Imperfect Gases Detail
Imperfect Gases Detail
Imperfect Gases Detail
PV = RT where V = V/n
An equation of state relates the pressure, volume, and temperature of the gas given a quantity of n
moles of gas. The properties of a gas are of two type.Extensive variables are proportional to the size
of the system.
Intensive variables do not depend on the size of the system.
If we divide an extensive quantity by the number of moles (or number of particles), we obtain an
intensive quantity. For example, volume V (L) is an extensive quantity, but molar volume V/n
(L/mole) is an intensive quantity.
Pressure in the ideal gas law has units of N/m2 which is corresponds to force per unit area. When
thinking about the unit of atmospheres which corresponds to the pressure at sea level, the force is that
due to the weight of the atmosphere above the surface of the earth. We look at some problems below.
---------------------------------------------------
Problem: what is the mass of the atmosphere above 1 m2 of the earth surface?
Solution: The pressure is a force per unit area. The force in this case is the weight of the atmosphere
(F = mg). If we assume that g is a constant for the entire column of the atmosphere above 1 m2 we
have
m = PA/g = (1.0325 x 105 N/m2)(1 m2)/(9.8 m/s2)
m = 1.05 x 104 kg.
SI units of pressure refer to the N/m2 as the Pascal (Pa). There are 1.0325 x 105 Pa per atm. A new
standard unit of pressure is the bar, where 1 bar = 105 Pa.
If m is the mass of the liquid and g is the gravitational
acceleration, the force is F = mg. The pressure is
where is the density, = m/V. Note that the area of the object cancels exactly as in our example
F mg hAg
P= = = = hg
A A A
above for the mass of the atmosphere. The application of P = hg is most common in liquids.
Problem: What is the pressure due to water at a depth of 100 m? (You can solve it).
We can also consider the pressure of a gas in gravitational field using the fluid formula above
and the ideal gas law. For example, we can solve the following problem.
Problem: What is the pressure of the atmosphere at an elevation of 6000 m (the top of Mt.
Kilimanjaro)? You may assume that T = 273 K.
We must recognize that the the pressure is a function of height P(h) = gh. The change in
pressure dP is related to the change in height dh by dP = - g dh. The minus arises from the fact that
the pressure decreases as the height above the earth's surface increases. We need to know how the
density changes with height. We obtain this from the ideal gas law. The density is = nM/V where n
is the number of moles, M is the molar mass and V is the volume. We can obtain n/V from the ideal
gas law: n/V = P/RT, thus = MP/RT. We can now substitute the density into the pressure vs. height
formula.
MPg
dP = dh
RT
P h
dP = Mg dh
1 P RT 0
Mgh
ln P =
RT
Mgh
P = exp
RT
At this point you can plug in numbers. We will use M = 29 grams/mole as an average molar mass for
the atmosphere.
0.029 kg/ mol 9.8 m/s 2 6000 m
P = 1 atmospere exp
8.31 J / mol K 273 K
Real gases differ from ideal gases in two ways. First, they have finite
size. Secondly, there are forces acting between the particles or molecules
in a real gas. The microscopic description of these forces has a
consequence for the macroscopic equation of state.
Answer: A hard sphere gas differs from an ideal gas in that it has a finite
size. As you increase the pressure on a hard sphere gas you will
eventually start packing the spheres into a solid. Since the spheres are
"hard" you will reach a point where you cannot compact them any
further. To find the formula for that point we solve for the density of a
hard sphere gas.At infinite pressure RT/P 0 and so = M/b is the
maximum density.
P V nb = nRT
P V
n b = RT
V = RT + b
n P
= nM = M
V RT + b
P
Van der Waal's gas: microscopic considerations
The van der Waal's gas includes both the finite extent of a hard sphere
gas and intermolecular attractions due to induced dipole-induced dipole
interactions. Next we consider the origin of attractive forces between
molecules. These are the so-called London dispersion forces and they
arise due to the fluctuating electron clouds in molecules.
London dispersion interactions or induced ipole-induced dipole interactions are always attractive.
21 2 22 1
u ind(r) =
4 0 r 6 4 0 r 6
where is the molecular polarizability.
I 1I 2 1 2
u disp(r) = 3
2 I 1 + I 2 4 2r 6
0
energy surface.
If the molecule has a permanent dipole moment as well there are dipole-
dipole interactions.
where is the ground state dipole moment. Note that the factor of kT in the denominator signifies that
2 1 2 1
u d,d(r) =
4 0 3kT r
6
thermal fluctuations tend to disrupt interactions between the dipole moments and to reduce the
magnitude of this term.
Potential Energy Surface
The attractive force is a mutual electrostatic interaction.
The repulsive force is due to the finite dimension of molecules. Repulsive
One common model for the potential energy surface is the Lennard-
Jones potential. Attractive
c 12 c 6 Energy
u(r) = 12 6 u(r)
r r
Internuclear Distance , r
-12
The r term accounts for repulsion due to molecular radii. This term
replaces the hard sphere model. The r-6 term accounts for attraction at
larger distances.
