1 Reaction based experiments

This section discusses the following 5 experimental setups that involve chemical reactions:
• Combined Flow Reactor
• Isothermal Batch Reactor
• Packed Bed Reactor
• Cascade CSTR
• Spinning Basket Reactor
It is worth to combine the common theoretical background for all the above experiments and then discuss their
individual properties in separate subsections.

1.1 Common theoretical background

The stoicheometry of a reaction involving two reactants is as follows:

aA + bB
cC + dD

or it can be written “as per mole of A” basis as

   
b c d
A+ B
C+ D (1)
a a a

In other words, one mole of A reacts with ab moles of B to produce ac moles of C and ad moles of D.

For batch reactors, the concentration CA can be determined from the number of moles (NA ) of A in the reactor per
unit volume(V ) of the reactor after a particular conversion (X) has been achieved.
NA
CA =
V
For liquids, volume change with reaction is negligible when no phase changes are taking place. One can now prepare the
following stoichiometric table involving A, B, C, and D for the general reaction given by Eq. (1) in terms of the initial
molar feed (NA0 , NB0 ), and the fraction of A converted/reacted (X)

Species Initial feed to reactor Change within reactor Remaining inside the reactor
A NA0 −NA0
X NA = NA0 − NA0
X
B NB0 −
ab NA0 X NB = NB0 − b
a NA0 X
c
NC = ac
NA0 X


C 0 a
NA0 X
d
D 0 a NA0 X ND = ad NA0 X

Further
NB0 V CB0 CB0
= =
NA0 V CA0 CA0
Hence the concentrations of species can be written as
NA NA0
CA = = (1 − X) = CA0 (1 − X) (2)
V V          
NB NA0 NB0 b CB0 b
CB = = − X = CA0 − X (3)
V V NA0 a CA0 a
NC NA0  c  c
CC = = X = CA0 X
V V a  a 
ND NA0 d d
CD = = X = CA0 X
V V a a

For the continuous reactors, the concentration CA at a given point can be determined from molar flow rate (FA ) of A
and the total volumetric flowrate (v) at that point:

FA moles/time moles
CA = = =
v volume/time volume

1
For liquids, volume change with reaction is negligible when no phase chqanges are taking place. Consequently, the
volumetric flow rate is taken to be constant. One can now prepare the following stoichiometric table for a flow system
involving A, B, C, and D for the general reaction given by Eq. (1) in terms of the entering molar flow rates (FA0 , FB0 ),
the fraction of A converted/reacted (X) and the total volumetric flow rate (v) passing through the reactor(s).
Species Feed rate to reactor change within reactor effluent rate from reactor
A FA0 −FA0
X FA = FA0 − FA0
X
B FB0 −
ab FA0 X FB = FB0 b

− a FA0 X
c c
C 0 a
FA0 X FC = a
FA0 X
d
D 0 a FA0 X FD = ad FA0 X
Further
FB0 vCB0 CB0
= =
FA0 vCA0 CA0
Hence the concentrations of species can be written as
FA FA0
CA = = (1 − X) = CA0 (1 − X) (4)
v v          
FB FA0 FB0 b CB0 b
CB = = − X = CA0 − X (5)
v v FA0 a CA0 a
FC FA0  c  c
CC = = X = CA0 X
v v a  a 
FD FA0 d d
CD = = X = CA0 X
v v a a
The rate of the reaction for either of batch or continuous flow systems is
     b
a b a a CB0 b
−rA = kCA CB = kCA0 (1 − X) CA0 − X
CA0 a
    b
(a+b−1) a CB0 b
= kCA0 (1 − X) − X (6)
CA0 a
where k is the rate constant. The CA and CB in Eq.(6) can be obtained from either Eqs.(2) and (3) or Eqs.(4) and (5)
depending on whether one is using batch system or continuous. The rate of reaction is further defined as number
of moles of reactant A reacting per unit time per unit volume of the reactor. This equation may also be
obtained from mole balance. Hence for batch reactors,
dCA dX
−rA = − = CA0
dt dt
or Z τ Z Xf
dX
dt = CA0
0 0 −rA
or
 
Z Xf
1 dX
kτ = (7)
 
(a+b−1)  n  ob 
CA0 0
(1 − X)
a CB0
− b


X
CA0 a

where Xf is the fractional conversion after time τ . For CSTRs,

FA0 − FA FA0 Xf vCA0 Xf
−rA = = =
V V V
or
V CA0 Xf
=τ =
v −rA
or
 
1 Xf
kτ = (8)
 
(a+b−1)  n  ob 
CA0 (1 − Xf )
a CB0
− b


Xf
CA0 a

2
where Xf is the fractional conversion in residence time τ inside the reactor. For plug flow reactor, the Eq.(1.1) may be
restructured as Z Xf
V dX
= τ = CA0
v 0 −rA
or
 
Z Xf
1 dX
kτ = (a+b−1)  (9)
 
n  ob 
CA0 0
(1 − X)
a CB0
− b


X
CA0 a

where Xf is the fractional conversion in residence time τ . Please note that Eqs.(7) and (9) are similar except the meaning
of their respective τ ’s.
With the above set of equations the experimentations may be carried out for any combination of reactor
configarations and any binary set of reactants with different flow rates and concentration.

