PROBLEMS

1. Aqueous A at a concentration C
Ao
=1 mol/li is introduced into a batch reactor where it
reacts away to form product R according to stoichiometry AR. The concentration of A in
the reactor is monitored at various times as shown below. Find a rate equation to
represent the kinetics of reaction.
(a) (b)
t, min 0 5 17 40
C
A
, mol/li 1000 600 180 18


t, min 0 100 200 40
C
A
, mol/li 1000 600 333 200


A. Given:
Stoichiometry: A R (liquid phase)
C
Ao
=1 mol/li = 1000 mol/m
3


Required: rate expression

Solution:
Assume elementary reaction: n=1
Rate equation: -r
A
=
A
dC
dt

=kC
A


( )
A
A
A
A
O
A A
A
O
C t
dC
C
C 0
-ln C /1000 C
C t
K dt
ln Kt ; K=
=
=
} }



1
1
2 Ave
3
K 0.1022/min
K 0.1009/min K is constant K 0.1012 min
K 0.1004/min

= =
`

=
)


rate expression; -r
A
=0.1012C
A
; mol/m
3
.min

B. Given:
Stoichiometry: A P
Data
t, min 0 100 200 40
C
A
, mol/li 1000 600 333 200

Required: rate equation/expression

Solution:
Assume n=z
rate eqn: -r
A
= -
dC
A
dT
= KC
A
2



A
A
2
A
o
A
C
dC
C
C
}
= KdT

A A
o
1 1
C C

= Kt

=

=

)
5
K 1x10
1
5
K 1.0015x10
3
3 2 m
K is constant K 1.0005x10
Ave mol.min
5
K 1.0x10
3
3
K 1.0x10
4


-r
A
= 1.005 x 10
5
C
A
2
; mol/m
3
.min


2. Aqueous A and B react to form products in a batch reactor. Find a rate equation to represent the
kinetics of the reaction for the following information:

a.) A + B R + S C
Bo
=C
Ao

t, min 0 20 40 90
C
A
, mol/m
3
1000 333 200 100

b.) A + B R + S C
Bo
=2C
Ao


t, min 0 3 10 16
C
A
,mol/ m
3
500 190 40 10

c.) A + 2B R + S C
Bo
=2C
Ao


t, min 0 10 40 90
C
A
,mol/m
3
1000 500 200 100

Given:
a.) A + B R + S C
Bo
=C
Ao
(M=1)

Required: rate equation

Solution:
Assume n=2
Rate eqn: -r
A
= -
A
dC
dT
= Kc
A
2


Stoichiometry: A + B Product
at start C
Ao
C
Bo
0
due to rxn C
Ao
- C
A
(C
Ao
- C
A
)(1/1)
at the end C
A
C
B
= C
Bo
- C
Ao
+ C
A

C
A
= C
Ao
- C
Ao
+ C
A

C
B
= C
A

=
1 1
1000 C
A
K
t

-
A
dC
dT
= KC
A
2


A
A
2
A
o
A
C
dC
C
C

}
=
}
t
K dT
0

2 1
C C C
2
A A A
C dC Kt
A A C C
Ao Ao 2 1
+

= =
} }
+



A Ao A
1 1 1 1
C C C 100
K
t t

= =


3
4
1
4 3 m
2 Ave
mol.min
4
3
K 1.0015x10
K 1x10 K 1.0005x10
K 1x10

= =
`

=

)


-r
A
= 1.0005 x 10
-4
C
A
C
B
=mol/li; C
B
=C
A

-r
A
= 1.0005 x 10
-4
C
A
2


Given:
b.) A + B R + S C
Bo
=2C
Ao
M=2
data:

t, min 0 3 10 16
C
A
,mol/ m
3
500 190 40 10

Required: rate eqn:

Solution:
Assume: n=2

-r
A
= -
A
dC
dT
= KC
A
C
B

C
B
= C
Bo
- C
Ao
+ C
A

C
B
=2 C
Ao
- C
Ao
+ C
A

C
B
= C
Ao
+ C
A

A
dC
dT
=KC
A
(C
Ao
+ C
A
)

( )
A
A
A A A A
o o
C
dC
C C C C +

}
=
t
K dT
0
}







1 1
Kt
C C
A Ao
=
By Partial Fractions:


( )
1 A B
C C C C C C
A Ao A A Ao A
= +
+ +


1= A(C
Ao
+ C
A
) + B(C
A
) = A C
Ao
+ A C
A
+ BC
A





C C
Ao A
ln KC t
Ao
2C
A
+
=



Constants: 1 = C
Ao
A ; A= 1/ C
Ao


C
A
= 0 = (A+B) C
A
; B=-A = -1/C
Ao

dC dC C C 1 1
A A A A
+ Kt
C C C C C
Ao Ao C C A Ao A
Ao Ao
C C C
Ao A A
ln + ln KC t
Ao
C 2C
Ao Ao
C C 500 C
Ao A A
ln ln
2C 2C
A A
K ; K=
C t 500t
Ao
=
} }
+
+
=
+ +
=



check: M=2

( )
( )
( )( )
C
B
ln KC M 1 t
Ao
MC
A
500 C
A
ln K 500 2 1 t
2C
A
500 C
A
ln 500Kt
2C
A
=
+
=
+
=

4
K 3.9768x10
1
4 4
K 3.8191x10 K 3.9481x10
Ave 2
4
K 4.0483x10
3

=

= =

)


-r
A
= 3.9481x 10
-4
C
A
C
B



Given:
c.) A + 2B R + S C
Bo
=2C
Ao
M=2





Solution:
Assume: n=2
1st wRTA
1st wRB
(
(







Stoichiometry: A + 2B Product
at start C
Ao
C
Bo
0
due to rxn C
Ao
- C
A
(C
Ao
- C
A
)(2/1)
at the end C
A
C
B
= C
Bo
- (C
Ao
- C
A
)2
C
A
= C
Ao
- 2C
Ao
+ 2C
A

C
B
= 2C
A


With n =2
-r
A
= -
A
dC
dT
= kC
A
2


-
A
dC
dT
= kC
A
2

| |
|
\ .

}
+
dC C
A A
C
A C C C
o
A A A
o
= 2
}
t
k dT
0





A A
o
1 1
C C

=2 kt






3
5
m
k 3x10
Ave
mol.min

=


-r
A
= 5 x 10
5
C
A
C
B
; m
3
/mol.min









t, min 0 10 40 90
C
A
,mol/m
3
1000 500 200 100
1 1
C C
A Ao
K
2t

=
3.For the reaction of 2FeCl
3
+ SnCl
2
2FeCl
2
+ SnCl
4
in aqueous solution obtained at 25C.




Where y is the amount
of FeCl
3
reacted in
mo/li. The initial concentration of SnCl
2
and FeCl
3
were, respectively, 0.03125 and 0.0625 mol/li. Show
that the reaction is third order.

Given:
2FeCl
3
+ SnCl
2
2FeCl
2
+ SnCl
4
Initial concentration of FeCl
3
= 0.0625 mol/li
Initial concentration of SnCl
2
= 0.03125 mol/li
Where: t is in min
y = amount of FeCl
3
reacted (mol/Li)

Required: Show that n=3
Solution:
Let A= FeCl
3
C
Ao
= 0.0625

B= SnCl
2
C
Bo
= 0.03125


Stoichiometry: 2A + B Product
at start C
Ao
C
Bo
0
due to rxn C
Ao
- C
A
(C
Ao
- C
A
)(1/2)
at the end C
A
C
B
= C
Bo
1/2(C
Ao
- C
A
)
C
A
= C
Ao
- 1/2C
Ao
+ 1/2C
A

C
B
= 1/2C
A


For n =3
-r
A
= -
A
dC
dT
= kC
A
2
C
B


-
A
dC
dT
= kC
A
2
(1/2 C
A
) = K/2 C
A
3

( )
dC C
A A
C
C C C A
o
A A A
o

}
+
=
K
t
dT
0
2
}





4. Find the reactant concentration in a batch reactor after 6 hours for 2AR +S,
-r
A
=0.05 C
Ao
2
[mol/(li)(h)], C
Ao
=1 mol/li.

Given:
2A R + S
-r
A
=0.5 C
Ao
2
[mol/(li)(h)]
C
Ao
=1 mol/li.

