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Equilibrium-Constant Expression

Ionic Equilibria
The equilibrium constant expression:

(Review)
by

Rey Y. Capangpangan, Ph.D.


If Z in the expression is the solvent H2O, the equilibrium expression can
be simplified as :

Chem 20 : Analytical Chemistry (Lec


(Lec))
Chemistry Division
College of Arts and Sciences
Caraga State University

Common Ion Effect

Shift in equilibrium that occurs because of the addition


of an ion already involved in the equilibrium reaction.

HF(aq) H 2 O (l)

F - (aq) H 3O (aq)

What happens to the equilibrium if 0.10 M NaF is added?

AgCl (s)

Ag (aq) 2 Cl (aq)

What happens to the equilibrium if 0.10 M NaCl is added?

Applying the ion-product constant for water

Example 1

Aqueous solutions contain small concentrations of hydronium


and hydroxide ions as a result of the dissociation reaction:

The concentration of water in dilute aqueous


solutions is enormous, however, when compared
with the concentration of hydronium and hydroxide
ions. As a result, [H2O]2 can be taken as constant,
and thus:

Kw = ion-product constant
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Example 2

Example 2

Using Solubility Product Constant

Using Acid/Base Dissociation Constants

For example, when an excess of barium iodate is equilibrated


with water, the dissociation process is adequately described by
the equation:

When a weak acid or a weak base is dissolved in water, partial


dissociation occurs. Thus, for nitrous acid, we can write:

Ka = acid dissociation constant

Kb = base dissociation constant


Ksp = solubility-product constant or solubility product
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Dissociation Constants for Conjugate Acid/Base Pairs

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Example

but
and therefore

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Hydronium Ion Concentration of Solutions of Weak Acids


When the weak acid HA is dissolved in water, two equilibria
produce hydronium ions:

Since

, then:

Normally, the hydronium ions produced from the first reaction


suppress the dissociation of water to such an extent that the
contribution of hydronium ions from the second equilibrium is
negligible, thus:
cHA = analytical concentration ( no other sources of A-)

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Example
Significant error has been introduced by the assumption that
[H3O+] << cC6H5NH3+ (just compare 7.09 x 10-5 with 2.0 x 10-4)

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Hydronium Ion Concentration of Solutions of Weak Bases

Example

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Example

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Example

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BUFFER SOLUTIONS: Calculating the pH of Buffer Solutions

The Henderson-Hasselbalch Equation

A solution containing a weak acid, HA, and its conjugate base, A-,
may be acidic, neutral or basic, depending on the positions of two
competitive equilibria:

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Example

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Example

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Example

Example

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Example

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The effect of Added Acids and Bases


Buffer solutions, their resistance to pH change after addition of
small amounts of strong acids and bases

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The effect of Added Acids and Bases

Preparation of Buffers
Buffer solution of any desired pH can be prepared by combining
calculated quantities of a suitable conjugate acid/base pair.

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Preparation of Buffers

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Sample Problems

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