PHYSICAL

CHEMISTRY
MET (201)
LECTURE (4)
GROUP (3)

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 2.4 Constant Volume Processes

Since δw = − Psur dV, then δw = 0 for

a constant volume process and based on the
First Law of Thermodynamics, the following
relation can be written:
dU = δq𝝂 ,
By integrating the previous relation, the
following relation can be written:
ΔU = q𝝂

2.5 Constant Pressure Processes

and Definition of Enthalpy (H)

If the pressure of the system is maintained

constant during a process (isobaric process)
which takes the system from state one to
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state two and if the process is reversible (in
other words, Psur = Pgas = P at all time) then
the work done by the system is given by the
following relation:
𝒗𝟐
𝒘 = − ∫𝒗 𝑷𝒅𝑽 = −𝑷(𝑽𝟐 − 𝑽𝟏 );
𝟏
then, ΔU = qP – [P(V2 – V1)],
or qP = (U2 + PV2) – (U1 + PV1)
As the expression (U + PV) contains only
state functions, then the expression itself is
a state function; this expression is termed the
enthalpy (H); thus,
H = U + PV
Hence, for a constant pressure process, we
can write the following relation:
qP = ΔH

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 2.6 Reversible Adiabatic
Processes for Ideal Gas

In a reversible adiabatic process for an ideal

gas, the value of 𝑞 = 0. Thus, based on the
first law of thermodynamics and by using
the equation of state of ideal gases, the
following relations are valid for reversible
adiabatic processes:
𝑷𝑽𝜸 = 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕,
and 𝑻𝑽𝜸−𝟏 = 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕,
also, 𝑻𝑷(𝟏−𝜸)/𝜸 = 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
where, 𝜸 = (𝒄𝒑 /𝒄𝝂 )
The irreversibility of any adiabatic
process will be discussed in Chapter (3)
in-detail.

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 2.7 Reversible Isothermal
Processes for Ideal Gases

For any isothermal process, dT = 0; then

dU = 0. Accordingly, the following relation
can be written: δq = −δw = P dV,
thus, q = −w = RT n(𝑽𝟐 /𝑽𝟏 ) = RT n(𝑷𝟏 /𝑷𝟐 )
The P-V relations for a reversible isothermal
process and a reversible adiabatic process
are shown on the binary P-V diagram of
figure (2.2). This figure shows that for a
given pressure decrease, the work done by
the reversible isothermal process exceeds
that done by the reversible adiabatic process.
The irreversibility of an isothermal
process will be discussed in Chapter (3)
in detail.

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Figure (2.2): The P-V Diagram for Isothermal and Adiabatic Processes

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 2.8 Heat Capacity

The heat capacity (C) of a system is the ratio

of the amount of heat added or withdrawn to
(or from) the system, respectively, to the
resultant change in the temperature of the
system; then, C = 𝒒/∆𝑻
Thus, for infinitesimal change the following
relation is obtained for C:
C = 𝜹𝒒/𝝏𝑻
The concept of heat capacity is only used
when the addition or withdrawal of heat
from the system produces a temperature
change and when a phase change does not
occur; thus, the concept of heat capacity is
not used when the process is isothermal.
The change of temperature of a system from
T1 to T2 due to the addition of a certain

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quantity of heat to the system is not a
complete thermodynamic statement since the
state of any system is defined only by two
independent variables; thus, this second
independent variable could be varied in a
specified manner or could be maintained
constant during the change.
Thus, the simplest methods to define the
heat capacity term are either by temperature
change at constant volume (𝐶𝑣 ), or at
constant pressure, (𝐶𝑃 ), according to the
following:
𝑪𝒗 = (𝜹𝒒/𝝏𝑻)𝑽 or 𝑪𝑷 = (𝜹𝒒/𝝏𝑻)𝑷
The heat capacity, as defined, is an extensive
function; however, by defining the specific
heat capacity as the heat capacity of the
system per unit mass (one gram, one gram
atom, or gram mole) of the system,

