© THERMOCHEMISTRY recoed for lant ‘amen th molecules prosucod by plans are Op ana even, CMWHAT’S AHEAD 5.1 The Nature of Energy WWebegin by considering the nature of energy ant {he fame aks, noah tic eng ad tet every We wil aso sus tre rt ed Inna energy and hc fc that ney can Be thd to acomplia oo ana a To sty ‘hergy Ganga we focus on particular pat of Oe Snivere which we cal the re Fertig le ald te suroendngs 5.2 The Fist Law of Thermodynamics ‘Weve then cxplore efit ln of erodes Energy cannot ected o destroyed, but ean be transfered between systems and surroundings. Internal nergy nena onergy fan, {guanety whose value depends only onthe tt, ‘Sreandtion ofa neem nove not on hate System came oe in tht sate 5.3. Exthalpy [Ne fe il encounter 3 state ncn called nig, hat lates to nergy Ts unction ‘ef Beaune the changes erty rcssires te giant oh eer pine Fat Dyasystm ina proces cece constant pros 54. Enthapls of Reaction We ise thal he ena change asncated sta chemical ection (Ap) ven By he rupee products as the ena pies of ‘he matans.Ta guy ely proportion "o theamoun of eactant consumed in th pros. 55. Calorimetry ‘We wl nen examine corny, which na ‘epemenial thru that wee onesie hast ‘Sings chee proces, 56 Hes’s Law ‘We willbe hat theenthnpy change for ‘micton can be cleulated using appropiate Spy fer i wehich ue the fot at eel Iter tate funn 5.7. Enthalpies of Formation ‘Than we wl aroha to estabih tandard ‘ales fo enapy changes in che ects ed owe fouse hen tute enthalpy changes forrectns (3a. 548 Foods and Fuss rally we wil amie fods and fl source ‘enemy and cue oe ito ealth ad ‘esa een MODERN SOCIETY DEPENDS ON ENERGY for its existence. Energy is used to drive our ma chinery and appliances, to power our transportation vehicles, and to keep us warm in the winter and cool in the s mmer. It is not just modern society, however, that depends on energy. Energy is secessry for al ie Plants, such as those in the chapter opening photogeaph, ‘Se solar energy to carey out photosynthesis allowing the plants to grove. The plans in ture provide fod, fom which we humans derive the energy we ‘eed to move, to maintain body temperature, an o cart out bodily functions What exaty is nergy though, and what prineipes are involved in sMsmany transactions and wanslormations, such as those fom the sun plants 0 animals? Tn this chapter we begin to explore nergy an its changes. We are moti vated party by the foc! that ence changes invariably accompany chemical reserons Indes, sometimes we use 3 chemical reaction specially to obtain enengy a5 when we bur fuels. Thus, energy is very mucha chemical topic [Nest all ofthe energy on which we depend is derived fron chemical yc ‘ions, whether those reactions are associated with the combustion of fuels the ‘lscharge ofa battery, or the metabolism of our foods, If we are to properly 165166 CHAPTER 5 Thermoche ® ‘A flgure 5.1 Work and meat. Egy {iss Wok energy wea to sean Shpet nih stone heat Seige aca pete > Figure 5.2 Potent energy an faetcenegy. 9) Myce top ‘tani ra ah poten eer Bike ae srocea wn e understand chemistry, we mst lo derstand he energy changes that “Tet ofenesgy and fs anformaton is koown a themodynales (Greeks homes “heats ay nem, “power his chaper we wl xanga pet of thrnyna that involves the elatonhips between chemical tetera and energy changes involving best. Thispotlon of hermod yaaa icalledthermacheminty We wl ius adtonalepects of hemody ‘ami in Chapter 5.1 THE NATURE OF EN! Although the idea of energy i familar one, it bit challenging to deal with the concept in a procve way Energy is contnonly deine wo Eh opty fo do worker fo transfer het. This definition requires us to understand the concepis of work and heat We ean think of work asthe energy used 1 anus a ej ik ras to move agunst force and eat the energy aed cae the teperator f ‘abet to inease Figure 5.14) We will consider each a these concepts ote loony 40 give them fuller meaning. Les begin by examining the ways ‘which matter ean possess energy and how that energy can be transferred fo tne pace of matter to another RGY kinetic Energy and Potential Energy ‘Objects, whether they are tennis alls or molecules, can possess Kinetic energy, the energy of mution The mapritude ofthe kines ener, Fy of an abject de pends on temas, mand speed b= bt 6 Equation 5.1 shows that the kinetic energy increases as the speed of an abst increases, For example, a car moving a 35 mules per hous (mph) has greater etc energy than i docs at 40 mph For a given speed the Kinet coerey Increases with increasing mass. Thus, 2 large spor-utily vehicle waveling at 55 mph has greater lineic energy than a sll sedan traveling atthe same speed because the SUV has greter mass than the sedan. Atoms and moles ave mass and are in motion. They therefore possess kinetic energy. All other Kinds of energy—the energy stored in chemical bonds, the energy of atwaction of north and south poles of magnets for example are potential nergy. An objec can possess potential energy by virtue of i postion relative to other abjees. Potontal energy arises when 2 force operates on an obo. {forces any kind of push or pull exerted onan objec. The most aml ores isthe pullof gravity. Think o cyclist posed at the fop of hill, asillatated Figure 32. Gravity acts upon her and her bcye exerting 3 force directed 19 ward the coner of Barth Atte top ofthe il the eylist and her bicycle possess $ certain potential energy by sre of thir levaton. The pono energytsgiven bythe equation E, = mgh, where mi the mass of the object in question fin this case the eyeist and her bicycle), His the height of the objet relative to some reference haighl, and gs the gravitational constant, 9.8 n/s™-Once in mo fon, without any further efor om her part the cyclist ins sped a the bie lerolle down the ill Hee potental energy decreases ar she moves downoad, but the energy does not simply disappear It is converted to other forma of en cngy principally kinetic energy he energy of motion. This example lustrates that forms of energy ate interconvertbe Geavty isan important fore fr lange objects such as the eyls¢ and Fath Chemistry, however, deals mostly with exttemely small objets atoms and molecules, Gravitational forces play a negligible role inthe ways these sbmn- ‘roscapie abject interact with ane another. Forces that are from eeccl ‘charges are more important when dealing with stome and molecules, ‘One of the most important forms of polenta energy in chemistry is clectosttc poten energy, which arises fom the interactions betwoen charged partles. The electrostatic potential energy, Ez proportional to the electrical ‘charges on the fo interacting objets, and Qs and is inversely proportional to the distance separating the by i521 Here is simply 2 constant of proportionality, 8.99 10" an/C® (Cs the ‘coulomb, suns of electrical change = Seton 2), and) 8 the ole uni of ‘energy tat we will soon discuss) When dealing with molecularevelobjees, the estrialcharges Ot and Osage typically om the order of magnitude of he charge ofthe electron (69 * 10" C)-When Q, and Qzhave the same sgn (fr ‘example, both are positive), the two changes repel one another, pushing them part Es pasitive. When they have opposite signs, they atract one another, pulling them toward each ther Ey s negative. The lower the enegy of 25s" fem dhe more tablet Ths, the more stongly oppente changes interact, the more sable the system ‘One of our goals in chemistry iso late the energy changes thal we seein ‘our macroscopic world to the kinetic or potential energy of substances athe ‘tom or molecular level. Many substances ful, for example—zeleaseeneY when they react The chemi energy ofthese substances dse to te potential ‘nergy stored in the arrangements of thor atoms. Likewise, we will sce that the energy «substance porseaes because of temperature (ts thomal energy) iasociated with the Kinetic enegy of the moles in he substance ‘What arth tema forthe energy an abject poses (a bese of matin, (Be ‘hospi? Wha tern ced oder changes of eng sented ‘h(a empertare change (2) moving an jet past aoe? Units of Energy “The