MEDICAL COLLEGES OF NORTHERN PHILIPPINES

Alimannao Hills, Peñablanca, Cagayan

Telefax No.: (078) 304-1010
Website: www.mcnp.edu.phE-Mail Address: adminoffice@mcnp.edu.ph

COLLEGE OF PHARMACY

FINAL COVERAGE: TITRIMETRIC TECHNIQUES, GRAVIMETRIC ANALYSIS AND SPECIAL METHODS

o Titration of ____ with a standard _____

Overview:
I. Types of Titrations based on the Chemical Reaction Aqueous Non-Aqueous
Involved
VS Naoh Na Methoxide
A. Neutralization Methods
KOH Li Methoxide
• Based on the media used
• Based on Titrant Primary Standard K Biphthalate Benzoic Acid In
B. Reduction – Oxidation Dimethylformamide
• Permanganometry
Direct Hcl Phenytoin
• Iodine Methods: Iodimetry andIodometry
H3PO4
• Diazotization Assay Boric Acid
C. Reactions involving Combination of Ions Tartaric Acid
• Complexation
D. Volumetric Precipitation Residual ASA (HPLC)
• Volhard Method Indicators Methyl Orange Azo-Violet
• Mohr Methyl Red Thymol Blue
• Fajans Phenolphthalein O-Nitroaniline
• Gay – Lussac
II. Gravimetric Method B. Reduction – Oxidation
III. Special Method ➢ Methods of analysis involving a ________ in __________ of
A. Ash Content Determination the reacting substances.
➢ Reduction (LEORA)
B. Water Content Determination
C. Assay of Fatty substances, waxes, balsams and resins
D. Assay of Volatile oils ➢ Oxidation (GEROA)
E. Assay of Nitrogen

I. • OF TITRATIONS BASED ON THE CHEMICAL REACTION

TYPES a. Permanganometry
INVOLVED: Volumetric solution KMnO4

A. Neutralization Reaction Primary standard Na oxalate

➢ Chemical reactions or chemical processed in which an
________ reacts with a _______ Direct titration H2O2
➢ Product:
Indirect Titration Malic acid in Cherry juice
a. Based on the Media Used
1. Aqueous Titration Residual titration Na and K nitrite

Indicator Permanganate solution

2. Non-aqueous Titration
b. Iodimetry
o Analysis of REDUCING AGENTS with standard
b. Based on Titrant
solution of iodine
1. Acidimetry
o EP:
o Titration of ____ with standard _____
o Indicator:
AQUEOUS NON-AQUEOUS
Volumetric Solution Iodine Solution
VOLUMETRIC Hcl, H2SO4 Perchloric Acid In
Primary Standard Arsenic trioxide
STANDARD Glacial Acetic Acid
Direct titration Antimony potassium tartrate
PRIMARY Anhydrous Sodium
Ascorbic acid
STANDARD Carbonate
Sodium ascorbate
SECONDARY Naoh, KOH Sodium thiosulfate
STANDARD
Indirect titration Calomel, antipyrine, NaHSO,
Direct Titration Naoh, Naco3, NAHCO3, Metacholine NaSO
Na Salicylate
c. Iodometry
Residual Zno Phenytoin
o Indirect analysis of OXIDIZING AGENTS
Titration Nak Tartrate
o EP:
Milk Of Magnesia
o Indicator:
Indicators Methyl Orange Crystal Violet Volumetric Solution Iodine Solution
Methyl Red Malachite Green Sodium Thiosulfate
Phenolphthalein Methyl Rosaniline
Chloride Primary Standard IS: Arsenic trioxide
ST: Potassium dichromate
2. Alkalimetry

RICA CARMELA STA. INES, RPH 1

 MEDICAL COLLEGES OF NORTHERN PHILIPPINES
Alimannao Hills, Peñablanca, Cagayan
Telefax No.: (078) 304-1010
Website: www.mcnp.edu.phE-Mail Address: adminoffice@mcnp.edu.ph

COLLEGE OF PHARMACY
Direct titration CuSO4, NaOCl Primary Std Silver Nitrate

Residual Titration Phenol, resorcinol, PbO Manifestation Colored Precipitate

Assay Aminophylline Sodium

d. Diazotization Assay with Nitrile Chloride
o Assay of the ___________ and other compounds
containing _________ group.
o VS: b. Mohr Method
o Reference Std: o Conducted in the presence of _________
o EP o Type of titration:
e. Cerimetry o Used for:

