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Kinetic Theory of Gases CM2004 States of Matter: Gases
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A Theory for 10 23 Particles In classical theory a particle’s next move depends upon (equated to) its position, velocity and force acting on it Trying to solve such equations for a mole of gas with 10 23 particles each with x,y,z coordinates and different speeds is almost impossible So we theoretically describe the kinetic system on average in terms of a large set of no-volume “points”, which do not attract or repel each other
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Pressures on Average On average the speed term is best represented by as given in the Maxwell-Boltzmann distribution. Furthermore a particle is equally likely to hit any one of the 6 available walls of the box. Hence: “Mean- square speed”
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Microscopic Energies Can be reformulated as: is called the average kinetic energy per particle
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Macroscopic Energies and Boyle’s Law N 0 is the Total Kinetic Energy of one mole and is called E k, the macroscopic energy: PV=nRT So TEMPERATURE is a direct measure of the INTERNAL ENERGY of moving gas particles
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Internal Energies T 2 >T 1 COLDHOT Each particle moves with an average kinetic energy of:
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Root Mean Square Speeds These (v RMS )represent a single chosen speed to associate with every gas particle, as if they were all moving at this rate. START END Molar Mass
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Thermal Energy: Energy at a Definite Temperature Kinetic Energy of 1 mole is: Define Boltzmann’s constant: Because: Then Kinetic Energy of 1 particle is:
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Equipartition of Energy The EQUIPARTITION theorem states that a molecule gains ½ k B T of thermal energy for each DEGREE OF FREEDOM (i.e. x,y, z directions). So the total is ³/ 2 k B T
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Quantifying Collision Rates Collision Rate (Z*) per face of cube p = 2mv x Z/6A Z = 6pvA/ 2mv 2 Z = pvA/(k B T ) A is termed, , the collision cross-section v is termed c rel the relative mean speed NOTE: But, mv 2 = 3k B T TOTAL pressure in the cube volume, where Z=6Z*
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Relative Mean Speeds, c rel Same Direction Direct Approach Typical “on average” approach
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Mean Free Path, The average distance between collisions is called the MEAN FREE PATH, Hence if a molecule collides with a frequency, Z, it spends a time, 1/Z in free flight between collisions and therefore travels a distance of [(1/Z) x c] = c/Z Z = p c rel /(k B T) = c k B T/p c rel c rel = 2 ½ c Therefore: and = k B T/2 ½ p =d/2) 2 d is the collision diameter
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Maxwell-Boltzmann and v RMS Probability that particle has specific energy, INCREASING TEMPERATURE MORE PARTICLES MOVE FASTER
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Populations We shall return to the importance of Maxwell- Boltzmann Distributions in CM3006 next year Molecules and atoms consist of many “micro” states and the higher the temperature the higher the probability that “excited” states become populated
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Important Equations (1)
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Important Equations (2) Z = p c rel /(k B T) = k B T/ 2 ½ p
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