5.

2 NEUTRALIZATION AND PRECIPITATION TITRIMETRY

Ms. Melissa Calambro || October 2022 PHARCHEM3
Transcribers: Navarro
Editors: Montepio

 Analytes are too weak to be titrated with water

Type of volumetric analysis based on the type of chemical reaction  The limit of Moisture should be less than 0.05%
involved
1. Neutralization
 Aqueous Neutralization Sample procedure:
○ Acidimetry Transfer to a conical flask about 400 mg of Methacholine
○ Alkalimetry Chloride, previously dried and accurately weighed, dissolve it in
 Non-Aqueous Neutralization 50 mL of glacial acetic acid, add 10 mL of mercuric acetate TS
○ Non-aqueous Acidimetry and 1 drop of crystal violet TS, and titrate with 0.1N perchloric
○ Non-aqueous Alkalimetry acid to a blue green endpoint
2. Precipitation
 Gay-Lussac's NON-AQUEOUS ACIDIMETRY
 Leibig ANALYTE TIRANT / “VS” 1° INDICATOR
Standar
 Mohr d
 Fajan's  Amines, amines  Perchloric Potassium  Crystal
 Volhard's Salt Acid VS in Biphthalat violet
 Heterocyclic Glacial e  a-naphthol
3. Complexation Acetic Acid
Nitrogen benzoin
 Ca, Mg, Zn, Mn, Al, Bi Compounds (or  Quinaldine
3. RedOx Reaction  Alkali salts of Dioxane) red
organic and  Hydrogen  Malachite
 Permanganometry bromide
inorganic acids green
 Iodine methods  Amio acids
○ Iodimetry Example: Assay of
○ Iodometry Diazepam, Assay of
Metacholine Chloride
NON-AQUEOUS ACIDIMETRY
Neutralization NON-AQUEOUS NON- NON- NON-
It is a reaction between an acid and base to form water and a ACIDIMETRY AQUEOUS AQUEO AQUEOUS
salt. ACIDIMETRY US ACIDIMETRY
ACIDIM
 Acidimetry ETRY
○ It is the measurement of a base of a given sample by  Acid halide; acid Sodium or Lithium Benzoic  Azo violet
titration with a standard solution of an acid. anhydride Methoxide in Acid  Thymol
○ Analyte: Basic  Amino acids; Methanol Blue
○ Carboxylic acid  Thymolpht
Titrant: Acidic ; sulfuric acid or hydrochloric acid VS
 Barbiturates; halein
○ Primary Standard: sodium carbonate Xanthine
○ Sample assays:  Penol;
○ Direct : Sodium bicarbonate, sodium hydroxide Sulfunamide
Example: Assay of
○ Residual: Beef extract, Methenamine, Zinc
Phenyton
oxide, Rochelle salt, Milk of Magnesia (MOM)

 Alkalimetry Non-aqueous solvent

○ It is the measurement of an acid of a given sample by
titration with a standard solution of a base.
○ Analyte: Acidic
○ Titrant: Basic ; sodium hydroxide VS
○ Primary standard: potassium biphthalate
○ Sample assays:
○ Direct: hydrochloric acid, diluted phosphoric
acid, boric acid
○ Residual: Aspirin capsules
INDICATORS used in Acidimetry and Alkalimetry
SA + SB (T) → Neutral Salt － Use phenolphthalein
SA (T) + SB → Neutral Salt － Use Methyl Red
SA(T) + WB → Acidic Salt － Use Methyl Red
WA + SB (T) → Basic Salt － Use phenolphthalein
NOTE:
if the TITRANT is ACID － Use Methyl Red
if the TITRANT is BASIC － Use phenolphthalein
Nonaqueous Neutralization
 Performed when the analyte is water insoluble.
 Reactants and products react with water
Ex. Acetic anhydride
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1. PROTOGENIC SOLVENT – proton-giving e.g. formic acid,
glacial acetic acid
2. PROTOPHILIC SOLVENT – proton-receiving e.g. ether,
acetic anhydride
3. APROTIC SOLVENT – neither gives or receives e.g.
chloroform, hydrocarbon, benzene
Precipitation
 Also known as saturation method or precipitimetry
 Reactions that involve the formation of an insoluble
substance.
 A substance is titrated by precipitating it with a standard
solution of a precipitating agent.
○ It may be direct or indirect; that is the precipitating
agent may be added to a direct endpoint; or an
excess may be added and the excess determined by
titration
Sample procedure:
Assay of sodium Lauryl Sulfate for sodium chloride content
Dissolve about 5g of sodium lauryl sulfate, accurately weighed
in about 50 mL of water. Neutralize the solution with dilute nitric
acid (1 in 20), using litmus paper as the indicator.
[PHARCHEM3] 5.2 NEUTRALIZATION AND PRECIPITATION TITRIMETRY – Ms. Melissa Calambro
Add 2 mL of potassium chromate TS, and titrate with 0.1 N
silver nitrate. Each milliliter of 0.1 N silver nitrate is equivalent to
5.844 mg of NaCl.

mL x N x mEq
% P or %NaCl =
g
x 100
P= percentage of the precipitate that will be formed

Where:
mL is the volume of Titrant
N is the normality of Titrant
mEq of the Analyte or substance being identified
g is the weight in grams of the Analyte

Types of Precipitimetry
 Fajan (Direct Titration)
○ Involves the change of color on the surface of the
precipitate
○ Standard solution: Silver nitrate
○ Indicators: eosin, tetrabromophenolphthalein ethyl
ester (TEE) dichlorofluorescein (DCF)
○ Sample assay:
– Phenylephrine HCl
– Tubocurarine HCl
– Meperidine HCl

 Volhard (Residual Titration)

○ Involves the formation of a soluble red colored
complex
○ Standard solution: potassium thiocyanate
○ Indicator: Ferric ammonium sulfate (FAS)
○ Sample assay:
– Aminophylline for theophylline
– Sodium chloride
– Dextrose and Sodium chloride injection

 Mohr (Direct Titration)

○ Formation of a second precipitate which is of a
different color from the primary precipitate – It forms
a red precipitate of silver chromate which is seen
against the background of white silver chloride
○ Standard solution: silver nitrate
○ Indicator: potassium chromate
○ Sample assay:
Sodium Lauryl Sulfate for sodium chloride
content

 Liebig (Direct Titration)

○ Formation of a blue colored complex
○ Standard solution: sodium tetraphenyl boron
○ Indicator: Bromophenol blue
○ Sample assay:
– Assay of organic nitrogen compounds

 Gay-Lussac (Direct Titration)

○ Otherwise known as Equal turbidity method
○ Cessation of precipitate or turbidity
○ This makes use of a technique where the liquid was
drawn off from the reaction mixture and it is placed in
a spot plate. A drop of titrant is added. If turbidity of
precipitate is formed, the process is continued.
○ Standard solution: silver nitrate \No indicator is
used.
○ Sample assay: assay of sodium chloride

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