Chapter 14 Chemical Equilibrium

Characteristics of Chemical Equilibrium

Many reactions fail to go to completion. [Reactants] stop decreasing, and [Products] stop increasing. The reaction reaches equilibrium. If there are more: products than reactants = product favored. reactants than products = reactant favored.

Equilibrium is Dynamic
Reactants convert to products aA+bB cC+dD BUT, products can also react to make reactants. Equilibrium occurs when [A], [B], [C] and [D] stop changing - a dynamic equilibrium:
Species do not stop forming OR being destroyed. Rate of formation = rate of removal. Concentrations are constant.

Equilibrium is Independent of Direction

N2(g) + 3 H2(g)
Start with: 1 mol N2 + 3 mol H2

2 NH3(g)
or with: 2 mol NH3

They will form identical equilibrium mixtures

Equilibrium & Catalysts

Catalysts do not affect equilibrium concentrations. Catalysts: speed up the forward reaction but also speed up the reverse reaction. decrease the time needed to reach equilibrium.

The Equilibrium Constant

2-butene isomerization: At equilibrium: rateforward = ratereverse

The Equilibrium Constant

The isomerization is elementary, so: kforward[cis] = kreverse[trans] or [trans] kforward = [cis] kreverse

This ratio is named the equilibrium constant, Kc: kforward Kc = = kreverse [trans] = 1.65 (at 500 K) [cis]
c concentration based

Equilibrium constants are temperature dependent:

T (K) Kc 500 1.65 600 1.47 700 1.36

The Equilibrium Constant

For a general reaction: aA+bB cC+dD
Products raised to stoichiometric powers

kforward Kc = = kreverse

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

divided by reactants raised to their stoichiometric powers

The Equilibrium Constant

Examples N2(g) + O2(g) 2 NO(g) [NO]2 Kc = [N ] [O ] 2 2

S8(s) + O2(g)

SO2(g)

[SO2] Kc = [O ] 2

S8 is ignored. All pure solids are omitted from Kc.

Equilibria Involving Pure Liquids & Solids [Solid] is constant throughout a reaction. density pure solid concentration = mol. wt
[S8] = dS / mol. wt S8
8

g/L g / mol

d and mol. wt. are constants, so [S8] is constant. This constant factor is absorbed into Kc.

Pure liquids are omitted for the same reason.

Equilibria in Dilute Solutions

Water is omitted from Kc in dilute solution reactions:
It is in large excess (pure water = 55.5 M). Even if consumed or produced, [H2O] constant. The constant factor is incorporated into Kc.

NH3(aq) + H2O()

NH4+(aq) + OH-(aq)

[NH4+][OH-] Kc = [NH ] = 1.8 x 10-5 3

(at 25 C)

(Units are customarily omitted from Kc)

The Equilibrium Constant

What is the equilibrium constant for: SiH4(g) + 2 O2(g) SiO2(s) + 2 H2O(g) ? Omit SiO2 (a solid) Include H2O (a gas) Write down Kc for: 2 NaOH(aq) + H2SO4(aq) Omit H2O (aq. solution) [H2O]2 [SiH4][O2]2

Na2SO4(aq) + 2 H2O() [Na2SO4] [H2SO4][NaOH]2

Kc for Related Reactions

N2(g) + 3 H2(g) 2 NH3(g) [NH3]2 Kc = [N2][H2]3 change Kc [NH3] Kc = [H ]3 2 [N2] 2

Change the stoichiometry N2(g) + 3 2 H2(g)

(original reaction)

NH3(g)

This new Kc is the square root of the original Kc. Multiply an equation by a factor Raise Kc to the power of that factor.

