Bioenergetics and Thermodynamics
Bioenergetics - Study of how organisms manage their
energy resources
Thermodynamics - the study of energy transformations
An organisms metabolism transforms matter and
energy, and it is therefore subject to the laws of
thermodynamics
Laws of Thermodynamics
First law of thermodynamics Second law of thermodynamics
in any physical or chemical change, the universe always tends toward
the total amount of energy in the more and more disorder: in cell
universe remains constant, although natural processes, the entropy of
the form of the energy may change. the universe increases
Heat
co2
+
H2O
Every energy transfer or transformation
the chemical (potential) energy
increases the disorder (entropy) of the
in food will be converted to the
universe. E.g. disorder is added to the
kinetic energy of the cheetahs
cheetahs surroundings in the form of heat
movement in (right)
Free Energy Change, G
The Gibbs Free Energy is a measure of the energy
available from a reaction
G = H T S
For a chemical or physical process, the free energy change (G
(J/mol) is expressed in terms of the change in enthalpy (heat
content, H, J/mol) and entropy (S, J/mol.K) as the reactants are
converted to products
Free Energy Change, G= H T S
G Negative Exergonic A reaction can occur spontaneously only ;
Reaction proceeds in the direction it is written
G Positive Endergonic A reaction cannot occur spontaneously . An input of free
energy is required to drive such a reaction.
Reaction proceed in the reverse direction
G Zero A system is at equilibrium and no net synthesis of product
Changes in enthalpy and entropy contribute to G
The sum of these contributions at a given temperature
should be negative for a spontaneous reaction
If S is negative (products are more ordered than reactants), a
sufficiently negative H can overcome the decrease in entropy
If H is positive (products have a higher heat content than reactants),
a sufficiently positive S can overcome the increase in enthalpy
S is positive when entropy increases and H is negative when heat is
released by the system to its surroundings. Either of these conditions,
which are typical of favorable processes,will tend to make G negative
Free Energy Change, G
Predicts if the reaction can occur spontaneously or an input of
energy is required.
The G of a reaction is independent of the path (or molecular
mechanism) of the transformation. The mechanism of a reaction
has no effect on G. For example, the G for the oxidation of
glucose to CO2 and H2O is the same whether it occurs by
combustion in vitro or by a series of enzyme-catalyzed steps in a
cell.
The G provides no information about the rate of a reaction. A
negative G indicates that a reaction can occur spontaneously, but
it does not signify whether it will proceed at a perceptible rate.
The rate of a reaction depends on the free energy of activation
(G), which is largely unrelated to the G of the reaction.
Free Energy Change, G
G = Gproducts - Greactants
The G of a reaction depends only on the free energy of
the products (the final state) minus the free energy of the
reactants (the initial state).
Standard Free Energy Change, G
G = - RT In Where R = 8.314 J/(mol. K)
G = - RT In Keq
Under standard conditions (25 C or 298K; pH 7.0), when reactants and products are
initially present at 1 M concentrations or, for gases, the force driving the system toward
equilibrium is defined as the standard free-energy change, G. Each chemical reaction
has a characteristic G, which may be positive, negative or zero, depending on the
equilibrium constant of the reaction. Just as K'eq is a physical constant characteristic
for each reaction, so is G' a constant: it has a characteristic, unchanging value for
a given reaction.
Relation between G and Keq (at 25C)
G = - RT In Keq
-1 -1
Keq kcal mol kJ/mol
-5
10 6.82 28.53
-4
10 5.46 22.84
-3
10 4.09 17.11
-2
10 2.73 11.42
-1 Keq G Direction
10 1.36 5.69
1 0 0 <1 Negative Proceeds forward
10 -1.36 -5.69
2
1 Zero At Equilibrium
10 -2.73 -11.42
3 <1 Positive Proceeds in reverse
10 -4.09 -17.11
4
10 -5.46 -22.84
5
10 -6.82 -28.53
Actual Free Energy Change, G
G = G + RT In
G = G + RT In Q Where R = 8.314 J/(mol. K)
G, of a given chemical reaction is a function of the concentrations and of
the temperature actually prevailing during the reaction.
The G of any reaction proceeding spontaneously toward its equilibrium is
always negative, becomes less negative as the reaction proceeds, and is
zero at the point of equilibrium, indicating that no more work can be done by
the reaction
Even a reaction for which G' is positive can go in the forward direction, if
G is negative. This is possible if the term RT ln ([products]/[reactants]) is
negative and has a larger absolute value than G.
Summary: Equations
Standard Free Energy change
G = -RT In Keq Where
G = -2.303 RT log Keq R = 8.314 J/(mol. K)
Actual Free Energy change
G = G + RT In Q
Units of energy-
A calorie (cal): the amount of heat required to raise the temperature of 1
gram of water from 14.5C to 15.5C.
A joule (J): amount of energy needed to apply a 1-newton force over a
distance of 1 meter.
1 kcal = 4.184 kJ
Standard Free-Energy Changes Are
Additive
In the case of two sequential chemical reactions,
A B and B C, each reaction has its own equilibrium
constant and each has its characteristic standard free-energy
change, G'1 and G'2.
As the two reactions are sequential, B cancels out and the
overall reaction is A C. Reaction A C will also have its own
equilibrium constant and thus will also have its own standard
free-energy change, G'total.
The G values of sequential chemical reactions are additive.
For the overall reaction A C, G'total is the sum of the G'1
and G'2
Standard Free-Energy Changes Are Additive
Endergonic reaction:
G is positive, reaction is Glucose + Pi glucose-6-phosphate + H2O
not spontaneous
. . . G' = 13.8 kJ/mol
Exergonic reaction: G is ATP + H2O ADP + Pi
negative, reaction is
spontaneous . . . G' = -30.5 kJ/mol
Coupled reactions: (1) Glucose + Pi glucose-6-phosphate + H2O +13.8 kJ/mol
Overall G is negative; (2) ATP + H2O ADP + Pi -30.5 kJ/mol
together, reactions are ATP + glucose ADP + glucose-6-phosphate -16.7 kJ/mol
spontaneous
Standard Free-Energy Changes Are
Additive
G' is a way of expressing the equilibrium
constant for a reaction
K'eq1= [glucose-6-phosphate] =3.910-3M-1
[glucose][Pi]
K'eq2= [ADP][Pi] =2105M-1
[ATP]
K'eq3= [glucose-6-phosphate][ADP][Pi] =K'eq1K'eq2 = 7.82M-1
[glucose][Pi][ATP]
Example 1:
If the equilibrium concentrations of ATP = 1.0 x107 M,
ADP = 0.165 M and Pi = 0.1 M, what are the equilibrium constant and
Go' for the hydrolysis of ATP at 37C?
a) Use the data to calculate Keq'.
b) Use the value of Keq' to calculate Go'.
In a typical cell at 37 C, the concentration of
ATP = 8 x 103 M,
ADP = 1 x 103 M, and
Pi = 8 x 103 M.
What is the actual free energy change (G') for ATP hydrolysis under
these conditions?
Example 2
Calculate G and G for the isomerization of dihydroxyacetone
phosphate (DHAP) to glyceraldehyde 3-phosphate (GAP). This
reaction takes place in glycolysis. At equilibrium, the ratio of GAP to
DHAP is 0.0475 at 25C and pH 7. Hence, Keq = 0.0475.
