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CHEM 1000 3.

0 Gases 1
Gases
· Petrucci, Herring Madura and Bissonnette :
Chapter 6
CHEM 1000 3.0 Gases 2
Problem set
Chapter 6
· Questions 5, 9, 13, 26, 39, 41, 50, 57, 69,
73, 74, 78, 82
CHEM 1000 3.0 Gases 3
· We will be looking at Macroscopic and
Microscopic properties:
Macroscopic
· Properties oI bulk gases
· Observable
Pressure, volume, mass, temperature.
Microscopic
· Properties at the molecular level
· Not readily observable
Mass oI molecules, molecular speed, energy, collision
Irequency
CHEM 1000 3.0 Gases 4
Macroscopic Properties
· Our aim is to look at the relationship
between the macroscopic properties oI a gas
and end up with the gas laws
CHEM 1000 3.0 Gases 5
Pressure
· To contain a gas you must have a container
capable oI exerting a Iorce on it (e.g. the
walls oI a balloon).
· This implies that the the gas is exerting a
balancing Iorce
· Normally we talk about the pressure
(Iorce/area) rather than Iorce
CHEM 1000 3.0 Gases 6
Measuring Pressure
· The simplest way to measure gas pressure is
to have it balance a liquid pressure.
· ThereIore we need to quantiIy the liquid
pressure
CHEM 1000 3.0 Gases 7
A
h
· Consider a cylinder oI liquid with area A
and height h
· The Iorce exerted at the bottom oI the
cylinder is its weight
F ÷ m.g
· The pressure exerted is
P ÷ F/A ÷ m.g/A
· The density oI the liquid is
d÷m/V so m ÷ V.d but V÷A.h
· So
P ÷ m.g/A ÷ g.V.d/A ÷ g.A.h.d/A ÷ g.h.d
CHEM 1000 3.0 Gases 8
Barometer
To measure Atmospheric
Pressure
On the leIt the tube is open
On the right the tube is closed
and a liquid column is
supported by the
atmospheric pressure:
Air pressure equals the liquid
pressure
CHEM 1000 3.0 Gases 9
Barometer (continued)
So Ior a barometer
P ÷ g.h.d P ÷ atmospheric pressure
h ÷ height oI liquid column
d ÷ density oI the liquid
CHEM 1000 3.0 Gases 10
Barometer (continued)
For a barometer
P ÷ g.h.d
Note that iI we have a constant 'g¨ and constant 'd¨
(like with a mercury barometer on earth)
P·h
so we can use h as a way oI describing pressure
CHEM 1000 3.0 Gases 11
Atmospheric Pressure
· The average pressure at sea level will
support a column oI 760 mm oI mercury.
· This is the deIinition oI the pressure unit oI
'atmospheres¨
1 atm ÷ 760 mm Hg
Also the unit mm Hg has become known as
Torr (aIter Torricelli)
1 atm ÷ 760 mm Hg ÷ 760 Torr
CHEM 1000 3.0 Gases 12
Atmospheric Pressure
· What is 1 atm in pressure units?
P ÷ g.h.d
g ÷ 9.81 m.s
-2
, h ÷ 0.76 m,
d
Hg
÷ 13.6 g.cm
-3
÷ 13.6x10
3
kg.m
-3
P ÷ 9.81x0.76x13.6x10
3
÷ 1.013x10
5
Pa (N.m
-2
)
CHEM 1000 3.0 Gases 13
II we made a barometer out oI water, what would be the height
oI the water column iI the pressure is 745 torr?
The problem calls Ior the relationship between P and h
P ÷ g.h.d
2 -
3 - 3 3 -
5
s m 9.81 g
m kg 10 00 . 1 cm g 1.00 d
Pa 10 1.013
760
745
P
=
× = =
× × =
3 5
10 1.00 h 81 . 9 10 013 . 1
760
745
g.h.d P
× × × = × ×
=
h ÷ 10.1 m
CHEM 1000 3.0 Gases 14
Measuring Gas Pressures
Gas pressures can be measured with a
manometer. This is similar to a barometer
but measures pressure diIIerences using a
liquid.
CHEM 1000 3.0 Gases 15
When one side oI the manometer is open to the atmosphere
CHEM 1000 3.0 Gases 16
Gas Laws
· The aim is to determine the relationship
between the gas observables (pressure,
volume, mass, temperature).
· These were determined experimentally
CHEM 1000 3.0 Gases 17
Boyle`s Law
· Boyle (~1622) kept the mass oI gas and the
temperature constant and studied the
relationship between pressure and volume
Volume oI
gas
P
CHEM 1000 3.0 Gases 18
Boyle`s Law
· Boyle Iound that pressure and volume were
inversely proportional. (double the pressure
and the volume goes to one halI).
· This is usually expressed as
P.V ÷ constant
or
P
1
V
1
÷ P
2
V
2
CHEM 1000 3.0 Gases 19
Charles`s Law
· Charles (1787) and Gay-Lussac (1822) kept
the mass oI gas and the pressure constant
and studied the relationship between
temperature and volume
375 . 1
V
V
Iound They
) 0 (
) 100 (
=
C
C
o
o
CHEM 1000 3.0 Gases 20
Charles`s Law
· Further experiments showed that volume
and temperature were linearly related
CHEM 1000 3.0 Gases 21
Charles`s Law
· Further experiments showed that volume and
temperature were linearly related and that the
temperature intercept (when volume is zero) was
at 273.15
o
C.
· This temperature is now deIined as absolute zero
and the Kelvin temperature scale given by
T(K) ÷ t(°C) ¹ 273.15
CHEM 1000 3.0 Gases 22
Charles`s Law
· Graphically:
CHEM 1000 3.0 Gases 23
Charles`s Law/Combined Gas Law
2
2 2
1
1 1
T
.V P

