Академический Документы
Профессиональный Документы
Культура Документы
&
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
A products
Tutorial
Problem
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
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
=
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
20
18
16
14
12
10
8
6
4
2
0
0
dC A
2
n 1
The
order
of
polynomial
should
not
be
too
low
or
too
high.
Higher
order
does
not
imply
a
better,
more
accurate
Rit.
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 )
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
= 0
C A = C A0 kt
time
C
ln A0 = kt
C A
time
= 2
1
1
=
+ kt
C A C A0
time
time
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)
t1/ 2
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.
(0.8)1 1 1
tF =
C A0
k ( 1)
ln ( rA0 ) = ln k + ln C A0
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
= rHCl , 0 = kCHCl
,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
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
Differential
Reactors
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