US1019002A - Process of producing cyanogen compounds. - Google Patents

Description

C. E. ACKER. l PROCESS 0F PRODUGINGYANOGEN COMPOUNDS.

K APPLIOATION FILED 1350.12, v1910. 1,019,002 l Patented Feb. 27, 1912.

s SHEETS-4mm@ E. ACKER. PROCESS OF PRODUOING CYANOGEN COMPOUNDS.

APPLICATION FILED DEO; l2, 1910.

l l1,019,002'. Patented Feb. 27, 1912.

3 SHEETS-SHEET 2.

C. E. ACKER. PROCESS OF PRODUGING CYANOGEN COMPOUNDS. APPLIOATION FILED ppc. 12, 1910.

` 1,019,002. Patntea Feb.27,i1912.

SHHEETS-SHEET 3.

wi C4/wesen I S woe vyofo procese therein. f M

UNITED STATES PATENT GFFICE.

CHARLES E. ACKER, OF OSSINING, NEW YORK, ASSIGNOR TO THE NITROGEN COMPANY,

A CORPORATION OF YORK.

PROCESS 0F PR-ODUCING CYANGGEN COMPOUNDS.

Speccation of Letters Patent,

Patented Feb. 27, 1912.

Original application filed August 30, 1910, Serial No. 579,763. Divided and this application filed December 12, 1910. Serial No. 596,752.

To all whom it may concern Be it known that l, Giannone E. Aem-zn, u citizen oifY the United Staten, residing :1t Ossinin, in the county of "ii/Tesf-r-luzstcr and State of New York, have invented certain new and useful improveuients in 'iroressee of liocllieirig Cyan@ 'in (loinpounde und the Like, of which the curing is a, full, clear, and exact descriptioi'i.

'Iliisin'W-:ntion relates to e process for the manufacture ot' aiknli metal cyanide, cyan- :miids and the hice, und more p :ulnrly to certain innn'ovenients in the process described in iny United applicatii'in Serial No. S-,ebL filed March 1909, the

closed consisting in initially reacting on :i particnlnriy reactive metal, Such barium, lithium, calcium, strontium, manganese, etc., with coi-hon or u carbonaccons reagent, for the purpose of producing,` i carbid of snc-h .ine-tai, c. g., barium carbid; in then treating' 'this carbid with nitrogen or a nitroejeiious reagent, for the purpoee of produc/ins, thecyanid of such nietzil, in this cese barium cyn-nidg and in finally renc-ting,r on the barium eyenid with un ulkaii motel, 9 sodium with the consequent production of sodium cyanid and meteliic barium.

It was Stated in the appiicntion aforementioned that the reactive metal, c. g., barium, might combine directly with nitrogen to forni. barium nitrid, which would then react with the cnrbonaceous reagent to form barium cyanid; and that Jthis cyanid would 5 in turn be decomposed by sodium ns above with former-ion of sodium cynnid and metallic barium. it was further Stated that both carbid and nitrid might be formed under the conditions ofthe process, and that these producten-iight in turn then reacttogether to form f reactive metal i cyanid, c'. '57., barium cy'frnid-Which would then be similzirly decomposed by metallic. sodium.

While is is` possibie to bring about th reactions Substzrntiaily as hereinbefore described, I find, as aresnltzof'furtherinvestigation of; the-phenomenon, therein practice by fer the',A greater, prrr-tof the finiti product is produced as the result of the initial fon mation of "l, reactive met-l carbid,` in Whit seems .to be 'a particularly favorable physical condition, suchcerbid When in such condi.-

tion readily absorbing and combining With nitrogen; und that as a consequence, but o' compnintivciy small proportion of the 'final product is; obtained as n result of the initial forn'intion of renc-tive metal nitrid; this small proportion of course combining with oni-bon in the manner above described to for-1n the cyanid, etc.

