MME215 Thermodynamics of Materials

Lecture 11 & 12
A. K. M. Bazlur Rashid Thermodynamic Variables and Relations
Professor, Dept. of Materials and Metallurgical Eng.
Bangladesh Univ. of Eng. and Tech., Dhaka-1000 2 – General procedure to develop thermodynamic relations

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Lecture Outcome (LO)

At the end of this lecture, students should be able to

• develop a general strategy to obtain a thermodynamic relation between

the sought variable and the given variables,

• derive a general procedure of developing a thermodynamic relation

using the genera strategy,

• solve thermodynamic problems by deriving new thermodynamic relation, and

• apply thermodynamic relations to ideal gases, solids and liquids.

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How to Tackle a Thermodynamic Problem?

 Identify the properties of the system about which the information is given.
 Independent variables

 Identify the property of the system about which one is seeking information.
 Dependent variable

 Find or derive a relationship between the sought and the given variables.
 The generic form of this relation Z = Z (X, Y)
 Contains quantities such as a, b, CP, etc.

 Obtain values for these quantities.

 Tabulated data (books, databases, graphs, experiments)

 Substitute values into relationship and carry out mathematical operations.

 Get a value for the dependent variable

Step 3 is critical
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General Strategy for

Deriving Thermodynamic Relations

❑ To develop a general procedure for deriving a relation for the function Z = Z (X, Y) :
• Choose T and P as the independent variables
• Express all state variables as functions of T and P: Z = Z (T, P)
• Convert this function to the required function: Z = Z (X, Y)

4/24
 State Functions Combined Statements

Equation of state variables: T, P, V 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉

Energy functions: U, H, F, G 𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃

𝑑𝐹 = −𝑆𝑑𝑇 − 𝑃𝑑𝑉
Entropy function: S
𝑑𝐺 = −𝑆𝑑𝑇 + 𝑉𝑑𝑃

❑ We need to express V and S as functions of T and P:

V = V (T, P)
S = S (T, P)

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Expressing V as a function of T and P

𝑉 = 𝑉 (𝑇, 𝑃)

𝜕𝑉 𝜕𝑉 1 𝜕𝑉
𝑑𝑉 = 𝑑𝑇 + 𝑑𝑃 𝛼=
𝜕𝑇 𝜕𝑃 𝑉 𝜕𝑇 𝑃
𝑃 𝑇
1 𝜕𝑉
𝛽=−
𝑑𝑉 = 𝑉𝛼 𝑑𝑇 − 𝑉𝛽 𝑑𝑃 𝑉 𝜕𝑃 𝑇

6/24
 Expressing S as a function of T and P

𝛿𝑄𝑟𝑒𝑣 = 𝑇𝑑𝑆
𝑆 = 𝑆 (𝑇, 𝑃)
𝛿𝑄𝑟𝑒𝑣,𝑃 = 𝑇𝑑𝑆𝑃 = 𝐶𝑃 𝑑𝑇𝑃

𝜕𝑆 𝜕𝑆 𝜕𝑆 𝐶𝑃
𝑑𝑆 = 𝑑𝑇 + 𝑑𝑃 =
𝜕𝑇 𝜕𝑃 𝜕𝑇 𝑃
𝑇
𝑃 𝑇

Using Maxwell relation

𝐶𝑃
𝑑𝑆 = 𝑑𝑇 − 𝑉𝛼 𝑑𝑃 𝜕𝑆 𝜕𝑉
𝑇 = − = −𝑉𝛼
𝜕𝑃 𝑇
𝜕𝑇 𝑃

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TABLE 4.2: Thermodynamic state functions expressed in terms T and P

𝑉 = 𝑉 𝑇, 𝑃 : 𝑑𝑉 = 𝑉𝛼 𝑑𝑇 − 𝑉𝛽 𝑑𝑃
𝐶𝑃
𝑆 = 𝑆 𝑇, 𝑃 : 𝑑𝑆 = 𝑑𝑇 − 𝑉𝛼 𝑑𝑃
𝑇
𝑈 = 𝑈 𝑇, 𝑃 : 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉; 𝑑𝑈 = 𝐶𝑃 − 𝑃𝑉𝛼 𝑑𝑇 − 𝑉 𝑃𝛽 − 𝑇𝛼 𝑑𝑃

