CHAPTER 17

GIBBS ENERGY AND THERMODYNAMICS

 Chapter 17 - Introduction
1. Kinetics: How fast does a reaction proceed?
2. Equilibria: How far towards completion does a reaction go?

For all of these observations, we want to understand:

Why do they happen in the first place?

This Chapter we will discuss Entropy, a driving force behind

physical and chemical change.
• In general terms, entropy describes the dispersion of energy
• Nature tends toward a state where energy is spread out as much as
possible
• We will find that the universe has entropy that always increases

2
Spontaneous and Non-Spontaneous Processes
Spontaneous Process: a process that occurs without ongoing external
intervention
Easy to predict in the physical world:
• Water flows and balls roll downhill spontaneously to reach lower potential
energy in the presence of gravity

3
Spontaneous and Non-Spontaneous Processes
Spontaneous reactions can occur both slow and fast.
• Spontaneity determines the direction and extent that a reaction proceeds
to
Some spontaneous processes can be very slow:
A catalyst can increase the rate of a
spontaneous process.

A catalyst cannot do so for a non-

spontaneous process.

Non-spontaneous processes are not

IMPOSSIBLE, they require the input
of external energy or coupling to a
more spontaneous reaction to
proceed

4
 Entropy and The 2nd Law of Thermodynamics
Entropy (S): A thermodynamic function that increases with the
number of EQUIVALENT ways to arrange the energy among the
components of the system to achieve a particular overall state

5
 Entropy and The 2nd Law of Thermodynamics
Entropy (S): A thermodynamic function that increases with the
number of EQUIVALENT ways to arrange the energy among the
components of the system to achieve a particular overall state

Mathematically, entropy is described by:

𝑺 = 𝒌 𝐥𝐧 𝑾
Where:
𝑹
k is Boltzmann’s constant = 𝟏. 𝟑𝟖 × 𝟏𝟎−𝟐𝟑 J K-1
𝑵𝑨
W is the number of equivalent energy arrangements in the
system (microstates, unitless)
Note: Entropy has units of J K-1 and as W increases, entropy increases 6
 Entropy and The 2nd Law of Thermodynamics
Mathematically, entropy is described by:

𝑺 = 𝒌 𝐥𝐧 𝑾
The key to understanding entropy is to understand W
• We will investigate this to learn what it signifies by considering a closed
system
While this system’s overall energy does not change, within it
we can distribute the energy to the gas particles in various
Macrostate ways:
Gas with constant • Translational energy
T, P, and V • Vibrational energy
• Rotational energy
• Electronic excitations within atoms or bonds

7
 What Does W Signify?
𝑺 = 𝒌 𝐥𝐧 𝑾
Energy within this system is redistributed
continuously through collisions between the gas
Macrostate particles.
• An instantaneous snapshot of the energy in
Gas with constant this system is called a microstate
T, P, and V • In each instant the energy distribution might
change its microstate while the energy of the
macrostate remains constant

The quantity W describes the number of microstates that can

potentially exist within a given macrostate

8
 What Does W Signify?
𝑺 = 𝒌 𝐥𝐧 𝑾
If the quantity W describes the number of microstates that can potentially
exist within a given macrostate, then let’s consider an example.

If we have 2 particles with 8 J of energy to distribute, how many ways can

we arrange the particles with this energy in System A which has 4 available
energy levels compared to System B which has 8 available energy levels?
WA = 2
WB = 4

∴ System B has more

microstates and more entropy
(S) than A because there are
more ways to distribute the
total energy

9
 Entropy and The 2nd Law of Thermodynamics
Practical Example of Microstates: Ice (H2O(s)):
• Energy is dispersed in inter- and
intra-molecular vibrations
• Molecules are constrained to their
lattice positions

Water (H2O(l)):
• Vibrations still exist
• Molecules gain translation motion
in liquid phase
(W) • Molecules can also have rotational
motion

