TDA301T 2023

Lecture Notes
LESSON FOUR
Compiled by
Mr. Leshabane LJ
(MEng: Chem Eng TUT)
Department of Chemical, Metallurgical and
Materials Engineering
Please note:
• MyTutor – Official media for academic activities
• Assessment date to follow soon
• Classes every Wednesday and Thursday (11:00 AM)
• Practical's are on Monday – schedule will be posted.
• Consultation – Wednesdays (10:00-15:00PM).
• Cellphones must switched off or on silent mode at all
times during lectures.

2
 Course Contents
1. First Law of Thermodynamics (Revision)
2. Conservation of Energy (Application of Revision)
3. Power Cycles, Liquefaction, Refrigeration
4. Thermodynamic Properties of Real Substances
5. Equilibrium and Stability – One Component & Multi-
Component Systems
6. Estimation of Gibbs Energy and Fugacity of a
Component in a Mixture
7. Vapor-Liquid Equilibrium in Mixtures
8. Chemical Equilibrium

3
 Course Content
Any Thermodynamics book with Engineering Approaches
Examples:
– Chemical, Biochemical & Engineering Thermodynamics (Fifth
Edition) by Stanley I. Sandler
– Applied Thermodynamics by Eastop and McConkey
– Fundamentals of Chemical Engineering Thermodynamics by
Themis Matsoukas
– Introduction to Chemical Engineering Thermodynamics by
JM Smith

4
 Deviations From Ideal Behaviour

• Ideal estimations of matter and phenomenon are essential to

communicating the core concepts of topic.
• The ideal gas equation: PV = nRT is one such example of a
simplified concept.
• In practice, changes in pressure and temperature of any
substance causes a deviation from ideal behaviour.
• This can be observed through:
– Thermal Expansion of Matter
– Compressibility of Gas
– Equations of State.

5
 Thermal Expansion

• Thermal expansion describes the tendency of an object to

change its dimension either in length, area or volume due to
heat.
• Heating up a substance increases its kinetic energy.
• Depending on the type of expansion thermal expansion is of 3
types– Linear expansion, Area expansion, and Volume
expansion.

6
 Thermal Expansion
Real Life Applications
Mercury thermometer
Examples
• Volume gas thermometers
• Mercury thermometers
• Bimetallic strip in thermostats
• In a mercury thermometer, a glass tube is filled • Sagging in Power lines
with mercury and a standard temperature scale • Expansion joints in bridges
is marked on the tube.
• With changes in temperature, the mercury
expands and contracts, and the temperature can
be read from the scale.
• Mercury thermometers can be used to determine
body, liquid, and vapor temperature.
• Mercury thermometers are used in households,
laboratory experiments, and industrial
applications.

7
 Thermal Expansion in Solids
Linear Expansion
L0 ΔL

• Linear expansion is the change in length due to temperature.

• Linear expansion formula is given as

• Where,
– L0 = original length,
– α = length expansion coefficient,
– ΔT = temperature difference,
– ΔL = change in length

8
 Thermal Expansion in Solids
Volume Expansion
Vo V

• Volume expansion is the change in volume due to temperature.

• Volume expansion formula is given as

• Where,
– V0 = original volume,
– αv = volume expansion coefficient,
– ΔT = temperature difference,
– ΔV = change in volume after expansion

9
 Thermal Expansion in Solids
Volume Expansion
Vo V

• Area expansion is the change in area due to temperature change. Area

expansion formula is given as

• Where,
– Ao = original area,
– ΔA = change in the area,
– αA = area expansion coefficient
(some references use ᵝ)
– ΔT = temperature difference,

10
Thermal Expansion in Liquids
Phase Transition In Water
• This graph shows the phase diagram of water.
• At the beginning we have ice at -20 ºC. Ice gain
heat in the interval of points A and B, and its
temperature becomes 0 ºC that is the melting
point of it. We have only ice in the 1st region.
• As you can see between the points B and C,
temperature of the mass does not change,
because its state is changing in this interval.
Gained heat is spent on breaking the bonds of
molecules. 2nd region includes both water and ice.
• After melting process completed, in the 3rd region
there is only water and temperature of water
starts to increase.
• When the temperature of the water becomes 100
ºC, it starts to boil and evaporation of it speeds
up. In region 4 our mass exists in two state, water
and steam. After completion of evaporation, all
water is converted to steam
• In region 5 we have only vapor of water

11
Thermal Expansion in Liquids
Phase Transition In Water
• As temperature (or energy transferred)
increases, volume (or specific volume)
also increases
• The specific volume values at various
temperatures are tabulated in
thermodynamic tables (see steam
tables)
• Have a look of thermodynamic
properties of various refrigerants.

