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Unit 1: Chemical Kinetics

Collision Theory: collisions must take place b/w reactant molecules

Reaction Mechanism: a series of steps making up a complete reaction

The reaction rate of any step in a reaction is directly proportional to:


- # collisions per second b/w reacting particles
-fraction of collisions that are effective

To be effective (produce new substances) 2 conditions:


1. must be enough kinetic energy in collision to let reacting molecules overcome
repulsion forces (due to nucleus-nucleus & e- - e- interactions) and, if
necessary, to break bonds (this energy called Activation Energy, EA)
2. reacting molecules must be aligned appropriately (correct geometry) to allow
e-‘s and/or atoms to change positions

Since motion of reacting molecules is (usually) random, reaction rate depends on factors that influence the 2
conditions.
The more collisions that occur, the greater the chance that some of them will have the correct geometry.
The greater the speed (average KE) of the reactants, the more likely some of the collisions will have
enough energy for a successful collision.

5 factors:
-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

In general, reactions occurring b/w small ionic species in aqueous solution are very rapid (often instantaneous)

Reactions involving large molecules, molecules w/ many bonds to break (or form), or many molecules tend to be
slower

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


PE diagrams are used to show the PE (& any change in PE) over the course of a reaction

PH

R
E A
PE
heat
content

P
R
E
∆AH PE
heat
content

Exothermic Endothermic

progress f rxn. progress f rxn.

∆H – enthalpy
EA – activation energy

Activation Energy: minimum amount of KE required by molecules in order to react

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

∆H
P
R
EA
==PE
89.5
-77.2kJ
reaction kJ
co-ordinate (or progress of rxn.)
progress
∆H
EArf
PE of rxn.

KE
progress of rxn

EAf = EAr + ∆H

Reaction Mechanisms

One step in a reaction could be


-unimolecular
-bimolecular
-termolecular

Elementary Process: each step, involving 1 collision

aA
E
∆H
creaction
b
intermediates

Reaction Intermediate: substance produced in 1 elementary process & used up in another

a, b, c are the activated complexes


for the 3 steps

activated complex:
-unstable, short-lived, high PE species
consisting of the colliding molecules
-bonds are being broken and/or made;
atoms are being re-arranged
Reaction Kinetics
Determining Rate Law from Experimental Data

faster the reaction = the more economical

Rate Law: relationship b/w rate & concentration of the reactants in a reaction
A+B→C+D
rate law: R = k[A]m[B]n
R is the rate w/ units of (mol/L)/s or M/s or mol L-1 s-1
k is the rate constant (specific to each rxn. at given temp)
[A] & [B] are conc. Of reactants A & B
m & n are exponents determined by experimentation
order of reaction: sum of exponents (m + n)
higher order = more complex reaction

Effect of changing the conc. of each reactant must be measured separately. Thus all reactants except 1 must be
held constant. Rate is then measured at several different conc.’s of the reactant in question. Process is
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 (0.0010 to 0.0020) rate increased by factor of 4 (0.0020 to 0.0080). when [NO]
tripled (0.0010 to 0.0030) rate increased by factor of 9. The increase in rate is the square of the
increase in conc. so the rate law w/ respect to the NO reactant is R [NO]2.
Experiments 4, 5, 6:
When [H2] doubled from exp. 4 to 5 the 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)

(homogeneous)
eg. H2O2 + I- → H2O + IO- (slow) reaction intermediate: IO-
IO- + H2O2 → H2O + O2 + I- (fast) catalyst: I-
2H2O2 → 2H2O + O2

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. on same graph (assume 1 step fro uncatalyzed)

CH3OH + H+ → CH3OH2+
CH3OH2+ → CH3+ + H2O
CH3+ + CH3COOH → CH3COOHCH3+
CH3COOHCH3+ → CH3COOHCH3+ + H+
H+
Overall rxn: CH3OH + CH3COOH → CH3COOHCH3+ + H2O

Catalyst: H+

PE diagram:

progress of rxn.
PE
cat.
uncat.

Sample Written Response

Questions:

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?
2. Using collision theory give 2 reasons why increasing temperature will increase reaction rate.

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

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

0.100 0.100 3.00 x 10-3

0.400 0.100 12.00 x 10-3

0.400 0.200 24.00 x 10-3

Answers:

1. (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. 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.
[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

Most reactions don’t go to completion. As product molecules form, they may collide and reform the original
reactants.
A+B↔C+D rate(f) = k[A]x[B]y
rate (r) = k[C]m[D]n
Unless otherwise specified the term ‘reactant’ is still used to refer to things to the left of the equilibrium arrows &
‘product’ refers to those to the right of the arrows.
Initially the forward & reverse rxn’s may have different rates.

Equilibrium: point of time where the f.rate = r.rate; no further changes are visible

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

N2O
NO
[time
] 24 at which vol.
suddenly decreases

change in temp. or conc. the effects of pressure change are considered insignificant

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) /(0.800) (0.400)
2 2

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

I 0.80 0.80 0 0 SO2 (g)


+ NO2
C -x -x +x +x (g) ↔
SO3 (g) +
E 0.80 - x 0.80 - x x x NO (g)

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 SO2 (g)


+ NO2
C -x -x +x +x (g) ↔
SO3 (g) +
E 4.0 - x 4.0 - x 4.0 + x 4.0 + x 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