Encl: S065 \Ape] 20> Raffles Institution Year § H2 Chemistry 2020 Lecture Notes 5b ~ Chemical Energetics 2 Me Yeo. Ext 69. Content * Entropy = © Free energy change, spontaneity of reactions AG® = AH® — TAS? Learning Outcomes AG = AH a TAS Candidates should be able to: (@) explain and use the term entropy (b) discuss the effects on the entropy of a chemical system by the following: () change in temperature (ii) change in phase (iii) change in the number of particles (especially for gaseous systems) (iv) mixing of particles [quantitative treatment is not required] (©) _ predict whether the entropy change for a given process or reaction is positive or negative (@) state and use the equation involving standard Gibbs free energy change of reaction, AG®, AG® = AH® - TAS® [the calculation of standard entropy change, AS®, for a reaction using standard entropies, S®°, is not required) (@) state whether a reaction or process will be spontaneous by using the sign of AG® (understand the limitations in the use of AG® to predict the spontaneity of a reaction (@) predict the effect of temperature change on the spontaneity of a reaction, given standard enthalpy and entropy changes © Lecture Outline Direction of chemical change Entropy and Entropy Change Gibbs Free Energy Change Effect of Temperature on the Spontaneity of Reaction RONHH 1 Direction of chemical Change When a piece of hot sodium metal and chlorine gas come in contact, a violent reaction occurs ‘and sodium chloride is formed. 2Na(s) + Cla(g) —+ 2NaCi(s) Why do sodium and chiorine react readily to form sodium chloride? Why does sodium chloride not form sodium and chlorine on its own accord? Chemists are always interested in the direction of change. By understanding the factors that Make a reaction go in a particular direction, itis possible to predict the conditions which might allow a reluctant reaction to go the way that is wanted. 1.4 __Spontaneous Change What is a spontaneous process? A spontaneous process is one that, once started, will continue without any external assistance. Conversely, a non-s; pontaneous process will not occur unless some external assistance is continuously applied Examples of spontaneous processes: H;0(s) —>H,0\() at 298 K and 4 atm. NaQH(aq) + HClaq) —> NaCl(aq) + H:0() CHA(g) + 20:(g)—> COx(g) + 2H:0(1) If a process is spontaneous, the reverse process is non-spontaneous. Both spontaneous and non-spontaneous processes are possible, but only spontaneous processes will occur without intervention. Non-spontaneous processes require the system to be acted on by an extemal agent. Note: The term ‘spontaneous" signifies nothing about how fast a process occurs and has nothing to do with how long a process takes to occur. A spontaneous process can either be slow or fast. 1.2 Criteria for Spontaneity In early days of physical chemistry, it was thought that systems reacted or changed so as to minimize their energy. In the 19" century, Marcellin Berthelot suggested that all exothermic reactions are spontaneous. However, things are not quite simple since many endothermic processes do take place spontaneously. Examples include the following: © NH«NO,(s) +.aq.—> NH:NOs(aq) AH® = +26 kJ molt © H:0(s)—> H.0(|) AHP = 46.01 kJ mol ‘Since some spontaneous reactions are exothermic and others are endothermic, enthalpy (H alone cannot account for the direction of spontaneous change; a second factor must be involved. This second thermodynamic factor is termed entropy (S). There are two natural tendencies behind spontaneous processes: ©. the tendency to achieve a lower energy state and ©. the tendency toward a state of greater entropy.y Hl 2 Entropy and Entropy Change 24_Whatis Entropy? Candidates should be able to: (@)__ explain and use the term entropy * Definition ‘The entropy (symbol: S) of a system is a measure of the disorder of matter and energy in the system. The more ways matter in the system can be arranged, and the more ways energy in the system can be dispersed, the more disordered the system is and the larger is its entropy. Simplified version: ‘The entropy (symbol: S) of a system is a measure of the disorder in the system. The more & disordered the system is, the larger is its entropy. «The entropy of a system is related to the number of ways the