Physical Chemistry

CHEM-214

The properties of gases

Dr. Fouzi mouffouk
 Conversion

1 m = 100 cm = 10 dm = 1000 mm

1 m3 = 1003 cm3 = 103 dm3 = 10003 mm3

• When convert from larger unit to smaller one , the result

becomes larger .

• When convert from smaller unit to larger one , the result

becomes smaller .

• The S.I unit of volume is m3 , but for the concentration we

use L ( 1 L = 10 dm3 = 1000 cm3 ) .
 Conversion
Pressure = or

1 atm = 101.325 kPa = 760 Torr = 760 mmHg

1Pa = 1 Nm-2 = 1 Jm-3 = Kg m s-2 m-2

Energy : J = Kg m2 s-2

Force : = N = J m-1 = Kg m s-2

Temperature : Kelvin , K

State Function: Thermodynamic properties that depend only on

the current state of the system and is independent of the previous
history of the system ( i.e. Internal energy , entropy … )
 The properties of gases
We can picture a gas as a collection of molecules ( or atoms) in
continues random motion , with average speeds that increase as
the temperature is raised.

States of gases:
• The state of a pure gas, for is specified by giving its volume, V,
amount of substance (number of moles), n, pressure, p, and
temperature, T.

• A substance is described by an equation of state:

An equation that interrelates these four variables:
V, n, p, and T.

• The general form of an equation of state is

p = f(T, V, n)
 The equation of state of a ‘perfect gas’
pV = nRT
• R is the universal gas constant
8.314 J K-1 mol-1 (p = Pa , V = m3 , T = K)
0.0826 L atm mol-1 K-1 (p = atm , V =L , T = K)
82.6 cm3 atm mol-1 K-1 (p = atm , V = cm3 T = K)

• p : pressure , atm , mmHg , Torr , bar , Pa … etc.

• V : volume , m3 , cm3 , L , f t3 … etc.

• T : Absolute ( thermodynamic ) temperature in K

• n : number of moles

STP : Standard Temperature and Pressure - Under STP conditions ,

the molar volume of an ideal gas is Vm = 22414 cm3 mol-1 .
The conditions 0 0C and 1 atm are called standard
temperature and pressure (STP).

Experiments show that at STP, 1 mole of an ideal

gas occupies 22.414 L.

PV = nRT
PV (1 atm)(22.414L)
R= =
nT (1 mol)(273.15 K)

R = 0.082057 L • atm / (mol • K)

13
 Pressure
• The pressure defined as a force divided by the area to which the
force is applied

• The S.I unit of pressure is “Pa” = 1N m-2 = 1 Kg m-1 s-2

the most commonly used unit is atmosphere ( 1 atm = 101325 Pa )
and bar ( 1bar = 105 Pa )

Movable wall Mechanical equilibrium

same pressure
 Pressure
• There are only two element in the
periodic table which are liquid at
standard condition Hg and Br.

Barometer:
• The column of air is pressing
on the surface of Hg at sea level
resulting in moving Hg inside
the Hg column up ( h α pex )

Standard atmospheric pressure (1 atm) is equal

to the pressure that supports a column of mercury
exactly 760 mm (or 76 cm) high at 0°C at sea
level.
Manometer: A manometer is an instrument that uses a
column of liquid to measure pressure

• Barometers measures the pressure of the ambient atmosphere

external
pressure, pex vacuum

h
h

ρ: density of the ρ
fluid
pgas = pex - h ρ g pgas = h ρ g
(g = acceleration of gravity)

Open end manometer Closed end manometer

P2 P1 = PW + P2 how much the value of Pw
0
Pw : is fluid pressure in our case is water
h
Pw = P1 - P2

So P = F (the force)/A (the area) = m.g/A

V = h.A ρ = m/v

P = m.g/(v/h) P = m.g.h/v = ρ.g.h

p  hg
Ρ = density
g = Gravity acceleration
h = height
 Derivation
V
Mass of a column of a liquid = ρ . h . A
T
p  hg

pex pex

Note that in the h

h
calculation, we
did not consider
the shape or the
diameter of the pex ˂ pgas pex ˃ pgas
column. pgas - pex = ρhg pex - pgas = ρhg
pgas = pex + ρhg pgas = pex - ρhg

pgas = pex + ρhg

 Temperature
• Temperature, T: is the property that indicates the direction of the
flow of energy “as heat” through a thermally conducting, rigid
interface

If energy flows from When the two objects are in

A to B when they are
in contact (diathermic
wall), then we say that
A has a higher
temperature than B
contact “ diathermic wall “
and there is no heat transfer
(net heat transfer is zero ),
then the two objects are in
thermal equilibrium
There are two types of boundries “ walls”:

• Diathermic wall : Thermally conducting wall , the energy can

pass between the two sides as a result of temperature difference,
(e.g. metal container )

• Adiabatic wall : thermally insulating , no exchange of energy as

heat between the sides even if there are a temperature difference,
(e.g. vacuum flask ).

