1530
JOHN
n. CORBETT A4NDALEX HERSHAFT
satisfactory in that equilibrium pressures were not obtained over a sufficiently broad range of flow rates to give a reliable basis for establishing the corr e d value. Apparent Pressures a t intermediate flow rates (varied from 0.5 to 45 cc./min.) agreed with those obtained from effusion data, but, con-
VOl.
so
sidered independently, no satisfactory basis for choosing the correct value was evident. A&nowledgment.--We wish to acknowledge with thanks financial support received from the Office of Ordnance Research, U. S. Army. SEATTLE,
IVASIIINGTON
[CONTRIBUTIOX NO. 565 FROM THE INSTITUTE FOR ATOMICRESEARCH AND DEPARTMENT O F CHEMISTRY, I O W A STATE COLLEGE. IVORK WAS PERFORMED I N THE AMESLABORATORY O F THE ATOMICESERGY COMMISSION]
u.s.
The Lower Oxidation States of Gallium. 11. The GazBr4-GaBr System BY JOHN D. CORBETT AND ALEX HERSHAFT RECEIVED AL-GUST26, 1957 T h e compound GasBr, is dimorphic, with melting points of 153 and 164.5' for the a-(metastable) and t h e &forms, respectively. Reduction of this compound with gallium metal a t 170' gives a liquid containing 31.4 mole % ' GaBr in GanBra; the monobromide is stable in the solid state below the syntectic temperature of 164'. Complete reduction t o GaBr(s) below this temperature is limited by kinetic effects t o about 75% GaBr. Addition of A1Br3 to the liquid Ga-Ga2Bra system allows complete reduction of Ga(II1) t o Ga(AlBr4). Isomorphism between each of the two crystalline forms of Ga(A1Br4) a n d Gn?Br4shows the latter compound t o be Ga(GaBr4).
Introduction Although a t one time the formulation of the socalled gallium "dihalides" presented somewhat of a problem, i t has been shown recently in a number of ways that the chloride is actually Ga(GaC14) Furthermore, the reason for the formation of such an intermediate in spite of the instability of GaC14 has been given.' Since GaI has been isolated,j there is no reason to believe that GaJ4 is not formed by a similar acid-base interaction. The present paper deals with the GazBr4-GaBr system and the analogy between Ga(GaBr4) and Ga(AlBr4). Results and Discussion The compound GapBr4 exists in two crystalline forms with the transition near 90". Due to the slowness of the transformation and a considerable tendency for the liquid to supercool, i t is possible to observe melting points for both forms. These are 153 and 164.5" for the low (a) and high ( p ) temperature forms, respectively. The ease of the transformation depends markedly on composition. -4 liquid of composition GaBrz.ooshad to be quenched very rapidly from 170" in order to keep i t in the higher melting configuration, while very SIOW cooling was necessary to put a GaBrl,99bsample into the a-form. The transformation solid-liquidsolid was observed several times when the latter preparation was placed in the furnace a t 157". Only the @-formwas observed in powder patterns of quenched Ga2Brr-GaBr mixtures. Reduction of molten GazBr4with excess gallium gives a pale yellow liquid containing 31.4 mole 7 0 GaBr in GazBr4 (GaBrl.81) a t 170",and 30.070 (GaBrl,sz),a t 290". In comparison, reduction of the corresponding chloride and iodide a t 180 and (1) J . D . Corbett a n d R. K . McMullan, THISJOURNAL, 78, 2906 (1933). ( 2 ) L . A. Woodward, G . Garton and H. L. Roberts, J. Chem. Soc.,
3723 (1956). (3) G . Garton and H. M . Powell, J . I n o r g . Nucl. Chem., 4 , 84 (1957). 7 7 , 3964 (4) 1, D. Corbett and S . von Winbush, THISJOURNAL, (19651. (5) J . D . Corbett and R . K. McMullan, ibid.,7 7 , 4217 (1955).