Volumetric solution Cerric sulfate

Volumetric Solution Silver Nitrate
Primary standard Arsenic trioxide
Indicator Potassium chromate
Direct titration Menadione, Ferrous sulfate
Primary Std Sodium chloride
Indicator Orthophenanthroline
Manifestation Formation of secondary
precipitate
C. Reactions involving Combination of Ions
a. Complexation Assay Sodium Lauryl Sulfate
o Ligand:
c. Fajans Method
o Monodentate Ligand
Volumetric Solution Silver Nitrate solution

o Multidentate Ligand Indicator Adsorption indicator

Primary Std Sodium chloride

o Masking – Metal detection in the presence of Manifestation Change in the color of
another metal precipitate
▪ Protects other components form
reacting with EDTA Assay Phenylephrine
2.3 dimercapto-1-propanol Bi, Cd, Cu, Hg, Pb Tubocurarine
Meperidine
o Fajans Indicator
Triethanolamine Al, Fe, Mn ▪ AKA:
▪ D
o Demasking Agent – Releases the metal ion form ▪ E
the masking agent ▪ T
o Auxiliary complexing agent – used to permit
metals to be titrated in alkaline solution for EDTA. d. Gay – lussac Method
Volumetric Solution Disodium EDTA Volumetric Solution Silver Nitrate

Primary standard Ca carbonate Indicator None

Direct titration Ca carbonate Primary Std Sodium chloride

Ca gluconate
ZnO Manifestation Cessation of precipitate

Residual titration Alum Example NaCl

Aluminum hydroxide
o Metal Ion INDICATORS (CHEMP) II. GRAVIMETRIC METHODS
C ➢ Analysis by __________
H ➢ Process of __________ and _______ the compound of
E known composition
M ➢ Equation:
𝒈𝒓𝒆𝒔𝒊𝒅𝒖𝒆 𝒙 𝑴𝑾𝒔𝒂𝒎𝒑𝒍𝒆
P %𝑷 = 𝒙 𝟏𝟎𝟎
𝒈𝒔𝒂𝒎𝒑𝒍𝒆 𝒙 𝑴𝑾𝒓𝒆𝒔𝒊𝒅𝒖𝒆
D. Volumetric Precipitation o Problem 1: If a 0.46 g sample of KI yielded 0.7215
a. Volhard Method g of AgI precipitate by gravimetric assay. What
o ___________ titration method would be the percentage purity of KI?
o Complete precipitation of insoluble silver salts ▪ MW of AgI : 234. 7745
from nitric acid solution by the addition of excess ▪ MW of KI: 166.0045
standard silver nitrate solution to a soluble salt.
o ____________ titration with standard
__________________________.
Volumetric Solution Ammonium thiocyanate

Indicator Ferric ammonium sulfate

RICA CARMELA STA. INES, RPH 2

 MEDICAL COLLEGES OF NORTHERN PHILIPPINES
Alimannao Hills, Peñablanca, Cagayan
Telefax No.: (078) 304-1010
Website: www.mcnp.edu.phE-Mail Address: adminoffice@mcnp.edu.ph

COLLEGE OF PHARMACY
III. SPECIAL METHOD
A. Ash Content Determination c. Method III
o Gravimetric
Importance Methods
o For vegetable drugs

