NEUTRALIZATION ANALYSIS

TITRATION CURVES

(A)

analyte

(R)

titrant

(P)

product

Outline
NEUTRALIZATION
ANALYSIS

Introduction
Titrants
Titration curves
End point
detection
Applications

Important points and regions:

2 points:
before titration
at the end point
2 regions:
before the end point
after the end point
Titration curves:
1. Strong acid with
strong base,
2. Weak acid with
strong base,
3. Polyprotic acid with strong base

(at 0%)
(at 100 %)
(0.00..1 99.99%)
(100.00..1 )

I. [A]
III. [A] = [R]
II. [A] + [P]
IV. [P] + [R]

Strong base with strong acid

Weak base with strong acid
1

TITRATION CURVES
1. Strong acid with strong base,

Strong base with strong acid

Outline
NEUTRALIZATION
ANALYSIS

Introduction

e.g.
I.

Titrants
Titration curves

II.

End point
detection
Applications

III.

IV.

HCl + NaOH

Cl

acid1 +

base1
+
acid2
(very weak)

base2

Na+(H2O)

At the start:
[H+] = [H3O+]=[HCl]0
[OH] = [NaOH]0
pH = lg [HCl]0
pOH = lg [NaOH]0 pH = 14 pOH
Before the end point:
[H+] = [H3O+]=[HCl]unreacted
[OH] = [NaOH]unreacted
pH = lg [HCl]unreacted
pOH = lg [NaOH]unreacted
At the end point:
[H+] [OH]
KW = 1014
pH 7
After the end point:
[OH] = [NaOH]excess
[H+] = [H3O+]=[HCl]excess
2
pOH = lg [NaOH]excess
pH = lg [HCl]excess

TITRATION CURVES
Titration curves:
1. Strong acid with
2. Weak acid with
3. Polyprotic acid with

Outline
NEUTRALIZATION
ANALYSIS

strong base,
strong base,
strong base

Strong base with strong acid

Weak base with strong acid

EFFECTS ON THE TITRATION CURVE:

1. Effect of the temperature:
25C

[H+][OH] = Kw = 1014

Neutr. point: pH = 7

100C

12
[H+][OH] = Kw = 1012

Neutr. point: pH = 6

Introduction
Titrants
Titration curves

100

End point
detection
Applications

EFFECTS ON THE TITRATION CURVE

2. Dependence on the initial concentrations (e.g. [HCl]):
[HCl]0

0%

50%

90%

99%

99.9%

100%

100.1%

101%

110%

1N

0,3

11

12

13

0,1 N

1,3

10

11

12

0,01 N

2,3

10

11

0,001 N

3,3

10

Outline

pH change around the end point

pH

NEUTRALIZATION
ANALYSIS

3 11
4 10
5 9
6 8

Introduction
Titrants
Titration curves
End point
detection
Applications
0

100

EFFECTS ON THE TITRATION CURVE

3. Dependence on the acid strength (dissociation constants):

Outline
NEUTRALIZATION
ANALYSIS

Introduction
Titrants
Titration curves
End point
detection
Applications

A. Weak acid with strong bases ,

0
100
e.g. 101 N CH3COOH is titrated with NaOH (Ka = 2x105)
%

50

90

99

99.9

100

100.1

101

110

pH

2.9

4.7

5.7

6.7

7.7

8.9

10

11

12

pH pKInd 9 PHENOLPHTALEIN
B. Weak base with strong acid
e.g. 101 N NH4OH is titrated with HCl
(Kb = 2x105)
%

50

90

99

99.9

100

100.1

101

110

pH

11.1

9.3

8.3

7.3

6.3

5.1

pH pKInd 5 METHYL RED5

TITRATION CURVES

II. Weak acid with strong base

Weak base with strong acid
e.g. Titration of CH3COOH with NaOH , Titration of NH4OH with HCl:
I. At the start:
Weak acid
Weak base
pH

K a C acid H

Outline
NEUTRALIZATION
ANALYSIS

Introduction
Titrants
Titration curves
End point
detection
Applications

K a CH 3 COOH

OH

K b C base

OH

K b NH 4 OH

II. Before the end point:

Buffer (acid / salt)
Buffer (base / salt)
pH

H K

C acid
C salt

OH K

CH COOH
H KCH
COO

C base
C salt

OH K NH OH

NH
4

III. At the end point:

Hydrolysing salt (Brnsted base) pH
Hydrolysing salt (Brnsted acid)
OH

OH

Kw
C salt
Ka

K b C salt OH

K b CH 3 COO

Kw
C salt
Kb

IV. After the end point:

Excess of strong base
pH
[OH] = Cexcess base

[OH] = [NaOH]excess

K a C salt

K a NH 4

Excess of strong acid

[H+] = Cexcess acid

[H+] = [HClexcess

TITRATION CURVES
III. Polyprotic acid with strong base
e.g. Titration of H3PO4 with NaOH
1.
2.
3.

