Second Year Module H3053

THERMAL POWER CYCLES

Lecture 2A: The Second Law and Entropy

Module Convenor: Prof Martin G. Rose

TFMRC (Thermo Fluid Mechanics Research Centre).

Room TF7 (ground floor to the right).
01273 678945
[email protected]
Office Hours for student enquiries;
Tuesdays 9:00 to 11:00.
Atmospheric Steam Powered Beam Engine C1700
The Second Law of Thermodynamics
Famously this is a difficult abstract topic, I found it quite unsettling when I was an undergraduate. The
second law arises from Physicists trying to explain why Engineers had consistently failed to achieve high
efficiency heat engines. Firstly an isolated body cannot continuously produce work (Perpetual Motion
Machine of the first kind PMM1). PMM1 breaks the first law.

Secondly to paraphrase Planck he said “a perpetual motion machine (PMM2) of the second kind does not
exist”. A PMM2 is an engine which communicates with a single source of heat and continuously delivers
work. How helpful is that? This would break the second law.

PMM1 is Impossible! T uniform PMM2 Also Impossible!

Q
Wx

Wx

An important part of coping with the second law is learning about Reversible and Irreversible
processes. A reversible process is one that can be run backwards to allow the results of a process
to be perfectly converted back into their initial (before the process) state. Many processes are
Irreversible e.g. friction, mixing, shockwaves, heat transfer across a significant temperature
difference, most chemical reactions etc.
 ENTROPY
Entropy (symbol s J/kgK) arises from the second law after a great deal of thought from some
very bright people. Both the second law and entropy are very powerful concepts applicable to all
matter in the universe. One statement of the second law is that the entropy of an isolated system
can only increase. Some (rather romantic) people have named the second law as the “Arrow of
Time”. The idea being that the law defines the direction in which time must advance (never
backwards). This is because the conclusion that the Entropy of an isolated system always
increases does involve the definition of a direction of time.

So what can we say about entropy? You can’t see it. You can’t smell it. You can only indirectly
measure it (generally you need to measure two other parameters to evaluate it), It has no absolute
value, no datum state so equations only refer to the changes in entropy. Entropy is a property of
matter it helps to define the physical state of anything. The equations which define entropy are
simple equations with very few terms. They can be learnt and usefully applied. It is
experimentally clear that entropy changes control the performance of Thermal Power Cycles!

Physicists say that Entropy has to do with order and disorder, I do not find this helpful, since I
cannot see or measure the “order” of a mass of steam or water! When I met a senior academic
thermodynamicist I asked him “What is Entropy?” he smiled and said “It’s a green gas”, we both
knew that there is no satisfactory answer to the question.
 Entropy Cont. 𝛿𝑄
𝛿 𝑠≥ ∫
𝑇
s is Entropy Joules/kgK, Q is a quantity of heat transferred in Joules, T is
the temperature of the body in the absolute temperature scale Kelvin,
gaining or loosing this amount on heat. Note that a closed Control
Volume which may either receive or loose heat does not have the
necessity to always increase in Entropy. If heat is lost from a body its
entropy reduces! Also note that the higher the Temperature is the lower
the change in Entropy is. This is why overtime our development of better
heat engines involves higher and higher peak temperatures. If we are
dealing with a reversible system (a realisable but theoretical extreme) we
can write:
𝛿𝑄
𝛿 𝑠=
𝑇

The best way to deal with it as an undergraduate is to simply accept the

equations, learn them and apply them. Those of you awake will have just
noticed that I have just contradicted my self. But I recommend this approach
because intuitive understanding of these specific subjects is illusory after
centuries of thought we have nothing to show. But we do know that the ideas
work and match experiment.
 Gibbs Equations
An expression of the second law u
Q Heat Work Wx
∆ 𝑢=𝑄 − 𝑊 𝑥
= pdv 𝛿𝑄
𝛿 𝑠=
𝑇
Using the closed control volume and the statement of the first law we had previously.
Also taking both the relationship between heat transfer and entropy change and the
expression for the work of a closed CV.

