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Unit 1: Chemical Kinetics

To be effective (produce new substances) 2 conditions:

1. must be enough KE in collision to let reacting molecules overcome repulsion forces and, if
necessary, to break bonds (EA)
→ The greater the speed (average KE) of the reactants, the more likely some of the
collisions will have enough energy for a successful collision.
2. reacting molecules must be aligned appropriately (correct geometry) to allow
e-‘s and/or atoms to change positions
→ The more collisions that occur, the greater the chance that some of them will have the
correct geometry.

5 factors influencing above conditions:

-concentration of reactants
-temperature
-surface area of reactants (heterogeneous reactions)
-nature of reactants
-presence of catalysts or inhibitors

Nature of Reactants

Includes:
-shape & size of molecules
-polarity of molecules
-ionic charges (& their magnitude: +1, +2, etc.)
-phase (solid, liquid, aqueous, gas)
-electron affinity
-bond type (ionic, covalent) & strength
-# bonds to break or form

Note: bond-breaking is endothermic

bond-formation is exothermic

Heterogeneous reactions (those involving different phases) tend to be slow due to limited surface areas;
however, if finely powdered solids react with gases the rate may be fast.

Potential Energy (PE) Diagrams

PH
∆
R
E A
PE
heat
content

Exothermic Endothermic

P
R
E
∆AH PE
heat
content
 progress f rxn. progress f rxn.

∆H – enthalpy
EA – activation energy

Activation Energy: minimum KE required by molecules to react

Activated Complex: formed if colliding molecules have EA; species w/ high potential energy but very
unstable (short-lived). If energy & geometry conditions met, activated complex quickly breaks into
products (if not it will break up into the original reactants).

KE
progress of rxn

progress
E
∆H PE of rxn.
∆ AH
P
R
E rf
==PE
89.5
reaction
A
-77.2kJ
kJ
co-ordinate (or progress of rxn.)

EAf = EAr + ∆H

reaction
E
∆Hactivated complexes
A
intermediates

Reaction Mechanisms
 Rate Law

Rate Law: relationship b/w rate & conc. of reactants

A+B→C+D
rate law: R = k[A]m[B]n
R - rate w/ units of (mol/L)/s or M/s or mol L-1 s-1
k - rate constant
m & n - exponents determined by experimentation
order of reaction: sum of exponents (m + n)

Effect of changing conc. of each reactant measured separately (thus all reactants except 1 must
be held constant). Rate then measured at several different conc.’s of reactant in question. Process
repeated for each reactant.
In most reactions the rate is not constant throughout the whole reaction but the initial rate is
customarily used to determine the rate law.

Example – determine rate law, order of reaction, & rate constant

2H2 (g) +2NO (g) → N2 (g) + 2H2O (g)

Exper. # [NO] mol/L [H2] mol/L Rate mol/L/s

1 0.0010 0.0040 0.0020

2 0.0020 0.0040 0.0080

3 0.0030 0.0040 0.018

4 0.0040 0.0010 0.0080

5 0.0040 0.0020 0.016

6 0.0040 0.0030 0.024

Experiments 1, 2, 3:
When [NO] doubled rate increased by factor of 4
When [NO] tripled rate increased by factor of 9
increase in rate is the square of the increase in conc. so rate law w/ respect to NO r is R [NO]2.

Experiments 4, 5, 6:
When [H2] doubled from exp. 4 to 5 rate also doubled
When [H2] tripled the rate tripled.
Thus, rate law is R [H2].

