CHAPTER

KINETICS OF FLUID-PARTICLE
REACTIONS
This chapter deals with the kinetics of fluid-particle reactions - non-catalytic heterogeneous
reactions in which a gas or liquid is brought in contact with a solid and reacts with the solid to
transform (convert) it into a product. Fluid-particle reactions yield fluid and/or solid products and
thus may be represented by
A (fluid)+ bB (solid) ➔ Fluid products ... (4.1)
➔ Solid products ... (4.2)
➔ Fluid and solid products ... (4.3)
In case of such reactions we have two different cases to consider :
1. The particle size remains unchanged during reaction. In fluid-solid reactions this will
happen when -
(a) solid particles contain large amount of inert material which remain as a non-flaking ash.
or
(b) a firm product material is formed by the reactions of Equation (4.2) or Equation (4.3).
Examples of fluid-solid reactions in which the solid does not appreciably change in size
during reaction are :
(i) The roasting of sulphide ores in air to yield the metal oxides. For example, zinc sulphide
is roasted to produce zinc oxide.
1
ZnS (s) + ➔
2 0 2 (g) ZnO (s) + SO2 (g)

(ii) The reduction of metal oxides to the corresponding metals. For example, reduction of
magnetite, Fe 3Q4 , by hydrogen occurs according to the following reaction to produce
iron.
Fe3O4 (s) + 4H2 (g) ➔ 3Fe (s) + 4H2O (g)
. 2. The particle size changes with the progress of reaction (the particle decreases in size,
1.e., shrinks during the course of reaction until it disappears).
(4.1)
 • • 1W ~ -11 _...............................~.'.~........... Ki"..f::~.~~~....?!. Fluid-Pa'"'•
. ···-·-·····-·..... ............................'. LICle ~
111 ~!.~~!~~'.'....~'.'.~.l.~13,.'3..r..i'.'.~ - II
~ l e reactions this will happen when - ...........,. . . . ~ 11elfl 0............. .....4.3
. .......... . Kinetic
/ / 1 kinetic ,nodds have been developed for ~-------~ , _
0
rJallY. Je 'fo descnbe the progress of the no progress of th ~ .....1 I j
tlakiDg ash or product material is formed or .d .,uc . n-cata1 r • '"-'Ii
1 soil P on sider two simple models regarded Y ic reaction of Parti' on Withia ~ .
·d we c . . as pedect.10 clos.,·11, -
01.1 ' . ...., del and the shnnking unreacted _co reality .,... __1 i Blln'rlnadl-

~
(b) pore Bis used in the reaction of Equation (4.1) 00,ersion
1 '"0 re model. •- Ythe - ~
w.wnlM of fluid-solid reactions in which the size of solid changes are : ' .,. . conversion Model (PCM) :
yrogreSs•
fh!S. rnodel assumes. that reactant gas enters and reacts through 1
(i) The production of carbon disulphide from the elements : . Proceeds continuously 1
,uon . .throughout the part·"e). The out the paru·"at all ·
C(s) +2S (g) ➔ CS2 (g) (rea iocations within the particle. rate of reaction . . -
difle!eot . . IS difleralt II
,nenc e, the whole reactant . particle 1s continuously d
an progressiv J
(ii) The production of water gas by the action of steam on coal (with low ash content): io Fig. 4.2 (which also
as sbowo1
. . shows how the co ncentralton . of ethY convened
. into product
tlU"'g out th• solid parucle .at different instants after the onset of the reacti
e sohd reactant chllllgCI

~·
C (s) + H20 (g) ➔. CO (g) + 2H2 (g) .
.tts'If ,·sh a firrn solid, the particle size remains unchanged • bUt I.f teprod
h t'on). [If the product.IS
(ii) The burning of pure carbon in air : icle size decreases until it disappears.] uc " volatile or flaking
C (s) + 02 (g) ➔ CO2 (g) art
LoW .
(At anposition)
intermediate
Low
(Nearly fully
converted particle)
.
1.

