Studies on the Depilatory Activity of Sodium Sulphide and Some Related Compounds

STUDIES ON THE DEPILATORY ACTIVITY OF SODIUM SULPHIDE AND SOME RELATED COMPOUNDS By J. M. GILLESPIE4 [Manuscript received August 22, 1950] Summary The depilatory action of sodium sulphide on sheepskin has been investigated by measuring the pull required to remove wool from skin, the swelling of wool root shafts, and the mechanical strength of wool. The rate of action is augmented by increase in temperature, pH value, and concentration of sulphide in the solu tion employed up to 1.0M, but is reduced by increase to higher concentrations. The reciprocal action of the hydroxyl and hydrosulphide ions in digesting keratin is explained in Appendix I in terms of the ionization of sulphydryl groups. Solutions of l.OM sodium sulphide, partially oxidized with peroxide and adjusted to pH 12.8, completely loosen wool in 18 hours at 20°C. only if the oxidation-reduction potential is lower than -400 millivolts. Salts of various oxyacids of sulphur are less effective depilatories than sodium sulphide, the activity diminishing with increase in the number of oxygen atoms in the anion and approximately with the heat of formation. Sodium selenide and sodium telluride possess depilatory activity equal to that of sodium sulphide. I. INTRODUCTION For hundreds of years, chemicals have been used in the leather industry to remove hair, wool, and epidermis from skins and hides prior to tanning .. Lime, alone or "sharpened" with arsenic sulphide, was used originally, but recently sodium sulphide was found to have pronounced depilatory powers and it is today the most widely used adjunct to lime. Merrill (1925), Marriott (1928), and others have determined the optimal conditions for the un-hairing of hides. The findings of these workers are not directly applicable to the pro blem of de-wooling sheepskins for, whereas hair is of so little value that in the tannery the usual procedure is to immerse the hides completely in the un-hairing solution, wool is such a valuable product that precautions must be taken to prevent damage by the alkaline solutions used to loosen it from the skin. Consequently, the technique of applying the depilatory as a paste to the flesh side of the skin has been developed to minimize contamination of the wool. This chemical de-wooling process has received practically no scientific in vestigation in the past and it is still largely empirical. The viscosity of the paste, the concentration of sodium sulphide, and the time of application vary from place to place and, although the concentration is sometimes varied ac cording to the thickness of the skins, strict control is seldom exercised. Usually, 4 Formerly Division of Industrial Chemistry, now Biochemistry Unit, Wool Textile Re search Laboratory, C.S.I.R.O., Melbourne. J88 J. M. GILLESPIE too, the wool is removed approximately 24 hours after application of the depila tory to the skins, regardless of the hastening or retarding influences of such factors as temperature and thickness of skin. If the depilatory has low viscosity, and is therefore easily applied, excess may contaminate the wool at the edge of the skin and weaken or even dis solve it. Contamination also occurs when the wool is pushed off the skin onto the depilatory-contaminated pulling beam. In addition, the calcium compounds in this contaminated wool and on the root ends of the detached wool precipi tate calcium soaps during scouring and contribute further to deterioration in the quality of the wool. Consequently, wool obtained by chemical loosening may be characterized by a harsh handle, lack of lustre, and the presence of particles of calcium salts, disintegrated wool, and weakened fibres, which break up and are lost during combing. It was with the object of defining more accurately the minimum require ments for depilatory activity, with special reference to the influence of physical and chemical factors, that the present investigation was undertaken. II. METHODS OF INVESTIGATION ( a) Preparation of Reagents Except when otherwise stated, the reagents used were of analytical reagent quality 'or better. The sodium salts of hydrogen sulphide, selenide, and tellu ride were specially prepared. Sodium sulphide was prepared from the chemically pure salt, hydrogen sulphide being liberated by mixing it with hot hydrochloric acid, washed by bubbling through water, and absorbed in pure sodium hydroxide. This solu tion of sodium hydrosulphide was stored in sealed paraffin wax-lined bottles and diluted with water and adjusted to the required pH with sodium hydroxide immediately before use. Although, at the pH values used in these investiga tions, the material was actually a mixture of sodium sulphide and hydro sulphide, for convenience it is referred to as sodium sulphide and its properties are accurately defined by the pH and the molarity in terms of the hydrogen sulphide content. Sodium selenide and sodium telluride were prepared immediately before use by direct combination of the elements at