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Collection

&
Analysis
of Rate Dat
a
M. Ali Haid
er
Departmen
t of Chemic
al Engineer
Indian Inst
ing
itute of Tec
h
n
o
logy Delhi
CRE-I, Wed
nesday 7 th J
anuary 201
4

Experimental Data in CRE

ACS Catal. 2012, 2, 20222028

Analysis of Batch Reactor Data



A products


Tutorial Problem


Analysis of Batch Reactor Data


A products

rA = kC


A

A

A



dC A
ln
= ln k + ln C A


dt


experimentally determine order of reaction () and speciRic reaction rate
(k),

dC

= kC
dt

Methods of Differentiation
1. Graphical Method
Plotting CA/t vs time (t) and
approximate dCA/dt from the histogram

Refer to Equal Area Graphical


Differentiation (Appendix A.2,
Fogler- 4th Edition)

Methods of Differentiation
2. Numerical Method
Used when data points in independent variable (in this case, time) are
equally spaced, i.e., t2-t1 = t1-t0 = t

In such a case, three-point numerical differentiation formulas can be
used-

Initial point:


Interior point:


Final point:

3C A0 + 4C A1 C A 2
dC A

=
2t
dt t0

C A(i +1) C A(i 1)


dC A

=
2t
dt ti
C A( n 2 ) 4C A( n 1) + 3C An
dC A

=
2t
dt tn

Methods of Differentiation
3. Polynomial Fit Method
Fitting the concentration-time data
to an nth-order polynomial results in
CA as a function of t that can be
differentiated at any point to get
dCA/dt.

Computer software may be used (MS
Excel included, up to 6th order) to Rit
curves

C A = a0 + a1t + a2t 2 + ... + ant n

20
18
16
14
12
10
8
6
4

y = 0.1458x4 - 0.8843x3 - 3.2986x2 + 24.017x - 14.167


R = 0.93499

2
0
0

dC A
2
n 1

= a1 + 2a2t + 3a3t + ... + nant


dt

The order of polynomial should not be too low or too high. Higher order does not
imply a better, more accurate Rit.

Differential Method of Analysis


Finding the rate law parameters
Time

Concentration

Derivative

t0

t1

t2

t3

CA0

CA1

CA2

CA3

dC A

dt

dC A

dt



Plotting derivative vs conc on a log-log plot,
gives us rate law parameters

Slope =

dC A

dt

dC A

dt

dC
ln A = ln k + ln C A
dt

kA =

(dC A / dt ) p
(C Ap )

Example: Finding the rate equation using Differential Method


Q: Reactant A decomposes into products in a batch reactor.

A products
Find the rate equation to represent the data using the differential method.

Example: Finding the rate equation using Differential Method


Soln: *Plot the data in column 1 & 2 and
get a smooth curve
dC A
*(column 3) Draw tangents to get dt
*(column 4) Take log of negative of value
in column 3
*Plot column 4 and 5

Batch Reactor Data & Analysis


Integral method of analysis







Since is an unknown parameter that we want to Rind out, this method
requires guesswork.

dC A

= kC A

dt

The above equation yields different equations upon integration for different
values of .

dC A
C A = C A0 kt

=k
For zero order,
dt
These equations

are then plotted to
C A0
dC A
= kt
ln

= kC A
the experimental
For Rirst order,
dt
C A
data and checked

for Rit
1
1
dC
For second order,
A
=
+ kt
= kC A2
C A C A0
dt

Integral Method of Analysis


= 1

= 0

C A = C A0 kt
time

C
ln A0 = kt
C A
time

= 2

1
1
=
+ kt
C A C A0
time

time

Batch Reactor Data & Analysis


Method of Half-Lives
The half-life (t1/2) of a reaction is deRined as the time it takes for the
concentration of the reactant to fall to half of its initial value.
(What happens when there are two reactants?)

dC A
= kC A
dt


Integrating the equation for any (1),

C
1 1
1
1

1 1
A0
t = 1
t=
kC A0 ( 1) C A
k ( 1) C A
C A0



2 1 1
t=t1/2 when CA = CA0 ! t1/ 2 =
1

kC A0 ( 1)

Batch Reactor Data & Analysis


Method of Half-Lives

t1/ 2

Taking the natural log on both sides-



2 1 1
ln t1/ 2 = ln
+ (1 ) ln C A0

k ( 1)

2 1 1
= 1
kC A0 ( 1)


Method of Fractional Life is a superset of the method of half-life. Fractional
life (tF) can be calculated at any percentage of initial concentration
depletion, not jut 50%.

( F )1 1 1
tF =
C A0

k ( 1)

Where F is a fraction (0<F<1) and percentage of the initial concentration,
not percentage of reaction completed.

Same Example: Finding the rate equation


Q: Reactant A decomposes into products in a batch reactor.

A products
Find the rate equation to represent the data using the integral method or
fractional life method.

Example: Finding the rate equation using Integral Method


Soln: Integral method involves guesswork. Guess each zero, Rirst and second
order kinetics and look for straight line.









Since the data does not Rit either the Rirst- or second-order kinetics, we need
to guess nth-order kinetics using fractional life method. Say F=0.8-

(0.8)1 1 1
tF =
C A0
k ( 1)

Example: Finding the rate equation using Fractional Life


Method
Soln: *Plot CA vs t accurately, draw a smooth curve to represent the data
*Pick CA0 = 10, 5, 2 and calculate tF

Batch Reactor Data & Analysis


Method of Initial rates
For reactions that are reversible, or have the presence of a signiRicant
reverse reaction, differential method fails and method of initial rates is
useful.

It requires multiple reaction runs and a collection of initial concentration
vs initial rate data.

rA0 = kC A0

The slope of a log-log plot of rA0 and CA0 gives the reaction order

ln ( rA0 ) = ln k + ln C A0

Example: Finding rate equation using method of Initial Rates


Q: The dissolution of dolomite (calcium magnesium carbonate, CaMg(CO3)2), in
hydrochloric acid (HCl) is a reaction of particular importance in the acid simulation
of dolomite oil reservoirs. The dissolution reaction is-

4HCl + CaMg(CO3)2 Mg2+ + Ca2+ + 4Cl- + 2CO2 + 2H2O



The concentration of HCl at various times was determined from atomic absorption
spectrophotometer measurements of the calcium and magnesium ions.






Determine the reaction order with respect to HCl from the data above.
Assume that the rate law is in the form
dC

HCl = kCHCl
rHCl = kCHCl
dt

Example: Finding rate equation using method of Initial Rates


The mole balance on a constant-volume batch reactor at time t=0 gives

dC HCl

= rHCl , 0 = kCHCl

,0

dt 0

Taking log on both sides of the equation-


dC

ln HCl = ln k + ln C HCl , 0
dt 0

The initial rate (derivative at t=0) can be found from the slope of the plot. From the
Rigures, we have (given 30 cm2 of solid per liter of solution)

3)
C

(
mol/dm
1.0
4.0
2.0*
0.1*
0.5*
HCl,0

-rHCl,0 (mol/cm2-s) x 107

1.2

2.0

1.36

0.36

0.74

This gives the following plot



0.44
rHCl = kCHCl

Differential Reactors
Reactors used to determine the rate of reaction as a function of either
Inert material
concentration or partial pressure.

FA0
FAe
A differential reactor consists of a
tube containing a small amount of
catalyst in the form of a thin disk.
L
Catalyst

In addition, the reactor is considered as a differential reactor if-

C C

A L

A L + L

The differential reactor is considered to be gradient less


reaction rate is considered spatially uniform within the bed.

Measuring rate of the reaction


AP
The volumetric Rlow rate (F) through the catalyst bed is monitored and with
the weight of catalyst (W) known, the rate is found by mass balance.

Differential Reactors

Measuring rate of the reaction


AP
[FA0] [FAe] + [(Rate/mass of cat)*(mass of cat)] = 0
Inert material

FA0 FAe + (rA)(W) = 0
FA0
FAe

FA0 FAe 0C A0 C Ae FA0 X
FP
r ' A =
=
=
=
L
Catalyst
W
W
W
W

Assuming constant volumetric Rlow rate,

0 (C A0 C Ae ) 0C P

r
'
=
=

A
W
W

Thus the reaction rate can be found by measuring the product concentration
Note: When collecting data for Rluid-solid reaction systems, care must be taken that
we use high Rlow rates and small catalyst particle sizes in order to avoid mass
transfer limitations