Thermodynamics

Elena N. Laricheva, Ph.D.

Let’s finish this one first
Calculate the molar solubility of AgCl in a 1.0 M NH3 solution.
Ksp of AgCl = 1.6 × 10−10
Thermodynamics
Module 9 Outline
• Thermodynamics
• Heat, work, internal energy, first law
• Spontaneity, entropy, second law
• Gibbs free energy
• Standard free energy changes
Thermodynamics
• Classical thermodynamics:

Was developed during the 19th century without ever

mentioning atoms and molecules; it’s the study of bulk
matter

• Statistical thermodynamics:

Properties of atoms and molecules determine properties of

bulk matter => provides connection between the atomic
and bulk thermodynamic properties
Thermodynamics

Goodstein, “States of matter”

Thermodynamics
• Classical thermodynamics:

Was developed during the 19th century without ever

mentioning atoms and molecules; it’s the study of bulk
matter

Sadi Carnot (1824) "Reflections on the motive power of fire"

Thermodynamics vs. kinetics
Thermodynamics:
Is the reaction feasible? (ΔG)

Transition state

Kinetics:
How fast is the reaction (Ea)?
What is its mechanism?
 Spontaneous  Fast
Are diamonds forever (?)

Immeasurably slow!

Diamond
Graphite
kJ
G = −3.0
mol
(1 atm , 25 0C )
 System and surroundings

• System – the part of the world of interest

• Surroundings – the region outside of the system
where observations and measurements are made
System and surroundings
Thermodynamic systems
Thermodynamic systems
Heat and work
Heat
Diathermic vs. adiabatic walls
•Diathermic walls – walls that permit
the transfer of energy as heat
between the system and the
surroundings

•Adiabatic walls – walls that do not

permit the transfer of heat even
though there is a temperature
difference between the system and
the surroundings
 Molecular interpretation

When energy is transferred When a system does work, it

to the surroundings as heat, stimulates orderly motion in
the transfer stimulates the surroundings.
random motion of the
atoms in the surroundings
 Internal energy, U

Example:
Suppose do 622 kJ of work on an exercise bicycle and lose
82 kJ of energy as heat. What is the change in your internal
energy? Disregard any matter loss by perspiration.
Q3
Which of the following signs on heat (q) and work (w) represent a
system that is doing work on the surroundings, as well as losing heat
to the surroundings?

A) q = -, w = -
B) q = +, w = +
C) q = -, w = +
D) q = +, w = -
E) None of these represent the system referenced above.
Q1
Which of the following is TRUE if ΔUsys = -95 J?

A) The system is gaining 95 J, while the

surroundings are losing 95 J.
B) The system is losing 95 J, while the surroundings
are gaining 95 J.
C) Both the system and the surroundings are
gaining 95 J.
D) Both the system and the surroundings are losing
95 J.
E) None of the above are true.
Spontaneity
Spontaneous processes
Spontaneous processes
• A spontaneous process is one that occurs naturally
under certain conditions.

• A non–spontaneous process will not take place unless

it is “driven” by the continual input of energy from an
external source.
Thermodynamics and spontaneity
• Thermodynamics predicts whether a process will occur
under the given conditions.

• Processes that occur without outside intervention are

called spontaneous.

• Nonspontaneous processes require energy input to go.

• Spontaneous != fast
Spontaneous processes
Are all spontaneous processes exothermic?
Spontaneous processes
• No, but most exothermic
processes are spontaneous.

Fe2O3(s) + 2 Al(s) -->

2 Fe(s) + Al2O3(s)

∆H = - 848 kJ

∆Hsys < 0 helps!

(“enthalpy-driven”)
Spontaneous processes
But there are spontaneous reactions or
processes that are endothermic (∆Hsys > 0).