∴ There are more ways to distribute

the energy in the water and it has
greater entropy compared to the ice

10
 Entropy and The 2nd Law of Thermodynamics
Entropy: Some General Findings

1. A system with higher entropy has a larger number of

accessible energy levels than a system with lower
entropy

2. A system where a given amount of energy can be

dispersed in many different ways has more entropy that
a system whose energy can only be dispersed in a few
ways

11
 Entropy and The 2nd Law of Thermodynamics
The Second Law of Thermodynamics: For any spontaneous
process the entropy of the universe increases (∆𝑺𝒖𝒏𝒊𝒗 > 𝟎)

∴ spontaneous processes increase the entropy of the

universe. Those that do not increase ∆𝑺𝒖𝒏𝒊𝒗 , are non-
spontaneous.

Entropy is a state function. Any change depends only on

the initial and final states and NOT the path traveled.
∆𝑺 = 𝑺𝒇𝒊𝒏𝒂𝒍 − 𝑺𝒊𝒏𝒊𝒕𝒊𝒂𝒍
Entropy determines the direction of chemical and
physical change where ∆𝑺𝒖𝒏𝒊𝒗 > 𝟎 12
 Entropy and The 2nd Law of Thermodynamics
When entropy increase during a chemical or physical process,
then, it has a positive value for the change in entropy:
∆𝑺 = 𝑺𝒇𝒊𝒏𝒂𝒍 − 𝑺𝒊𝒏𝒊𝒕𝒊𝒂𝒍

Some other considerations:

1. Temperature: more total energy in a system means there are
more possible ways to distribute that energy, so a positive
change in entropy results with an increase in temperature
2. Number of particles in system: Each new particle brings an
equal energy to a system to keep its temperature constant,
resulting in systems with more particles having more
microstates and, thus, entropy
13
 Entropy and The 2nd Law of Thermodynamics
3. Change in State: Entropy
increases with state change
from solid → liquid → gas
because there are more ways of
distributing energy into the
composite particles (e.g. solid –
vibrations; gas – vibration,
translation, rotation) where the
system then has more total
energy and more accessible
energy levels (i.e. more
microstates)
14
 Entropy and The 2nd Law of Thermodynamics
With this understanding, we can start to predict that ∆𝑺 > 𝟎 when:
1. There is a phase transition from solid to liquid (melting)
2. There is a phase transition from solid to gas (sublimation)
3. There is a phase transition from liquid to gas (evaporation)
4. There is an increase in the number of particles of gas in a
reaction.
Examples:
Predict the sign of ∆𝑺 for the process of:
a) Boiling water

b) I2(g) → I2(s)

15
Predict the sign of ∆𝑺 for the process of:
CaCO3(s) → CaO(s) + CO2(g)

a) ∆𝑺>0
b) ∆𝑺<0
c) ∆𝑺=0

16
 Heat Transfer and ∆𝑺𝒔𝒖𝒓𝒓𝒐𝒖𝒏𝒅𝒊𝒏𝒈𝒔
Some spontaneous processes occur where entropy of the system
under observation decreases.

For example, we all know that:

• Water freezes when temperatures are below 0 °C
• Fog droplets can form on ground surfaces overnight

Why is this? Because we forgot to consider the surroundings and

overall effect on the entropy of the universe!
∆𝑺𝒖𝒏𝒊𝒗𝒆𝒓𝒔𝒆 = ∆𝑺𝒔𝒚𝒔𝒕𝒆𝒎 + ∆𝑺𝒔𝒖𝒓𝒓𝒐𝒖𝒏𝒅𝒊𝒏𝒈𝒔
OR
∆𝑺𝒖𝒏𝒊 = ∆𝑺𝒔𝒚𝒔 + ∆𝑺𝒔𝒖𝒓𝒓
17
 Heat Transfer and ∆𝑺𝒔𝒖𝒓𝒓𝒐𝒖𝒏𝒅𝒊𝒏𝒈𝒔
This means for spontaneous processes where the entropy of the
system decreases, then the entropy of the surroundings must
increase more in order to satisfy the 2nd Law of Thermodynamics
∆𝑺𝒖𝒏𝒊 = ∆𝑺𝒔𝒚𝒔 + ∆𝑺𝒔𝒖𝒓𝒓

