Chap 10 Chemreactions

Mass Transfer
Chapter 10
Hererogeneous and Homogeneous g g
Chemical reactions
Dr R Bchel Lecture 28 11 2012 Dr. R. Bchel - Lecture 28.11.2012
28. November 2012
Definition
Overview: Chemical reactions
- Definition
Reaction rate
order reaction order reaction
equilibrium constant
- Heterogeneous & Homogeneous reactions g g
- Diffusion-Controlled Reaction Diffusion-Controlled Reaction
- Diffusion and 1
st
Order Heterogeneous Reactions
Mechanism of Irreversible Heterogeneous Reactions - Mechanism of Irreversible Heterogeneous Reactions
- Heterogeneous Reactions of Unusual Stoichiometries
Mass Transfer Chemical reactions 10-2
Introduction to chemical reactions
A chemical reaction is a conversion of one set of chemical
substances into another.
AB+CD AD +BF
The reaction rate is the decrease in reactant concentration or the
increase in product concentration with time:
(1)
The reaction rate is proportional to the concentration of the The reaction rate is proportional to the concentration of the
reactants:
(2) (2)
With k being the rate constant.
Many chemical reactions are reversible and forward and
reverse reactions finally lead to an equilibrium
We can define (1) and (2) also for the reverse reaction:
Now, the rate of the total reaction is the difference in the rates
of the forward and reverse reactions:
If and
the reaction has reached the chemical equilibrium and the ratio
of the rate constants is the equilibrium constant of the chemical of the rate constants is the equilibrium constant of the chemical
reaction:
Reaction order Reaction order
Apart from temperature and pressure, the reaction rate can
depend on the concentration of the reactants.
A reaction rate depending on the concentration of one A reaction rate depending on the concentration of one
reactant is a first order reaction, e.g.:
one depending on two concentrations is of second order:
F i ibl d d ti For an irreversible second order reaction
The forward reaction
is third order, since:
Note: Reactions typically occur in a series of multiple reactions. One step
is the rate determining one. Therefore, the overall reaction would be g
of second or first order. (depending also on concentration)
A reaction rate not depending on any concentration is called a
zero order reaction zero order reaction.
Reactions and mass transfer
Chemical reactions are always coupled with mass transfer Chemical reactions are always coupled with mass transfer
since the reactants have to travel to the location where the
conversion takes place (sink for the reactants) while the
products have to travel away (source for the products).
Comparing the speed of mass transfer with the speed of the Comparing the speed of mass transfer with the speed of the
reaction allows to determine the rate-limiting step and whether
the reactions have to be accounted for: the reactions have to be accounted for:
reaction rate >> mass transfer neglect reactions reaction rate >> mass transfer neglect reactions
mass transfer >> reaction rate include reactions
When reaction rate and mass transfer are comparable then we
need to incorporate reaction into the models.
i i i
i
r c c D
t
c
+ v V V =
c
c
0 2
t c
(see: Generalized Mass Balances)
Activation energy
A ti ti i i d f th ti t t t d t Activation energy is required for the reaction to start and to carry
on. The activation energy is typically supplied as heat (higher
temperature) but sometimes it can be other electromagnetic temperature) but sometimes it can be other electromagnetic
radiation, such as UV light.
A catalyst lowers the activation energy and increases the speed of A catalyst lowers the activation energy and increases the speed of
the reaction at a certain temperature. The catalyst (typically a
solid, but could also be a liquid) is not consumed after the solid, but could also be a liquid) is not consumed after the
reaction.
Examples of chemical reactions Examples of chemical reactions
Combustion (gaseous, liquid or solid fuels)
Production of chemicals (catalysts)
Fuel cells, batteries (catalysts)
Gas cleaning (e.g. removal of SO
2
by CaO)
(Nano ) particle synthesis
(Nano-) particle synthesis
Heterogeneous & Homogeneous reactions

