Rate law expression with solids and liquids

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Discussion Overview

The discussion revolves around the incorporation of solids and liquids in rate law expressions within chemical kinetics and equilibrium. Participants explore how these phases affect reaction rates and the implications for rate laws, particularly in the context of introductory chemistry education.

Discussion Character

  • Exploratory
  • Technical explanation
  • Debate/contested
  • Homework-related

Main Points Raised

  • One participant notes the absence of examples involving solids or liquids in rate law expressions in their textbooks and questions how to incorporate them into the rate law.
  • Another participant asserts that solids and liquids are not included in the K constant for kinetics because their concentrations are assumed constant.
  • A distinction is made between equilibrium (where the presence of a solid does not affect the equilibrium position) and kinetics (where the reaction rate is influenced by the surface area of the solid).
  • It is mentioned that the rate law is also dependent on the reaction mechanism, complicating predictions about the reaction order involving solids.
  • A later post seeks clarification on how to include the order of the reaction of solids in the rate expression, indicating a lack of resources on the topic.
  • Another participant suggests that the reaction rate depends on the surface area of the solid and recommends searching for textbooks on surface chemistry or heterogeneous catalysis for more information.

Areas of Agreement / Disagreement

Participants express differing views on the treatment of solids and liquids in rate laws, with some agreeing on the constancy of their concentrations while others highlight the complexities involved in kinetics. The discussion remains unresolved regarding how to formally include solids in rate expressions.

Contextual Notes

Limitations include the lack of detailed examples in introductory materials, the dependence on specific reaction mechanisms, and the need for further exploration of surface area effects in kinetics.

Who May Find This Useful

This discussion may be useful for students studying chemical kinetics and equilibrium, particularly those interested in the role of different phases in reaction rates and rate laws.

yolo123
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Hello Forum!

I was wondering:

In the rate law expressions, I could never find an example with a solid or a liquid in the reactants in my textbook (Chemistry by Zumdahl). I searched Chemistry (Raymond Chang) and Principles of Molecular Chemistry, without any success.

What happens to solids and liquids who act as reactants in reactions? How do I incorporate them into the rate law? Are they ALWAYS already included in the k constant?
 
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Solids and liquids are not incorporated into the K constant because their concentrations are assumed to be constant (which is a pretty good approximation; as you consume either a solid or a liquid, you decrease the total amount but do not generally affect their concentrations).
 
k (kinetics) or K (equilibrium)?

For equilibrium presence of the solid is enough - no matter how much of the solid there is, the result (in terms of the final equilibrium position) is always the same.

For kinetics it is much more complicated, as reaction rate depends on the surface area of the solid. But I have never seen it addressed in the introductory courses.
 
Oops, true, I should have specified that I meant equilibrium Ks only. As Borek says, Ks for kinetics differ.
 
Not to mention, the rate law also depends on the reaction mechanism. So, it is impossible to guess on your own unless provided with some incentive.
 
I meant k as in the rate law: for example, rate=k[NO2]^2.
 
"For kinetics it is much more complicated, as reaction rate depends on the surface area of the solid. But I have never seen it addressed in the introductory courses."
Hi, it's three years too late but I'm hoping someone could elaborate on the complicated concept here. How do you include the order of the reaction of solid in the reaction rate expression? This is the only post on the internet where someone has hinted that there is an answer to this question. If you can't answer, it will still be helpful if you can point me to some resources as I have no idea what the answer to this is and I am tasked to find one. Any help will be appreciated, thank you.

(This is for both interest and homework.)​
 
In general, the reaction rate will depend on the surface area of the solid exposed to reactants. How the surface area changes over time will depend on the exact geometry of the material. Likely you would be able to find more information by searching for textbooks on surface chemistry or heterogeneous catalysis.
 
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