Fuel value per em? =3.94 keal @ CCL, CCI, (g) AHP +30.5 kj mol Gi) CG) +2C1g) + CCI, (a) AHP ~ -135.5 kj mol Gil) C(s) + C(g) AHe= +715 kj mol (iv) Clg) > 2Cl(g) AHP ~ +242 kj mol Energetics @ 4.71 Required equation CCI (g) + C(g) + 4Cl(g) AH = ? Equation (ii) +2 » Equation (iv) ~ Equation Gi) Equation (i) gives the required equation AH = 715 + 2(242) ~30.5 ~(-135.5) = 1304 kj mol Bond enthalpy of (C-Cl) bond = ~ 326 Kj mol"CHAPTER 5A multiple-choice questions. Chapter Contents Law of mass action; Equilibrium constant, Le Chatelier’s principle (effect of concentration, temperature and pressure); Significance of AG and AGo in chemical equilibrium; and Various levels of Type of Reactions Chemical reactions are of two types: Irreversible Reaction: Such reactions occur in one direction only and get completed. Example, (i) When unreactive products or solid products are formed NH,NO, —4> N, + 2H,0 2KC1O, —4—> 2KCl +30, (ii) All precipitate reactions are irreversible Example, BaCl, +H,SO, + BaSO, + 2HCI aq ag ppt aq Pb(NO, ), + 2KI + Pbl, + 2KNO, (iii) Neutralization reactions are also irreversible: H,SO, + 2KOH = K,SO, + 2H,O (iv) Redox reactions are also irreversible 2FeCl, + SnCl, > SnCl, + 2FeCl, (¥)_ Combustion reactions are also irreversible: 2Mg + 0, > 2MgO Reversible Reactions: Such reactions occur in both directions ie., forward and backward direc tion however never complete as the products can give back the reactants under same or different conditions. Example, N, +0, + 2NO 3Fe + 4H,O + Fe,0, + 4H, = Vepourization of water in open flask is imevers- ible reaction while in closed flask it is reversible m= Decomposition of CaCO, in open flask is irre- versible reaction while in closed flask it is reversible.5.2 ™ Chemical Equilibrium ible Differences between Reversible and Irreve Reactions: Irreversible Reaction It takes place in forward It takes place only in as well as in backward forward direction. directions. It can never be com- Itmay be completed pleted. Equilibrium state can be Equilibrium state is attained never attained. The change in free The change in free energy (AG) is zero, _ energy is negative ie, AG<0, EQUILIBRIUM The word “equilibrium” in physical sense in explained as the “No change of state of the body” When the two opposing process (reaction) occur simultaneously with equal rates, the system is in the state of equilibrium. Equilibrium is classified as follows Equilibrium Physical Equilibrium — Chemical Equilibrium ——— Homogenous Heterogeneous Chemical Equilibrium Chemical Equilibrium When an equilibrium exists between same chemical species, itis called physical equilibrium. Example, HO® _ OC) HO® lee Tatm Water When an equilibrium exists between different chem- ical species, it is called chemical equilibrium. N, (@) +3H,(@) = 2NH,(@) CaCO, (3) = CaO (5) +C0, (@) If a chemical equilibrium has only one phase, i called homogenous and if more than one phase it is called heterogeneous, H,(g)+1,(g) = 2HI(@) R-COOH (1) + R-OH() = R-COOR() + H,00) Phase = I. Homogenous chemical equilibrium 2HgO (s) = 2Hg () +O, (@) Phase Heterogeneous chemical equilibrium CHEMICAL EQUILIBRIUM It is defined as: “It is the stage of a reversible reac- tion at which the active masses of the reactants and the products become constant in mixture and do not change with time” and rate of forward reaction is ‘equal to that of backward reaction. Or “Itis the state of a reversible reaction at which mea- surable properties like colour, density, pressure con- centration are nearly unchangeable.” Equilibrium state Rate —> ‘Time at which {equilibrium acheived time —> Here V, and V, are rate of forward and backward reactions respectively. i.e., Equilibrium is the state in a reversible reac- tion at which the rate of forward and backward reac- tions or two opposing reactions are same. Features of Chemical Equilibrium = It is obtained only when reversible reaction is carried out in a closed space. = Here rate of forward reaction is equal to rate of backward reaction. = Here both forward and backward reactions are taking place with same rate hence the relative amounts of the reactants and products present at equilibrium does not change with time. m= At constant temperature it is characterized by properties like colour, density, pressure ete. = Itis possible from both the sides, m= It is dynamic in nature. It means the reaction or process is not going to be ceased as reaction occurs in both directions with equal rates. = A catalyst cannot alter the positive of equilibrium as it accelerates both the forward and backwardChemical Equilibrium m™_5.3 reactions to the same extant this means the same state of equilibrium is reaction ie., a positive cata- lyst can set up equilibrium in less time but can not change it = At equilibrium AG is equal to zero ie., AG = AH-TAs So AH = TAS ‘= Under the similar conditions of temperature con- centration and pressure, the same state of equilib- rium is reached Example, When an equimolar mixture of H, and I,is heated to 713 K, 80% of this mixture changes into the prod- uct (HI) and if product is again heated as 713 K only 20% of it changes into H, and I, Active Mass or Molar Concentration It means the concentration of the reactant expressed in moles per litre or the pressure of a reacting gas, in atmosphere. It is usually denoted by putting the symbol of the reactant in square bracket. E.g., [A] Cyor A= EVO (A) = molarity Here 7 is the activity coefficient In case of very dilute solution, y is one. This means we can used molarity. = Its unit is mol it = At constant temperature Partial pressure 0¢ Active mass = Active mass of a pure solid or a pure liquid is assumed to be one, = Active mass of any gas at NTP. is 1/224 Law of Mass Action It was introduced by Guldberg and Waage. It states that “the rate at which a substance reacts is directly proportional to its active mass(effective molar con- centration) and the rate at which substances react together is directly proportional to the product of their active masses” each raised to a power which is equal to the corresponding stoichiometric number the substance present in the chemical reaction, \ A+B <——~ C+D If active masses of A, B, C and D are [A], (BI, [C], [D] respectively then Rate of reaction of A ot [A] Rate of reaction of B & [B] V, & [AI [BI=K, [A] [B] V, « (C] [D]=K, (C) DI] Law of mass action is not applicable for solids as for them active mass is always one Example, KC1O, > 2KCl +30, Solid Reaction Quotient or Concentration Quotient (Q): It is defined as the ratio of concentration of prod- uct upon the reacting species at any point of time other than the equilibrium stage. It can be deter- mined as follows: If we consider a reaction m,A+m,B +n,C +n,D than - Jon pre = BF Q can be denoted as Q,. or Q, if we use concentra- tion in terms of mole per litre or partial pressure respectively. fw When [C" [DJ* = [A BP". Q=K (reaction is at equilibrium and rate of for- ward and backward reactions are equal) = When Q> K here reaction will proceed or favour backward direction this means product changes into reactant to attain equilibrium. = When Q c+D V,@(A][B] or=K, [A] [B] V,a[C][D] or=K, [C] [D] We know that at equilibrium V, So K, [A] [B]=K, [C] [D] {C] 1D} [AT B] [C][D] | [product] TATIB] © [reactant] * cO™st temp or For a reaction given below equilibrium constant can be given as mA+mBenC+nD (ch! pyr REMEMBER Completion of reaction & Ke Stability of reaction 0 I/Ke Stability of product o Ke Factors Effecting Equilibrium Constant Ke does not depend upon: = Initial concentration or pressure of reactants and products involved m= The presence of a catalyst = The presence of an inert gas material. = The direction from which equilibrium has been set up. Ke depends upon: Equilibrium constant depends upon following factors, 1. Temperature The variation of equilibrium constant with tempera- ture is given by Van’t Hoff equation as follows: K=Ae-anr K,__ ane (,-T) 8 K-2303R —T, KaT (AH=+ve) K @1/T (AH=-ve) When a graph is ploted between log,,K and I/T a straight like will be formed and the slope is equal to =AH? 2303R ‘A log,,K log,.K Wr i Endothermic Exothermic = Incase of AH = 0, equilibrium constant does not depend upon temperature. = In case of AH = positive or endothermic reac- tions, equilibrium constant is more at higher tem- perature, = In case of AH = negative or exothermic reactions, ‘equilibrium constant is more at lower temperature. 2. Mode of Representation of Reaction Let us consider a reaction A+BeC+D _ (1D) Ke> Tay IB) ‘Now if we write the above reaction as follows: C+D SA+BChemical Equilibrium ie., Ke = I/ Ke” Example, 280, + 0, = 280, (So, Ke=i50, If the reaction is reversed 280, $0, +0, eon SOF IO} 1 [So,F ~ Ke 3. Ste jiometric Representation of Chemical Equation Let us consider a reaction A+B—C+D (C}[D] Ke = MCD) °° TATIB] If we write the above reaction as follows: mA+mBon,C+nD then (cr pe Kear BF eg.-(I) 2NO, + N,+20, [NO,}* Here Ke= NTTOF (2) NO, +4 N,+0, . (NO _ Here Ke= Ty rrjoj = VKe (3) N, +3H, + 2NH, and NH, + 4N, +3/2H, then Ke’ INKe 4. Nature of reactant or product ‘The value of equilibrium constant also depend on the nature of reactants as well as of the products it means the value of equilibrium constant changes by changing them Example, N, +0, = 2NO N, +20, = 2NO, For these reaction the value of equilibrium con- stant differs as product differs Equilibrium Constant in Terms of Partial Pressure: If partial pressures of A, B, C, Dare given as P,, P,P. P,, respectively then for the reaction Kp is given as mAvmpeon-rnD an If we use total pressure, moles of reactant and prod- ucts than Kp can be find out as follows a Kp= Itis interesting to know that Kp can exist only when equilibrium satisfies these two conditions. (One of the reactant or the product must be in gaseous phase. Gi) No component of the equilibrium must be present in solution phase Relation between Kp and Ke: _ el" PI PRP Pa As PV=nRT So P=y RT As n/V = Concentration So P=CRT K,= [CP (RT [DP RTE T Px BP RT [RT] 12) cet +m) Kp=Ke(RT) t= -tat>m um of gaseous products ~ Sum of gaseous reactants An=(n, +n,)-(m, +m) e (RT Kp Units of Equilibrium Constant (K): Ke = (mollit) Kp= (atm)5.6 ™ Chemical Equilibrium REMEMBER = If Aniszero Kp =Ke Here Kp and Ke have no units eg.-N+0, + 2NO = If Anis positive then Kp > Ke eg.-PCl, PC, +Cl, 2NH, + N, + 3H, m= If Anisnegative then Ke> Kp e.g.,- 280, + 0, > 280, Equilibrium Constant for a Multi step Reac- tion: For a multistep reaction equilibrium constant is given as K=K,.K,.K, It means if a equilibrium reaction can be expressed as the sum of two or more equilibrium reactions, then the equilibrium constant for the overall reac- tion is given by the product of the equilibrium con- stants of the individual reactions. e.g. H,0, + 2H" + 2b +1, + 2H,0 Steps: HO, + OH-+HOI (K,) H’+OH-+H,0(K,) HOI +H" +P +H,0+1,,) Here K =K,.K,.K, Expressions of K, and K, for Some Reactions (@ Evaluation of KC and Kp for HI forma- tion H,@ + 1,@) = 2HI@) Initially amole — bmole O mole Ateq @-X) (@-X) 2X mole mole mole Molar concentration or active mass of the various species at equilibrium will be According to law of mass action (HIP HIG] 4X? @=X)O=X) Evaluation of K,: H,@ + L(g) = 2HI@) Initially amole — bmole O mole Ateg. (a-X) (b-X) 2X mole. mole mole Total number of moles = (a - X) + (b= X) + 2X =atb Partial pressure of the three species can be caleu- lated as: (a-X)P P= ar) -X)P Pa) "arb) (2X) P pan= 2or On substituting the values in the law of mass action. _ Oye PPD - —4x__ GX) 0-H (i) In case of NO formation: Following the process used in HI formation, we get = 4x2 Ke= Gaye) ax? (@x\OX) Gil) In case of NH, formation: (iv)Chemical Equilibrium Illustrations 1. At 440°C the equilibrium constant (K) for the following reaction is 49.5. H,(g) +1, (2) = 2HI(@) If 0.2 mole of H, and 0.2 mole of I, are placed in a 10 L vessel and permitted to react at this temperature, What will be the concentration of each substance at equilibrium? Solution H,(g) + Lig) = 02 02 i} 0.2-X 0.2-xX 2x oe Keo TH . xy © @2=X)O2-X) 2HI (8) Initially Ateq. — xy 495 = @2-xF On solving X= 016 [HI]=2 «0.16 2 32 (H,] = [1] =0.2-0.16 = 0.04 2. 0.5 mole of hydrogen and 0.5 mole of iodine react in a 10 litre evacuated vessel at 450°C hydrogen iodide is formed. The equilibrium constant K,, for the reaction is 50, (@ Calculate the value of K, (ii) Calculate the moles of iodine which are in excess Solution (i) H, +1, = 2HI Imole Imole — 2mole As K,=K,QT)"= SORT! So K,=50 (i) Hy + 1, = 2HI 0s 0s 0 Initially 05-X 05-X 2X Ateq x = Hur ce) (ATL 5 (oxy © @35=X) 3-X) x X=039 Excess of iodine = 0.5 - 0.39 = 0.11 moles 3. Onemole of H,, two moles of I, and three moles of HI are injected in a one litre flask. What will be the concentration of H,, I, and HI at equi- librium at 490°C? The equilibrium constant for the reaction at 490°C is 45.9. Solution [11] mole L* o[L) Suppose X mole of H, and X mole of I, reacted at equilibrium, then 2, (HI H+ 1, = mI 1-X 2-X 342K Ateg (HI)? Kee wit om #59> ao On solving, we get X =0.684 At equilibrium (H,J=1-X = 0.684 = 0.316 mole L* (J=2-X 20.684 = 1.316 mole L" {HI =3+2: 3 + (2) (0.684) = 4.368 mole L* 4, The concentration equilibrium constant, K for the reaction N,+3H, 2NH, At 400 K is 0.5. Find K, (R= 0.082 L atm K+ mol) Solution K,=K (RT) For the equilibrium N,+3H, = 2NH, K,=05,T=400K An=2-(1+3)5.8 M@ Chemical Equilibrium R=0.082L atm K+ mol K, = (0.5) * (0.082 « 400)? = 4.65 « 10+ atm? For the reaction, CO, (g) + H, (g) = CO (g) + H,0 (g) At 1100 K and 1.02 « 10° N m* pressure. the partial pressure of CO,, H, and CO are 2.18 x 10*, 2.58 x 10% and 2.72 x 10* N m= respec- tively. Find the K, for the reaction. Solution CO, (g)+H, (g) = CO(g)+H,0(g) Poo * Puzo k= ‘cor * Paz Partial pressure of H,O (g) = 1.02 x 1082.18 x 108+ 2.58 x 10'+2.72 x 104 =2.72x 108 So 2.72 * 10! x 2.72 x 10¢ 218% 10" 2.58 10" = 13154 6. For the reaction H, + I, © 2HI. The equilib- rium concentration of H,, I, and HI are 8.0, 3.0 and 28.0 mo21 per litre respectively. Calculate the equilibrium constant of the reaction. Solution H,(g) + I, (g) + 2HI(g) 80 3.0 28.0. molar cone. at eq. re (HIP (28.07 THU] * 80~30 = 32.66. 7. Find the value of Kp for dissociation of 2H H, +1, If the equilibrium concentration of HI, H, and I, are 3.53, 0.4789 and 0.4789 mole litre respectively. Solution 2HI > H, + 1, 3.53 0.4789 0.4789 molar cone. atleq, 0.4789 x 0.4789 (353F = 184 102 K,=K.@1)* Here An=0 Kp=K, = 1.814 107 A gaseous mixture contains 0.30 mol CO, 0.10 mol H, and 0.2 mol H,O, plus an unknown amount of CH, in each litre. This mixture is in equilibrium at 1200 K. CO (g) +3H, (@) + CH, @ +10 @) ‘What is the concentration of CH, in this mix- ture? The equilibrium constant, K,.= 3.92 Solution CO (g) +3H, (g) > CH, (g) +H,0 (g) % Solution K 030 0.30, 1 0.10 x 0.10 1 0.2 eq. moles X22 oa cone re [CH,] [H,0] e [Co] [HP _ _Xx02 392 = 930 x @.10y X= 5.88 « 10? mol litre Iron filings and water were placed in a 5.0 liter tank and sealed, The tank was heated to 1000°C. Upon analysis the tank was found to contain 1.10 g of hydrogen and 42.50 g of water vapour. The following reaction occurred in the tank: 3Fe + 41,0 = Fe,0,+4H, Calculate the equilibrium constant for the reaction (FeO, [1]! [FeP [H,0}'Chemical Equilibrium 10. Here k and k, are the concentrations of [Fe,O,] and [Fe] respectively. Ka. eT Ki Keg Tor (1) 1102.02 ~ 0.11 moles perlite = 0.47 mole per litre 42.50/18.02 HO S9 1 OAs K'= ony 0.0030. The K, value for the reaction: H, +I, = 2H, at 460°C is 49. If the initial pressure of H, and I, is 0.5 atm respectively. Determine the partial pressure of each gas at equilibrium, Solution Ho+ 1 = 2M Initial p05 05 0 Ateg @5-X) 5-X) 2X (xy K oe 2X w5-x = 2X=35-71X 9X=35 x= 43 = 0389 nL At equilibrium: 50.389 = 0.111 atm P'I, = 0.5-0.389 = 0.11] atm PHI 0.389 x 2= 0.778 atm K, for CO (g) + H,0 (g) = CO, (g) +H, (g) at 986°C is 0.63. A mixture of | mole H,0 (g) and 3 mole CO (g) is allowed to react to come to an equilibrium. The equilibrium pressure is 2.0 atm. (i) How many moles of H, are present at equilibrium? (ii) Calculate partial pressure of each gas at equilibrium, Solution @ CO (g) + H,0 (g) = CO, (g) +H, (g) Initial mole 31 0 0 Moleateg.G-X) (I-X) xX x Total mole at equilibrium =3-X+1-X+X+X=4 x K.