Collision theory and rates of reaction

 Chemical Kinetics: The study and discussion of chemical reactions with respect to
reaction rates
 Rate of Reaction: The change in concentration of reactants or products per unit
time.

Experimental measurements of reaction rates

 Δc, the change in concentration can be measured indeirectly by monitoring a
property which changes when reactants are converted to products. Examples
include:
 pH (acid – base reactions)
 Conductivity (reactions with electrolytes)
 Mass/volume (reactions involving gases)
 Colour (reactions with transition metals or other colored
compounds)
 To measure reaction rate, plot concentration vs time graph. The rate is
determined from slope of gradient at point t on the graph.
 Rate of reaction can be measured in three ways
 Average rate
 Avg rate = Δc/Δt
 Instantaneous rate
 Slope of tangent at a point
 Initial rate
 Slope of tangent at point t 0

Kinetic molecular theory of gases

 Explains why gases act the way they do
 Theory
1. Gases have many particles moving at high velocities in random
directions
2. Size of a gaseous particle is negligible
3. Collisions between gaseous particles are elastic; no energy is
lost
4. Ke  is proportional to the absolute temperature in kelvin
av

Occam’s razor
 Used as a guide to develop a theory
 A principle which states that “Entities should not be multiplies unnecessarily”
  This means if you have two competing theories, use the simpler one
unless there is proof otherwise
 Collision theory was built using Occam’s razor

Catalysts
 A substance that increases the rate of a chemical reaction by lowering the
activation energy and is not consumed in the reaction.
 This can be demonstrated using a potential energy profile


 Activation energy: The minimum energy required for a reaction to occur
 Catalysts come in two types:
 Homogeneous:
 In the same physical state as the reactants
 Example is destruction of ozone, O , by chlorine atoms.
3

In the stratosphere, ozone absorbs over 95% of UV

radiation from sun. It under goes homolytic fission and
converts UV radiation to heat. Chlorine atoms are
produced in the reaction of a chlorofluorocarbon (CFC)
with UV light.
 Heterogeneous:
 In a different state from the reactants
 Example is catalytic converter in exhaust system of car
which converts harmful gaseous into water oxygen or
carbon dioxide

Maxwell – Boltzmann energy distribution and

temperature
 Shows the probability of finding particles with a specific kinetic energy
  Number of particles represented by area of green (in the picture) have enough
energy to react
 For a catalyzed reaction, the activation energy decrease, and there are more
particles which have enough energy to react
 As temperature increases, the mean velocity of particles increases and thus the
distribution become flatter and wider

Factors that affect the rate of chemical reaction

1. Increasing temperature
 Gives particles more kinetic energy, faster rate of reaction
2. Addition of catalyst
 Reduces activation energy, faster rate of reaction
3. Increasing concentration of reactants
 Increasing concentration means more collisions, faster rate of
reaction
4. Increasing surface area in solid phase
 Breaking down solid into smaller pieces means larger overall SA,
more collisions, faster rate of reaction

Equilibrium
Equilibrium Reactions in Chemistry
 Many chemical reactions are reversible and exist in state of equilibrium
 Dynamic Equilibrium: The forward and reverse reactions occur at equal rates
 Single arrows are for non-reversible reactions
  Double headed arrow are for reversible reactions which are in equilibrium

Chemical Systems
 The terms “Reactants” and “Products” implies a reaction goes to completion
when in reality, many reactions are in equilibrium
 Relative rates of a reaction depend on:
 Temperature and Pressure
 Concentration of reactants and products
 Presence of catalyst
 At equilibrium:
 Forward and reverse reactions occur at equal rates
 No change in concentration of reactants or products

Equilibrium Law
 Law: At a given temperature, the ratio of the concentration of products to the
concentration of reactants (each raised to the power of their molar coefficients) is
a constant


 Constant is called equilibrium constant denoted by K c

 This constant changes at different temperatures

 Large K  value (K  > 1) means products are favored over reactants
c c

 Small K  value (K  < 1) means reactants are favored over products

c c

 Pure solids and liquids are not included in when calculating the K value

c 

 Homogenous equilibrium: reactants and products are present in one phase.

