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Consider the reaction $$2 \mathrm{O}(g) \longrightarrow \mathrm{O}_{2}(g)$$ a. Predict the signs of \(\Delta H\) and \(\Delta S\). b. Would the reaction be more spontaneous at high or low temperatures?

Short Answer

Expert verified
∆H is negative and ∆S is negative. The reaction would be more spontaneous at low temperatures.

Step by step solution

01

Analyze the reaction and predict the signs of ∆H and ∆S

For the formation of O2 from two separate O atoms, the reaction goes from dispersed atoms to a single molecule, so the entropy ∆S should be negative. Furthermore, upon bond formation, energy is released, so the enthalpy change ∆H should be negative as well. Answer: ∆H is negative and ∆S is negative.
02

Determine the spontaneity at high or low temperatures

The spontaneity of a reaction is determined by the sign of the Gibbs free energy change (∆G), which is given by the equation: \(∆G = ∆H - T∆S\) Since both ∆H and ∆S are negative, we can infer the following information: 1. At low temperatures (T is small), the term -T∆S is small and positive, making the overall ∆G negative. This means that the reaction is spontaneous at low temperatures. 2. At high temperatures (T is large), the term -T∆S becomes larger and more positive, causing a positive or less negative ∆G. This would make the reaction less spontaneous or not spontaneous at all at high temperatures. Answer: The reaction would be more spontaneous at low temperatures.

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Key Concepts

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

Enthalpy (∆H)
Enthalpy, represented by the symbol ∆H, is a measure of the total heat content of a system. It indicates the energy change during a reaction, particularly the heat absorbed or released at constant pressure. Understanding enthalpy is crucial because chemical reactions often involve energy changes, which can be crucial in determining spontaneity.

For instance, when a reaction releases energy, such as in the formation of a chemical bond, ∆H is negative, which is referred to as an exothermic process. This means the surroundings absorb heat from the system. On the contrary, if a reaction absorbs energy from the surroundings, ∆H is positive, and this is an endothermic process. Enthalpy changes are vital for predicting how temperature affects the spontaneity of a reaction, as seen in the given exercise.
Entropy (∆S)
Entropy, conveyed as ∆S, is a fundamental concept in chemistry that describes the degree of disorder or randomness in a system. Every substance has some intrinsic entropy, and changes in physical states, mixing of substances, or chemical reactions can alter this entropy.

The second law of thermodynamics states that the entropy of the universe tends to increase over time, which often means that processes that increase entropy are naturally favored. A positive ∆S indicates an increase in disorder—such as solid melting into liquid—while a negative ∆S, as in the formation of O_2 from separate atoms, implies a decrease in disorder. By examining the entropy change in chemical reactions, scientists can discern important aspects of the reaction's spontaneity and the conditions under which it will proceed.
Gibbs Free Energy (∆G)
Gibbs free energy, designated as ∆G, is the single most useful criterion for predicting the spontaneity of a reaction at constant temperature and pressure. It combines the concepts of enthalpy and entropy to offer a holistic view:ΔG = ΔH - TΔSWhere T is the absolute temperature in Kelvin. If ∆G is negative, the reaction is spontaneous, and if ∆G is positive, it is non-spontaneous.

For reactions where both ∆H and ∆S are negative, temperature plays a pivotal role in determining spontaneity. At lower temperatures, the reaction is more likely to be spontaneous because the entropic penalty (-TΔS) is less significant. This is why, as in the discussed exercise, certain reactions are more spontaneous at lower temperatures. Understanding how Gibbs free energy can predict the conditions under which reactions proceed is a cornerstone of chemical thermodynamics.

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Most popular questions from this chapter

Two crystalline forms of white phosphorus are known. Both forms contain \(\mathrm{P}_{4}\) molecules, but the molecules are packed together in different ways. The \(\alpha\) form is always obtained when the liquid freezes. However, below \(-76.9^{\circ} \mathrm{C}\), the \(\alpha\) form spontaneously converts to the \(\beta\) form: $$\mathrm{P}_{4}(s, \alpha) \longrightarrow \mathrm{P}_{4}(s, \beta)$$ a. Predict the signs of \(\Delta H\) and \(\Delta S\) for this process. b. Predict which form of phosphorus has the more ordered crystalline structure (has the smaller positional probability).

