Lecture 1

SCH 215; Introduction to kinetics and Thermodynamics

Matter

Anything that has mass and occupies space. Chemists classify matter as either a substance or a
mixture of substances. A substance may further be classified as either an element or a compound.
A substance is a form of matter that has a definite composition and distinct properties.

States of matter

A substance can in principle exist as a solid, a liquid or a gas.

 In a solid, particles are held together in orderly fashions with little freedom of motion. As a
result, a solid does not conform to the shape of its container.
 Particles in a liquid are close together but not held rigidly in position. They are free to move
past one another. Thus a liquid conforms to the shape of its container (or the part of the
container it fills)
 In a gas, the particles are separated by distances that are very large compared to the size of
the particles. A sample of a gas assumes both the shape and volume of the container.

The three states of matter can be interconverted without changing the chemical composition of
the substances. Upon heating, a solid (e.g ice) will melt to form a liquid (water). Further heating
will vaporize the liquid converting it to a gas (water vapour).

Conversely, cooling a gas will cause it to condense into a liquid. When a liquid is cooled further,
it will freeze into a solid.

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Gas Laws

1. Boyles law; The pressure volume – relationship

Imagine that you have a plastic syringe filled with air. If you hold your finger tightly against
the tip of the syringe and push the plunger with your other hand, decreasing the volume of
air, you will increase the pressure in the syringe.

During the 17th century, Robert Boyle (1627 – 1691) conducted systematic studies of the
relationship between gas volume and pressure using a simple apparatus like the one shown
below.

The J-shaped tube contains a sample of a gas confined by a column of mercury. The
apparatus functions as an open-ended manometer. When the mercury levels on both sides are
equal, the pressure of the confined gas is equal to the atmospheric gas. When more mercury
is added through the open end, the pressure of the confined gas is increased by an amount
proportional to the height of the added mercury – and the volume of the gas decreases.

If for example, we double the pressure on the confined gas by adding mercury to make a
difference in the levels on the left and right, the volume of gas is reduced by half. If we triple
the original pressure, the volume of the gas is reduced to one- third of the original volume.

A set of data from Boyle’s experiment shows volume data as a function of pressure

P (mmhg) 760 855 950 1045 1140 1235 1330 1450

V (ml) 100 89 78 72 66 59 55 54

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 The data illustrates Boyle’s law which states that the pressure of as fixed amount of gas at
constant temperature is inversely proportional to the volume.

Mathematically,

Vα

V = K1 (at constant temperature)

K1 is a constant of proportionality

Thus PV = K1

According to Boyle’s law, the product of pressure and volume of a given sample of gas (at
constant T) is constant.

Although the individual values of pressure and volume can vary greatly for a given sample of
gas, the product of P and V is always equal to the same constant as long as the temperature is
held constant and the amount of gas does not change.

Therefore, a given sample of gas under two different sets of conditions at constant
temperature, we can write;

If P1V1 = K1 and P2V2 = K1

Then P1V1 = P2V2

Graph of volume against pressure

V V
ol ol
u T2
u
m T1
V1
Slope = K1
V2 T2
T1

P1 P2
3
⁄
 One common use of Boyle’s law is to predict the new volume of a gas when the pressure is
changed (at constant T) or vice versa.

Example

Freon-12 (the common name for the compound CCl2F2 is widely used in refrigeration
systems. Consider a 1.53 L sample of gaseous CCl2F2 at a pressure of 5.6×103 Pa. If the
pressure is changed to 1.5×104 Pa at a constant temperature, what will be the new volume of
the gas.

Solution

V1 = 1.53 L P1V1 = P2V2

P1 = 5.6×103 Pa
V2 = V1
P1 = 1.5×104 Pa
. ×
V2 = ? = × 1.53
. ×

= 0.5712 L

2. Charles’ and Gay-Lussac’s Law; The Temperature – Volume relationship

The first to study the relationship between gas volume and temperature were French
scientists Jacques Charles and Charles Gay-Lussac. Their studies showed that at constant
pressure, the volume of a gas sample increases when heated and decreases when cooled. A
plot of data typical of Charles’ and Gay-Lussac’s experiments are shown below

Plot of the volume of a sample of gas at different pressure as a function of temperature.

Volume

Ar
bit Volume as a function
rar of temperature
y

0 0C 200 Temperatur
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 Volume
P1
Arb
itra
ry
P2
Uni
ts
P3

– 273.15 0C 0 0C

These experiments were carried out at several different pressures each yielding a different
straight line. Interestingly, if lines are extrapolated to zero volume, they all meet at the X–axis at
a temperature – 273.15 0C.

