KWARA STATE UNIVERSITY, MALETE

FACULTY OF PURE AND APPLIED SCIENCES

DEPARTMENT OF CHEMISTRY AND INDUSTRIAL CHEMISTRY

CHM231: Basic Physical Chemistry

Prepared by: Dr. Lukman B. Abdulrauf (08057157696)
– Kinetic theory of gases – Real gases – Corresponding state
– Distribution of molecular speed – Chemical kinetics – Reaction mechanism

1 Atkins, P., and de Paula, J. (2006). Physical Chemistry, 8th edition, Oxford University Press,
2 House, J. E. (2007). Principles of Chemical Kinetics, 2nd edition, Elsevier Inc.
3 Sharma, K. K., and Sharma, L. K. (2016). A Textbook of Physical Chemistry, 8th edition Vikas
Publishing House

Real Gases
Experimental evidences have shown that very few gases obey the ideal gas equation only at low pressure and
high temperature, and that most gases show marked deviation from the ideal behavior at high pressure and low
temperature.
Real gases do not obey ideal (perfect) gas laws and general gas equation (pV = nRT) except at high pressure
and low temperature
That is, the observed relationships between the pressure, volume, and temperature of gas are not accurately
described by the gas laws. Thus, real gas deviates from ideal gas behaviour.

The extent of deviation from ideal gas behaviour can be expressed as a function of pressure (which is related
to the density of the gas) by introducing a quantity called the Compressibility or Compression factor Z.
𝑚𝑜𝑙𝑎𝑟 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑔𝑎𝑠 𝑎𝑡 𝑠𝑎𝑚𝑒 𝑇 𝑎𝑛𝑑 𝑝 𝑝𝑉𝑚
𝑍 = 𝑚𝑜𝑙𝑎𝑟 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑖𝑑𝑒𝑎𝑙 𝑔𝑎𝑠 𝑎𝑡 𝑠𝑎𝑚𝑒 𝑇 𝑎𝑛𝑑 𝑝 = 𝑅𝑇
Ideal gas behavior is therefore indicated when this ratio is equal to 1 (under all conditions), and any deviation
from 1 is an indication of non-ideal behavior.

For real gases, Z is a function of both temperature and pressure and its value varies. The amount by which the
actual factor differs from unity gives a measure of deviation from ideality for the gas.

Deviation from ideality occurs because of the following weak assumptions in the postulates of kinetic theory
of gases.
1. The volume occupied by the molecule is negligible compare to the total volume of the gas.
This is not true at lower temperature and high pressure where the molecules of the gas get so closed that
the liquefaction and finally solidification of the gas occur. Since solids cannot be compressed, it confirms
that molecules of the gas occupy some volume.
2. Molecules exert no force on each other. However, liquefaction occurs because there is force of attraction
between the molecules of the gas.

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Van der Waals Assumptions
1. Gas molecules have finite size and behave as incompressible rigid spheres.
2. Gas molecules attract each other with a weak force which is a function of distance between them. (This
implies that molecules of a real gas have kinetic as well as potential energies.) However, only nearest
neighbour interactions are important.
3. The number of collisions with the walls of the container remain the same for point and finite size molecules
𝑎𝑛2
van der Waals equation of state (𝑝 + ) (𝑉 − 𝑛𝑏) = 𝑛𝑅𝑇 For n mole of gas 1
𝑉2
𝑛𝑅𝑇 𝑛 2
𝑝 = 𝑉−𝑛𝑏 − 𝑎 (𝑉) 2
𝑎𝑛2
The correction to the pressure term and molecular attraction in the ideal gas law is , while nb is the
𝑉2
correction of volume of molecules
𝑎
For 1 mole of gas (𝑝 + 𝑉 2 ) (𝑉 − 𝑏) = 𝑅𝑇 3
𝑅𝑇 𝑎
𝑝= − 4
𝑉−𝑏 𝑉2
The constants a and b are known as van der Waals’ constants (coefficient). They are characteristic of each gas
but independent of the temperature. The constant a corresponds to the strength of the attraction between
particles of a particular gas, and the constant b corresponds to the size of the particles of a particular gas.

Van der Waals Critical Phenomenon

Critical Temperature Tc: is that temperature above which gas cannot be liquefied no matter how great the
8𝑎
pressure the applied. It is given by the expression 𝑇𝑐 = 27𝑅𝑏 5

Critical Pressure Pc: is the minimum pressure required to liquefy a gas at its critical temperature. It is given
𝑎
as 𝑃𝑐 = 2
6
27𝑏

Critical Volume Vc: it is the volume occupied by 1 mole of it at its critical temperature and pressure. It is
expressed as 𝑉𝑐 = 3𝑏 7

The van der Waals constant a and b can be expressed in terms of critical constants by means of the following
equations:
27𝑅𝑏𝑇𝑐
From equation 5 𝑎= 8
8
From equation 6 𝑎 = 27𝑏 2 𝑇𝑐 9
1
From equation 7 𝑏 = 3 𝑉𝑐 10
Combine equations 5 and 6 and make b subject of the formula
𝑅𝑇𝑐
𝑏= 11
8𝑃𝑐
27𝑅 2 𝑇 2
Substitute b (equation 11) in equation 8 𝑎= 12
64𝑃𝑐

