CTDCHA2: Chemical Thermodynamics 2A

LEARNING UNIT 1C

The Second Law of

Thermodynamics

1
Introduction
• First Law places no restriction on direction of a process.
• But satisfying the First Law does not ensure that a process can
actually occur.
• E.g. hot coffee getting ‘even
hotter’ in a cooler room as a
result of heat transfer from room
air to hot coffee. This process
cannot occur.

• Yet, if a cup of cool coffee in the

same room were to get hotter by
itself, doing so would not violate
First Law as long as amount of
energy lost by air is equal to
amount of energy gained by
coffee.

Click video icon for the 1st law.

2
Second Law of Thermodynamics
• Accordingly, the Second Heat flows in the direction of decreasing
Law of Thermodynamics temperature

assesses in which direction a

process will occur. It is based
on experimental evidence
like every other physical law.

• Second Law of Thermodynamics is not limited to identifying direction of

processes only as it says that energy has ‘quality’ as well as quantity.
• First Law is concerned with quantity of energy and transformations of
energy from one form to another with no regard to its quality.
• Preserving the quality of energy is a major concern to engineers and
the second law provides necessary means to determine quality as well
as degree of degradation of energy during a process i.e. during
conversion, energy cannot be converted 100%. Processes must
satisfy both the First and Second Laws of Thermodynamics to
proceed.

3
Second Law of Thermodynamics (cont.)
• Second Law of Thermodynamics is also used to determine theoretical
limits for performance of commonly used engineering systems like heat
engines and refrigerators and predicting degree of completion of
chemical reactions.
• When left alone systems/
processes tend to undergo
spontaneous changes until a
condition of equilibrium is
achieved, both internally and with
their surroundings. In some
cases equilibrium is reached
quickly, in others it is achieved
slowly e.g. some chemical
reactions reach equilibrium in
fractions of seconds – ice cubes
require a few minutes to melt
while an iron rod requires years
to rust away.
Click video icon for the 2nd law.

4
Uses of Second Law of
Thermodynamics (cont.)
Second Law has many important uses, including:
1. Predicting direction of processes.
2. Establishing conditions for equilibrium.
3. Determining best theoretical performance of cycles,
engines and other devices.
4. Evaluating quantitatively factors that preclude the
attainment of best theoretical performance level.
5. Defining a temperature scale independent of properties
of any thermometric substance (Kelvin scale).
6. Developing means for evaluating properties such as U
and H in terms of properties that are more readily
obtained experimentally.

5
Statements of Second Law of
Thermodynamics
• No single statement of the Second Law brings out each of its many
aspects. Three alternative statements of Second Law are given i.e. (1)
Kelvin–Planck, (2) Clausius and (3) Entropy statement
1. Kelvin–Planck statement:
It is impossible for any system to operate in a thermodynamic cycle and deliver a
net amount of energy by work to its surroundings while receiving energy by heat
transfer from a single thermal reservoir.
• ‘Cycle’ in Kelvin–Planck statement requires that system be restored
periodically to its original state e.g. for a gas in a piston-cylinder assembly,
its initial expansion and re-compression to original state constitute a
complete cycle.
2. Clausius statement:
It is impossible for any system to operate in such a way that the sole result would
be an energy transfer by ‘heat’ from a cooler to a hotter body.
3. Entropy statement:
It is impossible for any system to operate in a way that entropy is destroyed.

6
Heat Engines
• Are devices/ machines that produce work from heat in a cyclic process e.g. a steam
power plant in which the working fluid (steam) periodically returns to its original
state.

• Differ from one another, but all can be

characterised by the following:
• Receive heat (QH or QIN) from a high-T source e.g.
solar energy, oil furnace, nuclear reactor etc.
• Convert part of this heat to work (usually in the form
of a rotating shaft) (WOUT). Part of heat received
by a heat engine is
• Reject the remaining waste heat (QC or QOUT) to a converted to work,
while rest is rejected
low-T sink e.g. the atmosphere, rivers etc. to a sink

• Operate on a cycle.

• A reservoir that supplies energy in the form of

heat is called a heat source.
• A reservoir that absorbs energy in the form of
heat is called a heat sink.

