KULIAH

TEKNIK REAKSI KIMIA

HOMOGEN

Jurusan Teknik Kimia

FT-Unsri
1.1. Basis of Kine-cs
1.2. Constant-Volume Batch Reactor
1.3. Varying-Volume Batch Reactor

Lecture 1.1 Basis of Kinetics

The Rate Equation

Suppose a single-phase reaction：
The most useful measure of reaction rate for reactant A is

The rates of reaction of all molecules are related by

Temperature

Experience shows that the rate of reaction is influenced by the composition and energy
of the material.
26
Lecture 1.1 Basis of Kinetics

The Rate Equation

Suppose a single-phase reaction：
The most useful measure of reaction rate for reactant A is

The rates of reaction of all molecules are related by

Temperature

Experience shows that the rate of reaction is influenced by the composition and energy
of the material.
27
Lecture 1.1 Basis of Kinetics

Single and Multiple Reactions

When a single stoichiometric equation and single rate equation are chosen
to represent the progress of the reaction, we have a single reaction.

When more than one stoichiometric equation is chosen to represent the

observed changes, then more than one kinetic expression is needed to
follow the changing composition of all the reaction components, and we
have multiple reactions.

Series reactions, more complicated,

Parallel reactions,

28
Lecture 1.1 Basis of Kinetics

Elementary and Nonelementary Reactions

aA + bB cC + dD

The rate-controlling
mechanism involves The number of collisions
The number of
the collision or is proportional to the
collisions of molecules
interaction of a A concentration of
A with B is proportional
molecules with b B reactants in the mixture
to the rate of reaction
molecules (T constant)

Such reactions are called elementary reactions.

Otherwise, the ones are called nonelementary reactions.

Mass interaction law

For an elementary reaction: -rA = k CAa CBb

29
Lecture 1.1 Basis of Kinetics

Representation of an Elementary Reaction

any measure equiva-
lent to concentration

the order unchanged, but k different

However,
I
AMBIGUITY:
correct -r expression?
k1 refers to ?

II 1) write the stoichiometric

equation followed by the
complete rate expression.
2) give the units of the rate
constant

30
Lecture 1.1 Basis of Kinetics

Representation of a Nonelementary Reaction

Stoichiometry: Rate:

Develop a multistep reaction model to explain the kinetics

Br2 → 2Br ·
Br · and H ·
Br · + H2 → HBr + H · unobserved intermediates
H · + Br2 → HBr + Br ·

Suggested by chemistry of the materials

Determined by experiments

31
Lecture 1.1 Basis of Kinetics

Molecularity and Order of Reaction

Must be integer
 The molecularity of an elementary reaction (must be an elementary reaction)
is the number of molecules taking part in the reaction.
 This has been found to have the values of one, two, or occasionally three.

ath order with respect to A bth order with respect to B nth order overall

k: rate constant, (time)-1(concentration)1-n

 For non-elementary reaction: a, b, . . . , d are not necessarily related to the
stoichiometric coefficients.

 We call the powers to which the concentrations are raised the order of the Reaction.

A fractional value
is allowable
32
Lecture 1.1 Basis of Kinetics

Kinetic Model Development

 Type 1

A B: A X X B

For unseen and unmeasured intermediate X

Pseudo-steady-state approximation
-rX = 0

 Type 2

A+B C: A+B X X C

X C is rate-determining step
Quasi-equilibrium approximation
k1
A+B X K=k1/k2=[X]/([A][B])
k2
33
Lecture 1.1 Basis of Kinetics

Kinetic Model Example

(8)

(9)

(10) (11)

Type 1, steady-state
approximation

d[X]/dt ≈ 0 (12) (13)

Michaelis-Menten
(14)
type

34
Lecture 1.1 Basis of Kinetics

Temperature Dependency from Arrhenius' Law

Activation energy
Arrhenius’ Law J/mol

Frequency factor

Same concentration

Actually,
Mask pre-
sensitive
exponential term
Collision and transition
state theories

35
Lecture 1.1 Basis of Kinetics

Activation Energy and Temperature Dependency

1, Reactions with high activation

energies are very temperature-
sensitive.

2, Reactions are much more

temperature-sensitive in low
temperature range than in a
high temperature range.

Fig 1.1 Sketch showing temperature dependency of the reaction rate

36
Lecture 1.2 Constant-Volume Batch Reactor

Constant-Volume Constant-density
Constant-Volume
of reaction mixture reaction system

Most liquid-phase reactions and all gas-phase

reactions occurring in a constant-volume bomb

(15) (16)

For gas reactions with ri is to follow the change

changing numbers of moles in total pressure π

37
Lecture 1.2 Constant-Volume Batch Reactor

The Conversion
XA: the conversion of A

(17)

(18)

 Irreversible Unimolecular-Type First-Order Reactions

(19)

Suppose the first-order rate equation,

(20)

38
Lecture 1.2 Constant-Volume Batch Reactor

Separating and integrating,

(21)

In terms of conversion ( Eqs. 17 and 18) and the rate equation Eq. 20,

Rearranging and integrating,

21 or 22

(22)

