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Chapter 13

Bioenergetics and Biochemical Reaction


Types

CHEM 641

Prof. Zhihao Zhuang


Oct. 20 2009
Bioenergetics
•! Living cells need to perform work to stay alive, to
grow, to reproduce.
•! The ability of organism to harness chemical energy
and to channel it into biological work is a
fundamental properties of all living organisms.
•! Chemical energy is needed to
1.! Synthesize highly ordered macromolecules from simple
precursors (DNA, RNA, proteins).
2.! Generate motion, heat, concentration gradient.
3.! Light (firefly and deep see fishes) and electricity.

Definition of bioenergetics:
Quantitative study of energy transductions, from one
form into another, in living cells. Also the chemical
reactions underlying these transductions.
The laws of thermodynamics
Bioenergetics obey the Laws of Thermodynamics

The first law is the conservation of energy. The total amount of


energy in universe remains constant;
The second law states the entropy of an isolated system that is not
in equilibrium will tend to increase over time, approaching a
maximum value at equilibrium.

Gibbs free energy, G, (joule/mole, cal/mole) expresses the amount


of energy capable of doing work during reactions at constant
temperature and pressure. !G is the change in Gibbs free energy of
the reaction system. !G <0, exergonic, system releases energy. !G
>0, endergonic, system gains energy.

Enthalpy, H, (joule/mole, cal/mole) is the heat content of the reacting


system, determined by the nature and numbers of chemical bonds
in the reactants and products. !H <0, exothermic, release heat; !H
>0, endothermic, take up heat.
The laws of thermodynamics
Entropy, S, (J/mol"K) quantitative expression for the randomness or
disorder in a system. !S>0, gain in entropy, increase in
randomness. The product of a reaction is less complex, and more
disordered than the reactants, gain in entropy.

Under constant temperature and pressure, the changes in free


energy, enthalpy and entropy can be related to each other using
equation
!G = !H - T!S or !G = !H + T(-!S)

The order produced within cells as they grow and divide is more
than compensated for by the disorder they create in their
surroundings. Living organism preserve their internal order by taking
from surroundings free energy in the form of nutrients or sunlight,
and returning to their surroundings energy as heat and entropy.
The Gibbs free-energy in biological system

Gibbs free energy


1.! Dictate the direction of chemical reactions;
2.! Determine the equilibrium of a reaction;
3.! Decide the amount of work that can be performed.

Sources of free energy


For heterotrophic organisms from nutrient
molecules;
For photosynthetic organisms from sunlight;

The form of free energy


The free energy is conserved or stored in energy-
rich compound, such as ATP, which can be used
as fuel for a diverse array of biological work.
Standard free-energy change and
equilibrium constant

aA + bB ! cC + dD
Keq, equilibrium constant
Keq = [C]c[D]d/[A]a[B]b
!G represents the driving force that move a
reaction system to equilibrium.
!Go standard free-energy change
!G´o standard transformed free-energy
change
Equilibrium constant and standard free-
energy change

•! !G’o= - RT lnKeq’
•! R=8.315 J/mol•K T=298 K
•! At 25 degree, RT=2.478 kJ/mol

•! Keq’ =1, !G’o= 0, at equilibrium


•! Keq’ >1, !G’o < 0, proceeds forward
•! Keq’ <1, !G’o > 0, proceeds in reverse
Actual free energy change

•! !G = !G’o + RT ln ([C]c[D]d/[A]a[B]b)
•! !G = !G’o + RT ln Q
•! Q is mass-action ratio

At equilibrium !G=0, !G’o= - RT lnKeq’


Question? !G’o >0, reaction won’t occur spontaneously.
True or not?
!G>0, reaction would not occur spontaneously.
!G, not !G’o, determines the spontaneity of a reaction.
!G represents the maximum amount of energy that can
used to do the work. The actual amount of work done
by the reaction is always less than the theoretical
amount. Need a perfectly efficient device.

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