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Non-aqueous titration
-Non-aqueous titration is the titration of substances dissolved in non-aqueous solvents by titrant prepared in non-aqueous solvent .(neutralization or acidimetry & alkalimetry). -This titration is frequently used in the assay of various pharmaceutical compound. -Two problems in titrations carried out in aqueous solvent can be solved by this technique: 1.Too weakly basic or too weakly acidic substances fail to give sharp end points in aqueous solution. -Often these can be titrated in non-aqueous solvents. 2.Many water insoluble substances are sufficiently soluble in organic solvents to permit their titration in these non- aqueous media. The Lowry Bronsted theory can explain the reactions occuring during many non-aqueous titrations. “an acid is a proton donor & a base is a proton acceptor” HB
acid

H+ + Bproton base

-An acid may be either an electrically neutral molecule, such as HCl, or a positive charged cation such as C6H5NH3+ -A base may be either an electrically neutral molecule, such as C6H5NH2 or a negatively charged anion, such as Cl-An acidic substance can function as acids only in the presence of a base to which they can donate a proton. -basic properties do not become apparent unless an acid also is present. -Ability of substances to act as acids or bases depend very much upon the nature of the solvent system used. -Solvent system surfaces & covers the acidic or basic properties of substances. Types of solvents: -Aprotic solvents: Carbon tetrachloride, benzene, toluene etc. -Protophilic solvents: Ammonia, amines, ketones etc. -Protogenic solvents: Anhydrous acids such as hydrogen fluoride, sulphuric acid etc. -Amphiprotic solvents-: Water, acetic acid, alcohols etc. Amphiprotic solvent: -Enjoys protogenic and protophilic properties. - Acetic acid is frequently used solvent in non-aqueous titration of basic substances. -Acetic acid dissociates to produce protons: CH3COO H ⇌ CH3COO - + H+ (acetic acid is functioning as an acid) -Accepts proton(in presence of perchloric acid(strong acid): HClO4 ⇌ H+ + ClO4CH3COOH + H+

⇌ CH3COOH2+
(onium ion)

functioning as a base)

-The CH3COOH2 + so formed (as an acid) can readily give its proton to base(pyridine, a weak base). Levelling effect. - A weak base has its basic properties enhanced.

2)Potentiometric:(If the solution is colourful. .3H2O ≡ HClO4 ≡ 1000ml M 0.5%w/v in G. turbid etc) -Indicator & glass electrodes are used. . HClO4 + CH3COOH ⇌ CH3COOH2+ +ClO4C5H5N + CH3COOH ⇌ C5H5NH+ +CH3COOCH3COOH2+CH3COO-⇌ 2CH3COOH ____________________________________________________________ Adding HClO4 + C5H5N ⇌ C5H5NH + + ClO4End-point determination in non-aqueous titration: 1)Using colour changing indicators. -Used in the assay of alkali metal salts of organic acids. acetic acid) etc. acetic acid).2%w/v in G. primary . . -The effect enhances the basic properties of the pyridine.acetic acid ). -All acids tend to become indistinguishable in strength when dissolved in strongly basic solvents owing to the greater affinity of strong bases for protons. however weak bases are differentiating solvents for acids.2 -As a consequence titration between weak bases and perchloric acid can readily be carried out.crystal violet(0.01361g CH3. -Standardised against potassium hydrogen phthalate(PHP). -Result is the titration of pyridine with perchloric acid( end-point is sharp).COOH + NaClO4 136.3H2O CH3.1g CH3. -Initially the titration in the aqueous solution was unsuccessful.1-naphthol benzein(0.3H2O ≡ 1ml 0.5%w/v solution in G.methyl red(0.COONa. -Generally glass electrode is the indicator & saturated calomel electrode (SCE) is reference. RNH2 + HClO4 → [RNH3]++ClO4 Sodium acetate: Determination of percentage purity of CH3.oracet bule B(0.2%w/v in dioxan).COONa.1M. Leveling effect: -A weakly basic solvent has less tendency than a strongly basic one to accept proton & same in a weakly acidic solvent. Non-aqueous titration: 1)Acidimetry: -Titrant used: Perchloric acid(V. amino acids and other organic base salts with organic acids. -Strong bases are leveling solvents for acids.S.) in glacial acetic acid.COONa + HClO4 → CH3. secondary and tertiary amines.COONa. -The solvent used is acetic acid. . the acetic acid exerts it levelling effect. It is called leveling effect. . -Upon addition of pyridine(weak)base in acetic acid.

NH2 .) +2CH3COO2CH3COOH2 + 2CH3COO.HCl ⇌ 2RNH3+ + 2Cl(CH3COO)2Hg (undisso.Mercuric acetate(which is undissociated in acetic acid solution) is added. -Used in the assay of cyclic imides. sulphonamides & phenols. 2R. .) + 2Cl.→ HgCl2(undisso. . .3 In the halogen acid salts of bases or the halide ions(very feeble base).Halide salt replaces the halide ion by an equivalent quantity of acetate ion.Acetate ion is a strong base in acetic acid. .⇌ 4CH3COOH 2)Akalimetry: -Titrant used: Tetrabutylammonium hydroxide in methanol (Not common nowadays: potassium. thiazide. sodium or lithium methoxide) -Standardised against benzoic acid in dimethylformamide(DMF).

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