Sufficient free carbon being present, I consider that the pri. cipal reactions are as fol lows:

anhydrous ammonia is einployedinstead of 'free nitrogen, the second of the above equations will be as follows:

(e) eecnennnncmnn..

lar, or lump charcoal., coal, colte, or a hydrocarbon gus, fuel oii, 'lmnp black, or cyanids or cyzinniuids. H; the source' of carbon is a gee fuel oil or ,lmnp black, the resultant carbid produced by the combination of the reactive metal a with carbon as pointed out in the patent application above referred to, is found to be preeent soiely in finely divied forni. have discovered that the ear id produced in the present proces is appar# entiy amorphous and iinpalpable, which is evidently a, 'result= ofthe very low temperature at 'which it is produced, gencrally'he- 10W 900o C. rind under moet 'radically different conditionsfrein the4 impure, hard, iridescent, crystalline carbide which are produced at temperatures ranging from 14000' to 1800" C., or more. The terms amorehous and impalpable? particularly Well escribe this substance since the separate Cai particles of it lwhich are produced, if indeed they may be termed particles, are so `minute that they cannot be seen by the naked eye; and are mon-crystalline and robably porous. Thxey Iare ioon-crystalline ily reason. of the fact that the temperature at which this form of carbid is formed, under the condition of the process, is suffe cientl to permit the formation thereof; but is not' sufficient to fuse or liquefy the same: as a result of which fact the molecules of the material have no opportunity to arrange themselves to form, and the resultant substance is amorphous. In so far as I ain aware, it has never been possible to produce this form ofcarbid up to the time of my invention and discovery thereof. It is obviousv that the physical characteristics above referred to promote the reactions whereby the cyanid is formed.

I desire now to differentiate the particular process herein described and that set forth in the aforementioned patent application. The present application is a division of mv application Serial Number 579,763, filed Aug. 30, 1910, for a' process of iroducing cyanogen compounds; the claims hereinafter presented being directed 'more particularly to a process involving the alternate reaction of two metals, c., sodium and barium on nitrogen and carbon. The particular methods described in my application, Serial Number 485,3454, above referred to, involved the interaction. of various substances (1) Within the mass of molten metals or alloyf-or in other Words when partly or Wholly submerged therein. (2) When brought into intimate contact with each other and with the changing surfaces of the molten reactive metal, alkali metal, or alloy, While contained in a revolving retort or cylinder, and under pressure, if desired; (3) and by first reacting on the alloy with carbon. tov produce carbid; then Withdrawing the alloy from a chamber containing carbid. coated charcoal or colte, or carbid containing masses, introducing nitrogen or other reagent into the chamber under pressure so that the samemay intimately contact With the carbid, and in finally returning the molten alkali metal alloy to the chamber. I have discovered, however, that greatly increased eliciency and speed in carrying out the process may be had by causing. or permitting both carbon and carbid. in very finely divided. form to risc from the surface of 'the alloy and from thence become diffused -throughout the accumulated molten cyanid itself. In other Words, I have now discovered that it is possible and most de# sirable to,V induce most of the reactions in vquestion to occur outside of the mass of alloy in contradistinction to the process originell described, wherein the reactions occur prmcipally at or below the surface of the alloy, With the primary object of there effecting the synthesis of sodium cyanid. lJVhen the original process was carried out the sodium eyanid by reason of its low specific gravity flowed t'lirougl'l and accumulated on the surface of the alloy, and it was this action that led to the discovery that both the carbon and carbid would, if in sufficiently finely divided form, rise to the surface and become diffused in the manner above described.

Referring to the aceon'lfmnying drawings, which form a part hereof: Figure 1 is a vertical cross section of an apparatus adapted for the carrying out of'my improved process; said section being taken on line I-I of Ifig. 2. Fig. 2 is a horizontal section through the said apparatus taken on the line Il'MII of Fig. 1. Fig. 3 is a trans versc vertical section of .said apparatus taken on the line IIIvIII of liig. Fig. 4 is a fragmentary section taken on line IVHIV of Fig. Fig. 5 is a centra] verti cal section of a reaction vessel or pot which is especially Well adapted for carrying out the latter steps of my process.

Lilie parts are designated by the same reference sign throughout the respective views. v

