An air gap has a much higher breakdown level than non-coppered surfaces on a circuit board. There are two mechanisms at play - physical air-gap (clearance) and what is called "tracking" on PCB surfaces (creepage).
Creepage Distance. Creepage is the shortest path between two
conductive parts (or between a conductive part and the bounding
surface of the equipment) measured along the surface of the
insulation. A proper and adequate creepage distance protects against
tracking, a process that produces a partially conducting path of
localized deterioration on the surface of an insulating material as a
result of the electric discharges on or close to an insulation
surface. The degree of tracking required depends on two major factors:
the comparative tracking index (CTI) of the material and the degree of
pollution in the environment.
and,
Clearance Distance. Clearance is the shortest distance between two
conductive parts (or between a conductive part and the bounding
surface of the equipment) measured through air. Clearance distance
helps prevent dielectric breakdown between electrodes caused by the
ionization of air. The dielectric breakdown level is further
influenced by relative humidity, temperature, and degree of pollution
in the environment.
As a practical example of air gap over PCB distance I once designed a high-voltage PSU (50kV dc). The output stages were diode triplers (unimportant for this example) but the PCB mounting the diodes and capacitors that took 6kV and turned it into 50kV had to have big holes around the components thus the "creapage" across the circuit board could not make a direct straight line across the PCB surface, rather it had to weave around the slots and holes and this gave it significantly higher breakdown voltage capabilities.
There is a similar question on stack exchange here that has tables of voltages and gaps for creapage and clearance.