MODERN THERMODYNAMICS MACE11005

SHORT HANDBOOK

First Year BEng/MEng Mechanical/Aerospace Engineering

Lecturer: Dr Amir Keshmiri

Telephone: 0161 306 5752

Office: C42, George Begg Bld.
Email: a.keshmiri@manchester.ac.uk

Acknowledgements
The lecture notes presented herein are founded on
an original set of lecture notes composed by Dr R.
Prosser, School of Mechanical, Aerospace and Civil
Engineering, University of Manchester.
 BASIC CONCEPTS IN THERMODYNAMICS
Introduction
Among the multitude of laws that described the workings of the universe there exists some whose importance
transcends all others. The isolated phrase “the second law” is often sufficient information in itself to inform the
intended audience that the second law of thermodynamics is meant. Thermodynamics defines and describes the
properties of energy and its transformation from one form to another. Thus, thermodynamics is not simply about
steam engines but applies to every aspect of physics invoking energy transport; put simply, it applies to all the
sciences, be it chemical, electrical, mechanical, nuclear, and including natural sciences. As engineers we are often
concerned with the analysis, workings and design of large scale systems such as power plants, heat engines,
refrigerators, air conditioning, heat pumps etc. and consequently our focus (and the focus of thermodynamics) is on
the macroscopic rather than the microscopic although an atomistic viewpoint (describable by statistical mechanics)
can sometimes illuminate our conceptual understanding.

Thermodynamics is founded on just four laws:

(i) The Zeroth Law establishes the familiar yet enigmatic property temperature T [K].
(ii) The First Law establishes the property internal energy U [kJ].
(iii) The Second Law establishes the (often considered recondite) property entropy S [kJ/K].
(iv) The Third Law establishes a barrier that prevents the reaching of the temperature absolute zero [K].
The first and second laws are the most useful for practical purposes as they provide us with transport equations
which can be applied to a moving/stationary control volume, which encompasses the thermodynamic system. The
invariance of energy (in an isolated system) is the preserve of the first law but what energy changes are permitted is
the preserve of the second.

Definition of a System: Thermodynamics (as with the rest of science) takes familiar words and confers upon them
an exact and unambiguous meaning.
(i) A system is a collection of matter enclosed within a prescribed boundary.
(ii) A closed system is a system distinguished by the absence of matter flowing across its boundary.
(iii) An open system is a system distinguished by matter flowing across it boundary.
(iv) A system is separated from its surroundings by a boundary. The boundary may be fixed or may move
to contain the prescribed matter.
(v) The surroundings are everything not contained within the system boundaries. The surroundings can
often be considered vast, unaffected by the system (e.g. a bath of water, the atmosphere, the world, our
solar system, the universe).
(vi) An isolated system is a system distinguished by the absence of energy flowing across its boundary.
(vii) A control volume is commonly used in the analysis of open systems and is typically defined to
encompass the space occupied by an open system. The boundary of the control volume is denoted the
control surface and matter is free to flow across this boundary.

Definition of a Property: A property is any quantity whose change is fixed by the end states, and is independent of
the path between the end states.
An essential feature of a property is that it has a unique value when a system is in a particular state and that this
value does not depend on previous states the system may have passed through. Thus a property is not dependent on
2
path and this can be represented mathematically by the equation:  1
d  2  1 , where  is the property and 1
is the value of the property at state 1, 2 is the value at state 2 and 2  1 represents the change in the property as
the system moves from state 1 to state 2.
The state of a system is its condition as described by giving values to its properties at a particular instant. The two-
property rule states that the state of a simple (e.g. consisting of a pure substance) closed system of constant mass is
defined by two independent properties. Pressure and volume are commonly used to define the state of a gas for
example.
Thermodynamic properties can be further divided into intensive, extensive and specific properties. Intensive
properties are independent of the mass of the system. Extensive properties depend on the mass (or extent) of the
system. Specific properties are a subclass of intensive properties obtained on division of extensive properties by the
mass.

Definition of a State: The state of a system is a complete description of all the properties of the system, i.e. both the
mechanical and thermodynamic properties. A simple system is defined by its volume, pressure, velocity and
position.
 BASIC CONCEPTS IN THERMODYNAMICS
Important properties:
Pressure p: Pressure is the force per unit area exerted by a system on its surface in the direction normal to that
Fn
surface. Mathematically this can be defined as: p  lim , where Fn is the normal component of force
A0 A

acting on the small surface area A . It is important to appreciate that in the vast majority of thermodynamic
relationships absolute pressure is used, i.e. p  pabs  pgauge  patm , where pgauge is gauge pressure (measured
with a pressure gauge) and patm is atmospheric pressure (measured with a barometer).
Density : Density is a continuum concept and is defined as mass per unit volume:   lim  m V  , where
V 0

m is the mass in the small region with volume V . The units of density are kg/m3.
Specific volume  : Specific volume is the reciprocal of density. The units of specific volume are m3/kg.
Temperature (t or T): Temperature is a measure of molecular activity but since classical thermodynamics deals
with macroscopic properties, molecular definitions are not that useful. Temperature is a property introduced by
thermodynamics (the Zeroth law) and since temperature differences drive thermodynamic processes it is the most
important property for the study of this subject. Temperature is a measure of how "hot" or "cold" a body is.
However, in making that measurement it is important that the device used for measuring the temperature is in
thermal (temperature) equilibrium with the body. Various (somewhat arbitrary) temperature scales have been
established. Celsius [0C] (formally called centigrade) and Fahrenheit [ 0F] are related by
9 5
t F  tC  32 [0F] or tC   tF  32  [0C]
5 9
chosen to have 100 0C (180 0F) between the ice (freezing) point (0 0C, 1.013 bar) and the steam (boiling) point
(1000C, 1.013 bar) of water.
Absolute (continuous) scales can be established with the help of the second law, Kelvin [K] and Rankine [0R] and
take the form
5
TR  tF  459.67 [0R] and T  tC  273.15 [K]; it follows that T  TR , where T  0 K ( TR  0 0 R )
9
denotes absolute zero, where loosely speaking, all molecular activity stops.
The only way to obtain an accurate measurement of temperature (by a contact method) is when the measuring device
and the system being measured are at the same temperature; this is referred to as being in thermal equilibrium.

