Second Law of Thermodynamics - Spring 2020

 1 
CHME 212 – Ch. Eng. Thermo. I, Prof. S. Al-Muhtaseb/ A. Benamor @ QU, 2020
• Asserts that processes occur in a certain direction
and that energy has quality as well as quantity.
• Also used in determining the theoretical limits for

the performance of engineering systems such as
Heat Engines & Refrigerators, as well as predicting
the degree of completion of chemical reactors.
• A process cannot occur without both laws

satisfied
CHME 212 – Ch. Eng. Thermo. I, Prof. S. Al-Muhtaseb/ A. Benamor @ QU, 2020 2
Any body with a large thermal energy capacity
m*cv (with either large cv or large mass) that can
absorb OR supply finite amounts of heat without
undergoing any change in temperature.
Q Infinitesimal (small)
T  0 temperature difference
mcv
• Thermal energy SOURCE
• Thermal energy SINK
Examples:
 Oceans, lakes, rivers, etc.
 Atmospheric air
 Two-phase systems (constant Temp.)
 Heat sources (Furnaces) -- supply heat
 Heat sinks (Condensers) -- absorb heat
• This term is often used for devices which
produce work and do not undergo a complete
thermodynamic cycle (e.g., gas turbines).
• Work can be converted to heat directly and

completely, but converting heat to work
requires the use of some special devices (i.e.,
Heat Engines).
Hot reservoir at TH
𝑄𝐻
System 𝑊𝑜𝑢𝑡
𝑄𝐿
Cold reservoir at TL
• Receive heat from a source.
• Convert part of heat into work.
• Reject the remainder waste heat into a
sink.
• Operate on a cycle.
 NO !!!
 Waste energy (QL) is rejected from the
condensers or cooling towers to rivers, lakes,
oceans, atmosphere, etc.
 Without heat rejection process, the cycle
cannot be completed -- the working fluid
cannot return to its initial state without heat
rejection.
Copyright © The
McGraw-Hill
Wnet , out  Wout  Win (kJ)
Companies, Inc.
• The four basic components are treated as
open systems. However, the whole cycle is
treated as a closed system, if leakage is
terminated.
• Recall, E=0 for a closed system undergoing
a cycle. Thus,
Wnet , out  Qin  Qout (kJ)
• Heat engines operate on a repeating cycle
• Cycles have four elements: compression,

heating, expansion & cooling.
• Refrigeration engines and heat pumps
also operate on repeating cycles.
• Cycles are: Carnot, Rankine, Brayton, Otto,
plus others.
To unify treatment for all cyclic device, we
define:
• QH = magnitude of HT between the
cyclic device and the high-temperature
reservoir (TH) Heat Source TH
• QL = magnitude of HT between the QH
cyclic device and the low-temperature Heat Wnet

Engine
reservoir (TL)
QL
where QH & QL are positive magnitudes.
Heat Sink TL
Heat Source TH
QH 𝑈𝑠𝑒𝑓𝑢𝑙 𝑊𝑜𝑟𝑘 𝑂𝑢𝑡𝑝𝑢𝑡

𝑡ℎ =
Heat Wnet 𝐸𝑛𝑒𝑟𝑔𝑦 𝑅𝑒𝑞𝑢𝑖𝑟𝑒𝑑
Engine
𝑾𝒏𝒆𝒕,𝒐𝒖𝒕 𝑄𝐻 −𝑄𝐿 𝑄𝐿
QL = = =1 −
𝑸𝑯 𝑄𝐻 𝑄𝐻
Heat Sink TL
 th  1
Gasoline Diesel Industrial Frame Power Plant
Engines Engines Gas Turbine
25-28% 34-38% 35% 40-60%
* The rejected heat into the sink represents the wasted

energy.
It is impossible for any device that
operates on a cycle that receives heat
from a single reservoir and produce a net
amount of work, i.e.,
 Two reservoirs are needed for continuous

