1 Gases

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
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
Macroscopic Properties
Our aim is to look at the relationship
between the macroscopic properties oI a gas
and end up with the gas laws
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
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
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
dm/V so m V.d but VA.h
So
P m.g/A g.V.d/A g.A.h.d/A g.h.d
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
Barometer (continued)
So Ior a barometer
P g.h.d P atmospheric pressure
h height oI liquid column
d density oI the liquid
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)
Ph
so we can use h as a way oI describing pressure
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
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
)
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
Measuring Gas Pressures
Gas pressures can be measured with a
manometer. This is similar to a barometer
but measures pressure diIIerences using a
liquid.
When one side oI the manometer is open to the atmosphere
Gas Laws
The aim is to determine the relationship
between the gas observables (pressure,
volume, mass, temperature).
These were determined experimentally
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
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
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
Charles`s Law
Further experiments showed that volume
and temperature were linearly related
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) 273.15
Charles`s Law
Graphically:
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'
= =
= =
=
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
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.
Vn or V/n constant
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)
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
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)
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
= =
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
Dalton`s Law
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
P
2
P
3
..
Also note that the mole Iraction in the gas phase
P
P

n
n
i i
i
= =
Dalton`s Law
A common use oI Dalton`s Law is when
gases are collected over water
P
sample
P
water
P
bar
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
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
Collision
between
molecules
Collision
with wall
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
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)
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
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 , how Iast
they are moving u
x
.
i.e N/V u
x
Pressure
Pressure depends on 2mu
x
AND N/V u
x
Hence PN/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
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
Temperature/kinetic energy/speed
The kinetic energy oI a molecule is:
mu
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
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
= =
=
= = =
RT
2
3
E =
This shows that the temperature oI the gas is a
measure oI the kinetic energy oI the molecules
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
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
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?
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
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
= = =
= = = =
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.
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?
u
m
2u
m
3u
m
Clearly the distribution is narrow
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
DiIIusion and EIIusion
DiIIusion
EIIusion
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 =
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
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
pressures EQUAL Ior and
M
M
P
P
A
B
A
B
B
A
=
=
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
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.
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
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 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
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
= =
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
= =
= =
= = =
= = =
=

= =
~ =

= =

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
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 Z1
DiIIerent gases deviate
Irom ideal behaviour in
diIIerent ways
Deviation can be
positive (Z~1) or
negative (Z1)
Deviation always
positive at suIIiciently
high pressure
The compressibility
Iactor is an empirical
(experimental)
predictor oI real gas
behaviour but doesn`t
tell us anything about
WHY?
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.
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
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
RT
bP
1
nRT
PV
Z + = =
This equation Iits H
2
and the high pressure
end well but not all
gases at all pressures
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
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
|
.
|
\
|
+ =
|
.
|
\
|
=
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
=
|
|
.
|
\
|
|
.
|
\
|
+
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
II 'a and 'b are zero, Z1
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
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
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.
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.
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

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CHEM 1000 3.

CHEM 1000 3.0 Gases 65

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