Sulphate control

Caraco, N.F., Cole, J.J., and Likens, GE. (1989) Evidence for sulphate-controlled phosphorus release from sediments of aquatic systems. Nature 341, 316-318. 

Where foil is laminated to paper, attention must be paid to both the composition of the paper and moisture content if subsequent corrosion is to be avoided. Ideally the moisture should be 7% and less, and chloride and sulphate controlled so that the pH (acidity) is not below 5. If the foil is laminated by an adhesive, similar factors apply. 

Figure 7.32 Permeation curves for 10% sodium lauryl sulphate (control) containing (a) 5 % various ethoxylated compounds, PEG6000, Tergitol 25-L-3 (Cj i 15 E3) and Tergitol 25-L-20 (Cl 1E20) and (b) 5 % of a series of PEG homologues. The membranes used were neonatal rat stratum corneum membranes. From Faucher et al. [137].

Use the apparatus detailed in Section 111,20. Dissolve 100 g. (123 ml.) of methyl n-butyl ketone (2-hexanone) (Section 111,152) in 750 ml. of ether and add 150 ml. of water. Introduce 69 g. of clean sodium in the form of wire (or small pieces) as rapidly as possible the reaction must be kept under control and, if necessary, the flask must be cooled in ice or in running water. When all the sodium has reacted, separate the ethereal layer, wash it with 25 ml. of dilute hydrochloric acid (1 1), then with water, dry with anhydrous potassium carbonate or with anhydrous calcium sulphate, and distil through a fractionating column. Collect the fraction of b.p. 136-138°. The yield of methyl n-butyl carbinol (2-hexanol) is 97 g. 

Equip a 1-litre three-necked flask with a powerful mechanical stirrer, a separatory funnel with stem extending to the bottom of the flask, and a thermometer. Cool the flask in a mixture of ice and salt. Place a solution of 95 g. of A.R. sodium nitrite in 375 ml. of water in the flask and stir. When the temperature has fallen to 0° (or slightly below) introduce slowly from the separatory funnel a mixture of 25 ml. of water, 62 5 g. (34 ml.) of concentrated sulphuric acid and 110 g. (135 ml.) of n-amyl alcohol, which has previously been cooled to 0°. The rate of addition must be controlled so that the temperature is maintained at 1° the addition takes 45-60 minutes. AUow the mixture to stand for 1 5 hours and then filter from the precipitated sodium sulphate (1). Separate the upper yellow n-amyl nitrite layer, wash it with a solution containing 1 g. of sodium bicarbonate and 12 5 g. of sodium chloride in 50 ml. of water, and dry it with 5-7 g. of anhydrous magnesium sulphate. The resulting crude n-amyl nitrite (107 g.) is satisfactory for many purposes (2). Upon distillation, it passes over largely at 104° with negligible decomposition. The b.p. under reduced pressure is 29°/40 mm. 

Quinoline may be prepared by heating a mixture of aniline, anhydrous glycerol and concentrated sulphuric acid with an oxidising agent, such as nitrobenzene. The reaction with nitrobenzene alone may proceed with extreme violence, but by the addition of ferrous sulphate, which appears to function as an oxygen carrier, the reaction is extended over a longer period of time and Is under complete control. 

Fluoride production consists on reacting fluorspar mineral (CaF ) with H SO (cc) to form HF and calcium sulphate. However, reactions do not achieve 100 % yield, so fluorogypsum or anhydrite (CaSO ) obtained contains small amounts of fluoride as CaF in its stmcture. The application of this kind of subproduct is well-known as constmction material, so that the flouride content has to be controlled. 

Other additives that may be incorporated include sodium hydrogen phosphates as buffering agents to stabilise that pH of the reaction medium, lauryl mercaptan or trichlorethylene as chain transfer agents to control molecular weight, a lubricant such as stearic acid and small amounts of an emulsifier such as sodium lauryl sulphate. 

Dissolved mineral salts The principal ions found in water are calcium, magnesium, sodium, bicarbonate, sulphate, chloride and nitrate. A few parts per million of iron or manganese may sometimes be present and there may be traces of potassium salts, whose behaviour is very similar to that of sodium salts. From the corrosion point of view the small quantities of other acid radicals present, e.g. nitrite, phosphate, iodide, bromide and fluoride, have little significance. Larger concentrations of some of these ions, notably nitrite and phosphate, may act as corrosion inhibitors, but the small quantities present in natural waters will have little effect. Some of the minor constituents have other beneficial or harmful effects, e.g. there is an optimum concentration of fluoride for control of dental caries and very low iodide or high nitrate concentrations are objectionable on medical grounds. 

