Yes, sorry, it seems I didn't understand it fully - is it that you have steam/hot water heat exchanger where hot water (with glycol) is heated side?
I still don't beleive that you can handle this problem with measuring conductivity.
Secondary exchanger for purpose of separation is allways the best, but also the most expensive solution.
I had problem similar to yours in food industry, where we had to prevent any possible leak in plate heat exchanger. Temporary solution was to maintain higer pressure on clean side (it was water-water exchanger so it was not a big problem) so if some leak occurs, it would run in non-critical direction.
But you have steam-water system and problem is that pressure drops on steam side when you shutdown the boiler. There are some design possibilities, to install check valve downstream the boiler, automatic on-off valve upstream the steam trap, which closes when boiler shuts down, and you additionaly need one safety valve between these two. That way you can achive contolled minimum pressure on steam side when boiler is off. This is not so simple, but maybe it is cheaper then additional heat exshanger (for which you will also need additional piping, control valve trim and so on).
In my mentioned situation we decided on permanent solution - to replace plate exchanger with monster-big shell and tube exchanger, beacuse they are much, much more resistant to any leaks! But you already have shell & tube?! It shouldn't leak so easily - when it leaks it means it is significantly damaged - has apparent crack on plate-tube weld or on tube itself (while with plate exchanger slightly imbalanced gasket tightening can cause big leak).
Interesting?!