0 iime

Q iime

0 . convers1on oco
ersion
nv con~~~ion

O
Time '.,~·· + •· Ti1me ., ·
Initial Partly
unreacted reacted particle Completely
particle (at an intermediate instant) reacted particle : I --- : '•-,. : - ~ I
(Prior to reaction) (Final particle is hard, I I •
firm and unchanged in size) I I I I I I
I I I I I I

0
(fully converted particle)

~oroc: ___ ....-rl ______~I_ _ _ _ _ _ --r----------

~~ ®
.. I I I I I I
iime
2. ,o I
'
I I
-- --r-----r
I I
OrlQ;""
nme I ~ I
0 roro I I I ·
Oo I I I I -
Initial
unreacted Flaking ash Particle shrinks
i~
)S
I
I
I
I
~ I
I
I
I
I
I
particle or ga~eous P.roducts with passage of time, o"' I I I I I I
caus,~g shnnkage
m size and finally disappears (.) I I I I
I I I I I I
F1g• ••
~
I I I I I I
. 4 I . Different sorts of behaviour of reacting SOiid Particles in fluid-solid reactions I I I I I I
Selection of a kinetic model :
R O R R O R
R 0 R
Every conceptual picture or model describing the pro
F' Radial position
mathematical representation, its rate equation. Therefore if we gress of reaction . . own
has its
, 1
seecta t a sohd particle and concentration profde of solid reactant (B) with
its rate equation and vice versa. If a model matches closely with Wh rnodel we have to accep rg. 4.2 : Sketch 0 f ·
equation will closely predict and describe the actual kinetics of theat real~y happens, then its rate Sbrbtki progress of reaction · · unchanging size . progressive - conversion model
. . . reactio . I
differs widely from what really happens, then its rate equation Will be n, Whereas 1f a mode
. . . useless I . Th· ng • Core Model (SCM) :
select a model which mvolves too many mathematical complexities e · t 1s worthless to model assumes at reaction begins first at the outer surface of the sobd
1"l'Ct"iayer · parttc
· 1e and th•
reflects/represents reality. One has to select a model which is the close:;:ethough it very closely
and at the same time it should be easy to treat mathematically (i.e., the kin ~resentation of reality
liotous
th
th
,«:i
do not take part in the reaction until all the outer layer has ttansfonned into solid O!
I .
be descnbed with relatively simple equations).
~~
OdeJ selected can
1 %tc
( ing Gradually, the reaction zone then moves inward (into the"'.'-
e ,olid), constonll)1
SOiid P<oduct)size of. core of the unreacted solid and leaving L,ehind completely converted sof d
and mert matenal
. (mert
. . reactant) ·
constituent of the sohd
•
 .II
._...-·---··-···--~.:~
. ..... ....-. ..... t5ine!!_cs
...... of.....Flu1·d
..... ·Part1
.. . Cle t1on E..!.1.S, inee_
. g - II
···· ··· · ~~O ... ..
4.5 K...____- .,. fll 1611
····· ····· ··--•-.....:.~.~- " •?: J , f
I ~e.~~···· ········· b diffusion through pores and cracks in the blanket (I...-,...._
~ We ,lolinO conwited ,olid (i.e.. sobd product) and mert matenal as ash · ' \ i'~~....-·
0116.~····
. of A Y
:;.--- . penetrauon of the unreacted core ... pore or internal d1ffus1on.
. . . ·~ • -•
..1 -~A
.. - - ,.,...nnuously deCte"" in size I shrinks in size during reacti on · unnAn1unrc.,.:
. -.
(it) rface
_.,cl (llco: the _.n1
of solid ,naterialto be consumed by reaction isshri • 11 is ' tbe su
·on° f g aseous
A with solid B at the surface of the unreacted core {lllelkia
. React!
Al r,ry gr,en instaD~ the solid particle comprises of a core surrounded b nl<ing •i~~
core is the unreacted reactant (that shrinks Y an toenvelor..I'<'
. so this model is re",erred
. with time) (iii) sorf•c•l· roducts back to the exterio, su<face of 1he solid lbroug!, tho Ill,
f gaseous P . .
unreacted-core model. The envelope consists of a sohd product and inert malenal.
. as shn,' ¼ . p1 u·ff sion °
reverse m temal d1ffus1on. .
The shrinking of size of unreacted core of solid wilh reaction time is sh own .in Fig. 4.3. (iV) (asb layer) · · · roducts through the gas film back into the main body of gas
. (Nearly fu . of gaseous p .
At intermediate converted lfy Diffusion al diffusion.
Low instant Higt~ (v) reverse extern fil fa gaseous reactant A reacting with a solid particle
Prior to convt11Sion conversion t ation pro i e o .
reaction 4 show s the concent rA at d1.ffere nt points of the reaction space.

