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Simple. It's the timing process. With a 4 cyl car, there are only 4 times in the crankshaft cycle where the conditions are met where the piston, crank, and cam gears are aligned, and when the spark will ignite the fuel mixture.
On a 6 cyl car, there's 6 times per revolution where those things occur. So, the odds are that most of the time, the 6 cyl is going to be closer to its proper ignition timing upon startup than with a 4 banger.
To me, picturing in my mind the schematic, it seems intuitive to me that the more firing points in a single rotation of a crank shaft, the higher the probability of enough fire per rotation to sustain a running condition. Granted, there is a lot more resistance to turning an engine with more pistons, but presumably that has been taken into account in the power output of the stock starter.
As a general rule, the bigger engines get, the smoother they get.
Actually the general rule is that the more cylinders an engine has the smoother they are.
"Big" four cylinders engines are rougher because the pistons have so much mass they cause vibration. Hence the use of balance shafts in larger displacement four cylinder engines.
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