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Chapter 3

Interpretation of Batch
Reactor Data

Dr. Enshirah Da'na 1

CONSTANT-VOLUME BATCH REACTOR

• The constant-volume batch reactor refers to the volume of reaction
mixture, and not the volume of reactor.
• This term actually means a constant-density reaction system.
• Most liquid-phase reactions as well as all gas-phase reactions
occurring in a constant-volume bomb fall in this class.
• In a constant-volume system the reaction rate of component i
becomes: 𝑵
𝟏 𝒅𝑵𝒊 𝒅 𝒊(𝑽 𝒅𝑪𝒊
𝒓𝒊 = = =
𝑽 𝒅𝒕 𝒅𝒕 𝒅𝒕
for ideal gases, where C = p/RT,
𝟏 𝒅𝑷𝒊
𝒓𝒊 =
𝑹𝑻 𝒅𝒕
Dr. Enshirah Da'na 2

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Analysis of Total Pressure Data Obtained in a Constant-Volume System.

• For isothermal gas reactions, the number of moles of material changes
during reaction.
• Write the general stoichiometric equation, and under each term
indicate the number of moles of that component:

Initially the total number of moles present in the system is:

𝑵𝟎 = 𝑵𝑨𝟎 + 𝑵𝑩𝟎 + ⋯ + 𝑵𝑹𝟎 + 𝑵𝑺𝟎 … + 𝑵𝒊𝒏𝒆𝒓𝒕
but at time t it is
𝑵 = 𝑵𝟎 + 𝒙 𝒓 + 𝒔 + … … − 𝒂 − 𝒃 − … … = 𝑵𝟎 + 𝒙∆𝒏 (𝟏)
Dr. Enshirah Da'na 3

∆𝒏 = 𝒓 + 𝒔 + … … − 𝒂 − 𝒃 − … …
Assuming the ideal gas law, we may write for any reactant A in the
system of volume V:
𝑷𝑨 𝑵𝑨 𝑵𝑨𝟎 − 𝒂𝒙
𝑪𝑨 = = = (𝟐)
𝑹𝑻 𝑵 𝑽
Combining Eqs. 1 and 2: 𝑵𝑨𝟎 𝒂 𝑵 − 𝑵𝟎
𝑪𝑨 = −
𝑽 ∆𝒏 𝑽
𝒂
𝒑𝑨 = 𝑪𝑨 𝑹𝑻 = 𝒑𝑨𝟎 − 𝝅 − 𝝅𝟎 (𝟑)
∆𝒏
𝝅 is the total pressure at time t.

𝝅𝟎 is the initial total pressure.

Dr. Enshirah Da'na 4

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Similarly, for any product R:

𝒓
𝒑𝑹 = 𝑪𝑹 𝑹𝑻 = 𝒑𝑹𝟎 + 𝝅 − 𝝅𝟎 (𝟒)
∆𝒏
• If the precise stoichiometry is not known, or if more than one
stoichiometric equation is needed, the "total pressure" cannot be used.

The Conversion.
If 𝑵𝑨𝟎 is the initial amount of A in the reactor at time t = 0, and 𝑵𝑨 is
the amount at time t. Then the conversion of A is:
𝑵𝑨
𝑵𝑨𝟎 − 𝑵𝑨 𝑵𝑨 𝑪𝑨
𝑿𝑨 = =𝟏− =𝟏− 𝑽 =𝟏−
𝑵𝑨𝟎 𝑵𝑨𝟎 𝑵𝑨𝟎 𝑪𝑨𝟎
𝑽
𝒅𝑪𝑨
𝒅𝑿𝑨 = −
𝑪𝑨𝟎
Dr. Enshirah Da'na 5

Integral Method of Analysis of Data

• It tests rate equation by integrating and comparing the predicted C
versus t curve with the experimental data.
• If the fit is unsatisfactory, another rate equation is tested.
• It is useful for fitting simple elementary reactions.
Irreversible Unimolecular-Type First-Order Reactions.
𝑨→𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒔
Test the first-order rate equation:

𝒅𝑪𝑨
−𝒓𝑨 = − = 𝒌𝑪𝑨
𝒅𝒕
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Separating and integrating: 𝑪𝑨 𝒅𝑪 𝒕

𝑨
−F = 𝒌 F 𝒅𝒕
𝑪𝑨𝟎 𝑪𝑨 𝟎

𝑪𝑨
−𝒍𝒏 = 𝒌𝒕 (𝟏)
𝑪𝑨𝟎
In terms of conversion:
𝒅𝑿𝑨
= 𝒌 𝟏 − 𝑿𝑨
𝒅𝒕
Rearranging and integrating:
𝑿𝑨 𝒕
𝒅𝑿𝑨
−F = 𝒌 F 𝒅𝒕
𝟎 𝟏 − 𝑿𝑨 𝟎

−𝒍𝒏 𝟏 − 𝑿𝑨 = 𝒌𝒕 (𝟐)
Dr. Enshirah Da'na 7

𝑪
• A plot of 𝒍𝒏 𝟏 − 𝑿𝑨 or 𝒍𝒏 𝑪 𝑨 Vs. t
𝑨𝟎
gives a straight line through the
origin.
• The slope of the line is k.

• If the experimental data better fitted

by a curve try another rate form.

Caution.
𝒅𝑪𝑨
• Equations as − = 𝒌𝑪𝟎.𝟔 𝟎.𝟒
𝑨 𝑪𝑩 are first order but can not be treated with
𝒅𝒕
this analysis.
Dr. Enshirah Da'na 8

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Irreversible Bimolecular-Type Second-Order Reactions.

𝑨 + 𝑩 = 𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒔
𝒅𝑪𝑨 𝒅𝑪𝑩
−𝒓𝑨 = − =− = 𝒌𝑪𝑨 𝑪𝑩
𝒅𝒕 𝒅𝒕
Amounts of A and B reacted at any time t are equal and given by
𝑪𝑨𝟎 𝑿𝑨 , then:
𝑪𝑨 = 𝑪𝑨𝟎 − 𝑪𝑨𝟎 𝑿𝑨

𝑪𝑩 = 𝑪𝑩𝟎 − 𝑪𝑨𝟎 𝑿𝑨
𝒅𝑿𝑨
−𝒓𝑨 = 𝑪𝑨𝟎 = 𝒌 𝑪𝑨𝟎 − 𝑪𝑨𝟎 𝑿𝑨 𝑪𝑩𝟎 − 𝑪𝑨𝟎 𝑿𝑨
𝒅𝒕

Dr. Enshirah Da'na 9

Letting 𝐌 = 𝑪𝑩𝟎 /𝑪𝑨𝟎 the initial molar ratio of reactants,

𝒅𝑿𝑨
−𝒓𝑨 = 𝑪𝑨𝟎 = 𝒌𝑪𝟐𝑨𝟎 𝟏 − 𝑿𝑨 𝑴 − 𝑿𝑨
𝒅𝒕
Separation and formal integration:
𝑿𝑨 𝒕
𝒅𝑿𝑨
F = 𝑪𝑨𝟎 𝒌 F 𝒅𝒕
𝟎 𝟏 − 𝑿𝑨 𝑴 − 𝑿𝑨 𝟎

𝟏 − 𝑿𝑩 𝑴 − 𝑿𝑨 𝑪𝑩𝑪𝑨𝟎 𝑪𝑩
𝒍𝒏 = 𝒍𝒏 = 𝒍𝒏 = 𝒍𝒏 = 𝑪𝑨𝟎 𝑴 − 𝟏 𝒌𝒕 = 𝑪𝑩𝟎 − 𝑪𝑨𝟎 𝒌𝒕 (𝟑)
𝟏 − 𝑿𝑨 𝑴 𝟏 − 𝑿𝑨 𝑪𝑩𝟎 𝑪𝑨 𝑴𝑪𝑨

