Ch.

18: Entropy, Free Energy, and Equilibria

Chemistry: Atoms First

1
Julia Burdge & Jason Overby

Thermodynamics
Recall thermochemistry (study of heat changes) from
CHM 151: Chapter 10 specifically sections 1, 2
(except work), 3, and 6.

Also review Ch. 12, section 6 Phase Changes

Thermodynamics allows us to determine IF a
reaction will occur as well as telling us the direction
in which (and extent to which) a reaction will occur
(like Q vs K)

18.1 Spontaneous Processes

A process that does occur under a specific set of conditions is called a
spontaneous process. Processes that result in a decrease in energy of a system
are often spontaneous.
A process that does not occur under a specific set of conditions is called
nonspontaneous.

Spontaneous Processes
Spontaneity is determined by enthalpy (H: measure of
energy change) and entropy (S: measure of disorder)
of a reaction.

A system tends to move toward a lower state of energy.

The enthalpy of many spontaneous processes are exothermic

(e.g., combustion reactions), but some spontaneous processes

can be endothermic under the right conditions (e.g., melting of
ice).

A system tends to become more disordered.

The entropy of a spontaneous system tends to increase. There
is an increase in the disorder or randomness of a system (i.e.,
your room or office naturally becoming messier over time).
4

151 Thermochemistry Review

1st Law of Thermodynamics: Energy is conserved, it cannot
be created or destroyed
If a system / reaction gives off heat, the surroundings /
universe must absorb it (and vice versa).
Heat flow (enthalpy, H) is always defined with reference
to the system
System absorbs heat, H > 0
Associated with breaking bonds or Intermolecular forces.
Heat energy goes into a system to break the bonds or pull
atoms/molecules apart.

System gives off heat, H < 0

Associated with making bonds or Intermolecular forces
5

Defining Hof, Calculating Horxn

Heat of formation, Hof , is the enthalpy change when 1
mole of a substance is made from its elements in their
standard state

The o symbol refers to the standard state, 1.00 atm

pressure, 25.0oC, 1.00 M for solutions

Horxn = nHof (products) - nHof (reactants)

n is moles (coefficient in balanced equation)
Hof values, Appendix 2, reported in kJ/mol
Hof for elements is 0 (no energy needed!)
6

Defining Hof, Calculating Horxn

Write the equation for the heat of formation of water.
H2 (g) + O2 (g) H2O (g)
0

-241.8 kJ/mol

This is how the values in Appendix 2 are obtained.

We then use these values to calculate the enthalpy of a
reaction.

Horxn = nHof (products) - nHof (reactants)

Calculating Horxn
Calculate Horxn for the following reaction:
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g).

What information do you need?

Find Hof values in Appendix 2.

NH3(g) = - 46.3 kJ/mol

O2(g) = 0 kJ/mol
NO(g) = 90.4 kJ/mol
H2O(g) = - 241.8 kJ/mol
Answer: -904.0 kJ (sig figs by decimal places!)
Watch physical states when looking up values
8
(l) versus (g) has a different value!

Group Work, Calculating Horxn

Calculate Horxn for the following reaction:
C2H4(g) + O2 (g) CO2 (g) + H2O(l)
Predict sign of Horxn first.

Find Hof values in Appendix 2.

C2H4(g) = 52.3 kJ/mol

O2(g) = 0 kJ/mol
CO2 (g) = -393.5 kJ/mol
H2O(l) = - 285.8 kJ/mol

Answer: -1410.9 kJ

18.2 Entropy
To predict spontaneity, both the enthalpy and entropy must be
known.
Entropy (S) of a system is a measure of how spread out or
how dispersed the systems energy is.
Change in entropy of a system is the difference
between the final & initial state.

10

Entropy
Standard entropy (So) is absolute entropy of a substance
at 1 atm; units of entropy are J/K mol
For a given substance, So is greater in liquid phase than in solid
phase.
For a given substance, So is greater in gas phase than in liquid
phase.
For 2 monatomic species, one with the larger molar mass has
greater So
For 2 substances in same phase (similar masses) substance
with more complex molecular structure has the greater So
In cases where an element exists in 2 or more allotropic forms,
the form in which the atoms are more mobiles has greater So

Standard Entropy Values (So)

Note: The standard entropy for a pure element in its most stable
form is NOT zero (like for Hof).
12

Which phase has greatest entropy?

