κίνησις "kinesis", movement or to move

APPLIED REACTION KINETICS

Friday A032 09:00-11:00 (Assoc. prof. Bohumil Bernauer, A27, Bohumil.Bernauer@vscht.cz,

+420220444017 )
Friday AS44 11:00-13:00 (Dr. Milan Bernauer, H08, Milan.Bernauer@vscht.cz,
+420220444287)
Project report

Resources and references

• Notes from lectures

• Internet
web.vscht.cz/bernauem/

• Textbooks
Fogler Scott H.: Elements of Chemical Reaction Engineering, 4th Edition, Prentice
Hall, 2006. (http://www.engin.umich.edu/~cre/)

Missen R.W., Mims C.A., Saville B.A., Introduction to Chemical Reaction

Engineering and Kinetics, J. Wiley&Sons, N.Y. 1999.

• Journals (on-line)

• Software
MS Excel, (Matlab, Octave, Athena Visual Studio, FORTRAN,
Maple….)
 Fischer-Tropsch (SASOL, RSA ) WGS (BASF, FRG)
N2O decomposition (IPC AS, CZ)

Chemical reactor(s)  heart of

chemical process

Methane aromatization (ICTP, CZ)

Raw material separation  reaction  separation  product

r ( com position , T , P , ..., param s )
 "  " the m aterial elem ent (P lato)
1. Stoichiometry, reaction rate
2NO  N2 + O2 closed (batch) system
t =0 t>0

Atoms of oxygen o
n N O  2 nO2 
o
n N O  2 nO2

Atoms of nitrogen o
n NO  2 n N 2 
o
n NO  2 n N 2
o o o o
n N O  2 nO2  n N O  2 nO2 n NO  2 n N 2  n NO  2 n N 2
o o o o
n N O  n N O   2( n O 2  n O 2 ) n N O  n N O   2( n N 2  n N 2 )

o o
n NO  n NO
o
( nO2  nO2 ) (nN2  nN2 )
 
2 1 1
-2NO + O2 + N2 = 0
Symbols for species NO = A1 O2 = A2 N2 = A 3
Stoichiometric coefficients 1 = -2 2 = 1 3 = 1
i  0 p ro d u cts
3

 i
Ai  0 i  0 in erts
i 1

i  0 reac tan ts
 Molar extent of the reaction
 [ksi:]
o o
o
n NO  n NO ( nO2  nO2 ) (nN2  nN2 )
   
2 1 1
o
ni  ni
 
i

From the definition of the reaction extent follows:

1. The reaction extent has the dimension of moles (number of molecules)
2. The reaction extent value depends on stoichiometry of reaction
3. The reaction extent is an extensive variable
Reaction extent for a single reaction in closed (batch) system
t=0 t>0

o
ni ni Closed system

i  0 p ro d u cts
N

 i
Ai  0 i  0 in erts
i 1

i  0 reac tan ts

o
ni  ni
 
i

ni  ni   i
o
Example

2NO  N2 + O2

A1  N O , A2  N 2 , A3  O 2
 1   2, 2  1, 1  1
 A1 
 
ν   2 1 1  , A  A2
T
 
A 
 3
Matrix notation
 A1 
 
ν A   2 1 1  A2  0
T
 
A 
 3
 Fractional conversion of key component, j X j


X j

 m ax

* o
nj  nj Number of moles of key
 max  component in limits
 j
(chemical equilibrium or 0)
o
nj  nj
*
nj  0 ni  ni
o
i j
Xj o
X j  (0,1)
n
 i  j
o
n  ni
j
X j
   i

 max i
o o
 nj nj o
nj  nj
 j
X j
 100 o
X j  (0,100)
n j

o
nj i
  X j m ax   X j ni  n 
o
i
o
njX j
 j  j
Stoichiometric matrix in the case of several reactions

 ki
Ai  0 k  1, N R
i 1
reaction component

Stoechimetric matrix has NR rows and N columns

  11  12 ...  1N   A1 
   
 21  22 ...  2N A2
ν  ,A   
 .   . 
   
  N R ,1  N R ,2 ...  N R , N   AN 

νA  0
Number of moles of i-th component consumed or created in k-th reaction : o
n ki  n ki
o
n ki  n ki
Molar extent of k-th reaction : k 
 ki

NR

 k
o
Number of moles of i-th
components:
ni  n  i ki
k 1

o T
Matrix notation
nn ν ξ
 n1   n1o   1 
   o   
n2  n  2
n ,n  ,ξ   
o 2

 ..   ..   .. 
  
 no   
 nN   N    NR 
Problem 1.1

Oxidation of ammonia on Pt-Rh catalyst

NH3 + 1.25 O2  NO + 1.5H2O (1)

NH3 + O2  0.5 N2O + 1.5H2O (2)
NH3 + 0.75O2  0.5 N2 + 1.5H2O (3)

Task: To write down the stoichiometric matrix.

