Sciencemadness Discussion Board

List of deep eutectic solvents/ionic liquids

gatosgr - 30-4-2015 at 01:09

I thought about making a list of all the known combinations for deep eutectic solvents and ionic liquids, if you know of any others please post them here. :D

There are four types of eutectic solvents:
Type I Eutectic (metal salt + organic salt (e.g. ZnCl2 + choline chloride)
Type II Eutectic (metal salt hydrate + organic salt (e.g. CoCl2*6H2O + choline chloride)
Type III Eutectic (organic salt + hydrogen bond donor (e.g. choline chloride + urea)
Type IV Eutectic (metal salt (hydrate) + hydrogen bond donor (e.g. ZnCl2 + urea)


Choline:
Code:
Hydrogen Bond Acceptor: Hydrogen Bond Donor (MOLAR RATIO) Choline Acetate 1:1.5 Glycerol choline fluoride 1:2 Urea choline nitrate 1:2 Urea choline chloride 1:2 1-methylurea Choline Chloride : Imidazole 3:7 56 Degrees C choline chloride 1:2 acetamide choline chloride 1:2.5 2,2,2-trifluoroacetamide choline chloride 1:3 1,4-butanediol ChCl 1:2 Glycine ChCl 1:1 glucose ChCl 1:1 xylitol ChCl 1:1 sorbitol ChCl 1:2 urea ChCl 1:2 ethylene glycol ChCl:glucose:glycerol 1:0.5:0.5 ChCl:xylitol:glycerol 1:0.5:0.5 ChCl:sorbitol:glycerol 1:0.5:0.5 ChCl 1:2 Glycerol ChCl 1:2 Malonic Acid ChCl 1:2 Phenylacetic Acid ChCl 1:2 Oxalic Acid ChCl 1:2 Propionic Acid ChCl 1: 2 Resorcinol ChCl 1:2 Acetic Acid ChCl 4:1 Lactic Acid ChCl 4:1 Glucose ChCl 4:1 Fructose ChCl 4:1 Sucrose ChCl 4:1 Raffinose ChCl 4:1 Maltose ChCl 4:1 Mannitol ChCl 4:1 Lactose ChCl 4:1 Sorbitol Lactic Acid 1:1.2 - 1.2:1 Choline Chloride


Metal Salts:
Code:
Hydrogen Bond Donor : Hydrogen Bond Acceptor (MOLAR RATIO) [BMIm]Cl 1:1 LiCl NH4Al(SO4)2 7:2 Urea Al(NO3)3 2:2.3 Urea AlCl3 anhydrous 2.4:2 Urea AlCl3 anhydrous 2.4:2 Acetamide K2CO3 1:5 Glycerol K2CO3 1:6 ethylene glycol ChCl 1:2 CrCl3 ethylene glycol 4: 1 ZnCl2 ethylene glycol 4: 1 SnCl2 ethylene glycol 4: 1 FeCl3 urea 4:1 ZnCl2 urea 7:2 ZnCl2 urea 7:2 SnCl2 urea 7:2 FeCl3 urea 7:2 CrCl3 AlCl3 anhydrous 2:1 Urea acetamide 4:1 ZnCl2



Sugars:
Code:
Hydrogen Bond Donor : Hydrogen Bond Acceptor Saccarose/Urea/CaCl2 70:20:10 w/w% Sorbit/Urea/NH4Cl 70:20:10 w/w% Glucose/Dimethylurea/NH4Cl 50:40:10 w/w% Glucose/Urea/NH4Cl 60:30:10 w/w% Fructose/Urea/NaCl 70:20:10 w/w% Maltose/Dimethylurea/NaCl 50:40:10 w/w% Sorbit/Dimethylurea/NH4Cl 70:20:10 w % Citric acid/ Dimethylurea 40:60 w% Lactose/Dimethylurea/NH4Cl 60:30:10 w % Mannose/Dimethylurea 30:70 w % Maltose/Dimethylurea/NaCl 50:40:10 w%


