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What is the hybridisation in HCN molecule?

Chemistry Asked by sfsg on December 31, 2021

According to VSEPR theory hybridisation of the central atom should be sp. However, my teacher says that there exists a near-100% s-character in the carbon orbital that bonds with hydrogen due to some other reasons. I couldn’t get why that would be the case. One can think of it as the nitrogen that polarizes the carbon atom, but shouldn’t it lower the s-character of the C-H bond? What am I missing?

Is it based on quantum calculations (which are beyond my scope) , as a commentator points out?

One Answer

$ce{HCN}$ and $ce{HC#CH}$ are linear, triple bonded, with a $π$ system consisting of two perpendicular $π$ bonds. They would be symmetrical in $ce{HC#CH}$, and slightly distorted in $ce{HCN}$, and they leave two orbitals for the sigma system.

In $ce{HCN}$, we hybridize/combine the two remaining orbitals on the carbon atom to form two bonding orbitals, one to the hydrogen, another to the atom on the other side of the carbon (a $ce{C}$ or an $ce{N}$). The natural first combination is a $50$$50$ split to form two $mathrm{sp}$ orbitals, one directed to the $ce{H}$ and the other directed toward the $ce{N}$.

That's enough most of the time, but if you get picky, you could point out that the electronegativities of $ce{H}$ and $ce{N}$ are quite different ($ce{H}$ $2.1$, $ce{C}$ $2.5$, $ce{N}$ $3.0$), so the nitrogen will be pulling on its $mathrm{sp}$ bond more than hydrogen pulls on its $ce{sp}$ bond, so the $50$-$50$ split readjusts to maybe $70$-$30$ (did your teacher say $~100%$-$0%$?), meaning that the hydrogen gets less of the carbon orbital (i.e., less $mathrm p$-character, more $mathrm s$-character from the carbon orbitals), while the nitrogen gets more of carbon's $mathrm p$-orbital.

If this is so, the $ce{H}$ atom in $ce{HCN}$ should be more easily removed than a H atom in $ce{HC#CH}$. This appears to be correct: the $pK_mathrm a$ of acetylene is $24$ (which is considered to be quite acidic for a hydrocarbon), whereas the $pK_mathrm a$ of hydrocyanic acid is $9.21$, much more acidic (although a weak acid by any other measure).

Your teacher pointed out something interesting, but the exact split ratio remains to be calculated.

Answered by James Gaidis on December 31, 2021

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