Referring nou7 to the first four figures, the furnace or inner container 1 should prefH erably be made of cast iron or cast steel, and the inner walls of such chamber should preferably be lined Wit-h refractory material 2, such as alumina or magnesia. The furnace casting is inclosed at the bottom and 'on all sides by heat insulating material 3, preferably brick or the like. The furnace comprises two principal chambers, an elec trolytic chamber 4 and a reaction chamber 5,y these chambers being separated by a sep tum or Wall (5; the bottom flanges 7 of this wall serving to support the adjacent side linings 9.. A set of anodes 8 extend into the electrolytic chamber and are preferably made of some'form of carbon. The electrolytie chamber 4 is covered With a slab'9 of suitable refractory material; andthe gasesliberated at the anodes are conducted avvay through flues 10. The reaction chamber 5 is fitted With a spout 11 for conducting off the final product, such compartment having a cover 12 spaced from the container by an air tight gasket to prevent the admission of air into the reaction chamber. A casting 13, called a plunger, projects through the cover into the mass of a Huid salt 14 olis-A posed in the reaction chamber; the electrolyte inthe electrolyt-ic chamber being designated 15. A body of heavy metal or alloy 16 is disposed in the bottom of the respective compartments or chambers, and a plnrality of conduits, filled by s'aid alloy, adord means for effectively circulating the heavy metal or alloy through and sealing the re- Loiaooe 3 spective chambers. ln the form of furnace 1n question, one of such conduits is shown in section 'in Fig. l and has been. designated i7; a passage 18 leading down into it from chamber 4- and a corresponding passage 19, leading from it to chamber 5v. The second conduit- 20 is in communication with the farther of the respective chambers through passages 2l, 22, the conduit 20 leading therefrom to a suitable pump 23.A This pump is preferably of the centrifugal type, but any sui'L le apparatus may be employed for this p irpose. The vmoveimznt of the mass of huid alloy through the chambers, results in stirring up the respective molten salts, since such b'od'es float upon the surfaces of tl e alloy in the respective chambers. The circulation of this alloy may beeliccted intermittently or continuously by mechanical means or otherwise, and suitable s, such as a hopper 2e, may be provided for permitting the continuous or intermittent introduction of the salt required in 'the electrolytic chamber. The plunger is advjustable in the air tight cover l2 and has a hole .ei-llena i through its shank, the upper s fitted with a valved pipe 95 for introducing nitrogen or' ammonia into the molten mass in reaction chamber;

.and is also tted with an oil feed device 26,

thror which del oil or other hydrocarbon may be introduced vin care-fully regulated ities into the reaction chamber. An li ry supp-ly pipe 2? extends through the side of the reaction chamber, which pipe may be used to introduce nitrogen or hydrocarbon, or both, directly into the mass of molten metal, when desired. The cover l2- is also litted with a. specially constructed hopper 28, which an air tight cover and is so arranged that'it may be filled with charcoal and. then subjected to a vacuum tor the purpose of exhausting the air from the hopper and the charcoal contained therein, before it is charged intothe reaction chamber, the connections for exhausting the air being indicated at 29. The molten cyanid is produced in 'the react-ion. chamber and normally rises to a relatively high level before it is permitted to run oli through the spout ll; this spout being temporarily closed, when desired, to permit the cyanid to ac# cumulate in the chamber before. being tapped oil'.

In starting the apparatus the electric current is passed through the electrolyte inthe electrolytic chamber, such electrolyte consisting, for example, of barium chlorid and sodium chlorid, at a sutliciently high voltage and current density to simultaneously liberate both metallic barium and sodium on the surface of the molten lead constituting the cathode. The liberated metals combine lvvith'the lead to 'forman alloy of barium, sodium and lead, which is conducted `casting or plunger may be lowered to a point lWhere its llovver surface or face is submergedin the molten alloy. Fuel oil under pressure may lthen be introduced through the oil feed device and will come in contact with the red hot alloy below the' surface of the plunger, at which temperature the oil Will be broken upeinto finely d1- lvided carbon (lamp black) and hydrogen1 the latter oi: which will escape through the overow spout 1l. If there isl sufficient barium in the alloy it Will combine with the carbon of the charcoal or with the carbon produced by the decompositionA of the oil tov lorm barium carbid, some of Which will be held submerged in the alloy against the lower surface of the plunger, and some of which will be` forced out by the escaping hydrogen.- Nitrogen may be introduced through pipe 25 and will theii pass down through the hollow shank of the plunger to the lower surface'thereoi, and then spread. out in the form of a thin layerbetween the face of the plunger and the molten alloy and thus come into more or less effective Contact with the ,carbids which will have been produced in accordance 'with the reaction herein before referred to. That portion of the nitrogen Whichcomes into reactive contact with some ofl the barium carbid then combines therewith to produce barium cyanid. The barium in the bariumcyanid is then displaced by metallic sodium in the alloy with the consequent production of sodium cyanid and metallic barium; the barium immediately'becoming available for the production of more carbid. vAs soon as a sutticient proportion of barium (or other reactive metal has been incorporated into the alloy to react readily with the carbon it becomes unnecessary tosupply more `for the reason that the reactive metal is used over and over again and therefore no more barium wchlorid need be'added tp the 'electrolyte. If any loss of available barium occurs in` the alloy or of barium. carbid or cyanid in the melt through any unavoidable or inadvertent circumstanceror if as in some cases, a certain proportion of the barium cyanid is allowed to be drawn 0H together Wit-h the sodium cyanid produced, or i for any other reason, the delciency may be supplied troni tii'ne to time by adding,` loan riuni clilorid to the electrolyte or by supply iup;- it iii any other-manner,

