Kinetics

Definition: chemical kinetics is the basis for the quantitative description of the course of a chemical reaction with time, that is of the reaction rate. Goal: establishing a functional relation between the rate of the reaction and the parameters influencing the reaction rate (concentrations and temperature).

Microkinetics and macrokinetics: The microkinetics is the kinetics of the pure chemical process. The macrokinetics includes heat and mass transport processes.
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Scope of chemical microkinetics

1. If the kinetics of a chemical reaction is known, it is possible to postulate a reaction mechanism which is a sequence of elementary steps that explains how the overall reaction proceeds.
A+ B C + D

reaction mechanism

A+ B E + F E+F C+D A+ B C + D

The reaction mechanism is only a hypothesis (model, proposal). We cannot know the reaction mechanism, we can only test it. The fact that a mechanism explains the experimental results (kinetic data, detection of intermediates, etc.) is not a proof that the mechanism is correct. 2. The knowledge of the reaction kinetics is an important factor for the choice of reactor type.
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Outline
Reaction rate: IUPAC and other useful definitions Parameters affecting the reaction rate: temperature and composition Effect of temperature: Arrhenius law Interpretation of the activation energy. Effect of composition: power law expression Elementary and composite reactions; molecularity and reaction order Methods for reaction order determination: method of integration (0, 1st, 2nd, nth order) and differential method (two variations). Method of isolation Single and multiple reactions (consecutive and parallel) Reversible and irreversible reactions

Reaction rate: IUPAC definition

According to IUPAC-guidelines, the reaction rate is the change of number of moles, caused by the reaction, per unit of time, referred to the stoichiometric coefficient i
i < 0 for reactants

1 A1 + 2 A2 3 A3 + 4 A4

i > 0 for products

1 dni r* = i dt

mol s

r* always >0 !

Here the reaction rate is an extensive magnitude (depends on the size sample).
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Reaction rate: useful definitions

It is advisable to refer the reaction rate to extensive properties characterizing the reaction system

r* r= (extensive property )
(for homogeneous reactions the volume V or the mass m of the reaction mixture, for heterogeneous reactions the interfacial surface S, the volume of the solid Vs, the mass m of the solid ms etc.)

This yields to several definitions of reaction rate, all intensive (invariant regarding the size of the system) and all interrelated :
r * 1 1 dni 1 dci mol r' = = = dt 3 V V i dt i m s

r* = r 'V = r ' ' m = r ' ' ' S = etc.

r' ' =
r' '' =

r * 1 1 dni mol = m m i dt Kgs

r * 1 1 dni mol = S S i dt m 2 s

etc.

Rate of formation (consumption) vs. reaction rate

1 A1 + 2 A2 3 A3 + 4 A4
r' = r * 1 dci = V i dt

i < 0 for reactants i > 0 for products

(intensive) rate of reaction, for V=cost

dc i ri = >0 dt
dci ri = >0 dt

(intensive) rate of product i formation (intensive) rate of reactant i consumption

If we use ri, we must always specify the reaction component to which it is referred and remember to include the appropriate sign !
H 2 + Br2 2 HBr 1 rH 2 = rBr2 = rHBr 2

3H 2 + N 2 2 NH 3 1 1 rN 2 = rH 2 = rNH 3 3 2

Graphic representation of the rate

A products

rA =

d [A] dt

Typical concentration profile in a batch reactor

[Ao] [A]
-rA = slope of the curve [A] vs. time

t
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Parameters which affect the reaction rate

For many reactions, the rate expression can be written as a product of a temperature-dependent term and a compositiondependent term, or

r = f1 (temperature) * f 2 (composition)
= k * f 2 (composition)

k = rate constant Determination of the activation energy

Determination of the reaction orders

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Effect of temperature on reaction rate: the Arrhenius law

The temperature-dependent term, the rate constant k, is well represented by the Arrhenius law:

k = k0 e

E / RT

k0 = pre-exponential factor E = activation energy

R = universal gas constant= 8,314 J/molK T = absolute temperature (K)

ln k = ln k0 E / RT
ln k

E= -Slope*R

Common range for E: 40-200 kJ/mol

I/T (K-1)

Activation energy and temperature dependency

1. Reaction with high activation energies are very temperaturesensitive; reaction with low activation energies are relatively temperature-insensitive. 2. Any given reaction is much more temperature-sensitive at low temperature than at high temperature.
high E k

ln k

low E

ln k

T= 1000 for doubling of rate

T= 87 for doubling of rate

1/T (k-1)

2000K 1000K

463K 376K

1/T (k-1)