Combined: R = k[NO]2[H2]
Order of rxn.: 3
 Rate Constant: k = R/([NO]2[H2]) = 5.0 x 105 mol-2 L2 s-1

Formal Method for Determining Rate Law from Experimental Data

Exper. # [S2O32-] mol/L [I-] mol/L Rate mol/L/s

1 1.0 x 10-4 1.0 x 10-2 6.5 x 10-7

2 2.0 x 10-4 1.0 x 10-2 13.0 x 10-7

3 3.0 x 10-4 1.0 x 10-2 19.5 x 10-7

4 1.0 x 10-4 2.0 x 10-2 6.5 x 10-7

5 1.0 x 10-4 3.0 x 10-2 6.5 x 10-7

Pick 2 trials where one reactant conc. changes & the others are constant

rate2/rate1 = (13.0x10-7)/(6.5x10-7) = 2.0

rate2/rate1 = (rate law trial 2)/(rate law trial 1) = (k[S2O32-]x2 [I-]y2) / (k[S2O32-]x1 [I-]y1)

therefore
2.0 = (k[S2O32-]x2 [I-]y2) / (k[S2O32-]x1 [I-]y1)

k cancels out and [I-] is kept constant

2.0 = ([S2O32-]x2) / ([S2O32-]x1)

therefore
2.0 = (2.0x10-4)x/(1.0x10-4)x
2.0 = (2.0x10-4/1.0x10-4)x
2.0 = 2.0x
log2.0 = xlog2.0
x = log2.0/log2.0
x=1

repeat for [I-] using trials 1 & 4

Catalyzed Reactions
Homogeneous: catalyst & reactants are in the ‘same phase’ (miscible)
Heterogeneous: catalyst & reactants are in ‘different phases’ (immiscible)
Miscible - property of liquids to mix in all proportions, forming a homogeneous solution

Heterogeneous Catalysts
-Usually solids; reactants will be liquid or gas
-ex: platinum in catalytic converter of car’s exhaust system
iron powder & metal oxides in the Haber process (ammonia production)
nickel for changing vegetable oils into ‘solid’ fats (margarine)
-usually 4 steps:
1. adsorption & activation of the reactants
2. migration of the adsorbed reactants on the surface
3. reaction of the adsorbed substances
4. escape (or desorption) of the products

Example
1 CH3OH + H+ → CH3OH2+ (slow)
2 CH3OH2+ → CH3+ + H2O (fast)
3 CH3+ + CH3COOH → CH3COOHCH3+ (fast)
 4 CH3COOHCH3+ → CH3COOHCH3+ + H+ (fast)
What is the overall reaction?
What is the catalyst?
Draw the PE diagram for uncatalyzed & catalyzed rxn. (assume 1 step for uncatalyzed)

CH3OH + H+ → CH3OH2+
CH3OH2+ → CH3+ + H2O
CH3+ + CH3COOH → CH3COOHCH3+
CH3COOHCH3+ → CH3COOHCH
H+ 3 + H
+ +

Overall rxn: CH3OH + CH3COOH → CH3COOHCH3+ + H2O

Catalyst: H+
PE diagram:
progress of rxn.
PE
cat.
uncat.

Sample Written Response

1. Consider C12H22O11 (s) → 11H2O (g) + 12C (s)

The rate of decomposition of C12H22O11 is 0.75 mol/min. What mass of C is produced in 10.0 s?
(0.75 mol C12H22O11/min) (12 mol C/1 mol C12H22O11 ) = 9.00 mol C/min
(9.00 mol C/min) (1 min/60 s) = 0.150 mol C/s
(0.150 mol C/s) (10.0 s) = 1.50 mol C
(1.50 mol C) (12.0 g C/1 mol C) = 18 g C

2. Using collision theory give 2 reasons why increasing temperature will increase reaction rate.
1-higher temp = faster particles, therefore more likely to collide, therefore faster reaction
2-higher temp = more energetic collisions, therefore more molecules have min. Energy requirement

3. Given the following data write the rate law and the rate constant

[H2] (M) [I2] (M) Rate (M/s)

x4 R [H2]
x4 0.100 0.100 3.00 x 10 -3

x2 R [I2]
0.400 0.100 12.00 x 10-3 x2

0.400 0.200 24.00 x 10-3

R = k[H2][I2]
K = R/[H2][I2]
= (3.00x10-3 M/s)/(0.100 M)(0.100 M)
= 0.3 M-1 s-1

Unit 2: Chemical Eqilibrium

A+B↔C+D rate(f) = k[A]x[B]y

rate (r) = k[C]m[D]n

Conditions for equilibrium:

 -a reversible reaction
-a closed system
-f.rate = r.rate
-no macroscopic (visible) changes
-it is dynamic (changes still occurring at molecular or atomic level)

Le Châtlier’s Principle

Le Chatlier’s Principle: If a closed sytem at equilibrium is subjected to a change, processes will occur
that tend to counteract that change, and restore equilibrium.

