BIOENERGETICS BCH 315

INTRODUCTION 260224
Bioenergetics Energy changes associated with biochemical reactions
constitute the study of bioenergetics or biochemical thermodynamics. The
environment of living cells or organisms is very essential to them; not only as a
source of free energy but also as a source of raw material. In the language of
thermodynamics, living cells are open systems because they exchange both
energy and matter with their environment and in so doing transform it. Living
cells are never in equilibrium with their environment. A cell at any given
moment exists in a steady state in which the rate of input of matter equals the
rate of output of matter. In this steady state, the concentration of all components
of the cell, including the ATP, remains constant. Under these conditions, the
rate of formation of each component is exactly equal to its rate of utilization.
This is the basis of non-equilibrium thermodynamics which contrasts with the
classical or equilibrium thermodynamics that operate in closed systems whereby
energy and matter are not exchanged with the environment. The energy
transforming machinery of living cells is built entirely of relatively fragile and
unstable organic molecules that are unable to withstand high temperatures,
strong electric currents or extremely acid or basic conditions. Cells are unable to
utilize heat as a source of energy as in thermal engines, rather they function as
isothermal chemical engines. The energy the cells absorb from their
environment is transformed into chemical energy (ATP) which is then used to
carry out chemical work involved in biosynthesis of cell components, the
osmotic work required to transport materials into the cell and the mechanical
work of contraction and locomotion.
Thermodynamic Principles
The qualitative treatment of energy transformation falls within the framework of
the science of thermodynamics which is the same for reactions in the living
system as for ordinary chemical systems. In practice however, more simplifying
assumptions are required in dealing with living systems since molecules in
living systems are complex and in a multi-component system. Thermodynamic
studies are usually carried out on small, isolated group of objects, called
System. There are two main types – closed system and open system.
In closed system, there is no exchange of energy and matter with the
surrounding or environment. Analysis of closed systems is relatively simple
since the initial and final states of the matter in the system are considered when
equilibrium is attained. In open system, there is exchange of energy and matter
with the environment. The analysis of the magnitude and the efficiency of
energy exchanges in open systems or steady state condition is much more
complex than in closed systems.
Interest in the study of thermodynamic properties lies in the fact that it helps to
predict the direction in which a reaction will proceed and how it is related to the
flow of energy. It answers the question ‘How far, if at all?’ The first and second
laws of thermodynamics help to make such predictions.

First Law of Thermodynamics

This is often known as the law of conservation of energy. It asserts that energy
can neither be created nor destroyed but can be transformed from one form to
another. The total energy of the universe is constant. This implies that if an
amount of heat Q is added to a system, it will be utilized to raise the internal
energy of the system and will be used to perform any external work done by
that system as a result of the absorption of heat.
If E1, is the internal energy of the system in its initial state, and EF is the internal
energy in its final state then EF - E₁ = ΔΕ………………. (1)
Where ΔΕ represents the change in internal energy of the system and depends
only on the initial and final states of the system and is independent of the
pathway or method used to attain that state. If W is used to designate the work
done by the system on its surroundings, then
Q = ΔΕ + W…………………….……………………… (2)
ΔΕ = Q - W.……………………………………………. (3)
Equation (3) is statement of the first law of thermodynamics and defines the
concept of energy in terms of that (Q) and work (W), which are directly
measurable. The dimension of heat is that of energy and the unit assigned to it is
the calorie, the work done or energy required to raise the temperature of 1 gm of
water by 1°C or precisely from 15°C to 16°C.
The work done by the system (W) may be expressed as the energy utilized to
effect a change in volume (V) against a pressure (P). In determination of the
calorimetric type, it is the pressure that is maintained constant and the volume is
allowed to change. The system that absorbs heat increases its volume, thus
performing work.
The work done for a change in volume (ΔV) at constant pressure is equal to
PΔV and equation (2) becomes
Q = ΔΕ + PΔV = ΔΗ ............................................................................ (4)

Where the change, in the energy at constant pressure (ΔΗ) refers to the change
in Heat content or Enthalpy. If ΔΗ is -ve, heat is evolved and the reaction is
EXOTHERMIC: if absorbed AH is +ve, and the reaction is
ENDOTHERMIC. ΔΗ can be determined by using a calorimeter.
C6H12O6 (solid) + 6O2 (gas) ↔ 6H2O (liquid) + 6CO2 (gas)
glucose ΔΗ = -673 Kcal per mole
This is known as heat of combustion of glucose. The first law of
thermodynamics describes an ideal reversible system. If heat energy is put into
this system, it can either do useful work or increase the enthalpy. It does not
indicate the direction of the chemical reaction.

