Welcome to CHEM1000 Chemical Structure

Fall 2021

Professor: Dr. William Pietro

[email protected]

1
 Course Content

Gases (Chapter 5)
Thermochemistry (Chapter 6)
Atomic structure (Chapter 7)
Periodic properties (Chapter 8)
Chemical bonding (Chapters 9, 10)
Solids, liquids and intermolecular forces (Chapter 11)

2
 CHAPTER 5

Gases

3
Oxygen masks

“In the unlikely event of a sudden change in

cabin pressure….”

O2 not stored, but generated chemically by

the decomposition of sodium chlorate

2 NaClO3 (s) → 2 NaCl(s) + 3 O2 (g)

4
SI Units for Gases

• The SI unit for volume is:

− Common alternatives:

• The SI unit for temperature is:

− Common alternatives:

• The SI unit for amount of substance is:

• The SI unit for mass is:

− Common alternatives:
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Gas properties
• We will be looking at macroscopic and microscopic properties:
− Macroscopic
▪ Properties of bulk gases
▪ Observable
o Pressure, volume, mass, temperature…

− Microscopic
▪ Properties at the molecular level
▪ Not readily observable
o Mass of molecules, molecular speed, energy, collision frequency

Our aim is to look at the relationship between the macroscopic properties of a

gas and end up with the gas laws
6
Measuring Pressure

• What is pressure?
− Gaseous atoms or molecules exert a force when they collide with a
surface
− The total sum of these molecular collisions is pressure.

• The simplest way to measure gas pressure is to have it balance a

liquid pressure (due to gravity)

• A barometer is used to measure atmospheric pressure

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Barometer
• Tube closed at one end, fill with Hg, invert into a
pool of Hg
• Weight of Hg causes level in tube to drop until
PHg = Patm

Derivation:

𝑚𝐻𝑔 × 𝑔
𝑃𝐻𝑔 =
𝐴
𝑉𝐻𝑔 × 𝑑 × 𝑔
𝑃𝐻𝑔 =
𝐴

𝑃𝐻𝑔 = ℎ × 𝑑 × 𝑔

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Polling Question
Barometers don’t have to use mercury. If an identical barometer is
constructed but uses water instead, how will the height of the water
column compare to the mercury one?

Patm = hdg

A) The water height will be higher than the mercury height

B) The water height will be the same as the mercury height
C) The water height will be lower than the mercury height

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Atmospheric Pressure
• The average pressure at sea level will support a column of 760
mm of mercury.

• This is the definition of the pressure unit of “atmospheres”

1 atm = 760 mmHg

• Also the unit mm Hg has become known as Torr (after Torricelli)

1 atm = 760 Torr

• But this is not the SI unit for pressure!

10
The Pascal
• The SI unit for pressure is the Pascal (Pa) 1 Pa = 1 N/m2

• 1 Pa is a small amount of pressure, so using kPa is more common

• It can be shown that 1 atm = 101325 Pa ≈ 101.3 kPa

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The Bar
• Yet another common pressure unit, mainly used instead of atm
these days

• 1 bar is defined as:

• How many atm in 1 bar?

12
Standard Pressure
The International Union of Pure and Applied Chemistry
(IUPAC) has defined standard pressure as exactly 1 bar.

13
Let’s work a problem
Aircraft tires operate at high pressures: 13.8 bar on average. What is this
pressure in kPa and in atm?
Measuring Gas Pressures
Gas pressures can be measured with a manometer, which measures pressure
differences using a liquid (usually Hg)

15
Polling question
In which of the figures below is the pressure in the gas bulb greater than
atmospheric pressure?

A) B) C)

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Gas Laws

• The aim is to determine the relationship between the gas

observables (pressure, volume, moles, temperature).

• These were determined experimentally

• Later, kinetic molecular theory attempts to explain these laws

using molecular scale assumptions

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Boyle’s Law: Volume and Pressure (n & T constant)
Boyle (~1622) studied the effect of changing pressure on a sample of
gas on its volume while keeping its temperature constant

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Boyle’s Law
• Boyle found that pressure and volume were inversely proportional.
(double the pressure and the volume goes to one half).

• How do we express this mathematically?

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Charles’s Law: Volume and Temperature
• Charles was one of the first people to ascend in a
hydrogen-filled balloon

• Charles found that the volume of the balloon was

directly proportional to the absolute temperature
(i.e. V a T)

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Charles’s Law
Volume and temperature are linearly related.

The Kelvin temperature scale is:

How do we express Charles’s Law

mathematically?

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What about this situation?
According to Charles’ Law, volume increases with temperature.

What happens if the gas is in a rigid container that can’t expand or contract?

