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Homework:
Exercises (a only) : 1.4,6, 9, 11, 14, 16, 17, 18, 21
Problems: 1.1, 3, 12(a & b only), 20, 32
Equations of State
Gases are the simplest state of matter
» Completely fills any container it occupies
» Pure gases (single component) or mixtures of components
Equation of state - equation that relates the variables defining its physical properties
» Equation of state for gas: p = f (T,V,n)
» Gases (pure) Properties - four, however, three specifies system
Pressure, p, force per unit area, N/m2 = Pa (pascal)
Standard pressure = pø = 105 Pa = 1bar
Measured by manometer (open or closed tube), p = p external + gh
g = gravitational acceleration = 9.81 m/s -2
Mechanical equilibrium - pressure on either side of movable wall will equalize
Volume, V
Amount of substance (number of moles), n
Temperature, T, indicates direction of flow of energy (heat) between two bodies;
change results in change of physical state of object
Boundaries between objects
» Diathermic - heat flows between bodies. Change of state occurs when bodies of
different temp. brought into contact
» Adiabatic - heat flows between bodies. No change of state occurs when bodies of
different temp brought into contact
Heat Flow and Thermal Equilibrium
High Low TA = T B
Temp. Temp.
A B
A B A B No Heat
Heat No Heat
http://www.chem1.com/acad/webtext/gas/gas_2.html#PVT
Ideal (Perfect) Gas Law - Mixtures
p
J
This becomes : V
total
P
If xJ is the fraction of the molecule, J, in mixture {x J
= nJ / nTotal ), then xJ =1
If xJ is the partial pressure of component J in the pA = xAp
mixture, pJ = xJ p, where p is the total pressure
0 1
» Component J need not be ideal
Mole Fraction B, xB
» p = pJ = xJ p this is true of all gases, not just
ideal gases
Real Gases - General Observations
Deviations from ideal gas law are particularly important at
high pressures and low temperatures (rel. to condensation
point of gas)
Real gases differ from ideal gases in that there can be
interactions between molecules in the gas state
» Repulsive forces important only when molecules are nearly in contact,
i.e. very high pressures
Gases at high pressures (spn small), gases less compressible
» Attractive forces operate at relatively long range (several molecular
diameters)
Gases at moderate pressures (spn few molecular dia.) are more
compressible since attractive forces dominate
» At low pressures, neither repulsive or attractive forces dominate -
ideal behavior
Compression Factor, Z
Compression factor, Z, is ratio of the
actual molar volume of a gas to the molar
volume of an ideal gas at the same T & P
» Z = Vm/ Vm°, where Vm = V/n
Using ideal gas law, p Vm = RTZ
The compression factor of a gas is a
measure of its deviation from ideality
» Depends on pressure (influence of
repulsive or attractive forces)
» z = 1, ideal behavior
» z < 1 attractive forces dominate, moderate
pressures
» z > 1 repulsive forces dominate, high
pressures
Real Gases - Other Equations of State
Virial Equation
Consider carbon dioxide CO2
» At high temperatures (>50°C) and high
molar volumes (Vm > 0.3 L/mol),
isotherm looks close to ideal
» Suggests that behavior of real gases can
be approximated using a power series
(virial) expansion in n/V (1/Vm)
{Kammerlingh-Onnes, 1911}
B C
pV RT 1 .......
V V
m 2
m m
a is a constant
» van der Waals (1873)
n
2
nRT RT a
p a
V nb V V b V m m
2
Dieterici (1899)
»
RTe a / RTVm
p
V b m
n
2
nRT RT a
van der Waals Equation p a
V nb V V b V
m m
2
30
20
10
0
0.1 1 10
V (Liters)
350
Ideal Gas
300
CO2 (van der Waals)
250
200
150
100
50
0
0.01 0.1 1
V (L)
Effect of T and Vm
» Ideal gas isotherms obtained
» 2nd term becomes negligible at high enough T
» 1st term reduces to ideal gas law at high enough V m
At or below Tc
» Liquids and gases co-exist
» Two terms come into balance in magnitude and oscillations occur
1st is repulsive term, 2nd attractive
» At Tc, we should have an flat inflexion point, i.e., both 1st and 2nd derivatives of equation w.r.t
Vm = 0 » Solving these equations for p,Vm and T gives pc,Vc and Tc in terms
RT a of a and b
d Hint: you must use original eqn to do this
V b V
2
dp RT 2a
m
m
0 pc= a/27b3, Vc pc= 3b and Tc = 8a/27Rb
V b V
2
dV dV
3
m m m m
Critical compression factor, Zc, can be calculated using
RT 2a
d definition for Z:
2
V b V
3
dp
2
2RT 6a pVm = RTZ
0
m m
p V a 27Rb 3
V b V
3
dV dV Z c c 3b
4