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實(shí)驗室反應釜擴散控制方式

來(lái)源: 時(shí)間:2013-12-09 09:23:38 瀏覽次數:

我們已經(jīng)看到許多實(shí)驗室反應釜當溫度升至足夠高時(shí)便變成為擴散控制?,F在還將證明,在向擴散控制方式過(guò)渡時(shí),也能導致s形的放熱曲線(xiàn),因之,也能得到反應的上部和下部的穩定狀態(tài)。 考慮某一涉及氣體在固體表面的放熱反應。
我們已經(jīng)看到許多實(shí)驗室反應釜當溫度升至足夠高時(shí)便變成為擴散控制?,F在還將證明,在向擴散控制方式過(guò)渡時(shí),也能導致s形的放熱曲線(xiàn),因之,也能得到反應的上部和下部的穩定狀態(tài)。
考慮某一涉及氣體在固體表面的放熱反應。在這樣的反應中,固體的作用可能只作為催化劑存在(例如氨在鉑網(wǎng)上的氧化反應),或者是固體也可能參與了反應,并生成新的固相產(chǎn)物或全部轉化為氣體產(chǎn)物。
在足夠低的溫度下,上述所有過(guò)程中緩慢的一步可能是在表面進(jìn)行的化學(xué)反應。但是,在化學(xué)反應發(fā)生之前,氣體首先必須擴散到達固體表面,這個(gè)擴散可能包括通過(guò)固體產(chǎn)物層的擴散(如上例中的ZnO)或通過(guò)存在于系統中的其它氣體的擴散。在所有這些例子中,其中一個(gè)擴散過(guò)程應在化學(xué)反應過(guò)程之前發(fā)生,而另一個(gè)擴散過(guò)程,也就是反應的氣體產(chǎn)物向外擴散的過(guò)程,必盆緊接在反應之后。由于擴散的溫度系數通常比化學(xué)反應的沮度系數小得多,因而在足夠高的溫度下,通常是擴散過(guò)程真正慢于表面反應,這就導致擴散控制方式。其結果是得到反應放熱速率為一S形的曲線(xiàn),
這樣的情況可根據模型加以說(shuō)明。為簡(jiǎn)化計,設反應速率正比于在氣固表面上氣相的單一組分濃度的一次方。且假定反應只在固體的幾何表面上進(jìn)行(也就是它的內部多孔性是不重要的)。
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