CHM 151: FOUNDATION CHEMISTRY II

2nd Semester 2021/2022

Lecture Notes
Course Outline
• States of matter-gas, liquid, and solid
• Gaseous state of matter: The Kinetic theory of gases.
• The gas laws – Boyles Law, Charles Law, Gay-Lussac’s Law, Avogadro's Law, The
Ideal gas equation, Dalton's, law of partial pressure, Graham's law of diffusion.
• Behaviour of real gases and deviation from ideal behaviour. (Van der Waals
equation)
• Critical constants and liquefaction of gases.
• Liquids - pressure and temperature relationship.
• Raoult's and Henry's laws.
• Azeotropic mixtures.
• Partition/distribution law.
• Colligative properties - boiling point elevation, freezing point depression and osmotic
pressure.
• Solid state - structure of solids, types of crystal structure.
• Eutectic mixtures and phase diagram.
• Thermochemistry: entropy, free energy, Hess' laws and heat of reaction.
• Introduction to chemical kinetics: First order reactions, rate constant, half-life, rate
and factors affecting rate of reaction.
• Activation energy and catalysis.

Page 1 of 24
Introduction
Matter and energy
Matter is anything that has mass and occupies space. Matter exists mainly in three states;
solid, liquid and gas. Liquids and gases together are called fluids. On the basis of properties
of matter (both physical and chemical) it can be classified in the following ways:

For example, water can exist as ice - which is a solid state of mater, as liquid water -
which is a liquid state of matter, and as water vapour or steam - which is a solid state of
mater.

Physical properties of ice, liquid water and steam are very different but composition of
water remains the same H2O (H and 0 in 2 : 1 atomic ratio, molar mass = 18 g mol -1.
Characteristics
three slates (of H2O) depend on the energies of molecules, and the manner in which the
molecules attract each other. In all cases, one should specify the state in which substance
exists.
Comparison of various properties of solids, gases and liquids has been summarised in the
table below.
Table. 1.1 Some properties of solids, liquids and gasses

Physical classification of matter

(i) Solids In solid state, the constituent particles of matter are held close to each other and
in an ordered arrangement. The constituent particles in a solid species, therefore, cannot
leave their positions. Thus, solids have definite shape and volume, e.g. ice cube, iron bar,
sugar crystals etc. In this state, the intermolecular forces between constituent particles are
very strong.
(ii) Liquid In liquid state, the constituent particles are not as much close as in solid state.
They
have space around them so that they can leave their positions and move in a limited
manner.

Page 2 of 24
Thus, liquid has definite volume but no definite shape; they take the shape of the vessel in
which they are stored, e.g. water, oil, mercury etc. In this state, the intermolecular forces
between constituent particles are very moderate.
(iii) Gases In gaseous state the constituent particles are far apart from each other as
compared to solid state and liquid slate. These can leave their position and move
everywhere in different directions with different velocities colliding among themselves and
against sides of the container, e.g. waler vapour, air, oxygen, gas, nitrogen gas etc. In the
gaseous stale, the intermolecular force between constituent particles are very weak or
negligible and molecules lie far apart from one another.
(iv) Plasma Along with solid, liquid and gases there are two more stales of matter, plasma
and Bose-Einstein condensate. It is a state containing gaseous ions and free electrons
which is formed when gaseous state is taken to a very high temperature, e.g. electric arc,
sun etc.
(v) Bose-Einstein condensate The concept and existence of this state is totally opposite
to plasma. The state is achieved by a gas of extremely low density, at supercooled
conditions, i.e. near absolute zero temperature.

Change of state
These three states of matter are interconvertible by changing the conditions of the
temperature and pressure, as shown in the Fig. 1.1.below. Typically, change of state or
what is known as phase transition, occurs when the there is a temperature change i.e
heating or cooling. Thus, when a substance is heated it acquires kinetic energy, and when
cooled it becomes less energetic.

