Solution to Problem 3.

25
Chemical Engineering Reaction by Octave Levenspiel
 Problem 3.25
The following data are obtained at 0 ⁰C in a constant – volume batch reactor using
pure gaseous A:

Time, min 0 2 4 6 8 10 12 14 ∞
Partial Pressure of
760 600 475 390 320 275 240 215 150
A, mm

The stoichiometry of decomposition is A  2.5R. Find the rate equation which

satisfactorily represents the decomposition.
 Given
Decomposition of A:
A  2.5R

Data obtained @ 0oC in a constant-volume batch reactor using pure gaseous A:

 Required

The rate equation which satisfactorily represents the decomposition of

pure gaseous A.
 Nomenclature
Symbols Definiton

𝑘1 Rate constant of the forward reaction (min-1)

𝑘2 Rate constant of the backward reaction in (min-1)

𝑝𝑎 Partial pressure of reactant A (mm)

𝑝𝑟 Partial pressure of product R (mm)

𝑝𝑎𝑜 Initial parial pressure of reactant A (mm)

𝑝𝑟𝑜 Initial parial pressure of product R (mm)

𝑝𝑎𝑒 Partial pressure of reactant A @ equilibrium (mm)

𝑝𝑟𝑒 Partial pressure of product R @equilibrium (mm)

t Time (min)
 Solution

In this problem, we can use integral method of analysis of data.

 Solution
Time, min 0 2 4 6 8 10 12 14 ∞
Partial Pressure of
760 600 475 390 320 275 240 215 150
A, mm

As shown in the data above, after 14 minutes, the partial pressure of A remains
at 150 mm Hg. This can possibly represent two things:

✘ The overall fractional conversion of A is less than 1 (XA,Overall < 1); or

𝑑𝑝𝑎
✘ The decomposition of A is at equilibrium. (− = 0 𝑎𝑛𝑑 𝑝𝑎𝑒 = 150 𝑚𝑚 𝐻𝑔)
𝑑𝑡
 Solution

✘ We can assume two kinds of reaction based on the two possible

representation of the partial pressure of A after 14 minutes:

✘ First – First-order Irreversible Reaction

k1
AR

✘ Second – First-order Reversible Reaction

k1
A  R
k2
 Solution

First, we will try the first assumption which is the first-order irreversible
reaction.
 First-order Irreversible Reaction
✘ Assumed reaction:
k1
AR
✘ Rate of reaction:
𝑑𝑝𝑎
− = 𝑘1 𝑝𝑎 (1)
𝑑𝑡

✘ Integrating the rate equation:

𝑑𝑝𝑎
− = 𝑘1 𝑑𝑡 (2)
𝑝𝑎

𝑝𝑎 𝑑𝑝𝑎 𝑡
− 𝑝𝑎𝑜 𝑝𝑎
= 𝑘 𝑑𝑡
0 1
(3)
 First-order Irreversible Reaction
✘ Integrating the rate equation:
𝑝𝑎
− ln = 𝑘1 𝑡 (4)
𝑝𝑎𝑜

✘ Which is in the form of a linear equation

𝑦 = 𝑚𝑥 (5)

𝑝𝑎
Where y = − ln
𝑝𝑎𝑜
X = t (minutes)
m = 𝑘1 (minute-1)
 First-order Irreversible Reaction
✘ Tabulating the data needed for the plotting of the graph
Time (min) pa (mm) pao (mm) pa/pao -ln(pa/pao)
0 760 760 1.0000 0.0000
2 600 760 0.7895 0.2364
4 475 760 0.6250 0.4700
6 390 760 0.5132 0.6672
8 320 760 0.4211 0.8650
10 275 760 0.3618 1.0165
12 240 760 0.3158 1.1527
14 215 760 0.2829 1.2627
∞ 150 760 0.1974 1.6227
 First-order Irreversible Reaction
✘ Plot the data with time as x and the -ln(pa/pao) as y
Time (min) pa (mm) pao (mm) pa/pao -ln(pa/pao)
0 760 760 1.0000 0.0000
2 600 760 0.7895 0.2364
4 475 760 0.6250 0.4700
6 390 760 0.5132 0.6672
8 320 760 0.4211 0.8650
10 275 760 0.3618 1.0165
12 240 760 0.3158 1.1527
14 215 760 0.2829 1.2627
∞ 150 760 0.1974 1.6227
 First-order Irreversible Reaction
✘ Testing the assumed first order rate equation:
1.6
1.4
1.2
1
-ln(pa/pao)

0.8
y = 0.0981x
0.6 R² = 0.9756
0.4
0.2
0
0 3 6 9 12 15
t (min)
 Solution

The R2 of the first assumption is equal to 0.9756 which is close to 1.

