CHEM 1043

General Chemistry II
2022-2023
Semester 1

Course Information:
Course website: Moodle course (access via Student Portal à My eLearning)
No. of credits: 6
Pre-requisite: Pass in CHEM1042 General Chemistry I
Duration: Semester 1
Teaching: 36 hours of lectures plus ~10 hours of tutorials
Course Coordinator: Dr. A P L Tong
Teachers: Dr. A P L Tong ([email protected], Rm 602, CYM Chemistry Building)
Dr. Seungkyu Lee ([email protected], Rm 107, HOC Science Building)
Assessment: Exam (50 %), Test (20 %, tentatively on Nov 21) and
Assignments (tentatively by Oct 6 and Nov 4, 15 % each)
Please refer to the document “CHEM1043_2021S2 T&L Schedule”.
 Teaching Assistants for CHEM1043

Cherry Cheuk Ying CHU Derek Chun Lung CHAN Kevin Ziqi DENG
For Topics 1 - 2 For Topics 3 - 4 For Topics 5 - 6
([email protected]) ([email protected]) ([email protected])

Please refer to the document “CHEM1043 Tutorial & Consultation Schedule” for more
details.

Your Prior Knowledge

CHEM1042 General Chemistry I
in Chemistry
(1) Chemistry: its nature and method
Physical properties; chemical changes and chemical properties; elements and compounds;
measuring mass, length, volume and temperature; atomic structure and subatomic particles;
the mole concept and stoichiometry; solutions and concentrations; uncertainty in measurement and significant
figures.
(2) Atoms: the quantum world
Electromagnetic radiation and matter; Planck's quantum theory; the Bohr model of the hydrogen atom; the
quantum mechanical model of the atom; quantum numbers, energy levels, and atomic orbitals; shapes of atomic
orbitals; electron configurations; periodic trends: atomic radii, ionic radii, ionization energies, and electron
affinities.
(3) Chemical bonding and structures
Review on covalent, ionic and metallic bond. Covalent bonds and molecular structures (VSEPR, VB theory).
(4) Energetics and kinetics of reactions
Heat and work; the first law of thermodynamics; heat of reactions; spontaneity of changes.
Reaction rate; factors that influence reaction rate; rate laws: differential and integrated rate laws; temperature and
reaction rate; reaction mechanisms.
(5) Acid-Base equilibria
Acid-base concepts; equilibria in solutions of weak acids and in weak bases; ionization constants; molecular
properties and acid strength; acid-base properties of salt solutions; buffer solutions; acid-base titrations.

4
Course Objectives:
• This course is a continuation of CHEM1042 General Chemistry I.
It aims to further consolidate some of the important
fundamentals of chemistry that underlie many topics and
principles across the physical sciences.

• The course prepares students to pursue a major in chemistry or

in other aspects that require a good foundation in chemistry.

Course Contents: This content list is subject to minor change.

(1) Gases
(2) Simple gas laws; ideal gas equation; gases in chemical reactions; mixture of gases; kinetic-molecular
theory of gases; diffusion and effusion; non-ideal gases.
(2) Structure and Bonding: The Delocalized Approach: Molecular Orbital Theory
Bonding in homonuclear and heteronuclear diatomic molecules of first and second period of elements;
bonding in some simple polyatomic molecules; bonding in metals (band theory).
(3) Solutions and their Properties
Types of solutions; intermolecular forces and the solution process; solution formation and equilibrium;
solubilities of gases; vapor pressures of solutions; osmotic pressure; freezing-point depression and boiling-
point elevation of nonelectrolyte solutions; solutions of electrolytes; colloidal mixtures.
(4) Solubility and Complex-Ion Equilibria
Solubility product constant; relationship between solubility and Ksp; common-ion effect in solubility equilibria;
limitations of the Ksp concept; precipitation; solubility and pH; equilibria involving complex ions; qualitative
cation analysis.
(5) Entropy & Gibbs Energy
A quick review on entropy and the second & third laws of thermodynamics. Standard Gibbs energy change;
Gibbs energy change and equilibrium; coupled reactions.
(6) Electrochemistry
Electrode potentials and their measurement; standard electrode potentials; Ecell, DG, and K; Ecell as a functions
of concentrations; batteries; corrosion; electrolysis; industrial electrolysis processes.

