CHAPTER 13 CHEMICAL EQUILIBRIUM

Questions
10. Because of the 2 : 1 mole ratio between NH3 and N2 in the balanced equation, NH3 will disappear at a rate that is twice as fast as the rate that N2 appears. Because of the 3 : 1 mole ratio between H2 and N2 in the balanced equation, H2 will appear at a rate that is three times the rate that N2 appears. At equilibrium, however, all rates of appearance and disappearance will be equal to each other. This always occurs when a reaction reaches equilibrium. No, equilibrium is a dynamic process. Both reactions: H2O + CO H2 + CO2 and H2 + CO2 H2O + CO are occurring at equal rates. Thus 14C atoms will be distributed between CO and CO2. 12. No, it doesn't matter from which direction the equilibrium position is reached. Both experiments will give the same equilibrium position because both experiments started with stoichiometric amounts of reactants or products. A K value much greater than one (K >> 1) indicates there are relatively large concentrations of product gases/solutes as compared with the concentrations of reactant gases/solutes at equilibrium. A reaction with a very large K value is a good source of products. A K value much less than one (K >> 1) indicates that there are relatively large concentrations of reactant gases/solutes as compared with the concentrations of product gases/solutes at equilibrium. A reaction with a very small K value is a very poor source of products. H2O(g) + CO(g)

11.

13.

14.

15.

H2(g) + CO2(g)

K=

[H 2 ][CO 2 ] = 2.0 [H 2 O][CO]

K is a unitless number because there is an equal number of moles of product gases as moles of reactant gases in the balanced equation. Therefore, we can use units of molecules per liter instead of moles per liter to determine K. We need to start somewhere, so lets assume 3 molecules of CO react. If 3 molecules of CO react, then 3 molecules of H2O must react, and 3 molecules each of H2 and CO2 are formed. We would have 6 ! 3 = 3 molecules of CO, 8 ! 3 = 5 molecules of H2O, 0 + 3 = 3 molecules of H2, and 0 + 3 = 3 molecules of CO2 present. This will be an equilibrium mixture if K = 2.0:

454

CHAPTER 13

CHEMICAL EQUILIBRIUM

455

3 molecules H 2 3 molecules CO 2 L L = 3 K= 5 5 molecules H 2 O 3 molecules CO L L Because this mixture does not give a value of K = 2.0, this is not an equilibrium mixture. Lets try 4 molecules of CO reacting to reach equilibrium. Molecules CO remaining = 6 ! 4 = 2 molecules of CO Molecules H2O remaining = 8 ! 4 = 4 molecules of H2O Molecules H2 present = 0 + 4 = 4 molecules of H2 Molecules CO2 present = 0 + 4 = 4 molecules of CO2
4 molecules H 2 4 molecules CO 2 L L = 2 .0 K= 4 molecules H 2 O 2 molecules CO L L Because K = 2.0 for this reaction mixture, we are at equilibrium. 16. When equilibrium is reached, there is no net change in the amount of reactants and products present because the rates of the forward and reverse reactions are equal to each other. The first diagram has 4 A2B molecules, 2 A2 molecules, and 1 B2 molecule present. The second diagram has 2 A2B molecules, 4 A2 molecules, and 2 B2 molecules. Therefore, the first diagram cannot represent equilibrium because there was a net change in reactants and products. Is the second diagram the equilibrium mixture? That depends on whether there is a net change between reactants and products when going from the second diagram to the third diagram. The third diagram contains the same numbers and types of molecules as the second diagram, so the second diagram is the first illustration that represents equilibrium. The reaction container initially contained only A2B. From the first diagram, 2 A2 molecules and 1 B2 molecule are present (along with 4 A2B molecules). From the balanced reaction, these 2 A2 molecules and 1 B2 molecule were formed when 2 A2B molecules decomposed. Therefore, the initial number of A2B molecules present equals 4 + 2 = 6 molecules A2B. 17. K and Kp are equilibrium constants, as determined by the law of mass action. For K, concentration units of mol/L are used, and for Kp, partial pressures in units of atm are used (generally). Q is called the reaction quotient. Q has the exact same form as K or Kp, but instead of equilibrium concentrations, initial concentrations are used to calculate the Q value. The use of Q is when it is compared with the K value. When Q = K (or when Qp = Kp), the reaction is at equilibrium. When Q K, the reaction is not at equilibrium, and one can deduce the net change that must occur for the system to get to equilibrium. H2(g) + I2(g) 2 HI(g) K=

18.

[HI] 2 [H 2 ][I 2 ]
[HI]2 (Solids are not included in K expressions.) [H 2 ]

H2(g) + I2(s) 2 HI(g)

K=

456
Some property differences are:

CHAPTER 13

CHEMICAL EQUILIBRIUM

(1) the reactions have different K expressions. (2) for the first reaction, K = Kp (since n = 0), and for the second reaction, K Kp (since n 0). (3) a change in the container volume will have no effect on the equilibrium for reaction 1, whereas a volume change will affect the equilibrium for reaction 2 (shifts the reaction left or right depending on whether the volume is decreased or increased). 19. We always try to make good assumptions that simplify the math. In some problems we can set up the problem so that the net change x that must occur to reach equilibrium is a small number. This comes in handy when you have expressions like 0.12 x or 0.727 + 2x, etc. When x is small, we can assume that it makes little difference when subtracted from or added to some relatively big number. When this is the case, 0.12 x 0.12 and 0.727 + 2x 0.727, etc. If the assumption holds by the 5% rule, the assumption is assumed valid. The 5% rule refers to x (or 2x or 3x, etc.) that is assumed small compared to some number. If x (or 2x or 3x, etc.) is less than 5% of the number the assumption was made against, then the assumption will be assumed valid. If the 5% rule fails to work, one can use a math procedure called the method of successive approximations to solve the quadratic or cubic equation. Of course, one could always solve the quadratic or cubic equation exactly. This is generally a last resort (and is usually not necessary). Only statement e is correct. Addition of a catalyst has no effect on the equilibrium position; the reaction just reaches equilibrium more quickly. Statement a is false for reactants that are either solids or liquids (adding more of these has no effect on the equilibrium). Statement b is false always. If temperature remains constant, then the value of K is constant. Statement c is false for exothermic reactions where an increase in temperature decreases the value of K. For statement d, only reactions that have more reactant gases than product gases will shift left with an increase in container volume. If the moles of gas are equal, or if there are more moles of product gases than reactant gases, the reaction will not shift left with an increase in volume.

20.

The Equilibrium Constant

21. a. K = [ NO]2 [ N 2 ][O 2 ] [SiCl 4 ][H 2 ]2 [SiH 4 ][Cl 2 ]2
2 PNO PN 2 PO 2
2 PSiCl 4 PH 2 2 PSiH 4 PCl 2

b. K =

[ NO 2 ]2 [ N 2O 4 ] [PCl 3 ]2 [Br2 ]3 [ PBr3 ]2 [Cl 2 ]3

2 PNO 2

c. K =

d. K =

22.

a. Kp =

b. Kp =

PN 2O 4
2 3 PPCl3 PBr 2 2 3 PPBr 3 PCl 2

c. Kp =

d. Kp =

CHAPTER 13
23.

CHEMICAL EQUILIBRIUM
[ NH 3 ]2 for N2(g) + 3 H2(g) 2 NH3(g). [ N 2 ][H 2 ]3

457

K = 1.3 10 2 =

When a reaction is reversed, then Knew = 1/Koriginal. When a reaction is multiplied through by a value of n, then Knew = (Koriginal)n. a. 1/2 N2(g) + 3/2 H2(g) NH3 (g) KN= b. 2 NH3(g) N2(g) + 3 H2(g) [ NH 3 ]2 = K1/2 = (1.3 10 2 )1/2 = 0.11 1/ 2 3/ 2 [ N 2 ] [H 2 ]

KO =

[ N 2 ][H 2 ]3 [ NH 3 ]
2

1 1 = = 77 K 1.3 10 2
1/ 2

c. NH3(g) 1/2 N2(g) + 3/2 H2(g)

[ N 2 ]1/ 2 [H 2 ]3 / 2 1 KNNN = = [ NH 3 ] K

1 = 1.3 10 2 = 8.8

1/ 2

d. 2 N2(g) + 6 H2(g) 4 NH3(g) K = H2(g) + Br2(g) 2 HBr(g)

[ NH 3 ]4 = (K)2 = (1.3 10 2 )2 = 1.7 10 4 2 6 [ N 2 ] [H 2 ]

24.

Kp =

2 PHBr = 3.5 104 ( PH 2 ) ( PBr2 )

a. HBr 1/2 H2 + 1/2 Br2

K 'p

(PH 2 )1/ 2 (PBr2 )1/ 2 PHBr

1 = Kp

1/ 2

1 = 3.5 10 4

1/ 2

= 5.3 103 b. 2 HBr H2 + Br2

' K 'p =

(PH 2 )(PBr2 )
2 PHBr

1 1 = = 2.9 105 4 Kp 3.5 10

c. 1/2 H2 + 1/2 Br2 HBr

' K 'p' =

(PH 2 )

PHBr 1/ 2

(PBr2 )1/ 2

= (K p )1/ 2 = 190

25.

2 NO(g) + 2 H2(g) N2(g) + 2 H2O(g) K=

(5.3 10 2 )(2.9 10 3 ) 2 (8.1 10 ) ( 4.1 10 )
3 2 5 2

K=

[ N 2 ][H 2 O]2 [ NO]2 [H 2 ]2

= 4.0 106

26.

K=

[ NO]2 ( 4.7 10 4 M ) 2 = = 6.9 104 [ N 2 ][O 2 ] (0.041 M )(0.0078 M )

458
27. [NO] =

CHAPTER 13

CHEMICAL EQUILIBRIUM

4.5 10 3 mol 2.4 mol = 0.80 M = 1.5 10 3 M; [Cl2] = 3 .0 L 3 .0 L

1.0 mol = 0.33 M; 3.0 L

[NOCl] =

K=

[ NO]2 [Cl 2 ] [ NOCl]2

(1.5 10 3 ) 2 (0.80) (0.33) 2

= 1.7 10 5

28.

[N2O] =

2.00 10 2 mol 2.80 10 4 mol 2.50 10 5 mol ; [N2] = ; [O2] = 2.00 L 2.00 L 2.00 L
2

2.00 10 2 2.00 (1.00 10 2 ) 2 [ N 2 O ]2 K= = = (1.40 10 4 ) 2 (1.25 10 5 ) [ N 2 ]2 [O 2 ] 2.80 10 4 2 2.50 10 5 2.00 2.00 = 4.08 108 L/mol If the given concentrations represent equilibrium concentrations, then they should give a value of K = 4.08 108. (0.200) 2 = 4.08 108 (2.00 10 4 ) 2 (0.00245) Because the given concentrations when plugged into the equilibrium constant expression give a value equal to K (4.08 108), this set of concentrations is a system at equilibrium. 29. Kp =
2 PNO PO 2 2 PNO2
2 PNH 3 3 PN 2 PH 2

(6.5 10 5 ) 2 (4.5 10 5 ) (0.55) 2

= 6.3 10 13

30.

