Chapter 2:

Equilibrium: The Extent of Chemical Reactions

Chemical Equilibrium
Key Concepts
Equilibrium constant Dynamic equilibrium Equilibrium constant expression Equilibrium constant, K Calculating K Reaction quotient, Q Finding equilibrium concentrations Le Chteliers principle

Key Equations and Relationships

Expression for the Equilibrium Constant, Kc aA + bB cC + dD

[C]c [D]d Kc ! [A]a [B]b

Key Equations and Relationships

Key Skills/Learning Outcome

Express Eq constants for chemical equations Relate Kp and Kc Write Eq expressions for reactions involving a solid or liquid Find Eq constants from experimental concentration measurements Predict the direction of a reaction by comparing Q and K Calculate Eq concentrations from the Eq constant and one or more Eq concentrations Find Eq concentrations from initial concentrations and Eq constant Calculate Eq partial pressures from the Eq constant and initial partial pressures Determine the effect of concentration, volume (pressure), temperature change on Eq

2.1 The Equilibrium State and the equilibrium constant. 2.2 Expressing Equilibria with pressure terms: Relation between Kc and Kp. 2.3 The Reaction Quotient and the Equilibrium Constant 2.4 How to Solve Equilibrium Problems 2.5 LeChateliers Principle 2.6 Heterogeneous Equilibrium.

Introduction Reversible Reactions

Forward

A+B

C+D
Backward / reverse

[A] or [B]
Forward

[C] or [D]
Backward / reverse

Time

Time

2.1 The Equilibrium state and the equilibrium constant.

Equilibrium applies to the extent of a reaction, the concentration of product that has appeared after an unlimited time, or once no further change occurs. At equilibrium: rateforward = ratereverse

A system at equilibrium is dynamic on the molecular level; no further net change is observed because changes in one direction are balanced by changes in the other.

Chemical Equilibrium

rf

rf ! k f [A][B] rb ! kb [C][D]
rb

1. When the rate of the back reaction becomes equal to the rate of the forward reaction the [A], [B], [C], and [D] no longer change and the system is said to have attained chemical equilibrium.

Dynamic Equilibrium

A+B p C+D and C+D p A+B

A , B C , D

1. Although it would appear that no further change takes place once the system has reached equilibrium, be aware that at the molecular level the following two reaction processes take place continuously. 2. There does not appear to be any change taking place because the two processes take place at exactly the same rates

Equilibrium constant, Kc.

aA+ bB cC + dD
i

a moles of substance A reacts with b moles of substance B to produce c moles of substance C and d mole of substance D.

rf ! rb @ k f [A][B] ! kb [C][D] [C][D] k f @ ! ! a constant ! K [A][B] kb

[ ] = concentrations in mol/dm3 Kc has a constant value at a particular T. Eg: [HI]2 / [H2] [I2] = Kc = x

For reactions in which the # of reactant and product particles are not equal, Kc will have units. eg : N2 + 3H2 2NH3.

2.1 Determination of equilibrium constant a. only applies to systems at equilibrium b. Kc is only constant if T remains constant c. The Kc value is unaffected by change in concentration of either reactants or products. d. The magnitude of Kc provide a useful indication of the extend of a chemical reaction. A large value of Kc indicates a high proportion of products to reactants and vice versa.

The magnitude of equilibrium constants

aA + bB cC + dD

[C]c [D]d Kc ! a b [A] [B]

What kind of informations we can gain from equilibrium constant ?

1. If K c } 1 then we would expect that, when the system has reached equilibrium [C] , [D] } [A] , [B]. The equilibrium mixture will contain significant amounts of all the reactants and products. 2. If K c "" 1 then we would expect that, when the system has reached equilibrium [C] , [D] >> [A] , [B]. 3. The equilibrium mixture will contain much more product than reactant. 4. The position of equilibrium is said to be far to the right.

1then we would expect that, when the system 5. If K c has reached equilibrium [C] , [D] << [A] , [B].
6. The equilibrium mixture will contain much more reactant than product. 7. The position of equilibrium is said to be far to the left.

