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EXERCISE Q.

Reaction quotient and equilibrium constant The initial concentrations or pressure of reactants and products are given for each of the following systems. Calculate the reaction quotient and determine the directions in which each system will shift to reach equilibrium. ; [H2] = 1.00 M 2NH3 (g) ^ N2 (g) + 3H2 (g) Kp = 6.8 x 104 atm2 Initial pressure : NH3 = 3.0 atm; N2 = 2.0 atm; H2 = 1.0 atm 2S03(g) 2S0 2 (g) + 0 2 (g) " K = 0.230 atm [S03] = 0.00 M ; [S02] = 1.00 M ; [02] = 1.00 M 2S03(g) ^ 2S0 2 (g) + 0 2 (g) Kp = 16.5 atm Initial pressure: S0 3 = 1.0 atm; S0 2 =1.0 atm; 0 2 = 1.0 atm 2NO(g) + Cl2 (g) ^ 2NOC1 (g) K = 4.6 x 104 [NO] = 1.00 M ; [Cl2] = 1.00 M; [NOC1] = 0 M N2 (g) + 0 2 (g) ^ 2NO (g) Kp = 0.050 Initial pressure: NO =10.0 atm; N2 = 0 2 = 5 atm Among the solubility rules is the statement that all chlorides are soluble except Hg2Cl2, AgCl, PbCl2, and CuCl. Write the expression for the equilibrium constant for the reaction represented by the equation. AgCl(s)^Ag + (aq) + Cl-(aq) Is K greater than 1, less than 1, or about equal to 1 ? Explain your answer Write the expression for the equilibrium constant for the reaction represented by the equation Pb2+ (aq) + 2C1- (aq) ^ PbCl2 (s) Is K greater than 1, less than 1, or about equal to 1 ? Explain your answer. Among the solubility rules is the statement that carbonates, phosphates, borates, arsenates, and arsenites, except those of the ammonium ion and the alkali metals are insoluble. Write the expression for the equilibrium constant for the reaction represented by the equation CaC03 (s) ^ Ca2+ (aq) + C032" (aq) Is K greater than 1, less than 1, or about equal to 1 ? Explain your answer Write the expression for the equilibrium constant for the reaction represented by the equation. 3Ba2+ (aq) + 2P043" (aq) ^ Ba^PO,), (s) Is K greater than 1, less than 1, or about equal to 1 ? Explain your answer. Benzene is one of the compounds used as octane enhancers in unleaded gasoline. It is manufactured by the catalytic conversion of acetylene to benzene. 3C2H2 > C6H6 Would this reaction be most useful commercially if K were about 0.01, about 1, or about 10? Explain your answer. Showthe complete chemical equation and the net ionic equation for the reaction represented by the equation KI (aq) + I2 (aq) ^ KI3 (aq) give the same expression for the reaction quotient. KI3 is composed of the ions K+ and
Pffj-hxaoY^et? b\ p\JKOVTY-NA/ ^
6i
2NHJ (g) ^ N 2 (g) + 3H 2 (g) [NH3] = 0.20 M ; [N2] = 1.00 M K=17

(a)

(b) (c) (d) (d) (f)

Q. 2 (a)

(b)

Q.3 (a)

(b)

Q.4

Q.5

{'

"

JcxOij [11]

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CHEMICAL EQUILIBRIUM

Q. 6 (a) (b) Q. 7 (a) (b) (c) Q. 8

Using the equilibrium constant Which of the following reactions goes almost al 1 the way to completion, and which proceeds hardly at all? N2(g) + 02(g) ^ 2NO (g); Kc = 2.7 * 10"18 2NO(g) + 02(g) ^ 2N0 2 (g); Kc = 6.0 x l O13 For which ofthe following reactions will the equilibrium mixture contain an appreciable concentration of both reactants and products? Cl 2 (g)^2Cl(g); Kc = 6.4xi 0 - 3 9 Cl2(g) + 2NO (g) ^ 2NOC1 (g) ; Kc = 3.7 x 108 Cl2(g) + 2N0 2 (g) ^ 2N02C1 (g); Kc = 1.8 The value of Kc for the reaction 30 2 (g) ^ 20 3 (g) is 1.7 x 10"56 at 25C. Do you expect pure air at 25C to contain much 0 3 (ozone) when 0 2 and 0 3 are in equilibrium? If the equilibrium concentration of 0 2 in air at 25C is 8 x 10~3 M, what is the equilibrium concentration of 0 3 ? At 1400 K, Kc = 2.5 x 10"3 for the reaction CH4 (g) + 2H2S ^ CS2(g) + 4H2(g). A10.0 L reaction vessel at 1400 K contains 2.0 mol of CH4,3.0 mol of CS2,3.0 mol of H2 and 4.0 mol ofH2S. Is the reaction mixture at equilibrium? Ifnot, in which direction does the reaction proceed to reach equilibrium?

Q.9

Q.10 Thefirststep in the industrial synthesis of hydrogen is the reaction of steam and methane to give water gas, a mixture of carbon monoxide and hydrogen. H 2 0 (g) + CH4(g) ^ CO (g) + 3H2(g)Kc = 4.7 at 1400 K A mixture of reactants and product at 1400 K contains 0.03 5 M H20,0.050M CH4,0.15 M CO, and 0.20 M H2. In which direction does the reaction proceed to reach equilibrium? Q.ll An equilibrium mixture of N2, H2, and NH3 at 700 K contains 0.036 M N2 and 0.15 M H2. At this temperature, Kc for the reaction N2(g) + SH^g) ^ 2NH3(g) is 0.29. What is the concentration ofNH3?

