‘Spontaneous chemical reactions 7A. The Gibbs energy minimum 7.2 The description of equilibrium ‘The response of equilibria to the conditions 7.9 How equilibria respond to pressure 74 The response of equilibria to temperature 7A Impact on engineering: The extraction of metals from their oxides Equilibrium electrochemistry 7.8 Hall-zeactions and electrodes 78 Varieties of ells 7.7 The electromotive force 7.8 Standard potentials 79 Applications of standard potentials 172 Impact on biochemistry Energy conversion in biological cals (Checklist of key ideas Further reading Discussion questions Bxarcisos Problems Chemical equilibrium This chapter develops the concept of cherrical potential and shows how itis used 10 ‘account for the equilibrium composition of chercal reactions, The equioium composiion| corresponds to &minimurn in the Gibbs energy potted against the extent of reaction, and by locating this minimum we establish the relation between the equilbrizn constant and the stenderd Gibbs energy of reaction. The thermedynemic formultion of equiium trables us to establish the quantitative effects of changes in the conditions. The principles of thermodynamics estebished in the preceding chapters can be applied to the descrip tion of the thermodynemic properties of reactions thal take place in electrocherical Cel, in which, es the reaction proceeds, it dives electrons through an exteral circu ‘Thamodynamic arguments can be used to derive an expression forthe electric potential of ‘such Cals anc the potential can be rotated to their composition, There are two mejor topics {develepedin this comection. One i the defriton and tebultion of stander poten; the second isthe use of these standard potentials to precict the equilorium constants and ther thermodynamic properties of chernical reactions. (Chemical reactions tend to move towards « dynamic equilibrium in which both reac- tants and products are present but have no further tendency to undergo net change. Jn some eases the concentration of products in the equilibrium mixture is so much greater than that of the unchanged reactants that for all practical purposes the reac- tion is ‘complete’, However, in many important cases the equilibrium mixture has significant concentrations of both reactants and products. In this chapter we see how to use thermodynamics to predict the equilibrium composition under any reaction conditions. Because many reactions of ions involve the transfer of electrons, they can be studied (and utilized) by allowing them to take place in an electrochemical cell. ‘Measurements like those described in this chapter provide data thet are very useful for discussing the characteristics of electrolyte solutions and of ionic equilibria in solution Spontaneous chemical reactions ‘We have scen that the direction of spontaneous change at constant temperature and pressure is towards lower valu of the Gibbs energy, G. The idea is entirely general, and inthis chapter we apply it to the discussion of chemical reactions. 7.1 The Gibbs energy minimum. ‘Welocate the equilibrium composition ofa reaction mixture by calculating the Gibbs ‘energy of the reaction mixture and identifying the composition that comesponds to ‘minimum G.7.1 THE GIBBS ENERGY MINIMUM 201 (2) The reaction Gibbs enersy Consider the equilibrium A = B. Even though this reaction looks trivia, there are ‘many examples fit, such as the isomerization of pentane to 2-methylbutane and the conversion of t-alanine to p-alanine. Suppose an infinitesimal amount d& of A turns into B, then the changeiin the amount of A present isdn, =—d8 and the change in the amount of B present is dri, = +a, The quantity & (xi is called the extent of reaction; it has the dimensions of amount of substance and is reported in moles. When the extent of reaction changes by @ finite amount AE, the amount of A present changes from rag to Myo A and the amount of B changes from tay 0 Myo + AE. So if initially 20 mol A is present and we wait until Ag = +1.5 mol, then the amount of A remaining will be0.5 mol, “The reaction Gibbs energy, A,G, is defined asthe slope ofthe graph of the Gibbs «energy plotted against the extent of reaction: re) mu pears ml Although A normally signi a difference in values here A, sighs a derivative, the slope of G with respect to & However, tose that there is a close relationship with the normal usage, suppose the reaction advances by 4. The corresponding change in Gis energy is AG = peg + Hyd = —HyE + Hyd B= Hy — Hyd “This equation can be reorganize (=) aa TE}, tees Thats, AG= by (72) We sce that 4,G can also be interpreted a8 the diference between the chemical potentials (dhe partial molar Gibbs energies) ofthe rectantsand products a the con- Postion ofthe reaton mixture. ‘Beem chemical potential vis wth composition, the slope ofthe pl of Gibbs ‘nergy against extent of reaction changes asthe reaction proceeds. Moreover, because the reaction runsin the direction of decreasing G (thats, down the lope of G potted aginst), we se from eqn 7.2 thet the rection A ~> Bis spontaneous when > Hy ‘whereas the reverse reaction is spontaneows when fl > fi. The slope i ero, and the reaction is spontancous in neither direction, when AG=0 73) This condition occurs when fly =H, (Fig. 7.1) It follows that, if we can find the ‘composition of the reaction mixture that ensures fly fla then we can identify the ‘composition of the reaction mixture at equilibrium. {b) Exergonic and endergonic reactions ‘We ean express the spontaneity ofa reaction at constant temperature and pressure in terms of the reaction Gibbs energy: 1f4,G <0, the forward reaction is spontaneous, If4,G> 0, the reverse reaction is spontaneous. Ifa, 0, the reaction ist equilibrium, Gibbs eneray, G Extent of reaction, xi 14 Asthereaction advances (represented by motion fro let to right along the horizontal axis) the slope ofthe Gibbs energy changes. Equilibria corresponds to 210 dope atthe fot ofthe valley.202 7 CHEMICAL EQUILIBRIUM ° | ° 'he.72 IFtwo weights te coupled as shown here, then the heavier weight will move the lighter weight in ts non-spontancous direction: overall, the proces is still spontancous, The veightsare the analogues of two chemical reactions: reaction witha large negative AG exn force nother reaction with aless AG to run in its ‘non- spontaneous direction, Comment 7-1 Note that in the definition of A,G*, the 2, has its normal meaning 2 a difference whereas in the definition of A,G the A, signifies a derivative. ‘Axeaction for which A,G-<0 is called exergonic (from the Greck words for work pro- ducing). The name signifies thst, because the process spontaneous, itcan be used to drive another process, such as another reaction, or used to do non-expansion work. A simple mechanical analogy is a pair of weights joined by a string (Fig, 7.2): the lighter of the pair of weights will be pulled up asthe heavier weight falls down. Although the lighter weight has a natural tendency to move downward, its coupling to the heavier ‘weight results in it being raised. In biological cells, the oxidation of carbohydrates act asthe heavy weight that drives other reactions forward and results in the formation of proteins from amino acids, muscle contraction, and brain activity. 4 reaction for hich A,G > 0 is called endergonic (signifying work consuming). The reaction can bbemade to occur only by doing work on it, such as electrolysing water to reverse its spontaneous formation reaction. Reactions at equilibrium are spontaneous in neither direction: they are neither exergonic nor endergonic. 72 The description of equilibrium With the background established, we are now ready to see how to apply thermody- ‘namics to the description of chemical equilibrium. (a) Perfect gas equilibria ‘When A and B ave perfect gases we can use eq 5.14 (n= p+ RT In p, with printer preted as pip") to write AG Hy a= (us + RT In py) ~ (RFR In py) =AG°+RTInE® (ay - If we denote the ratio of partial pressures by Q, we obtain 4 =A,G°+RTINQ sy Pa The ratio Qis an example ofa reaction quotient. It ranges from O when py =0 (cor responding pute A) toinginity when p,~0 (corresponding to pure). Thestandard reaction Gibbs energy, 4,G*, i defined (lke the standard reaction enthalpy) asthe difference in the standard molar Gibbs energies ofthe reactants and products. For our reaction NG*=Gin— Cin = HEH 7) In Section 3.6 we sa thatthe dtferencein standard molar Gibbs energies ofthe prod ucts and reactants is equal tothe difference in their standard Gibbs energies of forms- tion, so in practice we calculate A,G* from A.G*= 4,6) -4,6°) 7) At equilibrium A, and eqn 7.5 becomes, = 0. The ratio of partial pressures at equilibrium is denoted K, 24+ RTInK ‘This expression rearranges to RTInK=-A,G° «-(") (78° Pr qin7.2 THE DESCRIPTION OF EQUILIBRIUM 203 ‘This relation is a special case of one of the most important equations in chemical ‘thermodynamics itis the link between tables of thermodynamic data, such as thosein the Data section at the end of this volume, and the chemically important equi constant, K. Molecular interpretation 7.1 The approach to eqs 1 molecular terms the minimurn inthe Gibbs energy, which corresponds to A,G =6, stems from the Gibbs energy of mixing ofthe two gases. Henes, an important contibution tothe position of chemical equilibrium isthe mixing of the products with the ractantsas the products ae formed. Consider a hypothetical reaction in which A molecules change into B molecules ‘without mingling together. The Gibbs energy ofthe system changes from G%(A) to G°(B) in proportion to the amount of B that had been formed, and the slope of the plot of G against the extent of reaction isa constant and equal to A,G* at all, stages of the reaction (Fig. 73). There is no intermediate minimum ia the graph. However, in fact, the newly produced B molecules do mix with the surviving A fa.73 Ifthemixing of reactants and molecules. We have seen that the contribution of mixing process thechangein Products isigpored, then the Gibbs energy Gibbs energy is given by eqn 5.27 (dpj,G=nRTUXy In y+ In Xy)). Tis expres-__ 0, the equilibrium constant K < 1, ofthe two contributions has a minimum. “Therefore, at equilibrium the partial presurcofAexcecdsthatofB, which meansthat _Thtinimum corsponds tothe the reactant Ais favoured in the equilibrium, When 4,G® <0, the equilibrium con-_“siltoiumcompostin ofthe sytem. stant K> 1, sot equilibrium the partial pressure of B exceeds that of A. Now the prod ‘uct Bis favoured in the equilibrium. Gibbs eneray, 6 Extent of reaction, & (0) The general case ofa reaction ‘Weecan easily extend the argument that led to eq 7.8 to a general reaction Ftst, we need to generalize the concept of extent of reaction Consider the reaction 2.A+ B 3 C-+D. A more sophisticated way of expressing the chemical equation is to write it in the symbolic form 0=3C+D-2A-B8 by subtracting the reactants from both sides (and replacing the arrow by an equals sig). This equation has the form oD 9) 7 where J denotes the substances and the ¥; ate the corresponding stoichiometric ‘numbers in the chemical equation. In our example, these numbers have te values Va="2, Yy=—ls Vo=45, and vp=41. A stoichiometric number is positive for prod: ucts and negative for reactants. Then we define & so tha, iit changes by Ag, then the change in the amount of any species is v6. IMustration 7.1 Kientiyng stoichiometric rumbers ‘To express the equation Na(g) +3 Hag) 92 NH,(g) (7.10)204 7 CHEMICAL EQUILIBRIUM, in the notation of eqn 7.9, we rearrange it to O=2NHG(g) Nya) +3 HG) and then identify the stoichiometric numbers as Vy, ‘ ‘Therefore, if initially there is 10 mol N, present, then when the extent of reetion changes from €=0 to = 1 mol, implying that Ag = +1 mol the amount of Ny ‘changes from 10 mol to 9 mol. All the N has been consumed when When Ag=-+1 mol, theamount of H, changes by 3 x (1 mel) =-3 mol and the ‘amount of NH, changes by +2><(I mol) =42 ml A note on good practice Stoichiometric numbers may be positive or negative; stoichiometric coeficients are always positive. Few, however, make the distinction between the two types of quantity. ‘The reaction Gibbs energy, A,G, is defined in the same way asbefore, eqn 7-1. In the Justification below, we show thatthe Gibbs energy of reaction cen always be written A,G=A,G*+RTINQ ay with te standard reaction Gibbs energy calculated from acr= Dvaor- Dace (7328) a (or, more formally, AG*= PF yA) (7.120) o The reaction quotient, Q, has the form activities of products 7.13) ‘activities of reactants eo with each species raised to the power given by its stoichiometric coefficient. More for- mally, to write the general expression for Q we introduce the symbol TI to denote the product of what follows it (just as Y denotes the sur), and define Q as OTe (7.136) Because reactants hve negative stoichiometric numbers, they automaticaly appear as the denominator when the product is written out explicitly. Recall from Table 5.3 that, for pure solids and liquids, the activity is 1, so such substances make no contri- bution to even though they may appear in the chemical equation lustration 7.2 Ving a reaction quotient Consider the reaction 2A-+3B->C+2D, in which case Vy and v= #2. The reaction quotient is then17.2 THE DESCRIPTION OF EQUILIBRIUM, Justification 7.1. The dependance of tha reaction Giabs energy onthe reaction quotient ‘Consider the reaction with stoichiometric numbers vj, When the reaction advances bby d, the amounts of reactants and products change by dx = yd. The resting infinitesimal change inthe Gibbs energy at constant temperature and pressures a= Sra, = Daas (Somos aay Te fetlows that a6 se-(3),, Dae 3) ‘Tomukefurther progres vente that the chemical potential of species Jisrlated tots activity by eqn 5.25 = 1? + RT In). When this expression i substituted jntoegn 7.15 we obain 46=Dyap+RT Dying, AG*+RTIn [ay A," RTD Ino} 5 =A.GP+RTINQ with Q given by eqn 7.136. Now we conclude the argument based on eqn 7.11. At equilibrium, the slope of G is zero: A,G = 0. The activites then have their equilibrium values and we ean k (114) me trol ‘This expression has the same form as Q, eqn 7.13, but is evaluated