Department of Chemical and Biomolecular Engineering

CN2121 – Introduction to Chemical Engineering

Thermodynamics
Lecture 1: Introduction

Read Chapter 1 & 2

 Case Study: Monsanto Process 2

o  Can the reaction occur? At what temperature?

o  How much energy does it require to heat the starting material to a certain
temperature?
o  Is the reaction endothermic or exothermic?
o  How can you separate the products? How much purity can you reach?
o  How much energy do you need to purify 1 kg of acetic acid from raw
Case Study: Monsanto Process 3

o  How does the catalyst work at the

molecular level?
o  How can we design cheaper catalyst
with higher activity/stability?
o  How can we better mix CO and
methanol? What are the flow behaviors
for each of them?
o  How can we better design the reactor
to enhance the space time productivity?
o  How can we take the heat away from
the reactor at an appropriate rate, so
that the temperature is kept just right?
 Thermodynamics: Fundamental Science 4

Albert Einstein
Thermodynamics is the only physical theory of general
nature of which I am convinced that it will never be
overthrown.
Arnold Sommerfield
Thermodynamics is a funny subject. The first time you go
through it, you don't understand it at all. The second time
you go through it, you think you understand it, except for one
or two small points. The third time you go through it, you
know you don't understand it, but by then you are so used to
it, it doesn’t bother you any more.
Thermodynamics in Chemical Engineering 5
 Classical vs. Statistical Thermodynamics 6

Classical Thermodynamics Statistical Thermodynamics

Macroscopic Microscopic

Temperature, Atoms,
Pressure, Molecules,
… …

The Measurable Results of Molecular Interactions

​3/2 𝑘𝑇=​1/2 𝑚​𝑣↑2 
Four Laws of Thermodynamics 7
 Thermodynamics: Module Content (Part I) 8

o  Heat
o  Energy
•  Forms of energy (chemical, mechanical, heat…)
•  Conservation of energy
•  Energy transformation
Typical Systems that Transform Energy!
 Thermodynamics: Power Plant 9

http://www.alstom.com/power/gas-power/turnkey-power-plants/combined-cycle/ka24/
Power Plant 10
 Thermodynamics: Internal Combustion Engine 11

http://www.driving-test-success.com/how-cars-work.htm

How a car engine

works?
Internal Combustion Engine 12
 Thermodynamics: Gas Turbine Engine 13

https://www.scitecheuropa.eu/making-aircraft-combustion-chambers-sustainable/
98382/
 Gas Turbine Engine 14

2 3
1 4

h
ttp://www.yourdictionary.com/gas-
turbine
Brayton Cycle
 Thermodynamics: Air Conditioner 15

h
ttp://www.airintelligence.co.uk/cooling-air-
conditioners/

In the cycle on the right,

which side is indoor and
which is outdoor?
 Quiz 16

What can not be obtained

by using thermodynamic
principles?

A.  Power generated from the turbine

B.  The existing temperature of water from the condenser
C.  The time required to heat the water into steam with
desired temperature and pressure in the boiler
D.  The overall efficiency of the process
 Department of Chemical and Biomolecular Engineering

CN2121 – Introduction to Chemical Engineering

Thermodynamics
Lecture 2: Basic Concepts

Read Chapter 1 & 2

Basic Concepts: Temperature (T) and Pressure (P) 2

o Temperature (T)

o Pressure (P)
𝐹
𝑃 = = 𝜌𝑔ℎ
𝐴
• Absolute pressure and gauge pressure
 Basic Concepts: Energy 3

o Energy
• Energy is the ability to work.
• Various forms of energy:
§ Kinetic Energy (Ek)
1
𝐸) = 𝑚𝑣 .
2
§ Potential Energy (Ep)

𝐸/ = 𝑚𝑔𝑧
§ Photo Energy (Eph)

• Are there any other form of energy?

 Basic Concepts: Internal Energy (U) 4

o Internal Energy (U)

• Internal energy refers to energy of the molecules internal to
the substance. It includes kinetic energy of translation, of
rotation, and of internal vibration, as well as potential
energy resulting from intermolecular forces.
• Internal energy is just a thermodynamic primitive with no
concise thermodynamic definition and unknown absolute
values. However, only changes in internal energy are
required.
• What is internal energy related to?
 Basic Concepts: Work (W) 5

o Work (W)
• Work is performed whenever a force acts through a
distance. 46
𝑑𝑊 = 𝐹𝑑ℎ 𝑊 = 3 𝐹 𝑑ℎ
45

• Different forms of work

§ Mechanical work
§ PV (pressure–volume)
§ Electrical work
§ Shaft work
§ Elastic work
§ Others
 Basic Concepts: Work (W) 6

46
𝑑𝑊 = 𝐹𝑑ℎ 𝑊 = 3 𝐹 𝑑ℎ
45

• Work: 𝑑𝑊 = 𝐹𝑑ℎ
𝑑𝑉
• Consider: 𝐹 = 𝑃89: 𝐴 𝑑ℎ =
𝐴
46 76 76
𝑑𝑉
𝑊 = 3 𝐹 𝑑ℎ = 3 𝑃89: 𝐴 = 3 𝑃89: 𝑑𝑉
45 75 𝐴 75

Later on, we add a negative sign in front of P, due to the sign conversion used in
this module.
 Basic Concepts: Heat 7

o Heat
• Heat is a form of energy transferred solely as a result of
temperature difference.
o 0th Law of Thermodynamics

• The addition of heat to a substance increases its energy,

and work done on it can also have the same effect.
 Basic Concepts: System 8

o System
• System is a quantity of matter.

o Surroundings
• Surroundings is everything external to the system.

o Boundary
• Boundary is the “interface” that separates a system with
the surroundings.
 Basic Concepts: System 9

o Closed System
• No mass transfer between the system and the
surroundings
o Open System
• Mass crosses boundary

o Isolated System
• Nothing crosses boundary

For any system, if there is no change in T, there is no change

in U, correct? How about closed systems?
Basic Concepts: System 10
 Basic Concepts: Properties 11

o Extensive Properties
• Vary directly with the mass
• Volume, energy…
o Intensive Properties
• Independent of the amount of the mass
• Temperature, pressure
How can we convert an extensive property into an intensive
property?
𝐸
• Specific Energy: 𝐸< =
𝑚 (J/kg, kJ/kg, J/g)
• Specific Volume: 𝑉 (m3/kg, cm3/g)
𝑉< =
𝑚
12
 Basic Concepts: State Functions 13

o Thermodynamic State
• A specific condition determined by its thermodynamic
properties
o State Functions
• Macroscopic properties that describe a system
• Temperature, pressure, volume, energy, Cv, Cp, fugacity,
chemical potential…

How many state functions are needed to describe a system?

Hint: Phase Rule answer this question, read Section 2.7.
 Basic Concepts: Equilibrium 14

o Equilibrium
• A condition of balance characterized by the absence of
driving potentials
 Basic Concepts: Process 15

o Process
• A transition from one state to another

o Process Paths
• A succession of states during a process

o Cycle State 1 State 2

• System returns to the initial state.

 Basic Concepts: Reversible Process 16

o Reversible Process
• A process in which each intermediate state is only
infinitesimally removed from equilibrium.
 Basic Concepts: Reversible Process 17

o Reversible Process
• Under which condition can these processes be reversible?

P1 P2
 Excercise: Reversible Process 18

o Reversibility of Process
• Determine the reversibility of each of the following
processes:
§ Friction induces heat generation.
§ Sugar dissolves in water.
§ N2 mixes with O2.
§ Water boils into steam, under standard atmospheric
pressure, 373 K.
 Basic Concepts: Reversible Process 19

o Reversible Process
• Frictionless
• Never more than differentially removed from equilibrium
• Driven by forces whose imbalance is differential in
magnitude
• Can be reversed at any point by a differential change in
external conditions
• When reversed, retraces its forward path and restores the
initial state of system and surroundings
 Basic Concepts: Type of Process 20

o Isobaric process:
• Constant pressure

o Isothermal process:
• Constant temperature

o Isochoric process:
• Constant volume
o Adiabatic process:
• No heat across (Q = 0)
 Basic Concepts: Type of Process 21

o Isobaric process:
• Constant pressure

o Isothermal process:
• Constant temperature

o Isochoric process:
• Constant volume
o Adiabatic process:
2 ×
• No heat across (Q = 0)
 Sign Convention of Work and Heat 22

o Historically:
• When a system absorbs heat, Q > 0; releases heat, Q < 0.
• Work done by the system is positive; work done to the
system is negative.
o Modern Sign Convention
• Recommended by IUPAC and adopted by
textbook
• **When a system absorbs heat, Q > 0; releases
heat, Q < 0.
• **Work done to a system is positive, W > 0; done
by the system is negative, W < 0.
 Basic Concepts: Work (W) 23

46
𝑑𝑊 = 𝐹𝑑ℎ 𝑊 = 3 𝐹 𝑑ℎ
45

• Work: 𝑑𝑊 = 𝐹𝑑ℎ
𝑑𝑉
• Consider: 𝐹 = 𝑃89: 𝐴 𝑑ℎ =
𝐴
46 76 76
𝑑𝑉
𝑊 = 3 𝐹 𝑑ℎ = 3 𝑃89: 𝐴 = 3 𝑃89: 𝑑𝑉
45 75 𝐴 75

Later on, we add a negative sign in front of P, due to the sign conversion used in
this module.
 Department of Chemical and Biomolecular Engineering

CN2121 – Introduction to Chemical Engineering

Thermodynamics
Lecture 3 - 2: First Law of Thermodynamics

Read Chapter 2
 Energy Balance for Closed Systems 2

Energy Closed Energy

System

• Mass balance: ∆𝑚 = 0
• Energy balance:
∆𝐸 = ∆𝐸& + ∆𝐸( + ∆𝑈 = 𝑄 + 𝑊
• In many cases,
∆𝐸& = ∆𝐸( = 0
• Thus:
∆𝑈 = 𝑄 + 𝑊
𝑑𝑈 = 𝑑𝑄 + 𝑑𝑊 = 𝑑𝑄 − 𝑃𝑑𝑉
 Example 2.9 3
1 mol of air at 1 bar and 298.15 K is compressed to 5 bar and
298.15 K by two different mechanically reversible processes:
(a) Cooling at constant pressure followed by heating at
constant volume;
(b) Heating at constant volume followed by cooling at
constant pressure.

Calculate the heat and work requirements and ΔU and ΔH of

the air for each path. The following heat capacities for air may
be assumed to be independent of temperature:

𝐶1 = 20.78 and 𝐶6 = 29.10 𝐽 𝑚𝑜𝑙 <=𝐾 <=

Assume also for air that PV/T is a constant, regardless of the

changes it undergoes. At 298.15 K and 1 bar, the molar
volume of air is 0.02479 m3 mole−1.
 Example 2.9 4

1 mol
1 bar
? m3
Cooling at ?K Heating at
P = constant V = constant

1 mol 1 mol
Heating at Cooling at
1 bar 5 bar
V = constant P = constant
298.15 K 298.15 K
0.02479 m3 1 mol
? m3
5 bar
0.02479 m3
?K
 Example (2.9)
Example 2.9 5
Solution
Solution
1? 6? The1Afinal
6A volume is
@?
= = 𝑐𝑜𝑛𝑠𝑡
@A 𝑉1 𝑃1
The 1final volume is
𝑉2 = = 0.02479 = 0.004958 m3
𝑃2 5 𝑇′
1? 6? =
𝑉F = = 0.02479 = 0.004985 𝑚J
6A H
For path a
For In
path
the A, the
first first
step, step –
cooling at cooling
constantat constant
pressure of 1pressure
bar of 1 bar
@? 1A 𝑇 𝑉
𝑇L =𝑇 ′1= = 1 2298.15 0.004958/0.02479 = 59.63 𝐾
= 298.15 ( 0.004958/0.02479 )= 59.63 K
? 𝑉1

𝑄P =𝑄∆𝐻 = 𝐶𝑖 6=∆𝑇𝐶𝑃=
𝑖 =P ∆𝐻 ∆𝑇29.10 59.63
= 29.10 − 298.15
59.63 − 298.15==−6941
−6941𝐽J
∆𝑈P ∆𝑈
= ∆𝐻 − 𝑃∆𝑉 = −6941 − 1×10 H 0.004958 − 0.02479
P
= ∆𝐻 − ∆(𝑃𝑉) = −6941 − 1 × 105 0.004958 − 0.02479
𝑖 𝑖
= −4958
= −4958 𝐽 J
∆𝑈𝑖 = 𝑄𝑖 + 𝑊𝑖 𝑊𝑖 = ∆𝑈𝑖 − 𝑄𝑖 = −4958 − −6941 = 1983 J
∆𝑈P = 𝑄P + 𝑊P
𝑊P = ∆𝑈P − 𝑄P = −4958 − −6941 = 1983 𝐽
 Example 2.9 6

For path A, the second step – heating at constant volume

𝑊PP = 0
∆𝑈PP = 𝑄PP = 𝐶1 ∆𝑇 = 20.78 298.15 − 59.63 = 4958 𝐽
∆𝐻PP = ∆𝑈PP + ∆ 𝑃𝑉 = 4958 𝐽 + 0.004958× (5 − 1) ×10H
= 6941 𝐽

For the complete process (first step + second step)

𝑄 = 𝑄P + 𝑄PP = −6941 + 4958 = −1983 𝐽
𝑊 = 𝑊P + 𝑊PP = 1983 + 0 = 1983 𝐽
∆𝑈 = ∆𝑈P + ∆𝑈PP = −4958 + 4958 = 0 𝐽
∆𝐻 = ∆𝐻P + ∆𝐻PP = −6941 + 6941 = 0 𝐽
 Example 2.9 7
Example (2.9)
For path B, the first step – heating at constant volume
For path b
@? 6A In the first step, heating at constant volume
𝑇L = 6?
= 298.15 5/1 𝑇= 1490.75 5𝐾
1 𝑃2
𝑇′ = = 298.15 = 1490.75 K
𝑃1 1
Volume is constant, 𝑊 P = is
Volume 0constant, 𝑊𝑖 = 0

𝑄P = ∆𝑈P = 𝐶1 ∆𝑇 = 20.78
𝑄𝑖 = ∆𝑈𝑖1490.75 − 298.15
= 𝐶𝑉 ∆𝑇 = 20.78 1490.75 −= 24788
298.15 𝐽 J
= 24788

∆𝐻P = ∆𝑈P + ∆ 𝑃𝑉 = ∆𝐻
24788 +∆0.02479
𝑃𝑉 = 247885+− 1 10H = 34704
= 34704𝐽J 5
𝑖 = ∆𝑈𝑖 + 0.02479(5-1)10

In the second step, cooling at constant pressure

For path B, the second step – cooling at constant pressure
𝑄𝑖𝑖 = ∆𝐻𝑖𝑖 = 𝐶𝑃 ∆𝑇 = 29.10 298.15 − 1490.75 = −34704 J
𝑄PP = ∆𝐻PP = 𝐶6 ∆𝑇 ∆𝑈
=𝑖𝑖29.10
= ∆𝐻𝑖𝑖 − 298.15 − 1490.75
∆(𝑃𝑉) = −34703 − 5 × 105 = −34704
0.04958 𝐽
− 0.02479 = −247

∆𝑈PP = ∆𝐻PP − ∆𝑃𝑉 = −34703 − 5×10H 0.04958

𝑊𝑖𝑖 = ∆𝑈𝑖𝑖 − 𝑄𝑖𝑖 = −24788
− 0.02479
− −34703 = 9915 J

= −24788 𝐽
𝑊PP = ∆𝑈PP − 𝑄PP = −24788 − −34703 = 9915 𝐽
 Example 2.9 8

For the complete process (first step + second step)

𝑄 = 𝑄P + 𝑄PP = 24788 − 34703 = −9915 𝐽
𝑊 = 𝑊P + 𝑊PP = 0 + 9915 = 9915 𝐽
∆𝑈 = ∆𝑈P + ∆𝑈PP = 24788 − 24788 = 0 𝐽
∆𝐻 = ∆𝐻P + ∆𝐻PP = 34704 − 34704 = 0 𝐽

• ΔU and ΔH are independent of paths, while Q and W are

depending on the paths.
• Why ΔU and ΔH are 0 in these processes?
 Open Systems (Control Volume) 9

T, P

Vacuum

• Classification of open systems:

steady and transient state
ass Balance for Open
Mass Balance Systems
for Open Systems 10

• ∆𝑚 = 𝑚PU − 𝑚VWX
= 𝑚𝑖𝑛 − 𝑚out mሶ 𝑖𝑛
𝑑𝑚
𝑑𝑚
• Mass flow rate: 𝑚̇ =
s flow rate: 𝑚ሶ = 𝑑𝑡
𝑑𝑡
𝑑𝑚Y1 mሶ 𝑜𝑢𝑡
= 𝑚PU̇ − 𝑚VWX
̇
𝑑𝑡
𝑑𝑚
• ሶ 𝑖𝑛At−steady
=𝑚 𝑚ሶ out state: =0
𝑑𝑡
𝑚̇ = 𝑚PU
̇ = 𝑚VWX
̇
𝑑𝑚determine 𝑚?
• How can we ̇
teady state, =0
𝑑𝑡 𝑚̇ =How
𝜌𝑣𝐴 can you determine 𝑚?
ሶ
refore:
Cross section area: A
Cross section area: A
= 𝑚ሶ 𝑖𝑛 Flow velocity: v
= 𝑚ሶ out Flow velocity: v
 Energy Balance for Open Systems
Energy Balance for Open Systems 11

V: specific volume (m3/kg) U: specific internal energy (J/kg or kJ/kg)

H: specific enthalpy (J/kg or kJ/kg)

mሶ 𝑜𝑢𝑡

mሶ 𝑖𝑛
 Energy Balance for Open Systems 12

𝑑𝑄
• Heat: 𝑄̇ =
𝑑𝑡

𝑑𝑊
• Other work (shaft work, stirring, electric work): 𝑊̇ =
𝑑𝑡

• Energy carried by the flowing mass:

𝑚PU
̇ 𝐸PU − 𝑚VWX
̇ 𝐸VWX

• Work done by the flowing mass:

𝑚PU
̇ (𝑃𝑉)PU −𝑚VWX
̇ (𝑃𝑉)VWX
 Energy Balance for Open Systems 13

^(_`)ab
• ^X
=

𝑄̇ + 𝑊̇ + 𝑚̇ PU 𝐸PU − 𝑚̇ VWX 𝐸VWX + 𝑚̇ PU 𝑃𝑉 PU − 𝑚̇ VWX 𝑃𝑉 VWX

^(_`)ab
• ^X
= 𝑄̇ + 𝑊̇ + 𝑚̇ PU 𝐸PU + (𝑃𝑉)PU − 𝑚̇ VWX 𝐸VWX + (𝑃𝑉)VWX

• Consider:
𝐸PU = 𝑈PU + (𝐸& )PU +(𝐸( )PU 𝐸VWX = 𝑈VWX + (𝐸& )VWX +(𝐸( )VWX
^(_`)ab
= 𝑄̇ + 𝑊̇ + 𝑚̇ PU 𝑈PU + (𝐸& )PU +(𝐸( )PU +(𝑃𝑉)PU
^X