6
Course Learning Outcomes:
On successful completion of this course, students should be able to:
1. Demonstrate a knowledge and understanding of the properties and behavior of gases and
apply gas laws and kinetic-molecular theory to processes involving gases.
2. Demonstrate a knowledge and understanding in relation to solutions and their properties,
solubility and complex-ion equilibria, and also electrochemistry.
3. Apply molecular orbital theory to explain the formation and properties of diatomic
molecules of first and second period of elements and of some simple polyatomic
molecules.
4. Demonstrate a knowledge and understanding of the relationship between free energy
and spontaneity of reaction.
5. Apply the theories and concepts introduced in the course to solve problems, perform
calculations, make predictions and rationalize trends.
6. Organize and present chemical ideas in a clear, logical and coherent way.
7. Demonstrate awareness of the relevant applications of chemistry in society and in
everyday life.
7

Textbook & Reference Books:

Reading is important!
Textbook:
Petrucci; Herring; Madura; Bissonnette:
General Chemistry: Principles and Modern
Applications, 11th edition, Pearson

Other reference books:

1) Moore; Stanitski; Jurs: Chemistry: The Molecular
Science, latest edition, Brookes/Cole
Purchase link @ Online
2) Zumdahl; Zumdahl: Chemistry, latest edition, Bookshop for HKU Students:
Brookes/Cole https://apbookshop.com/HK
U/EN/Display/PrintedBook?I
SBN=9780134097329&ForM
3) Silberberg: Chemistry: The Molecular Nature of aterials=False&Created=False
Matter and Change, latest edition, McGraw Hill

4) Raymond Chang: Chemistry, latest edition,

McGraw Hill
8
Class Schedule (2022 – 2023 Semester 1):
Lectures
Mon 3:30 pm – 5:20 pm (2 hr)
Thu 3:30 pm – 4:20 pm (1 hr)

September 1, 5, 8, 15, 19, 22, 26, 29

October 3, 6, 17, 20, 24, 27, 31
November 3, (5), 7, 10, 14, 17, 21, 24, 28
__ Those underlined are Monday 2-hour lectures.
Lectures highlighted in green are conducted by Dr. A P L Tong (topics 4 – 6). Others are delivered
by Dr. Seungkyu Lee (topics 1 – 3).

Consultation Sessions & Tutorials

Please refer to the document “CHEM1043 Tutorial & Consultation Schedule” for details.

CHEM 1043 General Chemistry II

Topic 1 Gases:
Properties and Behaviour

10
 Why study gases?

• E.g.) the earth’s atmosphere is a mixture of gases that consists mainly

of nitrogen (N2), oxygen (O2), and carbon dioxide (CO2) molecules. The
atmosphere supports life.

• E.g.) How can we remove CO2 from the atmosphere?

• E.g.) Many industrial sectors are trying to develop safe and efficient H2-
storage systems for the hydrogen economy.

• E.g.) Neon lights in Hong Kong are beautiful (Nobel Prize in Chemistry in
1904).

• E.g.) Gasoline (gas) reacts with O2 and releases energy in engines.

11

Elements that exist as gases at 25°C and 1 atmosphere

12
 13

What to learn in this topic?

1. Properties of gases
2. The simple gas laws
3. The ideal gas equation & general gas equation
4. Reaction stoichiometry
5. Mixture of gases
6. Kinetic-molecular theory of gases
7. Gas properties relating to the kinetic-molecular
theory
8. Non-ideal (real) gases
14
 Your reading:

Chapter 6) Gases
Petrucci; Herring; Madura; Bissonnette:
General Chemistry: Principles and Modern
Applications, 11th edition, Pearson

15

In this topic,
We will look at
• the properties of gases

• how the bahaviour of the atoms and molecules that are the basic
components of gases determine the properties of gases.

