72
REVIEW O F IXDVSTRIAL CHEMISTRY.
it will he found that they are within 5% of the real value in all the figures, ancl mitliiri 3$ in the first five columns, oak, hemlock, etc. From this it may be seen that the error in the execution of this method in ascc1rt:iining the percentage of tannic acid in an oak, hemlock, siirnacli, ctc., would not excetd one 1' of one per cent., while in the cst,irnatioii (Jf catechu, kino, etc., the error is quite large. Thc cause o f this is that the tannate of copper precipitated from these last materials is contaminated with considcral)le other matter, and besides this tlic peculiar principles preseiit i n these materials excrt a solvent action upon the tanriatc of coi)perr. This method niay b e iisetl for these last deterniin:ttions, hiit tlie kino niay be more accur;ttelp ctetcrmined by Lewentlial's mc'tliocl. This metliod Iias been in use iii nu? laboratory ever since I first investigated it, and the nunicrons analyses I ani called u1)otit o make of tanning materials anti csccuted by it give tlie iitriiost satisfaction. I will continue to use it in all niy leatlier researches 11ow about to be coinmeiioeil, also in commercial work. I n conclusion I wish to ,tender ~ n tlianks p to Mr, Jackson S. Schiiltz fur valuable advice, and to d l ot1ic.r.; w l i ~f;tvIJrctl me w i t l i illaterials for this rese~i.cli,a ~ i dfst.ilitnted it.
REVIEW OF INDUSTRIAL CHEMISTRY. 13Y.
A, A.
1SIcl:YsE~rav.
Scwiii.ixic iiciix*--JJtotye has undertaken to study agairit he plienonirtia of the lead clinniber in order to test the coiiclusions put forward by R. W e h e r (t) in 1Sri: as to the action of SO, on NO am1 S , O B . He finds that SO2 aiid SO tlo not react i i p n one anotlier, e ~ c i at i 100° (', whc'ti both arc' dry, 1 J l I t in presence of water tiley act sloaly, thc I-eaction requiring 48 Iioiirs f o r its coml)letion at S , O is fGrined: but the retliiction docs not cstend further, no ir; lieing detected. Srilpliuric nc.iiI of 1.45 sp-gr, Iltw not hasten the reaction unless free 0 is also present. K 2 0 is 1~rodiicedin the latter case even when 0 is iu es nf tlic1 amount rcqtiitwl by the reaction 2 SO,+d S O f 3 0 + 3 H z O = 2 H, SO, + 2 I I S 0 2 . In tlie normal condition of tlic ch;imler both steam :tn(l 0 are in excess and a loss of nitlogen corresponrlitig t,o t h e iiitrntc used ,in
("1 IXiitr. Jour. 243.1; Bel,. D. Cli. G c s 14-2196. (I) l ) i t i , r .Jour. 184-246.
Cliem. C. El. Dcc. 7, '81.
REVIEW OF INDUSTRIAL CHEMISTBY.
73
the pyrites burned must result, as N,O is not absorbed by strong sulphuric acid in the Gay-LuRsac tower. The author also describes a new form of gas burette used in the investigation. Xaske and Belaher (*) propose to reduce the waste of nitric acid in the chamber process by two-thirds through the introduction of SO, at the outlet of the, last chamber. NO, being reduced by this means to N,Os which is more soluble in H,SO,, complete absorption occurs in the Gay-Lussac tower. Richter (t) effects thorough mixture of the gases of the lead chamber by aspirating them through one opening in the wall of the chamber and injecting them again at another. A steam jet is used for the purpose. SODA.-Scheurer-Kestner(f) discusses the method of Pauli (5) for the ,oxidation of soda lyes. The oxidation of sulphites to hyposulphites and sulphates through the action of MnO, is considerable but still incomplete at a t,emperature of 7 5 O . RamrneZsberg (11) finds in the soda liquors from the manufactory of Schoenebecker, peculiar red and yellow crystals containing vanadium and yielding, on re-crystallization, colorless octahedra of the general formula, N a F 2 Na, RO, 18 H20, in which R may be P or V. He ascribes the origin of the phosphorus to the limestone, the ash of coal arid to the clay of the furnace, the latter being also the source of the vanadium. The same author(?) finds crystals of Gay-Lnssite ( N a 2 C 0 , C a C 0 3 5 H,O) in soda liquors from the above works a n d ascribes to the formation of this substance one o € the principal losses of soda in the Leblanc process. Reic?emeister(t+) finds the sanie substance t o separate from crude soda 1yes during carbonation, but n c w r from the fully carbonated liquor. I t also occurs in the lime mud of the causticising vats in the inmufacture of caustic soda. It is insolnble in water, but is decomposed by prolonged action of cold water, more readily with the aid of heat. I t forms most nbnnda:itly in concentrated caustic liquors. An anhydrous soda-lime carbonate occurring in over(*) Coinptes Reudus, 03-181.