− 𝑚̇ VWX 𝑈VWX + (𝐸& )VWX +(𝐸( )VWX + 𝑃𝑉 VWX

 Energy Balance for Open Systems 14

• Since: 𝐻 ≡ 𝑈 + 𝑃𝑉
^(_`)ab
• ^X
= 𝑄̇ + 𝑊̇ + 𝑚̇ PU 𝐻PU + (𝐸& )PU +(𝐸( )PU

−𝑚̇ VWX 𝐻VWX + (𝐸& )VWX +(𝐸( )VWX

General energy balance equation for open systems

^(_`)ab = F
̇ ̇
= 𝑄 + 𝑊 + 𝑚̇ PU 𝐻PU + F 𝑢PU + 𝑔𝑧PU −
^X

=
F
𝑚̇ VWX 𝐻VWX + F 𝑢VWX + 𝑔𝑧VWX

Units to be used (SI unit):

𝑚 (kg); 𝑡 (sec); 𝑈 (J/kg); 𝑄̇ (J/sec); 𝑊̇ (J/sec); 𝑚̇ (kg/sec)
𝐻 (J/kg); 𝑢 (m/sec); 𝑔 (9.807 N/kg); 𝑧 (m) [Often KJ is used]
 Energy Balance for Open Systems 15

Simplification of energy balance equation for open systems

1. For open systems under steady state
= F = F
0 = 𝑄̇ + 𝑊̇ + 𝑚̇ PU 𝐻PU + 𝑢PU + 𝑔𝑧PU − 𝑚̇ VWX 𝐻VWX + 𝑢VWX + 𝑔𝑧VWX
F F

2. Ignore 𝐸& and 𝐸(

𝑑(𝑚𝑈)Y1
= 𝑄̇ + 𝑊̇ + 𝑚̇ PU 𝐻PU − 𝑚̇ VWX 𝐻VWX
𝑑𝑡
3. Steady state, ignore 𝐸& and 𝐸(
0 = 𝑄̇ + 𝑊̇ + 𝑚̇ PU 𝐻PU − 𝑚̇ VWX 𝐻VWX
4. Closed system:

𝑑𝑈
𝑚 =𝑄+𝑊
𝑑𝑡
 Example 4.2 16
Calculate the heat required to raise the temperature of 1 mol
of methane from 533.15 K to 873.15 K in a steady-flow
process at a pressure sufficiently low that methane may be
considered as an ideal gas.
Methane Q=? Methane

533.15 K 873.15 K

Solution
𝑑(𝑚𝑈)Y1 1 F
̇ ̇
= 𝑄 + 𝑊 + 𝑚̇ PU 𝐻PU + 𝑢PU + 𝑔𝑧PU −
𝑑𝑡 2
= F
𝑚̇ VWX 𝐻VWX + F 𝑢VWX + 𝑔𝑧VWX

• Steady state; ignore 𝐸& and 𝐸( ; 𝑊̇ = 0

0 = 𝑄̇ + 𝑊̇ + 𝑚̇ PU 𝐻PU − 𝑚̇ VWX 𝐻VWX 𝑄̇ = 𝑚∆𝐻
̇
 Example 17
A steam turbine is operating under
steady state. Related parameters
are listed in the figure. In addition,
the turbine releases the heat to the
surroundings at a rate of 8.5 kW.
Determine the power delivered by
the turbine. 𝑚̇ PU = 1.5 𝑘𝑔/𝑠 𝑃VWX = 0.1 𝑀𝑃𝑎
𝑃PU = 2 𝑀𝑃𝑎 𝑃VWX = 100 °𝐶
Solution 𝑇PU = 350 °𝐶 𝑣VWX = 100 𝑚/𝑠
𝑣PU = 50 𝑚/𝑠 𝑧VWX = 3 𝑚
𝑧PU = 6 𝑚
Energy balance
1 F 1 F
̇ ̇
0 = 𝑄 + 𝑊 + 𝑚̇ PU 𝐻PU + 𝑢PU + 𝑔𝑧PU − 𝑚̇ VWX 𝐻VWX + 𝑢VWX + 𝑔𝑧VWX
2 2

Mass balance
𝑚̇ PU = 𝑚̇ VWX
 Example 18

𝑚̇ PU = 1.5 𝑘𝑔/𝑠 𝑃VWX = 0.1 𝑀𝑃𝑎

𝑃PU = 2 𝑀𝑃𝑎 𝑃VWX = 100 °𝐶
𝑇PU = 350 °𝐶 𝑣VWX = 100 𝑚/𝑠
𝑣PU = 50 𝑚/𝑠 𝑧VWX = 3 𝑚
𝑧PU = 6 𝑚

1 F 1 F
𝑊̇ = −𝑄̇ − 𝑚̇ 𝐻PU + 𝑢PU + 𝑔𝑧PU − 𝐻VWX + 𝑢VWX + 𝑔𝑧VWX
2 2
1 F 1 F
= −𝑄̇ − 𝑚̇ 𝐻PU − 𝐻VWX + 𝑢PU − 𝑢VWX + 𝑔𝑧PU − 𝑔𝑧VWX
2 2

From Table F.2: Superheated steam, 𝐻PU = 3138.6 𝑘𝐽/𝑘𝑔

From Table F.1: Saturated steam, 𝐻VWX = 2676.0 𝑘𝐽/𝑘𝑔

 Example 19

𝑚̇ PU = 1.5 𝑘𝑔/𝑠 𝑃VWX = 0.1 𝑀𝑃𝑎

𝑃PU = 2 𝑀𝑃𝑎 𝑃VWX = 100 °𝐶
𝑇PU = 350 °𝐶 𝑣VWX = 100 𝑚/𝑠
𝑣PU = 50 𝑚/𝑠 𝑧VWX = 3 𝑚
𝑧PU = 6 𝑚

=
𝑊̇ = −𝑄̇ − 𝑚̇ F
𝐻PU − 𝐻VWX + F 𝑢PU F
− 𝑢VWX + 𝑔𝑧PU − 𝑔𝑧VWX

&k =
= − −8.5 𝑘𝑊 − 1.5 l
×m 3138.6 − 2676.0 + F×=ooo (50F

&p
− 100F) + 9.807(6 − 3)/1000n &k

= 8.5 𝑘𝑊 − 1.5× 462.6 − 3.75 + 0.029 𝑘𝑊

= −680 𝑘𝑊
 Example 2.17 20
Example (2.17)
Water at 366.15 K is pumped from a storage tank at the rate
of 3.15×10−3 m3 s−1. The motor for the pump supplies work at
Water at 366.15 K is pumped from a storage tank at the rate of 3.15×
the−3rate of 1.5 kW. The water goes through a heat exchanger,
10 m3 s −1 . The motor for the pump supplies work at the rate of 1.5
giving up heat at the rate of 700 kW, and is delivered to a
kW. The water goes through a heat exchanger, giving up heat at the
second storage
rate of 700 kW, tank
and isatdelivered
an elevation
to a of 15 mstorage
second above tank
the first
at an
tank. What
elevation is the
of 15 temperature
m above of the
the first tank. water
What is thedelivered to the
temperature of the
second tank? to the second tank?
water delivered

T=?

15 m
𝑉ሶ = 3.15× 10−3 m3 s −1
𝑊ሶ = 1.5 kW 𝑄ሶ = −700 kW

Tin = 366.15 K
 Example 2.17 21

Solution
• What is your system?
It is a steady-state, steady-flow process,

From Table F.1,

𝜌qrXst 366.15 𝐾 = 963 𝑘𝑔 𝑚<J
𝑚PU
̇ = 𝑚VWX ̇ qrXst = 3.15×10<J×963 = 3.033 𝑘𝑔 𝑠 <=
̇ = 𝑉𝜌

1 F 1 F
̇ ̇
0 = 𝑄 + 𝑊 + 𝑚̇ PU 𝐻PU + 𝑢PU + 𝑔𝑧PU − 𝑚̇ VWX 𝐻VWX + 𝑢VWX + 𝑔𝑧VWX
2 2

• ∆𝐸& can be omitted.

 Example 2.17 22

𝑄̇ + 𝑊̇
𝐻VWX = + 𝐻PU − 𝑔 𝑧VWX − 𝑧PU
𝑚̇ PU

−700 + 1.5 9.807×15

= + 389.6 −
3.033 1000
= −230.3 + 389.6 − 0.15 = 159.1 𝑘𝐽 𝑘𝑔<=

• From Table F.1, the temperature of water having this enthalpy

is found to be 𝑻𝒐𝒖𝒕 = 𝟑𝟏𝟏 𝑲

• What if we do not have a Steam Table with us?

(see next page…)
 Example 2.17 23

𝑄̇ + 𝑊̇
𝐻VWX = + 𝐻PU − 𝑔 𝑧VWX − 𝑧PU
𝑚̇ PU

𝑄̇ + 𝑊̇
∆𝐻 = 𝐻VWX − 𝐻PU = + 𝐻PU − 𝑔 𝑧VWX − 𝑧PU
𝑚̇ PU

−700 + 1.5 9.807×15

= − = −230.45 𝑘𝐽 𝑘𝑔<=
3.033 1000
• From liquid water:
𝐶1 ≈ 𝐶6 ≈ 𝐶 = 4.18 𝐽 𝑔<=𝐾 <= = 4.18 𝑘𝐽 𝑘𝑔<=𝐾 <=
∆𝐻 = 𝐶6 𝑇VWX − 𝑇PU

∆𝐻 −230.45
𝑇VWX = + 𝑇PU = + 366.15 = 311 𝐾
𝐶6 4.18
 Example 2.14 Example 2.14 24
An insulated electrically heated tank for hot water contains
An insulated electrically heated tank for hot water contains 190 kg of
190 kg of liquid water at 333.15 K when a power outage
liquid water at 333.15 K when a power outage occurs. If water is
occurs.
flowingIfthrough
water istheflowing
tank through
at a therate
steady tankofat𝑚ሶ a=steady
0.2 𝑘𝑔 𝑠rate
−1 of
, how
𝑚̇ long
= 0.2 <=
𝑘𝑔it𝑠take, how long will it take for tank
the Ttoofdrop
water
will for the T of water in the to in the K.
308.15
tank to drop
Assume coldtowater
308.15 K. Assume
enters the tank at cold water
283.15 K, enters the tank
and negligible heat
atlosses
283.15 K, the
from andtank
negligible heatwater,
(For liquid losses𝐶𝑉 from
= 𝐶𝑝 = the𝐶,tank (for
independent of
liquid P). 𝐶1 = 𝐶6 = 𝐶, independent of T and P).
T andwater,

mሶ 𝑖𝑛 mሶ 𝑜𝑢𝑡
m = 190 kg
T=?

𝑚ሶ in = 0.2 kg/s 𝑚ሶ out = 0.2 kg/s

Tin = 283.15 K Tout = ?

Assumption: T = Tout
Assumption: 𝑇 = 𝑇VWX
𝑊ሶ 𝑄
=̇ = ሶ
Solution:
Solution: In
Inthis
thissystem,
system, 𝑊̇ ==0,0,Ep𝐸and
0, 𝑄 E can be ignored
( & 𝐸k& can be ignored.
 Example 2.14 25

𝑑(𝑚𝑈)Y1
= 𝑚̇ PU 𝐻PU − 𝑚̇ VWX 𝐻VWX
𝑑𝑡
𝑑𝑈Y1
𝑚 = 𝑚(𝐻
̇ PU − 𝐻VWX )
𝑑𝑡
𝑑𝑈Y1 𝐶1 𝑑𝑇
= 𝐻PU − 𝐻VWX = 𝐶6 (𝑇PU − 𝑇VWX ) = 𝐶(𝑇PU − 𝑇)
𝑑𝑡 𝑑𝑡
𝑑𝑇 𝑚 𝑑𝑇
𝑚𝐶 = 𝐶 𝑚(𝑇
̇ PU − 𝑇) 𝑑𝑡 = −
𝑑𝑡 𝑚̇ 𝑇 − 𝑇PU
@
𝑚 𝑇 − 𝑇PU 190 308.15 − 283.15
𝑡 = − ln } =− ln
𝑚̇ 𝑇o − 𝑇PU @ •JJJ.=H 0.2 333.15 − 283.15
€

= 658.5 𝑠𝑒𝑐𝑜𝑛𝑑𝑠
 Example 2.13 26
An evacuated tank is slowly filled with gas from a
constant-pressure line. What is the relation between the
enthalpy of the gas in the entrance
Example (2.13) line and the internal
energy of the gasAninevacuated
the tank? Neglect heat transfer
tank is slowly filled with gas
between the gasfrom
anda constant-pressure
the tank. line. What is the T, P
𝑚ሶ 𝑖𝑛
Solution: relation between the enthalpy of the gas in
the entrance line and the internal energy of
the gas in the𝑑𝑚 Y1 Neglect heat transfer
tank?
The mass balance is the gas and the=tank.
between 𝑚PU̇
Solution:
𝑑𝑡
For energy balance, 𝐸 & 𝐸 can
The mass(balance&is
be ignored
𝑑𝑚𝐶𝑉
= 𝑚ሶ 𝑖𝑛 Vacuum
𝑑𝑡
𝑑(𝑚𝑈)
For energy balance, ignore Ek and Ep
Y1
= 𝑄̇ 𝐶𝑉
𝑑(𝑚𝑈) + 𝑊̇ + 𝑚̇ PU 𝐻PU − 𝑚̇ VWX 𝐻VWX
𝑑𝑡 𝑑𝑡
= 𝑄ሶ + 𝑊ሶ + 𝑚ሶ 𝑖𝑛𝐻𝑖𝑛 − 𝑚ሶ 𝑜𝑢𝑡𝐻𝑜𝑢𝑡

In this system, 𝑄̇ In=this𝑊system,

̇ = 0,𝑊ሶ 𝑚=̇ 0, 𝑄ሶ =
VWX = 0,0,
( 𝐸 =&0 𝐸 can be
𝑚ሶ 𝑜𝑢𝑡
& ignored.
𝑑(𝑚𝑈)𝐶𝑉
= 𝑚ሶ 𝑖𝑛𝐻𝑖𝑛
𝑑(𝑚𝑈)Y1𝑑𝑡
= 𝑚̇ PU 𝐻PU
𝑑𝑡
 Example 2.13 27

• Combining the two balance equations,

𝑑(𝑚𝑈)Y1 𝑑𝑚Y1
= 𝐻PU
𝑑𝑡 𝑑𝑡
• Integrating
∆(𝑚𝑈)Y1 = 𝐻PU ∆𝑚Y1
𝑚F𝑈F − 𝑚=𝑈= = 𝐻PU (𝑚F − 𝑚=)
1 and 2 denote initial and final states of the tank.
• Since 𝑚= = 0,
𝑈F = 𝐻PU
 Tips for Solving Problems 28

• Draw a diagram schematically;

• Define the system clearly;
• Write down the MB & EB equations;
• In many cases, simplify your MB and EB equations;
• Evaluate your MB and EB equations.
 Summary 29

• First Law of Thermodynamics

∆𝐸lƒlXs_ + ∆𝐸lWttVU^PUkl = 0
• Energy Balance in Closed Systems
∆𝑈 = 𝑄 + 𝑊 ∆𝑈 = 𝑄 + 𝑊
• Enthalpy
𝐻 ≡ 𝑈 + 𝑃𝑉
• Heat Capacity
„` „…
𝐶1 ≡ 𝐶6 ≡
„@ 1 „@ 6

• Mass and Energy Balances for Open Systems

^(_`)ab = F
= 𝑄̇ + 𝑊̇ + 𝑚̇ PU 𝐻PU + 𝑢PU + 𝑔𝑧PU
^X F 𝑑𝑚Y1
= 𝑚PU
̇ − 𝑚VWX
̇
F=
−𝑚̇ VWX 𝐻VWX + 𝑢VWX + 𝑔𝑧VWX 𝑑𝑡
F
 Department of Chemical and Biomolecular Engineering

CN2121 – Introduction to Chemical Engineering

Thermodynamics
Lecture 4: Equations of States

Read Chapter 3
 Outline 2

o Phase Rule & Equation of State

o PVT Diagram & Steam Table
o The Ideal Gas Law
o Different Processes: A Revisit
o The Virial Equations of State
o Cubic Equations of State
o Generalized Correlation for Gases and Liquids
 Phase Rule 3

• Recall: What is a thermodynamic state?

What is a thermodynamic property?
• Common properties: Temperature, pressure, specific
volume, specific internal energy, specific enthalpy…
• Phase rule: 𝐹 = 2 − 𝜋 + 𝑁
F: Degree of freedom of the system
𝜋: Number of phases N: Chemical species
• Pure substance is one that has a uniform chemical
composition throughout.
• Question: How many properties are needed to describe a
system with H2O(g) and H2O(l) in equilibrium?
 Equation of States 4

• In principle: for pure fluids, any property can be

described as a function of at most two other properties.
• Q: How can we describe the relationships among various
properties?
A: By three major ways.

• We will focus this

chapter on the PVT
Relations of Pure
Fluids.
 PVT Diagrams 5

Pà∞ P = 1 atm P = 1 atm

1 atm Tc
150 oC
100 oC

P = 1 atm P→0 T = 100 °C

• A reversible isothermal expansion of water (at T = 100 °C)

from P à ∞ to P à 0.
PVT Diagrams 6
 PVT Diagrams 7

A compressed liquid is one that is

NOT about to evaporate. An
increase in temperature will not
bring about evaporation.

A saturated liquid is one that is

about to evaporate. Any slight
increase in temperature (or
decrease in pressure) will cause
evaporation.

A saturated vapor is one that is about to condense. Any slight

decrease in temperature (or increase in pressure) will cause
condensation.

A superheated vapor is one that is not about to condense. Any

decrease in temperature will not bring about condensation.
 Two-Phase Liquid/Vapor Systems 8

• For a system consisting of saturated-liquid and saturated-

vapor phases coexisting in equilibrium,
𝑛𝑉 = 𝑛+ 𝑉 + + 𝑛, 𝑉 , 𝑛 = 𝑛+ + 𝑛,
𝑉 = 𝑥+𝑉+ + 𝑥,𝑉, 1 = 𝑥+ + 𝑥,
𝑉 = (1 − 𝑥 , )𝑉 + + 𝑥 , 𝑉 ,
Quality: mass or molar fraction of vapor 𝑥 ,
• In general,
𝑀 = 𝑥 + 𝑀+ + 𝑥 , 𝑀,
𝑀 = (1 − 𝑥 , )𝑀 + + 𝑥 , 𝑀 ,
, where 𝑀 represent 𝑉, 𝑈, 𝐻, 𝑆, etc.
 PVT Diagrams 9

Figure 3.1 PT diagram of a pure substance. Triple point of a

substance is the
temperature and
pressure at which
the three phases (g,
l, and s) coexist in
thermodynamic
equilibrium.

