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Lecture Notes 5b - Chemical Energetics II

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Lecture Notes 5b - Chemical Energetics II

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Travis Sim
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Lecture Notes 8 ~ Chemical Energetics I RAFFLES INSTITUTION Year 5 H2 CHEMISTRY 2017 Lecture Notes 5b — Chemical Energetics II Prepared by: Dr Wong Poh Lee and ‘Mrs Goh-Chua Juan Juan A Content Entropy Free energy change, spontaneity of reactions B Learning Outcome Candidates should be able to (a) (b) (2 (d) (e) (fh (g) explain and use the term entropy discuss the effects on the entropy of a chemical system by the following: (i) 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 4 Entropy 2 Free Energy 1.1. Entropy and Entropy Change 2.1_—_Standard Gibbs Free Energy 1.2 Factors affecting Entropy ofa 2.2 Relationship between AG® and the Spontaneity of Chemical System a Reaction 2.3 Limitations of the use of AG® 2.4 Calculations involving Standard Gibbs Free Energy Change, AG? 2.5 Effect of Temperature on the Spontaneity of a Reaction © Raffles institution 2017 1 ‘Lecture Notes Sb ~ Chemical Energetics i 4 ENTROPY 44 Entropy and Entropy Change Cardidates should be abe io |and use the term entropy : Entropy (S) ‘a measure of the disorder in a system. The more disordered a system, the larger its entropy. + a measure of the different ways a system can arrange itself. A system with more different ways of arranging has a higher entropy. Entropy Change (AS): Entropy change (AS) is a measure of the change in disorder in a system. It depends only on the entropy of initial state and entropy of final state of the system (its composition, volume, pressure, temperature) AS = Sina (entropy of final state) ~ Sinsai (entropy of initial state) Entropy change is positive (AS > 0) negative (AS <0) = final state is more disordered |= final state is less disordered : than initial state than initial state In general, the entropy of a chemical system is affected by the following factors: 4.2.4 mixing of particles 1.2.3. change in phase 1.2.2 change in temperature 1.24 change in the number of gas molecules 1.2 Factors affecting Entropy of a Chemical System £ Candidates shuld be abit £0) discuss the effects on the entropy ofa chemical system by the folowing se change mn temperture 1G) change in phase | i) change inthe numberof particles (especialy for gaseous systems) {)__ mixing of paces : {quantitative teatment not requied) : (0,__predict whether the entropy change for a given process or reaction is postive or negative 1.2.1 Mixing of Particles (a) Mi ing of gas particles Gases always mix completely to create a more disordered state. rs er) ODO aoe! Poe} __, 2 OF ° ‘eo oe e fe e A G Oe ¥@ © Raffles Institution 2017 2 Lecture Notes Sb ~ Chemical Energetics i 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. (b) Mixing of liquid particles Liquids of similar polarities, eg. benzene and hexane, mix together to form a solution in which the molecules are mixed. The solution has greater disorder than the liquids in their unmixed state. {c) Dissolution of an ionic solid in water Sodium chloride (case of AS > 0 + The dissolving of sodium chloride in water involves the disruption of the crystal structure of solid NaC/ and the hydration of the Na* and CI- ions, + Disruption of the crystal increases disorder, since the Na* and Cr ions were previously rigidly held in the solid but are now free to move about in the 60802 © oS € © + The hydration process, however, increases order about the Na‘ and C/- ions because it puts the water molecules into an orderly arrangement about the Na* and CI-ions in forming a hydration sphere. separation of ions hou af Vs. . wel [bow & & H. 3. Be Aone T Na 7 nde Bef faq Be Ne Oe + ar Na‘(g) + Cr(g) ——> 8 bg 3° Sa ea er ™, j—H ae a5.) | pF 2 om Hoa hydration of Na* hydration of Ct + It turns out that the overall dissolution process results in a net increase in randomness and AS > 0. Calcium sulfate (case of AS <0) For salts such as CaSO,, which contain more highly charged ions, more water molecules are ordered about the ions, and the dissolution process often results in decrease in entropy. CaSO,(s) + aq —> Ca™(aq) + SO.