Module 4 2nd Law of Thermodynamics

MODULE 4
2nd Law of Thermodynamics

2nd Law of Thermodynamics: Entropy
■ Entropy is the measure of disorderliness of a system
■ It is a measure of the energy dispersed in a process
■ It lets us assess whether one state is accessible from
another by a spontaneous change
■ The entropy of an isolated system increases in the
course of a spontaneous change: ∆Stot>0
2nd Law of Thermodynamics: Entropy
■ Differential form
𝑑𝑄
𝑑𝑆 =
𝑇
■ Entropy associated with sensible heat
𝑇2
Δ𝑆 = 𝑚𝐶𝑝 𝑙𝑛
𝑇1
■ Entropy change during phase change
∆𝐻𝑡𝑟𝑎𝑛𝑠
∆𝑆 =
𝑇
Entropy Formula for Ideal Gases
Entropy Formula for Ideal Gases (Bifunctional)
𝑇2 𝑉2
∆𝑆 = 𝑓 𝑇, 𝑉 = 𝑛𝐶𝑣 𝑙𝑛 + 𝑛𝑅𝑙𝑛
𝑇1 𝑉1
𝑇2 𝑃2
∆𝑆 = 𝑓 𝑇, 𝑃 = 𝑛𝐶𝑝 𝑙𝑛 − 𝑛𝑅𝑙𝑛
𝑇1 𝑃1
𝑉2 𝑃2
∆𝑆 = 𝑓 𝑃, 𝑉 = 𝑛𝐶𝑝 𝑙𝑛 + 𝑛𝐶𝑣 𝑙𝑛
𝑉1 𝑃1
Sample Problem 1
A 40kg steel casting (CP=0.5kJ/kg-K) at a
temperature of 450˚C is quenched in 150kg of
oil (CP=2.5kJ/kg-K) at 25˚C. If there are no
heat losses,
a. What is the entropy change of the casting?
b. What is the change in entropy of the oil?
c. What is the entropy change of both
considered together?
Sample Problem 2
Consider A (l, 75˚C) → A (g, 155˚C) which is
carried out at constant pressure. The total ΔS
for this process was found to be 75J/mol-K. For
A (l) and A (g), the CP are 75J/mol-K and
29J/mol-K, respectively, and are independent
of temperature. Calculate ΔHVAP for A (l) at
125˚C (boiling point).
Sample Problem 3
For a certain ideal monoatomic gas, calculate
the change in entropy experienced by 3mol of
the gas on being heated from 300 to 600K at
(a)constant pressure and
(b)constant volume
Sample Problem 4
Calculate the entropy change when argon at
25°C and 1bar in a container of volume
0.5dm3 is allowed to expand to 1dm3 and is
simultaneously heated to 100°C.
Sample Problem 5
Hydrogen, initially at 15psia and 80˚F, is
compressed at the rate of 20cfm in a hot
environment to a pressure of 75.3psig. The
details of the process are unknown but it is
estimated that heat enters at the rate of
20BTU/min. For a change in entropy of
0.0268BTU/min-R, determine the final
temperature.
Sample Problem 6
For a certain reaction, ΔS˚298.2K=-59.2eu, and:
5
−3
3.985 × 10
𝐶𝑝 = −7.58 + 17.42 × 10 𝑇 −
𝑇2
From these data, find ΔS of the reaction at
400K.
Sample Problem 7
Methane gas at 550K and 5bar undergoes an
adiabatic reversible expansion to 1bar.
Assuming methane to be an ideal gas at these
conditions, find its final temperature.
Cp/R=1.702+9.081x10-3T-2.164x10-6T2.
2nd Law of Thermodynamics: Heat Engines
■ A heat engine is a device or machine that produces
work from heat in a cyclic process. An example is a
steam power plant in which the working fluid
periodically returns to its original state.
■ The Kelvin-Planck statement of the 2nd law of
thermodynamics gives the idea that there is no such
heat engines that can convert 100% of absorbed heat
to work. The Clausius statement on the other hand
states that there is no such heat engine that transfers
100% of heat from hot to cold reservoir.
2nd Law of Thermodynamics: Heat Engines
■ Carnot Efficiency
𝑇𝑐
𝜂𝑐 = 1 −
𝑇ℎ
■ Energy Balance in a Heat Engine

𝑄ℎ = 𝑊 + 𝑄𝑐
■ Efficiency of a Heat Engine

𝑊
𝜂=
𝑄ℎ
Sample Problem 8
A central power plant, rated at 800,000kW,
generates steam at 585K and discards heat to
a river at 295K. If the thermal efficiency of the
plant is 70% of the maximum possible value,
how much heat is discarded to the river at the
rated power?
Sample Problem 9
A nuclear power plant generates 750MW; the
reactor temperature is 315˚C and a river with
water temperature of 20˚C is available.
a. What is ideal the rate at which heat must be
discarded to the river?
b. If the actual efficiency of the plant is 60% of
the maximum, what is the temperature rise
in ˚C of the river if it has a flow of
165m3/s?
Sample Problem 10
A heat engine operating at a Carnot cycle
between 1540˚F and 40˚F rejects 250BTU/lb
of working fluid to the sink.
a. What is the Carnot efficiency?
b. What is the work produced by the heat
engine?
c. What is the maximum entropy change for
any process in the cycle?

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MODULE 4

2nd Law of Thermodynamics

■ Energy Balance in a Heat Engine

■ Efficiency of a Heat Engine

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