ESR evidence of the dynamic crossover in the supercooled liquid states of a series of solid n-alkanes.

A study of the rotation dynamics of the spin probe TEMPO by electron spin resonance (ESR) spectroscopy in a series of six short- and medium-sized n-alkanes is presented. In addition to the usual crossover effects connected with solid-liquid phase transitions at temperature Tm and the solid-solid transition at Tss, we find a strong correlation between the change in reorientation at the characteristic ESR temperature TfastX1 < Tss and/or Tm with the ratio TfastX1/Tm = 0.76 ± 0.03 and the characteristic dynamic temperature, TX, obtained from the viscosity data. This indicates the presence of local disordered regions in the crystalline structure which is indeed sensitive to dynamic change at the crossover temperature TX ≅ TfastX1.

[1]  S. Arrese-Igor,et al.  Molecular dynamic heterogeneity in relation to free volume and relaxation dynamics in organic glass-formers: oligomeric cis-1,4-poly(isoprene). , 2017, Physical chemistry chemical physics : PCCP.

[2]  B. Zgardzińska,et al.  Positronium in Normal Alkanes , 2012 .

[3]  H. Švajdlenková,et al.  The Spin Probe Dynamics and the Free Volume in a Series of Amorphous Polymer Glass‐Formers , 2011 .

[4]  H. Eugene Stanley,et al.  Transport properties of glass-forming liquids suggest that dynamic crossover temperature is as important as the glass transition temperature , 2010, Proceedings of the National Academy of Sciences.

[5]  H. Švajdlenková,et al.  Spin probe mobility in relation to free volume and relaxation dynamics of glass‐formers: A series of spin probes in poly(isobutylene) , 2009 .

[6]  R. Zaleski,et al.  Positronium Formation in Solid Long-Chain Alkanes , 2005 .

[7]  Ding-hai Huang,et al.  Chain length dependence of the thermodynamic properties of linear and cyclic alkanes and polymers. , 2005, The Journal of chemical physics.

[8]  W. Wakeham,et al.  The Viscosity and Density of n-Dodecane and n-Octadecane at Pressures up to 200 MPa and Temperatures up to 473 K , 2004 .

[9]  R. Zaleski,et al.  Odd-Even Differences in o-Ps Properties in Some Solid Long-Chain Alkanes , 2004 .

[10]  R. Zaleski,et al.  Temperature, pressure and source-irradiation effects in positronium formation in some solid long-chain alkanes , 2003 .

[11]  I. Marrucho,et al.  Viscosity and Liquid Density of Asymmetric Hydrocarbon Mixtures , 2003 .

[12]  M. Bouroukba,et al.  Models for Estimation of Pure n-Alkanes' Thermodynamic Properties as a Function of Carbon Chain Length , 2003 .

[13]  A. Sokolov,et al.  Universality of the dynamic crossover in glass-forming liquids: a "magic" relaxation time. , 2003, Physical review. E, Statistical, nonlinear, and soft matter physics.

[14]  Michel Dirand,et al.  Normal Alkanes, Multialkane Synthetic Model Mixtures, and Real Petroleum Waxes: Crystallographic Structures, Thermodynamic Properties, and Crystallization , 2002 .

[15]  A. Schönhals.  Evidence for a universal crossover behaviour of the dynamic glass transition , 2001 .

[16]  M. Deutsch,et al.  Measurements of homogeneous nucleation in normal-alkanes , 2000 .

[17]  A. Sokolov.  The glass transition: general scenario and crossover temperature , 1998 .

[18]  C. Alba-Simionesco,et al.  Study of the depolarized light scattering spectra of supercooled liquids by a simple mode-coupling model , 1997 .

[19]  A. Sokolov.  The glass transition: New ideas in an age-old field , 1997 .

[20]  S. Rice,et al.  Backbone ordering in amphiphile monolayers , 1995 .

[21]  Takashi Yamamoto,et al.  Solid–solid phase transitions in n‐alkanes C23H48 and C25H52: X‐ray power diffraction study on new layer stacking in phase V , 1995 .

[22]  R. Richert,et al.  DYNAMICS OF GLASS-FORMING LIQUIDS. I: TEMPERATURE-DERIVATIVE ANALYSIS OF DIELECTRIC RELAXATION DATA , 1995 .

[23]  E. Sirota,et al.  PHASE TRANSITIONS AMONG THE ROTATOR PHASES OF THE NORMAL ALKANES , 1994 .