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Avogadro’s Law: Volume and Moles (T & P constant)
The amount of gas (n) is directly
proportional to its volume (V)

Vn

This assumes the following

stays constant:

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Ideal Gas Law
Let’s combine Boyle’s Law, Charles’s Law and Avogradro’s Law to
develop a general expression that relates P, T, n and V!

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Ideal Gas Constant
R = 8.314 J mol-1 K-1 (SI) but what are the units of P, V, n and T we
need to use? Why is the joule unit present?

Other values of R = 0.0821 L atm mol-1 K-1

= 0.0831 L bar mol-1 K-1
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Ideal Gas Constant
IMPORTANT TIP: The value of R you use to solve problems depends
on the units! Dimensional analysis is your friend!

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Other useful forms of the ideal gas law
PV = nRT

This equation can be reorganized to solve for any individual variable:

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Other useful forms of the ideal gas law
Other forms of the ideal gas law can be produced by substituting
equations for n, P, V, etc.

What if we know the mass of the gas?

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Other useful forms of the ideal gas law
What about the densities of gases (mass per volume)?

29
Polling question
Without doing detailed calculations, which of the following gases has the
greatest density if they are at the same temperature and pressure?

A) O2
B) N2
C) Kr
D) CH4
E) C3H6

30
Applications of the Ideal Gas Law
Molar Volume
• The volume occupied by one mole of a substance is its molar volume. This
will be constant for any fixed temperature and pressure.
• Usually specified at STP conditions

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Let’s work a problem
A sample of gas has a mass of 0.311 g. Its volume is 0.225 L at a
temperature of 55°C and a pressure of 886 torr. Find the molar mass of
the gas (in g/mol).

32
Mixtures of Gases and Partial Pressures

• Many gases are not pure but are actually a mixture of

gases

• Dry air is a mixture of many gases (N2, O2 , Ar, CO2, etc.)

• Each gas in the mixture acts independently, they do not

interact.

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Mixtures of Gases and Partial Pressures

• The following is the percent composition of our atmosphere:

Gas Percentage

N2

O2

Ar

• But percentages according to what? mass? moles?

pressure?
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Dalton’s Law of Partial Pressures
• It turns out percentages (fractions) by pressure or moles are
essentially the same!

• If we assume gas molecules don’t interact or react with each

other, then individual parameters can be added together to give
the overall sum

Example: For our atmosphere,

nT =

35
Dalton’s Law of Partial Pressures
• But using the ideal gas law, we can express the number of moles
in terms of pressures assuming a container with volume V:

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Dalton’s Law of Partial Pressures
• The total pressure of a mixture of ideal gases is given by the sum
of their partial pressures
Ptotal = Pa + Pb + Pc +….

• Another useful quantity is the mole fraction (χ)

37
Polling question
The contents of two 5 L containers, one containing H2 and the other containing He are
combined as depicted to the right. What is the final pressure of the 5.0 L vessel?

0.50 mol H2
0.50 mol H2 1.25 mol He 1.25 mol He
P=2.4 atm P=6.0 atm P=?
A) 1.75 atm
B) 2.4 atm
C) 6.0 atm ?????

D) 8.4 atm
E) 10.8 atm

5.0 L @ 20 oC 5.0 L @ 20 oC 5.0 L @ 20 oC

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Collecting Gases over Water
A common use of Dalton’s Law is when gases are collected over
water

For example, H2 can be produced by a

reaction with HCl and collected over
water

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Collecting Gases over Water
The gas collected above the water contains H2, but it also contains
water vapour.
The partial pressure of the water in
the mixture, called its vapour
pressure, depends on temperature.

PT = PH2+ PH2O

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Collecting Gases over Water
• If the liquid levels inside and outside the bottle are the same, then
the pressure inside the bottle is equal to the atmospheric pressure

• For this course you may

assume the levels are
equal, hence
Patm = PT = Pgas + PH2O

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Gases in Chemical Reactions
When solving stoichiometry problems involving ideal gases, you can
convert between moles and any other parameter using the Ideal Gas
Law

Example: Methanol (CH3OH) can be synthesized by the following

reaction:
CO(g) + 2 H2 (g) → CH3OH(g)

What volume (in L) of H2 at a temperature of 355 K and a pressure of

984 mbar, is needed to synthesize 35.7 g of methanol? Assume CO
is in excess.

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Let’s work a problem

43
Let’s work a problem

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Gases in Chemical Reactions
Be creative and look for shortcuts!

Consider the following reaction:

2 H2 (g) + O2 (g) → 2 H2O (g)

In a container of constant volume of 10.0 L and a temperature of 298

K, what will the partial pressure of H2O (in bar) be produced if PH2 =
0.20 bar and PO2 = 0.40 bar at the start of the reaction?

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Let’s work a problem

46
Microscopic Properties of Gases (Kinetic Molecular Theory)

• So far we have seen the gas laws, derived empirically

• In this section we want to look at the KMT that explains the gas
laws

• From a series of simple postulates, the ideal gas law can be

derived from first principles

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Kinetic Molecular Theory (KMT): Postulates
1. The size of each gas particle is extremely small. (Most
of the container is empty space).

