One of the simplest types of molecular motion to describe is the random motion of Application of KMT to the Gas Laws

molecules of a perfect gas. We see that a simple theory accounts for the pressure of a gas 1. Effect of volume increase on pressure at constant temperature
and the rates at which molecules and energy migrate through gases. In this chapter, we • The speed at which molecules travel remains unchanged when temperature is
will review the kinetic theory of gases, focusing on ideal gases. constant. Remember that the kinetic energy of gas molecules is proportional to
the temperature.
OBJECTIVES • An increase in volume also increases the distance at which the molecules travel.
When this happens, there will be fewer collisions on the container walls per unit
1. State the major concepts behind the kinetic molecular theory of gases. time. Fewer collisions result to decrease in pressure.
2. Demonstrate the relationship between kinetic energy and molecular speed.
3. Apply the kinetic molecular theory to explain and predict the gas laws. 2. Effect of temperature increase on pressure at constant volume
• No change in volume means constant number of collisions against the container
walls.
STATEMENT OF THE KINETIC MOLECULAR THEORY • An increase in temperature means an increase in kinetic energy. The greater the
Kinetic Molecular Theory - formulated by Rudolf Clausius that provides a model to kinetic energy, the more collisions occur with the walls of the container. Hence,
explain the regularity observed in the behavior of ideal gases. While the ideal gas equation the pressure of the gas increases.
describes how gases behave, the kinetic molecular theory explains why they behave as
they do.
KINETIC ENERGY AND TEMPERATURE
In summary, the kinetic molecular theory states that: • The last assumption can be written in equation form as:
1. Gases consist of large number of molecules that are in continuous, random motion 𝟏 𝟑 𝟑
𝑬𝑲 = 𝒎𝒗𝟐 = 𝑹𝑻 = 𝒌𝐁 𝑻
colliding each other and with the walls of the container. 𝟐 𝟐 𝟐
2. These gaseous molecules are widely separated in space. The combined volume of Where 𝑘B is Boltzmann's constant (𝑘B = 1.381 × 10−23 m2 kg s −2 K −1 ) and 𝑇 is
all the molecules of a gas is negligible relative to the total volume in which the gas the absolution temperature (in Kelvin)
is contained. Molecules of a particular gas are identical in all respects. • This equation says that the speed of gas particles is related to their absolute
3. The pressure exerted by a gas in a container result from collisions between the gas temperature. In other words, as their temperature increases, their speed
molecules and the container walls. increases, and finally their total energy increases as well. However, it is impossible
4. There is no intermolecular force (Attractive and repulsive forces) between the gas to define the speed of any one gas particle. As such, the speeds of gases are
molecules and hence the molecules move independent of each other. defined in terms of their root-mean-square speed.
5. Energy can be transferred from one molecule to the other during collisions but the
average kinetic energy of the molecules remains constant (perfectly elastic) as long KINETIC ENERGY AND PRESSURE
as the temperature remains constant.
6. The effect of gravitational force on the motion of molecules is also negligible. • The pressure of a gas results from collisions between the gas particles and the
7. The average kinetic energy of the molecules is proportional to absolute temperature walls of the container. Each time a gas particle hits the wall, it exerts a force on
of the gas. At any given temperature, the molecules of all gases have the same the wall.
kinetic energy. • An increase in the number of gas particles in the container increases the frequency
of collisions with the walls and therefore the pressure of the gas.
• The macroscopic phenomena of pressure can be explained in terms of the kinetic
molecular theory of gases. Assume the case in which a gas molecule (represented

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 by a sphere) is in a box, length 𝑳 (Figure 1). Through using the assumptions laid SAMPLE PROBLEMS
out above, and considering the sphere is only moving in the x-direction, we can
1. What is the total kinetic energy of 0.50 mol of an ideal monatomic gas confined to
examine the instance of the sphere colliding elastically with one of the walls of the
8.0 dm3 at 200 kPa?
box.
− The momentum of this collision is given by Solution: The kinetic energy of an ideal gas could be solve using the equation:
𝑝 = 𝑚𝑣 , in this case 𝑝 = 𝑚𝑣𝑥 , since we are 3
𝐸𝐾 = 𝑅𝑇
only considering the 𝑥 dimension. The total 2
momentum change for this collision is then Since RT = PV/n, Therefore,
given by 3 𝑃𝑉 3 (200 kPa)(8.0 dm3 )
𝐸𝐾 = ∙ = = 𝟒. 𝟖 𝐤𝐉 𝐦𝐨𝐥−𝟏
𝑚𝑣𝑥 − 𝑚(𝑥−𝑣𝑥 ) = 2𝑚𝑣𝑥 2 𝑛 2 0.5 mol