Sl unit for nergy is the joule (pronounced “oo, Jin honor of James Joule (618-1889, 8° Britsh scientist who investigated. work and. heat TT = Tg Amassof 2 kg moving ata speed of m/s possess a Kinetic cvengy of Fe = bro! = Hogi mys = 1g! = 1) Aju isnot large amount of energy and we wil often use jue 8) in “isushing the energies associated with chemical reactons ‘rationally, energy changes accompanying chemical reactions have been ‘expressed in calories, nonSt unit tll widely used in chemistry, biology, teal biochemistry. calorie (cal) was originally defined as the amount of ners) 51 “The Neture of Energy 167168 CHAPTER 5 Thermochemistry ‘A fgure 83. Adloved system and ‘erounaings. Yysrnge a angen Sura cofined ns inde wih ‘tonal penn ae eee Sry ie propertes of se gases, be [her ar te ye an ede apn pa te sures. Iceni the een schange eer Cintneform obec ara er) Bure Sosed Sten raguired to aise the temperature of 1g of water from 145°C to 155°C. Acalo- Fes now deine in frm of te joule 4:18 (exactly) related energy unit used in nutrition isthe ntritional Calorie (noe that this ‘sexptaizady 1 Cal = TOO) eal ~ 1 kel tal System and Surroundings ‘When we analyze energy changes, we need to focus our atention on nite and well defined part of the universe fo keep track ofthe energy changes that ‘Secu The portion we single out for study is calles the system everything ele i ‘led the suretundings, When we study the energy change that accompanies ‘chemical reaction in the laboratory, he reactants and products constitute the sys tem, The container and everything beyond tare considered the surroundings ‘Systems may be open, closed, oF aolate. An oe system is one in which matter and energy can be exchanged with the surroundings. A boing pot of ‘water on a stove, without its ld, isan open sytem: heat comes into the syste From the stwe, and waters released othe sterundings as seam, "The systems we can most readily study in thermochemistry are called closed systems closed system ean exchange energy but ot mater with roundings For example, considers mixta of ayarogen gas Il, and oxygen {s, Oy ine cylinder a lustrated in Figure 5.3 «The astem ia this cases us, the hydrogen anal oxygen the cylinder, piston, and everything beyond them (including us) are the surroundings I the hydrogen and oxygen reel to orm ‘Wate, energy is bere: 2Halg) + O2lg) —+ 21,06) + energy Although the chemical form ofthe hydmgen and oxygen atoms the sytem it ‘hanged by this reaction, the system has not lost or gained mass it undergoes no exchange of matter wit ts surroundings. However ean exchange energy ‘with ts surroundings inthe form of work and heat. "An slated system is one in which neither energy nor matter can be ex: ‘hanged with the surroundings. An insulted thermoe containing hot coffe sp proximatesan isolated syst. We know, however, that the cvfee eventually ool, 0 ss not perfec lated, sito ii nl open psn ‘Transferring Energy: Work and Heat Figure 5.1 llstates the wo ways that we experience energy changes fn out ‘everyday livin the form of work or heat. In Figure 51(3) energy i rane ferred fom th tennis racquet othe bal, changing the diction ad speed of| the Ball's movement. In Figure 5.6) energy is transfered inthe form of het. Indeed, energy is tansferred between systems and surroundings in wo genet always ax work o hes. Energy used ta cause an object to move agains afore icalled work Taus, wean deline work, w, as the energy transfered when a force moves an abject, The magnitude of this work equals the product ofthe force, Fan the distance, 4, that the objects moved! worxa 31 ‘Wie perform work for example, when we ian object agains the force of av ity or when we bring two lke charges closer together If we define the object fs the sytem, then eas pat ofthe sutroundinge are performing work on that syste ranstering energy to“The other way in which energy i transferee is a het. Hat is the enengy transfered fom a hotter object toa colder ane. Or stating this idea ina slightly ‘more abstract but nevertheless useful way, heat the energy transfered be- toveen system and its surroundings beease of thei diference i temperature ‘combustion reaction, suchas the burning of natural gas Mustrated in Figure 510), leas the chemical energy slored in the molecules of the fel. {Sn Gacsion 2) If we define the substance involved in the escton as the ys tem and everything els as the surroundings, we ind thatthe rleased energy “auses the temperate ofthe sytem to inerease Energy i the form of eat then transferred fom the hotter system tothe coker sroxndings Im SAMPLE EXERCISE 5.1 | Describing and Caleuating Energy Changes ‘Abort 54.4 (1259 bowing Dal fom ground level to a height of 16 m {Eterm ofthe owing Sal ei el om the gn Wha uy of ‘Etenery ote hi ase rom th gr tut sk in umd tau tbl (@ Aer tbl Sopp pas tec [pif nue atl ofthe work Sein pr hos en come tose ast the tne theal ste te rosa wha hopend oe al a hein fn befor tt te ground? (Noe The one et gravy is =m Xgeherem {Septet objet gna conan = 98 m2) sowution ‘Anatye: We ed sate th potential cosy oe bowling bal ots poston ‘hange in penal energy ofthe bil Finally, we need to cnet he change po fait entay hes Oe Eu cropped nee Ov nesses ry oe lan: We cn acute the work doe in ing the bal by using Equation 53 Fsenil energy We can othe inc energy and Equnon St cline Frets artmpace (a) crate bowling tls to greater eight above the grounds ote. ‘tlenegy incense (0) The bana mas of and ts ie 3 dtance of Lm. Tce he ‘ook pesto to rase the bal, we se bth Equaton 83 and F'= m % fore Wire fatten togery: meg 4= G4 IOR M/E) = AB Ag Me = 85) ‘Thus the bower as done 8 of work oli he alto a oight of 1.6 (nes tcl. croppe pci eng caved Hacc ery: AL ‘he instant jst befor the bal se ground we asim tal he Ke energy qual thewore done pr) 8} Bf! = 85) ~ Sig a? Wecan now ste this ution for +) Cae”) namie Vasa ‘Check: Work aust ne dane in pat (bo eease the poten energy of he bal Sisk ein aco eh “Tae unis ee oppropritc Eo prs {sich Te wok om ns of [and he speed nuns of ns put) we ve a ‘od sn aatann apt th nro leuton nel the quae Tsu ‘neraport heal value toon twosiguiian igus as appeoprate Comment: speed of I mys is roughly 2 mph, so the owing ball has a speed fat than 10 mph upon pac. im PRACTICE EXERCISE What he kine nergy in J fa an Ar stom moving with 3 spot f 5.6 BhnwicorArstsmngtlng wih sped b.nye Ga tam = Toa 10 Samer aA WCB > 8) 51 “The Neture of Energy 169170 CHAPTER “FFgure $4 Changes tn erat ete hen ete ne re ‘Srey released he ‘eoresented by an arom Pits ‘Serward bebe tet al Stef heer nthe ne Seoycunge ete yt, ha Fa negate Bh ome aye gene energy hat egy ged om he sronaias {peor beeen tei ar al Stes of he seman the erry Shang fhe sion poste Nae [Sate and) hat fe verte sow Cte atte il sate ar has S| Fotsystem decenves ® “Thermochemistry 5.2 ‘THE FIRST LAW OF THERMODYNAMICS. ‘ichave sen that the potential energy ofa system canbe converte into kine ‘energy, and vce versa, We have also een that energy canbe transferred back ‘and forth between a sytem and ts urroundinga in the forms of work nd heat. in general, energy can be converted from one form to another, and i an be ttansferred from one place to another. ll of thee transactions proceed in ac ‘ord with one of the most important observations in scence tt enengy cm ‘beneither rested nor destroyed. A sine statement known asthe is law of ‘hermodyaamics summarize ths smple tt: Energy conser. AY energy that is lost bythe system must be gained by the surroundings, and vie versa “To apply the first law of thermodynamics quantitatively we must fist define theenergy of sytem more prise. Internal Energy ‘The intemal energy ofa systems the gum of al the kinetic and potential ene ies ofa ts components or the system in Figure 3, for example, the internal ‘nergy includes the motions of the Hy and Oy molecules through space their rotations, and ther intemal vibrations. It ako inclades the enecpies oF the ‘nace of each atom and of the component electrons. We represent the intemal ‘nergy with the symbol F Some lees, particularly more advanced ones, use the symbol