Catalyze Reaction

CHM3103 Chemical
Kinetics
Dr. Md. Saiful Islam
Faculty of Science
UPM, ext- 6981
E-mail: msaifuli2007@gmail.com

Outline:

Homogenous catalysis

General and acid/base catalysis

Acidity function

Bronsted relation and

Enzyme reaction
 Learning outcomes (LO)

1. Explain general catalytic mechanism and identify Arrhenius & Vant Hoff
intermediate
2. Derive rate equations for case involving for these intermediates.
3. Expalin Acid base catalysis and apply case involving Arrhenius & Vant Hoff
intermediates.
4. Differentiate general and specific acid-base catalysis
4. Rate Determination for acid-base catalysis reaction system
5. Bronsted relationship for acid-base catalysis reaction
6. Derive Hammett acidity function (H o) for highly concentrated acidic solution
7. Derive Michaelis-Menten equation for enzyme kinetics reaction
8.
Refs: 1. keith J. Laidler, chemical kinetics, 3rd ed. 2. J.E House, principles of chemical
kinetics, 3. Frank Wilkinson,chemical kinetics and reaction mechanismother books on
chemical kinetics
 Catalyst and Catalysis

A catalyst is a substance that accelerates the rate of a

chemical reaction without being part of its final products

A catalyst is a substance that increases the rate of a reaction

without affecting the position of equilibrium

Catalysis is a process whereby a reaction is being

accelerated by the presence of a catalyst .

Haber's Process - manufacture of NH3 from N 2 and H2 using
iron as catalyst.
FeN2 + 3H2 = 2NH3
Hydrolysis of esters in the presence of H2SO4 catalyst.
CH3COOC2H3 +H2O ---------------
H2SO4 CH3COOH + C2H3OH
 Effect of Catalyst on reaction rate

A catalyst changes the reaction path by lowering its

activation energy and consequently the catalyst
increases the rate of reaction
k(T) = k0e-Ea/RT
Ea < Ea
k0 > k0
Ea k > k Ea

G = G

A+B A+B+
G catalyst G

C C + catalyst

uncatalyzed catalyzed
Catalysts Open Up New Reaction Pathwa
 Types of Catalysts Homogeneous vs.
Heterogeneous

Homogeneous catalysis Heterogeneous catalysis

Single phase Multiphase
(Mostly solid-liquid and solid-gas)
(Typically liquid) High temperature
Low temperature Design and optimization tricky
Separations are tricky

Zeolite catalyst
Catalyst powders

Catalyst and reactant are in the

Catalyst and reactant are in the same
different phase
phase
 Types of Catalysts General and Specific Acid/Base

General acid/base catalysis: When the rate law depends on the concentration
of all acids or bases present in the solution then this is known as general acid/base
catalysis.
Specific acid/base catalysis: When the rate law depends only on [H+] or [OH-]
but not on the concentration of other acids or bases present in the solution, such
reactions are known specific catalysis.

1. General Acid Catalysis :

uncharged acids : (CH3COOH)
1. Specific Acid Catalysis : (H3O+) cationic acids : (NH4+)
2. General Base Catalysis :
2. Specific Base Catalysis : (OH-)
uncharged bases : (NH3)
anionic bases : (CH3COO-)
 Types of Catalysts - Enzymes
The Gold Standard of
catalysts
Highly specific
Highly selective
Highly efficient
Catalyze very difficult
reactions
N2 NH3
CO2 + H2O C6H12O6
Triosephosphateisomerase
TIM Works better in a cell
Cytochrome C Oxidase
than in a 100000 l
Highly tailored active sites
reactor
Often contain metal atoms
 General Catalytic Mechanism

The rate of a catalyzed reaction is often proportional to the concentration of the catalyst
[C]
= k[C]
where [C] represent the concentration of the catalyst, k is a function of the concentration of substrate.
At zero concentration, the velocity would be zero ( o). Therefore, it can be introduce an additional term
that is independent of the catalyst concentration.
= k[C] + o

Mechanism:
All catalyzed reactions appear to involve the formation of some kind of intermediate species, therefore
wide variety of mechanism could be found. However, usually one pattern applies to homogeneous
catalysis such acid-base and enzyme reactions.
The over-all reactions can be written as-
 General Catalytic Mechanism

Where, C= Catalyst, S= substrate, X, Y = intermediates, P, Z = products

The 2nd reaction does not occur in reverse direction eg by removing P as it formed

In acid catalysis: C = H+, X = OH-

Reaction 2: proton is transferred to W, => W is basic or amphoteric

In some cases (ii) is slow, => k2[X][W]<< k-1[X][Y], in these case X Arrhenius intermediate
(Equilibrium concept)
If the reverse case applies, => k2[X][W] > > k-1[X][Y], X Vant Hoff intermediate (Steady state
concept). If neither case applies-complex.
General Catalytic Mechanism

At equilibrium [C] = [C]o-[X] and [S] = [S]o-[X]

[S]o

[S]o
 General Catalytic Mechanism

If W and Y are non-existent (such as in acid-base catalysis)

= or written as, = [Michaclis-Menten equation],

In acid base catalysis remain linear with [S]o due to rapid equilibrium in this solution.

