Chemistry 360

Spring 2012
Dr. Jean M. Standard
February 8, 2012
Review of Expansion/Compression of Gases
A review of various types of compression and expansion processes is given below. The examples focus on ideal
gases , but most of the equations can also be developed using the various equations of state for real gases. The
examples concentrate on determining the values of the First Law quantities q, w, and
!
"U, and in addition the
enthalpy change
!
"H is also given. In most cases, the processes considered are reversible processes.
I. CONSTANT TEMPERATURE (ISOTHERMAL) PROCESSES
For a reversible isothermal process,
!
w = " P dV
#
Using the ideal gas equation,

!
w = "nRT !n V
2
/V
1
( )
or

!
w = "nRT !n P
1
/ P
2
( ) .
Since
!
"U
" V
#
$
%
&
'
(
T
= 0 for an ideal gas, and
!
dT = 0 for an isothermal process, we have that
!
"U = 0. Then, from the
First Law,
!
q = "w.
Using the definition
!
H = U + PV ,
!
"H = "U + " PV ( ) .
Substituting the ideal gas expression,
!
"H = "U + " nRT ( ) ,
or
!
"H = "U + nR"T .
So, for an isothermal reversible expansion or compression of an ideal gas, since
!
"U = 0 and
!
"T = 0, we also
have that
!
"H = 0.
Summary Isothermal Reversible Processes
!
q = w
!
w =
!
"nRT !n V
2
/V
1
( )
!
"U = 0
!
"H =
0
2
II. CONSTANT PRESSURE (ISOBARIC) PROCESSES
Since P is constant,
!
w = " P
ext
#V , and if the process is reversible , then
!
w = " P #V .
We showed in class that if
!
C
p
is independent of temperature for an ideal gas, then
!
q
p
= "H = C
p
"T .
From the First Law,
!
"U = q + w = C
p
"T # P "V .
Summary Isobaric Reversible Processes
!
q =
!
"H = C
p
"T
!
w =
!
"P #V
!
"U =
!
C
p
"T # P "V

(For an isobaric process, this is actually the same as
!
C
v
"T .)
!
"H =
!
C
p
"T
III. CONSTANT VOLUME (ISOCHORIC) PROCESSES
Since the process is constant volume,
!
dV = 0. The work is therefore
!
w = " P
ext
dV
#
w = 0.
We showed in class that if
!
C
v
is independent of temperature for an ideal gas, then
!
q
v
= "U = C
v
"T .
From the definition of enthalpy,
!
"H = "U + " PV
( )
= C
v
"T + P"V + V"P.
Since the process is constant volume,
!
"V = 0 and therefore
!
"H = C
v
"T + V"P.
Summary Isochoric Processes
!
q =
!
"U = C
v
"T
!
w = 0
!
"U =
!
C
v
"T
!
"H =
!
C
v
"T + V"P

(For an isochoric process, this is actually the same as
!
C
p
"T .)
3
IV. ADIABATIC PROCESSES
For an adiabatic process,
!
q = 0 by definition. Then, from the First Law,
!
w = "U.
For an ideal gas, since
!
"U
" V
#
$
%
&
'
(
T
= 0, we have as long as
!
C
v
is independent of temperature that
!
"U = C
v
"T .
In order to calculate the temperature difference in the equation above, an expression for the initial and final
temperatures must be developed. If the process is reversible, then
!
dw = " P dV .
We also know for an ideal gas that
!
dU = C
v
dT , and for an adiabatic process
!
dU = dw. We can substitute
these two relations to obtain
!
C
v
dT = " P dV .
Using the ideal gas equation for P and integrating yields

!
C
v
!n T
2
/T
1
( ) = " nR !n V
2
/V
1
( ) .
Using properties of logarithms, we have
!
ln
T
2
T
1
"
#
$
%
&
'
C
v
= ln
V
2
V
1
"
#
$
%
&
'
(nR
.
Taking the exponential of both sides yields
!
T
2
T
1
"
#
$
%
&
'
C
v
=
V
2
V
1
"
#
$
%
&
'
(nR
or
!
T
2
T
1
"
#
$
%
&
'
C
v
=
V
1
V
2
"
#
$
%
&
'
nR
.
Isolating the temperature ratio yields
!
T
2
T
1
=
V
1
V
2
"
#
$
%
&
'
nR / C
v
.
Using the relation
!
C
p
= C
v
+ nR, we can solve to get
!
nR = C
p
"C
v
the temperature ratio becomes
!
T
2
T
1
=
V
1
V
2
"
#
$
%
&
'
C
p
(C
v ( )
/ C
v
.
4
We can define the exponent as
!
" =
C
p
#C
v
C
v
.
Note that this is not the same ! as used in the CHE 361 Heat Capacity of Gases experiment. Substituting, the
temperature ratio in a reversible adiabatic process is
!
T
2
T
1
=
V
1
V
2
"
#
$
%
&
'
(
.
If the initial and final pressures are known rather than the initial and final volumes, the temperature ratio can be
rewritten as
!
T
2
T
1
=
P
2
P
1
"
#
$
%
&
'
nR / C
p
.
Summary Adiabatic Reversible Processes
!
q = 0
!
w =
!
"U
!
"U =
!
C
v
"T
!
"H =
!
C
p
"T