Kp =

(3.1 10 2 ) 2 = 3.8 104 atm2 (0.85)(3.1 10 3 ) 3

(0.167) 2 = 1.21 103 3 (0.525) (0.00761) When the given partial pressures in atmospheres are plugged into the Kp expression, the value does not equal the Kp value of 3.8 104. Therefore, one can conclude that the given set of partial pressures does not represent a system at equilibrium. 31. Kp = K(RT)n, where n = sum of gaseous product coefficients ! sum of gaseous reactant coefficients. For this reaction, n = 3 ! 1 = 2. K= [CO][H 2 ]2 (0.24)(1.1) 2 = = 1.9 mol2/L2 (0.15) [CH 3OH]

Kp = K(RT)2 = 1.9(0.08206 L atm/KCmol 600. K)2 = 4.6 103

CHAPTER 13
32. 33.

CHEMICAL EQUILIBRIUM
Kp (RT )
n

459
0.25 (0.08206 1100) 1

Kp = K ( RT ) n , K =

; n = 2 3 = 1; K =

= 23

Solids and liquids do not appear in equilibrium expressions. Only gases and dissolved solutes appear in equilibrium expressions. a. K = PH 2O [ H 2 O] ; Kp = 2 2 [ NH 3 ] [CO 2 ] PNH 3 PCO 2
3 b. K = [N2][Br2]3; Kp = PN 2 PBr2

3 c. K = [O2]3; Kp = PO 2

d. K = b. Kp = 1 PCO 2
3 PO 2 2 PH O
2

PH 2O [ H 2 O] ; Kp = [H 2 ] PH 2

34.

a. Kp =

1 (PO 2 )
3/ 2

c. Kp =

PCO PH 2 PH 2O

d. Kp =

35.

Kp = K(RT)n, where n equals the difference in the sum of the coefficients between gaseous products and gaseous reactants (n = mol gaseous products ! mol gaseous reactants). When n = 0, then Kp = K. In Exercise 33, only reaction d has n = 0, so only reaction d has Kp = K. Kp = K when n = 0. In Exercise 34, none of the reactions have Kp = K because none of the reactions have n = 0. The values of n for the various reactions are 1.5, 1, 1, and 1, respectively. Because solids do not appear in the equilibrium constant expression, K = 1/[O2]3.
1 1.0 10 3 mol 1 1 ; K= = = = 8.0 109 4 3 2.0 L 3 3 [O 2 ]3 (5.0 10 ) 1.0 10 2 .0 4 PH Kp = 4 2 ; Ptotal = PH 2O + PH 2 , 36.3 torr = 15.0 torr + PH 2 , PH 2 = 21.3 torr PH 2 O

36.

37.

[O2] =

38.

1 atm 21.3 torr 760 torr = 4.07 Because l atm = 760 torr: Kp = 4 1 atm 15.0 torr 760 torr

Note: Solids and pure liquids are not included in K expressions.

Equilibrium Calculations
39. H2O(g) + Cl2O(g) 2 HOCl(g) K= [HOCl]2 = 0.0900 [H 2 O][Cl 2 O]

460

CHAPTER 13

CHEMICAL EQUILIBRIUM

Use the reaction quotient Q to determine which way the reaction shifts to reach equilibrium. For the reaction quotient, initial concentrations given in a problem are used to calculate the value for Q. If Q < K, then the reaction shifts right to reach equilibrium. If Q > K, then the reaction shifts left to reach equilibrium. If Q = K, then the reaction does not shift in either direction because the reaction is at equilibrium.

1.0 mol 1 .0 L 2 [HOCl]0 a. Q = = = 1.0 102 [H 2 O]0 [Cl 2 O]0 0.10 mol 0.10 mol 1.0 L 1.0 L Q > K, so the reaction shifts left to produce more reactants at equilibrium.
0.084 mol 2 .0 L b. Q = = 0.090 = K; at equilibrium 0.98 mol 0.080 mol 2.0 L 2.0 L 0.25 mol 3.0 L c. Q = = 110 > K 0.56 mol 0.0010 mol 3.0 L 3.0 L Reaction shifts to the left to reach equilibrium. 40. As in Exercise 39, determine Q for each reaction, compare this value to Kp (= 0.0900), and then determine which direction the reaction shifts to reach equilibrium. Note that for this reaction, K = Kp because n = 0. a.
2 2

Q =

2 PHOCl (1.00 atm) 2 = = 1.00 PH 2O PCl 2O (1.00 atm) (1.00 atm)

Q > Kp, so the reaction shifts left to reach equilibrium. b. Q = ( 21.0 torr ) 2 = 4.43 102 < Kp (200. torr ) (49.8 torr )

The reaction shifts right to reach equilibrium. Note: Because Q and Kp are unitless, we can use any pressure units when determining Q. c. Q = (20.0 torr ) 2 = 0.0901 Kp; at equilibrium (296 torr ) (15.0 torr )

CHAPTER 13
41. CaCO3(s)

CHEMICAL EQUILIBRIUM

461

CaO(s) + CO2(g)

Kp = PCO 2 = 1.04

a. Q = PCO 2 ; we only need the partial pressure of CO2 to determine Q because solids do not appear in equilibrium expressions (or Q expressions). At this temperature, all CO2 will be in the gas phase. Q = 2.55, so Q > Kp; the reaction will shift to the left to reach equilibrium; the mass of CaO will decrease. b. Q = 1.04 = Kp, so the reaction is at equilibrium; mass of CaO will not change. c. Q = 1.04 = Kp, so the reaction is at equilibrium; mass of CaO will not change. d. Q = 0.211 < Kp; the reaction will shift to the right to reach equilibrium; mass of CaO will increase. 42. CH3CO2H + C2H5OH CH3CO2C2H5 + H2O K = a. Q = (0.22)(0.10) = 220 > K; (0.010)(0.010)
(0.22)(0.0020) = 2.2 = K; (0.0020)(0.10) (0.88)(0.12) = 0.40 < K; (0.044)(6.0) (4.4)(4.4) = 2.2 = K; (0.88)(10.0) [CH 3CO 2 C 2 H 5 ][H 2 O] = 2.2 [CH 3CO 2 H][C 2 H 5 OH]

reaction will shift left to reach equilibrium, so the concentration of water will decrease. reaction is at equilibrium, so the concentration of water will remain the same. because Q < K, the concentration of water will increase because the reaction shifts right to reach equilibrium. at equilibrium, so the water concentration is unchanged.

b. Q =

c. Q =

d. Q =

e. K = 2.2 = f.

( 2.0)[H 2 O] , [H2O] = 0.55 M (0.10)(5.0)

Water is a product of the reaction, but it is not the solvent. Thus the concentration of water must be included in the equilibrium expression because it is a solute in the reaction. When water is the solvent, then it is not included in the equilibrium expression. [ H 2 ]2 [O 2 ] [ H 2 O ]2
2 PNOBr 2 PNO PBr2

43.

K=

, 2.4 10 3 =

(1.9 10 2 ) 2 [O 2 ] (0.11) 2

, [O2] = 0.080 M

44.

KP =

, 109 =

(0.768) 2
2 PNO 0.0159

, PNO = 0.0583 atm

462
45.

CHAPTER 13
SO2(g) + NO2(g) SO3(g) + NO(g) K = [SO 3 ][ NO] [SO 2 ][ NO 2 ]

CHEMICAL EQUILIBRIUM

To determine K, we must calculate the equilibrium concentrations. The initial concentrations are: 2.00 mol = 2.00 M [SO3]0 = [NO]0 = 0; [SO2]0 = [NO2]0 = 1.00 L Next, we determine the change required to reach equilibrium. At equilibrium, [NO] = 1.30 mol/1.00 L = 1.30 M. Because there was zero NO present initially, 1.30 M of SO2 and 1.30 M NO2 must have reacted to produce 1.30 M NO as well as 1.30 M SO3, all required by the balanced reaction. The equilibrium concentration for each substance is the sum of the initial concentration plus the change in concentration necessary to reach equilibrium. The equilibrium concentrations are: [SO3] = [NO] = 0 + 1.30 M = 1.30 M; [SO2] = [NO2] = 2.00 M - 1.30 M = 0.70 M We now use these equilibrium concentrations to calculate K: K=
[SO 3 ][ NO] (1.30)(1.30) = = 3.4 [SO 2 ][ NO 2 ] (0.70)(0.70)

46.

S8(g) 4 S2(g)

Kp =

PS42 PS8

Initially: PS8 = 1.00 atm and PS2 = 0 atm

Change: Because 0.25 atm of S8 remain at equilibrium, 1.00 atm 0.25 atm = 0.75 atm of S8 must have reacted in order to reach equilibrium. Because there is a 4 : 1 mole ratio between S2 and S8 (from the balanced reaction), 4(0.75 atm) = 3.0 atm of S2 must have been produced when the reaction went to equilibrium (moles and pressure are directly related at constant T and V). Equilibrium: PS8 = 0.25 atm, PS2 = 0 + 3.0 atm = 3.0 atm; solving for Kp: Kp =

(3.0) 4 = 3.2 102 0.25

47.

When solving equilibrium problems, a common method to summarize all the information in the problem is to set up a table. We commonly call this table an ICE table because it summarizes initial concentrations, changes that must occur to reach equilibrium, and equilibrium concentrations (the sum of the initial and change columns). For the change column, we will generally use the variable x, which will be defined as the amount of reactant (or product) that must react to reach equilibrium. In this problem, the reaction must shift right to reach equilibrium because there are no products present initially. Therefore, x is defined as the amount of reactant SO3 that reacts to reach equilibrium, and we use the coefficients in the balanced equation to relate the net change in SO3 to the net change in SO2 and O2. The general ICE table for this problem is:

CHAPTER 13

CHEMICAL EQUILIBRIUM
2 SO3(g)

463
+ O2(g) K= [SO 2 ]2 [O 2 ] [SO 3 ]2

2 SO2(g)

Initial Change Equil.

