PCII FS25: Practical exercises Series 05

Samra Qehaja & Celina Gonzales

1a)
𝑘1 𝑘2
The reaction scheme: 𝐴 → 𝑃1 , 𝐴 → 𝑃2

Differential equations:
𝑑[𝐴]
𝐹𝑜𝑟 𝐴: = −𝑘1 [𝐴] − 𝑘2 [𝐴] = −(𝑘1 + 𝑘2 )[𝐴]
𝑑𝑡
𝑑[𝑃1 ]
𝐹𝑜𝑟 𝑃1 : = 𝑘1 [𝐴]
𝑑𝑡
𝑑[𝑃2 ]
𝐹𝑜𝑟 𝑃2 : = 𝑘2 [𝐴]
𝑑𝑡

1b)
Solving for [A](t):
𝑑[𝐴]
= −(𝑘1 + 𝑘2 )[𝐴]
𝑑𝑡

𝑑[𝐴]
= −(𝑘1 + 𝑘2 )𝑑𝑡
[𝐴]

[𝐴](𝑡) 𝑡
𝑑[𝐴]
∫ = ∫ −(𝑘1 + 𝑘2 )𝑑𝑡
[𝐴]0 [𝐴] 0

𝑙𝑛[𝐴](𝑡) − 𝑙𝑛[𝐴]0 = −(𝑘1 + 𝑘2 )𝑡

[𝐴](𝑡)
𝑙𝑛 = −(𝑘1 + 𝑘2 )𝑡
[𝐴]0

[𝐴](𝑡)
= 𝑒 −(𝑘1 +𝑘2 )𝑡
[𝐴]0

[𝐴](𝑡) = [𝐴]0 𝑒 −(𝑘1 +𝑘2 )𝑡

Solving for [P1] (t):
𝑑[𝑃1 ]
= 𝑘1 [𝐴](𝑡)
𝑑𝑡

Substitute [A](t) that was determined before into equation:

𝑑[𝑃1 ]
= 𝑘1 [𝐴]0 𝑒 −(𝑘1 +𝑘2 )𝑡
𝑑𝑡
[𝑃1 ](𝑡) 𝑡
∫ 𝑑[𝑃1 ] = ∫ 𝑘1 [𝐴]0 𝑒 −(𝑘1 +𝑘2 )𝑡 𝑑𝑡
0 0

𝑡
[𝑃1 ](𝑡) − 0 = 𝑘1 [𝐴]0 ∫ 𝑒 −(𝑘1 +𝑘2 )𝑡 𝑑𝑡
0

𝑡
−1
[𝑃1 ](𝑡) = 𝑘1 [𝐴]0 ∫ 𝑒 −(𝑘1 +𝑘2 )𝑡 𝑑𝑡
0 𝑘1 + 𝑘2

−1 −1
[𝑃1 ](𝑡) = 𝑘1 [𝐴]0 ( 𝑒 −(𝑘1 +𝑘2 )𝑡 ) − ( )
𝑘1 + 𝑘2 𝑘1 + 𝑘2

−1
[𝑃1 ](𝑡) = 𝑘1 [𝐴]0 (𝑒 −(𝑘1 +𝑘2 )𝑡 − 1)
𝑘1 + 𝑘2

𝑘1 [𝐴]0
[𝑃1 ](𝑡) = (1 − 𝑒 −(𝑘1 +𝑘2 )𝑡 )
𝑘1 + 𝑘2

Solving for [P2](t) follows the same pattern as solving for [P1] (t). Therefore:
𝑘2 [𝐴]0
[𝑃2 ](𝑡) = (1 − 𝑒 −(𝑘1 +𝑘2 )𝑡 )
𝑘1 + 𝑘2

The constant of integration “C” was not solved for in these examples, as definitive integrals
were applied. By integrating with limits, the initial conditions [A]0 (=c0) and P0(=0) account for
the constant.
1c)
As t → ∞, the Term e−(k1 +k2 )t → 0

Therefore:
lim [𝐴](𝑡) = 0
𝑡→∞

𝑘1 [𝐴]0
lim [𝑃1 ](𝑡) =
𝑡→∞ 𝑘1 + 𝑘2

𝑘2 [𝐴]0
lim [𝑃2 ](𝑡) =
𝑡→∞ 𝑘1 + 𝑘2

This means that the initial concentration [A]0 will get completely distributed between P1 and
P2 after an infinite amount of time.

