Chem 221

Acid- Base Reactions II

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 Objectives
 Construct titration curves of weak bases
with strong acids.
 Compare between different titration
curves.
 Select an Indicator for a certain
titration.
 Apply double indicators.

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 Example
 Hydrogen cyanide gas (HCN), is very weak acid (Ka=
6.2x10-10) when dissolved in water. If a 50.0 ml
sample of 0.10 M HCN is titrated with 0.10 M NaOH,
calculate the pH of the solution at the equivalence
point of the titration.

At the equivalence point

 The equivalence point will occur when a total
of 5 mmol OH- has been added. Since the NaOH
solution is 0.1M, the equivalence point will occur
when 50 ml NaOH are added.

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 Example (cont.)
 CN-(aq) + H2O(l) HCN(aq) + OH-(aq)

 Then, pOH = -log (5.0x10-2 x 1.6x10-5)1/2 = 3.04

 and pH = 10.96

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 Notice the following:
 Comparing the titrations of acetic acid
and that of HCN , we found the
following:
 1. The same amount of 0.1 M NaOH is
required to reach the equivalence
point in both cases. (the fact that HCN is
a much weaker acid that HC2H3O2 has no
effect on the amount of base required)

 2. The pH value at the equivalence

point is affected by the acid strength .
The weaker the acid, the greater the pH
value at the equivalence point.
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 In General,
 The amount of the acid and not its
strength that determines the
equivalence point.

 The weaker the acid, the greater

the pH value at the equivalence
point.

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 Titrations of weak bases with strong
acids
 Titrations of weak bases with strong acids
Can be treated using the same
procedures as before.
 Always, you should think first about the
major species in solution and decide whether
a reaction occurs that runs to completion.
 Run stoichiometry and equilibrium
calculations a to get the pH.

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 Titrations of weak bases with strong acids

 Before adding any acid:

 Before End point, basic buffer

calculations:

 At the End point: its an acidic salt

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Titration curve of weak base with a
strong acid

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Slide prepared By Dr/Ahmed Moustafa 10
 TITRATION CURVE OF WEAK BASE
WITH A STRONG ACID
• Example : Titration of acetic acid (Ka = 1.75 x 10-5)
against ammonium hydroxide (Kb = 1.8 x 10-5)
This titration cannot be performed in a direct way. Why?
• The titration lack a sharp break at the end point
i.e no suitable indicator can be used.
• At the end point the pH will be:
• pH = ½ pKw + ½ pKa – ½ pKb
• = 7.0 + 2.37 -2.37 = 7.0
( Ka, Kb were almost equal, so the salt formed as the end
point is neutral) 11
 Effect of Concentration of reagents
on the titration curve
Strong Acid - Strong Base Titration

14

12

10

1
8
0.1
pH

0.01
6 0.001

0
0 10 20 30 40 50 60

The jump in the pH value occurring at the

Volume of Base Added

equivalence point decreases with decrease of

reagent and analyte concentrations as shown in the
above figure.
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 Acid –Base indicators
 There are two common methods
for determining the equivalence
point of an acid- base titration:
 1. Use a pH meter to monitor pH
and then plot the titration curve.
 2. Use an acid- base indicator
which marks the end point of a
titration by changing color.
 Although the equivalence point of
titration is defined by the
stoichiometry, is not necessarily the
same as the end point, careful
selection of the indicator will
ensure that the error is
negligible.
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 Acid –Base indicators ( cont.)
 The most common acid-base
indicators are complex molecules
that are themselves weak acids or
bases represented.
 They exhibit one color when
the proton is attached to the
molecule and a different color
when the proton is absent.
 For example:phenolphthalein,
a commonly used indicator, is
colorless in its HIn form and pink
in its In-, or basic form.

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Ph.Ph. in acidic medium Ph.Ph. in Basic medium

Methyl orange in basic Methyl orange in acidic

medium medium 15
 Notice that
 For most indicators, about one tenth of
the initial form of the indicator should be
converted to the other form before a new
colour is apparent so that the human eye
can detect this colour change.

 We will assume, then, that in the titration of

an acid with a base, the colour change will
occur at a pH where [In− ] 1
=
[HIn] 10
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 Applying Handerson Equation,

Therefore,
For a typical acid-base indicator with dissociation
constant Ka, the colour transition occurs over a range
of pH values given by:
pka ± 1. 17
 Choice of Indicator for a certain
titration
 When we choose an indicator for a titration, we
want the indicator endpoint (where the
colour changes) and the titration equivalence
point to be as close as possible.
 Choosing an indicator is easier when there is a large
change in pH near the equivalence point as in case of
strong acid-strong base titration, where the pH changes
from 5.3 to 8.7 so any indicator working in the range from
5-9 can be used.

 While in case of weak acid-strong base titration, e.g.

(HC2H3O2 against NaOH) the pH at the end point was 8.7.
The choice is not that easy as we should use an indictor
close to this value for example Phenolphethalin.
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19
 pKa

half way point

As clear from the curves, of titration of a strong

acid (to the left) and the titration of the weak acid (to
the right) against NaOH, that :
both phenolphthalein and methyl red can be used to
determine the end point fort the strong acid titration.
While for the weak acid only phenolphtalein can be used.
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 Neutralization of a weak Diprotic
acid with a strong base
Neutralization of a weak diprotic (dibasic acid) H2A with
a strong base can take place on two steps:
H2A + OH-  H2O + HA-
HA- + OH-  H2O + A-

i.e. each mole of the dibasic acid requires 2 moles of

OH- for complete the reaction.

