CCTD101B Internal Energy and Enthalpy

1

UNIVERSITY OF TRINIDAD AND TOBAGO

B.A.Sc. Utilities Engineering

February 09, 2009

CCTD101B Engineering Thermodynamics (Lecture Notes 5)
Properties that Depend on the First Law - I nternal Energy and Enthalpy

5. Internal Energy and Enthalpy ............................................................................................................. 1
5.1 Internal Energy and Enthalpy of Substances ...................................................................................................... 1
5.2 Latent Heat ............................................................................................................................................................. 1
5.3 Evaluating Specific Heats, c
v
, c
p
............................................................................................................................ 2
5.4 Approximations for liquids using saturated liquid data ..................................................................................... 3
5.4.1 Incompressible Substance model .................................................................................................................... 3
5.5 Internal Energy and Enthalpy of Ideal Gases ..................................................................................................... 4
5.5.1 Specific heats of Ideal Gases .......................................................................................................................... 4
5.5.2 Ideal Gases with constant Specific heats ........................................................................................................ 5
5.5.3 Polytropic processes ....................................................................................................................................... 5

5. Internal Energy and Enthalpy
5.1 Internal Energy and Enthalpy of Substances
The first law allows us to define additional properties of a system: internal energy, enthalpy and specific
heats.

For any phase of a pure substance, two independent intensive properties usually define the state. Under
such conditions the internal energy and enthalpy are functions of two independent variables. The
functional relationship is typically complex, so for most substances u and h values are obtained from
correlations of properties based on experimental data.

In many thermodynamic analyses the sum of the internal energy U and the product of pressure p and
volume V appear. Because the sum U + pV occurs so frequently it is convenient to give the combination
a name, enthalpy H. By definition


Since U, p and V are all properties, the combination is also a property. Enthalpy can be expressed on a
unit mass basis


5.2 Latent Heat
For a fluid, the enthalpy/ internal energy relationship is given by; pv u h + = . This relationship is used to
calculate the value of u, if not tabulated. For liquids, the difference between internal energy and enthalpy
is small because v for liquids is very small.

For most substances, thermodynamic property data are published for saturated liquid, saturated vapour
and superheated vapour. Occasionally, compressed liquid data are included.
CCTD101B Internal Energy and Enthalpy
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When compressed liquid data are not available, a useful approximation is that the properties of the
compressed liquid are equal to the properties of saturated liquid at the same temperature.

The difference between the enthalpy of saturated vapour and that of saturated liquid at the same pressure
(and temperature),
fg f g
h h h = , is called the latent heat of vapourisation.

In a closed system initially composed of a saturated liquid, if heat is added in a quasiequilibrium process
while pressure is held constant, the amount of heat added per unit mass of fluid is;

1 2
h h q =

Heating of the saturated mixture at constant pressure to cause phase change is referred to as latent
heating (process 2-3) because the temperature does not change, heating of a single phase is called
sensible heating (process 1-2 and 3-4) because the temperature does change.

5.3 Evaluating Specific Heats, c
v
, c
p

Several properties related to internal energy are important in thermodynamics. One of these is the
property enthalpy. Two others, known as specific heats are considered. The specific heats are
particularly useful for thermodynamic calculations involving the ideal gas model.

Specific heats are intensive properties and are defined for pure simple compressible substances as partial
derivatives of the functions u(T,v) and h(T,p) respectively;
v
v
T
u
c
|
.
|

\
|
c
c

p
p
T
h
c
|
.
|

\
|
c
c

Where the subscripts v and p denote the variables held constant during differentiation.

The property k called the specific heat ratio, is simply the ratio

The properties c
v
, c
p
are referred to as specific heats (or heat capacities) because under certain special
conditions they relate the temperature change of a system to the amount of heat added by heat transfer.
CCTD101B Internal Energy and Enthalpy
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However, it is generally preferable to think of c
v
and c
p
in terms of their definitions and not with
reference to this limited interpretation involving heat transfer.

In general c
v
is a function of v and T (or p and T) and c
p
depends on both p and T (or v and T).

Specific heats of a substance vary with both temperature and pressure and are used in the evaluation of u
and h. Unit for c
v
and c
p
is kJ/kg.
0
C or kJ/kg.K.

5.4 Approximations for liquids using saturated liquid data
Approximate values for v, u and h at liquid states can be obtained using saturated liquid data. Because
the values of v and u vary only gradually as pressure changes at fixed temperature, the following
approximations are reasonable for many engineering calculations:

( )

()
( )

()
( )

()

That is for liquids, u and v may be evaluated at the saturated liquid state corresponding to the
temperature at the given state.

5.4.1 Incompressible Substance model
To simplify calculations involving liquids or solids the specific volume (density) is often assumed to be
constant and the specific internal energy assumed to vary only with temperature. A substance idealized
in this way is called incompressible.

Since the specific internal energy of a substance modeled as incompressible depends only on
temperature, the specific heat c
v
is also a function of temperature alone.
dT
du
c
v
=


Although the specific volume is constant and internal energy depends on temperature only, enthalpy
varies with both pressure and temperature only according to

( ) ()

For a substance modeled as incompressible, the specific heats c
v
and c
p
are equal.

Thus for an incompressible substance it is unnecessary to distinguish between c
v
and c
p
and both can be
represented by the same symbol c.

Using the above two equations, the changes in specific internal energy and specific enthalpy between
two states are given by

()

(incompressible)

)
()

) (incompressible)
CCTD101B Internal Energy and Enthalpy
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If the specific heats are taken as constant

) (

)

(

) is often small compared to the first term in the latter equation and may be dropped without
significantly affecting accuracy.

5.5 Internal Energy and Enthalpy of Ideal Gases
For an ideal gas, specific internal energy depends on temperature only.

()

(ideal gas)

This is expressed as an ordinary derivative because u depends only on T.

By separating the variables

()

On integration
(

) (

()

Similarly for an ideal gas the specific enthalpy depends only on temperature so the specific heat is given
by

()

(ideal gas)

By separating the variables

()

On integration
(

) (

()

For real gases, u and h are not functions of temperature only.
5.5.1 Specific heats of Ideal Gases
Two important relations involving specific heats of ideal gases are;
R c c
v p
= and
v
p
c
c
k =
The difference between c
p
and c
v
is the constant R.

Since

, it follows that k > 1. Combining the two equations

CCTD101B Internal Energy and Enthalpy
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()

()

5.5.2 Ideal Gases with constant Specific heats
For the special case of ideal gases with constant specific heats;

(

) (

)

(

) (

)

5.5.3 Polytropic processes
Recall that for a polytropic process =
n
pv constant where n is a constant.

For a polytropic process between two states

, or

When n = 1 the process is isobaric (constant pressure) and when , the process is isometric
(constant volume).

Introducing the ideal gas equation

into the above equation

( ) 1
2
1
1
1
2
1
2

|
|
.
|

\
|
=
|
|
.
|

\
|
=
n n n
V
V
p
p
T
T


Example
Air undergoes a polytropic compression in a piston cylinder assembly from p
1
= 1 bar, T
1
= 20
o
C to p
2
= 5 atm.
By employing the ideal gas model, determine the work and heat transfer per unit mass in kJ/kg if n = 1.3, R =
8.31 kJ/kgmol and M = 28.97 kg/kmol.
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