5 CHEMICAL EQUILIBRIUM —___ Chemical reaction can be classified as . Ree reactions: The reactions which move only in one (i je reactions: The reactions which move in both direct do not reach to completion. art is - ae characteristic property of reversible reactions which can be defined as the saris eA ire backward reactions occurs at the same speed. r= k{APBT n= ke(C}IDT ky Equilibrium constant, K,=> direction, i.e. forward direction. ‘ions under similar conditions and Time = FACTORS AFFECTING EQUILIBRIUM CONSTANT Methods of representing the equation: For a reversible reaction, N, +3H, == 2NH, i [NH] “pl? Consider the backward reaction, then , [Ns] HAP ne 2 [Nas] akied K, Stoichiometry representation: ifferent stoichiometric equations, then the value of ‘When a reversible reaction can be represented by di equilibrium constant will be numerically different. (a) 2NO2(g) == Nols) + 20,8) _ [lot [No,] (b) NOg) == GNsW)# 020) [Na]"[02] [No,] The relation is Kema CESS Use of partial pressure: aA + bB == cC + dD x, (Py Tope Ke = KedRT) P > Kp (D(a Where An=n-m Temperature: log Ke. _aH_[ 1, ~1 ] KK, 2303R| TT, DEGREE OF DissociaTION (Dissociated amount by 1 mole) The degree of dissociation 1s dependent on density measurement PClsig) PCIi(g) + Chie) Initial moles a 0 0 At equilibrium acl - «) aa aa Since total mass is constant, M a(l+a)_M a m M_ D orl+a-M mi d D ~ V.D of undissociated PCIx d= V Dof gascous mixture at equilibhum Hence, Reaction Quotient (Q.) For the reaction; aA+bB == cC+dD g -/ctPI (ay [B] (i) Q.> Ke ~ backward reaction occurs Gi) Qe 0, reaction moves in forward direction, if AH < 0, reaction moves in backward direction. (ii) When pressure is increased, if An > 0, reaction moves in backward direction. if An <0, reaction moves in forward direction. SAT ore TOLi (iii) When volume is increased if An > 0, reaction moves in forward direction, if An <0, reaction moves in backward direction i in that (iv) Tf concentration of only one of the species of the reaction is increased, then reaction occurs direction in which concentration gets decreased. (v) Addition of an inert gas (a) At constant volume: no effect on equilibrium constant but total pressure is increased. (b) At constant pressure, if An > 0, reaction moves in forward direction, if An <0, reaction moves in backward direction. (vi) Addition of catalyst: Equilibrium constant remains unaffected but rate of reaction increases. Standard Free Energy & Equili AG? = -RTInKeq = ~2.303 RT log Keg (i) AG? = ~ve of Keq > 1; forward reaction is feasible (ii) AG? = +ve of Key < 1; reverse reaction is feasible (iii) AG® = 0 or Kay = 0; reaction is at equilibriumILLUSTRATIVE PROBLEMS x For the dissociation reaction jon in terms of Ky and (otal pressure p, N20. (g)2no. (g) derive the expression for the degree of dissociati Sot N20, (g)===2No: (g) 1 0 t30 tot, (I-a) vtalleP 2a a “Tapas ay At a certain temperature and total pressure of 10° Pa iodine vapour contain 40% by volume at atoms I2(g) = 2h (g) calculate Kp for equilibrium. ‘Sol Partial pressure of I atom is 40 Fh 99 Prt =O 10% = 4410" Pa 100 Partial pressure of In molecule is = xp 6 Pp 1s 799 Pot = Gaxl0 = 6x10" Pa For given reaction 2 : =P) Lo 67.10! Pa (,) Ly K, SE Setar MOTO TOT TT)A Sol. Sol. ‘A.280 wl fn, and 100 ml Mavk aro separated by a stop cock, At 380 K, the nltrie oxide in the ‘irger flask exerts a pressure of 046 atm, and the smaller one contains oxygen at 0.86 atm, The knses are mixed by opening the stop cock. The reaction occurring are 2NO + Or —> 2NO: = NO. ‘The first reaction ts complete while the second one is at equilibrium, Assuming all the gases to behave Ideally, caleutate the Ky for the equlltbrlum rection if the final total pressure Is 0.37 atm, 0.46% 250x10" 0082x350 0.86% 100% 10"" 0.082350 Aor the completion of first reaction, Moles of oxygen left = 10°, Moles of NOs left = 4 x 10°? 