A sampling system for a high-temperature liquid includes a sampling loop, a venturi pump nebulizer, and an optical cell. The sampling loop includes a liquid inlet configured for the high-temperature liquid to flow into the sampling loop from a high-temperature liquid vessel and a liquid return configured for returning the high-temperature liquid to the high-temperature liquid vessel. The venturi pump nebulizer includes a nozzle positioned in the sampling loop downstream of the liquid inlet. The nozzle is configured to introduce a gas stream into the sampling loop to produce a vacuum within the sampling loop that draws the high-temperature liquid into the sampling loop and aerosolizes the high-temperature liquid in the gas stream. The optical cell is configured to receive the aerosolized high-temperature liquid for on-line chemical monitoring thereof. The optical cell includes at least one optical window configured for data acquisition to perform the on-line chemical monitoring.