Oxidation-reduction titrations involve changing the valence state of reactants through electron transfer, where the reactant losing electrons is the reducing agent and the one gaining electrons is the oxidizing agent. Standard solutions of oxidizing agents like potassium permanganate and ceric sulfate and reducing agents like ferrous ammonium sulfate are used in these titrations, and the equivalence point relates electrical charge to molecular weight to quantify the reactants. Common methods include permanganometry, cerimetry, iodimetry, and iodometry.
Oxidation-reduction titrations involve changing the valence state of reactants through electron transfer, where the reactant losing electrons is the reducing agent and the one gaining electrons is the oxidizing agent. Standard solutions of oxidizing agents like potassium permanganate and ceric sulfate and reducing agents like ferrous ammonium sulfate are used in these titrations, and the equivalence point relates electrical charge to molecular weight to quantify the reactants. Common methods include permanganometry, cerimetry, iodimetry, and iodometry.
Oxidation-reduction titrations involve changing the valence state of reactants through electron transfer, where the reactant losing electrons is the reducing agent and the one gaining electrons is the oxidizing agent. Standard solutions of oxidizing agents like potassium permanganate and ceric sulfate and reducing agents like ferrous ammonium sulfate are used in these titrations, and the equivalence point relates electrical charge to molecular weight to quantify the reactants. Common methods include permanganometry, cerimetry, iodimetry, and iodometry.
Oxidation-reduction titrations involve changing the valence state of reactants through electron transfer, where the reactant losing electrons is the reducing agent and the one gaining electrons is the oxidizing agent. Standard solutions of oxidizing agents like potassium permanganate and ceric sulfate and reducing agents like ferrous ammonium sulfate are used in these titrations, and the equivalence point relates electrical charge to molecular weight to quantify the reactants. Common methods include permanganometry, cerimetry, iodimetry, and iodometry.
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Oxidation-Reduction
Titrations • The chemical reactions that occur in neutralization and precipitation methods of analysis take place without a change in valence. • Oxidation-reduction methods of analysis involve a change in valence of the reacting substances, Theory • The simplest type of oxidation-reduction is the direct combination of elements. • When oxygen unites with hydrogen gas forming water • O2 + H2 -> H2O • When carbon burns in the presence of oxygen to form carbon dioxide, C + O2 -> CO2, it is oxidized and then the oxygen is reduced. • When carbon unites with sulfur to form carbon disulfide C + 2 S -> CS2, the carbon is oxidized and the sulfur is reduced. • Reduction need not imply a reaction of hydrogen, since oxygen is reduced by carbon, and that oxidation need not imply a reaction of oxygen, since carbon is oxidized by sulfur. • When one substance is oxidized, some other substance must be correspondingly reduced and vice versa. • The oxidation-reduction reactions that take place in the official assay procedures are for the most part, between electrolytes in aqueous solutions. • Their quantitative value is based upon the fact that metals, non- metals, and their ions, under suitable conditions can be made to undergo a change in the quantity of electric charge associated with them and in that change, there exists a relationship between the quantity of electricity lost or gained and the weight of the reacting substances. • YOU RELATE ELECTRICAL CHARGE WITH MOLECULAR WEIGHT • The reactant which LOSES ELECTRONS in an oxidation-reaction is the REDUCING agent and can be identified in the equation for the reaction as the reactant containing a constituent atom or atoms converted to a higher state of oxidation. Fe+2 -> Fe+3 + e 2I- -> I2 + 2e
• Take note when you lose electrons you gain a MORE POSITIVE CHARGE. • The electrons lost by the reducing agent are gained by the OXIDIZING AGENT. the reactant containing a constituent atom or atoms which are converted to a lower state of oxidation. • Ce+4 + e -> Ce+3 • Fe+3 + e -> Fe+2 Mnemonic • LEORA • LOSE ELECTRON / GAINS A POSTIVE CHARGE • OXIDATION HALF REACTION • REDUCING AGENT
