Crystal - Rotator-I - Rotator-II Phase Transitions in the Mixtures of Alkanes

Prabir Kumar Mukherjee

Article ID: 1134
Vol 3, Issue 1, 2020, Article identifier:1–5

VIEWS - 527 (Abstract) 337 (PDF)


Using the combination of Flory–Huggins theory of isotropic mixing and Landau theory, we discuss the crystal – rotator-I – rotator-II phase transitions in the binary mixture of alkanes. The influence of concentration on the order parameters and the transition temperatures is discussed. Theoretical results show the first order character of both the rotator-I to crystal and rotator-II to rotator-I phase transitions in the mixture of alkanes. A good agreement between theoretical and experimental results are presented in this paper.


Rotator Phases; Alkanes; Phase Transitions; Landau Theory

Full Text:



Ungar G. Structure of rotator phases in n-alkanes. J. Phys. Chem. 1983; 87: 689-695. doi: 10.1021/j100227a032.

Sirota EB, King Jr. HE, Singer DM, et al. Rotator phases of the normal alkanes: An x-ray scattering study. J. Chem. Phys. 1993; 98: 5809-5824. doi: 10.1063/1.464874.

Sirota EB, Singer DM. Phase transitions among the rotator phases of the normal alkanes. J. Chem. Phys. 1994; 101: 10873-10882. doi: 10.1063/1.467837.

Sirota EB. Remarks concerning the relation between rotator phases of bulk n-alkanes and those of Langmuir monolayers of alkyl-chain surfactant on water. Langmuir 1997; 13: 3849-3859. doi: 10.1021/la9702291.

Doucet J, Denicolo I, Craievich A. X-ray study of the rotator phase of the odd-numbered paraffins C17H36, C19H40, and C21H44. J. Chem. Phys. 1981; 75: 1523–1529. doi: 10.1063/1.442185.

Craievich A, Denicolo I, Doucet J. Molecular motion and conformational defects in odd-numbered paraffins. Phys. Rev. B 1984; 30 4782–4788. doi: 10.1103/PhysRevB.30.4782.

Kruger J K, Jimenez R, Bohn K -P, et al. Phase-transition behavior of n-alkanes on nanostructured polytetrafluorethylens films: Brillouin spectroscopic and calorimetric investigations on pentacosane. Phys. Rev. B 1997; 56: 8683–8690. doi: 10.1103/physrevb.56.8683.

Paoloni S, Mercuri F, Zammit U, et al. Analysis of rotator phase transitions in the linear alkanes hexacosane to triacontane by adiabatic scanning calorimetry and by photopyroelectric calorimetry. J. Chem. Phys. 2018; 148: 094503-1-10. doi: 10.1063/1.5020146.

Dutta S and Prasad SK. Confinement-driven radical change in a sequence of rotator phases: a study on n-octacosane. Phys. Chem. Chem. Phys. 2018; 20: 24345-24352. doi: 10.1039/c8cp03603a.

Mukherjee PK. Phase transitions among the rotator phases of the normal alkanes: A review. Phys. Rep. 2015; 588: 1-54. doi: 10.1016/j.physrep.2015.05.005.

Denicolo I, Craievich AF, Doucet J. X-ray diffraction and calorimetric phase study of a binary paraffin: C23-C48-C24H50. J. Chem. Phys. 1984; 80: 6200–6203. doi: 10.1063/1.446722.

Ungar G, Masic N. Order in the rotator phase of n-alkanes. J. Phys. Chem. 1985; 89:1036-1042. doi: 10.1021/j100252a030.

Snyder RG, Goh MC, Srivatsavoy VIP, et al. Measurement of the growth kinetics of microdomains in binary n-alkane solid solutions by infrared spectroscopy. J. Phys. Chem. 1992; 96: 10008–10019. doi: 10.1021/j100203a078.

Snyder RG, Conti G, Strauss HL et al. Termally-induced mixing in partially microphase segregated binary n-alkane crystals. J. Phys. Chem. 1993; 97: 7342–7350. doi: 10.1021/j100130a037.

Sirota EB, King HE, Hughes Jr. GJ, et al. Novel phase behavior in normal alkanes. Phys. Rev. Lett. 1992; 68: 492-495. doi: 10.1103/PhysRevLett.68.492.

Sirota EB, King HE Jr., Shao Henry H, et al. Rotator phases in mixtures of n-alkanes. J. Phys. Chem. 1995; 99: 798–804. doi: 10.1021/j100002a050.

Dutta S, Srikanthamurthy S, Mukherjee PK, et al. Nanometer confinement-driven promotion and stabilization of a hexatic phase intervening between ordered rotator phases. J. Phys. Chem. B. 2018; 122(48): 10953–10963. doi: 10.1021/acs.jpcb.8b09017.

Kumar MV, Prasad SK. Influence of quenched disorder created by nanosilica network on phase transitions in tetracosane. RSC Adv. 2012; 2: 8531–8538. doi: 10.1039/c2ra21480f.

Zammit U, Marinelli M, Mercuri F, et al. Effect of quenched disorder on the R1–RV , RII–RI and Liquid-RII rotator phase transition in alkanes. J. Phys. Chem. B. 2011; 115: 2331–2337. doi: 10.1021/jp111067z.

Kumar MV, Prasad SK, Rao DSSS, et al. Competition between anisometric and aliphatic entities: an unusual phase sequence with the induction of a phase in an n-alkane–liquid crystal binary system. Langmuir. 2014; 30: 4465–4473. doi: 10.1021/la500367y.

Mukherjee PK. Landau model of the RII–RI–RV rotator phases in mixtures of alkanes. J. Chem. Phys. 2007; 127: 074901-1-6. doi: 10.1063/1.2764483.

Mukherjee PK. Tricritical behavior of the RI–RV rotator phase transition in a mixture of alkanes with nanoparticles. J. Chem. Phys. 2011; 135: 134505-1-6. doi: 10.1063/1.3646213.

Mukherjee PK. Effect of liquid crystal solute on the rotator phase transitions of n-alkanes. RSC Adv.. 2015; 5:12168-12177. doi: 10.1039/C4RA14116D.

Mukherjee PK. Effect of nanoparticles on the RII-RI-RV rotator phase transitions of alkane. Chem. Phys. Lett. 2017; 681: 75-79. doi: 10.1016/j.cplett.2017.05.038.



  • There are currently no refbacks.

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.

Creative Commons License

This site is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.