Lecture Notes

Week 3
CHEM*2880 Physical Chemistry
Prof. Jennifer Murphy
Class Schedule – Part I
Week Dates Topics Text Ref Seminar

Week 0 Sept. 5 Introduction Review Chapter 1 First Class

Properties of Gases Ch 2, 2.1 – 2.3 Meeting

Properties of Gases Ch 2, 2.4 – 2.6 (p. 21) Properties of

Week 1 Sept. 8 – 12 & Spectroscopy Ch 14, 14.1 Gases Quiz #1
Ch 14, 14.2 – 14.4

Spectroscopy & 1st Ch 14, 14.5 – 14.8 Spectroscopy

Week 2 Sept. 15 – 19 Law of 14.9; Ch 3, 3.1 – 3.2 Quiz #2
Thermodynamics Ch 3, 3.3 – 3.4
1st & 2nd Law of Ch 3, 3.5 – 3.7 Thermodynamics
Week 3 Sept. 22 – 26 Thermodynamics Ch 4, 4.1 – 4.3 Quiz #3
Ch 4, 4.4 – 4.5
2nd Law of Review Test #1 (material
Week 4 Sept. 29 – Oct. 3 Thermodynamics & Ch 4, 4.6 – 4.9 up to Sept. 29
Solutions Ch 5, 5.1 – 5.2 lecture.)
Practice Problem (3.81 Textbook)
Indicate whether the following thermodynamic quantities are positive,
zero, or negative for the system described. Clearly state your reasoning
for each answer.
i. heating of a gas at constant volume
w
q
ΔH
ΔU

ii. irreversible isothermal expansion (ideal gas)

w
q
ΔH
ΔU
Physical Changes – Liquids and Solids
Isobaric (i.e., ∆P = 0)
 Heating a solid or liquid at constant P can be handled by:
qP = C p ∆T = nC p ∆T
 For work at constant P, ΔV ≈ 0: wP =− Pex ∆V ≅ 0
∴∆U = q + w = nCP ∆T
∴∆H = ∆U + ∆( PV ) =∆U + P∆V ≅ ∆U
Isochoric (i.e., ∆V = 0) q = C ∆T = nC ∆T
V v v

w=− Pex ∆V =0
∆U = q + w = Cv ∆T
∆H = ∆U + ∆( PV ) ≅ ∆U
Physical Changes – Liquids and Solids
Isothermal (i.e., ΔT = 0)
 Changing pressure leads to negligible volume changes (in
most cases) at constant T
qT ≅ 0
∆U =+ 0 ∆H
q w ==
wT ≅ 0
For changes of state for a pure solid or liquid, use a convenient
path to find q & w values, and sum to get ΔU.
e.g., isobaric path + isothermal path
isochoric path + isothermal path
For solids & liquids, since V doesn’t change appreciably with P:
CP ≅ CV , ΔUP ≅ ΔUV and ΔH = ΔU
Phase Transitions
A change of state or phase transition is a change of a substance from
one state (solid, liquid, gas) to another. The specific name or names for
each of these transitions are given below. Remember, temperature is
constant during a phase change!
Heating Curve for Water
q = mCs(steam)∆T

boiling point qp = n∆H°vap gas

100°C

Temp q = mCs(liquid)∆T
(°C)
liquid
qp = n∆H°fus (kJ/mol)
= m∆H°fus (kJ/g)
0°C melting point
solid q = mCs(ice)∆T = n𝐂𝐂�(ice)∆T
Time heat supplied
Practice Problem
Compare the difference between ∆H & ∆U for the following:
(a) 1 mol ice → 1 mol water at 273K & 1 atm
(b) 1 mol water → 1 mol steam at 373 K & 1 atm
Given: Vm (L/mol) @ 273 K Vm (L/mol) @ 373 K
Ice: 0.0196
Water: 0.0180 0.0188
Steam 30.61
Practice Problem Solution
(a)
Practice Problem (3.79 Textbook)
State the conditions for each of the following:
(a) ∆H = ∆U + P∆V (b) Cp = CV + nR (c) γ = 5/3
Constant Pressure Ideal Gas Monoatomic
Ideal Gas