Inorganic salts (naturally- Total Ash C. Assay of fatty substances, waxes, balsams and resins
occurring or as Acid-Insoluble ash a. Acid value
adulterants) Sulfated ash o Acid number or acidity index
o No. of mg of KOH necessary to _______ the
___________ in 1 g of substance.
o Equation:
➢ Total Ash 𝑵 𝒙 𝑽 𝒙 𝟓𝟔. 𝟏𝟏
𝑨𝒄𝒊𝒅 𝒗𝒂𝒍𝒖𝒆 =
𝒘𝒕 𝒊𝒏 𝒈
➢ Acid Insoluble Ash
b. Ester value
o Part of the total ash which is insoluble in diluted
o Ester number
HCl
o No of mg of KOH required to ______ the _______
o Represents the ________ content of the sample
contained in 1 g of oil, fat, wax, resin or balsam.
o Equation:
c. Saponification Value
𝒂𝒄𝒊𝒅 𝒊𝒏𝒔𝒐𝒍𝒖𝒃𝒍𝒆 𝒂𝒔𝒉
%𝑨𝑰𝑨 = 𝒙 𝟏𝟎𝟎 o Saponification number or _____________ number
𝒘𝒕 𝒐𝒇 𝒕𝒉𝒆 𝒕𝒐𝒕𝒂𝒍 𝒂𝒔𝒉
o No of mg of KOH necessary to ________ the
➢ Sulfurated ash
________ and _____ the _______ in 1 g of
o Ash treated with _________
substance
➢ Approximate Temperature Equivalent
o Equation:
𝑺𝑽 = 𝑨𝑽 + 𝑬𝑽
d. Iodine Value
Very dull red heat 500C- 550C
o Iodine number
Dull red heat 550C-700C o Number of mg of ______ absorbed by 100 g of oil,
fat, wax or other substance
Bright red heat 800C-1000C o Measure degree of __________
o Method I :
Yellow Heat 1000C-1200C o Method II:
o Method III:
White Heat 1200C-1600C
o Equation:
[(𝑵𝒙𝑽)𝒃𝒍𝒂𝒏𝒌 − (𝑵𝒙𝑽)𝒂𝒄𝒕𝒖𝒂𝒍 ] 𝒙 𝟎. 𝟏𝟐𝟔𝟗
B. Water Content Determination 𝑰𝑽 = 𝒙 𝟏𝟎𝟎
𝒘𝒕 𝒊𝒏 𝒈
a. Method I
o Titrimetric or _____________
o Reagent is freshly prepared Type IV Examples
▪ Pyridine, methanol, SO2, iodine Drying oils >120 Linseed oil
o Primary standard: Fish oil
o Equation: Cod liver oil
𝑽𝑲𝑭𝑹 𝒊𝒏 𝒎𝑳 𝒙 𝑬𝑭
%𝑯𝟐 𝑶 = 𝒙 𝟏𝟎𝟎
𝒘𝒕 𝒐𝒇 𝒔𝒙 𝒊𝒏 𝒎𝒈 Non-Drying oils <100 Olive oil
o Sample problem: Calculate the water content of Almond oil
streptomycin powder using 3.50 g sample. The
water equivalence factor is 4.6 and the volume Semi-drying oils 100-120 Cottonseed oil
consumed was 9.2 mL. the water content was: Sesame seed oil

D. Assay of Volatile Oils

a. Acetylization Flask
o Assay of __________ volatile oils: (LiBoG Me)
▪ Li
o Karl fischer reagents: ▪ Bo
▪ Anhydrous methanol ▪ G
▪ Me
b. Cassia Flask – bisulfite method
▪ Iodine o Assay of _______ volatile oils
▪ Cinnamaldehyde, citral
o Assay of _______ volatile oils
▪ Sulfuric Acid ▪ Camphor, carvone
c. Cassia flask – KOH method
o Assay of ________ volatile oil
▪ Pyridine ▪ Anethol, eugenol, thymol
o Equation:
𝑽𝒔𝒂𝒎𝒑𝒍𝒆 − 𝑽𝒓𝒆𝒔𝒊𝒅𝒖𝒂𝒍
b. Method II %𝑷𝒉𝒆𝒏𝒐𝒍 = 𝒙 𝟏𝟎𝟎
𝑽𝒔𝒂𝒎𝒑𝒍𝒆
o ________ Distillation or _________ method
o Sample Problem: In phenol content determination of
o Toluene Moisture apparatus
volatile oil, the insoluble layer in the graduated neck
o For samples containing 2-4 ml moisture
of the Cassia flask reached 3.1 mL which is contained
o Also used in ________ content determination
from a sample of 10 mL after treatment with KOH.
o Equation:
What is the percentage phenol sample?
𝒎𝑳 𝒓𝒆𝒂𝒅𝒊𝒏𝒈
%𝒘𝒂𝒕𝒆𝒓 = 𝒙 𝟏𝟎𝟎
𝒘𝒕 𝒐𝒇 𝒔𝒂𝒎𝒑𝒍𝒆

RICA CARMELA STA. INES, RPH 3

 MEDICAL COLLEGES OF NORTHERN PHILIPPINES
Alimannao Hills, Peñablanca, Cagayan
Telefax No.: (078) 304-1010
Website: www.mcnp.edu.phE-Mail Address: adminoffice@mcnp.edu.ph

COLLEGE OF PHARMACY
E. Assay of Nitrogen
➢ _____________ method
➢ Used in determining nitrogen content of substances.

•conversion of organic nitrogen into ______ by adding

______
Digestion

•Conversion of ______ into ______

Distillation

•Titrating with ________

Titration

RICA CARMELA STA. INES, RPH 4