Chapter 25 Summary: 1. Experimental techniques: flow method, stopped-flow method, flash photolysis, quenching. 2.

The rates of reaction: rate laws, rate constants, reaction order. 3. Integrated rate laws: first and second order, half lives. 4. Reactions near equilibrium 5. Temperature dependence of reaction rates: The Arrhenius equation, transition states, activation energy 6. Accounting for the rate laws: Elementary reactions, molecularity, rate determining step, steady state approximation.

Chapter 26

The Kinetics of Complex Reactions

Chapter 26 Outline 26.1 The Rate Laws of Chain Reactions 26.2 Explosions 26.5 Features of Homogeneous Catalysis 26.6 Enzymes 26.11 Kinetics of Photophysical and Photochemical Processes 26.12 Complex Photochemical Processes Homework: 26.1, 26.2, , 26.5, 26.6, 26.7, 26.8, 26.10, 26.12 parts (a) only.

The Rate Laws of Chain Reactions Many gas-phase reactions and liquid phase polymerizations are chain reactions. In a chain reaction a reaction intermediate (or chain carrier) produced in one step generates an intermediate in a subsequent step and so on. In a radical chain reaction the chain carriers are radicals i.e. chemical species with unpaired electrons. Chain reactions can have simple or complicated rate laws.

The Rate Laws of Chain Reactions A Simple Example The pyrolysis of ethanal CH3CHO(g) CH4(g) + CO(g) (+ a little bit of C2H6 (g)) v = k[CH3CO]3/2
Mechanism: Initiation: Propagation: Propagation: Termination: CH3CHO CH3 + CHO v = ki[CH3CHO] CH3CHO + CH3 CH4 + CH3CO v = kp[CH3CHO][CH3] CH3CO CH3 + CO v = kp'[CH3CO] CH3 + CH3 CH3CH3 v = kt[CH3]2

We can test the proposed mechanism by showing that it gives the observed rate law. Lets do this using the steady state approximation.

The Rate Laws of Chain Reactions A Complicated Example The hydrogen-bromine reaction: H2(g) + Br2(g) 2 HBr(g)
d[ HBr ] k [ H 2 ] [ Br2 ] = [ Br2 ] + k ' [ HBr ] dt
3/ 2

Mechanism: Initiation: Propagation: Retardation: Termination: Br2 + M Br + Br + M v = ki[Br2][M] Br + H2 HBr + Hv = kp[Br][H2] H + Br2 HBr + Brv = kp' [H][Br2] H + HBr H2 + Br v = kr[H][HBr] Br + Br + M Br2 + M* v = kt[Br]2[M]

d[ HBr ] = k p [ Br ][ H 2 ] + k p ' [ H ][ Br2 ] k r [ H ][ HBr ] dt

See Example 26.1

The Rate Laws of Chain Reactions A Complicated Example

How did we select:
Br2 + M Br + Br + M as

initiation over, say: H2 + M H + H + M? Because of the lower bond energy. Similarly for termination. You have to play around with different "chemically reasonable" steps until the predicted v is in accord with experiment. There is not necessarily a unique solution!

Chain Reactions - Explosions

Solid-state explosions (e.g. the explosion of ammonium nitrate or TNT) are very rapid decomposition reactions that produce large amounts of gas-phase molecules. Some explosions are due to chain reactions. There are two types: Thermal Explosions and Chain-Branching Explosions.

Both types of explosion may be illustrated using the reaction of hydrogen and water. H2(g) + O2(g) 2H2O(g)

Chain Reactions - Explosions

H2(g) + O2(g) 2H2O(g)
Partial Mechanism: Initiation: Propagation: Branching: Termination: H2 H + H H2 + OH H2O + H O2 + H O + OH O + H2 H + OH H + wall H2 H + O2 + M HO2 + M* v = constant (vinit) v = kp[OH][H2] v = kb [H][O2] v = kb[O][H2] v = kt[H] v = kt[H][O2][M]

Chain Reactions - Explosions

EXPLOSION LIMITS for the H2/O2 system. At very low pressures chain carriers quickly diffuse to the container walls (H + wall H2) and there is no explosion. At moderate pressures diffusion is slowed and branching is explosively efficient. e.g. O2 + H O + OH and O + H2 H + OH At high pressures H atoms are lost via H + O2 + M HO2 + M*. At very high pressures a thermal explosion occurs.

Example 26.2: For the reaction of hydrogen and oxygen described above, show that an explosion occurs when the rate of chain branching exceeds that of chain termination.

