Acid Base Equilibria

Bronsted Lowry Theory of Acid and bases

 An acid is a proton (hydrogen ion) donor.

 A base is a proton (hydrogen ion) acceptor.

Conjugate Pairs

Consider an acid HA, and think of the reaction as being reversible.

Thinking about the forward reaction:

 The HA is an acid because it is donating a proton (hydrogen ion) to the water.

 The water is a base because it is accepting a proton from the HA.

But there is also a back reaction between the hydroxonium ion and the A- ion:

 The H3O+ is an acid because it is donating a proton (hydrogen ion) to the A- ion.
 The A- ion is a base because it is accepting a proton from the H3O+.

The reversible reaction contains two acids and two bases. We think of them in pairs,
called conjugate pairs.

When the acid, HA, loses a proton it forms a base, A-. When the base, A-, accepts a proton back
again, it obviously refoms the acid, HA. These two are a conjugate pair.

Members of a conjugate pair differ from each other by the presence or absence of the
transferable hydrogen ion.

A second example of conjugate pairs

This is the reaction between ammonia and water :

Think first about the forward reaction. Ammonia is a base because it is accepting hydrogen ions
from the water. The ammonium ion is its conjugate acid - it can release that hydrogen ion again
to reform the ammonia.

The water is acting as an acid, and its conjugate base is the hydroxide ion. The hydroxide ion can
accept a hydrogen ion to reform the water.

Looking at it from the other side, the ammonium ion is an acid, and ammonia is its conjugate
base. The hydroxide ion is a base and water is its conjugate acid.

Strong and Weak Acids

Strong Acids and pH

pH is a measure of the concentration of hydrogen ions in a solution
Hydrochloric acid is a strong acid - virtually 100% ionised. Each mole of HCl reacts with the
water to give 1 mole of hydrogen ions and 1 mole of chloride ions

That means that if the concentration of the acid is 0.1 mol dm-3, then the concentration of
hydrogen ions is also 0.1 mol dm-3.

Use your calculator to convert this into pH.

log10 [0.1] = -1

But pH = - log10 [0.1]

- (-1) = 1

The pH of this acid is 1.

Weak acids and pH

The equilibrium for the dissociation of ethanoic acid is properly written as:

The Ka expression is:

If you are using the simpler version of the equilibrium . . .

. . . the Ka expression is:

[H+] = [CH3COO-]

Further examples will be done in class.

Strong Bases and pH

Remember that:

Since pH is a measure of hydrogen ion concentration, how can a solution which contains
hydroxide ions have a pH?
Calculate the pH of a solution of NaOH(aq) of concentration 0.005 mol dm-3.
NaOH(aq) Na+(aq) + OH-(aq)
From the equation:
1 mole of NaOH produces 1 mole of OH-
0.005 mole of NaOH produces 0.005 mole of OH-
pOH = -log[OH-] = -log[0.005] = 2.3
pH= 14- pOH = 14- 2.3 = 11.7

Weak acids an pH
The Base Dissociation Constant
Calculate the pH of 0.15 moldm-3 NH3(aq), given that Kb for NH3(aq) is 1.8 x 10-5 moldm-3.

Since x<< 0.15 then 0.15-x≈ 0.15 :

Calculating the pH of a weak Base given Ka

pKa + pKb =14
What is the pH of Mrthylamine of concentration 0.45 mol dm-3 given that pKa of CH3NH3+ is
9.25.
If we have pKa, then we maust calculate pKb
pKb= 14- pKa
= 14- 9.25
= 4.75
Then calculate Kb
Kb = 10-pKb
= 10 -4.75
 = 1.775 x 10-5 mol dm-3

Now that we have Kb the procedure is the same as before.

CH3NH2(aq) + H2O(l) CH3NH3+(aq) + OH-(aq)

Initial 0.45 0 0
Change -x x x
Equil’m 0.45-x x x

Since x<< 0.45 then 0.45-x≈ 0.45 :

Kb= x2
0.45
1.775 x 10 -5 = x2
0.45
X= 2.829 x 10 -3 mol dm-3 = [OH-]

pOH = - log[2.829 x 10 -3]

= 2.55
pH= 14 –pOH
= 14 – 2.55
= 11.45

Ionic Product of Water , Kw

Water molecules can function as both acids and bases. One water molecule (acting as a base)
can accept a hydrogen ion from a second one (acting as an acid). The net effect is that an
equilibrium is set up.
This equilibrium written in a simplified form:

Kw is essentially just an equilibrium constant for the reactions shown. You may meet it in two
forms:

Based on the fully written equilibrium . . .

. . . or on the simplified equilibrium:

Like any other equilibrium constant, the value of Kw varies with temperature. Its value is usually
taken to be 1.00 x 10-14 mol2dm-6 at room temperature. In fact, this is its value at a bit less than
25°C.

The relationship between Kw and pKw is exactly the same as that between Ka and pKa, or [H+]
and pH.
Acid Base Indicators

Litmus is a weak acid. It has a seriously complicated molecule which we will simplify to HLit.
The "H" is the proton which can be given away to something else. The "Lit" is the rest of the
weak acid molecule.

There will be an equilibrium established when this acid dissolves in water. Taking the simplified
version of this equilibrium:

The un-ionised litmus is red, whereas the ion is blue.

Now use Le Chatelier's Principle to work out what would happen if you added hydroxide ions or
some more hydrogen ions to this equilibrium.

Adding hydroxide ions:

Adding hydrogen ions:

pH Range of Indicators
Indicators don't change colour sharply at one particular pH. Instead, they change over a narrow
range of pH.
The graph below is the typical graph of an acid base titration where the pH is measure on
addition of small amounts of acid or base until well beyond endpoint.
An indicator can only be used if it falls within the vertical section of the graph.

Both phenolphthalein and methly orange do that. BUT the most suitable indicator also has to be
close the the equivalence point. Since phenolphthalein is closer than methyl orange, it is the most
suitable indicator for the titration.

Examples of different titration curves.