CHEM 1043 General Chemistry II: Semester 2 Dr. A P L Tong

Course Information:
No. of credits: 6
Pre-requisite: Pass in CHEM1042 General Chemistry I
Duration: Semester 1, repeated in Semester 2
Teaching: 36 hours of lectures plus additional classes/tutorials to be
scheduled as necessary
CHEM 1043 Course Coordinator

Teachers
Dr. A P L Tong
Dr. A P L Tong (Topics 1 4) (apltong@hku.hk, Rm 602, CYM
Chemistry Building)
General Chemistry II Prof. D L Phillips (Topics 5 6) (phillips@hku.hk, Rm 401,

CYM Chemistry Building)
Teaching Assistants: Miss Ka Yan Tong (Topics 1 4) (u3507274@connect.hku.hk)
Mr. Ka Pan Shing (Topics 5 6) (pan524@hku.hk)
2016-2017 Assessment: Exam (70 %), Test (15 %), and 2 Assignments (15 %)
Semester 2 Course website: Moodle course (access via Student Portal My eLearning)
Dr. A P L Tong Practical e-learning: LabSkills

(Link: http://www.chemistry.hku.hk/eLearning/LabSkills/
Password: hkuchemlab)
CHEM1043 Dr. A P L Tong 2016-17
2
Your Prior Knowledge Course Objectives:

CHEM1042 General Chemistry I
in Chemistry
This course is a continuation of CHEM1042 General
(1) Chemistry: its nature and method
Physical properties; chemical changes and chemical properties; elements and compounds; Chemistry I. It aims to further consolidate some of the
measuring mass, length, volume and temperature; atomic structure and subatomic particles;
the mole concept and stoichiometry; solutions and concentrations; uncertainty in measurement and important fundamentals of chemistry that underlie many
significant figures.
topics and principles across the physical sciences.
(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; The course prepares students to pursue a major in
shapes of atomic orbitals; electron configurations; periodic trends: atomic radii, ionic radii, ionization
energies, and electron affinities. chemistry or in other aspects that require a good
(3) Chemical bonding and structures
Review on covalent, ionic and metallic bond. Covalent bonds and molecular structures (VSEPR, VB
foundation in chemistry.
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.
3 4
CHEM1043 Dr. A P L Tong 2016-17 CHEM1043 Dr. A P L Tong 2016-17
Course Contents: This content list is subject to minor change. Course Learning Outcomes:
(1) Gases
Simple gas laws; ideal gas equation; gases in chemical reactions; mixture of gases; kinetic-
On successful completion of this course, students should be able to:
molecular theory of gases; diffusion and effusion; non-ideal gases.
1. Demonstrate a knowledge and understanding of the properties and behavior of
(2) Structure and Bonding: The Delocalized Approach: Molecular Orbital Theory gases and apply gas laws and kinetic-molecular theory to processes involving
Bonding in homonuclear and heteronuclear diatomic molecules of first and second period of gases.
elements; bonding in some simple polyatomic molecules; bonding in metals (band theory).
(3) Solutions and their Properties
2. Demonstrate a knowledge and understanding in relation to solutions and their
Types of solutions; intermolecular forces and the solution process; solution formation and properties, solubility and complex-ion equilibria, and also electrochemistry.
equilibrium; solubilities of gases; vapor pressures of solutions; osmotic pressure; freezing-point
depression and boiling-point elevation of nonelectrolyte solutions; solutions of electrolytes; 3. Apply molecular orbital theory to explain the formation and properties of diatomic
colloidal mixtures. molecules of first and second period of elements and of some simple polyatomic
molecules.
(4) Solubility and Complex-Ion Equilibria
Solubility product constant; relationship between solubility and Ksp; common-ion effect in solubility 4. Demonstrate a knowledge and understanding of the relationship between free
equilibria; limitations of the Ksp concept; precipitation; solubility and pH; equilibria involving
complex ions; qualitative cation analysis. energy and spontaneity of reaction.
(5) Entropy & Gibbs Energy 5. Apply the theories and concepts introduced in the course to solve problems, perform
A quick review on entropy and the second & third laws of thermodynamics. Standard Gibbs calculations, make predictions and rationalize trends.
energy change; Gibbs energy change and equilibrium; coupled reactions.
6. Organize and present chemical ideas in a clear, logical and coherent way.
(6) Electrochemistry
Electrode potentials and their measurement; standard electrode potentials; Ecell, G, and K; Ecell 7. Demonstrate awareness of the relevant applications of chemistry in society and in
as a functions of concentrations; batteries; corrosion; electrolysis; industrial electrolysis
everyday life.
processes. 5 6
Recommended Reading: Reading is important! Class Schedule (2016-17 Sem 2): (In case there are any minor changes to the
following information, announcements will be
made in class and through the Moodle course.)
Day Time Venue
1) Petrucci; Herring; Madura; Bissonnette:
Mon 3:30 pm 5:20 pm (2-hour) MWT2 MW= Meng Wah Complex
General Chemistry: Principles and Modern
Applications, 11th edition, Pearson Thu 3:30 4:20 pm (1-hour) MWT2
(It is okay to use the 10th edition if you have already Dates of Lectures:
got this book.) January 16, 19, 23, 26
February 6, 9, 13, 16, 20, 23, 27
2) Moore; Stanitski; Jurs: Chemistry: The Molecular
March 2, 13, 20, 23, 27, 30
Science, latest edition, Brookes/Cole
April 3, 6, 10, 13, 20, 24, 27
3) Zumdahl; Zumdahl: Chemistry, latest edition, hku Swindon __ Those underlined are Monday 2-hour lectures.
listed price $405
Brookes/Cole 3 April (Mon) class will be used to hold the mid-term test (for Dr. A P L Tongs part).
(after 10 % student
Lectures highlighted in blue (i.e. 23, 27 and 30 March, 10, 13, 20, 24 and 27 April) are conducted
discount $364.5)
4) Silberberg: Chemistry: The Molecular Nature of by Prof. Phillips. Others are delivered by Dr. Tong.
Matter and Change, latest edition, McGraw Hill
Test:
5) Raymond Chang: Chemistry, latest edition, Date: 3 April 2017 (Mon)
Time: 3:30 pm 4:30 pm (the remaining time of this 2-hr session will be used for teaching)
McGraw Hill
Scope: To be announced
Weighting: 15 % of the course total
Venue: To be announced
7 8
What to learn in this topic?
Gases: Their Properties and Behaviour
Properties of gases: gas pressure