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Corresponding States
Law (Principle) of Corresponding States: states that If any two gases have equal values of reduced pressure
and reduced temperature, then they have same values of reduced volume; i.e., Vr = f(Tr , pr) for all gases and
the function is the same.
The principle is only an approximation. It works best for gases composed of spherical molecules; it fails,
sometimes badly, when the molecules are non-spherical or polar
The dimensionless reduced variables of a gas can deduced by dividing the actual variable by the corresponding
critical constant:

𝑇 𝑝 𝑉
𝑇𝑟 = 𝑇 𝑝𝑟 = 𝑝 𝑉𝑟 = 𝑉 13
𝑐 𝑐 𝑐
Substituting equation 13 into the van der Waals equation (equation 4)
𝑅𝑇 𝑇 𝑎
𝑝𝑟 𝑝𝑐 = 𝑉 𝑉𝑟−𝑏
𝑐
− 𝑉2𝑉2 14
𝑟 𝑐 𝑟 𝑐
To express the critical constant in terms of a and b, substitute equations 5, 6 and 7 into equation 14
𝑎𝑝𝑟 8𝑎𝑇 𝑎
= 27𝑏(3𝑏𝑉𝑟 −𝑏) − 9𝑏2 𝑉 2 15
27𝑏 2 𝑟 𝑟
Equation 15 can be reorganized into
𝑟 8𝑇 3
𝑝𝑟 = 3𝑉 −1 − 9𝑏2 𝑉 2 16
𝑟 𝑟

Example 1: A 4.25-L flask contains 3.46 mol CO2 at 229 ℃ (273 +229 – 502K). Calculate the pressure of this
sample of CO2:
Given a = 3.59 L2atm/mol2 b = 0.0427 L/mol
(a) From the ideal gas law
(b) From the van der Waals equation
(c) Explain the reason(s) for the difference.

Solution
𝑛𝑅𝑇
(a) Using 𝑝 = = 33.5 atm
𝑉

𝑛𝑅𝑇 𝑛2 𝑎
(b) Using 𝑝 = 𝑉−𝑛𝑏 − 𝑉2

= 32.4 atm
(c) The values are very close, because the pressure is not very high and the temperature is not very low. The
value is somewhat different because CO2 particles do have some volume and attractions between particles, and
the ideal gas law assumes they do not have volume or attractions. The van der Waals equation takes into
account the volume of the gas particles as well as intermolecular attractions

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Example 2: One mole of CO2 occupies 192 cm3 at 32.5 ℃ and 70 atm. Calculate the pressure exerted by CO2
molecules, if we assume that it obeys
(i) perfect gas equation, and
(ii) van der Waals’ equation. Given a = 3.59  106 atm m6 mol2, b = 42.7 106 m3 mol1 and R = 8.2  105
atm m3 K1 mol1.

Solution: Volume of CO2 = 192  106 m3 mol1, T = 273 + 32.5 = 305.5 K

𝑛𝑅𝑇
(i) 𝑝 = =
𝑉

𝑅𝑇 𝑎
(ii) 𝑝 = 𝑉−𝑏 − 𝑉 2 = − = 70.4 atm

Note: (a) the pressure calculated for a van der Waals’ gas is close to the observed value of 70 atm, and
(b) it is much less than that calculated by assuming CO2 to be an ideal gas. It means that the cohesive pressure
and co-volume account for nearly 60.6 atm

Example 2: Graphs showing the behavior of several different gases follow. Which of these gases exhibit
behavior significantly different from that expected for ideal gases? (Answer: Gases C, E, and F)

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Example 3: Explain why the plot of PV for CO differs from that of an ideal gas.

Answer: CO2 interacts intermolecularly with other molecules, and occupies a volume in space. Hence the CO2
molecules repel other molecules and create pressure through collisions, leading to a non-linear relationship
between PV and P.

Example 4: Under which of the following sets of conditions does a real gas behave most like an ideal gas,
and for which conditions is a real gas expected to deviate from ideal behavior? Explain.
a. high pressure, small volume
b. high temperature, low pressure
c. low temperature, high pressure

Answer: The gas behavior most like an ideal gas will occur under the conditions in (b).
Molecules have high speeds and move through greater distances between collisions; they also have shorter
contact times and interactions are less likely.
Deviations occur with the conditions described in (a) and (c).
Under conditions of (a), some gases may liquefy.
Under conditions of (c), most gases will liquefy.

Example 5: Describe the factors responsible for the deviation of the behavior of real gases from that of an
ideal gas.

Answer: An ideal gas is assumed to have no volume or intermolecular interaction. Molecules that portray real
gas behaviour show attraction between other molecules resulting in a deviation in ideal gas behaviour. Real
gases only show ideal behaviour at high temperatures and low pressures.

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