operation & th < 100%
Fuel’s Heating Value: The amount of heat
released when a specific amount of fuel (unit mass)
at room temperature is completely burned; and the
combustion product are cooled to the room
temperature.
 LHV: Lower Heating Value
 combustion product in vapor form
 HHV: Higher Heating Value
 combustion product in liquid form
𝒌𝒈 𝑯𝟐 𝑶 𝑷𝒓𝒐𝒅𝒖𝒄𝒆𝒅
𝑯𝑯𝑽 = 𝑳𝑯𝑽 + 𝒉𝒇𝒈,𝑯𝟐 𝑶 @ 𝟐𝟓 𝒐𝑪
𝒌𝒈 𝑭𝒖𝒆𝒍 𝒃𝒖𝒓𝒏𝒆𝒅
See full
table in
book
Q
Automobiles :  combustion 
m fuel .LHV
Q
Furnaces :  combustion 
m fuel .HHV
Fuel
heat transfer output QH
 combustion   Combustion
rate of fuel energy input m fuel .HHV
QH
net shaft work output of turbine Wout ,net
thermal   Heat Engine
heat input of working fluid QH
Cycle
Wnet,out
electrical power output Wel
 generator  
mechanical power input Wout ,net
Electric
Welec Generator
CHME 212 – Ch. Eng. Thermo. I, Prof.
S. Al-Muhtaseb/ A. Benamor @ QU, 20
2020
Fuel
The overall efficiency for a
power plant is defined as: Combustion
QH
𝑊𝑛𝑒𝑡,𝑒𝑙𝑒𝑐
𝜂𝑜𝑣𝑒𝑟𝑎𝑙𝑙 = 𝜂comb 𝜂𝑡ℎ 𝜂𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑜𝑟 =
𝑚𝑓𝑢𝑒𝑙 𝐻𝐻𝑉
Heat Engine
Cycle
Wnet,out
Electric
Welec Generator
2020
• This term is often used for work-consuming
cyclic devices that transfer heat from a low-
temperature reservoir medium to a high-
temperature reservoir.
• The working fluid is called refrigerant. The

most common cycle is vapor-compression
refrigeration cycle.
Hot reservoir
𝑄𝐻 Clausius says
we can’t have
𝑊𝑛𝑒𝑡,𝑖𝑛 System the system as
drawn:
We need to have some work
input to make it happen.
𝑄𝐿
Cold reservoir
Related to Refrigerators
and Heat Pumps
It is impossible to construct a device that

operates in a cycle and produces no effect
other than the transfer of heat from a lower-
temperature reservoir to a higher-
temperature reservoir.
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Basic components of a refrigeration

system and typical operating
conditions.
The objective of a
refrigerator is to
remove QL from the
cooled space.
The objective of a
heat pump is to
supply heat QH into
the warmer space.
Desired output
COP 
Required input
QL QL 1
COPR    (compare it with th )
W net , in Q H  Q L Q H / Q L  1
QH QH 1
COPHP    (compare it with th )
Wnet , in QH  QL 1  QL / QH
• COPHP  COPR  1 ( 1)
for similar values of QH &QL
Heat
Solution: Removal
𝐷𝑒𝑠𝑖𝑟𝑒𝑑 𝑂𝑢𝑡𝑝𝑢𝑡
𝐶𝑂𝑃𝑅 =
𝑅𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝐼𝑛𝑝𝑢𝑡
𝑘𝐽 𝑚𝑖𝑛 Power
𝑄ሶ 𝐿 750 𝑚𝑖𝑛 60 𝑠
𝐶𝑂𝑃𝑅 = = = 2.08
𝑊 ሶ 𝑘𝐽
6
𝑠
(b) Heat Rejected to the atmosphere:
Air Conditioning
cycle
Overall Energy Balance:

𝑘𝐽 60 𝑠 𝑘𝐽 𝑘𝐽
𝑄ሶ 𝐻 = 𝑊ሶ + 𝑄ሶ 𝐿 = 6 + 750 = 1,110
𝑠 𝑚𝑖𝑛 𝑚𝑖𝑛 𝑚𝑖𝑛
• Looking for highest efficiency Idealization.
• An idealized process is called a reversible process.
• A reversible process is defined as a process

