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 —|[=‘ > 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. &16.3 The Effect of Temperature on Spontaneity Exothermic reactions give off energy to the surroundings. Therefore, random motions of particles in the surrounding increase. When random motions increase, positional probabilities increase. Exothermic reactions increase the entropy of the surroundings (ASsrr)- The magnitude of the increase in AS..., depends on the temperature. Exothermic reaction (at constant pressure), AH = - Endothermic reaction (at constant pressure), AH = + ASsur = AH “T (in Kelvins) in Kelvins no 1. Caloulate ASzup for each of the following reactions at 25°C and 1 atm. a. CHe@ + 5Q@ > 3C2@ + 4HO@ 4H = -2045k] b. (NHaeCr2O7@) > N@ + CeO + 4HO0 c. HOg > HO@ a) 2045 kJ/298 K = 6.86 kK = 6860 JK b) 315 kJ/298 K = 1.06 KK = 1060 VK ce) -44 1/298 K= -0.15 kK =-150 VKASuniv = ASsys + ASsunr * Areaction will be spontaneous if ASuniy > 0. * Areaction will be endothermic if AS. fe referring to the system) : ASuniv = -AG AHuriverse is Zero ALWAYS. T 1st Law of Thermodynamics ‘The first equation giveg'us an explicit way of calculating free energy. It further says that there are crfumstances under which temperature will determine areactiorfis spontaneous. Note also that since the temperature in Ceehins wp) always b& greater then zero, that -AG = +ASunv, always: ’ , Watch out for unit switches negative AG = Spontaneous AH in kJ AS in J \KT > poy DK = TT= W-TSS Various Possi & Combinations of AH and AS for a Process And the Resulting Dependence of Spontaneity on Temperature Case Result 4S positive, AH negative Spontaneous at all temperatures 4S positive, AH positive Spontaneous at high temperatures (where exothermicity is unimportant) 2S negative, AH negative ‘Spontaneous at low temperatures (where exothermicity is dominant) 4S negative, 4H positive TOCess NOt Spon temperature (reverse process is spontaneous at all temperatures) ‘The case of the temperature dependence of ioe melting, as described in your textbook, is a perfect example of this. You have two opposite entropy facters Ch the cne hand, the reaction is endothermic, which opposes the process (ASaxr = -). On the other hand, melting increases the positional probability of the system (453 = +). The temperature will determine which process will dominate (whether ice melts) The second equation says the AS must be negative (<0) in order for a reaction to proceed, _ on 4 =(- seo = (») nor Or Soret 28 tAz rh 20 &® 1. Given the values for 4H, AS and, determrine whether each of the following sets of data represent spontaneous or nonspontaneous processes. 4H (k3) 4S OK) TK) AG a 40 300 O.3kK 130 1kJ Non b 40 300 0.3k/K 150 -5kJ Spon c 40 300 -O.3k/K 150 85kJ Non d ~40 “300 -03kK/K 130 -1kJ Spon Cn) 300 0.3K/K 150 -85 kJ Spon UseAG = AH - T AS a AG= 40kJ- 130K (0.3 kJ/K) = 1kJ Repeat to test each data set. You know that the boiling point of water is 373K. See how this compares to the Minimum temperature for reaction that you deterrrine thermodynarricdly for the phase change: H09 = HO@ -0.387=AG =0 Where AH = 44k] and AS = 119 JK AG= AH - TAS AG = 44 kd - 373 K (0.119 kJ/K) AG = -0.387 kJ As the excess energy is released into the gas phase AG of the remaining liquid goes back below zero and boiling ceases.16.5Entropy Changes in Chemical Reactions Wi noodle X ws This section in your textbook begins by reminding us that ASeur is related to heat flow from the system, BUT, AS... is related to the positional probabilities for each of the reactants. Ss MAS - For example, VAS ee) = a 2H + Cay > 2H AS = -89k1 (at 25°C). We lose entropy because 3 total moles of the gases on the left have more positicnal possibilities than 2 moles of vapor on the right. * For achemical reaction involving only the gas phase, entropy is related to the total number of moles on either side of the equation. A decrease means lower entropy, an increase means higher entropy. * For a chemical reaction involving different phases, the production of a gas will (in general) increase the entropy much more than an increase in the number of moles of a liquid of solid. For example, 2 HNDs (a9) + Na2CO3%—) > 2 NaNO3 (aq) + HOq + CO2(@ 2S = +88 kJ (at 25°C) The products have more moles and the states of matter of