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Q.

The following initial rate data were obtained for the reaction:

2NO (g)+Br2 (g)→2NOBr (g)2NO\,(g) + Br_2\,(g) \rightarrow 2NOBr\,(g)

Expt. No.[NO]/mol L⁻¹[Br₂]/mol L⁻¹Initial Rate (mol L⁻¹ s⁻¹)
10.050.051.0×10⁻³
20.050.153.0×10⁻³
30.150.059.0×10⁻³
  1. What is the order with respect to NO and Br2Br_2 in the reaction?
  2. Calculate the rate constant (k).
  3. Determine the rate of reaction when concentration of NO and Br2Br_2 are 0.4 M and 0.2 M, respectively. (1+1+1=3)
CBSECBSE Class XII Board 2024Subjective· 3mImportance★★★★★
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By comparing initial rates from experimental data, we find the reaction is second order with respect to NO and first order with respect to Br2Br_2. The rate constant is 8 mol−2L2s−18\, mol^{-2} L^2 s^{-1}, and the reaction rate at the specified concentrations is 0.256 molL−1s−10.256\, mol L^{-1} s^{-1}.

The rate of a chemical reaction is often dependent on the concentrations of the reactants. This relationship is expressed by the rate law, which is an experimentally determined equation. It's crucial to understand that the exponents in the rate law (the reaction orders) are not necessarily the stoichiometric coefficients from the balanced chemical equation. They must be found through experiments.

The initial rate method involves conducting several experiments where the initial concentrations of reactants are systematically varied, and the corresponding initial reaction rates are measured. By observing how the rate changes when one reactant's concentration is altered while others are kept constant, we can deduce the order of the reaction with respect to each reactant.

Let's break down the problem into parts.

Part (a): Determine the order with respect to NO and Br2Br_2.

  1. Write the general form of the rate law. For the reaction 2NO (g)+Br2 (g)→2NOBr (g)2NO\,(g) + Br_2\,(g) \rightarrow 2NOBr\,(g), the general rate law can be written as:

Rate=k[NO]x[Br2]yRate = k[NO]^x[Br_2]^y

where $k$ is the rate constant, $x$ is the order with respect to NO, and $y$ is the order with respect to $Br_2$. Our goal is to find the values of $x$ and $y$.

2. Determine the order with respect to Br2Br_2 (yy).

To find yy, we need to select two experiments where the concentration of NO remains constant, but the concentration of Br2Br_2 changes. Comparing Experiment 1 and Experiment 2 fits this criterion:

| Expt. No. | [NO]/mol L⁻¹ | [Br₂]/mol L⁻¹ | Initial Rate (mol L⁻¹ s⁻¹) |
|---|---|---|---|
| 1 | 0.05 | 0.05 | 1.0×10⁻³ |
| 2 | 0.05 | 0.15 | 3.0×10⁻³ |

From the table, we can see that:
*   $[NO]$ is constant (0.05 M).
*   $[Br_2]$ triples from 0.05 M to 0.15 M ($0.15 / 0.05 = 3$).
*   The initial rate triples from $1.0 \times 10^{-3}$ to $3.0 \times 10^{-3}$ ($3.0 \times 10^{-3} / 1.0 \times 10^{-3} = 3$).

We can set up a ratio of the rate laws for these two experiments:

Rate2Rate1=k[NO]2x[Br2]2yk[NO]1x[Br2]1y\frac{Rate_2}{Rate_1} = \frac{k[NO]_2^x[Br_2]_2^y}{k[NO]_1^x[Br_2]_1^y}

3.0×10−31.0×10−3=k(0.05)x(0.15)yk(0.05)x(0.05)y\frac{3.0 \times 10^{-3}}{1.0 \times 10^{-3}} = \frac{k(0.05)^x(0.15)^y}{k(0.05)^x(0.05)^y}

3=(0.150.05)y3 = \left(\frac{0.15}{0.05}\right)^y

3=(3)y3 = (3)^y

Therefore, $y = 1$. The reaction is **first order** with respect to $Br_2$.

3. Determine the order with respect to NO (xx).

To find xx, we need to select two experiments where the concentration of Br2Br_2 remains constant, but the concentration of NO changes. Comparing Experiment 1 and Experiment 3 fits this criterion:

| Expt. No. | [NO]/mol L⁻¹ | [Br₂]/mol L⁻¹ | Initial Rate (mol L⁻¹ s⁻¹) |
|---|---|---|---|
| 1 | 0.05 | 0.05 | 1.0×10⁻³ |
| 3 | 0.15 | 0.05 | 9.0×10⁻³ |

From the table, we can see that:
*   $[Br_2]$ is constant (0.05 M).
*   $[NO]$ triples from 0.05 M to 0.15 M ($0.15 / 0.05 = 3$).
*   The initial rate increases by a factor of 9 from $1.0 \times 10^{-3}$ to $9.0 \times 10^{-3}$ ($9.0 \times 10^{-3} / 1.0 \times 10^{-3} = 9$).

Setting up the ratio of rate laws:

Rate3Rate1=k[NO]3x[Br2]3yk[NO]1x[Br2]1y\frac{Rate_3}{Rate_1} = \frac{k[NO]_3^x[Br_2]_3^y}{k[NO]_1^x[Br_2]_1^y}

9.0×10−31.0×10−3=k(0.15)x(0.05)yk(0.05)x(0.05)y\frac{9.0 \times 10^{-3}}{1.0 \times 10^{-3}} = \frac{k(0.15)^x(0.05)^y}{k(0.05)^x(0.05)^y}

9=(0.150.05)x9 = \left(\frac{0.15}{0.05}\right)^x

9=(3)x9 = (3)^x

Therefore, $x = 2$. The reaction is **second order** with respect to NO.

> [!IMPORTANT]
> The complete rate law for the reaction is $Rate = k[NO]^2[Br_2]^1$. The overall order of the reaction is $2+1=3$.

Part (b): Calculate the rate constant (k).

  1. Calculate the rate constant using the determined rate law and data from any experiment.

    We can use the rate law Rate=k[NO]2[Br2]1Rate = k[NO]^2[Br_2]^1 and substitute the values from any of the experiments to solve for kk. Let's use Experiment 1:

    • [NO]=0.05 molL−1[NO] = 0.05\, mol L^{-1}
    • [Br2]=0.05 molL−1[Br_2] = 0.05\, mol L^{-1}
    • Rate=1.0×10−3 molL−1s−1Rate = 1.0 \times 10^{-3}\, mol L^{-1} s^{-1}

    Substitute these values into the rate law:

1.0×10−3 molL−1s−1=k(0.05 molL−1)2(0.05 molL−1)11.0 \times 10^{-3}\, mol L^{-1} s^{-1} = k(0.05\, mol L^{-1})^2(0.05\, mol L^{-1})^1

1.0×10−3=k(0.0025)(0.05)1.0 \times 10^{-3} = k(0.0025)(0.05)

$$1.0 \times 10^{-3} = k(0.000125)$$ …

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