Gaseous State of Matter

Gaseous state is the simplest, both to describe and in terms of their internal structure but
they are of immense importance. The intermolecular interactions between gas molecules
are negligible. When the two molecules are far apart, they move independent of each other.
At a given pressure, as the molecules come closer, the molecular interactions become
important.
All substances that are gases at room temperature may be liquefied by cooling and
compressing them. Volatile liquids are easily converted to gases at room temperature or
slightly above. The term "vapour" refers to a gas that is formed by evaporation of a liquid
or sublimation of a solid, it is commonly used when some of the liquid or solid remains in
contact with the gas.
Kinetic theory of gases

Page 3 of 24
All gases are miscible, i.e. they mix completely unless they react with each other. The
kinetic theory of gases attempts to explain the microscopic properties of an ideal gas in
terms of the motion of its molecules. In its modern form, the Kinetic theory of gases is
based on the following postulates.
• A gas is made up of small identical particles called molecules. These gas molecules
move randomly in all directions, colliding with each other and with the walls of the
containing vessel.
• There is no force of attraction between gas molecules.
• Molecular collisions are perfectly elastic i.e no loss of energy when molecules collide
with each other or with the walls of the container wall.
• The volume of the gas molecule is negligible compared to the container volume.
• The temperature of the gas is directly proportional to the kinetic energy of the molecules.
• The collision of the gas molecule with the container wall give rise to what is called the
gas pressure.

The characteristics of gases can be described in terms of the following parameters:

(i) Pressure (p) Pressure of the gas is the force exerted by the gas molecules per unit area
on the walls of the container in all directions. Instrument used for the measurement of the
pressure of a gas is called manometer.

(ii) Atmospheric pressure It is defined as the pressure exerted by the gases of the
atmosphere at the sea level. Instrument used for the measurement of atmospheric
pressure is called a barometer.
Atmospheric pressure = pgh
where, h = height of mercury column (in barometer)
g = acceleration due to gravity
p = density of the mercury' at room temperature
The SI unit of pressure, is pascal (Pa). It is defined as 1 newton per metre square (1 Pa =
1 N m-2). Several other units used for pressure are summarised below:

Table 1.2 Various units of pressure

Page 4 of 24
(iii)Volume (v) The volume of a gas is defined as the space occupied by the gas. It is
always equal to the volume of the container in which the gas is enclosed. The SI unit of
volume is m3. Other units of volume are cm3 and dm3 etc.

(iv)Temperature (T) It is the measure of hotness of the system and energy of the system.
As the temperature of a gas increases, the kinetic energy of gas molecules increases. SI
unit of temperature is kelvin (K). Other units of temperatures are Celsius (°C) and
Fahrenheit (°F).

(v) Mass (m) The mass of a gas can be determined by weighing the container in which the
gas is enclosed and again weighing the container after removing the gas. The difference
between the two masses gives the mass of thegas. The amount of gas is related to number
of moles of gas.

SI unit of mass is kg and unit of amount of substance is mol.

The Gas Laws

The relationships among pressure, temperature and volume of a given mass of a gas are
described by gas laws.

Boyles Law
(Pressure-Volume relationship)
In 1662, Anglo-Irish scientist Robert Boyle formulated this law which states that:
"At constant temperature, the pressure of a fixed amount of a gas (number of moles, n)
varies inversely with its volume".

The value of constant k depends upon the amount of gas, temperature of the gas and the
units in which p and V are expressed.
On changing from State I to State II at constant temperature (T).

Page 5 of 24
Practical significance of Boyle's law
Gases are highly compressible. When a given mass of a gas compressed, number of
molecules remain same but occupy smaller volume (space). Gases are denser at high
pressure. Boyl’s law can thus be expressed in term of density as follows.

Thus, at constant temperature, Boyle' law can also be expressed in terms of density as:

Graphical Representations of Boyle's Law

(a) Graph between p and V at constant temperature is called isotherm. Various isotherms
are given in figure 1.2(a) below

Figure 1.2(a) various isotherms of variation of p and V (each taken at constant

temperature). It is in the form of equilateral (or rectangular) hyperbola.

From the curve it is clear that same volume of gas exerts a larger pressure at a higher
temperature. Instead of V, density (d) can be taken.

