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INTRODUCTION
H20
H + OH
If there is nothing but water (pure water) then the concentration of H must equal that of OH . The actual value is
-7
10 M. Thus indicating concentration by square bracket we have:
+
-14
[H ] [OH ] = 10
This value, called the ionic product of water, Kw, is related to the equilibrium constant of water
+
[H ] [OH ]
Keq =
[H2O]
+
As the concentration of undissociated H2O is large (55 M) and essentially constant, then [H ] [OH ] is also a
+
constant. That is, even when impurities are present to give a preponderence of H or OH the relationship
+
-14
[H ] [OH ] = 10
must hold.
+
-14
H concentration can vary between about 10 M in solution of strong acids to 10 M in solutions of strong bases.
To compact this huge range we represent hydrogen ion concentration as an exponential, designated pH.
+
pH = -log10 [H ]
+
Thus to represent a molarity of H as a pH value we take logs and change the sign.
When molarity is represented in the exponential notation its conversion to pH is easily done as we just take the
value of the index and change its sign.
Examples
What is the pH of 0.01 M HCl?
+
HCl is practically completely dissociated in water into H and Cl
+
-2
[H ]
= 10 M
pH
=2
What is the pH of 0.01 M NaOH?
+
NaOH dissociates in water to Na and OH
-2
Thus
[OH ]
= 10 M
+
-14
But
[H ] [OH ]
= 10 M
+
-12
[H ]
= 10 M
pH
= 12
+
-5
When [H ] = [OH ] the solution of course has a pH of 7 and is said to be neutral. An acid solution has a pH less
than 7. An alkaline solution has a pH greater than 7.
2.
It is simple to prepare:
a solution of pH 2, because
+
[H ]
e.g.
0.01 M HCl
or a pH 10 solution, because
+
[H ]
-4
e.g.
10 M NaOH
-2
=
=
10 M
pH 2
=
=
10 M
pH 10
-10
But for most occasions where biological material is being studied, solutions of a pH nearer neutrality will be
required.
-6
To attempt to produce a pH of 6 with 10 M HCl will be extremely difficult as any slight atmospheric or container
contamination will alter this very small concentration.
-6
Similarly, to prepare a solution of pH 8 with 10 M NaOH is practically impossible just due to traces of dissolved
CO2.
+
However, solutions can be prepared which are able to maintain a more stable H concentration in the mid
ranges of the pH scale. These solutions are called buffer solutions. They usually consist of a mixture of a weak
acid or base and a definite proportion of a suitable salt. (A strong acid is one that largely dissociates in aqueous
+
solution, i.e. it liberates many H ions; e.g. HCl. A weak acid is one that only partially dissociates in water.
Conversely, a strong base dissociates to provide many OH ions and a weak base dissociates little giving few
OH ions).
Take for example a weak acid:
-
HA
[ H + ][ A! ]
[ HA]
A +H
=
Keq
[ HA]
[ A! ]
[H +] ]
log[ H + ]
= log Ka + log
Ka
! log[ H + ] =
[ HA]
[ A! ]
[ A! ]
[ HA]
pH
! log Ka
pKa
pH
pKa + log
[ A! ] ]
[ HA]
pH = pKa + log
[ SALT ]
[ ACID]
A prime mark is usually placed over pKa (i.e. pK) to denote that the value was determined and is strictly valid
only for a specified concentration.
But within certain limits of dilution we can see that the pH of a solution is determined simply by the ratio of salt to
acid. Thus knowing the pKa of the acid it is possible to prepare a solution of a required pH simply by using
+
different ratios of salt to acid. What happens if we add OH or H to such a solution?
+
Adding H : these will combine with acidic ions, [A ], to form undissociated HA. Similarly on adding OH , these will
+
+
+
combine with H . The equilibrium HA H + A will be disturbed and more acid will dissociate to replace the H
ions removed. In either case, provided the concentration of HA and A are initially made large in comparison
+
with H , their concentration will not be appreciably changed.
Thus pH defined above as
[ A! ]
will not be largely affected.
[ HA]
pKa + log
-3
H + H2 PO
+
2H + H PO 4
+
3H + PO 4
K1 = 7.5 x 10
-8
K2 = 6.3 x 10
-13
K3 = 4.0 x 10
pK1 = 2.12
pK2 = 7.22
pK3 = 12.4
We are mainly concerned with the pKa' at 6.86 because at pH 6.32 practically none of
3the ions will be as H3 PO4 or PO4 .