CHEM 1043 General Chemistry II
The simple gas laws
The ideal gas law & the general gas equation
Topic 1 Gases: Reaction stoichiometry
Properties and Behaviour Mixture of gases

Kinetic-molecular theory of gases
Gas properties relating to the kinetic-molecular theory
Dr. A P L Tong
Non-ideal (real) gases

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Your prior knowledge related to this topic If you have done

HKDSE Physics
HKDSE Chemistry or the equivalent,
Topic IX Rate of Reaction you have learnt
the following.
(Note that just some
students but not all
have this physics
background).

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Why study gases?
Suggested reading:
Although relatively few substances exist in the gaseous
state under typical condition, gases are very important.
E.g.) the earths atmosphere is a mixture of gases that consists
Chapter 6) Gases
mainly of elemental nitrogen (N2) and oxygen (O2). The
Petrucci; Herring; Madura; Bissonnette: atmosphere supports life.
General Chemistry: Principles and Modern 11E Elements that exist as gases at 25C and 1 atmosphere
Applications, 11th (or 10th) edition, Pearson
10E

13 14
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.
15 16
Properties of Gases: Gas Pressure
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
The gas particles are in constant random
3. the temperature of the gas motion. The rapidly moving particles
constantly collide with each other and with
4. the pressure of the gas
the walls of the container.
(Left) Chlorine gas (greenish yellow),

