Generally, buffer solutions are prepared from a conjugate acid/base pair, such as acetic acid/sodium acetate or ammonium chloride/ammonia.

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1 Buffer Solution

2 A buffer solution resists changes in ph when it is diluted or when acids or bases are added to it. Generally, buffer solutions are prepared from a conjugate acid/base pair, such as acetic acid/sodium acetate or ammonium chloride/ammonia.

3 1) 2) When we have a weak acid and its conjugated bases, which is the ph of the solution?

4 If the first equilibrium lies farther to the right than the second, the solution is acidic. If the second equilibrium is more favorable, the solution is basic. These two equilibrium constant expressions show that the relative concentrations of the hydronium and hydroxide ions depend not only on the magnitudes of Ka and Kb but also on the ratio between the concentrations of the acid and its conjugate base.

5 To find the ph of a solution containing both an acid, HA, and its conjugate base, NaA, we need to express the equilibrium concentrations of HA and NaA in terms of their analytical concentrations, c HA and c NaA

6 Similarly, the first equilibrium will increase the concentration of A - by an amount equal to [H 3 O + ], and the second will decrease this concentration by the amount [OH - ].

7 1) Because of the inverse relationship between [H 3 O + ] and [OH - ], and it is always possible to eliminate one or the other from Equations. 2) Additionally, the difference in concentration between [H 3 O + ] and [OH - ] is usually so small relative to the molar concentrations of acid and conjugate base

8 The assumption leading to Equations previously described sometimes breaks down with acids or bases that have dissociation constants greater than about 10-3 or when the molar concentration of either the acid or its conjugate base (or both) is very small. In these circumstances, either [H 3 O + ] and [OH - ] must be retained in Equations depending on whether the solution is acidic or basic.

9 1) Within the limits imposed by the assumptions made in deriving Equation, it says that the hydronium ion concentration of a solution containing a weak acid and its conjugate base depends only on the ratio of the molar concentrations of these two solutes. 2) Furthermore, this ratio is independent of dilution because the concentration of each component changes proportionally when the volume changes.

14 Properties of Buffer Solutions The Effect of Dilution The ph of a buffer solution remains essentially independent of dilution until the concentrations of the species it contains are decreased to the point where the approximations used to develop Equations previously reported become invalid.

15 The resistance of the buffered solution to changes in ph during dilution is clearly shown.

16 The Effect of Added Acids and Bases

17 Buffers do not maintain ph at an absolutely constant value, but changes in ph are relatively small when small amounts of acid or base are added.

18 The Composition of Buffer Solutions as a Function of ph: Alpha Values The composition of buffer solutions can be visualized by plotting the relative equilibrium concentrations of the two components of a conjugate acid/base as a function of the ph of the solution. These relative concentrations are called alpha values.

19 Alpha values depend only on [H 3 O + ] and Ka, and are independent of c T.

22 Note that most of the transition between α0 and a α 1 occurs within ±1 ph unit of the crossover point of the two curves. Acetic Acid example: At this pka, the concentrations of acetic acid and acetate ion are equal, and the fractions of the total analytical concentration of acid both equal one half.

23 Buffer Capacity The buffer capacity,ß, of a solution is defined as the number of moles of a strong acid or a strong base that causes 1.00 L of the buffer to undergo a 1.00-unit change in ph.

24 Buffer capacity depends not only on the total concentration of the two buffer components but also on their concentration ratio. The buffer capacity decreases fairly rapidly as the concentration ratio of acid to conjugate base becomes larger or smaller than 1 (the logarithm of the ratio increases above or decreases below zero).

Chapter 9 Aqueous Solutions and Chemical Equilibria

Chapter 9 Aqueous Solutions and Chemical Equilibria At equilibrium, the rate of a forward process or reaction and that of the reverse process are equal. 9A The chemical composition of aqueous solutions