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analysis: NON-AQUEOUS TITRATIONS
It’s is used for the assay of certain materials which cannot be easily titrated in aqueous systems
Reasons for titration in NON-AQUEOUS solvents:-there are 3 common reasons The reactants or products might be insoluble in water. The reactants or products might react with water. The analyte too weak an acid or base to be titrated in water.
Solvents in NON-AQUEOUS TITRATIONS:1) 2) 3) 4) The solvents are classified into 4 types Protogenic solvents Protophillic solvents Amphiprotic solvents Aprotic solvents
1) Protogenic solvents:-
2) Protophilic solvents:-
They are acidic solvents they enhances the basicity of weak bases. E.g.:- sulfuric acid, formic acid They are basic in nature .they enhances the acidity of weak acids. E.g.:-pyridine, n-butylamine, ethylene-di-amine,
3) Amphiprotic solvents:-
They category of solvents behave as acid or base depending upon the substance dissolved in it. They accept or donate protons. E.g.:- Glacial acetic acid , Dioxon
In non-aqueous solutions the Selection of solvents based on the following considerations:1) Solubility & nature of sample 2) There should not be any side reactions between the sample or titrant & the solvent 3) The solvent should not effect on the sharpness of the End-point during titrations. 4) The titrant & solubility should be readily miscible with the solvent. 5) The solvent should have high dielectric constant. 6) The solvent should be readily available of low toxicity, easily purified and in expensive.
Solvents in neutral in nature These solvents do not accept or donate protons. These are useful in dissolving the drugs & they act as solvents. E.g.:- Benzene, Carbon tetrachloride.
Formic acid Ethylene diamine Acitic acid,glacial acetic acid
58.5 12.9 6.13
Example of drugs
Levodop, methyl dopa Phenols Adrenaline
Titrating in NON-AQUEOUS solvents:Acidic titrants Basic titrants
20 & 30 amines Ex:-Adrenaline can be titrated with acetous perchloric acid. 2) They are mainly categorized mainly into two classes. Detect the volume of perchloric acid consumed by 50ml of glacial acetic acid. Perchloric acid 0.0241g of potassium hydrogen phthalate is equivalent to 1ml of N\10 perchloric acid. the end point can be detected by the color change of the indictors or by the potentiometric method.Allow tht solution to stand for 24 hours before use. Standardization Weight accurately about 0. iodide are very weakly basic & do not react quantitatively with acetous perchloric acid. Ex:. Titration of basic substances Titration of primary.7g of potassium hydrogen phthalate dissolved in 50ml of glacial acetic acid.4-dinitrobenzene sulphonic acid 2.crystal violet-violet-yellowish green Orange blue –blue – pink 2-naphthol benzein – blue – dark green Classification of NON-AQUEOUS solvents:1) A. Each 0. Acetic anhydrade reacts with water in the perchloric acid & acetic anhydrade & readers the mixture virtually anhydrous.5 ml Perchloric acid + 500ml glacial acetic acid+ 30 ml of acetic anhydrade Cool & add more glacial acetic acid to makeup 1000ml . . The primary standards available for the standardization of acidic titrants are potassium hydrogen phthalate. secondary & tertiary amines Titration of halogen acid slts of bases Titration of acidic substances 1) Titration of basic substances:Preparation Mix 8. The titrants are standardized before the assay of any pharmaceutical substances. Titration of halogen acid salts of bases Chlorides.1 N in glacial acetic acid:- Titration of 10. diphenyl guanidine & anhydrous sodium carbonate. Add 2 drops of crystal violet solution & titrate with perchloric acid solution until the violet changes to green. In basic titrants methoxide of sodium or potassium or lithium & tetrabutylammonium hydroxide are widely used.Perchloric acid in Dioxon Perchloric acid in glacial acetic acid P-toluene sulphonic acid 2. Benzoic acid & phenyl cinchonic acid are suitable primary standards for the standardization of the basic titrations.4. Detection of end point:- In non aqueous titrimetry. Bromides.6-trinitrobenzene sulphonic acid Tetra alkyl ammonium hydroxide Tetra butyl ammonium hydroxide Sodium methoxide Potassium methoxide Lithium methoxide Among the acidic titrants perchloric acid in glacial acetic acid is mostly used. B.
