GASES

Properties of Gases
 Gases expand to fill the volume of any container.
 Gases have much lower densities than solids or liquids.
 Gases have highly variable densities, depending on the conditions.
 Gases mix with one another readily and thoroughly.
 Gases change volume dramatically with changing temperature.

Four properties determine the physical behavior of a gas: the amount of the gas (in moles) and the volume,
temperature, and pressure of the gas. If we know any three of these, we can usually calculate the value of the
remaining one by using a mathematical equation called an equation of state (such as the ideal gas equation.)

Kinetic Molecular Theory of Gases

Kinetic Molecular Theory provides connections between the observed macroscopic properties of gases, the
gas law equation, and the behavior of gas molecules on a microscopic scale. The following are the postulates of
KMT:
1. A gas is made up of a vast number of particles, and these particles are in constant random motion.
2. Particles in a gas are infinitely small; they occupy no volume.
3. Particles in a gas move in straight lines except when they collide with other molecules or with the walls
of the container. Collisions with each other and with the walls of the container are elastic, so that the
total kinetic energy of the particles is conserved.
4. Particles in a gas interact with each other only when collisions occur.
5. The average kinetic energy of the particles in a gas is proportional to the absolute temperature of the
gas and does not depend on the identity of the gas.

Pressure of Gas
Pressure is defined as force exerted per unit area:

𝐹
𝑃=
𝐴

In SI, the unit of force is a newton (N), which is the force, F, required to produce an acceleration of one
meter per second per second (1m/s2) in a one kilogram mass (1 kg), that is, 1N = 1kg-m/s2. The corresponding
force per unit area—pressure-- is expressed in the unit N/m2. A pressure of one newton per square meter is
defined as one pascal (Pa). Thus, a pressure in Pascals is
𝐹(𝑁)
𝑃(𝑃𝑎) =
𝐴(𝑚2 )

A pascal is a rather small pressure unit, so the kilopascal (kPa) is more commonly used. The pascal
honors Blaise Pascal (1623 1662), who studied pressure and its transmission through fluids the basis of modern
hydraulics.

Gas Laws

I. Boyle’s Law( Pressure-Volume Relationship)

The pressure exerted by a gas results from the impact of its molecules on the walls of the container.
The rate, or the number of molecular collisions with the walls per second, is proportional to the number of
molecules per unit volume of the gas.
Boyle’s Law states that the volume of a fixed amount of gas maintained at a constant temperature is
inversely proportional to the gas pressure.
Mathematically speaking, it is written as
1
𝑉∝
𝑃
  It means that when the pressure is increased, the volume will decrease or when the pressure is
decreased, the volume will increase.
 It means that that if the volume is doubled, the pressure will only be half as great; if the pressure is
three times as great, the volume must be one-third of what it was originally.

The symbol  means proportional to. To change the proportionality sign to an equals sign, K is written
and it becomes
1
𝑉=𝐾×
𝑃
𝐾
𝑉=
𝑃
𝑃𝑉 = 𝐾
Where: K is the proportionality constant and represents the number with a constant value—the value is
dependent on temperature, weight of the gas, its nature and units in which P and V are
expressed.

To compare the properties of the same amount of the same gas at the same temperature, set two
conditions, initial and final. Under the two conditions whey will have the same constant.
(𝑃𝑉)𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = (𝑃𝑉)𝑓𝑖𝑛𝑎𝑙
𝑃𝑖 𝑉𝑖 = 𝑃𝑓 𝑉𝑓
The use of Boyle’s Law is to predict the new volume of gas when the pressure is change.

Sample Problem:

1. In addition to ongoing sources, such as car engines, pollutants can also be introduce into the air through
isolated incidents like the rupture of a gas storage tank. Most gases are stored and transported at high
pressures. A common laboratory cylinder of methane, for example, has a volume of 49.0 L and is filled to a
pressure of 154 atm. Suppose that all of the CH4 from this cylinder is released and expands until its pressure
falls to 1.00 atm. What volume would the CH 4 occupy?

