The reactions of acetylene and propyne at the surface of liquid sodium

C. C. Addison, M. Hobdell, R. J. Pulham
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引用次数: 3

Abstract

The reactions of acetylene and propyne at the surface of liquid sodium have been studied at 110, 150, and 200 °C. A fresh metal surface was maintained by magnetic stirring, so arranged that the metal poured continuously over a baffle plate. The course of the reactions was followed from pressure–time curves, and the i.r. spectra of the gas phase. At 110 °C, propyne reacts smoothly according to equation (i) and all hydrogen atoms produced at the 3MeCCH + 2Na → 2NaCCMe + MeCHCH2(i), surface of the metal are employed in the hydrogenation of propyne to propene. A smaller effect (probably polymerisation) also becomes evident at 200 °C. The behaviour of acetylene is markedly different, and the reaction proceeds in two stages. In the first, disodium acetylide (but no hydrogen acetylide) is formed, and the gas phase consists of hydrogen and ethylene in the ratio 1·42 : 1 at 150 °C. No ethane was detected. The second stage involves reaction of hydrogen with sodium metal, and this does not commence until all acetylene is removed from the gas phase. The results are discussed qualitatively in terms of the relative absorption of the gases at the sodium surface, which may have some analogies with their absorption coefficients at transition-metal surfaces.
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乙炔和丙炔在液态钠表面的反应
研究了乙炔和丙炔在110℃、150℃和200℃液钠表面的反应。磁搅拌使金属表面保持新鲜,使金属连续地倒在挡板上。用压力-时间曲线和气相红外光谱跟踪了反应过程。在110℃时,丙烯根据式(i)进行了平稳反应,金属表面3MeCCH + 2Na→2NaCCMe + MeCHCH2(i)生成的氢原子全部用于丙烯加氢生成丙烯。在200°C时,较小的效应(可能是聚合)也变得明显。乙炔的反应行为明显不同,反应分两个阶段进行。第一种反应生成乙酰二钠(但不生成乙酰氢),在150℃下气相由氢和乙烯组成,比例为1·42:1。没有检测到乙烷。第二阶段涉及氢与金属钠的反应,直到所有乙炔从气相中除去后才开始。结果定性地讨论了气体在钠表面的相对吸收,这可能与它们在过渡金属表面的吸收系数有一些相似之处。
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