Lecture 5: Introduction

to Physical Chemistry
(CHM 103)

Facilitator: Prof. Nnabuk Okon Eddy

Okon.nnabuk@unn.edu.ng
National Open
University of Nigeria National Open University Of Nigeria
Objectives

• To understand what is critical conditions and critical constants (critical

temperature, critical volume and critical pressure)
• Relationship between critical constants and van der Waals constants (a
and b)
• Forces of interactions
• (i) Dipole-dipole interaction
• (ii) Dipole-induced dipole interaction
• (iii) Induced dipole-induced dipole interaction
• Effect of interaction forces on physical properties
• Hydrogen bonding and its effect on physical properties
Critical condition and critical constants
• Real gas obeys ideal gas laws at low pressures and at high temperatures
• At high pressures and sufficiently low temperature, the gas is liquefied
• The critical temperature above which the gas cannot liquefied , no matter
how much pressure is applied
• All gases have their respective critical temperature
• The pressure required to liquidify a gas at the critical temperature is called
critical pressure
• . The volume occupied by one mole of a fluid at its critical temperature and
pressure is called critical volume
• This phenomenon was first observed by Andrew
Explanation

• At high temperature. the isothcrm is a hyperbola in accordance

with Boyle's law.
• At low temperatures. the isotherms show considerable deviation
from ideal gas behaviour
• The critical point is indicated as C. The corresponding
temperature, volume and pressure are the critical temperature,
volume and pressure respectively
Derivation
• The van der Waal equation can be written as
𝑎
• 𝑃+ 𝑉 − 𝑏 = 𝑅𝑇 (1)
𝑉2
𝑎 𝑎𝑏
• 𝑃𝑉 + − 𝑃𝑏 − = 𝑅𝑇 (2)
𝑉 𝑉2
𝑎 𝑎𝑏
• 𝑃𝑉 − 𝑃𝑏 + − = 𝑅𝑇 (3)
𝑉 𝑉2
2
𝑉𝑚
• The multiplication of equation 3 by gives
𝑃
2
𝑉𝑚 2
𝑉𝑚 𝑎 2
𝑉𝑚 𝑎𝑏 2
𝑉𝑚 2
𝑉𝑚
• (𝑃𝑉𝑚 )𝑥 − 𝑃𝑏 𝑥 + 𝑥 − 2 𝑥 = 𝑅𝑇 𝑥
𝑃 𝑃 𝑉𝑚 𝑃 𝑉𝑚 𝑃 𝑃
𝑎𝑉𝑚 𝑎𝑏 2
𝑅𝑇𝑉𝑚
• 𝑉𝑚3 − 2
𝑏𝑣𝑚 + − −
𝑃 𝑃 𝑃
Derivation

𝑎𝑉𝑚 𝑎𝑏 𝑅𝑇𝑉𝑚2
• 𝑉𝑚3 − 2
𝑏𝑣𝑚 + 𝑃 − 𝑃 − 𝑃
𝑅𝑇𝑉𝑚2 𝑎𝑉𝑚 𝑎𝑏
• 𝑉𝑚3 − 2
𝑏𝑣𝑚 − 𝑃 + 𝑃 − 𝑃 = 0
𝑅𝑇 𝑎𝑉 𝑎𝑏
• 𝑉𝑚3 − 2
𝑣𝑚 𝑏 − 𝑃 + 𝑃𝑚 − 𝑃 =0
• The cubic equation will yield three values for 𝑉𝑚 corresponding to a
given pressure and temperature.
• All the three values of 𝑉𝑚 may be real or one may be real and the
other two may be complex conjugates
Values of a and b

𝑎
• 𝑃+ 𝑉 − 𝑏 = 𝑅𝑇 – van der Waal equation
𝑉2
27𝑅𝑇 2 9
•𝑎 = = 8 𝑅𝑇𝑐 𝑉𝑐 (PV = RT, V = RT/P)
64𝑃𝑐
𝑅𝑇𝑐 𝑉𝑐
𝑏= =
8𝑃𝑐 3
• ‘a’ and b are van der Waal constants
Question