12.0 mol/3.0 L 0 0 Let x mol/L of SO3 react to reach equilibrium. x +x +x/2 x x/2 4.0 x

From the problem, we are told that the equilibrium SO2 concentration is 3.0 mol/3.0 L = 1.0 M ([SO2]e = 1.0 M). From the ICE table setup, [SO2]e = x, so x = 1.0. Solving for the other equilibrium concentrations: [SO3]e = 4.0 x = 4.0 1.0 = 3.0 M; [O2] = x/2 = 1.0/2 = 0.50 M. K= [SO 2 ]2 [O 2 ] (1.0) 2 (0.50) = = 0.056 [SO 3 ]2 (3.0) 2

Alternate method: Fractions in the change column can be avoided (if you want) be defining x differently. If we were to let 2x mol/L of SO3 react to reach equilibrium, then the ICE table setup is: [SO 2 ]2 [O 2 ] 2 SO3(g) 2 SO2(g) + O2(g) K= [SO 3 ]2 Initial 4.0 M 0 0 Let 2x mol/L of SO3 react to reach equilibrium. Change 2x +2x +x 2x x Equil. 4.0 2x Solving: 2x = [SO2]e = 1.0 M, x = 0.50 M; [SO3]e = 4.0 2(0.50) = 3.0 M; [O2]e = x = 0.50 M These are exactly the same equilibrium concentrations as solved for previously, thus K will be the same (as it must be). The moral of the story is to define x in a manner that is most comfortable for you. Your final answer is independent of how you define x initially. 48. When solving equilibrium problems, a common method to summarize all the information in the problem is to set up a table. We commonly call this table the ICE table because it summarizes initial concentrations, changes that must occur to reach equilibrium, and equilibrium concentrations (the sum of the initial and change columns). For the change column, we will generally use the variable x, which will be defined as the amount of reactant (or product) that must react to reach equilibrium. In this problem, the reaction must shift right since there are no products present initially. The general ICE table for this problem is: 2 NO2(g) Initial Change Equil.

2 NO(g)

O2(g)

K=

[ NO]2 [O 2 ] [ NO 2 ]2

8.0 mol/1.0 L 0 0 Let x mol/L of NO2 react to reach equilibrium x +x +x/2 8.0 x x x/2

464

CHAPTER 13

CHEMICAL EQUILIBRIUM

Note that we must use the coefficients in the balanced equation to determine the amount of products produced when x mol/L of NO2 reacts to reach equilibrium. In the problem, we are told that [NO]e = 2.0 M. From the set up, [NO]e = x = 2.0 M. Solving for the other concentrations: [NO]e = 8.0 x = 8.0 2.0 = 6.0 M; [O2]e = x/2 = 2.0/2 = 1.0 M. Calculating K: K= [ NO]2 [O 2 ] [ NO 2 ]2

(2.0 M ) 2 (1.0 M ) ( 6 .0 M ) 2

= 0.11 mol/L

Alternate method: Fractions in the change column can be avoided (if you want) by defining x differently. If we were to let 2x mol/L of NO2 react to reach equilibrium, then the ICE table set-up is: [ NO]2 [O 2 ] 2 NO(g) + O2(g) K= 2 NO2(g) [ NO 2 ]2 8.0 M 0 0 Let 2x mol/L of NO2 react to reach equilibrium 2x +2x +x Change Equil. 8.0 2x 2x x Solving: 2x = [NO]e = 2.0 M, x = 1.0 M; [NO2]e = 8.0 2(1.0) = 6.0 M; [O2]e = x = 1.0 M These are exactly the same equilibrium concentrations as solved for previously; thus K will be the same (as it must be). The moral of the story is to define x in a manner that is most comfortable for you. Your final answer is independent of how you define x initially. 49. Initial Change Equil 3 H2(g) + N2(g)

2 NH3 (g)

[N2]0 0 [H2]0 x mol/L of N2 reacts to reach equilibrium ! 3x !x +2x [N2]0 ! x 2x [H2]0 ! 3x

From the problem: [NH3]e = 4.0 M = 2x, x = 2.0 M; [H2]e = 5.0 M = [H2]0 !3x; [N2]e = 8.0 M = [N2]0 !x 5.0 M = [H2]0 ! 3(2.0 M), [H2]0 = 11.0 M; 8.0 M = [N2]0 ! 2.0 M, [N2]0 = 10.0 M 50. N2(g) + 3 H2(g) 2 NH3(g); with only reactants present initially, the net change that must occur to reach equilibrium is a conversion of reactants into products. At constant volume and temperature, n P. Thus, if x atm of N2 reacts to reach equilibrium, then 3x atm of H2 must also react to form 2x atm of NH3 (from the balanced equation). Lets summarize the problem in a table that lists what is present initially, what change in terms of x that occurs to reach equilibrium, and what is present at equilibrium (initial + change). This table is typically called an ICE table for initial, change, and equilibrium.

CHAPTER 13

CHEMICAL EQUILIBRIUM
N2(g) + 3 H2(g)

465
Kp =
2 PNH3 3 PN 2 PH 2

2 NH3(g)

Initial Change Equil.

1.00 atm 2.00 atm 0 x atm of N2 reacts to reach equilibrium !x ! 3x +2x 2.00 ! 3x 2x 1.00 ! x

From the setup: Ptotal = 2.00 atm = PN 2 + PH 2 + PNH 3 2.00 atm = (1.00 x) + (2.00 3x) + 2x = 3.00 2x, x = 0.500 PH 2 = 2.00 3x = 2.00 3(0.500) = 0.50 atm Kp = 51. (1.00) 2 (2 x) 2 [2(0.500)]2 = = = 16 (1.00 x)(2.00 3 x) 3 (1.00 0.500)[2.00 3(0.500)]3 (0.50)(0.50) 3

Q = 1.00, which is less than K. The reaction shifts to the right to reach equilibrium. Summarizing the equilibrium problem in a table: SO2(g) Initial Change Equil. + NO2(g)

SO3(g)

+ NO(g)

K = 3.75

0.800 M 0.800 M 0.800 M 0.800 M x mol/L of SO2 reacts to reach equilibrium !x !x +x +x 0.800 ! x 0.800 + x 0.800 + x 0.800 ! x

Plug the equilibrium concentrations into the equilibrium constant expression: K= [SO 3 ][ NO] (0.800 + x) 2 ; take the square root of both sides and solve , 3.75 = [SO 2 ][ NO 2 ] (0.800 x) 2 for x:

0.800 + x = 1.94, 0.800 + x = 1.55 ! (1.94)x, (2.94)x = 0.75, x = 0.26 M 0.800 x The equilibrium concentrations are: [SO3] = [NO] = 0.800 + x = 0.800 + 0.26 = 1.06 M; [SO2] = [NO2] = 0.800 ! x = 0.54 M 52. Q = 1.00, which is less than K. Reaction shifts right to reach equilibrium. [HI] 2 + I2(g) 2 HI(g) K = = 100. H2(g) [H 2 ][I 2 ] 1.00 M 1.00 M Initial 1.00 M x mol/L of H2 reacts to reach equilibrium Change !x !x +2x 1.00 ! x 1.00 + 2x Equil. 1.00 ! x K = 100. = (1.00 + 2 x) 2 (1.00 x) 2
; taking the square root of both sides:

466
10.0 =

CHAPTER 13

CHEMICAL EQUILIBRIUM

1.00 + 2 x , 10.0 ! (10.0)x = 1.00 + 2x, (12.0)x = 9.0, x = 0.75 M 1.00 x

[H2] = [I2] = 1.00 ! 0.75 = 0.25 M; [HI] = 1.00 + 2(0.75) = 2.50 M 53. Because only reactants are present initially, the reaction must proceed to the right to reach equilibrium. Summarizing the problem in a table: N2(g) Initial Change Equil. Kp = 0.050 = + O2(g)

2 NO(g)

Kp = 0.050

0.80 atm 0.20 atm 0 x atm of N2 reacts to reach equilibrium x x +2x 0.80 x 0.20 x 2x
2 PNO (2 x) 2 = , 0.050[0.16 (1.00)x + x2] = 4x2 (0.80 x)(0.20 x) PN 2 PO 2

4x2 = 8.0 103 (0.050)x + (0.050)x2, (3.95)x2 + (0.050)x 8.0 103 = 0 Solving using the quadratic formula (see Appendix 1 of the text):
x=

b (b 2 4ac)1/ 2 0.050 [(0.050)]2 4(3.95)(8.0 10 3 )]1/ 2 = 2a 2(3.95)

x = 3.9 102 atm or x = 5.2 102 atm; only x = 3.9 102 atm makes sense (x cannot be negative), so the equilibrium NO concentration is:

PNO = 2x = 2(3.9 102 atm) = 7.8 102 atm 54. H2O(g) + Cl2O(g) 2 HOCl(g) K = 0.090 = [HOCl] 2 [H 2 O][Cl 2 O]

a. The initial concentrations of H2O and Cl2O are: 1 .0 g H 2 O 2.0 g Cl 2 O 1 mol 1 mol = 5.5 10 2 mol/L; = 2.3 10 2 mol/L 1.0 L 18.02 g 1.0 L 86.90 g H2O(g) Initial Change Equil. K = 0.090 = + Cl2O(g)

2 HOCl(g)

5.5 10 2 M 2.3 10 2 M 0 x mol/L of H2O reacts to reach equilibrium !x !x +2x 2 2 5.5 10 ! x 2.3 10 ! x 2x (2 x) 2 (5.5 10 2 x)(2.3 10 2 x)

1.14 10 4 ! (7.02 10 3 )x + (0.090)x2 = 4x2

CHAPTER 13

CHEMICAL EQUILIBRIUM

467

(3.91)x2 + (7.02 10 3 )x ! 1.14 10 4 = 0 (We carried extra significant figures.) Solving using the quadratic formula: 7.02 10 3 (4.93 10 5 + 1.78 10 3 )1 / 2 = 4.6 10 3 or !6.4 10 3 7.82 A negative answer makes no physical sense; we can't have less than nothing. Thus x = 4.6 10 3 M. [HOCl] = 2x = 9.2 10 3 M; [Cl2O] = 2.3 10 2 ! x = 0.023 ! 0.0046 = 1.8 10 2 M [H2O] = 5.5 10 2 ! x = 0.055 ! 0.0046 = 5.0 10 2 M b. Initial Change Equil. K = 0.090 = H2O(g) + Cl2O(g)

2 HOCl(g)

0 0 1.0 mol/2.0 L = 0.50 M 2x mol/L of HOCl reacts to reach equilibrium +x !2 x +x x x 0.50 ! 2x [ HOCl]2 (0.50 2 x) 2 = [H 2 O][Cl 2 O] x2

The expression is a perfect square, so we can take the square root of each side: 0.30 =
0.50 2 x , (0.30)x = 0.50 ! 2x, (2.30)x = 0.50 x

x = 0.217 (We carried extra significant figures.) x = [H2O] = [Cl2O] = 0.217 = 0.22 M; [HOCl] = 0.50 ! 2x = 0.50 ! 0.434 = 0.07 M 55. Initial Change Equil. Kp = 0.25 = 2 SO2(g) + O2(g)

2 SO3(g)

Kp = 0.25

0.50 atm 0.50 atm 0 2x atm of SO2 reacts to reach equilibrium 2x x +2x 0.50 2x 0.50 x 2x
2 PSO 3 2 PSO 2 PO 2

(2 x) 2 (0.50 2 x) 2 (0.50 x)

This will give a cubic equation. Graphing calculators can be used to solve this expression. If you dont have a graphing calculator, an alternative method for solving a cubic equation is to use the method of successive approximations (see Appendix 1 of the text). The first step is to guess a value for x. Because the value of K is small (K < 1), not much of the forward

