Sulphuric acid, determination

The above considerations will be illustrated by the simultaneous determination of manganese and chromium in steel and other ferro-alloys. The absorption spectra of 0.001 M permanganate and dichromate ions in 1M sulphuric acid, determined with a spectrophotometer and against 1M sulphuric acid in the reference cell, are shown in Fig. 17.20. For permanganate, the absorption maximum is at 545 nm, and a small correction must be applied for dichromate absorption. Similarly the peak dichromate absorption is at 440 nm, at which permanganate only absorbs weakly. Absorbances for these two ions, individually and in mixtures, obey Beer s Law provided the concentration of sulphuric acid is at least 0.5M. Iron(III), nickel, cobalt, and vanadium absorb at 425 nm and 545 nm, and should be absent or corrections must be made. 

Fig. 51 The experimental curve of the molecular weight distribution of a PpPTA polymer dissolved in sulphuric acid determined with size-exclusion chromatography. The relation between molecular weight and retention time t (in minutes) 10log(Mw)=0.345-0.1321 1. The position of the vertical line at f=42 min corresponds with Mw=6,200... 

Stowmarket, manufacture of gun-cotton at, 57. Sulphuric acid, determination of strength of, 24. Sy on test for nitro-cellulose, 269. 

A small company purchases 98 per cent sulphuric acid and produces 85 per cent sulphuric acid for internal use. The cooled mixing vessel to which water and 98 per cent acid are fed is initially filled with 98 per cent sulphuric acid. Determine the minimum time for the acid concentration to reach 86 per cent strength if the maximum water flow rate is 0.01 m s and the working volume of the vessel is 1 m. State any assumptions. 

The extent of dissociation at a given temperature can be determined by measuring the density of the vapour. Since anhydrous sulphuric acid is less volatile than hydrogen chloride, ammonium sulphate does not readily sublime on heating some ammonia is evolved to leave the hydrogensulphate ... 

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. 

To determine which halogen is present, take 1-2 ml. of the filtrate from the sodium fusion, and add dilute sulphuric acid until just acid to litmus. Add about 1 ml. of benzene and then about 1 ml. of chlorine water and shake. A yellowish-brown colour in the benzene indicates bromine, and a violet colour iodine. If neither colour appears, the halogen is chlorine. The result may be confirmed by testing the solubility of the silver halide (free from cyanide) in dilute ammonia solution silver chloride is readily soluble, whereas the bromide dissolves with difficulty, and the iodide not at all. 

The student should read Sections 1,10 to 1,16 carefully before commencing any experimental work. A supply of melting point capillaries is prepared as described in Section 11,10 (compare Fig. 77, R , I). The apparatus illustrated in Fig. 77. 10, 2, a is assembled with concentrated sulphuric acid as the bath liquid the thermometer selected should have a small bulb. The melting points of pure samples of the following compounds are determined in the manner detailed in Section 11,10 —... 

Chakactkrisation of Unsaturatkd Aliphatic Hydrocarbons Unlike the saturated hydrocarbons, unsaturated aliphatic hydrocarbons are soluble in concentrated sulphuric acid and exhibit characteristic reactions with dUute potassium permanganate solution and with bromine. Nevertheless, no satisfactory derivatives have yet been developed for these hydrocarbons, and their characterisation must therefore be based upon a determination of their physical properties (boiling point, density and refractive index). The physical properties of a number of selected unsaturated hydrocarbons are collected in Table 111,11. 

Acidify the residue in the flask with dUute sulphuric acid and distil off 10-15 ml. of the solution. Test a smaU portion of the distillate for acidity, and also observe the odour. Neutralise the main portion with sodium hydroxide solution (add a drop of phenolphthalein to act as indicator), evaporate to smaU bulk, and convert the sodium salt into the p-bromophenacyl ester or into some other suitable derivative (Section 111,85) determine the m.p. of the derivative. 

Hydrolysis of a nitrile to an amide. Warm a solution of 1 g. of the nitrile benzyl cyanide) in 4 ml. of concentrated sulphuric acid to 80-90°, and allow the solution to stand for 5 minutes. Cool and pour the solution cautiously into 40 ml. of cold water. Filter oflT the precipitate stir it with 20 ml. of cold 5 per cent, sodium hydroxide solution and filter again. RecrystaUise the amide from dilute alcohol, and determine its m.p. Examine the solubility behaviour and also the action of warm sodium hydroxide solution upon the amide. 

