CHAPTER 12(15)

Chemical Equilibrium

CONTENTS
12.1 12.2 12.3 12.4 12.5 12.6 The Concept of Equilibrium The Equilibrium Constant Heterogeneous Equilibria Calculating Equilibrium Constants Application of Equilibrium Constants Le Chteliers Principle

Learning Outcomes

Student should be able to use concept of equilibrium to calculate equilibrium constant and equilibrium concentrations. Able to apply Le Chaterliers Principle to predict the direction of a reaction hence apply it in commercial sense in increasing yield, reduce cost etc. Differentiate homogenous and heterogeneous equilibria, reaction quotient and Equilibrium constant
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12.1 The Concept of Equilibrium

Consider Colorless frozen N2O4. At room temperature, it decomposes to brown NO2. N2O4(g) 2NO2(g) At some time, the color stop changing and we have a mixture of N2O4 and NO2.

the concentration of all reactants and products no longer change with time.

N2O4 (g) 2 NO2 (g)

12.1 The Concept of Equilibrium

N2O4 (g) 2 NO2 (g)

Chemical equilibrium is the point at which the concentrations of all species are constant. (concentrations of reactants and products cease to change with time)

Chemical equilibrium occurs

opposing reactions are proceeding at equal rate.

fo a rwrd

Rate

= Rate

re e e v rs

N2O4 (g) - colorless NO2 (g) - reddish brown Concentration (color) remains constant at equilibrium
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time

12.1 The Concept of Equilibrium

Consider a simple reaction: A(g) B(g) We can write rate expressions for each reaction: Forward reaction: A B

Rate = kf[A] reaction) Rate = kr[B] reaction)

kf = rate constant (forward

Reverse reaction: B A

kr = rate constant (reverse

12.1 The Concept of Equilibrium

For gaseous substances we can use the ideal gas equation to convert between concentration and pressure: PV=nRT so M(Molarity) = (n/V) =(P/RT) For substances A and B:

[A] = (PA/RT) and [B] = (PB/RT) Ratefwd = kf(PA/RT) and Raterev = kr(PB/RT)

12.1 The Concept of Equilibrium

Place some pure compound A into a closed container. As A reacts to form B, the partial pressure of A will decrease and the partial pressure of B will increase. Expect forward reaction rate to slow and reverse reaction rate to increase. Eventually, we get to equilibrium where forward and reverse rates are equal.

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Haber Process
N2(g) + 3H2(g) 2NH3(g)

The reaction is carried out under conditions of high pressure and high temperature. Equilibrium can be established either by starting with N2 and H2 or by starting only with NH3.

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12.1 The Concept of Equilibrium

At Equilibrium:

Rearrange: a constant

PA PB kf = kr RT RT

( PB / RT ) = PB = k f = ( PA / RT PA kr This mixture is called an) equilibrium mixture.

This is an example of dynamic equilibrium.

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12.2 The Equilibrium Constant, K

We can write an expression for the relationship between the concentration of the reactants and products at equilibrium. This expression is based on the law of mass action. For a general reaction: aA + bB cC + dD Equilibrium expression:

[ C ] [ D] K= a b [ A] [ B]
c

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12.2 The Equilibrium Constant, K

When the reactions and products are all in gaseous form, equilibrium constant is expressed in terms of partial pressures of the gases.

( PC ) ( PD ) K= a b ( PA ) ( PB )
c d

The value of Keq does not depend on the initial concentrations of reactants and products.
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12.2 The Equilibrium Constant, K

When the reactants and products are all in aqueous form, Kc is used for equilibrium constant. c indicates the molar concentration (M) When the reactants and products are all in gaseous form, Kp is used for equilibrium constant. p indicates the partial pressures of the gases.
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12.2.1 The Magnitude of Equilibrium Constants, K

K is the ratio of products to reactants. The larger K the more products are present at equilibrium. The smaller the K the more reactants are present at equilibrium. If K >> 1, then products dominate at equilibrium and equilibrium lies to the right. K << 1, then reactants dominate at equilibrium and equilibrium lies to the left.
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The range of equilibrium constants, K

A: reaches product. K = 1/49

equilibrium,

little

B:reaches equilibrium, nearly all product K = 49/1 C: reaches equilibrium significant concentrations reactant & product. K = 25/25 =1 with of

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12.2.2 The Direction of the Chemical Equation and K

An equilibrium can be approached from any direction: Eg: N2O4 (g) 2 NO2 (g) The equilibrium constant for this reaction (at 100C) is:

Kp =

( PNO2 ) 2 ( PN 2O4 )

= 6.49

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12.2.2 The Direction of the Chemical Equation and Keq

For the reverse reaction: 2 NO2 (g) N2O4 (g) The equilibrium constant for this reaction (at 100C) is:

Kp =

( PN 2O4 ) ( PNO2 )
2

= 0.154

The equilibrium constant for a reaction in one direction is the reciprocal of the equilibrium constant of the reaction in the opposite direction.