1
(b) Fig. 4.2 (b) below gives isotherms of the variation of p with (𝑣) or density at constant
1
temperature. The straight line indicates that (𝑣) regularly increases with an increase in p

Figure 1.2(b) isotherms of the variation of p with (1/v) or density at constant temperature.

(c) Since, (pV = constant), hence isotherm between (pV) and p is linear with zero slope as
shown below.

Page 6 of 24
Figure 1.2(c) isotherm between (pV) and p

Example 1
Volume of CO2 gas equal to 20.0 dm3 was collected at 300 K and 1.00 bar pressure. What
would be the volume of CO2 collected at 300 K and at a pressure reduced by 25%?
Strategy
Temperature has been kept constant and volume of CO2 would change on changing the
pressure. Thus, Boyle's law is applicable p1V1 = p2V2 at constant temperature.

Charles’ Law
(Temperature-volume relationship)
Variation of volume with temperature was first studied by French chemist, Jacques Charles,
in 1787 and then extended to another French chemist Joseph Gay-Lussac in 1802.
According to Charles's law, 'for a fixed mass of a gas under isobaric condition
(constant pressure), the gas expands as the temperature rises.'

Page 7 of 24
Graphical Representations of Charles Law
Graphs between V and T at constant pressure are called isobars as shown in figures (1.3(a)
and (b).

Figures (1.3(a) and (b). Graphs between V and T at constant pressure

If temperature is taken in kelvin scale then the straight line obtained passes through the
origin (fig 1.3(a)). If temperature is taken in Celsius then line intercepts the temperature
axis at -273.15°C.(fig 1.3(b)). The slopes of lines obtained at different pressures are
different but at zero volume all lines meet the temperature axis at -273.15°C. The volume
should, therefore, become zero at - 273.15° C. Any further lowering is impossible, since it
would imply negative volumes - a meaningless concept.

Example 2
Density of a given mass of an ideal gas at 300 K changes from 0.4 g dm-3 to 0.2 g dm-3
What is the final temperature

Page 8 of 24
Gay-Lussac’s law
(Pressure-temperature relationship)
At constant volume, for a given mass of a gas the pressure is directly proportional to the
pressure.

Pressure coefficient is the change in pressure per degree change in temperature.

Graphical representation of Gay-Lussac's law

A graph between p and T at constant V is called isochore. The shapes of various isochores
at different volumes are different, but all lines meet temperature axis at 0 K.

Figure 1.4 Pressure versus temperature (K) graph (isochores) of a gas

Avogadro's law
(Volume-amount relationship)
Equal volumes of any two gases at the same temperature and pressure contain the same
number of molecules. One mole of any gas contains the same number of molecules
(Avogadro's number = 6.02 x 102)) and by Avogadro's law must occupy the same volume

Page 9 of 24
at a given temperature and pressure. The volume of one mole of a gas is called molar
volume, Vm which is 22.4 Lmol-1 at STP (at 273.15 K and 1 atm).
We can re-express Avogadro's law as follows: The molar gas volume at a given
temperature and pressure is a specific constant independent of the nature of the gas
specific constant =22.4 Lmol-1 (at 273.15 K and 1 atm)

Note that STP conditions are: Temperature = 273.15 K, Pressure = 1 bar (= 105 Pa)
These values are freezing point of water and atmospheric pressure at sea level.

Example 3
Based on the following chemical reactions,

Calculate moles of KCIO3(s) to form O2(g) that can react with 2 L of 2SO2(g) under standard
state.
Solution

The ideal gas equation

The simple gas laws relating gas volume to pressure, temperature and amount of gas,
respectively, are stated below.

Page 10 of 24
If all four variables considered simultaneously, then:

This equation (pV = nRT) is called ideal gas equation. R is called ideal gas constant.
The three experimentally observed laws of gas behaviour have been combined in ideal
gas equation.

Page 11 of 24
Determination of Density and molar mass from ideal gas equation

Gas densities differ from those of solids and liquids in some important ways:
• Gas densities are generally stated in g/L instead of g cm-3.
• Gas densities are strongly dependent on pressure and temperature, increasing as the
gas pressure increases and decreasing as the temperature increases.