1.1.1 The case of saponification of ethyl acetate with sodium hydroxide

As most of the experiments (first four) involve saponification of ethyl acetate (abbreviated as EAc) with NaOH, a special
case study may be useful. The relevant reaction is equimolar:
N aOH + CH3 COOC2 H5
CH3 COON a + C2 H5 OH (10)
Hence, a = b = c = d = 1. Hence Eqs.(7) and/or (9), i.e. for batch and/or plug flow reactors, takes the form
Z Xf
1 dX
kτ = n  o
CN aOH0 0 (1 − X) CEAc0
− X
CN aOH0
 
Z Xf 
1 1 1 
=   − CEAc0
dX
− 1 0 1 − X
C
CN aOH0 CNEAc CN aOH0 − X
0 
aOH0
 
CEAc0
1 CN aOH0 − X f
= 
CEAc0
 ln 
CEAc0

CN aOH0 CN aOH − 1 CN aOH (1 − Xf )
0 0

or
 
CEAc0
1 CN aOH0 − Xf
kτ = 
CEAc0
 ln 
CEAc0
 (11)
CN aOH0 CN aOH0 −1 CN aOH0 (1 − Xf )

and for CN aOH0 = CEAc0 .

Z Xf
1 dX Xf
kτ = 2 = (12)
CN aOH0 0 (1 − X) CN aOH0 (1 − Xf )
or
  
1 1 1
τ= − (13)
k CN aOH CN aOH0

And Eqs.(8), i.e. for CSTRs, takes the form

X
kτ = n
CEAc0
 o (14)
CN aOH0 (1 − X) CN aOH0 −X

and for CN aOH0 = CEAc0

X
kτ = 2 (15)
CN aOH0 (1 − X)
or
  
1 CN aOH0 − CN aOH
τ= 2 (16)
k CN aOH0

3
1.1.2 The case of catalytic hydrolysis of ethyl acetate
As the spinning basket reactor experiment involves hydrolysis reaction, it is worth discussing the theory. The relevant
reaction is first order
CH3 COOC2 H5 + H2 O
CH3 COOH + C2 H5 OH
In batch mode the rate of reaction is
dCEAc
−rEAc = = −kCEAc
dt
where CEAc (in mol L−1 ) is the concentration of ethyl acetate at a particular time t. Integrating the above with initial
condition, CEAc = CEAc0 at t = 0
CEAc CEAc0 − CAcA
−kt = ln = ln
CEAc0 CEAc0
or
1 CEAc0
k = ln (17)
t CEAc0 − CAcA
or
1 CEAc0
t= ln (18)
k CEAc0 − CAcA

where CAcA (in mol L−1 ) is the concentration of acetic acid.

In the continuous mode, the mole balance equation is
FEAc − FEAc0
−rEAc = = −kCEAc (19)
VR
where FEAc0 and FEAc are the inlet and outlet molar flow rate of ethyl acetate in the reactor, while VR is the volume of
the reactor. Eq.(19) can further be re-written in terms of volumetric flow rate v as

vCEAc − vCEAc0 CEAc − CEAc0

−kCEAc = =
VR τ
or
1 CEAc0 − CEAc 1 CEAc0 − (CEAc0 − CAcA )
k= =
τ CEAc τ CEAc0 − CAcA
1 CAcA
k= (20)
τ CEAc0 − CAcA
or
1 CAcA
τ= (21)
k CEAc0 − CAcA

1.2 Common reagent preparation procedure

Look at the bottles of NaOH, ethyl acetate and HCl to find out the density (ρ), concentration and/or purity of the species.
The following steps need to be carried out:

(a) Prepare VN aOH L of NaOH solution by dissolving xN aOH g of NaOH into water. NaOH is obtained in pellet form.
Its molecular weight is 40 g mol−1 . The concentration of the solution is c1 = {(xN aOH /40) /VN aOH } mol L−1 .
(b) Prepare VEAc L of Ethyl Acetate solution by dissolving xEAc mL of Ethyl Acetate into water. Ethyl acetate is
obtained in liquid solution of known concentration (c2 mol L−1 ). In case of solution with unknown concentration, its
concentration can be calculated from its molecular weight 88.11 g mol−1 and density 0.9 g mL−1 . The concentration
of the solution is c2 = {(xEAc × 0.9/88.11) /VEAc } mol L−1 .
(c) Prepare sufficient quantity (say 2 L) of HCl solution by dissoving xHCl mL of HCl into water. HCl s obtained in
liquid solution of known concentration (c3 mol L−1 ). We know that 36.5 g L−1 of HCl is a 1 N solution of HCl and its
molecular weight is 36.5 g mol−1 as well. In case of 0.1 N solution HCl, cHCl = {(0.1 × 36.5) /36.5} = 0.1 mol L−1 .
Fill up the burrette and keep it aside for titration purpose.

4
1.3 Combined Flow Reactor
The schematic of the experimental setup is shown in the Fig. 1. The outlet condition of PFR is the inlet condition of the
CSTR. The volumes of two reactors may be indicated as VP F R and VCST R (both in L).

