Thermodynamics

ECH 2063

Lecture Notes 2a
Thermodynamics Processes - Heat
 Course Learning Outcomes
1. Understand the principles of thermodynamics and definitions and
properties associated with it.
2. Explain the different thermodynamics processes related to
chemical engineering and understand the different energy transfer
mechanisms during chemical processes.
3. Explain the First law of thermodynamics and the basic relationships
between the various forms of energy in closed and open systems.
4. Explain the entropy concept of the Second Law of thermodynamics
and apply your understanding to heat engines, refrigerators and
heat pumps.
5. Represent a typical thermodynamic cycle on a T-S diagram and
calculate the performance of a steam power plant.

Sep-16 EO: Thermodynamics-LO2 2

 Define Thermodynamic state, state in
balance

 The thermodynamic state of a system is defined by

specifying a set of measurable properties sufficient so
that all remaining properties are determined. Examples of
properties: pressure, temperature, density, internal
energy, enthalpy, and entropy.

 Intensive properties do not depend on mass (e.g. p, T, r ,

v=1/r, u and h); extensive properties depend on the total
mass of the system (e.g. V, M, U and H). Uppercase
letters are usually used for extensive properties.

Sep-16 EO: Thermodynamics-LO2 3

 Thermodynamics and Equilibrium

 Thermal Equilibrium – system and surroundings at the same

temperature.

 Mechanical Equilibrium – system and surroundings at the same

pressure.

 Chemical Equilibrium – system and surroundings at the same chemical

concentrations.

Sep-16 EO: Thermodynamics-LO2 4

 Thermal and Mechanical Equilibrium

Sep-16 EO: Thermodynamics-LO2 5

 The Zeroth Law of Thermodynamics

 If two bodies are in thermal equilibrium with a third body, they are
also in thermal equilibrium with each other.

 This obvious fact cannot be concluded from the other laws of

thermodynamics, and it serves as a basis of temperature
measurement.

 By replacing the third body with a thermometer, the zeroth law

can be restated two bodies are in thermal equilibrium if both have
the same temperature reading even if they are not in contact

Sep-16 EO: Thermodynamics-LO2 6

 Zeroth Law of Thermodynamics
 There exists for every
thermodynamic system in
equilibrium a property called
temperature. (Absolute
temperature scales: K =
273.15+oC, R = 459.9 +oF)
 Equality of temperature is a
necessary and sufficient
condition for thermal
equilibrium, i.e. no transfer of
heat.

Sep-16 EO: Thermodynamics-LO2 7

 CHANGING THE STATE OF A
SYSTEM WITH HEAT AND WORK
 Changes in the state of a system are produced by interactions
with the environment through heat and work.

 During these interactions, equilibrium (a static or quasi-static

process) is necessary for the equations that relate system
properties to one-another to be valid.

 Heat and work are transfers of energy across a system

boundary

Sep-16 EO: Thermodynamics-LO2 8

 Changing the State of a System :
Heat

 Heat is energy transferred between a

system and its surroundings by virtue
of a temperature difference only.
 This transfer of energy can change the state
of the system.
 "Adiabatic" means no heat is transferred.

Sep-16 EO: Thermodynamics-LO2 9

 Changing the State of a System:
Work
 Definition of Work
 We saw that heat is a way of changing the energy of a system by
virtue of a temperature difference only.
 Any other means for changing the energy of a system is
called work. We can have push-pull work (e.g. in a piston-cylinder,
lifting a weight), electric and magnetic work (e.g. an electric
motor), chemical work, surface tension work, elastic work, etc.
 In defining work, we focus on the effects that the system (e.g. an
engine) has on its surroundings. Thus we define work as being
positive when the system does work on the surroundings (energy
leaves the system). If work is done on the system (energy added
to the system), the work is negative.

Sep-16 EO: Thermodynamics-LO2 10

 Changing the State of a System:
Work
 Consider a simple
compressible substance
 Work done by system
𝐹𝑜𝑟𝑐𝑒
𝑑𝑊 = .[Link]
𝐴𝑟𝑒𝑎
dW = [Link]
dW = [Link]

Sep-16 EO: Thermodynamics-LO2 11

 Changing the State of a
System: Work

or in terms of the specific volume, v:

where m is the mass of the system

Sep-16 EO: Thermodynamics-LO2 12

 Changing the State of a
System: Work

 If system volume expands against a force, work is done

by the system.
 If system volume contracts under a force, work is done
on the system.
 Why pexternal instead of psystem?
 Consider pexternal = 0 (vacuum). No work is done by the
system even though psystem changes and the system
volume changes.