But before we can conclude, let us try now the second assumption which
is the first-order reversible reaction.
 First-order Reversible Reaction
✘ Assumed reaction:
k1
A  R
K2
✘ Rate equation of the reaction:
𝑑𝑝
− 𝑎 = 𝑘1 𝑝𝑎 − 𝑘2 𝑝𝑟 (6)
𝑑𝑡
✘ At equilibrium:
𝑑𝑝𝑎
− =0 (7)
𝑑𝑡

𝑘1 𝑝𝑎 − 𝑘2 𝑝𝑟 = 0 (8)

𝑘1 𝑝𝑟𝑒
= (9)
𝑘2 𝑝𝑎𝑒
 First-order Reversible Reaction
✘ Relating the partial pressure of R to partial pressure of A

𝑝𝑎𝑜 = 𝑝𝑎 + 𝑝𝑟 (10)
𝑝𝑟 = 𝑝𝑎𝑜 − 𝑝𝑎 (11)

𝑝𝑎𝑜 = 𝑝𝑎𝑒 + 𝑝𝑟𝑒 (12)

𝑝𝑟𝑒 = 𝑝𝑎𝑜 − 𝑝𝑎𝑒 (13)

✘ Solving k2 in terms of k1 and substituting equation (13) to equation (9)

𝑘1 𝑝𝑟𝑒
= (9)
𝑘2 𝑝𝑎𝑒
𝑘1 𝑝𝑎𝑒
𝑘2 = (14)
𝑝𝑎𝑜 −𝑝𝑎𝑒
 First-order Reversible Reaction
✘ Substituting equation (14) to equation (6)
𝑑𝑝
− 𝑎 = 𝑘1 𝑝𝑎 − 𝑘2 𝑝𝑟 (6)
𝑑𝑡

𝑑𝑝𝑎 𝑘1 𝑝𝑎𝑒
− = 𝑘1 𝑝𝑎 − 𝑝𝑟 (15)
𝑑𝑡 𝑝𝑎𝑜 −𝑝𝑎𝑒

✘ Substituting equation (13) to equation (15)

𝑑𝑝𝑎 𝑘1 𝑝𝑎𝑒
− = 𝑘1 𝑝𝑎 − 𝑝𝑟 (15)
𝑑𝑡 𝑝𝑎𝑜 −𝑝𝑎𝑒

𝑑𝑝𝑎 𝑘1 𝑝𝑎𝑒
− 𝑑𝑡
= 𝑘1 𝑝𝑎 − 𝑝𝑎𝑜 −𝑝𝑎𝑒
𝑝𝑎𝑜 − 𝑝𝑎 (16)
 First-order Reversible Reaction
✘ Simplifying equation (16)
𝑑𝑝𝑎 𝑝𝑎𝑜
− = 𝑘1 𝑝𝑎 − 𝑝𝑎𝑒 (17)
𝑑𝑡 𝑝𝑎𝑜 −𝑝𝑎𝑒

𝑑𝑝𝑎 𝑝𝑎𝑜
− = 𝑘1 𝑑𝑡 (18)
𝑝𝑎−𝑝𝑎𝑒 𝑝𝑎𝑜 −𝑝𝑎𝑒

𝑝𝑎 𝑑𝑝𝑎 𝑡 𝑝𝑎𝑜
− 𝑝𝑎𝑜 𝑝𝑎 −𝑝𝑎𝑒
= 0 𝑝𝑎𝑜 −𝑝𝑎𝑒
𝑘1 𝑑𝑡 (19)

𝑝𝑎 −𝑝𝑎𝑒 𝑝𝑎𝑜
− ln = 𝑘1 𝑡 (20)
𝑝𝑎𝑜 −𝑝𝑎𝑒 𝑝𝑎𝑜 −𝑝𝑎𝑒
 First-order Reversible Reaction
✘ Which is also similar to equation (5)
𝑦 = 𝑚𝑥 (5)

