I apparently can't see the difference in a compilation (pdflatex) between \mathrm and \operatorname. So, as in the title the question is: is there a difference? Which one is preferable in what occasions?
3 Answers
There are many differences. The main one is in the fact that \mathrm{xyz} behaves like an ordinary letter, while \operatorname{xyz} behaves like function names such as \sin. Here's an illustration
$\sin x + \sin(x+y) + a\sin z$
$\mathrm{sin} x + \mathrm{sin}(x+y) + a\mathrm{sin}z$

where it's clear that the second line is typeset wrong. Even if your "operator" requires parentheses after it, it should be \operatorname, as the third summand shows, where a thin space separates the coefficient from the operator.
Another subtle difference is in how some characters are interpreted in \mathrm and in \operatorname. Suppose you have an operator to be called "pre-norm", with a hyphen. Here's the example
$\operatorname{pre-norm}(\mathbf{v})$
$\mathrm{pre-norm}(\mathbf{v})$

and now it's clear what is to be used. Indeed \operatorname (and the same holds for macros defined with \DeclareMathOperator) treats punctuation symbols in a special way; \mathrm, instead, treats them as math symbols.
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11Can you please tell the full form of the
rminmathrm? Thank you! – Gaurang Tandon Feb 14 '18 at 05:12 -
22@GaurangTandon
rmstands for “roman”, that conventionally denotes the upright type used in the document. – egreg Feb 14 '18 at 08:59 -
2Wrapping
\mathrmwith\mathopaddresses the first point (spacing). Replacing\mathrmwith\textrmaddresses the second point (characters interpreted as math inside\mathrm{...}). So the next question is: what’s the difference between\mathop{\textrm{...}}and\operatorname{...}? – Maëlan May 11 '22 at 22:03 -
2@Maëlan Try
$\mathop{\textrm{xyz}}$inside a theorem statement typeset in italics. – egreg May 11 '22 at 22:19
\operatorname:
The argument is written in upright mode but with some additional space before and behind.
\mathrm:
It is like math mode (no spaces), but in upright mode. The font size isn't changed.
The following example shows the differences:
\documentclass[]{article}
\usepackage{amsmath}
\begin{document}
\[x\operatorname{foo}y\]
\[x\mathrm{foo}y\]
\end{document}

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In other LaTeX environments \mathrm{xyz} is useful. In MathJax v 2.0
$ i \\, \mathrm{sinh} \; $
gave the equivalent output as $ i \sinh x $. MathJax did not recognize \operatorname.
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15
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8Typo in the comment by @ChrisR (important if you're searching): it's AMSmath.js, (not ASMmath.js). – Toby Bartels Feb 14 '20 at 20:24
\mathrmis used to make variables and units appear in roman (non-italic) text." - You can use it for units for example. – Avatar Oct 21 '20 at 06:50