CHEMICAL FOUNDATION OF BIOCHEMISTRY - 1

Course Code: 21BCH2T411

UNIT-5
REDOX REACTIONS

Prepared by
Dr. Austin Richard S
Department of Lifesciences
Kristu Jayanti College
Kothanur, Bengaluru - 560077
 THERMODYNAMICS
➢ Thermodynamics deals with the concepts of heat and temperature and the inter-conversion
of heat and other forms of energy.

For example :
1. Chemical energy stored by molecules may be released as heat during
chemical reactions when a fuel like methane, cooking gas or coal burns in air.
2. The chemical energy may also be used to do mechanical work when a fuel burns in an
engine or can be convert into electrical energy.

➢ The study of these energy transformations forms the subject matter of thermodynamics.
➢ The laws of thermodynamics deal with energy changes of macroscopic systems involving
a large number of molecules rather than microscopic systems containing a few
molecules.

➢ Thermodynamics is not concerned about how and at what rate these energy
transformations are carried out, but is based on initial and final states of a system
undergoing the change.

➢ Laws of thermodynamics apply only when a system is in equilibrium or moves from one
equilibrium state to another equilibrium state. Macroscopic properties like pressure and
temperature do not change with time for a system in equilibrium state.
System
A thermodynamic system is a specific portion of matter with a definite boundary on which our
attention is focused. The system boundary may be real or imaginary, fixed or deformable.
There are three types of systems:

1. Isolated System – An isolated system cannot exchange energy and mass with its
surroundings. Example: Thermo flask

2. Closed System – Across the boundary of the closed system, the transfer of energy with its
surrounding but not the mass. Example : Refrigerator

3. Open System – In an open system, the mass

and energy both may be transferred
between the system and surroundings. A
steam turbine is an example of an open
system.
Surrounding
Everything outside the system that has a direct influence on the behaviour of the system
is known as a surrounding.
Thermodynamic Process
A system undergoes a thermodynamic process when there is some energetic change within
the system that is associated with changes in pressure, volume and internal energy.

There are four types of thermodynamic processes that have their unique properties, and they
are:
1. Adiabatic Process – A process where no heat transfer into or out of the system occurs.
2. Isochoric Process – A process where no change in volume occurs and the system does
no work.
3. Isobaric Process – A process in which no change in pressure occurs.
4. Isothermal Process – A process in which no change in temperature occurs.
Properties of Thermodynamics
Intensive Properties
➢ An intensive property is a physical property of a system that does not depend on the
system size or the amount of material in the system.
Example : density, pressure and temperature
Extensive Properties
➢ There are properties such as length, mass, volume, weight, etc. that depend on the
quantity or size of the matter, these properties are called an extensive property of
matter
➢ Their value changes if the size or quantity of matter changes.
Example : volume, internal energy, length, mass, volume, weight.
Enthalpy
What is Enthalpy?
Enthalpy is the measurement of energy in a thermodynamic system. The quantity of
enthalpy equals the total heat content of a system, equivalent to the system’s internal
energy plus the product of volume and pressure.
In the International System of Units (SI), the unit of measurement for enthalpy is the joule.

