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Ideal Gas (PV=nRT)
• Boyle’s Law: Isothermal Processes (family of
parabolas in the PV plane
P ~ 1/V
• Charles’ Law: Isobaric processes (family of
straight lines in the VT plane
V ~ T
• GayLussac Law: Isochoric processes (family of
straight line in the PT plane
P ~ T
P
1
V
1
=P
2
V
2
2
2
1
1
T
V
T
V
=
P=P(V,T)
V=V(T,P)
T=T(P,V)
Four key processes that we should be familiar with (processes in PVT space)
Equations of State for Nonideal Gases
Critical Temperature and Pressure
Suppose a quantity of water is kept in a closed pistonfitted
cylinder.
The cylinder temperature is first set to a specified
value with the cylinder pressure low enough for all
the water to be vapor; then the water is compressed
at constant temperature by lowering the piston until
a drop of liquid water appears (i.e., until
condensation occurs).
The pressure at which condensation begins (P
cond
) and the densities of the
vapor (µ
v
) and of the liquid (µ
l
) at that point are noted, and the experiment is
then repeated at several progressively higher temperatures. The following
results might be obtained (observe the pattern for the three observed variables
as T increases):
At 25°C, water condenses at a very low pressure, and the density of the
liquid is more than four orders of magnitude greater than that of the vapor.
At higher temperatures, the condensation pressure increases and the
densities of the vapor and liquid at condensation approach each other.
At 374.15°C, the densities of the two phases are virtually equal, and above
that temperature no phase separation is observed, no matter how high the
pressure is raised.
The highest temperature at which a species
can coexist in two phases (liquid and vapor)
is the critical temperature of that species, T
c
and the corresponding pressure is the
critical pressure P
c
.
A substance at T
c
and P
c
is said to be at its
critical state.
A vapor is a gaseous species below its critical
temperature.
A gas is a species above its critical temperature at a
pressure low enough for the species to be more like a
vapor than a liquid.
Nonideal behavior
RT PV =
1 =
RT
PV
1 lim
0
=

.

\

÷
RT
PV
P
Ideal gas:
Real gases:
Let’s define a “compressibility factor”
( )
RT
PV
T P Z ÷ ,
where deviation from unity indicates the
degree of departure from ideal behavior.
For constant temperature, we can measure and
plot Z(P) for different gases.
NOTE:
At low pressure, Z(P) is nearly linear.
Virial Equation of State
(
¸
(
¸
+ + + + =
3 2
) ( ) ( ) (
1
m m m
m
V
T D
V
T C
V
T B
RT PV
(8.4)
RedlichKwong Equation
2 / 1
) ( T b V V
a
b V
RT
P
m m m
+
÷
÷
= (8.3)
Real Gas Equations of
State
The limited accuracy of the data allows evaluation of only B(T) and
sometimes C(T).
Virial Equation of State
] ) ( ' ) ( ' ) ( ' 1 [
3 2
+ + + + = P T D P T C P T B RT PV
m
(8.5)
2 2 2
) ' ' ( , ' T R C B C RT B B + = =
(8.6)
B
P
RT
V
m
+ =
(8.7)
low P
m m m m
m m
RTV
a
V b RTV
a
b V
V
Z
RT
PV
÷
÷
= ÷
÷
= =
/ 1
1
vdW gas
2
m m
V
a
b V
RT
P ÷
÷
= (8.2)
×
RT
V
m
(
¸
(
¸
+ + + + =
3 2
) ( ) ( ) (
1
m m m
m
V
T D
V
T C
V
T B
RT PV
(8.4)
Power series in 1/V
m
Power series in P
Nonideal Gas Properties
The critical point is a point in P—v—T space
defined by the highest possible temperature and the
highest possible pressure for which distinct liquid
and gas phase can be observed.
At the critical point, we designate the
thermodynamic variables with subscript c, so that
critical temperature ≡ T
c
critical pressure ≡ P
c
critical specific volume ≡v
c
State (PvT) Relationship
Presents a Tv diagram showing the
designations of the various regions and lines
associated with the liquid and vapor states of
a fluid. Although the numerical values shown
apply to H
2
O, the general ideas presented in
this figure and discussed in the following apply
to many liquidvapor system.
State (PvT) Relationship
Van der Waals constants for several gases
( ) RT b V
V
a
P = ÷

.

\

+
2
RT
PV
Z ÷
0
N·b
unstable
V
P
LowT vs highT behavior
P
S
V
T
V
Vapor
Gas
Liq.
Liquid
+
Vapor
T
C
How can we describe this “critical” behavior?
Interactions and nonideal behavior
V
P
Vapor
Gas
Liq.
V
P
V
Liquid
+
Vapor
0 =

.

