US1376207A

US1376207A - Process i

Info

Publication number: US1376207A
Authority: US
Publication date: 1921-04-26
Anticipated expiration: 1938-04-26

Description

c. B, JACOBS. PROCESS FOR THE PRODUCTION OF COMPOUNDS BY GAS REACTIONS AND APPARATUS KNEBEFOR.

APPHCATION FILED SEPT-27, I919.

mum Apr. 26, 1921.

13 Suva-whoa; C 5. JZz c 0/66,

2 SHEETSSHEET I C. B. JACOBS. PROCESS FOR THE PRODUCTION OF COMPOUNDS BY GAS REACTIONS AND APPARATUS THEREFOR.

APPLICATION FILED SEPT.27, I919.

Patented Apr. 26, 1921;

2 SHEETS-SHEET 2- F F I 1 1 I5 0 i v IIIIIJ amvawtoz C 5. Ja cabs,

35 Mom 1M CHARLES B. JACOBS, F l/VlILllIINGZEf/N, DELAWARE, .ASSIGNOR TO E. I. D FONT DE l LolTOURS a CUIEEPANEZ, 0F W'ILMENGION, DELAWARE, A CORPORA OF BEILJZUJVARE. v

PROGEFW FOR THE PRODUCTION OF COItiPQUNDS BY GAS REACTIONS AND APPARATUS THEREFOR.

y gg'gg fg, gfl Specification of Letters Patent. Patqgnt d A 2 1 2 Application filed September 27, 1919.

To all whom 711 may concern: v

ii. known that l, Gunners l3. Jnoons, you of the United States, and a resioi' Wilmington, inithe county of New I see ed i ltate of Delaware, have invented z certain. new and useful Process for the *duOion Compounds by Gas Reactions and Apparatus 'lhereior, of which the t'ollowiu;g is a specification.

's H ivention relates to a process for the in oi compounds by gas reactions, etus therefor. More particularly, to a process of, and apparatus for, compounds by electrolysis, and, lads application in the fixation oi describe it with particular rerercnce [o the production oi nitrogen com; pounds. But, it will be understood that i do not restrict the invention to that particnlar art.

account of the extreme chemical in activity of free or elemental nitrogen, it has, heretofore, not been possible to make it c ihinc directly in any material quantlty with or oxygen or hydrogen, except by the ac 1 ot the electric are or the electric disch in the case of oxygen; or the in a ca'ralytic agent, in the ease oi oi the methods are,

on ,t oxids oi nitrogen by the I l auling', and similar arc the formation of ammonia nocess lint the commercial ope. of the are process .is confined to loom. where cheap power 1n large quantities iS :inihible, since its power efficiency nuiringg from 6.5 to 8 kilowatt the prmluction of one pound of I. or i s equivalent. rind the rlaber the direct union 0t nitrogen and to form ammonia, while very ethir m the standpoint oi power consumed, has up to the present time been of benefit only to those trained and by its originators. l have dem electrolytic process, and an ap- For the performance thereof, wheren can he fixed in suthcient quan- 'iently high current ciliis low Serial No. 326,763.

ciency, to make the production of nitrogen compounds, by this process, of commercial si -niiicance, and by the use of which various oi the diihculties of previous processes are avoided.

One object of the invention is to provide a process for the production of compounds by gas reactions.

Another object is to provide a process for the electrolytic production of nitrogen compounds.

Another object is to provide a process for the electrolytic production of oxids of nitrogen.

Another object is to-provide a process for the fixation of nitrogen in which an aqueous solution of an electrolyte is electrolyzed and nitrogen, introduced into the solution, oxidized in such quantities and with such current efiiciency as to make the process of commercial significance.

Another object is to provide apparatus suitable for use in, and for aid in, the pertormance of processes embodying the invention.

To these ends, and also to improve generally upon processes and apparatus of the character indicated, my invention consists in the iollowing matters hereinafter described and claimed.

