Chapter Eight Thermodynamics: The Second and Third Laws CHEM1211K Spring2013

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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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Spontaneous Change (8.1)

A spontaneous process is one that has a tendency to occur without needing to be driven by an external influence (thermodynamics) Spontaneous processes include: Expansion of a gas into a vacuum Cooling of heated objects Conversion of diamond into graphite Combination of hydrogen and oxygen to give water Chemical processes may be very fast or very slow depending upon their activation energy (kinetics/rates of reaction chapter 14)

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Entropy and Disorder (8.2)

Entropy, S, is a measure of disorder The second law of thermodynamics states that the natural progression of a system and its surroundings (which together make up the universe) is: from order to disorder from organized to random from lower to higher entropy According to the second law, the entropy of an isolated system increases in any spontaneous process Entropy is a state function

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Entropy and Disorder (8.2)

At constant temperature: S =

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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Entropy and Disorder (8.2)

At constant temperature: S =

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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Changes in Entropy (8.3)

Example: Calculate the change in entropy (in J/K) when 18.02 g of water is heated from 1.00 to 20.0oC at constant pressure. The CP,m for water is 75.3 J/mol.K

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Changes in Entropy (8.3)

We have already considered the expression the entropy change for isothermal expansion of an (ideal) gas S = nR(Vf/Vi) or nR(V2/V1) Since P1V1 = P2V2, V2/V1=P1/P2 this expression can be converted to an expression for the entropy change accompanying a pressure change at constant T S = nR(P1/P2)

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Changes in Entropy (8.3)

Example: What is the change in entropy when 1.00 mol Ar(g) is compressed suddenly (and irreversibly) from 5.00 L to 1.00 L by driving a piston, and in the process its temperature is increased from 20.0 C to 25.2 C.

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Entropy Changes Accompanying Changes in Physical State (8.4)

Changes in phase occur reversibly at constant temperature and pressure so qrev = H and S = H/T Fusion Sfus = Hfus/T Vaporization Svap = Hvap/T Sublimation Ssub = Hsub/T Ssub= Sfus + Svap

Zumdahl, 5th edition

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Entropy Changes Accompanying Changes in Physical State (8.4)

Troutons rule The standard molar entropy of vaporization is approximately 85 J K-1 This is because liquids without specific intermolecular interactions have approximately the same disorder upon vaporization Substantial deviations of the value of the standard molar entropy of vaporization from this value result when there are specific interactions between liquid molecules that increase the order

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Entropy Changes Accompanying Changes in Physical State (8.4)

Example: What is the molar entropy of vaporization of water at 25.0 C and 1 atm in J/molK? CP for liquid water = 75.3 J/molK and Hvap = 40.7 kJ/mol.

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A Molecular Interpretation of Entropy (8.5)

The third law of thermodynamics states that entropies of all perfect crystals approach zero as the absolute temperature approaches zero Because of this at temperatures other than absolute zero, substances have finite entropies, which can be estimated on a statistical basis and determined experimentally

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A Molecular Interpretation of Entropy (8.5)

Statistically S = k ln(W) where W is the number of ways the system can be arranged without changing its energy Experimentally, S = 0 P , and is determined graphically T by plotting CP/T vs T and taking the area under the curve
T

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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Standard Molar Entropies (8.7)

Molar entropies can be determined experimentally Large, complex molecules have higher molar entropies than smaller, simpler ones Liquids have higher molar entropies than solids because the greater freedom of movement of the molecules in the liquid results in less order For the same reason, gases have higher molar entropies than liquids.
Table 8.3 Standard molar entropies at 25 C (J K-1 mol-1)

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Standard Reaction Enthalpies (8.8)

An increase in the number of moles of gaseous substances causes an increase in entropy Increasing the number of particles causes an increase in entropy

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Standard Reaction Enthalpies (8.8)

In many cases, the sign for the entropy of the system can be predicted with no calculation. Increase in T Increase in V Mixing of two liquids or dissolving a solid in a liquid Phase changes Melting, vaporization, and sublimation Freezing, condensation, and deposition

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Standard Reaction Enthalpies (8.8)

The standard reaction entropy S:
o o S o = n S m n S products m reactants

n = stoichiome tric coefficients

Temperature must be specified since the value of the molar entropy varies with T frequently tabulated at 25 C We can calculate an entropy of reaction, Srxn, or the difference between the entropies of the products and the reactants

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Standard Reaction Entropies (8.8)

Predict the sign of S for: CO2(s) CO2(g) 2 SO3(g) 2 SO2(g) + O2(g) Na+(aq) + Cl-(aq) NaCl(s) Freezing of water

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The Surroundings (8.9)

The second law refers to an isolated system. Any system must be considered to be part of a larger isolated system that includes the surroundings of the system of interest. The process is spontaneous only if the TOTAL change in entropy is positive.

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The Surroundings (8.9)

A process in which Ssys is negative may actually be spontaneous if the entropy increases enough in the surroundings.