A1 A2 A3 A4 A5 A6

Reaction NH3 O2 NO N2O N2 H2O

(1) -1 -1.25 1 0 0 1.5

(2) -1 -1 0 0.5 0 1.5

(3) -1 -0.75 0 0 0.5 1.5

Molar balance table of component in closed (batch) system

Component t=0 t >0

NH3 n1
o
n1  n1  ( 1   2   3 )
o

O2 o
n2 n 2  n 2  1.25 1   2  0.75 3
o

NO o
n3 n3  n3  1
o

N2O n4
o
n 4  n 4  0.5 2
o

N2 o
n5 n 5  n 5  0.5 3
o

H2O n6
o
n 6  n 6  1.5( 1   2   3 )
o

 6 6

 0.25   1   3 
n n
o o
i i
i 1 i 1

e.g . m o lar fractio n o f N H 3

n1  (  1   2   3 )
o

y1  6

 n i  0 .2 5   1   3 
o

i 1
 Independent reactions

Set of NR reactions in reaction network is independent if

Rank()=NR

or

number of independent reactions = Rank()

Problem 1.2
NH3 + 1.25 O2  NO + 1.5H2O (1)
NH3 + O2  0.5 N2O + 1.5H2O (2)
NH3 + 0.75O2  0.5 N2 + 1.5H2O (3)
2NO  N2 + O2 (4)

Task: To calculate the number of independent reactions.

We determine the rank of stoichiometric matrix by Gaussian elimination:

 1  1.25 1 0 0 1.5   1  1.25 1 0 0 1.5 

   
1 1 0 0.5 0 1.5 0 0.25 1 0.5 0 0
   
 1  0.75 0 0 0.5 1.5   0 0.5 1 0 0.5 0 
   
 0 1 2 0 1 0   0 1 2 0 1 0 

 1  1.25 1 0 0 1.5   1  1.25 1 0 0 1.5 

   
0 0.25 1 0.5 0 0 0 0.25 1 0.5 0 0
    
 0 0 1 1 0.5 0   0 0 1 1 0.5 0 
   
 0 0 2 2 1 0   0 0 0 0 0 0 

Rank()=3  only 3 reactions

are independent
 Extent of the reaction in a flow system
o
Fi Fi
REACTOR
Inlet molar flow rates Outlet molar flow rates
[mole of i-th species/s] [mole of i-th species/s]
N

 ki
Ai  0 k  1, N R Open (flow) system in a steady state
i 1 NR
k
 k k 
o
Fi  Fi  ki
k 1 
o
Fi , Fi -o u tlet, in let m o lar flo w rates o f i-th sp ecies [m o le/s]

 k  ex ten t o f k -th reactio n p er u n it o f tim e [m o le/s]

  m ean resid en ce tim e [s]  F1o   1 
 F1 
o T    o  
F =F +ν ξ 
F2 F 
,Fo   2 ,ξ   2 
F 
 ..   ..   .. 
   o   
 
 FN  F
 N   NR 
A reaction is at steady-state if the concentration of all species in each
element of the reaction space (i.e. volume in the case of homogeneous
reaction or surface in the case of heterogeneous reaction) does not
change in time.
 Balance of chemical elements
o
 j  j
REACTOR

 ki
Ai  0 k  1, N R Open (flow) system at steady state
i 1

o
j  j

o
 j ,  j -outlet, inlet m olar flow s
of j-th chem ical elem ent [m ole/s]
o
Φ =Φ  1    1o 
   
2 o

Φ   ,Φo    2  NEL - Number of

 ..   ..  chemical elements
   o 
  NEL    NEL 
 Formula matrix E

NEL elements  NEL=3

N components  N H O
N=6
NH3 1 3 0 Formula vector of NH3

O2 0 0 2

NO 1 0 1

N2O 2 0 1

N2 2 0 0

H2O 0 2 1

There are no creation or annihilation of chemical elements in chemical reactions:

  11  12 ...  1 N   E 11 E 12 ... E 1, N E L   0 0 ... 0

    
  22 ...  2N E ... ... E 2, NEL
 21   21   0 0 ... 0

νE = 0  .  .  . 
NR
     
  N R ,1  N R ,2 ...  N R , N   E N ,1 E N ,2 ... E N , N E L   0 0 ... 0

NEL
Molar* weight (relative molecular mass) of i-th species:

NEL

Mi  E ij
mj
j 1

Atomic weights (relative atomic mass) of j-th element

M = Em
 M1   m1 
   
M2 m2
M   ,m   
 ..   .. 
   