Without restricting my invention thereto, I show in the accompanying drawings,

and describe, an apparatus embodying the invention and for'use in, and for aid in, the performance of processes embodying the invention. In the drawings F'igure 1 is a vertical, diametrical, section of a cell, substantially on line 1-1 2;

Fig. 2 is a horizontal section substantially on line 22 of Fig. 1, of the cell illustrated in Fig. 1, and

Fig. 3 is a conventional, diagrammatic, elevational, assembly view of an apparatus for the fixation of nitrogen and including a cell of the type illustrated in Figs. 1 and '2.

I have discovered that it a body of free or elemental nitrogen be finely divided, as into fine streams, and the divisions brought into intimate physical contact with active electrolytic oxygen and hydrogen at the moment of: their liberation, combination between the nitrogen and these gases takes place in suihcient quantity to make the production of nitrogen compounds, by a process based on the discovery, of. commercial significance. In utilizing this discovery I prefer to make use of porous electrodes for the electrolysis and to "force the nitrogen through the pores of the electrodes.

lVith. such a procedure, the great number oi? small pores in the porous anodes and cathodes serves to break up the introduced body oi nitrogen passing through the pores into such a line state or' division as to approach the ideal condition of having the nitrogen in solution in the electrolyte. ll ith the body in this finely divided state, the nitrogen comes into very intimate contact with the active electrolytic oxygen, or hydrogen, at the moment of their liberation on and within the anode, or cathode, and is in a condition to yield readily to oxidation and hydrogenation in the electrolytic cell. The greater the porosity and the smaller the individual. pores of the anode and cathode structures, the more nearly is the body of nitrogen subdivided into a state aoproaching a condition which, for the purpose, amounts to having the nitrogen in actual. solution in the electrolyte.

It will be seen that each stream of nitrogen as it passes along a pore is surrounded by oxygen, or hydrogen, and thus on one; mous extent of contact between the nitrogen and the oxygen and hydrogen is arrived at. The fineness of the porous structure of the anodes and cathodes which may be used is limited only by that degree oi fineness which would cause the passage or the nitrogen through the structure to force the solution out of the pores and thus stop electrolysis and, consequently, the l'. tion at or; on and hydrogen on the act! surfaces of the anode and cathode.

Various compositions for the porous anodes and cathi'ides, having the desired. rosity and electrical con-:uretivity and retaining these properties by virtue of their resistance to chemical action within a cell, may be used. For anode construction for use in acid unolytes, I have :lound porous graphited petroleum coke to give the best results. in alkaline anolytes, such as sodium hydroxir, solutions, line steel wool, ramn'ied into position in the electrode compartments, gives excellent results for both anodes a cathodes. For a wide variety oi? work, electrolytes oi varying composition, I have used satisfactorily graphitized petroleum coke for the construction of both anodes and cathodes.

l, shall now describe the i l tratefl cell, explain briefly one way of carrying on the process with the aid of the cell, and then note certain other matters, including results of certain of my experiments, as a further aid to the understanding of my invention. Referring now to the drawings The coil, whic i i desirably cylindrical in form, comprises the outer container 1, desirably glass, and the inner porous cup 2, say of ungiazcd earthen ware. The relative dimensions are such as to provide the annular space 3, the space shown having substantially one and one-half times the capacity of the cup 2. The cup 2, or cathode compartment, and the space 3, of the con tainer l, or anode compartment, are each partially filled with graphitized petroleinn coke, as 4- or 5, to give porous electrodes, each composed either of a large porous single piece as is preferable, or, if desired, of a large number of packed small porous pieces. Graphite rods as 6, (3, G, with suitable electrical connections as T, for each, are inserted in the anode compartment for carrying the current to the colic Similarly, a grapnite member 8, having suitable electrical connections 9, is inserted in thcolzed.

The member 8 serves also as a means for introducing nitro en to the cathode, being or a tube lnrving, as shown,

in the charactr A rated as at 1:. idc for the pa of the nitrogen, tlqreby to introduce the nitrogen at the bottom oi"? the cathode. Conveniently the member enlarged, at its lower end, into a box film; as indicated at 12.

