REACTION OF METHANE AND ALSO OF ACETYLENE UPON 

 ZIRCONIUM TETRACHLORIDE 



By F. P. Venable and R. 0. Deitz 



The reactions of zirconium tetrachloride with certain hydrides as 

 ammonia, phosphine, and hj^drogen sulphide have been investigated 

 in so far as the changes taking place in the zirconium compound are 

 concerned. There are first formed with ammonia addition com- 

 pounds which on heating yield nitrides and hydrogen chloride. With 

 phosphine zirconium phosphide is formed and with hydrogen sul- 

 phide the product is zirconium sulphide. 



As zirconium carbide is somewhat imperfectly known, it seemed 

 of interest to examine the reaction between zirconium tetrachloride 

 and certain hydrocarbons. The carbide was prepared by Troost,^ 

 who heated powdered zircons with carbon in an electric furnace, 

 obtaining a substance which on analysis yielded results agreeing 

 fairly with the formula ZrCo, but no distinction was made between 

 free and combined carbon. Moissan^ prepared the carbide by fusing 

 zirconia with carbon, varying the amount of carbon in different 

 fusions and obtaining a substance of consistent composition agree- 

 ing with the formula ZrC. Wedekind^ later confirmed the work of 

 Moissan. So it may be concluded that normally zirconia reacts with 

 carbon at high temperatures, forming a carbide containing one atom 

 of each of the combining elements in the molecule. 



For the following experiments zirconium tetrachloride was pre- 

 pared and freed from traces of iron by the method used by Venable 

 and Bell."* It was retained in a hard glass tube where it could be 

 volatilized by means of an electric sleeve. Every precaution was 

 taken to avoid the presence of traces of water which would hydrolyze 

 the tetrachloride. 



Methane was prepared by heating anhydrous sodium acetate and 

 soda lime and was dried before admission to the reaction tube. This 

 tube contained about 5 grams of ZrCl^ which was volatilized during 

 the passage of the methane. Apparently no reaction took ])lace 



» Conijit. rend. 110, 1227. 1893. 

 » Conipt. rend. 116. 1222. 1893. 

 "Ann. 395. 149. 1912. 

 *Amer. Cheni. Soc. 39. 1598. 1917. 



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