• GEROA • GAIN ELECTRON / GAINS A NEGATIVE CHARGE • REDUCTION HALF REACTION • OXIDIZING AGENT • A combination of oxidizing and reducing agents results in a reaction which may be used as basis for the quantitative measurement of one of the reactants • Example: Assay of ferrous sulfate by reacting it with ceric sulfate • Fe+2 + Ce+4 -> Fe+3 + Ce+3 • The two half reactions may be expressed as: Fe+2 -> Fe+3 + e Ce+4 + e -> Ce+3 • The amount of reducing agent or oxidizing agent in the sample can be determined by measuring a chemically equivalent amount of the oxidizing agent or reducing agent, respectively. Equivalent weight of RA • The equivalent weight of a reducing agent is that weight which loses electrons equivalent to 96,500 C and it can be calculated by dividing the gram-molecular weight by the number of electrons lost by each molecule. • The equivalent weight of ferrous sulfate when oxidized to ferric sulfate (Fe+2 -> Fe+3 + e) is 151.91 or 1 gram-molecular weight. • In short • Equivalent weight of reducing agent = MW/# of electrons lost. Equivalent weight of OA • An equivalent weight of an oxidizing agent is that weight which gains electrons to 1 faraday, or to the electrons gained by 1 gram-ion of hydrogen ions 2H+ + 2e -> H2. • It can be calculated by dividing the gram-molecular weight by the number of electrons gained by each molecule. The gram equivalent weight of ceric sulfate, (Ce+4 + e -> Ce+3) is 1 gram molecular weight 332.24. • While equivalent weight of potassium permanganate , MnO4- + 5e -> Mn+2 is 158.034 / 5 or 31.61 • IN SHORT – EQUIVALENT WEIGHT = MW/ELECTRONS GAINED Standard Solutions • The standard solutions used in the official assays by oxidation reduction methods include Oxidizing agents • Ferric Ammonium Sulfate • Potassium Permanganate • Potassium Dichromate • Potassium Bromate • Potassium Iodate • Potassium Ferricyanide • Ceric Sulfate • Iodine • Bromine Reducing Agents • Ferrous ammonium sulfate • Oxalic acid • Potassium Arsenite • Titanium Chloride • Sodium Thiosulfate • The number of electrons gained by a given oxidizing agent sometimes depends on the conditions. • The equivalent weights of oxidizing agents which determine the concentrations of standard solutions can be calculated as indicated in the following equiations. • The next part I will write on the board. Oxidizing Agents • Permanganate Ion -> Manganous Ion MnO-4 + 5e -> Mn+2 • Dichromate ion -> Chromous ion Cr2O7-2 + 6e -> 2 Cr+3 • Bromate ion -> Bromide ion • BrO3- + 6e -> Br- • Ceric ion -> Cerous ion • Ce+4 + e -> Ce+3 • Iodine -> Iodide ion • I2 + 2e -> 2I- Reducing Agents • Oxalate ion -> Carbon Dioxide • C2O4-2 -> 2 CO2 + 2e • Thiosulfate ion -> Tetrathionate ion • 2 S2O3-2 -> S4O6-2 + 2e • Arsenite ion -> Asenate ion • AsO2- + H2O -> AsO-3 + 2H+ + 2e • Titanous ion -> Titanic Ion • Ti+3 -> Ti+4 + 1e • Ferrous ion -> Ferric Ion • Fe+4 -> Fe+3 + 1e Permanganate Methods • Potassium Permanganate solution can be standardized easily and retains its concentration over long periods of time. • The reactions of permanganate is also rapid, it also serves as an indicator in titrations where it is used, since a very slight excess of permanganate imparts to solutions a distinct pink color. Ceric Sulfate Titration Methods • A solution of ceric sulfate in diluted sulfuric acid is a strong oxidizing agent and more stable than permanganate solutions. Although permanganate can be reduced to any of several oxidation states, Ce+3 always results on reduction of Ce+4. • Solutions of ceric sulfate combine many advantages of permanganate and dichromate. Permanganometry • Titrant: KMnO4 • Standard: Na Oxalate NaC2O4 • Indicator: No indicator. KMnO4 acts as the indicator • Endpoint: Disappearance of violet Color • Analytes: • Direct – H2O2 topical solution • Indirect: Assay of cherry juice for malic acid content • Residual: Sodium nitrite/Chile saltpeter – additive to prevent botulism Cerimetry • Titrant: CeSO4 (OA) • Perchloric acid: Solvent in preparing CeSO4 • Arsenic trioxide (AsO3) – primary standard • Analyte: Ferrous sulfate tablets, Menadione • Indicator: Orthophenantroline • Ferrous ion forms complex with indicator • Ferroin (red) -> Ferritin (blue) Iodimetry Iodometry
Analyte Reducing Agent Oxidizing Agent
Titrant Iodine VS Na Thiosulfate VS
Titration Direct Indirect
Primary Standard Arsenic Trioxide Potassium dichromate
