Mec1058

Energy auditing and management

Week 5 Thermodynamics 1
Section overview

• Thermodynamic definitions
• First and Second laws of Thermodynamics
• Exergy
− Dead state
− Physical exergy
• Exergy/Second Law Analyses
• Practical rules for improving thermodynamic
performance
Recommended reading list

−Cengel and Boles, Thermodynamics: An Engineering

Approach, McGraw-Hill.
https://ebookcentral-proquest-
com.dcu.idm.oclc.org/lib/dcu/detail.action?docID=71900
38&pq-origsite=primo

−Other good resources:

−Dincer and Rosen, Exergy, Energy, Environment and
Sustainable Development, Elsevier.
− Moran and Shapiro, Engineering Thermodynamics,
Wiley.
Applications of Thermodynamics

http://www.engineeringexpert.net/Engineering-Expert-Witness-Blog/thermodynamics-
in-mechanical-engineering-part-iii-refrigeration-cycles

http://www.engineeringexpert.net/Engineering-Expert-Witness-Blog/thermodynamics-in-mechanical-
engineering-part-ii-power-cycles

https://www.researchgate.net/publication/262219373_Theoretical_Analysis_of_the_Energy_Performance_of_Three_Low_Global_Warming_Pot
ential_Hydro-fluorocarbon_Refrigerants_as_R134a_Alternatives_in_Refrigeration_Systems/figures?lo=1
Applications of Thermodynamics

Widely applicable
• Chemical Plant
• Food Industry
• Pharmaceutical Industry
• Imperative for any system
involving heat, work, energy
https://www.sciencedirect.com/science/article/pii/S0360544216307277#fig1

http://web.mit.edu/16.unified/www/SPRING/propulsion/notes/node27.html
Thermodynamic definitions

• Some engineering disciplines tend to have their own

way of doing things and can be quite specific
(pedantic?) in the language and definitions they use
and their problem solving approach

• Mechanics – free body diagrams, application of

Newton’s laws etc.
• Material Science – phase diagrams, stress/strain
graph, mechanical properties of materials
Thermodynamic definitions

• Thermodynamics is no different

• Classical thermodynamics versus Statistical

thermodynamics

• Heat transfer and fluid mechanics vs. thermodynamics

– slight variations in symbols, conventions (but not
contradictory)
Thermodynamic System
• A system is a quantity of matter or a region in space
chosen for study (Cengel and Boles).

• A system or region in space is surrounded by a boundary

that may be real or imaginary.

• Boundary can be fixed or moveable

• Boundary has zero thickness, so mathematically it has zero

mass nor does it occupy any volume in space

• Choice of boundary is somewhat arbitrary as it depends on

what you want to study

• Useful source:

https://web.mit.edu/16.unified/www/FALL/thermodynamics/not
es/node11.html
Thermodynamic definitions

−System examples
− Could be one simple process (e.g. heat exchanger) or could
be an entire plant (chemical plant, water purification plant,
power plant)
− Could be a body of fluid within a rigid tank or could be a
pipeline containing fluid (gas/liquid)
− External to the system is called the surroundings (and the
environment)
− The system and its surroundings are separated by a
specified system boundary
− Somewhat arbitrary choice - choose for convenience where
possible
Thermodynamic System
• Chosen system can be large and complex with multiple
processes or it can be simple (e.g. water in a pot)
Thermodynamic definitions

System choice governed by two considerations

1. What we know about the system (and in particular

what we know at the system boundary)

1. What we want to determine in our analysis

Thermodynamic definitions

• Closed System
− Fixed quantity of mass – no transfer of mass (matter) across
the system boundary (transfer of heat, work but not mass)
− Specific closed system that does not interact in any way with
its surroundings is called an isolated system (no transfer of
heat, work or mass)

• Open System (Control Volume)

− Mass transfer across the system boundary or a region of
space through which mass flows
− e.g. pump/turbine/heat exchanger
Thermodynamic definitions