𝐌≠𝟏
Dr. Enshirah Da'na 10

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Test 1:
𝟏 − 𝑿𝑩 𝑴 − 𝑿𝑨 𝑪𝑩𝑪𝑨𝟎 𝑪𝑩
𝒍𝒏 = 𝒍𝒏 = 𝒍𝒏 = 𝒍𝒏 = 𝑪𝑨𝟎 𝑴 − 𝟏 𝒌𝒕 = 𝑪𝑩𝟎 − 𝑪𝑨𝟎 𝒌𝒕
𝟏 − 𝑿𝑨 𝑴 𝟏 − 𝑿𝑨 𝑪𝑩𝟎 𝑪𝑨 𝑴𝑪𝑨
𝑪𝑩𝑪𝑨𝟎
𝒍𝒏 = 𝑪𝑩𝟎 − 𝑪𝑨𝟎 𝒌𝒕
𝑪𝑩𝟎 𝑪𝑨
𝐌≠𝟏
𝑪𝑩 𝑪𝑩𝟎 𝑪𝑩
𝒍𝒏
𝑪𝑨
− 𝒍𝒏
𝑪𝑨𝟎
= 𝒍𝒏
𝑪𝑨
− 𝒍𝒏𝑴 = 𝑪𝑩𝟎 − 𝑪𝑨𝟎 𝒌𝒕 𝑪𝑩𝟎 ≠ 𝑪𝑨𝟎
𝑪𝑩
𝒍𝒏 = 𝑪𝑩𝟎 − 𝑪𝑨𝟎 𝒌𝒕 + 𝒍𝒏𝑴
𝑪𝑨

𝑺𝒍𝒐𝒑𝒆 = 𝑪𝑩𝟎 − 𝑪𝑨𝟎 𝒌

𝑪𝑩𝟎
𝑰𝒏𝒕𝒆𝒓𝒄𝒆𝒑𝒕 = 𝒍𝒏 = 𝒍𝒏𝑴
𝑪𝑨𝟎
Dr. Enshirah Da'na 11

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Test 2:
𝟏 − 𝑿𝑩 𝑴 − 𝑿𝑨 𝑪𝑩𝑪𝑨𝟎 𝑪𝑩
𝒍𝒏 = 𝒍𝒏 = 𝒍𝒏 = 𝒍𝒏 = 𝑪𝑨𝟎 𝑴 − 𝟏 𝒌𝒕 = 𝑪𝑩𝟎 − 𝑪𝑨𝟎 𝒌𝒕
𝟏 − 𝑿𝑨 𝑴 𝟏 − 𝑿𝑨 𝑪𝑩𝟎 𝑪𝑨 𝑴𝑪𝑨

𝑪𝑩𝑪𝑨𝟎
𝒍𝒏 = 𝑪𝑩𝟎 − 𝑪𝑨𝟎 𝒌𝒕 𝐌≠𝟏
𝑪𝑩𝟎 𝑪𝑨
𝑪𝑩𝟎 ≠ 𝑪𝑨𝟎
𝑺𝒍𝒐𝒑𝒆 = 𝑪𝑩𝟎 − 𝑪𝑨𝟎 𝒌

𝑰𝒏𝒕𝒆𝒓𝒄𝒆𝒑𝒕 = 𝟎

Dr. Enshirah Da'na 12

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If 𝑪𝑩𝟎 is much larger than 𝑪𝑨𝟎 then:

• 𝑪𝑩𝟎 − 𝑪𝑨𝟎 ≅ 𝑪𝑩𝟎
• 𝑪𝑩 remains approximately constant at all times (𝑪𝑩𝟎 ≅ 𝑪𝑩) and (𝑿𝑩 ≅ 𝟎).
• Eq. 3 approaches Eq. 1 or 2 for the first-order reaction. Thus, the
second order reaction becomes a pseudo first-order reaction.
𝟏 − 𝑿𝑩 𝑴 − 𝑿𝑨 𝑪𝑩𝑪𝑨𝟎 𝑪𝑩
𝒍𝒏 = 𝒍𝒏 = 𝒍𝒏 = 𝒍𝒏 = 𝑪𝑨𝟎 𝑴 − 𝟏 𝒌𝒕 = 𝑪𝑩𝟎 − 𝑪𝑨𝟎 𝒌𝒕 (𝟑)
𝟏 − 𝑿𝑨 𝑴 𝟏 − 𝑿𝑨 𝑪𝑩𝟎 𝑪𝑨 𝑴𝑪𝑨

𝑪𝑩𝑪𝑨𝟎 𝑪𝑨𝟎
𝒍𝒏 ≅ 𝒍𝒏 ≅ 𝑪𝑩𝟎 − 𝑪𝑨𝟎 𝒌𝒕 ≅ 𝑪𝑩𝟎 𝒌𝒕 ≅ 𝒌𝒑𝒔𝒆𝒖𝒅𝒐𝒕
𝑪𝑩𝟎 𝑪𝑨 𝑪𝑨

𝑪𝑨𝟎
𝒍𝒏 ≅ 𝒌𝒑𝒔𝒆𝒖𝒅𝒐𝒕 𝑬𝒒𝒖𝒊𝒗𝒆𝒍𝒆𝒏𝒕 𝒕𝒐 𝑬𝒒. 𝟏
𝑪𝑨
𝑪𝑩𝟎 𝒌 = 𝒌𝒑𝒔𝒆𝒖𝒅𝒐
Dr. Enshirah Da'na 13

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𝟏 − 𝑿𝑩 𝑴 − 𝑿𝑨 𝑪𝑩𝑪𝑨𝟎 𝑪𝑩
𝒍𝒏 = 𝒍𝒏 = 𝒍𝒏 = 𝒍𝒏 = 𝑪𝑨𝟎 𝑴 − 𝟏 𝒌𝒕 = 𝑪𝑩𝟎 − 𝑪𝑨𝟎 𝒌𝒕 (𝟑)
𝟏 − 𝑿𝑨 𝑴 𝟏 − 𝑿𝑨 𝑪𝑩𝟎 𝑪𝑨 𝑴𝑪𝑨

𝑿𝑩 ≅ 𝟎
𝑪𝑩𝟎 − 𝑪𝑨𝟎 ≅ 𝑪𝑩𝟎
𝟏 − 𝑿𝑩 𝟏
𝒍𝒏 ≅ 𝒍𝒏 ≅ 𝑪𝑩𝟎 𝒌𝒕
𝟏 − 𝑿𝑨 𝟏 − 𝑿𝑨
𝑪𝑩𝟎 𝒌 = 𝒌𝒑𝒔𝒆𝒖𝒅𝒐

−𝒍𝒏 𝟏 − 𝑿𝑨 ≅ 𝒌𝒑𝒔𝒆𝒖𝒅𝒐𝒕 𝑬𝒒𝒖𝒊𝒗𝒆𝒍𝒆𝒏𝒕 𝒕𝒐 𝑬𝒒. 𝟐

Dr. Enshirah Da'na 14

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Caution 1.
• If reactants are introduced in their stoichiometric ratio, the integrated
rate expression becomes indeterminate and this requires taking limits
of quotients for evaluation.

