Proposed m ethod for the determ ination of the enzym e value of artificial bating m aterials. V.
Kubelka and J. Wa g n er (J. Soc. Leather Trades’
Cliem., 1926, 10 , 432—443).—The bating material is taken up with distilled water a t 37°, filtered, the insoluble residue dried and weighed. I t is examined microscopi
cally for sawdust or ground straw and chemically after ignition for weighting materials. Ammonium sulphate and chloride should be determined in the filtrate. The enzymic activity of the latter should be determined on a 0-05% casein solution in a series of 10 tubes arranged in a thermostat maintained a t 40°. Ten 1 c.c. graduated pipettes fixed in a frame are connected with each other a t their upper ends by a T-tube, each being fitted with a stopcock. An automatic pipette holding 1000 c.c.
in its bulb portion and 5 c.c. in the stem is used to deliver 5 c.c. of the casein solution to each of the ten tubes, 1 c.c. of distilled water being added to each tube from a series of ten pipettes. When the tubes and contents have reached 40°, measured quantities 0-1—
1-0 c.c. of enzyme solution are run in from a second series of pipettes. The tubes are kept a t 40° for 30 min.
after running in the enzyme solution, cooled to 15—20°, and 0-5 c.c. of 0-25% acetic acid solution is run into each tube from a third series of pipettes. The tube which shows only a very faint opalescence and no Tyndall effect with transm itted light marks the end
point. The amount of casein digested by 1 kg. of the bate can then be calculated. This apparatus enables the comparative digestions to commence simultaneously, arid thus avoids errors due to separate pipetting.
D. W o o d r o f fe . Extraction of tanning m aterials u sin g a m odified T e a s ’ extractor. H. E . W illia m s (J. Amer. Leather Chem. Assoc., 1927, 2 2 , 97—102).—A 2500 c.c. flask is fitted with a Teas’ extractor (cf. B., 1905,1055) the cock of which is soldered tight, and in the side of the tube above the cock a smaller tube is soldered to allow a thermometer to be inserted into the material to be extracted. A flanged copper pipe is soldered to the top of the extractor, and into this pipe is set a stopper carrying a condenser, the upper end of which is connected to a glass tube set in a 3-hole stopper in the neck of a 2-litre receiver attached to the delivery tube of the extractor through a tube set in the second hole in the stopper. The third hole is fitted with a tube leading to a vacuum break, which is connected by means of a T-tube to a filter pump. To extract a t temperatures below 100°, the pump is started and the vacuum break adjusted so th a t the temperature of the boiling water is th a t desired. The vacuum break can also be used as a pressure gauge for extracting under pressure a t temperatures below 100°. D. Wood ro ffe.
Leather d yeing. V. II. S a l t (J. Soc. Leather Trades’
Chem., 1926, 10, 468—470).—Samples of skivers were tanned with 12 different vegetable tanning materials and one synthetic tannin respectively, and then dyed with 0-25% and 1% titanium potassium oxalate, 0-5% ferrous sulphate, a mixture of 5% ammonium acetate and 0-5% ferrous sulphate, and various acid and basic dyestuffs respectively. The treated leathers showed little variation in shade between one tannage and another, except th a t due to the original colour of the leather. Valonia-tanned leather took up less dye- stuff. Only sumach-tanned leather gave a grey with iron ; other tannages showed no tendency to a black.
. D. W o o d r o f fe . Effect of tim e and tannin on the analytical resu lts, yield, cut, and colour of [sole] leather. C a s te and E . P a r s y (J. Soc. Leather Trades’ Chem., 1926, 10, 471—476).—Samples of sole leather which had been tanned for 15 days in liquors (d 1-004—1-045) consist
ing of f quebracho and J chestnut extracts, then for 36 hrs.
in equal parts of quebracho and chestnut extract liquors (d 1-075) were dried, and submitted in sets of three to immersion in chestnut extract (d 1-074) a t 17—20° (a) alone, (b) with 0-8% of added sodium bisulphite
solu-B ritU h C h em ica l A b tt r a c t*— solu-B .
Cl. XV.—L e a t h e r ; G l u e . 261
tion (d 1 • 320), (c) with ground oak bark, and (d) with a solution of 10% acetic acid respectively. Samples were withdrawn in each case after 11,30, and 60 days’ immer
sion and analysed. The increase in the weight of the leather was less with ground bark than without it. The acetic acid treatm ent made no difference. The degree of tannage was greatest with the bark and extract.
