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CHEMICAL EQUILIBRIUM

Chapter 16

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Properties of an Equilibrium
Equilibrium systems are • DYNAMIC (in constant motion) • REVERSIBLE • can be approached from either direction

Copyright (c) 1999 by Harcourt Brace & Company All rights reserved

3

Properties of an Equilibrium
Equilibrium systems are • DYNAMIC (in constant motion) • REVERSIBLE • can be approached from either direction Pink to blue Co(H2O)6Cl2 ---> Co(H2O)4Cl2 + 2 H2O

Copyright (c) 1999 by Harcourt Brace & Company All rights reserved

4

Properties of an Equilibrium
Equilibrium systems are • DYNAMIC (in constant motion) • REVERSIBLE • can be approached from either direction Pink to blue Co(H2O)6Cl2 ---> Co(H2O)4Cl2 + 2 H2O Blue to pink Co(H2O)4Cl2 + 2 H2O ---> Co(H2O)6Cl2
Copyright (c) 1999 by Harcourt Brace & Company All rights reserved

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Chemical Equilibrium
Fe3+ + SCNFeSCN2+

+
Fe(H2O)63+ + SCNFe(SCN)(H2O)53+ + H2O

Copyright (c) 1999 by Harcourt Brace & Company All rights reserved

Copyright (c) 1999 by Harcourt Brace & Company All rights reserved . • The forward and reverse reactions continue after equilibrium is attained.Chemical Equilibrium Fe3+ + SCNFeSCN2+ 6 • After a period of time. the concentrations of reactants and products are constant.

7 Examples of Chemical Equilibria Phase changes such as H2O(s) H2O(liq) Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .

8 Examples of Chemical Equilibria Formation of stalactites and stalagmites CaCO3(s) + H2O(liq) + CO2(g) Ca2+(aq) + 2 HCO3-(aq) Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .

Copyright (c) 1999 by Harcourt Brace & Company All rights reserved . [Ca2+] and [HCO3-] can be found from the EQUILIBRIUM CONSTANT.9 Chemical Equilibria CaCO3(s) + H2O(liq) + CO2(g) Ca2+(aq) + 2 HCO3-(aq) At a given T and P of CO2.

10 THE EQUILIBRIUM CONSTANT For any type of chemical equilibrium of the type aA + bB cC + dD the following is a CONSTANT (at a given T) Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .

11 THE EQUILIBRIUM CONSTANT For any type of chemical equilibrium of the type aA + bB cC + dD the following is a CONSTANT (at a given T) conc. of reactants equilibrium constant If K is known. of products K = [C]c [D]d [A]a [B]b conc. of products or reactants. then we can predict concs. Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .

Solution Set of a table of concentrations [NOCl] [NO] [Cl2] Before 2.00 L flask.00 0 0 Change Equilibrium 0.66 mol/L of NO. Calculate K. At equilibrium you find 0.12 Determining K 2 NOCl(g) 2 NO(g) + Cl2(g) Place 2.00 mol of NOCl is a 1.66 Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .

66 0.34 0. Solution Set of a table of concentrations [NOCl] [NO] [Cl2] Before 2. Calculate K.66 +0.66 mol/L of NO.00 L flask.66 +0.00 0 0 Change -0. At equilibrium you find 0.00 mol of NOCl is a 1.13 Determining K 2 NOCl(g) 2 NO(g) + Cl2(g) Place 2.33 Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .33 Equilibrium 1.

66 1.66 2 [NO] [Cl2 ] K [NOCl]2 [Cl2] 0 +0.00 0 -0.33 Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .66 +0.34 0.33 0.14 Determining K 2 NOCl(g) Before Change Equilibrium 2 NO(g) + Cl2(g) [NOCl] [NO] 2.

66 1.33) (1.34)2 = 0.080 Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .33 0.66 +0.66 2 [NO] [Cl2 ] K [NOCl]2 [Cl2] 0 +0.66)2 (0.15 Determining K 2 NOCl(g) Before Change Equilibrium 2 NO(g) + Cl2(g) [NOCl] [NO] 2.33 K [NO]2 [Cl2 ] [NOCl]2 = (0.00 0 -0.34 0.

