Asymmetrical Dependence of {Ba2+}:{SO42-} on BaSO4 Crystal Nucleation and Growth in Aqueous Solutions: A Dynamic Light Scattering Study

The impact of solution stoichiometry, upon formation of BaSO4 crystals in 0.02 M NaCl suspensions, on the development of particle size was investigated using dynamic light scattering (DLS). Measurements were performed on a set of suspensions prepared with predefined initial supersaturation, based on the quotient of the constituent ion activity product {Ba2+}-{SO42-} over the solubility product Ksp (omega barite = {Ba2+}{SO42-}/ Ksp = 100, 500, or 1000-11,000 in steps of 1000), and ion activity solution stoichiometries (raq = {Ba2+}:{SO42-} = 0.01, 0.1, 1, 10 and 100), at circumneutral pH of 5.5-6.0, and ambient temperature and pressure. DLS showed that for batch experiments, crystal formation with varying raq was best investigated at an initial omega barite of 1000 and using the forward detection angle. At this omega barite and set of raq, the average apparent hydrodynamic particle size of the largest population present in all suspensions increased from similar to 200 to similar to 700 nm within 10-15 min and was independently confirmed by transmission electron microscopy (TEM) imaging. Additional DLS measurements conducted at the same conditions in flow confirmed that the BaSO4 formation kinetics were very fast for our specifically chosen conditions. The DLS flow measurements, monitoring the first minute of BaSO4 formation, showed strong signs of aggregation of prenucleation clusters forming particles with a size in the range of 200-300 nm for every raq. The estimated initial bulk growth rates from batch DLS results show that BaSO4 crystals formed fastest at near-stoichiometric conditions and more slowly at nonstoichiometric conditions. Moreover, at extreme SO4-limiting conditions, barite formation was slower compared to Balimiting conditions. Our results show that DLS can be used to investigate nucleation and growth at carefully selected experimental and analytical conditions. The combined DLS and TEM results imply that BaSO4 formation is influenced by solution stoichiometry and may aid to optimize antiscalant efficiency and regulate BaSO4 (scale) formation processes.

Automated summary

In this study, the impact of solution stoichiometry on the particle size development of BaSO4 crystals in 0.02 M NaCl suspensions was investigated using dynamic light scattering (DLS). The results showed that the average hydrodynamic particle size of the largest population in the suspensions increased from around 200 nm to around 700 nm within 10-15 min as the initial supersaturation and ion activity solution stoichiometries changed. The formation kinetics of BaSO4 crystals were found to be faster at near-stoichiometric conditions and slower at nonstoichiometric conditions.