C)
I
I
.
.
..
I
Q - I
I
T1me

I
I
-
Time

~
fig. 4.

the cone
. of reactan
entrauon
surface
.
Of particle~

Ash I I
.
Moving reaction surface
Shrinking unreacted
r-- core containing B
r-
I I I I I I --- Gasfilmx
0
I
I
I
I
I
I
I I
I I
I
I ..... ,, /
t=
)
I I I I I I
! I I I I I \ I
I

'D
i! I I I

e!
8~ \ I
I
I
I
I
I
I
I
I I
I
1 Tim~ I
I\
I \ I II
I I I / I ,J ..... I I l)/I
I I I / I I -.I_ -r- _.. I I I
I I I /,, I I I I t I I
R 0 R R 0 R R 0 R R I I t t I I
I I I I t I I

J_-±-rrc;
Radial position
<! C 1_ I
Fig. 4.3 : Sketch of a solid particle and concentrat·1on profil1 e of solid
• reactan t - 01:0:::
Ag ::, -,
C CO_, CAs - I I -'- -,
unchanging size - the shrinking · core model Ou U C -7--r ' I
~
~
m-6
\.,. e
A
C Ac -t--
...l-
I
-~-
I
As the shrinking - core model (SCM) has been reported t0 . be , C Ul 0. I I I
. . . . . approximate closely a num ro. Q):, "O
I I I
fluid - sohd reactions, let us develop its kinetic equation f • ooc
. . . . s or fixed as well as variable siZI g ~ co
t) co
I
I
I I
partlcles. In domg this, we consider the surrounding fluid to be a . . and O>
R re 0 rC
irreversible reaction between a gas and a solid [any one of the . gas, sphencal particles Radial position
reacttons i b E . (4 I),
(4.2) and (4.3)]. Please note that in the analysis to follow we . g ven Y quations ·
. . . . consider the . fl .d to be
a gas but keep m mmd that the analysis given below is applicabl surround mg UJ A(g)4·4+:bB
Fig. s
Concentr af_,on Profile of a gaseous reactant Areacting with a solid parli<k :
e equally well to liquids ( ) -> sohd product • particle of unchanging ~,re • shriokiog-core model
Shrinking - Core Model (SCM) for Spherical Particles of Un chan · ·
ging Size/ F" d 1 s·ze · "'P>ln(iv)
~
According to this model, the following five steps occur in sue . ixe •
and
all g actions, all these steps may not exist. If no gaseous products aie formed.
. re · .
cession d . as-~ohd

~
unng react"1on · \le offe, .(v) do not e m· t and thus do not contribute to the resJStance
· to reacuon.
· Al\ thesi
(i) Diffusion of gaseous reactant A through the gas film su rrounct· •

surface of the solid particle ... reactant A diffuses to the ing the particle co the tly from
res,stance tO reacllon
. and the magnitude of the resistances of 1hese 51eps usually d\11<
.
ellternat
particle from the bulk gas phase through the gas film ...... ellte surface of the solid "'. '''"n>llin
each other· In such cases, the step with
. the tugbesl
• ·
reSJstance"· conSI·dered as
rnai diffu s1on.
·
g / rate _ determmmg
. . for the overall reaction process.
 Kinetics of
•• " .. ----···...4.6
- -.................~.1~.\.~:Pa!tic
.. • ··········•···•"'"'
Reacti 0 ~ ....~.'.1.~.1i:.1!.1:1.~!.'.1.~ . II --.. ...~:.?__ .. kl
.,..... ..,. st,i,s roaY control the overall reaction rat ·---lo~ lfl1oal ...................... --·-~
-! ~ for spherical particles by considering e.eachThere~
., wa--~-. .-tinos
CJ_!................... A (g) + bB (s) ➔ products