How does the system change the entropy of the

surroundings? Let’s go back to our phase changes for water.
• Freezing and condensation are both exothermic processes
(i.e. they release energy to the surroundings)
• This release of energy increases the temperature of the
surroundings (i.e. increase total energy, and number of
levels)
• The overall increase in the entropy of the
surroundings then is sufficient to offset 18
the decrease in entropy of the system
 Heat Transfer and ∆𝑺𝒔𝒖𝒓𝒓𝒐𝒖𝒏𝒅𝒊𝒏𝒈𝒔
Some general conclusions:
1. Exothermic processes increase the entropy of the
surroundings
2. Endothermic processes decrease the entropy of the
surroundings
What type of process does the
entropy change depicted in the figure
to the left represent?

a) Endothermic process
b) Exothermic process

19
 Quantifying ∆𝑺𝒔𝒖𝒓𝒓
• When a process releases heat to the surroundings (qsys, negative) it
increases ∆𝑺𝒔𝒖𝒓𝒓
• When heat is absorbed from the surroundings by a system (qsys, positive)
it decreases ∆𝑺𝒔𝒖𝒓𝒓

At constant T and P:
−∆𝑯𝒔𝒚𝒔
∆𝑺𝒔𝒖𝒓𝒓 =
𝑻
Practice

21
Practice

22
 Entropy Changes for Phase Transitions
If the system is at constant pressure q=∆𝑯, then we can calculate the change
in entropy for the system:
∆𝒓 𝑯 (𝒇𝒐𝒓 𝒑𝒉𝒂𝒔𝒆 𝒕𝒓𝒂𝒏𝒔𝒊𝒕𝒊𝒐𝒏)
∆𝒓 𝑺 =
𝑻
Worked Example:
Water freezes with ∆𝑯 =-6.02 kJ mol-1 at 273.15 K. Calculate ∆𝒓 𝑺 for this
phase change.

Note: This is consistent with our concept of a liquid → solid

phase change having a decrease in entropy 23
 Gibbs Energy and Spontaneity
For any process, we can calculate the change in entropy of the universe by:
∆𝑺𝒖𝒏𝒊𝒗 = ∆𝑺𝒔𝒚𝒔 + ∆𝑺𝒔𝒖𝒓𝒓
If the process is spontaneous:
∆𝑺𝒖𝒏𝒊𝒗 > 𝟎
−∆𝑯𝒔𝒚𝒔
We have also found that: ∆𝑺𝒔𝒖𝒓𝒓 =
𝑻

So:
∆𝑯𝒔𝒚𝒔
∆𝑺𝒖𝒏𝒊𝒗 = ∆𝑺𝒔𝒚𝒔 −
𝑻
24
 Gibbs Energy and Spontaneity
∆𝑯𝒔𝒚𝒔
∆𝑺𝒖𝒏𝒊𝒗 = ∆𝑺𝒔𝒚𝒔 −
𝑻
Now, if we multiply both sides by -T:
−𝑻 ∙ ∆𝑺𝒖𝒏𝒊𝒗 = ∆𝑯𝒔𝒚𝒔 − 𝑻 ∙ ∆𝑺𝒔𝒚𝒔

∆𝑮𝒔𝒚𝒔 ≡ Gibbs Energy

∴ for any reaction system:

∆𝒓 𝑮 = ∆𝒓 𝑯 − 𝑻∆𝒓 𝑺

25
 Gibbs Energy and Spontaneity
∆𝒓 𝑮 = ∆𝒓 𝑯 − 𝑻∆𝒓 𝑺

Since ∆𝒓 𝑮 ∝ −∆𝑺𝒖𝒏𝒊𝒗 :