*(aq) AS <0 © Raffles Institution 2017 3 Lecture Notes 5b - Chemical Energetics 1.2.2. Increase in Temperature Low temperature number of molecules with a given energy Intermediate temperature High temperature kinetic energy (ri lei T, nere The Maxwell-Boltzmann distribution above shows the distribution of kinetic energies for etids wt a-given sample of molecules at diferent temperatures. katy te ugh KE, grey Jowey KE ; ie As the temperature increases, there is a broadening of the energy distribution of the particles. Thus, there are more possible energy states in which the molecules can adopt at a higher temperature. Hence, an increase in temperature leads to an increase in entropy. high Tr oe party ville bigher be 1.2.3. Change in Phase Entropy of solid < liquid << gas Solid Liquid Gas Solid to Liquid Phase When a solid melts into a liquid, the order in the solid is destroyed. Particles in a liquid are more disordered than 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 as the gaseous state is the most disordered. This change of phase is also accompanied by a large increase in volume. 1.2.4 Change in the Number of Gas Molecules The arrangement of molecules in a gas is the most disordered amongst the three states of matter as the molecules are in constant random motion. ‘When the products of a reaction contains more gas molecules than the reactants, the entropy of the system increases. ‘Some examples of such reactions include * decomposition of CaCOs: CaCOx(s) —> CaO(s) + CO%g) + decomposition of N,O: N-O(g) —> Nag) + %O2(g) * combustion of propane: CsHe(g) + 501g) —> 3CO2(g) + 4H.0(a) © Raffles institution 2017 4 we Lecture Notes Sb ~ Chemical Energetics t Example 4 For each of the following processes, state, giving a reason in each case, whether the change in entropy of the system is positive or negative. (a) Crrhts(s) > Crt AS>oO Liquid has higher entropy than that of solid as there is greater disorder in the liquid {b) Nag) + O2(g) > 2NO) AS=0 (very small, can be positive or negative) There is no change in the number of gas, molecules, hence there is little change in the ‘state than the solid state. Gog oF phase number of ways for the molecules to arrange . Pere dap bo gun (ec), 2H20() — 2Hx(g) + Og) (4) Na‘(g) + Cig) + NaCi(s) AS>0 AS<0O Gaseous products have higher entropy than in liquid reactants due to greater disorder in the gaseous state. Large amount of gaseous products produced further increase entropy. inn gprrrs jodi © Raffles Institution 2017 5 shovpe i anct gover pail 2 moles of gaseous ions to form 1 mole of solid NaCl. A decrease in entropy of the system as solid has much lower entropy than gas since the particles in solid are significantly more ‘ordered than in a gas. Lecture Notes 5b ~ Chemical Energetics I 2__ FREE ENERGY Candidates should be able to (a) state and use the equation involving standard Gibbs ree energy change of reaction, AG®, AG® = AH —TA5® [the cieulation of standard entropy change, 85°, fora reaction using standard entropies, S, isnot required | (@) state whethera reaction or process willbe spontancous by using the sign of AG? (understand te tations inthe use of AG® to pedi the spontancity of reaction 24 Standard Gibbs Free Eneray ‘The Gibbs Free Energy change, AG, is given by the equation: bens pas | talon “ AG= AH- TAS tee pres > oegsiclly feuill ‘The Standard Gibbs Free Energy change, AG®, is given by the Eaton nat Reville. AG®= AH? — TAS® + AG?