, Volume 26, Issue 5, pp 3031–3045 | Cite as

Preparation and characterization of physicochemical properties and application of novel ternary deep eutectic solvents

  • Michal JablonskyEmail author
  • Veronika Majova
  • Katarina Ondrigova
  • Jozef Sima
Original Research


In this work preparation of 23 new three-component DESs is described. Based on their stability 15 of them were finally selected and subjected to further investigation. DESs are eco-friendly solvents and due to their involving in treatment of lignocellulosic materials, some properties related to this topic were determined in detail, among them density, electrical conductivity and viscosity. The potential of the selected 15 DESs in delignification of unbleached pulp was examined. It was manifested that the addition of a third component to classical two-component DESs allow to purposefully control density and viscosity of the ternary DESs and thus upgrade pulp delignification efficiency. The addition of an alcohol leads to a decrease of both DES density and viscosity. Contrary, the addition of an organic acid causes their increase. Moreover, DES properties can be purposefully governed via changing the structure and complexity of the chain of a given acid.


Ternary deep eutectic solvents Physicochemical properties Density Viscosity Cellulose Delignification 



This work was supported by the Slovak Research and Development Agency under the contracts No. APVV-15-0052, APVV-0393-14, APVV-16-0088 and VEGA Grants 1/0543/15 and 1/0403/19. The authors would like to thank the STU Grant scheme for the Support of Young Researchers under contract Nos. 1696 and 1697 for financial assistance.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interests.


