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For the first order thermal decomposition reaction, following data was obtained : C2H5Cl(g)⟶C2H4(g)+HCl(g)C_2H_5Cl(g) \longrightarrow C_2H_4(g) + HCl(g)

S. No.Time (s)Total Pressure (atm)
100.30
2300.50

Calculate rate constant. [Given : log 3 = 0.48]

CBSECBSE Class XII Board 2026Subjective· 3mImportance★★★★★
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For a first-order gas-phase reaction, the rate constant can be determined by relating the total pressure to the partial pressure of the reactant over time. Using the given data, the rate constant for the decomposition of C2H5ClC_2H_5Cl is 0.037 s−1\boxed{0.037 \text{ s}^{-1}}.

When a reaction occurs in the gas phase, the concentration of reactants and products can be directly related to their partial pressures, assuming ideal gas behavior. For a first-order reaction, the rate depends linearly on the concentration (or partial pressure) of a single reactant. The key to solving this problem is to use the given total pressure data to determine the partial pressure of the reactant, C2H5ClC_2H_5Cl, at a specific time, and then apply the integrated rate law for a first-order reaction.

Here's how we approach this:

  1. Understand the reaction stoichiometry and pressure relationships.

    The given reaction is:

    C2H5Cl(g)⟶C2H4(g)+HCl(g)C_2H_5Cl(g) \longrightarrow C_2H_4(g) + HCl(g)

    Let P0P_0 be the initial partial pressure of C2H5ClC_2H_5Cl at t=0t=0.

    At t=0t=0, the total pressure Ptotal(0)P_{total}(0) is solely due to C2H5ClC_2H_5Cl, as no products have formed yet.

    So, Ptotal(0)=PC2H5Cl(0)=P0P_{total}(0) = P_{C_2H_5Cl}(0) = P_0.

    From the data, at t=0t=0, Ptotal=0.30P_{total} = 0.30 atm.

    Therefore, P0=0.30P_0 = 0.30 atm.

    At any time tt, let xx be the decrease in the partial pressure of C2H5ClC_2H_5Cl due to decomposition.

    According to the stoichiometry of the reaction:

    • Partial pressure of C2H5ClC_2H_5Cl at time tt: PC2H5Cl(t)=P0−xP_{C_2H_5Cl}(t) = P_0 - x
    • Partial pressure of C2H4C_2H_4 formed at time tt: PC2H4(t)=xP_{C_2H_4}(t) = x
    • Partial pressure of HClHCl formed at time tt: PHCl(t)=xP_{HCl}(t) = x

    The total pressure at time tt, Ptotal(t)P_{total}(t), is the sum of the partial pressures of all gases present:

    Ptotal(t)=PC2H5Cl(t)+PC2H4(t)+PHCl(t)P_{total}(t) = P_{C_2H_5Cl}(t) + P_{C_2H_4}(t) + P_{HCl}(t)

    Ptotal(t)=(P0−x)+x+xP_{total}(t) = (P_0 - x) + x + x

    Ptotal(t)=P0+xP_{total}(t) = P_0 + x

  2. Express the partial pressure of the reactant in terms of total pressure.

    From the total pressure equation, we can find xx:

    x=Ptotal(t)−P0x = P_{total}(t) - P_0

    Now, substitute this expression for xx back into the equation for the partial pressure of the reactant, PC2H5Cl(t)P_{C_2H_5Cl}(t):

    PC2H5Cl(t)=P0−(Ptotal(t)−P0)P_{C_2H_5Cl}(t) = P_0 - (P_{total}(t) - P_0)

    PC2H5Cl(t)=2P0−Ptotal(t)P_{C_2H_5Cl}(t) = 2P_0 - P_{total}(t)

    This equation allows us to calculate the partial pressure of the reactant at any time tt using the initial pressure and the total pressure at that time.

  3. Calculate the partial pressure of the reactant at t=30t=30 s.

    We have:

    • P0=0.30P_0 = 0.30 atm (from t=0t=0 data)
    • Ptotal(30 s)=0.50P_{total}(30 \text{ s}) = 0.50 atm (from t=30t=30 s data)

    Using the derived relationship:

    PC2H5Cl(30 s)=2(0.30 atm)−0.50 atmP_{C_2H_5Cl}(30 \text{ s}) = 2(0.30 \text{ atm}) - 0.50 \text{ atm}

    PC2H5Cl(30 s)=0.60 atm−0.50 atmP_{C_2H_5Cl}(30 \text{ s}) = 0.60 \text{ atm} - 0.50 \text{ atm}

    PC2H5Cl(30 s)=0.10 atmP_{C_2H_5Cl}(30 \text{ s}) = 0.10 \text{ atm} …

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