Chapter 5

Exercise 1:
part a)
The full BET equation is as follows:
c 1 P
P
1

=
+
Vads ( Po P) cVm cVm Po

(1)

After dividing both the numerator and denominator of the left hand side of equation (1)
by Po,
P

Po
Vads (1 P

Po

c 1 P
1

+
cVm cVm Po
P

By plotting

Po

P
Vads (1 )
Po

vs P

Po

(2)

for sample 1, the following can be concluded (only the

following data points were used in these calculations 0.05 P

Po

0.3 ):

c 1
= 0.035 g cm-3
cVm
1
The regressed y-intercept of the resulting line =
= 9.15x10-5 g cm-3
cVm
2
R value of the fitted line = 0.99
The regressed slope of the resulting line =

Therefore c = 386.4 and Vm = 28.3 cm3 g-1

The one-point BET equation is as follows:
1 P
P
=
Vads ( Po P) Vm Po

(3)

where we assume that c>>1.

Choose one point to calculate Vm. Choose P/Po = 0.3.
5.1

At P/Po = 0.3, Vads = 39.1 cm3 g-1.

Therefore Vm= V(1-P/Po) = (39.1cm3 g-1)(0.7) = 27.4 cm3 g-1.
Note that assuming c >>1 was a good assumption, as seen from the calculations done
using the full BET equation.
Now we need to calculate the surface area, Sg, for each solution.
The surface area is related to the number of molecules adsorbed in a monolayer, N, in the
following way.
S g = N

(4)

where is the cross-sectional area of the adsorbing gas (dinitrogen in this case).
Vm N o
where No is Avagadros number and V
V
is the volume of gas at STP (1 atm and 273 K) per mol, 22400 cm3 mol-1.
N = # molecules adsorbed per monolayer =

For dinitrogen, = 0.162 nm2.

For the full BET equation
2

molecules
1m
)(0.162) 9

mol
10 nm = 123 m2g-1.
22400 cm 3 mol 1

28.3 cm 3g 1 (6.02 x10 23

Sg =

Similarly for the one-point BET equation,

Sg = 119 m2g-1.
These values are essentially the same (3% difference).
part b)
Repeat the same analysis as in part a) except on Sample 2.
Full BET equation:
c = 22.4
Vm = 0.689 cm3g-1.
5.2

Note that this sample has a smaller BET constant than sample 1 (c is not much greater
than 1 here).
For the one-point equation:
Vm = V(1-P/Po) = (0.89cm3 g-1)(1-0.3) = 0.623 cm3g-1.
The surface areas for the full BET equation and the one-point equation are 3.00 m2 g-1
and 2.7 m2 g-1, respectively.
Due to the small BET constant, the two methods do not give the same answer (10%
difference).

Exercise 2:
Note that:
# moles H chemisorbed irreversibly (strong sites) =
#moles H chemisorbed in Run 1- # moles H chemisorbed in Run 2
H
First, plot H/Pt vs P for each run; find the y-intercepts
Pt
Dispersion= H/Pt irreversibly adsorbed =

H
Pt

P = 0 , Run1

H
Pt

.
P =0
= 0.93 0.34 = 0.59

P = 0 , Run 2

The average particle size is estimated using the following relationship, assuming that the
particles are spherical:
Particle diameter (nm)=1/dispersion.
In this case the particle diameter is 1.69 nm.

Exercise 3:
The reaction investigated by A. Peloso is
CH3CH2OH = CH3CHO + H2
(Et)
(Ad)
(DH)

(1)

5.3

The proposed mechanism is:

r =

k [PEt ( PAd PDH ) / K e ]

(2)

[1 + K Et PEt + K Ad PAd ]2

To formulate a mechanism the following clues can be gained from inspection of the
proposed expression:
1) PDH is raised to the 1st power, so the adsorption and desorption of DH is
equilibrated (it is not dissociative adsorption).
2) The denominator is raised to the 2nd power, so surface sites are involved in the
RDS.
The following mechanism is proposed:
1

Et + *

Et* + *

Ad*

DH*

Et*
Ad* + DH*
Ad + *
DH + *

The following analysis is used to derive the expression in equation (2).

