Applications of Aqueous Equilibria

1 Neutralization Reactions
2 The Common-Ion Effect

Acid-base reactions play a very important role (pH of lakes, blood, acid
rain (section at end of chapter 15) and also the solubility of salts and
the factors that affect solubility are also of great importance.

1 Neutralization reactions
Usually acids react with bases to produce water and salt:
HBr(aq) + NaOH(aq) -----> NaBr(aq) + H2O
Strong Acid-Strong Base
This is the case illustrated above and the acid/base reaction is called a neutralization.
In the strong acid/strong base case the resulting pH of the final solution is actually 7
(neutral) hence the use of theterm neutralization.
As we will see later, neutralization reactions involving weak acids and/or weak bases
result in non-neutral solutions but the term neutralization is still used.

Since strong acids and bases are totally dissociated in solution the net
ionic equation for the above reaction is:
H2O (l)
H+ (aq) + OH-(aq)
(or

H3O+ (aq) + OH-(aq) -->

2H2O (l))

K eq is a very large number so the equilibrium for a strong acid /strong

base neutralization lies essentially 100% to the right.
The other ions, Na+ and Br- , are spectator ions, The pH of a solution
made by adding equal molar amounts of acid and base is neutral.
Weak Acid-Strong Base
Because a weak acid (HA) is largely undissociated, the net ionic
equation for the neutralization reaction involves proton transfer from HA
to the strong base, OH-.
Net ionic equation
HA(aq) + OH-(aq) H2O + A-(aq)
The weak acid, acetic acid, reacts with aqueous NaOH to produce
water and the acetate ion.
The weak acid, HF reacts with aqueous NaOH to produce water and Fion. Note that in each case the Na+ ion doesn t appear in the equation
because both NaOH and NaF are completely dissociated and the Na+
ion is a spectator ion.

To obtain the equilibrium constant for the reaction (not 100% to the right
as before) we add the reactions that give the net ionic equation and
multiply the appropriate K values.
The calculation for the acetic acid/NaOH case is given in the book and
the HF/NaOH case follows:
We want the net ionic eqn.

HF(aq) + OH- (aq)

H2O + F- (aq)

Ka = 3.5 x 10-4
1/Kw = 1 x 10+14
------------------K = Ka / Kw
= 3.5 x 1010
The value of K is still pretty large so the reaction goes mostly to the right.

Add

F-(aq) + H3O+
HF(aq) + H2O
H3O+(aq) + OH-(aq) 2H2O
+ ------------------------------------------------HF(aq) + OH- (aq) H2O + F- (aq)

As a general rule, any weak acid is essentially 100% neutralized by a

strong base since the OH- ion has a very strong affinity for protons.

The resulting solution when equimolar quantities of weak acid and

strong base are mixed has a pH > 7 (basic) since the Na+ is a
spectator ion and the F- ion hydrolyzes in water and is a weak base...
F-(aq) + H2O

HF(aq) + OH-(aq)

Strong Acid- Weak Base

A strong acid is completely dissociated into H3O+ and A- ions so the
neutralization reaction in this case involves proton transfer from the
H3O+ to the weak base, B.
General case

H3O+ (aq) + B(aq)

Specific case

H3O+ (aq) + NH3(aq)

BH+(aq) + H2O
NH4+ (aq) + H2O

The value of K for the neutralization is found by multiplying known K s

for reactions that add up to give the required neutralization reaction.

Example in text uses ammonia and strong acid, I will use a different weak
base, aniline.
C6H5NH2 (aq) + H2O C6H5NH3+ (aq) + OH-(aq) Kb = 4.3x10-10
(aniline)
H3O+ (aq) + OH-(aq) 2H2O
1/Kw = 1.0x1014
------------------------------------------------------------------------------------------C6H5NH2 (aq) + H3O+ (aq) C6H5NH3+ (aq) + H2O
K = Kb / Kw
= 4.3 x 104
Again the neutralization proceeds mostly to the right since K is a pretty large
number (example in book for NH3 + H3O+ is an even bigger number, 109).
If equimolar quantities of the strong acid and weak base are mixed, the
resulting solution will be acidic (pH <7) since the Cl- (from HCl) is a
spectator ion and the C6H5NH3+ ion hydrolyzes in water producing H3O+.
C6H5NH3+ (aq) + H2O

C6H5NH2 (aq) + H3O+ (aq)

Weak Acid-Weak Base

Here both the acid and the base are largely undissociated, so the
neutralization reaction therefore involves proton transfer from the weak
acid to the weak base. (Example done in the text is for acetic acid
reacting with ammonia. I will do example of benzoic acid, C6H6COOH,
reacting with hydroxylamine, NH2OH)
The neutralization reaction is
C6H6COOH(aq) + NH2OH(aq) < > C6H6COO-(aq) + NH3OH+(aq)
Addition of 1) the acid dissociation reaction, 2) the base protonation of
the hydroxylamine reaction and 3) the reverse of the water dissociation
reaction gives the required neutralization reaction.

