College of Engineering, Pune

(An Autonomous Institute of Government of Maharashtra)

Applied Science Department

Tel: 020-25507034 Fax: 020-
25507219

CT16002 – Biology for Engineers

UNIT III: Bioenergetics and Metabolism

-------------------------------------------------------------------------------------------------------------

1. Energy Dynamics in Biology –

a. Photosynthesis and energy assimilation: aerobic and anaerobic systems.
Applications
b. Respiration and Electron Transport Chain: Mitochondria and respiration,
ATP generation.
2. Bioenergetics: Thermodynamic principles applied to biology, negative entropy
changes in biological systems, Free Energy, Chemical Equilibrium
-----------------------------------------------------------------------------------------------------------------------

1
 1) PHOTOSYNTHESIS

(PHOTOSYNTHETIC ELECTRON TRANSFER, CALVIN CYCLE)

Introduction:

Solar energy is the prime source of energy to entire living world . 2] All living organis m s
require energy for their life processe s. 3] Solar energy can’t be utilize d by organism s.

Important Features of Photosynthesis:

1) It is an intrace llu la r process. 2) It takes place only in green cells of plant 3) Du ring
this process organic food is synthesized . 4) It utilize s solar or light energy. 5) It uses C O 2
& H2 O as raw materia ls. 6) Solar energy is converte d into chemica l energy. 7) Only 1 to
5% of solar energy received by earth is utilized in photosynthe sis. 8) It is redox reactio n
where water is oxidized to oxygen & CO2 is reduced to carboh yd rates. 9) At first sim p le
sugar like glucose is formed & then complex food like starch, prote ins, fats are formed .
10) Chlorophy ll acts as a catalyst.

Definitio n:- It is a bioche m ica l process in which organism s prepare complex organ ic
food from simple , inorga nic substances like CO2 & H2 O with the help of chlorop h yll &
light energy, releasing O2 as by produ ct.

Overall reaction: -

6CO2 + 12H2 O ---------------- C 6 H12O 6 + 6H2O + 6O2

Photosynthesis is an anabolic (biosynthetic ) & endergonic ( E dependent ) process.

Pigments and their role :--1] Photosynthe tic pigments of chloroplast in higher plants
are chlorophy ll & carotenoids.

2] Chlorophyll : - Each chlorophyll molecule looks like a kite or tennis racket with head &
tail. Head is made up of 4 pyrol rings with Mg in center. It is hydrophilic Tail is made up
of phytol which is long chain alcohol. It is lipophilic, hydrophobic.

3] Chlorophyll a : - It is bluish green, with molecular formula C 55 H 72 O 6 N 4 Mg,

absorbs – blue, yellow, red wave lengths of light.

4] Chlorophyll b – It is yellowish green, molecular formula C 55H70O6N 4Mg ,absorbs –

blue, orange wave lengths of light.

2
5] Carotenoids are carotenes & xanthophylls. Carotenes are yellowish orange with
molecular formula C 40H56. Xanthophylls are yellow with molecular formula C40H56O2
Carotenoids are long chain hydrocarbons. They don’t have definite shape.

6] All photosynthetic pigments trap light energy in form of photons.

7] Chlorophyll b, Crotenes & Xanthophylls transfer trapped light energy to chlorophyll a

by resonance transfer, do not participate actively in photosynthesis. Hence they are called
as accessory pigments/antennae pigments/light gatherers. These accessory pigments
avoid photo-oxidation of reaction center in intense light.

8] Chlorophyll a collects light energy from these pigments. It also absorbs light energy.
It uses light energy for formation of ATP. Hence it is called as active pigment. It acts as a
center of chemical reaction. It shows fluorescence.

9] Middle region of quantosomes are called as photocentres or reactive centers.

10) Chlorop hyll a has two pigment systems called photosyste ms i.e. PSI , PSII are
involve d . PS I absorbs far red light of wavelength 700 nm & PSII absorbs short red light
of wavelength 680 nm. Each system has its own type of chloroph yll a i.e. P700 & P6 80.
Both system work in coope ra tion to capture radiant energy.

