1. ChemE 260 Reversibility and Irreversibility April 27, 2005 Dr. William Baratuci Senior Lecturer Chemical Engineering Department University of Washington TCD 6: D CB 5: 7

2. Reversible and Irreversible Processes Reversible Processes –Processes in which the system and the surroundings can both simultaneously return to their initial states after the process is completed. Irreversible Processes –Processes in which the system and the surroundings cannot both simultaneously return to their initial states after the process is completed. Baratuci ChemE 260 April 27, 2005

3. Sources of Irreversibility Heat Transfer through a finite temperature difference Friction Unrestrained, or fast, expansion or compression Mixing of two different substances Spontaneous chemical reactions Electric current flowing through a finite resistance Inelastic deformation of solids Baratuci ChemE 260 April 27, 2005

4. Heat Transfer Heat transfer from the system to the surroundings occurs spontaneously because T 1 > T surr. But the system cannot spontaneously return to the initial state because heat cannot spontaneously flow from T surr = 25 o C to T sys = 30 o C. We could use a heat pump to transfer heat from the surroundings into the system to return the system to state 1. –But the HP would require work from the surroundings to run and this would leave the surroundings in a different state than they started in ! P 1, V 1 T 1 =100 o C P A = P 1 V A < V 1 1A cool T surr = 25 o C T A = 30 o C Any heat transfer through a finite  T is therefore irreversible. Baratuci ChemE 260 April 27, 2005

5. Friction Friction converts kinetic energy into internal energy when two bodies in contact with each other are in motion relative to each other. Consider what happens when the block spontaneously slides down the inclined plane. Baratuci ChemE 260 April 27, 2005

6. Friction As the block slides down the inclined plane, the potential energy of the block decreases. Friction acts in the direction that opposes motion. The block does work on the surroundings in order to overcome the frictional force that resists motion. Friction converts the work into an increase in T and U of the system and surroundings Baratuci ChemE 260 April 27, 2005

7. Friction The block never spontaneously slides back up the inclined plane ! Work must be input to increase E pot and to overcome friction. Friction again converts the work input into another increase in T and U of the system and surroundings. To return both the block and the surroundings to their original states, we must take heat out of the block and the surroundings and completely convert it to work and return this work to the surroundings. A device that completely converts heat into work violates the K-P Statement of the 2 nd Law and is impossible ! We conclude that any process that includes friction is irreversible ! Baratuci ChemE 260 April 27, 2005

8. Expansion & Compression Even without friction, fast expansion and compression are irreversible. P 1, V 1, T 1 P 2 > P 1 V 2 < V 1 T 2 > T 1 12 Compress Rapidly Expand Very Slowly 1 P 1, V 1, T 1 Force that must be overcome during the fast compression is greater than P 1 A piston. Force that is overcome during the slow expansion is equal to P 1 A piston. We put more work in during the fast compression than we got back out during the slow expansion ! Assume: Q = 0  E pot = 0  E kin = 0 Baratuci ChemE 260 April 27, 2005

9. Expansion & Compression If we put in more work than we got out, then U sys and T sys must have increased ! P 1, V 1, T 1 P 2 > P 1 V 2 < V 1 T 2 > T 1 12 Compress Rapidly Expand Very Slowly 1 P 1, V 1, T 1 Assume: Q = 0  E pot = 0  E kin = 0 To return both the system and the surroundings to their original states, we must take heat out of the system and completely convert it to work and return this work to the surroundings. A device that completely converts heat into work violates the K-P Statement of the 2 nd Law and is impossible ! We conclude that compression or expansion at a finite rate are irreversible ! Baratuci ChemE 260 April 27, 2005

10. Internally Reversible Processes No irreversibilities within the boundary of the system –No friction inside the system –No rapid expansion or compression inside the system –No mixing of two different substances inside the system –No spontaneous chemical reactions inside the system –No electric current flowing through a finite resistance inside the system –No inelastic deformation of solids inside the system Irreversibilities can exist outside the system –This usually means that heat can be exchanged between the system and surroundings through a finite temperature difference. Baratuci ChemE 260 April 27, 2005

11. Externally Reversible Processes Irreversibilites do not exist in the surroundings –This usually means that heat can only be exchanged between the system and surroundings through an infinitely small or infinitessimal temperature difference. Irreversibilites can exist inside the system Baratuci ChemE 260 April 27, 2005

12. Reversible Processes No irreversibilities exist within the system or in the surroundings No real process is reversible Some real processes are very nearly reversible –They have very little friction –They involve only very slow compression or expansion –Heat transfer only takes place between bodies at very similar temperatures. Why bother studying reversible processes if they do not exist ? –Reversible processes are easier to analyze –Reversible processes provide a best-case to which we can compare the performance of any real process. Baratuci ChemE 260 April 27, 2005

13. Next Class … The Carnot Cycle –The gold-standard ! –Maximum efficiency ! –A reversible cycle to which we will compare the performance of all of the real cycles we will analyze in te rest of this course. –We will return to example problems and numbers ! Baratuci ChemE 260 April 27, 2005