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Activation energy
Following a thermodynamic approach, the activation energy can be interpreted as the energetic barrier between reactant and products. Between the initial states (reactants) and the final states (products) the potential energy passes through a maximum (activated complex), which corresponds to the top of the barrier. For reaction from left to right the barrier height is E1 and for the reaction from right to left it is E-1. These energies are related by the equation E1-E-1=H
Exothermic reaction (H<0)
Activated complex

Endothermic reaction (H>0)

Activated complex

E1
reactants

E-1 H
products

E1
reactants

E-1 H
products

The reaction coordinate corresponds to the pathway with minimum energy between reactants and products.
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Reaction coordinate

Reaction coordinate

Potential-energy surfaces and reaction coordinate

If the reaction occurs between two atoms A and B, the potential energy of the system can be described by a two-dimensional diagram (energy plotted vs. interatomic distance A-B). The potential energy is zero for big interatomic distances (A and B are not interacting). As the interatomic distance decreases, the potential energy first decreases (the attractive interactions prevail), then it reaches a minimum corresponding to the bond distance. Finally, for interatomic distances below the bond distance the potential energy rapidly increases due to repulsive interactions.
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Potential energy

Bond distance Interatomic distance A-B

Potential-energy surfaces and reaction coordinate

If the reaction occurs between three atoms, as in the reaction A-B + C A-C + B we need three parameters to describe it, for example the A-B, B-C and A-C distances or two distances and an angle. To plot energy against these three parameters a four-dimensional diagram would be necessary. Since this diagram cannot be visualized, it is necessary to use a series of three-dimensional diagrams, in each of which one parameter (for example the angle) is fixed. All these diagrams are sections of the four-dimensional surface. The reaction coordinate is the path Potential corresponding the minimum energy with energy respect to all the possible paths between reactants and products. The section through the minimum-energy dA-B path is the potential-energy profile.
E
Bond distance A-C Bond distance A-B

dA-C

reactants

Reaction coordinate

products

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Parameters which affect the reaction rate

For many reactions, the rate expression can be written as a product of a temperature-dependent term and a compositiondependent term, or

r = f1 (temperature) * f 2 (composition) r = k * f 2 (composition)

k = rate constant =k0e-E/RT

Determination of the reaction orders

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Effect of composition on reaction rate: power law rate expression

1 A1 + 2 A2 3 A3 + 4 A4
or generally

r = k * c1 * c2 * c3 * c4 * c5
r = k * ci
i mi

(5 = hidden factor in reaction e.g. catalyst, intermediate)

k : rate constant mi : partial reaction order with respect to the species i

(may be positive, negative, zero, full number or a fraction, mi are purely experimental quantities)
i

m = mi : overall reaction order

Sometimes the reaction rate does not follow a power law and the reaction order should not be used. Ex. k [ H ][ Br ]1 / 2

H 2 + Br2 2 HBr

rHBr =

k 2 + [ HBr ]/ [ Br2 ]

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Molecularity vs. reaction order

It is important to distinguish molecularity from reaction order: The reaction order is an empirical quantity obtained from the experimental rate law. The molecularity is the number of reactant particles (atoms, molecules, free radicals, ions) colliding together successfully in the microscopic chemical event. Molecularity must be 3: 3H 2 + N 2 2 NH 3 is not elementary,
H 2 + Br2 2 HBr could be elementary, but it is not

The molecularity is defined only for elementary reactions (reactions which occur in a single step, without intermediates), which are proposed as an individual step in a reaction mechanism. Non elementary reactions are referred as composite reactions. Only for the so-called elementary reactions: the reaction order mi corresponds to the stoichiometric coefficient i; 16 the overall order m is also designed as molecularity.

Determination of reaction order

Two main procedures exist:

1. Method of integration
This method deals with the integrated form of the rate equation. First a tentative decision of the reaction order is made, the corresponding differential reaction is integrated, and after mathematical manipulation, the plot of a certain concentration function versus time should yield a straight line. If the experimental data fit reasonably well the integrated equation, the suggested rate equation is accepted.