Q.12 The air pollutant NO is produced in automobile engines from the high temperature reaction N2(g) + 02(g) ^ 2NO (g); Kc = 1.7 x 10-3 at 2300 K. If the initial concentrations ofN 2 and 0 2 at 2300 K are both 1.40 M, what are the concentrations of NO, N2, and 0 2 when the reaction mixture reaches equilibrium? Q.13 At a certain temperature, the reaction PCl5(g) ^ PCl3(g) + Cl2(g) has an equilibrium constant Kc = 5.8 x 10"2. Calculate the equilibrium concentrations of PC15, PC13 and Cl2 if only PC15 is present initially, at a concentration of 0.160 M. Q.14 At 700 K, Kp = 0.140 for the reaction C1F3 (g) ^ C1F (g) + F2(g). Calculate the equilibrium partial pressure of C1F3, C1F, and F2 if only C1F3 is present initially, at a partial pressure of 1.47 atm. Homogeneous equilibria degree of dissociation, vapour density and equilibrium constant Q. 15 The degree of dissociation of N 0 0 4 into N0 2 at 1.5 atmosphere and 40C is 0.25. Calculate its Kp at 40C. Also report degree of dissociation at 10 atmospheric pressure at same temperature. Q.16 At 46C, Kp for the reaction N204(g) ^ 2N02(g) is 0.667 atm. Compute the percent dissociation of N 2 0 4 at46C at a total pressure of 380Torr,

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[13]

Q.17 When 36.8gN 204(g) is introduced into a 1.0-litre flask at 27C . The following equilibrium reaction occurs : N 2 0 4 (g) ^ 2N0 2 (g); Kp = 0.1642 atm. (a) Calculate Kc of the equilibrium reaction. (b) What are the number of moles of N2 0 4 and N0 2 at equilibrium? (c) What is the total gas pressure in the flask at equilibrium? (d) What is the percent dissociation of N204? Q.18 At some temperature and under a pressure of 4 atm, PC15 is 10% dissociated. Calculate the pressure at which PC15 will be 20% dissociated, temperature remaining same. Q.19 In a mixture of N2 and H2 in the ratio of 1:3 at 64 atmospheric pressure and 300C, the percentage of ammonia under equlibriumis 33.33 by volume. Calculate the equilibrium constant ofthe reaction using the equation. N2(g) + 3H2(g) ^ 2NH3(g). Q. 20 The system N 2 0 4 ^ 2 N0 2 maintained in a closed vessel at 60 C & a pressure of 5 atm has an average (i.e. observed) molecular weight of 69, calculate Kp. At what pressure at the same temperature would the observed molecular weight be (23 0/3) ? Q.21 The vapour density of N 2 0 4 at a certain temperature is 3 0. Calculate the percentage dissociation of N 2 0 4 at this temperature. N204(g) ^ 2N0 2 (g). Q.22 In the esterfication C2H5OH (1) + CH3COOH (1) ^ CH3COOC2H5 (1) + H 2 0 (1) an equimolar mixture of alcohol and acid taken initially yields under equilibrium, the water with mole fraction=0.333. Calculate the equilibrium constant. Hetrogeneous equilibrium Q.23 Solid Ammonium carbamate dissociates as: NH2 COONH4 (s) ^ 2NH3(g) + C02(g). In a closed vessel solid ammonium carbamate is in equilibrium with its dissociation products. At equilibrium, ammonia is added such that the partial pressure ofNH, at new equilibrium now equals the original total pressure. Calculate the ratio of total pressure at new equilibrium to that of original total pressure. Q. 24 A sample of CaC03(s) is introduced into a sealed container of volume 0.821 litre & heated to 1000K until equilibrium is reached. The equilibrium constant for the reaction CaC03(s) ^ CaO(s) + C02(g) is 4 x LO-2 atm at this temperature. Calculate the mass of CaO present at equilibrium. Q.25 Anhydrous calcium chloride is often used as a dessicant. In the presence of excess of CaCl2, the amount of the water taken up is governed by Kp = 6.4 x 1085 for the following reaction at room temperature, CaCl2(s) + 6H20(g) ^ CaCl2,6H20(s). What is the equilibrium vapour pressure of water in a closed vessel that contains CaCl2(s) ? Q. 26 20.0 grams of CaC03(s) were placed in a closed vessel, heated & maintained at 727 C under equilibrium CaC03(s) ^ CaO(s) + C02(g) and it is found that 75 % of CaC03 was decomposed. What is the value of Kp ? The volume of the container was 15 litres. Changes in concentration at equilibrium Le Chatelier's principle Q.27 Suggest four ways in which the concentration of hydrazine, N2H4, could be increased in an equilibrium described by the equation N2 (g) + 2H2 (g) ^ N2H4 (g) AH = 95 kJ

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[13]

Q.28 (a) (b) (c) (d)

How will an increase in temperature affect each of the following equilibria? An increase in pressure? 2NH 3 (g)^N 2 (g) + 3H2(g) AH = 92 kJ N2 (g) + 0 2 (g) ^ 2NO (g) AH = 181 kJ AH = - 285 kJ 20 3 (g) ^ 30 2 (g) CaO (s) + C0 2 (g) ^ CaC03 (s) AH = - 176 kJ

Q. 29(a) Methanol, a liquid fuel that could possibly replace gasoline, can be prepared from water gas and additional hydrogen at high temperature and pressure in the presence of a suitable catalyst. Write the expression for the equilibrium constant for the reversible reaction. AH = - 90.2 kJ 2H2(g) + CO(g)^CH 3 OH(g) (b) Assume that equil ibrium has been established and predicthowthe concentration ofT^, CO and CH, OH will differ at a new equilibrium if(1) more H^ is added. (2) CO is removed. (3) CH^OH is added. (4) the pressure on the system is increased. (5) the temperature ofthe system is increased. (6) more catalyst is added. Q.30(a) Water gas, a mixture of H2 and CO, is an important industrial fuel produced by the reaction of steam with red-hot coke, essentially pure carbon. Write the expression for the equilibrium constant for the reversible reaction. C(s) + H 2 0 (g) ^ CO (g) + ^ (g) AH = 131.30 kJ Assume that equilibrium has been established and predict how the concentration of each reactant and (b) product will differ at a new equilibrium if (1) more C is added. (2) H 2 0 is removed. (3) CO is added. (4) the pressure on the system is increased. (5) the temperature of the system is increased. Q.31 Ammonia is a weak base that reacts with water according to the equation NH3 (aq) + H 2 0 (I) ^ NH4+ + OH- (aq) Will any of the following increase the percent of ammonia that is converted to the ammonium ion in water? (a) Addition of NaOH. (b) Addition of HCl. (c) Addition ofNH4Cl. Q.32 Suggest two ways in which the equilibrium concentration ofAg+ can be reduced in a solution ofNa+, Cl~, Ag+ and N03~, in contact with solid AgCl. Na+ (aq) + Cl~ (aq) + Ag+ (aq) + N0 3 - (aq) ^ AgCl (s) + Na+ (aq) + N03~ (aq) AH = -65.9 kJ Q.33 Additional solid silver sulfate, a slightly soluble solid, is added to a solution of silver ion and sulfate ion in equilibrium with solid silver sulfate. Which ofthe following will occur? (a) The Ag+ and S042- concentration will not change, (b) The added silver sulfate will dissolve, (c) Additional silver sulfate will form and precipitatefromsolution as Ag+ ions and S042" ions combine, (d) The Ag+ ion concentration will increase and the S042 ion concentration will decrease. Kinetics and equilibrium constant Q.34 Consider a general, single-step reaction of the type A+ B ^ C. Show that the equilibrium constant is equal to the ratio of the rate constant for the forward and reverse reaction, Kc = k/kr. Q.35 Which ofthe following relative values of kf and kr results in an equilibrium mixture that contains large amounts of reactants and small amounts of product? (a)k f >k r (b) kf = kr (c)k f <k r Q.36 Consider the gas-phase hydration of hexafluoroacetone, (CF3)2CO: (CF3)2CO (g) + H2O (g) % (CF3)2C(OH)2 (g)
k

