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Dobereiner (1829), Wilhelmy (1850) supposed that reaction rates would be simply related to the stoichiometry of the reaction 1878: Van¶t Hoff showed that the rate equation had little correlation to stoichiometry.

Reaction
4 PH3 2 AsH3 P4 + 6 H2 As2 + 3 H2 P2O5 + 3 H2O
H

Rate Equation
rPH3 ! k 3 ™ [PH3 ] rAsH3 ! k 4 ™ [ AsH3 ] rPH3 ! k 5 ™ [PH3 ] ™ [O 2 ]1/ 2 rS ! k 6 ™ [suksrose ] ™ [H ] rAc ! k 7 ™ [CH3COOR] ™ [H ] rAc ! k 8 ™ [CH3 COOH] ™ [ROH] ™ [H ] rC 2H3 ClO 2 ! k 9 ™ [C2H3ClO2 ] r r
Fe 3 
Fe
3

2 PH3 + 4 O2

C12H22O11 + H2O €€ p C6H12O6 + C5H9O5CH2OH € CH3COOR + H2O €€ p CH3COOH + ROH € CH3COOH + ROH €€ p CH3COOR + H2O € ClCH2COOH + H2O HOCH2COOH + HCl 2 FeCl3 + SnCl2 KClO3 + 6 FeO FeCl2 + SnCl4 KCl + 3 Fe2O3
H H

! k10 ™ [Fe3  ]2 ™ [Sn2  ] ! k11 ™ [Fe2  ] ™ [ClO3 ] 

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Van¶t Hoff: the kinetics of a reaction related to molecularity, i.e. the number of molecules participating in some critical step in the reaction Unimolecular reaction: Cyclopropane Propylene Bimolecular reaction: *OH + C2H6 H2O + C2H5* Termolecular reaction: CH3* + CH3* + N2 C2H6 + N2
4 PH3 P4 + 6 H2
rPH3 ! k 3 ™ [PH3 ]

: all first-order reactions are unimolecular : all second-order reactions are bimolecular : all third-order reactions are termolecular Critical step: what about?

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When a reaction involves the formations and subsequent reactions of intermediate species, it is not uncommon to find a non-integer order or other type of kinetic expression: CH3CHO CH4 + CO oC: -r 3/2 At +/- 500 CH3CHO = k.CCH3CHO H2 + I2 (CH3)2N2 At low pressures below 50 mmHg: At high pressures greater than 1 atm: -rN2 ~ CAZO2 -rN2 ~ CAZO
An elementary reaction is defined as a chemical reaction going from reactants to products without going through any stable intermediates. In this context, a species is said to be stable if it has lifetime longer than ~10-11 sec
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2 HI

k1 ™ k 3 ™ CI2 ™ CH2  rHI ! k 2  k 3 ™ CH2

C2H6 + N2

Reactive Intermediates are by definition reactive. The undergo many reactions David Chapman (1913), Muriel Chapman & Max Bodenstein (1907): H2 + Cl2 2 HCl Cl ‡ as reactive intermediates Every overall chemical reaction can be divided into a sequence of elementary reaction. Every reaction has a mechanism, defined as the sequence of elementary reactions that occur at appreciable rates when the reactants come together and react to form products
H

CH3CH2HC=CH2 €€ p CH3HC=CHCH3 €

Mechanism:

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A + B ²2p P +Q

r2 = k2 [A] [B] -rA = k2 [A] [B] -rB = k2 [A] [B]

+rP = k2 [A] [B] +rQ = k2 [A] [B]

-rA = -rB = +rP = +rQ 2 A ²4p P +Q r4 = k4 [A] [A] = k4 [A]2 +rP = k4 [A]2 +rQ = k4 [A]2 rA/2 = +rP/1 = +rQ/1 = k4 [A]2

-rA = 2k4 [A]2

-

Collosion Partner
Incorrect: A ²1p P Correct: A + X²1p P + X -rA = k1 [A]

-rA = k1 [A] [X]

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A
€ I €3 A H € € n €€ 
2 1

P

P  H

For each reaction:
r1 ! r2 ! r3 !
1 [ A] [ 2 [I] 3 [I] 

]

For each species: rA ! r1  r2 r  ! r1  r2  r3 rI ! r1  r2  r3 rP ! r3

In a constant volume batch reactor:
d[ A ] ! k1 ™ [ A ] ™ [H ]  k 2 ™ [I] dt d[H ] ! k1 ™ [ A ] ™ [H ]  k 2 ™ [I]  k 3 ™ [I] dt d[I] ! k1 ™ [ A ] ™ [H ]  k 2 ™ [I]  k 3 ™ [I] dt d[P] ! k 3 ™ [I] dt
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A
€ I €3 A H € € n €€ 
2 1

P

P  H

According to pseudo-steady-state approximation, one can compute accurate values of the concentrations of all of the intermediates in a reaction by assuming that the net rate of the intermediates is negligible.

d[  ] ! dt d[I] ! dt

™[ ]™[  

]

™ [I] 

™ [I] $ 0   [I] ! ™[ ]™[ 

™[ ]™[

]

™ [I] 

™ [I] $ 0 

]

d[ ] ! dt

™ [I] !