Sulphate in general appears to behave very similarly Hatch and Rice have shown that small concentrations in distilled water increase corrosion more than similar concentrations of chloride". In practice, high-sulphate waters may attack concrete, and the performance of some inhibitors appears to be adversely affected by the presence of sulphate. Sulphates have also a special role in bacterial corrosion under anaerobic conditions. Both sulphates and nitrates are acceptable in low-pressure boiler feed water as they are believed to be of value in controlling caustic cracking. 

Duncan and Frankenthal report on the effect of pH on the corrosion rate of gold in sulphate solutions in terms of the polarization curves. It was found that the rate of anodic dissolution is independent of pH in such solutions and that the rate controlling mechanism for anodic film formation and oxygen evolution are the same. For the open circuit behaviour of ferric oxide films on a gold substrate in sodium chloride solutions containing low iron concentration it is found that the film oxide is readily transformed to a lower oxidation state with a Fe /Fe ratio corresponding to that of magnetite . 

The furnace scales which form on alloy steels are thin, adherent, complex in composition, and more difficult to remove than scale from non-alloy steels. Several mixed acid pickles have been recommended for stainless steel, the type of pickle depending on the composition and thickness of the scale For lightly-scaled stainless steel, a nitric/hydrofluoric acid mixture is suitable, the ratio of the acids being varied to suit the type of scale. An increase in the ratio of hydrofluoric acid to nitric acid increases the whitening effect, but also increases the metal loss. Strict chemical control of this mixture is necessary, since it tends to pit the steel when the acid is nearing exhaustion. For heavy scale, two separate pickles are often used. The first conditions the scale and the second removes it. For example, a sulphuric/hydrochloric mixture is recommended as a scale conditioner on heavily scaled chromium steels, and a nitric/hydrochloric mixture for scale removal. A ferric sulphate/ hydrofluoric acid mixture has advantages over a nitric/hydrofluoric acid mixture in that the loss of metal is reduced and the pickling time is shorter, but strict chemical control of the bath is necessary. 

The Watts Solution, is a relatively cheap, simple solution which is easy to control and keep pure. The nigkel sulphate acts as the main source of nickel ions, though nickel chloride is an additional source. Higher deposition rates can be, used when the ratio of nickel chloride to nickel sulphate is raised and some proprietary bright nickel solutions are available in a high-speed version which contains an increased concentration of nickel chloride. 

Self regulating chromium The self-regulating chromium solutions were introduced to eliminate the need for maintaining the correct catalyst concentration by periodic analysis they depend on the addition of a sparingly soluble sulphate to the bath which supplies the correct amount of SO 4 automatically. Initially strontium sulphate (solubility approx. l-75g/l at 30°C and 21 g/1 at 40°C) was employed for this purpose. The strontium sulphate forms a layer on the bottom of the bath, which must be stirred from, time to time. A bath with a CrO, concentration of 250 g/1 would have a catalyst content of l 52g/l SrS04 and 4-35 g/1 of KjSiF. Potassium dichromate and strontium chromate have also found application as additives for the control of the saturation solubility of the catalyst. 

In order that a chromate film may be deposited, the passivity which develops in a solution of chromate anions alone must be broken down in solution in a controlled way. This is achieved by adding other anions, e.g. sulphate, nitrate, chloride, fluoride, as activators which attack the metal, or by electrolysis. When attack occurs, some metal is dissolved, the resulting hydrogen reduces some of the chromate ion, and a slightly soluble golden-brown or black chromium chromate (CtjOs CrOs xHjO) is formed. 

Urea possesses negligible basic properties (Kb = 1.5 x 10 l4), is soluble in water and its hydrolysis rate can be easily controlled. It hydrolyses rapidly at 90-100 °C, and hydrolysis can be quickly terminated at a desired pH by cooling the reaction mixture to room temperature. The use of a hydrolytic reagent alone does not result in the formation of a compact precipitate the physical character of the precipitate will be very much affected by the presence of certain anions. Thus in the precipitation of aluminium by the urea process, a dense precipitate is obtained in the presence of succinate, sulphate, formate, oxalate, and benzoate ions, but not in the presence of chloride, chlorate, perchlorate, nitrate, sulphate, chromate, and acetate ions. The preferred anion for the precipitation of aluminium is succinate. It would appear that the main function of the suitable anion is the formation of a basic salt which seems responsible for the production of a compact precipitate. The pH of the initial solution must be appropriately adjusted. 

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