Law of mass action Vs order of reaction

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SUMMARY

The discussion clarifies the distinction between the law of mass action and the order of reaction in chemical kinetics. The law of mass action states that the rate of a reaction is proportional to the active mass (molar concentration) of the reactants, while zero-order reactions exhibit rates independent of reactant concentration. Misinterpretations arise from historical developments by Guldberg and Waage, leading to confusion between equilibrium constants and rate formulas. Understanding these concepts requires careful consideration of reaction mechanisms and elementary steps.

PREREQUISITES
  • Understanding of chemical kinetics and reaction rates
  • Familiarity with the concepts of molar concentration and active mass
  • Knowledge of elementary reaction steps and mechanisms
  • Basic grasp of equilibrium constants and their significance in chemistry
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  • Study the derivation of rate laws from elementary reaction steps
  • Learn about the implications of zero-order reactions in practical scenarios
  • Explore the historical context of the law of mass action and its evolution
  • Investigate the differences between kinetic and thermodynamic perspectives in chemical reactions
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Chemistry students, educators, and professionals in chemical research who seek to deepen their understanding of reaction kinetics and the law of mass action.

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According to law of mass action " The rate of reaciton is directly proportional to the active mass of the reactants. (I understand active mass as molar concentration of the reactants ) "

So for a general reaction aA-------->Product

The rate of forward reaction turns out to be

R=K[A]a (R=K [A]^a)

but for a zero order reaction the rate of reaction is independent of the concentration of the reactants.

How can these two laws of chemistry exist together?
 
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According to law of mass action " The rate of reaciton is directly proportional to the active mass of the reactants. (I understand active mass as molar concentration of the reactants ) "

I don't know where you got that statement from, but it is definitely not a correct formulation of the law of mass action.
 
Then what is the statement of law of mass action? Please clarify me.
 
The law of mass action makes statements about the position of the equilibrium, not about the rates of a reaction.
 
However it seems there is variation in terminology also in textbooks and teaching so the student may well have encountered mass action as a kinetic concept; I think I did.

"The fact that Guldberg and Waage developed their concepts in steps from 1864 to 1867 and 1879 has resulted in much confusion in the literature as to which equation the Law of Mass Action refers. It has been a source of some textbook errors.[10] Thus, today the "law of mass action" sometimes refers to the (correct) equilibrium constant formula[11] [12] [13] [14] [15] [16] [17] [18] [19] [20], and at other times to the (usually incorrect) rf rate formula.[21] [22]" http://en.wikipedia.org/wiki/Law_of_mass_action Better to focus on concepts and facts than their names if possible. I would not recommend the above historical article for first learning, it could confuse.

E.g. you cannot deduce R=K[A]a (R=K [A]^a) from aA-------->Product - it will be wrong more often than not.

Chemical reactions take place in a series of elementary steps (sometimes with parallel pathways of different steps). The rates of elementary steps are all of form rate = k[A], or rate = k[A]2 or rate = k[A] where [A] and are concentrations of substances reacting. But in the intermediate steps the substances reacting are not the original ones so you have to work out mathematically for any hypothetical mechanism, i.e. reaction sequence, the resulting rate laws in terms of the concentrations of initial substances which may be all sorts. It is just an area of study which I hope I have not made sound more complicated than it really is.

(On this site and no other, when I type B inside [ ] I get )
 

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