Mathematically, the enthalpy, H, equals the sum of the internal energy, U, and the product
of the pressure, P, and volume, V, of the system.
H = U + PV Where U : internal energy
P: Pressure
V : Volume
What is Entropy?
Entropy is the measure of disorder in a thermodynamic system. It is represented as
ΔS = ΔQ /T where Q is the heat content and T is the temperature.
Entropy is a thermodynamic quantity whose value depends on the physical state or condition of
a system. In other words, it is a thermodynamic function used to measure the randomness or
disorder.
For example, the entropy of a solid, where the particles are not free to move, is less than the
entropy of a gas, where the particles will fill the container.
Properties of Entropy
➢ Entropy is higher in malleable solids compared to brittle, hard substances.
➢ Dissolving a gas in water decreases entropy, while dissolving a liquid or solid in
water increases it.
➢ Entropy rises with increasing chemical complexity.
➢ As mass increases, entropy increases.
The relationship between enthalpy and entropy:
The relationship between enthalpy and entropy is seen in the calculation of Gibbs free
energy. Developed by Josiah Willard Gibbs in the 1870s,
Gibbs free energy :
Gibbs energy represents the available energy in a system that can perform work, when
the temperature and pressure are kept constant.
It is defined as the sum of the system's enthalpy and the product of its entropy and
temperature and is denoted by G. Where,
G is Gibbs free energy
G = H – TS or G = U + PV - TS U is the internal energy in joules
P is the pressure in Pascal
If the reaction is carried out under constant temperature V is the volume in m3
T is the temperature in Kelvin
S is the entropy in joules/Kelvin
ΔG = Δ H – T Δ S H is the enthalpy in joules
 GIBBS FREE ENERGY CHANGE
➢ The standard Gibbs free energy change, ΔG°, indicates the thermodynamic favorability of a physical
or chemical process. It’s defined as the energy available to do work at a constant temperature and
pressure.
➢ Gibbs free energy change (ΔG) is a measure of the spontaneity of a reaction at constant temperature
and pressure.
If ΔG is Negative = indicates a spontaneous reaction. Reaction is thermodynamically favored
If ΔG is Positive = indicates a non-spontaneous reaction.
If ΔG is Zero = indicates reaction is at equilibrium
The value of ΔG° can be calculated directly from the values of ΔH° and ΔS° using the following equation:
ΔG° = ΔH° - TΔS°.
When equilibrium attained there is no further energy change , then ΔG° = -2.303 RT log K . Where K is
reaction quotient . R is the gas constant.
Example : Breakdown of glucose where ΔG is Negative Where as photosynthesis ΔG is Positive
Example: Calculate the ΔG for the oxidation of glucose in cellular respiration at standard
temperature
The oxidation of glucose in cellular respiration can be represented by the reaction:
C6H12O6 ---→ 6CO2+12H20

we use the Gibbs free energy formula:

ΔG° = ΔH° - TΔS°.

1.Enthalpy (ΔH) : The oxidation of glucose is an exergonic (energy-releasing) reaction.

ΔH is negative: -673kcal
2.Entropy (ΔS) : 1 molecule of glucose breakdown into 6CO2+12H20 increasing
disorder. ΔS is positive: +0.182kcal
3.Calculating ΔG for Glucose Oxidation under standard conditions (25°C or 298 K):
ΔG° = ΔH° - T ΔS°
ΔG = −673−(298×0.182)

ΔG ≈ −727.24kcal/mol. The reaction is spontaneous and exergonic.

EFFECT OF TEMPERATURE ON SPONTANEITY OF REACTION

ΔG° = ΔH° - TΔS°

ΔG ΔH ΔS Description Example Process

- - + Reaction spontaneous at all Burning of wood Exothermic

temperature
- (at low T) - - Reaction spontaneous at low Freezing (ice formation) Exothermic
temperature
+ (at high T) - - Reaction nonspontaneous at Formation of calcium Exothermic
high temperature carbonate from calcium
oxide and carbon dioxide.
+ (at low T) + + Reaction nonspontaneous at Ammonium Chloride Endothermic
low temperature Dissolution
- (at high T) + + Reaction spontaneous at high Melting of Iron above Endothermic
temperature melting point
+ (at all T) + - Reaction nonspontaneous at formation of graphite from Endothermic
all temperature diamond.
 LAWS OF THERMODYNAMICS

There are four laws of thermodynamics :

1. First law of thermodynamics

2. Second law of thermodynamics
3. Third law of thermodynamics
4. Zeroth law of thermodynamics
1. First law of thermodynamics
“It is also called as law of conservation of energy, states that energy can neither be created
nor destroyed, but it can be changed from one form to another.”