The colour with bisulphite and chestnut extract was better than th a t of chestnut alone or with bark. The cut was slightly darker with the oak bark. The analyti
cal results show th a t the use of sodium bisulphite with chestnut extract as a vatting liquor is superior to chest
nut extract alone or with oak bark as regards yield of leather, the preservation of the liquors, and the colour
of the tannage. D. Woodroffe.
A cidity of chrom e[-tanned] leather. K. H.
Gustavson (J. Amer. Leather Chem. Assoc., 1927, 22, 60—69).—Treatment of moist or finished chrome-tanned leathers with a 3—5% pyridine solution for 16 hrs.
removes the sulphuric acid combined with the collagen, but does not affect the sulphato-chromium complex.
The two-bath chrome-tanned leather contained a complex of higher acidity than th a t of a one-bath leather tanned in a moderately acid chromium sulphate at relatively low concentration and without any addition of sodium sulphate. The addition of the latter to a one-bath chrome-tanning liquor, followed by heating the same, produced a chromium-collagen complex of similar or higher acidity than th a t of the two-bath chrome-tanned leather. I t is suggested th a t the electro
negative chromium complexes associated with the basic groups are more easily hydrolysed than the ordinary sulphato-chromiuni-collagen complexes. Solutions of chromium chloride of moderate concentrations and 50—70% acidity gave leathers containing a cliloro- chromic complex of about 10% acidity. With extremely basic chlorides the acidity was only 4-2% . Addition of neutral chlorides to the basic chromium chloride tanning liquors did not cause much increase in the acidity of the chloro-complex. Chromium sulphate liquors gave a diminished acidity of the sulphato- chromiuni-collagen complex with increased basicity.
Addition of sodium sulphate to the sulphate liquors increased the acidity of the complex, i.e., caused a migration of sulphate groups into the internal sphere.
A basic chromium sulphate liquor (acidity 60%) con
taining organic acids from the reduction process gave a leather With acidity 62-1% before and 19% after pyridine treatm ent. The organic acids must have replaced some of the sulphate groups in the complex, since the latter is usually 30%. The addition of formates and acetates to chrome-tanning liquors diminished the acidity of the complex from 29-4% to 16-0% in a 63%
acid chromium sulphate. Acetates diminish the tanning power of both chloride and sulphates of chromium.
Formates added to sulphate liquors to give -ph 5-0 yielded an excellent tanning agent, but with decreased chromium fixation ; in chloride liquors in quantities up to 1—1 -5M there wTas nearly double the fixation of chromium. These experiments prove the existence of acidic groups in direct combination with chromium in chrome-tanned leathers. D. Woodroffe.
N ew m ethod of chrom e tannage. M. S iiim idzu (J. Amer. Leather Chem. Assoc., 1927, 2 2 , 93—97).—
The pickled hides are drummed with 3% of potassium dichromate and 150% of water, hung up to drain, trans
ferred to a fuming chamber of sulphur dioxide, left until completely reduced, and afterwards neutralised in the usual wTay. The leather produced compares favourably with th a t tanned by the ordinary methods. There is an economy in time, labour, and material. Only 1% of sulphur (on the hide weight) is required to be burnt to produce the sulphur dioxide necessary, instead of 3% of acid and 6% of sodium thiosulphate. D. W o o d r o f fe .
“ A g e in g ” of chrom e[-ianned] leather. K. H.
G u s ta v s o n (J. Amer. Leather Chem. Assoc., 1927, 2 2 , 102— 105).—Samples of leather tanned with a one-bath chrome liquor of the cationic type and by the two-bath tannage using sodium bisulphite as the reducing agent, respectively, were allowed to age, and portions analysed after different periods to determine the acidity of the sulphato-ehromium-collagen complex in the leather.
The j>u value of the water was determined after it had been 24 hrs. in contact with the aged leathers. The chromium complex in one-bath chrome leather had 29-5% acidity without ageing, and diminished to 2 4 -4 % after 2 weeks’ ageing. The value of the water was 3-12 on the original sample, and 2-96 after 6 weeks’
ageing. The acidity of the chromium complex in two- bath chrome leather was 27-8% , and remained practically constant during ageing. The f n value of water in contact with the samples of two-bath chrome-tanned leather diminished from 3-98 in the original, to 3-0 after 3 weeks’ ageing. The acidity of the sulphato-chromiuni- collagen complex in two-bath chrome leather was only slightly greater than th a t of the one-bath leather. The amount of acid removed by pyridine treatm ent was greater from two-bath than from one-bath tanned leathers, bu t there is 7 times as much hydrolysis with the latter. The acidity of the cationic chromium complex was about the same for both tannages. Probably the sulphato-groups in the anionic complex are more labile, and those in the cationic complex may serve as connecting links with the protein. On ageing, chrome- tanned leather does become more acid. D. W o o d r o f fe .