® is obtained at a pressure of 1 bar and at a specified temperature, which is commonly 298 K. + Generally, we can assume that AH? and AS® do not vary significantly with temperature ie. AH® and AS® can be assumed to be constant. 22_Rel jonship between AG® and the Spontaneity of a Rea n A spontaneous reaction is one that can occur without any external assistance. It is irreversible, as it cannot be brought back to its original state again under the same condition, Generally, a spontaneous reaction results in a system moving from a less stable state to a more stable state. Example: Ice melts spontaneously at room temperature but melted water does not form ice spontaneously at room temperature. Thus, the melting of ice is a spontaneous reaction at room temperature. ‘AG®< 0 (negative value) ‘AG® > 0 (positive value) the forward reaction is spontaneous the forward reaction is not spontaneous (ce. itis thermodynamically feasible). (i.e. it is not thermodynamically feasible), Itis said to be exergonic. It is said to be endergonic. 8 uremitle - _ ave rat chin oginal sta Hig atter 23 itations of the use of AG® Bien are free AG® indicates the thermodynamic feasibility (spontaneity) of a reaction i.e. whether it can occur. pruicd wht peuchon U spectonin | thesme me dy rer Peasrhle It gives no information about the kinetic feasibility (whether the reaction proceeds at an observable rate). The kinetic feasibility of a reaction depends on the activation energy. here dynpaa. Rul iby 4 Linc Peat Lily © Raffles Institution 2017 6 Lecture Notes Sb ~ Chemical Energetics Calculations involving Standard Gibbs Free Energy Change, AG® Standard Gibbs free energy change, AG®, can be calculated using the equation: 7 tka counerly weal AG® values are measured at 1 bar and a specified temperature. AG® in kJ mot, AH® in kJ mot and AS® in J mol" K+ AG® = AH® ~ TAS® Example 2 Calculate AG® at 00 K for the following reactions and predict whether reaction is spontaneous at 500 K. (a) 20019) + 2NHs(g) —> C2He(g) + (b) 20) + xg) —> 2NOxg) 2NO(g) 114.1 kJ mot He AS® = 146.2 J mob K* AS? _ AG® = AH® — TAS® AG® = AH® — TAS® 2 oa AG? =_+4e} -s00 (Tan) aG?=_-l-l = sw (57) (convert J mol K* to kJ mol K"') (convert J mol K*to kJ mol? K*t) AG® = +474 kJ mol">0 AG® = ~41.0 kJ mol The reaction is not spontaneous at 500 K. _| The reaction is spontaneous at 500 K. Check for consistency of units. In example 2, AH° is given in ki mot-* and 4S? is given in J mol'K-*, The necessary conversion must be made. © Raffies Institution 2017 7 Lecture Notes 5b ~ Chemical Energetics Effect of Temperature on the Spontaneity of a Reaction } Candidates should be able to: (@)_predien the effect of snperature change on th Since AG = AH ~ TAS and assuming that AH and AS do not change with temperature: * AGis dependent on temperature * By comparing the signs and the magnitude of AH and —TAS, the sign of AG can be determined: ‘Scenario 1 AS. ‘Scenario 3 AH0 AS>0 AS>0 Spontaneous at aif Spontaneous at temperatures. high temperatures aa Scenarioa AH <0 sH>o ‘Scenario 2 ASO ‘AG <0 at all temperatures "| Explanations: Comparing signs of AH and ‘These reactions are spontaneous _| ~TAS: (Le thermodynamically feasible) at all | AH < 0 and since AS > 0 then-TAS <0 temperatures. Both AH and -TAS are negative Examples of such processes include: = decomposition of ozone and dinitrogen monoxide + organic combustion * explosives Example 3 For the following process, explain why AH and AS have the signs as shown and comment on the feasibility. HO.) > H.O() + 40.9) AH<0,AS>0 Solution AS > 0: There is an increase in number of