Applied Physical Chemistry by C. Heald, A. C. K. Smith (auth.)

By C. Heald, A. C. K. Smith (auth.)

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A thermodynamic study usually commences by focusing attention on a system, which is merely a portion of bulk matter undergoing a process of chemical reaction or physical transformation. An isolated system is one that cannot exchange either matter or energy with its surroundings; the inside of a sealed Dewar flask approximates to such a system. A closed system cannot exchange matter with its surroundings but may exchange energy. An open system can exchange both matter and energy with its surroundings.

5, yields the corresponding value of for c; B. In the case of a monatomic gas such as argon, there is close agreement between thes~ predicted values for molar heat capacity and those measured experimentally. For polyatomic gases, on the other hand, the predicted values are usually toq low and this must be attributed to contributions to U and H from rotational and vibrational motions not possible with monatomic species. RT to the total kinetic energy of translation; this, in effect, is the equipartition principle.

The unit for heat capacity is J K- 1 , that for molar heat capacity J K- 1 mol- 1 . 1 The mofLlr heat capacity of an ideal gas The value of U8 for a gas B varies with temperature because of the dependence of the kinetic energy of translation on temperature. 4a would suggest therefore that Ua = Uo,B +~RT where U0,s is the value of UB at 0 K. If this equation is differentiated with respect to T, it follows from equation 2. 5, yields the corresponding value of for c; B. In the case of a monatomic gas such as argon, there is close agreement between thes~ predicted values for molar heat capacity and those measured experimentally.

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