K Et =

[ Et ]
[ Ad ]
[ DH ]
, K Ad =
, K DH =
[ Et ][]
[ Ad ][]
[ DH ][]

(3)

From the RDS,

r=

k1[ Et ][] k 1[ Ad ][ DH ]
[]0

(4)

The site balance is

[]o = [] + [ Et ] + [ Ad ] + [ DH ]

(5)

After substituting equation (3) into equation (5)

5.4

[]o
= 1 + K Et [ Et ] + K Ad [ Ad ] + K DH [ DH ]
[]

(6)

After substituting equation (6) into equation (4), with the assistance of equation (3), the
proposed rate expression can be derived. Note that the constants are all lumped into k
and Ke. In addition, the assumption that KDH[DH]<<1 is needed in order to arrive at the
proposed rate expression.

Exercise 4:
This is the same reaction as Exercise 3, however a different catalyst is used. The
proposed rate expression with the new catalyst is as follows:
r=

k [PEt ( PAd PDH ) / K e ]

(1)

[1 + K Et PEt + K Ad PAd + K DH PDH ]2

The same reaction mechanism as in Exercise 3 is proposed here. The only difference
between the rate expression in Exercise 3 and in Exercise 4 is that in Exercise 4, KDHPDH
is not << 1.
Exercise 5:
The overall reaction is
IP + DO = At + W

(1)

The proposed rate expression is of the form:

1

k[ IP][ DO] 2
r=
1
(1 + K1[ IP] + K 2 [W ])1 + K 3 [ DO] 2

(2)

We shall assume that At cannot adsorb on the surface of the catalyst and that the rate of
surface reaction between adsorbed IP and adsorbed oxygen is the rate determining step.
Since there are two terms in the denominator, there must be two types of surface sites.
Therefore, the RDS is proposed to be the following step:
IP*1 + O2

At + W1 + 2

(3)

where *1 and *2 represent two different types of active sites. Since DO is raised to the
power, DO adsorption/desorption is dissociative.
5.5

DO + 22

2O2

Therefore a reaction mechanism that is consistent with the rate expression is the
following:
IP + 1

IP1

DO + 22
IP*1 +O2
W1

2O2

(4)

At + W1 + 2

W + 1

The following analysis is used to derive the rate expression from the proposed
mechanism.
Since the surface reaction step is the RDS, all other steps must be equilibrated.
Therefore,
[ IP 1 ]
[O 2 ] 2
[W 1 ]
K1 =
, K2 =
, K3 =
(5)
2
[ IP][1 ]
[W ][1 ]
[ 2 ] [ DO]
The site balance for site type 1 is
[1 ]o = [1 ] + [ IP 1 ] + [W 1 ]

(6)

while the site balance for site type 2 is

[ 2 ]o = [ 2 ] + [O 2 ]

(7)

After substituting equation (5) into equation (6), the site balance on site type 1 becomes
[1 ]o = [1 ] + K 1 [ IP][1 ] + K 3 [W ][1 ]

(8)

Therefore,

[1 ] =

[1 ]o
(1 + K1[ IP] + K 3 [W ])

(9)

After substituting equation (5) into equation (7), the site balance on site type 2 becomes

5.6

[ 2 ]o = [ 2 ] + K 21 / 2 [ 2 ][ DO]1 / 2

(10)

Therefore,
[ 2 ] =

[ 2 ]o
1 + K 21 / 2 [ DO]1 / 2

(11)

The rate of the reaction is the rate of the RDS, therefore,

r = k[ IP 1 ][O 2 ]

(12)

After substituting equations (5), (9) and (11) into equation (12),

k K1[ IP][1 ]o K 21 / 2 [2 ]o [ DO]1 / 2

r=
(1 + K1[ IP] + K 3 [W ]) 1 + K 21 / 2 [ DO]1/ 2

(13)

The rate expression in equation (2) is obtained by grouping all of the constants.

Exercise 6:
The overall reaction that is being studied here is the following:
CO + Cl2 = COCl2

(1)

The proposed rate expression for this reaction is the following:

r=

kPCO PCl2

[1 + K P

1 Cl2

+ K 2 PCOCl2

(2)

The exponent in the denominator suggests that there are two adsorbed species in the
RDS.
The lack of a K3PCO term in the denominator suggests that CO does not adsorb strongly
on the surface.
The following mechanism is suggested to explain the functional form of the rate
expression given in equation (2).