™ 

™[ ]™[ ]  

p

! o ™[ ]™[ 

]

According to stoichiometry: 

rA ! rp ! k o ™ [ A ] ™ [H ]

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(CH3)2N2 C2H6 + N2 AZO C2H6 + N2 At low pressures below 50 mmHg At high pressures greater than 1 atm : : -rN2 ~ CAZO2 -rN2 ~ CAZO

Reaction mechanism [F.A. Lindemann,Trans. Faraday Soc., 17, 598 (1922)] (CH3)2N2 + (CH3)2N2 ²k1p (CH3)2N2 + [(CH3)2N2]* (CH3)2N2* + (CH3)2N2 ²k2p (CH3)2N2 + (CH3)2N2 (CH3)2N2* ²k3p C2H6 + N2 PSSH: rAZO*= k1.CAZO2 - k2.CAZOCAZO* -k3.CAZO*| 0 Then, rAZO*= k1.CAZO2 rAZO*= -k2.CAZOCAZO* rAZO*= -k3.CAZO*
k1 ™ C ZO 2   C ZO ! k 2 ™ C ZO  k 3

k1 ™ k 3 ™ C ZO 2 rN2 ! k 3 ™ C ZO ! k 2 ™ C ZO  k 3

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2 N2O5 Mechanism:
k

4 NO2 + O2

1 €€p € X  N2O5 n€ € NO2  NO3  X €

k2

3 NO2  NO3 €€ p NO  O 2  NO2 € 4 NO  NO3 €€ p 2 NO2 €

k

k 

What rate expression is consistent with this mechanism?
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2 NO + 2 H2
k

N 2 + 2 H2 O

Mechanism A

1 € : 2 NO  H2 €€p N2  H2O 2 2 € H2O 2  H2 €€ p 2 H2O

k

MechanismB

3 €€ p € : 2 NO n€ € N2O2 €

k

k4

5 € N2O2  H2 €€ pN2  2 H2O2 2 € H2O2  H2 €€ p 2 H2O

k

k 

What rate expression is consistent with these mechanism?
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H2+ Br2 Mechanism: Initiation Propagation

2 HBr

X + Br2 ²1p 2 Br‡ + X Br ‡ + H2 ²2p HBr + H ‡ H ‡ + Br2 ²3p HBr + Br ‡ X + 2 Br ‡ ²4p Br2 + X H ‡ + HBr ²5p H2 + Br ‡

Terminatiion 

What rate expression is consistent with this mechanism?
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H-Il4.3 Mekanisme berantai di bawah ini diusulkan untuk reaksi dekomposisi ozon: Inisiasi : k1
Cl 2  O 3 €€p ClO y  ClO 2 y

Propagasi

:

k2 ® ClO 2 y  O 3 €€p ClO 3 y O 2 ± ¯ k3 ± 3 y O 3 €€p ClO 2 y 2O 2 ClO °

Terminasi

:

k4 ® ClO ± 3 y ClO 3 y €€p Cl 2  3O 2 ¯ k5 ± ClO y ClO y €€p Cl 2  O 2 ° 

Bagaimana persamaan laju reaksi dekomposisi ozon menurut mekanisme ini?  Hasil percobaan pada suhu rendah menunjukkan bahwa persamaan laju dekomposisi ozon mengikuti persamaan: 3 1 d[O 3 ] 2 ™ [O ] 2  ! k ™ [Cl 2 ] 3 dt Apakah mekanisme yang diusulkan konsisten dengan hasil percobaan ini?
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H4.1 Houser & Lee [J. Phys. Chem., 71 (3422), 1967] have studied the pyrolysis of ethyl nitrate using a stirred flow reactor. They have proposed the following mechanism for the reaction. Initiation :
€€p € y

Propagation

:

2 C2H5O y €€ p CH3 y CH2O € 3 CH3 y C2H5 ONO2 €€ p CH3NO2  C 2H5O y €

k

k

Termination

:

4 € 2C 2H5O y €€ p CH3CHO  C 2H5 OH

k 

What rate expression is consistent with this mechanism?
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Ex.7-2 The thermal decomposition of ethane to ethylene, methane, butane, and hydrogen is believed to proceed in the following sequence:
Initiation : €p C2H 6 € 1 2CH 3 y Pr opagation :
2 CH3 y C2H 6 €€p CH 4  C2 H5 y 3 C2H 5 y €€p C2 H 4  H y 4 H y C2 H 6 €€p C2H 5 y  H 2

k

k

k

k

Ter min ation :
5 2C2H 5 y €€p C4H10

k

Use PSSH to derive a rate law for the formation of ethylene
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P7-3B Hydrogen radicals are important to sustaining combustion reactions. Consequently, if chemical compounds that can scavenge the hidrogen radicals are introduced, the flame can be extinguished. While many reactions occur during the combustion process, we shall choose CO flames as a model system to ilustrate the process [S. Senkan et al., Combustion and Flame, 69, p. 113 (1987)] . In the absence of inhibitors: O 2 € O y O y €p The last two reactions are rapid compared to the firs two. When HCl is introduced to the flame, the following additional reactions occur:
H 2O  O y € 2OH y €p CO  OH y € CO 2  H y €p H y  O 2 € OH y  O y €p

H  HCl € €

H 2  Cl HCl

€ H Cl €

Derive a rate law for consumption of CO for both when no retardant present and when HCl is introduced

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P7f ll r l i f t ldehyde i i equence:
k

elieved t t

e l

e

rdi

t the

€p H 3 y  H y H3 H € 1
2 H 3 y  H 3 H €€p H 3 y  3 H y  H 3 H €€p H 3 y 2 4 2 H 3 y €€p

k 

H4  H2

k

k

2H6

Derive the r te ex ressi n f r the r te f disa

earance f acetaldehyde

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P7-7C One of the major reasons for engine oil degradation is the oxidation of the motor oil. To retard the degradation process, most oils contain an antioxidant [see Ind. Eng. Chem. 26, 902 (1987)].
I 2 €€p 2I y
 

Without an inhibitor to oxidation present, the suggested mechanism at low temperature is:

k

€p I y  RH € i R y  HI
p1 R y O 2 €€p ROO y p2 € ROO y  RH €€p ROOH  R y

k

Where I2 is an initiator and RH is the hydrocarbon in the oil. When the temperature is raised to 100oC, the following additional reaction occurs as a result of the decomposition of the unstable ROOH:
p3 € ROOH €€p RO y  HO y

€p 2 ROO y € t i ctiv

k

€ RO y  RH €€p ROH  R y
p5 € HO y  RH €€p H 2O  R y

kp4 k

Derive the rate expression for the degradation of the uninhibited motor oil: a. At low temperature (25oC) b. At high temperature (100oC) 82

P7-7C (cont¶) When an antioxidant is added to retard degradation at low temperatures, the following additional termination step occur:
A1 ROO y  AH €€ p ROOH € A A y ROO y €€4 p inactive €

k

Ay

k

Derive the rate expression for the degradation of the uninhibited motor oil: a. At low temperature (25oC) b. At high temperature (100oC)
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Free Radical Polymerization
1. The Reaction INITIATION

This reaction produces the formation of the Primary Radical PROPAGATION

TERMINATION Transfer To solvent To chain transfer agent To monomer To initiator

Addition Disproportionation
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When one of the steps is much slower than all of the other steps in the mechanism, the rate of this step is fully control the overall rate, thus considerable 1 simplification can be gained: € €p
AX

n2 €€

A#  X

A# € B €p
Using PSSH:

3

k 3 ™ k1 ™ [ A ] ™ [X ] rB ! k 2 ™ [X ]  k 3

If it is known that reaction (3) is much slower than (1) & (2) reactions, it is easily derived that:

rB !

k 3 ™ k1 ™ [A ] k3
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RateRate-determining (-limiting) Step (When one of the steps is much slower than all of the other steps in the mechanism, the rate of this step is fully control the overall rate, one can often derive a suitable rate equation for the reaction using somewhat less algebra
2 N2O5 Mechanism:
k

4 NO2 + O2

1 €€p € X  N2O5 n€ € NO2  NO3  X €

k2 

Fast  Slow Fast

3 NO2  NO3 €€ p NO  O 2  NO2 € 4 NO  NO3 €€ p 2 NO2 €

k

k 

What rate expression is consistent with this mechanism?
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Example : P7-8A P7Consider the application of the PSSH to epidemology. We shall treat each of the following steps as elementary in that the rate will be proportional to the number of people in a particular state of health. A healthy person, H, can become ill, I, spontaneously,
(P7-11.1) H I Or he may become ill through contact with another ill person k1

I+H 2I The ill person may become healty I Or he may expire
k3

k2

(P7-11.2)

H

(P7-11.3)

(P7-11.4) I D The reaction given in equation (P7-11.4) is normally considered completely ireversible, although (P7the reverse reaction has been reported to occur : (a) Derive an equation for death rate. (b) At what concentration of healty people does the death rate become critical? (c) Comment the validity of the PSSH under the condition of part (b).

k4

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