Zumdahls Chapter 5

Gases
Contents
Importance of Gases
Gas Pressure
Kinetic Theory of Gases
Gas Laws
Boyle: PV constant
Charles: V / T constant
Avogadro: V / n constant
Ideal Gas Law: PV = nRT
Gas Stoichiometry
Partial Pressures and Mole
Fractions, X
i
Effusion
Diffusion
Our Atmosphere
Ideal gas + g + condensible,
heated from the bottom
Real Gases
The Significance of Gases
Gases are elementary phases.
Neither condensed (hence low intermolecular forces)
Nor electrified (as would be plasmas)
Equation of State (n,P,V,T) extremely simple.
Vapor pressures betray the equilibrium balance in
solutions and tell us of chemical potential (G
molar
)
of solution components!
Relation to Other Phases
Gases share the fluidity of liquids & plasmas but
not their nonideal high intermolecular interactions.
Gases share the simplicity of geometry (none) with
solids (perfectly regular).
Gases share an equilibrium with all of their
condensed phases, and their pressure comments
upon the shift of that equilibrium.
Gas Pressure
Gases naturally expand to fill all of their container.
Liquids fill only the lower (gravitational) volume equal
to their fixed (molecular-cheek-by-jowl) volume.
Fluids (gases and liquids) exert equal pressure
(force) in all directions.
Pressure, P, is the (expansive) force (Newtons)
applied per unit area (m
2
).
Measured with manometers as Pascals = 1 N m
2
= 1 J m
3
Isotropic Fluid Pressure
Auto repair hoists work by isotropic oil pressure.
Pressure on one arm of a fluid-filled U is transmitted
by the fluid to the other arm, raising the car.
But P equivalence is not just up-down.
A pinhole anywhere leaks.
Gas too is a fluid with isotropic P.
Gravitational force influences P.
Whats wrong with this picture?
Pressure and Gravity
While isotropic at every point, P increases linearly
with depth in the sea.
Shallow objects must support only shallow columns of
water above them.
Deep objects must bear the weight of the deep columns
of water above them.
The linearity follows from waters constant density, but
airs density varies with pressure hence altitude.
Air Pressure
With gravity, the change, dP, with altitude, dh,
varies with the instantaneous density, = m / V.
well find is proportional to P. And since F=mg,
dF = gdm or dP = dF/A = gdm/A = gd(h) = gdh
dP/dh = aP or dP/P = dlnP = a dh and P = P
0
e
ah

a includes g and the proportionality between P and .
And atmospheric P falls off exponentially with
altitude, being only ~1/3 atm on top of Everest.
Pressure Rules
While it may be instinctively satisfying that
varies linearly with P, it would be nice to prove it.
Well need Boyles and Avogadros Laws to
confirm the atmospheric pressure profile.
Theyll need to turn g off and rely on the inherent
expansion of gases.
AND well have to understand Kinetic Theory.
Forces and Molecular Forces
Force = mass times acceleration, like mg
Gravitational force is continuous, but the force of
gas pressure is discrete.
The pummeling of molecular collisions may be
relentless but it is discontinuous.
F = ma = m dv/dt = d(mv)/dt = dp/dt
p = momentum, so F = the rate of momentum change
KINETIC THEORY
The 800 lb gorilla of free molecular motion, and
roaring success of Bernoulli, Maxwell, and Herepath.
EQUIPARTITION THEOREM
Every mode of motion has average thermal energy of
kT per molecular motion or RT for a mole of them.
It works only for continuous energies; it fails if quantum level
energy spacings approach kT. Translations perfect!
Importance: kinetic energy is fixed at fixed T.
Prerequisites for K.T. of Gases
Molecules might as well be mass points, so distant
are they from one another in gases. ID irrelevant.
Those distances imply negligible intermolecule
forces, so presume them to be zero. KE fixed
Until they hit the walls, and those are the only
collisions that count. dp/dt on walls gives P.
Kinetic Energy, KE, directly proportional to T.
Boyles Law: PV fixed (iff n,T also)
P
1
V
1
= P
2
V
2
= PV as long as n and T unchanged!
Invariant T means that average Kinetic Energy remains
the same; so we expect the same molecular momenta, p
That means that collisions between the molecules and
the wall transfer the same average force, f.
+ p
0
p
0
Ap = 2p
0
f +2p
0
and conservation requires
Boyles Geometry I
Regardless of the volume change, each collision
transfers the same impulse to the walls.
But if the dimensions double, theres more wall, and P
is force per unit area of wall!
Doubled dimensions means 4 as much wall; thus P
should drop to its original value?
A
2
= 4A
1
Is P
2
therefore P
1
?
But V
2
= 8V
1
, so P
2
must be 1/8P
1
!?!
Boyles Geometry II
Ahhh but we forgot that the molecules have
twice as far to fly to get to a wall!
That makes those collisions only as frequent!
The total surface experiences only as many
impulses per unit time, so there are as many
collisions spread over 4 the area.
Yes! P
2
= 1/8 P
1
when V
2
= 8 V
1
. Boyle is right!