2. Differential method
This method deals directly with the differential rate equation. First, the reaction rate is measured by determining the slopes of concentration-time experimental curves. Then, the ln(rate) is plotted vs. the ln(conc). The slope of this straight line gives the reaction order.
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Determination of reaction order: integral method

zero-order reaction
A products
(irreversible unimolecular reaction) If the reaction is zero order, the rate of reaction is independent from the concentration:

d [A] 0 rA = = k [A] = k dt
Separating and integrating:
1,2 1

A0

d [A] = k dt
0

[A]

0,8 0,6 0,4 0,2 0 0 0,2 0,4 0,6 0,8 1 1,2 1,4 1,6 1,8 2

Slope = -k

[A] = kt + [A0 ]

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Determination of reaction order: integral method

1st order reaction

A products
(irreversible unimolecular reaction) If the reaction is of first order: Separating and integrating:

d [A] 1 rA = = k [A] dt

[A] = kt ln [A0 ]

d [A] = kdt [A]

d [A] [A] = k dt 0 A0
A t

1,2 1 0,8

[A] = [A0 ]e kt
ln[A]

1 0 0 -1 -2 -3

ln[A] = ln[A0 ] kt
0,2 0,4 0,6 0,8 1 1,2 1,4 1,6 1,8 2

[A]

0,6 0,4 0,2

-4 0 0 0,2 0,4 0,6 0,8 1 1,2 1,4 1,6 1,8 2 -5

Slope = -k
t
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Determination of reaction order: integral method

2nd order reaction

A products d [A] 2 = k [A] If the reaction is of second order: dt A t d [A] d [A] = kdt Separating and integrating: 2 [A]2 = k dt [A] 0 A0 rA =
(irreversible unimolecular reaction)

1 1 = + kt [A] [A0 ]
3 1,2 1

[A] = [A0 ] / (1 + kt[A0 ])

[A]
1,6 1,8 2 0,8 0,6 0,4 0,2

1/[A]

Slope = k
0 0,2 0,4 0,6 0,8 1

1,2

1,4

0 0 0,2 0,4 0,6 0,8 1

1,2

1,4

1,6

1,8

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Comparison of reaction rates

1.2 1 0.8

Same initial concentration [A0] and same k

0 order 1st order 2nd order

[A]

0.6 0.4 0.2 0 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2

The 2nd order reaction is slower than the 1st order reaction

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Determination of reaction order: integral method

d [A] n rA = = k [A] If the reaction is order: dt A t d [ A] d [A] = k dt = kdt n Separating and integrating: 0 A0 [ A] [A]n
nth
3

A products

nth order reaction

(irreversible unimolecular reaction)

[A]1-n

1 1 n 1 n [A] [A0 ] = kt (1 n)

for n1

Slope = k(n-1)
0 0,2 0,4 0,6 0,8 1 1,2 1,4 1,6 1,8 2

t The order n cannot be found explicitly from this equation, so a trial-and-error solution must be found. Select a value for n and calculate k. The value of n which minimizes the variation in k is 22 the desired value of n.

Determination of reaction order: differential method

This method deals directly with the differential rate equation

A products

rA =

d [A] n = k [ A] dt

1. Plot [A] vs. time 2. Determine the slope of this curve for selected concentration values. These slopes are the rates rA at these concentrations. 3. Plot ln(rA) vs. ln[A]. The slope give the reaction order n.

ln rA = ln k + n ln[A]

Experimental data

[A], mol/lit

ln (rA)

Slope = n

Tangents

Time, s

ln [A]

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Determination of reaction order: differential method:

Method of the initial rate

The differential mode may be applied in a different way, which is often called method of the initial rate. The reaction is run at different initial concentrations [A0] and the initial rates determined by measuring initial slopes. A double-logaritmic plot gives the initial reaction order ni.

[A] mol/lit

ln (rA0) Slope = ni

Time, s

This procedure avoids possible complications due to interference by products.

ln[A0]

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Determination of reaction order: differential method:

Comparison of the two variants

The reaction orders determined by the two variants of the differential method are not always the same for a given reaction. The fact that the reaction order with respect to time (n) is greater than the order with respect to initial concentration (ni), means that, as the reaction proceeds, the rate falls off more rapidly that if the order ni applied for the complete reaction. This means that some products are acting as inhibitors. Conversely, the products have a positive effect on the reaction rate and the reaction is said to be autocatalytic.

Slope = ni ln rA

Slope = n

The blue symbols correspond to rate obtained in individual runs; the green points correspond to the initial rates

ln [A]

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Comparison between integral and differential methods

In the integral method of analysis we guess a particular form of rate equation and we use its integrated form. In the differential method we test the fit of the rate expression to the data directly and without integration. There are advantages and disadvantages to each method. The integral method: + is easy to use - creates a prejudice in favor of integral orders and deviation from such orders might escape notice (if for example the reaction order is 1.8, the experimental data might fit
the second-order integrated equation within the experimental error).

