Chemical Engineering Thermodynamics II

CHE-303

INSTRUCTOR: Dr. NAYEF M. ALSAIFI

Chapter 6: Thermodynamic Properties of Fluids

 Measurements in daily life

 In daily life, many physical quantities are used in measurements such as temperature,
volume, length and pressure.

Pressure

Temperature Volume

2
 Thermodynamic measurements

 In thermodynamics, experimental measurements are also very important because

thermodynamics alone is generally not sufficient to solve engineering problems

 Unfortunately, not all thermodynamic properties are measurable.

 Let’s focus on the following main thermodynamic properties:

A U H T: Temperature
P: Pressure
Thermodynamic V: Volume
Properties U: Internal energy
T P V S : Entropy
H: Enthalpy
A : Helmholtz free energy
G : Gibbs free energy
G S

 Note that, two new thermodynamic properties (A & G) are introduced. 3

 Thermodynamic properties

 There are three types of thermodynamic properties:

1 Measured Properties P, V, T, composition

(measurable)

U (From the first law of thermodynamics)

2 Fundamental Properties

(not measurable) S (From the second law of thermodynamics)

3 Derived thermodynamic properties H, A, G

(not measurable)

Enthalpy Helmholtz energy Gibbs energy

𝐻 = 𝑈 + 𝑃𝑉 𝐴 = 𝑈 − 𝑇𝑆 𝐺 = 𝐻 − 𝑇𝑆
4
 Thermodynamic properties

Process Main Problem Calculate heat & work?

HOW?
Heat and work are related to
changes of internal energy and
entropy.

 Are work and heat related to internal energy and entropy?!!

Yes. For example, you could see that from the 1st and 2nd laws in a closed system
and reversible process:

 1st law 𝑑𝑈 = 𝑑𝑄𝑟𝑒𝑣 + 𝑑𝑊 ( Q and W are related to ∆𝑈)

 2nd law 𝑑𝑄𝑟𝑒𝑣 = 𝑇𝑑𝑆 𝑑𝑈 = 𝑇𝑑𝑆 + 𝑑𝑊 ( Q and W are related to ∆𝑆)

5
 Thermodynamic properties

 The problem is now: how to obtain the change of internal energy and entropy?

Internal energy and entropy cannot directly be measured from experiment.

Therefore, we cannot find the values of Q and W for a process unless we

find the change of internal energy and entropy.

If internal energy and entropy cannot directly be measured, Is there a method

that would assist to find them indirectly?

Yes, this could be done by first relating

internal energy and entropy to measurable
properties such as T, P and V.

 Chapter 6 sheds light on how to relate unmeasurable properties such as change in

internal energy, entropy, Helmholtz energy and Gibbs energy to measurable properties
such as T, P and V. 6
 Towards relating unmeasurable to measurable properties

Thermodynamic potentials
U
S T
H P
A V
G

 The initial step towards relating the unmeasurable to measurable properties is to

define the total differentials of energy functions (i.e. dU, dH, dA and dG) in terms
of two independent variables* which are called natural variables.

 The four fundamental thermodynamic potentials (U, H, A and G) are defined in

terms of their natural variables as follows:

Thermodynamic Natural
potential variables
U S&V
H S&P
A T&V
G T&P

* Two variables because we consider a pure component and a single phase in this chapter. 7
 The differential expression of the potential U (dU)

 For a closed system and single phase

 The first law of thermodynamics for a closed system and reversible process is given by:

𝑑𝑈 = 𝑑𝑄𝑟𝑒𝑣 + 𝑑𝑊𝑟𝑒𝑣 (6.1)

 𝑑𝑊𝑟𝑒𝑣 and 𝑑𝑄𝑟𝑒𝑣 are defined as follows:

𝑑𝑊𝑟𝑒𝑣 = −𝑃𝑑𝑉 (6.2) 𝑑𝑄𝑟𝑒𝑣 = 𝑇𝑑𝑆 (6.3)

 From the above equations, we get the first fundamental equation:

𝑑𝑈 = 𝑇 𝑑𝑆 − 𝑃 𝑑𝑉 (6.4)

 Note that the change in dU is given in terms of the change of S and V (i.e dS and dV)
which arise naturally. This is why S and V are called the natural variables of U.

8
 The differential expression of the potential U (dU)

 The first fundamental equation for a closed system is given by:

𝑑𝑈 = 𝑇 𝑑𝑆 − 𝑃 𝑑𝑉 (6.4)

 The first fundamental equation

 is a combination of the first and second laws of thermodynamics

 contains only properties of the system.

 represents a differential change between equilibrium states.

 Is the first fundamental equation limited to reversible processes?

 The equation was derived for a reversible process as seen in the previous
slide. However, it depends on the change between the properties and not
on the path of the process . Therefore, the equation can be applied to any
process whether it is reversible or irreversible process.

9
 The differential expression of the potential H (dH)

 Enthalpy is a derived thermodynamic property and defined as:

𝐻 = 𝑈 + 𝑃𝑉 (6.5)

 The enthalpy is defined this way because in open systems, two terms contribute
to the energy; internal energy and flow work (PV). This is why it is convenient to
define a property that includes both contributions.

 The change of enthalpy is given by the differential form of 6.5:

𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 (6.6)

 dU is defined by equation 6.4. Therefore, substitute 6.4 into 6.6:

𝑑𝐻 = 𝑇 𝑑𝑆 − 𝑃 𝑑𝑉 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 (6.7)

 Equation 6.7 is simplified to:
𝑑𝐻 = 𝑇 𝑑𝑆 + 𝑉𝑑𝑃 (6.8)

 Note that dS and dP appear naturally. This is why S and P are called natural variables of H.

10
 The differential expression of the potential A (dA)

 The Helmholtz free energy is defined as follows:

𝐴 = 𝑈 − 𝑇𝑆 (6.9)

 The change of the Helmholtz free energy is given by the following differential form :

𝑑𝐴 = 𝑑𝑈 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 (6.10)

 By using equation 6.4, 6.10 becomes:

𝑑𝐴 = 𝑇 𝑑𝑆 − 𝑃 𝑑𝑉 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 (6.11)

 Finally, the change of the Helmholtz free energy is given by:

𝑑𝐴 = −𝑆𝑑𝑇 − 𝑃 𝑑𝑉 (6.12)

11
 The differential expression of the potential G (dG)

 The Gibbs free energy is defined as follows:

𝐺 = 𝐻 − 𝑇𝑆 (6.13)

 The change of the Helmholtz free energy is given by the following differential form :

𝑑𝐺 = 𝑑𝐻 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 (6.14)

 By using equation 6.8, 6.14 becomes:

𝑑𝐺 = 𝑇 𝑑𝑆 + 𝑉𝑑𝑃 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 (6.15)

 Finally, the change of the Gibbs free energy is given by:

𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 (6.16)

12
Summary of the four fundamental thermodynamic potentials

dU  TdS  PdV

dH  TdS  VdP

dA  PdV  SdT

dG  VdP  SdT

 The above four equations are also called Gibbs equations.

