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Consider a large system of Nindistinguishable, noninteracting molecules (perhaps an ideal gas or a dilute solution). Find an expression for the Helmholtz free energy of this system, in terms of Z1, the partition function for a single molecule. (Use Stirling's approximation to eliminate the N!.) Then use your result to find the chemical potential, again in terms ofZ1.

Short Answer

Expert verified

F=-NkTlnZ1N+1

μ=-kTlnZ1N

Step by step solution

01

Step1. Given information

The partition functionZ for a system of Nindistinguishable, noninteracting molecules is given by

role="math" localid="1647058886923" Z=1N!Z1N...........................(1)

02

Step 2. Calculation for Helmholtz free energy

The formula to calculate the Helmholtz free energy of the system is given by

F=-kTlnZ.............(2)

Substitute the value for Zfrom equation (1) into equation (2) and simplify to obtain the free energy.

role="math" localid="1647059254929" F=-kTln1N!Z1N=-kTNlnZ1-lnZ!=-kTNlnZ1-NlnN+N=-NkTlnZ1N+1...................(3)

03

Step 3. Calculation for chemical potential

The formula to calculate the chemical potential of the system is given by

μ=∂F∂NT,V......................(4)

Substitute the value of the free energy from equation (3) into equation (4) and simplify to obtain the chemical potential of the system.

role="math" localid="1647059391759" μ=∂-NkTlnZ1N+1∂N=-kTlnZ1N+1-NkT∂∂N-lnN=-kTlnZ1N

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