• The density of a gas is directly proportional to its molar mass.

Page 12 of 24
Example 4 (ideal gas equation)
Calculate the density of helium at 21 °C and 752 mmHg.

1. A 200.0 mL flask at 100°C and a pressure of 1 atm is filled with the vapour of the
volatile liquid. If mass of the substance in the flask is 0.970 g, what is the molar
mass of the liquid?

Example 5
A1,27g sample of an oxide of nitrogen believed to be either NO or N 2O occupies a volume
of 1.07 L at 25°C and 737 mmHg pressure. Which oxide is it?

Page 13 of 24
Example 6
What is the density of air at STP? Assume air is a mixture of 80% N2 and 20% O2 by weight.

Dalton's law of partial pressure

When two or more gases which do not react together chemically, are present in the same
container, the total pressure exerted by the mixture is the sum of the partial pressure of
each
constituent gas.

where, p1, p2, p3, ... are the partial pressure of gas number 1,2, 3. In a mixture of gases,
the pressure exerted by the individual gas is called partial pressure.
If V is the total volume and n1, n2... etc., are the number of moles of the gases 1, 2,... etc.,
then

Partial pressure in terms of mole fraction

Page 14 of 24
So, we can say that the partial pressure of a gas in a mixture is equal to the product of its
mole fraction and the total pressure of the gas.

Example 7 (Partial pressure of gases)

Unpurified natural gas delivered from the gas field is a mixture of gases with volume
percentage as: methane: 80%, ethane: 6%, propane : 3%, butane: 4% and others (N2, H2S,
CO2): 7%. Calculate the partial pressure of methane if the gas comes from the field at a
pressure of 5.0 x 105Pa.

Example 8 (Daltons law of partial pressure)

A neon (20 g mol-1) and dioxygen (32 g mol-1) mixture contains 70.6 g dioxygen and 167.5
g neon. If pressure of the mixture of gases in the cylinder is 25 bar, what is the partial
pressure of dioxygen and neon in the mixture?

Page 15 of 24
Graham's law of diffusion (and effusion)
Diffusion, the spread of one substance throughout a space or through a second substance,
is one of the properties of a gas. The property of intermixing of gas is called diffusion.
Diffusion of gases does not depend on their densities and does not require
the help of any external agency. A second property is called effusion, which is the escape
of gas molecules under pressure through a tiny hole such as a pinhole in a balloon.
• All gases diffuse spontaneously into one another when they are brought into contact.
• Diffusion into a vacuum will take place much more rapidly than diffusion into another gas.
• The process of diffusion also depends on the movement of molecules. Diffusion occurs
when two (or more) gases come into contact and mix.

Graham's law states that

"Rates of diffusion of gases are inversely proportional to the square roots of their densities
(or their molar masses)".

Page 16 of 24
If two gases diffuse under different pressures, p1 and p2 then,

Hence, relative rate of diffusion of a gas under different pressures is:

Effect of temperature on rate of effusion

Thus, if temperature increases, rate of effusion or rate of diffusion also increases. In cold
countries (where temperature remains low), there are more chances of smog since heavier
gases as NO, NO2, SO2 do not effuse easily. In hot countries (where temperature remains
high) chances of smog are very rare as gases effuse easily.

Example 9 (Rate of effusion)

A gas of unknown identity effuses at the rate of 83.3mL s -1 in an effusion apparatus in which
carbon dioxide effuses at the rate of 102mL s-1. Calculate the molar mass of the unknown
gas.

Page 17 of 24
Example 10 (Rate of effusion)
The pressure in a vessel that contained pure oxygen dropped from 2000 torr to 1500 torr
in 55 min, as the oxygen leaked through a small hole into a vacuum. When the same vessel
was filled with another gas, the pressure dropped from 2000 torr to 1500 torr in 85 min.
What is the molar mass of the second gas?

