Dipole moment of PCl3F2 molecule is zero while dipole moment of PCl2F3 molecule is non zero why?

According to bent’s rule more electronegative atom or group attached those hybrids orbital have minimum s-character.

There is sp3d (Sp2+pd) hybridization trigonal bipiramidal(TBP) geometry in PCl₃F₂ molecule. we known that axial orbital (pd) have no s-character so F  atoms are attached with axial positions while chlorine atoms attach with equatorial (Sp2) position. Hence net dipole moment becomes zero. While in case of PCl₂F₃ one of the fluorine atom is also present at equatorial position hence there is net dipole moment.

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