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the specific heat capacity becomes an
intensive function.
Since: 𝑪𝒗 = (𝜹𝒒/𝝏𝑻)𝑽 = 𝜹𝒒𝒗 /𝝏𝑻 ,
or 𝑪𝒗 = (𝒅𝑼/𝒅𝑻)𝑽
Thus, 𝒅𝑼 = 𝑪𝒗 𝒅𝑻
Also, 𝑪𝑷 = (𝜹𝒒/𝝏𝑻)𝑷 = 𝜹𝒒𝑷 /𝝏𝑻 ;
thus, 𝑪𝑷 = (𝒅𝑯/𝒅𝑻)𝑷
Then, 𝒅𝑯 = 𝑪𝑷 𝒅𝑻
It is expected that for any substance, the
value of Cp will be of greater magnitude than
the value of 𝑪𝒗 . This is because the heat
required to increase the body temperature by
one degree involves the amount of heat
required to cause expansion of the body
against external constant pressure.
The relation between Cp and 𝑪𝒗 can be
calculated by using the following relation:
𝑪𝑷 − 𝑪𝒗 = (𝝏𝑯/𝝏𝑻)𝑷 − (𝝏𝑼/𝝏𝑻)𝑽 ,
thus, 𝑪𝑷 − 𝑪𝒗 = (𝝏𝑼/𝝏𝑻)𝑷 + 𝑷(𝝏𝑽/𝝏𝑻)𝑷 − (𝝏𝑼/𝝏𝑻)𝑽
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As 𝑼 = 𝒇(𝑽, 𝑻),
then, 𝒅𝑼 = (𝝏𝑼/𝝏𝑽)𝑻 𝒅𝑽 + (𝝏𝑼/𝝏𝑻)𝑽 𝒅𝑻;
thus, (𝝏𝑼/𝝏𝑻)𝑷 = (𝝏𝑼/𝝏𝑽)𝑻 (𝝏𝑽/𝝏𝑻)𝑷 + (𝝏𝑼/𝝏𝑻)𝑽
or 𝑪 − 𝑪 = (𝝏𝑼/𝝏𝑽) (𝝏𝑽/𝝏𝑻) + (𝝏𝑼/𝝏𝑻) + 𝑷(𝝏𝑽/𝝏𝑻) − (𝝏𝑼/𝝏𝑻)
𝑷 𝒗 𝑻 𝑷 𝑽 𝑷 𝑽

thus, 𝑪𝑷 − 𝑪𝒗 = (𝝏𝑽/𝝏𝑻)𝑷 [(𝝏𝑼/𝝏𝑽)𝑻 + 𝑷]

The difference between 𝑪𝑷 and 𝑪𝒗 is thus
given by the following relation:
𝑪𝑷 − 𝑪𝑽 = 𝑷(𝝏𝑽/𝝏𝑻)𝑷 + (𝝏𝑼/𝝏𝑽)𝑻 (𝝏𝑽/𝝏𝑻)𝑷
The term 𝑷(𝝏𝑽/𝝏𝑻)𝑷 represents the work
done by the system per one degree rise in
temperature due to expansion against the
constant external pressure (P) acting on the
system; the term (𝝏𝑼/𝝏𝑽)𝑻 (𝝏𝑽/𝝏𝑻)𝑷
represents the work done due to
intermolecular expansion against the internal
cohesive forces acting between the atoms
(or molecules) of the substance when the
temperature rises by one degree. Thus, for
perfect gases the value of (𝝏𝑼/𝝏𝑽)𝑻 (𝝏𝑽/𝝏𝑻)𝑷 = 𝟎;

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for real gases the magnitude of 𝑷(𝝏𝑽/𝝏𝑻)𝑷
is much greater than the value of
(𝝏𝑼/𝝏𝑽)𝑻 (𝝏𝑽/𝝏𝑻)𝑷 which approaches the
zero value. For condensed phase, however,
the magnitude of (𝝏𝑼/𝝏𝑽)𝑻 (𝝏𝑽/𝝏𝑻)𝑷 is
much greater than the value of 𝑷(𝝏𝑽/𝝏𝑻)𝑷
which approaches the zero value.
Joule proved through experimentation
that (𝝏𝑼/𝝏𝑽)𝑻 = 𝟎. Joule's experiment
involved two copper vessels, one is filled
with an amount of gas at some pressure
connected to a similar evacuated vessel via
a stopcock. The two-vessel system was
immersed in a quantity of adiabatically
contained water. The stopcock was then
opened; thus, free expansion of the gas into
the evacuated vessel is allowed. After this
expansion, Joule could not detect any
change in the system temperature.
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As the system was adiabatically contained
and no work was performed; then, based
on the First Law of Thermodynamics the
following relations can be write:
∆𝑼 = 𝟎
Accordingly, 𝒅𝑼 = (𝝏𝑼/𝝏𝑽)𝑻 𝒅𝑽 + (𝝏𝑼/𝝏𝑻)𝑽 𝒅𝑻 = 𝟎
Since 𝒅𝑻 = 𝟎 and 𝒅𝑽 ≠ 𝟎, thus (𝝏𝑼/𝝏𝑽)𝑻 = 0;
in other words, the internal energy of a
perfect gas is not function of volume (and
hence pressure). Thus, the Internal energy is
function only of temperature. Therefore, for
ideal (or perfect) gases, the following
relations can be written:
1. 𝑪𝑷 − 𝑪𝑽 = 𝑷(𝝏𝑽/𝝏𝑻)𝑷 = 𝑷(𝝏(𝑹𝑻/𝑷)/𝝏𝑻)𝑷 = 𝑹,
2. 𝑼 = 𝒇(𝑻) since (𝝏𝑼/𝝏𝑽)𝑻 = 𝟎
The reason for not observing a temperature
rise in the original experiment of joule was
that the heat capacity of copper vessels and
water was considerably greater than the heat

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capacity of the gas; thus, the small
temperature changes which might occur in
the gas were not detected in the copper
vessels and water.

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