Click video icon heat engines and

the 2nd law of thermodynamics.
7
Heat Engines
• A reservoir is a hypothetical body with a relatively large thermal energy capacity
(mass x specific heat) that can supply or absorb finite amounts of heat without
undergoing any change in temperature e.g.
• Large bodies of water such as oceans, lakes and rivers as well as the atmospheric
air can be modelled accurately as thermal energy reservoirs.
• The atmosphere does not warm up as a result of heat losses from residential buildings
in winter.

• ‘Work-producing device’ that best fits into definition of heat engines is steam
power plant, which is an external-combustion engine (next slide).
• Combustion takes place outside the engine and thermal energy released during
this process is transferred to steam as heat operating in a thermodynamic cycle.
• Devices that do not operate in a thermodynamic cycle involve engines with
internal combustion e.g. gas turbines and car engines:
• Operate in a mechanical cycle since working fluid (combustion gases) does not
undergo a complete cycle.
• Exhaust gases are purged and replaced by fresh air and fuel mixture at end of the
cycle instead of being cooled to initial temperature.

8
For the steam power plant, the process
becomes:
2. Heat from a fuel (heat of combustion of a fossil fuel or heat from a
nuclear reaction), QIN is transferred in boiler to water, converting it to high-
T steam at boiler pressure.

3. Energy is transferred
1. Liquid water at as shaft work (WOUT) from
ambient T is pumped steam to surroundings by
into a boiler at high a device such as a
pressure (WIN) turbine, in which steam
required by boiler. expands to reduced P
and T.

4. Exhaust steam from turbine is condensed by transfer of heat (QOUT) to

surroundings, producing liquid water that returns to boiler, thus
completing the cycle.

9
Heat Engines (cont.)

10
Example

Click here for solution

11
Example

A car engine with a power output of 65 hp has a

thermal efficiency of 24%. Determine the fuel
consumption rate of this car if the fuel has a
heating value of 19000 Btu/lbm (i.e. 19 000 Btu of
energy is released for each lbm of fuel burned).

Click here for solution

13
Thermal Efficiencies of Work-
producing Devices
• Thermal efficiencies of work-producing devices are relatively low.
• Ordinary spark-ignition automobile engines have a thermal efficiency
of ~25% i.e. an automobile engine converts about 25% of chemical
energy of fuel to mechanical work.
• Efficiency becomes as high as 40% for diesel engines and large gas-
turbine plants. Efficiency becomes as high as 60% for large combined
gas-steam power plants.
• Today, even with most efficient heat engines available, almost one-
half of energy supplied ends up in rivers, lakes, or atmosphere as
waste energy.
• If a thermal efficiency of 100% is not possible for heat engines, what
then determines the upper limit? The upper limit for thermal
efficiency (100%) is dependant on degree of reversibility of its
operation.

15
• Heat engine operating in a completely reversible manner is called a Carnot
Engine.
• Since Carnot Engine is reversible, may be operated in reverse thereby,
becoming a reversible refrigeration cycle for which quantities IQHI, IQCI and
IWI are same as for engine cycle but are reversed in direction i.e. transfer
of heat from a low-T medium to a high-T one.

Basic components of a
refrigeration system and typical
operating conditions

• Working fluid used in refrigeration cycle is called refrigerant and most

frequently used refrigeration cycle is vapour-compression refrigeration cycle
involving 4 main components: a compressor, a condenser, an expansion valve
and an evaporator.
16
Four Steps that make up a Carnot Cycle are:
■Figure A: P-V diagram of the Carnot Cycle
1. System maintains contact with hot reservoir at
TH and undergoes a reversible isothermal
expansion process (1-2) during which heat
IQHI is absorbed from hot reservoir.

2. System undergoes a reversible adiabatic

expansion process (2-3) reducing TH back to
that of the cold reservoir TC
(A) P-V diagram of the Carnot Cycle

3. System maintains contact with reservoir at T c

and undergoes a reversible isothermal
compression process (3-4) rejecting heat IQCI
to the cold reservoir.