H3PO4 + OH
H2PO4 + OH
HPO42 + OH

H2PO4 + H2O
Ka1 = 7x103
HPO42 + H2OKa2 = 6x108
PO43 + H2O Ka3 = 1012

Outline
NEUTRALIZATION
ANALYSIS

Introduction
Titrants
Titration curves
End point
detection
Applications

ACID / BASE INDICATORS

1.

Azo-compounds

Genearal structure:

Outline
NEUTRALIZATION
ANALYSIS

Mechanism:

Introduction
Titrants
Titration curves
End p. detection
- chemical
- instrumental
Applications

Yellow
Yellow
Red
(basic) (intermediate) (acidic)
(aromatic) (protonated) (quinoid)

ACID / BASE INDICATORS

2.

PHTHALEIN-derivatives

General structure:

Outline
NEUTRALIZATION
ANALYSIS

Mechanism:

Thymol blue

Introduction
Titrants
Titration curves
End p. detection
- chemical
- instrumental
Applications

Colorless
(acidic)

Colorless
(intermediate)

Purple
(basic)

INSTRUMENTAL DETECTION
(Summary)

Outline
INSTRUMENTAL
DETECTION

Advantages
Types
Potentiometric
end point
detection
Conductometric
end point
detection

The titration process is followed by electrochemical,

photometric or other sensing devices.

Method

Sensing device

Type of titration

POTENTIOMETRY
(Potential vs %)

Different types of
electrodes

AMPEROMETRY
(Current vs %)

Pt electrode
(dead stop)

CONDUCTOMETRY

Conductivity cell

Neutralization titr.
Precipitation titr.

PHOTOMETRY

Spectrophotometer

Complexometric
titr.

ENTALPHYMETRY

Thermistor

Neutralization titr.
Complexometric titr.
Precipitation titr.
Redox titr.
10

(Conductivity vs %)

(A = c l vs %)
(Q = f (c, H) vs %

Neutralization titr.
Complexometric titr.
Precipitation titr.
Redox titr.
Redox titr.

POTENTIOMETRY
Electrode potential developed
between:

Outline

Indicator electrode
Potential (Eind) varies
Depends on
the analyte concentration

INSTRUMENTAL
DETECTION

Solid metal / its unsoluble salt / saturated conc. of anion

e.g. Ag / AgCl / KCl
Hg / Hg2Cl2 / KCl
Hg / Hg2SO4 / K2SO4

Advantages
Types
Potentiometric
end point
detection
Conductometric
end point
detection

Reference electrode
Known, constant potential (Eref)
Independent
of the analyte concentration
Common reference electrodes:

Nernst equation: E E
Glass electrode
Metal
electrode
Ion-selective
electrode
Nobel metal
electrode

0.059
lg c
n

Neutralization titration:

E = E0 + 0.059 lg [H+]

Complexometric titration:

E = E0 + 0.059 lg [Mn+]
n

Precipitation titration:

E = E0 + 0.059 lg [X]

Redox titration:

E = E0 + 0.059lg [ox]
[red]
n
11

POTENTIOMETRY
Neutralization analysis
Indicator electrode:
Indicator electrode:

Outline

External
reference electrode

Glass electrode

GLASS ELECTRODE

INSTRUMENTAL
DETECTION

H+ conc. to be determined

Electrochemical cell for measurement of pH:

Advantages
Types
Potentiometric
end point
detection
Conductometric
end point
detection

External reference || H+ conc. |pH-sensitive

electrode
|| to be
| glass(Hg/Hg2Cl2/KCl) ||determined | membrane

| Internal
| buffer sol.

| Internal reference
| electrode

| (KCl) (pH = 7) | (Ag/AgCl/KCl)

External Dry glass Internal

hydrated
hydrated
gel layer
gel layer

12

POTENTIOMETRY
Glass electrode
Composition of glass:
E.g. 22 % Na2O, 6 % CaO, 72 % SiO2.

Outline
INSTRUMENTAL
DETECTION

Advantages
Types

Na+ mobile

membrane

solution
+

Na++
H
Na+

Ion-exchange reaction:
between
H++
Na
+
H in the solution and
Na+ in the glass:
glass
K
H+ + Na+Gl
Na+ + H+Gl
K = LARGE!
solution glass
solution glass
Combination glass electrode:

Potentiometric
end point
detection
Conductometric
end point
detection

13

POTENTIOMETRY
Titration curve
Outline
INSTRUMENTAL
DETECTION

Advantages

Potentiometric titration curve:

Titration curve

Measuring the potential of a suitable

indicator electrode (pH) as a function
of volume titrant.