• This difficulty is avoided if we go back to the original differential

rate expression and solve it for this particular reactant ratio.
• Thus, for the second-order reaction with equal initial concentrations
of A and B, or for the reaction:

Dr. Enshirah Da'na 15

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𝟐𝑨→𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒔

𝑨 + 𝑩→𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒔, 𝑪𝑩𝟎 = 𝑪𝑨𝟎

𝒅𝑪𝑨
−𝒓𝑨 = − = 𝒌𝑪𝟐𝑨 = 𝒌𝑪𝟐𝑨𝟎 𝟏 − 𝑿𝑨 𝟐
𝒅𝒕

which on integration yields:

𝟏 𝟏 𝟏 𝑿𝑨
− = = 𝒌𝒕
𝑪𝑨 𝑪𝑨𝟎 𝑪𝑨𝟎 𝟏 − 𝑿𝑨

Dr. Enshirah Da'na 16

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𝟏 𝟏 𝟏 𝑿𝑨
− = = 𝒌𝒕
𝑪𝑨 𝑪𝑨𝟎 𝑪𝑨𝟎 𝟏 − 𝑿𝑨

𝟏 𝟏 𝑿𝑨
Test 1: = 𝒌𝒕 + Test 2: = 𝑪𝑨𝟎 𝒌𝒕
𝑪𝑨 𝑪𝑨𝟎 𝟏 − 𝑿𝑨

Dr. Enshirah Da'na 17

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Caution 2.
The integrated expression depends on the stoichiometry as well as
the kinetics. To illustrate, if the reaction 𝑨 + 𝟐𝑩→𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒔
is first order with respect to both A and B, hence second order overall, or
𝒅𝑪𝑨
−𝒓𝑨 = − = 𝒌𝑪𝑨 𝑪𝑩 = 𝒌𝑪𝟐𝑨𝟎 𝟏 − 𝑿𝑨 𝑴 − 𝟐𝑿𝑨
𝒅𝒕
Integration: 𝑪𝑩𝑪𝑨𝟎 𝑴 − 𝟐𝑿𝑨
𝒍𝒏 = 𝒍𝒏 = 𝑪𝑨𝟎 𝑴 − 𝟐 𝒌𝒕, 𝑴≠𝟐
𝑪𝑩𝟎 𝑪𝑨 𝑴 𝟏 − 𝑿𝑨
When a stoichiometric reactant ratio is used the integrated form is:
𝟏 𝟏 𝟏 𝑿𝑨
− = = 𝟐𝒌𝒕, 𝑴=𝟐
𝑪𝑨 𝑪𝑨𝟎 𝑪𝑨𝟎 𝟏 − 𝑿𝑨
• These two cautions apply to all reaction types. Thus, special forms appear
whenever reactants are used in stoichiometric ratios, or when the reaction
is not elementary. Dr. Enshirah Da'na 18

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Irreversible Trimolecular-Type Third-Order Reactions.

𝑨 + 𝑩 + 𝑫→𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒔
𝒅𝑪𝑨
−𝒓𝑨 = − = 𝒌𝑪𝑨 𝑪𝑩 𝑪𝑫
𝒅𝒕
𝒅𝑿𝑨 𝑪𝑩𝟎 𝑪𝑫𝟎
𝑪𝑨𝟎 = 𝒌𝑪𝟑𝑨𝟎 𝟏 − 𝑿𝑨 − 𝑿𝑨 − 𝑿𝑨
𝒅𝒕 𝑪𝑨𝟎 𝑪𝑨𝟎

On separation of variables, breakdown into partial fractions, and

integration, we obtain after manipulation:
𝟏 𝑪𝑨𝟎 𝟏 𝑪𝑩𝟎 𝟏 𝑪𝑫𝟎
𝒍𝒏 + 𝒍𝒏 + 𝒍𝒏 = 𝒌𝒕
𝑪𝑨𝟎 − 𝑪𝑩𝟎 𝑪𝑨𝟎 − 𝑪𝑫𝟎 𝑪𝑨 𝑪𝑩𝟎 − 𝑪𝑫𝟎 𝑪𝑩𝟎 − 𝑪𝑨𝟎 𝑪𝑩 𝑪𝑫𝟎 − 𝑪𝑨𝟎 𝑪𝑫𝟎 − 𝑪𝑩𝟎 𝑪𝑫

Now if 𝑪𝑫𝟎 is much larger than both 𝑪𝑨𝟎 − 𝑪𝑩𝟎 the reaction becomes
second order. Dr. Enshirah Da'na 19

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𝟏 𝑪𝑨𝟎 𝟏 𝑪𝑩𝟎 𝟏 𝑪𝑫𝟎

𝒍𝒏 + 𝒍𝒏 + 𝒍𝒏 = 𝒌𝒕
𝑪𝑨𝟎 − 𝑪𝑩𝟎 𝑪𝑨𝟎 − 𝑪𝑫𝟎 𝑪𝑨 𝑪𝑩𝟎 − 𝑪𝑫𝟎 𝑪𝑩𝟎 − 𝑪𝑨𝟎 𝑪𝑩 𝑪𝑫𝟎 − 𝑪𝑨𝟎 𝑪𝑫𝟎 − 𝑪𝑩𝟎 𝑪𝑫

𝟏 𝑪𝑫𝟎
𝑰𝒇 𝑪𝑨𝟎 ≪ 𝑪𝑫𝟎 ≫ 𝑪𝑩𝟎 ∶ 𝒍𝒏 ≅𝟎
𝑪𝑫𝟎 − 𝑪𝑨𝟎 𝑪𝑫𝟎 − 𝑪𝑩𝟎 𝑪𝑫
𝟏 𝑪𝑨𝟎 𝟏 𝑪𝑩𝟎
𝒍𝒏 + 𝒍𝒏 = 𝒌𝒕
𝑪𝑨𝟎 − 𝑪𝑩𝟎 𝑪𝑨𝟎 − 𝑪𝑫𝟎 𝑪𝑨 𝑪𝑩𝟎 − 𝑪𝑫𝟎 𝑪𝑩𝟎 − 𝑪𝑨𝟎 𝑪𝑩

𝟏 𝑪𝑨𝟎 𝟏 𝑪𝑩𝟎
𝒍𝒏 + 𝒍𝒏 = 𝒌𝒕
−𝑪𝑫𝟎 𝑪𝑨𝟎 + 𝑪𝑫𝟎 𝑪𝑩𝟎 𝑪𝑨 −𝑪𝑫𝟎 𝑪𝑩𝟎 + 𝑪𝑫𝟎 𝑪𝑨𝟎 𝑪𝑩

𝟏 𝑪𝑨𝟎 𝑪𝑩𝟎
𝒍𝒏 − 𝒍𝒏 = 𝒌𝒕
−𝑪𝑫𝟎 𝑪𝑨𝟎 + 𝑪𝑫𝟎 𝑪𝑩𝟎 𝑪𝑨 𝑪𝑩
𝑪𝑨𝟎 𝑪𝑩
𝒍𝒏 = −𝑪𝑨𝟎 + 𝑪𝑩𝟎 𝑪𝑫𝟎 𝒌𝒕, 𝑪𝑫𝟎 𝒌𝒕 = 𝒌′𝒕
𝑪𝑨 𝑪𝑩𝟎

𝑪𝑨𝟎 𝑪𝑩
𝒍𝒏 = 𝑪𝑩𝟎 − 𝑪𝑨𝟎 𝒌′𝒕
Dr. Enshirah Da'na 𝑪𝑨 𝑪𝑩𝟎 20

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All trimolecular reactions found so far are of the form of :

𝑨 + 𝟐𝑩→𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒔
𝒅𝑪𝑨
−𝒓𝑨 = − = 𝒌𝑪𝑨 𝑪𝟐𝑩
𝒅𝒕

In terms of conversions the rate of reaction becomes:

𝒅𝑿𝑨
= 𝒌𝑪𝟐𝑨𝟎 𝟏 − 𝑿𝑨 𝑴 − 𝟐𝑿𝑨 𝟐
𝒅𝒕
𝐌 = 𝑪𝑩𝟎 /𝑪𝑨𝟎
𝟐𝑪𝑨𝟎 −𝑪𝑩𝟎 𝑪𝑩𝟎 − 𝑪𝑩 𝑪𝑩𝑪𝑨𝟎
+ 𝒍𝒏 = 𝟐𝑪𝑨𝟎 −𝑪𝑩𝟎 𝟐 𝒌𝒕, 𝑴≠𝟐
𝑪𝑩𝟎 𝑪𝑩 𝑪𝑩𝟎 𝑪𝑨
𝟏 𝟏
− = 𝟖𝒌𝒕, 𝑴=𝟐
Dr. Enshirah Da'na
𝑪𝟐𝑨 𝑪𝟐𝑨𝟎 21