Equilibrium constant, Kc. The direction of the chemical equation and Keq

[C]c [D]d Kc ! a b [A] [B]

If we invert the chemical equation for the reversible reaction:

[A]a [B]b K c' ! [C]c [D]d

We see that

K c' ! 1

Kc

Equilibrium constant, Kp. Kp is the equilibrium constant in terms of partial pressures. It can only be applied to gas reactions. aA(g)+ bB(g) cC(g) + dD(g) (Pc) c (PD) d/(PA) a (PB) b = Kp PA = partial pressure of gas A etc. Like Kc, the value and units for Kp depend on the way in which the chemical equilibrium is written eg : H2(g) + I2(g) 2HI(g)

 we can either write: [HI]2/[I2] [H2] = Kc or (PHI)2 /(PI2) (PH2) = Kp When the amount of moles of substances on both sides of the chemical equilibrium, in a gas reaction, is the same, Kp = Kc (RT)0 Kp= Kc Kp and Kc have no units Ex: H2(g) +Br2(g) 2HBr(g), where n =0.

2.2 Expressing Equilibria with pressure terms: Relation between Kc and Kp. When dealing with reactions taking place in the gas phase, it is often more convenient to deal with partial pressures of reactants and products than with concentrations. From the ideal gas equation for a component of a gas mixture

piV ! ni RT

ni @ pi ! RT V @ pi ! ci RT

2.2 Expressing Equilibria with pressure terms: Relation between Kc and Kp.

aA bB
[B]b Kc ! [A]a PB Kp ! a PA (c BRT) KP ! a (c ART)
b b

[B] (RT) Kp ! [A]a

Kp = Kc (RT)n Kp = Kc (0.0821T)n

b a

n = moles of gaseous product moles of gaseous reactants.

R = 0.0821 L. atm / K. mol

Equilibrium constant, Kp.

Balanced chemical equation

N2 (g)  3H2 (g) p 2NH3 (g)

Kc
[NH 3 ] Kc ! [N 2 ][H 2 ]3
2

Kp
Kp ! Kp !
Kp !
2 pNH3 3 p N 2 pH 2

2HI (g) p H2 (g)  I2 (g)

2SO 2 (g)  O 2 (g) p 2SO 3 (g)

[H 2 ][I 2 ] Kc ! [HI]2
[SO3 ] Kc ! [SO 2 ]2 [O 2 ]
2

pH 2 pI2
2 pHI
2 pSO3 2 pSO2 pO2

Sample Problem 2.1

PROBLEM: For the reaction 2NH3(g) . N2(g) + 3H2(g) Prove that Kc = Kp(RT)2 Do not use the formula Kp = Kc(RT)n, start from Pi = ci RT, where Pi is the partial pressure of substance i and ci is its molar concentration. Substitute into Kc.

Sample Problem 2.2 PROBLEM:

Converting Between Kc and Kp

2NO2(g)

2 NO (g) + O2 (g)

Find Kc for this reaction. (Kp = 2.2 x 1012 at 25oC)

Sample Problem 2.3

Calculating Kc from Concentration Data

PROBLEM: In order to study hydrogen halide decomposition, a researcher fills an evacuated 2.00-L flask with 0.200mol of HI gas and allows the reaction to proceed at 4530C. 2HI(g) H2(g) + I2(g)

At equilibrium, [HI] = 0.078M. Calculate Kc. PLAN: First find the molar concentration of the starting material and then find the amount of each component, reactants and products, at equilibrium.

SOLUTION: [HI] =

0.200 mol 2.00 L

= 0.100 M

Let x be the amount of [H2] at equilibrium. Then x will also be the concentration of [I2] and the change in of [HI] will be the original concentration minus the stoichiometric amount that reacted, 2x, or 0.078M.