Compressor is a Control
Volume
Source: Cengel and Boles
Consider the gas as our system
Closed system
Fixed and moving boundary

Open system (often referred to as a control volume)

Fixed and moving boundary
Thermodynamic definitions
Classical thermodynamics
• Continuum hypothesis
− Matter is distributed continuously throughout a region (in
agreement with actual measurement data for many engineering
systems)
− Allows us to talk of system intensive properties at a point: treat
properties a point functions e.g. density of a gas in a container,
velocity of a fluid
− Macroscopic level – observations of the overall system and the
effects of that system

Statistical thermodynamics
− Microscopic level – to characterise the average behaviour of
particles making up the system using statistical means
Thermodynamic definitions

Use absolute pressure and temperature in thermodynamics equations (differences in T)

 Thermodynamic definitions

−
Thermodynamic definitions
• State
− Refers to the condition of a system as described by its properties
− May require a subset of properties to define the thermodynamic state
(e.g. water boils at a specific temperature only when it is at a specific
pressure)
− State postulate: It has been found that the state of a pure substance in
equilibrium is completely defined if any TWO independent intensive
properties of the substance are known.

• Process
− Transformation from one state to another

• Steady state
− None of the system properties change with time (can have different
property values within a system but the property value at each location in
the system remains constant)
Thermodynamic definitions

Steady state: property values can vary spatially in the system but
each property value does not vary with respect to time.

Spatial but not temporal variation.

Thermodynamic definitions

• Thermodynamic cycle
− A sequence of processes that begins and ends at the same
state (e.g. refrigeration cycle or steam cycle in a power plant)

• Phase
− Liquid, gas and solid
− A system may contain one or more phases
Phases: solid, liquid, gas
Liquids and gases are
collectively called fluids

Phase changes very

important in thermodynamics

Couple of things to note:

• Gas often referred to as
vapour
• We will consider pure
substances
• Water, refrigerants
• Air (N2, O2, CO2, H2O
etc.)

Phase changes
Triple point of water: three phases co-exist: 273.16K, 611.7 Pa

https://www.youtube.com/watch?v=Juz9pVVsmQQ
Thermodynamic definitions
−
Thermodynamic definitions

• Equilibrium
− Idealised and studied as quasistatic (quasiequilibrium)
processes

− A system passes through a series of equilibrium states (an

idealisation)

− Qualitative information about system behaviour (similar to

using simplifications such as a point mass or frictionless
pulley to simplify mechanics models)
Thermodynamic definitions

−
(Atkins, P., The Elements of Physical Chemistry)
 Be consistent in
your choice of units
- in this case it
makes sense to use
kmol because the
units for the
molecular weight
are in kg/kmol

Molar quantities are often denoted by an over bar

Specific enthalpy

Molar enthalpy
Problem solving approach
− General approach of engineering disciplines is very similar
− Clear problem statement (what do I want to know?)
− Identify the system/subsystem you want to study (draw a sketch of
the system and the identify the system boundary)
− Write down the information you know (e.g. property information
and relevant units at thermodynamic states)
− Identify/find any other information you may need to solve the
problem
− List any assumptions you make in your analysis
− Identify the relevant engineering/scientific principles that apply
− Solve the problem
− Assess the solution (i.e. does your answer make sense?)
− May need to revisit your initial assumptions
Problem solving approach

− Solving engineering problems using Thermodynamics

principles

− Conservation of mass principle

− First Law of Thermodynamics (Conservation of Energy)

− The Second law of Thermodynamics

First and Second laws of
thermodynamics
− First law simply states that energy is conserved.

− Second law acknowledges that although the quantity of energy is conserved

the quality (or availability) of that energy is not necessarily conserved.

− The work of Clausius and Carnot amongst others in the analyses of heat
engines showed that heat could not be fully converted to mechanical work –
entropy and entropy generation.