using equilibrium activities, From now on, we shall not write the ‘equilibrium’ subscript explicitly, and will rely on the context to make it clear that for K we use equilibrium valuesand for Q ‘we use the values atthe specified stage ofthe rection, ‘An equilibrium constant K expressed in terms of activities (or fugacities) is called a thermodynamic equilibrium constant. Note that, because activities are dimension- less numbers, the thermodynamic equilibrium constant i also dimensionless. Inele- ‘mentary epplications, the activities thet occur in eqn 7.16 are ofien replaced by the ‘numerical values of molalites (that is by replacing aby by", where Y= 1 mol kg"), ‘molar concentrations (that is, as (JJ/c®, where c*= 1 mol dm”), or the numerical values of partial pressures (that by pp, where f°= 1 bar) In such cases the result- {ng expressions are only approximations. The approximation is particularly severe for electrolyte solutions, for in them aetvity coefficients differ from 1 even in very dilute solutions (Section 5.9). ‘Comment 7.2 205 Recall that ala x=In.x“and In.x-+In y Inxy- asa J2067 CHEMICAL EQUILIBRIUM ‘Comment 7.3 In Chapter 17 we shall see thatthe right- hhand side ofeqn 7.17 may be expressed in terms of spectroscopic data for gas- phase species; so this expression also ‘provides link between spectroscopy and equilibrium composition. Mustration 7.3 Whting an equitrium constant “The equilibrium constant for the heterogeneous equilibrium CaCO, (s) =* CaO(s) +CO,(g) is eae (Cable 5.3). Provide the carbon dioxide can be treated as perfect gas, we can go conto write K=Peolf” ‘and conclude thet in this case the equilibrium constant is the numerical value of the decomposition vapour pressure of calcium carbonate. Atthis point we set ,G= RTInK=-4,6° a7) ‘This is an exact and highly important thermodynamic relation, for it enables us to predict the equilibrium constant of any reaction from tables of thermodynamic data, and hence to predict the equilibrium composition ofthe reaction mixture. jn eqn 7.11 and replace Qby K. We immediately obtain Example 7.1 Calculating an equibrium constant Calculate the equilibrium constant forthe ammonia synthesis reaction, eqn 7.10 3t 298 K and show how K is related to the partial pressures of the species at equi- Iibrium when the overall pressure is low enough for the gases to be treated as perfec. Method Calculate the standard reaction Gibbs energy from eqn 7.12 and convert ittothe value ofthe equilibrium constant by using eqn 7.17. The expression forthe ‘equilibrium constant is obtained from eqn 7.16, and because the gases ae taken to bbe perfect, we replace each activity by the rato pip? where pisa partial pressure. “Answor The standard Gibbs energy ofthe reaction is 4,G"=24,6"(NHy 8) —{4,G"(N 8) + 34,6°(H 8) 1A G*(NH,,g) =2 (16.5 k] mol") Then, 2x(165%10'}mol") __2«165%10" (E3145 KC mol) xQ98K)_#3145%298 Hence, K= 6.1 x 10° This result is thermodynamically exact The thermodynamic ‘equilibrium constant forthe reaction is Sa, yh K7.2 THE DESCRIPTION OF EQUILIBRIUM and this ratio has exactly the value we have just calculated. At low overall pressures, the activities can be replaced by the ratios p/p", where p isa partial pressure, and an approximate form of the equilibrium constant is end PhP © yJP MELOY Probie Solf-test 7.1. Evaluate the equilibrium constant for N;O,(g) +22 NO;(g) 3t 298 K. (K=015] Example 7.2 Estimating the degree of cissociation at equim “The degree of dissociation, is defined as the fraction of reactant that has decom posed if the initial amount of reactant i and the amount at equilibrium i ray then a= (n~11,)/n. The standard Gibbs energy of reaction forthe decomposition H,O(g) H,(g)+ + 0,(g)is+118.08K) mot at 2300 K. What isthe degree of dis- sociation of H,O at 2300 K and 1.00 bar? ‘Method ‘The equilibrium constant is obtained from the standard Gibbs energy of reaction by using eqn 7.17, so the taskis to relate the degree of dissociation, to K and then to find its numerical value. Proceed by expressing the equ positions in terms of a, and solve for crin terms of K. Because the standard Gibbs ‘energy of reaction is large and positive, we can anticipate that K will be small, and hence that a 1, which opens the way to making approximations to obtain its numerical value Answor The equilibrium constant is obtained from eqn 7.17 inthe form r AG* (4118.08 x 10° J mol") TRE (63145) K mol) x (2300 K) 1180810" 3145 %2300 Te follows that K = 2.08 x 10°, The equilibrium composition can be expressed in terms of aby dravsng up the follwing table: Ho cs ° Insane : o ° (Change to reach qulibeium ‘Amount at qulibium Touk(1+ Jaw Mle feton, Ponti presues 7, where, forthe entries in the lst row, we have used p,=25p (eqn 1.13). The equilib rium constants therefore gata oe! Pao U=oi2+a)"? 207208 7 CHEMICAL EQUILIBRIUM Comment 7.4 ‘The textbook’s web site contains links to ‘online tools forthe estimation of equilibrium constants of gas-phase reactions. Boltzmann distribution Population 9.74 ‘The Boltzmann distribution of poptlations over the energy levels of two species A and B with similar densities of energy levels the reaction A —» Bis ‘endothermic inthis example. The bulk of the population i associated with the species 50 that species is dominant at equilibrium, In this expression, we have written p in place of p/p" to keep the notation simple. "Now make the approximetion that o-<: 1, and hence obtain empl se Under the stated condition, p = 1.00 bar (that is, pip? = 1.00), s0 a= (2K = (0.0205. That is, about 2 per cent ofthe water has decomposed. Ante on good practice Always check that the approximation is consistent with the final answer. In this case a: 1 in accord with the original assumption, Solf-test 7.2 Given that the standard Gibbs energy of reaction at 2000 K is +135.2 kJ mot for the same reaction, suppose that steam at 200 kPa is passed through a furnace tube at that temperature. Calculate the mole fraction of O, present in the output gas stream. {0.00221} (6) The relation between equilibrium constants “The only remaining problem is to express the thermodynamic equilibrium constant interms ofthe mole fractions, x, of molalities, ly, ofthe species. To do so, we need to know the activity coefficients, and then to use a= 73 oF a= by/U" (recalling thet the activity coefficients depend on the choice), For example, inthe latter case, for an equi- librium ofthe form A+B = C+D, where al four species are solutes, we write n= Sto 1b, be (as) At Tate “The activity coeficients must beevalusted atthe equilibrium composition ofthe mix- ture (for instance, by using one of the Debye-Htickel expressions, Section 5.9), which ‘may involve complicated calculation, because the activity coeficientsare known only ifthe equilibrium composition is already known. In elementary applications, and to begin the iterative calculation of the concentrations ina real example, the assumption is often made that the activity coefficients are all so close to unity that K,= 1. Then we obtain the result widely used in elementary chemistry that K'= Ky and equilibria are discussed in terms of molalities (or molar concentrations) themselves. ‘We can obtain a deeper insight into the origin and significance ofthe equilibrium constant by considering the Boltzmann distribution of molecules over the avail able states of a system composed of reactants and products (recall Molecular inter- ‘pretation 3.1). When atoms can exchange partners, as in a reaction, the available states of the system include arrangements in which the atoms are present in the form of reactants and inthe form of products: these arrangements have their char- ‘acteristic sets of energy levels, but the Boltzmann distribution does not distinguish between their identities, only their energies. The atoms distribute themselves over ‘both sets of energy levels in accord with the Boltzmann distribution (Fig. 74). Ata given temperature, there willbe a specific distribution of populations, and hence a specific composition ofthe reaction mixture. It can be appreciated from the illustration thet if the reactants and products both have similar srrays of molecular energy levels, then the dominant species in a reaction mixture at equilibrium will be the species with the lower set of energy7.2 THE DESCRIPTION OF EQUILIBRIUM 209 levels However, the fact that the Gibbs energy occurs inthe expression is signal that entropy plays role as well as energy ts ole can be appreciated by referring to Fig. 75. We sce that, although the B energy levels lic higher than the A energy levels, in this instance they are much more closely spaced. Asa result, their total population may be considerable and B could even dominate in the reaction mix treat equilibrium. Closely spaced energy levels correlate with a high entropy (see ‘Molecular interpretation 3.1), so in this ease we see that entropy effects dominate adverse encrgy effets. This competition is mirrored in eqn 7.17, as ean be seen most clearly by using A,G*=A,H°— T,S* and writing iti the form, Kaestnrensin as) Note that a positive reaction enthalpy results in a lowering of the equilibriam ‘constant (that is, an endothermic reaction can be expected te have an equilibrium ‘composition that favours the reactants). However, if there is pesitive reaction ‘entropy, then the equilibrium composition may favour products, despite the ‘endothermic characte ofthe reaction. {@) Equilibria in biological systems ‘We saw in Section 5.7 that for biological systems itis appropriate to adopt the biolo- gical standard state in which a.= 10’? and pH_=—logay).=7. It follows from eqn 5.56 thatthe relation between the thermodynamic and biological standard Gibbs energies of reaction fora reaction ofthe form A+ VEI(aq) > P (7.20a) is A,G°=A,6°+7vRTin 10 (7.206) [Note that there is no difference between the two standard values if hydrogen ions are not involved in the reaction (v=0), lustration7.4 Using the biobgtcal standard stato Consider the reaction NADH(¢q) + H'(aq) > NAD"(aq) + H(@) at 37°C, for which A,G*=—21.8 k] mol, NADH is the reduced form of nicoti: znamide adenine dinucleotide and NAD‘ isits oxidized forms the molecules play an {important roe in the later stages ofthe respiratory proces. It follows that, because v=1and71Ini0= 16.1, 21,8 KJ mol! + 16.1 (8.3145 x 10 KJ K mol") x (310K) 419.7 Kj mot! ‘Note that the biological standard value is opposite in sign (inthis example) to the ‘thermodynamic standard value: the much lower concentration of hydronium ions (by seven orders of magnitude) at pH =7 in place of pH =O, has resulted in the reverse reaction becoming spontaneous. Solttest 7.3 For a particular reaction of the form A —> B+ 2 HT in aqueous solution, it was found that A,G* = +20 kJ mol"! at 28°C. Estimate the value of AC. [-61 KI mor} Boltemann distibution Population 'a.78 Eventhough the reaction A> Bis endothermic, th density of energy levels in Bissomuch greater than thatin A that the population associated with Bis greater than {hat associated with A, s0 8 is dominant at cguilibrium,210 7 CHEMICAL EQUILIBRIUM compressed (from ato B), the reaction respondsby reducing the number of _molecules in the gas phase (inthiscase by producing the dimers represented by the linked spheres). The response of equilibria to the con Equilibria respond to changes in pressure, temperature, and concentrations ofreactants and products. The equilibrium constant for a reaction is not affected by the presence (fa catalyst or an enzyme (a biological catalyst) As we shall seein detail in Sections 225 and 256, catalysts increase the rate at which equilibrium is attained but do not affect its position. However, itis important to note that in industry reactions rarely reach equilibrium, partly on account of the rates at which reactants mix. 73 How equilibria respond to pressure ‘The equilibrium constant depends on the value of A,G°, which is defined ata single, standard pressure. The value of A,G*, and hence of K,is therefore independent of the pressure at which the equilibrium is actually established. Formally we may express this independence as a) <0 7.21 ), (an) ‘The conclusion that K is independent of pressure does not necessarily mean that the equilibrium composition is independent of the pressure, and its effect depends on how the pressure is applied. "The pressure within a reaction vessel can be increased by injecting an inert gas into it. However, so longas the gases are perfect, this addition of gas leaves all the partial pressures of the reacting gases unchanged: the partial pres- sures of a perfect gasis the pressure it would exert if it were alone in the container, so the presence of another gas has no effect. I follows that pressurization by the addition ‘ofan inert gus has no effect on the equilibrium composition of the system (provided the gases are perfect) Alternatively, the pressure of the system may be increased by confining the gases to a smaller volume (that is, by compression). Now the individual partial pressures are changed but theirratio (ast appears inthe equilibrium constant) remains the same. Consider, for instance, the perfect gas equilibrium A= 2B, for ‘which the equilibrium constant is i Pap ‘The right-hand side of this expression remains constant only ifan increase in p, can- «els an increase inthe square of py. 