At 76C, the forward and reverse rate constants are k f =0.13 M ' V 1 and kr = 6.02 x 1 O^s"1. What is the value ofthe equilibrium constant Kc? <!\Bansal Classes CHEMICAL EQUILIBRIUM [13]

Q.37 Consider the reaction of chloromethane with OH in aqueous solution kf


Ct^Cl (aq) + OH- (aq) ^ CH3OH (aq) + CI" (aq)
k

At 25 C, the rate constant for the forward reaction is 6 * 10-6 M_1 s"1, and the equilibrium constant Kc isl x 1016. Calculate the rate constant for the reverse reaction at 25C. Q.38 The progress of the reaction A ^ nB with time, is presented infigure.Determine (i) the value of n. (ii) the equilibrium constant k (iii) the initial rate of conversion ofA

Time / Hour

Temperature dependence of equilibrium constant Q.39 Listed in the table are forward and reverse rate constants for the reaction 2NO (g) ;N2(g)+02(g) Temperature (K) (IVTV1) k,. (lVHs-1) 1400 0.29 1.1 x 10-6 1500 1.3 1.4 xlO"5 Is the reaction endothermic or exothermic? Explain in terms of kinetics. Q. 40 Forward and reverse rate constant for the reaction C02(g) + N2(g) CO(g) + N 2 0 (g) exhibit the following temperature dependence. Temperature (K) (M'V 1 ) k r (M-1s_1) 1200 9.1 1CT11 1.5 105 9 1500 2.7 x 10~ 2.6 x 105 Is the reaction endothermic or exothermic? Explain in terms of kinetics.
X X

Q.41 The equilibrium constant K for the reaction PCl5(g) ^ PCl3(g) + Cl2(g) is 3.81 x 102 at 600 K and 2.69 x 1 o3 at 700 K. Calculate AjH. Q.42 As shown infigurea catalyst lowers the activation energy for the forward and reverse reactions by the same amount, AEa. (a) (b) Apply the Arrhenius equation, K = Ae a/ to the forward and reverse reactions, and show that a catalyst increases the rates of both reactions by the same factor. Use the relation between the equilibrium constant and the forward and reverse rate constants, Kc = kj/kr, to show that a catalyst does not affect the value ofthe equilibrium constant.
~E /RT

Reaction progress

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[13]

Temperature dependence of equilibrium constant Q. 43 Variation of equilibrium constant K' with temperature T is given by equation AH log K = log A - 2.303 RT A graph between log K and 1 /T was a straight line with -ve slope of 0.5 and intercept 10. Calculate AH Pre exponential factor Equilibrium constant at 298 K Equilibrium constant at 798 K assuming AH0 to be independent of temperature.

(a) (b) (c) (d)

Q. 44 Rate of disappearance of the reactant Aat two different temperature is given b y A ^ B dt = (2xl0-2 S-1) [A] - 4 x 10~3 S- ! [B]; 300K

= (4x 10"2 S"1) [A] - 1 6 x 1 0 ^ [B]; 400K dt Calculate heat of reaction in the given temperature range. When equilibrium is set up. Q.45 The Kp for reaction A+ B ^ C + D isl .34 at 60C and 6.64 at 100C. Determine the free energy change ofthis reaction at each temperature and AH for the reaction over this range of temperature? Equilibrium expressions and equilibrium constants Q. 46 If Kc = 7.5 x 10~9 at 1000 K for the reaction N2 (g) + 0 2 (g) ^ 2NO (g), what is Kc at 1000 K for the reaction 2NO (g) ^ N2 (g) + 0 2 (g)? Q.47 An equilibrium mixture of PC15, PC13 and Cl2 at a certain temperature contains 8.3 x 10~3 M PC15, 1.5 x 1 (T2 M PC13, and 3.2 x l"(T2 M Cl2. Calculate the equilibrium constant Kc for the reaction PCl 5 (g)^PCl 3 (g) + Cl2(g). Q.48 AsampleofHI(9.30 x 1CT3 mol) was placed in an empty 2.00 L container at 1000 K. After equilibrium was reached, the concentration of I2 was 6.29 x 10-4 M. Calculate the value of Kc at 1000 K for the reaction H2 (g) +12 (g) ^ 2HI (g). Q. 49 The vapour pressure of water at 25C is 0.0313 atm. Calculate the values of Kp and Kc at 25C for the equilibrium H 2 0 (1) ^ H 2 0 (g). Q.50 For each ofthe following equilibria, write the equilibrium constant expression for Kc. Where appropriate, also write the equilibrium constant expression for K . (a) Fe 2 0 3 (s) + 3 C 0 ( g ) ^ 2 F e ( / ) + 3C0 2 (g) (b) 4Fe(s) + 30 2 (g) ^ 2Fe203 (s) (c) BaS04 (s) ^ BaO (s) + S0 3 (g) (d) BaS04 (s) ^ Ba2+(aq) + S042" (aq) Generalproblems Q. 51 When 0.5 mol of N 2 0 4 is placed in a 4.00 L reaction vessel and heated at 400 K, 79.3% ofthe N 2 0 4 decomposes to N0 2 . Calculate Kc and Kp at 400 K for the reaction N 2 0 4 (g) ^ 2N02(g) Q.52 What concentration ofNH3 is in equilibrium with 1.0 x 10~3MN2and2.0 x 10-3MH2at700K?At this temperature Kc = 0.291 for the reaction N2(g) + 3H2 (g) ^ 2NH3 (g). Q.53 At 100 K the value of Kc for the reaction C (s) + I^O (g) ^ C 0 ( g ) + H 2 (g)is3.0x 1 o~2. Calculate the equilibrium concentrations ofH20, C02, and Hj in the reaction mixture obtained by heating 6.0 mol of steam and an excess of solid carbon in a 5.0 L container. What is the molar composition ofthe equilibrium mixture? <!\ Bansal Classes CHEMICAL EQUILIBRIUM [13]

