Standard acid

Ammonia may be estimated by dissolving the gas in a known volume of standard acid and then back-titrating the excess acid. In a method widely used for the determination of basic nitrogen in organic substances (the Kjeldahl method), the nitrogenous material is converted into ammonium sulphate by heating with concentrated sulphuric acid. The ammonia is then driven off by the action of alkali and absorbed in standard acid. 

By the evolution of ammonia with Devarda s alloy in alkaline solution in absence of ammonium ions this is used quantitatively, the ammonia being absorbed in excess standard acid and the excess acid back-titrated. 

Excess standard acid is added, and the excess (after disappearance of the solid oxide) is estimated by titration with standard potassium manganate(VII). 

The method is based on the conversion of urea to amnionium carbonate and the estimation of the latter by titration with standard acid. For this purpose, two equal quantities of urea (or urine) are measured out into two flasks A and B. A is treated with 10 ml. of a strong urease preparation and some phenol-phthalein, warm water is added and the mixture is adjusted by the addition of V/io HCl from a burette A until the red colour is just discharged. This brings the mixture to about pH 8 (the optimum for urease) and also prevents loss of ammonia. 

Hydrazine hydrate may be titrated with standard acid using methyl orange as indicator or, alternatively, against standard iodine solution with starch as indicator. In the latter case about 0-1 g., accurately weighed, of the hydrazine hydrate solution is diluted with about 100 ml. of water, 2-3 drops of starch indicator added, and immediately before titration 6 g. of sodium bicarbonate are introduced. Rapid titration with iodine gives a satisfactory end point. 

The saponiflcatlon equivalent or the equivalent weight of an ester is that weight in grams of the ester from which one equivalent weight of acid is obtainable by hydrolysis, or that quantity which reacts with one equivalent of alkali. The saponification equivalent is determined in practice by treating a known weight of the ester with a known quantity of caustic alkali used in excess. The residual alkali is then readily determined by titration of the reaction mixture with a standard acid. The amount of alkafi that has reacted with the ester is thus obtained the equivalent can then be readily calculated. 

Determine the methylamine content of the commercial solution by titration with standard acid using methyl orange as indicator. Adjust the quantity of methyl-amine solution in accordance with the methylamine content for some commercial samples, the figure may be 33-40 per cent. 

Basic substances for standardizing acidic solutions continued)... 

Total basicity is measured by standard acid—base titration techniques. The activity divided by the total basicity should be greater than 90%. If it is not, then the Grignard reagent should be checked for unreacted alkyl or aryl haUde, homo-coupled product, hydrolysis products, and oxidation products. 

Devarda s Method. Nitrogen in nitrates or nitric acid also may be deterrnined by the Kjeldahl method or by Devarda s method. The latter is both convenient and accurate when no organic nitrogen is present. The nitrate is reduced by Devarda s alloy to ammonia in an alkaline solution. The ammonia is distilled and titrated with standard acid. 

The alkalinity is determined by titration of the sample with a standard acid (sulfuric or hydrochloric) to a definite pH. If the initial sample pH is >8.3, the titration curve has two inflection points reflecting the conversion of carbonate ion to bicarbonate ion and finally to carbonic acid (H2CO2). A sample with an initial pH <8.3 only exhibits one inflection point corresponding to conversion of bicarbonate to carbonic acid. Since most natural-water alkalinity is governed by the carbonate—bicarbonate ion equiUbria, the alkalinity titration is often used to estimate their concentrations. 

The preparation of cyclohexylmagnesium bromide is described on p. 22. The solution may be standardized by titrating against 0.5 N hydrochloric acid, and exactly one mole equivalent is used in the preparation. Five cubic centimeters of cyclohexylmagnesium bromide solution is slowly added to 20 cc. of water, an excess of the standard acid is added, and the excess acid titrated with sodium hydroxide. If 85 g. (3.5 moles) of magnesium, one liter of dry ether, and 571 g. of cyclohexyl bromide (3.5 moles) are used, a solution results which is about 2 molar. 

The calcium salt of the principal product, d/-tartaric acid, crystallizes with four molecules of water, while the secondary product, meso-tartaric acid, forms a calcium salt which crystallizes with three molecules of water. The amount of sulfuric acid actually required may readily be calculated from the percentage of calcium found on analysis in the regular way or it may be estimated by igniting a sample, and titrating the residue with standard acid. 