UL) We generally do not know the acts! numerical vale of ‘What we can hope to know, however, i= AF (ead "delta E" the change in E that accompanies a change the syst. Tagine that we tat with a system with an inital internal energy, Ens “Thesystem then undergoes a change, which might involve work being done heat Being rafered. After the change he Fin internal energy of the syste 15 Fea. We define the cage in internal energy, AZ, asthe diference between gah Evo AE = Fapt ~ Ene a1 ‘To apply the frst law of thermodynamics, we need only the value of AE, We do ‘ot eeally need fo know the actual vals of Egat of Ea fo the system, Thermodynamic quantities sich as A. have tree parts (3 momen and (2) a unit that together give the magnitude of the change, and (3) a sign that inves the diection. A posite value AF revals when Fes Fas indicat Ing the system has gained energy from its surroundings A negative value of AE ISoblained when Eng = Fyuay indicating the system has lst energy Ws surroundings. Notice that we are taking the point of view ofthe system rather than that of the suroundings In discussing the energy changes We need to remember, however that any change in the energy ofthe syste is accomps ried by an opposite change inthe energy ofthe surroundings. These features of ‘nergy changes are summarized in igure 54, i E> lan, ST =) Fie Eofaytem cease ai “nest 3 comm le doe ane acl, hg hah he ed ae5.2 The First Law of Thermodynamics 171 Ina chemical reaction, the iii tate ofthe system refers othe reactants, and the final state refers tothe products, When hydrogen and oxygen form “water at 2 given temperature the system loses enargy to the surroundings Because energy lost from the system, the internal energy ofthe products (final state) cles than tho he reactants inal tte) and AL for he process Isnegatve. Thus, the egy diagram in Figure 5p shows thatthe internal es cngy ofthe mixture of H and Osi greate than that of 10. Bagh 04) vegans] |posewe) "he eteralenry for Mig) and Chg grater than that of Mg). Set an ‘rca digram a presets the esto MECC)» te)" Cl). HOO) A Figure 5.5 emery eagram forthe interconversion F9) Ong yoan, Asytem corpora Relating AE to Heat and Work BS tig fara gree narra wey As we nated in Seton 51a sytem may exchange energy with ts suround. han one compose HO The ings as heat or as work Te internal energy ofa system changes in magnitude 9 es regy(9¢ Own iy astheat is added too removed from the sytem or as workisdoneonitorby it, sngOraeconveted @ HO, Kaas If we think of intemal enengyas the system's bank account of energy we sce Ses toon Oy that deposits or withdrawals canbe made ether in ems of het orn rts of work Deposits increase the energy ofthe system (postive AE), wheres with 0 done om the system by the surroundings, has a positive value (igure 56) ‘Work alu is deposi increasing he internal energy ofthe system, Conversely, both th het os by the system fo she surroundings andthe work done by the Fe 5 Sam conentans for system on the surroundings have negative values; that they lower the nee. Bett and work, Gare by ‘al energy ofthe syste They are energy withdrawals and es a result, ower eran ek w done 0.99 the ota amount of energy inthe energy account, The sign conventions forge, ew he real enero and AE are summarized in Table 51. Notice that any energy entering the sys: tur enang Setooe poste tem aseltherheat or work carts «poe sign smn ~ mans sytem eset fee meas work done system Forde 1 SAMPLE EXERCISE 5.2 | Relating Heat and Werk to Changes of internal Ener ‘wo gee, A and Bl) are confined in acynder and piston atangenant he hat ings $a blancs Aud Brac te em asad oduct AG's Be) Co. ‘Rs the scion sear the stem ses 180 of eat ote surroundings The piston Ses under he constant posure ofthe atnospher the surroundngs do 30) of work fnheaytem Waa athe chanpein ie termal energy Shey?172 CHAPTER 5 Thermochemistry A Figure 5.7 Semple ot Siero cyst snd ‘See aay ied FNiugschey wxowya-6 009) —+ asco * ania “10005 San does tom abut 20°C to 9° Bi erestton of powdered sinus sit f04 te berate acion 5 ‘igh ethene he eacton proceeds ‘gpeay toorm AyO, aed meen ro 2G) FeO — drow +3, “Anata: Tho question ssh us fo determine AE, given infomation about ¢ and Plan West dtemie te sgn of and w Cable 5.1) ad han use Equation 5, Solve: esis ransomed fom the sat tothe sroundings, an work done on ‘heSjtem by the suroundings, 20 mpi and Ws paive q = 1150) and ae 0x) Thus AE = 9+ w-(us0p + sop = -<70) ‘Thenegatve valu of Ets that ne quant of 670} of energy has been ase {ered om he epee aeoondng ‘Comment: You can think ofthis change asa decease of 67 in the net vale of he Sone energy are sun (bene the negative 150 J wera he ‘yen aa, whl #80 ie doped nthe orm of work Notice hat the ole (the guse decease wrk bang daneon he sytem by he sarang, a ‘ngin epost tency Im PRACTICE EXERCISE Caleult te change inthe ineralenegy ofthe system ora process in which ‘he ytem sore 0) oat rom he sounding and doce 88] oF work on he anandings ‘answer #35) Endothermic and Exothermic Processes ‘When a process occurs in which the stom absosbs heat, dhe process i called ‘endothermic. (Endo-is a prefie meaning “into") During an endothermic process, such asthe melting oie eat vs nto the system from is suround Ingo Ie, as par ofthe surroundings, touch a container n which ce melt sng feels cold ous because heat has pased irom our hands to the container. ‘A process in which he system loses heat called enothermie, Exot pe fix meaning “ost of") Daring an exothermic proces, such a the combustion of {gasoline eat exis or flows cu of the system and into the surroundings: Figure £74 shows two examples of chemical reactions: one endothermic and the ther hrghly exothermic Inthe endothermic process shown in Figure 5 7() the tom perature inthe beaker decreases. In this example the system consists of the ‘hemical reactants and products. The solvent in which they are dissolved | part of the surroundings. Heat lows from the solvent 35 par ofthe suroun fngs, nto the system a eatants are converted product. Thus, he tempers- tre ofthe solston drops Using gaze 55 ap 2 merece, indicate whether the ection 2H0() —+ 2g) + O46) senothermic or endothermic Wha ature) the igure indie these acho berotheuac oe endothe? State Functions Although we usvally have no way of knowing the precise value ofthe intemal nergy ofa system, Fit doos have a fixed Vale fora given st of conditions “The conditions that naan internal energy include ihe temperature and pres sure. Furthermore the total intemal energy ofa system i proportional tothe total quanity of matter inthe system because energy is an extensive property. ‘a Gection 13) ‘Suppose we define our system 05 50g of water at 25°C a in Figure 58>. ‘The ayer could have ared at this state by cooling 50 g of water frm 100°C or by melting 80g of iceand subsequent warming the water to 25°C5.2 The First Law of Thermodynamics 173, « * ° 0 endothermic ea aH 0) Fie Sur oss heat ner proces) Bi negate CaN176 CHAPTER 5 Thermochemistry Ayer ENERGY, ENTHALPY, AND P.V WORK nechensty we a intersted mainly in evo types of work ‘incl work and mechanical work done y expanding ise Ne wl focus hore oly onthe ater called presse ‘Shue, P-V, wark Expanding pase inte eying of $itorodie engine do PU work an he piston ths work eve tion vewel do P-Y work the atmosphere. This ork complies noting i practical see, ul we fut hee teak fall work, nfl sea whon monn the ney hago ays, ‘Eider a gw confned toa cylinder with movable pe on of erospscctona aan gure 512¥)_A downed {orc fat am the poston The pose onthe as the fence pe aes P= F/A We ol ero thatthe pon Se wwe and tht the ony” presure acting an i the npr psa tat i dt the neigh of Fan's aoe her which weil anume tone constant “pnosethe pin the cinder expands and the piston moves nalstance, 8h Pom uation 53 themagnadeo he Cros sctional— nal aa ‘figure 5.12 premare sels work Apion vn ware expat trelume fe site” aga an ‘xa reste, des wort one suoundngs. The rst dwar anette sen on euros work doe bythe sytem aguas the distance moved tines the Forex Sng the ton Magnitude ofwork = force