Example :
1. Plants use sunlight to make chemical energy through photosynthesis. When we eat
plants, our bodies turn this chemical energy into kinetic energy, which helps us do
activities and move.
2. Turning on a light doesn’t make new energy; it just changes electrical energy into light
energy.
2. Second law of thermodynamics

“Entropy of an isolated system always increases over time. Any isolated system will naturally
move toward thermal equilibrium, which is the state of maximum entropy for the system.”
The entropy of the universe only increases and never decreases.

Example:
A hot cup of coffee cooling down in a room. The heat from the
coffee spreads into the cooler air around it, and over time, the
coffee and the room reach the same temperature. The heat
energy spreads out, increasing the overall disorder or entropy
in the system. This process happens naturally and can’t
reverse on its own—once cooled, the coffee won’t warm up
again without adding more energy.
3. Third law of thermodynamics
“The entropy of any pure crystalline substance approaches zero as the temperature
approaches absolute zero (0 Kelvin or -273.15°C)”.
This means that at absolute zero, a system(pure crystal) reaches a state of perfect
order with minimum possible energy, and there is no movement or randomness in the
particles. However, reaching absolute zero in practice is impossible, as it would require
removing all thermal energy from the system, which is beyond current technological
capabilities.
Example :
In a perfect crystal, the atoms are arranged in a highly ordered, repeating pattern. As the
temperature decreases, the atoms move less, and at absolute zero, the crystal reaches its
lowest possible energy state with perfect order and no entropy (disorder).
4. Zeroth law of thermodynamics
“If two systems are each in thermal equilibrium with a third system, then they are in thermal
equilibrium with each other. “

Example: Imagine two cups, A and B, both containing boiling water.

When a thermometer is placed in cup A, it heats up until it reaches
a reading of 100 °C, indicating that it is in thermal equilibrium with
cup A. Moving the thermometer to cup B, it still reads 100 °C,
showing that it is also in equilibrium with cup B. According to the
Zeroth Law of Thermodynamics, we can conclude that cup A and
cup B are in thermal equilibrium with each other.
 REDOX REACTIONS
➢ Redox reactions are chemical processes involving
oxidation and reduction, where the reactants
experience changes in their oxidation states.
➢ The term "redox" combines "reduction" and
"oxidation."
➢ Each redox reaction can be divided into two distinct parts: the reduction process and the
oxidation process.
➢ The oxidation and reduction reactions always occur simultaneously in redox or oxidation-
reduction reactions.
➢ The substance getting reduced in a chemical reaction is known as the oxidizing agent, while a
substance that is getting oxidized is known as the reducing agent.
Types of redox reactions
The different types of redox reactions are
1. Decomposition Reaction
2. Combination Reaction
3. Displacement Reaction
4. Disproportionation Reactions
1. Decomposition Reaction
This kind of reaction involves the breakdown of a compound into different compounds.
Examples of these types of reactions are
Example 1.
2NaH → 2Na + H2
(Sodium is reduced (oxidation state goes from +1 to 0) .
Hydrogen is oxidized (oxidation state goes from -1 to 0)

Example 2.
2H2O → 2H2 + O2
Oxygen is oxidized (oxidation state changes from -2 to 0).
Hydrogen is reduced (oxidation state changes from +1 to 0).
2. Combination Reaction
These reactions are the opposite of decomposition reactions and hence, involve the
combination of two compounds to form a single compound in the form of A + B → AB.

For example,
H2 + Cl2 → 2HCl
Hydrogen is oxidized (oxidation state changes from 0 to +1).
Chlorine is reduced (oxidation state changes from 0 to -1).

C+O2→CO2
Carbon is oxidized (oxidation state changes from 0 to +4). Oxygen is reduced (oxidation state changes from 0 to -2).
3. Displacement Reaction
In this kind of reaction, an atom or an ion in a compound is replaced by an atom or an
ion of another element.
It can be represented in the form of X + YZ → XZ + Y.

