Thermodynamics 1 ACM

TOPIC 4, THE SECOND LAW OF THERMODYNAMICS

LECTURE 1/ 4 , TOWARDS A “REVERSIBLE HEAT ENGINE”

"It is impossible for any device that operates on a cycle to receive heat from a single
reservoir and produce an amount of work"

LECTURE 1 HEAT ENGINES AND TWO STATEMENTS OF THE SECOND LAW

1. Preamble

The second law concerns the quality of heat - not only do hot liquids and gases
contain more energy, but a bigger fraction of that energy can be converted by an engine
to useful work. Discussion of the second law takes in the reversible engine, a theoretical
cycle that would yield the maximum possible efficiency. To test the concept of the
reversible engine we shall envisage it as operating between two reservoirs, a reservoir
being a very large heat store that changes its own temperature only infinitesimally when
heat is added or rejected (Q = m c T and m c is huge). Hoter reservoirs are called
"sources" and colder reservoirs "sinks". A further concept is the reversible heat pump.

2) Heat Engines

A heat engine accepts heat from a hot reservoir, does useful work, and rejects
heat to a cold reservoir. Flames and solar heat approximate hot reservoirs (or sources).
The atmosphere or an ocean can approximate a cold reservoir (or sink) - note heat
transfer via power station cooling towers, automobile exhausts and radiators.

Hot reservoir at T1

Q1

Heat
Engine W

Q2

Cold reservoir at T2

Fig. 1, Showing heat and work transfers associated with a heat engine

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 The efficiency of the heat engine is the ratio of desired outcome (W) to
necessary input (Q1). From the first law,

W   Q1  Q2 (1)

Then the efficiency becomes,

W Q1  Q2 Q - Q2
   1 (2)
Q1 Q1 Q1

(Many text books omit the modulus, | |.)

We shall see that heat engines operate in cycles. That is, the working gas
passes through a sequence of states, possibly mapped by p-versus-V, before returning
to the start condition (1-2-3-4-1-2-3-4-1...). This is done by repeated expansion and
compression of gas in a piston-cylinder, or by the use of compressors and turbines.

3) Kelvin-Planck Statement of the Second Law

"It is impossible for any device that operates on a cycle to receive heat from a single
reservoir and produce an amount of work"

We point out the second law is axiomatic. That is, it is self-evident, it has been observed
in practice and has yet to be disproved (although no formal proof exists). Referring
back to Fig. 1, we see that a cyclic engine not only accepts heat but must reject it too
(see consequence (a) below). Any cyclic engine connected to one reservoir only and
producing work would be termed a “perpetual motion machine of the second kind”. The
consequences of the second law are:

(a) If a system does a net amount of work on surroundings during one cycle, it must
exchange heat with two or more reservoirs
(b) If a system exchanges heat with one reservoir only during one cycle, the work
transfer (to the system) is greater than or equal to zero.
(c) Heat can never be converted completely to work whereas work can be converted
to heat: work is the more valuable form of energy.

The second law has eight corollaries, investigated in this series of lecture.

4) Clausius Statement of the Second Law

Corollary 1: "It is impossible to construct a device that operates in a cycle and

transfers heat from a cooler to a hotter body without work being done on the system by
the surroundings" (Clausius statement of the second law.).

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 We shall study the null hypotheis. (A null hypothesis is one that the researcher
tries to disprove).

Null Hypothesis (Fig. 2) Consider a heat pump (part a) which accepts Q from the
cold reservoir, accepts no work, and rejects Q to the hot reservoir. Alongside place a
heat engine that, following the Kelvin-Planck statement, accepts W + Q from the hot
reservoir, produces work W and rejects heat Q to the cold reservoir. The net heat
transfer to the cold reservoir is Q – Q = 0 and the cold reservoir might as well be
removed from the complete system. We then have a single (hot) reservoir that produces
an amount of work W, and contravenes the Kelvin-Planck statement. The null
hypothesis is disproved.

Fig. 2 Proof of corollary 1. Heat pump H.P. is falsely claimed to transmit

heat Q from cold to hot reservoir with no work addition. Reversible heat engine
R.H.E. rejects equivalent heat Q to the cold reservoir. The cold reservoir is
redundant because the net heat crossing the (dotted) boundary from it is zero.
Net heat (W+Q-Q = W) crosses from the hot reservoir and net work W is derived.
This contravenes the Kelvin-Planck statement (no net heat crosses from the cold
reservoir).