t'lodiuni cliianid is rei-y fusible at the teni- ]vierature oit the operation and rises 'to and accumulates on the surface of the alloy. l have :toiiiid that the presence of a oonsiderable body ol molten cyaniifl on the surface ci the alloy is highly beneficial, in that the presence ol this tluid ,mass permits the amorphous barium carbid and Finely divided carbon to become ditliised therein; being mined and suspended to a considerable ententand thus much iiiore easily brought and held in reactive contact with the nitrogen or nitrogenous reagent. The entire mass 'ot oyanid is practically saturated with iiii palpable carbid and it a sample of the niol` ten cyanidlie iiiitlidrawn during; the process', and moistened with Water, the presence ot' carbid is 'ifery evident troni, the odor olf the evolved acetylene, altliiiuggli no lumps or ci'jiistals of carbide iiiliatsoever may be 'visi ble, very line state ot division and is probably entirely amorphous, although itis possible that it niay' in part, at least, be in actual so lution. f yll7lien the cyanid is examined under the niicrosiuipe the pure colorless crystals of cy unid loin up 'iiery large and clear, and squeezed in betii en the crystals is the darlr or black carbid apparently in the iorin oi a liliii. rlllie iiioi re in "the air attacks this tilni of carbid between the crystals at the exposed edges of the iilin and iiiinute bubbles oit are constantly given oill all alongtlie exposed edges Evidently the carbid is in irery soi't condiv tion since it is squeezed into the thin spaces between tlie crystals ot the cyanid. in the y manner described; but it is impossible to er till ' amine it directly in the open air on account ol2 the nunute bubbles of 'which instantly cover its siii-tace. y y

The specific gravity ot some carbide, e. g., barium carbid, is considerably greater than that of molten sodium cyanid, but owing to the fact that these carbide are apparently in amorphous condition, very little agitation required to maintain them in sus- A. little 'tuel oil injected into "the i into the molten eyanid and used primarily as a source oit carbon, sullices to produce all the agitation required to maintain both the carbon and amorphous carbid in suspension in the molten-cyanid; and if there is then' escaping around the edge of the plunger and passing up through the alloy an excess ot nitrogen or ammonia, I llnd that suoli gases arising in the torni of bubbles into tlie superimposed body ont molten cya' carbid in ainiiiioiiiia t,

i and.

l`lie carbid is therefore presentina' also lreep the 'carbon and nitrogen or s with 1' f the suspended and impalpable, or possibly even dissolved barium carbid, to torni barium cyanid. The latter compound, dise ,solving in the molten sodium cyanid, is then or :iiteriifard easily brought into contact with the necessary alliali metal or alkali metal alloy and transformed into sodium cyanid and metallic barium. This liberated barium soon seizes upon more carbon to reform amorphous barium carbid `which again becomes suspended in the molten cyanid ready to combine 'with more nitrogen, ammonia, or other nitrogenous reagent;

lill

this cycle being `indefinitely repeated. l-

liave discovered, furthermore, in employing either i'ree nitrogen or ammonia as the nitrogenous reagent, that ity is not necessary at any time to bring tlie'g'as into actual contact with the molten metal, either at the surtace of the molten alkali" instal, reactive metal, when used in a pure state, or molten alloy, containing either oi them; nor to inject it into the mass, 27,. e., below' the sur face thereof, provided there is present on the surface of the alloy a suliicient body ot molten cyanid. lThe plunger may, hence, in such case, be raised so that its lower surtace is entirely above the niolten alloy, but still submerged in the cyanid.

