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The first excited energy level of a hydrogen atom has an energy of 10.2 eV, if we take the ground-state energy to be zero. However, the first excited level is really four independent states, all with the same energy. We can therefore assign it an entropy of S=kln4, since for this given value of the energy, the multiplicity is 4. Question: For what temperatures is the Helmholtz free energy of a hydrogen atom in the first excited level positive, and for what temperatures is it negative? (Comment: When F for the level is negative, the atom will spontaneously go from the ground state into that level, since F=0 for the ground state and F always tends to decrease. However, for a system this small, the conclusion is only a probabilistic statement; random fluctuations will be very significant.)

Short Answer

Expert verified

Helmholtz free energy is positive when temperature T < 8.5 x 104K and it is negative when temperature T < 8.5 x 104K .

Step by step solution

01

Given Information

Entropy, S=kln(4)
Where value of k=8.62×10-5eVK-1
Helmholtz free energy, F=0 (For ground state)
First excitation of energy level, U=10.2eV

02

Explanation

Helmholtz free energy of the first excited level is given by

F=U-TSF=U-T[kln(4)]

Substitute the given value and calculate

F=U-T[kln(4)]

Rearrange

T=U-Fkln(4)

Since, for a ground state F=0,
After substituting the given values in the above equation we get

T=10.2eV-08.62×10-5eVK-1ln(4)=8.5×104K

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Most popular questions from this chapter

The metabolism of a glucose molecule (see previous problem) occurs in many steps, resulting in the synthesis of 38 molecules of ATP (adenosine triphosphate) out of ADP (adenosine diphosphate) and phosphate ions. When the ATP splits back into ADP and phosphate, it liberates energy that is used in a host of important processes including protein synthesis, active transport of molecules across cell membranes, and muscle contraction. In a muscle, the reaction ATP → ADP + phosphate is catalyzed by an enzyme called myosin that is attached to a muscle filament. As the reaction takes place, the myosin molecule pulls on an adjacent filament, causing the muscle to contract. The force it exerts averages about 4 piconewtons and acts over a distance of about 11nm. From this data and the results of the previous problem, compute the "efficiency" of a muscle, that is, the ratio of the actual work done to the maximum work that the laws of thermodynamics would allow.

Suppose you have a liquid (say, water) in equilibrium with its gas phase, inside some closed container. You then pump in an inert gas (say, air), thus raising the pressure exerted on the liquid. What happens?

(a) For the liquid to remain in diffusive equilibrium with its gas phase, the chemical potentials of each must change by the same amount: dμl=dμg Use this fact and equation 5.40 to derive a differential equation for the equilibrium vapour pressure, Pv as a function of the total pressure P. (Treat the gases as ideal, and assume that none of the inert gas dissolves in the liquid.)

(b) Solve the differential equation to obtain

Pv(P)-PvPv=eP-PvV/NkT

where the ratio V/N in the exponent is that of the liquid. (The term Pv(Pv) is just the vapour pressure in the absence of the inert gas.) Thus, the presence of the inert gas leads to a slight increase in the vapour pressure: It causes more of the liquid to evaporate.

(c) Calculate the percent increase in vapour pressure when air at atmospheric pressure is added to a system of water and water vapour in equilibrium at 25°C. Argue more generally that the increase in vapour pressure due to the presence of an inert gas will be negligible except under extreme conditions.

Most pasta recipes instruct you to add a teaspoon of salt to a pot

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Justify your answer with a rough numerical estimate.

Functions encountered in physics are generally well enough behaved that their mixed partial derivatives do not depend on which derivative is taken first. Therefore, for instance,
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a nontrivial identity called a Maxwell relation. Go through the derivation of this relation step by step. Then derive an analogous Maxwell relation from each of the other three thermodynamic identities discussed in the text (for H, F, and G ). Hold N fixed in all the partial derivatives; other Maxwell relations can be derived by considering partial derivatives with respect to N, but after you've done four of them the novelty begins to wear off. For applications of these Maxwell relations, see the next four problems.


Plot the Van der Waals isotherm for T/Tc = 0.95, working in terms of reduced variables. Perform the Maxwell construction (either graphically or numerically) to obtain the vapor pressure. Then plot the Gibbs free energy (in units of NkTc) as a function of pressure for this same temperature and check that this graph predicts the same value for the vapor pressure.

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