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ChemicalKinetics
Study of the speed of a reaction

ChapterFourteen
ChemicalKinetics Ch i l Ki ti

P Physical state of Reactants y P Concentration of Reactants P Temperature P Any catalyst

Chemistry: The Central Science, 12th ed. CH 112 - General Chemistry II Passaic County Community College Dr. Fred Safarowic

ReactionRates
Speed of a reaction

RateoverTime
C4H9Cl + H2O C4H9OH + HCl

B
Rate decreases over time since the reactant concentration decreases

Average rate =

change in moles B (moles B) (moles A) = = change in time t t

Average rate = -

[C4 H 9 Cl] t

= -

[C4 H 9Cl]final time - [C4 H 9Cl]initial time (final time) - (initial time)

InstantaneousRate

RatesandStoichiometry
aA + bB cC + dD

Rate = -

1 [A] 1 [ B] 1 [C] 1 [D] = = = a t b t c t d t

C4H9OH + HCl
[C4 H 9 Cl] [C4 H 9 OH] = t t
H2 + I2

Rate at a particular time

C4H9Cl + H2O
Rate = 2HI

Slope of the tangent of a line at a single point in time

Rate = -

[H 2 ] [I 2 ] 1 [ HI] = = t t 2 t

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RateLaw
Rates change as product is produced and reactant is consumed. Not linear relationship.
NH4+ + NO2N2 + 2H2O

ReactionOrder
General Rate Law

Rate = k[A]m [B]n

m & n are reactant orders for each reactant m + n = reaction order ti d m + n are found by experimentation. They have no relation to stoichiometry Can be positive or negative, usually whole numbers. Most common values are 0, 1 or 2

Rate Law

Rate = k[NH + ]m [NO-2 ]n 4

k is the rate constant. Constant no matter what the concentrations and rate are. More useful than the actual rate.

SampleRateLaw
2N2O5
CHCl3 + Cl2

Unitsfork
Varies depending on the reaction order
1 First Order unit is s-1

4NO2 + O2

Rate = k[N 2 O5 ]
CCl4 + HCl

Rate = k[CHCl 3 ][Cl 2 ]1/2

H2 + I2

2HI
Second Order unit is M-1 s -1

Rate = k[H 2 ][I 2 ]

MethodofInitialRates
First Order

FirstOrderReactions
Predict conc. @ any time
A Products
Rate = [A] = k[A] t

Used to get m & n experimentally

Rearranging gives:

ln [A]t = - kt + ln[A]o
y = mx + b

Slope is k

rate 2 concentration 2 m ) = ( rate 1 concentration 1

m is order, can also be n

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SecondOrder
[ A] Rate = = k [ A]2 t
NO2 (g)

Halflife
t1/2 = time it takes for half of a reactant to be used up For first order ONLY

1 1 = kt + [ A]t [ A]o
NO (g) + 1/2O2 (g)

t 1/2 =

0.693 k

Any other order is meaningless

Temperature&Rate
Rate increases with temperature 1. Reaction occurs because reactants collide. Higher temperature, increases speed of molecule so more f l l collisions. Faster Rate. 2. Arrhenius Model
Based on activation energy, Ea

ActivationEnergy
Molecules must have energy to react Minimum amount is Ea Can be viewed as climbing a hill with products on the other side of the hill Top of the hill is the energy maximum and is called the transition state. Higher temp means that more molecules have energy to get over hill Molecules must also be in correct orientation (like a key into a lock.

TransitionState

MolecularFraction

Activated Complex
Lower Ea is faster reaction

f = e Ea / RT

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ArrheniusEquation
Rate depends on: # of molecules w/Ea, # of collisions, correctly oriented molecules Combine as Arrhenius Equation Rearranging for Graph
ln k = Ea + ln A RT

ReactionMechanisms
Need to know how reaction occurs Pathway is called the reaction mechanism Describes order bonds are broken/formedand changes in position of any atoms Temperature dependant

k = Ae -Ea/ Rt

Or if you have data at two temps, get k

k Ea 1 1 ln 1 = ( ) k2 R T2 T1

ElementaryReactions
Single step processes are called elementary steps Molecularity Unimolecular: one molecule

MultistepMechanisms
Sequence of elementary steps that shows the path from reactant to product. Elementary steps must add to give overall reaction; just lik j like Hesss law type problems. l bl Material that is formed in an elementary step & then used up in a following step and doesnt appear in overall reaction is an intermediate.

Bimolecular: two molecule collision Termolecular: Rarer, three molecules

ElementaryRateLaws
Cant predict the number of steps in a mechanism from the chemical equation. Still must be determined experimentally

MultistepMechanisms
Rate of a reaction is determined by the rate of the slowest elementary step. This is called the rate determining step (RDS). Elementary steps that occur after the rate determining step do not affect the rate. Mechanism must be supported by an experimentally determined rate law. If the experiment indicates a different concentation dependance (ie rate law), then mechanism is wrong.

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InitialSlowStep

InitialFastStep

You must be able to perform the transformations and calculations on pages 601 and 602 as well as sample exercise 14.14

You must be able to perform the transformations and calculations on pages 602 to 604 as well as sample exercise 14.15

HomogeneousCatalysts
Everything is in the same phase

HeterogeneousCatalysts
Catalyst is in a different phase

Enzymes
Biological catalyst Lock and key model