ZOO

Last revised: 16 August 2006 Part I

pH M - 81

Questions: What do you mean by pH? How it is related to the equilibrium constant of water
molecule? How pH scale designates the H+ and OH- concentration? What are the relations
among pH, pKa & buffer concentration? Add a short note on the biological role of pH solution.
Q1. Describe the preparation of 1000 ml of a 0.1 M phosphate buffer pH 7.2 starting with 0.5 M H 3PO4 and 0.5 M NaOH.
Assume the following pKas: H3PO4 H2PO4 -= 2.2; H2PO4 HPO4 = 6.8; HPO4 PO4 = 12.4.
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Q2. What is the final pH of a solution made by mixing 100 ml of 0.05 M acetic acid and 100 ml of 0.1 M sodium acetate?
Assume the pKa for acetic acid is 4.76
Q3. For a solution that is 0.08 M K2HPO4 and 0.12 M KH2PO4, calculate the concentration of H3PO4, H2PO4 -, HPO4 -2,
PO-3; H+, OH-, and K+. Use the pKas given above.

pH : (+2)
The term pH is first use by Srensen as the negative logarithm of the hydrogen ion concentration to the
base ten, where the [H] is expressed in mol lit -1. pH may also defined as the index of the exponential term
obtained by writing the molar concentration of H+ at a power of 10.
So, pH = -log [H+] = log 1/[H+]. Where 'p' denoted as 'negative logarithm of'.

Relation to the equilibrium constant of water: (+6)

Water disassociates to a small but definite extant, depending on the temperature to give H+ & OH- ions. This
H+ soon after origin, reacts with H2O and yield H3O+ ion as the following reactions:

H2O H+ + OH-
+
H + H2 O H3O+

Such protolysis directly proportional to temperature; however, in solution there are H3O+ always present
instead of H+ which are similar in number to that of OH- ion concentration.
According to the lows of mass action, at equilibrium for the reaction of

H2O H+ + OH-

[ H ] [OH ]
= Keq [Keq is the equilibrium constant of water dissociation at a given
[ H 2 O] temperature]

[H+]+[OH-] = Keq [H2O] = Kw .(1)

Where Kw known as dissociation constant of water or ion product at a given temperature.

Here we can write Kw = Keq [H2O].

Only a few molecule of water mass ordinarily undergoes protolysis, therefore the mass of un-dissociated
water remain constant; so that, when it dissociated, yield equal number of both ions. i.e. number of H+
ion and OH- ion is equal, therefore we can write:
[H+][OH-] = Kw = [H+]2 or [OH-]2
or [H] = and [OH] = Kw

In pure water at 25C the concentration of water is 55.5M.

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(Grams of H2O in 1 lit divided by the molecular weight or 1000/18 = 55.5M)

So, at 25C we can right [H+][OH-] = Keq [H2O]

= Keq (55.5M)..(2)
= Kw
Where, the Kw designated the product of (55.5M)(Keq), which is usually known as ion product of the
water at 25C.
The value of the Keq has been determined by electrical conductivity measurements of pure water (in which
only the ions arising from the dissociation of H2O can carry current) and found to be 1.8 x 10-16 M at 25C.
Substituting the value for Keq gives :
[H+][OH-] = Keq [55.5 M]
= (1.8 x 10-16 M) (55.5 M)
= 99.9 x 10-16 M2
= 9.99 x 10-15 M2
= 0.99 x 10-14 M2
= 1.0 x 10-14 M2(3)
= Kw
Thus the product of [H+][OH-] in aqueous solution at 25C always equal to 1.0 x 10-14 M2. When there are
exactly equal concentration of both H+ and OH- as in pure water, the solution said to be the neutral pH. At
this point, the concentration of H+ and OH- can be calculated from the ion product of the water as follows :

Kw = [H+][OH-] = [H+]2 or [OH-]2

Solving for [H+] gives [H+] =
Putting the value Kw, we found, Kw
[H+] = 1.0 x10 14 M 2
[H+] =10-7 M taking -log from both side it will be found,
-log[H+]= -log 10-7M by simplification,
-log[H+] = = -log10-7 = log 107M
pH = 7 where p stands for the Power of anti log of hydrogen ion concentration

NOTE: The ion product of the water molecules makes possible to calculate the concentration of H +, given
the concentration of OH- and vice versa. As,