Definition of a Process:
Path: If a system changes state slowly (compared to the reaction time of the system) it passes through a series of
equilibrium states called a path.
Process: The path through the succession of equilibrium points is called a process. The process is defined by the two
end states and the path.

Thermal equilibrium: Consider if systems A and B are not at the same state initially. If they are brought into
contact with a diathermal wall then their states will spontaneously change until they ultimately reach a steady state:
this steady state is called thermal equilibrium.
Zeroth law of thermodynamics: If three systems are brought into contact through a diathermal wall, then the
following statement can be made after some time.
 A and C are in thermal equilibrium
 B and C are in thermal equilibrium
hence
 A and B are in thermal equilibrium, even though they are
connected through an adiabatic wall.
This leads directly to the Zeroth law of thermodynamics

Two systems are in thermal equilibrium with each other if they are both in
thermal equilibrium with a third system.
It is evident that system A and system B must have a common property
which is given the name temperature. A system is in thermal equilibrium if
and only if its temperature is uniform. Moreover, systems in thermal
equilibrium with each other are said to be at the same temperature.

MODERN THERMODYNAMICS
 WORK AND HEAT
Introduction
Understanding the first law of thermodynamics requires some familiarisation with two quantities of energy transfer
across the boundary of a system: work and heat. Work is considered in some detail but heat is covered in somewhat
broader terms since detailed analysis is beyond the scope of a first level module (examined further in the third year).
The first law is often considered to be relatively benign (i.e. easy to understand) by students being an extension of
the law of conservation of energy, which infers that energy can neither be created nor destroyed, i.e. whatever energy
was present at the start of the universe remains the same and will remain invariant until its end. However,
thermodynamics is a subtle subject and like the zeroth law (which inferred the existence of the property temperature)
the first law infers the existence of a property (termed energy); there is no requirement for us to assume a priori that
the property energy exists. It transpires that energy is a property of a system yet work and heat are not. Is this
obvious? How can it be shown? How do we quantify work and heat if they are not properties?
Both work and heat are described by their interaction between the system and its surroundings. For a closed system
the flow of energy between a system and its surroundings principally takes only one of two forms and these forms
are work and heat. But if it is true that work and heat are merely forms of energy transfer, then what distinguishes
them?
Work is motion against an opposing force and in mechanical terms is the product of force times the distance moved
in the direction of the force. In thermodynamic terms however all types of work can be shown to be equivalent to
raising a weight in a gravitational field. Heat on the other hand is energy transfer resulting from a temperature
difference. Prior to examining these issues in detail it is prudent at this point to introduce the first law, which for a
closed system in mathematical terms is:
dU   Q  W (or dU   Q  W ) depending on the sign convention used for positive work.
The first law relates an increment in energy dU (a property) to increments in heat  Q and work  W which are
not properties (the notation reflects this). Surprising as it appears the expression  Q   W is a property despite
 Q and  W not being so.
Moreover, the notation used here (i.e. d and  ) requires some explanation but note that (for a non-quasi-static
process, i.e. a real process involving time) dU  Udt ,  Q  Qdt and  W  Wdt with dt an increment of time
dU
and U but it WOULD NOT BE CORRECT to replace the heat and work rates Q and W with derivatives
dt
dQ dW
and , respectively; the use of the symbols d and  reflects this. It is appreciated however that these
dt dt
nuances require further explanation but are introduced here merely to illustrate that the first law is not as obvious as
it first appears.
Thermodynamic definition of Work: Work is done by a system when the sole effect on everything external to a
system (the surroundings) would be the raising of a weight.
Quasi-Static Processes: The thermodynamics of principal concern in this course is essentially equilibrium
thermodynamics. Equilibrium in this case means that, in the absence of external stimuli, the thermodynamic state of
the system will not change spontaneously.
Quasi-static change in a system is change that takes place whilst maintaining equilibrium. On a practical level such
changes take place very slowly.
The Effect of Work on the Surroundings: work is a kind of energy transfer. Energy can neither be created nor
destroyed, merely transferred, so
 If work is done by a system, it is done on the surroundings.
If Wsys  0 then Wsurr  0 and Wsys  Wsurr  0
 If work is done on a system, it is done by the surroundings.
If Wsys  0 then Wsurr  0 and Wsys  Wsurr  0
where Wsys and Wsurr represent the work done by the system and surroundings, respectively.
‘Mechanical’ work is the type of work covered in A-level and introductory mechanics modules.
Wm  F  du   F1i  F2 j  F3k    dui  dvj  dwk   F1du  F2dv  F3dw  F du cos
where  is the angle between the vectors F and du .
Displacement work: In thermodynamic systems, one of the most common types of work is displacement work:
 WD  pdV .
Work done in creating a surface:  WS  dA , where dA is the surface area created and  is surface tension.
Shaft work:  Ws  Td , where T is the torque acting on the shaft.

Polytropic processes capture many practical compression/expansion processes that satisfy the relationship
pV n  constant , where typically 0  n   .
or equivalently pv  constant , which obtained on dividing through by m for mass m. The constant n is called
n n

the polytropic index of expansion or compression (or simply polytropic index).

1
 Process n  0 takes place at constant volume. (isochoric)
 Process n  0 takes place at constant pressure. (isobaric)
 If pV  mRT (or pv  RT ), then process n  1 takes place at constant temperature. (isothermal)
 If n   , where  is the ratio of specific heats (adiabatic index), then process takes place at constant
entropy. (isentropic)
p1v1  p2v2 p2v2  p1v1
Displacement work in a polytropic process: w12   or
n 1 1 n
   
w12  p1v1 ln  2   p2v2 ln  2  for n  1
 1   1 
Note that since work done per unit mass is the area under a p-v curve. Thus, it is evident that different paths between
two states will give different values for work; hence work is not a property.