particles (atoms, molecules or ions) in the system can be arranged or distributed and also the number of ways the energy in the system can be dispersed or spread out. Example: For any substance, the entropy increases as the substance changes from solid to liquid to gas. | ee The solid state The liquid state ‘The gaseous state ordered structure in ‘state greater freedom of motion than only able to vibrate ‘energy to undergo translational © more ways to arrange the ys! about fixed positions in ‘motion to some extent portles. * Sornesmectene | [+ memmearemte2.2 Some Entropy Values : : lues * Using a variety of experimental methods, itis possible to work out the absolute entropy val of elements and compounds under different conditions. The tables below list the standard entropies, $°, of some substances at 298 K. Element [S%J«'mol* | [Compound | 8°73 K* mol? H,0(s) — H:0(1) (graphite) 5.6 CH«(g) 186 (diamond) 24 CsHe(g) 229 aS?= Cia) 158 CaHe(g) 270 Cals) 41.6 CHsOH(!) 427 Ar(g) 155 CO(g) | ae He(a) 431 er 214 (g)—> C(graphite) x(a) 205 | He0(s) 48.0 = Ne(a) 192 H2O() 70.0 ae F(a) 203 H20(g) 189 ‘Ch(a) 223, NaGi(s) 724 Bra(!) 152, [ Mgo(s) 26.9 & Ios) 116 CaCOs(s) 91.7 * When comparing the same or similar substances, entropies of gases are much larger than those for liquids, and entropies of liquids are larger than those for solids. For example, the standard entropies of 12(s), Bra(!) and C/o(g) are 116, 152 and 223 J Kt mol" respectively. * Fora series of related compounds, entropy increases with increasing molecular complexity 2.3 Entropy Change * The entropy change (AS) for a reaction or a process is a measure of the change in disorder in a system. ‘* This entropy change (AS) depends only on the entropy of the initial state (Sinua) and entropy of the final state (Sina) of the system (its composition, volume, pressure, temperature). * The entropy change (AS) for a reaction can be worked out using tabulated standard entropy values but this is not required as stated under learning outcome (d) in the syllabus. © Note: entropy change is positive entropy change is negative (AS > 0) (AS <0) => final state is more disordered than initial state than initial state * A qualitative idea of the entropy change can be obtained by inspecting the equation for the reaction, and taking note of the various factors affecting entropy as discussed in the next section.© Candidates should be able to: (0) discuss the effects on the entropy of a chemical system by the following: (change in temperature (1) change in phase (Gil) change in the number of particles (especially for gaseous systems) (iv) mixing of particles [quantitative treatment is not required] | (© predict whether the entropy change fora given process or reaction is positive or negative L In general, the following factors affect entropy of a chemical system: ‘poy-:ayt! change in temperature change in phase ‘change in the number of particles (especially for gaseous: systems) 1g of particles BON (1) Change in Temperature ‘The entropy of a system increases as the temperature increases. ‘An increase in temperature increases the average kinetic energy of the particles in the system, giving the particles more energy to move. For liquids and gases, the particles undergo more rapid Tandom motion causing greater disorder. Hence the entropy of the system increases. But this explanation is not sufficient. Explanation wanted: When the temperature of a system is increased, the increase in entropy comes about because in the broadening of the Boltzmann energy distribution, there are more ways of arranging energy quanta in the hotter system. To understand the explanation, there is a need to know the Maxwell-Boltzmann distribution curve of kinetic energies which is described briefly below. © The kinetic energy of any | Maxwell-Boltzmann Distribution of Kinetic Energies particular molecule in a gas is always changing. This is due to collisions and the resultant change in speed and hence number of energy. molecules with a given * However, at any given instant, energy due to the large number of molecules involved, the distribution of kinetic energies is . always the same at the same ‘Kinetic energy temperature and it follows the Maxwell-Boltzmann distribution * The area under the curve is equal to the total diagram shown on the right. number of particles in the system. +The peak in the curve corresponds to theynumber of particles with the most probable energy.