Rate Constants and Concentration-Time Equations: Exploring aA→B

  • Thread starter Thread starter sodium.dioxid
  • Start date Start date
  • Tags Tags
    Constants Rate
Click For Summary

Discussion Overview

The discussion revolves around the derivation of rate constants and concentration-time equations for chemical reactions, specifically focusing on the reaction of the form aA → B. Participants explore whether the stoichiometric coefficient "a" should be included in the derivation of the rate equation and the implications for generalizing the concentration-time equation.

Discussion Character

  • Debate/contested
  • Technical explanation
  • Conceptual clarification

Main Points Raised

  • One participant questions why the stoichiometric coefficient "a" is not included in the standard rate equation derivation, suggesting a more general approach using rate = -Δ[A]/aΔt = k[A].
  • Another participant argues that the concept of speed as a change of concentration per time unit does not necessitate the inclusion of "a" in the rate equation.
  • A different participant mentions bimolecular reactions as an example and states that treatments for a=2 exist, but reactions with a>2 are unlikely due to the improbability of productive trimolecular collisions.
  • Another contribution highlights that the general problem is often set up as aA + bB → cC + dD, and that simplifying assumptions are crucial for deriving the equations used in practice.
  • This participant also notes that experimental data must fit these equations, and poor fits may require new experiments and reanalysis.

Areas of Agreement / Disagreement

Participants express differing views on the necessity of including the stoichiometric coefficient "a" in the rate equation derivation. There is no consensus on whether the standard derivation adequately addresses reactions of the form aA → B.

Contextual Notes

The discussion touches on the limitations of standard rate equations and the assumptions required for their application, particularly in the context of more complex reactions beyond simple first or second order kinetics.

sodium.dioxid
Messages
50
Reaction score
0
Every book I look at, they state

rate = -Δ[A]/Δt = k[A] , for A → B

From there, they go on to derive the concentration-time equation.

Well, my concern is what if we have: aA → B

Shouldn't "a" be accounted for in the derivation.

In other words, why don't we derive a more general equation using rate = -Δ[A]/aΔt = k[A]?

It seems like the book wants me to use ln[A]_t = -kt + ln[A]_0 even when I have aA → B

For some reason, it's always the chemistry books horrible at explaining things (unlike Biology and Physics).
 
Last edited:
Chemistry news on Phys.org


sodium.dioxid said:
In other words, why don't we derive a more general equation using rate = -Δ[A]/aΔt = k[A]?

I don't see how it is more general. Speed is a change of concentration per time unit, period.
 


Maybe he means bimolecular reactions sUch as maybe 2NO2 → N2O4 ?

The answer is that treatments are found in the texbooks for a=2. For a>2 they assentially do not happen becuase of the high improbablilty of a productive trimolecular collision. Of course soichiometries a>2 exist, but the fundamental kinetic laws for elementary i.e. essentially single-step reactions which you are styuding now are only ever straight first order or second order.
There are then more complicated mechanisms which you will come across with all sorts of kinetic laws, but they are all made of several elementary reactions which each follow first or second order kinetic law.
 


Na:O2

Have you checked the wiki page for derivations of rate equations? the general problem is set up as aA + bB --> cC + dD and the equations are then resultant of several assumptions that simplify solving the differential equations and integrating the results.

It is these simplifying assumptions that always have to be met by the experiments if one can attempt to use the simple 0, 1st, and 2nd order integrated equations under steady state approximations. Experimental data fits to the equations are then used to model the system. Bad fits usually mean new experiments with different simplifying criteria, and then a reanalysis.

see wikipedia Rate_equation_(chemistry) and in the english article use the link for Steady_state_approximation
 
Last edited:

Similar threads

  • · Replies 131 ·
5
Replies
131
Views
11K
  • · Replies 8 ·
Replies
8
Views
8K
  • · Replies 1 ·
Replies
1
Views
3K
  • · Replies 16 ·
Replies
16
Views
7K
  • · Replies 4 ·
Replies
4
Views
3K
  • · Replies 9 ·
Replies
9
Views
8K
Replies
4
Views
2K
  • · Replies 1 ·
Replies
1
Views
3K
Replies
17
Views
4K
Replies
3
Views
3K