MN   m NEL 

and we have for molar weights of species

νM = νE m  0
because νE  0
*The mole is the amount of substance of a system which contains as many elementary
entities as there are atoms in 0.012 kilogram of carbon 12.
Avogadro constant = 6.022 141 29(27) × 1023 mol−1 (http://www.nist.gov)
 Balances of atoms in batch and flow systems
C lo sed (b atch ) system :
o T
n =n +ν ξ
T
E n = E n + E ν ξ  E n +  νE  ξ  E n
T T o T T T o T o

O p en (flo w ) system at stead y state:

o T
F =F +ν ξ
T
E F = E F + E ν ξ  E F +  νE  ξ  E F
T T o T T T o T o

b ecau se νE  0
Finally
These equations are used
E
T
n  n   E n
o T o

n  0 in data reconciliation tasks
around chemical reactors.
E
T
F  F  = E F
o T o
F 0  The last equation (flow
system) is valid only at
steady state.
 Problem 1.3
Selective reduction of NOx by C3H8 Steady state,
o unknown
Fi Fi stoichiometry
of reactions

NO NO2 CO C3H8 CO2 H2O O2 N2

Fi [  m ole / m in]
o
4.563 0.1845 0 2.943 0 0 90 0
Fi [  m ole / m in] 2.2905 2.3355 0 2.898 x x x x

Calculate the missing outlet molar flow rates

E
T
F o
- F  = E F  0
T

  F1 
1-NO 2-NO2 3-CO 4-C3H8 5-CO2 6-H2O 7-O2 8-N2
 
N 1 1 0 0 0 0 0 2  F2
O 1 2 1 0 2 1 2 0
 
C 0 0 1 3 1 0 0 0   F3 
H 0 0 0 8 0 2 0 0  
T   F4 
E1
T
E2
 F 
5
T T
E 1  F1  E 2  F 2  0  
  F6 
T
E 2  F2   E 1  F1
T
 F  unknowns
1 1  7
  Fi
 F2   E  T
2  T
E  F1  Q  F1
1
Q   E  T
2  T
E1  F
 8


 We obtain using Excel (homework 1)

 0 0 1 3 
 
0 0 0 4
Q   
  0.5 1 0.5 5 
 
  0.5  0.5 0 0 

1
and taking 
 F2   E 2
T
 T
E 1  F1  Q  F1 we have
NO NO2 CO C3H8 CO2 H2O O2 N2
Fi [  m ole / m in]
o
4.563 0.1845 0 2.943 0 0 90 0
Fi [  m ole / m in] 2.2905 2.3355 0 2.898 0.135 0.18 88.76 0.061
Selectivity
Moles of a particular product generated per mole of key reactant consumed

Yield
Moles of a particular product generated per one initial mole of key reactant

Ammonia oxidation

Component t=0 t >0

NH3 o
n1 n1  n1  ( 1   2   3 )
o

O2 o
n2 n 2  n 2  1.25 1   2  0.75 3
o

NO o
n3 n3  n3  1
o

N2O o
n4 n 4  n 4  0.5 2
o

N2 o
n5 n 5  n 5  0.5 3
o

H2O o
n6 n 6  n 6  1.5( 1   2   3 )
o

n3  1
o
1
S NO  NH 3  
( 1   2   3 ) ( 1   2   3 )

n  1  
o
o n 3 0

YNO  NH 3  3
o
 1
o
n
1
n1
 Reaction rate

(IUPAC Gold Book = rate of conversion )



 m ax d 1 d ni 1
r   m ole.s Closed system
 i dt
d
dt dt of uniform
pressure,
temperature
dk and

rk 
composition.

0; 0 t
dt
Rate of generation (consumption) of component Ai

d ni d o n e reactio n
R Ai    i.   i .r  R = νr
dt dt
NR
dk NR several reactio n s

  ki .   ki .rk
T
R Ai    R = ν r
k 1 dt k 1
 We measure usually the rates of generation (consumption) of
components R and we want to calculate r

  R 
T
 r   R
exp T exp T exp T
R  ν r  O bjective function ν r ν r

m inim ization of   r  = least squares solutio n of overdefined system (N > N R )

1

r  νν
T
 νR
exp

Problem 1.4
Steam reforming of methane (5 species, N=5, 2 reactions, NR=2)
1 2 3 4
CH4 + H2O  CO + 3H2 (1)
5
CO + H2O  CO2 + H2 (2)
Measured R : (-0.97572, -2.88778, -1.02127, 4.832804, 2.078537)T (mol/s)