,......,., ... ~
O It
rlhc;.;; . biometry of the reaction :
the stoic
1)iffmion dlOOgb the ~ film. J,. fro(ll dNA __ (.!.1 dNa _ l dN 8
(ii) DiffmioB mrougb the a.sh (converted solid and inert material) / ash 1 - dt - (b) dt - - b dt
r.•i)l"L.-:-, . ayer.
,■ ~ reaction.
dN 8 dNA
...._...,.. GM. Film Controls (Controlling resistance-gas film d1'ffns1on) . - dt = - b dt
... (4.5)
Wbmew:r the resistance of the gas film controls the overall reaction :
pdile for gaseous reactant Awill be as shown in Fig. 4.5. rate, the co nee . . Equations (4.4) and (4.5), we get
~~~ Moving reaction surface
~ Co(llb1ntng
1 dN 8 _l_dNa b dNA
- Sex dt = - 41tR2 dt = - 41tR2 dt = bkg CAg = constant ... (4.6)
Ash layer
Gas film
, The amount of B present in a particle is given by
I
I
I
Surface of shrinking NB = PB V ... (4.7)
I unreacted core
3
'I . the molar density of B in the solid in moles/m solid and V is the volume of particle
",,,..._,,,,
I 'II ~ y I
where Pa is
(ill3 solid).
< I l'.J I \,'I I ·n volume or radius of unreacted core as a result of the disappearance of dN8
Oc I I l''"t"'i I I The decreas e l
cs I I I I I I I
.g ~ I I I I I I 1 solid reactant is given by
l!!G>
_._ I I I I I I 1 moesI Of
Ca, t
gs
0 CD
L_I
CAgr,-,-1-1-r-r-
I
I
I
I
I
I
I
I
I I
It
-dNB = -bdNA = -d(Pa V) = -PadV = -Pad(~xr~)
(.) ~ 1 I I I I t Concentration in main
Ol
I I I I I I body of gas 2
I I I I I For irreversible ... (4.8)
= - 41tPa rc drc
CAs = CAc I I I
reaction
R re O re R
CAc = 0 Substituting the value of - dNB from Equation (4.8) into Equation (4.6), we get an expression
Radial Position
Fig. 4.5 : Representation of a reacting . for the rate of reaction in terms of the shrinking radius of unreacted core :
controlling resistance is diffusion thr P:~•cle When the 2 2
1 dN 8 41tpB rc drc Pa fc drc
hi, d"" from Fig. 4.5 th,r "° ""'°"'
'"""'t A;,
ou&, the gas film
~ -Sex dt = - 41tR2 dt = -7Tt = bkgCAg ... (4.9)

thus, the concentration driving force, CAg - CAs, becomes Cpr:sen_tat the surface of particle
3 2
reaction. nd is constant during the course ol where kg is the mass transfer coefficient between fluid and particle, m /(m ·s).
Ag

As the rate of mass transfer is defined as the rate of flow f

Rearranging Equation (4.9) gives
we base the rate on the unchanging exterior surface of a Partic\ o lllatena\
· normal to a unit surface,
llllit surface is equal to the molar flux of A from the main bll(jy e. 1'he rate of reaction of A per PB 2
""°"" of th, ponkle.
1 dNA l dNA
Of &as (
the buJk ':'' phase) to lilt
- R2 re drc = bkg CAg dt
... re= R, At t = t, ... re= re ,
-Sex dt = - 41tR 2 dt = kg(CAg-C"")::::: ¾C Integrating the above equation between the limits : At t = O
We get
[as CA& and kg both are constant for the case under consideration] °'g : : : constant ... (4.4)
p re t
_-.!l..J
R2 rc
2
drc = bkg f dt
R 0
 4.8 --------~i~tics of Fl~~d:"~~~!..~ t1on E~_fLlneerin_~
....... • 11 ... -~:.~--..·-····-·~ ~Of lllt&W rs'!!!!
~ -3- --- 1 ~~.!'.~.... . .............
errilo.l'...........
O!. . -_.. . 1·011 tbro•glt
Ash
Laye r Controls (Controlling resistance-ash layer . . . . . :
of the ash layer eonttols the <Werall n1o of ....._ •
~R 3 3
l!!.rcR3J
-11)-) •'jii[R-r,]
,.
vv·
~ffUS
istance
ver the resf the gaseous reactant A will be as shown in Fig. 4.6.
-----. -
\ Wheoe profile o Ash l a y e r ~
PsRf (rc''\31 atiofl .,. - - - ... -r- Gas film
= 3 L1-\jl)J :: bkg CAg t
coll~# /' , ''~',

- _2!!_J1 (rc13V surface of shrinking I

I \
011.. - flux of A. through
surtace of any radius r
t = 3bk, c~ L - ~R) J ... (4.lt unreacted core
containing B
I
t
I
Equation (4.10) gives us the idea regarding how the unreacted core shrinks with time Typical position in
'
\ 1
I ~ 1I/ diffusion region
let the time for complete conversion of a particle be 't. At complete conversion : 11 \. 1 ,,(
1 'I I I I,
Therefore, by putting re= 0 in &juation (4.10), we obtain an expression for,: (for thi s, ·replace
re ~ I l' ' I-. - L - .,. _ ..,,
