pharmaceutical analysis
Properties and Standards in Pharmaceutical Analysis
Properties of Chemical Reactions in Titration
Specific to the substances being analyzed.
Must be quantitative and fast (instantaneous).
Requires a suitable indicator to show when the reaction is complete.
Referenced to a suitable standard.
Choosing an Indicator
Must show a visible response (color change) when the reaction reaches an endpoint.
Should change color at the equivalence point to minimize titration error.
Primary Standard Requirements
Very high purity.
Easily tested for impurities.
Heat stable.
Non-reactive with air, water, and CO2.
High molar mass to minimize weighing errors.
Soluble in the solvent used in titration (commonly water).
Uses of Primary Standards
Benzoic Acid: Acts as a standard acid; low solubility in water. Good redox standard.
Potassium Iodate: Standard for redox reactions.
Anhydrous Sodium Carbonate: Acts as a standard base, absorbs water and CO2 from the atmosphere.
Sodium Chloride: Standardizes silver nitrate solutions.
Zinc: Standardizes EDTA solutions.
Titration Reactions and Agents
Titration Reactions
Acid-base (neutralization), redox, complex formation, precipitation.
Choosing Acid-Base Indicators
Chosen to ensure color change occurs near the equivalence point.
Typically weak organic acids with color differences in ionized states.
Common Oxidizing Agent
KMnO4: Used in acidic medium. Color change from pink to deep purple.
Common Reducing Agent
Thiosulfate: Used in iodine reactions. Iodine's color indicates the endpoint; starch is added for sharper detection.
Common Standard Complexing Agent
EDTA: Forms 1:1 complexes with metal ions. Polydentate ligand, forms chelate complexes.
Medium Requirements: pH must be constant, often maintained using an alkaline buffer. Metal stability depends on pH; excess H+ can compete with metal ions for the ligand. Disodium edetate is commonly used due to higher solubility.
Properties of Indicators and Chloride Determination
Properties of Metal Indicators
Form 1:1 complexes that are weaker than EDTA. Should not compete with EDTA, and the indicator color must differ from the metal indicator complex.
Determining Halide Concentration
Silver Nitrate and Halide Ions: Method primarily used for chlorine determination. A reverse procedure can be applied, e.g., Ag+ + Cl- → AgCl.
Indirect Titration
When to Perform Indirect Titration
Preferred when many substances cannot be titrated directly due to:
No suitable reaction.
Reaction may be too slow.
Volatile analyte.
Back Titration Procedure
Known quantity of a standard titrator solution is added in excess.
Allow reaction with the sample.
Determine excess by titration with another standard solution.
The difference indicates the amount reacted by the sample.
Non-Aqueous Titration
When to Perform Non-Aqueous Titration
Conducted using solvents other than water.
Role of Water in Acid/Base Titrations
Necessary for certain reactions, but non-aqueous solutions can extend the range of acids and bases measurable.
Targets for Non-Aqueous Titration
Very weak acids (e.g., phenolic compounds).
Very weak bases (e.g., organic amines).
Compounds insoluble in water.