I.

RATES OF REACTION

Collision theory – indicates that a reaction takes place only when molecules collide with the proper
orientation and sufficient energy

Three conditions required for a reaction to occur:

1. Collision – reactants must collide

2. Orientation - reactants must align properly to break and form bonds
3. Energy – collision must provide the energy of activation

• rate (speed) of reaction – determined by measuring the amount of a reactant used up, or the
amountof a product formed in a certain period of time

change in concentration
rate of rxn = ---------------------------
change in time

Factors that affect the rate of a reaction

• temperature
• changes in the concentration of the reactants
• addition of catalysts

Temperature – high temperature = molecules move faster

– more collisions, more colliding molecules

Concentration of reactants – rate of rxn increase = concentration of reactants increases

Catalysts – speed up a rxn by providing an alternate pathway that has a lower energy of activation

II. CHEMICAL EQUILIBRIUM

Reversible reactions - consists of both a forward and a reverse reaction

– the rate of the forward reaction and the rate of the reverse reaction
– rate of the forward reaction is faster than the rate of the reverse reaction

Chemical equilibrium – when there is no further change in the concentration of the reactants and
products
– reactants formed products as products form reactants
– rates of forward and reverse rxn are equal

1
Exercise:
Reversible rxns:
 N2(g) + 3H2(g) 2NH3(g)
forward rxn N2 + 3H2 N2 + 3H2
reverse rxn 2NH3 N2 + 3H2

f: 2 CO (g) + O2(g) 2 CO2 (g)

r: 2 CO2 (g) O2 (g) + 2CO(g)

III.EQUILIBRIUM CONSTANTS, Kc
• numerical value obtained by substituting molar concentation at equilibrium into the expression

products [C]c [D]d

Kc = --------------- = coefficients
reactants [A]a [B]b

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

[HI]2
Kc = ---------------
[H2] [I2]

Boardwork:
Write the equilibrium constant expression for each of the following:
a. 2SO2 (g) + O2 (g) 2SO3(g)

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

Hot Question!!
Write the balanced chemical equation that would give the following equilibrium constant expression.

[NO2]2
Kc =
[NO]2 [O2]

2
• Heterogenous Equilibrium - reactants and products are in two or more states
– concentration of pure solids and liquid are constant, therefore
they are not included in the equilibrium constant expression
 CaCO3 (s) CaO(s) + CO2 (g)

Kc = [CO2]
Exercise:
Write the equilibrium constant expression for the ff. Heterogenous equilibria:
a) Si (s) + 2Cl2 (g) SiCl4(g)

b) 2Mg (s) + O2 (g) 2MgO(s)

• Calculating Equilibrium Constants

Equilibrium Constants for H2(g) + I2(g) 2HI(g) at 427ºC.

[HI]2
Kc=
Experiment [H2] [I2] [HI] [H2][I2]

1 0.10M 0.20M 1.04M 54

2 0.20M 0.20M 1.47 54
3 0.30M 0.17M 1.66 54

Reactants Products
[H2] = 0.10M [HI] = 1.04M
[I2] = 0.20M

IV. Using Equilibrium Constants

[products] = Large Kc
[reactants]

• The numerator (products) is greater than the concentrations of the reactants in the
denominator.
 [products] = Small Kc
[reactants]

• Kc small, numerator is smaller, the reaction favors the reactants

if Kc = 1 x 103 or 1000
Therefore: [B] would be 1000 times greater than [A] at equilibrium

Kc – [B] = 100 or [B]= 1000[A]

[A]

Small Kc
if Kc = 1x 10-2
Therefore: [A] is 100 times greater than [B] at equilibrium

Kc – [B] = 1 or [A]= 100[B]

[A] 100

Table 9.4

Effect of concentration Changes on Equilibrium PCl5(g) PCl3(g) + Cl2(g)

Stress Shift Equilibrium Changes

PCl5(g) PCl3(g) Cl2(g)

Increase PCl5 Toward products added more more
Decrease PCl5 Toward Reactants removed less less
Increase PCl3 Toward Reactants more added less
Decrease PCl3 Toward Products less removed more
Increase Cl2 Toward Reactant more less added
Decrease Cl2 Toward Products less more removed

• Large Kc
2SO2(g) + O2(g) 2SO3(g)

Kc = [SO3]2 Mostly Product

[SO2]2[O2] little reactant

= 3.4 x 102
• Small Kc
N2(g) + O2(g) 2NO(g)

Kc = [NO]2 = little product

[N2][O2] more reactants

= 2 x 10-9

• Calculating Concentrations Using an Equilibrium Constant

 Phosgene (COCl2) is a toxic substance that is produced by the reaction of CO and Cl2; the
Kc for the reaction is 5.

CO(g) + Cl2(g) COCl2(g)

If the equilibrium concentrations for the reaction are [Cl2] = 0.25 and [COCl2] = 0.8m,
What is the equilibrium concentration of CO(g)?

given: [Cl2] = 0.25M

[ COCl2]= 0.8M
Kc= 5.0

Need: [CO]
Solution:
[COCl2]
Kc = [Co][Cl2]

Kc[CO]pCl2] = [COCl2]x [CO][Cl2] * multiply both sides by [CO][Cl2]

[CO][Cl2]

Kc[CO]pCl2] = [COCl2]

Kc[CO]pCl2]= [COCl2 * Divide Both sides by Kc [Cl2]

Kc[ Cl2 ] Kc [Cl2]

[CO] = [COCl2] * Substitute values

Kc [Cl2]

[CO] = 0.8 M CHECK:

5 x 0.25 M Kc = [COCl2] = 0.8 M
[Co][Cl2] 0.64 x 0.25
= 0.64 M
= 0.64 =5

Assignment / Seatwork:

Ethanol can be produced by reacting ethylene C2H4 with water vapor. At 327o C, Kc is 9 x 103

C2H4(g) + H2O(g) C2H5OH(g)

if an equilibrium mixture has concentrations of [C2H4] = 0.020 M and [H2O] = 0.015M,

What is the equilibrium concentration of C2H5OH?

V. Changing Equilibrium Conditions: Le Chatelier's Principle

 > When a stress (Change in Conditions) is placed on a
reaction at equilibrium. The equilibrium shifts in the direction
that relieves the stress.

• Effect of Concentration Changes: Chapter Review

Table 9.5

Equilibrium Shifts for Temperature Chages in an Endothermic Reaction

Kc Temperature Change Equilibrium Shift Change in Kc Value

[NO]2 Increase More Product Increase

[N2][O2]

[NO]2
[N2][O2]

Less reactant
Less product

[NO]2
[N2][O2] Decrease Decrease

[NO]2
[N2][O2]
More reactant

Table 9.6

Equilibrium Shifts for Temperature Changes in an Exothermic Reaction

• If heat is removed, the equilibrium of an exothermic reaction favors the products, which
provides heat
• Increase T, decrease Kc
• decrease T, increase Kc
Table 9.7

Effects of Condition Changes on Equilibrium

Condition Change (Stress) Reaction to Remove Stress
Concentration Add reactant Forward
Remove reactant Reverse
Add product Reverse
Remove product Forward
Volume (Container) Decrease Toward fewer moles in the gas phase
Increase Toward more moles in the gas phase
Temperature Endothermic reaction
Raise T Forward, new value for Kc
Lower T Reverse, new value for Kc
Exothermic reaction
Raise T Reverse, new value for Kc
Lower T Forward, new value for Kc
Catalyst Increase rates equally No effect