Contributions to the r-6 term include both dipole-dipole and induced-
dipole-induced-dipole interactions. d
Van der Waal's gas: macroscopic equation Finite Electrostatic
Size Attraction
There are non-ideal equations of state designed to account for the deviations of gases from ideal
behavior. The best known of these is the van der Waals equation
Where V bar designates the molar volume. The constants a and b are called van der Waals constants,
and they depend on the gas being described. The parameter a depends on the strength of
intermolecular interactions. The parameter b depends on the size of the molecules.
P + a2 V b = RT
V
The van der Waals equation can be rewritten a number of ways:
(a) in terms of pressure
P= RT a
2
Vb V
(b) in terms of the compressibility factor Z
Z= V a
Vb RTV
(c) in terms of the molar volume
V b + RT V + a V ab = 0
3 2
P P P
The last form shows clearly that the van der Waals equation of state is a cubic polynomial. This is
important since it implies that below a critical temperature there will be a phase transition. In other
words this simple equation also serves as an equation of state for the liquid!
Equations of State: Virial and van der Waal's
The ideal gas law (PV = nRT) assumes that atoms and molecules have no extent (no finite size) and
there are no interactions between particles.
The virial equation of state shows a natural connection between the microscopic and macroscopic
view.
The coefficients B(T) are called virial coefficients.
B (T) B3V(T)
Z = PV = 1 + 2V + 2 + ...
RT V V
Z is called the compressibility. The second virial coefficient is negative at low temperature.
A negative B2V represents the dominance of intermolecular attractions. B2V can be related to the
intermolecular potential through
0 0
3
2
2 NA
= 2N A r dr =
0 3
which is equal to four times the volume of NA hard spheres.
The van der Waals equation has a natural interpretation in terms of finite size since b is the volume
reduction due to the size of the gas molecules and a is a pressure reduction due to interactions between
molecules.
P = RT a2
Vb V
The interpretation the van der Waals parameters can be obtained by writing a virial expansion
2
Z= PV =1+ b a 1 + b + ...
RT RT V V 2
B2V(T) = b a
RT
we can use a hard sphere 1/r6 potential,
u(r) = for r < and u(r) = -c6/r-6 for r > .
with(plots):plot(0.082*298/(v-0.037)-4.248/(v*v),v=0.05..1);
You will note that this isotherm has a strange shape. The reason is that the cubic polynomial is
giving rise to inflection. At high enough temperature this will no longer be important (and the
van der Waals equation will begin to approach the ideal gas law).
plot({0.082*298/(v-0.037)-4.248/(v*v),0.082*400/(v-0.037)-4.248/(v*v),0.082*500/(v-0.037)-
4.248/(v*v)},v=0.05..0.3);
Note that we have changed the range on the abcissa (the molar volume axis) to better see how the
shape of the curves is changing. You can compare the ideal gas law to the van der Waals
equation at 300 K
with(plots):plot({0.082*300/v,0.082*300/(v-0.037)-4.248/(v*v)},v=0.05..0.3);
and 500 K
with(plots):plot({0.082*500/v,0.082*500/(v-0.037)-4.248/(v*v)},v=0.05..0.3);
The plot at 500 K shows more similarity than the plot at 300 K. Above a critical temperature there is
no inflection point and the curves for real and ideal equations of state begin to have the same shape.
This behavior corresponds to the known behavior of substances. They all have a critical temperature
(and pressure) beyond which there is no distinction between liquid and gas. Below the critical
temperature there will be a phase transition for a given temperature and pressure. Since the molar
volume changes (think about liquid water turning to vapor) there should be an abrupt change in the
molar volume as shown in Figure 16.7 in your text for isotherms below the critical point.
The critical point in a van der Waal's gas
The critical point is defined mathematically as an inflection point. At the critical temperature the
curve will no longer turn down. For ammonia the critical point must be between 300 K where the
isotherm shows a change in the sign of curvature and 500 K where it does not. At the inflection point
the slope of the curve will be zero and the curvature will be zero.
In pressure-volume space this means
P = 0 and P = 0
2
V V
2
There is an elegant and simple way of solving this. They note that at the critical point there is only one
root. Therefore, the cubic equation can be written
3 3 2 2 3
V Vc = 0 or V 3VcV + 3Vc V Vc = 0
The coefficient Vc bar can be equated with the coefficients above for the van der Waals equation of
state expressed as a cubic polynomial. A single point in P-V space is solved for, thus, there is a critical
temperature, Tc, pressure, Pc, and volume, Vc. To find these we equate the terms in the van der Waal's
expression to the above cubic polynomial. At the critical point:
RTc 2 a
V + V ab = 0
3
V b+
Pc Pc Pc
PR + 32 VR 1 = 8 TR
VR 3 3
This equation is a universal equation for all gases. Although the actual pressures and volumes may
differ, two gases are said to be in corresponding states if their reduced pressure, volume, and
temperature are the same.
The compressibility factor Z can also be cast into the form of corresponding states showing that
Z also can be expressed as a universal function of VR and TR or any other two reduced quantities.
VR
Z = 9
VR 1/3 8V RTR