A tube 133, 01 any suitable material, as glass, and extending to the bottom of the coke 5 and around the annulus T3 in form, as ind ited at 13 serves tor the troduct of 1 itrogen to the bottom of the anode. is shown, the tube perioratet alon the ring l3, as at '34:, For the passage 0? the nitrogen.

compa tn] ent the conducting away of the gases, LO, produced by the anodic reactions; i i-townie, a 17, t extending into cathode cenn a posiiou above the level of the s 1 l6, serves mr the conducti away c. ll},

Perf orate'il pa rtitio re rubber d sk in and t e rubber ring la, inserted in the cor uents l hold the coho in position, the spaces above t partitions serving as gas chambers 20 and To close the cathode compartment and hold the various rods and so forth in position, a stopper 22, desirably or": rubber, is inserted .1 *3 to the compartments. ll deare appl red vllll sired,

thermometers

25 and 26 may be provided.

The cell may be operated and the process carried out in the following manner, the process when carried out in such manner being of the Class C type mentioned later in the giving of experimental data :The anode and cathode compartments of the cell are filled to a suitable level with the electrolytic solution which may be an aque ous solution of an electrolyte, say nitric acid, sodium nitrate, sodium hydroxid, etc., containing the electrolyte in sufficient quantity, say 5 to 20%, to give a proper conductivity to the solution. Operating desirably at about 19 (1., nitrogen is forced through the porous electrodes, from the bottom. The current is so regulated that the oxygen liberated on and within the porous structure of the anode is, for practical purposes, sufiicient to oxidize the introduced nitrogen only to NO.

The amount of nitric oxid formed at the anode is dependent on current regulation in relation to the amount of nitrogen introduced. Also, the progress of the oxidation is affected by the anodic current density. As will be understood by those familiar with the art, these can be varied at will, to obtain the desired conditions in each particular case. With the illustrated cell I have found an anodic current density of .04: to .05 ampere per square inch of superficial area of the anode satisfactory.

llhe nitrogen forced through the cathode combines only as NH and the current regulation at the cathode is not of such importance as the regulation at the anode. Ammonia forms within the cathode compartment until the catholyte is saturated with ammonia whereupon ammonia gas is evolved through the outlet 17 The evolved gases are passed into suitable absorbing systems, as will be understood, the apparatus being say as conventionally outlined in Fig. 3 there, the source of supply of nitrogen under pressure is indicated by the tanlc. N; the ammonia gas is absorbed in water from IV in an ammonia absorption column A; the N0 gas is passed first to the oxidization chamber 0, air being introduced at (1., and the NO, passes to the absorption column ll and to the absorption column H water bein supplied at W" for the formation of llNO, the dilute acid being transferred from H to H by acid egg E.

As described above, the process is, so far as practicable, so carried out that in the cell the nitrogen is oxidized only to NO, the further oxidation to IINU taking place outside of the cell and, so, not at the expense of the oxygen being liberated by the cell. Thus, the most efficient condition is approached. That comlition is, of course, that only one molecular equivalent of oxygen is required from the cell for one molecular equivalent of nitrogen oxidized, the cell acting merely as a nitric oxid generator. (As a matter of fact, some NO, is always formed, and will, depending upon the anolyte, form some nitric acid or nitrates within the cell, but the amount is small and does not detract materially from the action of the anode as a nitric oxid generator.)

It will be understood that, depending upon conditions, a principal one being the amount of nitrogen supplied to the oxygen liberated (supposing a constant liberation of oxygen), nitric acid or its salts may, if desired, be produced within the cell instead of merely (as above indicated) producing an anode gas containing a mixture of NO and N0 in which the ratio is very large.

In any case, I prefer to supply nitrogen somewhat in excess of the amount theoretically necessary for the particular reaction desired.