Problem 1. What is the concentration of H+ in a solution 0f 0.1M NaOH ? (+4)

Kw = [H+][OH-]
Solving for [H+] gives
Kw 1x10 14 M 2 10 14 M 2 10 14 M 2
+
[H ] = [OH ] = = = = 10-13 M (Ans.)
0.1M 0.1M 10 1 M
Problem 2. What is the concentration of OH- in a solution in which H+ concentration is
0.000013M? (+4)

Kw = [H+][OH-]
Solving for [OH-] gives,
Kw
[OH-] =
[H ]
Putting the value of Kw, yield,
1x10 14 M 2 1x10 14 M 2
[OH-] = = 4
= 7.69 x 10-11 M (Ans.)
0.00013 M 1.3 x10 M
Problem 3. What will be the concentration of H+ in a given solution of a pH value 4.72? (+4)
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PH = 4.72 = log104.72

= log 1 = 1
4.72
10 1.9 x10 5
So, [H+] = 1.9 x 10-5 (Ans.)

As the ion product of the water (Kw) is constant, whenever the concentration of H+ ion is greater
than 1x10-7 M, the concentration of OH-must be less than 1 x 10-7 M & vice versa. The [H+] when found
lower than 1 x 10-7 M in a solution which indicated that the solution is acidic in nature and when the
[H+] become greater than 1 x 10-7 M in a solution; this indicated that the solution is alkaline in nature.

What is pH scale and what is the concentration gradient of the H+ and OH- ion concentration in a
solution (+5)

The ion product of water, Kw, is the basis of the pH scale. It is a convenient means of designating
the actual concentration of H+ (and thus of OH-) in any aqueous solution in the range between 1.0 M H+ and
1.0 M OH-. The pH of a solution containing 1M H+ is 0 and that of another one 1M OH- is 14, therefore pH
scale expressing [H+] between 1M strong acid and 1M strong alkali extend from 0-14. This value of the
pH

The pH scale

In the solution is not arbitrarily chosen, it is derived from the absolute value of the ion product of water at
25C at its specific point. The pH scale is logarithmic, i.e. two solution differ in pH by 1 unit, means that
one solution has 10 times of the other in relation to the [H+] or [OH-] concentration. As for example, pH 1 to
pH 7 are 7 times differ from each other in relation to the said ionic concentration. Similarly from pH 0 to pH
14 are differ 14 times in the same way.

pH of a solution may be change due to addition of acid or base in the solution (+5)

According to proton transfer theory of Bronsted & Lowry, acid are substance which donate proton (H+) to
increase the [H+] of their solution while addition of base which receive the protons as a result decreased the
[H+] in the same solution.
The acid may be of two types according to the number of proton liberated to the solution. HCl is Monoprotic
i.e. contain one freely available H+ while the anion (Cl-), liberated by the ionization of an acid behave like a
base and thus it is called as conjugate base of the acid.

We know, any acid (HA) yield by ionization as,

HA + H2O ==== H3O+ + A-
[ H 3 O ][ A ] [ H ][ A ]
Keq = = = Keq [H2O] = Ka. .(4)
[ HA][H 2 O] [ H 2 O][HA]
Where Ka = Ion product and also known as acid dissociation constant. Its value is more conveniently
expressed as pKa called ionization exponent of an acid.
1

Ka -3-
Likewise pH, pKa = -log Ka = log

Therefore, stronger acid has greater ionization properties & thus higher of its Ka and its pKa, so HCl
possesses higher Ka and weak acid (lactic acid) has low Ka . So, lower of its pKa.

'a' of pKa is designated as acid &

'b' of pKb is designated as base &
'p' denoted as ' Anti log of '

the relationship between pH and pKa

Ka Kb = Kw = 10-14
So, pKa + pKb = pKw = 10-14 = [H+][A-]

Relation among pH, pKa & buffer concentration (+7)

