Thermodynamics

Thermodynamics

The first law of thermodynamics

Energy cannot be created or destroyed, it can only be converted from one
form to another.

The second law of thermodynamics

All systems tend to become more disorganized.

Biological systems cannot violate the laws of thermodynamics

Reactions tend to occur if
they release heat (I.e. if they are exothermic)
reactions can also be isothermic or endothermic

they lead to disorder (increase in entropy)

Thermodynamics

Thermodynamics

Gibbs free energy (G) is a function that is useful in determining the

spontaneity of a reaction
G cannot be measured directly

The difference in Gibbs free energy (G) for a reaction determines

whether the reaction is spontaneous
if G is negative, the reaction is spontaneous
if G is zero, the reaction is at equilibrium
if G is positive, the reaction is non-spontaneous

G = H - TS
where

G = the difference in Gibbs free energy

H = the difference in enthalpy
T = the absolute temperature in degrees Kelvin
S = the change in entropy of the universe

Thermodynamics

Thermodynamics

How can reactions be spontaneous?

if G is negative the reaction is spontaneous, so if

G = H - TS

a reaction can be spontaneous if

H is negative, S is positive
H is positive, S is very positive
H is very negative, S is negative
it itself is non-spontaneous but it is coupled to a spontaneous one!

Thermodynamics

Thermodynamics

G describes the free energy change under any specified conditions

G describes the free energy change under standard conditions

solutes at 1 M concentration (except water)
temperature at 25 degrees C
pressure at 1 atmosphere

G = -2.303 RT log Keq

G = -2.303 RT log [products]
[reactants]

G describes the free energy change under standard conditions

solutes at 1 M concentration, including H+

if H+ is involved in a reaction, this means pH 0!

G is the free energy change under standard conditions at pH 7.0

Thermodynamics

Thermodynamics

Example:

ATP is a common form of energy currency within cells

ATP hydrolysis has a high G (-30.5 kJ mol-1)

ATP + H20 ADP + Pi + H+

The equilibrium for this reaction lies heavily towards the products

Thermodynamics

Thermodynamics

Reactions that are not spontaneous can be coupled to spontaneous

reactions
under these conditions, the overall reaction can be spontaneous

A+B
C+D
F+G
C+E
A+B+ED+F+G

G overall reaction = G reaction 1 + G reaction 2

The coupling of metabolism, particularly to ATP hydrolysis, can drive

thermodynamically unfavorable reactions forward.

G reaction 1
G reaction 2
G overall reaction

Thermodynamics

Thermodynamics

Reactions that are not spontaneous, can be coupled to spontaneous

reactions

glucose-6-phosphate fructose-6-phosphate
G = +1.7 kJ mol-1

fructose-6-phosphate + ATP fructose-1,6-bisphosphate + ADP

G = -14.2 kJ mol-1

overall reaction:

glucose-6-phosphate + ATP fructose-1,6-bisphosphate + ADP

G = -12.5 kJ mol-1

The coupling of metabolism, particularly to ATP hydrolysis, can drive

thermodynamically unfavorable reactions forward.

Thermodynamics

Thermodynamics

If biochemical reactions release energy (G is negative), some of this

energy can be harnessed to do work

Catabolism
breakdown of large molecules to smaller ones
starch to glucose to carbon dioxide

releases energy

Anabolism
synthesis of large molecules from smaller ones
carbon dioxide to glucose to starch

requires input of energy

Two major types of reactions are involved in metabolic energy

conversions
oxidation reduction (redox) reactions
phosphorylation reactions

Thermodynamics

Redox Reactions

Oxidation reduction (redox) reactions

redox reactions involve the transfer of electrons
oxidation is the loss of electrons (leo)
reduction is the gain of electrons (ger)
often accompanied by H+

redox reactions occur between redox partners

A(reduced)

B(oxidized)

A(oxidized)

B(reduced)

the more reduced compound is oxidized

this compound is the reductant

the more oxidized compound is reduced

this compound is the oxidant

redox reactions have an associated G

this energy can be used in metabolism
Thermodynamics

Redox Reactions

NAD+ (reduced form NADH, H+) (nicotinamide adenine dinucleotide)

NADP+ (reduced form NADPH, H+) (nicotinamide adenine dinucleotide
phosphate)

Redox Reactions

FAD (reduced form FADH2) (flavin adenine dinucleotide)

FMN (reduced form FMNH2) (flavin mononucleotide)

Thermodynamics

ATP

ATP is a universal energy currency within cells

the biosynthesis of ATP from ADP and Pi requires an input of energy
G for synthesis = 30.5 kJ mol-1
energy derived directly or indirectly from catabolism
animals, microorganisms, plants

energy derived directly from photosynthesis

plants, cyanobacteria

phosphoanhydride bonds are high energy bonds

sometimes drawn as ~ to denote high energy

Thermodynamics

ATP

ATP is not the energy storage form within cells

glycogen or fat in animals
sucrose, starch in plants

ATP is rapidly used and resynthesized

most ATP is synthesized indirectly from the oxidation of NADH in the

mitochondria
some metabolic intermediates can lead directly to phosphorylation of
ADP to ATP

Thermodynamics

Redox Reactions

Enzymes that catalyze biological redox reactions use coenzymes to

trap redox energy from catabolism
energy later converted into potential energy of ATP

Thermodynamics

Redox Reactions

Enzymes that catalyze biological redox reactions use coenzymes to

trap redox energy from catabolism
energy later converted into potential energy of ATP
in metabolism, energy is converted from one form to another
food (carbohydrates, lipids, etc) NADH ATP work

the interconversion of energy from one form to another in metabolism is

like a biochemical Rube Goldberg machine

Thermodynamics