(Common one is reactions in gaseous phase)
 Heterogeneous equilibrium: reactants and products exist in more than one phase
 K  of the reverse reaction is the same as 1/K  of the forward reaction
c c

 Kc (reverse) = 1/K  (forward)

c

Effect of conditions on equilibrium constant

 

Pressure:

 If there are 4 mols of gaseous reactants and 3 mols of gaseous products, an

increase in pressure would result in forward reaction being favored to reduce
number of mols overall
Temperature:

 In exothermic reaction, heat is a product. Increase in heat would cause

equilibrium position to move left to counter the imbalance caused by heat. A
summary of all possibilities is in table below

Catalyst:

 Catalyst reduces activation energy

 It increases rate of forward and reverse reaction by equal amount thus no change
in K
c

Le Châtelier principle
 Le Châtelier principle: If a change is made to a system that is in equilibrium, the
balance between the forward and reverse reactions will shift to offset this change
and return system to equilibrium
  If concentration of reactant is increased, forward reaction will be
favored to counteract this. Vice Versa
 Value of K  does not change
c

Reaction Quotient

 If system has not reached equilibrium yet, then

 Q is for reaction quotient and helps determine the progress of reaction as it moves
toward equilibrium

Theory of acids and bases

The role of acids and bases
 Acids and bases are opposites
 Many theories describe how they work
1. Arrhenius Theory of acids and bases
 Acids produce H  ions, bases produce OH  ions
+ –

 Neutralization is the process of combining an acid and a base

 Limitation: weak base ammonia and hydrogen chloride gas could
not be explained, as ammonia does not contain OH –

2. Bronsted-Lowry acids and bases

 Refer to hydrogen ion as a proton;
 Acid is proton donor, base is proton acceptor

Conjugate acids and bases

 In a reversible reaction between acid and bases, there are conjugates as well
Amphiprotic species
 Amphiprotic species: Substances which can be both Bronsted-Lowry acids or
bases depending on the reaction
 Examples:

Properties of acids and bases

Reactions of acids with metals, bases, and

carbonates
 Most acids react with metals, metal oxides, hydroxides, hydrogencarbonates and
carbonates
 All these reactions produce a salt which is a compound of anion and cation
 Standard enthalpy change of neutralization: the energy change associate with
the formation of 1 mol of water from the reaction between a strong acid and
a strong base under standard conditions
 Negative value because neutralization is exothermic
 For acids and bases:

 For metals higher than hydrogen on activities series:
 
 For metal carbonates and hydrogencarbonates:

The pH scale
 pH scale is effective way of representing concentration of hydrogen ions [H ] in a
+

solution
 It is a logarithmic scale with base 10, easy way for non-scientist to understand
safety of materials
 pH distinguishes between acidic, neutral and alkaline

Calculating pH
 The concentration of an acid with one proton is the same as the concentration of
hydrogen ions [H ] +

 [HCl] = [H ] +

 For more protons:

 [H SO ] = 2[H ]
2 4
+

Ionization of water
 

Strong and weak acids and bases

 Strength of an acid or base depends on the degree to which it ionizes (dissociates)
in water
  In the following reactions, an acid or a base reacts with water to produce
conjugates
 Strong acid is an effective proton donor that is assumed to
completely dissociate in water.
 Examples: HCl, H SO  and HNO
2 4 3

 Conjugate base of strong acid is weak base

 Weak acid only partially dissociates in water; it is a poor proton
donor.
 Examples: CH COOH and H CO
3 2 3

 The dissociation of a weak acid is a reversible reaction

that reaches equilibrium
 Only small portion of acid molecules have dissociated
at equilibrium
 Conjugate base of weak acid is strong base
 Strong base completely dissociates in water
 Examples: KOH, NaOH (Any group 1 metal hydroxides)
 Note: Metal hydroxides don’t act as Bronsted-Lowry
bases, however in solution the hydroxide ion OH  acts
–

as a base
 Weak base partially dissociates in water
 Example: NH 3

 Words strong and concentrated, and weak and diluted have very different

meanings.
 Strong: completely dissociated into ions
 Concentrated: a high number of moles of solute per litre of solution
 Weak: slightly dissociated
 Diluted: a low number of moles of solute per litre of solution

