A multimeter's diode test function can be used to distinguish between the emitter and collector. Connect the anode lead to the base and the cathode to one pin, then the other. The emitter-base junction will have a slightly higher voltage drop, than the collector-base.
Another way is to connect the transistor's emitter/collector to a 5V supply, via a 10k resistor and the base to +V, via a 1M resistor. The correct direction should give the lower voltage drop cross the transistor's emitter and collector.