Illustrative of the above, the process may be performed to meet the conditions of several classes, say three, which three, for convenience, I designate A, B, and C. These classes are characterized by :A-the formation of nitric acid within the anode compartment of the cell, with acid electrolytes; B-the formation of nitrates within the anode compartment of the cell, with alkaline electrolytes; C-the formation of nitric oxid (NO) within the anode compartment of the cell for subsequent oxidation to nitrogen peroxid (N0 by air and eventual conversion of the N0 to nitric acid or equivalent salts in the usual manner. I give an example in each of the classes. (In all cases, except Class A, where no attempt was made to produce it, ammonia was formed at the cathode by the combination of electrolytic hydrogen with the nitrogen introduced at the cathode. Since it was not possible to determine accurately the internal surface areas of the porous electrodes, the superii cial areas were used for purposes of comparison in recording current densities during the experiments) Class A which a rod of graphite was hung to act as a cathode, the following typical results were obtained, the cell being operated at about room temperature (19 C.) and with a current density in both cases of about .054 ampere per square inch at the anode, that at the cathode not being; not being determ1ned:

HNO: in cell.

N. B.Gur rent efilciency calculated on the basis of nitrogen oxidation taking place to N20 electrolytically.

Class B.

In a cell similar to that used in Class A, except that the porous cathode graphitized petroleum woke conta, unglazed porcelain battery jar with means for forcing nitrogen tiroug'h it, the anode and cathode bein submerged in the jars by dilute sodium hydroxid solution, and surrounded by the same solution contained in a glass vessel, the following typical results were obtained, the cell being; operated at about room temperature, and with a current density in the first case of about 09% ampere per square inch at each electrode, and, in the second case, about .016 at the anode and .197 at the cathode The cited experiments were carried out with a cell substantially like the illustrated and described cell (and it will be understood that such a cell may be used for Cla, s A and Class B work).

The following table shows the effect on the anodic reactions oi? varying the current density, other conditions remaining constant:-

Anode Current (1 e n s it y fig an per sq. in. NO superficial area of N0 NO anode.

Par ct. Per 01.

7. 1 61. l?! 3. 65 0. 0333 4. 713 20. 18 1. 30 (l. 929 21. 16 Q6. 09 1. OS t). O" 14. l 1. 0S 0. 075 12.08 12. 0S 1. 00 O. 068 18. 75 18. 75 1. 0O O. 9138 Operating the cell with an anode current density of from 0.03 to 0.04: ampere per square inch of superficial area for 9-41: amperc hours, the nitric acid found in the ab sorption columns from the oxidation of the I CZESG Original clectrolots-sodium a Zvmtc solu tion.

Anolyte contained 91.1, gfl'llll'lS of nitrogen as NaNO Catho gen as Fla-3 0 Total in cell, 9"488 grains of nitrogen as smo End of cmpcrimcat-cftar 30 compare hows.

Anolyte contained 6.01 grams of nitrogen as HNO Anolyte contains as NaNO Catho *te contained 6.69 grams of nitrogen as HH Absorption column #1. gins. of nitrogen as HNO of nitrogen as NIL.

1 -3 nitrogen contained 23.65

Total in eel ann absoi eels 00. !8 Original amount 97. 88

Grain by electrolysis 37. 90

The 37.9 grams of nitrogen .lX-ed were present as follow From the anodic reaction HNO From the cathodic reaction 9.99 grams as NH 330 amuere hours should theoreticalhq oxh disc on 1 on to to produce ifilfiifi grams inc anode itlielly produced 1622 of llNO hence the current elliciency was At the cathode 330 ampere hours produced 9.99 grains of h Theore Mira.

63.19 'i'ams or". NH, should have been formed. The actual curn it ell cncy at the cathode was tn The ainmonni. ield in this a case was low. Yields as high as 4.0% and 60%, and in one case 70%. or" the theoretical have been obtained.