* The Maxwell-Boltzmann distribution diagram below shows the distribution of kinetic energies for a given sample of molecules at different temperatures. umber of molecules with a given energy kinetic eneray ‘As temperature increases from T;to Ts K, 1. the maximum of the curve is displaced to the ht andis_lowe(— 2. there is a greater spread of kinetic energies i.e. the distribution curve broadens * As the temperature increases, there is a broadenit the ener; ‘bution of the (Particles. Thus, there are more possible e1 States in which the particles can adopt at a higher temperature. Hence, an increase in temperature leads to an increase in entropy. or + As the temperature increases, there is a broadening of the energy distribution of the Particles. Thus, there are more packets of energy available to spread out within the system, resulting in more ways to spread out the larger number of packets of energy. Hence, an increase in temperature will lead to an increase in entropy. (i) Chrsinee, Variation of entropy with temperatire os * Fora substance, the entropy increases in the following order solid < Stiqua << Sgas E a slid, | oF me * Solid to Liquid Phase fe eae ‘When a solid melts into a liquid, the order in the solid is destroyed. Particles in a liquid are more randomly arranged and more disordered than those in the solid, resulting in an increase in entropy. ¢ Liquid to Gas or Solid to Gas Phase The change from liquid to gas or solid to gas is accompanied by an even larger increase in entropy. This is because the gaseous state is the most disordered since the gas particles can move freely and are the most randomly arranged. This change of phase is also accompanied by a large increase in volume.4) (a) (b) Change in the number of particles (especially for gaseous systems) The entropy of a system increases as the number of particles in the system increases. With more particles, there are more ways to arrange the particles and more ways to distribute the energy in the system, and hence creating greater disorder in the system. For processes that result in an increase in the number of moles of gaseous particles in a system, the entropy of the system increases more significantly. This is because the arrangement of molecules in a gas is the most disordered amongst the three states of matter as the gas molecules move randomly in all directions. ‘Some examples of such reactions include © decomposition of CaCOs: CaCOs(s) —» CaO{s) + CO2g) * decomposition of NzO: NsO(g) —> Na(g) + 40219) ‘© combustion of propane (at 100 °C): CsHa(g) + 502g) —» 3CO2(g) + 4H20(g) 19 of Particles (without chemical reaction) (a) Mixing of gas particles (b) Mixing of liquid particles (6) Dissolution of an ionic solid in water Mixing of gas particles Gases always mix completely to create a more disordered state. ae) 7 Oo. @ > 0 +] 90 oes 9 2 rt » 2 Meo 5. Oy 25:48) Upon mixing, each gas expands to occupy the whole container. Hence there is an increase in entropy as there are now more ways for the molecules to arrange themselves in the larger volume. Mixing of liquid particles Liquids of similar polarities, e.g. benzene and hexane, mix together to form a solution in which the molecules are randomly mixed. The solution has greater disorder than the liquids in their unmixed state. There is an increase in entropy as there are now more ways for the molecules to arrange themselves in the larger volume of the solution{c) Dissolution of an ionic solid in water in disorder The dissolution of an ionic solid in water can lead to a net increase or decrease in ‘depending on the constituent ions of the ionic solid. Example 1: NaCi(s) + aq, —> Na‘(aq) + Cr(aq) * Inthis case, AS > 0. * The dissolving of sodium chloride in water involves the disruption of the crystal structure of solid NaC/ and hydration of the gaseous Na’ and Cr ions. * The disruption of the crystal increases disorder, since the Na* and Ci" ions previously rigidly held in the solid lattice are now free to move about. NaCi(s) —> Na'(g) + rg) * The hydration process, however, decreases disorder (or increases order) about the Nat and Cr ions because it puts the hydrating water molecules into an orderly arrangement about the Na* and Cr ions. Na*(g) + Cr(g) + aq. —> Na*(aq) + Ci(aq) 8°" 4+ Ion-dipole interaction EB a 8+ 70 Na* .O. + iat W by bee HY Be ar, ee a7] | Se /_H HAN + b- be Hehe 3. * It tums out that in this case, the overall dissolution process results in a net increase in disorder and entropy change is greater than zero i.e. AS > 0. Example 2: CaSO,(s) + aq. —> Cat(aq) + SO?