The zeroth law of thermodynamics:

• If A is in thermal equilibrium with B, and B in thermal
equilibrium with C, then C is also in thermal equilibrium with A.
 What is the Zeroth Law of
Thermodynamics?

The Zeroth Law of Thermodynamics states if system A is in thermal

equilibrium with system C and system B is also in thermal equilibrium with
system C, system A and system B are in thermal equilibrium with each other.
 The gas laws
The equation of a state of a gas was established by combining
a series of empirical laws.

Boyle’s law:
At constant temperature, the pressure of fixed amount of gas is
inversely proportional to its volume:

1 1 cont.
p , V , p , pV  constant
V p V
(at constant T & n)
 The gas laws
Boyle’s law: p

For two p & two V :

p1V1  const. , p2V2  const .

1/V

p1 V1 p Isotherm
p1V1  p2V2 or 
p2 V2

T
increases

V
The gas laws
 Charles’s law:
The volume of fixed amount of gas at constant pressure is
proportional to the temperature, T, (the volume increases linearly
with T at low p)
 Charles’s law V

p V
 const. ,  const.
T T

p1 p2 V1 V2 T
 , 
T1 T2 T1 T2

p
p1 T1 V1 T1
 , 
p2 T2 V2 T2

T
An ideal gas : is a theoretical gas composed of a set of randomly
moving, non-interacting .point particles

The ideal gas law : It was first stated by Émile Clapeyron in

1834 as a combination of Boyle's law and Charles' law. Therefore
The ideal gas law is often introduced in its common form:
N DIRECT RELATION
N
V V
T and P must remain constant
 The gas laws
From Avogadro’s principle:
The molar volume, Vm of ideal gases is a constant for all ideal gases, Vm =
V/n = RT/p = 22414 cm3 mol-1 at STP.
Vm increase at higher T or lower p.

• Combining the equation of Boyle’s law, Charles’s law and Avogadro’s

Principle leads to a single expression :

p V = const. n T PV=nRT

(the perfect “ideal” gas equation)

Boyle’s law Charles’s law
 Boyle’s law: this inverse proportional relationship can be written as P 1 Or PV= K
V

Therefore: p × V is a constant (For all gases and p → 0).

V
Charles ‘s law: this directly proportional relationship can be written as  K Or V α T
T
 Ex 1:
What pressure is exerted by 1.25 g of N2 in flask of volume
250 ml at 20 °C .

pV=nRT p = nRT/V

n = mass / M.W. = 1.25/28 = 0.0446 mol

p = (0.0446 * 0.0826 * 293.15) / (250 * 10-3) = 4.35 x 102 Pa

Ex 2:
Nitrogen is heated to 500 K in a vessel of constant volume. if
it enters the vessel at 100 atm and 300 K, what pressure it
would exert at the working temperature if it behaved as a
perfect gas?

V= constant , p1 = 100 atm , T1 = 300 K , T2 = 500 K , P2 = ?

p1/T2 = p2/T2

100/300 = p2/500

p2 = 167 atm
Dalton’s law of partial pressures:
Pressure is proportional to the
number of mole
Idea gas theory do not care about the nature of gas that
you have
Ex: ( 1.3 p.13 )
The mass percentage composition of dry air at sea level is
approximately 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?
 Real gases
Real gases – as opposed to a perfect or ideal gas – exhibit properties that cannot be explained
entirely using the ideal gas law. To understand the behaviour of real gases, the following must be
taken into account:

 compressibility effects;
 variable specific heat capacity;
 van der Waals forces;
 non-equilibrium thermodynamic effects;

pV  nRT  pV  ZnRT
 deal gas is based on assumption that are not correct ( exp. no interaction between atoms)
therefore PV/T is not constant for real gas . This ratio can change.

Only at STP real gas ≈ ideal gas

In realty
 Random Less collision of molecules with
straight line the walls it means less pressure
because when molecules
motion
moves slowly at low
temperature have more
chance to change
course
 Ideal gases
1- Gases molecules occupy no space
2- No interaction between gases molecules (van der Waals forces)
3- Perfect elasticity

PV = nRT

Real gases
1- Gases molecules occupy space
2- There are interaction between gases molecules
3- No elasticity
(a) The Compression Factor, Z

- At very low p, all gases have

Z ≈ 1 and behave nearly
perfect.

