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Chemical Kinetics

2018/2019.

Prof. Mike Lyons

Room 3.2 Chemistry Building

School of Chemistry

Trinity College Dublin.

Email : melyons@tcd.ie

Course Summary.

• Contact short but sweet. 5 Lectures in total (4 this week (wk3),

1 next week (wk4)), 3 tutorials next week (wk 4).

• We revise quantitative aspects of JF kinetics and discuss some

new more advanced topics and introduce the mathematical

theory of chemical kinetics.

• Topics include:

– Lecture 1-3. Quantitative chemical kinetics, integration of rate

equations, zero, first, second order cases, rate constant . Graphical

analysis of rate data for rate constant and half life determination

for each case . Dependence of rate on temperature. Arrhenius

equation and activation energy. Kinetics of complex multistep

reactions. Parallel and consecutive reactions. Concept of rate

determining step and reaction intermediate.

– Lecture 4-5. Enzyme kinetics (Michaelis-Menten case) and surface

reactions involving adsorbed reactants (Langmuir adsorption

isotherm).

• If we have time we will cover the following topic:

– Theory of chemical reaction rates : bimolecular reactions. Simple

Collision Theory & Activated Complex Theory.

Recommended reading.

• Burrows et al Chemistry3, 1st edition, OUP (2009) Chapter 8. pp.339-403. 2nd edition,

OUP(2013) Chapter 9, pp.378-443, 3rd edition, Ch9, pp.382-443.

• P.W. Atkins J. de Paula.The elements of physical chemistry. 5th Edition.

OUP (2009). Chapter 10, pp.219-243; Chapter 11, pp.244-269. 6th Edition OUP (2013),

Chapter 10, pp.235-260; Chapter 11, pp.261-286, 7th edition, Focus 6 pp.249-314.

• P.W. Atkins and J. de Paula. Physical Chemistry for the Life Sciences. 2nd edition. OUP

(2011). Part II entitled The kinetics of life processes (Chapters 6,7,8, pp.217-310) is

especially good.

• Both of these books by well established authors are clearly written with an excellent style and both

provide an excellent basic treatment of reaction kinetics with emphasis on biological examples. These

books are set at just the right level for the course and you should make every effort to read the

recommended chapters in detail. Also the problem sheets will be based on problems at the end of

these chapters!

Chapter 21, pp.782-830 ; Chapter 22, pp.831-875;

Chapter 23, pp.876-908.

P. Atkins, J de Paula, J Keeler, OUP 2018, Atkins’ Physical Chemistry 11th Edition, Focus 17

Chemical Kinetics pp.721-777. Focus 18 Reaction Dynamics, pp.779-821. especially Topic 18A

and 18B.

• A more advanced and complete account of the course material. Much of chapter 22 is JS material.

• Modern textbook providing a complete account of modern

chemical reaction kinetics. Good on experimental methods and theory.

• Another modern kinetics textbook which does as it states in the title, i.e. provide a readable

introduction to the subject ! Well worth browsing through.

SF Chemical

Kinetics.

Lecture 1-3.

Quantitative Reaction

Kinetics.

Reaction Rate: The Central Focus of

Chemical Kinetics

The wide range of reaction rates.

Reaction rates vary from very fast to very slow : 1 femtosecond (fs)

from femtoseconds to centuries ! = 10-15 s = 1/1015 s !

Picosecond (10-12s)

techniques

Femtosecond

(10-15 s)techniques

5th edition, Chapter 10, section 10.2, pp.221-222

Mixing of reactants must occur more rapidly than reaction occurs.

Start of reaction pinpointed accurately.

Method of analysis must be much faster than reaction itself.

Chemical reaction kinetics.

reactants products

• Chemical reactions involve the

forming and breaking of

chemical bonds.

H ( g)+ I2( g)→ 2HI( g)

2

• Reactant molecules (H2, I2)

approach one another and

collide and interact with • Thermodynamics tells us all

appropriate energy and about the energetic feasibility

orientation. Bonds are of a reaction : we measure the

stretched, broken and formed Gibbs energy ΔG for the chemical

and finally product molecules Reaction.

(HI) move away from one

another. • Thermodynamics does not tell us

• How can we describe the rate how quickly the reaction will

at which such a chemical proceed : it does not provide

transformation takes place? kinetic information.

Basic ideas in reaction kinetics.

• Chemical reaction kinetics deals with the rate of velocity of chemical

reactions.

• We wish to quantify

– The velocity at which reactants are transformed to products

– The detailed molecular pathway by which a reaction proceeds (the reaction

mechanism).

underlying basis of chemical reactions can be understood at a

microscopic molecular level.

thermal (heat) energy) must be introduced into the system so that

chemical transformation can occur. Hence chemical reactions occur

more rapidly when the temperature of the system is increased.

reactants can be transformed into products.

Geometric definition of

reaction rate.

d[R]

R=−

Rate expressed as tangent line dt

To concentration/time curve at a

Particular time in the reaction.

d ⎡⎣ P ⎤⎦

R=

dt

2 H2O2 (aq) à 2 H2O (l) + O2 (g)

Reaction rate and reaction order.

• The reaction rate (reaction velocity) R is quantified in terms

ofchanges in concentration [J] of reactant or product species J

with respect to changes in time.

• The magnitude of the reaction rate changes (decreases) as the

reaction proceeds.

• Rate of reaction is often found to be proportional to the molar

concentration of the reactants raised to a simple power (which

need not be integral). This relationship is called the rate

equation.

• The manner in which the reaction rate changes in magnitude with

changes in the magnitude of the concentration of each

participating reactant species is called the reaction order.

• Hence in other words:

– the reaction order is a measure of the sensitivity of the reaction

rate to changes in the concentration of the reactants.

Working out a rate equation. k = 5.2 x 10-3 s-1

2 5

T = 338 K

concentration of reactant.

(rate)0 ∝ ⎡⎣ N2O5 ⎤⎦ k = rate constant

0

Initial rate determined by (rate)0 = k ⎡⎣ N2O5 ⎤⎦

evaluating tangent to 0

curve at a given time t0. Equation. rate = − = k ⎡⎣ N2O5 ⎤⎦

dt

xA + yB k

⎯→

⎯ Products rate constant k

empirical rate

1 d ⎡⎣ A ⎤⎦ 1 d ⎡⎣ B ⎤⎦ α β

equation (obtained R = − =− = k ⎡⎣ A ⎤⎦ ⎡⎣ B ⎤⎦

from experiment) x dt y dt

α, β = reaction

stoichiometric orders for the

coefficients

reactants (got

Reaction order determination. experimentally)

Vary [A] , keeping [B] constant and Rate equation can not in

measure rate R. general be inferred from

Vary [B] , keeping [A] constant and the stoichiometric equation

for the reaction.

measure rate R.