= ==) 0.63 = Sy3GT GK (asK, = 0.63) X=0681 Mole of H, formed = 0.681 Gi) Total pressure at equilibrium = 2 atm Total mole at equilibrium = 4 P*, =P, mole fraction of that gas G=X)P_ PHO 12. An equilibrium mixture at 300 K contains N,O, and NO, at 0.28 and 1.1 atmosphere respectively. If the volume of container is doubled, calculate the new equilibrium pres- sure of two gases. Solution 0, = 2NO, Pressure ateq. 0.28 ra (NO, _ de K,= py, 7 oze 7 432 am If volume of container is doubled i.e., pressure decreases and will become half, the reaction will proceed in the direction where the reaction shows an inerease in mole ie., decomposition of N,0, is favoured. N,0, = 2NO, (0.28-P) (1.1 +2P) ‘New pressure at eq. “5— +5.10 Chemical Equilibrium Here reactant N,O, equivalent to pressure P is used up in doing so. [Q.1\2)+2PP_ [0.55 +2PP _ K,= [oom-P] > ola=Py 7432 P=0.045 PN,O, = 0.14 - 0.045 = 0.095 atm PNO, at new equilibrium = 0.55 +2 « 0.045 PNO, = 0.64 atm. 13. At 25°C and | atmospheric pressure, the par- tial pressures in equilibrium mixture of gaseous 1N,O, and NO, are 0.7 and 0.3 atm respectively. Calculate the partial pressures of these gases when they are in equilibrium at 25°C and a total pressure of 10 atm, Solution N,O, = 2NO, Pressure ateg. 0.7 03 (PNO,? _ 03%0.3 _ K,= pygo, 7 Sg = 0.1286 atm ‘Suppose decomposition at 10 atm pressure N,0, = 2NO, Initial mole 1 0 Moleateg. (I-X) 2X x PE ~ 2% «to +309 4X2 x 10 d=) X= 0.0565 1.286 = = 20.0565 «10 (1 +0.0565) P'NO, = 1.07 atm, (10.0565) “Trooses * 10 =8.93 atm PN, 14, At 540 K, 0.10 mole of PCI, are heated in a 8 litre flask. The pressure of the equilibrium mix- ture is found to be 1.0 atm, Calculate K, and K, for the reaction, Solution Pcl, = PC, + Cl Mole before diss. 0.1 0 0 Mole after diss. .1-X) x Given: Volume of container = 8 litre (POLI {CL} _ (X/8). (XB) Pay “O1-xXys @ 1x 8= (0.1 +X) « 0.082 x 540 X=0.08 wi) From Equation (i) and (ii) = 0.08008 4, jos z Ko= 30 2008 74 * 107 mol litre K,=K.@1) As an=+! x 10? x (0.082 x 540) 77 atm 15, At some temperature and under a pressure of 4 atm, PCI, is 10 % dissociated. Calculate the pressure at which PCI, will be 20 % dissoci- ated, temperature remaining same. Solution PCI, +c Mole before diss. 0.1 0 Mole after diss. @.1-a) a a Given: a = 0.1 at 4 atm pressure axa (=a) Pat _ 4x OL d-a) 1-@1F K,= 0.040 atm Again when a is needed at 0.2, K, remains constant. Pa’ Tg Px O.2F 1-27 P=0.96 atm pia +a} So K, 0.040 =Degree of Dissoci ion (a): It is the ratio of number of molecules dissociated at equilibrium to initial number of molecules. Itis given as: X = aY Initial no, of moles 1 0 No. ofmolesateq. (I-a) na Total number of moles at eq, = (1 - a) + na =1+(@-Da Suppose the initial volume be V litre. Thus the v ume at equilibrium =[1+@-Dalv. Suppose ‘d’ is the observed vapour density at a par- ticular temperature when degree of dissociation is a” and D is the vapour density when there is no dis- sociation. Day @ 1 $0 Ta Dalv w Dividing eq, (i) by Gi), = 1+@-Da D d Jois abe D d @ Vt Heep = Medeor wei = Vapour density - m «=M-Ra-1 Here M = Initial molecular mass m= Molecular mass at equilibrium e.g., In the dissociation of PCI,, NH,Cl and N,O, the value of n= 2 so PCI, = PCI, +Cl, NH,CI = NH, +HCI N,0, = 2NO, Chemical Equilibrium @ 5.14 Illustrations 16. Calculate the per cent dissociation of H,S (g) if 0.1 mole of H,S is kept in 0.4 litre vessel at 1000 K. For the reaction 2HS(@) = is 1.0 x 10%. 2H, (g) +S, (g) the value of K, Solution 21,S(g) = 2H, ()+S,(@) 01-xX x X/2 At eq V=04L ULF IS] {H,S} _ BVP X2V) ~ [O1=X)VP As X is very-very small so 0.1 -X=0.1 xX > IOP x = 8x 10° X=2«107 % dissociation = >= 107+ 100 K = 10x 10¢ 10 10% 2x04%0.1x01 =2% The vapour density of N,O, at a certain tem- perature is 30. Calculate, the percentage disso- ciation of N,O, at this temperature Solution Normal molecular mass of N,O =28+64 =92 ‘Normal vapour density (VD. before dissociation) y= Nomnal moleeularmass_ 92 _ 4g Vapour density after dissociation (d) = 30. N,O,(g) > 2NO, (8) Degree of dissociation (x) = 46-30. = 6 = 302-1) ~ 301 x%= 535 18, What is the value of K, for the reaction, 1,(@) = 2)5.12 Chemical Equilibrium at 1473 K, when 1 mole of I, (g) introduced into an evacuated | litre flask such that only 5 % of it gets dissociated? Solution For this reaction L@ = 2@) (itially) 1-x 2x (at eq) oP __@xy fy 1-x As degree of dissociation is 5% X=0.05 (2 «0.05 T=0.05 = 0.01 _ = Qos 70.0105 So Ke= 19. The K, for the reaction N,O, = 2NO, is 640 mm at 775 K. Calculate the percentage dis- sociation of N,O, at equilibrium pressure of 160 mm. At what pressure, the dissociation will be 50%? Solution N,O, = 2NO, Mole beforeeg. 1 0 Mole at eq a-x) 2X Pe = 4X _ 160 o40= Ty * +X) X= 0.107 = 70.7% 2x O5P 640 = (asX=05) P= 480mm 20. 0.1 mole of N,O, (g) was sealed in a tube under atmospheric conditions at 25°C. Calculate the num- ber of mole of NO, (g) present, if the equilibrium 1N,O, (g) = 2NO, (g), (K, = 0.14) is reached after some time. Solution N,O, = 2NO, ol « @l-a) 2a As PaO.l So 100.1 If V and T are constant Paol+ta P=[.1 +ay0.1] 2 K, = ay « Porta 40 a? K,= @1-a) 40a @I-a) a =0.017 NO, = 01d 017 x 2 = 0,034 mole. 21. NH, is heated at 15 atm from 27°C to 347°C assuming volume constant. The new pressure becomes 50 atm at equilibrium of the reaction 2NH, = N, + 3H,, Calculate per cent of mole of NH, actually decomposed. Solution 2NH, = N, + 3H, Initial mole a 0 0 Mole at eq, (@Q-2X%) X 3x Initial pressure of NH, of a mole = 15 atm at 27°C The pressure of « mole of NH, =Patm at 347°C JS . P 300 ~ 620 P=31 atm At constant volume and at 347°C Mole 0 Pressure aw 31 a+ 2X 0 50 Before eq, After eqChemical Equilibrium ™ 5.13 a 42x _ 50 a 31 -19 X=@qa % of NH, decomposed = 2X x 100 = 2190 xa = 61.3% * 100 22. (i) Find the vapour density of nitrogen tetroxide which dissociates according to this equation. N,O, (g) = 2NO, (g) at 373 K given the degree of dissociation of N,0, is0.8 (i) Also find the total pressure of the mixture at equilibrium (Given Ke = 0.2616 mole litre) Solution i) The relationship between th degree of dis- sociation and the densities is given as q = DoD Here D = calculate vapour density D bserved vapour density at equilibrium lecular weight DofNo,= Nee B= 46 As ais given as equal to 0.8, Gi) As K=K RT)" N,O, = 2NO, a So K, = K, RT? = 0.2616 x 0.082 x 373 = 8 atm ‘Suppose the initial concentration of NO, is | mole. 0 Initial concentration of NO. As the degree of dissociation is 0.8 equilibrium con- centrations of N,O, and NO, are (1 — 0.8 = 0.2) and (2 0.8 = 1.6) respectively. So the total number of moles at equilibrium =02+16=18mole, If Pis the total pressure at equilibrium, we get 208 738 xp im ="O2 PS On solving, we get Total pressure (P) = 1.125 atm Relation between Standard Gibb’s Free Energy and Equilibrium Constant: Or \Van’t Hoff Reaction Isotherm It shows the free energy change of a reaction at any given temperature, pressure and composition of the reacting system as follows: AG= AG*+RT In} As at equilibrium AG is 0 so AG' RT Ind, Here J stands for reaction quotient of partial pres- sures of products and reactants. Concentration terms of products Concentration terms of reactants J,,means the partial pressure of the products and the reactants at the equilibrium i.c., J,, can be replaced by Kp. So AG -RT InKp AG’ 2.303 RT log, K IfaGe> 0 (He), K<1 Backward reaction is feasible IfAG°<0(-ve), K>1 Forward reaction is feasible If AG , K=0 Equilibrium state is obtained. Illustrations 23. Calculate the value of log K, for the reaction, N, (@) + 3H, (@) = 2NH, (@®)5.14 Chemical Equilibrium at 25°C. The standard enthalpy of formation of NH, (g) is 46 KJ and standard entropies of N, (g), H, (g), and NH, (g) are 191, 130, 192 JK mot" respectively. (R= 8.3 JK“! mol") Solution _N, (g) +3H, (g) = 2NH, (g) Atequilibrium AG? = 2.303 RT log, Ky... @ AG*= AH® - TAS* Given: AH? for NH, = ~46 kI AS*reaction = 2 x S°NH, ~ S'N, -3 = S°H, = 2% 192-191-3130 =-1975 T= 273 +2: 98K, AG*=-92 x 10° 298 x (-197) (AHP for reaction = ~46 * 2 kJ) = -92000 + 58706 From equation (i) +33294 = 2.303 x 298 x 83 log,, K, log, K,= 5.845. 24. Given values of AG®, at 25°C for liquid etha- nol (174 ki/mol) and gaseous ethanol (— 168.6 kJ/mol), Calculate the vapour pressure of ethanol at 25°C? Solution C,H,OH () = CH,OH @) AG? = [AG®, (C,H,OH) (g) ~ AG", (C,H,OH) (g)] AG* = (1) (-168.6 )= (1) 174.9) =463KI AG°=-RT InK =aGe InK= RT 6.3 kI/mol) [R314 = 10° KIAKmoh] @9BK) ~ 254 K= e8=0.079 (C,H,OH = 0.079 atm LE CHATELIERS PRINCIPLE It describes the effect of change in concentration, pressure and temperature on the reversible system. According to it, “If the system at equilibrium is subjected to a change of concentration or tem- perature or pressure, the system adjusts itself in such a way as to annual the effect of that change i.e, the effect of these changes can be neglected or minimized.” Effect of Concentration m= An increases in concentration of any substance favours the reaction in which it is used up i, in opposite direction, = An increase of concentration of reactant favours formation of more product i.e., forward reaction. m= Increase in concentration of product favours backward reaction. ic, its continuous removal is essential for more formation of it. Effect of Pressure = High pressure is favorable for the reaction in which there is a decrease in volume or nr > np. = Low pressure is favorable for the reaction in which there is an increase in volume or nr < np. m= Pressure is kept constant when volume is con- stant or nr = np, Here nr = moles of gaseous reactant np = moles gaseous product Effect of Temperature t= Increase in temperature favours the forward reac- tion in the endothermic reaction (AH = +ve) m Decrease in temperature favours the forward reaction in the exothermic reaction (AH = -ve). Applications of Le Chatelier’s Principle 1. On Physical Equilibrium (i) Tee-Water System (Melting of Ice) Ice «water —heat (AH = +ve) Asitis an endothermic process and there isa decrease in volume so, the favourable conditions for melting of ice are high temperature and high pressure)) Water-Steam System (Evaporation of Water): Water «> steam — heat (AH = +ve) (As it is an endothermic process and there is a) increase in volume so, the favourable conditions for evaporation of water are high temperature and low pressure. ii) Solubility of Gases in Liquids: When a gas, dissolves in a liquid, there is a decrease in its volume so an inerease in pressure will favour the dissolution of a gas in liquid i... solubil- ity of a gas is directly proportional to partial pressure of the gas (Henry's law) On opening carbonated water bottle, CO, comes out as its pressure decreases. (iv) Effect of Temperature on Solubility: Exothermic substances like CaO, Ca(OH), , KOH are more soluble in cold water than in hot water ic., low temperature favours their solubility Endothermic substances like sugar, urea are_ more soluble in hot water than in cold water i.e., high tem- perature favours their solubility. (¥) Effect of Pressure on Boiling Point: Onjnereasing pressure boiling point increases as vapour pressure decreases (vi). Effect of Pressure on Melting Point: Solid (V,) = Liquid (V,) If V, > V, melting is favoured by increase of pressure so melting point decreases for such solids. If V, < V, melting is favoured by lower pres- sure'So melting point increases for such solids Chemical Equilibrium ™ 5.15 REMEMBER m= Conversion of a solid into liquid, liquid into gas is favoured by high temperature in most of the cases. m= Melting of solids is accompanied by increase of volume so low pressure favours their melt- ing while high pressure favours solidification. 2. On Chemical Equilibrium (i) Formation of Nitrie Oxide: N, (g) +0, (g) + 2NO (g) ~ 43200 calorie Here favourable conditions for formation of NO are more concentration of N,, ©, constant pressure (as np =nr) and high temperature (as itis endothermic) (i) Formation of Ammonia: N, (g) + 3H, (g) «+ 2NH, (g) + 22400 cal Favourable conditions for NH, formation are more concentration of N,, H, high pressure (as np < nr) and low temperature (as itis exothermic). Effect of Adding Inert Gas on Equilibrium = When np is equal to nr there is no effect of adding an inert gas either at constant volume or pressure. = When np # nr there is no effect of adding an inert gas at constant volume. = When np # nr at constant pressure on adding inert gas equilibrium will shift towards more volume side. e.g., Dissociation of ammonia will be more at constant pressure by adding inert gas like argon (Ar) Solved Problems from the IITs 1. For the reaction, CO (g) + 2H, (g) = CH,OH (g) hydrogen gas is introduced into a five litre lask at 327°C, containing 0.2 mole of CO (g) and a catalyst, until the pressure is 4.92 atmosphere. At this point 0.1 mole of CH,OH (g) is formed. Calculate the equilibrium constants K,, and K,. [IT 1990] Solution Let the number of moles of hydrogen introduced be ‘m’ moles.5.16 ™ Chemical Equilibrium Total moles of CO and hydrogen = 0.2 +m. As PV=nRT P= 4.92 atm, V=Silitre R= 0.082 T= (273 +327) = 600K 4.92 « 5 = 0,082 x 600 x (0.2 +m) 492%5 0.2 m= F082 x 600 m=03 mole CO (g) + 2H, (g) = CH,OH (g) Ateq 0.2-X 03-2X xX 02-01 03-02 Ol =01 =01 Active SL ot ot Masses According to law of mass action [CH,OH] Ke = (col ——_0.1/5) “O15 «Oly = 2500 mol K,=K,@D* As An=-2 K, = 2500 (0.082 x 600)? 2500 W2x 492 = 1.0327 atm. K, 2. 0.15 mole of CO taken in a 2.5 litre flask is ‘maintained at 705 K along with a catalyst so that the following reaction can take place: CO (g) + 2H, (g) = CH,OH (g) Hydrogen is introduced until the total pressure of the system is 8.5 atm at equilibrium and 0.08 mole of methanol is formed. Calculate GK, and K,, (ii) the final pressure if the same amount of CO and H, as before are used, but with no catalyst so that the reaction does not take place. [IT 1993} Solution Let the total number of moles of gases be n at equilibrium. As PV= oRT. Given P=8.5 atm, V=2.5L R= 0.0821 atm L mol K* T=705K = 8525 B= Togzt x 705 ~ 0-367 mol CO (g) + 2H,(@) = CHOH® Initial = «1S @H), 0 mole Ateq 0.15-X [(aH),-2X] X=008 Number of moles of CO at equilibrium 15 ~0.08 = 0.07 mole ‘Number of moles of H, at equilibrium = total moles ~ moles of CO ~ moles of CH,OH = (0.367 -0.07 -0.08) =0.217 mole According to law of mass action __ [cHOH) {CO} [HF (0.08/25) (0.07/25) * (0.217 = 2.5¥ K. = 151.6 mol*L? K,=K.(RT)" 151.6 (0.0821 x 705)? = 0.045 atm? AS [(M,))~ 2X] = 0.217 (y)y = 0.217 +2 * 0.08 377 mole (ep)p = 0.15 Total moles (n,) = 0.377 + 0.15 n, RT So p, x 0.0821 x 705 2.5 = 12.20 atm,3. At temperature T, the compound AB, (g) dis- sociates according to the reaction, 2AB, (g) = 2AB (g) +B, (g) with a degree of dissociation, X, which is small compared with unity. Deduce the expression or X in terms of the equilibrium constant, K, and the total pressure P. [IT 1994) Solution 2AB,(g) = 2AB(g)+B, (e) Ateq (1-X) x x Total moles at equilibrium = = 24x 2 _ U2X/(2 + X)}. PP (X/2+X).P = R= Xa FX) P = xOP ~ @FX)U-XF As X is very small, (2+X)=2 and (1-X)=1 xP So K,= “9 3 = 2Ke w= X= KP) 4. A sample of air consisting of N, and O, was heated to 2500 K until the equilibrium N, (g) + 0,(@) = 2NO(@) ‘was established with an equilibrium constant Ke =2.1 « 10°, At equilibrium, the mole % of ‘NO was 1.8. Estimate the initial composition of air in mole fraction of N, and O, [IT 1997] Chemical Equilibrium 5.17 Solution N, (g) +0, (g) = 2NO(e) Let the total number of moles of N, and O, at initially = 100 Number of moles of N, at initially = a Let the number of moles of NO present at equi- librium =X. N,(g) + O,(g) = 2NO(g) Initially a loo 0 Ateq (=X) (100-a-X) 2X 2X _ 18, 106 = 100 X=09 [Nop AS Ke = INTTOT so 2x10" = @xy © @=X) 100=a=X) - 2x09 2.1*10°= G—apy aK 05 a=79 %iEN, in air = 79% % of O, in air = 100-79 = 21% 5. When 3.06 g of solid NH,HS is introduced into a two-litre evacuated flask at 27°C, 30% of the solid decomposes into gaseous ammonia and hydrogen sulphide. (Calculate K,, and K, for the reaction at 27°C. Gi) What would happen to the equilibrium when more solid NH,HS is introduced into the flask? [UIT 1999} Solution () NHHS(s) = NH,(@) +HS(@) 3.06 Initial moles 35° = 0.06 0) 0 Eq. moles (0.06-0.018) 0.018 0.018 0.018 0.018, Molar conc. 1 ee 0.06 x. a 10 0.0185.18 M Chemical Equilibrium 6 (NH [HS] 7 NHS] __(0.018/22 oe = 81105 molL* Kx)" 1 x 10 « (0.082 « 300)? K = 0.079 atm? Gi) Addition of NH,HS will not effect the equilibrium position In the following equilibrium, N,O, (g) = 2NO, (8) When 5 moles of each is taken and the tem- perature is kept at 298 K, the total pressure was found to be 20 bar. Given: AG*, (N,O,) = 100 KI AG", (NO,) = 50k (a) Find AG of the reaction at 298 K. (b) Find the direction of the reaction. [UT 2004) P (NO) F = 100_ = 0 10 AG aca = 2 4G", (NO) ~ AG", (N,O,) = 2«50-100=0 Here negative value of AG shows that reaction will be in forward direction, The equilibrium constant of the reaction, A,(g) +B, (g) = 2AB (g) at 100°C is 50. If a one litre flask containing one mole of flask containing one mole of A, is connected to a two litre flask containing two moles of B,, how many moles of AB will be formed at 373 K? [IT 1985] Solution A,@+B,@® = 2B® Initially 12 0 ateg. (1-X) Q-X) 2X (total volume =31ip Active (1-X) @-X) 2x masses According to law of mass action, [AB (AJ BJ = ax d-X)Q-X) 4x? =x) @=x) 7? 