mmWave frequency bands have gained much research interest in 5G NR for their extreme data speeds, capacity, and availability on a licensed/unlicensed basis. As the propagation losses are very high in mmWave bands, it requires directional beamforming, which can additionally be beneficial in time-of-arrival (TOA)-based ranging techniques. To satisfy high reliability and low latency requirements of industrial Internet-of-things (IIoT) in a factory environment, estimation of location-dependent propagation delays for essential industrial devices is critical. In this paper, we first model the mmWave TOA-based ranging coverage and error behavior for a single industrial device at various distances in an indoor factory environment. Later, the ranging error statistics are used to study the timing advance (TA) mechanism as an estimator for ToA-based indoor ranging, which can alternately be used to assess the coordination/synchronization accuracy among industrial devices. Our results reveal that mmWave-based ranging performs significantly better, bringing over-the-air timing synchronization accuracy to the nanosecond level. Specifically, the observed maximum synchronization errors for line-of-sight (LOS) and non-LOS (NLOS) scenarios are 6.4 ns and 16 ns, respectively.