Why are sigma bonds stronger than pi bonds?
The reason behind this is the orientation of the overlapped orbitals. Sigma bonds result from head-on(co-axial) overlapping while pi bonds are outcome of lateral(para-axial) overlapping. Here is a pictorial representation of ethene(sp2 hybridized C atoms) :
The greater the extent of overlapping, the higher the probability of finding the valence electrons in between the nuclei and hence the bond will be stronger & shorter.
In MOT, this can be explained using Overlap Integral. This is how Atkins depicts it :
In simple terms, after forming a sigma-bond (a pre-requisite for pi-bonds), the two atoms get locked along the inter-nuclear axis. As a result, the orbitals available for pi-bonding can only partially overlap, thus forming a weaker bond.
As stated previously, it is due to the head-on overlap of sigma bonds and the lateral overlap of pi-bonds.
The smaller overlap of pi bonds also explains why double and triple bonds basically exist only for 2nd row elements (C,N,O especially) and not for higher row elements. A C=C bond has a length of 133 pm. A Si-Si bond length is at around 186 pm, therefore the contribution of the pi-integral overlap is almost negligible.
The inability of Silicium to form strong pi bonds is also one of the answer why life on earth is carbon based and not silicium based, since the richness of organic chemistry is in part due to the ability of carbon to form strong double and triple bonds.
Unsaturated compounds (due to the existence of a double bond) are more reactive than saturated compounds, because the electron density at the internuclear axis is zero in a pi bond (in contrast to the sigma bond).
Pi bonds involve sideways overlap while sigma bond involves head on or axial overlap. Axial overlaps have higher degree of overlapping than sideways overlap.
protected by jonsca♦ Jun 19 '14 at 13:00
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