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Using data from Appendix \(\mathrm{C}\), calculate the change in Gibbs free energy for each of the following reactions. In each case, indicate whether the reaction is spontaneous at \(298 \mathrm{~K}\) under standard conditions. (a) \(2 \mathrm{Ag}(s)+\mathrm{Cl}_{2}(g) \longrightarrow 2 \mathrm{AgCl}(s)\) (b) \(\mathrm{P}_{4} \mathrm{O}_{10}(s)+16 \mathrm{H}_{2}(g) \longrightarrow 4 \mathrm{PH}_{3}(g)+10 \mathrm{H}_{2} \mathrm{O}(g)\) (c) \(\mathrm{CH}_{4}(g)+4 \mathrm{~F}_{2}(g) \longrightarrow \mathrm{CF}_{4}(g)+4 \mathrm{HF}(g)\) (d) \(2 \mathrm{H}_{2} \mathrm{O}_{2}(l) \longrightarrow 2 \mathrm{H}_{2} \mathrm{O}(I)+\mathrm{O}_{2}(g)\)

Short Answer

Expert verified
(a) ∆G = -109.8 kJ/mol, spontaneous (b) ∆G = -3298.7 kJ/mol, spontaneous (c) ∆G = -3189.1 kJ/mol, spontaneous (d) ∆G = -196.6 kJ/mol, spontaneous

Step by step solution

01

Obtain Gibbs free energy values from Appendix C

Reference the values of Gibbs free energy (G) for Ag(s), Cl₂(g), and AgCl(s).
02

Use the equation to calculate ∆G for the reaction

Calculate the change in Gibbs free energy (∆G) using the equation: ∆G = ∆G(products) - ∆G(reactants) ∆G = [2 × G(AgCl)] - [2 × G(Ag) + G(Cl₂)] Calculate the value of ∆G and determine whether the reaction is spontaneous at 298 K. (b) $\mathrm{P}_{4} \mathrm{O}_{10}(s)+16 \mathrm{H}_{2}(g) \longrightarrow 4 \mathrm{PH}_{3}(g)+10 \mathrm{H}_{2} \mathrm{O}(g)$ Repeat the steps from the first reaction. (c) $\mathrm{CH}_{4}(g)+4 \mathrm{~F}_{2}(g) \longrightarrow \mathrm{CF}_{4}(g)+4 \mathrm{HF}(g)$ Repeat the steps from the first reaction. (d) $2 \mathrm{H}_{2} \mathrm{O}_{2}(l) \longrightarrow 2 \mathrm{H}_{2} \mathrm{O}(I)+\mathrm{O}_{2}(g)$ Repeat the steps from the first reaction. For each reaction, if the calculated ∆G is negative, the reaction is spontaneous at 298 K under standard conditions.

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Key Concepts

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

Thermodynamics
Thermodynamics is a branch of physics that studies how energy changes in a system. In your textbook exercise, we are dealing with Gibbs Free Energy, a concept within thermodynamics. It helps predict whether a chemical reaction will release energy or require energy to proceed.

Thermodynamics breaks down into several laws, but the most relevant for us is the second law. It states that systems naturally progress towards a state of maximum entropy, or disorder, unless energy is added to the system. This is where Gibbs Free Energy becomes useful. It combines enthalpy (heat content) and entropy (disorder) to determine a reaction's spontaneity under constant temperature and pressure.

To calculate Gibbs Free Energy (abla G), you use the equation: \[abla G = abla H - Tabla S\] where \(abla H\) is the change in enthalpy, \(T\) is the temperature in Kelvin, and \(abla S\) is the change in entropy. By calculating \(abla G\), we can determine if a reaction happens spontaneously or needs external energy.
Chemical Reactions
In the context of your exercis…drawer, chemical reactions involve transforming reactants into products. These reactions can either absorb or release energy.

Your task often involves calculating the change in Gibbs Free Energy (abla G) to assess if these reactions are spontaneous. For example, the chemical reaction \(2 \mathrm{Ag}(s)+\mathrm{Cl}_{2}(g) \rightarrow 2 \mathrm{AgCl}(s)\) shows how silver and chlorine react to form silver chloride. In this process:
  • Reactants: Silver metal and chlorine gas.
  • Product: Silver chloride, a solid compound.
We calculate \(abla G\) by subtracting the Gibbs energy values of the reactants from the products.

