Assessing the Temperature-Dependent Tunable Polarity of N,N-Dimethylcyclohexylamine (DMCHA) and Water MixturesClick to copy article linkArticle link copied!
- Ryan T. BerryRyan T. BerryChemical and Biomolecular Engineering, Lafayette College, Easton, Pennsylvania 18042-1775, United StatesMore by Ryan T. Berry
- Elizabeth DachElizabeth DachEarth and Environmental Engineering, Columbia University, New York, New York 10027-6623, United StatesMore by Elizabeth Dach
- Jessica A. MelhornJessica A. MelhornChemical and Biomolecular Engineering, Lafayette College, Easton, Pennsylvania 18042-1775, United StatesMore by Jessica A. Melhorn
- Ngai Yin YipNgai Yin YipEarth and Environmental Engineering, Columbia University, New York, New York 10027-6623, United StatesColumbia Water Center, Columbia University, New York, New York 10027-6623, United StatesMore by Ngai Yin Yip
- Lindsay Soh*Lindsay Soh*Email: [email protected]. Phone: +1-610-330-5447.Chemical and Biomolecular Engineering, Lafayette College, Easton, Pennsylvania 18042-1775, United StatesMore by Lindsay Soh
Abstract
The promise of switchable solvents as green solvent alternatives lies in the ability to drastically alter their properties based on an external trigger. Switchable hydrophilicity solvent N,N-dimethylcyclohexylamine, DMCHA, is known to change properties based on both CO2 addition and variations in temperature, both in the presence of water. While the impact of temperature has been observed via changes in water solubility, the solvent properties underlying these observations have not been quantified. Kamlet–Taft solvatochromic parameters (α, β, and π*) and dielectric constants for DMCHA and DMCHA–water mixtures were measured across a temperature range of 25–60 °C. Temperature swing effects of DMCHA in addition to CO2-switching capabilities were validated and quantified on the Kamlet–Taft polarity scale. Notably, binary mixtures of water in DMCHA show promising tunability in terms of its β and π* parameters induced by moderate variations in temperature. Potential applications for this CO2-switchable and temperature-tunable solvent are discussed.
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Creative Commons (CC): This is a Creative Commons license.
Attribution (BY): Credit must be given to the creator.
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You are free to share(copy and redistribute) this article in any medium or format within the parameters below:
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Attribution (BY): Credit must be given to the creator.
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Synopsis
DMCHA exhibits tunable properties by varying temperature and water content, which enhances its range as a potential green solvent alternative.
Introduction
Experimental Section
Chemicals and Reagents
Kamlet–Taft Parameter Determination
Spectroscopic Measurements
Water Content Measurements
Dielectric Measurements
Results and Discussion
Effect of Temperature on Kamlet–Taft Parameters
source | DMSO | cyclohexane | water | dry DMCHA |
---|---|---|---|---|
Wavenumbers for NND4 | ||||
Wyatt et al. (26) | 24.54/24.67 | 28.08 | ||
Laurence et al. (27) | 24.66 | 28.18 | 27.2 | |
Pasham et al. (14) | 23.56 | |||
this work | 24.54 | 28.14 | 23.59 | 27.14 |
Wavenumbers for 4NAi | ||||
Wyatt et al. (26) | 25.71 | 30.98 | ||
Pasham et al. (14) | 26.33 | |||
Laurence et al. (28) | 25.75 | 28.16 | ||
Kamlet and Taft (17) | 25.71 | 31.01 | 26.28 | |
this work | 25.71 | 31.04 | 26.29 | 27.99 |
Effect of Water Content on Temperature Swing Effect
π* Is a Function of Temperature and Water Content
Dielectric Constant Measurements Validate Bulk Properties
β Values Further Indicate Synergism between DMCHA and Water
Conclusions
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acssuschemeng.2c00293.
α, β, and π* values for all solvents measured in this work, sample UV–vis spectra for dry and wet DMCHA, and dielectric constants for dry and wet DMCHA (PDF)
Terms & Conditions
Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.