(a) Prepare 20 L each of NaOH (concentration c1 mol L−1 ) and Ethyl Acetate solution (concentration c2 mol L−1 ) and
2 L HCl
(b) Open the valves for PFR-CSTR in series experiment. The flowrates in Rotameter 1 (connected to Tank 1) and
Rotameter 2 (connected to Tank 2) indicate a value v1 and v2 respectively. Hence

v = v1 + v2
c1 v1
CN aOH0 =
v
c2 v2
CEAc0 =
v

(c) Wait 10 minutes after the flowrates through both the rotameters are stable. Take samples VSP F R and VSCST R (both
in mL) from the sampling ports of PFR and CSTR respectively.
(d) Titrate the samples with HCl. Suppose VTP F R and VTCST R (both in mL) quantity of HCl of strength cHCl is needed

Reactant A Operation Opened valves

Only PFR V1, V2, V6
Only CSTR V3, V4, V7
V3 Combined V1, V2, V5, V6 (only during sampling), V7

V1
V5
PFR
V6

V2
Products C and D
CSTR
V4 V7

Products C and D
Reactant B

Figure 1: Schematic of combined flow reactor

5
 to neutralize the contents of sample. Then do the following calculations with i ∈ {P F R, CST R}:

cHCl VTi
CN aOHi =
VSi
CN aOH0 − CN aOHP F R
XfP F R =
CN aOH0
CN aOHP F R − CN aOHCST R
XfCST R =
CN aOHP F R
  
CEAc0
CEAcP F R = CN aOH0 − XfP F R
CN aOH0
 
CEAc0
1 CN aOH0 − XfP F R
kP F R = 
CEAc0
 ln 
CEAc0
 (22)
VP F R


v CN aOH0 CN aOH0 −1 CN aOH (1 − XfP F R )
0

XfCST R
kCST R = 
CEAcP F R
 (23)
VCST R


v CN aOHP F R (1 − XfCST R ) CN aOHP F R − XfCST R

In case of CN aOH0 = CEAc0 , Eqs.(22) and (23) would take the form
  
VP F R 1 1 1
= − (24)
v kP F R CN aOHP F R CN aOH0
  
VCST R 1 CN aOHP F R − CN aOHCST R
= 2 (25)
v kCST R CN aOHP F R

(e) Repeat the steps (b)-(d) for 3 samples of the same flow rate and take the average value of k using Eqs.(22) and (23)
(f) Repeat the steps (b)-(e) for 2 more flow rates.
   
VP F R 1 1
(g) Alternatively, for equimolar case, one can use Eq.(24) to plot a graph of vs. − to
 v  CN aOHP F R CN aOH0 
−1 VCST R CN aOHP F R − CN aOHCST R
obtain a slope of kP F R and one can use Eq.(25) to plot a graph of vs. 2 to
v CN aOHP F R
−1
obtain a slope of kCST R

Experimental results and calculation

The concentrations of NaOH, ethyl acetate and HCl are c1 , c2 and cHCl as calculated through the procedure described in
common reagent preparation procedure (Sec 1.2). The following table may be populated and calculated:

PFR CSTR
v1 v2 CN aOH0 CEAc0 Samples
VS VT CN aOH Xf CEAc k kavg VS VT CN aOH Xf k kavg
1
2
3
1
2
3
1
2
3

or follow the step (g) above.

6
1.4 Packed Bed Reactor
The packed bed reactor is regarded as similar to plug flow reactor where, in addition to the longitudinal direction,
concentration of reactants vary along the radial direction too. Hence the equation of PFR will be valid in all calculations.

(a) Prepare 20 L each of NaOH and Ethyl Acetate solutions and 1 L of HCl of known concentrations (say c1 , c2 and cHCl
mol L−1 respectively).
(b) Operate the packed bed reactor with v1 L h−1 of NaOH and v2 L h−1 of ethyl acetate in the packed bed reactor.
Hence,

v = v1 + v2
c1 v1
CN aOH0 =
v
c2 v2
CEAc0 =
v

(c) Wait for τ minutes. Take samples VS mL from the reactor and titrate it with HCl. Suppose VT mL quantity of HCl
of strength cHCl is needed to neutralize the contents of sample. Then do the following calculations:
cHCl VT
CN aOH =
VS
CN aOH0 − CN aOH
Xf =
CN aOH0

(d) Use appropriate equations to obtain the value of k. Do the sampling thrice.

(e) Repeat the steps (b)-(d) for 2 more flowrates.

 
1 1
(f) Alternatively for equimolar case one can use Eq.(13) to plot τ vs. − to obtain the slope of k −1
CN aOH CN aOH0

Experimental results and calculation

The concentrations of NaOH, ethyl acetate and HCl are c1 , c2 and cHCl as calculated through the procedure described in
common reagent preparation procedure (Sec 1.2). The following table may be populated and calculated:

v1 v2 CN aOH0 CEAc0 Samples VS VT CN aOH Xf k kavg

1
2
3
1
2
3
1
2
3

or use the step (f) stated above.

7
1.5 Cascade CSTR
The volumes of the reactors are same, say V L. For saponification reaction, the steady state material balance over nth
reactor is

vCN aOH(n) = vCN aOH(n−1) + (−rN aOH ) V

CN aOH(n−1) = CN aOH(n) + τ kCN aOH(n) CEAc(n)
CN aOH(n−1) − CN aOH(n)
k= (26)
τ CN aOH(n) CEAc(n)

where
CEAc(n) = CEAc(n−1) − CN aOH(n−1) X = CEAc(n−1) − CN aOH(n−1) + CN aOH(n)
and τ is the residence time. The Eq.(26) may also be expressed as
( )
1 CN aOH(n−1) − CN aOH(n)
τ= (27)
k CN aOH(n) CEAc(n)

Experimentation procedure is as follows:

(a) Prepare 20 L each of NaOH and Ethyl Acetate solutions and 1 L of HCl of known concentrations (say c1 , c2 and cHCl
mol L−1 respectively).
(b) Operate the cascade CSTR with v1 L h−1 of NaOH and v2 L h−1 of ethyl acetate in the CSTRs in series. Hence,

v = v1 + v 2
c1 v1
CN aOH0 =
v
c2 v2
CEAc0 =
v

(c) Wait for 10 minutes after the product comes out of 3rd reactor. Take samples VS(n) mL from nth reactor and titrate
it with HCl. Suppose VT(n) mL quantity of HCl of strength cHCl is needed to neutralize the contents of sample. Then
do the following calculations:
cHCl VT(n)
CN aOH(n) =
VS(n)

(d) Use Eq.(26) to obtain the value of k.