Case 2: =>k= , = ? Calculate Assignment

Steady-state treatment: Vant Hoff intermediate:

K2 = > [X] small and steady state applicable

 General Catalytic Mechanism

[C][S] - [X][Y]- [X][W] = 0

Since [C] = [C]o [X] & [S] = [S]o [X] and [X] small => can be neglected

=> [X] =

=> =

At low concentration of either substrate or catalyst the rate varies linearly with [C] o ; or [S]o
however independent at higher concentration.

For surfaces and enzymes, w and Y are non-existent.

[C]o
=>

[C]o
 Acid-Base Catalyzed Reactions
23.
14
In most reactions that are acid- or base- catalyzed, there is no reaction at all in the absence
of at least a trace of catalyst.
Bronsted-Lowry Definition: According to this theory, an acid is a proton donor
and a base a proton acceptor.

1. Specific Acid Catalysis : (H+/H3O+), 2. Specific Base Catalysis : (OH-)

3. General Acid Catalysis : uncharged acids : (CH3COOH), cationic acids: (NH4+)
4. General Base Catalysis :uncharged bases : (NH3), anionic bases : (CH3COO-)
Acid-Base Catalytic Mechanism
 Acid-Base Catalytic Mechanism

in solution of low pH, k varies linearly with [H+] and high pH, k varies linearly [OH-s
K is likely to depends on one or other of the terms on the right hand side of equation

The rate is minimum when the second and third terms are equal in eq.(1). Thus for acidic
solution equation 1 in logarithmic form often becomes-
logk = log kH+ + log [H+]
=
logk = log kH+ - pH ----- (2), While in basic solution (1) =>

logk = (log kOH- + logKw ) - log [H+]

logk = (log kOH- + logKw ) + pH ------- (3).
If under any condition ko>kH+[H+] + kOH-[OH-] then (1) => logk = logko ------- (4).

Specific acid catalysis Specific base catalysis

k = kH [H+] k = kOH [OH-]
logk = log kH+ - pH logk = (log kOH- + logKw ) + pH
Relation between rate constant and [H+] ion concentration

Figure log k
verses pH,
for acid
catalysed
slope = -1,
and for
base
catalysed
slope= +1

Skrabal diagram
17
 Rate Determination for Acid-Base Reaction
If proton transfer to solvent (protolytic/acid catalysis i.e. SH + + H2O S + H3O+), then the
process are-
k1
S + BH SH+ + B
k-1
k2 where, P = the products of
SH+ + H2O P + H3O+
reaction.
The equilibrium for the ionization of the acidic species BH +,
BH+ + H2O P + H 3 O+
The equilibrium constant for this reaction is K.
Apply steady state treatment to the species SH+ gives-
k1[S][BH+] - k-1[SH+][B] - k2[SH+] = 0

The concentration of water being assumed to be incorporated in the rate constant k2. The
concentration of SH+ is thus-
[SH+] = k1[S][BH+]/ k-1[B]+ k2 ---------- (1)
18
 Rate Determination
The rate of formation of products is therefore
= k2[SH+] = k1k2[S][BH+]/ k-1[B]+ k2 ---------- (2)

if is k-1[B] much greater than k2 (it is an Arrhenius complex). In this case the above equation
=>
= k1 k2[S][BH+]/ k-1[B] ---------- (3)
The acid dissociation constant K is, however, given by-
K = [B][H3O+]/[BH+]
And this with eqn. (3) gives-
= k1 k2[S][H3O+]/k-1K[B]

If k2 is much greater than k-1[B], which means that the complex is a vant Hoff complex, the
rate equation (3) becomes-
= k1[S][BH+] ----- (4)
19
 Rate Determination
The prototropic mechanism, in which the proton transfer from SH + is to a basic species B
present in solution, may be written as-
k1
S + BH + SH+ + B
k-1
k2
SH+ + H2O P + H3O+
The equilibrium for the ionization of the acidic species BH +,
BH+ + B P + H 3 O+
Again the equilibrium constant for this reaction is K.
Apply steady state equation is-
k1[S][BH+] - k-1[SH+][B] - k2[SH+][B] = 0