Owing to the secondary reactions that may talte in the region of the anode, it is iinpoc to describe def tely the exact g'rhenoniena of the nitr. en oxidation. There are several steps or stages of oxidation, all possible under different conditions, and all phone; nitric acid or its equivai by reactions with the electrolyte, if 2 oxidation occur in the cell, as

xidation may take place with the in- .to formation of nitric oxid (NO), the nitric oxid then taking on additional oxygen to form nitrogen peroxid (N0 and finally, by further successive oxidation, nitrogen pentoxid may be formed. The latter reacts directly with water to form nitric acid 1- Or the nitrogen peroxid (N0 may first react with water to form a m1xture of nitric acid and nitrous acld, thus the nitr'ius acid then being further oxidized to nitric acid:-

If the electrolyte be cold, reaction (2) would probably take place; if the electrolyte be heated a little below the boiling point of water, the reaction would form nitric acid and nitric oxid, thus snoan o (hot): IINO +NO,

the nitric oxid split off from this reaction taking on. additional oxygen to form nitro* gen pcroxid (N0 in which case the above reaction would be repeated. In whatever manner the oxidation reactions take place, if complete oxidation to nitric acid takes place within the cell, it is necessary to liberate five molecular equivalents of oxygen for every two molecular equivalents of nitrogen oxidized.

I am aware that it is possible to find traces of nitrogen compounds in aqueous electrolytes, through which air or gases containing free nitrogen have been bubbled dur ing electrolysis, in order to agitate the solution or to disengage electrolytic gas from the surface of the anode or cathode. And these tra es of nitrogen compounds are with" out much question due to the direct chemical combination of the nitrogen dissolved in the solution and the oxygen and hydrogen liberated on the surface of the anode and cathode. But the fact that nitrogen is only very slightly soluble in water,0.00295 gram in 100 cc. of water at 0 Ca and less at higher tciuperaturea-makes the oxidation or hydrogenation of the dissolved nitrogen in aqueous electrolytes of no commercial significance.

It will be understood that the conditions of operating, and the particular cell used, may be changed in many ways without departing from the spirit of my invention. A nd it will also be understood, that many of title prinw ples and features of the invention;

are broadly applicable to the performance of gas reactions other than the particular ones referred to by way of example, and therefore, so far as the principles of the invention are applicable to gas reactions other than those having to do with nitrogen, i do not restrict the invention to processes lllVOlVlilg nitrogen reactions. Also, references to nitrogen gas, and so on, in the claims are not to be understood as restricting the invention to the use of isolated nitrogen, as the nitrogen may be supplied as the constituent of a mixture, as by passing air through the cell, the process then serving for the direct fixation of atmospheric nitro gen; the use of air being more particularly applicable to the oxidizing of the nitrogen at the anode. In performing the process conformable to the conditions of Class C, with air, the electric current and the supply of air are so regulated that, so far as practicable, the supply of oxygen liberated by the cell is sufficient to oxidize the nitrogen to NO only.

In the carrying on of the process, after the manner of Class A, or of Class B, where, as nearly as practicable, complete oxidation of the nitrogen takes place in the cell, it will be understood that the supply of electric energy and the supply of nitrogen are preferably so relatively regulated that the oxygen liberated is sufficient to fully oxidize the nitrogen. When air is used rather than isolated nitrogen a reduction in the amount of oxygen liberated, can be made, in consideration of the available oxygen in the air.

As previously indicated, the greater the porosity and the smaller the individual pores, the more nearly is the ideal condition approached in the subdivision of the body of the nitrogen gas. By the use of the graphitiaed petroleum COliG electrones, having, for pores, merely the minute pores in enormous number, characteristic of coke, the desired condition of a great number of small pores, is arrived at conveniently. And so, too, with the fine steel wool suggested. But it will be understood that other materials, giving the desirable condition, can be used without departing from the invention.

As will appear from the context, I have, in the foregoing description, generally used the term electrolyte in its newer sense of solution of a substance capable of being electrolyzed, but have, on occasion and for the sake of clearness, used it in its older sense to designate the substance itself. Also the terms anolyte and catholyte are used to designate the solution in the anode and cathode compartment-s respectively.

i/Vhen, as illustrated, each electrode is in substai'itially single piece, they may inelude separable sub-structures as

conical plugs

25 and 26, and 12, and the annulus 13, permitting the introduction of the thermometers, the tube 8 and the tube 13 With its ring-like part 18, such structures being forced into proper electrical contact with the major portions oi the electrodes. The

tubes

8 and 1 may be slid into place from below before the introduction oi? the electrodes into the containers, proper receiving spaces for the various tubes, and for the members (3, being pro .*i 'le in the electrodes as made, and the tube 8 and the members 6 being received in their respective electrodes in electrical contact tlerewith; the upper end of tube 13 being bent over, after the positioning of the tube and application of the ring In an assembly such as that illust 'ated in lf ig'. 3, it will be understood that such pipe couplings and other fittings (not shown) as desired may be provided to facilitate convenient assembly.