+ it is recommended when testing specific mechanism or when the data are so scattered that we cannot reliably determine the rate with the differential method The differential method: + It is used when there are no previous information about the kinetics - requires more accurate or larger amount of data + It distinguishes between the two reaction order n and ni and therefore reveals information about the influence of products on the rates.
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Determination of reaction order:

isolation method
Up to now, we have assumed that the reaction rate only depends on the concentration of the reactant A and we have written: d [A] n
rA = dt = k [ A]

However, in general, the overall reaction rate is also affected by the concentration of other species, for example the B and C: d [ A] n m o
rA = dt = k [A] [B ] [C ]

How can we separate the effects of the different species on the overall reaction rate and determine the partial reaction orders? The isolation method or excess method.

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Determination of reaction order:

isolation method
If a reaction is of order m, n, o with respect to A,B and C, and if B and C are in excess of A, the apparent order determined by any of the methods described, will correspond to m. In fact:
A B+C

rA =

d [ A] n m o = k [A] [B ] [C ] dt

ln rA = ln k + m ln[A] + n ln[B ] + o ln[C ] ln rA = ln k '+ m ln[A]

The concentration of the components in excess will not change very much during the course of the reaction and can be considered constant.

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Single and multiple reactions

Up to now, we have described just single reactions, for ex.

A+ B C + D

In these cases, a single stoichiometric equation and a single rate equation are sufficient to describe the progress of the reaction:

r = k * ci
i

mi

When more than one stoichiometric reaction equation is needed to describe the system, more kinetic expressions are needed to follow the changing composition. These reactions are called multiple reactions. Multiple reactions may be classified as: consecutive reactions: parallel reactions:

A RS

R A S
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Irreversible consecutive reactions

A RS
With the assumption that all the reactions are 1st order:
rA = rR = rs = d [A] = k1 [A] dt

k1

k2

d [S ] = k 2 [R ] dt

d [R ] = k1 [A] k 2 [R ] dt

We will not consider the mathematical solution of this system of linear differential equations limiting ourselves to the qualitative/intuitive description of the concentration profiles of A, R and S.
1 0.8

k1 = k2
The maximum of R corresponds to the inflection point of S

[x]/[A0]

1. [A] always decreases 2. [R] exhibits a maximum

(two opposite processes, where in the long run the second always wins)

0.6 0.4 0.2 0 0

3. [S] always increases

Initial slope of S is zero

1 2

5 30

Irreversible consecutive reactions

ARS
The ratio k1/k2 affects the concentration profiles
1 0.8

k1

k2

[x]/[A0]

k1 k2
[x]/[A0]

0.8 0.6 0.4 0.2

0.6 0.4 0.2 0 0 1 2

k1 = 20k2

0
3 4 5

1 0.8

[x]/[A0]

0.6 0.4 0.2 0 0

k1 = k2 / 20

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Irreversible parallel reactions

R A S
k2 k1

With the assumption that all the reactions are 1st order: We will not consider the mathematical solution of this system of linear differential equations limiting ourselves to the qualitative/intuitive description of the concentration profiles of A, R 1 and S.
0.8

rA = rR = rS =

d [R ] = k1 [A] dt

d [A] = (k1 + k 2 )[A] dt

d [S ] = k 2 [A] dt

[x]/[A0]

1. [A] always decreases 2. [R] and [S] always increase 3. .

0.6 0.4 0.2 0 0 1 2

d [R ] [R ] = = k1 / k 2 d [S ] [S ]

32 5

Irreversible and reversible reactions

Up to now, we have described just irreversible reactions, for ex.

A + B C + D
However, any reaction is basically reversible. In practice a reaction is considered reversible only if the forward and reverse reaction can be measured.

k1

A + B C + D
k 1

k1

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Reversible reactions
We consider only the simplest case: reversible reaction of 1st order in both directions:
1

A P
[x]/[A0]
k 1

k1

0.8 0.6 0.4 0.2 0 0 1 2

[ P ] eq

rA =

d [A] = k1 [A] k 1 [P ] dt

[ A ] eq

After a certain time the system reaches a dynamic equilibrium state and the overall reaction rate is zero.

k1 [P ]eq = = K eq k 1 [A]eq

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Books
Octave Levenspiel Chemical Reaction Engineering, third edition, Wiley (1999). Keith J. Laidler Chemical Kinetics, third edition, Harper & Row, New York (1987). http://www.ltc1.uni-erlangen.de/htdocs/e/index.htm Chapter III-Kinetics of Chemical Reactions Microkinetics.

