Can negations be arbitrarily added to both sides of an equation?

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In Vellemen's proof book, I keep encountering deriving-second-law-from-first-law type of exercises whose given answers say to just add a negation. For example,

Question 4 of section 2.2:

Show that the second quantifier negation law, which says that ¬∀x P(x) is equivalent to ∃x¬P(x), can be derived from the first, which says that ¬∃x P (x ) is equivalent to ∀x ¬ P (x ). (Hint: Use the double negation law.)

gives a hint saying to replace P(x) with ¬P(x).

I remember being told that we can do whatever we want to an equation as long as we apply it to both sides. Does this apply here?

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The "first negation law" says that $\lnot \exists x P(x)$ is equivalent to $\forall x \lnot P(x)$ for every formula $P(x)$. The key word here is: every formula. We can replace $P(x)$ by any formula we want.

So we may replace $P(x)$ by $\lnot P(x)$, because if $P(x)$ is a formula, then so is $\lnot P(x)$.

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Can negations be arbitrarily added to both sides of an equation?

We have the tautology:

$(A\iff B) \iff (\neg A \iff \neg B)$

'$\neg$' can be "added" to both sides of the '$\iff$'.

'$\neg$' can be "removed" from both sides of the '$\iff$'.

Disclaimer: A good "rule of thumb" in most cases, this rule may not be built into in the particular formal system you are working in.