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作 者:夏树屏[1] 高世扬[1] 胡满成[1] 高胜利[2] 蒋育澄[1]
机构地区:[1]陕西师范大学应用化学研究所 [2]西北大学化学系,陕西西安710062
出 处:《南开大学学报(自然科学版)》2005年第4期22-27,共6页Acta Scientiarum Naturalium Universitatis Nankaiensis
基 金:Supported by the National Natural Science Foundation of China (20271051)
摘 要:用Rb2CO3(或Cs2CO3)与NTO(3-硝基-1,2,4三唑-5酮,C2N4O3H2)的水溶液混合制备Rb(NTO)·H2O,Cs(NTO)·H2O.用量热法测定了在298.15 K时M(NTO)·H2O(M=Rb,Cs)在水中的溶解焓.(NTO)·H2O和Cs(NTO)·H2O的标准生成焓分别是(-587.57±2.12) kJ·mol-1和(-596.92±2.11) kJ·mol-1.还分别计算了它们的晶格能、晶格焓、脱水生成焓[(RbNTO,cr)是551.46、546.96、-428.33 kJ·mol-1,(CsNTO,cr)是526.31、521.31、-432.35 kJ·mol-1].计算得到Rb(NTO)·H2O和Cs(NTO)·H2O的标准脱水焓分别为(126.57±2.12)kJ·mol-1和(124.26±2.1)kJ·mol-1.并讨论了碱金属的NTO盐的生成焓之间的关系:从Li+→K+的标准生成焓随离子半径增加而增大,但从K+→Cs+,虽离子半径增加但标准生成焓几乎不变.Rb (NTO) · H2O and Cs (NTO) · H2O were prepared by mixing the aqueous solution of NTO (3- nitro-1,2,4-triazol-5-one) with Rb2CO3(or Cs2CO3). The enthalpies solutions of M(NTO) · H20 (M=Rb,Cs) in water have been measured by calorimetrical method at 298.16K. The standard formation enthalpies were obtained to be (-687.67±2.12)kJ·mol^-1 for Rb(NTO) · H2O and (-596.92±2.11)kJ ·mol^-1 for Cs(NTO) · H2O using date reported by us and others and Kapustinskii's equation. The lattice energies, lattice'enthalpies and standard formation enthalpies of were calculated to be 551.46, 546.96, - 428.33 kJ·mol^-1 for (RbNTO, cr)and for (CsNTO,cr), 626.31, 621.31, -432.36 kJ·mol^-1 for (CsNTO ,cr) respectively. The standard dehydration enthalpies of Rb(NTO) · H2O [(126.57 ±2.12) kJ ·mol^-1] and Cs(NTO) · H2O[(124. 264±2.1) kJ ·mol^-1] were calculated. A relation between enthalpies of alkali metal salts of NTO and radii of metals has also been discussed, the values of standard formation enthalpies are increased as the radius increases of cation ions. (Li^+→K^+). But the standard formation enthalpies of (K^+→Cs^+) have hardly any change.
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