Analytical Chemistry

Buffers A buffered solution resists changes in pH when acids or bases are added or when dilution occurs. The buffer is a mixture of an acid and its conjugate base or vice versa.

While there is a weak acid equilibrium going on, it is usually so weak that it can be ignored. Thus most of the time it is assume that the weak acid stays in its weak acid form (HA) and the conjugate base stays in its base form (A-).
To exert significant buffering, there must be a comparable amount of the conjugate acid and base.
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 Mixing

a weak acid and its conjugate base

If A moles

of a weak acid is mixed with B moles of its conjugate base, then the moles of acids remain close to A and the moles of base remain close to B. example consider an acid with pKa = 4.00 and its conjugate base with pKb = 10.00. Thus calculating the fraction of dissociation for the acid in a 0.10 M solution of HA. HA H+ + A pKa = 4.00 0.10-x x x
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For

The Ka is obtained from pKa, thus Ka = 1.0x10-4. The concentration is obtained as follows

The fraction of dissociation is obtained as follows

The acid is only 3.1% dissociated under these conditions. In a solution containing 0.10 mol of A dissolved in 1.00L, the extent of the reactant of A with water is much smaller A + H2O HA + OH pKb = 10.00 0.10-x x x
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The concentration is obtained as follows

The fraction of dissociation is obtained as follows

A is only 0.0032% dissociated under these conditions. HA dissociates very little, and adding extra A to the solution makes HA dissociate even less. Also A does not react much with water, and adding extra HA makes A react even less.
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Henderson-Hasselbalch equation The central equation for buffers is the HendersonHasselbalch equation, which a rearranged form of the Ka equilibrium expression

Rearranging the upper equation gives

Thus the Henderson-Hasselbalch equation for an acid is

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 If

the solution is prepared from a weak base B and it conjugate acid, then the Henderson-Hasselbalch equation is

The

pKa applies to the acid BH+. Where pKa is the dissociation constant of the weak acid BH+. important feature of the above two equations that the base (A- or B) appears in the numerator, and the acid is in the denominator. is for the acids in the denominator.

The

Ka

 If

[HA] = [A-] then pH = pKa.

When

the ratio of [A-]/[HA] changes by a factor of 10, then the pH changes by 1 unit. the concentration of the base (A-) increases, then the pH goes up. the concentration of the acid (HA) increases, then the pH goes down. any conjugate acid-base pair, if the pH = pKa-1 then there must be 10 times as much as HA as A-.
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As

As

For

 The

effect of [A-]/[HA] on pH is given in the following table.

Example

Sodium hypochlorite (NaOCl the active ingredient of almost all bleaches) was dissolved in a solution buffered to pH 6.20. Find the ratio [OCl-]/[HOCl]?
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 Example

Find the pH of a 1.00 L aqueous solution prepared with 12.34 g of tris (FM 121.135) plus 4.67 g of tris hydrochloride (FM 157.569)?
Example

If we add 12.0 mL of 1.00 M HCl to the solution in the previous example, what will be the new pH?

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 The

pH of buffer does not change very much when a limited amount of strong acid or base is added. resists the change in pH because the added strong acid or base is consumed by B or BH+.

Buffer

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