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Gases

• 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

If a fixed amount of gas


is released into a larger
container,
how much force does it
exert?
If the volume of a gas is constrained to a smaller container,
how much force does it exert?

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?

• Ex. 2 A sample of O2 occupies 10.0 L at 785 torr.


At what pressure would it occupy 14.5 L?
If the temperature of gas is increased, how will its volume respond
(if the pressure is kept constant)?

Charle’s Law:

V1/T1 = V2 / T2
Gas 1

Gas 2

Gas 3

Gas 4

The point where a gas


would have zero volume!
If a gas is heated, how much force does it exert
(if the volume is kept constant)?

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

1) Gas equations should make sense: volume, pressure, temperature


2) Watch your units! (K, L, atm)
One standardized set of conditions =

“STP”
• 0o C (273 K)

• 1 atm (760 Torr)


• Ex. 3 A balloon filled with He occupies 413 mL at
100.oC. At what temperature would it occupy 577 mL if
the pressure was constant?

• Ex. 4 A sample of hydrogen sulfide (H2S) occupies 210 L


at 27oC at 1200 T. What volume would it occupy at STP?
How much volume does 1 mole of gas occupy
at 0o C, 1 atm?

If one mole of Argon occupies 22.1 L, how much volume


will be occupied by:

one mole CO2

one mole N2

one mole O2

one mole H2
How much volume does 1 mole of gas occupy
at 0o C, 1 atm?

Liters

Ideal gas: 22.41 L per mole


Ex. 5 What is the density of a gas that has a
molar mass of 44.01 g/mol at STP?
Ideal Gas Law: PV = nRT
(where n = moles)

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?

• Ex. 7 The Goodyear blimp must be inflated with Helium


prior to a football game. Its volume is 7601 ft3. How
many grams of He are needed for a pressure of 740 torr at
22o C?
(1 ft3 = 28.3 L)
• Ex. 9 A 0.723 g sample of a gas occupies
176 mL at 100.o C and 750. torr. What is its
molar mass?
Stoichiometric Calculations Involving Gases
C3H8 + 5O2  3CO2 + 4H2O
25.0 g of propane produces how many moles of CO2?
25.0 g of propane produces how many liters of CO2 at STP?
How many grams of propane are need to react with
50.0 L of O2 at 25o C and 1.0 atm?
Key Concepts:
• Ideal Gas Law PV = nRT

• STP (0o C and 1 atm)

• Standard molar volume: 22.4 L/mole at STP

• Gases in stoichiometric calculations


An airbag inflates in less than 50 msec by the reaction of NaN3
to produce Na and nitrogen gas:
NaN3  Na + N2
The volume of the airbag is about 30 L when inflated, and it is
filled to a pressure of 1.4 atm. How many grams of NaN3 must
be used for each air bag? The molar mass of NaN3 is 65.1
g/mole. Assume the process occurs at room temperature.
Gas mixtures
• Dalton’s Law of partial pressures
The total pressure of a mixture of gases equals the
sum of the pressures that each would exert if it
were present alone
PT=P1+P2+P3+….Pn

Exercise: A gaseous mixture is made from 6.00g oxygen and


9.00g methane placed in a 15L vessel at 0oC. What is the partial
pressure of each gas and the total pressure in the vessel?
Dalton’s law of
partial pressures

PT = Pa + Pb + Pc + Pd = …

Remember that each pressure


is also equal to: nXRT/V
Mole Fractions
• The ratio n1/nT is called the mole fraction (denoted x1), a
dimensionless number between 0 and 1.
P1 n1RT / V n1
 
PT nT RT / V nT
 n1 
P1    PT
 nT 
Mole fraction of N2 in air is 0.78, therefore if the total
barometric pressure is 760 torr, the partial pressure of N2 is
(0.78)(760) = 590 torr.
Kinetic –Molecular Theory
Theory describing why gas laws are obeyed (explains both pressure and
temperature of gases on a molecular level).
• Complete form of theory, developed over 100 years or so, published by
Clausius in 1857.
 Gases consist of large numbers of molecules that are in continuous,
random motion
 Volume of all molecules of the gas is negligible, as are
attractive/repulsive interactions
 Interactions are brief, through elastic collisions (average kinetic energy
does not change)
 Average kinetic energy of molecules is proportional to T, and all gases
have the same average kinetic energy at any given T.

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?

• Ex. 12 One tank of gas contains 5.00 L of N2 at 32.0 atm.


A second tank contains 3.00 L of O2 at 24.0 atm. What
pressure is attained when the valve between the tanks is
opened?
Mole fraction: the portion of a specific substance
within a mixture

What is the portion (mole fraction) of red spheres?


Kinetic model of 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
– VT
– 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

(What happens at high pressures and low


temperatures???)
• The molar volume is not constant as is expected for ideal
gases.
• These deviations due to an attraction between some
molecules.
• Finite molar molecular volume.
• For compounds that deviate from ideality the van der
Waals equation is used:
 n 2a 
P + (V - nb) = nRT
 2 
 V 

where a and b are constants that are characteristic of the


gas.
• Applicable at high pressures and low temperatures.
Ideal: PV = nRT

Real: (P + a n2/V2) (V – nb) = nRT

• a is a molecular attractivity factor

• b is a molecular volume factor


Ideal: P = nRT/V

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

Pressure depends on frequency of collisions with walls and


force of each collision – both reduced by attractive forces
proportional to molar concentration (n/V)
Pressure is then reduced according to a(n/V)2
Phase Transition: Condensation
Imagine you are compressing gas with piston
At C, piston slides without further change in
pressure
Liquid begins to appear – Two phases coexist
Going to E – amount of liquid increases
Pressure along CDE is vapour pressure
At E, sample is liquid – now the compressibility
changes ….

Similar behave happens in lipidic or polymeric


systems, which exhibit a rich variety of phase
transitions …

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

If you compress along Tc, liquid


does not appear – these highly
dense materials are called
“supercritical fluids” and their
properties are a subject of intense
current research
Virial Equation of State
Most fundamental and theoretically sound
Polynomial expansion – Viral Expansion

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

B2V (T =) 0 at Boyle temperature

Used to summarize P, V, T data


Also allow derivation of exact correspondence between
virial coefficients and intermolecular interactions