Pharmaceutical Analysis 2: Instrumental Methods of Analysis

(Review of Analysis 1 and Introduction)

Classifications of Analysis Base on the Reactions Involved

I. Neutralization
A. Acidimetry –measurement of base by a standard acid
Aqueous
Direct Titration: Assay of Sodium bicarbonate (VS: HCl/H2SO4; Primary Standard/Analyte: Na2CO3)
Residual Titration: Assay of ZnO; Assay of Milk of magnesia
Non-aqueous
Direct Titration: Standardization of 0.1N HClO4 (VS: HClO4; Primary Standard/Analyte: Potassium biphthalate)
B. Alkalimetry –measurement of an acid via a standard base
Aqueous
Direct Titration: Assay of Hydrochloric Acid (VS: NaOH; Primary Standard/ Analyte: HCl)
Residual Titration: Assay of Aspirin Capsules
Non-aqueous
Direct Titration: Standardization of 0.1N Sodium Methoxide (VS: Na methoxide; Primary Standard/ Analyte: Benzoic Acid)

II. Reduction-Oxidation Reaction

A. Permanganometry
-involves oxidation process (K permanganate serves as a reducing agent in the process)
VS: KMnO4 Primary standard/ Analyte: Sodium oxalate Indicator: None (VS is self-indicating) Endpoint: Slightly pink
Examples: Direct- Assay of H2O2 Solution, Assay of Cherry Juice for Malic Acid
Residual –Assay of Sodium Nitrate; Standardization of 0.1N Oxalic Acid
B. Iodimetry
-assay for iodine; involves oxidation process (Iodine serves as an oxidizing agent (also the VS) in the process undergoing reduction)
VS: Iodine Solution Primary standard/Analyte: Arsenic trioxide Indicators: Starch T.S.; ChCl3&/ CCl4 Endpoint: Starch-colorless to blue; ChCl3&/ CCl4-colorless to
Purple
Examples: Direct- Assay of Vitamin C; Standardization of 0.1N Iodine Solution;
Residual- Assay of Methionine; Assay of Na bisulfide
C. Iodometry
-assay of oxidizing agent (sample) and iodine serves (VS) as reducing agent (undergoing oxidation process)
VS: Sodium thiosulfate Primary Standard/Analyte: Potassium chromate Indicators: Starch T.S.; ChCl3&/ CCl4 Endpoint: Starch- blue to colorless; ChCl3&/ CCl4-purple to
Colorless
Examples: Direct- Assay of Cupric sulfate; Assay of Sodium hypochlorite Solution
Residual –Assay of Phenol; Assay of Thyroid Hormones
D. Cerimetry
-involves the use of cerium salts
VS: Ceric sulfate Primary standard/Analyte: Arsenic trioxide (new)/ Iron fillings (old) Indicator: Orthophenanthroline Endpoint: blue violet
Examples: Assay of Ferric sulfate tablets

III. Complexation/Compleximetry
-aka “Chelometry”
VS:EDTA(ethylenediaminetetraacetic acid Primary standard/Analyte: CaCO3 Indicator: eriochrome black T- Mg analysis; hydroxynaphthol blue-Ca analysis; Dithiazone-Al analysis
Examples: Direct- Assay of CaCO3
Residual- Bismuth content of glycobiarsol
Special Technique
“Masking” –determination of a metal in the presence of another metal
1. Triethanolamine- Fe3+, Al3+, Mn2+
2. Thioglycols-Ag2+, Cu2+, Bi3+, Pb2+
3. CN-1- Zn2+, Co2+, Ni2+, Cu2+
4. Ammonium F-Mg2+,Al3+, Ca2+

IV. Precipitimetry
-aka Volumetric Precipitation
-most common: Argentometric Titrations
-determination of halides
A. Volhard Method
VS: Ammonium thiocyanate Primary standard/ analyte: Silver nitrate Indicator: Ferric alumn Endpoint: blood red precipitate
B. Mohr Method
VS: Silver nitrate Primary standard/ analyte: NaCl Solution Indicator: K chromate T.S. Endpoint: brick red precipitate
C. Fayan’s Method
VS: Silver nitrate Primary standard/ analyte: NaCl Solution Indicator: Dichlorofluorescein Endpoint: green  pink