abstract
The solid-liquid phase behaviour of two tertiary alcohols, perfluoro-tert-butanol and tert-butanol, was studied here using experimental (ITC, DSC and density measurements) and theoretical (MD simulations) approaches. The phase diagram of the binary mixture reveals highly negative deviations from ideality at low concentrations, as well as the formation of co-crystals and is characterized by two eutectic points, a congruent melting point and a peritectic reaction corresponding to TBH : TBF stoichiometries of 2 : 1 and 1 : 1 respectively. Excess molar enthalpies and volumes were calculated, showing negative and positive deviations from ideality, respectively. The effect of acidity, stereochemical hindrance and phobic effects and how they affect intermolecular interactions in these binary mixtures is discussed, with the aim of designing and fine-tuning type V deep eutectic solvents. The results showed that the fluorination of tertiary alcohols can be used for the tuning of the mixing properties and solid-liquid phase diagrams.
keywords
PARTICLE MESH EWALD; T-BUTYL ALCOHOL; LIQUID-MIXTURES; THERMODYNAMIC PROPERTIES; BINARY-MIXTURES; DYNAMICS; PHASE; HYDROCARBONS; ASSOCIATION; TEMPERATURE
subject category
Chemistry; Physics
authors
Vaz, ICM; Ferreira, AIMCL; Silva, GMC; Morgado, P; Abranches, DO; Bastos, M; Santos, LMNBF; Filipe, EJM; Coutinho, JAP
our authors
Dinis O. Abranches
Assistant Researcher
Gonçalo Miguel Carvalho da Silva
Junior Researcher
Inês C. M. Vaz
Junior Researcher
Groups
G4 - Renewable Materials and Circular Economy
G6 - Virtual Materials and Artificial Intelligence
Projects
CICECO - Aveiro Institute of Materials (UIDB/50011/2020)
Associated Laboratory CICECO-Aveiro Institute of Materials (LA/P/0006/2020)
acknowledgements
This work was partly developed within the scope of the project CICECO-Aveiro Institute of Materials (UIDB/50011/2020, UIDP/ 50011/2020 and LA/P/0006/2020), CIQUP, Centro de Investigaca~o em Qui ' mica da Universidade do Porto (UIDB/00081/ 2020); IMS, Institute of Molecular Sciences (LA/P/0056/2020), and Centro de Qui ' mica Estrutural, Institute of Molecular Sciences, (UIDB/00100/2020/LA/P/0056/2020), financed by national funds through the FCT/MEC (PIDDAC). AIMCLF is financed by national funds through the FCT-I.P., in the framework of the execution of the program contract provided in paragraphs 4, 5, and 6 of art. 23 of Law no. 57/2016 of 29 August, as amended by Law no. 57/2017 of 19 July.