(aq) * Inthis case, AS <0 * For salts such as CaSO,,which cont (ate ordered about the ions, and the entropy. * In this case, the perense, In enttePy in the hydration process outweighs the inéréase in [entropy due to isruption of the crystal lattice ’ : 4Bl Worked Example 4 For each of the following processes, state, givit i i , state, giving a reason in each case, whether the entropy ofthe system is positive or negative. see (a) (b) (c) CrHoe(s) —> CrrHee() AS>0 ‘The entropy change is positive because the reaction produces a liquid from a solid, The molecules in the liquid can move about and hence there are more ways to arrange the molecules in the liquid state than in the solid state. This results in greater disorder, and hence an increase in the entropy of the system Ne(g) + O2(g) —> 2NO(g) AS=0 (very small, can be positive or negative) The entropy change is close to zero because the reaction does not cause any change in the number of moles of gaseous molecules in the system. Hence there is little change in the disorder in the system and the entropy of the system remains almost the same. 2H20(1) —> 2HA(g) + Ox(9) S>0 The entropy change is positive because the reaction produces gases from a liquid and results in an increase in the number of moles of gaseous molecules in the system (from 0 to 3 moles). With more gaseous molecules which can move more randomly, there are more ways to arrange them. Thus, disorder increases and hence entropy increases, (a) (e) (f) Na‘(g) + Cg) —> NaC(s) as 2Ci(g) AS>0O ‘The entropy change is positive because the reaction results in an increase in the number of moles of gaseous particles in the system. With more particles, there are more ways to arrange the particles and more ways to distribute the energy in the system, and hence creating greater disorder and higher entropy in the system. Mg(s) + ZnO(s) —> MgO(s) + Zn(s) ASwO (very small, can be positive or negative) The entropy change is close to zero because the reaction does not cause any change in the number of moles of particles in the system and also there is no phase change in any substance. ‘There is little change in the number of ways to arrange the particles in the system and the entropy of the system remains almost the same.HH 3 Gibbs Candidates should be able to: (4) state and use the equation involving standard Gibbs free energy change of reaction, AG®, AG® = AH® - TAS? [the Caleulation of standard entropy change, AS, fora reaction using standard entroples, $ fst required] (e) state whether a reaction or process wil be spontaneous by using the sgn of AG? (©) understand the limitation in the use of AG® to pret the spontaneity ofa reaction ‘+ There are two natural tendencies behind spontaneous processes: «the tendency to achieve a lower energy state and © the tendency toward a state of greater entropy. * Fora process or reaction, neither AH nor AS alone can be used predict whether the process or reaction is spontaneous or not. Both AH and AS affect the spontaneity of a reaction or process. ‘* How can AH and AS be considered together to predict whether a reaction or a process is, ‘spontaneous? This problem was first solved by J. Willard Gibbs, who introduced a new quantity, now called the Gibbs free energy (or just free energy) and given the symbol G. © 34 dard Gibbs Free Eneray Change * The Standard Gibbs Free Energy change, AG®, of a reaction is given by the equation: AG® = AH® — TAS® * Standard conditions: * AG® is obtained at a pressure of 1 bar and at a specified temperature, which is commonly 298 K. * The reactants and products are in their standard states. ‘+ Generally, we can assume that AH® and AS® do not vary significantly with temperature i.e. ‘AH? and AS® can be assumed to be constant unless there is a phase change. * Similarly, at constant temperature and pressure, the Gibbs