Reaction process of vanadium tetrachloride with ammonia in the vapor phase and properties of the vanadium nitride formed.

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The reaction products of gaseous VCl4 with ammonia were VCl4·4NH3 at 200 °C, VCl4·4NH3, VNx, and NH4Cl at 250–550 °C, and VNx and NH4Cl at 600–1000 °C. At 1100 °C, small amounts of VCl2 and HCl were formed in addition to VNx and NH4Cl. The N/V atomic ratio, x, of the VNx formed was 1.20 at 600 °C, 1.15 at 700 °C, 1.14 at 800 °C, and 1.13 at 900 and 1000 °C. The lattice constants of the VNx formed were shown. The reaction process of gaseous VCl4 with ammonia can be represented as follows: The reaction of gaseous VCl4 with ammonia first occurs to form VCl4·4NH3. Above about 215 °C, the reaction of VCl4·4NH3 with ammonia also occurs to form VNx. At 1100 °C, in addition to these reactions, the reaction of gaseous VCl4 with hydrogen formed by the thermal dissociation of ammonia occurs to form VCl2. On heating the VNx, formed by the vapor-phase reaction, at temperatures higher than 500 °C in an argon atmosphere, the value of x decreased with the increase in the heating temperature to 1.03 at 900–1000 °C.
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