Critical point of a
substance is the
maximum P and T
at which a pure
chemical species is
observed to exist in
g/l equilibrium.
 Recall: An Example in Last Chapter 10

A steam turbine is operating under

steady state. Related parameters
are listed in the figure. In addition,
the turbine releases the heat to the
surroundings at a rate of 8.5 kW.
Determine the power delivered by
the turbine. 𝑚̇ ;< = 1.5 𝑘𝑔/𝑠 𝑃ABC = 0.1 𝑀𝑃𝑎
𝑃;< = 2 𝑀𝑃𝑎 𝑃ABC = 100 °𝐶
Solution 𝑇;< = 350 °𝐶 𝑣ABC = 100 𝑚/𝑠
𝑣;< = 50 𝑚/𝑠 𝑧ABC = 3 𝑚
𝑧;< = 6 𝑚
Energy balance
1 > 1 >
̇ ̇
0 = 𝑄 + 𝑊 + 𝑚̇ ;< 𝐻;< + 𝑢;< + 𝑔𝑧;< − 𝑚̇ ABC 𝐻ABC + 𝑢ABC + 𝑔𝑧ABC
2 2

Mass balance
𝑚̇ ;< = 𝑚̇ ABC
Search Values in Steam Table 11
12
13
14
 Quiz 15

o Which of the following is (are) correct?

• The melting point of water is a constant.

• The boiling point of water is a constant.
• The sublimation point of water is a constant.
• The critical point of water is a constant.
• The triple point of water is a constant.
 The Ideal Gas Law 16

• Define ideal gas as one whose macroscopic behavior is

𝑃𝑉 = 𝑅𝑇
V is the molar volume of a gas.

Assumptions for the ideal gas law:

• There are no attractive or repulsive forces between the
molecules or the surroundings;
• The volume of the molecules is negligibly small compared
to the volume occupied by the gas.
 Implied Property Relations for Ideal Gases 17

𝐻 ≡ 𝑈 + 𝑃𝑉 = 𝑈 𝑇 + 𝑅𝑇 = 𝐻(𝑇)

𝜕𝑈 𝑑𝑈 𝑇
𝐶S ≡ = = 𝐶S (𝑇)
𝜕𝑇 S 𝑑𝑇

𝜕𝐻 𝑑𝐻 𝑇 𝑑𝐻 𝑑𝑈
𝐶V ≡ = = 𝐶V (𝑇) 𝐶V = = + 𝑅 = 𝐶S + 𝑅
𝜕𝑇 V 𝑑𝑇 𝑑𝑇 𝑑𝑇

𝑑𝑈 = 𝐶S 𝑑𝑇 ∆𝑈 = ∫ 𝐶S 𝑑𝑇

𝑑𝐻 = 𝐶V 𝑑𝑇 ∆𝐻 = ∫ 𝐶V 𝑑𝑇
• 𝑈, 𝐻, 𝐶S , 𝐶V , ∆𝑈, ∆𝐻 only depend on temperature, we define:

𝐶V 𝑅 𝑅 𝛾𝑅
𝛾≡ =1+ →→→ 𝐶S = 𝐶V =
𝐶S 𝐶S 𝛾−1 𝛾−1
 𝑊, 𝑄, ∆𝑈, ∆𝐻 of Various Processes 18

Isochoric Process (constant V)

>
𝑊= − ∫[ 𝑃𝑑𝑉 =0
>
𝑄 = ∆𝑈 = ∫[ 𝐶S 𝑑𝑇
>
∆𝐻 = ∫[ 𝐶V 𝑑𝑇

Isobaric Process (constant P)

>
𝑊= − ∫[ 𝑃𝑑𝑉 = −𝑃 𝑉> − 𝑉[ = −𝑅 𝑇> − 𝑇[
>
∆𝑈 = ∫[ 𝐶S 𝑑𝑇
>
𝑄 = ∆𝐻 = ∫[ 𝐶V 𝑑𝑇
 𝑾, 𝑸, ∆𝑼, ∆𝑯 of Various Processes 19

Isothermal Process (constant T)

> >
∆𝑈 = ∫[ 𝐶S 𝑑𝑇 =0 ∆𝐻 = ∫[ 𝐶V 𝑑𝑇 =0
> > `a > bS Sd
𝑊= − ∫[ 𝑃𝑑𝑉 = − ∫[ 𝑑𝑉 = −𝑅𝑇 ∫[ = −𝑅𝑇𝑙𝑛( )
S S Se

Sd Ve
𝑄 = −𝑊 = 𝑅𝑇𝑙𝑛 = 𝑅𝑇𝑙𝑛
Se Vd

Adiabatic Process (𝒅𝑸 = 𝟎)

> >
∆𝑈 = ∫[ 𝐶S 𝑑𝑇 ∆𝐻 = ∫[ 𝐶V 𝑑𝑇 =0
>
𝑄=0 𝑊 = ∆𝑈 = ∫[ 𝐶S 𝑑𝑇
 Check Your Understanding 20

1. U of ideal gas depends on volume and temperature.

2. 𝐶V and 𝐶S of ideal gas are constants.
3. 𝐶V can only be used in isobaric process while 𝐶S can only
be used in isochoric process.
4. 𝑑𝑈 = 𝐶S 𝑑𝑇, 𝑑𝐻 = 𝐶V 𝑑𝑇
can be used for ideal gas in any process.
`a `a
5. 𝑑𝑊 = − S
𝑑𝑉, 𝑑𝑄 = 𝐶S 𝑑𝑇 +
S
𝑑𝑉

can be used for ideal gas in any process.

Ture or False?
Polytropic Process
Polytropic Process 21

𝑃𝑉 i𝛿 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 “Equation of Process”

𝑃𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 A model of some versatility! “Equation of Process”
im[ ([mi)/i
For an ideal gas, 𝑇𝑉𝛿−1 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑇𝑃
(1−𝛿)/𝛿 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
For an ideal gas 𝑇𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑇𝑃 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

Isobaric process: 𝛿 = 0
Isobaric process: 𝛿 = 0 𝑃𝑉 0 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
Isothermal process: 𝛿 = 1
Isothermal process: 𝛿 = 1
Isochoric process:
Isochoric
1 process:
1
𝑃𝛿 𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝛿 [/i
[/i
𝑃𝑖𝑓 𝛿 𝑉 𝑃𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
== 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
±∞
1
[/i
𝑉=
𝑖𝑓 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝛿
𝛿 = ±∞, V = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
Adiabatic 𝛿 = 𝛾𝛿 = 𝛾
process:
Adiabatic process: 𝑃𝑉 ∞ = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
24
 Polytropic Process 22

Adiabatic process (𝑑𝑄 = 0)

`a
𝑑𝑄 = 𝐶S 𝑑𝑇 + 𝑃𝑑𝑉 = 0 𝐶S 𝑑𝑇 = −𝑃𝑑𝑉 = − 𝑑𝑉
S

ba ` bS ad Se `/st
Rearrange: =− →→→ =
a st S ae Sd

Alternatively: 𝐶S 𝑑𝑇 = −𝑃𝑑𝑉 = − 𝑅𝑑𝑇 − 𝑉𝑑𝑃

`a
𝐶V − 𝑅 𝑑𝑇 = − 𝑅𝑑𝑇 − 𝑉𝑑𝑃 𝐶V 𝑑𝑇 = 𝑉𝑑𝑃 = 𝑑𝑃
V

ba ` bV ad Vd `/su
Rearrange: = →→→ =
a su V ae Ve

Se `/st Vd `/su Vd Se su /st Se v

Therefore: = →→ = =
Sd Ve Ve Sd Sd

𝑃𝑉 v = 𝑐𝑜𝑛𝑠𝑡. or 𝑇𝑉 vm[ = 𝑐𝑜𝑛𝑠𝑡. or 𝑇𝑃 ([mv)/v = 𝑐𝑜𝑛𝑠𝑡.

 Example 3.2 23

1 mole of air is compressed from an initial state of 1 bar and

298.15 K to a final state of 5 bar and 298.15 K by three
different mechanically reversible processes in a closed
system:

a. Heating at constant volume followed by cooling at

constant pressure.
b. Isothermal compression.
c. Adiabatic compression followed by cooling at constant
volume.

Assume air to be an ideal gas with constant,

w x
𝐶S = 𝑅 and 𝐶V = 𝑅
> >

Calculate 𝑊, 𝑄, ∆𝑈, ∆𝐻 of the air for each process.

 Example 3.2 24

Solution
w
𝐶S = 𝑅 = 20.785 J 𝑚𝑜𝑙 m[ 𝐾 m[
>

x
𝐶V = 𝑅 = 29.099 J 𝑚𝑜𝑙 m[ 𝐾 m[
>

su
𝛾≡ = 1.4
st

From ideal gas law:

𝑉[ = 0.02479 𝑚 ~
𝑉> = 0.00496 𝑚 ~
Since State 1 and 2 has the same T,
∆𝑈 = ∆𝐻 = 0 (∆𝑈 and ∆𝐻 is irrelevant of the path.)
 Example 3.2 25

(a) 𝑄 = −9915 𝐽 and 𝑊 = 9915 𝐽

Hint: constant P, 𝑄 = ∆𝐻; constant V, 𝑄 = ∆𝑈
V [
(b) 𝑄 = −𝑊 = 𝑅𝑇𝑙𝑛( e ) = 8.314 298.15 ln = −3990 𝐽
Vd w

Se vm[ ƒ.ƒ>„x… ƒ.„

‚
(c) 𝑇 = 𝑇[ ( ) = 298.15 = 567.57 𝐾
Sd ƒ.ƒƒ„…w†

For the first adiabatic step:

𝑄[ = 0 𝑊[ = 𝐶S ∆𝑇 = 20.785 567.57 − 298.15 = 5600 𝐽
For the second constant volume step:
𝑊> = 0 𝑄> = 𝐶S ∆𝑇 = 20.785 298.15 − 567.57 = −5600 𝐽
Combined 𝑄 = −5600 𝐽 𝑊 = 5600 𝐽
 Example 3.3 26

1 mole ideal gas undergoes the following sequence of

mechanically reversible processes in a closed system:

a. From an initial state of 343.15 K and 1 bar, it is

compressed adiabatically to 423.15 K.
b. It is then cooled from 423.15 K to 343.15 K at constant
pressure.
c. Finally, it is expanded isothermally to its original state.

Calculate 𝑊, 𝑄, ∆𝑈, ∆𝐻 for each of the three processes and for

the entire cycle.

Assume air to be an ideal gas with constant,

~ w
𝐶S = 𝑅 and 𝐶V = 𝑅
> >
 Example 3.3 27

Solution
~
𝐶S = 𝑅 = 12.471 J 𝑚𝑜𝑙 m[ 𝐾 m[
>

w
𝐶V = 𝑅 = 20.785 J 𝑚𝑜𝑙 m[ 𝐾 m[
>

su
𝛾≡ = 1.667
st

For the first adiabatic step:

𝑄=0
∆𝑈 = 𝑊 = 𝐶S ∆𝑇 = 12.471 423.15 − 343.15 = 998 𝐽
∆𝐻 = 𝐶V ∆𝑇 = 20.785 423.15 − 343.15 = 1663 𝐽
 Example 3.3 28

For the second isobaric step:

𝑄 = ∆𝐻 = 𝐶V ∆𝑇 = 20.785 343.15 − 423.15 = −1663 𝐽
∆𝑈 = 𝐶S ∆𝑇 = 12.471 343.15 − 423.15 = −998 𝐽
𝑊 = ∆𝑈 − 𝑄 = −998 − −1663 = 665 𝐽
For the third isothermal step:
∆𝑈 = ∆𝐻 = 0
V
𝑄 = −𝑊 = 𝑅𝑇𝑙𝑛( ‡ ) Need to find 𝑃~ Note 𝑃~ = 𝑃>
Ve

Go back to the first adiabatic step: 𝑇𝑃 ([mv)/v = 𝑐𝑜𝑛𝑠𝑡.

𝑇> v 423.15 >.w

𝑃> = 𝑃[ ( ) = 1(
vm[ ) = 1.689 𝑏𝑎𝑟
𝑇[ 343.15
 Example 3.3 29

𝑃~ 1.689
𝑄 = −𝑊 = 𝑅𝑇𝑙𝑛 = 8.314 343.15 𝑙𝑛 = 1495 𝐽
𝑃[ 1

For the entire cycle,

𝑄 = 0 − 1663 + 1495 = −168 𝐽
𝑊 = 998 + 665 − 1495 = 168 𝐽
∆𝑈 = 998 − 998 + 0 = 0 𝐽
∆𝑈 = 1663 − 1663 + 0 = 0 𝐽
 Virial Equations of State 30

Define Compressibility Factor

N2
𝑃𝑉
𝑍≡
𝑅𝑇
For ideal gas: 𝑍 = 1
For real gas, 𝑍 is a function of P:
𝑍 = 1 + 𝐵‚ 𝑃 + 𝐶 ‚ 𝑃> + 𝐷‚ 𝑃~ + ⋯

𝐵 𝐶 𝐷
𝑍 =1+ + >+ ~+⋯
𝑉 𝑉 𝑉
These are the Virial equations of states.
• B’, C’, D’,… are the Virial coefficients; B’ is the 2nd Virial coefficient, C’ is
the 3rd Virial coefficient, etc.
• Virial coefficients are depending on the substance and T, and are usually
obtained from experimental data.
 Virial Equations of State 31

The Virial expansion is often truncated at 𝐵 ‚ (𝑇) or 𝐵 𝑇 , which

is usually applicable for P < 10 bar and moderate T or above
(rule of thumb).
The 2nd order Virial equation:
VS VS Ž
𝑍≡ = 1 + 𝐵‚𝑃 𝑍≡ =1+
`a `a S

Relation between 𝐵 ‚ and 𝐵,

Ž ‚ ‚ •`a ‚ ‚ Ž s •
=𝐵𝑃= 𝐵 𝐵 = 𝐵 𝑍𝑅𝑇 = 𝐵 𝑅𝑇 1 + + + +⋯
S S S Sd S‡

‚ Ž
Ignore the high order term, 𝐵 =
`a

ŽV
𝑍 =1+ This is the most often used 2nd order Virial equation.
`a
 Example 3.8 32

Reported values for the virial coefficients of isopropanol vapor

at 473.15 K are:
𝐵 = −388 𝑐𝑚 ~ 𝑚𝑜𝑙 m[ 𝐶 = −26000 𝑐𝑚 ‘ 𝑚𝑜𝑙 m>

Calculate 𝑉 and 𝑍 for isopropanol vapor at 473.15 K and 10

bar by
a. the ideal gas equation,
b. 2nd order Virial equation,
c. 3rd order Virial equation.
 Example 3.8 33

Solution
(a) For an ideal gas, 𝑍 = 1, and

𝑅𝑇 8.314 473.15 ~ m[
𝑉≡ = = 0.003934 𝑚 𝑚𝑜𝑙
𝑃 10×10w
= 3934 𝑐𝑚 ~ 𝑚𝑜𝑙 m[
(b) For 2nd order Virial equation,

𝐵𝑃 𝑅𝑇
𝑍 =1+ →→→ 𝑉 = + 𝐵 = 3934 − 388 = 3546 𝑐𝑚 ~ 𝑚𝑜𝑙 m[
𝑅𝑇 𝑃
(Pay attention to the units.)

𝑃𝑉 𝑉 3546
𝑍= = = = 0.9014
𝑅𝑇 𝑅𝑇/𝑃 3934
 Example 3.8 34

(c) For 3nd order Virial equation,

𝐵 𝐶 𝑅𝑇 𝐵 𝐶
𝑍 = 1 + + > →→→ 𝑉 = (1 + + > )
𝑉 𝑉 𝑃 𝑉 𝑉
Solve this cubic equation,
𝑉 = 3488 𝑐𝑚 ~ 𝑚𝑜𝑙 m[

𝑃𝑉 𝑉
𝑍= = = 0.8866
𝑅𝑇 𝑅𝑇/𝑃
 Cubic Equations of State 35

The van der Waals Equation of State

𝑅𝑇 𝑎 ~
𝑅𝑇 > 𝑎 𝑎𝑏
𝑃= − > →→→ 𝑉 − 𝑏 + 𝑉 + 𝑉− =0
𝑉−𝑏 𝑉 𝑃 𝑃 𝑃
• Volume of molecules:
𝑉;b“”+ = 𝑉 − 𝑏
𝑏 is roughly the molar volume of molecule themselves.
• Intermolecular interactions (predominantly attractive in
low/mediate densities):
𝑎
𝑃;b“”+ =𝑃+ >
𝑉
𝑎
is the inner pressure.
𝑉>
 Cubic Equations of State: Isotherm 36

~
𝑅𝑇 > 𝑎 𝑎𝑏
𝑉 − 𝑏+ 𝑉 + 𝑉− =0
𝑃 𝑃 𝑃

• For isotherm 𝑇[ > 𝑇– , P

decreases monotonically with
increasing V.

• For the critical isotherm, also a

monotonically decreasing
function containing a horizontal
inflection at critical point.

• For isotherm 𝑇[ < 𝑇– , P decreases rapidly in the subcooled-

liquid region with increasing V; after crossing the 𝑉˜”C(+;™) line,
P passes through a minimum, rises to a maximum, and then
decreases finally to the superheated-vapor region.
 Determination of a and b 37

For isotherm at 𝑇[ > 𝑇– , the solution for V at any P yields only

one root.
At critical isotherm, also true. Except at critical point, where there
are 3 roots.
For isotherm at 𝑇[ < 𝑇– , the equation may exhibit one or three
real roots, depending on P.
At critical point, the isotherm exhibits a horizontal inflection.

𝜕𝑃 𝜕>𝑃
=0 =0
𝜕𝑉 aš 𝜕𝑉 > aš

These two equations will provide the value of a and b.

 Determination of a and b 38

For van der Waals equation, at 𝑇– , 𝑃– ,

~
𝑅𝑇 > 𝑎 𝑎𝑏
𝑉 − 𝑏+ 𝑉 + 𝑉− =0
𝑃 𝑃 𝑃
Also, (𝑉 − 𝑉– )~ = 𝑉 ~ − 3𝑉– 𝑉 > + 3𝑉– > 𝑉 − 𝑉– ~ = 0

𝑅𝑇– 𝑎
> ~𝑎𝑏
3𝑉– = 𝑏 + 3𝑉– = 𝑉– =
𝑃– 𝑃– 𝑃–
Combining these results,

> 1 3𝑅𝑇– 𝑃– 𝑉– 3
𝑎 = 3𝑉– 𝑃– 𝑏 = 𝑉– 𝑉– = 𝑍– = =
3 8𝑃– 𝑅𝑇– 8
Eliminate 𝑉– for a and b, we have

27𝑅 > 𝑇– > 𝑅𝑇–

𝑎= 𝑏=
64𝑃– 8𝑃–
 Improved Cubic Equations of State 39

𝑅𝑇 𝑎
𝑃= − The van der Waals equation (1873)
𝑉 − 𝑏 𝑉>
𝑅𝑇 𝑎𝛼 1
𝑃= − (𝛼 = ) Redlich-Kwong (RK) equation (1949)
𝑉−𝑏 𝑉 𝑉+𝑏 𝑇

𝑅𝑇 𝑎𝛼
𝑃= − > Peng-Robinson (PR) equation (1976)
𝑉 − 𝑏 𝑉 + 2𝑉𝑏 − 𝑏 >

Expression of α can be found on Page 98 in the textbook.

Improved Cubic Equations of State 40

http://people.ds.cam.ac.uk/pjb10/thermo/pure.html
 Generalized Correlations for Gases 41

Q: What are the limitations of Virial and cubic equations of

state?
A: For each chemical species, we must find few parameters.

𝐵𝑃
𝑍 =1+
𝑅𝑇
Q: Can we find generalized correlations?
A: Yes. N2

Reminder: Z is also related to the

substance and T.
 Generalized Correlations for Gases 42

𝑇 𝑃
Define reduced T and P: 𝑇œ = 𝑃œ =
𝑇– 𝑃–
 Generalized Correlations for Compressibility 43

For simple fluids (Ar, Ks, Xe, other non-polar or slightly polar
gases):
𝑍 = 𝐹(𝑇œ , 𝑃œ )
𝑍 = 𝑍ƒ
For non-simple fluids, introduce the acentric factor 𝜔:
𝑍 = 𝐹(𝑇œ , 𝑃œ , 𝜔)
𝑍 = 𝑍 ƒ + 𝜔𝑍 [

𝑍 ƒ can be found in Table E.1.

𝑍 ƒ can be found in Table E.2.
𝜔 can be found in Table B.1.
 Correlations for Second Virial Coefficient 44

𝐵𝑃 𝐵𝑃– 𝑃œ 𝑃œ 𝐵𝑃–
𝑍 =1+ =1+ = 1 + 𝐵ž (𝐵ž = )
𝑅𝑇 𝑅𝑇– 𝑇œ 𝑇œ 𝑅𝑇–
Pitzer and coworkers proposed: 𝐵ž = 𝐵 ƒ + 𝜔𝐵[

ƒ
0.422 [
0.172
𝐵 = 0.083 − [.‘ 𝐵 = 0.139 −
𝑇œ 𝑇œ „.>

Q: What are the two advantages of this correlation compared

with correlation with Z ?

Self-Study: Correlations for Third Virial Coefficient (Page 103).

 Example 3.10 45

Determine the molar volume of n-butane at 510 K and 25 bar

by each of the following:
a. The ideal-gas equation,
b. The van der Waals equation,
c. The generalized compressibility-factor correlation,
d. The generalized second virial coefficient correlation.

An experimental value for V is 1480.7 cm3 mol-1. Compare

and comment the calculated and experimental data.
 Example 3.10 46

Solution
The ideal-gas equation

𝑅𝑇 8.314 510 ~ m[ ~ m[
𝑉= = = 0.0016961 𝑚 𝑚𝑜𝑙 = 1696 𝑐𝑚 𝑚𝑜𝑙
𝑃 25×10w
The van der Waals equation

~
𝑅𝑇 > 𝑎 𝑎𝑏
𝑉 − 𝑏+ 𝑉 + 𝑉− =0
𝑃 𝑃 𝑃
From the web:
http://people.ds.cam.ac.uk/pjb10/thermo/pure.html
𝑉 = 0.001463 𝑚 ~ 𝑚𝑜𝑙 m[ = 1463 𝑐𝑚 ~ 𝑚𝑜𝑙 m[
Let us check whether web data is correct.
 Example 3.10 47

Let us check, from Table B.1

>x` d aš d `aš
𝑎= 𝑏= 𝑇– = 425.1 𝐾 𝑃– = 37.96 𝑏𝑎𝑟 (Table B.1)
‘„Vš †Vš

27𝑅 > 𝑇– > 27(8.314) > (425.1)> ‘ [ m>

𝑎= = = 1.388 𝑚 𝑃𝑎 𝑚𝑜𝑙
64𝑃– 64×37.96×10w
𝑅𝑇– 8.314×425.1 m„ ~ m[
𝑏= = = 1.164×10 𝑚 𝑚𝑜𝑙
8𝑃– 8×37.96×10w
~
𝑅𝑇 > 𝑎 𝑎𝑏
𝑉 − 𝑏+ 𝑉 + 𝑉− =0
𝑃 𝑃 𝑃
~ m„
8.314×510 >
(0.001463) − 1.164×10 + 0.001463
25×10w
1.388 1.388×1.164×10m„
+ w
0.001463 − w
=0
25×10 25×10
 Example 3.10 48

The generalized compressibility-factor correlation

510 25
𝑇œ = = 1.200 𝑃œ = = 0.659
425.1 37.96
𝑍 ƒ = 0.865 𝑍 [ = 0.038 (Interpolation of data in Table E.1 and E. 2)
𝜔 = 0.200 (Table B.1)

𝑍 = 𝑍 ƒ + 𝜔𝑍 [ = 0.865 + 0.002 0.038 = 0.873

𝑍𝑅𝑇 (0.873) 8.314 510 ~ m[

𝑉= = = 0.001481 𝑚 𝑚𝑜𝑙
𝑃 25×10w
= 1481 𝑐𝑚 ~ 𝑚𝑜𝑙 m[
 Example 3.10 49

The generalized second Virial coefficient correlation

ƒ
0.422 0.422
𝐵 = 0.083 − = 0.083 − = −0.232
𝑇œ [.‘ 1.2[.‘

[
0.172 0.172
𝐵 = 0.139 − = 0.139 − = 0.059
𝑇œ „.> 1.2 „.>

𝐵ž = 𝐵 ƒ + 𝜔𝐵[ = −0.230 + 0.200 0.059 = −0.220

𝑃œ 0.659
𝑍 = 1 + 𝐵ž = 1 + (−0.220) = 0.879
𝑇œ 1.200

𝑍𝑅𝑇 (0.879) 8.314 510 ~ m[

𝑉= = = 0.001491 𝑚 𝑚𝑜𝑙
𝑃 25×10w
= 1491 𝑐𝑚 ~ 𝑚𝑜𝑙 m[
 Generalized Correlations for Liquids 50

Estimation of molar volume of saturated liquids:

˜”C ([maŸ )d/
Rackett Equation 𝑉 = 𝑉– 𝑍–
Unsaturated liquids:
 Department of Chemical and Biomolecular Engineering

CN2121 – Introduction to Chemical Engineering

Thermodynamics
Lecture 5 - 1: Second Law of Thermodynamics

Read Chapter 5.1-5.7

 Outline 2

o Statements of the Second Law

o Heat Engines
o Entropy
o Mathematical Statement of the Second Law
o Entropy Balance for Open Systems
 Two Typical Apparatuses 3

Heat Engine Refrigerator

 Statements of the Second Law 4

• Statement 1 (Kelvin Statement):

Th No apparatus can operate in such a way
that its only effect (in system and
Qh
surroundings) is to convert heat

Heat
W absorbed by a system completely into
Engine work done by the system.
• The 2nd law does not prohibit the
Qc
production of work from heat, but places
Tc a limit on how much of the heat directed
into a cyclic process can be converted
Th > Tc
into work done by the process.
 Statements of the Second Law 5

• Statement 2 (Clausius Statement):

Th No process is possible which consists
solely in the transfer of heat from one
Qh
lower temperature level to a higher one.

Heat
W
Engine • Apply first law
𝑊 + 𝑄* = 𝑄,
Qc

Tc Statement 2 says: 𝑊 > 0.

Th > Tc
 Equivalence of the Two Statements 6

• Net Q:
Th
𝑄, − 𝑄*
Qc Qh Qh > Qc • Net W:
𝑄, − 𝑄*
W = Qh - Qc
Heat Heat
Pump Engine
• Q to W efficiency is

Qc Qc 100%, which
violates the Kelvin
Tc
Statement.

• If violating the Clausius Statement, one will violate the Kelvin

Statement.
Equivalence of the
Equivalence of Two Statements
the Two Statements 7

• Net Q:
Th
0
Qh + Q c Qh
• Net W:
W = Qh
Net Q: 0
0
Heat Heat Net W: 0
Pump Engine
• Net effect: transfer 𝑄*
Netfrom
effect: transfer
a cold Qc from
object to a a
cold object to a hot object
Qc hot object
without workwithout
input, work
which
violates the Clausius statement
input, which violates the
Tc
Clausius statement.
Th > Tc

If• violating
If violating the Kelvin
the Kelvin Statement,
statement, one will
one will violate the violate
Clausius the Clausius
statement
8

Statement.
 Heat Engines 8

• To all heat engine cycles, absorption of

Th heat into the system at a high
temperature, rejection of heat to the
Qh
surroundings at a lower temperature,

Heat
W production of work are essential.
Engine 𝑊 = 𝑄, − 𝑄*

Qc
• Define the thermal efficiency of engine
Tc as:

Th > Tc 𝑊 𝑄, − 𝑄* 𝑄*
𝜂≡ = =1−
𝑄, 𝑄, 𝑄,
Check your understanding 9

• Statement 1: based on the 2nd

law, it is impossible for any
PROCESS to convert heat 100%
to work.

• Statement 2: based on the 2nd

law, it is impossible for any
ENGINE to convert heat 100% to
work.

Right or Wrong?
 Carnot Engine: the Most Effective Engine 10

• Step 1: The system maintains contact with the hot reservoir at 𝑇, , and
undergoes a reversible isothermal process during which heat 𝑄, is
absorbed from the hot reservoir (expansion step).
• Step 2: The system undergoes a reversible adiabatic process that brings
its temperature from 𝑇, to that of the cold reservoir at 𝑇* (expansion step).
• Step 3: The system maintains contact with the reservoir at 𝑇* , and
undergoes a reversible isothermal process in the opposite direction of
step 1, with rejection of heat 𝑄* to the cold reservoir (compression
step).
• Step 4: The system with temperature at 𝑇* undergoes a reversible
adiabatic process that causes its temperature to rise to that of the hot
reservoir at 𝑇, , after which the system recovers to its initial state at the
beginning of step 1 (compression step).
 Carnot
Carnot Engine:the
Engine: the Most
Most Effective
EffectiveEngine
Engine11

12
 Determine the Efficiency of Carnot Engine
Carnot Engine: the Most Effective Engine
12

• For ideal gas: 𝑃𝑉 = 𝑅𝑇

• For isothermal step 1:
∆𝑈 = 0

𝑉:
𝑄, = 𝑊9: = 𝑅𝑇, 𝑙𝑛
𝑉9
12

• Similarly, for isothermal step 3,

𝑉=
∆𝑈 = 0 𝑄* = 𝑊=> = 𝑅𝑇* 𝑙𝑛
𝑉>
𝑉
𝑄, 𝑇, 𝑙𝑛( 𝑉: )
9
=
𝑄* 𝑇* 𝑙𝑛( 𝑉= )
𝑉>
 Determine the Efficiency of Carnot Engine 13

• Generally, for adiabatic processes:

𝑃𝑉 A = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 or 𝑇𝑉 AGH = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
• For adiabatic steps 2 and 4:
𝑇: 𝑉: AGH = 𝑇= 𝑉= AGH 𝑇> 𝑉> AGH = 𝑇9 𝑉9 AGH

• Consider: 𝑇9 = 𝑇: = 𝑇, 𝑇= = 𝑇> = 𝑇*

𝑇, 𝑉: AGH = 𝑇* 𝑉= AGH
𝑉= 𝑉:
=
𝑉> 𝑉9
𝑇, 𝑉9 AGH = 𝑇* 𝑉> AGH
 Determine the Efficiency of Carnot Engine 14

𝑉
𝑄, 𝑇, 𝑙𝑛( 𝑉: ) 𝑇,
9
= =
𝑄* 𝑇* 𝑙𝑛( 𝑉= ) 𝑇*
𝑉>

𝑊 𝑄, − 𝑄* 𝑄* 𝑇*
𝜂≡ = =1− =1−
𝑄, 𝑄, 𝑄, 𝑇,
• The thermal efficiency of a Carnot engine depends only on
the temperature levels and not upon the working substance of
the engine.
• Is it possible that the efficiency of an engine reaches 100%?
Carnot Refrigerator
Carnot Refrigerator 15

• 1 to 4: Adiabatic expansion
𝑄ℎ 1 to 4: Adiabatic expansion
• 4 to 3: Isothermal expansion
4 to 3: Isothermal expansion
𝑇ℎ
• 3 to 2: Adiabatic compression
3 to 2: Adiabatic compression
• 2 to 1: Isothermal compression
𝑄𝑐 𝑇𝑐 2 to 1: Isothermal compression

•All the
Allarguments
the arguments for Carnot
for Carnot engine are validengine
for Carnotare valid for Carnot
Refrigerator

refrigerator.
𝑄ℎ 𝑇ℎ | W| 𝑄𝑐 𝑇𝑐
So, = =1− =1−
𝑄𝑐 𝑇𝑐 𝑄ℎ 𝑄ℎ 𝑇ℎ
𝑄, 𝑇,
=
𝑄* 𝑇* 16

𝑊 𝑄, − 𝑄* 𝑄* 𝑇*
𝜂≡ = =1− =1−
𝑄, 𝑄, 𝑄, 𝑇,
 Carnot’s Theorem 16

• For two given heat reservoirs no engine can have a thermal

efficiency higher than that of a Carnot engine.
Proof:

Th Suppose the two

Th
Qh’ engines deliver the
Qh
same W.
Carnot W Super W
If “Super Engine” has
Engine Engine
a higher efficiency,
Qc Qc’ then 𝑄,J < 𝑄,

Tc Tc
 Carnot’s Theorem
Carnot’s Theorem 17

• For two given heat reservoirs no engine can have a thermal

For two given heat reservoirs no engine can have a thermal efficiency
efficiency
higher than thathigher thanengine.
of a Carnot that of a Carnot engine.
Proof:
Proof:
We use the “Super
Engine” to drive the
Th Th
Carnot refrigerator
We use the “Super
Qh Qh’ 𝑄𝑐 = 𝑄ℎ − 𝑊
Engine” to drive the
′ = 𝑄 ′ − 𝑊
W 𝑄
Carnot ℎrefrigerator.
𝑐
Carnot Super
Refrigerator Engine

𝑄* = 𝑄, − 𝑊
Qc Qc’
𝑄*J = 𝑄,J − 𝑊
Tc Tc
18
 Carnot’s Theorem 18

• The net heat extracted from the cold reservoir is

𝑄* − 𝑄*J = 𝑄, − 𝑊 − 𝑄,J − 𝑊 = 𝑄, − 𝑄,J

• The net heat delivered to the hot reservoir is also

𝑄, − 𝑄,J . This contradicts the second law of
thermodynamics!
• Note, all reversible engines operating between heat
reservoirs at the same two temperatures have the same
efficiency.

𝑇*
𝜂MNO =1−
𝑇,
 Example 5.1 19
A central power plant generates power at a rate of 800,000 kW.
The hot steam has a temperature of 585 K and the power plant
discards heat to a river at 295 K. If the thermal efficiency of the
plant is 70% of the maximum possible value, how much heat is
discarded to the river?

Solution
• According to Carnot’s theorem,
𝑇* 295
𝜂MNO = 1 − = 1 − = 0.4957
𝑇, 585

𝜂 = 0.7×0.4957 = 0.3470

1−𝜂 1 − 0.3470
𝑄* = 𝑊 = 800000 = 1505500 𝑘𝑊
𝜂 0.3470
 Department of Chemical and Biomolecular Engineering

CN2121 – Introduction to Chemical Engineering

Thermodynamics
Lecture 5 - 2: Second Law of Thermodynamics

Read Chapter 5.1-5.7

 Entropy 2

𝑄" 𝑇"
=
𝑄# 𝑇#

𝑄" 𝑄#
=
𝑇" 𝑇#
Add up the Q/T for the entire cycle,

𝑄" 𝑄#
+0+ +0=0
𝑇" 𝑇#
Conclusion: for a Carnot cycle,

𝑑𝑄*+,
( =0
𝑇
 Entropy 3

𝑑𝑄" 𝑑𝑄#
+ =0
𝑇" 𝑇#
when the isothermal steps are
infinitesimal.
For the whole arbitrary
reversible cycle,

𝑑𝑄*+,
( =0
𝑇

𝑑𝑄*+,
is a property!
𝑇
 Entropy 4

• We define a property called entropy 𝑆, which is an intrinsic

property of a system, functionally related to the measurable
coordinates which characterize the system.

𝑑𝑄*+,
• For a reversible process, 𝑑𝑆 = 𝑑𝑄*+, = 𝑇𝑑𝑆
𝑇

𝑑𝑄*+,
• For a finite reversible process, ∆𝑆 = 2
𝑇

• ∆𝑆 is independent of path, for a change from A to B.

∆𝑆 = 𝑆/ − 𝑆1
𝑑𝑄*+,
• If the process is irreversible, ∆𝑆 = 𝑆/ − 𝑆1 ≠ 2
𝑇
 The Second Law Based on Entropy 5

• Situation 1
𝑇4 > 𝑇6 Irreversible process
• Situation 2
𝑇4 𝑇6
𝑇4 = 𝑇6 + 𝑑𝑇 Reversible process
• Situation 3
𝑇4 < 𝑇6 Forbidden process 𝑄

−𝑄 +𝑄
∆𝑆8+9: = ∆𝑆*;<": =
𝑇4 𝑇6

𝑄 𝑄
∆𝑆:=:=>8 = −
𝑇6 𝑇4
 The Second Law Based on Entropy 6

• Situation 1
𝑇4 > 𝑇6 Irreversible process

𝑄 𝑄 𝑄 𝑇4 − 𝑇6
∆𝑆:=:>8 = − = >0
𝑇6 𝑇4 𝑇4 𝑇6
• Situation 2
𝑇4 = 𝑇6 + 𝑑𝑇 Reversible process
∆𝑆:=:>8 = 0
• Situation 3

∆𝑆:=:>8 < 0
 The Second Law Based on Entropy 7

Mathematic Statement: Every process proceeds in such a

direction that the total entropy change is positive, with a limiting
value of zero only for a reversible process. No process is
possible for which the total entropy decreases.

For irreversible process, ∆𝑆:=:>8 > 0,

For reversible process, ∆𝑆:=:>8 infinitely approaches 0.