4 2-3K +X) x 50 2-3X +X?) x25 23X2—75X +50=0 yea DE NEGS) = 4 «23 « 50} ~ 2x23 X=2317 or 0.934 ‘The value of X cannot be more than one that is, greater than the number of moles of A, so X=0943 Number of moles of AB = 2X = (20.934) = 1.868 8. Ata certain temperature, equilibrium constant (Kis 16 for the reaction: SO, (g) + NO, (g) = SO, (g) + NO (g) If we take one mole of each of the four gases in one litre container, what would be the equilib- rium concentration of NO and NO,? (IT 1987] Solution $0, (g) +NO, (g) = SO, (g) + NO) Initial 1 1 1 1 cone Eq (1-X) (I-X) 1+X 1+X cone.Chemical Equilibrium ™ 5.19 9. According to law of mass action [SO] [NO] e [S0,] [NO] _ +x) +X) ~ U=X) =X) 1+x T-x74 16 1+X=4-4X 5X=3 X=3/5=06 Concentration of NO, at equilibrium = (1 - 0.6) =0.4 mole Concentration of NO at equilibrium = (1 + 0.6) = 16 mole N,O, is 25% dissociated at 37°C and one atmo- spheric pressure. Calculate (i) K, and (ii) the percentage dissociation at 0.1 atmospheric and 37°C [IT 1988] Solution N,O,(g) = 2NO, (g) Initial a) Ateq. (1-X) 2X Total moles = (1 - X)+2X = (1 +X) (=X) (+X) pWNO)=qMy-P PON,0)= P Given X = 0.25 and P = 1 atm = (1-025) PW,0)= yp 75 * 10.6 atm (20.25) PNO)= 7025) *1=0.4 atm yo.) _ 0.4 x 0.4 PN,O,- 06 = 0.267 atm Let the degree of dissociation of N,O, at 0.1 atm be ‘a’ then, d-» (Fa) * PN,O) On 10. Solution =a, PNO)= Tay (al +a)? x @.1)? ol K, x01 (Fa) = 48x01 _ 04 ata) (a 0.4 a (=a) 0.267 = 0.667 a* a= 0.632 So dissociation of N,O, = 63.2% 0.267 = ‘One mole of nitrogen and three moles of hydro- gen are mixed in a 4 litre container. If 0.25 % of nitrogen is converted into ammonia by the following reaction: N, (@) + 3H, (@) = 2NH, (@®), Find the equilibrium constant (K,) in concen- tration units. What will be the value of K for the following equilibrium? ‘AN, (8) + 3/2 H, (8) NH, @). [IT 1989] N, (@ + 3H,(g) = 2NH, (g) Ateg. (1-X) G-3X) 2X Active (1 0.0025) (3 - 0.0075) (0.0050) masses 4 + z According to law of mass action (NH,P IN] TH], (0.0050/4)¢ C9975) B.INSAY = 1.49 « 10° lit'mol? K for the reaction, ‘AN, (g) + 3/2 H, (g) = NH, (g) is equal to VK. 86 « 10" lit mol5.20 @ Chemical Equilibrium u The equilibrium constant K, for the reaction, 280, (g) + O, (@) = 280, (8) is 900 atm” at 800 K. A mixture containing SO, and O, having initial partial pressure of | and 2 atm respectively is heated at constant volume to equilibrate. Calculate the partial pressure of ‘each gas at 800 K. [IT 1989] Solution The system in the initial stage does not have SO,. SO, decomposes to form SO, and O, until equilibrium is reached. The partial pressure of SO, decreases. 12. ‘Suppose the decrease in partial pressure is 2X. 280, (2) + 0, (g) = 280, (g) 2x 24x 1-2x According to law of mass action Ateq (1 =2xy 8 GXGH [As 2+X)=2] (= 2x 900 = Sy 12x. 84.45 On solving X= 0.0115 atm So the partial pressures at equilibrium are: p(SO,)=2 « 0.0115 = 0.023 atm p(0,)=2+0.0115 = 2.0115 atm p(SO,) 2 0.0115 = 0.977 atm For the reaction, CO (g) + 2H, (@) HOH) hydrogen gas is introduced into a five litre flask at 327°C, containing 0.2 mole of CO (g) and a catalyst, until the pressure is 4.92 atmo- sphere. At this point 0.1 mole of CH,OH (g) is formed. Calculate the equilibrium constants K, and K,, [IT 1990] Solution Let the number of moles of hydrogen introduced be ‘m’ moles, 1B. Total moles of CO and hydrogen = 0.2 +m As PV=nRT P=4.92 atm, V=S5 litre R= 0.082 T= (273 +327) = 600K 4.92 « $= 0.082 x 600 (0.2 + m) = 4.925 0.2-+m= 7082 x 600 m=0.3 mole CO (g) + 2H, (g) = CH,OH (g) Ateg, 0.2-X 03-2X X 02-01 03-02 01 =01 =01 Active 0.1 Massss 5 55S According to law of mass action, [CH,OH] [co] [HP (0.15) * 15) O15 = 2500 mol* L? 2500 * (0.082 x 600)? 2500 Ke x43 = 1.0327 atm 0.15 mole of CO taken in a 2.5 litre flask is maintained at 705 K along with a catalyst so that the following reaction can take place: CO (g) + 2H, (g) = CH,OH (@) Hydrogen is introduced until the total pressure of the system is 8.5 atm at equilibrium and 0.08 mole of methanol is formed. Calculate (i) K,Chemical Equilibrium ™@ 5.21 Solution ben at equilibrium, and K,, (i) the final pressure if the same amount of CO and H, as before are used, but with no catalyst so thal the reaction does not take place. [HT 1993} Let the total number of moles of gases As PV=nRT Given P=8.5 atm, V=2.5L R= 0.0821 atm L mol? K+ T=705K = 85425 _ B= TO8IT « 705 ~ 0.367 mol CO (g) + 2H, (g) = CH,OH (g) Initial 0.15 @H), 0 mole Ateq. 0.15-X [(nH,),-2X] X= 0.08 Number of moles of CO at equilibrium = 0.15 0.08 = 0.07 mole ‘Number of moles of H, at equilibrium = total moles ~ moles of CO ~ moles of CH,OH = (0.367 - 0.07 - 0.08) =0.217 mole According to law of mass action _ (0.08/25) = (0725) O217* 255 = 151.6 mol? K,=KoR1)* = 151.6 x (0.0821 « 705)? = 0.045 atm? AS [(Oyy)y- 2X] = 0.217 (n,,), = 0.217 +2 x 0.08 = 0.377 mole (M6), = 0.15 14. 0.377 +0.15 =0.527 Total moles (n,) o,RT So p= —V 0.527 « 0.0821 x 705 25 = 12.20 atm, At temperature T, the compound AB, (g) dissociates according to the reaction, 2AB, (g) = 2AB (g) + B, (g) with a degree of dissociation, X, which is small compared with unity. Deduce the expression for X in terms of the equilibrium constant, K, and the total pressure P. UIT 1994) Solution 2AB, (g) = 2AB (g)+B, (2) Ateg (I-X) x ¥ 15. Total moles at equilibrium =24+X 2 20.-X) paB)= GaP p(AB)= GP PB) mw P x5) Pn) Oa? [2X/2 +9}. PP (K2 +X) P ~~ BRO-Xyv2 FX). PF = XP (2+X)(1=XP As Xis very small, (2+X)= 2 and (I -X)= K, So K, 2K, P X= (QKyP)” ‘A sample of air consisting of N, and O, was heated to 2500 K until the equilibrium N, (g) +0, (g) = 2NO (g) was established with an equilibrium constant Ke =2.1 x 10°. At equilibrium, the mole % of, x5.22 @ Chemical Equilibrium NO was 1.8. Estimate the initial composition of air in mole fraction of N, and O, (IT. 1997] Solution N, (g) + 0, (g) = 2NO(g) 16. Let the total number of moles of N, and O, at initially = 100 ‘Number of moles of N, at initiall Let the number of moles of NO present at equi- librium = X N,(@) + O,(@) = 2NO() Initially a 100-a 0 Ateg. (1-X) (100-a-X) 2X 2X 18 100 100 X=09 (Nop As Ke“ INTIO So 2.110? (ese =X) (100. x09 (a-0.9) (100 =a-0.9) 21 «10 a=79 % if, in air =79 % % of O, in air= 100-79 = 21% When 3.06 g of solid NH,HS is introduced into a two-litre evacuated flask at 27°C, 30% of the solid decomposes into gaseous ammonia and hydrogen sulphide. (@ Calculate K and K, for the reaction at 27°C, (ii) What would happen to the equilibrium when more solid NH HS is introduced into the flask? UT 1999} Solution (i) NHHS(s) = NH,(@) +H,S(@) Initial moles 2285906 9 0 31 Eq. moles (0.06 - 0.018) 0.018 0.018 17. Solution Reaction quotient (NH) [HS] “THEST (.018/2)* T =8.1* 10% molL* K,=K,* (RT) K,=8.1 10% x (0.082 « 300)? 079 atm? Gii) Addition of NH,HS will not effect the equilibrium position, In the following equilibrium, N,O, (g) = 2NO, (g) When 5 moles of each is taken and the tem- perature is kept at 298 K, the total pressure was found to be 20 bar. Given: AG*,(N,0,) = 100 kI AG®, (NO_) = 50 KI (a) Find AG of the reaction at 298 K (b) Find the direction of the reaction. [IT 2004] [P(NO = 100 =T0 10 DCs 2.G,(NO)- AG" (N,0,) =2x50-100=0 As AG =AG*—2.303 RT log,, Q, =0- 2.303 x 8.314 298 log, 10 = 57.05.85 = 5.705 kI Here negative value of AG shows that reaction will be in forward direction,Chemical Equilibrium ™@ 5.23 MULTIPLE-CHOICE QUESTIONS Straight Objective Type Questions (Single Choice only) 1 In a reaction A, (g) + 4B, (g) ++ 2AB, (g); AH <0. The formation of AB, (g) will be favoured by ‘a. low temperature and high pressure bb. high temperature and high pressure ¢. low temperature and low pressure d. high temperature and low pressure For which of the following reaction, K, ‘a, 2NOCI (g) + 2NO (g) + Cl, (@) ‘b.N, (g) +3H, (g) + 2NH, (g) C. H, (g) + Cl, (g) «+ 2HCI (g) 4. PCI, (@) + Cl, (g) + PCL (@) In what manner will increase of pressure affeet the following equation? (6) +H,0@) + CO@) +H, (@) ‘8, shift in the reverse direction b. shift in the forward direction C. inerease in the yield of hydrogen 4. no effect Which one of the following statements does not describe the equilibrium state? 1. The rate of forward reaction is equal to the rate of the reverse reaction. b. Equilibrium is dynamic and there is no net conversion to reactants and products. . The concentration of the reactants is equal to the concentration of the products. 4. The concentration of the reactants and prod ucts reach a constant level Which of the following statements is false regard- ing the equilibrium constant, Ke? 1, When quoting K, it is customary to omit units 'b, The numerical value of K, depends on the form of the balanced equation ©. K, fora reaction at a particular temperature always has the same value. 4d. K,, for the reverse reaction is the negative of K,, for the forward reaction. u. Which statement is true about equilibrium con- stant? The value of K, . changes as product concentration changes . changes as reactant concentration changes d. changes as temperature changes. Write the equilibrium equation for the forward 2CH, (g) + 30, (g) = 2CO (g) + 4H,0 (g) (CH? + (0, ©” [COP = DLO} (cor H,0K » Ko" TCH PIOP kK 2(CHJ+3[0) ©" 2[CO}=4 HO] 2 [CO] +4 [H,0] ©” 2(CH I 310, Nitric oxide reacts with oxygen to form nitrogen dioxide: 2NO (g) + O,(g) = 2NO, (g) ‘What is K,” for the reverse reaction if the equill rium concentration of NO is 0.300 M, O, is 0.200 M, and NO, is 0.530 Mat 25C? a 0.1584 b. 624 ©. 0.0641 4d. 1.641 IK. the equilibrium constant fora forward reac- tion what is K,, for the reverse reaction? a UK, ek, b-K, . None of these Given the reaction 2HI = H, + I,, If K,’ for the reverse reaction is, 185 * 10° at 425°C, what is K, for the forward reaction atthe same temperature? a 581 b. 642 © 54.1 . 541 For the reaction N, (g) + 20, (g) = 2NO, (g),5.24 ™ Chemical Equilibrium 12. 13. 14 15. 16, 1. K, 83 = 10" at 25°C. What is the concentration of N, gas at equilibrium when the concentration of ‘NO, Is twice the concentration of O, gas? a. 24 107M. b. 48 10°M . 28 107M 4. 28« 10M IfK, = 7.04 » 10° for the reaction: 2HBr (g) = H, (@) + Br, () What is the value of K, forthe reaction ‘4H, (g) + 4 Br, (@) = HBr(g)? a 2.68 b. 0.385 6377 4.377 If K, equals to 0.11 at 25°C for the reaction: b. 30 455 Which one of the following statements about the equilibrium constant (Kp) is false? a Total pressures are used in the equilibrium «equation in place of molar concentrations. bb. The units for Kp are usually omitted €. An= the sum of the coefficients of the gaseous products — the sum of the coefficients of the ‘gaseous reactants 4. The relationship between Kp and K is: Kp-K, RT)" Given the reaction ata certain temperature 2HI (g) = H, (g) +1, (g). At equilibrium, the par- tial pressure of HI is 1.8 « 10° atm and the partial pressures for H, and I, are 0.10 atm each, Find Kp at that temperature, a 3110 b. 3:1 «10° © 4810" 4. 28107 If K, = 20 « 10 at 25°C, for the following reaction: H, (g) + Cl, (g) = 2HCI (@), then find Kp at the same temperature. a. 3.5» 10" b. 2.0 « 10" ce. 18» 108 d. 4.0» 10" Phosphorous pentachloride decomposes to phosphorous trichloride and chlorine gas at elevated temperatures by the following reaction: PCI, (g) = PCI, (g) + Cl, (g). IK, = 1.8 at 250°C, what is the value of Kp at the same temperature 19. 20. 21. 22, atl ©. 7.7» 104 b. 67 . 6.7% 107 ‘The decomposition of ammonia is: 2NH, (g) = N, (g) + 3H, () IPKp is L5 «10 at 400°C, what isthe partial pressure of ammonia at equilibrium when N, is 0.10 atm and H, i 0.15 atm? a 4.1% 10%aum b. 1.5 10° atm ©. 38 «10am d. 4.7 * 104 atm ‘The decomposition of ammonia is: 2NH, (g) = N,(@) * 3H, (g). Ifthe partial pressureof ammonia is 1.6 * 10° atm and the partial pressures of N, and H, are each 0.25 atm at equilibrium, ‘what is the value for K,, at 400°C for the forwar reaction? a. 020 ©. 28108 b. 0.50 4. 1.50 ‘The decomposition of ammonia is: 2NH, (g) = N,(g) + 3H, (g). If the pressure of ‘ammonia is 10 » 10- atm, and the pressures of N, and H, are each 0.20 atm, what is the value for Kp at 400°C for the reverse reaction? a 62*104 b. 26 104 ©. 62 104 d. 42104 A150 L vessel contains an equilibrium mixture of 0.100 mol of NO, 0.150 mol of Br,, and 0.250 mol of NOBr at 25°C. What is the value of Kp for the following reaction: 2NO (g) + Br, (g) = 2NOBr (g) a. 256 b 128 ©. 2.56 4. 526 As a rule, which of the following phases are not included in the equilibrium constant expression? I. Pure liquids IL. Pure solids IIL. Aqueous solutions IV. Gases a Tand b. Land I ¢ Hand I . Land IV ‘Which equilibrium below is homogeneous? a 2CO(g) +0, (g) = 2CO, (@) b. NHNO, (3) = N,O(@) + 2,0 (2) © BaSO, (s) = Ba** (aq) + S0,* (aq) 4. 2H,0, () = 24,0) + 0@)Chemical Equilibrium ™@ 5.25 27. ‘What is the equilibrium equation for the dissocia- tion of formic acid in water? HCOOH (aq) + H,0.() = HO" (aq) + HCOO" (aq) __ [HCOOH] '©~ [H,0'] [HCOO} 1,07] [100] Ke" [HCOOH] 11,07 [C00] Xo” Tcoon} [H,0] [HCOOH] [H,0] Ke" THOT[HCOO} e ‘What is the equilibrium equation for the following reaction? CH, (8) + 30, (g) = 2C0, (g) + 2H,0 0) aba Raitt a kp = Beal Pasl © Peal Pol For which one of the following reactions will K.=Kp? a. COCI, (g) = CO(g)+ Cl, (e) b. 20, (@) = 30,() ¢. ZnO (s) + CO (g) = Zn(s) + CO, (e) 4. CO (@) + 2H, (g) = CHOH @) If K, = 0.900 and Kp = 538 for a hypothetical reaction, which of the equations below could represent the reaction at 25°C? a. AGG) = 2C() +D®) b. Big) =CQ)+ DA) . A(1) + 2B (g) = 2C (g) 4. A+B) =3C(@) 28, 29. 30. 31. 32, Given the hypothetical reaction: 2A (8) + nB(g) = 3C (@), Kp = 0.0105 and K, = 0.45 at 250°C. What is the value of the coefficient ‘n'? a2 b3 e4 a For the reaction, A(Q) + 2B) = 2C @),K, = 1 * 10° at 25°C, ‘Which of the following statements is true? a. The reaction is favoured in the reverse diree~ tion b. The value of Kp will be larger than the value fork, © An=41 4d. ‘The concentration of the products is greater than the concentration of the reactants, ‘Which statement is true fora reaction with K, equal 102.43 » 10" ‘a The reaction proceeds nearly all the way to completion b. The reaction proceeds hardly at all towards completion ¢. Increasing the temperature will not change the value of K. 4d. ‘There are appreciable concentrations of both reactants and products For the reaction: 4HCI (2) + O, (g) = 2Cl, (B) + 2H,0 (0), the equilibrium constant is 0.063 at 400 K. If the reaction quotient is 0.100, which of the following statement is not correct? a [0,] will inerease b. [Cl] will decrease ©. [H,0] will increase 4. {HCI} will inerease The equilibrium constants equal to 5.00 at 1300 K. for the reaction: 280, (g) +O, (g) = 280, (2) If initial concentrations are [SO,] = 1.20 M, [0,] 45 M and [SO] = 1.80 M, the system is a Not at equilibrium and will remain in an unequilibrated state . At equilibrium €. Not at equilibrium and will shift to the right to achieve an equilibrium state. 4. Not at equilibrium and will shift to the left to achieve an equilibrium state.5.26 ™ Chemical Equilibrium 33. 38, 37. The equilibrium constant (Kp) equals to 3.40 at 25°C for the isomerisation reaction: Cis-2-butene = trans-2-butene Ifa flask initially contains 1.00 atm of each gas, in ‘what direction will the system shift to reach equi- librium? ‘a. The system is already at equilibrium b. The system is not at equilibrium and will remain in an unequilibrated state, twill shift left 4 It will shift right ‘At a certain temperature, bromine and nitric oxide react to form nitrosyl bromide Br, (g) + 2NO (g) = 2NOBr (a) When initial amounts of Br,, NO and NOBr are mixed, the concentration of NOBr increases. Which of the statements is true? a K.=Q bK.Q 4. More information is needed to make a state~ ‘ment about K,.. At a certain temperature, bromine and nitric oxide react to form nitrosyl bromide. Br, (g) + 2NO () = 2NOBr (g). When 0.010 mol Br, is mixed with 0.025 mol NO and 0.015 mol NOBr in @ 2.50 litre flask, the concentration of NOBr decreases. Which of the statements is true? a. K.<90. eK ‘At a certain temperature, K, equals 1.4» 10° for the reaction: 2CO (g) + O, (g) = 2CO, (g) Ifa 2.50 litte flask contains 0.400 mol of CO, and 0.100 mol of 0, at equilibrium, how many moles of CO are also present in the flask? 0.169 mol b. 0.238 mol ©. 1.69 mol 4. 0.0894 mol For the isomerisation reaction: Butane = Isobutane Kp equals 25 at SOO°C. If the initial pressures of butane and isobutane are 10. atm and 0.0 atm respectively, what are the pressures of the two gases at equilibrium? a. P (butane) P (isobutane) = 0.40 atm 0 atm and 38, 39. 40. Al. 2. b. P (butane) = 9.8 atm and P (isobutane) = 0.38 atm € P (butane) = 0.46 atm and P (isobutane) = 10 atm d. P (butane) = 0.38 atm and P (isobutane) = 9.6 atm Ata certain temperature the equilibrium constant (K.) equal 0.11 forthe reaction 2ICI(@) = 1, (@) + Cl, What is the equilibrium concentration of ICI if 0.75 mol of I, and 0.75 mol of Cl, are initially mixed in a 2.0 litre flask? a 045M b. 145M © 01MM 4. 0.90M ‘The esterification of acetic acid and ethanol is tziven by the reaction below: C,H,OH (aq) + CH,COOH (aq) = CH,COOC,H, (aq) + H,0 (0) When 1.00 mol of ethanol was mixed with 2.00 mol of acid in a 1,00 litre flask, 0.86 mol of ester was formed at room temperature. What is the value of the equilibrium constant (Ke)? a 28 bs4 © 64 4. 108 Kp is equal to 48.70 at 731 K for the reaction: H, (@)+1,(@) = 2H (g) Initially the mixture contains 0.08592 atm each of H, and I, and 1,0000 atm of HI, What is the pressure of HI at equilibrium? a, 0.9108 atm b. 0.8796 atm ©. 0.1908 . 