Acids:
Code:
Hydrogen Bond Donor : Hydrogen Bond Acceptor (MOLAR RATIO) choline chloride phenylacetic acid 1:2 choline chloride phenylpropionic acid 1:2 choline chloride glutaric acid 1:1 choline chloride glycolic acid 1:1 choline chloride levulinic acid 1:2 choline chloride itaconic acid 1:1 choline chloride l-(+)-tartaric acid 1:0.5 Lactic Acid 9:1 Alanine Lactic Acid 2:1 Betaine Lactic Acid 1.3 : 1 - 15:1 Choline Chloride Lactic Acid 1:9 Glycine Lactic Acid 5:1 - 9:1 Histidine Lactic Acid 1:1 - 4:1 Proline Malic Acid 1:1 Alanine Malic Acid 1:1 Betaine Malic Acid 1:1.2 - 1.2:1 Choline Chloride Malic Acid 1:1 Glycine Malic Acid 1:1-2:1 Histidine Malic Acid 9:1 Nicotinic Acid Malic Acid 1:3 - 3:1 Proline Oxalic Acid (Anhydrous) 1:1 Alanine Oxalic Acid (Anhydrous) 1 : 1.5 - 1.5:1 ChCl Oxalic Acid (Anhydrous) 1:1 - 1.5:1 Proline Oxalic Acid (Dihydrate) 2:1 Alanine Oxalic Acid (Dihydrate) 1 :1 Betaine Oxalic Acid (Dihydrate) 1:1 Choline Chloride Oxalic Acid (Dihydrate) 1:1 - 3:1 Glycine Oxalic Acid (Dihydrate) 1 :1 Histidine Oxalic Acid (Dihydrate) 1:1 Proline Oxalic Acid (Dihydrate) 9:1 Nicotinic Acid


Misc.
Code:
menthol 5:5 camphor








[Edited on 30-4-2015 by gatosgr]

j_sum1 - 30-4-2015 at 03:36

Gorgeous. Thanks for doing this. I think there are some here that I will have to try. Urea and zinc chloride is very accessible.
What is your source for this information?

These are fascinating in my view and there are some really interesting potential applications.
Sorry, no additional info to add but I am bookmarking this list as a reference.

WGTR - 30-4-2015 at 04:21

I. http://www.sigmaaldrich.com/chemistry/chemistry-products.htm...
II. Attachment: al_chemfile_v5_n6.pdf (2.4MB)
This file has been downloaded 1647 times

gatosgr - 30-4-2015 at 04:36

I've got these ratios from research papers and patents, the ZnCl2 I used was hydrated you need 353K.

That sigma list is long but those ILs are not easy to make.

If you want to reduce viscosity most of the times either glycerol or MEG will work at different ratios.


[Edited on 30-4-2015 by gatosgr]

WGTR - 30-4-2015 at 09:53

Quote: Originally posted by gatosgr  

That sigma list is long but those ILs are not easy to make.

If you want to reduce viscosity most of the times either glycerol or MEG will work at different ratios.



It depends on how one defines "not easy to make". A lot of them are straightforward if certain starting materials are purchased. Most of the time, only common labware is needed to perform the synthesis.

The main questions, I suppose, are what function does one want the ionic liquid to perform, and what parameters are important? Viscosity, hydrophobicity, electrochemical window, melting point, chemical stability, solubility in various solvents, and much more; these are some parameters considered when selecting an ionic liquid.

An ionic liquid like 1-butyl-3methylimidazolium hexafluorophosphate sounds intimidating, but it can be made by refluxing 1-methylimidazole with butyl chloride for week or so, and then reacting the purified product with sodium hexafluorophosphate. The ionic liquid separates out from the water, and the sodium chloride gets washed out with the water. Repeated washings with Na-PF6 and fresh water help remove residual chloride ions. It can be dried for the most part under vacuum, but it tends to hang on to residual water in the amount of 100-300 ppm.

The end goal of a lot of my little projects here is to perform a total synthesis on an imidazolium-based ionic liquid...just for fun. Eventually I'll post it here.

Endo - 30-4-2015 at 09:57

Here are more using imidazole. See: http://www.sciencedirect.com/science/article/pii/S0167732208001529

Choline Chloride : Imidazole 3:7 56 Degrees C.

The other two listed in the paper are not so easy to get.

papaya - 30-4-2015 at 10:50

There's also ethyl-, methyl imadazolum salts (acetate, phosphate, etc) in case you didn't know it, also was some based on LiCL/DMF or tetrabuthylammonium chloride/DMF or DMSO, don't remember exactly with which one exactly

gatosgr - 1-5-2015 at 09:15

Can some moderator replace the first post with this updated post? I've added a lot more combinations. :D
Quote:

I thought about making a list of all the known combinations for deep eutectic solvents and ionic liquids, if you know of any others please post them here. :D

There are four types of eutectic solvents:
Type I Eutectic (metal salt + organic salt (e.g. ZnCl2 + choline chloride)
Type II Eutectic (metal salt hydrate + organic salt (e.g. CoCl2*6H2O + choline chloride)
Type III Eutectic (organic salt + hydrogen bond donor (e.g. choline chloride + urea)
Type IV Eutectic (metal salt (hydrate) + hydrogen bond donor (e.g. ZnCl2 + urea)


Choline:

Code:
Hydrogen Bond Acceptor: Hydrogen Bond Donor (MOLAR RATIO) choline chloride 1:2 ZnBr2 anhydrous Choline Acetate 1:1.5 Glycerol choline acetate 1:2 urea choline acetate 1:2 ethylene glycol choline fluoride 1:2 Urea choline nitrate 1:2 Urea choline chloride 1:2 1-methylurea Choline Chloride : Imidazole 3:7 56 Degrees C choline chloride 1:2 acetamide choline chloride 1:2.5 2,2,2-trifluoroacetamide choline chloride 1:3 1,4-butanediol ChCl 2:1 Zn(NO3)2 ChCl 1:2 MgCl2 ChCl 1:2 SnCl2 ChCl 1:2 ZnCl2 ChCl SnCl2 ZnCl2 1:1:1 ChCl 1:2 CrCl3 ChCl 1:2 Glycine ChCl 1:1 glucose ChCl 1:1 xylitol ChCl 1:1 sorbitol ChCl 1:2 urea ChCl 1:2 ethylene glycol ChCl:glucose:glycerol 1:0.5:0.5 ChCl:xylitol:glycerol 1:0.5:0.5 ChCl:sorbitol:glycerol 1:0.5:0.5 ChCl 1:2 Glycerol ChCl 1:2 Malonic Acid ChCl 1:2 Phenylacetic Acid ChCl 1:2 Oxalic Acid ChCl 1:2 Propionic Acid ChCl 1: 2 Resorcinol ChCl 1:2 Acetic Acid ChCl 4:1 Lactic Acid ChCl 4:1 Glucose ChCl 4:1 Fructose ChCl 4:1 Sucrose ChCl 4:1 Raffinose ChCl 4:1 Maltose ChCl 4:1 Mannitol ChCl 4:1 Lactose ChCl 4:1 Sorbitol Lactic Acid 1:1.2 - 1.2:1 Choline Chloride choline chloride 1:2 d-isosorbide choline chloride 1:3 phenol choline chloride 1:3 o-cresol choline chloride 1:3 xylenol


Metal Salts:
Code:
Hydrogen Bond Donor : Hydrogen Bond Acceptor (MOLAR RATIO) NH4Al(SO4)2 7:2 Urea Al(NO3)3 2:2.3 Urea AlCl3 anhydrous 2.4:2 Urea AlCl3 anhydrous 2.4:2 Acetamide AlCl3 anhydrous 1:1 Acetamide K2CO3 1:5 Glycerol K2CO3 1:6 ethylene glycol ethylene glycol 4: 1 ZnCl2 ethylene glycol 4: 1 SnCl2 ethylene glycol 4: 1 FeCl3 urea 4:1 ZnCl2 urea 7:2 ZnCl2 urea 7:2 SnCl2 urea 7:2 FeCl3 urea 7:2 CrCl3 urea 7.4:1 CaCl2 AlCl3 anhydrous 2:1 Urea [BMIM]Cl ZnCl2 acetamide 1:1:1 [BMIM]Cl ZnBr2 acetamide 2:1:1 acetamide 4:1 ZnCl2 [BMIm]Cl 1:1 LiCl [BMIm]Cl 1:2 ZnCl2 urea ZnBr2 1-butyl-3-methylimidazolium bromide 2:1:1 glycerol ZnBr2 1-butyl-3-methylimidazolium chloride 2:1:1 acetamide ZnCl2 1-butyl-3-methyl-imidazol-mixed 1:1:1 [BMIm]Cl 1:2 TiCl4 ? [BMIm]Cl 1:2 AlCl3 anhydrous ?



Sugars:
Code:
Hydrogen Bond Donor : Hydrogen Bond Acceptor Saccarose/Urea/CaCl2 70:20:10 w/w% Sorbit/Urea/NH4Cl 70:20:10 w/w% Glucose/Dimethylurea/NH4Cl 50:40:10 w/w% Glucose/Urea/NH4Cl 60:30:10 w/w% Fructose/Urea/NaCl 70:20:10 w/w% Maltose/Dimethylurea/NaCl 50:40:10 w/w% Sorbit/Dimethylurea/NH4Cl 70:20:10 w % Citric acid/ Dimethylurea 40:60 w% Lactose/Dimethylurea/NH4Cl 60:30:10 w % Mannose/Dimethylurea 30:70 w % Maltose/Dimethylurea/NaCl 50:40:10 w%


