Presentation on theme: "Chapter 3 Classical Statistics of Maxwell-Boltzmann"— Presentation transcript:
1Chapter 3 Classical Statistics of Maxwell-Boltzmann
21- Boltzmann Statistics - Goal:Find the occupation number of each energy level (i.e. find(N1,N2,…,Nn)) when the thermodynamic probability is a maximum.- Constraints:N and U are fixed- Consider the first energy level, i=1. The number of ways of selectingN1 particles from a total of N to be placed in the first level is
31- Boltzmann Statistics We ask:In how many ways can these N1 particles be arranged in the firstlevel such that in this level there are g1 quantum states?For each particle there are g1 choices. That is, there arepossibilities in all.Thus the number of ways to put N1 particles into a level containingg1 quantum states is
41- Boltzmann Statistics For the second energy level, the situation is the same, except thatthere are only (N-N1) particles remaining to deal with:Continuing the process, we obtain the Boltzmann distribution ωB as:
62- The Boltzmann Distribution Now our task is to maximize ωB of Equation (3)At maximum, Hence we canchoose to maximize ln(ωB ) instead of ωB itself, this turns theproducts into sums in Equation (3).Since the logarithm is a monotonic function of its argument, themaxima of ωB and ln(ωB) occur at the same point.From Equation (3), we have:
72- The Boltzmann Distribution Applying Stirling’s law:
82- The Boltzmann Distribution Now, we introduce the constraintsIntroducing Lagrange multipliers (see chapter 2 in ClassicalMechanics (2)):
92- The Boltzmann Distribution We will prove later that
102- The Boltzmann Distribution and hencewhere fi is the probability of occupation of a single state belongingto the ith energy level.The sum in the denominator is called the partition function for asingle particle (N=1) or sum-over-states, and is represented by thesymbol Zsp:
112- The Boltzmann Distribution orΩ = total number of microstates of the system,s = the index of the state (microstate) that the system can occupy,εs = the total energy of the system when it is in microstate s.Example:A system possesses two identical and distinguishable particles (N=2),and three energy levels (ε1=0, ε2=ε, and ε3=2ε) with g1=2, andg2=g3=1. Calculate Zsp by using Eqs.(6) and (7)
122- The Boltzmann Distribution MacrostateNb. microstates(N1,N2,N3)ωBεs(1,0,0)2(0,1,0)1ε(0,0,1)2ε
132- The Boltzmann Distribution If the energy levels are crowded together very closely, as they arefor a gaseous system:whereg(ε)dε: number of states in the energy range from ε to ε+dε,N(ε)dε: number of particles in the range ε to ε+dε.We then obtain the continuous distribution function:
143- Dilute gases and the Maxwell-Boltzmann Distribution The word “dilute” means Ni << gi, for all i.This condition holds for real gases except at very low temperatures.The Maxwell-Boltzmann statistics can be written in this case as:
153- Dilute gases and the Maxwell-Boltzmann Distribution The Maxwell-Boltzmann distribution corresponding to ωMB,max:ωMB and ωB differ only by a constant – the factor N!,- Since maximizing ω involves taking derivatives and the derivativeof a constant is zero, so we get precisely the Boltzmann distribution:
163- Dilute gases and the Maxwell-Boltzmann Distribution - Boltzmann statistics assumes distinguishable (localizable) particlesand therefore has limited application, largely solids and some liquids.Maxwell-Boltzmann statistics is a very useful approximation forthe special case of a dilute gas, which is a good model for a realgas under most conditions.
174- Thermodynamic Properties from the Partition Function In this section, we will state the relationships between the partitionfunction and the various thermodynamic parameters of the system.
184- Thermodynamic Properties from the Partition Function - Calculation of average energy per particle:- Calculation of internal energy of the system:
194- Thermodynamic Properties from the Partition Function - Calculation of Entropy for Maxwell-Boltzmann statistics:with
204- Thermodynamic Properties from the Partition Function
214- Thermodynamic Properties from the Partition Function - Calculation of β
224- Thermodynamic Properties from the Partition Function - Calculation of the Helmholtz free energy:- Calculation of the pressure:
235- Partition Function for a Gas The definition of the partition function isFor a sample of gas in a container of macroscopic size, the energylevels are very closely spaced.Consequences:The energy levels can be regarded as a continuum.We can use the result for the density of states derived in Chapter 2:
245- Partition Function for a Gas γs = 1 since the gas is composed of molecules rather than spin 1/2particles. ThusThenThe integral can be found in tables and isPartition function depends on both thevolume V and the temperature T.
256- Properties of a Monatomic Ideal Gas - Calculation of pressure:where NA is the Avogadro’s number and n the number of moles.
266- Properties of a Monatomic Ideal Gas - Calculation of internal energy:
276- Properties of a Monatomic Ideal Gas - Calculation of heat capacity at constant volume:CV is constant and independent of temperature in an ideal gas.- Calculation of entropy