0.02859 When baking soda is heated it decomposes according to the following reaction: 2NaHCO, (5) = Na,CO, (8) + H,0 (@) + CO,(@) If sufficient baking soda is placed in a container and heated to 90°C, the total pressure of the gases is 0.5451 atm. What is the value of Kp at the temperature? a 0.08428 ©. 04728 b. 0.18754 4. 0.07428 Ammonium carbamate can dissociate into gases at 25°C according to the reaction NH,COONH,(s) = 2NH, (g) + CO, (8)Chemical Equilibrium 5.27 If sullicient ammonium carbamate is sealed in a flask, the total pressure will be 0.117 atm at equi- librium, What is the value of Kp at 25°C? a. 147 10" b. 237 10+ 477 «104 4. 3.58» 10+ Gaseous hydrogen bromide decomposes at elevated temperatures according to the following equation: 2HBr (g) = H, (g) + Br, (g) At a certain temperature @ 2.00 litre flask is ini- tially filled only with 0.600 mol of HBr. What is the value of K,, at that temperature ifthe flask contains 0.104 mol of H, at equilibrium? a. 3.04 « 107 b. 640» 104 ©. 7.04 «102 . 224» 107 K, is 167 » 10™ at 25°C for the formation of iron(II} oxalate complex ion: FCO), ea If 0.0100 M Fe is initially mixed with 1.00 M oxalate ion, what is the concentration of Fe ion at equilibrium? a. 2.48 «10M b. 6.56» 10M. ©. 1.67 10M. d. 5.68 « 108M Fe (aq) +3C,0,7(a9) Acids donate protons to water according to the gen- eral equation: HA (aq) +H,0 () = H,0" (aq) +A (aq) Consider the following acids and their equilibrium constants for reaction with water at 25°C. Ifall the acids have same initial concentration, which is the strongest acid (that is, which donates the most pro- tons to water)? 4104 b. HIO,.K,= 1.7 = 107 ¢. HBrO,K,= 3.7 10% 4. HE, K,=22 «10° ‘The solubility of 1:1 salts is measured by the equi- librium constant for the general reaction: MX (s) =M" (aq) +X (aq). Given the following salts and their equilibrium constants for the reaction above at 25°C, which salt isthe least soluble? a. BaCO, K,=3.6 » 10? b. S1CO,,K, = 5.6» 10 ©. MgCO,,K,=64 «107 . CaCO, K, = 4.5» 10 47. 48, 49. Which of the following changes in reaction condi- tions will after the composition of an equilibrium mixture of gases? a Increasing the temperature b. Decreasing the pressure or volume ©. Addition of reactants or products 4. All ofthe above will alter the equilibrium concentrations Which of the following changes in reactions condi- tions will not alter the equilibrium concentrations? a Increasing the temperature b. Decreasing the pressure or volume €. Addition of an inert gas to the reaction mixture 4. Addition of reactants or products “If. stress is applied to a reaction mixture at equi- librium, the reaction occurs in the direction that ‘will relieve the stress”. This statement is called a Law of mass action b, Le Chatelier’s principle ¢. First law of thermodynamies 4. Law of combining volumes The pink and blue species below form a violet coloured mixture at equilibrium: [Co(H,0),}* (aq) + 4CI (aq) = ink) [CoCL}* (aq) + 6H,0 0) (Bluey As the concentration of [Co(H,O) ‘hat happens to the solution? s increased, a No colour change is observed b. The solution becomes colourless ©. The concentration of [CoCI,}* decreases 4. ‘The concentration of [CoCl,}* inereases ‘The overall reaction for photosynthesis can be represented by the following equation 6H,O( + 6CO, (@) = C4H,,0, (6) + 60{) The enthalpy change for this reaction is 2802 ky. ‘Which of the following changes in condition will shift the equilibrium to the right? ‘a Increase the temperature b. Remove one-half of C,H,,0,(s) €. Increase the pressure of O, 4. Remove CO, by reaction with CaO (6). The dissolution exothermic. of calcium hydroxide is5.28 M Chemical Equilibrium Ca(OH), (8) = Ca* (aq) +201 (aq) What happens when the solution of Ca(OH), is heated? a. The Ca(OH), (6) completely dissolves. b. The amount of Ca(OH), () decreases. ¢. The amount of Ca(OH), (6) increases. 4. The amount of Ca(OH), (6) remains unchanged. Which change in the system will drive equilibrium to the left in the following reaction? N,Q, (g) = NO, (g) + NO, (g) ‘a, Inerease the volume bb Increase the pressure ¢. Decrease the amount of NO, 4. Increase the amount of N,O, Iron oxide ores are reduced to iron metal by exothermic reaction with carbon monoxide, FeO (8) + CO (a) = Fe (8) + CO, (@) Which of the following changes in condition will cause the equilibrium to shift tothe right? a. Add CO, b. Add FeO «Add CO 4. Raise the temperature Ammonium bromide is a crystalline solid that decomposes endothermically when heated: NH,Br () = NH, (@®) + HBr (g). When solid NH,Br is added to an evacuated flask at 300°C, which change in reaction conditions below will cause the equilib- rium to shift to the right? ‘a, Decrease the temperature b. Double the volume of the container ©. Add more NH, 4. Add more NHBr ‘A crude type of disappearing ink is based on the following endothermie equilibrium: {Co(HH,0),1C1, (aq) (Colourless) [CoCl,(H,0),] (aq) + 21,0 (@) (Bluey Ifthe reactant solution is used to write on a piece of paper and the paper is allowed to partially dry, what can be done to bring out the coloured handwriting. ‘a, Put the paper in the oven b, Add water 0. 61. . Put the paper in the freezer 4. Decrease the volume ‘The enthalpy for the following reaction is 136 ki. If the reaction takes place in a closed container, which one of the following reaction conditions will not decrease the concentration of water vapour? 2NaHCO, (8) = Na,CO, (8) + CO, (g) + 1,0 (@) & Cool the container b. Add CO, ¢. Remove some NaHCO, 4. Decrease the volume of the container Calcium carbonate is relatively insoluble and the dissolution reaction is endothermic. CaCO, (8) = Ca* (aq) + CO,* (aq) Which change in reaction condition bellow will shift the equilibrium to the right? ‘a, Increase the temperature b. Add an anion with which Ca** is even more soluble than calcium carbonate ©. Add an acid to react with CO,*ion 4. All ofthe above will shift reaction fo the right The decomposition of nitrosyl bromide is exothermic: 2NOBr (g) = 2NO (g) + Br, (g). Which of the following changes in reaction condition will shift the reaction to the left? a, Decrease the temperature . Increase the container volume © Add more NOBr 4. None of these Which of the following changes in reaction conditions will not alter the composition of a homo- ‘geneous equilibrium mixture of gases? ‘a Increasing the pressure or volume b. Decrease the temperature ¢. Addition of reactants or products, 4. Addition of a catalyst Which of the following statements about a catalyst is true? ‘A catalyst provides a lower energy pathway for a reaction. . A catalyst changes the position of the equilib- rium in a reactionChemical Equilibrium Ml 5.29 2, A catalyst increases the temperature of reaction 4. A catalyst is consumed in a chemical reaction, A catalyst increases the rate of a chemical reaction by providing a lower energy mechanism for the reaction. When this occurs, which one of the fol- lowing is not affected? ‘a. Activation energy for the reverse reaction b. Equilibrium constant . Activation energy for the forward reaction 4. Rate of the reverse reaction A reaction reaches dynamic equilibrium at a given temperature when ‘a, Opposing reactions cease and the system is static. 1b, The amount of products exceeds the amount of reactants ¢. The relative amounts of reactants and products are constant and rate (forward) ~ rate (reverse) 4. (forward) ~ k (reverse) At 25°C, a certain first order reaction has a rate constant equal to 1,00 « 10° sand an equilibrium constant (K,) equal to 4.18, What is the rate con- stant for the reverse reaction? a 148 «10? 5 b. 239% 104s" ©. 429 «10st d. 3.39% 104s ‘Nickel metal can be prepared by the reduction of nickel oxide: NiO (8) + CO(g) = CO, (g) + Ni) At936 K, Kp = 4.54 « 10° and at 1125 K, Kp = 1.58 » 10%. Which statement is true? ‘a, The reaction is exothermic b. The activation energy decreases with increas- ing temperature, . The reaction is endothermic 4. The activation energy increases with inereas- ing temperature, ‘The reaction below virtually goes to completion because cyanide ion forms very stable complexes with Ni* ion [NEO (aq) + 4 CN (aq) > [NKCN) (aq) + 64,0 0) At the same time, incorporation of “C labeled eya- nide (CN?) is very rapid: Which statement below is correct with regard to stability and rate of reaction? a. Unstable species react rapidly b. Equilibrium is static €. Stable species can react rapidly d. Stable species do not react rapidly Brainteasers Objective Type Questions (Single choice only) 67. When reaction (1) and (2) below are added together, the result is reaction 3) 1. H,0() + HNO, (aq) = HO" (aq) + NO, (aq) TL. 10" (aq) + OFF (aq) = 21,0 IIL. HINO, (aq) + OH (aq) = NO, (aq) + H,0 0) IFK, ~ 4.50 = 10, and K, ~ 1.00 = 10% find the equilibrium constant K,. a. 25010" b. 0.50 « 10” ©. 4.50 « 10” d. 3:56 «10 68. Find the equilibrium constant for the reaction: A@) + Bg) = 2C (B) at 25°C when k equals 1.4 = 10°? M5" for the reaction A (g) +B (g) > 2€ (g) at 25°C and k equals 27 = 10-? M# s* for the reaction 2C (g) DA(g) + Big) at 25°C. a 52 b. 64 © 36 a7 69. For the reaction: PCI, (g) + PCI, (g) + Cl, (2) the forward reaction at constant temperature is, favoured by 1. introducing an inert gas at constant volume TL. introducing ehlorine gas at constant volume TI, introducing an inert gas at constant pressure 1V. increasing the volume of the container V. introducing PCI, at constant volume. a Lud bIV,V ILIV 4. ILIV,5.30 Ml Chemical Equilibrium 70. 2 23. An equilibrium mixture of CO, O, and CO, at @ certain temperature contains 0.0010 M CO, and 0.0015 MO, A‘ this temperature (K,. equals 1.4 » 10° for the reaction: 2C0 (g) +0, (g) = CO, (2) What is the equilibrium concentration of CO? a. 11 109M b. 2.2 10°M © 48" 10°M 4. 66 « 10°M ‘The equilibrium constant (Kp) equals 3.40 for the isomerization reaction cis-2-butene = trans-2-butene If a flask initially contains 0.250 atm of cis-2-butene and 0.125 atm of trans-2-butene, what is the equilibrium pressure of each gas? a. P(cis-2-butene) = 0.085 atm, P (trans-2-butene) = 0.290 atm b, P(cis-2-butene) = 0.058 atm, P (trans-2-butene) = 0.230 atm €. P(cis-2-butene) = 0.028 atm, P (trans-2-butene) = 0.156 atm 4. P(cis-2-butene) ~ 0.034 atm, P (trans-2-butene) ~ 0.128 atm ‘The following two isomers of C,H.NO exist in equilibrium with each other in solution: ° oH I | H,C -C-NHCH, = H.C -C =NCH, IfK,,= 0.57 at 25°C and the initial concentration of the reactant is 0.50 M and the product is 0.70 M, what are the concentrations at equilibrium? ‘a, [Reactant] = 0.46 Mand [Product] = 0.28 M b. [Reactant] = 0.69 M and [Product] = 0.48 M . [Reactant] = 0.96 M and [Product] = 0.47 M 4. [Reactant] ~ 0.76 M and [Product] = 0.44M For the chemical equilibrium, CaCO, (8) = CaO) + COLR) 4. AH? can be determined from which one of the fol- lowing plots? log, Peo. is Z log, Peo. b vt — LZ s & z log? —* Phosphorous pentachloride decomposes to Phosphorous trichloride at high temperatures according to the reaction: PCI, (g) = PCI, (g) + Cl, (@) ‘At 250°C, 0.250 M PCI, is added to a flask. If K,, = 1.80, What are the equilibrium concentrations of each gas? a. [PCI] = 2.26 M, [PCI,] = 204M, [Cl,]=204M . [PCI] = 0.0280 M, [PCI,] = 0.222 M, 222M . [PCI] ~ 1.28 M, [PCI] = 1.028 M, [cl] = 1.028 MChemical Equilibrium mi 5.34 78 76. 7. 78, 4. [PCI,] = 3.82 M, [PCI] = 0.879 M, [cl] =204M Cyclohexane (C,H,,) undergoes a molecular rear- rangement in the presence of AICI, to form methyl- cyclopentane (MCP) according to the equation: C\H,, = MCP IfK,, = 0.143 at 25°C for this reaction, predict the direction the reaction will shift, if the initial con- centrations of C,H,, and MCP are 0.200 M and 0.100 M, respectively. The system ‘a. is already at equilibrium b. will shift right . will shift let 4. isnot at equilibrium and will remain in an uncquilibrated state Oxalie acid ean donate two protons to water in sue- cessive reactions: 1 HCO, (aq) + 1,0) = H,0°(aq) + HCO, (aq) I HC,O, (aq) + H,0 0) = 1,0" (aq) + C,0," (aq) IfK,, = 59 « 10% and K,, = 64 » 10% at 25°C, what Is the value of K, for reaction (3)? IIL. HCO, (aq) +240.) = 2H,0" (aq) + C,0,* (aq) 7.6104 b, 58 «10% 6.6.4 «109 4.38 «10% The equilibrium constant for gaseous reaction: A+B=C+D is 100 at 25°C. Consider the following statements in this regard. Ifthe initial concentration of all the four species were 1.0M each, then the equilibrium concentration of L. Awould be 0.182 mol/L. I. Cwould be 0.818 mol/L. IIL. D would be 1.818 mol/L Of these statements: a. Land III are correct b, Land IL are correct, ¢. [and III are correct 4. I, and II are correct What is the equilibrium constant (K,) for the reaction: 2Hlg () + O, (@) = 2H1g0 (s) if the amounts of reactants and products at equilibrium are 1.00 g of 7. 80, 81. 82, HgO (s), 2.00 ml of Hg (D), and 1,60 MO, (5)? (The molar mass and density of HgO (6) is 217 g/mol and 1.10 glem’, The molar mass and density of Hg (Dis 201 g/mol and 13.6 g/ml) a 0.625, b. 1.625 © 6.25 « 107 4. 1.2810? ‘An equilibrium mixture for the reaction 2H (g) + 2H, (@) +8, (@) had 1 mole of H,S, 0.2 mole of H, and 0.8 mole of S, ina 2 litre flask. The value of Ke in mol L" is a 0.08 b. 0.016 ©. 0.004 4. 0.160 Cyclohexane (C,H,,) undergoes a molecular rear- rangement in the presence of AICI, to form methyl- cyclopentane (CH,C,H,), according to the equation CH, = CHCH, IK, = 0.143 at 25°C for this reaction, find the ‘equilibrium concentrations of C,H,, and CH,C,H, if the initial concentrations are 0.200 M and 0.100 respectively a (CH,,) [CH,C.H,] = 0.016 M b. [CH] = 0.262 and [CH,C.H,] ~ 0.038 M ¢. [C,H,,] = 0.186 and [CH,C,H,] = 0.162M 4. [CH] =0.164 and [CH,C,H,] = 0.621 M What is the correct sequence of active masses in increasing order in gaseous mixture containing one ‘gram per litre of each of the following? 1.NH, IL, MIL H, Iv. 0, 286 and Select the correct answer using the codes given below a WLLIV.0 © ILLIVO b. MLIVILT 4. IVIL 1,0 ‘The equilibrium SO.CI, (g)+ $0, (g) + Cl, (@) is attained at 25°C in a closed container and inert gas helium is introduced. Which of the following statement(s) is/are correct? 1. concentrations of $O,, Cl, and SO,CI, change IL, more chlorine is formed5.32 Ml Chemical Equilibrium 84, 88, IIL, concentration of SO, is reduced IV. more $O,Cl, is formed a. L100 b, ILULIV . HLIV . none One mole of N,O, (g) at 300 K is kept in a closed container under one atmosphere. Its heated to 600 K when 20% by mass of N,O, (g) decomposes to ‘NO, (g). The resultant pressure is. b. 24 atm 4. 10.atm a 12atm ¢. 2.0atm The solubility of a solute in water varies with tem- perature and given as S = Aes™™ Here AH is enthalpy of the solution. For the given solute, variation of log, S with temperature can be shown by the figure given below vt This solute may be ‘a. CaSO, «. CuS0,5H,O b. CuSO, @. Zn0 ‘A mixture of carbon monoxide, hydrogen and ‘methanol is at equilibrium. The balanced chemical equation is CO (g) + 2H, (g) = CH,OH (. At250°C, the mixture contains 0,0960 M CO, 0.191 M H, and 0,150 M CH,OH. What is the value for K,? a 452 b. 428 «529 4. 0.581 ‘The oxidation of sulphur dioxide by oxygen to sulphur trioxide has been implicated asan important step in the formation of acid rain: 280, (g) + 0, (g) = 280, (g) If the equilibrium partial pressures of SO,, O, and SO, are 0.564 atm, 0.102 atm, and 0.333 atm respec- tively at 1000 K,, what isthe Kp at that temperature? a 2.24 b. 468 © 3.42 @. 13.42 For the dissociation of PCI, into PCI, and Cl, in gascous phase reaction, if is the observed vapour density and D the theoretical vapour density with 89. “a” as degree of dissociation. Variation of Did with 1a” is given by which graph? ‘ *t Do | “t 7 | d. None of these What is the value for K,, for the following reaction: POCI, (5) = Pb* (aq) + 2CI- (aq), if PEI, (s) = 1.50 g, [Pb*] = 16 « 10? Mand [CI] = 32 » 10 M at equilibrium? (The molar mass of PbCI. (5)is 278 gimol and its density is 5.85 g/cm’). & 26» 10% ©. 1.6» 108 b. 08 * 10* d. 64» 104 ‘The hexaammine cobalt(II ion is very unstable in acidic aqueous solution: [Co(NH,),}” (aq) + 6H,0° (aq) > [Co(H,0),}* (aq) + 6NH, (aq) However, solutions of hexaammine eobalt(D) can be stored in acidie solution for months without noticeable decomposition. Which statement below about the equilibrium constant and the activation ‘energy for the reaction is true? a Keq> 10° and Ea is very large b. Keq < 10° and Ea is very small &. Keq < 10° and Ea is very large 44. Keq> 10° and Ea is very smallChemical Equilibrium 5.33 a1. 93. 94, For the decomposition of PCL, (g) ina closed vessel the degree of dissociation is «at total pressure (P), PCI, (g) = PCL, (8) + Cl, (@)s K, Which among the following relations is correct? a. a= MK, +PYK,] b. a= IKK, +P] ea WK, +P) 4. a= \(K, +P) The equilibrium constant Ke for the reaction N, (@) + 20, (g) + 2NO, (g) at a particular temperature is 6.0 « 10%. The ratio of the concentration of NO, to O, at equilibrium is 0.0152. ‘The equilibrium concentration of N, is a, 0.253 molilitre b, 3.85 » 10 molflitre ¢. 3.85 molllitre 4. 