12
 Thermal Expansion in Gases
Reversible Isothermal Expansion of an Ideal Gas
• In this process like what happens in car engine, heat or
gas has to be pushed out of the cylinder so that the next
heat/expansion cycle can take place. The temperature is
therefore kept constant
• An ideal gas obeys the equation of state
P = nRT ( = specific volume),
• So that, if a fixed mass of gas kept at constant
temperature is compressed or allowed to expand, its
pressure and volume will vary according to P  = constant.
This is Boyle's Law.
• We can calculate the work done by 1 kg of an ideal gas in
a reversible isothermal expansion from volume  i to
volume  f as follows.

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 Thermal Expansion in Gases
Reversible Isothermal Expansion of an Ideal Gas
• When work is done in an Isothermal process
𝑣𝑓 𝑣𝑓
W=‫𝑣׬ =𝑣𝑑𝑝 𝑣׬‬ 𝑐𝑜𝑛𝑠𝑡. 𝑑𝑣/𝑣
𝑖 𝑖
Where const. = RT;
R has units of J/kgK

𝑣𝑓
𝑊 = 𝑅𝑇𝑙𝑛
𝑣𝑖
i.e replace P = const./

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 Thermal Expansion in Gases
Adiabatic Expansion: Gas Turbine
Brayton cycle consist of four thermodynamic processes. Two adiabatic processes
and two isobaric processes.

1. adiabatic compression – ambient air is drawn into the compressor, where it

is pressurized (1 → 2). The work required for the compressor is given by WC =
H2 – H1.

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 Thermal Expansion in Gases
Adiabatic Expansion: Gas Turbine

1. .
2. isobaric heat addition – the compressed air then runs through a
combustion chamber, where fuel is burned and air or another medium is
heated (2 → 3). It is a constant-pressure process, since the chamber is open
to flow in and out. The net heat added is given by Qadd = H3 – H2
3. adiabatic expansion – the heated, pressurized air then expands on turbine,
gives up its energy. The work done by turbine is given by WT = H4 – H3
4. isobaric heat rejection – the residual heat must be rejected in order to
close the cycle. The net heat rejected is given by Qre = H4 – H1

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 Thermal Expansion in Gases
Adiabatic Expansion: Gas-Cycle Refrigeration

1. .

The cycle can be described as follows:

• 1-2 Adiabatic compression.
• 2-3 Constant pressure cooling.
• 3-4 Adiabatic expansion.
• 4-1 Constant pressure heating (cooling effect).

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 Thermal Expansion in Gases
Adiabatic Expansion of an Ideal Gas
• When work is done in an Isothermal process
𝑣𝑓
W=‫=𝑣𝑑𝑝 𝑣׬‬
𝑖
𝑣
‫𝑡𝑠𝑛𝑜𝑐 𝑓 𝑣׬‬. 𝑑𝑣/𝑣
𝑖

𝑃2 𝑣2 − 𝑃1 𝑣1
𝑊=
1−

𝐶𝑝
=
𝐶𝑣

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 Thermal Expansion in Gases
Comparison between Isothermal and Adiabatic
Expansions
• The difference in the nature of the process results in a difference in their final
states and hence, the equations for work done are different as well.

19
 Thermal Expansion in Gases
Polytropic Expansion Process
• The term "polytropic" was originally coined to describe any reversible
process on any open or closed system of gas or vapor which involves
both heat and work transfer, such that a specified combination of
properties were maintained constant throughout the process. In such
a process, the expression relating the properties of the system
throughout the process is called the polytropic path.

• A polytropic process is a thermodynamic process that obeys the

relation:

where p is the pressure, V is volume, n is the polytropic index, and C is

a constant

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 Thermal Expansion in Gases
Polytropic Expansion Process

• The term "polytropic" was originally coined to describe any reversible process
on any open or closed system of gas or vapor which involves both heat and
work transfer, such that a specified combination of properties were
maintained constant throughout the process. In such a process, the
expression relating the properties of the system throughout the process is
called the polytropic path.