Partial Mechanism: Initiation: Propagation: Branching: Termination: H2 H + H H2 + OH H2O + H O2 + H O + OH O + H2 H + OH H + wall H2 H + O2 + M HO2 + M* v = constant (vinit) v = kp[OH][H2] v = kb [H][O2] v = kb[O][H2] v = kt[H] v = kt[H][O2][M]

Introduction to Polymerization Kinetics

Briefly, we consider two types of polymerization process: Stepwise polymerization: Any two monomers in the reaction mixture can link together at any time. Growth of the polymer is not confined to chains already forming. Monomers removed early during the reaction. Molar mass of product grows with time. Condensation type processes are common second order rate law. Chain polmerization: Activated monomer attacks another monomer, resulting dimer attacks another monomer, resulting trimer attacks another monomer etc. Monomer used up as it adds to growing chain. Rate is proportional to square root of the initiator concentration.

Homogeneous Catalysis
Introduction: Pre-equilibria In chapter 25 we considered the progression of a reaction through the formation of an intermediate: A I P Now lets consider a slightly more complicated situation:

A+B
Fast, Dynamic Equlibrium!

I reaches equilibrium with A and B

ka

ka

kb

Homogeneous Catalysis
Introduction: Pre-equilibria

A+B

d[ P ] = k b [ I] dt d[ I ] = ka [ A ][ B] k a' [ I] k b [ I] dt
We may show that:

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

ka k b k = kb K = ' ka

ka

ka

kb

Homogeneous Catalysis Catalysts provide alternative routes through which reactions may proceed. In this way catalysts speed up reaction rates. A homogenous catalyst is a catalyst that exists in the same phase as the reaction mixture. A heterogeneous catalyst is in a different phase to the reaction mixture.

Homogeneous Catalysis The bromide-catalyzed decomposition of hydrogen peroxide: 2 H2O2 (aq) 2 H2O (l) + O2 (g) Proposed mechanism: H3O+ + H2O2 H3O2+ + H2O H3O2+ + Br- HOBr + H2O HOBr + H2O2 H3O+ + O2 + BrK= a H O + aH 2 O
3 2

aH 2 O 2 aH O +
3

aH O +
3 2

aH 2 O 2 aH O +
3

[H O ] [ H O ][ H O ]
3 + 2 + 2 2 3

v = k H 3O + Br 2

][ ]

Fast!

d[ O 2 ] = k eff [ H 2 O 2 ] H 3O + Br dt

][ ]

keff = kK

Homogeneous Catalysis Enzymes 1. For any given initial concentration of substrate, [S]0, the initial rate of product formation is proportional to the total concentration of enzyme, [E]0. 2. For any given [E]0 and low values of [S]0, the rate of product formation is proportional to [S]0. 3. For any given [E]0 and high values of [S]0, the rate of product formation becomes independent of [S]0 reaching a maximum velocity vmax.

Homogeneous Catalysis The Michaelis-Menten Mechanism Proposed mechanism: E + S ES ES P + E ka , ka kb

The Michaelis-Menten Equation

k b [ E ] 0 [ S] 0 v= ' ka + k b + [ S] 0 k a

Homogeneous Catalysis
The Michaelis-Menten Mechanism

k b [ E ] 0 [ S] 0 v= ' ka + k b k + [ S] 0 a

1.

For any given initial concentration of substrate, [S]0, the initial rate of product formation is proportional to the total concentration of enzyme, [E]0. For any given [E]0 and low values of [S]0, the rate of product formation is proportional to [S]0. kk

2.

v=

a b

k + kb
' a

[S] 0 [ E] 0

3.

For any given [E]0 and high values of [S]0, the rate of product formation becomes independent of [S]0 reaching a maximum velocity vmax. v = vmax = k b [ E ] 0

Homogeneous Catalysis
The Michaelis-Menten Mechanism

k b [ E ] 0 [ S] 0 v= ' ka + k b k + [ S] 0 a

The Michaelis Constant

ka' + k b KM = ka

v = vmax = k b [ E ] 0

vmax [ S] 0 v= ( K M + [S] 0 )

The PChem of Thanksgiving.

(turkey) vs (oven) Physical and Chemical Changes. Important to quench the reaction. The turkey is the rate determining step in the prep. Post-cooking: (turkey) vs (house) Physical changes. Decreasing G, thermal equilibrium etc. Cooling rates determined by Cp=(dq/dT)p. Water-containing foods vs surface area. Digestion proceeds via a Michaelis-Menton mechanism. (The kinetics can be enhanced when the mechanism is performed in the presence of football, family, and an ice cold beverage) .