PS I – 670 , 683, 700. P – 700 is Reaction center. PSII – 680, 673. P – 680 is Reaction
center. PSI – lies on outer surface of thyllacoid, PSII – lies in inner surface of thyllacoid.

Mechanism of Photosynthesis --
Reaction of photosynthesis takes place in two phases i.e. photochemical phase &
biochemical phase.

I] Primary Process / Photochemical phase / Light reaction

1) It takes place in presence of solar energy i.e. light & only in granna of chloroplast.
Hence it is light reaction.
2) Light energy is converted into chemical energy with formation of ATP &
NADPH2. Hence it is photochemical phase.
3) ATP is formed by addition of 1 inorganic phosphate to ADP with the help of
energy. This is called as phosphorylation.
4) Energy required for phosphorylation is obtained from light in form of photons.
Hence it is called as photophosphorylation.
5) During this process e ◌ s are transfered through a system of e ◌ acceptors.

6) Two pathways are there of e ◌transfer i.e. cyclic & non cyclic

(A) Cyclic e ◌transfer / Cyclic photophosphorylation

3
(1)It involves PS I (Pigment system I). (2) Light strikes chloroph y ll-a i.e.P – 700
trap(3) It absorbs quantum of light energy. (4)As a result it is exited i.e. its energy level
increases.(5) Hence it emits a pair of high energy electrons. (6)Energy rich e ◌leave
chlorophyll molecule & hence the chlorophyll molecule becomes +vely charged (ionized)
i.e. unstable .(7)E le ctrons move through various electron acceptors such as FRS(Z) ,
ferredoxin, cytoch rome b6, cytoch rome f & plastocyanin.(8)As energy rich electro n s
move through electron acceptors, they loose some of their energy which is used for
synthesis of ATP from ADP & inorganic phosphate . (9)Fina lly de-energised electro n s
return to unstable chlorophyll a molecu le which becomes stable . (In one millionth of a
second) (10)Thus the electrons lost by chlorop hyll molecu les return to the sam e
chlorophyll molecu le . Hence it is called as cyclic electron transfe r.

Cyclic electron transfe r occurs when light intensity is low, CO2, O2 low.

B] Non cyclic photophosphorylation / Non cyclic e – transfer

4
1) It involves pigment system I & II i.e. PS I & PS II
2) Light strikes chlorophyll – a of PS I & PSII i.e. P-- 700 trap & P680 trap.
3) They absorb quantum of light energy .
4) As a result they are exited i.e. their energy level increases.
5) Hence they emit a pair of high energy electrons
6) Energy rich e –s leave chlorophyll a molecule which becomes + vely charged
(Ionised) i.e. unstable.
7) These e –s from PS II system, which is the primary electron donor, move through
various e – acceptors such as FRS, ferredoxin and finally accepted by NADP, that
from PS I through plastoquinone, cytochrome b6 , Cytochrome f, plastocyanin.
8) As energy rich electrons move through electron acceptors, they loose some of their
energy which is used for synthesis of ATP from ADP & inorganic phosphate.
9) In presence of light & chlorophyll a molecule photolysis of water takes place & two
electrons , two H + ions & O2 are released. O2 is released outside. These electrons
are accepted by chlorophyll –a of PS II & it becomes stable. H ions are accepted by
NADP.
10) Two electrons emitted from PSII are accepted by chlorophyll- a of PS I after it emits
two e – s when light strikes on it. Thus chlorophyll-- a of PS I becomes stable.
11) Finally two H + ions released by photolysis & two e – s released by PSI combine
together & reduce NADP to NADPH2

12 ) Thus e – s emitted from one pigment system don’t return to it. Hence it is called
as non cyclic e – transfer.

FRS – ferredoxin reducing system

Ferredoxin – Fe containing flavo protein

Cytochromes – Fe containing proteins

Platocyanin – Cu “ “

5
 Significance of Non cyclic e – transfer :-

1] In this path wa y ATP & NADPH 2 are formed .

2] ATP acts as an energy donar in dark reaction

3] NADPH2 acts as a hydrogen donar in dark reaction
4] Photolysis of water takes place.
5] Oxygen is liberated as bi product.
6] It is more efficient than cyclic photophosphorylation.

