01 Chapter 6 Gases

GENERAL CHEMISTRY
PRINCIPLES AND MODERN APPLICATIONS

ELEVENTH EDITION
PETRUCCI HERRING MADURA BISSONNETTE
Gases
6
PHILIP DUTTON
UNIVERSITY OF WINDSOR
DEPARTMENT OF CHEMISTRY AND BIOCHEMISTRY
Slide 6 - 1 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Gases
CONTENTS
6-1 Properties of Gases: Gas Pressure
6-2 The Simple Gas Laws

6-3 Combining the Gas Laws: The Ideal
Gas Equation and The General Gas
Equation
6-4 Applications of the Ideal Gas
Equation
6-5 Gases in Chemical Reactions
6-6 Mixtures of Gases
6-7 Kinetic—Molecular Theory of Gases
6-8 Gas Properties Relating to the Kinetic
—Molecular Theory
6-9 Nonideal (Real) Gases

FIGURE 6-1
The gaseous state of three halogens (group 17)

6-1 Properties of Gases: Gas Pressure
The Concept of Pressure
Force
Force (N) = g (m/s2) x m (kg)
Pressure
Force (N)
P (Pa) =
Area (m2)
FIGURE 6-2
Illustrating the pressure exerted by a solid

Otto von Guericke 1602-1686

Barometric Pressure
FIGURE 6-4
Measurement of atmospheric pressure with a mercury barometer

FIGURE 6-3
The concept of liquid pressure

Liquid Pressure
P (Pa) =
F = W = gxm = gxVxd = gxhxAxd = gxhxd
A A A A A
liquid pressure is directly proportional to the liquid density and the height of the liquid column

Manometers
FIGURE 6-5
Measurement of gas pressure with an open-end manometer

Units of Pressure: A Summary

6-2 Simple Gas Laws
FIGURE 6-6
Relationship between gas volume and pressure – Boyle’s Law

Boyles Law
1
P PV = a (constant)
V
For a fixed amount of gas at a constant temperature, the gas volume

is inversely proportional to the gas pressure.

Only true if A, B, and C are present in different amounts!
FIGURE 6-7
Gas volume as a function of temperature

Charles’s Law
VT V=bT
The volume of a fixed amount of gas at constant pressure is directly

proportional to the Kelvin (absolute) temperature.

Standard Conditions of Temperature
and Pressure
Gas properties depend on conditions.
We use the definition of STP recommended by the

International Union of Pure and Applied Chemistry (IUPAC).
Standard Temperature and

Pressure (STP) 0ºC and 1 Bar = 105 Pa

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

(at STP)
FIGURE 6-9
Molar volume of a gas visualized

Avogadro’s Law
Gay-Lussac 1808
gases react by volumes in the ratio of small whole numbers.
Avogadro 1811
At fixed T and P
V∝n or V=cn
At a fixed temperature and pressure, the volume of a

gas is directly proportional to the amount of gas.

FIGURE 6-8
Formation of Water – actual observation and Avogadro’s hypothesis

6-3 Combining the Gas Laws:
The Ideal Gas Equation
and the General Gas Equation
Boyle’s law V ∝ 1/P

nT
Charles’s law V∝T V∝
Avogadro’s law V∝n
P

The Ideal Gas Equation
PV = nRT
PV
R=
nT

Applying the ideal gas equation

The General Gas Equation
PiVi PfVf
=
niTi n f Tf
If we hold the amount constant (n = constant):
PiVi PfVf
=
Ti Tf

6-4 Applications of the Ideal Gas Equation
Molar Mass Determination
m
PV = nRT and n=
M
m
PV = RT
M
m RT
M=
PV

Gas Density
m
d= KEEP IN MIND
V
that gas densities are
typically much smaller than
m those of liquids and solids.
PV = RT
M Gas densities are usually
expressed in grams per liter
rather than grams per
milliliter.
m MP
=d=
V RT

6-5 Gases in Chemical Reactions
Stoichiometric factors relate gas quantities to quantities of

other reactants or products.
Ideal gas equation relates the amount of a gas to volume,

temperature and pressure.
Law of Combining Volumes can be developed using the gas

law.

