The activity series

• Oxidizing & reducing agents are of different strength depending on their

relative tendencies to lose or gain electrons
o Metals at the top of the activity series are more reactive and
stronger reducing agents (more readily oxidized)
o Metals at the bottom of the activity series are less reactive and
weaker reducing agents (less readily oxidized)
• Reactivity can be checked through displacement reactions
o A metal can only displace another in a compound if it is higher in
the activity series (more reactive)
• Activity series can be used to determine whether a reaction will occur or
not
o more reactive elements will replace less reactive elements in a
compound.
• Ex)

Electrochemical cells
• Two types of electrochemical cells: Voltaic (galvanic cells) & electrolytic cells
o Voltaic cells – generate electricity from chemical reactions (makes electricity)
o Electrolytic cells – drive chemical reactions using electrical energy (add electricity)

Voltaic cells
• Voltaic cells convert energy from spontaneous redox reactions (exothermic)
• Chemical processes to electrical energy
o voltaic cells create electricity using a chemical reaction
• Voltaic cells consist of two different half cells
o half-cell = a metal in contact with an aqueous solution of its ions

• Two half cells are connected to form a voltaic cell, allowing electrons to
flow during the redox reaction and produce electrical energy
o Half cells connected are called electrodes
• Anode = electrode where oxidation occurs, negative charge (-)
• Cathode = electrode where reduction occurs, positive charge (+)
• Voltaic cell consists:
o External electronic circuit
▪ Electrons will flow from the anode to the cathode
through the wire
 o A salt bridge
▪ Contains aqueous solution of ions, neutralizes
any build up of charge and maintain potential
difference
▪ Aqueous NaNO3 and KNO3 often used
▪ Anions in the salt bridge move from the
anode to the cathode
▪ Cations move in the salt bridge move from
the cathode to the anode

• Electrons always flow in the external circuit from anode to cathode

• The metal higher in the activity series is oxidized and the metal lower in the activity series is
reduced
o Remember: An Ox, Red Cat (Anode Oxidation, Reduction Cathode)
• The direction of electron flow and the voltage generated will be determined by the difference in
reducing strength of the two metals

• In a voltaic cell, electrons from the stronger reducing agent to the weaker one
o The metal with the more negative E° (stronger reducing agent) gets oxidized → anode
o The metal with the more positive E° (weaker reducer / better oxidizer) gets reduced →
cathode

Cell diagram
• A cell diagram is a shorthand notation to represent the
redox reactions of an electrical cell
• For the cell above, the cell diagram is as follows:
• A single vertical line is used to separate different states of
matter on the same side
• A double vertical line represents a salt bridge between the
half-cells
• The anode (where oxidation occurs) is placed on the left
side of the ||
• The cathode (where reduction occurs) is placed on the right side of the ||
 Electrolytic cells
• Electrolytic cells convert electrical energy to chemical energy, by bringing about non-
spontaneous processes. The electrical energy from a battery can force a non-spontaneous
reaction to happen
o Uses an external source of electrical energy to bring about a redox reaction that would
otherwise be non-spontaneous
o The electrodes are placed in the electrolyte, connected to the power source by electrical
wires
o The electrodes cannot touch each other.
• Reactant in the process of electrolysis: electrolyte
o Substance that conducts electricity as a liquid/aqueous and is chemically decomposed in
the process

o The power source should be a battery or a DC power source

o The electrodes are placed in the electrolyte, connected to the power source by electrical
wires
o Electrodes must be made from an inert, heat resistant material like graphite or platinum
• Unlike in voltaic cells, the power source causes the polarity of the electrodes to change
o Anode of the electrolytic cell is positive
o Cathode of the electrolytic cell is negative
• Two forms of flow of energy in electrolytic cell:
o Electrons (electrical energy) move from Anode → Cathode
o Flow of current in electrolyte is facilitated by ions or chemical energy
▪ Positive ions towards cathode and negative ions towards anode

Voltaic cell Electrolytic cell

Chemical energy is converted to electrical energy Electrical energy is converted to chemical energy

Reaction is exothermic Reaction is endothermic

A spontaneous reaction produces an electric current An electric current drives a non-spontaneous reaction

