1,1′-二羟基-5,5′-联四唑二羟胺盐及碱金属盐的合成、溶解度测定及关联

Synthesis,Measurement and Correlation of Solubility of Dihydroxylammonium and Alkali Metal Salts of 5,5′-Bistetrazole-1,1′-diolate

以1,1′-二羟基-5,5′-联四唑为原料,分别与氢氧化锂、氢氧化钠、氢氧化钾反应得到1,1′-二羟基-5,5′-联四唑的碱金属盐：1,1′-二羟基-5,5′-联四唑二锂盐（Li2DHBT）、1,1′-二羟基-5,5′-联四唑二钠盐（Na2DHBT）、1,1′-二羟基-5,5′-联四唑二钾盐（K2DHBT）,收率分别为90.6%、91.9%、90.2%。以Li2DHBT为原料,通过与盐酸羟胺的复分解反应得到1,1′-二羟基-5,5′-联四唑二羟胺盐（HATO）,收率为94.1%。利用激光监测技术,采用动态法测定了20-60℃下,HATO、Li2DHBT、Na2DHBT和K2DHBT在水中的溶解度,利用理想溶液模型和Apelblat方程对实验数据进行了关联。结果表明,四种盐在水中的溶解度均随温度的升高而增加。理想溶液模型、Apelblat方程的拟合值与实验值的平均相对误差在3.5%以内,但Apelblat方程对实验数据的关联结果较优。溶解热力学计算结果表明,HATO、Li2DHBT、Na2DHBT、K2DHBT的溶解焓分别为27.991,27.632,31.125,17.991kJ·mol^-1,溶解熵分别为23.431,36.807,41.251,3.139J·mol-1·K^-1。

Dilithium5,5′-bistetrazole-1,1′-diolate（Li2DHBT）,disodium5,5′-bistetrazole-1,1′-diolate（Na2DHBT）and dipotassium5,5′-bistetrazole-1,1′-diolate（K2DHBT）were synthesized from 5,5′-bistetrazole-1,1′-diole with high yields over 90%,while dihydroxylammonium5,5′-bistetrazole-1,1′-diolate（HATO）was synthesized by ion exchange reaction with lithium ions with high yield of 94.1%.Using the laser monitoring technique,the solubilities of HATO、Li2DHBT、Na2DHBT and K2 DHBT in water from20 ℃to 60 ℃ were measured by dynamic method.The experimental data were correlated with the ideal solution model and Apelblat equation.Results show that the solubilities of four kinds of salts increase with increasing temperature.The average relative deviations between experimental and calculated data by ideal solution model and Apelblat equation are less than 3.5%,while the Apelblat equation gives the better fit with the experimental data.The enthalpies of dissolution of HATO,Li2 DHBT,Na2DHBT,K2 DHBT are 27.991,27.632,31.125 kJ·mol^-1 and 17.991 kJ·mol^-1,and the entropy of dissolution of HATO,Li2 DHBT,Na2DHBT,K2 DHBT are 23.431,36.807,41.251-1J·mol^-1·K^-1 and 3.139 J·mol·K^-1,respectively.