distance = FX (SA We can msrrange the dfinton of peut, P= F/A, to PoP a In sddiion the volume change AV, euling from the movesnnt ofthe pstan the prods ofthe co Secon ara of the pston and the ditnce & move: SVS Sint ino Bquston Magnitude of work =F dt Pav Because the stem (the confine ga) doing wask on the srrounings te works ops guy “pay Bm Nove, BV work i the only work that an be dane, we an ‘tte Equation 512 nto Equation Stage ae Pav 1 (AV ~ 0, he haat easter equal the change seal cn AE= ay Constant volume) “The subscript V indicts tha th ole icons Mont acions ave rin adr constant pesute cond tion inthis cae uation 818 beans AE gp Pav or aerarepav 11 (oonstan presse) [515] But ese rom Equation 9 thatthe righthand ide of Equa tion 51815 ost the erhalpy change under constant peste ‘ondion Ths, SH = pan eso caren Eguadons 10. In summary, the change intel energy ea 9 he at gn olan at conan wolume he chunge ms enulay trogtat ith het gine rot tconetat peer The Irene between Af and AH! ithe aunt of PV work dane ty the agen hen ie proces cova a coat prea pV" The volume change acompanying many reactions dove to er, wich makes PV, aa theron he erence Tetcen AE ae AH, sa Is general satstatry to se SH ae the measure of energy changes during ost cereal rsesce Felted Bese: 58,53, 535,535 I SAMPLE EXERCISE 5.3 | Determining the Sgn of AH al ut under semosphareprosute odindiate wheter he proc enotheie revotbrmi a Ano cabs mat Io butane Cli combate ‘Sent onygento pve complet enbustion €0 COs and 0 souution ‘anya Out gua st deernine wither AH is pose o og ‘recess Bente each process appens fo oct at cnsantpresur. fe enDalpy hangs leach one equi he seu ol Rest abated een, 18gproces Procaets in which het absoed are endothermic and fave a postve Solve: In) he water at mas up the ke cabels the span The ie cae aborts ric nthe sytem ite of butane and de oxygen eqs to combust The sm PRACTICE EXERCISE ‘Scipe tothe suroundig A spac inate conGastion the bute, which forme ‘change in the reaction, would the piston rie allo stay the same? ‘roduc in ore oles of gan Ube aca, as shown by ebuanced as 2Cyl) + BOM) — BOM) + 1014.08) ‘As rel the pon would ae ome oom forthe adional mck of gs ‘expansion ofthe gave because of te lperate ease A ENTHALPIES OF REACTION Because AH = Hy) — Hie the enthalpy change fora chemical reaction is jen by the enthalpy oft products mins Uh enthalpy ofthe reactant AH = Hyun ~ Hess (5.0 The enthalpy change that accompanies a rection is called the enthalpy of reacton, of merely the heat of reaction, and is sometimes writen APs, Where an is commonly used abbrevistion fr “reson The cambustion of hyrogen i shoven in Figure 513. When the reaction Is controled so that 2 mol Hy) buon to forin 2 mol HyO() al «constant pres. sure, the system releases 48088 of heat, Wecan summarize this information 9s 2HiG@) OG) —* 240) A= 886K) (5.7 ss Flgure 5.13 drogen with oxygen. (0) ads sd ne (gu haonygen a O Tose ares tence wih Ox teem OA Treen Same Toe se ger thea fe auroondingh (oe rap 5A Enthalpies of Reaction Jos v7178 CHAPTER 5 Thermochemistry Premera lord de dete eptin ‘State Rew ey nk rege Bp ga Mirrors oa gets ngs) - 2046) (Coxe) = B10 AH s negative, so this reaction is exothermic. Notice hat AH is reported atthe ered ofthe balanced equation, without explicitly mentioning the amounts of chemicals invotved, In sich tases the cafficents in the balanced equation ‘presen! the nuber of moles of raclanis and products producing the assoc sed enthalpy change. Balanced chemiesl equations that show the associated Snubalpy change in ths way ate called thermochemical equation the enthalpy change accompanying a rene tion may also be represented in an enthalpy diagram such ns that shown in Figure 513) Because the combustion of Hh) is exothermic, the enthalpy ofthe products in the reaction is lower than the enthalpy ofthe reactants. The enthalpy of the stem is lower afer the reac tion because energy hasbeen lot i the form of host lensed to the surroundings The reaction of hydrogen with oxygen is highly evothermic (AZT is negative and has © large magnitude), and it cccursrapialy onc it starts Team ocr with explosive violence, to, Ssdemonstrated bythe dissstous explosions of the German airship Hindenburg in 1937 (Pigure 5.144) and the space shut Clullenger in 1988 The following guidelines are helpful when using thermochemical equations and enthalpy dagen 1. Pini ian extensive property. The magnitade of AH, therefore, dirsetly proportional tothe amount of reactant consume in the proces. For the ontbuston of methane io form carbon dicxide and liquid wate, for ext Ple, 890k of heat i produced sehen I mol of CH is uemed in 8 constant pressure system Cig) + 2046) —> COYG) +210] AH = ~s90K) 15:18) Because the combustion of 1 mol of CH, with 2 mal of O; reeases 890M of heat, the combustion of 2 mol of CHy with 4 mol of Op releases fice 38 rich heat, 1780 K). The enthalpy coe fora reaction egal magnitude, but oposite in sign, 10 AH for theese ation. or example if we could reverse Bquation 51850 that CHG) and Os() forme from CO3G) and H,04), AH forthe process woul be 890K CO4g) +2110) — CHG) + 20,6) SH = SOK 15.19 When we reverse a reaction, we revere the rls ofthe products and the Alanis Ara resul the reactant in easton become the products of the reverse reaction, an so forth From Equation 5.16, we can se that revers ing the prodcts and reactants lens to he sme magnitide, Sut a change insign for Aj. This relaonship ls dlagrammed for Equations 5.18 and 519 in Figure Si. 2 The enthalpy change for rection depends om the sate of he reactants ant products the product nthe combustion of methane (Equation 518) were {gaseous HO instead of liquid #0, AP/yy would be ~802 4) instcad of890K]. Less heat would be available for transfer tothe surroundings be- ‘cause the enthalpy of HaO{) is prester than that of H>O(). One way #0 see this sto imagine that the produc sintally quid water The liquid water must be converted to water vapor and the conversion of? mol HOU) 10 2 mo! 104g) isan endothermic process that absorbs 8K 21,00) —211.0@) alt = +884 (520) "Thus, its important to specify the states ofthe reactants and products in thermochemical equation. In addition, we will generally assuine thatthe reactants and products are both af the same temperate, 25°C, unless fotherseindiated, (SAMPLE EXERCISE 5.4 | lating to Quanties of Reactants nd Products ‘ow much est eles when 450 oF methane ga x bared in 3 constant pressure ston” (Use te formation gen in Bguabon 318) sowurion Ana: Oulton than oto na tet re Tou ioe by he myntenwhen {mol Cl Dured ont pane (aie sok “To90 Ths we cn convert mae of Cytol of ene. Fast ower ‘we ast conver gram of Cito moles of Ct, Th, he caneton somes © ‘ans CH (gen) molesCH,-+W anknown be found) Solve: By adding he ston weighs of Cand 4H, we hive mal CH = 160g CH, ‘We'an sue he Sppropratconceson fact conve ams of to mole Gio gout! ‘mate nage ‘hemp it te yon ad 1 te tig im reacrce extn a a ee en ee 2HGA—= 2) + O40) aH = PN) Cale the als ag whan 510 go HO, decomposes a cnstnt presure ‘annven “iat ve = 40 ca: In many situations it s valuable to know the enthalpy change associated with given chemical proces. As we wilseein the following sects, AH can be determined direty by experiment or calculate from the known enthalpy ‘changes of ther reactions by invoking the first aw of thermodynamics. -5_ CALORIMETRY. “Thevalueof AI canbe determined experimentally by measuring the heat foe accompanying a reaction at constant pressure. Typically, we ean determine he magnitude ofthe heat Dow by measuring the magnitude ofthe temperature ‘change the hat flow produces. The measurement of heat flow is calorimetry ‘device used to maasire heat lw ew ealosimeter Heat Capacity and Specific Heat “The more heat an obact gains, the hoter it ges All substances change temper- ature when they ae hested, but the magnitude ofthe temperature change produced by given quantity of heat varies from substance to substance. 