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STATES OF MATTER
Gas: Empirical Gas Laws, Kinetic Theory
Liquid: Macroscopic Properties,
Evaporation, etc.
Solids: Types, Properties, Ionic & Crystalline Solids

Lecturer: Dr Etchie, A. T.
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KINETIC THEORY OF GASES

• The kinetic theory of gases explains the three
macroscopic properties of a gas in terms of the
microscopic nature of atoms and molecules making up
the gas.

• Usually, the physical properties of solids and liquids can

be described by their size, shape, mass, volume, etc.

• However, when we talk about gases, they have no

definite shape or size, while mass and volume are not
directly measurable.
• The kinetic theory of gases is useful and can be
3

applied in this case.

• The kinetic molecular theory of gases explains the

laws that describe the behaviour of gases.

• With the kinetic theory of gases, the physical

properties of any gas can generally be defined in
terms of three measurable macroscopic properties:
the pressure, volume and temperature of the
container where the gas is stored or present.
 Postulates of the Kinetic Molecular Theory 4

1. Gases contain tiny (of negligible size) particles (atoms

and molecules) which are extremely small compared to
the distance between the particles.

2. Particles in a gas move in straight line paths and random

directions. Direction changes as a result of collision.

3. Particles in a gas collide frequently with the sides of the

container and less frequently with each other. All
collisions are elastic (no energy is gained or lost as a
result of the collisions).
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4. Particles in a gas do not attract or repel one another.

There is no intermolecular attractions.

5. The average kinetic energy of all gas particles/molecules is

proportional to the kelvin temperature of the gas.
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The Relationships Among Pressure, Volume, and

Temperature

• The kinetic molecular theory of gases explains

some of the important relationships among
pressure, volume and temperature.
 Pressure versus Volume 7

• At constant temperature, the kinetic energy of the molecules of a gas

and hence the average speed remain unchanged.
• If a given gas sample is allowed to occupy a larger volume, then the
speed of the molecules does not change, but the density of the gas
(number of particles per unit volume) decreases, and the average
distance between the molecules increases.
• Hence the molecules must, on average, travel farther between
collisions.
• They therefore collide with one another and with the walls of their
containers less often, leading to a decrease in pressure.
• Conversely, decreasing the volume, thus increasing the pressure forces
the molecules closer together and increases the density, until the
collective impact of the collisions of the molecules with the container
walls just balances the applied pressure.
 Volume versus Temperature
8

• Raising the temperature of a gas increases the average

kinetic energy and therefore the average speed of the gas
molecules.
• Hence as the temperature increases, the molecules collide
with the walls of their containers more frequently and with
greater force.
• This increases the pressure, unless the volume increases to
reduce the pressure.
• Thus an increase in temperature must be offset by an
increase in volume for the net impact (pressure) of the gas
molecules on the container walls to remain unchanged.
 Pressure of Gas Mixtures
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• Postulate 4 of the kinetic molecular theory of gases states

that gas molecules exert no attractive or repulsive forces on
one another.

• If the gaseous molecules do not interact, then the presence

of one gas in a gas mixture will have no effect on the
pressure exerted by another, and Dalton’s law of partial
pressures holds.
 Question 10

The temperature of a 4.75 L container of N2 gas is increased from 0°C

to 117°C. What is the qualitative effect of temperature change on the:
• average kinetic energy of the N2 molecules?
• average speed of the N2 molecules?
• impact of each N2 molecule on the wall of the container during a
collision with the wall?
• total number of collisions per second of N2 molecules with the walls of
the entire container?
• number of collisions per second of N2 molecules with each square
centimeter of the container wall?
• pressure of the N2 gas?
Solution 11

• Increasing the temperature increases the average kinetic energy of

the N2 molecules, resulting from increase in speed of the gas particles.
• If, on average, the particles are moving faster, then they strike the
container walls with more energy.
• Because the particles are moving faster, they collide with the walls of
the container more often per unit time.
• The number of collisions per second of N2 molecules with each square
centimeter of container wall increases because the total number of
collisions has increased, but the volume occupied by the gas and
hence the total area of the walls are unchanged.
• The pressure exerted by the N2 gas increases when the temperature is
increased at constant volume, as predicted by the ideal gas law.
Question 12