(e) Alternatively one can use Eq.(27) to obtain the value of k −1
(f) Repeat the steps (b)-(d) for 3 more flowrates and find the average k.

Experimental results and calculation

The concentrations of NaOH, ethyl acetate and HCl are c1 , c2 and cHCl as calculated through the procedure described in
common reagent preparation procedure (Sec 1.2). The following table may be populated and calculated:

v1 v2 CN aOH0 CEAc0 n VSn V Tn CN aOHn CEAcn k kavg

0 Not Applicable Not Applicable Not Applicable
1
2
3
0 Not Applicable Not Applicable Not Applicable
1
2
3
0 Not Applicable Not Applicable Not Applicable
1
2
3

8
1.6 Isothermal Batch Reactor
Further
E
k = k0 e− RT (28)
E
ln k = ln k0 − (29)
RT
where T is in K. Perform the experiment with four different temperatures and find k for each of them. Plot ln k vs. T1
and obtain a graph of the following nature (Fig 2). It is possible to obtain E and k0 from the slope and intercept of the
graph

ln 𝑘0

1
𝐶𝐴
𝐸
Slope = − 𝑅

ln 𝑘

1
𝐶𝐴0
1
𝑇

Figure 2: Temperature dependence of reaction constant in terms of Arrhenius equation

(a) Prepare 20 L each of NaOH (concentration c1 mol L−1 ) and Ethyl Acetate solution (concentration c2 mol L−1 ) and
1 L HCl
(b) Take v1 L of NaOH and v2 L of ethyl acetate in the isothermal batch reactor at temperature T . Hence,

v = v1 + v2
c 1 v1
CN aOH0 =
v
c2 v2
CEAc0 =
v

(c) Wait for τ minutes. Take samples VS mL from the reactor and titrate it with HCl. Suppose VT mL quantity of HCl
of strength cHCl is needed to neutralize the contents of sample. Then do the following calculations:
cHCl VT
CN aOH =
VS
CN aOH0 − CN aOH
Xf =
CN aOH0

(d) Use appropriate equation to obtain the value of k.

 
1 1
(e) Alternatively for equimolar case one can use Eq.(13) to plot τ vs. − to obtain the slope of k −1
CN aOH CN aOH0
(f) Repeat the steps (b)-(d) at 3 more temperatures. Plot the graph of Eq.(29) to obtain the constants of Arrhenius
Equation (Eq. 28).

9
Experimental results and calculation
The concentrations of NaOH, ethyl acetate and HCl are c1 , c2 and cHCl as calculated through the procedure described in
common reagent preparation procedure (Sec 1.2). The following table may be populated and calculated:

T v1 v2 CN aOH0 CEAc0 Samples VS VT CN aOH Xf k kavg

1
2
3
1
2
3
1
2
3
1
or use the step (e) stated above to obtain the value of k. Further, kavg vs. T may be plotted to obtain the constants of
Arrhenius Equation (Eq. 28)

1.7 Spinning Basket Reactor

Th Eq.(17) will be applicable in this experiment. Let us consider the following:

VEAc = volume of ethyl acetate taken for feed preparation (in L)

ρEAc = density of ethyl acetate (902 kg m3 )
MEAc = molecular weight of ethyl acetate (88.11)
VW = total volume of distilled water taken for feed preparation (in L)
VS = volume of sample taken out of reactor for titration (in mL)
VT = volume of NaOH needed for neutralization (in mL)

Then
ρEAc VEAc
CEAc0 =
MEAc (VW + VEAc )
VT CEAc0
CAcA = (30)
VS
The reaction rate constant k will depend on weight of catalyst and speed of rotation of spinning basket.

1.7.1 Observation and calculation table (batch mode)

no. Speed (RPM) t (min) VS VT CAcA (using Eq.30) k (using Eq.17)
1
2
3
CEAc0
or alternatively one can use Eq.(18) to plot t vs. ln in order to obtain k −1
CEAc0 − CAcA

1.7.2 Observation and calculation table (continuous mode)

no. Speed (RPM) τ (min) VS VT CAcA (using Eq.30) k (using Eq.20)
1
2
3
CAcA
or alternatively one can use Eq.(21) to plot τ vs. in order to obtain k −1
CEAc0 − CAcA

