BUFFERS

A buffer is a solution containing both an acid and a base. A buffer can absorb excess acid (H+)
or base (OH-) without the pH of the solution changing significantly. It usually consists of 2
solutes, one is a weak Bronsted acid and the other is its conjugate base supplied by a soluble salt
of the acid. (Eg. Acetic acid and sodium acetate)

eg) Consider a buffer solution containing 0.2 M NaHCO3 and 0.3 M Na2CO3.

Both are soluble salts:NaHCO3  Na+1(aq) + HCO3-1(aq)

Na2CO3  2Na+1(aq) + CO3-2 (aq)

Therefore the buffer system set up consists of a conjugate acid/base pair

HCO3-1(aq) + H2O  H3O+1(aq) + CO3-2 (aq)

eg) What is the pH of the buffer?

HCO3-1(aq) + H2O  H3O+1(aq) + CO3-2(aq) Ka = 4.7*10-11

I 0.2 0 0.3
R -x +x +x
E 0.2 - x (0.2) x 0.3 + x (0.3)

Ka = ([H3O+1] [CO3-2])/[HCO3-1]
4.7*10-11 = (x)(0.3)/0.2
x = 3.1*10-11

[H+1] = 3.1*10-11  pH = 10.5

HOW DOES A BUFFER WORK?

We will first add an acid to the buffer which is called acid shock.

eg) Add 0.01 M HCl(aq) to the buffer.

This increases the [H+1] and Le Chatalier will cause the equilibrium to shift to the left to
use up the added hydrogen ions. (Remember [H+1] = [H3O+1])

What is the pH after the acid shock?

HCO3-1(aq) + H2O  H3O+1(aq) + CO3-2(aq) Ka = 4.7*10-11

I 0.2 0.01 0.3
R +0.01 -0.01 -0.01
E 0.21 About 0 0.29

Ka = ([H3O+1] [CO3-2])/[HCO3-1]
4.7*10-11 = (x)(0.29)/0.21
x = 3.4*10-11
 [H+1] = 3.4*10-11  pH = 10.46 (hardly changed)

We will now add a base to the buffer which is called base shock.

eg) Add 0.02 M NaOH(aq) to the buffer.

H+1 + OH-1  H2O
This decreases the [H+1] and Le Chatalier will cause the equilibrium to shift to the right to
make hydrogen ions. (Remember [H+1] = [H3O+1])

What is the pH after the base shock?

HCO3-1(aq) + H2O  H3O+1(aq) + CO3-2(aq) Ka = 4.7*10-11

I 0.2 -0.02 0.3
R -0.02 +0.02 +0.02
E 0.18 About 0 0.32

Ka = ([H3O+1] [CO3-2])/[HCO3-1]
4.7*10-11 = (x)(0.32)/0.18
x = 2.6*10-11

[H+1] = 2.6*10-11  pH = 10.58 (hardly changed)

What is the pH of a buffered solution compared to a non-buffered solution?

Calculate the pH of a 0.09 M acetic acid solution. (pH = 2.89)

Calculate the pH of a 0.09 M acetic acid solution when it is buffered with 0.11 M sodium acetate.
(pH = 4.82)

SHORT CUT = HENDERSON - HASSELBALCH EQUATION

This equation is used to determine/predict the pH of a buffer.

Recall that:
(take the -log of both sides)
OR
(take the -log of both sides)
Ka = ([H+1] [anion])/[acid]
pKa = -log [H+1] - log [anion]/[acid]
pH = pKa + log [anion]/[acid]
Kb = ([OH-1] [cation])/[base]
pKb = -log [OH-1] - log [cation]/[base]
pOH = pKb + log [cation]/[base]

TO DETERMINE WHICH FORMULA TO USE, COMPARE Ka TO Kb. WHICHEVER ONE

IS GREATER WILL DETERMINE IF THE SOLUTION WILL BE ACIDIC OR BASIC.

eg) for the previous problem:

pH = pKa + log [anion]/[acid]
= -log(1.8*10-5 ) + log (0.11/0.09)
 = 4.74 + log (1.2)
= 4.74 + 0.079
= 4.82
PREPARING A BUFFER

If you want a buffer of a specific pH, the pKa of the weak acid chosen must be within 1 unit of
the desired pH. (pH = pKa +/- 1)

eg) Can acetic acid and sodium acetate be used to make a buffer with pH = 5.00. If so, what
ratio of acetic acid to sodium acetate is required.

I) Ka (acetic acid) = 1.8*10-5  pKa = 4.74 (yes, it is within range)

II pH = pKa + log [anion]/[acid]

5.00 = 4.74 + log [anion]/[acid]
0.26 = log [anion]/[acid]
10.26 = [anion]/[acid]
1.8 = [anion]/[acid]

you can make a solution where the mole ratio is 1.8 mol sodium acetate

eg) Make a 1 L buffer solution (about 0.5 M) and with a pH of 3.85

pH = 3.85 [hydrogen ion] = 1.4*10-4

check pKa=s for the one closest to 3.85  benzoate Ka = 6.6*10-5 pKa = 4.18

pH = pKa + log [anion]/[acid]

3.85 = 4.18 + log 0.5/[acid]
-0.33 = log 0.5/[acid]
10-.33 = 0.5/[acid]
0.4677 = 0.5/[acid]
[acid] = 1.069 M

For 1 L , amount of sodium benzoate needed (conjugate base)

n = C*V m = n*M
= (0.5)(1) = (0.5)(132)
= 0.5 mol = 66 g

For 1 L, amount of benzoic acid needed

n = C*V m = n*M
= (1.069)(1) = (1.069)(122)
= 1.069 mol = 130.42 g
Try these:

What is the pH of a 0.2 M ammonium nitrite solution? (pH = 4.97)

Hint: NH4NO2  NH4+1 + NO2-1 (salt type question)

To make 250 mL buffer with pH = 9.0, how many grams of ammonium chloride would be added
to 250 mL of a 0.2 M NH3 solution?

Hint: the pH needed means the solution will be basic so use the appropriate formula!

NH3 + H2O  NH4+1(aq) + OH-1(aq) base

Kb of NH3 = 1.0*10-14/5.7*10-10 pOH = pKb + log [cation]/[base]

 pKb = 4.8 5 = 4.8 + log [cation]/0.2
0.2 = log [cation]/0.2
100.2 = [cation]/0.2
1.585 = [cation]/0.2
[cation] = 0.317 M
n = C*V m = n*M
n = (0.317)(0.25) m = (0.0792)(53.5)
n = 0.0792 mol m = 4.24 g

OR
NH4+1 + H2O  H3O+1 + NH3 acid (treated as an acidic buffer)

Ka of NH4+1 = 5.7*10-10 pH = pKa + log [anion]/[acid]

 pKa = 9.2 9 = 9.2 + log 0.2/[acid]
-0.2 = log 0.2/[acid]
10-0.2 = 0.2/[acid]
[acid] = 0.317 M = [NH4+1]

n = C*V m = n*M
n = (0.317)(0.25) m = (0.0792)(53.5)
n = 0.0792 mol m = 4.24 g