C6H6COOH(aq) + H2O C6H6COO-(aq) + H3O+ (aq) Ka = 6.5x10-5

NH2OH(aq) + H2O NH3OH+(aq) + OH-(aq)
Kb = 9.1x10-9
H3O+ (aq) + OH-(aq) 2H2O
1/Kw = 1.0x1014
--------------------------------------------------------------------------- ----------------C6H6COOH(aq) + NH2OH(aq) C6H6COO-(aq) + NH3OH+(aq)
K= Ka Kb / Kw
= 5.9 x 101
Here the value of K is much lower than the previous three cases and
neutralizations of weak acids and weak bases do not proceed as far
towards completion.
e.g HCN(aq) + NH3(aq) NH4+ (aq) + CN- (aq)
K = 0.88
Here, K is less than unity so the reaction goes less than halfway to
completion.

2 The Common Ion Effect

In Chapter 15, solutions containing only one solute (an acid, base, or a
salt) were considered. In this chapter, solutions which contain two
solutes are considered.
The particular two component solutions considered here are ones
which contain a common ion. They fall into two categories:
1. a weak acid, HA, and its conjugate base, B-. e.g. a solution of
acetic acid, a weak acid, and acetate ion from a salt, say, sodium
acetate.
2. a weak base , and its conjugate acid. e.g. NH3, a weak base and
an ammonium salt , NH4Cl
In both cases, the salt dissolves in the water 100% and provides a
common ion, i.e. an ion that is also produced by the acid or base
equilibrium.

According to Le Chatelier s Principle, the presence of this common ion

from a source other than the equilibrium reaction, will alter the position
of the equilibrium. This is known as the common ion effect .
These solutions containing a common ion are highly resistant to
changes in pH upon addition of a strong acid or strong base and the
solution pH has a value close to the pKa of the weak acid or pKb of the
weak base. These solutions are known as buffers or buffer solutions
Weak acid/conjugate base system:
solution of HOAc + NaOAc where OAc - is the acetate ion (C2H3O2 -)
HOAc H+ (aq) + OAc -(aq)
NaOAc
Na+ (aq) + OAc -(aq)

Ka = 1.8x10-5
100% to completion

since the OAc - ion is a common ion , changing [OAc-] from the salt
will affect the position of the equilibrium.

To illustrate the effect of the common ion , we will first calculate the pH of
a solution of HOAc alone with no common ion (no OAc- ion).
Problem #1
What is the pH of a solution made by dissolving
0.25mol of HOAc and making up to 1.00L?
HOAc

H+ (aq) + OAc -(aq)

Ka = 1.8x10-5

set up table
initial
change
final

[HOAc]
0.25
-x
0.25-x

[H+]
0 (10-7)
+x
x

[OAc -]
0
+x
x

Substitute into Ka equation and find x

Ka = 1.8x10-5 = [H+][OAc -] / [HOAc] = x2 / 0.25-x
Assuming 0.25-x = 0.25, then x = 2.1x10-3M (which is << 0.25)
pH = - log (2.1 x10-3) = 2.67
Also assumption that initial [H+] of 10-7M can be ignored is OK since final
[H+] of 2.1x10-3 M is >> 10-7M.

Problem #2 What is the pH if the above acid solution also

contains 0.1 mol of NaOAc (along with 0.25 mol of HOAc) ?
Remember that the salt will dissolve completely providing an initial conc
of OAc-.
Set up table as before but now including a non-zero initial [OAc -]

initial
change
final

[HOAc]
0.25
-x
0.25-x

[H+]
0 (10-7)
+x
x

[OAc -]
0.1
+x
0.1+x

Substitute into Ka equation and find x

Ka = 1.8x10-5 = [H+][OAc -] / [HOAc] = x (0.1+x) / 0.25-x
Solve using the quadratic equation or simplify....

Assuming 0.25-x = 0.25, and 0.1+x =0.1

then x = 4.5x10-5M (which is << 0.25 and also << 0.1. Also x >> 10-7)
pH = - log (4.5x10-5) = 4.35
The original pH was 2.67 so the addition of the NaOAc has made the
solution less acidic (higher pH)

Addition of the OAc- ion shifts the acid dissociation reaction back to the
left (Le Chatelier s Principle) which produces less H+ and produces a
less acidic solution as we have seen.