'Thiseelatvely steep increase ofp, compared to a will occur ifthe equilibrium composition shifts in favour of A at the expense of B.Then the number of A molecules will increase as the volume of the container is decreased and its patial pressure will vise more rapidly than can be ascribed to a simple change in volume alone (Fig. 7.6) ‘The increase in the number of A molecules and the corresponding decrease in the ‘number ofB molecules in the equilibrium A-=+2B isa special ease ofa principle pro- ‘posed by the French chemist Henri Le Chateic.' Le Chateier’s principe states that A system at equilibrium, when subjected to a disturbance, responds in a way that tends to minimize the effec ofthe disturbance ‘The principle implies tha, ifa system at equilibrium is compressed, then the reaction, will adjust so as to minimize the increase in pressure. This it can do by reducing the ‘number of particles in the gas phase, which implies a shift A 2B. * Le Chair ko iventod oxyacetylene welding74 ‘THE RESPONSE OF EQUILIBRIA TO TEMPERATURE 211 To treat the effect of compression quantitatively, we suppose that there is an amount r of A present initially (and no B). Atequilibrium the amount of Ais (1) and the amount of Bis 2am, where is the extent of dissociation of A into 2B. I fl- lows that the mole fractions present at equilibrium are (ran ine 2a (-@nv20n 140 2 lea The equilibrium constant forthe reaction is Xie" _ 40°(pip*) Pa PT which rearranges to _. (te van) Leaping “hinjene sng th cre tnd pa ep ‘and B do depend on pressure (ig. 77), It aio shows that a pe nceased, decreases nator with Le Chat principle. lustration 7.5 Predicting ihe effect of compression ‘Topreictthecfe ofenincrssein presse onthe composition theammonia synthesis at equilibrium, eqn 7.10, we note that the number of gas molecules de- Greases (rom 40 2) So, Le Chat’ principe pedis that ances pre Sew favour the product. The eg constant is Bau? sao Kat Pah, ANA where Ks the prt ofthe eqlirium constant expression that contains the cqu- librium moe factions of reactants and products (ote tha, unlike Kil, is not an esl constant). Therefore, doubling the presre must increase K, bya factor of4to preserve the vale ofK x Solftest 74 Predict the effect ofa tenfold pressure increase on the equilibrium composition of the reaction 3 N,(g) + H,(8) ~> 2 NH). [100-folinereasein K,} 7.4 The response of equilibria to temperature Le Chateier's principle predicts that a system at equilibrium will tend to shift in the ‘endothermic direction ifthe temperatures raised, for then energy isabsorbed as heat and the rise in temperature is opposed. Conversely, an equilibrium can be expected to shift in the exothermic direction if the temperature is lowered, for then energy is released and the reduction in temperature is opposed. These conclusions can be sum marized as follows: Exothermic reactions: increased temperature favours the reactants. Endothermie reactions: inereased temperature favours the products. We shall now justify these remarks andl see how to expres the changes quantitatively 10, Extent of dissociation, « pip’ fg. 7.7 The pressure dependence ofthe degree of issoctation, dat equilibrium for an A(g) = 2B(g) reaction for diferent values ofthe equilibrium constant K. The value 0 corresponds to pre corresponds to pure B. [tag Seaton Pots ands erin the pressure for several values of the quilibrium constant K,2127 CHEMICAL EQUILIBRIUM {@) The van *tHotf equation ‘The van’t Hoff equation, whichis derived in the Justification below, isan exprestion for the slope ofa plot ofthe equilibrium constant (specifically, In K) asa function of temperature. It may be expressed in either of two ways: dink _ AH dink 4 He a ) Q eo aa Cc at) R (723) Justification 7.2 Thevan 't Hoff equstion rom eg 7.17, weknow that Age ORT Diflerentiationofln Kwith respect to temperature then gives dink 14(4G%r) ar Rat Ink ‘The differentialsare complete because Kand A,G*depend only on temperature, not ‘on pressure, To develop this equation we use the Gibbs-Helmholtz equation (eqet 3.83) in the form, WAGrT) AH a Te \where A, H® isthe standard reaction enthalpy atthe temperature 7. Combi two equations gives the van "t Hoff equation, eqn 7.23a, The second form of the ‘equation is obtained by noting that aur) aT PauiT) Ti follows that eqn 7.23a can be rewritten as dink AH? “TaqyT) RT which simplifies inte eqn 7.23b, quation 723a shows that dn K/d7°<0 (and therefore that AKTA<0) fora reac tion thatisexothermiic under standard conditions (A, H®<0).A negative slope means that In K, and therefore K itself, decreases asthe temperature rises. Therefore, as asserted above, in the ease ofan exothermic reaction the equilibrium shiftsaway from products. The opposite occurs in the case of endothermic reactions. Some insight ito the thermodynamie basis of this behaviour comes from the expression A\G"= AH? A,S* written in the form A,G°/T =A, H°/T + AS". ‘When the reaction is exothermic, ~A,1*/T corresponds to a positive change of ‘entropy ofthe surroundings and favours te formation of products. When the te perature is raised, ~A,7°/T decreases, and the inereasing entropy ofthe surroundings has a ess important role. As a result, the equilibrium les less tothe ight. When the reaction is endothermic, the principal factor isthe increasing entropy ofthe reaction system. The importance ofthe unfavourable change of entropy ofthe surroundings reduced if the temperature is raised (because then A, HV is smaller), and the reac tion isable to shift towards produts.7.4 THE RESPONSE OF EQUILIBRIA TO TEMPERATURE 213 “th i | Eneray Energy smpereture ‘temperature {E Low temperature |EGHigh temperature (oS (o) Molecular interpretation 7.3 Te temperature dopendence ofthe equitvirn constant ‘The typical arrangement of energy levels for an endothermic reaction is shown in Fig, 7.8a, When the temperature is increased, the Boltzmann distribution adjusts and the populations change as shown. The change corresponds to an increased ‘population ofthe higher energy states atthe expense ofthe population of the lower ‘energy states. We see thatthe states that arise from the B molecules become more populated at the expense ofthe A molecules. Therefore, the total population of B states increases, and B becomes more abundant in the equilibrium mixture. ‘Conversely, if the reaction is exothermic (Fig. 7.8b), then an increase in tempera- ture increases the population of the A states (which start at higher energy) at the ‘expense of the B states so the reactants become more abundant. Example 7-8 Maasuring a reaction enthalpy ‘The data below show the temperature variation of the equilibrium constant of the reaction Ag,CO,(s) = Ag,0(s) + CO,(g). Calculate the standard reaction enthalpy of the decomposition. TK 350 400 450 500 K 3.9810 14x10? 86x10 148 Method It follows from eqn 7.23b that, provided the reaction enthalpy can be assumed to be independent of temperature, a plot of In against should be a straight line of slope A,H®/R. Answer We draw up the following table: TK 350 400450500, (OKT 286-250 2.22 2.00 Ank ae a ne) ‘These points are plotted in Fig, 7.9. The slope of the graph is +9.6 10°, so A,H*= (49.6210 K) x R=+80K) mol p78 Theeffec oftemperature ona chemical equilibrium can be interpreted in terme ofthe change in the Boltzmann distribution wth temperature and the effec ofthat change in the population of the specics. (a) In an endothermic eaction, the population of increases tthe expense fof Aas the temperaturcis raised. (b) In an ‘exothermic reaction, the opposite happens. 2922 24 28 28 28 Go Ky e.79 When In Kis plotted against VT, straight ine is expected with slope equal to A, HIRI the standard reaction enthalpy does not vary appreciably with temperature. Thisisanon-calorimetsic method forthe measurement of reaction enthalpies. xploratlon The equilibrium ‘constant ofa reaction is found to fitthe expresion In K= a+ b(TIR) + GICTIK) over range of temperatures. (@) Write expressions for A,H® and 48°. (b) Plotin K against UT between 400 Kand 20,b=-1.0% 10 and24 7 CHEMICAL EQUILIBRIUM Selttest 7.5 The equilibrium constant of the reaction 2 $O,(g) + 0,(g) = 2 SOs(g) is 4.0% 10" at 300 K, 25x 10!” at 500 K, and 3.0 x 10*at 700 K. Estimate the reaction enthalpy at 500 K. [-200 kj mot") ‘The temperature dependence of the equilibrium constant provides a_non- «calorimetric method of determining A, H®. A drawback is thatthe reaction enthalpy is actually temperature-dependent, so the plot is not expected to be perfectly linear. ‘However, the temperature dependence is weak in many cass, so the plots reasonably straight. In practice, the method is not very accurate, but itis often the only method available. (8) The value of K at diferent temperatures ‘To find the value ofthe equilibrium constantat a temperature K, at another temperature T,, we integrate eqn 7.23b between these two temperatures: Ink,-Ink, {If we suppose that 4, 1° varies only slightly with temperature over the temperature range of interes, then we may take it outside the integra. It follows that AHe(1 1 Inyo, = (725) ream cr Mustration 7.6 Estimating an equiitrium constant ata ciferent temperature ‘Toestimate the equilibrium constant forthe synthesis of ammonia at 500 K from its valueat 298 K (6.1 10° forthe reaction as written in eqn 7.10) we use thestand- ard reaction enthalpy, which can be obtained from ‘Table 2.7 in the Data section by using A, H®=24,H*(NHs ), and assume that its value is constant over the range of temperatures. Then, with A,H*=~92.2kI mot! from eqn7.25 we find (92.2%10%Jmot") (11 83145)" mol In K,=In(6.1> 10°) ~ EE It follows that K, =0.18, a lower value than at 298 K, as expected for this exother- mic reaction, Satttest 7.6 ‘The equilibrium constant for N,O,(¢) = 21NO,(g) was calculated in SelFtest7.1, Estimate its value at 100°C. is} Knowledge ofthe temperature dependence of the equilibrium constant for areac- tion can be useful in the design of laboratory and industrial processes. For example, synthetic chemists can improve the yield of a eaction by changing the temperature of the reaction mixture, Also, reduction of a metal oxide with carbon or carbon ‘monoxide results in the extraction of the metal when the process is carried out at a temperature for which the equilibrium constant for the reaction is much greater than one,‘7A THE RESPONSE OF EQUILIBRIA TO TEMPERATURE 215 AY IMPACT ON ENGINEERING NSU 17.1 The extraction of metals from their oxides ‘Metals can be obtained from their oxides by reduction with carbon or carbon monox- ide if any of the equilibria MO(s) + C(s) = M(s) +CO(g) MO(9)+4.C(s) EM(s)+ C0.) MO(s) +CO(g) = M(s)+CO,(e) ico the right (thats, have K'> 1). As we shal see, these equilibria can be discussed in terms of the thermodynamic functions for the eactions GMs) +4.0,(g) > MO() (i) $C(8) +4 Og) > COG) GiiNC() +4 04g) > COW (iv) COlg) ++ 05{g) >» CO.(g) “The temperature dependences ofthe standard Gibbs energies of reactions (i)-(iv) depend on the reaction entropy through d,G*/4T =—,S°, Because in reaction i) there sa net increase in the amount of asthe standard reaction entropy is large and positive; therefore, its A,G* decreases sharply with increasing temperature. In reac- tion (iv) there isa similar net decrease inthe amount of yas. s0A,G*increases sharply with ineteasing temperature. In reaction (i), the amount of gas i constant, so the entropy change is small and A,G° changes only slightly with temperature. These Femarksare summarized in Fig. 7.10, which called an Ellingham digram, Note that {A,G° decreases upwards! ‘At room temperature, A,G* is dominated by the contribution ofthe reaction ‘enthalpy (1,5 being relatively small), othe order of increasing A,G*isthe same as, the order of increasing A, H* (Al, s most exothermic; AO is est). The standard reaction entropy is similar forall metals because in each ease gaseous oxygen i eimin sted and a compact, sold oxide is formed. Asa result, the temperature dependence ‘ofthe standard Gibbs energy of oxidation shouldbe similar forall metals, asi shown bby the similar slopes of the lines in the diagram. The kinks at high temperatures cor~ respond tothe evaporation of the metals less pronounced kinks occur atthe meting temperatures ofthe metals and the oxides Successful reduction ofthe oxide depends on the outcome ofthe competition ofthe carbon forthe oxygen bound to the metal. The standard Gibbs energies forthe redc- tions can be expresed in termsof the standard Gibbs nerges forthe reactions above: MO(s) + C{s) > Mis) + CO(@) 4,64) MO(s) +4015) 9 MGs) +4 CO,(e)_8,6°=A,6%G)-4,67G) MOG)+CO(g) > M(9)+COg)—_-,G*=A,6%G) 4,60) ‘The equilibrium ies tothe right iA,G*< 0. This thease when the line for reaction {lies below (is more positive than) the line for one ofthe reactions (i) (iv). “Thespontaneity ofa reduction at any temperature canbe predicted simply by look- ing atthe diagram: a metal oxide is reduced by any carbon reaction lying above because the overall reaction then has A,G® <0. For example, CuO can be reduced to Cuatany temperature above room temperature. Evenin the absence of arbon, Ag,O decomposes when heated abave 2007C because then the standard Gibbs energy for reaction (i) becomes positive (and the reverse reaction is then spontaneous). On the other hand, Al,O, is not reduced by carbon until the temperature has been raised to above 2000°C. Temperature, 61°C "ig. 740 An Ellingham diagram forthe discussion ofthe reduction of metal oes.216 7 CHEMICAL EQUILIBRIUM Equilibrium electrochemistry We shall now see how the foregoing ideas, with certain changes of technical detail,can be use to describe the equilibrium properties of reactions taking place in electrochem- ical eels. The ability to make very precise measurements of currents and potential dilerences( voltages’) means that electrochemical methods can be used to determine thermodynamic properties of reactions that may be inaccessible by other methods. ‘An electrochemical cell consists of two electrodes, or metallic eonductors, in con- tact with an electrolyte, an ionic conductor (which may be a solution, aliquid, or a solid). An electrode and its electrolyte comprise an electrode compartment. The two clectrodes may share the same compartment. The various kinds of electrode are sum- ‘marized in Table 7.1. Any ‘ner metal shown as part ofthe specification is present to actas a source or snk of electrons, but takes no other part in the reaction other than acting as a catalyst for it. IFthe electrolytes are different, the two compartments may be joined by a salt bridge, which isa tube containing a concentrated electrolyte solu- tion (almost always potassium chloride in agar jelly) that completes the electrical cuit and enables the cello function. A galvanic cell isan electrochernical cell that produces electricity as a result of the spontaneous reaction occurring inside it. An electrolytic cells an electrochemical cell in which a non-spontancous reaction is driven by an external source of current. 