Thermodynamics: Equilibrium HELP

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Discussion Overview

The discussion revolves around determining the temperature at which an equilibrium mixture of the gases N2O4 and NO2 contains equal amounts of both species. Participants explore the relationships between free energy, equilibrium constant, and temperature, while considering assumptions about heat of formation and entropy.

Discussion Character

  • Exploratory
  • Technical explanation
  • Mathematical reasoning
  • Debate/contested

Main Points Raised

  • One participant poses a problem involving the equilibrium reaction N2O4(g) <--> 2NO2(g) and seeks to find the temperature for equal amounts of the gases, noting the presence of two unknowns, K(eq) and T.
  • Another participant suggests a substitution method involving free energy values and the equilibrium constant, but does not provide a clear resolution to the participant's query.
  • A later reply questions the effectiveness of the substitution method, highlighting the persistence of two unknowns in the equations.
  • One participant provides a calculation for K(eq) based on the dissociation of N2O4, suggesting that if starting with 1 mole of N2O4, the equilibrium condition leads to K(eq) = 2/3.
  • Another participant expresses skepticism about the problem's setup, referencing an answer book that assumes both gases are at a partial pressure of 1 atm, questioning the rationale behind this assumption.
  • Further replies emphasize the need to express the equilibrium constant in terms of pressure and relate it to the molar ratios of the gases at equilibrium.

Areas of Agreement / Disagreement

Participants express differing views on the approach to solving the problem, with some proposing substitution methods and others questioning the assumptions made in the problem statement. No consensus is reached regarding the correct method or assumptions.

Contextual Notes

Participants note the dependence of the problem on assumptions about the gases' partial pressures and the relationship between concentrations and pressures in equilibrium expressions. There are unresolved mathematical steps and conditions that affect the interpretation of K(eq).

Who May Find This Useful

This discussion may be useful for students studying thermodynamics, particularly those grappling with concepts of equilibrium, free energy, and the relationships between temperature, pressure, and concentration in chemical reactions.

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Thermodynamics: Equilibrium HELP!

Consider the following equilibrium:

N2O4(g) <--> 2NO2(g)

We can assume the heat of formation and standard change in entropy do not vary with temperature.

At what temperature will an equilibrium mixture contain equal amounts of the two gases?

where G = standard free energy change

-G/(R*ln(K(eq))) = T

delta G = delta H - T*(delta S)

There's two unknowns K(eq) and T. How do i figure out the value of K(eq) to solve this problem? Like, is there some sort of relationship of the K(eq) when both the gases are at the same amount?

K(eq) = X^2/X = X <---- this will become a variable, so how can i determine the K(eq).
Please help. Thanks in advance...
 
Last edited:
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A particular temperature of a reaction will be associated with a specific free energy value. A free energy value will have a relationship with the ratio of product over relationship, that is the equilibrium K of the reaction.

The solution to this problem lies in a simple substitution method, you'll need to substitute the free energy value (G). Try and figure it out. I believe this is all you'll need.

Feel free to ask further questions.
 
Last edited:
Just fixing a typo in GenChem's post :

"A particular temperature of a reaction will be associated with a specific free energy value. A free energy value will have a relationship with the ratio of products over reactants , that is the equilibrium K of the reaction."
 
GeneralChemTutor said:
A particular temperature of a reaction will be associated with a specific free energy value. A free energy value will have a relationship with the ratio of product over relationship, that is the equilibrium K of the reaction.

The solution to this problem lies in a simple substitution method, you'll need to substitute the free energy value (G). Try and figure it out. I believe this is all you'll need.

Feel free to ask further questions.

I don't see this substitution going anywhere. First of all if we try to remove one variable such as T, we can solve for:

T = (G - H)/S. However We'll end up having 2 unknowns still with G and
K(eq).

If I substitute G = H - T*S into -G/(RlnK(eq)), I'll still have 2 unknowns T and K(eq).

How can i solve this? Please help, thanks...
 
[tex]N_2O_4(g) \equiv 2NO_2(g)[/tex]
If you start with 1 mole of [itex]N_2O_4(g)[/itex], then at equilibrium, you have some [itex]1-x[/itex] moles, where [itex]x[/itex] is the dissociation constant. As a result, you will have produced [itex]2x[/itex] moles of [itex]NO_2(g)[/itex].

[tex]K(eq) = \frac{[NO_2]^2}{[N_2O_4]} = \frac{4x^2}{1-x}[/tex]

But, you are given that, at equilibrium,

[tex][NO_2] = [N_2O_4] [/itex]<br /> [tex]=> 2x = 1-x => x = 1/3 moles[/tex]<br /> <br /> Plugging this into the above expression gives K(eq) = 2/3.[/tex]
 
Gokul43201 said:
[tex]N_2O_4(g) \equiv 2NO_2(g)[/tex]
If you start with 1 mole of [itex]N_2O_4(g)[/itex], then at equilibrium, you have some [itex]1-x[/itex] moles, where [itex]x[/itex] is the dissociation constant. As a result, you will have produced [itex]2x[/itex] moles of [itex]NO_2(g)[/itex].

[tex]K(eq) = \frac{[NO_2]^2}{[N_2O_4]} = \frac{4x^2}{1-x}[/tex]

But, you are given that, at equilibrium,

[tex][NO_2] = [N_2O_4] [/itex]<br /> [tex]=> 2x = 1-x => x = 1/3 moles[/tex]<br /> <br /> Plugging this into the above expression gives K(eq) = 2/3.[/tex]
[tex] <br /> <br /> I really think there's something definitely wrong with this problem. I took a look at the answer book at school and they assumed the gases were at a partial pressure of 1 atm each. That's how they figured out the problem. Is there some reason they might use this?[/tex]
 
Could you write down the question exactly as it appears in your text/homework ?
 
Gokul43201 said:
Could you write down the question exactly as it appears in your text/homework ?
Consider the following equilibrium:

N2O4(g) <--> 2NO2(g)

At what temperature will an equilibrium mixture contain equal amounts of the two gases? Assume the heat of formation and standard change in entropy do not vary with temperature.
 
Of course, that makes sense. Rememeber when you devised the formula K(eq) = X^2/X in your first post? Instead of concetrations it is in terms of pressure, first find the relationship, the corresponding way you should write it in terms of pressure and that should solve your problem.

1 atm should be divided equally since the molar ratios are equivalent (same amount of each gases refers to #, and this relates directly to moles). Each gas should take up .5 atm (deduced according to PV=nRT), remember that equilibrium also relates to Keq. You need to find this relationship.
 

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