Mass balance with reaction -- Chemical kinetics POV

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Discussion Overview

The discussion revolves around the differences and potential inconsistencies between the chemical kinetics perspective and the chemical reaction engineering approach regarding reaction rates and rate equations. Participants explore the implications of these differences in the context of a specific reaction and its representation in an ideal batch reactor.

Discussion Character

  • Debate/contested
  • Technical explanation
  • Mathematical reasoning

Main Points Raised

  • One participant notes that the reaction rate according to chemical kinetics is defined in terms of concentrations of reactants and products, while questioning whether the net chemical generation rate used in reactor engineering is equivalent to the reaction rate in kinetics.
  • Another participant suggests that the reaction rate and rate constant should be adjusted when considering the production of a specific species, indicating that they would need to be divided by the stoichiometric coefficient for that species.
  • A different participant challenges the mole balance approach, proposing that the mole balance should include the stoichiometric coefficient for the product species D, leading to a revised equation that aligns with both perspectives.
  • One participant expresses a preference for reaction engineering methods, stating that they are more accustomed to thinking in terms of mass and energy balances, despite acknowledging the validity of the kinetic approach.
  • Another participant references a specific text, noting that it uses a species-specific reaction rate in the mole balance, which aligns with the previous discussions and suggests a potential agreement between the two approaches.

Areas of Agreement / Disagreement

Participants express differing views on the application of reaction rates and stoichiometric coefficients in mole balances. While some suggest that both approaches can agree under certain conditions, others highlight inconsistencies that remain unresolved. Overall, multiple competing views persist without a clear consensus.

Contextual Notes

There are limitations regarding the assumptions made about the equivalence of reaction rates and the application of stoichiometric coefficients in different contexts. The discussion does not resolve these assumptions or clarify the implications of using different approaches.

MexChemE
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Good evening, people of PF. Recently, while studying chemical kinetics, I have come across some questions about reaction rates and rate equations. I've noticed some inconsistencies between the chemical kinetics point of view, and the approach taken by chemical reaction engineering and reactor design authors. Consider the following reaction.
aA + bB → cC + dD
According to chemical kinetics, the reaction rate is given by
r = -\frac{1}{a} \frac{\textrm{d} C_{\textrm{A}}}{\textrm{d} t} = -\frac{1}{b} \frac{\textrm{d} C_{\textrm{B}}}{\textrm{d} t} = \frac{1}{c} \frac{\textrm{d} C_{\textrm{C}}}{\textrm{d} t} = \frac{1}{d} \frac{\textrm{d} C_{\textrm{D}}}{\textrm{d} t}
And the rate equation is (usually) given by
r = k C_{\textrm{A}}^a C_{\textrm{B}}^b
So, for instance, if we want to know the rate at which D is produced we write
\frac{\textrm{d} C_{\textrm{D}}}{\textrm{d} t} = d k C_{\textrm{A}}^a C_{\textrm{B}}^b
and we solve the differential equation.
Now, we assume the same reaction occurs inside an ideal batch reactor, and again we want to know the rate at which D is produced. We perform a mole balance for the species D.
\frac{\textrm{d} n_{\textrm{D}}}{\textrm{d} t} = rV
Where V is the volume of the reactor, and r is the net chemical generation. If we apply nD = V⋅CD, we have
V \frac{\textrm{d} C_{\textrm{D}}}{\textrm{d} t} = rV
\frac{\textrm{d} C_{\textrm{D}}}{\textrm{d} t} = r
Finally, we have
\frac{\textrm{d} C_{\textrm{D}}}{\textrm{d} t} = k C_{\textrm{A}}^a C_{\textrm{B}}^b
Although similar, this is not the same result one arrives at when studying chemical kinetics. Maybe it is a ridiculous concern, or I am missing something obvious, but it has been bugging me since I noticed it. Is the r (net chemical generation) used when studying chemical reactor engineering not the same as the r (reaction rate) used when studying chemical kinetics?
Thanks in advance for any input!
 
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It seems to me, in the second case you're just considering species D and your r and k would apply just to CD. To then consider r and k for the overall reaction, you'd have to divide your species-specific r and k by d.
 
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This step doesn't look right to me:
MexChemE said:
Now, we assume the same reaction occurs inside an ideal batch reactor, and again we want to know the rate at which D is produced. We perform a mole balance for the species D.
\frac{\textrm{d} n_{\textrm{D}}}{\textrm{d} t} = rV

If each reaction produces ##d## molecules of species D shouldn't it be this, instead?
\frac{\textrm{d} n_{\textrm{D}}}{\textrm{d} t} = drV

If so, it looks like both approaches agree.
 
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rikblok said:
If each reaction produces ##d## molecules of species D shouldn't it be this, instead?
\frac{\textrm{d} n_{\textrm{D}}}{\textrm{d} t} = drV

If so, it looks like both approaches agree.
Well, I've never seen reaction engineering literature using stoichiometric coefficients on mole balances before, but it doesn't seem like we're breaking any rules here. And it does agree with the result from chemical kinetics. I do prefer using reaction engineering methods though, as a chemical engineering student, I'm more inclined to think and reason in terms of mass and energy balances.
 
insightful said:
It seems to me, in the second case you're just considering species D and your r and k would apply just to CD. To then consider r and k for the overall reaction, you'd have to divide your species-specific r and k by d.
While reading deeper into Fogler's Elements of Chemical Reaction Engineering I noticed they do use r_{\textrm{D}} in the mole balance for species D, and r_{\textrm{D}} = dr, which agrees with both your post and rikblok's.

Thank you both for your input!
 

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