75 Half-reactions and electrodes Te willbe familiar from introductory chemistry courses that oxidation isthe removal ‘of electrons from a species, a reduction is the addition of electrons to a species, anda redox reaction is a reaction in which there isa transfer of electrons from one species to another. The electron transfer may be accompanied by other events, such as atom cr ion transfer, but the net effect is electron transfer and hence a change in oxidation number of an element. The reducing agent (or ‘reductant’) is the electron donor; the oxidizing agent (or ‘oxidant’ is the electron acceptor. It should also be familiar that any redox reaction may be expressed as the difference of two reduction hal reactions, which are conceptual reactions showing the gain of electrons. Even reac tions that are not redox reactions may ofien be expressed as the difference of two reduction half-reactions. The reduced and exidized species ina half-reaction form a redox couple. In general we write a couple as Ox/Red and the corresponding reduc tion half-reaction as Ox+ ve" Red (726) Table 7.1 Varictiesofclectrode Hlctedetype Designation alereacion Meulmtlion — M)IN(0q) arm Mag) +> Ms) cas PUS)XLEDIN aq) XK, Wag) te EX) PUS)IX (BX (aq) XX FX) +E 9X (aa) Metainsclubleslt M(S)IMX(S)D (0g) MIXIMX OG) Fe 9 Mis +E CaQh Redox PM"). A(aq) ME Nag) + Mag)7.6 VARIEEIES OF CELLS 217 Mlustration 7.7 Excressing 2 reaction in terns of hal-eactions ‘The dissolution of silver chloride in water AgCI(s) —> Ag'(ag) + CI (aq), which is nota redox reaction, can be expressed a the difference of the following two reduc: tion half-reactions: Ags) +e Agls)+ CP (aa) Ag'(aq) +e > Agis) “The redox couples are AgC/Ag,CT and Ag'/Ag, respectively. Set-test 7.7 Express the formation of H,0 from H, and O, in aciie solution (a redox reaction) asthe difference of two reduction half reactions. [AH(aq) +4 & 92 H(g), On(g) + 4H (aq) +4e~92 1,000] ‘We shall often find it useful to express the composition of an electrode compart- ‘ment in terms of the reaction quotient, Q, for the half-reaction. This quotient is defined like the reaction quotient forthe overall reaction, but the electrons are ignored. ‘The reaction quotient for the reduction of O, to H,O in acid solution, O,(@) + 4HGq) +4 921,00), i8 ae Electrons, Q & Anode Cathode’ “The approximations used in the second step are thatthe activity of water is 1 (be- + ‘cause the solution is dilute) and the oxygen behaves asa perfect gas, 50 do, = Po /P* ‘Sotttest 78 Write the half-reaction and the reaction quotient fora chlorine gas electrode, [C,(g) +26 4 2CF (aq), Q= a@-¥"IPc:) The reduction and oxidation processes responsible forthe overall reaction in a cell are separated in space: oxidation takes placeat one electrode and reduction takes place atthe other. As the reaction proceeds, the electrons released in the oxidation Red, —> Ox, + ve" at one electrode travel through the external circuit and re-enter the cell Oxidation Reduction through the other clectzode. There they bring about reduction Ox, + Ve" ~> Red. ‘The electrode at which oxidation occurs is called the anode; the electrode at w reduction occurs is called the cathode. In a galvanic ell, the cathode has a higher py.71 When spontaneous reaction potential than the anode: the species undergoing reduction, Ox, withdraws electrons takes place in galvanic el, lectons are from its electrode (the cathode, Fig. 7.11), so leaving a relative positive charge on it deposited in one electrode (the sit of (correspondingto a high potential). At the anode, oxidation results inthe transfer of oxidation, theanode) and cllecel from electrons tothe electrode, so giving ita relative negative charge (corresponding to a athe (the site of eduction, the een ‘athode),ands0thereis 2 net flow of ‘rent which can be sed todo work ‘Note that the + sig a the cathode canbe 76 Varieties of cells interpreted asindcating the electrode st ‘which elecwons enter declan the “The simplest type of cell has a single electrolyte common to both electrodes (as in Sgn ofthe anedefs where he electrons Fig.7.11) Insome asesitisnecessaryto immerse the electrodesindiflerentelecteoytes, leave the cll.218 7 CHEMICAL EQUILIBRIUM os Zine Zine sulfate ‘solution Porous, pot ‘Copper my sulfate ‘solution 5.742 One version ofthe Daniell ell The ‘copper electrode isthe cathode andthe zine electrode isthe anode Electrons leave the call from the zine electrode and enterit agin through the copper electrode. Electrode compartments e713 The sat ridge, sentially an inverted U-tube fll of concentrated salt sclution in jelly, has two opposing liquid junction potest that almost ane asin the ‘Daniel cel’ in which the redox couple at one electrode is Cu"/Cuand at the other is Zn!"/Zn (Fig. 7.12). In an electrolyte concentration eel, the electrode com- partments are identical except for the concentrations ofthe electrolytes. In an elee- trode concentration cell the electrodes themselves have different concentrations, either because they are gas electrodes operating at different pressures or because they are amalgams (solutions in mercury) with different concentrations. {2) Liquid junction potentials, Ina cll wth two diferent electrolyte solutions in contact, asin the Daniell ell there js an adlitional source of potential difference across the interface of the two elec- trolytes. This potential is called the liquid junetion potential, Fy. Another example ‘ofa junction potential is that between different concentrations of hydrochloric acid. [Atthe junction, the mobile Hons difase into the moe lute solution. The bulkier (CL ions fll, bt initially do s more slowly, hich revolts in potential difference at the junction. The potential then settles dosin to value sich tha, after that brief intial period the ions diffuse atthe sme rates. Electrolyte concentration cells alvays have aliquid junction; electrode concentration cells do not. “The contribution ofthe liquid junction tothe potential canbe reduced (to about 1 0.2 mV) by joining the eleccelyte compartments through sl bridge (Fig. 7.13). “The reaon for the success ofthe salt bridge i that the liquid junction potential a cithercnd ar lrgely independent of the concentrations ofthe two dilute solutions, and so nearly cancel {0) Notation In the notation for cells, phase boundaries are denoted by a vertical bar. For example, PUS)IH,(@) HHCH(aq)|AgCIGS)1Ag(s) liquid junction i denoted by :, so the cell in Fig 7.12, i denoted Znls) {ZnSO ,(aq)?CuSO,ag)1Ca\s) double vertical line, ], denotes an interface for which itis assumed thatthe unetion potential has been eliminated, Thus the cell in Fig 7.13 is denoted Zn(s){ZnSO,(aq) CuSO, (aq) Cuts) ‘An example ofan electrolyte concentration cell in which the liquid junction potential is assumed to be eliminated is Pt(s)Ha(g)| HCUGag, by HHCH(ag, b,)1(@) LPs). 77 The electromotive force ‘The current produced by a galvanic cell arises from the spontaneous chemical reac- tion taking place inside it. The cell reaction is the reaction in the cell written on the assumption thatthe right-hand electrode isthe cathode, and hence thatthe spontan- ‘ous reaction isone in which reduction is taking place inthe right-hand compartment. Later we see how to predict ifthe right-hand electrode is infact the cathodes if itis, then the cell reaction is spontaneous as written Ifthe left-hand electrode turns out to be the cathode, then the reverse of the corresponding cell action i spontaneous. ‘To write the cell reaction corresponding toa cell diagram, we ist writ the right- hhand half-reaction asa reduction (because we have assumed that to be spontaneous). ‘Then we subtract fromit the left-hand reduction halfeaction (for by implication, that7.7 THE ELECTROMOTIVE FORCE electrode is the site of xidation).Thus, inthe cellZn(s)|Zn$O (aq) CuSO,(aq) | Culs) the two electrodes and their reduction half-reactions ate Right-hand electrode: Cu2(aq) +2€°—» Cuts) Lefichand electrode: Zn"(ag) +2€°— Zn(s) Hence, the overall cell reaction isthe difference: Cu" (aq) + Zn(s) > Cuts) + Zn*(aq) (a) The Nernst equation ‘Accallin which the overall cell reaction has not reached chemical equilibrium can do ‘electrical work as the reaction drives electrons through an external circuit. The work that a given transfer of electrons can accomplish depends on the potential difference between the two electrodes. This potential difference is called the cell potential and is ‘measured in volts V (1 V= 1 C's). When the cell potential is large, given number ofelectrons travelling between the electrodes an do large amount of electrical work. When the cell potential is small, the same number of electrons can do only a small amount of work. A cell in which the overall reaction i at equilibrium can do no work, and then the cell potentials zero. According to the discussion in Section 3.5e, we know that the maximum non- expansion work, which in the current context i clectrical work, that asystem (the cell) can do is given by eqn 3.38 (Wax AG), with AG identified (as we shal show) with the Gibbs energy ofthe cell reaction, A,G. It follows that, to draw thermodynamic ‘conclusions from measurements ofthe work cell an do, we must ensure that the cell is operating reversibly, for only then ist producing maximum work. Moreover, we saw in Seetion 71a that the reaction Gibbs energy is actually a property relating to a specified composition ofthe reaction mixture. Therefore, to make use of 4,G we must censure that the cells operating reversibly ata specific, constant composition. Both these conditionsare achieved by measuring the cll potential when itisbalanced by an exactly opposing source of potential so that the cell reaction occurs reversibly, the compexition is constant, and no current flows: in effect, the cell reaction is poised for change, but not actually changing, The resulting potential differences called the elec- tromotive force (emf), F, ofthe cll ‘As we show in the Justification below, the relation between the reaction Gibbs energy and the emf ofthe cell is -VEE=A,G (727) where F is Faraday’s constant, F = eN and v is the stoichiometric coefficient of the electrons in the half-reactions into which the cell reaction can be divided, This ‘equation is the key connection between electrical measurements on the one hand and thermodynamic properties on the other. It ill be the basis of all that follows. Justification 7.3. The elation betwean the eleciramatne force ard the reaction bbs eneray We consider the change in G when the cell reaction advances by an infinitesimal amount dé at some composition. From eqn 7.15 we can write (at constant temnper- ature and pressure) c= Aca ‘The maximum non-expansion (electrical) work that the reaction ean do as it advances by df at constant temperature and pressure i therefore a, O65 219220 7 CHEMICAL EQUILIBRIUM Gibbs eneray, 6 " Extent of reaction, € fp. A spontancous reaction occurs in the direction of decreasing Gibbs energy. ‘When expressed in terms ofa cell potential, the spontancous direction of change cn be expressed in terms ofthe cll emf, F.The reaction is spontaneous 2s written (from leftto right on the illustration) when E> 0. ‘The reverse reaction i spontaneous when E<0. When the cell action ist ‘quiliriuns, the cell potential is zero, ‘This work is infinitesimal, and the composition of the system is virtually constant when itoccurs Suppose that the reaction advances by A, then v6 electrons must travel from the anode to the cathode. The total charge transported between the electrodes when this change occurs is ~veN a (because wg is the amount of electrons and the charge per mole of electronsis~eN,). Fence the total charge transported is -vFag, because eN, =F. The work done when an infinitesimal charge —VFAg travels from the anode (o the cathode is equal to the product of the charge and the potential Aifference F (see Table 2.1 and Appendix 3): dy =-VFEAE ‘When we equate this relation tothe one above (dw, cancels, and we obtain eqn 7.27 GA), the advancement d& It fellows from eqn 7.27 that, by knowing the reaction Gibbs energy ata specified ‘composition, we can state the ell emt at that composition. Note that a negative reac- tion Gibbs energy, corresponding to a spontancous cell reaction, corresponds to a positive cell emf. Another way oflookingatthe content of eqn 7.27 is thatit shows that the driving power of cel (that is, its emt) is proportional tothe slope of the Gibbs ‘energy with respect tothe extent of reaction. Its plausible that a reaction that is far fiom equilibrium (when the slope is steep) has a strong tendency to drive electrons through an external circuit (Fig, 7-14). When the slope is dase to zero (when the cell reaction is lose to equilibrium), the ems small. Imustration 7.9 Cornering betveen the cal ef and the reaction Gibbs eneray Equation 7.27 providesan electrical method for measuring reaction Gibbsenergy at any composition of the reaction mixture: we simply measure the cell's emf and convert itto A,G. Conversely, ifwe know the value of Gata particular com- position, then we can predict the emf. For example, if,G=~1> 10? mot! and then 4 (1x10 } mot!) VP 1% (9.6485%108C mol) ‘where we have used 1 J= 1 CY, We can go on to relate the emf to the activites ofthe participants inthe cell reac~ tion. We know that the reaction Gibbs energy is related to the composition of the reaction mixture by eqn 7.11 (A,G=4,G*+RT'In Q)it follows, on division of both sides by -vF “The fist term on the right is writen act E (7.28) ve and called the standard emf ofthe cell. That is, the standard emf is the standard reac- tion Gibbs energy expressed as a potential (in volts). It follows that7.7 THEELECTROMOTIVEFORCE 221 RI vE This equation for the emf in terms of the composition is called the Nernst equation; the dependence of cell potential on composition that it predicts is summarized in Fig. 7.15. One important application of the Nernst equation isto the determination of the pH ofa solution and, with a suitable choice of electrodes, of the concentration of other ions (Section 7.90). ‘Wesee from eqn 729 that the standard emf (which will shortly move to centre tage cof the exposition) can be