Phase Equilibrium and Density of CO2 + Acetic Acid Systems from 308.15 to 338.15 K and 15 to 45 MPa.

Using a high-pressure phase equilibrium apparatus and vibrating-tube densimeter, phase transition pressures of CO2 (1) + acetic acid (2) binary systems with x 2 = 0.000, 0.107, 0.163, 0.222, and 1.000 were measured under temperatures from 308.15 to 338.15 K. Besides, the densities at the same composition and temperature under pressure from 15 to 45 MPa were also detected, and the volumes of mixing (ΔV m) were calculated. Three prediction models (SRK EOS, PC-SAFT EOS, and TS model) were introduced to predict and correlate the density of binary systems, which was found to have positive relationships with temperature and acetic acid concentration and a negative relationship with pressure. Thereinto, the variation trend of CO2 density with pressure tends to be flat under high pressure, and which of acetic acid density increased linearly with pressure. ΔV m are negative, and their absolute value increases with the increase of temperature and the decrease of pressure. The work herein could provide a theoretical guide and basic data for supercritical CO2 extraction technology and CO2 application in oil field development.

Rheological behaviors of microbial polysaccharides with different substituents in aqueous solutions: Effects of concentration, temperature, inorganic salt and surfactant.

Rheological behaviors of microbial polysaccharides with different substituents in aqueous solutions have been systematically investigated. Both the saccharide side chains and acetyl substituents improve the gelation of welan gum (WG), diutan gum (DG) and gellan gum (GG) in pure water at 25 °C. For the polysaccharides with saccharide side chains (WG and DG), the relationship between the apparent viscosity and concentration conforms to the linear equation, while that of the polysaccharide with acetyl (GG) is exponential. More importantly, the roles of substituents on the stability of the molecular conformation of polysaccharides are significantly depended on the surrounding environment. Disaccharide side chains promote the stability of helical conformation and gel aggregates of GG at high temperature (85 °C) or in the presence of inorganic salts with the ionic strength of 2.0 mol L-1. The stability of gel structure containing acetyl (GG) shows higher temperature/salt sensitivity. Additionally, deacylated gellan gum (GG(d)) solutions transform into hydrogels in the presence of dodecyltrimethylammonium bromide (DTAB). This study will help to obtain a better understanding on the rheological properties of polysaccharides with respect to the conformation and applications.

Rheological properties and thickening mechanism of aqueous diutan gum solution: Effects of temperature and salts.

Rheological properties of a new microbial polysaccharide, diutan gum in aqueous solution have been systematically investigated. It is found that molecular aggregates of diutan gum can be formed at a very low concentration (0.12 g/L), and the mechanism of thickening by diutan gum is proposed. The viscosity retention rate of diutan gum changes little when increasing the temperature from 298 K to 348 K or in a high salinity solution (55.5 g L(-1)). Gel structure can be formed in the diutan gum solution, owing to the finding that the dynamic modulus has an exponential relationship with the concentration. The gel properties of diutan gum are not sensitive to temperature, and are virtually independent of cationic environment (Na(+) and Ca(2+)). The temperature/salt tolerance of the diutan gum solution is mainly attributed to its perfect double helix molecular conformation, the location of the side chains of its molecules, and its water retention capacity.

Effects of inorganic cations on the rheology of aqueous welan, xanthan, gellan solutions and their mixtures.

The effects of different inorganic cations (Na(+), K(+), Ca(2+) and Al(3+)) on the rheological properties of single and mixture polysaccharide solutions have been systematically investigated. The apparent viscosity and viscoelasticity of welan solutions decrease with the addition of inorganic cations. Meanwhile, the addition of Al(3+) and K(+), respectively, enhances the apparent viscosity and viscoelasticity of xanthan and gellan solutions by promoting the gelation. The viscosity retention rate of welan/xanthan mixtures is higher than that of the single components in Na(+), K(+) and Ca(2+) solutions, and the viscosity retention rate of welan/gellan mixtures is higher than that of the single components in Ca(2+) solutions. The salt induced gelation expands the application for polysaccharides, and it is also believed that the method of combining welan and xanthan (or gellan) is an effective strategy to control the rheology and morphology of solutions in the presence of inorganic salts.

The comparison of rheological properties of aqueous welan gum and xanthan gum solutions.

