THERMODYNAMIC CONCEPTS

1st thermodynamic principle: HEAT: ENTHALPY concept 2nd thermodynamic principle: ENTROPY GIBBS FREE ENERGY

BIOCHEMICAL EXEMPLES

Master en Nanscience and Nanotechnology 2008-09 Dr. TERESA MAIRAL

THERMODYNAMIC CONCEPTS

In thermodynamics three types of systems are studied: ISOLATED (or adiabatic) : systems completely autonomous, exchanging neither material nor energy with their surroundings. CLOSED: CLOSED materially self-contained, but exchange energy across their boundaries. OPEN: OPEN exchange both energy and material with the environment

THERMODYNAMIC CONCEPTS

1st thermodynamic principle: HEAT: ENTHALPY concept It is the manifestation of the internal energy of a system. In 1842 Julius Meyer established the equivalence between heat and energy: 1st principle of thermodynamic: principle of conservation of energy SETTING UP THE ENERGY IS NEITHER CREATED NOR DESTROYED, JUST CHANGING. The heat spreads through 3 mechanisms: conduction, convection and radiation Conduction: direct contact between the heat source and the body: FOURIER LAW Convection: Convection when there is a translation of particles presents in a fluid moving from cold to hot spots and vice. Radiation: Radiation It is the process by which the heat in the form of radiant energy is transmitted into the vacuum, using electromagnetic waves.

THERMODYNAMIC CONCEPTS E is an extensive property, whose units in thermodynamic problems are calories or joules (1 cal = 4.184 J or electron-volts (1 eV = 1.6 x 10-19 J).

The internal energy E of a system is altered by exchange of work, W and heat Q with the surroundings. E or U = Q+W dE = Q+W (1)

The pressure-volume work (pV) done on the surroundings by a systems changing its volume against an external pressure p is: W= -pdV ENTHALPY concept H=E + pV (2)

dH = E+pdV (1) and (2) H=Q .H < 0--> the reaction is exothermic and heat is given off. H > 0--> the reaction is endothermic and heat is absorbed

THERMODYNAMIC CONCEPTS

2nd thermodynamic principle: ENTROPY For any spontaneous process, the Entropy(disorder) of the universe, .Suniverse, must increase. "The amount of entropy of any isolated system thermodynamically tends to increase with time ENTROPY: it is the disorder DEGREE OF A SYSTEM: BOLZMAN law S=klnW where k = Boltzmanns constant, which equals R, the gas constant (8.31 J K-1mol-1) divided by Avogadros number, = 1.38 X 10-23 J/ K. S = S(2)- S(1)= kln W2/W1

THERMODYNAMIC CONCEPTS

Relation between Heat and Entropy Change: The 19th century physicist, Clausius, proposed that the differential entropy change, dS, is proportional to the heat absorbed,dQrev, for a reversible process, with 1/T : dS= dQrev/T MORE ENTROPY-----MORE DISORDER----LOW INFORMATION In a CLOSED systems a process will occur SPONTANEOUSLY if the entropy of the system + its surroundings increases. In an open system (alive systems), the disorder is the return results of two processes: the exchange-system environment and changes that occur in the interior. Non-Isolated System (dS dQ/T) In an isolated system, the art on the inside moves to a state of equilibrium where the disorder is maximum (dS 0)

THERMODYNAMIC CONCEPTS

???????? HOW WE ARE GOING TO MEASURE THE ENTROPY CHANGES IN THE REST OF THE UNIVERSE CAUSED BY THE ENERGY FLOW ACROSS THE BOUNDARY OF THE SYSTEM??????-------- NOT POSSIBLE !!! however ===> we need a criterion of spontaneity which applies to our system (organism). At constant Temperature and Pressure (conditions under which we exist, more or less): it is possible to calculate the entropy from the flow of ENTHALPY (heat) across the boundaries of the system. The thermodynamic function that links ENTHALPYENTROPY: GIIBBS ENERGY: information about if a process is or not favourable, and is a quentitative measure of the net driving force flow at constant temperature and pressure conditions.

Gibbs Free Energy = . G

G = H-T S

THERMODYNAMIC CONCEPTS

Gibbs Free Energy = . G

G = H-T S

G <0 -- The net reaction will be in the forward direction G >0 -- The net reaction will be in the reverse direction G = 0 -- The reaction is at equilibrium, and no net change in either direction occurs aA + bB === cC + dD

= observed mass action ratio not equilibrium

Keq= equilibrium R = Ideal Gas Const. (1.99 cal mole-1 deg-1); T = is the Absolute Temperature ( Kelvin)

THERMODYNAMIC CONCEPTS

Gibbs energy content of a reaction Vs displacement from equilibrium

(a) Any change in away from the equilibrium requires an increase in the Gibbs energy : not spontaneous (b) Slope=0 : Equilibrium G = - R T ln [B]b / [A]a= - R T ln Keq (c) When the reaction has not yet proceeded as far as equilibrium, a conversion of A to B results is a decrease in G : the mechanism exist (d) The slope of the curve decreases as equilibium is approached. (e) The reaction requiere an input of Gibbs energy: not spontaneaus

THERMODYNAMIC CONCEPTS

BIOCHEMICAL EXEMPLES
CATABOLIC REACTIONS OF METABOLISM

ATP + H2O

ADP + Pi

ATP has more free energy than ADP and Pi The free energy change for this reaction, G, is less than 0 and the reaction is favorable, i.e. it is Exergonic.

THERMODYNAMIC CONCEPTS

BIOCHEMICAL EXEMPLES
CATABOLIC REACTIONS OF METABOLISM

ATP Provides Energy for:

Mechanical Work: Muscle contraction, flagella and cilia movement etc. Transport Work: Pumping ions and molecules across membranes against a concentration gradient Chemical Work: Coupling energy from ATP to Endergonic reactions to make them go

THERMODYNAMIC CONCEPTS

THERMODYNAMIC CONCEPTS

BIOCHEMICAL EXEMPLES Energy coupling by phosphate transfer

Glutamate + Ammonia Glutamine Go = +3.4 kcal/mole

This reaction is catalyzed by an enzyme in two steps Energetically, this can be described as the sum of the following two reactions :
Glu + NH3 ----> Glu-NH2 + H2O Go = +3.4 kcal/mole ATP + H2O ----> ADP + Pi Go = -7.3 kcal/mole

Glu + NH3 + ATP ----> Glu-NH2 + ADP + Pi Go = - 3.9 kcal/mole

THERMODYNAMIC CONCEPTS

BIOCHEMICAL EXEMPLES
PROTEIN DENATURATION

Protein denaturation. (A) Schematic diagram of the initial and final final states of a native denatured transition

Tm is defined by the temperature of the equilibrium, G=0 between the native and denatured states

Tm= H/ S

BIBLIOGRAPHY
Molecular biophysics part: Biophysics, W. Hoppe, W. Lohmann, H. Markl, H. Ziegler (eds). Springer-Verlag, Berlin, 1983. Chapter 3. (Chapters 1 and 2 are recommended for students with no previous exposure to biology/biochemistry although in this case a better introduction would be a general Biochemistry book such as Lehningers Biochemistry). Bioenergetics part: Bioenergetics3, D.G. Nicholls, S.J. Ferguson, Academic Press, Amstedam, 3rd ed, 2002. Chapters 3 and 4. Bioelectrochemistry: Electrode Dynamics, A.C. Fisher, Oxford University Press, Oxford, 1996.