(Centre) Bromine gas (brownish red) above
liquid bromine,
(Right) Iodine gas (violet) above solid iodine.
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The Concept of Pressure Liquid Pressure

The molecules of a gas are in constant motion, The pressure of a gas is measured
frequently colliding with one another and with indirectly, by comparing it with a liquid
the walls of their container. pressure.
In the collisions, the gas molecules exert a force The pressure of a liquid depends only
on the container walls. on the height (h) of the liquid column and
the density (d) of the liquid. All the interconnected vessels fill to
the same height. As a result, the
Pressure is defined as a force per unit area. liquid pressures are the same
despite the different shapes and
W = weight, m = mass, g = gravity, V = volume volumes of the containers.
Force (N) F = W = m g = Vdg = hAdg =hd g

P (Pa) = The two cylinders have the
P (Pa) =
Area (m2) A A A A A
same mass and exert the
same force on the supporting weight W=mxg m=Vxd V=Axh g is constant
surface. is force
Force (N) = m (kg) x g (m/s2)
Conclusion:
Which one exerts a greater pressure? Liquid pressure liquid _______and the _______of the liquid column
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Barometric Pressure Class Practice 1: Comparing Liquid Pressures
Petrucci Example 6-1
Barometer, is a device constructed What is the height of a column of water that exerts the same pressure
by Evangelista Torricelli to measure 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.
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

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Manometers Class Practice 2

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.
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Units of Pressure Class Practice 3
Some Common Pressure Units
green red

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Class Practice 3 (Cont) The Simple Gas Laws

(1) Boyles Law
For a fixed amount of gas at a constant temperature, the
gas volume is inversely proportional to the gas pressure.
At constant n & T,
PV = constant
1
P
V
Relationship between gas volume and pressure Boyles Law

A doubling of the pressure causes the volume to decrease to one-half its
original value.
27 28
Class Practice 4 Class Practice 4 (Cont)
A 50.0 L cylinder contains nitrogen gas at a pressure of 21.5 atm.

The contents of the cylinder are emptied into 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

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(2) Charless Law Standard Conditions of Temperature and

Pressure
The volume of a fixed amount of gas at a constant pressure is
directly proportional to the Kelvin temperature. Gas properties depend on conditions.
It is useful to have a set of standard conditions of
250K, 500K, At constant n & P,
25mL 50mL temperature and pressure that can be used for comparing
V different gases.
= constant
T IUPAC defines standard conditions of temperature
and pressure (STP) as follows:
VT
P = 1 bar = 105 Pa
From a volume of zero at 0K,
V T (K)
T = 0 C = 273.15 K
Gas volume as a function of temperature Charless Law
The volumes of three different gases (A, B, and C) are measured at 1 atm and
500 K. As the temperature is lowered, the volume decreases as predicted by
Charles s law. 31 32
(3) Avogadros Law Densities and Molar Volumes of Various Gases
At a fixed temperature and pressure, the volume of a gas is

directly proportional to the amount of gas. 0 C, 1 bar
At constant T & P,
At 0C 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

Vn
Same molar volume (Theoretically)
1 mol gas = 22.414 L (at 0 C, 1 atm) = 22.711 L (STP)

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Combining the Gas Laws:

The Ideal Gas Equation Five Common Values of R (in various units)
When the three laws combine, we obtain the ideal gas equation.
1
V V T V n PV
P R=
nT
nT
V
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) atmL
R = = 0.082057
(1 mol)(273.15K) mol K
35 36
Applying the ideal gas equation Class Practice 5

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Class Practice 5 (Cont) Class Practice 6
39 40
The General Gas Equation Class Practice 7
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 n f Tf
PiVi PV
= f f -- General Gas Equation
niTi n f Tf
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
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Class Practice 7 (Cont) 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).
43 44
Class Practice 8: Class Practice 8 (Cont)

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Determination of gas densities Class Practice 9:

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 M (for gas)
d 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 48
Gases in Chemical Reactions Class Practice 10

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.