1. ∆𝒓 𝑮 < 𝟎 corresponds to a spontaneous process

2. ∆𝒓 𝑮 > 𝟎 corresponds to a non-spontaneous process

This means there are four combinations of sign (+ or -) for

enthalpy and entropy that need to be considered for a
reaction system to predict OR calculate its spontaneity
26
 Gibbs Energy and Spontaneity
Case 1: ∆𝒓 𝑯 < 𝟎 (exothermic), ∆𝒓 𝑺 > 𝟎 (increase in entropy)

∆𝒓 𝑮 = ∆𝒓 𝑯 − 𝑻∆𝒓 𝑺
- +
-
∴ ∆𝒓 𝑮 is always negative, no matter the temperature

Example: 2 N2O(g) → 2 N2(g) + O2(g) ∆𝒓 𝑯° = −163.2 kJ mol-1

∆𝒓 𝑯 ∆𝒓 𝑺 ∆𝒓 𝑮

27
 Gibbs Energy and Spontaneity
Case 2: ∆𝒓 𝑯 > 𝟎 (endothermic), ∆𝒓 𝑺 < 𝟎 (decrease entropy)

∆𝒓 𝑮 = ∆𝒓 𝑯 − 𝑻∆𝒓 𝑺
+ -
+
∴ ∆𝒓 𝑮 is always positive, no matter the temperature

Example: 3 O2(g) → 2 O3(g) ∆𝒓 𝑯° = 285.4 kJ mol-1

∆𝒓 𝑯 ∆𝒓 𝑺 ∆𝒓 𝑮

28
 Gibbs Energy and Spontaneity
Case 3: ∆𝒓 𝑯 < 𝟎 (exothermic), ∆𝒓 𝑺 < 𝟎 (decrease entropy)

∆𝒓 𝑮 = ∆𝒓 𝑯 − 𝑻∆𝒓 𝑺
- -
+
∴ ∆𝒓 𝑮 is now temperature-dependent, - at low T, + at high T

Example: 2 H2O(l) → H2O(s) ∆𝒓 𝑯° = −6.01 kJ mol-1 (at 0℃)

∆𝒓 𝑯 ∆𝒓 𝑺 ∆𝒓 𝑮

29
 Gibbs Energy and Spontaneity
Case 4: ∆𝒓 𝑯 > 𝟎 (endothermic), ∆𝒓 𝑺 > 𝟎 (increase entropy)

∆𝒓 𝑮 = ∆𝒓 𝑯 − 𝑻∆𝒓 𝑺
+ +
-
∴ ∆𝒓 𝑮 is still temperature-dependent, but now + at low T, - at high T

Example: H2O(l) → H2O(g) ∆𝒓 𝑯° = 40.7 kJ mol-1 (at 100 ℃)

∆𝒓 𝑯 ∆𝒓 𝑺 ∆𝒓 𝑮

30
Summary: Gibbs Energy and Spontaneity

31
 Gibbs Energy and Spontaneity
Worked Example

32
 Calculating Entropy Change in Reactions
To calculate ∆𝒓 𝑺𝒐 , we need to remember definition of standard state:

Gases: standard state is pure gas at 1 bar

Liquids or solids: pure substance at 1 bar
In solution: 1 M concentration

∆𝒓 𝑺𝒐 : can be calculated by the following formula:

∆𝒓 𝑺𝒐 = Σ ν𝑝 𝑺𝒐 (𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔) − Σ ν𝑝 𝑺𝒐 (𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔)

where 𝑺𝒐 values are standard molar entropies of reactant and product

molecules

vp are coefficients from balanced chemical equation

33
 Standard Molar Entropies & 3rd Law of Thermodynamics
Standard entropies (𝑺𝒐 ) used are the absolute entropies of the compound at
standard state conditions

Standard entropy of zero defined by:

Third Law of Thermodynamics

The entropy of a pure perfect crystal at 0K is zero

S°(0K) = k ln W = 0

34
 Standard Molar Entropy Values, 𝑺𝒐

Note the general trend, the 𝑺𝒐 of gases > 𝑺𝒐 of liquids > 𝑺𝒐 of solids

35
Relative Standard Entropies: gas, liquid, solid
Substance Phase 𝑺𝒐 (J K-1 mol-1)
H2O gas 188.8
H2O liquid 70.0
CH3OH gas 239.9
CH3OH liquid 126.8
CH3CH2OH gas 281.6
CH3CH2OH liquid 160.7

For the same compound, gases have higher standard entropies than liquids

36
Relative Standard Entropies: molar mass
The larger the noble gas, the larger the molar
mass; the greater the standard entropy (a
relatively minor effect)

Heavier atoms have more closely spaced energy

levels, allowing greater dispersal of energy, a
larger value of W, and thus larger 𝑺𝒐 .