How to proceed?
• We will proceed from the macroscopic to the microscopic.
• To examine the properties of gases, such as pressure, volume,
temperature, and amount of gas (the simple gas laws and the ideal gas
equation).
• These laws will be explained by the kinetic-molecular theory of gases.

16
1. Properties of Gases
• Gases expand to fill and assume the shapes of their containers.
• They diffuse into one another and mix in all proportions.
• Gases are the most compressible state of matter.
• Gases have much lower densities than liquids and solids.

• Four properties determine the physical behaviour of a gas:

1. the amount of the gas (i.e. no. of moles)
2. the volume of the gas
3. the temperature of the gas
4. the pressure of the gas

17

The Concept of Pressure

The gas particles are in constant random motion.

The rapidly moving particles constantly collide
with each other and with the walls of the
container.

• The molecules of a gas are in constant motion,

frequently colliding with one another and with
the walls of their container.
• In the collisions, the gas molecules exert a force
on the container walls.
• Pressure is defined as a force per unit area.
18
The Concept of Pressure
• Pressure is defined as a force per unit area.

Force (N)
P (Pa) =
Area (m2)

The two cylinders have the

same mass and exert the
same force on the supporting
surface.

Force (N) = m (kg) x g (m/s2)

Which one exerts a greater pressure?

19

How to measure pressure: liquid Pressure

• The pressure of a gas is measured indirectly, by comparing
it with a liquid pressure.
• The pressure of a liquid depends only on the height (h) of the
liquid column and the density (d) of the liquid.

W = liquid weight, m = liquid mass, V = liquid volume, d = liquid density,

and g = gravity

F = W = m´ g = V´d ´ g = h ´A´ d´ g = h´ d´ g
P (Pa) =
A A A A A
weight W=mxg m=Vxd V=Axh g is constant
is force

Conclusion:
Liquid pressure µ liquid _______and the _______of the liquid column
20
Barometer
• Barometer, is a device constructed by
Evangelista Torricelli to measure
atmospheric pressure.

• Mercury flows out of the tube until the

pressure of the column of mercury
standing on the surface of the mercury
in the dish is equal to the pressure of
the air on the rest of the surface of the
mercury in the dish.

Standard Atmospheric Pressure

1 atm = 101.325 kPa = 1.01325 bar = 760 Torr » 760 mmHg

21

Class Practice 1: Comparing Liquid Pressures

Petrucci Example 6-1

What is the height of a column of water that exerts the same pressure as a
column of mercury 76.0 cm (760 mm) high? Given that the dHg = 13.6 g/cm3
and dH2O = 1.00 g/cm3.

22
Manometer
• A manometer is used to measure gas pressures.

• By using a manometer, the pressure of the gas to be measured

can be compared with barometric pressure.

Measurement of gas pressure with an open-end manometer

The possible relationships between barometric pressure and a gas pressure
under measurement are pictured here. 23

Class Practice 2

24
Units of Pressure

Some Common Pressure Units

1 bar = 100,000 Pa

1 atm » 1 bar

25

Class Practice 3

green red

26
 Class Practice 3 (Con’t)

27

2. The Simple Gas Laws

(1) Boyle’s Law (1662)
For a fixed amount of gas kept at a fixed temperature, the
gas pressure and volume are inversely proportional.

At constant n & T,

PV = constant
1
Pa
V

Relationship between gas volume and pressure – Boyle’s Law

A doubling of the pressure causes the volume to decrease to one-half its
original value.
28
Class Practice 4

A 50.0 L cylinder contains nitrogen gas at a pressure of 21.5 atm. The

cylinder is then connected to an evacuated tank of unknown volume. If
the final pressure in the tank is 1.55 atm, then what is the volume of
the tank?