Try the rest of these on your own, we will go through them during review.
Enthalpy (ΔH) Changes
For a chemical reaction: nAA + nBB → nCC + nDD

∆H
= ∑H products − ∑ H reagents
∆H
= nC H C + nD H D − nA H A − nB H B
Using standard enthalpy of formation values:
ΔH°Rxn = ΣnΔHf° (products) – ΣnΔHf° (reagents)

Can also use Hess’ Law to determine ΔH°Rxn values.

Refer to Metabolism of Glycine Example in Prof. Jones Notes
Dependence of ΔH on T
If ΔH or ΔU are known at one temperature, and need to be calculated at another, an
appropriate paths can be chosen.
Follow the path:
1 H2O (l) (35°C, 1 atm) → H2O (l) (100°C, 1 atm) (isobaric )
2 H2O (l) (100°C, 1 atm) → H2O (g) (100°C, 1 atm)
3 H2O (g) (100°C, 1 atm) → H2O (g) (35°C, 1 atm) (isobaric)
H2O (l) (35°C, 1 atm) → H2O (g) (35°C, 1 atm)

Step 1 is an isobaric heating of liquid water: ΔH1 = qP = CP(l)ΔT1

Step 2 is the vaporization of water at 100°C which we can look up in our standard
tables
Step 3 is the isobaric cooling of water vapour: ΔH2 = qP = CP(g)ΔT2
Note that ΔT2 = -ΔT1
Thus, for the overall reaction
ΔH(35°C) = ΔHvap(100°C) + CP(l)ΔT1 + CP(g)ΔT2 (Use: ΔT2 = -ΔT1)
= ΔHvap(100°C) + CP(l)ΔT1 – CP(g))ΔT1
Dependence of ΔH on T
Kirchoffs Law
∆H(T2) – ∆H(T1) = [CP(products) – CP(reactants)][T2 – T1]
OR
∆H(T2) = ∆H(T1) + ∆CP∆T

This equation does not apply only to phase changes. It can be

used to determine the enthalpy change for any reaction at
another temperature. It does assume that the heat capacities
are constant over the range of T.
Practice Problem
25℃,1 𝑎𝑎𝑎𝑎𝑎𝑎
Question: Fe2O3(s) + 3H2(g) 2Fe(s) + 3H2O(l)
What is the enthalpy change at 358K?
Practice Problem Solution
At 298K: ΔH°Rxn = when using values measured at 298K.
ΔH°Rxn @ 298K= 2(0) + 3(-285.830) – (-824.2) – 3(0) = -33.3 kJ/mol
If we assume ΔH is independent of T, then this would be our answer (e.g., 1st -year
chemistry).

If we want to correct for the temperature dependence of ΔH at 358 K, then we need to

use
Kirchoff’s Law: ∆H(T2) = ∆H(T1) + ∆CP∆T
i.e.,
ΔH°Rxn @ 358K= ΔH°Rxn @ 298K + ([2(25.10)+ 3(75.3)- 103.8 - 3(28.8)]J·mol-1·K-1)
[358-298K])/(1000 J/kJ)
ΔH°Rxn @ 358K = -33.3 kJ/mol + 5.15 kJ/mol = -28.1 kJ
So, in this case, if we were to assume enthalpy is independent of T and used -33.3
kJ/mol, we would be off by ~15%. In some cases that’s not a problem, while others it’s a
big issue!
Bond Enthalpy
∆HB or BDE, is the energy required to dissociate the bond into
its constituent atoms or free radicals (species must be in the
gas phase)
e.g., H–H(g) → H•(g) + H•(g); ∆HB = +436 kJ/mol
Note: ∆HB = +436 kJ/mol ≅ 2 ∆H°f (H(g))

Tabulated bond enthalpies are averages.