Airbag reaction
https://www.youtube.com/watch?v=NmCFrYiGb5g
6-6 Mixtures of Gases
Dalton’s law of partial pressures

Each component of a gas mixture exerts a pressure that it
would exert if it were in the container alone.
The total pressure of a mixture of gases is the sum of the

partial pressures of the components of the mixture.
Ptot = Pa + Pb +…

The volume that each gase would individually occupy at a
pressure equal to Ptot is
naRT nbRT
Va =
Ptot
, Vb = , …..
Ptot
and Vtot = Va + Vb +…
Percent by volume can be expressed as:

Va Vb
volume % A = ✕100% volume % B = ✕100%
Vtot Vtot

Pa naRT/Vtot na Va naRT/Ptot na
= = = χa = = = χa
Ptot ntotRT/Vtot ntot Vtot ntotRT/Ptot ntot
na Pa Va
= = = χa
ntot Ptot Vtot
Pa = χaPtot Va = χaVtot

FIGURE 6-12
Dalton’s law of partial pressures illustrated

FIGURE 6-13
Collecting a gas over water

Ptot = Pbar = Pgas + PH2O
Pgas = Pbar − PH2O

6-7 Kinetic Molecular Theory of Gases
• Particles are point masses in constant,

random, straight line motion.
• Molecules are separated by great
distances.
• Molecules collide only fleetingly, and
most of the time are not colliding.
• Assumed to be no forces between
molecules.
• Individual molecules may gain or lose
energy but total energy remains constant.
FIGURE 6-14
Visualizing Molecular Motion

The Kinetic-Molecular Theory
Oxtoby, Nachtrieb, Modern Chemistry 3rd Edition

Maxwell-Boltzmann distribution of speeds
Ekin
Modal speed Average speed Root mean

Most probable square speed
speed

Distribution of Molecular Speeds
FIGURE 6-15
Pressure and Molecular Speed

FIGURE 6-16
Distribution of molecular speeds – the effect of mass and temperature

Gas molecules are fast!
---
FIGURE 6-18
A model for calculating the pressure exerted by a single molecule

Speed and velocity are related by the Pythagorean
theorem:
u2 = ux2 + uy2 + uz2
The momentum of a particle is (in x-direction):
p = m ux
When the particle slams in the wall, it will be reflected

elastically, no energy is lost, px and pz do not change
px,particle =  2 m ux
Momentum
Oxtoby, Nachtrieb,conservation requires:3rd Edition
Modern Chemistry
The time between two collisions with the same face of

the box:
t = 2 l / ux
Momentum transferred to the wall per second:
p / t = 2 m ux / 2 l / ux = m ux2 / l
Using the definition of force F = m x a

F = m v / t = p / t
F = m ux2 / l
Force exerted by one particle

In the presence of N particles, with a range masses and
velocities:
F = N m ux 2 / l
Using the definition of pressure P = F / A
P = N m ux 2 / A x l
A x l being the volume V
P V = N m ux 2
Pressure exerted by N particles

In three dimensions, considering that no direction is

preferred:
u2 = ux2 + uy2 + uz2 = 3 ux2
P V = 1/ 3 N m u2
With the ideal gas law: P V = n R T
1/ 3 N m u2 = n R T
Quantitative relationship between speed and temperature

The number of particles can be expressed in terms of
Avogadro’s number NO :
N = n NO
1/3 n NO m u2 = n R T
1/3 NO m u2 = R T
With NO m equals molar mass M:
u2 = 3 R T /M
mean square speed
T ~ u2

Kinetic energy
Ekin = 1/2 m u2
For one mole of ideal gas
Ekin = 1/2 NO m u2 = 3/2 1/3 NO m u2
Ekin = 3/2 R T
The average kinetic energy of an ideal gas depends only

on the temperature
Ekin is independent of mass and density

FIGURE 6-17
Distribution of molecular speeds – an experimental determination

6-8 Gas Properties Relating to the
Kinetic-Molecular Theory
FIGURE 6-20
Diffusion and effusion

A Portion of a Plant for Separating
Uranium Isotopes by Effusion of
UF6
Graham’s Law
The rate of effusion of a gas is inversely proportional to the square root of its
molar mass.
1
Rateeffusion
MW
Only for gases at low pressure (natural escape, not a jet).

Tiny orifice (no collisions)
Does not apply to diffusion.