Acids:
Code:
Hydrogen Bond Donor : Hydrogen Bond Acceptor (MOLAR RATIO) Citric Acid 1:1,1:2,1:3 Proline Lactic Acid 9:1 Alanine Lactic Acid 2:1 Betaine Lactic Acid 1.3 : 1 - 15:1 Choline Chloride Lactic Acid 1:9 Glycine Lactic Acid 5:1 - 9:1 Histidine Lactic Acid 1:1 - 4:1 Proline Acotinic Acid 1:1 Chloride Malic Acid 1:1 Alanine Malic Acid 1:1 Betaine Malic Acid 1:1.2 - 1.2:1 Choline Chloride Malic Acid 1:1 Glycine Malic Acid 1:1-2:1 Histidine Malic Acid 9:1 Nicotinic Acid Malic Acid 1:3 - 3:1 Proline Oxalic Acid (Anhydrous) 1:1 Alanine Oxalic Acid (Anhydrous) 1 : 1.5 - 1.5:1 ChCl Oxalic Acid (Anhydrous) 1:1 - 1.5:1 Proline Oxalic Acid (Dihydrate) 2:1 Alanine Oxalic Acid (Dihydrate) 1 :1 Betaine Oxalic Acid (Dihydrate) 1:1 Choline Chloride Oxalic Acid (Dihydrate) 1:1 - 3:1 Glycine Oxalic Acid (Dihydrate) 1 :1 Histidine Oxalic Acid (Dihydrate) 1:1 Proline Oxalic Acid (Dihydrate) 9:1 Nicotinic Acid choline chloride phenylacetic acid 1:2 choline chloride phenylpropionic acid 1:2 choline chloride glutaric acid 1:1 choline chloride glycolic acid 1:1 choline chloride levulinic acid 1:2 choline chloride itaconic acid 1:1 choline chloride l-(+)-tartaric acid 1:0.5 dl-Malic acid d-Xylose 1:1a dl-Malic acid d-(+)-Glucose 1:1, 1:2 dl-Malic acid Sucrose 1:1 dl-Malic acid d-(−)-Fructose 1:1 dl-Malic acid d-Mannose 1:1 dl-Malic acid Sucrose 1:1, 2:1 dl-Malic acid Maltose 2:1 dl-Malic acid d-(+)-Trehalose 2:1 dl-Malic acid Lactose 2:1, 1:1 dl-Malic acid Raffinose 3:1a dl-Malic acid Xylitol 1:1a dl-Malic acid Adonitol 1:1a dl-Malic acid d-Sorbitol 1:1 dl-Malic acid d-(+)-Glucose d-(−)-Fructose 1:1:1 dl-Malic acid d-(+)-glucose Glycerol 1:1:1 dl-Malic acid Sucrose Glycerol 1:1:2 dl-Malic acid l-Proline Choline chloride 1:1:1 Citric acid d-Xylose 1:1 Citric acid d-(+)-Glucose 2:1 Citric acid d-(−)-Fructose 1:1 Citric acid Sorbose 1:1 Citric acid d-(+)-Galactose 1:1a Citric acid Sucrose 1:1 Citric acid Maltose 2:1 Citric acid d-(+)-Trehalose 2:1 Citric acid Raffinose 3:1 Citric acid d-Sorbitol 1:1 Citric acid Ribitol 1:1 Citric acid Xylitol 1:1 Citric acid Adonitol 1:1 Citric acid l-Proline 1:1, 1:2, 1:3 Citric acid dl-Malic acid 1:1a Phytic acid sodium Betaine 1:6 Phytic acid sodium dl-Malic acid 1:6 Phytic acid sodium Glycerol 1:6 Phytic acid sodium l-Proline 1:6 Phytic acid sodium d-(+)-Glucose 1:6 Phytic acid sodium Choline chloride 1:3


Ammonium Salts:
Code:
Hydrogen Bond Donor : Hydrogen Bond Acceptor (MOLAR RATIO) NH4Cl 1:2 urea 286.51 Degrees C methanaminium chloride 1:2 urea 210.28 Degrees C dimethylammonium chloride 1:2 urea 123. 61 Degrees C trimethylammonium chloride 1:2 urea 215.12 Degrees C tetramethylammonium chloride 1:2 urea 240.06 Degrees C dodecyltrimethylammonium chloride 1:2 urea 145.75 Degrees C hexadecyltrimethylammonium chloride 1:2 urea 120.09 Degrees C phenyltrimethylammonium chloride 1:2 urea 213.16 Degrees C benzyltrimethylammonium chloride 1:2 urea 180.48 Degrees C (vinylbenzyl)trimethylammonium chloride 1:2 urea 170.55 Degrees C


