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• Properties of Gases
• Gas Laws (pressure, volume, temperature,
moles)
• Gases in Chemical Reactions
• The Kinetic Model of Gases
Gaseous elements
Pressure = Force/Area
Boyle’s Law
V ~ 1/P
P ~ 1/V
Boyle’s Law:
P1V1 = P2V2
Relationship V1
between
volume and
pressure. P1
P1V1 = P2V2
Decrease volume
more collisions
V2
• Ex. 1 A sample of gas occupies 21 liters at a
pressure of 2.2 atm. What would be the volume if
the pressure was increased to 6.2 atm?
Charle’s Law:
V1/T1 = V2 / T2
Gas 1
Gas 2
Gas 3
Gas 4
P~T
Combined Gas Law
(Boyle and Charle’s)
P1 V1 = P2 V2
T1 T2
Re-cap of Gases:
Boyle’s Law: Charles’s Law:
P1 V1 = P2 V2 V1/T1 = V2 / T2
P1 V1 = P2 V2
T1 T2
“STP”
• 0o C (273 K)
one mole N2
one mole O2
one mole H2
How much volume does 1 mole of gas occupy
at 0o C, 1 atm?
Liters
What is “R”?
“STP” = 0 o C and 1 atm
• Ex. 6 What is the volume of a balloon filled with 32.02
grams of Helium when the atmospheric pressure is 722 torr
and the temperature is 40o C?
PT = Pa + Pb + Pc + Pd = …
Because each molecule of gas will have an individual kinetic energy, and thus
individual speed, the speed of molecules in the gas phase is usually characterised
by the root-mean-squared (rms) speed, u,(not the same though similar to the
average speed). Average kinetic energy є = ½mu2
Application to Gas Laws
• Increasing V at constant T:
Constant T means that u is unchanged.
But if V is increased the likelihood of
collision with the walls decreases,
thus the pressure decreases (Boyle’s
Law)
• Increasing T at constant V:
Increasing T increases u, increasing
collisional frequency with the walls,
thus the pressure increases (Ideal Gas
Equation).
• Ex. 10 A 20.5 L bulb contains 0.200 moles of methane,
0.300 moles of hydrogen, and 0.400 moles of nitrogen at
20.0 o C. It is stinky and explosive. What is the pressure
inside the bulb? How much pressure is contributed by
each of the three gases?
each dot is
one gas
molecule
The Kinetic-Molecular Theory
• The basic assumptions of kinetic-molecular theory
are:
• Postulate 1
– Gases consist of discrete molecules that are relatively far
apart.
– Gases have few intermolecular attractions.
– The volume of individual molecules is very small compared
to the gas’s volume.
• Proof - Gases are easily compressible.
The Kinetic-Molecular Theory
• Postulate 2
– Gas molecules are in constant, random, straight
line motion with varying velocities.
• Proof - Brownian motion displays
molecular motion.
The Kinetic-Molecular Theory
• Postulate 3
– Gas molecules have elastic collisions with
themselves and the container.
– Total energy is conserved during a collision.
• Proof - A sealed, confined gas exhibits no
pressure drop over time.
The Kinetic-Molecular Theory
• Postulate 4
– The kinetic energy of the molecules is
proportional to the absolute temperature.
– The average kinetic energies of molecules of
different gases are equal at a given
temperature.
• Proof - Brownian motion increases as
temperature increases.
The Kinetic-Molecular Theory
• The kinetic energy of the molecules is
proportional to the absolute temperature. The
kinetic energy of the molecules is proportional to
the absolute temperature.
• Displayed in a Maxwellian distribution.
The Kinetic-Molecular Theory
• The gas laws that we have looked at earlier in this chapter are
proofs that kinetic-molecular theory is the basis of gaseous
behavior.
• Boyle’s Law
– P 1/V
– As the V increases the molecular collisions with container
walls decrease and the P decreases.
• Dalton’s Law
– Ptotal = PA + PB + PC + .....
– Because gases have few intermolecular attractions, their
pressures are independent of other gases in the container.
• Charles’ Law
– VT
– An increase in temperature raises the molecular velocities,
thus the V increases to keep the P constant.
The Kinetic-Molecular Theory
• The root-mean square velocity of gases is a
very close approximation to the average gas
velocity.
• Calculating the root-mean square velocity is
simple:
3RT
u rms
Mm
• To calculate this correctly:
– The value of R = 8.314 kg m2/s2 K mol
– And M must be in kg/mol.
The Kinetic-Molecular Theory
• Example 12-17: What is the root mean square
velocity of N2 molecules at room T, 25.0oC?
kg m 2
3 8.314 2 298 K
sec K mol
u rms
0.028 kg / mol
515 m / s = 1159 mi / hr
The Kinetic-Molecular Theory
• What is the root mean square velocity of
He atoms at room T, 25.0oC?
The Kinetic-Molecular Theory
kg m
2
3 8.314 2 298 K
sec K mol
u rms
0.004 kg / mol
1363 m / s = 3067 mi / hr
• Can you think of a physical situation that proves
He molecules have a velocity that is so much
greater than N2 molecules?