the products are more entropic than the reactants, ergo +AS Use logic reasoning skills to deduce the Entropy change Tell us your reasoning. Predict the sign of AS® for each of the following reactions: a. (NH42Cr2O7) > CreO3s@) + 44200 + R@ b. Mg(OH)@ > MgO ® + HO@ c. Pls@ = PClig + Chip -All three are +\S because more particles (moles) and more entropic states of matter -AND reactions are more likely to occur when there is an increase in Entropy. -They can occur with a decrease in Entropy, however there must be a considerable negative Enthalpy change to over come it.The Third Law of Thermodynamics says that the entropy of a perfect crystal at 0 K is zero. This means that the absolute entropy of substances can be explicitly measured. As was true with AH’ (a state function), AS* (also a state function) can be determined as the difference between the sum of entropy of products minus the sum of the entropy of the reactants, AS "reaction = ZNpS"produets ~ 2S*reactants © Calculate AS° for each of the following reactions, using data from Appendix 4 in your ‘textbook, agi AS* = 2(240) - 304 = 176 Jmol b. FexO3:@ + 2Alg@ = 2Fe@ + Ake -41 J/mol 6. 4Ntb@ + 5Q2@ > 4NO@ + 6HO@ = 181 J/mol16. $Eree Eneray and Chemical Reactions f reactants in their standard states (1 atm and 25%C) are converted to ts in their standard states. Your textbook points out that AG° cannot be measured directly, but is an important value because it represents @ standard set of conaiitions at which to compare properties of reactions Three methods of calculating AG’ are introduced in this section 1, AG°= AH? - TAS? 2. by manipulating known equations, a la Hess’ Law problems for AH®. 3. AG?= menage ~ DAG Teactants 1 sna data e ae and AS°, calaulate AG° for the following reactions at 25°C and a er AiOsg + 20 Try these on your own a. Cr) @ > Ae Fe = B. Greet 509 > 3Cw +A. 9) a eucad 4 aS = 5c i difference of -11 kJ1. Given the following data: £ yt" s (Equation 1) ERO > Se AG? = -371kI (Equation 2) FO2@ > 25SQ@L9 AG -142kI REA ATO Caculate AG? for the reaction (God Equation) S@ + &@ > SQi@ Is the reaction spontaneous ? So, FS ¥RO0 ~A Calculate AG® for the reaction using AG? data from Appendix 4. CHa + 5Q2.@ 3CO® + 4HO@ ae =P=Q AG= -2014 KI1679 The Dependence of Free Eneray on Pressure We hat onditions. This section deals will free For an ideal gas, enthalpy is not pressure dependent. Entropy, however is affected by pressure. More positions are possible a€lower pressireythan higher pressure, therefore a eS Stow pressure > Shigh pressure ‘Your textbook derives the relationship: AG = AG° + RTIn( as ome vk 38.5155 Yr cs ame Temperature in Kelvire Q =reaction quotient ( the mass action expression with initial) cua For the following reaction [ese + Ce ey ke se (Bes gs ae Pra» = 0 ey Poo = 0.00010 atm, Pre = 0.08020 Cnr tRT I/foPy. \ = AU AG. ae tiie HE) BO 72kS KS * (-\O223 * G25 + (-\0U23\ XS) db G21 10. <7 A spontaneous reaction will not necessarily go to completion. Rather, there may be some intermediate point that reflects the lowest possible AG value for the reaction. AG wy > Ser id wo CAN per ©16.8 Free Energy and Equilibrium Equilibrium occurs at the lowest free energy available to the system. ercreston—< Greverseresdion Peddie), In other word’ is = O'at equilbriutt Xe Boawds If AG C0, it means thet Greats > Grodits ard the reaction will go to the right 5 UNtII Genctants = Gproducts, If 4G > 6, it means that Gaacants S Gorotuns 270 the reaction will go to the left Until Greactents = Gproducts. Qualitative Relationship between the Change In Standard Free Energy and the Equilibrium Constant for a Given Reaction AS K 2B" =O K=1 46°60 Kot AG > 0. Kea Remerrber that if K=1 (the equilibrium condition), hk =0 and &G = 48°. A equillorium therefore, AG? = -RTInK Yok Oo 2K H~ ZO React Nen + BO eh 1H Given the for AG® that you cdaulated in #9, calculate K for the following reaction ( r Cros + 2A ALw + 2Cr@ AGE 527 REA “SIF ~B349T Gee k\ \w A -537000T Gian) 6 ToT aK Oe ly K (wk 5 Kw owl = K = s k= 17510" P Se \ R e, er e =Finish Chapter 16 Notes Homework p. 828 #17, 21, 25, 27, 29, 31, 33, 37, 39, 43, 45, 49, and 51Wa) AG= O-TAS a \O.5kT —T Corned) QW= NS -T( 30) =l.5- 1) Bess To) 270 = eoPeoamets) ° Qs [Ren cats t DAg NO, + BOADA aC. + GD) rout ESerm) Poe (ays a GMT. sxe? 0 fol “Oot TV a