Well to try to descientize what Norman said.
There are many places were error can be introduced.
First is error with the measuring instrument, if you have a rule that has 1mm accuracy you can't get any more accurate than that, in the same way you have a test kit that each drop = 1dkH of alkalinity you can't get any more accurate than that... by following the directions, however by doubling the volume you can effectively half the precision down to 0.5 dKh, however I'm unsure how this works for non-linear values like pH (or if it does)..
The next error is the error is the human error, how accurately are you measuring your vial to be at 5ml? Are you sure you're dropping a single drop and not touching the sides so you're prematurely "popping" the droplet that's forming? These sorts of errors are human errors, and often I call them "sloppy errors" because these are ones that can be fixed if you spend a little more time and effort in doing your measurements.
Ok so maybe that doesn't clear things up, but then again I teach the physics version of this rather than a chemical version, but I'm guessing the ideas are the same.