Rheological properties of welan gum and xanthan gum solutions have been characterized systematically at various concentrations, temperatures and salinities. It is found that the viscoelasticity of welan gum is higher than that of xanthan gum at the same condition though the molecular weight of welan gum is lower. In view of this, welan gum will make a good performance in enhanced oil recovery, especially in high temperature and high salinity reservoirs. Network structure can be formed in solutions of welan gum and xanthan gum for the dynamic modulus has exponential relationship with the concentration. Moreover, the molecular aggregates of welan gum adopt a different arrangement with that of xanthan gum, adjacent double helices of welan gum arrange in parallel as the zipper model. The structure formed by zipper model is still stable in high temperature and high salinity.

Aggregation behaviors of PEO-PPO-ph-PPO-PEO and PPO-PEO-ph-PEO-PPO at an air/water interface: experimental study and molecular dynamics simulation.

The block polyethers PEO-PPO-ph-PPO-PEO (BPE) and PPO-PEO-ph-PEO-PPO (BEP) are synthesized by anionic polymerization using bisphenol A as initiator. Compared with Pluronic P123, the aggregation behaviors of BPE and BEP at an air/water interface are investigated by the surface tension and dilational viscoelasticity. The molecular construction can influence the efficiency and effectiveness of block polyethers in decreasing surface tension. BPE has the most efficient ability to decrease surface tension of water among the three block polyethers. The maximum surface excess concentration (Γ(max)) of BPE is larger than that of BEP or P123. Moreover, the dilational modulus of BPE is almost the same as that of P123, but much larger than that of BEP. The molecular dynamics simulation provides the conformational variations of block polyethers at the air/water interface.

Effect of alcohols on aggregation behaviors of branched block polyether Tetronic 1107 at an air/liquid surface.

The aggregation behaviors of branched block polyether Tetronic 1107 (T1107) at an air/liquid surface was investigated in mixed solvents consisting of water and one of the following polar cosolvents: ethanol, n-propanol, ethylene glycol (EG), or glycerol (GLY). Surface tension measurements provide information about the effects of cosolvents on the critical micellization concentration (cmc), the standard Gibbs energy (ΔG°(mic)), the maximum surface excess concentration (Γ(max)), the minimum area per polyether molecule at the air/liquid surface (A(min)), and the standard free energy of adsorption (ΔG°(ads)). The addition of ethanol and n-propanol to water disfavors the micellization and progressively increases the cmc of T1107, whereas the cmc decreases with the addition of EG and GLY. The values of ΔG°(mic) of T1107 are all negative in mixed solvents, and their absolute values become smaller as the ethanol or n-propanol content increases but become larger as the EG or GLY content increases. The cosolvents have a significant effect on the surface adsorption and cmc, and the order is as follows: n-propanol-water > ethanol-water > water > EG-water > GLY-water. The octanol/water partition coefficient (log P) of the cosolvent is used to correlate the effects, and it could capture the effect of cosolvents on the cmc qualitatively. The surface dilational rheological properties of T1107 in water and water-alcohol mixtures were also studied by surface dilational viscoelasticity and surface tension relaxation measurements. The dilational elasticity decreases monotonously in the presence of ethanol or n-propanol. With the increasing concentration of EG and GLY, the dilational elasticity of T1107 passes through a maximum that coincides with the change in Γ(max).

Effect of amino acids on aggregation behaviors of sodium deoxycholate at air/water surface: surface tension and oscillating bubble studies.

The aggregation behaviors of sodium deoxycholate (NaDC) at the air/water surface were investigated via surface tension and oscillating bubble measurements in the absence and presence of three alkaline amino acids, namely, L-Lysine (L-Lys), L-Arginine (L-Arg), and L-Histidine (L-His). The results of surface tension measurements show that NaDC has a lower ability to reduce the surface tension of water, because NaDC molecules orient at the surface in an oblique direction and tend to aggregate together, which is approved by molecular dynamics (MD) simulation. L-Lys is the most efficient of the three amino acids in reducing the critical aggregation concentration (cac) of NaDC in aqueous solution. The influence of amino acids on the dilational rheological properties of NaDC was studied using the drop shape analysis method in the frequency range from 0.02 to 0.5 Hz. The results reveal that the absolute modulus passes through a maximum value with increasing NaDC concentration. The addition of amino acids increases the absolute modulus of NaDC, and the maximum value is observed at much lower concentration. From the perspective of structures of amino acids, the performance of L-Arg is similar to that of L-His, and both of them bring out a smaller effect on the absolute modulus than that of L-Lys. From the above results, it may be presumed that electrostatic and hydrophobic effects are important impetus during the interaction between amino acids and NaDC at the air/water surface. Hydrogen bonding is so ubiquitous in the system that the difference of hydrogen bonding between NaDC and amino acid is ignored.