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Chapter 7

Solutions for Practice Problems

Student Textbook page 336 Write the equilibrium expression for each homogeneous reaction. 1. Problem The reaction between ethanol and ethanoic acid to form ethyl ethanoate and water: CH3CH2OH( ) + CH3COOH( ) CH3CHOOCH2CH3( ) + H2O( ) What Is Required? You need to nd an expression for Kc . What Is Given? You know the balanced chemical equation. Plan Your Strategy Kc is a fraction with product concentrations in the numerator and concentrations of reactants in the denominator. Each concentration term must be raised to the power of the coefcient in the balanced equation. Act on Your Strategy [CH3COOCH2CH3][H2O] Kc = [CH3CH2OH][CH3COOH] Check Your Solution Each chemical formula is enclosed in square brackets, indicating concentration. The products are in the numerator, and the reactants in the denominator. There are no coefcients in the balanced equation, and therefore no power terms in the equilibrium expression (other than the value 1).

2. Problem

The reaction between nitrogen gas and oxygen gas at high temperatures: N2(g) + O2(g) 2NO(g) What Is Required? You need to nd an expression for Kc . What Is Given? You know the balanced chemical equation. Plan Your Strategy Kc is a fraction with product concentrations in the numerator and concentrations of reactants in the denominator. Each concentration term must be raised to the power of the coefcient in the balanced equation. Act on Your Strategy 2 Kc = [NO] [N2][O2]

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Check Your Solution The products are in the numerator, and the reactants in the denominator. Each chemical formula is enclosed in square brackets, and the concentration of NO is raised to the power of the coefcient in the chemical equation.

3. Problem

The reaction between hydrogen gas and oxygen gas to form water vapour: 2H2O(g) 2H2(g) + O2(g) What Is Required? You need to nd an expression for Kc . What Is Given? You know the balanced chemical equation. Plan Your Strategy The expression for Kc is a fraction. The concentration of product is in the numerator, and the concentrations of the reactants are in the denominator. Each concentration term must be raised to the power of the coefcient in the balanced equation. Act on Your Strategy 2 Kc = [H22O] [H2] [O2] Check Your Solution The products are in the numerator, and the reactants in the denominator. Each chemical formula is enclosed in square brackets, and the concentrations of H2O and H2 are raised to the power of the coefcient in the chemical equation.

4. Problem

The reduction-oxidation equilibrium of iron and iodine ions in aqueous solution: 2Fe2+(aq) + I2(aq) 2Fe3+(aq) + 2I(aq) Note: You will learn about reduction-oxidation reactions in the next unit. What Is Required? You need to nd an expression for Kc . What Is Given? You know the balanced chemical equation. Plan Your Strategy The expression for Kc is a fraction. The concentrations of the products are in the numerator, and the concentrations of the reactants are in the denominator. Each concentration term must be raised to the power of the coefcient in the balanced equation. Act on Your Strategy 2+ 2 Kc = [Fe3+ ]2 [I2]2 [Fe ] [I ] Check Your Solution The products are in the numerator, and the reactants in the denominator. Each chemical formula is enclosed in square brackets, and the concentrations of Fe3+ , I, and Fe2+ are raised to the power of their respective coefcient in the chemical equation.

5. Problem

The oxidation of ammonia (one of the reactions in the production of nitric acid): 4NO(g) + 6H2O(g) 4NH3(g) + 5O2(g)

Chapter 7 Reversible Reactions and Chemical Equilibrium MHR

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What Is Required? You need to nd an expression for Kc . What Is Given? You know the balanced chemical equation. Plan Your Strategy The expression for Kc is a fraction. The concentrations of products are in the numerator, and the concentrations of the reactants are in the denominator. Each concentration term must be raised to the power of the coefcient in the balanced equation. Act on Your Strategy 4 6 Kc = [NO] [H2O] 4 5 [NH3] [O2] Check Your Solution The products are in the numerator, and the reactants in the denominator. Each chemical formula is enclosed in square brackets, and the concentration of each chemical is raised to the power of its coefcient in the chemical equation.

Student Textbook page 338

6. Problem

The following reaction took place in a sealed ask at 250C. PCl3(g) + Cl2(g) PCl5(g) At equilibrium, the gases in the ask had the following concentrations: [PCl5] = 1.2 102 mol/L, [PCl3] = 1.5 102 mol/L , and [Cl2] = 1.5 102 mol/L. Calculate the value of Kc at 250C. What Is Required? You need to calculate the value of Kc . What Is Given? You have the chemical equation and the concentration of each substance at equilibrium. Plan Your Strategy Write the equilibrium expression. Then substitute the equilibrium molar concentrations into the expression. Act on Your Strategy The equilibrium expression is [PCl3][Cl2] Kc = [PCl5] Substitute the equilibrium molar concentrations into the expression. 2 2 Kc = (1.5 10 ) (1.5 10 ) 2 (1.2 10 ) Kc = 1.9 102 Check Your Solution The equilibrium expression has the product terms in the numerator and the reactant terms in the denominator. The exponents in the equilibrium expression match the corresponding coefcients in the chemical equation. The molar concentrations at equilibrium were substituted into the expression.

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7. Problem

Iodine and bromine react to form iodine monobromide, IBr. 2IBr(g) I2(g) + Br2(g) At 250C, an equilibrium mixture in a 2.0 L ask contained 0.024 mol of I2(g) , 0.050 mol of Br2(g), and 0.38 mol of IBr(g) . What is the value of Kc for the reaction at 250C? What Is Required? You need to calculate the value of Kc . What Is Given? You have the chemical equation, the amount of each substance at equilibrium, and the volume of the ask. Plan Your Strategy Step 1 Calculate the molar concentration of each compound at equilibrium. Step 2 Write the equilibrium expression. Then substitute the equilibrium molar concentrations into the expression. Act on Your Strategy The reaction takes place in a 2.0 L ask. Calculate the molar concentrations at equilibrium. [I2] = 0.024 mol = 0.012 mol/L 2.0 L 0.050 mol = 0.025 mol/L [Br2] = 2.0 L 0.38 mol = 0.19 mol/L [IBr] = 2.0 L Step 2 Write the equilibrium expression. Substitute the equilibrium molar concentrations into the expression. 2 Kc = [IBr] [I2][Br2] (0.19)2 = (0.012)(0.025) = 1.2 102

Step 1

Check Your Solution The equilibrium expression has the product terms in the numerator and the reactant terms in the denominator. The exponents in the equilibrium expression match the corresponding coefcients in the chemical equation. The molar concentrations at equilibrium were substituted into the expression. The answer has the correct number of signicant digits.