Indicator is QUINOLINE RED. Standardization Weigh accurately 0.7 g of lithium +150ml of methyl alcohol cooling the flask during the addition of methyl When the reaction is complete add 850ml of toluene If cloudiness or precipitate occurs add sufficient methyl alcohol to clarity the solution Store the solution in a container protected from co2 & moisture. Preparation Dissolve 40g of tetrabutyl ammonium iodide in 90ml of dehydrated methanol in a glass stoppered flask. Tetrabutyl ammonium hydroxide 0. Filter through fine sintered glass filter. Alkali methoxides or tetrabutyl ammonium hydroxide. This replaces the halides ion by an equivalent quantity of acetate ion. Each 0. Flush the solution for 10min with dry carbon dioxide free nitrogen Store the container protected from carbon dioxide and moisture Standardization Weigh accurately 0.1 lithium methoxide. Rinse the flask & filter with three quantities Each of 50ml anhydrous toluene Add washing to the filtrate and dilute to 1000 ml with anhydrous toluene. and continue to stir for 30 min when all iodide has reacted. Which is strong base in acetic acid? 2R. Protect the solution from carbon dioxide during the titration.Hcl (CH3 Coo)2 HG +2CL2R+ NH2 + 2ClHgCl2 + 2CH3Coo4CH3CooH (un dissolved) 2CH3 CooH2+ +2CH3Coo- 2) Titration of acedic substances: Basic titrants are used. Place the flask in ice bath add 20g of powdered silver oxide. Solvents required to dissolves the substances include • dimethyl formamide • N-butylamine • Ethylene diamine • Pyridine Preparation Lithium methoxide 0.01221g of benzoic acid is equivalent to 1ml of 0.1 N .25g of benzoic acid dissolved in 80ml of dimethylformamide.1 N Dissolve 0. insert the stopper in the flask and agitate vigorously for one hour. Centrifuge a few minutes & test the super titrant liquid for iodide.NH2. Lithium mithoxide is preferred because less quantity of lithium metal is required to prepare the solution & the solution is easy to prepare.25g of benzoic acid dissolved in 25ml of dimethylformamide & titrates with lithium methoxide solution. A solution of mercuric acetate is added during the titration. Perform the blank titration using 25ml of dimethyl formamide. If the test is positive add another 2g of silver oxide.
A). There are several reasons for the versatility of EDTA.g.D. can act as a hexadentate ligand. with a metal ion.. The link with the metal in the complex is covalent involving either the sharing of two electrons. which by its ability to form a bond or bonds (Covalent or dative). A complexing agent in its widest sense includes any electron-donating system. e. EDTA).T. Once the complex is formed. undissociated and stoichiometric complex is-formed during the addition of titrant to the sample solution (usually solution of a metal ion).. Add 3 drops of 1% solution of thymol blue in dimethylformamide & titrate with tetra butyl ammonium hydroxide. There are also neutral groups involving lone pairs of electrons forming a covalent bond. The term chelating agent is generally applied to ligands which form waterinsoluble complexes with metal ions (e. ethylenediamine is a bidentate ligand and E.. the fluoride ion in K+ (BF4)—. commonly known as ethylene diaminetetraacetic acid disodium salt (E.. There are several organic compounds which possess more than one donating group which may be neutral or charged and thus form bi-.A.T.the iodide ion in 2K+ (HgI4)--2 and complex anions. Pharm.g. NH3 in the complex Co(NH3)36+). salicylaldoxime). Complexometric titrations are those reactions in which simple metal ion are transformed into complex by the addition of a reagent which is known as ligand or complexing agent. the cyanide ion in potassium ferri-and ferrocyanides.These are called simple ligands. They are: .1 tetrabutyl ammonium hydroxide. End point is blue. The complex formed is stable and water-soluble.g..D. For example. It is a method of volumetric analysis developed after the introduction of the analytical reagent. tri-. there is hybridization and equalization of all the bonds. usually from a nitrogen atom (e.g. e. The term sequestering agent is generally applied to ligands which form water-soluble complexes with metal ions (e.01221g of benzoic acid is equivalent to 1ml of 0. or polydentate ligand.g. EDTA disodium salt is the most widely used titrant in complexometric titrations. produces with it a complex which has different properties from that of the free metal ion.analysis: Complexometric Titrations A complexometric titration is one in which a soluble. Perform blank titration Each 0. The simplest complexing agents are elementary anions. one from metal and one from the ligand or donation of a lone pair of electrons from the ligand.
