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9 • Outline

– Defining the Gibbs Free Energy (ΔG) – Calculating ΔG – Pictorial Representation of ΔG

• Problems Z10.49-51, Z10.54, Z10.56-58

1

Entropy Summary

Three different ways the system and environment entropies can combine to produce spontaneous conditions.

ΔΗ°sys < 0

ΔS°sys

ΔS°surr

ΔS°univ

ΔΗ°sys < 0

ΔS°surr

ΔS°univ

ΔS°sys

ΔΗ°sys > 0

ΔS°sys

ΔS°univ ΔS°surr

2

Defining ΔG • Recall. 3 . when there is no subscript on H or S it means for the system.T ΔS Notice. the second law of thermodynamics: ΔSuniv = ΔStotal = ΔSsystem + ΔSsurr • Also: q ΔH ΔSsurr = − =− T T Therefore rev P ΔP = 0 −T ΔStotal = ΔH .

because we define: G = H − TS or ΔG = ΔH − Δ ( TS ) • At constant Pressure then the heat out out of the system is the heat into the surroundings (or environment). so these are the correct values of S. H and G regardless of path. {However. the other perspective • G is a state function. the actual amount of heat depends on path.ΔG as a state function. Does the reaction have to be done reversibly? No.} 4 . surr system qrev qrev ΔH ΔS surr = =− =− T T T ΔH = −T ΔS surr @ constant T: ΔG = ΔH − T ΔS We used reversible heat. because the state functions are independent of path.

the Gibbs energy of the system is: ΔG = ΔH . Notice that the sign of the criterion of spontaneity does change (between total entropy and Gibbs energy).T ΔS = −T ΔStotal So the Gibbs energy (which is only of the system and does not mention the surroundings) is as valid a criterion of spontaneity as the total entropy (of the universe). 5 .Gibbs (Free) Energy and spontaneity If a reaction (or physical change such as ice melting) is happening at constant temperature and pressure.

equilibrium • In our derivation of ΔG.. therefore. the direction of the inequality changes relative to entropy.process is spontaneous – If ΔSuniv < 0…. we divided by -T.ΔG and Spontaneous Processes • Recall from the second law the conditions of spontaneity: • Three possibilities: – If ΔSuniv > 0….. – If ΔSuniv = 0…. 6 .process is spontaneous in opposite direction.

. P processes) – If ΔG < 0….process is spontaneous – If ΔG > 0…..process is spontaneous in opposite direction.equilibrium • In terms of ΔG: (only for constant T..process is spontaneous – If ΔSuniv < 0….equilibrium 7 .process is spontaneous in opposite direction..ΔG criterion of spontaneous • Three possibilities: (for any process) – If ΔSuniv > 0…. – If ΔG = 0…. – If ΔSuniv = 0….

spontaneous at low T If ΔH > 0 and ΔS > 0…. Such that: If ΔH < 0 and ΔS > 0….TΔS • A reaction is spontaneous if ΔG < 0.not spontaneous at any T If ΔH < 0 and ΔS < 0….spontaneous at any T If ΔH > 0 and ΔS < 0….spontaneous at high T 8 .ΔG and Spontaneous Processes • Note that ΔG is composite of both ΔH and ΔS ΔG = ΔH .

• We found that the enthalpy for melting and boiling were rather independent of temperature. and water freezes below 0C. • This is a model (we can remember) for any chemical transformation 9 . If possible. But need to raise T to some critical value so that the entropy can take over and melt ice. So the melting should be entropically favorable. Ice (like all solids) is the stable form at low temperatures because melting is endothermic (the ice must have heat to melt).Ice Melting • Know ice melts above 0C. Melting is not enthalpically favorable. • Competing with this is the entropy which (statistically) was the tendency to disorder (greater positional possibilities). • Why? What does thermodynamics tell us about this process? • It is a trade off of two (large) competing tendencies. if the water molecules can have more places to go they will do that. Liquid water affords molecules an opportunity to migrate (unlike solid water).