4. System at temperature of a cold reservoir T c

(B) P-V diagram of the reversed Carnot cycle
undergoes reversible adiabatic compression
process (4-1) causing its temperature to rise to
that of a hot reservoir at TH and returning to its
initial state.
17
Carnot’s Theorem

Click video icon for the derivation of

the efficiency of a Carnot engine
18
Example

Click here for solution

19
Example

Click here for solution

21
Thermodynamic Temperature Scale
• Temperature scale independent of properties of substances that
are used to measure temperature is called a thermodynamic
temperature scale.
• Carnot engine allows establishment of a thermodynamic
temperature scale that is independent of any material properties.
• Reversible heat engines have same thermal efficiency when
operating between same two reservoirs i.e. efficiency of a
reversible engine is independent of working fluid employed
and its properties, the way the cycle is executed, or the type of
reversible engine used.
• Energy reservoirs are characterised by their temperatures
 thermal efficiency of reversible heat engines is a function
of reservoir temperatures only.

23
• Let θ represent temperature on some empirical
scale
that identifies temperature levels.

• Consider two Carnot Engines, one operating

between a hot reservoir at temperature θ H and a cold
reservoir at temperature θC ; and a second operating

between the reservoir at θC and a still colder

reservoir at θF

24
• Even though thermodynamic temperature scale is defined
with help of reversible heat engines, it is not possible, nor
is it practical, to actually operate such an engine to
determine numerical values on the absolute temperature
scale.
• Absolute temperatures can be measured accurately by
other means, such as constant-volume ideal-gas
thermometer together with extrapolation techniques.
• However, validity of equation can be demonstrated from
physical considerations for a reversible cycle using an ideal
gas as working fluid.

25
Ideal-Gas Temperature Scale;
Carnot's Equations
• Cycle traversed by an ideal gas serving as the working fluid in a Carnot
engine is shown by a PV diagram:

26
Ideal-Gas Temperature Scale;
Carnot's Equations (cont.)

27
Example

Click here for solution

28
Entropy
 
Definition:
• The concept of entropy can be an awkward one to grasp due to its
intangibility. In this section I will give some equivalent definitions of
entropy and consider methods of determining entropy changes for
various types of processes.

• Entropy was defined by Clausius as follows: When a system passes in

a reversible way from one state to another state, at an absolute
constant temperature T, its change in entropy is equal to the heat Q it
absorbs, divided by T.

30
Entropy (cont.)
Definition:

• It could also be defined as "a thermodynamic quantity representing the

unavailability of a system's thermal energy for conversion into
mechanical work, often interpreted as the degree of disorder or
randomness in the system".

• Another writer has defined entropy as an intrinsic property of matter,

so defined that an increase in the unavailability of the total energy of
the system is quantitatively expressed by a corresponding increase in
its entropy. If entropy is defined as a measure of the unavailability of
internal energy, any degradation of this energy to heat or any other
form of energy will obviously lead to an increase in entropy.

31
Entropy (cont.)

Click video icons for entropy

in a Carnot cycle
32
Entropy (cont.)

Entropy change between two specified

states is the same whether the process is
reversible or irreversible

33
Entropy (cont.)

34
Entropy (cont.)
• Entropy owes its existence to Second Law, from which it arises
in much the same way as internal energy does from First Law.
• If:
> 0 (+) – Irreversible process
S =0 – Reversible process
< 0 (-) – Impossible process

35
Summary
• Processes occur in a certain direction only, not in any direction i.e.
S  0. A process violating this principle cannot occur i.e. it is
impossible.
• Entropy is a non-conserved property and there is no such thing as
the conservation of entropy principle. It is conserved during the
idealised reversible processes only and increases during all actual
processes.
• The value of entropy of a system is
fixed once the state of the system
is fixed.
• Specifying two intensive independent
properties (e.g. T and P) fixes the
state of a simple compressible
system, as well as values of other
properties at that state as well as the
value of entropy.

36
Example

Click here for solution

37
Example

A piston–cylinder device contains a liquid–vapour mixture of

water at 300K. During a constant P process, 750 kJ of heat is
transferred to the water. As a result, part of the liquid in the
cylinder vaporises.
Determine S of the water during the process.

