VIETNAM NATIONAL UNIVERSITY, HO CHI MINH CITY

INTERNATIONAL UNIVERSITY

LECTURE 11

THERMODYNAMICS AND
THERMOCHEMISTRY
Semester 3_2023-2024

Instructor: Dr. Ngo Thi Thuan

8/15/2024 1
Learning outcomes
STUDENTS SHOULD BE ABLE TO…

G1 Distinguish potential energy and kinetic energy

G2 Describe spontaneous vs nonspontaneous process
G3 Predict and explain sign of entropy change
G4 Calculate entropy change in the system from table of
standard values, entropy surrounding and entropy for
universe
G5 Calculate free energy change in the system from table
of standard values, entropy surrounding and entropy for
universe

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 1. BASIC CONCEPTS
❖Energy: is the ability to do work or transfer heat.
 REVIEW
Energy: Potential and Kinetic energy
Potential energy: the stored energy of position or state
Kinetic energy: the energy of motion or movement
Example:
- Raising a hammer: potential energy
due to position or state when falling
down has kinetic energy (the energy of
motion)

- A moving car has a lot of kinetic

energy.
 REVIEW

Example: Potential and Kinetic energy

- These skydivers have potential energy due to being

high up.
- After they jump this potential energy gets
converted into kinetic energy (and heat) as they speed
up.
Energy: Potential and Kinetic energy REVIEW

The total potential energy of the

molecule is the sum of the repulsions
and attractions between electrons and
nuclei:

The total kinetic energy of a molecule is the sum:

Trans Rot Vib

Energy: Potential and Kinetic energy
❖ An example of the kind of vibrations experienced by water
molecules

❖ The total energy of the molecule (its internal

energy E) is just the sum:

E = KEtotal + PEtotal
 REVIEW
Definitions: System and Surroundings
• The portion of the universe
that we single out to study
is called the system
(chemical reaction).

• The surroundings are

everything else (here, the
cylinder, piston and
everything beyond).
Exchange of Heat Between System and Surroundings
When heat is released by the system into the
surroundings, the process is exothermic.
Heat flows (violently) from system into
surrounding, temperature of the water and
System = K + H2O surrounding air increases
Exchange of Heat Between System and Surroundings
When heat is absorbed by the system from the surroundings,
the process is endothermic.
 REVIEW
Types of Systems
Vacuum

open closed isolated

Exchange:

mass & energy energy nothing

Spontaneous Processes
• Spontaneous processes
proceed without any outside
assistance.

• Processes that are

spontaneous in one direction
are nonspontaneous in the
reverse direction.
 2. DEFINITION OF THERMODYNAMICS AND
THERMOCHEMISTRY
❖ Thermodynamics: the study of energy change and
spontaneity.
Specifically, thermochemistry is the study of chemical
reactions and energy changes that involve heat.
Example_ energy change of burning CH4

CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)

Hf = - 824 kJ/mol

Q/A: How do we calculate this energy change?

 Review from lecture 5_bond energy
Example_ energy change of burning CH4
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)
Solution: (check bond energy in table 8.4)
Energies required to break each bond: C-H, O=O: 413, 495
kJ/mol
Energy release to form each bond: C=O, H-O: 799, 467
kJ/mol
Energy of CO2 and H2O formation:
ΔH =(1mol4DC-H+2molDO=O) – (1mol2DC=O +
2mol2DH-O)
= (1mol  4  413kJ/mol + 2mol  2  495kJ/mol) – (1mol  2
 799 kJ/mol+2mol  2  467 kJ/mol)
= - 824 kJ/mol
Since the value is negative → exothermic and released 824 kJ/
mol.
CH4(g) + O2(g) →CO2(g) + H2O(g) + 824 kJ/mol
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Enthalpy (H) is used to quantify the heat flow into or out
of a system in a process that occurs at constant
pressure. H = H (products) – H (reactants)
∆H = heat given off or absorbed during a reaction at constant
pressure

Hproducts > Hreactants Hproducts < Hreactants

H > 0 H < 0
16
 First Law of Thermodynamics
Energy can be converted from one form to another but
cannot be created or destroyed.
Esystem+Esurroundings = 0 or Esystem = -Esurroundings
Example:
CH4(g) + O2(g) →CO2(g) + H2O(g) + 824 kJ/mol
→ the system released energy to the surroundings.