(a) (21.5/1.55) x 50.0 L (b) (1.55/21.5) x 50.0 L

(c) 21.5/(1.55 x 50.0) L(d) 1.55/(21.5 x 50.0) L

29

Class Practice 4 (Con’t)

30
CHEM1043 2021-2022 S2
(2) Charles’s Law (1787)
For a fixed amount of gas kept at a fixed pressure,
the gas volume and temperature (K) are directly
proportional

250K, 500K, At constant n & P,

25mL 50mL

V
= constant
T

VaT

From a volume of zero at 0K,

V µ T (K)
31

Standard Conditions of Temperature and Pressure

• Gas properties depend on conditions.

• It is useful to have a set of standard conditions of
temperature and pressure that can be used for comparing
different gases.
• IUPAC defines standard conditions of temperature
and pressure (STP) as follows:

P = 1 bar = 105 Pa
T = 0 °C = 273.15 K

32
(3) Avogadro’s Law (1811)
At the same temperature and pressure, equal volumes of
all gases have the same number of molecules
At constant T & P,
At 0°C and 1 atm,
V
4.0 g Helium 16.0 g CH4 44.0 g CO2 n = constant
1 mole 1 mole 1 mole

V = 22.4 dm3 V = 22.4 dm3 V = 22.4 dm3

Vµn

Same molar volume (Theoretically)

1 mol gas = 22.414 L (at 0 °C, 1 atm) = 22.711 L (STP)

33

Densities and Molar Volumes of Various Gases

0 °C, 1 bar

34
 Check Questions

(1) A sample of N2 gas occupies 2.40 L at 20°C. If the gas is in a container that
can contract or expand at constant pressure, at what temperature will the
N2 occupy 4.80 L?
A. 10°C
B. 40°C
C. 146°C
D. 313°C
E. 685°C

(2) 0.820 mole of hydrogen gas has a volume of 2.00 L at a certain temperature and
pressure. What is the volume of 0.125 mol of this gas at the same temperature
and pressure?
A. 0.0512 L
B. 0.250 L
C. 0.305 L
D. 4.01 L
E. 19.5 L 35

3. The Ideal Gas Equation : Combining the Gas

Laws
• When the three laws combine, we obtain the ideal gas equation.
1
Vµ Vµ T Vµ n
P
nT
Vµ
P

PV = nRT where R = Universal Gas Constant

For one mole of a gas at 273.15 K and 1 atm,

(1 atm)(22.4140L) atm·L
R = = 0.082057
(1 mol)(273.15K) mol ·K
36
Five Common Values of R (in various units)

PV
R=
nT

The value of R depends on which units are used to

express pressure and volume.

37

Applying the ideal gas equation

38
Class Practice 5

39

Class Practice 6

40
3. The General Gas Equation
• The ideal gas equations must be applied twice in order to
determine an initial condition and a final condition.
PiVi PV
PV = nRT R= = f f
niTi nfTf
PiVi PV
= f f -- General Gas Equation
niTi nfTf
• This is often used in cases in which one or two of the gas properties
are held constant, and the equation can be simplified by eliminating
these constants.
E.g. For a constant amount of gas (fixed n),
PiVi PV
= f f
Ti Tf 41

Class Practice 7

0°C 100°C
1 bar ? bar

42
 Class Practice 7 (Con’t)

43

Applications of the Ideal Gas Equation

1. Determination of molar masses
2. Determination of gas densities

Determination of molar masses

• If the volume of a gas (V) at a fixed T & P is known, we can
obtain the amount of the gas in moles (n).

• Because = , if we know the mass (m) and no. of moles (n)

of the gas, we can find out the molar mass (M).

44
Class Practice 8

45

Class Practice 8 (Con’t)

46
Determination of gas densities
KEEP IN MIND
× that gas densities are
= = = × typically much smaller than
those of liquids and solids.
Gas densities are usually
expressed in grams per liter
• Replace n/V by its equivalent, P/RT, rather than grams per
milliliter.

d µ M (for gas)
= = d µ 1/T (for gas)

• The density of a gas at STP can be calculated by dividing its

molar mass by the molar volume (22.7 L/mol).