that can be reversed w/o affecting the
surroundings.
• Real processes are irreversible.
• Easy to analyze.
• Set the theoretical limits for the corresponding
irreversible process.
 Second law efficiency for actual processes:
Defined as the degree of approximation to the
corresponding reversible process:
𝑎𝑐𝑡𝑢𝑎𝑙 𝐶𝑂𝑃𝑎𝑐𝑡𝑢𝑎𝑙
𝐼𝐼 = 𝑂𝑅
𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝐶𝑂𝑃𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒
• Friction.
• Non-quasi-equilibrium
expansion & compression.
• Mixing processes.
• Heat transfer.
• Electric resistance.
• Chemical reaction.
• An internally reversible process is where no
irreversibilites occur within the boundaries of
the system during the process.
• An externally reversible process is where no
irreversibilites occur outside the system
boundaries of the system during the process.
• A totally reversible process is both internally
and externally reversible during the process.
• Proposed by Sadi Carnot in 1824.
• It is the best known reversible (theoretical) cycle,
which is based on reversible processes.
• It consists of 4 reversible processes:

two isothermal and two adiabatic.
• The Carnot heat engine is based on Carnot cycle.
Reversible Isothermal
Execution of Carnot cycle in a closed
Expansion
Reversible Adiabatic
Expansion
Quasi-equilibrium
system.
& frictionless
Reversible Isothermal
Compression
Reversible Adiabatic
Compression
36
P-V diagram of the Carnot

cycle.

2020
• Only the directions of any heat
and work interaction are
reversed.
• It becomes Carnot
refrigeration (or Heat Pump)
cycle.
reversed Carnot cycle.

P-V diagram of the
39
1. The efficiency of an irreversible heat
engine is always less than the efficiency
of a reversible one operating between the
same two reservoirs.
2. The efficiencies of all reversible heat

engines operating between the same two
reservoirs are the same.
The Carnot principles.
Low Temperature Reservoir at TL
• For a reversible engine operating between two
reservoirs, we write:
QH  (TH )

QL  (TL )
• Kelvin proposed the Kelvin scale by setting
(T)=T:
 QH  TH
  
 Q L  rev TL
where T is in absolute temperature.
• The thermal efficiency for any
QL
heat engine (rev. or Irrev.) is th  1 
defined as: QH
• Carnot engine efficiency: TL

th ,rev  1
TH
Desired output
• COP 
Required input
1 1
• Carnot refrigerator: COPR, rev  
QH / QL  1 TH / TL  1
1 1
• Carnot heat pump: COPHP,rev  
1  QL / QH 1  TL / TH
than a reversible refrigerator operating

No refrigerator can have a higher COP
between the same temperature limits.
Solution: calculated efficiency is
higher than reversible
𝑊 160 𝐵𝑡𝑢 efficiency  this
𝜂𝑡ℎ = = = 𝟎. 𝟓𝟑𝟑 = 𝟓𝟑. 𝟑 %
𝑄𝐻 300 𝐵𝑡𝑢 process is not possible
𝑊 𝑄𝐻 − 𝑄𝐿 𝑄𝐿 𝑇𝐿 540 𝑅
𝜂𝑡ℎ,𝑟𝑒𝑣 = = =1− =1− =1−
𝑄𝐻 𝑟𝑒𝑣 𝑄𝐻 𝑟𝑒𝑣
𝑄𝐻 𝑟𝑒𝑣
𝑇𝐻 900 𝑅
= 𝟎. 𝟒𝟎 = 𝟒𝟎%
𝑄ሶ 𝐿 = 𝑊ሶ 𝑖𝑛 × 𝐶𝑂𝑃𝑅 = 540 𝑊
𝐶𝑂𝑃𝑅 = 1.2 𝑸ሶ 𝑳
𝑪𝑶𝑷𝑹 =
𝑊ሶ 𝑖𝑛 = 450 𝑊 𝑾ሶ 𝒊𝒏 𝑸ሶ 𝑯 = 𝑸ሶ 𝑳 + 𝑾ሶ 𝒊𝒏
= 𝟓𝟒𝟎 + 𝟒𝟓𝟎 = 𝟗𝟗𝟎 𝑾
Energy Balance on Evaporator:
Assumptions:
• Steady state, steady flow
• No work
• Negligible KE & PE
• Single input, single output
Energy Balance Equation:
𝑽𝟐𝒊 𝑽𝟐𝒆
𝑸ሶ − 𝑾ሶ + ෍ 𝒎ሶ 𝒊 𝒉𝒊 + + 𝒈𝒛𝒊 − ෍ 𝒎ሶ 𝒆 𝒉𝒆 + + 𝒈𝒛𝒆 = ∆𝑬𝒔𝒚𝒔
𝟐 𝟐
Steady state, Single input-single output  𝑚ሶ 𝑖 = 𝑚ሶ 𝑒 = 𝑚ሶ 