Log R Log R

Slope = α Slope = β

Integrated rate equation.

Burrows et al Chemistry3, Chapter 8, pp.349-356.

Atkins de Paula 5th ed. Section 10.7,10.8, pp.227-232

• Many rate laws can be cast as differential equations which may then be

solved (integrated) using standard methods to finally yield an

expression for the reactant or product concentration as a function of

time.

• We can write the general rate equation for the process A à Products

as

dc

− = kF(c)

dt

where F(c) represents some distinct function of the reactant

concentration c. One common situation is to set F(c) = cn where n =

0,1,2,… and the exponent n defines the reaction order wrt the reactant

concentration c.

• The differential rate equation may be integrated once to yield the

solution c = c(t) provided that the initial condition at zero time which is

c = c0 is introduced.

Zero order kinetics. The reaction proceeds at the same rate R

regardless of concentration.

Rate equation : R R ∝ c0

units of rate constant k :

dc mol dm-3 s-1

R=− =k

dt

c

c = c0 when t = 0

integrate

using initial c0

condition half life t = τ 1/2 when c =

2

c0

τ 1/2 ∝ c0

slope = -k 2k

τ 1/ 2

c0 1

slope =

diagnostic 2k

plot c0

t

k

First order kinetics. A ⎯→

⎯ products First order differential

Initial rate equation.

concentration c0

dc

− = kc

rate = −

dc dt

dt

Initial condition

t = 0 c = c0

Solve differential

equation

via separation

of variables

(rate)t ∝ c

(rate)t = kc

k = first order Reactant concentration

rate constant, units: s-1 as function of time.

Half life τ½ c0

First order kinetics. t = τ 1/2 c=

2

θ = θ1/2 u = 1/ 2

ln2 0.693

τ 1/2 = =

k → s −1 k k

Mean lifetime of reactant molecule

c(t)

u= = exp ⎡⎣ −θ ⎤⎦

1 1 1

c0 c ( t ) dt =

∞ ∞

τ=

c0 ∫

0 c0 ∫

0

c0 e− kt dt =

k

θ = kt

First order kinetics: half life.

u=

a u = 1

a0

t = τ 1/2 c = c0 / 2

In each successive period

of duration τ1/2 the concentration

of a reactant in a first order reaction

decays to half its value at the start

of that period. After n such periods, u = 0.5

the concentration is (1/2)n of its

initial value.

u = 0.25

τ 1/ 2 u = 0.125

ln2 0.693

τ 1/2 = =

k k

c0 initial reactant concentration

Second order kinetics: equal dm3mol-1s-1

k

reactant concentrations. 2A

⎯→

⎯ P

slope = k

1

separate variables

dc integrate

c

− = kc 2 1 1

dt = kt +

c c0

t = 0 c = c0 t

c0

half life t = τ 1/2 c= c0

2

c (t ) =

1+ kc0t

τ 1/2 =

1 τ 1/2

kc0

1

rate varies as

τ 1/2 ∝ square of reactant

c0

concentration

τ 1/2 ↓ as c0 ↑ c0

1st order kinetics 2nd order kinetics

u(θ ) − kt

u(θ ) c(t) =

c0

c(t) = c0 e 1+ kc0t

u(θ ) = e−θ 1

u(θ ) =

1+ θ

θ = kt θ = kc0t

1st and 2nd order kinetics : Summary .

Reaction Differential Concentration Diagnostic Half

rate equation variation with Equation Life

time

A ⎯⎯

1

→

k

dc c(t ) = ln c(t) = −k1t + ln c0 ln 2

Products

− = k1c c0 exp [ −k1t ]

τ 1/ 2 =

k1

dt

k2

2 A ⎯⎯→ dc c(t ) = 1 1 1

− = k2 c 2 = k2t + τ 1/ 2 =

Products c0 c(t ) c0 k2 c0

dt

1 + k2 c0t

ln c(t) Diagnostic

Slope = - k1 1/c(t)

τ½ 1st order Plots .

Slope = k2

2nd order

t t c0

n th order kinetics: equal reactant k

concentrations. nA ⎯→

⎯ P

1

separate variables

dc integrate c n−1

− = kc n

dt 1 1

= ( n − 1) kt +

t = 0 c = c0 c n−1 c0 n−1

n ≠1

n = 0, 2,3,….. rate constant k

(

slope = n −1 k )

obtained from slope

t

Half life

ln τ 1/2

2 −1 n−1

⎧⎪ 2 − 1 ⎫⎪

n−1

τ 1/2 = ⎬ − ( n − 1) ln c0

( ) 0

n − 1 kc n−1

ln τ 1/2 = ln ⎨

⎪⎩ ( n − 1) ⎪⎭

k

(

slope = − n −1 )

τ 1/2 ∝ c01−n reaction order n determined

from slope

n > 1 τ 1/2 ↓ as c0 ↑

n < 1 τ 1/2 ↑ as c0 ↑

ln c0

k

Second order kinetics: A + B ⎯→

⎯ P

Unequal reactant concentrations. Pseudo first

order kinetics

half life when b0 >>a0

rate equation

⎧ 1⎫

ln ⎨2− ⎬ 1

da db dp ⎩ ζ⎭ ζ >> 1 →0

R=− =− = = kab τ 1/2 =

dt dt dt ( )

ka0 ζ −1

ζ

ln2 ln2

b0 τ 1/2 ≅ =

initial conditions ζ= kb0 k ′

a0 k ′ = kb0

t = 0 a = a0 b = b0 a0 ≠ b0

dm3mol-1s-1 pseudo 1st order

integrate using rate constant

partial fractions

( )

F a,b slope = k

1 ⎧⎪ ⎛ b b0 ⎞ ⎫⎪

( )

F a,b = ⎨ln ⎜ ⎟ ⎬ = kt

b0 − a0 ⎩⎪ ⎝ a a0 ⎠ ⎭⎪

t

Temp Effects in Chemical

Kinetics.

Atkins de Paula

Elements P Chem 5th edition

Chapter 10, pp.232-234

Burrows et al Chemistry3,

Section 8.7,

pp.383-389.

Van’t Hoff expression:

TS

Energy

⎛ d ln K c ⎞ ΔU 0

⎜⎝ dT ⎟⎠ = RT 2

P

E

Standard change in internal

E’

energy:

ΔU 0 = E − E ′ R

ΔU0

k P

!!!