2.53 » 10? molflitre ‘NiO is to be reduced to nickel metal in an industrial, process by use of the reaction, NiO(s) + CO() = Ni(s) + CO(g) At 1600 K the equilibrium constant for the reaction isK, = 60 = 10°. Ifa CO pressure of 150 torris to be employed in the furnace and total pressure never exceeds 760 torr, will reduction occur? a. No b. Yes ‘¢. Cannot be said 4. May or maynot For the reaction N, (@) + 3H, (@) © 2NH, (@) , AH = -936 J mol, the concentration of Hat equilibrium can be increased by 1. lowering the temperature TH. increasing the volume of the system MI. adding N, a constant volume IV. adding H, a constant volume a. ILIV b. only is correct . 1, I and Ill are correct d. IIL and IV are correct «only 1Viseorret Which of the following reactions, initially at equi- librium, will shift to the left when the temperature is decreased at constant pressure? 96. I. 2C,H(g) + 50, (g) = 4CO,(g) +2H,0() AH = 1297 KI I. COJg) = Og) + CO) AH = 393k) IIL, 4Fe(s) +30, (g) = 2Fe,OYs) AH =—1644kI add b. Gi) © Gii) 4. all of them ‘The graph which represents all the equilibrium concentrations for the reaction N,0{@) = 2NO, (the concentrations of N,O,(g) and of NO, (a) for which the following reation will be at equilibrium \ill lie on which of the following graph) (NO] INO.) —> INO], {NO — (No]_, {N,0,) — (No. {N,0,) —> K, = 00112 at 25°C for the reaction N,(g) +0, = 2NO(e) ‘What the change in the state of the reaction ocours (if any) if [N,], =2.00M, [0,], = 0.500M?5.34 Ml Chemical Equilibrium ‘8, Reaction produces more NO, QK, Multiple Correct Answer Type Questions 97. N,0, = 2NO,K, i,+%0, = NO.K, 2NO = N,+0,K, NO = 4N,+%0,K, Correct relation between K,, K,,K, and K, is/are a WK,*K)=1 BK *K,= « VK, *Ky .\K,*K, 1 98, The following reaction attains equilibrium at high temperature N, (g) +2H,0 (g) + heat = 2NO (g) + 2H, (@) ‘The amount of NO is affected by a. Addition of catalyst b, Compressing the reaction mixture ¢. Increasing the nitrogen concentration 4. Decreasing the hydrogen concentration 99, ‘The equilibrium constant for the reaction CaCO, (8) = CaO (8) + CO, (g) can be given as . K, = ((CaO][CO,}/1CacO,] b. K.= [CO] © Ko Poy, 4. K, =[€aCO,J({C20]{C0,)) 100, Which of the following does not affect the value of equilibrium constant of a reaction? ‘a. Change in temperature b. Addition of a catalyst Change in the concentration of the reactants 4. Change in pressure 101. Which of the following statement is/are incorrect here? 1, Equilibrium constant of an exothermic reaction decreases with the increase of temperature b. K, is always greater than K, 102, 103. 104. 105, 106. €. At equilibrium, concentrations of reactants and produets become constant as the reaction stops 4. Addition of a catalyst speeds up the forward reaction more than he backward reaction For the reaction PCI, (2) = PCI, (g) + Cl, (@) the forward reaction at constant temperature is favoured by ‘a Increasing the volume of the container b. Introducing PCI, at constant volume ¢. Introducing an inert gas at constant volume 4. Introducing Cl, (g) at constant volume ‘When NaNO, is heated in a closed vessel oxygen is liberated and NaNO, is left behind. At equilibrium, which are not correct? a Increase of pressure favours reverse reaction . Increase of temperature favours forward reac- tion ©. Addition of NaNO, favours reverse reaction 4. Addition of NaNO, favours forward reaction Which of the following statement (s) is/are correct: a A plot of P vs 1/Vis linear at constant tempera- ture b. A plot of log,, K, vs 1/T is linear ¢. A plot of log [X] vs time is linear for a first ‘order reaction, X —> P 4. A plot of log,, P vs I/T is linear at constant volume Which of the following have K,=K, here? a 2NO(g) + Cl, (g) = 2NOCI (g) b. N,(@) + 3H, (@) = 2NH@) © H,(@)+X,(@) = 2X @) 4. N, (g) + 0, (g) = 2NO(@) Which of the following statement is/are correct about the equilibrium? a AG=0 . Catalyst has no effect on equilibrium ©. K,,changes with temperature 4. Value of K,, changes by increasing concentra tion of equilibrium107, 108, 109, 110. i. Which of the following reaction can have same units of K,? a. NH,HS (8) = NH, (g) + 11S (@) b. 280, (g) = 280, (2) + 0, (8) «. PCL @ = PCI, (2) + Cl(g) @. XX,@ X¥@)+Y¥@ ‘The degree of dissociation (a) g-D=d (add Incorrect match for the equilibrium 4ng,2 5 Qt2R er bp=to+™r © Sno,n ~ 6 e 6 a a patgrtr Which of the following statement is/are correct for a reversible easton? a. Ata given temperature both Q and K vary with the progress of the reaction b. When Q> K, the reaction proceeds in back- ward direction before coming to stand still «. Reaction quotient (Q) isthe ratio of the prod- uct or arbitrary molar concentrations of the products to those of the reactants @. Qmay be <>=K. Which of the following factors will not disturb the cquilibrium state of tis reaction? N, (g) +0,(@) = 2NO(@) 1. Change in temperature b. Change in pressure ©. Addition of N, 4. Addition of a catalyst For the gas phase reaction, cH,+ CH, (AH = -32.7 keal), carried out in a closed vessel, the equilibrium concentration of CH, can be inereased by ‘a. Decreasing the pressure b. Adding some C,H, «Increasing the temperature 4d. Removing some H, 112, 113, 14, us, 16. 47. Chemical Equilibrium 5.35 Ifthe volume of the reaction flask is reduced to half ofits initial value and temperature is kept constant then in which of the following eases the position of ‘the equilibrium will shift? & CO) +H,0(@) = CO,()+H,(@) b. L(g) = 21g) c. NHS (3) = NH, (g) + HLS (6) 4, 2NOCI(g) = 2NO (g) + Cl, (@) For the reaction, 2X (g) + ¥ (g) = 2Z (g), AH = +15.6 kT Which of the following will increase the extent of the reaction at equilibrium? a. Addition of catalyst . Increasing concentration of Z , Increasing the temperature 4. Increasing the pressure In this three step endothermic reaction Step Step I A,(g) +B, (g) ——+-AC (g) ——> Step I 3D (g) ——+ 2E (@) Which of the following statement is/are correct? & Step IIL is favoured by low temperature and high pressure b. Step Lis favoured by high temperature and low pressure ©. Step IL is favoured by high temperature and high pressure 4. Step II is favoured by high temperature and ow pressure For which of the following reactions, KK, = RT? a. 2HX (g) = H, @) + X,@) b. N, (g) + O, (g) = 2NO (g) ©. PCI, (g) = PCI, (g) + Cl, (@) d.N,O, (g) = 2NO, (g) ‘Which of the following are homogeneous equilibria? a. NO, (g) = 2NO, (g) b. H, (g) + X, (g) = 2HX (g) ©. HO() = H0@) . CaCO, (s) = CaO (s) +CO, (g) Consider the following reversible reaction: CO (g) + 2H, (@) = CHOH (g) AH =-92.5 kT5.36 Ml Chemical Equilibrium Which factor(s) will increase the yield of methanol at equilibrium? ‘8, Addition of inert gas at constant volume b. Increased pressure on the system . Increased temperature 4. Increased partial pressure of hydrogen 118. ‘The variation of equilibrium constant K with tem- perature is represented by AH Rw log, K,— log, K, saat) AHL b. [Glog Kya «log, K ~ constant 4. log, K = constant RT 119. ‘The reactions in which the yield of the products ean not be increased by the applications of high pres- sure is/are a, 280, (g) + 0,(g) = 280, b, NH,HS(s) = NH\(g) +H,S(g) «. N,O{g) = 2NO,@) 4. N,@) + 3H,@) = 2NH@) 120. An inert gas is added to the reaction N,+3H, = 2NH, at constant volume. Which of the following is/are incorrect? ‘a, Backward reaction is favoured b. The reaction remains unaffected . The reaction ceases to proceed 4. Forward reaction is favoured 121. Which of the following is/are correct? a. The equilibrium constant does not depend upon pressure b. When pressure is applied on ice = librium more water will be formed ater equi- . The equilibrium constant increases when a catalyst is introduced 4. Changes with temperature Linked-Comprehen: n Type Questions Comprehension 1 The decomposition of NH HS (s) takes place as follows NILHS (6) = NH, () + H,$ @) If we take 3.06 gm of solid NHHS into a two litre evacuated vessel at 300 K. It undergoes 30% decomposition, 122. Forthis decomposition the value of K, & 16.2 « 10% mol? lit® b.8.1 » 10 mo it® 6.4.05 « 10° mo lit® 4.1.62 » 10° mol? lit 123. The value of K, is a 0.0245 atm? 8.1» 105 atm? b. 0.049 atm? 4. 0.081 atm? 124, What will be the effect of adding more amount of NHLHS on equilibrium? ‘a. Equilibrium will shift in forward direction b. Equilibrium will shift in backward direction ¢. Equilibrium remains unaffected 4, Equilibrium first shifts in forward direction and then becomes constant 125. Which relation is correct here? 4. Can’t be predicted here Comprehension 2 The dynamic nature of chemical equilibrium can be easily demonstrated by in the synthesis of ammonia by Haber’s method. N, (@) + 3H, (@) = 2NH, (g) + Q keal Habertook definite amount of N, and H, at suitable conditions of temperature and pressure, He was able to find amount of NH, and unreacted amount of H, N, at various time intervals. 126. Which of the following condition is not favourable for formation of more ammonia in this processChemical Equilibrium ml 5.37 1. Higher temperature IL More pressure IIL. More concentration of NH, IV. More concentration of N, and H, a. 11,1 ¢. ILILIV b. Lm a LULIV 127. Ifthe value of K,, for this reaction at 673 K is found, to be 16.4 = 10° then the value of AG" is, ‘8, 11.733 keal 11.733 cal €. 931.6 keal 4.9316 cal 128, Ifat a temperature the value of K, for the reaction N, + 3H, = 2NH, is 1.49 « 10% mol” lit, What will be the value of K.” for 2NH,? a. 1.49» 10° litimole b. 3.86» 10° it mol 3.86 « 10° lit’ mol? 4. 1N(1.49 10°) lit? moP 129. If the initial molar concentrations of NH, and NH, at 400°C are 0.142 M and 0.0265 M and 0.0384 M respectively prediet which statements are correct here? IL. Here Q>K, IL. The reactants are favoured ML, Here Q Ke with given quantity ofA, B, and C hence reaction is reversed (A): The equilibrium constant for a reaction hav- ing positive AH® increases with increase of temperature. (R): The temperature dependence of the equi rium constant is related to AH® and not AH? for the reaction. (A): The value of K gives us a relative idea about the extent to which a reaction proceeds. ‘The value of K is independent of the stoichi- ometry of reactants and products atthe point of equilibrium, ®: (A): On opening a sealed soda bottle dissolved carbon dioxide gas escapes. ®: Gas escapes to each the new equilibrium con- dition of lower pressure. (A): The equilibrium constant is fixed and a char= acteristic for any given chemical reaction ata specified temperature, ®): ‘The composition of the final equilibrium mixture at a particular temperature depends upon the starting amount of reactants, Ay ®: Ice melts slowly at higher altitudes, ‘The melting of ice is favoured at high pres- sure because ice —» water shows decrease in volume. librium ay (R) At equilibrium AG is 0. When Q=K, reaction is at eq (A): Dissociation of PCI, decreases of Cl in presence (B) An increase in concentration of Cl, favours backward reaction to decrease dissociation of PCI,Chemical Equilibrium 5.39 152, (A): Water boils at high temperature in pressure cooker (B) Inside the pressure cooker pressure is less than Latm, 153. (A): Some hydrated salts like blue vitriol dissolve in water with absorption of heat (R) LeChatellers principles no valid fr sold —solid heterogencous systems. 184, (A): For every chemical reaction at equilibrium standard Gibbs energy of reaction is zero. (R): At constant temperature and pressure, chemi- cal reactions are spontaneous in the direction of deceasing Gibbs energy. [nr 2008] Matrix-Match Type Questions 158, Match the following: Column 1 (Column I A. N, (g) + 3H, (g) = (P) Increase of pressure 2NH, (8) favours forward reaction B.N, (g) + ©, (g) = (q) Constant pressure 2NO(e) favours forward reaction C. NH,COONH, (8) =) 2NH@) + CO,(g) log, K v7 D. CaCO, (s) = CaO(s) (5) +C0,@) log, K Ww (®) Decrease in pressure favours forward reaction 156. Match the following: Column 1 (Column I (A) 280, +0, +280, ee 8 () No effect of catalyst onk, (B) N,+0,>2NOgg g (q) No effect of pres- (©) P+Q>2R+8 AH = Positive (9) Ky increases with rise in temperature (D) PCI, -+ PCI, + Cl, (8) K,, decreases. with rise in temperature 157, Match the following Column 1 Column 11 A. N, (g) + 3H, (g) = 2NH,(g) (Pp) K,0 D, CHCOOCH,() +HOM= 6) K.>K, CH,COOH() + C,HOH() © Pra? 188, Match the following: Column I Column I A Lawofmass.action _(p) Guldberg wage B, Active mass of CaCO, (q) Kp =Ke (RT) 6) ©. 280, +0, +280, @ : PCI, + PCI, +Cl, (8) zero () Kp=Ke (RT) 159, Match the following: Column 1 Column It ALN, (@) + 3H, (g) © (p) heterogeneous 2NH, reversible reaction B, CaCO, (8) + C20 (9) + (q) 2H > H,(@)* 1,8) CO, (@) ©. Kp=Ke (© equilibrium state D. rate of forward reaction = rate of backward (6) homogeneous ible reaction revers- 160, Match the following: Column I (Process) Column I (Favourable conditions) ‘A. Melting of ice (P) High pressure B. Vaporization of water (q) High temperature5.40 Ml Chemical Equilibrium C. Formation of nitric (r) More concentration of oxide N, D. Formation of NH, by Haber’s method (3) Presence of inert gases (®) No change in pressure 161. Match the following: Column 1 Column Tt AN, (@) +0, (@) = 2NO (p) K,>K, () B. 280, (g) + 0, (g) = @ K,~K, 280, (g) C. PCI, (g) = PCI, () + @ K, nr. SoChemical Equilibrium ™@ 5.43 85, 87. 91. 182M 818M [A]=1-0818 [c]=1 +0818 [D] = 1.818 M, 0.2 molelL. [S]= 0.8204 mole/L, [HS] = 1 motesL (0.2F [0.4] Ke = E1041 770.016 motel. ‘Active masses of 1 g/17 ¢mol jo eee ol g28gmol_ = ag moll Lg2gmol_} eee =} mol 1 ©, > 1 932 gmol = 35 mol/L Increasing order of active masses is 1/32 < 1/28 < 1/17 < 1/2 mol/L. 0, K, (RT 1» 10 » (0.082 » 300)* 0.049 atm? Since NH,HS (3) is a compound so its active mass is assumed as unity in any condition. As An,=2 that is, K=K, As AG? =-2.303 RT log,, KP AG? =-2:303 « 2 « 673 » log,, (1.64 » 10%) (On solving, we get AG" = 11.733 keal As Ke’ = Ke = (1.49 « 10°) 3.86 « 10” lit mol D-d (1d Asa~5.44 Ml Chemical Equilibrium (As D = M2 = 208.5/2 = 104.25) _ 104.25 ~ $7.92 Q-1) = 5792 On solving, we get a= 0.8% = 0.8 « 100 80% 132, On solving, we get a= 0344 ‘Volume percent of Cl, = Mole fraction » 100 * 100 = 25.6% 134, «Rty"’ An~ +1, T= 700K, 076 = (0.082)(700)" = 0.01323 = 0.013 Assertion-Reason Type Questions 138. CCI(g) = C(@) +2Cl(e) Initialy —2.00atm =O atm Change x atm +2x atm Atequil (2.00-x)atm 2x atm K,-0.76 1,52 —0.76x = 4x*, 4x! + 0.76x 152-0 Using the quadratie formula a=4,b=0.76,¢= 152 0:76 + V (0.76) (4) (1.52) 204) 016 +4.99 _ 9 so 8 = 0.53 atm xatm, 2.00 atm fraction CCl, reacted = 140, 143, 4, 150, 154. The 162, 163. 164. 165. 166, 167. 168, =053 2.00 = 0.264 = PCI, = 2x = 2(0.5287) = 1.06 atm PCI, = 2.00 x = 2.00 0.5287 = 1.47 atm 2NO (g) +0, (g) + 2NO, ‘When pressure is increased then equilibrium shift in those direction where volume that is, number of moles decreases, ‘The rate of a reaction is first order of equilibrium. ‘The temperature dependence of the equilibrium constant is related to AS® as well as AH? for the reaction. ‘At equilibrium its free energy change , AG which is zero fora spontaneous process, AG <0 lIT-JEE Corner Catalyst has no effect on equilibrium. Decreas- ing the volume or pressure has no effect because nr ~ np. Therefore, the equilibrium shifts in the forward direction by increasing the cone. of reac tants CO, (g). ‘Temperature and pressure both effect equilibrium but catalyst has no effect (Le ~ Chatelir’s principle). Concentration of products increase with time so Q _ {eID (AJB) Ang=2-4=-2 Kp~Ke(Rty" Ke =KpiRT)" = 144 «10 oat = 7737 K, (equilibrium constant) is independent of pres- sure and concentration ‘When volume is decreased, pressure increases and this will favour backward reaction. Thus, degree of dissociation decreases but K, does not change since ‘temperature is constant [AgNH,), K-35 «10 Re TINE]Chemical Equilibrium ™@ 5.45 k (Ag¢NH),)° * (AgONH)F (NET ne _ (Ag(NH,),* 1 KS TAg TINE], formation constant K, for Ag’ +2.NH, = [Ag(NH,) I" K-35» 109 1.74 « 107 08 » 10 Numericals For Practice ‘Three moles of PCI, three moles of PCI, and two moles of Cl, are taken in a closed vessel. If at equi- librium the vessel has 1.5 moles of PCI, the num- ber of moles of PCI,, present in itis a8 b45 e21 a. 10 An acid reacts with glycerine to form complex and equilibrium is established, NiO (8) + CO (@) = Ni(s) + CO, (g), Ifthe heat of reaction at constant volume for above reaction is 1200 cal more than at constant pressure and the temperature is 300 K, then which of the following expression is true? a. K,=K b.K, P°H) #H, (g) +I, (g) = 2HI(g) K= ee (sy yO) K’= W64. H.N.COONH, (s) + 2NH, (g) + CO, (g) em © QpFp~ 4p =2.8 «10° tor p'=0.7 » 10° tor = 70 » 10" torr” p= 412 torr Total dissociation pressure = 3p = 123.6 torr 2B, (g) = 2AB (g) + B, (2) 2 0 0 intially 2U-X) 2K X ateg Amount of moles at equilibrium =2(1—X)+2X+X=2+X Pak Bus] Pyoal 40x 4X Kn? (As 1-X =1824+X=2) X > (KAP = OK Py" As(@) *B(@) + 2AB@) @-») @-» @ (otal number of moles = 2a) Equilibrium constant (Kor KJ GP, = 49 Total numberof moles tequila5.50 ™ Chemical Equilibrium xl ax 7 a lla 9 2x0 27772814 2x/a= 14/9 wa=7/9 a-x/2a= 19, 15. 