I I I I I I
<i I I I I I I
by't). oc I I I I I I
3

't
PsR \ (0~ 1
= 3bkgCA,L1- R) j
C: co
Oo
:;::; ro C
co Q)
!:i '-
c: r/)
Ag
=CAsr-=N
CA - - - - 1-
I I

I I
I
I
I

-r-r-r
I
I
I
I
t
I
I
I
I

~ ... (4.l\1
Q) :,
() 0
C: Q)
I I I

~ 0 r/)
I I I
(.) co I I I
en
Dividing Equation (4.10) by Equation (4.11), we get
CAe = O
I I
R
I lre O: re' I
r R
I 1

~ = I -(~J ... (4.12' Radial position

Equation (4.12) ex.presses the radius of unreacted core in terms of fractional time fix Fig. 4.6 : Representation of a reacting particle when the
complete conversion. controlling resistance is diffusion through the ash layer
The radius of unreacted core in terms of fractional conversion is given by Under this condition, the instantaneous rate of reaction of A at any time is given by the rate
I - Xll = fraction of B unreacted
of diffusion of A to the reaction surface, that is,
where Xll is the fractional conversion of 8.
dNA ... (4.14)
_ Volume of unreacted core - dt = 41tr2 QA = 47tR2 QAs = 4rtrc2 QAc = constant
- Total volume of panieie
4 3 where Q" is the flux of A through a spherical surface of any radius r in the ash layer, QA> is the
-- 4}~C- -- (!.s)J flux of Athrough the exterior surface of particle and QAc is the flux of A to the reaction surface.
1
R
- nR
3 ... (4.13) The flux of A through the ash layer may be given by Fick's law :
Combining Equations (4.12) and (4.13), wc get dCA ... (4.15)
QA= <JIJe(k
'tt = 1-
(rc) 3
R = X11 (Please
· n0tc both QA and dCA/dr are positive.)
---- ~-- ... (4.14)
Where r1J 18
•
Equation (4.14) gives the relationhhip of time with the radiu~ ot e the effective diffusion coefficient of gaseous reactant A in th e ash layer.
. ~~-
convcn1on of B. Cd core and fractional Combining i:;,. .
'-"iuations (4.14) and (4.15), we get for any r
dNA dCA ... \1\.\6
Tt = 4nr2 f1Je dr = constant
ne••--are:
Atr■ll
.11_.. ...-.----..... ..................

,.. CAsC"'=CAJ andatr=rc ... CA=CAc= 0

4.10
, ,,_ ...... Kinetlc~....~!. . ~~~-i~:.~.!!11c1e ~
~ ...... -.....:_

~
....
I
0t,erfll~.lil............
_
t1on En.~_li:_i~.~-r lng - II
~elil~..................... -

Po
[ 2

I-~ -
2 r3 R3]
3~ + 3R = - Pe
....... -~-1
I R2
~ ... . .•
r2
L-6 + -f- ;iJ = bfll, C~ t
~~• of
3\
:~~!.,! --
""lid•-- la
·~·--..

- -Equation (4.16) across the ash layer, we get R2 r~ r~] .

Pe [ 6 - 2 + 3R = b~e CAg t
dN re
f 7= 4ltq,c f dCA
o
- dt Pe \ R2 r~ r~ \
R CAg
t = b!?lle cAJ6-2+ 3RJ
dNAf.l 1l '/6 common from the RHS of the above equation, we get
-1tLR>rcJ = -4itaieCAg 'faking R' \ Pe R2 \2 (~131
t = 6b!ile CAg l - 3 (R) + 2 \R) j
l (~ ... (4.20)
dNAf.l 17 C
-dtl~-Rj = 4ltqe Ag ... (4.1· . (4 20) re lates the radius .of a unreacted core with time when the diffusion through
equauon · 1 the overall reaction rate.
Equation (4.17) represents the condition of a reacting particle at any time.
dNA l dNB . . (he ash layer
. con tr? sd for the complete conversion
require . . ('t) is obtained by putting re= o
of a particle
We have : - dt = - ii dt (from the stoichiometry of reaction) 'fhe .ume( 20) as for the complete conversion of the particle : re= 0. Therefore, putting rc = o
. Equation 4. .
Replacing dN,./dt by-1/b (dNsfdt) in Equation (4.17), we obtain 10 . t by -c gives 2
and replacing
I7 Ps R [ (.OJ2 2 (9J3l
'C = 6b!?lle CAg l - \_R) + \_R) J
ldNef.1 3
-bdtl~-RJ = 41t~eCAg
2
Rearranging gives Pe R
't---
- 6b!ile CAg ... (4.21)
- dNe [ t-½] = 41tb!le CA& dt
... (4.18, Dividing Equation (4.20) by Equation (4.21), we get
We have:
- dNe = - Pe dV = - Ped (3 4 1trc3) = - 41tp re2drc !. (rcj2 (rc'\3
8
8 't = 1 - 3 \ji) + 2 (i) ... (4.22)
Replacing - dN in Equation (4.18) by its value given above, we get
2 [ 1 I]
- 47Cj)e re drc ~- R = 47tb~e CAg dt
Equation (4.22) gives us idea regarding the progress of reaction in terms of time required for
the complete conversion .
... (4.19)
f [t-½] r~ drc = b~e f dt
(rc~3
- Pe CAg We have, l - Xs = (R)

- Pe J [re - i] dre ::: b~e Jdt CAg (l - Xs)l/ =