Organic Compounds:
Code:
Hydrogen Bond Donor : Hydrogen Bond Acceptor (MOLAR RATIO) (Betaine is Trimethylglycine a Zwitterion) Trimethylglycine urea 1:2 Trimethylglycine glycolic acid 1:2 Trimethylglycine glycerin 1:2 Betaine d-(+)-Glucose 5:2 Betaine Sucrose 4:1, 1:1 Betaine Sucrose 2:1 Betaine d-(+)-Trehalose 4:1 Betaine d-Sorbitol 3:1 Betaine dl-Malic acid 1: Betaine l-(+)-Tartaric acid 2:1 Betaine d-Mannose 5:2 Betaine Inositol Raffinose 9:1:1 Betaine Sucrose Proline 1:1:1 Betaine Sucrose Proline 5:2:2 Betaine d-(+)-Glucose Proline 1:1:1 Betaine dl-Malic acid d-(+)-Glucose 1:1:1 Betaine dl-Malic acid Proline 1:1:1 Betaine dl-Malic acid Inositol 1:1:1 Betaine Oxalic acid d-(+)-Glucose 1:1:1 Betaine Citric acid 1:1 d/l-Proline Sucrose 2:1, 3:1 d/l-Proline Sucrose 4:1,1:1a d/l-Proline d-Sorbitol 1:1 d/l-Proline d-(+)-Glucose 1:1, 5:3 d/l-Proline Lactic acid 1:1 d/l-Proline dl-Malic acid 1:1 d/l-Proline Citric acid 1:1, 2:1 d/l-Proline Malonic acid 1:1a d-Proline d-(+)-Glucose 5:3 l-Proline d-(+)-Glucose 5:3 l-Serine dl-Malic acid 3:2, 1:1 l-Serine d-(+)-Glucose 5:4a l-Glutamic salt Sucrose 2:1 l-Glutamic salt d-(+)-Glucose 1:1 d-(+)-Glucose dl-Malic acid 1:1a d-(+)-Glucose Citric acid 1:1 d-(+)-Glucose l-(+)-Tartaric acid 1:1 d-(+)-Glucose d-(−)-Fructose Sucrose 1:1:1a d-(−)-Fructose Sucrose 1:1 beta-Alanine dl-Malic acid 3:2, 1:1 beta-Alanine Citric acid 1:1



Misc.
Code:
Hydrogen Bond Donor : Hydrogen Bond Acceptor (MOLAR RATIO) menthol 5:5 camphor 2-acetyloxy-N,N,N-trimethylethanaminium chloride ZnBr2 anhydrous 1:2 2-acetyloxy-N,N,N-trimethylethanaminium chloride SnCl2 1:2 N-(2-hydroxyethyl)-N,N-dimethylanilinium chloride SnCl2 1:2 N-(2-hydroxyethyl)-N,N-dimethylanilinium chloride FeCl3 1:2 N-ethyl-2-hydroxy-N,N-dimethylethanaminium chloride urea 1:2 N-benzyl-2-hydroxy-N,N-dimethylethanaminium cloride urea 1:2 N,N,N-trimethyl(phenyl)methanaminium chloride urea 1:2 2-(acetyloxy)-N,N,N-trimethylethanaminium chloride urea 1:2 2-chloro-N,N,N-trimethylethanaminium chloride urea 1:2 N-benzyl-2-hydroxy-N-(2-hydroxyethyl)-N-methylethanaminium chloride urea 1:2 2-fluoro-N,N,N-trimethylethanaminium bromide urea 1:2 ethylammonium chloride urea 1:1.5 ethylammonium chloride methylurea 1:1.5 ethylammonium chloride 1-(trifluoromethyl)urea 1:1.5 tetrabutylammonium bromide imidazole 3:7 1-ethyl-3-butylbenzotriazolium hexafluorophosphate imidazole 1:4 tetrabutylammonium chloride glycerol 1:5 tetrabutylammonium chloride ethylene glycol 1:3 tetrabutylammonium chloride triethylene glycol 3:1 methyltriphenylphosphonium bromide glycerol 1:3 methyltriphenylphosphonium bromide ethylene glycol 1:4 methyltriphenylphosphonium bromide triethylene glycol 1:5.25 N,N-diethylethanolammonium chloride glycerol 1:2 N,N-diethylethanolammonium chloride ethylene glycol 1:2 N,N-diethylethanolammonium chloride triethylene glycol 1:2 methyltriphenylphosphonium bromide glycerol 1:3 methyltriphenylphosphonium bromide ethylene glycol 1:4 methyltriphenylphosphonium bromide triethylene glycol 1:5 methyltriphenylphosphonium bromide 2,2,2-trifluoroacetamide 1:8 benzyltriphenylphosphonium chloride glycerol 1:5 benzyltriphenylphosphonium chloride ethylene glycol 1.3 tetrapropylammonium bromide glycol 1:3 tetrapropylammonium bromide ethylene glycol 1:4 tetrapropylammonium bromide triethylene glycol 1:3 lithium bis[(trifluoromethyl)sulfonyl]imide N-methylacetamide 1:4 1-butyl-3-methylimidazolium chloride ZnCl2 1:1






[Edited on 1-5-2015 by gatosgr]

Reduce DES viscosity

Leonardjanus - 5-11-2015 at 13:47

Someone has report of reducing DES viscosity with Dichlorometane?

