CHAPTER 8: CHEMICAL EQUILIBRIUM

Any chemical reaction will never stop but continue in equilibrium condition What is equilibrium?

Definition: Chemical equilibrium = the condition where the concentrations of all reactants and products constant with time Chemical equilibrium involves forward and reverse reaction 2H2 + O2 2H2O

Example:

Forward reaction (Right direction) = 2H2 + O2 Reactant 2H2O Product

1

Reverse reaction (Left direction) =

Audi Majdan DMC 101 KLIUC

2H2 + O2 Reactant

2H2O Product

Any reaction at chemical equilibrium: Forward rate = Reverse rate

Example:

2H2 + O2 2H2O Reactant Product Direction Right Left Producing Products Reactants

Forward rate Reverse rate

Equilibrium can be reached if there are NO reactant or product removed from the system

Examples of Equilibrium
Audi Majdan DMC 101 KLIUC 2

a)

Vapor pressure: equilibrium of molecule movement between the liquid and gas phase.

Rate of molecules leaving the liquid phase (evaporation) = Rate of molecules entering the gas phase (condensation)

b)

Formation of crystal of the ionic solid in a saturated aqueous solution:

3

Audi Majdan DMC 101 KLIUC

Rate of ions leaving the crystal = Rate of ions entering the crystal lattice

The Equilibrium Characteristics

Audi Majdan DMC 101 KLIUC 4

 Consider: AB (Forward Reaction) Reaction rate = k [A] (Reverse Reaction) Reaction rate = k [B] Forward reaction rate = kf [A] Reverse reaction rate = kr [B] At Equilibrium: Forward Rate = Reverse Rate kf [A] = kr [B] (kf) (kr) (Both rate constants are not equal even though both rates are equal) Representation of equilibrium:
Audi Majdan DMC 101 KLIUC 5

What happens at equilibrium? Characteristics Concentrations of BOTH reactant and product (A and B) Forward and reverse reaction rates Forward and reverse rate constant Properties constant equal unequal

Audi Majdan DMC 101 KLIUC

Classic Example of Equilibrium Process: The Haber Process Haber Process: a chemical process to produce ammonia N2(g) + 3H2(g) 2NH3(g)

Forward Reaction (Producing Ammonia):

Audi Majdan DMC 101 KLIUC 7

Reverse Reaction (Producing Nitrogen & Hydrogen):

Audi Majdan DMC 101 KLIUC

Equilibrium concentrations of reactants and products will be the same if reached from either direction (starting from either pure reactants or pure product) The Equilibrium Constant & Equilibrium Expression

Equilibrium expression = an expression to show the relationship between reactants and products at equilibrium Equilibrium Expression

In Concentration

In Pressure

Audi Majdan DMC 101 KLIUC

a) Equilibrium Concentration, Kc

Expression

in

Equilibrium expression =

Equilibrium constant

Equilibrium expression

[ ] = equilibrium concentration of the reactants and products.

Audi Majdan DMC 101 KLIUC

10

Example: Haber process: N2(g) + 3H2(g) 2NH3(g)

Exercise 1 Write the equilibrium expression for Kc for these reactions:

a) b)

2O3 (g) 3O2 (g) 2NO (g) + Cl2 (g) 2NOCl (g)

Equilibrium Expression in Pressure, Kp Kc = equilibrium constant in concentration (M) If reactants and products are gases = equilibrium expression in partial pressures:

Audi Majdan DMC 101 KLIUC

11

Exercise 2 Write the equilibrium expression for Kp for these reactions:

a) b)

N2(g) + 3H2(g) 2NH3(g) N2(g) + O2(g) 2NO(g)