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Class Practice 10 (Cont) Law of Combining Volumes

2NO (g) + O2 (g) 2NO2 (g)
2 mol + 1 mol 2 mol
At constant T & P, 2VL + 1VL 2VL
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-Lussacs Law of Combining Volumes
(See next slide for an example)
51 52
E.g.) Applying the Law of Combining Volumes Mixtures of Gases
Petrucci Example 6-10
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

53 54
Daltons Law of Partial Pressures Partial Pressures

John Dalton proposed that in a mixture, each gas expands For a mixture of gases, A, B, and so on,
to fill the container and exerts the same pressure (called its Ptot = PA + PB +
partial pressure) that it would if it were alone in the container.
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,
Daltons law of partial pressures illustrated PA n RT/Vtot n VA n RT/Ptot n
= A = A = A = nA
Ptot ntotRT/Vtot ntot Vtot ntotRT/Ptot tot
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. The mole ratio
of A, A
55 56
Partial Pressures Class Practice 11
The mole ratio

of A, A
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.

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Collecting a Gas over Water Ptot = Pbar = Pgas + PH2O Collecting a Gas over Water
Vapour Pressure of Water
A pneumatic trough
at Various Temperatures
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

the atmosphere water vapour depends on the temp. 59 60

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Kinetic-Molecular Theory of Gases Kinetic-Molecular Theory of Gases

A gas is composed of a very large
The simple gas laws and the ideal gas equation are used number of particles in constant,
to predict gas behaviour. They are natural laws. random, straight-line motion.
Particles are point masses and
To explain the gas laws, we need a theory. separated by great distances.
Collisions are rapid and elastic.
Kinetic-Molecular Theory of Gases was developed in
No force between particles.
mid-19th century.
Individual particles may gain or lose
energy as a result of collisions. But total Visualizing Molecular Motion
energy remains constant.
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.
63 64
Distribution of Molecular Speeds Distribution of Molecular Speeds
/
The molecules in a gas travel at different speeds. Because N is too
4
large, we cannot know the speed of each molecule. 2 Distribution of molecular speeds
hydrogen gas at 0C
um is the modal speed; uav is the average speed;
A statistical prediction of how many molecules have a particular urms is obtained from the average of u2: i.e. The percentages of molecules with a
speed can be made. certain speed are plotted as a function of
speed.
The fraction, F, of molecules that have speed u is given by the
Three different speeds are noted.
following equation called Maxwell distribution of speeds:
1. the most probable speed is ~1500 m/s;
/
2. the average speed is ~1700 m/s; and
4
2
3. the root-mean-square speed is ~1800 m/s.
This equation can help us understand how the distribution of

Notice that um < uav < urms
speeds depends on molar mass, M, and temperature, T. The shape of the distribution depends on
the product of two opposing factors:
(1) u2 , and (2)

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Distribution of Molecular Speeds Distribution of Molecular Speeds
Look at the 3 characteristic speeds: Distribution of molecular speeds
/
hydrogen gas at 0C
4 The distribution depends on temperature 1. The most probable speed, or modal
2
and molar mass. speed is denoted by um; more
Look at the two curves for O2: molecules have this speed than any
other speed.
As T
range of speeds broadens, and 2. The average speed is denoted by uav.
distribution shifts towards higher speed, 3. The root-mean-square speed, urms, is
obtained from the average of u2,
Look at the curves for O2 and H2 at 273 K: which is denoted by .
The lighter the gas, the broader the
range of speeds. These characteristic speeds can be calculated by using the
following expressions:
Note that the area under each curve
is the same because N is the same
2 8 3
-- eqn 1
Distribution of Molecular Speeds
the effect of mass and temperature
(R = 8.3145 J K1mol1)
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Class Practice 13: Calculating a Root-Mean-Square Speed Class Practice 13 (Cont)
9.75 102 m/s