After adding 1 mole of the base, the acid is said to

be titrated as monobasic acid.
After adding 2 moles of the bases, it is said to be
titrated as dibasic acid.
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 Neutralization of a weak Diprotic
acid with a strong base (Cont.)
The titration of the acid as monobasic or dibasic
depends on:
1. The pH value at the end point of the first step
which can be calculated as:
pH=1/2 (pK1+pK2)
 In General , if K1/K2> 104 i.e 10,000
The polyprotic acid can be titrated as monobasic
acid

2. If the pH lies within the pH interval of a

certain indicator ( it can be titrated as monobasic
acid) , Otherwise, it will only be titrated as a dibasic
acid. 22
 Neutralization of a weak Diprotic
acid with a strong base (Cont.)
Consider the titration of 0.1 N malonic acid
(Ka1=1.5x10-3 and Ka2=8.0x10-7 using NaOH

K1/ K2 = 1.1x104 , i.e this acid can be titrated as

monobasic
To calculate the pH at the end point:
pK1=2.8 and pK2=6.1
pH=1/2(pK1+pK2)
pH=1/2(2.8+6.1)=4.45

Therefore, methyl orange indicator of pH range (3-5)

or methyl red(4-6) can be used for detection of the
endpoint of the titrtion. 23
 Neutralization of a weak Diprotic acid with
a strong base (Cont.)

Figure supplied by
Prof. Faten Nour El-Dien
10/24/2016 24
 Neutralization of a weak Diprotic
acid with a strong base (Cont.)
Consider the titration of 0.1N Oxalic acid
K1=6.5x10-2 and K2=6.1x10-5 using 0.1 N NaOH
K1/K2 = 1037 i.e less than 104
Thus , oxalic acid cant be titrated as monoprotic
acid,

Also,
pK1=1.19 and pK2=4.22
pH=1/2(pK1+pK2)
pH=1/2(1.19+4.22)=2.7
There is no indicator lies this pH in its pH range, so,
Oxalic acid can not be titrated as monobasic acid.
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 Neutralization of a weak Diprotic
acid with a strong base (Cont.)
Accordingly, Oxalic acid can only be titrated as
diprotic acid.
At Equivalence point, after addition of 20 mlx 0.1M
(2mmol) NaOH will react with 10 ml x 0.1 M (1.0 mmol)
oxalic to produce 2 mmol of salt. i.e. total volume
=10+20=30 mL
[salt] = no of moles/ Vtotal= 2 mmol/ 30 = 0.66 mol/L
Kb = Kw/ Ka2 of oxalic acid = 1.0x10-14/ 6.1x10-5=
1.64x10-10
pOH = -log 0.66 x 1.64x10 −10 = 4.98
pH = 14 – 4.98 =9.01
Accordingly, Phenolphethalien (8-10) can be used to
detect E.P. 26
 Neutralization of a weak Diprotic acid with
a strong base (Cont.)

Figure supplied by
10/24/2016
Prof. Faten Nour 27
El-Dien
 Tribasic acid: Phosphoric acid
pKa1= 2.12
pKa2= 7.21
pKa3= 12.3

Here, K1/K2 = 1.2x105, and stepwise titration is

possible. The pH at the first equivalence point is
[1/2(pK1+pK2)=4.77) and indicators such as methyl
orange or bromocresol green are the most
appropriate.

 For the second stage of dissociation, K2/K3 = 1.2x105

, so that separate titration of the 2nd hydrogen is
possible. However, the 2nd end point is less sharp
than the first one since the solution is well buffered
by the HPO42- present. 28
 Tribasic acid: Phosphoric acid (cont.)
•The pH at the 2nd
equivalence is approximately
[1/2(pK2+pK3) = 9.7].
•The only suitable indicator is
thymolphthalein (pKin = 9.2) .
While for phenolphthalein, there
will be some error.
•The 3rd hydrogen, being very
weakly dissociated (pK3 =
12.3) so that its ionization is very
near that of water, no indicator
can serve to show this point. 29
 Titration of easily hydrolizable salts
(displacement titrations)
 Example: sodium carbonate
 Na2CO3 + HCl NaHCO3 +NaCl
NaHCO3 + HCl H2CO3 + NaCl
Na2CO3 + 2 HCl H2CO3 + 2 NaCl

 The pH at the 1st equivalence point is

calculated to be 8.3 i.e. within the range of
phenolphthalein indicator.

 This solution can further be titrated to the

2nd equivalence point where NaCl and
carbonic acid are produced and the pH
drops to 3.5, which is in the range of
Methyl orange indicator.
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 Titration of a mixture of Na2CO3+ NaOH
against HCl

 On Using Phenolphethaein,
 The volume of the acid is equivalent to all
OH- and half CO32-.

 On using methyl orange,

 The volume of the acid is equivalent to all
OH- and CO32-.
 By subtracting the 2 volumes we get half
CO32-.
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 Mixture of Sodium carbonate and
sodium hydroxide

10/24/2016 Dr/Ahmed Moustafa 32

 Titration of a mixture of Na2CO3+ NaHCO3
against HCl

 On Using Phenolphethaein,
 The volume of the acid is equivalent to half
CO32- only.

 On using methyl orange,

 The volume of the acid is equivalent to all
CO32- and HCO3-.
 By multiplying the volume we get from the
first titration by 2 we get the CO32- and then
we can get HCO3- by subtraction.
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Mixture of Sodium carbonate and
sodium bicarbonate

Prepared By Dr/Ahmed Moustafa 34

 References

 D. A. Skoog, D.A. W est, F.J. Holler,

S.R . Crouch , Analytical Chemistry,
an introduction, 7th Edition, ISBN
0-03-020293-0.
 Lectures of Prof. Dr. Faten Nour El Din.
 https://www.youtube.com/watch?v=3B5Sb
bvdUgk

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