(t) Diiig. Jour. 243.1.
Diug. .Joui,. 243.1.
($) Ding Jour. 235-390.
($) Comptes Reiitlms, 93.878. (11) Diiig. Joru. 242.4.
P-)
( '
"
"
(tt) Diiig. Jour., 2$3.-4.
Ding. Jour. 242.4.
74
REVIEW OF INDUSTRIAL CHEMISTRY.
heated or " burnt " balls in the black ash process gives crystalline structure to the inass and hinders subsequent lixiviation. The temperature of the black ash furnace shoulcl therefore he maintained a t a point below t h e melting puiiiL uf this clonble c*arl)oii,ite W.Smith a n d T Lidtlb ,*) have shown that the 1 w of soda in t h e residue left from the lixiviation of black ash may be I r w n e d , and the soda r w o i ered by prolonged digestion with cold N ater, which decoinposes the insoluble G;iy-Lussite s i Soda wa5te '* 1ic:ited one hour at GOo yielded 22 per cent, Sa,O out of 3 4 pcr cent of soda present, arid a ramplc of causticising mud yielded by the iame treatment 2 62 per cent of soda, while 2 5-3 per cent. rcniained insoluble. By ushg this mud t o replace lime i n the balliiip process the insoluble soda is recovered, but M hen t h e mud is rejected a loss as high as 7 per cent. of soda ~ i i a occur. j Wright ha5 already shown that the total loss of Xa,O 111 t h c Leblanc proweas may anioutit to 20 per cerit. The writers confirm tliv btaeeiiient of Scheurer-Kestner that an excesea {Jf lime 111 thc balling furnace favorb the pfoduction of insoluble compoiinds of soda duriiig lixiviation. The manufaclure of soda by the ammonia piocesr of Solvay has been improved byNonigrrza?i(t), who employs a moderately elevated temperature in the absorbing vessel, securing by this means a granlar precipitate of bicarbonate instead of the slimy mud commonly produced in the cold. The precipitate is easily washed. After washing, it is pressed in the cakes which are decarbonated in an upright furnace, on the grate of which the cakes ale exposed to a current of hot CO, from the generator The dry powder falls through the grate, and the additional volume of (20, obtained is carried t o the absorber. Improvements ir, the apparatus of the ammonia procebs have also been made by JfodDlctnc and Gnulcircl Pechilzey ( 5 ) and by the Societe AiLoizynie de Prochiits Chinziyice de P u r L I/ ) Ortlich and MZLZZ(r) W apply the method of Soliay to the production of potassium carbonate, also through the substitution of trituethylamine f o r ammonia. Triniethylnrnine, through the recent discovery of Camille Vincent, has become an abundant commercial product, being made
(I),
* Chem. News, No.
43.
(t)Ding. Jniir., 243.-1.
($, 11). (11) Ib. Bul. SOC.Cliiniiqiie, J:rii. 5tll. '82.
(Sj Ding. .Jour. 243.1. (w)
Ding. Jour., 2 4 2 . 4 .
REVIEW OF INDUBTRIAL CHEMISTRY.