A sample of helium gas is confined in a cylinder with a gas-tight sliding piston. The
initial volume was 1.34 L, and the temperature, 22°C. The piston was moved to
allow the gas to expand to 2.12 L at constant temperature. What is the qualitative
effect of this change on the
• average kinetic energy of the He atoms?
• average speed of the He atoms?
• impact of each He atom on the wall of the container during a collision with the
wall?
• total number of collisions per second of He atoms with the walls of the entire
container?
• number of collisions per second of He atoms with each square centimeter of the
container wall?
• pressure of the He gas?
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Answer:
a. no change;
b. no change;
c. no change;
d. no change;
e. decreases;
f. decreases;
g. decreases
 THE EMPIRICAL GAS LAWS 14

• The empirical gas laws are those that have

been arrived at by experiment.

• They include:
• Boyle’s law,
• Charles’ law,
•Gay-Lussac’s law,
•Graham’s law of partial pressures and
•Graham’s law of diffusion.
 Boyle’s Law: Volume-pressure Relationship 15

• Gas was trapped in a U-tube and allowed to come to

constant temperature.
• Then its volume and the difference in the heights of the two
mercury columns were recorded.
• This difference in height plus the pressure of the atmosphere
represents the pressure on the gas.
• Addition of more mercury to the tube increases the pressure
by changing the height of the mercury column.
• As a result, the gas volume decreases. The results of several
such experiments are tabulated.
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A representation of Boyles experiment. A sample of air is trapped in a tube in

such a way that the pressure on the air can be changed and the volume of the air measured.
P is the atmospheric pressure, measured with a barometer. P1 = h1+ Patm, P2 = h2 + Patm.
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• When the volume of a gas is plotted against its pressure at constant

temperature, the resulting curve is one branch of a hyperbola. The
figure is a graphic illustration of this inverse relationship.
• Volume is plotted versus the reciprocal of the pressure, straight line
results.
• In 1662, Boyle summarized the results of his experiments on various
samples of gases in an alternative statement of Boyle's Law:
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Boyle’s Law
• At constant temperature, the
volume, V, occupied by a definite
mass of a gas is inversely
proportional to the applied
pressure, P.

1 1
𝑉∝ 𝑜𝑟 𝑉 = 𝑘
𝑃 𝑃
(constant n, T)
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• At normal temperature and pressure, most gases obey Boyle’s Law

rather well. This is ideal gas behavior. Deviations from ideality will be
discussed later.
• Let us think about a fixed mass of gas at constant temperature, but at two
different conditions of pressure and volume. For the first condition we can
write
P1V1 = k (constant n, T)
and for the second condition, P2V2 = k (constant n, T)

• Because the right-hand sides of these two equations are the same,
• Then,
P1V1 = P2V2 (for a given amount of a gas at constant temperature)
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• Question
1. At room temperature, an amount of a gas exerts a pressure of 3 kPa on the
walls of container A. When container A was quantitatively emptied into a
10 litre container (B) at the same temperature, the pressure exerted by the
gas increased to 6 kPa. Find the volume of container A.

2. A sample of oxygen gas has a volume of 225 mL when its pressure is 1.12
atm. What will the volume of the gas be at a pressure of 0.98 atm if the
temperature remains constant?

3. A helium balloon has a volume of 735 mL at ground level. The balloon was
transported to an elevation of 5 km, where the pressure was 0.8 atm. At this
altitude, the gas occupied a volume of 1286 mL. Assuming constant
temperature, what was the ground level pressure?
• Solution
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1. Given initial Pressure (P1 ) = 3 kPa, Final Volume (V2 ) = 10 L and

final Pressure (P2 ) = 6 kPa
Initial Volume (V 1 ) = ?

Boyle’s law: P1 V1 = P2 V2

3 X V 1 = 6 X 10
3 X V 1 = 60
V 1 = 60 / 3
V 1 = 20 L
Hence the initial volume of the gas at pressure of 3 kPa is
equivalent to 20 L.
2. Initial Volume (V1 ) = 225 mL 23

Initial Pressure (P1 ) = 1.12 atm

Final Pressure (P2 ) = 0.98 atm
Final Volume (V 2 ) = ?