10
2 Experiments involving Residence Time Distribution studies only
The amount of tracer material, ∆m, leaving the reactor betwen time t and (t + ∆t) is ∆m = vc (t) ∆t where v is the
volumetric flow rate of effluent and c (t) is the concentration of tracer in the effluent. In differential form
dm = vc (t) dt
In other words, dm is the amount of tracer exiting the reactor that has spent an amount of time between t and (t + dt) in
the reactor. If the total amount of tracer, M , that was injected into the reactor is not known directly, it can be obtained
as Z M Z ∞
M= dm = vc (t) dt
0 0
Now the fraction of tracer that has a residence time in the reactor between time t and (t + dt) is
( )
dm vc (t) dt c (t)
= R∞ = R∞ dt = E (t) dt
M 0
vc (t) dt 0
c (t) dt
where the quantity E (t) is called the residence time distribution (RTD) function. It is the function that describes in a
quantitative manner how much time different fluid elements have spent in the reactor. Please note that v is assumed to
be constant throughout the reactor operation. An alternative way to interprete the RTD function R t is in its integral form,
i.e. fraction of material leaving the reactor that has resided in it for times between t1 and t2 is t12 E (t) dt. We know that
the fraction of all the material that has resided for a time t in the reactor between t = 0 and t = ∞ is 1. Therefore
Z ∞
E (t) dt = 1
0

The first moment (or the mean) of the RTD function

R∞ Z ∞
0
tE (t) dt
tm = R ∞ = tE (t) dt
0
E (t) dt 0

The second moment is taken about the mean and is called the variance (or the square of the standard deviation)
Z ∞ Z ∞
2
σ2 = t2 − 2tm t + t2m E (t) dt


(t − tm ) E (t) dt =
Z0 ∞ Z ∞0 Z ∞
= t2 E (t) dt − 2tm tE (t) dt + t2m E (t) dt
Z0 ∞ 0 0

= t2 E (t) dt − 2tm × tm + t2m

0
Z ∞
2
σ = t2 E (t) dt − t2m
0

Often a normalized RTD, E (θ), is used with dimensionless time

t
θ=
tm
Then ( )
c (θ) c (t) c (t)
E (θ) = R ∞ = R∞   = tm R∞ = tm E (t)
0
c (θ) dθ c (t) d t
0
c (t) dt
0 tm

as the profiles of c (t) and c (θ) , when mapped both in numerator and denominator, do not alter the ratio. Similarly,
Z ∞ Z ∞
2
σθ2 = θ2 − 2θ + 1 E (θ) dθ


(θ − 1) E (θ) dθ =
0 0
Z ∞ ( 2   )   
t t 1
= −2 + 1 {tm E (t)} dt
0 tm tm tm
Z ∞ Z ∞ Z ∞
1 2 2
= 2 t E (t) dt − tE (t) dt + E (t) dt
tm 0 tm 0 0
1 2 σ2
= 2 σ 2 + t2m −


(tm ) + 1 = 2 + 1 − 2 + 1
tm tm tm
2
σ
σθ2 = 2 (31)
tm

11
2.1 RTD in a CSTR
The nominal space time or average residence time, τ is defined as being equal to V /v where V is the volume of the reactor.
In the absence of dispersion and for a constant volumetric flow rate, no matter what RTD exists for a particular reactor,
ideal or non-ideal, this nominal space time τ is equal to tm . A material balance on tracer that has been injected at time
t = 0 yields (for t > 0)

In − Out = Accumulation
dc (t)
0 − vc (t) = V
dt
because the reactor is perfectly mixed; c (t) is the concentration of tracer either in the effluent or within the reactor. Here
C
v t
Z Z
dc
=− dt
C0 c V 0
1
ln C − ln C0 = − (t − 0)
τ
t
C = C 0 e− τ

Then
( ) ( t
)
c (t) C0 e− τ
E (θ) = τ E (t) = τ R∞ =τ R∞ t
0
c (t) dt 0
C0 e− τ dt
t
τ e− τ t
=h −t
i ∞ = e− τ
e τ
− τ1 0
E (θ) = e−θ

2.2 RTD for reactors based on dispersion model

The dispersion model uses a dimensionless term, Peclet number,
Rate of transfer by convection Ul
Pe# = =
Rate of transfer by diffusion or dispersion D

where l is the characteristics length term, D is the effective dispersion coefficient (m2 s−1 ) and U is the superficial velocity
of the fluid. There are two types of Pe# in common use. The first one is reactor Per which uses reactor length as the
characteristic length. Other type is fluid Pef which incorporates fluid mechanical behaviour to decide the characteristics
length. In a packed bed, this length is particle diameter dp .

U dp
P ef =
φD

where φ is the voidage. For packed bed we often use average superficial velocity as thus Uφ is commonly used as packed
bed velocity term. In an empty tube, the fluid behavior is determined by the tube diameter dt and
U dt
P ef =
D
It is, of course, very simple to convert P ef to P er . Multiply by the ratio L/dp or L/dt . The reciprocal of P er is sometimes
called the vessel dispersion number. The dispersion coefficient can be determined from the pulse tracer experiment. The
effluent concentration of the reactor is measured as a function of time. From the effluent concentration data, the mean
residence time and variance are calculated, and these values are then used to determine dispersion coefficient.
There are two cases that we need to consider: boundary conditions for closed vessels and for open vessels (Fig. 3). In
the case of closed-closed vessels, we assume that there is no dispersion or radial variation in concentration either upstream
(closed) or downstream (closed) of the reaction section; hence, this is a closed-closed vessel, as shown in Fig. 3(a). In
an open vessel, dispersion occurs both upstream (open) and downstream (open) of the reaction section; hence, this is an
open-open vessel as shown in Fig. 3(b). A closed-open vessel boundary condition is one in which there is no dispersion
in the entrance section but there is dispersion in the reaction and exit sections. For closed-closed system tm = τ and (see
Eq. 18-39 of Fogler’s book)

12
 condition is one in which there is no dispersion in the entrance section but
there is dispersion in the reaction and exit sections.