NH4NO3(s) + heat ---> NH4NO3(aq)

Spontaneous processes
• Some spontaneous reactions or processes are
even isenthalpic: ∆H = 0.

ethanol
water solution of
ethanol and
water
Spontaneous processes
Formation of lime from chalk:

CaCO3 (s) → CaO (s) + CO2 (g) dH = +178.3 kJ

Reaction becomes spontaneous > 800 0C,

even though it is endothermic !
Spontaneous processes
• One property common to
spontaneous processes is
that the final state is more
disordered

∆Ssys > 0 helps!

(“entropy-driven”)
Tendency towards disorder
• One property common to
spontaneous processes is
that the final state is more
disordered

∆Ssys > 0 helps!

(“entropy-driven”)
Tendency towards disorder
• One property common to
spontaneous processes is
that the final state is more
disordered

∆Ssys > 0 helps!

(“entropy-driven”)
 Entropy
• For years, scientists wondered why some
reactions or processes proceed spontaneously
and others do not.

• At one time, they believed that a criterion for a

reaction or a process to proceed spontaneously
was that it should be exothermic

• But there are many processes that are

spontaneous and not exothermic
Examples
Gases do not
spontaneously
occupy only part
of a container,
leaving the other
part as a vacuum.

Mixtures of gases
do not
spontaneously
unmix.
Entropy
Entropy
Entropy
Entropy
Tendency towards disorder

• Some factor other than energy, is important to the

spontaneity of a process.

• It appears that greater, more uniform dispersal of

matter and energy can also be the driving force of a
spontaneous process.

• This other factor is entropy.

Entropy
Entropy
• Spontaneity is favored by an increase in entropy (S).

S = k ln W

k is the Boltzmann constant (1.38 x 10–23 J/K)

W is the number of microstates.

Microstate (W) – A specific configuration of the locations and

energies of the particles in a system.
• The number of microstates possible is given by:

W = nN

n is the number of boxes

N is the number of particles 41
Entropy
Consider 2 particles (N=2) distributed amongst 2 boxes (n=2):
Entropy
Now consider 4 particles (N=4) distributed among 2 boxes (n=2):

Microstates with equivalent particle arrangements are grouped

together and called distributions (or, macrostates)
Entropy

There are five possible distributions for this system.

Which distribution is most probable?
Statistical definition of entropy
Entropy
• The most probable distribution has the largest number
of microstates.

• The most probable distribution is therefore the one of

greatest entropy.

S = k ln W

• States of high entropy are favored because they are the

most probable.
Statistical definition of entropy
Entropy
This same principle applies to all systems including those
with larger numbers of particles: the most probable state
will be the one in which the particles are divided evenly
throughout the container.
Entropy changes
• Entropy is another state function.

• The change in entropy for a process is the difference in entropy

between the final state and the initial state.

ΔSsys = Sfinal – Sinitial

49
Factors that influence entropy
1) The phase of the substance.

2) The temperature of the substance.

– Temperature is proportional to the average kinetic

energy of the particles.

– With higher temperature, the particles have greater

freedom to move around.

50
Entropy changes
Entropy changes

52
Factors that influence entropy
3) The type and number of particles that make up the
substance.

4) Variations in the type of particles.

Pure substances vs. mixture?

53
 Second law of
thermodynamics
Second law of thermodynamics

In any spontaneous process there is always

an increase in the entropy of the universe.

Suniverse > 0

• The universe is composed of the system and

the surroundings.

• Therefore,
Suniverse = Ssystem + Ssurroundings > 0
Spontaneous processes
• Can processes with ∆Ssys < 0 be spontaneous?
Water spontaneously freezes at a temperature
below 0oC.
Second law of thermodynamics

Since the process is

spontaneous below
0oC, ΔSsurr, which is
positive, must be
greater in
magnitude than ΔS
of the water
molecules.
Second law of thermodynamics

• The freezing of water (an exothermic process)

releases heat to the surroundings, and thus
increases the entropy of the surroundings.

• The process is spontaneous at or below 0oC

because of the increase in entropy of the
surroundings is greater than the decrease in
entropy of the water as it freezes.
Entropy changes in the surroundings
• Heat that flows in or out of the system
changes the entropy of the surroundings.

