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Test 2-Ch.16 B Kinetics
N/A
26
Chemistry
Undergraduate 1
03/28/2011

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Term
Arrhenius Equation
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))

Term
Effect of Temperature on Reaction Rate
Definition
Temperature affects the rate by affecting the rate constant
Term
Activation Energy
Definition

-Does NOT change with temperature

-it is the minimum energy the molecules must have to react

Term
Graphical Determination of the Activation Energy
Definition
A plot of lnk vs. 1/T gives a straight line with slope = -Ea/R
Term
Collision Theory
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

Term
Effect of Temperature on Collisions
Definition

-a temperature rise enlarges the fraction of collisions w/ enough energy to exceed the Ea

 

Term
Fraction of Molecular Collisions (f)
Definition

f = e^(-Ea/(R*T))

- the magnitudes of both Ea and T affect the fraction of sufficiently energetic collisions

Term
Reversible Reactions
Definition
A reversible reaction has two activation energies
Term
Comparing Ea of fwd and rev reactions
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

Term
Relation of Ea,T,k, and the rate
Definition

-smaller Ea(or higher T) = larger k = increased rate

-larger Ea(or lower T) = smaller k = decreased rate

Term
Effective Collisions
Definition

-molecules must collide so that the reacting atoms make contact

-collison must have enough energy and a particular nolecular orientation

Term
Frequency Factor(A)
Definition

-the product of the collision frequency Z and an orientation probability factor, p

*A = pZ

Term
The Transition State
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

Term
Transition State or Activated Complex
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

Term
Reaction Mechanism/Intermediate
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

Term
Reaction Energy Diagram
Definition

-the potential energy of the system during the reaction as a smooth curve

-deltaH of rxn = Ea(fwd) - Ea(rev)

Term
Elementary Reactions
Definition

-each describes a single molecular event, not made up simpler steps

-can be unimolecular or bimolecular

Term
Termolecular Elementary Steps
Definition
-rarely occur bc the probability of three particles colliding simultaneously w/ enough energy and w/ an effective orientation is small
Term
Rate Law for an Elementary Step
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

Term

The Rate-Determining Step/

Rate-Limiting Step

 

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

Term
Correlation Mechanism with the Rate Law
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

Term
Mechanisms and Transition States
Definition
Each step in the mechanism has its own transition state
Term
Catalyst
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

Term
How A Catalyst Functions
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

Term
Homogeneous Catalyst
Definition
-exists in solution w/ the reaction mixture
Term
Heterogeneous Catalyst
Definition
-speeds up a rxn that occurs in a separate phase
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