gaseous molecules, resulting in an increase in disorder of the system. AH <0: H,0(I) and 1%402(g) are energtically more stable compared to H2O,(I) or the bonds in H-O()) and %0-(g) are stronger compared to those in H2O2(I) Explanation for feasibility (i.e. comment on sign of AG) Since AH and ~TAS are both < 0, AG < 0 at all temperatures. Thus the reaction is spontaneous (i.e. thermodynamically feasible) at all temperatures. © Raffies Institution 2017 8 Lecture Notes 5b — Chemical Energetics i Scenario2 AH>OandAS<0 AG > 0 at all temperatures Explanations: These reactions are not spontaneous | Comparing signs of AH and -TAS: (ie not thermodynamically feasible) at all | AH > 0 temperatures. Since AS < 0 then -TAS > 0 at all T Both AH and -TAS > 0 ‘Thus these reactions have to be driven continuously with external assistance. Examples of such processes include: = photosynthesis "formation of ozone from oxygen Scenario3 AH and AS both > 0 These reactions are Explanations: + not spontaneous (ie not Comparing signs of AH and TAS: thermodynamically feasible) at low | AH> 0 temperature, and Since AS > 0 then -TAS <0 + spontaneous (i.e feasible) at high temperature. At low T, The sign of AG is determined by the sign ice. of AH AG > 0 at low temperature (T < AHIAS) | > the positive AH term outweighed the AG < 0 at high temperature (T > AHIAS)| ~ negative -TAS if TAS > AH >AG>0 Examples of such processes include: At high T, = metting and boiling The sign of AG is determined by the sign * most decomposition reactions of -TAS | + electrolysis : Dnegative TAS outweighed the + dissolving (for certain solids) positive AH DAG <0 Example 4 For the following process, explain why AH and AS have the signs as shown and comment on the thermodynamic feasibility, NH4NOs(s) > NH«*(aq) + NOx(aq) AH > 0, AS> 0 Solution AS > 0: The disorder achieved in breaking up the lattice into ions is greater than the ordering of water molecules around the ions. AH > 0: Recall AHsoin = AMhyg ~ AHist, AH-oe(NHsNOs) is positive since the lattice energy of NH«NOs is more exothermic than the SUM Of AHnys of NH” and NOs- Explanation for feasibility (i.e. comment on sign of 4G) At low temperatures, AG is positive because the positive AH outweighs negalive —TAS. At higher temperature, the negative -TAS outweighs AH, so AG becomes negative. The reaction is not spontaneous (i.e. not thermodynamically feasible) at low temperatures, but spontaneous (i.e. thermodynamically feasible) at high temperatures. © Raffles Institution 2017 9 Lecture Notes 5b ~ Chemical Energetics I Scenario4 AH and AS both <0 These reactions are + spontaneous (i. themodynamically feasible) at low temperature, and not spontaneous (i.e. not thermodynamically feasible) at high temperature. ie. AG <0 at low temperature (T < AHIAS) if TAS < AH AG > 0 at high temperature | (T> AHIAS) Examples of such processes include: = condensation and freezing Explanations: ‘Comparing signs of AH and ~TAS: AH<0 : Since AS < 0 then -TAS > 0 AtlowT, The sign of AG is determined by the sign of AH the negative AH term outweighing the positive -TAS 3aG<0 these exothermic reactions are spontaneous (i.e thermodynamically feasible) at low temperature Athigh T, The sign of AG is determined by the sian of + addition and combination reactions | "= : ee ar Dthe positive -TAS outweighs the precipitation fb >AG>0 these exothermic reactions are not spontaneous (i.e not thermodynamically feasible) at high temperature Example 5 For the following-process, comment on the feasibility. 4Fe(s) + 302(g) > 2Fe20.