Citation:
. [J]. University Chemistry,
;2012, 27(2): 65-68.
doi:
10.3969/j.issn.1000-8438.2012.02.018
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[5] 谭天恩,麦本熙,丁惠华.化工原理.北京:化学工业出版社,1984
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[6] 陈敏恒,丛德滋,方图南.化工原理.北京:化学工业出版社,1985
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[7] 刘炼,叶寒芳,刘志刚.金属工艺学.成都:四川科学技术出版社,1985 (上接第51页) 表2中f表示—COOH中的C—O单键和O—H键之间的相对强弱,该值越小,O—H键越弱、C—O单键越强,则越易离解出质子,pKa也就越小。对于含2个或2个以上羧基的化合物来说,应该是f最小的羧基优先离解并决定其一级酸离解常数的大小。从表2可以看出,化合物1~5的一级酸离解常数对应的f分别为0.85446、0.85352、0.85268、O.84839和0.82977,这与表2中的pKa 实验值的大小顺序是完全相同的。以上分析表明,由量子化学计算得到的f可以作为比较苯氧乙酸类化合物酸性强弱的判据。此外,化合物5中的羧甲氧基和羧基的f分别为0.82977和0.85631,这说明羧甲氧基比羧基更易离解,其酸性强于苯甲酸,这与电子效应的解释相符,也与测定结果完全一致。因此f可以作为定性分析分子酸性强弱的参数之一。通过这个示例,学生不仅能学会利用计算的方法判断分子酸性强弱,而且能更深入理解酸离解常数pKa的意义及影响因素。 参 考 文 献
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