5.

3 COMPLEXATION AND OXIDATION/REDUCTION TITRATIONS

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

Sample Assays - Complexation

Type of volumetric analysis based on the type of chemical reaction Direct Indirect
involved Calcium carbonate Bismuth content of glycobiarsol
1. Neutralization
Zinc oxide; zinc chloride Ammonium alum
 Aqueous Neutralization
○ Acidimetry Calcium chloride Potassium alum
○ Alkalimetry Milk of magnesia Aluminum sulfate
 Non-Aqueous Neutralization
○ Non-aqueous Acidimetry Magnesium sulfate Aluminum chloride
○ Non-aqueous Alkalimetry Magnesium gluconate
2. Precipitation
 Gay-Lussac's MASKING
 Leibig
Process in which a substance without physical separation of it
 Mohr
or its products, is transformed that it doesn't enter into a
 Fajan's
particular reaction.
 Volhard's
✓ Adjusting pH
3. Complexation ✓ Precipitation
 Ca, Mg, Zn, Mn, Al, Bi ✓ Use of Masking Agent
3. RedOx Reaction – an agent which will remove interfering ions in the
 Permanganometry sample
 Iodine methods ○ Cyanide ion – copper, zinc, cadmium, iron,
○ Iodimetry silver
○ Iodometry ○ Iodide ion – mercury
○ Ammonium fluoride – calcium, aluminum and
COMPLEXATION magnesium
○ Triethanolamine - aluminum
 Reaction between a metal and an electron donating group
or ligand.
OXIDATION - REDUCTION METHODS
 A substance is titrated with a standard reagent to the
formation of a complex ion. Otherwise known as Reduction-oxidation/REDOX
OXIDATION REDUCTION
 These methods are applied to determine metals present in
Reaction where there is an increase in Reaction where there is a decrease
the sample oxidation number and loss of electrons in oxidation number and gain of
○ COMPLEX – product between a metal and a ligand electrons
which contains a single electron donating group (or a
complexing agent); the process is termed Combination of a substance with oxygen Combination of a substance with
hydrogen
complexation.
○ CHELATE – product between a metal and a ligand  VDGEROA – Valence Decrease, Gain Electron,
which contains 2 or more electron donating groups Reduction, Oxidizing Agent
(or a chelating agent); the process is termed  VILEORA – Valence Increase, Loss Electron, Oxidation,
chelation. Reducing Ag

 TITRANT: Na EDTA (EthyleneDiamineTetraAcetic Acid)  Oxidizing Agent – substance that undergoes reduction and
 STANDARD SOLUTION: Chelometric Calcium Carbonate causes the oxidation of the other reagent.
 ANALYTE: Divalent & Polyvalent Cations  Reducing Agent – substance that undergoes oxidation and
– Calcium causes the reduction of the other reagent.
– Magnesium, Zinc, Manganese For example:
– Aluminum, Bismuth Fe2+ + Ce4+ ↔ Fe3+ + Ce3+

Analyte Ca ” Mg, Zn, Mn Al, Bi General types of redox analyses

containing
Divalent and A. PERMANGANOMETRY
Polyvalent  Standard solution: potassium permanganate
Cations  Primary standard: oxalic acid/sodium oxalate
Type of Titration Direct Direct Residual
(indirect)
 Indicator: none/self-indicating (endpoint is faintly pink)
Titrant Na EDTA Na EDTA Na EDTA Zinc  Sample Assays:
Sulfate VS ○ Direct: Hydrogen Peroxide
pH 12-13 10 4-5 ○ Indirect: Cherry juice for malic acid, precipitated
Buffer Requirement NaOH NH3- NH4Cl CH3COOH-
NH4CH3COO
manganese dioxide, titanium dioxide
Indicator Hydrocynaphth Eriochrome Dithizone ○ Residual: Sodium nitrite, Lead monoxide
ol blue Black Xylenol Orange
(Bi) B. CERIMETRY
Endpoint Red to blue Wine red to Purple green to
Blue purple Rose  Standard solution: Ceric sulphate
 Primary standard: Arsenic trioxide or sodium
chromate

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[PHARCHEM3] 5.3 COMPLEXATION AND OXIDATION/REDUCTION TITRATION – Ms. Melissa Calambro
 Indicator: orthophenanthroline (color change: red to 5. RESIDUAL IODOMETRY INVOLVING PRECIPITATION
blue) OF A CHROMATE OR A DICHROMATE
 Sample assays: ○ Sample assay: lead monoxide
○ Direct:
– Ferrous sulfate (ferrous fumarate) 6. POTASSIUM IODATE ASSAY: Analysis of iodides and
– hydroquinone, homatropine hydrobromide, arsenites
– Menadione (Vitamin K3) ○ Indicator: chloroform
○ Sample assay: potassium iodide
C. IODIMETRY and IODOMETRY
 Iodimetry – assay where sample analyzed is a 7. SODIUM NITRITE ASSAY/ **DIAZOTIZATION
reducing agent ○ Used in the analysis of sulfa drugs and
 Iodometry - assay where sample analyzed is an other arylamino compounds
oxidizing agent ○ Indicator: starch iodide paste
 Standard solutions: ○ Sample assay: Sulfanilamide, benzocaine,
○ Iodine – primary standard is arsenic trioxide sulfa drug
(**specifically for iodimetry)
○ Sodium thiosulfate – primary standard is D. MISCELLANEOUS
potassium dichromate (**specifically for  Titration with Diclorphenol Indophenol VS
iodometry)  Titration with Sodium Tetraphenyl Boron VS
○ Potassium arsenite – primary standard is  Titration with Titanium Trichloride VS
arsenic trioxide  Titration with Potassium Iodate VS
 Indicator for iodimetry and iodometry:
○ 1% starch solution (IODIMETRY: appearance of
blue color ; IODOMETRY: disappearance of
blue color)
○ Chloroform and carbon tetrachloride

Specific Assay types:

1. DIRECT
○ Sample assay (with iodine): antimony potassium
tartrate (tartar emetic), ascorbic acid, dimercaprol
○ Sample assay (with sodium thiosulfate): povidone
iodine, iodine
○ Sample assay (with potassium arsenite): iodine
tincture, lugol’s solution

2. RESIDUAL TITRATION of excess iodine with sodium

thiosulfate
○ Sample assay: methenamine mandelate, calomel,
antipyrine

3. INDIRECT: Liberation of iodine from KI and titration

with sodium thiosulfate
○ Sample assay: selenium sulfide, thyroid, sodium
hypochlorite; cupric sulfate

4. BROMINE ASSAY
○ Residual iodometry involving precipitation of a Bromo
derivative
○ Used in the analysis of aniline, phenol compounds
○ Sample assays: phenol, resorcinol

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