Free Energy change, AG, of a reaction is given by the equation: AG=AH-TAS Note ‘AG? ‘AHe As? orAG | orAH a or AS units | kJmolt | kJmot? | K Jmol K+3.2__Relationship between AG® and the Spontaneity of a Reaction * The sign of AG® can be used to deduce whether a reaction or process is spontaneous under standard conditions (i.e. 1 bar and a specified temperature, usually 298 K). AG®= AH® — TAS® AGe<0 the forward reaction is spontaneous or AG*is negative (or thermodynamically feasible) or the reaction/process ig exergonic’ | under standard conditions AG? >0 the forward reaction is not spontaneous or AG? is positive (or not thermodynamically feasible) or the reaction/process is endergonic | under standard conditions Note: This part will be discussed again in the topic on Chemical Equilibrium. © Similarly, the sign of AG can be used to deduce whether a reaction or process is spontaneous | | © _nder non-standard concitions (ie. ata particular temperature and pressure) | AG= AH- TAS | AG<0 + the forward reaction is spontaneous | oF AG is negative (or thermodynamically feasible) | or the reaction is exergonic | AG>0 ‘the forward reaction is not spontaneous | ‘or AG is positive (or not thermodynamically feasible) | or the reaction is endergonic AG=0 * the system is at equilibrium | + there is no net change Putting it in another way, A\ ‘© Reactions, at constant pressure and ‘temperature, goin such a direction as to decrease the free energy of the system. ‘a measure of the driving force of a reaction. ‘© This means thatthe direction in which ‘a reaction takes place is determined / on | Bes | by the rlave. fee ‘energies of | | Tree ey () Premera (9) Products and reactants Syonteoe Tesponancous escson recon 3.3 _ Limitations of the use of AG ¢ _AG® indicates the thermodynamic feasibility (spontaneity) of a reaction i.e. whether it can occur under standard conditions. observable rate). The kinetic feasibility of a reaction depends on the activation energy of the | | : : | + It gives no information about the Kinetic feasibility (whether the reaction proceeds at an | reaction. In practice, a reaction with AG® < 0 may not occur due to the very high activation energy of the reaction. + Note: The same limitations apply to the use of AG under non-standard conditions.3.4_Calculations involving Standard Gibbs Free Eneray Change, AG® WB Worked Example 2 Calculate AG® at 500 K for each of the following Not Teaction is spontaneous at 500 K. calculations. (a) 2CO(g) + 2NHs(g) > CzHe(g) + 2NO(Q) | (a) AG? = AHP TAS? There is a need to convert AS? from Teactions and hence predict whether the | — | Jmol K-'to kJ mot* Kwhen doing the AHP = +408.0 bd molt 4 Ga HHoH.OKT nol ~CDOEL ~o-ragrelE ; = +41"keTnd" - Note: Sihe. AG? 70, the reactron®s Or The units of AH®and AS* are oferent Spartanenss at 500K . ) (b) 2NO(g) + O.(g) —> 2NOAg) (b) AG® = AH? -TAS® —14h.2. - AHP = 114.1 kJ mol =e) —500( Toe , AS® = 146.2 J mol K+ oe . oe » & StreAg? 0 oe “ther enctonrs sportanemt at S00K. i Worked Example 3 ‘Substance MgCOs(s) ‘MgO(s) CO-g) AGP kJ mor? | ~1012 569 304 (a) Use the AG#* data given and the formula, AG® = mAG/(products) - EnAGP(reactants), to calculate the standard free energy change, AG®, for the reaction below. MgCO;(s) —> MgO(s) + CO;(9) Will the above reaction take place spontaneously? (b) Given that the AH? of the above reaction is +101 kJ mot, and the AS® for the reaction is +159 J mot K-', determine the temperature above which the reaction will take place spontaneously. Note: The AG? ofa reaction can be calculated in a similar way (via formula or energy cycle) to that of the AH® of a reaction, using AG? data instead of AHP data, Solution (a) AG° = - 569 - 394 - (-1012) = +49 kJ mot* Since AG® > 0, the reaction will not take place spontaneously. (AGP QH® Tas? CO lor~ Ti) <0 Jo, + DISF 7 Tb3bk | Fherencttnwil] fake S| arfurenaty efx. emptohve Shoe 635h /Assumptro. aH OP to net change, waiters rotureLM Worked Example 4 ‘Substance C:He(Q) H2O() CO-(g) AGP /kJ mol 32.9 =237.2 394.4 With the aid of the given data and an energy cycle, calculate AG® for the combustion of ethane, C:He(g). Note: The AG° of a reaction can be Solution calculated in a similar way (via formula or 200,{g) + 3H20(1)__, | eneray cycle) to that of (344) SS 35 ate, [So iota of AH data KJ Cty +l) By Hess law, A@= (32.4) HASHD H3L-2512) = HLF Tinoj! CaHe(g) +2 Oxo) 1B Worked Example 5 For the reaction, CzH.