Note: Equilibrium constants = unit less

Relationship of Magnitude of Kc/Kp & Direction of a Chemical Equation

Case 1:
Audi Majdan DMC 101 KLIUC 12

 If [Products] > [Reactants] = LARGE Kc = The equilibrium move to the right: the equilibrium mixture contains mostly product aA + bB cC + dD Case 2: If [Reactants] > [Products] = SMALL Kc = The equilibrium move to the left: the equilibrium mixture contains mostly reactant aA + bB cC + dD Conclusion: Kc >> 1 More Products produced Kc << 1 More Reactants produced Calculation of Kc or Kp given either direction

Direction of equilibrium "forward" and "reverse"

reaction:

Audi Majdan DMC 101 KLIUC

13

Forward Reaction: AB Kc = x Reverse Reaction: AB Kc = ? = 1/x The equilibrium expression for a reaction written in one direction is the reciprocal of the one for the reaction written in the reverse direction

Example: Forward:
Audi Majdan DMC 101 KLIUC 14

Kc = 0.212 (100 C) Equilibrium expression:

2 [ NO 2 ] Kc = [ N 2 O4 ]

Reverse:

Equilibrium expression:

Kc =

1 0.212

= 4.72 Types of Equilibrium

Two types of equilibrium: Homogenous & Heterogeneous Homogeneous reactions: all reactants and products existing in the same phase
15

Audi Majdan DMC 101 KLIUC

Homogeneous reaction at equilibrium = homeogeneous equilibrium Example: 4NH3 (g) + 7O2 (g) 4NO2 (g) + 6H2O (g) Heterogeneous reactions = a reactant or a product in a different phase from the other components Heterogeneous reaction at equilibrium = heterogeneous equilibrium Example: CaCO3 (s) CaO (s) + CO2 (g) Equilibrium Expression for Heteregenous Equilibrium Example:

Audi Majdan DMC 101 KLIUC

16

What is the Kc for this reaction?

The correct equilibrium expression: Kc = [CO2] Why ?

Audi Majdan DMC 101 KLIUC

17

For a heterogeneous equilibrium expression: 1) The concentrations of solids and liquids is not included

Solid

Liquid

2)

Only concentrations of gases and aqueous solution are included Aqueous Gas

Calculation of Equilibrium Constants, Kc 2 MAIN POINTS: Only equilibrium concentration for both reactant and product can give the value of Kc Initial concentration of both reactant and product WILL NOT give the value of Kc Calculation of Kc depends on the type of information given:
Audi Majdan DMC 101 KLIUC 18

All equilibrium concentrations of reactant and product given

1)

Example: Calculate the equilibrium constant for the decomposition of N2O4 which has the equilibrium concentration of 5.3 M N2O4 and 0.75 M NO2 at 337 K.

Solution

N2O4 (g) 2NO2 (g) [ NO ] Kc = [ N O ]

2 2

= (5.3) = 0.106 Example: A mixture of H2, N2 and NH3 was allowed to reach equilibrium conditions at 472 C. The
Audi Majdan DMC 101 KLIUC 19

( 0.75 )

concentration at equilibrium was found to contain 0.1207M H2, 0.0402M N2 and 0.00272M NH3. Determine the equilibrium constant, Kc.

Kc = (0.00272)2/(0.0402)(0.1207)3 Kc = 0.105 2) Initial concentrations and ONLY several equilibrium concentrations of the components given General steps:
1.

2.

3.

List initial and equilibrium concentrations of all reactants and products involved in the equilibrium Calculate the change in concentration when reaches equilibrium for reactants or products when both the initial and equilibrium concentrations given Calculate the predicted changes in concentration for all reactants and products
20

Audi Majdan DMC 101 KLIUC

4.

in the equilibrium by using the stoichiometry of the reaction Calculate the equilibrium concentrations & Kc from initial and changes in concentration

Example: In Haber's reaction, 0.025 mole of H2(g) and 0.010 mole of N2(g) are mixed in a 2L vessel at 472 C. The mixture is allowed to come to equilibrium and the concentration of NH3(g) is recorded to be 3.18 x 10-5M. Calculate Kc. Solution 1. Information given: Initial concentrations: Concentration (M) = number of moles per unit volume (n/V) [H2] = 0.025 mole / 2L = 0.0125M [N2] = 0.010 mole / 2L = 0.005M
Audi Majdan DMC 101 KLIUC 21