2NO.(x) === N,0,(g) initial 4 0 equilibrium 4x10%(I-x) 4x10" (x/2) ‘Total moles at equilibrium = 4x10 ((1~ x) + (x/2) }+ 107 0.37 x 350 x 10 = 10%4 ~ 4+ 2 + 1) x 0,082 x 350 On solving we get, x = 0.2439 Moles of nitric oxide 4x10! Moles of oxygen 3x10! cNo, = 3X0. Partial pressure of NOs 7 121 9s and Partial pressure of N20 25%037 9,04 Kp Ok 64 atm! 025x025 Following equilibria are established on mixing two gases Az and C. () 3Ax(g) == Ao(g); Kp = 1.6 atm? (ii) Aa(g) + C(g) Arig) If Az and C are mixed in 2 : 1 molar ratio, calculate equilibrium partial pressures of Az, C and AC and Ky for equation (i). The total pressure is 1.4 atm and partial pressure of Ac is 0.2 3A.(g) == Ad(g) => Py, =0.5 atm Let the partial pressure of Az and C before the start of reaction be a and a/2 atm respectively Aa(g) + C(g) = ArC(g) Ifx moles of Ao reacts to form x moles of AzC, then 14=05+0.2+ pyc tPe = Pac +Po=0.7 vi) aW2—x+x=0.7 > a= 14 atm Now, partial pressure of Az consumed in Ist reaction = 3 x 0.2 = 0.6 atm Partial pressure of As consumed in IInd reaction = 1.4~3 x 0.2~0.5 =03 atm=> Py. = 0.3 atm6. Sol. ___ iE woclation of HI at a particular femperature Is 0.8 find the volume of 1,5 Tequlred to react completely with the fodine Present at equilibrium in aciaje 0.135 mole of each Hh and Is are heated at 440 K in a closed vessel of capacity The degree of dis Na$10s solution Conditions when 1, 2HKy) | LOR 04 Kok. 04x04 "(02 = WB) + egy 04 HR) + gy 2HKig) K O.135 0.135 O13S-x 0.135-x« 2x k, <1. 20 4° (0.135—x) x= 0.045 moles of ly at equivalence point = 0,09 L Vs hypo Equivalents of 1p = hypo equivalents 0.092 =1.5%Vx1 V= 144 m1 4 Container whose volume is V, contains an equilibrium mixture that consists of 2 moles each of PCls, PCly and Ch: (all gases). The pressure is 30.3975 kPa and temperature is T. A certain Amount of Cl: (g) is now introduced keeping the pressure and temperature constant until the (Guilibrium volume changes to 2V, Calculate the amount of Cl that was added and the value of Ky. PCIs(g) ==" PChi(g) + Ch(g) Atequilibrium — 2mol 2mol — 2mol Total pressure = 30.3975 kPa = 3 atm = P(say) PP Ky= Presa a) When chlorine is added to the system. The system will try to nullify the effect and hence formation of PCIs will be preferred Since, P and T are constant m=6 — [“Vi=V,V2=2V] *. m= 12 moles Say, ‘a’ moles of Clz were added PCls = PCh + Cl; GESTS)pT Xe ehN] ae lc CC CC Initial © 2 2 2 Final 2+x 2-x 24a-x mr -12=6+a-x 1 A-X=6 sep oe 242°X)(2-x) _ ioe cers w@) Solving equations (1) and (2), we get 0 a=— moles 20 Hence, ap moles of Cl: was added. a PCls dissociates into PCls and Ch: thus PCls(g) ———_ PCh(g) + Chg) If the total pressure of the system in equilibrium is P at a density p and temperature T, show that Degree of dissociation a= a where M is the relative molar mass of PCs. If the vapour density of the gas mixture at equilibrium has the value of 62 when the temperature is 230°C, what is the value of P/p? Sol. PCIs(g) == PCh(g) + Chg) Since