\

c
c
T
V
P
0
2
2
=


.

\

c
c
T
V
P
At the critical point:
The Critical Point
The critical point is the unique point where both
(dP/dV)
T
= 0 and (d
2
P/dV
2
)
T
= 0
ˆ ˆ ˆ
C C C
P V T
P V T
P V T
= = =
The change in internal
energy is equal to the heat
flowing into the system
minus the work done by
the system.
dU = oqow
The energy of the universe is constant. Energy can be neither created or destroyed.
The First Law of Thermodynamics
P,V,T
w
q
+
+


AU = Q + W
on
work done
on the system
change in
total internal energy
heat added
to system
or
AU = Q  W
by
State Function Process Functions
Isoprocesses
• apply 1st law of thermodynamics to closed
system of an ideal gas
• isoprocess is one in which one of the
thermodynamic (state) variables are kept
constant
• use pV diagram to visualise process
We now consider different paths for an ideal gas, which, starting from an arbitrary pressure and
volume, result in increasing the temperature of the system from T
1
to T
2
.
P
V
T
1
< T
2
T
1
T
2
Constant Volume
The pressure is increased by
allowing heat to flow into the
system from an external heat
reservoir.
Constant Pressure
The volume of the system is
increased (i.e. in our model,
we slowly pull the piston out
from the cylinder). Enough
heat is permitted to flow into
the system to “just maintain”
constant pressure, until T
2
is
reached.
How much work or heat flow is involved for each process path?
O
A
B
Process paths on the PVT surface
P,V,T
w
q
dU = oqow
P,V,T
w
q
No work is done by the system during a constant volume process. The change in internal energy,
therefore, is determined only by the heat flow into or out of the system.
(ow)
V
= 0 = PΔV
dU
V
= oq
The ConstantVolume Process (Isochoric)
The heat flow into the system is equal to the change in internal energy.
P,V,T
w
q
Because the pressure is constant, the work is easily determined as PAV.
}
÷ =
2
1
PdV q
w q U ÷ = A
( ) ( )
1 2 1 2
V V P q U U ÷ ÷ = ÷
U
2
+ PV
2
( )
÷ U
1
+ PV
1
( )
= q
P
Define the Enthalpy: H = (U+PV)
AH = q
P
AV
The ConstantPressure Process (Isobaric)
P
V
T
1
T
2
T
1
< T
2
Constant Volume
Constant Pressure
q =
q =
How much heat is required to increase the temperature from T
1
to T
2
in each case?
Summary of constantP and constantV paths
Note: The heat required to change the
temperature from T
1
to T
2
is greater for
the constant pressure process.
w =
AU
0
AU + PAV
= AH
w = PAV
We now define the quantity “Heat Capacity” as the incremental heat
required per unit temperature to move the system along these paths.
More heat is required to traverse the constant pressure path.
V
V
dT
q
C

.

\

=
o
P
P
dT
q
C

.

\

=
o
All of the heat goes toward
increasing the internal
(kinetic) energy of the gas.
Some of the heat is “spent”
as work in expanding the
system from V
1
to V
2
.
The Heat Capacity
V
dT
dU

.

\

=
P
dT
dH

.

\

=
Constant
Volume
Constant
Pressure
Further analysis shows that the difference is given by the ideal gas constant.
c
p
÷c
v
=
cU
cT

\

.

P
+ P
cV
cT

\

.

P
÷
cU
cT

\

.

V
c
p
÷c
v
=
cH
cT

\

.

P
÷
cU
cT

\

.

V
Recall that internal energy is a
function only of T for an ideal gas.
cU
cT

\

.

P
=
cU
cT

\

.

V
c
p
÷c
v
= P
cV
cT

\

.

P
c
p
÷c
v
= P
R
P

\

.

= R
cV
cT

\

.