E.g. For O2 at STP, the density is 32.0 g/22.7 L = 1.41 g/L

47

Class Practice 9

48
4. Gases in Chemical Reactions
∆
E.g. 2NaN3 (s) ® 2Na (l) + 3N2 (g)

• For reactions involving gases, we can

(1) use stoichiometric factors to relate gas quantities to

quantities of other reactants or products,

(2) use the ideal gas equation to relate the amount of a gas
to volume, temperature and pressure.

• Law of Combining Volumes can be developed using the gas law

to deal with stoichiometric calculation in which the reactants
and products are gases.

49

Class Practice 10

50
 Class Practice 10 (Con’t)

51

Law of Combining Volumes

2NO (g) + O2 (g) ® 2NO2 (g)
2 mol + 1 mol ® 2 mol

At constant T & P, 2 V L + 1 V L ® 2 V L

2 L NO (g) + 1 L O2 (g) ® 2 L NO2 (g)

• The volume ratio of gases consumed and produced in a chemical

reaction is the same as the mole ratio (at constant
T & P) - - Gay-Lussac’s Law of Combining Volumes

(See next slide for an example)

52
E.g.) Applying the Law of Combining Volumes
Petrucci Example 6-10

3O2 (g) : 2SO2 (g)

53

5. Mixtures of Gases
• Gas laws apply to mixtures of (nonreactive) gases as well as
to individual gases.
• Simplest approach is to use the total number of moles of the
gaseous mixture, ntotal.
E.g.) Applying Ideal Gas Eqn to a Gas Mixture Petrucci Example 6-11

PiVi PfVf
=
niTi nfTf

54
 This is a blank page

55

Dalton’s Law of Partial Pressures

• John Dalton proposed that in a mixture, each gas expands
to fill the container and exerts the same pressure (called its
partial pressure) that it would if it were alone in the container.

Dalton’s law of partial pressures illustrated

The pressure of each gas is proportional to the number of moles of

gas. The total pressure is the sum of the partial pressures of the
individual gases.
56
Partial Pressures
• For a mixture of gases, A, B, and so on,
Ptot = PA + PB +…

• In a gaseous mixture of nA moles of A, nB moles of B, and so on,

the volume each gas would individually occupy at a pressure
equal to Ptot is VA = nART/Ptot

• The total volume of the gaseous mixture is Vtot = VA + VB+…

• We can derive a particularly useful expression from the following
ratios,
PA nART/Vtot nA VA nART/Ptot nA
= = n = = ntot
P ntotRT/Vtot tot Vtot ntotRT/Ptot
tot

The mole fraction = = =

of A, cA 57

Partial Pressures

The mole fraction = = =

of A, cA

• The mole fraction of a component in a mixture is the fraction of

all the molecules in the mixture contributed by that component.

• The sum of all the mole fractions in a mixture is one.

58
 Class Practice 11

59

Collecting a Gas over Water Ptot = Pbar = Pgas + PH2O

A pneumatic trough

• The bottle is filled with water and its open end is held below the water level in the container.
• Gas from a gas-generating apparatus is directed into the bottle.
• As gas accumulates in the bottle, water is displaced from the bottle into the container.
• To make the total gas pressure in the bottle equal to barometric pressure, the position of
the bottle must be adjusted so that the water levels inside and outside the bottle are the
same.
Ptot = Pbar = Pgas + PH2O

Pressure of The pressure of

60
the atmosphere water vapour depends on the temp.
Collecting a Gas over Water
Vapour Pressure of Water
at Various Temperatures

61

Class Practice 12

62
 Class Practice 12 (Con’t)

63

6. Kinetic-Molecular Theory of Gases

• The simple gas laws and the ideal gas equation are used to
predict gas behaviour. They are natural laws.

• To explain the gas laws, we need a theory.

• Kinetic-Molecular Theory of Gases was developed in mid-19th

century.

