PHYSICAL CHEMISTRY I (Chem2106)

Cr. Hr: 3

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 UNIT 1 IDEAL AND REAL GASES

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Equation of State

The physical state of a substance is defined by its physical properties.

Example: The state of a pure gas is specified by its volume (V),

pressure (P), temperature (T) and number of moles (n).

Equation of State – An equation that inter-relates the variables: V, P,

T and n.

General Form of an Equation of State:

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Units of Pressure:

SI Unit: – Pascal (Pa)

1 Pa = 1Nm-2 = 1Kgm-1s-2 = 1Jm-3

Other Units:

• Bar: 1bar = 105 Pa

• Atmosphere: 1atm = 1.01325 × 105 Pa

• Torr: 1Torr = 133.322 Pa

• Pound per square inch: 1psi = 6.89 kPa

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 Barometer: An instrument that measures the atmospheric
pressure.

The pressure at the base of a column of a liquid of height h, and

density ρ is:

𝑃𝑃 = ρ𝑔𝑔𝑔

where g = gravitational acceleration (9.8 ms-2)

Pressure gauge: It measures the pressure of a gas inside a

container.

Temperature Unit: Kelvin (K)

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T (K) = T (oC ) + 273.15
 1.1. Ideal Gases and Ideal Gas Laws

Ideal Gas: A gas is said to be ideal if

i. The size of the molecules is considered to be negligible
ii. The molecules do not interact with each other.

The Ideal Gas Law

Boyle’s law: V α 1/P (T, n = constant)
Charles’s law: V α T (P, n = constant)
Avogadro’s law: V α n (P, V = constant)

Therefore:

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 Let the Constant = R (universal gas constant)

Accordingly,

PV = nRT (ideal gas equation)

Values of R

R = 8.314 J K-1 mol-1

= 8.2 × 10-2 dm3atm K-1mol-1
= 8.314 Pa m3 K-1 mol-1
= 8.314 ×10-2 dm3 bar K-1mol-1

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Example: In an industrial process, nitrogen enters a vessel of
constant volume at 100 atm and 300 K. To what temperature
should the gas be heated in order to exert a pressure of 300 atm?

Solution:

Given: P1 = 100 atm, P2 = 300 atm, V1 = V2, n1 = n2, T1 = 300 K,

T2 = ?

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 Mixtures of gases

• The partial pressure (PJ) of a gas J in a mixture of gases is

given by
PJ = XJP

Where XJ = mole fraction of J

nA, nB … = number of moles of gas A, B, etc,

P = total pressure of the mixture,

P = PA + PB + …, P = (XA + XB + …)P

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Dalton’s law

 The pressure exerted by a mixture of gases is the sum of the

pressures that each gas would have exerted if it occupied the
container alone.

Example: The mass percentage composition of dry air at sea level is:
N2 = 75.5, O2 = 23.2, Ar = 1.3.

What is the partial pressure of each component when the total

pressure is 1.00 atm?

Let the mass of air = 100 g

Mass of N2 = 75.5 g, Mass of O2 = 23.2g, Mass of Ar = 1.3g

Molar masses: N2 = 28 g mol-1, O2 = 32 g mol-1, Ar = 39.95 g mol-1

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 nTotal = 2.7 + 0.7 + 0.03 = 3.43 mol

P (N2) = 0.79 × 1 atm = 0.79 atm

P (O2) = 0.2 × 1 atm = 0.2 atm
P (Ar) = 0.009 × 1 atm = 0.009 atm

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 Real gas: A gas sample that does not obey the ideal (perfect) gas
law exactly.

 The deviations are significant at high pressures and low

temperatures.
Molecular Interactions:

 Real gases deviate from the ideal gas law because of molecular
interactions.
 Repulsive forces between molecules assist expansion while
attractive forces assist compression.

 Repulsive forces are short range interactions.

 They are significant when the molecules are close to each

other, as under high pressure.
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  Attractive forces are relatively long-range interactions.
 They are significant when the molecules are fairly close
to each other.
 They are ineffective when the molecules are far apart.
 At low pressures, the molecules are far apart.
 the intermolecular forces have no significant role.
 Therefore, a gas sample at low pressure behaves ideally.

