Ionic Product under Ionic Equilibrium
1. Introduction to Ionic Equilibrium
Ionic equilibrium is an important part of physical chemistry that deals with the equilibrium established in electrolyte solutions due to partial or complete ionization of substances. When acids, bases, or salts are dissolved in water, they produce ions. In many cases, this ionization is reversible, and a dynamic equilibrium is established between ions and undissociated molecules.
The concept of ionic equilibrium helps in understanding the behavior of weak electrolytes, strength of acids and bases, solubility of salts, and precipitation reactions. One of the most important ideas derived from ionic equilibrium is the ionic product.
2. Meaning of Ionic Product
The ionic product of a solution is defined as the product of the molar concentrations of the ions present in solution, each raised to the power of its stoichiometric coefficient at any given moment.
For a general salt:
AxBy ⇌ xAy+ + yBx−
The ionic product (IP) is given by:
IP = [Ay+]x [Bx−]y
Ionic product represents the current state of the solution and does not necessarily indicate equilibrium conditions.
3. Ionic Product and Solubility Product
Ionic product is closely related to solubility product (Ksp), but the two are not the same. Solubility product is a constant value for a sparingly soluble salt at a given temperature, whereas ionic product can have different values depending on the concentrations of ions present in solution.
Ionic product can be less than, equal to, or greater than the solubility product. Comparison of IP with Ksp helps in predicting whether a precipitate will form or not.
4. Relationship between IP and Ksp
Case 1: IP < Ksp
The solution is unsaturated. More solute can dissolve, and no precipitation occurs.
Case 2: IP = Ksp
The solution is saturated and the system is in equilibrium. No precipitation occurs.
Case 3: IP > Ksp
The solution is supersaturated. Excess ions combine to form a solid precipitate.
5. Ionic Product of Water
Water is a weak electrolyte and undergoes slight ionization as shown below:
2H2O ⇌ H3O+ + OH−
The ionic product of water is given by:
Kw = [H+][OH−]
At 25°C, the value of Kw is:
Kw = 1.0 × 10−14
This constant is useful in determining pH, acidity, and basicity of solutions.
6. Ionic Product in Weak Electrolytes
Weak acids and weak bases do not ionize completely in solution. For a weak acid HA:
HA ⇌ H+ + A−
The ionic product is:
IP = [H+][A−]
At equilibrium, this ionic product becomes the acid dissociation constant (Ka). Similarly, for weak bases, ionic product leads to the base dissociation constant (Kb).
7. Ionic Product and Precipitation
When two electrolyte solutions are mixed, precipitation may occur if the ionic product exceeds the solubility product of the resulting salt.
Example:
Ag+ + Cl− → AgCl(s)
Ionic product:
IP = [Ag+][Cl−]
If IP is greater than Ksp of AgCl, precipitation takes place.
8. Selective Precipitation
Selective precipitation is the method of separating ions in a mixture based on differences in their solubility products.
For example, silver chloride precipitates before lead chloride when chloride ions are added slowly because AgCl has a much smaller Ksp value.
This method is widely used in qualitative analysis.
9. Common Ion Effect and Ionic Product
The addition of a common ion increases the ionic product of a solution. This shifts the equilibrium in accordance with Le Chatelier’s principle and reduces the solubility of the salt.
Example:
AgCl(s) ⇌ Ag+ + Cl−
Addition of NaCl increases chloride ion concentration, thereby increasing IP and decreasing solubility of AgCl.
10. Numerical Example
If the concentration of Ag+ is 2 × 10−4 M and Cl− is 1 × 10−6 M, then:
IP = (2 × 10−4) × (1 × 10−6) = 2 × 10−10
Since this value is greater than Ksp of AgCl, precipitation occurs.
11. Importance of Ionic Product
The concept of ionic product is important in predicting precipitation, understanding solubility, explaining common ion effect, qualitative salt analysis, environmental chemistry, and industrial processes.
12. Common Errors by Students
Students often confuse ionic product with solubility product, ignore stoichiometric coefficients, or use incorrect concentrations. Careful application of the concept avoids these errors.
13. Conclusion
Ionic product is a fundamental concept of ionic equilibrium that helps in understanding the behavior of electrolyte solutions. By comparing ionic product with solubility product, it becomes possible to predict precipitation and solubility behavior accurately. This concept is essential for board examinations and competitive exams like JEE and NEET.