CH4,
2O2
Energy

Change in energy +
heat
CO2,
H2O
17
 Thermodynamics vs. kinetics 2
Domain of thermodynamics
(the initial and final states)

❖ Thermodynamics →energy
Domain of kinetics
(the reaction pathway)

change and spontaneity of a

reaction which depends on
the properties of the reactants
and products

❖Chemical kinetics →rate of

reaction which depends on the
pathway from reactants to
products

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3. Calculating Reaction Enthalpies (Hr)
1. Bond energy (HB) (lec 05_chemical bonding)
Hint:

2. Hess’s law: combination of different reaction enthalpies to

get formation enthalpy (lec 10_solution and its properties)
C

H1
Enthalpy A + 2B H2

3. Standard enthalpies of formation (Hfo) m, n:

∆𝐻𝑟𝑜 = σ 𝑛∆𝐻𝑓𝑜 (products) - σ 𝑚∆𝐻𝑓𝑜 (reactants) stoichiometric
coefficients
Standard enthalpies of formation (Hfo)
Standard heat of a reaction forming 1 mol of compound from
pure elements in their most stable form at standard state
(P = 1atm, T = 298K) and measured from experiments
Example: CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
𝐻𝑖𝑛𝑡: ∆𝐻𝑟𝑜 = σ 𝑛∆𝐻𝑓𝑜 (products) - σ 𝑚∆𝐻𝑓𝑜 (reactants)

∆𝐻𝑟𝑜 = [2∆𝐻𝑓𝑜 (H2O) + ∆𝐻𝑓𝑜 (CO2)] − [∆𝐻𝑓𝑜 (CH4)+ 2∆𝐻𝑓𝑜 (O2)]

QA: How do we have ∆𝐻𝑓𝑜 for each reactants or products?
𝑜 𝑜
H2(g)+1/2O2(g)→H2O(l) ∆𝐻𝑓(𝐻 2
𝑂) =∆𝐻𝑟(𝐻2𝑂) = −285.8 𝑘𝐽/𝑚𝑜𝑙

𝑜 𝑜
Cgr + O2(g) → CO2(g) ∆𝐻𝑓(𝐶𝑂2
) = ∆𝐻𝑟(𝐶𝑂2
) = −393.5 𝑘𝐽/𝑚𝑜𝑙
O2(g) → O2(g) 𝑜
∆𝐻𝑓(𝑂 ) = ∆𝐻 𝑜
𝑟(𝑂 ) = 0
2 2

∆𝐻𝑓𝑜 of an element in its most stable state is zero

 Standard Enthalpies of Formation
Table 3.1. Standard Enthalpies of Formation,
Hf , at 298 K
Example: calculating reaction energy _ standard
enthalpies of formation
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
∆𝐻𝑟𝑜 = 𝑛∆𝐻𝑓𝑜 (products)- 𝑚∆𝐻𝑓𝑜 (reactants)
Solution: (check standard enthalpies of formation in table 3.1)
Standard enthalpies of reactants formation:
CH4, O2: -74.80, 0 kJ/mol
Standard enthalpies of products formation:
H2O,CO2:-285.8, -393.5 kJ/mol
Reaction energy:
∆𝐻𝑟𝑜 = [2∆𝐻𝑓𝑜 (H2O)+ ∆𝐻𝑓𝑜 (CO2)] − [∆𝐻𝑓𝑜 (CH4)+ 2∆𝐻𝑓𝑜 (O2)]
= (-2285.8 + (-393.5) - (-74.80 + 2  0) = - 1039.9 kJ/mol
Results from bond energy’s method: - 824 kJ/mol
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4. Spontaneous Processes
• Spontaneous processes
proceed without any outside
assistance.