Cyclic Photohosphorylation Non cyclic Photophosphoryltion

1. e –s return to same chlorophyll 1. e –s don’t return to same chlorophyll
molecule from which they are molecule from which they are emitted.
emitted. 2. Photolysis of water take place.
2. Photolysis of water doe not take 3. O2 is evolved as bi product.
place. 4. NADPH2 is formed
3. O2 is not evolved 5. NADP takes part as e - acceptor
4. NDPH2 is not formed 6. Both pigment systems I & II are involved.
5. NADP doesn’t take part.
7. More efficient as more energy is formed.
6. Only pigment system I is involved
8. Primary acceptor is FRS (Z) &
7. Less efficient as less energy is
plastoquinone .
formed.
9. It takes place in green plants.
8. Primary acceptor is FRS (Z)
10. Occurs in normal light, aerobic condition,
9. It takes place in photosynthetic
sufficient CO2
bacteria
10. Occurs in low intensity light,
anaerobic condition, less CO2 availa ble

6
II) Secondary Process / Biochemical Phase / Dark Reaction
1) It takes place in stroma of chloroplast, independent of chlorophyll
2) Light is not required for it. Hence it is known as dark reaction.
3) ATP, NADPH2 formed during light reaction are used in dark reaction for reducing
& fixing CO2 in carbohydrate i.e. hexose sugar. Hence it is also known as CO2

fixation or synthetic phase.

4) Energy in ATP is used for various reactions.

5) Enzymes & coenzymes necessary for dark reaction are present in stroma of
chloroplast.
6) Blackman in 1950 observed this reaction first. Hence it is also called as
Blackman’s reaction

7
7) Melvin Calvin & Benson traced path of carbon during dark reaction. They were
awarded Nobel prized in 1961.
8) During their experiment they fed unicellular algae chlorella & Scenedesmus with
radio active carbon isotope i.e. C¹4O2 Algae were allowed to carry photosynthesis.
At different time intervals algal cell extract was chemically analysed by paper
chromatography to find out compound containing C ¹4. On the basis of products
obtained they suggested a cycle for dark reaction which is called as Calvin Cycle.
It has three phases

A] Carboxylation Phase B] Reduction Phase C] Regeneration & Synthetic Phase.

A] Carboxylation Phase.

i) Atmospheric CO2 is taken by stroma of chloroplast.

ii) RuMP ( Ribulose Mono Phosphate ) – 5 carbon compound is present
in stroma. It is phosphroylated into RuDp (RuDP—Ribulose Di
Phosphate) It is called as CO2 acceptor
iii) RuDP absorbs atmospheric CO2 & forms unstable 6 C compound.
iv) 6 C compound immediately undergoes hydrolysis & splits into 2
molecules of 3C compound i.e. 3 PGA. This is first stable compound
in Calvin Cycle. Hence it is also called as C 3 Cycle.
B] Reduction Phase –

i) 3PGA is phosphorylated to 1, 3 DPGA( Di Phospho Glyceric Acid )

ii) 1, 3 – DPGA is reduced to 3 – PGAL ( Phospho Glyceraldehyde ) by using
hydrogen from NADPH2 & in this reaction one inorganic phosphate is
released. The process is reverse of oxidation in glycolysis. Hence it is known
as glycolytic reversal.
C] Regeneration & Synthetic Phase

i) 10 molecules of 3 – PGAL are used for regeneration of RuMP through

various phases with formation of 10C, 9C, 8C …… compounds.
ii) Two molecules of 3PGAL are used to form hexose sugar i.e. glucose which
is converted into starch by polymerization.

Action spectrum – rate of photosynthesis at different wavelengths of light.

Absorption spectrum – absorption of light of different wave lengths.

Quantun require me nt – no. of photons/q ua nta required to release 1 molecu le of

O2

Emerson & Lewis showed that it is 8 quanta.

Red drop – sudden fall in photosynthesis yield beyond red region of spectrum.
Showed by Emerson & Lewis.

8
 Emerson’s enhancement effect – if simultaneously shorter & longer wave lengths
are provided, rate of photosynthesis is higher than total rate from the beams
separately.

