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 freeThe analysis of this section applies also to liner polyatomic molecules, for which no rotation about the axis of symmetry is possible. An example is , with . Estimate the rotational partition function for a molecule at room temperature. (Note that the arrangement of the atoms is, and the two oxygen atoms are identical.)
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).
Estimate the temperature at which the translational motion of a nitrogen molecule will freeze out, in a box of width.
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 the real world, most oscillators are not perfectly harmonic. For a quantum oscillator, this means that the spacing between energy levels is not exactly uniform. The vibrational levels of an H2 molecule, for example, are more accurately described by the approximate formula
where is the spacing between the two lowest levels. Thus, the levels get closer together with increasing energy. (This formula is reasonably accurate only up to about n = 15; for slightly higher n it would say that En decreases with increasing n. In fact, the molecule dissociates and there are no more discrete levels beyond n 15.) Use a computer to calculate the partition function, average energy, and heat capacity of a system with this set of energy levels. Include all levels through n = 15, but check to see how the results change when you include fewer levels Plot the heat capacity as a function of . Compare to the case of a perfectly harmonic oscillator with evenly spaced levels, and also to the vibrational portion of the graph in Figure 1.13.
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