(a) Closed-closed vessel (b) Open-open vessel

Figure 18-7 Types of boundary conditions.
Figure 3: Open/closed vessels dispersion

18.4.2A Closed-Closed Vessel

2 2Boundary
2 Condition
−P e


σθ = − 1−e r
(32)
P er P e2r
For a closed-closed vessel, we have plug flow (no dispersion) to the immediate
When a tracer is injected into a packed bed at a location more than two or three particle diameters downstream from
left
the entrance andofmeasured
the entrance line (z
some distance = 0–) (closed)
upstream andthe
from the exit, toopen-open
the immediate right of
vessel boundary the exit
conditions apply. For
(see +
Eq. 18-45 of Fogler’s book) + –
z = L (z = L ) (closed). However, between z = 0 and z = L , we have dispersion
open-open system
and reaction. The corresponding entrance 
2 boundary condition is

tm = 1 + τ (33)
At z = 0: – P er +
FA(0 ) = FA(0 )
thereby two cases arise. When space time τ of the reactor is known then (see Eq. 18-46 of Fogler’s book)
2 8
σθ2 = + (34)
P er P e2r
and when τ is unknown. This situation arises when there are dead or stagnant pockets that exist in the reactor along
with the dispersion effects. (see Eq. 18-47 of Fogler’s book)
2P er + 8
σθ2 = (35)
P e2r + 4P er + 4
One needs to use one’s own discretion which of the equations amongst Eqs.(32) to (35) need to be used for Plug Flow
Tubular Reactor (PFTR) and Packed Bed Reactor (PBR).

2.3 Common calculation procedure for all reactors

Let
-1
CN aOH = Concentration of NaOH taken in the burette for titration (mol L )
VN aOH(i) = volume of NaOH needed to neutralize the collected sample (mL)
-1
CH2 SO4(i) = concentration of H2 SO4 in the nth sample (mol L )
VR = volume of reaction mass in the reactor (L)
VSamp = fixed volume of sample collected every time from the reactor (mL)
F = volumetric flow rate of liquid flowing through the reactor at steady state (L h−1 )

The acid-base reaction is as follows:

H2 SO4 + 2N aOH −→ N a2 SO4 + 2H2 O

CN aOH VN aOH(i)
hence, 2 mol of N aOH reacts with 1 mol of H2 SO4 . Thereby, CN aOH VN aOH(i) mols of N aOH reacts with
2
mols of H2 SO4 . Then for an experiment with a particular flow rate, the concentration of H2 SO4 (in mol) in the ith sample
of quantity Vsamp taken from the effluent is
CN aOH VN aOH(i)
CH2 SO4(i) = (36)
2Vsamp

13
then populate the following table for a particular flow rate of effluent through sample collection, titration and calculation

i ti VN aOH(i) CH2 SO4(i) ∆ti θi E (θi )

0 Not applicable
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15

with the following calculations

VR
τ=
F
∆ti = ti − ti−1
15
X
I= CH2 SO4(i) ∆ti
2
15
X
tm = I −1 ti CH2 SO4(i) ∆ti
2
15
X
σ 2 = I −1 t2i CH2 SO4(i) ∆ti − τ 2
2
ti
θi =
tm
E (θi ) = tm I −1 CH2 SO4(i)

Plot a graph between θ and E (θ). Repeat the above with some other flow rate.

2.4 Additional calculation procedure for PFTR and PBR

Use Eq.(31) and Eqs.(32) through (35) to compute relevant Peclet Number (by trial method or otherwise) and find the
dispersion coefficient.

14
3 Trickle Bed Reactor
The experimental study is limited only to the hydrodynamic study of two-phase flow along the trickle bed reactor. The
total two-phase flow pressure drop may be written as sum of three major components.
       
∆P ∆P ∆P ∆P
= + +
∆L tp ∆L a ∆L f ∆L h

where
 
∆P
= Total two-phase pressure drop
∆L tp
 
∆P
= Two-phase flow pressure drop due to acceleration
∆L a
 
∆P
= Two-phase flow pressure drop due to frictional losses
∆L f
 
∆P
= Hydrostatic pressure drop
∆L h

Hydrostatic pressure drop is the two-phase flow pressure drop due to change in elevation. Since the focus of this study
deals with a small length only, the hydrostatic pressure drop is neglected. Also the pressure drop due to acceleration
in isothermal flows in relatively uniform diameter and short pipes is very small and it is often negligible. Therefore,
fthe term two-phase flow pressure drop refers to the frictional pressure drop component only. Frictional pressure drop
is the result of an irreversible work done due to shear at the pipe wall and at the gas-liquid interface. The frictional
pressure drop in two phase flow is much more complex to predict than single phase flow. This is due to the fact that it
is dependent on many flow parameters such as pipe diameter, mass flux, pipe orientation, pipe surface roughness, fluid
properties and interfacial contact area between the phases. There are many two-phase flow pressure drop correlations
in the open literature. Sometimes it becomes difficult to know which correlation would be more accurate or suitable for
the task at hand. Moreover, the lack of good understanding of the two-phase flow behavior had led many researchers to
develop correlations that are limited to a certain range of flow parameters. Therefore, the user of the correlation must
understand those restrictions and must make sure the task at hand is within the restrictions. Literature on two-phase
flow pressure drop correlations can be classified in different ways, such as

