Thermodynamics

Y Y Shan

Chapter 3 Heat engines and the Second law of thermodynamics

3.1

Heat capacity (or specific heat)

Heat capacity,(also known as the specific heat) is the amount of heat energy per unit

mass required to raise the temperature by one degree. More heat energy is required to increase
the temperature of a substance with high specific heat capacity than one with low specific heat
capacity.

The specific heat of water is 1 calorie/gram C = 4.186 joule/gram C which is higher

than any other common substance. As a result, water plays a very important role in temperature
regulation. The specific heat per gram for water is much higher than that for a metal. The
above relationship does not apply if a phase change is encountered, because the heat added or
removed during a phase change does not change the temperature.
3.1.1 Heat capacity at constant volume and constant pressure
More scientifically in thermodynamics, the heat capacity C should be mathematically
defined as the ratio of a small amount of heat Q added to the body, to the corresponding small
increase in its temperature dT under some specific conditions or constraint:

Q
Cx =

dT x
x refers to the constraint or conditions under which heat capacity is measured. The most
common and conditions are under constant volume and constant pressure.
, i.e., the most important heat capacities are heat capacity at constant volume V,

Q
CV =

dT V
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and heat capacity at constant pressure P,

Q
CP =

dT P
When heat capacity is measured at constant volume, from the first law:

dU = Q + W ,
where W = PdV = 0, so that

Q = dU , and
Q dU

U
CV =
=
=

dT V dT V T V

eq3 - 1

When heat capacity is measured at constant pressure, from the first law:

dU = Q + W
Q = dU W = dU + PdV
so that
Q dU + PdV U
V
CP =
=
=
+ P

dT
dT P
P T P
T P

eq3 - 2

If we define a state function:

H = U + PV

then under the conditionof constant pressure,

dH = dU + PdV
and
Q dU + PdV H
CP =
=
=

dT
dT

P
P T P
The defined function H is namely enthalpy.

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3.1.2 The CP~CV relationship for an ideal gas

In general, for any system, a relationship between CV and CP can be obtained by using
the first law, and it can be simplified after applying the second law
(a) Internal energy for an ideal gas and Joules law
The state function U is the function of temperature and volume, the two state coordinates of
gases, i.e.

U = U (T ,V )
From partial differential calculus,

U
U
dU (T ,V ) =
dT +
dV
T V
V T
It can be derived that (see math appendix later)

U
U T

=

, i.e.
V T
T V V U
U
T

= CV

V T
V U
T
where
is called Joule's coefficient
V U

eq3 - 3

Now look at the Joules experiment, in 1845, Joule performed an experiment where a
gas at high pressure inside a bath at the same temperature was allowed to expand into a larger
volume.

Two vessels, labeled A and B, are immersed in an insulated tank containing water. One
thermometer is used to measure the temperature of the water in the tank. The two vessels A
and B, being thermally equilibrium with the bath, are connected by a tube, the flow through

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which is controlled by a stop. Initially, A contains gas at high pressure, while B is nearly empty.
The stop is removed so that the vessels are connected and the final temperature of the bath is
noted.
The fact that the temperature of the bath was unchanged at the end of the process
indicates that the temperature of gas does not change either ( T = 0 ) when its volume
changes ( V 0 ), i.e .

T
= 0,
V
From eq3-3, we obtain

=0
V T

eq.3-4

This concludes that the internal energy of an ideal gas is volume independent, it is the function
of temperature alone, U=U(T,V)=U(T). The equation above is called Joule's law which stated
as (U/V)t = 0
(b) Ideal gass (C P CV ) value and C P / CV value
It can be proved that, for ideal gas,

C P CV = nR

eq3-5

Derivation:

U
U
dU (T ,V ) =
dT +
dV
T V
V T
= CV dT + 0( Joule' s law) = CV dT
First law : dU = Q + W = Q PdV = CV dT
therefore : Q = CV dT + PdV
nR
Q
dV
CP =
, (using PV = nRT), so
= CV + P
= CV + P
dT
dT
P

P
C P CV = nR
The ratio C P / CV is defined as: C P / CV = , so that

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CP =
CV =

nR

1
nR
1

The most common values being air = 1.4 for air, and monoatomic gas = 1.66 .
3.2 Heat engines

(a) Thermodynamic cycle: Thermodynamics began as the study of the efficiency of heat
engines. An engine will be defined as a machine which at the end of a complete cycle,
consisting several thermal processes, can convert some heat energy into useful mechanical
work. The process can then be repeated another cycle and so on. As we know that work done
in a thermal process is not a state function, meaning it depends on the path (which curve you
consider for integration from state 1 to 2). For a system in a cycle which has states 1 and 2, the
work done depends on the path taken during the cycle. If, in the cycle, the movement from 1 to
2 is along A and the return is along C, then the work done is the lightly shaded area. However,
if the system returns to 1 via the path B, then the work done is larger, and is equal to the sum of
the two areas

