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Lecture 3

Lecture 6b First Law of Thermodynamics

(Specific Heats)
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

where C 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 C.

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.

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 = (, )

Consider the form = (, ) , and use the chain rule to write how u changes with respect
to T and v:

= +

For a constant volume process, the second term is zero since there is no change in volume,
= 0. Now if we write the First Law for a quasi-static process, with = ,

= ,

we see that again the second term is zero if the process is also constant volume. Equating
above equations with dv cancelled in each,

= =

By definition of specific heat; the specific heat for a constant volume process,

=

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Lecture 3

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 depend only the state.

Over small temperature changes( 200 ), 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. It is thus often useful to treat them as constant. If so

= and =

Therefore; 2 2 = (2 1 ) and 2 2 = (2 1 )

A very important relation between the constant-pressure and constant-volume specific heats
of an ideal gas may be developed from the definition of enthalpy

= + = +

Differentiating and substituting, we have = +

0 = 0 +

Therefore, 0 0 =

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

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

The simple relations between changes in energy (or enthalpy) and temperature are a consequence
of the behaviour of an ideal gas, specifically the dependence of the energy and enthalpy on
temperature only, and are not true for more complex substances.
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Lecture 3