Raman spectroscopic measurements of ν₁ band of hydrogen sulfide over a wide range of temperature and density in fused‐silica optical cells

Abstract

A method was developed to determine the fluid density of pure hydrogen sulfide (H2S) at a fixed temperature using Raman spectroscopic measurements. The positions of the H2S Raman ν1 band were measured at a wide range of temperatures (188.15 K ≤ T ≤ 633.15 K) and pressures (P ≤ 506 bar) using fused‐silica capillary capsules and high‐pressure optical cells. The relation among H2S density (ρ), H2S ν1 peak position, and T can be represented by ρ = 2447.680 + 0.127 × T − 1.876 × ν1 − 0.000001 × T2 − 0.000048 × T × ν1 + 0.00036 × ν12 (root‐mean‐square error = 0.0197 g/cm3 and correlation coefficient = 0.9963). This equation can be applied to calculate the density of the H2S fluid from the measured H2S ν1 peak position at a given temperature. Finally, the effects of temperature and H2S density on ν1 peak position were examined using isochoric and isothermal experiments.

Species of Sulfur in Sour Gas Reservoir: Insights from In Situ Raman Spectroscopy of S–H2S–CH4–H2O System and Its Subsystems from 20 to 250°C

“…The sample-loading system utilized was according to that reported in Chou et al [28]. Because H 2 S is highly corrosive and toxic, a corrosion-resistant type of pressure valves (HiP 15-15AF1HC276) was used [30]. Chou et al [28] have reported detailed procedures for constructing FSCCs.…”

“…As only S is present in the sample, the bands at 1248 cm −1 , 1439 cm −1 , and 1513 cm −1 should be attributed to it, although details on vibrational modes are not clear at present. Based on the Raman spectra of H 2 S, the predominant band at 2500-2700 cm −1 was assigned to the symmetrical S-H stretching vibration (ν 1 ) [30,43]. The ν 1 ðH 2 SÞ Raman shift could be used to measure the H 2 S density [30].…”

“…As a result, in situ high-temperature experiments on S species are quite limited. Experimental investigations on the properties of geological fluids have proven that the use of fused silica capillary capsules (FSCCs) [28,29] in combination with in situ Raman spectroscopy is a suitable method to study experimental systems containing S and H 2 S [14,30]. FSCCs are made of SiO 2 , which is inert to S and H 2 S. Raman spectroscopy allows real-time and rapid analysis of the composition of FSCC samples at high temperatures.…”

Recent advances in linear and nonlinear Raman spectroscopy. Part XIII

“…J. Hetmanczyk and L. Hetmanczyk studied the dynamics of H 2 O ligands and ReO 4 − anions at the phase transition in [Mn(H 2 O) 2 ](ReO 4 ) 2 by complementary spectroscopic methods . Jiang et al carried out Raman spectroscopic measurements of ν 1 band of hydrogen sulfide over a wide range of temperature and density in fused silica optical cells . Kirtley and co‐workers compared pulsed and continuous lasers for high‐temperature Raman measurements of anhydrite.…”

Progress of Raman spectroscopic investigations on the structure and properties of coal

“…Raman spectroscopy is a type of molecular vibrational spectroscopy based on the Raman scattering effect. It has the advantages of simple sample preparation, in situ analysis, and nondestructive treatment of samples and has been widely used in geology, [37,38] material, [39,40] environmental, [41][42][43][44][45] and other fields. [46] Raman spectroscopy gives detailed information on the chemical structure and crystallinity of carbonaceous materials.…”