For closed systems,

∆𝑆:=:>8 = ∆𝑆?@?:+A + ∆𝑆?B**=CD;C< ≥ 0

The first law of thermodynamics states the total energy of the

universe is conserved.
The second law of thermodynamics states the total entropy of
the universe keeps increasing.
 Check Your Understanding 8

Statement1: The 2nd law tells us that the entropy change of

a system in a process must be >0.

Statement 2: The entropy change of water during

freezing/melting phase transition is zero.

Statement 3: The entropy change of a system is ΔS = Q/T for

any process.

Statement 4: An adiabatic and reversible process is an

isentropic process.

Right or wrong?
 Example 5.4 9

A 40-kg steel casting (CP = 0.5 kJ kg−1 K−1) at a

temperature 723.15 K is quenched in 150 kg of oil (CP =
2.5 kJ kg−1 K−1) at 298.15 K. If there are no heat losses,
what is the change in entropy of
(a) the casting,
(b) the oil,
(c) both considered together?

Solution
First, determine the final temperature T of the oil and steel
casting,

40 0.5 𝑇 − 723.15 + 150 2.5 𝑇 − 298.15 = 0

𝑇 = 319.67 𝐾
 Example 5.4 10

For this problem: 𝑑𝑄*+, 𝑑𝐻 𝐶S 𝑑𝑇

𝑑𝑆 = = =
𝑇 𝑇 𝑇
(a) Change in entropy of the casting
𝐶S 𝑑𝑇 𝑇6 319.67
∆𝑆4 = 𝑚 2 = 𝑚𝐶S 𝑙𝑛 = 40 0.5 𝑙𝑛
𝑇 𝑇4 723.15
= −16.33 𝑘𝐽 𝐾 X4

(b) Change in entropy of the oil

𝐶S 𝑑𝑇 𝑇6 319.67
∆𝑆6 = 𝑚 2 = 𝑚𝐶S 𝑙𝑛 = 150 2.5 𝑙𝑛
𝑇 𝑇4 298.15
= 26.13 𝑘𝐽 𝐾 X4

(c) Total entropy change

∆𝑆:=:>8 = ∆𝑆4 + ∆𝑆6 = −16.33 + 26.13 = 9.80 𝑘𝐽 𝐾 X4 > 0
 Entropy Changes of An Ideal Gas 11

In a mechanically reversible process,

𝑑𝑈 = 𝑑𝑄*+, − 𝑃𝑑𝑉
𝑑𝐻 = 𝑑 𝑈 + 𝑃𝑉 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃
Eliminating 𝑑𝑈,
𝑑𝐻 = 𝑑𝑄*+, − 𝑃𝑑𝑉 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 = 𝑑𝑄*+, + 𝑉𝑑𝑃
𝑑𝑄*+, = 𝑑𝐻 − 𝑉𝑑𝑃
For an ideal gas, 𝑑𝐻 = 𝐶S 𝑑𝑇 and 𝑉 = 𝑅𝑇/𝑃
𝑑𝑄*+, 𝑑𝑇 𝑑𝑃
= 𝐶S −𝑅 = 𝑑𝑆 Are these two equations
𝑇 𝑇 𝑃 only applicable to
Integrate from (𝑇4 , 𝑃6 ) to (𝑇6 , 𝑃6 ), we get: reversible process of
ideal gas? Why?
ac Sc ac
𝑑𝑇 𝑑𝑃 ∆𝑆 𝐶S 𝑑𝑇 𝑃6
∆𝑆 = 2 𝐶S −2 𝑅 or =2 − 𝑙𝑛
ab 𝑇 Sb 𝑃 𝑅 ab 𝑅 𝑇 𝑃4
 Example 12

For an ideal gas undergoing a mechanically reversible

process, prove that ∆𝑆 ac
𝐶f 𝑑𝑇 𝑉6
=2 + 𝑙𝑛
𝑅 ab 𝑅 𝑇 𝑉4
Solution
𝑑𝑈 𝑑𝑄*+, 𝑃𝑑𝑉
𝑑𝑈 = 𝑑𝑄*+, − 𝑃𝑑𝑉 = −
𝑇 𝑇 𝑇
For an ideal gas,
𝑃 𝑅
𝑑𝑈 = 𝐶f 𝑑𝑇 =
𝑇 𝑉
𝑑𝑇 𝑑𝑉 𝑑𝑆 𝐶f 𝑑𝑇 𝑑𝑉
𝑑𝑆 = 𝐶f +𝑅 𝑜𝑟 = +
𝑇 𝑉 𝑅 𝑅𝑇 𝑉

Integrate from (𝑇4 , 𝑉4 ) to (𝑇6 , 𝑉6 ), ac

∆𝑆 𝐶f 𝑑𝑇 𝑉6
=2 + 𝑙𝑛
𝑅 ab 𝑅 𝑇 𝑉4
Example (5.2) Example 5.2 13

For an ideal gas with constant heat capacities undergoing a reversible, adiabatic
process, 𝑇𝑃(1−𝛾)/𝛾 = 𝑐𝑜𝑛𝑠𝑡 can be written as:
𝑇2 𝑃2 (𝛾−1)/𝛾
=( )
𝑇1 𝑃1
Show that this same equation results from application of
𝑇
∆𝑆 𝐶𝑃 𝑑𝑇 𝑃
=න − 𝑙𝑛 with ∆𝑆 = 0
𝑅 𝑇0 𝑅 𝑇 𝑃0

Solution ∆𝑆 = 0, 𝐶𝑃 is constant, the equation can be written as:

𝑇2 𝑅 𝑃2
0 = 𝑙𝑛 − 𝑙𝑛
𝑇1 𝐶𝑃 𝑃1
𝐶𝑃 𝐶𝑃 𝑅 𝛾−1
𝛾≡ = =
𝐶𝑉 𝐶𝑃 − 𝑅 𝐶𝑃 𝛾

𝑇2 𝛾 − 1 𝑃2 𝑇2 𝑃2 (𝛾−1)/𝛾
Thus, 𝑙𝑛 = 𝑙𝑛 =( ) Self-study
𝑇1 𝛾 𝑃1 𝑇1 𝑃1 31
Example Example 14

Calculate ∆𝑆 for the following process in an isolated system. N2 behaves

as an ideal gas. The two chambers have equal volumns.

1 mol N2 1 mol N2
Vacuum
T1, P1, V1 T2, P2, V2

For the process, 𝑊 = 0 𝑄=0 Δ𝑈 = 𝑊 + 𝑄 = 0

For ideal gas, internal energy is only a function of T: Δ𝑇 = 0

𝑑𝑇 𝑑𝑃 𝑑𝑃
𝑑𝑆 = 𝐶𝑃 −𝑅 = −𝑅
𝑇 𝑃 𝑃

𝑃2 𝑉1 1
∆𝑆 = −𝑅𝑙𝑛 = −𝑅𝑙𝑛 = −8.314𝑙𝑛 = 5.76 𝐽/𝐾
𝑃1 𝑉2 2
32
 Example Example 15

Calculate ∆𝑆 for the following process in an isolated system. N2 and O2 behave

7
as ideal gases with 𝐶𝑃 = 𝑅. The two chambers have equal volumns.
2

1 mol N2 1 mol O2
1 mol N2 + 1 mol O2
10 ºC 20 ºC

As N2 and O2 have the same CP, the final T is 15 ºC

𝐶𝑉 𝑑𝑇 𝑅𝑑𝑉
𝑑𝑆𝑁2 = +
𝑇 𝑉
𝑇2 𝑉2 5 288.15
∆𝑆𝑁2 = 𝐶𝑉 𝑙𝑛 + 𝑅𝑙𝑛 = × 8.314𝑙𝑛 + 8.314𝑙𝑛2 = 6.11 𝐽/𝐾
𝑇1 𝑉1 2 283.15

Similarly: ∆𝑆𝑂2 = 5.42 𝐽/𝐾

∆𝑆𝑡𝑜𝑡𝑎𝑙 = ∆𝑆𝑁2 + ∆𝑆𝑂2 = 11.53 𝐽/𝐾

33
 Example
Example 16

Calculate ∆𝑆 for the following process in an isolated system. N2 and O2 behave as ideal
gases, with the same Cp and temperature. The two chambers have equal volumns.
Hint: the temperature for the following 𝑇2
∆𝑆 𝐶𝑉 𝑑𝑇 𝑉2 𝑉2
processes remains constant So: =න + 𝑙𝑛 = 𝑙𝑛
𝑅 𝑇1 𝑅 𝑇 𝑉1 𝑉1

1 mol N2 Vacuum 1 mol N2 ∆𝑆 = 𝑅𝑙𝑛2

1 mol N2
1 mol N2 1 mol O2 ∆𝑆 = 2𝑅𝑙𝑛2
1 mol O2

1 mol N2
1 mol N2 1 mol N2 ∆𝑆 =?
1 mol N2
Gibbs Paradox 34
 Example
Example 17

One mole of ideal gas undergoes the following reversible processes:

a) From 𝑇1 = 700 K and 𝑃1 = 1.5 bar, cooled to T2 = 350 K at
constant pressure.
b) From 𝑇2 = 350 K and 𝑃2 = 1.5 bar, compressed to a pressure 𝑃3
isothermally.
c) Back to initial state along a path of which PT = C (constant).
Calculate W, Q, ∆𝑈, ∆𝐻, and ∆𝑆 for each of the three processes and for
the entire cycle. What is the thermal efficiency for the cycle? Take 𝐶𝑉 =
(3/2)R and 𝐶𝑃 = (5/2)R.

Solution

35
 Example
Example 18

(a) Isobaric cooling (1→2),

∆𝑈𝑎 = 𝐶𝑉 𝑇2 − 𝑇1 = 1.5 8.314 350 − 700 = −4364.85 𝐽

∆𝐻𝑎 = 𝐶𝑃 𝑇2 − 𝑇1 = 2.5 8.314 350 − 700 = −7274.75 𝐽

𝑇2
𝑑𝑇 𝑃2 𝑇2 350
∆𝑆𝑎 = 𝐶𝑃 න − 𝑅𝑙𝑛 = 𝐶𝑃 𝑙𝑛 = 2.5 8.314 𝑙𝑛 = −14.41 𝐽 𝐾 −1
𝑇1 𝑇 𝑃1 𝑇1 700

𝑄𝑎 = ∆𝐻𝑎 = −7274.75 𝐽

𝑊𝑎 = ∆𝑈𝑎 − 𝑄𝑎 = −4364.85 − (−7274.75) = 2909.90 𝐽

36
 Example
Example 19

(b) Isothermal compression (2→3)

∆𝑈𝑏 = ∆𝐻𝑏 = 0
𝑇3
𝑑𝑇 𝑃3 𝑃3
∆𝑆𝑏 = 𝐶𝑃 න − 𝑅𝑙𝑛 = −𝑅𝑙𝑛 need to find P3
𝑇2 𝑇 𝑃2 𝑃2

Consider the relationship between State 3 and State 1

𝑃1 𝑇1 𝑃1 𝑇1 1.5 × 105 × 700
𝑃3 𝑇3 = 𝑃1 𝑇1 𝑃3 = = = = 3 × 105 𝑃𝑎 = 3 𝑏𝑎𝑟
𝑇3 𝑇2 350
𝑃3 3
∆𝑆𝑏 = −𝑅𝑙𝑛 = −8.314𝑙𝑛 = −5.76 𝐽 𝐾 −1
𝑃2 1.5

𝑃3
𝑊𝑏 = −𝑄𝑏 = 𝑅𝑇2 𝑙𝑛 = 2016.99 𝐽
𝑃2

37
 Example
Example 20

(c) PT = C (3→1)
∆𝑈𝑐 = 𝐶𝑉 𝑇1 − 𝑇3 = 1.5 8.314 700 − 350 = 4364.85 𝐽

∆𝐻𝑐 = 𝐶𝑃 𝑇1 − 𝑇3 = 2.5 8.314 700 − 350 = 7274.75 𝐽

𝑇1
𝑑𝑇 𝑃1 𝑇1 𝑃1
∆𝑆𝑐 = 𝐶𝑃 න − 𝑅𝑙𝑛 = 𝐶𝑃 𝑙𝑛 − 𝑅𝑙𝑛 = 14.41 + 5.76 = 20.17 𝐽 𝐾 −1
𝑇3 𝑇 𝑃3 𝑇3 𝑃3
𝑑𝑃 𝑅𝐶𝑑𝑃
𝑑𝑊𝑐 = −𝑅𝑑𝑇 + 𝑅𝑇 = −𝑅𝑑𝑇 +
𝑃 𝑃2
1 1
𝑊𝑐 = −𝑅 𝑇1 − 𝑇3 − 𝑅𝐶 − = −2𝑅 𝑇1 − 𝑇3 = −5819.80 𝐽
𝑃1 𝑃3
Why?

𝑄𝑐 = ∆𝑈𝑐 − 𝑊𝑐 = 4364.85 − (−5819.80) = 10184.65 𝐽

38
 Example
Example 21

For the entire circle

∆𝑈 = ∆𝑈𝑎 + ∆𝑈𝑏 + ∆𝑈𝑐 = 0

∆𝐻 = ∆𝐻𝑎 + ∆𝐻𝑏 + ∆𝐻𝑐 = 0

∆𝑆 = ∆𝑆𝑎 + ∆𝑆𝑏 + ∆𝑆𝑐 = 0

𝑄 = 𝑄𝑎 + 𝑄𝑏 + 𝑄𝑐 = 892.91 𝐽

𝑊 = 𝑊𝑎 + 𝑊𝑏 + 𝑊𝑐 = −892.91 𝐽

Summary: U, H, S are state functions, thus ∆𝑈 = ∆𝐻 = ∆𝑆 = 0

for the entire cycle.
𝑊 892.91
Thermal Efficiency 𝜂= = = 8.8 %
𝑄𝑐 10184.65

Which Q should you use?

39
 Entropy Balance for Open System
Entropy Balance for Open Systems 22

For closed systems,

mሶ 𝑖𝑛
∆𝑆𝑡𝑜𝑡𝑎𝑙 = 𝑆𝐺 = ∆𝑆𝑠𝑦𝑠 + ∆𝑆𝑠𝑢𝑟𝑟 ≥ 0

𝑄
∆𝑆𝑠𝑢𝑟𝑟 =−
𝑇𝜎
mሶ 𝑜𝑢𝑡
For open systems,

𝑇𝑖𝑚𝑒 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑇𝑖𝑚𝑒 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑁𝑒𝑡 𝑟𝑎𝑡𝑒 𝑜𝑓

𝑇𝑜𝑡𝑎𝑙 𝑟𝑎𝑡𝑒 𝑐ℎ𝑎𝑛𝑔𝑒 𝑜𝑓 𝑐ℎ𝑎𝑛𝑔𝑒 𝑜𝑓 𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛
𝑜𝑓 𝑒𝑛𝑡𝑟𝑜𝑝𝑦 = 𝑒𝑛𝑡𝑟𝑜𝑝𝑦 + +
𝑒𝑛𝑡𝑟𝑜𝑝𝑦 𝑖𝑛 𝑒𝑛𝑡𝑟𝑜𝑝𝑦 𝑜𝑓
𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 𝑖𝑛 𝑐𝑜𝑛𝑡𝑟𝑜𝑙 𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 𝑓𝑙𝑜𝑤𝑖𝑛𝑔 𝑠𝑡𝑟𝑒𝑎𝑚𝑠
𝑣𝑜𝑙𝑢𝑚𝑒

The equivalent equation of entropy balance is

𝑑(𝑚𝑆)𝐶𝑉 𝑑𝑆𝑠𝑢𝑟𝑟
𝑆𝐺ሶ = + − 𝑆𝑖𝑛 𝑚ሶ 𝑖𝑛 + 𝑆𝑜𝑢𝑡 𝑚ሶ 𝑜𝑢𝑡 ≥ 0
𝑑𝑡 𝑑𝑡
40
 Entropy Balance for Open System
Entropy Balance for Open Systems 23

𝑑𝑆𝑠𝑢𝑟𝑟 𝑄𝑗ሶ
= −෍
𝑑𝑡 𝑇𝜎,𝑗
𝑗

𝑑(𝑚𝑆)𝐶𝑉 Qሶ j
So we have 𝑆𝐺ሶ = −෍ − 𝑆𝑖𝑛 𝑚ሶ 𝑖𝑛 + 𝑆𝑜𝑢𝑡 𝑚ሶ 𝑜𝑢𝑡 ≥ 0
𝑑𝑡 Tσ,j
j

𝑆𝐺ሶ = 0 only when the process is internally reversible within the control volume,
and heat transfer between the control volume and its surroundings is reversible.

For a steady-state flow process,

Qሶ j
𝑆𝐺ሶ = − ෍ − 𝑚(𝑆
ሶ 𝑖𝑛 − 𝑆𝑜𝑢𝑡 ) ≥ 0
Tσ,j
j

In a uniform surroundings with temperature 𝑇𝜎 :

𝑄𝑗ሶ 𝑄ሶ
෍ =
𝑇𝜎,𝑗 𝑇𝜎
𝑗
41
 Example 5.5
Example 5.5 24

In a steady-state flow process, 1 mol/s of air at 600 K and 1 atm is continuously

mixed with 2 mol/s of air at 450 K and 1 atm. The product stream is at 400 K
and 1 atm. A schematic representation of the process is shown in the figure.
Determine the rate of heat transfer and rate of entropy generation for the
process. Assume that air is an ideal gas with 𝐶𝑃 = 7R/2, that the surroundings
are at 300 K, and that kinetic/potential energy changes are negligible.

