1. CHROME-NERADOL D liquors, containing comparatively larger amounts of Neradol D, act too rapidly on the pelt and draw the grain; smaller amounts of Neradol D seem without influence on the finished leather, which possesses pronounced characteristics of chrome leather. Another disagreeable factor is the following: the chrome salts must possess a certain degree of basicity in order to produce good leather; the Neradol D must, on the other hand, possess a certain acidity to produce the optimum results, and it is hence impossible to balance practically the basicity of the chrome salts and the acidity of the Neradol in order to justify the presence of both. If one of the two is used separately before the other, a leather always results possessing the characteristics of the material first employed, provided the time of action has been sufficiently extended. If insufficient time has been allowed, the characteristics imparted by the main tanning agent are not altered.
2. ALUMINIUM SALTS AND NERADOL require practically the same basicity and acidity respectively, and when combined always yield a leather possessing mainly the properties of one of the components. In addition to this fact, leathers tanned with aluminium salts possess great softness and stretch, those tanned with Neradol D greater firmness and less stretch, and these opposing qualities completely compensate one another and render nil the value of such mixtures.
In addition to this, the presence of aluminium salts produces no better fixation on the leather fibre of basic coal-tar dyes, so that in this respect also a combination of aluminium salts and Neradol D is of no value.
3. FAT NERADOL D TANNAGE: Just as aluminium salts impart special characteristics to leather, this property is exhibited by fatty matters, especially so as regards stretchiness and softness. Both of the latter are not apparent to the same extent in an oil tannage into which Neradol D and oil enter as constituents. It is, however, not excluded that, in view of the fact that the combination of oils and Neradol D appear to produce the most promising results of the three from a technical point of view, such combination would yield products possessing less stretch and greater softness which, by occupying an intermediary position, might possess certain advantages and be useful for certain technical purposes.
9. Analysis of Leather Containing Neradol D
Chemical examination of leathers tanned with Neradol D or with mixtures of natural tannins and Neradol D often involve a determination of the materials employed in tannage. In most leathers exclusively tanned with vegetable tanning materials, it is usually possible to determine at least the nature of the main tanning agent, whereas the attempts at determining those tannins which are only present in minor quantities rarely succeed. Since Neradol D usually is employed in comparatively small quantities, it has been imperative to find a method which also permits of the detection of smaller quantities of Neradol D. Provided the presence of not less than 5 per cent. (on the weight of the leather) of Neradol D, the following method yields reliable results:—20-30 gm. of the leather are ground or sliced as finely as possible and the powder (or the slices) treated in the cold with a sufficient volume of dilute ammonia solution (5 c.c. ammonia plus 95 c.c. of water) for eight to twelve hours. The object of this is to dissolve the tannins, but no protein should go into solution. The solution is filtered and the filtrate evaporated on the water bath till it occupies a volume of about 30 c.c. A few c.c. of aniline hydrochloride are now cautiously added, when it should be carefully noted if a precipitate is thrown down which might be either completely or only partly soluble in excess of aniline hydrochloride. A precipitate is always thrown down when Neradol D or wood pulp is present; only the Neradol D precipitate is soluble in excess of aniline hydrochloride. Partial solubility of the precipitate therefore indicates the presence of both wood pulp and Neradol D.
The quantitative determination of sulphuric acid—the detection and estimation of which in leather is important—is considerably influenced by the presence of Neradol D. Practically all methods in vogue dealing with its determination were based on the estimation of the sulphur introduced into leather by sulphuric acid. The presence of Neradol D, the main constituent of which is dicresylmethanedisulphonic acid, renders it impossible by such methods to determine whether the combined sulphur owes its origin to sulphuric or sulphonic acid. It remains yet to be determined whether the sulphonic acid influences the leather substance to the extent that sulphuric acid does; it must, however, be borne in mind that Neradol D in addition to free sulphonic acid also contains sulphonates and sulphates, which may enter into the leather and thus increase the sulphur contents of the latter. A method must hence be devised which estimates the free acid only and provides the means of distinguishing this from all other acids of organic and inorganic acids. Paessler, [Footnote: Collegium, 1914, 527, 126; 531, 509; 532, 567.] by extracting the leather and dialysing the filtrate, has effected a separation of the acids and the tanning and colouring matters and quantitatively estimated the sulphuric acid in the dialysate.
Immerheiser [Footnote 1:Collegium, 1918, 582, 293.] devised a method, based upon the property of sulphuric acid of combining with ether, for the purpose of determining free sulphuric acid in leathers:—10 gm. of the leather, cut into small pieces, are extracted three times with 200 c.c. distilled water at room temperature, the time of each extraction being ten to twelve hours, and the combined extracts evaporated to dryness on the water bath, 5 gm. of quart sand being added. The dry residue is now powdered, introduced into an Erlenmeyer flask provided with a glass stopper, and 200 c.c. of anhydrous ether [Footnote 2: To be tested for water by shaking with anhydrous copper sulphate.] added. After about two hours, during which the flask is occasionally shaken, the ether is poured through a filter, the residue washed with a little ether, and the operation repeated twice with each 40 c.c. anhydrous ether, using the same filter. To the combined ether extracts (about 200 c.c.) HCl and [Greek: b]aCl_2 are added, the ether distilled off and the residue evaporated on the water bath, in order to decompose the ether-sulphuric acid compound. 50 c.c, of hot water acidified with HCl are now added, the precipitate allowed to settle, filtered, washed, dried, and weighed. The sulphuric acid thus estimated was present in the leather as free sulphuric acid. That present as sulphates soluble in water is estimated in the residue on the filter: the residue is extracted with hot water, the sand filtered off, the filtrate acidified with HCl, boiled for one quarter hour and filtered if necessary. The clear filtrate, which may be coloured, is brought to boil and [Greek: b]aCl_2 is added. The barium sulphate indicates the sulphuric acid present in the leather as water-soluble sulphates.
Whether the latter be sulphates or bisulphates may be indicated by the aqueous extract of the above residue, since neutral reaction would indicate the absence of bisulphates, acid reaction their presence in addition to possible normal sulphates; the quantitative estimation of the metals would decide this point definitely.
10. Properties of Leathers Tanned with Neradol D