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Has anyone else thought about this? I've browsed the Wikipedia for mathematical constants and only things I saw that were definitely rational AFAIK were 0, 1, 2, and 1/2, which don't really count.

I think 777480/8288641 counts also. Fermat's/ Euler's Diophantine problem.

Are there any questions which have been asked where a rational answer is expected to be the answer?

Seeking tags also because I'm unsure what area of math this relates to most.

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From Wikipedia, Legendre's constant was first conjectured to be $1.08366...$ but later proved to be exactly $1$.

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There are whole sequences of important rational numbers. See these pages on "integer" sequences (although they may have some non-integer rational values, e.g. the earliest Bernoulli numbers, which are the basis for results such as the famous $-\tfrac{1}{12}$ result @jojobo mentioned) & this page for rational ones.

Then there are quantities of the form $\zeta(2n)/\pi^{2n}$ with $n$ a positive integer.

One could argue every rational $s$ is important for a suitably chosen complex analysis problem due to factors of $e^{2\pi is}$ or $(1-e^{2\pi is})^{\pm1}$.

J.G.
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