CH 14 Kinetics study Guide
Reaction Rate with time
The speed at which a reaction occurs is called the Reaction rate
Reaction rate is a measure of how fast the reaction makes products or used up reactants with
time.
Change in concentration of reactant/product
Rate =
Change in time
Δ [Product] Δ [Reactant] (-ve sign indicates that [reactant]
Average rate =
Δ time
= - Δ time decreases with time)
Rate values are ALWAYS positive!
Instantaneous Rate is the Rate of the reaction at any instant during the reaction.
Determined by taking the slope of a line tangent to the curve at that particular point.
Initial Rate: Reaction rates measured at the start of a reaction.
Reaction Rate and Stoichiometry
In general, for a reaction:
The rate is given by,
Rate Laws
Rate law for a reaction aA → products is:
1 ∆[A]
rate = − = 𝑘[A]!
𝑎 ∆𝑡
When n = 0, the reaction is zero order with respect to A.
When n = 1, the reaction is first order with respect to A.
When n = 2, the reaction is second order with respect to A.
Reaction Example Chemical Example Rate
Units of k
Order Equation Law
0 −1
0 aA → products Rate = k[A] = k M·s
−1
1 aA → products Rate = k[A] s
2 −1 −1
2 aA → products Rate = k[A] M s
−1 −1
2 aA + bB → products Rate = k[A][B] M s
2 −2 −1
3 aA + bB → products Rate = k[A] [B] M s
2 different methods exist for calculating Reaction orders
1. Initial Rate Method: Calculates m & n by changing 1 reactant conc. & keeping the other
reactant conc. constant
-See what happens to rate
2. Graphical Method: Plot concentration vs time
-Look for a straight line
Rate constant, k
Unit of k depends on the order of the reaction
Reaction Units Straight Half-Life
Rate Law Integrated Rate Law
Order of k Line Plot Expression
[A] vs. t A!
0 Rate = '[A]! M , s "# [A]$ = −'/ + [A]! /½ =
slope = −k 2'
ln[A] vs. t ln 2
1 Rate = '[A] s-1 ln[A]$ = −'/ + ln[A]! /½ =
slope = −k '
'
1 1 1/[A] vs. t /½ =
2 Rate = k[A]2 M−1s−1 = '/ + A!
A$ A! slope = k
Half Life, t½ – time needed for original conc. to decrease by ½
Collision theory
1. Molecules must collide for a reaction to occur (More collisions ® faster rates)
2. Colliding molecules must be orientated properly to react
3. Properly oriented molecules must have sufficient energy ( Activation Energy, Ea )
Activation Energy, Ea – minimum energy required to break bonds
- Is a barrier that must be overcome
- Often results in an activated complex or unstable transition state
- More important than orientation
Energy profiles
Rate depends upon Ea:
The smaller the Ea, the faster the reaction.
Able to determine enthalpy (DH) associated with rxn:
Exothermic (DH neg): Products energy is lower than reactants
Endothermic (DH pos): Products energy is higher than reactants
Arrhenius Equation
If want to relate k at 2 different temps:
æ k ö Ea æ 1 1 ö
lnçç 2 ÷÷ = çç - ÷÷
k
è 1ø R è T1 T2 ø
Note: R is 8.314 J. mol-1K-1
Reaction Mechanisms
Reaction Mechanism – series of sequential elementary reactions
Indicates:
Order of breaking & forming bonds
Changes in atom position during a rxn
Elementary Step rxns – a 1 step event, a single collision of correctly orientated & energetic
reactants
• MOLECULARITY – describes # of molecules (or atoms) on the reactant side of an
elementary chemical reaction
a) Unimolecular reaction: 1 reactant
b) Bimolecular reaction: 2 reactants
c) Termolecular reaction: 3 reactants
Rate law CAN BE determined from stoichiometry!
a) Each STEP is an elementary rxn AND must ADD ALL steps to get Overall rxn
b) Each step also proceeds at a different rate
- The overall reaction can only go as fast as the SLOWEST step!
The slowest step is also called the Rate-determining step (r.d.s.)
- Rate law of OVERALL RXN is the same as the Rate Law of the SLOW step!
Intermediates
How to identify intermediates: Intermediates are molecules that are produced in an elementary
step and is used up in a subsequent elementary step.
Intermediates never show up in the overall chemical reaction.
Catalysts
A chemical that changes the reaction rate, without being consumed during a reaction.
A catalyst increases reaction rate by increasing k:
1. New mechanism, by lowering Ea
2. Correctly orientating reactants, by increasing A
Types of Catalysts:
1. Homogeneous – catalyst same phase as reactants
2. Heterogeneous – catalyst in different phase than reactants
How to identify catalysts: Catalysts are reactants in an elementary step that get produced in a
subsequent elementary step.
Catalysts never show up in the overall chemical reaction.