Solid, liquid or gas? (ice, water, or steam)

13

Standard Entropy Values

As temperature increases, entropy increases because of
increased kinetic energy and molecular motion.
Entropy increases as a
substance is heated from
solid to liquid; even
more increase is seen as
its heated from liquid
to gas.

14

Which temp. has greater entropy?

Low or high?

High T: more motion, more possible arrangements

15

Standard Entropy Values, So

Entropy change of a reaction is the difference
between entropies of the products & reactants
aA =bB cC + dD

Sorxn = nSo (products) nSo (reactants)

Use Standard Molar Entropies, So, (Table 18.2 and

Appendix 2) - entropy of 1 mole of a pure substance

at 1 atm and 25oC
16

Calculate Entropy of Reaction

Calculate Sorxn for:
Na(s) +

Cl2(g)

2Na(s) +

Cl2(g) 2NaCl(s)

NaCl(s)

Na(s) = 51.05 J/molK,

Cl2(g) = 223.0 J/molK,
NaCl(s) = 72.38 J/molK
Sorxn = nSo (products) nSo (reactants)
Sorxn = (2)72.38 ((2)51.05 + 223.0)

Sorxn = -180.3 J/K (the reaction becomes more

ordered due to formation of solid and combination17

rxn)

Entropy of Dissolution
Dissolving a substance can lead to an increase or a decrease in
entropy, depending on the nature of the solute.
Molecular solutes (i.e. sugar): entropy increases
Ionic compounds: entropy can decrease or increase

18

Entropy Trends
Entropy increases as the number of particles (molecules)
increases:
N2O4(g) 2 NO2(g)
Comparing entropy of molecules Entropy increases as:
1) temperature increases.
H2O at 10oC vs H2O at 100oC
2) mass of an atom or molecule increases (more
electrons moving around)
F2 (158 J/Kmol) < Cl2 (165 J/Kmol)
3) molecular complexity increases (i.e., number of
atoms, number of heavier atoms, etc.)
CH4 (186 J/Kmol) < C2H6 (230 J/Kmol)
19

Group work: Which has greater entropy?

Determine which example in each scenario will have more
entropy.

Temperature: C(s) at 25oC

Volume:
Phase:

C(s) at 35oC

1 mol O2(g) in 1 L
O2(g)

1 mol O2(g) in 2 L

O2(l)

Molar mass: He(g)

Ne(g)

Molecular Complexity:

C2H6(g)

CH4(g)
20

Greater entropy?
Determine which example in each scenario will have more
entropy.

Temperature: C(s) at 25oC

Volume:
Phase:

C(s) at 35oC

1 mol O2(g) in 1 L
O2(g)

1 mol O2(g) in 2 L

O2(l)

Molar mass: He(g)

Ne(g)

Molecular Complexity:

C2H6(g)

CH4(g)
21

Processes that Increase Entropy

Entropy usually increases for the following:
Melting, vaporization, or sublimation
Temperature increase
Reaction resulting in a greater number of gas
molecules (or greater molar mass of solid)
Decomposition reactions
22

Predict the sign of S

Does entropy increase (S > 0) or decrease (S < 0) for
the following? Why?
2SO2 (g) + O2 (g) 2SO3 (g)
2O3 (g) 3O2 (g)
CaCO3(s)+2HCl(aq) CaCl2(aq)+H2O(l)+CO2(g)
I2 (s) I2 (g)
NaCl (s) Na+ (aq) + Cl- (aq)
4 Al(s) + 3 O2(g) 2Al2O3(s)

23

Entropy Changes in the Universe

The second law of thermodynamics states that for a process to
be spontaneous, Suniverse must be positive. Suniverse (or Stotal)

takes the entropy of both the system and the surroundings

into consideration.
Stotal = Ssys + Ssurr where
Ssystem is Srxn (that we just calculated)
Ssurroundings is entropy change for surroundings
Stotal > 0 for a spontaneous process
Stotal < 0 for a nonspontaneous process
Stotal = 0 for an equilibrium process
24

Entropy Changes in Surroundings

Ssurr is related to the enthalpy of the reaction; if
heat enters surroundings, molecules have more
energy and entropy increases.