Heat
Heat (transfer) is the interaction between systems which occurs by virtue of temperature differences.

1. Heat interactions are associated with energy transfers

2. Heat interactions are transitory phenomena.
3. Heat is energy transmitted across a boundary.
4. Heat is NOT a quantity of energy contained in a system.
5. If two points at different temperatures are brought into contact, then heat is the energy transferred; the process
ceases when the temperatures are equal (Zeroth Law).
6. Heat is not a property.

Sign Convention and Units:

In this course, the following sign conventions are adopted.
 Heat into a body is positive;
 Heat out of a body is negative
which are opposite to those adopted for Work. As with work, total and a specific heat transfer can be defined. The
Q
capital letter Q is reserved for total heat transfer, and use a lower case q for the specific heat transfer, i.e. q  ,
m
where q is the heat transfer associated with 1kg of working fluid. The standard SI unit of heat is the Joule.
Remember that 1J  1Nm . This emphasises the similarity between heat and work.
Appreciation of Magnitudes:
1. 1Cal = 4.1868 J (Cal = Calories)
2. 1 kilocalorie (kcal) is the amount of energy required to raise the temperature of 1 kg of water by 1 C, when
the water is initially at 15C.

Heat Processes on State Diagrams:

Provided the heat transfer takes place infinitely slowly (to avoid temperature gradients), the system will have well
defined, single values for pressure, temperature etc. Consequently, it is possible to draw the process on a state
diagram.

MODERN THERMODYNAMICS
 THE FIRST LAW AND ENERGY TRANSPORT
Introduction
As mentioned in previous notes the first law of thermodynamics gives rise to intrinsic internal energy U. However, it
gives no indication to what U actually is other than it being a property of a system. In this respect it is rather similar
to the zeroth law which establishes temperature yet gives little insight to what temperature actually is. Further
insight about temperature, work heat and energy can be gleaned on consideration of the molecular world. Quantum
mechanics reveals that energy is not continuous but is discrete. From this point of view temperature is the parameter
that determines the most probable distribution of populations of molecules over the available energy states of a
system at equilibrium. Work on the other hand is a form of energy transfer that makes use of the uniform motion of
atoms in the surroundings (movement of piston, lifting of a weight, etc.). Similarly heat is the form of energy transfer
that makes use of the random motion of atoms in the surroundings. Thus work is organised energy transfer and heat
is random and this distinction is worth bearing in mind. Energy associated with molecules can be viewed in purely
mechanical terms (neglecting nuclear and chemical) and U is no more that a measure of the potential and kinetic
energy of molecules although classical thermodynamics makes no reference to this fact. It is established in this
section that U is a property of the system, i.e. it does not depend on path. Thus whilst energy can be transferred to a
system by means of work and heat, once the energy is inside a system then the system has no “knowledge” of how
the energy was transferred. The system has no “knowledge” of the past (is not history (path) dependent) which is of
course what defines a property. Distinguishing between heat and work is done in the surroundings, i.e. raising or
lowering temperature or lifting or lowering a weight.

The First Law of Thermodynamics

The equivalence between work and heat (from the point of view of its effect on a system) was established by Joule
between 1840 and 1848. Joule was led to postulate the First Law of Thermodynamics.
When a system executes a cyclic process, the algebraic sum of the work transfers is proportional to the algebraic sum

 J δQ W  0 , where J
~
of the heat transfers. The First Law of Thermodynamics applicable to a cycle is: is a
constant referred to as the mechanical equivalent of heat.
Corollary 1: There exists a property of a closed system such that a change in its value is equal to the net heat and
work transfers occurring during any change of state. This property is called the internal energy and is denoted by
U.
2 2
Q12  W12    Q    W  U 2  U1
1 1
Corollary 2: The internal energy of a closed system remains unchanged if the system is isolated from its
surroundings.
Corollary 3: A perpetual motion of the first kind (a PMM 1) is impossible.

The general form of the First Law

2
Q12  W12    Q   W   E2  E1  E    E p  Ek  U   E p   Ek   U
1

where kinetic energy Ek  12 mv2 &  

Ek  12 m v2 2  v12 , potential energy E p  mgz &

E p  mg  z2  z1  , intrinsic internal energy U  mu & U  m  u2  u1  , which on substitution gives

 v2   v2 
Q12  W12  m  gz2  2  u2   m  gz1  1  u1   m  e2  e1  .
 2   2 
This is the most general form of the First Law on the 1st year course and on dividing through by m gives
q12  w12  e2  e1
where q1 2 and w1 2 are the specific heat and work transfers (i.e. the amount of heat and work transferred
per unit mass in the system).

The differential form of the first law

An alternative, equivalent formulation can be written as (in terms of specific quantities)

 q   w  de  gdz  d  12 v2   du
 THE FIRST LAW AND ENERGY TRANSPORT
which is the differential form of the first law. The advantage of this latter form is that it is often possible to write q
and w in terms of state variables and thereby obtain analytic relationships between the heat and work transfers, and
the internal energy.

Rate forms of the First Law

Rate forms of the first law are not directly applicable to quasi-static processes since rates are invariably zero and time
is not an explicit feature. Nevertheless change involves the passage of time and a slowly varying process can
provide a good approximation of a quasi-static process with finite rates. The expectation here is that U can be
expressed using a volume integral whilst Q and W involve surface integrals since we have discovered that heat
and work are forms of energy transfer between a system and the surroundings. The expressions are:
U   udm , Q   qdA and W     vdA (work rate (power) considered here)
  

where dm   dV   dV ,  is density, q is heat flux (rate per unit area-see previous notes) whilst  is a
1

surface stress (i.e. force per unit area and dF  dA ). Note that a displacement power flux is of the form stress
times velocity.

