BIOLOGICAL CHEMISTRY

REACTIONS IN BIOMOLECULES

- Oxidation and reduction

reactions
- Condensation

Noor Dina Muhd Noor, PhD

Department of Biochemistry,
FBSB, UPM.
 Oxidation and reduction reaction

Redox

REDOX reactions are reactions that involves both

Reduction & Oxidation simultaneously.
• Definition :
Redox reactions describe all chemical reactions in which
there is a net change in atomic charge.
• It is a class of reactions that include:
• Formation of a compound from its element
• All combustion reactions
• Reactions that generate electricity
• Reactions that produce cellular energy
 Redox reactions

• There are 4 ways to look at whether a substance has been oxidized or

reduced, and they are:

1) Gain / loss of oxygen atoms

2) Gain/ loss of hydrogen atoms
3) Gain/loss of electrons
4) Increase/ Decrease in oxidation states/numbers

OIL RIG : Oxidation Is Loss (of electron) ; Reduction Is Gain (of electrons)
 Oxidation states or
oxidation number (O.N)

• The oxidation state is the apparent charge of an atom in a

free element, molecule or ion.
• In term of oxidation state:
• Oxidation describes a process in which the oxidation state increases
• Reduction describes a process in which the oxidation states
decreases
• To determine if a reaction is a redox reaction, observe if
there is a change in oxidation states for each element.
• Elements is their natural states
• Eg; Carbon dioxide are considered to have oxidation number of 0
 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 oxidations
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
• Eg; KMnO4 is potassium manganate (VII) as Mn has an oxidation number of
+7
Oxidation states of transition metals. The most stable oxidation states
are marked in green.
Oxidation/reduction based on oxygen atoms

• When a substance gains oxygen in a chemical reaction, we

say it has been oxidised. The reaction is called OXIDATION.
• When a substance loses oxygen in a chemical reaction, we
say it has been reduced. The reaction is called REDUCTION.

E.g. Magnesium reacts with copper (II) oxide to produce magnesium

oxide and copper metal.

Mg(s) + CuO(s) –> MgO(s) + Cu(s)

 Oxidation/reduction based on electrons

• Oxidation
• This is the name given to removal of electrons from a species - the
reagent causing the loss of electrons is called the oxidising agent.
• Reduction
• This is the gain of electrons - the species donating the
electrons is called the reducing agent
Summary :
• Obviously the electrons / oxygen leave one species and go to
another.
• Consequently reduction has to be accompanied by oxidation and vice
versa. For this reason reactions involving transfer of electrons are
called reduction and oxidation or redox for short
• An OXIDISING AGENT helps the other substance to get OXIDISED, and
itself gets REDUCED.
• A REDUCING AGENT helps the other substance to get REDUCED, and
itself gets OXIDISED.
Oxidising agents

These are the chemicals that cause the oxidation in a redox

reaction. We call the reacting compounds in a reaction the
reagents (short form of the words reacting agents).

We consider that the removal of electrons from a species is

oxidation and these electrons have to be taken away by another
compound or species.

This species that attracts the electrons is said to be the

oxidising agent i.e. the reagent that causes the oxidation.
Reducing agents

Similarly the reagent that causes reduction in a redox reaction is

said to be the reducing agent.
The oxidising agent takes the electron and is itself reduced, the
reducing agent loses the electrons and is itself oxidised.
Oxidation number of an element in a compound

Oxidation number
• This is the apparent valency of an atom within a compound. It is
usually considered as if the element were bonded ionically to allow
the apparent number of electrons gained or lost to be assessed.
• The sum of all the oxidation numbers in a compound must add up to
0. By convention, the oxidation number is written as a Roman
numeral in the name, eg. iron II sulphate, sulphur VI oxide.
• The oxidation number of an uncombined element is always zero (0)
 Calculating the oxidation number

• There are some elements that virtually always have the same
oxidation number and these can be used to calculate the oxidation
numbers of the atoms in question.
• Hydrogen, for example always has an oxidation number of -1 when
bonded to a metal (more electropositive element) and +1 when
bonded to a more electronegative element (non-metal).
• Oxygen is always -2 (except when in the form of the peroxide ion
when it has an O-O bond giving it an oxidation number of -1).
• Group 1 and 2 metals usually have an oxidation number of 1+ and 2+
respectively.
Electronegativity relate to
oxidation number
Identification of element whether it is oxidized or reduced
by using oxidation numbers

Oxidation and reduction

• For the purposes of oxidation and reduction, the oxidation

number can be thought of as the apparent ionic charge of an
atom within a compound.

• Eg: in sulphuric acid the sulphur is in the VI (6+) oxidation

state. For the purposes of redox we can consider that it has an
ionic charge of +6 (even though it is clearly covalently bonded).
This makes it easier to follow any transfer of electrons.

• If the sulphur changes to an oxidation state of IV during a

chemical reaction then it has gone from an apparent ionic
charge of +6 to a charge of +4, i.e. it has gained two electrons
(negative charges). It has therefore been reduced (gain of
electrons) in the process.
Relationship between oxidation numbers and the names of
compounds

Names of compounds

• Where there is any doubt about the oxidation state of

an element within a compound it is stated using Roman
numerals immediately after the ambiguous element.