• Processes that are

spontaneous in one direction
are nonspontaneous in the
reverse direction.
 Spontaneous reaction
• A spontaneous reaction proceeds in the forward direction
without any outside assistance (heat)
Example: rusting process 4Fe(s) + 3O2(g) → 2Fe2O3(s)
Q/A: Is Ho positive or negative?
Ho = - 824 kJ/mol
→ Exothermic reaction
→ Spontaneous reaction
Example: HgO decomposition 2HgO(s) → 2Hg(l) + O2(g)
Ho = 90.7 kJ/mol
→Endothermic reaction
→Nonspontaneous reaction
Spontaneous reaction and Gibbs free energy

Δ𝐺𝑜 = Δ𝐻𝑜 − 𝑇𝜟𝑺𝑜

ΔG<0: The reaction is spontaneous in the forward direction.

ΔG>0: The reaction is nonspontaneous. The reaction is
spontaneous in the opposite direction.
ΔG=0: The system is at equilibrium. There is no net change.

• The driving force for a spontaneous process is an increase in

the entropy

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 5. Entropy
• Entropy is a measure of the randomness or disorder of a
system.
Q/A: order disorder of system?
Liquid
Gas
Solid

Ssolid < Sliquid < Sgas

Δ𝑆 > 0 → 𝑖𝑛𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 𝑑𝑖𝑠𝑜𝑟𝑑𝑒𝑟
S = S final − Sinitial
Δ𝑆 < 0 → 𝑑𝑒𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 𝑑𝑖𝑠𝑜𝑟𝑑𝑒𝑟
Processes leading to an increase in entropy of the system

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Example: Br2(l) → Br2(g) I2(s) → I2(g)

S > 0 S > 0 28
Example
• Predict the sign of the entropy change (∆S) for
each of the following processes
a) Solid sugar is added into water to form solution
b) Iodine vapor condenses on a cold surface to form
crystals.
SOLUTION:
a) Sugar molecules in water becomes randomly
dispersed in larger volume → disorder increased in
solution (Sfinal > Sinitial → ∆S > 0).
b) Iodone molecules in crystal are retricted to vibration
only → disorder decreased in crystal (Sfinal < Sinitial →
∆S < 0).
 IE1
• Predict the sign of the entropy change (∆S) for
each of the following processes

a) H2O(g) → H2O(l)
b) 2N2O(g) → 2 N2(g) + O2(g)

2NO2(g) 2N2(g) + O2(g)

SOLUTION:
a) Water molecules becomes randomly dispersed in
larger volume → disorder decreased (Sfinal > Sinitial →
∆S < 0).
b) Net increase in the overall number of gas molecule →
disorder of system increases (Sfinal > Sinitial → ∆S > 0).
 Calculating Entropy Changes in reaction
Entropy changes for a reaction can be calculated in a
manner analogous to that by which H is calculated:

Δ𝑆° = Σ𝑛𝑆° products − Σ𝑚𝑆° reactants

Where:
n and m are the coefficients in the balanced chemical
equation.
So: standard entropy is the absolute entropy of a substance at
1 atm and 25°C.
Unit: J/mol.K
Standard Entropies (So)
Table 19.1 Standard Molar Entropies of Selected Substances
at 298 K
Substance So (J/mol.K)
H2(g) 130.6
N2(g) 191.5
O2(g) 205.0
H2O(g) 188.8
NH3(g) 192.5
CH3OH(g) 237.6
C6H6(g) 269.2
H2O(l) 69.9
CH3OH(l) 126.8
 Standard Entropies
• Standard molar entropies for gases are generally
greater than liquids and solids.
• Standard entropies increase with molar mass.
• Standard entropies increase with number of atoms in
a formula.
• Entropies of elements and compounds are all
positive (that is, S°>0) (By contrast, the standard enthalpy of
formation (H°f) for elements in their stable form is equal to zero, and
for compounds, it may be positive or negative)
Example _ Calculating ∆So
• Calculate ∆So at 25oC for the reaction:
H2O(g) → H2O(l) given the following standard entropy
values:
Substance So (J/K. mol)
H2O(g) 188.8
H2O(l) 69.91
Solution
Δ𝑆° = Σ𝑛𝑆° products − Σ𝑚𝑆° reactants
Δ𝑆° = 1𝑆° H2O(l) − 1𝑆° H2O(g) = 69.91 − 188.8
= −118.9 J/(K. mol) < 0
Water molecules becomes randomly dispersed in smaller
volume → disorder decreases (Sfinal < Sinitial → ∆S < 0).
Example
• Calculate ∆So at 25oC for the reaction:
2NiS(s) + 3O2(g) → 2SO2(g) + 2NiO(s) given the following
standard entropy values:

Substance So (J/K. mol)

SO2 (g) 248
NiO (s) 38
O2 (g) 205
NiS (s) 53
 2NiS(s) + 3O2(g) → 2SO2(g) + 2NiO(s)

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6. Relationship between entropy, enthalpy and Gibb
free energy - Second Law of Thermodynamics
❖Entropy of the universe increases in any spontaneous
processes.
❖This results in the following relationships:
∆𝑆𝑢𝑛𝑖𝑣 =∆Ssys + ∆Ssurr >0
∆Ssys and ∆Ssurr : changes in entropy occuring in the
system and the surroundings, respectively
Closed system → P
constant & no matter
changes, only heat
changes.
 6.1. Entropy Changes in system
Entropy changes in the system is entropy change for a
reaction:

Δ𝑆° = Σ𝑛𝑆° products − Σ𝑚𝑆° reactants

where n and m are the coefficients in the balanced

chemical equation.
 6.2. Entropy Changes in Surroundings
QA: What make disorder of system or entropy change?
• Heat that flows into or out of the system (reaction)
changes the entropy of the surroundings.
• For an isothermal process:

q surr −q sys
Ssurr = =
T T Exothermic Process
Ssurr > 0

• At constant pressure,

−Δ𝐻sys
Δ𝑆surr = at constant P
𝑇
Endothermic Process
Ssurr < 0
Example
• In the metallurgy of antimony, the pure metal is
recovered via different reactions, depending on
the composition of the ore. For example, iron is
used to reduce antimony in sulfide ores:
Sb2S3(s) + 3Fe(s) → 2Sb(s) + 3FeS(s) ∆H = -125 kJ
Calculate ∆Ssurr at 25oC and 1 atm?
SOLUTION: Δ𝑆𝑠𝑢𝑟𝑟 = -∆H/T
T = 25 + 273 = 298 K
Δ𝑆𝑠𝑢𝑟𝑟 = -∆H/T = -(-125 kJ)/(298K) = 419 kJ/K
Since this reaction is exothermic and heat flow occurs to
the surroundings, increasing the randomness of the
surroundings
 6.3.Entropy Change in the Universe
• The universe is composed of the system and the
surroundings.
• Therefore,
Δ𝑆universe = Δ𝑆system + Δ𝑆surroundings

• For spontaneous processes

Suniverse  0
• For unspontaneous processes
∆Suniverse < 0
Example
• Consider the combustion of propane gas
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(g) ∆H = -2044 kJ/mol
Determine sign of ∆Suniverse at 25oC and 1 atm? Is the
reaction spontaneous?
𝑘𝐽
−Δ𝐻sys −2044
𝑚𝑜𝑙
Δ𝑆surr = =− = +6.86 x103 J/mol.K
𝑇 298𝐾

C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(g)

6 mol gas 7 mol gas →Ssys > 0

Suniverse = Ssystem + Ssurroundings
>0 >0 >0
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8/15/2024 43
 6.4.Total Entropy and spontaneous process
Δ𝑆universe = Δ𝑆system + Δ𝑆surroundings > 0

