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We have the following equilibrium established in a container with movable piston at atmospheric pressure. $$\ce{N_2 (g) + 3 H2 (g) ⇌ 2NH_3 (g)}$$ Now how does the concentration of the reacting species change upon addition of $\ce{He(g)}$ to the container?

I know that the reaction would shift towards left because it has larger number of moles than the right side due to Le-Chateliers principle. So the moles of the reacting species increases. Also, the volume of the container increases. So how to determine whether concentration, which is $\ce{\frac{Moles}{Volume}}$ increases or decreases as both Moles and Volume increases.

Zoraya
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  • No,it doesn't talk abt the problem I mentioned. – Zoraya Jun 06 '21 at 19:06
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    First, pretend the reaction is super-slow and just consider what happens to the concentrations. Then and only then consider in which direction the reaction will have to go to attain equilibrium. This reaction will counteract the change imposed, but not completely to back to the original concentrations. https://chemistry.stackexchange.com/a/18717/72973 is relevant here. – Karsten Jun 06 '21 at 22:32

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Suppose initially you had 1 mole of $\ce{N2}$ and 3 moles of $\ce{H2}$, and that $n$ moles of $\ce{N2}$ had reacted. Then you would have, at equilibrium, $1-n$ moles of $\ce{N2}$, $3(1-n)$ moles of $\ce{H2}$, and $2n$ moles of $\ce{NH_3}$. So the total moles at equilibrium would be $4-2n$, and the mole fractions (equal to the partial pressures in atm) would be $$x_{\ce{N2}}=\frac{1-n}{4-2n}$$$$x_{\ce{H2}}=\frac{3(1-n)}{4-2n}$$ and $$x_{\ce{NH3}}=\frac{2n}{4-2n}$$So the equilibrium relation would be $$\frac{(2n)^2(4-2n)^2}{3(1-n)^4}=K_p$$If we had added $\delta$ moles of inert to the mix, we would have obtained:$$\frac{(2n)^2(4+\delta-2n)^2}{3(1-n)^4}=K_p$$or equivalently $$2n(4+\delta-2n)=\sqrt{3K_p}(1-n)^2\tag{1}$$

ADDENDUM

If we solve Eqn. 1 analytically for $n=n_0$ in the base case $\delta=0$, we obtain: $$n_0=1-\frac{2}{\sqrt{4+\sqrt{3K_p}}}\tag{2}$$Furthermore, if we differentiate Eqn. 1 with respect to $\delta$ and take the limit as $\delta\rightarrow 0$, we obtain: $$\left(\frac{dn}{d\delta}\right)_{\delta \rightarrow 0}=-\frac{n_0}{2\sqrt{4+\sqrt{3K_p}}}\tag{3}$$Therefore, the conversion decreases as we add inert gas to the reaction mixture.

The overall molar concentration $C_0$ in the cylinder is constant (irrespective) of addition of inert to the mixture), and is given by: $$C_0=\frac{P}{RT}$$where P is the total pressure. Therefore, the concentration of NH3 is equal to the overall molar concentration times its mole fraction: $$C_{NH3}=\frac{2n}{4-2n+\delta}C_0$$If we employ Eqn. 3 to evaluate the derivative of $C_{NH3}$ with respect to $\delta$ at $\delta\rightarrow 0$ we obtain: $$\left(\frac{dC_{NH3}}{d\delta}\right)_{\delta\rightarrow 0}=\frac{-n_0}{2\left(1+\frac{2}{\sqrt{4+\sqrt{3K_p}}}\right)}C_0$$Therefore, as the number of moles of inert gas increases, not only does the number of moles of ammonia decrease, but so also does the ammonia concentration in the gas mixture.

Chet Miller
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    I agree that n is decreased which means moles of $\ce{N_2}$, which is $1-n$ is increased. but what happens to the concentration, which is $n/V$? Increase of moles alone doesn't imply that concentration is increased right? As there is a volume term. – Zoraya Jun 07 '21 at 06:07
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    SEE THE ADDENDUM – Chet Miller Jun 07 '21 at 12:35
  • You can see this graphically as well, as $\delta=\sqrt{3^3K_p}(1-x)^2/2n+2n-4$ plot the rhs on the x axis and $n=0\to 1$ on y. As $\delta$ increases $n$ decreases. – porphyrin Jun 07 '21 at 13:46
  • @Chet Miller: Can you please explain why you made $\delta \to 0$ after differentiating? – Zoraya Jun 08 '21 at 03:31
  • The analytic solution I got for $n = n(K_p, \delta) $ was complicated and it wasn't obvious from it if n and C increased or decreased if inert was added. Also, the question implied that the main interest was the direction (sign) of the effect. So I judged that it would be easier if I just evaluated the incremental effect on n and C of adding a small incremental amount of inert. This would be by expanding n in a Taylor series about $\delta = 0$. This gave a clearcut analytical answer. – Chet Miller Jun 08 '21 at 12:16