8. Problem

At high temperatures, carbon dioxide gas decomposes into carbon monoxide and oxygen gas. At equilibrium, the gases have the following concentrations: [CO2(g)] = 1.2 mol/L, [CO(g)] = 0.35 mol/L, and [O2(g)] = 0.15 mol/L. Determine Kc at the temperature of the reaction. What Is Required? You need to calculate the value of Kc . What Is Given? You know the reactant and products, and the concentration of each substance at equilibrium.

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Plan Your Strategy Step 1 Write the chemical equation. Step 2 Write the equilibrium expression. Then substitute the equilibrium molar concentrations into the expression for Kc .

Step 1

2 Kc = [CO] [O2] [CO2]2 2 = (0.35) (0.15) (1.2)2 = 0.013

Step 2

Check Your Solution The chemical equation is balanced. The equilibrium expression has the product terms in the numerator and the reactant terms in the denominator. The exponents in the equilibrium expression match the corresponding coefcients in the chemical equation. The molar concentrations at equilibrium were substituted into the expression. The answer has the correct number of signicant digits.

9. Problem

Hydrogen sulde is a pungent, poisonous gas. At 1400 K, an equilibrium mixture was found to contain 0.013 mol/L hydrogen, 0.046 mol/L sulfur in the form of S2(g) , and 0.18 mol/L hydrogen sulde. Calculate the equilibrium constant, at 1400 K, for the following reaction. 2H2S(g) 2H2(g) + S2(g) What Is Required? You need to calculate the value of Kc . What Is Given? You have the chemical equation and the amount of each substance at equilibrium. Plan Your Strategy Write the equilibrium expression. Then substitute the equilibrium molar concentrations into the expression. Act on Your Strategy 2 Kc = [H2] [S2] [H2S]2 2 = (0.013) (0.046) (0.18)2 = 2.4 104 Check Your Solution The equilibrium expression has the product terms in the numerator and the reactant terms in the denominator. The exponents in the equilibrium expression match the corresponding coefcients in the chemical equation. The molar concentrations at equilibrium were substituted into the expression.

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10. Problem

Methane, ethyne, and hydrogen form the following equilibrium mixture. C2H2(g) + 3H2(g) 2CH4(g) While studying this reaction mixture, a chemist analysed a 4.0 L sealed ask at 1700C. The chemist found 0.46 mol of CH4(g) , 0.64 mol of C2H2(g), and 0.92 mol of H2(g) . What is the value of Kc for the reaction at 1700C? What Is Required? You need to calculate the value of Kc . What Is Given? You have the chemical equation and the amount of each substance at equilibrium in a 4.0 L ask. Plan Your Strategy Step 1 Calculate the molar concentration of each compound at equilibrium. Step 2 Write the equilibrium expression. Then substitute the equilibrium molar concentrations into the expression. Act on Your Strategy The reaction takes place in a 4.0 L ask. Calculate the molar concentrations at equilibrium. [CH4] = 0.46 mol = 0.115 mol/L 4.0 L 0.64 mol = 0.16 mol/L [C2H2] = 4.0 L 0.92 mol = 0.23 mol/L [H2] = 4.0 L Step 2 Write the equilibrium expression. Substitute the equilibrium molar concentrations into the expression. 3 Kc = [C2H2][H2] 2 [CH4] 3 = (0.16)(0.23) 2 (0.115) = 0.15 Check Your Solution The equilibrium expression has the product terms in the numerator and the reactant terms in the denominator. The exponents in the equilibrium expression match the corresponding coefcients in the chemical equation. The molar concentrations at equilibrium were substituted into the expression. The answer has the correct number of signicant digits.

Step 1

Student Textbook pages 347348

11. Problem

At 25C the value of Kc for the following reaction is 82. I2(g) + Cl2(g) 2ICl(g) 0.83 mol of I2(g) and 0.83 mol of Cl2(g) are placed in a 10 L container at 25C. What are the concentrations of the three gases at equilibrium? What Is Required? You need to nd [I2 ], [Cl2] and [ICl] at equilibrium. What Is Given? You are given the chemical equation. You know the initial amount of each gas, the volume of the container, and the equilibrium constant.

Chapter 7 Reversible Reactions and Chemical Equilibrium MHR

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Plan Your Strategy Step 1 Calculate the initial concentrations. Step 2 Set up an ICE table. Insert the initial concentrations you calculated in Step 1 in your ICE table. Let the change in molar concentrations of the reactants be x. Use the stoichiometry of the chemical equation to write and record expressions for the equilibrium concentrations. Step 3 Write the equilibrium expression. Substitute the expressions for the equilibrium concentrations into the expression. Solve the equilibrium expression for x. Step 4 Calculate the equilibrium concentration of each gas. Act on Your Strategy The initial amount of I2 is equal to the initial amount of Cl2. [I2] = [Cl2] = 0.83 mol = 0.083 mol/L 10 L Step 2 Set up an ICE table.

Step 1 Concentration (mol/L) Initial Change Equilibrium

2 Kc = [ICI] [I2][Cl2]

2ICl(g) 0 +2x 2x

Step 3

(2x)2 (0.083 x)(0.083 x) (2x)2 = (0.083 x)2 The right side of the equation is a perfect square. (2x) 9.06 = (0.083 x) Solving for both values, x = 0.068 and x = 0.11 Step 4 The value x = 0.11 is physically impossible because it is a larger concentration than was initially placed in the container. To achieve equilibrium, the initial [I2 ] and [Cl2] must decrease. [I2] = [Cl2] = 0.083 0.068 = 0.015 mol/L [ICl] = 2 0.068 = 0.14 mol/L 82 = Check Your Solution The equilibrium expression has product concentrations in the numerator and reactant concentrations in the denominator. Check Kc : 2 Kc = (0.14) 2 = 87 (0.015) This is close to the given value, Kc = 82. The difference is due to mathematical rounding.

