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ICE 204 KINETIKA & KATALISIS CHAPTER 3

CHP 3 NON CATALYTIC & HOMOGENEOUS REACTION KINETICS


This section covers homogeneous reaction rate expressions, the rates of irreversible, reversible, and complex reactions Missen Chapter 4 5 + Smith Chapter 2

3.1 Rate of SIMPLE homogeneous reactions the effect of reactant concentrations and reaction temperature (T).

A+ B

k C + D

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ICE 204 KINETIKA & KATALISIS CHAPTER 3

The rate law for HOMOGENEOUS reactions : r [=] mol.V-1.time-1 = k.CAn.CBm * in most cases, ONLY reactant concentrations affect r ** n and m can be different with and (for elementary reaction >> n-m = - ; but NOT vice versa) *** elementary reaction order is normally 1 or 2 **** k, n, and m must be obtained by experiment ***** the relation between each component rates: (power law)

(rA )

( rB )

(rC )

(rD )

= r

m = k.C n CB A

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ICE 204 KINETIKA & KATALISIS CHAPTER 3

k = A.e

Ea RT

(Arrhenius Equation)

NOTE : in addition to the power law (as an empirical rate law) above, there is also a rate law constructed based on concepts of reaction mechanism. Such rate law is called fundamental rate law (see Chp 7 Missen). The latter can be extrapolated outside the experimental conditions range. eg:

CO( g ) +

1 O2( g ) 2

Pt CO2( g )

a (fundamental) rate law derived from reaction mechanism is :

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ICE 204 KINETIKA & KATALISIS CHAPTER 3

k(T).CCO .C1/2 O2 ( rCO ) = [1 + K(T).CCO + K '(T ).C1/2 ] O2


3.1.1. First Order Reaction

r = k.CA In constant volume batch reactor, at t = 0 CA = CAo :

CA vs t = ? k = ??

dC A = ( rA ) = k.CA dt

3.1.2. Second Order Reaction

r = k.CA2

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ICE 204 KINETIKA & KATALISIS CHAPTER 3

# in constant volume batch reactor at t = 0 CA = CAo:

CA vs t = ? k = ??

dC A = ( rA ) = k.C2 A dt

r = k.CA.CB ## in constant volume batch reactor at t = 0 CA = CAo, CB = CBo:

CA vs t = ?

dC A = (rA ) = k.C A .CB dt

k = ?? (go to page 14)

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ICE 204 KINETIKA & KATALISIS CHAPTER 3

EXAMPLE # 1: At 518 oC, acetaldehyde vapor decomposes into methane and carbon monoxide:

CH 3CO

k CH 4

+ CO

Hinselwood & Hutchison (1962) carried out an experiment in a constant-volume batch reactor. The initial pressure of CH3CO was 48.4 kPa, and the following increases of pressure (P) were noted t (s) P (kPa) 42 4.5 105 9.9 242 17.9 480 25.9 840 32.5 1440 37.9

Determine the reaction order, and calculate the rate constant (in pressure and molar units).

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ICE 204 KINETIKA & KATALISIS CHAPTER 3

3.1.3. Third Order Reaction

r = k.CA2.CB In constant volume batch reactor at t = 0 CA = CAo, CB = CBo:

CA vs t = ?

dC A = ( rA ) = k.C2 .CB A dt

k = ?? >>> Read Missen page 72 75 !!

3.1.4. n-th Order Reaction

r = k.CAn In constant volume batch reactor at t = 0 CA = CAo:

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ICE 204 KINETIKA & KATALISIS CHAPTER 3

dC A = ( rA ) = k.Cn A dt
For n = 1 and n 1 find CA vs t = ? k = ??

SUMMARY: (i) reaction order 1 or 2 is normally for simple, elementary reactions (ii) reaction order 0 is normally NOT observed for reaction in a single-phase fluid, but it may occur in enzyme reactions and in the case of gas (solid catalyzed) reactions refer to Missen Chp 8 & 10
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ICE 204 KINETIKA & KATALISIS CHAPTER 3

(iii)

reaction order 3 is rare, but includes: the gas phase reaction between NO and O2 or H2 or Cl2 or Br2; acids or bases catalyzed reactions in aqueous phase

(iv)

reaction order may be other numbers (even negative!), eg under certain conditions the decomposition of CH3COH is 3/2-order; reaction between CO (1-order) and Cl2 (3/2-order) to form COCl2.

