CHEM1020 Module1 Viewing

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NIVERSITY OFF QUEENSLAND
UEENSLAND
CHEM1020
Chemical Energetics and
Equilibria
Lecturers: Assoc. Prof. Ian Gentle i.gentle@uq.edu.au
Dr Michael Monteiro m.monteiro@uq.edu.au
Prof Curt Wentrup c.wentrup@uq.edu.au
Prof John Drennan j.drennan@uq.edu.au
Website: http://blackboard.elearning.uq.edu.au
Text: Zumdahl, Chemistry, 6th or 7th Edn
CHEM1020 Insert
Chemical
section
Energetics
name and Equilibria School of Molecular and Microbial Sciences
1
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Outline of this section of the course
• Gases
• Condensed phases (liquids, solids)
• Thermochemistry
• Chemical equilibrium
• Phase equilibria
• Properties of solutions
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The Gaseous State

Zumdahl Sections 5.1, 5.2, 5.3, 5.5
States of Matter
Why are some substances gases at room

temperature, while others are solids or
liquids?
- intermolecular forces
Elements in their pure state are mostly solids,

with exceptions
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Chemical
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Gaseous Elements
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Characteristics of Gases
• Gases have no fixed volume or shape; they
expand to fill all available space.
• What is a gas? – at the molecular level
• Atoms in a gas are free to move
independently from each other. Because the
atoms in a gas are moving at random, the
gaseous state is the simplest to describe
mathematically. There are three gas laws.
CHEM1020 Insert
Chemical
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Energetics
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Gas Pressure
Gases exert pressure on surroundings due to
constant movement of molecules.
force
Pressure is defined as
area
A
F
N
Units: 1 Pa (pascal)= 1 N m-2
m2
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Chemical
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Another common pressure unit: atmosphere (atm)

1 atm = 760 mm Hg
= 1.01325 × 105 Pa
= 101.325 kPa
The Gas Laws

How does the volume of a gas change when we
vary the pressure, temperature, number of
moles?
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Boyle’s Law
How does the volume of a gas change if we vary
the pressure?
If we increase pressure on a gas, its volume
decreases (c.f. solids, liquids which are relatively
incompressible)
P P
V 1/V
CHEM1020 Insert
Chemical
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1
Boyle: P∝
V
1
V = k×
P
i.e. PV = k
Example
A sample of chlorine gas occupies a volume of
946 mL at a pressure of 726 mmHg. Calculate
the pressure of the gas if the volume is
reduced to 154 mL (assume temperature
remains constant)
CHEM1020 Insert
Chemical
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Solution: Since PV = constant,

P1V1 = P2V2, hence
P1V1
P2 =
V2
946 mL
= 726 mm Hg ×
154 mL
= 4.46 × 10 3 mm Hg
or to convert 4.46 × 10 3 mm Hg
to Pa:
P2 = × 101.3 kPa
760 mm Hg
= 594 kPa
CHEM1020 Insert
Chemical
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Charles’ Law
How does a change in temperature affect the
volume of a gas at constant pressure?
Charles & Gay-Lussac: V decreases as T decreases
P1
V
P2
condensation P3
-273.15 °C T (°C)
CHEM1020 Insert
Chemical
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Note that the intercept of each line lies at

-273.15°C, known as absolute zero
Kelvin: absolute
temperature scale
0 K = -273.15°C
T / K = t / °C + 273.15
CHEM1020 Insert
Chemical
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Energetics
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Seen on a
London bus…
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Chemical
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From above plot, V = bT

V
=b Charles’ Law
T
For changes in temperature from T1 to T2,
V1 V2
=
T1 T2
CHEM1020 Insert
Chemical
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Avogadro’s Law
Avogadro postulated that at a given T and P, equal

volumes of gases contain equal number of
molecules, ie the volume is proportional to the
number of moles present
V = an
Example: Suppose we have a 12.2 L sample

containing 0.50 mol oxygen gas at pressure of 1
atm. If all this oxygen were converted to ozone
(O3) at same T and P, what would be the volume?
CHEM1020 Insert
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Answer: Equation is: 3O 2 (g) → 2O3 (g)
2 mol O3
No. moles O3 produced = 0.50 mol O2 ×
3 mol O2
= 0.33 mol O3
V1 V2
Since V/n is constant, =
n1 n2
 n2 
∴ V2 = V1 
 n1 
0.33 mol
= × 12.2 L
0.50 mol
= 8.1 L
CHEM1020 Insert
Chemical
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Air bags
Rely on the explosive
decomposition of sodium
azide to produce nitrogen
gas
2NaN3 (s) → 2Na(s) + 3N2 (g)
• Causes inflation in less than

0.05 s
• 100 g NaN3 produces 56 L of
gas at room temperature
howstuffworks.com
and pressure
CHEM1020 Insert
Chemical
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Energetics
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Ideal Gas Law

k
V =
So far we have: P
V = bT
V = an
nT
∴ V = const. ×
P
PV = nRT Ideal Gas Equation
R: gas constant R = 8.314 J K −1 mol −1(SI)

= 0.082057 L atm K −1 mol −1
CHEM1020 Insert
Chemical
section
Energetics
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The ideal gas law holds only for ideal gases,

in which molecules:
•do not interact with each other in any way
•do not occupy any volume
No real gases obey it perfectly, but it’s good

enough for many gases at low pressure.
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Chemical
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Uses of Ideal Gas Equation

Changes in P, V, T or n
Suppose we change any of the Initially R = P1V1
above variables: n1T1
P2V2
Finally R =
n2T2
If one variable remains P1V1 P2V2

∴ =
constant, it cancels. n1T1 n2T2
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Example: A sample of diborane gas (B2H6) has a

pressure of 45.8 kPa at a temperature of -15°C
and a volume of 3.48 × 10-3 m3. If conditions are
changed such that temperature is 36°C and
pressure is 62.2 kPa, what will be the volume of
the sample?
P1V1 P2V2
Answer: n remains constant, so =
T1 T2
P1V1 T2
∴ V2 = ×
T1 P2
CHEM1020 Insert
Chemical
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P1 = 45.8 kPa P2 = 62.2 kPa

T1 = -15°C + 273 = 258 K T2 = 36°C + 273 = 309 K
V1 = 3.48 × 10-3 m3 V2 = ?
45.8 kPa ⋅ 3.48 × 10 −3 m3 ⋅ 309 K

V2 =
258 K ⋅ 62.2 kPa
= 3.07 × 10 −3 m3
CHEM1020 Insert
Chemical
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Energetics
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Dalton’s Law of Partial Pressures
Often mixtures of gases, rather than pure

substances, are of interest.
Dalton:the total pressure of a mixture of gases

is the sum of the pressures that each gas
would exert if it were alone in the container
i.e., if sample contains gases A and B, total

pressure is given by:
CHEM1020 Insert
Chemical
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PT = PA + PB
nA RT nB RT
= +
V V
RT
= (nA + nB )
V
nT RT
=
V
How does the pressure of one gas relate

to the total?
CHEM1020 Insert
Chemical
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PA nA RT /V
=
PT (n A +nB )RT /V
nA
=
n A + nB
= xA
xA is the mole fraction of A; xA: 0 → 1

PA = x A PT
Hence
PB = x B PT
and in general for component i Pi = x i PT

CHEM1020 Insert
Chemical
section
Energetics
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CHEM1020 Insert
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Liquids and Solids

Zumdahl Sections 10.1-10.7
Compared to gases, liquids and solids have high

density and low compressibility: condensed states
(or condensed phases).
CHEM1020 Insert
Chemical
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The three states of matter
Intermolecular forces (between molecules) are

much stronger in condensed phases than in gases.
CHEM1020 Insert
Chemical
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Dipole-dipole forces
Molecules with dipole moments can line up so that
negative and positive ends are in proximity,
leading to electrostatic attraction.
These are only important over short distances.
CHEM1020 Insert
Chemical
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Hydrogen bonds are special

forms of dipole-dipole
interactions due to:
• highly polar bond
• small size of hydrogen
atom (leading to close
approach).
CHEM1020 Insert
Chemical
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London dispersion (or van der Waals) forces
Why do non-polar atoms or molecules exist in

condensed states under some conditions?
For example helium exists as a liquid below about
4 K.
phys.kent.edu
CHEM1020 Insert
Chemical
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Momentary changes in
the charge distribution
around a nucleus (or
molecule) can occur, and
when this happens near
another atom, the dipole
can induce a dipole in the
other atom.
This results in a weak and short-lived interaction

known as London dispersion force.
CHEM1020 Insert
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Liquids
Surface tension
Molecules in liquids
experience attractive forces
from other molecules, but
molecules at the surface
experience uneven forces →
surface tension
Result is that the surface area stays as small as

possible.
CHEM1020 Insert
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Surface properties of liquids depend on balance

between cohesive and adhesive forces. Solid
surfaces are described as either hydrophobic or
hydrophilic depending on their interactions with
water.
Structure exists in liquids, but hard to model.