ALWAYS a positive quantity

∴ΔHrxn° = ∑ BE(broken) – ∑ BE(formed)

 Hess’ Law
∆HRxn = Σn∆Hf (products)
Lattice -Σn∆Hf (reactants)
vap., fus., sub.,
comb., atom. Enthalpies
qSurr = C∆T = nc∆T
Bond = mCS∆T
Enthalpies ∆HRxn = qP
≈ -∆ngasesRT
∆H = ∆U + ∆ngasesRT PV = nRT
qSyst. = - qSurr.
= qRxn -Pext.∆V
qV = ∆U
Internal Energy (∆U) = heat(q) + work(w)
17
Chapter 4 – The Second Law of
Thermodynamics
4.1 Spontaneous Processes
4.2 Entropy
4.3 The Second Law of Thermodynamics
4.4 Entropy Changes
4.5 The Third Law of Thermodynamics
4.6 Gibbs Energy
4.7 Standard Molar Gibbs Energy of Formation
4.8 Dependence of Gibbs Energy on Temperature and
Pressure
4.9 Phase Equilibria
Spontaneous Processes
We learned previously that energy
cannot be created or destroyed but
flows from one part of the universe to
another or is converted. This is the 1st
Law of Thermodynamics. But the 1st law
cannot help us predict the direction of a
reaction.
Changes in energy do not tell the full
story of a spontaneous process Systems will change spontaneously such
because for example, a gas will expand that they reduce their capacity for change,
outwards until it reaches an equilibrium or in other words will approach equilibrium.
pressure, but the internal energy of the The reverse process of a spontaneous
system has not changed.
process will never occur under the same
This is where we introduce another conditions.
term: Entropy
Spontaneous Processes
Spontaneous processes increase the amount of disorder in a
system
 Water running downhill
 Heat flowing from high temperature to low temperature
 Solutes distributing uniformly throughout a solution (sugar
in coffee)
 Ice melting at 20 °C
 Objects falling from height
Probabilities
Probability
 If we consider gas expansion: a container of V1 is
# atoms
filled with an ideal gas, and if the container volume is
doubled to V2, the gas will expand to fill that space.
We know intuitively that they will not move back into
V1 spontaneously, but why?
 The probability of finding a gas molecule in V2 is 1,
while the chances of finding a gas molecule in V1 is ½.
If we want to find 2 gas molecules in V1 the
probability becomes ½ x ½ = ¼. Volume
 The system moves from a state of low probability, to
one of high probability.
The Boltzmann Equation
In the statistical interpretation, entropy is related to probability by
the Boltzmann equation:

where kB is the Boltzmann constant, 1.381×10-23 J/K. Note: R = kBNA,

where NA is Avogadro’s number. W refers to the number of
“microstates” that the system can exist in. The value of lnW is
unitless, so entropy has units of J/K.

Recall: We cannot measure entropy directly, we can only measure

the change in entropy
This equation only holds for
isothermal (constant T) processes. If
T increases there is an additional
randomness which is not taken into
account by this equation.
Entropy – Review P.51-60 in notes
Entropy, S, is a thermodynamic quantity that is a measure of
how dispersed the energy of a system is among the different
possible ways that system can contain energy.
 Entropy is a state function. It depends on variables, such as
temperature and pressure, that determine the state of the
substance.
 Measures probability or number of equivalent arrangements
of the same energy
 Entropy is an extensive property. It depends on the amount
of substance present.

23
Entropy Cont’d
There are two situations where the energy can be dispersed
in a system, and entropy will increase
1. Positional – the distribution of a species in space
e.g., mixing of two gases or the expansion of gas into a vacuum

2. Thermal – the distribution of energy among species, or

distribution over energy levels
e.g., heat flow from hot to cold objects

Note: Entropy is a measure of energy dispersal, not a measure of energy

itself.

