Steam undergoes decomposition at high temperature as per the reaction \(\mathrm{H}_{2} \mathrm{O}(\mathrm{g}) \rightleftharpoons \mathrm{H}_{2}(\mathrm{~g})+\frac{1}{2} \mathrm{O}_{2}(\mathrm{~g})\) \(\Delta \mathrm{H}^{\circ}=200 \mathrm{~kJ} \mathrm{~mol}^{-1}, \Delta \mathrm{S}^{\circ}=40 \mathrm{~kJ} \mathrm{~mol}^{-1}\). The temperature at which equilibrium constant is unity is : (1) 3000 Kelvin (2) 5000 Kelvin (3) 5333 Kelvin (4) 5 Kelvin

Short Answer

Expert verified
The temperature at which the equilibrium constant is unity is 5000 Kelvin.

Step by step solution

01

Identify the Given Information

The problem provides the following data: - A chemical reaction: \[\text{H}_{2} \text{O} (\text{g}) \rightleftharpoons \text{H}_2 (\text{g}) + \frac{1}{2} \text{O}_2 (\text{g})\] - Change in enthalpy, \(\Delta \text{H}^\circ = 200 \text{ kJ mol}^{-1}\) - Change in entropy, \(\Delta \text{S}^\circ = 40 \text{ kJ mol}^{-1}\)
02

Determine the Relationship Between Enthalpy, Entropy, and Temperature

The equilibrium constant can be expressed in terms of the Gibbs free energy change (\(\Delta G^\circ\)). At equilibrium, \(\Delta G^\circ = 0\) when the equilibrium constant \(K = 1\). The relationship is given by the equation: \[\Delta G^\circ = \Delta H^\circ - T \Delta S^\circ\]
03

Set the Gibbs Energy Change to Zero

Since \(K = 1\) at equilibrium, set \(\Delta G^\circ\) to 0: \[0 = \Delta H^\circ - T \Delta S^\circ\] Rearrange to find the temperature \(T\): \[T = \frac{\Delta H^\circ}{\Delta S^\circ}\]
04

Plug in the Given Values

Substitute the values for \(\Delta H^\circ\) and \(\Delta S^\circ\) into the equation: \[T = \frac{200 \text{ kJ mol}^{-1}}{40 \text{ kJ mol}^{-1}} = 5 \text{ kJ/K} \] Note that \(kJ/K\) can be converted to Kelvin by direct comparison since the units are consistent.
05

Convert to Temperature in Kelvin

The calculation gives: \[T = 5 \times 10^3 \text{ K} = 5000 \text{ K}\]

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Key Concepts

These are the key concepts you need to understand to accurately answer the question.

Gibbs Free Energy
Gibbs free energy (\text{G}) is a thermodynamic potential that measures the maximum reversible work a thermodynamic system can perform at constant temperature and pressure. It is used to predict the direction of chemical reactions and determine equilibrium positions. The change in Gibbs free energy (\text{ΔG}) for a reaction is given by the equation:

\[\text{ΔG} = \text{ΔH} - T\text{ΔS}\]
Here, \text{ΔH} represents the change in enthalpy, \text{ΔS} is the change in entropy, and T is the temperature in Kelvin.

When \text{ΔG} is negative, the reaction proceeds spontaneously in the forward direction. When \text{ΔG} is zero, the system is at equilibrium. Lastly, a positive \text{ΔG} means the reaction is non-spontaneous in the forward direction.
Equilibrium Constant
The equilibrium constant (K) provides insight into the proportions of reactants and products when a chemical reaction reaches equilibrium. For the reaction:

\[\text{H}_{2}\text{O}(\text{g}) \rightleftharpoons \text{H}_{2}(\text{g}) + \frac{1}{2}\text{O}_{2}(\text{g})\]
When K equals 1, the concentrations of reactants and products are equal under standard conditions. The link between Gibb's free energy and the equilibrium constant is expressed as:

\[\text{ΔG}^{\text{°}} = -RT\text{ln}K\]
At equilibrium, where \text{K} is 1, \text{ln}1 equals 0, leading to \text{ΔG} = 0, which further simplifies to:

\[\text{ΔH}^{\text{°}} = T\text{ΔS}^{\text{°}}\]
This equation can be used to calculate the temperature at which the equilibrium constant is unity, as we did in the provided solution.
Enthalpy and Entropy
Enthalpy (\text{H}) represents the total heat content of a system. It includes both the internal energy of the system and the product of its pressure and volume. The change in enthalpy (\text{ΔH}) is an important factor in predicting reaction behavior:
  • A negative \text{ΔH} indicates an exothermic reaction, releasing heat to the surroundings.
  • A positive \text{ΔH} signifies an endothermic reaction, absorbing heat.

Entropy (\text{S}), on the other hand, is a measure of the disorder or randomness of a system. The change in entropy (\text{ΔS}) reflects how much the disorder increases or decreases during a reaction:
  • A positive \text{ΔS} suggests an increase in disorder.
  • A negative \text{ΔS} indicates a decrease in disorder.

Both \text{ΔH} and \text{ΔS} are crucial in determining the feasibility and spontaneity of a reaction through the Gibbs free energy equation:

\[\text{ΔG} = \text{ΔH} - T\text{ΔS}\]
In summary, understanding \text{ΔH} and \text{ΔS} allows us to predict how a chemical reaction will behave under different temperature conditions.

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