21

Similarly, for the reaction: 𝑨 + 𝑩→𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒔

𝒅𝑪𝑨
−𝒓𝑨 = − = 𝒌𝑪𝑨 𝑪𝟐𝑩
𝒅𝒕
𝑪𝑨𝟎 −𝑪𝑩𝟎 𝑪𝑩𝟎 − 𝑪𝑩 𝑪𝑩𝑪𝑨𝟎
+ 𝒍𝒏 = 𝑪𝑨𝟎 −𝑪𝑩𝟎 𝟐 𝒌𝒕, 𝑴≠𝟏
𝑪𝑩𝟎 𝑪𝑩 𝑪𝑩𝟎 𝑪𝑨

𝟏 𝟏
− = 𝟐𝒌𝒕, 𝑴=𝟏
𝑪𝟐𝑨 𝑪𝟐𝑨𝟎

Dr. Enshirah Da'na 22

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Empirical Rate Equations of nth Order

When the mechanism of reaction is not known, we often attempt to fit the
data with an nth-order rate equation of the form:
𝒅𝑪𝑨
−𝒓𝑨 = − = 𝒌𝑪𝒏𝑨
𝒅𝒕
which on separation and integration yields
𝑪𝟏,𝒏
𝑨 − 𝑪𝟏,𝒏
𝑨𝟎 = 𝒏 − 𝟏 𝒌𝒕, 𝒏≠𝟏

• The order n can be found by a trial-and-error solution.

• Select a value for n and calculate k. The value of n which minimizes the
variation in k is the desired value of n.
• One curious feature of this rate form is that reactions with order n
> 1 can never go to completion in finite time.
Dr. Enshirah Da'na 23

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• for orders n < 1 this rate form predicts that the reactant concentration
will fall to zero and then become negative at some finite time, so
𝑪𝟏,𝒏
𝑨𝟎
𝑪𝑨 = 𝟎 𝒂𝒕 𝒕≥
𝟏−𝒏 𝒌

• Since the real concentration cannot fall below zero we should not
carry out the integration beyond this time for n < 1.

In real systems the observed fractional order will shift upward to

unity as reactant is depleted.

Dr. Enshirah Da'na 24

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Zero-Order Reactions.
A reaction is of zero order when the rate of reaction is independent of the
concentration of materials; thus
𝒅𝑪𝑨
−𝒓𝑨 = − =𝒌
𝒅𝒕
Integrating and noting that 𝑪𝑨 can never become negative,
𝑪𝑨𝟎
𝑪𝑨𝟎 − 𝑪𝑨 = 𝑪𝑨𝟎 𝑿𝑨 = 𝒌𝒕 𝒕<
𝒌
𝑪𝑨𝟎
𝑪𝑨 = 𝟎 𝒕≥
𝒌
As a rule, reactions are of zero order only in the higher concentration
ranges.
If the concentration is lowered far enough, the reaction becomes
concentration-dependent, the order rises from zero.
Dr. Enshirah Da'na 25

25

𝑪𝑨𝟎
𝑪𝑨𝟎 − 𝑪𝑨 = 𝑪𝑨𝟎 𝑿𝑨 = 𝒌𝒕 𝒕<
𝒌
𝑪𝑨𝟎
𝑪𝑨 = 𝟎 𝒕≥
𝒌

Dr. Enshirah Da'na 26

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Overall Order of Irreversible Reactions from the Half-Life t1/2

𝒂𝑨 + 𝒃𝑩 + ⋯ →𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒔
𝒅𝑪𝑨
−𝒓𝑨 = − = 𝒌𝑪𝒂𝑨 𝑪𝒃𝑩 …
𝒅𝒕

If the reactants are present in their stoichiometric ratios, they will

remain at that ratio throughout the reaction. Thus, for reactants A and B
at any time 𝑪𝑩 /𝑪𝑨 = b/a, and:
𝒃 𝒃
𝒅𝑪𝑨 𝒃 𝒃
−𝒓𝑨 = − = 𝒌𝑪𝒂𝑨 𝑪𝑨 …=𝒌 … . 𝑪𝒂>𝒃…
𝑨
𝒅𝒕 𝒂 𝒂
𝒃
𝒃
𝒌 W
= 𝒌 𝑪𝒂>𝒃… = 𝑪𝒏𝑨
𝒂 𝑨
Dr. Enshirah Da'na 27

27

𝒅𝑪𝑨
−𝒓𝑨 = − W 𝒏𝑨
= 𝒌𝑪
𝒅𝒕
Integrating for n # 1: 𝑪𝟏@𝒏
𝑨 − 𝑪𝟏@𝒏 W
𝑨𝟎 = 𝒌 𝒏 − 𝟏 𝒕

Defining the half-life of the reaction, t1/2, as the time needed for the
concentration of reactants to drop to one-half the original value,
𝟎. 𝟓 𝟏@𝒏 − 𝟏 𝟏@𝒏
𝒕𝟏 = 𝑪𝑨𝟎
𝟐
W 𝒏−𝟏
𝒌

This expression shows that a plot of log t1/2 vs. log 𝑪𝑨𝟎 gives a straight
line of slope 1-n,

Dr. Enshirah Da'na 28

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• The half-life method requires making a series of runs at different 𝑪𝑨𝟎.

• The 𝑿𝑨 in a given time rises with increased 𝑪𝑨𝟎 for orders greater than
one.
• 𝑿𝑨 drops with increased 𝑪𝑨𝟎 for orders less than one.

• 𝑿𝑨 is independent of 𝑪𝑨𝟎
for reactions of first
order.

Dr. Enshirah Da'na 29

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If all but one component, A in large excess, find the order with respect
to that component A. The general expression reduces to:

𝒅𝑪𝑨
−𝒓𝑨 = − Y 𝒂𝑨
= 𝒌𝑪
𝒅𝒕
Y = 𝒌 𝑪𝒃𝑩𝟎 …
𝒌 𝒂𝒏𝒅 𝑪𝑩𝟎 ≅ 𝑪𝑩

Fractional Life Method tf.

The half-life method can be extended to any fractional life method in
𝑪𝑨
which the concentration of reactant drops to any fractional value 𝐅 = 𝑪𝑨𝟎
in
time tf. The derivation is a direct extension of the half-life method giving

Dr. Enshirah Da'na 30

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𝑭 𝟏@𝒏 − 𝟏 𝟏@𝒏
𝒕𝑭 = 𝑪𝑨𝟎
𝒌 𝒏−𝟏

a plot of log 𝒕𝑭 versus log 𝑪𝑨𝟎 give the reaction order.

Irreversible Reactions in Parallel.

A decomposing by two competing paths, both elementary reactions:

[]
! #
[\ !
! "

Dr. Enshirah Da'na 31

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𝒅𝑪𝑨
−𝒓𝑨 = − = 𝒌𝟏 𝑪𝑨 + 𝒌𝟐 𝑪𝑨 = 𝒌𝟏 + 𝒌𝟐 𝑪𝑨 (𝟏)
𝒅𝒕
𝒅𝑪𝑹
𝒓𝑹 = = 𝒌𝟏 𝑪𝑨 (𝟐)
𝒅𝒕
𝒅𝑪𝑺
𝒓𝑺 = = 𝒌𝟐 𝑪𝑨 (𝟑)
𝒅𝒕
• Write N stoichiometric equations:
• In this system following 𝑪𝑨 , or 𝑪𝑹 , or 𝑪𝑺 , alone will not give both 𝒌𝟏 ,
and 𝒌𝟐 . At least two components must be followed.