2. The average kinetic energy of a particle is proportional

to the temperature in Kelvin)

3. The collision of one particle with another (or the wall of

the container) is completely elastic.

48
Kinetic Molecular Theory (KMT): Explaining Gas Laws
1
Boyles Law: 𝑉 ∝ , n & T constant
𝑃

Charles’s Law: (𝑉 ∝ T, n & P constant)

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Kinetic Molecular Theory (KMT): Explaining Gas Laws
Avogadro’s Law: (𝑉 ∝ n, T & P constant)

Dalton’s Law: (Ptotal = Pa + Pb + Pc +….)

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Kinetic Molecular Theory and the Ideal Gas Law
It can be shown that from these basic postulates of KMT (if interested
consult the textbook for the full derivation)

PV = nRT

which matches empirical measurements, thus supporting the theory!

However KMT breaks down under extreme situations, which will be

discussed later (real gases)

51
Temperature and Molecular Velocities
The kinetic energy of one particle is:

1
𝐾𝐸 = 𝑚𝑢2
2

but for many particles in a sample, there is a velocity distribution so

we need to consider average kinetic energies and velocities:

Per mole of gas,

1
𝐾𝐸𝑎𝑣𝑔 = 𝑁𝐴 𝑚𝑢2
2
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Temperature and Molecular Velocities
but 𝐾𝐸𝑎𝑣𝑔 ∝ 𝑇 and 𝑁𝐴 𝑚 = 𝑀

3
specifically, 𝐾𝐸𝑎𝑣𝑔 = 𝑅𝑇 per mole of ideal gas
2

1 3
𝑁𝐴 𝑚𝑢2 = 𝑅𝑇
2 2

3𝑅𝑇 3𝑅𝑇
𝑢2 = =
𝑁𝐴 𝑚 𝑀
where M is the molar mass.

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Temperature and Molecular Velocities
3𝑅𝑇
= 𝑢2
𝑀
We can then define the root mean square velocity (urms) as:

3𝑅𝑇
urms = 𝑢2 =
𝑀
and urms will be in m/s if:
• R:
• T:
• M:
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Let’s work a problem
What is the urms (in m/s) of a hydrogen molecule at 25°C?

55
Polling question
The cruising speed of a Boeing 767 is 854 km/r (237 m/s). Xe (131.29 g/mol) has
about the same root mean square speed at 298 K. Which of the following gases
would (using rms velocities) beat the Boeing 767 in a race?

A) Cl2
B) Kr
17 35 36
C) Br2
Cl Br Kr
D) Both Cl2 and Kr
35.4527 79.904 83.80
E) All of these.

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Distribution of molecular speeds
All speeds are possible but
not equally likely – there
will be a distribution of
speeds.

um is the “most probable

speed” (mode)

uav is the average speed

(mean)

urms is the root mean

square speed
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Variation in speed with molar mass (M)
Lighter molar mass gases have the distribution shifted
towards higher speeds and it broadens.

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Variation in speed with temperature (T)

As the temperature increases, the

average velocity increases and the
distribution broadens.

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Polling Question
Consider a 1.0 L sample of helium (He) and a 1.0 L sample of argon
(Ar) at the same temperature and pressure.

Do the atoms of He have the same average kinetic energy as the atoms
of Ar?

A) YES

B) NO

60
Polling Question
Consider a 1.0 L sample of helium (He) and a 1.0 L sample of argon
(Ar) at the same temperature and pressure.

Do the atoms of He have the same average velocity as the atoms of Ar?

A) YES

B) NO

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Mean Free Path, Diffusion and Effusion of Gases
• The average distance traveled between collisions is the mean free
path. It increases as the concentration, or partial pressure, of the
gas decreases.

Effusion
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Mean Free Path, Diffusion and Effusion of Gases

• The process by which gas

molecules spread out in
response to a difference in
concentration is called
diffusion.
• A related process in which a
gas escapes from a container
through a small hole into a
vacuum is called effusion.
(diagram to the right)
Effusion
63
Mean Free Path, Diffusion and Effusion of Gases

The rate of effusion is related to the root mean square velocity.

This is an inverse relationship (i.e. as one goes up, the other
goes down). This can be illustrated as follows:

𝑟𝑎𝑡𝑒 ∝ 𝑢𝑟𝑚𝑠

1
𝑢𝑟𝑚𝑠 ∝
𝑀

Effusion
64
Mean Free Path, Diffusion and Effusion of Gases

The ratio of effusion rates for two different gases is given by

Graham’s law of effusion:

in which rateA and rateB are the effusion rates of gases A and B
and MA and MB are the molar masses, respectively.
Effusion
Do not confuse effusion rate with effusion time!
65
Polling question

Which of the following are true? Pick one.