𝟏 𝟐
𝑸ሶ 𝑳 = 𝒎ሶ 𝒉𝒆 − 𝒉𝒊 + 𝑽𝒆 − 𝑽𝟐𝒊 + 𝒈 𝒛𝒆 − 𝒛𝒊
𝟐
𝒌𝑱
ሶ
𝑸𝑳 𝟎. 𝟓𝟒𝟎 𝒌𝒈
𝒔
 𝒎ሶ = =
𝒌𝑱
= 𝟎. 𝟎𝟎𝟑𝟏𝟏𝟑
𝒉𝒆 − 𝒉𝒊 𝟐𝟑𝟖. 𝟖𝟒 − 𝟔𝟓. 𝟑𝟗 𝒔
𝒌𝒈
Exercise: Find How?
Refrigerant R-134a is used to keep a room at 25 °C while the
outside temperature is 10 °C and the atmospheric pressure is 100
kPa. The evaporator and condenser operate at 120 and 800 kPa,
respectively. The refrigerant enters the condenser as a saturated
vapor and exits as a saturated liquid. The second law efficiency
for this cycle is 85%. If the power required for this cycle is 800 W,
find the following:
a) The efficiency or COP of the cycle (whichever
is relevant)
b) The heat transfer rate from the outside
atmosphere
c) The heat transfer rate to the room
d) The refrigerant temperatures and phases in
each stream
e) Draw the process on Pv and Tv diagrams
Assumptions:
1. Steady State
2. Single-input, single-output for all devices
3. Negligible Change of KE and PE in all devices
4. Negligible pressure drop in all lines (e.g., pressure of the outlet
of the valve = pressure at the inlet of the evaporator)
5. Negligible Heat Transfer in expansion valve and the compressor
a. Cycle Type: Heat Pump (why??) 
−1
𝑄𝐻 𝑄𝐻 𝑄𝐿
𝐶𝑂𝑃𝐻𝑃 = = = 1−
𝑊𝑖𝑛 𝑄𝐻 − 𝑄𝐿 𝑄𝐻
Reversible COP:
−1 −1 −1
𝑄𝐿 TL 283
𝐶𝑂𝑃𝐻𝑃,𝑟𝑒𝑣 = 1− = 1− = 1− = 19.87
𝑄𝐻 rev
TH 298
Second Law Efficiency: Ans. (a)

𝐶𝑂𝑃𝐻𝑃
𝜂𝐼𝐼 =  𝐶𝑂𝑃𝐻𝑃 = 𝜂𝐼𝐼 𝐶𝑂𝑃𝐻𝑃,𝑟𝑒𝑣 = 0.85 × 19.87 = 16.89
𝐶𝑂𝑃𝐻𝑃,𝑟𝑒𝑣
Ans. (c)
𝑄ሶ 𝐻
𝐶𝑂𝑃𝐻𝑃 =  𝑄ሶ 𝐻 = 𝐶𝑂𝑃𝐻𝑃 𝑊ሶ 𝑖𝑛 = 16.89 × 0.8 = 13.51 𝑘𝑊
𝑊ሶ 𝑖𝑛
Ans. (b)
Overall Energy Bal.: 𝑄ሶ 𝐿 = 𝑄ሶ 𝐻 − 𝑊ሶ 𝑖𝑛 = 13.51 − 0.8 = 12.71 𝑘𝑊
d. Phase and temperature of
each stream:
Numbering all streams as

shown in the Figure 
Energy Balance on the Condenser:
… Simplification [review unit 5] …  𝑄ሶ 𝐻 = 𝑚ሶ ℎ2 − ℎ1