𝑝𝑎 −𝑝𝑎𝑒
Where 𝑦 = − ln
𝑝𝑎𝑜 −𝑝𝑎𝑒
X = t (minutes)
𝑝𝑎𝑜
m = 𝑘1 𝑝𝑎𝑜 −𝑝𝑎𝑒
(minute-1)
 ✘ Tabulating the data needed for the plotting of the graph

Time (min) pa (mm) pao (mm) pae (mm) pa - pae pao - pae 𝑝𝑎 − 𝑝𝑎𝑒
− ln
𝑝𝑎𝑜 − 𝑝𝑎𝑒
0 760 760 150 610 610 0
2 600 760 150 450 610 0.3042
4 475 760 150 325 610 0.6296
6 390 760 150 240 610 0.9328
8 320 760 150 170 610 1.2777
10 275 760 150 125 610 1.5851
12 240 760 150 90 610 1.9136
14 215 760 150 65 610 2.2391
∞ 150 760 150 0 610 ∞
 𝑝𝑎 −𝑝𝑎𝑒
✘ Plot the data with time as x and the − ln as y
𝑝𝑎𝑜 −𝑝𝑎𝑒

Time (min) pa (mm) pao (mm) pae (mm) pa - pae pao - pae 𝑝𝑎 − 𝑝𝑎𝑒
− ln
𝑝𝑎𝑜 − 𝑝𝑎𝑒
0 760 760 150 610 610 0
2 600 760 150 450 610 0.3042
4 475 760 150 325 610 0.6296
6 390 760 150 240 610 0.9328
8 320 760 150 170 610 1.2777
10 275 760 150 125 610 1.5851
12 240 760 150 90 610 1.9136
14 215 760 150 65 610 2.2391
∞ 150 760 150 0 610 ∞
 First-order Reversible Reaction
✘ Testing the assumed first-order reversible reaction
2.5

y = 0.1591x
1.5
R² = 0.9998
y

0.5

0
0 2 4 6 8 10 12 14 16
t (min)
 Solution

We will now compare the two graphs.

 First-order Reversible Reaction
✘ From the two graphs, it can be seen that the R2 of the second assumption is much closer to
1 compared to the R2 of the first assumption.
2.5
1.6
1.4
2
1.2
1
y = 0.1591x
1.5
R² = 0.9998
-ln(pa/pao)

0.8 y = 0.0981x

y
0.6 R² = 0.9756 1

0.4
0.5
0.2
0 0
0 3 6 9 12 15 0 2 4 6 8 10 12 14 16
t (min)
t (min)
 First-order Reversible Reaction
✘ Therefore the second assumption satisfactorily represent the data.
✘ Solving for the value of k1

𝒑𝒂𝒐
slope = 0.1591 = 𝒌𝟏 𝒑𝒂𝒐 −𝒑𝒂𝒆
(21)

With pao = 760 mm Hg and pae = 150 mm Hg

𝑘1 = 0.1277 min-1
✘ Solving for k2 using equation (14)
𝒌𝟐 = 0.0314 min-1
✘ The rate equation of the decomposition of pure A in terms of partial pressure is
𝒅𝒑𝒂
− = 𝟎. 𝟏𝟐𝟕𝟕𝒑𝒂 − 𝟎. 𝟎𝟑𝟏𝟒𝒑𝒓
𝒅𝒕
 First-order Reversible Reaction
✘ In terms of concentration:
𝑑𝑝𝑎
− = 0.1277𝑝𝑎 − 0.0314𝑝𝑟
𝑑𝑡
𝑝 = 𝐶𝑅𝑇
𝑑𝐶𝑎
− 𝑅𝑇 = 0.1277(𝑅𝑇)𝐶𝑎 − 0.0314(𝑅𝑇)𝐶𝑟
𝑑𝑡

𝒅𝑪𝒂
− = 𝟎. 𝟏𝟐𝟕𝟕𝑪𝒂 − 𝟎. 𝟎𝟑𝟏𝟒𝑪𝒓
𝒅𝒕
✘ Therefore for isothermal 1st order kinetics, 𝑘𝑐 = 𝑘𝑝
thanks!