Pa t e n t s.
Tanning a gen ts. I. G. Fa r b e n i n d. A.-G. (G.P.
433,163, 26.8.24. Addn. to 420,647 ; B., 1926, 456).—
The oxidation products obtained by treating fossilised vegetable m atter with oxidising agents such as nitric acid or nitrous fumes are replaced by the oxidation products of lignite, brown coal, peat, etc. The formaldehyde condensation products of naphthalenesulphonic acids or their salts are wholly or partially replaced by other synthetic tannins containing one or several sulpho-groups in the molecule. The dry oxidation products obtained by the action of nitric acid on lignite are mixed with the sodium salt of the formaldehyde condensation product of naphthalenesulphonic acid. This mixture gives a bright Teddish-brown leather with a good feel. By replacing the sulphonic acid partially or entirely with the condensation products of naphthalenesulphonic acid and sulphur, or sulphur and phenol, or glycollic acid,
Cl. X V L —AQMODI.TTOK.
or cresolsulplionic acid and formaldehyde, and neutral
ising to a suitable acidity, the product tans a bright coloured leather. A mixture of equal parts of a 20%
solution of the tannin obtained by oxidising brown coal with nitric acid, and a concentrated solution of the formaldehyde condensation product of cresolsulplionic acid, after diluting with water, gives a well-filled, pale brown coloured leather. D. Wo o d r o f f e.
T anning agen ts. I. G. Fa r b e n i n d. A.-G. (G.P.
433,162, 29.6.24).—Fossilised material of vegetable origin, e.g., coal, brown coal, humus coal, or peat, is treated to remove the iron content by stirring the finely-powdered material with 20% sulphuric acid and heating. The product is filtered, washed with water, and the damp or dried residue used in the manufacture of tannins. The removal of the iron increases the yield of tannin when the material is oxidised, and the product gives brighter coloured leather, especially when mixed with vegetable tannin extracts. D. Wo o d r o f f e.
XVI.— AGRICULTURE.
D eterm ination of the m anurial requirem ent of s o ils. Ge r l a c h (Landw. Jahrb., 1926, 339—368 ; Bied. Zentr., 1927, 56, 58—60).—Comparison is made of the methods of Lemmermaiin, Neubauer, and Mitscher- licli. All soils, except peats, possessed insufficient reserves of active nitrogen compounds, and in most cases the amounts of available potash and phosphate present were such th a t ordinary dressings of farmyard manure sufficed. P eat soils were usually deficient in potash.
Light sandy soils needed lime, especially for barley and wheat and on pastures, and were usually lacking in phosphate. Farmyard manure was not adequate to remedy this deficiency for wheat crops. Interrelation
ships between the total phosphate, citric-soluble phos
phate, phosphate utilised by crops in field trials, and the root-soluble phosphate (Neubauer) were not apparent.
The value of adequate basal manuring with phosphate and potassium salts and the application of nitrogenous
material as a top-dressing is emphasised.
A. G. Po l l a r d.
N itrogen-m anuring, and the profitable cultiva
tion of cereals. 0 . No l t e and R. Le o n h a r d s (Mitt, deut. Landw. Ges., 1926, 27, 563 ; Bied. Zentr., 1927, 5 6, 60—63).—Field trials with rye showed profitable results from the use of ammonium sulphate. Best results followed early application of the fertiliser. When used as a spring dressing the optimum quantity of fertiliser remained the same, bu t the yields were smaller.
When applied in early summer, ammonium sulphate produced still smaller yields, and no relationship was here apparent between the quantity of fertiliser used and the crop return. A. G. Po l l a r d.
Phosphate m anuring. O . No l t e and R. Le o n h a r d s (Mitt. deut. Landw. Ges., 1926, 34, 701 ; Bied.
Zentr., 1927, 56, 63—66).—Records of field trials of various phosphate fertilisers with different crops are recorded. For winter-sown cereals better crops resulted from spring application of phosphates than when applied just previous to sowing. A. G. Po l l a r d.