37
Relative Standard Entropies: Molecular Complexity
Molecules have more modes to disperse energy
compared to atoms. The more complex the
molecule (i.e. the more atoms and vibrational
modes), the greater is 𝑺𝒐
Gas Mw 𝑆𝑜
(g mol-1) (J K-1 mol-1 )
F2 has vibrational and rotational modes of energy, Ar (g) 39.95 154.8
hence higher 𝑺𝒐 compared to Ar (~ similar MW) F2 (g) 38.00 202.8

C2H4 and N2H4 have 6 atoms compared to 2 atoms Gas Mw 𝑆𝑜

(g mol-1) (J K-1 mol-1 )
for N2 and O2 respectively, hence more vibrational N2 (g) 28.02 191.6
modes and a higher 𝑺𝒐 C2H4 (g) 28.05 219.3
O2 (g) 32.00 205.2
N2H4 (g) 32.05 238.5
38
Calculating Standard Entropy Changes for Reactions, Δ𝒓𝑺𝒐
∆𝒓 𝑺𝒐 = Σ ν𝒑 𝑺𝒐 𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 − Σ ν𝒓 𝑺𝒐 𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔

𝑺𝒐 (H2S (g)) = 205.8 J mol-1 K-1 𝑺𝒐 (O2 (g)) = 205.2 J mol-1 K-1
𝑺𝒐 (H2O (g)) = 188.8 J mol-1 K-1 𝑺𝒐 (SO2 (g)) = 248.2 J mol-1 K-1

39
Gibbs Energy Changes in Chemical Reactions
There are three main methods to calculate ∆𝒓 𝑮𝒐

1) Calculate ∆𝒓 𝑮𝒐 using tabulated Gibbs Energy of formation ∆𝒇 𝑮𝒐 : (tables

usually valid for 298 K only)
∆𝒓 𝑮𝒐 = Σ ν𝑝 Δ𝑓 𝑮𝒐 𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 − Σ ν𝑟 Δ𝑓 𝑮𝒐 𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔

2) i) Calculate ∆𝒓 𝑯𝒐 and ∆𝒓 𝑺𝒐 separately

ii) Calculate ∆𝒓 𝑮𝒐 using the following relationship and given T
∆𝒓 𝑮𝒐 = ∆𝒓 𝑯𝒐 − 𝑻∆𝒓 𝑺

3) Calculate ∆𝒓 𝑮𝒐 by taking a linear combination of the free energies of

related chemical reactions (similar to Hess’s law for enthalpies)

40
 Method 1: Gibbs Energy of Formation
The Gibbs energy of formation, Δ𝑓 𝑮𝒐 , is defined as: “the change in Gibbs
energy when 1 mole of a compound forms from its constituent elements in
their standard states. The Gibbs energy of formation of pure elements in
their standard states is zero.” NOTE: Appendix II values valid @ 298 K

41
 Question
Which reaction correctly depicts the Gibbs energy of formation of N2O (g) ?

A) 2 N2 (g) + O2 (g) → 2 N2O (g)

B) N2 (g) + ½ O2 (g) → N2O (g)

C) 2 N (g) + O (g) → N2O (g)

D) N2 (l) + ½ O2 (l) → N2O (g)

42
 Method 1: Gibbs Energy of Formation
Because Gibbs energy is a state function, we can use the following equation
to calculate the change in Gibbs energy for a reaction:

