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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
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]
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!
Both types of explosion may be illustrated using the reaction of hydrogen and water. H2(g) + O2(g) 2H2O(g)
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]
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!
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.
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
ka' + k b KM = ka
v = vmax = k b [ E ] 0
vmax [ S] 0 v= ( K M + [S] 0 )
Homogeneous Catalysis
The Michaelis-Menten Mechanism
vmax [ S] 0 v= ( K M + [S] 0 )
1 1 KM = + v vmax vmax
1 [ S] 0
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
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
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 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 +
O3 + hv O2 + O
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.
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
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)
Singlet state
E1
Singlet state
Energy
At large internuclear distances the atoms cannot attract one another. They are separated.
v2 v1
hv
J2 J1
hv
Fluorescence
AB (singlet, S) + UV radiation
Phosphorescence
AB (singlet, S) + UV radiation
* + hv
200 fs 0.25 ms
Biological cascade
hv (UV) + Phosphor powder Phosphor powder* Phosphor powder* Phosphor powder + hv (visible)
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*]
S + hvi S* S* S + hvf S* S S* T*
kf f = kf + kic + kisc