Q. 54 When 1.0 mol of PC15 is introduced into a 5.0 L container at 500 K, 78.5 % of the PC15 dissociates to give an equilibrium mixture of PC15, PC13, and Cl2. PCl 5 (g)^PCl 3 (g) + Cl2(g) (a) Calculate the values of Kc and Kp. (b) If the initial concentrations in a particular mixture of reactants and products are [PC15] = 0.5 M, [PC13] = 0.15 M, and [C1J = 0.6 M, in which direction does the reaction proceed to reach equilibrium? What are the concentrations when the mixture reaches equilibrium? Q.55 The equilibrium constant Kc for the gas-phase thermal decomposition of cyclopropane to propene is 1.0 x 105 at 500 K. /CH 2 cyclopropane Propene What is the value ofK p at 500 K? What is the equilibrium partial pressure of cyclopropane at 500 K when the partial pressure of propene is 5.0 atm? Can you alter the ratio ofthe two concentrations at equilibrium by adding cyclopropane or by decreasing the volume ofthe container? Explain. Which has the larger rate constant, the forward reaction or the reverse reaction? Why is cyclopropane so reactive? Thermodynamic and equilibrium constant Q.56 a-D-Glucose undergoes mutarotation to P-D-Glucose in aqueous solution. If at 298 K there is 60% conversion. Calculate AG ofthe reaction. a-D-Glucose ^ P-D-Glucose Q.57 For the reaction at 298 K A(g) + B(g)^C(g) + D(g) AH = - 29.8 kcal; AS0 = -0.1 kcal / K Calculate AG and K. Q.58 The equilibrium constant of the reaction 2C3H6(g) ^ CjH^g) + C4Hg(g) is found to fit the expression 1088K lnK = -1.04 T Calculate the standard reaction enthalpy and entropy at 400 K.

(a) (b) (c) (d) (e)

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[13]

PROFICIENCY TEST 1. K for the reaction 2A+B ^ 2C is 1.5 x 1012. This indicates that at equilibrium the concentration of would be maximum. The reaction N2 + 0 2 ^ 2NO - Heat, would be favoured by temperature. .

2. 3. 4.

K for the reaction X 2 +Y 2 ^ 2XY is 100 K. For reaction XY ^ ^ X ^ - Y2 would be

Compared to K for the dissociation, 2HjS ^ 2H++2HS , then K' for the H+ + HS ^ I^S would have

5.

The equilibrium constant for a reaction decreases with increase in temperature, the reaction must be

6. 7.

For the reaction, PCl5(g) ^ PCl3(g) + Cl2(g), K p and K c are related as

For the reactions, N204(g) ^ 2N02(g), at equilibrium, increase in pressure shifts the equilibrium in direction. AG is related to K by the relation Vant Hoff s equation is . . . .

8. 9. 10. 11 . 12. 13. 14.

When the reaction is at equilibrium, the value of AG is

Dimensions of equilibrium constant for the reaction 2NHJ ^ N2 + 3H2, are The value ofK for a reaction can be changed by changing The law of mass action was proposed by .

The degree of dissociation of PC15 [PCl5(g) ^ PCl3(g) + Cl2(g)], at equilibrium.

with increase in pressure

15. 16. 17. 18. 19. 20. 21.

If concentration quotient, Q is greater than K^, the net reaction in taking place in The reaction, N2 + 3H2 ^ 2NH3 would be favoured by Kp is related to K c as . pressure.

direction.

Solubility of a gas in water with increase in temperature. Introduction of inert gas at constant volume to a gaseous reaction at equilibrium results in formation of product. The product is more stable than reactants in reaction having K.

Van't Hoff s equation gives the quantitative relation between change in value of K with change in temperature.

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CHEMICAL EQUILIBRIUM

[18]

22. 23. 24. 25. 26.

The larger value of K indicates that the product is more stable relative to reactants. The value of equilibrium constant changes with change in the initial concentration ofthe reactants. Extent of a reaction can always be increased by increasing the temperature. Kp is related to K c as Kp = K c (RT) An . Introduction of inert gas at a gaseous reaction at equilibrium keeping pressure constant has no effect on equilibrium state. For the reaction, N 2 0 4 (g) ^ 2N02(g), Kp = K c (RT). For a reaction the value of Q greater than K indicates that the net reaction is proceeding in backward direction. Solubilities ofall solids in water increase with increase in temperature. Dissolution of all gases in water is accompanied by evolution of heat. For the reaction, N2 + 3H2 ^ 2NHL, the equilibrium expression may be written as K = For the reaction, CaC03(s) ^ CaO(s) + C02(g), Kp = p C o 2 . A catalyst increases the value ofthe equilibrium constant for a reaction. If concentration quotient of reaction is less than K, the net reaction is proceeding in the backward direction. In case ofendothermic reactions, the equilibrium shifts in backward direction on increasing the temperature. The value of K increases with increase in pressure. For the reaction, F^ + I ^ 2EH, the equilibrium constant, K is dimensionless. The reaction 2S02(g)+02(g) ^ 2S03(g), AH=-XkJ, is favoured by high pressure and high temperature. Avery high value of K indicates that at equilibrium most of the reactants are converted into products. The value of K for the reaction, N2 + 2H2 ^ 2NHJ, can be increased by applying high pressure or by using a catalyst. [NH3]2
3

27. 28.

29. 30. 31. 32. 33. 34.

[N2]|H2J

35. 3 6. 37. 38. 39. 40.

