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(17) Eppler, B.; Neis, U.; Hahn, H. H. Prog. Water Technol. 1975, 7, 207-216. (18) Hunt, J. R. Ph.D. Dissertation, California Institute of Technology, 1980. (19) Gibbs, R. J. J. Sediment. Petrol., in press. (20) Pravdic, V. Limnol. Oceanogr. 1970, 15, 230-233. (21) Martin, J. M.; Jednacak, J.; Pravdic, V. Thalassia Jugosl. 1971, 7, 619-636. (22) Hunter, K. A.; Liss, P. S. Nature (London) 1979, 282, 823-825. (23) Neihof, R. A.; Loeb, G. I. Limnol. Oceanogr. 1972,17,7-16. (24) Neihof, R. A.; Loeb, G. I. J. Mar. Res. 1974, 32, 5-12. (25) Loeb, G. I.; Niehof, R. A. In "Applied Chemistry at Protein Interfaces"; Baier, R. E., Ed.; 1975; pp 319-335.
(26) Ham, R. K.; Christman, R. F. J. Sanit. Eng. Diu. Am. SOC. Civ. Eng. 1969, 95, 481-502. (27) Lathrop, J. E. M.S. Thesis, University of Delaware, 1980. (28) Kester, D. R.; Duedall, I. W.; Connors, D. N.; Pytkowitz, R. M. Limnol. Oceanogr. 1967,12, 176-179. (29) Anderson, J. V. Clays Clay Miner. 1963, Tenth National Conference, 380-388. (30) Smoluchowski, M. v. 2. Phys. Chem. 1971, 92, 129-168. (31) Camp, T. R.; Stein, P. C. J. Boston SOC.Civ. Eng. 1943, 30, 219-237. (32) Reeink, H.; Overbeek, J. T. Faraday SOC.Discuss. 1954, 18, 74-84.
Received for review July 14,1982. Accepted December 27,1982.
NOTES Reductive Destruction of Hydrazines as an Approach to Hazard Control George Lunn and Eric B. Sansone
Environmental Control and Research Program, NCI-Frederick
Cancer Research Facility, Frederlck, Maryland 2 1701
Larry K. Keefer"
Analytical Chemistry Section, Division of Cancer Cause and Prevention, National Cancer Institute, Bethesda, Maryland 20205 Hydrazine and 14 of its mono- and disubstituted alkyl, aryl, and acyl derivatives were quantitatively destroyed by using either of two nickel-based catalytic reductive procedures. Small volumes of solutions containing hydrazines were made alkaline and treated with aluminumnickel powder; large volumes were treated with preformed Raney nickel with or without an exogenous hydrogen source. No interference was discovered except from acetone. The only products detected were ammonia and the amines corresponding to the hydrazine reduced. No benzidine could be detected when 1,2-diphenylhydrazine was reduced. These procedures appear to provide a reliable, efficient, one-step approach to conversion of potentially carcinogenic hydrazines to innocuous products in laboratory wastes or in the environment. Hydrazine and its derivatives can enter the environment by a number of routes. Hydrazine has been used for boiler-water treatment, in the manufacture of blowing agents, agricultural chemicals, and medicinal agents, and (principally) as a propellant (1-3). Hydrazine may also be a product of nitrogen fixation by certain bacteria ( 4 ) . Substituted hydrazines have been used as drugs, herbicides, and propellants (4-9); two hydrazine derivatives, agaritine and N-methyl-N-formylhydrazine, have been isolated from edible mushrooms ( 4 ) . Hydrazine and several of its derivatives are carcinogenic (1,8-11). Attempts have been made to destroy residues of these compounds to prevent or reverse environmental contamination by them. Much of the emphasis in these chemical destruction studies has been on oxidative pathways, using reagents such as ozone (12) or hypochlorite (2). Unless carefully controlled, however, these pathways can lead to products that may be more hazardous than the starting material. For example, 1,l-dimethylhydrazine 240
Environ. Sci. Technol., Voi. 17, No. 4, 1983
(UDMH), used as a propellant in a variety of military and space applications (2,6-8)) can be oxidized to N-nitrosodimethylamine (7, 13). After noting that Seebach and Wykypiel(l4) used Raney nickel and hydrogen to convert hydrazines and nitrosamines to amines, we studied the applicability of catalytic reductions to the decontamination of wastes containing hydrazines. In this paper we report that hydrogenolytic cleavage of hydrazine and its derivatives can be conveniently, inexpensively,and quantitatively achieved under a wide variety of conditions, according to eq 1. The H2
-
+ R1R2NNHR3
Ni catalyst
R1R2NH + R3NHz
(1) results indicate that nickel-based reductive methods hold considerable promise as an approach to preventing environmental contamination by hydrazines.
Experimental Section Materials. With three exceptions, the hydrazine and amine standards used were purchased from Aldrich Chemical Co., Milwaukee, WI. 1,l-Diethylhydrazine, 1,l-diisopropylhydraine,and 1,l-di-n-butylhydrazinewere prepared by reducing the corresponding nitrosamine with lithium aluminum hydride (15). The products were distilled before use. The boiling points of the products were 90-94 OC (1,l-diethylhydrazine), 89-90 OC (180 mmHg) (1,l-diisopropylhydrazine),and 135 OC (200 mmHg) (1,ldi-n-butylhydrazine). The reported boiling points of these compounds are 96-99 OC, 41 OC (16 mmHg), and 87-90 "C (21 mmHg), respectively (15). Satisfactory purity was indicated in each case by the boiling point and gas chromatographic homogeneity. Aluminum-nickel alloy powder (50:50, w:w) was also obtained from Aldrich. Reduction Procedures with i n Situ Generation of Hydrogen and Nickel Catalyst. In a typical reaction,
0013-936X183/0917-0240$01 S o l 0
0 1983 American Chemical Society
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~
~
Table I. Reduction of Hydrazines (R' RZNNHR3)to the Corresponding Amines with Nickel-Aluminum Alloy in Potassium Hydroxide Solution column yield of amine, hydrazine, retention time, min R3 % %'" amine hydrazine columnb temp, "C R' RZ H Me
Et
i-Pr n-Bu
H Me
Et i-Pr n-Bu
Ph Ph
Me H
Ph
H H H
H H H H H H H H H Me H
Ph
C( 0)NHNHPh H H