T
.V P
or constant
T
P.V
gives
constant
T
V
and constant P.V
Law s Charles' and Law s Boyle' Combining
constant
T
V
as expressed be can Law s Charles'
= =
= =
=
CHEM 1000 3.0 Gases 24
Avogadro`s Law
· From Gay-Lussac`s experiment on reacting
gases Avogadro concluded
'Equal volumes oI diIIerent gases, at the same
temperature and pressure, contain equal
numbers oI molecules¨
CHEM 1000 3.0 Gases 25
Avogadro`s Law
· 'Equal volumes oI diIIerent gases, at the same
temperature and pressure, contain equal numbers
oI molecules¨
· Take 2 equal volumes oI gas. They have equal
numbers oI molecules. Add them together, you
have twice the volume and twice the number oI
molecules.
· Hence gas volume is proportional to number oI
molecules and subsequently to number oI moles.
V·n or V/n ÷ constant
CHEM 1000 3.0 Gases 26
Gas Law
constant
n.T
P.V
to leads
Law) s (Avogadro' constant
n
V
Law) s (Charles' constant
T
V
Law) s (Boyle' constant P.V
: Given that
=
=
=
=
Usually written PV = nRT
(Where R is a constant)
CHEM 1000 3.0 Gases 27
Ideal Gas Law
· The ideal gas law can be written in terms oI
moles or molecules
PV ÷ nRT
n ÷ number oI moles R ÷ gas constant
PV ÷ NkT
N ÷ number oI molecules k ÷ Boltzmann`s constant
CHEM 1000 3.0 Gases 28
Ideal Gas Law
· Values oI the constants
· R ÷ 8.314 J K
-1
mol
-1
(Pa m
3
K
-1
mol
-1
, kPa L K
-1
mol
-1
)
R ÷ 0.0821 L atm K
-1
mol
-1
· k ÷ 1.38x10
-23
J K
-1
(really J K
-1
molecule
-1
but
molecule is just a number)
CHEM 1000 3.0 Gases 29
weight) (molecular mass molar M
gas oI mass m RT
M
m
PV
law gas ideal the oI Iorms useIul Other
=
= =
RT
PM