- At intermediate p, most gases

have Z < 1, the attractive
force reducing the Vm.

- At high p, all the gases have

Z > 1, they have larger Vm
than a perfect gas. Repulsive
forces are dominate.
 (b) Virial Coefficient
PV = A + BP + CP2
Empirical equation of virial equation of state
A, B, C…. Are varial coefficients
In science, an empirical formula is a mathematical equation that
predicts the observed results

In case or a real gas

PV = ZRT

2
pressure Z= 1 + B’P + C’P + ….
2
volume Z= 1 + B/V + C/V + ….
At low pressure or high volumes Z = 1, which represent an ideal gas
(d) Critical Constants
 The van der Waals equation

+/- a: Coefficient of attraction

+interaction , - repulsion
 The van der Waals equation

Water molecules has a lot of type of interaction between them (hydrogen bending Van
der The van der Waals interaction and dipole-dipole interaction
 The van der Waals equation
 For real gas, there are attractive and repulsive interactions:

• In case of repulsive interaction:

-The actual volume for molecules to travel is not V but V-nb
(where n is the number of mole of molecules , and b is a constant),
i.e. nb is approximately the total volume taken up by the molecules
themselves.
p V = n R T  p (V-nb) = n R T  p = nRT/(V-nb)
(b is the incompressible volume of a gas)

• In case of attractive interaction:

-The pressure depend on both:
1- The frequency of collisions with the walls
2- The force of each collision
In which both are reduced by the attractive force
 The van der Waals equation
• The frequency of collisions and collision force are reduced by the
attraction , and this reduction increases as the concentration increase.

... p is reduced in properties to the square of the concentration.

... reduction in p  reduction of frequency (i)  reduction of

strength (ii)
• But reduction of frequency of collision and collision strength are
dependant on the molar concentration ( molar concentration) and
allowing for both attractive and repulsive interaction:

2
nRT n p
RT a
 2
p  a  Or in terms of
V  nb  V  molar volume: Vm  b Vm
- where a is the amount of attractive force and b is the incompressible volume
 The features of van der Waals equation
1) Perfect gas isotherms are obtained at high temperature
and large Vm :
when T is high, the term (RT/Vm-b) may be so large and
exceeds the second term. Also, when Vm is larger than b
(Vm >> b), then: “p = RT/Vm” the perfect gas equation.

2) Liquids and gases coexist when cohesive and dispersing

effects are in balance, liquid phase is in equilibrium with gas
phase.

3) The critical constants are related to the van der waals

coefficients (pc , Vc , Tc related to a, b).
For T < Tc, the calculated isotherm oscillate ( ). The
oscillation decreases as T → Tc, and at T = Tc the curve has a
flat inflexion ( ).
 The features of van der Waals equation

• It is known that an inflexion of this type occurs when both the 1st
and 2nd derivatives of van der Waals equation are zero:

dp  RT 2a d 2
p 2RT 6a
1st :   0 2 nd : 2   0
dVm Vm  b  Vm
2 3
dVm Vm  b  Vm
3 4

• The solution of these two equations at the critical point results in:

a 8a
Vc  3b pc  Tc 
27b 2 27 Rb

• These relations provide an alternative route to calculate a & b by

knowing the values of the critical compression factor Zc (Zc=
pcVc/RTc = 3/8).
The principle of corresponding state
 The principle of corresponding state
• van der Waals equation the principle of corresponding state :

RT a
p  2 Introducing the reduced variables
Vm  b Vm

RTrTc a
pr pc   2 2 We have : Vc  3b pc 
a
Tc 
8a
VrVc  b Vr Vc 27b 2 27Rb

- Replacing the critical variables by their values in the equation:

a pr 8aTr a 8Tr 3
  2 2  pr   2
27b 2
27b(3bVr  b) 9b Vr 3Vr  1 Vr

- This equation does not depend on a & b which are different for different gas.
Therefore, only one curve is observed for all gases if Vr & Tr are the same
 Exercises & Problems

• Exercises
• 1.1(b), 1.7(b), 1.9(b), 1.10(b), 1.16(b), 1.17(b),
1.21(b).

• Problems
• 1.7, 1.9, 1.13, 1.25, 1.27.

• “It is advisable that students solve as many

exercises and problems as possible.”