24
Standard Molar Entropy
o o
=∆r S o
∑ nS (products) − ∑ nS (reactants)

You will see that unlike with enthalpy, there is no delta or

subscript f for standard molar entropy values. This is because
these are absolute values.
An additional note: unlike with ΔfH°, S° values for elements in
their most stable forms at 298 K are not zero.
One convention: nS° (H+, aq) = 0
Factors Affecting Entropy
Entropies are strongly dependent on pressure, concentration, and
temperature.
 So increases with melting and vaporisation
 So increases when a solid or liquid dissolves in a solvent
 So decreases when a gas dissolves in a solvent
 So for similar substances increases with increasing mass
 So increases with an increasing number of atoms
 So increases with increasing molecular flexibility (rotation about C-C
bonds)
Second Law of Thermodynamics
The Second Law of Thermodynamics states that in any
spontaneous process, the total entropy of the universe must
increase.
ΔSTOTAL = ΔSuniverse = ΔSsystem + ΔSsurroundings > 0

There are THREE scenarios:

1) Spontaneous processes, ΔSuniv > 0
2) Processes at equilibrium, Δ Suniv = 0
3) Non–spontaneous processes, Δ Suniv < 0
(i.e., spontaneous in the reverse direction)

27
Practice Problem (4.19 Textbook)
Predict whether ∆S is + or – for the following at 298 K.

a) 4Fe(s) + 3O2(g) → 2Fe2O3(s)

c) NH4Cl(s) → NH3(g) + HCl(g)

d) H2(g) + Cl2(g) → 2HCl(g)

Practice Problem (4.21 textbook)
A quantity of 0.35 mole of an ideal gas initially at 15.6°C is
expanded from 1.2 L to 7.4 L. Calculate the values of w, q, ∆U
and ∆S if the process is carried out
(a) isothermally & reversibly, and
(b) isothermally & irreversibly against Pext = 1.0 atm.
Thermodynamic Definition of Entropy
We can express ΔS in terms of heat absorbed in a reversible,
isothermal expansion, but the expression is applicable to any
isothermal process.

 Unlike energy, entropy is not conserved and will occur

spontaneously. It will also tend to increase.
 Any local decreases in entropy are always accompanied by a
larger increase in entropy of the surroundings. Either ΔSsys or
ΔSsurr can be negative, but the sum of both quantities must be
greater than or equal to zero. i.e, ∆Suniverse ≥ 0
2 nd Law of Thermodynamics
The entropy of an isolated system increases in an irreversible
process and remains unchanged in a reversible process. It can
never decrease.

∆Suniv = ∆Ssys + ∆Ssurr

where ∆Suniv = 0 for a reversible process and ∆Suniv > 0 for an

irreversible process

Recall: a reversible process is a theoretical process near

equilibrium.
Mixing of Ideal Gases
Mixing of two ideal gases at the same temperature and
pressure leads to an increase in entropy since xA and xB (mole
fractions) are always less than 1 and render the ln terms to be
negative.

No heat exchange from mixing, so qsurr = 0 and ΔSuniv = ΔSmix

ΔS during a Phase Change
Phase transitions normally take places at the equilibrium
transition temperature and at constant pressure. Therefore,
𝑞𝑞𝑟𝑟𝑟𝑟𝑟𝑟,𝑝𝑝 ∆𝐻𝐻𝑓𝑓𝑓𝑓𝑓𝑓 ∆𝐻𝐻𝑣𝑣𝑣𝑣𝑣𝑣
∆𝑆𝑆𝑓𝑓𝑓𝑓𝑓𝑓 = = or ∆𝑆𝑆𝑣𝑣𝑣𝑣𝑣𝑣 =
𝑇𝑇 𝑇𝑇𝑓𝑓𝑓𝑓𝑓𝑓 𝑇𝑇𝑣𝑣𝑣𝑣𝑣𝑣

