Chapter 6: Q. 6.50 (page 255)
Show explicitly from the results of this section thatfor an ideal gas.
Short Answer
Gibb's free energy is given by
Chapter 6: Q. 6.50 (page 255)
Show explicitly from the results of this section thatfor an ideal gas.
Gibb's free energy is given by
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Get started for freeIn this problem you will investigate the behavior of ordinary hydrogen, , at low temperatures. The constant is. As noted in the text, only half of the terms in the rotational partition function, , contribute for any given molecule. More precisely, the set of allowed values is determined by the spin configuration of the two atomic nuclei. There are four independent spin configurations, classified as a single "singlet" state and three "triplet" states. The time required for a molecule to convert between the singlet and triplet configurations is ordinarily quite long, so the properties of the two types of molecules can be studied independently. The singlet molecules are known as parahydrogen while the triplet molecules are known as orthohydrogen.
(a) For parahydrogen, only the rotational states with even values of j are allowed.Use a computer (as in ) to calculate the rotational partition function, average energy, and heat capacity of a parahydrogen molecule. Plot the heat capacity as a function of
(b) For orthohydrogen, only the rotational states with odd values of are allowed. Repeat part (a) for orthohydrogen.
(c) At high temperature, where the number of accessible even-j states is essentially the same as the number of accessible odd-j states, a sample of hydrogen gas will ordinarily consist of a mixture of parahydrogen and orthohydrogen. A mixture with these proportions is called normal hydrogen. Suppose that normal hydrogen is cooled to low temperature without allowing the spin configurations of the molecules to change. Plot the rotational heat capacity of this mixture as a function of temperature. At what temperature does the rotational heat capacity fall to half its hightemperature value (i.e., to per molecule)?
(d) Suppose now that some hydrogen is cooled in the presence of a catalyst that allows the nuclear spins to frequently change alignment. In this case all terms in the original partition function are allowed, but the odd-j terms should be counted three times each because of the nuclear spin degeneracy. Calculate the rotational partition function, average energy, and heat capacity of this system, and plot the heat capacity as a function of .
(e) A deuterium molecule, , has nine independent nuclear spin configurations, of which six are "symmetric" and three are "antisymmetric." The rule for nomenclature is that the variety with more independent states gets called "ortho-," while the other gets called "para-." For orthodeuterium only even-j rotational states are allowed, while for paradeuterium only oddj states are allowed. Suppose, then, that a sample of gas, consisting of a normal equilibrium mixture of ortho and para, is cooled without allowing the nuclear spin configurations to change. Calculate and plot the rotational heat capacity of this system as a function of temperature.*
The energy required to ionise a hydrogen atom is 13.6 eV, so you might expect that the number of ionised hydrogen atoms in the sun's atmosphere would be even less than the number in the first excited state. Yet at the end of Chapter 5 I showed that the fraction of ionised hydrogen is much larger, nearly one atom in 10,000. Explain why this result is not a contradiction, and why it would be incorrect to try to calculate the fraction of ionised hydrogen using the methods of this section.
Imagine a world in which space is two-dimensional, but the laws of physics are otherwise the same. Derive the speed distribution formula for an ideal gas of nonrelativistic particles in this fictitious world, and sketch this distribution. Carefully explain the similarities and differences between the two-dimensional and three-dimensional cases. What is the most likely velocity vector? What is the most likely speed?
A water molecule can vibrate in various ways, but the easiest type of vibration to excite is the "flexing' mode in which the hydrogen atoms move toward and away from each other but the HO bonds do not stretch. The oscillations of this mode are approximately harmonic, with a frequency of 4.8 x 1013Hz. As for any quantum harmonic oscillator, the energy levels are , and so on. None of these levels are degenerate.
(a) state and in each of the first two excited states, assuming that it is in equilibrium with a reservoir (say the atmosphere) at 300 K. (Hint: Calculate 2 by adding up the first few Boltzmann factors, until the rest are negligible.) Calculate the probability of a water molecule being in its flexing ground
(b) Repeat the calculation for a water molecule in equilibrium with a reservoir at 700 K (perhaps in a steam turbine).
The dissociation of molecular hydrogen into atomic hydrogen, can be treated as an ideal gas reaction using the techniques of Section 5.6. The equilibrium constant K for this reaction is defined as
whereis a reference pressure conventionally taken to beand the other P's are the partial pressures of the two species at equilibrium. Now, using the methods of Boltzmann statistics developed in this chapter, you are ready to calculate K from first principles. Do so. That is, derive a formula for K in terms of more basic quantities such as the energy needed to dissociate one molecule (see Problem 1.53) and the internal partition function for molecular hydrogen. This internal partition function is a product of rotational and vibrational contributions, which you can estimate using the methods and data in Section 6.2. (An molecule doesn't have any electronic spin degeneracy, but an H atom does-the electron can be in two different spin states. Neglect electronic excited states, which are important only at very high temperatures. The degeneracy due to nuclear spin alignments cancels, but include it if you wish.) Calculate K numerically at Discuss the implications, working out a couple of numerical examples to show when hydrogen is mostly dissociated and when it is not.
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