V
m
d
gas
= =
CHEM 1000 3.0 Gases 30
Dalton`s Law
· In a gas mixture each component Iills the
container and exerts the pressure it would iI
the other gases were not present.
· Alternatively, each component acts as iI it
were alone in the container
CHEM 1000 3.0 Gases 31
Dalton`s Law
CHEM 1000 3.0 Gases 32
Dalton`s Law
· Thus Ior any component i
P
i
V ÷ n
i
RT
We call P
i
the partial pressure oI component i
· The total pressure is given by the sum oI the
partial pressures
P ÷ P
1
¹ P
2
¹ P
3
¹..
· Also note that the mole Iraction in the gas phase
P
P

n
n

i i
i
= =
CHEM 1000 3.0 Gases 33
Dalton`s Law
· A common use oI Dalton`s Law is when
gases are collected over water
P
sample
¹ P
water
÷ P
bar
CHEM 1000 3.0 Gases 34
Microscopic Properties oI Gases
· So Iar we have seen the gas laws.
· These came Irom observations.
· In this section we want to look at a theory that
explains the gas laws:
The kinetic theory oI gases
or The kinetic molecular theory
CHEM 1000 3.0 Gases 35
Kinetic Theory oI Gases: Assumptions
1. A gas is made up oI a large number oI extremely
small particles (molecules or atoms) in constant,
random, straight line motion
2. Molecules occupy very little volume (most oI the
container is Iree space)
3. Molecules collide with one another and with the
walls oI the container
4. There are no Iorces between the molecules
5. Molecules can gain or lose energy on collision but
the total energy remains constant
CHEM 1000 3.0 Gases 36
Collision
between
molecules
Collision
with wall
CHEM 1000 3.0 Gases 37
The theory will give inIormation on the
speeds oI molecules, the Irequency with
which they collide, and the distribution oI
energy
It is only useIul iI it can predict the gas laws
CHEM 1000 3.0 Gases 38
Pressure
· Pressure comes Irom the gas molecules
hitting the walls oI the container
· The pressure will depend on:
How many molecules hit the wall
How Iast they are travelling
· (how 'hard¨ they hit the wall)
CHEM 1000 3.0 Gases 39
Pressure
· Put a gas in a box oI volume V.
N molecules each oI mass m
each molecule has a speed u
· Think about one side oI the box
· Call that the x direction
CHEM 1000 3.0 Gases 40
Pressure
· When a molecule hits the wall it changes direction.
We assume the speed doesn`t change so the change in momentum
is 2mu
x
· The number oI molecules hitting the wall depends how
many molecules are in the container and how big it is
N/V.
· It also depends on which way they are going ½, how Iast
they are moving u
x
.
· i.e ½N/V u
x
CHEM 1000 3.0 Gases 41
Pressure
· Pressure depends on 2mu
x
AND ½N/V u
x
· Hence P·N/Vmu
x
2
· Not all molecules have the same speed so we
should use the average oI u
x
and all directions
are the same so u
x
÷ u
y
÷u
z
÷1/3u
· hence
V
u Nm
3
1
P
2
=
where
2
u ÷ the average oI the
squares oI the speeds
CHEM 1000 3.0 Gases 42
constant PV like lot a looking is This
u Nm
3
1
PV
V
u Nm
3
1
P
2 2
=
= =
Law s Boyle' is This
. emperature constant t at constant a is u II
2
We will not prove this but assume it is true and use
the PV equations Irom the macroscopic and
microscopic sections to learn about speed and
temperature
CHEM 1000 3.0 Gases 43
Temperature/kinetic energy/speed
The kinetic energy oI a molecule is:
½mu
2
The average kinetic energy oI a molecule is:
2
u m
2
1
The kinetic energy oI a mole oI molecules is
number) s Avogadro' is N ( u m N
2
1
A
2
A
CHEM 1000 3.0 Gases 44
A
2 2
A
N
2E
u m u m N
2
1
E = =
The kinetic energy oI a mole oI molecules (E) is
But
RT
2
3
E
n.E
3
2
nRT
nRT PV given that
n.E
3
2
N
N.E
3
2 u Nm
3
1
PV
A
2
= =
=
= = =
CHEM 1000 3.0 Gases 45
RT
2
3
E =
This shows that the temperature oI the gas is a
measure oI the kinetic energy oI the molecules
CHEM 1000 3.0 Gases 46
Molecular Speeds
M
RT 3
m N
3RT
u
RT
2
3
u m N
2
1
E
A
2
2
A
= =
= =
Equating
Gives
RT
2
3
E and u m N
2
1
E
2
A
= =
M
3RT
u u
2
rms
= = The root mean square speed
CHEM 1000 3.0 Gases 47
What is the speed oI a hydrogen
molecule at 25
o
C?
) km/hr 000 , 7 (
s m 10 92 . 1
mol kg 10 016 . 2
K 298 mol K J 314 . 8 3
M
RT 3
u
1 - 3
1 - 3
-1 -1
rms
× =
×
× ×
= =
÷
The Iactor oI 10
-3
in the denominator is to put the
molar mass in SI units (i.e. in kg)
Note: 1 Joule ÷ 1 kg m
2
s
-2
CHEM 1000 3.0 Gases 48
Distribution oI molecular speeds
So Iar we have calculated the root mean square speed
only
What other speeds are possible?
What is the real average speed?
CHEM 1000 3.0 Gases 49
Distribution oI molecular speeds
All speeds are possible
but are not equally
likely
u
m
is the 'most
probable speed¨
(mode)
u
av
is the average speed
(mean)
u
rms
is the root mean
square speed
CHEM 1000 3.0 Gases 50
Average speeds
The three average speeds can be obtained Irom the distribution
m av rms
av rms
m m
2RT 8RT 3RT
u u u
M M M
8RT 3RT
u u 8 3
M M
÷ 1.13 ÷ 1.22
u 2 u 2
2RT 2RT
M M
t
t
= = =
= = = =
CHEM 1000 3.0 Gases 51
Variation in speed with temperature and
molar mass
The average speeds vary
with T and 1/M
The red curves are Ior O
2
at two temperatures.
The leIt O
2
curve and the
blue H
2
curve are at the
same temperature.
CHEM 1000 3.0 Gases 52
How broad is the speed distribution
We know the average speeds. Do most
molecules have speeds similar to the
average? Do a lot go Iaster?
CHEM 1000 3.0 Gases 53
u
m
2u
m
3u
m
Clearly the distribution is narrow
CHEM 1000 3.0 Gases 54
It is possible to calculate the Iraction oI molecules that
have a speed greater than u
Speed u Fraction oI molecules with
speeds greater than u
0 1 (all molecules go Iaster than 0)
3u
m
4.5x10
-4
5u
m
4x10
-10
10u
m
4x10
-43
Most molecules have speeds close to u
m
CHEM 1000 3.0 Gases 55
DiIIusion and EIIusion
DiIIusion
EIIusion
CHEM 1000 3.0 Gases 56
Collisions with the Wall
The number oI collisions that molecules make with
the wall depend on how many molecules there are
(per unit volume) and how Iast they are moving. Z
wall
will have units oI m
-2
s
-1
av wall av wall
u .
V
N
4
1
Z actually u .
V
N
Z = ·
CHEM 1000 3.0 Gases 57
EIIusion
We can obtain a quantitative understanding oI eIIusion
by recognizing that eIIusion is the loss oI a molecule
that would normally hit the wall.
av wall
u .
V
N
4
1
Z =
.A .u
V
N
4
1
.A Z eIIusion oI Rate
av wall
= =
The rate at which molecules leave the container is the
wall collision rate times the area oI the hole
CHEM 1000 3.0 Gases 58
A
B
B
A
B
A
B
A
av
av
B
A
av
B
av
A
wall
wall
M
M
N
N
M RT 8
M RT 8
N
N
u(B)
u(A)
N
N
.A .u(B)
V
N
4
1
.A .u(A)
V
N
4
1
(B).A Z
(A).A Z

B oI eIIusion oI rate
A oI eIIusion oI rate
container same in the B) and (A gases 2 Ior
= = =
= =

