The amount of space around a binary operation symbol is stored in the internal parameter \medmuskip; the standard value is set in fontmath.ltx, which is read at format creation, together with the values of its siblings \thinmuskip (the space inserted between a math operator and an ordinary symbol and in other situations) and \thickmuskip (the space around a relation symbol)
\thinmuskip=3mu
\medmuskip=4mu plus 2mu minus 4mu
\thickmuskip=5mu plus 5mu
The unit mu is 1/18 of an em in the math symbol font, so it adjusts itself according to the font settings.
In the standard Computer Modern fonts at 10pt size, the em in the math symbol font is 10pt (12pt at 12pt font size). It scales when the size is changed by commands such as \large, \small and similar.
So the space is 4mu, extendable to 6mu (or more, if need be, because stretchable glue can stretch without limit, but stretching it more than stated increases the badness of the line) and shrinkable to 0mu.
In order to change it, just add a declaration similar to the default one, say
\setlength{\medmuskip}{6mu plus 1mu minus 6mu}
Note that this glue is automatically inserted, but it's never inserted in subscripts or superscripts. It's compulsory to use mu units.
\setlength{\medmuskip}{0.5mu}\setlength{\thinmuskip}{1mu}\setlength{\thickmuskip}{2mu}or something like\thickmuskip=4.4mu plus 3mu minus 1mu\medmuskip=3.6mu plus 2mu minus 3mu- found this somewhere when trying to do something similar, but can't remember where – prettygully Feb 25 '14 at 04:30\setminus, classified as a binary operation (for set difference), the other one is\backslash, which behaves like/(that is, as an ordinary symbol). Usually the set difference is treated as a binary operation. Are you asking about this particular symbol or in general for binary operation symbols? – egreg Feb 25 '14 at 13:49\cup/\capare usually the worst. – Blender Feb 25 '14 at 21:50