Consider a system consisting of a single hydrogen atom/ion, which has two possible states: unoccupied (i.e., no electron present) and occupied (i.e., one electron present, in the ground state). Calculate the ratio of the probabilities of these two states, to obtain the Saha equation, already derived in Section 5.6 Treat the electrons as a monotonic ideal gas, for the purpose of determining μ. Neglect the fact that an electron has two independent spin states.

Short Answer

Expert verified

The ratio of probabilities of unoccupied state to occupied state is kTPeνQe-1kT.

Step by step solution

01

Step 1. Formula Gibb's Factor

Formula for Gibb's Factor is given as:

G(s)=e-(ε-μ)kT

G(s)=e-(ε-μ)kT

where, μis chemical potential, εis energy occupied, kis Boltzmann's constant, Tis temperature.

02

Step 2. Ratio of Probabilities

Substitute ε=0andμ=0for unoccupied state.

G(s)=e-(0-0)kT=e0=1

Substitute ε=-1for occupied state.

role="math" localid="1647153963926" G~(s)=e-(-1-μ)kT=e(1+μ)kT

The ratio of probability of unoccupied state to occupied state is:

role="math" localid="1647154152958" G(s)G~(s)=1e(1+μ)kT

03

Step 3. Substitution in chemical potential formula

Formula for chemical potential is given as:

μ=-kT×lnVZinNνQ

Substitute VN=kTPewhere Peis partial pressure of electron gas.

role="math" localid="1647154444368" μ=-kT×lnkTZinPeνQ

For mono atomic gas, substitute Zin=1

-μkT=lnkTPeνQe-μkT=kTPeνQ
04

Step 4. Final calculation

Ratio of probability can be written as,

G(s)G~(s)=1e(1+μ)kT=e-1kT×e-μkT

Substitute e-μkT=kTPeνQin above equation,

role="math" localid="1647155185719" G(s)G~(s)=e-1kT×kTPeνQ=kTPeνQe-1kT

Hence, the ratio of probabilities of unoccupied state to occupied state is kTPeνQe-1kT .

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Most popular questions from this chapter

Evaluate the integral in equation N=2π2πmh23/2V0ϵdϵeϵ/kT-1numerically, to confirm the value quoted in the text.

Although the integrals (7.53and 7.54) forNand Ucannot be

carried out analytically for all T, it's not difficult to evaluate them numerically

using a computer. This calculation has little relevance for electrons in metals (for

which the limit kT<<EFis always sufficient), but it is needed for liquid H3eand

for astrophysical systems like the electrons at the center of the sun.

(a) As a warm-up exercise, evaluate theNintegral (7.53) for the casekT=εF

and μ=0, and check that your answer is consistent with the graph shown

above. (Hint: As always when solving a problem on a computer, it's best to

first put everything in terms of dimensionless variables. So let t=kTεFrole="math" localid="1649996205331" ,c=μεF

, and x=εkT. Rewrite everything in terms of these variables,

and then put it on the computer.)

(b) The next step is to varyμ holdingT fixed, until the integral works out to

the desired value,N. Do this for values of kTεFranging from 0.1 up to 2,

and plot the results to reproduce Figure7.16. (It's probably not a good idea

to try to use numerical methods when kTεF is much smaller than 0.1, since

you can start getting overflow errors from exponentiating large numbers.

But this is the region where we've already solved the problem analytically.)

(c) Plug your calculated values ofµ into the energy integral (7.54), and evaluate

that integral numerically to obtain the energy as a function of temperature

forkTup to 2εF Plot the results, and evaluate the slope to obtain the

heat capacity. Check that the heat capacity has the expected behavior at

both low and high temperatures.

Consider an isolated system of Nidentical fermions, inside a container where the allowed energy levels are nondegenerate and evenly spaced.* For instance, the fermions could be trapped in a one-dimensional harmonic oscillator potential. For simplicity, neglect the fact that fermions can have multiple spin orientations (or assume that they are all forced to have the same spin orientation). Then each energy level is either occupied or unoccupied, and any allowed system state can be represented by a column of dots, with a filled dot representing an occupied level and a hollow dot representing an unoccupied level. The lowest-energy system state has all levels below a certain point occupied, and all levels above that point unoccupied. Let ηbe the spacing between energy levels, and let be the number of energy units (each of size 11) in excess of the ground-state energy. Assume thatq<N. Figure 7 .8 shows all system states up to q=3.

(a) Draw dot diagrams, as in the figure, for all allowed system states with q=4,q=5,andq=6. (b) According to the fundamental assumption, all allowed system states with a given value of q are equally probable. Compute the probability of each energy level being occupied, for q=6. Draw a graph of this probability as a function of the energy of the level. ( c) In the thermodynamic limit where qis large, the probability of a level being occupied should be given by the Fermi-Dirac distribution. Even though 6 is not a large number, estimate the values of μand T that you would have to plug into the Fermi-Dirac distribution to best fit the graph you drew in part (b).

A representation of the system states of a fermionic sytern with evenly spaced, nondegen erate energy levels. A filled dot rep- resents an occupied single-particle state, while a hollow dot represents an unoccupied single-particle state . {d) Calculate the entropy of this system for each value of q from 0to6, and draw a graph of entropy vs. energy. Make a rough estimate of the slope of this graph near q=6, to obtain another estimate of the temperature of this system at that point. Check that it is in rough agreement with your answer to part ( c).

Consider a Bose gas confined in an isotropic harmonic trap, as in the previous problem. For this system, because the energy level structure is much simpler than that of a three-dimensional box, it is feasible to carry out the sum in equation 7.121 numerically, without approximating it as an integral.*

(a) Write equation 7.121 for this system as a sum over energy levels, taking degeneracy into account. Replace Tandμwith the dimensionless variables t=kT/hfandc=μ/hf.

(b) Program a computer to calculate this sum for any given values of tandc. Show that, for N=2000, equation 7.121 is satisfied at t=15provided that c=-10.534. (Hint: You'll need to include approximately the first 200 energy levels in the sum.)

(c) For the same parameters as in part (b), plot the number of particles in each energy level as a function of energy.

(d) Now reduce tto 14 , and adjust the value of cuntil the sum again equals 2000. Plot the number of particles as a function of energy.

(e) Repeat part (d) for t=13,12,11,and10. You should find that the required value of cincreases toward zero but never quite reaches it. Discuss the results in some detail.

In a real hemoglobin molecule, the tendency of oxygen to bind to a heme site increases as the other three heme sites become occupied. To model this effect in a simple way, imagine that a hemoglobin molecule has just two sites, either or both of which can be occupied. This system has four possible states (with only oxygen present). Take the energy of the unoccupied state to be zero, the energies of the two singly occupied states to be -0.55eV, and the energy of the doubly occupied state to be -1.3eV(so the change in energy upon binding the second oxygen is -0.75eV). As in the previous problem, calculate and plot the fraction of occupied sites as a function of the effective partial pressure of oxygen. Compare to the graph from the previous problem (for independent sites). Can you think of why this behavior is preferable for the function of hemoglobin?

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