A heat pump moves heat from a cold reservoir to a hot reservoir, and demands a
work input. The heating power per unit applied work is termed the "coefficient of
performance",
Q1 Q1
COPHP   (3)
W Q1  Q2

A refrigerator is a special instance of a heat pump.

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LECTURE 2 REVERSIBILITY AND THE THERMODYNAMIC TEMPERATURE SCALE

5) Reversibility

For quasi-equilibrium, where process passes through a series of equilibrium states

(a) heat is transferred by virtue of infinitesimally small temperature differences

(b) for all work done the force exerted by the surroundings on the moving boundary
is only infinitesimally different from that owing to fluid pressure in the system.

Definition: When a fluid undergoes a reversible process, both the fluid and the
surroundings can always be restored to their original states.

Let us consider friction and heat transfer as sources of irreversibility.

Friction

Consider paddle wheel work as an example of irreversible process

W = U2 – U1

Once this work has been expended in changing the internal energy of the fluid, it
is irretrievable. (See R+M for fuller description.)

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 Fig. 3 Showing the effect of fluid friction. Reversible work is the area under the
dashed line. Applied work is the area under the solid line

Alternatively, consider a reciprocating compressor, such that gas within a sealed

cylinder is compressed from 1 to 2 (Fig. 3). The Figure shows the pressure versus
volume plot. However, we should account (at least) for the sliding friction owing to
piston rings, and for an applied force, F, we find F > pA. The area under the pV curve
only indicates work for reversible processes. Even if perfect piston rings were
manufactured, one would still need to account for frictional effects of the working fluid,
particularly in high speed machines. (R+M discuss the case of a piston trapping
compressed gas and held pack by a pin – the pin is rapidly removed whereupon forces
on either side of the piston are out of balance.)This is particularly true of turbines, where
the enthalpy change is less than one would expect for a reversible process. Fig. 4
shows a turbine expansion on a plot of pressure versus specific enthalpy (p-versus-h).
In the reversible case (1-2’) h is reduced and the available work per unit mass of
working fluid is (h2’ – h1). However, friction heating increases internal energy u, so that
the exit stream has bigger enthalpy, h2 and the useful work (h2 – h1) is reduced. It is
useful to define an isentropic efficiency as the ratio of real-world to reversible work.

W h2  h1
t   (4)
W ' h2 '  h1

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Likewise the isentropic efficiency for a compressor is

W ' h2 '  h1
c   (5)
W h2  h1

Isentropic means “constant entropy”, entropy being a measure of the disorder of a

system. We shall engage entropy later.

Fig. 4 Showing reversible (solid) and real world (dashed) expansion in a turbine

Transfer of heat across a finite temperature difference.

Consider transfer heat from a hot reservoir (temperature T h) to a fluid (Tf) when
Th > Tf. From the Clausius statement, Corollary #1, the process can be reversed only by
an input of mechanical work, i.e. a disruption to the surroundings. Furthermore, the
greater is the temperature difference the greater is the irreversibility.

Example: Air enters a turbine at 10 bar, 900 K and a flow rate of 2 kg s -1 and
expands to 1 bar. The isentropic efficiency is 90%. Find the power produced.

Solution.

Problem Statement: Power from irreversible expansion in a turbine.

Diagrams: See Fig. 4, - we shall later on prefer T-s diagrams..
Assumptions: Adiabatic, Steady Flow, Provisionally isentropic.
Physical Laws: Isentropic expansion. Definition of isentropic efficiency.
Calculation
Isentropic process T2’ = T1 (p1/p2) ((-1)/) = 900 x 0.1 (2/7) = 466 K
W’ = m_dot cp (T2’ – T1 ) = 2 x 1.005 x (466 – 900) = -872 kW
W = 0.9 x W’ = -785 kW

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6 Reversible Engine between two Reservoirs

Corollary 2: It is impossible to construct an engine operating between only two

reservoirs which will have a higher efficiency than a reversible engine operating
between the same two reservoirs.