1. Temperature Changes
endothermic: (ex. N2O4 + 59.4 kJ ↔ 2NO2) increased temp means more heat available to the
system; therefore allowing more of the reactant (N2O4) to react. Thus, the system shifts right
(more product produced while the amount of reactant decreases). If the higher temp. is
maintained, the system will establish a new equilibrium, one in which there are more products &
less reactants (therefore the Keq is higher). The opposite occurs in an exothermic reaction
*only factor that will cause the value of Keq to change
new
N
[NO
from
time
x2 x2O
] 24 eq.
at
mole
which
ratio
temp. increases

2. Concentration Changes
If the conc. of a reactant or product increases, the equilibrium will shift to the opposite side.

time
extra
[[NO
N]2O
NO 2
] NO
doesn’t
2
return to
24
injected value
original

(increased conc.’s results in more effective collisions)

3. Volume Changes
-for (g) rxn.’s if vol. ↓ rapidly, the conc. of all gases will ↑ (b/c same # moles in fewer L); an ↑ in
conc.
also means ↑ in pressure. To counteract this, system shifts to reduce the total # of moles of gas
-if pressure ↑ due to addition of an inert gas there is no change
-if pressure changes due to change in temp. or # moles the problem is considered to involve only
a
change in temp. or conc. the effects of pressure change are considered insignificant
 N2O
NO
[time
] 24 at which vol.
suddenly decreases

4. Addition of a Catalyst
-no change if added to equilibrium

addition
N
[NO
time
O
]
2 24
of
catalyst

-if added before equilibrium, equilibrium will be established faster

The Equilibrium Expression (Law)

Relating the concentrations of products and reactants in an equilibrium situation

coefficients → exponents (ex. 2Cl2 → [Cl2]2)

rate = k[A]a[B]b

at equilibrium f.rate=r.rate
kf[A]a[B]b = kr[C]c[D]d
kf/kr = [A]a[B]b/[C]c[D]d
Keq = [A]a[B]b/[C]c[D]d

Equilibrium expression for a rxn. includes only substances which could undergo a measurable change in
conc.
-all gases must be included
-all aqueous ions must be included
-solids not included (density of solid constant under norm. conditions; density=measure of conc. of
solid)
-pure liquids not included (same reason as solid). Note that mixtures of miscible liquids must be
included; immiscible liquids are not included.

Interpreting Keq – magnitude of Keq indicates ‘position’ of the equilibrium

 -“large” Keq (1, 104, 1010) → forward rxn. is favoured (rxn. more complete; more products than
reactants)
-“small” Keq (0.2, 10-5) → reverse rxn. is favoured (more reactants than products)
-“intermediate” Keq (0.9, 1, 2) → neither rxn. favoured (~similar amounts of reactants & products)
*these are relative terms; there is no specific range of values

Ktrial < Keq → system shifts right (more products, less reactants)
Ktrial > Keq → system shifts left (less products, more reactants)

Equilibrium Calculations

Example 1 – A 2.0 L bulb contains 6.00 mol NO2 (g), 3.0 mol NO (g), & 0.20 mol O2 (g) at equilibrium.
Calculate the Keq. 2NO (g) + O2 (g) ↔ 2NO2 (g)

[NO]eq = 3.0 mol/2.0 L = 1.5 M NO

[O2]eq = 0.20 mol/2.0 L = 0.10 M O2
[NO2]eq = 6.00 mol/2.0 L = 3.00 M NO2

Keq = [NO2]2/[NO]2[O2] = (3.00)2/(1.5)2(0.10) = 40

Example 2 – 4.00 mol NO2 (g) is introduced into a 2.00 L bulb. After some time equilibrium is attained
according to the equation 2NO (g) + O2 (g) ↔ 2NO2 (g). At equilibrium 0.500 mol NO (g) is found. What is
Keq?