Homogeneous Catalysis
The Michaelis-Menten Mechanism

vmax [ S] 0 v= ( K M + [S] 0 )

1 1 KM = + v vmax vmax

1 [ S] 0

Homogeneous Catalysis The catalytic efficiency of enzymes:

Proposed mechanism:

E + S ES
ES P + E

ka , ka kb

kcat is the number of catalytic cycles (turnovers) performed by the active site in a given interval divide by the duration of the interval.

kcat

vmax = kb = [ E] 0

The catalytic efficiency, , of an enzyme is given by:

kcat k a kb = = ' K M k a + kb

Homogeneous Catalysis
Example 26.3 Determining the catalytic efficiency of an enzyme. The enzyme carbonic anhydrase catalyses the hydration of CO2 in red blood cells to give bicarbonate ion: CO2 + H2O HCO3- + H+ The following data were obtained for the reaction at pH = 7.1, 273.5 K and an enzyme concentration of 2.3 nmol L-1; [CO2] / (mmol L-1) Rate / (mol L-1 s-1) 105 1.25 2.5 2.78 5.0 5.00 20.0 8.33 16.7

1 1 KM = + v vmax vmax
1/[CO2] / (mol L-1) 10-2 1/Rate / (mol L-1 s-1) 10-4 8.0 3.6

1 [ S] 0
4.0 2.0 2.0 1.2 0.5 0.6

Homogeneous Catalysis
Example 26.3 contd

y-intercept = 4.0 103 L-1 mol s-1 Slope = 40 s

vmax = 1/(y-intercept) KM = vmax slope

1 1 KM = + v vmax vmax 1 [ S] 0

kcat

vmax = [ E] 0

kcat = KM

Oscillating Reactions The concentrations of reactants, intermediates, and products of certain chemical reactions can vary periodically in either in space or time. If we make up a mixture of potassium bromate, malonic acid and a cerium (IV) salt in acidic solution and watch we see:

Oscillating Reactions This is an example of autocatalysis. The Belousov-Zhabotinski reaction: BrO3- + HBrO2 + H3O+ 2BrO2 + 2H2O 2BrO2 + 2Ce(III) + 2H3O+ 2HBrO2 + 2Ce(IV) + 2H2O

Oscillating Reactions The Belousov-Zhabotinski reaction mechanism. 18 elementary steps! 21 different chemical species involved! The main features of the reaction can be reproduced using a model called the oregonator. 1. 2. 3. 4. 5. A+YX+C X + Y 2C A + X 2X + 2Z 2X A + C B+ZY+P v = k1[A][Y] v = k2[X][Y] v = k3[A][X] v = k4[X]2 v = k5[B][Z]
A = BrO3B = Malonic Acid C = HOBr P = additional products X = HBrO2 Y = Br Z = Ce4+

Oscillating Reactions The Belousov-Zhabotinski reaction mechanism. Just as we have done before we: 1. Play spot the intermediate 2. Create Steady State equations 3. Set up a rate expression in which the concentrations of the intermediates have been substituted out. Then if we want to track the concentrations of the reactants or products with time we must integrate the rate law (differential equation). We may then make plots of concentrations of species and see how they change with time. (See movie).

Photochemistry

Examination of the Arrhenius Parameters show us that chemical reactions need an energy source to get going. Many reactions can be initiated by the absorption of electromagnetic radiation. The earth is constantly bathed in electromagnetic radiation.

Photochemistry The electromagnetic spectrum

Planks Equation E = hv h = Planks constant v = frequency = wavelength =c/v c = speed of light

Photochemistry What chemicals exist in the earths atmosphere and what chemical processes can occur? Normal Gases N2 O2 H2O CO2 Ar Bio. Processes CH3Cl CH4 H2S NaCl Soot Atmos. Chem. NO N2O N2O4 O3 H2SO4 ClO OH O Cl Anthropogenic CFCs +

Photochemistry The Chemistry of the Earths Atmosphere.

Photochemistry The Chapman Model: O2 + hv O + O 185 nm < < 220 nm Initiation

O3 + hv O2 + O

210 nm < < 300 nm

Propagation

Hr = -106.6 kJ mol-1 O + O2 + M O3 + M

O + O3 2O2 O + O + M O2 + M

Hr = -391.9 kJ mol-1

Termination

Photochemistry
The Chapman Model predicts a net formation of trace amounts ozone. However, it overestimates the amount of ozone in the stratosphere. Other species contribute to the termination step O + O3 2O2 according to: X + O3 XO + O2 XO + O X + O2 X can be H, OH, NO or Cl.

Photochemistry A cause of concern is the effect of anthropogenic pollutants on the ozone concentration. CFCs may be photolysed: CF2Cl2 + hv CF2Cl + Cl A reduction in stratospheric ozone will cause an increase in the amount of UV radiation reaching the earths surface.

Photochemistry
Global warming (for): Rise in CO2 and other greenhouse gases is human caused. Historical temp. record shows an increase of 0.4 0.8 oC over the last 100 years. Unusual warmth over last 1000 years. CO2 conc. is the most important indicator of climate change.

Climate models can reproduce warming trend but only when greenhouse gases are included. The theory has scientific consensus.