R↽!! ⇀

!P

k′

Reaction coordinate

k

Kc =

k′

d ln k E

= This leads to formal

⎛ d ⎛ k ⎞⎞ d ln k d ln k ′ ΔU 0

dT RT 2 definition of Activation

⎜⎝ dT ln ⎜⎝ k ′ ⎟⎠ ⎟⎠ = dT − dT = RT 2 d ln k ′ E′ Energy.

P =

dT RT 2

Temperature effects in chemical kinetics.

• Chemical reactions are activated processes : they require an

energy input in order to occur.

• Many chemical reactions are activated via thermal means.

• The relationship between rate constant k and temperature T

is given by the empirical Arrhenius equation.

• The activation energy EA is determined from experiment, by

measuring the rate constant k at a number of different

temperatures. The Arrhenius equation ⎡ EA ⎤

is used to construct an Arrhenius plot k = Aexp ⎢ − ⎥

⎢⎣ RT ⎥⎦

of ln k versus 1/T. The activation energy

Pre-exponential

is determined from the slope of this plot. factor

ln k EA

Slope = −

⎛ d lnk ⎞ ⎛ ⎞ R

2 d lnk

E A = −R ⎜ ⎟ = RT ⎜

(

⎜⎝ d 1/T ) ⎟⎠ ⎝ dT ⎟⎠ 1

T

In some circumstances the Arrhenius Plot is curved which implies that

the Activation energy is a function of temperature.

Hence the rate constant may be expected to vary with temperature

according to the following expression.

⎡ E ⎤

k = aT exp ⎢ −

m

⎥

⎣ RT ⎦

We can relate the latter expression to the Arrhenius parameters A and EA

as follows.

E

ln k = ln a + mlnT −

RT

⎛ d ln k ⎞ ⎧m E ⎫

E A = RT 2 ⎜ ⎟ = RT 2 ⎨ + 2⎬

= E + mRT

⎝ dT ⎠ ⎩ T RT ⎭

E = E A − mRT

Hence ⎡ E ⎤ ⎡ E ⎤

k = aT mem exp ⎢ − A ⎥ = Aexp ⎢ − A ⎥

⎣ RT ⎦ ⎣ RT ⎦ Svante August

A = aT mem Arrhenius

Consecutive reaction : Case I.

Intermediate formation fast, intermediate decomposition slow.

k2

Case I . κ= << 1

k1 TS II

k << k1

2

TS I

k k

A ⎯⎯

1

→ B ⎯⎯

2

→C ΔGI‡ ΔGII‡

energy

I : fast II : slow

rds

A

‡ ‡

ΔGI << ΔGII B

C

since it has the highest

activation energy barrier. The reactant species A will be

more reactive than the intermediate B.

Consecutive reactions Case II: k2

Intermediate formation slow, intermediate decomposition fast. κ=

k1

k k

A ⎯⎯

1

→ B ⎯⎯

2

→C

k2

κ= >> 1 key parameter

Case II . k1

k >> k1

Intermediate B fairly reactive.

2 [B] will be small at all times.

k k

A ⎯⎯

1

→ B ⎯⎯

2

→C TS I

energy ΔGI‡

ΔGI‡ >> ΔGII‡

ΔGII‡

Step I rate determining A

since it has the highest B

activation energy barrier. C

reaction co-ordinate

k >> k2 Rate Determining Step

1

k1 k2

A ⎯⎯

→ B ⎯⎯

→C

Fast Slow

is high for much of the reaction and product C concentration rises

gradually since B--> C transformation is slow .

Step

k1 k2

A ⎯⎯

→ B ⎯⎯

→C

Slow Fast

• Reactant A decays slowly, concentration of intermediate species B

will be low for the duration of the reaction and to a good approximation

the net rate of change of intermediate concentration with time is zero.

Hence the intermediate will be formed as quickly as it is removed.

This is the quasi steady state approximation (QSSA).

Parallel reaction mechanism. A ⎯⎯

1

→X

k

k2

⎯

→Y

or parallel reaction scheme which is often met in

real situations. k1, k2 = 1st order rate constants

• A single reactant species can form two We can also obtain expressions

distinct products. for the product concentrations

We assume that each reaction exhibits 1 order x(t) and y(t).

st

kinetics.

• Initial condition : t= 0, a = a0 ; x = 0, y = 0 .

dx

dt

(

= k1a = k1a0 exp ⎡⎣ − k1 + k2 t ⎤⎦ )

( )

t

• Rate equation: x(t ) = k1a0 ∫ exp ⎡⎣ − k1 + k2 t ⎤⎦ dt

0

da

( )

R = − = k1a + k2a = k1 + k2 a = kΣ a

ka

{ (

x(t ) = 1 0 1− exp ⎡⎣ − k1 + k2 t ⎤⎦

k1 + k2

) }

dt

dy

(

= k2a = k2a0 exp ⎡⎣ − k1 + k2 t ⎤⎦ )

( )

a(t ) = a0 exp ⎡⎣ −kΣt ⎤⎦ = a0 exp ⎡⎣ − k1 + k2 t ⎤⎦

dt

t

( )

y(t ) = k2a0 ∫ exp ⎡⎣ − k1 + k2 t ⎤⎦ dt

0

1/2

kΣ k1 + k2

ka

{ (

y(t ) = 2 0 1− exp ⎡⎣ − k1 + k2 t ⎤⎦

k1 + k2

) }

• All of this is just an extension of simple Final product analysis x(t ) k1

yields rate constant ratio. Lim =

1st order kinetics. t→∞ y(t ) k2

Parallel Mechanism: k1 >> k2 Parallel Mechanism: k2 >> k1

1.0

κ = 0.1

normalised concentration

0.8

x(t)

u(τ)

0.6 v(τ)

w(τ)

0.4

a(t) κ = k2 /k1

/

0.2

y(t)

0.0

0 1 2 3 4 5 6

τ = k1t

k2

κ= = 0.1

k1

k1

= 10 =

( )

v ∞

k w(∞)

2

Reaching Equilibrium on the

Macroscopic and Molecular Level

N2O4

NO2

N2O4 (g) 2 NO2 (g)

colourless brown

Chemical Equilibrium :

a kinetic definition.

Concentrations time

• Countless experiments with chemical Concentrations vary invariant

systems have shown that in a state of with time

equilibrium, the concentrations of

reactants and products no longer change ⎡⎣ NO2 ⎤⎦ t ↑ ⎡⎣ NO2 ⎤⎦

eq

with time.