A) As molar mass goes up, effusion time goes up

B) As molar mass goes up, effusion rate goes up
C) As effusion rate goes up, effusion time goes down
D) As molar mass goes down, effusion time goes up
E) Both A and C are true

66
Mean Free Path, Diffusion and Effusion of Gases

So how do we solve problems involving effusion times, rather

than rates?

Effusion
67
Real Gases
• The molar volumes of gases at STP closely match the ideal gas
calculation we did earlier

68
Real Gases
• The gas laws were obtained from experiments performed under
“normal” conditions of temperature and pressure (i.e. near STP)

• Under more extreme conditions (usually high pressures and/or

low temperatures) we get deviations from the ideal gas law

• Two postulates of KMT that must be modified under extreme

conditions:
− Gas particles occupy have no volume
− Gas particle collisions are completely elastic (no intermolecular
forces)
69
Real Gases: The Effect of the Finite Volume of Gas Particles

Although it was assumed in KMT that gas particles occupy essentially

zero space, their size does become more significant at higher pressures.

70
Real Gases: The Effect of the Finite Volume of Gas Particles

Let’s conduct an experiment by measuring the volume of a fixed

amount of gas by applying pressure at a constant temperature

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Real Gases: The Effect of the Finite Volume of Gas Particles

What causes higher than expected volumes?

𝑉𝑐𝑜𝑛𝑡𝑎𝑖𝑛𝑒𝑟 = 𝑉𝑒𝑚𝑝𝑡𝑦𝑠𝑝𝑎𝑐𝑒 + 𝑉𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠

For an ideal gas, Vparticles = 0 , hence

𝑉𝑐𝑜𝑛𝑡𝑎𝑖𝑛𝑒𝑟 =

Empty space can be reduced in volume, so by applying pressure we essentially

get Boyle’s Law

72
Real Gases: The Effect of the Finite Volume of Gas Particles

𝑉𝑐𝑜𝑛𝑡𝑎𝑖𝑛𝑒𝑟 = 𝑉𝑒𝑚𝑝𝑡𝑦𝑠𝑝𝑎𝑐𝑒 + 𝑉𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠

Unlike empty space, the gas particles themselves can’t really be compressed (or
would liquify) so Vcontainer is higher than expected based on the applied pressure

Van der Waals applied an empirical correction term to the Ideal Gas Law for
volume

𝑛𝑅𝑇
𝑉=
𝑃

𝑛𝑅𝑇
𝑉= + 𝑛𝑏
𝑃
73
Real Gases: The Effect of Intermolecular Forces
• At “normal” temperatures and pressures, intermolecular attractive
forces between particles are very weak and are ignored
• At lower temperatures (and/or higher pressures), intermolecular
forces can be significant since particles are closer together on
average

74
Real Gases: The Effect of Intermolecular Forces
Let’s conduct an experiment by measuring the pressure of a gas by
lowering its temperature at a constant volume

75
Real Gases: The Effect of Intermolecular Forces
What causes lower than expected pressures?

Intermolecular forces cause gas particles to attract one another, reducing their
collision frequency/momentum with the walls of the container

Van der Waals applied a correction term for pressure

of a real gas (non-intuitive)

𝑛𝑅𝑇
𝑃=
𝑉

𝑛𝑅𝑇 𝑎𝑛2
𝑃= − 2
𝑉 𝑉
76
Real Gases: van der Waals Equation
The VDW equation empirically corrects for both
intermolecular forces and finite particle size

Under “normal” situations, reduces to PV = nRT

𝑛 2
𝑃+𝑎 X 𝑉 − 𝑛𝑏 = 𝑛𝑅𝑇
𝑉

Correction for Correction for

intermolecular forces particle size

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Real Gases: Positive and Negative Deviations
• In this graph, assume we are applying
pressure to 1 mol of gas at constant
temperature

• PV/RT can tell us information about the gas

volume at a given pressure

• PV/RT > 1 means volume higher than ideal

gas

• PV/RT = 1 means volume matches ideal gas

law

• PV/RT < 1 means volume less than ideal gas

78
Real Gases: Positive and Negative Deviations

• Positive deviations (>1) are due to the

finite volume effect being more
significant than the intermolecular
forces

• Negative deviations (<1) are due to

the intermolecular forces being more
significant than finite volume effect

• All gases display positive deviations

at high enough pressures

79
Polling Question

Which of the gases in the graph to the

right probably has the strongest
intermolecular attractive forces?

A) He
B) Ar
C) Ne
D) Kr
E) CO2

80
Polling Question

In this (poorly drawn) graph, the same

gas is plotted at three different
temperatures. Which likely represents
the lowest temperature?

A) Curve A
B) Curve B
C) Curve C

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