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
The discussion centers on the derivation of rate constants and concentration-time equations, specifically questioning why the stoichiometric coefficient "a" in reactions of the form aA → B is not included in the standard rate equation. It is argued that while textbooks present the equation as rate = -Δ[A]/Δt = k[A], a more general approach could involve rate = -Δ[A]/aΔt = k[A]. However, it is noted that treatments for a=2 exist, and reactions with a>2 are rare due to the improbability of trimolecular collisions. The conversation also highlights that elementary reactions typically follow first or second-order kinetics, and more complex mechanisms involve multiple elementary reactions. Simplifying assumptions are crucial in deriving these equations, and experimental data must fit these models for accurate analysis.
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
9K
  • · 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
7K
Replies
4
Views
2K
  • · Replies 1 ·
Replies
1
Views
2K
Replies
17
Views
4K
Replies
3
Views
3K