• For an isothermal process:

−qsys
Ssurr =
T

• At constant pressure, qsys is simply

Hsys
Entropy changes in the universe
−qsystem
• Since Ssurroundings = T
and qsystem = Hsystem
This becomes:
−Hsystem
Suniverse = Ssystem +
T

Multiplying both sides by −T, we get

−TSuniverse = Hsystem − TSsystem
Entropy changes in the universe

• ΔSuniverse > 0 for a spontaneous process

• ΔSuniverse < 0 for a nonspontaneous process

(spontaneous in the reverse direction).

• ΔSuniverse = 0 for a process at equilibrium

61
Spontaneity and dSuniverse
Gibbs free energy
Gibbs free energy
Recall, that:

−TSuniverse = Hsystem − TSsystem

• We call −TSuniverse the change in the Gibbs Free

Energy (ΔG)

ΔG = Hsystem − TSsystem

• For a process to be spontaneous ΔG must be <0

Gibbs free energy and spontaneity

ΔG = Hsystem − TSsystem

• The sign of G indicates if a reaction will be spontaneous or

not.
– If ΔG < 0, the reaction is spontaneous in the forward
direction.

– If ΔG > 0, the reaction is non-spontaneous in the forward

direction

– If ΔG = 0, the system is at equilibrium

Q1
C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(g) ΔHrxn = -2044 kJ

1) Is the reaction endo- or exothermic?

2) Determine the sign of ΔSrxn
3) Determine the sign of ΔGrxn
4) Is this reaction spontaneous?
5) Predict the sign of ΔSuniverse
6) Calculate ΔSuniverse at 25 ’C

66
Q2
2N2(g) + O2(g) → 2N2O(g) ΔHrxn = +162.3 kJ

1) Is the reaction endo- or exothermic?

2) Determine the sign of ΔSrxn
3) Determine the sign of ΔGrxn
4) Is this reaction spontaneous?
5) Predict the sign of ΔSuniverse
6) Calculate ΔSsurr at 25 ’C

67
Q3
Spontaneous or not? All T? Or some T?

2N2O(g) → 2N2(g) + O2(g) ΔH0rxn = -163.2 kJ

3O2(g) → 2O3(g) ΔH0rxn = +285.4 kJ

H2O(l) → H2O(s) ΔH0 = -6.01 kJ

H2O(l) → H2O(g) ΔH0 = +40.7 kJ

68
Determining T
Consider this decomposition reaction:

CCl4(g) → C(s; graphite) + 2Cl2(g)

ΔH = +95.7 kJ
ΔS = 142.2 J/K

a) Calculate ΔG at 25 ‘C. Is the reaction spontaneous?

b) If the reaction is not spontaneous at 25 ‘C, determine
at what T (if any) it becomes spontaneous.

69
Determining T
Consider this decomposition reaction:

C2H4(g) + H2(g)→ C2H6(g)

ΔH = -137.5kJ
ΔS = -120.5 J/K

a) Calculate ΔG at 25 ‘C. Is the reaction spontaneous?

b) Does ΔG become more negative or more positive as
the temperature increases.

70
Gibbs free energy and spontaneity
• To calculate the temperature at which the
spontaneity of a reaction changes from …
– Spontaneous to non-spontaneous
– Or, non-spontaneous to spontaneous
… find the temperature at which ΔG = 0

ΔG = 0 = ΔH – TΔS
T = ΔH / ΔS
This is the temp. at which ΔG = 0 and by definition the
system is at equilibrium.
71
Concept check
Which statement is true regarding the sublimation of dry
ice (CO2)?

