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Question 49

Chlorine reacts with hot and concentrated NaOH and produces compounds (X) and (Y). Compound (X) gives white precipitate with silver nitrate solution. The average bond order between Cl and O atoms in (Y) is


Correct Answer: 1.67

We have chlorine reacting with hot and concentrated sodium hydroxide. 

$$3\,\text{Cl}_2 + 6\,\text{NaOH}\;(\text{hot, conc.}) \;\longrightarrow\; 5\,\text{NaCl} + \text{NaClO}_3 + 3\,\text{H}_2\text{O}$$

From this single reaction we can immediately identify the two products that contain chlorine in different oxidation states:

$$\text{NaCl}\;(\text{X}) \quad\text{and}\quad \text{NaClO}_3\;(\text{Y}).$$

Compound (X) is $$\text{NaCl}$$. When treated with silver-nitrate solution $$\text{AgNO}_3$$, it forms a curdy white precipitate of $$\text{AgCl}$$, exactly as described in the statement of the question, so our identification of (X) is consistent.

Therefore compound (Y) must be $$\text{NaClO}_3$$. In aqueous solution this salt furnishes the chlorate ion $$\text{ClO}_3^-$$, and it is in this ion that we have to discuss the average bond order of the Cl-O bonds.

First, recall the definition that will be used. For a species that shows resonance, the conventional (Pauling) bond order is defined as

$$\text{Bond order} \;=\; \frac{\text{Total bond multiplicity in all canonical forms}}{\text{Number of equivalent bonds}\;\times\;\text{Number of canonical forms}}.$$

Put colloquially, we count the value (1 for a single, 2 for a double, etc.) of each Cl-O bond in every possible resonance structure, add them all up, and then divide by the number of resonance structures times the three equivalent Cl-O positions. Every Cl-O bond in the real molecule has the same “average” order obtained in this way.

Now let us draw the lowest-energy (formal-charge-minimised) resonance structures of $$\text{ClO}_3^-$$. In each of them chlorine is hypervalent (uses a 3d orbital) and expands its octet. The pattern is

Cl has two Cl=O double bonds and one Cl-O− single bond.

Because any one of the three oxygen atoms can be the one that bears the negative charge, we obtain three canonical forms, all of equal weight:

  Structure 1: O=Cl=O with one O−
  Structure 2: O=Cl-O−=O
  Structure 3: O−-Cl=O=O

Let us now tabulate the bond multiplicities.

• In any one canonical form there are exactly two Cl=O double bonds. Each double bond carries a multiplicity of 2.
• In the same canonical form there is exactly one Cl-O single bond. A single bond carries a multiplicity of 1.

Therefore, in a single canonical form the total Cl-O bond multiplicity is

$$2 + 2 + 1 \;=\; 5.$$

There are exactly $$3$$ such canonical forms. Hence the grand total of Cl-O bond multiplicity summed over all canonical forms is

$$5 \times 3 \;=\; 15.$$

The number of equivalent Cl-O bond positions is $$3$$ (because there are three oxygens attached to the same chlorine). The Pauling definition now gives

$$\text{Average bond order} \;=\; \frac{15}{3 \times 3} \;=\; \frac{15}{9} \;=\; \frac{5}{3} \;=\; 1.67.$$\

Thus every Cl-O bond in the chlorate ion possesses an average order of $$\displaystyle 1.67$$, exactly as required.

So, the answer is $$1.67$$.

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