55 Calorimetry vw180 CHAPTER 5 Thermochemistry Agere USING ENTHALPY AS A GUIDE £ you hod brick in thea ade gt wl al 6 he fore of gravity pula toward Eat A process that ‘emeadynsncaly favored fo happen, sich ar falling bck scaled a spontncns proces. Asponansous procs fan Be ether fet oto Spd ena the sae sh ero Anais. ‘Many chemic proces ae themodynamically fa wore 9F spontaneods, to. By "spontaneous we Ao nat ‘pean tht he acon Wl orm product Wino any inter ‘eon. That cane he es, ut often some egy mst be Unpartedt ete procs tare The ey change 2 ‘tion pc one ination a ower heaton ke Iyte be spontancus The combustion of Hg) and Ox) fot ‘kample rs gh cantor pence: Thy) = $049) —- HO) AH Hyogo gs andonygen gs can exist together na 0 tune define without notable ection ecg ost igure 3.133} Once init Poeever, ery Is pip lected om he ster he encanto the suraund ing Ae he mace, Taope amounts of a ee letsed, which grey sneeses the temperature of tbe ‘scan and the pots Thesystom then ose enilpy by ‘tanafering the at oth surrounding Real hat he ist low of thermodynamics snicats Ut he total nergy of Use spam ine sorandngs Wl ot cane ee 20K) Entalpy change isnot the only consideration inthe spontaneity facts, however, ors sat pie orexampie the malting afi san endothermic poco 09 — 00 AH = +6015) Even though his process endo ts spontangous at temperate ove te enn point of wate {°C}. The ‘ore procs, he feng of Water os pono at lemperstue teow OC. Thus, welow duce at room ee erate wl ale and tht water potinto fre t= 20°C WL tin ice. Bo of tee process ae spontaneous Under diferent condition even theagh thy athe eves of tne anther In Chap 19 we wl addres he sponta of frosect mon filly We wills why a proce nb rou atone temperature but ata anothe ais the cs fot Beconrenion water tice Devpl these complicating fc however, you should payattenton othe ehuipy anges erections Aaa gener SVoberston, when the ely changes ag, ithe omirant fats in determing spontanety Ths, teactons for whch AP loge and tte tend fo be pontoons Reaction for which AH is rg’ and poste wend be spond erat only he rene diction The eiblpy ofa macs ‘ante estimate ns numberof ways rom tse ext, Uelieiood ofthe ecto being ermadynamilly foe hlecan be predicted Felted Eee 545,546 ‘The temperature change experienced by an object when it absorbs a certain amount of heat is determined by ts heat capalty, C. The eat capacity ofan ‘objet isthe atnount of heat sequied to aise ia temperature by 1K (or 1°), “The greater the heat capacity, the greater the heat required to produce a gives Increase in lemperature For pore sobtances the heat capacity is usally given for a specified amount of the substance. The heat capacity of one mole of @ substances {alle is molar heat capacity, Cy TAs heat capacity of ene gram of a substance is called its spec hat eapaciy, or merely Hs specific heat (Figure 516-4 ‘The specific hea, C,of a substance canbe determined experimentally by mes suring the temperature change, AP, that 3 ows mas, m, ofthe substance ‘undergoes when gains of loses specific quantity of het + 4354) ‘thea Figure 5.16 Space neat ot water. Spec beat reas the sound (quantity of het wansferred) See sot mnie nea 3 Speciichest ~ Grams of substance) (lempertare ang {i k¢er "peer cn vary 4 Sight with temperate ote rece c (21) ‘enunnerss he tempera war ‘pectic The specie Meat o 100 a Tete etn me sats of 4ieejofheata gol igs wae at ‘tempers asthe sempre oiss'e Ths amourtat ergy (rare caer eal 188) G For example, 208 Js required to increas the temperature of 50.0 g of water by {100K Thus, the specifi heat af waters 209) 1s Boog YER ‘A temperature change in Kelving Is equal in magnitude tothe temperature ‘change in degress Celsius: AT in K AT im C2 (Section 7) Wham the55. Calorimetry 181 Elements Compounds Speafc Hea Specific Heat Submance eK) Suberance ie Ne 104 aie) 090 Feo) oss Hx oa 2 sample gains het (positive) the temperature of the sample incesss (postive AT) Reareanging Equation 9.21, 6 get a= Gxmx ar [52 Thus, we ean caleulte the quantity of heat that substance has gine or lost by using ite specific hea together with is messured mass ad temperature change "The spectc heats of several substances ae Usted ia Table #24, Nice hal the specific heat of liquid seater is higher than those of the other substances listed. For example itis about five times a great as tha of aluminum meta ‘Thehigh specific heat of water ales Earth scimate because it makes the te peratures of the oceans atively resistant to change Italo very myporant in Thalntaining a constant tempersture In our bodies, as we will ices lo the ‘Chemistry and Lite” box ater inthis chapter. ‘Which ubsanc in Table. ll undergo the geste emperaur change when he ae mas ofeach sistance absorbs the sans anya Ra” sae anos 5 enna empire any ay Prone eet espe erteet ear rien eee erage ste sme Seay deer orn gu tun mr nmi roi Soles bee ents entire ea ee ae ea oe st uarke Tatas eon ren mt ote oy it ig nin i eo em ec eee ewer eee eee (4) Th water undergo temperatirechange of ar = 980 = 22°C = 76°C = 76K ing Equation 522, wehave a= Gxmx ar = (618) /g 41250176) = 79 14) (2) the mola eat eapacty the heat capac of one mole tt sabstance Using stoic wight of ysrogen an aypen we have 1 mal 0 ~ 18058,0 rom the spect "noe (nga) mn) wm meacrice xen COL ar tn neh fh ee at pcb a ta 2 i Ruse tytn ihe wb ba toned noah) HO ©) hhacapame Ags ‘would dee rch undergo ey ersaed 450 Aa ea ‘ers a) 88% 10,0) 11K decrease ~ 11°C ders enn part a, weave « T32y/molk182 CHAPTER 5 Thermochemistry _Themometr Constant-Pressure Calorimetry “The techniques and equipment employed in calorimetry depend on the nature ‘of the processing saded, For many reactions, sich those occuring i 0° |_-Glam ater Fusion its easy to contol pressure so that is measured direc (Rocll that AH ~ 99) Altwough the clloiasers used for highly accurate work are prec Cork topper ‘on instruments very simple “coffee cup" calorimeter, a shown in Figure S174 is often used in general chemistry labs t0 illustrate the principes of ‘lorimety Because theclornter snot saled, the reaction occurs unde the “ssn constant pressure a the stmosphere Tnthis ease there Is no physial boundary benceen the system and the sur rowndings. The reactants sh prot of he reaction are he sytem, and the ‘waterin which they solve as well asthe calorimeter are part he surround Ings I we assume thatthe calorimeter perfectly prevents the gah oles of 4 Inst from the olin, the heat gine bythe solution must be Proce rom “Stwosiymicam® —__thechemieal ection understudy. In ther word, the hext produced by there capac io, dae ently absorbed by the solution itdoes nt expe the clone fone contsning, fer qe lc asnume thatthe calorimeter self doesnot absorb heat In the case reicansinsolaton ofthe effec calorimeter, this a reasonable approximation because the ‘a figure 517 coffees “alormetcr hss a very low thermal eandaesvity and! hest capacity) For 3 Ctarimeter Tarsimpiepparnunie_ exothermicreaction, heats “ost” by th reaction and "gained" bythe solution, Sediomese estaccomparying” So the temperature ofthe soliton res. The opposite cours for an endothermic ‘reson a consant presse reaction. The heat gained by the solution, fy therefore equal in magnitude today Butoppestieinsign fig ~ ~fay-The value of ats eal calculated from the mass ofthe solutions spetic heat and the temperate change ‘dain ~ (specific hea of solution) x (gram af salution) X AT dan [5231 For dilute aqueous solutions the specie eat ofthe solution will be approxi- imately the same as that of water, £18 /6°K ‘Equation 323 makes Wt posable to calculate gag from the temperature change ofthe solution in which the reaction occur A temperature increase (AT > 0} meang the reaction is exothermic (ay < 0. (a) Howarth energy changes ofa system and i stodgy mated?) How = {he heat gained oF lost Bf system mated tO the eat gained oF lost Bye I SAMPLE EXERCISE 5.6 | Measuring 4H Using a Coffe-Cup Calorimeter When a student miss 50 ml of 1.9 M HC) and mo 1.1. NaOH in coffe-up cslornetes the empernta of the resultant sem 10% in 3 Col he tp cag i natn nM nel ag ate {tlie oes oly a nelgbeguanty of het tate tl volme ofthe solution 10) ml, tha te ena © LO ga Sedaris opecicheat