06523 Kinetics.

Lecture 7

Kinetics and Mechanism IV. Chain reactions

Rate laws revisited Unimolecular reactions Chain reactions Polymerization Explosions
Dr John J. Birtill

pptpres7 1

Rate laws revisited (lectures 1 and 5)

Consider two similar looking bromination reactions, both in aqueous solution (1) C6H5NH2 + Br2 BrC6H4NH2 + H+ + Br(2) CH2(CN)2 + Br2 BrCH(CN)2 + H+ + Brr1 = d[Br2 ] = k1 [C6 H 5 NH 2 ][Br2 ] dt d[Br2 ] k 2 [CH 2 (CN) 2 ][Br2 ] = dt k 3[H + ] + k 4 [Br2 ] +

r2 = -

Similar reaction stoichiometries but very different rate laws. Reaction 1 has a simple rate expression that is similar to the reaction stoichiometry. The mechanism really does have single bimolecular reaction step Bimolecular electrophilic substitution Reaction 2 has a complex rate expression (lecture 5). The initial forward step is unimolecular dissociation to a carbanion but the overall rate is the defined by the overall mechanism. When [Br2] is >> k3[H+] then rate expression simplifies to 1st order.
pptpres7 2

Rate laws revisited (lectures 1 and 5)

The reaction stoichiometry defines the overall proportions of reactants and products. is equivalent to the sum of all the elementary steps in the reaction mechanism does not define the reaction mechanism unless there is only one elementary step. The rate law and reaction order for the overall reaction is made up of the combined rate laws for all the elementary reaction steps In other words it derives from the fundamental reaction mechanism For this reason the rate law for the overall reaction is empirical (determined by experiment) and cannot be predicted automatically from the reaction stoichiometry. The rate law of an elementary reaction step can be deduced directly from its stoichiometry. k1 Rate 1 forward = k1[CH2(CN)2] unimolecular Step 1: CH2(CN)2 CH(CN)2- + H+ Rate 1 reverse = k-1[CH(CN)2 ][H+] bimolecular k -1 Step 2: CH(CN)2- + Br2
k2

CHBr(CN)2 + Br- Rate 2 = k2[CH(CN)2 ][Br2] bimolecular Overall rate = complex (previous slide)

Overall: CH2(CN)2 + Br2 BrCH(CN)2 + H+ + Brpptpres7 3

Unimolecular reactions
Some reactions are 1st order because an initial fast step is unimolecular but the overall reaction involves more than one molecule SN2 and SE1 reactions involve initial dissociation to carbocations and carbanions. Some gas phase reactions are 1st order and but again they are not truly unimolecular overall The overall mechanism is multi-step (e.g., decomposition of N2O5) or catalysed by the surface of the vessel. Example: 2N2O5 2N2O4 + O2 multi-step mechanism

Some gas phase reactions are 1st order and can be described as unimolecular overall but even here the situation is a little more complex and the rate laws are pressure-dependent.
Example: isomerization of cyclopropane (strained molecule)

H2C

CH2 CH2

CH3CH=CH2

Rate = k[cyclo-C3H6]

pptpres7 4

Unimolecular reactions: Lindemann (-Christiansen) mechanism

Consider the unimolecular reaction A B
Step (1) A reactant molecule A gains energy by collision with any other molecule M. Reverse step (1) The excited molecule A* can lose energy by collision with another molecule

rate1 = k1[A][M] rate-1 = k -1[A*][M] rate 2 = k 2 [A*]

d[A*] Step (2) A* decomposes by unimolecular decay =0 k1 dt (1) A + M A* + M k1[A][M] - k -1[A*][M] - k 2 [A*] = 0 k
-1

B Can apply the quasi-equilibrium approximation to step (1) but more general solution is to apply the steady state approximation to [A*] and rearrange to solve for [A*] (Hinshelwood).
At high pressure k1[M] >> k2 and the order rate law applies (step 1 at quasi-equilibrium).
pptpres7 5