Current is conducted by electron flow in wires and mo Current is conducted by electron flow in wires and mo
vement of ions in salt bridge vement of ions in electrolyte

Anode is negative (oxidation) Anode is positive (oxidation)

Cathode is positive (reduction) Cathode is negative (reduction)
 Standard electrode potential
• Tells us how strongly a substance wants to gain electrons compared to hydrogen under standard
conditions
→ Reference standard: Standard hydrogen electrode (기준점)
• Standard Conditions:
o 298K
o 1.0 mol dm-3 ion conc.
o 100 kPa pressure

Standard hydrogen electrode

• The SHE is a hydrogen half-cell comprising a solution of 1 mol dm–3 H+ ions at 298 K, hydrogen
gas at 100 kPa and 298 K and a platinum electrode
o Used as a reference to measure the electrode
potential of other half-cell
• Value of the standard hydrogen electrode is assigned an
electrode potential (𝐸 𝜃 ) value of 0 V
• Standard electrode potential (𝐸 𝜃 ): EMF generated when a
half cell is connected to the standard hydrogen electrode
by an external circuit and a salt bridge, measured under
standard conditions
• The standard hydrogen electrode is set up as:
o A wire attached to a piece of platinum (or covered in platinum)
o The wire is immersed in a 1.0M strong acid
solution (Generally HCl)
o A glass tube around the wire (electrode)
o H2 gas is bubbled in at a pressure of one
atmosphere and a temperature of 25°C through the
glass tube into the solution
o This gives 0.0V
o However, when the SHE is attached to another
half-cell this will give the 𝐸 𝜃 𝑐𝑒𝑙𝑙 of the other half cell

examples)

• The standard electrode potential is always given for the reduction reaction
o Oxidized species on left, reduced species on right
 • 𝐸 𝜃 values refer to the reduction reaction
• 𝐸 𝜃 values do not depend on the total number of electrons, so do not have to be scaled up or
down according to the stoichiometry of the equation
• the more positive the 𝐸 𝜃 value for a half-cell, the more readily it is reduced
o The half cell with the higher (more positive) electrode potential is the cathode, and the
half cell with the lower (more negative) electrode potential is the anode
• Electrons always flow towards the half cell with the highest 𝐸 𝜃 value

Calculating Cell potential

Electrolysis *discharge = the loss or gain of electrons by ions at the electrodes

Electrolysis is solved differently depending on the state of the electrolyte

• In molten electrolysis: No water → only salt ions discharge

• In aqueous electrolysis: Water competes with ions, so use E° values to determine which
species is discharged.

Molten Electrolyte Electrolysis

• Contains only one type of cation and one type of anion
• No water present, so no competition from H2O or OH-
• Ex) Molten NaCl

Aqueous Electrolyte Electrolysis

• Contains ions from the salt + water molecules (H2O)
• Competition between ions and H+ / OH- from water
→ Use electrode potential to determine who gets discharged
• Ex) Aqueous NaCl
• * For negative ions the order of discharge: OH- > Cl- > SO42-
Concentrated vs. Dilute Electrolysis

• Cathode reactions are typically dictated by electrode potential values only

• Anode reactions are influenced by both electrode potential & concentration

• In dilute solutions:
o Aren’t enough halide ions to compete with OH- effectively

• In concentrated solutions:
o Halide ions outnumber OH-

Electrolysis of CuSO4 (copper electrode )

1. Ions present:

2. At cathode possible reactions:

o Cu2+ is preferentially reduced and Cu(s) is discharged

3. At anode possible reactions:

o Cu electrode itself is oxidized, supplying electrons for the reaction and dissolving as Cu 2=
Electrolysis of CuSO4 (carbon=graphite, or inert electrodes)
1. Ions present:

2. At cathode possible reactions:

o Cu2+ is preferentially reduced and Cu(s) is discharged

3. At anode possible reactions:

o OH- (H2O) is preferentially oxidized

Free radical substitution
• Alkanes undergo free radical substitution reactions
o An atom or group of atoms is replaced by another atom or group
o Most commonly involve halogenation
• Substitution reactions happen in which hydrogen atoms are replaced one by one by a
halogen
Replacing hydrogen atoms in an alkane molecule with chlorine or bromine is called chlorination
or bromination
• Requires a catalyst usually in the form of UV light
• Free radicals are species with unpaired electrons which are represented by a dot
• Three stages of the mechanism: initiation, propagation and termination