Temperature dependence of Entropy

 Entropy rises with temperature; more motion leads to more
disorder
𝐶𝐶𝑝𝑝∆𝑇𝑇 𝑆𝑆2 𝑇𝑇2 𝐶𝐶𝑝𝑝
 Since ∆H = Cp∆T, then ∆S = or ∫𝑆𝑆 𝑑𝑑𝑑𝑑 = ∫𝑇𝑇 𝑇𝑇 𝑑𝑑𝑑𝑑
𝑇𝑇 1 1
 If Cp is independent of T, then
𝑇𝑇2 𝑇𝑇2
∆S = Cp ln and at constant V: ∆S = Cv ln
𝑇𝑇1 𝑇𝑇1
ΔS during a Phase Change
If the transition takes place at the Entropy rises with temperature and
equilibrium transition temperature, can be calculated under constant
these are “reversible” processes pressure or constant volume
and qrev = ΔH conditions.
Practice Problem (Textbook 4.14)
A sample of neon (Ne) gas initially at 20 °C and 1.0 atm expanded from 1.2
to 1.6 L and simultaneously heated to 40 °C. Calculate the entropy
change for this process.
 Entropy Equation Summary
Isothermal Process Reversible Isothermal Process

qrev
∆S =
T
2nd Law of Thermodynamics
Phase Transitions
∆S sys + ∆S surr ≥ 0
∆Suniv = ∆ transition H
∆ transition S =
Mixing of Ideal Gases
Ttransition
Constant V or P
T2
Change in Entropy for a Reaction ∆S =nC ln
∆r S o
∑ nS
o o
(products) − ∑ nS (reactants) T1
Absolute Entropies
We said last lecture that you can’t measure S, you can only
measure ΔS. This is only partly true.
If we look again at the Boltzmann equation, and want to
determine the entropy of a perfect, crystalline substance at T
= 0 K, we know that there is only one possible microstate in
which the system can exist, so W = 1. We know that ln(1) = 0
and therefore Szero = 0 J/K.
By setting entropy at 0 K to be zero, we can calculate absolute
entropies relative to absolute zero.

lim S = 0 =S k=B ln W k=B ln(1) 0 J / K

T →0 K
Boltzmann equation
3 rd Law of Thermodynamics
The entropy of any pure, perfect crystalline material is 0 at 0 K.
As T increases from 0 K, entropy
increases due to thermal motion.
The figure shows the increase in
entropy of a perfect crystalline
substance from absolute zero to its
gaseous state.
Note that melting and boiling phase
transitions contribute to the total
entropy value.
Entropy and Life
 Plants and animals develop spontaneously in complex
organized structures seemingly in violation of the 2nd Law of
Thermodynamics, but we know that living organisms are not
in equilibrium.
 The entropy of living organisms is extremely difficult to
measure because we would have to use a reversible pathway.
 Therefore, using ΔS as a criterion of spontaneity often
becomes impossible and it would be useful to have another
measure of spontaneity which is known as the Gibbs Free
Energy.
Gibbs Energy
 If we want to know the spontaneity of a reaction just by
studying the system, we can define a new extensive state
function that uses both enthalpy and entropy to predict the
direction of reactions.
 This is known as the Gibbs Energy and is valid under
conditions of constant temperature and constant pressure.
 If ΔG is positive the process is endergonic
 If ΔG is negative the process is exergonic
Derivation of Gibbs Free Energy (G)
We know that: ΔSuniverse = ΔSsurroundings + ΔSsystem (1)

We also know that at constant T:

ΔSsurroundings = qsurroundings/T = - qsystem/T

If P is also constant, then

ΔSsurroundings = - qsystem,P / T = - ΔHsystem / T (2)
(This is a key relationship!)
Therefore, substituting (2) into equation (1):
ΔSuniverse = - qsystem/T + ΔSsystem

Multiply both sides by –T:

–T ΔSuniverse = ΔHsystem – T ΔSsystem

We define: –T ΔSuniverse = ΔG = ΔH – T ΔS
41
∆G as a Criterion for Spontaneity
The spontaneity of a reaction can now be determined by the
sign of ∆G.