Notice it is positive.The entropy of melting H 2O ( s ) H 2O ( ) ΔH = ΔH ( ) − ΔH ( s ) = 6 kJ / mole • Ice melts at 0C. so ΔG=0=ΔH-TΔS. • What is the entropy change for ice to melt? • At the transition temperature. so the Gibbs Energy becomes negative at higher temperatures. breaking water-water bonds. as one expect. • The favorable bonding of water to water (enthalpically favored) is broken by the randomization forces of entropy. the two phases are in equilibrium. The latent heat of fusion is 6kJ/mole. 10 . Solve for the entropy difference: ΔH 6 ⋅10 ΔS = = = 22 J mol ⋅ K T 273 3 • Notice Entropy change is positive. and the liquid form is favored (by entropic terms).

ΔS° = 93.Esoteric Example (A liquid boils) • At what T is the following reaction spontaneous? Br (l) Br (g) 2 2 ΔH° = 30. then 0 = ΔG = ΔH . Assume that the enthalpy and entropy changes upon boiling are rather independent of temperature.T Δ S ΔG° = ΔH° .K @T=25°C ΔG = Δ H .91 kJ/mol.T ΔS Tboiling ΔH ΔH 0 = ≈ = 331K 0 ΔS ΔS 11 .2 J/mol.TΔS° only @ T=25°C The criterion of spontaneity is Gibbs Energy Change is zero.

Boiling Example • Try 298 K just to see: ΔG° = ΔH° .91 kJ/mol .TΔS° ΔG° = 30.91 − 27.2 J/mol.78) kJ/mol = 3. Br2 will boil.(298K)(93.e. Above that temperature the process will be spontaneous (i.) 12 . but the two big numbers are just about canceling.K) ΔG° = (30. we need to go up from 300 to 330 to get cancellation.13 kJ/mol > 0 Not spontaneous at 298 K.

Need more going on. such as the number of moles changing.Gibbs Energy for reactions • Cannot have a change in the gas in a box for a process at constant T and P. 13 . • We wrote the enthalpy in terms of the molar enthalpies of formation of each of the species. This is where a chemical reaction comes in. • For a chemical reaction at constant T and P the only contributions to the changing free energy are due to the changes in the concentrations of the various species. now write the total Gibbs energy as the sum of the molar Gibbs energies for each of the species.

ΔG is a state function. 14 . therefore. −∑ creact ΔG°react .Calculating ΔG°rxn • Can evaluate all reaction energies at standard thermodynamic conditions (1 Atm 25C) where the superscirt “naught” is applied. • Previously we needed to determine ΔH°rxn and ΔS°rxn to determine ΔG°rxn • Now. we can use known ΔG° for each of the chemical species to determine ΔG°rxn using: ΔG°rxn = ∑ c prod ΔG° prod .

ΔGf° = 0 for an element in its standard state: Example: ΔGf° (O2(g)) = 0 15 .Standard ΔG of Formation: ΔGf° • (Like ΔHf° and S°) • ΔGf° is defined as the “change in free energy that accompanies the formation of 1 mole of that substance for its constituent elements with all reactants and products in their standard state.” • Like ΔHf°.

Gibbs Energy of Reaction (Example) • Determine the ΔG°rxn for the following: C2H4(g) + H2O(l) C2H5OH(l) • Tabulated ΔG°f from Appendix 4: ΔG°f(C2H5OH(l)) = -175 kJ/mol ΔG°f(C2H4(g)) = 68 kJ/mol ΔG°f(H2O (l)) = -237 kJ/mol 16 .