Initiation:
• Initiation occurs in the presence of UV light
• Photochemical homolytic fission then occurs where the bond
between the halogen is broken by UV light which produces two
halogen radicals
• In initiation steps the number of free radicals increases

Propagation:
• Start with a reactive radical and end with a reactive radical
o Allows the reaction to continue
• In propagation the number of free radicals stays the same

Termination:
• Removes free radicals from the mixture by causing them to react
together and pair up their electrons
o 2 radicals react to make no radicals
• In termination steps the number of free radicals decreases
Alcohol Reactions

• [𝑂] = an oxidizing agent

Primary Alcohols:
• The oxidation of any primary alcohol is a two-step process that first produces an aldehyde which
is then further oxidized to a carboxylic acid
• The alcohol is heated under reflux with an excess of the oxidizing and using K 2Cr2O7

Secondary Alcohols:
• The oxidation of any secondary alcohol is a one-step process that produces a ketone
 Nucleophilic Substitution Reactions
• Two major classes of nucleophilic substitution reactions: SN1 and SN2

SN2: Nucleophilic biomolecular substitution reaction

• One step reaction that involves the formation of an unstable transition state
• Primary halogenoalkanes undergo SN2 reactions
• Example) chloroethane

Overall reaction:

• The nucleophile will attack the opposite side of the leaving group, despite the leaving group
haven’t not departed yet
• An unstable transition state is then formed in which the carbon is weakly bonded to the leaving
group and the nucleophile
• The carbon to the leaving group breaks heterolytically and the leaving group departs

• The rate is bimolecular. The rate determining step (slow step) depends on both the concentration
of the leaving group and the nucleophile

SN1: Nucleophilic unimolecular substitution reaction

• Two step reaction that involves the formation of a carbocation intermediate
• Tertiary halogenoalkanes undergo SN1 reactions
• Example) 2-chloro-2-methylpropane

Overall reaction:
• Halogenoalkane ionizes by breaking its carbon-halogen bond heterolytically creating a stable
intermediate
o Carbocation intermediate
• Nucleophile will attack and bond to the intermediate which results in the final product

• Carbocation is stabilized by the presence of the three alkyl groups → positive inductive effect
(electron donating)
 Electrophilic addition reactions
Definitions

Electrophile: An electron deficient species that can accept an electron pair to form a new cova
lent bond (Acts like a Lewis Acid)

• An addition reaction occurs when two reactants combine to form a single product.
o Characteristic of unsaturated compounds containing double or triple bonds
• An electrophilic addition reaction is an addition reaction where a molecule with a region of high
electron density is attacked by something carrying some degree of positive charge

• Nature of double bond in alkenes:

• Carbon atoms of the double bond are sp2 hybridized, fairly open structure making it relatively easy
for incoming groups to attack
• Pi bonds are less closely associated with the nuclei, breaks more easily during addition reactions
• Pi bond is attractive to electrophiles

Ethene + bromine

• Bromine molecule is polarized by an alkene

• Bromine molecule splits heterolytically forming Br+ and Br – and the initial attack on the ethene is
carried out by the positive ion, Br+
o Slow step, results in unstable carbocation intermediate

• The unstable species reacts rapidly with Br – forming the product

Ethene +Hydrogen bromine

• HBr (polar molecule) undergoes heterolytic fission to form H+ and Br –

• The electrophile H+ makes the initial attack on the alkene’s double bond
• Unstable carbocation reacts quickly with Br – to form the addition product

• Reactivity: HI > HBr > HCl

Markovnikov’s Rule
• Markovnikov’s rule states the hydrogen will attach to the carbon that is already bonded to the
greater number of hydrogens
o The more electropositive part of the reacting species bonds to the least highly substitute
carbon atom in the alkene (the one with smaller number of carbons attached)

• Hydrogen and bromine can be bonded to two different spots

• 2-bromopropane is the main product
o Reason: secondary carbocation thus greater stabilization due to positive inductive effect,
more likely to persist and react with Br -