NEUTRALIZATION

TITRIMETRIC/VOLUMETRIC METHODS
- Neutralization
- Precipitation
- Complexation
- Oxidation-Reduction (REDOX)
OUTLINE:
• 4 chemical reactions
• Indicators
• Acidimetric
• Alkalimetric
• Direct and residual titration
• Aqueous and non-aqueous titration
Chemical Reactions in Titrimetry:
4 Types:
1. Neutralization (acidimetry and
alkalimetry)
2. Precipitation
3. Complexation
4. Oxidation-reduction
a. permanganate
b. ceric sulfate
c. iodimetry and iodometry
d. bromine
e. potassium iodate
f. diazotization assay w/ nitrite
4 Requirements Must be Met if the
Reaction is to be Used:
1. The reaction must proceed to completion.
2. The reaction must proceed in a
stoichiometric manner.
3. A suitable endpoint detecting device
(indicators).
4. For direct titrimetric method, the reaction
must be rapid so a sharp endpoint is
discernible.
NEUTRALIZATION METHOD
• Neutralization reactions are chemical
processes in which an acid reacts with a
base. The products are water and salt.
Indicators
• Are complex organic compounds used
to:
1. Determine endpoint
2. Determine the pH
3. To indicate that a desired change in pH
has been effected
Indicators
 Maybe weakly acids or weakly basic, capable
of existing in 2 forms of different color that
are mutually convertible.
 The usual concentration of indicator solution
is 0.05%.
 From 0.1 to 0.2 mL of the indicator solution
is used for 10 mL of liquid examined.
 Solutions. of indicators of basic type and of
the phthaleins are prepared by dissolving in
alcohol.
 In preparing solutions of acid group, this
must be neutralized with NaOH.
 Unless otherwise stated each acid-base
indicator solution is so adjusted that when
0.15 mL of the indicator solution is added
to 25 mL CO2 free water, 0.25 mL of 0.02N
acid or alkali, will develop the characteristic
color changes.
 Most of the indicators for acid - base
titration are acidic.
Commonly used pH Indicators
Color Change

Indicator pH Range Acid Base

Malachite green 0.0 – 2.0 yellow green

Methyl Yellow 2.9 – 4.0 red yellow

Bromophenol blue 3.0 - 4.6 yellow blue

Methyl Orange 3.2 – 4.4 pink yellow

Bromocresol green 4.0 -5.4 yellow blue

• Methyl red 4.2 – 6.2 red yellow

• Bromocresol purple 5.2 – 6.8 yellow purple

• Bromothymol blue 6.0 – 7.6 yellow blue

• Phenol red 6.8 – 8.2 yellow red

• Cresol red 7.2 – 8.8 yellow red

• Thymol blue 8.0 – 9.2 yellow blue

• Phenolphthalein 8.0 – 10.0 colorless red

• Thymolphthalein 9.3 – 10.5 colorless blue

 Phenolphthalein
Approximate pH range for color change: 8.0-
9.8
Color of acid form: clear
Color of base form: red-violet
 Methyl Red:
Approximate pH range for color change: 4.4-
6.2
Color of acid form: red
Color of base form: yellow
Rules for the Use of Indicators:
1. Use 3 drops of indicator TS unless otherwise
directed.
2. Strong Acid (SA) + Strong Base (SB) = use
methyl orange, methyl red or phenolphthalein
3. SA + WB = methyl red
4. Weak Acid (WA) + SB = phenolphthalein
5. WA + WB = no indicator
SA: HCl, HNO3, H2SO4, HI

SB: NaOH, KOH

WA: Acetic acid, Oxalic acid

WB: NH3
Indicator Papers:
 Lead acetate test paper
 Litmus paper
 Mercuric bromide test paper
 Phenolphthalein paper
 Potassium iodate-starch paper
 Starch iodate paper
 Starch iodide paper
 Turmeric paper
ACIDIMETRIC ANALYSIS
Acidimetry
• Direct or residual titrimetric analysis of
BASES using an acid as titrant
• Analyte = base
Titrant = acid
• Types
Direct titration = std. acid soln. from a buret
into a soln. of base being assayed
Residual Titration = 1st vol. soln. (acid) is added
in excess and the excess acid is titrated with std.
base
Examples:
 Organic substances : urea, sodium salicylate,
diphenhydramine, emetine hydrochloride,
meprobamate, paramethadione, pyrazinamide
 Inorganic substances : sodium bicarbonate,
milk of magnesia, ammonium chloride,
calcium hydroxide, lithium carbonate, zinc
oxide etc.
Computation:
DIRECT TITRATION

% Purity = N x V x meq. wt. x 100

wt. of sample
Ex.Assay of NaHCO3
1. What is the purity of NaHCO3 if 0.29 g
sample is titrated w/ 0.9289 N H2SO4. It
consumed 3.6 mL to reach the endpoint.
(MW of NaHCO3 = 84 g/mole)
RESIDUAL TITRATION:

% Purity = N1V1 - N 2V2 X meq. wt. X 100

wt. of sample
Ex.Assay of ZnO, Mg(OH)2
1. Calculate the Mg(OH)2 content of milk of
magnesia, 12.32 g of w/c was dissolved in 50
mL of 1.0340 N H2SO4, producing a mixture
that required 24.6 mL of 1.1255 N NaOH?
(at.Wt. Mg = 24.31; O=16; H=1)
ALKALIMETRIC ANALYSIS
ALKALIMETRY
• the direct or residual titrimetric analysis of
ACIDS
Direct: - sample is acid
- titrant is base
Residual : - sample is acid
- treated with excess standard base
- titrated with acid
 NONAQUEOUS TITRIMETRIC
ANALYSIS
• For substances that are poorly soluble and
weakly reactive in water
• Make use of organic solvents
• Moisture is be avoided in using non aqueous
procedures; limit of moisture is 0.05%
Acidimetry in Non-aqueous:

Solvents: acetonitrile, alcohol, dioxane, benzene,

chloroform

Titrant used:
1.perchloric acid in glacial acetic acid or
dioxane
2. hydrogen bromide
Ex: assay of methacholine chloride
Indicators:
crystal violet
quinaldine red
naphtholbenzein
malachite green
methyl red
methyl orange
thymol blue
Alkalimetry in Non-aqueous:

Titrants: Na methoxide
Lithium methoxide

Ex. Assay of phenytoin (organic acid)

Indicators:
azo violet
thymol blue
nitroaniline
thymolphthalein
hydroxyazobenzene