an elevated temperature in the absence of oxygen (Vallance, Twiss, and Russell 1931). The exact stoichio metric weights of the elements were used to avoid the formation of poly compounds. Sodium selenide was also prepared by reduction of sodium: sele nate with carbon, and by combination of the elements in the vapour phase at low· pressure. The kieselguhr and kaolin employed were finely ground commercial mineral specimens. (b) Preparation of Depilatories The chemical substances used in the depilatories were dissolved in distilled water. The actual content of active reducing material was determined by standard iodometric procedures (Hall 1936). Unless otherwise stated, the DEPILATORY ACTION OF SODIUM SULPHIDE 189 solutions were adjusted to a suitable physical state with kieselguhr. Before use, the pH of the depilatory was adjusted to the required value by the addi tion of hydrochloric acid or sodium hydroxide. For pH measurements, a Leeds and Northrup valve potentiometer was used in combination with a Cambridge high alkalinity glass electrode. ( c) Measurement of Wool Loosening Activity The method of measuring wool loosening was that due to Lennox (1945). From the central area of a fresh sheep skin, pieces 5 X 5 cm. were cut, and blood and dirt removed by thorough rinsing in running water. In most ex periments the skin pieces were then immersed for 30 min. in an alkaline buffer of the same pH as the depilatory to be applied. Sodium carbonate (0.2M) or 0.2M trisodium phosphate was used for this purpose. A measured amount of the depilatory was applied to the flesh side of. the skin, covered with a glass plate to restrict evaporation and oxidation, and the whole then placed in a moist chamber at 20°C. The progress of wool loosening was followed by the determination, at suitable time intervals, of the depilation load. A depilation load of less than 1 was considered to indicate complete loosening of the wool. (d) Measurement of Eh Any chemical process that depends for its efficiency on reduction must be influenced by the reducing intensity of the system. The normal measure of this, particularly in biological systems, is the oxidation-reduction potential, but this only applies if the system is reversible. In the system now under study there are the reversible reactions: 2 NaHS ~ Na2S2 + 2 (H), 2 (H) + cystine ~ 2 cysteine, and the irreversible oxidation of sulphide to sulphite or thiosulphate. The irreversible nature of the latter reaction and the ease with which the platinum electrodes are poisoned by systems containing sulphydryl compounds render Eh measurements difficult and of doubtful accuracy. However, some measurements were made using a valve potentiometer and platinum electrodes similar to those described by Gillespie (1946). The electrodes were cleaned in boiling concentrated nitric acid after each reading, a mean value from four electrodes being obtained for each Eh. The potentials were converted to the H2 standard and the results given later are presented in this form. ( e) Fibre Strength Measurements Histological observation has shown that most de-wooling chemicals act by reducing the strength of the keratinous region of the wool root, and conse quently the mode of action of depilatories can be investigated by determining their effect on wool fibres. The single fibre breaking-strength apparatus described by Fookes (1946) was used in these investigations. The technique is open to t~e criticism that 190 J. M. GILLESPIE no provision was made for constant loading rates or for maintaining a humidi fied atmosphere. These were overcome by care in operation and the inclusion of samples of wool of known strength at frequent intervals during testing. Observations on these revealed any change in testing conditions. 'Vith these precautions, satisfactory comparative figures were obtained. The chemicals under test were dissolved in air-free distilled water, some times with the addition of the wetting agent, cetyl trimethylammonium bromide. The wool used was merino 60-64's cleaned by extraction with solvents in the fol lowing order: high aromatic light petroleum, acetone, water, acetone. About 30 kg. of wool was thus treated and after careful picking to remove foreign matter, it was thoroughly randomized. It had a normal content of cystine and possessed no detectable sulphydryl groups. (f ) Wool Root Studies The wool fibres with roots attached were pulled from a sheep each day. The roots, consisting of root bulb with about 5 mm. of attached shaft, were placed in the cavity of a well slide, a few drops of the reagent under test was added, and the preparation covered with a slip and placed on the stage of a dissecting microscope. Swelling was detected and semi-quantitatively mea sured with an eyepiece micrometer. There was usually a lag period before swelling commenced, followed by a period of rapid expansion lasting about 30 sec., and finally a much longer period during which the rate of swelling be came progressively slower.

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