(s) Solution AH<0,AS<0 ‘At low temperatures, AG < 0 because the negative AH outweighs the positive -TAS. At higher temperature, the positive TAS outweighs AH, AG becomes positive, ‘Thus the reaction is spontaneous (i.e. thermodynamically feasible) at low temperatures if the negative AH outweighs the positive TAS, but not spontaneous (i.e. not thermodynamically feasible) at high temperatures aH, 85 op sry > AG wlepudl ot foaprotuc ‘Summary of Effect of Temperature on the Spontaneity of a Reaction 4G aH | as | -Tas . Atlow T At high T 2 Sale ‘Always <0 A. | Temperature | <0 | >0 | <0 (Spontaneves atallT) | independent pita =o 8 coo 0 | sei 8] (Non-spontaneous at all T) >0 <0 ©. | Temperature | >0 | >0 | <0 | (ionspontancous) | _ (Spontaneous) dependent ontane taneous) 2 cee eee | ieee | oo (Spontaneous) (Non-spontaneous)_| © Raffles Institution 2017 10 aH, AS same seyh 6G depovled ve teapot. Lecture Hotes Sb ~ Chemical Energetics Quick Check 1. For the following process, explain why AH and AS have the signs as shown and comment on the feasibility, CoHa(g) + Hog) > C2He(g) AH<0,AS<0 Solution, AS <0: there is a decrease in number of gas molecules (2 mol of gas reactants to 1 mol of gaseous products) -TAS is therefore positive. AH < the reaction involves a greater amount of energy in bond formation than bond: breaking, (i.e. 1 C=C x bond and 1 H-H bond are broken, and 2 C-H bonds are formed. AH = (+610 ~ 350 + 436) ~ 2(410) = 124 kJ mol"' <0) Explanation for feasibility (i.e. comment on sign of AG) At low temperatures, AG is negative because the negative AH outweighs the =TAS. At higher temperature, the positive -TAS outweighs 4H, so AG becomes posi 2. Areaction is non-spontaneous at room temperature but is spontaneous at -40 °C. What can you say about the signs of AH and AS? the negative AH outweighs the positive -TAS. Ata higher T of room temperature, AG > 0 because the positive ~TAS outweighs AH. E <0 and AS<0. Ata low T of 40°C, AG <0 (reaction is spontaneous) because Substance "| MgCOa(s) | MgQs) | coxa) | AGP kJ mot =1012_ | 569 -394 |} (a) Use the standard AG;® given above and the formula AG = EmAG/(pdt) ~ ENAGP(nt) to calculate the free energy change, AG, for the reaction below: MgCOs(s) ———» MgO(s) + CO2(g) . | Will the above reaction take place spontaneously? (b) Given that the AH® of the above reaction is +101 kJ mol-’, and the AS® for the reaction is +159 J mol"' K", estimate the temperature at which the reaction will take place spontaneously. (a) AG® = (569-394) ~ (1012) = +49 kJ mort The reaction will not take place spontaneously because AG® > 0 (b) Applying AG = AH-TAS For reaction to be spontaneous, AG= AH-TAS=_'el - Tle-ls4) <0 101 <1(0.159) i 635K arcane ‘So a temperature of above 635 K or 362 °C is needed for the reaction to take place. (assuming that AH and AS do not change with temperature.) © Raffles Institution 2017 "1 Lecture Nates Sb ~ Chemical Energetics I 4. Give explanations as to whether the following reactions are feasible: (a) 2X(g) + 2¥(g) ——* 3Z(9) AH? = —150 kJ mol (b) X() ——* Y@ * Z(9) AHP = +200 kJ molt {a) aS <0 (4 mol of gaseous reactants to 3 mol of gaseous products), so -TAS > 0. ‘At low temperatures, AG < 0 because the negative AH outweighs the positive -TAS. At higher temperature, the positive TAS eventually outweighs the negative AH, and so AG = AH — TAS becomes > 0. The reaction is thermodynamically feasible at low temperatures but not feasible at high temperatures. (b) AS > 0 (due to formation of gaseous product from liquid reactant) so-TAS < 0 and AH > 0. At low temperature, AG = AH ~ TAS > 0 because the positive AH outweighs the negative ~TAS. At high temperatures, AG positive AH. ‘The reaction is thermodynamically feasible at high temperatures but not feasible at low temperatures. 1H — TAS < 0 as the negative -TAS outweighs the oe becgilon ot tye fae sm damier she t : mid tOG) > at 0 Se AS <0 207 = am Tas 20 rly ber we tremhon eb rrng Youre bed i hyd 5+ AH

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