For example this methods work for to reduce viscosity and increase conducibility of an electrolyte made with Propylene Carbonate + Lithium Perchlorate.
Dichlorometane do not react with this electrolyte but is similar to an emulsion.

MrHomeScientist - 5-11-2015 at 14:00

An extensive and helpful list to be sure, but information on each liquid's properties would be much more helpful. Melting point, viscosity, and reactivity particularly! Otherwise it's just a list of names, really.

aga - 5-11-2015 at 14:40

Harsh MrHS. Harsh.

The List at least provides a Starting Point if one were interested in deep eutectic solvents/mixtures.

careysub - 5-11-2015 at 14:52

Good list, but at least the MP of eutectic please!

aga - 5-11-2015 at 14:59

Yes.

The MP of each eutectic would make the List far more interesting.

Edit:

Exciting even !

[Edited on 5-11-2015 by aga]

DeIonizedPlasma - 19-11-2015 at 11:28

I believe the eutectic ratio you have for Choline Chloride and Malonic Acid is incorrect. I just tried making some but the ratio seems to be 1:1 rather than 1:2, and this agrees with every paper I have found on the matter.

BOD513 - 15-2-2016 at 11:22

Type IV eutectics (metal chloride + hydrogen bond donor) are always described in papers as metal chloride (hydrate) and a hydrogen bond donor, but these descriptions are usually in the introduction sections of papers that disregard that and use anhydrous salts. Ive found one paper describing the use of CrCl3 hexahydrate, but never one about this magical AlCl3 hydrate/urea solvent that is always talked about- there was even a topic here a while back where someone reported difficulty making a type IV with a hydrated salt and another user told them that the hydrates are basically useless. In my own experience I can't seem to get zinc chloride hydrate and urea to work in various ratios.

Has anybody here successfully made a type IV with a hydrate? In people's experience, are any of the "recipes" in this thread referring to hydrate salts? The use of hydrates, especially the more temperature stable ones like zinc and manganese, is attractive because of the lower viscosity and higher conductivity of type II solvents compared to the corresponding type I's.

gatosgr - 24-2-2016 at 01:59

Hello, I know that it's just a list of names but I've made my own eutectic solvents by using that list , in order to reduce viscosity one could try adding glycerin or ethyl glycol depending on what you're trying to make, the ZnCl2 + Urea DES was the first one I made, I believe it was 1:4 molar ratio and it was hydrated because I didn't keep it sealed. The AlCl3 must be in anhydrous form as far as I remember. The hydrates I've tried are SnCl2 and ZnCl2.

I might add melting temperatures if I can find them later on, another point to consider is that with ternary systems the step of addition matters. I've found that using a pyrex tube over a bunsen burner is much better to using beakers especially for smaller quantities.
Quote: Originally posted by DeIonizedPlasma  
I believe the eutectic ratio you have for Choline Chloride and Malonic Acid is incorrect. I just tried making some but the ratio seems to be 1:1 rather than 1:2, and this agrees with every paper I have found on the matter.


I will correct the list if the moderators let me.

It should be
ChCl 1:1 Malonic acid
ChCl 1:1 Oxalic acid

Most of the solvents have room for improvement I mean if you adjust the ratio a little bit you will get different viscosity that's why you see some papers quoting 1:2 ratio and some others 1:1 ratio.

[Edited on 24-2-2016 by gatosgr]

gatosgr - 14-5-2016 at 12:08

Just an insight on the deep eutectic solvents with metal hydrates(Some will work with other hydrogen donors Urea e.t.c.):

Preparation of deep eutectic solvent [ChCl][CrCl3·6H2O]2. A mixture of the
chromium(iii) chloride hexahydrate (CrCl3·6H2O) and choline chloride in a molar
ratio of 2:1 was heated to 70℃ with gentle stirring until a green liquid formed.

Preparation of deep eutectic solvent [ChCl][FeCl3]2. A mixture of the ferric
chloride (FeCl3) and choline chloride in a molar ratio of 2:1 was heated to 100℃ with
gentle stirring until a dark brown liquid formed.

