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ChemWiki: The Dynamic Chemistry E-textbook > Physical Chemistry > Equilibria > Solubility > Common Ion Effect

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Common Ion Effect

Le Châtelier's Principle states that if an equilibrium becomes unbalanced, the reaction will shift to restore the balance. If a common ion is added to a weak acid or weak base equilibrium, then the equilibrium will shift towards the reactants, in this case the weak acid or base.

Introduction

The common-ion effect is used to describe the effect on an equilibrium involving a substance that adds an ion that is a part of the equilibrium.

Example 1

Consider the lead(II) ion concentration in this saturated solution of PbCl2. The balanced reaction is

\[ PbCl_2 \; (s) \rightleftharpoons Pb^{2+} \; (aq) + 2Cl^- \; (aq) \]

Defining s as the concentration of dissolved lead(II) chloride, then:

\[[Pb^{2+}] = s \]

\[[Cl^- ] = 2s\]

These values can be substituted into the solubility product expression, which can be solved for s:

\[\begin{eqnarray} K_{sp} &=& [Pb^{2+}] [Cl^-]^2 \\ &=& s \times (2s)^2 \\ 1.7 \times 10^{-5} &=& 4s^3 \\ s^3 &=& \frac{1.7 \times 10^{-5}}{4} \\ &=& 4.25 \times 10^{-6} \\ s &=& \sqrt[3]{4.25 \times 10^{-6}} \\ &=& 1.62 \times 10^{-2}\ mol\ dm^{-3} \end{eqnarray} \]​

The concentration of lead(II) ions in the solution is 1.62 x 10-2 M. Consider what happens if sodium chloride is added to this saturated solution. Sodium chloride shares an ion with lead(II) chloride. The chloride ion is common to both of them; this is the origin of the term "common ion effect".

Look at the original equilibrium expression again:

\[ PbCl_2 \; (s) \rightleftharpoons Pb^{2+} \; (aq) + 2Cl^- \; (aq) \]

What happens to that equilibrium if extra chloride ions are added? According to Le  Châtelier, the position of equilibrium will shift to counter the change, in this case, by removing the chloride ions by making extra solid lead(II) chloride.

 


Note:  Of course, the concentration of lead(II) ions in the solution is so small that only a tiny proportion of the extra chloride ions can be converted into solid lead(II) chloride.


The lead(II) chloride becomes even less soluble, and the concentration of lead(II) ions in the solution decreases. This type of response occurs with any sparingly soluble substance: it is less soluble in a solution which contains any ion which it has in common. This is the common ion effect.

A Simple Example

If an attempt is made to dissolve some lead(II) chloride in some 0.100 M sodium chloride solution instead of in water, what is the equilibrium concentration of the lead(II) ions this time? As before, define s to be the concentration of the lead(II) ions.

\[[Pb^{2+}] = s\]

The calculations are different from before. This time the concentration of the chloride ions is governed by the concentration of the sodium chloride solution. The number of ions coming from the lead(II) chloride is going to be tiny compared with the 0.100 M coming from the sodium chloride solution.

In calculations like this, it can be assumed that the concentration of the common ion is entirely due to the other solution. This simplifies the calculation.

So we assume:

\[[Cl^- ] = 0.100 M\]

The rest of the mathematics looks like this:

\begin{equation} \begin{split} K_{sp}& = [Pb^{2+}][Cl^-]^2 \\ & = s \times (0.100)^2 \\ 1.7 \times 10^{-5} & = s \times 0.00100 \end{split} \end{equation}

therefore:

\begin{equation} \begin{split} s & = \dfrac{1.7 \times 10^{-5}}{0.0100} \\ & = 1.7 \times 10^{-3} \, \text{M} \end{split} \end{equation}

Finally, compare that value with the simple saturated solution:

Original solution:

\[Pb^{2+}] = 0.0162 \, M\]

Solution in 0.100 M NaCl solution:

\[ [Pb^{2+}] = 0.0017 \, M \]

The concentration of the lead(II) ions has decreased by a factor of about 10. If more concentrated solutions of sodium chloride are used, the solubility decreases further.

Common Ion Effect on Weak Acids and Bases

 Adding a common ion prevents the weak acid or weak base from ionizing as much as it would without the added common ion. The common ion effect suppresses the ionization of a weak acid by adding more of an ion that is a product of this equilibrium.