Ssurr

H sys
T

25

Standard Entropy Values, So

3rd Law of Thermodynamics: The entropy of a
perfectly ordered crystalline substance at 0 K is
zero.

This enables us to determine experimentally

absolute entropies of substances

S = S (final) S (initial)

Where Sinitial is zero then measured change is equal

to absolute entropy

S = S (final)
26

18.5 Predicting Spontaneity

Second law of thermodynamics, DSuniv > 0 for a spontaneous
process.

Substitute DHsys / T for DSsurr
DHsys / T) > 0
TDHsys > 0
-TDHsys - < 0
Gibbs free energy (G)

G = H TS

Change in free energy

DG = DH TDS

In a spontaneous process (when G < 0), the free energy of the

system always decreases.

Predicting Spontaneity
G = H TS
G < 0
G > 0
G = 0

The reaction is spontaneous in the forward direction.

The reaction is nonspontaneous in the forward direction.
The system is at equilibrium

28

Gibbs Free Energy and Temperature

G = H TS: Notice that G is temperature dependent!
Temperature plays a role in determining spontaneity.
Endothermic reactions will be spontaneous at higher
temperatures (where TS > H)
Exothermic reactions will be spontaneous at lower
temperatures (where H > TS)
Higher and lower temps are reaction-specific. Every
reaction has a cut-off temperature depending on values of
H and S.

Gibbs Free Energy

G = Gibbs Free Energy (or free energy), kJ/mol: Uses
both enthalpy and entropy to determine if a reaction will be
spontaneous.
In a spontaneous process, the free energy of the system always
decreases.
Calculate G when H = -227 kJ, S = - 309 J/K, T = 1450 K.
Is this process spontaneous?

Entropy of Phase Changes

G = 0: turning point between spontaneous and nonspontaneous; phase changes (occur at equilibrium)

G = H - TS = 0; solving for T tells us the temperature

cut-off for high and low temps. We can also use this to
determine the temperature for a phase change.

For a given system, H = -227 kJ, S = - 309 J/K, T =

1450 K. We calculated G = +221 kJ. At what temperature

will the system become spontaneous? Will it be
spontaneous above or below this temp?

31

Temperature of Phase Change

1) What is the melting point of ice? H2O(s)
H2O(l)

Hfusion = 6.01 kJ/mol; Sfusion = 22.0 J/Kmol

For ice:
263K (-10oC): G = +0.22 kJ/mol (non-spontaneous)
283K (10oC): G = -0.22 kJ/mol (spontaneous)
2) Calculate the boiling point (in oC) of ethanol if
the entropy of vaporization is 111.9 J/K and the
enthalpy of vaporization is 39.3 kJ
T = H / S = 39.3 kJ / 0.1119 kJ/K = 351.206 K = 78.2oC
32

Predicting Spontaneity
Write the equation for the formation of rust.
4Fe+3(s) + 3O2(g) 2Fe2O3(s)

Calculate Horxn and Sorxn using the table below.

Is the reaction spontaneous or nonspontaneous at 500oC?
Hof (kJ/mol)

So (J/Kmol)

Fe(s)
O2(g)

0
0

27.2
205.0

Fe2O3(s)

-822.2

90.0
33

Predicting Spontaneity
Horxn = [2 mol * -822.2 kJ/mol] [0] = -1644.4 kJ
Sorxn = [2 mol * 90.0 J/Kmol] [4 mol * 27.2 J/Kmol + 3
mol * 205 J/Kmol] = -543.8 J/K = -0.5438 kJ/K

G = Ho TSo = -1644.4 kJ (773.15 K * -0.5438 kJ/K)

= -1224.0 kJ, spontaneous

Hof (kJ/mol)

So (J/Kmol)

Fe(s)
O2(g)

0
0

27.2
205.0

Fe2O3(s)

-822.2

90.0

Predicting Temp. of Spontaneity

At what temperature will the rusting of iron become
non-spontaneous?

Will it be spontaneous above or below this

temperature? How can you determine this?

