5.

60 Spring 2005

Lecture Summary #25

page1

Kinetics: Reaction Rates, Orders, Half Lives

Up to this point, we have dealt with chemical systems at equilibrium, which means that their properties do not change in time. Most real systems are not at equilibrium, and undergo chemical change as they seek to approach the equilibrium state. Chemical kinetics deals with changes in chemical properties with time. Consider a chemical reaction having the overall stoichiometry aA + bB cC + dD The Rate of Reaction is defined as (1)

d [ A] d [ B] 1 d [C] 1 d [ D] Rate = 1 = 1 = = a dt b dt c dt d dt
Experimentally we find that the Rate = k Ci i
i=1 N

(2) (3)

where

k = rate coefficient Ci = Concentration of Reactant i or [i] i = Order of reaction with respect to reactant i p=

ii = overall order of reaction (1)

k has the units [concentration]-(p-1)[time]-1

5.60 Spring 2005

Lecture Summary #25

page2

I)

Zero Order Reactions (rare)

The rate of the reaction is independent of the concentration of the reacting substance (can you think of an example?) A products

d[A] =k dt

{k is in [moles/(liter sec)]}

[A]t = [A]o - kt

The reaction half-time t1/2 is the time required for the concentration to decrease to one-half of its initial value. [A] t1/2 = [A]o/(2k) [A]o

[A]o/2

t1/2

5.60 Spring 2005

Lecture Summary #25

page3

II) First Order Reactions The rate of the reaction is proportional to the first power of the concentration of the reacting substance (order = 1) A products

d[A] = k[A] dt

{k is in [1/sec]} l n[A]t = -kt + ln[A]o

[A]t = [A]o e-kt ln[A]

ln[A]o

Slope = -k

t1/2 = (ln 2) / k = 0.693/k

k = (0.693)/(t1/2)

Examples: decay of radioactive nuclei fluorescence decay of electronically excited molecules isomerization of cyclobutene to butadiene milk turns sour when left out overnight

5.60 Spring 2005

Lecture Summary #25

page4

III) Second Order Reactions The rate of the reaction is proportional to the second power of the concentration of one reactant or to the first power of the concentrations of two reactants (order = 2) a) Second order in one component

A products

d[A] = k[A]2 dt

1 1 = + kt [A] [A]o
1/[A]

Slope = k 1/[A]o t t1/2 = 1/(k[A]o)

5.60 Spring 2005

Lecture Summary #25

page5

b) First order in each of two components

A +B products

d[A] = k[A][B] dt

kt =

[A][B]o 1 ln [A]o [B]o [A]o [B]

[A]o [B]o

Special cases:

1 1 = + kt [A] [A]o
i) [A]o = [B]o

[A] = [B]
This is like 2nd order in one component

ii)

[B]o <<[A]o [B] = [B]oe-kt where k = [A]ok

This is called a pseudo 1st order reaction (discuss later)

5.60 Spring 2005

Lecture Summary #25

page6

IV) Third Order Reactions Several possible cases. Could be: (a) three identical chemical molecules interact simultaneously (unusual) (b) two molecules of one species interact with one of another Example: recombination of homonuclear molecules such as iodine

I+I+M

I2 + M

M is a non-reactive gas molecule called a "Reaction Chaperone" 1 It could also be the wall of the reaction vessel. Mechanism:

I + I interact to form a "hot" I2* molecule I2* falls apart unless stabilized by M Excess energy in M released to gas

Recombination rate = -d[I]/dt = k [I]2[M] Concentration of M doesn't change, so reaction follows case (a) 2nd order kinetics, -d[I]/dt = k' [I]2 but k' is proportional to the concentration (pressure) of M ! (c) three different chemical species interact with each other Very important example: formation of ozone in the stratospheric ozone layer, O + O2 + M O3 + M (M = air)

Chaperone: an older person who accompanies young men and women to ensure their proper behavior