42
 Example 5.5
Example 5.5 25

Solution
General energy balance equation
𝑑(𝑚𝑈)𝐶𝑉 1 1
= 𝑄ሶ + 𝑊ሶ + 𝑚ሶ 𝑖𝑛(𝐻𝑖𝑛 + 𝑢𝑖𝑛2 + 𝑔𝑧𝑖𝑛) − 𝑚ሶ 𝑜𝑢𝑡(𝐻𝑜𝑢𝑡 + 𝑢𝑜𝑢𝑡2 + 𝑔𝑧𝑜𝑢𝑡 )
𝑑𝑡 2 2
𝑑(𝑚𝑈)𝐶𝑉
For the system: = 0, 𝑊ሶ = 0, Ignore Ek, Ep
𝑑𝑡
𝑄ሶ = 𝑚ሶ 𝑜𝑢𝑡𝐻𝑜𝑢𝑡 − 𝑚ሶ 𝑖𝑛𝐻𝑖𝑛

Replace 𝑚ሶ with 𝑛ሶ

𝑄ሶ = 𝑛ሶ 𝑜𝑢𝑡 𝐻𝑜𝑢𝑡 − 𝑛ሶ 𝐴 𝐻𝐴 − 𝑛ሶ 𝐵 𝐻𝐵 = 𝑛ሶ 𝐴 𝐻𝑜𝑢𝑡 − 𝐻𝐴 + 𝑛ሶ 𝐵 (𝐻𝑜𝑢𝑡 − 𝐻𝐵 )

= 𝑛ሶ 𝐴 𝐶𝑃 𝑇𝑜𝑢𝑡 − 𝑇𝐴 + 𝑛ሶ 𝐵 𝐶𝑃 𝑇𝑜𝑢𝑡 − 𝑇𝐵 = 𝐶𝑃 [𝑛ሶ 𝐴 𝑇𝑜𝑢𝑡 − 𝑇𝐴 + 𝑛ሶ 𝐵 𝑇𝑜𝑢𝑡 − 𝑇𝐵 ]

7
= 8.314 1 400 − 600 + 2 400 − 450 = −8729.7 𝐽 𝑠 −1
2
43
 Example 5.5
Example 5.5 26

𝑑(𝑚𝑆)𝐶𝑉 Qሶ j
𝑆𝐺ሶ = −෍ − 𝑆𝑖𝑛 𝑚ሶ 𝑖𝑛 + 𝑆𝑜𝑢𝑡 𝑚ሶ 𝑜𝑢𝑡 ≥ 0
𝑑𝑡 Tσ,j
j
𝑑(𝑚𝑆)𝐶𝑉 𝑄𝑗ሶ 𝑄ሶ
For the system: =0 ෍ =
𝑑𝑡 𝑇𝜎,𝑗 𝑇𝜎
𝑗

𝑄ሶ
𝑆𝐺ሶ = − − 𝑆𝑖𝑛 𝑚ሶ 𝑖𝑛 + 𝑆𝑜𝑢𝑡 𝑚ሶ 𝑜𝑢𝑡 ≥ 0
𝑇𝜎
Replace 𝑚ሶ with 𝑛ሶ
𝑄ሶ 𝑄ሶ
𝑆𝐺ሶ = 𝑛ሶ 𝑜𝑢𝑡 𝑆𝑜𝑢𝑡 − 𝑛ሶ 𝐴 𝑆𝐴 − 𝑛ሶ 𝐵 𝑆𝐵 − = 𝑛ሶ 𝐴 𝑆𝑜𝑢𝑡 − 𝑆𝐴 + 𝑛ሶ 𝐵 𝑆𝑜𝑢𝑡 − 𝑆𝐵 −
𝑇𝜎 𝑇𝜎
𝑇 𝑇 𝑄ሶ 𝑇 𝑇 𝑄ሶ
= 𝑛ሶ 𝐴 𝐶𝑃 𝑙𝑛 + 𝑛ሶ 𝐵 𝐶𝑃 𝑙𝑛 − = 𝐶𝑃 (𝑛ሶ 𝐴 𝑙𝑛 + 𝑛ሶ 𝐵 𝑙𝑛 ) −
𝑇𝐴 𝑇𝐵 𝑇𝜎 𝑇𝐴 𝑇𝐵 𝑇𝜎
7 400 400 8729.7
= 8.314 1 ln + 2 ln +
2 600 500 300

= 10.446 J K −1 s −1 What if we mix O2 and N2?

44
What if the fluids are not ideal gases?
 Problem-Solving Problem
Problem-solving Procedure 27

Tips:

1. Draw a diagram schematically

2. Define the system (state, paths, flows)
3. Write and evaluate mass balance equation
4. Write and evaluate energy balance equation
5. Write and evaluate entropy balance equation

45
 Entropy at the Microscopic Viewpoint
Entropy at the Microscopic Viewpoint 28

𝑆 = 𝑘𝐵 𝑙𝑛 𝑊

𝑊2
∆𝑆 = 𝑘𝐵 𝑙𝑛
𝑊1

𝑘𝐵 : Boltzmann Constant

VS.
W: number of dispersed ways
(probability)
Ludwig Boltzmann

Synonym of S: probability, configuration, disorder, etc

46
47
 The Third Law of Thermodynamics
The Third Law of Thermodynamics 29

The absolute entropy is zero for all perfect crystalline substances at

absolute zero temperature. In other words, all these substances lose
their energy at absolute zero temperature.

48
 Summary
Summary 30

1. The Second Law of Thermodynamics

Two statements
2. Heat Engines
|W| 𝑇𝑐
𝜂≡ 𝜂𝑚𝑎𝑥 =1−
𝑄ℎ 𝑇ℎ
3. Entropy
𝑑𝑄𝑟𝑒𝑣
𝑑𝑆 = ∆𝑆𝑡𝑜𝑡𝑎𝑙 = ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + ∆𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔 ≥ 0
𝑇
𝑇2
∆𝑆 𝐶𝑃 𝑑𝑇 𝑃2
=න − 𝑙𝑛 Ideal gas, reversible process
𝑅 𝑇1 𝑅 𝑇 𝑃1

4. Entropy Balance for Open Systems

𝑑(𝑚𝑆)𝐶𝑉 Qሶ j
𝑆𝐺ሶ = −෍ − 𝑆𝑖𝑛 𝑚ሶ 𝑖𝑛 + 𝑆𝑜𝑢𝑡 𝑚ሶ 𝑜𝑢𝑡 ≥ 0
𝑑𝑡 Tσ,j
j 52
 Department of Chemical and Biomolecular Engineering

CN2121 – Introduction to Chemical Engineering

Thermodynamics
Lecture 6: Thermodynamic Properties of Fluids

Read Chapter 6
MathematicMathematic
EquationsEquations
in This Chapter 2

Product rule: 𝑑 𝑥𝑦 = 𝑥𝑑𝑦 + 𝑦𝑑𝑥

Power rule: 𝑑𝑥 𝑛 = 𝑛𝑥 𝑛−1 𝑑𝑥

𝑥 𝑦𝑑𝑥 − 𝑥𝑑𝑦
Quotient rule: 𝑑( ) =
𝑦 𝑦2
𝑑𝑥 𝑑𝑥 𝑑𝑢
Chain rule: =
𝑑𝑦 𝑑𝑢 𝑑𝑦
𝜕𝑥 𝜕𝑦 𝜕𝑧
Cyclic rule: ( )𝑧 ( )𝑥 ( )𝑦 = −1
𝜕𝑦 𝜕𝑧 𝜕𝑥
Mixed derivative theorem: If Z is a function of X and Y
𝜕2𝑍 𝜕2𝑍
=
𝜕𝑋𝜕𝑌 𝜕𝑌𝜕𝑋 2
 Outline 3

o Property Relations for Homogenous Phases

o Residual Properties
o Residual Properties by Equation of State
o Generalized Property Correlations for Gases
Recall from 1st and 2nd Laws of Thermodynamics 4
Two New Two
Concepts: A andA G
New Concept: and G 5

At constant P = Pext and S:

𝑑𝑈 + 𝑃𝑒𝑥𝑡 𝑑𝑉 − 𝑇𝜎 𝑑𝑆 < 0
𝑑𝑈 + 𝑑(𝑃𝑉) < 0 𝑑(𝑈 + 𝑃𝑉) < 0
𝑑𝐻 < 0
Implication: for a spontaneous process at constant P and S, the enthalpy of
the system will decrease.

What are the disadvantages of using dU and dH to judge a

spontaneous process?

5
Two New Two
Concepts: A andA G
New Concept: and G 6
At constant V and T = Tσ:
𝑑𝑈 + 𝑃𝑒𝑥𝑡 𝑑𝑉 − 𝑇𝜎 𝑑𝑆 < 0
𝑑𝑈 − 𝑇𝑑𝑆 < 0 𝑑(𝑈 − 𝑇𝑆) < 0
Define: 𝐴 ≡ 𝑈 − 𝑇𝑆
𝑑𝐴 < 0 A is called Helmholtz free energy
At constant P = Pext and T = Tσ:
𝑑𝑈 + 𝑃𝑒𝑥𝑡 𝑑𝑉 − 𝑇𝜎 𝑑𝑆 < 0
𝑑𝑈 + 𝑑(𝑃𝑉) − 𝑑(𝑇𝑆) < 0 𝑑(𝑈 + 𝑃𝑉 − 𝑇𝑆) < 0 𝑑(𝐻 − 𝑇𝑆) < 0
Define: 𝐺 ≡ 𝐻 − 𝑇𝑆
𝑑𝐺 < 0 G is called Gibbs free energy
Implications: for a spontaneous process at constant V and T, the Helmholtz
free energy of the system will decrease; at constant P and T, the Gibbs free
6
energy of the system will decrease.
Fundamental RelationsRelations
Fundamental 7

Purpose: to derive equations which allow calculation of U, H, S, G and A

from PVT and heat-capacity data.
For a closed system, where the change occurs between equilibrium states

𝑑𝑈 = 𝑑𝑄 + 𝑑𝑊 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉

𝐻 ≡ 𝑈 + 𝑃𝑉 For a homogeneous fluid

of constant composition.
𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
𝐴 ≡ 𝑈 − 𝑇𝑆 𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃
𝑑𝐴 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇
𝑑𝐴 = 𝑑𝑈 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇 𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇
𝐺 ≡ 𝐻 − 𝑇𝑆
𝑑𝐺 = 𝑑𝐻 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇

7
Maxwell Relations
Maxwell Relations 8

All the fundamental relations have the general equation:

𝑑𝐹 = 𝑀𝑑𝑥 + 𝑁𝑑𝑦
𝜕𝐹 𝜕𝐹
or 𝑑𝐹(𝑥, 𝑦) ≡ ( )𝑦 𝑑𝑥 + ( )𝑥 𝑑𝑦
𝜕𝑥 𝜕𝑦
𝜕𝐹 𝜕𝐹
Therefore 𝑀 ≡ ( )𝑦 𝑁 ≡ ( )𝑥
𝜕𝑥 𝜕𝑦
𝜕𝑀 𝜕2𝐹 𝜕𝑁 𝜕2𝐹
Then ( )𝑥 = ( )𝑦 =
𝜕𝑦 𝜕𝑦𝜕𝑥 𝜕𝑥 𝜕𝑥𝜕𝑦
The order of differentiation in mixed second derivatives is immaterial, so
𝜕𝑀 𝜕𝑁
( )𝑥 = ( )𝑦
𝜕𝑦 𝜕𝑥

8
Maxwell Relations
Maxwell Relations 9

𝜕𝑀 𝜕𝑁
𝑑𝐹 = 𝑀𝑑𝑥 + 𝑁𝑑𝑦 ( )𝑥 = ( )𝑦
𝜕𝑦 𝜕𝑥
Apply this to the expressions of dU, dH, dA and dG,
𝜕T 𝜕P
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 ( )S = −( )V
𝜕V 𝜕S
𝜕𝑇 𝜕𝑉
𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 ( )𝑆 = ( )𝑃
𝜕𝑃 𝜕𝑆
Maxwell’s
𝜕𝑃 𝜕𝑆 equations
𝑑𝐴 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇 ( )𝑉 = ( ) 𝑇
𝜕𝑇 𝜕𝑉
𝜕𝑉 𝜕𝑆
𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 ( )𝑃 = −( ) 𝑇
𝜕𝑇 𝜕𝑃

What are the significance of Maxwell’s equations?

9
 10

𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃
𝑑𝐴 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇
𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇

𝜕T 𝜕P 𝜕𝑃 𝜕𝑆
( )S = −( )V ( )𝑉 = ( ) 𝑇
𝜕V 𝜕S 𝜕𝑇 𝜕𝑉
𝜕𝑇 𝜕𝑉 𝜕𝑉 𝜕𝑆
( )𝑆 = ( )𝑃 ( )𝑃 = −( ) 𝑇
𝜕𝑃 𝜕𝑆 𝜕𝑇 𝜕𝑃
10
 Check your understanding
Check Your Understanding 11

Statement 1. The fundamental relations are only right in a reversible

process.

Statement 2. In an isobaric process, H increases with increasing S.

Statement 3. In an isothermal process, S decreases with increasing

P.

Right or wrong?
 Properties
Propertiesfor
for Ideal Gasand
Ideal Gas andReal
Real Substances
Substances 12

1 mol gas changes from initial state (T1, P1) to final state (T2, P2)
For ideal gas For real substances
𝑅𝑇2 𝑅𝑇1 𝑍2 𝑅𝑇2 𝑍1 𝑅𝑇1
∆𝑉 = − ∆𝑉 = −
𝑃2 𝑃1 𝑃2 𝑃1
𝑇2 𝑑𝑈 = 𝐶𝑉 𝑑𝑇+? 𝑑𝑉
∆𝑈 = න 𝐶𝑉 𝑑𝑇 (𝑑𝑈 = 𝐶𝑉 𝑑𝑇)
𝑇1 𝑇2 𝑉2

𝑇2
∆𝑈 = න 𝐶𝑉 𝑑𝑇 + න ? 𝑑𝑉
𝑇1 𝑉1
∆𝐻 = න 𝐶𝑃 𝑑𝑇 (𝑑𝐻 = 𝐶𝑃 𝑑𝑇)
𝑇1
𝑑𝐻 = 𝐶𝑃 𝑑𝑇+? 𝑑𝑃
𝑇2
𝑑𝑇 𝑃2 𝑑𝑇 𝑑𝑃
∆𝑆 = න 𝐶𝑃 − 𝑅𝑙𝑛 (𝑑𝑆 = 𝐶𝑃 −𝑅 ) 𝑇2 𝑃2
𝑇1 𝑇 𝑃1 𝑇 𝑃
∆𝐻 = න 𝐶𝑃 𝑑𝑇 + න ? 𝑑𝑃
𝑇1 𝑃1
𝑇2
𝑑𝑇 𝑉2 𝐶𝑉 𝑑𝑇 𝑑𝑉
∆𝑆 = න 𝐶𝑉 + 𝑅𝑙𝑛 (𝑑𝑆 = +𝑅 )
𝑇1 𝑇 𝑉1 𝑇 𝑉 𝑑𝑆 ? ∆𝑆 ? 13
H and SH as
andFunctions of T of
S and Functions and P P
T and 13

𝜕𝐻 𝜕𝐻 𝜕𝐻
𝑑𝐻 = ( )𝑃 𝑑𝑇 + ( ) 𝑇 𝑑𝑃 ( )𝑃 ≡ 𝐶𝑃
𝜕𝑇 𝜕𝑃 𝜕𝑇
𝜕𝐻 𝜕𝑆
𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 ( ) 𝑇 = 𝑇( ) 𝑇 + 𝑉
𝜕𝑃 𝜕𝑃

𝜕𝑆 𝜕𝑉 𝜕𝐻 𝜕𝑉
Since ( ) 𝑇 = −( )𝑃 ( ) 𝑇 = 𝑉 − 𝑇( )𝑃
𝜕𝑃 𝜕𝑇 𝜕𝑃 𝜕𝑇

𝜕𝑉
𝒅𝑯 = 𝐶𝑃 𝑑𝑇 + [𝑉 − 𝑇( )𝑃 ]𝑑𝑃
𝜕𝑇

Since 𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃

𝑑𝐻 𝑉𝑑𝑃 𝑑𝑇 𝜕𝑉
𝒅𝑺 = − = 𝐶𝑃 − ( )𝑃 𝑑𝑃
𝑇 𝑇 𝑇 𝜕𝑇
14
U and SU as
andFunctions of T of
S and Functions and V V
T and 14

𝜕𝑈 𝜕𝑈 𝜕𝑈
𝑑𝑈 = ( )𝑉 𝑑𝑇 + ( ) 𝑇 𝑑𝑉 ( )𝑉 ≡ 𝐶𝑉
𝜕𝑇 𝜕𝑉 𝜕𝑇

𝜕𝑈 𝜕𝑆
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 ( ) 𝑇 = 𝑇( ) 𝑇 − 𝑃
𝜕𝑉 𝜕𝑉
𝜕𝑆 𝜕𝑃 𝜕𝑈 𝜕𝑃
Since ( ) 𝑇 = ( )𝑉 ( ) 𝑇 = 𝑇( )𝑉 − 𝑃
𝜕𝑉 𝜕𝑇 𝜕𝑉 𝜕𝑇

𝜕𝑃
𝒅𝑼 = 𝐶𝑉 𝑑𝑇 + [𝑇( )𝑉 − 𝑃]𝑑𝑉
𝜕𝑇
1
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 𝑑𝑆 = (𝑑𝑈 + 𝑃𝑑𝑉)
𝑇

𝑑𝑇 𝜕𝑃
𝒅𝑺 = 𝐶𝑉 + ( )𝑉 𝑑𝑉
𝑇 𝜕𝑇 15
Example Example 15

(a) Show that :

𝜕𝐶𝑃 𝜕2𝑉
( ) = −𝑇( 2 )𝑃
𝜕𝑃 𝑇 𝜕𝑇
What is the result of application of this equation to an ideal gas?