Heterogeneous reactions take place AT an interface (e.g. solid
catalyst surface, coal combustion) and diffusion and reaction
occur by steps IN SERIES occur by steps IN SERIES.
Homogeneous reactions take place THROUGHOUT the volume Homogeneous reactions take place THROUGHOUT the volume
in the same phase (fuel combustion in engine). Diffusion and
reaction occur by steps partially in PARALLEL.
For simplification of mass transfer problems some p p
heterogeneous reactions can be treated as homogeneous
ones, depending on the definition of the observation space.
For example, in combustion of coal
ti l i fl idi d b d i iti ll
CO
2
O
2
particles in fluidized beds initially
reaction takes place AT the coal
surface so heterogeneous reaction
O
2
O
2
Coal
surface so heterogeneous reaction.
2
O
2
CO
2
O
2
O
2
O
2
L t h hi hl
CO
2
Later on, however, a highly porous
inorganic structure (e.g. fly ash)
develops and combustion takes place
O
2
O
2
develops and combustion takes place
THROUGHOUT the particle.
CO
2
Even though microscopically the reaction still is a surface reaction,
i b ti f th ti ti l i th i t f
macroscopic observation of the entire particle gives the picture of
reactions occurring homogeneously throughout the particle.
Thus, this case can be described as a homogeneous reaction
and the homogeneous reaction model can be applied:
The above example shows that the The above example shows that the
assignment of the reaction type can be
subjective! subjective!
Combustion is an irreversible reaction, so
In summary, coal particle combustion can be described as:
a) Heterogeneous reaction and transport: a) Heterogeneous reaction and transport:
0
1 1
2 1
v V V =
c
c
c c D
t
c
ct
The reaction is introduced at the boundary conditions!
b) Homogeneous (homogeneous-like) reaction model and
transport:
1
0
1 1
2 1
r c c D
t
c
+ v V V =
c
c
t c
Examples of reaction assignment
Oxidation of lead sulfide (semiconductor) particles: Oxidation of lead sulfide (semiconductor) particles:
PbS particles porous PbO
heat
R l f i f ff Removal of ammonia from off-gas:
NH / air + H O NH OH
scrubbing
NH
3
/ air + H
2
O NH
4
OH
Adsorption of sulfur dioxide (from combustion off-gas):
SO + Ca(OH) /H O CaSO
scrubbing
SO
2
+ Ca(OH)
2
/H
2
O CaSO
4
using Ca(OH)
2
slurry
8.1 Diffusion-Controlled Reaction
Every diffusion-controlled process involves
multiple steps. E.g. in dehydrogenation of
(a)
u p e s eps g de yd oge a o o
C
2
H
6
on Pt crystals
(1) C
2
H
6
diffuses to Pt surface
(2) C
2
H
6
reacts on the surface
(3) Product diffuses away from the (3) Product diffuses away from the
surface
When step 1 takes much longer than step 2 then we have a
diffusion-controlled reaction.
In a) we have a diffusion-controlled
heterogeneous reaction where the
(a)
reactant diffuses to a (e.g. hot or
catalytic) surface, reacts and the
product diffuses away product diffuses away.
In b) we have a porous particle and
(b)
the reactant diffuses to catalytically
active sites where it reacts and the
d t diff hil ti
(b)
product diffuses away while reaction
continues. Very important in catalysis,
scrubbing and extraction
scrubbing and extraction
(homogeneous reaction model).
In c) a slow-moving molecules
react with more mobile ones
(c)
facilitating the transport of the
former across a membrane
( l k b (example: oxygen uptake by
hemoglobin in the lungs).
In case d), molecules are well
mixed and react upon contact. The
(d)
p
reaction rate depends on the
Brownian motion of the molecules
( id/b ti CH
(d)
(acid/base reactions, CH
4
combustion etc.)
(a)
(b)
Goal: To find the overall rate of the process
8 2 Diff i d 1
st
O d H t 8.2 Diffusion and 1
st
Order Heterogeneous
Reactions (dilute solutions)
A first-order reaction with respect
to a reactant is one where the
ti t i ti l t th reaction rate is proportional to the
reactant concentration:
r = c k
i i
r = c k
At the steady state the overall
reaction rate/area equals the
diffusion fluxes
) ( c c k n
2 2 3 2
1 1 1 1
) (
) (
= =
=
c c k n
c c k n
i
i
2
r =
The surface reaction is
Species 1 Species 2
-2
And the reaction rate is given by
i 2 2 i 1 2 2
c c r k k =
i 2 2 i 1 2 2
c c r

k k =
Note that the equilibrium constant is q
2
2
2
K
k
k
=
To find the overall reaction we must eliminate the surface (or
interfacial) concentrations that are hard to measure.
interfacial) concentrations that are hard to measure.
Following the analysis of the mass transfer across interfaces
(overall MTC) we obtain: ( overall MTC ) we obtain:
|
|
.
|
\
|
= =
2
1 1 2
K
c
c K n r
|
.
\ 2
1 1 2
K
Wh th ll MTC i t i Where the overall MTC or resistance is:
1
K =
( )
2 3 2 1
K k 1 1 k 1
K
+ k +
=
Similarities/differences with interfacial mass transfer:
1. The resistances 1 / k
1
, 1 /
2
and 1 / (k
3
K
2
) add to the total
resistance 1/K
|
|
|
|
i ti th ith ilib i i
1 species of ion concentrat
/ K
|
|
.
2 species of ion concentrat bulk