𝐻 = 𝐻 𝑇, 𝑃 : 𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃; 𝑑𝐻 = 𝐶𝑃 𝑑𝑇 + 𝑉 1 − 𝑇𝛼 𝑑𝑃

𝐹 = 𝐹 𝑇, 𝑃 : 𝑑𝐹 = −𝑆𝑑𝑇 − 𝑃𝑑𝑉; 𝑑𝐹 = − 𝑆 + 𝑃𝑉𝛼 𝑑𝑇 − 𝑃𝑉𝛽 𝑑𝑃

𝐺 = 𝐺 𝑇, 𝑃 : 𝑑𝐺 = −𝑆𝑑𝑇 + 𝑉𝑑𝑃; 𝑑𝐺 = −𝑆 𝑑𝑇 + 𝑉 𝑑𝑃

❑ The coefficients in these differential equations contain the following factors:

• T and P (the independent variables specified in any application)
• a, b and CP (the experimental variables to be available in tables or data bases)
• S and V (can be evaluated as functions of T and P, given the value of a, b and CP) 8/24
General Procedure to Obtain Thermodynamic Relations
1. Identify the variables: 𝑍 = 𝑍 𝑋, 𝑌

2. Write the differential form: 𝑑𝑍 = 𝑀𝑑𝑋 + 𝑁𝑑𝑌

3. Use Table 4.2 to express dX and dY in terms of the variables T and P:

𝑑𝑍 = 𝑀 𝑋𝑇 𝑑𝑇 + 𝑋𝑃 𝑑𝑃 + 𝑁 𝑌𝑇 𝑑𝑇 + 𝑌𝑃 𝑑𝑃

4. Collecting like terms:

𝑑𝑍 = 𝑀𝑋𝑇 + 𝑁𝑌𝑇 𝑑𝑇 + 𝑀𝑋𝑃 + 𝑁𝑌𝑃 𝑑𝑃 8. Check Units:
5. Obtain 𝑍 = 𝑍(𝑇, 𝑃) from Table 4.2: Energy: PV
Entropy: PV/T
𝑑𝑍 = 𝑍𝑇 𝑑𝑇 + 𝑍𝑃 𝑑𝑃 Heat capacity: PV/T
a: 1/T
6. Equating the like terms for the function 𝑍 = 𝑍 𝑇, 𝑃 : b: 1/P
𝑀𝑋𝑇 + 𝑁𝑌𝑇 = 𝑍𝑇 (4.37a)
𝑀𝑋𝑃 + 𝑁𝑌𝑃 = 𝑍𝑃 (4.37b)

7. Solving Eq.(4.37) will result expressions for M and N. 9/24

Example 4.3
Relate the entropy of a system to its temperature and volume.

1. 𝑆 = 𝑆(𝑇, 𝑉)

2. 𝑑𝑆 = 𝑀𝑑𝑇 + 𝑁𝑑𝑉

3. 𝑑𝑆 = 𝑀𝑑𝑇 + 𝑁 𝑉𝛼𝑑𝑇 − 𝑉𝛽𝑑𝑃

4. 𝑑𝑆 = 𝑀 + 𝑁𝑉𝛼 𝑑𝑇 − 𝑁𝑉𝛽𝑑𝑃 Check units:

5. 𝑑𝑆 = 𝐶𝑃 /𝑇 𝑑𝑇 − 𝑉𝛼𝑑𝑃 PV/T = (1/T)(PV/T – TVP/T2)T + (P/T)V

PV/T = PV/T – PV/T + PV/T
6. 𝑀 + 𝑁𝑉𝛼 = 𝐶𝑃 /𝑇; −𝑁𝑉𝛽 = −𝑉𝛼
1 𝑇𝑉𝛼 2
7. 𝑁 = 𝛼/𝛽 ; 𝑀 = 𝐶𝑃 −
𝑇 𝛽

1 𝑇𝑉𝛼 2 𝛼
8. 𝑑𝑆 = 𝐶𝑃 − 𝑑𝑇 + 𝑑𝑉
𝑇 𝛽 𝛽

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 Example
Find the relationship needed to compute the change in Gibbs free energy
when the initial and final states are specified by their pressure and volume.