Sample Problem 2.3

Calculating Kc from Concentration Data

continued

concentration (M) initial change equilibrium

2HI(g) 0.100 -2x 0.100 - 2x ;

H2(g) 0 + x x

I2(g) 0 + x x

[HI] = 0.078 = 0.100 - 2x

x = 0.011M

Qc =

[H2] [I2] [HI]2

[0.011][0.011] (0.078)2

= 0.020 = Kc

2.3 The Reaction Quotient and equilibrium constant. aA + bB

Q (and K) can be calculated as
[C]c[D]d [A]a[B]b We use the molar concentrations of the substances in the reaction. This is symbolized by using square brackets - [ ].

cC + dD

Q=

At any time, t, the system can be sampled to determine the amounts of reactants and products present. A ratio of products to reactants, calculated in the same manner as K tells us: 1) 2) 3) whether the system has come to equilibrium (Q = K) or whether the reaction has to proceed further from reactants to products (Q < K) or in the reverse direction from products to reactants (Q > K).

Predicting the direction of reaction..

[C] [D] Q! a b [A] [B]

1. If Q > K then the reverse reaction must occur to reach equilibrium (i.e., products are consumed, reactants are formed, the numerator in the equilibrium constant expression decreases and Q decreases until it equals K). 2. If Q < K then the forward reaction must occur to reach equilibrium.

Initial and Equilibrium Concentration Ratios for the N2O4-NO2 System at 2000C(473 K)

Ratio(Q) Initial Experiment [N2O4] [NO2] 1 2 3 4 0.1000 0.0000 0.0500 0.0750 0.0000 0.1000 0.0500 0.0250 [NO2]2 [N2O4] 0.0000 Equilibrium [N2O4]eq [NO2]eq 3.57x10-3 9.24x10-4 2.04x10-3 2.75x10-3 0.193 9.83x10-3 0.146 0.170

Ratio(K) [NO2]eq2 [N2O4]eq 10.4 10.4 10.4 10.5

0.0500 0.00833

The change in Q during the N2O4-NO2 reaction.

Reaction direction and the relative sizes of Q and K.

Reaction Progress

Reaction Progress

reactants

products

Equilibrium: no net change

reactants

products

Sample Problem 2.4

Writing the Reaction Quotient from the Balanced Equation.

PROBLEM:

Write the reaction quotient, Qc, for each of the following reactions: NO2(g) + O2(g) CO2(g) + H2O(g)

(a) The decomposition of dinitrogen pentoxide, N2O5(g) (b) The combustion of propane gas, C3H8(g) + O2(g)

PLAN: Be sure to balance the equations before writing the Qc expression.

SOLUTION: (a) 2 N2O5(g) 4 NO2(g) + O2(g) [NO2]4[O2] Qc = [N2O5]2 [CO2]3[H2O]4 Qc = [C3H8][O2]5

(b)

C3H8(g) +

5 O2(g)

3 CO2(g) + 4 H2O(g)

Sample Problem 2.5 PROBLEM:

Comparing Q and K to Determine Reaction Direction

For the reaction N2O4(g) 2NO2(g), Kc = 0.21 at 1000C. At a point during the reaction, [N2O4] = 0.12M and [NO2] = 0.55M. Is the reaction at equilibrium. If not, in which direction is it progressing?

PLAN:

Write an expression for Qc, substitute with the values given, and compare the Qc with the given Kc.

SOLUTION: Qc =

[NO2]2 [N2O4]

(0.55)2 (0.12)

= 2.5

Qc is > Kc, therefore the reaction is not at equilibrium and will proceed from right to left, from products to reactants, until Qc = Kc.

Sample Problem 2.6

Predicting Reaction Direction and Calculating Equilibrium Concentrations

PROBLEM: The research and development unit of a chemical company is studying the reaction of CH4 and H2S, two components of natural gas. CH4(g) + 2H2S(g) CS2(g) + 4H2(g) In one experiment, 1.00mol of CH4, 1.00mol of CS2, 2.00mol of H2S, and 2.00mol of H2 are mixed in a 250-mL vessel at 9600C. At this temperature, Kc = 0.036 (a) In which direction will the reaction proceed to reach equilibrium? (b) If [CH4] = 5.56M at equilibrium, what are the equilibrium concentrations of the other substances? PLAN: Find the initial molar concentrations of all components and use these to calculate a Qc. Compare Qc to Kc, determine in which direction the reaction will progress, and draw up expressions for equilibrium concentrations.