Fig 1.2 Test for the first-order rate equation

39
Lecture 1.2 Constant-Volume Batch Reactor

 Irreversible Bimolecular-Type Second-Order Reactions

(23)

Note: The reacted amounts of A and B at any time t are equal, i.e., CA0XA= CB0XB,

Let M = CB0/CA0 be the initial molar ratio of reactants,

After separation and integration it becomes

40
Lecture 1.2 Constant-Volume Batch Reactor

After breakdown into partial fractions, integration, and rearrangement, the final result in
a number of different forms is

CA0  CB0

(24)

Fig 1.3 Test for the bimolecular mechanism A + B → R with CA0 ≠ CB0

41
Lecture 1.2 Constant-Volume Batch Reactor

Reactants are introduced in their stoichiometric ratio

go back to the original diff-

erential rate expression

For a second-order reaction with equal initial CA0 and CB0 or for the reaction

the defining second-order differential equation becomes

(25)

On integration it yields

(26)

42
Lecture 1.2 Constant-Volume Batch Reactor

Rate Equations of nth Order reaction

When the mechanism of reaction is not known

(27)

On separation and integration it yields

(28)

Trial-and-error solution select a value for n and calculate k. The value of n which minimizes
the variation in k is the desired value of n

n>1 the reaction never goes to completion

Curious features
the reactant concentration will fall to zero and
n<1
then become negative

43
Lecture 1.2 Constant-Volume Batch Reactor

Zero-Order Reactions high concentration

concentration independent
(29)
radiation intensity,
available surface

Integrating and noting that CA can never become negative

(30)

30

30

Fig 1.4 Test for a zero-order reaction

44
Lecture 1.2 Constant-Volume Batch Reactor

Overall Order of Irreversible Reactions from the Half-Life t1/2

If CB0/CA0 = β/α…, at any time CB/CA = β/α…

(31)

Integrating for n ≠ 1 gives

Half-Life t1/2 (Time needed for CA /CA0 =1/2) is

32a

(32a)

45
Lecture 1.2 Constant-Volume Batch Reactor

Irreversible Reactions in Parallel

(33)

(34)

(35)

Eq. 33, which is of simple first order, is integrated to give

(36)

dividing Eq. 34 by Eq. 35 we obtain the following

(37)

46
Lecture 1.2 Constant-Volume Batch Reactor

36
37

Fig 1.6 Plotting for Eqs. 36, 37 Fig 1.7 Concentration-time curves for Parallel reactions

47
Lecture 1.2 Constant-Volume Batch Reactor

Irreversible Reactions in Series

First consider consecutive unimolecular type first-order reactions

(38)

(39)

(40)

Start with a concentration CA0 of A, no R or S present. Integrate Eq. 38,

(41)

Substitute CA in Eq. 39

(42) (43)

48
Lecture 1.2 Constant-Volume Batch Reactor

Because there is no change in total number of moles,

(44)

In general, for any number of reactions in series it is the slowest

step that has the greatest influence on the overall reaction rate

Differentiate Eq. 43 and set dCR/dt = 0, CR, max occurs

(45) (46)

49
Lecture 1.2 Constant-Volume Batch Reactor

41

44
Evaluate k1 and k2

46 43

45

Fig 1.8 Typical concentration-time curves for consecutive first-order reactions

50
Lecture 1.2 Constant-Volume Batch Reactor

First-Order Reversible Reactions

Irreversible reactions can be considered as reversible ones with large equilibrium constants.

equilibrium constant (47)

Starting with M = CR0/CA0

(48)

Now at equilibrium dCA/dt = 0, Hence

(49) and (50)

Combining the above three equations (48, 49, 50)

(51)

51
Lecture 1.2 Constant-Volume Batch Reactor

Reversible i

(51) 51

special case CAe=0 or

XAe=1 or
KC= ∞

Irreversible ii

(21) (22)
21-22

Fig 1.9 Test for the unimolecular type reversible (i) and irreversible (ii) reactions

52
Lecture 1.2 Constant-Volume Batch Reactor

Second-Order Reversible Reactions

For the bimolecular-type second-order reactions

(52a) (52c)

(52b) (52d)

When CA0=CB0 and CR0=CS0=0

53

(53)

Fig 1.10 Test for the reversible bimolecular reactions

53
Lecture 1.3 Varying-Volume Batch Reactor

The progress of the reaction is followed

by noting the movement of the bead with
time

Fig 1.11 A varying-volume batch reactor

Isothermal constant Volume is linearly related

pressure operations to the conversion (54)

(55)
Fractional change in volume of the system between no
conversion and complete conversion of reactant A

pure A 50% A
Example
50% Ar

54
Lecture 1.3 Varying-Volume Batch Reactor

Noting that (56)

On combining with Eq. 54

(57)

(isothermal varying-volume systems)

In general

Replace V (Eq. 54) and NA (Eq. 56)

(58)

in terms of volume (Eq. 54)

(59)

55
Lecture 1.3 Varying-Volume Batch Reactor

 Zero-Order Reactions

(60)

 First-Order Reactions

Replace XA by V from Eq. 54 and integrate it gives

(61)

 Second-Order Reactions
or

(62)

56