13
Let’s review a little mathematics

14
 Total differential of F (dF)

 If F is a function of x and y (i.e. F(x,y)), the total differential of F is given by

𝜕𝐹 𝜕𝐹
𝑑𝐹 = 𝑑𝑥 + 𝑑𝑦 (6.17)
𝜕𝑥 𝑦
𝜕𝑦 𝑥

or 𝑑𝐹 = 𝑀 𝑑𝑥 + 𝑁𝑑𝑦 (6.18)

𝜕𝐹 𝜕𝐹
𝑀= 𝑁=
𝜕𝑥 𝑦
𝜕𝑦 𝑥

 Note that x and y is called independent variables and F is dependent function.

 If f is a function of x and y, the right hand side of 6.17 is called an exact differential expression
when:

𝜕𝑁 𝜕𝑀
= (6.19)
𝜕𝑥 𝑦
𝜕𝑦 𝑥

 Equation 6.19 is considered as the criterion of exactness.

15
 Exact differential

 Test the following differential expression to determine if it is an exact differential:

 𝑑𝑧 = (𝑦 2 − 2𝑥)𝑑𝑥 + (2𝑥𝑦 + 1)dy

 The exactness criterion should be tested:

𝜕𝑀
𝑀 = 𝑦 2 − 2𝑥 = 2𝑦
𝜕𝑦 𝑥

𝜕𝑁
𝑁 = (2𝑥𝑦 + 1) = 2𝑦
𝜕𝑥 𝑦

𝜕𝑁 𝜕𝑀
=
𝜕𝑥 𝑦
𝜕𝑦 𝑥

2𝑦 = 2𝑦

 The above differential expression is an exact differential.

16
 Exact differential

 Test the following differential expressions to determine which one is an exact differential:
4
𝑥
 𝑑𝑧 = 𝑥 3 𝑦𝑑𝑥 + dy
4

 𝑑𝑧 = 𝑥 3 𝑦 3 𝑑𝑥 + 𝑥 3 𝑦 3 dy

 𝑑𝑧 = 𝑥 2 𝑦 3 𝑑𝑥 + 𝑥 3 𝑦 2 dy

17
 Why exact differential ?

 In thermodynamics, the exact differential criterion would help:

 to derive many thermodynamic relationships.

 to express thermodynamic properties in terms of measurable quantities

18
 Maxwell Equations

 Maxwell used the exact differential criterion with the four Gibbs energy:

 For example, the total differential of U (dU) is given by:

𝑑𝑈 = 𝑇 𝑑𝑆 − 𝑃 𝑑𝑉

 Maxwell used the criterion of the exact differential as follows

 T   P 
    
 V S  S V

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 Maxwell relations

 Maxwell gave the exact differential for the four Gibbs equation:

dU  TdS  PdV  T   P 
    
 V S  S V

dH  TdS  VdP  T   V 
   
 P S  S P

 P   S 
dA  PdV  SdT    
 T V  V T

 V   S 
dG  VdP  SdT     
 T P  P T

20
 Internal energy as function of temperature and volume
𝑼 = 𝑼(𝑻, 𝑽)
𝜕𝑈 𝜕𝑈
𝑑𝑈 = 𝑑𝑇 + 𝑑𝑉
𝜕𝑇 𝑉
𝜕𝑉 𝑇

𝜕𝑈 𝜕𝑈
𝜕𝑇 𝑉
𝜕𝑉 𝑇

 The fundamental equation of dU is given by

dU = TdS − PdV

𝜕𝑈 𝜕𝑈 𝑇𝜕𝑆 − 𝑃𝜕𝑉 𝜕𝑆
𝐶𝑉 = = =𝑇 −𝑃
𝜕𝑇 𝑉
𝜕𝑉 𝑇
𝜕𝑉 𝑇
𝜕𝑉 𝑇

 From Maxwell’s relations, we know that

𝜕𝑆 𝜕𝑃
=
𝜕𝑉 𝑇
𝜕𝑇 𝑉

 Recall: Cv is measurable property 𝜕𝑈 𝑇𝜕𝑆 − 𝑃𝜕𝑉 𝜕𝑃

= =𝑇 −𝑃
𝜕𝑉 𝑇
𝜕𝑉 𝑇
𝜕𝑇 𝑉

𝜕𝑈 𝜕𝑈 𝜕𝑃
𝑑𝑈 = 𝑑𝑇 + 𝑑𝑉 = 𝐶𝑉 𝑑𝑇 + 𝑇 − 𝑃 𝑑𝑉
𝜕𝑇 𝑉
𝜕𝑉 𝑇
𝜕𝑇
𝑉

𝜕𝑃
∆𝑈 = 𝐶𝑉 𝑑𝑇 + 𝑇 − 𝑃 𝑑V
𝜕𝑇 𝑉 21
 CV in terms of entropy

𝜕𝑈
𝐶𝑉 =
𝜕𝑇 𝑉

 The fundamental equation of dU is given by

dU = TdS − PdV

𝜕𝑈 𝜕𝑆 𝜕𝑉
𝐶𝑉 = =𝑇 −𝑃
𝜕𝑇 𝑉
𝜕𝑇 𝑉
𝜕𝑇 𝑉

0
𝜕𝑆
𝐶𝑉 = 𝑇
𝜕𝑇 𝑉

𝐶𝑉 𝜕𝑆
=
𝑇 𝜕𝑇 𝑉

22
Entropy as function of temperature and volume
𝑺 = 𝑺(𝑻, 𝑽)
𝜕𝑆 𝜕𝑆
𝑑𝑆 = 𝑑𝑇 + 𝑑𝑉
𝜕𝑇 𝑉
𝜕𝑉 𝑇

𝜕𝑆 𝜕𝑆
𝜕𝑇 𝑉
𝜕𝑉 𝑇

 From Maxwell’s relations, we know that

𝜕𝑆 𝐶𝑉
=
𝜕𝑇 𝑉
𝑇 𝜕𝑆 𝜕𝑃
=
𝜕𝑉 𝑇
𝜕𝑇 𝑉

𝐶𝑉 𝜕𝑃
𝑑𝑆 = 𝑑𝑇 + 𝑑𝑉
𝑇 𝜕𝑇 𝑉

𝐶𝑉 𝜕𝑃
∆𝑆 = 𝑑𝑇 + 𝑑𝑉
𝑇 𝜕𝑇 𝑉

23
 Enthalpy as function of temperature and pressure
𝑯 = 𝑯(𝑻, 𝑷)
𝜕𝐻 𝜕𝐻
𝑑𝐻 = 𝑑𝑇 + 𝑑𝑃
𝜕𝑇 𝑃
𝜕𝑃 𝑇

𝜕𝐻 𝜕𝐻
𝜕𝑇 𝑃
𝜕𝑃 𝑇

 The fundamental equation of dH is given by

dH = TdS + VdP

𝜕𝐻 𝜕𝐻 𝑇𝜕𝑆 + 𝑉𝜕𝑃 𝜕𝑆
𝐶𝑝 = = =𝑇 +𝑉
𝜕𝑇 𝑃
𝜕𝑃 𝑇
𝜕𝑃 𝑇
𝜕𝑃 𝑇

 From Maxwell’s relations, we know that

𝜕𝑆 𝜕𝑉
=−
𝜕𝑃 𝑇
𝜕𝑇 𝑃

 Recall: Cv is measurable property 𝜕𝐻 𝑇𝜕𝑆 + 𝑉𝜕𝑃 𝜕𝑉

= = −𝑇 +𝑉
𝜕𝑃 𝑇
𝜕𝑃 𝑇
𝜕𝑇 𝑃

𝜕𝐻 𝜕𝐻 𝜕𝑉
𝑑𝐻 = 𝑑𝑇 + 𝑑𝑃 = 𝑑𝐻 = 𝐶𝑝 𝑑𝑇 + −𝑇 + 𝑉 𝑑𝑃
𝜕𝑇 𝑃
𝜕𝑃 𝑇
𝜕𝑇
𝑃

𝜕𝑉
∆𝐻 = 𝐶𝑝 𝑑𝑇 + V−𝑇 𝑑𝑃
𝜕𝑇 𝑃 24
 Cp in terms of entropy

𝜕𝐻
𝐶𝑝 =
𝜕𝑇 𝑃

 The fundamental equation of dH is given by

dH = TdS + VdP

𝜕𝐻 𝜕𝑆 𝜕𝑃
𝐶𝑝 = =𝑇 +𝑉
𝜕𝑇 𝑃
𝜕𝑇 𝑃
𝜕𝑇 𝑃

0
𝜕𝑆
𝐶𝑝 = 𝑇
𝜕𝑇 𝑃

𝐶𝑝 𝜕𝑆
=
𝑇 𝜕𝑇 𝑃

25
Entropy as function of temperature and volume
𝑺 = 𝑺(𝑻, 𝑷)
𝜕𝑆 𝜕𝑆
𝑑𝑆 = 𝑑𝑇 + 𝑑𝑃
𝜕𝑇 𝑃
𝜕𝑃 𝑇

𝜕𝑆 𝜕𝑆
𝜕𝑇 𝑃
𝜕𝑃 𝑇

 From Maxwell’s relations, we know that

𝜕𝑆 𝐶𝑃
=
𝜕𝑇 𝑃
𝑇 𝜕𝑆 𝜕𝑉
=−
𝜕𝑃 𝑇
𝜕𝑇 𝑃

𝐶𝑃 𝜕𝑉
𝑑𝑆 = 𝑑𝑇 − 𝑑𝑃
𝑇 𝜕𝑇 𝑃

𝐶𝑃 𝜕𝑉
∆𝑆 𝑇, 𝑃 = 𝑑𝑇 − 𝑑𝑃
𝑇 𝜕𝑇 𝑃

26
Change of volume as a function of T and P

𝑉 = 𝑉(𝑇, 𝑃)

 Two new measurable intensive properties:

 Volume expansivity (𝛽)

 Isothermal compressibility(𝜅)

27
 Change of volume as a function of T and P

 If V is a function of T and P (i.e. 𝑉 = 𝑉(𝑇, 𝑃) ), the change in 𝑑𝑉 is given by:

𝜕𝑉 𝜕𝑉
𝑑𝑉 = 𝑑𝑇 + 𝑑𝑃
𝜕𝑇 𝑃
𝜕𝑃 𝑇

 There are two thermodynamic properties related to the above partial derivatives:

1 𝜕𝑉
 Volume expansivity: 𝛽=
𝑉 𝜕𝑇 𝑃

1 𝜕𝑉
 Isothermal compressibility: 𝜅 = −
𝑉 𝜕𝑃 𝑇

 The change of volume could be given in terms of 𝛽 and 𝜅 as:

𝑑𝑉
= 𝛽𝑑𝑇 − 𝜅𝑑𝑃
𝑉

28
 Volume expansivity

1 𝜕𝑉
 Volume expansivity: 𝛽=
𝑉 𝜕𝑇 𝑃

 volumetric property

 intensive property

 Measurable property

 dimension is 1/T
 Always positive (except for liquid water between 0 and 4 oC)

 The volume expansivity is an indication of the change in volume that

occurs when temperature changes while pressure remains constant.

 At normal boiling point,

𝛽 = 270 ∗ 10−5 𝐾 −1 for water vapor

𝛽 = 75 ∗ 10−5 𝐾 −1 for water liquid

 The above values indicate that if you heat a substance at fixed pressure, it is:
 easier to change the volume of the gas (bigger value).
 more difficult to change the volume of a liquid.
29
 Isothermal compressibility

1 𝜕𝑉
 Isothermal compressibility: 𝜅 = −
𝑉 𝜕𝑃 𝑇
 volumetric property

 intensive property

 Measurable property

 dimension is 1/P
 positive

 The isothermal compressibility is an indication of the change in volume that

takes place when pressure changes while temperature remains constant. The
value is always positive for all substances in all phases.

 At normal boiling point,

𝜅 = 1 𝑏𝑎𝑟 −1 for water vapor

𝜅 = 4.9 ∗ 10−7 𝑏𝑎𝑟 −1 for water liquid

 The values indicate that it is easy to change the volume of vapour but difficult
for liquid

30
 Volume expansivity & isothermal compressibility in the literature

 Volume expansivity and isothermal compressibility are vary important in research;

practically for liquids

31
 U as a function of T and P

 Example
 If U is a function of T and P, determine dU?

32
 Example

 One mole of propane gas is to be expanded from 0.001 m3 to 0.04 m3 while in

contact with a heating bath at 100 oC. The expansion is not reversible. The heat
extracted from the bath is 600 J. Using the van der waals equation of state, determine
the work for the expansion?

Solution:
∆𝑈 = 𝑄 + 𝑊

𝜕𝑃
∆𝑈 = 𝐶𝑉 𝑑𝑇 + 𝑇 − 𝑃 𝑑V
𝜕𝑇 𝑉

Answer W=336 J/mol

33
 If Gibbs energy is known, other properties are easily derived

 The Gibbs energy serves as a generating function for the other thermodynamic properties.