Charless Law: V/T fixed (iff n,P too)
Kinetic Theory helps here.
Imagine a fixed volume heated such that T
2
= 8 T
1
That means K.E.
2
= 8 K.E.
1
or v
2
2
= 8 v
1
2
More to the point, v
2
= 8

v
1
(if v is a speed), so wall
collisions are 8

times more frequent.

And molecules have 8

the momentum when they hit.

Therefore, P
2
= 8

8

P
1
= 8 P
1
.
Want P fixed? Watch how to do it.
Charless Law (Geometry)
What weve shown is that P/T is fixed when n and V
are fixed. Another expression of Charless Law.
But if we simply apply our understanding of Boyle to
this understanding of (modified) Charles
Keeping the high T
2
fixed, we can expand V to 8V
1

which will lower the P
2
from 8 P
1
to exactly P
1
.
Thus, T
2
= 8 T
1
implies V
2
= 8 V
1
at fixed P.
P, V, T 8P, V, 8T P, 8V, 8T

Avogadros Law: V/n fixed (iff P,T too)
If we double n, the wall experiences twice the
frequency of collisions, but each one has the same
force as before.
So P doubles.
To reduce P back to its original value, Boyle says
to double V instead.
So Avogadro is right, if Boyle is right.
And Boyle is right.

Since Everybody is Right
What Equation of State embodies Boyle, Charles,
and Avogadro all at the same time?
Playing with the algebra, convince yourself that
only PV / nT = universal constant works.
Doing any number of gas law experiments reveals
that the Gas Constant, R = 8.314 J mol
1
K
1
If PV is in atm L, then R = 0.08206 atm L mol
1
K
1
In fact, R = kN
Av
where k is Boltzmanns Constant.
PV = nRT
From this Ideal Gas equation, much Chemistry flows!
Take density, , for example.
= m / V = n M / V M is the molar weight of the gas.
/ M = n / V = P / RT
= P ( M / RT ) It really is proportional to P for an Ideal Gas.
Returning to the Barometric Formula:
dP = g dh = P g ( M / RT ) dh now gives
P = P
0
e
( Mgh / RT )
( assuming fixed T which really isnt the case)
They were All balloonists.
Why do you think Charles was fascinated with the
volume of heated air?
When you heat a filled hot air balloon, P and V stay the
same, but T increases. How can that be?
Rearrange the i.g. eqn., and n = PV / RT must decrease.
Gas molecules leave the balloon! And decreases.

hot
V is the weight of air left. If A =
cold

hot
,
(A)V is the lifting power of the balloon (air mass gone).
Prosaic Problems
Concentration of O
2
in air.
[O
2
] = n
O2
/ V = P
O2
/ RT
Need P and T; say STP:
0C, 1 atm. P
O2
= 0.21 atm
Must use absolute T, so the
RT = 22.4 L / mol
0.0821 atm L/mol K (273 K)
[O
2
] = 0.21 atm/22.4 L/mol
[O
2
] = 0.0094 M
Volume of H
2
possible at
STP from 10 g Al?
Assume excess acid.
3 H
+
+ Al Al
3+
+ 1.5 H
2
n
H2
= 1.5 n
Al
n
Al
= 0.37 mol
10 g (1 mol/27 g)
n
H2
= 0.55 mol
V = nRT/P = 12 L
Gas Stoichiometry
Last example was one such; finding gas volume
since thats usually its measure.
While a gas has weight, buoyancy corrections are needed to
measure it that way since air as weight too.
So the only new wrinkle added to our usual
preoccupation with moles in stoichiometry is:
V
A
= n
A
RT / P
A
, but unless A is pure, P
A
= P
total