Sep-16 EO: Thermodynamics-LO2 13

 Changing the State of a
System: Work

 Work is a path dependent process

 Work depends on path
 Work is not a function of the state of a system

 Must specify path if we need to determine work

 Example: Work during quasi-static, isothermal

expansion of a thermally perfect gas from p1,

V1 to p2, V2 .
 Along Path a: W = 2p0(2V0 - V0) = 2p0V0
 Along Path b: W = p0(2V0 - V0) = p0V0
 [Link]
amics/thermo_3.htm

Sep-16 EO: Thermodynamics-LO2 14

 Path Functions
 Path functions are functions that
depend on the path taken to reach
that specific value.
 Examples are: w and q

Sep-16 EO: Thermodynamics-LO2 15

 State Functions
 A state function is a property whose value does not
depend on the path taken to reach that specific value.
 State functions are important as they are often
encountered in thermodynamics.
 State functions can be thought of as integrals because
integrals depend on only three things: the function, the
lower limit and the upper limit.
 Similarly, state functions as well depend on three things:
the property, the initial value, and the final value.
 Examples are: U and H

Sep-16 EO: Thermodynamics-LO2 16

 Comparison between State and
Path Functions

State Function Path Function

Independent of path taken to Dependent on path taken to
establish property or value. establish property or value.
Can integrate using final and initial Need multiple integrals and limits of
values. integration in order to integrate.
Multiple steps result in different
Multiple steps result in same value.
value.
Based on established state of
Based on how state of system was
system (temperature, pressure,
established.
amount, and identity of system).
Normally represented by an Normally represented by a
uppercase letter. lowercase letter.

Sep-16 EO: Thermodynamics-LO2 17

 4 types of thermal processes
An isobaric process is a process that occurs at
constant pressure.

An isochoric process is a process that occurs at

constant volume.

An isothermal process is a process that occurs at

constant temperature.

An adiabatic process is a process during which no

energy is transferred to or from the system as [Link].
 4 Thermal Processes

An isobaric process is one that

occurs at constant pressure.

W  Fs  P As   PV

Isobaric process: W  PV

 4 Thermal Processes

Example: Isobaric Expansion of Water

One gram of water is placed in the cylinder and
the pressure is maintained at 2.0x105Pa. The
temperature of the water is raised by 31oC.
The water is in the liquid phase and expands by
the small amount of 1.0x10-8m3.
Find the work done and the change in internal
energy.
 4 Thermal Processes

W  PV
  
 2.0 10 5 Pa 1.0 10 8 m 3  0.0020 J

U  Q  W  130 J  0.0020 J  130 J

   
Q  mcT  0.0010 kg  4186 J kg  C 31 C  130 J
 4 Thermal Processes

isochoric: constant volume

U  Q  W  Q

W 0
Why is work equal to 0 for an isochoric process?
Thermal Processes Using an Ideal Gas

ISOTHERMAL EXPANSION OR COMPRESSION

Isothermal expansion or
compression of an ideal gas

Vf 
W  nRT ln  
 Vi 
 Thermal Processes Using an Ideal Gas

Example: Isothermal Expansion of an Ideal Gas

Two moles of the monatomic gas argon expand

isothermally at 298K from an initial volume of
0.025m3 to a final volume of 0.050m3. Assuming that
argon is an ideal gas, find
(a) the work done by the gas,
(b) the change in internal energy of the gas, and
(c) the heat supplied to the gas.
 Thermal Processes Using an Ideal Gas
Vf 
(a) W  nRT ln 
 Vi 
 0.050 m 3 
 2.0 mol8.314 kJ mol  K 298 K  ln   3400 kJ
3 
 0.025 m 

(b) U  32 nRTf  32 nRTi  0

(c) U  Q  W

Q  W  3400 kJ
Thermal Processes Using an Ideal Gas

ADIABATIC EXPANSION OR COMPRESSION

Adiabatic expansion or compression of a

monatomic ideal gas

W  32 nRT f  Ti 
 CYCLES

1. Rankine Cycle (Steam)

2. Vapor Compression
Cycle (Refrigeration)
3. Otto Cycle (Gasoline
Engine)
 Basic Cycles

Power Generation Refrigeration, Air-

(Heat Engine) Conditioning, Heat Pump
 Basic Cycles: Definitions
Cycle: Series of processes that eventually brings the
system back to its original state
Power Cycle:
• A cycle that uses heat energy to do work on the surroundings
• Performance is measured by thermal efficiency, which is the ratio of
useful work output to the energy input required to run the cycle:
work done BY system
work done ON system

Wnet Wout  Win

th  
Q in Q in heat OUT OF system
Q net Q in  Q out
 
Q in Q in heat INTO system
 Carnot Cycle
A B
Carnot Cycle:
(1) Theoretical implementation of a
cycle without any irreversibilities
(2) Work output is the maximum
possible for any heat engine
due to reversible processes D C

Processes
A to B: isothermal expansion of saturated liquid to saturated vapor
B to C: isentropic expansion of vapor (Q = 0; s = 0)
C to D: isothermal compression of vapor
D to A: isentropic compression of vapor (Q = 0; s = 0)
 Carnot: P-v and T-s Diagrams

B A B
A

D C
D C

Carnot Efficiency: cold reservoir

TH  TL
temperature
TL
th,Carnot   1
TH TH hot reservoir
temperature
 Problem 1
Given: A Carnot engine receives 100 kJ of heat from a hot reservoir at 370 oC and
rejects 37 kJ of heat. Determine the temperature of the cold reservoir.
TH
Analysis: Q net Q H  Q L 100 kJ  37 kJ
 th   
Qin QH 100 kJ QH
th  0.63 or 63% W

