Gases, Chapter 6
1
Part 6.1: Supersonic Skydiving and the Risk of Decompression
&
Part 6.2: Pressure: The Result of Molecular Collisions
Slide 3: Pressure
Slide 4: Measuring the Pressure in the Laboratory
2
Pressure
• Pressure is the force exerted per unit area by gas particles as they strike the surfaces
around them. Mathematically, we define pressure as follows:
P=
• Several different units are used to report the quantity pressure:
1 mmHg = 1 torr
1 atm = 760 mmHg or 760 torr
1 atm = 29.92 inches Hg
1 atm = 14.7 psi (pounds per square inch)
The SI unit of pressure is the pascal (Pa). 1 Pa =
1 atm = 101,325 Pa
3
Measuring the Pressure in the Laboratory
• A manometer is used to measure gas pressure of a gas sample in the laboratory and a
barometer is used to measure atmospheric pressure.
manometer barometer
4
Part 6.3: The Simple Gas Laws: Boyle’s Law, Charles’s Law, and Avogadro’s Law
Slide 6: Boyle’s Law: Volume and Pressure
Slide 7: Charles’s Law: Volume and Temperature
Slide 8: Avogadro’s Law: Volume and Amount (in Moles)
5
Boyle’s Law: Volume and Pressure
• Boyle’s law states that pressure (P) and volume (V) are inversely related at constant
temperature (T) and no. of moles of gas (n). Mathematically, this can be expressed:
PV = constant or P1V1 = P2V2
• The graphic below (left) shows that doubling the P reduces the volume in half. The
plot of P vs. V show the two quantities are inversely related. The plot of P vs. 1/V
gives a straight line.
6
Charles’s Law: Volume and Temperature
• Charles’s law states that volume (V) and temperature (T) are directly related at constant
pressure (P) and no. of moles of gas (n). Mathematically, this can be expressed:
= constant or =
• The graphic below (left) shows as the temperature is raised the volume increases. The
plot below shows that volume and temperature are directly related.
7
Avogadro’s Law: Volume and Amount (in Moles)
• Avogadro’s Law states that volume and no. of moles of gas are directly related at constant
temperature and pressure. Mathematically, this can be expressed:
= constant or =
• The graphic below (left) shows that at constant pressure and temperature balloons of
equal volume contain the same amount (in moles) of gas. The plot below shows
volume and no. of moles are directly related.
8
Part 6.4: The Ideal Law
Slide 10: The Ideal Gas Law
Slide 11: Special Cases of the Ideal Gas Law
9
The Ideal Gas Law
• If Boyle’s law, Charles’s law and Avogadro’s law are combined we arrive at the ideal gas
law. Put another way, these three laws are just special cases of the ideal gas law.
Mathematically, the ideal gas law can be expressed:
PV = nRT, where R = 0.082
R is the ideal gas constant.
10
Special Cases of the Ideal Gas Law
PV = nRT
Constant n & T Constant P & T
Constant n & P
Boyle’s Law Charles’s Law Avogadro’s Law
P1V1 = P2V2 = =
11
Part 6.5: Applications of the Ideal Gas Law: Molar Volume, Density, and Molar Mass of a Gas
Slide 13: Molar Volume and Density of a Gas
12
Molar Volume and Density of a Gas
• STP stands for standard temperature and pressure. At STP:
Temperature = 0oC or 273 K (Note: when doing gas law problems, you must express
temperature in degrees Kelvin)
Pressure = 1 atm
• The molar volume (the volume occupied by one mole of a gas at STP) is for an ideal
gas 22.4 L.
• The ideal gas law can be modified in away that allows us to find the density of a gas
(in grams per liter). The mathematical expression for finding the density of a gas, d, is:
d=
where P = pressure (in atm), M = mass of gas (in g/mol), T = temperature (in K), and
R = 0.082 .
13
Part 6.6 Mixtures of Gases and Partial Pressures
Slide 15: Partial Pressures
Slide 16: Water Vapor Pressure Table
14
Partial Pressures
• Since each gas in a mixture acts independently of the other gases in that mixture, the
total pressure of the gas mixture is the sum of the individual pressures.
• Dalton’s law of partial pressures is expressed mathematically as: Ptotal = Pa + Pb + Pc + …
• The partial pressure of one component in a gas mixture is expressed mathematically as:
Pa = χaPtotal, where χa is the mole fraction of a in the mixture, namely χa =
• When a gaseous product is collected by the displacement of water, the gas is not pure
but rather contains water vapor plus the gaseous product. For example, if the gaseous
product is NO(g), the total pressure is: Ptotal = PNO + PH O .
2
• The vapor pressure of water increases with temperature. The vapor pressure of water
can be determined by measuring the temperature of water. So, the pressure of NO(g),
PNO, can be determined by measuring atmospheric pressure, Ptotal, and looking up PH2O
15
based on the temperature of the water. See the chart on the next slide.
16
Part 6.7: Gases in Chemical Reactions: Stoichiometry Revisited
Slide 18: Stoichiometry Problems Involving Gases
17
Stoichiometry Problems Involving Gases
• In stoichiometry problems involving gases volumes of R or P are often used. This can be
handled by using the ideal gas law.
• For example, consider the combustion of propane. If we ask what volume of propane is
needed to produce 500.0 g CO2 at 47oC and pressure of 741.0 mm Hg, we proceed as
follows:
C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(g)
500 g CO2 x x = 3.78 mol C3H8
V(C3H8) = = = 101.73 L C3H8
Note: P = 741 mmHg x = 0.975 atm
18
Part 6.8: Kinetic Molecular Theory: A Model for Gases
Slide 20: Kinetic Molecular Theory
Slide 21: Temperature and Molecular Velocities
Slide 22: Variation of Gas Velocity Distributions with Molar Mass
Slide 23: Variation of Velocity Distribution with Temperature
19
Kinetic Molecular Theory
• The three basic postulates of kinetic molecular theory are:
1. The size of a gaseous particle is negligibly small. If at STP an argon (Ar) atom were the
size of a golf ball (d = 1.68 inches), the nearest Ar atom would be 47.2 inches away,
which is 28x the diameter of the golf ball.
2. The average kinetic energy of a gaseous particle is proportional to the temperature
expressed in Kelvin. It is important realize there is always a wide distribution of
velocities of the gas particles at any given temperature.
3. The collision of one gaseous particle with another (or the wall of the container) is
completely elastic, which means no energy is lost. However, it may be redistributed.
Also, between collisions one gaseous particle does not influence the trajectory of
another gaseous particle.
20
Temperature and Molecular Velocities
• Increasing the temperature of a collection of gas particles causes their velocity to increase.
• The following mathematical expression supplies the relationships between velocity,
temperature , and molar mass:
urms = or ()½
where:
The quantity urms is the root mean square velocity of the gas particles.
M is the molar mass of the gas particle expressed as kilograms per mole.
T is temperature expressed in Kelvin.
R is the gas law constant with equals 8.314
• This relationship shows:
The urms is proportional to the square root of the temperature expressed in Kelvin.
The urms is inversely proportional to the square root of the molar mass (in kg/mole)
of the particles. 21
Variation of Gas Velocity Distributions with Molar Mass
• The higher the molecular weight of a gas the slower the gas particles move. However, remember that at a
given temperature, all gases have the same average kinetic energy (½mv2).
• At any given temperature, there is a distribution of gas velocities. Gases with a low molecular weight have
a broader distribution of velocities. Gases with a high molecular weight have a narrower distribution of
velocities.
At a Given Temperature
22
Variation of Velocity Distribution with Temperature
• For a given gas (below it is N2) as the temperature of the gas is raised, the average velocity
increases and the distribution of velocities broadens.
In contrast to N2,
the urms of H2 at
25oC is 4295 mi/hr. The urms of N2 at 25oC
1152 mi/hr.
23
Part 6.9: Mean Free Path, Diffusion, and Effusion of Gases
Slide 25: Mean Free Path and the Diffusion of Gas Particles
Slide 26: Diffusion of Ammonia (NH3) and Hydrogen Chloride (HCl)
to Form Ammonium Chloride (NH4Cl)
Slide 27: Effusion of Gases
24
Mean Free Path and the Diffusion of Gas Particles
• Diffusion occurs when a new gas is introduced into a larger volume and the new gas
particles spread out to occupy the entire volume.
• An example of diffusion: a bottle of concentrated ammonia (NH3, MW = 17.0 g/mol) is
opened at one end of the lab. It takes some time before a second student at the other
end of the lab will smell it. If the ammonia bottle were replaced with triethylamine
(N(CH2CH3)3, MW = 101.2 g/mol) with a similar smell, it will take longer for the second
student to smell it than it did with the ammonia. Heavier gas particles diffuse more slowly.
• The average distance that a gaseous particle travels between collisions is defined as its
mean free path.
• A N2 molecule (diameter = 300 pm) at room temperature and atmospheric pressure has
a mean free path of 93,000 pm, which is 310 molecular diameters. Collisions occur
frequently.
25
Diffusion of Ammonia (NH3) and Hydrogen Chloride (HCl) to Form Ammonium Chloride (NH4Cl)
• The photo (bottom right) and the diagram (bottom left) illustrate that if gaseous NH3
(MW = 17.0 g/mol) and gaseous HCl (MW = 36. 5 g/mol) are allowed to diffuse, the
product of the reaction NH4Cl(s) forms closer to the HCl source (and further from the
NH3 source) because the lighter NH3 travels further than the heavier HCl. HCl has a
molar mass roughly twice that of NH3.
NH3(g) + HCl(g) → NH4Cl(s)
26
Effusion of Gases
• Effusion is the escape of a gas molecule through a small hole into a vacuum. It is simpler
than diffusion because it does not depend on collisions.
• Graham’s law of effusions states that the ratio of rates of effusion of two gases , , is
equal to the square root of the inverse ratio of the molar masses, .
27
Part 6.10: Real Gases: The Effects of Size and Intermolecular Forces
Slide 29: The van der Waals Equation
Slide 30: Van der Waals Constants of Some Common Gases
28
The van der Waals Equation
• The van der Waals equation is an equation that addresses deviations from ideal gas
behavior.
• These deviations occur at:
High pressure where the volume of gas particles can no longer be considered negligible.
Low temperature where interactions between gaseous particles become important.
They must be important, because cooled gases liquify (become liquids).
• The van der Waals equation, supplied below, modifies the pressure and the volume in the
ideal gas law, where n equals number of moles and a and b are van der Waals constants
that are different for each gas.
Correction factor to account
for intermolecular attractions
Correction factor to account
corrected corrected for the finite size of molecules
pressure volume 29
Van der Waals Constants of Some Common Gases
Helium (He) shows the smallest deviation from
ideal behavior because it is very small and the
intermolecular forces between He atoms are very
weak. Boiling point for He is 4.2 k.
Even at 1 atm pressure CO2(g) shows considerable
deviation from ideal behavior. Compare a for He
(0.0341) with that for CO2 (3.59).
30
