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In A-level chemistry we are taught that:

To every reaction: $$\sum_{i=1}^n c_iA_i\to\sum_{j=1}^m d_jB_j$$There is a rate equation: $$r=\kappa[A_1]^{\alpha_1}[A_2]^{\alpha_2}\cdots[A_n]^{\alpha_n}$$With the $(\alpha_i)$ called the partial orders and $\sum_{i=1}^n\alpha_i$ the overall order, $\kappa$ some constant.

Since the case of multiple reactants is confusing (e.g. I have not been able to get a clear answer of how 'rate' is defined in general) I'll stick to a reaction with only one reactant, $A\to bB+cC+dD+\cdots$.

We can then explicitly solve the differential equations, for $[A]_t$ treated as a function in time $t\ge0$, with $[A]_0>0$: $$\frac{\mathrm{d}[A]_t}{\mathrm{d}t}=\kappa\cdot[A]_t^\alpha\implies\kappa t+C=\begin{cases}\frac{1}{1-\alpha}[A]_t^{1-\alpha}&\alpha\neq0\\\ln[A]_t&\alpha=0\end{cases}$$After some shuffling, you get: $$[A]_t=\begin{cases}\{(1-\alpha)(\kappa\cdot t+C)\}^{\frac{1}{1-\alpha}}&\alpha\neq1\\Ce^{\kappa t}&\alpha=1\end{cases}$$Where $C$ is some constant in both cases. If $\alpha=1$, we get $C=[A]_t$: otherwise, $C=\frac{1}{1-\alpha}[A]_0^{1-\alpha}$.

I played with this a little, plotting concentration-time reaction curves on Desmos, and I quickly noticed a significant difference between the cases $\alpha<1$ and $\alpha\ge1$: if the order $\alpha$ is less than $1$, the model predicts the reaction terminates in finite time, at $t=-C/\kappa$. Else, the reaction never terminates!

Intuitively, I don't think a chemical reaction can ever fully terminate, so I'm inclined to believe the following conjecture:

In a reaction with only one reactant, the order of reaction must be greater than or equal to $1$.

More generally, I suppose:

In any reaction for which the rate equation holds, the overall order must be greater than or equal to $1$.

Does that make sense? I imagine I'm quite wrong, since I'm doing this on the back of relatively little chemical knowledge. In particular, it's hard to picture what solving the differential equations looks like for multiple reactants.

FShrike
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    Aside of photochemical reactions of zeroth order, consider complex, multistep reactions with reaction loopbacks. Things about their order can go rather wild. Even for the simple looking $\ce{Br2 + H2 -> 2 HBr}$. – Poutnik Dec 06 '22 at 17:16
  • see https://www.coursehero.com/file/21287225/Chemical-Kinetics-3/ – Poutnik Dec 06 '22 at 17:22
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    Long story short, if the reaction is truly elementary, then all orders would be positive integers; and if it isn't, then its order is just an approximation that won't hold all the way down to zero concentrations. – Ivan Neretin Dec 06 '22 at 17:33
  • :( Even or all this nice formatting, I'm still tempted to downvote. It maybe could be a duplicate target, if well answered, but the topic's being asked so many times before... – Mithoron Dec 06 '22 at 21:26
  • @IvanNeretin That essentially answers the question, thank you. – FShrike Dec 06 '22 at 21:38
  • @Mithoron This topic has been asked about before, sure. My question is specific though: from my mathematical manipulation of the differential equations, is my conclusion about the possible orders correct? Ivan suggests an answer, though I might like some more detail – FShrike Dec 06 '22 at 21:40
  • Irreversible reaction with just one substrate can of zeroth order. Like Poutnik said it could be photochemical, but there are also other reactions that simply aren't controlled by concentration. And yes it leads to equation with finite end of recation. – Mithoron Dec 07 '22 at 00:07
  • See https://chemistry.stackexchange.com/questions/154182/are-pseudo-zeroth-order-reactions-possible https://chemistry.stackexchange.com/questions/94965/can-a-zeroth-order-reaction-be-reversible https://chemistry.stackexchange.com/questions/263/how-to-identify-zero-order-reactions – Mithoron Dec 07 '22 at 00:13
  • @FShrike Since you have got the answer, would you mind self answering it? Self answers are encouraged, it completes the post and it will also be helpful for future readers. – Nilay Ghosh Dec 07 '22 at 04:10
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    @NilayGhosh I often self-answer over at MSE. However, I don't have the authority to self-answer here, since I am not even close to knowing the details properly. – FShrike Dec 07 '22 at 17:37

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