64
6. Kinetic-Molecular Theory of Gases
1) A gas is composed of a very large number
of tiny spherical particles in constant,
random, straight-line motion.
2) Particles are point masses (no volume)
and are separated by great distances.
3) Collisions are rapid and elastic. No forces
between particles except very briefly
during collisions
4) The average kinetic energy of gas
particles is dependent upon the
Visualizing Molecular Motion
temperature of the gas.

The validity of this model can be checked by comparing predictions based on the
model with experimental facts. It was proven that the predictions based on this
model are consistent with several observed macroscopic properties.
65

Kinetic-Molecular Theory of Gases

Distribution of Molecular Speeds
• The molecules in a gas travel at different speeds. Because N is too large,
we cannot know the speed of each molecule.

• A statistical prediction of how many molecules have a particular speed

can be made.

• The fraction, F, of molecules that have speed u is given by the following

equation called Maxwell-Boltzmann distribution of speeds:
For a certain value of u (in
/ m/s), the corresponding value
=4 ( ) of F represents the fraction
2 of molecules having speed
between u and (u+1) m/s.

• This equation can help us understand how the distribution of speeds

depends on molar mass, M, and temperature, T.

66
 Distribution of Molecular Speeds

/
( )
=4
2 Distribution of molecular speeds –
um is the modal speed; uav is the average speed; hydrogen gas at 0°C
urms is obtained from the average of u2: i.e. The percentages of molecules with a certain
speed are plotted as a function of speed.

Three different speeds are noted.

1. the most probable speed is ~1500 m/s;

2. the average speed is ~1700 m/s; and

3. the root-mean-square speed is ~1800 m/s.

Notice that um < uav < urms

The shape of the distribution depends on

the product of two opposing factors:
(1) u2 , and (2) ( )

67

Distribution of Molecular Speeds

/
( )
=4
2
The distribution depends on temperature and
molar mass.
Look at the two curves for O2:
As T ­
• range of speeds broadens, and
• distribution shifts towards higher speeds,

Look at the curves for O2 and H2 at 273 K:

• The lighter the gas, the broader the range
of speeds.

Note that the area under each curve is

the same because N is the same
Distribution of Molecular Speeds –
the effect of mass and temperature
68
 Distribution of Molecular Speeds
Look at the 3 characteristic speeds:
1. The most probable speed, or modal Distribution of molecular speeds –
hydrogen gas at 0°C
speed is denoted by um; more molecules
have this speed than any other speed.

2. The average speed is denoted by uav.

3. The root-mean-square speed, urms, is

obtained from the average of u2, which
is denoted by .

• These characteristic speeds can be calculated by using the following

expressions:

2 8 3
= = = -- eqn 1

(R = 8.3145 J K-1mol-1)
69

Kinetic-Molecular Theory of Gases

Class Practice 13: Calculating a Root-Mean-Square Speed

9.75 ´ 102 m/s

70
 Kinetic-Molecular Theory of Gases

Class Practice 13 (Con’t)

71

Kinetic-Molecular Theory of Gases

Experimental Determination –
Distribution of Molecular Speeds
• An oven (in which gas molecules are heated)
and attached evacuated chamber are
separated by a wall with a small hole in it.
The gas molecules emerging from the hole
pass through a series of slits, called
collimators, as a beam. The beam then
passes through a series of rotating disks,
each disk has a slit cut in it.

• Only those molecules with the correct

speed to pass through all rotating disks will
reach the detector, where they can be
counted.

• By changing the rate of rotation of the disks, the complete distribution of

molecular speeds can be determined.
72
 Kinetic-Molecular Theory of Gases
Effect of Temperature
• urms is of particular interest because we can use the value of urms to
calculate the average kinetic energy, , of a collection of molecules.

• The average KE of a collection of molecules, each having a mass m = M/NA,

is the average of ½mu2:

= = × ×

• Since urms = 3 / , then u2rms = , the expression above can be

rewritten as:
= -- eqn 2

That means, = constant x T

The Kelvin temperature (T) of a gas is directly proportional to the average
kinetic energy ( ) of its molecules .
73

Kinetic-Molecular Theory of Gases

Derivation of Boyle’s Law
• Kinetic-Molecular Theory of Gases provides a satisfactory
explanation of Boyle’s law.