5.7

CO +
Cl2 +

CO
Cl2

CO + Cl2
COCl2

(3)
COCl2 +

COCl2 +

The rate of the RDS is

r=

k[CO][Cl 2 ]
[]o

(4)

The following equilibrium relationships are valid since the surface reaction step is the
RDS:
K1 =

[Cl 2 ]
[COCl 2 ]
[CO]
, K2 =
and K 3 =
[CO ][]
[Cl 2 ][]
[COCl 2 ][]

(5)

The site balance for this system is

[]o = [] + [CO] + [Cl 2 ] + [COCl 2 ]

(6)

After substituting equation (5) into equation (6),

[] =

[]o
1 + K1[CO] + K 2 [Cl2 ] + K 3 [COCl2 ]

(7)

Substituting equation (7) into equation (4),

r=

kK1[CO ][]o K 2 [Cl 2 ]

(8)

(1 + K1[CO] + K 2 [Cl 2 ] + K 3 [COCl 2 ])2

Again, in order to arrive at the rate equation in equation (2) we must assume that
K1[CO]<<1.

5.8

Exercise 7:
The proposed reaction rate has the form:
r=

kK A PA
(1 + K A PA + K B PB )2

(1)

If a large quantity of inerts readily adsorb on the catalyst surface, KIPI is large compared
to KAPA and KBPB and 1. The reaction rate is as follows:
r=

kK A PA
(1 + K A PA + K B PB + K I PI )2

(2)

It can be simplified to
r=

kK A PA
K I2 PI2

(3)

The reaction order with respect to A is 1 with a large quantity of inerts that adsorb on the
catalyst surface.
Exercise 8:
The following reaction is studied over a zirconium oxide-silica gel catalyst:
C2H4 + HCl = C2H5Cl

(4)

Step 1: Assume a plausible reaction mechanism.

C2H4 + *
HCl + *

C2H4*
HCl*

C2H4* + HCl*

C2H5Cl* + *

C2H5Cl*

C2H5Cl + *

CH4 + *

CH4*

(5)

5.9

Step 2: Derive a rate expression for this mechanism.

The equilibrium relationships are as follows:
K1 =

[C 2 H 4 ]
[CH 4 ]
[ HCl ]
, K2 =
, K3 =
[C 2 H 4 ][]
[ HCl ][]
[CH 4][]
(6)

[C 2 H 5 Cl ]
and K 4 =
[C 2 H 5 Cl ][]
The rate of reaction is that of the RDS:
r=

k1[C 2 H 4 ][ HCl ] k 1[C 2 H 5Cl ][]

[]o

(7)

The site balance is

[]o = [] + [C 2 H 4 ] + [ HCl ] + [C 2 H 5 Cl ] + [CH 4 ]

(8)

After substituting equation (6) into the site balance:

[] =

[]o
1 + K 1 [C 2 H 4 ] + K 2 [ HCl ] + K 3 [CH 4 ] + K 4 [C 2 H 5 Cl ]

(9)

The rate expression in terms of only the reactants and products is:
r=

k1 K1[C 2 H 4 ][]o [ HCl ]K 2 k 1 K 4 [C 2 H 5 Cl ][]o

(1 + K1[C 2 H 4 ] + K 2 [ HCl ] + K 3 [CH 4 ] + K 4 [C 2 H 5Cl ])2

(10)

From the overall equation, equation (4),

Ke =

[C 2 H 5 Cl ]
= 35
[C 2 H 4 ][ HCl ]

(11)

After substituting equation (11) into equation (10) and rearranging

[C H Cl ]
k [C 2 H 4 ][ HCl ] 2 5
K e

r=
(1 + K1[C2 H 4 ] + K 2 [ HCl ] + K 4 [C2 H 5Cl ] + K 3 [CH 4 ])2

5.10

where k is a grouping of constants.

Use nonlinear regression to fit the data to this form.
Each program that is used to solve for the best fit parameters will give a slightly different
answer depending on initial values. We obtained the following parameters:
k = 3.86
K1 = 25.14
K2 = 32.95
K3 = 1.98
K4 = 32.19
The following graph shows that how these parameters represent the data.