𝑄=∆𝑢 +𝑊 𝑥
𝑇𝑑𝑠=𝑑𝑢+ 𝑝𝑑𝑣

This is Gibbs first equation. A confusion arises here for me. The expression for
the heat transferred in terms of entropy change and temperature is for a reversible
process, yet Gibbs equation is universally applicable. Text books make
statements like these terms are properties so the changes in them are independent
of route. I’m afraid this is an issue I have just accepted: I recommend you do the
same.
The Second Gibbs Equation

This equation can be used when we are dealing with open control volumes and the energy of
the flowing fluid is best expressed as its Enthalpy h. We start off with the definition of
Enthalpy. Remember!
h = enthalpy J/kg
h=𝑢+ 𝑝𝑣 u = internal energy J/kg
p= pressure N/m2
v = specific volume m3/kg

If we now differentiate this expression we can write:

𝑑h =𝑑𝑢 +𝑝𝑑𝑣 + 𝑣𝑑𝑝 (1)

Taking Gibbs first equation from the previous foil and substituting from equation (1):

𝑇𝑑𝑠=𝑑𝑢+ 𝑝𝑑𝑣
𝑇𝑑𝑠= 𝑑h −𝑣𝑑𝑝
We have the Gibbs second equation. If we apply these equations to an ideal lossless pump of
incompressible fluid, one in which the entropy does not rise we can draw two immediate
conclusions: since ds = 0 and dv = 0 then du = 0 and dh = vdp. So in such a pump of lossless
incompressible fluid the internal energy does not rise (only irreversible changes will cause the
internal energy to rise) and the enthalpy rise is equal to dp/ρ, where ρ is the density.
We have just shown using Gibbs second equation that for a machine with an open
control volume with incompressible fluids the work term becomes vdp.

𝑑h =𝑣𝑑𝑝
This is specific volume v m3/kg (a constant for incompressible flow). Multiplied by
the change in pressure dp N/m2.

The units of vdp are: m3/kg * N/m2 : i.e. Nm/kg or J/kg: this looks like specific work

But what is the mechanism? We expect to see a force move through a distance, but we
have a constant specific volume mass of fluid simply changing pressure:

WHERE IS THE WORK?

 In order to find the work we look at a control volume:
Area A m2
Density ρ kg/m3

Pressure N/m2
Velocity V m/s
The force on the inlet is equal to Pressure times Area F = pA :N
The volume flow rate of the fluid entering the CV is
equal toVelocity times Area Q = VA :m3/s
The massflow rate coming in through the inlet equals
Volume flow rate times density m = ρQ kg/s
Rate of Work done on CV due to fluid entering it: Power = FV Nm/s
Specific work done by fluid as it enters the CV Wx = Power/m
Wx = FV/ρQ = pAV/ρVA = p/ρ = vp
So vp is the specific work of the fluid entering the CV. This is why it appears in the
definition of enthalpy. Work causes a change in the enthalpy so we differentiate as
shown on the previous foil vdp is the change of enthalpy flux due to work in an
incompressible fluid. It is independent of velocity but only exists due to it.
Equations for the Change in Entropy of an Ideal or Perfect Gas

For such a gas we have simple expressions for the internal energy and also for the
enthalpy and we have the equation of state.

dT dT R

Taking Gibbs first equation 𝑇𝑑𝑠=𝑑𝑢+ 𝑝𝑑𝑣

Divide through by T +R

Substituting: + R
Taking cv and R as constants and integrating
-=
-=

Alternatively if we use the second Gibbs equation we get

- = Ln
The Isentropic Relationships

It is necessary to make reference to ideal lossless processes in Thermal Power Cycles these
processes are reversible and they are characterised by having constant entropy. For example such
processes can represent the ideal compression in a car engine or ideal power output of a steam
turbine. These expressions are most easily derived from the equations of entropy change just
given. We start from the closed control volume form:

-=

If we set the entropy rise to zero (isentropic) we get: =-n

Rearrange = Ln

=
so

Often written: = const.