 This could be done by the following procedure:

𝐺
 Start with
𝑅𝑇

𝐺 𝐺 1 𝐺
 Differentiate 𝑑 = 𝑑𝐺 − 𝑑𝑇 *
𝑅𝑇 𝑅𝑇 𝑅𝑇 𝑅𝑇 2

𝐺 𝑉𝑑𝑃 𝑆𝑑𝑇 𝐺
 Use 𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 in * 𝑑 = − − 𝑑𝑇 **
𝑅𝑇 𝑅𝑇 𝑅𝑇 𝑅𝑇 2

𝐺 = 𝐻 − 𝑇𝑆 𝐺 𝑉𝑑𝑃 𝑆𝑑𝑇 𝐻 𝑇𝑆
 Use in ** 𝑑 = − − 𝑑𝑇 + 𝑑𝑇
𝑅𝑇 𝑅𝑇 𝑅𝑇 𝑅𝑇 2 𝑅𝑇 2

𝐺 𝑉 𝐻
 Finally 𝑑 = 𝑑𝑃 − 𝑑𝑇
𝑅𝑇 𝑅𝑇 𝑅 𝑇2

 The last equation could be used as a generating function for all other thermodynamic
properties as you can see in the next slide.
34
If Gibbs energy is known, other properties are easily derived

𝐺 𝑉 𝐻
𝑑 = 𝑑𝑃 − 𝑑𝑇
𝑅𝑇 𝑅𝑇 𝑅 𝑇2

 For constant T
𝑉 𝜕 𝐺/𝑅𝑇
 Volume =
𝑅𝑇 𝜕𝑃 𝑇

 For constant P
𝐻 𝜕 𝐺/𝑅𝑇
 Enthalpy = −𝑇
𝑅𝑇 𝜕𝑇 𝑃

𝑈 𝐻 𝑃𝑉
 Internal energy = −
𝑅𝑇 𝑅𝑇 𝑅𝑇

𝑆 𝐻 𝐺
 Entropy = −
𝑅 𝑅𝑇 𝑅𝑇

35
 Back to Gibbs equations

 The four fundamental equations of Gibbs are given by:

dU  TdS  PdV
dH  TdS  VdP
dA   PdV  SdT
dG  VdP  SdT

 “From these four, more than 50,000,000 equations relating the thermodynamic properties
of the system can be derived using relatively simple mathematics”

Ott J. Bevan and Boerio-Goates J.

36
 Back to Gibbs equations

 Let’s derive some equations based on the first fundamental equation:

 dU = TdS − PdV
𝜕𝑈
 If S is constant dU = TdS − PdV 𝑃=−
𝜕𝑉 𝑆
0
𝜕𝑈
 If V is constant dU = TdS − PdV 𝑇=
𝜕𝑆
0 𝑉

𝑇 𝜕𝑉
 If U is constant dU = TdS − PdV 𝑃
=
𝜕𝑆
0 𝑈

 By the combinations of the above derived relations, we could also drive more relations.
For example, by the combination of the first and third relations, we define the temperature as:

𝜕𝑉 𝜕𝑈
𝑇=−
𝜕𝑆 𝑈
𝜕𝑉 𝑆

 If the results of all the four Gibbs energy are combined, one would get hundreds of equations.

Question Are all the derived relations from Gibbs equation useful?

Answer No, fortunately, most of them have little use 37

 Let’s take some
useful relations

Expressions for partial derivatives of state functions with respect to

temperature and pressure:

 closed system
 single phase: solid, gas or liquid

38
Expressions at constant temperature

Partial derivative General expression Ideal gas

𝜕𝑝 1 𝑝
− −
𝜕𝑉 𝑇 𝜅𝑉 𝑉

𝜕𝑉 𝑉
𝜅𝑉 −
𝜕𝑝 𝑇
𝑝

𝜕𝑈
− 𝛽𝑇 + 𝜅 𝑝 𝑉 0
𝜕𝑝 𝑇

𝜕𝑈 𝛽𝑇
− 𝑝 0
𝜕𝑉 𝑇 𝜅

𝜕𝐻
1 − 𝛽𝑇 𝑉 0
𝜕𝑝 𝑇

𝜕𝐻 𝛽𝑇 − 1 0
𝜕𝑉 𝑇 𝜅

𝜕𝑆 𝑉
− 𝛽𝑉 −
𝜕𝑝 𝑇 𝑇

𝜕𝑆 𝛽 𝑝
𝜕𝑉 𝑇 𝜅 𝑇

𝜕𝐺
𝑉 𝑉
𝜕𝑝 𝑇

𝜕𝐺 1
− −𝑝
𝜕𝑉 𝑇 𝜅

1 𝜕𝑉 1 𝜕𝑉
𝛽= 𝜅=−
𝑉 𝜕𝑇 𝑃
𝑉 𝜕𝑃 𝑇
39
Expressions at constant pressure

Partial derivative General expression Ideal gas

𝜕𝑇 1 𝑇
𝜕𝑉 𝑝
𝛽𝑉 𝑉
𝜕𝑉 𝑉
𝛽𝑉
𝜕𝑇 𝑝 𝑇

𝜕𝑈
𝐶𝑝 − 𝛽𝑝 𝑉 𝐶𝑉
𝜕𝑇 𝑝

𝜕𝑈 𝐶𝑝 𝐶𝑉 𝑇
− 𝑝
𝜕𝑉 𝑝 𝛽𝑉 𝑉

𝜕𝐻
𝐶𝑝 𝐶𝑝
𝜕𝑇 𝑝

𝜕𝐻 𝐶𝑝 𝐶𝑝 𝑇
𝜕𝑉 𝑝 𝛽𝑉 𝑉

𝜕𝑆 𝐶𝑝 𝐶𝑝
𝜕𝑇 𝑝 𝑇 𝑇

𝜕𝑆 𝐶𝑝 𝐶𝑝
𝜕𝑉 𝑝 𝛽𝑇 𝑉 𝑉

𝜕𝐺
−𝑆 −𝑆
𝜕𝑇 𝑝

𝜕𝐺 𝑆 𝑇𝑆
− −
𝜕𝑉 𝑝
𝛽𝑉 𝑉

1 𝜕𝑉 1 𝜕𝑉
𝛽= 𝜅=−
𝑉 𝜕𝑇 𝑃
𝑉 𝜕𝑃 𝑇
40
Expressions at constant volume

Partial derivative General expression Ideal gas

𝜕𝑇 𝜅 𝑇
𝜕𝑝 𝛽 𝑝
𝑉

𝜕𝑝 𝛽 𝑝
𝜕𝑇 𝑉 𝜅 𝑇

𝜕𝑈
𝐶𝑉 𝐶𝑉
𝜕𝑇 𝑉

𝜕𝑈 𝜅 𝐶𝑝 𝑇 𝐶𝑉
− 𝛽𝑇 𝑉
𝜕𝑝 𝑉
𝛽 𝑝

𝜕𝐻 𝛽𝑉
𝐶𝑝 + 1 − 𝛽𝑇 𝐶𝑝
𝜕𝑇 𝑉 𝜅

𝜕𝐻 𝜅 𝐶𝑝 𝐶𝑝 𝑇
+ 𝑉 1 − 𝛽𝑇
𝜕𝑝 𝑉
𝛽 𝑝

𝜕𝑆 𝐶𝑉 𝐶𝑉
𝜕𝑇 𝑉 𝑇 𝑇

𝜕𝑆 𝜅 𝐶𝑝 𝐶𝑉
− 𝛽𝑉
𝜕𝑝 𝑉
𝛽𝑇 𝑝

𝜕𝐺 𝛽𝑉 𝑝𝑉
− 𝑆 − 𝑆
𝜕𝑇 𝑉 𝜅 𝑇

𝜕𝐺 𝜅𝑆 𝑇𝑆
𝑉 − 𝑉 −
𝜕𝑝 𝑉
𝛽 𝑝

1 𝜕𝑉 1 𝜕𝑉
𝛽= 𝜅=−
𝑉 𝜕𝑇 𝑃
𝑉 𝜕𝑃 𝑇 41
 Class work

 A general relationship between Cv and Cp is given by:

𝜕𝑃 𝜕𝑉
𝐶𝑝 = 𝐶𝑣 + 𝑇
𝜕𝑇 𝑉
𝜕𝑇 𝑃

 Determine the relationship between Cp and Cv for ideal gas?

42
 What we have taken so far

1 2
Change of properties in terms of Mathematical expressions to relate
measurable properties thermodynamic properties to each other

∆𝐻 ∆𝑆 ∆𝐺
3
∆𝐴 ∆𝑈 If the Gibbs energy is known, other properties
could be derived in a straightforward manner

V P T 4
𝐶𝑉 𝛽 𝜅 𝐶𝑃 Residual properties

43
Residual properties

44
 Deviation from the ideal gas

 Using the ideal gas law, determine the volume needed to store 1 mole of
methane gas in a tank at P= 19.13 atm and T=160 K?

The experimental value of the volume 516 cm3?

Answer:
𝑅𝑇
𝑉= = 686 cm3
𝑃

∆𝑉 = The experimental value – the ideal gas value

516 – 686 = -170 cm3

∆𝑉 = The actual value – the ideal gas value

 The ideal gas properties are easy to compute

45
 Deviation from the ideal gas

∆𝑉 = The actual value – the ideal gas value

The ideal gas properties

are easy to compute

∆𝑉 = The actual value – the ideal gas value

∆𝑉 = 𝑉 - 𝑉 𝑖𝑔

𝑉𝑅 = 𝑉 - 𝑉 𝑖𝑔

 The actual value could be given by:

𝑉 = 𝑉 𝑅 + 𝑉 𝑖𝑔
46
 Residual volume ( 𝑉 𝑅 )

𝑅𝑇
𝑉 𝑅 = 𝑉 − 𝑉 𝑖𝑔 𝑉 𝑖𝑔 =
𝑃

𝑍𝑅𝑇
𝑉=
𝑃

 Example:
Calculate the residual volume of methane at P=1.31 atm and T=115 K?

 Answer:
𝑅𝑇 𝑅𝑇
𝑉 𝑖𝑔 = 𝑉 𝑖𝑔 = = 7.20 𝐸 + 3 cm3/mol
𝑃 𝑃
𝑍𝑅𝑇 Z could be obtained by different methods such as
𝑉= Lee-Kesler method or equation of state. Here, we are
𝑃
going to use the virial equation of state
𝑉 = 6.88 𝐸 + 3 cm3/mol
𝑉 𝑅 = 𝑉 − 𝑉 𝑖𝑔 = 6.88𝐸3 − 7.20𝐸3 = −𝟓𝟐𝟎 cm3/mol

This value represents the deviation from the ideal gas law.
47
 Residual properties

 For any property that could be extensive :

 Residual property is the difference between the actual and ideal gas
properties:

residual property 𝑀 𝑅 = 𝑀 − 𝑀𝑖𝑔 ideal gas property

actual property

where M is V, U, H, S, A or G.

 For example, residual volume is given by:

𝑉 𝑅 = 𝑉 − 𝑉 𝑖𝑔

and residual entropy is given by:

𝑆 𝑅 = 𝑆 − 𝑆 𝑖𝑔

48
 How to get residual properties

 Residual properties serves as a difference measure for how our substance

deviates from ideal-gas behavior.

 Residual properties could be positive, negative or zero.

 At constant temperature residual properties are determined by the following expressions:

𝑅𝑇
 Residual volume 𝑉𝑅 = (𝑍 − 1)
𝑃

𝑃
𝐻𝑅 𝜕𝑍 𝑑𝑃 𝐻𝑅 𝜌
𝜕𝑍 𝑑𝜌
 Residual enthalpy: = −𝑇 or = −𝑇 +𝑍−1
𝑅𝑇 0 𝜕𝑇 𝑃
𝑃 𝑅𝑇 0 𝜕𝑇 𝜌
𝜌

𝜌
𝐺𝑅 𝑃
𝑑𝑃 𝐺𝑅 𝑑𝜌
 Residual Gibbs = 𝑍−1 or 𝑅𝑇
= 𝑍−1
𝜌
+ 𝑍 − 1 − ln (𝑍)
𝑅𝑇 0 𝑃 0
free energy

𝑃 𝑃
𝑆𝑅 𝜕𝑍 𝑑𝑃 𝑑𝑃
 Residual entropy = −𝑇 − 𝑍−1
𝑅 0 𝜕𝑇 𝑃
𝑃 0 𝑃

𝜌 𝜌
𝑆𝑅 𝜕𝑍 𝑑𝜌 𝑑𝜌
or = 𝑙𝑛 𝑍 − 𝑇 − 𝑍−1
𝑅 0 𝜕𝑇 𝜌
𝜌 0 𝜌
49
 Estimation of Z

 To estimate the residual property using the given expressions in the previous slide, it is
obvious that the compressibility factor (Z) needs to be evaluated. Different methods
could be used such as virial equation of state, cubic equation of state and generalized
property correlations.

Compressibility factor (Z)

Virial equation of state Cubic equation of state Generalized correlations

50
 Virial equation of state

 If the virial equation is given by:

𝐵𝑃
𝑍−1=
𝑅𝑇

 The residual properties could be obtained using the given relations in slide 49.

 For example, to find 𝐺 𝑅 , the following expression could be used:

𝑃
𝐺𝑅 𝑑𝑃
= 𝑍−1
𝑅𝑇 0 𝑃

𝑃
𝐺𝑅 𝐵𝑃 𝑑𝑃
𝑅𝑇
=
𝑅𝑇 𝑃
𝐺 𝑅 = 𝐵𝑃
0

 The other properties could be obtained in a similar manner.

