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Exercises · 3.28

Q.The decomposition of A into product has value of kk as 4.5×103 s−14.5\times10^{3}\ \text{s}^{-1} at 10°C and energy of activation 60 kJ mol−160\ \text{kJ mol}^{-1}. At what temperature would kk be 1.5×104 s−11.5\times10^{4}\ \text{s}^{-1}?

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Using the Arrhenius equation in its two-point form, the temperature at which the rate constant rises to 1.5×104 s−11.5 \times 10^{4}\ \text{s}^{-1} is approximately 297 K297\ \text{K} (or 24∘C24^\circ\text{C}).

The key to this problem is the Arrhenius equation, which tells us how the rate constant kk depends on temperature and activation energy. The equation is:

k=Ae−Ea/RTk = A e^{-E_a / RT}

where AA is the pre-exponential factor, EaE_a is the activation energy, RR is the gas constant, and TT is the absolute temperature. When we have two different temperatures and their corresponding rate constants, we can eliminate AA by taking a ratio. This gives the very useful two-point form:

ln⁡k2k1=EaR(1T1−1T2)\ln\frac{k_2}{k_1} = \frac{E_a}{R}\left(\frac{1}{T_1} - \frac{1}{T_2}\right)

This is the formula we'll use. Notice the order: k2k_2 is the rate constant at the unknown temperature T2T_2, and k1k_1 is the known rate constant at T1T_1. The activation energy must be in the same energy units as RR, so we'll use R=8.314 J mol−1K−1R = 8.314\ \text{J mol}^{-1}\text{K}^{-1} and convert EaE_a from kJ to J.

Let's work through it step by step.

  1. Convert all data to consistent units.

    The activation energy is 60 kJ mol−1=60 000 J mol−160\ \text{kJ mol}^{-1} = 60\,000\ \text{J mol}^{-1}.

    The first temperature is 10∘C=283 K10^\circ\text{C} = 283\ \text{K} (since T(K)=T(∘C)+273T(\text{K}) = T(^\circ\text{C}) + 273).

    The first rate constant is k1=4.5×103 s−1k_1 = 4.5 \times 10^{3}\ \text{s}^{-1}.

    The second rate constant is k2=1.5×104 s−1k_2 = 1.5 \times 10^{4}\ \text{s}^{-1}.

    We need to find T2T_2.

  2. Write the two-point Arrhenius equation with the known values.

ln⁡(1.5×1044.5×103)=60 0008.314(1283−1T2)\ln\left(\frac{1.5 \times 10^{4}}{4.5 \times 10^{3}}\right) = \frac{60\,000}{8.314}\left(\frac{1}{283} - \frac{1}{T_2}\right)

  1. Simplify the left-hand side.

1.5×1044.5×103=154.5=103≈3.333\frac{1.5 \times 10^{4}}{4.5 \times 10^{3}} = \frac{15}{4.5} = \frac{10}{3} \approx 3.333

So ln⁡(3.333)≈1.204\ln(3.333) \approx 1.204 (using a calculator or knowing ln⁡(10/3)=ln⁡10−ln⁡3≈2.303−1.099=1.204\ln(10/3) = \ln 10 - \ln 3 \approx 2.303 - 1.099 = 1.204).

  1. Simplify the right-hand side constant.

EaR=60 0008.314≈7217 K\frac{E_a}{R} = \frac{60\,000}{8.314} \approx 7217\ \text{K}

So the equation becomes:

1.204=7217(1283−1T2)1.204 = 7217 \left(\frac{1}{283} - \frac{1}{T_2}\right)

  1. Solve for the bracket. …

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