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CHEMICAL EQUILIBRIUM

[13]

EXERCISE III Q. 1 At high temperatures phosgene, COCl2decomposetogiveCO&Cl2. Inatypical experiments x 1CT4 kg of COCl2 is injected into a flask of volume 0.4105 dm3 at 1000 K. When equilibrium is established it is found that the total pressure in the flaskis3.039 x 105 pascals. Calculate the equilibrium constant (Kp) for this reaction at 1000 K. 2 moles ofA& 3 moles of B are mixedinl litre vessel and the reaction is carried at 400C according to the equation; A+ B ^ 2 C. The equilibrium constant of the reaction is 4. Find the number of moles ofC at equilibrium. 2NOBr(g)^2NO(g) + Br2(g). If nitrosylbromide(NOBr) is33.33% dissociated at25C& a total pressure of 0.28 atm. Calculate Kpfor the dissociation at this temperature. At 90C, the following equilibrium is established : H2(g) + S(s) ^ H2S(g) Kp = 6.8 x lO-2 If 0.2 mol of hydrogen and 1.0 mol of sulphur are heated to 90C in a 1.0 litre vessel, what will be the partial pressure of E^S at equilibrium? The equilibrium constant for the reaction is 9.40 at 900C S2(g) + C(s) ^ CS2(g). Calculate the pressure oftwo gases at equilibrium, when 1.42 atm of S2 and excess of C(s) come to equilibrium. A mixture of 2 moles of CH4 & 34 gms ofFLjS was placed in an evacuated container, which was then heated to & maintained at 727 C. When equilibrium was established in the gaseous reaction CH4 + 2 H2S ^ CS2 + 4 H2 the total pressure in the container was 0.92 atm & the partial pressure of hydrogen was 0.2 atm. What was the volume of the container ? At 817 C, Kp for the reaction between pure C0 2 and excess hot graphite to form 2 CO(g) is 10 atm. What is the analysis of the gases at equilibrium at 817C & a total pressure of 4.0 atm ? What is the partial pressure of C0 2 at equilibrium ? At what total pressure will the gas mixture analyze 6%, C0 2 by volume ? The equilibrium mixture S0 2 + N0 2 ^ S0 3 + NO was found to contain 0.6 mol of S03,0.40 mol of NO, 0.8 mol of S0 2 & 0.1 mol of N0 2 in a 1L vessel. One mole of NO was then forced into the reaction vessel with V & T constant Calculate the amounts of each gas in the new equilibrium mixture. For the reaction N 2 0 4 ^ 2N02, equilibrium mixture contains N0 2 at P = 1.1 atm & N 2 0 4 at P=0.28 atm at 3 50 K. The volume of the container is doubled. Calculate the equilibrium pressures of the two gases when the system reaches new equilibrium.

Q.2

Q.3

Q.4

Q.5

Q.6

Q.7 (a) (b) Q.8

Q.9

Q.10 In the preceding problem, calculate the degree of dissociation, a at both pressures corresponding to mean molar masses of 65 & 76.667. Use data from the preceding problem. Q. 11 PC15 dissociates according to the reaction PC15 ^ PCl3(g) + Cl2(g). At 523 K, Kp = 1.78 atm. Find the density of the equilibrium mixture at a total pressure of 1 atm. Q.12 The reaction 3/2H2(g) + 112 N2(g) ^ NH(g) was carried out at T = 620 K & P = 10 atm with an initial mixture of H^: N 2 =3 :1, the mixture at equilibrium contained 7.35 % NH^. Find Kp and Kc.

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CHEMICAL EQUILIBRIUM

"[28]

Q. 13 For the reaction S02(g) + 1/2 02(g) ^ S03(g) AH29g = - 98.32 kJ/mole, AS298 = - 95.0 J/K/mole. Find the Kp for this reaction at 298 K. Q.14 The following data for the equilibrium composition ofthe reaction 2Na(g) ^ Na2(g) at 1.013 MPa pressure and 1482.53 K have been obtained, mass % Na (monomer gas) = 71.3 mass % Na2 (dimer gas) = 28.7 Calculate the equilirium constant Kp. Q.15 The degree of dissociation of HI at a particular temperature is 0.8. Find the volume of 1. 5M sodium thiosulphate solution required to react completely with the iodine present at equilibrium in acidic conditions, when 0.135 mol each of H2 and I2 are heated at 440 K in a closed vessel of capacity 2.0 L. Q.16 A reaction system in equilibrium according to the equation 2 S0 2 + 0 2 ^ 2 S03 in 1 litre reaction vessel at a given temperature was found to contain 0.11 mol of S0 2 ,0.12 mol of S0 3 and 0.05 mol of 0 2 . Another 1 litre reaction vessel contains 64 g of S02 at the same temperature. What mass of 0 2 must be added to this vessel in order that at equilibrium half of S0 2 is oxidised to S0 3 ? Q.17 Amixture ofhydrogen & iodine in the mole ratio 1.5 :1 is maintained at 450 C. After the attainment of equilibrium H2(g) + I2(g) ^ 2 HI(g), it is found on analysis that the mole ratio of I2 to HI is 1 : 18. Calculate the equilibrium constant & the number of moles of each species present under equilibrium, if initially, 127 grams of iodine were taken. Q.18 In a closed container nitrogen and hydrogen mixture initially in a mole ratio of 1:4 reached equilibrium. It is found that the half hydrogen is converted to ammonia. Ifthe original pressure was 180 atm, what will be the partial pressure of ammonia at equilibrium. (There is no change in temperature) Q.19 The equilibrium constant for the reaction C0(g)+H 2 0(g)^C0 2 (g)+H 2 (g) is7.3at450C& latm pressure. The initial concentration of water gas [CO + FL,] & steam are 2 moles & 5 moles respectively. Find the number of moles of CO, H2, C0 2 & F^O (vapour) at equilibrium. Q.20 At 1200C, the following equilibrium is established between chlorine atoms & molecule: Cl2(g) ^ 2C1 (g) The composition of the equilibrium mixture may be determined by measuring the rate of effusion of the mixture through a pin hole. It is found that at 1200C and 1 atm pressure the mixtureeffuses 1.16 times as fast as krypton effuses under the same condition. Calculate the equilibrium constant kc. Q.21 Two solids X and Ydisssociate into gaseous products at a certain temperature as follows: X(s) ^ A(g) + C(g), and Y(s) ^ B(g) + C(g). At a given temperature, pressure over excess solid X is 40 mm and total pressure over solid Y is 60 mm. Calculate: (a) the values of K for two reactions (in mm) (b) the ratio of moles ofA and Bin the vapour state over a mixture of X and Y (c) the total pressure of gases over a mixture of X and Y Q. 22 S03 decomposes at a temperature of 1000 K and at a total pressure of 1.642 atm. At equilibrium, the density of mixture is found to be 1.28 g/1 in a vessel of 90 literes. Find the degree of dissociation of S03 for S03 ^ S0 2 + l/20 2 .