(v)

reaction rate may also depend on the product concentration; if the order is + the effect is known as autocatalysis, but if the order is the effect is called product inhibition (common in

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ICE 204 KINETIKA & KATALISIS CHAPTER 3

catalytic reaction). This effect can be known if measurements at low reactant-conversions are conducted. Refer to Missen Chp 8
3.1.5. Effect of T

T affects the rate as indicated in Arrhenius equation. The values of A and EA may be estimated using the linearized form

Ea 1 ln k = ln A ( ) R T
EXAMPLE # 2:

Determine the Arrhenius parameters for the reaction

C2 H 4

+ C4 H 6
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k C6 H10

ICE 204 KINETIKA & KATALISIS CHAPTER 3

The following data was collected by Rowley & Steiner (1951):

T (K) 760 780 803 832 822 823 826

k (L.mol-1.s-1) 0.38 0.56 0.94 1.57 1.34 1.23 1.59

T (K) 863 866 867 876 894 921

k (L.mol-1.s-1) 3.12 4.05 3.47 3.74 5.62 8.20

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ICE 204 KINETIKA & KATALISIS CHAPTER 3

3.2 Rate of REVERSIBLE homogeneous reactions Many reactions are reversible, in which reaction thermodynamics apply (remember Chapter 2!). The rate only measures changes PRIOR TO the equilibrium condition. In the way to equilibrium, the rate diminishes and near equilibrium r 0. Examples of reversible reactions:

n C4 H10

k1 i C4 H10 k 1

SO2

1 O2 2

k2 SO3 k 2

CH 3COOCH 3

k3 CH 3COOH + H 2O k 3

+ CH 3OH

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EXAMPLE # 3: The isomerization of A to D follows first order in both directions


k1 D A k 1

Following data were obtained at a certain T from a constant-volume batch reactor: t (h) 100CA/CA0 0 100 1 72.5 2 56.8 3 45.6 4 39.5 30

find the values of k1 and k-1.

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Table 2.10 Rate Equation for simple reactions (p 82 Smith read also p 62 74)

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ICE 204 KINETIKA & KATALISIS CHAPTER 3

3.3 Rate of COMPLEX homogeneous reactions Types of complex reactions: - Parallel reactions, eg:

C2 H 5OH C2 H 5OH C6 H 5 NO2 C6 H 5 NO2 C6 H 5 NO2 +

C2 H 4

H 2O H2 + H 2O + + H 2O H 2O

C2 H 4 O +

HNO3

o C6 H 4 ( NO2 ) 2 m C6 H 4 ( NO2 ) 2 p C6 H 4 ( NO2 ) 2

+ HNO3 + HNO3

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ICE 204 KINETIKA & KATALISIS CHAPTER 3

- Series reactions, eg:

(CH 3 ) 2 CO CH 4
CH 2CO
- Series & reversible, eg:

+ CH 2CO
+ CO

1 C2 H 4 2

N 2O5

N 2O4

1 O2 2

N 2O4
- Series & parallel, eg:

2 NO2

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ICE 204 KINETIKA & KATALISIS CHAPTER 3

CH 4

+ O2

HCHO + CO +

H 2O H 2O

HCHO + 1/ 2O2 CH 4
NOTE:

+ 2O2

CO2

+ 2 H 2O

For a complex reaction system, we can find the maximum number of linearly independent chemical equations (TTSL reaction in Azas TK). The number tells us the minimum number of species that need to be analyzed in a kinetic study. However, those equations have NOTHING to do with the kinetics (real

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reactions or mechanism). But, they can be useful for mass balance purposes. Read 5.2.1 Missen p 90!! 3.3.1 Parallel reactions The (most common) conversion, yield and selectivity in parallel reactions:

A + A +
(C A0 C A ) Conversion = C A0
CP Yield of P = C A0

B P B S
CP Selectivity to P = (C C ) A0 A
Yield = conversion x selectivity

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ICE 204 KINETIKA & KATALISIS CHAPTER 3

EXAMPLE # 4: Describe how experiments in a constant-volume batch reactor should be carried out to measure k1 and k2 for these 1st order parallel reactions:

A B + C
A D +
3.3.2 Series reactions
k1 A B

rB = k1.CA rD = k2.CA

k2 C

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Typical concentration profile in a batch reactor

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EXAMPLE # 5: Describe how experiments in a constant-volume batch reactor should be carried out to measure k1 and k2 for a 1st order series reactions? HOMEWORK 1. For the series reaction above, calculate the time at which the CB is maximum, and what is the CB maximum if initially CA = CA0 and CB = CC = 0.
k1 A R is carried out 2. An elementary reversible liquid phase reaction k 1

isothermally in a constant-volume batch reactor. After 8 minutes, A conversion is 1/3 and at equilibrium A conversion is 2/3. Calculate the rate constants.

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ICE 204 KINETIKA & KATALISIS CHAPTER 3

3.3.3 Series-parallel reactions (see Levenspiel, Chemical Reaction Engineering, 3rd edition,
p 188 & 190)

A +

k1 R

R + B

k2 S

If the individual reactions follow 1st order in respect to each reactant: (-rA) = k1.CA.CB (-rB) = k1.CA.CB + k2.CR.CB Mol balances: CA0 CA = CR CR0 + CS CS0 CB0 CB = CR CR0 + 2(CS CS0) rR = k1.CA.CB - k2.CR.CB rS = k2.CR.CB

MORE EXERCISES: Hill examples 5-1, 5-3 up to 5-6


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