Whence, [SH+] = k1[S][BH+]/(k-1+ k2 )[B]---------- (1)

The rate is now, = k2[S][BH+] = k1k2 [S][BH+]/(k-1+ k2 )---------- ---------- (2)

This is now general acid catalysis, irrespective of weather the complex is an Arrhenius or a
vant Voff complex.
20
 Bronsted Relationship
Consider the following reaction
HA+ H2O H3O+ + A-

This constant being written as

ka = [H3O+][A-]/[HA]
Since acid catalytic constant ka = dissociation constant ka

---------- (1)
Where Ga and are constant. For basic catalysis equation (1) =>
---------- (2)

Where kb and are constant. The kb is now the basic dissociation constant. For the basic
dissociation-

B + H2 O BH+ + OH-

Kb = [BH+][HO-]/[B] ---------- (3)

Again consider, the acid dissociation of the conjugate acid BH +,
BH+ + H2O B + H3O+
21
 Bronsted Relationship
for which the constant is, ka = [B][H3O+]/[BH+] ------- (4)

From equation (3) & (4) => kakb = kw since, kw = [OH-][H3O+]

so (2) =>kb = kw/ka --------------------- (5)

= -------- (6)

where is the new constant. Equation (2), (3) & (6) are commonly spoken of as
Bronsted relationship.
If more than one ionizable proton (e.g.HOOCCH2COOH), or any base that can accept
more than one proton (e.g. PO4- - - ), the equation (6) need to modified as follows-

Ka/p = Ga(qKa/p)-------- (7)

Kb/q = Gb(p/qKa)--------(8)
In eqn. (7), p is the number of dissociable proton and q is the number of conjugate base. In eqn. (8), q
is the number of base and p is the number of dissociable protons in conjugate acid.
22
 Acidity Functions & Reaction Rates
For highly concentrated acidic solution Hammett proposed an empirical function to measure
proton donating power of strong acidic solution. Consider the following reaction where acid
dissociation of the conjugate acid BH+ of an uncharged base B.
BH+ + H2O B + H 3 O+
ka = [B][H3O+]/[BH+]. H3O+B /BH+ --------------------- (1)

Where s are the activity coefficients. In acid solution, H3O+ = B = BH+ = 1

Since (1) => ka = [B][H3O+]/[BH+]

log ka = log[H3O+] + log[B]/[BH+] ----------- (2)

However, in concentrate solution H3O+ = B = BH+ 1

= > log ka = log H3O+B /BH+ + log[B]/[BH+] ----------- (3)

The Hammatte acidity function, Ho, is defined by the following equation-

Ho = - log H3O+B /BH+, since -logka = pka, so equation (2) & (3) =>
Ho = pka+ log[B]/[BH+] ----------- (4)

pka values can be determined in dilute solution from eqn.(2). And [B]/[BH+] using
spectrophotometrically in concentrate acidic solution. This allows Ho to be determined from
 Hammett Acidity Function

The acidity function is by no means

a universal indication of the
tendency of an acid solution to
protonate a base.
B and H3O+ relate to the Hammett
indicator, and may not relate to your
substrate.
H0 measures the tendency of a
solution to protonate a neutral base,
not to a base of any other electrical
charge.
Other Hammett measures (H-,
derived from p-toluene sulfonate)
can be used for anionic substrates.

CHEE 323
 Ho and Acid Catalyzed Reaction Kinetics

For those acid catalyzed reactions in which protonation of a neutral substrate is a kinetically
significant step, there may exist a relationship between the reaction rate and the acidity
function. Consider a reaction proceeding by the following mechanism:

K
r1: AH
AH
k2

r2: AH H P

where reaction 2 is rate limiting: r2 k 2 [AH ]
and reaction1 is at equilibrium
a Aa H
a H A
Ka [AH ] [A]
a AH K a AH
CHEE 323
Ho and Acid Catalyzed Reaction Kinetics
23.
26
 ToolsoftheLaboratory

