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Mean Free Path The mean free path or average distance between collisions for a gas molecule may

be estimated from kinetic theory. Serway's approach is a good visualization - if the molecules have diameter d, then the effective cross-section for collision can be modeled by

using a circle of diameter 2d to represent a molecule's effective collision area while treating the "target" molecules as point masses. In time t, the circle would sweep out the volume shown and the number of collisions can be estimated from the number of gas molecules that were in that volume.

The mean free path could then be taken as the length of the path divided by the number of collisions.

The problem with this expression is that the average molecular velocity is used, but the target molecules are also moving. The frequency of collisions depends upon the average relative velocity of the randomly moving molecules. Refinement of Mean Free Path The intuitive development of the mean free path expression suffers from a significant flaw - it assumes that the "target" molecules are at rest when in fact they have a high average velocity. What is needed is the average relative

velocity, and the calculation of that velocity from the molecular speed distribution yields the result Sho w which revises the expression for the effective volume swept out in time t

The resulting mean free path is

The number of molecules per unit volume can be determined from Avogadro's number and the ideal gas law, leading to

Mean Free Path Calculation Top of Form The mean free path equation depends upon the temperature and pressure as well as the molecular diameter.

For pressure P0 =

mmHg =

inHg =

kPa

and temperature T=

K=

C=

F,

Molecules of diameter

x 10-10 meters (angstroms)

should have a mean free path of

= m

x 10^

which is

times the molecular diameter

and

times the average molecular separation of

x 10^

m.

The values for pressure, temperature, and molecular diameter may be changed above to recalculate the mean free path. A nominal molecular diameter of 0.3nm = 3 x 10-10 m will give you a reasonable approximation. The pressure required for a given mean free path can be calculated by changing the value of the mean free path above. The calculation is not designed to allow any other changes (their values will be replaced unchanged by the calculation.) From the mean free path and the average velocity, the mean time between collisions and the frequency of collision can be calculated.

Mean Free Path Perspective You may be surprised by the length of the mean free path compared to the average molecular separation in an ideal gas. An atomic size of 0.3 nm was assumed to calculate the other distances.

Average Relative Velocity In order to calculate the mean free path for a molecule of a gas, it is necessary to assess the average relative velocity of the molecules involved rather than just the average velocity of any given molecule. The relative velocity of any two molecules can be expressed in terms of their vector velocities.

The magnitude of the relative velocity can be expressed as the square root of the scalar product of the velocity with itself.

This expression can be expanded as follows.

Taking the average of the terms leads to

Since the same average velocity would be associated with each molecule, this becomes

Weighing a Gas Can you weigh the gas in a closed container? The answer from Newton's laws is yes! If you weigh an "empty" compressed gas cylinder and fill it with high pressure gas, it will then weigh more on an ordinary scale since you are weighing the gas in the cylinder. This will be demonstrated with a single molecule moving vertically, but the same result is obtained with any number of molecules moving in random directions so long as the collisions between them are elastic collisions.

The difference between the average force on the bottom and top of the container is just the weight, mg, of the molecule. This can be generalized to any number of molecules traveling in random directions. If a molecule traveling in a random direction has a y-component of velocity, it will eventually collide with the top or bottom of the container. In an elastic collision with the fixed wall, the y-component of velocity will be reversed, giving a change inmomentum of twice the mass times the original velocity. The force on the wall during that brief collision is quite high, but the much smaller average force of the collision is obtained by dividing the change in momentum by the entire round-trip time to the opposite end of the container and back. Taking an average force like this allows you to determine average forces and average pressures on the walls of a container of gas. The fact that the molecules may undergo many collisions on the way from top to bottom does not change this outcome. If a molecule has a certain momentum toward the bottom as it starts from the top, that net momentum toward the bottom will not be changed, even if it undergoes billions of collisions. It will transfer momentum to many other molecules and the particles which eventually

reach the bottom with that momentum will exert the same average force as if the original molecule got there. What do you think? If a closed truck is carrying a lot of birds, will the truck weigh less if the birds are flying around in the truck? Is the atmospheric pressure times the area of the Earth's surface equal to the weight of the atmosphere?

Kinetic The average translational kinetic energy possessed by free particles given theory byequipartition of energy is sometimes called the thermal energy per particle. concepts It is useful in making judgements about whether the internal energy possessed by a system of particles will be sufficient to cause other phenomena. It is also useful for comparisons of other types of energy possessed by a particle to that which it possesses simply as a result of its temperature. Define constants

Thermal Energy

Index

Top of Form

If the temperature is

C=

F=

K=

x10^

K,

the average "thermal energy" is 3kT/2 = 3kT/2= eV = x 10^ MeV = joules = GeV x10^ amu, eV.

For an atom or molecule of mass

this corresponds to an effective or rms speed of vrms = m/s = mi/hr.


Bottom of Form

(The default mass of 18 amu, the mass of a water molecule, is used in the above calculation if you do not choose a value. The velocity of a water molecule at different temperatures is a good example of the molecular speeds associated with the internal energy of molecules.) The calculated thermal energy provides a useful comparison for the energies involved in other physical phenomena. For example, in the interaction of radiation with matter it is useful to compare the quantum energy of the photons of the radiation with the thermal energy at the existing temperature.

The photon energy associated with the photons in a microwave oven at frequency 2.45 GHz is about 10-5 eV. The average thermal energy at 20C is 0.04 eV, about 3700 times higher. This suggests that the specific effects of the microwave photons in rotating molecules will be quickly randomized by the overwhelming thermal energy of the surroundings, so that the contribution of the microwaves will be "thermalized" or appear as a contribution to raising the temperature of the material.

Molecular speed distribution for ideal gas Fraction of particles above a certain energy

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Internal Energy for Ideal Gas


Internal energy in general includes both kinetic energy and potential energy associated with the molecular motion. But the potential energy is associated with intermolecular forces and is presumed to be zero in an ideal gas where the only molecular interactions are the perfectly elastic collisions between molecules. Therefore the internal energy of an ideal gas is entirely kinetic energy.

While steam at 100 degrees Celsius is not strictly an ideal gas, the diagram illustrates the fact that the phase change to the gaseous state leaves only the kinetic portion of the internal energy. For a monoatomic ideal gas this internal energy is given by

If rotation and vibrational kinetic energies are involved (polyatomic molecules) then