ΔG°f(C2H4(g) −ΔG°f(H2O (l)) ΔG°rxn = -175 kJ .68 kJ -(-237 kJ) ΔG°rxn = -6 kJ < 0 . 17 . Spontaneous at low T.Partially Burn a Hydrocarbon (see Z10. therefore. −∑ creact ΔG°react . ΔG°rxn = ΔG°f(C2H5OH(l)) . from this get ΔS°rxn =-120J/K. spontaneous Why is it spontaneous and for what temperatures is this true? ΔH°rxn =-44kJ.56) • Using these values: C2H4(g) + H2O(l) C2H5OH(l) ΔG°rxn = ∑ c prod ΔG° prod .

graphite) + O2(g) CO2(g) ΔG° = -397 kJ CO2(g) ΔG° = -394 kJ 18 . diamond) + O2(g) C(s.More ΔG°rxn • Similar to ΔH°. one can use the ΔG° for various reactions to determine ΔG° for the reaction of interest (a “Hess’ Law” for ΔG°) • Example: C(s.

ΔG°rxn Calculations C(s.. graphite) + O2(g) ΔG° = +394 kJ C(s. graphite) + O2(g) CO2(g) CO2(g) ΔG° = -397 kJ CO2(g) ΔG° = -394 kJ C(s.rxn is spontaneous 19 . diamond) ΔG°rxn < 0…. graphite) ΔG° = -3 kJ C(s. diamond) + O2(g) C(s.

• Example: CO2(g) C(s. it does not tell us how fast a reaction will proceed.ΔG°rxn ≠ Reaction Rate • Although ΔG°rxn can be used to predict if a reaction will be spontaneous as written. diamond) + O2(g) ΔG°rxn = -397 kJ <<0 20 But diamonds are forever?…. ΔG°rxn ≠ rate .

first? 21 .1 151.7 S° (J/mol.Example Problem • Is the following reaction spontaneous under standard conditions? 4 KClO3 ( s ) ⎯⎯ 3KClO4 ( s ) + 1KCl ( s ) → ΔH°f (kJ/mol) KClO3(s) KClO4(s) KCl (s) -397.8 -436.6 What would you guess qualitatively.7 -432.K) 143.0 82.

6 J K ) − 4(143.1 J K ) = −36.Example Problem Solution • Calculating ΔH°rxn 4KClO3 (s) ⎯ → 3KClO4 (s) + KCl(s) ⎯ ΔH°rxn = 3ΔH° f (KClO4 ) + ΔH° f (KCl) − 4ΔH° f (KClO3 ) = 3(−432.7kJ) = −144kJ • Calculating ΔS°rxn ΔS°rxn = 3S°(KClO4 ) + S°(KCl) − 4S°(KClO3 ) = 3(151.8kJ) + (−436.0 J K ) + (82.7kJ) − 4(397.8 J K 22 .

57-58. there is a temperature above which it will not be spontaneous. but that must be very large.therefore. See also Z10.6 J = −133kJ ( ⎛ 1kJ ⎞ K ⎜ 1000J ⎟ ⎠ ⎝ ) ΔG°rxn < 0 . reaction is spontaneous. The entropic term is very weak. Notice entropy and enthalpy have the same sign. 23 . Yes.Example Problem Solution • Calulating ΔG°rxn ΔG°rxn = ΔH°rxn − TΔS°rxn = −144kJ − (298K ) −38. so it is enthalpically driven.

6 J K ⎜ 1000 J ⎟ ⎝ ⎠ ) Spontaneous as long as T < 3446 K. ΔGrxn = ΔH rxn − T ΔS rxn 0 = ΔH rxn − T ΔS rxn o o ΔH rxn ≈ ΔH rxn and ΔS rxn ≈ ΔSrxn o ΔH rxn ΔH rxn T= ≈ = o ΔSrxn ΔSrxn ( −133kJ = 3446 K ⎛ 1kJ ⎞ −38.Example Problem (End) For what temperatures will this reaction be spontaneous? Answer: For T in which ΔGrxn < 0. it is so large that it is very approximate. 24 . However. Whenever the enthapy and the entropy have the same sign. there is always a temperature at which equilibrium will exist.

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