The rate form of the energy equation is a rather tricky looking equation of the form
d

dt 
 u  12 v2  gz  dm   qdA     vdA (i.e. E  Q  W )
 
Specific heat capacity:
The temperature change of the working fluid is related to the heat transfer via the specific heat capacity at constant
volume, c v
q  J 
c
T  kgK 
Definition: The specific heat capacity c is defined mathematically as: , where T is the absolute

temperature and  T represents a partial derivative with respect to temperature.

 q   u 
cv       specific heat at constant volume
 T v  T 
 q   h 
cp       specific heat at constant pressure
 T  p  T  p
Integration gives
2
u2  u1   c p dT  c p T2  T1 
1
2
h2  h1   c p dT  c p T2  T1 
1

where the last term is obtained with the assumption that cv and c p are constant (generally it is a function of T ).
The specific heat capacity is not an appropriate concept when dealing with phase changes (since  q  0 with
dT  0 ).
Enthalpy
The quantity h  u  p is called the specific enthalpy of the system. The actual enthalpy for the system is
H  mh  m  u  p   U  pV
The enthalpy is a very important quantity in thermodynamics, especially in open systems. It is a quantity that
automatically captures the displacement work performed in pushing back the surroundings. It is similar to internal
energy in that it is a property (being a combination of properties U , p and V ) and has the units of energy. Its
ability to automatically capture the displacement work done in pushing back the surroundings is particularly
convenient and thus has been tabulated for many materials (see steam tables for example).

MODERN THERMODYNAMICS
 WORKING FLUIDS: PURE SUBSTANCES (VAPOURS)
Introduction
Up to this point in the course attention has been directed towards general principles, i.e. Work, Heat and the First
Law. However, in order to take on practical problems (analyse heat exchangers, boilers, engines etc.) and perform
calculations some understanding of the behaviour and properties of fluids as temperature and pressure varies is
required. This section focuses on a particular type of working fluid referred to as a vapour. A vapour is an example
of a pure substance, and includes fluids such as steam and refrigerant-12.
The three phases of H20, which are familiar to us all, are: solid (ice), liquid (water) and vapour (dry steam).
Combinations of these phases can coexist at particular temperatures and pressures and bearing in mind the two-
property rule this behaviour can be represented pictorially as an equilibrium surface on a p   T state diagram.
Note that an equilibrium surface represents the behaviour of a pure substance at equilibrium which practically means
changes that are performed relatively slowly.
The focus here is on the practicalities of reading steam tables, which require students to have access to:
Thermodynamic and transport properties of fluids (SI units 5th edition)
By G.F.C. Rogers and Y. R. Mayhew
(Blackwell publishers)
Reading Steam Tables
One of the difficulties with dealing with vapours is that their states are not usually amenable to simple analytic
expression (such as the gas laws). Therefore dealing with vapours for engineering calculations, requires the use of
steam tables.
Steam tables are a calculation tool. In the case of steam tables, the p    T surface of a pure substance such as
water, ammonia or dichlorodifluromethane is tabulated in terms of temperature and pressure.
Recall that in the introductory lectures, the two property rule was mentioned. For any homogeneous
thermodynamic system, two properties are sufficient to define entirely the thermodynamic state of that system. In
steam tables, temperature and pressure are used as the reference properties because these are the easiest to use
experimentally and practically.

Where to find what for various pure substances in the steam tables (left sketch H 2 O , right sketch for other pure
substances)
Reading properties for saturated water and steam (pages 2-5)
Along the top of page 2 you will see

t ps vg hf h fg hg sf s fg sg
 o C  bar   m3 /kg   kJ/kg  kJ/kgK
Along the top of pages 3-5, you will see
 WORKING FLUIDS: PURE SUBSTANCES (VAPOURS)
p ts vg uf ug hf h fg hg sf s fg sg
 bar   o C   m3 /kg  kJ/kg  kJ/kg  kJ/kg  kJ/KgK 
Interpolation
The steam tables do not contain entries for every possible state point on the p   T surface. Therefore, it is
often necessary to interpolate between values given in the tables. The interpolation is linear as this is accurate
enough for engineering calculations.

Fitting a straight line between y1  f ( x1 ) and y2  f ( x2 ) gives by means of similar triangles:

ya  y1 y2  y1 y  y1 xa  x1  x  x1 
 or a  or ya  y1   a  y2  y1 
xa  x1 x2  x1 y2  y1 x2  x1  x2  x1 
This formula is linear, so the procedure is referred to as linear interpolation.
Dryness Fraction
The dryness fraction (or quality) is denoted by x and is defined to be:
mg Mass of vapour in the system
x 
m f  mg Total mass in system
x0  fluid is entirely liquid just starting to boil.
x 1  fluid is dry saturated vapour just about to enter superheat region.
The dryness fraction is ONLY defined in the wet vapour region and by definition 0  x  1 . It has no meaning
to ask for the value of x either in a liquid or a superheated vapour.
Dryness fraction provides the needed measure of how far along the vaporisation process we are in a given problem.
From this point on, we use a suffix x to denote quantities at a given/desired dryness fraction x.
Consider a closed system of volume V containing H20 in the form of a wet vapour. The mass of the wet vapour is
m  m f  mg . The volume V, internal energy U, enthalpy H, entropy S can be expressed by the formulae:

 g  1  x  f  x g   f  x  g  f 
mf mg
V  m x  m f f  mg g   x  f 
m m

ug  1  x  u f  xug  u f  x u g  u f 
mf mg
U  mux  m f u f  mg ug  ux  uf 
m m

hg  1  x  h f  xhg  h f  x  hg  h f   h f  h fg
mf mg
H  mhx  m f h f  mg hg  hx  hf 
m m

sg  1  x  s f  xsg  s f  x  sg  s f   s f  xs fg
mf mg
S  msx  m f s f  mg sg  sx  sf 
m m
Each of these equations offers a formula for determining the dryness fraction x , i.e.
 x  f ux  u f hx  h f sx  s f
x or x or x or x
 g  f ug  u f h fg s fg
Bilinear Interpolation
When dealing with superheated vapours it is observed that the entries in the tables are quite widely spaced. Often it
is necessary to us bilinear interpolation, i.e. interpolation on two variables ( p & t ).

