The 'turning sphere', quoted by Hero of Alexandria, 120 B.C.

1 1.1

Revision of basic thermodynamics Properties and SI units p pressure (Pa) T temperature (K) V volume (m3) u internal energy (J/kg)

s entropy (J/kg.K) r density (kg/m3) v specific volume (m3/kg) h enthalpy (J/kg)

1.2 Thermodynamic state the thermodynamic state is defined by two thermodynamic properties. That is, once we know two thermodynamic properties, we can determine the rest. we can therefore draw state diagrams using only 2 axes: e.g. p - v , T - s and h - s diagrams for example, the ideal gas equation is the equation of state for ideal gases because it relates two thermodynamic properties to a third thermodynamic property: p = r RT numerous other equations of state exist for various substances. All of these perform the same function as the ideal gas equation i.e. they relate thermodynamic states to one another. some substances, such as steam, have very complex equations of state. In these cases, we usually refer to tables rather than calculate the equations.

1.3 Useful relations for any substance the density is the reciprocal of the specific volume: 1 r= v enthalpy is defined as:
h = u + pv

definition of Cv (specific heat at constant volume):

u Cv = T v =const
definition of CP (specific heat at constant pressure): h CP = T p =const infinitesimal work output:
dW = p.dV

1.4 Relations for an ideal, calorifically perfect gas unless stated otherwise (such as for the refrigeration and steam cycles), we will assume that all gases in this course are ideal (sometimes refereed to as perfect or even thermally perfect): p = r RT furthermore, any ideal gas that we encounter will be assumed to be calorifically perfect i.e. CP , Cv and g are constant. from the definition of enthalpy and the ideal gas equation, it can be shown that a calorifically perfect gase follows the following relations: C P - Cv = R or, expressed differently: (g - 1) R R & g -1 = = Cv Cp g where g =
CP is referred to as the ratio of specific heats. Cv

note that the assumption of calorific perfection is only valid in certain cases. Cases where calorific perfection cannot be assumed are studied mainly in 4th year thermodynamics.

1.5 Processes when considering a transition between two thermodynamic states, the following processes are often used:

constant volume constant pressure constant temperature constant entropy no heat transfer

isochoric isobaric isothermal isentropic adiabatic

a general (polytropic) process is defined as occurring when: Pv n = constant it follows that if:
n = 0 then p = constant and the process is isobaric

n = then v = constant and the process is isochoric

n = 1 then T = constant and the process is isothermal (only true for an ideal gas) n = g then Pvg = constant and the process is adiabatic (only true for an ideal, calorifically perfect gas)

p - v diagram of polytropic processes:

process diagrams:

note that these process diagrams apply only for dry gases. Wet regions are dealt with later. if CP is assumed constant, the h - s diagrams have the same form as T - s diagrams since h = CPT

1.6 The first law of thermodynamics energy equations convention: heat into system is +ve, heat out of system is ve work into system is -ve, work out is +ve 1.6.1 Non-flow energy equation (NFEE) if the mass in a system is constant and identifiable (e.g. that within a balloon or the cylinder of a reciprocating compressor or engine), we can use the non-flow energy equation (NFEE) to describe the work and heat exchange: q - w = Du where q and w denote the heat exchange and the work per unit mass ( J / kg ) respectively. It follows that: Q - W = DU = mDu where m is the mass of the system ( kg ) and Q and W are in joules ( J ).

1.6.2 Steady flow energy equation (SFEE) when the mass in a system is no longer constant and identifiable, we can use a control volume that defines the system and in which the total mass is constant but changing (i.e. unidentifiable): in this case we often use the steady energy equation (SFEE) to describe the work and heat exchange: V2 V2 q - w = D u + pv + + gz = D h + + gz 2 2

where V is the fluid velocity ( m / s ), z is the elevation ( m ) relative to some datum and g is the gravitational constant ( m / s 2 ) the SFEE can be written as a rate equation: V2 & -W & =m &Dh+ Q + gz 2 & and W & are in watts ( W ). & is the massflow rate ( kg / s ) and Q where m & = 0 we have an adiabatic process and: note that, if Q

V2 & =m &Dh + -W + gz 2 & = 0 we have no work into or out of the system and: and if W V2 & =m &Dh + Q + gz 2
note that it is often possible to neglect the potential energy ( gz ) and kinetic energy ( V 2 / 2 ) terms. This will be done often during this course, but should always be stated. The second law of thermodynamics second law of thermodynamics is a further restriction on the first law.