16 Writing and Manipulating K Expressions Solids and liquids NEVER appear in equilibrium expressions. S(s) + O2(g) SO2(g) Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .

S(s) + O2(g) SO2(g) [SO2 ] K [O2 ] Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .17 Writing and Manipulating K Expressions Solids and liquids NEVER appear in equilibrium expressions.

NH3(aq) + H2O(liq) NH4+(aq) + OH-(aq) Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .18 Writing and Manipulating K Expressions Solids and liquids NEVER appear in equilibrium expressions.

19 Writing and Manipulating K Expressions Solids and liquids NEVER appear in equilibrium expressions. NH3(aq) + H2O(liq) NH4+(aq) + OH-(aq) [NH4+ ][OH.] K [NH3 ] Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .

Writing and Manipulating K Expressions Adding equations for reactions S(s) + O2(g) SO2(g) + 1/2 O2(g) SO2(g) K1 = [SO2] / [O2] SO3(g) K2 = [SO3] / [SO2][O2]1/2 NET EQUATION S(s) + 3/2 O2(g) SO3(g) 20 Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .

Writing and Manipulating K Expressions Adding equations for reactions S(s) + O2(g) SO2(g) K1 = [SO2] / [O2] SO2(g) + 1/2 O2(g) SO3(g) K2 = [SO3] / [SO2][O2]1/2 NET EQUATION S(s) + 3/2 O2(g) SO3(g) 21 Knet  Copyright (c) 1999 by Harcourt Brace & Company All rights reserved = K • K 1 2 3/2 [O2 ] [SO3 ] .

Writing and Manipulating K Expressions Changing coefficients S(s) + 3/2 O2(g) 2 S(s) + 3 O2(g) SO3(g) K  2 SO3(g) 22 [SO3 ] [O2 ]3/2 Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .

Writing and Manipulating K Expressions Changing coefficients S(s) + 3/2 O2(g) 2 S(s) + 3 O2(g) SO3(g) K  2 SO3(g) 23 [SO3 ] [O2 ]3/2 K new  [SO3 ]2 [O2 ]3 Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .

Writing and Manipulating K Expressions Changing coefficients S(s) + 3/2 O2(g) 2 S(s) + 3 O2(g) SO3(g) K  2 SO3(g) 24 [SO3 ] [O2 ]3/2 K new  Knew  Copyright (c) 1999 by Harcourt Brace & Company All rights reserved [SO3 ]2 [O2 ]3 [SO3 ]2 [O2 ]3 = (K old )2 .

Writing and Manipulating K Expressions Changing direction S(s) + O2(g) SO2(g) SO2(g) K  25 [SO2 ] [O2 ] S(s) + O2(g) Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .

Writing and Manipulating K Expressions Changing direction S(s) + O2(g) SO2(g) SO2(g) K  26 [SO2 ] [O2 ] S(s) + O2(g) [O2 ] Knew  [SO2 ] Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .

Writing and Manipulating K Expressions Changing direction S(s) + O2(g) SO2(g) SO2(g) K  27 [SO2 ] [O2 ] S(s) + O2(g) [O2 ] Knew  [SO2 ] [O2 ] 1 Knew  = [SO2 ] Kold Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .

so we can write K in terms of P.Writing and Manipulating K Expressions Concentration Units We have been writing K in terms of mol/L. Kc and Kp may or may not be the same. These are designated 28 by Kp. P = (n/V)•RT = conc • RT P is proportional to concentration. Copyright (c) 1999 by Harcourt Brace & Company All rights reserved . These are designated by Kc But with gases.

29 The Meaning of K 1. Can tell if a reaction is productfavored or reactant-favored. For N2(g) + 3 H2(g) 2 NH3(g) Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .

30 The Meaning of K 1. Can tell if a reaction is productfavored or reactant-favored. For N2(g) + 3 H2(g) 2 NH3(g) Kc = 8 = 3.5 x 10 [N2 ][H2 ]3 [NH3 ]2 Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .

5 x 10 [N2 ][H2 ]3 [NH3 ]2 Conc. Copyright (c) 1999 by Harcourt Brace & Company All rights reserved . of products is much greater than that of reactants at equilibrium.31 The Meaning of K 1. For N2(g) + 3 H2(g) 2 NH3(g) Kc = 8 = 3. Can tell if a reaction is productfavored or reactant-favored.

32 The Meaning of K 1.5 x 10 [N2 ][H2 ]3 [NH3 ]2 Conc. The reaction is strongly product- favored. Can tell if a reaction is productfavored or reactant-favored. For N2(g) + 3 H2(g) 2 NH3(g) Kc = 8 = 3. Copyright (c) 1999 by Harcourt Brace & Company All rights reserved . of products is much greater than that of reactants at equilibrium.

is product-favored.8 x 10-5 Conc.33 The Meaning of K For AgCl(s) Ag+(aq) + Cl-(aq) Kc = [Ag+] [Cl-] = 1. The reaction is strongly Ag+(aq) + Cl-(aq) AgCl(s) reactant-favored. of products is much less than that of reactants at equilibrium. Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .

Can tell if a reaction is at equilibrium.5 34 K = Copyright (c) 1999 by Harcourt Brace & Company All rights reserved . If not.The Meaning of K 2. which way it moves to approach equilibrium. n-butane H H H H H—C—C—C—C—H H H H H [iso] [n] iso-butane H H H H—C—C—C—H H H H C H H = 2.

The Meaning of K n-butane H H H H H—C—C—C—C—H H H H H [iso] [n] iso-butane H H H H—C—C—C—H H H H C H H = 2.5 35 K = If [iso] = 0.35 M and [n] = 0. are you at equilibrium? Which way does the reaction “shift” to approach equilibrium? See Screen 16.15 M.9. Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .

The Meaning of K In general. Q. Copyright (c) 1999 by Harcourt Brace & Company All rights reserved . all reacting chemical systems are characterized by their REACTION QUOTIENT. 36 product concentrations Q = reactant concentrations If Q = K. then system is at equilibrium.

35 Q = = = 2. of n 0.15 M. If [iso] = 0. Q.3 conc.15 Q (2.The Meaning of K In general. then system is at equilibrium.3) < K (2. 37 product concentrations Q = reactant concentrations If Q = K.35 M and [n] = 0. Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .5). all reacting chemical systems are characterized by their REACTION QUOTIENT. of iso 0. are you at equilibrium? conc.

The Meaning of K In general. Copyright (c) 1999 by Harcourt Brace & Company All rights reserved 38 .15 Q (2. then system is at equilibrium. conc.5). Q. of iso 0. of n 0.3 conc. Reaction is NOT at equilibrium.35 Q = = = 2. all reacting chemical systems are characterized by their REACTION QUOTIENT.33) < K (2. so [Iso] must become ________ and [n] must ____________. product concentrations Q = reactant concentrations If Q = K.

00 L flask. H2(g) + I2(g) ¸ 2 HI(g) [HI] Kc = = 55.3 [H2 ][I2 ] 2 Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .00 mol each of H2 and I2 in a 1. Calc. equilibrium concentrations.39 Typical Calculations PROBLEM: Place 1.

3 Step 1.00 [HI] 0 Copyright (c) 1999 by Harcourt Brace & Company All rights reserved . Kc = 55.40 H2(g) + I2(g) 2 HI(g). [H2] Initial Change Equilib 1. Set up table to define EQUILIBRIUM concentrations.00 [I2] 1.

41 H2(g) + I2(g) 2 HI(g). Set up table to define EQUILIBRIUM concentrations. [H2] Initial Change Equilib 1.3 Step 1.00 -x 1. Kc = 55. Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .00 -x 1.00-x [I2] 1.00-x [HI] 0 +2x 2x where x is defined as am’t of H2 and I2 consumed on approaching equilibrium.

00 .x] Copyright (c) 1999 by Harcourt Brace & Company All rights reserved . [2x]2 Kc = = 55.3 Step 2.42 H2(g) + I2(g) 2 HI(g). Put equilibrium concentrations into Kc expression.3 [1. Kc = 55.x][1.00 .

take square root of both sides. Solve Kc expression .43 H2(g) + I2(g) 2 HI(g). Kc = 55. Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .3 Step 3.