PV=nRT= “RT M Sat sone PV P pRT 2 VD. (d= PRE @ ?P PCls(g) === PCh(g) + Cla(g) Initial = C 0 0 Ategm. C(I -a) Ca Ca Total moles at equilibrium ___Initial vapour density Total initial moles Vapour density at equilibrium cl+a) _ D cd site M2 pRT/2P pRT casey oe ORT M ifd= 62, 2 104.25-62 _ 9 6g 0 2 coe = 0.3327 atm ((gm/L)When 1-pentyne (A) is treated with 4N alcoholic KOH at 175°C , it is converted slowly into an equilibrium mixture of 13% 1-pentyne (A), 95.2% 2-pentyne (B) and 3.5% of 1, 2-pentadiene (©). The equilibrium was maintained at175°C . Calculate AG" for the following equilibria, BSA B=C From the calculated value of AG; and AG; indicate the order of stability of (A), (B) and (C), Write a reasonable reaction mechanism showing all intermediates leading to (A), (B) and (C). Sol. Pentyne =“ 2 - Pentyne + 1,2 ~ Pentadiene (A) (B) (c) Ateg.m% 13 95.5 35 = [BIIC] _ 95.235 [A] 13 For eqm. BA x, - [4] ~[B] From Eqs. (i) and (ii), K, = Ke = 256.31 0” i) K, =35_ 20013 256.31 AG" =-2.303RTlog,, K = -2.303 «8.314 448log,, 0.013 = 161787 = 16.178 kJ Stability order for A and B is B>A Similarly, B= C [4 [B] _KlA] (By _ 256.31x1.3 © 95.2%95.2 + AG? = -2.303RT og, K = -2,303 «8.314% 448log,, 0.037 K, = 12282) = 12,282) Thus, stability order for B and C is B>C Total order of stability is B>C>A Esea SOLVED PROBLEMS Subjective Question Prob. 1. Sol. A theoretically completed equilib dehyde to glucose in aqueous solution ig ene ibrium constant for the polymerization of formaldehyde t0 g 6HCHO—=C,h,,0, Ma 1.0 M solution of glucose were to reach dissociation equilibrium with respect to above equilibrium ‘what would be the concentration of formaldehyde in the solution? [0] “~ [HcHoy 6x10” = —1_ [HCHO] [HCHO] = 1.6 « 104M Objective Questions Prob. 1. The equilibrium, PCIs(g) = PCI3(g) + Clx(g), is attained at 25°C in a closed container and an inert gas He is introduced. Which of the following statements are correct? (A) Concentration of PCls, PCl; and Clz are changed (B) More Cl. is formed (C) Concentration of PChs is reduced (D) Nothing happens Sol. Since decomposition of PCls is carried out in a closed container. When helium gas is introduced the volume remains constant and there is no change in the partial pressures of PCls, PCls and Clh. Therefore, nothing happens on introduction of helium gas and constant volume. Hence, (D) is the correct answer. Prob. 2.40% of a mixture of 0,2 mol of No and 0.6 mol of Hz react to give NH; according to the equation, Nz(g) + 3Ha(g) = 2NHs(g), at constant temperature and pressure. Then the ratio of the final volume to the initial volume of gases are (A) 4:5 (B) 5:4 (C710 (D) 8:5 Sol. Ne+ 3H; = 2NHs t=0 02 06 0 att=t 0.2-x 0.6-3x 2x 40% of N2 = 0.2 x0.4 = 0.08 40% of Ha= 0.6 x0.4 = 0.24 ¢. Number of moles of No remaining = 0.2 - 0.08 = 0.12 Number of moles of Hy remaining = 0.6 ~ 0.24 = 0.36 ‘Number of moles of NHs formed = 0.16 Total number of moles = 0.12 + 0.36 + 0.16 = 0.64 Final volume _ Final_moles _ 0.64 "Initial volume Initial moles 0.80 Hence, (A) is the correct answer. Prob. 3. In the following equilibrium, the example of phase equilibria is (A) H(g) + b(g) = 2HI(g) {B) CaCO; (s) = CaO(s) + COr(s) (C) H20(s) = 1200) (D) PCIs(g) = PCh(g) + Ch(g) So. Ae CaeEL GEE Prob. 4. In a system, A(s) = 2B (g) + 3C (g) Sol. Prob. 5. K, for a reaction at 25 Sol. Prob. 6. The dissociati Sol. If the conc. of C at equilibrium is increased by a factor of 2, it