SOLUTION:

[CH4]initial = 1.00mol/0.25 L = 4.0M [CS2]initial = 1.00mol/0.25 L = 4.0M [H2S]initial = 2.00mol/0.25 L = 8.0M [H2]initial = 2.00mol/0.25 L = 8.0M

Sample Problem 2.6 continued Qc = [CS2][H2]4

Predicting Reaction Direction and Calculating Equilibrium Concentrations

[CH4][H2S]2

[4.0][8.0]4 [4.0][8.0]2

A Qc of 64 is >> than Kc = 0.036 = 64 The reaction will progress to the left. CS2(g) + 4H2(g) 4.0 -x 4.0 - x 8.0 - 4x 8.0 - 4x

concentrations initial change equilibrium

CH4(g) + 2H2S(g) 4.0 +x 4.0 + x 8.0 + 2x 8.0 + 2x

At equilibrium [CH4] = 5.56M, so 5.56 = 4.0 + x and x = 1.56M

Therefore -

[H2S] = 8.0 + 2x = 11.12M [CS2] = 4.0 - x = 2.44M [H2] = 8.0 - 4x = 1.76M

2.4 How to Solve Equilibrium Problems.

Calculations of Equilibrium Concentrations.
Sample Problem 2.7

A 5.00 dm3 flask is charged at 700 K with 2.00 mol each of hydrogen gas and iodine vapour. Determine the equilibrium concentrations of H2, I2 and HI. (Kc = 57).

Step 1.

Write down a balanced chemical equation for the reaction.

H2 (g)  I2 (g) 2HI(g)

Step 2. Note the volume of the reaction vessel (if given). If not given, treat it as an unknown, V.

V = 5.00 dm3
Step 3. Construct a table below the chemical equation, with a column underneath each reactant and product.

H2 (g)  I2 (g) 2HI(g)

Amounts (mol) present initially: Changes in amounts (mol): Amounts (mol) present at equilibrium: Concentrations (mol dm-3) present at equilibrium:

Step 4.

Supply the information required in the table. When information is required that is not available from the statement of the problem, introduce an unknown: x

H2 (g)  I2 (g) 2HI(g)

Amounts (mol) present initially: 2.00 2.00 -x 2.00 x (2.00 x)/5 = 0.4 0.2x 0 +2x 2x 0.4x

Changes in amounts (mol): -x Amounts (mol) present at equilibrium: Concentrations (mol dm-3) present at equilibrium: 2.00 x (2.00 x)/5 = 0.4 0.2x

Step 5.

Substitute expressions for the equilibrium concentrations into the equilibrium constant expression and solve for x

[HI]2 (0.4 x)(0.4 x) ! ! 57 Kc ! [H 2 ][I 2 ] (0.40  0.2 x)(0.40  0.2 x) 0.4 x @ ! 57 0.40  0.2 x 0.4 x @ ! 57 ! s7.55 0.40  0.2 x
2

0.4 x ! s7.55(0.40  0.2 x) @ 0.4 x ! 3.02  1.51x or 0.4x ! 3.02  1.51x @1.91x ! 3.02 or  1.1x ! 3.01 @ x ! 1.58 or x ! 2.74
It seems as though we have two possible answers for the quantity x. Do both answers make sense? If we started off with 2 mol of H2 it is possible that we could have used up 1.58 mol. We could not have used up 2.74 mol of H2. So disregard latter result.

Step 6. Using the acceptable value of x, we return to the table we set up earlier and we use x to calculate the concentrations present at equilibrium.

H2 (g)  I2 (g) 2HI(g)

Amounts (mol) present initially: 2.00 2.00 -x 2.00 x (2.00 x)/5 = 0.4 0.2x 0 +2x 2x 0.4x

Changes in amounts (mol): -x Amounts (mol) present at equilibrium: Concentrations (mol dm-3) present at equilibrium: 2.00 x (2.00 x)/5 = 0.4 0.2x

So: [H ] ! 0.4  0.2 x ! 0.4  0.2 v 1.58 ! 0.084 mol dm -3 2

[I 2 ] ! 0.4  0.2 x ! 0.4  0.2 v1.58 ! 0.084 mol dm -3 [HI] ! 0.4 x ! 0.4 v 1.58 ! 0.632 mol dm -3

Step 7: Check your answers by substituting the answers back into the equilibrium constant expression and checking to see whether the correct equilibrium constant is obtained.