• The critical temperature of a gas is 298 K and the molar critical

volume is 22.4 dm3. Calculate the van der Waal constant, a. (ii)
At what pressure will the gas have this critical constant
27𝑅𝑇 2 9
•𝑎 = = 8 𝑅𝑇𝑐 𝑉𝑐 = 9/8 x 8.314 J/mol/K x 298 K x 22.4 dm3
64𝑃𝑐
27𝑅𝑇 2 𝑇𝑐2
• = 9/8 x 8.314 J/mol/K x 298 K x 22.4 dm3
64𝑃𝑐
𝑗
8.314
27× 𝑚𝑜𝑙× 298 2 𝐾 ×(298)2 𝐾
• 𝑃𝑐 = 𝐾
64×9/8 x 8.314 J/mol/K x 298 K x 22.4 dm3
Liquefaction: Significant
• Liquefaction is a process of making a gas or solid to become liquid.
• We can make a solid become liquid by melting and a gas can be changed
to liquid by condensation.
• The critical phenomena and our knowledge of the critical constants are
useful in the liquefaction of gases.
• liquefaction of air is important in the manufacture of nitrogen and oxygen
which are both important industrial chemicals.
• The liquefied petroleum gas (mixture of propane and butane) is used as a
domestic fuel.
• Liquid helium and nitrogen are important for making the materials
superconducting. liquefiable gases such as ammonia and
dichlorofluoromethane (Freon) are used in refrigeration and air
conditioning.
• Many substances like water, ethyl alcohol. etc . have high critical
temperatures and hence exist as liquids even at room temperature.
• Others like ammonia. sulphur (IV) oxide, etc.. under ordinary
conditions have low critical temperature but can be easily liquefied by
cooling using freezing mixtures under moderate pressure.
• Freezing of mixture lowers the temperature of a substance below its
critical temperature and the moderate pressure is then sufficient to
liquefy the gas.
• What does freezing lowers temperature and boiling increases
temperature

• Note
• One of the condition for freezing is that the temperature of the
system must be reduced below its critical temperature and for a
system to remain in gaseous state, the temperature should be
above its critical temperature
Liquefaction

• On the other hand. there are many gases like oxygen. nitrogen.
hydrogen and helium whose critical temperatures are much
lower.
• Special methods are adopted to cool these gases below their
critical temperature.
• Two common methods of liquefaction
• (i) Linde’s method
• (ii) Claude’s method
Linde’s method

• The method is based on the principle of Joule-Thompson effect.

The expansion of a gas from a region of high pressure to a
region of low pressure, its temperature falls.
• The gas does not do any external work but the kinetic energy of
the molecules expend some work to overcome the attractive
forces between the molecules.
• The temperature of the gas is lowered.
• To have a cooling effect. a gas is brought below a temperature
called its inversion temperature before allowing It to expand.
Definition: Inversion temperature

• The inversion temperature in thermodynamics and cryogenics

is the critical temperature below which a a gas that is
expanding at constant enthalpy will experience a temperature
decrease, and above which will experience a temperature
increase.
• Substances with positive values of Joule Thompson coefficient
undergoes cooling by expansion but those with negative values
of the Joule-Thompson coefficient experience a rise in
temperature on expansion
Clause’s method

• Claude"s method is more efficient than Linde’s method. The

compressed gas in the insulated vessel (i.e.. under adiabatic
conditions) is partly used to do work against a piston in a
cylinder and partly expanded through a valve.
• The cooled gas obtained by adiabatic expansion is used for
cooling the incoming gas in the heat exchanger.
• The process is repeated till the gas is liquefied
Intermolecular forces

• Real gases deviate from the ideal gas behaviour because of the
presence of intermolecular forces.
• The intermolecular forces are also responsible for the
conversion of gases into liquids and solids.
• Van der Waals also developed a model that can explain the
behaviour of liquids.
• In recognition of his work. the weak internolecular forces in
liquids and solids are often called Van der Waals forces.
Van der Waal forces

(i) Dipole-dipole interaction

(ii) Dipole-induced dipole interaction
(iii) Induced dipole- induced dipole interaction
(London or dispersion forces)
Dipole Dipole interaction

• Polar molecules can attract each other electrostatically. During this

attraction the positive end of one molecule is close to the negative end of
the adjacent molecule.
• Such an attraction is called dipole-dipole interaction.
• In the liquid state. although molecules are in continuous motion. they tend
to align themselves so that. on the average. the intermolecular attractions
are maximum
• The interaction energy between two polar molecules separated by a
distance r is found to be directly proportional to the square of the product of
the dipole moments of the two molecules and inverselv proportional to
temperature
Dipole- induced dipole interaction

