College of Mechanical Engineering Technology / Benghazi CHEMICAL ENGINEERING DEPARTMENT Chemical Engineering Thermodynamics II CHE 407 THE STANDARD GIBBS ENERGY CHANGE AND THE EQUILIBRIUM CONSTANT TT Aystpegsth easigt oo dy) pall alah op GS dil, «iHeat Effects STANDARD HEAT OF REACTION Heat effects of chemical processes are fully as important as those for physical processes. Chemical reactions are accompanied by the transfer of heat, by temperature changes during reaction, or by both, The ultimate cause lies in the difference between the molecular configurations of products and reactants. For an adiabatic combustion reaction, reactants and products possess the same energy, requiring an elevated temperature for the products. For the corresponding isothermal reaction, heat is necessarily transferred to the surroundings. Between these two extremes an infinite combination of effects is possible. Each reaction carried out in a particu- lar way is accompanied by particular heat effects. Their complete tabulation is impossible. Our object is therefore to devise methods of calculation of the heat effects for reactions carried out in diverse ways from data for reactions carried out in an arbitrarily defined standard way, thus leading to standard heats of reaction. This reduces the required data to a minimum. Heats of reaction are based on experimental measurements. Most easily measured are heats of combustion, because of the nature of such reactions. A simple procedure is provided by a flow calorimeter. Fuel is mixed with air at a temperature 7, and the mixture flows into a combustion chamber where reaction occurs. The combustion products enter a water-jacketed section in which they are cooled to temperature 7. Because no shaft work is produced and the calorimeter is designed to eliminate potential- and kinetic-energy changes, the overall energy balance, Eq. (2.32), reduces to AH=0 Thus the enthalpy change caused by the combustion reaction is equal in magnitude to the heat flowing from the reaction products to the water, and may be calculated from the temperature rise and flow rate of the water, The enthalpy change of reaction AM is called the heat of reaction. If the reactants and products are in their standard states, then the heat effect is the standard heat of reaction. The definition of a standard siate is straightforward. For a given temperature, A standard state is defined as the state of a substance at specified pres- sure, composition, and physical condition as, e.g., gas, liquid, ot solid. ‘The standard states in use throughout the world have been established by general agree- ‘ment. They ate based on a standard-siate pressure of 1 bat (10° Pa). With respect to composi- tion, the standard states used in this chapter are states of pure species. For liquids and solids it is the actual state of the pure species at the standard-state pressure, Nothing could be simpler. However, for gases there is a small complication, as the chosen physical state is the ideal-2as state, for which we have already established heat capacities. In summary, the standard states used in this chapter are: + Gases: The pure substance in the ideal-gas state at 1 bar. + Liquids and solids: The real pure liquid or solid at 1 bar. One must understand that standard states apply at any temperature. ‘There is no specification of temperature for any standard state. Refer- ence temperatures, also in use with heats of reaction, are entirely inde- pendent of standard states.Standard Heat of Reaction With respect to the chemical reaction, aA + bB > IL + mM, the standard heat of reac- tion at temperature 7 is defined as the enthalpy change when a moles of A and » moles of B in their standard sues ai temperanure T react to form 1 moles of Land m moles of M in their standard states at the same temperature T. The mechanism of this change is immaterial to the calculation of the enthalpy change. One may view the process shown in Fig. 4.2 as occurring in a “box of tricks.” If the properties of reactants and products in their standard states are not significantly different from the properties of actual reactants and products, the standard heat of reaction is a reasonable approximation to the actual heat of reaction. If this is not the case, then additional steps must be incorporated into the calculation scheme to account for any ifferences. The most common difference is caused by pressures higher than appropriate to the ideal-gas state (as for the ammonia-synthesis reaction). In this case, enthalpy changes for ‘transformation from real-gas states t0 ideal-gas states and the reverse are required. These are readily made, as shown in Chapter 6 fy =a mol-s! —> — fi, =1 mol: . “Box of Tricks” . tig = b mol-s1 —+ 1+ jig = m mol-s* In standard states, at T In standard states, at T OJs1= AHG J Figure 4.2: Schematic representation of the standard heat of reaction at temperature T. Property values in the standard state are denoted by the degree symbol. For exam- ple, Cf is the standard-state heat capacity. Because the standard state for gases is the ideal-gas state, C> is identical with Cj, and the data of Table C.1 apply to the standard state for gases. All conditions for a standard state are fixed except temperature, which Is always the temperature of the system. Standard-state properties are therefore functions of temperature only. ‘The standard state chosen for gases is hypothetical or fictitious because at 1 bar actual ‘gases deviate from the ideal-gas state. However, they seldom deviate much, and for most pur- Poses enthalpies for the real-gas state at | bar and the ideal-gas state are negligibly different ‘When a heat of reaction is given for a particular reaction, it applies for the stoichiometric coefficients as written. If each stoichiometric coefficient is doubled, the heat of reaction is doubled. For example, two versions of the ammonia synthesis reaction are written: No+3H)—+NH; AHiyy=—46,110) No+3H)—2NHy AH3yg = —92,220)Heat Effects ‘The symbol AH indicates that the heat of reaction is the standard value for a temperature of 298.15 K (25°C) and for the reaction as written STANDARD HEAT OF FORMATION Tabulation of data for just one temperature and for just the standard heats of reaction for all of the vast number of possible reactions is impractical. Fortunately, the standard heat of any reaction at temperature T can be calculated if the standard heats of formation at the same temperature are known for the compounds taking part in the reaction, A formation reaction is defined as a reaction that forms a single compound from its constituent elements, For example, the reaction C+ 40; + 2H» > CH,OH is a formation reaction for methanol. The reaction H,0 + S03 + H,80, is nota formation reaction, because it forms sulfuric acid not from the clements but from other compounds, Formation reactions are understood to produce 1 mol of product; the heat of formation is therefore based on I mot of the compound formed. Heats of reaction at any temperature can be calculated from heat-capacity data if the value for one temperature is known; the tabulation of data can therefore be reduced to the compilation of standard heats of formation at a single temperature. The usual choice for this reference temperature is 298.15 K or 25°C. The standard heat of formation of a compound at this temperature is represented by the symbol AHj,,. The degree symbol denotes the standard-state value, subscript f identifies a heat of formation, and the 298 is the rounded absolute temperature in kelvins. Tables of these values for common substances may be found in standard handbooks, but the most extensive compilations available are in specialized reference works.!? An abridged list of values is given in Table C.4 of App. C, and values for many additional compounds are given in publicly available online databases."> When chemical reactions are combined by addition, the standard heats of reaction may also be added to give the standard heat of the resulting reaction. This is possible because enthalpy is a state function, and its changes for given initial and final states are independent of path, In particular, formation reactions and standard heats of formation may be combined to produce any desired reaction (not itself a formation reaction) and its accompanying standard heat of reaction. Reactions written for this purpose often include an indication of the physical state of each reactant and product—that is, the letter g, , os is placed in parentheses after the chemical formula to show whether it isa gas, a liquid, or a solid. This might seem unnecessary because a pure chemical species at a particular temperature and | bar can usually exist only in ‘one physical state. However, fictitious states (e.g, the ideal-gas state) are often employed for convenience in such calculations,Standard Heat of Formation ‘The water-gas-shift reaction, CO(g) + Hx(g)> CO(g) + H2O(g) at 25°C, is commonly encountered in the chemical industry. Although it takes place only at temperatures well above 25°C, the data are for 25°C, and the initial step in any calculation of heat effects for this reac- tion is evaluation of the standard heat of reaction at 25°C. The pertinent formation reactions and the corresponding heats of formation from Table C.4 are: CO%(g): Cls) + Oxlg) > COA) H4{g): Because hydrogen is an element CO(g): Cls) + $O2(g) + COL) H,O(g): Ho (g) +402(g) > H20(g) ‘Because the reaction is actually carried out entirely in the gas phase at high temperature, con- venience dictates that the standard states of all products and reactants at 25°C be taken as the ideal-gas state at 1 bar, even though water does not actually exist as a gas at these conditions." ‘Writing the formation reactions so that their sum yields the desired reaction requires that the formation reaction for CO» be written in reverse; the heat of reaction is then of opposite fd heat of formation: COs(g) + Cls) + 021g) Cs) + 502 (g) + CO{g) AHSy¢ = —110,525 J H3(g) + $O2(g) + H20(g) AMT5gg = -241,818 T COx(g) + Ha(g) > COlg) + HzO(g) AH 395 = 41,166 J ‘The meaning of this result is that the enthalpy of 1 mol of CO plus 1 mol of HzO is greater than the enthalpy of | mol of CO plus 1 mol of Hp by 41,166 T when each product and reae- tant is taken as the pure gas at 25°C im its idee 1 bar. In this example the standard heat of formation of H,O is available for its hypothetical ideal-gas state at 25°C. One might expect the value of the heat of formation of water to be listed for its actual state as a liquid at 1 bar and 25°C. Asa matier of fact, Values for both states are given in Table C.4 because they are both often used. This is true for many compounds that normally exist as liquids at 25°C and 1 bar. Cases do arise, however, in which a value is given only for the standard state asa liquid or for the ideal-gas state when what is needed is the other value, Suppose this were the case for the preceding example, with only the standard heat of formation of liquid H2O available. We would then include an equation for the physical change that transforms water from its standard state as a liquid into its ideal-gas state. The enthalpy change for this physical process is the difference between the heats of formation of water in its ‘two standard states: —241,818 — (—285,830) = 44,012 7Heat Effects ‘This is approximately the latent heat of vaporization of water at 25°C. The sequence of steps is now: CO2(g) + Cls) + Org) AHg = 393,509 J Cs) +4.02(g) + CO(g) AH5gg = 110,525 J Hy(g) + $02(g) + 1200 AH qg = -285,830 I 2 0(0) > H20(g) AHig = 44,012 COA(g) + Hog) + CO(g) + H2O(g) AH Soy = 41,166 F This result is of course in agreement with the previous answer. Example .5 Calculate the standard heat of reaction at 25°C for the following reaction: AHCI(g) + O2(g) + 2H;0(g) + 2Cl2(g) Solution .5 Standard heats of formation at 298,15 K from Table C.4 are: HCI(g):—92,307 J H20(g): 241,818) The following combination gives the desired result 4HCK(g) > 22g) + 2Cla(g) A395 = (4)(92,307) 2H(g)+ Ox(¢) > 2H20(g) AMBpg = (2)(—241,818) 4HCI(g) + 02g) > 2H20(g) + 2Cls(g) AH Sng = 114,408 JCalculation of Equilibrium Constant from Data ‘The Gibbs energy of reaction may be obtained from the Gibbs energy of formation which is the Gibbs energy of reaction when the species of interested is formed from its pure elements, as found in nature, that is, Elements Ag, Species ° The Gibbs energy of formation of a pure element, as it is found in nature, is equal to zero. ‘The Gibbs energy of formation is available for many species at 25°C and | bar. The Gibbs energy of reaction is then given by Ag" rxn.29 = Siv,Ag’ rao (64-1) In this equation, the stoichiomettic coefficients for products are positive and those for reactants are negative. The equilibrium constant is then evaluated: (64-2) Example -I - Calculate the equilibrium constant for the following reaction using the data at 298°K H2O(g) + CHsOH(g) <> CO2(g) + 3H2(8) H,O(g) CH;OH(g) COAg) Ha(g) Ag": (ki/mol) 228.57 = 161.96 = 394.36 0 Solution —-—— Ag’ mas = Y1v,Ag? 298 Ag’ nn.an = (Ag* eos + 3(Ag" D2 — (Ag"Di20~ (Ag cro Ag? rmn.298 = (— 394.36)co2 + 3(O)n2 — (— 228.57)20- (— 161.96 )crs0H Ag’ ron205 =— 3.83 kJ/mol The equilibrium constant is then _ Ag’rno ) -3830 0) _ Ke = 389 _| - 4.69 os RL PL (e314)(298.15)Example -2 Find the equilibrium concentration of N:O.(g) [Nitrogen nitroxide] due to the chemical reaction at 25°C and 1 atm. 'N:0:(2) <> 2NO2(g) The following data are available: (1) N2O4(g) <> Nog) + 202(g) Ag’rn.1 =~ Ag*enzo4 = ~ 23.41 kcal/mol (2) 0.5Nolg)+ Ox(g) <= NO2g) Ag'an2= Ag"svo2 = 12.24 keal/mol Solution — The reaction NxO,(g) <> 2NOx(z) may be obtained by combining reactions (1) and (2) (1) + 2(2) => N2Ox(g) <> 2NO2(g) Therefore Ag’an = Ag’nat + 2Ag" a= Ag*nn = 1.11 keal/mol = 4644 J/mol = - RT In K Ag’tx204 + 2Ag"tnoz = — 23.41 +2(12.24) K= exn(- Me } The equilibrium constant K can also be expressed in terms of the activities 4644 i aS) = 0.1563 (8.314)(298.15) «1 | atm, equation (E-1) becomes Po) (YoY Pro, ( Tatm ) Pro, Yaol) fio, Pro, Late } Since P= 1 atm, equation (E-2) becomes (2)(E-3) We have N03 NO: Total Initial 1 0 1 Final 1-¢ 2g 14g The mole fractions of N.O, and NO; are given by yaoi yroa 2 Me TE PN eS Substituting yyaos and yyoo into equation (E-3) gives (2) 167 = 9.1563 —“S__ = .1563 ee (oy +¢) 1 0.1536 = = # = 0.19: 42 = 0.186301 — > G= PEE = $= 0.1923 The equilibrium concentration of N:O«(g) is then ee YN204= 0.6774 14 If the Gibbs energies of formation are available at the reaction temperature, the equilibrium constant can be calculated directly from K= wo ‘=| However most reactions we want to study are at temperatures different than 25°C where data are not available. We need an expression to determine the equilibrium constant at any temperature from one set of Gibbs energy data