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Eint and the Molecular Specific Heats

K avg

3 kT 2

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3 Eint (nN A ) K avg ( nN A ) kT 2


k R NA

Eint (nN A )

3 R 3 T nRT 2 NA 2

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Eint nCV T

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Eint nCV T
A change in the internal energy Eint of a confined ideal gas depends on the change in the gas temperature only; it does not depend on what type of process produces the change in the temperature.

Three paths representing three different processes that take an ideal gas from an initial state i at temperature T to some final state f at T+T temperature. The change in the internal energy of the gas is the same for these three processes and for any others that result in the same change of temperature.

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Eint nCV T

nCV T nC p T nRT C p CV R

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The figure here shows five paths traversed by a gas on a p-V diagram. Rank the paths according to the change in internal energy of the gas, greatest first.

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All three types of molecules can have translational motions and rotational motions. In addition, we would assume that the diatomic and polyatomic molecules can have oscillatory motions, with the atoms oscillating slightly toward and away from one another, as if attached to opposite ends of a spring.

To keep account of the various ways in which energy can be stored in a gas, James Clerk Maxwell introduced the theorem of the equipartition of energy:
Every kind of molecule has a certain number f of degrees of freedom, which are independent ways in which the molecule can store energy. Each such degree of freedom has associated with iton averagean energy of kT per molecule (or RT per mole).

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As the temperature increases, the value of CV/R gradually increases to 2.5, implying that two additional degrees of freedom have become involved. Quantum theory shows that these two degrees of freedom are associated with the rotational motion of the hydrogen molecules and that this motion requires a certain minimum amount of energy. At very low temperatures (below 80 K), the molecules do not have enough energy to rotate. As the temperature increases from 80 K, first a few molecules and then more and more obtain enough energy to rotate, and CV/R increases, until all of them are rotating and CV/R = 2.5. As the temperature increases beyond 1000 K, more molecules have enough energy to oscillate and CV/R increases, until all of them are oscillating and CV/R = 3.5.

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