Kc for Related Reactions

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

[NH3]2 Kc = [N2][H2]3 Reverse a reaction 2 NH3(g) Invert Kc: N2(g) + 3 H2(g)

[N2][H2]3 Kc = [NH3]2

Kc for a Combined Reaction

If a reaction can be written as a series of steps: step 1 N2(g) + O2(g) 2NO(g) 2 NO2(g) 2 NO2(g) [NO]2 Kc = [N2][O2] [NO2]2 Kc = [NO]2[O2] [NO2]2 Kc = [N2][O2]2

step 2 2 NO(g) + O2(g) overall N2(g) + 2 O2(g)

The overall Kc is the product of the steps: [NO2]2 [NO]2 [NO2]2 Kc(step1) x Kc(step2) = = 2[O ] [N2][O2] [NO] 2 [N2][O2]2

Equilibrium Constants in Terms of P

In a constant-V reaction, partial pressures change as concentrations change. At constant T, P is proportional to molar conc.: Ideal gas: and for gas A: PV = nRT PAV = nART nA RT = [A]RT PA= V

P is easily measured, so another K is used

Equilibrium Constants in Terms of P

For a gas-phase reaction: a A(g) + b B(g) c C(g) + d D(g)

PCc PDd Kp = PAa PBb

p pressure based

In general:

Kp = Kc(RT)ngas

with ngas = ngaseous products ngaseous reactants = (c + d) (a + b)

Equilibrium Constants in Terms of P

Calculate Kp from Kc for: 2 NH3(g) N2(g) + 3 H2(g) Kp = Kc(RT)ngas T = 25 + 273 = 298 K ngas = 2 (3 + 1) = 2 Kp = 5.8 x 105 0.0821 L atm Kc = 5.8 x 105 @ 25 C.

Use R in L/mol units. [ ] has mol/L units. -2

mol-1

K-1(298

K)

= 9.7 x 102 mol2 L-2 atm-2 Kp = 9.7 x 102 atm-2

mol and L units are assumed to cancel (units omitted from Kc).

Determining Equilibrium Constants

If all the equilibrium concentrations are known its easy to calculate Kc for a reaction. Example Consider: 2 A (aq) B (aq) At equilibrium [A] = 2.0 M & [B] = 4.0 M. What is Kc? [B] kforward Kc = = [A]2 kreverse 4.0 Kc = 2 = 1.0 (2.0)

Determining Equilibrium Constants

Determine Kc for these three equilibrium mixtures of 2-butene:

[trans] (# of ) Kc = [cis] = (# of ) (45 ) =9 a) Kc = (5 ) c) Kc = (5 ) = 9 (45 ) (25 ) b) Kc = =1 (25 )

Determining Equilibrium Constants

In other cases stoichiometry is used to find some concentrations. Example H2(g) and I2(g) were added to a heated container. [H2]initial = 0.0100 mol/L and [I2]initial = 0.00800 mol/L. At equilibrium [I2] = 0.00560 mol/L. Determine Kc. H2(g) + I2(g) 2 HI(g)

Determining Equilibrium Constants

Write a balanced equation; fill in [ ]initial: H2(g) +
[ ]initial 0.01000

I2(g)
0.00800

2 HI(g)
0
Let HI made = 2x

Use stoichiometry to predict changes:

[ ]change -x -x 2x

1H2 2HI so H2 lost = x

1I2 2HI so I2 lost = x

Add [ ]initial and [ ]change to get [ ]equilib

[ ]equilib 0.01000 - x 0.00800 - x 2x

Determining Equilibrium Constants

[ ]equilib H2(g) + 0.01000 - x I2(g) 2 HI(g) 0.00800 - x 2x

Since [I2] = 0.00560 M at equilibrium 0.00560 = 0.00800 - x x = 0.00240 M [H2]equilib = 0.01000 - (0.00240) = 0.00760 M [I2]equilib = 0.00800 - (0.00240) = 0.00560 M [HI]equilib = 2(0.00240) = 0.00480 M [HI]2 (0.00480)2 Kc = = = 0.541 [H2][I2] (0.00760)(0.00560)

Meaning of the Equilibrium Constant

When: Kc >> 1 Reaction is strongly product favored. very little reactant remains. often written as a forward reaction only. assume reaction goes to completion. Kc << 1 Reaction is strongly reactant favored. very little product forms. usually written as no reaction or NR. Kc 1 Reactants & products present at equilibrium. use equilibrium methods discussed here.

