Hydrates of organic compounds. II. The effect of alkyl groups on the formation of quaternary ammonium fluoride hydrates.
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概要
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The solid-liquid phase diagrams for the binary mixtures of water with various quaternary ammonium fluorides, (<I>n</I>-C<SUB>4</SUB>H<SUB>9</SUB>)<SUB>3</SUB>RNF (R=H, CH<SUB>3</SUB>, C<SUB>2</SUB>H<SUB>5</SUB>, <I>n</I>-C<SUB>3</SUB>H<SUB>7</SUB>, <I>i</I>-C<SUB>3</SUB>H<SUB>7</SUB>, <I>n</I>-C<SUB>4</SUB>H<SUB>9</SUB>, <I>i</I>-C<SUB>4</SUB>H<SUB>9</SUB>, <I>n</I>-C<SUB>5</SUB>H<SUB>11</SUB>, <I>i</I>-C<SUB>5</SUB>H<SUB>11</SUB>, <I>n</I>-C<SUB>6</SUB>H<SUB>13</SUB>, <I>n</I>-C<SUB>7</SUB>H<SUB>15</SUB>, and C<SUB>6</SUB>H<SUB>5</SUB>CH<SUB>2</SUB>), have been determined in order to see the effect of alkyl groups on the formation of clathrate hydrates. It has been found that, among these compounds, not only (<I>n</I>-C<SUB>4</SUB>H<SUB>9</SUB>)<SUB>4</SUB>NF, which has been known as a clathrate hydrate-forming salt, but also several other compounds with R=C<SUB>2</SUB>H<SUB>5</SUB>, <I>n</I>-C<SUB>3</SUB>H<SUB>7</SUB>, <I>i</I>-C<SUB>3</SUB>H<SUB>7</SUB>, <I>i</I>-C<SUB>4</SUB>H<SUB>9</SUB>, <I>n</I>-C<SUB>5</SUB>H<SUB>11</SUB>, and <I>i</I>C<SUB>5</SUB>H<SUB>11</SUB> can form hydrate type. These hydrates are believed to be of the clathrate hydrates since they have almost the same hydration numbers as that of (<I>n</I>-C<SUB>4</SUB>H<SUB>9</SUB>)<SUB>4</SUB>NF hydrate. From the melting points of these hydrates, it has been concluded that the most suitable alkyl chain length of quaternary ammonium salts for their clathrate-hydrate formation is C<SUB>4</SUB>-chain (butyl or isopentyl). In the cases of R=CH<SUB>3</SUB> and C<SUB>6</SUB>H<SUB>5</SUB>CH<SUB>2</SUB>, hydrates having lower melting points and smaller hydration numbers than those of the above group of hydrates have been detected. No hydrates have been observed for the salts with R=H, <I>n</I>-C<SUB>6</SUB>H<SUB>13</SUB> and <I>n</I>-C<SUB>7</SUB>H<SUB>15</SUB>.
- 公益社団法人 日本化学会の論文
著者
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Nakayama Haruo
Department of Applied Chemistry, Faculty of Engineering, Yokohama National University
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Watanabe Kazuichi
Department of Chemistry, Faculty of Engineering, Yokohama National University
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