− Now, in comprehensive analyses, we consider both the quantity of energy

(First law) and the quality of energy (Second law).

− Combining the first and second laws of thermodynamics results in an Exergy

analysis (sometimes referred to as a Second Law analysis or availability
analysis)
First law
A number of different ways of writing the First law: for
example, you may have seen variations of the following:
• Energy can be stored, converted, transferred but is always
conserved
• In a control volume the rate of energy increase is equal to
the sum of the energy rates entering the control volume
minus the sum of the energy rates leaving the control
volume
• In steady state the sum of the energy rates entering the
control volume is equal to the sum of the energy rates
leaving the control volume
 Thermodynamic energy

− Total energy of a system (consider changes at the macroscopic level)

− Kinetic, Potential, Internal energy (U) and enthalpy (H)

• Kinetic energy (motion of the system as a whole relative to some external coordinate
reference frame)
• Potential energy (position of the system as a whole in the earth’s gravitational field)
• Internal energy (U) , specific internal energy (u)

• Internal energy – microscopic level (translation, vibration and rotation of the

molecules/atoms, chemical bonds and atomic energy associated with orbital states,
nuclear spin)
Enthalpy

• Internal energy (U)

• A very important property arises when we consider control volumes/open systems
• Work required to move a fluid element into and out of a control volume

• Given a special name Enthalpy (H in J) and specific enthalpy (h in J/kg)

Thermodynamic definition of work

• In mechanics work is defined in terms of moving a force through a distance – for example lifting a
weight

• In thermodynamics the scope is broader

− “Work is done by a system on its surroundings if the sole effect on everything external to the
system could have been the raising of a weight.” (Moran and Shapiro)

• Doesn’t necessarily mean that a weight was lifted but that sole effect could have been the raising
of a weight
• Electrical work, shaft work, moving boundary work
Thermodynamic definition of work

• Convention
− W > 0 if work has been added to or done on the system
− W < 0 if work has been done by the system (varies by text)

• Work is not a property of the system or the surroundings

− Work is an inexact differential (that is, it depends on the details of the process)

− Work at a state has no meaning

− A Property is an exact differential (does not depend on details of the process)

Thermodynamic definition of work

−
 Work Transfer
• Normal work or displacement work is work that involves only
a displacement normal to the boundary of a system.

W= ∫ Fds = ∫ pA ds
F=pA
since dV = -Ads
W= -∫ pdV
irrespective of the shape
of the boundary.

Consider work done by the

gas – what is different? W=Fxd
Thermodynamic definition of work

• Power is the time rate of work

− (Very often in thermodynamics problems we determine a ‘specific’ quantity of interest, e.g. specific
enthalpy (kJ/kg) and we multiply by the mass flow rate (kg/s) to get kW (units are very important –
always check dimensional accuracy)

− Examples:
• Combustion engine – work rate done by expansion of gas
• Turbine – Electric power generated
• Power transmitted by a shaft (Torque X angular velocity)
Thermodynamic definition of heat

• Convention
− Q > 0 if heat has been added to the system
− Q < 0 if heat has been removed from the system

− Heat is the transfer of energy by means of a temperature difference and occurs only in the
direction of decreasing temperature
• Transfer by conduction (Fourier’s law of conduction), convection (Newton’s law of cooling) and
radiation (Stefan-Boltzmann law)
• Heat is not a property of the system or the surroundings
− Heat is an inexact differential (that is, like work, it depends on details of the process)

− Rate of heat transfer given by

− Should never be evaluated as an exact differential, e.g. not

− Heat at a given state has no meaning

Thermodynamic definition of heat

− Is heat transfer negligible?