• What happens to your voice when you breathe
He?
Diffusion and Effusion of Gases
• Diffusion is the intermingling of gases.
• Effusion is the escape of gases through
tiny holes.
Diffusion and Effusion of Gases
• This is a demonstration of diffusion.
Diffusion and Effusion of
Gases
• The rate of effusion is inversely proportional
to the square roots of the molecular weights
or densities.
R1 M2
R2 M1
or
R1 D2
R2 D1
Diffusion and Effusion of Gases
• Calculate the ratio of the rate of effusion of He
to that of sulfur dioxide, SO2, at the same
temperature and pressure.
R He M SO 2
R SO 2 M He
641
. g / mol
4.0 g / mol
16 4 R He 4R SO 2
Diffusion and Effusion of Gases
• Example 12-16: A sample of hydrogen, H2, was found to
effuse through a pinhole 5.2 times as rapidly as the same
volume of unknown gas (at the same temperature and
pressure). What is the molecular weight of the unknown
gas?
R H2 M unk
R unk M H2
M unk
5.2
2.0 g/mol
M unk
27
2.0 g/mol
M unk 27( 2.0 g/mol) = 54 g/mol
Real Gases:
Deviations from Ideality
• Real gases behave ideally at ordinary
temperatures and pressures.
• At low temperatures and high pressures real
gases do not behave ideally.
• The reasons for the deviations from ideality are:
1. The molecules are very close to one another, thus
their volume is important.
2. The molecular interactions also become important.
Real Gases:
Deviations from Ideality
• van der Waals’ equation accounts for the
behavior of real gases at low temperatures and
high pressures.
n 2a
2
P + V nb nRT
V
• The van der Waals constants a and b take into
account two things:
1. a accounts for intermolecular attraction
2. b accounts for volume of gas molecules
• At large volumes a and b are relatively small
and van der Waal’s equation reduces to ideal
gas law at high temperatures and low
pressures.
Real Gases:
Deviations from Ideality
• What are the intermolecular forces in
gases that cause them to deviate from
ideality?
1. For nonpolar gases the attractive forces
are London Forces
2. For polar gases the attractive forces are
dipole-dipole attractions or hydrogen
bonds.
Real Gases:
Deviations from Ideality
• Example 12-19: Calculate the pressure exerted by
84.0 g of ammonia, NH3, in a 5.00 L container at
200. oC using the ideal gas law.
1 mol
n = 84.0 g NH3 4.94 mol
17.0 g
L atm
4.94 mol 0.0821 473 K
P=
nRT
mol K
V 5.00 L
P 38.4 atm
Real Gases:
Deviations from Ideality
• Solve Example 12-19 using the van der
Waal’s equation.
L2 atm
n = 4.94 mol a = 4.17 b = 0.0371 L
mol 2 mol
n 2a
P + 2 V - nb nRT
V
nRT n 2a
P= 2
V - nb V
Real Gases:
Deviations from Ideality
4.94 mol 0.0821 473K 4.94 mol 4.17
L atm
2 L2 atm
P mol K
mol 2
5.00 L (4.94 mol )(0.0371 mol )
L
5.00 L 2
191.8 L atm
P 4.07 atm (39.8 atm 4.1 atm )
4.817 L
P 35.7 atm which is a 7.6% difference from ideal
“Real” gases
• Deviations from ideal behavior as gases are
exposed to:
– high pressures
– low temperatures
Real:
P = nRT/(V – nb) - a 2
n /V 2
“Real” gases
Ex. 13 Calculate the pressure exerted by 5.00 moles
of NH3 in a 1.00 L vessel at 25.0oC assuming ideal
and non-ideal behavior.
Compression Factor
Variation of Z with Pressure
At 0 C
molar volume
Z
molar volume perfect gas
pV
Z
RT
Low pressures, Z=1, all gases ideal
At high pressures, Vreal >Videal ; Z>1
repulsive forces dominate
Low pressure, Vreal <Videal, Z< 1
attractive forces dominate
Low temperatures -> molecules moving
less rapidly more influenced by
attractive forces
Van der Waals Equation (1873)
2
RT a nRT n
p 2 p a
Vm b Vm V nb V
a reflects how strongly molecules attract each other
b corrects for the molecule’s size
“Derivation” of vdw Eq. State
Repulsive interactions cause molecules to behave as
impenetrable spheres
Molecules restricted to smaller volume V-nb, where nb is
volume molecules take up
Experimental isotherms of
CO2 at several temperatures.
Critical Constants
The `critical isotherm', the isotherm
at the critical temperature Tc, is at
31.04 C. The critical point is
marked with a star.
Critical pressure Pc
Critical molar volume Vc
Tc, Pc,Vc critical constants
PV
Z 1 B2 P ( P) P B3 P ( P) P 2 ...
RT
PV B (T ) B3V (T )
Z 1 2V 2
...
RT V V