2. For 1 mole of He gas, a volume of 25.00 L of gas exerts a pressure of 0.8770 bar.
Figure 1 What is the average velocity of the helium atoms in the system?
− Given that the amount of time it takes between collisions of the molecule with the Solution We can substitute the various values directly into the expression
wall is 𝐿/𝑣𝑥 we can give the frequency of collisions of the molecule against a given 2
𝑁 ∙ 𝑚 ∙ 𝑣avg
wall of the box per unit time as 𝑣𝑥 /2𝐿. One can now solve for the change in 𝑃=
3𝑉
momentum per unit of time: recognizing that the product of the variables 𝑁 ∙ 𝑚 is the molar mass of He, or
(2𝑚𝑣𝑥 )(𝑣𝑥 /2𝐿) = 𝑚𝑣𝑥2 /𝐿 0.004003 kg, and that 25.00 L is equal to 0.02500 m3 (in standard units):
− Solving for momentum per unit of time gives the force exerted by an object (𝐹 = 𝑁 (0.004003 kg)(𝑣avg2
)
𝑚𝑎 = 𝑝/𝑡𝑖𝑚𝑒 ). With the expression that 𝐹 = 𝑚𝑣𝑥2 /𝐿 one can now solve for the 87, 700 2 = 3
m 3(0.02500 m )
pressure exerted by the molecular collision, where area is given as the area of one Since 1 N = 1 kg m/s2, we have
wall of the box, 𝐴 = 𝐿2 : kg (0.004003 kg)(𝑣avg 2
)
𝑚𝑣𝑥2 87, 700 =
𝑃 = 𝐹𝐴 ↔ 𝑃 = m ∙ s2 3(0.02500 m3 )
[𝐿(𝐿2) The various units cancel to give us
− The expression can now be written in terms of the pressure associated with 2
m2
collisions from 𝑁 number of molecules: 𝑣avg = 1. 643 × 106 2
s
𝑁𝑚𝑣𝑥2 Therefore 𝑣avg = 𝟏𝟐𝟖𝟐 𝐦 𝐬 −𝟏
𝑃=
𝑉
− This expression can now be adjusted to account for movement in the 𝑥, 𝑦 and 𝑧
directions by using mean-square velocity for three dimensions and a large value COLLISION FREQUENCY AND MEAN FREE PATH
of 𝑁. The expression now is written as: • Collision frequency describes the rate of collisions between two atomic or
𝑵 ∙ 𝒎 ∙ 𝒗𝟐𝐚𝐯𝐠 molecular species in a given volume, per unit time.
𝑷= • The mean free path 𝝀 is the average distance a particle travels without colliding
𝟑𝑽
− This expression now gives pressure, a macroscopic quality, in terms of atomic with other particles
motion. The significance of the above relationship is that pressure is proportional − Factors affecting the mean free path
to the mean-square velocity of molecules in a given container. Therefore, as 1. Density: As gas density increases, the molecules become closer to each
molecular velocity increases so does the pressure exert on the container. other. Therefore, they are more likely to run into each other, so the mean
free path decreases.

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 2. Radius of molecule: Increasing the radii of the molecules decreases the Average (Mean speed): is the sum of the speeds of all the molecules divided by the
space between them, causing them to run into each other more often. number of molecules.
Therefore, the mean free path decreases.
3. Pressure, temperature, and other factors that affect density can indirectly
affect mean free path 𝟖 𝑹𝑻 𝟖 𝑲𝐁 𝑻
̅ 𝐨𝐫 𝒗𝐚𝐯𝐠 = √ ∙
𝒗 = √ ∙
𝝅 𝑴 𝝅 𝐦

MAXWELL-BOLTZMANN DISTRIBUTION OF MOLECULAR SPEED

Root-mean-square speed (rms speed): The rms speed is the measure of the speed of
• All molecules in a sample of a gas do not travel with the same speed and their particles in a gas.
speeds are changing every second due to intermolecular collisions.
• Maxwell suggested that at a particular temperature, the fractions of molecules 𝟑𝑹𝑻 𝟑𝑲𝐁 𝑻
possessing particular speeds remain constant.
𝒗𝐫𝐦𝐬 = √ = √
𝑴 𝐦
• The distribution of molecules between different possible speeds was independently
Hence, particles of lighter gases have a higher rms speed than particles of heavier ones.
derived from statistical considerations by Maxwell and Boltzmann in 1860.