∆G < 0 kJ : spontaneous

∆G > 0 kJ: nonspontaneous

∆G = 0 kJ: at equilibrium

Only applies to reactions at constant T and P

42
 The 4 Possibilities of ΔG = ΔH – TΔSEntropy Driven i.e.,
good for
Entropy Driven i.e., spontaneity!
good for
spontaneity!

To Find ‘High T’ and ‘Low T’ values, use T = ΔH/ ΔS (when ΔG = 0)

43
Gibbs Energy and Work
It is helpful to be able to relate the Gibbs Energy to the amount of work
a process can do.

ΔG can be found to be equal to the maximum amount of non-expansion

work done on the system (i.e., reversible work).

∆G =wrev
Helmholtz Energy
Helmholtz Energy, A, is similar to the Helmholtz Energy
Gibbs Energy but is used in processes of
constant temperature and constant
volume.
This expression provides us the same ∆A =∆U − T ∆S
criteria for spontaneity as the Gibbs
Energy expression does, though we will
typically be working under constant Internal Energy
pressure conditions and prefer to use
Gibbs Energy.

If ΔA < 0 the process is spontaneous as written

If ΔA > 0 the process is not spontaneous as written
If ΔA = 0 the process is at equilibrium
Standard Molar Free Energies of Formation, ∆Gf°
The standard free energy of formation is the free−energy change
that occurs when 1 mol of substance is formed from its elements
in their standard states at 1 atm and at a specified temperature,
usually 25°C.

ΔG°m,f of any pure element (in its standard state) = 0

The corresponding reaction for the standard free energy of

formation is the same as that for standard enthalpy of formation,
∆Hf°.

46
Calculating ΔG°rxn
ΔG is a state function and we can get ΔG°rxn from:
a) Tables of ΔG°m,f data (at any specific temperature, e.g., 25 °C
To find the standard free energy change for a reaction where n = moles:

∑ nΔG (products) − ∑ nΔG (reactants)

 
ΔG =


b) ΔH°f and ΔS°m data (at any temperature, and make assumption) and
use:
ΔG°rxn = ΔH°rxn - TΔS°rxn

You should be able to calculate these at any time it is required – CHEM*1050

47
Gibbs Energy and Entropy Equations
Gibbs Energy of Reaction Fill in new ones here!
o o
∆rG =o
∑ n∆ f G (products) − ∑ n∆ f G (reactants)

Gibbs Energy at Constant P

∆G =∆H − T ∆S
Helmholtz Energy at Constant V

∆A =∆U − T ∆S
Maximum Amount Useful work

∆G =wrev
Properties of Gibbs Energy
Useful relationship: dG = VdP – SdT
(Also: dH = TdS + VdP and dU = TdS – PdV)
q and w

a) Pressure dependence of G (at constant T):

From dG = VdP – SdT, if T is constant then we get:

𝜕𝜕𝜕𝜕
dG = VdP or = 𝑉𝑉
𝜕𝜕𝜕𝜕 𝑇𝑇

V, is positive, this means when we ↑P that results in an ↑G at constant T.

 Properties of Gibbs Energy
a) Pressure dependence of G (at constant T):
The Gibbs energy of a process is also dependent on pressure, and we
can use this equation to determine if a process is more favourable at one
pressure vs another.
P2
∆G =nRT ln
P1
Ideal gases have a higher free energy when pressure is above 1 atm (lnP is
positive). Ideal gases have a lower free energy when the pressure is
below 1 atm (lnP is negative).
P
Use this equation it calculate G of
G G + nRT ln
= o
reaction at different pressures if
you know standard free energy at 1atm
1 atm. Example soon.
Practice Problem
What is the free energy of formation of CO2 in the atmosphere at its
normal sea level partial pressure of 0.00031 atm and T = 25 °C? (∆G°f =
–394.38 kJ/mol)
Properties of Gibbs Energy
b) Concentration dependence of G (@ ∆T = 0):
𝑐𝑐2
∆G = nRT ln where c refers to molarity (for now…)
𝑐𝑐1
Gibbs energy is dependent on the volume, though the volume may be
treated as a constant in the case of liquids and solids.

