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Unit 7 Study Guide – Thermodynamics, Entropy, Electrochemistry, and Equilibrium

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Q1. The combustion of C2H5OH is represented by the equation and the standard entropy and enthalpy changes for the reaction are provided. When the reactants are combined at 25°C, essentially no CO2 (g) or H2O (g) is produced after a few hours. Which of the diagrams above could help explain the low yield of the reaction under these conditions and why?

Background

Topic: Thermodynamics and Kinetics

This question tests your understanding of the difference between thermodynamic favorability (ΔG, ΔH, ΔS) and reaction kinetics (activation energy, reaction rate). Even if a reaction is thermodynamically favorable, it may not proceed quickly if the activation energy is high.

Key Terms and Formulas:

  • ΔH°: Standard enthalpy change

  • ΔS°: Standard entropy change

  • ΔG°: Standard free energy change,

  • Activation energy: The energy barrier that must be overcome for a reaction to proceed

Potential energy diagrams for combustion reaction

Step-by-Step Guidance

  1. Examine the values for ΔH° and ΔS°: (exothermic), (increase in entropy).

  2. Calculate the sign of ΔG° at 25°C using . Both terms favor spontaneity, so the reaction is thermodynamically favorable.

  3. Analyze the diagrams: Diagram 1 and Diagram 2 show potential energy profiles. Diagram 2 has a much higher activation energy barrier than Diagram 1.

  4. Consider the effect of activation energy: A high activation energy means the reaction proceeds very slowly, even if it is thermodynamically favorable.

Try solving on your own before revealing the answer!

Final Answer: Diagram 2, because it represents a reaction with a high activation energy barrier for molecules to overcome and a very slow reaction rate, even if it is thermodynamically favorable with ΔG° < 0.

Diagram 2 explains why the reaction has a low yield after a few hours: the high activation energy slows the reaction rate, so little product forms despite thermodynamic favorability.

Q4. When water is added to a mixture of Na2O2 (s) and S(s), a redox reaction occurs. Which of the following statements about the thermodynamic favorability of the reaction at 298 K is correct?

Background

Topic: Thermodynamics – Enthalpy and Entropy

This question tests your ability to interpret ΔH° and ΔS° values to determine if a reaction is thermodynamically favorable at a given temperature.

Key Terms and Formulas:

  • ΔH°: Standard enthalpy change ()

  • ΔS°: Standard entropy change ()

  • ΔG°: Standard free energy change,

Thermodynamic values for Na2O2 and S reaction

Step-by-Step Guidance

  1. Identify the signs: ΔH° is negative (exothermic), ΔS° is negative (entropy decreases).

  2. Recall that a negative ΔH° favors spontaneity, while a negative ΔS° opposes it.

  3. Use the formula to predict favorability at 298 K.

  4. At low temperatures, the enthalpy term dominates; at high temperatures, the entropy term becomes more important.

Try solving on your own before revealing the answer!

Final Answer: It is thermodynamically favorable at 298 K.

The large negative ΔH° outweighs the small negative ΔS°, so ΔG° is negative and the reaction is spontaneous at room temperature.

Q5. The reaction between AgNO3 and CaCl2 is represented in the equation, and the table provides the approximate S° values for the reactants and products. Which of the following is the approximate ΔS° for the reaction?

Background

Topic: Entropy Change in Chemical Reactions

This question tests your ability to calculate the change in entropy (ΔS°) for a reaction using standard entropy values for each substance.

Key Terms and Formulas:

  • ΔS°: Standard entropy change

  • Formula:

Standard entropy values for AgNO3, CaCl2, AgCl, Ca(NO3)2

Step-by-Step Guidance

  1. Write the balanced equation:

  2. List the S° values for each substance from the table.

  3. Calculate the total S° for products:

  4. Calculate the total S° for reactants:

  5. Set up the formula:

Try solving on your own before revealing the answer!

Final Answer: -68 J/mol·K

Plugging in the values: J/mol·K. The reaction results in a decrease in entropy.

Q6. Based on the values for the three reactions represented, what is the value of ΔG° for the reaction: 4 NH3 (g) + 8 O2 (g) → 4 HNO3 (aq) + 4 H2O (l)?

Background

Topic: Thermodynamics – Standard Free Energy Change

This question tests your ability to use the values of ΔG° for related reactions to calculate ΔG° for a target reaction, often using Hess's Law.

Key Terms and Formulas:

  • ΔG°: Standard free energy change

  • Hess's Law: The sum of ΔG° for individual reactions can be used to find ΔG° for a combined reaction.

Standard free energy values for three reactions

Step-by-Step Guidance

  1. Write out the three given reactions and their ΔG° values.

  2. Determine how to combine the reactions (add, subtract, multiply) to obtain the target reaction.

  3. Adjust the coefficients as needed, making sure to multiply ΔG° values accordingly.

  4. Sum the adjusted ΔG° values to set up the calculation for the target reaction.

Try solving on your own before revealing the answer!

Final Answer: -1319 kJ/mol

By combining the reactions using Hess's Law and summing the ΔG° values, you find the standard free energy change for the target reaction.

Q7. A stoichiometric mixture of CO (g) and H2 (g) was allowed to react in two different 2.0 L rigid containers at a constant temperature of 298 K. The reaction is represented by the equation. Diagram 1 represents the uncatalyzed reaction and diagram 2 represents the catalyzed reaction one hour after the reactants were mixed. Which of the following correctly explains the experimental results represented in the particle diagrams?

Background

Topic: Kinetics and Thermodynamics

This question tests your understanding of how catalysts affect reaction rates and the relationship between thermodynamic favorability and kinetics.

Key Terms and Formulas:

  • Catalyst: A substance that increases the rate of a reaction by lowering the activation energy, without affecting ΔG°.

  • ΔG°: Standard free energy change

  • K: Equilibrium constant

Particle diagrams for catalyzed and uncatalyzed reactions

Step-by-Step Guidance

  1. Examine the equilibrium constant (K = 2.2 × 10⁴): This indicates the reaction is thermodynamically favorable (ΔG° < 0).

  2. Compare the diagrams: Diagram 1 (no catalyst) shows little product formation; Diagram 2 (with catalyst) shows significant product formation.

  3. Recall that a catalyst lowers the activation energy, allowing the reaction to proceed faster.

  4. Understand that the catalyst does not change ΔG° or K, only the rate at which equilibrium is reached.

Try solving on your own before revealing the answer!

Final Answer: Although the reaction is thermodynamically favorable because ΔG° < 0 based on the value of K, only the catalyzed reaction could proceed in one hour because it has a lower activation-energy pathway.

The catalyst enables the reaction to reach equilibrium faster by lowering the activation energy, not by changing the thermodynamic favorability.

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