Thermodynamics and Propulsion

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Subsections

 2.4.1 Specific Heats of an Ideal Gas

 2.4.2 Reversible adiabatic processes for an ideal gas

2.4 Specific Heats: the relation

between temperature change and
heat
[VW, S& B: 5.6]

How much does a given amount of heat transfer change the temperature of a
substance? It depends on the substance. In general

(2..4)

where is a constant that depends on the substance. We can determine the

constant for any substance if we know how much heat is transferred. Since heat
is path dependent, however, we must specify the process, i.e., the path, to
find .

Two useful processes are constant pressure and constant volume, so we will
consider these each in turn. We will call the specific heat at constant

pressure , and that at constant volume , or and per unit mass.

 1. The Specific Heat at Constant Volume

Remember that if we specify any two properties of the system, then the
state of the system is fully specified. In other words we can

write , or . [VW, S & B: 5.7]

Consider the form , and use the chain rule to write

how changes with respect to and :

(2..5)

For a constant volume process, the second term is zero since there is no
change in volume, . Now if we write the First Law for a quasi-

static process, with ,

(2..6)

we see that again the second term is zero if the process is also constant
volume. Equating (2.5) and (2.6) with canceled in each,

and rearranging
 In this case, any energy increase is due only to energy transfer as heat.
We can therefore use our definition of specific heat from Equation (2.4)
to define the specific heat for a constant volume process,

2. The Specific Heat at Constant Pressure

If we write , and consider a constant pressure process, we

can perform a similar derivation to the one above and show that

In the derivation of , we considered only a constant volume process, hence

the name, ``specific heat at constant volume.'' It is more useful, however, to

think of in terms of its definition as a certain partial derivative, which is a

thermodynamic property, rather than as a quantity related to heat transfer in a
special process. In fact, the derivatives above are defined at any point in any
quasi-static process whether that process is constant volume, constant
pressure, or neither. The names ``specific heat at constant volume'' and
``specific heat at constant pressure'' are therefore unfortunate

misnomers; and are thermodynamic properties of a substance, and by

definition depend only the state. They are extremely important values, and have
been experimentally determined as a function of the thermodynamic state for an
enormous number of simple compressible substances2.1.
To recap:

or

Practice Questions Throw an object from the top tier of the lecture hall to the
front of the room. Estimate how much the temperature of the room has changed
as a result. Start by listing what information you need to solve this problem.

2.4.1 Specific Heats of an Ideal Gas

The equation of state for an ideal gas is

where is the number of moles of gas in the volume . Ideal gas behavior
furnishes an extremely good approximation to the behavior of real gases for a
wide variety of aerospace applications. It should be remembered, however, that
describing a substance as an ideal gas constitutes a model of the actual
physical situation, and the limits of model validity must always be kept in mind.

One of the other important features of an ideal gas is that its internal energy
depends only upon its temperature. (For now, this can be regarded as another
aspect of the model of actual systems that the ideal gas represents, but it can
be shown that this is a consequence of the form of the equation of state.)
Since depends only on ,

or
In the above equation we have indicated that can depend on . Like the
internal energy, the enthalpy is also only dependent on for an ideal gas.

(If is a function of , then, using the ideal gas equation of state, is

also.) Therefore,

and

If we are interested in finite changes of internal energy or enthalpy, we

integrate,

and

Over small temperature changes ( ), it is often assumed

that and are constant. Furthermore, there are wide ranges over which
specific heats do not vary greatly with respect to temperature, as shown in
SB&VW Figure 5.11. It is thus often useful to treat them as constant. If so
These equations are useful in calculating internal energy or enthalpy
differences, but it should be remembered that they hold only if the specific heats
are constant.

We can relate the specific heats of an ideal gas to its gas constant as follows.
We write the first law in terms of internal energy,

and assume a quasi-static process so that we can also write it in terms of

enthalpy, as in Section 2.3.4,

Equating the two first law expressions above, and assuming an ideal gas, we
obtain

Combining terms,

Since ,
An expression that will appear often is the ratio of specific heats, which we will
define as

Below we summarize the important results for all ideal gases, and give some
values for specific types of ideal gases.