⎡N O ⎤ ↓

• This apparent cessation of activity occurs ⎣ 2 4 ⎦ t ⎡⎣ N2O4 ⎤⎦

because under such conditions, all eq

reactions are microscopically reversible.

• We look at the dinitrogen tetraoxide/ Kinetic Equilibrium

nitrogen oxide equilibrium which regime state

concentration

occurs in the gas phase. NO2

N2O4

colourless brown

Equilibrium:

Kinetic analysis. t →∞ ! "

R=R

! time

R = k ⎡⎣ N2O4 ⎤⎦

2

k ⎡⎣ N2O4 ⎤⎦ = k ′ ⎡⎣ NO2 ⎤⎦

eq eq

" 2 2

R = k ′ ⎡⎣ NO2 ⎤⎦ ⎡⎣ NO2 ⎤⎦ k Equilibrium

eq

= =K constant

Valid for any time t ⎡⎣ N2O4 ⎤⎦ k ′

k

First order reversible reactions : A B

understanding the approach to chemical equilibrium. k'

Rate equation

u+ v =1

da

= −ka + k ′b τ = 0 u = 1 v = 0

dt

Rate equation in normalised form

Initial condition

t = 0 a = a0 b = 0 du 1

+u =

dτ 1+ θ

Mass balance condition

Solution produces the concentration expressions

∀t a + b = a0

()

uτ =

1

1+ θ

{

1+ θ exp ⎡⎣ −τ ⎤⎦ }

Introduce normalised variables.

()

v τ =

θ

1+ θ

{

1− exp ⎡⎣ −τ ⎤⎦ }

u=

a

a0

v=

b

a0

( )

τ = k + k′ t θ =

k

k′ (

v τ ) ⎧⎪ 1− exp ⎡ −τ ⎤ ⎫⎪

Q (τ ) = =θ ⎨ ⎣ ⎦

⎬

u(τ ) ⎩⎪ 1+ θ exp ⎡ −τ ⎤

⎣ ⎦ ⎭⎪

Reaction quotient Q

First order reversible reactions: approach to equilibrium.

Kinetic

regime

1.0

0.8

Product B Equilibrium

concentration

0.6

u (τ) (

K =Q τ →∞ )

v (∞)

v (τ)

0.4

Reactant A

=

0.2 u( ∞ )

0.0

0 2 4 6 8

= (k+k')t

ττ=(k+k’)t

Understanding the difference between reaction quotient Q and

Equilibrium constant K.

12

Approach to

Equilibrium

10

Q<θ

8

θ = 10 Equilibrium

Q=K=θ

Q(τ)

Q(τ)

0

0 2 4 6 8

ττ =

=(k+k’)t

(k+k')t

Q (τ ) =

(

v τ ) ⎧⎪ 1− exp ⎡ −τ ⎤ ⎫⎪

=θ ⎨ ⎣ ⎦

⎬ t → ∞ Q→ K =θ =

k

K=

( )

v ∞

u(τ ) ⎪⎩ 1+ θ exp ⎡ −τ ⎤

⎣ ⎦ ⎪⎭ k′

( )

u ∞

QSSA: a fluid flow analogy.

• QSSA illustrated via analogy

with fluid flow.

• If fluid level in tank is to

remain constant then rate of

inflow of fluid from pipe 1 P1

must balance rate of outflow Fluid level

from pipe 2.

• Reaction intermediate

concentration equivalent to

fluid level. Inflow rate

equivalent to rate of

formation of intermediate P2

and outflow rate analogous to

rate of removal of

intermediate.

• Detailed mathematical analysis of complex

Quasi-Steady State Approximation.

reaction mechanisms is difficult. QSSA

Some useful methods for solving sets of

coupled linear differential rate equations k k

include matrix methods and Laplace Transforms. A ⎯⎯

1

→ X ⎯⎯

→P

2

state approximation induction

leads to a considerable simplification in the period Consecutive reactions k1 = 0.1 k2 .

kinetic analysis.

1.0

Normalised concentration

u(τ)

induction period (during which the

A P

concentration x of intermediates X rise

from zero), and during the major part 0.5

concentrations of all reaction

intermediates are negligibly small.

v(τ)

0.0

Mathematically , QSSA implies 0.0 0.5 1.0

τ = k1t

τ = k1t

dx intermediate X

= RX formation − RX removal ≅ 0

dt concentration

approx. constant

RX formation = RX removal

Atkins de Paula P Chem, 9th Edition,

Chapter 23,Catalysis, pp.876-908.

SF Chemical Kinetics.

Lecture 3-4

Catalysis:

Heterogeneous Catalysis &

Biocatalysis.

Lecture preview.

• In this lecture we focus attention on the

catalysis of chemical reactions.

• We consider:

– Heterogeneous catalysis on solid surfaces

– Enzymatic bio-catalysis . Michaelis-Menten single

enzyme/substrate kinetics.

• Common concept: Adduct formation / Binding

Interaction between catalyst and reactant.

Catalysis.

• Catalysis involves the enhancement of the

rate of a reaction by a substance, which is

not consumed in the reaction. It turns out

that the vast majority of all industrial

chemical reactions involve surfaces as the

catalysts. The kind of processes involved

range from hydrogenation of

hydrocarbons to detoxification of

exhaust gases. The catalytic converter in

an automobile is a classic example.

• The image presented across illustrates

the general principles: a particular metal

surface (in this case, a Pt-Rh alloy) is

known to catalyze the desired reaction. In

order to maximize the surface area of

the metal per weight,

small particles are used. You can almost

count the atoms in the particle shown,

which was from a real catalyst and was

studied by Scanning Electron Microscopy.

The particle shown has 500-600 atoms,

based on a rough estimate from the

number of atoms at its circumference.

Oxide substrates are also a general

characteristic of such catalysts.

http://www.pt.hut.fi/teke/opetus/uusitutkinto/ymparistokatalyysi/luentokalvot/hUT2006%20Introduction.pdf

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http://www.pt.hut.fi/teke/opetus/uusitutkinto/ymparistokatalyysi/luentokalvot/hUT2006%20Introduction.pdf

Catalysis: general comments.

• The overall change in free energy

• Catalysts come in a variety of forms ΔG0 for the catalytic reaction equals

varying from atoms and molecules to that of the uncatalyzed reaction.

large structures such as enzymes Hence the catalyst does not effect

and zeolites. the equilibrium constant (recall that

• The catalyst offers an alternative ΔG0 = -RT ln K) for the reaction A +B

low energy pathway for the reaction, à P. Thus if a reaction is

which is perhaps more complex, but thermodynamically unfavourable, a

energetically more favourable. catalyst cannot change the situation.

