THE CATALYTIC PREPARATION OF HYDROXYLAMINE BY VALENTINE AUSTIN JONES B. S. University of Illinois 1921 THESIS Submitted in Partial Fulfillment of the Requirements for the Degree of MASTER OF SCIENCE IN CHEMISTRY IN THE GRADUATE SCHOOL OF THE UNIVERSITY OF ILLINOIS 1922 UNIVERSITY OF ILLINOIS THE GRADUATE SCHOOL Ja nuary 19, 192J? I HEREBY RECOMMEND THAT THE THESIS PREPARED UNDER MY SUPERVISION BY- Valenti n s Aust in jLcnes ENTITLED The Catalytic Preparation cf K ydroxylarjjn e BE ACCEPTED AS FULFILLING THIS PART OF THE REQUIREMENTS FOR THE DEGREE OF jjas t ery_of Science Recommendation concurred in* Committee on Final Examination* *Required for doctor’s degree but not for master’s 438978 Digitized by the Internet Archive in 2016 https://archive.org/details/catalyticpreparaOOjone Acknowledgment The writer wishes to express his appreciation and sincere thanks to Doctor J.H. Reedy for his assistance in the experimental work, and also for his aid in writing this thesis Table of Contents I. Introduction. II. Historical. III. Purpose of Research. IV. Experimental. V. Discussion. VI . Summary . VII. Bibliography. The Catalytic Preparation of Hydroxylamine . I . Introdu c tion . The question of procuring a good yield of Hydroxylamine by a simple and inexpensive method has been the subject of consi- derable investigation by chemists for many years. A few methods have been suggested and used for its preparation, but in all the yields are not good, and the methods of separation from by-products are difficult and not conducive to complete separation. Reduction of nitrites , nitric acid and nitric oxide to Hydroxylamine by such reducing agents as sulphurous acid, chromous chloride, hydrogen sulphide .hydrogen, etc. , have been attempted with but indifferent success , mainly , because of the fact that a good method of separation was lacking or that the reduction did not stop at Hydroxylamine, but continued further to give nitrous oxide, nitrogen or ammonia. It was noticed by Victor Meyer and others that often some substance used as a catalyser or by-products of the reactions would cause the immediate decomposotion of any Hydroxylamine which might be formed. The urgent need of a catalyser which could be used to facilitate the reduction of nitric oxide to Hydroxylamine alone and still not cause the decomposition of the Hydroxylamine formed, seeias a paramount necessity if we expect to obtain Hydroxylamine in nearly theoretical amounts. ' II* Historical In 1834 Faraday ' published an article wherein he described some experiments on the use of platinum sponge as a catalyser. Among the reactions he experminted with was the reduction of nitric oxide by means of hydrogen using the platinum sponge as a catalyses He passed a mixture of hydrogen and nitric oxide slowly over pla- tinum sponge at room temperature. Reduction of the nitric oxide took place but his final product was not Hydroxylamine as he ex- X 3 pected but ammonia and water. F.Kuhlmann and Jouve“also working on the reduction of nitric oxide by hydrogen with the use of pla- tinum sponge as a catalyser obtained ammonia and water as the final product, altho Jouve working at temperatures not exceeding 115°C, claims to have obtained 1-2 % of Hydroxylamine. Cooke working with a mixture of nitric oxide and hydrogen and using platinum sponge as a catalyser , states that he obtained ammonia, Hydroxylamine and nitrous oxide, the amounts of which he does not mention in his paper. He states that if one uses nitric oxide and hydrogen in the volume ratio of 1-2, the following re- action will take place 2N0 +- H2 H20 + N20 and for 2 volumes of nitric oxide and 8 volumes of hydrogen the equation is 2N0 + 4H2 —NH20H NH40H Sabatier and Senderens, - Neogie and Adhicary used nickel and copper as catalysers. They passed a mixture of nitric oxide and of hydrogen thru a glass tube which contained finely divided nickel or copper at temperatures ranging from 150-250 'C. The resulting product was ammonia and nitrogen. According to Divers and Hagaf Dummreicher* and Chesneau,^ Hydroxylamine and ammonia are produced when nitric oxide is passed thru a series of gas-washing bottles containing tin and cone, hydrochloric acid.. The yields, however, are small and the separa- tion of the Hydroxylamine hydrochloride is not easily accomplished. Chesneau 1 ' experimenting with a solution of chromous chloride claims to have reduced nitric oxide to Hydroxylamine and ammonia. He points out that a rapid constant amount of nitric oxide must be passed into an acid solution to form Hydroxylamine, otherwise a slow stream will cause the formation of ammonia. Ludwig and Hein, Divers and Haga" published papers in which they state that Hydroxylamine can be obtained in considerable amounts if nitric oxide is passed slowly into a heated mixture of tin and hydrochloric acid. They do not state the yields ob- tained by this method. Chromous chloride solution according to Chesneau and Kohl- schutter" reduces nitric oxide to ammonia in neutral solutions while in acid solution it reduced to Hydroxylamine . The same authors also found that hydroiodic acid reduces nitric oxide to ammonia and nitrous oxide. )3 Dummreicher reports that stannous chloride in strongly acid solution will reduce nitric oxide to Hydroxylamine in small amounts and not readily. /*- Hans Ziehl attempted to prepare Hydroxylamine by the reduc- tion of nitric oxide using a colloidal solution of platinum, which he prepared by reducing a sightly alkaline solution of chlor- platinic acid with hydrazine and adding a small amount of gum arabic. Equal volumes of hydrogen and nitric oxide were passed under pressure into a pressure bottle containing the colloidal platinum. The bottle is connected to a shaking devise and sha- ken vigerously. Ziehl found that no Hydroxylamine was formed by this method but that his final product consisted of ammonia and nitrogen. A mixture consisting of 2 volumes of nitric oxide and 3 volumes of hydrogen was tried but as before he obtained ammonia and nitrogen. They found that 82.34$ of the nitric oxide was changed to nitrogen while 15.73$ became ammonia. Divers and Haga'have succeeded in obtaining Hydroxylamine in the following manner. If sodium sulphide and sodium nitrite in solution are mixed, then acidified and boiled, Hydroxylamine is formed, and when the sulphide is in the proportion of 2 mols to 1 mol of the nitrite, and the hydrochloric acid added very slowly, almost all of the nitrogen is found on titration with iodine to have been converted into Hydroxylamine. NaN02 -r 2Na2S03 + HOH t RHCL — ^NH20H,HC1 3Nacl 2NaHS04 On evaporating the acid solution, separating the sodium salts by absolute alcohol and evaporating again, Hydroxylamine sulphate separates out. Further experiment proved that sodium meta- sulphide used with sodium nitrite gave the best yield of Hydroxy- lamine sulphate. In 1387 Raschig reported that Hydroxylamine can be gotten from a nitrite by sulphonation followed by hydrolysis. Divers .... it m 'M 111. I * 3 and Haga working on the suggestion given by Raschig's work used a concentrated solution of 2 raols of commercial sodium nitrite, 1 mol of sodium carbonate and then treated the solution with sulphur dioxide until just acid, while it was kept well agitated at2-3'"C below zero. It was claimed by them that at this temperature sul- phur dioxide will not act on Hydroxylamine but will reduce the nitrite completely. At this temperature the conversion of the ni- S * 2 trite into oximido-sulphonate^'^v, c r