12. Problem

At a certain temperature, Kc = 4.0 for the following reaction. 2HF(g) H2(g) + F2(g) A 1.0 L reaction vessel contained 0.045 mol of F2(g) at equilibrium. What was the initial amount of HF in the reaction vessel?

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What Is Required? You need to nd the initial amount of HF(g) placed in the reaction vessel. What Is Given? You are given the chemical equation. You know the amount of F2(g) at equilibrium, the volume of the container, and the equilibrium constant. Plan Your Strategy Step 1 Calculate the concentration of F2(g) at equilibrium and use the chemical equation to nd the equilibrium concentration of H2(g) . Step 2 Set up an ICE table. Insert the equilibrium concentrations you calculated in Step 1 in your ICE table. Let the change in molar concentrations of the reactants be x. Use the stoichiometry of the chemical equation to write and record expressions for the equilibrium concentrations. Step 3 Write the equilibrium expression. Substitute the expressions for the equilibrium concentrations into the expression. Solve the equilibrium expression for the initial [HF]. Step 4 Calculate the initial amount of HF(g) . Act on Your Strategy Step 1 The volume of the reaction vessel is 1.0 L. Therefore, [F2] = 0.045 mol = 0.045 mol/L 1.0 L [H2] = [F2] = 0.045 mol/L Step 2 Set up an ICE table.

Concentration (mol/L) Initial Change Equilibrium 2HF(g) [HF] 2x ([HF] 2x) H2(g) 0 +x 0.045 + F2(g) 0 +x 0.045

Therefore, x = 0.045 Kc = [H2][F22] Step 3 [HF] (0.045)(0.045) 4.0 = ([HF] 0.090)2 (0.045)2 = ([HF] 0.090)2 The right side of the equation is a perfect square. (0.045) 2.0 = ([HF] 0.090) Solving for both values gives [HF] = 0.112 and [HF] = 0.0675 Step 4 The value [HF] = 0.0675 is physically impossible because subtracting the change in concentration, 0.090, results in a negative value for the initial concentration of HF(g) placed in the container. Therefore, [HF] = 0.11 mol/L. Because the volume of the reaction vessel is 1.0 L, the initial amount of HF(g) placed in the reaction vessel was 0.11 mol.

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Check Your Solution The equilibrium expression has product concentrations in the numerator and reactant concentrations in the denominator. Check Kc : (0.045)2 Kc = = 5.1 (0.11 0.090)2 This is close to the given value, Kc = 4.0. The difference is due to mathematical rounding.

13. Problem

A chemist was studying the following reaction. NO(g) + SO3(g) SO2(g) + NO2(g) In a 1.0 L container, the chemist added 1.7 101 mol of SO2(g) to 1.1 101 mol of NO2(g). The value of Kc for the reaction at a certain temperature is 4.8. What is the equilibrium concentration of SO3(g) at this temperature? What Is Required? You need to nd the equilibrium [SO3]. What Is Given? You are given the chemical equation. You know the equilibrium constant for the reaction, Kc = 4.8. You also know the initial amounts of SO2(g) and NO2(g), and the volume of the container. Plan Your Strategy Calculate the initial concentrations of SO2(g) and NO2(g). Set up an ICE table. Insert the equilibrium concentrations you calculated in Step 1 in your ICE table. Let the change in molar concentrations of the reactants be x. Use the stoichiometry of the chemical equation to write and record expressions for the equilibrium concentrations. Step 3 Write the equilibrium expression. Substitute the expressions for the equilibrium concentrations into the expression. Rearrange the equilibrium expression into the form of a quadratic equation for x. Solve the quadratic equation for x. Step 4 Substitute x into the equilibrium line of the ICE table to nd the equilibrium concentration of [SO3].

Step 1 Step 2

Act on Your Strategy The volume of the reaction vessel is 1.0 L. Therefore, 1 [SO2] = 1.7 10 mol = 1.7 101 mol/L 1.0 L 1.1 101 mol = 1.1 101 mol/L [NO2] = 1.0 L Step 2 Set up an ICE table.

Step 1 Concentration (mol/L) Initial Change Equilibrium SO2(g) 1.7 101 x + NO2(g) 1.1 101 x NO(g) + SO3(g) 0 +x x 0 +x x

Step 3

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This equation must be rearranged into a quadratic equation. 3.8x 2 1.344x + 0.08976 = 0 Recall that a quadratic equation of the form ax 2 + bx + c = 0 has the following solution. 2 x = b b 4ac 2a Therefore, x = (1.344) 1.806 1.364 7.6 1.344 0.6648 = 7.6 x = 0.089 and x = 0.264 The value x = 0.264 is not physically possible. It would result in negative concentration of SO2 and NO2 at equilibrium. The concentration of each substance at equilibrium is found by substituting x = 0.089 into the last line of the ICE table.

Concentration (mol/L) Equilibrium SO2(g) + NO2(g) NO(g) + SO3(g) 0.089 0.089 (0.17 0.089) (0.11 0.089)

Applying the rules for subtraction involving measured values: [SO2] = 0.08 mol/L [NO2] = 0.02 mol/L [NO] = 0.089 mol/L [SO3] = 0.089 mol/L At equilibrium the concentration of SO3(g) is 0.089 mol/L. Check Your Solution The equilibrium expression has product concentrations in the numerator and reactant concentrations in the denominator. Check Kc : 2 =5 Kc = (0.089) (0.08)(0.02) Solving the quadratic equation gave a value of x known only to two decimal places. Subtracting the value of x from [SO2] and [NO2] gave values only good to one signicant gure. The calculated value of Kc is equal to the given value, 4.8, within the error introduced by rounding.