75
from the residues of beet root molasses. A single firm, Tilloy & Dulanne, of Coumeres, turn out 1800 kilos of crude salts of trimethylamine per day. A current of CO, is paseed into a solution of equal equivalents of potassium chloride and neutral trimethylamine hydrochloride a t 239 C. and potassium carbonate (KHCO,) is precipitated. The reaction is limited by the inverse reaction, but this difficulty is overcome by operating under pressure. An excess of trimethylamine (2.22 molecules to 2 KC1) has been found t o increase the yield, Liciigle (*) ha8 directed the examination of several reactions which have been suggested as indicating new methods of making soda, o r of improving existing methods. The results are given as follows: 1. The action of Al,O, on NaNO, at high temperatures with recovery of the nitric acid causes rapid attack of the vessels (platinum, iron and glass used) and ” 0 , is only partly recovered. The reaction is less available for manufacturing purposes than the earlier one of Schiappi, in which CaCO, and XaNO, are used. 2. The decomposition of sodium sulphate by a solution of calcium bicarbonate (Pongowski’s method) (t) was found impossible using a three-fold quanlity of pulverized marble, acting for ten hours upon sodium sulphate in a solution saturated with CO,. 3. Aarland’s process for substituting CaCl, for MgCl, in treatment of soda waste by the well known method of Schaffner aud Helbig failed entirely when tried in the laboratory. CaCI, decomposes Ca S only after prolonged boiling, a result which may be obtained with water alone. POTASH.Grunebery ($) reviews the progress of the Stassfurt industry in its relation to the production of potassium sulphate from the complex salts and mixtures of the natural deposit, He discusses a list of 20 patents which have appeared since 1877, and classifies them as follows:1. preparation of Schoenite (MgSO,, K,SO,GH,O) from Kieserite (MgSO,) and KCI or Carnallite ( K Mg C1, 6H, 0) 2. Preparation of Schoenite from Kainite. 3. Working of mother liquors for by-products, 4. Production of K,SO, from Schoenite by methods other than those depending on decomposition of HCl. The author concludes that a combination of different Drocessea (*) Ding. Jour. 243 Heft. 2. (t) French Patent, Mar. 27, 1873. ($) Ding. Jour. 248 Heft. 1.
76
ABSTRACTS.
will be found best in practice. Iri all processes it is advisable to use a minimum o f water, and to have all waste liquors as rich in MgCl,, and as poor i n potassium salts as possiblc before they are rejected. All methods of preparing potassiuni siilptiate from these salts must compete with the direct methotl of the Leblanc process, by which the alkaline chloride is converted into sulphate, and are at an additional disadvantage ill comparison with it, because of the loss of HCI in the waste liquors.
ABSTRACTS. Abstrncts from the Comptes IZcnd~s,by A. Bourgougnon.
Complex Function of Morphine, and its Transformation into Picric Acid; also its Holubility. BY 31. Crrzwr2iix(-+,No. 1. (Jan. 2nd, 1882).-Action of allcalics. Potassa, soda,baryta and lime dissolve morphia in the proportion of oiie equivalciit of morphia for one equivalent of base. The solutions evaporated in a vacuum give crystallized products contaiiiing oiie cqiiiv:~lentof base, one equivalent of morphia and t,wo equivalcnts of w t t e r . Action of Nitric acid. Tetr:tliydrntetZ nitric. acid at a temperature of 100° C. transforms morphia into :in acid with the formula C, oII,8 N , 0 , *, a tetrabasic acid ci.ystallizing with difficulty. Baryta and lead salts of this aciJ c:ontaiiietl S 11,O. Nonohydrated nitric acitl, i n senlerl tubes at 10O2 Cy. transform the acid C,,II, *S20,i n t o ~ ~ i c x~i di .~ i ~ ~ Solubility of iiiorpliia. 1 1iti.c. of w:Lter at, Ui' ('. dissolve traces Qf morphia, a t 10", 0 gr. 10; at 2 0 h ' ~ r 2r'l; , at 40;' ( I gr. 40, of crystallized morphia. 'The soliibility (if iiioq11ii:i st -Nois then represented by a straight line, but : , b o ~ e4.5'' tlic. soliibility is represented b)- :i larger nnmber tlinri the e l e ~ a t i o nof t,empcrature. From 450 to 100" the curve of solubility affects :t parabolic f o r m Carboiiic Ether of Borneol. B Y ,PI. II,ir,r,En. No. 2. Jan. 9th, 1SRP.-This ether was found in the residues of preparation of the compound described by the author under the name of llorneol Cyane. When pure it affects the form of very light white needles or hexagonal tables, irisoluble in water and the alkalies, not very soluble in cold alcoliol, soluble in boiling alcohol, ether, chloroform, benzine, glacial acetic acid. Melting point 21 5. C. and sublimes without decomposition. Melted with caustic potash it gives potass i c m carbonate and borneol.