This proof has similarities to that of the Clausius statement (Fig. 2). Consider (left
hand of Fig. 5) a reversible engine RHE and a second engine HE connected to hot and
cold reservoirs, producing work W R and W X respectively. In the centre RHE is reversed
to form a reversible heat pump RHP, and accepts work W R so that the system produces
net work W X – W R. Now let us consider just HE and RHP, surrounded by the (dotted)
boundary. The net heat transfer to the hot reservoir is Q – Q = 0, and net work W X – W R
is derived from the cold reservoir only. Comparing energy flows the net heat input is W x
– W r, equal to the net work. From the Kelvin-Planck statement of the second law W X-W R
≤ 0 or W X ≤ W R. The irreversible engine, HE, produces less work than the reversible
one, RHE.

Fig. 5 In support of corollary 2. Reversible heat engine RHE produces work Wr.
Reversible heat pump RHP accepts an equivalent Wr; all its energy flows are
reversed. RHP is compared with a heat engine of interest H.E., accepting Q so
that net heat crosses the boundary from the cold reservoir only. From Kelvin
Plank WR > Wx

Corollary 3: All reversible engines operating between the same two reservoirs
have the same efficiency.

This follows from the proof given for corollary 2. HE would refer to a second reversible
engine, which cannot perform better than the first reversible engine RHE.

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7 Thermodynamic Temperature Scale

Corollary 4: A scale of temperature can be defined which is independent of any

particular thermometric substance, and which provides an absolute zero of temperature.
R+M offer a formal proof; it is simplified here. Consider a reversible engine
between hot reservoir 1 and cold reservoir 2. The heat transfers from said reservoirs are
Q1 and Q2 and reservoir temperatures are T1 and T2. Let us recall that engine efficiency
is
W Q Q Q - Q2
  1 2  1 (2)
Q1 Q1 Q1

From corollary 3, the efficiency depends only on the temperatures T1 and T2.
Q2
1    f ( T1 , T2 ) (6)
Q1

Temperature is defined in such a way that

Q2 T2
1    (7)
Q1 T1

This definition is based uniquely on thermodynamics – not any material property

– and is termed the "thermodynamic temperature scale. It has an absolute zero, thus as
the cold reservoir tends to "zero temperature" then engine efficiency tends to unity. If
the above is rearranged the efficiency of a reversible engine becomes

Q2 T2
  1  1 (8)
Q1 T1

This is often termed the “Carnot efficiency”.

In reading R+M, you will find discussion of a reversible engine connected to a hot
reservoir at a reference state To. From said reservoir is removed a reference amount of
heat Qo (e.g. To = 1000 K always and Qo = 1000 kJ always). This "thought experiment"
allows us to envisage a "thermodynamic thermometer" which reports the temperature
(T) of the cold reservoir according to Q, the heat rejected to the cold reservoir from the
engine.
Q
T  To
Qo

(Lack of a subscript replaces my subscript 2 and subscript o replaces my 1.)

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 Source at T1

Q1

Heat
Engine W

Q2

Sink at T2

Fig. 6 Showing single heat engine with reservoirs 1 and 2

Corollary 5: The efficiency of any reversible engine operating between more than
two reservoirs must be less than that of a reversible engine operating between two
reservoirs which have temperatures equal to the highest and lowest temperatures of the
fluid in the original engine.
If T1’ and T2’ are highest and lowest temperatures, then the maximum efficiency
is 1 – T1’/ T2’ and all other subprocesses must achieve lower efficiencies.

LECTURE 3 TOWARDS ENTROPY

8 The Clausius Inequality

Corollary 6. Whenever a system undergoes a cycle,

dQ
 T
0 (9)

i.e. the cyclic integral is zero if the cycle is reversible and negative if irreversible.
I shall take a less rigorous approach than that offered by Rogers and Mayhew. Start with
the efficiency of a single reversible engine cycle, setting up the sign convention that heat flow is
positive when entering the engine and negative when leaving.

 Q2 T2
1    (reversible engine only)
Q1 T1

For the same T2/T1, the efficiency of an irreversible engine is less and 1- is greater.

