Introductory Physical

Chemistry
Professor Scott Donne
P: (02) 4921 5477
E: scott.donne@newcastle.edu.au

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2
 TOPIC AREAS
3

• Lectures 1-3
– Gases and Their Properties
• The gas laws
• Ideal gas equation
• Applying gas laws to chemical reactions
• Behaviour of real gases

• Lectures 4-6
– Atomic Structure
• Electromagnetic radiation
• Early theories on electron properties
• Quantum mechanical view of the atom
• Shapes of atomic orbitals
 TOPIC AREAS
4

• Lecture 7
– Electron Configurations and Chemical Periodicity
• Electrons in atomic orbitals
• Electron configurations in atoms and ions
• Periodic trends in atomic properties

• Lectures 8-9
– Bonding and Molecular Structure
• Valence electrons and bond formation
• Ionic and covalent bonds
• Shapes of molecules
 TOPIC AREAS
5

• Lectures 10-12
– Principles of Reactivity: Chemical Equilibria
• What is equilibrium?
• Equilibrium constant
• Reaction quotient
• Le Chatelier’s Principle
Gases
6
 Characteristics of Gases
7

• Many elements and compounds exist as gases

– e.g., the atmosphere – 78% N2, 21% O2, 0.9% Ar

• Those that exist as liquids can be vaporized

– e.g., H2O, Hg

• Some compounds like CO2 can sublime

– i.e., solid to a gas directly

• Gases are the simplest state of matter

 Characteristics of Gases
8

• Unlike liquids and solids, they:

– Expand to fill their containers
– Are highly compressible
– Have extremely low densities
• Understood in terms of the behaviour of the
molecules that constitute the gas
• Easily modelled mathematically
• Only need to quantify pressure (P), volume (V),
temperature (T) and amount of gas (n) for a
complete description
 Pressure
9

• Pressure is the amount of force applied to an area

F
P=
A

• Atmospheric pressure is the weight of air per unit

of area
 The Barometer
10

• In 1643 Evangelista Torricelli invented the

barometer

The Mercury
Barometer

• At sea level, height of the mercury column in the

barometer was 760 mm
 The Barometer
11

• Blaise Pascal recognised that the barometer was

measuring the atmospheric pressure
 Units of Pressure
12

• Pascals F
– 1 Pa = 1 N/m2 P=
A
• Bar
– 1 bar = 105 Pa = 100 kPa
• mm Hg or Torr
– The difference in the heights in mm (h) of two
connected columns of mercury

• Atmospheric pressure
– 1.00 atm = 760 Torr (760 mm Hg)
 Manometer
13

• Used to measure the difference in pressure

between atmospheric pressure and that of a gas
in a vessel
 Standard Pressure
14

• Normal atmospheric pressure at sea level

• Corresponds to:
– 1.00 atm
– 760 Torr (760 mm Hg)
– 101.325 kPa

– 1.00 atm = 760 mm Hg = 760 Torr = 101.325 kPa

• Standard atmospheric pressure is now defined as

1 bar
– 1 bar = 100 kPa = 750.1 mm Hg = 0.987 atm
 Example
15

• A meteorological map shows pressure at 99.8 kPa.

What is the pressure in atm and mm Hg?
 The Gas Laws
16

• Experiments with a large number of gases reveal

that four variables are required to define the
state of a gas:
– Temperature (T)
– Pressure (P)
– Volume (V)
– Amount of gas (n; moles)
• Throughout the 1600-1800s a number of
scientists made observations of fundamental
relationships between these variables
• These observations became the Gas Laws
 Boyle’s Law – 1662
17

• The volume of a fixed quantity of gas at constant

temperature is inversely proportional to the
pressure

Robert Boyle
“gentleman scientist”
 Boyle’s Law
18

• Consider a piston
– As we increase the pressure upon a volume of gas that
volume is decreased
• i.e., we compress the gas

• Boyle noted that:

– “The volume of a fixed amount of gas at a given
temperature is inversely proportional to the pressure
exerted by the gas”
1 P1V1 = P2V2 = P3V3 ....
V∝
P
CB
V= or PV = CB
P
 Pressure and Volume
19

• Pressure and volume are inversely related

– A plot of P versus V results in a curve.
• Since CB
V= or PV = CB
P
• This means that a plot of V vs 1/P should be a
straight line, slope CB
 Boyle’s Law – Example
20

• A sample of air occupies 120 L at 1.3 atm. What

pressure is required to compress it to 45 L at the
same temperature?
 Charles’s Law - 1787
21

• Charles’ Law
– Charles discovered that:
• “The volume of a fixed quantity of gas at constant pressure
increases with increasing temperature.”
– Model hot air balloons

V∝T V
V = CC × T or = CC
T
V1 V2 V3
= = ...
T1 T2 T3
Jacques Charles
Charles the Balloonist
22

Charles made the first

flight of a hydrogen
balloon on August 27,
1783. This balloon was
destroyed by terrified
peasants when it
landed outside of
Paris.