Calculated Rate

0.00029
0.00027
0.00025
0.00023
0.00021
0.00019
0.00019 0.00021 0.00023 0.00025 0.00027 0.00029
Observed Rate

Now assume a different mechanism, namely that of Rideal-Eley. The mechanism is as

follows:
C2H4 + *
C2H4* + HCl

C2H4*
C2H5Cl*

C2H5Cl*

C2H5Cl + *

CH4 + *

CH4*

(12)

The rate is then the rate of the RDS,

5.11

r = k 2 [C 2 H 4 ][ HCl ] k 2 [C 2 H 5Cl ]

(13)

The other three steps are assumed to be quasi-equilibrated, and the equilibrium
expressions are the following:
K1[C 2 H 4 ][] = [C 2 H 4 ]
K 3 [C 2 H 5 Cl ][] = [C 2 H 5 Cl ]

(14)

K 4 [CH 4 ][] = [CH 4 ]

The site balance is the following:
[]o = [] + [C 2 H 4 ] + [C 2 H 5 Cl ] + [CH 4 ]

(15)

After substituting equations (14) and (15) into equation (13), the rate is given by the
following expression:
[C H Cl ]
k [C 2 H 4 ][ HCl ] 2 5
K e

r=
(1 + K1[C2 H 4 ] + K 4 [C2 H 5Cl ] + K 3 [CH 4 ])

(16)

However, after fitting this expression to the data, negative numbers are found for some of
the constants. Since this is unreasonable, the Rideal-Eley mechanism does not fit the
data.
Exercise 9:
part a)
The proposed mechanism is as follows:
N2 +
N2 + 3H2

N2

(1)

2NH3 +

(2)

The rate of reaction is therefore,

r = k1[ N 2 ][] k 1[ N 2 ]

(3)

The equilibrium expression is

5.12

[ NH 3 ] 2 []
K2 =
[ H 2 ]3 [ N 2 ]

(4)

The site balance for this reaction mechanism is

[]o = [] + [ N 2 ]

(5)

After substituting equation (4) into the site balance,

[] =

[]o
[ NH 3 ] 2
1+
[ H 2 ]3 K 2

(6)

Substituting equations (5) and (6) into equation (3) results in the rate expression for the
reversible formation of ammonia with associative adsorption of dinitrogen.
r=

k1[ N 2 ][]o
k 1[ NH 3 ]2 []o

[ NH 3 ]2
[ NH 3 ]2
3
1+

K 2 [ H 2 ] 1 +
3
[ H 2 ]3 K 2
[
]
H
K
2
2

(7)

part b)
It is not possible to distinguish equation 5.3.7 from the rate expression in part a) from
experimental data. Equation 5.3.7 is
k1[]o [ N 2 ] k 1 K 22 []o
r=

[ NH 3 ]

1 + K 2
3 / 2
[ H 2 ]

[ NH 3 ]
if K 2
3/ 2
[H 2 ]
r=

[ NH 3 ]2
[ H 2 ]3

>> 1 or

k1[]o [ N 2 ]

[ NH 3 ]
K 2

3/ 2
[H 2 ]

(8)

[N ]

>> 1
[]

k 1[]o

(9)

5.13

[ NH 3 ] 2
[ N 2 ]
>>1 or
>>1
From part a) if
3
[]
[H 2 ] K 2
r=

k1[ N 2 ][]o
k 1[]o
[ NH 3 ]2
[ H 2 ]3 K 2

(10)

Since equation (10) and equation (9) are identical it is probably not possible to
distinguish between the two rate expressions experimentally unless an extremely wide
range of accurate data is used.
Exercise 10:
The proposed mechanism is:
N2O +
N2O
CO +
CO + O

N2O
N2 + O

(1)

CO
CO2 + 2*

The adsorption of N2O and CO on the surface is equilibrated.

Where the overall reaction is
N2O + CO N2 + CO2

(2)

part a)
The site balance for this mechanism is
[]o = [] + [ N 2 O] + [CO] + [O]

(3)

However, if the surface coverage of oxygen is assumed to be very small, the site balance
is reduced to
[]o = [] + [ N 2 O] + [CO]

(4)

The equilibrium relationships are as follows:

5.14

K1 =

[ N 2 O]
[CO]
and K 3 =
[CO ][]
[][ N 2 O]

(5)

After substituting equation (5) into the site balance and rearranging
[] =

[]o
1 + K1[ N 2 O] + K 3 [CO ]

(6)

The rate of reaction is either the rate of N2O reaction on the surface or the rate of CO2
formation.
r = k 2 [ N 2 O] = k 4 [CO][O]

