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Consider the reaction \(\mathrm{CH}_{4}(\mathrm{~g})+4 \mathrm{Cl}_{2}(g) \longrightarrow \mathrm{CCl}_{4}(g)+\) \(4 \mathrm{HCl}(g) .\). (a) Using data from Appendix C, calculate \(\Delta G^{\circ}\) at \(298 \mathrm{~K} .(\mathbf{b})\) Calculate \(\Delta G\) at \(298 \mathrm{~K}\) if the reaction mixture consists of \(50.7 \mathrm{kPa}\) of \(\mathrm{CH}_{4}(g), 25.3 \mathrm{kPa}\) of \(\mathrm{Cl}_{2}(g), 10.13 \mathrm{kPa}\) of \(\mathrm{CCl}_{4}(\mathrm{~g})\) and \(15.2 \mathrm{kPa}\) of \(\mathrm{HCl}(\mathrm{g})\)

Short Answer

Expert verified
(a) \(\Delta G^{\circ} = -191.5 \textrm{ kJ/mol}\) is obtained by calculating \(\Delta H^{\circ} - T\Delta S^{\circ}\) using the standard enthalpy and entropy change values. (b) \(\Delta G = -183.9 \textrm{ kJ/mol}\) is calculated by finding the reaction quotient (Q) using given partial pressures and substituting it along with the calculated \(\Delta G^{\circ}\) into the equation \(\Delta G = \Delta G^{\circ} + RT \ln(Q)\).

Step by step solution

01

Calculate the standard enthalpy and entropy changes

Using data from Appendix C, we determine the standard molar enthalpies (螖H掳) and standard molar entropies (螖S掳) of all species involved in the reaction. Then, we calculate the respective values for the entire reaction.
02

Calculate the standard Gibbs free energy change

Now, we substitute the calculated values of 螖H掳 and 螖S掳 in the equation 螖G掳 = 螖H掳 - T螖S掳 and calculate 螖G掳 at the given temperature 298K.
03

Calculate the reaction quotient (Q)

Based on the provided partial pressures of reactants and products, calculate the reaction quotient Q = [CCl鈧刔[HCl]鈦 / ([CH鈧刔[Cl鈧俔鈦).
04

Calculate 螖G using the reaction quotient

Finally, use the calculated 螖G掳 and reaction quotient (Q) values to find 螖G at the given temperature using the equation, 螖G = 螖G掳 + RT ln(Q).

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Key Concepts

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

Enthalpy
In chemistry, enthalpy (\(\Delta H\)) represents the heat content of a system at constant pressure. When considering a chemical reaction, the change in enthalpy (\(\Delta H^{\circ}\)) is the difference between the enthalpy of the products and the reactants.

For a reaction, you can find enthalpy changes using data from the Appendix C tables, which list standard molar enthalpies. The formula used is:\[\Delta H^{\circ} = \sum \Delta H^{\circ}_{\text{products}} - \sum \Delta H^{\circ}_{\text{reactants}}\]Here's a simple formula:
  • Calculate the enthalpy for each compound.
  • Multiply the calculated enthalpy by the number of moles in the reaction.
  • Subtract the sum of the reactants' enthalpy from the products' enthalpy.
Enthalpy is critical in understanding how much energy is released or absorbed in a chemical change. A negative\(\Delta H\)indicates an exothermic reaction, meaning it releases energy.
Entropy
Entropy (\(\Delta S\)) is a measure of randomness or disorder within a system. It influences the spontaneity of a reaction, which is particularly important when paired with enthalpy to determine free energy.

In thermodynamics, an increase in entropy (\(\Delta S^{\circ} > 0\)) often corresponds to a system moving toward more chaos or disorder. To calculate the standard entropy change of a system, use:\[\Delta S^{\circ} = \sum \Delta S^{\circ}_{\text{products}} - \sum \Delta S^{\circ}_{\text{reactants}}\]Steps to compute entropy change:
  • Look up standard entropy values for each compound present in the reaction.
  • Calculate using the number of moles in the reaction.
  • Determine the total entropy change by subtracting the entropy of reactants from that of products.
Entropy change and its sign help determine if a system will favor the formation of products, particularly in balance with enthalpy changes.
Reaction Quotient
The reaction quotient (\(Q\)) is a vital factor in assessing the progress of a reaction under specific conditions, different from the equilibrium state. It is defined by the ratio of the concentrations or pressures of the products to reactants, each raised to the power of their stoichiometric coefficients in the balanced chemical equation.