[HI] 0.632 v 0.632 ! ! 57 [H 2 ][I 2 ] 0.084 v 0.084

Notice: When the concentrations at equilibrium are substituted back into the expression for the equilibrium constant, the correct value of the equilibrium constant (57) is recovered. This is proof that the problem has been solved correctly.

Sample Exercise

1. 2.

3.

A flask contains 14 g of nitrogen and 48 g of oxygen. The total P in the flask is 50 kPa. Calculate the partial P of nitrogen. When 1 mole of hydrogen and 1 mole iodine are allowed to reach equilibrium in a 1 dm3 flask at 4500 C and 1.01 X 105 Pa, the amount of hydrogen iodide at equilibrium is 1.56 mole. Calculate Kp at 4500 C. Write an expression for the equilibrium constant for the reaction: A +B C + D. a) A, B, C, D are gases b) A, B, C, D are solution.

Partial pressure of N2,PN2 = (no. of moles of N2 / no. of moles of N2 & O2) x total pressure

Sample exercise

1.

The equilibrium mixture present in a 3 dm3 flask at 2500 C was found to contain:1 mole of PCl5, 2 mole of PCl3, 0.3 mole of Cl2. Calculate the equilibrium constant Kc for the equilibrium : PCl5 PCl3+ Cl2.

2.

A quantity of N2 O4 was dissolved in trichloromethane. The N2O4 dissociate accordingly to the equation: N2O4 2NO2. A solution of N2O4 and NO2 at equilibrium in trichloromethane at 100C was analysed . 0.5 dm3 of the sol was found to contain 0.0014 moles of NO2. 2 dm3 of the same sol was found to contain 1.04 mole of N2O4. a. Calculate Kc for the equilibrium above, and give its units b. What is Kc for 2NO2 N2O4?

3.

Calculate the amount of ethyl ethanoate formed when 1 mol ethanoic acid and 1 mole ethanol reach equilibrium. At room T, Kc= 4. CH3COOH(aq) + C 2H5OH(aq) CH3COOC 2H5 (aq) + H2O(aq).

4.

When 1 mole of methanol and 1 mole of ethanoic acid react together according to the equilibrium, CH3OH(aq) + CH3COOH(aq) CH3COOCH3(aq) + H2O(aq), The equilibrium mixture produced contains 0.2 mole of methyl ethanoat and 0.2 mole of water. a. Calculate the equilibrium constant b. 3.0 moles of methanol and 1 mole of ethanoic acid were mixed together at the same T. Calculate the amount of methyl ethanoate produced at equilibrium.

2.5 Le Chteliers Principle Principle.

equilibrium is subjected to a change, processes will occur which tend to counteract the change imposed.

Le Chteliers Principle states that If a system in

a. Concentration change. b. Temperature change. c. Pressure and volume change. a. Effect of a catalyst

A. Concentration changes.
1. If the concentration of one of the substances in a reversible equilibrium is altered, the equilibrium will shift to oppose the change in concentration. A +B C+D 2. @more A and B react to produce C and D until a new equilibrium attained. 3. @a new equilibrium mixture will contain more C and D, less B. 4. If extra A is added to the equilibrium mixture, according to LCP, the equilibrium will shift to remove the extra A. 5. If some A is removed, equilibrium will shift to replace A. 6. @more C and D will react to produce A and B in the backward reaction, until a new equilibrium is attained. 7. The new equilibrium mixture will contain less C and D, more B.

1. The equilibrium position shifts to the right if a reactant is added or a product is removed: [reactant] increases or [product] decreases. 2. The equilibrium position shifts to the left if a reactant is removed or a product is added: [reactant] decreases or [product] increases.

A. Concentrations changes Example 1

1. Haber process reaction

N2(g) + 3H2(g)

2NH3(g)

H= - 91.8 kJ

2. If H2 is added while the system is at equilibrium, the system must respond to counteract the added H2. 3. The system must consume the H2 and produce more of the products until a new equilibrium is established. 4. So, most of the additional H2 will be consumed, and [N2] will decrease, while [NH3] will increase. 3 ways to maximize the yield of NH3. i. ii. iii.

q [NH3], remove it as it forms. q volume ( o pressure) q temperature, exothermic.