PV = a The value of a depends on N and T of the sample.

Ø Because P is F/A, the key to deriving the above equation is in

assessing the forces associated with molecules hitting the walls of the
container.

Ø Consider a molecule travelling along the x direction toward a wall

perpendicular to it path. The speed of the molecule is denoted by ux.
The force exerted on the wall by the molecule depend on the
following:

74
 Derivation of Boyle’s Law

1. The collision frequency – the no. of collisions per unit time.

2. The momentum transfer, or impulse per collision (momentum is

transferred as the molecule reverses direction upon hitting the
container wall). The momentum transfer to the wall is +2mux.

A model for calculating the pressure exerted by a single molecule

A particle moving with speed ux toward the end wall of a cubical box has initial
momentum mux. After deflecting off the wall, it has final momentum –mux. The change
in momentum is –mux – mux = –2mux. The time between collisions is 2L/ux.

75

Derivation of Boyle’s Law

• The force exerted by the molecule on the wall is the product of the
momentum transfer and the collision frequency:

(+2mux)(ux/2L) = mux2/L

force /
∴ Pressure = area = = = (for one molecule)

• For a sample of gas containing N molecules each traveling in the x

direction but with different speeds. We multiply the previous expression
by N and replace with , the expression for pressure becomes:

P =

76
 Derivation of Boyle’s Law

P =

∵ = = = where = + +

Ø is called the mean-square speed. The average value of

taking into account all the molecules, not just those moving in the
x direction.

Ø Substitute for into the above expression for P, and

convert the expression into an equation because the factor of 1/3
is the proportionality constant, Thus, we get,

P= -- eqn 3

-- this is the basic equation of the

kinetic-molecular theory of gases.
77

Derivation of Boyle’s Law

Supplementary Information on
Cartesian Components of Speed
• To describe pressure using kinetic theory, a molecule is envisioned as
traveling through space with a velocity, u, that can be decomposed into
three Cartesian components: ux, uy, uz.

The square of the velocity (u2) in terms of the three

velocity components is

uz u2 = u·u = ux2 + uy2 + uz2

u
uy

ux If the particle motion is random, the average velocities

along all three Cartesian dimensions are equivalent.

Therefore,
Cartesian components of velocity
The particle velocity u can be
decomposed into velocity
components along three Cartesian
dimensions: ux, uy, uz.
78
 Derivation of Boyle’s Law

Ø Eqn 3 can be rewritten as P =

where n is the amount in moles and M is the molar mass.

Ø By comparing this result to the ideal gas equation, PV = nRT, it can be

1 3
concluded that , and
= thus . =
3

Ø \ the root-mean-square speed, urms, is defined as

= = -- eqn 1

79

Derivation of Boyle’s Law

= = -- eqn 1

R = 8.3145 J×mol-1×K-1
J = kg×m2×s-2
∵ urms µ µ 1/ M in kg×mol-1

∴ On average,

(1) molecular speeds ­ as T ­,

(2) speeds of lighter molecules > speeds of heavier molecules.

80
7. Gas Properties Relating to the
Kinetic-Molecular Theory
(a) Diffusion
• is the migration of molecules as a result of
random molecular motion.
• In this case, the H2 initially diffuses farther
through the N2 because it is lighter.
Eventually, a complete random mixing
occurs.

(b) Effusion
• a related phenomenon, is the escape of gas
molecules from their container through a
tiny pinhole into a vacuum.
• rate µ molecular speeds
• In this case, the lighter H2 effuses faster
across the empty space than does the N2.
81

NH3 (g) + HCl (g) à NH4Cl (s)

HCl (aq) NH3 (aq)

82
7. Gas Properties Relating to the
Kinetic-Molecular Theory

• Rate of effusion µ molecular speeds.

