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By Arther Adamson (Auth.)

A Textbook of actual Chemistry

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Chem. Phys. 19, 1 4 1 3 . GLASSTONE, S. ( 1 9 4 6 ) . " V a n N o s t r a n d - R e i n h o l d , Princeton, N e w Jersey. HIRSCHFELDER, J. , C U R T I S S , C . F . , A N D B I R D , R. B . ( 1 9 6 4 ) . " M o l e c u l a r T h e o r y o f G a s e s a n d Liquids," corrected e d . Wiley, N e w York. M A C D O U G A L L , F . H . ( 1 9 3 6 ) . / . Amer. Chem. Soc. 58, 2 5 8 5 . W E S T O N , F . ( 1 9 5 0 ) . " A n Introduction t o Thermodynamics. " Addison-Wesley, Reading, Massachusetts. EXERCISES A N D PROBLEMS A s noted in the Preface, each section o f this type is divided into three parts.

1-12 with the region showing a hori­ zontal line in Fig. 1-8. This is done as follows. For a real substance isothermal compression across the flat portion of an iso­ therm corresponds to conversion of vapor to liquid at constant pressure. The a m o u n t of mechanical work done, as in the piston and cylinder arrangement of Fig. 1-7, is given by = work= Γ ν w J PdV. (1-51) Vl Notice that if a piston under pressure Ρ sweeps a volume dV, then, as shown in the figure, the total force acting on the piston is / = Ps/ and this force acts through a distance dx, where dV = dx.

The constant β will be identified with I/kT in Section 2-6, when a consequence of Eq. (2-11) is com­ pared with the ideal gas law. First, we can obtain Eq. (2-11) as follows. Since we are considering a system at equilibrium, the distribution will be one for which W is at a maximum—that is, we expect the equilibrium distribution to be the one that is the most probable. We now imagine that a small redistribution δ of molecules takes place, subject to the restriction that neitherT V nor the total energy of the system changes, i Σ *δ^ = € 0.

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