H2 is consumed

[NH3] increased

[N2] decreased

N2(g) + 3H2(g)

2NH3(g)

A. Concentrations changes Example 2

Table The Effect of Added Cl2 on the PCl3-Cl2-PCl5 System Concentration (M) Original equilibrium Disturbance New initial Change New equilibrium 0.200 -x 0.200 - x PCl3(g) 0.200 + Cl2(g) 0.125 +0.075 0.200 -x 0.200 - x 0.600 +x 0.600 + x (0.637)*
*Experimentally determined value.

PCl5(g) 0.600

The effect of added Cl2 on the PCl3-Cl2-PCl5 system. PCl3(g) + Cl2(g) PCl5(g)

Sample Problem 2.8 PROBLEM:

Predicting the Effect of a Change in Concentration on the Equilibrium Position

To improve air quality and obtain a useful product, chemists often remove sulfur from coal and natural gas by treating the fuel contaminant hydrogen sulfide with O2; 2H2S(g) + O2(g) What happens to (a) [H2O] if O2 is added? (c) [O2] if H2S is removed? (b) [H2S] if O2 is added? (d) [H2S] if sulfur is added? 2S(s) + 2H2O(g)

PLAN: Write an expression for Q and compare it to K when the system is disturbed to see in which direction the reaction will progress. [H2O]2 [H2S]2[O2] (a) When O2 is added, Q decreases and the reaction progresses to the right to come back to K. So [H2O] increases.

SOLUTION:

Q=

Sample Problem 2.8

Predicting the Effect of a Change in Concentration on the Equilibrium Position

continued

Q=

[H2O]2 [H2S]2[O2]

(b) When O2 is added, Q decreases and the reaction progresses to the right to come back to K. So [H2S] decreases. (c) When H2S is removed, Q increases and the reaction progresses to the left to come back to K. So [O2] increases. (d) Sulfur is not part of the Q (K) expression because it is a solid. Therefore, as long as some sulfur is present the reaction is unaffected. [H2S] is unchanged.

B. Temperature changes.
1. Only temperature changes can alter K. 2. Consider heat as a product or a reactant. In an exothermic reaction, heat is a product. In an endothermic reaction, heat is a reactant.

3. A temperature rise will increase Kc for a system with a positive (H. 4. A temperature rise will decrease Kc for a system with a negative (H.

if (H > 0, adding heat favors the forward reaction, if (H < 0, adding heat favors the reverse reaction.

B. Temperature changes Example 1.

1. Consider

for which (H > 0. Co(H2O)62+ is pale pink and CoCl42- is blue. If a light purple room temperature equilibrium mixture is placed in a beaker of warm water, the mixture turns deep blue. Since (H > 0 (endothermic), adding heat favors the forward reaction, i.e. the formation of blue CoCl42-.

B. Temperature changes Example 2.

Haber process

At very high pressure and low temperature (top left), the yield is high, but the rate of formation is low.

Industrial conditions (circle) are between 200 and 300 atm at about 400C.

Percent yield of ammonia vs. temperature (0C) at five different operating pressures.

Sample Problem 2.9

Predicting the Effect of a Change in Temperature on the Equilibrium Position

PROBLEM: How does an increase in temperature affect the concentration of the underlined substance and Kc for the following reactions? (a) CaO(s) + H2O(l) (b) CaCO3(s) (c) SO2(g) PLAN: Ca(OH)2(aq) (H0 = -82kJ CaO(s) + CO2(g) (H0 = 178kJ S(s) + O2(g) (H0 = 297kJ

Express the heat of reaction as a reactant or a product. Then consider the increase in temperature and its effect on Kc.

Ca(OH)2(aq) heat SOLUTION: (a) CaO(s) + H2O(l) An increase in temperature will shift the reaction to the left, decrease [Ca(OH)2], and decrease Kc. (b) CaCO3(s) + heat CaO(s) + CO2(g) The reaction will shift right resulting in an increase in [CO2] and increase in Kc. (c) SO2(g) + heat S(s) + O2(g) The reaction will shift right resulting in an decrease in [SO2] and increase in Kc.

