Devil's Advocate:
Is there a practical example that the math would catch something but a diver skipping this step would not have multiple other ways to notice the issue (spiking O2 at 20ft or at depth, comparing behavior to other cells at any depth other than 1.0 ppO2, dil flush at depth), and it be problematic?
In your example above if one calibrates a cell in 100% O2 @ 38mV and then looks at the computer in air it would read >0.30 (12mV instead of the expected 8mV). No math done, know nothing about mV, understand almost nothing about cells, haven't compared the reading to other cells, and still see the problem before hitting the water. That example perhaps was an extreme error. Of course less error is less noticeable, but also becomes less of an issue going unnoticed.