3
~
lne limits of integration are : t == 0 ➔ re = R and t:: t ~ r :: r Th . . .
:. Equation (4.22) in terms of fractional conversion by making use of the above relation
becomes
Tc [ 2] I
- Pe fR
re -rt drc == b~e CAg f dt
e c• us, 1ntegratton gives
\~ = 1- 3 (1- x,J"" + 2 (t- x,J I ... (4.23)

re2 reJJC Wh Reaction Controls (Controlling resistance-chemical reaction step):

Chemical
- Pa [ 2- 3R = bfie CAg t
enever the resiStance
concentration . of chemical reaction step controls the overall rate of reaction, the
steps. diffu . profile for gaseous reactant A will be as shown in Fig. 4.7. In this case, diffusion
s1on of A. through the gas film and the ash layer - are rapid
reaction (slow . with
. respect to the surface
the ash lay ~eaction) and thus virtually no concentration gradients exist in the gas fl\m and in
er, 1.e., as neither the gas film nor the ash layer offers any significant resistance to
 I..........,.... A,1 2 V tr.-..tk:t tA
-~~--- 'I #
t 1it1... "'
411

·•--.• as t .,. ~~·A• «le 1u,A.1ur

Nl!'¥1,.-.,,.
,,
'. · ··I
•j1~ a,J,
,1,, , ·,,,t' 1
J 1~~ :~1~ !/Jl''i• ·

" {!~;I, .,
I h
1
.....
H.1 ,. ,.,
~,,. ~--
,1'•·~
it • µ*d'I

/41,Pt
,,*/\.,: ...,.,
ft,«°'·
!
.
.I I - , •1,,J£8.'.),.<yJ
, .
•NtJ
I ,t•".'(~f,J /-,,
.• r·r-•r.1-1,1:i .,. u,, 'Ff n.~ .,~,u,;: rti ~ rA dlc ~.._....._...,
........ .,_~
" , ? . 1..1J'f::1°
If"/'. ~✓1,J~ '•"'"
J·
I

'/Pl' I ,,,.,, <j/':, p

•. ,.r.,,~"' . r } ...:::, • - r·
v.r;w ,.-- 1 47hi -~ ch .,_ UO· -,. _ ...

! t,,,;:,,·~

,., • ,i r-; t~ ?:/fie V'j-;;;;tltHJ '1tf;.;n;1 ;j,; µ ,,,,,,

\} i::,ttl?,-.1~?
.
~: t"' U ,,, ·~
• A ;,t
~,-:::. !.i •~'j.."
1 .. . . s •, zt. . ·t1:
.., •.,, -- •.. ,,,, ,.
·~ •,.,
i
t! ".,'ts~•:;~··.-- - - - i ,.,,$ .Ir u,1.,.,; :
•,;r,.
!/ '' ,

• , ., C,.g
• f A,

ii - ::>-., sf)('/.
;,

- P» (;,:: - ~, = ?;d~ - ;,,-= rk" c," t

•• ~' :;,;,:.,-1~;1i!~
J -
'I:f',:,'7//, t :lt>a,.·r
J>11, {k - r:J 'I 41')
t:-r'A:,J!ii!r.r
~Jot V/J;U)
1"4 (.7: l q r ~ fl l l~t
~· ,,,,,. ~ ·v:-:u~ fo; com;,lm u;;,;;~.t.b;, r.1x:ttP»,6 to 1 s
».:.t U_,...,. , . ,, c.
ta::ro r-.
ul 6e
& a "-c~a~.llr~-A'~.; ;J El.)j-} prr/ln~
,; ,.~ C},A-<-J,JQJ
;, , ,,.,~ , ~{1,1;. ·-~·-' ·~" ·•,,ivI ,,,._, .J , 1,i~
..-y'l.¾ · ~'• .-,,,:;
• ,, t "
,.1J --~ ,'~I." , _ 1 ,c; (' ~u.i,,
1
,,!"/tJ~) ._,,i.- , "''" '!, ,:. I
h 1l1e: -~fit ·3W; ~ ~ -,..,.,).,,• ...,~;:,'l.ti,h, r,,t:- Z~
n. ~ i :IUll!.sir..JO-: Llw,-a..,. .... , '1#JI ';,

fda:'lle* 4.30,
~~ iW"'..JO-

v;;-.:."..:lE/1'?{:tl{J~J (4.29) ':J'f f:/f),:,UO,l (4,3HJ, •,;,:, v:,t

I ' Jf.
{ -,..V"' -~ --- , -
l
-. .
R- :,:,:
? -
it;
- ?.
'4.3
/, ,.
1-4
f4 2, a:.d {t..~:, y !..:.a7 ~ 1- 1/.g ~
rj
J·-; 't,,-' ::.~
4JZ
)VJ
= ,1:_
<> :-':'./2::.::,,.l .,, ({ £5 I ~/
( I - / ,.fs 'P
V _.,
'.,':,r.::.2·i o r:41irml (4.31) c:: nd (4 32,.
4,:.r; .-;n - --:,-!:!:;4
4z.;"_ a. z ~·Jl..~ ~,.,
r.
\ ~t 4.33
..__,..•1ie -~ (l, ,'/f; = 1-R
Tc
=1.- o-x1f?
1/. (4.33) '~i
="' ve~, t.i:e
•, U..;ie
, •,
t <lt w,mdn • r..ore ;.al
t.ie , , r, arid die
a r~ frxuoaai
~~
~ ·a b,
•it,.~~-
··;,,;J ~; ~ m
t:.e lk";::
-~rnc . . : le m
. terrr1., ,A-..
""V.! V ~ fw• bhinni'.m~
• v Sphtrieal Partkles (Variahlt/· 0 .........u.. m-: P'l,, .._a-,~
le , -~i (r.1--v-=" .
_ ,,4 C-r..:,o;;.,...;•., "' "'L-v'-' solids ar~ ir~ rr;;;tem1J form\ (no~ la"Yt' rovet ·~ \D
.,__ ~
~.,r. •WJ.) V,'/4-ef"./1 •)
Cr.J11 {'...: • · ' .
-~ , tl'ie reactin, pc:rtide u;trt.inll/'1JSN Wtuu m m.e ~uu Umt "
r •_t,,, • • ~ • '--
..--.
♦ 1; (~;,~Y•,
· ~, "'· 1"ms
• prr.iee1;s .isy illmtrated in fig. 4.8'
 14 Kinetics of Flui ~ .. . _ . . . . , 5
~ II . . . . ... •··...4...'............ ........ .......... .................~~.~8 ttici. uon Engineerlng-11
........-........ 4.16 -
~ - ·-· - ~. . layer is present, the following thr~·:· . . ' \ lfll~!}~!.11.~......................h ve been correlated for various wa-ys of contacung t\ui4 ""'1l to\i4. , -
0118 ....... ters a
reactions as no as
~~~~h
succcssioo/seriCS:
steps