Note that the ratio oI the number oI molecules is the ratio oI the partial
pressures
Law s Graham'
M
M
B oI eIIusion oI rate
A oI eIIusion oI rate
pressures EQUAL Ior and
M
M
P
P
B oI eIIusion oI rate
A oI eIIusion oI rate
A
B
A
B
B
A
=
=
CHEM 1000 3.0 Gases 59
Aside
Students oIten have problems with questions
involving rates and or time, because they are inverses
Always remember that Rate ÷ molecules
time
So the Iaster the rate the smaller the time
CHEM 1000 3.0 Gases 60
Collisions between molecules
When studying interactions between gas molecules
you need to know how oIten the molecules actually
collide
The collision Irequency is the number oI collisions a
particular molecule makes in one second. This will
depend on how many molecules there are (per unit
volume), how Iast they are moving, and how big they
are.
CHEM 1000 3.0 Gases 61
Collisions between molecules
For a gas where all the molecules are the same, and
have a diameter d, the collision Irequency is Z
A
kT
P
u d 2
V
N
u d 2 Z
av
2
av
2
A
= =
Z
A
will have units oI s
-1
CHEM 1000 3.0 Gases 62
Collisions between molecules
To calculate the total number oI collisions Ior all
molecules we must multiply Z
A
by N/V to count all the
molecules, and by ½ so we don`t count them twice.
2
av
2
av
2
AA
V
N
u d
2
1
V
N
u d 2
V
N
2
1
Z
|
.
|

\
|
= =
Z
AA
will have units oI s
-1
m
-3
CHEM 1000 3.0 Gases 63
Mean Iree path
A related parameter is the average distance a molecule
travels between collisions. This is the mean Iree path
The collision Irequency is Z
A
s
-1
The time between collisions is 1/Z
A
s
The average speed oI the molecules is u
av
Since distance is speed times time
N
V
d 2
1
Z
u

2
A
av
= =
CHEM 1000 3.0 Gases 64
So how big are these numbers??
Nitrogen at 298K and 1 atm
( )
nm 56 m 10 6 . 5
s 10 3 . 8
s m 475
Z
u

s 10 3 . 8 m 10 46 . 2 s m 475 m 10 4.0 2
V
N
u d 2 Z
s m 10 92 . 2 m 10 46 . 2 s m 475
4
1
V
N
u
4
1
Z
m 10 46 . 2
K 298 K J 10 38 . 1
Pa 10 013 . 1
kT
P
V
N
m 10 4.0 d s m 475
mol kg 10 28.01
K 298 mol K J 314 . 8 8
M
RT 8
u
8
1 - 9
1 -
A
av
1 - 9 3 - 25 1 -
2
10 -
av
2
A
1 - 2 - 27 3 - 25 1 -
av wall
3 - 25
1 - 23
5
10 - 1 -
1 - 3 -
-1 -1
av
= × =
×
= =
× = × × × × × × = =
× = × × × = =
× =
× ×
×
= =
× ~ =
× ×
× ×
= =
÷
÷
CHEM 1000 3.0 Gases 65
Real Gases
· The gas laws we obtained Irom experiments
perIormed under normal conditions oI
temperature and pressure
ThereIore we can usually use the ideal gas law
· Under more extreme conditions we get
deviations Irom the ideal gas law
CHEM 1000 3.0 Gases 66
Compressibility Iactor
· One way to measure the deviation Irom
ideal behaviour is to deIine a
compressibility Iactor Z as:
nRT
PV
Z =
·For an ideal gas Z÷1
CHEM 1000 3.0 Gases 67
Compressibility Iactor
· DiIIerent gases deviate
Irom ideal behaviour in
diIIerent ways
· Deviation can be
positive (Z~1) or
negative (Z·1)
· Deviation always
positive at suIIiciently
high pressure
CHEM 1000 3.0 Gases 68
Compressibility Iactor
· The compressibility
Iactor is an empirical
(experimental)
predictor oI real gas
behaviour but doesn`t
tell us anything about
WHY?
CHEM 1000 3.0 Gases 69
van der Waal Equation
· This is an attempt to correct the
assumptions oI the kinetic theory oI gases
Ior real gas behaviour, and to modiIy the
ideal gas equation to account Ior it.
· We will judge its success by its ability to
explain the shapes oI the compressibility
Iactor curves.
CHEM 1000 3.0 Gases 70
van der Waal Equation
· Assumption 2 oI the kinetic theory:
Molecules occupy very little volume (most oI
the container is Iree space)
What iI we allow them to have a volume (say
b L mol
-1
)
The molecules then have less volume in
which to move so
V
real
÷ V
measured
- nb
CHEM 1000 3.0 Gases 71
van der Waal Equation
V
real
÷ V
measured
nb
Substitute this into the ideal gas law
PV ÷ nRT becomes P(V-nb) ÷ nRT
To get in the compressibility Iactor Iorm
RT
bP
1
nRT
PV
Z
Pnb nRT PV
+ = =
+ =
A plot oI Z against P would be a straight line oI intercept 1
CHEM 1000 3.0 Gases 72
van der Waal Equation
RT
bP
1
nRT
PV
Z + = =
This equation Iits H
2
and the high pressure
end well but not all
gases at all pressures
CHEM 1000 3.0 Gases 73
van der Waal Equation
· Assumption 4 oI the kinetic theory:
There are no Iorces between the molecules
What iI we allow Ior van der Waal Iorces
to exist between molecules.
These have two eIIects
1. The number oI collisions with the walls goes
down
2. The Iorce that each collision makes with the
wall goes down
CHEM 1000 3.0 Gases 74
van der Waal Equation
Thus the observed pressure will be less than
expected Ior an ideal gas.
This decrease will depend on (n/V)
2
, one n/V
Ior the number oI collisions and one Ior the
Iorce oI each collision
2
measured ideal
2
ideal measured
V
n
a P P so
V
n
a P P
|
.
|