468

CHAPTER 13

CHEMICAL EQUILIBRIUM

reaction will occur to reach equilibrium. This tells us that x is small. Lets guess that x = 0.050 atm. Now we take this estimated value for x and substitute it into the equation everywhere that x appears except for one. For equilibrium problems, we will substitute the estimated value for x into the denominator and then solve for the numerator value of x. We continue this process until the estimated value of x and the calculated value of x converge on the same number. This is the same answer we would get if we were to solve the cubic equation exactly. Applying the method of successive approximations and carrying extra significant figures:
4x2 [0.50 2(0.050)]2 [0.50 (0.050)]

4x2 (0.40) 2 (0.45)

= 0.25 , x = 0.067

4x2 [0.50 2(0.067)]2 [0.50 (0.067)]

4x2 (0.366) 2 (0.433)

= 0.25 , x = 0.060

4x2 4x2 = 0.25, x = 0.063; = 0.25, (0.38) 2 (0.44) (0.374) 2 (0.437)

x = 0.062

The next trial gives the same value for x = 0.062 atm. We are done except for determining the equilibrium concentrations. They are: PSO 2 = 0.50 2x = 0.50 2(0.062) = 0.376 = 0.38 atm PO 2 = 0.50 x = 0.438 = 0.44 atm; PSO 3 = 2x = 0.124 = 0.12 atm 56. a. The reaction must proceed to products to reach equilibrium because no product is present initially. Summarizing the problem in a table where x atm of N2O4 reacts to reach equilibrium: N2O4(g) Initial Change Equil. Kp =
2 PNO 2

2 NO2(g) 0 +2x 2x

Kp = 0.25

4.5 atm !x 4.5 ! x

PN

2O 4

(2 x)2 = 0.25, 4x2 = 1.125 ! (0.25)x, 4x2 + (0.25)x ! 1.125 = 0 4 .5 x

We carried extra significant figures in this expression (as will be typical when we solve an expression using the quadratic formula). Solving using the quadratic formula (Appendix 1 of text): x= 0.25 [(0.25) 2 4(4)(1.125)]1/ 2 0.25 4.25 = , x = 0.50 (Other value is 2( 4) 8 negative.)

PNO 2 = 2x = 1.0 atm; PN 2O 4 = 4.5 ! x = 4.0 atm

CHAPTER 13

CHEMICAL EQUILIBRIUM

469

b. The reaction must shift to reactants (shifts left) to reach equilibrium. N2O4(g) Initial Change Equil. Kp = 0 +x x

2 NO2(g) 9.0 atm !2x 9.0 ! 2x

(9.0 2 x) 2 = 0.25, 4x2 ! (36.25)x + 81 = 0 (carrying extra sig. figs.) x (36.25) [(36.25) 2 4(4)(81)]1 / 2 Solving: x = , x = 4.0 atm 2( 4) The other value, 5.1, is impossible. PN 2O 4 = x = 4.0 atm; PNO 2 = 9.0 ! 2x = 1.0 atm c. No, we get the same equilibrium position starting with either pure N2O4 or pure NO2 in stoichiometric amounts. 57. a. The reaction must proceed to products to reach equilibrium because only reactants are present initially. Summarizing the problem in a table: 2 NOCl(g) Initial Change Equil.

2 NO(g)

Cl2(g)

K = 1.6 10 5

2.0 mol = 1.0 M 0 0 2.0 L 2x mol/L of NOCl reacts to reach equilibrium !2 x +2x +x 2x x 1.0 ! 2x

K = 1.6 10 5 =

[ NO]2 [Cl 2 ] [ NOCl]2

(2 x) 2 ( x) (1.0 2 x) 2

If we assume that 1.0 ! 2x 1.0 (from the small size of K, we know that the product concentrations will be small), then: 1.6 10 5 =
4x3 , x = 1.6 10 2 ; now we must check the assumption. 1 .0 2

1.0 ! 2x = 1.0 ! 2(0.016) = 0.97 = 1.0 (to proper significant figures) Our error is about 3%; that is, 2x is 3.2% of 1.0 M. Generally, if the error we introduce by making simplifying assumptions is less than 5%, we go no further; the assumption is said to be valid. We call this the 5% rule. Solving for the equilibrium concentrations: [NO] = 2x = 0.032 M; [Cl2] = x = 0.016 M; [NOCl] = 1.0 ! 2x = 0.97 M 1.0 M

Note: If we were to solve this cubic equation exactly (a longer process), we get x = 0.016. This is the exact same answer we determined by making a simplifying assumption. We saved time and energy. Whenever K is a very small value ( K << 1), always make the

470

CHAPTER 13

CHEMICAL EQUILIBRIUM

assumption that x is small. If the assumption introduces an error of less than 5%, then the answer you calculated making the assumption will be considered the correct answer. b. Initial Change Equil. 1.6 10 5 = 2 NOCl(g)

2 NO(g)

Cl2(g)

1.0 M 1.0 M 0 2x mol/L of NOCl reacts to reach equilibrium !2x +2x +x 1.0 ! 2x 1.0 + 2x x
(1.0 + 2 x) 2 ( x) (1.0 2 x) 2

(1.0) 2 ( x) (1.0) 2

(assuming 2x << 1.0)

x = 1.6 10 5 ; assumptions are great (2x is 3.2 103% of 1.0).

[Cl2] = 1.6 10 5 M and [NOCl] = [NO] = 1.0 M c. Initial Change Equil. 1.6 10 5 = 2 NOCl(g)

2 NO(g)

Cl2(g)

2.0 M 0 1.0 M 2x mol/L of NOCl reacts to reach equilibrium !2 x +2x +x 2x 1.0 + x 2.0 ! 2x (2 x) 2 (1.0 + x) (2.0 2 x) 2

4x2 (assuming x << 1.0) 4 .0

Solving: x = 4.0 10 3 ; assumptions good (x is 0.4% of 1.0 and 2x is 0.4% of 2.0). [Cl2] = 1.0 + x = 1.0 M; [NO] = 2(4.0 10 3 ) = 8.0 10 3 M; [NOCl] = 2.0 M 58. Initial Change Equil. K= N2O4(g)

2 NO2(g)

K=

[ NO 2 ]2 = 4.0 10 7 [ N 2O 4 ]

1.0 mol/10.0 L 0 x mol/L of N2O4 reacts to reach equilibrium !x +2x 2x 0.10 ! x

[ NO 2 ]2 (2 x) 2 = = 4.0 10 7 ; because K has a small value, assume that x is small [ N 2O 4 ] 0.10 x compared to 0.10, so that 0.10 ! x 0.10. Solving: 4.0 10 7 4x2 , 4x2 = 4.0 10 8 , x = 1.0 10 4 M 0.10

CHAPTER 13

CHEMICAL EQUILIBRIUM
1.0 10 4 x 100 = 100 = 0.10% 0.10 0.10

471

Checking the assumption by the 5% rule:

Because this number is less than 5%, we will say that the assumption is valid. [N2O4] = 0.10 ! 1.0 10 4 = 0.10 M; [NO2] = 2x = 2(1.0 10 4 ) = 2.0 10 4 M 59. Initial Change Equil. 2 CO2(g)

2 CO(g)

O2(g)

K=

[CO] 2 [O 2 ] [CO 2 ] 2

= 2.0 106

2.0 mol/5.0 L 0 0 2x mol/L of CO2 reacts to reach equilibrium 2x +2x +x 2x x 0.40 2x [CO] 2 [O 2 ] [CO 2 ] 2 = (2 x) 2 ( x) ; assuming 2x << 0.40 (K is small, so x is (0.40 2 x) 2 small.)

K = 2.0 106 = 2.0 10-6

4 x3 4x3 , 2.0 106 = , x = 4.3 103 M 0.16 (0.40) 2 2(4.3 10 3 ) 100 = 2.2%; assumption is valid by the 5% rule. 0.40

Checking assumption:

[CO2] = 0.40 2x = 0.40 2(4.3 103) = 0.39 M [CO] = 2x = 2(4.3 103) = 8.6 103 M; [O2] = x = 4.3 103 M 60. Initial Change Equil. COCl2(g)

CO(g) +

Cl2(g)

Kp =

PCO PCl2 PCOCl2

= 6.8 10 9

1.0 atm 0 0 x atm of COCl2 reacts to reach equilibrium !x +x +x 1.0 ! x x x PCO PCl2 PCOCl2 =

6.8 10 9 =

x2 x2 (Assuming 1.0 ! x 1.0.) 1 .0 x 1 .0

x = 8.2 10 5 atm; assumption is good (x is 8.2 10-3% of 1.0).

PCOCl 2 = 1.0 ! x = 1.0 ! 8.2 10 5 = 1.0 atm; PCO = PCl 2 = x = 8.2 10 5 atm 61. This is a typical equilibrium problem except that the reaction contains a solid. Whenever solids and liquids are present, we basically ignore them in the equilibrium problem.

472
NH4OCONH2(s) Initial

CHAPTER 13

CHEMICAL EQUILIBRIUM
Kp = 2.9 10 3

2 NH3(g) + CO2(g)

0 0 Some NH4OCONH2 decomposes to produce 2x atm of NH3 and x atm of CO2. Change +2x +x x Equil. 2x
2 Kp = 2.9 10 3 = PNH 3 PCO 2 = (2x)2(x) = 4x3

2.9 10 3 x= 4

1/ 3

= 9.0 10 2 atm; PNH 3 = 2x = 0.18 atm; PCO 2 = x = 9.0 10 2 atm

Ptotal = PNH 3 + PCO 2 = 0.18 atm + 0.090 atm = 0.27 atm 62. NH4Cl(s) NH3(g) + HCl(g) Kp = PNH 3 PHCl

For this system to reach equilibrium, some of the NH4Cl(s) decomposes to form equal moles of NH3(g) and HCl(g) at equilibrium. Because mol HCl produced = mol NH3 produced, the partial pressures of each gas must be equal to each other. At equilibrium: Ptotal = PNH 3 + PHCl and PNH 3 = PHCl Ptotal = 4.4 atm = 2PNH , 2.2 atm = PNH 3 = PHCl; Kp = (2.2)(2.2) = 4.8
3

Le Chatelier's Principle
63. a. No effect; adding more of a pure solid or pure liquid has no effect on the equilibrium position. b. Shifts left; HF(g) will be removed by reaction with the glass. As HF(g) is removed, the reaction will shift left to produce more HF(g). c. Shifts right; as H2O(g) is removed, the reaction will shift right to produce more H2O(g). 64. When the volume of a reaction container is increased, the reaction itself will want to increase its own volume by shifting to the side of the reaction that contains the most molecules of gas. When the molecules of gas are equal on both sides of the reaction, then the reaction will remain at equilibrium no matter what happens to the volume of the container. a. Reaction shifts left (to reactants) because the reactants contain 4 molecules of gas compared with 2 molecules of gas on the product side. b. Reaction shifts right (to products) because there are more product molecules of gas (2) than reactant molecules (1).