Be “Analye: Nisin solution of land NaOH ress in an ad-bae econ: Ka) + NaOH) —> HLOX) + NaC) Weneed to clelat the heat produced pet mole of HC given the lemperatur ines ofthe soto, the numberof mae of 1HCTnd NSOH ele) an te deny snd spose hc othe nate Plan: The otal heat produced can be aeulated using Equation 523. The numberof mols of HC consumed in the reaction ‘lt elle rm he volume and mola of us suontance, and hs sun th edt detrmane eet progr perme! HC55. Calorimetry 183 Because theta volume of he solutions 100m, smassis (100 mIN0 g/mL) = 00g lng Equation 2, weave doa 7G mx AT 4.18 10 163K) Because the proses cc a onset press, ‘To capone he ethlpy change on 2 mola a we se the it rte aber flea HL en bythe product ofthe Solution volumes (bmi ~ 50%) and onceneatars (101M = 1D mol (0050 Lt 0mol/) = 0050 mel ‘hus thecrhapy change per moleaf MCLs AH = -27 4y.H0 mat = -5: Ayo ‘Check snegaive(xothora) which expe forthe reaction of an aid witha Base and evidenced by the ft that he ‘ec each ees of hatin rene The aa agate beat pc se tab mt PRACTICE EXERCISE ‘When SO miof0.100 AgNO, nd 50.0 of 0.100 M,C are mien constant. pressure clormeeythetmpeate fhe ‘mnt incase om 230°C to 2411 The teaperaare nr cused by the fowig ecto ARNO,ag) + Cay) —> ACI) + HNO) Clelte afr thie ection in y/o AgNO, assaming hat the combine wolton hata mace 1900 ganda specfichest of Lasig'e ‘Anser: ~6400 Jmol ~ 68) Bomb Calorimetry (Constant-Volume Calorimetry) (One ofthe mot important types of reactions studied using calorimetry is com ‘ustion in which a compound (esually an organic compound) reacts completly With excess oxygen. (Section 52) Combustion wactions are most conve relly studied ing a bomb calorimeter, 4 device shown schemasealy in Figure 5.18», The substance tobe studied spaced ina small cup within sealed ‘vessel called elon. The bomb, which s designed to wilhsland high pressures, tras an il valve fr adding oxygen and clerical contacts to initiate the come ntact bustin. After the samp has bse placed Inthe bomb, the bon sealed end oe ‘pressurized with oxygen. leis hen placed i he calorimeter which essentially 7 fn insulated contaney, and covered with an accurately measured quantity of ‘water When all the components within the calorineter have come tothe sme Pom eation ‘ramen temperature, the combustion reaction i inated by passing an electrical carent Fine wise thane meta bn cortac with he ssl: When te becomes a Susy how tc spl ten: = Tat vekasd when combust ecu. Ths het sabe by the ad calorimeter costens, causing a se nthe temperature of the water The temp tate of the water very carly measured before reaction and then afer reaction when the contents of the calorimeter have again aved a COMMON A igure 518 samb calorimeter temperate ‘Tisdevce awed tomennse teat "To cleat the heat of combustion from the measured temperature ines ¥comparying cerbuion ean at inthe bom calorimeter we must Know the tal Rest capac ofthe calometr, Tart voune Car This quantity determined by combusting a sample tat releases» Krone «quantity of eat and measuring the resulting temperature change, For eae, thecombuston of exaely 1 go benzoie aid, CH,COOH, na bomb calorinetet ‘produces 25:38 kof het. Suppo 1:00 of bexvoic aid is combusted 8 lormete, and ineesses the temperature by 4857 °C The feat pact ofthe Clorneter i then given by Cat = 2636K)/4857°C ~ S431 WIC. Once we Know the vac of Cay we can mesure temperature changes produced by other recon and from thse we ean calculate the heat evolved in he react a = Coa % AT [241BL CHAPTER 5 Thermochemistry (SAMPLE EXERCISE 5.7 | Measuring dn Using 3 Bomb Calorimeter Metnylhydcazin (ENs) used aso Iisidvoket fe. The combuton of metylhydazine with nygen produces Nl) Cg and Ou 2CHANM) + 8OAg) — 2NAs) + 2046) + 61,000, ‘When 40g of metylydzaines coms na bomb caloctes he neat ofthe noite fom 250°C Dos hemo’ epenn heen copy of he caren icked be SUBULIPE Cee abet tae Sintort conbcaion fmol CHGN souurion “Analyze: Woe ven s tempertarechange nd the total hat capac of he calornetar We areas ven the amount ec (ant combusted Our goa eto cals then change per mae for combustion ofthe eacane Plan: ew st calelate the het evolved for the combustion of the 4.00-g sample, We wil he caver his het oa mae sant Solve: For combustion of the $006 simple of ‘pat hyrarine, te temperate change thecaionmetr= AT = 380°C — 250°C) = 1450°C calle te heat of ection (equation 523)" gay = Co % AT = ~(7794K/CMLASOC) = -11906) eee eye eae thesia (et) x (SESE) «rari ‘Check The uns ancl proper and thesgn of he answer i negative a it should be fran exten ction, sm PRACTICE EXERCISE AOStHS sample of act cd (HCHO) is ured in a costa whowe hea capacity is 48121". The tenet i ‘een in 1 10 Cf 2655 Cae the evo combustion once ai ap eam snd) per le ‘Smart =i52 xg (8) 10K) 0) Because the reactions in a bomb calorimeter are carted out under COxkg) 12400) + 2H) aH — BOK “Thenet equation is CHAlg) + 204) —> COs) + 24400) AH = 890K) “Tobtain the net equation, the sum ofthe eatants othe two equation i placed “mone sie of the arrow and the sum of the prods on the other ide, Because 502k 2H,0() occurs an bot sides, ean be cancaled Uke an alggbrale quant that appears on both sides of am equal sige. Figure 5.204 compares the 0 te rescton withthe dist one, feos +2110 | “Yee lesan tha farce & cit seri of lps, BH or the any ral! ction sl egal the sm of the enh hag for the nda tos r ‘Theoverall enthalpy change forthe process is independent ofthe numberof steps Daa ‘orthe panicle nature ofthe path by which te resction i aried out This pein ‘ple za consequence ofthe fact that enthalpy ia tate function and FT iter ‘A figure 5:20 An enthalpy dagram fore independent ofthe path betiven the tal and ial tate: We ca therefore comparing one step and etme 2p calculate AH for any process 3s lng as we finda route for which AH is known frome frapactl, The ene/” Groachaep. Tomcat eal sal bet of experimental mets cH 2050) henge the dctracson on OC nents can be used to culate AH for avast number of diffrent veacions ‘gh Th Siforhe ower eaten Hess's lw provides 2 wsefll means of calculating energy changes that are Chuisthesumaltbe Sivas forthe dificult to measur dirs. Fr intanc, ti impossibe fo measute acy the ‘wo tps show ‘enthalpy forthe combustion of carbon o form catoon monoxide, Combustion of Vmat of carbon with 0.5 mol of O> produces both CO and CO>, leaving some ‘carbon unread. However, solid cavbon and carbon monoride an both be cet pletely burned in 0; to produce COp We ean use the enthalpy changes ofthese fescton to calculate the heat of combustion of C to CO, ax shown in Sample Evers 38 ‘What ts do the folowing changes ave on AH or a racon a) evening ac ‘on, mulplyng coetcentsby 2? Im SAMPLE EXERCISE 5.8 | Using Hess's Law to Calulate AM The enthalpy of renton for the combustion of € to CO, ~2935 ble C and the nthaps Tr tho combustion of CO to CO, is 2550 CO: 0 Cis) Ox) —> COM) 814 = 395) @ 0) + 40%) —+ COW) He ~ -250.03) Ung how dats, caluteth enthalpy forthe cmbuston of 10 CO: o C49 +F0x8) —+ CO) Hs souution “Analyze Weare ven neo thermochemical susan a goal in combine ‘Seatauchawoy arose thd equnion andy change. Plan We wil se Hess aw In doing so we st ae Ue numberof moles > Fancr among hs ractaner sna produc neh tage equation) Wether sn ‘Stanton () and) get same nb of oe of se saan So {hat hen the aula equations ae added, ve stan te np equnton. AF anne, we exp tata the cndupy changes which wea56 HewsLaw 187 fake to Gyan (nl peng en emt {nd Col sorte product de othe er, a in eure acon exon ‘Sauce egaton (if har Cl) a 2 macaw can ‘et cunon sta ‘ened a turn equaton sound, however co that COQ) product Remember ‘wo equating tht the eam be added giveth dested equations + Ox6) — Cox) 3H = 9854 Ox) —+ COM + FOxs) At = 25505) a+ 0%) — cow ‘i, = 11055) {when we add the two equations, COs) appears on bth sides ofthe row and oot anedhour ktwan Jp einta am nchase ‘Comment: Is somite ssc tthe etpy change 2 fave dane hae to keep ack fhe associate eee the cere atone and Carbon occurs n ho forms raphe and diamond. The enthalpy ofthe combustion ‘fgets 