The quantitative relationship among pH, buffering action of a mixture of weak acid with its
conjugate base and the pKa of the weak acid is given by the Henderson Hasselbalch Equation. We know
that,
[ H ] [OH ] [H ] [ A ] [H ] [ A ] [ HA]
Ka = for water or for acid, Or, Ka = , Or,[H+] = Ka
[ H 2 O] [ HA] [ HA] [ A ]
[ HA]
Then take the negative logarithm of both side, -log[H+] = -log Ka - log
[ A ]
[ HA]
Substituting pH for -log[H+] and pKa for -log Ka, we found pH = pKa -log
[ A ]
[ HA]
Now invert -log , which involves changing its sign, to obtain the Handerson-Hesselbalch Equation.,
[ A ]
[A ]
pH = pKa +log
[HA ]
which is generally stated that pH = pKa + log [ Proton acceptor] = Henderson Hasselbalch Equation
[ Proton donor]
This equation fits with the titration curve of all weak acids and enables us to deduce a number of
important quantitative relationship, for, e.g. It shows why the pKa of a weak acid is equal to the pH of the
solution at the mid point of titration, at this point [HA] = [A-] and thus,
pH = pKa + log1.0 = pKa + 0 = pKa pH = pKa

pH and its biological roles :- (+6)

1. pH and change of structural configuration & ionization of amino acid.
2. pH and specificity of enzymatic activity
3. pH and oxygen affinity to hemoglobin (Bohr effect)
4. pH and hereditary materials
5. Cell membrane and pH level.

Some Problems relating to pH: Complete Answers

Q1. Describe the preparation of 1000 ml of a 0.1 M phosphate buffer pH 7.2 starting with 0.5 M
H3PO4 and 0.5 M NaOH. Assume the following pKas: H3PO4 H2PO4 - = 2.2; H2PO4 - HPO4 -2 = 6.8;
HPO4 -2 PO4 -3 = 12.4.

Answer:
The total phosphate is 100 mM = 200 ml of 0.5 M H3PO4.
At pH 7.2, the two predominant forms of phosphate will be H2PO4 - and HPO4 -2 .

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 The ratio of HPO4 -2 to H2PO4 -is calculated from the Henderson-Hasselbalch equation. 7.2 = 6.8 +
log {[HPO4 -2]/[H2PO4 -]}, which means that [HPO4 -2]/[H2PO4 -] = 2.5.
The sum of [HPO4 -2] + [H2PO4 -] = 100 mM and [HPO4 -2]/[H2PO4 -] = 2.5.
Therefore, [HPO4 -2] = 71.4 mM and [H2PO4 -] = 28.6 mM

To prepare the buffer

o Take 200 ml of 0.5 M H3PO4.
o Add 200 ml of 0.5 M NaOH to convert all the H3PO4to H2PO4 -.
o Add 142.8 ml 0f 0.5 M NaOH to make 71.4 mM HPO4 -2 .
o Add water to 1000 ml.

Q2. What is the final pH of a solution made by mixing 100 ml of 0.05 M acetic acid and 100 ml of 0.1
M sodium acetate? Assume the pKa for acetic acid is 4.76

Answer:
100 ml of 0.05 M acetic acid = 5 mmol.
100 ml of 0.1 M sodium acetate = 10 mmol.
Using the Henderson-Hasselbalch equation
pH = pKa+ log{[acetate]/[acetic acid]}.
pH = 4.76 + log{[10]/[5]}.
pH = 5.06

Q3. For a solution that is 0.08 M K2HPO4 and 0.12 M KH2PO4, calculate the concentration of H3PO4,
H2PO4 -, HPO4 -2, PO-3; H+, OH-, and K+. Use the pKas given above.

Answer:
[H2PO4 -] = 0.12 M (the initial value).
[HPO4 -2] = 0.08 M (the initial value).
pH = 6.8 + log {[0.08]/[0.12]} = 6.62.
[H+] = 2.4 x 10-7M.
[OH-] = 1 x 10-14/2.4 x 10-7= 4.17 x 10-8 .
For H3PO4. pH = pKa+ log{[H2PO4 -]/[H3PO4]}; 6.62 = 2.2 + log{[H2PO4 -]/[H3PO4]}; [H2PO4 -] /
[H3PO4] = 2.63 x 104; Therefore, [H3PO4] = 4.56 x 10-6M.
For PO4 -3. pH = pKa+ log{[PO4 -3]/[HPO4 -2]}; 6.62 = 12.4 + log{[PO4 -3]/[HPO4 -2]}; [PO4 -
3
]/[HPO4 -2] = 1.66 x 10-6; Therefore, [H3PO4] = 1.32 x 10-7M.
K+= 0.12 M + 2x 0.08 M = 0.28 M.

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