The Common-Ion Effect

Consider a solution of acetic acid:

CH3COOH(aq) + H2O(l) H3O+(aq) + CH3COO(aq)

If acetate ion is added to the solution,

Le Chtelier says the equilibrium will
shift to the left.

Aqueous
Equilibria

2009, Prentice-Hall, Inc.

 The Common-Ion Effect
The extent of ionization of a weak
electrolyte is decreased by adding to
the solution a strong electrolyte that
has an ion in common with the weak
electrolyte.

Aqueous
Equilibria

2009, Prentice-Hall, Inc.

What is the PH of a solution made by
adding 0.3 mol of acetic acid and 0.3
mol of soduim acetate to enough water
to make 1L of solution.

Aqueous
Equilibria
 The Common-Ion Effect
Calculate the fluoride ion concentration and pH
of a solution that is 0.20 M in HF and 0.10 M in
HCl.

Ka for HF is 6.8 104.

[H3O+] [F]
Ka = = 6.8 10-4
[HF]
Aqueous
Equilibria

2009, Prentice-Hall, Inc.

 The Common-Ion Effect
HF(aq) + H2O(l) H3O+(aq) + F(aq)

Because HCl, a strong acid, is also present,

the initial [H3O+] is not 0, but rather 0.10 M.

[HF], M [H3O+], M [F], M

Initially 0.20 0.10 0
Change x +x +x
At Equilibrium 0.20 x 0.20 0.10 + x 0.10 x

Aqueous
Equilibria

2009, Prentice-Hall, Inc.

 The Common-Ion Effect

(0.10) (x)
6.8 104 =
(0.20)
(0.20) (6.8 104)
=x
(0.10)

1.4 103 = x

Aqueous
Equilibria

2009, Prentice-Hall, Inc.

 The Common-Ion Effect

Therefore, [F] = x = 1.4 103

[H3O+] = 0.10 + x = 0.10 + 1.4 103 = 0.10 M

So, pH = log (0.10)

pH = 1.00
Aqueous
Equilibria

2009, Prentice-Hall, Inc.

Buffers

Buffers are solutions

of a weak conjugate
acid-base pair.
They are particularly
resistant to pH
changes, even when
strong acid or base is
added.
Aqueous
Equilibria

2009, Prentice-Hall, Inc.

 Buffers

If a small amount of hydroxide is added to an

equimolar solution of HF in NaF, for example, the HF
reacts with the OH to make F and water. Aqueous
Equilibria

2009, Prentice-Hall, Inc.

 Buffers

Similarly, if acid is added, the F reacts with it to form

HF and water. Aqueous
Equilibria

2009, Prentice-Hall, Inc.

 Buffer Calculations
Consider the equilibrium constant
expression for the dissociation of a
generic acid, HA:

HA + H2O H 3O + + A

[H3O+] [A]
Ka =
[HA]
Aqueous
Equilibria

2009, Prentice-Hall, Inc.

 Buffer Calculations

Rearranging slightly, this becomes

[A]
Ka = [H3O+]
[HA]
Taking the negative log of both side, we get
] base
[A
log Ka = log [H3O+] + log
[HA]
pKa
acid Aqueous
Equilibria
pH
2009, Prentice-Hall, Inc.
 Buffer Calculations

So
[base]
pKa = pH log
[acid]
Rearranging, this becomes
[base]
pH = pKa + log
[acid]
This is the HendersonHasselbalch equation.
Aqueous
Equilibria

2009, Prentice-Hall, Inc.

HendersonHasselbalch Equation

What is the pH of a buffer that is 0.12 M

in lactic acid, CH3CH(OH)COOH, and
0.10 M in sodium lactate? Ka for lactic
acid is 1.4 104.

Aqueous
Equilibria

2009, Prentice-Hall, Inc.