Murexide or Ammonium purpurate 2. All the metal-EDTA complexes are soluble and most complexes form rapidly. It is essential in a complexometric titration to use a buffer solution to maintain the required pH during the titration. Catechol violet 4. The complexometric indicator is a dye which is capable of acting as ligand to form dye-metal complex. Tiron In addition to the visual indicators. The titration is suitable for a semi micro to macro concentration range. this is accompanied by a change in colour. Methyl thymol blue 6. This dye-metal complex is different in colour from the dye itself. As soon as there is slight excess of EDTA. The colour of the solution. 2. Some examples of commonly used complexometric indicators are: 1. Amongst the visual category are important complexometric indicators (Metal-ion indicators. the metal-dye complex decomposes to produce free-dye. Metallochromic indicators or indicators). The end-point is readily detected by chemical or instrumental methods. and also has a lower stability constant than the chelate-metal complex. 4. stoichiometric 1:1 complexes with metal ions. Certain amount of selectivity can be obtained because of differences in stability constants and through the proper control of the pH of the solution. DETECTION OF END-POINT In complexometric titrations. the end-point is detected by using (i) visual indicators or (ii) instrumental methods. therefore. Diphenyl carbazone 9. Sodium alizarine sulphonate 8. Solochrome Black T or Eriochrome black T or mordant black II 3. instrumental methods like potentiometric titration. Xylenol organge 5. 5. soluble. Alizarin complexone 7.1. 3. If EDTA (can be generally represented as Na2H2Y) is used. TYPES OF COMPLEXOMETRIC TITRATIONS . EDTA forms stable. the reaction with a metal ion and the formation constant for the complex formed are represented by From the above reaction it is evident that complexometric titrations will be very sensitive to pH and all procedures in which EDTA is used as a titrant must include a buffer with sufficient capacity to take care of the hydrogen ion produced during the titration. remains that of dye-metal complex until the end-point. photometric titration and amperornetric titration are also employed to detect the end-point.
cobalt copper and lead) can be separated either in the form of insoluble sulphides using Na2S or as insoluble complexes using thioacetamide.y2— The titration is carried out in unbuffered solution. Alkalimetric Titration : In this method. but a potentiometric method of locating the end-point is also suggested. magnesium and lead. 3. Thioglycerol is used to mask copper by precipitation in the assay of lotions containing copper . 2. 4. Calcium. A visual pH indicator may be used. the metal may be determined by the displacement of an equivalent amount of magnesium or zinc from a less stable edetate complex according to the following scheme : M2+ + mgx 2— m x 2— mg +2 1. fluoride for calcium.eliminate the effects of possible impurities which would add to the titre. A blank titration may be performed omitting the sample as a check on the presence of trace of metallic impurities in the reagents. MASKING BY PRECIPITATION Many heavy metals (e. In this titration excess of standard EDTA solution and a suitable buffer solution to added to the metal solution or suspension. and for those metal ions which form more stable complexes with EDTA than with the desired indicator. for insoluble substances (like lead sulfate and calcium oxalate) for substances which do not react instantaneously with EDTA.g. The solution is heated to effect complex formation. ferrocyanide for zinc and copper. Indirect or Back Titrations : This procedure is necessary for metals which precipitate as hydroxides from solution at the pH required for titration.'.Direct Titrations: To the metal ion solution a suitable buffer solution and indicator are added and the solution is titrated with standard EDTA solution until the indicator just changes colour. lead and mercury can be estimated satisfactorily by this method using mordant black II as indicator. protons from EDTA are displaced by a heavy metal and titrated with standard alkali according to the following scheme : (m y ). oxalate for calcium and lead.. These act either by precipitation or by formation of complexes more stable than the interferring ion-edetate complex. decomposed and titrated with EDTA. "masking agents" are used. Replacement or Substitution Titrations : When direct or back titration do not give sharp endpoints. Other common precipitating agents are sulphate for lead and Barium.-4 2 H + mn+2 H. MASKING AND DEMASKING AGENTS Masking agents: When it is required to estimate selectively one or more ions in a mixture of cations and to .hypdroxyquinoline for many heavy metals. These are filtered. cooled and the EDTA not consumed by the sample back-titrated with magnesium or zinc chloride (or sulphate) using a suitable indicator. and cupferron and 8.