𝐺 = 𝐺(𝑃, 𝑉) 𝑁𝑉𝛼 = −𝑆
𝑆
𝑁=−
𝑉𝛼
𝑑𝐺 = 𝑀𝑑𝑃 + 𝑁𝑑𝑉
= 𝑀𝑑𝑃 + 𝑁 𝑉𝛼𝑑𝑇 − 𝑉𝛽𝑑𝑃
= 𝑁𝑉𝛼𝑑𝑇 + 𝑀 − 𝑁𝑉𝛽 𝑑𝑃 𝑀 − 𝑁𝑉𝛽 = 𝑉
−𝑆 𝑆𝛽
𝑀=𝑉+ 𝑉𝛽 = 𝑉 −
𝑑𝐺 = −𝑆𝑑𝑇 + 𝑉𝑑𝑃 𝑉𝛼 𝛼

𝑆𝛽 𝑆
𝐺 = 𝐺 𝑃, 𝑉 : 𝑑𝐺 = 𝑉 − 𝑑𝑃 − 𝑑𝑉
𝛼 𝑉𝛼

11/24

Example 4.4
Derive an expression for the increase in temperature for process in which
the volume of a system is changed at constant entropy.

Here, the function is: 𝑇 = 𝑇(𝑆, 𝑉)

Since we use T (and often V) as independent variable and S as dependent variable,

let us change the function to: 𝑆 = 𝑆(𝑇, 𝑉).

1 𝑇𝑉𝛼 2 𝛼
For the function S = S (T, V): 𝑑𝑆 = 𝐶𝑃 − 𝑑𝑇 + 𝑑𝑉
𝑇 𝛽 𝛽

𝑇 𝑇𝛼
Then, for the function T = T (S, V): 𝑑𝑇 = 𝑑𝑆 − 𝑑𝑉
𝑇𝑉𝛼 2 𝑇𝑉𝛼 2
𝐶𝑃 − 𝛽 𝐶𝑃 −
𝛽 𝛽

𝑇𝛼
For adiabatic process, dS = 0. Thus, 𝑑𝑇𝑆 = − 𝑑𝑉𝑆
𝛽𝐶𝑃 − 𝑇𝑉𝛼 2
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Application of Thermodynamic Relations
Ideal Gases

❑ All ideal gases follows the ideal gas law : 𝑃𝑉 = 𝑛𝑅𝑇

Universal gas constant

R = 1.98717 cal/K-mol = 1.986 Btu/R-lb mol
R = 10.73 ft3-psia/ R-lb mol = 1545 ft-lbf/R-lb mol
R = 82.06 cm3-atm/K-mol = 83.14 cm3-bar/K-mol
R = 62356 cm3-torr/K-mol = 8314 cm3-kPa/K-mol
R = 0.082056 litre-atm/K-mol = 0.7302 ft3-atm/R-lb mol
R = 0.082 m3-bar/K-mol
R = 8.31434 J/K-mol = 8.31434 m3-Pa/K-mol

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𝑃𝑉 = 𝑛𝑅𝑇

1 𝜕𝑉 𝑃 𝑛𝑅 1
𝛼= = =
𝑉 𝜕𝑇 𝑃
𝑛𝑅𝑇 𝑃 𝑇

1 𝜕𝑉 𝑃 −𝑛𝑅𝑇 1
𝛽=− =− =
𝑉 𝜕𝑃 𝑇
𝑛𝑅𝑇 𝑃2 𝑃

𝑇𝑉𝛼 2 𝑇𝑉 𝑃 𝑃𝑉
𝐶𝑃 − = 𝐶𝑃 − 2
= 𝐶𝑃 − = 𝐶𝑃 − 𝑛𝑅 = 𝐶𝑉
𝛽 𝑇 𝑇

For mon-atomic gases: CP = 5R/2, CV = 3R/2

For di-atomic gases: CP = 7R/2, CV = 5R/2

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 𝑑𝑈 = 𝐶𝑃 − 𝑃𝑉𝛼 𝑑𝑇 + 𝑉 𝑃𝛽 − 𝑇𝛼 𝑑𝑃

𝑃𝑉
𝑑𝑈 = 𝐶𝑃 − 𝑑𝑇 + 𝑉 𝑃/𝑃 − 𝑇/𝑇 𝑑𝑃 = 𝐶𝑃 − 𝑛𝑅 𝑑𝑇
𝑇

𝑑𝑈 = 𝐶𝑉 𝑑𝑇

𝑑𝐻 = 𝐶𝑃 𝑑𝑇 + 𝑉 1 − 𝑇𝛼 𝑑𝑃

𝑑𝐻 = 𝐶𝑃 𝑑𝑇 + 𝑉 1 − 𝑇/𝑇 𝑑𝑃

𝑑𝐻 = 𝐶𝑃 𝑑𝑇

• Changes in U and H are dependent to temperature only.

