Does it matter? You cannot read individual bits from a serial com port anyway. You get the whole byte with the significant bits in the right order. You can then convert the byte to a bit array. If this is still important, I would say the least significant is sent first. You can verify this by sending a byte at an extremely low speed (300 baud) and use a breakout box to see the bit pattern, or use a scope to display the waveform.