• A polytropic process is a thermodynamic process that obeys the relation:

where p is the pressure, V is volume, n is the polytropic index, and C is a constant

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 Thermal Expansion in Gases
Polytropic Expansion Process: 4 Cases of Focus
Case 1: n = 0 ; then pV0 = C or p = C Constant pressure process (Isobaric)
Case 2: n = 1 ; then pV1 = C or pV = C Constant temperature process
(Isothermal)
Case 3: n =  ; then pV = C No heat transfer (Adiabatic)
Case 4: n =  ; then pV  = C or V = C Constant volume process (Isochoric)

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 Thermal Expansion in Gases
Polytropic Expansion Process
• When work is done in an polytropic process
𝑣𝑓
W=‫=𝑣𝑑𝑝 𝑣׬‬
𝑖
𝑣
‫𝑡𝑠𝑛𝑜𝑐 𝑓 𝑣׬‬. 𝑑𝑣/𝑣
𝑖

𝑃2 𝑣2 − 𝑃1 𝑣1
𝑊=
1−𝑛

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 Equations of State

• An equation of state is a thermodynamic equation relating state

variables, which describe the state of matter under a given set of physical
conditions, such as pressure, volume, temperature, or internal energy.
Equations of state are useful in describing the properties of pure
substances and mixtures in liquids, gases, and solid states.
• These allow us to overcome the limitations of ideal gas law and predict
the properties for real gases, under real life conditions. Some of these
are:
– Van der Waals
– Peng-Robinson
– Redlich-Kwong
– Soave
– Soave-Redlich-Kwong
– Cubic equations

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 Equations of State
Van der Waals Equations
• Van der Waals equation is an equation of state which extends the ideal
gas law to include the effects of interaction between molecules of a gas,
as well as accounting for the finite size of the molecules.
• To account for the volume occupied by real gas molecules, the Van der
Waals equation replaces in the ideal gas law with ,
where 𝑽𝒎 is the molar volume of the gas and b is the volume occupied by
the molecules of one mole
• The Van der Waals equation includes intermolecular interaction by adding
to the observed pressure P in the equation of state a term of the form ,
where a is a constant whose value depends on the gas.

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 Equations of State
Equations of State for Gases
• Van der Waals (1873) a & b constants for Equations of State

• Peng-Robinson (1976)

• Redlich-Kwong (1949)

• Soave-Redlich-Kwong
𝑅𝑇 𝑎
P= -
𝑉−𝑏 𝑉(𝑉+𝑏)

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Solving for Entropy Changes in Non-Ideal Gases
using Equations of State requires the application
of calculus.

(Revise what you have forgotten)

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 Mathematical Preliminaries
• Eight thermodynamic state variables thus far discussed:
P, T, V, S, U, H, A, G
• If values of two of them were known: we could calculate
the values of the remaining six state variables
• thermodynamic state of pure, single-phase system is
fixed!
• Mathematically: we choose two variables as
independent variables (for the pure, single-phase
system, single component system)
• Remaining six variables are dependent variables

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 Mathematical Preliminaries
• EXAMPLE: T and V independent variables
➢ Any other thermodynamic state variables are
dependent variables:
➢ U: Internal Energy is a dependent variable!
• U = U ( T, V)
➢ This means that the Internal Energy is a function of
temperature and specific volume.
• The change in internal energy d U , which is a result
of differential changes in T and V is therefore:
•

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 Mathematical Preliminaries

• The subscript on each derivative denotes the variable

being held constant:

: Shows the differential change in molar

internal energy accompanying a diff. change
in temperature, whereby the molar volume is
constant.

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 Mathematical Preliminaries
• Keep in mind that : (𝜕U / 𝜕T)V and (𝜕U / 𝜕V)T are partial
derivatives of the type
𝜕𝑋
( )Z
𝜕𝑌
• At the same time: X , Y , Z are used to denote the state
variables and are used here to represent the state
variables P, T, V, S, U, H, A and G
• Goal of present chapter is to develop methods to allow us
to calculate the numerical values of these derivatives
➢ Needed for many thermodynamic applications

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 Thermodynamic Derivatives
• Definitions:

• Further Definitions:

• Energy Balance + G dN

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 Thermodynamic Derivatives
• For Closed Systems we can write *):

• Then we have: V =T

• And

• Alternatively we can write:

*) NOTE: U = U (S, V) ; dU =

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 Thermodynamic Derivatives
• However we may remember that:

• Then we have

• And if we now divide by N we get:

• Similarly we can derive:

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 Thermodynamic Derivatives
• Therefore from the First Law we can derive:

35
 Thermodynamic Derivatives
• The Maxwell Relations:
• Expressions for other derivatives:

• Then we can get:

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 Thermodynamic Derivatives
• The Maxwell Relations:
• Similar expressions for other derivatives:

• These are the famous Maxwell Relations

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 Fundamental Thermodynamic
Relation
• From the First Law we remember:
U = Q + W or as derivatives: dU = dQ + dW
• Since it is obviously true also for reversible changes,
we have:
dU = dQrev + dWrev
• We know that dWrev = - P dV reversible work
• Then we can write: dU = dQrev - P dV
• From the definition of entropy (Second Law) we
𝒅𝑸 𝒓𝒆𝒗
remember: dS =
𝑻
• And therefore: dQrev = T dS
• Expression for the reversible heat transfer
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 Fundamental Thermodynamic
Relation
• So we can put these together to form an expression
for dU which only involves functions of state.
• For a hydrodynamic system, for instance:
dU = T dS - P dV
• The fundamental thermodynamic relation
• It involves only functions of state, so it is true for all
changes, not just reversible ones
• This suggests that the natural variable in which to
express U are S and V: U = U (S , V)
• That means that internal energy will be unchanged
for processes at constant volume and entropy--

39
 Fundamental Thermodynamic
Relation - ENTHALPY
→ not the most common experimental conditions.
• It is therefore useful to introduce other functions of
state, called ``thermodynamic potentials'', which are
conserved, or whose change is easily calculated, in
common experimental conditions. These are:
➢ Enthalpy H = U + P V ; hence,
dH = d U +P dV + Vdp
and with: dU = T dS - P dV , the fundamental
thermodynamic relation, we obtain:
dH = d U +p dV + V dP = T dS - P dV + P dV + V dP
dH = T dS + V dP

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 Helmholtz Free Energy
dH = T dS + V dP
• At constant pressure (such as chemical reactions in a test
tube), dP = 0 → dH = T dS + V dP ; dH = T dS
• and therefore: dH = dQrev so that
➢ Heats of reaction are usually measured as enthalpies of
reaction (at constant pressure)
Helmholtz Free Energy (E)
• Similarly we get: E =U–TS
• The derivative is: dE = dU –TdS – S dT
• We remember that: dU = TdS – PdV
• By substitution: dE = – S dT – PdV
• E is constant at constant temperature and volume.
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 Gibbs Free Enthalpy Relation
dH = T dS + V dP
Gibbs Free Enthalpy (G)
• Similarly we get: G =H–TS
• The derivative is: dG = dH –TdS – S dT
• We remember that: dH = TdS + PdV
• By substitution: dG = TdS + PdV – S dT – PdV
• Therefore: dG = VdP – S dT
• The Gibbs Free Enthalpy is constant at constant
temperature and pressure.
• These are the conditions under which phase transitions
(melting, boiling) take place, and are also relevant to
chemical equilibrium
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 Maxwell’s Relations
• We remember: dU = T dS – P dV
fundamental thermodynamic relation
• On purely mathematical grounds, we may re-write this
as: U = U (S, V) ; or
𝜕𝑈 𝜕𝑈
dU = ( )V dS + ( )S dV
𝜕𝑆 𝜕𝑉
dU = T dS – P dV
• By comparison with the fundamental relation we see
that:
𝝏𝑼 𝝏𝑼
• Temperature T = ( )V ; Pressure: P = - ( )S
𝝏𝑺 𝝏𝑽

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 Maxwell’s Relations
𝝏𝑼 𝝏𝑼
• Temperature T = ( )V ; Pressure: P = - ( )S
𝝏𝑺 𝝏𝑽
• These definitions (especially the second) are interesting in
their own right.
• But we can go further, by differentiating both sides of the
first equation by V and of the second by S :
𝝏𝑻 𝝏 𝝏𝑼
( )S = ( ( )V ) S
𝝏𝑽 𝝏𝑽 𝝏𝑺
𝝏𝑷 𝝏 𝝏𝑼
( )V = - ( ( )S ) V
𝝏𝑺 𝝏𝑺 𝝏𝑽
• the order of differentiation in the second derivation is
irrelevant, → right hand sides are equal, and thus so are the
left hand sides, giving:
𝛛𝐓 𝛛𝐏
( )S = - ( )V
𝛛𝐕 𝛛𝐒

