Thermodynamics And Thermochemistry Result Question 14

14. The thermal dissociation of equilibrium of $\mathrm{CaCO}_3(s)$ is studied under different conditions.

(2013 Adv.)

$\mathrm{CaCO}_3(s) \rightleftharpoons \mathrm{CaO}(s)+\mathrm{CO}_2(g)$

For this equilibrium, the correct statement(s) is/are

(a) $\Delta H$ is dependent on $T$

(b) $K$ is independent of the initial amount of $\mathrm{CaCO}_3$

(c) $K$ is dependent on the pressure of $\mathrm{CO}_2$ at a given $T$

(d) $\Delta H$ is independent of the catalyst, if any

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Answer:

Correct Answer: 14. $(\mathrm{a}, \mathrm{b}, \mathrm{c}, \mathrm{d})$

Solution:

  1. PLAN: Heat of reaction is dependent on temperature (Kirchhoff’s equation) in heterogeneous system, equilibrium constant is independent on the molar concentration of solid species.

Heat of reaction is not affected by catalyst. It lowers activation energy.

$\mathrm{CaCO} _3(s) \rightleftharpoons \mathrm{CaO}(s) + \mathrm{CO} _2(g)$

By Kirchhoff’s equation,

$\Delta H_2^{\circ}\left(\text { at } T_2\right)=\Delta H_1^{\circ}\left(\text { at } T_1\right)+\Delta C_p\left(T_2-T_1\right)$

$\Delta H^{\circ}$ varies with temperature. Thus, (a) is correct.

$K=p_{\mathrm{CO}_2}$

$K$ is dependent on pressure of $\mathrm{CO}_2$ but independent of molar concentration of $\mathrm{CaCO}_3$. Thus, (b) and (c) are correct. At a given temperature, addition of catalysis lowers activation energy, $\Delta H$ remaining constant. Thus, (d) is also correct.

alt text

$E_a=$ Activation energy in absence of catalyst

$E_a^{\prime}=$ Activation energy in presence of catalyst



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