Required: C
A
after t=6hrs






t, min 1 3 7 11 40
y 0.01434 0.02664 0.03612 0.04102 0.05058
Solution:
-
A
dC
dT
= 0.5C
A
2


A
A
2
A
o
A
C
dC
C
C

}
=
t
0
0.5 dT
}







C
A
= 0.25 mol/Li




5. Find the needed for 80 conversion of reactant A in a batch reactor for A+B2R, -
r
A
=0.05C
A
C
B
[mol/(li)(min)], C
Bo
=2 C
Ao
=2 mol/li

Given:
A + B 2R
-r
A
=0.05C
A
C
B
[mol/(li)(min)]
C
Bo
=2 C
Ao
=2 mol/li

Required: t where x
A
= 0.8

Solution:
-
A
dC
dT
= 0.05C
A
C
B


Stoichiometry: A + B 2R
at start C
Ao
C
Bo
0
due to rxn C
Ao
- C
A
C
Ao
- C
A

at the end C
A
C
B
= C
Bo
- C
Ao
+ C
A

C
B
= C
A


-
A
dC
dT
= 0.05C
A
2

C
A
= C
Ao
(1-x
A
)



A
dC
dT
= C
Ao
dx
A


C
Ao

A
dx
dT
= 0.05C
A
2
(1-x
A
)
2

-
A
dx
dT
= 0.05C
A
2
(1-x
A
)
2

( )
dx x
A A
0 2
1 x
a
}

= 0.05C
Ao
t
0
dT
}


A Ao
1 1
0.5t
C C
=
Ao
A
1
1 0.05C t
1 x
= =

A
Ao
A
x
0.05C t
1 x
=

t = 40 min



6. For the stoichiometry AR in a batch reactor, reactant A is 50 converted in one hour. How long
will it take for 75 conversion if the kinetics are given by: a.) r
A
=kC
A
b.) r
A
=Kc
A
2

c.) r
A
=kC
A
1.5

Given: A R Required: time when x=0.75
x=0.50 at t=1 hr
Solution:
a.) -r
A
= KC
A
=
A
dC
dT
at X
A
=0.50 and t=1hr

C
A
= C
Ao
(1-x
A
)

( )
( )
1
1 K ' 1
1 0.50
=

-
A
dC
dT
= KC
Ao
(1-x
A
) K = 1______

( )
A
2
a
dx
1 x
}
= KC dT
Ao
}
at x =0.75
-ln (1-x
A
) = kt_____
( )
( )
1
1 1 t
1 0.75
=

t = 3 hrs____ans
- ln (1-0.50) = K(1hr) c.) -r
A
= KC
A
1.5

K = 0.6013 / Hr____ -
A
dC
dT
= KC
A
1.5

dC C
A A
C 1.5
C A
o
A

} =
t
0
K dT
}

At x = 0.75
1/ 2
A
o
A
1 1
(C )1/ 2
(C )

= Kdt
- ln (1-0.75) = 0.6013(t)
A Ao A
C = C (1-x )
= Kt


t = 2 Hrs____ans
1/2 1/ 2
A A A
o o
1 1
[C (1-x )] (C )

=Kdt

b.)
-r
A
= KC
A
2



1/ 2 1/ 2
A Ao
K'
1 1
1 t
(1 x ) K(C )
=

-
A
dC
dT
= KC
A
2
at X
A
=0.50 and t=1hr
A
A
2
A
o A
C
dC
C C

}
=
t
0
K dT
}

( )
( )
1
1 ' 1
1/2
1 0.50
=

K
A A
o
1 1
C C
= Kt K = 0.4142______
A A A
o
1 1
C (1-x ) C

= Kt At x
A
=0.75

Ao
A
K'
1
1 C Kt
1 x
=

( )
( )
1/ 2
1
1 0.4142 t
1 0.75
=

A
1
1 K'Kt
1 x
=

t = 2.414 hrs____ans



7. For the reaction stoichiometry AR and the following tabulated data, is it reasonable to represent
the rate concentration relationship by an nth order kinetic expression? If so, find the reaction order
and the rate expression.

a.)





b.)







C
A
6.1 8.2 8.5 9.1 13.3
-r
A
110 200 220 250 530
C
A
420 620 680 910
-r
A
1.9 2.8 3.0 4.0