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CHEMICAL EQUILIBRIUM

[13]

Q.23

Consider the equilibrium: P(g) + 2Q(g) ^ R(g). When the reaction is carried out at a certain temperature, the equilibrium conceentration of P and Q are 3M and 4M respectively. When the volume of the vessel is doubled and the equilibrium is allowed to be reestablished, the concentration of Q is found to be 3M. Find (A) Kc (B) concentration of R at two equilibrium stages.

Q. 24 When PC15 is heated, it dissociates into PC13 and Cl2. The vapor density of the gaseous mixture at 200C and 250C is 70.2 and 57.9 respectively. Find the % dissociation ofPCl5 at 200C and 250C. Q.25 The density of an equilibrium mixture of N 2 0 4 and N0 2 atl01.32KP a is3.62g dm"3 at 288 K and 1.84 g dm"3 at 348K. What is the heat ofthe reaction for N 2 0 4 ^ 2NOa (g). Q. 26 Two solid compounds A& C dissociates into gaseous productat temperature as follows A ( s ) ^ B ( g ) + E(g) C ( s ) ^ D ( g ) + E(g) At 20 C pressure over excess solid Ais 50atm & that over excess solid C is 68atm. Find the total pressure of gases over the solid mixture. Q.27 The equilibrium constant for the following reaction at 13 95 K. 2H20 ^ 2H2 + 0 2 Kj = 2.1 x 10"13 2C02 ^ 2CO + 0 2 K 2 = 1.4 x 10-12 Calculate the value ofK for the reaction : H2 + C0 2 ^ C0 + H 2 0 Q.28 A saturated solution of iodine in water contains 0.33g / L. More than this can dissolve in aKI solution because ofthe following equilibrium: I2(aq) +I~ (aq) ^ I3~(aq). A0.10M KI solution (0.10 MI") actually dissolves 12.5 g of iodine/L, most of which is converted to I3~. Assuming that the concentration ofI2 in all saturated solutions is the same, calculate the equilibrium constant for the above reaction. What is the effect of adding water to a clear saturated of I2 in the KI solution ? Q.29 The equilibriump-Xyloquinone + methylene white ^p-Xylohydroquinone + methylene blue may be studied convinently by observing the difference in color methylene white and methylene blue. One mmol ofmethylene blue was added to 1L of solution that was 0.24 M in p-Xylohydroquinone and 0.012 M in p-Xyloquinone. It was then found that 4% of the added methylene blue was reduced to methylene white. What is the equilibrium constant of the above reaction? The equation is balanced with one mole each of 4 substances. Q.30 A mixture of N2 & H2 are in equilibrium at 600 K at a total pressure of 80 atm. If the initial ratio of N2 and are 3:1 and at equilibrium NH3 is 10% by volume. Calculate Kp of reaction at given temperature. K, , NH3 is -16.5 kJ mol"1. Find the equilibrium Q.31 AG (298 K) for the reaction 1/2 N2 + 3/2 H, constant (Kj) at 25C .What will be the equilibrium constants K2 and K, for the following reactions: N2 + 3H2 ^ NI^ ^ l / 2 N
2 0

2NH3 + 3/2H 2

Q.32 A certain gas Apolymerizes to a small extent at a given temperature & pressure, nA^A n . Show that the gas obeys the approx. equation ZX = RT where K = ^ & V is the volume of the ' [A]" conatiner. Assume that initially one mole ofA was taken in the container.
   

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Q.33

1CT3 mol ofCuSC^.SHjO is introduced in a 1.9 Lvesselmaintained ata constant temperature of27C containing moist air at relative humidity of 12.5%. What is the final molar composition of solid mixture? For CuS0 4 .5^00) ^ CuS04(s)+51^0^), Kp(atm)= 1 CT10. Takevapor pressure ofwater at27Cas 28 tons.

Q.34 When 1 mol ofA(g) is introduced in a closed 1L vessel maintained at constant temperature, the following equilibria are established. A(g)^B(g) + 2C(g) ; Kj = ? C(g)^2D(g) + 3B(g); K2 = ? The pressure at equilibrium is
v

(13)

J times the initial pressure.

Calculate

& K c 2 if [ A j

4 = ~,

Q.35 When NO & N0 2 are mixed, the following equilibria are readily obtained; Kp = 6.8 atm-1 2N0 2 ^ N 2 0 4 N0 + N0 2 ^ N 2 0 3 Kp = ? In an experiment when NO & N0 2 are mixed in the ratio of 1:2, the totalfinalpressure was 5.05 atm & the partial pressure of N 2 0 4 was 1.7 atm. Calculate (a) the equilibrium partial pressure of NO. (b) Kp for NO + N0 2 ^ N 2 0 3 Q.36 Solid NH4I on rapid heating in a closed vessel at 357C develops a constant pressure of 275 mm Hg owing to partial decomposition ofNH4I into NF^ and HI but the pressure gradually increases further (when the excess solid residue remains in the vessel) owing to the dissociation of HI. Calculate thefinalpressure developed at equilibrium. NH4I(s) ^ NH3(g)+HI(g) 2HI(g) ^ H2(g) + I2(g), Kc = 0.065 at 357C Q.37 Given are the following standardfreeenergies of formation at 298K. H20(g) H20(/) CO(g) C02(g) ArG/kJmoH -137.17 -394.36 -228.57 -237.13 (a) Find AfG and the standard equilibrium constant K 0 at 298 K for the reaction C0(g) + H20(g) ^ C02(g) + H2(g) (b) If CO, C0 2 and H2 are mixed so that the partial pressure of each is 101.325 kPa and the mixture is brought into contact with excess of liquid water, what will be the partial pressure of each gas when equilibrium is attained at298K. The volume available to the gases is constant. Q.38 For the reaction C2H6(g) ^ C2H4(g) + H2(g) Kp is 0.05 and ArG is 22.384 kJmoH at 900 K. If an initial mixture comprising 20 mol of C2H6 and 80 mol ofN2(inert) is passed over a dehydrogenation catalyst at 900K, what is the equilibrium percentage composition of the effluent gas mixture? The total pressure is kept at 0.5 bar. Given: ArS = 13 5.143 J K"1 moF1 at 300K. Calculate ArG at 300K. (Assume ArCp = 0)