CHAPTER 13

CHEMICAL EQUILIBRIUM

473

c. No change because there are equal reactant and product molecules of gas. d. Reaction shifts right. e. Reaction shifts right to produce more CO2(g). One can ignore the solids and only concentrate on the gases because gases occupy a relatively huge volume compared with solids. We make the same assumption when liquids are present (only worry about the gas molecules). 65. a. Right b. Right c. No effect; He(g) is neither a reactant nor a product.

d. Left; because the reaction is exothermic, heat is a product: CO(g) + H2O(g) H2(g) + CO2(g) + heat Increasing T will add heat. The equilibrium shifts to the left to use up the added heat. e. No effect; because the moles of gaseous reactants equals the moles of gaseous products (2 mol versus 2 mol), a change in volume will have no effect on the equilibrium. 66. a. The moles of SO3 will increase because the reaction will shift left to use up the added O2(g). b. Increase; because there are fewer reactant gas molecules than product gas molecules, the reaction shifts left with a decrease in volume. c. No effect; the partial pressures of sulfur trioxide, sulfur dioxide, and oxygen are unchanged, so the reaction is still at equilibrium. d. Increase; heat + 2 SO3 2 SO2 + O2; decreasing T will remove heat, shifting this endothermic reaction to the left. e. Decrease 67. a. Left b. Right c. Left

d. No effect (reactant and product concentrations are unchanged) e. No effect; because there are equal numbers of product and reactant gas molecules, a change in volume has no effect on this equilibrium position. f. 68. Right; a decrease in temperature will shift the equilibrium to the right because heat is a product in this reaction (as is true in all exothermic reactions).

a. Shift to left b. Shift to right; because the reaction is endothermic (heat is a reactant), an increase in temperature will shift the equilibrium to the right. c. No effect d. Shift to right

474

CHAPTER 13

CHEMICAL EQUILIBRIUM

e. Shift to right; because there are more gaseous product molecules than gaseous reactant molecules, the equilibrium will shift right with an increase in volume. 69. An endothermic reaction, where heat is a reactant, will shift right to products with an increase in temperature. The amount of NH3(g) will increase as the reaction shifts right, so the smell of ammonia will increase. As temperature increases, the value of K decreases. This is consistent with an exothermic reaction. In an exothermic reaction, heat is a product, and an increase in temperature shifts the equilibrium to the reactant side (as well as lowering the value of K).

70.

Connecting to Biochemistry
71. a. [O 2 ] 6 [H 2 O] [CO 2 ] [O 2 ]6 [H 2 O] [CO 2 ]
6 6 6 6

b. K = [C2H5OH]2[CO2]2 ( 2.4 10 3 ) 6 (7.91 10 ) (0.93) K=

2 6

c. K =

[C 3 H 5 O 3 H ] [C3H 3O3H][H 2 ]

72.

K=

= 1.2 109

73.

alpha-glucose

beta-glucose

[beta - glucose] [alpha - glucose]

From the problem, alphaglucose = 2[beta-glucose], so: [beta - glucose] 1 = = 0.50 2 2[beta - glucose]
[dipeptide] 0.20 = = 0.83 [alanine][leucine] 0.60(0.40)

K=

74.

a. Q =

Q < K, so the reaction shifts right to reach equilibrium. b. Q = 0.40 (3.5 10 4 )3.6 0.30 (6.0 10 )( 9.0 10 )
3 3

= 3.2 102 = K; at equilibrium (no shift).

c. Q =

= 5.6 103

Q > K, so the reaction shifts left to reach equilibrium.

CHAPTER 13
75. Initial Change Equil. K = 5.0 =

CHEMICAL EQUILIBRIUM
cis fat(aq) + H2(aq)

475
K = 5.0 = [trans fat] [cis fat][H 2 ]

trans fat(aq)

0.10 M 0.10 M 0 Let x mol/L of cis fat react to reach equilibrium. x x +x 0.10 x 0.10 x x
x ; because K is fairly large, x will not be very small as (0.10 x)(0.10 x) compared to 0.10, so we must solve exactly.

5.0 =

(0.10 x)

, 5.0[0.010 (0.20)x + x2] = x, (5.0)x2 (2.0)x + 0.050 = 0

Solving using the quadratic formula (see Appendix 1 of the text):

x=
b (b 2 4ac)1 / 2 (2.0) [(2.0) 2 4(5.0)(0.050)]1 / 2 = 2a 2(5.0)

x = 0.373 M or x = 0.027 M; only 0.027 is possible, so the equilibrium concentrations are:

[cis fat] = [H2] = 0.10 0.027 = 0.07 M; [trans fat] = x = 0.027 M 76. Initial Change Equil. peptide(aq) + H2O(l)

acid group(aq) + amine group(aq) K = 3.1 105 0 +x x

1.0 mol 0 = 1.0 M 1 .0 L x mol/L peptide reacts to reach equilibrium. x +x x 1.0 x

Note: Because water is not included in the K expression, the amount of water present initially and the amount of water that reacts are not needed to solve this problem.

K = 3.1 105 =

x( x) x2 , 3.1 10 5 (assuming 1.0 x 1.0) 1 .0 x 1 .0

x=

3.1 10 5 = 5.6 103 M; assumption good (0.56% error).

[peptide] = 1.0 x = 1.0 5.6 103 = 1.0; [acid group] = [amine group] = x = 5.6 103 M

476
77. Initial Change Equil. HCO3(aq)

CHAPTER 13

CHEMICAL EQUILIBRIUM
[H + ][CO 3 2 ] [HCO 3 ] = 5.6 1011

H+(aq) + CO32(aq)

K=

0.16 mol/1.0 L 0 0 x mol/L HCO3 reacts to reach equilibrium +x +x x 0.16 x x x

x(x) x2 0.16 x 0.16

5.6 1011 =

(assuming x << 0.16)

x=

5.6 10 11 (0.16) = 3.0 106 M; assumption good (8 103% error).

[CO32] = x = 3.0 106 M 78. Initial Change Equil. CH3OH(aq)

H2CO(aq)

+ H2(aq)

K = 3.7 1010 =

[H 2 CO][H 2 ] [CH 3OH]

0 0 1.24 M x mol/L CH3OH reacts to reach equilibrium +x +x x 1.24 x x x

x( x) x2 (assuming x << 1.24) 1.24 x 1.24

3.7 1010 =

x = 2.1 105 M; assumption good (1.7 103% error).

[H2CO] = [H2] = x = 2.1 105 M; [CH3OH] = 1.24 2.1 105 = 1.24 M As formaldehyde is removed from the equilibrium by forming some other substance, the equilibrium shifts right to produce more formaldehyde. Hence the concentration of methanol (a reactant) decreases as formaldehyde (a product) reacts to form formic acid. 79. a. Reaction shifts right as a reactant solute is added. b. Reaction shifts right as a product solute is removed. c. Reaction shifts left as a product solute is added. d. When the volume of solution doubles, each concentration decreases by a factor of 1/2.

Q= 2

( [C 2 H 5OH]eq ) 2 ( [CO 2 ]eq ) 2

2 1 2

1 [C H OH]eq [CO 2 ]eq 1 = K = 2 5

2 2

[C6 H12 O 6 ]eq

[C 6 H12 O 6 ]eq

As the concentrations are halved, Q < K, so the reaction shifts right to reestablish equilibrium.

CHAPTER 13
80.

CHEMICAL EQUILIBRIUM

477

Assuming 100.00 g naphthalene: 93.71 C 6.29 g H 1 mol C = 7.802 mol C 12.011 g 1 mol H = 6.24 mol H; 1.008 g 7.802 = 1.25 6.24
32.8 g = 128 g/mol 0.256 mol

Empirical formula = (C1.25H)4 = C5H4; molar mass =

Because the empirical mass (64.08 g/mol) is one-half of 128, the molecular formula is C10H8. C10H8(s) Initial Equil.

C10H8(g)

K = 4.29 10 6 = [C10H8]

0 Let some C10H8(s) sublime to form x mol/L of C10H8(g) at equilibrium. x

K = 4.29 10 6 = [C10H8] = x Mol C10H8 sublimed = 5.00 L 4.29 10 6 mol/L = 2.15 10 5 mol C10H8 sublimed Mol C10H8 initially = 3.00 g
1 mol C10 H 8 = 2.34 10 2 mol C10H8 initially 128.16 g

Percent C10H8 sublimed =

2.15 10 5 mol 100 = 0.0919% 2.34 10 2 mol

Additional Exercises
81. K = 1/6.8 10 49 = 1.5 1048 O(g) + NO(g) NO2(g) NO2(g) + O2(g) NO(g) + O3(g) K = 1/5.8 10 34 = 1.7 1033 ___________________________________________________________________ K = (1.5 1048)(1.7 1033) = 2.6 1081 O2(g) + O(g) O3(g) Na2O(s) 2 Na(l) + 1/2 O2(g)

82.

a.

Na2O(s) + 1/2 O2(g) Na2O2(s) K= 2 10 25 = 4 103 29 5 10

1/K3 2 Na(l) + O2(g) Na2O2(s) ___________________________________________________ K = (K1)(1/K3)

K1

478
b.

CHAPTER 13
NaO(g) Na(l) + 1/2 O2(g) K2 K1

CHEMICAL EQUILIBRIUM

1/K3 2 Na(l) + O2(g) Na2O2(s) ____________________________________________________________ K = K2(K1)(1/K3) = 8 102 NaO(g) + Na2O(s) Na2O2(s) + Na(l) c. 1/K3 2 Na(l) + O2(g) Na2O2(s) ____________________________________________________________ K = (K 2 ) 2 (1/K 3 ) = 8 1018 2 NaO(g) Na2O2(s) 1 mol C 5 H 6 O 3 = 0.0493 mol C5H6O3 initially 114.10 g Ptotal V 1.63 atm 2.50 L = 0.105 mol = 0.08206 L atm RT 473 K K mol C2H6(g) + 3 CO(g) 2 NaO(g) 2 Na(l) + O2(g) (K2)2

Na2O(s) 2 Na(l) + 1/2 O2(g)

83.

5.63 g C5H6O3

Total moles of gas at equilibrium = ntotal = C5H6O3(g) Initial Change Equil.

