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Ch.18 - Thermodynamics: Entropy, Free Energy & Equilibrium
Chapter 18, Problem 107

Compare the values of ∆G and ∆G° when: (a) Q < 1. (b) Q = 1. (c) Q > 1. Does the thermodynamic tendency for the reaction to occur increase or decrease as Q increases?

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insert step 1> Identify the relationship between \( \Delta G \) and \( \Delta G^\circ \) using the equation: \( \Delta G = \Delta G^\circ + RT \ln Q \), where \( R \) is the gas constant, \( T \) is the temperature in Kelvin, and \( Q \) is the reaction quotient.
insert step 2> For case (a) when \( Q < 1 \), note that \( \ln Q \) is negative, which makes \( \Delta G < \Delta G^\circ \). This implies that the reaction is more spontaneous than under standard conditions.
insert step 3> For case (b) when \( Q = 1 \), \( \ln Q = 0 \), so \( \Delta G = \Delta G^\circ \). This means the reaction's spontaneity is the same as under standard conditions.
insert step 4> For case (c) when \( Q > 1 \), \( \ln Q \) is positive, which makes \( \Delta G > \Delta G^\circ \). This implies that the reaction is less spontaneous than under standard conditions.
insert step 5> As \( Q \) increases, \( \Delta G \) becomes larger, indicating that the thermodynamic tendency for the reaction to occur decreases.

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Key Concepts

Here are the essential concepts you must grasp in order to answer the question correctly.

Gibbs Free Energy (∆G)

Gibbs Free Energy (∆G) is a thermodynamic potential that measures the maximum reversible work obtainable from a thermodynamic process at constant temperature and pressure. It indicates the spontaneity of a reaction: if ∆G is negative, the reaction is spontaneous; if positive, it is non-spontaneous. The value of ∆G changes based on the reaction's conditions, including the concentrations of reactants and products.
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Standard Gibbs Free Energy Change (∆G°)

Standard Gibbs Free Energy Change (∆G°) refers to the change in Gibbs Free Energy under standard conditions (1 bar pressure, 1 M concentration for solutes, and a specified temperature, usually 298 K). It provides a reference point for predicting the direction of a reaction. Unlike ∆G, which varies with the reaction's progress, ∆G° remains constant for a given reaction at specified conditions.
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Reaction Quotient (Q)

The Reaction Quotient (Q) is a dimensionless number that reflects the ratio of the concentrations of products to reactants at any point in a reaction. It is used to determine the direction in which a reaction will proceed to reach equilibrium. When Q < 1, the reaction favors products; when Q = 1, the system is at equilibrium; and when Q > 1, the reaction favors reactants, indicating that as Q increases, the tendency for the reaction to occur decreases.
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Related Practice
Textbook Question
Ethanol is manufactured in industry by the hydration of ethylene: Using the data in Appendix B, calculate ∆G° and show that this reaction is spontaneous at 25 °C. Why does this reaction become nonspontaneous at higher temperatures? Estimate the temperature at which the reaction becomes nonspontaneous.
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Textbook Question
Consider the conversion of 1,2-dichloroethane to vinyl chloride, the starting material for manufacturing poly(vinyl chloride) (PVC) plastics: Is this reaction spontaneous under standard-state conditions? Would it help to carry out the reaction in the presence of base to remove HCl? Explain. Is it possible to synthesize vinyl chlo-ride from graphite, gaseous H2, and gaseous Cl2 at 25 °C and 1 atm pressure?
501
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Open Question
What is the relationship between the free-energy change under nonstandard-state conditions, ∆G, the free-energy change under standard-state conditions, ∆G°, and the reaction quotient, Q?
Textbook Question
Use the data in Appendix B to calculate ∆G for the decom-position of nitrosyl chloride at 25 °C when the partial pressures are 2.00 atm of NOCl, 1.00 * 10^-3 atm of NO, and 1.00 * 10^-3 atm of Cl2: Is the reaction spontaneous in the forward or the reverse direction under these conditions?
327
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Textbook Question
Urea (NH2CONH2), an important nitrogen fertilizer, is produced industrially by the reaction Given that ∆G° = -13.6 kJ, calculate ∆G at 25 °C for the following sets of conditions. . (a) 10 atm NH3, 10 atm CO2, 1.0 M NH2CONH2 (b) 0.10 atm NH3, 0.10 atm CO2, 1.0 M NH2CONH2 Is the reaction spontaneous for the conditions in part (a) and/or part (b)?
2195
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Open Question
What is the relationship between the standard free-energy change, ∆G°, for a reaction and the equilibrium constant, K? What is the sign of ∆G° when: (a) K > 1? (b) K = 1? (c) K < 1?