Click here for solution

39
Example

Click here for solution

41
Entropy Changes of an Ideal Gas

43
Entropy Changes of an Ideal Gas
(cont.)

44
Entropy Changes of an Ideal Gas
(cont.)

45
Entropy Changes of an Ideal Gas
(cont.)

46
Entropy Changes of an Ideal Gas
(cont.)

47
Example

Click here for solution

48
Example

Click here for solution

50
Example

Steam enters an adiabatic turbine at 5 MPa and

450°C and leaves at a pressure of 1.4 MPa.
Determine the work output of turbine per unit
mass of steam if process is reversible.

Click here for solution

52
Entropy and ‘Entropy Generation
in Daily Life’
• Entropy - measure of disorder or disorganisation in a system.
• Entropy generation is also a measure of disorder or disorganisation generated
during a process.
• Efficient people lead low-entropy (highly
organised) lives:
 have a place for everything (minimum
uncertainty) and takes minimum energy for them
to locate something.
• Inefficient people are disorganised and lead high-
entropy lives:
 takes them long to find something they need
and are likely to create ‘a bigger disorder’ when
searching since they probably conduct the
search in a disorganised manner.
• People leading high-entropy lifestyles are always
on the run and never seem to ‘catch up’.

55
Example
Liquid methane is commonly used in various cryogenic applications. The
critical temperature of methane is 191K (82°C), and thus methane must be
maintained below 191K to keep it in liquid phase.
Determine the entropy change of liquid methane as it undergoes a
process from 110K and 1 MPa to 120K and 5 MPa
(a) using tabulated properties and
(b) approximating liquid methane as an incompressible substance.
What is the error involved in the latter case?
State 1- (P1 = 1 MPa, T1 = 110K): S1 = 4.875kJ/kg.K and Cp1 = 3.471kJ/kg.K
State 2- (P2 = 5 MPa, T2 = 120K): S2 = 5.145kJ/kg.K and Cp2 = 3.486kJ/kg.K

Click here for solution

56
 Entropy Balance for Open
Systems
 ENTROPY IS NOT CONSERVED hence yielding equation (1):

Rate of change Net rate of Rate of Total rate of

of entropy
Entropy in + change in
entropy of
+ change of
entropy in = generation
control volume flowing steams surroundings

  𝑑 ( 𝑚𝑆 )𝐶𝑉 𝑑𝑆 𝑡 𝑠𝑢𝑟𝑟
+∆ ( 𝑆 𝑚
˙ ) 𝑓𝑠 + =𝑆
˙ 𝐺≥0
𝑑𝑡 𝑑𝑡
General equation for entropy

58
Entropy Balance for Open
Systems
 𝑑 ( 𝑚𝑆 )𝐶𝑉 Rate of change of entropy in
𝑑𝑡 the fluid in the CV

¿ ∑ 𝑚𝑖𝑛𝑙𝑒𝑡 𝑆 𝑖𝑛𝑙𝑒𝑡 − ∑ 𝑚𝑜𝑢𝑡𝑙𝑒𝑡 𝑆 𝑜𝑢𝑡𝑙𝑒𝑡

 
∆
  (𝑆𝑚
˙ )𝑓𝑠

𝑡
 𝑑𝑆 𝑠𝑢𝑟𝑟   𝑄˙ 𝑗
𝑑𝑡 −∑
𝑗 𝑇 𝜎, 𝑗
Rate of entropy generation
 𝑆
˙ 𝐺 • Must be positive for
irreversible process
• =0 for reversible process

59
Entropy Balance for Open
Systems
For steady state flow process, the mass and entropy of the
fluid in the control volume are constant:

 𝑑 ( 𝑚𝑆 )𝐶𝑉
=0
𝑑𝑡
  𝑄˙ 𝑗
 −
∆ ∑
( 𝑆 𝑚˙ )𝑓𝑠  𝑆
˙ 𝐺= ¿
𝑗 𝑇 𝜎, 𝑗

60
Entropy Balance for Open
Systems
Entropy Change of System: Ssystem

Click video icon for open system

entropy balance examples
61
Entropy Transfer: Sin and Sout
• Entropy is transferred to or from a system by two mechanisms
namely, heat transfer and mass flow.
• Entropy interaction associated with a fixed mass or closed system
is through heat transfer.
• Entropy transfer for an adiabatic closed system is zero:
Sadiabatic, closed = 0 = Sisentropic

• Entropy transfer by work is zero: Swork = 0

• Heat transfer to a system increases entropy of that system and
heat transfer from a system decreases it.
• Entropy transfer by mass flow: Smass = m(S)

62
Entropy Transfer: Sin and Sout
Entropy Generation: Sgen

• Irreversibilities such as friction, mixing, chemical reactions, heat

transfer through a finite temperature difference, unrestrained
expansion, non-quasi equilibrium compression, or expansion
always cause entropy of a system to increase.

