CHAPTER 6 : EQUILIBRIA

CHEMICAL EQUILIBRIA

During a game, players enter and leave. Always the same number of players on field.

H2O(l)

H2O(g)

Photochromic sunglasses

AgCl + light (transparent)

Ag + Cl (dark)

Reversible reaction

a chemical reaction that can occur in both the forward and the reverse directions

N2(g) + 3H2(g)

2NH3(g)

Chemical equilibrium a state in which the forward and reverse reactions balance each other because they take place at equal rates

dynamic state; no net change

Law of chemical equilibrium

At a given temperature, a chemical system might reach a state in which a particular ratio of reactant and product concentrations has a constant value.

Equilibrium constant expression

ratio of molar concentrations of products to reactants; each raised to a power equal to coefficient in balanced equation

aA + bB

cC + dD

Equilibrium constant (Keq)

numerical value of the ratio of product to reactant concentrations constant only at a specific temperature

Value of equilibrium constant (Keq) shows the extent to which reactants are converted into products.

Keq > 1: Products are favored at equilibrium

Keq < 1: Reactants are favored at equilibrium

Homogenous equilibrium applies to reactions in which all reacting species are in the same phase. N2O4 (g) [NO2]2 2NO2 (g)

P2 Kp = P NO2 Kc = [N2O4] N2O4 In most cases Kc Kp aA (g) + bB (g) cC (g) + dD (g) Kp = Kc(RT)Dn Dn = moles of gaseous products moles of gaseous reactants = (c + d) (a + b)

Homogeneous Equilibrium CH3COOH (aq) + H2O (l)

-][H O+] [CH COO 3 3 Kc = [CH3COOH][H2O]

CH3COO- (aq) + H3O+ (aq) [H2O] = constant

[CH3COO-][H3O+] = Kc [H2O] Kc = [CH3COOH] General practice not to include units for the equilibrium constant.
14.2

Homogeneous equilibrium
all reactants and products in same phase

Write an equilibrium constant expression for:

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

2 [NH ] 3 ___________ [N2] [H2]3

The equilibrium concentrations for the reaction between carbon monoxide and molecular chlorine to form COCl2 (g) at 740C are [CO] = 0.012 M, [Cl2] = 0.054 M, and [COCl2] = 0.14 M. Calculate the equilibrium constants Kc and Kp.

CO (g) + Cl2 (g)

COCl2 (g)

[COCl2] 0.14 = = 220 Kc = [CO][Cl2] 0.012 x 0.054 Kp = Kc(RT)Dn

Dn = 1 2 = -1

R = 0.0821

T = 273 + 74 = 347 K

Kp = 220 x (0.0821 x 347)-1 = 7.7

The equilibrium constant Kp for the reaction

2NO2 (g) 2NO (g) + O2 (g)

is 158 at 1000K. What is the equilibrium pressure of O2 if the PNO2 = 0.400 atm and PNO = 0.270 atm?
Kp = PNO PO2
2 PNO 2 2 2 2

PO

= Kp

PNO

P2 NO = 347 atm

PO 2 = 158 x (0.400)2/(0.270)2

Heterogeneous equilibrium reactants and products present in more than one physical state

H2O(l)

H2O(g)

Heterogenous equilibrium applies to reactions in which reactants and products are in different phases.

CaCO3 (s)
[CaO][CO2] Kc = [CaCO3]

CaO (s) + CO2 (g)

[CaCO3] = constant [CaO] = constant Kp = PCO2

[CaCO3] Kc = [CO2] = Kc x [CaO]

The concentration of solids and pure liquids are not included in the expression for the equilibrium constant.

Heterogeneous equilibrium
Since concentrations of pure liquids and solids remain constant, these substances are omitted from the equilibrium constant expression.

Write an equilibrium constant expression for: H2O(l) H2O(g)

Keq = [H2O(g)]

Equilibrium constant expression Keq = . . .

Products over reactants raised to power of coefficient; leave out pure solids and liquids.

Equilibrium position Equilibrium concentrations can vary from trial to trial.

H2(g) +I2(g)

2HI(g)

N2O4 (g)

2NO2 (g)
constant

N2O4 (g)

2NO2 (g)

2NO2 (g)

N2O4 (g)

[NO2]2 = 4.63 x 10-3 K= [N2O4]

[N2O4] 1 = 216 K = = 2 [NO2] K

When the equation for a reversible reaction is written in the opposite direction, the equilibrium constant becomes the reciprocal of the original equilibrium constant.

