The formula I am using is: DateDiff("s", Field1, Fields). The problem with different days is mentioned above. The DateDiff() function doesn't "consider the date when it looks at the hh:mm:ss tt section of the field's row values. In using my example above, when DateDiff() calculates the number of seconds between 11:57:08 PM and 12:15:01 AM the calculation looks like this: 12:15:01 AM subtract 11:57:08 PM. If you looked at it in military time 00:15:01 - 23:57:08 or 901 seconds subtract 86222 seconds or 901-86222 = -85321. The answer is -85321. I know how to do this in Excel, not ArcGIS.