Types of Displacement Reaction

a. Metal displacement reaction
b. Non-metal displacement reaction
a. Metal Displacement
In this type of reaction, a metal present in the compound is displaced by another metal.
These types of reactions find their application in metallurgical processes where pure metals
are obtained from their ores.
For example, CuSO4+Zn→Cu+ZnSO4

b. Non-metal Displacement
In this type of reaction, we can find a hydrogen displacement and, sometimes, rarely
occurring reactions involving oxygen displacement.
4. Disproportionation Reactions
Disproportionation reactions are known as reactions in which a single reactant is oxidized
and reduced.

For example, P4 + 3NaOH + 3H2O → 3NaH2PO2 + PH3

Some phosphorus atoms are oxidized (from 0 to +1 in NaH2​PO2​ ).
Other phosphorus atoms are reduced (from 0 to -3 in PH3​)
 OXIDIZING AGENTS
The substance (atom, ion and molecule) that gains electrons and is thereby reduced to a
low valency state is called an oxidising agent.

Important Oxidizing Agents

•Molecules are made up of electronegative elements.

Example : O2, O3, and X2 (halogens)
•Compounds containing an element that is in the higher oxidized state.
Example : KMnO4, K2Cv2O7, HNO3, KClo3
•Oxides of metals and non-metals.
Example : MgO, CuO, CrO3, P4O10

•Fluorine is the strongest oxidizing agent.

 REDUCING AGENT
The substance that loses electrons and is thereby oxidized to a higher valency state is called
a reducing agent.

Important Reducing Agents

➢ All metals, for example, Na, Zn, Fe, Al; A few non-metals, such as C, Hydrogen, S, P
➢ Hydracids, for example, HCl, HBr, HI, H2S
➢ A few compounds contain an element in the lower oxidation state. Examples include, FeCl2, FeSo4, SnCl2,
Hg2Cl2

➢ Metallic hydrides, including NaH, LiH, CaH2, etc.; Organic compounds like HCOOH
➢ Lithium is the strongest reducing agent in the solution, and caesium is the strongest reducing agent in the
absence of water. The substances which act as oxidizing as well as reducing agents are H2O2, SO2, H2SO3,
HNO2 and NaNO2
 STOCK NOTATION
“Stock notation is the representation of oxidation number by putting a Roman numeral in
parenthesis after the symbol of the metal in molecular formula.”

Example : Stock notation for HAuCl4(Auric chloride). Here we need to find the oxidation number for Au (metal) in HAuCl4

Let us consider oxidation number of Au is X

According to the rule, Oxidation number of Hydrogen is +1 Oxidation number of Chlorine is -1

Step 1. Find the oxidation number of Hydrogen in HAuCl4

There is one Hydrogen is present in the HAuCl4 . Therefore oxidation number of Hydrogen in HAuCl4 = 1 (+1) = +1

Step 2. Find the oxidation number of Chlorine in HAuCl4

There are 4 Chlorine is present in the HAuCl4. Therefore oxidation number of Chlorine in HAuCl4 = 4(-1) = -4

Step 3 . Now Find the Oxidation number of Au using this formula

H Au Cl4 = 0 Therefore oxidation state of Au in HAuCl4 is 3

1+ X+(-4) = 0
1 +X– 4 =0
Stock notation for HAuCl4(Auric chloride) represent as HAu(III)Cl4
X - 3 =0 ; X= 3
Rules of Common Oxidation Number
Using Stock notation, represent the following compounds:
HAuCl4(Auric chloride), Tl2O(thallium oxide), FeO, Fe2O3 ,Cul(copper Iodide), CuO,
MnO and MnO2.

