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Part II: Fundamental laws of chemical

processes

Chapter 1: Thermodynamics of
chemical reactions

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Chapter 1: Thermodynamics of chemical

reactions
1.1. Principles of heat flow
✓Almost chemical reactions absorb or release
energy, in the form of heat. It is important to
understand the distinction between thermal energy
and heat.
✓Heat is the transfer of thermal energy between two
bodies having different temperatures. Speak “Heat
flow” from a hot object to a cold one.
✓Thermochemistry is the study of the heat change in
chemical reactions

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Chapter 1: Thermodynamics of chemical

reactions
1.1.1. System and surroundings
1. The system is that part of the universe on which
attention is focused.
2. The surroundings are the rest of the universe outside the
system.
Example: a sample of solution in contact with a hot plate

The solution is the system

The hot plate and the glass

holding the solution is the
surroundings

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3. There are three types of systems:
✓ An open system can exchange mass and energy,
usually in the form of heat with its surroundings
An open system consist of a quantity of water in an
open container.
✓A closed system exchanges energy, but does not mass

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Chapter 1: Thermodynamics of chemical

reactions
✓An isolated system does exchange neither heat
nor mass with surroundings
If we place the above flask in totally insulated
container, we obtained an isolated system.
1.1.2. Direction and sign of heat flow
✓ Heat (q) has positive (q>0) value when heat flows
from the surroundings into the system.
✓Heat (q) has negative (q<0) value when heat flows
out of the system into the surroundings

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Part II: Fundamental laws of chemical

processes
✓ An endothermic process, in which heat flows from
the surroundings into the system
Example: the melting of ice:
H2O(s) → H2O(l)
The process absorb heat from the surroundings, the
temperature of surroundings drops as they give up
heat to the system
✓An exothermic process, in which heat flows from
system into the surroundings
CH4(g) + O2(g) → CO2(g) + H2O (l) q<0, it is an
exothermic process

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Chapter 1: Thermodynamics of chemical

reactions
1.1.3. State Properties
a. State Properties
T, P, composition (concentration, moles), V
2 kinds: - extensive property: depend on
amount of matter (mass(m), volume (V),
moles)
- Intensive property: does not depend
on amount of matter

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b. State function
Its value depends only on the state of the
system, not on the way by which the system
reached that state.
U (internal energy), S (entropy), H (enthalpy)

∆U=U2-U1; ∆S=S2-S1; ∆H=H2-H1

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Chapter 1: Thermodynamics of chemical

reactions
1.2. The first law of thermodynamics
1.2.1. U, q, W
- U: is the total energy contained in the
system.
- q: Heat
- W: Work

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Chapter 1: Thermodynamics of chemical

reactions
1.2.2. Statement of the first law of thermodynamic
-
- When the system transfers from state (1) to
state (2), the total of heat (q) and work (W)
exchanged with surrounding equal the
change of internal energy (U) of the system
∆U=q+W
+ for isolated system, q=0, W=0 → ∆U=0
+ initial and final state coinside → ∆U=0

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Chapter 1: Thermodynamics of chemical

reactions
1.2.3. qp and qv
We have: ∆U=q+W; W=-P*∆V
→ ∆U=q-P*∆V
- If a process taking place at constant V, so
∆V=0, → ∆U=qv
- If a process taking place at constant P
∆U=q-P*∆V →qp= ∆U + P*∆V= (U2-U1) + P*(V2-V1)
Or qp=(U2+PV2)-(U1+PV1)
H=U+PV (H: enthalpy); ∆H= ∆U+P*∆V
→qp= H2-H1 =∆H
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Chapter 1: Thermodynamics of chemical

reactions
qp=qv+P*∆V
- For liquid and solid system, qp=qv
- For gas system: qp=qv+P*∆V= qv+∆nRT
or ∆H= ∆U + ∆nRT
Ex: Cgr + O2(g) → CO2(g) ∆n=1-1=0
N2(g) + 3H2(g) → 2NH3(g) ∆n=2-(1+3)=-2

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1.3. The application of the first law of

thermodynamics to chemistry. Enthalpy (heat) of
reaction
1.3.1. The standard state
- Under standard pressure (P=1atm)
- Beside, we have some specific temperature
T=25 oC=298K
1.3.2. The standard enthalpy (heat) of reaction
When the substances of the reaction in the
standard state (P=1 atm), at temperature of T,
we have standard enthalpy (heat) of reaction
∆HoT

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• Note: the ∆HoT for reation refers to the

enthalpy ∆H when:
+ The reactants in stoichiometric ratios
+ are converted completely to the
products with stoichiometric ratios
+ Temparature of reactants and
products are the same

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1.3.3. Calculation the enthalpy of reaction

1. Calculation the enthalpy of reaction by enthalpy of
formation
a. Enthalpy (Heat) of formation (∆Hof)
The standard enthalpy (Heat) of formation (∆H of) of a
substance is the enthalpy change for the reaction in
which 1 mole of the substance is formed from its
elements in their standard and stable states.
Cgr + O2(g) → CO2(g) ∆HoT
From the definition, we have ∆HoT= ∆HoT,f(CO2)
→∆HoT,f(elements)=0
b. Calculation the enthalpy of reaction by enthalpy of
formation
aA + bB → cC + dD
∆H T= (c∆H T,f(C) + d∆HoT,f(D)) - (a∆HoT,f(A) + b∆HoT,f(B))
o o

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1.3.3. Calculation the enthalpy of reaction