The right figure above shows a typical indicator diagram as output by an automobile engine.
The shaded region is proportional to the work done by the engine, and the volume V in the xaxis is obtained from the piston displacement, while the y-axis is from the pressure inside the
cylinder. The work done in a cycle is given by W, where

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(b) Thermal efficiency of a heat engine

Thermal efficiency (

) is a performance evaluation of a thermal device such as an

car engine, or a furnace,. The input, Qin or QH , to the device is heat energy (or the heat
energy of a fuel that is consumed) . The desired output is mechanical work,

The thermal efficiency of a heat engine is the percentage of heat energy that is transformed
into work, the efficiency is defined as

,
When expressed as a percentage, the thermal efficiency must be between 0% and 100%.

Due to inefficiencies such as friction, heat loss, and other factors, thermal efficiencies
are typically much less than 100%. For example, a typical gasoline automobile engine
operates at around 25% thermal efficiency, and a large coal-fueled electrical generating
plant peaks at about 36%

(c) Schematic expression of a heat engine in thermodynamics

For a heat engine, the heat energy comes from a high temperature reservoir, TH, (such
as fuel burning or boiling water for creating steaming gas). This heat energy absorbed
from the high temperature reservoir, QH, will be partly converted to mechanical work, Wout,
and some heat energy released to low temperature reservoir, TH, (such as cooling water or
cooling fan). Schematically, it is often shown as:

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3.3

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Analysis of thermodynamic cycles (or engine cycles)

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A thermodynamic cycle is a series of thermodynamic processes (usually consists four)

which returns a system to its initial state, so that the change of the total internal energy is
zero: U = 0 . A thermodynamic cycle is a closed loop on a P-V diagram

A typical P-V diagram for a thermodynamic cycle represents a heat engine. The cycle
consists of four states (1, 2, 3, 4) and four thermodynamic processes (lines 1-2, 2-3, 3-4, 41). The area enclosed by the loop is the work (W) done by the process:

Wout = pdV = W12 +W23 + W34 + W41

The first law of thermodynamics dictates that the work is equal to the balance of heat (Q)
transferred into the system over any cycle:

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U = Q Wout = 0
where net heat obsorbed Q Qin Qout so that
Wout = Qin Qout
The efficiency :

th =

Wout
Qin

th = 1

3.3.1

Qout
Qin

Analysis of the typical four processes in a heat engine cycle

Each heat engine proces can be described on a PV diagram. Besides constant pressure,
volume and temperature processes, a useful process is the adiabatic process where no heat
enters or leaves the system.

(i)

Constant volume process (isometric or isochoric process)

The first law gives: U = Q + W = Q, W = 0

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(ii)

Y Y Shan

Constant pressure process(isobaric process)

The first law gives: U = Q + W = C P nT PV

(iii)

Isothermal Process: the result of expansion gives the work expression below.

The first law gives: U = Q + W

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For ideal gas, internal energy is only temperature dependent, so that for isothermal process:

U = 0, therefore
Q +W = 0
Q = W = PdV

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(iv) Adiabatic process: one in which no heat is gained or lost by the system. The first law
of thermodynamics with Q=0 shows that all the change in internal energy is in the form of
work done.

U = Q + W = W = PV
or its differential form
dU = dW = PdV

In an adiabatic process, the P-V cure of an ideal gas has an exponential form of

P = KV

or

PV = K

eq.3 - 7

where K is constant, is the ratio of specifice heats.

This is called the adiabatic condition of ideal gas. The derivation can be shown in the
following:

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step1 : firstlaw : dU = dQ + dW = dW = PdV , (dQ = 0, adiabatic)

step 2 : fromJoule' slaw : dU = CV dT
fromsteps1,2 : CV dT = PdV

- - - - - - - - - - - - - - - - - - - - - - - - - -(a)

step3 : StateEquation : PV = nRT , so, nRdT = d ( PV ) = PdV + VdP

step 4 : nR = C P CV = CV ( 1)
fromsteps3,4 : CV dT = ( PdV + VdP)( 1) 1 - - - - - - - - - - - - - - - - - -(b)
step5 : from a, b : PdV = ( PdV + VdP)( 1) 1 VdP + PdV = 0
dP
dV
+
=0
- - - - - - - - - - - -eqn3 - 8
P
V
This is called the differential equation of the adiabatic condition.
step6 : solve equation3 - 8, the adiabatic condition for ideal gas can be obtained
PV = const. = K

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