Predicting Solubilities of Cellulose in Ionic Liquids using COSMO-RS

Kai Masuch, Kai Leonhard, Jens Kahlen

Why predict cell. solubilities?

Tree: lignin, hemicellulose, cellulose, other stuff we dont want (e.g. water) cellulose: hydrogen-bonding hinders conversion to liquid.. ...which can be overcome when dissolved in appropriate solvents...

...e.g. ionic liquids (ILs)... ...which are trendy and referred as green by marketing strategists (negligible vapor pressure). Cations and anion can be combined freely: numerous (!!!) candidates.

Why COSMO-RS?

solubility (in general) can be predicted by COSMO-RS fast (contrary to MD and full scale ab-initio methods for liquids) huge database for screening purposes fully predictive due to previous ab-inito calculations for each molecule (contrary to group contribution methods e.g. UNIFAC)

nice colours (simplifies understanding of interactions) (Luckily) many weak points of COSMO-RS are touched:

Combinatorial entropy for polymers Electrolytes in general (no long range electrostatics) Hydrogen bonds Atomic ions

Octane

COSMO
ClH2O

COSMO: COnductor-like Screening MOdel QM-computation of surfacecharge-density in a conductor Only electrostatic interaction energy with dielectric continuum Screening charge probability distribution: sigma-profile Chemical potential is derived from sigma-profiles with COSMO-RS

Realistic Solvation COSMO (-RS)

Chemical potential:

Partition function:

Residual partition function:

COSMO-files
BMIM+

COSMO-database: 5000 neutral components Modelling Ionic Liquids: One COSMO-file for each IL, (conformers!) Combination of COSMOfiles of independent ions IL-database: 70 cations x 30 anions = 2100 ILs

ClPF6OAc-

Sigma-Profiles of Conformers

Conformers might have:

very different sigma-profiles (intramolecular bonds e.g. cellulose)

h-

very similar sigmaprofiles (Alkanes/Alkenes)

Cellulose in COSMO-RS
Dissolution

Structure for COSMO-file

(memory likewise)

(size and shape effects on entropy neglected)

pics on top: http://en.wikipedia.org/wiki/Cellulose

Weighting of atoms

Only screening surface charges of mid-unit should be used to calculate chemical potential

screening surface charges associated to atoms of end-units are excluded

Generation of conformers

Generation of cellotrioseconformers in gas phase Geometry optimization in COSMO-cavity Conformer clustering:

COSMO energies (conformer distribution by Boltzmann weighting) Similarities in sigma-profiles

Match!

(30 clusters)

Solubility-map
Anions
ba d

Guanidium+

go od

BMIM+ EMIM+/OAcClCations

Map for 0,1% Water-Content (similar to1% and 5%)

Anions

Guanidium+

Cations

BMIM+

Anions

BMIM: +H2O: 1000ppm exp.: 12% 20% 3% 2%

Data: Vitz, et.al. 09

no sol. no sol. no sol.

exp. Data: T, DP, chryst., water % = const.(!)

Anions

H-MeGu +H20 1000 ppm Hexamethylguanidinium+ Acetate-

BMIM+

Typical cation
PF6(bad)

Solubility mostly cation independent, probably due to homogenous charge distribution over large surface Solubility explanation: IL-selfassociativity when sigma-profiles of + mirrors -

Cl(good)

OAc(very good)

Guanidinium

Atypical cation
PF6(good)

G+/OAc- have strong symmetry to mirror plane: bad solubility G+/PF6- not: interaction with cellulose more likely

Cl(bad)

OAc(bad)

Summary/Outlook

Application of COSMO-RS as preselection tool for ILs dissolving cellulose ILs found which are expected to solve cellulose better than commonly used ILs... ...which seem to be highly intolerant to water (design has to include water effects) No kinetics included

Comparison with exp. Data is difficult Forthcoming transfer of the model in finite dilution might improve comparability Still degree of polymerisation and crystallinity have to be known State of aggregation for ILs should be included in the model

The End

Atomic Ions in COSMO-RS

activity of water in 1-Allyl-3-Methyl-Imidazolium-chloride

activity H2O

COSMO-RS no hb

measured (BioVT)

COSMO-RS hb H2O mol/mol

Continuum Solvation Model COSMO: COnductor-like Screening MOdel (infinite permittivity)

COSMO
H O H

electron density and screening charge: iteration to selfconsistency Dielectric solvent: scaling of screening charges by empiric function (function of permittivity) Only electrostatic interaction energy with dielectric continuum

-1.5 e/nm

+1.5 e/nm

H-Bonds + Dispersion

*
http://www.lsbu.ac.uk/water/

Solubility from COSMORS (constant for

cellulose with given DP and crystallinity) (iterative) Size/shape Basic COSMO-RS (entropy): e.g. Flory-Huggins COSMO-RS-comb. not suitable for polymers (Klamt)

Contact statistics

best typical: hexamethylguanidinium-acetate 6/30 conformers used best: weight of 83% (No.23 dE?)

best atypical: guanidinium-tris(pentafluoroethyl) trifluorophosphate 23/30 conformers used best: weight of 34%

Lignin

http://de.wikipedia.org/wiki/Lignin