Behaviour of real gases and deviation from ideal behaviour. (Van der Waals
equation)
Two types of gases exist. Real gas and Ideal gas. A real gas is defined as a gas that does
not obey gas laws at all standard pressure and temperature conditions. When the gas
becomes massive and voluminous it deviates from its ideal behaviour. Real gases have
velocity, volume and mass. When they are cooled to their boiling point, they liquefy. When
compared to the total volume of the gas the volume occupied by the gas is not negligible.
Examples include O2(g), He2(g), CO2(g), etc
Ideal gases have velocity and mass. They do not have volume. When compared to the
total volume of the gas the volume occupied by the gas is negligible. It does not condense

Page 18 of 24
and does not have triple point. There is no known deal gas. However, a few gases behave
as an ideal gas under specific temperature and pressure boundaries.
𝑝𝑉
For an ideal gas, all related gas laws are followed and a plot of against p at constant
𝑅𝑇
𝑝𝑉
temperature is a straight line. Thus, if a gas is ideal, = 1 for 1 mole of a gas.
𝑅𝑇
But for real gas this value is not 1. However, there exists no gas which can obey gas laws
in all conditions of temperature and pressure. So, ideal gas is just a hypothetical concept.
This behaviour is shown in the figure below.

Figure 1.5 Behaviour of real gases and an ideal gas.

Compressibility factor (Z)

Experimentally, it has been observed that at low pressure and high temperature, real gases
𝑝𝑉
obey gas laws approximately. The extent to which the measured value of , called
𝑅𝑇
compressibility factor (Z), deviates from 1, is a measure of the non-ideality of gas.

Deviations are observed if measurements are carried out at high pressure and low
temperature, especially when a gas is on the point of condensing to a liquid

Z > 1 indicates positive deviation. It implies that gas is less compressible than expected
from ideal behaviour.
Z < 1 indicates negative deviation. It implies that gas is more compressible than expected
from ideal behaviour.
From figure 1.5, we observe that even at 1 atm pressure there are small deviations from
ideality (Z =1) for all gases at any temperature. The extent of deviation at any given
temperature and pressure depends on the nature of gas. Z approaches unity as pressure
approaches zero, which means pV = nRT is an approximate equation applicable at low
pressure.

Page 19 of 24
Example 11 (Compressibility factor, Z)
Compressibility factor of a gas behaving non-ideally is 0.90 at 273 K and at a pressure of
1 bar. Calculate molar volume under given conditions.

Explanation for deviation from ideal behaviour

(i) According to the kinetic theory of gases, the volume of the molecules is negligible
compared to the total volume of the gas. However, this postulate can only be justified under
ordinary temperature and pressure.
• What happens when pressure is very high? Volume of molecules remains the same (as
they are incompressible) but volume of gas decreases appreciably
• What happens when pressure is very low? Volume of the gas becomes very high.
• What happens when temperature is low? In this case also volume of the gas decreases
appreciably
• What happens when temperature is high? Volume of the gas increases appreciably.
Therefore, under all conditions of temperature and pressure, the volume of molecules
cannot be considered negligible to the total volume of gas. For real gases this assumption
is true only at low pressure and high temperature.

(ii). According to the kinetic theory of gases, the force of attraction between gas molecules
is negligible. However, this postulate is only valid under low pressure and high temperature,
since molecules are far apart from one another under these conditions.
Recall, the pressure in the gas is due to collisions of molecules against sides of the
container in which gas is placed. When pressure is high or temperature is low, molecules
have force of attraction thus rate of collisions against sides of the container is decreased.
This decreases pressure of the gas.
Corrections applied to ideal gas
From the above explanations, it is therefore necessary to apply (i) volume correction and
(II) pressure correction to the ideal gas equation to make it applicable to real gases.
1. Volume correction
This correction arises due to finite size of molecules under the conditions of high
pressure/low temperature.

Page 20 of 24
2. Pressure correction
This arises due to existence of force of attraction among the molecules. Pressure is due to
collisions of some molecules against sides of the container, when no force of attraction
exists. Molecules of such type have resultant force of attraction as zero, hence they strike
the sides of the container freely causing pressure. Other molecules which have some
resultant force of attraction collide the side of the container with decreased striking power,
hence pressure developed due to such molecules is less. Hence, pressure correction is
required.

