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Worked Examples · Example 3.3

Q.Calculate the overall order of a reaction which has the rate expression

(a) Rate =k[A]1/2[B]3/2= k[A]^{1/2}[B]^{3/2}
(b) Rate =k[A]3/2[B]−1= k[A]^{3/2}[B]^{-1}
Telangana TsbieTextbookSubjective· 2mImportance★★★★★
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✓ Free question

The overall order of a reaction is the sum of the exponents in its rate law. For (a) the sum is 1/2+3/2=21/2 + 3/2 = 2, so the reaction is second order. For (b) the sum is 3/2+(−1)=1/23/2 + (-1) = 1/2, so the reaction is half order.

The overall order of a reaction tells you how the rate depends on the concentration of all reactants combined. It’s the sum of the individual orders with respect to each reactant. This is a straightforward addition problem, but the trick is to handle fractional and negative exponents correctly — especially the negative one, which can confuse students.

Let’s break it down.

  1. Recall the definition. For a rate law of the form

Rate=k[A]m[B]n\text{Rate} = k [A]^m [B]^n

the overall order is m+nm + n. The exponents mm and nn are the orders with respect to AA and BB, respectively. They can be integers, fractions, or even negative numbers.

  1. Part (a):

    Rate =k[A]1/2[B]3/2= k[A]^{1/2}[B]^{3/2}

    • Order with respect to AA: 1/21/2
    • Order with respect to BB: 3/23/2
    • Overall order =12+32=42=2= \frac{1}{2} + \frac{3}{2} = \frac{4}{2} = 2

    So the reaction is second order overall.

  2. Part (b):

    Rate =k[A]3/2[B]−1= k[A]^{3/2}[B]^{-1}

    • Order with respect to AA: 3/23/2
    • Order with respect to BB: −1-1
    • Overall order =32+(−1)=32−1=12= \frac{3}{2} + (-1) = \frac{3}{2} - 1 = \frac{1}{2}

    So the reaction is half order overall.

Watch out

A negative exponent does not mean the order is zero — it means the rate decreases as that reactant’s concentration increases. But you still add it algebraically. A common mistake is to ignore the negative sign or treat it as zero. Don’t.

Tip

When adding fractions, always get a common denominator. Here, 3/2−1=3/2−2/2=1/23/2 - 1 = 3/2 - 2/2 = 1/2. Quick mental check: if the sum is less than 1, the reaction is fractional order — unusual but possible in complex mechanisms.

✓Final answer

  1. The overall order is 2 (second order).
  2. The overall order is 1/2 (half order).

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