existing the with m equilibriu in /
2 2
K c
2. Henrys law constant (partition coefficient) characterizes
destribution between phases: K H destribution between phases: K
2
H
K
2
and H vary over a wide range. Here, similarly to H, the K
2
determines the relative impact of k
1
and k
3
.
p
1 3
Example 8.2.1: Limiting cases of 1
st
order reactions
(a) Fast stirring
|
|
|
2
c
Determine overall rate of the process when:
k
1
and k
3
are large, so K
2
. Then,
|
.
|
\
|
k =
2
2
1 2 2
K
c
c r
(b) High temperature
Usually at high T the reactions are fast
|
|
|
=
2
1 2
c
c
1
r
so 1/
2
is very small and can be
neglected
( )
|
.
\
+
=
2
1
2 3 1
2
K
c
K k 1 k 1
r
(c) Irreversible reaction
-2
= 0 so K
2

1
2 1
2
c
1 k 1
1
r
k +
=
Note that ONLY in this case the resistances are simply
additive.
Example 8.2.2: Cholesterol solubilization in bile
Bile* is the bodys "detergent" for fat digestion through cholesterol
excretion. Failure of bile leads to cholesterol gallstones. Typically,
gallstones are removed by surgery However lab data show that gallstones are removed by surgery. However, lab data show that
gallstones can be dissolved by administering certain components
of the bile. o t e b e
Goal: Find dissolution (reaction) rate of gallstone
As a cholesterol gallstone is a solid, mass transfer/chemical
reaction at a solid/fluid interface needs to be understood: rotating reaction at a solid/fluid interface needs to be understood: rotating
(spinning) disk apparatus for cholesterol dissolution rates.
*Bile = Galle (in German)
cholesterol dissolution rate= 5.39 10
-9
g/(cm
2
s) = r
2
solubility = 1 48 10
-3
g/cm
3
= c solubility 1.48 10 g/cm c
1
D = 210
-6
cm
2
/s
disk diameter, d = 1.59 cm
Re = 11200
bile kinematic viscosity, v = 0.036 cm
2
/s
h l t l l ti A d it th bil 1 10
5
/
3
cholesterol solution, A density over the bile = 110
-5
g/cm
3
If the reaction is irreversible find:
a) surface reaction rate constant a) surface reaction rate constant
b) dissolution rate of a 1 cm radius cholesterol gallstone
1
(a) For this case
2 1
/ 1 k 1
1
K
k +
=
( )
9 2
2
2 1 3 3
1
5.39 10 g cm s
r
r K c K
c 1.48 10 g cm
= = =
Find k
1
from the appropriate mass transfer coefficient using the
correlation for the spinning disk: correlation for the spinning disk:
s / cm 10 16 2
d D
62 0 k
3
3 1
2 1
2
=
|
|
|
v
|
|
|
|
e
= s / cm 10 16 . 2
D d
62 . 0 k
1
=
|
.
\
|
|
.
\
v
=
S b bt i d f k d K 3 6 10
6
/ So
2
can be obtained from k
1
and K as
2
= 3.610
-6
cm/s
(b) dissolution rate of a 1 cm radius cholesterol gallstone
The 1 cm cholesterol gallstone is assumed to stand still but the The 1 cm cholesterol gallstone is assumed to stand still, but the
density gradient between cholesterol and bile results in flow by
free convection so the mass transfer coefficient is:
1/ 4
1/3
3
1
k d d g
2 0 6
| |
A v | |
+
|
|
1
2
g
2 0.6
D D
| |
= +
|
|
|
v \ .
\ .
3 5 3 2
1 3 1
6 2 3 2 2
k 1cm (1cm) 1 10 g / cm 980cm/ s
2 0.6 (18000)
2 10 cm / s 1g / cm (0.036cm / s)
| |

= +
|
|
\ .
5
1
k 5.6 10 cm/ s
=
As we are still dealing with irreversible reactions:
1
K =
s / cm 10 6 3 / 1 s / cm 10 6 5 / 1
1
/ 1 k 1
K
6 5
2 1