44 = 2x 1. Kc = 55. Solve Kc expression .x Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .take square root of both sides.3 Step 3.00 . 7.44 H2(g) + I2(g) 2 HI(g).

Kc = 55.x Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .45 H2(g) + I2(g) 2 HI(g).44 = x = 0.3 Step 3. Solve Kc expression .take square root of both sides.00 .79 2x 1. 7.

x = 0.44 = x = 0. Kc = 55.21 M Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .46 H2(g) + I2(g) 2 HI(g).3 Step 3.00 .x Therefore.00 . 7.take square root of both sides. at equilibrium [H2] = [I2] = 1. Solve Kc expression .79 2x 1.

47 H2(g) + I2(g) 2 HI(g).00 .44 = x = 0. Kc = 55.3 Step 3. 7.79 2x 1.x Therefore. at equilibrium [H2] = [I2] = 1.21 M [HI] = 2x = 1.58 M Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .00 . Solve Kc expression .take square root of both sides.x = 0.

48 Nitrogen Dioxide Equilibrium N2O4(g) 2 NO2(g) Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .

50 0 Change Equilib Copyright (c) 1999 by Harcourt Brace & Company All rights reserved 2 . what are the equilibrium concentrations? Step 1.50 M.49 Nitrogen Dioxide Equilibrium N2O4(g) 2 NO2(g) [NO2 ] Kc = = 0.0059 at 298 K [N2O4 ] If initial concentration of N2O4 is 0. Set up an equilibrium table [N2O4] [NO2] Initial 0.

50 .50 M. what are the equilibrium concentrations? Step 1. Set up an equilibrium table [N2O4] [NO2] Initial 0.50 0 Change -x +2x Equilib 0.x 2x Copyright (c) 1999 by Harcourt Brace & Company All rights reserved 2 .50 Nitrogen Dioxide Equilibrium N2O4(g) 2 NO2(g) [NO2 ] Kc = = 0.0059 at 298 K [N2O4 ] If initial concentration of N2O4 is 0.

0029 .51 Nitrogen Dioxide Equilibrium N2O4(g) 2 NO2(g) Step 2.0059 Copyright (c) 1999 by Harcourt Brace & Company All rights reserved EQUATION c = -0.0059 (0.x) = 4x2 0.0.0029 = 0 This is a QUADRATIC ax2 + bx + c = 0 a = 4 b = 0.0.50 .0029 .0059 = = [N2O 4 ] (0.50 .0059x = 4x2 4x2 + 0.0059x . [NO2 ]2 (2x)2 Kc = 0. Substitute into Kc expression and solve.x) Rearrange: 0.

ax2 + bx + c = 0 a = 4 b = 0.0029 x = -b  2 b .4ac 2a Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .52 Nitrogen Dioxide Equilibrium N2O4(g) 2 NO2(g) Solve the quadratic equation for x.0059 c = -0.

0059)2 .0029 x = -b  2 b . ax2 + bx + c = 0 a = 4 b = 0.0059  (0.53 Nitrogen Dioxide Equilibrium N2O4(g) 2 NO2(g) Solve the quadratic equation for x.4(4)(-0.0059 c = -0.0029) 2(4) Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .4ac 2a x = -0.

00074 ± 1/8(0. ax2 + bx + c = 0 a = 4 b = 0.0059  (0.54 Nitrogen Dioxide Equilibrium N2O4(g) 2 NO2(g) Solve the quadratic equation for x.0059)2 .00074 ± 0.4(4)(-0.4ac 2a x = -0.027 Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .046)1/2 = -0.0029 x = -b  2 b .0029) 2(4) x = -0.0059 c = -0.

Conclusion [N2O4] = 0.026 or -0.00074 ± 1/8(0.55 Nitrogen Dioxide Equilibrium N2O4(g) 2 NO2(g) x = -0.0059  (0.028 But a negative value is not reasonable.046)1/2 = -0.0029) 2(4) x = -0.47 M [NO2] = 2x = 0.x = 0.00074 ± 0.052 M Copyright (c) 1999 by Harcourt Brace & Company All rights reserved .4(4)(-0.0059)2 .050 .027 x = 0.