Expression of molecular speeds SAMPLE PROBLEMS

• The actual mathematical equation for 1. Arrange the following in increasing rms speed: N2, O2, H2O, NO.
the Maxwell-Boltzmann distribution is Answer: O2 < NO < N2 < H2O
a little intimidating and not typically Molar masses: N2 = 28.02, O2 = 32.00, H2O = 18.02, NO = 30.01
needed for many introductory algebra
2. Find the most probable speed of oxygen molecules at 298 K.
classes 1⁄
• Figure 2 shows the summary that can 2𝑅𝑇 2(8.314 J mol−1 )(298 K) 2
Answer: 𝑣p = √ = ( ) = 𝟑𝟗𝟒 𝐦 𝐬 −𝟏
be assume from the Maxwell 𝑀 0.0320 kg
distribution.
3. Calculate the mean speed of oxygen molecules at 298 K.
• The y-axis of the Maxwell-Boltzmann
distribution graph gives the number of 8𝑅𝑇 8(8.314 J mol−1 )(298 K)
Answer: 𝑣avg = √ 𝜋𝑀 = √ 𝜋 (0.0320 kg)
= 𝟒𝟒𝟒 𝐦 𝐬 −𝟏
molecules per unit speed. The total
area under the entire curve is equal to
4. Calculate the mean speed of oxygen molecules at 298 K.
the total number of molecules in the
Figure 2. A summary of the conclusions that 3𝑅𝑇 8(8.314 J mol−1 )(298 K)
gas. can be deduced from the Maxwell distribution Answer: 𝑣rms = √ = √ = 𝟒𝟖𝟐 𝐦 𝐬 −𝟏
𝑀 𝜋 (0.0320 kg)
for molecules.
5. Calculate the rms speed of N2 molecule at 25oC.
Most probable speed: speed near which the speeds of most molecules are found, the
peak of the speed distribution function. Answer:

𝟐𝑹𝑻 𝟐𝑲𝐁 𝑻
𝒗𝐩 = √ = √
𝑴 𝐦

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ADDITIONAL EXERCISES
1. Use the kinetic theory to justify the following observations: (a) the rate of a
reaction in the gas phase depends on the energy with which two molecules collide,
which in turn depends on their speeds; (b) in the Earth’s atmosphere, light gases,
such as H2 and He, are rare but heavier gases, such as O2, CO2, and N2, are
abundant.
2. Determine the ratios of (a) the mean speeds, (b) the mean kinetic energies of He
atoms and Hg atoms at 25°C.
3. Using the Maxwell-Boltzmann function, calculate the fraction of argon gas
molecules with a speed of 305 m/s at 500 K.
4. If the system in problem 3 has 0.46 moles of argon gas, how many molecules have
the speed of 305 m/s?
5. Consider a sample of Ar gas. Determine the temperature of the gas if the following
velocities were equal to 500.0 m/s:
a. 𝑣rms c. 𝑣avg
b. 𝑣p d. Do the relative temperatures meet expectations?

6. The speed that a body of any mass must have to escape from the earth is 1.07 ×
104 m s–1. At what temperature would the average speed of (a) a H 2 molecule,
and (b) an O2 molecule be equal to this escape speed?

7. What is the temperature of the He gas if the 𝑣rms is equal to 1282 m s–1?

8. By what factor are the root-mean-square speeds changed if a gas is heated from
300 K to 400 K?

9. Suppose that two ideal gases are heated to different temperatures such that their
pressures and vapor densities are the same. What is the relationship between their
average molecular speeds?
10. What will have a larger speed distribution, helium at 500 K or argon at 300 K?
Helium at 300 K or argon at 500 K? Argon at 400 K or argon at 1000 K?

11. Nitrogen gas is maintained at 152 kPa in a 2.00-dm3 vessel at 298.15 K. If its molar
mass is 28.0134 g mol–1 calculate:
a. The amount of N2 present.
b. The number of molecules present.
c. The root-mean-square speed of the molecules.
d. The average translational kinetic energy of each molecule.
e. The total translational kinetic energy in the system.

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