MODERN THERMODYNAMICS
 OPEN SYSTEMS AND ENERGY TRANSPORT
Introduction
The thermodynamic analyses undertaken thus far have been based on closed systems, i.e. ones in which there is
no mass flux across the system boundaries. The following various mathematical forms of the energy equations
have been considered:
 1 2  1 
Integrated form: E2  E1  U 2  mgz2  mv2   U1  mgz1  mv12   Q12  W12
 2   2 
 1 2
Differential form: dE  d  U  mgz  mv    Q   W
 2 
Rate form:
d

dt 
 
u  12 v2  gz dm   qdA     vdA (or
dEcv
dt
 Q W )
 
Transport equations for open systems
The equations above do not account for changes in energy due to mass entering or leaving the control volume 
through the boundary  .
dEcv
dt 
The rate form of the energy equation for an open system follows at is:  edm  Q  W ,

which is known as the unsteady flow energy equation (USFEE), where e  u  12 v2  gz and for the case of a
stationary control volume dm   v  ndA .
Many situations arise where energy within the control volume  is unchanging, i.e. Ecv  0 and the resulting
equation is:  edm  Q  W , which is known as the steady flow energy equation (SFEE).

Simplified forms of the flow energy equations

Identifying shaft and displacement work rates at  gives W  Ws  WD  Ws  p dm , which on substitution



into the USFEE yields Ecv  e dm  Q  Ws , where e  e  p  u  p  12 v2  gz  h  12 v2  gz , and
h h

where h is specific enthalpy. On identifying exits and inlets the USFEE simplifies to Ecv  me ee  mi ei  Q  Ws
h h

Differential forms are obtained on multiplication by dt to give

Ecv dt   eh d  mdt   Qdt  WS dt  dEcv   eh d  m    Q   Ws

Specific forms of the energy equations

The simplified rate form of the USFEE is
 v2   v2 
Ecv  me he  e  gze   mi hi  i  gzi   Q  Ws W 
 2   2 
which for the steady state case reduces (since Ecv  0 and me  mi  m ) to
 ve2   vi2 
m he   gze   m hi   gzi   Q  Ws W 
 2   2 
which reduces further on dividing through by m to
 ve2   vi2  Q WS J 
he   gze   hi   gzi     q  ws  
 2   2  m m  kg 
where in this equation, q and ws are taken to mean the heat and shaft work transfers which take place per kg of
mass passing through the system.
MODERN THERMODYNAMICS
Adiabatic machines
Recall from earlier lectures that the term ‘adiabatic’ refers to a process in which there is no heat transfer.
Examples of machines that are almost adiabatic (i.e. heat transfer is low relative to flow of energy), and that are
common to engineering processes are compressors, pumps, turbines, nozzles and even heat exchangers.
Compressors and Pumps:
Compressors are found in jet engines, air receivers, good quality paint sprayers and fridges, as well as many other
applications. As the name implies, a compressor is designed to compress gas i.e. to raise gas pressure.
Compressors do work on the fluid and hence WS  0 . Applying the SFEE to the compressor, in terms of specific

quantities gives:  h2  h1   
1 2
2
v2  v12   g  z2  z1   q  ws  h2  h1  ws .
A similar device to a compressor is a pump and the SFEE is identical to a compressor but a useful approximation
with the pumping of an incompressible liquid is: ws  h2  h1  u2  u1   p2v2  p1v1   v  p2  p1  .
Turbines:
Turbines are found in jet engines and ground based power producing plant. A turbine is designed to extract energy
from the working fluid and convert it to shaft work. Turbines are power producers, i.e. Ws  0 . Applying the


1 2
SFEE to a turbine gives q  ws   h2  h1  
2
v2  v12   g  z2  z1   ws  h2  h1 , where the simplified

form assumes 2 v  h , g z  h and q  0 .

1 2

Throttling process:
Throttling processes occur commonly in engineering, when a fluid is passed from a high pressure to a lower one.
The SFEE simplifies to h2  12 v22  h1  12 v12  h0  const. , where the term h0  h  12 v2 is called the stagnation
enthalpy of the fluid; it is the enthalpy achieved in bringing the fluid to rest adiabatically. In many cases the
velocity of the fluid does not change significantly across the throttle, and the steady flow energy equation further
simplifies to h2  h1 .
Nozzles:
The purpose of a nozzle is to convert the energy stored in the fluid (in the form of pressure) into gas velocity. The
nozzle could be considered to be adiabatic, i.e. there are no heat losses, and for each kg of mass passing through

the device, q  0 . The SFEE simplifies to he  hi   12 ve2  vi2  and in many cases, the flow upstream of the
nozzle is from a reservoir, and hence is at the stagnation condition and vi  0 . Then, the previous equation
further simplifies to: ve  2  hi  he  .
Heat Exchangers:
A heat exchanger is a device that allows heat from a fluid (a liquid or a gas) to pass to a second fluid without the
two fluids having to mix together or come into direct contact. The SFEE simplifies to
m f1  hout
f1
 hinf1   m f2  hout
f2
 hinf2   0 , arising because there is no shaft work and it is reasonable to assume
negligible heat loss to the surroundings.

