Historically, different pH dependent behaviour at the mineral oxide/aqueous electrolyte interface has been observed by non-resonant second harmonic generation (SHG) and resonant sum frequency generation (SFG), despite a general understanding that both techniques are dominated by the response of water. Here we compare the two at the silica/aqueous interface at high salt concentration and as a function of pH to shed light on the origins of both measurements. From this comparison and SHG measurements at the silica/air interface, we conclude that SHG originates from the net order of water and the silica substrate, with the latter dominating the observed intensities below pH 6.5. In contrast, SFG is dominated by the higher SF activity, yet lower number density, of waters that contribute in the low wavenumber range, according to molecular dynamic simulations. Furthermore, spectral resolution in SFG of oppositely oriented water populations prevents cancellation of signal making it more difficult to relate SF intensity to the net order of water.

The molecular origin of overcharging at mineral oxide surfaces remains a cause of contention within the geochemistry, physics, and colloidal chemistry communities owing to competing "chemical" vs "physical" interpretations. Here, we combine vibrational sum frequency spectroscopy and streaming potential measurements to obtain molecular and macroscopic insights into the pH-dependent interactions of calcium ions with a fused silica surface. In 100 mM CaCl 2 electrolyte, we observe evidence of charge neutralization at pH~10.5, as deducted from a minimum in the interfacial water signal. Concurrently, adsorption of calcium hydroxide cations is inferred from the appearance of a spectral feature at ~3610 cm -1 . However, the interfacial water signal increases at higher pH, while adsorbed calcium hydroxide appears to remain constant, indicating that overcharging results from hydrated Ca 2+ ions present within the Stern layer. These findings suggest that both specific adsorption of hydrolyzed ions and ion-ion correlations of hydrated ions govern silica overcharging with increasing pH. File list (2) download file view on ChemRxiv Rashwan_Manuscript.pdf (1.77 MiB) download file view on ChemRxiv Rashwan_SupportingInformation.pdf (1.07 MiB)

The molecular origin of overcharging at mineral oxide surfaces remains a cause of contention within the geochemistry, physics, and colloidal chemistry communities owing to competing “chemical” vs “physical” interpretations. Here, we combine vibrational sum frequency spectroscopy and streaming potential measurements to obtain molecular and macroscopic insights into the pH-dependent interactions of calcium ions with a fused silica surface. In 100 mM CaCl₂ electrolyte, we observe evidence of charge neutralization at pH~10.5, as deducted from a minimum in the interfacial water signal. Concurrently, adsorption of calcium hydroxide cations is inferred from the appearance of a spectral feature at ~3610 cm^-1. However, the interfacial water signal increases at higher pH, while adsorbed calcium hydroxide appears to remain constant, indicating that overcharging results from hydrated Ca²⁺ ions present within the Stern layer. These findings suggest that both specific adsorption of hydrolyzed ions and ion-ion correlations of hydrated ions govern silica overcharging with increasing pH.

Treating the oil sands tailings ponds is a major challenge because of the vast amounts of tailings and the need for a reliable treatment technique for releasing water and generating the highly consolidated material required for land reclamation. Treatment with chemicals such as lime (calcium (hydr)oxide) is a promising technology for tailings dewatering and consolidation, particularly at higher pH. Given that kaolinite and silica minerals are the main constituents of many oil sands, we have investigated the influence of lime and NaOH addition on the silica/aqueous kaolinite interface over the pH range 7.4− 12.4 using vibrational sum frequency generation spectroscopy (SFG). With lime addition, at pH 12.0 and above we observe a complete disappearance of the vibrational features of the interfacial water molecules for planar silica in contact with an aqueous dispersion of kaolinite particles. A concurrent increase in the amount of adsorbed kaolinite on the silica surface at pH 12.0 and above is observed, shown in the increased intensity of the kaolinite SFG peak at 3694 cm −1 . This suggests that the absence of water features in the SFG spectra is associated with conditions that facilitate dewatering. With NaOH addition, however, the interfacial water SF intensity is still significant even under highly alkaline conditions despite the increase in adsorbed kaolinite at high pH. To better understand the SFG observations and get a deeper insight into the chemistry of the silica/aqueous kaolinite interface, we measure the ζ-potential on the planar silica/ aqueous interface and kaolinite aqueous dispersions under the same pH conditions with NaOH and lime addition.

The molecular origin of overcharging at mineral oxide surfaces remains a cause of contention within the geochemistry, physics, and colloidal chemistry communities owing to competing “chemical” vs “physical” interpretations. Here, we combine vibrational sum frequency spectroscopy and streaming potential measurements to obtain molecular and macroscopic insights into the pH-dependent interactions of calcium ions with a fused silica surface. In 100 mM CaCl₂ electrolyte, we observe evidence of charge neutralization at pH~10.5, as deducted from a minimum in the interfacial water signal. Concurrently, adsorption of calcium hydroxide cations is inferred from the appearance of a spectral feature at ~3610 cm^-1. However, the interfacial water signal increases at higher pH, while adsorbed calcium hydroxide appears to remain constant, indicating that overcharging results from hydrated Ca²⁺ ions present within the Stern layer. These findings suggest that both specific adsorption of hydrolyzed ions and ion-ion correlations of hydrated ions govern silica overcharging with increasing pH.