Chemical Kinetics

Rates of Reaction

 Kinetic = movement or change Chemical kinetics is the area of chemistry concerned with the speed, or rates, at which a chemical reaction occurs Reaction rate is the change in the concentration of a reactant or a product with time (M/s) Why reactions have such vastly different rates?

Where:

[ ] Rate t

Reactants A

Products B [] Rate t

[A] and [B] are the changes in concentrations (molarities) over a time period t . [A] is a negative quantity

The rate of reaction is a positive quantity, so a minus sign is needed to in the rate expression to make the rate positive

Products

Reactants

In an aqueous solutions, molecular bromine reacts with formic acid as follows: Br2(aq) + HCOOH(aq) 2Br2-(aq) + 2H+(aq) + CO2 (g)

Example

Measuring the change (decrease ) in [Br2] at some initial time and then at some final time enable s us to determine the average rate of the reaction during that interval. {Data in the Table provided} Rates of the reaction between Br2 and Formic acid
Time (s) [Br2] (M) Rate (M/s) 3.52 x 10-5 k = (rate/[Br2] )(s-1)

00.0
50.0 100.0 150.0 200.0 250.0

0.0120
0.0101 0.00846 0.00710 0.00595 0.00500 1.75 x 10-5

[r2 ] Averagerate t [ Br2 ] final [r2 ]initial Averagerate t final tinitial

Using the data provided in the Table let us calculate the over the 1st 50s time interval.

(0.0101 0.0120) M Average rate 3.80 105 M / s 50.0s If we choose the 1st 100 s as time interval the average rate would then be given by: (0.00846 0.0120) M Average rate 3.54 105 M / s 100.0s

instantaneous rate ()
We can obtain the rate for specific instant in time, which gives the instantaneous rate of the reaction at that time. The instantaneous rate at 100 s after the start of the reaction is given by the slope of the tangent to the curve at that instant. The instantaneous rate at any other time can be determined in a similar manner. Note that the instantaneous rate determined in this way will always have the same value for the same concentrations of reactants, as long as the temperature is kept constant. We do not need to be concerned with what time interval to use. Unless otherwise stated, we will refer to the instantaneous rate merely as the rate.

Reaction Rates
average rate the rate over a specific time interval instantaneous rate () the rate for an infinitely small interval (instantaneous = Physics existing or measured at a particular instant)

How to distinguish between average rate and instantaneous rate?

The distance between Makkah and Elmadinah is 512 miles. It takes 11.5 hours to go from one city to another at the average speed of 512 miles/11.4 hours or 44.9 mph. If the car is traveling at 55.3 mph after 3 hours departure, then the instantaneous speed of the car is 55.3 mph Speed of the car may increase or decrease, but the instantaneous rate of the reaction must always decrease with time.

 Going back to the previous Table conc. of Br2 is doubled, the rate of reaction also doubled. Thus the rate is directly proportional to the Br2 conc.

Integrated Rate Laws

A --- B A ---> products rate = - (D[A]/Dt) = k[A]m average rate

rate = - (d[A]/dt) = k[A]m

instantaneous rate

Average vs. Instantaneous Rate

Concept Test
For the reaction: The dependence of the concentration of H2 on time is shown. Is the reaction rate faster at point A or point B?
A, B, both rates are the same

Rate Determining Step

slowest step in a multistep mechanism the step which determines the overall rate of the reaction

Rate Law
an expression which relates the rate to the concentrations and a specific rate constant

Rate Law
Reaction rate = k [A]m [B]n
where m = order with regard to A

n = order with regard to B overall order = m + n

Concept Test
The empirical rate law for the reaction
is Rate = k[NO2][F2].

Which of the following mechanisms is consistent with this rate law?

A) NO2 (g) + F2 (g) <=> NO2F(g) + F(g) fast NO2(g) + F(g) --->NO2F(g) slow

B) NO2 (g) + F2(g) <==> NO2F(g) + F(g) slow NO2(g) + F(g) ---> NO2F(g) fast

C) F2(g) <==> F(g) + F(g) slow

2NO2(g) + 2F(g) ---> 2NO2F(g) fast

A, B, C

Order of Reaction
exponent of the concentration for a reactant that implies the number of molecules of that species involved in the rate determining step first order, exponent equals one second order, exponent equals two

Order of Reaction

Graphical Determination of Order of Reaction

This plot of ln[H2O2] vs. time produces a straight line, suggesting that the reaction is first order.

A Nanoscale View: Elementary Reactions

unimolecular - rearrangement of a molecule bimolecular - reaction involving the collision of two particles termolecular - reaction involving the collision of three particles

Unimolecular Reaction

Bimolecular Reaction

Collision Rate Model

Three conditions must be met at the nanoscale level if a reaction is to occur: the molecules must collide; they must be positioned so that the reacting groups are together in a transition state between reactants and products; and the collision must have enough energy to form the transition state and convert it into products.

Transition State: Activated Complex or Reaction Intermediates

an unstable arrangement of atoms that has the highest energy reached during the rearrangement of the reactant atoms to give products of a reaction

Activation Energy
the minimum energy required to start a reaction

Temperature & Reaction Rate

Catalyst
susbstance which speeds up the rate of a reaction while not being consumed Homogeneous Catalysis - a catalyst which is in the same phase as the reactants Heterogeneous Catalysis - a catalyst which is in the different phase as the reactants catalytic converter
solid catalyst working on gaseous materials

Concept Test
Which curve illustrates the effect of a catalyst on the reaction diagram, given that it speeds up the rate of a reaction?
A, B, C, D

Reaction Mechanism
A set of elementary reactions which represent the overall reaction

Catalytic Converter
H2O(g) + HCs -------> CO(g) + H2(g)
catalyst catalyst
(unbalanced)

2 H2(g) + 2 NO(g) ------> N2(g) + 2 H2O(g)

catalyst

HCs + O2(g) --------> CO2(g) + H2O(g) (unbalanced)

catalyst

CO(g) + O2(g) --------> CO2(g)

catalyst = Pt-NiO HCs = unburned hydrocarbons

(unbalanced)

Chain Mechanisms
chain initiating step - the step of a mechanism which starts the chain chain propagating step(s) - the step or steps which keeps the chain going chain terminating step(s) - the step or steps which break the chain

Chain Mechanisms
combustion of gasoline in an internal combustion engine chain initiating step - additives which generate free radicals, particles with unpaired electrons chain propagating step(s) - steps which generate new free radicals chain terminating step(s) - steps which do not generate new free radicals

ENZYMES
any one of many specialized organic substances, composed of polymers of amino acids, that act as catalysts to regulate the speed of the many chemical reactions involved in the metabolism of living organisms.