Reaction Kinetics

Reaction Rates Rate Laws How we measure rates. How the rate depends on amounts of reactants. How to calc amount left or time to reach a given amount. How long it takes to react 50% of reactants. How rate constant changes with T.

Integrated Rate Laws

Half-life Arrhenius Equation

C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)

Average rate = [C4H9Cl] t

In this reaction, the ratio of C4H9Cl to C4H9OH is 1:1. Thus, the rate of disappearance of C4H9Cl is the same as the rate of appearance of C4H9OH. -[C4H9Cl] [C4H9OH] Rate = = t t

Zero Order

Rate Law
Integrated Rate Law Graph

k
[A] = -kt + [A]0 [A] versus t

Rate Constant Life

Slope = - k t =[A]0/2k

First Order

Rate Law
Integrated Rate Law Graph

k[A]
ln[A] = -kt + ln[A]0 ln[A] versus t

Rate Constant Life

Slope = - k t =0.693/k

Second Order

Rate Law
Integrated Rate Law Graph

k[A]2

1 1 kt [A] [A] 0
1/[A] versus t

Rate Constant Life

Slope = k t =1/k[A]0

Half life for zero, first and second order reaction

First order

Second order

ORDER RATE LAW RATE CONSTANT UNIT, k

ZERO ORDER Rate = k[A]0 MS-1 Rate =k[2A]0 Rate = k

1ST ORDER Rate = k[A]1 S-1 Rate = k[2A]1 Rate = 2k[A]1

(Rxn rate increace 2x)

2ND ORDER Rate = k[A]2 M-1S-1 Rate = k[2A]2 Rate = 4k[A]2

(Rxn rate increace 4x)

DOUBLE [A] INTEGRATED RATE LAW GRAPH RATE VS [A]

(No change in rxn rate)

[A]0 [A] = kt
Rate Zero Order

ln[A]0 ln[A] = kt @ ln [A]0 = kt [A]

Rate

1 - 1 = kt [A] [A]0
Rate

[A]

[A]

[A]

STRAIGHT LINE GRAPH

[A] vs t (-ve slope)

[A]0 [A] = -kt+[A]0 t [A]o[A]

ln[A] vs t (-slope)
ln[A]
ln[A]o ln[A] = -kt+ ln[A]0 t

1 vs t (+ve slope) [A]

1 [A] 1 [A]o +ve slope t 1 = kt + - 1 [A] [A]0

[A]0 [A] = kt +ve slope t

ln[A]o/[A] ln[A]0 ln[A] = kt +ve slope t

HALF LIFE, t1/2 GRAPH

t1/2= [A]0 2k

t1/2 = ln 2 k

t1/2 =

1 k [A]0

t1= t2

t1= t2 = t3 = t4

t1= 2 x t2

Collision Theory
Collisions that yield product a significance of molecular orientation during collision.
Not all molecular collisions result in a reaction.

Orientation of reactants must allow formation of new bonds. Collisions must have enough energy to produce the reaction (must equal or exceed the activation energy, Ea).

Effect of concentration and temperature on rates of reaction

Number of molecular collisions is proportional to the concentration

The fraction of collisions that are sufficiently energetic to result in reaction increases rapidly with increasing temperature.

Plot of ln k vs. (1/T) from the data for the gasphase decomposition of hydrogen iodide. Using the Arrhenius equation to determine activation energy of a reaction