  1. Abbott AP, Capper G, Davies DL et al (2003) Novel solvent properties of choline chloride/urea mixtures. Chem Commun 1:70–71CrossRefGoogle Scholar
  2. Abbott AP, Capper G, Gray S (2006) Design of improved deep eutectic solvents using hole theory. ChemPhysChem 7:803–806CrossRefPubMedGoogle Scholar
  3. Abbott AP, Barron JC, Ryder KS, Wilson D (2007a) Eutectic-based ionic liquids with metal-containing anions and cations. Chem Eur J 13:6495–6501CrossRefPubMedGoogle Scholar
  4. Abbott AP, Capper G, Mckenzie KJ et al (2007b) Electrodeposition of zinc-tin alloys from deep eutectic solvents based on choline chloride. J Electroanal Chem 599:288–294CrossRefGoogle Scholar
  5. Abbott AP, Harris RC, Ryder KS (2007c) Application of hole theory to define ionic liquids by their transport properties. J Phys Chem B 111:4910–4913CrossRefPubMedGoogle Scholar
  6. Anastas P, Eghbali N (2010) Green chemistry: principles and practice. Chem Soc Rev 39:301–312CrossRefPubMedGoogle Scholar
  7. Aroso IM, Paiva A, Reis RL, Duarte ARC (2017) Natural deep eutectic solvents from choline chloride and betaine—physicochemical properties. J Mol Liquids 241:654–661CrossRefGoogle Scholar
  8. Bagh FSG, Shahbaz K, Mjalli FS et al (2013) Electrical conductivity of ammonium and phosphonium based deep eutectic solvents: measurements and artificial intelligence-based prediction. Fluid Phase Equilib 356:30–37CrossRefGoogle Scholar
  9. Dai Y, Spronsen J, Witkamp GJ et al (2013) Natural deep eutectic solvents as new potential media for green technology. Anal Chim Acta 85:61–68CrossRefGoogle Scholar
  10. Davis SJ (2015) Deep eutectic solvents derived from inorganic salts. Ph.D. dissertation. University of LeicesterGoogle Scholar
  11. Degam G (2017) Deep eutectic solvents synthesis, characterization and applications in pretreatment of lignocellulosic biomass. Ph.D. dissertation. South Dakota State UniversityGoogle Scholar
  12. Dios SLG (2013) Phase equilibria for extraction processes with designer solvents. Ph.D. dissertation. University of Santiago de CompostelaGoogle Scholar
  13. Durand E, Lecomte J, Baréa B et al (2012) Evaluation of deep eutectic solvents as new media for Candida antarctica B lipase catalyzed reactions. Process Biochem 47:2081–2089CrossRefGoogle Scholar
  14. Francisco M, Bruinhorst A, Kroon MC (2013) Low-transition-temperature mixtures (LTTMs): a new generation of designer solvents. Angew Chem Int Ed 52:3074–3085CrossRefGoogle Scholar
  15. Galbe M, Zacchi G (2007) Pretreatment of lignocellulosic materials for efficient bioethanol production. Adv Biochem Eng Biotechnol 108:41–65PubMedGoogle Scholar
  16. Hayyan A, Mjalli FS, AlNashef IM et al (2012) Fruit sugar-based deep eutectic solvents and their physical properties. Termochim Acta 541:70–75CrossRefGoogle Scholar
  17. Hayyan M, Hashim MA, Al-Saadi MA et al (2013) Assessment of cytotoxicity and toxicity for phosphonium-based deep eutectic solvents. Chemosphere 93:455–459CrossRefPubMedGoogle Scholar
  18. Haz A, Strizincova P, Majova V et al (2016) Thermal stability of selected deep eutectic solvents. Int J Recent Sci Res 7:14441–14444Google Scholar
  19. Hendriks AT, Zeeman G (2009) Pretreatments to enhance the digestibility of lignocellulosic biomass. Bioresour Technol 100:10–18CrossRefPubMedGoogle Scholar
  20. Huddleston JG, Visser AE, Reichert WM et al (2001) Characterization and comparison of hydrophilic and hydrophobic room temperature ionic liquids incorporating the imidazolium cation. Green Chem 3:156–164CrossRefGoogle Scholar
  21. Jablonsky M, Skulcova A, Hascicova Z et al (2016) Contribution of deep eutectic solvents for separation processing. In: Application of analytical methods in environmental and fire engineering. Technical University in Zvolen, ZvolenGoogle Scholar
  22. Jablonsky M, Majova V, Skulcova A, Haz A (2018a) Delignification of pulp using deep eutectic solvents. JHED 22:76–81Google Scholar
  23. Jablonsky M, Skulcova A, Malvis A, Sima J (2018b) Extraction of value-added components from food industry based and agro-forest biowastes by deep eutectic solvents. J Biotechnol 282:46–66CrossRefPubMedGoogle Scholar
  24. Kareem MA, Mjalli FS, Hashim MA, AlNashef IM (2010) Phosphonium-based ionic liquids analogues and their physical properties. J Chem Eng Data 55:4632–4637CrossRefGoogle Scholar
  25. Khandelwal S, Tailor YK, Kumar M (2016) Deep eutectic solvents (DESs) as eco-friendly and sustainable solvent/catalyst systems in organic transformations. J Mol Liquids 215:345–386CrossRefGoogle Scholar