1d)
If A decays through m parallel first order reactions k1, k2 ……., km:
The overall rate of decay of A is the sum of the rates of all individual pathways. This is similar
to the case in exercise 1b) where the total rate of change was −(𝑘1 + 𝑘2 )[𝐴]. Here we
generalize it by summing over all k.

𝑚
𝑑[𝐴] 𝑚
= − (∑ 𝑘𝑖 ) [𝐴] ⟹ [𝐴](𝑡) = [𝐴]0 𝑒 −(∑𝑖=1 𝑘𝑖)𝑡
𝑑𝑡
𝑖=1

𝑑[𝑃𝑖 ] 𝑚 𝑘𝑖 [𝐴]0 𝑚
= 𝑘𝑖 [𝐴]0 𝑒 −(∑𝑖=1 𝑘𝑖)𝑡 ⟹ [𝑃𝑖 ](𝑡) = 𝑚 (1 − 𝑒 −(∑𝑖=1 𝑘𝑖)𝑡 )
𝑑𝑡 ∑𝑖=1 𝑘𝑖

As t → ∞ ∶
𝑘𝑖 [𝐴]0
[𝑃𝑖 ](∞) = 𝑚
∑𝑖=1 𝑘𝑖

1e)
𝑚𝑜𝑙
𝑐0 = [𝐴]0 = 0.2 𝐿
𝑡1/2 = 16.7 𝑚𝑖𝑛
Product mixture at equilibrium: 41% 𝑃1
Total rate constant: 𝑘1 + 𝑘2

ln 2 ln 2 ln 2
For a first-order reaction: 𝑡1/2 = 𝑘1 +𝑘2
⇒ 𝑘1 + 𝑘2 = 𝑡1/2
= 16.7 𝑚𝑖𝑛
= 0.0415 𝑚𝑖𝑛−1

[𝑃1 ] 𝑘1
At equilibrium: [𝑃 = = 0.41
1 ]+ [𝑃2 ] 𝑘1 + 𝑘2

⇒ 𝑘1 = 0.41(𝑘1 + 𝑘2 ) = 0.41 ∗ 0.0415 𝑚𝑖𝑛−1 = 0.017015 ≈ 0.017 𝑚𝑖𝑛−1

⇒ 𝑘2 = (𝑘1 + 𝑘2 ) − 𝑘1 = 0.0415 𝑚𝑖𝑛−1 − 0.017 𝑚𝑖𝑛−1 = 0.0245 𝑚𝑖𝑛−1

1f)
𝑚𝑜𝑙 −(0.017𝑚𝑖𝑛−1 +0.0245𝑚𝑖𝑛−1 )𝑡
[𝐴](𝑡) = 0.2 𝑒
𝐿
𝑚𝑜𝑙
0.017𝑚𝑖𝑛−1 0.2
[𝑃1 ](𝑡) = 𝐿 −1 −1
(1 − 𝑒 −(0.017𝑚𝑖𝑛 +0.0245𝑚𝑖𝑛 )𝑡 )
0.017𝑚𝑖𝑛−1 + 0.0245𝑚𝑖𝑛−1

𝑚𝑜𝑙
0.0245𝑚𝑖𝑛−1 0.2 𝐿 −1 −1
[𝑃1 ](𝑡) = −1 −1 (1 − 𝑒 −(0.017𝑚𝑖𝑛 +0.0245𝑚𝑖𝑛 )𝑡 )
0.017𝑚𝑖𝑛 + 0.0245𝑚𝑖𝑛
2a)
𝑔
𝑀(𝑁𝐻4 𝐶𝑁𝑂 ) = 𝑀(𝑁𝐻2 𝐶𝑂𝑁𝐻2 ) = 60.06 𝑚𝑜𝑙

𝑚(𝑁𝐻4 𝐶𝑁𝑂 ) 22.9 𝑔

𝑛0 (𝑁𝐻4 𝐶𝑁𝑂 ) = = 𝑔 = 0.3813 𝑚𝑜𝑙
𝑀(𝑁𝐻4 𝐶𝑁𝑂 ) 60.06
𝑚𝑜𝑙

𝑚(𝑁𝐻2 𝐶𝑂𝑁𝐻2 ) (𝑡) 𝑚(𝑁𝐻2 𝐶𝑂𝑁𝐻2 ) (𝑡)

𝑛((𝑁𝐻2 𝐶𝑂𝑁𝐻2 ))(𝑡) = = 𝑔
𝑀(𝑁𝐻2 𝐶𝑂𝑁𝐻2 ) 60.06
𝑚𝑜𝑙

𝑛0 (𝑁𝐻4 𝐶𝑁𝑂 )− 𝑛((𝑁𝐻2 𝐶𝑂𝑁𝐻2 ))(𝑡) 0.3813 𝑚𝑜𝑙− 𝑛((𝑁𝐻2 𝐶𝑂𝑁𝐻2 ))(𝑡)
𝑐(𝑁𝐻4 𝐶𝑁𝑂)(𝑡) = =
𝑉 1𝐿

