Outlines of Theoretical Chemistry

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The following table contains a few of the results obtained by Bodenstein at 448 C. Hydrogen, b. Iodine, a. HI calculated, 2x. HI observed, 2z. 20. 57 5. 22 10. 19 10. 22 20. 60 14. 45 25. 54 25. 72 15. 75 11. 90 20. 65 20. 70 14. 47 38. 93 27. 77 27. 64 8. 10 2. 94 5. 64 5. 66 8. 07 9. 27 13. 47 13. 34 It is of interest to note that a change in pressure does not alter the equilibrium in this gaseous system. Making use of the partial pressures of the components of the gaseous system instead of t...he concentrations, we have Pff 2 * Ph _ j? rf ~ p ' PHI Now let the total pressure on the system be increased to n times its original value; then the partial pressures are all increased in the same proportion, and we have which is equivalent to the original expression, since n cancels out. The equilibrium is thus seen to be independent of the pres- sure. This is only true for those systems in which a change in volume does not occur. (b) Dissociation of Phosphorus Pentachloride. When phos- phorus pentachloride is vaporized it dissociates according to the following equation Applying the law of mass action, we have 320 THEORETICAL CHEMISTRY Starting with 1 mol of phosphorus pentachloride, which if undis- sociated would occupy the volume V, under atmospheric pressure, and letting a denote the degree of dissociation, the molecular con- centrations at equilibrium will be as follows: Cpa ' = Letting (1 + a) V = V, and substituting in the above equation, we have At 250 C.

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