Rate of effusion
Molecular speeds
Ratio of Effusion times = ratio of two molar masses
Distances traveled by molecules
Amounts of gas effused. (6.25)

Derivation of Graham’s Law

Increasing pressure and /or decreasing temperature leads to

deviations from the ideal gas law.
At high pressure, the volume of the particles is no longer

negligible.
At low T, the particles get slower and attractive forces become

non-negligible.
Figure 6-22
Intermolecular forces of attraction
Slide 59 of 41 General Chemistry: Chapter 6 Copyright © 2011 Pearson Canada Inc.

FIGURE 6-22
The effect of finite molecular size

Volume correction
Ideal gas:
particle volumes are neglected
free Volumei = Vcontainer
Vi = nRT/Pi
Real gas:
particles have a volume
Vr = free Volumer + Vr particles
real ideal
Vr = nRT/Pi + Vr particles = nRT/Pi + nb
Vr > Vi
Vr – nb = nRT/Pi

Pressure correction
Ideal gas:
Particles do not interact
Pi = nRT/Vi
Real gas:
particles cluster
clusters are heavier and move slower
 No pressure change
 Clustering reduces the number of
real ideal particles
Pr = nRT/Pi – a n2 / V2 (concentration2)
Pr < Pi
Pr + a n2 / V2 = nRT / Vi

The van der Waals Equation
n2 a
P+ V – nb = nRT
V2
The van der Waals equation reproduces the observed

behavior of gases with moderate accuracy. It is most
accurate for gases comprising approximately spherical
molecules that have small dipole moments.

Compressibility factor
PV/nRT = 1 for ideal gas.
Deviations for real gases.
PV/nRT > 1 - molecular volume
is significant.
PV/nRT < 1 – intermolecular
forces of attraction.
Figure 6-22
Intermolecular forces of attraction

6.9 Nonideal (Real) Gases
FIGURE 6-21
The behavior of real gases – compressibility factor as a function of pressure at 0ºC

End of Chapter

Meaning of Temperature
The Kelvin temperature (T) of a gas is directly proportional to the average

translational kinetic energy (Ek) of its molecules: T ∝ Ek.

Derivation of Boyle’s Law
Boyle’s Law stated mathematically PV = a
Pressure of a single molecule
Pressure of N molecules
Average speed in each direction

and overall average speed

Derivation of Molecular Speeds
Basic equation of KMT
Boyle’s Law from KMT
Since PV=nRT

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GENERAL CHEMISTRY

PRINCIPLES AND MODERN APPLICATIONS

PETRUCCI HERRING MADURA BISSONNETTE

Slide 6 - 1 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

6-1 Properties of Gases: Gas Pressure

6-2 The Simple Gas Laws

Slide 6 - 2 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Slide 6 - 3 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

The Concept of Pressure

Slide 6 - 4 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Slide 6 - 5 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Slide 6 - 6 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Slide 6 - 7 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Slide 6 - 8 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Slide 6 - 9 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Slide 6 - 10 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Slide 6 - 11 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

For a fixed amount of gas at a constant temperature, the gas volume

Slide 6 - 12 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Slide 6 - 13 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

The volume of a fixed amount of gas at constant pressure is directly

Slide 6 - 14 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

We use the definition of STP recommended by the

Standard Temperature and

Slide 6 - 15 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

1 mol gas = 22.711 L gas

Slide 6 - 16 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

At a fixed temperature and pressure, the volume of a

Slide 6 - 17 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Slide 6 - 18 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Boyle’s law V ∝ 1/P

Slide 6 - 20 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Slide 6 - 21 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Slide 6 - 22 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

If we hold the amount constant (n = constant):

Slide 6 - 23 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Slide 6 - 24 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Slide 6 - 25 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Stoichiometric factors relate gas quantities to quantities of

Ideal gas equation relates the amount of a gas to volume,

Law of Combining Volumes can be developed using the gas

Slide 6 - 27 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Dalton’s law of partial pressures

The total pressure of a mixture of gases is the sum of the

Slide 6 - 30 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Percent by volume can be expressed as:

Slide 6 - 31 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Slide 6 - 32 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Slide 6 - 33 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Slide 6 - 35 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Pgas = Pbar − PH2O

Slide 6 - 36 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

• Particles are point masses in constant,

Slide 6 - 37 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Oxtoby, Nachtrieb, Modern Chemistry 3rd Edition

Modal speed Average speed Root mean

Slide 6 - 39 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.

Slide 6 - 40 General Chemistry: Chapter 6 Copyright © 2017 Pearson Canada Inc.