatelier's
principle, if pressure is increased, then the equilibrium shifts to the side with the fewer number of
moles of gas., therefore the equilibrium in equation 1 shifts to the right and left by increasing the
concentrations of Cl– and H2O, respectively. When heating the system, an increase in
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temperature will cause the forward reaction to occur, increasing the amounts of the products and
decreasing the amounts of reactants. , that is, its enthalpy change is H > 0.
The equilibrium constant K for eq 1 is expressed by:
The complex equilibrium is made out of several steps including different kinds of cobalt(II)
complexes due to the transformation from the octahedral complex [CoCl(H2O)5]+ to the
tetrahedral complex [CoCl2(H2O)2, there is a color change from pink to deep blue that takes
place. According to the abundance of the cobalt(II) complexes as a function of HCl
concentration reported by Zeltmann et al. [12], the cobalt(II) complexes are negligible in the
region of HCl concentration where the color change is from pink to deep blue. Assuming the
concentration of H2O is constant in the aqueous solution. Zeltmann et al. reported that the result
of the equilibrium constant K2 to be (1.7 ± 0.4) × 10–3 at 300 K with the enthalpy change of
H2º = 8.8 ± 4.2 kJ mol–1.
Equation 8 tells us that the equilibrium constant K2 depends on [Cl–]0. At the same time, the
color change temperature td on heating or cooling the solution changes the [Cl–]0 when [Co2+]0
is constant. Accordingly, the temperature change of K2 can be estimated by an experiment that
measures the relationship between [Cl–]0 and td. According to the van’t Hoff equation for the
temperature dependence of the equilibrium constant, the relationship between K2 and Td (= td +
273.15 K) is expressed by
Where R and S2º are the gas constant and the enthalpy change, respectively. Using equation 8,
equation 9 can be rewritten as
By plotting ln [Cl–]0–1 against Td–1, the value of H2º can be calculated from the slope
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MATERIALS AND PROCEDURE

Materials: Safety goggles and gloves for handling the hydrochloric acid in this experiment,
cobalt(II) chloride hexahydrate, solutions of cobalt(II) chloride in hydrochloric acid, the aqueous
solution of cobalt(II) chloride,
Steps: Place Cobalt(II) chloride hexahydrate solutions for a short amount of time in a water bath
at 60 ºC until the discoloration from pink to deep blue is observe. Insert the thermocouple of a
digital thermometer in the warmed sample solution and cool down the sample solution slowly in
ambient air by comparing the color with that of the reference solution. Record the temperature of
the sample solution just when the color of the sample solution just becomes identical to that of
the reference solution. Repeat the above procedures for all the sample solutions.
DATA
Preparation Conditions for the Series of Sample Solutions (100 mL)
Sample Volume/ml^3 Initial

concentration /M
1M 6M [Co2+]0 [Cl–]0
CoCl2(aq) HCl(aq)
1 10 76 0.10 4.56
2 10 78 0.10 4.68
3 10 80 0.10 4.8
4 10 82 0.10 4.92
5 10 84 0.10 5.04
6 10 86 0.10 5.16
Referrence 10 90 0.10 5.40
Typical Measured Values of td for the Sample Solutions and the Calculated Values of [Cl–]0–1.
Sample t / ºC [Cl–] –1 / M
d 0
1 50.2 0.219
2 47.8 0.214
3 45.3 0.208
4 42.8 0.203
5 40.1 0.198
6 38.2 0.194
CONCLUSION
The complex equilibrium of cobalt(II) chloride in hydrochloric acid, the equilibrium constant at
the color-change temperature between the octahedral complex [CoCl(H2O)5]+ (pink) and
tetrahedral complex [CoCl2(H2O)2] (deep blue) is inversely proportional to the initial
concentration of hydrochloric acid. By experimenting with different color change temperatures,
and different concentrations of hydrochloric acid. The temperature change in the equilibrium
constant we can predict the color change of the temperature By plotting the van’t hoff graph of
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equilibrium constant against temperature according to the equation, the value of H2º for the
color-change reaction step can be calculated from the slope of the van’t hoff graph. This
experiment makes it possible for the measure of temperature on the equilibrium shift. Which
then can be used by students as a reference for an introductory experiment into chemical
thermodynamics.
References and Notes

1. Eberhardt, W. H. J. Chem. Educ., 1964, 41, A591.
2. Ophardt, C. E. J. Chem. Educ., 1980, 57, 453.
3. Martins, L. J. A.; Barbosa da Costa, J. J.Chem.Educ., 1986, 63, 989.
4. Shakhashiri, B. Z. Chemical Demonstrations, Vol. 1; The University of Wisconsin Press:
Madison, 1983; pp 280–285.
5. Summerin, L. R.; Ealy Jr., J. L. Chemical Demonstrations, Vol. 1; The American Chemical
Society: Washington D. C., 1988; pp 79–82.
6. Silberman, R. G. J. Chem. Educ., 1996, 73, 426.
7. Barreto, J. C.; Dubetz, T.; Brown, D. W.; Barreto, P. D.; Coates, C. M.; Cobb, A. Chem.
Educator, 2007, 12, 18
8. Furukawa, Y.; Takaoka, T. Kagaku-to-Kyoiku, 2002, 50, 458, in Japanese.
9. Hennis, A. D.; Highberger, C. S.; Schreiner, S. J. Chem. Educ., 1997, 74, 1340.
10. Tesaki, M.; Koga, N.; Kawasaki, Y.; Furukawa, Y. Chem. Educator, 2007, 12, 248.
11. Spears, Jr., L. G.; Spears, L. G. J. Chem. Educ., 1984, 61, 252.
12. Zeltmann, H. A.; Matwiyoff, N. A.; Morgan, L. O. J. Phys. Chem., 1968, 72, 121.
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Nathan 11a/17

MATERIALS AND PROCEDURE

Sample Volume/ml^3 Initial

References and Notes

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