2955 3) mol and haa sismond s 99841) Clerapite) + 044) —+ COM) 844 = 855%) Cldamond) + Of@) —+ COs) AM, = 1854 Calculate AH forthe conversion of graphite to damon grape) > Cimon) AH =? Answer: Hy = 119) I SAMPLE EXERCISE 5.9 | Using Thre Equation with He's Law to Galedate (Cabelas AH forthe rection 2C6) + 1h) —- Cath) en the flowing chemical equtions and their spective enthalpy changes Catldg) +404) — 2004) + HOM) 8H = 12964) ‘Co) + 048) — cOxs) SH = 3954) ig) + $0.6) — HO = 25588) “Analyze Wo ae ven choi equation and aed tcalelte RIT wing the ‘acl equation and thew esosted aly anges ms Px ri vs nny ec to eae eee arene Ee Stent ota! Athecane ine wo hang tak ee BA veoa ee SS ee maieromeeenen aca ee Suey irae mepemi nate a eee ee tin has Hye Fencan we beep the Nid equation a itis We hen add the ee pn inert ear 2COdg) + 1H08) —- Cattsg) + 204) 2C6) + 20:6) — 2COx) Hale) + 4046) — 00) 2CU) + Hi —> Gg aH BEB When te equations ae added, thee ae 2COy £0 nd HO om both ids of he ‘Sow These aw enced in wing th et aon,188 CHAPTER 5 Cig Ow co) Ethalpy ——> ‘a Figare 5.21 mental ‘stating West ne fate unto teeny “Thermochemistry sank = 28,00) Sarno conn change fr ‘ecombustin of mala Indepenet el wheter be reacton ‘Ske paein one ore sp Bi ar [Rass Ine du jou should go back over the nus uanipelatons ofthe AF ‘leo emt it you did ot ke ap avert ee wih ge fm PRACTICE EXERCISE Caleta forthe cto Noy) + 0 — Noxe) ven the following information NO) + O¥s) —> NOM) + 0X8) aH = 19894) 048) > 3036) AH = 1034) 04s) — 208) AH 4508) Answer: ~90418) “Theay point of thse examples is that Hla state function, so ora priulr set of rats ed products, AH he sre ether thereto tales place one Sey arin a seis of steps. For example, consider the reaction af mothane (CH) “and oxygen (03) lo form CO; and HO. We can envision the reaction forming CO, aitetly of with the intl formation of CO, hich is then combusted to CO, These to pats are compared in Figure 521. Bacause Hs a sate fancsion, both paths must produce the same value of AHL In the enthalpy siogram, that means Athy =" Alls Aly 5.7 ENTHALPIES OF FORMATION By using the methods we have just disease, we ean calculate the enthalpy changes fora great many reactions from fabulsted AH values, Many expert ‘menal data are tabulated according othe type of process. For example ext ‘ve ables exis of eal of epriaatne (AH for converting igus 0 ess), ntapics of fasion (AH for melting solids), enthalpic combuston (AH for com ‘busting a substance in oxygen, an so forth, A particularly important process tse foe abating thermochemical data is the formation of compound from is consutuent elements, The enthalpy change ssociated with ths process is called the enthalpy of formation (or hat of formation) and i labeled AH, ‘where the subscript indicates tat the substance has ben ome fom ts com ‘ponent elements "The magnitude of any enthalpy change éepends on the conditions of temperature, pressure, and state (gas liguld o slid crystalline form) of the reactants and products. To compare the enthalpies of diferent reactions, we ‘must define a set of conditions calle a stoned state at which most enthalpies fre tabulated. The slandard state of a substance isis pure form atalino ‘spheric pressure (1 atm; om Section 102) and the temperature of intrest, ‘hich we usually choose to be 298K (25 °C)" The standard enthalpy change ‘fa reaction is defined asthe enthalpy change when al reactants ane products sre in their standard states We denote a standard enthalpy change a= AI", ‘where the superscript Indicates standandsate conditions ‘erp nt se a hr a th a frat par eng sary dione i cng“Thestandard enthalpy of formation of «compound, AF, the changein ‘enthalpy forthe reaction that forms one mole of the campotind from ies le ments, with al/sbstances in hee standard states ements (in standard states) —> compound (in standard state) AH ‘We usually report AH} values at 298 K. [fan element exists in move than one focm unde standard conditions, the most sable frm of eh element fauslly used for the formation reaction. For example, the standard enthalpy of forma Hon for ethanol, CzHOH, the enthalpy change forthe following eeacton 2clompi = 3889 +404) — CHLOE a8) -wr7 Ky (825) “The elemental source of oxygen s ot O or Oy because Oris the stable form ‘oF oxygen at 298 K nd standard atmorpheriepresvure. Similarly, the element Source of carbon i graphite and not diamond, because graphite more stable (lower enargy) at 298 K and standard atmospheric pressure (see Practice Fxee= se 3.8). Likewis the most stable form o hydrogen under standard conditions| Is FG), s0 this used a he source of hydrogen in Equation 325, “The stoichiometry of formation arson always indicates that one mole of ‘the desired substance is produced as in Equation 525. As a result enthalpies fof formation ave reported in kml of the substance being formed, Several ‘Standard enthalpies of formation ae given in Table53¥-A more complet table Is provided in Appendix By defo, the sondard enthaly of formtion ofthe mot sae form of any lemnt zr bec there no formation rection needed when the element Is already ints standard sate. Ths, the values of A} for Cigraphite) 2), (Oxi) and the standard states of othe elements ae zero by deiniton 1p able 3, the standard enthalpy of font of CH sed a 2267) Wote the thermochemical equation asiacate wih i otis substance, Substance Formula __AN/(i/n Substance ‘Acetylene ihe) 87 Hydrogen hide ‘Armonia NIN) 6.19 Hydzope oie Benzene cau 30 Hydrogen ode Caleumeattonte — C2CO45)—~12071 Methane Cainmonde CaO) 85 Methanol Carbonionde COG) -935 Propane Carbon monoxide COK) =a108 iver horde Damend co 1 Sodium carton thane cattle) aus Sodio carton ao! HoH -277 Sodium conde nylene Cathie) S30 Sucrose Ghctee Cettrouey 1279 ter ydeopen bromide HBAs) 3628 ater vapor 5.7 Enthalpies of Formation Hay) HR) Hig) crip ccryoHt Cathie) Acs) NaiCoys) NacOs) Nace) CaltsOn9 100) Ho@ peas) 29 a0 10348 a7) «109 20 189190 CHAPTER 5 “Thermochemistry Im SAMPLE EXERCISE 5.10 | identyng Equations Associated with Enthalpies of Formation Foxyhih te lowing maa 25% wl heen cans pe Ibiteltanequifen whos Bf anenfalpy otfematent (a) 2Na() + 404g) — NaO6 2K + Cg) — 2x) 10 CaO) ~~ seldom +484) +3049 soution tna The andar ena raton eget econ awh ee re ace eee ee ree as pound We ed oi ch etn n nei nates th man Slate tl cheeclt ened et Sonne Neve edo uaa nurattian asians arisen Sete in) Lek Ne me i i eon ane ng nt pe ot od Ne andy napcte Teno cay ange ree cacy tents ie) pauline tt sts gi Wha Be aged wo sd om. Seeindapy neem ertin oie be nid estoy ESSN RAD Suns Reidel ec yy + Feu — xa action (0 et orm ince tom fs demented ce dncepeSlaciaore smn tat ert Neer Be cs ‘Gpecie and an posure TH etn Dat sone presen he enay ee ee él + 6184) + 3048) — C3049 sm rnacrce xanctt Wit th ean coespndng othe sn end oman of i Sete es eee Te eporad SS — ceun Using Enthalpies of Formation to Calculate Enthalpies of Reaction Tabulations of Af, such as those in Table 5.3 and Appendix C, have many Important uses As we wllscein this section, wean ust Hess's Taw to calculate the staudard enthalpy change for any reaction for which we know the AH) values forall reactants nd products For example, conser the combustion of Propane is, (6), wih gen to oem COX ad HO) under sadaed HAG) + 5 0x) —- 8COY) = 41,00 We can vite this equations the sum of thre formation reactions Gul) — 3CW9) + 41S) A= -ANCSHg] (526), 3CIs) + 3O44e) —+ 3COYG) Ait = SAHFICOM)) (27) 414) + 20:4) — 41.00 Hy = 4A7778,000) 1525) GGT 50:q —> 3CO@ = FOAM SAT ARS AR, 1525] From Hess awe we can write the standard enthalpy change forthe overall action, Equation 525, asthe sum af the enthalpy changes forthe processes Is57 Enthalpiesof Formation — 191 Equations 526 through 5.28, We can then use values fom Table 5.3 to compute | numerial vale for fr the overall reaction Alig = AU) + At + Ay ~AHTICSHylp)] + 38H FICO) + 4822700091 1530) = =-1038 kp + 34-3985) + (288.8) = 221995 Several aspects ofthis cleulation depend on the guidelines we discussed in Seton 54 1. Equation 5.25 isthe reverse of the formation section for C34), 0 the ‘enthalpy change fr this reaction is ~ AIT ICH 2. Bguation 527 the formation rton for 3 mal of COx() Because enthalpy isan extenive propery the enthalpy change for this sep is 24 7(COsG)] Similarly, he enthalpy change for Eauation 5.28 4 17/H20(0], There. tian species that 11,00), was produced, so be careful to use the value of SH} for H50(), not #508. 