Oxidation number for the metals in the given compound is as follows :

HAuCl4→Au has 3 Tl2O →Tl has 1
FeO →Fe has 2 Fe2O3→Fe has 3
CuI →Cu has 1 CuO→ Cu has 2
MnO→Mn has 2 MnO2→Mn has 4

Final Answer: Therefore, the stock notation for these compounds may be represented as:

HAu(III)Cl4, Tl2(I)O, Fe(II)O, Fe2(III)O3, Cu(I)I, Cu(II)O, Mn(II)O, Mn(IV)O2

Change in the oxidation number
➢ The oxidation number is the total number of electrons that atoms in a molecule can
share, lose, or gain while forming chemical connections with atoms of various elements.
➢ In an redox reaction involving two or more reactants, one reactant undergoes oxidation,
and another undergoes reduction. This process causes a change in the oxidation numbers
of the compounds and metals involved.

For example, in the reaction between elemental iron and copper sulfate:
Fe + CuSO4 → FeSO4 + Cu (precipitate)
During this reaction, the oxidation number of iron increases from 0 to +2, while the oxidation number
of copper decreases from +2 to 0. This behavior is consistent with the activity series of elements,
where iron is ranked above copper. As a result, iron is more likely to form Fe²⁺, while Cu²⁺ is reduced
to metallic copper (Cu).
 EXERGONIC REACTION
➢ An exergonic reaction is a reaction that releases free energy (Free energy, also called Gibbs
free energy (ΔG))
➢ In exergonic reaction free energy is released when reactants undergo reactions to form
products.
➢ In exergponic reaction ΔG is negative or less than zero(ΔG < 0) in exergonic
reaction.
➢ Exergonic reactions are spontaneous and thermodynamically favorable.
Example : Breakdown of glucose during cellular respiration,
where energy is released and used by the cell.
C6H12O6 → 6CO2+12H2O ;
ΔG ≈ −727.24kcal/mol. The reaction is spontaneous and exergonic.

Time
Some more Examples for exergonic reaction :
➢ ATP Hydrolysis: The hydrolysis of ATP to ADP and inorganic phosphate (Pi) releases energy (about -7.3 kcal/mol),
which is used to drive various cellular activities, including muscle contraction, active transport, and biosynthesis.
ATP+H2O→ADP+Pi+energy

➢ Electron Transport Chain (ETC): In mitochondria, electrons from NADH and FADH₂ are passed along a series of
complexes in the ETC, releasing energy used to pump protons across the inner mitochondrial membrane. The
ETC is exergonic overall and involve in ATP production.

➢ Glycolysis: The initial breakdown of glucose in the cytoplasm through glycolysis is an exergonic process. It
produces ATP and pyruvate. Pyruvate enters citric acid cycle for further energy production.

➢ Beta-Oxidation of Fatty Acids: This is the process of breaking down fatty acids in the mitochondria to produce
acetyl-CoA, NADH, and FADH₂. Each step in beta-oxidation releases energy, which is then used in the citric acid
cycle and electron transport chain to generate ATP.
 ENDERGONIC REACTIONS
➢ An endergonic reaction is a reaction that absorb free energy from its surrounding.
➢ In endergonic reaction free energy is absorbed when reactants undergo reactions to
form products.
➢ These reactions require an external energy source to occur, as they are not
spontaneous.
➢ In endergonic reaction ΔG is Positive or more than zero(ΔG > 0)
For example : Photosynthesis
6CO2​+6H2​O+ light energy →C6​H12​O6​+6O2​ Δ G = +2870 kJ/mol
In this process, light energy is absorbed and converted into chemical energy
stored in glucose, making it a classic endergonic reaction in biological systems.
In the endergonic process, light energy is
absorbed and converted into chemical
energy stored in glucose, making it a classic
endergonic reaction in biological systems.