51
 Residual properties from the Virial equation of state

 The Virial equation of state with two virial coefficients (B and C) is given in terms of
density as follows:

𝑍 − 1 = 𝐵𝜌 + 𝐶𝜌2

 The residual properties are obtained by evaluating the integrals in slide 49:

 Residual Gibbs free energy 𝐺𝑅 3

= 2 𝐵 𝜌 + 𝐶 𝜌2 − ln (𝑍)
𝑅𝑇 2

𝑆𝑅 𝐵 𝑑𝐵 1 𝐶 𝑑𝐶 2
 Residual entropy = 𝑙𝑛 𝑍 − 𝑇 + 𝜌+ + 𝜌
𝑅 𝑇 𝑑𝑇 2 𝑇 𝑑𝑇

𝐻𝑅 𝐵 𝑑𝐵 𝐶 1 𝑑𝐶 2
 Residual enthalpy =𝑇 − 𝜌+ − 𝜌
𝑅𝑇 𝑇 𝑑𝑇 𝑇 2 𝑑𝑇

52
 Residual properties by cubic equations of state

 van der Waals equation of state

𝑅𝑇 𝑎
𝑃= − 2
𝑉−𝑏 𝑉

𝐺𝑅 𝑅𝑇 𝑏 2𝑎
 Residual Gibbs free energy = 𝑙𝑛 + −
𝑅𝑇 𝑃 𝑉−𝑏 𝑉 − 𝑏 𝑅𝑇𝑉

𝑃 𝑉−𝑏
 Residual entropy 𝑆 𝑅 = 𝑅 𝑙𝑛
𝑅𝑇

𝑏𝑅𝑇 2𝑎
 Residual enthalpy 𝐻𝑅 = −
𝑉−𝑏 𝑉

53
 Residual properties by cubic equations of state

 Peng-Robinson equation of state

𝑅𝑇 𝑎
𝑃= −
𝑉 − 𝑏 𝑉 𝑉 + 𝑏 + 𝑏(𝑉 − 𝑏)

𝐺𝑅 𝑃𝑏 𝑎 𝑉+ 1+ 2 𝑏
 Residual Gibbs free energy = Z − 1 − ln 𝑍 − − 𝑙𝑛
𝑅𝑇 𝑅𝑇 2 2𝑏𝑅𝑇 𝑉+ 1− 2 𝑏

𝑑𝑎
𝑑𝑇 𝑍+ 1+ 2 𝐵
 Residual entropy 𝑆 𝑅 = 𝑅 𝑙𝑛 𝑍 − 𝐵 + ln
2𝑏 2 𝑍+ 1− 2 𝐵

𝑑𝑎
𝑇 −𝑎 𝑍+ 1+ 2 𝐵
𝑑𝑇
𝐻𝑅 = 𝑍 − 1 𝑅𝑇 + ln
 Residual enthalpy 2 2𝑏 𝑍+ 1− 2 𝐵

𝑃𝑏
𝐵=
𝑅𝑇 54
 Example 6.4 page 219

 Find values of residual entropy for n-butane gas at 500 K and 50 bar using
van der Waals equation of state

 For van der Waals equation of state the residual entropy and enthalpy is
given by (from slide 53):

𝑏 𝑉−𝑏
𝑆 𝑅 = 𝑅 𝑙𝑛
𝑅𝑇

 First find a & b for butane

27 𝑅 2 𝑇𝑐2 27 (83.14)2 425.1 2

𝑐𝑚3 𝑏𝑎𝑟 2
𝑎= = = 1.3882e + 007
64 𝑃𝑐 64 37.96 𝑚𝑜𝑙2

1 𝑅 𝑇𝑐 1 ∗ 83.14 ∗ 425.1
𝑏= = = 116.3818 𝑐𝑚3 /𝑚𝑜𝑙
8 𝑃𝑐 8 37.96
 Then, find the molar volume (V) for the gas using the van der Waals equation
of state where P=50 bar and T= 500K.
𝑉 = 549.3891 𝑐𝑚3 /𝑚𝑜𝑙

𝑅
𝑃 𝑉−𝑏 50 549.3891 − 116.3818 𝑐𝑚3 𝑏𝑎𝑟 𝑱
𝑆 = 𝑅 𝑙𝑛 = 83.14 𝑙𝑛 = −54.2369 = −𝟓. 𝟒𝟐𝟑𝟔𝟗
𝑅𝑇 83.14 ∗ 500 𝑚𝑜𝑙 𝐾 𝒎𝒐𝒍 𝑲
55
 Generalized correlations

 In chapter 3, the generalized correlations were used to estimate the compressibility

factor (Z) for gases.

 Two approaches were used:

 Lee-Kesler method

 The generalized second virial coefficient correlation

56
 Lee-Kesler correlations

 To estimate the compressibility factor using Lee-Kesler correlations, the compressibility

factor is given by:

𝑍 = 𝑍 0 𝑇𝑟 , 𝑃𝑟 + 𝜔𝑍1 𝑇𝑟 , 𝑃𝑟

 The same methodology could be used to estimate 𝐻 𝑅 and 𝑆 𝑅

𝐻𝑅 𝐻𝑅 0 𝐻𝑅 1 𝑆𝑅 𝑆𝑅 0
𝑆𝑅 1
= +𝜔 = +𝜔
𝑅𝑇𝑐 𝑅𝑇𝑐 𝑅𝑇𝑐 𝑅 𝑅 𝑅

 The values of 𝐻𝑅 0
and 𝐻 𝑅 1
are tabulated in Appendix E (Table E5-E8)

 The values of 𝑆𝑅 0
and 𝑆 𝑅 1
are tabulated in Appendix E (Table E9-E12)

Important: to estimate the residual properties from Lee-Kesler method, Z is

not required. However, the same procedure is used to estimate the residual
0 1 0 1
𝐻𝑅 𝐻𝑅 𝑆𝑅 𝐻𝑅
properties because , , and are tabulated in Appendix E.
𝑅𝑇𝑐 𝑅𝑇𝑐 𝑅 𝑅
57
 The generalized second virial coefficient correlation

 The residuals enthalpy and entropy are estimated by the following correlations:

𝐻𝑅 0
𝑑𝐵0 1
𝑑𝐵1
= 𝑃𝑟 𝐵 − 𝑇𝑟 + 𝜔 𝐵 − 𝑇𝑟
𝑅 𝑇𝑐 𝑑𝑇𝑟 𝑑𝑇𝑟

𝑆𝑅 𝑑𝐵0 𝑑𝐵1
= −𝑃𝑟 +𝜔
𝑅 𝑑𝑇𝑟 𝑑𝑇𝑟

where

0.422 0.172
𝐵0 = 0.083 − 𝐵1 = 0.139 −
𝑇𝑟1.6 𝑇𝑟4.2

𝑑𝐵0 0.675 𝑑𝐵1 0.722

= 2.6 = 5.2
𝑑𝑇𝑟 𝑇𝑟 𝑑𝑇𝑟 𝑇𝑟

 It should be noted that these correlations are not applicable at high pressure because
the virial equation of state with the second virial coefficient is not accurate at high
pressure.
58
Why do we need residual properties?