A. dH is positive, dS is positive, and dG is positive at low T

and negative at high T
B. dH is negative, dS is negative, and dG is negative at low
T and positive at high T
C. dH is negative, dS is positive, and dG is negative at all T
D. dH is positive, dS is negative, and dG is positive at all T

72
 Expansion work
• the work done when a system expands against an opposing
pressure (e.g. gas-producing and gas-consuming reactions)

𝑤 = −𝑃∆𝑉
Q2
Calculate the change in internal energy (ΔU) for a
system that is giving off 25.0 kJ of heat and is
changing from 18.00 L to 15.00 L in volume at 1.50
atm pressure. (101.3 J = 1 L∙atm)

A) +25.5 kJ
B) -16.0 kJ
C) -25.5 kJ
D) -24.5 kJ
E) 456 kJ
Standard Gibbs free
energy change
Standard entropy change (ΔS°rxn)
• For a chemical reaction:
mA + nB → xC + yD

ΔS°rxn = S°products - S°reactants

ΔS°rxn = [xS°(C) + yS°(D) ] – [mS°(A) + nS°(B)]

Where S° are standard molar entropies of

reactants and products

76
Standard molar entropies
Third Law of Thermodynamics: [The entropy of a perfect
crystal at absolute zero (0K) is zero].

Thus, we can measure all entropy values against the

absolute zero.

77
Example 1

S0, J mol-1 K-1

H2O (l) 70.0
H2O (g) 188.8

78
Example 2

S0, J mol-1 K-1

He(g) 126.2
Ne(g) 146.1
Ar(g) 154.8
Kr(g) 163.8
Xe(g) 169.4

79
Example 3

S0, J mol-1 K-1

C(s, diamond) 2.4
C(s, graphite) 5.7
entropy complexity

80
Example 4

S0, J mol-1 K-1

Ar(g) 154.8
NO(g) 210.8

81
Example
Calculate ΔS0rxn for the following reaction:

4NH3(g) + 5O2(g)→ 4NO(g) + 6H2O(g)

S0 J mol-1 K-1
NH3(g) 192.8
O2(g) 205.2
NO(g) 210.8
H2O(g) 188.8

82
Standard Gibbs free energy change
• Although the Change in Gibbs Free Energy equation is
valid under all conditions, we will most often apply it at
standard conditions.

• Standard conditions:
For a gas: Pure gas at 1 atm
For a liquid or solid: pure substance in its most stable form
at 1 atm and the temperature of interest
For a substance in solution: 1M concentration

• Under standard conditions, ΔG° = ΔH° – TΔS°

– Pay attention to J vs. kJ in calculations! 83

Example #1
A reaction has ΔH° = 100 kJ/mol and ΔS°=250 J/mol·K.
Is the reaction spontaneous at room temperature? If not,
under what temperature conditions will it become
spontaneous?

84
Example #2
Determine the free energy change for the following reaction, which
is run under standard state conditions and 25 °C. Identify it as either
spontaneous or nonspontaneous at these conditions.

Fe2O3(𝑠)+3CO(𝑔)⟶2Fe(𝑠)+3CO2(𝑔)

Substance ΔHf° (kJ mol–1) S° (J K–1 mol–1)

Fe2O3(s) –824.2 87.40
Fe(s) 0 27.3
CO(g) –110.52 197.7
CO2(g) –393.51 213.8

85
Standard free energy of formation
• The Standard Free Energy of Formation (∆Gf°) for a
compound is defined as the free energy change for the
formation of one mole of a substance from its elements
in their standard state at 1 bar and 25 °C.

• Analogous to the ∆Hf° discussed in Chapter 5

• Example:
H2 (g) + ½O2 (g) → H2O (l) ∆Gf° = -237.2 kJ/mol
Standard free energy change of reaction
ΔG° = ΣΔG°f (products) – ΣΔG°f (reactants)

• This equation only works for calculating ∆G° of a

reaction at the temperature for which the values of ∆Gf°
are tabulated, which is 298 K.

• ΔG°f for any element in its most stable form at

standard conditions is defined as zero.
Example #2
Determine the free energy change for the following reaction, which
is run under standard state conditions and 25 °C. Identify it as either
spontaneous or nonspontaneous at these conditions.

