boiler water pH is normally (I'm used to 9.6 to 10.2 range) to protect the steel -- makeup is normally around 6.8 to 7.2 which is not good for the boiler, so chemicals are added to raise the pH, usually PO4 (phosphates) -- other chemicals are added to address other issues as mentioned above...
These chemicals will concentrate at the steam water interface and are removed by blowdown (as mentioned above, they usually don't carryover with the steam except for some of the oxygen scavenging chemicals -- see below)-- this is why the chemistry is usually monitored continuously and fed accordingly (on power boilers) -- smaller boilers such as heating boilers may batch treated...
a couple of areas to watch -- if you have gotten oil in the boiler system, it will tend to foam at the steam water interface and will allow chemicals to carryover, not good for those chemicals that raise the pH such as phosphates... any oil will need to be cleaned out...
some of the chemicals such as the oxygen scavengers, etc. are made to breakdown in the SH sections and will produce ammonia (NH3) which will affect the pH of the condensate -- too much ammonia will also attack any copper or brass heat exhanger materials...
in all cases, though, the normal chemicals used for boiler chemistry tend to drive the pH up and not acidic -- if you have an acidic problem and you are treating your boiler, I'd look for a water contamination (check silica and cation conductivity) -- a small condenser leak (such as circulating water into the condensate -- don't know if this applies to your setup) will drive the pH down rapidly, consuming phosphates, etc... (bad news...) -- also, you should check your make-up stream for any problems...