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half life
the time it takes for reactant concentration to reach half of its initial value (concentration)
rate constant
proportionality constant in a rate law
reaction order
exponent to reactant concentration in rate law; shows how rate varies concentration
intermediate
forms in 1 step of a mechanism and is consumed in a subsequent step
catalyst
increases reaction rate without being consumed in the reaction
reaction rate
the increase in molar concentration of product of a reaction per unit time or the decrease in molar concentration of reactant per time
overall order of a reaction
equals the sum of the orders of the reactant species in the rate law
integrated rate law
mathematical relationship btwn concentration and time
first order integrated rate law
ln([A]t/[A]o) = -kt
2nd order integrated rate law
1/[A]t = kt + 1/[A]o
zero order integrated rate law
[A]t = -kt + [A]o
first order half life equation
t1/2 = ln(2) / k OR t1/2 = 0.693 / k *independent of initial concentration
2nd order half life equation
t1/2 = 1/k[A]o *relies on inital concentration
zero order half life equation
t1/2 = [A]o / 2k *relies on initial concentration
collision theory
a theory that assumes that, for a rxn to occur, reactant molecules must collide with an energy greater than some minimum value and with the proper orientation.
activation energy
the minimum energy of collision needed for 2 molecules to react. --catalysts (enzymes) will decrease this
transition state theory
explains the reaction resulting from the collision of two molecules in terms of an activated complex
activated complex (or transition state)
an unstable grouping of atoms that can break up to form products
Arrhenius Equation
the mathematical equation k = Ae^(-Ea/RT) which expresses the dependence of the rate constant on temperature --named after Svante Arrhenius
Frequency factor
the symbol A in the Arrhenius equation, which is assumed to be constant
2 point form of the Arrhenius equation
ln(k2/k1) = Ea/R (1/T1 - 1/T2)
elementary reaction
a single molecular event, such as a collision of molecules, resulting in a reaction
reaction mechanism
the set of elementary reactions whose overall effect is given by the net chemical equation
molecularity
the number of molecules on the reactant side of an elementary reaction 1 = unimolecular 2 = bimolecular 3 = termolecular
rate determining step
the slowest step in the reaction mechanism
catalysis
the increase in rate of reaction that results from the addition of a catalyst
Homogenous Catalysis
is in same phase as reactants and products and is usually in gas or liquid phase.
heterogenous catalysis
catalyst that exists in a different phase from the reacting species --usually a solid catalyst in contact with a gaseous or liquid solution of reactants
chemisorption
binding of a species to a surface by chemical bonding forces
substrate
the substance whose reaction the enzyme catalyzes
chemical equilibrium
the state reached by a reaction mixture when the rates of the forward and reverse rxns are equal
equilibrium constant expression
an expression obtained by multiplying the concentrations of products, dividing by the concentration of reactants, and raising each concentration term to a power equal to the coefficient in the chemical equation
equilbrium constant Kc
the value obtained for the eq-constant expression when equilibrium concentrations are substituted
law of mass action
a relation that states that the values of the eq-constant expression Kc are constatn for a particular reaction at a given temp, whatever eq concentrations are substituted
equilibrium constant Kp
an eq constant for a gaseous rxn in terms of partial pressures
homogeneous equilibrium
an equilibrium that involves reactants and products in a single phase
heterogeneousequilibrium
an equilibrium involving reactants and products in more than one phase
reaction quotient
represented by Qc has the same form as the equilibrium constant Kc but whose concentration values are not necessarily those at equilibrium
Le Chatelier's Principle
states that when a system in chem equilibrium is disturbed by a change in temp, pressure, or conc', the system shifts in equilibrium composition in a way that tends to counteract this change of variable
when adding reactants or removing products (le chatelier's)
when more reactant is added or product is taken away, the conc' changes of either, and net reaction occurs to left to right (in the FORWARD) direction, to give a new equilibrium and more products are produced
when adding products or removing reactants (le chateliers)
when more product is added or some reactant is removed, the conc' will change, and the net reaction occurs right to left (in the REVERSE) direction to give a new equilibrium, and more reactants are produced
pressure changed (le chatelier's)
if the pressure is increased by decreasing the volume of a reaction mixture, the reaction shifts in the direction of fewer moles of gas
temp changes (le chatelier's)
-->for an endothermic rxn (+ΔH), the amounts of products are increased at eq. by an increase in temp (kc is larger at higher T) -->for an exothermic rxn (-ΔH), the amounts of products are increased at eq. by a decrease in temp (Kc larger at lower T)
Temp Changes and Le Chatelier's Principle
-exothermic reactions: heat is a product -endothermic reactions: heat is a reactant -exothermic with increased temp: shift to the left to decrease heat present -exothermic with decreased temp: shift to the right -endothermic with increased temp: shift to the right -endothermic wi…

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