Problem Set #1 DUE January 16th, 2015

ChBE 4300 Kinetics and Reactor Design Spring 2015

School of Chemical & Biomolecular Engineering -- Georgia Institute of Technology

Problem Set #1 DUE January 16th, 2015

Reading: Fogler, Chapters 1-3
Direct questions to Dalar Nazarian
1. The following liquid-phase reaction is carried out in a batch reactor maintained at 54oC.
2A + B C
The reaction is first order in each of the two reactant species, and the reaction rate constant at 54oC
is 0.006 L/mol-min. An aqueous feed consisting of both A & B (CAo = 1 mol/L; CBo = 0.4 mol/L) is
placed in the batch reactor (volume = 2000 L) and allowed to react. How long will it take for the
concentration of C in the reaction mixture to reach a value of 0.3 mol/L?
Final Answer
= 391.694
Process:
Begin with the general mole balance equation:
0 + =

Since this is a batch reaction, by definition 0 = 0 . Also by definition,

. For this

reaction, the only generation/consumption term is . Therefore, the general mole balance
equation reduces to:
=

Assuming perfect mixing, = . Assuming constant fluid volume,

=
=

Problem Set #1 DUE January 16th, 2015

The system of equations is:

= 2

The Initial conditions are: (0) = 0 , (0) = 0 (0) = 0

We can solve for , , using the following relationships :

2
= ( 2 ) = 0

+
= ( + ) = 0

If we integrate the above given the initial conditions we find that,

( 2 ) = 0 20
( + ) = 0
This gives us a relationship between and of
= 0 20 + 2 = 0.2 + 2
We can plug this relationship into the equation for

and solve for

= (0.2 + 2 ) = 2(2 + 0.1 )

(2

0.4

= 2
+ 0.1 )

2
(2 + 0.1 )
0

10 ln (
) + 25.25 = 2
10 + 1
k=0.006 L/mol-min

0.08
0.8 + 0.0012

Problem Set #1 DUE January 16th, 2015

Then we can solve for using the initial relationship we set up between and
( + ) = 0 = 0.4
Plug in () = 0.3 and solve for t
= 391.694
An alternative method is to use fractional conversions (we will learn this later in the course):
Lets perform this balance for species C:
This is a first order reaction in each of the two reactant species, the reaction rate for species C is
= =

at 54oC.

Since , , and are all a function of time, lets rewrite the above equation in terms of x, the
fraction of species B (the limiting reagent) converted by time t.
() = 0 (1 )
() = 0 + 0 = 0 , 0 = 0
() = 0 20
And (0 20 )(0 0 ) = 0
We can solve for x using direct differentiation:
=

(0 20 )(1 )

=
0

(0 20 )(1 )

Which for convenience can be written as

=
0

(1 0.8)(1 )

Given that:
0 = 0.4
0 = 1

Integrating we find
5 4
= 5 ln (
) 8.047
1

Problem Set #1 DUE January 16th, 2015

At this point the only unknowns are x and t. To find x, we know () = 0 . So

4 ()
5
0
= 5 ln (
) 8.047
()
1
0
Given that:
= 0.006

L
mol min

() = 0.3

Solve for t:
= 391.66

Problem Set #1 DUE January 16th, 2015

2. Consider the following sequence of first-order reactions occurring in an isothermal batch reactor:

If the reactor only contains A with a concentration of 0 at t = 0, what is the concentration of each
species (A, B, C, and I) as a function of time?

Final Answer:
() = 0 (1 +3 )
() =

1 0
( 2 (1 +3 ) )
2 (1 + 3 )

() =
() =

3 0
(1 (1 +3 ) )
(1 + 3 )

1 2 0
1
1
( (1 2 ) +
( (1 +3 ) (1 +3 ) ))
(1 + 3 )
2 (1 + 3 ) 2

Process:
For this problem we will assume perfect mixing and constant fluid volume such that the general
mole balance reduces to

The system of equations then is:

dCA
= k1 CA k 3 CA
dt
dCI
= k1 CA k 2 CI
dt
dCB
= k 2 CI
dt
dCC
= k 3 CA
dt

Lets begin with species A. The reaction rate for A is :

Problem Set #1 DUE January 16th, 2015

= 1 3
Then,
= 1 3 =

We can using direct differentiation to solve for .

(1 + 3 ) =

()

(1 + 3 ) =
0

(1 + 3 ) = ln( ) ln(0 )
() = 0 (1 +3 )
For species I, the reaction rate is:
= 1 2
Then,
= 1 2 =

We can substitute for ,

1 0 (1 +3 ) 2 =
1 0 (1 +3 ) =

+ 2

To solve this differential equation, use the integrating factor:

1 0 (1 +3 ) =

+ 2

() = 1 0 (1 +3 )
= 2 = 2
() = 1 ( () + )
() = 2 ( 2 1 0 (1 +3 ) + )
() = 2 ( 1 0 2 (1 +3 ) + )

Problem Set #1 DUE January 16th, 2015

() = 2 (

1 0
2 (1 +3 ) + )
2 (1 + 3 )

1 0
() = (
(1 +3 ) + 2 )
2 (1 + 3 )

We know that (0)=0 from our initial conditions:

(0) = 0 =
=
() =

1 0
+
2 (1 + 3 )

1 0
2 (1 + 3 )

1 0
( 2 (1 +3 ) )
2 (1 + 3 )

For species B, the reaction rate is:

= 2
Then the mole balance becomes,

= = 2

We know that , so substituting we get

2 1 0
=
( 2 (1 +3 ) )

2 (1 + 3 )

2 (1 + 3 )
= ( 2 (1 +3 ) )
1 2 0

We integrate,
()

2 (1 + 3 )
= ( 2 (1 +3 ) )
1 2 0
0

Since 0 = 0
2 (1 + 3 )
1
1
1
1
() =
2+
(1 +3 ) +
(1 + 3 )
1 2 0
2
2 (1 + 3 )
() =

1 2 0
1
1
( (1 2 ) +
( (1 +3 ) 1))
(1 + 3 )
2 (1 + 3 ) 2

Problem Set #1 DUE January 16th, 2015

For species C, the rate constant is:

= 3
Then the mole balance becomes:

= = 3

We can substitute for such that

= 3 0 (1 +3 )

And write the equation as,

= (1 +3 )
3 0
We integrate to find
()

= (1 +3)
3 0
0

Since 0 = 0,
()
1
1
=
(1+3 )
(1 + 3 )
3 0 (1 + 3 )

() =

3 0
(1 (1 +3 ) )
(1 + 3 )

Problem Set #1 DUE January 16th, 2015

3. Consider the following elementary reaction occurring in a well-mixed batch reactor with
expandable walls (e.g., a balloon):
2
1
Your experiments show that the time-dependence of the reactors volume, V, can be described
by:
= 0 +
where Vo is the volume at the start of the reaction and a is a constant that describes the rate of
volume change. At the start of the reaction, the reactor is filled with A at a concentration of 0 .
Determine the concentration of A as a function of time assuming isothermal conditions.
Final Answer:
() = (

0 0
) (1 )
(0 + )

Process:
We assume perfect mixing such that the general mole balance reduces to:
=

In this case, V is a function of time.

Given an elementary first order reaction:
= 1
Resulting in a mole balance of
= 1 =

Break down the RHS :

1 =

We know =
1 =
1

1
+ 1
=

Problem Set #1 DUE January 16th, 2015

We can integrate both sides to find

()

Integrate the LHS

ln (

0
+ 1
)=

()

Expand the RHS

ln (
)=(
+ 1 )
()
0 0 +

0
ln (
) = ln(0 + ) + 1 ln(0 )
()
ln (

()
) = ln(0 + ) 1 + ln(0 )
0

ln (

()
0
)
) = 1 + ln (
(0 + )
0
() = (

0 0
) (1 )
(0 + )

Problem Set #1 DUE January 16th, 2015

4. The liquid-phase reaction

AB+C
is being studied in an isothermal CSTR with a space time of 1 min. The reaction is firstorder with
respect to A and exhibits a rate constant of 1 min-1. The reactor is initially operating at steady-state
with a feed concentration of A equal to 1 mol/m3. The feed concentration is suddenly changed to 2
mol/m3, with all other parameters held constant. Calculate the effluent composition 1 min after the
change in the input composition.

Final Answer:
= .

= .

= .

Process:
If first order with respect to A, the reaction rates are:
=
=
=
First lets find the concentration of each species before feed concentration is changed.
Since the process is initially at steady state,

= 0 and the general mole balance can be reduced to

+ = 0
Given that flow in is concentration times flow rate and the generation/consumption term is rate
times volume:
0 + = 0
Dividing everything by V we get

We know that

+ = 0

= = [=] , therefore,

+ = 0

Problem Set #1 DUE January 16th, 2015

= +
So system of equations are:
=
= +
= +
Then for species A:
= +
=
(1 + ) =
= /(1 + )
Given that = 1

,
3

=1

1
,
min

and = 1 .
= 0.5

For species B:
= +
= +
= 0 and = 0.5

,
3

therefore
= 0.5

For species C:
= +
= 0.5

These values can now be used as the initial condition for the next part of the problem, where the
concentration of A in the feed is increased.
Once the feed concentration is suddenly changed, the system is no longer at steady state, therefore,
the mole balance cannot be further reduced. Given that flow in is concentration x flow rate, the
number of moles is concentration x volume and the generation/consumption term is rate x volume:

Problem Set #1 DUE January 16th, 2015

The general mole balance is:

+ =

0 + =

Assuming constant fluid volume,

0 + =

We know that

+ =

+ =

= = [=] , therefore,

Our system of equations now are:

+ =

+ =

For species A:

+ =

( + ) =

1
=
+ ( + )

Solving the above equation we get:

() =

( +)
+
1
( + )

Problem Set #1 DUE January 16th, 2015

Where A is a constant. To find A we can use the initial conditions right before the feed concentration
was changed. () = 0.5

where t in this case is 0.We also know that = 2

into the above equation we get:

= 0.5

Plugging in all the values weve been given we get:

() = 1 [ 3 ] 0.5[ 3 ] 2

At t=1 min we find that = .

For species B:

+ =

+ =

We know what () is and can substitute it into the above equation:

+ (1 0.5 2 ) =

We plug in the values we know:

0

+ 1(1 0.5 2 ) =
1
1

0 + 1 0.5 2 =
1 0.5 2 =

Use integrating factor to find solution for CB(t):

() = [ (1 0.5 2 ) + ] ,
() = [ + 0.5 + ]

() = 1 + 0.5 2 +
We know at t=0, = 0.5

,
3

then A=-1
() = 1 + 0.5 2

Plugging this

Problem Set #1 DUE January 16th, 2015

At t=1 min = .

and and are equal