Predicting the Direction of a Reaction

The reaction quotient, Q can predict the direction of a reaction: For the reaction: aA + bB [C]c [D]d Q = [A]a [B]b cC + dD

Q looks identical to Kc, BUT the concentrations are not equilibrium values. (Kc = Q whenever a system is at equilibrium)

Predicting the Direction of a Reaction

[Products] Q = [Reactants]
Changes as a reaction moves to equilibrium

[Products]equilib Kc= [Reactants] equilib

Constant! (If T is constant)

If Q < Kc, Q must increase to reach equilibrium. make more product (and less reactant). move forward. If Q > Kc, Q must decrease to reach equilibrium. make less product (and more reactant). move back.

Predicting the Direction of a Reaction

Predicting the Direction of a Reaction

2 SO2(g) + O2(g) 2 SO3(g) Kc = 245 at 1000 K Predict the direction of the reaction if SO2 (0.085 M), O2 (0.100 M) and SO3 (0.250 M) are mixed in a reactor at 1000 K. [ SO3]2 (0.250)2 Q = [SO ]2[O ] = 2(0.100) = 86.5 (0.085) 2 2 Q < Kc, Q must increase to reach equilibrium. Need more product (less reactant). Forward direction.

Calculating Equilibrium Concentrations

If Kc is known, [ ]equilib can be calculated. Problem 2 HI(g) H2(g) + I2(g) 0.0500 mol of HI is placed in an empty 1.00 L flask at 600. K. What will be [HI], [H2] and [I2] at equilibrium? Kc = 76 at 600. K.

Calculating Equilibrium Concentrations

H2(g)
[ ]initial [ ]change [ ]equilib 0
1H2 2HI

I2(g)
0
1I2 2HI

2 HI(g)
0.0500
Amount lost

Change on reaching equilibrium:

+x +x +x +x -2x

0.0500 2x

[HI]2 (0.0500 2x)2 Kc = = [H2][I2] (x)(x) Since Kc = 76 76 x2 = (0.0500 2x)2

Calculating Equilibrium Concentrations

76 x2 = (0.0500 2x)2

Take the square root of both sides: 8.718 x = (0.0500 2x) 10.718 x = 0.0500 x = 4.67 x 10-3 or or 6.718 x = -0.0500 x = -7.44 x 10-3

Ignore the negative root (x cannot be negative).

Calculating Equilibrium Concentrations

So: [H2]equilib = x = 0.00467 M [I2]equilib = x = 0.00467 M [HI]equilib = 0.0500 2x = 0.0407 M Its a good idea to check your work:
Matches Kc given in the problem

[HI]2 (0.0407 M)2 Kc = = = 76. [H2][I2] (0.00467 M)(0.00467 M)

Calculating Equilibrium Concentrations

Enough A is added to an empty container so that [A]initial = 0.1000 M. What are [A], [B] and [C] at equilibrium? A(g) B(g) + C(g) Kc = 2.500
[ ]Initial [ ]change [ ]equilib 0.100 -x (0.100 - x) 0 x x 0 x x

(x)(x) [B][C] Kc = = (0.1000 x) [A] x2 + 2.500 x 0.2500 = 0

x2 2.500 = (0.1000 x)
A quadratic equation

Calculating Equilibrium Concentrations

ax2 + bx + c = 0 has two roots (solutions): Here: 1x2 + 2.500 x 0.2500 = 0 a b c x= 2.500 (2.500)2 (4)(1)(0.250) 2(1) or -2.596 M x = -b b2 - 4ac 2a

x = +0.0963 M

Calculating Equilibrium Concentrations

Ignore the negative root (negative concentration!) Then x = 0.0963 M, and: [ A ] = 0.1000 - x = 0.0037 M [ B ] = x = 0.0963 M [ C ] = x = 0.0963 M Most of the A is converted to products. [B][C] (0.093)(0.093) Check: = = 2.5 = Kc [A] 0.037

Le Chateliers Principle
If a system is at equilibrium and the conditions are changed so that it is no longer at equilibrium, the system will react to reach a new equilibrium in a way that partially counteracts the change
A system at equilibrium resists change. If pushed, it pushes back

Changing Concentrations
aA + b B cC + dD

Add A (or B) and the system adjusts to remove it. more product is created. the reaction shifts forward. Remove A (or B) the system adjusts to add more. more reactant is created. the reaction shifts backward.