[NH3] = 0M initially Final (equilibrium) concentrations: [H2] = ? [N2] = ? [NH3] = 3.18 x 10-5M 2. Only Initial and Final concentrations of NH3 known: Find changes in concentration: [NH3] = Equilibrium concentration - Initial concentration [NH3] = 3.18 x 10-5M - 0M = 3.18 x 10-5M 3. Find changes in concentration in other components by using stoichiometry: N2(g) + 3H2(g) 2NH3(g) [N2] [N2] =
Audi Majdan DMC 101 KLIUC 22

3[H2]

2[NH3]

1 [N2] 1.59 x 10-5M N2

2[NH3] 3.18 x 10-5M NH3

= (3.18 x 10-5M NH3) x (1 N2 / 2 NH3) = 1.59 x 10-5M of N2 [H2] = 3[H2] 4.77 x 10-5M H2 2[NH3] 3.18 x 10-5M NH3

(3.18 x 10-5M NH3) x (3 H2 / 2 NH3) = 4.77 x 10-5M of H2 4. Calculate the equilibrium concentration of all reactants and products: N2: Initial = 0.005M, Changes = 1.59 x 10-5M, Equilibrium = (0.005M - 1.59 x 10-5M) = 4.98 x 10-3M
23

Audi Majdan DMC 101 KLIUC

H2:

Initial = 0.0125M Changes = 4.77 x 10-5M Equilibrium = (0.0125M - 4.77 x 10-5M) = 1.245 x 10-2M Equilibrium = 3.18 x 10-5M

NH3:

5. Calculate Kc by substituting all equilibrium concentrations: Kc = [NH3]2/[N2][H2]3 = (3.18 x 10-5)2 / (4.98 x 10-3)(1.245 x 10-2)3 = (1.01 x 10-9) / (4.98 x 10-3)(1.95 x 10-6) = 0.104 Concentration N2(g) + 3H2(g) 2NH3(g) Initial 0.005M 0.0125M 0 Changes -1.59 x -4.77 x 10- +3.18 x 5 10-5M M 10-5M Equilibrium 4.98 x 1.245 x 3.18 x 105 10-3M 10-2M M Exercise 3
Audi Majdan DMC 101 KLIUC 24

A mixture of 0.2 mol of CO2, 0.1 mol of H2 and 0.16 mol of H2O is placed in a 2 L vessel. The following equilibrium is established: CO2 (g) + H2 (g) CO (g) + H2O (g) At equilibrium [H2O] = 0.0856 M. Calculate the equilibrium concentrations of CO2, H2 and CO. Determine the equilibrium constant, Kc. Uses of Equilibrium Constant, Kc
1.

2.

3.

Predicting direction of a reaction (towards making product or more reactant) Calculating equilibrium concentrations (Equilibrium concentration for some of the components given and determining the concentration of an unknown component) Calculating equilibrium concentrations (Only initial concentrations of reactants and products given)

1. Prediction of Reaction Direction

Audi Majdan DMC 101 KLIUC

25

The magnitude of the reaction quotient, Q indicates the direction of a reaction will proceed Reaction quotient, Q = value of equilibrium expression when initial concentration are substituted in the expression

Value Q < Kc Q = Kc Q > Kc NOTE:

Direction of Reaction Reaction will proceed to the right System = equilibrium Reaction will proceed to the left

a) Value of initial concentration substituted in equilibrium expression: K=Q b) Value of equilibrium concentration substituted in equilibrium expression:
Audi Majdan DMC 101 KLIUC 26

K = Kc Initial Concentration Equilibrium Concentration

Initial concentration t=0s

Equilibrium concentration t = 15 s

Audi Majdan DMC 101 KLIUC

27

Example: The value of Kc for the Haber reaction at 472 C is 0.105. The following amounts of H2(g), N2(g) and NH3(g) was put in a 3.0L container at 472 C. Determine the direction of the reaction. N2(g) + 2H2(g) 2NH3(g)