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  Q2 T2

Q1 T1
irreversible heat reversible heat (reversible or irreversible)
ratio ratio

Multiply throughout by -Q1 /T2 , note the change in inequality sign, and then add Q1/T1 to
LHS and RHS

Q1 Q2
 0
T1 T2

For a set of engine cycles, in each of which the engine exchanges heat with a different
pair of reservoir temperatures, (T1, T2), (T3, T4), (T5, T6) ... Then

Q1 Q2 Q3 Q4
    ...  0
T1 T2 T3 T4
1st cycle 2nd cycle

If very small amounts of heat are added from many reservoirs,

Q1 Q2
  ...  0 (9b)
T1 T2

Assume that the above is true when all heat additions occur over the same cycle. In the
limit Q1  0 etc and integrating over said cycle,

dQ
 T
0 (9) Q.E.D.
9 Entropy

Corollary 7: There exists a property of equilibrium state of a closed system such that a change in
its value is equal to

2  dQ 
S2  S1     (10)
1
 T  rev

for any reversible process undergone by the system between state 1 and 2.
The “closed system” is often a fluid, and entropy is often a fluid property.

Proof

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 2

Fig. 7 Showing that entropy is a property

Consider two reversible outward paths, A and B and a return reversible path C. From the
Clausius inequality (Eq. 9) note that

2  dQ  1  dQ 
  T
1

 rev
   T
2

 rev
 0

outward path return path

Use the definition of entropy in (Equation10) and consider outward paths A,B and return
path C on Fig 7.

S1,2,A + S2,1,C = 0 (if reversible)

S1,2,B + S2,1,C = 0 (if reversible)

That is, S12 is independent of path (A or B) and hence entropy S is a fluid property. We
should be careful about sign conventions here. For the Clausius inequality "positive heat" is
added to the engine whereas for entropy "positive heat" is added to the fluid.

Corollary 8 The entropy of any closed system which is thermally isolated from the surroundings
either increases or, if the process undergone by the system is reversible, remains constant.

In a thermally isolated system work may cross the system boundary, but no heat crosses
the system boundary.

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Proof
Corollary # 8 follows from the Clausius inequality. I replace the more rigorous version of
R+M with my own version.

Fig. 8 Proof of 8th corollary. Small amounts of heat cross boundaries B1, B2, B3 and
Be. No heat crosses Bs, which bounds the complete system.

Let an engine (E) exchange small amounts of heat with many packets of fluid. (Fig. 8).
Let the engine be bounded by Be, the fluid packets by B1, B2, …, and the entire system by Bs.
Only work can pass through Bs, no heat. Adapt the convention that heat crossing a boundary has
positive sign when entering a system and negative sign when leaving it. Revert to the form of the
Clausis inequality in Equation 9b, with heat flow seen from the engine viewpoint,

Q1 Q2
  ...  0 (9b) engine viewpoint, one cycle
T1 T2

From the viewpoint of the fluid parcels, the sign of Q1 etc changes. In Fig. 8, Q1 is
positive from the engine viewpoint but negative from the fluid viewpoint. For example,
Q1 = 10 kJ entering the engine becomes Q1 = -10 kJ entering the fluid. Then rewrite the above
inequality from the fluids’ viewpoint.

Q1 Q2
  ...  0 fluid viewpoint, one cycle
T1 T2

Over time the fluid temperatures will change. Take the limit Q1  0 and integrate from
the start to the end of a time interval.

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 end end
dQ1 dQ2

start
 
T1 start T2
 ...  0 fluid viewpoint, one cycle

Each term is an entropy term, as defined by corollary 7.

S1  S2  ...  0

A process is irreversible if the LHS > 0, reversible if the LHS = 0, and not possible if the
LHS < 0. Important point – the Clausius inequality considers heat from the viewpoint of the
engine. The 8th corollary considers heat from the viewpoint of the fluid, and conforms entropy
as a fluid property.
Example: Consider a heat engine with the following heat additions per cycle.

Reservoir temperature, T1 = 1500 K; heat addition to engine Q1 = 0.75 kJ

Reservoir temperature, T2 = 1000K; heat addition to engine Q2 = 0.5 kJ
Reservoir temperature, T3 = 800 K; heat addition to engine Q3 = 0.4 kJ

Find the minimum heat rejection to a fourth reservoir at 300 K

If the cycle is reversible then for entropy to sum to zero (8th corollary)

-0.75/1500 -0.5/1000 -0.4/800 + Q4/300 ³ 0

Note that signs in front of hot reservoir heat transfers are negative to indicate heat loss from the
reservoir.