+
=
k +
s / cm 10 4 . 3
s / cm 10 6 . 3 / 1 s / cm 10 6 . 5 / 1
6
6 5
=
+
In a unstirred bile, the rate is also controlled by the reaction.
8.3 Finding the Mechanism of Irreversible Heterogeneous Reactions
Typically, the reaction mechanism is not known so it has to be
inferred.
The surface reaction takes place as The surface reaction takes place as
( ) products
2 i
solid
1 i
gaseous
|
.
|
\
|
+ |
.
|
\
|
( )
2 species 1 species
. \ . \
Physical situation Rate-controlling
step
Size
R = (time, reagent)
Size = (temperature) Size = (flow) Remarks
A Shrinking Reaction R c
1
t strong temperature Independant of flow Other reaction
particle variation stoichomerties can
be found easily
B Shrinking External diffusion R
2
(c
1
t) small particles Weak temperature Independent for small The exact variation B Shrinking External diffusion R (c
1
t) small particles Weak temperature Independent for small The exact variation
particle R
3/2
(c
1
t)larger particles variation particles only with flow depends
on the mass transfer
coefficient
C Shrinking Reaction R c t strong temperature Independent of flow This is the same as C Shrinking Reaction R c
1
t strong temperature Independent of flow This is the same as
core
a
case A, except for
ash formation
D Shrinking External diffusion R c
1
t Weak Usually about square This case is
core
a
root of flow uncommon
E Shrinking Ash diffusion R (c
1
t)
1/2
Weak Independant of flow This case is common,
core
a
an interesting
contrast with the
previous one
Notes:
a
This is often called the topochemical model. The size R refers to the cone
Cases A and C: surface reaction controls
2 1 2 2
c c r k =
As the solid concentration (c
2
) is constant the reaction is 1
st
order with respect to c
1
.
Mass balance per particle: 2 3
4 d
| |
Mass balance per particle:
2 2
2
2 2
3
4
dr
4
r 4 r c r
3
4
dt
d
t =
|
.
|
\
|
t
2
2 1 2 2
2
c
dr
r 4 c c
dt
dr
c r 4
k
t k = t
Be careful, distinguish
between radius r and
1 2
c
dt
k =
between radius r and
reaction rate r
2
!
If the gas phase concentration c
1
is constant and the particle
has an initial radius R
0
t c R r k =
t c R r
1 2 0
k =
Case B: Diffusion outside of a shrinking particle controls
Identify correlation (forced convection around solid sphere)
v | | | |
1/2 1/3
k d dv v
v
| | | |
| |
\ . \ .
1
k d dv
=2+0.6
D D
B 1) F ll ti l R 0
D d k
B.1) For very small particles Re 0, so
r
D
k
D
d k
= = 2
Mass balance:
d | | 2 3
4
Mass balance:
D dr
c c r k c r
dt
d
i
t =
|
.
|
\
|
t
2 2
1 1
2
2
3
4 4
) ( 4
3
4
c
D dr
r
c
r
r
dt
c r
=
t = t
1
1
2
2
2
4 4
t
Dc
R r
c
c dt
r
|
|
|
|
=
1 2
0
2
1
2
2
t
c
|
|
.
\ 2
0
B.2) For large particles
3 / 1 2 / 1
1
v d
6 . 0
d k
|
.
|
\
|
v
|
|
|
~
2 / 1
6 / 1
3 / 2 2 / 1
1
r
D v
42 . 0 k
D
6 . 0
D
|
|
|
|
~
|
.
\
|
.
\
v
~
6 / 1
1
r 42 . 0 k
|
|
.
\
v
~
Similarly,
| |
=
|
v
\ .
1/ 2 2/ 3
1/ 2
2 1 1/ 6
dr v D
c r -0.42 c
dt
\ .
| | | |
=
| |
v
\ .\ .
1/ 2 2/ 3
3 / 2 3 / 2 1
0 1/ 6
2
c 0.64 v D
r R - t
c v
\ .\ . 2
c
Cases C, D, and E: shrinking core model:
Two diffusional resistances in series
Physical situation Rate-controlling step
A Shrinking Reaction
Bulk fluid
+
P ti l f
R
0
A Shrinking Reaction
particle
B Shrinking External diffusion
Particle surface
+
Unreacted core
B Shrinking External diffusion
particle
C Shrinking Reaction C Shrinking Reaction
core
a
D Shrinking External diffusion D Shrinking External diffusion
core
a
E Shrinking Ash diffusion
core
a
core
a
Case D: Diffusion in the surrounding bulk fluid controls
4 d
| |
Mass balance:
d
kc r 4 c r
3
4
dt
d
1
2
2
3
t =
|
.
|
\
|
t
kc r 4
dt
dr
c r 4
1
2
2
2
| |
t = t
t
c
c
k R r
2
1
0
|
.
|
\
|
=
Similar dependence of r with t as with cases A and C.
Dependence on flow (through k) but weak dependence on
temperature.
Case E: Diffusion in the ash (or shell) controls
Here the thickness of the shell is important Film model:
D
k =
r R
k
0