• Then, from the stoichiometry, noting that 𝑪𝑨 + 𝑪𝑹 + 𝑪𝑺 is constant,

we can find the concentration of the third component.
• The k values are found using all three differential rate equations.
Dr. Enshirah Da'na 32

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First integrate Eq. 1 :

𝒅𝑪𝑨
−𝒓𝑨 = − = 𝒌𝟏 𝑪𝑨 + 𝒌𝟐 𝑪𝑨 = 𝒌𝟏 + 𝒌𝟐 𝑪𝑨 (𝟏)
𝒅𝒕
𝑪𝑨
−𝒍𝒏 = 𝒌𝟏 + 𝒌𝟐 𝒕
𝑪𝑨𝟎

When plotted, the slope is 𝒌𝟏 + 𝒌𝟐 .

Dr. Enshirah Da'na 33

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Then dividing Eq. 2 by Eq. 3 :

𝒓𝑹 𝒅𝑪𝑹 𝒌𝟏
= =
𝒓𝑺 𝒅𝑪𝑺 𝒌𝟐
Integrate: 𝑪𝑹 − 𝑪𝑹𝟎 𝒌𝟏
=
𝑪𝑺 − 𝑪𝑺𝟎 𝒌𝟐

• The slope of a plot of 𝑪𝑹 versus 𝑪𝑺

𝒌
gives the ratio 𝟏 .
𝒌𝟐
𝒌𝟏
• Knowing 𝒌 and 𝒌𝟏 + 𝒌𝟐 , gives 𝒌𝟏 and 𝒌𝟐 .
𝟐

Dr. Enshirah Da'na 34

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Typical concentration-time curves for competing reactions.

Dr. Enshirah Da'na 35

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Homogeneous Catalyzed Reactions.

Suppose the reaction rate for a homogeneous catalyzed system is the sum
of rates of both the uncatalyzed and catalysed reactions,
[]
! #
[\ !
!$% #$%
𝒅𝑪𝑨 𝒅𝑪𝑨
− = 𝒌𝟏 𝑪𝑨 − = 𝒌𝟐 𝑪𝑨 𝑪𝑪
𝒅𝒕 𝟏 𝒅𝒕 𝟐

The overall rate of disappearance of reactant A is:

𝒅𝑪𝑨
− = 𝒌𝟏 𝑪𝑨 + 𝒌𝟐 𝑪𝑨 𝑪𝑪 = 𝒌𝟏 + 𝒌𝟐 𝑪𝑪 𝑪𝑨
𝒅𝒕
Dr. Enshirah Da'na 36

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On integration, noting that the catalyst concentration remains unchanged:

𝑪𝑨
−𝒍𝒏 = −𝒍𝒏 𝟏 − 𝑿𝑨 = 𝒌𝟏 + 𝒌𝟐 𝑪𝑪 𝒕 = 𝒌𝒐𝒃𝒔𝒆𝒓𝒗𝒆𝒅 𝒕
𝑪𝑨𝟎
Make a series of runs with different catalyst concentrations to find
𝒌𝟏 and 𝒌𝟐 .

Plot 𝒌𝒐𝒃𝒔𝒆𝒓𝒗𝒆𝒅 against the catalyst

concentrations.

The slope of such a plot is 𝒌𝟐 ,

and the intercept 𝒌𝟏 .

Dr. Enshirah Da'na 37

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Autocatalytic Reactions.
A reaction in which one of the products of reaction acts as a catalyst is
called an autocatalytic reaction.

𝑨 + 𝑹→𝑹 + 𝑹
𝒅𝑪𝑨
−𝒓𝑨 = − = 𝒌𝑪𝑨 𝑪𝑹
𝒅𝒕
Because the total number of moles of A and R remain unchanged as A is
consumed, we may write that at any time
𝑪𝟎 = 𝑪𝑨 + 𝑪𝑹 = 𝑪𝑨𝟎 + 𝑪𝑹𝟎 = 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕

𝒅𝑪𝑨
−𝒓𝑨 = − = 𝒌𝑪𝑨 𝑪𝟎 − 𝑪𝑨
𝒅𝒕
Dr. Enshirah Da'na 38

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Rearranging and breaking into partial fractions,

𝒅𝑪𝑨 𝟏 𝒅𝑪𝑨 𝒅𝑪𝑨
− =− − = 𝒌𝒅𝒕
𝑪𝑨 𝑪𝟎 − 𝑪𝑨 𝑪𝟎 𝑪𝑨 𝑪𝟎 − 𝑪𝑨

Integrate:
𝑪𝑨𝟎 𝑪𝟎 − 𝑪𝑨 𝑪𝑹 /𝑪𝑹𝟎
𝒍𝒏 = 𝒍𝒏 = 𝑪𝟎 𝒌𝒕 = 𝑪𝑨𝟎 + 𝑪𝑹𝟎 𝒌𝒕
𝑪𝑨 𝑪𝟎 − 𝑪𝑨𝟎 𝑪𝑨 /𝑪𝑨𝟎
In terms of the initial reactant ratio 𝑴 = 𝑪𝑹𝟎 /𝑪𝑨𝟎 and fractional
conversion of A, this can be written as
𝑴 + 𝑿𝑨
𝒍𝒏 = 𝑪𝑨𝟎 𝑴 + 𝟏 𝒌𝒕 = 𝑪𝑨𝟎 + 𝑪𝑹𝟎 𝒌𝒕
𝑴 𝟏 − 𝑿𝑨

Dr. Enshirah Da'na 39

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Conversion-time and rate-concentration curves for autocatalytic

reaction. This shape is typical for this type of reaction.
Dr. Enshirah Da'na 40

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Test for the autocatalytic reaction

Dr. Enshirah Da'na 41

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Irreversible Reactions in Series.

𝒌𝟏 𝒌𝟐
𝑨→𝑹→𝑺
𝒅𝑪𝑨
𝒓𝑨 = = −𝒌𝟏 𝑪𝑨 (𝟏)
𝒅𝒕
𝒅𝑪𝑹
𝒓𝑹 = = 𝒌𝟏 𝑪𝑨 − 𝒌𝟐 𝑪𝑹 (𝟐)
𝒅𝒕
𝒅𝑪𝑺
𝒓𝑺 = = 𝒌𝟐 𝑪𝑹 (𝟑)
𝒅𝒕

start with a concentration 𝑪𝑨𝟎 of A, no R or S present,

Dr. Enshirah Da'na 42

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𝑪𝑨
integration of Eq. 1: −𝒍𝒏 = 𝒌𝟏 𝒕
𝑪𝑨𝟎
𝑪𝑨 = 𝑪𝑨𝟎 𝒆𝒌𝟏 𝒕 (𝟒)
substitute the concentration of A from Eq. 4 into Eq. 2;
𝒅𝑪𝑹
+ 𝒌𝟐 𝑪𝑹 = 𝒌𝟏 𝑪𝑨𝟎 𝒆𝒌𝟏 𝒕 (𝟓)
𝒅𝒕
which is a first-order linear differential equation of the form:
𝒅𝒚
+ 𝑷𝒚 = 𝑸
𝒅𝒙
Applying this general procedure to the integration of Eq. 5

𝒆@𝒌𝟏 𝒕 𝒆@𝒌𝟐 𝒕
𝑪𝑹 = 𝑪𝑨𝟎 𝒌𝟏 + (𝟔)
𝒌𝟐 − 𝒌𝟏 𝒌𝟏 − 𝒌𝟐 43

Dr. Enshirah Da'na

43

The total number of moles is constant:

𝑪𝟎 = 𝑪𝑨 + 𝑪𝑹 + 𝑪𝑺 = 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
with Eqs. 5 and 6 gives:
𝒌𝟐 𝒌𝟏
𝑪𝑺 = 𝑪𝑨𝟎 𝟏 + 𝒆@𝒌𝟏 𝒕 + 𝒆@𝒌𝟐 𝒕 (𝟕)
𝒌𝟏 − 𝒌𝟐 𝒌𝟐 − 𝒌𝟏

if 𝒌𝟐 is much larger than 𝒌𝟏 Eq. 7 reduces to:

𝑪𝑺 = 𝑪𝑨𝟎 𝟏 − 𝒆@𝒌𝟏 𝒕 , 𝒌𝟐 ≫ 𝒌𝟏

the rate is determined by 𝒌𝟏 , or the first step of the two-step reaction.

