Question

19) In Nitrogen family basicity of Hydrides are
from N to Bi
a) increases b) decreases
c) remains constant d) zero​

Answer 1

Answer:

increases.....................

Answer 2

Answer:

OPTION (B) DECREASES

Explanation:

Each of these molecules has a pair of electrons in an orbital - this is termed a "lone pair" of electrons. It is the lone pair of electrons that makes these molecules nucleophilic or basic. As you move down the column from nitrogen to bismuth, you are placing your outermost shell of electrons, including the lone pair, in a larger and more diffuse orbital (the nitrogen lone pair is contained in the n=2 shell, while the bismuth lone pair is in the n=6 shell). As the electron density of the lone pair is spread over a greater volume and is consequently more diffuse, the lone pair of electrons becomes less nucleophilic, less basic.

Response to Comment: The ENs of the central atoms are N (3.04), P (2.19), As (2.18), Sb (2.05), Bi (2.02). All of these atoms, except for nitrogen have similar ENs and I think the electron density argument is valid for them. However, in the case of nitrogen and phosphorous there is a significant EN difference that would tend to argue in the direction opposite to my answer. However there is another important difference between N and P. The lone pair in ammonia is in an sp3 orbital. In all of the other cases the central atom is essentially unhybridized (~90° H-X-H angles) and the lone pair exists in an s orbital. Therefore the lone pair electron density in ammonia (being in an sp3 orbital) is effectively increased compared to phosphine where the lone pair is in an s orbital. So even though the EN difference between N and P is significant, when hybridization differences of the central atom are taken into account the electron density argument still explains the trend in basicity.

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