Chemical Engineering Thermodynamics

Applied Thermodynamics CHMT3040

Lecture 7

Isabella L. Greeff
Wits School of Chemical and Metallurgical Engineering
Lecture 7
The Second Law of Thermodynamics
- Power cycles interacting with two
reservoirs
Video: Cycles
- Refrigeration and heat pump cycles interacting with
interacting with two reservoirs two reservoirs
and max
- Kelvin temperature scale performance
- Maximum performance measures
for cycles
- Carnot cycle Video: Carnot Cycle
- Clausius inequality Video: Clausius inequality
Note: Videos do not necessarily comprise the
exact lecture slides, and also do not cover all
Study materials: Moran Chapter 5.5 to 5.11 study materials, always refer to study materials
listed.
 Power Cycles Interacting
with Two Thermal Reservoirs (1 of 2)
For a system undergoing a power cycle while
communicating thermally with two thermal
reservoirs, a hot reservoir and a cold reservoir,
the thermal efficiency of any such cycle is

Wcy cle QC
  1 (Eq. 5.4)
QH QH
 Power Cycles Interacting
with Two Thermal Reservoirs (2 of 2)
By applying the Kelvin-Planck statement of the
second law (eq. 5.3), three conclusions can be drawn:

{ < 0: Internal irreversibilities present

𝑊cycle ≤ 0 = 0: No internal irreversibilities (single reservoir) (Eq. 5.3)

• The value of the thermal efficiency must be less

than 100%. Only a portion of the heat transfer QH
can be obtained as work and the remainder QC is
discharged by heat transfer to the cold reservoir.

The two other conclusions, are called the Carnot

corollaries.
 Carnot Corollaries
• The thermal efficiency of an irreversible power
cycle is always less than the thermal efficiency of
a reversible power cycle when each operates
between the same two thermal reservoirs.
• All reversible power cycles operating between the
same two thermal reservoirs have the same
thermal efficiency.
A cycle is considered reversible when there are no
irreversibilities within the system as it undergoes the
cycle and heat transfers between the system and
reservoirs occur reversibly.
Refrigeration and Heat Pump Cycles Interacting
with Two Thermal Reservoirs (1 of 3)
For a system undergoing a refrigeration cycle or heat
pump cycle while communicating thermally with two
thermal reservoirs, a hot reservoir and a cold
reservoir, the coefficient of performance
for the refrigeration cycle is
QC QC
  (Eq. 5.5)
Wcy cle QH  QC

and for the heat pump cycle is

QH QH
  (Eq. 5.6)
Wcy cle QH  QC
Refrigeration and Heat Pump Cycles Interacting
with Two Thermal Reservoirs (2 of 3)

By applying the Kelvin-Planck statement of the

second law, three conclusions can be drawn:
• For a refrigeration effect to occur a net work input
Wcycle is required. Accordingly, the coefficient of
performance must be finite in value.
• The coefficient of performance of an irreversible
refrigeration cycle is always less than the
coefficient of performance of a reversible
refrigeration cycle when each operates between
the same two thermal reservoirs.
Refrigeration and Heat Pump Cycles Interacting
with Two Thermal Reservoirs (3 of 3)

• All reversible refrigeration cycles operating

between the same two thermal reservoirs have
the same coefficient of performance.

All three conclusions also apply to a system

undergoing a heat pump cycle between hot and cold
reservoirs.
 Kelvin Temperature Scale (1 of 2)
Consider systems undergoing a power cycle and a
refrigeration or heat pump cycle, each while
exchanging energy by heat transfer with hot and cold
reservoirs:

The Kelvin temperature is defined so that

 QC  TC
   (Eq. 5.7)
 QH  rev TH
cy cle
 Kelvin Temperature Scale (2 of 2)
- Eq. 5.7 states: When cycles are reversible, and only
then, the ratio of the heat transfers equals a ratio of
temperatures on the Kelvin scale, where TH is the
temperature of the hot reservoir and TC is the temperature
of the hot reservoir.