even though V
A
= V
total
. So n P at fixed V too.
Daltons Law: Partial Pressures
Same guy who postulated atoms as an explanation for
combining proportions in molecules went on to explain that
partial pressures add to the total P.
Kinetic Theory presumes gas molecules dont see one
another; so theyd contribute independently to the total
pressure. Makes sense.
P = P
A
+ P
B
+ P
C
+ ( Daltons Law; fixed V )
Note the similarity with Avogadros Law which states
that at the same pressures, V = V
A
+ V
B
+ V
C
+
Partial Pressures and Mole Fractions
P = P
A
+ P
B
+ P
C
+
n (RT/V) = n
A
(RT/V) + n
B
(RT/V) + n
C
(RT/V) +
So n = n
A
+ n
B
+ n
C
+ (surprise surprise)
Now divide both sides by n, the total number of moles of gas
1 = X
A
+ X
B
+ X
C
+ mole fractions sum to 1.
1 = P
A
/P + P
B
/P + P
C
/P +
Hence X
A
= P
A
/P for gases.
Grahams Law of Diffusion
Gas Diffusion
Mass transport of molecules
from a high concentration
region to a low one.
Leads to homogeneity.
Not instantaneous! Hence
molecules must collide and
impede one another.
Square of diffusion rate is
inversely proportional to

Gas Effusion
Leakage of molecules from
negligible pinhole into a
vacuum.
Leak must be slow relative
to maintenance of the gass
equilibrium.
Square of effusion rate is
inversely proportional to
( proportional to M.)
Kinetic Theory and Rates
Presumption behind rate M

is comparison of
rates at same T and same P.
Fixed T implies same K.E. = m v
2
regardless of
the identity of the gas molecules!
Thus m
A
v
A
2
= m
B
v
B
2
or
v
A
/ v
B
= ( m
B
/ m
A
)

= ( M
B
/ M
A
)


235
UF
6
diffuses (352/349)

= 1.004 faster than

238
UF
6
Airs Composition as Mole Fraction
Dry Atmosphere; X
A
0.7803 N
2
0.2099 O
2
0.0094 Ar
0.0003 CO
2
0.0001 H
2
!
Avg MW = 0.02897 kg/mol
Mass, 5.210
18
kg
Standard P, 1 bar = 10
5
Pa
100% Humid Atmosphere
At 40C, P
H2O
= 55.3 torr
1 torr = 1 mm Hg
1 bar = 750 torr
P
H2O
= 0.0737 bar
0.92630.7803=0.7228 N
2
0.1944 O
2
0.0087 Ar, etc.
Avg. MW = 0.02816 kg/mol
Consequences of M
air
Humid air may feel heavier but its 3% lighter than dry
air. That means a column of it has lower P.
The barometer is lower where its stormy, higher
where its dry. Winds blow from high P to low P.
Since 1 / T, higher T regions have less dense air; so
tropics get phenomenal thunderclouds as buoyancy
(heat) & incoming wind pile up air to flatiron clouds.
Up to the tropopause where it then spreads horizontally.
Moving Air on a Rotating Earth
Imagine a cannon at the N pole fires a shell at NY
that takes an hour to travel.
In that time, the Earth rotates to the next time zone, and
the shell hits Chicago instead!
The fusilier thinks his shell curved to the right!
Chicago retaliates by firing back.
But its shell is moving east with the city faster than the
ground at higher latitudes. It seems to veer right too!
Coriolis (non)Force
All flying things (in the northern hemisphere) veer right.
Wind approaching a low P region misses the center,
veering around to the right in a counterclockwise spiral.
Thus the shape of hurricanes (whose upper air is rained out).
Air fired from the tropics moves 1000 mph east.
But so does the ground there; its not a problem until
At about 30 N, the ground (and its air) slows too much,
and dry tropopause winds whip down, making deserts.
Height of a Uniform Dry Atmosphere
P
0
= 1 atm = 1.0132510
5
Pa = 1.0132510
5
N/m
2
Force on every m
2
is F = M
air
g = 1.0132510
5
N
N = J m
1
= kg m
2
s
2
m
1
= kg m s
2
in SI

