Calculation has to take into account the conductor temperature, so the formula given in BS7671 is rather complex, ... tabulated mV/A/m for 2.5 mm² is 18 mV/A/m but after correction as used to get the 106 meter limit it's 16.5 mV/A/m
As you say, it's quite complex. If one wants to calculate the maximum VD, one presumably has to do that in relation to the situation in which the current in the cable is at its 'maximum', and determining the VD at that current requires knowledge of the operating temp the conductors would achieve at that current.
The 18 mV/A/m for 2.5mm² cable (for a conductor temp of 70°C) presumably implies that the conductors are expected to achieve a temp of 70C when fully loaded to its tabulated CCC (27A for Method C). When ambient temp is 20°C and virtually no current flowing (i.e. no cable heating) that would correspond to a 'VD' of about 14.8 mV/A/m.
The 16.5 mV/A/m figure you mention would imply an operating conductor temp of about 48.7°C. Whether that is reasonable for the 'maximum current' flowing in each arm of the ring (13A, if one uses your assumption of an 'effective current' of 26A for a 'fully-loaded' 32A ring - see below), I don't know - but it is probably not an unreasonable assumption for Method C 2.5mm².
... it is assumed 20 amp mid ring and 12 amp even load so the design current for circuit Ib is 26 amp not 32. ... There is nothing official about these figures, so you will not find it in BS7671 it is up to the circuit designer to decide, so if for example setting out a ring final around work benches in a school one could take 13 amp centre and 19 amp even spread, there is no hard and fast rule.
As you say, there's nothing absolute about this, and certainly no regulations, or even associated guidance (that I have seen) about this. As you say, there are certainly situations in which an assumption that the load will be 'concentrated' near the centre of a ring does not really seem to be justified - in fact, I would suspect that this is, in practice, not a particularly common situation. On the other hand, as per my recent post, if one really wants to consider a 'worst-case scenario', one would have to assume that the entire full load (e.g. 32A) was applied at the mid-point of the ring.
The other associated thing which surprises me is that I have never heard of anyone correcting Zs measurements for temperature. Measurements are commonly undertaken on essentially 'cold' installations (i.e. conductors roughly at ambient temp) and, if those measurements are below the prescribed 'maximum Zs' figures, that is considered satisfactory/acceptable. However, if the measured Zs is close to the 'maximum', then it's quite possible that the Zs could be above the maximum permitted (for satisfactory ADS) if the circuit were 'fully loaded' (hence with conductors at their maximum operating temp).
Given that, frankly speaking ('in my opinion'!), Zs is far more important than VD, it seems odd that we do 'adjust' the latter for temp, but not the former!
Kind Regards, John