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12.3 Heterogeneous Equilibria

Equilibria in which all reactants and products are present in the same phase are called homogeneous equilibria. Equilibria in which one or more reactants or products are present in a different phase are called heterogeneous equilibria. Consider: CaCO3(s) CaO(s) + CO2(g) Experimentally, the amount of CO2 does not depend on the amounts of CaO and CaCO3. WHY?
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12.3 Heterogeneous Equilibria

The concentration of a pure solid or pure liquid equals its density divided by its molar mass. Neither density nor molar mass is a variable thus the concentrations of solids and pure liquids are constant.

[ CaO ] PCO K= [ CaCO3 ]

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12.3 Heterogeneous Equilibria

CaO and CaCO3 are pure solids and have constant concentrations.

( constant 1) PCO K= ( constant 2)

Rearrange:

'

( constant 2) =K ( constant 1)

= PCO2

Therefore K p = PCO2

)
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12.3 Heterogeneous Equilibria

If a pure solid or pure liquid is involved in the heterogeneous equilibrium, its concentration is not included in the equilibrium constant expression. The amount of CO2 formed (pressure of CO2) will not depends on the amounts of CaO and CaCO3 present. However, they do participate in the reaction and must be present for an equilibrium to be established.
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12.3 Heterogeneous Equilibria

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12.4 Calculating Equilibrium Constants, K

Steps:

Tabulate initial and equilibrium concentrations (or partial pressures) for all species in the equilibrium. If an initial and an equilibrium concentration is given for a species, calculate the change in concentration. Use the coefficients in the balanced chemical equation to calculate the changes in concentration of all species. Deduce the equilibrium concentrations of all species. Use these equilibrium concentrations to calculate the value of the equilibrium constant.

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Example 1

A mixture of hydrogen and nitrogen in a reaction vessel is allowed to attain equilibrium at 472C. The equilibrium mixture of gases was analysed and found to contain 7.38 atm H2, 2.46 atm N2, and 0.166 atm NH3. From these data, determine Kp for

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

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Answer 1 N2(g) + 3H2(g) 2NH3(g)

Kp

(P ) = ( P )( P )3
2 NH 3 N2 H2 2 5

( 0.166) = 3 ( 2.46)( 7.38)

= 2.79 10
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Example 2

Enough ammonia is dissolved in 5.00 L of water at 25C to produce a solution that is 0.0124 M in ammonia. The solution is then allowed to come to equilibrium. Analysis of the equilibrium mixture shows that the concentration of OH- is 4.64 10-4 M. Calculate Kc at 25C for the reaction:

NH3(aq) + H2O(l)

NH4+(aq) + OH-(aq)

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Answer 2
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq) Initial Change Eqm
4.64 10-4 M 0.0124 M 0M 0M

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Answer 2
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq) Initial Change Eqm
0.0124 M 0M 0M

-4.64 10-4 M

+4.64 10-4 M +4.64 10-4 M

0.0119 M

4.64 10-4 M 4.64 10 M

-4

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Answer 2
NH3(aq) + H2O(l)
+

NH4+(aq) + OH-(aq)

Kc Kc

[ NH ][OH ] =
( 4.64 10 ) =
( 0.0119)

[ NH 3 ]

4 2

= 1.81 10 5

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Exercise 1

Methanol is produced commercially by the catalysed reaction of carbon monoxide and hydrogen: CO(g) + 2H2(g) CH3OH(g). An equilibrium mixture in a 2.00 L vessel is found to contain 0.0406 mol CH3OH, 0.170 mol CO, and 0.302 mol H2 at 500 K. Calculate Kp at this temperature. (Answer = 6.22 10-3)

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12.5 Application of Equilibrium Constants, K

The equilibrium constant can be used:

(i) to predict the direction in which a reaction mixture will proceed to achieve equilibrium. (ii) to calculate the concentrations of reactants and products once equilibrium has been reached.