interpreted as the emf whenall the reactantsand products in the cell reaction are in their standard states, for then all activities are 1, so Q= 1 and. In Q=0. However, the fact that the standard emf is merely a disguised form of the standard reaction Gibbs energy (eqn 7.28) should always be kept in mind and uncler- lies alts applications. E=E*-—nQ (729) IMlustration 7.10 Using the Nernst equetion Because RTIF=25.7 mV at 25°C, a practical form of the Nernst equation is 25.7 mV Ee. Ing Itthen follows that, fora reaction in which v= 1, if Qs increased by factor of 10 then the emf decreases by 59.2 mV. (©) Celts at equilibrium A special case of the Nemst equation has great importance in electrochemistry and. provides a link to the earlier part of the chapter. Suppose the reaction has reached. ‘equilibrium; then Q = K, where K is the equilibrium constant of the cell reaction. However, a chemical reaction at equilibrium cannot do work, and hence it generates zero potential difference between the electrodes ofa galvanic cell. Therefore, setting Oand Q= Kin the Nernst equation gives re* nc (730) ET This very important equation (which could also have been obtained more directly by substituting eqn 7.29 into egn 7.17) lets us predict equilibrium constants from ‘measured standard cell potentials. However, before we use it extensively, we need to establish a further result. Mustration 7.11. Calculating an equilrium constant froma standard cll potential Because the standard emf ofthe Daniell cells +1.10 V, the equilibrium constant forthe call reaction Cu’*(aq) + Zn(s) -> Cals) + Zn'¥(ag), for which v= 2, is K=15x10" at 298 K. We conclude thatthe displacement of eopper by zine oes virtually to completion. Note that an emf ofabout 1 Vis easily measurable but cor- respondsto an equilibrium constant that would be impossible to measure by direct chemical analysis 32 z3 ot log a ‘g.148 The variation of ell emf withthe value of the reaction quotient for the cell reaction for different values of v (the ‘numberof electors tansferred). At298 K, RIVP= 25.69 mV, s0 the vertical scale refers to multiples of this value [lag Emtrton Pott varition ofl mf with the value ofthe reaction ‘quotient forthe cll reaction for difirent values ofthe temperature. Does the cell ‘em become more or les sensitive to ‘composition asthe temperature increases?m2 7 CHEMICAL EQUILIBRIUM 78 Standard potentials A galvanic cells a combination of two electrodes, and each one can be considered as ‘making a characteristic contribution to the overall cell potential Although itis not possible to measure the contribution ofa single electrode, we can define the potential ‘of one of the electrodes as zero and then assign values to others on that basis. The spe- ally selected electrode is the standard hydrogen electrode (SHE): PUI OMe) at all temperstures.'To achieve the standard conditions, the activity of the hydrogen ‘ons must be 1 (thatis, pH =0) and the pressure (more precisely, the fugacity) of the hnyclrogen gas must be I bar. The standard potential, £*, of another couple is then ‘assigned by constructing cll in which itis the right-hand electrode and the standard hydrogen electrode isthe lefi-hand electrode. “The procedure for measuring standard potential canbe illustrated by considering aspecficcase, the silver chloride electrode. The measurement is made onthe Harned call: 0 (7.311 Pe(s)|H,(2)|HCl(aq)|AgCl(s)|Ag(s) 5 H(g) + AgCl(s) > HCl(aq) + Ag(s) for which the Nernst equation is Rr. Ea E*(AgCliAg, Ch) —= In Weshalat y= sow on and for sn icy woe the ander potenti es RT In ayy F Re ‘The activities can be expressed in terms of the molality b of H1CI(aq) through ay bib" and acy = bib” as we saw in Section 5.9, 50 RT, RT — ne tinn P ge where for simplicity we have replaced b/b"by b. This expression rearranges to Beeline Ee. a (7.32) Be Inb= Be In : From the Debye-Huckel limiting law for @ 1,l-electrolyte (Section 5.9; a 1,1- electrolyte isa solution of singly charged M” and X~ ions), we know that In 7, = —b!” ‘The natural logarithm used here is proportional to the common logarithm that appears in eqn 5.69 (because In x= In 10 log x=2.303 log.x).'Therefore, with the con- stant of proportionality in this relation written as (F72RT)C eqn 7.32 becomes 2Rr E+ Sinb=Be+ co? 1733) ‘The expression on the left is evaluated at a range of molalites, plotted against U!”, and extrapolated to b =. ‘Ihe intercept at b= 0 is the value of E* for the silver! silver-chloride electrode. In precise work, the b"” term is brought to the left, and a higher-order correction tem from the extended Debye-Hickel law is used on the right.‘The emf of the cll P(s) Hi p*) | HClfaq, b)| AgCI(s)| Ags) at 25°C has the fol- lowing values: by(10 6°) 3215 5619 9.138 25.63 EV 0.52053 0.49257 0.46860 0.41824 ‘To determine the standard emf ofthe cell we draw up the following table, using 2RTIF=0.051 39 V: 10> 6) 3215 5619 9.138 25.63 {b1(10> 6)" 1793 2.370 3023 5.063 BY 052053 0.49257 0.46860 0.41824 FIV+005139Inb 0.2256 02263 «(0.2273 0.2299 ‘The data are plotted in Fig. 7.16; s can be seen, they extrapolate to E*= 0.2232 V. Soifsest 79 ‘The data below are for the cell PUs)IH,(e p")IHBr(aq, BDL ‘AgB(s)1Ag(s) at 25°C, Determine the standard emf ofthe el. bob") 408284443719 EV 0.47381 0.43636 0.36173 [oor v) ‘Table 7.2 lists standard potentials at 298 K. An important feature of standard emf ‘of ells and standard potentials of electrodes is that they are unchanged ifthe chem- ical equation for the cell reaction ora halfreacton is multiplied by a numerical factor. ‘A numerical factor increases the value ofthe standard Gibbs energy forthe reaction. Hloviever, it also increases the number of electrons transferred bythe same factor, and by eqn 7.27 the value of E* remains unchanged. A practical consequence is that cell cemfisindependent of the physical size ofthe cel. In other words, cell emfis an inten- sive property. “The standard potentials in Table 7.2 may be combined to give values for couples that are not lsted there. However, to do so, we must take into account the fact that different couples may correspond to the transfer of different numbers of electrons. ‘The procedure isillustrated in the following Example. Example 7.4 Evaluating stendrd potenti fom two others Given that the standard potentials of the Cu’*/Cu and Cut/Cu couples are +0340 V and +0.522 V, respectively, evaluate E*(Cu,Cu). ‘Method First, we note that reaction Gibbs energies may be added (asin a Hess's law analysis of reaction enthalpies). Therefore, we should convert the E* values to ‘AG* values by using eqn 7.27, add them appropriately, and then convert the over- all AG to the required B® by using eqn 7.27 again. This roundabout procedure is necessary because, as we shall see, although the factor F cancels, the factor Vin gen- eral does not. Answer ‘The electiode reactions areas follows: (@)Cu(ag)+2e>Culs) B= +0340V, $0 A,G*=-2(0.340 IF (b)Cuag) te Culs) B= 40522V, 50. A,G°=-(0.522 VF 7.8 STANDARD POTENTIALS 223 0.2300 0.2290 ENV + 0.05199 in b 0 10 20 30 40 60 (wno°6°)" p.746 The plotand the extrapolation used for the experimental measurement of ceptat b= 0 [bag Broatonstppese hatte procedure in Ilkstation 7.12 results ina plo that deviates from linearity. What right be the cause ofthis behaviour? How _might you modify the procedure o obtain arliable value ofthe standard potential? ‘Synoptic Table 7.2* Standard Cove ev CHtenre +ceCm) no. Gag) +26 96x) 4094 Hea +e $148) ° AaClsite rel) +Cag) 4022 ZaMeq) 2° 7019) ~076 Ne(aq) 4° Nals) 2n Moe value in inthe Dt scion.224 7 CHEMICAL EQUILIBRIUM ‘Table 7.3 The electrochemical series of the metalst east strongly reucng Gad Patina iver Mercury Copper yarn) Lead Tn Nickel ron ine ‘Ghromiom ‘Auminiom ‘Magnesium Soda Cakiom Potassium Most strongly redcing 1 The complete serie can einer fm water “The required reaction is (.Cur*ag) +e Cu"(ag)—E*=-A,G1F Because (c) = (a) ~(b) the standard Gibbs energy of reaction (c) is AG*=A,6%a)—4,6%) 158 V)xF ‘Therefore, E® = +0.158 V. Note that the generalization of the calculation we just performed is VE%e)= EMA) + ED) (734) Annote on good practice Whenever combining standard potentials to obtain the standard potential ofa third couple, always work via the Gibbs energies because they are additive, whereas, in genera, standard potentials are not. Solftest 7.10 Calculate the standard potential of the Fe/Fe couple from the valves for the Fe/Fe* and Fe"/Fe couples. (-0037V] 7.9 Applications of standard potentials Call emfs ate « convenient source of data on equilibrium constants and the Gibbs energies, enthalpies, and entropies of reactions. In practice the standard values of these quantities are the ones normaly determined. (a) The electrochemical series Wehave sen that fr two redox couples, Ox/Red, and Oxyd and the cll Red On[ Red Ox, E°=ES—Ef (7358) thatthe cell reaction Red, + Ox, > Ox, + Red, (73%) is spontancous as written if*> 0, and therefore if > E. Because inthe cell reac- tion Red, reduces Ox, we can conclude that Red, asa thermodynamic tendency to reduce Ox, if EP ADP(aq) +P; (aq) + HO%Caq) ‘where F; denotes an inorganic phosphate group, such as H,PO3. The biological stand- ard values for ATP hydrolysis at 37°C (310 K, blood temperature) are A,G®=—31 k) ‘mot !, A,H® =—20 kJ mot #, and 4,S°=+34 J K-" mol”. The hydrolysis is therefore exergonic (A,G® <0) under these conditions and 31 kJ mob? i available for driving ‘other reactions. Moreover, because the reaction entropy is large, the reaction Gibbs energy is sensitive to temperature. [n view of its exergonicty the ADP—phosphate bond has been called a ‘high-energy phosphate bond’. The name is intended to signify ahigh tendency to undergo reaction, and should not be confused with ‘strong’ bond. In act, even in the biological sense itis not of very ‘high energy’. The action of ATP depends on it being intermediate in activity. Thus ATP aets as a phosphate donor to number of acceptors (for example, glucose), but is recharged by more powerful phosphate donors ina number of biochemical processes. We now use the oxidation of glucose to CO, and H,O by O, as an example of how the breakdown of foods is coupled to the formation of ATP in the cell. The process begins with glycolysis, a partial oxidation of glucose by nicotinamide adenine dinu- leotide (NAD*, 2) to pyruvate ion, CHjCOCO;, continues with the citric aid eee, hich oxidizes pyruvate to CO, and ends with oxidative phosphorylation, which reduces ©, to 11,0. Glycolyss is the main source of energy during anaerobie metabolisry, a form of metabolism in which inhaled O, does not play a role. The citricacideycleand ‘oxidative phosphorylation are the main mechanisms fr the extraction of energy from ‘carbohydrates during aerobic metabolism, a form of metabolism in which inhaled O, does play role. 225226 7 CHEMICAL EQUILIBRIUM 2. NADY Grycolysis Glycolysis occurs in the eso, the aqueous material encapsulated by the cell mem: brane, and consists often enzyme-catalysed reactions. At blood temperature, A,G® = =147 kJ mot" for the oxidation of ghicose by NAD" to pyruvate ions. The oxidation cof one glucose molecule is coupled to the conversion of two ADP molecules to two ATP molecules, so the net reaction of glycolysis is: CHO ¢(ag) +2 NAD"(aq) +2 ADP(aq) +2 Pi(aq) +2 H,0(0) +2 CH,COCO;(aq) +2 NADH(aq) +2 ATP(aq) +2 H,0"(aq) ‘The standard reaction Gibbs energy is (-147) ~2(-31) kJ mot! =—85 kJ mol. The reaction is exergonic, and therefore spontaneous: the oxidation of glucase is used to ‘recharge’ the ATP. In cells that are deprived of O,, pyruvate ion is reduced to lactate ion, CH,C(OH)CO;, by NADH? Very strenuous exercise, such as bicycle racing, can decrease sharply the concentration of O, in muscle cells and the condition known as muscle fatigue results from increased concentrations of actate ion. The citric acid cycle “The standard Gibbs energy of combustion of glucose is-2880 kJ mol, so terminat Ingits oxidation at pyruvate isa poor use of resources. In the presence of O,, pyruvate is oxidized further during the citric acid cycle and oxidative phosphorylation, which ‘occur in a special compartment of the cell called the mitochondrion. The citric acid yee requires eight enzymes that couple the synthesis of ATP to the oxidation of pyruvate by NAD* and flavin adenine dinucleotide (FAD, 3) 2.CH,COCO3(ag) +8 NAD*(aq) +2 FAD(aq) +2 ADP(aq) +2 P| (aq) +8 H,0(0) + 6CO,(g) + 8 NADH(aq) +4 H,0"(aq) +2 FADH,(aq) +2 ATP(aq) ‘The NADH and FADH, go on to reduce O, during oxidative phosphorylation, which also produces ATP. The citric acd cycle and oxidative phosphorylation generate as many as 38 ATP molecules for each glucose molecule consumed. Each mole of ATP molecules extracts 31 kJ from the 2880 kJ supplied by 1 mol C,H, ,O, (180 g of 2 tyes the terminal products are ethanol nd CO,7.9 APPLICATIONS OF STANDARD POTENTIALS 227 oH, HO-E-H HO-c—H HO-c—H CH, t 9 3 FAD _lucose), so 1178 K} is stored for later use, Therefore, aerobic oxidation of ghucose is ‘much more efficient than glycolysis. In the cell, each ATP molecule can be used to drive an endergonic reaction for whieh A,G® does not exceed +31 kJ mot. For example, the biosynthesis of sucrose from glucose and fructose can be driven by plant enzymes because the reaction is cendergonicto the extent A,G® =423 KI mol '. The biosynthesis of proteinsis strongly endergonic, not only on account of the enthalpy change but also on account of the large decrease in entropy that occurs when many amino acids are assembled into a precisely determined sequence. For instance, the formation of a peptide link is cendergonic, with A,G® = +17 KI mot, but the biosynthesis occurs indirectly andl is ‘equivalent to the consumption of three ATP molecules for cach fink. In a moderately small protein like myoglobin, with about 150 peptide links, the construction alone requires 450 ATP molecules, and therefore about 12 mol of glucose molecules for {1 mol of protein molecules. The respiratory chain In the exergonic oxidation of glucose 24 electrons are transferted from each C,Hy:0, molecule to six O, molecules. The half-reactions for the oxidation of glucose and the reduction of O, are