Each set of equilibrium concentrations represent an equilibrium position. A system has only one value for Keq at a specific temperature, however there are unlimited number of equilibrium positions.

A system at equilibrium must: take place in closed system temperature remain constant all reactants and products are present (both reactions can occur)

Write the equilibrium constant expression for N2(g) + O2(g) 2NO(g)

Calculate the value of Keq if [N2] = 0.20 mol/L, [O2] = 0.15 mol/L, and [NO] = 0.0035 mol/L. Keq = 4.1 x 10-4 What does the value of Keq tell you about the equilibrium?

IF

The reaction quotient (Qc) is calculated by substituting the initial concentrations of the reactants and products into the equilibrium constant (Kc) expression. Vice versa for Kp Qc > Kc system proceeds from right to left to reach equilibrium Qc = Kc the system is at equilibrium Qc < Kc system proceeds from left to right to reach equilibrium

At 12800C the equilibrium constant (Kc) for the reaction Br2 (g) 2Br (g) Is 1.1 x 10-3. If the initial concentrations are [Br2] = 0.063 M and [Br] = 0.012 M, calculate the concentrations of these species at equilibrium. Let x be the change in concentration of Br2 Br2 (g) Initial (M) Change (M) [Br]2 Kc = [Br2] 0.063 +x 2Br (g) 0.012 -2x 0.012 - 2x Solve for x

Equilibrium (M) 0.063 + x

(0.012 - 2x)2 = 1.1 x 10-3 Kc = 0.063 + x

2 [Br] Qc = [Br i] 2 i

(0.012)2 Qc = 0.063

= 2.29 x 10-3 > Kc

Rx proceeds to the left to achieve eqm; prodt decompose to yield rxt

(0.012 - 2x)2 Kc = 0.063 + x = 1.1 x 10-3

ax2 + bx + c =0

2 4ac b b x= 2a

x = 0.0105 x = 0.00178
Br2 (g) 2Br (g)

Initial (M)
Change (M)

0.063
+x

0.012
-2x 0.012 - 2x

Equilibrium (M) 0.063 + x

At equilibrium, [Br] = 0.012 - 2x = -0.009 M or 0.00844 M At equilibrium, [Br2] = 0.062 + x = 0.0648 M

What happens when a system is at equilibrium and you upset the balance?

Le Chteliers Principle
When a system in dynamic equilibrium is to change, the system reacts to remove the change so equilibrium reestablish.
Changes in Concentration N2 (g) + 3H2 (g) Equilibrium shifts left to remove change 2NH3 (g) Add NH3

Le Chteliers Principle
Changes in Concentration continued Remove Remove Add Add aA + bB cC + d D

Change

Shifts the Equilibrium left right right left

Increase concentration of product(s) Decrease concentration of product(s) Increase concentration of reactant(s) Decrease concentration of reactant(s)

Le Chteliers Principle
Changes in Volume and Pressure PCl3 (g) + Cl2 (g) PCl5(g)

Change

Shifts the Equilibrium

Increase pressure Side with fewest moles of gas Decrease pressure Side with most moles of gas Increase volume Side with most moles of gas Decrease volume Side with fewest moles of gas

Le Chteliers Principle
Changes in Volume and Pressure H2 (g) + I2 (g) 2Hl(g)

Change

Shifts the Equilibrium

Increase pressure No effect on eqm system Decrease pressure since both sides contain Increase volume same no of molecules Decrease volume

Le Chteliers Principle
Changes in Temperature

Exothermic Rx Eqm position & eqm constant Endothermic Rx

Change

colder

hotter

The Effect Temperature on Equilibrium

Consider the following exothermic reaction: N2(g) + 3H2(g) 2NH3(g); DHo = -92 kJ,

The forward reaction produces heat => heat is a product. When heat is added to increase temperature, reverse reaction will take place to absorb the heat; If heat is removed to reduce temperature, a net forward reaction will occur to produce heat. Exothermic reactions favor low temperature conditions.

The Effect Temperature on Equilibrium

Consider the following endothermic reaction: N2O4(g) 2 NO2(g); DHo = +57 kJ 1. Endothermic reaction absorbs heat heat is a reactant; 2. If heat is added to increasing the temperature, it will cause a net forward reaction. 3. If heat is removed to reduce the temperature, it will cause a net reverse reaction. 4. Endothermic reactions favor high temperature condition.