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12.5.1 To Predict the Direction of Reaction: Writing Reaction Quotient

Consider: aA + bB

[ P ] p [Q] q Q= a b [ A ] [ B]

pP + qQ

Q is the called reaction quotient. a,b,p and q are the coefficients in the balanced chemical equation. The reaction quotient will equal the equilibrium constant, K, only if the system is at equilibrium: Q = K at equilibrium.
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12.5.1 To Predict the Direction of Reaction: Example

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

A mixture of 2.00 mol H2; 1.00 mol of N2 and 2.00 mol of NH3 in a 1.00L container is at 472C. Kp for the reaction at this temperature is 2.75 10-5 . Will N2 and H2 react to form more NH3?
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Answer
N2(g) + 3H2(g) 2NH3(g)

First, write the equilibrium-constant expression, Kp (or Q):

(P ) Q= To calculate the partial pressure of each gases, use PV=nRT (=P61.2Patm, P = 122 atm) )( ) (P = 122 atm, P
2 NH 3 3 N2 H2
H 2 N 2 N3 H

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Answer

Inserting the values into the reaction quotient, Q = 1.34 10-4 . Compare with Kp value, Kp =2.75 10-5 . Therefore the quotient will need to decrease for the system to achieve equilibrium. Can be achieved if decrease the pressure of NH3 or increase the pressures of H2 and N2. Thus the reaction proceeds toward equilibrium by producing H2 and N2 from NH3, i.e. the reaction proceeds from right to left.

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[Pr oducts ] [Re ac tan ts ] [Pr oducts ] Q= [Re ac tan ts ] K eq =

12.5.1 To Predict the Direction of Reaction

If Q < K,.. more product forms If Q > K,. more reactant forms If Q = K , no net change
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12.5.2 Calculating Equilibrium Concentrations

The same step used to calculate the equilibrium constants. Generally, we do not have a number for the change in the concentration. Therefore we need to assume that x mol/L of the species is formed (or used). The equilibrium concentrations are given as algebraic expressions.

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Example

A 1.000L flask is filled with 1.00 mol of H2 and 2.00 mol of I2 at 448C. Kp for the reaction at 448C is 50.5. H2(g) + I2(g) 2HI(g)

Question:

What are the partial pressures of H2, I2 and HI in the flask at equilibrium?

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Answer

First, calculate the initial partial pressures of H2 and I2 using PV=nRT. (PH2 = 59.17 atm, PI2 = 118.4 atm). Second, construct a table that consists of initial partial pressures.
H2(g) + I2(g)

2HI(g)

Initial Change Equilibrium

59.17 atm 118.4 atm

0 atm

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Answer

From the equation, 1 mol of H2 + 1 mol of I2 will produce 2 moles of HI. The partial pressures of H2 and I2 will decrease and the partial pressure of HI will increase.
H2(g) Initial (atm) Change (atm) Equilibrium (atm) + 59.17 -x 59.17 x I2(g) 118.4 -x 118.4 x 2HI(g) 0 +2x 2x

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Answer

Substitute the values into equilibrium-constant expression, Kp (value is 50.5).

Kp =

( P )( P
H2

( PHI ) 2
I2

( 2x) 2 = = 50.5 ) ( 59.17 x )(118.4 x )

4 x 2 = 50.5 x 2 177.6 x + 7.01103 b b 2 4ac then use x = 2a x = 137.6 or 55.3

46.5 x 2 8.97 103 x + 3.54 105 = 0

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Answer

Substitute x values into the expressions for equilibrium partial pressures. Using x = 137.6 will lead to negative partial pressures of H2 and I2 which are not chemically meaningful. So x = 55.3. PH2 = 59.17 x = 3.87 atm, PI2 = 118.4 x = 63.1 atm, PHI = 2x = 110.6 atm. Check:

Kp =

( P )( P
H2

( PHI ) 2
I2

(110.6) 2 = 50.1 = ) ( 3.87)( 63.1)

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12.6 Le Chteliers Principle

If a system at equilibrium is disturbed by a change in

temperature, Pressure (by changing the volume), the concentration of one of the components (adding or removing)

the system will shift its equilibrium position to reduce the effect of the disturbance. Changes in concentration or pressure cause shifts in equilibrium but K remains constant. Change in temperature increases or decreases the K value.
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12.6.1 Change in Reactant or Product Concentrations

A system at equilibrium: - if we add a substance (a reactant or a product) the reaction will shift reestablish equilibrium by consuming part of the added substance. - removal of a substance reestablish by forming more of the substance.

