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NCERT Exemplar · Q6

Q.The oxidation number of an element in a compound is evaluated on the basis of certain rules. Which of the following rules is not correct in this respect?

(i) The oxidation number of hydrogen is always +1.
(ii) The algebraic sum of all the oxidation numbers in a compound is zero.
(iii) An element in the free or the uncombined state bears oxidation number zero.
(iv) In all its compounds, the oxidation number of fluorine is – 1.
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Hydrogen's oxidation number is usually +1+1 but becomes −1-1 in metal hydrides; the other three rules hold universally. The incorrect rule is (i).

Oxidation numbers are a bookkeeping device to track electron distribution in compounds. They rest on a set of conventions that work together to assign a formal charge to each atom. Most of these rules are absolute, but a few have exceptions that trip up students who memorize without understanding the chemistry behind them.

The question asks which rule breaks down. Let's examine each one.

Evaluating each rule

Rule (i): The oxidation number of hydrogen is always +1+1.

Hydrogen is less electronegative than most elements, so it typically loses its share of the bonding electron and takes oxidation state +1+1. This is true in HX2O\ce{H2O}, HCl\ce{HCl}, CHX4\ce{CH4}, and the vast majority of compounds.

But when hydrogen bonds to metals—elements less electronegative than itself—the electron density shifts the other way. In metal hydrides like NaH\ce{NaH}, CaHX2\ce{CaH2}, and LiAlHX4\ce{LiAlH4}, hydrogen is the more electronegative partner and carries oxidation number −1-1. Sodium in NaH\ce{NaH} is +1+1, so hydrogen must be −1-1 to make the sum zero.

This exception is not obscure; metal hydrides are common reducing agents in organic chemistry. The word "always" makes this rule incorrect.

Rule (ii): The algebraic sum of all oxidation numbers in a compound is zero.

A neutral compound has no net charge, so the oxidation numbers—our formal charge assignments—must sum to zero. For a polyatomic ion, the sum equals the ion's charge. This is a defining principle of the oxidation-number system, not an empirical rule. It holds without exception.

Rule (iii): An element in the free or uncombined state bears oxidation number zero. …

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