Chapter 14

Principle of neutralization titrations

 Goal of this chapter
• To learn the concept of neutralization titration.
• To learn acid/base standard solution used in
neutralization titration, and how to standardizing
acid/base standard solutions.
• To learn how to indicate titration end-point using an
indicator agent.
• To learn titration curves of strong acid/strong base
titration.
• To learn the titration curve of weak acid/strong base
titration.
• To learn the composition of solutions during
neutralization titration
• To learn stoichiometric calculation for neutralization
titration
 Neutralization titration
• Definition: a titrametric method based on the
neutralization reaction of an acid with a base for
analyzing the concentration of an analyte (acid
or base) in a sample.
• Classification: aqueous neutralization titration
and non-aqueous neutralization titration.

Only neutralization titration in aqueous solutions

will be discussed in this chapter.
 Standard solutions used in
neutralization titrations
• Solutions of strong acid and base are used as
standard solutions in neutralization titrations.
- standard solution of acid: HCl, HClO4, H2SO4
- Standard solution of base: NaOH, KOH
• Prepare standard solutions:
- Acidic standard solution: through diluting
concentrated acidic solution from commercial
sources.
- Basic solution: Dissolve solid NaOH or KOH in DI
water.
 Q Question

• Warning: be careful to performing the dilution and

dissolving operation. These dilution and dissolving
are usually exothermal reactions. The temperature
of local solution in limited space could reach boiling
point.
• Question 1: How to dilute commercial
concentrated (18 M) H2SO4
• Question 2: why weak acids or bases are not used
as standard solutions in neutralization titration
 How to standardize acidic and basic
standard titrant solutions
Standards: reagents of exactly Characteristics of Primary
known concentration.
Standards.
Primary standard - a substance
• Easy to obtain, purify, dry and
of sufficient purity such that a
standard solution can be prepared preserve in a pure state.
from it by directly weighing a
• Unaltered in air during weighing.
quantity of it, dissolving it and
then diluting to a defined volume • High relative molecular mass.
of solution. • Readily soluble in solvent of
(eg KHP and Na2CO3 used in expt choice.
3).
• React stoichiometrically and fast.
Secondary – a solution whose
concentration has been eg: Na2CO3 as a primary standard for HCl
determined by comparison
against a primary standard. (eg CO32- + 2H3O+  CO2 + 3H2O
HCl, NaOH in expt 3,)
 How to standardize acidic and
basic standard solutions
• Primary standard substances used to calibrate acidic
standard solutions
- Na2CO3 (99.98%)
CO32- + 2H3O+  H2O + CO2
Equivalence point, pH = 3.8
- tris-(hydroxymethyl)aminomethane, (HOCH2)3CNH2
(HOCH2)3CNH2 + H3O+  (HOCH2)3CNH3+ + H2O
Equivalence point, pH = ??
- Sodium tetraborate decahydrate (Na2B4O7.10H2O)
B4O72- + 2H3O+ + 3H2O  4H3BO3
Equivalence point, pH = 5.3
 How to standardize acidic and
basic standard solutions
• Primary standard substances used to calibrate basic standard
solutions
- KHC8H4O4 (potassium hydrogen phthalate)
HC8H4O4- + OH-  C8H4O42- + H2O
Equivalence point, pH = 10
- KH(IO3)2
H(IO3)2- + OH-  2IO3- + H2O
Equivalence point, pH around 7
- C6H5COOH (benzoic acid)
C6H5COOH + OH-  C6H5COO- + H2O
Equivalence point, pH = 8.5
Indicators for neutralization titrations
• Most of the indicators used in neutralization titrations are
weak organic acids or bases.
• The dissociation of these organic acids or bases forms
conjugate bases or acids, which show different colors from
their conjugate acids or base.
Example:
 Indicator’s application pH range
Considering a HIn as an indicator
[H3O+][In-]
HIn + H2O H3O+ + In- Ka =
[HIn]
[HIn]
[H3O+] = Ka
[In-]
• Suppose our eyes can detect the change of color originated
from the change of [HIn]/[In-] = 10 to [HIn]/[In-] = 0.1
- Exactly before the point of detectable change, [H3O+] = 10Ka,
pH = pKa - 1
- Exactly after the point of detectable change, [H3O+] = 0.1Ka,
pH = pKa + 1
- Detectable pH change range = pKa + 1
• This is the guideline to select appropriate pH indicators for
neutralization titrations.
Error sources in using pH indicator
in neutralization titration
1. The pKa of an indicator does not match very well the
equivalent point
2. The capability of human eyes to reproducibly
distinguish the intermediate color of the indicator.
- uncertainty in 0.5 to 1 pH unit
3. Other parameters, such as temperature, ionic strength,
existence of colloid particles, can affect the function of
pH indicator and introduce larger error.
 Common pH indicator used in
neutralization titrations
Indicator pH range Quantity per 10 ml Acid Base
Thymol Blue 1.2-2.8 1-2 drops 0.1% soln. red yellow
in aq.
Methyl yellow 2.9-4.0 1 drop 0.1% soln. in red yellow
90% alc.
Methyl orange 3.1-4.4 1 drop 0.1% aq. soln. red orange
Bromphenol blue 3.0-4.6 1 drop 0.1% aq. soln. yellow blue-violet
Bromcresol 4.0-5.6 1 drop 0.1% aq. soln. yellow blue
green
Methyl red 4.4-6.2 1 drop 0.1% aq. soln. red yellow
Bromcresol 5.2-6.8 1 drop 0.1% aq. soln. yellow purple
purple
Phenol red 6.4-8.0 1 drop 0.1% aq. soln. yellow red
Phenolphthalein 8.0-10.0 1-5 drops 0.1% soln. colorless red
in 70% alc.
Thymolphthalein 9.4-10.6 1 drop 0.1% soln. in colorless blue
90% alc.
Acid-Base Titration
 Q Question

