Oxidation-Reduction Reactions

Lecture 7
 Electron Theory of Redox Reactions
Oxidation State - oxidation number (or oxidation state) of an atom in a substance as the actual charge of the atom
if it exists as a monatomic ion, or a hypothetical charge assigned to the atom in the substance by simple
rules.

Oxidation–reduction reaction (or redox reaction) is a type of chemical reaction that involves a transfer
of electrons between two species. It is any chemical reaction in which the oxidation number of a
molecule, atom, or ion changes by gaining or losing an electron
Reaction

reactions occurring without reactions occurring with changing the

changing the oxidation oxidation state of the atoms
state of the atoms (redox reactions)

Exchange Displacement
Reactions Reactions

Some Combination and Decomposition

reactions
 Oxidation is the process of giving up electrons by an atom, molecule or ion, and the degree of oxidation increases
Ca – 2e- = Ca+2 H02 – 2e- = 2H+
Recovery is the process of addition electrons to an atom, molecule, or ion. The oxidation state decreases.
Fe+3 + e- = Fe2+ Cl02 + 2e- = 2Cl-

oxidizing agent (oxidant, oxidizer), or oxidising agent (oxidiser)

- it gains one or more electrons
- elements with high electronegativity, i.e. non-metals : F2, O2, Cl2, Br2, S, etc.
- metal and hydrogen ions: Ag +, Au3+, Cu2+, H+, Fe3+, etc.
- molecules that contain atoms of non-metals that have high oxidation states K 2Cr+62O7, KMn+7O4, HN+5O3, H2S+6O4, HCl+7O4, K2Cr+6O4

reducing agent (reductant or reducer)

- an element or compound that loses (or "donates") an electron
- elements with low electronegativity, i.e. all metals and some non-metals (H2, B, C). The most active reducing agent is francium.
- molecules that contain atoms with low oxidation states: Fe+2Cl 2, Cr2+3(SO4)3, KCl-1, H2S-2, N-3H3, H2S+4O3

Substances with redox duality

- contain elements in intermediate oxidation states
- can be both oxidizing and reducing agents,
- for example:
N -3H3 - always a reducer
N2-2H4, N-1H2OH, N20, N2+1O, N+2O, N2+3O3, N+4O2 – have a redox duality
N2+5O5 - always a oxidiser
Nitrogen in the oxidation state -3 can be a reducing agent only, i.e. can only increase the oxidation state.
Nitrogen in the oxidation state +5 is always an oxidizing agent, it cannot increase the oxidation state, it can only lower it .
 Oxidation Reduction Reactions

dismutation

Intramolecular reactions Intermolecular reactions Disproportionation reactions Comproportionation reactions

oxidant and reductant same reactions in which the atoms of the same element in one reactions involving two
matter, but the oxidation of transition of electrons molecule are both an oxidizing substances containing atoms of
change therein atoms of occurs between parts of agent and a reducing agent the same element in different
different elements. different substances. oxidation states

2КClO3 = 2KCl- + 3O2 Ca+2H2O = Ca(OH)2+ H2 4KCl+5O3 = KCl- + 3KCl+7O4 Cu0 + Cu+2Cl2 = 2Cu+1Cl
 VOLTAIC CELLS Any spontaneous redox reaction can serve
as a source of energy in a voltaic cell
(also known as a Galvanic Cell)

It consists of two separate half-cells. A half-cell is composed of an electrode (a strip of metal, M) within a
solution containing Mn+ ions in which M is any arbitrary metal.
• the cathode is where reduction takes place
• the anode is where oxidation takes place
The two half cells are linked together by a wire
running from one electrode to the other.
A salt bridge also connects to the half cells.
Salt
• It is a tube filled with an electrolyte solution such as bridge
KNO3(s) or KCl(s). The purpose of the salt bridge is to
keep the solutions electrically neutral and allow the
free flow of ions from one cell to another.
 Notation for Voltaic Cells
The two half-cell reactions are:

Note that the sum of the two half-reactions (is the net reaction that occurs in the voltaic cell:
it is called the cell reaction.

It is convenient to have a shorthand way of designating particular voltaic cells.