• For isothermal processes, changes in U and H are zero.
15/24

Example 4.6
One mole of an ideal monatomic gas initially at temperature 298 K and occupying
volume 10 litres is compressed reversibly and adiabatically to a final volume of 2 litres.
Compute the final temperature of the system.

Here, the function is: 𝑇 = 𝑇(𝑆, 𝑉)

1 𝑇𝑉𝛼 2 𝛼
For the function S = S (T, V): 𝑑𝑆 = 𝐶𝑃 − 𝑑𝑇 + 𝑑𝑉
𝑇 𝛽 𝛽

𝑇 𝑇𝛼
Then, for the function T = T (S, V): 𝑑𝑇 = 𝑑𝑆 − 𝑑𝑉
𝑇𝑉𝛼 2 𝑇𝑉𝛼 2
𝐶𝑃 − 𝛽 𝐶𝑃 −
𝛽 𝛽

𝑇𝛼
For adiabatic process, dS = 0. Thus, 𝑑𝑇𝑆 = − 𝑑𝑉𝑆
𝑇𝑉𝛼 2
𝛽 𝐶𝑃 −
𝛽

16/24
 𝑇𝛼
𝑑𝑇𝑆 = − 𝑑𝑉𝑆
𝑇𝑉𝛼 2
𝛽 𝐶𝑃 −
𝛽

For ideal gas, a = 1/T, b = 1/P , and Integrating :

𝑇𝑉𝛼 2
𝐶𝑃 − = 𝐶𝑉 𝑛𝑅/𝐶𝑉
𝛽 𝑇2 𝑛𝑅 𝑉2 𝑉1
ln =− ln = ln
𝑇1 𝐶𝑉 𝑉1 𝑉2
𝑇 1/𝑇 𝑃
Then 𝑑𝑇 = − 𝑑𝑉 = − 𝑑𝑉 𝑛𝑅/𝐶𝑉
1/𝑃 𝐶𝑉 𝐶𝑉 𝑉1 Given data
𝑇2 = 𝑇1
𝑉2 n = 1 mol
V1 = 10 litre T1 = 298 K
Using ideal gas law, P = nRT/V : V2 = 2 litre CV = 3R/2

𝑛𝑅𝑇/𝑉 𝑑𝑇 𝑛𝑅 𝑑𝑉 2/3
𝑑𝑇 = − 𝑑𝑉 ; =− 10 𝑙
𝐶𝑉 𝑇 𝐶𝑉 𝑉 𝑇2 = 298 𝐾 = 871.36 𝐾
2𝑙

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Solids and Liquids

❑ a, b and CP are functions of T, P and X.

❑ For a given material, they are not strong functions of the state of the system.

❑ When only an estimate of the thermodynamic functions is sought,

a, b and CP can be considered to be as constants.

❑ For precise calculations, the dependence upon P and T must be obtained

for these experimental variables a, b and CP.

18/24
Example 4.6

One mole of nickel initially at 300 K and 1 atm pressure is taken through
two separate processes:
(1) an isobaric change in temperature to 1000 K, and
(2) an isothermal compression to 1000 atm.
Compare the change in enthalpy of nickel for these two processes.

Given data:
V (300 K, 1 atm) = 6.57 cc/mol
a = 40x10-6 K-1
b = 1.5x10-6 atm-1
CP = 16.99 + 2.95x10-2T J/mol-K.