• As a professional analytical chemist,

indicate problems in this neutralization
titration demonstration.
 Titration curves------Strong acid/Strong base
Titrate 50.0 mL of 0.100 M HCl with 0.100 M NaOH.
Titration Curve for Strong Acid with Strong Base
Vo – the initial volume in the flask; Vt – the volume of titrant added
13 Ma – molarity of the acid; Mb – molarity of the base.
12
b) pH11after adding Vt mL NaOH & prior to the equivalence point?
10
HCl +9 NaOH → H2O + Na+ + Cl- - note the neutral cations and anions.
8
Millimoles
7 base added = {Mb x Vt}
pH

6
∴ Millimoles
5 acid reacted = {Mb x Vt} (1:1 Stoichiometry)
4
Initial3millimoles of acid in flask = {Ma x Vo}
2
millimoles
1 acid remaining in flask = {Ma x Vo} – {Mb x Vt}
0
Volume of solution in flask = {Vo + Vt} mL.
0 10 20 30 40 50 60 70
∴ Concentration of acid in Volume
the flask = [H3O+]
Base pH =
= [ {Ma x Vo} – {Mb x Vt} ] / {Vo + Vt} mol/L -log[H3O+]
 Titration curves------Strong acid/Strong base

Concentration of acid in the flask:

[acid]flask = [ {Ma x Vo} – {Mb x Vt} ] / {Vo + Vt} mol/L

If Vt = 5 mL calculate the pH for Vt =

[acid]flask = [ {0.10 x 50} – {0.10 x 5} ] / {50 + 5} 1, 10, 20, 30, 40, 45, 49,
= 8.18 x 10-2 mol/L∴ pH = 1.09 49.5 & 49.9 mL.

Titration Curve for Strong Acid with Strong Base

Equivalence volume (Ve): 13

12
11
Vol. of NaOH (Vb) to neutralize Va of HCl 10
9
8
∴ Ma x Va / Mb = Vb {= Ve = 50 mL} 7
pH

6
5
∴the above expression for [acid]flask is 4
3
2
1
relevant up until just before 50 mL. 0
0 10 20 30 40 50 60 70
Volume Base
 Titration curves------Strong acid/Strong base
c) pH at equivalence volume?

Reaction that takes place as we add

base from the burette:
HCl + NaOH → H2O + Na+ + Cl-

After adding Ve all the HCl has reacted

(definition of Ve). Titration Curve for Strong Acid with Strong Base

13
+ -
Therefore only H2O, Na and Cl are 12
11
present in solution. 10
9
8
7

pH
6
5
4
3
2
1
0
0 10 20 30 40 50 60 70
Volume Base

Equilibrium at equivalence point is 2H2O ⇋ H3O+ + OH-

Kw = [H3O+][OH-] = 1 x 10-14: [H3O+]2 {=[OH-]2}: ∴ [H3O+] = 1 x 10-7 & pH = 7.
 Titration curves------Strong acid/Strong base

d) pH after equivalence volume?