 1 1 1 3 0  12 3 1
ν
1 1

T
νν     νν 
T
ν
-0.10256 -0.02564 0.179487 0.230769 -0.07692
0.076923 -0.23077 -0.38462 0.076923 0.307692
 0 1 1  3 4

 r1   0.94619 
  
 r2   1.99546 
 d
Specific reaction rate
The reaction rate dt is, like  , an extensive property of the system, a specific rate (intensive
property) is obtained by dividing d  by the total volume, mass, surface of the system:
dt

R eaction rate per vo l um e

1 1 d 1 1 dn i 3 1
rV  r   m ole.m . s
V V dt V  i dt
1 1 dk
rV , k  rk 
V V dt

R eaction rate per m ass

1 1 d 1 1 dn i 1 1
rM  r   m ole.kg . s
m m dt m  i dt
1 1 dk
rM , k  rk 
m m dt
 R eaction rate per surface
1 1 d 1 1 dn i 2 1
rS  r   m ole.m .s
S S dt S  i dt
1 1 dk
rS , k  rk 
S S dt

R eaction rate per active center (turn over num be r)

1 1 d 1 1 dn i 1
rR S  r  s
n RS n R S dt n R S  i dt
1 1 dk
rR S , k  rk 
n RS n R S dt
Problem 1.5 (homework 2)

In flow catalytic reactor the synthesis of methanol is carried out

CO(g) + 2H2(g)  CH3OH(g)

The inlet mass flow rate of CO is 1000 kg.h-1 of CO and the inlet flow rate of
hydrogen is supplied so that the inlet molar ratio H2:CO is equal to 2:1. 1200 kg of
the catalyst is placed in the reactor.
The outlet mass flow of CO is 860 kg.h-1.

To determine:
1. Mean reaction rate per mass of catalyst in mol.kg-1.s-1 .
2. If specific internal surface of catalyst is 55 m2.g-1, calculate mean reaction rate
per surface of catalyst in mol.m-2.s-1.
3. If per 1 m2 of catalyst contains 1019 active sites, calculate mean reaction rate
per active site in s-1.
4. Calculate inlet and outlet gas mixture composition in molar fractions.

Data:
MCO= 28.010 kg.kmol-1
NA=6.0221413x1023 mol-1 (Avogadro number)
C O  A1 , H 2  A2 , C H 3 O H  A3

 1   1 
   
ν  2 , R  2 r Fractional conversion of key com ponent
   
 1   1  1  key com ponent
   
NR   F  Fi o    F1o  o i o
X1   i /   Fi  Fi  F1 X 1
  k  Fi  Fi   i  
o o
Fi  Fi  ki  M AX  i   1  1
k 1
o o o
 Fi  Fi  Fi  Fi  Fi  Fi
rM   , rS   , rR S  
m CAT  i m CAT S  iS n RS  i n RS

inlet o
yi outlet yi

F1    1  
o o
F1 1
F1  F1    1  
o
y1  1  X1
o
1-CO F1
o
y1 
3 F1
o

3 3 F1    2  
o F1  F1
o

2 F1    2  
o o
2 F1 2 F2  F2    2  
o o o
o o
y2   F2  2 F1  2 F1 X 1
2-H2 2 F1
3 F1
o
3
y2 
3 F1    2  
o

0 F3  F3    1  
o  F3  F1 X 1
o

3-CH3OH 0 y3 
3 F1    2  
o

F  F   2  
o o o
F  3 F1  2 F1 X 1

o o
F  3 F1 1 1

 860  1000  / 0.02801 / 3600 1

i  1,    1.38839 m ol.s
1
1.38839 3 1 1 1.38839 8 2 1
rM   1.157  10 m ol.kg . s , rS  3
 2.104  10 m ol.m .s
1200 55  10  1200
23
1.38839  6.0221413  10 3 1
rR S  3 19
 1.267  10 s
55  10  1200  10
 1000  860 
X1   0.14
1000

inlet yi
o
outlet yi

1-CO o F1
o
1 F1
o
1  X1 1 X1
y1  o
 y1  o o
  0.3162
3 F1 3 3 F1  2 F1 X 1 3  2X1

2 F1
o
2 o
2 F1  2 F1 X 1
o
2 1  X 1 
2-H2 o
y2  o
 y2  o o
  0.6324
3 F1 3 3 F1  2 F1 X 1 3  2X1
o
F1 X 1 X1
3-CH3OH 0 y3  o
3 F1  2 F1 X 1
o

3  2X1
 0.05147

 1 1