0.0493 mol 0 0 Let x mol C5H6O3 react to reach equilibrium. !x +x +3x 0.0493 ! x x 3x

0.105 mol total = 0.0493 x + x + 3x = 0.0493 + 3x, x = 0.0186 mol 0.0186 mol C 2 H 6 3(0.0186) mol CO 3 2.50 L 2.50 L [C H ][CO] K= 2 6 = [C 5 H 6 O 3 ] (0.0493 0.0186) mol C5 H 6 O3 2.50 L 84. a. N2(g) + O2(g) 2 NO(g) PNO = 1 1016 atm In 1.0 cm3 of air: nNO = PV (1 10 16 atm)(1.0 10 3 L) = = 4 1021 mol NO RT 0.08206 L atm (298 K ) K mol Kp = 1 1031 =
3

= 6.74 10 6

2 2 PNO PNO = (0.8)(0.2) PN 2 PO 2

4 10 21 mol NO 6.02 10 23 molecules 2 103 molecules NO = mol NO cm 3 cm 3

CHAPTER 13

CHEMICAL EQUILIBRIUM

479

b. There is more NO in the atmosphere than we would expect from the value of K. The answer must lie in the rates of the reaction. At 25C, the rates of both reactions: N2 + O2 2 NO and 2 NO N2 + O2 are so slow that they are essentially zero. Very strong bonds must be broken; the activation energy is very high. Therefore, the reaction essentially doesnt occur at low temperatures. Nitric oxide, however, can be produced in high-energy or hightemperature environments because the production of NO is endothermic. In nature, some NO is produced by lightning, and the primary manmade source is automobiles. At these high temperatures, K will increase, and the rates of the reaction will also increase, resulting in a higher production of NO. Once the NO gets into a more normal temperature environment, it doesnt go back to N2 and O2 because of the slow rate. 85. a. Initial Equil. 2 AsH3(g) 392.0 torr 392.0 ! 2x

2 As(s)

3 H2(g) 0 3x

Using Daltons law of partial pressure: Ptotal = 488.0 torr = PAsH3 + PH 2 = 392.0 ! 2x + 3x, x = 96.0 torr PH 2 = 3x = 3(96.0) = 288 torr 1 atm = 0.379 atm 760 torr
1 atm = 0.2632 atm 760 torr

b.

PAsH3 = 392.0 2(96.0) = 200.0 torr Kp = (PH 2 )3 (PAsH3 ) 2

(0.379) 3 (0.2632) 2

= 0.786 SCN(aq) K = 9.1 10 4

86. Initial Change Equil. 9.1 10 4 =

FeSCN2+(aq)

Fe3+(aq)

0 0 2.0 M x mol/L of FeSCN2+ reacts to reach equilibrium !x +x +x 2.0 ! x x x [Fe3+ ][SCN ] [FeSCN 2+ ]

x2 x2 = (assuming 2.0 ! x 2.0) 2.0 x 2.0

x = 4.3 10 2 M; assumption good by the 5% rule (x is 2.2% of 2.0).

[FeSCN2+] = 2.0 ! x = 2.0 ! 4.3 10 2 = 2.0 M; [Fe3+] = [SCN] = x = 4.3 10 2 M

480
87.

CHAPTER 13

CHEMICAL EQUILIBRIUM

There is a little trick we can use to solve this problem without having to solve a quadratic equation. Because K is very large (K >> 1), the reaction will have mostly products at equilibrium. So we will let the reaction go to completion, and then solve an equilibrium problem to determine the molarity of reactants present at equilibrium (see the following setup). Fe3+(aq) Before Change After Change Equil. + SCN(aq)

FeSCN2+(aq)

K = 1.1 103

0.10 M 0 0.020 M 3+ Let 0.020 mol/L Fe react completely (K is large; products dominate). 0.020 0.020 +0.020 React completely 0 0.08 0.020 New initial x mol/L FeSCN2+ reacts to reach equilibrium +x x +x x 0.08 + x 0.020 x [FeSCN 2 + ] 0.020 x 0.020 = 3+ ( x)(0.08 + x) (0.08) x [Fe ][SCN ]

K = 1.1 103 =

x = 2 104 M; x is 1% of 0.020. Assumptions are good by the 5% rule. x = [Fe3+] = 2 104 M; [SCN-] = 0.08 + 2 104 = 0.08 M

[FeSCN2+] = 0.020 2 104 = 0.020 M

Note: At equilibrium, we do indeed have mostly products present. Our assumption to first let the reaction go to completion is good.
n PCl5 RT V PCl5(g) 2.450 g PCl 5 0.08206 L atm 600. K 208.22 g/mol K mol = = 1.16 atm 0.500 L

88.

a.

PPCl5 =

b.

PCl3(g)

Cl2(g)

Kp =

PPCl3 PCl 2 PPCl5

= 11.5

Initial 1.16 atm 0 0 x atm of PCl5 reacts to reach equilibrium Change x +x +x Equil. 1.16 x x x Kp =

x2 = 11.5, x2 + (11.5)x 13.3 = 0 1.16 x

Using the quadratic formula: x = 1.06 atm PPCl5 = 1.16 1.06 = 0.10 atm

CHAPTER 13
c.

CHEMICAL EQUILIBRIUM

481

PPCl3 = PCl 2 = 1.06 atm; PPCl5 = 0.10 atm Ptotal = PPCl5 + PPCl3 + PCl 2 = 0.10 + 1.06 + 1.06 = 2.22 atm

d. Percent dissociation = 89. Initial Change Equil. SO2Cl2(g) P0 !x P0 ! x

x 1.06 100 = 100 = 91.4% 1.16 1.16

Cl2(g) 0 +x x

SO2(g) 0 +x x P0 = initial pressure of SO2Cl2

Ptotal = 0.900 atm = P0 ! x + x + x = P0 + x

x 100 = 12.5, P0 = (8.00)x P0

Solving: 0.900 = P0 + x = (9.00)x, x = 0.100 atm

x = 0.100 atm = PCl 2 = PSO 2 ; P0 ! x = 0.800 - 0.100 = 0.700 atm = PSO 2Cl 2
Kp = PCl 2 PSO 2 PSO 2Cl 2

(0.100) 2 = 1.43 10 2 atm 0.700

90.

K=

[ HF]2 (0.400 M ) 2 = = 320.; 0.200 mol F2/5.00 L = 0.0400 M F2 added [H 2 ][F2 ] (0.0500 M )(0.0100 M )

After F2 has been added, the concentrations of species present are [HF] = 0.400 M, [H2] = [F2] = 0.0500 M. Q = (0.400)2/(0.0500)2 = 64.0; because Q < K, the reaction will shift right to reestablish equilibrium. H2(g) Initial Change Equil. K = 320. = 17.9 = + F2(g)

2 HF(g)

0.0500 M 0.0500 M 0.400 M x mol/L of F2 reacts to reach equilibrium x x +2x 0.0500 x 0.0500 x 0.400 + 2x (0.400 + 2 x) 2 ; taking the square root of each side: (0.0500 x) 2 0.400 + 2 x , 0.895 (17.9)x = 0.400 + 2x, (19.9)x = 0.495, x = 0.0249 mol/L 0.0500 x

[HF] = 0.400 + 2(0.0249) = 0.450 M; [H2] = [F2] = 0.0500 0.0249 = 0.0251 M

482
91. CoCl2(s) + 6 H2O(g)

CHAPTER 13

CHEMICAL EQUILIBRIUM

CoCl2C6H2O(s);

if rain is imminent, there would be a lot of water

vapor in the air. Because water vapor is a reactant gas, the reaction would shift to the right and would take on the color of CoCl2C6H2O, pink. 92. a. Doubling the volume will decrease all concentrations by a factor of one-half.
1

Q=

1 1 3+ [Fe ]eq [SCN ]eq 2 2

[FeSCN 2 + ]eq

= 2K, Q > K

The reaction will shift to the left to reestablish equilibrium. b. Adding Ag+ will remove SCN through the formation of AgSCN(s). The reaction will shift to the left to produce more SCN-. c. Removing Fe3+ as Fe(OH)3(s) will shift the reaction to the left to produce more Fe3+. d. Reaction will shift to the right as Fe3+ is added. 93. H+ + OH H2O; sodium hydroxide (NaOH) will react with the H+ on the product side of the reaction. This effectively removes H+ from the equilibrium, which will shift the reaction to the right to produce more H+ and CrO42. Because more CrO42 is produced, the solution turns yellow. N2(g) + 3 H2(g) 2 NH3(g) + heat a. This reaction is exothermic, so an increase in temperature will decrease the value of K (see Table 13.3 of text.) This has the effect of lowering the amount of NH3(g) produced at equilibrium. The temperature increase, therefore, must be for kinetics reasons. As temperature increases, the reaction reaches equilibrium much faster. At low temperatures, this reaction is very slow, too slow to be of any use. b. As NH3(g) is removed, the reaction shifts right to produce more NH3(g). c. A catalyst has no effect on the equilibrium position. The purpose of a catalyst is to speed up a reaction so it reaches equilibrium more quickly. d. When the pressure of reactants and products is high, the reaction shifts to the side that has fewer gas molecules. Since the product side contains two molecules of gas as compared to four molecules of gas on the reactant side, then the reaction shifts right to products at high pressures of reactants and products. 95. PCl5(g)

94.

PCl3(g) + Cl2(g)

K=

[PCl 3 ][Cl 2 ] = 4.5 10 3 [PCl 5 ]

At equilibrium, [PCl5] = 2[PCl3].

CHAPTER 13

CHEMICAL EQUILIBRIUM
[PCl 3 ][Cl 2 ] , [Cl2] = 2(4.5 10 3 ) = 9.0 10 3 M 2[ PCl 3 ] CaO(s) + CO2(g) Kp = 1.16 = PCO 2

483

4.5 10 3 =

96.

CaCO3(s)

Some of the 20.0 g of CaCO3 will react to reach equilibrium. The amount that reacts is the quantity of CaCO3 required to produce a CO2 pressure of 1.16 atm (from the Kp expression). 1.16 atm 10.0 L = 0.132 mol CO2 0.08206 L atm RT 1073 K K mol 1 mol CaCO 3 100.09 g = 13.2 g CaCO3 Mass CaCO3 reacted = 0.132 mol CO2 mol CO 2 mol CaCO 3 13.2 g Mass % CaCO3 reacted = 100 = 66.0% 20.0 g n CO 2 = = PCO 2 V

Challenge Problems
97. P0 (for O2) = n O 2 RT / V = (6.400 g 0.08206 684 K)/(32.00 g/mol 2.50 L) = 4.49 atm CH4(g) + x 2 O2(g) CO2(g) + 2 H2O(g) 2x +x +2x

Change Change

CH4(g) + 3/2 O2(g) CO(g) + 2 H2O(g) 3/2 y +y +2y y

Amount of O2 reacted = 4.49 atm 0.326 atm = 4.16 atm O2 2x + 3/2 y = 4.16 atm O2 and 2x + 2y = 4.45 atm H2O Solving using simultaneous equations: 2x + 2y = 4.45 2x (3/2)y = 4.16 (0.50)y = 0.29, y = 0.58 atm = PCO 2x + 2(0.58) = 4.45, x =
4.45 1.16 = 1.65 atm = PCO 2 2

98.