• Multiply by −T:
−𝑇Δ𝑆universe = −𝑇Δ𝑆system + Δ𝐻system < 0
• Rearrange:

−𝑇Δ𝑆universe = Δ𝐻system − 𝑇Δ𝑆system < 0

−T Suniverse the Gibbs Free Energy ( G ) :

Δ𝐺 = Δ𝐻 − 𝑇Δ𝑆 < 0
8/15/2024 44
 Total Entropy and nonspontaneous process
Δ𝑆universe = Δ𝑆system + Δ𝑆surroundings < 0

• Multiply by −T:
−𝑇Δ𝑆universe = −𝑇Δ𝑆system + Δ𝐻system > 0
• Rearrange:
−𝑇Δ𝑆universe = Δ𝐻system − 𝑇Δ𝑆system > 0

−T Suniverse the Gibbs Free Energy ( G ) :

Δ𝐺 = Δ𝐻 − 𝑇Δ𝑆 > 0
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7. Gibbs Free Energy
G = H − T S
1) If G < 0 → the forward
reaction is spontaneous.

2) If G = 0, the system is
at equilibrium.

3) If G >0 → the reaction

is nonspontaneous, but
spontaneous in the reverse
direction.
7.1. Calculating Free Energy Changes
1. Standard free energy of formation, ∆Gfo:

Analogous to standard enthalpies of formation are

standard free energies of formation, ∆Gfo:
G° =  nGf ° (products ) − mGf ° (reactants )
where n and m are the stoichiometric coefficients.

2. Ho, So

Δ𝐺𝑜 = Δ𝐻𝑜 − 𝑇𝜟𝑺𝑜

Standard free energy of formation, ∆Gfo
Table 19.2 Conventions Used in Establishing
Standard Free Energies
State of Matter Standard State
Solid Pure solid
Liquid Pure liquid
Gas 1 atm pressure
Solution 1 M concentration
Element Gof =0, for element in standard
state, example: Na, O2, F2...
Delta G naught of f = 0
 8/15/2024 49

Example _ Calculating Go from standard

Using the following data at 25oC
Cdiamond(s) + O2(g) → CO2(g) Go = - 397 kJ/mol
Cgraphite(s) + O2(g) → CO2(g) Go = - 394 kJ/mol

Calculate Go for the reaction: Cdiamond(s) → Cgraphite(s)

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Ho, So

G = H − T S
Example _ Calculating Ho, So, Go
Consider the reaction 2SO2(g) + O2(g) → 2SO3(g)
carried out at 25oC and 1 atm. Calculate Go using the
following data.

Substance Hof (kJ/mol) Sof (J/mol.K)

SO2(g) -297 248
SO3(g) -396 257
O2(g) 0 205
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7. Temperature of phase change in Δ𝐺𝑜 40

Go Ho
30
= - TSo
Go > 0 → nonspontaneous process
20

Free energy (Kj/mol)

Go = 0 10

T*
T*= Ho/So 0
298 318 338
Go = 0
358 378 398 418 438 458 478

Temperature (K)
-10

Example Go < 0 → spontaneous process

-20

2NaHCO3(s)→2Na2CO3(s)+CO2(g) + H2O(g)

Hor = + 135.6 kJ/mol So = + 0.334 kJ/mol

T= Ho/So = 135.6/0.334 = 406 K

T = 406 – 273 = 133oC
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8/15/2024 54
7.3. How signs of ΔH and ΔS affect on reaction
spontaneity
Consider the reaction: H2O2(aq) →H2O(l) + O2(g)

Hor = -196 kJ/mol So = + 125 J/K.mol

Go = Ho - TSo

Go = - 196 kJ/mol - (298K)x(0.125 kJ/K.mol) = -233 kJ/mol

H S -TS G = H – TS
Reaction Characteristics
Spontaneous at all
− + − −
temperatures
How signs of ΔH and ΔS affect on reaction
spontaneity
Consider the reaction: 3O2(g) → 2O3(g)
Hor > 0 So < 0
Go = Ho - TSo