2NH) = N,@) + 3H,(@) Initially A. o 0 Ateg. A(—a) Aaiz 3Aai2 % of NH, by volume . AC =o) Raa) + AE A According to conditions 16. % Kd») 4x4 e+e! P98 On solving, we get P,: Pi 1:36 17. The first equilibrium is multiplied by 2 and added to equilibrium (2) to get equilibrium (3) K,-(K)'*K, K, = (0.3299 «2.24 » 102 = 0.2424 10% = 2.424 « 108 18, 2NO,(g) = 2NO() + 0, (@) 104 For the reverse reaction, 2NO (g) +0, (g) = 2NO, (g) 19. 20. 2. Rea 108 ‘Multiplying with 2, NO (g) + 20, (g) = 4NO, (@) K= (2 «104? =0.25 « 107=2.5 « 10" D-glucose «+ D-glucose (1-x)mole x mole 28x=18 x~ 182.8 9/14 ~ 0.683 (==) = 0357 form inthe equilibrium mixture = 35.7% CH,COOH +H,0 = CH,COO-+H,0" Initially 005M 00 Ateq (05-X) XX ‘CH,COONa + CH,COO> + Na® Initially 05M 00 Ateq 0 05 05 [CH,COO]=0.5+X=05 [CH,COOH] = 0.05 X= 0.05 [CH,COO} [4,0] [CH,COOH] 15 «10% 05 * [HO] ~~ 0.05) LS = 10% = 0.05 BHO] = OOO {s0,}[0,}"” [so] 5 10°M K-49 10° (sor Ka" S0F 10] K.> (UK ,,)? = (1/49 » 1037 ~4165 N,0,(¢ = 2NO, (g) Vapour density = 5° = 46 Density = 30 So degree of dissociation = 50%,28, 21. NH,COONH, > 2NH, + CO, Initial 1 mole Afterdiss. 1a 2a @ Total=2+1a density (4) 3, 1 Observed density (€) & 5 ay Did=1+2a 10-0) 2 = 1 G8=160) _ "2 1600” Dezree of dissociation (VD),—(V.D),, “@- DD), 208.5 2 (vD), = 104.25 (PCI, at equilibrium = 5 atm) 2NO(g) + Cl, (@) = 2NOCI(e) Initially 20160 Ateq, 202K 16X-Y 2X Cl, (@) + Mg (s) = MgCl, (8) Initially 16 10 Ateq 16X-Y LY Y° 02 yr-08 (As Yin in moles while Y is pressure in atm) 8 « 0,082 » 300 10 As16-X-¥=5 y- (On solving, we get x= 9.08 $0 Pyoey 18.06 K,= Pay * Pas sPt= 0.6 14atm Ifthe equilibrium amounts of NH, and H,$ are due solely to the decomposition of NH,HS (3), the equi- librium pressure of the two gases are equal, and each is "4 of the total pressure. 28, 29. 30. 31. 32, Chemical Equilibrium ml 5.54 Pray = Ps = 0.614 atm/2 = 0,307 atm Kp~(0307)'= 0.0943 AHe_) 11 2.303 R '300 ~ 40K 303 1.987 AH? = 4576 cal mol log KK, ~ 1000 (1/1200) 10/12 = 516 ASK, ~P,o,- 2.25 atm So number of moles of CO, 2251 (0.0821 * 600 ‘The minimum moles of CaCO, needed = 0.0457 The minimum weight of CaCO, needed = 0.0457 « 100 = 4.57 g [SO,C1,] = 2.00mol/2.00 L = 1.00 M. The change in [SO,CI,], x, = 0.56 (1.00 M) = 0.56 M SO,Cl, (g) = SO, (g) + Cl, (g) Initialy 100M 0 oO Change -0.56M 40.56M +0.56M Atquil. 044M +056M_ +0.56M (so,tcl] ©" [s0.C1] 0.56) oad =0.7127=0.711M ‘As PCO< H'+ Cr = Purification of NaCl by passing HCI gas. Due to common ion effect the dissociation of | Isohydric Solution: These are the solutions hav- HS is suppressed and the [H’] in solution is | ing same concentration of common ions. due to HCL _ lA LHS] lonic Product of Water Ko "THS] Itis the product of the molar concentrations of H’ or » (031 [HS] H,O* and OH ions. It is denoted by Kw. 7 _ 10.3] +9 = torso [as (H']from Hcl =0.3] H,0 +H,0 + H,0 +0 Kw =[H,'0] [OH] [H'] Or and Ka, = PS Here Kw = Ionic product of water or auto [HS] pro-tolysis constant of watch [Hs] = 33x 10*M _ HHS} 21TH] 107 x01 035.56 Mi lonic Equilibrium = Kw=Ka K, pkw = Kw=KaxK, = pKw=pKa+ pK, wm At 25°C : Kw = 1 x 10" pKw= 14 ‘The value of Kw increases with the increase of temperature, 4og,. Kw For example, at 98°C, Kw is 1 x 10 pH Scale It was introduced by Sorrenson to measure acidity or basicity of a solution. pH Potential de — H'-ion concentration. Itis given as [H]= 10" pH = -tog,, [H"] pH of aqueous solution is equal to —ve log of H* (H,‘0) concentration in molefitre. 1 = pPH= log, Fy PH of Weak Acid In case of a weak acid like acetic acid CH,COOH ++ CH,COO- + HY 1 o 0 cd-x) cx tx K=Cx (Ka/C) [H" pH = -log,, Cx = Cx = CV(KalC) = VKaC pH =-log,, VKaC Here C = Molar concentration of acid x = Degree of dissociation Ka = Dissociation constant of an acid pH of Weak Base NH,OH «+ NH, + OH” 1 0 0 (x) cx x pOH = -log,, Cx pOH = =log,, VK,C issociation constant of a base. REMEMBER m= pi of strong acid or base does not depend ‘upon temperature m= pH of weak acid deceases with increase in temperature due to increase in ionization. m= pH of weak base increases with increase in temperature due to increase in ionisation or [OH] ion concentration. pOH {OH] = 10 pOH = —log,, [OH] 1 °"Tog,, [OF] pH + pOH = 14 pH + pOH = pkw pKa=—log,,Ka 1 Acidic Strength pka adi pK, =—log,,K, 1 1 ;, * Basie strength pK, ot pK: -ve log of dissociation constant. = Aweak acid has high pK, = A weak base has high pK, To Find the Nature of Solution = If["]> 107, pH is less than 7 and the solution is acidie. = If [H*] = 10°, pH is 7 and the solution is neutral a It (H)< 107 is basic. pH is more than 7 and the solutionpH Range of Some Substances Substance pH —range Gastric 1-30 Soft drink 2-40 Lemons 22-24 Vinegar 24-24 Urine 48-84 Milk 63-66 Saliva 65-75 Blood 13-15 Sea water 85 Tears 74 itation of pH-Scale = pl value of the solution does not give us at once idea of the relative strength of the solution. = pilis zero for IN solution of strong acid. = pH is negative for concentration 2N, 3N, 10N ete for strong acids = At higher concentration in place of pH Hammet acidity functions are used, Illustrations 5. How many grams of NaOH must be dissolved in one litre of solution to give it a pH value of 11? Solution Given pH! of solution = 11 pH = log [H"] 11 =-1og (H"] [Ht] = 10M Kw=[H'] [OH]= 1 * 10" tony = LE = 1x 10!M [OH]=1« 109M Strength = Molarity x mol. weight = 10? 40 = 0.04 g / litre. lonic Equilibrium @ 5.57 6. Find the pH of 0.004 M NH,OH having 3.2 % dissociation, Solution NH,OH — NH,* + OH" (weak base) © 0 0 cone, before ionization c(l-a) ca ca cone. after ionization [H}] =ca=3 x 109 x 435 = 1.29 104M pH =—log [H"] pH = 3.8894 7. Find the pH of solution obtained by mixing 20 ml of 0.1 M HCI and 30 ml of 0.2 MH,SO, Solution Milli equivalent of H* from HCl = 20 x 0.1=2 Milli equivalent of H* from H,SO, 10 0.2 « 2= 12 Total milli equiv. of H" in solution = 2 + 12 =14 ‘Total volume of solution = 20 + 30 = 50 My (H']= Vw 307 pH =-log [H"] 8. Calculate the pH of a solution containing 2.0 g of NaOH per litre of water. Solution As the solution contains 2.0 g of NaOH per litre of water, its normality = 35 = 25 N [OH] = 1/20 g-ion /titre (H*] [OH] 10" [H'] [1/20] = 10" [H'] =20 « 10" =2« 10 gion Aitre pH = —log [H"] = log [2 « 10]5.58 Mi lonic Equilibrium =~ [log 2-13 log 10] = -{0.3010- 13] = 12.699 9. Calculate the pH of a solution obtained by mix- ing 50 ml of 0.01 M Ba(OH), solution with 50 ml water, Solution N,V,=N,V, Ba(OH), mixture [Normality of solution of Ba(OH), = 2 * its molarity, as its mol, wt = 2 x eq. wt] 0.01 x 2 x 50 =N, x (50 +50) (as it is assumed as 100% ionized), 0.01 x 100 N=" T00 =0.01N [OH] =a. N=1*001=107 pOH = -log [OH] pOH=2 Jog 107=2 log 10 pH + pOH = 14 pH+2=14 pH=12 10. A 0.100 N NaOH solution was added to 50.0 ml of 0.100 N HC,H,O, solution. What would be the pH of the solution after the addition of 50.0 ml of NaOH solution and (it) 60.0 ml of NaOH solution? Solution (The addition of 50.00 ml of 0.100 N NaOH solution represents the end point of the titra~ tion. Therefore, the solution will be 0.00500 mole NaC,H,0, 0.100 Titre solution = 0.0500 M with respect to Nat Ky _ [HC,H,O,] [OH] KOK TIGHT As Suppose X = [HC,H,O,] = [OH] Since salt is essentially 100% ionized, [C,H,0, ] = 0.05 mole per litre _ LO x 10-4 Ky= [8x10 On solving, 3 10° mole OFF per litre As [H*] [OH-] = 1.0 x 10 at 25°C ery = Loto ~ 5.3% 104 a 50 x 10" X= = 19% 10° 1 pH=l0g,. 79793 = 87 Gi) All OFF ions will originate from the exeess of 10.0 ml of 0.100 N NaOH, therefore (0.010) (0.100) mole 0.100 Titre oH ]= = 9.1 « 10? mole per litre = 1 = POH = loge 5px Tos = 2-04 pH = 14,002.04 - 11.96 Saccharin (Ka = 2 x 10) is a weak acid represented by formula HSaC. A 4 * 10“ mole amount of saccharin is dissolved in 200 em? water of pH 3. Assuming no change in volume, calculate the concentration of SaC- ions in the resulting solution at equilibrium. Solution emole_ 4x10 4195 (HS2C] = Titre = 2007 1000 =? * 10° M The dissociation of HSaC takes place in pres- ence of [H']= 10° HSaC = H*+ SaC- Cone. before disso. 2107 10° 0 In presence of H* the dissociation of HSaC is almost negligible because of common ion effect. So at equilibrium [HSac] = 2 « 10° Hy = 10° _ [11 [8a] Ka="THsac] [10°] [Sac] 2x 10> «102M 2x 10% [Saclonic Equilibrium @ 5.59 12, An aqueous solution contains 10% ammonia by ‘mass and has a density of 0.99 g em. Caleu- late hydroxyl and hydrogen ion concentration in this solution, Ka for NH," = 5.0 = 10" M Solution Weight of NH, 19 Weight of solution 100 ‘As 100 g solution contains 10 g NH, 10 « 1000. 17 « (1000.99) (as V = mass/density) NH, + So MNH; = 5.82 — NH,OH = NH,’ + OH Before diss 1 0 0 (-a) a a After diss. [ol]=c a As C=5.82M [OH] = VI2 x 10 « 5.82] = 1.07 x 107M. pj= ot x 102 [HY] = Tgp qs = 0.9268 « 10"? M pH =—Iog,, [H"] = “log 0.9268 x 10-" = 12.0330 13. Calculate the pH at the equivalence point when a solution of 0.1 M acetic acid is titrated with a solution of 0.1 M NaOH. Ka for acid = 19% 105. Solution Suppose V ml of acid and V ml of NaOH is used concentration of both acid and NaOH are same. CH,COOH + NaOH — CH,COONa + H,0 OlxVolxv Cone, HXVOLXV 9 9 before reac. ; Olxv O1xy Cone, after 0 9 SEV OL reaction [CH,COONa] = 931 = 0.05 m CH,COONa + H,O = CH,COOH + NaOH [OH] =C a=CVK,/C)= VK, ©) =, /Ka).C] (10 = 0.05) 5.12 «10% 1.9% 105) pOH = 5.29 pH=871 14. How many moles of calcium hydroxide must be dissolved to produce 250.0 ml of an aqueous solution of pH 10.65? Assume complete dissociation. Solution pli +pOH=14 pOH = 14—pH =14-1065= 35 log [OH] = 3.35 log [OH"] =-3.35 = 4.65 [OH] = Antilog 4.65 = 4.47 x 104M = 4.47 x 104 mol L7 Moles of OH required for 250 ml = AaT x1 (250ml / 1000 mi). 1,12 « 10+ mol As I mol Ca(OH), produces 2 mol OH- ions. So moles of Ca(OH), dissolved = 112 « 10 mol 2 6 x 10 mol Ca(OH), 15, The pH of the 0.10 M hydrocyanic acid solutions is 5,2, What is the value of Ka for hydrocyanic acid? Solution pH =-log H’=5.2 log (H"] =-5.2=6.8 [1] = Antilog 6.8 = 6.31 « 10-°M HCN = Ht + cn 01-631 « 10-631 10*M631 = 10°M =0.1M —HICN] Ka-"THcN]5.60 Mi lonic Equilibrium _ (631 x 10M) x (6.31 x 10M) = 01M = 3.9816 « 10 =4.0 x 10 16. ‘The concentration of HCN and NaCN in a solu- tion is 0.01 M each. Calculate the concentration of hydrogen and hydroxy! ions if the dissocia- tion constant of HCN is 7.2 x 107”. Solution @ HCN = CN + (Q01-X)M XM XM (i) =~ NaCN = CN" + Nat Initial 001M 0M 0M Final 0.0M 001M 001M So at equilibrium, [H"] = X M [EN hay = FEN Iau * EON ha =XM+001 0.01M [HCN] = 0.01 M—XM=0.01M [CN 101M 00IM “log (H'] = log 7.2 « 10” (Ht) =7.2 « 10M = -log 7.2 * 10" + log Kw (OHI ~ 1x«lo“ 72K 10" 14 ™ 105M Buffer Solution Buffer solution is the solution whose pH does not change much by the addition of a small amount of a strong acid or a base. It is also called reserve acidity or basicity solution as it resists change of pH value and this action to resists pH change is called Butfer action. Features: m= Ithas a definite pH ie, reserve acidity or basicity. = It’s pH does not change on standing for a long time also = It’s pH does not change on dilution also = It’s pH slightly (unnoticeable) changes by the addi- tion of small quantity of a strong acid or base. Buffer Capacity Buffer capacity is the ratio of number of moles of the acid or base added in one litre of the solution so as to change its pH by unity, It is denoted by ©. added to 1 lit ‘No. of moles of acid / Change in pH © or It is also defined as the amount of a strong acid or strong base needed to change the pH of a buffer by one unit. Suppose we take a buffer solution of volume | L with ‘q’ mole of salt and ‘p’ mol of salt + acid . The pH of the buffer can be given as follows p= pK, oe On adding ‘x’ mol of a strong acid (monobasic), the pH changes to ax pH'= pk, +log GT a-x 4 ApH = log p> -log Gass ApH = log (5 4 oa ) 1 in(p4q Oats) 2.303, Pq a On differentiating with respect to x we get dx q ApH (= a UQ=9) «1 4p -4 48) * « = P © PFN (EN) 2308 On taking the inverse dx__ (P=4+8) (Gx) 2.303 “pH P Type of Buffer Solution 1. Acidic Buffer: It is a solution of a weak acid and its salt with a strong baselonic Equilibrium Ml 5.61 Example, CH,COOH + CH,COONa Phthalic acid + potassium phthalate Boric acid + Borax. HCO, + NaHCO, Citric acid + sodium citrate 2. Basic Buffer: It is a solution of a weak base and its salt with a strong acid Example, NH,OH +NHCI Glycine + glycine hydrogen chloride Glycerol + glycerine hydrogen chloride Ampholyte Solution: Example, Protein and amino acids also act like a buffer solution. 4. A mixture of acidic salt and normal salt of a polybasic acid Example, ‘Na,HPO, + NaPO, n Salt of weak acid and weak base (in water) Example, CH,COONH, , NH,CN Uses of Buffer Some of the important uses of buffer are as follows: (i) To determine pH value with the help of an indicator, (i) NHCl + NH,OH and (NH),CO, buffer solution is used to precipitate carbonates of Vih group (iii) CH,COOH and CH,COONa buffer is used to remove PO,? in qualitative inorganic analysis after IInd group, (iv) CH,COOH and CH,COONa buffer is used to precipitate lead chromate quantitatively in gravimetric analysis, (v) They are also used in paper, dye, printing ink, dairy product ete. (iv) H, CO, + NaHCO, maintains pH of blood. Illustrations 17, Calculate the pH of a 0.01 M NH,OH solu- tion containing 10 mol / litre of NH,Cl? (pK, = 4.76) Solution [Conjugate base] = 0.10 M NH, in H,O [Conjugate acid] = 1.0 M NH, Salt port, tog SE Lo =476+log ho = 4.76 + log 10 = 5.76 pH = 14-pOH 45.71 8.24 18. What volume of 0.1 M sodium formate solu- tion should be added to 50 ml of 0.05 M formic acid to produce a buffer solution of pH = 4.0, pKa of formic acid = 3.80? Solution Suppose V ml of 0.1 M HCOONa is mixed to 50 ml of 0.05 M HCOOH. ‘otal millimole [Molanty] =Total volume In mixture [HCOONa] = wes . (1x Vv) 4.0 = 3.80 + log, TS0VIS7T(V FSO) V=39.62 ml 19, Calculate the change in pH of | litre buffer solution containing 0.1 mole each of NH, and NH,Cl up on addition of, (@ 0.02 mole of dissolved gaseous HC1 Gi) 0.02 mole of dissolved NaOH. KNH, in volume. I (Assume no change 8x 105)5.62 Mi lonic Equilibrium Solution Initial pH of solution when, (NH) = °F and [HCI] = 5p Ol [Salt] POH = log, 1.8 10+ 10g, [Base] =Hlogy 18* 10° tog, 24 I pOH = 4.7447 pH = 9.2553 (@_ When 0.02 mole of HCI are added, HCI +NH,OH > NH,CI+H,0 Mole before diss. 0.02 0.1 0.1 Mole after diss. 0 0.08 (0.1 +0.02) As Volume = | litre So [NH,OH] = 0.08/1 [NH,CI] =0.12/1 pOH, =-log,, 1.8 « 10° + log,, O42 POH, = 4.9208 pH, = 9.0792 Change in pH = pH — pH, = 9.2553 - 9.0792 = 40.1761 Change in pH = 0.1761 unit ie, pH decreases (ii) When 0,02 mole of NaOH are added, NaOH + NH,CI —> NaCl + NH,OH Mole before diss. 0,02 0.1 0 0.1 Mole after diss. 0 0.08 0.02 0.12 pOH, = -log,, 1.8 « 10+ log, $98 POH, = 4.5686 pH, = 9.4314 Change in pH = pH ~ pH, = 9.2553 - 9.4314 =-0.1761 Change in pH = 0.1761 that is, pH increases. 20. Calculate the amount of NH, and NH, Cl required to prepare a buffer solution of pH 9.0 when total concentration of buffering reagents is 0.6 mol litre". pK, for NH, = 4.7, log,, 2 = 0.30 Solution pOH =-log,,K, +loz,, 5=47+108,,8 a/b=2 So a=2b atb=06 2b+b=06 3b=0.6 Given b=0.2 mole 2% 17=34 gfitre a=04 mole = 0.4 x 53.5= 21.4 gilitre [Salt] =0.4M [Base] = 0.2M 21, ‘The pH of 0.05 M aqueous solution of diethy amine is 12.0. Caleulate K, Solution (C,H),NH + H,0 = (CH,),NH, + OH Initial cone. 1 o 0 Eqecone. (I-a) a a [ol]=Ca Here C is cone. of base and C = 0.05 M As pH=12 (as C = 0.05) Ca? __ 0.05 x (0.2)? ~~ (=a) (1-02) 0.05 0.04 4 5. 193 OO = 25 * 10 K, 22. A solution contains 0.1 MHS and 0.3 M HCL. Calculate the cone. of S* and HS- ions in solution. Given Ka, and Ka, for HLS are 107 and 1.3 x 10° respectively,lonic Equilibrium m 5.63 Solution HS=H'+HS-— Ka,=107 HS=H'+S* — Ka=13 x10" HCI Ht + Cr Due to common ion effect the dissociation of HS is suppressed and the [H"] in solution is due to HCL. 197 = OFS (as [1] rom HCI = 0.3) fs] = 1704 3 10*M _ Hs] 1s] THs) eK TST (H'P [S*) TES) s) ny _ 037 [S*] 107 x13 x 10% = 77 Ka, x K L3 x10" xO. 0.09 [is] = 1.44 x 10M 23. Two buffers, (X) and (¥) of pH 4.0 and 6.0 respectively are prepared from acid HA and the salt Naa. Both the buffers are 0.50 M in HA. What would be the pH of the solution obtained by mixing equal volumes of the two buffers? (K,,,= 1.0 10) Solution pH =-1og,,Ke + log,, ep When pH=4 4=-log,, 1.0 105+ log,, Sau Salt] toe» 3M [Salt] = 0.1 « 0.5 =0.05M When pH= 6, 6=-log,, (1.0 « 10) + log,, oa 6=5 + 10g, Sant [Salt] = 10 x 0.5=5M Suppose V litre each of both buffers are mixed. The concentration of the salt in this solution will be: (0.05 Mx V) + (SMV) _ 5.05 44 [sal] Concentration of [HA] in mixed buffer (05M x V) x 05M XV) OSM HH = ~log,, (1.0 « 10°) + log, Berl = 5 +0,7033 = 5.7033 Solubility Itis the weight in gm of solute present in 100 ml of solvent . It is denoted by ‘s’ and is expressed in mol per litre or gm per litre, The number of moles of solute in 1 L of saturated solution is known as molar solubility Solubility 0 I/concentration of common ions ‘or number of common ions Example, The solubility of AgCl in water in presence of AgNO, Solubility formation. increases due to complex ion Example, AgCI has more solubility in ammonia due to complex formation. AgCl + 2NH, > Ag(NH,),Cl HCl, has more solubility in KI due to complex formation (Nesseler’s reagent). Hgl, +2KI > K Hel, In Hnd group analysis SnS, Sb,S, As,S, are soluble in (NH,),$ due to complex ion formation, SnS +S? — Sni Sb,S, +38 + 28bS,* AS,S, +387 > 2As8> Simultaneous Solubility: 1 is the solubility of a solution of two electrolytes having common ions.5.64 Ml lonic Equilibrium (1) AgBr+AgSCN Q) CaF, + Si, G3) MgF, + CaP, Solubility Product: It is the product of the molar concentrations of ions of an electrolyte in a saturated solution at a particular temperature. It is denoted by Ksp or S. Example, For a Binary Electrolyte AB: AB AB A‘+B Solid un-ionised (A°} 134 TAB] or K [AB] = [A*] [B>] or SoK= Ksp = [At] [B-] Atco tant temp. General Representation AxBy + XA" +yB* Ksp = [Aty]x [B-xly Example (1) CaF, + Ca? + 2F- Ksp =[Ca'] [FP Example (2) Ag,CrO, ++ 2Ag" + CrO, Ksp = [Ag'F [Cr0,-] Relation between Solubility(s) and Solubility Product (Ksp) AxBy © XA” + yB* a 0 0 a-s xs ys Ksp= (xs) (ys) or Ksp=x*y (57 Ifa is given Ksp=x*y (ay? Example Cu,Cl, «+ 2Cu' + 2C- "As 2s so Ksp = 2". 