Conductometric monitoring of a
reaction

Manometric monitoring of a
reaction
 Enzyme Catalysis
Enzymes are high molecular weight proteins that are linked by peptide bonds. In their
catalytic behavior, they provide a lower energy pathway for a reaction to take place. E.g
Beta-amylase, alpha- amylase, mw- 10,000- 100,000. Hundrate of amino acid peptide chain
and sometimes metals ions e.g. fe, Ca, Mg, Zn
Enzymes frequently exhibit catalysis in very specific ways-
1. Absolute specificity
2. group specificity amino acid groups
3. Linkage specificity that form an active
4. Stereochemical specificity site

Kinetic of enzymes reaction (Michaelis - Menten Approach):

Substrate + enzyme Substrate-enzymes product + enzyme

K1
k2
E+S ES P E
K-1
ES intermediate- apply steady state approach-

d[ES]/dt = k1[E][S]- k-1[[ES] k2[ES] = 0

 Enzyme Catalysis
or k1[E][S] = k-1[[ES] + k2[ES] -------(1)

The total enzyme concentration, [E]t, is equal to the sum of the concentration of free enzyme,
[E], and that attached to the substrate, [ES].
Therefore, [E]t = [E] + [ES]

Or [E] = [E]t - [ES]

By submitting this value in Eq.(1), we obtain-
k1([E]t [ES])[S] = k-1[[ES] + k2[ES]

k1[E]t[S] k1[ES][S] = k-1[[ES] + k2[ES]

we can rearrange to give-
k1[E]t[S] = k-1[[ES] + k2[ES] + k1[ES][S]

or [ES] = k1[E]t[S]/k-1+k2+k1[S] ------- (2)

Since the rate of production formation, written as R = k2[ES]

Thus, R = k2[ES] = k1k2[E]t[S]/k-1+k2+k1[S]

 Enzyme Catalysis
Dividing both numerator and denominator by k1 gives-

R = k2[E]t[S]/(k-1+k2)/k1+[S] ------ (3)

R = k2[E]t[S]/Km+[S] ---------- (4)

This equation is known as the Michaelis-Menten equation and the constant (k -1+k2)/k1 is

called the Michaelis-Menten constant, Km.

When [S] is large compared to Km, the denominator of Eq.(3) is approximately [S] so that-

R = k2[E]t[S]/[S] ------- (5), and the rate under these conditions is the maximum rate, R max. =>

Rmax = k2[E]t, this case is equivalent to saying that all of the enzyme is bound to the substarte
in comples form. Therefore,-
R = Rmax[S]/Km+[S]------ (6)

If the substrate concentration, [S], is equal to Km,

R = Rmax[S]/[S]+[S] = Rmax/2------ (7)

Therefore, while Km= (k-1+k2)/k1, it is also equal to the concentration of substrate when the
reaction rate is half of its maximum value.
 Enzyme Catalysis
When the substrate concentration is much larger than Km, [S] > Km

R = k2[E]t[S]/Km+[S] k2[E]t[S]/[S]-------(8)
And the reaction follows a zero order rate law with respect to substrate concentration [figure]
When Km>>[S],

R = k2[E]t[S]/Km+[S] k2[E]t[S]/ Km -------(9)

So the reaction follows a first-order rate law with respect to substrate concentration.
 Important of Michaelis constant

The Michaelis constant is a fundamental characterization of an enzyme. First, it

gives the concentration of substrate necessary to bind to half of the available sites
on the enzyme. Second, it gives an index of the relative binding affinity of the
substrate to the enzyme active sites. Since Km is a concentration, the values are
useually expressed in mM units.

Competitive Inhibition: (Assignment)

For the following competitieve reaction determine the Eqn. 1/R = Km/Rmax(1+

[I]/Ki)1/[S] +1/Rmax

K1 k2
E+S ES P E
K-1
Lineweaver-Burk Plot (Double-Reciprocal Plot)

Vm [ S ]
v
K m [S ]

Linearizing it in double-reciprocal form:

1 1 Km 1

v Vm Vm S
 Lineweaver-Burk plot (Double-reciprocal plot)

- a slope equals to Km/Vm

- y-intercept is 1/Vm.
- More often used as it shows the independent variable [S]
and dependent variable v.
-1/v approaches infinity as [S] decreases
- gives undue weight to inaccurate measurement
made at low concentration
- give insufficient weight to more accurate
measurements at high concentration.
 Eadie-Hofstee Plot

v
v Vm K m
[S ]

- the slope is Km
- y-axis intercept is Vm.
-Can be subject to large error since both coordinates contain
dependent variable v,
but there is less bias on points at low [s].
 Hanes-Woolf (Langmuir) Plot

[S ] K m 1
[S ]
v Vm Vm

- the slope is 1/Vm

- y-axis intercept is Km/Vm
- better fit: even weighting of the data