H2(g) = 0.5 mole N2(g) = 8.3 moles NH3(g) = 1.8 mole

Solution 1. Convert moles to concentration [H2] [N2] [NH3] = 0.5mol/3.0L = 0.167 M Initial = 8.3mol/3.0L = 2.77 M Concentration = 1.8mol/3.0L = 0.60 M N2(g) + 3H2(g) 2NH3(g)
Audi Majdan DMC 101 KLIUC

2. State the equilibrium expression:

28

3. Insert the initial concentration of reactants and products into the equilibrium expression: Q= (0.600)2 (2.77) x (0.167)3 Reaction Quotient (Q) = 27.9 27.9 > 0.105 Q > Kc the reaction proceed to the left Exercise 4 At 448 C, the equilibrium constant, Kc for the reaction H2(g) + I2(g) 2HI(g)

= 27.9

Audi Majdan DMC 101 KLIUC

29

is 51. Predict the direction of the reaction will proceed to reach equilibrium at 448 C if 2.0 x 10-2 mole of HI, 1.0 x 10-2 mole H2 and 3.0 x 10-2 mole I2 are in inserted into a 2.0 L tank. 2. Calculation of the Equilibrium Concentration/Pressure of a Reactant or Product Given:
1. 2.

Kc/Kp Equilibrium concentration/pressure for some of the species.

Example: (500 C) Kp = 1.45 x 10-5 for the Haber reaction: At equilibrium the partial pressure of the H2(g) is 1.32 atm and for N2(g) is 0.648 atm. What is the partial pressure of the NH3(g) in the equilibrium mixture? N2(g) + 3H2(g) 2NH3(g) Solution
Audi Majdan DMC 101 KLIUC 30

 Substitute equilibrium partial pressures of H2 and N2 and value for Kp: 1.45 x 10-5 = (PNH3)2 (0.648) x (1.32)3 PNH3 = (2.16 x 10-5)1/2 PNH3 = 4.64 x 10-3 atm Exercise 5 At 500K, the reaction PCl5(g) PCl3(g) + Cl2(g) has Kp = 0.497. In an equilibrium mixture at 500 K, the partial pressure of PCl5 is 0.860 atm and for PCl3 is 0.350 atm. Calculate the partial pressure of Cl2 in the equilibrium mixture.

Audi Majdan DMC 101 KLIUC

31

3. Calculation of Equilibrium Concentrations/Pressure of a Reactant or Product Given:

1. 2.

Kc/Kp Initial concentration/pressure species.

of

all

Example: N2(g) + O2(g) 2NO(g) Kc = 2.1 x 10-3 (2500K) A reaction is setup with 5.75M N2(g), 4.89M O2(g) and 0 M NO(g). What will be the equilibrium concentrations of all components?

Audi Majdan DMC 101 KLIUC

32

Solution Concentration N2(g) + O2(g) 2NO(g) Initial 5.75 M 4.89 M 0M Changes ?M ?M ?M Equilibrium ? M ?M ?M For Reactant: Equilibrium [ ] = Initial [ ] Changes [ ] For Product: Equilibrium [ ] = Initial [ ] + Changes [ ]
1)

Assume: x = changes in [N2] Equilibrium [N2] = (5.75M - x M) By using the stoichiometry: 1 mole N2 x M of [N2] 1 mole O2 x M of [O2]

2)

Equilibrium [O2] = (4.89M - x M)

Audi Majdan DMC 101 KLIUC

33

1 mole N2 x M of [N2]

2 moles NO 2x M of [NO]