Determination of the end point:

from the derivatives

1st derivative

Types
Potentiometric
end point
detection

2nd derivative

Conductometric
end point
detection

14

CONDUCTOMETRIC
TITRATION CURVES
Outline

I. Titration of strong acid (a) with strong base e.g. HCl with NaOH
(b) with weak base e.g. HCl with NH4OH

INSTRUMENTAL
DETECTION

Advantages
Types

II. Titration of weak acid (c) with strong base e.g. CH3COOH with NaOH
(d) with weak base e.g. CH3COOH with NH4OH

Potentiometric
end point
detection
Conductometric
end point
detection
%

15

APPLICATIONS
TITRATIONS
Direct

Outline
NEUTRALIZATION
ANALYSIS

Introduction

Back (indirect):
Analyte
Titrant in excess
to calculate

I.

to measure

Determination of strong acids / bases:

Equivalence point: pH = 7
e.g. NaOH

Titrants
Titration curves
End point
detection

Vphen.
Vmeth.r.

OH H2O

Applications

16

APPLICATIONS
II. Determination of weak acids :
Equivalence point: pH > 7 (phenolphtalein indicator)
weak bases :
Equivalence point: pH < 7 (methyl red indicator)

Outline
NEUTRALIZATION
ANALYSIS

Introduction
Titrants
Titration curves
End point
detection
Applications

II. (a) Determination of weak acids : Ka 105. (107 - 104)

Direct: e.g. carboxylic acids of low carbon atoms
e.g. CH3COOH
fatty acids (e.g. fat, wax, oil)
Back : if the weak acid is volatile
e.g. CO2 (as carbonate or hydrogencarbonate)
bubble-free
distillation
CO2
known amount of Ba(OH)2
Distillation apparatus

(Maros- Schulek)
back titration of excess Ba(OH)2
with standard HCl
Application of CO2 determination:

Determination of organic materials

Determination of CO2, HCO3 , CO32

content of natural waters
Nonaqueous solvents: Ka < 107
17
> 1012

APPLICATIONS
II. (b) Determination of weak bases : Kb 105 (107 - 104)
Direct:

e.g. NH4OH

Back:

NH4+ -salt

Outline
NEUTRALIZATION
ANALYSIS

Introduction
Titrants
Titration curves
End point
detection
Applications

strong base (NaOH)

boiling

NH3

distillation into known excess of acid

Kjeldahl method:

NH
back titration of excess acid (HCl)
known HCl
with basic titrant (NaOH)
Application of NH3 determination:
3

N-containing organic compounds (e.g. amino acids, proteins,)

Decomposition (mineralization) with cc. H2SO4, 300 C
+ catalyst: Se, or Cu2+
Ox. number: 3
(NH4)2SO4
(e.g.. NH2, N(CH3)2, =NH, N<)
Ox. number: + 3, +1
HNO3 (+5)
(e.g.,azo- (-N=N-), nitro-, nitrozo comp.)
Reduction

with Zn, Na2S2O4,..

NH4+
Nonaqueous solvents:

Kb < 107
> 1012

18

APPLICATIONS

Outline
NEUTRALIZATION
ANALYSIS

Introduction
Titrants

III. Determination of salts:

(a) Neutral salts: NOT MEASURABLE!
(b) Salt hydrolyzing to acid: Brnsted acid (strong acid + weak base)
MA +
H2O MOH + A + H+
if pK > 7!
can be TITRATED
with base
E.g. Aniline HCl; Benzidine H2SO4; Papaverine HCl
(c) Salt hydrolyzing to base: Brnsted base (strong base + weak acid)
MA +
H 2O
HA + M+ + OH
if pK > 7
can be TITRATED
with acid
E.g. Na2B4O7 (B4O72 +7 H2O 4H3BO3 + 2OH) methyl red
E.g. Na2CO3
NaHCO3

Titration curves

(CO32 + H2O HCO3 + OH) phenolpht.

(CO32 +2 H2O H2CO3 +2 OH) methyl red
(HCO3 + H2O H2O + CO2 +OH) methyl red

Na2CO3

End point
detection

NaHCO3

Applications

Vphen
Vmeth.r.

CO32 HCO3 H2CO3

Vphen = 0
Vmeth.r.

HCO3 H2CO3

19

(d)

APPLICATIONS

Specific determinations:
NaOH Na2CO3
in the presence of each other

NaHCO3 Na2CO3
in the presence of each other

Outline
NEUTRALIZATION
ANALYSIS

Introduction
Titrants
Titration curves
End point
detection
Applications

Vphen
Vmeth.r.

OH, CO32 HCO3 H2CO3

Vphen
Vmeth.r.

CO32 HCO3 HCO3 H2CO3

Warders method :
one sample :
Warders method :
A. OH + H+ H2O
phenolpht.
two samples :
CO32 + H+ HCO3.
B. HCO3 + H+ H2CO3 methyl red A. CO32 + H+ HCO3
two samples :
phenolpht.

+
B. OH
+ H H2O
B. HCO.3 + H+ H2CO3
methyl
red
2
+
CO3 +2H H2CO3
CO32 +2H+ H2CO3
Winklers method :
methyl red
A. + BaCl2
CO32 +Ba2+ BaCO3
20
OH + H+ H O
phenolpht.