(2)

A*

k2

k1[A][M] Hence [A*] = (k -1[M] + k 2 ) k1k 2 [A][ M] rate3 = (k -1[M] + k 2 ) rate3 = k' [A] where k' = k1k 2 /k -1

1st

Unimolecular reactions: Lindemann mechanism contd

The overall rate law can be re-expressed in terms of a rate constant k that varies with pressure. The Lindemann theory predicts that k is constant at high pressure but decreases at low pressure. This is observed in practice. See plot for azomethane. k = k1k2/k-1

rate3 =

k1k 2 [A][ M] = k' [A ] (k -1[M] + k 2 ) k1k 2 [M] (k -1[M] + k 2 )

where k' =

The Lindemann theory gives a qualitative fit to experimental data but estimates of k1 by simple collision theory did not agree with experiment plots of 1/k vs 1/[M] not linear.
More sophisticated theories (Hinshelwood, RRK etc) consider the distribution of vibrational energy within the molecule.
pptpres7 6

Decomposition of azomethane at 603K CH3N2CH3 C2H6 + N2

-2.4 -2.5 -2.6

log (k)
Ref: Reaction Kinetics M.J. Pilling & P.W. Seakins
-5 -4 -3 -2 -1 0

log( k/ s-1)

-2.7 -2.8 -2.9 -3.0 -3.1 -3.2 -3.3 log([A]/mol dm-3)

Chain reactions
Many gas-phase and liquid-phase reactions are chain reactions including many of industrial importance such as polymerizations. The chain carrier is commonly a free radical intermediate I but can also be an ion. Usually designate radical intermediate with in order to distinguish from nonradical species. The initiation step is slow but a reactive intermediate I (the chain carrier) forms the the product and another reactive intermediate and so the reaction keeps on going (propagation) over many cycles (the chain length) until the chain carrier is destroyed somehow (termination).

A I
I + A C + I I + I D I + B 2 I
pptpres7 7

initiation
propagation termination

(slow)
(fast) (slow)

A branching step increases the number of chain carriers.

Chain reactions continued

An inhibition step removes chain carriers by reaction with the vessel walls or with foreign radicals. Nitric oxide NO has an unpaired electron. It is a weak chain initiator but a very efficient chain terninator. CH3 + NO CH3NO H2O + HCN If a reaction is inhibited by NO then this is evidence for a radical chain mechanism The initiation step may be caused by collisions of energetic molecules (thermolysis reactions) or absorption of a photon (photolysis reactions). Br2 + h 2Br In polymerization processes a small amount of an unstable molecule such as benzoyl peroxide may be used as a radical initiator to start off a chain reaction. Note that in nuclear fission the chain carrier is a neutron.

pptpres7 8

The hydrogen bromine reaction

Overall reaction H2 + Br2 2HBr Complex rate law suggests a complex mechanism. Generally accepted mechanism (1) Br2 2Br (2) Br + H2 HBr + H (3) H + Br2 HBr + Br (-2) HBr + H Br + H2 Initiation Propagation Propagation Retardation

d[HBr] k' [H 2 ][Br2 ]3/2 = dt [Br2 ] + k' ' [HBr]

(-1) 2Br Br2

Termination

Note that there are 2 radical intermediates H and Br (the chain carriers). Apply the steady state hypothesis to both of them.

pptpres7 9

The hydrogen bromine reaction contd.