2. A 50.0 L cylinder contains nitrogen gas at a pressure of 21.5 atm. The contents of the cylinder are emptied
into an evacuated tank of unknown volume. If the final pressure in the tank is 1.55 atm, then what is the
volume of the tank?

II. Charles’ Law (Volume-Temperature Relationship)

Since the average kinetic energy of gas molecules is proportional to the sample’s absolute temperature,
raising the temperature increases the average kinetic energy. Consequently, molecules will collide with the
walls of the container more frequently and with greater impact if the gas is heated, and thus the pressure
increases. The volume of the gas will expand until the gas pressure is balanced by the constant external
pressure.
Charles’ Law states that the volume of a fixed amount of gas maintained at constant pressure is directly
proportional to the absolute temperature (Kelvin) of the gas.
 𝑉∝𝑇
𝑉 = 𝐾𝑇
𝑉
=𝐾
𝑇
𝑉 𝑉
( )𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = ( )𝑓𝑖𝑛𝑎𝑙
𝑇 𝑇
𝑉𝑖 𝑉𝑓
=
𝑇𝑖 𝑇𝑓

𝑉𝑖 𝑇𝑓 = 𝑉𝑓 𝑇𝑖

Sample Problem:

1. A balloon is filled with helium, and its volume is 2.2 L at 298 K. The balloon is then dunked into a
thermos bottle containing liquid nitrogen. When the helium in the balloon has cooled to the
temperature of the liquid nitrogen (77 K), what will the volume of the balloon be?

2. A balloon is inflated to a volume of 2.50 L inside a house that is kept at 24°C. Then it is taken outside
on a very cold winter day. If the temperature outside is -25°C, what will be the volume of the balloon
when it is taken outside? Assume that the quantity of air in the balloon and its pressure both remain
constant.

III. Gay-Lussac’s Law (Pressure-Temperature Relationship)

The pressure of a fixed amount of gas maintained at constant volume is directly proportional to its
absolute temperature.
𝑃∝𝑇
𝑃 = 𝐾𝑇
𝑃
=𝐾
𝑇
𝑃 𝑃
( )𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = ( )𝑓𝑖𝑛𝑎𝑙
𝑇 𝑇
𝑃𝑖 𝑃𝑓
=
𝑇𝑖 𝑇𝑓
𝑃𝑖 𝑇𝑓 = 𝑃𝑓 𝑇𝑖

Sample Problem:

1. A 400 mL sample of a gas in a steel cylinder has a pressure of 2.5 x10 -3 torr and a temperature of
100°C. if the closed cylinder is cooled to 20°C at constant volume, what is the new pressure of the gas
at atm?
 2. A gas exerts a pressure of 350 torr at 20°C. How many torr will it exert if its temperature is raised to
40°C without a change in volume?

IV. Combined Gas Law

Combination of Boyle’s Law, Charles’ Law, and Gay-Lussac’s Law gives the combined gas law
equation.
Boyle’s Law: 𝑃𝑖 𝑉𝑖 = 𝑃𝑓 𝑉𝑓
Charles’ Law: 𝑉𝑖 𝑇𝑓 = 𝑉𝑓 𝑇𝑖
Gay-Lussac’s Law: 𝑃𝑖 𝑇𝑓 = 𝑃𝑓 𝑇𝑖
𝑃𝑖 𝑉𝑖 𝑃𝑓 𝑉𝑓
=
𝑇𝑖 𝑇𝑓
𝑃𝑖 𝑉𝑖 𝑇𝑓 = 𝑃𝑓 𝑉𝑓 𝑇𝑖

Sample Problem:

1. Suppose that a balloon is launched when the temperature is 225°C and the barometric pressure is
754mmHg. If the balloon’s volume is 4.19 x 103L, what will it be at a height of 20 miles, where the
pressure is 76mmHg and the temperature is -33°C?

2. To what temperature in °C must 10L of nitrogen at 25°C and 700mmHg be heated in order to have a
volume of 15L and a pressure of 760mmHg?