(g) + HCI(g) —> C2HsCi(g), at 298 K, ‘AHP =-96.7 kJ mot" and AG® = ~25.9 kJ mol Determine by calculation, whether the reaction is feasible at 1000 K. Solution AR =SHP~ TS At 2ask, A =H APY T= oe Assumption Aefandds? donot change ay 923% Fee A= a ~-TA& At (080K, ACP= ATE) C0 2376) SF lteeTonst Sie 470, Heraxting hotfaslle aE DOEHl 4 Effect of Temperature on the Spontanolty of a Roactlon a @ changes 100) Predict the effect of temperature change on the spontanelty of a ranction,glvan standard enthalpy and entropy * Consider AG= AH- TAS, AG is dependent on temperature, T. So, for somo roactions, the spontanolly depends on temperature. AH and AS change comparatively ite with temparature ae long an no phase changos ocour, As an approximation, both terms can be assumed to bo tomparature independant as long as no phase changes occur. By comparing the signs and the magnitudo of AH and ~TAS for a reaction, tho sign of AG for the reaction can be determined, and hence the spontanelty of the reaction can bo predicted, ‘There are 4 scenarios to consider. AH<0 AH>O As>0 A8>0 Spontaneous at all Spontaneous at temperatures high temperatures AH<0 AH>O As 0 AG < 0 at all temperatures Explanation: These reactions are spontaneous (ie AG®AH-TAS thermodynamicall feasible) at all temperatures. | Comparing tho signa of AM and —TAS: + AH0=>-TAS<0 * decomposition of ozone and dinitrogen monoxide * organic combustion combustion of explosives Sinco both AH and =TAS are nogativo, AG< 0 for all valuos of T,(b) Scenario 2: AH> 0 and AS <0 AG > 0 at all temperatures: These reactions are not s} all temperatures. sicheheteahal Thus these reactions have to be driven Continuously with external assistance. Examples of such processes include: * photosynthesis ‘= _formation of ozone from oxygen. (c) Explanation: AG= AH-TAS ‘Comparing the signs of AH and -TAS: + AH>O + AS<0=-TAS>0 Since both AH and -TAS are positive, AG > 0 for all values of T. These reactions are ‘© not spontaneous at low temperatures, and © spontaneous at high temperatures. Examples of such processes include: ‘metting and boling ‘most decomposition reactions electrolysis dissolving (for certain solids) ‘Scenario 3: AH> 0 and AS> 0 ‘AG > 0 at low temperatures ae) Explanation: AH AG= AH-TAS AG <0 at high temperatures (T>-2) | Comparing the signs of AH and -TAS: + AH>O « AS>0=-TAS<0 AtlowT, ‘« the sign of AG is determined by the sian of AH «* the positive AH outweighs the negative -TAS + AG>0 At high T, ‘* the sign of AG is determined by the sian of -TAS «* the negative -TAS outweighs the positive AH + AG<0 (d) Scenario 4: AH <0 and AS <0 ‘AG < Oat low temperatures (T-<-2) | Explanation: ay, |20=4H-Tas ‘AG> Oat high temperatures (T >“) | Comparing the signs of AH and ~TAS: a «© AH0 + spontaneous at low temperatures, ban AtlowT, ‘* not spontaneous at high temperatures. ‘Examples of such processes includ = condensation and freezing ‘= addition and combination reactions = electrochemical cells = precipitation ‘+ the sign of AG is determined by the sian of AH « the negative AH outweighs the positive -TAS. + AG<0 Athigh T, ‘*the sign of AG is determined by the sign of -TAS ‘the positive ~TAS outweighs the negative AH *AG>04.2 Worked Examples @ Bl Worked Example 6 For the following reaction, explain why AH and AS have the signs 8 shown and comment on the feasibility H.Oa(l) —> H:0() + 40x9) AH<0,AS>0 Solution AS>O The entropy change is positive because the reaction produces a gas (and a liquid) from a liquid, and results in an increase in the number of moles of gaseous molecules (from 0 mole to 0.5 moles) in the ‘system, With more gaseous molecules which can move more randomly, there are more ways to arrange the molecules and hence creating greater disorder and higher entropy in the system. AH<0 ‘The enthalpy change is negative because H-O(1) and O2(g) are energetically more stable compared to H202{0) or the bonds in H20() and O2(g) are overall stronger compared to those in Hz02(). Comment on feasibility (i.e. comment on sign of AG) AG= AH-TAS AH<0,AS>0= -TaS<0 ‘Since AH and —TAS are both negative, AG < 0 at all temperatures. Thus, the reaction is spontaneous (i. thermodynamically feasible) at all temperatures. HB Worked Example 7 For the following process, explain why AH and AS have the signs as shown and comment on the thermodynamic feasibility NH«NOs(s) —> NH,*(aq) + NOs-(aq) AH>0,AS>0 Sol AS>0 The entropy change is positive because the disorder achieved in breaking up the solid ionic lattice into mobile ions is greater than the ordering of water molecules around the ions. AH> 0 Recall: AHsoin = ZAMna — LE © In this case, AH is AHscin[NH«NOs(s)] and it is positive because the lattice energy of NH«NOs is more negative than the sum of AHhya[NH4*(g)] and AMyo[NOs-(Q)] Comment on feasibility (i.e. comment on sign of AG) AG= AH-TAS AH>0,AS>0>-TAS<0 At low temperatures (i.e. T <1), AG > 0 because the positive AH outweighs the negative ~TAS. = The reaction is not spontaneous (i.e. not thermodynamically feasible) at low temperatures. At high temperatures (Le. T > 2), AG < 0 because the negative ~TAS outweighs the positive AH. => The reaction is spontaneous (i.e. thermodynamically feasible) at high temperatures.1B Worked Example 8 For the following reaction, explait |, explain why AH and AS have the signs as shown and comment on the feasibility of the reaction. CiH.(Q) + He{g)—> Catts(g) AH <0, AS <0 Solution ‘ASB The entropy change is negative because the reaction results in decrease in the number of moles 4&5<0 of gaseous molecules in the system. With fewer molecules, there are fewer ways of arranging the molecules and fewer ways of distributing the energy in the system, and hence creating less disorder and lower entropy in the system. AH<0 The enthalpy change is negative because the energy consumed to break bonds in the reactant molecules is less than the energy released from bonds formed in the product molecules. Note: Bonds broken: 1 C=C bond and 1 H-H bond Bonds formed: 1 C-C bond and 2 C-H bonds ‘AH = +610 + 436 — 350 -(2)(410) = -124 kJ moh <0 Comment on feasibility (i.e. comment on sign of AG) AG=AH-TAS ‘AH<0,AS<0=-TAS>0 At iow temperatures (.e. T< 2), AG < 0 because the negative AH outweighs the positive -TAS. = The reaction is spontaneous (i.¢. thermodynamically feasible) at low temperatures. [Athigh temperatures (Le. T > 424), AG > 0 because the positive ~TAS outweighs the negative AH. = The reaction is not spontaneous (i.e. not thermodynamically feasible) at high temperatures. IH Worked Example 9 ‘Areaction is non-spontaneous at room temperature but is spontaneous at ~4( ‘say about the signs of AH and AS? Solution athe ‘AHis negative and AS ieposhive ‘Ata low temperature of ~40 °C, AG <0 (Le, the reaction is spontaneous) because the negative AH outweighs the ras. ‘At 2 higher tempefatli& of room temperature, AG > 0 (:.. the reaction is non-spontaneous) because the positive -TAS outweighs the negative AH. 10 °C. What can you 4.3 Summary of Effect of Temperature on the Spontaneity of a ion AG aH | as | -Tas At low T At high T e Always <0 4 erent : - a (Spontaneous at all T) ‘Always > 0 es >o0 | 2 cas : (Non-spontaneous at all T) >0 <0 3) Temperature-| | >0 | >0 | <0 Sapendent (Non-spontaneous) (Spontaneous) _ 4 ‘cases <0 | <0} >0 oo a (Spontaneous) (Non-spontaneous) . ie4.4 Graph of AG° against temperature T ‘+ From the preceding sections, it should be clear that AG® is strongly dependent on temperature. A graph of AG® for a reaction against temperature T is sometimes plotted. AG? = (-AS®) T+ AHP y= mx +6 * Note that a graph of AG? against temperature T is a straight line with a gradient of -AS° and a y-intercept (at 0 K) of AH. * The plot below shows the variation of AG® with T for the following reaction: Fe,Os(s) + 3Ho(g) —> 2Fe(s) + 3Hz0(g) +200 +100 a [s TH [ ® 1B Worked Example 10 In 1944, T. Ellingham published plots of AG” against temperature T for a number of reactions, Today, such plots are called Ellingham diagrams. ‘An Ellingham diagram for three reactions involving the oxidation of Cand CO is shown below. AG" kJ mor 500 2900 Temperature, T/K Which of the following shows correctly the three reactions corresponding to I, and IIT in the above Elingham diagram? & SG 1 u m come, A 200+02200; +0460, 20+ 0,-+260 Of) a) 0 £ B 20+0;-+2CO 260+0;-4200, 6+0;-»00 COP) C69) So aD A © C#O,+60: 260+0,4260; 26+0,+260 2G) Hep) 9240) 0 D Te D 26040: 260; 26+0-260 6+0;-C0y