Eq (i) Overall rate Eq (ii) and Eq (iii): apply steady state approxm to [H] and [Br]. Eq (iv): add Eq (ii) and Eq (iii).
d[HBr] = k 2 [Br][H 2 ] + k 3 [H][Br2 ] - k -2 [H][HBr] dt d[H] (ii) = k 2 [Br][H 2 ] - k 3 [H][Br2 ] - k -2 [H][HBr] = 0 dt d[Br] (iii) = k1[Br2 ] - k 2 [Br][H 2 ] + k 3[H][Br2 ] + k -2 [H][HBr] - k -1[Br]2 = 0 dt k (iv) k1[Br2 ] - k -1[Br]2 = 0 (v) [Br] = ( 1 )1 / 2 [Br2 ]1/2 k -1 (i) k 2 (k1/k -1 )1 / 2 [H 2 ][Br2 ]1/2 (vi) [H] = k 3 [Br2 ] + k -2 [HBr] d[HBr] k 2 (k1/k-1 )1/ 2 [H 2 ][Br2 ]1/2 1/ 2 1/2 (vii) = k 2 (k1 / k -1 ) [Br2 ] [H 2 ] + k 3 [Br2 ] dt k 3[Br2 ] + k -2 [HBr] k 2 (k1/k-1 )1 / 2 [H 2 ][Br2 ]1/2 - k -2 [HBr] k 3 [Br2 ] + k -2 [HBr] = {k 2 (k1 / k -1 )1 / 2 k 3 [Br2 ]3/2 [H 2 ] + k 2 (k1 / k -1 )1 / 2 k -2 [Br2 ]1/2 [H 2 ][HBr] = + k 2 k 3 (k1/k -1 )1 / 2 [H 2 ][Br2 ]3/2 - k -2 k 2 (k1/k-1 )1 / 2 [H 2 ][Br2 ]1/2 [HBr]+ } + + k 3[Br2 ] + k -2 [HBr] = k' [H 2 ][Br2 ]3/2 [Br2 ] + k' ' [HBr]

Hence Eq (v) for [Br].

Eq (vi): substitute for [Br] in Eq (ii) and solve for [H].

Eq (vii): substitute for [H] and [Br] in Eq (i), cancel out terms and rearrange.
pptpres7 10

2k 2 (k1 / k -1 )1 / 2 k 3[Br2 ]3/2 [H 2 ] = k 3[Br2 ] + k -2 [HBr]

Free radical polymerization reactions

Radical adds to an alkene to form a larger radical which then adds to another alkene and so on.
R1 H R + C=C H H R1 H R- C- C H H R1 H R1 H R- C- C- C- C H H H H

(- C- C- )n
H H

R1 H

Polyethylene R1 = H

Polyvinylchloride R1 = Cl

Polystyrene

R 1 = C6 H 5

The base alkene is termed the monomer. Growing radicals are oligomers
Reaction proceeds via initiation step then propagation steps until any two radicals react together in the termination reaction O O O Use of radical initiator such as benzoyl peroxide:
C6H5COOCC6H5 2C6H5C- O

Multiple propagation steps very similar and so k is approximately constant with size Average polymer chain length depends on average number of propagation steps before termination.
pptpres7 11

Polymerization reactions are of world scale industrial importance

Gas-phase combustion: explosions

Thermal explosion: energy released in thermal reaction causes temperature to rise and reaction rate to increase.and so temperature rises faster ... and so the rate accelerates catastrophically. Chain-branching explosion: thermal explosion in which chain-branching occurs. Number of chain carriers grows exponentially as the reaction proceeds. Hydrogen-oxygen reaction has both characteristics and is explosive over wide range of conditions 2 H2 (g) + O2 (g) 2 H2O (g) Simple stoichiometry but complex mechanism. Chain carriers include H, O, OH, and O2H Some steps include: Initiation Propagation: H2 + O2 O2H + H O2 + H O + OH O + H2 OH + H H2 + OH H + H2O Consider reaction at 460 600 C Reaction occurs smoothly at low pressure because sufficient number of chain carriers can reach container walls and recombine before reacting At higher pressure (above lower explosion limit) explosion will occur. At still higher pressure reaction (above higher explosion limit ) occurs smoothly because rate of radical recombination reactions (termination) becomes significant.
pptpres7 12

branching branching