Experimental determination of the strength of

acids and bases
 Techniques to compare strength of acids and bases of equal concentration
 Conductivity
 All acids and bases dissociate in water to form ions. The conductivity
of an aqueous solution depends on the concentration of ions
present. Voltage is applied to different solutions (of equal
concentration), and the voltage reflects on concentration of ions,
and thus strength as well.
 Strong acids and bases have higher conductivities
 Weak acids and bases have lower conductivities

Energy changes on neutralization

  Neutralization: occurs when an acid and base react together
 This reaction is exothermic, ΔH < 0
 The enthalpy change of neutralization for a strong acid is almost identical to that
of weak acid
 For strong acid or base:
 They are completely dissociated in water, thus only
enthalpy change to consider is exothermic formation of
water from H  and OH  ions
+ –

 For weak acid or base:

 Dissociation of weak acid or base is mildly endothermic
 Enthalpy change for strong base-weak acid is less than
strong base-strong acid
 The weaker the acid, the more endothermic, and thus
lower enthalpy change of neutralization

Acid deposition
 Acid deposition: the process by which acid-forming pollutants are deposited on
the earth’s surface.
 Increased industrialization have led to rapidly increasing emission of nitrogen and
sulfur dioxides which cause acid rain, most prevalent form of acid deposition

Acid rain
 Pure water has pH of 7.0. Rainwater is acidic due to presence of dissolved carbon
dioxide which forms weak carbonic acid. Typical pH is 5.6
 Acid deposition is formed when nitrogen or sulfur oxides dissolve in water to form
HNO , HNO , H SO  and H SO
3 2 2 4 2 3


 The sources of nitrogen and sulfur are:
 Volcanic eruptions
 Decomposition of vegetation
 Combustion of fossil fuels
 Go over nitrogen and sulfur cycles which form the acids

Pre- and post-combustion technologies

Pre-combustion methods: refer to techniques used on fuels before their combustion
Post-combustion methods: focus on several complementary technologies to remove sulfur
dioxide, nitrogen oxides and other gases from combustion gases before they are released into
the atmosphere.
Oxidation and reduction
Redox Reactions
 Redox reactions are a type of chemical reactions which involves reduction and
oxidations

 A useful mnemonic for remembering how redox processes work is:

 OIL RIG
 Oxidation Is Loss (of electrons) ; Reduction Is Gain (of electrons)

Oxidation States
 The Oxidation state is the apparent charge of an atom in a free element, molecule
or ion.
 In terms of oxidation state:
 Oxidation describes a process in which the oxidation state increases
 Reduction describes a process in which the oxidation state
decreases
 To determine if a reaction is a redox reaction, observe if there is a change in
oxidation state for each element.
 Elements in their natural states and carbon dioxide are considered to
have oxidation number of 0
 Rules for oxidation states:
1. Charge always goes before the number
2. 0 for an atom in a free element (Na, O , S )
2 8

3. +1 for group 1 metals. +2 for group 2 elements

4. +1 for hydrogen when bonded to a non-metal. -1 when bonded
to a metal in hydride form (NaH)
5. -2 for oxygen except in any peroxide where it is -1
6. -1 for group 17 halogens. Oxidation state is positive in
combination with oxygen in oxoanions and oxoacids (Cl has
oxidation state of +7 in HClO )
4

7. In polyatomic ions, sum of oxidation states of all atoms equals

overall charge of the ion
Variable Oxidation States
 In addition to the rules for oxidation states, there are elements with variable
oxidation states. These consist mainly of transition elements

 Since compounds with transition metals have variable oxidation states, the roman
numeral system is used to name such compounds according to IUPAC
 Oxidation numbers are used for transition metals while oxidation states are used
for all other elements
 g. KMnO  is potassium manganate (VII) as Mn has an oxidation
4

number of +7

Balancing Redox Reactions

 Half equations are used to balance complex redox reactions
 Only required to balance an equation in acidic or neutral media
 Steps to balance equations:
1. Assign oxidation states for each atom in the reactant and
product species
2. Deduce which species is oxidized and which species is reduced
3. State the half-equation for the oxidation process and the
corresponding half-equation for the reduction process
4. Balance these half-equations so that the number of electrons
lost equals the number of electrons gained
 5. Add the two half equations together to write the overall redox
reaction
6. Check the total charge on the reactant and product sides
7. Balance charges by adding H  and H O to the appropriate sides
+
2