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

H2 added at this time Equilibrium reestablished

shift to reduce H2 conc. More NH3 will form N2 will be reduced

Concentration

i) Addition of H2

Initial Equilibrium H2 NH3

ii) Addition of NH3

shift to reduce NH3 conc. added NH3 will decompose to form N2 and H2 shift from left to right formation of more NH3.
N2

iii) Removal of NH3

Time
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12.6.2 Change in Pressure

Pressure will change if volume of the container changes. Volume decreases pressure increases equilibrium will shift towards the less number of gas molecules Volume increases pressure decreases equilibrium shift towards the more number of gas molecules

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12.6.2 Change in Pressure

E.g:

PCl5(g)

PCl3(g) + Cl2(g)

No. of gas molecules is more on RHS P , equilibrium shift to LHS producing more PCl5 (g) P equilibrium shift to RHS producing , PCl3(g) + Cl2(g) No change will occur if we increase the total pressure by the addition of a gas that is not involved in the reaction.

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12.6.3 Change in Temperature

Changes in concentration or total pressure cause shifts in equilibrium without changing the value of Keq . Applying Le Chteliers principle: Consider heat as a chemical reagent. Endothermic reaction (heat as a reactant)

A + B + Heat C
Exothermic reaction (heat as a product)

A + B C + Heat
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12.6.3 Change in Temperature

When the temperature is increased, the equilibrium shifts in the direction that absorbs heat. In an endothermic reaction, H>0: - increasing temperature or adding heat, the equilibrium shifts to the right (product) and K increases. In an exothermic reaction, H<0: - increasing temperature or adding heat, the equilibrium shifts to the left (reactant) and K decreases.
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12.6.3 Change in Temperature

Reaction Endothermic A + B + Heat C Exothermic A+BC+

Temperature Increase Decrease Increase Decrease

K Increase Decrease Decrease Increase

Heat

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Example
Consider the following equilibrium. N2O4(g) 2NO2(g) H = +58.0 kJ. Which direction will the equilibrium shift if: a) N2O4 is added
b) c) d) e)

NO2 is removed N2 is added the volume is increased. the temperature is decreased

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Answer
N2O4(g) 2NO2(g) H = +58.0 kJ

Kp

(P ) = (P )
2 NO 2 N 2O 4

a) N2O4 is added

Concentration of N2O4 increases, reaction shifts to the right to decrease back N2O4.

b) NO2 is removed

Concentration of NO2 decreases, reaction shifts to the right to increase back NO2. No effect, no shift in equilibrium position
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c) N2 is added

Answer
N2O4(g) 2NO2(g) H = +58.0 kJ d) The volume is increased.

V P the equilibrium shifts in the direction to , increase P by producing more gas molecules. It shifts to the right, 1 mol N2O4 molecules generates 2 mol NO2 molecules

e) the temperature is decreased.

The reaction is endothermic, heat is a reactant. Equilibrium shifts to the left, forming more N2O4, decreasing Kp.
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12.6.4 The Effect of Catalyst

A catalyst lowers the activation energy barrier for the reaction. Therefore, a catalyst will decrease the time taken to reach equilibrium. The catalyst has no effect on the equilibrium position. A catalyst does not effect the composition of the equilibrium mixture.
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Haber synthesis of ammonia

Ammonia is used for production of fertilizer, explosives and polymers.

57

N2 (g) + 3H2 (g) 2NH3 (g) H = -91.8 kJ/mol

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Haber Process

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Example
Methanol (CH3OH) is manufactured by reaction of carbon monoxide with hydrogen in the presence of a ZnO/Cr2O3 catalyst CO (g) + 2H2 (g) CH3OH (g) Ho = - 91 kJ

Does the amount of methanol (CH3OH) INCREASE, DECREASE or REMAIN THE SAME when an equilibrium mixture of reactants and product is subjected to the following changes?

The temperature is increased. CO is added. The volume of the vessel is decreased. The catalyst is removed
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Answer

Decrease. Because the reaction is exothermic. Reaction goes to the left (endothermic) to reduce back the T, Kp decreases, so concentration decreases. Increase. Because CO is a reactant, increasing CO, shift equilibrium to right. Increase. When the volume increases, pressure decreases. The reaction shifts to the sides with fewer molecules i.e. shifts to the right. Remains the same. Additional or removal of a catalyst does not affect the equilibrium composition.
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END of CHAPTER 12

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