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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]
Potential Energy
Spontaneous
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
A -> B
@ equilibrium
G = 0
@ equilibrium
Keq is a constant
% Hb bound
[O2]
COUPLED REACTIONS
Chemical Analogy
Mechanical Analogy
G +
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
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
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
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
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
The end