Standard conservation properties across devices

Device Assumption Property conserved Identity
Turbine Reversible and Adiabatic Entropy s2  s1
Compressor Reversible and Adiabatic Entropy s2  s1
Pump Incompressible Liquid Energy and Volume u2  u1 ,  2   1
Nozzle Reversible and Adiabatic Entropy s2  s1
Throttle Irreversible and Adiabatic Enthalpy h2  h1
Heat Exchanger Negligible Pressure Drop Pressure p2  p1

MODERN THERMODYNAMICS
 WORKING FLUIDS: GASES
Introduction
This section is principally concerned with ideal gases and in particular the equation of state that relates pressure, volume
and temperature for a fixed mass of gas in a state of thermodynamic equilibrium. The equation of state (or state equation)
takes on a number of equivalent forms. The founding principle that underpins the various relationships is Avogadro’s
hypothesis, which states that equal volumes of gas at equal pressures and temperatures contain the same number of
molecules. A consequence of this hypothesis is that the equation of state can apply to many gases and one form of the
state equation is
pV  NkT
where k is Boltzmann’s constant and equals 1.38065 1023 J / K and N is the number of molecules.
This form of the equation provides a link between the microscopic and the macroscopic but is not in a form ideal for use
by engineers since it involves both large and tiny numbers. An alternative form used by chemists (arising from
Avogadro’s hypothesis) uses moles (the amount of substance) rather than N where 1 mole contains the same number of
particles as there are in 12g of carbon-12 (12C) atoms, which equals 6.022 1023 (know as Avogadro’s number) and is
the numerical value of Avogadro’s constant N A  6.022 1023 mol-1 .

The number of moles n (units of mol) for an arbitrary gas is simply n  N N A and on replacing N in pV  NkT a more
convenient equation of state is obtained, i.e.
pV  n  N Ak  T  nT ,

where  is the universal gas constant and equals   8.3145 J / mol K (or   8.3145 kJ / kmol K )
Although this form is convenient as it now contains manageable numbers it is sometimes advantageous to utilise mass m
rather than mole n. This can be achieved on definition of the molecular weight (now more correctly called the relative
molecular mass) which is a dimensionless quantity equal to the ratio of the mass of a molecule and one twelfth the mass
of a carbon-12 atom. A quantity having the same numerical value as the molecular weight for 1 mole of substance is the
molar mass M (some books confusingly refer to this as molecular weight) measured in g / mol (or kg / kmol ). It
follows that n  m M , which can be substituted into pV  nT to give

pV  m   / M  T  mRT ,

where R is the characteristic gas constant for the gas under consideration and is measured in units J / g K (or more
conveniently kJ / kg K ). Dividing the equation of state through by m gives a particularly convenient form p  RT and
similarly dividing by V gives p   RT .
It transpires that it is possible to show that both U and H for a closed system of ideal gas at equilibrium are solely
functions of temperature, i.e. U T  and H T  .

Specific Heats for Ideal and Perfect gases

An ideal (and perfect) gas satisfies the relationship u  u (T ) but recall the definition of specific heats cv and cp , i.e.
 u   h  du dh
cv    cp    , so it immediately follows that cv  and c p  , i.e. partial derivatives collapse to
 T v  T  p dT dT
ordinary differentiation. Despite this these relationships they tell us nothing about the specific behaviour of the specific
heats but evidently for an ideal gas cv  cv T  and c p  c p T  . In the case of a perfect gas (by definition) the
behaviour of the specific heats is rather simple and is restricted to that subset of gases for which:
cv  const and c p  const .
 WORKING FLUIDS: GASES
Work done on a Polytropic Process
Using the gas laws, these may be re-written as
R T1  T2  R T2  T1 
n0 w12  R T2  T1  , n 1 w12  
n 1 1 n
    p  p 
n 1 w12  RT1 ln  2   RT2 ln  2   RT1 ln  1   RT2 ln  1 
 1   1   p2   p2 
Alternative forms for polytropic processes: p n  const, p1nT n  const, T n1  const .
The molar form for the equation of state
A mole of gas: A mole of gas contains NA molecules, where NA is Avagadro’s constant.
N A  6.022045 1023 mol1  6.022045 1026 kmol1
Molecular weight: The molecular weight Mw of a substance is defined as the dimensionless quantity
Mass of one molecule of substance
Mw 
(1/12) mass of one atom of carbon  12
A quantity having the same numerical value as M w for 1 mole of substance is the molar mass M measured in g / mol
(or kg / kmol ). To convert the molar mass M of a gas to its associated mass, is simply related by m  Mn , where n is
the number of moles.
The universal gas constant and the ideal (molar) gas law
Substitution of m  Mn into pV  mRT gives pV  nMRT , where MR    8.3145 kJ kmolK .
The definition above provides a method for calculating the characteristic gas constant for any gas.
The ratio of specific heats
cp
In many applications, the ratio of the specific heats plays an important part and it is useful to define   . One of the
cv
most important processes encountered in the course is an isentropic process (constant entropy). For ideal gases, an
isentropic process can be described by equations that look similar to the polytropic processes. The difference between
polytropic and isentropic processes is that the polytropic index n   , i.e. an isentropic process is defined by the
following equations: p   const , p1 T   const , T  1  const.
Other Equations of State
RT RT a  b c 
Clausius: p  ; Van der Waals’: p   2 Virial: p  RT 1    .... ; Beattie-Bridgeman:
 b  b    2

RT  c   b  1  a 
p  2 1  3   Bo 1     2 Ao 1   .
  T       
Gas mixtures
The difficulty with applying the equation of state p  RT to a mixture is that the characteristic gas constant is required
for the mixture. However, R is still obtainable from the relationship R   / M , but in this case M is the mean molar
mass defined to be M  m / n . Consider a two component gas system with n  n1  n2 , where ni is the number
of moles of gas component i. Similarly m  m1  m2 where mi is the mass of gas component i and note that
m m1  m2 n1M1  n2 M 2  n1  n 
M i  mi / ni and the mean molar mass is M       M1   2  M 2  y1M1  y2 M 2
n n n n n
where yi  ni n are the mole fractions.