14. Problem

Phosgene, COCl2(g) , is an extremely toxic gas. It was used during World War I. Today, it is used to manufacture pesticides, pharmaceuticals, dyes, and polymers. It is prepared by mixing carbon monoxide and chlorine gas. CO(g) + Cl2(g) COCl2(g) 0.055 mol of CO(g) and 0.072 mol of Cl2(g) are placed in a 5.0 L container. At 870 K, the equilibrium constant is 0.20. What are the equilibrium concentrations of the mixture at 870 K? What Is Required? You need to nd the equilibrium concentrations of CO, Cl2 and COCl. What Is Given? You are given the chemical equation. You know the equilibrium constant for the reaction, Kc = 0.20. You also know the initial amounts of CO(g) and Cl2(g) , and the volume of the container.

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Plan Your Strategy Step 1 Calculate the initial concentrations of CO(g) and Cl2(g) . Step 2 Set up an ICE table. Insert the equilibrium concentrations you calculated in Step 1 in your ICE table. Let the change in molar concentrations of the reactants be x. Use the stoichiometry of the chemical equation to write and record expressions for the equilibrium concentrations. Step 3 Write the equilibrium expression. Substitute the expressions for the equilibrium concentrations into the expression. Rearrange the equilibrium expression into the form of a quadratic equation for x. Solve the quadratic equation for x. Step 4 Substitute x into the equilibrium line of the ICE table to nd the equilibrium concentrations of CO, Cl2, and COCl. Act on Your Strategy The volume of the reaction vessel is 5.0 L. Therefore, [CO] = 0.055 mol = 0.011 mol/L 5.0 L [Cl2] = 0.072 mol = 0.0144 mol/L 5.0 L Step 2 Set up an ICE table.

Step 1 Concentration (mol/L) Initial Change Equilibrium Step 3 CO(g) 0.011 x (0.011 x) + Cl2(g) 0.0144 x (0.0144 x) COCl2(g) 0 +x x

Kc = [COCl2] [CO][Cl2] x 0.20 = (0.011 x)(0.0144 x) This equation must be rearranged into a quadratic equation x 2 5.025x + 1.58 104 = 0 Recall that a quadratic equation of the form ax 2 + bx + c = 0 has the following solution. b b 2 4ac x = 2a Therefore, 4 x = (5.025) 25.25 6.32 10 2.0 5.025 5.025 = 2.0 x = 5.02 or x = 0.0 The value x = 5.02 is not physically possible. It would result in negative concentration of CO and Cl2 at equilibrium. The concentration of reactants remains essentially unchanged with very little formation of COCl2(g) .

Check Your Solution Calculate the equilibrium [COCl2] to check that it is a very small value. [COCl2] Kc = 0.20 = 0.011 0.014 [COCl2] = 3.1 105 mol/L The equilibrium concentration of [COCl2] is a very small value.

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15. Problem

Hydrogen bromide decomposes at 700 K. Kc = 4.2 109 H2(g) + Br2(g) 2HBr(g) 0.090 mol of HBr is placed in a 2.0 L reaction vessel and heated to 700 K. What is the equilibrium concentration of each gas? What Is Required? You need to nd [HBr], [H2], and [Br2] at equilibrium. What Is Given? You are given the chemical equation. You know the initial amount of HBr, the volume of the container, and the equilibrium constant. Plan Your Strategy Step 1 Calculate the initial concentration of HBr. Step 2 Set up an ICE table. Insert the initial concentrations you calculated in Step 1 in your ICE table. Let the change in molar concentrations of HBr be x. Use the stoichiometry of the chemical equation to write and record expressions for the equilibrium concentrations. Step 3 Write the equilibrium expression. Substitute the expressions for the equilibrium concentrations into the expression. Solve the equilibrium expression for x. Step 4 Calculate the equilibrium concentration of each gas. Act on Your Strategy

Step 1

[HBr] = 0.090 mol = 0.045 mol/L 2.0 L Step 2 Set up an ICE table.

Concentration (mol/L) Initial Change Equilibrium Step 3 2HBr(g) 0.045 2x 0.045 2x H2(g) 0 +x x + Br2(g) 0 +x x

Kc = [H2][Br22] [HBr] x2 4.2 109 = (0.045 2x)2 The right side of the equation is a perfect square. x 6.48 105 = 0.045 2x

Solving for both values, x = +2.92 106 and x = 2.92 106 Step 4 The value x = 2.92 106 is physically impossible because it would result in negative concentration of both H2 and Br2 . Therefore, [H2] = [Br2] = 2.9 106 mol/L . [HBr] = 0.045 (2 2.9 106) = 0.045 mol/L Check Your Solution The equilibrium expression has product concentrations in the numerator and reactant concentrations in the denominator. The equilibrium concentrations are in mol/L. Check Kc : 2 Kc = (2.9) 2 = 4.2 109 (0.045) This is equal to the given value of Kc .

Chapter 7 Reversible Reactions and Chemical Equilibrium MHR

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Student Textbook pages 349350

16. Problem

2HI(g) , the value of Kc is 25.0 at 1100 K and For the reaction H2(g) + I2(g) 8.0 102 at room temperature, 300 K. Which temperature favours the dissociation of HI(g) into its component gases? What Is Required? Choose the temperature that favours the greater dissociation of HI. What Is Given? Kc = 25.0 at 1100 K and 8.0 102 at 300 K

Plan Your Strategy HI is on the right in the chemical equation. A greater dissociation of hydrogen iodide corresponds to a smaller value of Kc . Act on Your Strategy The value of Kc is smaller at 1100 K. The position of equilibrium lies more to the left and favours the dissociation of hydrogen iodide at the higher temperature. Check Your Solution The question asked to choose the conditions for a smaller concentration of a product. Kc is a fraction with product terms in the numerator, so the smallest value of Kc must correspond to the smallest concentration of product.

