Introduction to

Electrochemistry -
Redox
Lecture 1-4 BCHE 111L – Chemistry for Engineers
Introduction
• Electrochemistry is the branch of chemistry which deals with the chemical
changes caused in the matter by passage of electric current and
conversion of chemical energy into electrical energy and vice versa.
• Thus electrochemistry deals with the interaction between electrical
energy and chemical change.
• Conductors and nonconductors: Substances around us can be divided into
two classes based on their ability to conduct electricity.
Introduction
• Conductors – Substances which allow electric current to flow through
them.
• Metallic Conductors – Conductors that let electric current flow without chemical
reactions involved. These metals can conduct electricity in solid and molten state.
(e.g. Copper, Iron, Silver, Gold, etc.)
• Electrolytes – Conductors that only allow electricity to pass through when in an
aqueous solution and not in solid form. These conduct electricity by the movement
of ions in solutions.
• Non-conductors – Substances that do not allow electricity current to pass through them.
Another term used is insulator.
Introduction
• Difference between electronic and electrolytic conductors
Electronic Conductors
1. Flow of electricity take place
without the decomposition of
substance.
2. Conduction is due to the flow of
electrons
3. Conduction decreases with
increase of temperature.
Electrolytic Conductors
1. Flow of electricity take place by
the decomposition of substance.
2. Flow of electricity is due to the
movement of ions.
3. Conduction increases with the
increase in temperature.
Introduction
• Electrolytes are substances whose solution in water conducts electric current.
Conduction takes place in the movement of ions.
• Examples are salts, acids and bases.
• Substances whose aqueous solution that does not conduct electricity are called non-
electrolytes.
• Examples are solution of cane, sugar, glucose, urea, etc.
• Strong electrolyte are highly ionized in the solution.
• Examples are HCl, H2SO4, NaOH, KOH, etc.
• Weak electrolytes are only feeble in ionized solution.
• Examples are H2CO3, CH3COOH, NH4OH, etc.
Introduction
• Modern view of Ionization
• Electrolytes, when dissolved in H2O or other ionizing medium, produced
electrically charged particles called ions.
• Electrolytes, in water solution, produce two kinds of ions, cation (+) and anion
(-). The two types of charges occur in equivalent quantities.
• Conductance of an electric current by solution is due to the presence of ions
and the extent of this conductivity is dependent upon the number and kinds of
ions between electrodes.
• Ions are independent particles, which have specific chemical properties of
their own.
• Electrolytes in water solution have a greater effect upon the colligative
properties of the solution than those of non-electrolytes.
• Electrolytes maybe divided into two: strong electrolytes (completely ionized)
and weak electrolytes (with few ions)
Redox Reaction
• Electrons are transferred from one chemical species to another.
• Redox (short for reduction–oxidation reaction) is a chemical reaction in which the oxidation
states of atoms are changed. Any such reaction involves both a reduction process and a
complementary oxidation process, two key concepts involved with electron transfer
processes.
• Redox reactions include all chemical reactions in which atoms have their oxidation state
changed; in general, redox reactions involve the transfer of electrons between chemical
species.
• The chemical species from which the electron is stripped is said to have been oxidized,
while the chemical species to which the electron is added is said to have been reduced. It
can be explained in simple terms:
• Oxidation is the loss of electrons or an increase in oxidation state by a molecule, atom, or ion.
• Reduction is the gain of electrons or a decrease in oxidation state by a molecule, atom, or ion.
Redox Reaction

• Types:
• Direct Transfer
• Electrons are directly transferred between chemical species
• Examples: rusting of iron, cleanup of wastewater using iron fillings
• Indirect Transfer
• Electron transfer from one chemical species to another via an electrical circuit.
• Examples: Flashlight batteries, Aluminum smelters
• Electrochemical Reaction - Chemical reaction is coupled with electron
flow through a circuit.
Redox Reaction

• In redox processes, the reductant transfers electrons to the

oxidant.
• Thus, in the reaction, the reductant or reducing agent loses
electrons and is oxidized, and the oxidant or oxidizing
agent gains electrons and is reduced.
• The pair of an oxidizing and reducing agent that are involved in
a particular reaction is called a redox pair. A redox couple is a
reducing species and its corresponding oxidizing form, e.g.,
Fe2+/Fe3+.
Redox Reaction

Sodium and fluorine bonding ionically to form sodium fluoride. Sodium loses its outer electron to
give it a stable electron configuration, and this electron enters the fluorine atom
exothermically. The oppositely charged ions are then attracted to each other. The sodium is
oxidized, and the fluorine is reduced.
Redox Reaction

• Oxidizers
• Substances that have the ability to oxidize other substances (cause them
to lose electrons) are said to be oxidative or oxidizing and are known as
oxidizing agents, oxidants, or oxidizers. That is, the oxidant (oxidizing
agent) removes electrons from another substance, and is thus itself
reduced. And, because it "accepts" electrons, the oxidizing agent is also
called an electron acceptor. Oxygen is the quintessential oxidizer.
• Oxidants are usually chemical substances with elements in high
oxidation states (e.g., H2O2, MnO4-, CrO3, Cr2O72-, OsO4), or else highly
electronegative elements (O2, F2, Cl2, Br2) that can gain extra electrons
by oxidizing another substance.
Redox Reaction