• Entropy generation is a measure of entropy created by such

effects during a process.

63
Example
Consider steady heat transfer through a 5 m x 7 m brick wall of a
house of thickness 30 cm. On a day when the temperature of the
outdoors is 0oC, the house is maintained at 27oC.
The temperatures of the inner and outer surfaces of the brick wall
are measured to be 20oC and 5oC, respectively. The rate of heat
transfer through the wall is 1035 W.
Determine the rate of entropy generation in the wall, and the
rate of total entropy generation associated with this heat
transfer process

Click here for solution

64
Example

In a steady-state flow process , 1 mol s-1

of air at 600K and 1 atm is continuously
mixed with 2 mol s-1 of air at 450K and 1
atm. The product stream is at 400K and 1
atm. A schematic representation of the
process is shown below.
Determine the rate of heat transfer and
the rate of entropy generation for the
process.
Assume that the air is an ideal gas with
Cp = (7/2)R, the surroundings are at
300K, and PE and KE changes are
negligible.

Click here for solution

67
Calculation of Ideal Work

X X
70
Calculation of Ideal Work (cont.)

X X
71
Calculation of Ideal Work (cont.)

𝑊
  𝑖𝑑𝑒𝑎𝑙 =+ 𝑣𝑒

𝑊
  𝑖𝑑𝑒𝑎𝑙 =− 𝑣𝑒

72
Calculation of Ideal Work (cont.)
Lost Work

73
Calculation of Ideal Work (cont.)
Lost Work

  Actual work of a process

 ˙ 1 2
𝑊 𝑖𝑑𝑒𝑎𝑙 = ∆
[( 𝐻+
2
𝑢 + 𝑧𝑔 𝑚) ]
˙ −𝑇 𝜎 ∆ ( 𝑆 𝑚
˙ )𝑓𝑠

𝑊
  ˙ 𝑙𝑜𝑠𝑡 =𝑇 𝜎 ∆ ( 𝑆 𝑚
˙ ) 𝑓𝑠 − 𝑄˙
  a single surrounding temperature the steady state entropy balance
For
becomes:

 ˙ 𝑄˙
𝑊
  ˙ 𝑙𝑜𝑠𝑡 =𝑇 𝜎 𝑆
˙𝐺
𝑆 𝐺 =∆ ( 𝑆 𝑚˙ )𝑓𝑠 −
𝑇𝜎

74
Example
A nuclear power plant generates 750 MW; the reactor temperature is
588.15 K (315°C) and a river with water temperature of 293.15 K (20°C) is
available.
a. What is the maximum possible thermal efficiency of the plant, and
what is the minimum rate at which heat must be discarded to the
river?
b. If the actual thermal efficiency of the plant is 60% of the maximum,
at what rate must heat be discarded to the river, and what is the
temperature rise of the river if it has a flowrate of 165 m 3 s-1?
For river water:
= 165 m3/s;  = 1000 kg m-3; Cp = 1 cal g-1 K-1

Click here for solution

75
Example

Click here for solution

78
Third Law of Thermodynamics

• The 3rd law of thermodynamics states that the absolute entropy is zero
for all perfect crystalline substances at absolute zero temperature.

• You will not be tested on the 3rd law of thermodynamics, just know
it exists.

80
Summary

81
Engineering Council of South Africa
(ECSA) Exit Level Outcomes (ELO):
■ ELO 1
Problem solving: Apply engineering principles to
systematically diagnose and solve broadly-defined engineering
problems
■ ELO 2
Application of scientific and engineering knowledge:
Apply knowledge of mathematics, natural science and
engineering sciences to defined and applied engineering
procedures, processes, systems and methodologies to solve
broadly-defined engineering problems.

82
83