2? (s)'*7= 16 s* Fe(OH), + Fe"+ 30H s 3s Ksp = 11.395)" = 27 st AL(SO,), + 2AI +380, 2s 3s Ksp = 2°.3°(5)**? = 108 s* Na,Li,(AIF,), © 3Na’ + 3Li" + 2AIF? Ksp = 32.3°.22(s)'1?*2 = 2916 s Solubility Product and Precipitation = IfKsp= Ionic product Solution is saturated and for precipitation more solute is to be added. = If Tonic product > Ks.p solution is super saturated so easily precipitated = If Tonic product Ks.p Gii)_ In Analytical Chemistry: (A) Cation of IInd gp. [Cu*, Bi’, Hg”, Pb, Ca°*] are precipitatedas S* by using H,S + Hel at lower lene entration of $* due to the tact that they have lower Kp than other group cations. HS = 2H' +S? HCl = H*+Cr Common ionslonic Equilibrium 5.65 Here due to commonion effect cone* x S* decreases so far other gp. Cations Ksp > Ionic product hence they cannot be precipitated. B) Cations of Hird gp. (fe, AP*, Cr) are precipitated at low concentration of OH due to their lower Ksp than other gp. Cat-ions by using NH,OH +NH,CL NH,OH = NH, + OH NH,CI = NH, +Cr Common ions Due to common ions cone" of OH decreases so other gp. Cations cannot be precipitated as for them ksp > Ionic product. Illustrations 24, The solubility of Mg(OH), in water at 25°C is 0.00912 g per litre. Find Ksp for Mg(OH), assuming complete ionization Solution Mg(OH), = Mg* + OH-+OH- Imole I mole 2 mole Ksp = [Me™] [OH @ 0.00912 g Concentration of MeOH), = 3575 g male = 0.000156 mole per litre Since one mole of Mg(OH), yields one mole of Mg” ion and two moles of OH" ion, then [Mg*] = 0.000156 mole per litre [OH] = 2 * 0.000156 = 0.000312 mole per litre On putting the values in equation (i) Ksp = (0.000156) x (0.000312) = 1.52 « 10"" for Mg(OH), at 25°C The solubility product of StF, in water is 8 x 10". Find its solubility in 0.1 M NaF aqueous solution. Solution For SrF,, K, = FF Let the solubility of StF, in 0.1 M NaF be X, mol L* 8x 10=(%) OX +0.1F (Neglecting X* and X° terms) 0.01 X=8 x 10-8 X=8 x 10" mol 7 26. What (H,0") must be maintained in a saturated H,S solution to precipitate Pb®, but not Zn* from a solution in which each ion is present at a concentration of 0.01 M? (Ksp of HS = 11 * 10%, Ksp of ZnS = 1.0 1074) Solution For ZnS not to be precipitate from a solution of Zn** and Pb™, [Zn] [S*] 107 Example, FeCl, (weak base + strong acid): Solu- tion is acidic and involves cationic hydrolysis = A solution of the salt of strong base and weak acid is basic and for it pH> 7 or [H'] < 107 Example, KCN (strong base + weak acid): Solu- tion is basic and involves anionic hydrolysis. = A solution of the salt of weak acid and weak base ~ IfKa>K, itis acidic Ka Ka” 45% 10% 22x 10% 4H. Calculate for 0.01 N solution of sodium acetate, a. Hydrolysis constant b, Degree of hydrolysis « pH Given Ka=1.9 Solution CH,COONa +H,0 = CH,COOH + NaOH Before hydrolysis! 0 0 After hydrolysis (Ia) a alonic Equilibrium 5.69 Kyo | “i @ Ky Re= Se 752610 (&) a=V(K,/C) = 162610) 9.99 « 104 YO01 (©) [OH] from NaOH, a strong alkali = Ca =0.01 x 2.29 x 10" 29 « 10*M pOH = 5.64 pH=836 35. Calculate the percentage hydrolysis in 0.003 'M aqueous solution of NaOCN. Ka for HOCN, = 3.33 « 104 Solution NaOCN +H,O = NaOH +HCN VK, a=V(K,/C)= V(Ka.C) yo") “XG h= 104 % hydrolysis= 10“ = 100 = 107 % 10+ x 0.003) 36. Ka for butyric acid is 2.0 « 10. Calculate pH and hydroxyl ion concentration in 0.2 M aque- ‘ous solution of sodium butyrate. Solution NaBu +H,0 = NaOH + Bull Cone. before hydrolysis! 0 0 Cone. after hydrolysis 1-a a a [OH] = Ca=CVK,/0)= WK, ©) =\[(Ky/Ka) .C] lo «02 (OW ]= “y108 VIO"= 10-5 poH pH+pOH= 14 So pH=14-5=9 37. Kafor ascorbic acid (HAsC)is 5 * 10°, Calculate the hydrogen ion concentration and percentage of hydrolysis in an aqueous solution in which the concentration of AsC” ions is 0.02 M. Solution AsC-+H,O = HAsC + OH [OH] = Ca=C.VK,/C)=VK,.C) = WK,/Ka).C] V0" = 0.02) 2x 10¢ NGS « 10%) (y= a2 VK /O= Eo =O" Lge AGS « 105 * 0.02) 0.01% 38. Calcium lactate is a salt of weak acid and rep- resented as Ca(LaC),, A saturated solution of Ca(LaC), contains 0.13 mole of salt in 0.50 litre solution. The pOH of this 5.60, Assuming complete dissociation of salt, calculate Ka of lactic acid. Solution Ca(LaC), + 2H,0 = Ca(OH), + 2HLAC 2LaC-+2 20H: + 2HLac Before hydrolysis 1 0 Afterhydrolysis(I-a) a a [Ca(Lac),] = 913 = 0.26 [LaC] = 0.26 x 2=0.52M (as I mole Ca(LaC), gives 2 mole LaC.) [OH] =C a=CVK,/0)= VK, .©) VKyx.0) VKa Here C is the concentration of anion which undergoes hydrolysis. VO" = 0.52) \Ka Ka=825 x 104 1050=5.70 Mi lonic Equilibrium ACID AND BASES Strength of Acid and Base m= Acidic strength o Ka Arrhenius Concept of Acid . Dissociation const. of acid and Base m= Base strength o Kb According to it “Acids are H’ ion donor in water and Dissociation const. of base bases are OH- ion donor in water”. Relative strength = V(K, /K,) 1. Acids PERS SU arrreapear rch = HA + 1,0 > A> + 1,0" Hydronium ion or re Hydrated proton HPO, <2» HPO,? +H m= Water can accept H* to form hydronium ion _K, sate (H,0°) due to hydrogen bonding Lo tery ss Example,- (H,0,",H,0,") Here K, > K, >> K, so the correct acidic strength = Hi can hold water molecule by hydrogen bond as order is it has high heat of hydration. H,PO,> HPO, >HPO,* Example, - HNO, H,SO,, HX m= As negative charge develops the removal of H* = HO" has sp? hybridization and trigonal pyrami- | becomes more and more difficult so acidic nature dal shape, decreases. = Number of H* donated = Basic or protosity of the acid REMEMBER Example, . This concept fails to explain acidic and basic 1, HPO, (wibasic) nature in case of AICI, BX,, NH, ete. ° 1 H-0-P-0-H | Bronsted Lowry Concept an or Proton Concept 2. H,PO, (dibasic) 1. Acid: Acids are Proton or H* donor. H HA— A: + Ht | Acid conjugate base Beonteonk Example, -HX > H*+X- Conjugate b: 4 ‘onjugate base H,S0, + H* + Hso, 3. HPO. 2 SPO, acid conjugate base ° Fi HNO, > H'+ NO, H-P-H 2, Base: Bases are proton or H’ acceptor. | Base+H* + (Base H)* 0-H orproton conjugate base 2. Base: given by acid B.OH +H,0 +B’ +H,0, [other H,0,] Example, - OH-+ H' + H,0 Example, NaOH, KOH ete. Base conjugate acidlonic Equilibrium 5.74 Amphoteric or Ampholyte Substances Such substances can behave both like an acid and a base that is, can donate or accept H’ or proton Example, (1) a 0 NH, <2! nn, —# > nu Conjugate amphoteric conjugate acid base Example, (2) Ho’ <*— no —*. on Conjugate substance conjugate acid base Some other examples are HSO,", HCO,,H,PO,, HPO; H,PO,”, HS and HC,O, REMEMBER HPO, and HPO, are only bronsted bases as HPO, and H,PO, are monobasic and dibasic acid respectively so they can release only one and two H respectively. Lewis Concept of Acid and Base 1. Lewis Acid Lewis acids are electron deficient species which accept electron pair. Example, = Cations -Ct-, NO, +X" = Electron deficient central atom BeX,, BX,, FeX,, AIX, SnCl,, ZnCl, bed soud 4666 4 4 = Central atom with multiple bonds only O=C=0,0= 0,8 Ss = If in a molecule central atom has vacant ‘d-orbital. Itcan accept more than eight electrons that is, expansion of octate state so it can behave as a lewis acid. Example (1) PX, + X > PX, Lewis acid Lewis base Example (2) SIX, +2X— Six? Lewis acid m= Some Other Examples SnX,, PX,, GeX,, SF, SeF,, TeCl, = Elements with an electron sextet (Example, O, $ ete.) Strength of Lewis Acid Lewis acid strength o Electronegativity difference AF, AICI, AIBr, All, Acidic nature In case of Boron halide (BX,) BI, > BBr,> BCl, > BF, No back less back Example, ‘max back bonding bonding bonding Here, fluorine shifts its electron pairs back to boron atom as in F-atom due to its small size and more electron density (2p') there is more e- ~ e repulsion but in case of B atom size is large and 2p-orbital is almost vacant ‘The decreasing order of strength of some Lewis acids: BX, , AIX, FeX,, GaX,, SbX, InX,, SnX,, AsX,, ZnX,, HeX, 2. Lewis Base: These are electron efficient spe- cies which donate lone pair of electrons. Any anion or molecule with octet state and cen- tral atom with lone pair of electrons is a Lewis base as it can donate its lone pair. Example, ~X°, OH>, CN Example, No ON, R-NH, JN > PH, H-G-H R-G-H R-G-R2M lonic Equilibrium Some multiple bonded molecules which form complexes with transition metals, Example, CO, NO, C,H, ete Strength of Lewis Base Lewis base 0 1 /Electronegativity difference Example, ‘NH, > NI, > NBr> NCI, > NF, Less electronegativity difference REMEMBER CO, RCH =CH,,RC bases. Factors Effecting Acidic Strength: = Acidic strength Electronegativity difference Example (1) HF > H,0>NH,> CH, As electronegativity of F>O>N>C HNO, > H,CO, > HBO, As electronegativity of N>C>B Example (2) HCIO > HBr0 > HIO HCIO, > HBr0, > HIO, As clectronegativity of Cl > Br> I = Acidic strength o Size of central atom or easy removal of H” Example. HF HPO, >H,PO, Effect of Solvent on Acidic Strength: A sol- vent also effects acidic strength and it is called lev- cling effects Example (1) - CH,COOH CH,COOH behaves like a weak acid in water but in liquid ammonia itis a strong acid as ammonia has more tendeney than water to accept H Example, CH,COOH + H,0 «—+ CH,COO-+H,0° Acid Base CB CA. CH,COOH + NH, — CH,COO- + NH,” Acid Base CB CA CH,COOH in HF behaves like a base as HF is stronger acid than it CH,COOH + HF + CH,C 00° H, + F> Base Acid CA CB Example (2)— HNO, HINO, is although a strong acid in water but a weak acid in CH,COOH and a base in HF. = HCIO, (the strongest acid) becomes a weak acid in HF. ‘Some important acids in the decreasing order of acidie strength: HCIO, HCIO, HI, H,SO, HBr, HCI, H,0*,HNO,, HF, HSO, , H,PO,, HCOOH, CH,COOH,H,CO,,H,S, NH,, HCN, C,H,OH, HO, R - OH, HC = CH, NH, H,C=CH,, CH, C,H, C,H, (Cyclo hexane) ‘The strength of conjugate base will be in increasing order for the above acidic strength order that is, C10, ClO, , F, HO, NO, F-, SO", HPO, HCOO-, CH,COO-, HCO,, HS; NH,, CN, C,H,O-, “OH, “OR, C =CH, NH,, “CH = CH, “CH, “CH, “CH, Enhance Your Knowledge = According to Ingold concept an electrophile is an acid while a nucleophile is a base,Example, AICI, (El) is an acid and NH, (Nu) is a base. = In the reaction I,+ I I, the lewis base is T = [Fe(H,0),)* +H,0 + [Fe(H,0), OHP* +H,0" Acid Base CB CA lonic Equilibrium @ 5.73 = [Zn(H,0),OH}* + H,0° + [Zn(4,0),P+ H,0 Base Acid «CA. CB. = The reaction of a cation or anion with water accompanied by cleavage of © - H bond is called salt hydrolysis. Solved Problems from the IITs 1. The solubility of Mg(OH), in pure water is 9.57 x 107g L*. Caleulate its solubility in g Lt in 0.02 M Mg(NO,), solution, [IT 1986] Solution Solubility of Mg(OH), in pure water = 9.57% 107 gL _ 9.57 «109 ~ ‘Mol. mass = 9.57 «102 38 Mg(OH), = Mg?" + 20H- S 2s mol L* 65 « 10+ mol L* K,= [Mg] (O#-F =SxQsy =48° = 4x (1.65 x 104? = 17.9685 x 10? Let S” be the solubility of Mg(OH), in presence of Mg(NO,), As [Mg*]=(S’ +0) =(S’+0.02) [OH] = 2s" So K, +002) Qs’? 17.9685 * 10" 4(S' (S' + 0.02) 17.9685 = 10 a On neglecting (S’) we get, ‘S') + 0.02 (SF 4.4921 x 10? = 0,02 (S$ (sp = 44831 08 fe 4.9868 « 10-* mol L? Solubility of Mg(OH), in g L-!= S"* M = 14.9868 x 10-* x 58 =869« 104g Lt 2. What is the pH of the solution when 0.2 mole of hydrochloric acid is added to one litre of a solution containing 1 M acetic acid and acetate ion? Assume that the total volume is one litre. Ka for CH,COOH = 1.8 x 10°. [IT 1987] Solution On adding HCI, the free hydrogen ions ‘combine with CH,COO> ions to form CH,COOH. Thus, the concentration of acetic acid increases while that of CH,COO- ions decreases [CH,COOH] = (0.2 + 1) = 1.2 mol litre” [Salt] = (1 -0.2) = 0.8 mol litre According to Henderson's equation [Salt] PH=108,. 7agigy ~!08 Ka = og, $35 log, 1.8 x 10% = log,, 2 —1og,, 3~log,, 18 x 10 = 4.5687 3. How many gram moles of HCI will be required to prepare one lite of a buffer solution (having NaCN and HCN) of pH 8.5 using 0.01 g formula mass of NaCN? Ka for HCN = 4.1 x 10? [IT 1988] Solution Let “X’ moles of HCI be added. It combines with NaCN to form HCN.5.74 Mi lonic Equilibrium NaCN +HCl — NaCl +HCN x x x [NaCN] = (0.01 -X) [HCN] =X [NaCN] 0810 (HCN ~ 18 Ka DI 85 = log, 2°F=% _ tog,, 4.1 10” (0.01-X) 0X @01-X) x 0.01 X= 75} 99g = 0.0089 mole log, 85 +0.6127- 100 = 0.1296 Freshly precipitated aluminium and magnesium hydroxides are stirred vigorously in a buffer solution containing 0.05 mol L-! of NH,OH and 0.25 mol L-! of NH,Cl. Calculate’ the concentration of aluminium and magnesium ions in solution. Ksp Al(OH), = 6 « 10° K, NHOH= 1.8 « 10+ Ksp Mg(OH), = 6 * 10"? [OT 1989] Solution poH = log, gay oe kK, ~log,, [O11] = log,, 553 log, 18 x 10 Jog, [OF] =Iog,, !S< 10° [OH] = 0.36 « 10° mol L* Ksp AIOH), (ony = 610% 0.36% 105) [AP] = 1.29 10 mol L* Ksp Mg(OH), 5S. What is the pH of a 1.0 M solution of acetic acid? To what volume of one litre of this solution be diluted so thatthe pH of the resulting solution will be twice the original value? Given Ka=18% 104 [IT 1990] Solution As degree of dissociation (a) = \(Ka/C) =N.8« 105/1) = 4.2426 « 103 [H}=Cxa = 1 4.2426 x 109 = 4.2426 = 10° mol L* pH =—hg,, [1] = -log,, 4.2426 x 107 3724 So pH of the acetic acid solution after dilution = 2% 23724= 4.7448 New [H'] = 10478 = 1.8 x 105 Suppose the new concentration is C,, CH,COOH = H’ + CH,COO- At eg. C)= 1.8% 10% 1.8% 10% 18x 10% [H'] [CH,COO7] [CH,COOH] = 18x10 x 18 x 105 (C,-18% 107) As Ka= =18* 105 So C,=36x 104 Suppose the new volume is V litre 1*1=36«105xV 1 V" 36x10 = 2.78 * 10* litre 6. A certain weak acid has Ka = 1.0 x 104 Calculate the equilibrium constant for its reaction with a strong base. [OT 1991] Solution HA + BOH = BA+H,0 Weak Stronglonic Equilibrium @ 5.75 HA+B*+OH- = BY +A-+H,0 HA+OH-=A-+H,0 [Ay [HA] [OH] For the following reaction, [HA] [0H] K= The solubility product of Ag,C,O, at 25°C is 1.29 x 10" moP L>. A solution of K,C,0, containing 0.1520 mole in 500 ml of water is shaken with excess of Ag,CO, till the following equilibrium is reached. Ag,CO, +K,C,O, = Ag,C,0, +K,CO, At equilibrium, the solution contains 0.0358 mole of K,CO, Assuming the degree of dissociation of K,C,0, and K,CO, to be equal, calculate the solubility product of Ag,CO,, [UT 1991) Solution Ag,CO,+K,C,0, = Ag,C,0,+K,CO, Initial 0.1520mole 0 Ateq. (0.1520-0.0358) 0.0358 = 0.1162 mole mole Cone, 20.1162 2 0.0858 = 0.2324M =0.0716M Ksp Ag,C,0,= [Ag F [C021] (Ag']= [Ksp Ag,C,0, /1C,07 }"* Ksp Ag,CO, = [Ag'F [CO] (Ag'] = [Ksp Ag,CO, / [CO })”* so [Ksp Ag,C,0,/[C,02]]"? = [Ksp Ag,CO, /[CO,"1)"" Ksp Ag,C,0, * [CO,4] Ksp Ag,CO, = 1C.O21 . KK,cO] =Ksp 8.0.0, TKCO, = 129 x 19 x 2.0716 = 1.29 10" xh 5399 3.97 «10? moP L> ‘The Ksp of Ca(OH), is 4.42 x 10° at 25°C. 500 ml of saturated solution of Ca(OH), is mixed with equal volume of 0.4M NaOH. How much Ca(OH), in mg is precipitated? [UIT 1992} Solution Suppose ‘S’is the solubility of Ca(OH), in saturated solution. Ca(OH), = Ca®* + 20H Ss 2s Ksp Ca(OH), = [Ca*] [OH 4.42 « 10° =$x 4S" 4.42 x 105= 48° $= 0.0223 mol L* After mixing the two solutions, the total vol- ume becomes one litre. (ca*] = 99223 500 = 0.01115 mol L* - = 0.0223 x 2 x 500 , 0.4 x 500 fon] TO0O “1000 [From (Ca(OH), [From NaOH] = 0.2223 mol L Under the high concentration of OH- ions, some Ca(OH), will be precipitated. [Ca™],., [OH] *=Ksp 4.42 x 105 (0.2223)? = 8.94 « 10 mol L* [Ca hog = Moles of Ca(OH), precipitated = Moles of Ca* precipitate = [C8 asa ~ (CI = 0.01115 ~ 8.94 « 104 = ILS * 104 8.94 x 1045.76 Mi lonic Equilibrium = 102.56 104M = 102.56 x 104 « 74 g = 7589.44 « 104g = 758.944 mg 9. An aqueous solution of metal bromide, MBr, (0.05 M) is saturated with H,S. What is the minimum pH at which MS will precipitate? Ksp for MS 0 x 10*!, concentration of saturated H,S = 0.1 M. (K, = 10° and 1.3 = 10°" for H,8). [IT 1993} Solution Minimum concentration of S* ions required to precipitate MS is = 60107" 19 ig = 005 12* 10M HS ionizes in solution in following steps: HS=H+HS; K, HS- = H'+S>, fH] [HS] {HS} As K, = 10713 x10" x01 12x 107 = 1.08 « 107 (H’] = 1.04 « 10" pk = Hlog,, (1.04 x 10 ~Fog, [H'] =0.98 10. ThepH of blood stream is maintained by a proper balance of HCO, and NaHCO, concentrations What volume of 5 M NaHCO, solution should be mixed with a 10 ml sample of blood which is 2M in H,CO,, in order to maintain a pH of 7.47? Ka for H,CO, in blood is 7.8 « 10”. [IT 1993] Solution Suppose V ml of 5 M NaHCO, solution be mixed. Total volume = (V + 10) ml Concentration of H,CO, in the solution becomes [NaHCO,] = (H,CO,] According to Henderson’s equation, [NaHCO,} pH = -log,, Ka + logy. “EL CO,} : xVv_, (V+10) A=-log,, 7.8 « 107Hog,, wg “Tx 10 = Hog, 7.8 « 107 +1og,. log, Y= 7.4 + log,, 7:8 «107 V=78.32 ml 11. Find the pH of an aqueous solution of 1.0 M ammonium formed assuming complete dissociation. (pKa of formic acid = 3.8 and pK, [IT 1995] HCOONH, + HOH «+ HCOOH + NH,OH pH for a salt of weak acid and weak base pH =¥% [log,, K, - log,, Ka— log Kw] 4 [pKa + pKw- pK,] =% (38+ 14-48] =65. 