The activity series

 The activity series ranks metals according to the ease with which they undergo
oxidation
 Most reactive metals are found at the top of the series
 Series found in section 25 of the data booklet

Use of chlorine and ozone as disinfectants in

drinking water
 Access to clean water is determined to be a human right, yet over a billion people
do not have this
 Water supplies are normally disinfected using strong oxidizing agents such as
chlorine (Cl ) or ozone (O ) to kill microbial pathogens
2 3

 Chlorine can be added in three forms: Cl , NaOCl and Ca(OCl) . All three solutions
2 2

yield HOCl which is the antibacterial agent

 The use of chlorine can also cause problems for people. Some people object the
taste of water. Chlorine can also react with other chemical to from toxins such as
chloroform CHCl 3
Electrochemical Cells
 In an electrochemical cell, there can either be a conversion of chemical energy to
electrical energy, or the other way around
 There are two main types of electrochemical cells
1. Voltaic (Galvanic) Cells – convert chemical to electrical energy.
Reactions are spontaneous and exothermic.
2. Electrolytic Cells – convert electrical to chemical energy. Non
spontaneous.

Electrodes
 An electrode is a conductor of electricity used to make contact with a non-metallic
part of a circuit, such as the solution in a cell (electrolyte)
 Electrochemical cells contain two electrodes, anode and the cathode
 In both voltaic and electrolytic cells:
 Oxidation is at the anode
 Reduction is at the cathode
 Mnemonic is “An Ox, red cat“
 In voltaic cell
 Cathode is positive
 Anode is negative
 In electrolytic cell
 Cathode is negative
 Anode is positive

Cell Diagram
 Cell Diagrams are used as shorthand notation to represent a voltaic cell. By
convention, anode is always of left, and cathode on right. The salt bridge is
represented by two parallel lines
 Zn |Zn ||Cu |Cu
(s)
2+
(aq)
2+
(aq) (s)

Types of Cells
1. Voltaic (Galvanic) Cells
 Consists of two half-cells. These two are separated, connected only
by a salt bride. Oxidation occurs at one half-cell (anode), reduction
occurs at on half-cell (cathode)
 There are different types of electrodes used in voltaic cells, most
common one is metal/metal ion electrode
 Metal/metal ion electrode
 Consists of a bar of metal placed in a solution
containing cations of the same metal. Examples
include:
A. Zn |Zn
(s)
2+
(aq)

B. Cu |Cu
(s)
2+
(aq)

C.
 The vertical line represents a phase boundary
(junction)
 Salt bridge which connects both electrodes has
multiple functions:
A. Provides physical separation of
reduction and oxidation processes
B. Provides electrical continuity for
anions and cations
C. Reduces the liquid-junction
potential. This is the voltage generated
when two different solutions come into
contact with each other
 Salt bridge contains a concentrated solution of a
strong electrolyte. The high concentration allows ions
to diffuse out of it. The ions in a salt bridge must be
inert
 To determine which metal will be oxidized, or which
will be reduced, refer to the activity series. Zinc is
higher up on series than copper thus it is more easily
oxidized. The zinc half-cell acts as the anode.
 Voltaic Cell example:
2. Electrolytic Cells
 Electrolysis is the process by which electrical energy is used to drive
a non-spontaneous chemical reaction
 Electrolytic cells consist of a container of electrolyte, two electrodes,
and a battery which is considered an electron pump
 There are many types of electrolytic cells, most common one
is molten salt cell
 Molten Salt Electrolysis
A. Identify all species
B. Identify species attracted to cathode (negative
electrode) and anode (positive electrode)
C. Deduce the two half-reactions taking place at
each electrode, and overall cell reaction
D. Draw and annotate electrolytic cell and show
direction of electrons and of ions
E. State what would be observed at each electrode
 Electrolytic Cell example: