5.8 Concentration equilibrium constant (Kc) and Mole-fraction equilibrium constants (Kz) Previously we obtained expression for K’p of an ideal gas reaction. The subscript P in Kp emphasizes that equilibrium partial pressures of reactants and products ate used in equilibrium constant expression. It is possible to express equilibrium constants using: equilibrium concentrations or equilibrium mole fraction of reactants and products for an ideal gas reaction. Relation between Kp and Ke Concentration equilibrium constant (Kc) aA(g) + bB(g) = mM(g) + L(g) (5.48) is related to Kp as shown below. If n; moles of a component é in an ideal gas mixture is pI concentration C, = 7 and the partial pressure pi is given by pV = niRT p= ar = CRT (5.72) for a general reaction resent in volume V, then. Replacing all the pieq terms in equation (5.57) in terms of C;RT we may write Kep = (Cus RT/PY" (Crs RT/P*y! (Caeq RT/P°)" (Ci,eq RT/P?)? — Cotaa)” (Cra! (REE © (Caca)* (Caen)? (r) Multiplying and dividing each concentration in equation (5.73) by standard concentra tion C® which usually is taken as LinolL~! we can write for general ideal gas reaction (5.48), $ (5.73) (Cntea/ C2)" (Creal?) Gee HP Cy ea/C¥* (CaimlOP \P? (6.74) CORT ”/ mol 4 = Ke( Pe ) where m +1 — e = Ko( RTA (6.75)equation tere) esl that Kc is also independent of pressure and is a function of T only ee Ise 7 snd P® are constants. This relation (5.75) between Kp and Ke allows calculation of Ke from the known value of Kp of an ideal gas reaction at a given temperature. Kc for an ideal gas reaction of the general type represented by 0= 5 4A; is given by Ke= n(S Ce a)" (5.77) where C° = 1mol/L Kp and Kc have uo units and they are dimensionless quantities. It is to be noted that C°RT and P® in equation (5.74) have same units so that the ratio £ (5.74) is dimensionless, Cieq/C® terms in equation (5.74) and equation (5.76) has no units and no dimension. m +1 — a —b in equation (5. 74) must have no dimension. Since An has unit of mol, An is divided by mol so that An/ mol in equation (5.75) is dimension Earlier we have seen that Kp is a function of T only for an ideal gaseous reaction. It is to be emphasized that Kc is also a function of T only and independent of P for ideal gas reaction. This has already been indicated because Kp and Kc are related by equation (5.75) which does not contain any P term and where C°, P° are constants. It will be seen later that AX, depends on P for gaseous reactions where An # 0. in equation » Example 5.3 For the reaction, 3H2(g) + No(g) = 2NH3(g), the value of Kp = 6.80 x 10° at 25°C. Calculate the value of Ke at 25°C. Solution: The relation between Kp and Ke is given by RT An/ mol re(E) Kp Pe C°RT _ (LmolL7!)(0.083145 L bar mol”! K71)(298.15 1K) _ by ae a ee 2mol For the reaction given An =2-3-1= So, Kp = Ko(24.79)? 1c HOME (2479) = 6.80 x 10(24.79)? = 4.17 x 108 5.9 Relation between Kp and Ke Partial pressure p; of a component / in ideal gas mixture is given by Dalton’s law p= Pu where P is total pressure of the mixture and 2% is mole fretion of component é in the mixture,Eee — - (equation 5.57) we may way for Kp , in the expression for “PF Replacing each pi by Px ee, (Pameal PY” (PELs, Kp = ~f] Pxpea/ a metab ha 5) @ =-(— P %) FAeq” Beg mtt-a-b P 7 -k.(%) (ay where ri 3 Ky = b (5.89) wy eq Be i eactiol 5.48 Se 2 relaty is mole fraction equilibrium constant for ideal gas reaction (5.48). So the re ation between Kp and K, is eh Animal 2 Kp = K,(P/P?)™ (5.1) where An =m+l—a—b. the mole fraction equilibriuy For a general reaction represented by 0 = Lo viAi, constant K, will be given by Kz = [| (ticea)” (5.82) We have seen that K’p is independent of P and is dependent only on T and since P is involved in the relation between Kp and K., (5.81) we must say that KC, is dependent both on T and P in case when An # 0. For this reason Kp is more useful than K, 5.10 Relation between Kp, € and total pressure P for ideal gas reaction cage of appropriate physical property like of equilibrium concentration of a species “isnt ANd Pressure etc. Measuremet equilibrium extent of reacin es ees INES & Of the teaction. By measuring tt the value of equilibriu action (equilibrium advancement of reaction) can obtait Bicheleesan. ee Constant from the known st, artis tr, Se, one a eel ae Pree Ge and total see ee ide es ure ol lew Teactions are derived below. Th Pes ~ The meani. described in terms of equation (539). of the advancement of reaction € has beet conductance, absorbance, refractioe Dissociation of N2O4(g) at T and P N204(g) = 2NOo(q) (5.83) 5 ° we start wit atin Suppose we start with Lmole of NaO4 (g) and dissociation equilibrium is allowed to reach at a given T, P. Let advancemey L ; reach a e e et advancement of reactions (extent of reaction) at equilibrium é degree of dissociation at e ; is &¢ (The deg “ssociation at equilibrium ae for this reaction is same as €) Jarious quantities at é Various q equilibrium such as equilibrium mole numbers, equilibrium mole factions, equilibrium partial pressures of both the reactant (NgO4) and product (NO») are given in columns under the formul 1 ti las of reactant and product for the balanced chemical reaction N2Oa(g) 2NO2(g) (i) Initial mole numbers 1 0 (ii) Equilibrium mole numbers 1 2. (Using relation nj = n? + 14€, eq. (5.39)] (iii) Total mole numbers at equilibrium = 1—£ + 2€. =1+& if at i= Ea 2&e Equilibrium mole fractio (iy), cal ae 1+& Le (v) Equilibrium partial pressures ¢ =#) Be (5) da Using the equilibrium partial pressures for reactant and product, we can write es oral Aree) (e)} rol) (EE) (p) - ap EG) 4g (2) = Se i is Jation involving Kp, ¢ and total pressure P of the reaction. aes oe ale & at a given T, P we obtain Kp value at the temperature T from the expression (5.84). ‘This equation (5.84) is also used in calculating & at a given TP from the knowledge of Kp of the reaction at T. It will be discussed :°C) is obtained from the standard Gibbs ener, pin the r > is obtained f 2 roducts, the later that K’p for a reaction at 25 tos andl products, the valiey renctan compound) values of the reac i . For decompogit formation, AG} as0c ( td text book Ponti i standa: 7 "Thus eckael are available in tabular form in any 5 + solved for &. Thus eqiuati “ie Sone “INO2(9) the equation (5.84) can be solv’ On reaction, NoO4(g) = 9). (5.84) can be rearranged to give (1~€&) _ (P/P?) ace ie Kp 1 1 _ (p/P?) 424 Kp 11. P/pe we - it kp 1 _ Kp+4(P/P°) 4 Kp 2 Kp 1 8 Rp $a(P]P) = 14 (PIP) &=7—1__, 7B (5.85) {1 + ro(P/P?)} & value can be obtained using this equation for any gaseous dissociation equilibrium of the type A(y) = 2B(9), as for example N204(9) = 2NO2(g), Clo(g) = 2CX(g). Tt was pointed out earlier that since P° = Ibar, it is not always displayed and equation (5.85) is also written as___NAg)+ 3g) = __2NHG(9) {) Initial mole : ; - (ii) Equilibrium mole numbers : ap ~ &e 3 — 36 Ee [Using relation n, = nf +n, €4. (5.39)] (iii) Total mole numbers at equilibrium = 1~ £43 ~ 36, 496 = 4-26, = 22-6.) (iv) Equilibrium mole fractions Ee 3(1 = fe) 22-&) 2(2-&) 2(2-&) (v) Equilibrium partial pressures jaf) p 3=&) 266 22-€e) 22 Ee) 2(2—- Ee) For the reaction Na(g) + 3H2(g) = 2NH3(9) (pyi.eq/P°)? Kec ee 5.88 Prisca) PV Pie PP a Using the values of equilibrium partial pressure of No(9), Ha(g) and NH(g) in equation (5.88) we obtain Crear 2(2— &) P® T=GuP\ (30=&) P\ (cee B) Geass 9) 4c {2(2- &)}" 1 Ke = Gag * m0-&)* * PPE 462 (22 =e)? (6.89) Kp = a7 - &)(P/PY? If is small, then 2— & = 2 and 1 — = 1 and we have Kp = 2 64 (5.90) Tee | ney eae which is often written as, 2 64 91 es 64 fe (5.91)1 mixture it is possible to get €, ay is obtained by using equatig, i) fl otal prema Ff rt ent only on T aed not on P. Ta Oa is to be remembered that Kp 91) does not affect Kp but €, value eee, aoa et ie Ae Pe ema at constant T. Kp for the bes ee a from the relation AG? = _)#tiy Na(g) + 3Ha(g) = 2NHy(g) can be calculated fr ong whee AG ‘paaytNi) ~ AGH(Na) = BAG GUHA). Neca AGF (Conan are obtained from literature at 25°C. Once K’p is obtaine Knowing mae ANY oti temperature can be calculated. This will be discussed son. ene ae the value ; at a given temperature the equation (5.89) or (5.90) can ese 0 obtain Advair, of reaction at equilibrium (€, value) at a given T and P of experiment, For the reaction No(g) + 3H2(g) = 2NHs(y), Kp has been expressed in of total P and &. However, without using equilibrium advancement of reactig, it is sometimes convenient to express Kp in terms of total pressure P and Ping (equilibrium partial pressure of ammonia). Expression for Kp for this reaction i ggg by equation (5.88). Tt has already been mentioned that to simplify writing P° in (p/p, terms where P? = 1 har is very often not displayed (see equation 5.58) and equa, (5.88) is simply written as From the analysis of the equilibrium 2 P = — Nine (5, PN2caP itp ,eq For the mixing of 1 mole Ny and 3 mole Hp, we have the relation Plia.ea = 3? N2,0q (6.83) Also we have total pressure P= Prog + Pttz.0q + PNHa,eq (5.94) From (5.93) and (5.94) we see that P = ADs 0a + PNtIg.0q Bs PN2eq = es Combining (5.92) and (5.93) we may wri ia Se = 256 Pitts (5.97) 27 (P= prttseq)* ‘This equation (5.97) expresses K’p in terms of total pressure (P) and equilibrium partial pressure of ammonia (Pts .oq)- Itis known that Kp is a function of T only and not dependent on P. The appearance of P in right side of the above equation (5.97) clearly indicates that at different total P, the value of PNiis,eq Will be different in order to maintain the constancy of Kp at the given temperature of experiment. Equation (5.97) can be written also as 2 16 KY? = 16 __Pntiseg PS SPP = pita)? be If Kp of the reaction is known at a given T, the above equations can be used to calculate Nity.eq Value of any total pressure (P) at the given T. On the other hand if pyuis,eq is measured at total pressure P (constant value) at some experimental temperature then Kp of the reaction can be calculated using equation (5.98). If the balanced chemical equation is written as 3.Na(g) + $Ha(9) = NHs(9) then equilibrium constant for this reaction will be equal to the square root of Kp of the reaction represented by equation Na(g) + 3H2(g) = 2NHs(9) For the dissociation reaction equilibrium represented by 2NH3(g) = No(g) + 3H2(9) the equilibrium constant will be the reciprocal of Kp of the reaction represented by equation No(g) + 3Ha(g) = 2NHs(9) 1 mole Na(g) and 1 mole Hz represented by equation (5.87) we considered are 1 and 3 respectively (the reactants are in NHg(g) formation reaction from For the NH3(g) formation reaction that initial moles of Na(g) and Ha(9) stoichiometric proportions) and there was no deal with initial moles of No(g) an 4 tumbers of NHy(g) being zero. If advancement of reaction at ea equilibrium, moles of No is 1— whereas mole of Hy is 1 ~ 3Eo was 3—3€,) and mole of NH is 2. Total moles at en is assumed to occur at constant T, P (total pressureNa(g)+ _ 3H2(g) = 2NHy(G) (i) Initial mole numbers (ii) Equilibrium mole numbers 1-& = 1-3 2, (iii) Total mole numbers at equilibrium = 1-& +1-36e + 2e = 2-2. (iv) Equilibrium mole fractions 1-& pp 1- Sep _% (v) Equilibrium partial pressures 3-% = =2- 2 2-2 For the reaction No(g) + 3Ha(9) = 2NHs(9) (Prtsea/P°)? Le (5.88) KP = Daal P*)(Ptigeal PS Putting the values of equilibrium partial pressures of the three species No, Hy ani NHg given in the table into the above expression for Kp, we may write (ee) Kp = ave y Ge PA @ P ) (} = 36 P (= 2G Pe} \2— 2€. =) wp See (2 = 2€0)4 1 ‘Hp sees se No he) gs * 2-2 * 1 ej —36.)3 * (PPP - 462(2~ 26,)? ~ (= €)(1 = 36.)5(P/ Pe pe eae ea (1 ~ 36¢)3(P/Pe)? When one mole each of N. n 2(9) and H: reaction represented by equation (5.87) for the same reaction wh BY (a) are mixed the expression for Kp for Jen one mole Na(y) ae berm My ) ree moles H2(g) are mixed a