pBlock ElementsII 1 Question 16

16. The reaction of white phosphorus with aqueous $\mathrm{NaOH}$ gives phosphine alongwith another phosphorus containing compound. The reaction type, the oxidation states of phosphorus in phosphine and the other product respectively are

(2012)

(a) redox reaction, -3 and -5

(b) redox reaction, 3 and +5

(c) disproportionation reaction, -3 and +5

(d) disproportionation reaction, -3 and +3

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Solution:

  1. The reaction of white phosphorus with aqueous alkali is

$$ \mathrm{P}{4}+3 \mathrm{NaOH}+3 \mathrm{H}{2} \mathrm{O} \longrightarrow \mathrm{PH}{3}+\mathrm{NaH}{2} \mathrm{PO}_{2} $$

In the above reaction, phosphorus is simultaneously oxidised $\left[\mathrm{P}{4}(0) \longrightarrow \mathrm{NaH}{2} \stackrel{+1}{\mathrm{P}} \mathrm{O}{2}\right]$ as well as reduced $\left[\mathrm{P}{4}(0) \longrightarrow \stackrel{-3}{\mathrm{P}} \mathrm{H}{3}\right]$ Therefore, this is an example of disproportionation reaction. Oxidation number of phosphorus in $\mathrm{PH}{3}$ is -3 and in $\mathrm{NaH}{2} \mathrm{PO}{2}$ is +1 . However, +1 oxidation number is not given in any option, one might think that $\mathrm{NaH}{2} \mathrm{PO}{2}$ has gone to further decomposition on heating.

$$ 2 \mathrm{NaH}{2} \mathrm{PO}{2} \stackrel{\Delta}{\longrightarrow} \mathrm{Na}{2} \mathrm{H} \stackrel{+5}{\mathrm{P}} \mathrm{O}{4}+\mathrm{PH}_{3} $$