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Best way to determine which thermostat controls which zone valve?

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Florida native that just moved to Colorado so I am a total novice to heating systems. The house we just purchased has 2 of the thermostats hooked up in a weird way(there are a total fo 5 thermostats but just these two are in question). It's a hydronic baseboard system. Basically the thermostat in the office upstairs controls the downstairs dining room/kitchen baseboard heaters and the thermostat in the dining room controls office and extra bedroom baseboard heaters. It's a terrible design since it can create a situation where the thermostats never turn on or always stay on depending on what heats up first. I also suspect it's not on purpose. In any case, what I am getting what do you guys think is the best way to determine which zone valve goes to which thermostat? Nothing is labelled. Would shutting all thermo stats off and just using a volt meter be sufficient? Anything important I need to be aware of? Thanks!

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