Preparation of deep eutectic solvent [ChCl][AlCl3·6H2O]2. A mixture of the
aluminum chloride hexahydrate (AlCl3·6H2O) and choline chloride in a molar ratio of
2:1 was heated to 70℃ with gentle stirring until a colorless liquid formed.

Preparation of deep eutectic solvent [ChCl][MgCl2·6H2O]2. A mixture of the
magnesium chloride hexahydrate (MgCl2·6H2O) and choline chloride in a molar ratio
of 2:1 was heated to 70℃ with gentle stirring until a green clear liquid formed.

Preparation of deep eutectic solvent [ChCl][MnCl2·4H2O]2. A mixture of the
manganese(II) chloride tetrahydrate (MnCl2·4H2O) and choline chloride in a molar
ratio of 2:1 was heated to 70℃ with gentle stirring until a pink liquid formed.

Preparation of deep eutectic solvent [ChCl][CoCl2·6H2O]2. A mixture of the
cobalt(II) chloride hexahydrate (CoCl2·6H2O) and choline chloride in a molar ratio of
2:1 was heated to 70℃ with gentle stirring until a blue liquid formed.


Preparation of deep eutectic solvent [ChCl][NiCl2·6H2O]2. A mixture of the nickel
chloride hexahydrate (NiCl2·6H2O) and choline chloride in a molar ratio of 2:1 was
heated to 70℃ with gentle stirring until a green liquid formed.

Preparation of deep eutectic solvent [ChCl][CuCl2·2H2O]2. A mixture of the
cupric chloride (CuCl2·2H2O) and choline chloride in a molar ratio of 2:1 was heated
to 70℃ with gentle stirring until a brown liquid formed.

Preparation of deep eutectic solvent [ChCl][ZnCl2]2. A mixture of the Zinc
chloride (ZnCl2) and choline chloride in a molar ratio of 2:1 was heated to 100℃ with
gentle stirring until a colorless liquid formed.

Preparation of deep eutectic solvent [ChCl][SnCl2]2. A mixture of the anhydrous
stannous chloride (SnCl2) and choline chloride in a molar ratio of 2:1 was heated to
100℃ with gentle stirring until a colorless liquid formed.

[Edited on 14-5-2016 by gatosgr]

Aztral - 8-12-2016 at 17:29

Hey there.

I'm a newbie here and my first post :o
On hand I've been working on filling-out a spreadsheet, so I thought I'd share.
Not much here but as I get more data I can update
Code:
DES halide salt mp/C hbd mp/C salt/hbd Ratio MP Tf/°C Viscosity Conduc mS*cm^1 Potential Window ref ChCl 303 urea 134 1:2 12 750 (25°C) 0.20 (40°C) 13 ChCl 303 thiourea 175 1:2 69 12 ChCl 303 1-methyl urea 93 1:2 29 12 ChCl 303 "1,3-dimethyl urea" 102 1:2 70 12 ChCl 303 "1,1-dimethyl urea" 180 1:2 149 12 ChCl 303 acetamide 80 1:2 51 12 ChCl 303 banzamide 129 1:2 92 12 ChCl 303 ethylene glycol -12.9 1:2 37 (25°C) 7.61 (20°C) ChCl 303 glycerol 17.8 -35 359 (25°C) 1.05 (20°C) ChCl 303 phenol -40 ChCl 303 adipic acid 153 1:1 85 13 ChCl 303 benzoic acid 122 1:1 95 13 ChCl 303 citric acid 149 1:1 69 13 ChCl 303 malonic acid 134 1:1 10 13 ChCl 303 oxalic acid 190 1:1 34 13 ChCl 303 phenylacetic acid 77 1:1 25 13 ChCl 303 phenylpropionic acid 48 1:1 20 13 ChCl 303 succinic acid 185 1:1 71 13 ChCl 303 tricarballylic acid 159 1:1 90 13 ChCl 303 MgCl2?6H2O 116 1:1 16 42 methyltriphenylphosphonium bromide 231-233 glycerol 17.8 -4.03 44 methyltriphenylphosphonium bromide 231-233 ethylene glycol -12.9 -49.34 44 methyltriphenylphosphonium bromide 231-233 "2,2,2-trifluoroacetamide" 73-75 -69.29 44 benzyltriphenylphosphonium chloride 345-347 glycerol 17.8 50.36 44 benzyltriphenylphosphonium chloride 345-347 ethylene glycol -12.9 47.91 44 benzyltriphenylphosphonium chloride 345-347 "2,2,2-trifluoroacetamide" 73-75 99.72 44 ZnCl2 ChCl 1:1 3.74 V http://www.sciencedirect.com/science/article/pii/S0167732215000367 ZnCl2 ChCl 1:2 89 ZnCl2 ChCl 1:1.5 42.85 ZnCl2 293 urea 134 9 ~2.0V 21 ZnCl2 293 acetamide 81 -16 21 ZnCl2 293 ethylene glycol -12.9 -30 ~2.0V 21 ZnCl2 293 hexanediol 42 -23 21 ethylammonium chloride (EtNH3Cl) CF3CONH2 1:1.5 256 (40°C) 0.39 (40°C) ethylammonium chloride (EtNH3Cl) Acetamide 80 1:1.5 64 (40°C) 0.69 (40°C) ethylammonium chloride (EtNH3Cl) urea 134 1:1.5 128 (40°C) 0.35 (40°C) AcChCl urea 134 1:2 2214 (40°C) 0.02 (40°C)