Example 2

The common ion effect of H3O+ on the ionization of acetic acid

common ion 1.jpg

The common ion effect suppresses the ionization of a weak base by adding more of an ion that is a product of this equilibrium.

Example 3

Consider the common ion effect of OH- on the ionization of ammonia

common ion 2.jpg

Adding the common ion of hydroxide shifts the reaction towards the left to decrease the stress (in accordance with Le Châtelier's Principle), forming more reactants. This decreases the reaction quotient, because the reaction is being pushed towards the left to reach equilibrium. The equilibrium constant, Kb=1.8*10-5, does not change. The reaction is put out of balance, or equilibrium.

\[Q_a = \frac{[NH_4^+][OH^-]}{[NH_3]} \]

At first, when more hydroxide is added, the quotient is greater than the equilibrium constant. The reaction then shifts right, causing the denominator to increase, decreasing the reaction quotient and pulling towards equilibrium and causing Q to decrease towards K.

Common Ion Effect on Solubility

Adding a common ion decreases solubility, as the reaction shifts toward the left to relieve the stress of the excess product. Adding a common ion to a dissociation reaction causes the equilibrium to shift left, toward the reactants, causing precipitation.

Example 4

Consider the reaction:

\[ PbCl_2(s) \rightleftharpoons Pb^{2+}(aq) + 2Cl^-(aq)\]

What happens to the solubility of PbCl2(s) when 0.1 M NaCl is added? 

SOLUTION

\[K_{sp}=1.7 \times 10^{-5}\]

\[Q_{sp}= 1.8 \times 10^{-5}\]

Identify the common ion: Cl​-

Notice: Qsp > Ksp The addition of NaCl has caused the reaction to shift out of equilibrium because there are more dissociated ions. Typically, solving for the molarities requires the assumption that the solubility of PbCl2 is equivalent to the concentration of Pb2+ produced because they are in a 1:1 ratio. 

Because Ksp for the reaction is 1.7×10-5, the overall reaction would be (s)(2s)2= 1.7×10-5. Solving the equation for s gives s= 1.62×10-2 M. The coefficient on Cl- is 2, so it is assumed that twice as much Cl- is produced as Pb2+, hence the '2s.' The solubility equilibrium constant can be used to solve for the molarities of the ions at equilibrium.

The molarity of Cl- added would be 0.1 M because Na+ and Cl- are in a 1:1 ration in the ionic salt, NaCl. Therefore, the overall molarity of Cl- would be 2s + 0.1, with 2s referring to the contribution of the chloride ion from the dissociation of lead chloride. 

\[\begin{eqnarray} Q_{sp} &=& [Pb^{2+}][Cl^-]^2 \\ 1.8 \times 10^{-5} &=& (s)(2s + 0.1)^2 \\ s &=& [Pb^{2+}] \\ &=& 1.8 \times 10^{-3} M \\ 2s &=& [Cl^-] \\ &\approx & 0.1 M \end{eqnarray} \]
 

Notice that the molarity of Pb2+ is lower when NaCl is added. The equilibrium constant remains the same because of the increased concentration of the chloride ion. To simplify the reaction, it can be assumed that [Cl-] is approximately 0.1M since the formation of the chloride ion from the dissociation of lead chloride is so small. The reaction quotient for PbCl2 is greater than the equilibrium constant because of the added Cl-. This therefore shift the reaction left towards equilibrium, causing precipitation and lowering the current solubility of the reaction. Overall, the solubility of the reaction decreases with the added sodium chloride.

References

  1. Harwood, William S., F. G. Herring, Jeffry D. Madura, and Ralph H. Petrucci. General Chemistry Principles and Modern Applications. 9th ed. New Jersey: Prentice Hall, 2007. 670-a32.
  2. "Common Ion Effect." Common Ion Effect. Web. May 2012. <http://www.cartage.org.lb/en/themes/...nIonEffect.htm>.
  3. "Solubility Equilibrium." ThinkQuest. Oracle Foundation. Web. May 2012. <http://library.thinkquest.org/C00666...olubility.html>.

Contributors

  • Emmellin Tung, Mahtab Danai (UCD)
  • Jim Clark (ChemGuide)

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