[24]  T. Aminabhavi,et al.  Densities, Viscosities, Refractive Indices, and Speeds of Sound of the Binary Mixtures of Bis(2-methoxyethyl) Ether with Nonane,Decane, Dodecane, Tetradecane, and Hexadecane at 298.15, 308.15, and 318.15 K , 1994 .

[25]  Kremer,et al.  Anomalies in the scaling of the dielectric alpha -relaxation. , 1993, Physical review letters.

[26]  E. Sirota,et al.  Rotator phases of the normal alkanes: An x‐ray scattering study , 1993 .

[27]  W. Gotze,et al.  Relaxation processes in supercooled liquids , 1992 .

[28]  Marc J. Assael,et al.  Measurements of the viscosity of n-heptane, n-nonane, and n-undecane at pressures up to 70 MPa , 1991 .

[29]  T. Aminabhavi,et al.  Thermodynamic interactions in mixtures of bromoform with hydrocarbons , 1991 .

[30]  Yoshiaki Tanaka,et al.  Viscosity and density of binary mixtures of cyclohexane with n-octane, n-dodecane, and n-hexadecane under high pressures , 1991 .

[31]  M. Oguni,et al.  Thermo-analytical study of vapor-deposited n-alkanes , 1991 .

[32]  Rössler,et al.  Indications for a change of diffusion mechanism in supercooled liquids. , 1990, Physical review letters.

[33]  M. Oguni,et al.  A DTA apparatus for vapour-deposited samples. characterisation of some vapour-deposited hydrocarbons , 1990 .

[34]  Harald A. Øye,et al.  Viscosity of pure hydrocarbons , 1989 .

[35]  K. Marsh,et al.  Viscosities of nonelectrolyte liquid mixtures. I. n-hexadecane + n-octane , 1987 .

[36]  Bishop,et al.  Power-law behavior in the viscosity of supercooled liquids. , 1986, Physical review. B, Condensed matter.

[37]  H. Saint-Guirons,et al.  Pressure (1-1000 bars) and temperature (20-100.degree.C) dependence of the viscosity of liquid hydrocarbons , 1986 .

[38]  L. Chu,et al.  Some physical properties of long chain hydrocarbons , 1986 .

[39]  K. J. Young,et al.  Transport properties of nonelectrolyte liquid mixtures—I. Viscosity coefficients for n-alkane mixtures at saturation pressure from 283 to 378 K , 1980 .

[40]  M. J. Oliver,et al.  Homogeneous nucleation of n-alkanes measured by differential scanning calorimetry , 1975 .

[41]  D. Uhlmann,et al.  Crystal nucleation in normal alkane liquids , 1975 .

[42]  N. Ototake.  Prediction of Liquid Viscosity of Alkane , 1971 .

[43]  A. Buchachenko,et al.  Kinetics of molecular motions in liquids and its correlation with kinetics of radical liquid–phase reactions , 1969 .

[44]  D. L. Hogenboom,et al.  Viscosity of Several Liquid Hydrocarbons as a Function of Temperature, Pressure, and Free Volume , 1967 .

[45]  A. Barlow,et al.  Viscous behaviour of supercooled liquids , 1966, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[46]  P. H. Gross,et al.  Properties of the liquid state: II: Description of viscosity over the entire liquid range , 1964 .

[47]  M. Broadhurst,et al.  An Analysis of the Solid Phase Behavior of the Normal Paraffins , 1962, Journal of Research of the National Bureau of Standards. Section A, Physics and Chemistry.

[48]  D. Turnbull,et al.  Kinetics of Crystal Nucleation in Some Normal Alkane Liquids , 1961 .

[49]  F. Whitmore,et al.  Properties of High Molecular Weight Hydrocarbons , 1955 .

[50]  Arthur K. Doolittle,et al.  Studies in Newtonian Flow. I. The Dependence of the Viscosity of Liquids on Temperature , 1951 .

[51]  H. G. Drickamer,et al.  Viscosity of Normal Paraffins near the Freezing Point , 1949 .

[52]  J. Boelhouwer,et al.  Viscosity data and relations of normal and iso-paraffins , 1947 .

[53]  Kurt Eberlein,et al.  Über physikalische Daten von 1‐Olefinen und n‐Paraffinen , 1941 .

[54]  T. Midgley,et al.  PHYSICAL PROPERTIES OF THE NORMAL PARAFFIN HYDROCARBONS, PENTANE TO DODECANE , 1931 .

[55]  E. C. Bingham,et al.  Chemical Constitution and Association , 1930 .