For a diatomic gas near room temperature, the internal partition function is simply the rotational partition function computed in section 6.2, multiplied by the degeneracy Zeof the electronic ground state.

(a) Show that the entropy in this case is

S=NkInVZeZrotNvQ+72.

Calculate the entropy of a mole of oxygen at room temperature and atmospheric pressure, and compare to the measured value in the table at the back of this book.

(b) Calculate the chemical potential of oxygen in earth's atmosphere near sea level, at room temperature. Express the answer in electron-volts

Short Answer

Expert verified

(a) The statement is proved below and the entropy of a mole of oxygen at room temperature and atmospheric pressure isS=205.1J/k.

(b) The chemical potential of oxygen in earth's atmosphere near sea level, at room temperature isμ=-0.547eV.

Step by step solution

01

Part (a) step 1: Given information

We have given that a diatomic gas near room temperature, the internal partition function is simply the rotational partition function computed in section 6.2, multiplied by the degeneracy Ze

We need to calculate the entropy of a mole of oxygen at room temperature and atmospheric pressure, and compare to the measured value in the table at the back of this book.

02

Part (a) step 2: Simplify

The entropy is given as:

S=NkInVNvQ+52-ϑFintϑT

where Fintis the internal Helmholtz free energy and it's given in terms of the internal partition as:

Fint=-NktIn(Zint)

for a diatomic gas, the internal partition function is simply the rotational partition function multiplied by the degeneracy of the electronic ground state Ze,the at is:

Zint=ZeZrot

substitute into (2)to get:

Fint=-NkTIn(ZeZrot)

the partial derivative with respect to the temperature is, So(note that Zrotis proportional to T):

ϑFintϑt=-NkIn(ZeZrot0-nk

substitute into (1)to get:

S=NkInVNvQ+52+nKIn(ZeZrot)+NkS=NkInVNvq+In(ZeZrot)+52S+NKInVZeZrotNvQ+72 (3)

Considering an oxygen molecule at the room temperature and atmospheric pressure where Ze=3. The rotation partition for a diatomic gas is given by:

Zrot=kT2

Here,is the energy constant, which equals 0.00018eVfor oxygen. So at the room temperature, the rotational partition function is:

The quantum volume will be given as:

vQ=h22πmkT

The mass of the oxygen molecule O2is 32u,hereu=1.66-27kg, substituting (not that h=6.626×10-34J.sand k=1.38×10-23J/K):

vQ=(6.626×10-34J.s)22π(32×1.66×10-27kg)(1.38×10-23J/K)(300K)=5.66×10-33m3

the volume per particle is written as (from the ideal gas law):

VN=kTP

at a pressure of 1atmand the room temperature we have:

vN=(1.38×10-23J/K)(300K)1.01×105Pa=4.1×10-26m3

plug all these numbers into the natural logarithm in the equation (3)to get:

InVZeZrotNvQ=In(4.1×10-26m3)(3)(71.8)5.66×10-33m3=21.17

now substitute into the equation (3)to get the entropy as:

S=Nk21.17+72

but Nk=nR,

S=n(8.314J/K.mol)21.17+72

for one mole n=1,

S=(8.314J/K)21.17+72=205.1J/KS=205.1J/K

03

Part (b) step 1: Given information

We have given that a diatomic gas near room temperature, the internal partition function is simply the rotational partition function computed in section 6.2, multiplied by the degeneracy Zeof the electronic ground state.

We need to calculate the chemical potential of oxygen in earth's atmosphere near sea level, at room temperature.

04

Part (b) step 2: Simplify

The chemical potential is given by:

μ=-kTInVZeZrotNvQ

substitute with the values to get:

μ=-(8.62×10-5eV/K)(300K)(21.17)=-0.547eVμ=-0.547eV

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Most popular questions from this chapter

For a COmolecule, the constant is approximately 0.00024eV.(This number is measured using microwave spectroscopy, that is, by measuring the microwave frequencies needed to excite the molecules into higher rotational states.) Calculate the rotational partition function for a COmolecule at room temperature (300K), first using the exact formula 6.30 and then using the approximate formula 6.31

This problem concerns a collection of N identical harmonic oscillators (perhaps an Einstein solid or the internal vibrations of gas molecules) at temperature T. As in Section 2.2, the allowed energies of each oscillator are 0, hf, 2hf, and so on. (

a) Prove by long division that

11-x=1+x+x2+x3+

For what values of x does this series have a finite sum?

(b) Evaluate the partition function for a single harmonic oscillator. Use the result of part (a) to simplify your answer as much as possible.

(c) Use formula 6.25 to find an expression for the average energy of a single oscillator at temperature T. Simplify your answer as much as possible.

(d) What is the total energy of the system of N oscillators at temperature T? Your result should agree with what you found in Problem 3.25.

(e) If you haven't already done so in Problem 3.25, compute the heat capacity of this system and check t hat it has the expected limits as T0 and T.

Suppose you have 10 atoms of weberium: 4 with energy 0 eV, 3 with energy 1 eV, 2 with energy 4 eV, and 1 with energy 6 eV.

(a) Compute the average energy of all your atoms, by adding up all their energies and dividing by 10.

(b) Compute the probability that one of your atoms chosen at random would have energy E, for each of the four values of E that occur.

(c) Compute the average energy again, using the formulaE¯=sE(s)P(s)

Consider a hypothetical atom that has just two states: a ground state with energy zero and an excited state with energy 2 eV. Draw a graph of the partition function for this system as a function of temperature, and evaluate the partition function numerically at T = 300 K, 3000 K, 30,000 K, and 300,000 K.

In this section we computed the single-particle translational partition function,Ztr, by summing over all definite-energy wave functions. An alternative approach, however, is to sum over all position and momentum vectors, as we did in Section 2.5. Because position and momentum are continuous variables, the sums are really integrals, and we need to slip a factor of 1h3to get a unitless number that actually counts the independent wavefunctions. Thus we might guess the formula

role="math" localid="1647147005946" Ztr=1h3d3rd3pe-EtrkT

where the single integral sign actually represents six integrals, three over the position components and three over the momentum components. The region of integration includes all momentum vectors, but only those position vectors that lie within a box of volume V. By evaluating the integrals explicitly, show that this expression yields the same result for the translational partition function as that obtained in the text.

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