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The kinetic theory of gases is a model for gas behaviour. A model describes a given real system by some of its most important features. The ideal gas law, as used thus far, is an empirical model for gas behaviour. The kinetic theory of gases provides a theoretical justification (theoretical model) for the ideal gas law

Hypothesis (Assumptions) A gas is composed of a very large number of small particles in constant, random, straight-line motion Gas molecules are separated by a large distance ± a gas is mostly empty space Molecules collide with one another and with the walls of the container There are no intermolecular forces, except during collisions. Molecules act independently of one another Individual molecules may gain or lose energy during collisions but the energy of the entire gas remains constant. Molecular collisions are elastic

Relationships Between Gas Pressure and Velocity

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Translational kinetic energy of a molecule (ek): Frequency of molecular collisions ( ): Momentum transfer (µ) to the wall during a collision: Gas pressure (P):

P w Q v f w (mu ) v u v

1 N ! mu 2 3 V

N N ! mu 2 V V

Distribution of Average Velocities

y y

Molecules of a gas do not have the same translational velocity but instead a distribution of molecular velocities Therefore, the mean-square speed of the gas molecules should be used to calculate the pressure of the gas:

1 N P ! mu 2 3 V

**Non-Ideal Gases y
**

Ideal gas law is valid when intermolecular interactions can be neglected

This equation assumes, incorrectly, that all molecules of the gas have the same speed

**N = number of gas molecules 2 2
**

2

u1 u2 u3 2 ... uN 2 u ! ! mean square speed N

**y This is more likely to be true for non-polar gases at low pressures and high temperatures y
**

significant far from condensation because intermolecular forces in liquids are very

Non-Ideal Gases (2)

Z is called the compressibility factor Generally: 0.1 < Z < 1.

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For ideal gases For real gases

Z can be less than one as shown in the plot of Z versus P. However. The correct term is given by: RT a P! 2 Vm b Vm y y a is a positive constant that depends on gas type and is proportional to intermolecular forces. Z is always greater than one. Therefore. bP PVm P ¨ RT ¸ ! b¹ ! 1 © RT RT RT ª P º Van der Waals Equation (3) y Re-write the equation so that: P! RT Vm b y If the gas molecules attract each other. we know that the volume at 0 K should be equal to at least the volume of the molecules since gases do not disappear upon cooling but liquefy and then solidify Van der Waals Equation (2) A simple correction is: Vm ! b is a positive constant that depends on gas type and is proportional to the molecular volume of the gas. RT b P Z! According to this equation. Preal should be less than the predicted by the above equation. Vm2 is used in the denominator of the new term since molecular attractions are related to bi-molecular collisions Van der Waals Equation (4) P! RT a 2 Vm b Vm The van der Waals equation is cubic in volume ¨ a ¸ © P 2 ¹.Van der Waals Equation y Why isn¶t the ideal gas law always adequate? PVm ! RT Vm ! y y RT P When T = 0 K p Vm = 0 But.

m b ! RT V © Vm ¹ ª º PVm .

bP RT m aVm ab ! 0 V 3 2 .

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