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Objectives
Develop an understanding of spontaneity and entropy. Entropy changes accompanying changes in physical state Develop a molecular interpretation of entropy Examine the equivalence of statistical and thermodynamic entropy Understand how entropy of a system and entropy of surroundings is related. Be able to work with Gibbs free energy and relate it to spontaneity Understand the effect of temperature on Gibbs free energy Explore the relationship between Gibbs free energy and equilibrium
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Key Ideas
The direction of natural change corresponds to the increasing disorder of energy and matter. Disorder is measured by the thermodynamic quantity called entropy. A related quantityGibbs free energyprovides a link between thermodynamics and the description of chemical equilibrium
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Why is it important?
The second law of thermodynamics is the key to understanding why on chemical reaction has a natural tendency to occur by another one does not. The third law of thermodynamics is the basis of the numerical values of entropy and Gibbs free energy. The second and third laws jointly provide a way to predict the effects of changes in temperature and pressure on physical and chemical processes.
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qrev T
This equation can be used to calculate entropy changes for isothermal processes such as the reversible expansion of a gas Using equation 7.4 for the reversible w (done) = -nRTln(Vf/Vi) and realizing that q (absorbed) = -w so that S = nRTln(Vf/Vi)/T = nR(Vf/Vi). Note that the entropy increases because the same number of gas particles is contained in a larger container with more room to move about (greater disorder) This expression can be used to derive an equation to calculate the entropy change when a system is heated
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qrev T
However, many processes involve changes in temperature A modified version of this expression can be used to derive an equation to calculate the entropy change when a system is heated, i.e., dS = dqrev/T and that dqrev = CdT C is heat capacity at constant V or P as appropriate Now dS = CdT/T, which can be integrated for changes in T between T1 and T2 This gives the general expression S = Cln(T2/T1) If T2>T1 the entropy increases consistent with increased thermal motion and therefore disorder
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C dT
CP is not constant over wide ranges of temperature and must be determined as a function of temperature
Figure 8.11
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Equilibrium (8.11)
A system at equilibrium has no tendency to change in either direction (forward or reverse). The system will remain in its current state until disturbed by changing conditions (T, V, adding more reactants, etc.). When a system is in dynamic equilibrium, both the forward and reverse processes still continue but their rates are equal The general criterion for equilibrium in thermodynamics is Stotal = 0
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Equilibrium (8.11)
For a chemical system in dynamic equilibrium, there is no macroscopic evidence of change though there is a continuation of processes at the microscopic level. There is no NET change.
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Figure 8.23
http://en.wikipedia.org/wiki/ File:Josiah_Willard_Gibbs_-from_MMS-.jpg 8 30
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Of course, neither of these expressions are very useful since the absolute value of G cannot be determined only the difference between initial and final states
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Figure 8.27
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ATP
ADP
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