When you place a conductivity probe in an electrolyte, current will flow through the circuit - this means you can measure its conductivity.
When you place conductivity probe in a non-electrolyte, no current will flow - this means you will get a reading of 0 conductivity
Another way to determine whether a substance is an electrolyte or non-electrolyte is to set up an electrolytic cell - if the substance will undergo electrolysis then it is an electrolyte, if not, it is not.
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