Dr. Enshirah Da'na 44

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if 𝒌𝟏 is much larger than 𝒌𝟐 :

𝑪𝑺 = 𝑪𝑨𝟎 𝟏 − 𝒆@𝒌𝟐 𝒕 , 𝒌𝟏 ≫ 𝒌𝟐

in general, for any number of reactions in series it is the slowest

step that has the greatest influence on the overall reaction rate.

the values of 𝒌𝟏 and 𝒌𝟐 also govern the location and maximum

concentration of R.
𝒅𝑪𝑹
This may be found by differentiating Eq. 6 and setting 𝒅𝒕
= 𝟎.
The time at which the maximum concentration of R occurs is:
𝒌
𝟏 𝒍𝒏 𝟐(𝒌
𝟏
𝒕𝒎𝒂𝒙 = = (𝟖)
𝒌𝒍𝒐𝒈 𝒎𝒆𝒂𝒏
Dr. Enshirah Da'na 𝒌𝟐 − 𝒌𝟏 45

45

The maximum concentration of R is found by combining Eqs. 6 and 8:

𝒌𝟐
I 𝒌 @𝒌
𝑪𝑹,𝒎𝒂𝒙 𝒌𝟏 𝟐 𝟏
= (𝟗)
𝑪𝑨𝟎 𝒌𝟐

Dr. Enshirah Da'na 46

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• A decreases exponentially
• R rises to a maximum and then
falls
• S rises continuously

• The greatest rate of

increase of S occurring
where R is a maximum.
• We can evaluate 𝒌𝟏 and 𝒌𝟐 by
noting the maximum
concentration of intermediate
and the time when this
maximum is reached.
Dr. Enshirah Da'na 47

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First-Order Reversible Reactions

• No reaction ever goes to completion.
• we can consider many reactions to be irreversible because of the
large value of the equilibrium constant.
Consider reaction for which complete conversion cannot be assumed:
𝒌𝟏
𝑨 𝑹, 𝑲𝑪 = 𝑲 = 𝒆𝒒𝒖𝒊𝒍𝒊𝒃𝒓𝒊𝒖𝒎 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
𝒌𝟐
𝑪𝑹𝟎
Starting with a concentration ratio 𝐌 = ( 𝑪𝑨𝟎 th e rate equation is:
𝒅𝑪𝑹 𝒅𝑪𝑨 𝒅𝑿𝑨
=− = 𝑪𝑨𝟎 = 𝒌𝟏 𝑪𝑨 − 𝒌𝟐 𝑪𝑹 = 𝒌𝟏 𝑪𝑨𝟎 − 𝑪𝑨𝟎 𝑿𝑨 − 𝒌𝟐 𝑴𝑪𝑨𝟎 + 𝑪𝑨𝟎 𝑿𝑨
𝒅𝒕 𝒅𝒕 𝒅𝒕
at equilibrium 𝒅𝒕𝑹 = 𝟎, 𝐭𝐡𝐞𝐧: 𝑲𝑪 = 𝑪𝑹𝒆 = 𝑴 + 𝑿𝑨𝒆
𝒅𝑪
𝑪𝑨𝒆 𝟏 − 𝑿𝑨𝒆

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𝒌𝟏
𝑲𝑪 =
𝒌𝟐
Combining the three equations:
𝒅𝑿𝑨 𝒌𝟏 𝑴 + 𝟏
= 𝑿𝑨𝒆 − 𝑿𝑨
𝒅𝒕 𝑴 + 𝑿𝑨𝒆

With conversions measured in terms of 𝑿𝑨𝒆, this may be looked on as a

pseudo first-order irreversible reaction which on integration gives:

𝑿𝑨 𝑪𝑨 − 𝑪𝑨𝒆 𝑴+𝟏
−𝒍𝒏 𝟏 − = −𝒍𝒏 = 𝒌 𝒕
𝑿𝑨𝒆 𝑪𝑨𝟎 − 𝑪𝑨𝒆 𝑴 + 𝑿𝑨𝒆 𝟏

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49

• The similarity between

equations for the first-
order irreversible and
reversible reactions can
be seen.

• The irreversible
reaction is simply the
special case of the
reversible reaction in
which 𝑪𝑨𝒆 = 𝟎, or 𝑿𝑨𝒆
= 𝟏, or 𝑲𝑪 = ∞.
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Second-Order Reversible Reactions.

𝒌𝟏 𝒌𝟏
𝑨+𝑩 𝑹+𝑺 𝟐𝑨 𝑹 + 𝑺
𝒌𝟐 𝒌𝟐
𝒌𝟏
𝒌𝟏
𝟐𝑨 𝟐𝑹 𝑨 + 𝑩 𝟐𝑹
𝒌𝟐
𝒌𝟐

with the restrictions that 𝑪𝑨𝟎 = 𝑪𝑩𝟎 and 𝑪𝑹𝟎 = 𝑪𝑺𝟎 = 𝟎, the integrated
rate equations for A and B are all identical:

𝑿𝑨𝒆 − 𝟐𝑿𝑨𝒆 − 𝟏 𝑿𝑨 𝟏
𝒍𝒏 = 𝟐𝒌𝟏 − 𝟏 𝑪𝑨𝟎 𝒕
𝑿𝑨𝒆 − 𝑿𝑨 𝑿𝑨𝒆

Dr. Enshirah Da'na 51

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Dr. Enshirah Da'na 52

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Reactions of Shifting Order.

• In searching for a kinetic equation it may be found that the data are
well fitted by one reaction order at high concentrations but by
another order at low concentrations.
𝑨→𝑹
𝒅𝑪𝑨 𝒌𝟏 𝑪𝑨
−𝒓𝑨 = − =
𝒅𝒕 𝟏 + 𝒌𝟐 𝑪𝑨
• At high 𝑪𝑨 (or 𝒌𝟐 𝑪𝑨 ≫ 𝟏)the reaction is of zero order with rate
𝒌
constant 𝒌𝟏 .
𝟐

• At low 𝑪𝑨 (or 𝒌𝟐 𝑪𝑨 ≪ 𝟏)the reaction is of first order with rate constant

𝒌𝟏 .