RESPITATION

Introduction - Living beings need regular supply of energy for vital functions or
activities like cell division, transport of materials, locomotion, digestion etc .

Definitio n :– It is an intrace llu lar oxidation -- reduction reaction in which com p le x

organic substances are broken down stepwise to release chemica l energy in the form of
ATP & CO2 & H2O are given out as byprod ucts.

Important features :-- Overall Reaction

C 6 H12 O6 + 6O2↓ → 6CO2↑ + 6H2O + E (38ATP , 277.44 Kcal)

• In biochemical process the reaction is not so simple.

• Free molecular oxygen does not combine directly with substrate like in combustion.

• Hydrogen is gradually removed from the substrate & the electrons released (H2 → 2H
+ 2e‾ ) are transferred through a series of e‾ carriers to gene rate energy in the form
of ATP ( exergonic -- energy producing, catabolic – breakdown process )

• The process occurs at cellular temperature.

• Gases are exchanged in liquid medium by blood, tissue fluid etc.

• CO2 & H2O are given out as byproducts.

• All energy in glucose molecule is not converted into ATP but some of it is lost as heat
energy.

ATP –The Energy Currency of the Cell

These are bio-molecules which store energy in biologically usable form.

ATP – Adenosine Tri Phosphate

It is composed of a) Adenosine – which is made up of adenine [Nitrogen base] +

Ribose Sugar [Pentose sugar] b) 3 phosphate groups
α β γ
Adenine----- Ribose sugar ---- PO4 ~ PO4 ~ PO4

9
 Second & Third phosphate groups are attached to ribose sugar by high energy
bonds, when cell needs energy it breaks the third high energy bond & even the
second phosphate bond of ATP forming ADP & AMP respectively
ATP → ADP + iP + E

All living cells generate ATP by using energy trappe d in glucose molecu le during
photosynthesis. During this process glucose molecu le is oxidized . In this reaction
CO2 & H2 O are given out as by products. This is called as cellu la r respira t i o n.
Energy released is trapped in ATP molecu le by attaching phospha te group. This is
called as phosphory la tion. As glucose molecu le is oxidize d it is called as oxida t iv e
phosph oryla tion.

Significance : 1] It stores energy in biologica l usable form. 2] It supplie s energy

in

various cellula r activities by breaking phospha te bond in between 2nd & 3rd and

even 1st & 2nd phospha te groups. 3] It acts as a phospha te donar in variou s
bioche m ica l reactions.

• Cellular respiration is oxidation of food material into CO 2 and H2O.

• During this oxidation E released is trapped in ATP ( 1ATP traps 7.28 k cal)for
using in all cell activities.

This oxidation occurs in three phases.

1) Glycolysis – Breakdown of glucose to pyruvic acid (pyruvate). It occurs in

cytosol i.e. cytoplasm. Hence mitochondria are not necessary. In occurs in
prokaryotes as well as eukaryotes. As O2 is also not required it is common to aerobic
as well as anaerobic organisms. In glycolysis 2 ATP and 2 NADH + H+ also formed.

2) Citric Acid Cycle / Krebs cycle -

• Decarboxylation of pyruvic acid to CO2 and H2O along with formation of NADH +
H+ and FADH2.

• In eukaryotes it occurs in mitochondrial matrix. Matrix has complex mixture of

soluble enzymes for decarboxylation of pyruvic acid.

At the end 3CO2 , 4 NADH + H+, 1 FADH 2 are formed (when 2e – are remov e d
from malic acid transfe rred to NAD+ reducing it to NADH + H+, same way 2 e –
removed from saccinic acid and reduces FAD. To FADH2

10
 Outer membrane – contains many complexes of integral membrane proteins that
form channels – porins through which many molecules and ions move in and out
of mitochondria.

• e – from NADH and FADH2 are transferred to next phase i.e. respiratory chain.

3) Electron Transport Chain / Respiratory Chain -

• Inner membrane of mitochondria contains complexes of integral membrane

proteins.