Photochemistry
Global Warming (Against): The Earth has been colder and warmer than it is today. The overwhelming majority of greenhouse gases are not produced by humans. Climate models can be made which predict global warming without considering human activity. Solar and Volcanic activity is much more important than global warming supporters would like to admit. Atmospheric chemistry is more complicated than the global warming supporters would like to admit (Undiscovered feedback mechanisms). A majority argument doesnt make it fact.

Photochemistry some background

What happens when UV light strikes a molecule?
Molecules, just like atoms, consist of nuclei surrounded by orbiting electrons.

To displace an electron from one molecular orbital to a different orbital requires energy.

It so happens that for many molecules the energy required for an electronic transition is of a similar magnitude to the energy of UV radiation (E2 E1 = 400 kJ mol-1)

E2 E1
(Check using Planks Equation).

hv

Photochemistry The electromagnetic spectrum

Planks Equation E = hv h = Planks constant v = frequency = wavelength =c/v c = speed of light

Photochemistry some background

Just like atomic orbitals, each molecular orbital may contain two electrons, one of which is spin-up and one is spin-down

The vast majority of molecules possess even numbers of electrons in which each electron is paired up. If each electron is paired up the molecule is referred to as being in a singlet state. When UV light strikes a singlet molecule it can promote an electron into a higher energy, unoccupied molecular orbital: E'2 E2 E1
Triplet state
(Forbidden transition)

High Energy Singlet state

Singlet state

E1

Singlet state

Photochemistry some background

Now lets construct a potential energy plot for a diatomic molecule, AB, for a given electronic configuration, say a singlet state:
At very short internuclear distances the atoms repel one another

Energy

At large internuclear distances the atoms cannot attract one another. They are separated.

Internuclear Distance r(A-B)

Within the potential energy plot can the molecule possess any energy we choose? No! Only discrete (quantized) energy levels are allowed.

Photochemistry some background

What happens when IR light strikes a molecule?
Molecules are constantly vibrating at discrete frequencies. The difference in energy between a molecule vibrating at one frequency compared to the same molecule vibrating at a higher frequency corresponds to the energy of electromagnetic radiation from the Infra-red region. When a molecule interacts with light of IR frequencies a vibrational excitation may be induced.

v2 v1

hv

What happens when microwave light strikes a molecule?

Molecules are constantly rotating at discrete frequencies. The difference in energy between a molecule rotating at one frequency compared to the same molecule rotating at a higher frequency corresponds to the energy of electromagnetic radiation from the microwave region.

J2 J1

hv

Photochemistry some background

Photochemistry The fates of electronically excited states: Scenario 1.

Absorption: AB (singlet, S) + UV radiation AB (higher energy singlet, S*)

Emission: AB (higher energy singlet, S*)

Fluorescence
AB (singlet, S) + UV radiation

Photochemistry The fates of electronically excited states: Scenario 2.

Absorption: AB (singlet, S) + UV radiation AB (higher energy singlet, S*) Emission: AB (higher energy singlet, S*)

AB (intermediate energy triplet, T*)

Phosphorescence
AB (singlet, S) + UV radiation

The Timescales of Photophysical Processes

It takes about 10-16 seconds for absorption of UV and visible radiation to take place. So, the upper limit for a rate constant for a first-order photochemical reaction is about 1016 s-1. Fluorescence is slower than absorption but still very fast and can be used to initiate very fast reactions:

* + hv
200 fs 0.25 ms

Biological cascade

Phosphorescence is typically much slower than fluorescence.

The Fluorescent Light

Sealed glass tube, electrodes at each end, filled with argon and a little mercury at very low pressure. Glass coated with a phosphor powder. When we turn on the AC power electrons flow from one electrode to the other electrode.

Hg + e- {Hg-}* {Hg-}* + M Hg + e- +M* + hv (UV light)

hv (UV) + Phosphor powder Phosphor powder* Phosphor powder* Phosphor powder + hv (visible)

Photochemistry The Primary Quantum Yield

In keeping with the timescales of photochemical events there are two processes classifications: Primary processes: Products formed directly from excited state (photoisomerization of retinal) Secondary processes: Products formed from intermediates which have been formed directly from the excited state of the reactant. For a primary process we may define the primary quantum yield as:

number of events rate of process v = = = number of photons absorbed intensity of light absorbed I abs

The Mechanism of Decay of Excited Singlet States. Consider the formation and decay of an excited singlet state Rate Law: vabs = Iabs vf = kf[S*] vic = kic[S*] visc = kisc[S*]

Absorption: Fluorescence: Internal Conversion: Intersystem Crossing:

S + hvi S* S* S + hvf S* S S* T*

We find that the quantum yield of fluorescence is:

kf f = kf + kic + kisc