A catalyst changes the kinetics but

• The activation energy for the not the thermodynamics of a

catalytic reaction is significantly reaction.

smaller than that of the uncatalyzed

reaction. Hence the rate of the • The catalyst accelerates both the

catalyzed reaction is much larger. forward and the reverse reaction to

the same extent. If a catalyst

• Sabatier Principle: accelerates formation of product P

– The successful combination of from reactants A and B, it will do

catalyst and reaction is that in which the same for the decomposition of P

the interaction between catalyst and

reacting species is not too weak but into A and B.

also not too strong.

Catalysis.

• A catalyst accelerates the rate of a

reaction without itself being

consumed in the process.

separation

• The catalyst achieves its function by

forming bonds with the reacting A B P

molecules and allowing these to

react to form a product, which

detaches from the catalyst, and

leaves it unaltered such that it is P

available for the next reaction. catalyst

• Hence the elementary steps involved catalyst

in a catalytic process involve:

– Chemical bonding bonding

– Chemical reaction

– Separation

• Catalysis is subdivided into 3 sub- A B

areas:

– Homogeneous catalysis catalyst reaction

– Biocatalysis

– Heterogeneous catalysis.

Potential energy

A + B P Diagram for

Heterogeneously

Catalyzed reaction.

Non-catalytic

pathway

Activation

barrier

energy

ΔG † NC

ΔG †C Catalytic

pathway

A B

AB P

catalyst catalyst P

catalyst catalyst

bonding reaction separation

Reaction co-ordinate

Surface reactions.

• Diffusion of reactants to the active surface.

• Adsorption of one or more reactants onto

the surface.

• Surface reaction .

• Desorption of products from the surface.

• Diffusion of products away from the

surface.

Catalysis at solid surfaces

gas phase

pathway

energy

EG

EA

gas phase ED

reactants

ES

adsorbed

gas phase Ej = activation G : gas phase reaction

reactants adsorbed products energy for step j. A : adsorption

surface products S : surface reaction

catalysed D : desorption

pathway Reaction intermediates stabilized via bonding

to catalytic surface sites.

The Metal-Catalyzed Hydrogenation

of Ethylene H C CH (g) + H (g) H3C CH3 (g)

2 2 2

reaction between surface migration

C2 H 4 ads H •

ads adsorbed species

H ads

•

dissociative

adsorption

H 2C • − CH 3 ads

H ads

•

How do molecules bond to

surfaces?

• Two principal modes of adsorption of

molecules to surfaces.

– Physical Adsorption : the only bonding is by weak

Van der Waals - type forces. There is no

significant redistribution of electron density in

either the molecule or at the substrate surface.

– Chemisorption : a chemical bond, involving

substantial rearrangement of electron density, is

formed between the adsorbate and substrate. The

nature of this bond may lie anywhere between the

extremes of virtually complete ionic or complete

covalent character.

Potential energy versus distance curves for physisorption

and chemisorption.

long-range attraction will be present to varying

degrees in all adsorbate / substrate systems.

However, in cases where chemical bond formation

between the adsorbate and substrate can also

occur, the PE curve is dominated by a much deeper

chemisorption minimum at shorter values of d .

chemisorption curves.

strength of binding to the surface - in fact it is a direct

representation of the energy of adsorption, whilst the

location of the global minimum on the horizontal axis

corresponds to the equilibrium bond distance (re ) for the

adsorbed molecule on this surface.

The energy of adsorption is negative, and since it

corresponds to the energy change upon adsorption it is

better represented as ΔE(ads). However, you will also often

find the depth of this well associated with the enthalpy of

adsorption, ΔH(ads).

Terminology.

• Substrate - frequently used to describe the solid surface onto

which adsorption can occur; the substrate is also occasionally

(although not here) referred to as the adsorbent.

• Adsorbate - the general term for the atomic or molecular

species which are adsorbed (or are capable of being adsorbed)

onto the substrate.

• Adsorption - the process in which a molecule becomes adsorbed

onto a surface of another phase (note - to be distinguished from

absorption which is used when describing uptake into the bulk of

a solid or liquid phase)

• Coverage - a measure of the extent of adsorption of a species

onto a surface (unfortunately this is defined in more than one

way ! ). Usually denoted by the lower case Greek "theta", θ

• Exposure - a measure of the amount of gas which as surface has

seen; more specifically, it is the product of the pressure and

time of exposure (normal unit is the Langmuir, where 1 L = 10-6

Torr s ).

Typical Characteristics of Adsorption Processes

Physisorption

Chemisorption

Virtually unlimited

Temperature Range Near or below the condensation

(but a given molecule may

(over which adsorption point of the gas

effectively adsorb only over a

occurs) (e.g. Xe < 100 K, CO2 < 200 K)

small range)

Related to factors like molecular

Wide range (related to the

mass and polarity but typically

Adsorption Enthalpy chemical bond strength) -

5-40 kJ mol-1 (i.e. ~ heat of

typically 40 - 800 kJ mol-1

liquefaction)

Crystallographic Specificity

(variation between different Marked variation between Virtually independent of surface

surface planes of the same crystal planes atomic geometry

crystal)

Often dissociative Non-dissociative

Nature of Adsorption

May be irreversible Reversible

Saturation Uptake Limited to one monolayer Multilayer uptake possible

Very variable - often an Fast - since it is a non-activated

Kinetics of Adsorption

activated process process

Irving Langmuir Employed at General Electric (industrial

(1881 - 1957) research).

Examined oxygen adsorption on tungsten

filaments of light bulbs.

1932: Nobel Prize in Chemistry.

Ag

dynamic

surface equilibrium

Aads

Isotherm.

Kp

θ=

1+ Kp

Adsorption at gas/solid interface.

Adsorption. Term used to describe the process whereby a molecule (the

adsorbate) forms a bond to a solid surface (an adsorbent).

N number of sites occupied by adsorbate

θ θ= S

When θ = 1, NS = NΣ and an NΣ total number of adsorption sites

adsorbed monolayer is formed.

The fractional coverage θ depends A (g)

on pressure of adsorbing gas phase species.

This θ = θ (p) relationship is called an adsorption dynamic

isotherm. equilibrium

surface Aads

Langmuir Adsorption Isotherm.