Go = Ho - TSo

H S -TS G = H – TS
Reaction Characteristics
Nonspontancous at all
+ − + +
temperatures
How signs of ΔH and ΔS affect on reaction
spontaneity
Consider the reaction: NH3(g) + HCl(g) →NH4Cl(s)
Hor < 0 So < 0
Go = Ho - TSo ~ Y = ax + b

Free nonspontaneous
energy
Temperature
spontaneous

H S -TS G = H – TS
Reaction Characteristics
Spontaneous at low T;
− − + + or −
nonspontaneous at high T
How signs of ΔH and ΔS affect on reaction
spontaneity
Consider the reaction: 2HgO(s) →2H2O(l) + O2(g)
Hor > 0 So > 0
Go = Ho - TSo ~ Y = ax + b

nonspontaneous
Free
energy Temperature
spontaneous

H S -TS G = H – TS
Reaction Characteristics
Spontaneous at high T;
+ + − + or −
nonspontaneous at low T
Summary of ΔH and ΔS signs and spontaneity

No. H S -TS G = H – TS Reaction

Characteristics Example
Spontaneous at all H2O2(aq) →H2O(l) +
1 − + − −
temperatures O2(g)
Nonspontancous at
2 + − + + 3O2(g) → 2O3(g)
all temperatures
Spontaneous at
low T; NH3(g) + HCl(g)
3 − − + + or −
nonspontaneous at →NH4Cl(s)
high T
Spontaneous at
high T; 2HgO(s) →2H2O(l) +
4 + + − + or −
nonspontaneous at O2(g)
low T
9. Application of Free Energy in chemical equilibrium

9.1. Calculating G if Q is given and vice versa

Under any conditions, standard or nonstandard, the free
energy change can be found this way:

G = G° +RT ln Q
G = non-standard free energy
G° = standard free energy (from tables) =fixed value
R = 8.314 J/K·mole
T = temp in K
Q = reaction quotient
 Example _ Calculating Go
One method for synthesizing methanol (CH3OH) involves
reacting carbon monoxide and hydrogen gases:
CO(g) + 2H2(g) → CH3OH(l)

Calculate G at 25oC for this reaction where carbon

monoxide gas at 5.0 atm and hydrogen gas at 3.0 atm are
converted to liquid methanol

G = G° +RT ln Q

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8/15/2024 62
9.2. Predict direction of chemical equilibrium
Reactants  Products

G0 < 0 → G < 0 G0 > 0 → G > 0

G = G° +RT ln Q 63
 Example _ dissociation constant of water
Consider the dissociation reaction:
2H2O(l)  H3O+(aq) + OH-(aq)
Go = 79.98 kJ/mol.
Predict sign of K value?
Determine K?
Solution:

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 Example _ Free energy and equilibrium
Consider the ammonia synthesis reaction
N2(g) + 3H2(g)  2NH3(g)

Where Go = -33.3 kJ/mol of N2 consumed at 25oC. For each

of the following mixtures of reactants and products at 25oC,
predict the direction in which the system will shift to reach
equilibrium.
a. PNH3 = 1.00 atm, PN2 = 1.47 atm, PH2 = 1.00 x 10-2 atm
b. PNH3 = 1.00 atm, PN2 = 1.00 atm, PH2 = 1.00 atm

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9.3. Calculating constant (K) at equilibrium state
• At equilibrium, Q = K, and G = 0.
• The equation becomes

0 = G° +RT ln K
• Rearranging, this becomes
QA: How does sign of Go
G° = -RT ln K affect on K?

or G °
−
K =e RT
 Example _ Free energy and equilibrium
The overall reaction for the corrosion (rusting) of iron by
oxygen is 4Fe(s) + 3O2(g)  2Fe2O3(s)
Using the following data, calculate the equilibrium constant
for this reaction at 25oC.

Substance Hof (kJ/mol) Sof (J/mol.K)

Fe2O3(s) -826 90
Fe(s) 0 27
O2(g) 0 205

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