C. Pressure and volume changes.

i. Pressure of an equilibrium mixture is increased. ii. Mixture try to decrease the pressure by reducing the number of moles of gas. iii. A new equilibrium will be produced, containing fewer moles of gas. Example: 2SO2 (g)+ O2(g) 2SO3 (g)

If P increase, 3 moles are changed to 2 moles of gas, decrease of no of moles of gas, So, more SO3 are produced, less SO2 and O2 If P decrease, more SO2 and O2 will be produced, SO3 become less, increased the no of moles of gas

 There is no change in the no of moles of gas in a gaseous reaction, changes of P have no effect on the composition of the equilibrium mixture. H2(g)+ I2(g) 2HI(g) For gaseous reactions: an increase in P favours the reaction which produces fewer molecules. A decrease in P favours the gaseous reaction which produces more molecules.

Sample Problem 2.10

Predicting the Effect of a Change in Volume (Pressure) on the Equilibrium Position

PROBLEM: How would you change the volume of each of the following reactions to increase the yield of the products. (a) CaCO3(s) (b) S(s) + 3F2(g) (c) Cl2(g) + I2(g) PLAN: CaO(s) + CO2(g) SF6(g) 2ICl(g)

When gases are present a change in volume will affect the concentration of the gas. If the volume decreases (pressure increases), the reaction will shift to fewer moles of gas and vice versa.

SOLUTION:

(a) CO2 is the only gas present. To increase its yield, we should increase the volume (decrease the pressure).

(b) There are more moles of gaseous reactants than products, so we should decrease the volume (increase the pressure) to shift the reaction to the right. (c) There are an equal number of moles of gases on both sides of the reaction, therefore a change in volume will have no effect.

D. The effect of a catalyst

Enhances the rate of a reaction, By lowering the reactions activation energy. Does not alter the equilibrium constant, Does not shift the position of an equilibrium system. Does not alter the concentration if reacting substances at equilibrium.

Factors Catalyst Concentration Temperature Pressure

Rate

Composition at Eq x

Kc / Kp x x x

Position of Eq x

2.6 Heterogenous equilibrium A. Homogenous Equilibrium: Equilibrium reactions in which all the substances are in the same physical state (eg. all gases/ all liquids). 2SO2 (g)+ O2(g) 2SO3 (g)- all gases CH3COOH(l) + C 2H5OH(l) CH3COOC 2H5 (l) + H2O(l)- all liquids.

 B. Heterogenous Equilibrium: Equilirium reactions in which the substance are in different physical states (mixture of solid, liquid and gas). CaCO3 (s) CaO (s)+ CO2 (g) - solid + gas ICl(l) + Cl2 (g) ICl3 (s)- solid, lq, gas

Rule for equilibrium constants for heterogeneous equilibrium

If a pure solid or liquid is involved in a heterogeneous equilibrium, its concentration is not included in the equilibrium constant expression for the reaction. The concentration of solids are constants. Therefore in expressions for Kc and Kp the convention is to leave out all solids. Eg CaCO3 (s) CaO (s)+ CO2 (g) Kp = PCO2

Heterogeneous equilibrium - Examples

[CO2 ] Kc ! [CO]2

K p ! pCO2
2+

[Zn ] Kc ! [Cu 2+ ]

Sample exercise

1. Write an expression for Kp and Kc for the eq below : 3Fe(s) + 4H2O (g) Fe3O4 (s)+ 4 H2(g). 2. A mixture of iron and steam was allowed to reach equilibrium at 6000 C. The eq pressures of hydrogen and steam were 3.2 kPa and 2.4 kPa respectively. Calculate the value of the equilibrium constant in terms of partial P.

Sample exercise

3. a) b) c)

Write the equilibrium constant expression Kc and Kp if applicable, for each of the following heterogeneous systems: (NH4)2Se (s) 2NH3 (g) + H2Se (g) AgCl (s) Ag+ (aq) + Cl- (aq) P4(s) + 6Cl2(g) 4PCl3 (l)

Concentration of pure solid or liquid is constant!