1. write the equation

2NO (g) + O2 (g) ↔ 2NO2 (g)

2 .if not at equilibrium, use an I.C.E. table (all values are concentrations)
[NO2]start = 4.00 mol/2.0 L = 2.00 M NO2
[NO]eq = 0.500 mol/2.0 L = 0.250 M NO

2NO (g) +
I 0 0 2.00 O2 (g) ↔ 2NO2 (g)
C + 0.250 + 0.125 -0.250
(mole ratio)
E 0.250 0.125 1.75

Keq = [NO2]2/[NO]2[O2] = (1.75)2/(0.250)2(1.25) = 392

Example 3 – A certain amount NO2 (g) was introduced into a 5.00 L bulb. When equilibrium was attained
according to 2NO (g) + O2 (g) ↔ 2NO2 (g) the conc. of NO was 0.800 M. If Keq = 24.0 how many moles
NO2 were originally put into the bulb?

I 0 0 X

C + 0.800 + 0.400 - 0.800

E 0.800 0.400 x - 0.800

Keq = [NO2]2/[NO]2[O2]
24.0 = (x – 0.800)2/(0.800)2(0.400)
2.479 = x – 0.800
x = 3.279 M

3.279 M (5.00 L) = 16.4 mol NO2

Example 4 – Keq = 3.5. SO2 (g) + NO2 (g) ↔ SO3 (g) + NO (g). 4.0 mol SO2 & 4.0 mol NO2 placed in 5.00
L bulb & allowed to come to eq. What conc. of all species will exist?

[SO2]i = [NO2]I = 4.0 mol/5.00 L = 0.80 M

SO2 (g) + NO2 (g) ↔ SO3 (g) + NO (g)

 I 0.80 0.80 0 0

C -x -x +x +x

E 0.80 - x 0.80 - x x x
Keq =
[SO3][NO]/[SO2]
[NO2]
3.5 = (x)(x)/(0.80 – x)(0.80 – x)
1.87 = x/(0.80 – x)
x = 0.52
[SO3] = [NO] = x = 0.52 M
[SO2] = [NO2] = 0.80 – x = 0.28 M
Example 5 – 1.0 L vessel contained 1.0 mol SO2, 4.0 mol NO2, 4.0 mol SO3, & 4.0 mol of NO at
equilibrium SO2 (g) + NO2 (g) ↔ SO3 (g) + NO (g). If 3.0 mol SO2 added to mixture what will new conc.
NO be?

Keq = [SO3][NO]/[SO2][NO2]
Keq = (4.0)(4.0)/(1.0)(4.0)
Keq = 4.0

I 4.0 4.0 4.0 4.0

C -x -x +x +x

E 4.0 - x 4.0 - x 4.0 + x 4.0 + x

SO2 (g) + NO2 (g) ↔ SO3 (g) + NO (g)

Keq = [SO3][NO]/[SO2][NO2]
4.0 = (4.0 + x)2/(4.0 – x)2
2.0 = (4.0 + x)/(4.0 – x)
x = 1.33

[NO]new = 4.0 + x = 5.5 M

Example 6 – Keq = 49. 2NO (g) + O2 (g) ↔ 2NO2 (g). If 2.0 mol of NO & 0.20 mol O2 & 0.40 mol NO2 are
put in 2.0 L bulb, which way will the reaction shift?
(not asking for a #, no need for ICE; calculate numerical value of the eq. Expression
when system not at eq. → called Ktrial or Q; compare Ktrial & Keq)

[NO2] = 0.40 mol/2.0 L = 0.20 M

[O2] = 0.20 mol/2.0 L = 0.10 M
[NO] = 2.0 mol/2.0 L = 1.0 M

Ktrial = [NO2]2/[NO]2[O2] = 0.40

Ktrial < Keq, so system will shift right

 Entropy, Enthalpy, & Equilibrium

Enthalpy: the heat content

∆H → change in heat content
∆H > 0 → endothermic
∆H < 0 → exothermic

Most spontaneous chem. rxn.’s are exothermic

spontaneous rxn.’s proceed in given direction w/o outside assistance
if rxn. is spontaneous in 1 direction, it is non-spontaneous in the opposite direction