TH  TL TL
th,Carnot   1
Use absolute TH TH QL
temperatures! 
TL  TH  TH th,Carnot TL
TL  (370  273)  370  2730.63

TL = 237.91 K = -35.09 oC

 Problem 2
Given: What is the maximum thermal efficiency possible for a power cycle
operating between 600 oC and 110 oC?
Analysis:
Carnot yields maximum possible efficiency
TL
th,Carnot  1
TH

th,Carnot  1
110  273K
600  273K


th,Carnot  0.561 or 56.1%


 Problem 3
Given: A heat pump takes heat from groundwater at 7 oC and maintains a room at
21oC. What is the maximum coefficient of performance possible for this heat
pump? upper limit of heat pump is set
Analysis: by a Carnot heat pump cycle
TH QH QH TH
COPheat pump   
QH W Q H  Q L TH  TL
W
COPheat pump 
21  273K
21  273K  7  273K
QL
COPheat pump  21
TL
How does a refrigerator COP differ?
 Rankine Cycle
Rankine Cycle:
• Vapor-power cycle commonly used in power
plants with water as the working fluid
• Efficiency is ratio of useful output to required
input:
Wnet h1  h 2   h 4  h 3 
 th  
Qin h1  h 4 
Processes
1 to 2: Isentropic expansion of the working fluid through the turbine from saturated
vapor at state 1 to the condenser pressure (Q = 0; s = 0)
2 to 3: Heat transfer from the working fluid as it flows at constant pressure through
the condenser with saturated liquid at state 3
3 to 4: Isentropic compression in the pump to state 4 in the compressed liquid
region. (Q = 0; s = 0)
4 to 1: Heat transfer to the working fluid as it flows at constant pressure through the
boiler to complete the cycle
Rankine-Superheat
Superheat: Used to increase
the temperature of the working
fluid entering the low-pressure
turbine to reduce the wear on
turbine blades (point 3)
 Combustion Power Cycles
 Differ from vapor cycles since they cannot
return to their initial conditions
 Due to significant complexities with computing
mixtures of fuel and air, combustion power
cycles are often analyzed as air-standard cycles
 Air-Standard Otto Cycle: Hypothetical closed
system using air as the working fluid to simplify the
chemistry due to combustion
 Air-Standard Otto Cycle
Air-Standard Otto Cycle: Hypothetical closed system using air as the
working fluid to simplify the chemistry due to combustion

Processes
1 to 2: Isentropic compression of the working fluid (Q = 0; s = 0)
2 to 3: Constant volume heat addition
3 to 4: Isentropic expansion of the working fluid (Q = 0; s = 0)
4 to 1: Constant volume heat rejection
 Air-Standard Otto Cycle: Performance
Compression Ratio:
v1 v 4 v b
rv   
v 2 v3 va

compression from A to B expansion from C to D

Ideal Thermal Efficiency:

specific heat ratio

th 1 rv1k

compression ratio
 Refrigeration Cycles
• In refrigeration cycles, heat is transferred from a low-
temperature area (i.e. inside the refrigerator) to a high-
temperature area (e.g., in the kitchen)
• Since heat spontaneously flows only from high to low temperature
areas, work is required to force heat transfer
• Opposite of heat engines
• Systems:
• Refrigerator: Heat is removed from air inside
• Air conditioner: Heat is removed from air in an occupied space
• Heat Pump: Heat is supplied to air in an occupied space
• Chiller: Heat is removed from water
 Refrigeration Cycles: Performance
• In refrigeration cycles, the coefficient of performance
(COP) is used in place of thermal efficiency to measure
performance
• The COP is always the ratio of useful energy transfer to
the work input heat transfer from low-
QL temperature reservoir
COPrefrigerator,AC 
W work input

QH
COPheat pump  heat transfer to high-
temperature reservoir
W
 Modes of Heat Transfer
 All heat transfer driven by temperature difference
 Heat transfer occurs via 3 modes
 conduction (solid/fluid; molecular collision)

 depends on temperature gradient

 convection (fluid; motion)
 depends on temperature difference
 radiation (no medium needed –
electromagnetic waves)
 depends on T4
Conductive Heat Transfer
 Conduction heat transfer
 Transfer of energy by putting a hotter object in
contact with a cooler system)
 Convective Heat Transfer
 Convection heat transfer
 transfer of energy between a solid surface
and a moving fluid

Newton’s law of cooling,

h = heat transfer coefficient.
 Convective Heat Transfer
 The “wind chill” factor
is an example
 The air flow makes a
given temperature
“feel” (higher heat
loss) like a lower
temperature
 Radiant Heat Transfer
 Radiation heat transfer
 transfer of energy due to emission and absorption
of electromagnetic radiation
 Comfort in a Room

 At the same air temperature in a room

in a house it “feels” cooler in the winter
than the summer
 Why?
 Thermal Circuit Model
 A model used often to calculate the heat transfer through
a 1-D system is called the thermal circuit model
 In this model, each layer is replaced by an equivalent
resistor called the thermal resistance
 For conduction,

 For convection,
Example