Q4  0.45 kJ (indicates heat transfer from engine to cold reservoir)

From the first law, the work is 0.75+0.5+0.4-0.45 = 1.2 kJ

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Lecture 4 Application of Entropy

10) Entropy of Pure Substances

Consider an infinitesimally small change in internal energy. This is a property of

state and achievable through many processes, including reversible ones,

dU  dQ  d W  dQrev  dWrev  T dS  p dV (11)

The latter is know as the Gibbs equation. (We could also write

dH  d(U  pV)  T dS  pdV  d(pV)  TdS V dp )

Noting the specific properties (u = U/m, s = S/m, v=V/m), divide Eqn. 11

throughout by m T and rearrange.

du dv
ds  p (12)
T T

The above is my rearrangement of the Gibbs equation, citing specific entropy, an

intensive property. For liquids pdv  0 and du = c dT so,

2
dT T 
s 2  s1  c   c ln  2  (13)
1
T  T1 

For ideal gases p = RT / v, du = cv dT and

2
dT
2
dV T  V 
s 2  s1  c v  R   c v ln  2   R ln  2  (14)
1
T 1
V  T1   V1 

Substitute in the ideal gas law, V2/ V1 = T2/T1 * p1/p2

T  p 
s 2  s1  c p ln  2   R ln  2  (15)
 T1   p1 

In an isentropic expansion s2 = s1 and the above yields,

 1
T2 p  
  2  (16)
T1  p1 

where  = cp/cv = cp/(cp - R) is the heat capacity ratio.

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11) The Carnot Cycle

Sadi Carnot (1824) proposed a theoretical cycle that is reversible. Let T H and TL be the
temperatures of the hot and cold reservoirs. During heat exchange, the working gas
must differ from TH or TL only infinitesimally.

Heating at TH

Adiabatic expansion, Q =0

TL
3
Cooling at TL

4 TL

Adiabatic compression, Q =0

Fig. 8 Showing the piston positions for the Carnot cycle

15
 1
QH
p
TH = const
Adia-
batic 2

4 Adiabatic
TL = const

QL 3

Fig. 9 Showing the paths of the Carnot Cycle on a pV diagram

(1)The piston is at its lowest point.

(1-2) The working gas is heated isothermally and expands. The source-to-gas
temperature difference, is infinitesimally small (TH - Tgas  0).
(2-3) Expansion is adiabatic (no heat transfer) and frictionless. The working gas cools.
(3- 4) The working gas is cooled isothermally (Tgas - Tsink -> 0) and contracts.
(4- 1) Compression is adiababic and fricitonless. The working gas increases
temperature.

We note,

(1) All processes are reversible. The cycle will be more efficient than any cycle that
comprises irreversible processes.
(2) With regard to the p-V diagram,

work(out) = area under curves 1-2-3

work(in) = area under curves 3-4-1

If we compare the difference,

Net (useful) reversible work = area 1-2-3-4 (17)

The above holds true for any reversible cycle.

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(3) The Carnot cycle obeys the second law. Not only must heat be added to the system,
it must also be rejected.

(4) Net work is evident only if TH > TL.

This allows us to introduce a new diagram, the temperature entropy (T S)

diagram.

Figure 10. Carnot Cycle Shown on a TS Diagram

Here the isothermal heat exchange follows horizontal lines, whereas the
Isentropic expansion and compression follow vertical lines. Following dQ(rev) = T dS
the area under each line is the reversible heat transfer. If, for example, expansion and
compression are irreversibly the lines are inclined to the vertical and always show
increasing entropy.

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Figure 11 Carnot Cycle showing irreversible expansion and compression

Reversing the cycle creates a heat pump, shifting heat from a low temperature
reservoir to a high temperature reservoir. The magnitutes of W, Q H, and QL can be
matched to those of the Carnot Engine; the signs are reversed.

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 1 R’voir at TH

QH
QH
p
TH = const Heat
Adia- Pump W
batic
4
2 QL
Adiabatic R’voir at TL
TL = const

QL 3

Fig. 12 Reversed Carnot Cycle

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