CHAPTER 16 LECTURE NOTES SPONTANEITY, ENTROPY AND FREE ENERGY 16.1 Spontaneous Processes and Entropy Your textbook makes several points regarding spontaneous reactions. * Spontaneous means occurring without outside intervention. * Rate of reaction is irrelevant to spontaneity. Spontaneous means it will happen, not necessarily quickly, or even in the Earth's lifetime. * Spontaneous processes increase the entropy of the universe. (The entropy of a system can decrease if that of the surroundings increases.) = a —|[= =O 5am a5 am ®‘ > Entropy is a complex mathematical function that describes the numier of ce ae possble arrangements (positional probability) of the states of a substance | > Each arrangement available to a substance is called a microstate. Gases (in general) have 4 much higher positional entropy than liquids or solids, t 1. Youhave 3identicd atoms, “A”, “B" and “C”. They can go back and forth frm one — “dash” to the other via the ‘Wall” as shown \ it AB «> C (for example) a. List all the possible microstates that these three atoms can have on dashes. In other words, list all the ways they can arrange therselves\ b. How much more probable is arrangement II than arrangement I? Arrangement | Arrangement IL16.2 Entropy and the Second Law of Thermodynamics The following questions will test your understanding of the “second law” 1, State the second law of thermodynamics In ary spontaneous process there is always an increase in the entropy of the universe wc 2. State the second law in terms of the system and surroundings. SYS S DSuniverse = ASsystem + ASsurroundings — + ab Ss 3. Under what circumstance can the entropy of the system decrease for a +L spontaneous process ? Only when the increase ASsurcundnes is Qreater than the system. eA a 4, How db the first and second laws fundamentally differ Energy is a constant while the entropy is increasing. &