eH 2046) + 6H,0() ~ 6 CO,(g) +24 Haq) +24€ 6 Ong) +24 Haq) +24 6-9 121,010) ‘The electrons do not flow directly from glucose to O,, We have already seen that biological cells, glucose is oxidized to CO, by NAD* and FAD during glycolysis and the citric acid cycle: CH,,0,(8)+ 10 NAD" +2 FAD +4 ADP +4 P; +2H,0 > 6 CO, + 10NADH+2 FADH, +4 AIP + 6H"228 7 CHEMICAL EQUILIBRIUM ° H,CO CH, Ch, HCO i H i h 4 Coenzyme 0, 0 Inner membrane Matrix Outer A membrane tetermembrane space fg 747 The general features ofa typiesl mitochondrion. Proteins, s. Proteins, 's ‘co; 5 Heme c In the respiratory chain, electrons from the powerful reducing agents NADH and FADH, pass through four membrane-bound protein complexes and two mobile elec- tron carriers before reducing O, to H,O. We shal see that the electron transfer reac- tions drive the synthesis of ATP at three ofthe membrane protein complexes. ‘The respiratory chain begins in complex I (NADH-Q oxidoreductase), where NADH is oxidized by coenzyme Q (Q, 4) in a two-electron reaction: HY +NADH+Q 2, NAD'¥QH, B®=4042V, 4,6°=-81K) mol Additional Q molecules are reduced by FADE in complex I (succinate-Q reductase): FADH,+Q 22, FAD+QH, E°=+0015V, AG2=-29K) mol? Reduced Q migrates to complex III (Q-cytochrome ¢ oxidoreductase), which cata- Iyses the reduction ofthe protein cytochrome ¢ (Cyt ¢)- Cytochrome ¢ contains the haem group (5), the central iron ion of which can exist in oxidation states +3 and +2. ‘The net reaction catalysed by complex IIs OH, +2Fe*(Cyte) AM, C42 FeMCyRe +2 E®=+015V, — A,G°=-30kK) mol Reduced eytochrome ecartes electrons from complex Il to complex IV (cytochrome oxidase), where O, is reduced to HO: 2E(Cytg +21 +4 OFM 5 2Fe(Cyte)+H,0 F®=40815V, — A,G®=-109K} mol! Oxidative phosphoryiation “The reactions that occur in complexes I II, and IV are sufficiently exergonic to drive the synthesis of ATP in the process called exidative phosphorylation: ADP+P;+H' ATP ,G%=+31K) mot! ‘We saw above that the phosphorylation of ADP to ATP can be coupled tothe exer- genic dephosphorylation of other molecules. Indeed, this isthe mechanism by which ATP is synthesized during glycolysis and the citric acid cycle. However, oxidative phosphorylation operates by a different mechanism, ‘The structure of a mitochondrion is shown in Fig. 7.17, The protein complexes associated with the electron transport chain span the inner membrane and phosphor- ylation takes place in the matrix. The Gibbs energy of he reactionsin complexes I, Ul,7.9 APPLICATIONS OF STANDARD POTENTIALS and IV is first used to do the work of moving protons across the mitochondrial mem- brane. The complexes are oriented asymmetrically in the inner membrane so that the protons abstracted from one sce of the membrane can be deposited on the other side. For example, the oxidation of NADH by Q in complex Ii coupled to the transfer of four protons across the membrane. The coupling of electron transfer and proton purnping in complexes Il and IV contribute further to a gradient of proton concen- tration actoss the membrane. Then the enzyme H'-ATPase uses the energy stored in the proton gradient to phosphorylate ADP to ATP. Experiments show that 11 molecules of ATP are made for every three molecules of NADI and one molecule of FADH, that are oxidized by the respiratory chain. The ATTP is then hydrolysed on demand to perform useful biochemical work throughout the cell. “The chemiosmotictheory proposed by Peter Mitchell explains how H'-ATPases syn- thesize ATP from ADP. The energy stored ina transmembrane proton gradient come from two contributions. Firs, the difference in activity of 1" ion results ina difference in molar Gibbs energy across the mitochrondrial membrane AG n= Genin = Gayot Second, there is a membrane potential difference Ag = ¢, ~ Qo that arises from differences in Coulombic interactions on each side of the membrane. The charge difference across a membrane per mole of H' ions is Nye, or F, where P= eN, Itfol- lows from Justification 73, thatthe molar Gibbs energy dfferenceis then AG, =FAQ. ‘Adding this contribution to AG,,, gives the total Gibbs energy stored by the combi- nation of anan activity gradient and a membrane potential gradient. Un AG, =RTIn + FAG where we have replaced activities by molar concentrations. This equation also pro- vides an estimate of the Gibbs energy available for phosphorylation of ADP. After using In (H"] = In 10x og [H*] and substituting ApH = pl, ~ PH = og, [Hg + Jog [HT it follows that AG, FAG—(RTIn 10)ApHt Inthe mitochondrion, ApH =—1.4 and A= 0.14V,s0 AG, =+21.5KJ mol, Because 31K mol” is needed for phosphorylation, we conclude that atleast mol 1° (and probably more) must low through the membrane for the phosphorylation of ! mol ADP. (©) The determination of activity costficients Once the standard potential of an electrode in a cell is known, we can use it 10 determine mean activity coefficients by measuring the cell emf with the ions at the concentration of interest. For example, the mean activity coefficient of the ions hydrochloric acid of molality bis obtained from eqn 7.32.in the form ESE RTE ‘once Ehas been measured. Ing (7.36) (€) The determination of equilbrium constants ‘The principal use for standard potentials is to calculate the standard emf of a cell formed from any two electrodes. To do so, we subtract the standard potential ofthe left-hand electrode from the standard potential ofthe right-hand electrode: 229230 7 CHEMICAL EQUILIBRIUM Silver! silver chloride electrode: Phosphate buffer solution Glass ‘membrane 70 The glass electrode. Itis commonly ‘sed in conjunction with calomel clectrde that makes contact with the test solution through a salt bridge yeretod az som apsinO Glass perrneable to Li" and Na" ions Fg.730 A section through the wall ofa ass electrode. E*= Eight) — Ele) (737) Because AG* =—vFE*, it then follows that, ifthe result gives E® > 0, then the cor- responding cell reaction has K> 1. lMlustration 7.14 Calculating an equilbrium constant fom standard potentials ‘Adisproportionation isa reaction in which a species is both oxidized and reduced. To study the disproportionation 2 Cu'(aq) -> Cu(s) + Cu2(aq) we combine the following eectrod Right-hand electrode: Cuts)1Cu"(aq) Cutag) +e Culag) —-E*=4052V Left-hand electrode: PY(s)|Cu™(aq)Cu'(aq) — Cu™{ag)+e-> Cu"(s)—_B ‘where the standard potentials are measured at 298 K. The standard emfof the cell is therefore E*=4052V-0.16V=+0.36V 0.16V We can now calculate the equilibrium constant of the cell reaction. Because v= 1, from eqn 730 036V 036 0.025693 V 0.025603 2x 108 Solttest 7.11 Calculate the solubility constant (the equilibrium constant for the reaction Hg,Cl,(s) = He" (aq) +2 Cl (aq)) and the solubility of mercury() chlor- ide at 298.15 K. Hint. The mercury(I) ion is the diatomic species Hg". [2.6 10°, 8.7% 1077 mol ks] (@ Species-selective electrodes ‘Anion-selective electrode isan electrode that generates a potential in response to the presence ofa solution of specific ions. An example isthe glass electrode (Fig. 7.18), \hich is sensitive to hydrogen ion activity, and has a potential proportional to pH. It isfilled with a phosphate bufier containing CI ions, and conveniently has £=0 when the external medium i at pH =7.Itis necessary to calibrate the glass electrode before use with solutions of known pH. “The responsiveness of a glass electrode to the hydrogen ion activity is result of complex processes atthe interface between the glass membrane and the solutions on cither side of it. The membrane itself is permeable to Na* and Li* ions but not to 1” ions. Therefore, the potential difference across the glass membrane maust arise by @ _mechanisin diferent from that responsible for biological transmembrane potentials (impact on biochemistry 7.2). A clue to the mechanista comes from a detailed inspec- tion ofthe lass membrane, for each face is coated with a thin layer of hydrated silica (Fig, 7.19). The hydrogen ions in the test solution modify this layer to an extent that ‘depends on their activity in the solution, and the charge modification of the outside layer is transmitted to the inner layer by the Na* and Li* ions inthe glass. The hycro- gen ion activity gives rise toa membrane potential by this indirect mechanism.79 APPLICATIONS OF STANDARD POTENTIALS 231 Electrodes sensitive to hydrogen ions, and hence to pI, are typically glasses based on lithium silicate doped with heavy-metal oxides. The glass can also be made re- sponsive to Ne’, K’, and NH; ions by being doped with Al,O, and B,0,, A suitably adapted glass electrode can be used to detect the presence of certain ‘gases. A simple form of gas-sensing electrode consists ofa glass electrode contained in an outer sleeve filled with an aqueous solution and separated from the test solution ‘byamembrane that is permeable to gas. When a gas such as sulfur dioxide or ammo- nia diffuses into the aqueous solution, it modifies its pH, which in turn affects the potential ofthe glass electrode. ‘The presence of an enzyme that converts compound, such as urea or an amino acid, into ammonia, which then affects the pl, can be used, to detect these organic compounds. Somewhat more sophisticated devices are used as ion-selective electrodes that give ‘potentials according to the presence of specific ions present in a test solution. In one arrangement, a porous lipophilic (hydrocarbon-attracting) membrane is attached to asmall reservoir ofa hydrophobic (water-repelling) liquid, such as dioctyiphenyiphos. ‘phonate, that saturates it (Fig 7.20) The liquid contains an agent, such as (RO),PO; ‘with R a C, to Cyy chain, that acts as a kind of solubilizing agent for the ions with which it can form a complex. The complex’s ions are able to migrate through the lipophilic membrane, and hence give rise to a transmembrane potential, which is detected by asilver/silver chloride electrode in the interior ofthe assernbly. Electrodes Of this construction can be designed to be sensitive to a variety of ionic species, including calcium, zin, iron, lead, and copper ions. In theory, the transmembrane potential should be determined entively by differ- ‘ences in the activity of the species thatthe electrode was designed to detect. In prac- tice, a small potential difference, called the asymmetry potential, is observed even ‘when the activity of the test species is the same on both sides of the membrane. The asymmetry potential is due to the fact that it is not possible to manufacture a mem- brane material that has the same structure and the same chernical properties through cout. Furthermore, all species-selective electrodes are sensitive to more than one species. For example, a Na selective electrode also respond, albeit less effectively, t0 the activity of K* ions in the test solution. Asa result of these effects, the potential of an electrode sensitive to species X* that is also susceptible to interference by species Y's given by a modified form of the Nernst equation: RT. BoE y+ BH Ine + yt) (7.38) here B, isthe asymmetry potential, is an experimental parameter that captures deviations from the Nernst equation, and hy ys the selectivity coefficient ofthe elec- trode and is related to the response of the electrode to the interfering species Y°. A value of f= 1 indicates thatthe electrode responds tothe activity of ions in solution in a way that is consistent with the Nemst equation and, in practice, most species- selective electrodes of high quality have B= 1. The selectivity coefficient, and hence interference effects, can be minimized when designing and manufacturing @ species- selective electrode. For precise work, itis necessary to calibrate the response of the lectrode by measuring Ef and hy. before performing experimentson solutions of ‘unknown concentration of X" (6) The determination of thermodynamic functions ‘The standard emf ofa cell is related to the standard reaction Gibbs energy through eqn 7.28 (A,G® = -VFE*). Therefore, by measuring E* we ean obtain this important thermodynamic quantity Its value can then be used to calculate the Gibbs energy of, formation of ions by using the convention explained in Section 3.6. a on ees Ly a PF Peer ey wae he lipophilic coe ince, *s.720 The structure ofan ion-selective clectrode, Cheated ions are able to migrate ‘through te lipophilic rsembrane,232 7 CHEMICAL FQUTLIBRIUM, IMustration 7.18 Determining the Gibbs energy of formton of an en eectrochem cally “The cell reaction taking place in PUs)IH, II (aq) Aga |Ag(s) B= +0.7956V Agh(aa) +4118) 9 (eq) +Ag(s),G°=-A,G%Ag", a9) ‘Therefore, with v= 1, we find A,G*(Ag a9) = FE \which isin close agreement with the value in Table 2.6 of the Date section ‘The temperature coefficient ofthe standard cell emf, dE*AT, gives the standard en- {topy ofthe cell reaction. ‘This conclusion follows from the thermodynamic relation (GIT), =-Sand eqn 7.27, which combine to give (739) ‘The derivative is complete because E*, like A,G*, isindependent ofthe pressure. Hence swe have an electrochemical technique for obtaining standard reaction entropies and ‘through them the entropies of fons in solution. Finally, wecan combine the results obtained so far and use them to obtain the stand- ard reaction enthalpy: A,He=A.G*+ TAS u(r) (740) er This expression provides a non-calorimetric method for measuring A,H® and, through the convention A,H%(", aq) = 0, the standard enthalpies of formation of ions in solution (Section 2.8). Thus, electrical measurements can be used to caleulate allthe thermodynamic properties wth which this chapter began. Example 75 Using the temperature coefcient othe cel potential “The standard emf ofthe cell P(s)|#,(g) [1Br(aq) | AgBr(s)|Ag(s) was measured cover arange of temperatures, and the data were fitted tothe following polynomial E*/V =0.07131 ~4.99 x 10“ TIK— 298) ~3.45 x 10°(TIK— 298)" Fyaluate the standard reaction Gibbs energy enthalpy, and entropy at 298 K, Method "The standard Gibbs energy of reaction is obtained by using eqn7.28 after cvaluating E* at 298 K and by using 1 V C= 1. The standard entropy of reaction is obtained by using eqn 7.38, which involves differentiating the polynomial with respect to Tand then setting T= 298 K. The reaction enthalpy'is obtained by com- bining the values of the standard Gibbs energy and entropy. Answer AtT=298 K, E°=+0.07131 V, 30 VFE® = (1) x (9.6485 x 108 C mot!) x (#0.07131 V) == 6.880 10° VC mol"! =—6.880 kJ mot?