NADH dehydrogenase complex

Succinate dehydrogenase complex

Cytochrome c reductase complex

Cytochrome c oxidase cpmplex

ATP synthase complex

• It also consists ubiquinone, cytochrome a,b,c, which shuttle electrons from one
complex to another.

Inner membrane is selectively permeable.

(NADH carries e – from catabolic reactions to respiratory chain.

NADPH supplies e – to anabolic reactions.)

• Stepwise transfer of e – from NADH, Ubiquinone, Cytochromes and then finally to

O2 to form H2O takes place. Neither NADH nor NADPH can cross inner
mitochondrial membrane, but the e – carried by them can shuttle across.

• During e – transfer E is released.

• It is used to transfer/ pump H+ (protons) from matrix into inter membrane space
by active transport.

• Thus matrix becomes – vely charged and inter membrane space +vely charged.

• Gradient of protons formed across the inner membrane forms a miniature battery.
(Mitochondria contain 3 classes of cytochromes – a,b,c which absorb different light
spectra)

11
 [Plastoquinone is like ubiquinone. Ubiquinone ( Coenzyme Q) ⎯→ small,
hydrophobic, hence freely diffusible in lipid bilayer of inner mitochondrial
membrane and can shuttle reducing equivalents between other less mobile
electron carriers in the membrane. Cytochromes ⎯→ proteins with iron – heme
group; show strong absorption of visible light.)

• In mitochondrial respiratory chain, e – move as follows – NADH / FADH2 ⎯→

Co.Q ⎯→ Cytochrome b ⎯→ Cytochrome C 1 ⎯→ Cytochrome C ⎯→ Cytochrome
a ⎯→ Cytochrome a 3 ⎯→ O2.

FADH2
AH2

FAD

ATP ATP ATP

CoQ Fe+++ Fe +++ Fe +++ Fe +++ Fe +++ 1/2 O2

Cyt b Cyto C1 Cyt C Cyt a Cyt a3

H
CoQH2 Fe ++ Fe ++ Fe ++ Fe ++ Fe ++ H2O
AH

2H+

ADP + iP ADP + iP ADP+ iP

Chemiosmosis in Mitochondria:-

• As e – pass from NADH + H+ / FADH2 down the gradient to O2, E is released.

• This E is used to pump H+ (protons)from matrix into inter membrane space

against conc. / electrochemical gradient by active transport

• As proton conc. increases in inter membrane space; a strong diffusion gradient is

set up.
12
• These protons can only exit through ATP synthase complex into matrix .

13
• E is released as protons flow down their conc. gradient through specific protein
channels in inner membrane. This free E is utilized for ATP synthesis. The process
catalyzed by a membrane protein complex ATP synthase. ATP synthase is present
in elementary particles of inner membrane. Mitochondrial ATP synthase is an F-
type ATP ase . ATP synthase has two distinct components : F1 → peripheral
membrane protein & Fo → integral to above membrane. Fo has a proton pore
through which protons leak as fast as they are pumped by e‾ transport. Without a
proton gradient the F1 depleted vesicles can’t make ATP. On the other hand
isolated F1 catalyze ATP hydrolysis ( reversal of synthesis) hence originally called
as F1 ATP ase. When purified F1is added back to depleted vesicles, it reassociates
with Fo plugging its proton pore & restoring membrane’s capacity to couple e‾
transfer & ATP synthesis.

• This transfer of protons along concentration gradient from inter membrane space
to matrix is called chemiosmosis. It is an example of facilitated diffusion.

• Peter Mitchell proposed chemiosmotic model. According to this model

transmembrane differences in proton concentration are the reservoir for E
extracted biological oxidation reactions.

14
• Inhibitors of e – transfer to O2, like cyanide, CO, antimycin A, block ATP synthesis
and vice versa. (oligomycin inhibits ATP synthase activity. ) Thus these two
processes show obligatory coupling.

Mitochondrial DNA:-
• Human mitochondrion contains 5 – 10 circular DNA molecules – mt – DNA.
• Mutation in mt – DNA causes human diseases; affecting mainly brain and
muscles.
• In mammals 99.99% of mt DNA is inherited from mother. This is because in
zygote paternal mitochondria are only about 100, while maternal are 100,000.