• Separated flow models

• Homogeneous flow models
• Empirical models

• Phenomenological models
• Numerical models

A few of the separated flow models may be discussed as applicable to trickle bed reactor.
In separated flow models each phase/fluid is assumed to flow separately from one another. Most separated flow models
assume different velocities for each phase unlike homogeneous flow models where both of the fluids are assumed to have
the same velocity. A method of using a two-phase frictional pressure drop multiplier, φ, is a very popular method of
developing a separated flow model pressure drop correlation. This type of analysis was found to be appealing because
single-phase flow techniques and results are analogically related to two-phase flows by this method. This instance has
a benefit of avoiding ambiguity over which physical property of the phases to use, such as which viscosity of either of
the phases to use during calculation of two-phase pressure drop. There are two ways of modeling the two-phase friction
multiplier. The first one is assuming all the flow to be as one of the single phases such as all flow as liquid or all flow as
gas. The implication here is to use the total mass flux (the sum of the mass fluxes for each phase) instead of the mass
flow for each phase. Subscripts ‘lo’ and ‘go’ are used to indicate liquid only and gas only, respectively.
 ∆P 
∆L tp
φ2lo =  ∆P 
∆L
 ∆P lo
∆L tp
φ2go =  ∆P 
∆L go

15
The second method is to assume as if only one of the phases exist and use the respective mass flux only while calculating
the Reynolds number. Therefore in this case, only the respective mass flux is used to calculate the Reynolds number.
 ∆P 
∆Ltp
φ2l =  ∆P  (37)
∆L
 ∆P  l
∆L
φ2g =  ∆P tp
∆L g

Usually using the liquid two-phase friction multiplier is preferred because the liquid density generally does not vary too
much in most of the applications as compared to the gas density.
Lockhart and Martinelli (1949) proposed a two-phase flow pressure drop correlation based on experimental data
collected from several two-phase flow researchers. Their correlation development is based on two-phase pressure drop data
with simultaneous flow of air with several types of liquids including water, benzene, diesel, kerosene and various oils flowing
in a diameter ranging from 1.5 mm to 25 mm. The absolute pressure ranges from 16 to 52 psi. They developed their
correlation based on two basic assumptions. The first assumption states that the static pressure drop of the liquid phase
and the gas phase must be equal for all the flow patterns when there is no appreciable radial static pressure difference.
The second assumption states that the sum of the volume occupied by each phase must be equal to the total volume of
the pipe. According to the authors these two assumptions imply that the flow pattern does not change along the pipe
length. Therefore, the authors indicated that alternate slugs of liquid and gas moving down the pipe termed as the slug
flow is excluded from their investigation. Four types of flow mechanisms were assumed during the development of their
correlation. They categorized the flow mechanisms as:
Viscous-Viscous (vv): when the flow of both the liquid and the gas is laminar
Viscous-Turbulent (vt): when the flow of the liquid is laminar and the gas is turbulent
Turbulent-Viscous (tv): when the flow of the liquid is turbulent and the gas is laminar
Turbulent-Turbulent (tt): when the flow of both the liquid and the gas is turbulent
The authors introduced a new parameter called Xii , i ∈ v, t. This parameter is a function of the ratios of the mass
fluxes, densities, and viscosities of the liquid and the gas phase in addition to the diameter of the pipe. The parameter
Xii relates the single phase pressure drops for liquid and gas as if each fluid is flowing alone in the pipe.
   
∆P 2 ∆P
= Xii
∆L l ∆L g

They proposed a correlation to calculate the value of Xii for each type of flow mechanism listed above. They showed that
for the four types of flow mechanisms, the value of Xii can be calculated as
   
2 ṁl ρg µl
Xvv = (38)
ṁg ρl µg
    
ṁl ρg µl Cl
2
Xvt = Rel−0.8 (39)
ṁg ρl µg Cg
    
2 ṁl ρg µl Cl
Xtv = Re0.8
g (40)
ṁg ρl µg Cg
   (5/9)  (1/9)
2 ṁl ρg µl
Xtt = (41)
ṁg ρl µg

Rel and Reg are the Reynolds number of the liquid and gas respectively, as if each fluid is flowing alone in the pipe. Cl
and Cg are constants in the general form of Blasius equation for friction factor of the liquid and gas, respectively. The
general form of the Blasius equation is expressed as
Cl
fl =
Renl
Cg
fg =
Remg

The authors determined the values of the constants Cl and Cg from experimental data and they specified the value of Cl
and Cg for a smooth pipe. The values of n, m, Cl and Cg to be used for calculating Xii from the above equations is as

16
 Figure 4: Lockhart-Martinelli parameter

given in the following table.