 At moderate pressures,
 the attractive forces dominate the repulsive forces.
 As a result, a gas at moderate pressures is expected to be more
compressible than an ideal gas.
 At high pressures,
 the repulsive forces dominate.
 Therefore, a gas at high pressures is expected to be less
compressible
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 1.2.1 Characteristic Features of Gases

a) The Compression Factor (Z):

Vm = measured molar volume,

Vmo = molar volume of a perfect gas at the same T and P

Therefore,
or

 For a perfect gas, Z = 1 under all conditions.

 Deviation of Z from 1 is a measure of departure from a
perfect behavior.
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 Effect of Pressure on Z
 At very low pressure, all gases have Z = 1.
 At high pressures, all gases have Z > 1.
 At intermediate pressures, most gases have Z < 1.

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 b) Virial Coefficients

 In the presence of intermolecular forces among gaseous

molecules, the equation of state is expressed in terms of the
Virial Equation.

The coefficients; B, C… are called Virial coefficients.

 They are functions of temperature.

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 B – Second virial coefficient – Considers interactions between two
molecules.
C – Third virial coefficient – Considers interactions between three
molecules.

B is more dominant than others.

Therefore,

 Boyle temperature, TB: The temperature at which B = 0.

At Boyle temperature,

PVm = RTB
Therefore, the Virial equation reduces to the perfect gas equation of
state.
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 Example:

Gas T(K) B(cm3mol-1)

N2 273 -10.5
327.2 0
600 21.7
Ar 273 -21.7
411.5 0
600 11.9
CO2 273 -149.7
600 -12.4
714.8 0

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 c) Critical Constants

 When a gas sample is compressed at a certain temperature, its

pressure is expected to rise (Boyle’s law).

 When the pressure reaches a certain point, it remains constant

and the gas condenses to a liquid, forming a gas – liquid
distinct phases.

 If the compression takes place at or above a certain

temperature the pressure of the gas increases without
condensation.

 Critical temperature (Tc): The temperature at which the gas –

liquid interface vanishes.
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  The corresponding pressure and molar volume are called
critical pressure (Pc) and critical molar volume (Vc),
respectively.
 Tc, Pc and Vc collectively are called critical constants.
 The critical constants are characteristic of the type of the gas.
Example:

 Super critical fluid: The single phase that fills the entire
volume when T ≥ Tc.
 It is denser than gases under normal condition.
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 1.2.2. The van der Waals Equation

 In real gases, the volume available for moving gaseous molecules

is decreased because of the repulsive forces.
 The smaller volume is V – nb.
 The pressure of the gases is decreased because of the attractive
forces among the molecules.
 The decrease is proportional to the molar concentration and is
equal to a (n/V)2.

van der Waals equation

Or

Where: Vm= V/n – molar volume

a, b are van der Waals coefficients.
21  They are characteristics of a gas.
 Unit of a = atmdm6mol-2 Unit of b = dm3mol-1

Example: Calculate the pressure exerted by one mole of Ar at

100 oC. (Vm = 0.298dm3mol-1, a = 1.337 atmdm6mol-2, b = 3.2 ×
10-2 dm3mol-1)

Solution

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 Features of the van der Waals Equation

1. The equation reduces to a perfect gas equation at high

temperatures and large molar volumes.

Therefore,

2. Liquid and gaseous states coexist when repulsive

(dispersive) interactions and attractive (cohesive) interactions
are in balance, i.e.,

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 3. The critical constants are related to the van der Waals
coefficients.
At critical constants,

Using the van der Waals equation,

Using the critical constants,

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 Using the equations,

1.2.3. The Principles of Corresponding States

 Real gases at the same reduced volume (VR) and reduced

temperature (TR) exert the same reduced pressure (PR).

The reduced variables are given by;

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 Substitution for Pc, Vc and Tc yields

Accordingly, if two gases have the same VR and TR values, they

will have the same PR.

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