P
=
R
P
But recall also that PV=RT.
The Heat Capacity
P,V,T
w
q
We now consider a constant temperature process that takes the system from A to B.
What is the change in internal energy?
P
V
T
1
T
2
T
1
< T
2
A
B
The Isothermal Process
O
P
V
T
1
T
2
T
1
< T
2
A
O B
w= PdV = PAV
}
From O to B:
AU=q÷w
H V P U q A = A + A =
q = c
p
dT
T
1
T
2
}
From A to O:
q = c
v
dT
T
2
T
1
}
AU=q÷w
w= PdV =0
}
The Isothermal Process
We construct and examine the alternate path AOB.
P
V
T
1
T
2
T
1
< T
2
A
O B
q = c
v
dT
T
2
T
1
}
+ c
p
dT
T
1
T
2
}
= ÷AU+ AH
w = 0+ PAV
Summing AO and OB:
0 = ÷ = A w q U
V P H U w q A ÷ A + A ÷ = ÷
For an ideal gas internal energy is a state function of temperature only.
The Isothermal Process
H V P U A + A + A ÷ = ) (
0 =
Work:
Heat:
P
V
T
1
T
2
T
1
< T
2
A
O B
AU= w÷q =0
w = q
We now consider the direct isothermal path AB and compute the work and heat flow.
dU=ow÷oq =0
ow=oq
ow = PdV
=
RT
V

\

.

dV
Ideal Gas:
PV=RT
Integrating from A to B:
w = ow
A
B
}
= RT
dV
V

\

.

V
A
V
B
}
= RTln
V
B
V
A

\

.

The Isothermal Process
The work done by the system is positive.
The heat flow into the system is positive.
p
V
1
2
P
ln
C
AC A
A
V
w nRT
V
= ÷
( )
AB A B A
w P V V = ÷ ÷
0
BC
w =
0 ln
C
AC AC A
A
V
U q nRT
V
A = ¬ =
C
B
T
BC BC V
T
q U c dT = A =
}
B
A
T
AB V
T
U c dT A =
}
( )
B
A
T
AB AB AB V A B A
T
q U w c dT P V V = A ÷ = + ÷
}
C
B A
A
V
T T
V
=
reversible
isothermal
P
V
V
C
V
A
P
A
P
C
A
C
B
reversible
constant
pressure
Work and Heat along Reversible Isothermal Expansion
for an Ideal Gas, where U=U(T)
P
V
T
1
T
2
T
1
< T
2
A
O B
P,V,T
w
q
Suppose we perform the same expansion, but do not permit
any heat to flow into the system.
The Adiabatic Process
P
V
T
1
T
2
T
1
< T
2
A
O B
P,V,T
w
q
Suppose we perform the same expansion, but do not permit
any heat to flow into the system.
AV
Adiabatic
expansion
Without the heat input, the system cannot maintain its temperature. Thus,
an adiabatic expansion involves a decrease in temperature (and, therefore,
internal energy).
The Adiabatic Process
217
ow =
dU =
Recall that PV=RT.
oq =
0
PdV
c
v
dT
c
v
dT = ÷PdV
c
v
dT = ÷
RT
V

\

.

dV
Integrating:
c
v
ln
T
2
T
1

\

.

= Rln
V
1
V
2

\

.

c
v
T

\

.

dT = ÷
R
V

\

.

dV
T
2
T
1

\

.

=
V
1
V
2

\

.

R
c
v
=
V
1
V
2

\

.

¸ ÷1
Where
¸=c
p
/c
v
1
2
1
1 1
2 2
÷


.

\

=


.

\

¸
V
V
V P
V P
P
2
P
1

\

.

=
V
1
V
2

\

.

¸
i.e.
PV
¸
=const.
The Adiabatic Expansion Process
Note  For an ideal gas:
R c
v
2
3
=
First Law (permissible change)
1. There exists a state function, U
2. dU=dq+dw
enables us to compute ΔU and Δ H for different types of chemical reactions
and physical transformation
3. Heat exchange at constant P
heat exchange at constant V
Second Law (spontaneous change)
1. There exists a state function, S, the entropy, for the system
2. If the state of the system changes, the
T
dq
dS
rev
=
}
= A
f
i
rev
T
dq
S
Limitation of the first law of thermodynamics
1. Why do changes takes place in a particular direction
2. Who and why the systems are aware to proceed only in the
particular direction
3. What are the driving forces which lead the process in a given direction
Second law of thermodynamics
Introduces entropy, methods of evaluating entropy changes which act as
driving forces for spontaneous processes in isolated systems
U: capacity to do work
S: considered as an index of exhaustion of its capacity to do work
 a measure of unavailable portion of energy
 represent randomness
 greater the randomness, larger is the value of entropy
Characteristics of S
1. It is an extensive property
2. It is a state function, S (T,V,V
n
)
3. ΔS
system
does not depend on the path followed by the change but the
ΔS
surroundings
depends on the path
4. ΔS
total
= ΔS
system
+ ΔS
surroundings
5. In a reversible process ΔS
system
=  Δs
surroundings
6. In an irreversible process ΔS
total
> 0
7. S= J/K or J/Kmol
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