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Henry Rzepa's Blog

Henry Rzepa's Blog
Chemistry with a twist
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This comes to you from China, and the city of Suzhou. To set the scene, cities in China have a lot of motorbikes. Electric ones. With their own speed units, a % of Panda speed. Msny msny people ride bikes such as these; some even manage three passengers, or several boxes of shopping. And the streets will have dedicated lanes for them, although you do need eyes in the back of your head to spot their silent (often 15 kph) approach.

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A fascinating re-examination has appeared[cite]10.1002/anie.201505482[/cite] of a reaction first published[cite]10.1002/ange.19600721210[/cite] in 1960 by Wittig and then[cite]10.1002/jlac.19646790106[/cite] repudiated by him in 1964 since it could not be replicated by a later student.

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I recently followed this bloggers trail; link1 → link2 to arrive at this delightful short commentary on atom-atom bonds in crystals[cite]10.1107/S2052252515002006[/cite] by Jack Dunitz. Here he discusses that age-old question (to chemists), what is a bond? Even almost 100 years after Gilbert Lewis’ famous analysis,[cite]10.1021/ja02261a002[/cite] we continue to ponder this question.

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As I have noted elsewhere, Gilbert N. Lewis wrote a famous paper entitled “ the atom and the molecule “, the centenary of which is coming up.[cite]10.1021/ja02261a002[/cite] In a short and rarely commented upon remark, he speculates about the shared electron pair structure of acetylene,  R-X≡X-R (R=H, X=C). It could, he suggests, take up three forms. H-C:::C-H and two more which I show as he drew them.

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This might be seen as cranking a handle by producing yet more examples of acids ionised by a small number of water molecules. I justify it (probably only to myself) as an exercise in how a scientist might approach a problem, and how it linearly develops with time, not necessarily in the directions first envisaged.

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I do not play poker,‡ and so I had to look up a 5-4-3-2-1(A), which Wikipedia informs me is a 5-high straight flush, also apparently known as a steel wheel. In previous posts  I have suggested acids which can be ionised by (probably) 5, 4, 3 or  1 discrete water molecules in the gas phase;

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My previous posts have covered the ionization by a small number of discrete water molecules of the series of halogen acids, ranging from HI (the strongest, pKa -10) via HF (weaker, pKa 3.1) to the pseudo-halogen HCN (the weakest, pKa 9.2). Here I try out some even stronger acids to see what the least number of water molecule needed to ionize these might be. Firstly what must surely be the ultimate acid

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HCN is a weak acid (pKa +9.2, weaker than e.g. HF), although it does have an isomer, isocyanic acid or HNC (pka < +9.2 ?) which is simultaneously stronger and less stable. I conclude my halide acid series by investigating how many water molecules (in gas phase clusters) are required for ionisation of this “ pseudo-halogen ” acid.