M
air
= F / g = 1.0132510
5
N / 9.80665 m s
2
M
air
= 1.0332310
4
kg = V = Ah ; A = 1 m
2
h = M
air
/ A = ( M
air
/ A ) ( RT / M
air
) / P
h = 8721 m = 8.721 km = 5.420 mi (at 25C)
g on
g off
Real Gas: Volume Effect
Odors do NOT diffuse with the speed of sound; so gas
molecules must impede one another by collisions.
Kinetic Theory assumed molecules of zero volume, but that
would yield liquids of zero volume as well. No way.
Part of V is always taken up with a molecules molar
condensed volume, ~ b; we have to exclude nb from V.
That gives us the ideal volume the gas is free to use.
So a better gas equation is: P ( V nb ) = n RT
Waters exptl. b ~ 30.5 ml, while its liquid molar volume is 18.0 ml.
V
b
0.1%
Real Gas: Intermolecular Forces
For neutrals, all long-range forces are attractive!
In the bulk of a gas, molecular attractions to
nearest neighbors are in all directions; they cancel.
At the wall, such attractions are only from the
hemisphere behind; they retard the collider!
He strikes the wall less forcefully than had the
intermolecular forces actually been zero.
Real Gases: Pressure Effect
So the measured P
actual
is less than the Ideal P.
To use P
actual
in the Ideal Gas equation, we must
add back that lost molecular momentum.
The strength of intermolecular attraction grows as
the square of concentration; so the term is a[X]
2
or
a( n / V )
2
or a n
2
/ V
2
.
Pressure-corrected, its ( P + a n
2
/ V
2
) V = n RT

van der Waals Equation
( P + a n
2
/ V
2
) ( V n b ) = n RT
a and b are empirical parameters.
Ammonia has a large a value of 4.17 atm L
2
mol
2
So at STP, the pressure correction term is 0.0083 atm
or almost 1%. Hydrogen bonding has l o n g arms!
Van der Waals is an empirical equation and not
the only one, but a convenient one for estimates.
Other Non-Idealities
Even if PV = nRT, pressures and volumes can be
other than elementary.
An obvious source of mischief is uncertainty in n.
Chemical reaction in the gas phase may change n:
N
2
O
4
2 NO
2
K
300 K
= 11
If you evolve 1 mol of N
2
O
4
at 1 atm & 300 K, whats V ?
N
2
O
4
isnt a dimer, but HCO
2
H can dimerize a bit.
Gases with strong hydrogen-bonds mess with n.

NO
X
Volume Problem
N
2
O
4
2 NO
2
or A 2 B

1 mol of N
2
O
4
evolved at
300 K into P
total
= 1 atm
K = (P
B
)
2
/ P
A
= 11
K = P (X
B
)
2
/ X
A

K / P = X
B
2
/ X
A
= 11 / 1
(X
B
)
2
/ ( 1 X
B
) = 11
X
B
2
+ 11 X
B
11 = 0
X
B
= 0.9226; X
A
= 0.0774
n
B
= 2 ( 1 n
A
)
n = n
A
+ n
B
= 2 n
A

1 = ( 2 / n ) ( n
A
/ n )
1 = ( 2 / n ) X
A
n = 2 / ( 1 + X
A
)
n = 1.856
V = nRT / P = 45.69 L

Hydrostatic Pressure
Mercury is ~13.6 times as dense as water.
Thus, 1 atm = 0.76 m Hg 13.6 = 10.3 m H
2
O
Pressure increases by 1 atm with each 33 ft of water.
Mariana (deepest) Trench = 11,033 m for what total pressure?
P = 1 + 11,033 m /10.3 m/atm = 1 + 1,071 atm = 1,072 atm
But seawater has = 1.024 g/cc, so P = 1 + 1.0241,071 = 1,098 atm
Worlds Tallest Tree = 376.5 ft
How does it get water from the roots to its topmost leaves?
Pull a vacuum of NEGATIVE 10 atm?!? No
And what about waters vapor pressure?
Influence of Vapor Pressure @ 25C
Hg
760
Hg(g)
2 m
Hg
736
H
2
O(g)
24 mm
Hg
701
ethanol(g)
59 mm
Hg
222
ether(g)
538 mm
Acetone 231 mm
Methanol 127 mm
Propanal 317 mm
Gedanken Experiment
Gedanken is German for thought. Einstein loved them.
P
ether
+ P
acetone
= 538 mm + 231 mm = 769 mm
Does this mean that the total pressure for those two
liquids will exceed 1 atm?
If so, how about 1000 liquids with vapor pressures of,
say, atm each. Would they exert 500 atm?!?
If not, what happened to Daltons Law?
Has it gone bankrupt? See Chapter 11. (4)