Equilibrium [NO] = (0 M + 2x M) Concentration N2(g) + O2(g) 2NO(g) Initial 5.75M 4.89M 0 Changes -x M -x M +2x M Equilibrium (5.75-x M) (4.89-x M) 2x M Substitute expression:
3)

in

equilibrium

Kc =

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

2.1 x 10 = = 2.1 x 10 =
-3

-3

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

( 2x) ( 5.75 x )( 4.89 x )

2

4x ( 28.1 10.6 x + x
2

(2.1 x 10-3) x (28.1 - 10.6x + x 2) = 4x 2 0.0590 - 0.0223x + 0.0021x 2 = 4x 2

Audi Majdan DMC 101 KLIUC 34

4.00x 2 + 0.0223x - 0.059 = 0 Find x by using quadratic formula:

4)

Quadratic solutions: x = 0.119 M or x = -0.124 M (negative) x = 0.119 M

5)

Equilibrium concentrations: [N2]= (5.75 - 0.119) = 5.63M [O2] = (4.89 - 0.119) = 4.77M [NO] = (2 x 0.119) = 0.238M

Check answer. Substitute into equilibrium constant expression: Kc =

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

the

= (0.238)2 / (5.63) x (4.77)

Audi Majdan DMC 101 KLIUC 35

Kc = 2.11 x 10-3 Exercise 6 A 1.0 L flask is filled with 1.0 mole of H2 and 2.0 moles of I2 at 448 C. The value of the equilibrium constant, Kc for the reaction is 50.5 at 448 C. Determine the concentrations of H2, I2 and HI in the flask at equilibrium. H2(g) + I2(g) 2HI(g)

Relationship between Kc and Kp

Audi Majdan DMC 101 KLIUC

36

 Relationship between Kc and Kp: Kp = Kc(RT) n R = Gas constant = 0.0821 L atm mole-1K-1 n = moles of products - moles of reactants Example: N2O4(g) 2NO2(g) n = (2-1) = 1 Kp = Kc(RT)1 = Kc(RT) Exercise 7
Audi Majdan DMC 101 KLIUC 37

Calculate Kp for the Haber process with Kc of 9.6 at 300 C. N2(g) + 3H2(g) 2NH3(g)

Le Chtelier's Principle

Haber process has been studied in terms of factors affecting the equilibrium concentrations of NH3: N2(g) + 3H2(g) 2NH3(g)

Experiment Pressure Temperature Measurement 1 Maintained Varied Equilibrium concentration 2 Varied Maintained of NH3

Audi Majdan DMC 101 KLIUC

38

 Observation: o At constant P: o At constant T:

[NH3] when T [NH3] when P

Le Chtelier's Principle:

If a system is in equilibrium, and is disturbed by a change in temperature, pressure or concentration of one of the component, the system will shift its equilibrium so as to counteract the effect of this disturbance
Audi Majdan DMC 101 KLIUC 39

Removal of Component Equilibrium Non Equilibrium

One of the components removed

Addition of Component

Equilibrium

Non Equilibrium

One of the components added (added concentration)

Audi Majdan DMC 101 KLIUC

40

Effect of Concentration

Le Chtelier's principle states that if the concentration of one of the components of the reaction (either product or reactant) is changed, the system will respond in such a way as to counteract the effect CASE 1: Removal of a component

If a substance (either reactant or product) is removed from a system, the equilibrium will shift so as to produce more of that component to achieve equilibrium

Audi Majdan DMC 101 KLIUC

41

1 Reactant A B C

Equilibrium

Product

2 Reactant A is removed Reactant B C Equilibrium Product

Direction of reaction Reverse Reaction = produce BACK reactant A and MORE reactant B & C
Audi Majdan DMC 101 KLIUC 42

3 Reactant A is formed back Reactant New Equilibrium A B C Product

Reactant A reproduced B higher concentration C higher concentration

([A] ) ([B] ) ([C] )

Product All product with LOWER concentration because producing more reactant ([Product] )
Audi Majdan DMC 101 KLIUC 43

CASE 2: Addition of a component If a substance (either reactant or product) is added to a system, the equilibrium will shift so as to consume more of that component to achieve equilibrium Reactant A B C Equilibrium Product