Thev absorption of :tree or molecular nitrogen by the pure suspended barium carbid, formed under the conditions of the process, Wlienheated, may be attributed to either one or both of two things; namely, the amorphous condition of such carbid, in which respect it is radically different from the hard crystalline pure carbid which Meissen stated (mii'ptes Rendus 18%, page would not absorb free nitrogen; and because the molten cyanogen compound in which the carbid is suspended apparently assists l,the absorption in a Way not as yet' 'metallic heatfcmductor, l iind that sollioientheat may be conducted away through 'theisliank of the-plunger, to outside or the furnace, to materially reduce tbe temA perature of the tace and entire lowergend of the plunger and ot the molten cyanid in immediate contactfthereiivith; and this is a fact of great importance when ammonia .is

employed as the nitrogenous reagent. The combination ofthe nitrogen of the ammonia With the amorphous carbid suspended inthe molten cyani'd takes place with great ra pidity andeliiciency 'owing to the fact t t the nitrogen is liberated. in nascent lo l directly in contact `with the carbid, Whereas ii? the ainiiioniafweiie lirst introduced into the red liet alloyJ it `girouid be partly decora titl lll

vthey will neyertheless bring about the .synn

thesis oit sodium or potassium cyanid "under the `,process-the mechanism ot some of the intermediate reactions being necessarily difterent from those tor which equationsarc lgrit/en in this speciticatiomwand being in fact, not clearly understood. 'The process also Worlts somewhat more slowly when manganese, ceriuin, etc., are employed in,- stead ot barium, lithium, etc. Pure iron willy also-combine 'With carbon to form a cara bid in the process, but it will not combine 'with free nitrogen to form a stable nitrid and will not accomplish the synthesisot alkali cyanid under the process. y .Y

alkali-metal is employed in the pure state,

instead of in the form of any alloy with a heavy metal, or iit' both pure alkali-metal andaflloy be used, the react-ions and the final result Willloe substantially the same as those already' described. The pure sodium or po tassiuin will 'float on the surface of molten cyanid, however, or on. a' portion of the snri'ace, Wl'licl'i may be restricted t'or instance inside .ot a cylindrical casing 6l shown in the large pot in llTig. The ascending ni trogen or ammonia will in such. case pass upwardly into the cyanid adjaccntthe Walls of the pot and outside ot the cylinder, and may hence nass entirely through the mass ot cyanid, it not completely absorbed thereby, Withoutpassing through the `molten alkali metal o2. .llt ammonia, be employed instead ol pure nitrogen and some ot it cornes in physical contact with pure sodium, thus ltloatinn,r on the sur-.tace ol vthc molten oyanid, another' set ot Very transitory intermediate rel 'ations may come into play to a small cx- 1 and lilte result in the production olf' sodium cyanid but the tree carbon susl in the cyanid will continue toreact y reactive metal. as in equation l, andthe process will proceed substantially aceo?ruling` to equations l, l and 3.

.1li Wishto denne that in the claims the scope ol 'the term l nitrogenous reagent includes any reageiit Which will yield nitrogen under the condition of the process, as, tor example, either nitrogen, nitride, or ammo nia; and similarly', that carbonaccous reagent includes any reagent which will yield carbon under such conditions, as, for einem ple, charcoal, tuel oil, coal, cyanide, cyanamids, etc.

In conclusion l desire to call attention to the tact that iron when heated oloesino" conibine directly with free or molecular ,nitr ogen to .produce a stable nitrid, hence certain of the claims which deline the metal referred totherein as one which belongs, to that class olf metalswhich are capable when heated ot directly coinbrning,n with tree nitrogen to form nitrids, e1rclude potassium terre-cya nids, etc.; but do cover the use ol." manga` nese, chromium, titanium, cer-inni, etc., Which combine with tree nitrogen to form stable nitride, although they do not iorm cyanide like the all'aline earth and alkali metals. n

l. The process or producing cyanogen compounds and the like, which includes et 't'ecting Within a mass oit molten nonnqueous salt, a reaction in which nitrogen, carbon and a metal capable of being alloyed with a molte-n metal and belonging to that class otA metals whichY are capable when heated ot directly coinbininn'y with free nitrogen to form a stable nitrid, participate, to storm a compound ot the said tirst mentioned metal, and then reacting on the said compound with another metal capable oli .iforining'the base oit a stable cyanid, substantially as described.