It can sometimes be useful to define mass fractions Yi  mi m . Analysis of a mixture on the basis of mass (or
weight) is termed gravimetric analysis whilst analysis on the basis of moles (or volume) is termed volumetric
analysis.
MODERN THERMODYNAMICS
 HEAT ENGINES
Introduction
Thus far from our discourse we have seen that the formularisation and interpretation of the zeroth and first
laws gave rise to the thermodynamic properties temperature T and intrinsic internal energy U,
respectively. Likewise the second law implies the existence of the thermodynamic property entropy
(symbol S). Entropy is often considered recondite by students but at this stage can be viewed simply as a
measure of the quality of energy in contrast to U which a measure of the quantity of energy. Low entropy
infers high quality and conversely high entropy means low quality. Entropy is also linked with other
words such as disorder, spontaneous and reversibility.
As with T and U a microscopic description of entropy is possible with entropy being a measure of the
uncertainty in the precise energy levels molecules occupy (this is essentially what is meant by disorder).
This notion is encapsulated quantitatively by the formula for absolute entropy S  k ln W , where k is
Boltzmann’s constant and equals 1.38065 1023 J / K and W is a measure of the number of ways the
molecules of a system can be arranged to achieve the same total energy (the weight of an arrangement).
This formula does not belong to the realm of classical thermodynamics (more to do with statistical
mechanics really) so is only of passing interest here. It is of interest to note (again in passing) that at
absolute zero molecules are in their lowest state of energy (the ground state) and provided this state is
unique (non-degenerate), then W  1 and S  k ln1  0 ; reflecting that fact there is no uncertainty in the
distribution of energy at absolute zero. Entropy is essentially a measure of nature’s proclivity for disorder
as opposed to order.
The word spontaneous mentioned above refers to a change not needing to be driven by work. The flow of
energy from a hot reservoir to a cold reservoir in the form of heat is a spontaneous change. A particular
manifestation of the second law is that the entropy of the universe (system plus surrounding) increases in
the course of any spontaneous change. Since loosely speaking the word spontaneous is synonymous with
the word natural it is clear that second law in this form infers that natural processes result in the energy of
substances lowering in quality (which is rather worrying!).
Another word highlighted is reversibility which refers to a reversible process or reversible cycle if the
process is cyclic. This is a process that can be reversed by means of infinitesimal changes in some
property of the system without dissipation of energy (entropy production). The system is in
thermodynamic equilibrium throughout the entire process and since it would take an infinite amount of
time for the reversible process to finish, perfectly reversible processes are impossible. The importance of
reversible processes which are cyclic is that they do not involve entropy production. Moreover, the
 Qrev
classical definition for entropy in differential form is dS  , where  Qrev is an increment of heat
T
reversibly applied.
Classical thermodynamics introduces the second law via devices called heat engines, which operate
between thermal reservoirs, where a thermal reservoir is a hypothetical body with an infinite heat
capacity. The defining quality of a reservoir is that it can reject or absorb quantities of heat without
changing temperature. A heat engine is a continuously operating thermodynamic system, across the
boundaries of which only heat and work can flow, where the phrase continuously operating implies that
the working fluid in the heat engine undergoes a cycle.
Heat Engines
There are two types of heat engine; direct and reversed.
In a direct heat engine, Q1 is supplied to the engine at temperature T1 . Inside the engine, part of the heat
transfer is converted to work (shown here as shaft work Ws ). A quantity of heat Q2 is rejected to a
reservoir at temperature T2 .
In a reversed heat engine, a work transfer into the device occurs. This shaft work is then used to pump
heat from a low temperature reservoir at temperature T2 into the high temperature reservoir at T1 .
The refrigerator is called a reversed heat engine because work is transferred into the engine, and this work
is used to transfer heat from a cold environment (ice box) to a warm environment (the room in which the
fridge stands). The objective of a fridge is to draw heat from a low temperature reservoir and, using an
input work transfer, reject this heat into a higher temperature environment.
 HEAT ENGINES
A similar device to the fridge is the heat pump. This too is an example of a reversed heat engine. The
objective of a heat pump is to take heat from a low temperature reservoir and, using an input work
transfer, use it to provide (say) domestic heating.

Reversible processes
A reversible process is one that can be made to take place in either forward or reverse directions by
changing the conditions in the system by ONLY an infinitesimal amount. A reversible process is a one
that can be reversed without leaving any net effect on the surroundings.
A reversible heat engine is one that involves no irreversibility as a result of friction or heat transfer
across a finite temperature gradient. of the engine is at T2 -- no finite temperature gradient
The engine is externally reversible, because the heat transfer from the reservoirs (i.e. external to the
engine) takes place reversibly (without finite temperature gradient). The reversible heat engine is also
internally reversible. As the name implies, the components of such an engine are frictionless and do not
introduce transient phenomena such as pressure waves or pressure drops across valves.

Statements of the second law of thermodynamics

The Kelvin-Planck statement of the second law of thermodynamics: It is impossible for any device
that operates in a cycle to receive heat from a single reservoir and produce a net amount of work.

The Clausius statement of the second law of thermodynamics: 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
body to a higher temperature body.

The second law and efficiency

Ws Q
thermal efficiency of a heat engine  th   1 2
Q Q1
Q Q2 Q  Q1  Q2 Q1
coefficient of performance of a refrigerator    2   1  1
Ws Q1  Q2 Q1  Q2 Q1  Q2
Q
coefficient of performance of a heat pump   '  1    1
Ws
Corollaries of the second law
Corollaries 1 and 2 (The Carnot principles)
The efficiency of an irreversible heat engine is always less than the efficiency of a reversible one
operating between the same two reservoirs
The efficiencies of all reversible heat engines operating between the same two reservoirs are the same
Absolute temperature: Corollary 3: A temperature scale may be defined which is independent of
thermometric substance. A consequence of the definition of the thermodynamic temperature scale is the
 Q2  T2
result    pertaining to a reversible heat engine.
 Q1 rev T1
Reversible heat engines refrigerators and heat pumps
T2 T1 T2
th  1  , ' ,  ,  '   1
T1 T1  T2 T1  T2
From the equation for efficiency of a reversible heat engine, it is apparent that the most efficient heat
engines are those that operate with the largest possible difference in temperatures between hot and cold
T2
reservoirs. In that case,  1 , and th attains a high value. The idea that engines grow more efficient
T1
as the temperature ratio across them increases leads us to the idea that energy can have an associated
quality.