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53

Separate variables and integrate:

𝑪𝑨𝟎
𝒍𝒏 + 𝒌𝟐 𝑪𝑨𝟎 − 𝑪𝑨 = 𝒌𝟏 𝒕
𝑪𝑨

To linearize, rearrange:
𝑪𝑨𝟎 − 𝑪𝑨 𝟏 𝒌𝟏 𝒕
=− +
𝑪 𝒌𝟐 𝒌𝟐 𝒍𝒏 𝑪𝑨𝟎(
𝒍𝒏 𝑨𝟎(𝑪 𝑪𝑨
𝑨

𝑪𝑨𝟎
𝒍𝒏 (𝑪 𝒌𝟏 𝒕
𝑨
= −𝒌𝟐 +
𝑪𝑨𝟎 − 𝑪𝑨 𝑪𝑨𝟎 − 𝑪𝑨

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Dr. Enshirah Da'na 55

55

For the general rate form: 𝒌𝟏 𝑪𝒎

𝒅𝑪𝑨 𝑨
−𝒓𝑨 = − =
𝒅𝒕 𝟏 + 𝒌𝟐 𝑪𝒏𝑨
• shifts from order m - n at high concentration to order m at low
concentration.
• The transition taking place where 𝒌𝟐 𝑪𝒏𝑨 ≅ 𝟏.
• This type of equation can then be used to fit data of any two orders.
Another form which can account for this shift is:
𝒅𝑪𝑨 𝒌𝟏 𝑪𝒎
𝑨
−𝒓𝑨 = − = 𝒏
𝒅𝒕 𝟏 + 𝒌𝟐 𝑪𝑨
Mechanism studies may suggest which form to use. In any case, if
one of these equation forms will fit the data, so will the other. 56
Dr. Enshirah Da'na

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Example 1.
Reactant A decomposes in a batch reactor 𝑨→𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒔
The composition of A in the reactor is measured at various times with
results shown in the following columns 1 and 2. Find a rate equation to
represent the data.
Solution.
Guess First-Order Kinetics.
𝑪𝑨𝟎
This means that 𝒍𝒏 𝑪𝑨
Vs. t should give a
straight line.
𝑪𝑨
−𝒍𝒏 = 𝒌𝒕 (𝟏)
𝑪𝑨𝟎
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This does not give a straight line, so first-order kinetics

cannot reasonably represent the data, and we must guess another rate
form.

Dr. Enshirah Da'na 58

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Guess Second-Order Kinetics.

vs. t should give a straight line. 𝟏 − 𝟏 = 𝟏 𝑿𝑨
𝟏
𝑪𝑨 = 𝒌𝒕
𝑪𝑨 𝑪𝑨𝟎 𝑪𝑨𝟎 𝟏 − 𝑿𝑨

This does not give a straight line, so a second-order kinetic form is rejected.

Dr. Enshirah Da'na 59

59

Guess nth-Order Kinetics.

Use the fractional life method with F = 80%.
𝑭 𝟏@𝒏 − 𝟏 𝟏@𝒏
𝒕𝑭 = 𝑪𝑨𝟎
𝒌 𝒏−𝟏
take logarithms

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The procedure is as follows:

• First accurately plot the 𝑪𝑨 vs. t data.
• Draw a smooth curve to represent the data (most important)
• Pick 𝑪𝑨𝟎 = 10, 5, and 2 and fill in the following table from this figure.

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• plot log 𝒕𝑭 vs. log 𝑪𝑨𝟎 and find the slope.

• From the slope we have the reaction order n.

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• To evaluate the rate constant, take any point on the 𝑪𝑨 vs. t curve.
Pick 𝑪𝑨𝟎 = 10, for which 𝒕𝑭 = 18.5 s. Replacing all values gives:
𝑭 𝟏@𝒏 − 𝟏 𝟏@𝒏
𝒕𝑭 = 𝑪𝑨𝟎
𝒌 𝒏−𝟏
𝟎. 𝟖 𝟏@𝟏.𝟒 − 𝟏 𝟏@𝟏.𝟒
𝟏𝟖. 𝟓 = 𝟏𝟎
𝒌 𝟏. 𝟒 − 𝟏

𝒍𝒊𝒕𝒆𝒓𝟎.𝟒
𝒌 = 𝟎. 𝟎𝟎𝟓
𝒎𝒐𝒍𝟎.𝟒 . 𝒔

Therefore, the rate equation that represents this reaction is:

𝒅𝑪𝑨 𝒎𝒐𝒍
−𝒓𝑨 = − = 𝟎. 𝟎𝟎𝟓𝑪𝟏.𝟒
𝑨
𝒅𝒕 𝒍𝒊𝒕𝒆𝒓.𝒔

63
Dr. Enshirah Da'na

63

VARYING-VOLUME BATCH REACTOR

• These reactors are much more complex than the simple constant-
volume batch reactor.
• Their main use would be in the microprocessing field where a capillary
tube with a movable bead would represent the reactor.
• The progress of the reaction is followed by noting the movement of
the bead with time, a much simpler procedure than trying to measure
the composition of the mixture, especially for microreactors. Thus,

𝑽𝟎 = initial volume of the reactor.

𝑽 = volume at time t.

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• This kind of reactor can be used for isothermal constant pressure

operations, of reactions having a single stoichiometry.
• The volume is linearly related to the conversion, or
𝑽 = 𝑽𝟎 𝟏 + 𝜺𝑨 𝑿𝑨 (𝟏)
𝑽 − 𝑽𝟎
𝑿𝑨 = (𝟐)
𝑽𝟎 𝜺𝑨
𝒅𝑽
𝒅𝑿𝑨 = (𝟑)
𝑽𝟎 𝜺𝑨
where 𝜺𝑨 is the fractional change in volume of the system between no
conversion and complete conversion of reactant A. Thus

𝑽𝑿𝑨 J𝟏 − 𝑽𝑿𝑨 J𝟎
𝜺𝑨 = (𝟒)
𝑽𝑿𝑨 J𝟎
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Consider the isothermal gas-phase reaction 𝑨→𝟒𝑹

By starting with pure reactant A,

𝟒−𝟏
𝜺𝑨 = =𝟑
𝟏
but with 50% inerts present at the start, two volumes of reactant mixture
yield, on complete conversion, five volumes of product mixture. In this
case: 𝟓−𝟐
𝜺𝑨 = = 𝟏. 𝟓
𝟐
𝜺𝑨 accounts for both the reaction stoichiometry and the presence of
inerts. Noting that
𝑵𝑨 = 𝑵𝑨𝟎 𝟏 − 𝑿𝑨 (𝟓)
𝑵𝑨 𝑵𝑨𝟎 𝟏 − 𝑿𝑨 𝟏 − 𝑿𝑨
𝑪𝑨 = = = 𝑪𝑨𝟎 (𝟔)
Dr. Enshirah Da'na 𝑽 𝑽 𝟎 𝟏 + 𝜺𝑨 𝑿𝑨 𝟏 + 𝜺𝑨 𝑿𝑨 66

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𝑪𝑨 𝟏 − 𝑿𝑨
= (𝟕)
𝑪𝑨𝟎 𝟏 + 𝜺𝑨 𝑿𝑨
𝑪
𝟏 − 𝑨(𝑪
𝑨𝟎
𝑿𝑨 = (𝟖)
𝑪𝑨
𝟏 + 𝜺𝑨 (𝑪
𝑨𝟎
The rate of reaction (disappearance of component A) is:
𝒅𝑪𝑨 𝟏 𝒅𝑵𝑨
−𝒓𝑨 = − =−
𝒅𝒕 𝑽 𝒅𝒕
Replacing V from Eq. 1 and 𝑵𝑨 from Eq. 5 we end up with the rate in
terms of the conversion
𝑪𝑨𝟎 𝒅𝑿𝑨 or 𝑪𝑨𝟎 𝒅𝑽 𝑪𝑨𝟎 𝒅 𝒍𝒏𝑽
−𝒓𝑨 = −𝒓𝑨 = =
𝟏 + 𝜺𝑨 𝑿𝑨 𝒅𝒕 𝑽𝜺𝑨 𝒅𝒕 𝜺𝑨 𝒅𝒕
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67

Integral Method of Analysis

Zero-Order Reactions
𝑪𝑨𝟎 𝒅 𝒍𝒏𝑽
−𝒓𝑨 = =𝒌
𝜺𝑨 𝒅𝒕
Integrate:
𝑪𝑨𝟎 𝑽
𝒍𝒏 = 𝒌𝒕
𝜺𝑨 𝑽𝟎

The logarithm of the fractional change

in volume versus time yields a straight
𝒌𝜺
line of slope 𝑪 𝑨 .
𝑨𝟎

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First-Order Reactions
𝑪𝑨𝟎 𝒅 𝒍𝒏𝑽 𝟏 − 𝑿𝑨
−𝒓𝑨 = = 𝒌𝑪𝑨 = 𝒌𝑪𝑨𝟎
𝜺𝑨 𝒅𝒕 𝟏 + 𝜺𝑨 𝑿𝑨

Replacing 𝑿𝑨 by V from Eqs. 2 and integrating gives:

∆𝑽
−𝒍𝒏 𝟏 − = 𝒌𝒕
𝜺𝑨 𝑽𝟎

∆𝑽 = 𝑽 − 𝑽𝟎

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A semilogarithmic plot yields a straight line of slope k.

