Buer solutions
quantic-bolt


Weak acids and bases

Weak acids and bases are acids and bases which don't dissociate to a great extent in water. For example, consider acetic acid
(CH3 COOH), which has ka = 1.75 105 . Writing the equilibrium expression for the dissociation of acetic acid in water, we
then obtain, the following:

[CH3 COO ][H + ]

= 1.75 105
[CH3 COOH]
It then follows from this that weak acids must have weak conjugate bases. That is, because ka kb = kw = 1.0 1014 , given
the ka of acetic acid, kb (of CH3 COO- ) must be some number raised to a negative power of 10, such that it does not dissociate
1.01014
10
, and hence, the conjugate base of acetic acid, acetate
completely in water either. Specically, kb = 1.7510
5 = 5.7 10
(CH3 COO ) is obviously a weak base. This is an important observation, as the eect of buer systems comes into play when
titrating weak acids and weak bases with strong bases and strong acids respectively.
Conversely then, because the equilibrium constant for a strong acid/base is large (i.e. greater than 1000000), it follows that their
conjugate acids/bases, have equilibrium constants which are incredibly small.


Titration of a weak acid with a strong base

Assuming that we wish to observe the generation of a buer system, let's consider an example in which 50 mL of 1 M sodium
hydroxide is used to titrate 50 mL of 1 M acetic acid, by the reaction:

N aOH + CH3 COOH

N aCH3 COO + H2 O
We note two things about this reaction before proceeding:
1. The reagents react in a 1:1 ratio implying no need to worry about mole ratios.
2. The resulting salt (NaCH3 COO), is weakly basic, for the reason mentioned in the preceding section.
In order to observe the generation of a buer system, we'll make use of a table (Table 1), which will show us snapshots of the
amount of each species present at dierent periods in time (in which each subsequent measurement is taken after the addition of
7.5 M of NaOH), as well as the pH of the reaction mixture (calculated via the Henderson-Hasselbalch equation after the addition
of NaOH, and via the use of the equilibrium expression, prior to the addition of NaOH). Using this info, we will then also plot
a calibration curve to illustrate what is meant by a buer zone/region, graphically. See below the table for a summary of the
calculations.
NaOH added (mol)
0.0000
0.0075
0.0150
0.0225
0.0300
0.0375
0.0450

CH3 COOH remaining (mol)

0.0500
0.0425
0.0350
0.0275
0.0200
0.0125
0.0050

NaCH3 COO produced (mol)

0.0000
0.0075
0.0150
0.0225
0.0300
0.0375
0.0450

H2 O produced (mol)








pHn
2.37
4.00
4.38
4.66
4.93
5.22
5.70

Because there is initially no conjugate base (CH3 COO- ) present initially, it isn't possible to use the Henderson-Hasselbalch
equation to calculate the initial pH of the solution. However, knowing the equilibrium constant for acetic acid, we can simply
use the equilibrium expression instead, to determine the concentration of H+ ions present in solution, and then the negative
logarithm of that to obtain pH. Hence:

pH0 = log[H + ] = log(

1.75 105 ) = 2.37

After this however, due to the presence of conjugate base, it's possible to use the Henderson-Hasselbalch equation to calculate
the pH:

pH1 = pka + log10 [

CH3 COO
0.0075
] = log10 (1.75 105 ) + log10 (
) = 4.75 0.75 = 4.00
CH3 COOH
0.0425

It's important to note here, that it is acceptable to ignore the volume change upon addition of NaOH, as the moles of conjugate
acid/base, will yield the same ratio if they are expressed as concentrations instead (i.e. the volume terms cancel out in the
division). Repeating this process a few more iterations, yields the results in Table 1. We can then plot this information in the
form of a titration curve (Figure 1).

sEK,>

What's important to note in this graph, is the central region in which pH doesn't change drastically, when compared to the
pH changes at either end of the graph. This zone is referred to as the buer region, and occurs at the half-equivalance point.
The reason for its occurrence at the half-equivalence point is that it is at this point, where moles of conjugate acid/base are
equivalent, where, pH = pka , by the Henderson-Hasselbaclh equation.