(b) Show that: 𝜕𝑃 𝜕𝑉

𝐶𝑃 = 𝐶𝑉 + 𝑇( )𝑉 ( )𝑃
𝜕𝑇 𝜕𝑇
Evaluate this equation for an ideal gas and a gas that obeys the
van der Waals equation
Analysis:

For (a) 𝜕𝐻 𝜕𝐶𝑃 𝜕2𝐻

𝐶𝑃 ≡ ( )𝑃 ( )𝑇 = need to use H (T, P)
𝜕𝑇 𝜕𝑃 𝜕𝑇𝜕𝑃

For (b) need to replace Cp and Cv with H and U, and then use
fundamental relationships 16
Example Example 16

Solution:
𝜕𝑉
(a) 𝑑𝐻 = 𝐶𝑃 𝑑𝑇 + [𝑉 − 𝑇( )𝑃 ]𝑑𝑃
𝜕𝑇
𝜕𝐻 𝜕𝐻 𝜕𝑉
( )𝑃 ≡ 𝐶𝑃 ( ) 𝑇 = 𝑉 − 𝑇( )𝑃
𝜕𝑇 𝜕𝑃 𝜕𝑇
𝜕𝑉
2
𝜕 𝐻 𝜕𝐶𝑃 2
𝜕 𝐻 𝜕 𝑉 − 𝑇( )
𝜕𝑇 𝑃
=( ) ={ }𝑃
𝜕𝑇𝜕𝑃 𝜕𝑃 𝑇 𝜕𝑃𝜕𝑇 𝜕𝑇
𝜕𝑉
𝜕2𝐻 𝜕2𝐻 𝜕𝐶𝑃 𝜕 𝑉 − 𝑇( )
𝜕𝑇 𝑃
= ( )𝑇 = { }𝑃
𝜕𝑇𝜕𝑃 𝜕𝑃𝜕𝑇 𝜕𝑃 𝜕𝑇

𝜕𝑉
𝜕 𝑉 − 𝑇( )𝑃 𝜕𝑉 𝜕𝑉 𝜕2𝑉 𝜕2𝑉 𝜕𝐶𝑃
𝜕𝑇
{ }𝑃 = [ − −𝑇 ] = −𝑇( 2 )𝑃 = ( )
𝜕𝑇 𝜕𝑇 𝜕𝑇 𝜕𝑇 2 𝑃 𝜕𝑇 𝜕𝑃 𝑇

For ideal gas,

𝜕𝑉 𝑅 𝜕2𝑉 𝜕𝐶𝑃
( )𝑃 = , ( 2 )𝑃 = 0 So, ( )𝑇 = 0
𝜕𝑇 𝑃 𝜕𝑇 𝜕𝑃 17
Example Example 17

𝜕𝐻 𝜕(𝑈 + 𝑃𝑉) 𝜕𝑈 𝜕𝑉
(b) 𝐶𝑝 = ( )𝑃 = ( )𝑃 = ( )𝑃 + 𝑃( )𝑃
𝜕𝑇 𝜕𝑇 𝜕𝑇 𝜕𝑇

𝜕𝑈 𝜕𝑈 𝜕𝑈
𝑑𝑈 = ( )𝑉 𝑑𝑇 + ( ) 𝑇 𝑑𝑉 = 𝐶𝑉 𝑑𝑇 + ( ) 𝑇 𝑑𝑉
𝜕𝑇 𝜕𝑉 𝜕𝑉
𝜕𝑈 𝜕𝑈 𝜕𝑉
( )𝑃 = 𝐶𝑉 + ( ) 𝑇 ( )𝑃
𝜕𝑇 𝜕𝑉 𝜕𝑇

𝜕𝑈 𝜕𝑉 𝜕𝑉
𝐶𝑝 = 𝐶𝑉 + ( ) 𝑇 ( )𝑃 + 𝑃( )𝑃
𝜕𝑉 𝜕𝑇 𝜕𝑇

𝜕𝑃 𝜕𝑈 𝜕𝑃
Consider: 𝑑𝑈 = 𝐶𝑉 𝑑𝑇 + [𝑇( )𝑉 − 𝑃]𝑑𝑉 ( ) 𝑇 = 𝑇( )𝑉 − 𝑃
𝜕𝑇 𝜕𝑉 𝜕𝑇

𝜕𝑃 𝜕𝑉
Therefore, 𝐶𝑃 = 𝐶𝑉 + 𝑇( )𝑉 ( )𝑃
𝜕𝑇 𝜕𝑇
18
 Example Example 18
𝜕𝑃 𝜕𝑉
(b) 𝐶𝑃 = 𝐶𝑉 + 𝑇( )𝑉 ( )𝑃
𝜕𝑇 𝜕𝑇
𝜕𝑃 𝑅 𝜕𝑉 𝑅
For ideal gas 𝑃𝑉 = 𝑅𝑇 ( )𝑉 = ( )𝑃 =
𝜕𝑇 𝑉 𝜕𝑇 𝑃
𝑅𝑅
𝐶𝑃 = 𝐶𝑉 + 𝑇 = 𝐶𝑉 + 𝑅
𝑉𝑃
𝑅𝑇 𝑎 𝜕𝑃 𝑅
For a gas obey van der Waals equation 𝑃= − 2 ( )𝑉 =
𝑉−𝑏 𝑉 𝜕𝑇 𝑉−𝑏
𝜕𝑃 𝑅
𝜕𝑉 𝜕𝑇 𝜕𝑃 𝜕𝑉 ( )𝑉
( )𝑃 = − 𝜕𝑇 =− 𝑉−𝑏
( )𝑃 ( )𝑉 ( )𝑇 = −1 𝑅𝑇 2𝑎
𝜕𝑇 𝜕𝑃 𝜕𝑉 𝜕𝑇 𝜕𝑃
( )𝑇 [− + ]
𝜕𝑉 𝑉 − 𝑏 2 𝑉3

𝑅
𝑅 𝑉 − 𝑏 𝑅
𝐶𝑃 = 𝐶𝑉 − 𝑇 = 𝐶𝑉 +
𝑉 − 𝑏 [− 𝑅𝑇 2𝑎 2𝑎 𝑉 − 𝑏 2
+ ] 1−
𝑉 − 𝑏 2 𝑉3 𝑅𝑇𝑉 3
19
Example Example 19

One mole of propane expands from 0.001 m3 to 0.040 m3 in contact with

a heating bath at 100 oC. The expansion is not reversible. The heat
extracted from the bath is 1500 J. Using the van der Waals equation of
state, and 2nd order Virial equation, respectively, to determine the work
for the expansion.
𝑃𝑉 𝐵
For Virial equation, use 𝑍≡ =1+ regard B as a constant
𝑅𝑇 𝑉
Analysis
First law ∆𝑈 = 𝑄 + 𝑊

𝑄 = 1500 𝐽 Need to find ∆𝑈 to determine W

𝜕𝑃
Solution 𝑑𝑈 = 𝐶𝑉 𝑑𝑇 + [𝑇( )𝑉 − 𝑃]𝑑𝑉
𝜕𝑇
𝜕𝑃
Constant T, 𝑑𝑈 = [𝑇( )𝑉 − 𝑃]𝑑𝑉
𝜕𝑇 20
 Example Example 20

𝑅𝑇 𝑎 𝜕𝑃 𝑅
𝑃= − 2 ( )𝑉 =
𝑉−𝑏 𝑉 𝜕𝑇 𝑉−𝑏
(van der Waals equation)

𝜕𝑃 𝑅𝑇 𝑑𝑉
𝑑𝑈 = [𝑇( )𝑉 − 𝑃]𝑑𝑉 = − 𝑃 𝑑𝑉 = 𝑎 2
𝜕𝑇 𝑉−𝑏 𝑉
𝑉2
𝑑𝑉 1 1
∆𝑈 = 𝑎 න 2
= −𝑎( − )
𝑉1 𝑉 𝑉2 𝑉1

27𝑅2 𝑇𝑐 2
𝑎= = 0.96 𝐽 𝑚3 𝑚𝑜𝑙 −2
64𝑃𝑐

1 1
∆𝑈 = −0.96( − )
𝑉2 𝑉1

21
Example Example 21

1 1
∆𝑈 = −0.96 − = 936 𝐽
0.040 0.001

𝑊 = ∆𝑈 − 𝑄 = 936 − 1500 = −564 𝐽

For Virial equation of state

𝑃𝑉 𝐵 𝑅𝑇 𝐵𝑅𝑇
𝑍≡ =1+ 𝑃= + 2
𝑅𝑇 𝑉 𝑉 𝑉
𝜕𝑃 𝑅 𝐵𝑅
( )𝑉 = + 2
𝜕𝑇 𝑉 𝑉
𝜕𝑃 𝑅𝑇 𝐵𝑅𝑇 𝑅𝑇 𝐵𝑅𝑇
𝑑𝑈 = [𝑇( )𝑉 − 𝑃]𝑑𝑉 = + 2 − + 2 𝑑𝑉 = 0
𝜕𝑇 𝑉 𝑉 𝑉 𝑉

𝑊 = −𝑄 = −1500 𝐽
22
Residual Properties
Residual Properties 22

Residual properties are defined as MR ≡ M – Mig referring to ideal gas at

the same T and P. They represent the contributions from the
intermolecular interactions from the real fluids.

To obtain any property M

𝑀 ≡ 𝑀𝑖𝑔 + 𝑀𝑅
For example: 𝑉 ≡ 𝑉 𝑖𝑔 + 𝑉 𝑅 𝐺 ≡ 𝐺 𝑖𝑔 + 𝐺 𝑅 𝐻 ≡ 𝐻 𝑖𝑔 + 𝐻 𝑅 ……

For ideal gas, recall:

𝑇2 𝑇2
Δ𝑈 𝑖𝑔 = න 𝐶𝑉 𝑑𝑇 Δ𝐻𝑖𝑔 = න 𝐶𝑃 𝑑𝑇
𝑇1 𝑇1

𝑇2 𝑇2
𝑑𝑇 𝑃2 𝑑𝑇 𝑉2
Δ𝑆 𝑖𝑔 = න 𝐶𝑃 − 𝑅𝑙𝑛 or Δ𝑆 𝑖𝑔 = න 𝐶𝑉 + 𝑅𝑙𝑛
𝑇1 𝑇 𝑃1 𝑇1 𝑇 𝑉1

We still have to find ways to calculate 𝑀𝑅 23

 Residual Properties
Residual Properties 23

𝑅 𝑖𝑔
𝑅𝑇
For residual volume: 𝑉 ≡𝑉−𝑉 = (𝑍 − 1)
𝑃

For other residual properties, we use Gibbs Energy as a generating function:

𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇

𝐺 1 𝐺 1 𝐺 𝑉 𝑇𝑆 + 𝐺
𝑑 ≡ 𝑑𝐺 − 2
𝑑𝑇 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 − 2
𝑑𝑇 = 𝑑𝑃 − 2
𝑑𝑇
𝑅𝑇 𝑅𝑇 𝑅𝑇 𝑅𝑇 𝑅𝑇 𝑅𝑇 𝑅𝑇

𝐺 𝑉 𝐻
𝑑 = 𝑑𝑃 − 𝑑𝑇 (Eqn 1)
𝑅𝑇 𝑅𝑇 𝑅𝑇 2

𝐺 𝑖𝑔 𝑉 𝑖𝑔 𝐻 𝑖𝑔
For idea gas: 𝑑 = 𝑑𝑃 − 2
𝑑𝑇 (Eqn 2)
𝑅𝑇 𝑅𝑇 𝑅𝑇

𝐺𝑅 𝑉𝑅 𝐻𝑅 Fundamental
Subtracting Eqn 2 from Eqn 1 𝑑 = 𝑑𝑃 − 2
𝑑𝑇 residual-property
𝑅𝑇 𝑅𝑇 𝑅𝑇 relation 24
 Residual Properties
Residual Properties 24

𝐺𝑅 𝑉𝑅 𝐻𝑅
From: 𝑑 = 𝑑𝑃 − 2
𝑑𝑇
𝑅𝑇 𝑅𝑇 𝑅𝑇

𝐺𝑅 𝐺𝑅
𝑉𝑅 𝜕 𝐻𝑅 𝜕 𝑆 𝑅 𝐻𝑅 𝐺 𝑅
𝑅𝑇 𝑅𝑇 And further: = −
We have: =[ ]𝑇 = −𝑇 [ ]𝑃
𝑅𝑇 𝜕𝑃 𝑅𝑇 𝜕𝑇 𝑅 𝑅𝑇 𝑅𝑇

𝐺𝑅 𝑉𝑅
At const T, 𝑑 = 𝑑𝑃
𝑅𝑇 𝑅𝑇

𝑃 𝑅
𝐺𝑅 𝐺𝑅 𝑉 𝐺𝑅 𝐺𝑅 𝑃
(𝑍 − 1)
= ( )𝑃=0 + න 𝑑𝑃 = ( )𝑃=0 + න 𝑑𝑃
𝑅𝑇 𝑅𝑇 0 𝑅𝑇 𝑅𝑇 𝑅𝑇 0 𝑃

In application, we always look at the difference of a property

𝑃
𝐺𝑅 𝐺𝑅 (𝑍 − 1)
Therefore set ( )𝑃=0 = 0 for convenience =න 𝑑𝑃
𝑅𝑇 𝑅𝑇 0 𝑃 25
Residual Properties
Residual Properties 25

𝐺𝑅 𝑃 (𝑍 − 1)
𝐻 𝑅 𝜕 𝜕 ‫׬‬0 𝑑𝑃
𝑅𝑇 𝑃
= −𝑇 [ ]𝑃 = −𝑇[ ]𝑃
𝑅𝑇 𝜕𝑇 𝜕𝑇

𝑃
𝐻𝑅 𝜕𝑍 𝑑𝑃
= −𝑇 න ( )𝑃
𝑅𝑇 0 𝜕𝑇 𝑃

𝑃 𝑃
𝑆 𝑅 𝐻𝑅 𝐺 𝑅 𝜕𝑍 𝑑𝑃 𝑍 − 1 𝑑𝑃
= − = −𝑇 න ( )𝑃 −න
𝑅 𝑅𝑇 𝑅𝑇 0 𝜕𝑇 𝑃 0 𝑃

26
 Residual
ResidualProperties: anAlternative
Properties: An Alternative Approach
Approach 26
𝜕𝑉 𝜕𝑉
𝒅𝑯 = 𝐶𝑃 𝑑𝑇 + [𝑉 − 𝑇( )𝑃 ]𝑑𝑃 𝒅𝑯𝑹 = [𝑉 − 𝑇( )𝑃 ]𝑑𝑃
𝜕𝑇 𝜕𝑇
Ideal gas part Residual part

𝑃𝑉 𝜕(𝑃𝑉) 𝜕(𝑍𝑅𝑇)
Since 𝑍 ≡ 𝑃𝑉 = 𝑍𝑅𝑇 =
𝑅𝑇 𝜕𝑇 𝑃
𝜕𝑇 𝑃

𝜕𝑉 𝜕𝑍 𝜕𝑉 𝑅𝑍𝑇 𝑅𝑇 2 𝜕𝑍
𝑃 = 𝑅𝑍 𝑃 + 𝑅𝑇 𝑇 = +
𝜕𝑇 𝑃
𝜕𝑇 𝑃
𝜕𝑇 𝑃 𝑃 𝑃 𝜕𝑇
𝑃 𝑃

𝜕𝑉 𝑅𝑇 2 𝜕𝑍
𝑇 =𝑉+
𝜕𝑇 𝑃
𝑃 𝜕𝑇 𝑃

𝑹
𝜕𝑉 𝑅𝑇 2 𝜕𝑍
Therefore 𝒅𝑯 = 𝑉 − 𝑇 𝑑𝑃 = − 𝑑𝑃
𝜕𝑇 𝑃
𝑃 𝜕𝑇 𝑃

𝒅𝑯𝑹 𝜕𝑍 𝑑𝑃 𝑯𝑹 𝑃
𝜕𝑍 𝑑𝑃
= −𝑇 = −𝑇 න ( )𝑃 27
𝑹𝑻 𝜕𝑇 𝑃
𝑃 𝑹𝑻 0 𝜕𝑇 𝑃
Residual
ResidualProperties: anAlternative
Properties: An Alternative Approach
Approach 27

𝑑𝐻 𝑉𝑑𝑃 𝑑𝑇 𝜕𝑉 𝑑𝑇 𝑑𝑃
𝒅𝑺 = − = 𝐶𝑃 − ( )𝑃 𝑑𝑃 𝒅𝑺𝒊𝒈 = 𝐶𝑃 −𝑅
𝑇 𝑇 𝑇 𝜕𝑇 𝑇 𝑃

𝑑𝑃 𝜕𝑉
𝒅𝑺𝑹 = 𝒅𝑺 − 𝒅𝑺𝒊𝒈 =𝑅 − ( )𝑃 𝑑𝑃
𝑃 𝜕𝑇

𝜕𝑉 𝑉 𝑅𝑇 𝜕𝑍
From last slide we have: = +
𝜕𝑇 𝑃
𝑇 𝑃 𝜕𝑇 𝑃

𝑹
𝑑𝑃 𝑉 𝑅𝑇 𝜕𝑍 𝑅𝑇 − 𝑃𝑉 𝜕𝑍 𝑑𝑃
𝒅𝑺 = 𝑅 − 𝑑𝑃 − 𝑑𝑃 = 𝑑𝑃 − 𝑅𝑇
𝑃 𝑇 𝑃 𝜕𝑇 𝑃
𝑃𝑇 𝜕𝑇 𝑃
𝑃

𝑹
1−𝑍 𝜕𝑍 𝑑𝑃 𝒅𝑺𝑹 1 − 𝑍 𝜕𝑍 𝑑𝑃
𝒅𝑺 = 𝑅 𝑑𝑃 − 𝑅𝑇 = 𝑑𝑃 − 𝑇
𝑃 𝜕𝑇 𝑃 𝑹 𝑃 𝜕𝑇 𝑃
𝑃
𝑃

𝑃 𝑃
𝑺𝑹 𝜕𝑍 𝑑𝑃 𝑍 − 1 𝑑𝑃
= −𝑇 න ( )𝑃 −න
𝑹 0 𝜕𝑇 𝑃 0 𝑃 28
Residual Residual
Properties by EoS
Properties by EOS 28
Residual properties from the 2nd Virial Equation of State
𝑃𝑉 𝐵𝑃
≡𝑍 =1+
𝑅𝑇 𝑅𝑇

𝑃 𝑃
𝐺𝑅 (𝑍 − 1) 𝐵 𝐵𝑃
=න 𝑑𝑃 = න 𝑑𝑃 =
𝑅𝑇 0 𝑃 0 𝑅𝑇 𝑅𝑇

𝑃
𝐻𝑅 𝜕𝑍 𝑑𝑃 𝑃 1 𝑑𝐵 𝐵 𝑃 𝐵 𝑑𝐵
= −𝑇 න ( )𝑃 = −𝑇 − = ( − )
𝑅𝑇 0 𝜕𝑇 𝑃 𝑅 𝑇 𝑑𝑇 𝑇 2 𝑅 𝑇 𝑑𝑇

𝑃 𝑃
𝑆𝑅 𝜕𝑍 𝑑𝑃 𝑍 − 1 𝑑𝑃 𝑃 𝐵 𝑑𝐵 𝐵𝑃 𝑃 𝑑𝐵
= −𝑇 න ( )𝑃 −න = − − =− ( )
𝑅 0 𝜕𝑇 𝑃 0 𝑃 𝑅 𝑇 𝑑𝑇 𝑅𝑇 𝑅 𝑑𝑇

Note that 2nd Virial equation is a volume-explicit EoS (const T) 29

Residual Properties by EOS 29
Residual Residual
Properties by EoS
Properties by EOS 30
Residual properties from the van der Waals equation of state
𝑅𝑇 𝑎
𝑃= −
𝑉 − 𝑏 𝑉2
𝑃𝑉 𝑉 𝑎 1 𝑎𝜌
𝑍= = − = −
𝑅𝑇 𝑉 − 𝑏 𝑉𝑅𝑇 1 − 𝜌𝑏 𝑅𝑇
𝜌𝑏 𝑎𝜌 𝜕𝑍 𝑎𝜌
𝑍−1= − ( )𝜌 =
1 − 𝜌𝑏 𝑅𝑇 𝜕𝑇 𝑅𝑇 2
𝜌
𝐺𝑅 𝑍 − 1 𝑑𝜌 𝜌𝑏 2𝑎𝜌 𝑎𝜌 𝑎𝑏𝜌2
=න + 𝑍 − 1 − 𝑙𝑛𝑍 = − − 𝑙𝑛 (1 − + )
𝑅𝑇 0 𝜌 1 − 𝜌𝑏 𝑅𝑇 𝑅𝑇 𝑅𝑇