𝑄ሶ 𝐻 −13.51 𝑘𝑔 𝑠𝑎𝑡
 𝑚ሶ = = = 0.07863 𝑇1 = 𝑇2 = 𝑇800 𝑘𝑃𝑎
ℎ2 −ℎ1 95.47−267.29 𝑠
= 31.31 ℃
Energy Balance on the Expansion Valve:
… Simplification [review unit 5] …  ℎ3 = ℎ2
𝑘𝐽
 ℎ3 = 95.47
𝑘𝑔 Compare ℎ3 to ℎ𝑓 and ℎ𝑔 at 120 kPa 
stream 3 is a saturated liquid-vapor mixture
 𝑻𝟑 = 𝑻𝒔𝒂𝒕 𝟏𝟐𝟎 𝒌𝑷𝒂 = −𝟐𝟐. 𝟑𝟐 ℃
ℎ3 − ℎ𝑓 95.47 − 22.49
𝑥3 = = = 0.340
ℎ𝑓𝑔 214.48
Energy Balance on the Evaporator:
… Simplification [review unit 5] …  𝑄ሶ 𝐿 = 𝑚ሶ ℎ4 − ℎ3

𝑄ሶ 𝐿 12.71 𝑘𝐽
 ℎ4 = ℎ3 + ሶ = 95.47 + = 257.11
𝑚 0.07863 𝑘𝑔
Compare ℎ4 to ℎ𝑓 and ℎ𝑔 at 120 kPa  stream 4 is superheated vapor
 From Table A-13 
𝑘𝐽
ℎ4 = 257.11 @ 120 kPa
𝑘𝑔
Three Interpolations:
1. @ 𝑃 = 100 𝑘𝑃𝑎 → 𝑇 = 1.86 ℃
2. @ 𝑃 = 140 𝑘𝑃𝑎  𝑇 = 3.01 ℃
3. Interpolating between (1 and 2) for 𝑃 =
120 𝑘𝑃𝑎 → 𝑇4 = 2.44 ℃
T-v and P-v Diagrams:
T (°C)
P (kPa)
 
31.31
 
800

2.44
-22.32
120 
 
v v

Second Law of Thermodynamics - Spring 2020

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Second Law of Thermodynamics - Spring 2020

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 1 

• Also used in determining the theoretical limits for

• A process cannot occur without both laws

• Work can be converted to heat directly and

Wnet , out  Qin  Qout (kJ)

• Cycles have four elements: compression,

• QL = magnitude of HT between the QH

cyclic device and the low-temperature Heat Wnet

QH 𝑈𝑠𝑒𝑓𝑢𝑙 𝑊𝑜𝑟𝑘 𝑂𝑢𝑡𝑝𝑢𝑡

* The rejected heat into the sink represents the wasted

 Two reservoirs are needed for continuous

• The working fluid is called refrigerant. The

It is impossible to construct a device that

Basic components of a refrigeration

Overall Energy Balance:

• An idealized process is called a reversible process.

• A reversible process is defined as a process

• Real processes are irreversible.

• It consists of 4 reversible processes:

P-V diagram of the Carnot

CHME 212 – Ch. Eng. Thermo. I, Prof.

reversed Carnot cycle.

2. The efficiencies of all reversible heat

The Carnot principles.

Low Temperature Reservoir at TL

• Carnot engine efficiency: TL

than a reversible refrigerator operating

between the same temperature limits.

Energy Balance on Evaporator:

Steady state, Single input-single output  𝑚ሶ 𝑖 = 𝑚ሶ 𝑒 = 𝑚ሶ 

a. Cycle Type: Heat Pump (why??) 

Second Law Efficiency: Ans. (a)

Numbering all streams as

Energy Balance on the Condenser:

… Simplification [review unit 5] …  𝑄ሶ 𝐻 = 𝑚ሶ ℎ2 − ℎ1

… Simplification [review unit 5] …  ℎ3 = ℎ2

… Simplification [review unit 5] …  𝑄ሶ 𝐿 = 𝑚ሶ ℎ4 − ℎ3

Compare ℎ4 to ℎ𝑓 and ℎ𝑔 at 120 kPa  stream 4 is superheated vapor

 From Table A-13 

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