Changing Concentrations

Changing V or P in Gaseous Equilibria

K does not change if P or V change. Equilibrium position may change. Consider: N2O4(g) 2 NO2(g)

If V doubles, all concentrations divide by 2: 5 moles of NO2 in 1 L, goes to 5 moles in 2 L. [NO2] = 5 M becomes [NO2] = 2.5 M.
[ NO2 ]2 Kc=Q= [ N2O4] At equilibrium ([ NO2 ])2 [ NO2 ]2 [ NO2 ]2 Q= = = = Kc [ N2O4] [ N2O4] [ N2O4] After V change, Q < Kc. Equilibrium shifts towards products

Changing V or P in Gaseous Equilibria

Consistent with Le Chatelier N2O4(g) 2 NO2(g)

V doubled = lower concentration. Minimize change by: Making more molecules (increase concentration). Shifting toward products; convert 1 molecule into 2. P doubled. Minimize the change by: Removing molecules (decrease P). Shifting toward reactants; convert 2 molecules into 1.

Changing V or P in Gaseous Equilibria

P and V changes have no effect if ngas = 0: H2(g) + I2(g) 2 HI(g)

If V is doubled, the system cannot adjust (there are 2 gas molecules on each side).

[HI]2 Kc=Q= [H2][I2] At equilibrium

([HI])2 [HI]2 [HI]2 Q = [H ][I ] = = = Kc [H2][I2] [H2][I2] 2 2 After V change, Q = Kc still at equilibrium!

Changing V or P in Gaseous Equilibria

Adding an inert gas to change P has no effect.
Total P increases V does not change, nor do nreactants or nproducts [reactant] and [product] do not change.

nA RT = [A]RT PA= V

Changing V by Adding Solvent

Kc is not changed by solvent addition or removal, but equilibrium position may change. H3O+(aq) + SO42-(aq) HSO4-(aq) + H2O() [H3O+][SO42-] = 0.012 Kc = [HSO4-] (at 25 C)

If the volume is doubled: The concentration of every species halves Q = Kc = Kc The equilibrium adjusts (moving toward products)

Changing Temperature
A change in T changes Kc.
Kc may increase or decrease if T is increased.

N2(g) + O2(g)
T (K) 298 900 2300 Kc 4.5 x 10-31 6.7 x 10-10 1.7 x 10-3

2 NO(g)

H = 180.5 kJ

Kc increases as T increases. Explained by LeChatelier

Changing Temperature
N2(g) + O2(g) 2 NO(g) H = 180.5 kJ

T increased? Minimize by removing heat. Forward reaction is endothermic. Equilibrium shifts forward, removing heat. T reduced? Add heat. Reverse reaction is exothermic. Equilibrium shifts in reverse, releasing heat.

Changing Temperature
Exothermic reactions: Kc decreases as T increases. Are less product favored at higher T.

Endothermic reactions: Kc increases as T increases. Are more product favored at higher T.

The Haber-Bosch Process

Production of NH3 for fertilizer from atmospheric N2 N2(g) + 3 H2(g) 2 NH3(g)

Process developed by Fritz Haber (chemist) and Carl Bosch (engineer). Perfected in 1914. Germany could not import guano from S. America and needed to make explosives

The Haber-Bosch Process

N2(g) + 3 H2(g) 2 NH3(g) H = -92.2 kJ

It is: Exothermic = product favored at low-T, but very slow at room-T, and must be heated. Carried out at high-P (200 atm), to favor product. Uses a catalyst to speed the reaction. Run at 450 C; NH3 is continually liquefied and removed.

The Haber-Bosch Process