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Process 1 (Isobaric Process)

Here the function is : 𝐻 = 𝐻 𝑇, 𝑃 : 𝑑𝐻 = 𝐶𝑃 𝑑𝑇 + 𝑉 1 − 𝑇𝛼 𝑑𝑃

For isobaric process : 𝑑𝐻𝑃 = 𝐶𝑃 𝑑𝑇𝑃

𝑇2 Given data
Integrating : ∆𝐻 = න 𝐶𝑃 𝑑𝑇
𝑇1 P1 = 1 atm T1 = 300 K T2 = 1000 K
CP = 16.99 + 2.95x10-2 T J/mol-K
1000
∆𝐻 = න 16.99 + 2.95x10−2 𝑇 𝑑𝑇
300

∆𝐻 = 11893.0 + 13422.5 J/mol = 25315.5 J/mol

The second term on the RHS of the equation arises from the temperature dependent
contribution to the heat capacity.
If temperature dependency is ignored, CP = 16.99, and then H = 11893.0 J/mol.
20/24
Process 2 (Isothermal Process)

Here the function is : 𝐻 = 𝐻 𝑇, 𝑃 : 𝑑𝐻 = 𝐶𝑃 𝑑𝑇 + 𝑉 1 − 𝑇𝛼 𝑑𝑃

For isotheral process : 𝑑𝐻𝑇 = 𝑉 1 − 𝑇𝛼 𝑑𝑃𝑇

Here V and a depend upon pressure.

For an estimated calculation,

• V and a both can be treated as pressure independent.
Given data
𝑃2 T1 = 300 K V1 = 6.57 cc/mol
∆𝐻 = 𝑉 1 − 𝑇𝛼 න 𝑑𝑃 = 𝑉 1 − 𝑇𝛼 𝑃2 − 𝑃1 P1 = 1 atm P2 = 1000 atm
𝑃1 a = 40x10-6 K-1
𝑐𝑐 1
∆𝐻 = 6.57 1 − 300 𝐾 40x10−6 1000 𝑎𝑡𝑚 − 1 𝑎𝑡𝑚
𝑚𝑜𝑙 𝐾
𝑐𝑐−𝑎𝑡𝑚 𝑐𝑐−𝑎𝑡𝑚 8.314 𝐽
∆𝐻 = 6484.67 = 6484.67 = 657.0 J/mol
𝑚𝑜𝑙 𝑚𝑜𝑙 82.06 𝑐𝑐−𝑎𝑡𝑚 21/24

𝑑𝐻𝑇 = 𝑉 1 − 𝑇𝛼 𝑑𝑃𝑇

For an exact calculation,

• The values of a are within the range of 10–6 ; thus a can be considered as constant.
• But, pressure dependency of V cannot be ignored.

𝑉 = 𝑉 𝑇, 𝑃 : 𝑑𝑉 = 𝑉𝛼𝑑𝑇 − 𝑉𝛽𝑑𝑃
𝑑𝑉𝑇 = −𝑉𝛽 𝑑𝑃𝑇 (For isothermal process)

𝑑𝑉
= − 𝛽 𝑑𝑃
𝑉
𝑉
ln = −𝛽 𝑃 − 𝑃1
𝑉1

𝑉 = 𝑉1 𝑒 −𝛽 𝑃−𝑃1 = 𝑉1 1 − 𝛽 𝑃 − 𝑃1

22/24
 𝑑𝐻𝑇 = 𝑉 1 − 𝑇𝛼 𝑑𝑃𝑇

𝑑𝐻𝑇 = 𝑉1 1 − 𝛽 𝑃 − 𝑃1 1 − 𝑇𝛼 𝑑𝑃𝑇

𝑃2
∆𝐻 = 𝑉1 1 − 𝑇𝛼 න 1 − 𝛽 𝑃 − 𝑃1 𝑑𝑃𝑇
𝑃1

𝛽 𝑃 − 𝑃1 2 𝑃2
Given data
∆𝐻 = 𝑉1 1 − 𝑇𝛼 𝑃−
2 𝑃1 T1 = 300 K V1 = 6.57 cc/mol
P1 = 1 atm P2 = 1000 atm
a = 40x10-6 K-1 b = 1.5x10-6 atm-1
∆𝐻 = 657.0 − 0.07 J/mol = 656.93 J/mol

❑ Only 0.07 J/mol amount of enthalpy is subtracted

because of addition of the pressure variation of volume into the equation.

❑ For solids and liquids, energy changes associated with thermal influences
tend to be much larger than those arises from mechanical influences.
23/24

Next Class

Lecture 13
Thermodynamic Variables and Relations
3 – Problem solving tutorial