Gibbs free energy

G= H-T S
T, temperature on the Kelvin scale
units: Joule

G < 0 : reactants should convert into products

reaction goes forward
G > 0 : reverse reaction is favored

G = 0 : reaction goes forward as it goes

backward in the same rate, no changing
net effect on the system; equilibrium

Small delta G: close to zero means reaction might be reversible

Large delta G: irreversible in one or the other direction
The standard free energy change of a reaction is
related to the equilibrium constant
For G, the free energy of a reaction, standard conditions are defined:
 concentration of reactants and products at 1M
 temperature at 25°C
 acidity at pH 7.0
Under these standard conditions, ΔG 0' is defined as the standard free
energy change.
For a reaction

A+B C+D
the ratio of products to reactants is given by keq' (=keq at pH 7.0):

The relationship of ΔG0' and keq' is

0'
G = - R T ln keq' = - R T 2.030 log10 keq'
with
R = 8.315 [J mol-1 K-1] (molar gas constant)
T = temperature [K]
In theory, we can now decide if a reaction is favorable (G0' < 0).
A thermodynamically unfavorable reaction
can be driven by a favorable reaction
Pathway must satisfy two criteria:
l Specific (mediated by specific enzymes)
l Thermodynamically favorable (Change of free energy
G is negative)

Overall free-energy change for a chemically coupled

series of reactions is equal to the sum of the
free energy changes of the individual steps
ATP is the universal currency of free
energy in biological systems

ATP is an energy-rich molecule

because its triphosphate unit contains
two phosphoanhydride bonds
 ATP has a stronger
phosphoryl transfer potential

At pH7 the triphosphate unit of ATP carries

about 4 negative charges. They repel one
another because they are in close proximity.
 ATP hydrolysis drives metabolism by shifting
the equilibrium of coupled reactions

Thus, net conversion of A into B cannot occur spontanously as it is not

thermodynamically favourable (ΔG is positive!)
However, A can be converted into B under these conditions if the
reaction is coupled to the hydrolysis of ATP.
The new overall reaction is
ATP is continually regenerated from
ADP
 Metabolic pathways can be divided
in two broad classes

Pathways that convert energy into biologically useful forms

-> catabolism

Pathways that require energy input to proceed

->anabolism
 The oxidation of carbon fuels is an
important source of cellular energy
In aerobic organisms the ultimate electron acceptor in
the oxidation of carbon is O2 and the oxidation product
is CO2
 Oxidation and reduction
1) General definition
Oxidation is loss of electrons.
Reduction is gain of electrons

2) Biochemistry-applied definition
Oxidation is loss of hydrogen
Reduction is gain of hydrogen
 The oxidation of carbon fuels is an
important source of cellular energy
In aerobic organisms the ultimate electron acceptor in
the oxidation of carbon is O2 and the oxidation product
is CO2