• Good system insulation

• Small heat transfer surface area
• Small temperature difference between the system and its surroundings
Energy balance for closed system

−Example:
− Four kilograms of a gas is contained within a piston-cylinder assembly. The gas
undergoes a process for which the pressure volume relationship is as follows:

− The initial pressure is 3 bar, the initial volume is 0.1 m3, and the final volume is 0.2 m3.
The change in specific energy of the gas in the process is u2-u1= -4.6 kJ/kg. Kinetic and
potential energy are negligible, determine the heat transfer for the process.
Example solution

−
Example solution

−
Energy balance for cyclic processes

• Cyclic processes very common

− Power cycles

− Heat pump cycles (note that COP always>1)

Q in condenser

− Refrigeration cycles
Q in evaporator
Remember that a thermodynamic cycle is a sequence of processes
that begins and ends at the same state
Energy balance for open system
(control volume)
We generally talk in terms of rates for control volumes,
the energy rate is the mass flow rate multiplied by the
specific energy and so forth

Sum of the flow rates, more correctly

inlet

outlet

One inlet, one outlet tank

Energy balance for control volume
(open system)
3 common assumptions in practice
• Steady state
• Incompressible fluid model
• Ideal gas

−Naturally these assumptions must be assessed on a

case by case basis
Energy balance open system
Incompressible substance model (First Law)
• The specific internal energy varies only with temperature
• Effectively, the density is constant with respect to
pressure
• This holds true for many cases of interest
Incompressible substance model (First Law)

Let us consider changes in enthalpy

Ideal gas law
− Very often gases are assumed to behave ‘ideally’.

− What do we mean by ideal behaviour?

1. Gases consist of molecules in random motion that obey

the laws of mechanics
2. The number of molecules is large but the volume occupied
by the molecules is negligibly small relative to the volume
occupied by the gas
3. No appreciable forces act on the molecules except during
collisions
Ideal gas law
− What does this mean for us?
− Mathematically ideal gases will obey the ideal gas model.
− Ideal gas model:

− In reality gases do often approach ideal gas behaviour

(particularly at high temperature and low pressure).
Ideal gas law

−Important ideal gas law considerations

−Ideal gas:
 Retrieving thermodynamic properties
−Our thermodynamic states of interest in this course are
generally fixed by two independent properties
−Mixture region: may require dryness fraction x
−Assumed that you are comfortable retrieving
thermodynamic properties from the steam tables (e.g.
applications relating to air, water, refrigerants): P-v
diagrams, interpolation etc.
Example: compressed air
Air at 100 kPa and 280 K is compressed steadily to 600 kPa and 400 K. The
mass flow rate of the air is 0.02 kg/s. A heat loss of 16 kJ/kg occurs during the
process. Taking the compressor is the system; assuming steady state; that air is
an ideal gas; and that KE and PE are negligible, determine the necessary power
input to the compressor.
Example
Property data for air
(Cengel and Boles)
Example: steam turbine
−
Example: steam
−
Example: steam
−
Example: steam
−
 Second law
• Definite direction for
spontaneous processes
• Certain processes take
place spontaneously but
the inverse process does
not happen
spontaneously
• Require device to cause
the inverse process
• Need fuel/electricity to
power that device
• Not every process that
obeys the First law can
occur
 Second law
• Opportunity to do useful work for the aforementioned
spontaneous processes
• Energy could be delivered by heat transfer to a power
cycle
• High pressure stream could be passed through a
turbine to produce work
• The falling weight could be used to lift another weight
“…when an imbalance exists between two systems, there is an
opportunity to develop work that would be irrevocably lost if the systems
were allowed to come into equilibrium in an uncontrolled way”. (Moran
and Shapiro)
Second law
− Couple of key questions:
• What is the maximum theoretical work that could be developed?
• What are the factors that would preclude the realisation of the
maximum value?