∆G = V ∆P
Gibbs energy can also be expressed as having a dependence on the
concentration of a solution.
c
∆ f G + nRT ln
∆fG = o

1mol / L
Practice Problem
If ΔfG° for a particular substance in solution is -22.22 kJ/mol at 25 °C,
what is the value in a 0.01 mol/L solution?
c
∆ f G + nRT ln
∆fG = o

1mol / L
Properties of Gibbs Energy
c) Temperature dependence of G (@ ∆P = 0):
𝜕𝜕𝐺𝐺
From dG = VdP – SdT: dG = – SdT or = −𝑆𝑆
𝜕𝜕𝑇𝑇 𝑃𝑃
𝜕𝜕𝐺𝐺 𝐻𝐻 − 𝐺𝐺
From G = H – TS: = which produces:
𝜕𝜕𝑇𝑇 𝑃𝑃 𝑇𝑇

∆G2 ∆G1 1 1 Gibbs-Helmholtz equation

− = ∆𝐻𝐻 − (assumes ∆H is T independent)
T2 T1 𝑇𝑇2 𝑇𝑇1

See if rxn more favourable at a different T (or solve for ∆H)

Gibbs-Helmholtz Equation
The Gibbs-Helmholtz equation relates the temperature
dependence of the Gibbs energy change, and the equilibrium
of the process to the enthalpy change of the process.
Using this equation, we can determine whether a reaction will
be more favourable at a different temperature.

∆G2 ∆G1 1 1
− =∆H  − 
T2 T1  T2 T1 
or
∆∆GG22 ∆∆GG11 TT22−−TT11 The Gibbs energy of a
−− ∆HH
==
−∆ 
process is dependent on

TT22 TT11  TT21TT12 

temperature. Helpful
equation if you do not have S.
Practice Problem
The carbonylation of methanol produces acetic acid according to the
reaction:
CO(g) + CH3OH(l) → CH3COOH(l)
Data (25°C): ∆H f (kJ⋅mol-1) ∆G f (kJ⋅mol-1)
CO (g) -110.5 -137.3
CH3OH(l) -238.7 -166.3
CH3COOH(l) -484.2 -389.9

For the following questions, support your answers with a numeric value
and state any assumptions.

a) Will this reaction occur at 25°C and 1 atm?

b) Will this reaction occur at 500K and 1 atm?
c) How would decreasing the pressure from 1 atm to 0.02 affect this
reaction at 25 °C.
Practice Problem
Gibbs Energy and Phase Equilibria
Two phases in equilibrium with each other, e.g., solid ⇆ liquid
or liquid ⇆ gas
The molar Gibbs energy for the two phases must be equal at constant T
and P G =G where α and β represent the two phases
α β

If the external conditions (T and/or P) are changed, then the equilibrium

shifts until the molar Gibbs energies are again equal, e.g.,
if Gsol > Gliq some solid would melt because ∆G= Gliq − Gsol < 0
if Gsol < Gliq some liquid would spontaneously freeze, i.e., ∆G= Gsol − Gliq < 0
Gibbs Energy and Phase Equilibria
We will be considering here only one-component
systems (i.e., pure substances).
At some temperature and pressure, two phases are in
equilibrium.

G Phase1 = G Phase 2

The slope of the lines is based on the molar entropy for

the phase.
Dependence of 𝐺𝐺̅ on T for a gas,
𝜕𝜕𝜕𝜕 liquid & solid phase at constant P.
= −𝑆𝑆 ̅
𝑆𝑆𝑣𝑣𝑣𝑣𝑣𝑣 ̅ ≫ 𝑆𝑆𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠
≫ 𝑆𝑆𝑙𝑙𝑙𝑙𝑙𝑙 ̅ The phase with the lowest 𝐺𝐺̅ is
𝜕𝜕𝜕𝜕 𝑃𝑃
the most stable phase at that T.