2. Calculation the enthalpy of reaction by
enthalpy of combustion
a. The enthalpy of combustion (∆HoC)
The standard enthalpy of combustion ∆HoC of a
substance is the enthalpy change for the reaction in
which 1 mole of the substance is completely
combusted to form oxides with the highest oxidation
number at standard state
Cgr + O2(g) → CO2(g) ∆HoT(1)
Cgr + 1/2O2(g) → CO(g) ∆HoT(2)
→∆HoT(1)= ∆HoT,C(C)
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1.3.3. Calculation the enthalpy of reaction

b. Calculation the enthalpy of reaction by

enthalpy of combustion
aA + bB → cC + dD
∆HoT= (a∆HoT,C(A) + b∆HoT,C(B)) - (c∆HoT,C(C) + d∆HoT,C(D))

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1.3.3. Calculation the enthalpy of reaction

3. Hess’s law
a. Statement
The enthalpy change for a reaction in the
condition of P, or V =const is only depends on
the initial and final state, but not on the
intermediate states

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1.3.3. Calculation the enthalpy of reaction

b. Consequence of Hess law
- Calculate the enthalpy change of a reaction, if
the reaction is one of a process
- The enthalpy change of reverse reaction =-∆H

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1.3.3. Calculation the enthalpy of reaction

4. Calculation the enthalpy change by bond energy

∆H = ΣEproduct- ΣEreactants
Example: Use the bond energy to estimate the heat
of reaction at 298K
N2(g) + H2(g) ↔ 2NH3(g)
∆Ho298=2*3EN-H - (EN≡N + 3EH-H)

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1.4. The second law of thermodynamics

1.4.1. Spontaneous Process

1.4.2. Entropy, S
Entropy is a measure of the disorder of a system
The greater disorder of a system, the greater its
entropy

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• Entropy increases with dispersal of particles so,

entropies of gases are larger than liquids and liquid
entropies are larger than solids.
Ssolid < Sliquid < Sgas

• Entropies are greater for :

- More complex molecules
- Increased temperatures
- When volume increases for gases

• ΔS=ΣSf - ΣSi
ΔS > 0: Entropy increases
ΔS < 0: Entropy decreases

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* Entropy change of a system

Given a reaction: aA + bB → cC + dD
The standard entropy change of reaction:
∆So = (c.SoC + d.SoD) - (a.SoA + b.SoB)
S: J/mol.K

1.4.3. Statement of the second law of thermodynamics

- For the spontaneous process:
∆Sisolated sys = ∆Ssys + ∆Ssur>0
- For the equilibrium process
∆Sisolated sys = ∆Ssys + ∆Ssur=0
We have, ∆Hsys = - ∆Hsur
∆Ssur = ∆Hsur/T
→ ∆Ssur = -∆Hsys/T

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1.4.4. Gibbs free energy

∆Sisolated sys = ∆Ssys + ∆Ssur = ∆Ssys-∆Hsys/T>0

↔ T.∆S isolated sys = T.∆Ssys-∆Hsys>0
↔ -T.∆S isolated sys = ∆Hsys -T.∆Ssys<0
If ∆H -T.∆S<0, the process must be
spontanneous
G =H-TS
∆G = ∆H-T.∆S
We have: ∆G = ∆H-T.∆S <0

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1.4.5. Methods for calculating the standard free

energy change of reactions

1. The standard free energy change (∆GoT)

aA + bB → cC + dD
∆GoT=[c.∆Gof,(C) + d.∆Gof,(D)] - [a∆Gof,(A) + b.∆Gof,(B)]
(∆Gof,(i) : is standard free energy of formation of
a compound)

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1.4.5. Methods for calculating the standard free

energy change of reactions

2. Calculating
a. Calculating ∆Go of a reaction from ∆Gof of
substances in the reaction
Example:
CH4(g) + 2O2(g) → CO2(g) + 2H2O (l)
∆Gof,298 -50,8 0 -394,4 -237,2
(kJ/mol)
∆Go298 = -818 kJ<0, the reaction is
spontaneous at standard condition at 298K
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1.4.5. Methods for calculating the standard free

energy change of reactions
2. Calculating
b. Calculation with the equation ∆G = ∆H-T.∆S
∆G = ∆H-T.∆S
If in the standard condition, at temperature of T,
∆GoT = ∆HoT-T.∆SoT

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1.4.5. Methods for calculating the standard free

energy change of reactions
Example: Calculate the free energy change at
standard condition, at T=298K
N2(g) + O2(g) → 2NO(g)
∆Hof,298 0 0 90,25
(kJ.mol-1)
So298 191,5 205 210,7
(J.mol-1.K-1)
∆Ho298 = 2∆Hof,298 (NO) – (∆Hof,298 (N2)+ ∆Hof,298 (O2) )
=180,5 (kJ)
∆So298 = 2.So298 (NO) – (So298 (N2)+ So298 (O2) )= 24,9 (J.K-1)
∆Go298 = ∆Ho298 -T ∆So298 =180,5-298*24,9*10-3
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What are Spontaneous Processes ?

•Spontaneous processes are
those that can proceed without
any outside intervention.

• For example, the gas in

vessel B will spontaneously
effuse into vessel A, but once
the gas is in both vessels, it
will not spontaneously revert
to its original state.

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Spontaneous Processes

Processes that are

spontaneous in one direction
are nonspontaneous in the
reverse direction.

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For a constant-temperature process:

Gibbs free energy (G)

ΔG < 0 The reaction is favorable (spontaneous) in the forward direction.

No outside energy is needed
Product formation is favored

ΔG > 0 The reaction is unfavorable (non-spontaneous) as written.

The reaction is favorable (spontaneous) in the reverse direction
Reactant formation is favored

ΔG = 0 The reaction is at equilibrium and reactant and product

formation are equally favored

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