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Biochemistry 5 FUNDAMENTALS

Reaction Rates and Equilibrium AUSOM

Important concepts

Energy and Thermodynamics Kinetic Energy Temperature F, C, K F -> C C -> F C -> K TF = 1.80(Tc) + 32 Tc = (TF - 32)/1.80 TK = Tc + 273

BioChemical Reactions

Consider A <-> B

[A]

[B]

Loss of Energy, Exothermic Gain of Energy, Endothermic

Potential Energy

Biological Energy is the Gibbs Free Energy G

Heat can be measured by Calorimetry

Spontaneous

Combined 1st & 2nd Laws G = H - TS

Example Which would you expect to have higher entropy? Water Water 20 individual AA Solid NaCl Ice Steam a polypeptide containing 20 AA NaCl (aq)

Boltzmann

S = k ln ( )

= Number of States

Biological Energy is the Gibbs Free Energy G

A -> B

Types of reactions Consider if y-axis is Heat

Consider [A] -> [B]


!

@ equilibrium

G = 0

@ equilibrium

Changing the concentrations will move the reaction Le Chateliers

Keq is a constant

% Hb bound

[O2]

COUPLED REACTIONS

Chemical Analogy

Mechanical Analogy

ADP + Pi -> ATP

G +

COUPLED REACTIONS IN GLYCOLYSIS

ATP, ~ 7Kcal/mol

ADP, ~ 7Kcal/mol

AMP, ~ 2Kcal/mol

Oxidative Phosphorylation

Summary

Spontaneous and Nonspontaneous Changes. Spontaneous processes take place naturally with no apparent cause or stimulus. Process spontaneity depends on the energy and entropy changes that accompany the process. Energy decreases and entropy increases favor spontaneity. However, a nonspontaneous change in one of these factors can be compensated for by a large spontaneous change in the other to cause processes to be spontaneous. Reaction Rates. The speed of a reaction is called a reaction rate, and can be determined by measuring how fast reactants are used up or products are formed. Molecular Collisions. Explanations of how reactions take place are called reaction mechanisms. most mechanisms are based on three assumptions: (1) molecules must collide with each other, (2) the collision must involve a certain minimum of energy, and (3) some colliding molecules must be oriented in a specific way during collision in order to react.

Energy Diagrams. Energy relationships for reactions can be represented by energy diagrams in which energy is plotted versus the reaction progress. The concepts of exergonic and endergonic reactions and activation energy are clearly represented by such diagrams. Factors That Influence Reaction Rates. Four factors affect the rates of all reactions: (1) the nature of the reactants, (2) reactant concentrations, (3) reactant temperature, and (4) the presence of catalysts. Chemical Equilibrium. Reactions are in equilibrium when the rate of the forward reaction is equal to the rate of the reverse reaction. Equilibrium is emphasized in reactions by writing double arrows pointing in both directions between reactants and products. Position of Equilibrium. The relative amounts of reactants and products present in a system at equilibrium defines the position of equilibrium. The equilibrium position is toward the right when a large amount of product is present, and toward the left when a large amount of reactant is present. The position is indicated by the value of the equilibrium constant.

Factors That Influence Equilibrium Position. Factors known to influence the position of equilibrium include changes in amount of reactants and/or products, and changes in temperature. The influence of such factors can be predicted by using Le Chatelier's principle. Catalysts cannot change the position of equilibrium.

Formative Assessment

A nitrogen gas sample is compressed to the point of liquification. This change is state is accompanied by which of the following changes. Entropy and energy decrease Entropy and energy increase Entropy increases but energy decreases Energy increases but entropy decreases

Entropy and energy decrease

The rate of a chemical reaction must be expressed in minutes. True False

False

For the reaction depicted in Figure One, (b) refers to: time of flight heat of formation activated complex activation energy heat of sublimation
Figure one

activation energy

The reaction depicted in Figure One is exothermic True False

True

For a homogeneous catalysis: The reactants must reach the surface An enzyme is involved One must raise the activation energy The catalyst must be in the same state as the reactants

The catalyst must be in the same state as the reactants

For a system in equilibrium: the rate of the forward and reverse reactions are the same the concentrations of the reactants and products are the same the solution is saturated the solvent must be water

the rate of the forward and reverse reactions are the same

For the following system in equilibrium: 2NO2 (g) <---> N2O4 (g), what effect will increasing pressure have? shift to the left shift to the right no effect reduce the 2NO2 concentration

shift to the right

For a reaction to be spontaneous, which if the following must be true. delta H must be negative delta H must be positive delta S must be negative delta S must be positive delta G must be negative delta G must be positive

delta G must be negative

The end