The steeper the slope, the higher the entropy

Gibbs Energy and Phase Equilibria
Lines at
P1 and P2

When we change the pressure of a system,

we can see that the intersections of the
tangents occur at different temperatures.
This tells us that changing the pressure can
affect the temperature at which a substance
boils or melts.
Increases in external pressure will typically
raise both the melting and boiling points
(notable exception is water).
A shift in freezing point assumes that the molar
∂G  volume of the liquid is greater than that of the P dependence of 𝐺𝐺̅ , where P2 > P1. For
  =V solid. This is true for most substances, the most most substances (H2O is an exception) ↑ P
 ∂ P T notable exception being water where an leads to ↑ melting pt and boiling pt.
increase in pressure causes a decrease in the
melting point

G ↑ with ↑P, with greatest ∆ in vapour phase; shifts T higher w/ ↑P.

Classius-Clapeyron Equation
For a phase transition between 2 phases, at constant T and P, it can be
shown that:
𝑑𝑑𝑑𝑑 ∆𝑆𝑆 𝑑𝑑𝑑𝑑 ∆𝐻𝐻
= and =
𝑑𝑑𝑑𝑑 ∆𝑉𝑉 𝑑𝑑𝑑𝑑 𝑇𝑇∆𝑉𝑉
where T = temperature of phase transition, e.g.,
ln P
𝑑𝑑𝑑𝑑 ∆𝐻𝐻𝑣𝑣𝑣𝑣𝑣𝑣 slope = (–∆Hvap/R)
=
𝑑𝑑𝑑𝑑 𝑇𝑇𝑣𝑣𝑣𝑣𝑣𝑣 ∆𝑉𝑉𝑣𝑣𝑣𝑣𝑣𝑣

Assuming ΔVvap ≈ Vgas & after integration: 1/T

∆𝐻𝐻𝑣𝑣𝑣𝑣𝑣𝑣
ln P = − + 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
𝑅𝑅𝑅𝑅

𝑃𝑃2 ∆𝐻𝐻𝑣𝑣𝑣𝑣𝑣𝑣 𝑇𝑇2 −𝑇𝑇1

OR ln =
𝑃𝑃1 𝑅𝑅 𝑇𝑇1 𝑇𝑇2
Vaporization Curves showing VP increases as T increases

Vapor Pressures of Several Liquids as a Function of

Temperature. The point at which the vapor pressure
curve crosses the P = 1 atm line (dashed) is the
normal bpt of the liquid. (CC BY-SA-NC 3.0; Anonymous) 62
Slopes on Phase Diagrams
Recall our P-T phase diagrams for pure
substances.
The slopes of the equilibrium lines
between phases are dependent on molar
enthalpy and molar volume changes.
We can use the Clapeyron equation to
calculate the slope of an equilibrium
curve.
dP ∆ H
=
dT T ∆V Typical phase diagram for a pure substance
Practice Problem
Calculate the slope of the liquid-gas curve at 298.15 K in atm/K, given
that ΔHvap = 44.0 kJ/mol, the molar volume of the liquid is 1.56×10-2
L/mol and the molar volume of the gas is 23.74 L/mol.
Gibbs Phase Rule
Gibbs Phase Rule tells us the number of Examples:
intensive variables – such as pressure, In a one-component system where only one phase
temperature, and composition – that can be is present:
changed independently without disturbing the f = (1) – (1) + 2 = 2

number of phases in equilibrium. This means that we could change 2 intensive

variables, and the phase would remain the same

f =c − p + 2 In a one-component system where three phases

are present (i.e., triple point):
f = (1) – (3) + 2 = 0
f is the degrees of freedom which corresponds
This means that we can’t change any variables
to the possible changing variables without disrupting the three phases which are in
equilibrium.
c is the number of components

p is the number of phases