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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.

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-As a consequence titration between weak bases and perchloric acid can readily be carried out. -The solvent used is acetic acid. Leveling effect: -A weakly basic solvent has less tendency than a strongly basic one to accept proton & same in a weakly acidic solvent. -All acids tend to become indistinguishable in strength when dissolved in strongly basic solvents owing to the greater affinity of strong bases for protons. It is called leveling effect. -Strong bases are leveling solvents for acids; however weak bases are differentiating solvents for acids. -Upon addition of pyridine(weak)base in acetic acid, the acetic acid exerts it levelling effect. -The effect enhances the basic properties of the pyridine. -Result is the titration of pyridine with perchloric acid( end-point is sharp). -Initially the titration in the aqueous solution was unsuccessful. HClO4 + CH3COOH CH3COOH2+ +ClO4C5H5N + CH3COOH C5H5NH+ +CH3COOCH3COOH2+CH3COO- 2CH3COOH
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Adding HClO4 + C5H5N C5H5NH + + ClO4End-point determination in non-aqueous titration: 1)Using colour changing indicators. - crystal violet(0.5%w/v in G.acetic acid ), - methyl red(0.2%w/v in dioxan), - 1-naphthol benzein(0.2%w/v in G. acetic acid), - oracet bule B(0.5%w/v solution in G. acetic acid) etc. 2)Potentiometric:(If the solution is colourful, turbid etc) -Indicator & glass electrodes are used. -Generally glass electrode is the indicator & saturated calomel electrode (SCE) is reference. Non-aqueous titration:

1)Acidimetry:
-Titrant used: Perchloric acid(V.S.) in glacial acetic acid. -Standardised against potassium hydrogen phthalate(PHP). -Used in the assay of alkali metal salts of organic acids, primary , secondary and tertiary amines, amino acids and other organic base salts with organic acids. RNH2 + HClO4 [RNH3]++ClO4 Sodium acetate: Determination of percentage purity of CH3.COONa,3H2O CH3.COONa + HClO4 CH3.COOH + NaClO4 136.1g CH3.COONa,3H2O HClO4 1000ml M 0.01361g CH3.COONa,3H2O 1ml 0.1M.

In the halogen acid salts of bases or the halide ions(very feeble base), - Mercuric acetate(which is undissociated in acetic acid solution) is added. - Halide salt replaces the halide ion by an equivalent quantity of acetate ion. - Acetate ion is a strong base in acetic acid. 2R.NH2 .HCl 2RNH3+ + 2Cl(CH3COO)2Hg (undisso.) + 2Cl- HgCl2(undisso.) +2CH3COO2CH3COOH2 + 2CH3COO- 4CH3COOH

2)Akalimetry:
-Titrant used: Tetrabutylammonium hydroxide in methanol (Not common nowadays: potassium, sodium or lithium methoxide) -Standardised against benzoic acid in dimethylformamide(DMF). -Used in the assay of cyclic imides, thiazide, sulphonamides & phenols.