Some more examples for endergonic reaction

1.Muscle Contraction: ATP fuels muscle movement, converting chemical energy into
mechanical energy.
2.Protein Synthesis: Cells assemble amino acids into proteins, using ATP energy.
3.Nitrogen Fixation: Bacteria convert atmospheric nitrogen (N2) into ammonia
(NH3), using ATP energy.
4.Glucose Synthesis: Cells convert pyruvate into glucose, using ATP energy.
 REDOX POTENTIAL
Redox Potential (also called oxidation-reduction potential) is a measure of the tendency of a
chemical species to gain or lose electrons in a chemical reaction. It is measured in volts (V) or
millivolts (mV) and is denoted as E₀ or E’₀.

Positive redox potential

A more positive redox potential indicates a stronger tendency to accept electrons (oxidizing
agent).
Example
F2(g) + 2e- ⇌ 2F- Eo = +2.87 V
Cl2(g) + 2e- ⇌ 2Cl- Eo = +1.36 V
Au+ + e- ⇌ Au(s) Eo = +1.69 V
Negative redox potential
A more negative redox potential indicates a stronger tendency to donate electrons
(reducing agent).
Example :

Li+ + e- ⇌ Li Eo = -3.04 V
Mg2+ + 2e- ⇌ Mg Eo = -2.37 V
Al3+ + 3e- ⇌ Al Eo = -1.66 V
Application of redox potential
➢ Electron Transport Chain (ETC): In cellular respiration, redox potential drives the electron transport chain in
mitochondria. Electrons are transferred from NADH and FADH2, this electron transfer release energy which is used
to pump protons across the mitochondrial membrane, creating a proton gradient that drives ATP synthesis.
➢ Photosynthesis: During photosynthesis, redox potential helps in the transfer of electrons through the photosystems
in chloroplasts. The redox potential gradient helps split water molecules (photolysis), releasing oxygen and providing
electrons and protons for the synthesis of ATP and NADPH.
➢ Detoxification Processes: Enzymes involved in detoxification, like cytochrome P450 oxidases, utilize redox reactions
to modify and excrete foreign substances and toxins. The redox potential enables the transfer of electrons necessary
for these biochemical modifications.
➢ Metabolic Pathways: Several metabolic pathways, including the Krebs cycle, glycolysis, and fatty acid metabolism,
involve redox reactions. The redox potential of various coenzymes, such as NAD+/NADH and FAD/FADH₂, regulates
the flow of electrons, which is necessary for producing energy intermediates.
 Energy linked to redox reactions
Energy-linked redox reactions facilitate the transfer of electrons between molecules like
NAD+/NADH or FAD/FADH₂, and this electron transfer is coupled with the production of ATP
in the mitochondria. This energy is essential for vital activities, including growth,
reproduction, and maintaining cellular functions.

Several metabolic pathways, including glycolysis and the citric acid cycle, are involved in
producing high-energy molecules like NADH and FADH₂ through enzymatic redox reactions.
 Glycolysis pathway
Reactions which Produce NADH

1.NADH production in Glycolysis in aerobic condition

In the 5th step of glycolysis, glyceraldehyde -3-Phosphate is oxidized to 1,3

bisphosphoglycerate, which results in the production of NADH molecules.
This reaction is catalysed by enzyme glyceraldehyde-3-phosphate
dehydrogenase
2. NADH production when pyruvate oxidized to Acetyl CoA
Glucose
Pyruvate dehydrogenase 2 NAD+
complex GLYCOLYSIS
Pyruvate Acetyl CoA
(which enters citric acid cycle) 2 NADH

2Pyruvate
NAD+ NADH 2 NAD+
(Oxidized form) (Reduced form)
2 NADH

Pyruvate dehydrogenase is an enzyme that catalyses the irreversible 2Acetyl CoA

oxidation of pyruvate and produces acetyl-CoA, which enters the Krebs

cycle.
Kreb cycle
or
6 NAD+
citric acid cycle
2 FAD+
Mitochondria 6 NADH

2 FADH2
3. NADH and FADH2 production in Citric acid cycle

Here are the steps in the cycle where NADH are

produced:
Malate dehydrogenase

1. Isocitrate to α-Ketoglutarate:
2. α-Ketoglutarate to Succinyl-CoA Isocitrate
dehydrogenas
3. Malate to Oxaloacetate e

Succinate α
Here are the step in the cycle where FADH2 dehydrogenase ketoglutarate
dehydrogenas
produced: e

