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] .

Exothermic Gain of Energy.Loss of Energy. Endothermic Potential Energy .

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Biological Energy is the Gibbs Free Energy ΔG Heat can be measured by Calorimetry .

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Spontaneous .

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TΔS .Combined 1st & 2nd Laws ΔG = ΔH .

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 .

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Biological Energy is the Gibbs Free Energy ΔG A -> B .

Types of reactions Consider if y-axis is Heat .

Consider [A] -> [B] ! @ equilibrium ΔG = 0 ! ! .

@ equilibrium ! ! ! Changing the concentrations will move the reaction Le Chateliers .

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Keq is a constant .

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% Hb bound [O2] .

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COUPLED REACTIONS

Chemical Analogy

Mechanical Analogy

ADP + Pi -> ATP ΔG + COUPLED REACTIONS IN GLYCOLYSIS .

~ 7Kcal/mol AMP. ~ 7Kcal/mol ADP. ~ 2Kcal/mol .ATP.

Oxidative Phosphorylation .

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Summary .

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

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

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

Formative Assessment .

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

•  Entropy and energy decrease .

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

•  False .

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

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

•  shift to the right .

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 .•  For a reaction to be spontaneous. which if the following must be true.

•  delta G must be negative .

The end .

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