gatosgr - 10-1-2017 at 08:33

Any contribution is welcome. :D

Synthesis of Type 2 DES (Choline chloride-Mgcl2.6H2O)

eknew2 - 3-4-2017 at 20:34

Hi guys,
I was trying to synthesize Type 2 DES by mixing choline chloride and Mgcl2.6H2O (molar ratio of 1:2).

I mixed them in a 150 ml schott bottle (tightly closed with cap), at bath temperature of 90 C, and magnetic stirring. I was able to get liquid after approximately 1 hour of stirring. However, I was not able to get a colorless (transparent) liquid, despite after stirring for 48 hours. The color of the liquid that I have always obtained is milky white. Nevertheless, this synthesized DES should be a colorless liquid. I have even tried the same procedures for molar ratio of 1:1, 1:1.5, 1.5:1, 2:1 . But still, nothing gets better.

Therefore, i could not synthesize the respective DES. I'm very sure that the chemicals are pure enough (>98%) and no contamination as well as not up to expiry date yet.

Does anyone know how to synthesize this Type 2 DES of choline chloride and Mgcl2.6H2O ? I really really need help. :(

Thank you very much for assisting me :)

Regards,
Ken

[Edited on 4-4-2017 by eknew2]

gatosgr - 4-4-2017 at 10:54

Here is the reference for the MgCl2 DES: http://www.rsc.org/suppdata/c6/ra/c6ra01029f/c6ra01029f1.pdf

These solvents tend to be white when the ratio is not optimal.

clearly_not_atara - 4-4-2017 at 12:42

Quote:
The color of the liquid that I have always obtained is milky white. Nevertheless, this synthesized DES should be a colorless liquid. I have even tried the same procedures for molar ratio of 1:1, 1:1.5, 1.5:1, 2:1 . But still, nothing gets better.


I am sorta guessing here, but since MgCl2 and ChCl are both white powders, it seems plausible that you have made a certain quantity of the eutectic liquid with some excess salt suspended therein. Maybe try passing through a very fine mesh filter and see if it gets any clearer/there is a filter cake. If filtration is incomplete, but solids are obtained, you can examine them to determine which salt is present in excess, and adjust the ratio by adding a little of the other.

CrossxD - 9-4-2017 at 01:36

Where can I buy some of that choline?

stamasd - 31-7-2018 at 08:35

I guess you could add to the list the combination I'm working with now, KCr(SO4)2.12H2O : Urea, 1:2 molar ratio (type 4 DES). I posted about it in the main DES thread.

Also I plan on working soon with another DES, ChCl:propylene glycol 1:2 (type 3 DES) which I don't see posted in the list above (it's easier for me to obtain high purity propylene glycol than ethylene glycol, and much less toxic)

gatosgr - 18-10-2018 at 11:13

Quote: Originally posted by stamasd  
I guess you could add to the list the combination I'm working with now, KCr(SO4)2.12H2O : Urea, 1:2 molar ratio (type 4 DES). I posted about it in the main DES thread.

Also I plan on working soon with another DES, ChCl:propylene glycol 1:2 (type 3 DES) which I don't see posted in the list above (it's easier for me to obtain high purity propylene glycol than ethylene glycol, and much less toxic)


Sorry but I can't edit these post as they are very old, this thead used to show first page at google for deep eutectic solvents but now with so much research going into DES I guess it got lost somewhere.

Something that no one mentions is that reactions can take place when making the DES solvent, I haven't found any research regarding this matter but again I am not into organic synthesis at all, I've only done organic 1 and some organic 2 at university. I've noticed it when using amino acids there are some type of condensation reactions going on but I don't know about the mechanism involved, I have used it when incorporating a sulfur center in the solution , I guess some structures are very prone to side reactions especially with destabilized aminoacids, I don't know the isoelectric point of DES solutions but I guess that would be one way to guess the reactivity. Some organic junkies must have found better ways to measure these stuff.

[Edited on 18-10-2018 by gatosgr]