Documente Academic
Documente Profesional
Documente Cultură
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!
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
• 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).
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
T = 338 K
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
• 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
t = 0 c = c0
Solve differential
equation
via separation
of variables
ln2 0.693
τ 1/2 = =
k → s −1 k k
u = 0.25
τ 1/ 2 u = 0.125
ln2 0.693
τ 1/2 = =
k k
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
reaction co-ordinate
k >> k2 Rate Determining Step
1
k1 k2
A ⎯⎯
→ B ⎯⎯
→C
Fast Slow
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
1.0
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
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
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
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
http://www.pt.hut.fi/teke/opetus/uusitutkinto/ymparistokatalyysi/luentokalvot/hUT2006%20Introduction.pdf
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.
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
(
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
⎡ 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
1927
Kinetics of
Catalytic
Reactions
A P B
Eley-Rideal
A B
P
Kinetics of surface reactions. Langmuir-Hinshelwood Mechanism
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.
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
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*
EA lowered
A reactant molecule acted upon
catalyst absent by an enzyme is termed a substrate.
energy
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.
protein sheath
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
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