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Chapter 3 - Real Gases - Annotated PDF
Chapter 3 - Real Gases - Annotated PDF
Real gases
Chapter11111
Chapter 1 :1Slide
: Slide
1
1
Chemical Thermodynamics : Georg Duesberg
Real Gases
• Perfect gas: only contribution to energy is KE of molecules
• Real gases: Molecules interact if they are close enough, have a
potential energy contribution.
• At large separations, attractions predominate (condensation!)
• At contact molecules repel each other (condensed states have volume!)
Ideal (Isotherms) Real (CO2)
p Thermo
meter
Pressure
2 gauge
Chemical Thermodynamics : Georg Duesberg
Deviations from ideality can be described by the COMPRESSION
FACTOR, Z (sometimes called the compressibility).
Z = pV/(nRT) = pVm/(RT) For ideal gases Z = 1
Pressure region
II (moderate) Molecules are close -> attractive forces apply -> The gas
occupies less volumes as expected from Boyles law: Z<1
Chapter33333 1 : Slide
3
Chemical Thermodynamics : Georg Duesberg
Microscopic interpretation: Leonard Jones Potential
Z=
Z=
7
Chemical Thermodynamics : Georg Duesberg
Boyle Temperatur
The temperature at which this occurs
is the Boyle temperature, TB, and then
the gas behaves ideally over a wider
range of p than at other temperatures.
Each gas has a characteristic TB, e.g. 23
K for He, 347 K for air, 715 K for
CO2.
The compression factor approaches 1 at low pressures, but does so with different
slopes. For a perfect gas, the slope is zero, but real gases may have either positive
or negative slopes, and the slope may vary with temperature.
At the Boyle temperature, the slope is zero and the gas behaves perfectly over a
wider range of conditions than at other temperatures. Chapter 1 : Slide 8
Chemical Thermodynamics : Georg Duesberg
Virial Equation of State
Most fundamental and theoretically sound Polynomial expansion Viris (lat.):
force (Kammerling Onnes 1901)
Virial coefficients:
p Vm = RT (1 + B’p + C’p2 + ...)
i.e. p Vm = RT (1 + B/Vm + C/Vm2 + ...)
This is the virial equation of state and B and
C are the second and third virial coefficients.
The first is 1.
B and C are themselves functions of
temperature, B(T) and C(T).
Usually B/Vm >> C/Vm2
B = 0 at Boyle temperature
Also allow derivation of exact correspondence between virial coefficients
and intermolecular interactions
Real gas – Van der Waals equation.
ideal gas : PV = nRT
(P + x )(V − y ) = nRT
2 2
⎛ ⎞
⎜ P + a⎛⎜ n ⎞⎟ ⎟(V − nb ) = nRT or P = RT − ⎜ a ⎟
⎛ ⎞
⎜ ⎝ V ⎠ ⎟ V − b ⎜ V ⎟
⎝ ⎠ m ⎝ m ⎠
Chapter1010101010 1 :
Slide 10
Chemical Thermodynamics : Georg Duesberg
Real gas – Van der Waals equation: b
1. The molecules occupy a significant fraction of the volume.
-> Collisions are more frequent.
-> There is less volume available for molecular motion.
Real gas molecules are not point masses
(Vid = Vobs - const.) or Vid = Vobs - nb
– b is a constant for different gases
Very roughly, b ∼ 4/3 πr3 where r is the molecular radius.
Other explanation:
What happens if we reduce T to zero. Is volume of the gas, V, going to become
zero? We can set P ≠ 0. By the ideal gas law we would have V = 0, which cannot
be true. We can correct for it by a term equal to the total volume of the gas
molecules, when totally compressed (condensed) nb. Now at T = 0 and P ≠ 0
we have V = nb.
P(V − nb) = nRT
Chapter 1 : Slide 11
Chemical Thermodynamics : Georg Duesberg
Real gas – Van der Waals equation: a
2) There are attractive forces between real molecules, which reduce
the pressure: p ∝ wall collision frequency and
p ∝ change in momentum at each collision.
Both factors are proportional to concentration, n/V, and p is reduced
by an amount a(n/V)2, where a depends on the type of gas.
[Note: a/V2 is called the internal pressure of the gas].
Real gas molecules do attract one another (Pid = Pobs + constant)
Pid = Pobs + a (n / V)2 a is also different for different gases
2
n a describes attractive force between pairs
2
a of molecules. Goes as square of the
V concentration (n/V)2 .
Chapter 1 : Slide 14
Chemical Thermodynamics : Georg Duesberg
Carbon dioxide: a typical pV diagram for a real gas:
Chapter 1 :
Chemical Thermodynamics : Georg Duesberg
Critical Point
At the critical temperature the densities of the liquid and gas become equal - the
boundary disappears. The material will fill the container so it is like a gas, but may
be much denser than a typical gas, and is called a 'supercritical fluid'. The
isotherm at Tc has a horizontal inflection at the critical point
dp/dV = 0 and d2p/dV2 = 0.
Consider 1 mol of gas, with molar volume V, at
the critical point (Tc, pc, Vc)
The solution is
Vc = 3b, pc = a/(27b2),
Tc = 8a/(27Rb). 16
Chemical Thermodynamics : Georg Duesberg
Critical Point drying
Applications: TEM sample prep, porous materials, MEMS
Chapter1717171717 1 :
Slide 17
Chemical Thermodynamics : Georg Duesberg
CNT
Etch
Etch
Etch
Etch
31
Chemical Thermodynamics : Georg Duesberg
,
Features of vdW equation
• Reduces to perfect gas equation at high T
and V
• Liquids and gases coexist when
attractions ≈ repulsions
• Critical constants are related to
coefficients.
• Flat inflexion of curve when T=Tc.
• Can derive (by setting 1st and 2nd
derivatives of equation to zero)
expression for critical constants
• Vc = 3b,
• pc = a/27b2,
• Tc =8a/27Rb
• Can derive expression for the Boyle
Temperature
• TB = a/Rb
32
⎛ ∂p ⎞ − RT 2a ⎛ ∂ 2 p ⎞ 2 RT 6a
∴ ⎜ ⎟ = 2
+ 3 and ⎜⎜ 2 ⎟⎟ = 3
− 4
⎝ ∂v ⎠T (v − b) v ⎝ ∂v ⎠T (v − b ) v
At critical points the above equation reduces to
− RT 2a 2 RT 6a
2
+ 3 =0 and − 4 =0
(v − b ) v (v − b )3 v
33
Van der Waals hoped that different gases confined to the same Vr at
the same Tr would have the same pr.
Chapter 1 : Slide 36
Chemical Thermodynamics : Georg Duesberg
Proof: rewrite Van der Waals equation for 1 mol of gas, p = RT/(V-b)-
a/V2, in terms of reduced variables:
RTr Tc a
pr pc = − 2 2
Vr Vc − b Vr Vc Substitute for the critical values:
pra RTr 8a a
2
= − 2 2
27b 27Rb(Vr 3b − b) Vr 9b Thus
Also:
Zc =pcVc/RTc = 3/8 =0.375
3) Redlich-Kwong RT A
p= − 1/ 2
Vm − B T Vm (Vm + B)
4) Peng-Robinson RT α
p= −
Vm − β Vm (Vm + β ) + β (Vm − β )