I claim 1. The process oi producing compouiuls by gas reactions and substantially independ ently of the solubility phenomena of the hereafter-nanied gaseous element relative to the her softer-nomed. fluid, which includes electrolyzing an electrolytic fluid containing an element liberatable as a gas and combinable with a gaseous se ond element, nechanically minutely dividing a body said gaseous element, and mechanically, as distinguished from and substantially independent of yorking y virtue of the solubility of said gaseous element in said fluid, bringing the divisions of? said body into intimate, direct contact with said first unmet element at the moment oi. its liberation from the fluid.

2. The process of producing: compounds by gas reactions which inchules ing, in a roll having! a porous electrode. elevtrolytic fluid containing an element liberatable as a gas at said electrode and cimibiuaole with a gaseous second clenio t, and pass i said serond elemc i=1 through the pores of said e: the electrolyzing, thereby to mm W I r de the body 0'! r seous element into minute st eams and me hanically l); said streams info Contact with the lii alahle element, and on and Within the 11 ot jhe electrode, ad the moment oil it l atiou The yuovew of ru'odi'lcing a n trogen compound substantially independently of the solubility phenomena of nitrogen relative to the hereafter named fluid, Whi h in cludes electrolyzing an electrolytic fluid containing an element liberatable as gas and combinable with nitrogen, mechanically minutely dnuding a body of, nitrogen gas, and mechanically. as distinguished f our and substantially independent of Working by virtue of the solubility of nitrogen in said lirect contaet wit i the inoinuit 0' its liberat1o= of producing 1 llli'llltbC-S electr 1 said cl V V i Jen, and p: the pores oi said elect; trolyziig, thereby t the and

a a V L wliicllb, ane

el electrod at the ill of its liberation.

'ocess ot fixing nitrogen substan- "y of the solubi it i nh ,i aiiically minutely dividitrogen gas, and IYlGCl.l;irl inggnished from l substaneznlent of working by virtue of the solul of nitrogen in n bringing: the divisions of sail fl body into intimate, Contact with gas liberated by the ysis, a the moment of its liberation.

he lJl'Ol'CSS of ing nitrogen which ectrolyzing an aqueous electrol 'uticn in a cell havin a porous electrode, an L assiiig HlQZTO GE 0 s through pores i' said electrode du in the electron ysis, thereby to mechanically di ide the be? F i rogen into m'uute streams and ineolnuiically bring said streams into contact with the liberated (luring; eleczzrob ysis, and on and Within the pores ot the electrode, the moment of its libe 'ation.

process of oxidizing nitrogen The 'zaing an electroly :11, 1 .1 a cell having a passing n n j i s s id anode do thereln to met of nit ogen wally bring; said streams l Within the n i s aeration.

.. I ie procrss o uni nioaia \vh i ch an electro in a hell ha; n

nitrogen gas 1' its u fluid and i iss nej rough the pores of said vathode during "1 eh-ttrolyziiug, thereby o mech nically ,livide the b-r-dw 1- nitrogzfli into minute streams and nieeln eally bring: said streains into coi'ztact with the hydrogen l berated during elcctrolys's. and or and Within the pores oi the cathode, at the moment of its liberation.

The pro ess 0t producing; a nitrogen compound suostantially independently the solubility phenomena, of nitrogen rel liberate i ne at the moment of its liberation, and can the resulting product to react with a substance containing the element with which it is desired to fix the nitrogen to produce the desired compound.