Simple approach to quantitatively describe an adsorption

process at the gas/solid interface. Number of

N Σ = N S + NV Vacant sites

Assumptions :

• solid surface is homogeneous and contains a number of equivalent sites, each

of which is occupied by a single adsorbate molecule

• a dynamic equilibrium exists between gas phase reactant and adsorbed species

• no interactions between adsorbed species

• adsorbed species localised, ΔHads is independent of coverage θ

associative adsorption

kA adsorption rate constant

A (g) + S Aads

kD desorption rate constant

K measures affinity

kA of a particular

A2 (g) + S 2 Aads kA molecule for an

kD K=

kD adsorption site.

surface adsorption site

dissociative adsorption

At equilibrium : RA = RD

(

k A p 1− θ = kDθ )

Rate of adsorption :

(

RA = k A pNV = k A p 1− θ N Σ ) Kp

Langmuir adsorption

isotherm :

θ= associative adsorption.

pressure

fractional coverage 1+ Kp

slope = 1/K

of vacant sites 1

Rate of desorption : 1 1 θ

= 1+ 1 1

R = k N = kDθ N Σ

D D S θ Kp p

fractional surface coverage

A similar analysis can be done for dissociative adsorption.

Adsorption

( )

2

rate RA = k A pN 1− θ 2

Σ 1

Desorption RD = kD N Σ2θ 2 θ

rate

1

At equilibrium : RA = RD S=

K 1

( )

2

k A p 1− θ = kDθ 2 p

θ2 kA

Adsorption isotherm = p = Kp

(1− θ ) kD

2

for dissociative 1 1

adsorption. = 1+

Kp θ Kp

θ=

1+ Kp

high p Kp >> 1

Langmuir Adsorption Isotherm.

limit : 1+ Kp ≅ Kp

monolayer

formed θ → 1

1.0

0.8

Surface coverage θ K large

0.6

K = 10

0.4 K=1

K = 0.1

0.2 K small

Low p limit :

Henry Law 0.0

0.0 0.5 1.0 1.5 2.0

Kp << 1 P/atm

1+ Kp ≅ 1

θ ≅ Kp

Kp

θ=

1+ Kp

Adsorption Energetics

an exothermic process : Δ Hads is ED

negative.

A(g)

Both adsorption and desorption

processes follow the Arrhenius

equation. ΔHads

adsorption pre-exponential factor

⎡ EA ⎤ Aads

k A = AA exp ⎢ − activation energy for

⎥ adsorption

⎢⎣ RT ⎥⎦

⎡ ED ⎤ activation energy for

kD = AD exp ⎢ − ⎥ desorption

⎢⎣ RT ⎥⎦ kA AA ⎡ ΔHads ⎤

K = = exp ⎢ −

temperature (K) ⎥

kD AD ⎢⎣ RT ⎥⎦

desorption pre-exponential factor

ΔH = E A − E D

R = gas constant = 8.314 J mol-1 K-1 ads

How is ΔHads measured ? entropy of adsorption ΔHads ΔSads

0 0

lnK = − +

RT R

ΔGads

0

= −RT lnK = ΔHads

0

−TΔSads

0

⎛ ∂lnK ⎞ ΔHads

0

⎜⎝ ∂T ⎟⎠ = RT 2

entalphy of adsorption θ

Gibbs energy of adsorption

Langmuir adsorption assumed constant surface coverage

⎛ ∂ln p ⎞ ΔHads

0

θ constant surface ⎜⎝ ∂T ⎟⎠ = − RT 2

Kp = coverage θ

1− θ

⎡ ⎛ p ⎞ ⎤ ΔH 0 ⎧⎪ 1 1 ⎫⎪

⎧ θ ⎫ ⎢ln ⎜ 1 ⎟ ⎥ = ads

⎨ − ⎬

lnK + ln p = ln ⎨ ⎬ p

⎢ ⎝ 2 ⎠ ⎥⎦θ R ⎪⎩ T1 T2 ⎪⎭

⎩ 1− θ ⎭ ⎣

1.0

⎛ ∂lnK ⎞ ⎛ ∂ln p ⎞

⎜⎝ ∂T ⎟⎠ + ⎜⎝ ∂T ⎟⎠ = 0 T2 Determine adsorption

θ θ

Isotherm curves at

⎛ ∂ln p ⎞ ⎛ ∂lnK ⎞ T1 various temperatures.

= − θ 0.5

θ

⎜⎝ ∂T ⎟⎠ ⎜⎝ ∂T ⎟⎠

θ θ Measure values of p and T

at a constant surface

0.0

coverage.

0 1 2 Using this idea, p1, p2, T1

p and T2 can be measured so

p2 p1

ΔHads can be determined.

Constant θ Ln p

⎛ ∂ln p ⎞ ΔHads

⎜ ⎟ = −

(

⎜⎝ ∂ 1/T ) ⎟⎠

θ

R

coverage. 1/T

High T

Plot of ln p versus 1/T at

constant surface coverage

is linear.

Slope of plot enables one

Low T to evaluate ΔHads.

This can be repeated for

various set values of the surface

coverage, to enable ΔHads to be

Determine adsorption isotherm determined over the entire

at various temperatures. range of surface coverage θ .

Kinetics of surface reactions

• We probe the reaction kinetics

of surface processes assuming

Langmuir adsorption isotherm.

• Two principal types of reaction pA

mechanism are usually B

considered: A

– Langmuir- Hinshelwood fast RDS

fast

– Eley- Rideal. khet

ΘΑ

• In the Langmuir-Hinshelwood

mechanism the reactants are all

adsorbed on the surface and

react at the surface.

• In the Eley-Rideal mechanism

one has reaction between a pA

reactant in the gas phase and a A

reactant adsorbed on the pB AB

surface. B

RDS

khet

fast

ΘΑ

Langmuir - Hinshelwood Kinetics

1915

Langmuir

Isotherm

1927

Kinetics of

Catalytic

Reactions

Hinshelwood 1881 - 1957

1897 - 1967 Nobel Prize 1932

Nobel Prize 1956

Langmuir-Hinshelwood

A P B

Eley-Rideal

A B

P

Kinetics of surface reactions. Langmuir-Hinshelwood Mechanism

reacts and the product P does not adsorb.

A(g) → Aads → P(g)

Reaction Surface coverage of adsorbed gas

rate R = kθ A Surface coverage

related to gas

K A pA

θA = pressure p via

Langmuir adsorption

1+ K A p A isotherm

kK A p A

R= Example: decomposition of NH3 on W

1+ K A p A surfaces. Rate 1st order at low p, while

as pressure increases it changes to zero order

Limiting situations. corresponding to saturation kinetics.