17. Problem

Three reactions, and their equilibrium constants, are given below. Kc = 4.7 1031 2NO(g) I. N2(g) + O2(g) Kc = 1.8 106 2NO2(g) II. 2NO(g) + O2(g) Kc = 0.025 2NO2(g) III. N2O4(g) Arrange these equations in the order of their tendency to form products. What Is Required? Place the reactions in the order of their tendency to form products. What Is Given? Kc is given for each reaction. Plan Your Strategy The equilibrium constant, Kc , is a ratio of product concentrations divided by reactant concentrations. The larger the value of Kc , the greater the tendency to form products. Act on Your Strategy The largest value of Kc is 0.025, then 1.8 106 , and nally, 4.7 1031. From greatest to least tendency to form products, the order is III, II, I. Check Your Solution The question asked about the tendency to form products. Kc is a ratio of product concentrations divided by reactant concentrations. The largest value of Kc corresponds to the greatest tendency to form products.

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18. Problem

2NCl3(g) (a) N2(g) + 3Cl2(g) C2H6(g) + H2(g) (b) 2CH4(g) N2(g) + 2CO2(g) (c) 2NO(g) + 2CO(g)

Identify each reaction as essentially going to completion or not taking place. Kc = 3.0 1011 Kc = 9.5 1013 Kc = 2.2 1059 What Is Required? For each reaction, determine whether the equilibrium mixture consists mostly of products or reactants. What Is Given? Kc is given for each reaction.

Plan Your Strategy The equilibrium constant, Kc , is a ratio of product concentrations divided by reactant concentrations. A large value of Kc corresponds to mostly products, and a small value of Kc indicates mostly reactants. Act on Your Strategy Reaction (a): Kc = 3.0 1011 . At equilibrium, mostly products are present and the reaction essentially goes to completion. Reaction (b): Kc = 9.5 1013 . At equilibrium, mostly reactants are present and there is essentially no reaction. Reaction (c): Kc = 2.2 1059 . At equilibrium, mostly products are present and the reaction goes to completion. Check Your Solution Kc is a ratio of product concentrations divided by reactant concentrations. Reactions that go to completion have very large values for Kc . Reactions that do not take place have very small values for Kc .

19. Problem

Most metal ions combine with other ions in solution. For example, in aqueous ammonia, silver(I) ions are in equilibrium with different complex ions. [Ag(NH3)2]+(aq) + 2H2O( ) [Ag(H2O)2]+(aq) + 2NH3(aq) At room temperature, Kc for this reaction is 1 107. Which of the two silver complex ions is the more stable? Explain your reasoning. What Is Required? Decide which silver ion is more stable. What Is Given? Kc is given for the reaction. Plan Your Strategy The value of Kc indicates the relative concentrations of products and reactants at equilibrium. Act on Your Strategy Kc for this reaction is 1 107. Therefore, the concentration of products is much greater than the concentration of reactants. Consequently, [Ag(NH3)2]+(aq) must be the more stable silver ion. Check Your Solution Kc is a ratio of product concentrations divided by reactant concentrations. Kc for the reaction is a large value, therefore the concentration of silver ion on the product side of the equation must be greater than the concentration of silver ion on the reactant side of the equation.

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20. Problem

Consider the following reaction. Kc = 2.4 1033 at 25C 2HCl(g) H2(g) + Cl2(g) HCl(g) is placed into a reaction vessel. To what extent do you expect the equilibrium mixture to dissociate into H2(g) and Cl2(g) ? What Is Required? Describe the extent of dissociation of HCl at 25C. What Is Given? Kc = 2.4 1033 at 25C Plan Your Strategy HCl is on the right in the chemical equation. A small dissociation of HCl corresponds to a large [HCl] and a large value of Kc . Act on Your Strategy The value of Kc is large. The position of equilibrium lies to the right and very little HCl dissociates at 25C. Check Your Solution Kc is a fraction with product terms in the numerator. A large value of Kc corresponds to large concentration of product terms. Because HCl is on the product side of the equation, essentially no dissociation takes place.

Student Textbook page 352

21. Problem

The following equation represents the equilibrium reaction for the dissociation of phosgene gas. CO(g) + Cl2(g) COCl2(g) At 100C, the value of Kc for this reaction is 2.2 108 . The initial concentration of COCl2(g) in a closed container at 100C is 1.5 mol/L. What are the equilibrium concentrations of CO(g) and Cl2(g) ? What Is Required? You need to nd [CO] and [Cl2] at equilibrium. What Is Given? You are given the chemical equation. You know the value of Kc , and the initial concentration of COCl2(g) . Plan Your Strategy Step 1 Divide the initial concentration of COCl2(g) by Kc to determine whether you can ignore the change in concentration. Step 2 Set up an ICE table. Let x represent the change in [COCl2]. Step 3 Write the equilibrium expression. Substitute the equilibrium concentrations into the equilibrium expression. Solve the equilibrium expression for x. Step 4 Calculate [CO] and [Cl2] at equilibrium. Act on Your Strategy 1.5 initial concentration = Step 1 Kc 2.2 108 = 6.8 107 Because this is well above 500, the change in [COCl2] can be ignored.

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Step 2

Concentration (mol/L) Initial Change Equilibrium COCl2(g) 1.5 x 1.5 x 1.5 CO(g) 0 +x x + Cl2(g) 0 +x x

Step 3

= 1.8 104 Step 4 [CO] = [Cl2] = 1.8 104 mol/L Check Your Solution The assumption that x is negligible compared with the initial concentration is valid because, using the rules for subtracting measured quantities, 1.5 (1.8 104) = 1.5 . Next, check the equilibrium values: (1.8 104)2 = 2.2 108 1.5 This is equal to the equilibrium constant.

22. Problem

Hydrogen sulde is a poisonous gas with a characteristic, offensive odour. It dissociates at 1400C, with Kc equal to 2.4 104 . H2S(g) 2H2(g) + S2(g) 4.0 mol of H2S is placed in a 3.0 L container. What is the equilibrium concentration of H2(g) at 1400C? What Is Required? You need to nd the concentration of H2(g) at equilibrium. What Is Given? You are given the chemical equation. You know the value of Kc , and the initial amount of H2(g) . The volume of the container is given. Plan Your Strategy Step 1 Calculate the initial molar concentration of H2S(g). Step 2 Divide the initial concentration of H2S(g) by Kc to determine whether you can ignore the change in concentration. Step 3 Set up an ICE table. Let x represent the change in [H2S(g)]. Step 4 Write the equilibrium expression. Substitute the equilibrium concentrations into the equilibrium expression. Solve the equilibrium expression for x. Step 5 Calculate [H2] at equilibrium. Act on Your Strategy 4.0 mol = 1.33 mol/L Step 1 [H2S] = 3.0 L 1.33 initial concentration = Step 2 Kc 2.4 104 = 5.5 103 Because this is well above 500, the change in [H2S] can be ignored.

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Step 3

Concentration (mol/L) Initial Change Equilibrium H2S(g) 1.33 x 1.33 x 1.33 2H2(g) 0 +2x 2x + S2(g) 0 +x x

Step 4

x =

7.98 105

= 4.3 102 Step 4 [H2] = 2 (4.3 102) = 8.6 102 mol/L Check Your Solution The assumption that x is negligible compared with the initial concentration is valid because, using the rules for subtracting measured quantities, 1.3 (4.3 102) = 1.3 . Next, check the equilibrium values: (8.6 102)2(4.3 102) = 2.4 104 1.3 This is equal to the equilibrium constant.

23. Problem

At a certain temperature, the value of Kc for the following reaction is 3.3 1012. 2NCl3(g) N2(g) + 3Cl2(g) A certain amount of nitrogen trichloride, NCl3(g) is put in a 1.0 L reaction vessel at this temperature. At equilibrium, 4.6 104 mol of N2(g) is present. What amount of NCl3(g) was placed in the reaction vessel? What Is Required? You need to nd the initial amount of NCl3(g) placed in the reaction vessel. What Is Given? You are given the chemical equation and the value of Kc . You know the volume of the reaction vessel. You are told the amount of N2(g) at equilibrium. Plan Your Strategy Step 1 Calculate the equilibrium molar concentration of N2(g) . Step 2 Kc is very small. Assume you can ignore the change in concentration of NCl3(g) and set up an ICE table. Let x represent the change in [N2]. Step 3 Write the equilibrium expression. Substitute the equilibrium concentrations into the equilibrium expression. Solve the equilibrium expression for [NCl3]. Step 4 Determine the amount of NCl3(g) put in the reaction vessel.

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CHEMISTRY 12

Act on Your Strategy Step 1 The volume of the reaction vessel is 1.0 L. Therefore, the equilibrium [N2] = 4.6 104 mol/L. Step 2 Set up an ICE table.

Concentration (mol/L) Initial Change Equilibrium 2NCl3(g) [NCl3] 2x [NCl3] 2x [NCl3] N2(g) 0 +x 4.6 104 + 3Cl2(g) 0 +3x 3x = 3(4.6 104) = 1.38 103

3 Kc = [N2][Cl22] [NCl3] 4 3 3 3.3 1012 = (4.6 10 )(1.38 10 ) 2 [NCl3]

Step 3

[NCl3] =

3.66 101

= 6.1 101 mol/L Step 4 The reaction vessel has a volume of 1.0 L. The amount of NCl3(g) put in the vessel must have been 6.1 101 mol. Check Your Solution First, check your assumption that x is negligible compared with the initial concentration of NCl3(g) . Using the rules for subtracting measured quantities, 6.1 101 2(4.6 104) = 6.1 101 . Next, check the equilibrium values: (4.6 104)(1.4 103)3 = 3.4 1012 (6.1 101)2 This is equal to the equilibrium constant within mathematical rounding error.

24. Problem

At a certain temperature, the value of Kc for the following reaction is 4.2 108 . N2(g) + O2(g) 2NO(g) 0.45 mol of N2(g) and 0.26 mol of O2(g) are put in a 6.0 L reaction vessel. What is the equilibrium concentration of NO(g) at this temperature? What Is Required? You need to nd the concentration of NO(g) at equilibrium.

What Is Given? You are given the chemical equation. You know the value of Kc , and the initial amounts of N2(g) and O2(g) . The volume of the container is given. Plan Your Strategy Step 1 Calculate the initial molar concentrations of N2(g) and O2(g) . Step 2 Divide the smallest initial concentration by Kc to determine whether you can ignore the change in concentration. Step 3 Set up an ICE table. Let x represent the change in [N2(g)]. Step 4 Write the equilibrium expression. Substitute the equilibrium concentrations into the equilibrium expression. Solve the equilibrium expression for x. Step 5 Calculate [NO] at equilibrium.

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CHEMISTRY 12

Act on Your Strategy 0.45 mol = 0.075 mol/L Step 1 [N2] = 6.0 L 0.26 mol = 0.043 mol/L [O2] = 6.0 L Step 2 The smallest initial concentration is [O2]. initial concentration = 0.043 Kc 4.2 108 = 1.0 106 Because this is well above 500, the changes in [O2] and [N2] can be ignored. Step 3 Set up an ICE table.

Concentration (mol/L) Initial Change Equilibrium 0.075 x N2(g) 0.075 x 0.075 0.043 x + O2(g) 0.043 x 0.043 2NO(g) 0 +2x 2x

Step 4

x =

3.39 1011

= 5.8 106 Step 5 [NO] = 2 (5.8 106) = 1.2 105 mol/L Check Your Solution The assumption that x is negligible compared with the initial concentration is valid because, using the rules for subtracting measured quantities, 0.043 (5.8 106) = 0.043. Next, check the equilibrium values: (1.2 105)2 = 4.5 108 (0.075)(0.043) This is equal to the equilibrium constant, within the error introduced by mathematical rounding.

25. Problem

At a particular temperature, Kc for the decomposition of carbon dioxide gas is 2.0 106 . 2CO2(g) 2CO(g) + O2(g) 3.0 mol of CO2 is put in a 5.0 L container. Calculate the equilibrium concentration of each gas. What Is Required? You need to nd the concentration of CO2(g), CO(g) , and O2(g) at equilibrium. What Is Given? You are given the chemical equation. You know the value of Kc , and the initial amount of CO2(g). The volume of the container is given.