O.K. I know how to

estimate residual
properties but I am
still confused !! I
don’t know what
the point is of the
residual properties.

 Don’t get confused. Later, you are going to

learn about something called fugacity and
activity; you will see how the residual
relations are indeed useful.

 In the next slides, we are going to see some

more advantages of the residual properties.

59
 Estimating of real gas properties

 At the beginning of this chapter, the change of entropy is given in terms of

measurable properties as follows:

𝐶𝑃 𝜕𝑉
∆𝑆 𝑇, 𝑃 = 𝑑𝑇 − 𝑑𝑃
𝑇 𝜕𝑇 𝑃

 If the above equation is applied for ideal gas (PV=RT), the change of entropy is
given by:

𝑖𝑔
𝐶𝑃 𝑖𝑔 𝑃2
∆𝑆 𝑇, 𝑃 = 𝑑𝑇 − 𝑅𝑙𝑛
𝑇 𝑃1

 What if the gas under study is real gas (not ideal gas)?
 In this case, it is clear that the second term on the right hand side needs
a thermodynamic model (such as cubic equations of state) which involves
mathematical manipulations which makes it sometime not a trivial task.

 An alternative approach to estimate the change of entropy for the real gas is to
take advantage of the residual properties as illustrated in the next slide.
60
 What might residual properties do for us?

 Calculate ∆𝐻 ∆𝑆 ∆𝐴 ∆𝐺 etc.
?
𝜕𝑃
∆𝑈 = 𝐶𝑉 𝑑𝑇 + 𝑇 − 𝑃 𝑑V
𝜕𝑇 𝑉

𝐶𝑉 𝜕𝑃
Remember these ∆𝑆 = 𝑑𝑇 + 𝑑𝑉
𝑇 𝜕𝑇 Check slides 21, 23 & 24
equations? ! 𝑉

𝜕𝑉
∆𝐻 = 𝐶𝑝 𝑑𝑇 + V−𝑇 𝑑𝑃
𝜕𝑇 𝑃

…… etc.

 To find the change of thermodynamic properties from the above

equations, you need PVT relations.

 The above equations need good skills in integration and differentiation.

Let’s find an alternative

Method !
 If you prefer another method
that doesn’t need to integrate Always remember, residual
or differentiate, residual properties could be used to
properties could be helpful determine the change of
as you will see in the next slides thermodynamic properties

61
 Estimating of real gas properties

 Suppose a real gas undergoes a change  Our target is to find the change of entropy
from state 1 (𝑇1 , 𝑃1 ) to state 2 (𝑇2 , 𝑃2 ). which is ∆𝑆 = 𝑆2 − 𝑆1

𝑷 (𝑇2 , 𝑃2 ) 𝑷 (𝑇2 , 𝑃2 )

state 2 S2
(𝑇1 , 𝑃1 ) (𝑇1 , 𝑃1 ) ∆𝑆
state 1 S1

𝑻 𝑻

62
 Estimating of real gas properties

 Let’s focus on 𝑺𝟏  Let’s focus on 𝑺𝟐

𝑆1 = 𝑆 𝑅 1 + 𝑆 𝑖𝑔1 𝑆2 = 𝑆 𝑅 2 + 𝑆 𝑖𝑔 2
𝑷 𝑷 (𝑻𝟐 , 𝑷𝟐 )
𝑺𝟐
𝑺𝟏
(𝑻𝟏 , 𝑷𝟏 )
𝑺𝑹 𝟐
𝑆 𝑅1

𝑃𝑖𝑔 ………. 𝑆 𝑖𝑔1 𝑃𝑖𝑔 …………….……………………. 𝑆 𝑖𝑔 2

𝑻 𝑻

 Remember: residual properties give the deviation from the ideal gas

63
 Estimating of real gas properties

 The entropy change of the ideal gas is given by: ∆𝑆 𝑖𝑔 = 𝑺𝒊𝒈 𝟐 - 𝑺𝒊𝒈 𝟏

𝑷 (𝑇2 , 𝑃2 )

(𝑇1 , 𝑃1 )
𝑺𝑹 𝟐
𝑆 𝑅1
𝑺𝒊𝒈 𝟏 ………………………….…. 𝑺𝒊𝒈
𝟐
∆𝑆 𝑖𝑔
𝑻

64
 Estimating of real gas properties

 Remember entropy is a state function, it doesn’t depend on the path.

𝑷 (𝑇2 , 𝑃2 )
∆𝑺
(𝑇1 , 𝑃1 )
𝑺𝑹 𝟐
𝑺𝑹 𝟏
∆𝑺𝒊𝒈
𝑻
 To find the change of entropy from state 1 to state 2, the red path could
be taken since entropy change doesn’t depend on the path:

∆𝑺= - 𝑺𝑹 𝟏 + ∆𝑺𝒊𝒈 + 𝑺𝑹 𝟐

65
 Estimating of real gas properties

 Finally, ∆𝑆 = 𝑆 𝑅 2 − 𝑆 𝑅 1 + ∆𝑆 𝑖𝑔

 The entropy change of the ideal gas, ∆𝑆 𝑖𝑔 , is given by:

𝑖𝑔
𝐶𝑃 𝑖𝑔 𝑃2
∆𝑆 𝑇, 𝑃 = 𝑑𝑇 − 𝑅𝑙𝑛
𝑇 𝑃1

 Therefore,

𝑅
𝐶𝑃 𝑖𝑔 𝑃2 𝑅 𝑅
𝐶𝑃 𝑖𝑔 𝑃2
∆𝑆 = ∆𝑆 + 𝑑𝑇 − 𝑅𝑙𝑛 ∆𝑆 = 𝑆 2
−𝑆 1
+ 𝑑𝑇 − 𝑅𝑙𝑛
𝑇 𝑃1 𝑇 𝑃1

 It is clear from the final equation, the change of entropy could be estimated with
the aid of residual properties. Therefore, we could get advantages from the previous
explained methods for estimating of the residual properties such as Lee-Kesler method.