(7)

After substituting the site balance and the equilibrium relationships into equation (7), the
rate expression is then determined. The rate expression is as follows:
r=

k 2 K1[]o [ N 2 O]
1 + K1[ N 2 O] + K 3 [CO ]

(8)

In addition, let k 2 K1[]o = K 2 .

part b)
First, linearize the rate expression in equation (8) from part a).
PN 2O
r

Plot

Plot

1 K 2 PN 2O K 3 PCO
+
+
K1
K1
K1

PN 2O
r
PN 2O
r

(1)

vs PN 2O at constant PCO to get slope =

vs PCO at constant PN 2O to get slope =

K2
1 K 3 PCO
and the intercept =
+
K1
K1
K1

K3
1 K 2 PN 2 O
and the intercept =
+
K1
K1
K1

The results of the regression analysis are shown below:

5.15

Linear Regression (Holding Pco Constant)

2500
PN2O /r

2000
1500

y = 8.7x + 1486.6

1000

R = 0.9

500
0
0

20

40

60

80

P N2O

Linear Regression (Holding P N2O Constant)

5000

PN2O /r

4000
3000
2000

y = 45.3x + 460.4

1000

R = 1.0

0
0

20

40

60

80

P CO

There are now four equations to solve with three unknowns. Therefore, there are four
different ways to solve the set of overdetermined equations. The average of the 4 cases
was taken here.
K1 = 0.007 s torr-1
K2 = 0.069 torr-1
K3 = 0.320 torr-1
part c)
The results of the non-linear regression using the rate expression in part a) and the data in
part b) yielded the following results.
K1 = 0.004 s torr-1
K2 = 0.025 torr-1

5.16

K3 = 0.168 torr-1
The answers in parts b) and c) will be different because two different methods were used.
The answers in this case are within a factor of 3 of each other.
part d)
Since K3 is large compared to K1 and K2 where
K1 =

[ N 2 O]
[CO]
and K 3 =
[][ N 2 O]
[CO ][]

and K2 from the regression analysis was equal to the equilibrium constant K1,
The coverage of CO on the surface must be larger than the coverage of N2O on the
surface.
Exercise 11:
The proposed mechanism is the following:
H2O + V H2 + O
(1)

CO + O V CO2 +

Since we cannot assume that either step is the RDS, the steady state approximation is
used.
r = r1 = r2 = k1[ H 2 O][] k 1[ H 2 ][O] = k 2 [CO ][O] k 2 [CO2 ][]

(2)

Use equation (2) to solve for [O]

[O] =

k1 [ H 2 O][] + k 2 [CO2 ][]

k 2 [CO ] + k 1 [ H 2 ]

(3)

The site balance for this system is the following:

[]o = [] + [O]

(4)

After substituting equation (3) into the site balance and rearranging

5.17

[] =

[]o
k [ H O] + k 2 [CO2 ]
1+ 1 2
k 2 [CO ] + k 1 [ H 2 ]

(5)

Next, substitute equations (5) and (3) into equation (2).

r=

k1[ H 2 O][]o (k 2 [CO ] + k 1[ H 2 ]) k 1[ H 2 ][]o (k1[ H 2 O] + k 2 [CO2 ])

k 2 [CO ] + k 1[ H 2 ] + k1[ H 2 O] + k 2 [CO2 ]

part b)
The Langmuir-Hinshelwood type mechanism for the WGS reaction is:
CO +
H2O + 3
CO + O
2H

CO
2H + O
(1)
CO2 + 2*
H2 + 2

The rate of the RDS is:

k 3 [CO][O] k 3 [CO2 ][]2
r=

[]o
[]o

(2)

The adsorption of CO on the surface, the desorption of H2 from the surface and the
dissociation of water are all assumed to be equilibrated. Therefore the following
relationships are used.
K1 =

[ H 2 ][] 2
[CO]
[ H ] 2 [O]
, K2 = 3
and K 4 =
[CO ][]
[] [ H 2 O]
[ H ] 2

(3)

The site balance for this mechanism is:

[]o = [] + [CO] + [O] + [ H ]

(4)

After substituting the equilibrium expressions into the site balance and rearranging
5.18