• Consider the effusion of two different gases at the same T & P, we can
compare effusion rates with urms.

3RT
rate of effusion of A (urms)A MA MB
= = 3RT = -- eqn 4
rate of effusion of B (urms )B MA
MB

Refer to eqn 1

83

Gas Properties Relating to the

Kinetic-Molecular Theory
3RT
rate of effusion of A (urms)A MA MB
= = = -- eqn 4
rate of effusion of B (urms )B 3RT MA
MB

• Eqn 4 is a kinetic-theory statement of Graham’s law.

Graham’s law (applicable at low pressures only):

The rate of effusion of a gas is inversely proportional to the square
root of its molar mass.
Ø Only for gases at low pressure (natural escape, not a jet)
Limitations: Ø Tiny orifice (no collisions)
Ø Does not apply to diffusion

Ratio can be used to obtain:

· Molecular speeds · Distances traveled by molecules
· Effusion rates · Amounts of gas effused.
· Effusion times
84
 Gas Properties Relating to the
Class Practice 14 Kinetic-Molecular Theory

85

Gas Properties Relating to the

Class Practice 15 Kinetic-Molecular Theory

86
8. Non-ideal (Real) Gases
• Real gases are not ‘ideal’. They show deviations from ideal gas law
because molecules interact with one another.

• For one mole of gas, if it is an ideal gas, =1

• For non-ideal gas, the quotient may be greater/smaller than 1.

• The quotient, , is called the compressibility factor. It tells how

much a gas deviates from ideal gas behaviour.

87

8. Non-ideal (Real) Gases

Compressibility Factors and van der Waals
Constants for Various Gases (at 10 bar and 300 K)

88
 Non-ideal (Real) Gases
The behaviour of real gases –
Compressibility factor as a function of pressure at 0°C
Values of the compressibility factor < 1:
• signifies that intermolecular forces of
attraction are largely responsible for
deviations from ideal gas behaviour.

Values of the compressibility factor > 1:

• when the volume of the gas molecules
themselves is a significant fraction of the
total gas volume.

All gases behave ideally at sufficiently low

pressures (say below 1 atm).

­ Pressure Þ ­ deviation

89

Non-ideal (Real) Gases

Prediction from gas law: Kinetic Theory of Gases assumes no

At very high pressures, V à 0 intermolecular forces.
But actually this cannot be. But actually there are.
∴ At high P, PV(actual) > PV(predicted), ∴ At low T, PV(actual) < PV(predicted),
Þ compressibility ratio > 1 Þ compressibility ratio < 1

The effect of finite molecular size Intermolecular forces of attraction

Attractive forces of the red molecules for the
green molecule cause the green to exert less
force when it collides with the wall than if
these attractions did not exist.
90
 Non-ideal (Real) Gases

Plots of PV/nRT versus P for Plots of PV/nRT versus P for

several Gases (200 K) N2(g) at three Temperatures

Gases tend to behave ideally

at ____________________
and ______________________.
91

Non-ideal (Real) Gases

The van der Waals Equation
• A real gas equation of state, is defined with van der Waals equation
of state.
• It takes both the finite size of molecules and the attractive forces
into account.
• More accurate in calculating the relationship between P, V, and T for
gases than the ideal gas law.
a is a measure of how strongly
the molecules attract each other
= −
−
b is called the excluded volume per mole

• This equation of state has two parameters that are substance

dependent and must be experimentally determined. The parameters b
and a take the finite size of the molecules and the strength of
attractive interaction into account respectively.
92
 Non-ideal (Real) Gases
The van der Waals Equation
Compressibility Factors and van der Waals
Constants for Various Gases (at 10 bar and 300 K)

• The values of both a and

b ­ as the molecular
sizes ­.

• The smaller the values of

a and b, the more closely
the gas resembles an
ideal gas.

93

Non-ideal (Real) Gases

Class Practice 16

94
Class Practice 16 (Con’t)

95
End of Topic