Lecture 2.2.1.

2 LAW OF THERMODYNAMICS I
nd

Introduction to a lecture series by

Physical Chemistry Dr. T.A. Ntho
Fluid States and Thermodynamics Department of Chemistry
C2640
NUL
Limitations of the 1st Law of Thermodynamics

WORK
system surroundings
Internal Energy (U) HEAT internal energy (U)

∆𝑈𝑠𝑦𝑠 = −∆𝑈𝑠𝑢𝑟𝑟
Limitations of the 1st Law of Thermodynamics

WORK
system surroundings
Internal Energy (U) HEAT internal energy (U)

∆𝑈𝑠𝑦𝑠 = −∆𝑈𝑠𝑢𝑟𝑟
What is spontaneous?
What is spontaneous?
The 2nd Law of Thermodynamics

The 2nd law of thermodynamics leads to

the deduction of a state function, entropy,
that for isolated systems the equilibrium
position correponds to maximum entopy
Cyclic Heat Engines

cyclic heat engine:

converts heat to
continuous mechanical
work
Cyclic Heat Engines

cyclic heat
heat work
engine

Efficiency of |𝑤𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 𝑏𝑦 𝑒𝑛𝑔𝑖𝑛𝑒|

an engine
ϵ=
|ℎ𝑒𝑎𝑡 𝑖𝑛𝑝𝑢𝑡|
Cyclic Heat Engines

cyclic heat
heat work
engine

Efficiency of |𝑤𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 𝑏𝑦 𝑒𝑛𝑔𝑖𝑛𝑒|

an engine
ϵ=
|ℎ𝑒𝑎𝑡 𝑖𝑛𝑝𝑢𝑡|
Cyclic Heat Engines
Recall: reversible isothermal expansion of an ideal gas

Pext = Pgas
T

V
Vi Vf
Cyclic Heat Engines

cyclic heat
heat work
engine

Efficiency of |𝑤𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 𝑏𝑦 𝑒𝑛𝑔𝑖𝑛𝑒|

an engine
ϵ= = 𝟏𝟎𝟎%
|ℎ𝑒𝑎𝑡 𝑖𝑛𝑝𝑢𝑡|
Cyclic Heat Engines

Studies by French engineer, Sadi Carnot shows that

for an engine to produce continuous mechanical
work, it must exchange heat with 2 bodies at
different temperatures
Cyclic Heat Engines

cyclic heat
heat in work
engine
(heat reservoir)

heat out
(cold reservoir)
Kelvin-Planck Statement of the 2nd Law

“It is impossible for a system to undergo a

cyclic process whose sole effects are the
flow of heat into the system from a heat
reservoir and the performance of an
equivalent amount of work by the system
on the surroundings”
Layman’s Statement of Thermodynamics

The 1st Law The 2nd Law

says you says you
CAN’T WIN CAN’T BREAK EVEN
The Carnot Cycle
Basic principle of a heat engine:

piston
The Carnot Cycle
Basic principle of a heat engine:

high-temperature steam in:

piston cooler gas

The Carnot Cycle
Basic principle of a heat engine:

exhaust steam

piston
The Carnot Cycle
Basic principle of a heat engine:

high-temperature steam in

cooler gas
piston
The Carnot Cycle
Basic principle of a heat engine:

exhaust steam

piston
The Carnot Cycle
The Carnot Cycle: a reversible cycle that is the most efficient engine possible

TH

TC
The Carnot Cycle
The Carnot Cycle: a reversible cycle that is the most efficient engine possible
P

(1) isothermal expansion

(3) adiabatic
compression

TH
TH
(2) Adiabatic expansion

TC
(3) Isothermal compression TC
V
The Carnot Cycle
The Carnot Cycle: a reversible cycle that is the most efficient engine possible
P

P1

P2

TH
P4

P3 TC

V
V1 V4 V2 V3
The Carnot Cycle
(1) Isothermal Reversible Expansion:

P
Heat is absorbed from the high-
P1
A temperature reservoir to do work

P2 B
TH

TC
V
V1 V2
The Carnot Cycle
(1) Isothermal Reversible Expansion:

P1
A

P2 B
TH

TC
V
V1 V2
The Carnot Cycle
(2) Reversible Adiabatic Expansion

P Work is done by the engine

P2 B
TH

P3 C T
C

V
V2 V3
The Carnot Cycle
(2) Reversible Adiabatic Expansion

P Work is done by the engine

P2 B
TH

P3 C T
C

V
V2 V3
The Carnot Cycle
(3) Reversible Isothermal Compression
P Heat leaves the system into the cold
reservoir

TH
P4

P3
D C T
C

V
V4 V3
The Carnot Cycle
(3) Reversible Isothermal Compression
P

TH
P4

P3
D C T
C

V
V4 V3
The Carnot Cycle
(4) Reversible Adiabatic Compression

P System/engine returns to original

conditions
P1
A

TH
P4
D
TC
V
V1 V4
The Carnot Cycle
(4) Reversible Adiabatic Compression

P System/engine returns to original

conditions
P1
A

TH
P4
D
TC
V
V1 V4
The Carnot Cycle
Steps q w ΔU
P

B
TH
D
C TC
V
The Carnot Cycle
• Consider the adiabatic processes:
P

B
TH

D C T
C

V
V1 V4 V2 V3
The Carnot Cycle
• Consider the adiabatic processes:
P

B
TH

D C T
C

V
V1 V4 V2 V3
The Carnot Cycle
• Consider the adiabatic processes:
P

B
TH

D C T
C

V
V1 V4 V2 V3
The Carnot Cycle
• Simplifying wcycle
The Carnot Cycle
• Simplifying qcycle
The Carnot Cycle
• The overall carnot cycle:
Calculating Efficiency of the Carnot Cycle
|𝑤𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 𝑏𝑦 𝑒𝑛𝑔𝑖𝑛𝑒|
ϵ=
|ℎ𝑒𝑎𝑡 𝑖𝑛𝑝𝑢𝑡|

TH

TC
Calculating Efficiency of the Carnot Cycle
|𝑤𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 𝑏𝑦 𝑒𝑛𝑔𝑖𝑛𝑒|
ϵ=
|ℎ𝑒𝑎𝑡 𝑖𝑛𝑝𝑢𝑡|

TH

TC
Calculating Efficiency of the Carnot Cycle
• Additional Implications:
The Carnot Cycle
• Combining the equations for efficiency:

Equation considers all the heats involved in the system!

Since the system is cyclic (starts and ends at same

conditions), the fact that the heat/temperature ratios add
up to zero suggests that the relationship is a state function!

The reversible changes, a relationship between heat

and absolute temperature is a state function, which we
define as ENTROPY
Entropy
Entropy (S): a thermodynamic state function. Units: J/mol-K
Entropy
• Recall: the Carnot cycle (reversible steps) is the most efficient cycle
– Any irreversible change is a less efficient conversion of heat to work than a reversible change

Recall:
Entropy
• Recall: the Carnot cycle (reversible steps) is the most efficient cycle
– Any irreversible change is a less efficient conversion of heat to work than a reversible change

For a complete cycle with infinitely small steps:

Entropy
• Consider a cyclic process of both irreversible and reversible steps:

Since the cycle involves an

irreversible step, this
relationship holds:
Expression can be split into the two steps:
Entropy
• Consider a cyclic process of both irreversible and reversible steps:

Flip limits of integration

dS
Entropy
• Consider a cyclic process of both irreversible and reversible steps:

In general:
Entropy
• Generalizations: The Clausius Inequality

Irreversible, therefore spontaneous process reversible, spontaneous process

IMPLICATION:

NOT allowed
Entropy
For isolated systems:

Entropy increases with

spontaneous changes in an
isolated system
Entropy
For non-isolated systems, the entropy of the surroundings must also be
considered!
2nd Law of Thermodynamics
2nd Law of Thermodynamics
• Summary of the first 2 laws of thermodynamics:

1st LAW: energy of the universe is constant

2nd LAW: entropy of the universe is leading to a maximum

Calculating ΔSuniv
𝑑𝑆𝑢𝑛𝑖𝑣 = 𝑑𝑆𝑠𝑦𝑠 + 𝑑𝑆𝑠𝑢𝑟𝑟

đ𝑞𝑟𝑒𝑣 must use reversible heat!

