US EPA

8416617 

Journal Article 

The catalytic halides-XIII the interaction of gallium trichloride with ethyl, isopropyl, n-propyl, and t-butyl chlorides 

Wong, R; Brown, HC 

1955 

Yes 

Journal of Inorganic and Nuclear Chemistry
ISSN: 0022-1902 

1 

6 

402-410 

English 

10.1016/0022-1902(55)80049-8 

The phase diagrams for the ethyl chloride-gallium chloride system were determined at four temperatures, -78.5, -64, -50, and -36°. A 1 : 1 addition compound exists in the solution phase as shown by molecular weight determinations. A solid phase corresponding to the 1 : 2 compound, C2H5Cl : Ga2Cl6, was identified, and the heat of dissociation, C2H5Cl : Ga2Cl6(s) ⇄ C2H5Cl(g) + Ga2Cl6(s) is 9.74 kcal/mole. The heat of solution of the 1 : 2 compound in ethyl chloride is 5.0 kcal/mole and the calculated m.p. is -29°. The phase diagram for the isopropyl chloride-gallium chloride system was determined at -64°. Solid phases corresponding to both the 1 : 2 and 1 : 1 compounds, (CH3)2CHCl : Ga2Cl6 and (CH3)2CHCl : GaCl3, were identified. At higher temperatures, solutions of gallium chloride in isopropyl chloride evolved hydrogen chloride at an appreciable rate. Similar observations were obtained for solutions of gallium chloride in n-propyl and t-butyl chloride. Isomerization of n-propyl to isopropyl chloride was also observed. Under the same conditions the rate of hydrogen chloride evolution is t-butyl > isopropyl > n-propyl > ethyl chloride, which is also the order of stability of the carbonium ions of the respective alkyl groups. © 1955.