Term
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Definition
k = A*e^(-Ea/(R*T))
k = rate constant
T = temperature(abs)
A = constant that relates to the orientation of the colliding molecules
Also: ln(k2/k1) = -Ea/R((1/T2)-(1/T1)) |
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Term
Effect of Temperature on Reaction Rate |
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Definition
Temperature affects the rate by affecting the rate constant |
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Term
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Definition
-Does NOT change with temperature
-it is the minimum energy the molecules must have to react |
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Term
Graphical Determination of the Activation Energy |
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Definition
A plot of lnk vs. 1/T gives a straight line with slope = -Ea/R |
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Term
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Definition
-the reaction rate as the result of particles colliding w/ each other to react
-thus, concentration are multiplied in the rate law
-only those collision w/ enough energy to exceed Ea can lead to reaction |
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Term
Effect of Temperature on Collisions |
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Definition
-a temperature rise enlarges the fraction of collisions w/ enough energy to exceed the Ea
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Term
Fraction of Molecular Collisions (f) |
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Definition
f = e^(-Ea/(R*T))
- the magnitudes of both Ea and T affect the fraction of sufficiently energetic collisions |
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Term
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Definition
A reversible reaction has two activation energies |
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Term
Comparing Ea of fwd and rev reactions |
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Definition
-exothermic process-f of reactant collisions w/ energy exceeding Ea(fwd) is larger than the f of product collision w/energy exceeding Ea(rev) and fwd reaction is faster
-endothermic- opposite |
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Term
Relation of Ea,T,k, and the rate |
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Definition
-smaller Ea(or higher T) = larger k = increased rate
-larger Ea(or lower T) = smaller k = decreased rate |
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Term
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Definition
-molecules must collide so that the reacting atoms make contact
-collison must have enough energy and a particular nolecular orientation |
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Term
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Definition
-the product of the collision frequency Z and an orientation probability factor, p
*A = pZ |
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Term
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Definition
-At the moment of a head-on collision, the molecules stop and their Ek is converted to Ep of the collision
-if the Ep is less than the Ea, the molecules recoil |
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Term
Transition State or Activated Complex |
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Definition
-neither a reactant or a product but a transitional species with partial bonds
-it's extremely unstable
-the Ea is the quantity needed to stretch and deformm the bonds in order to reach the transition state
- a transition state can go in either direction |
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Term
Reaction Mechanism/Intermediate |
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Definition
Mechanism- a sequence of single reaction steps that sum to the overall reaction
Intermediate- a substance that is formed and used up during the overall reaction |
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Term
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Definition
-the potential energy of the system during the reaction as a smooth curve
-deltaH of rxn = Ea(fwd) - Ea(rev) |
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Term
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Definition
-each describes a single molecular event, not made up simpler steps
-can be unimolecular or bimolecular |
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Term
Termolecular Elementary Steps |
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Definition
-rarely occur bc the probability of three particles colliding simultaneously w/ enough energy and w/ an effective orientation is small |
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Term
Rate Law for an Elementary Step |
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Definition
-can be deduced from the reaction stoich.
-we use the equation coefficients as the reaction orders in the rate law for an elementary step: that is, the reation order equals molecularity |
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Term
The Rate-Determining Step/
Rate-Limiting Step
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Definition
-slower than the others, so it limits how fas the overall reaction proceeds.
-its rate law represents the rate law for the overall reaction
-a reactant can have a reaction order of zero because it takes part in the reaction only after the rate-determining step |
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Term
Correlation Mechanism with the Rate Law |
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Definition
-the elementary steps must add up to the overall balanced equation
-the elementary steps must be physicall reasonable (why termolecular step is rare)
-the mechanism must correlate with the rate law (must correlate with experimental facts)
-cannot include intermediates |
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Term
Mechanisms and Transition States |
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Definition
Each step in the mechanism has its own transition state |
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Term
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Definition
-a substance that increases the rate w/o being consumed in the rxn
-causes a lower Ea which in turn makes the rate constant larger and the rate higher |
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Term
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Definition
-Does not yield more product than one w/o a catalyst but it yields the product more quickly
-causes a lower Ea by providing a different mechanism for the reaction |
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Term
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Definition
-exists in solution w/ the reaction mixture |
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Term
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Definition
-speeds up a rxn that occurs in a separate phase |
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