Fe2O3(𝑠)+3CO(𝑔)⟶2Fe(𝑠)+3CO2(𝑔)

Substance ΔHf° (kJ mol–1) ΔGf° (kJ mol–1) S° (J K–1 mol–1)

Fe2O3(s) –824.2 –742.2 87.40
Fe(s) 0 0 27.3
CO(g) –110.52 –137.15 197.7
CO2(g) –393.51 –394.36 213.8

88
Additivity of dG
• As with enthalpy, free energy changes for reactions
are additive, if
Reaction 3 = Reaction 1 + Reaction 2

Then, ΔG3 = ΔG1 + ΔG2

- Also keep in mind that if a reaction is reversed

then the sign on G is also reversed.

- If a reaction is multiplied by a factor of “n” then G

is also multiplied by a factor of “n”.
89
Example #3
Given:

P4(s)+5O2(g)⟶P4O10(s) ΔG°=−2697.0 kJ/mol

2H2(g)+O2(g)⟶2H2O(g) ΔG°=−457.18 kJ/mol

6H2O(g)+P4O10(s)⟶4H3PO4(l) ΔG°=−428.66 kJ/mol

(a) Determine the standard free energy of formation, ΔGf°, for

phosphoric acid.

(b) How does your calculated result compare to the tabulated value
in Appendix G? Explain. ΔGf° (H3PO4(l) = –1124.3 kJ/mol)
Non-standard conditions
Non-standard conditions
Consider evaporation of water:

H2O (l) → H2O(g)

G°= +8.59 kJ/mol

Yet, the process is spontaneous?

Non-standard conditions
H2O (l) → H2O(g)

G°= +8.59 kJ/mol

• This value refers to standard, not ordinary conditions!

• In a flask containing liquid water and water vapor

under standard conditions (PH2O = 1 atm) at 25 C, the
water does not vaporize. Instead, reaction
spontaneously occurs in reverse–water vapor
condenses!
Non-standard conditions
H2O (l) → H2O(g)

G°= +8.59 kJ/mol

• In open air, under ordinary conditions PH2O < 1atm

• Thus, G° won’t apply
• We need to calculate G under non-standard conditions
Non-standard conditions
There is a general equation that enables you to calculate
G under non-standard conditions.

G = G° + RT ln Q

• G = non-standard free energy

• G° = standard free energy
• R = 8.314 J·K-1·mol-1
• T = temp in K
• Q = reaction quotient
Let’s have a closer look
Under standard conditions

Q = PH2O = 1 atm
G° = +8.59 kJ/mol
G = G° + RT ln Q = +8.59 kJ/mol + RTln(1) = +8.59 kJ/mol
G = G°; G > 0
• non-spontaneous in the forward direction
• spontaneous in reverse direction
Under equilibrium conditions

Q = K = PH2O = 0.0313 atm

G° = +8.59 kJ/mol
G = G° + RT ln Q = +8.59 kJ/mol + RTln(0.0313) = 0
G = 0
• Not spontaneous in either direction
• Reaction is at equilibrium
Other non-standard conditions

Calculate the actual Q. For example, on some dry non-humid day:

Q = K = PH2O = 5.00 * 10-3 atm
G° = +8.59 kJ/mol
G = G° + RT ln Q = +8.59 kJ/mol + RTln(5.00 * 10-3 ) = -4.5 kJ/mol
G < 0
• Spontaneous in forward direction
Example
Consider the reaction:

H2(g) + Cl2(g) → 2 HCl(g)

How does the value of G change when the pressures of the

gases are altered as follows at 25 C?

G°f(HCl(g)) = -95.27 kJ/mol

H2 = 0.25 atm; Cl2 = 0.45 atm; HCl = 0.30 atm
Gibbs Free Energy &
Equilibrium
Relationship between G° and K
• At equilibrium, G = 0 and Q = K
• The equation becomes:

0 = G° + RT ln K

or

G° = – RT ln K
Relationship between G° and K
Example
Use tabulated free energies of formation to calculate the equilibrium
constant for the reaction at 298 K:

N2O4 (g) → 2 NO2 (g)

G°f(N2O4(g)) = 99.8 kJ/mol

G°f(NO2(g)) = 51.3 kJ/mol