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The Surroundings (8.9)

The surroundings are always taken to be large, so their temperature remains constant however much energy is transferred to or from them as heat. The heat that leaves the system enters the surroundings. qsurr = -qsys

qsurr, rev Ssurr = T at constant pressure - H Ssurr = T

Figure 8.17 a) exothermeric process b) endothermic process

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The Surroundings (8.9)

Example: Calculate the entropy change of the surroundings when 2.50 mol of liquid water vaporizes at 85C and 1 bar. The enthalpy of vaporization of liquid water is 40.7 kJ/mol.

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The overall change in entropy (8.10)

Both the entropy change of the system AND the surroundings affect the direction of a reaction, because both contribute to the entropy of the universe If total S is positive (increases), a process is spontaneous If total S is zero a process has no tendency to proceed in either direction If total S is negative (decreases), a process is not spontaneous as written, but the reverse is

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The overall change in entropy (8.10)

Very exothermic reactions will deliver heat to the surroundings and increase their entropy This may be offset by a decrease in entropy for the system if the number of gaseous molecules or total particles decreases Very endothermic reactions will take heat from the surroundings and decrease their entropy

Figure 8.18 Exothermic process a) Ssys = + b) Ssys =

Figure 8.19 Endothermic process

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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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Equilibrium - Gibbs Free Energy (8.11)

One problem with using the second law to judge whether a reaction is spontaneous is that to get the total entropy change we must calculate three different quantities: Entropy change of the system Entropy change of the surroundings Total change in entropy The Gibbs Free Energy is a state function, which combines these calculations into one equation that can be used to Predict spontaneity The impact of temperature on spontaneity Determine non expansion work (heat)

Figure 8.23
http://en.wikipedia.org/wiki/ File:Josiah_Willard_Gibbs_-from_MMS-.jpg 8 30

Focusing on the System (8.12)

Gibbs free energy (also known as Gibbs energy) can be defined as: G = H TS constant pressure and temperature Since only differences in the Gibbs free energy can be determined the equation becomes G = H TS The criterion for spontaneity is a negative G, which corresponds to an increase in Stot If G = 0 system is at equilibrium (Stot = 0)

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Focusing on the System (8.12)

The criterion for spontaneity is a negative G, which corresponds to an increase in Stot For a process or reaction there are four possible combinations of H and S
H negative positive negative positive S positive negative negative positive negative positive negative if H>TS positive if H<TS negative if H<TS positive if H<TS G Spontaneous Yes No Yes No Yes No

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Focusing on the System (8.12)

For a system at equilibrium, G = 0. Example: If liquid water and ice are at equilibrium with each other at a certain temperature and pressure, then the Gibbs free energy for one mole of liquid water must be the same as the Gibbs free energy of one mole of ice.

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Focusing on the System (8.12)

Example: Calculate the change in molar Gibbs free energy for the melting of ice at 1 atm and -10.0oC. Is the process spontaneous? For H2O, Hfus = 6.01 kJ/mol and Sfus 22.0 J/mol.K

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Gibbs Free Energy of Reaction (8.13)

As with enthalpy and entropy, we might calculate the Gibbs free energy of reaction (Grxn) Grxn = nGproducts nG reactants n = stoichiome tric coefficients Or, we might calculate the standard Gibbs free energy of reaction (G)
o o Go = nGm n G m reactants products

n = stoichiome tric coefficients

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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Gibbs Free Energy of Reaction (8.13)

The standard Gibbs free energy of formation (Gf) is the standard Gibbs free energy of reaction per mole for the formation of a compound from its elements in their most stable form. Gf for elements in their most stable form is zero Now we can use the following expression to calculate the free energy change for a reaction
o G o = n G o f products nG f reactants

n = stoichiome tric coefficients

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Gibbs Free Energy of Reaction (8.13)

Gf at a given temperature is an indication of a compounds stability relative to its elements under standard conditions Temperature must be specified most tabulations are for 25 C If Gfo > 0, the Gibbs free energy of the compound is higher than that of its elements and the compound is poised to change spontaneously into the pure elements

Figure 8.27

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Gibbs Free Energy of Reaction (8.13)

A compound with negative standard Gibbs free energy of formation is said to be thermodynamically stable A compound with positive standard Gibbs free energy of formation is said to be thermodynamically unstable This may not happen in reality because the decomposition may be very slow; such compounds are said to be nonlabile, inert Substances that do decompose readily are reactive, labile

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Gibbs Free Energy of Reaction (8.13)

Keep in mind the distinction: Stable and unstable Labile, nonlabile, and inert

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The Gibbs free energy and nonexpansion work (8.14)

The change in Gibbs free energy for a process is equal to the nonexpansion work that the system can do at constant temperature and pressure

ATP

ADP

ATP + H2O ADP + Pi G = 30.5 kJ/mol (1 M)

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The Effect of Temperature (8.15)

Gibbs free energy is temperature dependent
G = H TS
H S + + + + G + if H>TS + if H<TS if H<TS + if H<TS

From Zumdahl, 5th edition

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The Effect of Temperature (8.15)

Example: Is the following reaction spontaneous at room temperature? At 1000 K? 2Fe2O3(s) + 3C(s) 4Fe(s) + 3CO2(g) H = +467.9 kJ S = +588.4 J/K

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