T = 3024 K; Temperatures below this occur

spontaneously because its exothermic.

35

Group Quiz #12

Calculate G for the reaction at 115oC. Will this
reaction be spontaneous or non-spontaneous?
N2(g) + H2(g) NH3(g)

Before you begin calculating, predict all quantities.

Hof (kJ/mol)

So (J/Kmol)

N2(g)

191.5

H2(g)

131.0

-46.3

193.0

NH3(g)

36

Group Quiz #12 Answers

N2(g) + 3H2(g) 2NH3(g)
Predict: Hrxn < 0 (combination), Srxn < 0 (more
moles of reactant), Grxn temperature-dependent

Horxn: -92.6 kJ
Sorxn: -198.5 J/K = -0.1985 kJ/K
T = 115.0 + 273.15 = 388.15 K
Grxn = -92.6 kJ (388.15 K)(-0.1985 kJ/K) =
- 15.6 kJ (spontaneous)

37

Standard Free Energy Changes

The standard free energy of reaction (Gorxn) is freeenergy change for a reaction when it occurs under
standard-state conditions.
Standard-state conditions are:
Solids, liquids, and gases in their pure form
1 M solutions, 1 atm gases, 25oC (298 K)
G (non-standard) predicts spontaneity
Go (standard at 25oC) determines whether reactants
or products are favored at equilibrium; relates to K
38

Standard Free Energy Changes

For a chemical reaction aA + bB cC + dD
We can calculate Gorxn = Horxn TSorxn.
Alternatively,

Gorxn = n Gof (products) n Gof (reactants)

Gof for any element in its most stable form at 1 atm is

defined as zero (just like Hof values).

39

18.6 Free Energy and Equilibrium

It is the sign of G (not Go) that determines spontaneity.
Go determines whether a reaction is reactant- or productfavored.
G = Go + RT lnQ

The relationship between G and Go is:

R is the gas constant (8.314 J/Kmol).
T is the Kelvin temperature.
Q is the reaction quotient (from Ch. 15).
40

18.6 Free Energy and Equilibrium

G is the actual free energy change under non-standard
conditions. It changes as a reaction proceeds (as
concentrations, pressures, etc. change).
G = Go + RT lnQ

G changes as a reaction proceeds (initially decreases).

This value determines the spontaneity of a reaction at a
given point in time.
Go is standard and does NOT change. It is a constant
for a reaction (like Ho and So). This value determines
whether a reaction is reactant- or product-favored.
41

Group Quiz #13

Calculate Gorxn for the reaction at 25oC. Will this
reaction be reactant- or product-favored?
N2(g) + H2(g) NH3(g)

Before you begin calculating, predict all quantities.

Hof (kJ/mol)

So (J/Kmol)

N2(g)

191.5

H2(g)

131.0

-46.3

193.0

NH3(g)

42

Group Quiz #13 Answers

N2(g) + 3H2(g) 2NH3(g)
Predict: Hrxn < 0 (combination), Srxn < 0 (more
moles of reactant), Grxn temperature-dependent

Horxn: -92.6 kJ
Sorxn: -198.5 J/K = -0.1985 kJ/K
T = 25.0 + 273.15 = 298.15 K
Grxn = -92.6 kJ (298.15 K)(-0.1985 kJ/K) =
- 33.4 kJ (product-favored)

43

Free Energy and Equilibrium

At equilibrium, G = 0 and Q = K:
Figure 18.6

44

Free Energy and Equilibrium

At equilibrium, G = 0 and Q = K:
Figure 18.6

45

G, G , and Equilibrium
o

The position of equilibrium depends on the value of

Go.