4.72 g CH3OH

1 mol = 0.147 mol CH3OH initially 32.04 g Rate1 = Rate 2 M2 M1

Grahams law of effusion:

484
Rate H 2 Rate CH 3OH

CHAPTER 13

CHEMICAL EQUILIBRIUM

M CH 3OH M H2

32.04 = 3.987 2.016

The effused mixture has 33.0 times as much H2 as CH3OH. When the effusion rate ratio is multiplied by the equilibrium mole ratio of H2 to CH3OH, the effused mixture will have 33.0 times as much H2 as CH3OH. Let n H 2 and n CH 3OH equal the equilibrium moles of H2 and CH3OH, respectively. 33.0 = 3.987 n H2 n CH 3OH , n H2 n CH 3OH = 8.28

CH3OH(g) Initial Change Equil. 0.147 mol x 0.147 x

CO(g) 0 +x x n H2 =

+ 2 H2(g) 0 +2x 2x

From the ICE table, 8.28 = Solving: x = 0.118 mol

n CH 3OH

2x 0.147 x
2

0.118 mol 2(0.118 mol) 1.00 L 1.00 L 2 [CO][H 2 ] = K= (0.147 0.118) mol [CH 3OH] 1.00 L 99.

= 0.23

There is a little trick we can use to solve this problem in order to avoid solving a cubic equation. Because K for this reaction is very small (K << 1), the reaction will contain mostly reactants at equilibrium (the equilibrium position lies far to the left). We will let the products react to completion by the reverse reaction, and then we will solve the forward equilibrium problem to determine the equilibrium concentrations. Summarizing these steps in a table: 2 NOCl(g) Before Change After Change Equil.

2 NO(g) +

Cl2(g)

K = 1.6 105

1.0 M 0 2.0 M Let 1.0 mol/L Cl2 react completely. (K is small, reactants dominate.) +2.0 2.0 1.0 React completely 2.0 0 0 New initial conditions 2x mol/L of NOCl reacts to reach equilibrium +2x +x 2x 2x x 2.0 2x (2 x) 2 ( x) 4x3 ( 2.0 2 x) 2 2.0 2 (assuming 2.0 2x 2.0)

K = 1.6 105 =

x3 = 1.6 105, x = 2.5 102 M; assumption good by the 5% rule (2x is 2.5% of 2.0).

CHAPTER 13

CHEMICAL EQUILIBRIUM

485

[NOCl] = 2.0 0.050 = 1.95 M = 2.0 M; [NO] = 0.050 M; [Cl2] = 0.025 M

Note: If we do not break this problem into two parts (a stoichiometric part and an equilibrium part), then we are faced with solving a cubic equation. The setup would be:

2 NOCl Initial Change Equil. 1.6 105 = 0 +2y 2y

2 NO 2.0 M 2y 2.0 2y

Cl2 1.0 M y 1.0 y

(2.0 2 y ) 2 (1.0 y ) (2 y ) 2 2 .0 2 ; we get y = 250. This is impossible! 4y2

If we say that y is small to simplify the problem, then: 1.6 105 =

To solve this equation, we cannot make any simplifying assumptions; we have to find a way to solve a cubic equation. Or we can use some chemical common sense and solve the problem the easier way. 100. a. Initial Change Equil. 2 NO(g) + Br2(g)

2 NOBr(g)

98.4 torr 41.3 torr 0 2x torr of NO reacts to reach equilibrium x +2x 2x 41.3 x 2x 98.4 2x

Ptotal = PNO + PBr2 + PNOBr = (98.4 - 2x) + (41.3 x) + 2x = 139.7 x Ptotal = 110.5 = 139.7 x, x = 29.2 torr; PNO = 98.4 - 2(29.2) = 40.0 torr = 0.0526 atm PBr2 = 41.3 29.2 = 12.1 torr = 0.0159 atm; PNOBr = 2(29.2) = 58.4 torr = 0.0768 atm Kp = b. Initial Change Equil.
2 PNOBr (0.0768 atm) 2 = = 134 2 PNO PBr2 (0.0526 atm) 2 (0.0159 atm)

2 NO(g)

Br2(g)

2 NOBr(g)

0.30 atm 0.30 atm 0 2x atm of NO reacts to reach equilibrium 2x x +2x 0.30 x 2x 0.30 2x

This would yield a cubic equation, which can be difficult to solve unless you have a graphing calculator. Because Kp is pretty large, lets approach equilibrium in two steps: Assume the reaction goes to completion, and then solve the back-equilibrium problem.

486
2 NO Before Change After Change Equil. + Br2

CHAPTER 13

CHEMICAL EQUILIBRIUM

2 NOBr

0.30 atm 0.30 atm 0 Let 0.30 atm NO react completely. 0.30 0.15 +0.30 React completely 0 0.15 0.30 New initial 2y atm of NOBr reacts to reach equilibrium +y 2y +2y 0.15 + y 0.30 2y 2y (0.30 2 y ) 2 (0.30 2 y ) 2 = 134 4y2 = 536y2 , 2 (0.15 + y ) ( 2 y ) (0.15 + y ) (0.30) 2 536y2 and y = 0.034; assumptions are poor (y is 23% of 0.15). 0.15

K p = 134 =

If y << 0.15:

Use 0.034 as an approximation for y, and solve by successive approximations (see Appendix 1 in the text): (0.30 0.068) 2 = 536y2, y = 0.023; 0.15 + 0.034 (0.30 0.046) 2 = 536y2, y = 0.026 0.15 + 0.023

(0.30 0.052) 2 = 536y2, y = 0.026 atm (We have converged on the correct 0.15 + 0.026 answer.) So: PNO = 2y = 0.052 atm; PBr2 = 0.15 + y = 0.18 atm; PNOBr = 0.30 2y = 0.25 atm 101. Initial Change Equil. N2(g) + 3 H2(g)

2 NH3(g)

Kp = 5.3 105

0 0 P0 P0 = initial pressure of NH3 2x atm of NH3 reacts to reach equilibrium +3x 2x +x x 3x P0 2x P0 , so P0 = (4.00)x 2.00

From problem, P0 2x =

Kp =

[(4.00) x 2 x]2 [(2.00) x]2 (4.00) x 2 4.00 = = = = 5.3 105, x = 5.3 104 atm 3 3 4 2 ( x)(3x) ( x)(3x) 27 x 27 x

P0 = (4.00)x = 4.00(5.3 104 atm) = 2.1 103 atm 102. P4(g) 2 P2(g) Kp = 0.100 =
2 PP2

PP4

; PP4 + PP2 = Ptotal = 1.00 atm, PP4 = 1.00 atm PP2

CHAPTER 13

CHEMICAL EQUILIBRIUM
y2 = 0.100 1.00 y

487

Let y = PP2 at equilibrium, then Kp =

2 4

Solving: y = 0.270 atm = PP ; PP = 1.00 - 0.270 = 0.73 atm To solve for the fraction dissociated, we need the initial pressure of P4 (mol % pressure). P4(g) Initial Change Equil.

2 P2(g)

0 P0 = initial pressure of P4 in atm. P0 x atm of P4 reacts to reach equilibrium !x +2x 2x P0 ! x

Ptotal = P0 ! x + 2x = 1.00 atm = P0 + x Solving: 0.270 atm = PP2 = 2x, x = 0.135 atm; P0 = 1.00 ! 0.135 = 0.87 atm Fraction dissociated = N2O4(g) 2 NO2(g)
x 0.135 = = 0.16, or 16% of P4 is dissociated to reach equilibrium. P0 0.87

103.

Kp =

2 PNO 2

PN 2O 4

(1.20) 2 = 4.2 0.34

Doubling the volume decreases each partial pressure by a factor of 2 (P = nRT/V).

PNO 2 = 0.600 atm and PN 2O 4 = 0.17 atm are the new partial pressures.

Q=

(0.600) 2 = 2.1, so Q < K; equilibrium will shift to the right. 0.17 N2O4(g)

2 NO2(g)

Initial Change Equil. Kp = 4.2 =

0.17 atm 0.600 atm x atm of N2O4 reacts to reach equilibrium !x +2x 0.600 + 2x 0.17 ! x (0.600 + 2 x) 2 , 4x2 + (6.6)x ! 0.354 = 0 (carrying extra sig. figs.) (0.17 x)

Solving using the quadratic formula: x = 0.052 PNO 2 = 0.600 + 2(0.052) = 0.704 atm; PN 2O 4 = 0.17 ! 0.052 = 0.12 atm

488
104. a. Initial 2 NaHCO3(s)

CHAPTER 13

CHEMICAL EQUILIBRIUM
Kp = 0.25

Na2CO3(s)

+ CO2(g) + H2O(g)

0 0 Let some NaHCO3(s) decompose to form x atm each of CO2(g) and H2O(g) at equilibrium. Change +x +x Equil. x x Kp = 0.25 = PCO PH
2 2O

, 0.25 = x2, x = PCO 2 = PH 2O = 0.50 atm

b.

n CO 2 =

PCO 2 V RT

(0.50 atm) (1.00 L) = 1.5 10 2 mol CO2 (0.08206 L atm / K mol) (398 K )

Mass of Na2CO3 produced: 1.5 10 2 mol CO2 Mass of NaHCO3 reacted: 1.5 10 2 mol CO2 2 mol NaHCO3 84.01 g NaHCO3 = 2.5 g NaHCO3 1 mol CO 2 mol 1 mol Na 2 CO 3 105.99 g Na 2 CO 3 = 1.6 g Na2CO3 mol CO 2 mol Na 2 CO 3

Mass of NaHCO3 remaining = 10.0 ! 2.5 = 7.5 g c. 10.0 g NaHCO3 1 mol NaHCO3 1 mol CO 2 = 5.95 10 2 mol CO2 84.01 g NaHCO3 2 mol NaHCO3

When all of the NaHCO3 has just been consumed, we will have 5.95 10 2 mol CO2 gas at a pressure of 0.50 atm (from a). V= 105. Initial Change Equil. nRT (5.95 10 2 mol)(0.08206 L atm/K mol) (398 K ) = = 3.9 L P (0.50 atm) SO3(g) P0 x P0 x

SO2(g) + 1/2 O2(g) 0 +x x 0 +x/2 x/2 P0 = initial pressure of SO3

Average molar mass of the mixture is: average molar mass =

dRT (1.60 g / L) (0.08206 L atm / K mol ) (873 K ) = P 1.80 atm = 63.7 g/mol

CHAPTER 13

CHEMICAL EQUILIBRIUM

489

The average molar mass is determined by: average molar mass = n SO3 (80.07 g/mol) + n SO 2 (64.07 g/mol) + n O 2 (32.00 g/mol) n total

Because A = mol fraction of component A = nA/ntotal = PA/Ptotal: 63.7 g/mol = = PSO 3 (80.07) + PSO 2 (64.07) + PO 2 (32.00) Ptotal

Ptotal = P0 x + x + x/2 = P0 + x/2 = 1.80 atm, P0 = 1.80 - x/2 (P0 x) (80.07) + x (64.07) + 1.80
(1.80 3/2 x) (80.07) + x (64.07) + x (32.00) 2

63.7 =

x (32.00) 2

63.7 =

1.80

115 = 144 (120.1)x + (64.07)x + (16.00)x, (40.0)x = 29, x = 0.73 atm PSO 3 = P0 x = 1.80 (3/2)x = 0.71 atm; PSO 2 = 0.73 atm; PO 2 = x/2 = 0.37 atm Kp = 106.
1 PSO 2 PO/22

PSO3

(0.73) (0.37)1/ 2 = 0.63 (0.71)

The first reaction produces equal amounts of SO3 and SO2. Using the second reaction, calculate the SO3, SO2 and O2 partial pressures at equilibrium. SO3(g) Initial Change Equil. P0
!x P0 ! x

SO2(g) P0 +x P0 + x

1/2 O2(g) 0 +x/2 x/2 P0 = initial pressure of SO3 and SO2 after first reaction occurs.

