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Exercises · 3.23

Q.The rate constant for the decomposition of hydrocarbons is 2.418×10−5 s−12.418\times10^{-5}\ \text{s}^{-1} at 546 K. If the energy of activation is 179.9 kJ/mol179.9\ \text{kJ/mol}, what will be the value of pre-exponential factor?

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Using the Arrhenius equation k=Ae−Ea/(RT)k = A e^{-E_a/(RT)}, we solve for the pre-exponential factor AA. With k=2.418×10−5 s−1k = 2.418 \times 10^{-5}\ \text{s}^{-1}, Ea=179.9 kJ/molE_a = 179.9\ \text{kJ/mol}, and T=546 KT = 546\ \text{K}, the value of AA is approximately 3.9×1012 s−13.9 \times 10^{12}\ \text{s}^{-1}.

The Arrhenius equation is the backbone of chemical kinetics when temperature dependence is involved. It tells us that the rate constant kk depends on two things: the fraction of molecules with enough energy to react (given by the exponential term e−Ea/(RT)e^{-E_a/(RT)}) and how often collisions happen in the right orientation (the pre-exponential factor AA). Here, we know kk, EaE_a, and TT, and we need to find AA — so we simply rearrange the equation.

k=Ae−Ea/(RT)k = A e^{-E_a/(RT)}

Where:

  • kk = rate constant (s−1\text{s}^{-1})
  • AA = pre-exponential factor (same units as kk)
  • EaE_a = activation energy (J/mol — careful with units!)
  • RR = gas constant (8.314 J mol−1 K−18.314\ \text{J mol}^{-1}\ \text{K}^{-1})
  • TT = temperature (K)
  1. Convert activation energy to consistent units. The given Ea=179.9 kJ/molE_a = 179.9\ \text{kJ/mol}. Since RR is in J/mol·K, we must convert:

Ea=179.9×103 J/mol=1.799×105 J/molE_a = 179.9 \times 10^3\ \text{J/mol} = 1.799 \times 10^5\ \text{J/mol}

  1. Compute the exponent EaRT\frac{E_a}{RT}. First, RT=8.314×546RT = 8.314 \times 546.

RT=8.314×546=4539.444 J/molRT = 8.314 \times 546 = 4539.444\ \text{J/mol}

Then,

EaRT=1.799×1054539.444≈39.63\frac{E_a}{RT} = \frac{1.799 \times 10^5}{4539.444} \approx 39.63

  1. Find e−Ea/(RT)e^{-E_a/(RT)}.

e−39.63=1e39.63e^{-39.63} = \frac{1}{e^{39.63}}

This is a very small number. Using a calculator:

e39.63≈1.62×1017e^{39.63} \approx 1.62 \times 10^{17}

So,

e−39.63≈6.17×10−18e^{-39.63} \approx 6.17 \times 10^{-18}

  1. Rearrange the Arrhenius equation to solve for AA.

A=ke−Ea/(RT)=k×eEa/(RT)A = \frac{k}{e^{-E_a/(RT)}} = k \times e^{E_a/(RT)}

Substitute the values:

A=(2.418×10−5)×(1.62×1017)A = (2.418 \times 10^{-5}) \times (1.62 \times 10^{17})

  1. Calculate AA. A=2.418×1.62×1012≈3.917×1012 s−1A = 2.418 \times 1.62 \times 10^{12} \approx 3.917 \times 10^{12}\ \text{s}^{-1} …

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