D eterm ination of m ineral nitrogen in fertilisers.
C. H. Jo n e s (Ind. Eng. Chem., 1927, 19, 269—271).—
The following method gives reliable results in the
determination of nitrate nitrogen in presence of cyan- amide or carbamide. 4 g. of fertiliser are dissolved in 200 c.c. of water and filtered. In one 50 c.c. portion ammoniacal nitrogen is determined by distillation with magnesium oxide. Another 50 c.c. are warmed with 2 g. of reduced iron and 10 c.c. of dilute sulphuric acid, diluted, cooled, and 100 c.c. of concentrated sodium hydroxide solution added. I t is then a t once distilled and the ammonia determined. A correction blank is carried through without any reduced iron. The differ
ence accurately represents the nitrogen present as nitrate.
The large excess of sodium hydroxide is necessary to minimise any action of the hydrogen other than on the nitrate. Tests on mixtures prepared in the laboratory gave much more accurate results than the U.S. official
procedure. C. Ir w i n.
O xidation of organic m atter and nitrification in sterilised so ils kept for a long period in contact w ith oxygen . E. P a r i s i and G . C a r b o n c i n i (Annali Chim. Appl., 1927, 17, 45—52. Cf. B., 1926, 641).—
Degradation of organic m atter and nitrification are favoured by the presence in the confined atmosphere of a considerable proportion of oxygen. P lant life being hampered or impossible under such conditions, the experiments now described aimed a t ascertaining if the oxidation phenomena observed are due to the microflora of the soil or to chemical action of the concentrated oxygen. The oxidation is due principally to biological phenomena, which are always accompanied by chemical phenomena. Soil repeatedly sterilised in an autoclave a t 130° absorbs far less oxygen th an th a t sterilised by treatm ent with antiseptics. When the space containing the soil is limited, the atmosphere is free from carbon dioxide a t the end of the experiment. Hence, a t the ordinary temperature and in presence of antiseptics, the chemical oxidation of the organic residues of the soil is caused mainly by substances which are altered when heated, and are, perhaps, analogous to those occurring in pulped leaves (cf. Ciamician and Ravenna, A., 1919, i, 58, 140). The formation of nitrates is arrested completely, or almost so, by the action of antiseptics, so th a t the oxidation of ammonia in soil in contact with oxygen is due to micro-organisms. T. H. P o p e .
Properties of soil colloids. A . N . S o k o v o l s k j i
(Pochvovedenie (Russian), 1924, 19, 59—79).—Elimina
tion of calcium from soils by replacement brings about a condition whereby extraction of such soils with distilled waiter brings into pseudo-solution some of the soil colloids. The structure of the soil is destroyed by such treatm ent. By continuous extractions and décanta
tions a certain fraction of peptised mineral and organic substances may be separated. By treating the residue with hydrogen peroxide another peptised fraction may be obtained. The first fraction is known as the active and the second as the passive. The absorbed calcium serves as a coagulator of the sols present, and liming serves the purpose of preserving the soil colloids.
Ch e m i c a l Ab s t r a c t s.
Colloid ch em istry of s o ils. E. Trtjog (Third Colloid Symposium Monograph, 1925, 22&—240).—A new ultrafilter and a colorimetric method of determining ps in soils are described. Ch e m i c a l Ab s t r a c t s.
Pow er of so ils to absorb w ater from air. F. J.
B r itis h C h em ica l A b s tr a c ta —B .
Cl. X V I I .— S u g a r s ; S t a r c h e s ; G um s. 263
Al w a y (Third Colloid Symposium Monograph, 1925,
241—246).—Davy’s view (1814) th a t the power of soils to adsorb water from air is much connected with fertility seems to be fully substantiated, but the ability of soils to adsorb water vapour is not a trustw orthy measure of their colloid content. Ch e m i c a l Ab s t r a c t s.
A dsorption b y activated sugar charcoal, with particular reference to soil acidity. E. J. Mi l l e r
(Mich. Agric. Exp. Sta. Tech. Bull., 1925, 73, 1—60).—
A discussion of the nature and origin of soil acidity, based on work previously published (A., 1922, ii, 741;
1923, ii, 464; 1924, ii, 734; 1925, ii, 656 ; Mich. Agric.