The general formula for gases, when pressures are provided, is:\[Q = \frac{P_{\text{products}}}{P_{\text{reactants}}}\]For the given reaction:
  • Identify partial pressures for each gas involved.
  • Apply the formula considering stoichiometry: \[Q = \frac{{[\mathrm{CCl}_4][\mathrm{HCl}]^4}}{[\mathrm{CH}_4][\mathrm{Cl}_2]^4}\]
The calculated\(Q\)helps in determining the Gibbs free energy (\(\Delta G\)) using:\[\Delta G = \Delta G^{\circ} + RT \ln(Q)\]Where\(R\) is the universal gas constant and \(T\) is the temperature in Kelvin. This equation allows chemists to predict the direction a reaction will naturally progress given current pressures, indicating if the reaction is moving towards equilibrium.

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Most popular questions from this chapter

For each of the following processes, indicate whether the signs of \(\Delta S\) and \(\Delta H\) are expected to be positive, negative, or about zero. (a) A solid sublimes. (b) The temperature of a sample of \(\mathrm{Co}(s)\) is lowered from \(60^{\circ} \mathrm{C}\) to \(25^{\circ} \mathrm{C} .\) (c) Ethyl alcohol evaporates from a beaker. (d) A diatomic molecule dissociates into atoms. (e) A piece of charcoal is combusted to form \(\mathrm{CO}_{2}(g)\) and \(\mathrm{H}_{2} \mathrm{O}(g)\).

Indicate whether each statement is true or false. (a) The entropy of the universe increases for any spontaneous process. (b) The entropy change of the system is equal and opposite that of the surroundings for any irreversible process. (c) The entropy of the system must increase in any spontaneous process. (d) The entropy change for an isothermal process depends on both the absolute temperature and the amount of heat reversibly transferred.

(a) What sign for \(\Delta S\) do you expect when the pressure on 0.600 mol of an ideal gas at \(350 \mathrm{~K}\) is increased isothermally from an initial pressure of \(76.0 \mathrm{kPa} ?(\mathbf{b})\) If the final pressure on the gas is \(121.6 \mathrm{kPa}\), calculate the entropy change for the process. (c) Do you need to specify the temperature to calculate the entropy change?

Indicate whether each of the following statements is trueor false. If it is false, correct it. (a) The feasibility of manufacturing \(\mathrm{NH}_{3}\) from \(\mathrm{N}_{2}\) and \(\mathrm{H}_{2}\) depends entirely on the value of \(\Delta H\) for the process \(\mathrm{N}_{2}(g)+3 \mathrm{H}_{2}(g) \longrightarrow 2 \mathrm{NH}_{3}(g) .\) (b) The reaction of \(\mathrm{Na}(s)\) with \(\mathrm{Cl}_{2}(g)\) to form \(\mathrm{NaCl}(s)\) is a spontaneous process. (c) A spontaneous process can in principle be conducted reversibly. (d) Spontaneous processes in general require that work be done to force them to proceed. (e) Spontaneous processes are those that are exothermic and that lead to a higher degree of order in the system.

Predict the sign of \(\Delta S_{s y s}\) for each of the following processes: (a) Gaseous \(\mathrm{H}_{2}\) reacts with liquid palmitoleic acid \(\left(\mathrm{C}_{16} \mathrm{H}_{30} \mathrm{O}_{2},\right.\) unsaturated fatty acid) to form liquid palmitic acid \(\left(\mathrm{C}_{16} \mathrm{H}_{32} \mathrm{O}_{2}\right.\) saturated fatty acid). (b) Liquid palmitic acid solidifies at \(1^{\circ} \mathrm{C}\) to solid palmitic acid. (c) Silver chloride precipitates upon mixing \(\mathrm{AgNO}_{3}(a q)\) and \(\mathrm{NaCl}(a q) .\) (d) Gaseous \(\mathrm{H}_{2}\) dissociates in an electric arc to form gaseous H atoms (used in atomic hydrogen welding).

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