MODERN THERMODYNAMICS
 ENTROPY
Introduction
Recall that the classical definition for entropy in differential form is dS   QR T , where  QR is an increment of heat
reversibly applied. An increment in entropy can also be consider to be formed in two parts, i.e. dS  de S  di S , where
de S   Q T (called the exchange entropy) and di S  0 is associated with entropy production and irreversibility. In the
event of a reversible increment then di S  0 and dS  de S   QR T . A rate equation can also be written, i.e.
S  Se  Si , which is a form appropriate for a control volume although any transfer of entropy resulting from material
transfer at the control surface must be accounted for.
Consider a control volume where an elemental volume of material exiting at dA is v  ndAdt from which it can be
deduced that the elemental mass exiting is  v  ndAdt and it immediately follows that the elemental entropy exiting is
 sv  ndAdt , which can be written as sdmdt . The rate form of the entropy equation for an open system follows and is
dScv q
  sdm   dA  Si
dt  
T
 
where Scv  sdm and Si  si dm , and for the case of a stationary control volume dm   v  ndA .
 

A similar interpretation is placed on  q T dA in the entropy equation with is interpreted to be a form of entropy transfer.

Note the absence of a work term in the entropy equation arising because work is an ordered form of energy transfer hence
does not transfer entropy unlike heat which is a disordered form of energy transfer. The entropy transport equation
includes a production term Si that captures entropy production in the control volume (arising from irreversibility). No
such similar term is present in the energy equation as a consequence of the conservation of energy (the 1 st law).
q
 e dm  Q  W  sdm   T dA  S
h
Applications of the SFEE s and the SFEntE i
  

 e dm  m  e  e1h   0  0  h2  h1 and  sdm  m  s2  s1   Si  s2  s1  Si  si  0 .

h h
Throttling: 2
 
m

 e dm  m  e  e1h   0  0  h2  v22  h1  v12 and  sdm  m  s2  s1   0  s2  s1 .

h h 1 1
Nozzle: 2

2 2 

 e dm  m  e  e1h   0  Ws  h2  h1  ws and  sdm  m  s2  s1   0  0  s2  s1 .

h h
Turbine: 2
 

 e dm  0  m  h h   m h  hinf2   0 and similarly for entropy  sdm  Si 

h f1 f1 f1 f2 f2
Heat Exchangers: out in out

Si  m f1  sout
f1
 sinf1   m f2  sout
f2
 sinf2   0 .
The Origins of entropy
Q
Corollary 4 of the second law is: whenever a system executes a cycle, T 0
QR Q R
Corollary 5:  T
 0 for any reversible cyclic process. Hence  T
is a property of any reversible process between
a reference state 0 and any other state 1. This property is called entropy.
The entropy of a system is denoted by a letter s or S, and is defined according to dS   QR T or ds   qR T or
2
S  m  s or S2  S1    QR T .
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MODERN THERMODYNAMICS
It is entropy, and not energy alone, which is the important ‘flowing quantity’ in machines producing work. The
production of motive power is not due to the ‘consumption’ of entropy, but due to its transportation from hot bodies to
cold ones.
Corollary 6: The entropy change of an isolated system always increases or, in the limit, stays the same
The word spontaneous mentioned above refers to a change not needing to be driven by work. The flow of energy from a
hot reservoir to a cold reservoir in the form of heat is a spontaneous change. A particular manifestation of the second law
is that:
The entropy of the universe (system plus surrounding) increases in the course of any spontaneous change.
Heat Engines revisited
Entropy (universe ) change for an heat engine is S  S1  S2   Q1 T1  Q2 T2  0 , which implies
 Q2 Q1   T2 T1 and 1  Q2 Q1  1  T2 T1 hence th  R . This proves that Carnot engines are the most efficient and
the reason why is that entropy is not produced. Heat spontaneously flows from a hot to a cold body and such spontaneity
can be used to produce work.
T-s diagrams (Reversible processes on the T-s diagram)
Recall that ds   qR T , or equivalently  qR  Tds . Consider a system undergoing a reversible change of state and let
2
us draw that change of state on a T-s diagram. The total area under the curve is: q12  1
Tds for a reversible process.
Reversible, adiabatic (isentropic processes): Since ds   qR T , where  qR is the reversible heat flux. As our system
is reversible and adiabatic,  q   qR  0 , hence ds  0 . On the T-s diagram, isentropes appear as vertical lines. Note
that an isentropic process need be neither reversible nor adiabatic.
Entropy changes for pure substances
For a given process, the heat transfer that takes place can of course be evaluated from the First Law as (in terms of
specific quantities) du   q   w . For a reversible process involving fully resisted expansion with reversible heat
transfer w  pd and  qR  Tds , which on substitution leads to a rather important equation (sometimes referred to as
the central equation of thermodynamics), i.e.
Tds  du  pd (or TdS  dU  pdV )
Observe that this equation only involves state variables and consequently applies for all process (on simple systems)
irrespective of whether or not the process is reversible. This is a significant advance since this equation provides a general
relation between p ,  , T and s . It is in essence a thermodynamic identity since it is not necessary to inquire whether
the process is reversible or irreversible to apply it.
Note also that h  u  p , giving dh  du  pd  dp which on substitution gives Tds  dh  dp .
T-s diagrams and cyclic processes
Assuming that all components of the plant are internally and externally reversible. From the first law applied to the plant
  
W  Q and, furthermore Q  TdS . 
It follows that the work done during a reversible cyclic process is represented by the area enclosed on a T-s diagram.
Entropy changes for perfect gases
The starting equation is the all-important central equation of thermodynamics, i.e. Tds  du  pd and in view of the
identities p  RT and du  cv dT , this equation gives on integration
T   
s2  s1  cv ln  2   R ln  2 
 T1   1 
Similarly Tds  dh  dp with p  RT and dh  c p dT gives
T  p 
s2  s1  c p ln  2   R ln  2 
 T1   p1 
The isentropic process in a perfect gas
Recall that an isentropic process is one in which ds  0 and in the case of a perfect gas.
 1 
 
T  1
 const. or Tp   
 const. or p   const.
MODERN THERMODYNAMICS