∆𝒓 𝑮𝒐 = Σν𝑝 Δ𝑓 𝑮𝒐 𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 − Σν𝑟 Δ𝑓 𝑮𝒐 𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔

Remember:
- Defining Δ𝑓 𝑮𝒐 for a pure element in its standard state as 0 is arbitrary

- Since all we require is ∆𝒓 𝑮𝒐 and not “absolute G” values, this method

always works

- Result is only valid at 298 K (using Appendix II data)

43
 Method 1: Gibbs Energy of Formation

Given: ∆𝒇 𝑮𝒐 (NO (g)) = 87.6 kJ mol-1 ∆𝒇 𝑮𝒐 (CO (g)) = -137.2 kJ mol-1

∆𝒇 𝑮𝒐 (CO2 (g)) = -394.4 kJ mol-1 ∆𝒇 𝑮𝒐 (N2 (g)) = 0 kJ mol-1

44
 Method 2: ∆𝒓 𝑮𝒐 = ∆𝒓 𝑯𝒐 − 𝑻∆𝒓 𝑺𝒐
Method 2: Calculate/use Δ𝑟 𝑯𝒐 and Δ𝑟 𝑺𝒐 values separately in the equation

∆𝒓 𝑮𝒐 = ∆𝒓 𝑯𝒐 − 𝑻∆𝒓 𝑺𝒐

∆𝒓 𝑺𝒐 can be calculated from standard molar entropies as shown earlier

∆𝒓 𝑯𝒐 might be provided directly, or could calculate from standard enthalpies of

formation

Allows ∆𝒓 𝑮𝒐 to be calculated at temperatures other than 298 K

NOTE: standard molar entropies and standard enthalpies of formation are

temperature-dependent, but not too significant for our purposes

45
 Method 2: ∆𝒓 𝑮𝒐 = ∆𝒓 𝑯𝒐 − 𝑻∆𝒓 𝑺𝒐
If you need to calculate ∆𝒓 𝑯𝒐 values, look up ∆𝒇 𝑯𝒐 values in Appendix II and
use a familiar looking formula:

∆𝒓 𝑯𝒐 = Σν𝑝 Δ𝑓 𝑯𝒐 𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 − Σν𝑟 Δ𝑓 𝑯𝒐 𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔

Definitions exactly the same as standard Gibbs energies of formation

Remember: enthalpy, entropy and Gibbs energy are all state functions so
this general method always works

46
 Method 2: ∆𝒓 𝑮𝒐 = ∆𝒓 𝑯𝒐 − 𝑻∆𝒓 𝑺𝒐

Given: ∆𝒇 𝑯𝒐 (NO (g)) = 91.3 kJ mol-1 ∆𝒇 𝑯𝒐 (O2 (g)) = 0 kJ mol-1 ∆𝒇 𝑯𝒐 (NO2 (g)) = 33.2 kJ mol-1
𝑺𝒐 (NO (g)) = 210.8 J mol-1 K-1 𝑺𝒐 (O2 (g)) = 205.2 J mol-1 K-1 𝑺𝒐 (NO2 (g)) = 240.1 J mol-1 K-1

47
Method 3: Calculating ∆𝒓 𝑮𝒐 from stepwise reactions
Could also calculate ∆𝒓 𝑮𝒐 by “adding” chemical reactions together with
known ∆𝒓 𝑮𝒐 values

Use the following rules for manipulating chemical reactions:

1. If a reaction is reversed, change the sign of ∆𝒓 𝑮𝒐

C3H8 (g) + 5 O2 (g) → 3 CO2 (g) + 4 H2O (g) ∆𝒓 𝑮𝒐 = -2074 kJ mol-1

3 CO2 (g) + 4 H2O (g) → C3H8 (g) + 5 O2 (g) ∆𝒓 𝑮𝒐 = 2074 kJ mol-1

48
Method 3: Calculating ∆𝒓 𝑮𝒐 from stepwise reactions
2. If reaction coefficients are multiplied by a constant n, multiply ∆𝒓 𝑮𝒐 by
the constant n