  26. Kudłak B, Owczarek K, Namieśnik J (2015) Selected issues related to the toxicity of ionic liquids and deep eutectic solvents—a review. Environ Sci Pollut Res 22:11975–11992CrossRefGoogle Scholar
  27. Kumar AK, Parikh BS, Pravakar M (2016a) Natural deep eutectic solvent mediated pretreatment of rice straw: bioanalytical characterization of lignin extract and enzymatic hydrolysis of pretreated biomass residue. Environ Sci Pollut Res 23:9265–9275CrossRefGoogle Scholar
  28. Kumar AK, Parikh BS, Shah E, Liu LZ, Cotta MA (2016b) Cellulosic ethanol production from green solvent-pretreated rice straw. Biocatal Agric Biotechnol 7:14–23CrossRefGoogle Scholar
  29. Li X, Row KH (2017) Application of novel ternary deep eutectic solvents as a functional monomer in molecularly imprinted polymers for purification of levofloxacin. J Chromatogr B 1068:56–63Google Scholar
  30. Lindholm CA (1990) Effect of dissolved reaction products on pulp viscosity in low consistency ozone bleaching. Paper Timber 72:254–256Google Scholar
  31. Liu TY, Chen YA, Xing YJ (2014) Synthesis and characterization of novel ternary deep eutectic solvents. Chin Chem Lett 25:104–106CrossRefGoogle Scholar
  32. Loow YL, New EK, Yang GH et al (2017) Potential use of deep eutectic solvents to facilitate lignocellulosic biomass utilization and conversion. Cellulose 24:3591–3618CrossRefGoogle Scholar
  33. Lynam JG, Kumar N, Wong MJ (2017) Deep eutectic solvents’ ability to solubilize lignin, cellulose, and hemicellulose; thermal stability; and density. Bioresour Technol 238:684–689CrossRefPubMedGoogle Scholar
  34. Majova V, Horanova S, Skulcova A et al (2017) Deep eutectic solvent delignification: impact of initial lignin. BioResources 12:7301–7310Google Scholar
  35. Osch DJGP, Kollau LJBM, Bruinhorst A et al (2017) Ionic liquids and deep eutectic solvents for lignocellulosic biomass fractionation. Phys Chem Chem Phys 19:2636–2665CrossRefPubMedGoogle Scholar
  36. Rydholm SA (1966) Pulping processes, 2nd edn. Wiley, New YorkGoogle Scholar
  37. Shahbaz K, Baroutian S, Mjalli FS (2012) Densities of ammonium and phosphonium based deep eutectic solvents: prediction using artificial intelligence and group contribution techniques. Thermochim Acta 527:59–66CrossRefGoogle Scholar
  38. Shahbaz K, Mjalli FS, Vakili-Nezhaad G (2016) Thermogravimetric measurement of deep eutectic solvents vapor pressure. J Mol Liquids 222:61–66CrossRefGoogle Scholar
  39. Smith EL, Abbot AP, Ryder KS (2014) Deep eutectic solvents (DESs) and their applications. Chem Rev 114:11060–11082CrossRefPubMedGoogle Scholar
  40. Soares B, Tavares DJ, Amaral JL (2017) Enhanced solubility of lignin monomeric model compounds and technical lignins in aqueous solutions of deep eutectic solvents. ACS Sustain Chem Eng 5:4056–4065CrossRefGoogle Scholar
  41. Steichen M, Thomassey M, Siebentritt S, Dale PJ (2011) Controlled electrodeposition of Cu–Ga from a deep eutectic solvent for low cost fabrication of CuGaSe2 thin film solar cells. Phys Chem Chem Phys 13:4292–4302CrossRefPubMedGoogle Scholar
  42. TAPPI T236cm-85 (1996) Kappa number of pulp. TAPPI Press, AtlantaGoogle Scholar
  43. Trajano HL, Wyman CE (2013) Fundamentals of biomass pretreatment at low pH. In: Wyman CE (ed) Aqueous pretreatment of plant biomass for biological and chemical conversion to fuels and chemical. Wiley, New York, pp 103–128CrossRefGoogle Scholar
  44. Troter DZ, Todorovic Z, Dokić-Stojanović DR (2017) The physico-chemical and thermodynamic properties of the choline chloride-based deep eutectic solvents. J Serb Chem Soc 82:1039–1052CrossRefGoogle Scholar
  45. Yan YC, Rashmi W, Khalid M et al (2017) Potential application of deep eutectic solvents in heat transfer application. JESTEC 12:1–14Google Scholar
  46. Zhang Q, Vigier K, Royer S, Jérôme F (2012) Deep eutectic solvents: syntheses, properties and applications. Chem Soc Rev 41:7108–7146CrossRefPubMedGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  • Michal Jablonsky
    • 1
    Email author
  • Veronika Majova
    • 1
  • Katarina Ondrigova
    • 1
  • Jozef Sima
    • 2
  1. 1.Institute of Natural and Synthetic Polymers, Department of Wood, Pulp and Paper, Faculty of Chemical and Food TechnologySlovak University of Technology in BratislavaBratislavaSlovak Republic
  2. 2.Institute of Inorganic Chemistry, Technology and Materials, Department of Inorganic Chemistry, Faculty of Chemical and Food TechnologySlovak University of Technology in BratislavaBratislavaSlovak Republic

Personalised recommendations