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 Maxwell’s Relations
• By starting with , E, H and G, we can get three more
relations
𝝏𝑼 𝝏𝑼
i. dU = TdS – PdV => T = ( )V and P = - ( )S
𝝏𝑺 𝝏𝑽
𝝏𝑬 𝝏𝑬
ii. dE = -SdT – PdV => S = ( )V and P = - ( )T
𝝏𝑻 𝝏𝑽
𝝏𝑯 𝝏𝑯
iii. dH = TdS + VdP => T = ( )P and V = - ( )S
𝝏𝑺 𝝏𝑷
𝝏𝑮 𝝏𝑮
iv. dG = -SdT + VdP => S = ( )V and V = - ( )T
𝝏𝑻 𝝏𝑷
• The two equations involving derivatives of S are
particularly useful; as they provide a possibility to
determine S,

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 Heat Capacities
➢ Heat capacities are related to changes of entropy with
temperature
• A heat capacity is the temperature change per unit
heat absorbed by a system during a reversible process
C dT = dQ rev
• Specific heat capacity (C)'; the latter is the heat
capacity C per kg or per mole
• The heat capacity is is different for different processes.
Useful heat capacities are those at constant volume or
constant pressure (for a fluid). Since
dQ rev = T dS
we have at constant volume CV dT = T dS , so
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 Heat Capacities
• we have at constant volume CV dT = T dS , so
𝝏𝑺
i. CV = T ( )V Heat Capacity at constant volume
𝝏𝑻
𝝏𝑺
ii. CP = T ( )P Heat Capacity at constant pressure
𝝏𝑻
• At constant volume (reversible conditions!) no work is done;
therefore: dU = dQ rev + PdV
dU = dQ rev
𝝏𝑼
i. CV = ( )V expressed in terms of internal Energy
𝝏𝑻
• Also (usefully for chemists), at constant pressure dP=0
d H = dQ rev where H is the enthalpy, so
𝝏𝑯
ii. CV = ( ) expressed in terms of Enthalpy
𝝏𝑻 P

47
 Heat Capacities
➢ The specific heat capacity is the heat capacity per unit mass
(or per mole).
➢ Heat capacities are not independent of temperature (or
pressure) in general, but over a narrow temperature range
they are often treated as such, especially for a solid.
➢ Together with two of Maxwell's relations, we now have
expressions for the partial derivatives of the entropy with
respect to all easily measurable variables (P, V , T).
➢ These can be used to derive expressions for the entropy
change in real processes as well! We can show how to do
that by using the Van der Waals Equation
𝑅𝑇 𝑎
P= -
𝑉−𝑏 𝑉2

48
 Heat Capacities
• We can also derive a relation between , , and other
measurable properties of a substance which can be
checked experimentally: If
➢ a is the isobaric thermal expansion coefficient and
➢ kT is the isothermal compressibility
• With
1 𝝏𝑽 1 𝝏𝑽
a= ( ) and kT = - ( )
𝑉 𝝏𝑻 P 𝑉 𝝏𝑷 T
• We obtain
𝑎2
CP – CV = VT
kT
which is always greater than zero.

49
 Heat Capacities
𝑎2
CP – CV = VT
kT
• This relation is a firm prediction of thermal physics
without any approximations whatsoever.
➢ It has to be true! For real gases and compressible
liquids and solids it can be checked.
• For relatively incompressible liquids and solids it is hard
to carry out processes at constant volume so CV may
not be well known and this equation can be used to
predict it.
• For one mole of a van der Waals gas this gives
2𝑎 (𝑉−𝑏)2 -1
CP – CV = R[ 1 - ]
RTV 3
50
 Heat Capacities
• For one mole of a van der Waals gas this gives
2𝑎 (𝑉−𝑏)2 -1
CP – CV = R[ 1 - ]
RTV 3
• In the ideal gas case a, b → 0 are zero (limit)
• Above equation then reduces to
CP – CV = R

51
 Application of Heat Capacities
Calculating Entropy Change
Question
What is the entropy change during the expansion of a van
der Waals gas for which CV is a constant?

𝑅𝑇 𝑎
• Equation of state for one mole: P= -
𝑉−𝑏 𝑉2

52
 Entropy Change Calculation
𝑅𝑇 𝑎
P= -
𝑉−𝑏 𝑉2

• b represents the volume taken up by the finite size of the

molecules,
• a/V2 is the reduction in pressure due to interactions
between the molecules.
• In this way the two most important corrections neglected in
the ideal gas are included.
• However, the heat capacity at constant volume is still
independent of temperature and volume, as in an ideal gas.
• During an expansion, both the temperature and the volume
may change.