C3H8 (g) + 5 O2 (g) → 3 CO2 (g) + 4 H2O (g) ∆𝒓 𝑮𝒐 = -2074 kJ mol-1

2 C3H8 (g) + 10 O2 (g) → 6 CO2 (g) + 8 H2O (g) ∆𝒓 𝑮𝒐 = -4148 kJ mol-1

3. If two (or more) reactions are summed together, add their ∆𝒓 𝑮𝒐 values

H2O (g) → H2 (g) + ½ O2 (g) ∆𝒓 𝑮𝒐 = 228.6 kJ mol-1

CO (g) + ½ O2 (g) → CO2 (g) ∆𝒓 𝑮𝒐 = -257.2 kJ mol-1

Overall: CO (g) + H2O (g) → H2 (g) + CO2 (g) ∆𝒓 𝑮𝒐 = -28.6 kJ mol-1

49
Method 3: Calculating ∆𝒓 𝑮𝒐 from stepwise reactions
Example: Calculate ∆𝒓 𝑮𝒐 for the following reaction:

Fe2O3 (s) + 3 CO (g) → 2 Fe (s) + 3 CO2 (g)

using the following data:

Rxn 1: 2 Fe (s) + 3/2 O2 (g) → Fe2O3 (s) ∆𝒓 𝑮𝒐 = -742.2 kJ mol-1

Rxn 2: CO (g) + ½ O2 (g) → CO2 (g) ∆𝒓 𝑮𝒐 = -257.2 kJ mol-1

Solution:

- Reverse “reaction 1” to account for Fe2O3 as reactant and 2 Fe as product

- Multiple “reaction 2” by 3 to account for 3 CO as reactant and

- 3 CO2 as product 50
Method 3: Calculating ∆𝒓 𝑮𝒐 from stepwise reactions
Rxn 1 (reverse): Fe2O3 (s) → 2 Fe (s) + 3/2 O2 (g) ∆𝒓 𝑮𝒐 = +742.2 kJ mol-1

Rxn 2 (x 3): 3 CO (g) + 3/2 O2 (g) → 3 CO2 (g) ∆𝒓 𝑮𝒐 = -771.6 kJ mol-1

Overall reaction and ∆𝒓 𝑮𝒐 :

51
 What is Gibbs Energy?
Once ∆𝒓 𝑮𝒐 is calculated, what does it physically represent?

∆𝒓 𝑮𝒐 is the maximum amount of useful work that can be done by the reaction
(if ∆𝒓 𝑮𝒐 < 0)

Example:
C8H18 (l) + 25/2 O2 (g) → 8 CO2 (g) + 9 H2O (l) ∆𝒓 𝑮𝒐 = -5296 kJ mol-1

Situation 1: Burning gasoline in a barrel: Most free energy “lost” as heat

Situation 2: Burning gasoline in a car engine: Some free energy used

towards work (engine operation), some “lost” as heat

52
 Gibbs Energy at Nonstandard States
Remember: ∆𝒓 𝑮𝒐 gives information on spontaneity when ALL substances are
present at standard state.

Example:
H2O (l) ⇌ H2O (g) ∆𝒓 𝑮𝒐 = 8.59 kJ mol-1 , at 298 K

Appears to be non-spontaneous, yet water can evaporate in a closed

container to some extent at 298 K

At standard state conditions, PH2O (g) = 1 bar. Water will condense in a closed
container at 298 K at this pressure (spontaneous in reverse direction)

However if PH2O (g) is 0 bar or very low, the reaction becomes spontaneous in
the forward direction
53
 Question
At standard state conditions, what is the reaction quotient Q for any
reaction?

A) 0

B) 1

C) Infinity

D) No way to tell without knowing the specific reaction

54
 Gibbs Energy at Nonstandard States
Previous clicker question gave a valuable piece of information:

If ∆𝒓 𝑮𝒐 < 0, then what is the relationship between Q and K?

If ∆𝒓 𝑮𝒐 > 0, then what is the relationship between Q and K?

If ∆𝒓 𝑮𝒐 = 0, then what is the relationship between Q and K?

