Thermodynamics

3.3.2

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Analysis of some thermodynamic cycles(heat engine cycle)

Any heat engine cycles (thermodynamic cycle) can be constructed from the combination
of the above four processes discussed in 3.3. Here are some engines and their efficiencies:
(a) Ideal cycle: the simplest kind cycle, is constructed out of a loop having a pair of parallel
isobaric processes and a pair of parallel isochoric processes

.
Net work out: W=(P2-P1)(V2-V1)
Or can be calculate: W=Wab+Wbc+Wcd+Wda=0-P2(V2-V1)+0-P1(V1-V2)=-(P2-P1)(V2V1)
Qadd=
Efficiency:

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(b) Otto cycle

Today internal combustion engines in cars, trucks, motorcycles, construction machinery
and many others, most commonly use a four-stroke cycle. The four strokes refer to intake,
compression, combustion and exhaust strokes that occur during two crankshaft rotations per
working cycle of an Otto Cycle engine. The four steps in this cycle are often informally
referred to as "suck, squeeze, bang, blow

Otto cycle is constructed out of : a pair of quasi-parallel adiabatic processes, : a pair of

parallel isochoric (constant volume) processes.
The efficiency of a reversible Otto cycle for an ideal gas is

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For the adiabatic strokes:

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so that

For the isochoric (constant volume) paths:

.
, so that

Also from adiabatic condition:

The total work done by the system is

so

where r=V2/V1, is called compression ratio, thus the maximum is (take r=1/9, =1.5)

The actual gasoline engine has efficiency much lower than 67%.

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Thermodynamics
3.4

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Carnot cycle (Carnot engine, Carnot efficiency) and Carnot theorem

3.4.1 Carnot cycle and its efficiency

The most efficient heat engine cycle is the Carnot cycle, consisting of two isothermal
processes and two adiabatic processes. The Carnot cycle can be thought of as the most
efficient heat engine cycle allowed by physical laws.

The efficiency of a heat engine cycle is given by

For the ideal gas of the Carnot cycle, this efficiency can be calculated and equals to:

Prove here:

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Note: In calculating the efficiency of heat-engine, or any other heat-engine related quantities,
the temperatures must be the values in Kelvins

3.4.2

Carnot theorem:
Carnot's theorem is a formal statement of this fact: No engine operating between two

heat reservoirs can be more efficient than a Carnot engine operating between the same
reservoirs( same TH, and same TC) This means that for any cycle operating between
temperatures TH and TC, none can exceed the efficiency of a Carnot cycle operating between
same TH and TC

Carnot

QCCar
T
W Car QHCar QCCar
= Car =
= 1 Car = 1 C
Car
QH
QH
QH
TH

any =

Q
T
W QH QC
=
=1 C 1 C
QH
QH
QH
TH

any Carnot
Cannot theorem was proposed well before the Second law of thermodynamics and can be
proved by using the Second law.
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Thermodynamics
3.5

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Heat pump and its coefficient of performance: If a thermodynamic cycle is operated

clockwise on the P-V diagram, the engine uses heat to do net work, that is called heat engine.
If operated counterclockwise, it uses external work to transport heat(suck heat from low
temperature heat source to high temperature reservoir), and is therefore called heat pump,
such as an air-conditioner and a refrigerator.

Comparing the above energy reservoir model and P-V cycle for heat engine and heat pump:
A heat pump is therefore a device which applies external work to extract heat QC from a
cold reservoir and delivers heat QH to a hot reservoir.
Heat pump can be applied either for cooling, such as refrigerator, air-conditioners used in
summer, or heating, such as air-conditioners used in winter.

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Coefficient of performance:

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Heat Pumps are usually characterized by a coefficient of

performance which is the heat energy sucked from the cold reservoir per unit work input.

CP =

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QC
QC
=
W QH QC

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3.5.1 Coefficient of performance of a reversible Carnot cycle

In thermodynamics: a reversible cycle, is defined that the system and its surroundings
will be exactly the same after each cycle.

For reversible Carnot cycle (14321), its coefficient of performance can be

derived as:

CP ,Carnot =

QC
QC
TC
=
=
W QH QC TH TC

For process 14(isothermal): T1=T4=TC, U=W+Q14=0 (QC=Q14)

4

nRTC
V
dV =nRTC ln 4 , (> 0, addingHeat)
V
V1
1

Q14 = W = PdV =
1

For process 43(adiabatic): Q43 = 0

For process 32(isothermal): T3=T2=TH, U=W+Q32=0 (QH= -Q32)
2

nRTH
V
dV =nRTH ln 2 , (< 0, releaseHeat )
V
V3
3

Q32 = W = PdV =
3

For process 14(adiabatic), Q21=0

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For the whole cycle, U =

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dU = 0, FirstLaw : U = W + Q,
11

W = Q = (Q14 + Q43 + Q132 + Q21 ) = (Q14 + Q32 )

CP ,Carnot =

3.6

TC
Q14
=
W
TH TC

Absolute zero degree, thermodynamic temperature scale(absolute temperature scale,

or Kelvin scale)
A limit to the degree of cold possible (the coldest point) should be placed as starting
point zero. Such scale is absolute temperature scale, or Kelvin scale.

What is the coldest coldness?

A definition can be given in terms of the efficiencies of Carnot engine operating between
hotter(TH) and colder(TC) thermal reservoirs.
Carnot efficiency is given by:

Carnot =

Q
T
W
=1 C =1 C
QH
QH
TH

It is obvious that the colder (smaller TC value) a cold reservoir is used, the less heat (QC) is
released to the cold reservoir. When the amount of heat, QC, is approaching zero, this means

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the reservoir used is the coldest of its kind, TC value will be mathematically zero. Temperature
scale referring to this mathematical zero as the zero degree is called absolute temperature
scale , themodynamic temperature scale, or the Kelvin temperature scale. A heat engine
whose coldest reservoir is zero degrees would operate with 100% efficiency.
If the size of the degree in absolute scale is taken as same as the Celsius-size
degrees(i.e the temperature difference between ice-water and boiling water is taken to be 100
units), the coldest temperature (defined as the absolute zero in Kelvin scale) will be 273.16
unites in Celsius scale.

Question: If a Carnot engine operating between two reservoirs, one is boiling water, the other
is ice water, it is found that for 100 Joule of heat absorbed from boiling water, 73.2 Joule of
heat will be released to ice-water, what is the absolute temperature of ice-water?

3.7 The second law of thermodynamics

The second law of thermodynamics is a general principle which places constraints upon
the direction of heat transfer , and the attainable efficiencies of heat engines. There are many
statements of the second law which use different terms, but are all equivalent.
The Lord Kelvin statement of the second law (often referred the "first form" of the
second law):
It is impossible to extract an amount of heat QH from a hot reservoir and use it all to
do work W .
Some amount of heat QC must be exhausted to a cold reservoir. Thus, a heat engine with 100%
efficiency is thermodynamically impossible.

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An equivalent statement of the second law is the statement by Clausius, often referred as the
second form of the second law:
It is impossible for heat to flow from a colder body to a warmer body without any
work having been done to accomplish this flow.
Informally, "Heat doesn't flow from cold to hot", which is obviously true from everyday
experience.

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