\
|
+ =
|
.
|

\
|
÷ =
CHEM 1000 3.0 Gases 75
van der Waal Equation
Combining this pressure term into the
previous equation:
P(V-nb) ÷ nRT
we obtain van der Waal`s equation
( ) nRT nb V
V
n
a P
2
= ÷
|
|
.
|

\
|
|
.
|

\
|
+
CHEM 1000 3.0 Gases 76
van der Waal Equation
Expressing as compressibility:
( )
|
.
|

\
|
÷ = =
|
.
|

\
|
÷ =
= ÷
|
|
.
|

\
|
|
.
|

\
|
+
RTV
an
nb - V
V
nRT
PV
Z
V
n
a
nb - V
nRT
P
nRT nb V
V
n
a P
2
2
CHEM 1000 3.0 Gases 77
van der Waal Equation
II 'a¨ and 'b¨ are zero, Z÷1
Neglecting 'a¨ Ior a minute, iI b is non-zero the Iirst
term and Z is greater than 1
Neglecting 'b¨, iI a is non-zero Z is less than 1
The Iirst term is responsible Ior positive deviations, the
second Ior negative deviations Irom ideal behaviour.
|
.
|

\
|
÷ = =
RTV
an
nb - V
V
nRT
PV
Z
CHEM 1000 3.0 Gases 78
van der Waal Equation
· Summary
Positive deviations are due to the molecules
having Iinite size and is quantiIied by the 'b¨
Iactor
Negative deviations are due to the molecules
having intermolecular Iorces and is quantiIied
by the 'a¨ Iactor
CHEM 1000 3.0 Gases 79
van der Waal 'b¨
( ) nRT nb V
V
n
a P
2
= ÷
|
|
.
|

\
|
|
.
|

\
|
+
· We deIined 'b¨ as the
volume oI the molecules.
This can be estimated
Irom the volume oI one
mole oI the pure liquid.
CHEM 1000 3.0 Gases 80
van der Waal 'a¨
( ) nRT nb V
V
n
a P
2
= ÷
|
|
.
|

\
|
|
.
|

\
|
+
· 'a¨ is a measure oI the intermolecular
Iorces. We will see more about this later in
the course.
CHEM 1000 3.0 Gases 81
van der Waal Constants
Molecule Forces
a
L
2
atm mol
-2
Size
b
L mol
-1
He 0.034 0.0237
H
2
0.244 0.0266
Cl
2
6.49 0.0564
Compare Cl
2
to He
variation oI a
Iactor oI 200
variation oI a
Iactor oI ·3