List three different ways to calculate the standard free energy change, \(\Delta G^{\circ}\), for a reaction at \(25^{\circ} \mathrm{C}\). How is \(\Delta G^{\circ}\) estimated at temperatures other than \(25^{\circ} \mathrm{C}\) ? What assumptions are made?

Impure nickel, refined by smelting sulfide ores in a blast furnace, can be converted into metal from \(99.90 \%\) to \(99.99 \%\) purity by the Mond process. The primary reaction involved in the Mond process is $$\mathrm{Ni}(s)+4 \mathrm{CO}(g) \rightleftharpoons \mathrm{Ni}(\mathrm{CO})_{4}(g)$$ a. Without referring to Appendix 4, predict the sign of \(\Delta S^{\circ}\) for the above reaction. Explain. b. The spontaneity of the above reaction is temperature dependent. Predict the sign of \(\Delta S_{\text {sarr }}\) for this reaction. Explain. c. For \(\mathrm{Ni}(\mathrm{CO})_{4}(g), \Delta H_{\mathrm{f}}^{\circ}=-607 \mathrm{~kJ} / \mathrm{mol}\) and \(S^{\circ}=417 \mathrm{~J} / \mathrm{K} \cdot \mathrm{mol}\) at \(298 \mathrm{~K}\). Using these values and data in Appendix 4, calculate \(\Delta H^{\circ}\) and \(\Delta S^{\circ}\) for the above reaction. d. Calculate the temperature at which \(\Delta G^{\circ}=0(K=1)\) for the above reaction, assuming that \(\Delta H^{\circ}\) and \(\Delta S^{\circ}\) do not depend on temperature. e. The first step of the Mond process involves equilibrating impure nickel with \(\mathrm{CO}(\mathrm{g})\) and \(\mathrm{Ni}(\mathrm{CO})_{4}(g)\) at about \(50^{\circ} \mathrm{C}\). The purpose of this step is to convert as much nickel as possible into the gas phase. Calculate the equilibrium constant for the preceding reaction at \(50 .{ }^{\circ} \mathrm{C}\). f. In the second step of the Mond process, the gaseous \(\mathrm{Ni}(\mathrm{CO})_{4}\) is isolated and heated to \(227^{\circ} \mathrm{C}\). The purpose of this step is to deposit as much nickel as possible as pure solid (the reverse of the preceding reaction). Calculate the equilibrium constant for the preceding reaction at \(227^{\circ} \mathrm{C}\). g. Why is temperature increased for the second step of the Mond process? h. The Mond process relies on the volatility of \(\mathrm{Ni}(\mathrm{CO})_{4}\) for its success. Only pressures and temperatures at which \(\mathrm{Ni}(\mathrm{CO})_{4}\) is a gas are useful. A recently developed variation of the Mond process carries out the first step at higher pressures and a temperature of \(152^{\circ} \mathrm{C}\). Estimate the maximum pressure of \(\mathrm{Ni}(\mathrm{CO})_{4}(g)\) that can be attained before the gas will liquefy at \(152^{\circ} \mathrm{C}\). The boiling point for \(\mathrm{Ni}(\mathrm{CO})_{4}\) is \(42^{\circ} \mathrm{C}\) and the enthalpy of vaporization is \(29.0 \mathrm{~kJ} / \mathrm{mol}\).

Consider the following reaction at \(25.0^{\circ} \mathrm{C}\) : $$2 \mathrm{NO}_{2}(g) \rightleftharpoons \mathrm{N}_{2} \mathrm{O}_{4}(g)$$ The values of \(\Delta H^{\circ}\) and \(\Delta S^{\circ}\) are \(-58.03 \mathrm{~kJ} / \mathrm{mol}\) and \(-176.6 \mathrm{~J} / \mathrm{K}\). mol, respectively. Calculate the value of \(K\) at \(25.0^{\circ} \mathrm{C}\). Assuming \(\Delta H^{\circ}\) and \(\Delta S^{\circ}\) are temperature independent, estimate the value of \(K\) at \(100.0^{\circ} \mathrm{C}\).

Consider the following energy levels, each capable of holding two objects: \(E=2 \mathrm{~kJ}\) ______ \(E=1 \mathrm{~kJ}\) ______ \(E=0 \quad \mathrm{XX}\) Draw all the possible arrangements of the two identical particles (represented by X) in the three energy levels. What total energy is most likely, that is, occurs the greatest number of times? Assume that the particles are indistinguishable from each other.

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