55
 Gibbs Energy at Nonstandard States
To calculate If ∆𝒓 𝑮 under non-standard conditions, ∆𝒓 𝑮𝒐 is
modified using the following equation :

∆𝒓 𝑮 = ∆𝒓 𝑮° + 𝑹𝑻 𝒍𝒏 𝑸

R = 8.314 J mol-1 K-1

Q is the unitless reaction quotient from chapter 14 (recall the law

of mass action)

NOTE: ∆𝒓 𝑮𝒐 value must be valid at the 𝑻 in the formula

56
 Gibbs Energy at Nonstandard States
Example: Consider the following reaction:

2 NO (g) + O2 (g) ⇌ 2 NO2 (g) ∆𝒓 𝑮𝒐 = -71.2 kJ mol-1 , at 298 K

What is ∆𝒓 𝑮 if PNO = 0.100 bar, PO2 = 0.100 bar, PNO2 = 2.00 bar?

57
 Gibbs Energy and Equilibrium Constants
The equation:
∆𝒓 𝑮 = ∆𝒓 𝑮° + 𝑹𝑻 𝒍𝒏 𝑸

can be used to calculate K if ∆𝒓 𝑮° is known

Once equilibrium is reached, ∆𝒓 𝑮 = 0 and Q = K

𝟎 = ∆𝒓 𝑮° + 𝑹𝑻 𝒍𝒏 𝑲

∆𝒓 𝑮° = −𝑹𝑻 𝒍𝒏 𝑲

Once again, T must match ∆𝒓 𝑮°

Due to “ln K” term, small changes in ∆𝒓 𝑮° values can produce large changes
in K
58
 Question
If ∆𝒓 𝑮° = 0 for a reaction at 298 K, what is K at 298 K?

A) 0

B) 1

C) Infinity

D) No way to determine without knowing the reaction

59
 Equilibrium Constants and Temperature
Chapter 14: We learned K changes with temperature and is also dependent
on whether a reaction is exothermic or endothermic

How to calculate K at a particular temperature?

Method 1: Use the following equation to calculate ∆𝒓 𝑮𝒐 at temperature T

∆𝒓 𝑮𝒐 = ∆𝒓 𝑯𝒐 − 𝑻∆𝒓 𝑺

then, use the following equation to calculate K at same T value:

∆𝒓 𝑮° = −𝑹𝑻 𝒍𝒏 𝑲

Method 2: Use the van’t Hoff equation to combine the above two equations
into a convenient form

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 van’t Hoff Equation
Derivation:
∆𝒓 𝑮𝒐 = ∆𝒓 𝑯𝒐 − 𝑻∆𝒓 𝑺

∆𝒓 𝑮° = −𝑹𝑻 𝒍𝒏 𝑲

−𝑹𝑻 𝒍𝒏 𝑲 = ∆𝒓 𝑯𝒐 − 𝑻∆𝒓 𝑺

−∆𝒓 𝑯° ∆𝒓 𝑺
𝒍𝒏 𝑲 = +
𝑹𝑻 𝑹

Also has a useful “two-point form” which doesn’t need entropy information

𝑲𝟐 −∆𝒓 𝑯° 𝟏 𝟏
𝒍𝒏( ) = −
𝑲𝟏 𝑹 𝑻𝟐 𝑻𝟏
61
 Question
Experiments were performed to measure K at various temperatures.

If a graph was plotted with ln K on the y-axis and 1/T on the x-axis, which of
the following would give ∆𝒓 𝑯° ?

A) y-intercept

B) -slope

C) -(slope)(R)

𝐬𝐥𝐨𝐩𝐞
D) −
𝐑

62
 van’t Hoff Equation
𝑲𝟐 −∆𝒓 𝑯° 𝟏 𝟏
𝒍𝒏( ) = −
𝑲𝟏 𝑹 𝑻𝟐 𝑻𝟏

If K1 is known at temperature T1, then K2 can be predicted at temperature T2

as long as ∆𝒓 𝑯° is known

63