‘The temperature coefficient ofthe cell potential is = 4.99 104 V Kt 2(3.45% 10-)(11K—298) V K+ At T=298 K this expression evaluates to aE 499x104 VK" ar So, from eqn 7.39, the reaction entropy is AS°=1 x (9.6485 x 10° Col) x (4.99% 104 VK) 482) K' mot! Te then follows that AH°=A,G"+ TAS®: =-21.2 mol 6.880 kj mol + (298 K) (~-0.0482 kj K CHECKLIST OF KEYIDEAS 233 (One difficulty with this procedure lies in the accurate measurement of small tem- perature coefficients of cell potential. Nevertheless, it is another example of the striking ability of thermodynamics to relate the apparently unrelated, inthis case to relate clectrcal measurements to thermal properties. Satf-test 7.12 Predict the standard potential ofthe Harned cell at 303 K from tables of thermodynamic data Checklist of key ideas Gi 1. theement of reaction () is defined such tat when the ‘extent of reaction changes bya finite arsount A, the amount OFA present changes B02 ag AE. “The seaction Gis energy isthe slope ofthe graph of the Gibbs energy plotted against the extent of ation: 4, = (G08: equilibrium, 8,6=0. -Anexeronic reaction is reaction for which 46-0; sucha reaction canbe used to dive another proces. Anendergonic reaction ina eaction for which A,G> 0. “The general expression for 4,Gat an arbitrary stage ofthe reaction in d\@= 4,64 RTI Q. “The equilibrium constant (K) may be writen in tems of 0* AG=RTINK. “he standard eation Gibts energy maybe caleulted om standard Gibbs energies of formation, A\G*= Say” Zhan G"= BNC) “Thermxtyamicequlibium consantisan eulitrum constant Kexptesed in ters of sctivities (or fgactien) [40.2222] [1 8. Acatalyst does not afect the equilibyiurs constant C1 98. Changesin pressure do not afect the equilibrium constant: (OK @p)_=0. However, partial pressures and concentrations ‘an change in response oa change in pressure LeChatlir’s principle states that a system at equilibrium, ‘when subjected to disturbance, responds ina way that tends ‘to minimize theeflect of the disturbance On. On. On. Increased temperature favours the reactants in exothermic reactions and the products in endothermic reactions, “The temperature dependence of the equilibrium constant is given by the van ‘t Hoffequation: din K/AT=A,H°7RT?. To calculate K a one temperature in terms ofits value at another temperature, and provided 4," is independent of temperature, we useln K,—In K,=—(4,H%R)(UT,~ UT). ‘galvanic cllisan electrochemical cell that produces ‘lecticty as. result of the spontaneous reaction occurring Inside it. An electrolytic cells an electrochemical cell in which, ‘anon-spontancous reaction is driven by an external source of current. ‘Oxidation iste removal of lctrons from a species; ‘eduction isthe addition ofelectzons toa species: a redox. On234 7 CHEMICAL FQUIIBRIUM ‘reaction is reaction in which thete sa transfer of electrons. from one species to another. (1s. Theanodeis the electrode at which oxidation occurs. The cathode’s the dlectrode at which reduction occurs. [116, The electromotive force (emf) i the call potential when tis balanced by an exactly opposing source of potential so that the call reetion oceuts reversibly, the composition is constant, snd no current flows. ‘The cal potential and the reaction Gibbs energy are related by VFE=4,6, ‘The standard emis the standard reaction Gibbs energy ‘expressed as potential: E*= A,C°7V8. ‘The Nemst equation i the equation for the emf of callin terms ofthe composition: E= E°~ (RT/VF) In Q. On. Os. Op. Further reading Articles and texts POW. Atkins and .C. de Paul, Physical chemistry for theif sciences WH. Freeman and Company, New York (2008), ‘AJ.Bardand LR. Faulkner, Hectrochemical methods. Wiley, "New York (2000), (MJ. Blandamer, Cherncal equilibria in solution. Fis ‘Horwood/Prentice Hall, Hemel Hempstead (1992) WA. Cramer and DA. Kealf, Energy ronsletion in biclgicel _membranes, a textbook of bioenergetics. Springer-Verlag, New York. (1950). D.R. Crow, Principles and applications of electrochemistry: Blackie, ‘London (1994). K. Denbigh, The principles of hemscal equilibrium, with applications inchemistry and chemical engineering. Cambridge University Press (198i). Discussion questions 114 plain bow the mixing of reactants ad produce fects the postion of chal equa. 1.2 Suggest how the thermodynamic eulbium consent may respond diesel to changes in pessure and temperature fom the etiam ‘constant expres in ers of pat pests 13 Account for Le Chater’ principle in ter therodyamic quantities 14 plain the molecular bas ofthe van’ Hef equation forthe temperature dependence ofK 1.5 (a) How mayan Eoghan daar be used to decide whether one metal ‘may bewsed to reduce the oxide of anther mata? (b) Usethe Hingham (C220. ‘The equilibrium constant for a cell reaction is related to the standard emfby In K= VEER “The standard potential of couple (E°) isthe standard emt ‘of callin which a couple forms the right-hand electrode and the standard hydrogen electrodes theleft-hand. ectrode. “To calculate the standard emt, form the difference of electrode potentials: B°= E°(right) ~ Elf) ‘The tersperature coefficient of cell potential i given by dENAT= ASE, “The standard reaction entropy and enthalpy are calculated from the temperature dependence ofthe standard emfby: A S*= VEAE*/AT, 6,1 =—MFE*- TOE") Oa. Dz, O23. C2. (CH.Hamann, A. Hamnett, and W. Vielstich, Hectrechemiry. Wiley-VCH, Weinbeim (1998). Sources of data and information MS. Antelman, The eneylopeia of chemical electrode potentials, Plenurs, New York (1982) AJ. Bard, R. Parsons and J. Jordan (o.), Standard potentials in ‘aqueous solution. Marcel Dekker, New York (1985). UN. Goldberg and ¥.B. Tewari Thermodynamics of enzyme catalyzed veactons. Phys. Chem, Ref Data. Part 122,515 (1993). art 2:23, 547 (1994). Part 3:23, 1035 (1994). Part 4:24, 1669 (1995). Part 5:24, 1765 (1995). igzamin it 7.10 t densify the lowes temperate t which rte olde can ‘reduced to zinc metal by carbon, 7 Distngun between cl potenti and clcrometive force and explain ‘vty the laters elated to thermodynamic quantities. 117 Dest the contusions ta the anf of ls formed by combining the detrodes specie in Table. 118 Describes mated forthe deamination of standard porn ofa redox couple 7.9 Devise a method forthe determination ofthe pH ofan aqueous eltonExercises 13) A12257 Kan 1.00 ate tal pressure waters .7 percent dissociated st equlvium by way of thereaction2H,O(g) = 21,8) + O,(g).Calelate (a) K(b) 4.6% and (6) 4 at this temperature 7.410) For te equi, N,O,() = 2 NOG) the degree of disecation, (2298 Kis0.20 at L.O0 bar ttl pressure. Cake) 8,6, (2) Kan (aera 208 K 7.2) Disitogen erodes 18.46 per cent dieined st 25°C and LOD bar inthe equilibrium N,0,(s) e® 2 NO,(g)- Calelate (a) Kat 9°, (0) 46% (6) Kat 1OCC gives that 0" = 457-2 mol" over the temperature range 172)) Molecular bromine 24 px cent discited at 1600 Kand .00barin ‘the egelibrum Br) = 2 Brg) Calulte (a) Ks 25°, (b) 6% () Kat 2000°C given hat = F112] mat over the temperate rage 73) From information in the Dra seton, cau the standard Gibbs energy a the equim constant at) 298 Kand (6) 400K forthe ‘action PLO(s) HCO) P(e) + CO), Assume tat the rection enthalpy is independent of terperture. 73) From information ia the Daa section, calculate the standard Giibs nery an the equim contant at) 25°Cand(b) °C forthe eation {CHL(g) + 3G) = CHA +3 HCA). Assume thatthe reaction eatinlpy Isindependent of tenperatre af) In the as phase reaction 2 A+B <3 12D, twa found thst when 1.00 mol A, 200 m6, an 1.00 ml D were mined ae allowed to come to qulbiumat 25°C, the euting miu contzned 030 mol Cata total Pressure of 1.0 bas Calculate (the mele fractions ofeach species at cequliem (6) K (eK, add) ,0% ap) Inthe gas phase rsction A+B = C+ 2, ses oud that, hen 200 mel A 1.0 el B snd 300 mel D were mined andallowedto come to equlbium at 25°C the reuting mire contained 79 mol Catto resurcaf 00 bat Calate (2) the mole fraction ofeach speci at ulin (6) Ky (6) Keand (@) 6% 15) The standard eactoneatalpy ofZa(s) + 140(g) > 220%) + Hii pprosimatey constant at +224 ket" fom 820 Kup 1280 K-The standard ection Gibbs eneigyis+381 mol a 1280 K Estimate the temperature at which the equi constant becomes eater than 7-8) The standard ebay of acestain reaction is approximately constnt 8141251] ma from 800 Kup to 1500 K. Th standard ection Gibbs ‘ner 122K] ml at 1120 Entiat the empertarea wich the eqlibrism constant becomes renter than | 7) Ti equlbrium constant ofthe eatin 2G H,() °C) + Gy (gs ound 0 ft the expression In K=A + BT + CIT” between 300K 0 00K, ith A= 106, = MARK, and C=1.51> 10°" Calelte the ‘sundard reaction enthalpy and standard reaction entropy 40K. 790) ‘The oir constant oa eeton is found to fit expesion InK= A+ BIT CT beren 400 Kand 50 Kwith A= 20, 8=-1176K, and C= 2.1% 10 K,Caleult the standard rection ebay spd standard ‘ection entopy at 450 K 7a) The standard eeation Gibbs energy ofthe merization of kernel (CeOH) to sobomec nthe gas phase at 03 Kis 4.4K ol" Caeate {he reaction Gib enegy ns mista comsting of 0.15 mol of borneol nd (030 mol ofscbornel when the ttl pressure 0" 77(0) Theequlibsisn presure of Hover sli uranium and rani | Iya, Uy t 500K 139 Po Calle the standard Gis energy of | formation of UH) 500K. EXERCISES 235 178{) Calulte he percentage change in K fo the ection H,CO(e) {CO(g) + H,() whe the total pressuteisinzessed rom LObar to 20barat consantempertire 7.8) Cakulate the percentage change in K; forthe ection CH OHI) + NOdi(g) = HCl) + CH,NO,(a} when the total presurisincreased from ‘Lobarto 20 barat costa terpersire. 7.9) The equilibrium constant forthe as phas omerzation of borneol (Ct/O1) to boborneal st 05 Kls0.106.A mtu consisting of750 gf horned and 14.0, wabornea is acantaioe of volume 0d heated 0 Si Kand allowed a comet ilitrsm Caleslate the mol actions of he ‘wo subtance at egitim, 7.9) The caiibsiam constant forthe eacton Ng) +O,(g) = 21NOK is 1.691021 200 KA mista consisting f5.0 of mitogen and 20 ‘oxygen in container of vlume 10 dns heated to 2300 Kand alowed to ‘come to equim, Calcul the mole fraction of NO at qui 7.0) Whatis the standard enthalpy of ection fr which the equllbrium onsen ss) doubled, baled when the tenipertuteincrened by 10K 2258 7.10) Whatis the standard enthalpy ofa reaction fr which the equiibium constants (2) doubled (6) halved when the temperturesincreased by 15K st310K 71a) The standard Gib ney of formation of Ng) s-165 J mal" ‘st 298K What thereaction Gibb energy when the parti presursof the IN Hy and NH, (ated as peel ass) are 3.0 ber, LObar, sad 40 ber, respective? Whats the spontaneous dtecton ofthe eacton in this ast “T21() The disocition vapour presure of NH,Clat 27°C 608 kPa bt ‘1 459°C thas rir to 113k. Caleulate (athe guia constant, (@) the standard reaction Gis energy, (the taeardentalpy,(@) the Mopar entropy ofdisciaton lla 27°C sure thatthe vapour beaves fsa perfct pa ed that AH an AS*arindependentoftemyeraturein the ‘ange given 7.1) Estimate the temperature a wich CaCO, (cakit) decomposes 32() Estimate the emproture at which C80, 5H,O undernes hydration 39) For Cas) = Cong) +27), K=3.9 10" 8 25°C a the Mandar Gib energy of formation of Caf) 1167 KI mol! Caleuste the nndard Gis energy’ formation of C309, 19910) For Pos) = PY! (oq)+ 21 (oq) K’= 14% 10 at 29°C and he Standard its energy of formation of PL) 173.64 aol" Caleute {he sandard Gibbs energy of formation of PbL,o9). 7-34) Wt the cell reaction and dctrode bal resction ed calculate the standard emf ofexchof the fllowingcl (@) Zalzas0(o9)IARNO,Loqhe (©) CajCact,oq) ENO aq) EL(@ PC (6) PUK, IFe(CN) oq). KylFe(CN, 0g) HCY) Ce 7.940) Wete the cell reaction and decode hall reaction and leat the standard emf of ech the following cells (2) PUCL()INGlag) IK.GO,oq)1A,CO,)IAK (b) Pr 1 Fe*(ag.e (aq SH (og) "(ap Pt (6) GalCx(aghhMnag).H°(2q)IMrO9)1P236 7 CHEMICAL FQUILIBRIUM 798() Devise cin wich the following arth rections and caste the standacd enfin ach ease (@) Zofs)+ C480, (09) +2080 0g) + Cul) (0) 2AgCls) +1 (g) + 214g) +2495) (© 2H,@ +0.) 921,00) “TA8() Devise cls in which he follwing ar the reactions ad calatehe standard emfin ech eae (@) 28s) +2100)» 2NOHKoq) + Hs) © H,@+1,@) 2409) (2 H,0(09)+ 01F(aq) 921,00) ‘6(@) Usethe Debye Hck limiting lw andthe Nernst equation o ‘timate the potential ofthe cel Ag Ags [KBe(a, 0.050 mag) CANO), 0010 mel bg) 25°C. 7.46) Consider the cl PH, (1°91 HICag) AGC), for hi he celleaction 2 AgCls) + H,(g) 2 Ag(e)+2CH(ag).At25°C and a molality of 1 of 0.010 mol hg B= 404688 V. (2) Wht the Noms Problems* Numerical problems 78 The cgi constant fr the reaction, Li) + Beg) <* 2180) 550.164 1 25°C. (a) Calculate 6" for this eacton. (6) Bromine sass introduced int contin with excess solid iodine The pesure and terperstre are ld at .168 stand 25°C, eopectively ind theft restreof eg) tel, Assume tall the bromine ein he gid fort and tht the vapour presse ofiodine negli. (6) Infact she Jodine has measurable vapour Presure at 25°C In this ease ow would he calelation have tobe modified? 172 Consider the diwocation of methane, CH,() into the elements Hg) ad Cs graphite) (a) Given that (CH, §) = 74884) mol and that 1,S°(CHl,.g)=-#067 1K" mal 2298, caleulate the value ofthe culm corstant t 298 K(b) Assuming that 4,1 isindependent of temperature, caltate Kat °C: () Cale the degre of doin, fof methane at 28°Cand total pesare of 1.010 bat (d) Without doing any ‘numeri cleans xpain ow the dese of discon for his action wil change asthe pressure and temperature ae varied. 