[] =

[]o
K K [ H O] [ H ]1 / 2
1 + K 1 [CO ] + 2 4 2 + 21 / 2
[H 2 ]
K4

(5)

Substituting equation (5) and the equilibrium expressions into equation (2) results in the
following rate expression:
r=

K1 K 2 K 4 k 3 [CO ][ H 2 O][]o k 3 [CO2 ][]o [ H 2 ]

K K [ H O] [ H ]1 / 2
[ H 2 ]1 + K1[CO ] + 2 4 2 + 21 / 2
[H 2 ]
K4

(6)

Exercise 12:
The overall reaction is the following
CH3CH2CHO + H2 = CH3CH2CH2OH
part a)
A reasonable sequence of reaction steps for this reaction is the following:
CH3CH2CHO +
H2 + 2

CH3CH2CHO

2H

CH3CH2CHO + H

CH3CH2CH2O +

CH3CH2CH2O +H

CH3CH2CH2OH +

CH3CH2CH2OH

(1)

+ CH3CH2CH2OH

part b)
The rate of consumption of CH3CH2CHO is (since the adsorption of CH3CH2CHO is the
RDS):
d [CH 3CH 2 CHO]
= r = k1[CH 3CH 2 CHO ][] k 1[CH 3CH 2 CHO*]
dt

5.19

(2)

Since the adsorption of CH3CH2CHO is the RDS, all other steps are quasi-equilibrated.
Therefore, the following equilibrium relationships are used.
K2 =

[ H ] 2
[ H 2 ][] 2

K3 =

[CH 3 CH 2 CH 2 O][]
,
[CH 3 CH 2 CHO][ H ]
(3)

[CH 3 CH 2 CH 2 OH ][]
K4 =
[ H ][CH 3CH 2 CH 2 O]

and

[][CH 3CH 2 CH 2 OH ]
K5 =
[CH 3 CH 2 CH 2 OH ]

The site balance for this mechanism is the following:

[]o = [] + [CH 3CH 2 CHO] + [ H ] + [CH 3CH 2 CH 2 O] + [CH 3 CH 2 CH 2 OH ] (4)
After substituting the equilibrium expressions into the site balance and then plugging the
result into the rate expression in equation (2), the rate of consumption of CH3CH2CHO is
the following:

k [CH 3 CH 2 CH 2 OH ]
k1 [CH 3CH 2 CHO ] 1
[]o
K
K
K
K
H
[
]
d [CH 3 CH 2 CHO ]
5 4 3 2
2

=
CH
CH
CH
OH
[CH 3CH 2 CH 2 OH ]
[
]
[CH 3 CH 2 CH 2 OH ]
dt
3
2
2
1+
+ K 21 / 2 [ H 2 ]1 / 2 +
+
1/ 2
1/ 2
K 5 K 4 K 3 K 2 [H 2 ]
K5
K 4 K 5 K 2 [H 2 ]
part c)
If PH 2 (or [H2]) is large and PCH 3CH 2CH 2OH (or [CH3CH2CH2OH]) is small, the reaction rate
reduces to
k [] [CH CH CHO ]
r = 1 o 1 / 2 3 12/ 2
K 2 [H 2 ]
Therefore, in order to reduce to r =

kPprop
PH02.5

, H2 must be large and that of CH3CH2CH2OH

must be small.

5.20

Exercise 13:
Use the steady state approximation since we cannot assume that one step is the RDS.
Therefore,
r = r1 = r2 = k1[ RH 2 ][2O 2 ] = k 2 [O2 ][2 vac]

(1)

Solving for the concentration of vacancy pairs yields,

[2vac]=

k1 [ RH 2 ][2O 2 ]
k 2 [O2 ]

(2)

The site balance for this system is

[]o = [2O 2 ] + [2vac]

(3)

After substituting the expression for the concentration of vacancy pairs into the site
balance and solving for the concentration of O-2,
[2O 2 ] =

[]o
k [ RH 2 ]
1+ 1
k 2 [O2 ]

(4)

Lastly, substitute equation (4) into the rate expression in equation (1).
r=

k1[ RH 2 ][]o
k [ RH 2 ]
1+ 1
k 2 [O2 ]

(5)

After simplification, the rate expression in equation (5) becomes

1
1
1
=
+
r k1[]o [ RH 2 ] k 2 []o [O2 ]
where K1 = k1[]o and K2 = k2[]o

5.21