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Experimental Determination Effect of Temperature
Distribution of Molecular Speeds
urms is of particular interest because we can use the value of urms to
An oven (in which gas molecules are
heated) and attached evacuated
calculate the average kinetic energy, , of a collection of molecules.
chamber are separated by a wall with a
small hole in it. The gas molecules The average KE of a collection of molecules, each having a mass m
emerging from the hole pass through a = M/NA, is the average of mu2:
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.
Since urms = 3 / , then u2rms = , the expression above can
Only those molecules with the correct
speed to pass through all rotating disks be rewritten as: R and NA
will reach the detector, where they can = -- eqn 2 are constant
be counted.
That means, = constant x T
By changing the rate of rotation of the disks, the complete distribution of
The Kelvin temperature (T) of a gas is directly proportional to the
molecular speeds can be determined.
average kinetic energy ( ) of its molecules .
71 72
Derivation of Boyles Law Derivation of Boyles Law
Kinetic-Molecular Theory of Gases provides a satisfactory 1. The collision frequency the no. of collisions per unit time.
explanation of Boyles law.
2. The momentum transfer, or impulse per collision (momentum is
transferred as the molecule reverses direction upon hitting the
PV = a The value of a depends on N and T of the sample. container wall). The momentum transfer to the wall is +2mux.
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.
Consider a molecule travelling along the x direction toward a

A model for calculating the pressure exerted by a single molecule
wall perpendicular to it path. The speed of the molecule is
A particle moving with speed ux toward the end wall of a cubical box has initial
denoted by ux. The force exerted on the wall by the molecule momentum mux. After deflecting off the wall, it has final momentum mux. The
depend on the following: change in momentum is mux mux = 2mux. The time between collisions is
2L/ux.

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The force exerted by the molecule on the wall is the product of the P =
momentum transfer and the collision frequency:
(+2mux)(ux/2L) = mux2/L
where
is called the mean-square speed. The average value of

force /
Pressure (for one molecule) taking into account all the molecules, not just those
area
moving in the x direction.
For a sample of gas containing N molecules each traveling in the x Substitute for into the above expression for P, and
direction but with different speeds. We multiply the previous
convert the expression into an equation because the factor
expression by N and replace with , the expression for of 1/3 is the proportionality constant, Thus, we get,
pressure becomes:
P = P -- eqn 3
-- this is the basic equation of the

kinetic-molecular theory of gases.
75 76
Eqn 3 can be rewritten as P
= -- eqn 1
where n is the amount in moles and M is the molar mass.

R = 8.3145 Jmol-1K-1
urms 1/ J = kgm2s-2
By comparing this result to the ideal gas equation, PV = nRT, it M in kgmol-1
1 3
can be concluded that 3
, and thus . On average,
(1) molecular speeds as T ,
the root-mean-square speed, urms, is defined as
(2) speeds of lighter molecules > speeds of heavier molecules.
= -- eqn 1

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Gas Properties Relating to the Gas Properties Relating to the

Kinetic-Molecular Theory Kinetic-Molecular Theory
(a) Diffusion
Rate of effusion molecular speeds.
is the migration of molecules as a result
of random molecular motion.
In this case, the H2 initially diffuses
Consider the effusion of two different gases at the same T & P,
farther through the N2 because it is we can compare effusion rates with urms.
lighter. Eventually, a complete random
mixing occurs.
3RT
rate of effusion of A urms A MA MB
rate of effusion of B

urms B
3RT
MA
-- eqn 4
(b) Effusion MB
a related phenomenon, is the escape of
gas molecules from their container Refer to eqn 1
through a tiny pinhole into a vacuum.
rate molecular speeds
In this case, the lighter H2 effuses faster
across the empty space than does the
N2.
79 80
Gas Properties Relating to the Gas Properties Relating to the
Kinetic-Molecular Theory Class Practice 14 Kinetic-Molecular Theory
3RT
rate of effusion of A urms A MA MB
3RT -- eqn 4
rate of effusion of B urms B MA
MB
Eqn 4 is a kinetic-theory statement of Grahams law.
Grahams law (applicable at low pressures only):

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

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Gas Properties Relating to the

Class Practice 15 Kinetic-Molecular Theory
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.
83 84
Non-ideal (Real) Gases The behaviour of real gases
Compressibility Factors and van der Waals Compressibility factor as a function of pressure at 0C
Constants for Various Gases (at 10 bar and 300 K)
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 deviation

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Non-ideal (Real) Gases Non-ideal (Real) Gases
Prediction from gas law: Kinetic Theory of Gases assumes

At very high pressures, V 0 no 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),
compressibility ratio > 1 compressibility ratio < 1
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

The effect of finite molecular size Intermolecular forces of attraction at _____________________
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
and _____________________.
these attractions did not exist.

87 CHEM1043 Dr. A P L Tong 2016-17
88
The van der Waals Equation
Non-ideal (Real) Gases Non-ideal (Real) Gases
The van der Waals Equation
A real gas equation of state, is defined with van der Waals Compressibility Factors and van der Waals
equation of state. Constants for Various Gases (at 10 bar and 300 K)
It takes both the finite size of molecules and the attractive

forces into account. The values of both a
and b as the
More accurate in calculating the relationship between P, V, and
T for gases than the ideal gas law. molecular sizes .
The smaller the values

of a and b, the more
closely the gas
resembles an ideal gas.
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.
89 CHEM1043 Dr. A P L Tong 2016-17
90


91 CHEM1043 Dr. A P L Tong 2016-17
End of Topic 92

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CHEM 1043 General Chemistry II: Semester 2 Dr. A P L Tong

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Course Information:

CHEM 1043 Course Coordinator

General Chemistry II Prof. D L Phillips (Topics 5 6) (phillips@hku.hk, Rm 401,

Dr. A P L Tong Practical e-learning: LabSkills

Your Prior Knowledge Course Objectives:

Properties of gases: gas pressure

Properties and Behaviour Mixture of gases

CHEM1043 Dr. A P L Tong 2016-17

Your prior knowledge related to this topic If you have done

CHEM1043 Dr. A P L Tong 2016-17

Applications, 11th (or 10th) edition, Pearson

CHEM1043 Dr. A P L Tong 2016-17

(Left) Chlorine gas (greenish yellow),

The Concept of Pressure Liquid Pressure

Force (N) F = W = m g = Vdg = hAdg =hd g

Mercury flows out of the tube until the

Standard Atmospheric Pressure

CHEM1043 Dr. A P L Tong 2016-17

Manometers Class Practice 2

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

Measurement of gas pressure with an open-end manometer

Some Common Pressure Units

CHEM1043 Dr. A P L Tong 2016-17

Class Practice 3 (Cont) The Simple Gas Laws

Relationship between gas volume and pressure Boyles Law

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

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

CHEM1043 Dr. A P L Tong 2016-17

(2) Charless Law Standard Conditions of Temperature and

At a fixed temperature and pressure, the volume of a gas is

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

Same molar volume (Theoretically)

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

Combining the Gas Laws:

PV = nRT where R = Universal Gas Constant

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

CHEM1043 Dr. A P L Tong 2016-17

Class Practice 5 (Cont) Class Practice 6

The ideal gas equations must be applied twice in order to

Class Practice 7 (Cont) Applications of the Ideal Gas Equation

Determination of molar masses

Because , if we know the mass (m) and no. of

CHEM1043 Dr. A P L Tong 2016-17

Determination of gas densities Class Practice 9:

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

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

For reactions involving gases, we can

(1) use stoichiometric factors to relate gas quantities to

Law of Combining Volumes can be developed using the

CHEM1043 Dr. A P L Tong 2016-17

Class Practice 10 (Cont) Law of Combining Volumes

2 L NO (g) + 1 L O2 (g) 2 L NO2 (g)

The volume ratio of gases consumed and produced in a

(See next slide for an example)

CHEM1043 Dr. A P L Tong 2016-17

Daltons Law of Partial Pressures Partial Pressures

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

We can derive a particularly useful expression from the