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Q.39(a) The equilibrium H2(g) + C02(g) < = > H20(g) + CO(g) is established in an evacuated vessel at 723 K starting with 0.1 mole of H2 & 0.2 mole of C02. If the equilibrium mixture contains 10 mole per cent of water vapour, calculate Kp, given that the equilibrium pressure is 0.5 atm. Calculate the partial pressures of the component species & the volume of the container, (b) If now, into the flask (mentioned in the preceding problem), solid CoO & solid Co are introduced two new equilibria are established. CoO(s) + H2(g) ^ Co(s) + H 2 0(g) ; CoO(s) + CO(g) ^ Co(s) + C02(g) The new equilibrium mixture contains 30 mole precent of water vapour. Calculate the equilibrium constants for the new equilibria. Q.40 Some iodine is dissolved in an aqueous solution ofKI of concentration 0.102 mole/1, and the solution is then shaken with equal volume of CC14 until equilibrium is reached (at 15C). The total amount of iodine (present as Ij" (aq) or as I2 (aq)) at equilibrium is found to be 0.048 mol/1 in the aqueous layer and 0.085 mol/1 in the CC14 layer. The distribution coefficient of iodine between CC14 and water is 85. Calculate the equilibrium constant at 15C for the reaction: l3~(aq) ^ I2 (aq) +I"(aq)

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CHEMICAL EQUILIBRIUM

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EXERCISE Q. 1

III

Consider following reactions in equilibrium with equilibrium concentration 0.01M of every species (I) PC15 (g) ^ PCl3(g) + Cl2(g) (II) 2HI(g) ^ H2(g) +12 (g) (m)N2(g) + 3H 2 (g)^2NH 3 (g) Extent of the reactions taking place is: (A)i>n>m (B)i<n<in (C)n<m<i (D)m<i<n For the reaction 3 A(g) + B (g) ^ 2 C (g) at a given temperature, Kc = 9.0 . What must be the volume of the flask, if a mixture of 2.0 mol each of A, B and C exist in equilibrium? (A) 6L (B)9L (C) 36 L (D) None of these Sulfide ion in alkaline solution reacts with solid sulfur to form polysulfide ions having formulas S22-, S32-, S42" and so on. The equilibrium constant for the formation of S22~ is 12 (Kj) & for the formation of S 3 2- is 132 (K^), bothfromS and S2_.What is the equilibrium constant for the formation of S32" from S 2 2- and S? (B) 12 (C) 132 (D) None of these (A) 11 For the following gases equilibrium. N 2 0 4 (g) ^ 2N0 2 (g) Kp is found to be equal to Kc. This is attained when (A) 0C (B) 273 K (C) 1 K

Q.2

Q.3

Q.4

(D) 12.19 K

Q.5

1 mole N2 and 3 mol H2 are placed in a closed container at a pressure of 4 atm. The pressure falls to 3 atm at the same temperature when the following equilibrium is attained. N2(g) + 3H2(g) ^ 2NH3(g). The equilibrium constant Kp for dissociation ofNFL, is: (A
(l.5)3atm-2(B)0.5x(l.5)W (C)^^atm
2

(D) q / ^ 3 atm'2

Q. 6

One mole of N 2 0 4 (g) at 3 00 K is left in a closed container under one atm. It is heated to 600 K when 20 % by mass of N 2 0 4 (g) decomposes to N0 2 (g). The resultant pressure is : (A) 1.2 atm (B) 2.4 atm (C) 2.0 atm (D) 1.0 atm For the reaction: 2H1 (g) ^ H^g)+l2(g), the degree of dissociated (a) ofHl(g) is related to equilibrium constant Kp by the expression 1 + 2 IK (A) - ^ J L 1 + 2K (B) e .
2K

Q.7

(C)

P
(
D

VKP

l + 2KP

H + 2/KP

Q. 8

The vapour density of N 2 0 4 at a certain temperature is 3 0. What is the % dissociation of N 2 0 4 at this temperature? * (A) 53.3% (B) 106.6% (C)26.7% (D)None For the reaction PCl5(g) ^ PCl3(g) + Cl2(g), the forward reaction at constant temperature is favoured by (A) introducing an inert gas at constant volume (B) introducing chlorine gas at constant volume (C) introducing an inert gas at constant pressure (D) increasing the volume of the container (E) introducing PC15 at constant volume. CHEMICAL EQUILIBRIUM "[28]

Q.9

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Q.10 When N 2 0 5 is heated at temp. T, it dissociates as N 2 0 5 N 2 3 + 0 2 , K C =: 2.5. At the same time N203 also decomposes as: N203 ^ N 2 0 + 0 2 . If initially 4.0 moles of N 2 0 5 are taken in 1.0 litre flask and allowed to attain equilibrium, concentration of 0 2 was formed to be 2.5 M Equilibrium concentration of N 2 0 is (D) 0.334 (A) 1.0 (B)1.5 (C) 2.166 Q. 11 Densities of diamond and graphite are 3.5 and 2.3 gm/mL. C (diamond) ^ C (graphite) ArH = -1.9 kJ/mole favourable conditions for formation ofdiamond are (A) high pressure and low temperature (B) low pressure and high temperature (C) high pressure and high temperature (D) low pressure and low temperature Q.12 When NaN03 is heated in a closed vessel, oxygen is liberated and NaN02 is left behind. At equilibrium (A) addition of NaN02 favours reverse reaction (B) addition of NaN03 favours forward reaction (C) increasing temperature favours forward reaction (D) increasing pressure favours reverse reaction Q. 13 The equilibrium S02Cl2(g) ^ S02(g) + Cl2(g) is attained at25C in a closed rigid container and an inert gas, helium is introduced. Which of the following statements is/are correct. (A) concentrations of S02, Cl2 and S02C12 do not change (B) more chlorine is formed < (C) concentration of S0 2 is reduced (D) more S02C12 is formed Q. 14 For the gas phase reaction, C2H4 + H2 ^ C2H6 (AH = -32.7 kcal), carried out in a closed vessel, the equilibrium concentration of C ^ can be increased by (A) increasing the temperature (B) decreasing the pressure (D) adding some C2H6 (C) removing some E^ Q.15 An exothermic reaction is represented by the graph:

/nK

InK
(B)
1/T

laK

/nK

(A)