Van der Waals equation

When pressure and volume corrections are applied to ideal gas:

And since,

Page 21 of 24
Equation obtained is therefore:

This is called van der Waals' equation for n moles of a gas a and b are called van der
Waals' constants.
Units of van der Waals' constants are given below:

Example 12 (van der Waals' equation)

Calculate pressure of 1 mole of SO2 at 273 K, it occupies volume of 22.4 dm3. Assume
real behaviour.
(Given a = 6.865 dm6 atm mol-2 and b = 0.057 dm3 mol-1).

Page 22 of 24
Critical constants and liquefaction of gases
Any gas can be liquefied by decreasing its temperature and increasing its pressure.
Decreasing of the temperature decreases the average kinetic energy of the molecules and
increasing of the pressure decreases the average distance between molecules. When the
molecules are close together, if their kinetic energy is lowered, they do not possess enough
energy to overcome the forces of attraction between molecules and liquid is formed.
For each substance however, there exists a temperature called critical temperature (Tc)
above which the substance cannot be liquefied, no matter how great the applied pressure.
Thus, Tc is the maximum temperature at which a gas can be liquefied.
The minimum pressure required to liquefy a gas at its critical temperature is called critical
pressure (pc). Volume occupied by one mole of a substance at critical temperature and
critical pressure is called its critical volume (Vc). In terms of van der Waals' constants a
and b,

Andrew isotherm (Concept of critical constants)

Thomas Andrew studied isotherms of CO2. He investigated that CO2 liquefied below 31.1°C
by increasing pressure. It could not be liquefied above 31.1 °C inspite of high pressure.
Thus, 31.1 °C is the critical temperature of CO2. At 50°C the isotherm for CO2 appears as
that of an ideal gas. As the temperature is lowered the deviation from the expected
theoretical curve becomes more and more pronounced. At a low temperature (at 13°C as
shown in Fig. 1.6) the isotherms ABCD consists of three parts.
As pressure is increased volume decreases along AB. From the point B to C along
horizontal line BC, volume drops suddenly without any change in pressure indicating that
gas changes to liquid state along BC which is completed at point C. After point 7 there is
rapid change in pressure along CD without appreciable change in volume. At 31.1 °C the
isotherm has a very small (almost negligible) flat portion, virtually reduced to point E. Above
31.1°C under all pressure, it remains in gaseous state.

Fig. 1.6 Isotherms of C02 and critical temperature

Page 23 of 24
Substances for which the intermolecular forces are large, such as polar molecules, NH3,
SO2 and H2O have high values of Tc. Substances for which the intermolecular forces of
attraction are small such as H2, N2, Ar and O2, have low values of Tc. The curve in the
phase diagram that gives the temperature and pressure at which the liquid and vapour
phase are in equilibrium comes to an end at the critical temperature and pressure.
Above that point, called the critical point, there is only a single fluid phase, and it is
impossible to distinguish liquid are vapour.
At critical point some significant features are as follow:
• At the critical point, the density of the substance in gaseous are liquid states remains
same.
• The surface of separation between liquid and gas disappears and there is no distinction
between liquid and gaseous stair
• No second phase is formed irrespective of the pressure of the system.
• Gases below their critical temperatures are called vapour.
• Fluids above critical temperature are called super critical fluids. Such fluids dissolve many
organic substances. These are used for speedy separation of a mixture into its
components. Carbon dioxide above 31.1°C and 600 bar pressure has density around 1g
cm-3 and is used to remove caffeine from coffee beans instead of using
chlorofluorocarbons, which are not environment friendly.

Significance of critical temperature

One significant consequence of the phenomenon of the critical temperature is that gaseous
substances whose critical temperatures are above room temperature can be liquefied by
applying sufficient pressure to the gas. To liquefy gaseous substances whose critical
temperatures are below room temperature requires both the application of pressure and a
lowering of the temperature (to a value below Tc). A distinction that is sometimes made
when describing the gaseous substance of a substance is to call it a vapour if temperature
is below and a gas if the temperature is above Tc. We can condense a vapour simply by
applying pressure, but to liquefy a gas we must both apply pressure and lower the
temperature.

Page 24 of 24