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Shifting Equilbrium by changes in concentration

Theory
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In the laboratory, a saturated aqueous solution of NaCl was prepared.


A saturated aqueous solution means that the maximum amount of NaCl which can be dissolved in a given amount of water is present. Additional crystals of NaCl when added to a saturated solution will not dissolve.

Kc = [Na+][Cl-] where Kc = Kc[NaCl(s)]. For dissolution processes, this constant is given a special name Constant of Solubility Product, and the symbol Ksp. Ksp of NaCl = [Na+][Cl-]
The constant of solubility product is, in fact, another statement of solubility. The higher the Ksp value is the higher the solubility.

Ksp gives the highest concentration for dissolved species before crystallization or precipitation will occur. If the product [Na+][Cl-] is greater than Ksp of NaCl, NaCl crystals will be formed. Thus, in a saturated solution Ksp = [Na+][Cl-]. The dynamic equilibrium can be easily disturbed by changing any one of these concentrations: either [Na+] or [Cl-]. Observations from the laboratory Addition of 1 mL concentrated HCl (12M) to 4 mL of a saturated solution of NaCl causes NaCl to crystallize. Concentrated HCl contains water and its addition increases the volume of the solution. However, one should keep in mind that it is 12M in Cl-. A saturated solution of NaCl is only 5.4 M which means that, at the most 5.4M of [Na+] and 5.4M of [Cl-] can exist in solution. Addition of HCl results in a dramatic increase in [Cl-] and disturbs the equilibrium. Upon addition of concentrated HCl, the reaction quotient [Na+][Cl-] becomes greater than Ksp of NaCl. Crystallization of NaCl thus occur to relieve this stress. Conclusion If a chemical system is at equilibrium and we add a substance (either a reactant or a product), the reaction will shift so as to re-establish equilibrium by consuming part of the added substance. Conversely, removal of a substance will result in the reaction moving in the direction that forms more of the substance.
Remember that this is a change in concentration so changing the amount of a pure solid or liquid which is already in equilibrium should not make the reaction consume the additional solid or liquid. Example, if solid NaCl is already in equilibrium with a saturated solution of NaCl, adding more pure NaCl solid will not cause additional dissolving. Conversely, removal of some of the solid NaCl which is in equilibrium with a saturated solution of NaCl will not cause further crystallization of NaCl from the saturated solution.

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