∆𝑽
−𝒍𝒏 𝟏 − = 𝒌𝒕
𝜺𝑨 𝑽𝟎

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Second-Order Reactions
𝟐𝑨→𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒔
𝑨 + 𝑩→𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒔, 𝑪𝑨𝟎 = 𝑪𝑩𝟎

𝟐
𝑪𝑨𝟎 𝒅 𝒍𝒏𝑽 𝟏 − 𝑿𝑨
−𝒓𝑨 = = 𝒌𝑪𝟐𝑨 = 𝒌𝑪𝟐𝑨𝟎
𝜺𝑨 𝒅𝒕 𝟏 + 𝜺𝑨 𝑿𝑨

Replacing 𝑿𝑨 by V from Eq. 2 and then integrating gives, after much

algebraic manipulation,
𝟏 + 𝜺𝑨 ∆𝑽 ∆𝑽
+ 𝜺𝑨 𝒍𝒏 𝟏 − = 𝒌𝑪𝑨𝟎 𝒕
𝑽𝟎 𝜺𝑨 − ∆𝑽 𝑽𝟎 𝜺𝑨

Dr. Enshirah Da'na 71

71

Dr. Enshirah Da'na 72

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nth-Order and Other Reactions.

For all rate forms other than zero-, first-, and second-order the integral
method of analysis is not useful.

TEMPERATURE AND REACTION RATE

In a typical rate equation:
𝒅𝑪𝑨 𝟏 𝒅𝑵𝑨
−𝒓𝑨 = − =− = 𝒌𝒇 𝑪
𝒅𝒕 𝑽 𝒅𝒕
it is the reaction rate constant 𝒌 the concentration-independent term,
which is affected by the temperature, whereas the concentration-
dependent terms f(C) usually remain unchanged at different
temperatures.
𝒌 ∝ 𝑻𝒎 𝒆@𝑬⁄𝑹𝑻
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• The exponential term is much more temperature-sensitive thanthe

power term, we can reasonably consider the rate constants to vary
approximately as 𝒆@𝑬⁄𝑹𝑻 .
• we can examine the variation of the rate constant with temperature
by Arrhenius relationship:
𝒌 = 𝒌𝟎 𝒆@𝑬⁄𝑹𝑻

𝑱
𝑬=
𝒎𝒐𝒍

Dr. Enshirah Da'na 74

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If the rate constant is found at two different temperatures

𝒌𝟐 𝑬 𝟏 𝟏
𝒍𝒏 = −
𝒌𝟏 𝑹 𝑻𝟏 𝑻𝟐

𝑹𝑻𝟏 𝑻𝟐 𝒌𝟐
𝑬= 𝒍𝒏
𝑻𝟐 − 𝑻𝟏 𝒌𝟏

• A shift in E with temperature

reflects a change in controlling
mechanism of reaction.

Dr. Enshirah Da'na

plotting In k versus 1/T 75

75

Warning on Using Pressure Measures.

• When dealing with gases, we measure compositions in terms of partial
and total pressures, and then develop their rate equations in terms of
pressures, without realizing that this can lead to problems.
• The reason is that the activation energy calculated when using these
units is incorrect.

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Example 2.
Experimental studies of a specific decomposition of A in a batch reactor
using pressure units show exactly the same rate at two different
temperatures:

(a) Evaluate the activation using these units

(b) Transform the rate expressions into concentration units and then
evaluate the activation energy.
The pressure is not excessive, so the ideal gas law can be used.
Dr. Enshirah Da'na 77

77

Solution.
(a) Using Pressure Units.
• A change in temperature does not affect the rate of reaction. This
means that E = 0.
𝑹𝑻𝟏 𝑻𝟐 𝒌𝟐
𝑬= 𝒍𝒏
𝑻𝟐 − 𝑻𝟏 𝒌𝟏

𝑹𝑻𝟏 𝑻𝟐 𝟐. 𝟑
𝑬= 𝒍𝒏 =𝟎
𝑻𝟐 − 𝑻𝟏 𝟐. 𝟑

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(b) Transform 𝒑𝑨 into 𝑪𝑨 then find E.

𝒎𝒐𝒍 𝒎𝒐𝒍
−𝒓𝑨 , 𝟑 = 𝟐. 𝟑, 𝒑𝟐𝑨 , 𝒂𝒕𝒎𝟐
𝒎 .𝒔 𝒎𝟑 . 𝒔. 𝒂𝒕𝒎𝟐
From ideal gas law: 𝑵𝑨
𝒑𝑨 = 𝑹𝑻 = 𝑪𝑨 𝑹𝑻
𝑽

−𝒓𝑨 = 𝟐. 𝟑𝑪𝟐𝑨 𝑻𝟐 𝑹𝟐
At 400 K:
𝟐
𝒎𝒐𝒍 𝒎𝒐𝒍 𝟐 @𝟔
𝒎𝟑 . 𝒂𝒕𝒎 𝟐
−𝒓𝑨𝟏 𝟑 = 𝟐. 𝟑 𝟑 𝑪 𝟖𝟐. 𝟎𝟔×𝟏𝟎 𝟒𝟎𝟎 𝑲
𝒎 .𝒔 𝒎 . 𝒔. 𝒂𝒕𝒎𝟐 𝑨 𝒎𝒐𝒍. 𝑲
𝒎𝟑
−𝒓𝑨𝟏 = 𝟎. 𝟎𝟎𝟐𝟓𝑪𝟐𝑨 𝒌𝟏 = 𝟎. 𝟎𝟎𝟐𝟓
𝒎𝒐𝒍. 𝒔
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At 500 K:
𝟐
𝒎𝒐𝒍 𝒎𝒐𝒍 𝟐 @𝟔
𝒎𝟑 . 𝒂𝒕𝒎 𝟐
−𝒓𝑨𝟐 = 𝟐. 𝟑 𝟑 𝑪 𝟖𝟐. 𝟎𝟔×𝟏𝟎 𝟓𝟎𝟎 𝑲
𝒎𝟑 . 𝒔 𝒎 . 𝒔. 𝒂𝒕𝒎𝟐 𝑨 𝒎𝒐𝒍. 𝑲

𝒎𝟑
−𝒓𝑨𝟐 = 𝟎. 𝟎𝟎𝟑𝟗𝑪𝟐𝑨 𝒌𝟐 = 𝟎. 𝟎𝟎𝟑𝟗
𝒎𝒐𝒍. 𝒔
𝑹𝑻𝟏 𝑻𝟐 𝒌𝟐
𝑬= 𝒍𝒏
𝑻𝟐 − 𝑻𝟏 𝒌𝟏
𝟖. 𝟑𝟏𝟒×𝟒𝟎𝟎×𝟓𝟎𝟎 𝟎. 𝟎𝟎𝟑𝟗
𝑬= 𝒍𝒏
𝟓𝟎𝟎 − 𝟒𝟎𝟎 𝟎. 𝟎𝟎𝟐𝟓
𝑱
𝑬 = 𝟕𝟗𝟗𝟒
Dr. Enshirah Da'na 𝒎𝒐𝒍 80

80

40
 07/03/2024

Important note:

• E values differ when either p or C used to

measure concentrations of materials.

• When making runs at different temperatures

first to change all p values to C values by
using the ideal gas law.

Dr. Enshirah Da'na 81

81

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