Raman spectroscopy provides the easiest way of estimating the concentration of nitronium ions in different media ( 2.4.1). The concentration, determined by infra-red spectroscopy, of nitronium ions in nitric acid was increased markedly by the addition of sulphuric acid. ... 

The activity coefficients in sulphuric acid of a series of aromatic compounds have been determined. The values for three nitro-com-pounds are given in fig. 2.2. The nitration of these three compounds over a wide range of acidity was also studied, and it was shown that if the rates of nitration were corrected for the decrease of the activity coefficients, the corrected rate constant, varied only slightly... 

As the medium is still further diluted, until nitronium ion is not detectable, the second-order rate coefficient decreases by a factor of about 10 for each decrease of 10% in the concentration of the sulphuric acid (figs. 2.1, 2.3, 2.4). The active electrophile under these conditions is not molecular nitric acid because the variation in the rate is not similar to the correspondii chaise in the concentration of this species, determined by ultraviolet spectroscopy or measurements of the vapour pressure. " ... 

TABLE 2.5 Some compounds for which the dependences of rate of nitration upon acidity, in aqueous sulphuric acid at 25 °C, have been determined... 

The phenomenon was established firmly by determining the rates of reaction in 68-3 % sulphuric acid and 61-05 % perchloric acid of a series of compounds which, from their behaviour in other reactions, and from predictions made using the additivity principle ( 9.2), might be expected to be very reactive in nitration. The second-order rate coefficients for nitration of these compounds, their rates relative to that of benzene and, where possible, an estimate of their expected relative rates are listed in table 2.6. 

Like added nitrate, sulphuric acid is not involved in the condition which determines the order of the reaction, and therefore its only effect will be to increase the observed rate constants. The rate under zeroth-order conditions is given by the first of the two expressions below,... 

Generally the determination of the reactivity of a particular compound depends upon comparison of its rate of nitration with that of benzene at the same acidity and temperature. Because of the spread of rates this may not be practically possible and, in any case, is usually not necessary because of the parallelism existing among rate profiles (fig. 2.4). Reactivities in aqueous sulphuric acid are, in fact, very nearly independent of acidity, and stepwise comparison of data for a compound with those of benzene determined at different acidities is possible. 

Sulphate process. The ilmenite is reacted with sulphuric acid giving titanium sulphate and ferric oxide. After separation of ferric oxide, addition of alkali allows precipitation of hydrous titanium dioxide. The washed precipitate is calcined in a rotary kiln to render titanium dioxide. The nucleation and calcination conditions determine the crystalline structure of titanium dioxide (e.g. rutile or anatase). 

In opocinchenine the hydroxyl group must, therefore, be in the ortho-position relative to the point of attachment of the benzene ring to the quinoline nucleus. The relative positions of the two ethyl groups are determined by the fact that apocincheninic acid ethyl ether on oxidation with lead peroxide and sulphuric acid gives the lactone of hydroxyopo-cincheninic acid ethyl ether (I), which, on oxidation by sodium hypo-bromite, yields quinolylphenetoledicarboxylic acid (II). 

It IS by a similar process that alizaiin has been synthesised w ith the oliject of ascertaining its constitution (see Notes on Prep. 110, p. 316), When two molecules of phenol and one molecule of phthalic anhydride are heated together with cone, sulphuric acid, then phenolphthalein is formed (Baeyei). Its constitution has been determined by its synthesis from phthalyl chloride and benzene by means of the Friedel-Crafts leaction (see Notes on Piep. 100, p. 309). Phthalyl chloride and benzene yield in presence of AlCl., phthalophenone. 

To prepare sabinenic acid for the identification of the terpene, Wallach operates as follows 10 grams of the crude terpene are mixed with the theoretical amount of potassium permanganate in water at ice temperature. The oxide of manganese is filtered off, the liquid rendered acid and extracted with ether, and the ethereal solution shaken with caustic soda solution. The sodium salt is very sparingly soluble, and is precipitated, collected, and decomposed with dilute sulphuric acid and purified by a further solution in ether. It must be well dried in a desiccator before its melting-point is determined. Sabinene has the following constitution —... 

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