The implication is that; a gas sample has zero volume at – 273.15 0C. This is not observed in
practice however, because all gases condense to form liquids or solids long before – 273.15 0C is
reached.

Lord Kelvin realized the significance of the extrapolated lines all meeting at – 273.15 0C. He
defined – 273.15 0C as Absolute Zero which is theoretically the lowest attainable temperature.
He set up an absolute temperature scale now known as the Kelvin scale, with absolute zero as
the lowest point.

On the Kelvin scale, 1 Kelvin (K) is equal in magnitude to 1 degree Celsius (0C). The difference
is simply an offset of 273.15. We obtain the absolute temperature by adding 273.15 to the
temperature expressed in Celsius. We often simply use 273 instead of 273.15. Several important
points on the two scales match as follows.

Kelvin scale (K) Celsius scale (0C)

Absolute zero 0 – 273.15
Freezing point of water 273.15 0
Boiling point of water 373.15 100

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The dependence of volume of a sample of gas on temperature is given by;

V = K2T (at constant P and n)

= K2

K2 is a proportionality constant

If 1 = K2 and 2 = K2
1 2

Then 1 = 2 = K2
1 2

The two expressions of Charles’ and Gay-Lussac’s law, often referred to simply as Charles’ law
states that the volume of a fixed mass of gas maintained at constant pressure is directly
proportional to its absolute temperature

Sample problem

As sample of Argon that originally occupied 14.6 L at 25.0 0C was heated to 50.0 0C at constant
pressure. What is its new volume?

Solution

T1 = 25.0 + 273 = 298K

=

V1 = 14.6 L

T2 = 50.0 + 273 = 323K V2 = V1

V2 = ?
= × 14.6

= 15.8 L

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3. Avogadro’s Law; The amount – volume relationship

Avogadro postulated that equal volumes of all gases at the same temperature and pressure
contain the same number of particles. This is called Avogadro’s law and can be stated
mathematically as;

V = K3n

V = volume of gas

n = number of moles of gas

K3 = proportionality constant

This equation implies that for a gas at constant temperature and pressure, the
volume is directly proportional to number of moles of the gas. It has been verified
experimentally and is obeyed closely at low pressures.

4. The Ideal Gas Law

We have considered three laws that govern the behavior of gases as revealed by experimental
observations. The three laws can be combined as follows;

V = K1K2K3 Tn

But K1K2K3 = R

Hence V = R Tn

Rearranging the equation yields;

PV = nRT The ideal gas law

Where R = the universal gas constant

= 0.082057 L mol – K – 1

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The ideal gas law is an equation of state for a gas where the state of a gas is its condition at a
given time. A particular sate is described by pressure, volume, temperature and number of
moles.

Knowledge of any three of the properties (parameters) is enough to completely define the state of
the gas, since the fourth property can then be determined from the equation of the ideal gas. It is
important to recognize that the ideal gas law is an empirical equation. It is based on the
experimental measurements of the properties of gases. A gas that obeys this equation is said to
behave ideally. That is; this equation defines the behavior of any ideal gas.

Most gases obey this equation closely at low pressure below 1 atmosphere.

The molecular mass (µ) of a gas

One very important use of the ideal gas law is in the calculation of the molecular mass of a gas

PV = nRT

But n=

PV = RT

P=

Since =d

Then P=d (y = mx + c)

This is equation gives a straight graph with as gradient if C = 0 in the equation y = mx + c

P
From the slope of the plot, one can
Slope = determine the molecular mass of an
unknown gas.

d
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Gas stoichiometry

The area of study that deals with the quantities of materials consumed and produced in a
chemical reaction is called Gas stoichiometry.

Suppose we have 1 mole of an ideal gas at 0 0C (273.15 0C) and 1 atmosphere. Then from the
ideal gas law, the volume of the gas is given by;

PV = nRT

V=

( . ) . × .
=
.

= 22.42 L

This volume (22.42 L) is called the Molar Gas Volume (MGV) of an ideal gas. The conditions
of 00C and 1 atmosphere are called s.t.p

Many chemical reactions involve gases. By assuming ideal behavior for these gases, we can
carry out stoichiometric calculation if the pressure, volume and temperature are known.

Sample problem.

Quicklime (CaO) is produced by the thermal decomposition of calcium carbonate (CaCO3).

Calculate the volume of CO2 gas produced from the decomposition of 152g of CaCO3 according
to the equation

CaCO3(s) CaO(s) + CO2(g)

solution

100g of CaCO3 22.4 L of CO2

152g of CaCO3 X

X = 22.4 ×

= 34.1 L of CO2 at s.t.p