5. We assume thatthe stoichiometic coefficients in the balanoed equation represent moles For Equation 5.25, thereor, the value li 3 change for the reaction of 1 mol C3Hy and 3 mol Oy ‘presents the ental San0 i tovorn mol COp and & mol HO. The pdt ofthe numberof mole and the enthalpy change in kJ/mol has the units KJ. (numberof moles) x (Gin bjjenol) ~ A). We therefore report AH Kl Figure 522 presents an enthalpy dia ‘can Be Broken into steps valving formation reactions, im for Bquaton 5.28, showing how it ‘Wiccan break down any reaction into formation reactions a we have done Ine, When we do, we oottn the general result thatthe standard enthalpy change of a reaction is the sun of the standand enthalpies of formation of the Drodzts minus the standard enthalpies formation ofthe reactants Alig = Bnd produets) ~ ZAI Hreactans) (31) ‘The symbol (Sigma) means “the su of” and and m are the stoiclo- retriceneicients the chemical equation. The fist term in uation 5.31 rep resents the formation reactions of the products, which are writen ithe onward” digecton, that elements reacting to form products. This tras analogous to Equations 5.27 and 5:28 in the previous example. The second erm represens the reverse of the ation reactions ofthe esctans, in Equation 525, why the APY values havea mss sign in front of thers, "Gamma £155 | Ooconnntin [Drom LOH 5000) | yy, non {Oramasonstsnho Pay athapy suey “Figure 5.22 An enthalpy agra relating the ntnipy change tora reaction to enthalpies ermine forte combustion of propane at CFD, he reacion sg) 9040) = SES) P so0n. econ age te acon curklg inte sto Foe CBG) ecerpened to Iedement, so ath = MTC Seca 3 m0. xg) se formed a iy ~ 33NTCOMG)) ray, Simos ae ome 0 ahs = AH HOD Hes remote ghenby Egon 537 beens AMOK192 CHAPTER 5 Thermochemistry 1m sari exercise 5.11 | Caetng an nha of Reaction fom rtp of Formation (0 cath snare hanger he comeing fm COA) nd HOD) Co ea ed peated na souvTion Anaya ge a eaton Kmustin oft fem COX) and HOO and sh eat andar cri ss Sif tien rc car eyo Kea rained Oy sana 13 gC wat produ by 18g Gs whose combustion was ented sbovein etext ee Equalors 839 and50) te: We dowels euton ocr ofa We th oko AH; vain Append Coin RES i tpi nn Soc te ly Cane bn ec) Vet lr mo Oa Sag thee ager mht pr gm Wetintary wee polar art Cand hen chang Per ec Serra be cbse Pains tenes een cfereimaes (oe lnow tats combasionmacon aires Oagyars act Tan he aed oton SetheconanimanctinselmalCgie CHAD + BOM) —» 6COM) + 3D Wecan calate for this action by using Epumion Sal end death les Reson yp + SAHA ~ ISAC + 3. Raat Soe din SS Rete hy = 6HACO + SANRLON ~ INNO + # HOD) ‘hernia byt naan Dceete = f(-29854) + 8(-298840] ~ (490) + BOK] ‘efi Reval ls that Alf) = for ay away) Sotto sabe en Under dard ee “Sy Se neers perlite Ble yup: Cb tip =-238)e Uuethe molar muses cower moles torus CH): (-3267 ali mol 781g) = ~A18 Kg onmant:Noanne aber hyroaons Aare. he eer eine fomthecnbustion ofa am oye. mm practice Exercise ‘sg sda espe of oman ted Tale 52a ena change fh combustion of mol of at0119 +5036) — 260x491 +31400) Answer: “13678 ‘SAMPLE EXERCISE 5.12 | Calculating an Emthapy of Formation Using an Enthalpyof Reaction ‘The standard eulpy change forthe ection exc 04s) — C404) + CO¥) 5517514 From he vl forth card enti of oman of CxO) and COM) given inal 53, cline he sta Shdenbaly sieenaton ofCHCO30) ” souurion ‘Analyze: Weed 0 obtain AI} CACO) Plan Wi ogi by sing the expression for the standant hay changer the acon Hin = ISH}CA0) + AHGCOD) ~ ANACACO Solve: nsetng the given AZ and the known HY valves Romie ccApp we have Psi) = 6355) — 38554) ~ AH HCACOS) Sving for 4 (CaCO. gives Hj (CaCO. = ~12071 mel (Ohad Weexpet the ety of fontion af sable sn ouch eam bora kobe egies58 Foodsend Fuels 198 sm PRACTICE EXERCISE ‘Given the fallowing standard enthalpy change, use he standard enthalpies of formation in Table. tcl the standard {hapy of formation of C0 CuO) +44) — Cul) + LOD AHY = 974) Aner: 1961 Kd 5.8 FOODS AND FUELS ‘Most chemical reactions used for dhe production of heat ace combustion nec ion. The energy elessed when one gram of a materia is combusted often ‘alle it fuel value. Although fuel var represent the est reseed in a com bustin reaction, fuel values are reported as postive numbers, The uel vals of any food or fel can be measured by elorimetry Foods Most ofthe energy our bodies ned comes fom carbohydrates and fats The {ors of carbohydrate known as starch are decomposed in the intestines into _lucose, CHO, Glace soluble in blood, and inthe human body i Known as blood Sugat. Is transported by the blood to cells where it reacts with Oz ina series of steps, eventually producing COxG), H0(0), and enerpy CHO) + 60x49) —> 6CORG) + HOM AH” = ~2600 4) “Thebreskdawm of carbohydrates is api, so their energy is quickly supplied to the body However, the body stores only 2 very small amount of carbohydrates, ‘The average fuel value ofcarbolyrates is 17 Kg (4 Kal) [ike carbohydrates, fats produce COz and H:O when metabolized and wien subjected 1 combustion ina bomb calorimete.The reaction of tstearn, Cote a type fat, ta follows 2CoHa O46) + 168 O34@) —> 14 COX) + 110,00) iP = 7552041 ‘Thode the cea eng fo ods msnnnbodyempere Pe Selata ae manana a rd os ‘iar tae Anya tuyere ete Povo outed are artapt aap ave hae ee ene Tye mos So ce am ey Ce eee Sanh eter of ev en a en ican eer Eerie smb ne weap seen wo sete 6 kag Tas peeronntesruyreias een nee ssn serine beau epee et oa Seaea ah mie me eee ater Ne antsy ‘Ber cds ap may vere CO. Proceso oy rach bila mace wpe ate ss Roe ae end Bem on atc antan ertae staan pe ie, tetane sete Reh hae ey of commen satin TleSA0 eet aheminereree norte iad tGnctoaed ian regen malar emo of gy wasty tetera iat) Meemcuntetteagy ss eae ets Ein reaping nhac an eet and mie IE ol na Lloret wag ai snes ee eee re eee pert expends shout ROD K/h when doing light work, such as sor AIQWG 3.23 abl of proceed fonds Saigo ah pry Stench orang en we rpm eatin, es SOR eee hrenacincerkereciocenarshcr Sammtamemneaase ater Eiamunoupwecpeniaataysasenponie” mocuratee194 CHAPTER 5 Thermochemistry ‘Appronimate Compost Fae Valve cabohydete Fa We Keli Cae) Caibahydae 100 = = v 4 tse “ Mo = 5 Apne 8 ashe 25 se ter 12 “ 03 tea hese 4 a) 2» a fee @ 0 @ eo ut age " " 2 8 a4 Hamburger a oo 8 Xe Mik¢wnoi) 50 4033 30 Om ‘Which alesis he pete aunt of ener pr gra pon metabolism, aby ins, potas orf? I SAMPLE EXERCISE 5.13 | Comparing Fuel Valves ‘Aan such ag calery contains carbo ats in the form of statch and coulse, ‘hice Linde of cobalydencs have cally Wess fol Yloca when a ‘usted ina bomb clormsier When we consume celery, however tu bos fe ‘ive fel vale Em the atch nl: What ea we corde sb! iiss etwson stich and clone a 0? seustion Hecln dc sot prt ul lc oe pat cmd att ot ore Science ath AR ete eee ee ee une ave eo meen pa aa er canie re eae eas | Sung iva ws belor sping a fe fat belpevsroeaod val im PRACTICE EXERCISE ‘The ntiiona eons bate of canola ol inate tht 10 ofthe oi hea eee sy vaio kel Aiur elon» bt pancake sup inde that 8 boat ass cn ae 30 eat Ae haere ‘Arower Theo hos aM vai of We heal whereas thes) has a fel vale ‘about 33 ea The higher onl vat forte cana rac cae the ‘Senay pure a when te srupnasolton of agar coors i wae ‘Theo havlahighes lve pes rane nadaton they ete by wane fm SAMPLE EXERCISE 5.14 | Estimating the Fuel Value ofa Food from ts Compostion ()A25 (1-2) serving ofa popular bake oa aved with 120 im proved gin gcaroyaaes and a Uang om serag foton ot ese Rave mboc etic cg tes nie cre a {Gy Aperonof average weight uses abou) Cal/ov when rang or oggng Hos anor Baal pve es crergy voce rpms ae ete? souution () Analyze: The eng value fhe serving wil be the sum of he energy values of theprwensearbohydaes and at