Audi Majdan DMC 101 KLIUC

44

2 Reactant A is added Reactant Equilibrium A B C Product

Direction of reaction Forward Reaction = produce MORE product

Audi Majdan DMC 101 KLIUC

45

3 Reactant A is reduced Reactant New Equilibrium A B C Product

Reactant A reduced B lower concentration C lower concentration

([A] ) ([B] ) ([C] )

Product All product with HIGHER concentration because reactant producing more product ([Product] )

Audi Majdan DMC 101 KLIUC

46

Example: Haber reaction: N2 (g) + 3H2 (g) 2NH3 (g) Scenario 1: Addition of H2 What happen if we started with a Haber reaction at equilibrium and then added more H2 (g) to the reaction?

Audi Majdan DMC 101 KLIUC

47

 Before the addition of H2, the system is in equilibrium. When the H2 is added, the system responds to counteract the disturbance caused by the added H2(g) by: consuming H2 and N2 (reactants) producing more NH3 (product) Forward rate = k1 [N2] [H2]3 The addition of H2(g) causes the system to shift to the right = production of more NH3

The system will reach a new equilibrium which different from the original equilibrium. The new equilibrium state contains: Product: Higher concentration of NH3 Reactant: Lower concentration of N2 Higher concentration of H2
Audi Majdan DMC 101 KLIUC

[NH3] [ N 2] [H2]
48

Value of Kc constant

Scenario 2: Addition of NH3 What would happen if we repeated the experiment, but added NH3(g) instead of H2(g)? The system would respond by decomposing some of the added NH3(g) a new equilibrium condition would be established: Reactant: Higher concentrations of H2 and N2 [H2] & Product: Higher concentrations of NH3 [NH3]

[N2]

Value of Kc constant

Audi Majdan DMC 101 KLIUC

49

Effects of Volume and Pressure

Le Chtelier's Rule: Increasing pressure (P) on a system, the system will responds by trying to reduce the pressure

The system will responds depending on the stoichiometry of the reaction: Increasing P: the reaction shifting to the direction with less number of molecules Decreasing P: the reaction shifting to the direction with higher number of molecules Example: A+B 2 molecules 3C 3 molecules

1)

Increase P: Reaction shifts to the less number of molecules (to the left) P
50

Audi Majdan DMC 101 KLIUC

2)

Decrease P: Reaction shifts to the higher number of molecules (to the right) P N2(g) + 3H2(g) 2NH3(g) 4 molecules 2 molecules

Example:

Increasing P shifts to the right (less number of product (NH3) molecules) Decreasing P shifts to the left (higher number of reactant molecules) Effects of volume (V) will have the opposite of changes in P. Increase V: Reaction shifts to the higher number of molecules V Decrease V: Reaction shifts to the less number of molecules V Value of Kc constant

Audi Majdan DMC 101 KLIUC

51

Effect of Temperature

Value of Kc remains constant when [ ] or P of components changes But Kc changes when there is changes in Temperature (T)

Chemical reactions have heat change associated with the reaction Exothermic reactions heat release when the reaction proceeds in the forward direction Endothermic reactions heat release when the reaction proceeds in the reverse direction (= heat is absorbed in the forward direction) Exothermic: Reactants Products + Heat Endothermic: Reactants + Heat Products Increasing T : the equilibrium will shift to minimize the effect of the added heat The reaction will shift in the appropriate direction such that the added heat is absorbed
Audi Majdan DMC 101 KLIUC 52

 When heat is added to: Exothermic reactions at equilibrium: products will be consumed to produce reactants (shift to the LEFT) Endothermic reactions at equilibrium: reactants will be consumed to produce products (shift to the RIGHT)

Effect of T on K:

Exothermic: T K Endothermic: T K The Effect of Catalysts A catalyst changes the rate, but does not change K (K constant)

Audi Majdan DMC 101 KLIUC

53