− Second law:
• Predicts the direction of processes
• Establishes conditions for equilibrium
• Determines the best theoretical performance
• Quantifies the factors that preclude the attainment of best
theoretical performance
Second law statements
Clausius statement:
− It is impossible for any system to operate in such a way that the
sole result would be an energy transfer from a cooler to a hotter
body.
(Think of heat pump/refrigerator – requires work input in the form of
compressor)

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.
(Think of a power cycle – heat rejected at a lower temperature)
Second Law statements

(Kelvin-Planck) (Clausius)
Second Law statements

Hot Qin Hot Qout

body body

System Wcycle=Qin-Qout System Wcycle=Qout-Qin

Cold Qout Cold

body body Qin

Kelvin-Planck statement Clausius statement

Irreversibilities
• Every real process involves irreversibilities
• Best theoretical performance can be determined for an
idealised process
• This can be compared to actual performance

− “A process is called irreversible if the system and all parts of

its surroundings cannot be exactly restored to their
respective initial states after the process has occurred.”
(Moran and Shapiro)

− Drive your car to Belfast

Irreversibilities
• As a system undergoes a process, irreversibilities may be
found within both the system and the surroundings

• Internal irreversibilities are irreversibilities that occur within

the system

• External irreversibilities are those that occur in the

surroundings (often the immediate surroundings)

• Somewhat arbitrary as it depends on the system boundary

location
Common Irreversibilities
• Heat transfer through a finite temperature difference (e.g.
heat exchanger)
• Unrestrained expansion of a gas or liquid to a lower
pressure (e.g. throttling valve)
• Spontaneous chemical reaction
• Spontaneous mixing of matter at different compositions or
states (salinity gradient systems)
• Friction – sliding friction and friction in fluid flow
• Electric current through a resistance
• Magnetisation or polarisation with hysteresis
• Inelastic deformation
 Irreversibilities
• Try to be aware of and recognise irreversibilities
• Tolerated to some degree because the cost of re-
design may be prohibitive
• Naturally there is a trade-off between the presence of
irreversibilities and economics
Heat exchanger cost curve, adapted from Moran and Shapiro.

Important to note that what

may be prohibitive today may
not be so in the near future
due to rising electricity/fuel
costs.
Entropy
Formal definition of entropy change

Entropy is defined in terms of an integral, note that no

physical picture is painted. However, as we will see, it is very
useful in thermodynamic analysis. We will see its important
applications, i.e. how it is used and what it is used for.
entropy
Thot res
Q
Tcold res

−
Entropy

• Entropy, like enthalpy, is a thermodynamic property

and is therefore independent of the process.

• Properties are listed in the steam tables for

water/steam and other common refrigerants

• Entropy, S, units J/K or conveniently kJ/K

• Specific entropy, s, units J/kg.K or kJ/kg.K

 Using entropy
−
 Using entropy
−
Draw a sketch
Using entropy

(Source: http://www.qrg.northwestern.edu/thermo/design-library/refrig/refrig.html)

From here we develop the ‘Tds’ equations

Using entropy
Using entropy
− The TdS equations are developed by considering a pure,
compressible system undergoing an internally reversible process.
Consider the following closed system energy balance:

− This is known as the first TdS equation

Using entropy

This is known as the second TdS equation

TdS equations

− Although they have been derived for an internally reversible

process, if we integrate the TdS equations we can
determine the entropy change for any process between two
equilibrium states.

− We consider these equations for an ideal gas and an

incompressible substance.
 TdS equations
−

What is R again and where

can I find information for R?
TdS equations

−
Entropy balance closed systems
Entropy balance closed systems
Entropy balance closed systems
Entropy balance for open systems
(control volumes)

Entropy generation
Entropy transfer
Entropy balance (open systems)
− Example: Data are provided for a device that at steady state produces hot and
cold streams of air from a single stream of air at an intermediate temperature
without energy transfers by work or heat. Evaluate whether the device can
operate as claimed. Sixty per cent of the mass entering the device exits at the
lower temperature. Air can be modelled as an ideal gas with a constant
specific heat capacity:
How can I go from
the earlier equation
for an ideal gas
below to version
on the left?