Chemical Engineering

Thermodynamics I

CHE 325
(3 Units)

Dr. F. B. ELEHINAFE
MODULE FOUR

ENTROPY
 Introduction
•1st Law of Thermodynamics -- analyzed using U

•2nd Law of Thermodynamics -- defined new property

S to use in analysis, to allow expansion of the 2nd law
beyond cycles.

Entropy (S) is a state property that serves as a measure

of reversibility/irreversibility and of the disorder of a
system. It was developed to account for losses in the
potential to do useful work, and so accounts for waste
in a process.
if a change is to spontaneously (as mentioned in the
examples of spontaneous processes) occur.
Note the inequality, since a reversible system is the
ideal, it serves as a bound; as a result, application of
the 2nd Law often gives equations with inequalities.
 Entropy Change Calculations
Scenario A: isothermal Removal or Addition of Heat
This occurs in the case of a bath large enough
that the addition or removal of an amount of heat Q
does not effect its temperature T, such as a bath
consisting of a system undergoing an isothermal
phase change.
1

It takes, for example, 2256.9 kJ to vaporize one kg of

saturated water at 373.15 K. Hence, according to
Eq.1, the entropy of vaporization is 6.0485 kJ/kg K.
Scenario B: Heating or Cooling of a Body
from T1 to T2
I) Constant volume (isochoric) process:

II) Constant pressure (isobaric) process:

Scenario C: Entropy Changes of an Ideal Gas
Consider one mole of an ideal gas that goes
from state 1 (T1, V1, P 1) to state 2 (T 2, V2, P2). Since
our hypothetical path is reversible, dW = PdV.

To obtain the final answer in terms of P1 and P2 we

introduce:

leading, after some algebra, to:

 **

Note: while the enthalpy and internal energy

changes of an ideal gas are functions of temperature
only, the entropy change depends on both, temperature
and pressure (or volume), changes.
Scenario D: Adiabatic process :
ΔS = 0 (qrev = 0)
Scenario E: Entropy of Mixing
Two pure ideal gases 1 and 2, both at the same
temperature T and pressure P, are mixed isothermally
with final composition y1 and y2• What is the entropy of
mixing per mole of mixture formed? We start by noticing
that as a result of the mixing process the pressure of
component 1 goes from P to its partial pressure p1,
i.e. its contribution to the mixture pressure; and the
same applies to component 2. Thus, according to
Eq.** above:

***
 The same equation applies in the isothermal
formation of an ideal solution. Returning to Eq. ***,
we notice that, since all y's are less than one, the
mixing process leads to an increase in entropy. This, of
course, should be expected. Mixing is a natural
(spontaneous) process, and as such it leads to an
entropy increase.
Important points to Remember
Example 1
Example 2
Note. We have assumed here that the flowrate of
steam is high enough that no cooling of the
condensate occurs. Will the entropy change of the
heating medium be the same, if such cooling did
occur?
 Example 3
One kg of water at 80°C is available. Calculate the
work produced using the entropy changes involved. The
atmosphere at 20°C will be the heat sink. Assume a
constant heat capacity for water of C = 1 kcal/kg K.
Solution
Amount of heat removed from the water:
Qw = (1)(C)(T2- T1) = -60 kcal
Entropy change of water:
dSw = (1)(C)ln(T2/T1)= -0.1862kcal/K
Since the cycle is reversible: .dSa = -.dSw and,
consequently, the amount of heat transferred to the
atmosphere is:
Qa = T2..1Sa = (293.15)(0.1862) = 54.59 kcal
 Let Q1 and Q2 the amounts of heat absorbed and
rejected by the cycle. Then:
W = Q1 +Q2 = 60 + ( -54.59) = 5.41 kcal

Example 4
A test of the Vortex Tube, as shown in the Fig. below,
gave the following data :
stream A: 5 atm, 20°C
stream B: 1 atm, -21°C
stream C: 1 atm, 26°C
moles C/moles B: nC/nB = 5.4
Determine the total entropy change. Assume, for
simplicity, ideal gas behavior with C p • temperature
independent and equal to 28 J/mol K.

Solution
Example 5
Example 6
Solution
Example 7
Solution
Example 8
Solution
Exercise