pH will be due to the excess base
Volume excess base = Vt – Ve that has been added to the flask
[OH-] = (Vt-Ve) x Mb/(Vt + Vo)
pOH = -log[OH-] = 14 – pH
Titration Curve for Strong Acid with Strong Base
Neutralization titrations (acid-
base): to be able to select the 13
12
indicator we must know the pH 11
10
at the equivalence point and 9
the rate change in pH with 8
7
pH

titrant volume (ΔpH/ Δvol) that 6

5
occurs around Ve (49.99 – 4
3
50.01). 2
1

Δ pH/ Δvol= (10-4)/0.02 0

0 10 20 30 40 50 60 70
Volume Base
Titration curves------Strong acid/Strong base
Strong Acid - Strong Base

a) pH before equivalence point: pH = -log[H3O+]

13
+
[H3O ] = [ {Ma x Vo} – {Mb x Vt} ]/{Vo + Vt} mol/L. 12

b) pH at equivalence point = 7 11

c) pH after equivalence point 10

P
9
pH = pKw + log(MOH(V - Veq)/(2Veq + V))
8

C: [HCl] = [NaOH] = 0.0001 M. 7 BB

pH
B: [HCl] = [NaOH] = 0.001 M. 6

A: [HCl] = [NaOH] = 0.01 M. 5

4 MO
(ΔpH/ Δvol) large 3

around Phenolphthalein (P)

2
8.3 – 10 (c – r)
equivalence point Bromothymol Blue (BB) 1

For A: pH 4 – 10 6.2 – 7.6 (y – b)

0 Volum e Bas e m L
Methyl Orange (MO) 40 45 50 55 60

For B: pH 5 – 9 3.1 – 4.4 (r – y)

For C: pH 6 - 8
 Titration curves------Strong acid/Strong base
1. In order to construct a titration curve - 2. To select the appropriate indicator –
a) Need to know which acid and which a) pH change through the equiv. point?
base are involved – strong or weak?
b) pH range through which the indicator
b) Need to know their concentrations. changes color?

3. Issues of Concern: end point vs equivalence point !!!

a) Normally we don’t know the analyte concentration.
b) What is the error associated with indicator selection and color change
detection?
i) Analyte concentration and ∴ ΔpH/ Δvol.
ii) When has the color changed? ± x mL. Error in addition to the burette reading
error (± 0.?) {error in burette volume = √(0.032 + 0.032 + x2)}

If use the wrong indicator: equivalence point ≠ end point,

the determined [analyte] will be wrong
 Buffer Characteristics
- Contain relatively large amounts of weak acid and its
conjugate base.
- Added H+ reacts to completion with weak base, A-.
- Added OH− reacts to completion with weak acid, HA.
- pH is determined by ratio of concentrations of weak acid
and weak base.

[A- ]
pH = pK a + log
[HA]
 Weak acid-strong base titrations

pH [ HA] = [ A- ]
pH = pK a
• equiv. point
Buffer region :

pH = pK a + log
[A- ] mol HA initial = molOH − added
[HA]
pH ≠ 7

• ½Vequiv • Vequiv VNaOH

 Q Question
What is the pH value at equivalent point in case
of titrating a 0.200 M acetic acid with a 0.200
M NaOH. (acetic acid, Ka =1.75 x 10-5)
 Solution

At equivalent point, cOAc- = 0.100 M.

OAc- dissociation reaction:
OAc- + H2O HOAc + OH- Kb = 1.00 x 10-14/1.75 x 10-5
= 5.71 x 10-10
[OH-] = (Kb*cOAc-)1/2 = (5.71x10-10x0.100)1/2 =7.56x10-6

pOH = 5.12
pH = 14-5.12 = 8.87
HPr = Propionic Acid
 Key points on the pH curve
HA + OH- A- + H2O

• 1) ½ Vequil [ HA] = [ A - ]
pH = pK a
molOH − added = mol HA initial
[ A − ] = cHA / 2
A − + H 2O → HA + OH −
[OH − ] = KbcHA / 2

• 2) Vequil pOH =
1
( pKb − log cHA / 2)
2
1 1
pH = 14 − pOH = 14 − pKb + (log cHA / 2) ≠ 7
2 2

• After Vequil pH = pKw + log(MOH(V - Veq)/(2Veq + V))

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.
pKa value vs. titration curve

Phenolphthalein
transition range

Bromothymol blue
transition range

Bromocresol green
transition range
 Determine pKas of amino acid by
using neutralization titration methods
• An amino acid of exactly
known concentration (Ma)
and volume (Vo) is
prepared.
• The amino acid in the
solution exists as
zwitterion, pH = pI.
• Add ½ Vo HCl
(concentration equals Ma),
and measure solution pH,
which equals pKa1.
• Add ½ Vo NaOH
(concentration equals Ma)
and measure solution pH,
which equals pKa2.