=
where D is the effective diffusivity through the shell where D is the effective diffusivity through the shell
Mass balance:
1 2
2
3
c D
r 4 c r
4 d
t =
|
|
|
t Mass balance:
2 / 1
1
0
2
t
c D 2
R r
r R
r 4 c r
3 dt
|
|
|

t =
|
.
\
t
2
1
0
t
c
R r |
.
\
=
8.4 Heterogeneous Reactions of Unusual Stoichiometries
8.4.1 Irreversible second-order heterogeneous reaction
(additivity of resistances)
Steady-state mass transfer to the surface:
) c c ( k n r
i 1 1 1 1 1
= =
Surface reaction:
2
i 1 2 1
c r k =
Find the c
1i
by equating the above
| |
= + k
4 k
0 c k c k c
1 1 i 1 1
2
i 1 2
|
|
.
|
\
|
k
+
k
= 1
k
c 4
1
2
k
c
1
1 2
2
1
i 1
So the overall reaction rate is:
( | |
k
= + ( |
|
k
(
\ .
1 2 1
1 1 1
1 2 1
k 4 c
r k c 1 1 1
2c k
k
(
\ .
1 2 1
2c k
C thi ith th di fi t d ti Compare this with the corresponding first order reaction:
( | |
k
= + ( |
|
k
(
\ .
1 2 1
1 1 1
1 2 1
k 4 c
r k c 1 1 1
2c k 1
2 1
1
/ 1 / 1
1
c
k
r
k +
=
\ .
2 1
/ 1 / 1 k k +
first order reaction
second order reaction
8.4.2 Heterogeneous Reactions in Concentrated Solutions
Until now we assumed that k
1
f(r
2
). This is good for dilute
solutions.
E l
Cracking of hydrocarbons:
Example:
Reforming
2

2
1 mol of species 1n moles of species 2,
n > 1
1 mol of species 1 n moles of species 2,
n < 1
2 2
In both cases we must account for CONVECTION in the calculation of mass transfer.
In cracking, convection is AWAY from the surface: The
reacting species must diffuse AGAINST the current of
product species.
In reforming, convection is TOWARDS the surface as
reaction "pulls" reactants The product must diffuse away reaction "pulls" reactants. The product must diffuse away.
> 1 cracking
< 1 reforming
f = 1 treat as before
Goal: To calculate the overall rate!
Overall rate of reaction across this film is:
n
= = = k
v
2
1 1 2 1i
n
r n c
We must calculate the flux n
1
for concentrated solutions:
0 1
dc
D
0
1
1
1
v c
dz
dc
D n + =
N th fl f ti i Now the flux from convection is
1 2 1
0
n ) 1 ( n n cv v = + =
1 2 1
n ) 1 ( n n cv v +
So the equation for flux n
1
can be written as:
0
n
c n
1 dc
1 1
+
v
+
So the equation for flux n
1
can be written as:
0
D
c n
Dc dz
1
1 1
1
= + +
B C s: z = 0: c = c B.C. s: z = 0: c
1
= c
10
z = l: c
1
= c
1i
| | + v k k c 1 ( 1)n /( c)
Solving for n
1
gives:
| | + v k
= =
|
v + v
\ .
1 1 2
1 1
10
k c 1 ( 1)n /( c)
r n ln
( 1) 1 ( 1)c / c
where
l
D
k
1
=
l
1
For diffusion control For diffusion control
(
2
c
10
/n
1
is large) the
following diagram shows
the rate relative to that of
dilute solutions:
Consider studying cracking of oil by flowing it over a hot plate.
If the molecular weight of the product is only 25% of that of the oil, g p y ,
by how much the convection introduced mass transfer changes
the cracking reaction rate?
1 molecule oil = x 0.25 molecules of the product.
So 4 So 4
As only oil is flowing (c
10
/c) = 1 So 1 + ( - 1) c
10
/c 4 From As only oil is flowing (c
10
/c) 1. So 1 + ( 1) c
10
/c 4 From
the above figure:
% 40
rate reaction 1 : 1
rate actual
=
rate reaction 1 : 1
The convection REDUCES the reaction rate when the effect of
reaction on the mass transfer coefficient is neglected.

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Mass Transfer

Heterogeneous & Homogeneous reactions

2 species of ion concentrat bulk

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