V. Avogadro’s Law
The volume of a gas maintained at constant temperature and pressure is directly proportional to the
number of moles of gas.
𝑉∝𝑛
The relationship between gases measured at the same temperature and pressure contain the same
number of moles.
𝑛𝐴 = 𝑛𝐵
Properties of gases are often given at STP (Standard Temperature and Pressure).
T = 0°C or 273K
P = 1 atm or 760 torr
V = 22.4 L
Ideal Gas Equation
Gas laws involving volume relationships:

1. Avogadro’s Law: 𝑉∝𝑛

1
2. Boyle’s Law: 𝑉=
𝑃
3. Charles’ Law: 𝑉∝𝑇

1
𝑉 ∝ 𝑛 ( ) (𝑇)
𝑃

𝑃𝑉 ∝ 𝑛𝑇

𝑃𝑉 = 𝑅𝑛𝑇

𝑷𝑽 = 𝒏𝑹𝑻 (Ideal Gas Law Equation)

Where: R = universal gas constant

Determination or Evaluation of R
𝑃𝑉 = 𝑛𝑅𝑇

𝑃𝑉
𝑅=
𝑛𝑇

(1 𝑎𝑡𝑚)(22.4𝐿)
𝑅=
(1 𝑚𝑜𝑙𝑒)(273𝐾)

𝑅 = 0.082 𝐿 − 𝑎𝑡𝑚⁄𝑚𝑜𝑙𝑒 − 𝐾

Other values of R:

𝑅 = 1.987 𝑐𝑎𝑙𝑜𝑟𝑖𝑒𝑠⁄𝑚𝑜𝑙𝑒 − 𝐾

𝐽𝑜𝑢𝑙𝑒𝑠⁄
𝑅 = 8.31 𝑚𝑜𝑙𝑒 − 𝐾

One important use of the Ideal Gas Law Equation is in the determination of the molecular weight of a
gas from its density.

𝑃𝑉 = 𝑛𝑅𝑇

𝑚
𝑃𝑉 = 𝑅𝑇
𝑀𝑊

𝑚(𝑅𝑇)
𝑃=
𝑉(𝑀𝑊)

𝜌𝑅𝑇
𝑃=
𝑀𝑊
𝜌𝑅𝑇
𝑀𝑊 =
𝑃

Where: m = mass
MW = molecular weight
 = density
Sample Problems:

1. What is the volume occupied by 13.7g Cl2(g) at 45°C and 745 mmHg?

2. What is the pressure, in kiloPascals, exerted by 1.0 x 10 20molecules of N2 in a 305 mL flask at 175°C?

3. Propylene is an important commercial chemical (about ninth in the amount produced among
manufactured chemicals) used in the synthesis of other organic chemicals and in production of plastics
(polypropylene). A glass vessel weighs 40.1305g when clean, dry, and evacuated; it weighs 138.2410g
when filled with water at 25°C (=0.997g/mL) and 40.2959g when filled with propylene gas at 740.3
mmHg and 24°C. What is the molar mass of propylene?

4. What is the density of oxygen gas at 298 K and 0.987 atm?

Dalton’s Law of Partial Pressure

Partial Pressure – pressure exerted by each gas in a mixture of gases.

It was observed by John Dalton that when 2 or more gases as long as they don’t react are placed in the
same container, the pressure exerted by each gas in the mixture is the same as if it is alone in the container
 Dalton’s Law of Partial Pressure states that the total pressure exerted by a mixture of gases is the sum
of the partial pressures of each gas in the mixture.

𝑃𝑇 = 𝑃𝐴 + 𝑃𝐵 + 𝑃𝐶 + ⋯

The partial pressure of each gas can be determined from the ideal gas law equation.