Le Chteliers Principle Adding a Catalyst does not change K does not shift the position of an equilibrium system system will reach equilibrium sooner

uncatalyzed

catalyzed

Catalyst lowers Ea for both forward and reverse reactions. Catalyst does not change equilibrium constant or shift equilibrium.

Relationship between Keq & T Given by Vant Hoff equation; ln K = - H + C RT K = eqm constant H = enthalpy change of rx R = gas constant T = temperature (K) C = constant

i) Exothermic rx :
ln K

ii) Endothermic rx
ln K
o

Grad = -H R

Grad = -H o R
o

* +ve slope 1/T (K-1)

* -ve slope

1/T (K-1)

Chemical Equilibria in Industrial Processes

Production of Sulfuric Acid, H2SO4 in Contact process; 1. S8(s) + 8 O2(g) 8SO2(g) 2. 2SO2(g) + O2(g) 2SO3(g); DH = -198 kJ 3. SO3(g) + H2SO4(l) H2S2O7(l) 4. H2S2O7(l) + H2O(l) 2H2SO4(l) The second reaction is exothermic and has high activation energy; reaction is very slow at low temperature,. At high temperature reaction goes faster, but the yield would be very low. An optimum condition is achieved at moderate temperatures and using catalysts to speed up the reaction. Reaction also favors high pressure.

Chemical Equilibria in Industrial Processes

The production of ammonia by the Haber process: N2(g) + 3H2(g) 2NH3(g); DH = -92 kJ This reaction is exothermic and very slow at low temperature. Increasing the temperature will increase reaction rate, but will lower the yield. An optimum condition is achieved at moderate temperature of 250 to 300oC with catalyst added to increase the reaction rate. Increasing the pressure will favor product formation. Reaction favors low temperature and high pressure conditions.

The production of nitric acid by the Ostwald process: Step 1: 4NH3 (gas) + 5O2 (gas) 4NO (gas) + 6H2O (gas) Step 2: 2NO (gas) + O2 (gas) 2NO2 (gas) Step 3: 3NO2 (gas) + H2O (liquid) 2HNO3 (aqueous solution) + NO (gas) Step 4: 4NO2 (gas) + O2 (gas) + 2H2O (liquid) 4HNO3 (aqueous)
reaction is exothermic...conditions that would favor the forward reaction and shift the equilibrium to the right would be decreasing the temperature, increase the concentration , and increasing the pressure and volume. The catalyst that is used for this reaction is a platinum gauze. It would be heated, however sometimes in substitute..a copper wire/rod can serve as a proper catalyst for this process

Formation of Ozone in Stratosphere

Concentration of Stratospheric Ozone

Depletion of Ozone in Stratosphere

Formation of ozone in the stratosphere

Ozone, O3 is formed from chemical reaction between nitrogen dioxide and oxygen in 2 steps.

Step 1 Photo dissociation of nitrogen dioxide

Step 2 Formation of Ozone

In the presence of UV light, nitrogen dioxide dissociates to form nitrogen monoxide and oxygen free radicals

Step 1: Photo dissociation of nitrogen dioxide

NO2(g) NO(g) + O (g)

Step 2: Formation of ozone

The oxygen free radicals rapidly react with oxygen in the air to form ozone molecules.

O (g) + O2(g) O3(g)

Depletion of ozone in stratosphere

Ozone reacts with nitrogen monoxide (formed in Step 1 of formation of O3) to produce nitrogen dioxide and oxygen. O3(g) + NO(g) O2(g) + NO2(g) Its actually the reverse of the formation of stratospheric ozone!

Rate of formation of ozone

=
UV light

Rate of depletion of ozone

The system is in dynamic equilibrium. NO2(g) + O2(g) NO(g) + O3(g)

Concentration of ozone remains constant

 Everyday, 3x108 tons of stratospheric ozone formed & destroyed by natural processes. Stratospheric O3 IMPORTANT ; photodissociation rx, prevent harmful uv radiation frm reaching earths surface. (200 310 nm) are absorbed frm the uv rays Photons in this range ; enough energy to cause skin cancer & damage to living plants For every 1% in stratospheric ozone, additional 2% damaging uv rays reach earths surface.

Le Chteliers Principle
Change Shift Equilibrium Change Equilibrium Constant

Concentration
Pressure Volume Temperature Catalyst

yes
yes yes yes no

no
no no yes no