Rate depends

Kp >> 1

Rate independent of

Gas pressure p Kp << 1 linearly on gas

Pressure p

Zero order kinetics. First order kinetics.

Adsorption process

R ≅ kKp

Adsorption rate very

R ≅ k large when p is high.

is rate determining

when p is low.

Decomposition step rds. Decomposition is fast.

kKp

R=

1+ Kp

Competitive adsorption and bimolecular surface kinetics.

for adsorption sites S.

k1

A(g) + S Aads k

Aads + Bads ⎯→

⎯ C ads

k-1

k2

Catalyst surface B(g) + S Bads

k-2 Bimolecular surface

Assuming an adsorption/desorption

reaction

equilibrium for each gas we get:

θA

K A pA

= K A pA θA =

1− θ A − θ B 1+ K A pA + K B pB

θB K B pB

= K B pB θB =

1− θ A − θ B 1+ K A pA + K B pB

k1

KA = kK AK B pA pB

k−1 dc

RΣ = = kθ Aθ B =

dt

( )

2

k2

KB = 1+ K A pA + K B pB

k−2

LH model bimolecular reaction

dc kK AK B pA pB

RΣ = = kθ Aθ B =

Maximum rate occurs where dt

( )

2

θA = θB = 0.5 1+ K A pA + K B pB

For constant PB

rate

Rate limited by

surface concentration of A

Rate limited by

surface concentration of B

pA

θΒ << θΑ

θΒ >> θΑ

Eley-Rideal Mechanism.

Mechanism describes a surface reaction in pA

which one reactant is adsorbed while A

the other is in the gas phase. pB AB

B

A(g) → Aads RDS

khet

Aads + B(g) → P(g) fast

ΘΑ

An adsorbed molecule may react

directly with an impinging gas

molecule by a collisional mechanism

Reaction rate R is dependent on the Rate always 1st order wrt pB.

pressure of B pB, and the surface 2 limiting cases for reaction order

coverage of A θA. wrt pA.

When KA (ΔHads) is small or pA is small

We assume that B and product P do then KApA <<1 and R = kKApApB.

not competitively bind for surface sites Rate is 1st order wrt pA.

with A. When KA (ΔHads) is large or pA is large

then KApA >>1 and R = kpB.

kK A p A pB Rate is zero order wrt pA.

R = kθ A pB = Competitive adsorption of products

1+ K A p A can complicate the kinetics.

Diagnosis of mechanism

If we measure the reaction rate as a function of the coverage by A, the

rate will initially increase for both mechanisms.

Eley-Rideal: rate increases until surface is covered by A.

Langmuir-Hinshelwood: rate passes a maximum and ends up at zero,

when surface covered by A.

The reaction B + S ó B-S

cannot proceed when A blocks all sites.

Catalyst Preparation

For a catalyst the desired properties are

• high and stable activity

• high and stable selectivity

• controlled surface area and porosity

• good resistance to poisons

• good resistance to high temperatures and temperature fluctuations.

• high mechanical strength

• no uncontrollable hazards

manufacture of the catalyst are

• If the catalyst should be supported or unsupported.

• The shape of the catalyst pellets. The shape (cylinders, rings, spheres,

monoliths) influence the void fraction, the flow and diffusion

phenomena and the mechanical strength.

• The size of the catalyst pellets. For a given shape the size influences

only the flow and diffusion phenomena, but small pellets are often much

easier to prepare.

• Catalyst based on oxides are usually activated by reduction in H2 in the

reactor.

Ammonia synthesis

A: Steam reforming

B: High temperature water-gas shift

C: Low temperature water-gas shift

D: CO2 absorption

E: Methanation

F: Ammonia synthesis

G: NH3 separation.

Ammonia Synthesis

Fe/K catalyst

exothermic

Mechanism

1 N2(g) + * N 2*

2 N 2* + * 2N*

3 N* + H* NH* + *

4 NH* + H* NH2* + *

5 NH2* + H* NH3* + *

6 NH3* NH3(g) + *

7 H2(g) + 2* 2H*

therefore apparent with d-block metals as catalysts.

Ru and Os are more active catalysts, but iron is

used.

Biocatalysis: Kinetics of enzyme reactions.

A catalyst is a substance that increases the rate of a described in most

Biochemistry texts.

reaction without itself being consumed by the process.

• A catalyst lowers the Gibbs energy of activation ΔG ‡ by providing a different

mechanistic pathway by which the reaction may proceed. This alternative mechanistic

path enhances the rate of both the forward and reverse directions of the reaction.

• The catalyst forms an intermediate with the reactants in the initial step of the reaction

( a binding reaction), and is released during the product forming step.

• Regardless of the mechanism and reaction energetics a catalyst does not effect ΔH or

ΔG of the reactants and products. Hence catalysts increase the rate of approach to

equilibrium, but cannot alter the value of the thermodynamic equilibrium constant.

EA lowered

A reactant molecule acted upon

catalyst absent by an enzyme is termed a substrate.

energy

ΔEA substrate reacts is called the active

reactants catalyst present site. Enzyme specificity depends on

the geometry of the active site and the

products spatial constraints imposed on this region

ΔH by the overall structure of the enzyme

thermodynamics molecule.

unchanged

reaction coordinate

Space filling models of

Enzyme lock/key mechanism : the two conformations of

the enzyme hexokinase.

natural molecular recognition. (a) the active site is not

occupied. There is a cleft in

the protein structure that allows

the substrate molecule glucose

to access the active site.

(b) the active site is occupied.

The protein has closed around

the substrate.

hexokinase

glucose

Classification of enzymes.

Amperometric Glucose Sensors

• Enzymes are very specific biological

catalysts.

• They interact with substrates via the

Michaelis/Menten mechanism.

• If enzymes can be incorporated and

immobilized within a matrix located next

to an electrode surface, then it is

possible to combine the specificity of

enzyme catalysis with the many

advantages of amperometric detection.

• We focus attention of glucose oxidase

and the amperometric detection of blood

glucose, since the glucose sensor is well

developed commercially.

sensors and their applications in diabetes

management. Chem. Rev. 2008, in press.

• J. Wang, Electrochemical glucose biosensors.

Chem. Rev., 108 (2008) 814-825.

• J. Wang, Glucose biosensors: 40 years of

advances and challenges. Electroanalysis, 13

(2001) 983-988.

• J. Wang, In vivo glucose monitoring: towards

‘sense and act’ feedback loop individualized

medical systems. Talanta, 75 (2008) 636-641.