53
 Entropy Change Calculation
• To calculate the change in entropy, we need
𝝏𝑺 𝑪𝑽 𝝏𝑺
( )V = from definition of CV = T ( )V
𝝏𝑻 𝑻 𝝏𝑻
• Equation can be modified:
• Differentiation of V.-d. Waals equation:
𝝏𝑷 𝑹
( )V =
𝝏𝑻 𝑽−𝒃
𝝏𝑺 𝝏𝑷 𝑹
( )T = ( )V =
𝝏𝑽 𝝏𝑻 𝑽−𝒃
𝝏𝑺 𝝏𝑺
• Then dS = ( )V dT + ( )T dV , using a Maxwell Relation
𝝏𝑻 𝝏𝑽
• If we now substitute:
𝝏𝑺 𝑪𝑽 𝝏𝑷 𝑹
( )V = and ( )V = we obtain:
𝝏𝑻 𝑻 𝝏𝑻 𝑽−𝒃

54
 Entropy Change Calculation
𝑪𝑽 𝑹
• Finally dS = dT + 𝑑𝑉
𝑻 𝑽−𝒃
• Choose variables, either (V, T) or , (P, T) and
• writing dS in terms of infinitesimal changes of these
variables
• then using the definition of the heat capacities, and a
Maxwell relation, we obtain something like the second
line.
• Then we can calculate the total entropy change by
integrating, first at constant T and then at constant V :
𝑽 𝝏𝑺 (𝑻𝟏,𝑽)
S ( T1, V2) = S ( T1, V1) + ‫[ 𝟐 𝑽׬‬ ]T dV
𝟏 𝝏𝑽

55
 Heat Capacities
• Then we can calculate the total entropy change by
integrating, first at constant T and then at constant
V:
𝑉2 𝜕𝑆 (𝑇1,𝑉)
S ( T1, V2) = S ( T1, V1) + ‫[ 𝑉׬‬ ]T dV
1 𝜕𝑉
𝑉2 𝑅
S ( T1, V2) = S ( T1, V1) + ‫( 𝑉׬‬ )T dV
1 𝑉−𝑏
𝑉2 −𝑏
=S ( T1, V1) + 𝑅𝑙𝑛( )
𝑉1−𝑏
• Similarly:
𝑇2 𝜕𝑆 (𝑇1,𝑉)
S ( T1, V2) = S ( T1, V2) + ‫[ 𝑇׬‬ ]T dP
1 𝜕𝑉
𝑇2 𝐶𝑉
=S ( T1, V2) + ‫𝑇׬‬ dT
1 𝑇

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 Entropy Change Calculation
𝑇 𝜕𝑆 (𝑇1,𝑉)
➢ S ( T2, V2) = S ( T1, V2) + ‫ 𝑇׬‬2 [ ]T dP
1 𝜕𝑉
𝑇2 𝐶𝑉
= S (T1 , V2) + ‫𝑇 𝑇׬‬ dT
1

T2
= S ( T1, V2) + CV ln
T1
𝑉2 −𝑏 T2
= S ( T1, V2) + CV 𝑅𝑙𝑛 + CV ln
𝑉1−𝑏 T1
➢ Therefore:
T2
𝑽𝟐 −𝒃
S ( T2, V2) - S ( T1, V2) = CV 𝑹𝒍𝒏 CV ln +
T1
𝑽𝟏−𝒃
where in the second integration we used the fact that
CV is constant.

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 Entropy Change Calculation
𝑉2 −𝑏 T2
S ( T2, V2) - S ( T1, V2) = CV 𝑅𝑙𝑛 + CV ln
𝑉1−𝑏 T1
➢ We can check our result against those we have
already calculated for an ideal gas just by setting
b=0 and using the correct CV
➢ for a monatomic gas CV = 3/2R
➢ for an isothermal expansion (T1 = T2) we get:
V2
ΔS = R ln
V1
➢ for a reversible adiabatic expansion we can use
T1 V1 Υ-1 = T2 V2 Υ-1
We remember heat capacities at constant pressure and
at constant volume differ by a constant for ideal gases:
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 Entropy Change Calculation
• We remember that heat capacities at constant
pressure and at constant volume differ by a constant
for ideal gases:
CP – CV = n R
• reversible adiabatic compression or expansion of an
ideal gas the pressure and volume change together
in such a way that:
γ 𝐶𝑃
P V = constant, where γ=
𝐶𝑉
• Then from the Ideal Gas Law: p V = n R T it follows
that: 1
( )
T V γ-1 = constant and T P γ−1 = constant

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[email protected]

Department of Chemical, Metallurgical and Materials Engineering

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