15
 2) BIOENER GE TIC S

Living cells and organisms must perform work to stay alive and to reproduce themselves.
The synthetic reactions that occur within cells, like synthetic processes in any factory,
require the input of energy. Energy is also consumed in the motion of a bacterium or an
Olympic sprinter.

Although the characteristic composition of an organism changes little through time, the
population of molecules within the organism is far from static. Small molecules,
macromolecules, and supra-molecular complexes are continuously synthesized and then
broken down in chemical reactions that involve a constant flux of mass and energy
through the system. The hemoglobin molecules carrying oxygen from your lungs to your
brain at this moment were synthesized within the past month; by next month they will
have been degraded and entirely replaced by new hemoglobin molecules. The amounts of
hemoglobin in the blood remain nearly constant because the rate of synthesis balances
the rate of its breakdown, the constancy of concentration is the result of a dynamic steady
state, a steady state that is far from equilibrium. Maintaining this steady state requires
the constant investment of energy; when the cell can no longer generate energy, it dies
and begins to decay toward equilibrium with its surroundings.

Metabolism –The sum of all chemical transformations taking place in a cell

/organism.

Metabolic pathways – A series of enzyme catalyzed reactions. Each step in it brings

about specific, small chemical change like removal, transfer / addition of a particular
atom / functional group.

Metabolites – Metabolic intermediates which convert precursors into products.

Intermediary metabolism – Combined activities of all metabolic pathways that

interconvert precursors, metabolites & products of low molecular weight

Catabolism --The degradative phase of metabolism in which organic nutrie n t

molecu le s (carboh yd rate s, fats, and prote ins) are converte d into smaller, simple r end
produ cts (such as lactic acid, CO2 , NH3 ). Catabolic path wa ys release energy, some of
which is conserved in the forma tion of ATP and reduced electron carriers (NADH ,
NADPH , and FADH2 ); the rest is lost as heat.

Anabolism –(also called biosynthesis ) Small, simple precursors are built up into larger
and more complex molecules, including lipids, polysaccharides, proteins, and nucleic
acids. Anabolic reactions require an input of energy.

16
Bioenergetics - The quantitative study of the energy transductions that occur in living
cells and study of the nature and function of the chemical processes underlying these
transductions. Biological energy is not in the form of heat mechanical or light energy
therefore word thermodynamics is not used but word bioenergetics is used. This energy
is termed as free energy and defined as energy available for work. It symbolizes change in
energy and not the absolute energy.

Two approaches to study physical or chemical processes:

Kinetic molecular approach: In this, process is studied in terms of molecules

and atoms.

Thermodynamic approach: Process id studied by considering energy changes

involved. Thermodynamics means study of heat flow. But actually not only relation
between heat and work but also deals with all kinds of inter conversion of one kind
of energy in to the other. Most of the energy forms are ultimately converted in to
heat.

Thermodynamics help to forecast whether certain physical or chemical

transformations are possible or not. Under given set of conditions of temperature,
pressure, concentration etc. But it can not give any information of time required
for completion of change as well as rate of reaction.

If the system exchanges neither matter nor energy with its surroundings, it is said
to be isolated. If the system exchanges energy but not matter with its
surroundings, it is a closed system; if it exchanges both energy and matter with
its surroundings, it is an open system.

A living organism is an open system; it exchanges both matter and energy with its
surroundings. Living organisms derive energy from their surroundings in two
ways:

1) They take up chemical fuels (such as glucose) from the environment and
extract energy by oxidizing them; or

2) They absorb energy from sunlight.

Homogenous system – System with same chemical composition throughout.

Heterogenous system – System with two or more phases which are

homogenous themselves but separated from each other by definite boundary. (ice
and water)

State of a system: Variable of a state are temperature, pressure, volume,

composition

17
 Gas Equation: PV = nRT

Therefore if 2 values are known the third can be determine d thus state of a sim p le
homogenous system can be defined. Physica l prope rties of a system are of two type s:

Extensive properties: Depend on quantity of matter in the system under

consideration e.g. mass, volume, energy

Intensive properties: Depend on nature of substance and independent of its

amount e.g. temperature, pressure, viscocity, refractive index

Thermodynamic equilibrium: It is said to achieved when observable

properties like temperature, pressure, volume does not change with time. For
thermodynamic studies a system must be in in 3 types of equilibria which must
exist simultaneously.

a) Thermal equilibrium

b) Chemical equilibrium

c) Mechanical equilibrium: No movement of particles of the constituents of

system itself and between itself and surroundings.