𝑃𝑉 = 𝑛𝑅𝑇

𝑛𝐴 𝑅𝑇 𝑛𝐵 𝑅𝑇 𝑛𝐶 𝑅𝑇
𝑃𝐴 = 𝑃𝐵 = 𝑃𝐶 =
𝑉𝐴 𝑉𝐵 𝑉𝐶

The partial pressure can also be determined by

𝑛𝐴 𝑛𝐵 𝑛𝐶
𝑃𝐴 = (𝑃𝑇 ) 𝑃𝐵 = (𝑃𝑇 ) 𝑃𝐶 = (𝑃𝑇 )
𝑛𝑇 𝑛𝑇 𝑛𝑇

𝑛 𝑇 = 𝑛𝐴 + 𝑛𝐵 + 𝑛𝐶

% 𝑏𝑦 𝑣𝑜𝑙𝑢𝑚𝑒𝐴 % 𝑏𝑦 𝑣𝑜𝑙𝑢𝑚𝑒𝐵 % 𝑏𝑦 𝑣𝑜𝑙𝑢𝑚𝑒𝐶

𝑃𝐴 = (𝑃𝑇 ) 𝑃𝐵 = (𝑃𝑇 ) 𝑃𝐶 = (𝑃𝑇 )
100 100 100

Sample Problem:

1. A mixture of gas composes of 1g H2 and 5g He. What are the partial pressures of H2 and He in the
gaseous mixture when the mixture is confined to a volume of 5L at 20°C?

2. A mixture of gases contains 4.46moles of Ne, 0.74mole of Ar and 2.15moles of Xe. Calculate the
partial pressures of the gases if the total pressure is 2 atm at a certain temperature.

3. A mixture of gases contains 40% by volume H2, 30% by volume N2, 20% by volume O2 and 10% by
volume He. If the total pressure of the mixture is 1.8atm, what is the partial pressure of each gas in torr
and in atm?
Gases in Chemical Reactions

1. What volume of N2, measured at 735mmHg and 26°C, is produced when 75g NaN3 is decomposed?

2. Zinc blende, ZnS, is the most important zinc ore. Roasting (strong heating) of ZnS in oxygen is the first
step in the commercial production of zinc.
2ZnS(s) + 3O2(g) 2ZnO(s) + 2SO2(g)
What volume of SO2(g) can be obtained from 1L O2(g) and excess ZnS(s)? Both gases are measured at
25°C and 745 mmHg.

3. When an experiment required a source of carbon dioxide, a student combined 1.4 g of sodium
bicarbonate (NaHCO3) with excess hydrochloric acid. If the CO2 produced is collected at 722 torr and
17°C, what volume will the gas occupy?

4. One way to reduce air pollution is to remove potential pollutant gases from an exhaust stream before
they are released into the air. Carbon dioxide can be removed from a stream of gas by reacting it with
calcium oxide to form calcium carbonate. If we react 5.50 L of CO2 at STP with excess CaO, what
mass of calcium carbonate will form?

Graham’s Law of Diffusion and Effusion

Diffusion
 Spread of one substance throughout a space or through a second substance
 Process by which one gas gradually mixes with another.
Effusion
 Process by which a gas under pressure escapes from one compartment of a container to another by passing
through a small opening

The rates of diffusion or rates of diffusion for gaseous substances are

a. Inversely proportional to the square roots of their molecular weights.

1
𝑅𝑎𝑡𝑒 ∝
√𝑀𝑊

1
𝑅𝐴 ∝
√𝑀𝑊𝐴

1
𝑅𝐴 = 𝑘 ( )
√𝑀𝑊𝐴

𝑅𝐴 (√𝑀𝑊𝐴 ) = 𝑘

1
𝑅𝐵 ∝
√𝑀𝑊𝐵

1
𝑅𝐵 = 𝑘 ( )
√𝑀𝑊𝐵

𝑅𝐵 (√𝑀𝑊𝐵 ) = 𝑘

𝑅𝐴 (√𝑀𝑊𝐴 ) = 𝑅𝐵 (√𝑀𝑊𝐵 )

𝑹𝑨 √𝑴𝑾𝑩
=
𝑹𝑩 √𝑴𝑾𝑨

b. Inversely proportional to the square roots of their densities.

1
𝑅𝑎𝑡𝑒 ∝
√𝜌

1
𝑅𝐴 ∝
√𝜌𝐴

1
𝑅𝐴 = 𝑘 ( )
√𝜌𝐴

𝑅𝐴 (√𝜌𝐴 ) = 𝑘

1
𝑅𝐵 ∝
√𝜌𝐵

1
𝑅𝐵 = 𝑘 ( )
√𝜌𝐵

𝑅𝐵 (√𝜌𝐵 ) = 𝑘

𝑅𝐴 (√𝜌𝐴 ) = 𝑅𝐵 (√𝜌𝐵 )
 𝑹𝑨 √ 𝝆 𝑩
=
𝑹𝑩 √ 𝝆 𝑨

c. Inversely proportional to their time to effuse through a barrier.