<0

46

Free Energy and Equilibrium

At equilibrium, G = 0 and Q = K:
0 = Go + RT ln K
Go = RT ln K

47

Free Energy and Equilibrium

Consider the following equilibrium:
H2(g) + I2(g) 2HI(g).
Go at 25oC = 2.60 kJ/mol.
Calculate G when PH2 = 2.0 atm; PI2 = 2.0 atm; and PHI =
3.0 atm.
QP

PHI

3.0

P P 2.0 2.0
H2

I2

9.0
2.25
4.0

2.60 kJ 8.314 103 kJ

G

298 K ln2.25 4.6 kJ/mol

mol
K mol

Worked Example 18.8

48

Practice Calculations
Gorxn for the formation of ethanol is -24.7 kJ/mol.
C(s) + O2(g) + H2(g) CH3OH(g)
Calculate the equilibrium constant, K, at 25oC.
2) Calculate Gorxn for the following reaction at 25oC:
P4 (g) + 6 Cl2 (g) 4 PCl3 (g)
3) Horxn for the melting of gold is 12.55 kJ/mol. Sorxn for
the melting of gold is 9.38 J/molK. What is the melting
point (in oC) of gold?
4) Calculate G for S(s) + O2(g) SO2(g) when MO2 = 0.140
M and MSO2 = 1.24 M at 25oC. In which direction will the
reaction proceed?
5) If K for the reaction CuO(s) Cu(s) + O2(g) at 25oC is
49
2.66 x 10-46, what is Go?

Free Energy and Equilibrium

Gorxn for the formation of ethanol is -24.7
kJ/mol.
C(s) + O2(g) + H2(g) CH3OH(g)

Calculate the equilibrium constant, K, at 25oC for

this reaction.
ln K = Go/-RT = -24.7 kJ / -(0.008314 kJ/molK *
298K)
ln K = 9.969; K = 2.14 x 104
Worked Examples 18.9 and 18.10

50

Practice Calculations
2) Calculate Gorxn for the following reaction at 25oC:
P4 (g) + 6 Cl2 (g) 4 PCl3 (g)
Gof (P4 (g)) = 24.4 kJ/mol
Gof (Cl2 (g)) = 0 kJ/mol
Gof (PCl3 (g)) = -269.6 kJ/mol
Gorxn = [4 mol(-269.6 kJ/mol] [1 mol(24.4 kJ/mol)
+ 0] = - 1102.8 kJ
51

Practice Calculations
Horxn for the melting of gold is 12.55 kJ/mol. Sorxn
for the melting of gold is 9.38 J/molK. What is the
melting point (in oC) of gold?

T = H / S = 12.55 kJ/mol / 0.00938 kJ/molK

T = 1337.95 K 273 = 1060 oC
What is Go for at 25oC? Is this reactant- or productfavored?

Go = Ho TSo = 12.55 kJ/mol (298K)(0.00938

kJ/molK) = 9.75 kJ/mol; reactant-favored
52

Practice Calculations
4) Calculate G for S(s) + O2(g) SO2(g) when MO2
= 0.140 M and MSO2 = 1.24 M at 25oC. In which
direction will the reaction proceed?

Need to calculate Go and Q.

Gof (SO2(g)) = -300.2 kJ/mol

Q = 1.24 M / 0.140 M = 8.8571

Go = -300.2 kJ
G = -294.8 kJ; spontaneous in the forward
direction.

53

Practice Calculations
5) If K for the reaction CuO(s) Cu(s) + O2(g) at
25oC is 2.66 x 10-46, what is Go?

Go = -RT ln K = -(8.314 J/Kmol)(298)(ln 2.66x10-46)

Go = 2.60 x 105 J/mol = 260. kJ/mol

54

Group Quiz #14

1) Use the solubility product constant, Ksp, of silver
chloride at 25oC to calculate Go for the reaction
AgCl(s) Ag+(aq) + Cl-(aq). Ksp = 1.6 x 10-10. Is
this process reactant- or product-favored?

2) If in the system above, [Ag+] = 0.0020 M and

[Cl-] = 0.0040 M, what is G at 25oC? Is the

reaction spontaneous or non-spontaneous? Explain
your answer!
55

Group Quiz #14 Answers

AgCl(s) Ag+(aq) + Cl-(aq); Ksp = 1.6 x 10-10.
Go = -RT ln K = -(0.008314 kJ/molK)(298.15K)(ln
1.6x10-10)

Go = 56 kJ; reactant-favored
G = Go + RT ln Q
Q = [Ag+][Cl-] = (0.0020 M)(0.0040 M) = 8.0x10-6
G = kJ + (0.008314 kJ/molK)(298.15K) ln Q
G = 27 kJ; non-spontaneous

56

The End

57