Isothermal process: Temperature remains same

For Exothermal process – heat evolved give out immediately to surroundings to

maintain the temperature. For endothermic process required amount of heat
enters the system from surroundings to maintain the temperature.

Adiabatic process – heat neither enters nor leaves the system during the
process.

Thermodynamic laws and living organisms

The molecular complexity and orderliness of structure of living organisms is much

higher in contrast to the randomness of non living matter.

The first law of thermodynamics, fully valid for biological systems

Photosynthe tic cells absorb light energy and use it to drive electrons from wa te r
to carbon dioxide , forming energy-rich produ cts such as glucose (C 6 H12 O 6 ) ,
starch, and sucrose and releasing O2 into the atmosphe re:

Light 6 CO2 + 6 H2 O ⎯⎯→ C 6 H12 O 6 + 6 O2

(light-d rive n reduction of CO2 )

18
Non – photosynthe tic cells and organism s obtain the energy they need by
oxidizing the energy-rich produ cts of photosynthesis and then passing electro ns
to atmosphe ric O2 to form water, carbon dioxide , and other end products, which
are recycled in the environment:

C 6 H12 O6 + O2 ⎯⎯→ 6 CO2 + 6 H2 O + energy

(energy-yie ld ing oxidation of glucose)

DNA, RNA, and proteins are informational macromolecules. In addition to using

chemical energy to form the covalent bonds between the subunits in these
polymers, the cell must invest energy to order the subunits in their correct
sequence. It is extremely improbable that amino acids in a mixture would
spontaneously condense into a single type of protein, with a unique sequence. This
would represent increased order in a population of molecules; but according to the
second law of thermodynamics, the tendency in nature is toward ever- greater
disorder in the universe: the total entropy of the universe is continually increasing.
To bring about the synthesis of macromolecules from their monomeric units, free
energy must be supplied to the system (in this case, the cell).

Second law of thermodynamics

How living organisms can create and maintain their intricate orderliness in an
environment that is relatively disordered and becoming more with the time ?
Living organisms do not constitute exceptions to thermodynamic laws. Their high
degree of molecular orderliness must be paid for in some way since it can not arise
spontaneously from disorder.

Living organisms have following characteristic properties such as,

1) Use free energy: Living organisms absorb useful form of energy that is free
energy from surrounding under specific temperature and pressure and return less
useful form of energy to the environment in equal amount. The useful form of
energy returned by the living organisms is heat or other form that is quickly
randomized in the environment and thus increase the entropy.

2) Open system: living organisms are not in equilibrium with the environment

3) Steady state: Cell is non equilibrium open system, a machine for extracting
free energy from the environment which it causes to increase in randomness. The

19
 rate of transfer of energy and matter from environment in to system is equal to
transfer of energy and matter from system to environment.

4) Non equilibrium: Open system in steady state can do work in non

equilibrium. Process under non equilibrium can be regulated. This is orderly state
of an open system.

5) Isothermal system: The living system is essentially isothermal that is at any

given time all parts of the cell have the same temperature. Furthermore, there are
no significant differences in pressure between one part of the cell and another. For
this reason, cells are unable to use heat as a source of energy, since, heat can do
work at constant pressure only if it passes from a higher to a lower temperature
zone.

6) Isothermal chemical engines: energy absorbed from environment id

transformed to carry out synthesis of cell components, osmotic work, transport of
material into cell, nerve conduction, muscle contraction etc. which takes place at
constant struggle against the tendency to produce entropy. Synthesis of large and
information rich macromolecules, the information of intricately structured cells,
development of an organization, all these are powerful anti entropic doom imposed
on all natural phenomenons. Under the second law of thermodynamics, living
organisms choose the least evil – they produce entropy at a minimum rate by
maintaining steady state.