• Not suitable for the explanation of attractive force between polar

molecules at high temperature (except at low temperature)
• A polar molecule can induce a dipole moment in a nieghbouring
polarisablc atom or molecule.
• An atom or molecule is said to be polarizable, if its electron cloud can
be distorted. The ability of a species to undergo electronic distortion
is described in terms of polarisability' The electron charge cloud of a
larger atom (one with higher atomic number) can be easily be
distorted due to the
Dipole-induced dipole interaction

• Larger number of electrons

• Insignificant influence of the nucleus since it is far from the nucleus
• The interaction energy between a dipole and an induced dipole separated
by a distance, r is
• (i) Directly proportional to the square of the dipole moments of the polar
molecule,
• (ii) Directly proportional to the polarisability of the molecule (in which dipole
is induced).
• (iii) Inversely proportional to the sixth power of didtance of separation, r.
Dipole induced dipole interaction

• A larger atom has a higher polarisability than a smaller atom For

example, argon has higher polarisability than helium.
• larger molecules (due to greater number of electrons) have higher
polarisability than smaller molecules. For example. ethane is more
polarisablc than methane: propane is more polarisable than ethane,
and so on.
• The dipole-induced dipole interaction between a polar molecule and
a neighbouring polarisable molecule (in which dipole is induced)
causes a lowering of energy. T
• An attractive interaction adds to the stability.
London force: Induced dipole-induced dipole
interaction

• The only one that can explain liquefaction of gases like

hydrogen, oxygen, chlorine. helium and argon - which are all
non-polar
• London gave an acceptable quantitative explanation for the
attractive forces existing between nonpolar molecules
• These forces are called dispersion forces since the oscillations
producing the attractive forces are also responsible for the
dispersion of light by the molecules.
London force in Helium

• On the average. the charge cloud around a helium atom is

symmetrical.
• The electrons surrounding the nucleus of the helium atom are in
constant motion, therefore, the helium atom can develop a
momentary non-sysmmetrical electron distribution.
• The consequence is a temporary dipolar arrangement of charge.
otherwise known as instantaneous polarity.
• The helium atom that has instantaneous polarity can then induce a
dipole in the neghbouring helium atom.
Hydrogen bonding

• Hydrogen bonding, interaction involving a hydrogen atom located between a

pair of other atoms having a high affinity for electrons; such a bond is weaker
• It is a special type of dipole-dipole attraction between molecules, not a covalent bond to a
hydrogen atom.
• It is due to the attractive force between a hydrogen atom covalently bonded to a very
electronegative atom such as a N, O, or F atom and another very electronegative atoms.
• Hydrogen bond strengths range from 4 kJ to 50 kJ per mole of hydrogen bonds.
• Because of the difference in electronegativity, the H atom bears a large partial positive
charge and the N, O or F atom bears a large partial negative charge
• A H atom in one molecule is electrostatically attracted to the N, O, or F atom in another
molecule.
Physical consequences of hydrogen bonding

• At 25oC, nitrosyl fluoride (ONF) is a gas whereas water is a liquid. Why?

• ONF and water have about the same shape. Hydrogen bond tends to increase boiling
point
• ONF has a higher molecular weight (49 amu) than water (18 amu).
• London dispersion forces is not responsible for the difference between these two
compounds.
• ONF and water have the same dipole moment.
• dipole-dipole forces not responsible for the difference between these two compounds.
• ONF cannot form hydrogen bonds; water can form hydrogen bonds.
Effect of molecular interaction on physical
properties

• Polar molecules have higher melting and boiling points than the non-polar
molecules of similar molecular size.
• Among the noble gases_ the boiling point increases with atomic number
because the London forces are more in large atoms due to higher
polarisability.
• Among a series of similar non-polar molecules such as hydrocarbons.
boiling point increases with the molecular size because a larger molecule
has higher polarisability and increased London forces.
• Among the hydrides of groups 5. 6 and 7 NH3 H20 and HF have higher
boiling point because of strong hydrogen bonding in these three
compounds
• There is a striking contrast in the boiling points of the isomeric
compounds. ethanol (351 K) and dimethyl ether (249 K)_ The
hydrogen bonding between the molecules of ethanol contributes to a
much higher boiling point but the other hand. the molecules of
dimethyl ether are held together only by weaker dipole-dipole
interaction
• London forces also depend on the molecular geometry For example.
among the isomeric hydrocarbons_ straight chain isomers have
higher boiling point than the branched cham Isomer