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Vocabulary
activated complex activation energy batch reactor composite reactions consecutive reactions differential method elementary reactions energetic barrier excess method extensive magnitude heat and mass transport processes method of integration intensive magnitude irreversible reactions isolation method Macrokinetics Mechanism method of the initial rate Microkinetics Molecularity multiple reactions overall reaction order parallel reactions partial reaction order power law rate expression pre-exponential factor reaction coordinate Reaction rate reversible reactions single reactions slope aktivierter Komplex Aktivierungsenergie Satzreaktor, diskontinuierlich betriebener Rhrkessel nicht elementare Reaktionen sequentielle Reaktionen, Konsekutivereaktionen Differentialmethode Elementarreaktionen Energiebarriere berschussesmethode Extensive Gre Stoff- und Wrmetransport Integralmethode intensive Gre irreversible Reaktionen Isolirmethode Makrokinetik Mechanismus Anfangsreaktionsgeschwindigkeitmethode Mikrokinetik Molekularitt Mehrstufenreaktionen Gesamtordnung Parallelreaktionen Teilordnung Potenzansatz Stofaktor, Preexponentieller Faktor Reaktionskoordinate Reaktionsgeschwindigkeit, Reaktionsrate reversible Reaktionen Einstufereaktion Steigung

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Exercises
1. Compare the formation and consumption rates for all the products and reactants involved in the following reactions: A + 2B P 3A + 2B 3C + D +2E Write the reaction rate of the following equation assuming it to be an elementary reaction: A + 2B P (irrev.) A + 2B P (rever.) a) A zero order reaction is 50% complete in 20 minutes. How much time will it take to complete 90%? b) How much time will take a first order reaction with the same rate contant to half the initial concentration of reactant?
37

2.

3.

Exercises
4. Reactant A decomposes in a batch reactor: A products. The composition of A in the reactor is measured at various times. Find a rate equation to represent the data. Time (sec) [A] (mol/liter) 0 20 40 60 120 180 300 10 8 6 5 3 2 1
[A] (mol liter )
-1 12 10 8 6 4 2 0 0 50 100 150 200 250 300 350

time (sec)

38

Integral method: guess 1st order kinetics. This means that ln[A]0/[A] vs time should give a straight line

[A]0 ln [A]

= kt

Time (sec) 0 20 40 60 120 180 300

[A] (mol/liter) 10 8 6 5 3 2 1

ln [A]0/[A] 0 0.2231 0.511 0.6931 1.204 1.609 2.303

The data do not fall on a2,5 straight line: 1st2 order rejected
ln [A]0/[A]
1,5

0,5

0 0 50 100 150 200 250 300 350

time (sec)
39

Integral method: guess 2nd order kinetics: This means that 1/[A] vs time should give a straight line

1 1 = + kt [A] [A0 ]

Time (sec) 0 20 40 60 120 180 300

[A] (mol/liter) 10 8 6 5 3 2 1

1/[A] 0 0.2231 0.511 0.6931 1.204 1.609 2.303

1/[A]

The data do not fall on 1,2 a straight line:

1

2nd order rejected

0,8 0,6 0,4 0,2 0 0 50 100 150 200 250 300 350

time (sec)
40

Differential method 1. Draw a smooth curve to represent the data 2. Determine the slopes rA= -d[A]/dt at different concentrations

Time (sec) 0 20 40 60 120 180 300

[A] (mol/liter) 10 8 6 5 3 2 1

rA 10/92=0,1087 10/92=0,1097 8,5/140=0,0607 8/160=0,0500 6/240=0,0205 4,5/260=0,0174

[A] (mol liter )
-1

12 10 8 6 4 2 0 0 50 100 150 200 250 300 350

rA=10/92

rA=6/240

time (sec)

41

3.

Plot lnrA vs ln[A]: the slope corresponds to the reaction order, the intercept corresponds to lnk
rA ln rA
0 0,0000 -0,5 -1

[A] Time (sec) (mol/liter ) 0 20 40 60 120 180 300 10 8 6 5 3 2 1

0,5000

1,0000

1,5000

2,0000

2,5000

0,1087 0,1097 0,0607 0,0500 0,0205 0,0174

-2,2192 -2,8016 -2,9957 -3,6889 -4,0566

ln(rA)

-1,5 -2 -2,5 -3 -3,5 -4 -4,5

-2,4027

y = 1,186x - 4,921 R2 = 0,996

ln[A]

nA=1,2 k=e-4,921=0,007 (liter0,2/mol0,2 s)

rA= -d[A]/dt = 0,007 [A]1,2 (mol/liter s)

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