Influence of polymer molecular weight and concentration on coexistence curve of isobutyric acid + water

J Phys Chem B. 2011 Oct 27;115(42):12065-75. doi: 10.1021/jp2070858. Epub 2011 Sep 30.

Abstract

We report the influence of variation of molecular weights (MWs = 2, 4, 6, and 9 × 10(5) g mol(-1)) and concentration (C) of a long-chain polymer (polyethylene oxide, PEO) on an upper critical solution temperature (UCST) of isobutyric acid (I) + water (W) using density (ρ) measurements as a function of temperature. The ρ values in each coexisting phase of IW have been measured at three different PEO concentrations (C = 0.395, 0.796, and 1.605 mg/cm(3)) in the near critical composition of IW at temperatures below the system's upper critical point for each molecular weight (MW) of PEO. Further, to ascertain the PEO behavior in IW we have measured the polydispersity values for both coexisting liquid phases by using dynamic light scattering (DLS). The data show that the polymer was significantly affected in the critical region of IW and these various MWs and concentrations of PEO show significant modulation on the critical exponents (β), the critical temperatures (T(c)), and critical composition (ϕ(c)), which are depicting the shape of the coexistence curve. The values of β and T(c) increase with increasing PEO MW and concentrations. Besides, the ϕ(c) values slightly decrease with increasing the C values in the mixture of IW. However, the rate of decrease in ϕ(c) is insignificant. Our experimental results explicitly elucidate that most of polymer chain entangles in water rich phase, thereby the polymer monomers strongly interact with neighbor solvent particles and also intra chain interaction between polymer monomers.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Isobutyrates / chemistry*
  • Light
  • Molecular Weight
  • Polyethylene Glycols / chemistry*
  • Scattering, Radiation
  • Temperature
  • Water / chemistry*

Substances

  • Isobutyrates
  • Water
  • Polyethylene Glycols
  • isobutyric acid