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Muhammed Irshad Shahul Hameed

The source for the N-N bond dissociation energy of 240 kJ/mol in the table

David Quinn  Follow

Your question about the source of Table 7.1 is correctly answered by the andselisk's comment. The value of $\pu{240 kJ\:mol-1}$ for $\ce{N-N}$ bond is probably initiated from Encyclopedia of Inorganic Chemistry, which has listed bond energies of wide variety of bonds and their respective bond lengths. It has given two values for $D_\circ$ of $\ce{N-N}$ bond: ~$\pu{167 kJ\:mol-1}$ for $\ce{N2H4}$ in general and $\pu{247\pm 13 kJ\:mol-1}$ for $\ce{H2N-NH2}$ in particular.

The reason is given in the very first paragraph of the article. In their words:

There are two different ways to define the bond energy even for the simplest diatomic molecule (see the diagram below). $\Delta D_{\circ'}$ is the dissociation energy measured from the very bottom of the potential energy well. However, the molecule possesses zero-point energy and thus, the experimentally measured dissociation energy $\Delta D_{\circ}$ is somewhat less:

Bond Energy and Bond length

In poly atomic compound there are other considerations. For example, the mean bond energy of $\ce{N-H}$ is the average of three bond energies associated with sequential fission of the three $\ce{N-H}$ bonds in ammonia ($\ce{NH3}$). These three values are different from each other and also different from their average, the mean bond energy of $\ce{N-H}$. Using this mean bond energy of $\ce{N-H}$ in $\ce{NH3}$ and the heat of atomization of $\ce{H2N-NH2}$, a value of $\pu{159 kJ\:mol-1}$ has been found for the $\ce{N-N}$ single bond energy. Then again, using the mean bond energy of $\ce{N-F}$ in $\ce{NF3}$ and the heat of atomization of $\ce{F2N-NF2}$, a value of $\pu{172 kJ\:mol-1}$ has been found for the $\ce{N-N}$ single bond energy. These two values are in somewhat good agreement. However, the dissociation of the two molecules are quite different:

$$\ce{H2N-NH2 -> 2 H2N^.} \qquad \pu{247 kJ\:mol-1}$$$$\ce{F2N-NF2 -> 2 F2N^.} \qquad \pu{88 kJ\:mol-1}$$

Therefore, it is warned that care should be exercised in using any values of the bond energies.

Source:

R. Bruce King (Editor in chief), "Bond Energies," Encyclopedia of Inorganic Chemistry; 2nd Edition, John Wiley & Sons, Ltd.: New York, NY, 2005 (ISBN: 978-0-470-86078-6). Bond Energies is available online: https://doi.org/10.1002/0470862106.id098

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Iqra Waseem  Follow
So once the N-N bond in hydrazine is broken, the N-H bonds are much weaker than they would be in ammonia? I like talking about bond dissociation energies in a General Chemistry setting, but always say it is a crude estimate. Even so, I think it is helpful in e.g. understanding how elemental oxygen is a reagent in many exothermic reactions while elemental nitrogen is not (at least not with the reaction partners that are sitting out on the shelf - I guess if they reacted with elemental nitrogen, they would not be sitting there anymore).More
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