'l5 he process oit producing cyanogen compounds and the like, which :includes footingn within a mass oi non-aqueous salt and at a temperature above 500D C, a reaction between .a plurality oli substances, one oit which. includes nitrogen as a constituent thereof, one of which comprises carbon as a constituent thereof, and one ot which comprises a metal capable ot being alloyed with a .molten metal and belonging; to that of nletals which are capable when heated ot directly coinbining with tree nitrogen to forni a stable nitrid, and then eli'c..ctin,fg, a second reaction between a product ot' the tirs-t reaction and' another metal capable ot forming; the base ot ars-table cyanid. A

3. The process ol producing cyanogen compounds and the litre, which includes et rooting; Within a mass ot molten cyanoggon.

(.:onipound alternate reactions in one ot which nitrogen and a metal capable ot' being alloyerl 'with a molten metal and belonging' to that group ot n'ietals wl'rich are capable when `heated oi" directly combinine,V with iree nitrogen to :torni stable nitride, participate, and in another ot which react-ions carbon and another metal capable ot torining' thebaso ot a stable cyanid participate.

4f.. The process ot producing; cyanogen compounds and the lilre which includes etlll@ fecting within a mass of molten alkali cyanogen compound and at a temperature above 500o l. which nitrogen and a. metal capable ot being alloyed with a molten metal and belonging lto that group ot metals which are capable when heated ot directly combining with free nitrogen to torni 'a stable nitrid, participate, and in anot-her 'of which reactions jarbon and an'alkali metal participate.-

The process ot'producing cyanfigen compounds and the .like which includes bringing a mass of molten 'cyanogen compound into Contact with nitrogen, carbon, a metal capable of being all'oyed with a molten metal and belonging to that class ot' metale which are capable when heated ot' directly "combining with tree nitrogen to t'orm a stable nitrid, and another metal capable ot forming the base of a Stable cyanid, and effecting react-ions between said ieubetances, eine of Said reactions forming a nitrid ot the tirst mentioned metal,

G. rflic process of producing alkali `cyanids, which comprises subjecting an alkaline earth metal to the action ot' heat and i'litrogenous and carbonaceous lsubstances while in contact with a molten non-aqueouay salt, thereby producing an alkaline earth metal compound containing carbon and nitrogen in Contact with said molten Salt, liberating the alkaline earth metal from such compound by lneane of an alkali metal, and

'repeating the cycle without permitting the alkaline earth metal to become cold.

7. The process ot' producing alkali cyanids, which comprise@y subjecting an alkaline earth metal to the action ot' heat and nitrogenous and carbonaceous substances while in Contact with a molten non-aqueous salt, thereby producing an alkaline earth metal compound containing carbon and nitrogen in contact with said molten salt, liberating the alkaline earth metal trom such compoun'd by mean@l ot an alkali metal contained in an alloy, and repeating the cycle Without permitting the alkaline earth metal to become cold.

8. The process offproducing alkali cyanids, which comprises subjecting barium to the action ot' heat and ot nitrogenous and carbonaceous substances while in contact with a molten non-aqueoul salt, thereby producing in contact with said molten salt a barium compound containing carbon and nitrogen, liberating the barium from such alternate reactions in one of' 9. The process of producing alkali cy-y anida, which comprises subjectmg barium to the actionl ot heat and ot' nitrogenous and carbonaceous substances while in Contact with a molten non-'aqueous Salt, thereby producingin contact with said molten Salt a barium compound containing carbon and nitrogen, and liberating the barium `from such compound by replacement with an alkali metal.

lO. The process of producing alkali cyanide, which comprises subjecting barium to the action ot' heat and of nitrogenous and carbonaceous substances while in Contact with a molten non-aqueous salt, thereby producing in contact with said molten Salt a. barium compound containing carbon and nitrogen, liberating the barium 'from such compound by replacement with an alkali 'metal contained in an alloy, and repeating the cycle without permitting the bariumto become cold.

ll. The process ot' producing alkali cyanids, which :comprises subjecting barium to the action of heat and of nitrogenous and y.carbonaceous Substances while in contact 4-with a molten noiraqueoue salt, thereby producing in contact with said molten salt a barium compound containing carbon and nitrogen, andA liberating the barium Jfrom euch compound by replacement with an alanother of said'ieactions converting Saidv nitrid into a c vanogcn compound.

ln witness whereof, I Subscribe my signature, in the presence ot two witnesses. l

CHARLES E. ACKER. lVitnesses:

lVALoo 1l. Unwin, lViLtiiAn C. `Iii-mr.

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