06

THERMODYNAMIC
CONSIDERATIONS

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 ATP is the cellular energy
currency -> how does that work?

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 CELLULAR ENERGY
CONVERSIONS
• In order to establish and
maintain a steady state
cells constantly need to
invest energy
• Biochemistry tries to
understand how energy is
converted in living cells
• Cellular energy
conversions can be
considered in the context
of thermodynamics
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 THE FIRST LAW OF THERMODYNAMICS
Principle of the conservation of energy:
In any physical or chemical change, the total
amount of energy in the universe remains constant,
although the form of the energy may change
relevant examples:
• plants transform light energy into chemical energy.
• cheetah transforms chemical energy into kinetic energy.

Heat co2
Chemical +
H2O
energy

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 THE SECOND LAW OF THERMODYNAMICS

• during energy transfer some

of the energy becomes M. C. Escher (1961) “Waterfall”
unavailable to do work
-> there is no perpetual
motion

• logically such loss makes

universe more disordered

• energy transfer or
transformation increases the
entropy of the universe

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 WHAT IS ENTROPY?
“Entropy is evil. It's worse than evil, because at least villains
usually have a purpose.” Oscar Wilde

• measure of a systems disorder and randomness

• allows understanding of why a
process will occur spontaneously
Ice melting in a warm
room is a common
example of increasing
entropy

Information has
‘negative entropy’
-> Protein sequence
-> DNA sequence
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 What is Entropy?

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 ENTROPY AND SPONTANEITY

• process will be spontaneous if it involves an

increase in disorder (positive entropy)
• process will not be spontaneous if it involves a
decrease in disorder (negative entropy)
– will only occur if energy is added to a system
2nd law of thermodynamics, alternative:
for a process to occur spontaneously it must
increase the entropy of the universe.

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 GIBBS FREE ENERGY

• portion of a systems energy that can perform work

when temperature and pressure are constant
• free energy change
ΔG = ΔH – TΔS
ΔH = change in enthalpy (change in heat)
TΔS = change in entropy (order of a system)

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 TΔS = CHANGE IN ENTROPY

Entropy is difficult to measure, but:

an increase in entropy is expected to accompany an

– increased temperature
– increased volume
– increased number of independently moving
particles

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 ΔG AS PREDICTOR OF THE
SPONTANEITY OF A PROCESS

https://www.khanacademy.org/science/biology/energy-and-
enzymes/free-energy-tutorial/v/gibbs-free-energy-and-spontaneous-
reactions

• if ΔG < 0 then process is spontaneous

• if ΔG = 0 then process is in equilibrium

• if ΔG > 0 then process is not spontaneous

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 FREE ENERGY CHANGE ΔG
(a) Exergonic reaction: energy released (b) Endergonic reaction: energy required
Reactants Products

Amount of
Amount of
energy
energy

Free energy
released
required
Free energy

(∆G < 0)
Energy Energy (∆G > 0)
Products Reactants

Progress of the reaction Progress of the reaction

ΔG = Gfinal state – Ginitial state

• Gfinal state = free energy of final state

• Ginitial state = free energy of initial state

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 EXERGONIC REACTIONS
- release free energy

Reactants

Amount of
energy
Energy released (∆G<0)
Free energy

Products

Progress of the reaction

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 EXERGONIC REACTIONS
• Glucose (C6H12O6) + 6 O2 → 6 CO2 + 6 H2O
ΔG = - 2870 kJ/mol

• ΔG < 0 indicates that reaction occurs spontaneous

• heat released
• more particles → increase in entropy

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 ENDERGONIC REACTIONS
• 6 CO2 + 6 H2O → Glucose (C6H12O6) + 6 O2
ΔG = 2870 kJ/mol
• absorbs free energy
• ΔG > 0, reaction not spontaneous
• input of energy required
• fewer particles → decrease in entropy (in system)
Products

Amount of
Free energy

energy
required
Energy (∆G > 0)
Reactants

CRICOS Provider Code: 00113B Progress of the reaction

 ΔG OF A REACTION
• independent of path taken!
• value depends on free energy of initial and final
products.
• Glucose (C6H12O6) + 6 O2 → 6 CO2 + 6 H2O
ΔG = - 2870 kJ/mol
• 2870 kJ/mol is maximum energy available to do
work.
• energy released regardless of whether glucose
is combusted at once or oxidised in a series of
enzyme catalysed steps.

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 ΔG OF A REACTION
ΔG is the same for combustion of H2 with O2 or electron transport chain
H2 + 1/2 O2 2H + 1/
2 O2
(from food via NADH)

Controlled
release of
2 H+ + 2 e– energy for
synthesis of
ATP

Elec
ATP

Free energy, G
Free energy, G

tron
Heat and light ATP

trans
ATP

port
chai
n 2 e–
1 /2 O2
2 H+

H2O H2O
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 ENERGY COUPLING LINKS
REACTIONS
Endergonic reaction: ∆G is positive, reaction is not spontaneous

NH2

+ NH3 ∆G = + 3.4 kcal/mol

Glu Glu
Glutamic Ammonia Glutamine
acid

Exergonic reaction: ∆ G is negative, reaction is spontaneous

ATP + H2O ADP + P ∆G = – 7.3 kcal/mol

Coupled reactions: overall ∆G is negative;

together, reactions are spontaneous ∆G = – 3.9 kcal/mol

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 ATP AND FREE ENERGY

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 ENERGY COUPLING IN
MECHANICAL PROCESSES

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 ENERGY COUPLING IN CHEMICAL
PROCESSES

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REDOX REACTIONS
IN
BIOLOGY

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 WHAT ARE REDOX REACTIONS?

All chemical reactions in which atoms have

their oxidation state changes!

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 REDOX REACTIONS

Oxidation is loss of electrons

à Oil Rig
Reduction is gain of electrons
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 OXIDATION AND REDUCTION
Oxidation Reduction

Loss/donation of electrons Gain/acceptance of electrons

Loss/donation of –H accompanied by Gain/acceptance of –H accompanied

2 e- by 2 e-

Gain/acceptance of oxygen Loss/donation of oxygen

Increase in oxidation number Reduction of oxidation number

• Na(s) + Cl2 (g)→ Na+ + 2 Cl-

• Na oxidised Oxidation number, 0 → +1
• Cl reduced Oxidation number, 0 → -1
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 OXIDATION NUMBER

The oxidation number (or the oxidation state) is the charge

that an atom in a molecule would possess if the shared electron
pairs in each covalent bond were assigned to the more
electronegative element in the bond.

Does not equal the actual charge on an atom!

Ox number +/- sign is always indicated before the number (Na+ -> +1)
Charge +/- sign is always indicated after the number (Na+ -> 1+)

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