• For example iron compounds may be iron in the oxidation

state +2 or +3 - it must therefore be stated as iron II or iron
III in the compound name.
 Balancing Redox Reactions

• When balancing redox reactions, make sure that the number of

electrons lost by the reducing agent equals the number of electrons

gained by oxidizing agent.

• Two methods can be used:

• Oxidation number method

• Half-reaction/ half equation method

 Balancing Redox Reactions

• Method 1: Oxidation number method

1. Assign oxidation numbers to all elements in the reaction

2. From the changes in O.N, identify the oxidized and reduced species

3. Compute the number of electrons lost in the oxidation and gained in the
reduction from O.N changes

4. Multiply one or both of these numbers by appropriate factors to make the

electrons lost equal the electrons gained, and use the factors as balancing
coefficients.

5. Complete the balancing by inspection, adding states of matter.

Practice

• Use the oxidation number method to balance the following

equations:

a) Al (s) + H2SO4 (aq) → Al2 (SO4)3 (aq) +H2 (g)

b) PbS (s) + O2 (g) → PbO (s) + SO2 (g)
 Balancing Redox Reactions

Method 2: Half equations

• Half equations are used to balance complex redox reactions
• Only require 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 H2O to the appropriate sides
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
 Half equation

• We can write 'half' equations to show only what happens to the

species losing electrons or a different 'half' equation to show the
species gaining electrons.

• The whole equation is put together by making sure that the numbers
of electrons are balanced in each half equation and adding them
together (when the electrons will cancel out)
Example: Write the half-equations for the reduction that occurs in the following reaction:

Reduced, (oxidizing agent)

Mg → Mg2+ + 2e Oxidized, (reducing agent)

 Constructing the ionic equation
Full equation can be constructed from two half-equations by adding them
together.

STEPS:
- Number of electron in each of half-equation must be made the same.
- Reduction half-reactions must be added to oxidation half equations and
vice versa.
- Add each left hand side together, then add each right hand side together, as
if it a simple maths sum.
- Eg:

The electrons that appears on either side of the reaction arrow cancel out,
leaving the ions that react.

The above reaction is uncomplicated, as the number of electrons on each side

of the reaction cancel out. The following example shows a situation in which the
electrons do not initially cancel out, in which one half-equation has to be
manipulated to equalise the electrons.
Example: Given the two following half-equations, construct the full ionic equation
for the redox reaction:
Example: Given the two following half-equations, construct the full ionic equation
for the redox reaction:
 Half reaction in acidic
• Use the half reaction method to balance the following equation:

a) ClO3- (aq) + I- (aq) → I2 (s) + Cl- (aq) [acidic]

 Hydrogenation as a redox reaction
• Hydrogenation is a reaction that occurs when molecular hydrogen is added to
an alkene to produce an alkane or hydrogen is added to an alkyne to produce
an alkene or alkane. The reaction is typically performed with the use of a
transition metal catalyst. For example, ethene reacts with hydrogen to form
ethane.

• Note that the hydrogenation reaction is also a redox reaction. Ethene

is reduced, because the oxidation numbers of the carbon atoms
change from −2 to −3 as a result of the reaction.
Redox or not a redox reaction?

• CaCO3 → CaO + CO2

• C2H5OH +O2 → CO2 +H2O

• NaOH +HCl → H2O +NaCl

• H2O + CO2 → H2CO3

• AgNO3 + NaCl → AgCl +NaNO3

 Condensation

Condensation:

a reaction in which two molecules combine to form a larger molecule,

producing a small molecule such as H2O as a by-product. For
example; esterification and formation of peptide bond.
 Condensation Reactions

A condensation reaction is a reaction in which two molecules

combine to form a single molecule. A small molecule, often water, is
usually removed during a condensation reaction.

A H + OH B A B + H2O
 Condensation reaction in formation of
polypeptide of amino acid
Amino acids are important biological molecules that have an amine
functional group on one end of the molecule and a carboxylic acid
functional group on the other end.

When two amino acids combine in a condensation reaction, a covalent

bond forms between the amine nitrogen of one amino acid and the
carboxyl carbon of the second amino acid. A molecule of water is then
removed as a second product.

Amino acids join together to form a molecule called a dipeptide.

The −OH from the carboxyl group of one amino acid combines with a
hydrogen atom from the amine group of the other amino acid to produce water (blue).
 Esterification
An esterification is a condensation reaction in which an ester is formed
from an alcohol and a carboxylic acid. Esterification is a subcategory of
condensation reactions because a water molecule is produced in the
reaction.

The reaction is catalyzed by a strong acid, usually sulfuric acid. When the
carboxylic acid butanoic acid is heated with an excess of methanol and a
few drops of sulfuric acid, the ester methyl butanoate is produced. Methyl
butanoate has the scent of pineapples. The reaction is shown below with
both molecular and structural formulas.