Jacques Charles

V
V = CC × T or = CC
T
 Volume and Temperature
23

• The volume of a fixed amount of gas at constant

pressure is directly proportional to its absolute
temperature

V
= CC
T

• A plot of V versus T will be a straight line.

– Note that T must be in Kelvin
 The Kelvin Scale - 1846
24

• Kelvin Temperature Scale

– Lord Kelvin proposed a temperature scale in which a
Kelvin degree (SI unit) equals a Celsius degree, and
where 0 K = -273.15°C
– Must use Kelvin in gas laws.

William Thomson
Lord Kelvin
Charles’ Law
25
 Example
26

• A 262 L weather balloon is filled with He on an

18°C day. What is the volume of the balloon that
night, when the temperature is -10°C (the
atmospheric pressure is constant at 760 mm Hg)?
 General Gas Law
27

• Combination of Boyle’s and Charles’ Laws

– For a fixed quantity of gas:

1
V ∝ and V ∝ T
P
– Combining gives:

T PV
V ∝ or =C
P T
P1V1 P2V2 P3V3
= = ...
T1 T2 T3
 Example
28

• The weather balloon containing 236.8 L of He at

-10°C and 760 mm Hg is now released. What is the
volume at an altitude of 30 km, where the
pressure is 76 mm Hg and temperature -33°C?
 Gas Laws
29

• Gay-Lussac observed:
– “Ratios of volumes of gases in a
reaction, measured at constant
temperature and pressure, are small
whole numbers”

Joseph Louis Gay-Lussac

• Avogadro went further:

– “Equal volumes of gases under the
same temperature and pressure have
equal number of molecules”

V ∝n V = CAn
Amedeo Avogadro
 Avogadro’s Law - 1811
30

• The volume of a gas at constant temperature and

pressure is directly proportional to the number of
moles of the gas

• Mathematically, this means that

V = CAn
Avogadro’s Law
31
 Example
32

N2(g) + 3H2(g) → 2NH3(g)

• If we have 15.0 L of H2, how many litres of N2 are

required for complete reaction? What is the
volume of NH3 produced, assuming other
conditions remain constant?
 The Ideal Gas Law - 1834
33

• Combining 1
– Boyle’s Law V∝
P
– Charles’ Law V ∝T

– Avogadro’s Law V ∝n

• Gives
nT ⎛ nT ⎞
V∝ or V = R⎜ ⎟
P ⎝ P ⎠
– where R is known as the gas constant
 The Ideal Gas Law
34

PV = nRT

• Adequately describes the behaviour of gases at 1

atm or less and around room temperature

• The value of R is determined experimentally

– Units of R are critical
 Calculating R (Common Units)
35

• 1 mole of any gas under STP [Standard

Temperature (0°C) and Pressure (1 atm)] occupies
22.414 L (called the standard molar volume)

PV
Pressure (atm) R=
nT
Volume (L) 1.0 (atm) × 22.424 (L)
n in moles (mol) =
1.0 (mol) × 273.15 (K)
Temperatur e (K) = 0.0821 L atm K −1
mol −1
 Calculating R (SI Units)
36

• 1 mole of any gas under STP [Standard

Temperature (0°C) and Pressure (1 atm)] occupies
22.414 L (called the standard molar volume)

PV
R=
nT
P (Pa) 3 -3 3
101.325 × 10 (Pa) × 22.424 × 10 (m )
V (m3 ) =
1.0 (mol) × 273.15 (K)
n (mol) = 8.3143 m3 Pa K −1 mol−1
T (K) −1 −1
= 8.3143 J K mol
 Example
37

• What is the pressure inside a television picture

tube given that its volume is 5 L, its temperature
23°C and it contains 0.01 mg of N2?