10. lhe process of producing a nitrogen compound substantially independently of the solubility phenomena of nitrogen rela tive to the hereafter named fluid, which consists in electrolyzing an electrolytic fluid containing oxygen, mechanically minutely dividing a body of nitrogen and mechanically, a. distinguished from and substantially iooependent of working by virtue of the solul ity of nitrogen in said fluid, bringing the divisions of said body into intimate, direct contact with the liberated oxygen at the moment of its liberation, while so regulating the supply of electric energy a 1d the supply of nitrogen that nitric oxid is formed, and removing said OXlCl from the cell and causing it to combine with the eleis. ut with whi h it is desired to fix the nit. gen to produce the desired compound.

11. The process of producing a nitrogen oompoui l substantially independently of the solu ility phenomena of nitrogen relahereafter-named fluid, which contire to t o sists in olectrolyzing an electrolytic fluid rontaln'm y oxygen, mechanically mlnutely 0 1 a 0 dividin a body of nitrogen and mechanically, distinguished trom and substare tially iiulopeiulent of working by virtue of the solubility of nitrogen in said fluid, bri ginu the divisions of said body into intimate, i irect contact with the liberated oxy gen at the moment of its liberation, while so rceul i'ng the supply of el ctric energy and ti o supply of nitrogen as to provide, as nearly as practicable, for the oxidation of the nitrogen to nitric did only in the cell. and removing said oxid from the cell and Causing it to c *nbiue with the element with wltih it is do ired to fix the nitrogen to pro ur the desired compound.

12. The process of producing a. nitrogen i substantially independently of lity phenomena of nitrogen relaivc to th hereafter-named fluid which cons in rlectrolyzing an electrolytic fluid containi, oxygen, said fluid also contain ing an e ment with which the nitrogen may be tired, mechanically minutely dividing a body of nitrogen an. mechanically, as distinguished from and substantially independent of Working by virtue of the solubility of nitrogen in said fluid, brir Y the divisions of said body into intimate, uirect contact with the liberated oxyat the moment of its liberation, and permitting the resulting product to combine in the cell with the said fiuid-contained element to fix the nitrogen.

18. in an electrolytic cell for the conducting of gas reactions, means for containing the electrolytic fluid, and electrodes therefor, one of said electrodes being porous to provide for the permeation thereof by gas.

14:. in an electrolytic cell, means for containing the electrolytic fluid, electrodes therefor, one of said electrodes being p0 rous, and means for conducting gas into such electrode and in communication with the pores thereof, thereby to provide for the introduction of gas into said pores to permeate such electrode.

15. In an electrolytic cell, means for containing the electrolytic fluid, electrodes therefor, one of said electrodes being porous, and means for conducting gas into such electrode, such means extending to adjacent the bottom of the electrode and being there in communication with the pores of such electrode thereby to provide for the introduction of gas into said pores to rise through such electrode.

16. In an electrolytic cell, means for containing the electrolytic fluid, electrodes therefor, one of said electrodes being porous, means for conducting gas into such electrode, means providing a gas chamber above such electrode, and means in communication with said chamber for conducting away gas.

17. In an electrolytic cell, means for containing the electrolytic fluid, electrodes therefor, one of said electrodes being porous and adapted to be submerged in the fluid, means for conducting gas into said electrode below the level of the fluid, and means above the level of the fluid and adjacent said electrode for conducting away the gaseous products from the electrode.

18. In an electrolytic cell, a container, means in the container dividing it into an anode compartment and a cathode compartment, an electrode for each compartment, one of said electrodes being porous and 0ccupying the major portion of its compartment thereby to provide that the major portion of the liquid in such compartment shall lie within electrode pores, and means for conducting gas into the pores of the said porous electrode.

19. In an electrolytic cell, a container, means in the container dividing it into an anode compartment and a cathode compartment, electrode for each compartment, one of said electrodes being porous and cocupying the major portion of its compart ment thereby to provide that the major portion of the liquid in such compartment shall lie within electrode pores means for conducting gas into the pores of the said porous electrode and means for conducting away the gaseous products from such elec trode.

20. In an electrolytic cell, means for con taining the electrolytic fluid, electrodes therefor, one of said electrodes being porous, and a member for conducting the current to such electrodes, said member being in the character of a tube providing a passage for gas.

In testimony whereof I ailix my signature.

CHARLES E. JACOBS,