Second Law of Thermodynamics

The second law of thermodynamics is defined mathematically in terms of a

quantity called entropy (S) or change in entropy (ΔS). Entropy is a measure of
the randomness or disorderliness of a molecular substance or matter. Only pure
crystalline substance at absolute zero of temperature would the entropy be zero.
This is so because the molecules at absolute zero are at rest and their positions
are fixed relative to each other. Increase in temperature increases randomness or
entropy as rotation, vibration or translation energies of the molecules increase.
The second law of thermodynamics therefore states that “Any process which
occurs in Nature is accompanied by an increase in total entropy” or Entropy of
the universe is ever increasing.
Entropy can also be defined as the most probable state i.e. the most random
state or least structured state. It is additive and depends on the final and initial
state and not on the process or path of achieving the state. If entropy increases,
changes will be spontaneous.
Entropy represents the fraction of enthalpy which is not available to do useful
work. The energy lost in randomness is the product of temperature (T) and
entropy (S). i.e. TS. In any change involving energy, a tax has to be paid to
Nature in the form of waste heat, which merely increases the entropy of the
universe. This is the reason heat energy cannot be completely converted to other
forms of energy since some of it is lost as entropy.
The following point must be noted with regards to the significance of the term
Entropy – A system is at equilibrium when the entropy is a maximum and the
heat absorbed ‘q’ is equal to TΔS.
q = TΔS or q-TΔS = 0
where ΔS is the change in entropy and T is the absolute temperature.

Physical and chemical processes occur spontaneously in only one direction

(e.g., water runs downhill or ball rolls downhill) until equilibrium is attained
and at equilibrium entropy is maximum and useful work could be performed as
equilibrium is attained. This is another way of stating the second law of
thermodynamics. As A. Katchalsky (1965) summarizes it, ‘life is a constant
struggle against the tendency to produce entropy.’ The synthesis of large
information-rich macromolecules, the formation of intricately structured cells,
the development of organization, all these are powerful antientropic forces. But
since there is no possibility of escaping the entropic doom imposed on all
natural phenomena under the second law of thermodynamics living organisms
choose the least evil, they produce entropy at a minimum rate by maintaining a
steady-state.

Free Energy

A combination of the first and second laws of thermodynamics gives the

condition which relates the direction (spontaneity) to the energy produced in a
chemical reaction. As it has been noted, the total heat energy or heat content of
a substance is called its ENTHALPY, and is represented by H. Of this, only
part of it represented by G, is called the Free Energy. Free energy is defined
as the useful form of energy which the cells use to do work at constant
temperature and pressure. It is not possible to find the absolute values of H
and G but interest is on the changes which H and G undergo. If H₁ and G₁ are
the enthalpy and free energy before a change and H₂ and G₂ are these quantities
after the change.

Then, ∆H = H₂ – H₁, and ΔG = G2-G1

For changes carried out at constant pressure and temperature, the difference
between ΔH and ΔG is the amount of energy involved in the entropy change
(disorderly, useless or unavailable energy).
Thus, if T is the Kelvin temperature
Or ΔH - ΔG = TΔS
ΔG = ΔH – TΔS

Free energy can be defined as the component of the total energy that is
available for useful work under constant temperature, pressure and
volume.
ΔG is the free energy change obtained at constant pressure, temperature
and volume. Almost all biological processes occur under these conditions.
Free energy change ΔG, at constant temperature and pressure must be negative
for spontaneity and the production of useful work.
At equilibrium, ΔG = O.
To displace the system from equilibrium will require the input of energy.
For a reaction A↔ B
The conversion of A to B can occur spontaneously if the free energy G A is
greater than the free energy GB thus:
The quantity GB - GA is the change in free energy ΔG and its value is negative
as energy is released in going from reactant A to product B. For a reversible
reaction to occur, an equivalent amount of energy will be supplied. Therefore, if
the free energies of the products and reactants are known, the change in free
energy (ΔG) for the reaction can be calculated and the direction of the
spontaneous change can be predicted (see example below).
For the exact definitions of these changes and for convenience, some arbitrary
reference state is chosen for calculations. The reference state is the standard
state. Standard states are strictly defined in terms of activity which is
approximately equal to molarity at low concentrations for discussions on
solutions. ΔGo, ΔHo are symbols for these quantities when reactants and
products are 1 molar, 25°C and 1 atmosphere pressure. At the biological pH of
7.0, free energy change becomes ΔGo1. These conditions are not attainable in
the cell because concentrations are less in the cell. Presence of ions affect the
value of ΔG. Temperature and pH are altered.
Standard conditions rarely occur in biological systems because concentrations
of reactants and products are less than one (1) molar, pressure and temperature
are less than standard.
This result indicates that the reaction proceeds spontaneously as written
and yields energy (exergonic, ΔGfo is – ve).