A through the gas film to the surface of th

' ................ e paraine
1'ties
rre\aU
·on for
inass trans
fer of a component with mole fraction 'Y in a fluid'° ~ - -

(i) Diffusion of gaseous reactant e SO\it' co . ~

"" -- 2+ 06N
1 113
. 11cn NSc ... l434)
iS· '::I.I

the main body of gas. .

between gaseous reactant A and solid reactant B. J!:...
NSc = p<JlJ .. . Schmidt number
ii) Reaction on the surface .
( . roducts from the surface of the sohd back into the rn .
(iii) Diffusion of reacuon P a1n ~
gas through the gas film. . · NRe =~
µ ... Reynolds number
. t pmay be gas film diffusion or cherrucal reaction.
Here the rate contro11mg s e ~ _ (JL'\'13(~,in ... (4.35)
Chemical lleaction Controls (Controlling resistance-reaction step) : <JlJ - 2+0.6\Pq,) \ µ -)
The expressions derived fort, 1 and X8-t (Equations (4.29), (4.30) and (4.33)] for .
. onship is referred to as the Froessling correlation
particles of unchanging size are directly applic~ble to the shrinking spherical particles (sp~ 'fhi.s
particles of changing size) when chermcal reacuon step controls the overall rate of reaction,
1
. reIaparticle
tl
changes in size with time, kg varies during· reaction. ln oenera\ " i - -
S1nce a " ' "' ....,,...,_.
Diffusion through Gas Film Controls (Controlling resistance-film diffusion) : . ase in gas velocity and with smaller particles.
with incre l
kg o: dp ... for small dp and \ow u ... {4.36)
When diffusion through the gas ftlm controls, the situation becomes more com 1·.
. ·1.. . . pie.;
because ofth e c.hangmg panic e size m tum changmg the film resistance. Film resistance at
surface of a particle depends upon the following parameters : uin ... {4.31)
... for large dp and high u
kg o: Tn
(i) Size of particle, dp
(ii) Properties of fluid,
(iii) Relative velocity between particle and solid. Equation (4.36) represents particles in the Stokes law regimeldp: P < 0.31
--~' ,'\ ,', __ , , Shrinking unreacted particle Let us derive the conversion-time relationship for such particles.

