Chapter 3 The Second Law of Thermodynamics.ppt

Chapter 3The Second Law of Thermodynamics The Statements of Second Law It is impossible for a system to undergo a cyclic process whose sole effects are the flow of heat into the system from a heat reservoir and the performance of an equivalent amount of work by the system on the surroundings. The Statements of Second Law It is impossible for a system to undergo a cyclic process whose sole effects are the flow of heat into the system from a cold (heat) reservoir and the flow (performance) of an equal equivalent amount of heat (work) out of (by the) system into a hot reservoir. (on the surroundings.) Calculation of entropy change ?S Summary * * Provide such information through S [N2]eq=? [H2]eq =? [NH3]eq =? Esys + Esurr =constant N2+3H2? 2NH3 (with a catalyst) The second law The first law Reaction Physical Chemistry Chapter 3 Kelvin-Plank statement Physical Chemistry Chapter 3 Heat reservoir Cyclic machine (system) Work output = q Fig. 3.1 Heat q Clausius statement (Kelvin-Plank statement) Physical Chemistry Chapter 3 HEAT ENGINES (3.3) Heat reservoir at TH Cold reservoir at TC qH -qC -w Fig. 3.2 Heat Engine A heat engine operating between two temperatures. The heat and work quantities are for one cycle. (3.1) -w = qH + qC (3.2) 1 Physical Chemistry Chapter 3 Converts some of the random molecular energy of heat flow into macroscopic mechanical energy (work) Carnot’s Principle Carnot Principle: No heat engine can be more efficient than a reversible heat engine when both engines work between the same pair of temperatures. The maximum amount of work from a given supply of heat is obtained with a reversible engine. Physical Chemistry Chapter 3 Carnot’s Principle A Carnot cycle: a reversible cycle that consists of two isothermal steps at different temperatures and two adiabatic steps. isotherm isotherm 1 2 4 3 V P ? ? ? ? (b) adiabat adiabat Fig. 3.4 1 2 4 3 V P ? ? ? ? (a) TH TC Physical Chemistry Chapter 3 AB：