Exp. Sta. Quart. Bull., 1925,8, No. 1, 37). The charcoal and soil systems are similar, but not perfectly analogous, in behaviour. Hydrolytic adsorption of the acids of salts with loss of the bases by leaching, promotion of
“ negative ” adsorption of bases by surface-tension effects, promotion by carbon dioxide of the adsorption of acids, displacement of adsorbed acids by neutral salts, and the irreversibility of the adsorption process with resulting apparent insolubility of such adsorbed acids, have been demonstrated for charcoal.
Ch e m i c a l Ab s t r a c t s.
Significance of nitrogen in so il organic matter relationsh ips. F. J. Si e v e r s and H . F. Ho l t z (Wash.
Agric. Exp. Sta. Bull., 1926, 206, 1—43).—Nitrogen accumulates in a soil only as a result of legume fixation, free fixation, and precipitation. The nitrogen : carbon ratio is stable, and the contents of these two elements indicate th a t of the organic m atter. Abundant precipi
tation and high temperature, which promote the accumu
lation of organic m atter, are also most effective in promoting its decomposition. In the process of decom
position of plant residues in the soil there is a tendency for the nitrogen : carbon ratio to be narrowed until it approaches th a t of the micro-organisms responsible for the decomposition. For the measurement of the decomposition the carbon dioxide evolved and the nitrate accumulated were measured.
Ch e m i c a l Ab s t r a c t s.
M obility of soil com pounds, and influence of calcium thereon. K. K. Ge d r o iz (Nosovsk [Russia]
Agric. Exp. Sta. Bull., 1926, 43, 1—18).—The calcium ion is beneficial in both acid and alkaline soils, in the former by preventing the hydrogen ions from rendering the soil unsaturated, and in the latter by preventing the sodium from getting into the colloidal fraction of the soil. Ch e m ic a l Ab s t r a c t s.
Im proved stain for bacteria in soil. H. J. Co n n
(Stain Technol., 1926, 1, 125—128).—A suspension of soil in a 0-015% gelatin solution is dried on a slide, treated for 1—3 min. in 40% acetic acid, washed, and dried on a boiling water-bath, and while still on the bath is stained for 1 min. with 1% aqueous rose bengal.
H. W. Du d l e y.
M echanical an alysis of soil by the method of decantation w ith w ater. M. Fil a t o v (Pochvovedenie [Russia], 1925,20, 33—41). Ch e m ic a l Ab s t r a c t s.
Pa t e n t s.
Producing artificial [nitrogenous] manures.
Si e m e n s & Ha l s k e A.-G. (E.P. 245,768, 5.1.26. Conv., 9.1.25.).—Carbon monoxide, ammonia, and chlorine are
allowed to react with each other in such a manner as to produce nitrogenous compounds. In the preferred method phosgene is first produced from carbon monoxide and chlorine, and then allowed to react with ammonia or an ammoniacal solution. By varying the proportions of the reacting materials a mixture of carbamide and ammonium chloride, or a mixture of ammonium chloride, carbamide, and such compounds as cyanamide, cyanurie acid, etc. may be obtained. G. W. Ro b in s o n.
Manufacture of alkali-nitrogen fertilisers having carbam ide as their base. J. Br e s l a u e r, Assr. t o Co m p, d e l’Az o t e e t d e s Fe r t i l i s a n t s S.A. (U.S.P.
1,618,266, 22.2.27. Appl., 22.6.25. C o n v ., 26.6.24).—
See F . P . 600,016 ; B ., 1926, 417.
Manufacture of nitrogenous fertilisers. E. H.
Ric h a r d s and II. B. Hu t c h in s o n, A s s r s . to Ad c o Lt d.
(U.S.P. 1,619,679, 1.3.27. A p p l., 15.4.24. Conv., 23.4.23).—See E.P. 219,384 ; B., 1924, 801.
XVII.— SUGARS ; STARCHES; GUMS.
Factors influencing char filtration [of sugar solution s]. E. W. Ri c e and G. W. Mu r r a y, j u n.
(Ind. Eng. Chem., 1927, 19, 214—215).—Aqueous solutions of various salts which might be present in raw sugar were percolated through refiners bone char a t the rate of 150 c.c./hr., and successive 50 c.c. portions tested by conductivity determinations. The temperature was maintained a t 11°. The adsorption varied from over 95% with calcium hydrogen phosphate to practically nil, even in the first portion, with sodium chloride.
This was from a 2% solution in each case. The results are disturbed by the adsorption of water and the variation of adsorptive power with different concen
This was from a 2% solution in each case. The results are disturbed by the adsorption of water and the variation of adsorptive power with different concen