1 ,
\ I '
..-<-Gas film --, Stokes Regime - Small Particles :
~I \ /,, ', At the time when a particle of the original size Ro has shrunk to a size R, we can write
/
1
I,
I\ I \
\~IQ\ I I
dN 0 = d (PB V) = p11 dV
... (4.38)
1 I ,J I /1 \
✓
/ (~ 3\
= P11 d \. 1tR ) = 4,Ww R dR
1
__ ,,,.. "'
,/ I I', ) I
II I ' ... _ - , ~ I
',
, __ ., ;, 3
~- I I
0 ffi I I I I The rate of reaction in term'> of 5j1.,e R of the shrinking unreacted particle is given by an
cu
2rv
C
NJ
I I
7------1
I I
I
-~
c~ C II I ~~-
I I c:i.prc~~ion bimilar to Equation (4.24). ... (4.39I
~§. ~=C~ ---~ ---- I 1 dN»
15 ~
U :j,
I
I
I
--
-- Sex dt = bk, c,,,
J< , Replacing dN, in IJquation (4.39) by its value ~vcn by Bqu,tion 14.38) and r<J>l•ci
I{ 9
R:1<Jlnl JJri•,lllr1r1 Sc~ hy 1tR1 (the 1,urfacc area of i,hrinking unreacted particl1;) 1n fl...quation (4.3 ), we get
4
1-'la. 4.K : Conl'entr11tl1111 11ronl1• of u 1(11~1'1111~ rl'lll.•ti.
111 I dN 11 ( I ) 4 11 2 !lli,
imrlnklng ,,olld 1mrtld1· 11nd l(UM'ou~ n•11c-ti.111 A Af11r lh" rl' • - sC.4 d1-· :c 41d{2 1tP R dt
A (I() f hll (11) • rit (Ill
Ille Pl'r lh
111 11
"~li1l1·h1
'Ill hctwccn
.lry :
11
dR
... (
111111 = P11 ctt = bk, c,,.,

..
 ~
~~- .. ' -· - " .~.:1~ ' ,,,Kin~!'~~ !I! Flu1 1 1
c~8"' ~_1,. .'!eeo~fl....~fl.1!. '.!~-~! fl.,
IIIJD81'P8• l!qllllion (4.35) reduces to
2!1' (/J
·
~~
-~f~ 10
. . . · · ··• •"••"··"· ,. re with this E,quati
O
k,=dp=R 1 1'11crc '

···I\
~ Equation (4.40) t,ecomes . (4 47) expresses
~ - MiCA_g ..
eqoatt00 .
kes regime and well r
-PBdt - R
1\ thC 510
. uid droplets.
iemanging, we get ~~!11 for cylindrical particl
dR - bCAg <j/ plfft!SjoP through Gas
dt - - Ps R
1· jlate of reaction is given b
sRdR = - bCAgPs ~) Jrit
The limits of integration are :
At t=O ... R=Ro and at t=t ... R=R.Integratinggives
R bC g, l
f RdR == _=&.:.. f dt
Ro Pa o
Il2R i"1 - -
1
- ~\ - bCAg at
Pa substituting for Sex and ~

Rearranging gives t = -~[R2~]

bCAg @ 2- 2
-J
21t~
2

t -~( 2
- 2bC-- ~- R2)
.e.
Ag~ -~
2

~ ... (4.4ll pj
-]
The time for complete disappe_arance of_a (latticle [i.e., for complete conversion] (t) ii
obtaioed by replacing t by t and putang R= 0 •• Equation (4.43). Therefore, ~E
Pe"'<>
1)27
~
t = (4.44), we get
Dividing Equation (4.43) by Equation '" (4,441

Eq
; = 1-(tJ
uation (4.45) can be written in terms of fractional convers ·
1onb\l
... (4.45)
.
1-Xa -- ~Ro)
( R_')3 J noting that is obtained by puttin!
't

R we get
(l -Xa)1'3 = Ro