Two very good questions! There was certainly an ad break just prior to 5.15 in very early days, as The Tube started at 5.15. This tended to be timed so the break finished before 5.15, so Thames will have provided the ads, with the next ad-break being handled by LWT.
Later the norm became to show a half-hour programme at 5pm, such as Alice, which had a commercial break about halfway through. The break would typically come at approx 5.10-5.13 (a pretty normal arrangement for any half-hour show) so perhaps C4 always made a point of not allowing a break to straddle 5.15 on the dot each Friday. I can't see that being too much of an issue unless a technical fault or late schedule change came into play.
There has been some discussion on this video uploaded by forum member Neil Miles. It contains footage of the ads played during a Good Friday Tube special in 1987, and appears to have been recorded in the London area. The first ad-break is only partially filled with commercials and we see a minute or so of a break-filler. Such break fillers were very rarely seen in London (or anywhere else for that matter as late as 1987), and one theory is that the break may have straddled the Thames/LWT switch, hence only part of the break being filled with ads from Thames. I've no idea what time of the evening this Tube programme was shown, so can't comment on whether or not this is a valid theory. [Both a horrible choice of lettering style and a bizarre choice of music in my opinion!]. Anyway, skip to about 4:30 for the caption:
I've no idea whether there was any visible 'jump' on Channel 4 London when the feed was switched from Thames to LWT.
Hopefully a Londoner will be able to give us some more information!