• Reducers
• Substances that have the ability to reduce other substances (cause them to gain electrons) are
said to be reductive or reducing and are known as reducing agents, reductants, or reducers. The
reductant (reducing agent) transfers electrons to another substance, and is thus itself oxidized.
And, because it "donates" electrons, the reducing agent is also called an electron donor. Electron
donors can also form charge transfer complexes with electron acceptors.
• Reductants in chemistry are very diverse. Electropositive elemental metals, such as lithium,
sodium, magnesium, iron, zinc, and aluminum, are good reducing agents. These metals donate or
give away electrons readily. Hydride transfer reagents, such as NaBH4 and LiAlH4, are widely used
in organic chemistry, primarily in the reduction of carbonyl compounds to alcohols.
• Another method of reduction involves the use of hydrogen gas (H2) with a palladium, platinum, or
nickel catalyst. These catalytic reductions are used primarily in the reduction of carbon-carbon
double or triple bonds.
Redox Reaction
• A good example is the reaction between hydrogen and fluorine in which hydrogen is being oxidized
and fluorine is being reduced:
H2 + F2 → 2HF
• We can write this overall reaction as two half-reactions:
• the oxidation reaction:
H2 → 2 H+ + 2 e−
• and the reduction reaction:
F2 + 2 e− → 2 F−
Redox Reaction
• Consider this chemical reaction:
2Na(s) + Cl2(g) →2NaCl
• The reactants are elements, and it is assumed that they are electrically
neutral; they have the same number of electrons as protons.
• The product, however, is ionic; it is composed of Na+ and Cl− ions.
Somehow, the individual sodium atoms as reactants had to lose an
electron to make the Na+ ion, while the chlorine atoms as reactants had
to each gain an electron to become the Cl− ion.
• This reaction involves the transfer of electrons between atoms.
Redox Reaction
• Assigning Oxidation Numbers
1. Atoms in their elemental state are assigned an oxidation number of 0.
• H2, F2, O2, P4, S8
• These pure neutral elements have 0 oxidation number
2. Atoms in monatomic (i.e., one-atom) ions are assigned an oxidation
number equal to their charge. Oxidation numbers are usually written
with the sign first, then the magnitude, which differentiates them
from charges.
• Ions do not share electrons with other ions. Each ion is an individual chemical
species with its own set of oxidation numbers. Treat ions separately
Redox Reaction
• Assigning Oxidation Numbers
3. In compounds, fluorine is assigned a −1 oxidation number; oxygen is usually assigned
a −2 oxidation number (except in peroxide compounds [where it is −1] and in binary
compounds with fluorine [where it is positive]); and hydrogen is usually assigned a
+1 oxidation number (except when it exists as the hydride ion, H−, in which case
rule 2 prevails).
• Hydrogen has an oxidation number of “+1”, except when it is bonded to a metal.
4. In compounds, all other atoms are assigned an oxidation number so that the sum of
the oxidation numbers on all the atoms in the species equals the charge on the
species (which is zero if the species is neutral).
• The most electronegative atom in a polyatomic species has an oxidation number equal to
its number of valence electrons minus eight.
Common Polyatomic Ions
Redox Reaction

• Example: Assign oxidation numbers to the atoms in each

substance.
Br 2

Answer:
Br2 is the elemental form of bromine. Therefore, by rule 1, each atom has an oxidation number of 0.
Redox Reaction

• Example: Assign oxidation numbers to the atoms in each

substance.
SiO2
Answer:
By rule 3, oxygen is normally assigned an oxidation number of −2. For the sum of the
oxidation numbers to equal the charge on the species (which is zero), the silicon atom is
assigned an oxidation number of +4.
Redox Reaction
• Example: Assign oxidation numbers to the atoms in each substance.
• Ba(NO3)2
Answer:
The compound barium nitrate can be separated into two parts: the Ba 2+ ion and
the nitrate ion. Considering these separately, the Ba2+ ion has an oxidation
number of +2 by rule 2.
Now consider the NO3− ion. Oxygen is assigned an oxidation number of −2, and
there are three oxygens.
According to rule 4, the sum of the oxidation number on all atoms must equal
the charge on the species, so we have the simple algebraic equation: x + 3(−2) =
−1; x = +5
Redox Reaction
• Consider the following reaction and identify if Redox Reaction or not;
identify if it is oxidized or reduced and identify the oxidizing and reducing
agent.
FeO(s) + CO(g)  Fe(l) + CO2(g)

FeCO3(s)  FeO(s) + CO2(g)

Redox Reaction
• Consider the following reaction and identify if Redox Reaction or not;
identify if it is oxidized or reduced and identify the oxidizing and reducing
agent.
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l)
Redox Reaction

• Common Mnemonics
• "OIL RIG" — oxidation is loss of electrons, reduction is gain of electrons.
• "LEO the lion says GER" — loss of electrons is oxidation, gain of
electrons is reduction.
• "LEORA says GEROA" — loss of electrons is oxidation (reducing agent),
gain of electrons is reduction (oxidizing agent).
• "RED CAT" and "AN OX", or "AnOx RedCat" ("an ox-red cat") — reduction
occurs at the cathode and the anode is for oxidation.
• "RED CAT gains what AN OX loses" – reduction at the cathode gains
(electrons) what anode oxidation loses (electrons).