CHEM1020 Insert
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Solids
Basic classification into
amorphous (eg glass, plastics) or
crystalline (eg silicon, diamond)
Crystalline solids are

described in terms of their
unit cell structure, measured
by X-ray crystallography.
Total solid is made up of a
lattice of unit cells.
CHEM1020 Insert
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X-ray Diffraction
An x-ray beam of known wavelength is focused on a
powdered sample and x-ray diffraction peaks are
measured using a detector. detector
Diffracted X-ray
2θ
Monochromatic X-ray
Constructive interference Destructive interference
CHEM1020 Insert
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When 2d sin θ is a multiple of the wavelength of the

incident X-ray wavelength, coherent reflection will result.
Diffraction condition, Bragg’s law: 2d sin θ =n λ

n = 1,2,…..
CHEM1020 Insert
Chemical
section
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Types of solids
Atomic solids (eg graphite, silicon, magnesium)
Atoms are at the points of the lattice
These can be further classified into metallic
solids, network solids, and Group 8A solids.
Molecular solids (eg sucrose, ice)

Molecules are at the points of the lattice
Ionic solids (eg sodium chloride)

Ions are at the points of the unit cell lattice
CHEM1020 Insert
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ionic
atomic
molecular
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Metals
Typically pictured as close-packed spheres.
Bonding in metals is characterised by non-
directional covalent bonding. Can be modelled
by layers of spheres, which can stack in two ways:
ABAB → hexagonal close

packing, eg Mg, Zn
ABCA → cubic close

packing, eg Al, Fe, Cu
CHEM1020 Insert
Chemical
section
Energetics
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Metals have unique properties: high electrical and

thermal conductivity, malleability
What causes these?
Bonding in metals
Electrons are arranged around metal atoms in
such a way that they are mobile.
“electron sea” model
CHEM1020 Insert
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Band model
When two metal atoms interact, two molecular
orbitals (bonding and antibonding) result. When
many atoms interact, many closely spaced
orbitals result.
Half are filled with
bonding electrons,
but half are empty
and can be easily
reached.
CHEM1020 Insert
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Insulators are materials

which have a large gap
between the filled and
unfilled bands.
Semiconductors (eg silicon) have a small gap,

especially when doped with other materials.
Choice of dopant leads to either excess of electrons
(arsenic) and an n-type semiconductor, or a deficiency
of electrons (boron) p-type semiconductor. In the
latter, holes are the charge carriers
CHEM1020 Insert
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Network Atomic Solids

Graphite and diamond are solids in which the bonding is
not localised between atoms, but form a huge “molecule”
or network.
The bonding is very different in the two:
Diamond: tetrahedral arrangement,
insulator, colourless.
Graphite: layers of fused six-

membered rings, conductive (electrons
in π-system are delocalised), black
solid.
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Graphite structure
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Silicates and Glasses

Silicon materials are major constituents of the earth’s
crust.
Silicates are based on a

network of tetrahedra
of SiO4 building blocks.
Silica is SiO2, and is the
basic building block of
glass. Additives give
glass particular
properties.
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Eg: borosilicate glass (Pyrex) contains B2O3 for thermal

properties; optical glass contains K2O for hardness.
Compositions of Some Common Types of Glass
Percentages of Various Components
Type of Glass SiO2 CaO Na2O B2O3 Al2O3 K2O MgO
Window (soda-lime 72 11 13 - 0.3 3.8 -

glass)
Cookware 55 15 - - 20 - 10
(aluminosilicate glass)
Heat-resistant 76 3 5 13 2 0.5 -
(borosilicate glass)
Optical 69 12 6 0.3 - 12 -
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Molecular Solids
These are materials in which individual molecules
occupy lattice positions (eg ice). Intermolecular
forces are relatively much weaker than the covalent
intramolecular forces.
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Ionic Solids
Held together by strong electrostatic forces.
Leads to high melting points.
Typically the larger ions (usually anions) are
close packed, and the smaller ions fit into holes
between them. Holes can be trigonal,
tetrahedral or octahedral.
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Zinc sulfide
Sodium chloride Thermochemistry
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Thermochemistry
Zumdahl Chapter 6 (not 6.5, 6.6)
Chemical reactions involve

changes in energy
Most of the energy used by

society comes from chemical
reactions (combustion of
coal, petroleum products and
natural gas)
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Thermochemistry:
- the study of energy changes involved with
chemical reactions
Definitions of energy:
(1) "the capacity to do work"
eg lifting an object, work done = force × distance
(2) “the capacity to transfer heat"
Heat: transfer of thermal energy between two
bodies at different temperatures
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Energy Changes in Chemical Reactions
Virtually all chemical reactions absorb or

release energy.
In order to understand this, we need to focus on

a limited, well-defined part of universe, called
the system. Everything else is called the
surroundings.
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Example: Study of heat from combustion of

methane
CH 4 ( g ) + 2O 2 ( g ) → CO 2 ( g ) + 2H 2O( g ) + energy
CH4
CO2
System: reactants and products
O2
Surroundings: vessel, room, etc
H2O
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Combustion of methane releases energy in

form of heat (energy flows from system to
surroundings). Said to be exothermic.
Other reactions cause energy to flow from

surroundings to system: endothermic.
e.g. N 2 ( g ) + O 2 ( g ) + energy → 2NO( g )
Notice: energy is not created or destroyed,

just transferred from one place to another
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Energy lost by system = energy gained by

surroundings
The First Law of Thermodynamics
Energy can be converted from one form to

another, but cannot be created or
destroyed.
Where does this energy come from?

- potential energy difference between
reactants and products.
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1 mol CH4
2 mol O2
Potential energy
2 mol H2O
1 mol CO2
Exothermic: products have lower potential

energy than reactants
Endothermic: reactants have lower potential
energy than products
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Internal Energy
Total energy of a system is the sum of kinetic and

potential energy of its parts. Can only measure
changes:
∆E = E final − Einitial E : internal energy
Positive sign ⇒ system gains energy from

surroundings.
Negative sign ⇒ system loses energy to
surroundings.
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Total energy of universe must remain constant,
∴ ∆Esys + ∆Esurr = ∆Euniverse = 0

or ∆Esys = − ∆Esurr
System can exchange energy with its

surroundings in two ways, as heat (q) or as
work (w), so write First Law as:
∆E = q + w q: heat added to system

w: work done on system
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Positive work or heat implies that energy of

system increases.
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Note that when the volume of a gas is changed

at constant temperature, the internal energy is
constant.
i.e. ∆E = 0 for compression/expansion of

gas at constant temperature
Another way of saying this: the internal energy

of a gas depends only on its temperature (and
number of moles)
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Work
There are many different types of work, eg
electrical, mechanical, etc. Here, interested in
mechanical work associated with expansion or
contraction of gas (“PV” work).
w = −Pext∆V where ∆ V = V final − Vinitial
Negative sign implies that expanding gas does

work on surroundings
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Rationalisation: w = F×d = F×∆h (change in height)

= P×A×∆h
= P∆V P=
F 06_73
F
P =
A
Area = A
A
∆h ∆h
∆V
(a) Initial (b) Final

state state
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Example: A gas expands in volume from 0.1 m3

to 0.2 m3 against a constant pressure of 100 kPa.
How much work is done?
Solution: w = − Pext ∆V
(
= −100 ×103 N m − 2 0.2 m 3 − 0.1 m 3 )
= −1.0 × 10 4 N m
= −10 kJ
Gas “does” 10 kJ of work.
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Under conditions of constant volume, ∆V = 0

so no work can be done (w = 0) and from the
First Law:
∆E = qv (subscript v ⇒ constant volume)
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In many cases we deal with constant pressure,

(volume may change)
Heat flow under conditions of constant pressure

is called enthalpy change, given symbol ∆H. ie
∆H = q p
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In general, enthalpy is defined as

Volume
Enthalpy
H = E + PV
Internal energy System pressure
So for changes from one state to another (such as

a chemical reaction)
∆H = ∆E + ∆(PV)
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Internal energy and enthalpy: how are

they related?
Let’s examine a reaction involving gases:
Using ideal gas law, at ∆E = ∆H − ∆ ( PV )

constant temperature = ∆H − ∆ ( nRT )
= ∆H − RT∆n
where ∆n = change in no. moles of gases

= number of moles of product gases
− number of moles of reactant gases
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Example:
C( graphite) + 12 O2 ( g ) → CO( g )
∆n = 1 mol - ½ mol = ½ mol
Another example:
At 298 K for the reaction shown below,
∆H 0 = −492.7 kJ
C 2 H 5 OH (l ) + O 2 ( g ) → CH 3 COOH(l ) + H 2 O(l )
What is the standard internal energy change for
this reaction at 298 K?
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Solution:
At constant temperature, we know that:
∆E = ∆H − RT∆n
In this case, ∆n = 0 mol –1 mol = -1 mol, and so
∆E = ∆H − RT ⋅ −1 mol
= −492.7 × 10 3 J − 8.314 J K −1 mol −1 ⋅ 298 K ⋅ −1 mol
= −490.2 × 10 3 J
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Enthalpy change for chemical reaction:
∆H = H ( products ) − H ( reactants )
Normally write enthalpy change with balanced

equation:
2SO2 ( g ) + O2 ( g ) → 2SO3 ( g ) ∆H = −196 kJ
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For exothermic reaction, enthalpy of products

less than that of reactants, so ∆H < 0
If endothermic: ∆H > 0
CHEM1020 Insert
Chemical
section
Energetics
75
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Important points
1. Enthalpy is an extensive property, ie if
the amounts of reactants are doubled,
enthalpy change is doubled. Implicit that
∆H as written applies to amounts in
balanced equation.
2SO2 ( g ) + O2 ( g ) → 2SO3 ( g ) ∆H = −196 kJ
CHEM1020 Insert
Chemical
section
Energetics
76
THE
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2. Enthalpy change of reverse reaction is of

same magnitude but opposite sign.
2SO3 ( g ) → 2SO2 ( g ) + O 2 ( g ) ∆H = +196 kJ
2SO2(g) + O2(g)
Products/reactants
∆H=-196kJ
Enthalpy, H
∆H=+196kJ
2SO3(g)
Reactants/products
CHEM1020 Insert
Chemical
section
Energetics
77
THE
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3. Enthalpy change for a reaction depends on

state of reactants and products
eg liquid water vs water vapour:
CH 4 ( g ) + 2O2 ( g ) → CO2 ( g ) + 2 H 2O( g ) ∆H = −802 kJ

CH 4 ( g ) + 2O 2 ( g ) → CO2 ( g ) + 2 H 2O(l ) ∆H = −890 kJ
Difference is:
2 H 2 O( g ) → 2 H 2 O( l ) ∆H = −88 kJ
CHEM1020 Insert
Chemical
section
Energetics
78
THE
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State Functions
Consider a beaker of water at 25 °C.
50 g 50 g 50 g
100 C 25 C 0C
Energy contained in system is same regardless

of history. Energy is a state function - depends
only on variables that define state of system (P,
V, T, number of moles).
Enthalpy is a state function, but work and
heat are not.
CHEM1020 Insert
Chemical
section
Energetics
79
THE
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charged
work
toy car
light bulb
heat heat
uncharged
Example: discharging of a battery
In each case, total energy change is same, but

work done by system depends on which pathway
taken by process.
CHEM1020 Insert
Chemical
section
Energetics
80
THE
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Hess's Law
Because enthalpy is state function, depends only

on initial and final conditions, ie overall ∆H will
be same if carried out in one step or series of
steps.
Hess's Law: If a reaction is carried out in a

series of steps, the enthalpy change will be
equal to the sum of the enthalpy changes for the
individual steps.
CHEM1020 Insert
Chemical
section
Energetics
81
THE
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CHEM1020 Insert
Chemical
section
Energetics
82
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Example:
Two forms carbon occurs

in are graphite and
diamond. Given the
following data, calculate
∆H for the conversion of
graphite to diamond:
C( graphite) + O2 ( g ) → CO2 ( g ) ∆H = −394 kJ

C( diamond ) + O 2 ( g ) → CO2 ( g ) ∆H = −396 kJ
CHEM1020 Insert
Chemical
section
Energetics
83
THE
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Solution:
Reverse second reaction and sum the two:
C( graphite) + O 2 ( g ) → CO2 ( g ) ∆H = −394 kJ

CO2 ( g ) → C( diamond ) + O 2 ( g ) ∆H = −( −396 kJ )
C( graphite) → C( diamond ) ∆H = 2 kJ
Thus 2 kJ of energy required to change 1 mol

of graphite to diamond (endothermic
process).
CHEM1020 Insert
Chemical
section
Energetics
84
THE
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Standard Enthalpy of Formation
Can use Hess's Law to calculate ∆H for many

reactions using tabulated enthalpies.
Important tabulated values are standard

enthalpies (or heats) of formation
Enthalpy of formation (∆Hf): enthalpy

change associated with formation of 1 mole of
a substance from its elements
e.g. C + 12 O 2 → CO
CHEM1020 Insert
Chemical
section
Energetics
85
THE
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but this depends on state, temperature and

pressure, so need to define standard state: the
most stable form at 1 atmosphere pressure and
temperature of interest (usually 298 K)
This definition works for elements

For compounds: Gases: one atmosphere
Liquids: pure
Solutions: 1 M
Standard enthalpy of formation ( ∆H 0f ):
enthalpy change that results when 1 mole of a
compound formed from its elements, with all
substances in standard states.
CHEM1020 Insert
Chemical
section
Energetics
86
THE
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Example:
Standard enthalpy of formation for ethanol
relates to the following reaction:
2C( graphite) + 3H 2 ( g ) + 12 O 2 ( g )
→ C2 H 5OH (l ) ∆H 0 = −277.7 kJ
i.e. ∆H 0f (ethanol ) = −277.7 kJ mol−1
Note: It follows from the definition that ∆H 0f of an

element in its most stable form is zero.
O2 ( g ) → O2 ( g ) ∆H = 0
CHEM1020 Insert
Chemical
section
Energetics
87
THE
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Note: ∆H0f is in kJ mol-1, but ∆H is in kJ !!!

CHEM1020 Insert
Chemical
section
Energetics
88
THE
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These values can be used to calculate enthalpies of

reactions:
1. Take reactants apart to their constituent
elements
2. Form products from the elements
Constituent Elements
-Σm∆H0f(reactants) +Σn∆H0f(products)
Reactants Products
CHEM1020 Insert
Chemical
section
Energetics
89
THE
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For general (hypothetical) reaction:
aA + bB → cC + dD
then ∆H rxn
0
[
= c∆H 0f (C) + d∆H 0f ( D) ]
[
− a∆H 0f ( A ) + b∆H 0f ( B) ]
In other words,
∆H rxn
0
= ∑ n∆H 0f ( products) − ∑ m∆H 0f ( reactants )
where n & m represent the coefficients in the balanced
equation, and the sums are over all reactants &
products.
CHEM1020 Insert
Chemical
section
Energetics
90
THE
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UEENSLAND
Example 1: combustion of methane
CH 4 ( g ) + 2O 2 ( g ) → CO 2 ( g ) + 2H 2 O(l )
CHEM1020 Insert
Chemical
section
Energetics
91
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Example 2:
Using standard enthalpies of formation, calculate
std. enthalpy change for combustion of ammonia in
air:
4NH 3 ( g ) + 7O 2 ( g ) → 4NO 2 ( g ) + 6H 2 O(l )
Solution:
∆H rxn
0
= 4∆ H 0f [NO 2 ( g )] + 6∆ H 0f [H 2 O(l )]
− 4∆ H 0f [NH 3 ( g )] − 7∆ H 0f [O 2 ( g )]
= 4 mol × 34 kJ mol −1 + 6 mol × −286 kJ mol −1
− 4 mol × −46 kJ mol −1 − 0
= −1396 kJ
CHEM1020 Insert
Chemical
section
Energetics
92
THE
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UEENSLAND
Example 3:
Given the following standard enthalpy of reaction,
use tabulated enthalpies of formation to
determine ∆H 0f of CuO(s):
CuO( s ) + H 2 ( g ) → Cu( s ) + H 2 O(l ) ∆H 0 = −130.6 kJ
Solution:
∆H 0 = ∆H 0f [Cu( s )] + ∆H 0f [ H 2O(l )]
− ∆H 0f [CuO( s )] − ∆H 0f [ H 2 ( g )]
CHEM1020 Insert
Chemical
section
Energetics
93
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i.e. − 130.6 kJ = 0 + 1 mol × −285.8 kJ mol −1

− 1 mol × ∆H 0f [CuO( s )] − 0
∆H 0f [CuO( s )] = (130.6 kJ − 285.8 kJ ) / 1 mol

= −155.2 kJ mol −1
CHEM1020 Insert
Chemical
section
Energetics
94
THE
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Calorimetry
Refers to the measurement of heat changes as a
result of chemical reactions. Experimentally,
measure temperature change, but:
“What is relationship between heat and
temperature change?”
Heat capacity (C): amount of heat required to
raise the temperature of a body by 1°C (ie 1 K)
heat absorbed J J
C= = or
increase in temperature K °C
CHEM1020 Insert
Chemical
section
Energetics
95
THE
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Specific heat capacity (s): heat required to

raise temperature of 1 g of a substance by 1°C.
ie C=ms m = mass in grams
heat capacity per gram = J/(°C g) or J/(K g)
Knowing specific heat or heat capacity, can

calculate amount of heat produced or absorbed
in process from temperature change
q = ms∆T
= C∆T where ∆T = T final − Tinitial
CHEM1020 Insert
Chemical
section
Energetics
96
THE
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CHEM1020 Insert
Chemical
section
Energetics
97
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Example: Calculate heat transferred when an

iron bar of mass 869 g cools from 94°C to 5°C.
The specific heat of solid iron is 0.444 J/g⋅°C.
Solution:
q = 869 g × 0.444 J/(g ⋅ °C) × (5°C − 94°C)
= −34339 J
= −34.3 kJ
ie 34.3 kJ of heat is moved from the system

to surroundings.
CHEM1020 Insert
Chemical
section
Energetics
98
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Constant Pressure Calorimetry

06_74
Thermometer
“Coffee cup”
calorimeter
Styrofoam
cover
Styrofoam
cups
Stirrer
Useful for solution-phase reactions, eg

neutralisation, heat of solution, dilution etc
CHEM1020 Insert
Chemical
section
Energetics
99
THE
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Note: from definition of enthalpy, heat flow at

constant pressure is ∆H, so constant pressure
calorimetry measures ∆Hrxn directly
∆H = q P
Example: 400 mL of 0.600 M HNO3 is mixed

with 400 mL of 0.600 M NaOH in a constant
pressure calorimeter, having a heat capacity of
387 J/°C. The initial temperature of both
solutions is 18.88 °C. What is the final
temperature?
CHEM1020 Insert
Chemical
section
Energetics
100
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UEENSLAND
Solution: Need to use fact that
H + + OH − → H 2 O ∆H = −56.2 kJ
Can assume no heat lost to surroundings.

Hence
qsystem = qwater + qcalorimeter + qrxn
=0
ie qrxn = −(qwater + qcalorimeter )
= −(mwater s water ∆T + Ccalorimeter ∆T )
= − ∆T ( ms + C )
CHEM1020 Insert
Chemical
section
Energetics
101
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UEENSLAND
400 mL −1
We have × 0.600 mol L
1000 mL L−1
= 0.240 mol
qrxn = −56.2 kJ mol −1 × 0.240 mol
= −13.49 kJ
− qrxn
Now ∆T =
ms + C
13.49 × 10 3 J
=
800 g ⋅ 4.18 J/g ⋅ °C + 387 J/°C
= 3.62°C
CHEM1020 Insert
Chemical
section
Energetics
102
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UEENSLAND
Finally ∆T = Tfinal − Tinitial

∴ Tfinal = Tinitial + ∆T
= 18.88°C + 3.62°C
= 22.50°C
CHEM1020 Insert
Chemical
section
Energetics
103
THE
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UEENSLAND
Constant Volume (Bomb) Calorimetry
Ideal for study of combustion.

06_75
Ignition
wires Thermometer
Stirrer
Insulating
container
Steel
bomb
Reactants
Water in sample
cup
CHEM1020 Insert
Chemical
section
Energetics
104
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UEENSLAND
As in previous example, we assume no heat is lost

to the surroundings during measurement, hence
qsystem = qwater + qbomb + qrxn

= qcalorimeter + qrxn
=0
∴ qrxn = − qcalorimeter
= −Ccalorimeter ∆T
CHEM1020 Insert
Chemical
section
Energetics
105
THE
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UEENSLAND
Usually a substance of known heat output is used

to calibrate the calorimeter, so the exact volume
of water is unimportant.
Heat measured this way is not ∆H, since constant

volume, not constant pressure.
We showed earlier that under conditions of

constant volume, measured heat flow equals
internal energy change:
∆E = q v
CHEM1020 Insert
Chemical
section
Energetics
106
THE
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UEENSLAND
Example:
Combustion experiments were carried out in

excess oxygen in a bomb calorimeter with a heat
capacity of 11.3 kJ/°C. When burning a 1.5 g
sample of methane, a 7.3°C temperature increase
was observed. When burning a 1.15 g sample of
hydrogen, a 14.3°C temperature increase was
found.
Calculate the heat of combustion (per gram) for
hydrogen and methane.
CHEM1020 Insert
Chemical
section
Energetics
107
THE
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UEENSLAND
Solution: Energy released in the combustion of

1.5 g methane:
qrxn = -(11.3 kJ/°C)(7.3°C) = -83 kJ (= ∆E)
For 1g:
qrxn = -83 kJ/1.5 g = -55 kJ g-1
Why? Because:
qsys = qrxn + qcalorimeter = 0

∴ qrxn = − qcalorimeter
= −Ccalorimeter ∆T
CHEM1020 Insert
Chemical
section
Energetics
108
THE
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Solution continued: Energy released in the

combustion of 1.15 g hydrogen:
qrxn = -(11.3 kJ/°C)(14.3°C) = -162 kJ
For 1g:
qrxn = -162 kJ/1.15 g = -141 kJ g-1
So hydrogen is theoretically a better heat source
Note the sign: negative sign of heat of combustion

means that the reaction is exothermic
Equilibrium
CHEM1020 Insert
Chemical
section
Energetics
109
THE
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Chemical Equilibrium
Zumdahl Chapter 13
Consider N2O4(g) in sealed
tube - begins to dissociate to
NO2(g), which in turn
recombines back to N2O4(g)
From Chang, Chemistry, 4th Edn, McGraw Hill, 1991

CHEM1020 Insert
Chemical
section
Energetics
110
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Eventually rate of forward reaction equals that of

reverse reaction - chemical equilibrium
N 2O 4 ( g ) 2NO 2 ( g )
After concentrations have stopped changing, find

that:
[NO 2 ] = 4.6 ×10−3
2
[N 2O 4 ]
regardless of starting concentrations. This
ratio is known as the equilibrium constant, K.
CHEM1020 Insert
Chemical
section
Energetics
111
THE
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UEENSLAND
Most reactions are reversible to some extent.

In general, for
aA + bB cC + dD
[C ]c [ D ]d
K=
[ A ]a [ B]b
Note: 1. [A] refers to the equilibrium

concentration of A in mol L-1.
2. K is dimensionless.
3. Equilibrium is a dynamic process
CHEM1020 Insert
Chemical
section
Energetics
112
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What information does value of K give?
Magnitude of K gives information as to

position of equilibrium.
K >> 1 ⇒ products favoured
K << 1 ⇒ reactants favoured
K≅1 ⇒ equilibrium concentrations

will be comparable
CHEM1020 Insert
Chemical
section
Energetics
113
THE
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Examples
1. 2O 3 ( g ) 3O 2 ( g )
K=
[O2 ]
3
= 2.54 × 1012
[O 3 ]2
If, at equilibrium [O 2 ] = 1.0 M , then
[O
[O 3 ]2 = 2 ]3
= 3.94 × 10 −13
K
and [O 3 ] = 6.3 × 10 −7 M
CHEM1020 Insert
Chemical
section
Energetics
114
THE
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2. Cl 2 ( g ) 2Cl( g )
K=
[Cl]
2
= 1.4 × 10 −38
[Cl 2 ]
If the equilibrium concentration of Cl2 is 1.0 M,
[Cl] = 1.2 × 10 −19 M
CHEM1020 Insert
Chemical
section
Energetics
115
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3. CO( g ) + H 2 O( g ) H 2 ( g ) + CO 2 ( g )
K=
[H 2 ][CO 2 ]
= 5.10
[CO][H 2 O]
Equilibrium concentrations of reactants

and products will be comparable.
CHEM1020 Insert
Chemical
section
Energetics
116
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Notes: 1. If the direction in which the equation is

written is reversed, K is inverted.
2. Value of K changes if equation is

balanced differently
e.g. (i) 2O 3 ( g ) 3O 2 ( g )
(ii) 2
3 O3 ( g ) O2 ( g )
1
K ii =
[O2 ]  [O 2 ]3 
=
3
= K
1
 3
[O 3 ]
2
3 [O
 3  ]2 i
CHEM1020 Insert
Chemical
section
Energetics
117
THE
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Example – the Haber Process

N 2 ( g ) + 3H 2 ( g ) 2 NH 3 ( g )
At 127ºC the following equilibrium concentrations

were found:
[H2] = 3.1x10-3 M [NH3] = 3.1x10-2 M
[N2] = 8.5x10-1 M
Calculate the value of K at 127ºC for this reaction.
K=
[NH 3 ]
=
(3.1× 10 )
2 −2 2
= 3 . 8 × 10 4
[N 2 ][H 2 ]3 (8.5 ×10−1 )(3.1×10−3 )3

CHEM1020 Insert
Chemical
section
Energetics
118
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Calculate the value of the equilibrium

constant at 127ºC for the reaction:
2 NH 3 ( g ) N 2 ( g ) + 3H 2 ( g )
K′ =
[N 2 ][H 2 ]
3
=
1
=
1
= 2 . 6 × 10 −5
[NH 3 ]2
K 3.8 × 10 4
CHEM1020 Insert
Chemical
section
Energetics
119
THE
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Calculate the value of the equilibrium

constant at 127ºC for the reaction:
1
2 N 2 ( g ) + 32 H 2 ( g ) NH 3 ( g )
1
K ′′ =
[ NH 3 ]  [NH 3 ]2 
=  
2
3  (xa)b = xab
[N 2 ] [H 2 ]  [N 2 ][H 2 ] 
1 3
2 2
( )
1 1
K ′′ = K = 3.8 × 10
2 4 2
= 1.9 × 10 2
CHEM1020 Insert
Chemical
section
Energetics
120
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Equilibrium Involving Pressures
Where gases are involved, the equilibrium constant

can be expressed either in terms of concentrations,
or in terms of the partial pressures of the gases.
2O 3 ( g ) 3O 2 ( g )
K P = PO32 / PO23
Usually use standard state of 1 atm, so pressures

expressed in units of atmospheres, and equilibrium
constants quoted with no dimensions.
CHEM1020 Insert
Chemical
section
Energetics
121
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UEENSLAND
How are K and KP related?
n P
Since concentration is =
V RT
K=
[O2 ]
3
=
( ) PO 2 3
RT
=
KP
[O 3 ]2
( ) PO3
RT
2
RT
or K P = K ( RT ) ∆n
where ∆n is change in moles of gas on going

from reactants to products
CHEM1020 Insert
Chemical
section
Energetics
122
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Example
Calculate the value of KP for the following
reaction at 300°C, when K = 9.60
N 2 ( g ) + 3H 2 ( g ) 2 NH 3 ( g )
Solution
Change in number of moles of gas is
∆n = 2 − (1 + 3) = −2 mol
T = 300 + 273 = 573 K
We use: K P = K ( RT ) ∆n
CHEM1020 Insert
Chemical
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UEENSLAND
Note that because K uses mol L-1 and KP uses atm,

the correct value for R is 0.0826 L atm mol-1 K-1
K P = K ( RT ) ∆n = (9.60) ⋅ (0.08206 × 573) −2

9.60 −3
= = 4 .34 × 10
(0.08206 × 573) 2
CHEM1020 Insert
Chemical
section
Energetics
124
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Heterogeneous Equilibria
If all substances are in the same phase (eg gas,
solution etc) we term it a homogeneous
equilibrium.
If substances in more than one phase are involved,
we call it heterogeneous equilibrium.
The position of a heterogeneous equilibrium does

not depend on the amounts of pure solid or pure
liquid present because their concentrations
cannot change.
CHEM1020 Insert
Chemical
section
Energetics
125
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CaCO 3 ( s ) CaO( s ) + CO 2 ( g )
K′ =
[CO 2 ][CaO] = [CO 2 ]C1 ; K=
K ′ ⋅ C2
= [CO 2 ]
[CaCO3 ] C2 C1
The constants are incorporated into the expression for K
CHEM1020 Insert
Chemical
section
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126
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UEENSLAND
Another example:
(NH4)2Se (s) 2NH3 (g) + H2Se (g)
We would write the equilibrium constant as:
K′ =
[NH 3 ] [H 2Se]
2
[(NH 4 )2 Se]
but because (NH4)2Se is a solid, its “concentration”
doesn’t change as the amount of solid changes.
CHEM1020 Insert
Chemical
section
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127
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K′ =
[NH 3 ] [H 2Se]
2
[(NH 4 )2 Se]
=
[NH 3 ] [H 2Se]
2
K = [NH 3 ] [H 2Se]
2
So where K = K′⋅C
Same applies to pure liquids.
CHEM1020 Insert
Chemical
section
Energetics
128
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Using the Equilibrium Constant

Knowing the equilibrium constant, we can
calculate equilibrium concentrations of reactants
and products from any initial state:
Example:
At a particular temperature, K = 54.3 for the
reaction:
H2 (g) + I2 (g) 2HI (g)
If the initial concentrations of both H2 and I2 are

0.50 M, what are the equilibrium concentrations of
each gas involved?
CHEM1020 Insert
Chemical
section
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Solution:
The concentrations of both reactants will have
decreased by the same amount (call it x) at
equilibrium, and the concentration of HI will be 2x.
Hence:
H2(g) + I2(g) 2HI (g)

Initial: 0.50 0.50 0.00
Change: -x -x +2x
Eqbm: (0.50 – x) (0.50 – x) 2x
CHEM1020 Insert
Chemical
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The equilibrium constant is given by:
[ HI ]2
K=
[H 2 ][I 2 ]
so 54.3 =
(2x)
2
(0.50 − x )(0.50 − x )
Solve for x (take square root of both sides), to

give x = 0.39 M.
CHEM1020 Insert
Chemical
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So the equilibrium concentrations are:
[H2] = (0.50 – 0.39) M = 0.11 M

[I2] = (0.50 – 0.39) M = 0.11 M
[HI] = 2 × 0.39 M = 0.78 M
CHEM1020 Insert
Chemical
section
Energetics
132
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Factors Affecting Equilibrium

Small changes in conditions may change the
position of equilibrium.
Le Chatelier’s Principle
“If a change is imposed on a system at
equilibrium, the position of equilibrium will shift
in a direction that tends to reduce the change.”
Such changes could be concentration, pressure,

volume, temperature.
CHEM1020 Insert
Chemical
section
Energetics
133
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Changes in Concentrations
Example:
FeSCN 2+ ( aq) Fe 3+ ( aq) + SCN − ( aq)
Addition of NaSCN leads to increase of [SCN-]. Find that

[FeSCN2+] increases and [Fe3+] decreases to offset the
change.
Addition of oxalate ions, C2O42-, which bind Fe3+ ions,
leads to a decrease in the concentration of FeSCN2+ and
increase in [SCN-].
Note that the value of K doesn’t change (if

temperature is constant)
CHEM1020 Insert
Chemical
section
Energetics
134
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Changes in Volume or Pressure
Important if gases are involved.
Can change pressure in three ways:
1. Add or remove a gaseous reactant or product

2. Add an inert gas (eg helium)
3. Change the volume
CHEM1020 Insert
Chemical
section
Energetics
135
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Case (1): Changes the concentration, since

concentration = n/V, so treat as
before.
Case (2): No change in concentrations, so

position of equilibrium unaffected.
Case (3): Concentration of gaseous species

changes, but may or may not change
equilibrium.
CHEM1020 Insert
Chemical
section
Energetics
136
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Example:
N 2O4 ( g ) 2NO2 ( g )
What is the effect of decreasing the volume of

this system at equilibrium at constant
temperature?
Solution:
The concentration of both species increases.
System can offset change by moving to the side
with fewer moles of gases, ie left.
CHEM1020 Insert
Chemical
section
Energetics
137
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Consider reaction quotient, Q:
Q=
[NO 2 ]
2
(any conditions)
[N 2 O 4 ]
Initially, Q = K, but after the decrease in
volume, Q > K. System adjusts by decreasing
[NO2] and increasing [N2O4] until Q = K once
more.
Again, the value of K doesn’t change.
CHEM1020 Insert
Chemical
section
Energetics
138
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Effect of Temperature
If temperature is changed, the value of K changes.