Redox enzymes.

• Redox enzyme contains • Flavoproteins are most often

tightly bound redox active studied.

prosthetic group (e.g. flavin, • They consist of ca. 80

haem, quinone) that remains different enzymes containing

bound to the protein either

throughout redox cycle. – Flavin adenine dinucleotide

– Prosthetic group = non amino (FAD)

acid component of – Flavin mononucleotide (FMN)

conjugated protein.

at the active site.

• Redox enzymes exist in both

oxidised and reduced forms. • The flavin unit is strongly

associated with the protein

• Redox enzymes can be structure and is sometimes

subclassified in terms of the covalently bound to the amino

redox centres present in the acid residues in enzyme.

enzyme.

Dimeric structure of glucose oxidase

Glucose oxidase GOx.

b-D-glucose: oxygen

1-oxidoreductase

EC1.1.3.4) : GOx .

with MW = 160 kDa.

Contains one tightly bound

flavin adenine dinucleotide

FAD unit per monomer as

cofactor. FAD is not

covalently bound and can be

released from the holo

protein following

denaturation.

FAD exhibits redox activity.

Gox exhibits a very high

degree of specificity for monomeric unit

β-D-glucose.

redox active

region

protein sheath

Enzyme catalysed reaction:

Variation of reaction rate with substrate (reactant)

concentration.

Rate variation adopts shape of rectangular hyperbola.

1.2

Ψ = RΣ Rmax = RΣ kc [E]Σ

1.0

Saturated enzyme

Ψ=RΣ/k erate

0.8

c Σ

kinetics

Normalized

0.6

Unsaturated enzyme

0.4 kinetics

0.2

Normalized substrate concentration

0.0

0 10 20 30 40 50

complex rate equation, where

the reaction rate varies with

In electrochemical biosensor output have current (rate) reactant concentration

vs substrate concentration. in a non linear way.

Time course of enzyme catalyzed reaction.

Single substrate Michaelis-Menten Kinetics.

Enzyme-substrate complex

Rate

number = max number of

enzymatic reactions catalyzed kc/KM measures catalytic efficiency of enzyme.

per second. Maximum value corresponds to

Diffusion control reaction between

S and E in solution (1010 M-1s-1).

Note: Biochemistry texts use υ

as symbol for reaction rate (velocity).

SF Chemical Kinetics.

Lecture 5.

Microscopic theory of chemical

reaction kinetics.

Microscopic theories of

chemical reaction kinetics.

• A basic aim is to calculate the rate constant for a chemical reaction

from first principles using fundamental physics.

• Any microscopic level theory of chemical reaction kinetics must

result in the derivation of an expression for the rate constant that

is consistent with the empirical Arrhenius equation.

• A microscopic model should furthermore provide a reasonable

interpretation of the pre-exponential factor A and the activation

energy EA in the Arrhenius equation.

• We will examine two microscopic models for chemical reactions :

– The collision theory.

– The activated complex theory.

• The main emphasis will be on gas phase bimolecular reactions since

reactions in the gas phase are the most simple reaction types.

References for Microscopic Theory

of Reaction Rates.

• Effect of temperature on reaction rate.

– Burrows et al Chemistry3, Section 8.7, pp.383-389.

• Collision Theory/ Activated Complex Theory.

– Burrows et al Chemistry3, Section 8.8, pp.390-395.

– Atkins, de Paula, Physical Chemistry 9th edition,

Chapter 22, Reaction Dynamics. Section. 22.1, pp.

832-838.

– Atkins, de Paula, Physical Chemistry 9th edition,

Chapter 22, Section.22.4-22.5, pp. 843-850.

SCT : a summary.

• The major problem with SCT is that the threshold energy E* is very

difficult to evaluate from first principles.

• The predictions of the collision theory can be critically evaluated by

comparing the experimental pre-exponential factor with that computed

using SCT.

• We define the steric factor P as the ratio between

the experimental and calculated A factors.

P=A A

• We can incorporate P into the SCT

exp calc

• For many gas phase reactions k = Pz AB

exp ⎢− ⎥

⎣ RT ⎦

P is considerably less than unity.

• Typically SCT will predict that Acalc will be in ⎡ E*⎤

k = Pz AA exp ⎢ − ⎥

the region 1010-1011 Lmol-1s-1 regardless of ⎣ RT ⎦

the chemical nature of the reactants and products.

• What has gone wrong? The SCT assumption of hard sphere collision

neglects the important fact that molecules possess an internal structure.

It also neglects the fact that the relative orientation of the colliding

molecules will be important in determining whether a collision will lead to

reaction.

• We need a better theory that takes molecular structure into account. The

activated complex theory does just that .

Transport

Summary of SCT. property

Energy criterion

k = Pz AB exp ⎢ − ⎥

1/2 ⎣ RT ⎦

⎧⎪ 8kBT ⎫⎪ ⎡ E*⎤

k = N Aσ ⎨ ⎬ exp ⎢−

⎪⎩ π µ ⎪⎭

⎥

⎣ RT ⎦ ⎡ E*⎤

k = Pz AA exp ⎢ − ⎥

⎡ E*⎤

= z AB exp ⎢ − ⎥ ⎣ RT ⎦

⎣ RT ⎦

Steric factor

(Orientation requirement)

A,A encounters Weaknesses:

• No way to compute P from molecular

parameters

1/2

⎧⎪ kBT ⎫⎪ • No way to compute E* from first principles.

⎡ E*⎤

k = 2N Aσ ⎨ ⎬ exp ⎢− ⎥ Theory not quantitative or predictive.

⎪⎩ π m ⎪⎭ ⎣ RT ⎦ Strengths:

• Qualitatively consistent with observation

⎡ E*⎤ (Arrhenius equation).

= z AA exp ⎢ − ⎥

⎣ RT ⎦ • Provides plausible connection between

microscopic molecular properties and

macroscopic reaction rates.

• Provides useful guide to upper limits for rate

constant k.

Course Summary

• Basic terms in reaction kinetics: reaction order, reaction rate.

• Simple rate equations: zero, first, second order kinetics

• Rate equations for more complex reactions

– Consecutive reactions

– Parallel Reactions

– Third order reactions

– Equilibrium

– Steady State Analysis of complex reactions

• Catalytic reactions

– Surface reactions & Heterogeneous catalysis

– Bio-catalysis & Enzyme kinetics

• Temperature Dependence of Reaction Rate

• The theory of reaction kinetics

– Simple Collision Theory (SCT)

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