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CHEMISTRY 12

Plan Your Strategy Step 1 Calculate the initial molar concentration of CO2(g). Step 2 Divide the initial concentration of CO2(g) by Kc to determine whether you can ignore the change in concentration. Step 3 Set up an ICE table. Let x represent the change in [O2(g)]. Step 4 Write the equilibrium expression. Substitute the equilibrium concentrations into the equilibrium expression. Solve the equilibrium expression for x. Step 5 Calculate the concentration of each gas at equilibrium. Act on Your Strategy 3.0 mol = 0.60 mol/L Step 1 [CO2] = 5.0 L

Step 2

0.60 initial concentration = Kc 2.0 106 = 3.0 105 Because this is well above 500, the change in [CO2] can be ignored. Step 3 Set up an ICE table.

Concentration (mol/L) Initial Change Equilibrium 0.60 2x 2CO2(g) 0.60 2x 0.60 2CO(g) 0 +2x 2x + O2(g) 0 +x x

Step 4

2 Kc = [CO] [O2] [CO2]2 2 2.0 106 = (2x) (x) 0.60 3 x = 3.0 107

= 6.7 103 Step 4 At equilibrium: [CO2] = 0.60 mol/L [CO] = 2(6.7 103) = 1.3 102 mol/L [O2] = 6.7 103 mol/L Check Your Solution The assumption that x is negligible compared with the initial concentration is valid because, using the rules for subtracting measured quantities, 0.60 2(6.7 103) = 0.59 0.60 . Next, check the equilibrium values: (1.3 102)2(6.7 103) = 1.9 106 0.60 This is equal to the equilibrium constant, within the error introduced by mathematical rounding.

Student Textbook page 356

26. Problem

The following reaction takes place inside a cylinder with a moveable piston. 2NO2(g) N2O4(g)

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CHEMISTRY 12

At room temperature, the equilibrium concentrations inside the cylinder are [NO2] = 0.0206 mol/L and [N2O4] = 0.0724 mol/L. (a) Calculate the value of Kc . (b) Calculate the concentration of each gas at the moment that the piston is used to halve the volume of the reacting mixture. Assume that the temperature remains constant. (c) Determine the value of Qc when the volume is halved. (d) Predict the direction in which the reaction will proceed to re-establish equilibrium. What Is Required? Calculate Kc . Find [NO2] and [N2O4] when the volume inside the cylinder is halved and calculate Qc . Predict the direction the reaction will proceed to re-establish equilibrium. What Is Given? You have the chemical equation and the equilibrium concentrations of NO2(g) and N2O4(g) . Plan Your Strategy

(a) Write the equilibrium expression. Substitute the equilibrium concentrations into

(b) Calculate [NO2] and [N2O4] when the volume of the cylinder is halved. (c) Calculate the value of Qc. (d) Compare the value of Qc with the value of Kc . Decide whether the system is at

equilibrium and, if not, in which direction the reaction will go. Act on Your Strategy [N2O4] (a) Kc = [NO2]2 = 0.0724 2 (0.0206) = 171 (b) The volume of the cylinder is halved. Therefore, [NO2] = 0.0206 mol/L = 0.0412 mol/L 0.5 0.0724 mol/L = 0.145 mol/L [N2O4] = 0.5 [N2O4] (c) Qc = [NO2]2 = 0.1448 2 (0.0412) = 85.3 (d) Qc < Kc . The system is not at equilibrium and will proceed by moving to the right. Check Your Solution Check your calculations of Kc and Qc. The value of Qc is less than that of Kc , so you should expect the reaction to re-establish equilibrium by forming more product.

27. Problem

Ethyl acetate is an ester that can be synthesized by reacting ethanoic acid (acetic acid) with ethanol. At room temperature, the equilibrium constant for this reaction is 2.2. CH3COOCH2CH3( ) + H2O( ) CH3COOH( ) + CH3CH2OH( )

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Various samples were analyzed. The concentrations are given in the table below. Decide whether each sample is at equilibrium. If it is not at equilibrium, predict the direction the reaction will proceed to establish equilibrium.

Sample [CH3COOH] (mol/L) [CH3CH2OH] (mol/L) [CH3COOCH2CH3] (mol/L) [H2O] (mol/L)

What Is Required? You must calculate Qc for each sample and interpret the value. What Is Given? You have the chemical equation. You know the value of Kc is 2.2. You also know the concentrations of the reacting substances in each sample. Plan Your Strategy Write the expression for Qc, and then calculate its value for each sample. Compare the value of Qc with the value of Kc . Decide whether the system is at equilibrium and, if not, in which direction the reaction will go. Act on Your Strategy [CH3COOCH2CH3][H2O] Qc = [CH3COOH][CH3CH2OH]

(a) Qc =

(0.10)(0.10) = 1.0 (0.10)(0.10) Qc < Kc The reaction proceeds to the right. (0.16)(0.28) = 4.1 (0.084)(0.13) Qc > Kc The reaction proceeds to the left. (0.33)(0.20) = 2.2 (0.14)(0.21) Qc = Kc The reaction is at equilibrium. (0.15)(0.17) = 3.7 (0.063)(0.11) Qc > Kc The reaction proceeds to the left.

(b) Qc =

(c) Qc =

(d) Qc =

Check Your Solution Check your calculations of Qc. When the value of Qc is less than that of Kc , the reaction proceeds to the right because more product must be formed to reach equilibrium.

28. Problem

In the past, methanol was obtained by heating wood without allowing the wood to burn. The products were collected, and methanol (sometimes called wood alcohol) was separated by distillation. Today methanol is manufactured by reacting carbon monoxide with hydrogen gas. CO(g) + 2H2(g) CH3OH(g) At 210C, Kc for this reaction is 14.5. A gaseous mixture at 210C contains the following concentrations of gases: [CO] = 0.25 mol/L, [H2] = 0.15 mol/L, and [CH3OH] = 0.36 mol/L. What will be the direction of the reaction if the gaseous mixture reaches equilibrium?