- As temperatures on the Rankine scale differ from Kelvin

temperatures only by the factor 1.8: T(oR)=1.8T(K), the T’s
in eq. 5.7 may be on either scale of temperature. Eq. 5.7 is
not valid for temperatures in oC or oF, for these do not
differ from Kelvin temperatures by only a factor, but
T(oC) = T(K) – 273.15
T(Fo) = T(R) – 459.67
 Maximum Performance Measures for Cycles
Operating between Two Thermal Reservoirs (1 of 2)
Previous deductions from the Kelvin-Planck statement of the
second law include:
1. The thermal efficiency of an irreversible power cycle is
always less than the thermal efficiency of a reversible power
cycle when each operates between the same two thermal
reservoirs.
2. The coefficient of performance of an irreversible
refrigeration cycle is always less than the coefficient of
performance of a reversible refrigeration cycle when each
operates between the same two thermal reservoirs.
3. The coefficient of performance of an irreversible heat pump
cycle is always less than the coefficient of performance of a
reversible heat pump cycle when each operates between the
same two thermal reservoirs.
 Maximum Performance Measures for Cycles
Operating between Two Thermal Reservoirs (2 of 2)
It follows that the maximum theoretical thermal efficiency and
coefficients of performance in these cases are achieved only
by reversible cycles. Using Eq. 5.7 in Eqs. 5.4, 5.5, and 5.6,
we get respectively:
TC
Power Cycle  max  1  (Eq. 5.9)
TH
TC
Refrigeration Cycle  max  (Eq. 5.10)
TH  TC
TH
Heat Pump Cycle  max  (Eq. 5.11)
TH  TC

where TH and TC must be on the Kelvin or Rankine scale.

Example Power Cycle Analysis (1 of 2)
(Example not in Textbook. Also review Moran Examples 5.1, 5.2 and 5.3.)

A system undergoes a power cycle while Hot Reservoir

TH = 500 K
receiving 1000 kJ by heat transfer from a
QH = 1000 kJ
thermal reservoir at a temperature of 500 K
Power Wcycle
and discharging 600 kJ by heat transfer to a Cycle

thermal reservoir at (a) 200 K, (b) 300 K, (c) QC = 600 kJ

400 K. For each case, determine whether
the cycle operates irreversibly, operates TC = (a) 200 K,
(b) 300 K,
reversibly, or is impossible. (c) 400 K
Cold Reservoir

Solution: To determine the nature of the cycle, compare

actual cycle performance () to maximum theoretical cycle
performance (max) calculated from eq. 5.9
Example Power Cycle Analysis (2 of 2)

Actual Performance: Calculate  using the heat

transfers: Q 600 kJ
C
  1  1  0.4
QH 1000 kJ

Maximum Theoretical Performance: Calculate

max from Eq. 5.9 and compare to :
 max
TC 200 K
(a)  max  1   1  0.6 0.4 < 0.6 Irreversibly
TH 500 K
TC 300 K
(b)  max  1   1  0.4 0.4 = 0.4 Reversibly
TH 500 K
TC 400 K
(c)  max  1   1  0.2 0.4 > 0.2 Impossible
TH 500 K
 Carnot Cycle

- The Carnot cycle provides a specific example of a

reversible cycle that operates between two thermal
reservoirs. Other examples are provided in
Chapter 9: the Ericsson and Stirling cycles.

- In a Carnot cycle, the system executing the cycle

undergoes a series of four internally reversible
processes: two adiabatic processes alternated with
two isothermal processes.
 Carnot Power Cycles (1 of 2)
The p-v diagram and schematic of a gas in a piston-
cylinder assembly executing a Carnot cycle are shown
below:
 Carnot Power Cycles (2 of 2)
The p-v diagram and schematic of water executing a
Carnot cycle through four interconnected components
are shown below:

In each of these cases the thermal efficiency is

given by TC
 max  1  (Eq. 5.9)
TH
Carnot Refrigeration and Heat Pump Cycles

- If a Carnot power cycle is operated in the opposite

direction, the magnitudes of all energy transfers
remain the same but the energy transfers are
oppositely directed.
- Such a cycle may be regarded as a Carnot
refrigeration or heat pump cycle for which the
coefficient of performance is given, respectively, by
TC
Carnot Refrigeration Cycle  max  (Eq. 5.10)
TH  TC

TH
Carnot Heat Pump Cycle  max  (Eq. 5.11)
TH  TC
 Clausius Inequality (1 of 3)
- Provides the basis for further development of
entropy, entropy production and entropy balances.

