Acid – Base

Reactions of Acids and Bases

Strong acids such as HCl and HNO3 are completely dissociated in dilute
aqueous solution. For example, in the reaction between hydrogen chloride
and water:

HCl + H2O ⎯⎯⎯⎯⎯→ H3O+ + Cl- (1)

Ionization is essentially complete, and no meaningful equilibrium constant

can be measured. Most acids, however, are incompletely dissociated, so their
equilibrium constants can be measured. Typical examples are CH3COOH and
benzoic acids and H2S.

If a simple dissociation reaction is written for the weak acid, HX:

HX ⇌ H+ + X- (2)

The equilibrium constant, Ka is given by the expression

[𝐻 +][𝑋 −]
𝐾𝑎 = (3)
[𝐻𝑋]

And is called the acid dissociation constant

If a weak acid is the only solute present, the concentration of [H+] ions
produced from nominal concentration, c, of the acid can be calculated as
follows:

[H+] = [X-] and [HX] = c – [H+]

So from equation 3
[H+ ]2
𝐾𝑎 = 𝑐−[𝐻 +] (4)

From which [H+] can be calculated

If the acid is very weak, dissociation is slight, so, [H+]≪ 𝑐,

𝑎𝑛𝑑 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 4 simplifies to Ka c = [H+]2 (5)

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Strong bases, such as NaOH/KOH, are also completely dissociated in
aqueous solution, but weaker bases, such as ammonia, take part in an
equilibrium reaction with H2O:

NH3 + H2O ⇌ NH4+ + OH- (6)

Thses equilibria of a weak bases with water can be tretaed similarly to
the equilibrium of weak acids with water, to give expression for the
dissociation of the weak bases, Kb. For ammonia,
Kb = [NH4+][ OH-] /[NH3] = 1.8 × 10-5 mole/litre at 250C

Dissociation of Water
Water itself is slightly dissociated into hydrogen ions and hydroxide ions

H2O ⇌ H+ + OH- ( 7)
As the concentration of water is essentially constant, it is possible to
define another constant,
Kw = [H+][ OH-] (8)
Called the ionic product of water, which has the value
1.0× 10-14 mole2/litre2 at 250C. It should be remembered that the value
of Kw changes with temperature. For instance,

At 00C it is ⎯⎯⎯⎯⎯→10-15 mole2/litre2

At 600C it is ⎯⎯⎯⎯⎯→10-13 mole2/litre2

The Concept of pH
As hydrogen ions often have important effects on reactions and
equilibria, it is essential to have knowledge of the hydrogen-ion
concentration in a solution, even if the concentration is very small.
Sørenson devised a convenient logarithmic means of expressing the
hydrogen-ion concentration. He defined an operator p such that
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 pH = -log[H+] (9)
Thus the pH of 10-5 M hydrochloric acid is –log(10-5) = -(-5) =5. On the
pH scale, a ten fold reduction in hydrogen ion concentration results in an
increase of one unit in the pH value.
Solutions which have [H+] greater than 1 M have negative pH values.

The system is extended to accommodate alkaline solutions. From equations 8

&9

pH = -log(Kw/[OH-]) (10)

= log 10-14 + log [OH-]

14 + log [OH-] (11)

pOH = -log [OH-] (12)

 pH + pOH = 14 at 250C (13)

Thus for 10-3M sodium hydroxide

pOH = 3

 pH = 14 – pOH = 11

Neutral solution has the pH 7.

Acid-Base Indicators

There are weak organic acids and bases which have appreciably different
colours when they are ionized and un-ionized, or when they are in different
ionic states. These can be used to indicate changes in acidity or alkalinity in
aqueous solution and are termed as acid-base indicators.

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For example, a solution of un-protonated Methyl Red [Ind-] is orange-
yellow whereas that of the protonated (Ind.H) is red:
+
H

(CH 3)2N N=N SO3-

Ind.H (red)

(CH 3)2N N=N SO3- + H+ (14)

Ind- (orange-yellow)

Ind.H (red) Ind- + H+

[Ind− ][H+]
𝐾𝐼𝑛𝑑 = (15)
[Ind.H]

❖ The colour intensity of a dilute solution is usually proportional to the

concentrations and the molar absorbances of the colored species
❖ When the pH of a solution is such that both forms of an indicator are
present, the colour observed is a mixture of the colours of the two
components and depends on the concentration ratio of the
components, which is determined by the pH.
❖ It is usually considered that a 10 : 1 ratio of one form of an indicator to
the other is sufficient to prevent visual detection of the minor
component, so the colour perceived is that of the major component.
❖  as the pH of a solution containing an indicator is changed, a colour
change is observed only between
[Ind.H] = 10[Ind-] and 10[Ind.H] = [Ind-]
Thus from equation (15) the colour change is observed when the
hydrogen-ion concentration changes over the range from
[H+] = KInd10[[Ind-]/[Ind-] = 10KInd (acid colour) to [H+] = KInd[Ind-
]/10[Ind-] =0.1kInd (alkaline colour) i.e. from pH = pKInd -1 to pKInd +1.

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 The pH range over which an indicator changes from its acid to its
alkaline colour is called the colour change interval or the transition range
of the indicator and usually given as pKInd ± 1> For Methyl Orange,
pKInd = 3.4, so the transition range is approximately from pH 2.4 to pH
4.4.

Some common Acid-Base Indicators

Indicator Colour change Transition pH range

Acid ⎯⎯→ alkali
Thymol Blue Red ⎯⎯→ yellow 1.2 – 2.8
Methy Orange Red ⎯⎯→ Orange 3.0 – 4.4
Methyl Red Red ⎯⎯→ yellow 4.2 – 6.3
Phenolphthalein Colouless⎯⎯→ Red 8.0 – 9.8
Thymolphthalein Colouless⎯⎯→ Blue 9.3 – 10.5

These observations refer only to two colour indicators.

For indicators which are colourless in one form, slightly different

considerations apply, and if the criterion for the colour change is the first
appearance (or final disappearance) of the color, the concentration of the
indicator will affect the pH at which this occurs.

Thus for a one colour indicator (e.g. colourless in acid), if c is the minimum
detectable concentration of the coloured form and C the total indicator
concentration, the colour change will be perceived at a pH equal to pK Ind
when C=2c, pKInd-1 when C = 10c, and pKInd-2 when C =100c.

Q. Mention the effect of indicator concentration on the colour change in

case of one colour indicator.

Q. Mention the applications of Acid-Base indicators with examples.

❖ They can be used to indicate the end point of appropriate acid-base

titrations.
❖ They can also be used to determine the pH of a solution.
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 For example, Methyl Orange is red at pH 3, orange at pH 4 and yellow at
pH 5. Thus pH of a solution between 3 and 5 can be estimated from the
colour of this indicator in the solution. The colour may be compared
either with that of the indicator in solution of known pH or, more
usually, with the colour chart found in books of pH indicator papers.

A single colored indicator covers only a small pH range, but judicious

mixture of indicators can give rise to progressive color changes over a wide
range of pH.

A typical example is a solution containing Methyl Orange, Methyl Red,

Bromothymol Blue and phenolphthalein. It is

Red ⎯⎯→ at pH 3

Orange ⎯⎯→ at pH 5

Yellow ⎯⎯→ at pH 6

Green-blue ⎯⎯→ at pH 8

Blue ⎯⎯→ at pH 9

Violet ⎯⎯→ at pH 810

This mixture is called a universal indicator.

What is universal Indicator?

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