Boyle’s law: P1 V1 = P2 V2

1.12 X 225 = 0.98 X V 2

252 = 0.98 X V 2
252 / 0.98 = V 2
V 2 = 257.14 mL ≈ 257mL
• Hence the final volume of the gas at pressure of 0.98 atm is
equivalent to 257 mL.
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3. Initial Volume (V1 ) = 735 mL

Final Pressure (P2 ) = 0.8 atm
Final Volume (V2 ) = 1286 mL
Find: Initial Pressure (P1 ) = ?

Boyle’s law: P1 V1 = P2 V2

P 1 X 735 = 0.8 X 1286

P1 = 1028.8 / 735
P1 = 1.39 ≈ 1.4 atm
• Hence the ground level pressure is 1.4 atm.
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CHARLES'S LAW: THE VOLUME-TEMPERATURE RELATIONSHIP;

THE ABSOLUTE TEMPERATURE SCALE

• Jacques Charles (1746-1823) and Joseph Gay-Lussac (1778- 1850) began

studying the expansion of gases with increasing temperature.
• Their studies showed that the rate of expansion with increased temperature was
constant (k) and was the same for all the gases they studied as long as the
pressure remained constant.
• The implications of their discovery were not fully recognized until nearly a
century later.
• Then scientists used this behavior of gases as the basis of a new temperature
scale, the absolute temperature scale.
• The change of volume with temperature, at constant pressure, is illustrated in the 26

figure below. From the table, volume (V, mL) increases as temperature (oC)
increases, but the quantitative relationship is not obvious. The line plot of the data
(line A), together with similar data for the same gas sample at different pressures
(lines B and C) is shown below.
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• Lord Kelvin, a British physicist, noticed

that an extension of the different
temperature-volume lines back to zero
volume (dashed line) yields a common
intercept at -273.150C on the temperature
axis.
• Kelvin named this temperature absolute
zero.
• The degrees are the same size over the
entire scale, so OOC becomes 273.15
degrees above absolute zero.
• In honor of Lord Kelvin's work, this scale
is called the Kelvin temperature scale.
• The relationship between the Celsius and
Kelvin temperature scales is:
• K = oC + 273.150.
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• If we convert the temperatures (oC) to absolute temperatures (K)

(the green scale in the figure), the volume-temperature
relationship becomes obvious. This relationship is known as
Charles's Law.

• Charles's Law
At constant pressure, the volume occupied by a definite mass of a
gas is directly proportional to its absolute temperature.
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We can express Charles's Law in mathematical terms as

VαT or V = k T (constant n, P)

Rearranging the expression gives

V / T = k, a concise statement of Charles's Law.

As the temperature increases, the volume must increase proportionally. If we let

subscripts 1 and 2 represent values for the same sample of gas at two different
𝑉1 𝑉2
temperatures, we obtain = (for a definite mass of gas at
𝑇1 𝑇2
constant pressure)

which is the more useful form of Charles's Law. This relationship is valid only when
temperature, T, is expressed on an absolute (usually the Kelvin) scale.
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Questions

(1) A tube is filled with hydrogen gas to a volume of 10dm3 at a temperature of

300C. If this tube is heated to a temperature of 1000C, what will be the new
volume of the tube?

(2) 200L of oxygen gas was compressed at a temperature of 370C to 20L.

Calculate the temperature of oxygen at the final volume.

(3) A noble gas occupies 3000mL of tube at a temperature of 373.15K. What

volume will it occupy in litres at 1000C?
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AVOGADRO’S LAW AND THE STANDARD MOLAR

VOLUME

• In 1811, Amedeo Avogadro postulated that:

at the same temperature and pressure, equal volumes of all gases

contain the same number of molecules.

• Many experiments have demonstrated that hypothesis is accurate

to about ±2% and the statement is now known as Avogadro's Law.
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• Avogadro's Law can also be stated as follows.

• At constant temperature and pressure, the volume, V, occupied by a gas

sample is directly proportional to the number of moles, n, of gas.

• Mathematically,
𝑉
Vα n or V = kn or =𝑘 (constant P& T)
𝑛

For two samples of gas at the same temperature and pressure, the relation
between volumes and numbers of moles can be represented as

𝑉1 𝑉2
= (constant T & P)
𝑛1 𝑛
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Questions
1. A 6.0 L sample at 25°C and 2.00 atm contains 0.5 mole of a gas. If an
additional 0.25 mole of gas at the same pressure and temperature are
added, what is the final total volume of the gas?

