1 INTRODUCTION
The specific heat of a substance is defined
by:
C=1 dq
N dt
where dQ is the amount of heat that must be
added (or removed) from a quantity
N of a substance in order to change its
temperature by dT. In general, the value
of c depends upon what constraints are
imposed upon the thermal expansion of the
material during the heating process. For
example, the substance might be heated
along a path of constant volume. Or, it might
be heated along a path of constant
pressure. For gases, differences in path lead
to significant differences in the specific
heat. Such differences can be understood in
terms of the first law of thermodynamics:
dQ=dU+PdV
or in words,Heat Added =Change in internal
energy
+ External Work done on
or by the system
For gases the external work obviously
depends upon the amount of expansion
allowed
during heating. Thus, no work is done on a
gas heated along a path of constant
volume; but work is done on a gas heated at
constant pressure. In heating most
liquids or solids, the amount of external work
is small compared to the amount of
heat absorbed as internal energy, so that the
specific heat depends only slightly
on the process. Thus for most liquids and
solids, the specific heat at constant
pressure, cp , is commonly given in tables
and handbooks as “the specific heat” of
such substances.
In gases, the difference between the two
specific heats is more pronounced. In this
experiment, you will measure the ratio of the
specific heats of a gas by an indirect
method that will be described later. In
dealing with gases, it is usual to consider
molar specific heats: we express the amount
of gas N in Equation (1) in terms ofmoles. Gases are particularly simple and
appropriate substances to study because:
1. To the extent that real gases approximate
ideal gases (a very good approxima-
tion in many cases), the internal energy U
depends only upon the temperature.
Except at very low temperatures or at very
high pressures, U does not depend
on either pressure or volume.
(The experimental basis for this assertion is
the Joule adiabatic free expansion
experiment—make sure you understand why.
A theoretical explanation is that
the potential energy arising from
intermolecular forces is a negligible fraction
of the internal energy because the molecules
are very far apart on the average.
The main contribution to the internal energy
is the kinetic energy of molecular
motion, which depends only upontemperature).
2. The dependence of the specific heat upon
the nature of the heating process is
pronounced.
3. Theoretical values of the specific heat of
an ideal gas can readily be com-
puted. Interestingly, one needs to use
quantum|to get the correct
theoretical result.
2 IDEAL GASES
In this section we shall review some of the
standard equations governing the behavior
of ideal gases. This material is discussed in
more detail in your text, to which you
should refer if any of this material seems
hard to understand.
We need to find a relation between the
specific heats for an ideal gas along paths
of
constant volume and constant pressure. We
begin with the former. Equations (1)
and (2) can be combined to obtain the heat
absorbed at constant volume (dV = 0):
dQ = dU = NcvdTwhere cv is the specific heat at constant
volume. (Note: Be sure you can derive
this result.)
For an ideal gas whose internal energy
depends only upon temperature, this
equation
has special significance; it is a general
expression which gives the change in
internal
energy dU for any process regardless of
whether or not work is done. In other words,
the change in internal energy for any process
which involves a temperature change
dT is the same as the heat needed to
produce the same temperature change in a
constant volume process.
We now turn to the specific heat at constant
pressure for an ideal gas. The equation
of state for an ideal gas is given by the
familiar equation
PV =nkRT.
If we take the differential of this equation, we
obtain
P dV + V dP = nRdTWe find cp as follows: Using Equations (1)
and (2), we obtain for any arbitrary
process
dQ = dU +P dV = ncvdT +P dV.
But if we set dP = 0 in Equation (4), we
obtain
P dV = nRdT,
and if we combine the last two equations, we
obtain
dQ = ncvdT + nRdT = N PDT.
Hence we obtain a general result for ideal
gases:
cp=cv+R
Again, be sure you can derive this result
yourself.
Our experiment will make use of adiabatic
processes—expansions (or compressions)
carried out with no exchange of heat
between the gas and its surroundings. Con-
sequently we need to review the behavior of
an ideal gas undergoing an adiabatic
process. If we set dQ = 0 in Equation (5), we
have
dQ =0= nCvdT + P dVIf this equation is multiplied by R/cv and
added to the gas law [Equation (4)], we
obtain the following expression, which
involves only P and V:
yP dV + V dP =0
where y is defined as
y=1+R
cv
=cp
CV
The second equality is based on Equation
(2). If we integrate Equation (7), we
obtain
PV y=constan
Equation (9) is a relationship between the
pressure and volume of an ideal gas
subjected to an adiabatic process. For an
isothermal process, of course, P V is
constant.
In this experiment we shall measure the
quantity y directly. We can find values for
cp and cv using Equation (8) and the gas
constant R.