𝜌 𝜌
𝐻𝑅 𝜕𝑍 𝑑𝜌 𝑎𝜌 𝑑𝜌 1 𝑎𝜌 𝜌𝑏 2𝑎𝜌
= −𝑇 න ( )𝜌 + 𝑍 − 1 = −𝑇 න 2
+ − = −
𝑅𝑇 0 𝜕𝑇 𝜌 0 𝑅𝑇 𝜌 1 − 𝜌𝑏 𝑅𝑇 1 − 𝜌𝑏 𝑅𝑇

𝜌 𝜌
𝑆𝑅 𝜕𝑍 𝑑𝜌 𝑑𝜌 𝑎𝜌 𝑎𝑏𝜌2
= 𝑙𝑛𝑍 − 𝑇 න ( )𝜌 −න 𝑍−1 = 𝑙𝑛 (1 − + )
𝑅 0 𝜕𝑇 𝜌 0 𝜌 𝑅𝑇 𝑅𝑇 31
Example Example 31

H2 S (hydrogen sulfide) gas is compressed from an initial state of 400 K

and 5 bar to a final state of 600 K and 25 bar. Estimated ∆H and ∆S from
the van der Waals equation of state.
𝑅𝑇 𝑎
𝑃= −
𝑉 − 𝑏 𝑉2

Analysis: Calculate the ideal gas property and residual property separately,
and then combine them
Solution
For H2 S, 𝑇𝑐 = 373.5 𝐾, 𝑃𝑐 = 89.63 𝑏𝑎𝑟

27𝑅2 𝑇𝑐 2 27 × 8.3142 × 373.52 6 𝑚𝑜𝑙 −2

𝑎= = = 0.454 𝑃𝑎 𝑚
64𝑃𝑐 64 × 89.63 × 105

𝑅𝑇𝑐 8.314 × 373.5 −5 𝑚3 𝑚𝑜𝑙 −1

𝑏= = = 4.33 × 10
8𝑃𝑐 8 × 89.63 × 105 33
Example Example 32
For state 1, 𝑇1 = 400 𝐾, 𝑃1 = 5 𝑏𝑎𝑟
𝑉1 = 0.006557 𝑚3 𝑚𝑜𝑙 −1 , ρ1 = 152.5 𝑚𝑜𝑙 𝑚−3
𝜌1 𝑏
𝐻1𝑅 = 𝑅𝑇1 − 2𝑎𝜌1
1 − 𝜌1 𝑏
152.5 × 4.33 × 10−5
= 8.314 × 400 − 2 × 0.454 × 152.5
1 − 152.5 × 4.33 × 10−5
= 22.1 − 138.5 = −116.4 𝐽 𝑚𝑜𝑙 −1
2
𝑎𝜌1 𝑎𝑏𝜌1
𝑆1𝑅 = 𝑅𝑙𝑛 1 − +
𝑅𝑇1 𝑅𝑇1
0.454 × 152.5 0.454 × 4.33 × 10−5 × 152.52
= 8.314𝑙𝑛(1 − + )
8.314 × 400 8.314 × 400

= 8.314𝑙𝑛 1 − 0.02082 + 0.000137

= −0.174 𝐽 𝑚𝑜𝑙 −1 𝐾 −1 34
Example Example 33

For state 2, 𝑇2 = 600 𝐾, 𝑃2 = 25 𝑏𝑎𝑟

𝑉2 = 0.001948 𝑚3 𝑚𝑜𝑙 −1 , ρ2 = 513.3 𝑚𝑜𝑙 𝑚−3

𝜌2 𝑏
𝐻2𝑅 = 𝑅𝑇2 − 2𝑎𝜌2 = −352.7 𝐽 𝑚𝑜𝑙 −1
1 − 𝜌2 𝑏
2
𝑎𝜌2 𝑎𝑏𝜌2
𝑆2𝑅 = 𝑅𝑙𝑛 1 − + = −0.388 𝐽 𝑚𝑜𝑙 −1 𝐾 −1
𝑅𝑇2 𝑅𝑇2

∆𝐻𝑅 = 𝐻2𝑅 − 𝐻1𝑅 = −236.3 𝐽 𝑚𝑜𝑙 −1

∆𝑆 𝑅 = 𝑆2𝑅 − 𝑆1𝑅 = −0.214 𝐽 𝑚𝑜𝑙 −1

35
Example Example 34
𝑇2 𝑇2
𝑖𝑔
∆𝐻𝑖𝑔 = න 𝐶𝑃 𝑑𝑇 = 𝑅 න (3.931 + 1.490 × 10−3 𝑇 − 0.232 × 105 𝑇 −2 ) 𝑑𝑇
𝑇1 𝑇1
600 𝐾
= 𝑅 (3.931𝑇 + 0.745 × 10−3 𝑇 2 + 0.232 × 105 𝑇 −1 ) ቤ
400 𝐾
= 7614.8 𝐽 𝑚𝑜𝑙 −1

𝑇2
𝑖𝑔 𝑑𝑇 𝑃2
∆𝑆 𝑖𝑔 = න 𝐶𝑃 − 𝑅𝑙𝑛
𝑇1 𝑇 𝑃1
𝑇2
= 𝑅 න (3.931𝑇 −1 + 1.490 × 10−3 − 0.232 × 105 𝑇 −3 ) 𝑑𝑇 − 𝑅𝑙𝑛5
𝑇1
600 𝐾
= 𝑅 3.931𝑙𝑛𝑇 + 1.49 × 10−3 𝑇 + 0.116 × 105 𝑇 −2 ቤ − 13.38
400 𝐾
= 2.00 𝐽 𝑚𝑜𝑙 −1 𝐾 −1

Δ𝐻 = ∆𝐻 𝑖𝑔 + ∆𝐻 𝑅 = 7614.8 − 236.3 = 7378.5 𝐽 𝑚𝑜𝑙 −1

𝛥𝑆 = ∆𝑆 𝑖𝑔 + ∆𝑆 𝑅 = 2.0 − 0.214 = 1.79 𝐽 𝑚𝑜𝑙 −1 𝐾 −1 36
Generalized Correlations
Generalized for
Correlations forGases
Gases 35

Recall: in chapter three, we introduced two general correlations for gases

Three parameter correlation

𝑍 = 𝐹(𝑇𝑟 , 𝑃𝑟 , 𝜔) 𝑍0 can be found in Table E.1

𝑍 = 𝑍0 + 𝜔𝑍1 𝑍1 can be found in Table E.2

𝜔 can be found in Table B.1

2nd virial coefficient correlation

𝑃𝑟
𝑍 = 1 + 𝐵෠
𝑇𝑟
𝐵෠ = 𝐵0 + 𝜔𝐵1
0.422 0.172
𝐵0 = 0.083 − 1.6 𝐵1 = 0.139 −
𝑇𝑟 𝑇𝑟 4.2
37
Generalized Correlations
Generalized for
Correlations forGases
Gases 36

𝑃
𝐻𝑅 𝜕𝑍 𝑑𝑃
= −𝑇 න ( )𝑃
𝑅𝑇 0 𝜕𝑇 𝑃

𝑃 𝑃
𝑆𝑅 𝜕𝑍 𝑑𝑃 𝑍 − 1 𝑑𝑃
= −𝑇 න ( )𝑃 −න
𝑅 0 𝜕𝑇 𝑃 0 𝑃

𝑃 = 𝑃𝑐 𝑃𝑟 𝑇 = 𝑇𝑐 𝑇𝑟 𝑑𝑃 = 𝑃𝑐 𝑑𝑃𝑟 𝑑𝑇 = 𝑇𝑐 𝑑𝑇𝑟

𝑃𝑟
𝐻𝑅 2 𝜕𝑍 𝑑𝑃𝑟
= −𝑇𝑟 න ( )𝑃𝑟
𝑅𝑇𝐶 0 𝜕𝑇𝑟 𝑃𝑟

𝑃𝑟 𝑃𝑟
𝑆𝑅 𝜕𝑍 𝑑𝑃𝑟 𝑑𝑃𝑟
= −𝑇𝑟 න ( )𝑃𝑟 −න 𝑍−1
𝑅 0 𝜕𝑃𝑟 𝑃𝑟 0 𝑃𝑟

38
Generalized Correlations
Generalized for
Correlations forGases
Gases 37

𝑍 = 𝑍 0 + 𝜔𝑍1 Three parameter correlation

𝜕𝑍 𝜕𝑍 0 𝜕𝑍1
( )𝑃𝑟 = ( )𝑃𝑟 + 𝜔( )𝑃𝑟
𝜕𝑇𝑟 𝜕𝑇𝑟 𝜕𝑇𝑟

𝑃𝑟 𝑃𝑟
𝐻𝑅 2 𝜕𝑍 0
𝑑𝑃 𝑟 2 𝜕𝑍 1
𝑑𝑃𝑟
= −𝑇𝑟 න ( )𝑃𝑟 − 𝜔𝑇𝑟 න ( )𝑃𝑟
𝑅𝑇𝐶 0 𝜕𝑇𝑟 𝑃𝑟 0 𝜕𝑇𝑟 𝑃𝑟

𝑃𝑟 𝑃𝑟
𝑆𝑅 𝜕𝑍 0 0
𝑑𝑃𝑟 𝜕𝑍 1
1
𝑑𝑃𝑟
= − න [( )𝑃𝑟 + 𝑍 − 1] − 𝜔 න [( )𝑃𝑟 + 𝑍 ]
𝑅 0 𝜕𝑃𝑟 𝑃𝑟 0 𝜕𝑃𝑟 𝑃𝑟

𝐻 𝑅 (𝐻𝑅 )0 (𝐻𝑅 )1 𝑆 𝑅 (𝑆 𝑅 )0 (𝑆 𝑅 )1
= +𝜔 = +𝜔
𝑅𝑇𝑐 𝑅𝑇𝑐 𝑅𝑇𝑐 𝑅 𝑅 𝑅

Three parameter correlation 39

 Generalized Correlations
Generalized for
Correlations forGases
Gases 38

𝐻𝑅 𝑃 𝐵 𝑑𝐵 𝑆𝑅 𝑃 𝑑𝐵
Recall: = ( − ) =− ( ) Based on 2nd Virial Equation
𝑅𝑇 𝑅 𝑇 𝑑𝑇 𝑅 𝑅 𝑑𝑇
𝐵𝑃𝑐 ෠ 𝐶
𝐵𝑅𝑇 𝑑𝐵 𝑅 𝑑 𝐵෠
𝐵෠ = 𝐵= =
𝑅𝑇𝑐 𝑃𝐶 𝑑𝑇 𝑃𝐶 𝑑𝑇𝑟

𝐻𝑅 𝑑 𝐵෠ 𝑆𝑅 𝑑 𝐵෠
= 𝑃𝑟 (𝐵෠ − 𝑇𝑟 ) = −𝑃𝑟
𝑅𝑇𝑐 𝑑𝑇𝑟 𝑅 𝑑𝑇𝑟

𝐵𝑃 𝑑 𝐵෠ 𝑑𝐵0 𝑑𝐵1
෠ = 𝑐 = 𝐵0 + 𝜔𝐵1
Consider: 𝐵 = +𝜔
𝑅𝑇𝑐 𝑑𝑇𝑟 𝑑𝑇𝑟 𝑑𝑇𝑟

𝐻𝑅 𝑑𝐵 0
𝑑𝐵 1 𝑆𝑅 𝑑𝐵0 𝑑𝐵1
= 𝑃𝑟 [𝐵0 − 𝑇𝑟 + 𝜔 𝐵1 − 𝑇𝑟 ] = −𝑃𝑟 ( +𝜔 )
𝑅𝑇𝑐 𝑑𝑇𝑟 𝑑𝑇𝑟 𝑅 𝑑𝑇𝑟 𝑑𝑇𝑟

0.422 0.172 𝑑𝐵0 0.675 𝑑𝐵1 0.722

𝐵0 = 0.083 − 1.6 𝐵1 = 0.139 − = 2.6 = 5.2
𝑇𝑟 𝑇𝑟 4.2 𝑑𝑇𝑟 𝑇𝑟 𝑑𝑇𝑟 𝑇𝑟 41
Example Example 39

𝐻2 𝑆 (hydrogen sulfide) gas is compressed from an initial state of 400 K

and 5 bar to a final state of 600 K and 25 bar. Estimated ∆H and ∆S from
the generalized correlation of 2nd virial coefficient.

Compare the results with those from the van der Waals equation of state.

Solution
For H2 S, 𝑇𝑐 = 373.5 𝐾, 𝑃𝑐 = 89.63 𝑏𝑎𝑟, 𝜔 = 0.094

State 1: 𝑇1 = 400 𝐾, 𝑇1,𝑟 = 1.071; 𝑃1 = 5 𝑏𝑎𝑟, 𝑃1,𝑟 = 0.056

0.422 0.172
𝐵0 = 0.083 − 1.6 = −0.295 𝐵1 = 0.139 − 4.2 = −0.010
𝑇1,𝑟 𝑇1,𝑟

𝑑𝐵0 0.675 𝑑𝐵1 0.722

= 2.6 = 0.565 = 5.2 = 0.505
𝑑𝑇𝑟 𝑇1,𝑟 𝑑𝑇𝑟 𝑇1,𝑟
42
 𝐻1 𝑅 𝑑𝐵0 𝑑𝐵1
= 𝑃1,𝑟 𝐵0 − 𝑇𝑟 + 𝜔 𝐵1 − 𝑇𝑟 = −0.053
𝑅𝑇𝑐 𝑑𝑇𝑟 𝑑𝑇𝑟
𝑆1 𝑅 𝑑𝐵0 𝑑𝐵1
= −𝑃1,𝑟 +𝜔 = −0.034
𝑅 𝑑𝑇𝑟 𝑑𝑇𝑟

State 2: 𝑇2 = 600 𝐾, 𝑇2,𝑟 = 1.606; 𝑃2 = 25 𝑏𝑎𝑟, 𝑃2,𝑟 = 0.279

0.422 0.172
𝐵0 = 0.083 − 1.6 = −0.115 𝐵1 = 0.139 − 4.2 = 0.115
𝑇2,𝑟 𝑇2,𝑟
𝑑𝐵0 0.675 𝑑𝐵1 0.722
= = 0.197 = = 0.061
𝑑𝑇𝑟 𝑇2,𝑟 2.6 𝑑𝑇𝑟 𝑇2,𝑟 5.2

𝐻2 𝑅 𝑑𝐵0 𝑑𝐵1
= 𝑃2,𝑟 𝐵0 − 𝑇𝑟 + 𝜔 𝐵1 − 𝑇𝑟 = −0.120
𝑅𝑇𝑐 𝑑𝑇𝑟 𝑑𝑇𝑟

𝑆2 𝑅 𝑑𝐵0 𝑑𝐵1
= −𝑃2,𝑟 +𝜔 = −0.057
𝑅 𝑑𝑇𝑟 𝑑𝑇𝑟
43
Example Example 41

𝑇2
∆𝐻 𝑖𝑔 = න 𝐶𝑃 𝑖𝑔 𝑑𝑇 = 7614.8 𝐽 𝑚𝑜𝑙 −1
𝑇1

𝑇2
𝑖𝑔 𝑖𝑔 𝑑𝑇 𝑃2
∆𝑆 = න 𝐶𝑃 − 𝑅𝑙𝑛 = 2.00 𝐽 𝑚𝑜𝑙−1 𝐾 −1
𝑇1 𝑇 𝑃1

∆𝐻 = ∆𝐻𝑖𝑔 + 𝐻2 𝑅 − 𝐻1 𝑅 = 7406.4 𝐽 𝑚𝑜𝑙−1

∆𝑆 = ∆𝑆 𝑖𝑔 + 𝑆2 𝑅 − 𝑆1 𝑅 = 1.82 𝐽 𝑚𝑜𝑙 −1 𝐾 −1

44
Summary Summary 42

1 Property Relations for Homogeneous Phases

𝑈 𝐻 ≡ 𝑈 + 𝑃𝑉 𝐴 ≡ 𝑈 − 𝑇𝑆 𝐺 ≡ 𝐻 − 𝑇𝑆 Definition

𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃

Fundamental Relations
𝑑𝐴 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇 𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇

𝜕T 𝜕P 𝜕𝑇 𝜕𝑉 𝜕𝑃 𝜕𝑆 𝜕𝑉 𝜕𝑆
( )S = −( )V ( )𝑆 = ( )𝑃 ( )𝑉 = ( ) 𝑇 ( )𝑃 = −( ) 𝑇
𝜕V 𝜕S 𝜕𝑃 𝜕𝑆 𝜕𝑇 𝜕𝑉 𝜕𝑇 𝜕𝑃
Maxwell Relations

𝜕𝑉 𝑑𝐻 𝑉𝑑𝑃 𝑑𝑇 𝜕𝑉
𝑑𝐻 = 𝐶𝑃 𝑑𝑇 + [𝑉 − 𝑇( )𝑃 ]𝑑𝑃 𝑑𝑆 = − = 𝐶𝑃 − ( )𝑃 𝑑𝑃
𝜕𝑇 𝑇 𝑇 𝑇 𝜕𝑇
𝜕𝑃 𝑑𝑇 𝜕𝑃
𝑑𝑈 = 𝐶𝑉 𝑑𝑇 + [𝑇( )𝑉 − 𝑃]𝑑𝑉 𝑑𝑆 = 𝐶𝑉 + ( )𝑉 𝑑𝑉
𝜕𝑇 𝑇 𝜕𝑇
H, U and S as Functions of T, P and V 49
Summary Summary 43

2 Residual Properties: 𝐺 𝑅 , 𝑆 𝑅 , 𝐻 𝑅
𝑀 ≡ 𝑀𝑖𝑔 + 𝑀𝑅
𝑃
𝐺𝑅 𝑃
(𝑍 − 1) 𝐻𝑅 𝜕𝑍 𝑑𝑃
=න 𝑑𝑃 = −𝑇 න ( )𝑃
𝑅𝑇 0 𝑃 𝑅𝑇 0 𝜕𝑇 𝑃
𝑃 𝑃
𝑆𝑅 𝜕𝑍 𝑑𝑃 𝑍 − 1 𝑑𝑃
= −𝑇 න ( )𝑃 −න
𝑅 0 𝜕𝑇 𝑃 0 𝑃

3 Residual Properties by Equations of State

𝑃𝑉 𝐵𝑃
For 2nd Virial equation ≡𝑍 =1+
𝑅𝑇 𝑅𝑇
𝐺 𝑅 𝐵𝑃 𝐻 𝑅 𝑃 𝐵 𝑑𝐵 𝑆𝑅 𝑃 𝑑𝐵
= = ( − ) =− ( )
𝑅𝑇 𝑅𝑇 𝑅𝑇 𝑅 𝑇 𝑑𝑇 𝑅 𝑅 𝑑𝑇

𝑑𝑃 𝑑𝜌 𝑑𝑍
For non-volume-explicit EoS, replace = +
𝑃 𝜌 𝑍 50