173 Thecuiivium pressure of Hover Us) and UH,(s) between 450 Kand 715K ftstheexpreson lapfPa) = A+ BIT + Cl), wth A= 69.32,0 14642108 Ky and C=—5.65 Find an expression forthe standard enthalpy of formation of H,(s) and fom teaeust Cf 14 Thedegec of dissociation of CO,() ito CO(e) and () at bigh temperatures was fone to vary wih temperate as fous: at 1a 25047 _Asuning 6, #1 tobe constant over tis temperature range, calculate K, {2.11% and 5°. Make any jotifable appronmations 175 Thestandod ection ental forthe decompesiton of CaClNH(9) {eto Cas) and NH,(@) ine constant at +764) mol beiwear 350 K nd 470K. The equim presi of Nin he presence of CCL, NH, quation forthe cal eacton (0) Calelate AG forthe cll reaction (6 Assuming thatthe Debye-HAcke iting lw bolt this concetration, calelte E*UAGCL, Ap) xT) Caleulat the euibeism constants ofthe allowing rections a 25°C fiom standard potenti daa: (2) Sofa) +0) = 280(ag) (01 So(o) 428g) = SOC (0) +2 00) 1TH) Casula the equim constant ofthe folowing reactions at 25°C fiom standard potenti date: (2) Sofa) + GSO) = Cal) + S180,09) () Cu2(ag) + Cuts) 22 Cag) 738) The emf ofthe cll Ag Al) Allag) Ags 109509 Vat 25°C (Calelate (a) te solubity product of Al ad () tsb. 16() ‘The eaofthe cl BiH, 1B) Bi is~096 Vat 2°, Calelate (3) the selubty product of Bi, nd (b) tesolubiy 1.71 kPa 400K Find an expression forthe temperature dependence of 0,6" nthe sare range. 78 Cleat the equi constant ofthe reiction OO(g) + Hyg) <2 11,004 given that, fr the production oii formaldeyde, 4" 112895 mol at 28 Kan thatthe vapour pressure of formalde 1500 Towra ht ternperatare, Er hectic aid was evapora in container of voime 2145 cm at 437 Kand stan extemal presse of 1091s andthe container was hen sealed. The ‘a of ai pesntin the seal taner wa 0.0519 The experiment wis ‘peated withthe same container but at 471K, ant was found Ut C380 ‘acetic awa preset Calelatetheequbriam constant forthe ‘Simeriaton of the acd inthe vapour and te enthalpy of vaporization. 178 Asc container wos filed with 0.00 eal Hg) 040 mat (and (6200 mat lg) t 870K antl pressure 1.00 br Calelate the szounts of the componcrsin the misture acquit given hat K = 970 forthe reaction Fife) + L(g) = 211. 79 Thedlsocation of, canbe monitorod by measting the and theese sults are fallow: ial pressure, m1; = ws Toop 62447500 SRL Wm 249 ASS 2A wheres theamount of atoms perk of molecules in the mitre, ‘which occupied 42.68 cr! Calalat the gulf constant ofthe QH,(oq) E*= #06004 V. the ell Hg gC) HClaq)Q-QH, las prepared, andthe measured cel potest i 40190 ¥, whats the pH ofthe HClsleion? Assume thatthe Detye-Hickl iting law is appiable 748 Consider thecal Za(s'Z2C, (0.0050 mally") [H.C gl. oe which the all reactions Hg, C,) + Za(o) > 21g) +2G faq) +209), (Giver that #* (Zn Zn) = 0.7628, f° (HCl Hi) = #02676, and that theerafis 1.2272 V (a) write the Nernst equation forte cll Determine (@ the standard emf (6) 6,46" and forthe cel action, (6) the mean ionic activity and activity coefcent of ZC fom the meastred cl pote and (e)themeas oni activity cote of ZA rm the Debye-Hch lit law (0) Given that QEIOT), = 452. 104V KL Calculates and At TA7 Thecef ofthe cel P| Eg] HCleg) Hes Ha) hasbeen ‘measured with high prec (G). HillsandD.LG. Ie, J. Gh See, 311 (4951) wit the following eu 125°C: iemalhg) 60775469 nv oto 06825 asi366 70938 asa nossrs sess PROBLEMS — 237 Determine the standard emf ofthe el rd the mean activity coefcent of| HCLat hae mollis. (Makes least-squares ofthe data tothe best straight line) 7.98 Cael mesurent of th fof th cl Pe p9INSOHog {20100 moll), Nang 01125 mol | ABCs) TAg heen {cpored (CP. Beton MEGEC: Canacs AK Covigin and}. Dolson Chere So Fredy Tons 16,49 1873), Arg ne data ithe {eowingifomation @c mp 30m HN ume ste .0012 Cae pk, a hes tenpratres and he standard etapa atopy of Ue auoprtcasar waters 250 7139 Measurements ofthe eof cls ofthe ype AglARXC)[MXC)IM, HgIMX{0,)1AgX(0) Ag, whereM, Hs denotes an amalgx andthe leo isan lal metal halide sled in thlen lca ave bee reported (U. Se, Cte, So. Faraday Tras 168, 2006 (1973) and some selec for LiCl are gives blew Estimate the acti coeticient the oncenration motked snd then we this alco cele activity Cecfcens fom the measured el potential atthe othe coneeitations Base your answer athe following version a the eatended Debye Hackal lane egy with A= 1.461, B=1.70,4=020, an jcotig) 0555 OusNAIY 162 02IL LOD 1350, av cuz 4H mK 07915601856 17.20 Thestandatd potenti ofthe AgCUAg,CT couple has been measured ‘very carefully ones range of temperature (RG. Hats and VE Bowers. Res [Nat Bia Stand. 3, 28 (1854) an te resus were ound tft tbe expesion Y= 0.23699 ~ 4.8564 10-“(G°C) ~ 3.4205 10 (6°) +569 100°C) (Calelate the standard Gib energy and ethapy of formation of (aq) 30d Itsentopy st 298 K. 724¢ (a) Dervea genera ton fr (212p), for decuochemical cls cmploying recantin any sate of mater, (5) ECafen an K.Pepentrock (Z Physik Chom. 167A, 465 (193) ealuted the change n vue forthe seaction TIG(S) + CNS (oq) > TIERS) + Cl (eq) at °C fom density data and bisa ,V=-2.666 + 0.080’ mol. They ako meawired the em of ‘he cll lg) |TICNS() KCNC TCI TI) a presses wp to 1500 stn. Theis results are given inthe following abe pin 100 250750805 rom this information, obtain (E0P), t XFC and compare tothe vale obtained fom 4,V.() Fitthe dt toa polmonial for E agains p. How constants (Q0p),(€) From the plots etinateanefective ‘sothermal compres forthe cell as wae. 1.224 Thelabe belo summarizes the efobserved forthe cal AIH, 1b) BL, ), Bag 1 AgC1 Lg. Fach easement i made atequ may coecnvations of aio chore (BI and 2 aminopyiin (B). The dare for 25°C ents oudthat E*= 22251. Uethe ata to dtermine pK, forthe acid t 29°C andthe mean activity ‘orice (of BH as faeton of molality (2) anni strength U).Use theodended Debye-Hrcel equation forth rian activity coef in the form For, = 009141 mol ame tog = 1081. = ga238 7 CHEMICAL EQUILIBRIUM where A=0.5051 and B and kare paremetes that depend upon theions Draw araph ofthe mean activity coeciet wih b= 0.4 lk! a osreon inet) oor onze FOSoIV a7Ms2o77ss o7igaR asks 7080 Wine) ce =a? BRSOIV O76 O75 00 MEST O68 Hin Use thera software ors spreadsheet. 1.28 Superhemyy dements are now ofconsideabe intrest, partially because sigs of ability ae starting to emerge with cement 14, which has recently een made. Shorty before wn (lsc) bleed that theft superheay cement had been discovered, an atempt waemade to prdict the chemical proprtics of ununpentium (Up element 115, 0. Keller, CW. Nestor ad B Fricke Pps. Chon. 78,1945 (1974) none part of he paper ‘hestandard enthalpy aad entropy of the reaction Up aq) 31) > [ups + #(a) were estimated fom the following at: (Uup) = #15eVs Up) = 552€V, Ag (Up aq) =—3.22 eV, Supa): #1 MmeV I, S7Uup,s)=59 meV K Esinate the expected standard potential ofthe Uap Wap couple 17.26 Sodive Morideiswoutnaly added wo pubic water supplies Because itis ‘pow that Muerte ion can prevent tooth decay In eid scctive ‘decode used inthe als f water samples crystal ofa, doped with Ee, denoted ara provides a semipermeable bre twee the tee. solution ond th sotion inside the etre (he filing sion), which contains 0. mol bg! NaF) and 1 rol NaCl). A iver-siber ‘horde electrode immerse the filing slsion somes 02 potestiomiter apd temo the xl canbe mcessted apis an oppropriate {efeenc lsrod. ie follow that te balf-celfor a frie sectve cestode isrepresented by ‘Aa{s)| AGC) NeCag by), NAF (aq, by IEuLAF() ag.) ‘whereby and ae the mollis of uotdeion inthe Eling and et ‘alton, especie} Desive an expen for the emo this acl (b) The fori setve electrode just described is ot sensivet aq). ‘irae io isthe only interfering species, with yg =O. Use thi ‘information and theft that K, of HE 3.5% 1 at 298 Kt specify ange ‘of pt values which the electrode responds accurately tothe actty of in ‘ete slsion a 298K. ‘Theoretical problems 125 Beprssthe qulibrium constant ofa pat-phae reaction A432 2 in ems of the qulibrium alucof the extent of reaction, & gen that ‘nly And Bere preset in stoichiometric proportions. Find an ‘eapresion for $a faretion of the total presse, po he reaction mitre snd sketch graph ofthe expression obtain 7.28 Find an expresion forthe tarcad section Git energy ata terperstre Tn terme of ts ale st nother temperature T andthe cefent, and cin the expression for the mala eat expat ited in “Talie22 Flat the standard Gibbs ene of formation of H,O(0 31372 K Gocnits value 21258 K. 721 Shove that the onc strength of soation ofthe sparing slublesat ‘Mocand the fie soluie sat NX is dominated by the concentration Caf the later, anit yl vo we de Debye“ init aw, the salty ithe rsned nln given by seis when K, ssl (ina sense tobe pei). ‘Applications: to biology, environmental science, and chemical engineering 7.28 Hereweinvestgne the molecular bsisfor the aberration that the yds oF ATP is exergonic at pH=70and 310K. (a) eis though thatthe eergoniity of ATP hydrolysis i dc part to the fat het the anda “etopies of hydrolysis of polyphosphates are pesive Why woulda increase in catopy accompany the hyelyais of iphosphate group intoe 10 at, Po, =0.132 tm, plese] = 5.610 ma ds [ATE|=[ADP|=[P] = 117 moldm °-pHt=7.4, T=310K. Assoming tht actives canbe replaced by the mimrieal values of molar concentrations, sult the ickencyofserobi respiration unde: these pysologial conditions. (6) Atypical diesel engine operates between 1.473 Kad T, = 1923 Koith ficiency that is appronimately 75 per cent ofthe theoretical imi of (1=1,/,) (ce Section 32). Compare the effcenc of peal deel engine with tha of aerobic espiration under tcl physical conditions ce put. Why sbiolgial energy convention more rls fen tha energy aversion ina diesel engine? 721 Inanarobi bacteria, the source carbon may bea molecule other tha Lucas ad the final electron acceptor issemne molec the than O, Could Abocterium evolve to use the cthanlitrat painstead of the gucncO, palracasource of melabotic ney? 7.82 Ifthe mitockondsa electric potential between matrix andthe internembrane space were 70 mV, as iscommen for oger membranes how ‘ich ATP could be eyhesined from the teanspatof4 ma 1, asming the ll dierence semaine esate! 1.89 The standard potenti of proteins ae not commonly meatred by themethods described inthis chapecr Boss proteins often lone he tive ‘sructure and function when they react on the surfaces of decodes Ina iterative method, th oxidized protin i llowed to eet with ae appropiate dacton door in elton, The standard potential ofthe ten then determined from the Nero equation the brim ‘oncentaion fal pein solution andthe known standard pte foftheclctron donor Wesbal strat thie meth withthe protein ‘jtochromec The one-lecron reaction betwee etecome rf and 26-chlovoindophera, 0, ane flowed pectrophotomtrcly baaise ‘each ofthe four eis in solution ha disint alo, or sbsorption sectrum. Wet th eaction 38694, +D gg €7y* Dy wet thesubsriptsox anid ed refer io oniied sd educa tates respectively. (a) Consider, and Fo be the standard potentials of ¢rochrome cand D, respectively Show that tequila Ce), pltofla((D,Jo/lDale) seit ln l/l is iear with ope of ae yimerepe FES, ERT, ere equim activites ae replaced by the merical als of ‘quiibrum molar ancentatins(b) The fellowig data were obtained for ‘the reaction between onized tochrome cand reduced Dina pH. buffer 21298 K-The 260s [Dyl/Dyale 24 Feeley mereadused by tiratinga elton containing Oude cpochrome cond vedoced Dvith scluion of dium ascorbate, which isa strong reuctat. rom the ta and {he standard potential of D of 0.27 V, detec the standard potential ‘jtochrome cat pE6S ad 296K, [Pae/lPaily, 0279 N008S 0257 00K? OWES 0238 0534 lertle/lotla, 00106 00250 O6RSK 0197 0535 OOS 138 7.38 Thedlimerination of AO inthe Antarctic winter stratosphere isbeleved to play an important prt in that eio's severe seasonal dplton of orone “The allowing equilibrium constant are based on measurements by RA. Cex sand CA Hayman (Natute 382, 796 (158) on the reaction 210 (g) > (20), K4xnh Sexo) Lasxac? sa7xtet sanxtet 62x? TK 18 ow K 62x sri Zon. (2) Deie the values of 4,11 and 4,5*for this reaction. (b) Compute the Standard eshalpy formation andthe standard mar entropy of (10), sven ,F1%(C1O}= #10188) mot! and $y(C10) =226.6] 1 mob (CHC “Handbeok 200). PROBLEMS 239 15. Nitric ac hydrates have received much attention as posublecatahts forheterogencous reactions thatbring about the Antarctic azone bole. Wersnop eral investigated the thermodynamic stability of these hydats under conditions typical ofthe pla winter stratosphere (DE Warsaop, LE. Fox MS. 7ahniner and SC. Woly, Sere 258,71 (1983). Standard reaction Gibbs energies canbe compute for the following reactions at 190 K from thir at: © HO@)H.00) 2,6°=-23.68 mot* (i) H.0(@) + HNO (@) 5 HNO,#,0G) ——_A\GT=-872KI mot (Gi) 2140 (g)+ HNO, (g)-> HNO; 21,06) _4,67=-856 4 mo (i) 3F0(@) HNO, (@) HNO3H,0(8) _A,G*= 1128) mot" Which slid isthermodyamialy mos stable at 190 Kf yy =13%10" bar 204 jo, ba bart Hint Ty computing 4G for each resion under the prevaing conditions sf more than oz solid fons spoetaneousy, amine AG forthe conversion of oe slid to ashe 17. Suppose that an iron catalyst» prticlar manfactutng part predcesarpmonia inthe most est-effective manner at 450°C whenthe resure isch that Gor the reaction $N,(g)+ 4 Hy(g)—>NE,(g) i ol 500 mol (a) What presaresnceded? b) Now suppse tat anes ‘tats develop that is most est fective at 400°C wen the presse pve the same vlc of 8,6 Whit presure seeded wen the new ety i ‘ed! What rth advantages of the ne ctalt Assume that (al ass fre perfect ses ce that (al aes are van der Wasl gases Isotherm oF '3.1T, inthe pressre ange 100 atm p< 400 ata ae nended wo derive the answer (¢) Do theisetherms you pleted enti Le Chater’ principle concerning the response of equilibrium changes in temperature and pres?PART 2 Structure In Part 1 we examined the properties of bulk matter from the viewpoint of thermodynamics. In Part 2 we exarrine the structures and properties of individual atoms and molecules from the viewpoint of quantum mechanics. ‘The two viewpoints merge in Chapters 16 and 17. 8 Quantum theory: introduction and principles 9 Quantum theory: techniques and applications 10 Atomic structure end atomic spectra 11. Molecular structure 12 Molocular symmetry 18. Molecular spectroscopy 1: rotational and vibrational spectra 14 Molecular spectroscopy 2: electronic transitions 15 Molecular spectroscopy 3: magnetic resonance 16 Statistical themedynarrics 1: the concepts 17 Stalistical hemodynamics 2: applications 18 Molecular interactions 19 Vateriais 1: macromolecules and aggregates 20. Materials 2: the sod state