2-
[HPO4 ]
pH = pK + log
[H2PO 4]
2-
[HPO 4]
[H2PO 4]
2-
-0.48 =
[HPO 4]
-
[H2PO 4]
-
1
=
3
5
4
3
2
1
3
5
pH
When the curve flattens at the mid-point, half the HA has been neutralised, i.e. [HA] = [A ].
Thus
[A - ]
[ HA ]
The pKa is therefore seen to be numerically equal to the pH at which half of the acid is dissociated (neutralised).
In other words, the value of the pKa of a given weak acid can be obtained by mixing equal quantities of the
weak acid and its salt.
Notice that the half neutralisation point marks the steepest part of the graph, i.e. it is the point at which the pH
+
changes least on adding OH (or H ). Thus if we require a buffering solution we use
[A ! ]
is close to 1 then relatively large changes
[ HA ]
[A ! ]
in [HA] and [A ] will result in only small changes in pH. To obtain a pH one unit away from the pKa then
[ HA ]
[A ! ]
must change tenfold in order that log
changes by 1. At a pH of one unit above and below the pKa' the
[ HA ]
a weak acid whose pKa is close to the desired pH. As long as
ratio of salt to acid is 10 and 0.1 respectively. Now very small changes in [HA] and [A ] will cause large changes
in pH.
+
[A ]
5
1
to
then changes from
.
[ HA]
50 54
!
The ratio of
The addition of the acid has thus lead to a pH shift from pKa + (-1) to pKa + (-1.7).
3.
THE MEASUREMENT OF pH
Electrometric pH determinations:
The voltage is measured between two half cells, one of known potential and the other an unknown, which
+
contains as part of the chemical system the H ion solution under test.
The standard electrode has been set as the Hydrogen electrode. This consists of a piece of inert metal such as
platinum covered with platinum black by electrolysing a solution of platinic chloride. The platinum black is
saturated with hydrogen gas and maintained in this condition. The platinum black can catalyse the reaction.
H2
H +e
The metal in fact becomes covered with electrons until equilibrium has been reached. This then has a certain
+
potential. At unit activity of H ions this potential is arbirtarily called zero.
The voltage of other half cells is given in reference to this standard.
The usual reference cell is the calomel electrode, i.e. metallic mercury in contact with KCl solution saturated with
mercurous chloride.
The other half cell is now nearly always the glass electrode (Figure 2).
Silver/silver electrode
HCl
pH sensitive glass
Figure 2 A silver electrode for pH measurement.
The glass behaves as a site for hydrogen ion transfer and the potential at the surface changes as H ion are
acquired or lost.
Thus we have:
Reference electrode
Salt Bridge
Electrode reversible to H
e.g. calomel : Hg
test soln:glass:HCl
AgCl:Ag
pH =
E ! E0
RT
F
A +H
[ A! ]
changes slowly from 0.1 to 10.
[ HA]
Thus the indicator phenol red, pKa 7.9 will contain at pH 6.9 ten times as many molecules of the yellow
undissociated form as of the red dissociated form. It could not be used to differentiate between a pH of 5 and 4
as the proportion of molecules changing from red to yellow would be too small for observation. Similarly, at pH
10 it would be virtually all red and could not differentiate between two solutions of pH 10 and 12.
Thus indicators are useful in differentiating pH values only within the range of about one pH unit above the pKa
of the indicator.
Indicators are used for two main purposes:
to measure the pH of a given solution.
to indicate when a titration is complete.
For the first use we need an indicator with a pKa near the pH to be measured. E.g., say we are titrating a weak
acid to find how concentrated it is. At what point do we terminate the titration? At the pKa of the acid we have
only titrated half of it. Suppose we would like to know the amount of acid to within 0.1%. We must continue to
titrate until a pH is reached where 99.9% of the HA is converted to A .
Take a weak acid pK = 5
At 99.9% Neutralisation
[ A! ]
=
[ HA]
999
1
[ A! ]
= 3
[ HA]
pH
pH
pH
=
=
pKa
[ A! ]
[ HA]
5+3
8
Thus for this degree of accuracy we need to select an indicator which will give its main colour change three pH
units above the pKa of the acid being titrated.