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CHEMISTRY 12

What Is Required? You must calculate Qc and interpret its value. What Is Given? You have the chemical equation. You know the value of Kc is 14.5. You also know the concentrations of the gases: [CO] = 0.25 mol/L, [H2] = 0.15 mol/L, and [CH3OH] = 0.36 mol/L. Plan Your Strategy Write the expression for Qc, and then calculate its value. Compare the value of Qc with the value of Kc . Decide whether the system is at equilibrium and, if not, in which direction the reaction will go. Act on Your Strategy [CH3OH] Qc = [CO][H2]2 0.36 = (0.25)(0.15)2 = 64 Qc > Kc The system is not at equilibrium. The reaction proceeds to the left. Check Your Solution Check your calculations of Qc. When the value of Qc is greater than that of Kc , the reaction proceeds to the left because less product must be formed to reach equilibrium.

Student Textbook page 366367

29. Problem

Consider the following reaction. 2HI(g) H2(g) + I2(g) + 52 kJ In which direction does the equilibrium shift if there is an increase in temperature? What Is Required? You need to determine whether increasing the temperature causes the equilibrium to shift to the left or to the right. What Is Given? You have the chemical equation. You know that heat is shown on the left of the equation. Therefore, the reaction is endothermic. Plan Your Strategy Use the chemical equation to determine the shift in equilibrium that will minimize the change. Act on Your Strategy The temperature is increased. Therefore, the equilibrium must shift in the direction in which the reaction is endothermic. From left to right, the reaction is endothermic. The reaction shifts to the right if the temperature is increased. Check Your Solution An increase in temperature must result in a shift in the reaction that minimizes the temperature increase. The shift must be in the direction in which the reaction is endothermic.

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CHEMISTRY 12

30. Problem

A decrease in the pressure of each equilibrium system below is caused by increasing the volume of the reaction chamber. In which direction does the equilibrium shift? CO(g) + H2O(g) (a) CO2(g) + H2(g) N2O4(g) (b) 2NO2(g) 2CO(g) + O2(g) (c) 2CO2(g) CS2(g) + 4H2(g) (d) CH4(g) + 2H2S(g) What Is Required? You need to determine whether decreasing the pressure causes the equilibrium to shift to the left or the right, or whether it has no effect. What Is Given? You have each chemical equation. Plan Your Strategy Use the chemical equation to determine the shift in equilibrium that will minimize the decrease in pressure. The shift must be towards the side with the largest number of gas molecules. Act on Your Strategy (a) As the reaction proceeds there is no change in the number of gas molecules. Therefore, increasing the volume of the container has no effect on the position of equilibrium. (b) There are more gas molecules on the left side of the equation. Therefore, increasing the volume of the container causes the reaction to shift to the left. (c) There are more gas molecules on the right side of the equation. Therefore, increasing the volume of the container causes the reaction to shift to the right. (d) There are more gas molecules on the right side of the equation. Therefore, increasing the volume of the container causes the reaction to shift to the right. Check Your Solution An increase in volume must result in a decrease in pressure. The reaction must shift in the direction that minimizes the pressure decrease. The shift must be in the direction in which more gas molecules are formed.

31. Problem

The following reaction is exothermic. N2(g) + 2H2O(g) 2NO(g) + 2H2(g) In which direction does the equilibrium shift as a result of each change? (a) removing the hydrogen gas (b) increasing the pressure of gases in the reaction vessel by decreasing the volume (c) increasing the pressure of gases in the reaction vessel by pumping in argon gas while keeping the volume of the vessel constant (d) increasing the temperature (e) using a catalyst What Is Required? You need to determine whether each change causes the equilibrium to shift to the left or the right, or whether it has no effect. What Is Given? You have the chemical equation. You know the reaction is exothermic. Plan Your Strategy Identify the change. Then use the chemical equation to determine the shift in equilibrium that will minimize the change.

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CHEMISTRY 12

Act on Your Strategy (a) [H2] is reduced. Therefore, the equilibrium must shift to increase [H2]. The reaction shifts to the left. (b) The pressure is increased by decreasing the volume of the reaction vessel. Therefore, the equilibrium must shift to decrease the pressure. Because there are fewer gas molecules on the right of the equation, the reaction shifts to the right. (c) Argon does not react with any of the gases in the mixture. The position of equilibrium does not change. (d) The temperature increases. Therefore, the equilibrium must shift in the direction in which the reaction is endothermic. From left to right, the reaction is exothermic. Therefore, the reaction is endothermic from right to left. The reaction shifts to the left if the temperature is increased. (e) A catalyst has no effect on the position of equilibrium. Check Your Solution Check the changes. Any change that affects the equilibrium reaction must result in a shift that minimizes it.

32. Problem

In question 31, which changes affect the value of Kc ? Which changes do not affect the value of Kc ? What Is Required? You must determine which changes affect the value of Kc . What Is Given? You have the chemical equation. You know the reaction is exothermic. Plan Your Strategy For a given reaction at equilibrium, Kc depends on temperature. Act on Your Strategy Change (d) is the only one that affects the temperature of the reaction. Therefore, change (d) is the only one that affects the value of Kc . Therefore, changes (a), (b), (c), and (e) have no effect on the value of Kc . Check Your Solution The value of Kc for a particular equilibrium system depends on temperature.

33. Problem

Toluene, C7H8 , is an important organic solvent. It is made industrially from methyl cyclohexane. C7H14(g) C7H8(g) + 3H2(g) The forward reaction is endothermic. State three different changes to an equilibrium mixture of these reacting gases that would shift the equilibrium toward greater production of toluene. What Is Required? You must identify three different changes that would shift the equilibrium toward greater production of toluene. What Is Given? You have the chemical equation. You know the reaction is endothermic. Plan Your Strategy Each change must shift the reaction to the right. Use the chemical equation to identify changes that will shift the equilibrium to the right as the change is minimized.

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CHEMISTRY 12

Act on Your Strategy - The equilibrium will shift to the right if any chemical on the left is added. Therefore, increasing [C7H14] increases the production of toluene. - The equilibrium will shift to the right if any chemical on the right is removed. Therefore, decreasing either [C7H8] or [H2], or both, increases the production of toluene. - The number of gas molecules increases as the reaction proceeds from left to right. Therefore, decreasing the pressure of the gases in the reaction vessel increases the production of toluene. - The reaction is endothermic from left to right. Therefore, increasing the temperature increases the production of toluene. Check Your Solution Check each change. Minimizing each change must result in a shift in the reaction to the right.

126

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