HendersonHasselbalch Equation

[base]
pH = pKa + log
[acid]
(0.10)
pH = log (1.4 104) + log (0.12)

pH = 3.85 + (0.08)

pH = 3.77
Aqueous
Equilibria

2009, Prentice-Hall, Inc.

 pH Range
The pH range is the range of pH values
over which a buffer system works
effectively.
It is best to choose an acid with a pKa
close to the desired pH.

Aqueous
Equilibria

2009, Prentice-Hall, Inc.

When Strong Acids or Bases Are
Added to a Buffer
it is safe to assume that all of the strong acid
or base is consumed in the reaction.

Aqueous
Equilibria

2009, Prentice-Hall, Inc.

Addition of Strong Acid or Base to a
Buffer
1. Determine how the neutralization
reaction affects the amounts of
the weak acid and its conjugate
base in solution.
2. Use the HendersonHasselbalch
equation to determine the new
pH of the solution.

Aqueous
Equilibria

2009, Prentice-Hall, Inc.

Calculating pH Changes in Buffers
A buffer is made by adding 0.300 mol
HC2H3O2 and 0.300 mol NaC2H3O2 to
enough water to make 1.00 L of
solution. The pH of the buffer is 4.74.
Calculate the pH of this solution after
0.020 mol of NaOH is added.

Aqueous
Equilibria

2009, Prentice-Hall, Inc.

Calculating pH Changes in Buffers

Before the reaction, since

mol HC2H3O2 = mol C2H3O2

pH = pKa = log (1.8 105) = 4.74

Aqueous
Equilibria

2009, Prentice-Hall, Inc.

Calculating pH Changes in Buffers

The 0.020 mol NaOH will react with 0.020 mol of the
acetic acid:

HC2H3O2(aq) + OH(aq) C2H3O2(aq) + H2O(l)

HC2H3O2 C 2 H 3 O2 OH
Before reaction 0.300 mol 0.300 mol 0.020 mol
After reaction 0.280 mol 0.320 mol 0.000 mol

Aqueous
Equilibria

2009, Prentice-Hall, Inc.

Calculating pH Changes in Buffers

Now use the HendersonHasselbalch equation to

calculate the new pH:

(0.320)
pH = 4.74 + log
(0.200)

pH = 4.74 + 0.06

pH = 4.80
Aqueous
Equilibria

2009, Prentice-Hall, Inc.

*What is the pH of a solution containing 0.30 M HCOOH and 0.52 M HCOOK?
HCOOKaq (0.52 M ) K+aq + HCOO-aq ( 0.52 M )
HCOOH H+aq + HCOO-aq
initial : 0.30M 0.00 0.52M
Change : -x +x +x
Equilibrium: 0.30-x x 0.52+x , 0.30-x x , 052+x 0.52
pH = pKa + log [HCOO- ] / [HCOOH] = 3.77 + log [0.52] / [0.30] = 4.01
-----------------------------------------------------------------------------------------------------
* Which of the following are buffer system ?
a) KF /HF (buff.) b) KBr/HBr ( not buff.) c) Na2CO3 /NaHCO3 (buff.)
d) KH2PO4 / H3PO4 ( buff.) e) NaClO4 / HClO4 (not buff.) f) C5H5N/C5H5NH+
(buff. ) g) K2HPO4 / H3PO4 ( not buff.) .

----------------------------------------------------------
Calculate the pH of the 0.30 M NH3 /0.36 M NH4Cl buffer system. What is the pH
After the addition of 0.01 mol of NaOH to 1.0 L of buffer solution ? . Assume that
the volume of the solution does not change when the NaOH is added .
NH4+ (aq) H+ (aq) + NH3 (aq) , pH = pKa + log [NH3] /[NH4 +]
pH = 9.25 + log [0.30] / [0.36] = 9.17 :
NH4+(aq) + OHaq H2O(l) + NH3(aq)
start : 0.36 M 0.01 M 0.30 M
end : 0.35 M 0.00 0.31 M
pH = 9.25 + log [0.31] / [0.35] = 9.20 Aqueous
-------------------------------------------------------------------------------------------------------------- Equilibria

2009, Prentice-Hall, Inc.