66
 Estimating of real gas properties

 The enthalpy change could be given in a similar approach

𝑇2
∆𝐻 = 𝐻 𝑅
2
−𝐻 𝑅
1
+ 𝐶𝑝 𝑖𝑔 𝑑𝑇
𝑇1

 To sum up, the change of entropy and enthalpy of real gas is given in terms
of residual properties by:

𝑅 𝑅
𝐶𝑃 𝑖𝑔 𝑃2
∆𝑆 = 𝑆 2
−𝑆 1
+ 𝑑𝑇 − 𝑅𝑙𝑛
𝑇 𝑃1

𝑇2
∆𝐻 = 𝐻 𝑅
2
−𝐻 𝑅
1
+ 𝐶𝑝 𝑖𝑔 𝑑𝑇
𝑇1

 At constant heat capacity, the equations are given by:

𝑇2 𝑃2
∆𝑆 = 𝑆 𝑅 2 − 𝑆 𝑅 1 + 𝐶𝑃 𝑖𝑔 𝑙𝑛 − 𝑅𝑙𝑛
𝑇1 𝑃1

∆𝐻 = 𝐶𝑃 𝑖𝑔 𝑇2 − 𝑇1 + 𝐻 𝑅 2 − 𝐻 𝑅 1
67
 Problem 6.50 page 246

 Propane gas at 1 bar and 35 oC is compressed to a final state of 135 bar and 195 oC.
Initial state Final state

Propane gas
1 bar 135 bar
35 oC 195 oC

a. Estimate the molar volume of the propane in the final state

b. Estimate the enthalpy and entropy changes for the process.
In its initial state, propane may be assumed an ideal gas.

Solution:
a. Find the molar volume at 135 bar and 195 oC
The molar volume could be obtained by cubic equation of state or Lee-Kesler correlation.

 Lee-Kesler correlation: 𝜔 = 0.152 𝑇𝑐 = 369.8 𝐾 𝑃𝑐 = 42.48 𝑏𝑎𝑟

𝑇 195 + 273.15 𝑃 135

𝑇𝑟 = = = 1.266 𝑃𝑟 = = = 3.178
𝑇𝑐 369.8 𝑃𝑐 42.48

𝑍 = 𝑍 0 + 𝜔𝑍1 Interpolation in tables E3 and E4 𝒁 = 𝟎. 𝟔𝟑𝟗

𝑍𝑅𝑇 𝒄𝒎𝟑
𝑉= 𝑽 = 𝟏𝟖𝟒. 𝟐 Answer
𝑃 𝒎𝒐𝒍 68
 Problem 6.50 page 246

b. Estimate the enthalpy and entropy changes for the process.

𝑷 (𝑇2 , 𝑃2 )
135 bar
195 oC Question: why this figure is different from
the one in slide no. 65?
∆𝑯 Answer: the initial state in this problem is
∆𝑺 𝑺𝑹 𝟐
already an ideal gas where the one in
1 bar slide no. 65 both states behave as real
35 oC
𝑯𝑹 𝟐
gas.
∆𝑺𝒊𝒈
∆𝑯𝒊𝒈 𝑻

Enthalpy change Entropy change

∆𝐻 = ∆𝐻 𝑖𝑔 + 𝐻 𝑅 2 ∆𝑆 = ∆𝑆 𝑖𝑔 + 𝑆 𝑅 2
𝑇2
∆𝐻 = 𝐻 𝑅
2
+ 𝐶𝑝 𝑖𝑔 𝑑𝑇 𝑅
𝐶𝑃 𝑖𝑔 𝑃2
𝑇1 ∆𝑆 = 𝑆 2
+ 𝑑𝑇 − 𝑅𝑙𝑛
𝑇 𝑃1

69
 Problem 6.50 page 246

Enthalpy change

∆𝐻 = ∆𝐻 𝑖𝑔 + 𝐻 𝑅 2
𝑇2
∆𝐻 = 𝐻 𝑅
2
+ 𝐶𝑝 𝑖𝑔 𝑑𝑇
𝑇1

𝑇2
𝐻𝑅 2 𝐶𝑝 𝑖𝑔 𝑑𝑇
𝑇1
𝑅 𝑅 0 𝑅 1
𝐻 𝐻 𝐻
= +𝜔
𝑅𝑇𝑐 𝑅𝑇𝑐 𝑅𝑇𝑐 A=1.213 B=28.785E-3 C=-8.824E-6
𝑇𝑟 = 1.266 𝐻𝑅 0
= −2.4966
𝑃𝑟 = 3.178 𝑅𝑇𝑐 𝑇2
𝐽
From 𝐶𝑝 𝑖𝑔 𝑑𝑇 = 1.4683𝐸4
Appendix E 𝑇1 𝑚𝑜𝑙
𝑇𝑟 = 1.266 𝐻𝑅 1
= −0.58797
𝑃𝑟 = 3.178 𝑅𝑇𝑐
𝑇2
∆𝐻 = 𝐻 𝑅
2
+ 𝐶𝑝 𝑖𝑔 𝑑𝑇 = −7.9507E3 + 1.4683E4
𝐻𝑅 𝐽 𝑇1
𝑅𝑇𝑐
= −2.5860 𝐻 𝑅 2 = −7.9507𝐸3
𝑚𝑜𝑙 𝑱
∆𝑯 = 𝟔𝟕𝟑𝟐. 𝟑
𝒎𝒐𝒍 70
 Problem 6.50 page 246

Entropy change

∆𝑆 = ∆𝑆 𝑖𝑔 + 𝑆 𝑅 2

𝑅
𝐶𝑃 𝑖𝑔 𝑃2 𝑃2
∆𝑆 = 𝑆 2
+ 𝑑𝑇 − 𝑅𝑙𝑛 𝑅𝑙𝑛
𝑇 𝑃1 𝑃1

𝑃2 135
𝑅𝑙𝑛 = 8.314 ∗ ln( )
𝑃1 1

𝑇2 𝐶 𝑖𝑔 𝑃2 J
𝑅 𝑝 𝑅𝑙𝑛 = 40.783
𝑆 2 𝑑𝑇 𝑃1 mol K
𝑇1 𝑇
𝑆𝑅 𝑆𝑅 0
𝑆𝑅 1
= +𝜔 A=1.213 B=28.785E-3
𝑅 𝑅 𝑅
C=-8.824E-6
𝑇𝑟 = 1.266 𝑆𝑅 0
= −1.4625 𝑇2 𝐶 𝑖𝑔
𝑃𝑟 = 3.178 𝑅 𝑝 𝐽
From 𝑑𝑇 = 37.952
𝑇1 𝑇 𝑚𝑜𝑙 𝐾
𝑆 𝑅 1 Appendix E
𝑇𝑟 = 1.266
= −0.71700
𝑅
𝑃𝑟 = 3.178 𝐶𝑃 𝑖𝑔 𝑃2
∆𝑆 = 𝑆 𝑅 2 + 𝑑𝑇 − 𝑅𝑙𝑛 = −13.065 + 37.952 − 40.783
𝑇 𝑃1
𝑆𝑅 𝐽
𝑅
= −1.5715 𝑆 𝑅 2 = −13.065 𝑱
𝑚𝑜𝑙 𝐾
∆𝑺 = −𝟏𝟓. 𝟖𝟗𝟔
𝒎𝒐𝒍 𝑲 71