With the last generalized equation, the concentration of ammonium cyanate can be
calculated at any given time t. The concentrations are listed in this Table:

t [min] m(𝑁𝐻2 𝐶𝑂𝑁𝐻2 ) [𝑔] 𝑐(𝑁𝐻 𝐶𝑁𝑂) 𝑚𝑜𝑙

4 [ ]
𝐿

0 0 0.3813
20 7.0 0.2647
50 12.1 0.1798
65 13.8 0.1515
150 17.7 0.0866

2b)
To determine the reaction-order the Integration Method was used, because we are given only
the concentrations and the time. We cannot assume a zero-order reaction in this case, as
that would imply, that the rate is independent of the concentration of the reactant. In an
isomerization, that is typically not the case.

To test for First-order reaction ln[c(NH4CNO)] vs. time was plotted. If the reaction is first-
order the Graph of this plot should linear:

ln[c(NH₄CNO)] vs. Time

0
-0.5 y = -0.0095x - 1.1298
R² = 0.9439
ln[c(NH₄CNO)]

-1
-1.5
-2
-2.5
-3
0 20 40 60 80 100 120 140 160
Time [min]

ln[c(NH₄CNO)] Linear (ln[c(NH₄CNO)])

To test for Second-order reaction 1/c(NH₄CNO) vs. Time was plotted. If the reaction is
second-order the Graph of this plot should be linear:

1/c(NH₄CNO) vs. Time

14
12
1/c(NH₄CNO) [mol/l]-1

10
8
6
4 y = 0.0597x + 2.6203
R² = 0.9997
2
0
0 20 40 60 80 100 120 140 160
Time [min]

1/c(NH₄CNO) [L/mol] Linear (1/c(NH₄CNO) [L/mol])

The graph for the second-order reaction shows higher linear correlation than the one for the
first-order.

The rate k is equal to the slope of the Graph. In this case k= 0.0597 (mol/L)-1min-1
1 1
With the integrated rate law for the second-order = + 𝑘𝑡 the concentration of 𝑁𝐻4 𝐶𝑁𝑂
𝑐 𝑐0
at given times can then be calculated to confirm that our Assumption matches the
experimental data:

t [min] 𝑐(𝑁𝐻 𝐶𝑁𝑂) [𝑚𝑜𝑙] 𝑐(𝑁𝐻4 𝐶𝑁𝑂) [

𝑚𝑜𝑙
] 𝑤𝑖𝑡ℎ 𝑘 = 0.0597 𝑀−1 𝑚𝑖𝑛−1
4
𝐿 𝐿

0 0.3813 0.3813
20 0.2647 0.2620
50 0.1798 0.1783
65 0.1515 0.1538
150 0.0866 0.0864

The methodically determined values are close to the experimental values. Making reaction
(2) a second-order reaction with respect to ammonium cyanate and with a rate of k = 0.0597
M-1min-1.

Question: We would have expected that this reaction is first-order, because it is an

Isomerization and ammonium cyanate is the only reactant. However, using the integrated
rate law for the first order the results were much further away form the experimental ones.
How can we explain this? We have researched a bit and found that ammonium cyanate
normally dissociates in NH4+ and CNO-. Can it be explained by that? Or perhaps we have
done something else wrong.
3a)
Chain initiation: An initiator species reacts to form chain carriers, such as radicals. This
applies to the following reaction:

(4) CH3CHO → CH3• + CHO•

Chain propagation: A radical chain carrier reacts with the original reactant or other non-
radical species to form both radical and non-radical products.

(1) CHO• → CO + H•

(2) CH3• + CH3CHO → CH4 + CH3CO•

(6) CH3CO• → CH3• + CO

(7) H• + CH3CHO → H2 + CH3CO•

Chain termination: Radicals are removed from the system.

(3) H• + H• → H2

(5) CH3• + CH3• → C2H6

(8) CH3• + H• → CH4

3b)
Branching chain reaction: An elementary reaction, where more than one chain carrier is
generated in propagation steps.

For the mechanism to be classified as a branching chain reaction, at least one propagation
step has to generate more than one radical. In this case however, each propagation step
produces exactly one radical. Therefore, this mechanism is not a branching chain reaction.