Sunday, September 29, 2019

inorganic chemistry - Why does nitric acid have a different molecular structure from phosphoric and arsenic acids?


I remember that this really bugged me as an undergrad, and upon revisiting some inorganic chemistry notes I realized I still don't have a satisfactory answer for it. The structure of nitric acid, $\ce{HNO3}$, is quite different from the structure of phosphoric acid, $\ce{H3PO4}$ and arsenic acid, $\ce{H3AsO4}$:


Structures of Group 15 oxoacids



Something tells me there should be an easy, intuitive argument explaining this, perhaps something about p-orbitals being more diffuse in phosphorus and arsenic? I find it kind of difficult to analyze this as a sort of "trend", since other groups don't really seem to have well defined oxyacids for the first two or three elements.


There is no oxyacid for water, but sulphuric and selenic acids are similar in structure; there is no oxyacid for fluorine either, but the oxyacids of chlorine and bromine are also analogous. In the carbon group something kind of strange also happens, with silicic acid (I believe) not really being a well-defined compound but a plethora of different things with different relative stabilities.




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