Ptotal = P0 ! x + P0 + x + x/2 = 2P0 + x/2 = 0.836 atm PO 2 = x/2 = 0.0275 atm, x = 0.0550 atm 2P0 + x/2 = 0.836 atm; 2P0 = 0.836 ! 0.0275 = 0.809 atm, P0 = 0.405 atm PSO 3 = P0 ! x = 0.405 ! 0.0550 = 0.350 atm; PSO 2 = P0 + x = 0.405 + 0.0550 = 0.460 atm For the reaction 2 FeSO4(s) Fe2O3(s) + SO3(g) + SO2(g):

490

CHAPTER 13
Kp = PSO 2 PSO3 = (0.460)(0.350) = 0.161 For the reaction SO3(g) SO2(g) + 1/2 O2(g): Kp =
1 PSO PO/22
2

CHEMICAL EQUILIBRIUM

PSO O2(g)

(0.460) (0.0275)1 / 2 = 0.218 0.350 Assume exactly 100 O2 molecules.

107.

2 O(g) 0 +166 166

Initial 100 Change !83 Equil. 17 Thus: O =

166 = 0.9071 and O 2 = 0.0929 183

PO 2 = O 2 Ptotal ; and PO = OPtotal Because initially Ptotal = 1.000 atm, PO 2 = 0.0929 atm and PO = 0.9071 atm. Kp =
2 PO (0.9071) 2 = = 8.86 atm 0.0929 PO 2

O2 Initial Change Equil.

2O 0 +2y 2y

x !y x!y

(2 y ) 2 y 100 = 95.0; we have two equations and two unknowns. = 8.86; x x y Solving: x = 0.123 atm and y = 0.117 atm; Ptotal = (x y) + 2y = 0.240 atm 108. a. N2O4(g) Initial x Change !(0.16)x Equil. (0.84)x

2 NO2(g) 0 +(0.32)x (0.32)x (0.42) 2 = 0.16 atm 1.1

(0.84)x + (0.32)x = 1.5 atm, x = 1.3 atm; Kp = b. N2O4 Equil. x

2 NO2 ; x + y = 1.0 atm;

y

y2 = 0.16 x

Solving: x = 0.67 atm (= PN 2O 4 ) and y = 0.33 atm (= PNO 2 )

CHAPTER 13
c.

CHEMICAL EQUILIBRIUM
N2O4

491

2 NO2 0 +2x 0.33 atm P0 = initial pressure of N2O4

Initial Change Equil.

P0 !x 0.67 atm

2x = 0.33, x = 0.165 (using extra sig. figs.) P0 ! x = 0.67, P0 = 0.67 + 0.165 = 0.84 atm; 109. 0.165 100 = 20.% dissociated 0.84

a. Because density (mass/volume) decreases while the mass remains constant (mass is conserved in a chemical reaction), volume must increase. The volume increases because the number of moles of gas increases (V n at constant T and P). V n Density (initial) 4.495 g/L = = 1.100 = equil. = equil. Density (equil.) 4.086 g/L Vinitial n initial Assuming an initial volume of 1.000 L: 4.495 g NOBr
1 mol NOBr = 0.04090 mol NOBr initially 109.91 g

2 NOBr(g) Initial Change Equil. n equil. n initial 0.04090 mol 2x 0.04090 2x

2 NO(g) + Br2(g) 0 +2x 2x 0 +x x

0.04090 2 x + 2 x + x = 1.100; solving: x = 0.00409 mol 0.04090

If the initial volume is 1.000 L, then the equilibrium volume will be 1.110(1.000 L) = 1.110 L. Solving for the equilibrium concentrations: [NOBr] = [Br2] = K= 0.03272 mol 0.00818 mol = 0.02975 M ; [NO] = = 0.00744 M 1.100 L 1.100 L

0.00409 mol = 0.00372 M 1.100 L

(0.00744) 2 (0.00372) = 2.33 104 (0.02975) 2

b. The argon gas will increase the volume of the container. This is because the container is a constant-pressure system, and if the number of moles increases at constant T and P, the volume must increase. An increase in volume will dilute the concentrations of all gaseous reactants and gaseous products. Because there are more moles of product gases

492

CHAPTER 13

CHEMICAL EQUILIBRIUM

versus reactant gases (3 mol versus 2 mol), the dilution will decrease the numerator of K more than the denominator will decrease. This causes Q < K and the reaction shifts right to get back to equilibrium. Because temperature was unchanged, the value of K will not change. K is a constant as long as temperature is constant. 110. Initial Change Equil. CCl4(g) P0 x P0- x

C(s) +

2 Cl2(g) Kp = 0.76 0 +2x 2x P0 = initial pressure of CCl4

Ptotal = P0 x + 2x = P0 + x = 1.20 atm Kp = (2 x) 2 4 x 2 + (0.76) x = 0.76, 4x2 = (0.76)P0 (0.76)x, P0 = P0 x 0.76

Substituting into P0 + x = 1.20: 4x2 + x + x = 1.20 atm, (5.3)x2 + 2x 1.20 = 0; solving using the quadratic formula: 0.76
x = 2 (4 + 25.4)1/ 2 = 0.32 atm; P0 + 0.32 = 1.20, P0 = 0.88 atm 2(5.3)

Integrative Problems
111. Initial NH3(g) + H2S(g)

NH4HS(s)

K = 400. =

1 [ NH 3 ][H 2S]

2.00 mol 2.00 mol 5.00 L 5.00 L x mol/L of NH3 reacts to reach equilibrium Change !x !x Equil. 0.400 ! x 0.400 ! x

1 1 , 0.400 ! x = K = 400. = (0.400 x)(0.400 x) 400. Mol NH4HS(s) produced = 5.00 L

1/ 2

= 0.0500, x = 0.350 M

0.350 mol NH 3 1 mol NH 4 HS = 1.75 mol L mol NH 3

Total mol NH4HS(s) = 2.00 mol initially + 1.75 mol produced = 3.75 mol total

CHAPTER 13

CHEMICAL EQUILIBRIUM
51.12 g NH 4 HS = 192 g NH4HS mol NH 4 HS

493

3.75 mol NH4HS

[H2S]e = 0.400 M x = 0.400 M 0.350 M = 0.050 M H2S PH 2S = 112. n H 2S RT V

n H 2S V

RT =

0.050 mol 0.08206 L atm 308.2 K = 1.3 atm L K mol

See the hint for Exercise 81. 2 C(g) 2 A(g) + 2 B(g) 2 A(g) + D(g) C(g) C(g) + D(g) 2 B(g) K1 = (1/3.50)2 = 8.16 10 2 K2 = 7.10

______________________________________________________________________________________________

K = K1 K2 = 0.579

Kp = K(RT)n, n = 2 (1 + 1) = 0; because n = 0, Kp = K = 0.579. C(g) Initial 1.50 atm Equil. 1.50 x 0.579 = K = + D(g) 1.50 atm 1.50 x

2 B(g) 0 2x

(2 x) 2 (2 x) 2 = (1.50 x)(1.50 x) (1.50 x) 2

2x = (0.579)1/2 = 0.761, x = 0.413 atm 1.50 x PB (at equilibrium) = 2x = 2(0.413) = 0.826 atm Ptotal = PC + PD + PB = 2(1.50 0.413) + 0.826 = 3.00 atm PB = BPtotal, B = PB 0.826 atm = = 0.275 Ptotal 3.00 atm

113.

Initial moles VCl4 = 6.6834 g VCl4 1 mol VCl4/192.74 g VCl4 = 3.4676 102 mol VCl4 Total molality of solute particles = im =
5.97 o C T = 0.200 mol/kg = Kf 29.8 o C kg/mol

Because we have 0.1000 kg CCl4, the total moles of solute particles present is: 0.200 mol/kg(0.1000 kg) = 0.0200 mol

494
2VCl4 Initial Equil.

CHAPTER 13

CHEMICAL EQUILIBRIUM
[V2 Cl8 ] [VCl 4 ]2

V2Cl8

K=

3.4676 102 mol 0 2x mol VCl4 reacts to reach equilibrium x 3.4676 102 2x

Total moles solute particles = 0.0200 mol = mol VCl4 + mol V2Cl8 = 3.4676 102 2x + x 0.0200 = 3.4676 102 x, x = 0.0147 mol At equilibrium, we have 0.0147 mol V2Cl8 and 0.0200 - 0.0147 = 0.0053 mol VCl4. To determine the equilibrium constant, we need the total volume of solution in order to calculate equilibrium concentrations. The total mass of solution is 100.0 g + 6.6834 g = 106.7 g. Total volume = 106.7 g 1 cm3/1.696 g = 62.91 cm3 = 0.06291 L The equilibrium concentrations are: [V2Cl8] =
0.0147 mol 0.0053 mol = 0.234 mol/L; [VCl4] = = 0.084 mol/L 0.06291 L 0.06291 L

K =

[V2 Cl8 ] 0.234 = = 33 2 [VCl 4 ] (0.084) 2

Marathon Problem
114. Concentration units involve both moles and volume, and since both quantities are changing at the same time, we have a complicated system. Lets simplify the setup of the problem initially by only worrying about the changes that occur to the moles of each gas. A(g) Initial Change Equil. + B(g)

C(g)

K = 130.

0 0 0.406 mol Let x mol of C(g) react to reach equilibrium +x x +x x x 0.406 x

Let Veq = the equilibrium volume of the container, so: [A]eq = [B]eq =
x 0.406 x ; [C]eq = Veq Veq

0.046 x Veq (0.406 x) Veq [ C] = = K = x x [A ][B] x2 Veq Veq

CHAPTER 13

CHEMICAL EQUILIBRIUM

495

From the ideal gas equation, V = nRT/P. To calculate the equilibrium volume from the ideal gas law, we need the total moles of gas present at equilibrium. At equilibrium: ntotal = mol A(g) + mol B(g) + mol C(g) = x + x + 0.406 - x = 0.406 + x Therefore: Veq = n total RT (0.406 + x)(0.08206 L atm / K mol)(300.0 K ) = P 1.00 atm

Veq = (0.406 + x)24.6 L/mol Substituting into the equilibrium expression for Veq: K = 130. = (0.406 x)(0.406 + x)24.6 x2

Solving for x (we will carry one extra significant figure): (130.)x2 = (0.1648 x2)24.6, (154.6)x2 = 4.054, x = 0.162 mol Solving for the volume of the container at equilibrium: Veq = (0.406 + 0.162 mol)(0.08206)(300.0 K ) = 14.0 L 1.00 atm