1.7

the first law of thermodynamics is a statement of the conservation of energy. The

1.7.1 Statements of the second law

there are two common prose statements of the second law:

The Kelvin-Planck statement It is impossible for any engine working in a cyclic process to draw heat from a single reservoir and convert it into work. The Clausius statement It is impossible for any engine working in a cyclic process to produce no effect other than the transfer of heat from a cooler body to a hotter body.

it can be shown that a violation of one of these statements infers the violation of
the other.

the two statements of the second law can also be shown to infer Clausius
statement:

T
respectively

dq

where the equality and inequality represent reversible and irreversible processes considering a reversible cyclic process, Clausius gives

dq dq dq + =0 T = T 2 T 1

each of these integrals depend only on the end points, and not on the path. They
are therefore properties of the system, from which we will define the entropy s :
dq s2 - s1 = T rev 1
2

or, infinitesimally:

Tds = dqrev

note that this is an entropy difference. The third law of thermodynamics

(discussed in 4th year) states that the entropy of a pure substance is zero at absolute zero.

1.7.2 Equations arising from the second law

combining the NFEE and the infinitesimal definition of entropy gives:

Tds = du + { pdv
dw

since h = u + pv , we can write the infinesimal change in enthalpy as

dh = du + pdv + vdp

thus

Tds = dh - pdv - vdp + pdv

= dh - vdp

the two equations, describing reversible processes, are known as Gibbs

equations:
Tds = du + pdv Tds = dh - vdp

assuming a calorifically perfect, ideal gas, Gibbs equations can be integrated to

give:
T v s2 - s1 = Cv ln 2 + R ln 2 T1 v1 T p & s2 - s1 = C p ln 2 - R ln 2 T1 p1

1.8 Wet and near-wet substances the ideal gas law only describes gases that are well removed from any phase change boundary. It is therefore completely incorrect to use the ideal gas equation for mixtures of gas & liquid (eg. wet steam) and for any gas near a phase change boundary. therefore, thermodynamic charts and tables should instead be used for wet and near-wet substances

in order to determine thermodynamic properties within the wet region:

the specific entropy s ( J / kgK ) is then:

s = s f + x ( sg - s f ) 1 4 24 3
s fg

the specific enthalpy h ( J / kg ) is:

h = h f + x ( hg - h f ) 1 4 24 3
h fg

the specific volume v ( m / kg ) is:

v = v f + x ( vg - v f ) 1 4 24 3
v fg

where x = the dryness fraction, subscripts f and g refer to the liquid and gas
states and fg refers to the phase change between liquid and gas 1.9 Polytropic relationships for an ideal gas

since for a polytropic process: it follows that:

pv n = constant
p2 v1 = p1 v2
n

using the perfect gas equation:

p1v1 p2 v2 = T1 T2

thus, for a polytropic process involving an ideal gas:

T2 p2 = T1 p1
1.10 Stagnation quantities

n -1 n

v = 1 v2

n -1

a stagnation quantity is defined as the quantity attained when a fluid is brought

to rest isentropically

for example, stagnation enthalpy ht is defined as:

ht = h + V2 2

note that from the SFEE on a control volume with W = Q = DP.E. = 0 :

Dht = 0

i.e. the stagnation enthalpy is conserved throughout the control volume. This is
true irrespective of whether the flow is isentopic or entropic, and is a very important result in both thermodynamics and fluid dynamics.

for a calorifically perfect gas:

ht - h = CP (Tt - T )
V2 2CP
2

the stagnation temperature is therefore related to the static temperature by:

Tt = T +

2 V 1 g R V T 1 = T 1 + = + CP g RT 2{ 2CPT 1 4 2 4 3 g -1 M2

thus,

(g - 1) M 2 Tt = 1+ 2 T
g

since an isentropic process is by definition adiabatic:

Pt Tt (g -1) = P T the stagnation pressure is therefore:

V 2 g -1 Pt = P 1 + 2CPT

these expressions can also be written in terms of the Mach number

M = V / g RT rather than the velocity V :

(g - 1) M 2 Tt = 1+ T 2
Pt (g - 1) 2 M = 1 + P 2 g / (g -1)

rt (g - 1) 2 M = 1 + r 2

1/ (g -1)

stagnation quantities are denoted is this course by the subscript t e.g. Pt is the
stagnation pressure. However, they are often denoted with the subscripts s & 0 in other texts. Stagnation quantities are also referred to as total quantities in other references e.g. total pressure. 1.11 Important questions to answer when solving problems 1. What is the system boundary or control volume? 2. Is the problem steady flow or non-flow?

if non-flow, use the NFEE if steady, use the SFEE

3. What is the working fluid?

single phase: ideal gas, calorifically perfect gas? condensable vapour: use tables & charts mixture of ideal gases: use mass weighted mean values of CP , Cv & R reacting mixtures: typically a 3 stage calculation in which the reactants and
products may be ideal gas mixtures, chemical stoichiometry describes the reaction and composition of products and DH R gives the heat release 4. What processes are involved? adiabatic, dq = 0 isothermal, dT = 0 isobaric, dP = 0 free expansion, w = 0 Isentropic, ds = 0 isochoric, dv = 0 throttling, dh = 0