1. All ideal gases:

1. The specific heat at constant volume ( for a unit mass

or for one kmol) is a function of only.

2. The specific heat at constant pressure ( for a unit mass

or for one kmol) is a function of only.

3. A relation that connects the specific heats , , and the gas

constant is

where the units depend on the mass considered. For a unit

mass of gas, e.g., a kilogram, and would be the specific

heats for one kilogram of gas and is as defined above. For one
kmol of gas, the expression takes the form

where and have been used to denote the specific heats

for one kmol of gas and is the universal gas constant.

4. The specific heat ratio, (or ), is a function

of only and is greater than unity.
2. An ideal gas with specific heats independent of

temperature, and , is referred to as a perfect

gas. For example, monatomic gases and diatomic gases at ordinary
temperatures are considered perfect gases. To make this distinction the
terminology "a perfect gas with constant specific heats" is used
throughout the notes. In some textbooks perfect gases are sometimes
also referred to as ideal gases, and to avoid confusion we use the stated
terminology2.2.
3. Monatomic gases, such as He, Ne, Ar, and most metallic vapors:

1. (or ) is constant over a wide temperature range and is

very nearly equal to [or , for one kmol].

2. (or ) is constant over a wide temperature range and is

very nearly equal to [or , for one kmol].

3. is constant over a wide temperature range and is very nearly

equal to [ ].

4. So-called permanent diatomic gases, namely H ,O ,N , Air, NO,

and CO:

1. (or ) is nearly constant at ordinary temperatures, being

approximately [ , for one kmol], and increases

slowly at higher temperatures.

2. (or ) is nearly constant at ordinary temperatures, being

approximately [ , for one kmol], and increases

slowly at higher temperatures.

3. is constant over a temperature range of

roughly to and is very nearly equal

to [ ]. It decreases with temperature above this.

5. Polyatomic gases and gases that are chemically active, such as CO ,

NH , CH , and Freons:
 The specific heats, and , and vary with the temperature, the
variation being different for each gas. The general trend is that heavy
molecular weight gases (i.e., more complex gas molecules than those

listed in 2 or 3), have values of closer to unity than diatomic gases,

which, as can be seen above, are closer to unity than monatomic gases.

For example, values of below 1.2 are typical of Freons which have
molecular weights of over one hundred.2.3

In general, for substances other than ideal gases, and depend on pressure
as well as on temperature, and the above relations will not all apply. In this
respect, the ideal gas is a very special model.

In summary, the specific heats are thermodynamic properties and can be used
even if the processes are not constant pressure or constant volume. The simple
relations between changes in energy (or enthalpy) and temperature are a
consequence of the behavior of an ideal gas, specifically the dependence of the
energy and enthalpy on temperature only, and are not true for more complex
substances.2.4

2.4.2 Reversible adiabatic processes for an ideal

gas

From the first law, with , , and ,

(2..7)

Also, using the definition of enthalpy,

(2..8)

The underlined terms are zero for an adiabatic process. Rewriting (2.7) and
(2.8),
Combining the above two equations we obtain
(2..9)

Equation (2.9) can be integrated between states 1 and 2 to give

For an ideal gas undergoing a reversible, adiabatic process, the relation

between pressure and volume is thus:

We can substitute for or in the above result using the ideal gas law, or
carry out the derivation slightly differently, to also show that

We will use the above equations to relate pressure and temperature to one
another for quasi-static adiabatic processes (for instance, this type of process is
our idealization of what happens in compressors and turbines).

Practice Questions

1. On a - diagram for a closed-system sketch the thermodynamic paths

that the system would follow if expanding

from to by isothermal and quasi-static,

adiabatic processes.
2. For which process is the most work done by the system?
3. For which process is there heat exchange? Is it added or removed?
4. Is the final state of the system the same after each process?
 5. Derive expressions for the work done by the system for each process.

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