will cause the equilibrium concentration of B to change to (A) bwo times the original value (C)2N2 times the original value (B) one half of its original value (D)1/22_ times the original value A(s) = 2B(g) + 3C(g) jum respectively Let, x and y be the concentrations of B and C at equilibri Ke = x?y’ a) Now, the concentration of C is changed from y to y’ such that y’ = 2y. If x" is the new concentration of B Ke = ('P (y'P = ('FQy)? (2) From Eqs. (1) and (2) ((8y) x 8 22 Equilibrium concentration of B changes 10 nA times the original value . Hence, (D) is the correct answer. °C is 10 atm. The activation energy for forward and reverse reactions are 12 and 20 kJ/ mol respectively. The Ke for the reaction at 40°C will be (A) 433» 10'M (B) 3.33 x 107M (C) 3.33 x 10'M (D) 4.33 107M Enthalpy changed of a reaction is given by AH = Exn~ Exo where Eyip and Eq are energies of activation for the forward and backward reactions AH = 12- 20=-8 ki/mol K, forthe reaction at 25°C = 10 atm. Since Ky is expressed in atmosphere, An = +1 10 eK) = Ke(RT), Ke= = 0. Ko= Ke(RTI™ Keo ogp 1x 298 K, at 40°C is given by K, “8 (K.), _ AH (3 +]- 8100 15 __ ogni eK), “330K | TT, | 2303*8314 298313 (Ke)il(Ke)os = 0.85 (Ke)uo = 0.85 x0.4= 0.34 M Hence, (C) is the correct answer. ion of phosgene, which occurs according to the reaction COCI; (g) == CO(g) + Cha (8) rocess, Which of the following will increase the degree of dissociation of COCI3? (B) Adding helium to the system at constant pressure (D) Reducing the total pressure is an endothermic pt (A) Adding Clz to the system (C) Decreasing the temperature of the system (B,D) IGMP-CHEMISTRY-CHEMICAL EQUILIBRIUMff MEGACOSM See ecco yA REASONING TYPE QUESTIONS This section contains reasoning type questions. Each question has 4 choices (A), (B), (C) and (D), out ‘of which ONLY ONE is correct. 1 Net Kp can be equal to or less than or greater than Ke STATEMENT-2: K, =K, (RT)", thus, Ke and Ke depend upon temperature (A) STATEMENT: is Tre, STATEMENT.2 is True; STATEMENT? is comet explanation for @) oe is Troe STATEMENT-2 is True; STATEMENT-2 is NOT a correct explanation Hane oe tomnsyeu Sol —(B) 2 STATEMENT-1: The concentration term of pure liquids and solids can be ignored while writing equilibrium constant expression, and STATEMENT-2: The concentration of pure liquids and solids donot remain constant. (A) STATEMENT-1 is True, STATEMENT-2 is True; STATEMENT-2 is correct explanation for STATEMENT-1 (B) STATEMENT-1 is True, STATEMENT-2 is True; STATEMENT-2 is NOT a correct explanation for STATEMENT-1 (C) STATEMENT-1 is True, STATEMENT-2 is False (D) STATEMENT-1 is False, STATEMENT-2 is True Sok — (C) COMPREHENSION Read the following passage and answer the questions: The dissociation constant is related to the standard free energy difference between products and reactants in the following way. If Ky is the dissociation constant, then standard free energy dissociation is related ask, =10°° 7", If AG® is negative, this means that product P is more stable than starting material and vice-versa. Following is a type of association reaction, where standard entropies of A, B and C are 191, 130 and 192 J K* mol respectively at 25°C, Aig +3By) = 2Cips AH? = 46 KT kk Sol. 2 Sol. 3 Sol. 4. Sol. wt Value of AS’ for above reaction is: (A) 137]! mol! (B)-197 JK" mot? (©) +127 K' mot! (D) +227) K! mot! (B) AG® for above reaction is (A) -3.3%10°d (B) -3.98x10'J (©) -1.3x10°U (D) -1.0x10°J (A) log Ky for the above reaction is (A) 5.84 (B) 5.98 (©) 3.85 (D) 484 (a) Value of K, for the reverse reaction, 2C=—==A +2B is: (A) 1.2%10° atm? (B) 1.4107 atm? (C) 1.44%10% atm? = (D)1.4x 40° atm? © RATS aSMATRIX ~ MATCH TYPE QUESTION _ Match the followmy 1B) NH COONH, (s) === 2NH, +CO, (2) Lop ee | O) Ha(g) <1, (g) === 2HI(g) 1D) | 280, (x) +0, —=280,(e) | es ee | | @ K | (r) | Ke? K | __| |] (3) | Addition of inert gas at constant pressure shift the equilibrium in the | lem side | Sol. 2 (A) NHHS(s) == NH, (g) + (B) | QqQBop;Cors;Dor 3 Match the followin, | (A) | AG (p) Reaction is at equilibrium } — —— ets —— | (B) For a heterogeneous endothermic equitation | (q) | Equilibrium constant decrease as term is | with equilibrium constant K increased | | (©) | A(g)—=B(g)+C(g) + heat (1) | The equilibrium is unaffected | equilibrium constant K Sol. A>pBornCoq STAT :Ci) a Answer 4, 5 and 6 by a table. PPropriately ‘matching the information given in the three columns of the following | (iii) | atm! [| 30, () | nount |) K> Ke eee gc Oma OD ere ay | So, 70:8) =80,(g) Gi) | am! } 2HF(g) = H,(2)+F,(g) | Hy F Ly) | atm? LOS) | Ky 2 Ke a aii 4. Which of the followin, g combination is correct ? [A] () (ii) (S) [B] (11) (ii) (Py (C} @) Gi) (Q, (D] (Iv) () (P) 5. In the given column-Il, only correct combination for (R) Ky = K ? {A] (IV) (i) (P) (B} (11) (i) (Ry {C] di (iti) (Q) (D] at) @) ) 6 In the given column-II, which combination is correct for (iv) atm=?? {A} (D Gi) (sy [B} (IV) (iv) (Q) (C] ) Git) @ 1D} dv) Gi) P) Sok 4.C3 5D; 6B SINGLE INTEGER ANSWER TYPE 1. 280, +0, ==280, Starting with 2 mol of SO, and 1 mol of Oo in I-L flask, mixture required 0.4 mol of MnO; in acidic medium. Find the K. value, Sol. (2) 5SO, +2MnO, —>2Mn?* + SSO} 2 mol of MnO, =5 mole of SO>. +04 mlof MnO; = 1 mol SOs. 280, + 0,280, 2 1 0 (2-2x) (I-x) 2x (2 - 2x) = I mol (as determined by MnO; ) 22x _ — 2x i =—*=1M, [so; IM [80,]=7=1 (so; -_ [Sof {s0.J'[0.] 2. For the equilibrium NH,CONH,(s) == 2NH(g) + COa(g) Poo, = tatm at 100°C. What will be the equilibrium constant at 100°C in atm, Sol. (4) NH,CONH,(s)===2NH,(g) +O, (g) 1 0 0 (I-x) 2x x Let Proiat be p ; “ Peo, “Beate g el Pus, = egay egos am WES ee ee[NUMERICAL VALUE ANSWER TYPE_ Prob. 1. Sol. Prob. 2. Sol. Prob. 3. Sol. Prob. 4. Sol. Prob. 5. Sol. GSS 2803(g) is 4.0 atm at 1000 K, he constant, Kp for the g) + Og) = The equilibrium constant, Kv for the reaction 280x(g) + O2(8) S02 and $Os is the same ? What would be the partial pressure of O> ifat equilibrium the amount of 0.25 atm The equilibrium SO2(g) + Foxe) = SOQ) is established in a container of 4I- at & Particular tivel: temperature, If the number of moles of SO2, O2 and SOs at equilibrium are 2, | and 4 respectively then find the value of equilibrium constant 4.00 The equilibrium constant of the reaction Hy(g) + In(g) = is reduced to one fourth of its original volume, the value of the equi 2HI(g) is 64. If the volume of the container librium constant will be 64.00 In the following reaction started only with As, 2Ax(g) = 2As(g) + 3A2(g) + Ad(g) le f Mole fraction of Ap is found to 0,36 at a total pressure of 100 atm at equilibrium. The mole fraction of Ag(g) at equilibrium is 0.28 Two solid compounds X and Y dissociates at a certain temperature as follows X(s) = A(g) + 2Blg); K, = 9x10 * atm’ Y(s) = 2B(g) + Clg); K,, = 4.510? atm’ The total pressure of gases over a mixture of X and Y is 0.45 atm