Two other isentropic relationships can be derived using the other expression for
entropy change and the re-use of the above result:
= const. = const.
The best possible cyclic heat engines will be the reversible ones: CARNOT

The CARNOT cycle was proposed in 1824 by Sadi Carnot a French man. T H and TL are
uniform reservoirs of high and low temperature respectively. The cylinder contains air. The
cylinder is perfectly insulated except for the end where the insulation comes and goes.

(1) (2) (2) (3)

1-2 2-3
.

TH
TH = const

TH Q
TL

(1) (4) (4) (3)

TH

.TL = const
TL Q
TL 4-1 3-4

The perfect piston in cylinder acts like a closed Control Volume. There is no friction it
does not leak. The process is slow so that the gas temperature is always uniform. heat
transfer is only across a negligible temperature difference.

Process 1 – 2 is Reversible Isothermal Expansion. The gas temperature is uniform

and constant at TH The temperature difference is small.
Process 2 – 3 Reversible adiabatic expansion The fluid temperature drops from TH to
TL the process is slow no friction and no leakage. Ana additional insulator is
introduced for this process on the end of the cylinder.
Process 3 – 4 Reversible Isothermal Compression. The additional insulator is
removed. The gas is at constant Temperature TL and looses heat to the cold reservoir
with negligible temperature difference.
Process 4 – 1 Reversible Adiabatic Compression. The additional insulator is re-
installed. The gas heats up as it is compressed until it reaches the temperature of the T H
reservoir.
If the absolute temperature scale Kelvin
is used we can write the CARNOT
efficiency in terms of temperature.
p =1-
(1)
QH

(2) TH = const. = 1-
(4)

(3)
QL TL = const.

v
Two Phase Thermodynamics

Real pure (i.e. not mixtures) substances change phase depending on the temperature
and pressure. Substances can be solid, liquid, gas or plasma these are the “phases”.

It is possible to exploit the phase change of the working fluid to greatly improve the
specific work of a cycle (work output per kg). Two of the thermal power cycles we
will address use phase change; steam cycles and refrigeration cycles.

Here we will introduce the pure substance phase diagram since it is a fundamental to
help understand the steam and refrigeration lectures.
T ⁰C
Steam

100

Water
Bunsen
Burner
Flame Simple boiling
experiment
T time s
 Weight

Modified Boiling Experiment

A slightly different arrangement of the boiling experiment. The

piston is frictionless and has a weight providing a constant
force down on to the piston. The fluid may expand but the
Water pressure is constant.
Bunsen
Burner
Flame
T ⁰C

ur
po
Va
e.g. 125 Vapour & Liquid

idu
Liq

V specific volume m3/kg

If this new boiling experiment is repeated many times with a range of different
weights applied to the piston we can build up a map of the behaviour of the substance

5
re
In the two phase zone pressure

su

4
es

re
Critical Point and temperature are not

Pr

su

3
es
independent. The pressure

re
Pr
T ⁰C

su

2
determines the temperature

es

re
Pr

su
374.14 and vice versa

es
Su Vap

1
Pr

re
pe ou

su
rh r

es
ea

Pr
ted
uid d
Liq oole

Vapour & Liquid

b-c
Su

Two Phase
Saturated Vapour
Zone
or ‘Wet’
The “Quality”, x or dryness of the
fluid in the two phase zone is
V specific volume m3/kg
defined as follows
Saturated 𝑚𝑣𝑎𝑝𝑜𝑢𝑟
𝑥=
Liquid 𝑚𝑡𝑜𝑡𝑎𝑙

At the saturated vapour line the dryness x is 1 and at the saturated liquid line the dryness is
zero.
 This marks the end of the
“fundamental Thermodynamics”
part of the Thermal Power Cycles Module

We will need to make reference back to these pages as we start to

define and analyse the various cycles

Does anyone have any questions about the fundamentals?

It is also fine to address such questions at any time during the

remainder of the lecture series.