The cell, consisting of a zinc metal–zinc ion half-cell and a copper metal–copper ion half-cell, is written:
Zn(s) | Zn2+(aq) ║Cu2+(aq) |Cu(s)
In this notation,
• the anode, or oxidation half-cell, is always written on the left;
• the cathode, or reduction half-cell, is written on the right.
Zn(s) | Zn2+(aq) ║ Cu2+(aq) |Cu(s)
Anode salt bridge Cathode

A single vertical bar indicates a phase boundary between a solid terminal and the electrode solution.
The two electrodes are electrically connected by means of a salt bridge, denoted by two vertical bars.
 Cell Potential
Work is needed to move electrons in a wire or to move ions through a solution to an electrode. An electric
charge moves from a point at high electric potential (high electrical pressure) to a point at low electric potential
(low electrical pressure). The work needed to move an electric charge through a conductor depends on the total
charge moved and the potential difference. Potential difference is the difference in electric potential (electrical
pressure) between two points. The standard electrode potential, Eo , is the electrode
potential when:
Nernst • the concentrations of solutes are 1 M,
ЕMe = E0Me + (R∙T/n · F) / ln[Men+], • the gas pressures are 1 atm,
Equation
• the temperature has a specified value (usually 25C).

where E0Me- standard potential

R- universal gas constant R=8,314 J⋅K−1⋅mol−1.
F- Faraday constant F=96487
C·mol−1
T – temperature T=298,15 К
n – charge of metal ion

[ Men+] – concentration of the metal , mol·L−1

 Calculation of Cell Potentials Using Standard
Reduction Potentials
The maximum potential difference between the electrodes of a voltaic cell is
referred to as the cell potential or electromotive force (emf) of the cell, or Ecell. emf can be measured
using a digital voltmeter
Ек > Еа that is, the cathode is an electrode with a higher electrode potential.

Standard electrode potentials are useful in determining the strengths of oxidizing and reducing agents under standard-
state conditions.

• the strongest oxidizing agents in a table of standard electrode potentials are the oxidized species corresponding to half-
reactions with the largest (most positive) Eo values
• the strongest reducing agents in a table of standard electrode potentials are the reduced species corresponding to half-
reactions with the smallest (most negative) Eo values.

A system with a high electrode potential is always an oxidizing agent in relation to a

emfrxn = Е0Ox – E0Red system with a lower potential.

Possibility and direction of Redox-processes • if emf > 0 – reaction is possible;

• if emf <0 – reaction is impossible
Relation between
Eo, ΔGo, and K
 Possibility and direction of Redox-processes

1. According to emf emf > 0

2. According to Free Energy ∆G0 < 0 ΔG0= - n ·F · ΔE0

At Non-Standard conditions: the electrode potential is determined as:

Eoх/Red = E00х/Red - (RT/n· F) · ln(CRed/СOx)

0.059
0 𝐶 𝑂𝑥
𝐸=𝐸 + ⋅l o g
𝑛 𝐶ℜ 𝑑 CRed и Cox - molar concentration
 Example 1

Is it possible to oxidize Br- to elemental bromine using elemental chlorine, i.e. carry
out the reaction according to the equation:
2Br -+ Cl02 = Br02 + 2Cl-

Е0 Br2/2Br- = 1,0652V ≈ 1,07 V

Е0 Cl2/2Cl - = 1,3595V ≈ 1,36 V

emf = ∆ Е = Е0оx. – Е0red.= 1,3695 – 1,0652 = 0,29V > 0,

So the reaction is possible.
 Example 2
Select potassium salt as a reducing agent for FeCl3

2KX- + 2 Fe 3+Cl3 = X02 + 2KCl + 2 Fe 2+Cl2

(X = F-, Cl-, Br-, I- )
E0Fe3+/Fe+2 = +0,77 V

E0F2/2F- = + 2,86 V

E0Cl2/2Cl- = + 1,36 V

E0Br2/2Br- = +1,07 V

E0I2/2I- = +0,54 V < 0.77 V

Let's calculate the emf with the participation of halides for KI
ΔЕ0298 = Е0оx. – Е0red. = 0,77 – 0,54 = 0,23V > 0. Only potassium iodide will

reduce FeCl3, because Δ Е0298 > 0.