1
𝑅𝑎𝑡𝑒 ∝
𝑡
1
𝑅𝐴 ∝
𝑡𝐴
1
𝑅𝐴 = 𝑘
𝑡𝐴
𝑅𝐴 𝑡𝐴 = 𝑘
1
𝑅𝐵 ∝
𝑡𝐵
1
𝑅𝐵 = 𝑘
𝑡𝐵
𝑅𝐵 𝑡𝐵 = 𝑘

𝑅𝐴 𝑡𝐴 = 𝑅𝐵 𝑡𝐵

𝑹𝑨 𝒕 𝑩
=
𝑹𝑩 𝒕 𝑨

Lighter gases effuse through a small opening more rapidly than the heavier ones.

Sample Problems:

1. Calculate the ratio of effusion rates of CO2 and SO2, from the same container and at the same temperature
and pressure.. Which will diffuse faster?

2. Tetrafluoroethylene, C2F4, effuses through a barrier at the rate of 4.6 x 10 -6mole/hr. an unknown gas,
consisting only of boron and hydrogen, effuses at the rate of 5.8 x 10 -6 mole/hr under the same conditions.
What is the molecular weight of the unknown gas?
Nonideal (Real) Gases

Real gases are not ideal. We should comment briefly on the conditions under which a real gas is ideal
or nearly so and what to do when the conditions lead to nonideal behavior. A useful measure of how much a gas
deviates from ideal gas behavior is found in its compressibility factor. The compressibility factor of a gas is the
ratio PV/nRT. From the ideal gas equation we see that for an ideal gas, PV/nRT=1. For a real gas, the
compressibility factor can have values that are significantly different from 1. Values of the compressibility
factor are given in Table 1 for a variety of gases at 300 K and 10 bar. The data in Table 1 show that the
deviations from ideal gas behavior can be small or large, depending on the gas. At 300 K and 10 bar, He, H2,
CO, N2, and O2 behave almost ideally but NH3 and SF6 do not. You have to take note that all gases behave
ideally at sufficiently low pressures, say, below 1 atm, but that deviations set in at increased pressures. At very
high pressures, the compressibility factor is always greater than one.

Table 1. van der Waals Constants and Compressibility Factors (at 10 bar and 300K) for Various Gases
Gas Van der Waals Constants Compressibility Factor
a, bar-L2/mol2 b, L/mol
H2 0.2452 0.0265 1.006
He 0.0346 0.0238 1.005
*Ideal gas 0 0 1
N2 1.370 0.0387 0.998
CO 1.472 0.0395 0.997
O2 1.382 0.0319 0.994
CH4 2.303 0.0431 0.983
NF3 3.58 0.0545 0.965
CO2 3.658 0.0429 0.950
N 2O 3.852 0.0444 0.945
C2H6 5.580 0.0652 0.922
NH3 4.225 0.0371 0.887
SF6 5.580 0.0651 0.880
C3H8 9.39 0.0905 a
SO2 7.857 0.0879 a
rd
Source: van der Waals constants are from the CRC Handbook of Chemistry and Physics, 83 ed., David R. Lide
(ed.)., Boca Raton, FL: Taylor & Francis Group, 2002. Compressibility factors are calculated by using data from
the National Institute of Standards and Technology (NIST) Chemistry WebBook, available online at
http://webbook.nist.gov/chemistry/

Nonideal gas behavior can be described as follows: Boyle’s law predicts that at very high pressures, a
gas volume becomes extremely small and approaches zero. This cannot be, however, because the molecules
themselves occupy space and are practically incompressible. Because of the finite size of the molecules, the PV
product at high pressures is larger than predicted for an ideal gas, and the compressibility factor is greater than
one. Another consideration is that intermolecular forces exist in gases. Because of attractive forces between the
molecules, the force of the collisions of gas molecules with the container walls is less than expected for an ideal
gas. Intermolecular forces of attraction account for compressibility factors of less than one. These forces become
increasingly important at low temperatures, where translational molecular motion slows down.
To summarize:
 Gases tend to behave ideally at high temperatures and low pressures.
 Gases tend to behave nonideally at low temperatures and high pressures.

The van der Waals Equation

A number of equations can be used for real gases, equations that apply over a wider range of
temperatures and pressures than the ideal gas equation. Such equations are not as general as the ideal gas
equation. They contain terms that have specific, but different, values for different gases. Such equations must
correct for the volume associated with the molecules themselves and for intermolecular forces of attraction. Of
all the equations that chemists use for modeling the behavior of real gases, the van der Waals equation, is the
simplest to use and interpret.
𝑎𝑛2
(𝑃 + 2 ) (𝑉 − 𝑛𝑏) = 𝑛𝑅𝑇
𝑉
The equation incorporates two molecular parameters, a and b, whose values vary from molecule to
molecule, as shown in Table 1.
The van der Waals equation and the ideal gas equation both have the form 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑓𝑎𝑐𝑡𝑜𝑟 ×
𝑣𝑜𝑙𝑢𝑚𝑒 𝑓𝑎𝑐𝑡𝑜𝑟 = 𝑛𝑅𝑇. The van der Waals equation uses a modified pressure factor, 𝑃 + 𝑎𝑛2 /𝑉 2 , in place of
P and a modified volume factor, 𝑉 − 𝑛𝑏 , in place of V. In the modified volume factor, the term nb accounts for
the volume of the molecules themselves. The parameter b is called the excluded volume per mole, and, to a
rough approximation, it is the volume that one mole of gas occupies when it condenses to a liquid. The volume
of the container must be no smaller than nb, and the volume available for molecular motion is 𝑉 − 𝑛𝑏. As
suggested in Figure 6-21(b), the volume available for molecular motion is quite small at high pressures.
To explain th significance of the term an2/V2 in the modified pressure factor, it is helpful to solve for P:
𝑛𝑅𝑇 𝑎𝑛2
𝑃= − 2
𝑉 − 𝑛𝑏 𝑉
Provided V is not too small, the first term in the equation above is approximately equal to the pressure
𝑛𝑅𝑇 𝑛𝑅𝑇
exerted by an ideal gas: ≈ = 𝑃𝑖𝑑𝑒𝑎𝑙 .The equation given above for P predicts that the pressure exerted
𝑉−𝑛𝑏 𝑉
by a real gas will be less than that of an ideal gas. Because of attractive forces, molecules near the container
walls are attracted toward the molecules behind them; as a result, the gas exerts less force on the container walls.
The term 𝑎𝑛2 /𝑉 2 takes into account the decrease in pressure caused by intermolecular attractions. In 1873, the
Dutch physicist Johannes van der Waals reasoned that the decrease in pressure caused by intermolecular
attractions should be proportional to the square of the concentration, and so the decrease in pressure is
𝑎𝑛2
represented in the form . The proportionality constant, a, provides a measure of how strongly the molecules
𝑉2
attract each other.
A close examination of Table 1 shows that the values of both a and b increase as the sizes of the
molecules increase. The smaller the values of a and b, the more closely the gas resembles an ideal gas.
Deviations from ideality, as measured by the compressibility factor, become more pronounced as the values of a
and b increase.

Sample Problem:

1. Use the van der Waals equation to calculate the pressure exerted by 1 mole Cl2(g) confined to a volume of
2L at 273K. the value of a =6.49L2-atm/mol2, and that of b=0.0562L/mol.

2. Consider a CH4 storage tank with a volume of 49.0 L. When empty, the tank has a mass of 55.85 kg, and
when filled, its mass is 62.07 kg. Calculate the pressure of CH4 in the tank at an ambient temperature of
21°C using both the ideal gas equation and the van der Waals equation. What is the percentage correction
achieved by using the more realistic van der Waals equation?