12, The ionization constant of NH,’ in water is 56 = 10 at 25°C. The rate constant for the reaction of NH,” and OH to form NH, and H,O at 25°C is 3.4 * 10" litre mol" sec“, Find the rate constant for proton transfer from water to NH,, [IT 1996] NH,’ + H.OH «—» NH,OH + H* Ka=56« 10"lonic Equilibrium @ 5.77 NH, +HOH 4, NH, +0H- 2 Ky=3.4x 10" Kil Kw KWH)=K" RaQ) ei __ 1x10" 3.4% 10" 56x 10% K, = 6.07 « 10° 13. For 0.50 M aqueous solution of sodium eya- nide, (pK, of CN> is 4,70), calculate (i) hydro- lysis constant (ii) degree of hydrolysis (iii) pH [IT 1996} Solution Ky _Ky*K, © Ky" Ka "TK, (ASK, * K,=Ky) So Ky VK, /0) = VQ « 105/05) =63% 10? Gi) [OH] = ch=0.5 x 6.3 x 10° [OH] =3.15 102 pOH = pH=14-25= = 2 «105 w 14, What is the pH of a 0.5 M aqueous NaCN solution? pK, of CN is 4.70. [IT 1996} Solution p=4 pk, +4 pK, +410g,,M pK, +pK,=14 pK +4.7=14 pk,=93 atx 1444x9341 109,05 | 2 2 * 108. =74465-0.15 =1s 15. An acid type indicator, Hin differs in colour from its conjugate base (In-). The human eye is sensitive to colour differences only when the ratio [In] / [Hin] is greater than 10 or smaller than 0.1 what would be the minimum change in pH of the solution to observe a complete colour change (Ka = 1.0 x 10)? [IT 1997] Solution pH of the two given acidic buffers is as 16. follows: Salt] pit ka +g, Casel: pH =-log,, 1 x 10+ log,, 10 =S5+1=6 Case I: pH =—log,, 1 « 10+ log,, 0.1 =5- 4 So the minimum change in pH = 6 -4=2 What will be the resultant pH when 200 ml of ‘an aqueous solution of HC! (pH = 2) is mixed with 300 ml of an aqueous solution of NaQH (pH = 12)? [IT 1998] Solution 17. As pH of HC1=2 So [HCI] = 102M pH of NaOH = 12 [NaOH] = 10? M HCI + NaOH = NaCl +H,O M, 0 100x107 after reaction = 1 [OH after reaction =2x10°M pOk Jog,,2 «10° =27 ~log,, [01] pH=14-27=113 Given Ag(NH,),” = Ag’ +2NH,, K,=6.2 * 10 and Ksp of AgClis 18x 10" at 298 K. Calculate concentration of the complex in 1 M aqueous ammonia. [IT 1998]5.78 Mi lonic Equilibrium Solution Agcl = Ag* +Cl- On adding ammonia solution, complex forma- tion takes place. Ag’ + 2NH, &-y 1 oY Here [Ag(NH,),I° X= Solubility of AgCl in NH, Y= Amount of complex formed Ksp of AgCl = [Ag’] [CH] 18 «10 =(X-Y).X ......Gi) K,, for equation (i) _ [Aes [Ag TINH,F —1_-__Y__ 62x10" K=¥)xT ai) On solving equation (i) and (iii), we obtain Y= 0,0539M. 18. The solubility of Pb(OH), in water is 6.7 x 10* M, Calculate the solubility of Pb(OH), in a buf- fer solution of pH = 8 [UIT 1999) Solution Pb(OH), = Pb**+20H- Ksp = [Pb*] [OH = 6.7 x 10% «(2% 6.7 x 105? =4x (6.7 10) = 1.2% 10° Solubility of Pb(OH), in buffer system of pH & pH of buffer solution = 8 pOH=6 [OH] = 10 (pbe]= EIS = 1.2 109M 19, The average concentration of SO, in the atmosphere over a city on a certain day is 10 ppm, when the average temperature is 298 K Given that the solubility of SO, in water at 298 K is 1.3653 mol litre” and the pKa of H,SO, is 1,92, estimate the pH of rain on that day. [ITT 2000] Solution pKa= 1.92 Ka=Antilog (1.92) = 0.012 LF (802) o.o12 C8 ACO = gor “"Cd=a) (=a) 0.012 = 4 x (1.3653 a=0.117 = 2 1.3653 «0.117 3194 PH = -log,, x 0.3194 495 20, 500 ml of 0.2 M aqueous solution of acetic acid is mixed with 500 ml of 0.2 M HCI at 25°C. (a) Calculate the degree of dissociation of acetic acid in the resulting solution and pH of the solution. (b) If 6g of NaOH is added to the above solution, determine final pH. Assume there is no change in volume on mixing. Ka for acetic acid is 1.75 « 10M. [IT 2002) Solution (a) Concentration of HCl and CH,COOH after mixing will be 0.1 M CH,COOH = CH,COO- +H* t=0 0.1 0 0.1 (from HC) tl, O1-X X O1+x _[€H,C004 IF) Ka="[cH,COOH]lonic Equilibrium @ 5.79 21. X*x@1+X) @1-X) On solving, we get 1.75 «10 X= 175 «105 [1']=0.1+X=01M pH=—log,, [0.1]=1 Degree of dissociation of acetic acid = 175 «108 OT 1.75 « 104 (b) Number of moles of NaOH added =; =0.15 CH,COOH + HC1+NaOH = 0 O01 01 0.15 005 0 0 CH,COONa + NaCl +H,0 0 0 0 00s 0 0 [Salt] pH=pKa + logy facay =Aog,, 1.75 10+ log, 303 = 4.757 Will the pH of water be same at 4°C and 25°C? Explain. [IT 2003} Solution 22. K, =H") (O14 At25°C — [H'] = [OH]= 1.01 x 107M pH =—log,, [H'] = Hog, [10°] =7 At4°C, ionization of water will be less than that at 25°C, As at 25°C K,,= [H"] [OH] will be less than 10 so pH of water will be more than 7 at 4°C 0.1 M NaOH is titrated with 0.1 M HA till the end point; Ka for HA is 5.6 x 10 and degree of hydrolysis is less compared to one. Calculate pH of the resulting solution at the end point. [IT 2004] Solution Neutralization of HA with NaOH may be given as, HA+NaOH > NaA+H,O Concentration of salt will be 0.1 /2M that is, 0.05 M, as volume will be double. pH of salt after hydrolysis may be calculated as, pH=4 (pk, +pKatlogC] .....@) pK y= 14 pKa=-log,,Ka = -log,, (5.6 « 10) = 5.2518 log,, C = log,, 0.05 = -1.3010 On putting the values of pK.,, pKa and log,, C in equation (i), we obtain pH=4 [14 +5.2518- 1.3010] = 8.9754 23. 0.1 mol of methyl amine (K, = 5 « 10+) is mixed with 0.08 mol of HCI and the solution is diluted to 1 litre. Determine the hydrogen ion concentration of the resulting solution [IT 2005] Solution CH,NH, + HCI - CH,N‘H,Cr Initially 0.1 mol 0.08 mol 0 mol On 0.02mol Omol 0.08 mol completion This resulting solution is a basic buffer for which [Salt] POH=pK, +108, 73ase] Jog,, 5 * 104+ log, 098 =33+06=3.9 pH=14-39=10.1 H'=8x10"M5.80 M lonic Equilibrium MULTIPLE-CHOICE QUESTIONS Straight Objective Type Questions (Single Choice only) 1. At 90°C, pure water has [H,O"] 10% mole litre What is the value of Kw at 90°C? a 10* b. 10 «10 a. 10" 2. Which of the following has the highest pH? a. 0.1 MNaOH b. 0.1 MCH,COOH ©. 0.01 MNeOH 4. 0.1 MHC! 3. Which among the following is the least soluble? a. MnS (Ksp =7« 10°) b. FeS Ksp = 4 10") €. PIS (Ksp =8 « 107) 4. NiS (Ksp=3 = 10") 4. Of the given anions, the strongest bronsted base is a. ClO; b. clo, « Clo- 4. Clo- 5. The conjugate acid of O ion is a. HO bo © HO 4. OF 6 The pHofa 10 molar solution of HCI in water is a8 bs €. between 6and7 — d. between 7 and & 7. Aacidic buffer solution can be prepared by mixing the solutions of a. sodium chloride and sodium hydroxide b. sulphuric acid and sodium sulphate ¢. ammonium chloride and ammonium hydroxide 4, ammonium acetate and acetic acid 8 At 25°C, the pH of pure water is 7. It dissociates as 1,0 (I) + H,0 () + HO" + “OH, AH? =-13.7 Keal mol", pH water of 37°C is expected to be b.=7 4. none of these a>7 <7 u. 2 1B. 4. 16. Molten sodium chloride conduets electricity due to the presence of a free ions b. free molecules & free electrons, 4, atoms of sodium and chlorine Conjugate base of hydrazoie acid is a HN, bNS © Azide ion 4. Nitride ion The precipitate of CaF, (Ksp= 1.7 = 10°") is obtained when equal volumes of the following are mixed 10° M Ca? +103 MF b. 10°M Ca + 10* MF & 104M Ca + 104M F- . 109M Ca + 10° MF Out of Ca®, AP*, Cr, Mg and Zn*, the reagents, NH,Cl and aqueous NH, will precipitate a. Cae, AD b. AP, Cr ©. Bi*, Mg d. Mg, Zn? A certain weak acid has a dissociation constant of 1.0 = 10+, the equilibrium constant for its reaction with a strong base is a 10% 10" © 1010" b. 10 10" d. 1.0 104 Which of the following compounds ean form a buf fer solution? &, Na,HPO, and NaH,PO, b. HCl and NH,CI ©. CH,COOH and HCOOH d. Na,PO, and NaOH ‘The compound that is not a Lewis acid is a SnCl, b. BeCl, © BF, 4. AICI, 10 ml of 0.2 M acid is added to 250 ml of a buf fer solution with pH = 6.34. The pH of the solution, becomes 6.32. The bufler capacity of the solution is a 04 b. 03 © 02 4.01lonic Equilibrium 5.81 17. 18. 19, 20, 21, 2, ‘The conjugate acid of NH, is a. NH, b. NH, «. NHOH 4. NH, The solubility products of AKOH), and Zn(OH), are 8.5 = 10 and 1.8 * 10" respectively. If NHOH is added to solution containing AV” and Zn** ions, then substance precipitated that is a. Zn(OH), b. AIOH), «. both (a) and (b) _d. none of these ‘The best indicator for detection of end point in titration of a weak acid and a strong base is ‘a, methyl red (5 t0 6) 'b, methyl orange (3 to 4) . phenolphthalene (8 to 9.6) 4. bromothymol blue (6 to 7.5) ‘The pKa of acetylsalicylic acid (aspirin) is 3.5 = 10%. The pH of gastrie juice in human stomach is about 2 ~ 3 and the pH in the small intestine is about 8. Aspirin will be ‘8, ionized to the stomach and almost unionized in the small intestine b. ionized in the small intestine and almost union- ized in the stomach . unionized in small intestine and in the stomach 4. completely ionized in the small intestine and in the stomach ‘The pKa of acetyl salicylic acid (aspirin) is 3.5 ‘The pH of gastric juice in human stomach is about 23 and pH in the small intestine is about 8, Aspi- rin will be ‘ionized in the small intestine and almost union- ized in the stomach b. unionized in the small intestine and in the stom- ach . completely ionized in the small intestine and in the stomach 4. ionized in the stomach and almost unionized in the small intestine ‘The aqueous solution of NH,CN is slightly alkaline because itis a salt . CN ion hydrolyses to a greater extent than NIH, ion ¢. NH,’ ion hydrolyses to a greater extent than CN*ion 4. both hydrolyses to an equal extent ‘The compound whose 0.1 M solution is basic is ‘4. ammonium acetate >, ammonium sulphate 24, 28, 26. 27. 28, 29. 30, ¢. sodium acetate 4. ammonium chloride ‘Which among the following acts as @ basic butler? a. NH,Cl+ NHOH b, NaCl + NaOH ©. NH,Cl + CH,COOH 4, CH,COONa + CH,COOH Amongst the following hydroxides, the one which has the lowest value of Ksp at ordinary temperature (about 25°C) is a MeOH), ©. B(OH), b. CuoH, 4. BOR, ‘The strongest Bronsted base among the following a. CHO ©. (CH,),CHO- b. CHO” 4. (CH,),CO ‘The pH of the neutralization point of 0.1 N ammo- nium hydroxide with 0.1 NHCL is, b.6 a7 al 69 ‘The following reactions are known to occur in the body CO, + H,0 ++ H,CO, ++ Ht + HCO," IFCO, escapes from the system a pH will decrease . Hydrogen ion concentration will diminish €. H,CO, concentration will remain unchanged 4. the forward reaction will be favoured ‘The following equilibrium is established when hydrogen chloride is dissolved in acetic acid HCI + CH,COOH + Cl + CH,COOH,” The set that characterizes the conjugate acid base pair is a (HCI, CH,COOH) and (CH,COOH,, CI) b. (HCI, CH,COOH,’) and (HCI, CH,COOH,) and (CH,COOH, Cl) ©. (CH,COOH,’, HCl) and (Cl, CH,COOH) 4. (HCI, CI) and (CH,COOH,”, CH,COOH) Which of the following are Lewis acids? WBF, diy H,o Gi) HO, Gv) SO, a. (and Gii) b. Gand Gi) ©. (and iv) 4. Gii)and Gv)5.82 M lonic Equilibrium 31. 32. 38, 37. 39. ‘The pKa pf HCN is 9.30, The pH of a solution pre- pared by mixing 2.5 moles of KCN and 2.5 moles Of ICN in water and making up the total volume to 500 ml is a. 930 «730 b. 830 4. 1030 ‘What is the pH ofa 0.25 M weak acid that is 2.2% ionazied ? a, 0.60 . 1.00 b. 2.00 4. 2.26 Fear or excitement, generally causes one to breathe rapidly and it results in the decrease of CO, con- centration in blood. In what way will it change the pH of blood? ‘8, pH will increase b. pHwill decrease no change 4. pH will adjust to 7, Which of the following is correet order of inereas- ing acidity? a. HI HCl HCI >HBr> HI 4. HF > HCL HI ‘The pH of a 0.1 M aqueous solution of a weak acid (HA) is 3. What is its degree of dissociation? a 1% ©. 50% Ammonium cyanide is salt of NH,OH of Kb=2.5 * 10° and HCN of Ka = 4.0 » 10° The hydrolysis, constant of NH,CN at 25°C is a 46 b. 44 «24 a4 Ifthe acids HA and HB have dissociation constants 1 10" and 1 = 10+ respectively, then ‘a, HAs five times stronger than HB b, HA js ten times stronger than HB ¢. HAis ten times weaker than HB 4. HA js five times weaker than HB ‘The dissociation constant of two acids HA, and HA, are 3.0 « 10 and 1.8 « 10 respectively. The relative strengths of the acids is a 116 bla e 4 @. 16:1 ‘The strongest Bronsted base in the following 40. al a2, 48, 46. 48, a ClO” « Clo, When solid potassium eyanide is added in water, then its a. pHi will decrease », pH will increase «. electrical conductivity will not change 4. pH will remain the same ‘The solubility of CuBr is 2 » 10 mol L-! at 25°C The Ksp value for CuBr is a 410% be 410% 6 4x10" 4410 ‘The solubility of MX, type electrolyte is 0.5 10* mol L*. The value of Ksp of the electrolyte is a 135108 b. 25 «108 510% 5+ 10" The solubility product of PCI, at 20°C is 1.5 = 10+ Its solubility is & 3.45 «10? mol Lb, 3.34» 10¢ mol L? © 334 10? mol L*) d. 3.85» 104 mol L* Which has highest pH? a CH,COOK b. Na,CO, « NHCI . NaNO, How do you differentiate between Fe" and Cr" in ‘group III? a By increasing NH,” ion concentration . By decreasing OH-ion concentration ©. By taking excess of NHOH 4, Both (a) and (b) 0.005 M acid solution has 5 pH. The percentage ionization of acid is, a 08% © 04% b. 0.6% d. 0.2% Which one of the following order of acid strengths is correct? &, RCOOH > HC = CH > HOH > ROH b. RCOOH >HOH> HC = CH> ROH ©. RCOOH > ROH > HOH > HC = CH d. RCOOH > HOH > ROH > HC = CH ‘The concentrations of H* and OH-of a 0.1 aqueous, solution of 2% ionized weak acid are [ionie product of water = 1» 10] a. 3 10*Mand 5 « 10M b. 0.1 x 10?Mand 3 « 10" Mlonic Equilibrium 5.83 49. 02% 10° Mand 5 «10M 4, 2 10° Mand 5 « 10" M. When rain is accompanied by thunderstorm, the collected rain water will have a pH value ‘a. slightly lower than that of rain water without thunderstorm, 'b. which depends on the amount of dust in air . slightly higher than that of rain water without thunderstorm 4. uninfluenced by the occurrence of thunder- storm ‘The pH value of an acid is 5 and its concentration is 1 M. Whatis the value of Ka for the acid? a. 104 b. 10" 10? 4.10" Which of the following is not a buffer solution? . 0.05 MKCIO, + 0.05 MHCIO, b. 2MC,H,NH, + 2M C,H,’NH,Br ©. 08 MHS + 0.8MKHS 4. 3MH.CO, +3 MKHCO, ‘The conjugate base of H,PO,-is a. HPO b. HPO, © PO, 4. P.O, ‘A rapid change of pH near stiochiometric point of an acid-base titration is the basis of indicator detection. The pH of solution is related to the ratio of concentrations of conjugate acid (HIn] and base forms of the indicator by the expression On] a log qpitey ~PH-PK Hn bs tog OTS) = pt—pk, tog Ut! = pk, —plt {in} 4. log [tay ~ PK. PH ‘Two solutions A and B are prepared by adding ‘NaOH and HCI acid into water respectively. The ionic product of water will ‘a, increase in B and decrease in A b. increase in A and B . remain the same in two solutions 4. increase in A and decrease in B Dimethyl glyoxime gives a red precipitate with Ni’, which is used for its detection. To get this precipitate readily, the best pH range is 59, 60, a. 02, a 01 6 9.11 v.23 4. 3.6 The molar solubility of a sparingly used soluble salt MX, is “S”. The corresponding solubility prod- uctis Ksp. The value of “S’is given in terms of Ksp by the relation a. $= (Ksp /128)"" $= (Ksp/256)"" ‘The conjugate base of OH-is, a HO b. OF oO 4.0, b. $= (256 Ksp)!* . $= (128 Ksp)"* ‘What is the correct relationship between the pHs of isomolar solutions of sodium oxide (pH,), sodium sulphide (pH), sodium selenide (pH,) and sodium telluride (pH)? a. pH,> pH, ~ pH,> pH, ». pH, pH,> pH,> pH, When 10 mL. of 0.1 M acetic acid (pKa = 5.0) is titrated against 10 mL of 0.1 M ammonia solution (pKb = 5.0) the equivalence point occurs at pH a 50 b. 60 90 4.70 SS gas when passed through a solution of cations containing HCI precipitates the cations of second group of qualitative analysis but not those belong- ing to the fourth group. It is beeause & Solubility product of group II sulphides is more than that of group IV sulphides b. Presence of HCI increases the sulphide ion con- centration © Sulphides of group IV cations are unstable in HCL d. Presence of HCI decreases the sulphide ion concentration A solution has pH ~ 5, itis diluted 100 times, then it will become: b. More acidic d. Unaffected a Neutral ©. Basic A buffer solution has equal volume of 0.2 M NH{OH and 0,02 M NH{Cl. The pX, of the base is 5. The pllis ad b. 10 a7 a9 Solubility product of a salt AB is 1 = 10% M? in a solution in which the concentration of A* ion is 107