Equilibrium reaction ICE method to ideal gas law

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Discussion Overview

The discussion revolves around the application of the ICE method to determine the equilibrium composition and pressure of a gas reaction involving carbon monoxide (CO) and oxygen (O2) forming carbon dioxide (CO2) at elevated temperatures. Participants explore the calculations related to the equilibrium constant (Kp) and the implications of stoichiometric mixtures in a closed vessel.

Discussion Character

  • Technical explanation
  • Mathematical reasoning
  • Debate/contested

Main Points Raised

  • One participant presents their calculations for Kp using the ICE method and questions the correctness of their approach, particularly regarding the initial amounts of reactants and products.
  • Another participant points out that the initial amount of oxygen must be considered in the context of stoichiometry, suggesting that the initial composition affects the calculations.
  • There is a discussion about the degree of dissociation (α) and how it relates to the final equilibrium state, with some participants noting that different definitions of α could lead to different expressions for the final results.
  • A participant expresses confusion regarding the book's solution, which uses CO2 as an initial species, contrasting it with their own approach that starts with CO and O2.
  • Another participant mentions the need to see specific equations referenced in the discussion to provide more targeted insights, indicating that the equilibrium expressions may vary based on the definitions used.
  • There is a reference to the Ostwald dilution law, with a participant attempting to relate it to the equilibrium expressions being discussed, although they express uncertainty about the units and relationships involved.

Areas of Agreement / Disagreement

Participants express differing views on the initial conditions of the reaction and how they affect the calculations. There is no consensus on the correct approach to determining the equilibrium composition and pressure, as multiple interpretations of the initial conditions and definitions of α are presented.

Contextual Notes

Participants note that the initial amounts of reactants and products are crucial for accurate calculations, and there is mention of potential confusion arising from different definitions of the degree of dissociation. The discussion also highlights the importance of specific equations referenced in the literature, which may not be fully resolved in the thread.

marellasunny
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QUESTION: Say I have the following equilibrium reaction
CO+\frac{1}{2}O_2\leftrightharpoons CO_2
The stoichiometric mixture of CO and $O_2$ in a closed vessel, initially at 1 atm and 300K, is exploded. Calculate the composition of the products of combustion at 2500K and the gas pressure.
Take $K_p$=27.5. Take $\alpha$ as the degree of dissociation.
$$$$
MY ATTEMPT AT AN ANSWER:
I use the ICE method to find out the reactant and product composition
$$CO+\frac{1}{2}O_2\leftrightharpoons CO_2$$
The reaction quotient can be given as Q=0/0.5=0. Therefore, the products must have plus sign.

Then I get the final composition(/concentration) as
$$CO=[1-\alpha] $$
$$O_2=[1-\alpha/2]$$
$$CO_2=[\alpha]$$

then, $$ K_p= \frac{\alpha}{[1-\alpha][1-\alpha/2]^{0.5} } $$
I would then use the IDEAL GAS LAW to find the product mixture

i.e $$ p_RV=n_RRT_R$$ $$p_pV=n_PRT_p$$

I would then substitute these values into the expression for $K_P$.

MY QUERY:
1.Is my calculation for K_P correct? I take CO_2 as the product and CO and O_2 as the reactants.

2.I am not able to figure out what is the number of moles of the products n_P and the number of moles of the reactants n_R.The book's solution gives n_R=3/2 and n_P=1+\alpha/2.

The author solves with the initial species as CO_2 and obtains the compositions CO_2=(1-\alpha);CO=\alpha;O_2=\alpha/2, which is confusing given that the question states the reaction starts with CO and O2 in a closed vessel.
 
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marellasunny said:
$$O_2=[1-\alpha/2]$$

If the mixture was stoichiometric, initial amount of oxygen was not 1. Unless I am missing something.

1.Is my calculation for K_P correct? I take CO_2 as the product and CO and O_2 as the reactants.

See above. Other than that looks like you are on the right track.

The author solves with the initial species as CO_2 and obtains the compositions CO_2=(1-\alpha);CO=\alpha;O_2=\alpha/2, which is confusing given that the question states the reaction starts with CO and O2 in a closed vessel.

Actually initial composition doesn't matter (as long as it is stoichiometric), as if the mass balance doesn't change, final equilibrium will be identical. Calling α degree of dissociation suggests CO2 and its decomposition as a starting point. Doesn't mean your approach is wrong, it should yield the same result in terms of final pressures. But as α's are different, final result expressed using your α and using book's α won't look identical.
 
Borek,please find attached the problem I'm struggling with. I've highlighted the step which I do not understand also.

The K_p values were arrived from the temperatures empirically. But,what is the expression to the left in page 89?
 

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Hard to say something specific without seeing eq 3.40. But in general it looks like equilibrium expressed using reaction degree (fraction) - as defined at the very top of the page. In a way similar to http://en.wikipedia.org/wiki/Ostwald_dilution_law
 
Oswald Dilution Law, very helpful insight.Since, concentration=n/V , this is not how it is expressed in the red highlighted area(attachment previous post). I first thought this was a relation between K_p and K_c,but the units didn't agree. It doesn't agree even in the Oswald dilution law.
$$\frac{1-\alpha }{\alpha (\alpha /2)^{0.5}}{\frac{n_p}{p_p}^{0.5}}=K_p $$
I also Attached 3.40 eq.
 

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