2. A flexible container at an initial volume of 5.120 L contains 8.500 mol of gas.

More gas is then added to the container until it reaches a final volume of
18.10 L. Assuming the pressure and temperature of the gas remain
constant, calculate the number of moles of gas added to the container.

3. A flexible container at an initial volume of 6.13 L contains 7.51 mol of gas.

More gas is then added to the container until it reaches a final volume of
13.5 L. Assuming the pressure and temperature of the gas remain constant,
calculate the number of moles of gas added to the container.
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THE COMBINED GAS LAW EQUATION

• Boyle's Law relates the pressures and volumes of a sample of gas at

constant temperature, P1V1 = P2V2

• Charles; Law relates the volumes and temperatures at constant

𝑉1 𝑉2
pressure, =
𝑇1 𝑇2

• Combination of Boyle's Law and Charles's Law into a single expression

gives the combined gas law equation.

𝑃1 𝑉1 𝑃2 𝑉2
= (constant amount of gas (n))
𝑇1 𝑇2
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SUMMARY OF GAS LAWS: THE IDEAL GAS EQUATION

• We can summarize the behavior of ideal gases as follows:

1
Boyle's Law: 𝑉 ∝ (at constant T and n)
𝑃

Charles 's Law: 𝑉 ∝ T (at constant P and n)

Avogadro's Law : 𝑉 ∝ 𝑛 (at constant T and P)

𝑛𝑇
Summarizing: 𝑉 ∝ (no restrictions)
𝑃
As before, a proportionality can be written as an equality by Introducing
a proportionality constant, for which we'll use the symbol R.
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• This gives

𝑛𝑇
𝑉= ( )𝑅 or P𝑉 = nRT
𝑃

• This relationship is called the ideal gas equation or ideal gas law. R is the
universal gas constant.
• The numerical value of R depends on the choices of the units for P, V and
T
• At standard temperature and pressure (STP), one mole of an ideal gas
occupies 22.414 liters (≈ 22.4 L/mol) at 1.0000 atmosphere and 273.15 K
(≈ 273 K).
• R = 0.0821 L * atm/ mol * K
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• Question
1. A sample of argon gas at STP occupies 56.2 liters. Determine the number of
moles of argon and the mass of argon in the sample. (Ar = 39.948 g/mol;
Molar volume = 22.414 L/mol)

2. At what temperature will 0.654 moles of neon gas occupy 12.30 liters at
1.95 atmospheres? (R = 0.0821 L * atm/ mol * K)

3. 96.0 g. of a gas occupies 48.0 L at 700.0 mm Hg and 20.0 °C. What is its
molecular weight? (1 atm = 760 mm Hg; R = 0.0821 L * atm/ mol * K)
 Solution 38

1)At STP, P = 1 atm, T = 273 K and 2) T = PV/nR =

R = 0.0821 L * atm/ mol * K (1.95*12.3)/(0.654*0.0821)
n = PV/RT = 1 * 56.2/22.426 = 2.51 moles = 446.7 ≈ 447 K
Or
Molar volume given = 22.414 L/mol 3) P = 700 mm Hg divided 760
mm g per atm
Volume at STP = 56.2 L 700
×48
No of moles of Ar = 56.2 L / 22.414 L/mol n= 760
= 1.838 mol
0.0821×293
= 2.51 moles

Molecular weight or molar mass =

Mass = n * molar mass
96/ 1.838 = 52.2 g/mol
= 2.51 mol * 39.948 g/mol ≈ 100 g
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REAL GASES: DEVIATIONS FROM IDEALITY

• Until now our discussions have dealt with ideal behaviour of gases. By
this we mean that the identity of a gas does not affect how it behaves,
and the same equations should work equally well for all gases.

• Under ordinary conditions most gases do behave ideally; their P and V

are predicted by the ideal gas laws, so they do obey the postulates of the
kinetic—molecular theory.

• Under some conditions, however, most gases can have pressures and/or
volumes that are not accurately predicted by the ideal gas laws. I.e. not
behaving entirely as postulated by the kinetic—molecular theory.
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• Nonideal gas behavior (deviation from the predictions of the ideal gas
laws) is most significant at high pressures and/or low temperatures, that
is, near the conditions under which the gas liquefies.