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Ch.19 - Chemical Thermodynamics
Chapter 19, Problem 94b

Consider the following three reactions: (i) Ti(s) + 2 Cl2(g) → TiCl4(1g) (ii) C2H6(g) + 7 Cl2(g) → 2 CCl4(g) + 6 HCl(g) (iii) BaO(s) + CO2(g) → BaCO3(s) (b) Which of these reactions are spontaneous under standard conditions at 25 °C?

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1
Understand the concept of spontaneity: A reaction is spontaneous under standard conditions if it has a negative Gibbs free energy change (ΔG°). The standard conditions are 25 °C (298 K) and 1 atm pressure.
Use the Gibbs free energy equation: ΔG° = ΔH° - TΔS°, where ΔH° is the change in enthalpy, T is the temperature in Kelvin, and ΔS° is the change in entropy.
Determine the standard enthalpy change (ΔH°) and standard entropy change (ΔS°) for each reaction. These values can be found in standard thermodynamic tables.
Calculate ΔG° for each reaction using the equation ΔG° = ΔH° - TΔS°. Remember to convert temperature to Kelvin by adding 273.15 to the Celsius temperature.
Compare the calculated ΔG° values: If ΔG° is negative, the reaction is spontaneous under standard conditions. If ΔG° is positive, the reaction is non-spontaneous.

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Key Concepts

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

Spontaneity of Reactions

A reaction is considered spontaneous if it occurs without external intervention under standard conditions. This is often determined by the change in Gibbs free energy (ΔG); if ΔG is negative, the reaction is spontaneous. Factors such as enthalpy (ΔH) and entropy (ΔS) changes also play a crucial role in assessing spontaneity.
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Standard Conditions

Standard conditions refer to a set of specific conditions used to measure and compare the properties of substances, typically defined as 1 atm pressure and a temperature of 25 °C (298 K). Under these conditions, the standard enthalpy and Gibbs free energy of formation can be used to evaluate the spontaneity of reactions, providing a consistent framework for analysis.
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Thermodynamic Data

Thermodynamic data, including standard enthalpy of formation (ΔH°f) and standard entropy (S°), are essential for calculating the Gibbs free energy change of a reaction. By using these values, one can determine whether the overall reaction is energetically favorable and thus spontaneous. This data is typically found in tables and is crucial for predicting reaction behavior.
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Related Practice
Textbook Question

Trouton’s rule states that for many liquids at their normal boiling points, the standard molar entropy of vaporization is about 88 J/mol‐K. b. Look up the normal boiling point of Br2 in a chemistry handbook or at the WebElements website (www.webelements.com) and compare it to your calculation. What are the possible sources of error, or incorrect assumptions, in the calculation?

Textbook Question

(c) In general, under which condition is ΔG°f more positive (less negative) than ΔH°f ? (i) When the temperature is high, (ii) when the reaction is reversible, (iii) when ΔS°f is negative.

Textbook Question

Consider the following three reactions: (i) Ti(s) + 2 Cl2(g) → TiCl4(1g) (a) For each of the reactions, use data in Appendix C to calculate ΔH°, ΔG°, K, and ΔS ° at 25 °C.

Textbook Question

Consider the following three reactions: (i) Ti(s) + 2 Cl2(g) → TiCl4(1g) (ii) C2H6(g) + 7 Cl2(g) → 2 CCl4(g) + 6 HCl(g) (iii) BaO(s) + CO2(g) → BaCO3(s) (c) For each of the reactions, predict the manner in which the change in free energy varies with an increase in temperature.

Textbook Question

Using the data in Appendix C and given the pressures listed, calculate Kp and ΔG for each of the following reactions:

(a) N2(g) + 3 H2(g) → 2 NH3(g) PN2 = 2.6 atm, PH2 = 5.9 atm, PNH3 = 1.2 atm

(b) 2 N2H4(g) + 2 NO2(g) → 3 N2(g) + 4 H2O(g) PN2H4 = PNO2 = 5.0 × 10-2 atm, PN2 = 0.5 atm, PH2O = 0.3 atm

(c) N2H4(g) → N2(g) + 2 H2(g) PN2H4 = 0.5 atm, PN2 = 1.5 atm, PH2 = 2.5 atm

Textbook Question

(a) For each of the following reactions, predict the sign of ΔH° and ΔS° without doing any calculations. (i) 2 Mg(s) + O2 (g) ⇌ 2 MgO(s) (ii) 2 KI(s) ⇌ 2 K(g) + I2(g) (iii) Na2(g) ⇌ 2 Na(g) (iv) 2 V2O5(s) ⇌ 4 V(s) + 5 O2(g)