267' gives solutions containing 7.404 and 89.5%5 monohalide, respectively.6 This trend of increasing stability of a lower halide with increasing atomic number of the halide also has been observed in a number of similar systems involving the formation of subhalides in solution or as solids.' Similar to other metal halide systems the trend noted here can be related primarily to a corresponding decrease in the stability of the complexes of the higher oxidation state, in this case GaXd-, that are being reduced.8 Although disproportionation of gallium monochloride results when the GaC1-GasC14 melt solidifies, the monobromide, like the monoiodide,j is stable in the solid state. The liquid of composition GaBrl.81gives a canary yellow solid when quenched and a white one when cooled slowly. The yellow material turns white when heated above about 120" ; the reverse change cannot be accomplished short of remelting and quenching. The nature of the yellow form is not understood, since the powder patterns of the yellow and white materials are identical. The stability of solid GaBr is in accord with the phase relationships observed, Fig. 1. The eutectic is near GaBrl,sband 152". As with the iodide system, where the eutectic is near Ga2I4 (GaIl,sl), and reduction in the liquid takes place to Ga11,19,5 the hypothetical melting point (or, less likely, the heat of fusion) of GaBr must be considerably greater than that of Ga2Br4. As can be seen in Fig. 1, the solution of composition GaBrl 81 is in equilibrium with solid GaBr and liquid gallium metal a t 164", the syntecticg ( 6 ) I n aII three systems, very smaIl temperature coefficients for the reduction limit, corresponding t o a heat of reaction of nearly zero, make t h e temperature variable unimportant in a qualitative comparison of t h e relative stabilities of t h e G a X products. (7) J. D Corhett, S von Winbush and F C Albers, THISJ O U R N A L , 79, 3020 (1957). ( 8 ) T h e thermal history effect in melting point noted f o r G a d & is probably t h e result of dissociation of GaId- into GaIa and I - ; no such behavior has been observed for t h e bromide or chloride. (9) An invariant system involving equilibrium between two liquids and an intermediate solid phase. F. R . Rhines, "Phase Diagrams in
LOWEROXIDATION STATES OF GALLIUM
April 5, 1958
temperature. Since a system containing excess metal and GasBr4 is unstable below this point, i t is possible in principle to achieve complete reduction to GaBr. In practice, however, due to both the limitations of physical contact between the liquid phases once an appreciable amount of solid GaBr has been formed and the low volatility of the components, reduction to the composition GaBrl.do (75 mole yo)a t 158' is the best that has been achieved.IO As expected from the phase relationships, the GaBr in such a mixture in excess of that required to form the liquid GaBrl.81 was observed to disproportionate to metal and this liquid a t 164165". Complete separation of GaBr from this mixture has not been accomplished. In spite of the marked solubility of GanBr4 in benzene (5.35 wt. yo) extraction of this from the finely powdered solid is very inefficient a t room temperature. The best product that has been obtained by this technique is GaBrl.3. More important, the stability of GaBr with respect to disproportionation is so slight that under conditions where GapBr4 dissolves, decomposition takes place a t an appreciable rate a t 35-40', and slowly even a t room temperature. This reaction is more pronounced with stronger bases such as mesitylene and dioxane. Powder patterns of mixtures with Br/Ga ratios of 1.8, 1.6, 1.4 and 1.3 show no evidence of intermediate compounds in this system, and readily allow the pattern of what is presumed to be GaBr to be deduced (Experimental section). I t is possible to achieve complete reduction of GazBr4to GaBr by the addition of the strong Lewis acid A1Br3, forming Ga(A1Br4)according to the reaction GazBr4 2Ga 4AlBr3 = 4Ga(AlBr4). In view of the similar properties of aluminum and gallium tribromides considerable physical and chemical similarity between Ga(GaBr4) and Ga(A1Br4) would be expected. Such a relationship has been noted with the corresponding acid-stabilized gallium(1) chlorides.' That there is a marked analogy between the two gallium(1) bromide complexes is clearly shown by the fact that Ga(AIBr4) is also dimorphic, with each form being isomorphous with the respective Ga(GaBr4) phase. As indicated by the powder pattern data (Experimental section) the AlBr4- ion is very similar in size to the corresponding gallium anion. Because of a more rapid transition in Ga(AlBr4) i t was not possible to determine the metastable melting point; the @-formmelts at 159".
+
+
Experimental Vacuum-sublimed GaBro or distilled Brt (A. D. Mackay,