Variables Viscous-Viscous Viscous-Turbulent Turbulent-Viscous Turbulent-Turbulent

n 1 1 0.2 0.2
m 1 0.2 1 0.2
Cl 0.046 16 0.046 16
Cg 0.046 0.046 16 16

Lockhart and Martinelli (1949) correlation was presented graphically as plot of the two-phase friction multiplier φ versus
the dimensionless parameter Xii as in the Fig. 4.
Alternatively the total pressure drop can also be computed through
 ∆P  !
∆L tp 0.416
log  ∆P   ∆P  = 2 (42)
∆L l + ∆L g (log Xii ) + 0.666

As has been noted above, the parameter Xii has unique value for each of the four flow mechanisms. The authors suggested
tentative criteria for determining the flow mechanism based on Reynolds number of each single phase. They suggested
Re = 1000 to be the end of laminar two-phase flow and Re = 2000 to be start of turbulent flow mechanism. The authors
claim Re = 2000 is a conservative criterion because of the following reasons. If we consider the gas phase flowing alone in
a pipe at Re = 2000 the flow mechanism of the gas is turbulent. An introduction of a liquid phase in the pipe will increase
the Reynolds number and will eventually lower the transition point of the flow mechanism. This way, the transition point
ensures that at Re = 2000 the flow is turbulent.
Chisholm (1967) presented a theoretical analysis of Lockhart and Martinelli (1949) correlation by including the effect of
interfacial shear forces. Considering the interfacial shear force between the phases while developing the correlation enabled
to predict the hydraulic diameters of the phases more accurately than Lockhart and Martinelli (1949). Although Lockhart
and Martinelli developed and plotted the relationship between φ and Xii , using graphs to calculate values is inconvenient
and raises concerns in degree of accuracy while reading from the plots. This made the Chisholm (1967) correlation more
useful and convenient for two-phase flow pressure drop calculation in many practical applications. Simplified equations
were proposed by Chisholm (1967) in terms of Lockhart and Martinelli (1949) parameters.

C 1
φ2l = 1 + + 2 (43)
Xii Xii

17
The values of C are given for four different fow mechanisms, shown in the table below.

Flow mechanism (Liquid-Gas) Value of C

Viscous-Viscous 5
Turbulent-Viscous 10
Viscous-Turbulent 12
Turbulent-Turbulent 20

3.1 Experimentation and calculation procedure

(a) Run liquid flow at 3 different flow rates and measure the pressure drops in each case

(b) Run gas flow at 3 different flow rates and measure the pressure drops in each case
(c) Run both liquid and gas flow at 3×3 different flow rates and measure the pressure drops in each case
(d) Calculate velocity and Reynold’s number in each case to find whether they are in which ii zone (vv, vt, tv or tt)
(e) Calculate Xii from Eq.(38) to (41)

(f) Find φl either from Fig. 4 and/or from Eq.(43)

(g) Calculate theoretical ∆P
 
∆L tp from Eq.(37) and/or (42)

(h) Compare the value of theoretical ∆P

 
∆L tp,expt with that of experimentally found value in Step (c).

3.2 Necessary data and other available information

dp = diameter of packing material (mm)
D = diameter of the column (mm)
π D

2
A = cross-sectional area of the column (m2 ) = 4 1000
Z = height of packing between manometer taps (m)
T = ambient temperature (K)
ρL = density of liquid phase (kg m−3 ) ρL(water) = 1000
ρG = density of gas phase (kg m−3 ) ρG(air) = Patm Mair
RT = 101325×28.96
8314T = 353T −1
ρu = density of upper manometer liquid (kg m−3 ) ρu(Hg) = 13593
ρl = density of lower manometer liquid (kg m−3 ) ρl(CCl4 ) = 1590
µL = viscosity of liquid phase (Pa s) µL(water) = 8.9 × 10−4
−1
µG = viscosity of gas phase (Pa s) µG(air) = 1.458 × 10−6 T 3/2 (T + 110.4)
ε = porosity of trickle bed
QL = liquid flow rate (LPH)
QG = gas flow rate (LPM)
VL = superficial velocity of liquid phase (m s−1 )
VG = superficial velocity of gas phase (m s−1 )
Re#L = Reynold’s number of liquid phase
Re#G = Reynold’s number of gas phase

3.3 Observations and experimental results

Populate the following tables
QL (in LPH)
Upper pu = (ρu −ρL100
)g|u1 −u2 | Lower pl = (ρl −ρL )g|l1 −l2 |
100 (in ∆pL = |pu − pl |
manome- (in Pa) manome- Pa) (in Pa)
ter reading ter reading
(in cm) (in cm)
u1 u2 l1 l2

18
 QG (in LPM)
Upper pu = (ρu −ρG100
)g|u1 −u2 | Lower pl = (ρl −ρG )g|l1 −l2 |
100 (in ∆pG = |pu − pl |
manome- (in Pa) manome- Pa) (in Pa)
ter reading ter reading
(in cm) (in cm)
u1 u2 l1 l2

QG QL Upper pu = (ρu −ρG100

)g|u1 −u2 | Lower pl = (ρl −ρG )g|l1 −l2 |
100 (in ∆ptp = |pu − pl |
(in (in manome- (in Pa) manome- Pa) (in Pa)
LPM) LPH) ter reading ter reading
(in cm) (in cm)
u1 u2 l1 l2

10−3 QL dp VL ρL
No. QL VL = 3600A Re#
L = µL (1−ε) Laminar or Turbulent
1
2
3

10−3 QG dp VG ρG
No. QG VG = 60A Re#
G = µG (1−ε) Laminar or Turbulent
1
2
3
and
No. QL QG Flow mechanism Xii (using Eqs.38 φ (Using Eq. 43 ∆ptp,theo (using %error=
∆ptp,exp t −∆ptp,theo
(vv,vt,tv,tt) to 41) or Fig.4) Eq.37 or 42) ∆ptp,exp t ×
100
1
2
3
4
5
6
7
8
9

19