1.Succinate to Fumarate
4. Energy linked to redox reaction - oxidative phosphorylation
ATP synthesis in the electron transport chain (ETC) is the final step of cellular respiration, occurring in
the inner mitochondrial membrane. This process, known as oxidative phosphorylation, uses energy
from electrons transported by NADH and FADH₂ to drive ATP production.
Outer membrane
Electrons from NADH and FADH₂, produced in the citric acid
cycle and glycolysis pass through a series of protein Inner membrane

complexes(I,II,III, IV) present in the inner mitochondrial

membrane.
NADH NAD+ + H+ + 2e-
FADH2 FAD+ + 2H+ + 2e-

As electrons move through these complexes, energy is released, which is used to pump protons (H⁺ ions)
from the mitochondrial matrix into the intermembrane space, creating a proton gradient.
The pumping of protons into the intermembrane space creates a high concentration of protons outside
the inner mitochondrial membrane compared to the matrix, establishing both a chemical gradient
(difference in H⁺ concentration) and an electrical gradient (charge difference) which create proton motive
force .
Protons flow back into the mitochondrial matrix through
ATP synthase due to the proton gradient in a process
called chemiosmosis. As protons pass through ATP
synthase, the enzyme rotates, providing the energy
needed to convert ADP (adenosine diphosphate) and
inorganic phosphate (Pi) into ATP.

Each NADH contributes enough energy to generate

approximately 2.5 ATP molecules, and each FADH₂
contributes enough for about 1.5 ATP molecules.
Reduction of oxygen in oxidative Phosphorylation
Oxygen acts as the final electron acceptor at the end of the ETC, and get reduced by combining
with electrons and protons to form water. This removal of electrons from the ETC keeps the
chain functioning continuously, allowing further electron flow and ATP synthesis.

⅟2 O2 + 2e- + 2 H+ -----------> H2O

O2 reducing to
H20
Oxidation and reduction of iron in hemoglobin

➢ Hemoglobin (Hb) is a globular protein found in red

blood cells (RBCs) that plays a crucial role in
transporting oxygen throughout the body via the
bloodstream.
➢ Hemoglobin is a tetrameric protein with 4 subunits and Oxygen
molecules
each subunit contains a heme prosthetic group. (O2)

➢ Heme prosthetic group contains Protoporphyrin IX with

Iron (Fe2+ ) at its centre which allows it to bind oxygen
molecule (O2).

Heme binding with oxygen

molecule
➢ When oxygen binds to the ferrous iron(Fe2+), hemoglobin forms oxyhemoglobin. The
binding of oxygen is reversible and it does not change the oxidation state of Fe2+.
➢ One molecule of hemoglobin (with four hemes) can bind with four molecules of O2.
When hemoglobin releases oxygen in tissues, it reverts to deoxyhemoglobin.
➢ Occasionally, reactive oxygen species (ROS) or oxidizing drugs and chemicals can cause
the iron in hemoglobin to be oxidized from its ferrous (Fe²⁺) to ferric (Fe³⁺) state,
resulting in the formation of methemoglobin. In this state, hemoglobin cannot bind
oxygen. Reactive oxygen species/
oxidant chemicals drugs
Fe²⁺ (hemoglobin) ---------------------------------> Fe³⁺ (methhemoglobin)
However, enzymes like methemoglobin reductase present in the cytoplasm of RBC reduce Fe³⁺
back to Fe²⁺, maintaining hemoglobin's oxygen-carrying capacity.

Methemoglobin
reductase
Fe³⁺ (methhemoglobin) ---------------------------------> Fe²⁺ (hemoglobin)
Reduction

Reduction