(C)
1/T 1/T

(D)
1/T

Q.16 The correct relationship betweenfreeenergy change in a reaction and the corresponding equilibrium constant K is (A) -AG = RT /n K (B) AG = RT /n K (C) -AG = RT /n K (D)AG = RT/nK Q.17 The value of AG^. of gaseous mercury is 31 K J/mole. At what total external pressure mercury start boiling at 25C. [R=8.3] (A) 10~5-44 (B) 10"12-5 (C) 10^ 52 (D) 10-312

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Q.18 What is ArG (KJ/mole) for synthesis of ammonia at298 K at following sets of partial pressure: N2(g) + 3H2(g) # 2NH,(g); ArG = -33 KJ/mole. [TakeR = 8.3 J/Kmole, log2 = 0.3; log3 = 0.48] Gas N2 H2 NH3 1 3 0.02 Pressure (atm) (A)+ 6.5 (B) - 6.5 (C) + 60.5 (D)-60.5 Q.19 In a 7.0 L evacuated chamber, 0.50 mol H2 and 0.50 mol I2 react at 427C. H2(g) + I2(g) ^ 2HI(g). At the given temperature, Kc=49 for the reaction. (i) What is the value of K p ? (A) 7 (B)49 (C) 24.5 (D)None (ii) What is the total pressure (atm) in the chamber? (A) 83.14 (B) 831.4 (C) 8.21 How many moles of the iodine remain unreacted at equilibrium? (B) 0.112 (C)0.25 (A) 0.388 What is the partial pressure (atm) ofHI in the equilibrium mixture? (A) 6.385 (B) 12.77 (C) 40.768

(D)None

(iii)

(D) 0.125

(iv)

(D) 646.58

Q.20 Equilibrium constants are given (in atm) for the following reactions at 0 C: SrCl2 6H 2 0(S ) ^ SrCl2 2 H 2 0 (s) + 4 H 2 0 ( g ) Kp = 5 x 10~12
N a 2 H P 0 4 12 H 2 0(S ) ^ N a 2 H P 0 4 7 H 2 0 (s) + 5H 2 O(g) N a 2 S 0 4 10 H 2 0(S ) ^ N a 2 S 0 4 (s) + 10 H 2 0 (g) K p = 2.43 x 10~ 13 K p = 1.024 x 10 27

(i)

The vapor pressure of water at 0C is 4.56 torr. Which is the most effective drying agent at 0C? (A) SrCl2 2H 2 0 (B) Na2HP04-7 H 2 0 (C) Na2S04

(D) all equally

(ii)

At what relative humidities will Na^O,, 10 H20 be efflorescent when exposed to air at 0C? (A) above33.33% (B) below33.33 % (C) above 66.66% (D)below66.66% At what relative humidities will Na2S04 be deliquescent (i.e. absorb moisture) when exposed to the air at 0C? (A) above 33.33% (B)below33.33 % (C) above 66.66% (D) below 66.66%

(iii)

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EXERCISE III Q.l A sample of air consisting of N2 and 0 2 was heated to 2500K until the equilibrium N2(g) + 02(g) ^ 2NO was established with an equilibrium constant Kc = 2.1 x 10~3. At equilibrium, the mol% of NO was 1.8. Estimate the initial composition of air in mol fraction of N2 and 0 2 . [JEE 1997] For the reaction CO(g) + H 2 0 ^ C02(g) + H2(g) at a given temperature the equilibrium amount of C02(g) can be increased by: (A) adding a suitable catalyst (B) adding an inert gas (C) decreasing the volume of the container (D) increasing the amount of CO(g). [JEE 1998] The degree of dissociation is 0.4 at 400 K & 1.0 atm for the gaseous reaction, PC15 ^ PC13 + Cl2. Assuming ideal behaviour of all the gases, calculate the density of equilibrium [JEE 1998] mixture at400 K & 1.0 atmosphere. (atomic mass ofP = 31.0&Cl = 35.5) For the reaction, N205(g) = 2N02(g) + 0.5 02(g), calculate the mole fraction of N205(g) decomposed at a constant volume & temperature, if the initial pressure is 600 mm Hg & the pressure at any time is 960 mm Hg. Assume ideal gas behaviour. [JEE 1998] The degree of dissociation is 0.4 at 400K & 1.0 atm for the gasoeus reaction PC15 ^ PCI3 + Cl2(g). Assuming ideal behaviour of all gases. Calculate the density of equilibrium , [JEE 1999] mixture at 400K & 1.0 atm pressure. When 3.06g of solid NH4HS is introduced into a two litre evacuated flask at 27C, 30% ofthe solid decomposes into gaseous ammonia and hydrogen sulphide. Calculate K c & K p for the reaction at 27C. What would happen to the equilibrium when more solid NH4HS is introduced into the flask? [JEE 2000] When 1 -pentyne (A) is treated with 4N alcoholic KOH at 175C, it is converted slowly into an equilibrium mixture of 1.3% 1 -pentyne (A), 95.2% 2-pentyne (B) & 3.5% of 1,2,-pentadiene (C). The equilibrium was maintained at 175C. Calculate AG for the following equilibria. B =A AGj = ? B= C AG2 = ? From the calculated value of AG;0 & AG2 indicate the order of stability ofA B & C. Write a reasonable reaction mechanism sharing all intermediate leading to A B & C. [JEE 2001] N204(g) ^ 2N02(g) This reaction is carried out at 298 K and 20 bar. 5 mol each of N 2 0 4 and N0 2 are taken initially. Given: AGj2o4 = lOOkJmol-1; AGno2 =50kJmol" 1 Find AG for reaction at 298 K under given condition. Find the direction in which the reaction proceeds to achieve equilibrium. [JEE 2004] N2 + 3 H 2 ^ 2NH3 Which is correct statement if N2 is added at equilibrium condition? (A) The equilibrium will shift to forward direction because according to II law ofthermodynamics the entropy must increases in the direction of spontaneous reaction. (B) The condition for equilibrium is GN^ + 3GH^=2GNH^ where G is Gibbsfreeenergy per mole ofthe gaseous species measured at that partial pressure. The condition of equilibrium is unaffected by the use of catalyst, which increases the rate of both the forward and backward reactions to the same extent. (C) The catalyst will increase the rate offorward reaction by a and that of backward reaction by p. (D) Catalyst will not alter the rate of either ofthe reaction. [JEE 2006] CHEMICAL EQUILIBRIUM "[28]

Q.2

Q.3

Q.4

Q.5

Q.6 (i) (ii) Q. 7

Q.8

(i) (ii) Q.9

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