An attempt to produce a machine which could produce more mechanical work than
the equivalent energy used is failed. This compels to accept the first law of
thermodynamics in biological systems.

Mathematical formulation of first law

Suppose some amount of heat is put in the system, Since heat can not be lost it
must remain either partial or whole in the system, or can used up by the system in
doing mechanical work.

In general case, when both happen,

Heat absorbed = increase of internal energy + work done by the system

If final and initia l interna l energy of the system is E2 and E1 respective ly , th e n

increase interna l energy is ∆E = E2- E1

If heat absorbed is q and work done is w then

∆E = E2 – E1 = q – w (this is first law of thermod yna m ics)

20
 Although the heat absorbed / the work done by the system might vary the path by
which the change is affected ∆E is always same.

Second law of thermodynamics:

1. First law explains the equivalence between heat and work but imposes no
condition on their mutual convertibility. It never explains under what
circumstances and to what extent it is possible to convert one form of energy in to
other.

2. It also explains about the amount of heat lost by a hot body must be equivalent
to the gain by cold body. But is does not explains that heat has to flow
spontaneously from hot to cold body and not in reverse direction.

3. Different forms of energy can be readily and completely converted in to heat but
not possible to convert back heat completely in to work. Hence, there must be some
other law besides the first law that governs the direction of flow of heat and extent
of its convertibility in to work. This limitation forms the basis for second law of
thermodynamics. The total entropy of a system must increase if the
process has to occur spontaneously.

Entropy: The quantitative expression for randomness or disorder of the

components of a chemical system is expressed as entropy, S.

When the products of a reaction are less complex & more disordered than the
reactants, the reaction proceeds with a gain in entropy. Any change in randomness
of the system is expressed as entropy change, S, which by convention has a
positive value when randomness increases. J. Willard Gibbs, who developed the
theory of energy changes during chemical reactions, showed that the free energy
content, G, of any closed system can be defined in terms of three quantities:

Enthalpy, H – heat content of reacting system, reflecting the number and kinds
of chemical bonds in the reactants & products; Entropy, S; and the absolute
temperature, T (in degrees Kelvin).

The definition of free energy is G = H – TS.

When a chemical reaction occurs in biological system at constant temperature &

pressure, the free-energy change, G, is determined by the enthalpy change, H,
reflecting the kinds and numbers of chemical bonds and non covalent interactions
broken and formed, and the entropy change, S, describing the change in the
system’s randomness:

21
 G / ∆F = H – T S (F → Heltmoz free E, T→ absolute temp.)

Also ∆G / ∆F = ∆E – T ∆S ( E/Q → internal energy)

Hence total energy of the system is ∆E = ∆G + T ∆S

If ∆G is negative, the reaction would proceed spontaneously with loss of free

energy that is exergonic reaction. If in addition, ∆G is of great magnitude, the
reaction goes virtually to completion and is essentially irreversible.

If ∆G is positive, the reaction can not occur spontaneously and would proceed
only if the free energy can be gained that is endergonic.

If ∆G is zero, the system is at equilibrium and no net change takes place.

Relationship between equilibrium constant and standard free energy change in a

model reaction. Thus, in a reaction, A + B ↔ C + D

[C] [D]

∆G = ∆G0+ RT ln ---------------------

[A] [B]

When the concentra tion of [A] [B] [C] [D] ∆G is 0.1 M, ∆G0 known as stand ard
free energy change. At equilibriu m , ∆G0 = 0

[C] [D]

i.e. ∆G = ∆G0+ RT ln ---------------------

[A] [B]

For biochemical reactions, a standard state is defined as having a pH of 7. the

standard free energy change at this standard state is denoted by ∆G 0 since the
equilibrium constant under standard condition is;

K’eq = [C] [D] / [A] [B]

Substitution gives ∆G0 = - RT ln K’ eq

Thus, the standard free energy change can be calculated from the equilibrium
constant K’ eq it is important to note that ∆G may be larger or smaller than ∆G 0’
depending on the concentration of various reactants.

22