Direction of change depends on ∆H
Example:
CoCl 2−
4 + 6H 2 O ( )2+
Co H 2 O 6 + 4Cl −
blue pink
Left to right reaction is exothermic.

Heating forces equilibrium to left, cooling to
right, ie heating favours an endothermic reaction
CHEM1020 Insert
Chemical
section
Energetics
139
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Phase Equilibria
Zumdahl, Sections 10.8, 10.9
Condensed Phases
We saw earlier that if forces between

molecules (intermolecular forces) are
sufficiently strong, they form condensed
phases (liquid, solid)
Phase changes involve material moving from

one phase (solid, liquid, vapour) to another.
CHEM1020 Insert
Chemical
section
Energetics
140
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Phase Changes
What happens as a solid is heated?
10_247
140
Steam
120
Water and steam
100
Temperature (°C)
80
Phase
60
Water equilibrium
40
Ice and
occurs here
20 water
0
Ice
– 20
Time From Zumdahl 4th
Edn
CHEM1020 Insert
Chemical
section
Energetics
141
THE
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Liquid-Vapour Equilibrium
When a liquid is placed in a closed container,
pressure increases, then levels out and remains
constant - increased pressure due to
vaporisation.
Eventually rate of vaporisation equals rate of
condensation. Pressure is then equilibrium
vapour pressure.
CHEM1020 Insert
Chemical
section
Energetics
142
THE
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Equilibrium
CHEM1020 Insert
Chemical
section
Energetics
143
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Vapour pressure is temperature dependent, since fraction

of molecules with sufficient kinetic energy to escape liquid
increases with temperature.
1 atm
1 torr = 1 mm Hg
How can we explain this behaviour?
CHEM1020 Insert
Chemical
section
Energetics
144
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Phase equilibria are special cases of

heterogeneous equilibria. Hence if we know
how the equilibrium constant changes with
temperature, we know how the vapour pressure
changes.
Temperature Dependence of Equilibrium

Constant
∆H
ln K P = − + constant
RT
CHEM1020 Insert
Chemical
section
Energetics
145
THE
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For one mole of liquid changing to one mole of gas:
A(l) A(g)
K P = PA( g )
− ∆H vap  1  Clausius-
hence ln PA =  +C Clapeyron
R T  Equation
where ∆H vap = enthalpy of vaporisation,

= energy required to vaporise one
mole of the liquid
C = a constant
CHEM1020 Insert
Chemical
section
Energetics
146
THE
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− ∆H vap  1 
ln PA =  +C
R T 
This implies that a plot of ln PA against 1/T should
be a straight line:
Slope = -∆Hvap/R
ln PA
1/T
CHEM1020 Insert
Chemical
section
Energetics
147
THE
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UEENSLAND
∆H vap increases as intermolecular forces increase:
Boiling point (temperature at which vapour

pressure equals external pressure) also increases.
CHEM1020 Insert
Chemical
section
Energetics
148
THE
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The other way to use the equation is to relate P at

two temperatures:
If at temp. T1 we have P1 and at temp. T2, P2, then
− ∆H vap  1 
ln P1 =   + C
R  T1 
− ∆H vap  1 
ln P2 =   + C
R  T2 
Subtract second equation from first:

CHEM1020 Insert
Chemical
section
Energetics
149
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− ∆H vap  − ∆H vap 
ln P1 − ln P2 = −  
RT1  RT2 
P1 ∆H vap 1 1
i.e. ln =  − 
P2 R  T2 T1 
Can be used to determine P at a second

temperature if ∆H vap is known, or to calculate ∆H vap
if vapour pressure measured at two
temperatures.
CHEM1020 Insert
Chemical
section
Energetics
150
THE
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Example:
The vapour pressure of water at 25ºC is 3.17 kPa,
and the enthalpy of vapourisation of water is 43.9
kJ mol-1. Calculate the vapour pressure at 50ºC.
Solution:
P1 = 3.17 kPa P2 = ?
T1 = 298 K T2 = 323 K
 3.17 kPa  43.9 × 10 3 J mol −1  1 1 

ln  = −1 −1 
 − 
 P2  8.314 J K mol  323 K 298 K 
= −1.37
CHEM1020 Insert
Chemical
section
Energetics
151
THE
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3.17 kPa
Hence = e −1.37 = 0.254
P2
3.17 kPa
so P2 = = 12.5 kPa
0.254
P increases as expected.
CHEM1020 Insert
Chemical
section
Energetics
152
THE
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UEENSLAND
Solid-Liquid Equilibrium
What happens as a solid is heated? Typically
melts to liquid. Melting point is temperature at
which solid and liquid phases coexist in
equilibrium. 10_247
140
Steam
120
Water and steam
100
Temperature (°C)
80
60
Water
40
Ice and
20 water
0
Ice
– 20
Time
Temperature remains constant while two

phases coexist.
CHEM1020 Insert
Chemical
section
Energetics
153
THE
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UEENSLAND
Energy required to melt one mole of solid: molar

enthalpy of fusion, ∆H fus
Supercooling
Very pure water can be cooled to -42°C without
freezing (supercooled). If cooled very quickly to
liquid N2 temperature it forms “amorphous ice”.
CHEM1020 Insert
Chemical
section
Energetics
154
THE
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UEENSLAND
Extent of
supercooling
When crystallisation starts energy is released since the process l → s

is exothermic
CHEM1020 Insert
Chemical
section
Energetics
155
THE
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Solid-Vapour Equilibrium
Solids also have vapour pressures. Some

substances sublime under normal circumstances,
eg naphthalene, iodine, carbon dioxide.
Energy required to sublime 1 mole of solid: molar
enthalpy of sublimation, ∆H sub
By Hess’ Law,
∆H sub = ∆H fus + ∆H vap
CHEM1020 Insert
Chemical
section
Energetics
156
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Phase Diagrams
These describe the conditions under which a
substance is in a pure phase, eg water
10_252
Critical
point Solid lines: 2
Pc = 218 phases can exist in
Pressure (atm)
Solid Liquid equilibrium

eg solid/liquid line
1.00
P3 = 0.0060
Gas passes through 0ºC,
Triple
point
1 atm.
Tm T3 Tb Tc
0 0.0098 100 374 From Zumdahl 4th Edn
Temperature ( ° C)
CHEM1020 Insert
Chemical
section
Energetics
157
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Heating experiments:
10_252
Critical
1. Heat from 1 atm Pc = 218

point
pressure, -20ºC. Goes
Pressure (atm)
Solid Liquid
through liquid phase 1.00 Gas
to vapour.
P3 = 0.0060
Triple
point
2. Repeat with pressure Tm T3 Tb Tc
0.003 atm, -20ºC. 0 0.0098

Temperature ( ° C)
100 374
Sublimes at -10ºC.
3. Use pressure of 0.006 atm. At 0.0098ºC, three
phases in equilibrium - triple point. Both liquid
and solid have identical vapour pressure of 0.006
atm at this temperature.
CHEM1020 Insert
Chemical
section
Energetics
158
THE
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UEENSLAND
Above 374ºC water cannot be liquified at any

pressure. Called critical temperature, Tc.
Pressure required to liquify substance at Tc.
called critical pressure, Pc (= 218 atm for
water)
Hence, if heat at 225 atm from 300ºC, liquid

changes to vapour through fluid region
(neither liquid nor gas).
CHEM1020 Insert
Chemical
section
Energetics
159
THE
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UEENSLAND
CHEM1020 Insert
Chemical
section
Energetics
160
THE
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Applications of Phase
Diagrams
1. Ice skating
Solid/liquid boundary for water

has negative slope - opposite to
most substances (eg CO2).
Thin blade produces high

pressure at constant temp., so
solid/liquid boundary crossed,
giving lubricating layer between
blade and ice.
CHEM1020 Insert
Chemical
section
Energetics
161
THE
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UEENSLAND
At high pressure volume can

be reduced by melting
CHEM1020 Insert
Chemical
section
Energetics
162
THE
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2. Boiling and pressure
Shape of liquid/vapour boundary actually

Clausius-Clapeyron equation (lnP vs 1/T).
As pressure decreases, boiling point decreases.

Hence water boils at 70ºC on Mount Everest.
3. Sublimation of carbon dioxide
Phase diagram of CO2 → liquid occurs only above

1 atm pressure. At 1atm, CO2 sublimes at -78ºC.
CHEM1020 Insert
Chemical
section
Energetics
163
THE
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UEENSLAND
10_255
Critical
point
Pc =
72.8
Liquid
Pressure (atm)
Solid
P3 =
5.1
Gas
Triple
point
1.00
Tm T3 Tc
– 78 – 56.6 31
Temperature (°C)
From Zumdahl 4th

Carbon dioxide phase diagram Edn
CHEM1020 Insert
Chemical
section
Energetics
164
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Properties of Solutions
Zumdahl, Sections 11.1, 11.3-11.6
Solution - homogeneous mixture of two or more

substances.
Six types of solutions are possible:
Example State of State of Solute State of Solvent
Solution
Air, natural gas Gas Gas Gas

Vodka in water, Liquid Liquid Liquid
Antifreeze
Brass Solid Solid Solid
Carbonated Liquid Gas Liquid
water (soda)
Seawater, sugar Liquid Solid Liquid
Solution
Hydrogen in Solid Gas Solid
platinum
Driving forces are entropy (randomness) and enthalpy.

CHEM1020 Insert
Chemical
section
Energetics
165
THE
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UEENSLAND
Concentration Units
Solution concentration can be described in

many ways - choice depends on usefulness.
Percent by mass
Defined as:
mass of solute
percent by mass = × 100%
mass of solution
CHEM1020 Insert
Chemical
section
Energetics
166
THE
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Mole fraction (χ)
moles of A
Mole fraction of A = χ A =
sum of moles of all components
χ has no units since it is ratio of like quantities
Molarity (M)
moles of solute
molarity = mol L-1
litres of solution
CHEM1020 Insert
Chemical
section
Energetics
167
THE
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Molality (m)
Number of moles of solute dissolved in 1 kg of

solvent
moles of solute
molality =
mass of solvent (kg)
CHEM1020 Insert
Chemical
section
Energetics
168
THE
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Conversions between units

Example:
What is the molarity of a solution of 8.00%
cadmium nitrate (F.M. = 236.4 amu) by mass?
The density of the solution is 1.08 g/mL.
Solution:
Suppose you had 1 litre of the solution. It
would weigh 1080 g, and so from the definition
of percentage by mass, the mass of cadmium
nitrate is (8.00/100) x 1080 g = 86.4 g.
mass of solute
percent by mass = × 100%
mass of solution
CHEM1020 Insert
Chemical
section
Energetics
169
THE
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This corresponds to
86.4 g
−1
= 0.365 mol of cadmium nitrate
236.4 g mol
in 1 L of solution. The concentration expressed

as a molarity is therefore 0.365 mol L-1.
moles of solute
molarity =
litres of solution
CHEM1020 Insert
Chemical
section
Energetics
170
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Factors Affecting Solubility
Solubility: maximum amount of solute that will

dissolve in a given amount of solvent at specific
temperature (heterogeneous equilibrium)
Molecular Structure
Polar solvent/polar solute or nonpolar
solvent/nonpolar solute favoured
eg hexane (C6H14) is better solvent for grease

(C20H14) than methanol (CH3OH)
CHEM1020 Insert
Chemical
section
Energetics
171
THE
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Solubility of vitamins
Hydrophobic Hydrophilic
Fat soluble: A, D, E, K Water soluble: B, C
CHEM1020 Insert
Chemical
section
Energetics
172
THE
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Temperature
- Solutions of solids in
water
Solubility normally
increases with
increasing temperature
(with exceptions)
CHEM1020 Insert
Chemical
section
Energetics
173
THE
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UEENSLAND
Not simply related to ∆H soln
CaCl 2 ∆H soln < 0

NH 4 NO3 ∆H soln > 0
but both are more soluble at elevated temperature.
∆H soln Enthalpy change of solution (dissolving 1

mol of solute)
CHEM1020 Insert
Chemical
section
Energetics
174
THE
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- Solutions of gases in
water
Gas solubility decreases
with increasing
temperature (all gases
dissolve exothermically).
(example - bubbles form
in heated water)
CHEM1020 Insert
Chemical
section
Energetics
175
THE
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Consequences -
• thermal pollution of lakes
• scale formation in boilers, kettles:
CO32− (aq) + CO2 (aq) + H 2O(l ) 2 HCO3− (aq)
Heating drives CO2 off, leading to more

carbonate which reacts with dissolved Ca2+ to
form CaCO3(s).
CHEM1020 Insert
Chemical
section
Energetics
176
THE
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Pressure
Solubility of solids and liquids not affected by

pressure. For gases, though, higher pressure
leads to higher solubility:
c = k·P Henry’s Law
k is constant for a given solution at a given

temperature.
The amount of gas dissolved in a solution is
directly proportional to the pressure above the
solution.
CHEM1020 Insert
Chemical
section
Energetics
177
THE
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Example
cCO2 = kCO2 PCO2
For CO2,
At 25°C, kCO2 = 0.0313 mol L−1 atm −1
If a soft drink is bottled at 5 atm pressure, and

the partial pressure of CO2 in the atmosphere is
4 × 10-4 atm, what is concentration in solution
before and after opening bottle?
CHEM1020 Insert
Chemical
section
Energetics
178
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UEENSLAND
Solution
Unopened: cCO2 = 0.0313 mol L−1 atm −1 × 5 atm

= 0.16 mol L−1
Opened: cCO2 = 1.2 × 10−5 mol L−1
Note: Henry’s Law not obeyed when a reaction

occurs,
HCl( g ) H

2O
→ H + ( aq) + Cl − ( aq)
CHEM1020 Insert
Chemical
section
Energetics
179
THE
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Colligative Properties
Presence of solute affects properties of solvent.
Four related effects:
•vapour pressure lowering

•boiling point elevation
•freezing point depression
•osmotic pressure
Each depends only on the number of solute

particles, not on nature of particles - colligative
properties.
CHEM1020 Insert
Chemical
section
Energetics
180
THE
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Eg, a solution of glucose (mole fraction 0.01)

has same vapour pressure, Tb, Tm as solution of
sucrose of same mole fraction.
CHEM1020 Insert
Chemical
section
Energetics
181
THE
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The vapour pressure of solutions

An experimental observation:
The vapour pressure of pure water is greater than that

of the solution.
CHEM1020 Insert
Chemical
section
Energetics
182
THE
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Vapour Pressure Lowering

Pure H2O at 40°C has v.p. of 7.3 kPa
0.1 M solution of NaCl has v.p. of 5.8 kPa
Raoult’s Law (for nonvolatile solute):
Psoln = xsolvent Psolvent

0
0
Psolvent is vapour pressure of pure solvent
CHEM1020 Insert
Chemical
section
Energetics
183
THE
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UEENSLAND
Vapour
pressure of
Psoln pure solvent
0 xsolvent 1
CHEM1020 Insert
Chemical
section
Energetics
184
THE
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Example: Calculate vapour pressure of solution

prepared by dissolving 5.00 g of sucrose
(C12H22O11)(MW=342.3) in 100 g water at 100°C.
Solution: Moles sucrose = 0.0146 mol

Moles water = 5.549 mol
5.549 mol
x H 2O = = 0.9973
5.549 mol + 0.0146 mol
Psoln = xsolvent Psolvent

0
Psoln = 0.9973 × 101.3 kPa = 101.0 kPa

(Note: Pwater @ 100ºC is 1 atm = 101.3 kPa)
CHEM1020 Insert
Chemical
section
Energetics
185
THE
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Example: Calculate vapour pressure of solution

prepared by dissolving 35.00 g of Na2SO4 (MW 142
g/mol) in 175 g water at 100°C.
Solution: Moles Na2SO4 = 0.246 mol
Moles water = 9.72 mol
When the material is a salt take into account that upon

dissolving ions are produced: Na2SO4 → 2Na+ + SO42-
Moles solute = 3 × 0.246 mol = 0.738 mol

9.72 mol
xH 2 O = = 0.929
9.72 mol + 0.738 mol
Psoln = 0.929 × 101.3 kPa = 94.1 kPa

CHEM1020 Insert
Chemical
section
Energetics
186
THE
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Solutions of Two Volatile Components
If Raoult’s Law obeyed, vapour pressure is the

sum of the vapour pressures of components.
For binary solution of A and B:

Psoln = PA + PB
= x A PA0 + x B PB0
Solutions which obey this are ideal (no real

solution is ideal, but some are close).
CHEM1020 Insert
Chemical
section
Energetics
187
THE
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UEENSLAND
Vapour
pressure of
pure B Psolution
PB Vapour
pressure of
Pressure
pure A
PA
0 xA 1
1 xB 0
CHEM1020 Insert
Chemical
section
Energetics
188
THE
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UEENSLAND
Solutions of very similar compounds can

approach ideal behaviour, eg:
CH3
benzene toluene
Interaction between benzene and benzene,

between toluene and toluene, and between
benzene and toluene are very similar.
CHEM1020 Insert
Chemical
section
Energetics
189
THE
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If solute & solvent interact more strongly with each

other than they do with themselves, then:
• the process is exothermic ∆H soln < 0
• tendency for solvent molecules to escape is
lower
• vapour pressure is lower than expected
→ negative deviations
If mixing is not effective, then:

• the process is endothermic ∆H soln > 0
• tendency for solvent molecules to escape is
higher
• vapour pressure is higher than expected
→ positive deviations
CHEM1020 Insert
Chemical
section
Energetics
190
THE
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11_279
Vapour pressure for a solution of two
volatile liquids
Vapor pressure
Vapor pressure of pure B of solution Vapor pressure
Va Vapor pressure of solution
Pa por pr
ess of pure A
Vapor pressure
rti ure
al
pr of s
es olu
su tion
re
B
re A
r essu
l p
rtia
Pa
χA χA χA
χB χB χB
(a) (b) (c)
Ideal solution Ptotal larger than Ptotal smaller than

calculated for calculated for
Raoult’s law Raoult’s law
From Zumdahl 4th Edition, © Houghton Mifflin
CHEM1020 Insert
Chemical
section
Energetics
191
THE
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Boiling Point Elevation
Since an involatile solute lowers the vapour

pressure, boiling occurs at higher temperature.
∆Tb = Tb − Tb0
where Tb = boiling point of solution

Tb0 = boiling point of pure solvent
CHEM1020 Insert
Chemical
section
Energetics
192
THE
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UEENSLAND
Elevation of boiling point is proportional to

molality:
∆Tb ∝ m
= K b msolute
Kb = boiling point elevation constant

(°C kg mol-1)
(characteristic of solvent)
CHEM1020 Insert
Chemical
section
Energetics
193
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Freezing Point Depression
Solute lowers freezing point. ∆T f = T f0 − T f

= K f msolute
Kf = freezing point depression constant

(°C kg mol-1)
Example For H2O, Kb = 0.52 °C kg mol-1
Kf = 1.86 °C kg mol-1
A solution contains 1.00 kg of ethylene glycol

CH2OHCH2OH in 2.00 kg of water. Calculate the
boiling point and freezing point of the solution.
CHEM1020 Insert
Chemical
section
Energetics
194
THE
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UEENSLAND
Answer
16.13 mol
Molality = = 8.06 mol kg -1
2.00 kg
∆Tb = 0.52°C kg mol −1 ⋅ 8.06 mol kg −1 = 4.2°C
Hence solution will boil at 104.2ºC.
∆T f = 1.86°C kg mol −1 ⋅ 8.06 mol kg −1 = 15.0°C
Solution will freeze at −15ºC.
CHEM1020 Insert
Chemical
section
Energetics
195
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Osmotic Pressure
Solvent molecules pass through a

semi-permeable membrane.
Pressure π required to stop osmosis
from occurring.
Osmotic pressure is given by:
π = MRT M = molarity of solution

R = gas constant
T = absolute temperature
CHEM1020 Insert
Chemical
section
Energetics
196
THE
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Solutions with identical osmotic pressure called

isotonic.
If unequal, one with higher concentration is
hypertonic, one with lower conc. is hypotonic.
Osmosis is important for:
•blood cells
•preservation of foods
•transpiration in trees
•intravenous solutions
•reverse osmosis
CHEM1020 Insert
Chemical
section
Energetics
197
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Use of Colligative Properties for Molar Mass

Calculations
Normally use osmotic pressure or freezing point
depression.
Example
1.00 × 10-3 g of a protein was dissolved in water and
made up to 1.00 mL. Osmotic pressure was found to
be 0.149 kPa at 25.0ºC. Calculate the molar weight
of the protein.
Answer
Use π = MRT and solve for M
CHEM1020 Insert
Chemical
section
Energetics
198
THE
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UEENSLAND
π 0149
. × 10 3 N m −2
M= = = 6.03 × 10 −2 mol m −3
RT 8.314 J K −1 mol −1 298 K
1J=1Nm
6.03 × 10 −2 mol m −3 = 6.03 × 10 −5 mol L-1
1 L contains 1.00 g ≡ 6.03 × 10-5 mol.
1.00 g +4
∴ MW= = 1.66 × 10 g mol -1
6.03 × 10−5 mol

If pressure given in atm use:
R = 0.08206 L atm K-1 mol-1
CHEM1020 Insert
Chemical
section
Energetics
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THE

Outline of this section of the course

The Gaseous State

Why are some substances gases at room

Elements in their pure state are mostly solids,

Another common pressure unit: atmosphere (atm)

The Gas Laws

Solution: Since PV = constant,

Note that the intercept of each line lies at

From above plot, V = bT

For changes in temperature from T1 to T2,

Avogadro postulated that at a given T and P, equal

Example: Suppose we have a 12.2 L sample

Answer: Equation is: 3O 2 (g) → 2O3 (g)

• Causes inflation in less than

Ideal Gas Law

PV = nRT Ideal Gas Equation

R: gas constant R = 8.314 J K −1 mol −1(SI)

The ideal gas law holds only for ideal gases,

No real gases obey it perfectly, but it’s good

Uses of Ideal Gas Equation

If one variable remains P1V1 P2V2

Example: A sample of diborane gas (B2H6) has a

P1 = 45.8 kPa P2 = 62.2 kPa

45.8 kPa ⋅ 3.48 × 10 −3 m3 ⋅ 309 K

Dalton’s Law of Partial Pressures

Often mixtures of gases, rather than pure

Dalton:the total pressure of a mixture of gases

i.e., if sample contains gases A and B, total

How does the pressure of one gas relate

xA is the mole fraction of A; xA: 0 → 1

and in general for component i Pi = x i PT

Liquids and Solids

Compared to gases, liquids and solids have high

The three states of matter

Intermolecular forces (between molecules) are

These are only important over short distances.

Hydrogen bonds are special

London dispersion (or van der Waals) forces

Why do non-polar atoms or molecules exist in

This results in a weak and short-lived interaction

Result is that the surface area stays as small as

Surface properties of liquids depend on balance

Structure exists in liquids, but hard to model.

Crystalline solids are

Constructive interference Destructive interference

When 2d sin θ is a multiple of the wavelength of the

Diffraction condition, Bragg’s law: 2d sin θ =n λ

Molecular solids (eg sucrose, ice)

Ionic solids (eg sodium chloride)

ABAB → hexagonal close

ABCA → cubic close

Metals have unique properties: high electrical and

“electron sea” model

Insulators are materials

Semiconductors (eg silicon) have a small gap,

Network Atomic Solids

Graphite: layers of fused six-

Silicates and Glasses

Silicates are based on a

Eg: borosilicate glass (Pyrex) contains B2O3 for thermal

Compositions of Some Common Types of Glass

Percentages of Various Components

Type of Glass SiO2 CaO Na2O B2O3 Al2O3 K2O MgO