- Corollary of the Second Law applicable to any cycle

without regard for the body, or bodies, from which the
system undergoing a cycle receives energy by heat
transfer or to which the system rejects energy by
heat transfer. Such bodies need not be thermal
reservoirs.
 Q 
   ≤cy0cle
 T b
 Clausius Inequality (2 of 3)
The Clausius inequality is developed from the Kelvin-
Planck statement of the second law and can be
expressed as:

 Q 
   ≤cy0cle (Eq. 5.12)
 T b
where
indicates integral is to be performed over all parts of the
boundary and over the entire cycle.
b subscript indicates integrand is evaluated at the boundary
of the system executing the cycle.
 Clausius Inequality (3 of 3)

 Q 
    cy cle (Eq. 5.13)
 T b

The nature of the cycle executed is indicated by the

value of cycle:

cycle = 0 no irreversibilities present within the system

cycle > 0 irreversibilities present within the system
cycle < 0 impossible
(Eq. 5.14)
Example Use of Clausius Inequality (1 of 2)
(Example not in Textbook)

A system undergoes a cycle while receiving 1000

kJ by heat transfer at a temperature of 500 K and
discharging 600 kJ by heat transfer at (a) 200 K,
(b) 300 K, (c) 400 K. Using eqs. 5.13 and 5.14,
what is the nature of the cycle in each of these
cases?

Solution: To determine the nature of the cycle,

perform the cyclic integral of eq. 5.13 to each case
and apply eq. 5.14 to draw a conclusion about the
nature of each cycle.
Example Use of Clausius Inequality (2 of 2)

 Q  Qin Qout
Applying Eq. 5.13 to each cycle:       cy cle
 T  b TH TC
1000 kJ 600 kJ
(a)   cy cle    1 kJ/K cycle = +1 kJ/K > 0
500 K 200 K

Irreversibilities present within system

1000 kJ 600 kJ
(b)   cy cle    0 kJ/K cycle = 0 kJ/K = 0
500 K 300 K

No irreversibilities present within system

1000 kJ 600 kJ cycle = –0.5 kJ/K < 0

(c)   cy cle    0.5 kJ/K
500 K 400 K
Impossible
The End
Additional slides used
in videos
 Cycles interacting with two reservoirs

Koeberg in Western Cape Duvha in Mpumalanga

Hot reservoir: nuclear reactors Hot reservoir: coal boilers

Cold reservoir: ocean Cold reservoir: atmospheric air

Cycles interacting with two reservoirs
 Maximum performance of cycles

 QC  TC
   (eq 5.7)
 QH  rev TH
cy cle

Wcy cle QC QC QC QH QH
  1    
Wcy cle QH  QC Wcy cle QH  QC
QH QH

TC TC TH
 max  1   max   max 
TH TH  TC TH  TC
Carnot Cycles
Clausius Inequality
Clausius Inequality
 Q 
   
≤ cy
0 cle
 T b

• Basis for further development of entropy, entropy

production and entropy balances.
• Any cycle regardless of reservoirs from which it receives
heat or rejects heat to.
δQ2

T2 δQ1 𝛿𝑄 𝑄1 𝑄2 𝑄3 𝑄4
T1 = + + +
δQ3 Any cycle 𝑇 𝑏
𝑇1 𝑇2 𝑇3 𝑇4
T3
T4

δQ4
System boundary
Clausius Inequality
 Q 
    cy cle
 T b

The nature of the cycle is indicated by the value of cycle

cycle = 0 no irreversibilities present within the system

cycle > 0 irreversibilities present within the system
cycle < 0 impossible