ACIDS AND BASES
Titration of weak acid/weak base with strong titrant
The neutralization reaction is
HOAc + Na+ + OH- = H2O +Na+ + OAc-
NH4OH + H+ + Cl- = NH4+ + Cl- +H2O
Before titration
[H+] = √ KA. CHA
Calculate the pH value
If the sample is weak base, then use
KB = [NH4+] [OH-]/NH4OH
[OH-] = √ KB. CB
pH = 14 – pOH
Before equivalence point
As soon as the titration is started a buffer system is set up.
As the titration proceeds, the pH slowly increases as the ratio of salt/acid changes
Equilibrium expression used is the Henderson –Hasselbach equation
At midway pH = pKa
At Equivalence point
All sample is converted to its conjugate form.
If the sample is an acid, then
[OH-] = √KW.CA-/KA
pH = 14- pOH
If the sample is a base, then
[H+] = √KW.CBH+/KB
pH= -log[H+]
Titration curve
Weak acid-strong base titration curve
Weak Base –strong acid titration curve
The four Major Differences Between a Strong Acid-Strong Base Titration
Curve and a Weak Acid-Strong Base Titration Curve
1. The initial pH is higher.
2. A gradually rising portion of the curve, called the buffer region, appears before the steep rise
to the equivalence point.
3. The pH at the equivalence point is greater than 7.00.
4. The steep rise interval is less pronounced
Dependence of Titration curve
Depends on acid concentration
Inflection point or maximum slope
decreases with lower acid
concentration
Equivalence point becomes
more difficult to identify
Eventually cannot titrate acid
at very low concentrations
Low concentration small slope change in titration curve
High concentration Large slope change in titration curve
Depends on pKa or acid strength
Inflection point or maximum slope
decreases with weaker acid
Equivalence point becomes more
difficult to identify
weak acid small slope change in
titration curve
Difficult to detect equivalence point
Strong acid large slope change in
titration curve
Easy to detect equivalence point
Conclusion
Suppose a weak acid (Ka =10-9) is titrated against NaOH, degree of dissociation will be less as it is
weak, hence concentration of H+ ion which is equal to αc is low.
The pH value initially is higher and so the pH jump at equivalence is smaller.
We get a poor titration curve.
Smaller the Ka value, lower the pH jump at equivalence point.
Higher the Ka value, greater the pH jump at equivalence point.
Problem
Calculate the pH at 0, 10.0, 50.0 and 60.0 mL titrant in the titration of 50.0 mL of 0.100M acetic acid
with 0.100 M NaOH.
At 0 mL, we have a solution of only 0.100M HOAc:
( x)(x )
=1.75 ×10−5
0.100−x
[H+] = x = 1.32 x 10-3 M
pH = 2.88
At 10.0 mL, we started with 0.100 M X 50.0 ml =5.00 mmol HOAc; part has reacted with OH- and
has been converted to OAC-
mmol HOAc at start = 5.00 mmol HOAc
mmol OH- added = 0.100 M X 10.0 mL = 1.00 mmol OAc- formed
mmol HOAc left = 4.00 mmol HOAc in 60.0 mL
we have a buffer, since volumes cancel, use millimoles:
pH = pKa + log ¿ ¿
1.00
pH = 4.76 + log 4.00 = 4.16
At 25.0 mL, one – half the HOAc has been converted to OAc-, so pH = pKa:
mmol HOAc at start = 5.00 mmol HOAc
mmol OH- added = 0.100 M X 25.0 mL = 2.50 mmol OAc- formed
mmol HOAc left = 4.00 mmol HOAc in 60.0 mL
2.50
pH = 4.76 + log 2.50 = 4.76
At 50.0 mL, all the HOAc has been converted to OAc- (5.00 mmol in 100 mL, or 0.0500 M):
¿
√
−14
1.0 ×10
¿ −5
×0.0500=5.35 ×10−6 M
1.75 ×10
pOH = 5.27
pH = 8.73
At 60.0 mL, we have a solution of NaOAc and excess added NaOH. The hydrolysis of the acetate is
negligible in the presence of added OH-. So, the pH is determined by the concentration of excess
OH-:
mmol OH- = 0.100 M x 10.0 mL = 1.00 mmol in 110 mL
[OH-] = 0.0090 M
pOH = -2.04; pH = 11.96
Titration of weak acid with weak base
Acetic acid (CH3COOH) which is a weak acid and ammonium hydroxide (NH4OH) which is a weak
base.
The reaction can be shown as:
CH3COOH + NH4OH —-> CH3COO NH4+ H2O
Before Titration
[H+] = √Ka.C
pH= -log[H+]
Before Equivalence point
pH= pKa + log [salt]/[acid]
At Equivalence
pH= ½ pKw + ½ pKa – ½ pKb
Titration of weak acid with weak base
After equivalence point
pH= pKw – pKb - log [salt]/[base]
No single indicator is suitable, a mixed indicator of phenol red and methylene blue may be used.
Titration curve
Problem
100ml.of 0.1MCH3COOH (Ka= 1.78×10-5) is titrated against 0.1M NaOH and 10ml was required for
titration. Which of the following indicators will you use?
Methyl orange pH range 3.1-4.4
Methyl red pH range 6.8-8.4
Phenolphthalein pH range 8.3-10.0
Solution
Total volume =100+10 =110
Conc of CH3COONa = 0.1×100/110=0.09M
For hydrolysis of salt of weak acid and strong base the relation used is
pH= ½ pKw + ½ pKa + ½ log c
pH= 7 + 4.74/2 + ½ log 0.09
= 9.37 -0.5229
= 8.8491
Factors determining the exact form of a pH curve
The exact form of pH curve depends on
1. Whether acid or base is strong or weak electrolyte
2. The molarities of the solution used in the titration
The above factors may give rise to the following curves.
1. pH curve obtained by titration of strong acid with a strong base.
2. pH curve obtained by titration of strong acid with a weak base.
3. pH curve obtained by titration of weak base with a strong acid.
4. pH curve obtained by titration of a weak base with weak acid.
If either acid /alkali is weak, the parallel part of the curve become shorter as compared to strong
acid-strong base curve. On the other hand, if both the acid and base are weak, the range is usually
non – discernible.
Factors determining the exact form of a pH curve
For acid-base titration, the primary reaction involved is the neutralization reaction. At the point of
equivalence, the pH of the solution will be =,> or < 7 depending on the hydrolysis of the salt formed
i.e.
(i) Titration of strong acid with a strong base pH=7
(ii) Titration of strong acid with a weak base pH < 7
(iii) Titration of weak acid with a strong base pH > 7