𝑑𝑆𝑠𝑦𝑠 =
𝑇
Calculating ΔSuniv
𝑑𝑆𝑢𝑛𝑖𝑣 = 𝑑𝑆𝑠𝑦𝑠 + 𝑑𝑆𝑠𝑢𝑟𝑟

irreversible

S1 đ𝑞𝑟𝑒𝑣 S2
𝑑𝑆𝑠𝑦𝑠 =
𝑇

reversible

a reversible pathway can be used to calculate ΔS for an irrevesible process

Calculating ΔSuniv
𝑑𝑆𝑢𝑛𝑖𝑣 = 𝑑𝑆𝑠𝑦𝑠 + 𝑑𝑆𝑠𝑢𝑟𝑟

Example 1. Heat flow from the system to the surroundings

System -q Surroundings
(Tsys) (Tsurr)
Calculating ΔSuniv
𝑑𝑆𝑢𝑛𝑖𝑣 = 𝑑𝑆𝑠𝑦𝑠 + 𝑑𝑆𝑠𝑢𝑟𝑟

Example 2. Cyclic heat engine with no cold reservoir

heat in work
System
Calculating ΔSuniv
𝑑𝑆𝑢𝑛𝑖𝑣 = 𝑑𝑆𝑠𝑦𝑠 + 𝑑𝑆𝑠𝑢𝑟𝑟

Example 2. Cyclic heat engine with a cold reservoir

heat in work
System

heat out
Calculating ΔSuniv
Problem 2.2.1. (a) Calculate ΔSuniv when 1 mol of ice melts at in a room at 25°C, 1 atm. Is the
process spontaneous? (b) Calculate ΔSuniv when 1 mol of ice melts in a room at -10°C, 1 atm. Is the
process spontaneous? ΔHfusion=6.02 kJ/mol.
Calculating ΔSuniv
Problem 2.2.1. (a) Calculate ΔSuniv when 1 mol of ice melts at in a room at 25°C, 1 atm. Is the
process spontaneous? (b) Calculate ΔSuniv when 1 mol of ice melts in a room at -10°C, 1 atm. Is the
process spontaneous? ΔHfusion=6.02 kJ/mol.
Calculating of ΔSsys for other processes
Additional processes for closed systems:
1. Isochoric
2. Isobaric
3. Isothermal
4. Adiabatic
5. Combined processes
6. Reversible phase changes
7. Irreversible phase changes
8. Mixing of inert, ideal gases at constant T and P
Calculating of ΔSsys
1. Isochoric Process
Calculating of ΔSsys
2. Isobaric Process
Calculating of ΔSsys
3. Isothermal Process
Calculating of ΔSsys
4. Adiabatic Process: Revesible
Calculating of ΔSsys
4. Adiabatic Process: Irreversible
Calculating of ΔSsys
5. Combined Processes
Problem 2.2.2. Determine ΔS for 1 mole of He undergoing the following process
(assume ideal gas behavior):
He(298K, 1.50 atm) → He(100.0 K, 15.0 atm)
Calculating of ΔSsys
6. Reversible Phase Changes
Calculating of ΔSsys
7. Irreversible Phase Changes
Calculating of ΔSsys
8. Mixing of Inert, Ideal Gases at constant T, and P
Calculating of ΔSsys
8. Mixing of Inert, Ideal Gases at constant T, and P
Calculating of ΔSsys
8. Mixing of Inert, Ideal Gases at constant T, and P
Calculating of ΔSsys
8. Mixing of Inert, Ideal Gases at constant T, and P
Calculating of ΔSsys
8. Mixing of Inert, Ideal Gases at constant T, and P
Calculations of Entropy Changes
Problem 2.2.3. Calculate the entropy of mixing 10.0 L of N2 with 3.50 L of N2O at
300.0 K and 0.550 atm. Assume that the volumes are additive.