Experimental Binary Phase Diagram of Bilayer Compounds [n-CnH2n+1N(CH3)3]2CoCl4

doi:10.1007/s40242-015-4418-6

Abstract

Abstract:

Compounds [n-C_nH_2n+1N(CH₃)₃]₂CoCl₄(n=16, C₁₆C₃Co; n=18, C₁₈C₃Co) containing lipid-like bilayers embedded in a crystalline matrix exist in solid-solid phase transition. The low-temperature bilayer structures of the two compounds were organized by neutralizing CoCl₄^2- with alkylammonium ions. Alkyl chains lay parallel to each other and slightly tilted with respect to the normal of the inorganic layers. The adjacent alkyl chains interacted with each other by van der Waals interaction. When the temperature increased, the two compounds underwent a reversible solid-solid phase transformation within 310―330 K. In such a case, the chains showed a large motional freedom, and a disordered phase appeared. The structures can alternatively be viewed as a double layer of alkylammonium ions between CoCl₄^2- sheets and be considered as crystalline models of lipid bilayers. The experimental subsolidus binary phase diagram of [n-C₁₆H₃₃N(CH₃)₃]₂CoCl₄-[n-C₁₈H₃₇N(CH₃)₃]₂CoCl₄ was constructed over the entire composition range by differential scanning calorimetry and X-ray diffraction technique. Experimental phase diagram indicates one stable intermediate phase [n-C₁₆H₃₃N(CH₃)₃][n-C₁₈H₃₇N(CH₃)₃]CoCl₄ at w_{C₁₆C₃Co}= 39.89% and two invariant three- phase equilibria, which shows two eutectoid temperatures: T_e1 at (316±1) K for w_{C₁₆C₃Co}= 27.35% and T_e2 at (313±1) K for w_{C₁₆C₃Co}=59.76%. These three noticeable solid-solution ranges are α-phase at the left, β-phase at the right, and γ-phase in the middle of the phase diagram.

Key words: Quaternary ammonium tetrachlorometallate, Differential scanning calorimetry, Eutectoid temperature, Phase equilibrium, Phase diagram

WU Kezhong, SUN Xiaolong, RUAN Bei, XIONG Yuanyuan, CHEN Jing. Experimental Binary Phase Diagram of Bilayer Compounds [n-C_nH_2n+1N(CH₃)₃]₂CoCl₄[J]. Chemical Research in Chinese Universities, 2015, 31(4): 611-614.

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Experimental Binary Phase Diagram of Bilayer Compounds [n-C_nH_2n+1N(CH₃)₃]₂CoCl₄

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