Titrier-flasche,/. titration bottle (for feeding a buret), -fliissigkeit, /. titrating solution, standard solution, -gerate, n.pl. titrating apparatus, -methode, /. titration method, volumetric method, -saure, /. titrating acid, standard acid. 

Alkalinity and Lime Content. The whole mud alkalinity test procedure is a titration method which measures the volume of standard acid required to react with the alkaline (basic) materials in an oil mud sample. The alkalinity value is used to calculate the pounds per barrel unreacted excess lime in an oil mud. Excess alkaline materials, such as lime, help to stabilize the emulsion and also neutralize carbon dioxide or hydrogen sulfide acidic gases. 

A second major use of sulfuric acid of commerce is in reactions with bases. In laboratory use it is diluted to a much lower concentration and can be used as a standard acid. A typical problem would be the titration of a base solution of unknown concentration using a sulfuric acid solution of known concentration. For example, What is the concentration of a sodium hydroxide solution if 25.43 ml of the NaOH solution just reacts with 18.51 ml of 0.1250 M HiSOt (to produce a neutral solution) ... 

To use the above expression for measuring the strength of an acid, a standard acid-base pair, say A2-B2, must be chosen, and it is usually convenient to refer acid-base strength to the solvent. In water the acid-base pair H30 + -H20 is taken as the standard. The equilibrium defining acids is therefore ... 

Neutralisation reactions, or addimetry and alkalimetry. These include the titration of free bases, or those formed from salts of weak acids by hydrolysis, with a standard acid (addimetry), and the titration of free acids, or those formed by the hydrolysis of salts of weak bases, with a standard base (alkalimetry). The reactions involve the combination of hydrogen and hydroxide ions to form water. 

Procedure B. The experimental details for the preparation of the initial solution are similar to those given under Procedure A. Titrate 25 or 50 mL of the cold solution with standard 0.1M hydrochloric acid and methyl orange, methyl orange-indigo carmine, or bromophenol blue as indicator. Titrate another 25 or 50 mL of the cold solution, diluted with an equal volume of water, slowly with the standard acid using phenolphthalein or, better, the thymol-blue cresol red mixed indicator in the latter case, the colour at the end point is rose. Calculate the result as described in the Discussion above. 

A slight excess of 10 per cent barium chloride solution is added to the hot solution to precipitate the carbonate as barium carbonate, and the excess of sodium hydroxide solution immediately determined, without filtering off the precipitate, by titration with the same standard acid phenolphthalein or thymol blue is used as indicator. If the volume of excess of sodium hydroxide solution added corresponds to timL of 1M sodium hydroxide and u mL 1M acid corresponds to the excess of the latter, then v — v = hydrogencarbonate, and V— v — v ) = carbonate. 

Another sample of equal volume is then titrated with the same standard acid using methyl orange, methyl orange-indigo carmine or bromophenol blue as indicator. The volume of acid used (say, ymL) corresponds to carbonate+ hydrogencarbonate. Hence 2y = carbonate, and y — 2Y = hydrogencarbonate. 

In the direct method, a solution of the ammonium salt is treated with a solution of a strong base (e.g. sodium hydroxide) and the mixture distilled. Ammonia is quantitatively expelled, and is absorbed in an excess of standard acid. The excess of acid is back-titrated in the presence of methyl red (or methyl orange, methyl orange-indigo carmine, bromophenol blue, or bromocresol green). Each millilitre of 1M monoprotic acid consumed in the reaction is equivalent to 0.017032 g NH3 ... 

In the indirect method, the ammonium salt (other than the carbonate or bicarbonate) is boiled with a known excess of standard sodium hydroxide solution. The boiling is continued until no more ammonia escapes with the steam. The excess of sodium hydroxide is titrated with standard acid, using methyl red (or methyl orange-indigo carmine) as indicator. 

The ammonia is distilled into excess of standard acid as in Section 10.35. 

The 42 per cent hydrazine hydrate solution supplied by the Eastman Kodak Company is too dilute for use as such, but may be concentrated by distillation with xylene.1 A mixture of r44 cc. (150 g.) of the 42 per cent solution and 230 cc. of xylene is distilled from a 500-cc. flask through a 17-cm. Hempel column fitted into a cork covered with tin foil. After distillation of the xylene, with about 85 cc. of water, the residue yields on distillation 45-50 g. of 80-85 per cent hydrazine hydrate. This material, assayed best by titration with standard acid using methyl orange as indicator, may be used as such or concentrated further (see Note 6). 

Technical aqueous methylamine solution (28-33 Per cent) may be used. The amine content should be determined by titration with standard acid. 

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