antimony. Tiron (Aluminium and Titanium) and triethanolamine (Aluminium). Therefore. iron.005 g of AnalaR CaCO3 in water (25 ml) 2 containing the minimum quantity of dil. Buffer Solution:Dissolve 67.0 and transition elements form EDTA complexes stable down to pH 3. DEMASKING AGENTS These are substances which release masked metal ion. magnesiuni and manganese can be determined in their presence. Another simple method of masking is pH control. tin. An example is that the alkaline earth metals do not form EDTA complexes below pH 7. Add sufficient water to produce 1000 ml (the small amount of magnesium edetate complex is included in the buffer to render the endpoint sharper in calcium titrations).93 g of sodium edetate in 50 ml of water. zinc. dilute to 900 ml with water and add a solution of 0. Dimercaprol forms precipitates with many cations like mercury. cobalt and nickel ions to form complexes in alkaline solution which are more stable than corresponding EDTA complexes. HC1. arsenic. Method: Pipette 20 ml of standard calcium chloride solution into a conical flask. Formaldehyde or chloral hydrate can be used to release the masked zinc ion by potassium cyanide.6 g of disodium edetate in sufficient quantity of distilled water to produce 1000 ml. M/20 CaC1 solution: Dissolve 5. PREPARATION AND STANDARDISATION OF M/20 EDTA M/20 EDTA solution: Dissolve 18. These agents are useful in the determination of specifc metal ion from their mixture with other cations. APPLICATIONS Many pharmacopoeias drugs and chemicals are assayed by complexometric method. A blank titration should be performed on the reagents. copper. Other examples of masking agents belonging to this category are potassium iodide (He+). MASKING BY COMPLEX FORMATION Potassium cyanide reacts with silver. add 1 ml of buffer (pH 10) solution and 3 drops of solochrome black T indicator and titrate with EDTA solution until the colour changes from winered to blue. cadmium. These are given the below Table Drugs Assayed by Complexometry Drug Type of titration . ions such as lead.5 g of ammonium chloride in 570 ml of strong ammonia solution. cool and transfer quantitatively to a 1000 ml flask. cadmium.0. mercury. Dilute with distilled water to 1000 ml.616 g of magnesium sulphate and 0. lead and bismuth. zinc.and zinc. Boil off carbon dioxide.
Direct Calcium aminosalicylate Calcium carbonate Calcium chloride Dibasic calcium phosphate Tribasic calcium phosphate Magnesium chloride Heavy magnesium carbonate Heavy magnesium oxide Magnesium sulphate Zinc chlroide Zinc stearate Zinc Sulphate Zinc undecylenate Aluminium hydroxide gel Aluminium sulphate Alum Calcium gluconate Calcium lactate Indirect (Back) Indirect (Back) Indirect (Back) Replacement Replacement Replacement .
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