Some rxn.’s are spontaneous and endothermic

there is another ‘driving force’ → entropy
S is used to represent entropy

Entropy: measure of disorder (chaos, randomness); greater the disorder, greater the entropy
(high entropy) gases > solutions > liquids >solids (low entropy)

The outcome of a rxn. depends on enthalpy & entropy changes involved

The tendency towards minimum enthalpy (exothermic) (∆H –)
The tendency towards maximum entropy (∆S +)
4 possible combinations
∆H ∆S Result

- + complete rxn. (spontaneous)

- - equilibrium state
(temperature dependant)
+ +

+ - no rxn. (non-spontaneous)

In general ∆S>0 (+) when:

-liquids or solutions are formed from solids
-gases are formed from either solids or liquids
-the # molecules of gas increases during a rxn.
-the temp. Of substance increases

Example 1 – Zn (s) + 2HCl (aq) → ZnCl2 (aq) + H2 (g) (exothermic)

∆H < 0 (–) complete rxn.
∆S > 0 (+)

Example 2 – heat + N2O3 (g) ↔ NO (g) +NO2 (g)

 ∆H > 0 (+) equilibrium
∆S > 0 (+)

Example 3 – N2 (g) + 3Cl2 (g) ↔ 2NCl3 (g) ∆H = 490 kJ

∆H < 0 (+) non-spontaneous (no rxn.)
∆S > 0 (–)

Unit 3: Solution Eqilibria

Solvent – a substance that does the dissolving. It dissolves the solute. Present in greater quantity
Solute – a substance that gets dissolved. Dissolves in a solvent. Present in lower quantity.
Solution – solute(s) + solvent creates a solution
Electrolyte – a solution containing ions which will conduct electricity
Dissociation – when ionic compounds are ‘pulled apart’ into their ions as they dissolve
Saturated – when a solvent can no longer dissolve any more solute
Unsaturated – a solution that could still dissolve more solute
Concentration: how much solute is in a litre (or other volume) of solution
Molarity: most common way of expressing a concentration (mol/L)

concentration example:
What is [Cl-] if 15.0 g CuCl2 dissolved in 100.00 mL of sol.?
CuCl2 ↔ Cu2+ + 2Cl-
15.0 g CuCl2 (1 mol/134.5 g) (2mol Cl-/1 mol CuCl2) = 0.2230 mol Cl-
[Cl-] = 0.2230 mol/0.10000 L = 2.230 M

When solution is saturated, some solid is present, therefore equilibrium exists

AgI (s) ↔ Ag+ (aq) + I-

Keq = [Ag+][I-] = Ksp

Ksp expression – solubility product

The product of ion concentrations for a saturated solution

Solubility – the amount of solute that dissolves in a given volume of solution

Ktrial = Ksp saturated

Ktrial < Ksp unsaturated
Ktrial > Ksp excess ions ppt until Ktrial = Ksp → saturated
(same as earlier, of Keq and Ktrial where the system shifts left or right)

Common Ion Effect

Application of Le Châtelier’s Principle to aqueous solutions

CaSO4 (s) ↔ Ca2+ (aq) + SO42- (aq)

Given a saturated solution of CaSO4,if another solution containing Ca2+ ions (or SO42- ions) is added, the
stress of additional Ca2+ ions (the “common ion”) will cause a shift to the left according to Le Châtelier’s
Principle. As a result there will be more CaSO4 (s) formed, therefore the solubility of CaSO4 is decreased.

The solubility of CaSO4 can be increased by causing the system to shift to the right. This can be done by
adding a substance that will cause the precipitation of Ca2+ (or SO42-).
Example: addition of NaOH. The OH- ion precipitates (is of low solubility) with Ca2+ causing a shift to the
right