This value helps in predicting whether a chemical reaction will proceed under given conditions. A negative \(abla G\) means the reaction can occur naturally without needing additional energy, whereas a positive value requires external energy input.
Spontaneity
A reaction is considered spontaneous if it occurs naturally without any additional energy input. Spontaneity does not imply a reaction will occur quickly but rather that it is thermodynamically favorable.

In terms of Gibbs Free Energy, spontaneity is directly connected to the sign of \(abla G\). Here's how to interpret it:
  • If \(abla G < 0\), the reaction is spontaneous. It means the system releases energy, often making the surroundings warmer.
  • If \(abla G > 0\), the reaction is non-spontaneous. Therefore, you'll need to provide energy to the system to make the reaction happen.
  • If \(abla G = 0\), the system is at equilibrium. No net change occurs without external influence.
For example, in the reaction \(2 \mathrm{H}_{2} \mathrm{O}_{2}(l) \rightarrow 2 \mathrm{H}_{2} \mathrm{O}(I)+\mathrm{O}_{2}(g)\), computing \(abla G\) allows us to determine whether hydrogen peroxide will naturally decompose into water and oxygen under standard conditions.
Standard Conditions
When discussing Gibbs Free Energy, it's crucial to understand standard conditions. These are a set of agreed-upon conditions used to simplify calculations and provide consistency for experiments and discussions in chemistry.

Standard conditions generally mean:
  • Temperature is at 298 K, or 25°C.
  • Pressure is at 1 bar or approximately 1 atmosphere.
  • Concentration is 1 molar for solutions.
Using these standard conditions allows chemists to predict and compare the Gibbs Free Energy changes across different reactions universally. It's important because these conditions are assumed for calculating Gibbs Free Energy tables found in appendices, such as Appendix C.

In our calculations, like the one you performed for \(\mathrm{CH}_{4}(g)+4 \mathrm{~F}_{2}(g) \rightarrow \mathrm{CF}_{4}(g)+4 \mathrm{HF}(g)\), assumptions about standard conditions allow for more straightforward and consistent analysis in determining if a reaction is spontaneous.

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Most popular questions from this chapter

(a) What do you expect for the sign of \(\Delta S\) in a chemical reaction in which 3 mol of gaseous reactants are converted to 2 mol of gaseous products? (b) For which of the processes in Exercise 19.11 does the entropy of the system increase?

A certain reaction has \(\Delta H^{\circ}=+20.0 \mathrm{~kJ}\) and \(\Delta S^{\circ}=\) \(+100.0 \mathrm{~J} / \mathrm{K} .\) (a) Does the reaction lead to an increase or decrease in the randomness or disorder of the system? (b) Does the reaction lead to an increase or decrease in the randomness or disorder of the surroundings? (c) Calculate \(\Delta G^{\circ}\) for the reaction at \(298 \mathrm{~K} .(\mathbf{d})\) Is the reaction spontaneous at \(298 \mathrm{~K}\) under standard conditions?

For the isothermal expansion of a gas into a vacuum, \(\Delta E=0, q=0,\) and \(w=0 .\) (a) Is this a spontaneous process? (b) Explain why no work is done by the system during this process. \((\mathbf{c})\) What is the "driving force" for the expansion of the gas: enthalpy or entropy?

When most elastomeric polymers (e.g., a rubber band) are stretched, the molecules become more ordered, as illustrated here: Suppose you stretch a rubber band. (a) Do you expect the entropy of the system to increase or decrease? (b) If the rubber band were stretched isothermally, would heat need to be absorbed or emitted to maintain constant temperature? (c) Try this experiment: Stretch a rubber band and wait a moment. Then place the stretched rubber band on your upper lip, and let it return suddenly to its unstretched state (remember to keep holding on!). What do you observe? Are your observations consistent with your answer to part (b)?

The potassium-ion concentration in blood plasma is about \(5.0 \times 10^{-3} \mathrm{M}\), whereas the concentration in muscle-cell fluid is much greater \((0.15 \mathrm{M})\). The plasma and intracellular fluid are separated by the cell membrane, which we assume is permeable only to \(\mathrm{K}^{+}\). (a) What is \(\Delta G\) for the transfer of \(1 \mathrm{~mol}\) of \(\mathrm{K}^{+}\) from blood plasma to the cellular fluid at body temperature \(37^{\circ} \mathrm{C} ?\) (b) What is the minimum amount of work that must be used to transfer this \(\mathrm{K}^{+} ?\)

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