Acknowledgments
The authors gratefully acknowledge the financial support of the National Science Foundation (CBET#1934368) as well as the Henry Dreyfus Teacher-Scholar Award, Clare Booth Luce Program (Henry Luce Foundation, Inc) and Lafayette College EXCEL Scholars Program. Additionally, we acknowledge the support of the Research Initiatives in Science and Engineering (RISE) program of Columbia University.
References
This article references 43 other publications.
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- 16Lagalante, A. F.; Spadi, M.; Bruno, T. J. Kamlet–Taft Solvatochromic Parameters of Eight Alkanolamines. J. Chem. Eng. Data 2000, 45, 382– 385, DOI: 10.1021/je990212fGoogle Scholar16https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3cXotl2isA%253D%253D&md5=9c7afc85856a5e6fd5195cf7b2f3c9c2Kamlet-Taft Solvatochromic Parameters of Eight AlkanolaminesLagalante, Anthony F.; Spadi, Melanie; Bruno, Thomas J.Journal of Chemical and Engineering Data (2000), 45 (2), 382-385CODEN: JCEAAX; ISSN:0021-9568. (American Chemical Society)The frequency maxima of four solvatochromic probes were measured (25, 50, and 75 °C) in eight liq. alkanolamine solvents. Addnl., the indexes of refraction of the alkanolamine solvents were measured. The frequency maxima were used to calc. solvatochromic interaction parameters. The values of the solvatochromic parameters did not vary greatly from one alkanolamine to another; however, the values of the solvatochromic parameters were high, indicating strong interaction abilities in these solvents.
- 17Kamlet, M. J.; Taft, R. W. The solvatochromic comparison method. I. The .beta.-scale of solvent hydrogen-bond acceptor (HBA) basicities. J. Am. Chem. Soc. 1976, 98, 377– 383, DOI: 10.1021/ja00418a009Google Scholar17https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaE28XovFeqtA%253D%253D&md5=d5dbfaf6ec62e2a1380ae9d5cb190045The solvatochromic comparison method. I. The β-scale of solvent hydrogen-bond acceptor (HBA) basicitiesKamlet, Mortimer J.; Taft, R. W.Journal of the American Chemical Society (1976), 98 (2), 377-83CODEN: JACSAT; ISSN:0002-7863.The solvatochromic comparison method was outlined. Magnitudes of enhanced solvatochromic shifts in HBA (H-bond acceptor) solvents were detd. for 4-nitroaniline relative to N,N-diethyl-4-nitroaniline and for 4-nitrophenol relative to 4-nitroanisole [-ΔΔυ(3-4)B←HO]. The values for the HBD (H-bond donor) substrates in corresponding HBA solvents proportional to one another, proportional to limiting 19F NMR shifts of H-bonded complexes of 4-fluorophenol with the same HBA's, and linear with log association consts. of H-bonded complexes between 4-fluorophenol and PhOH and the same HBA mols. A scale of solvent HBA basicities was detd.
- 18Kamlet, M. J.; Abboud, J. L.; Taft, R. W. The solvatochromic comparison method. 6. The .pi.* scale of solvent polarities. J. Am. Chem. Soc. 1977, 99, 6027– 6038, DOI: 10.1021/ja00460a031Google Scholar18https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaE2sXlsVajurs%253D&md5=fd2206ba578969a27b790e4c709af2ffThe solvatochromic comparison method. 6. The π* scale of solvent polaritiesKamlet, Mortimer J.; Abboud, Jose Luis; Taft, R. W.Journal of the American Chemical Society (1977), 99 (18), 6027-38CODEN: JACSAT; ISSN:0002-7863.Seventy solvents are arranged in a π* scale of solvent polarities, so named because it derives from and best correlates solvatochromic effects on p → π* and π → π* electronic spectral transitions. Solvent effects on νmax values of 7 primary indicator compds. are employed in the initial construction of the π* scale, and correlations with 40 addnl. spectral indicators are used to expand and refine the data base. Std. deviations in the 47 correlation equations of νmax with solvent π* values av. 0.11 kK, which compares well with the 0.10 kK precision limit of the solvatochromic comparison method. A no. of stratagems are employed to exclude or minimize H bonding effects in detg. π* values of HBA (H bond acceptor) and amphiprotic HBA-D (H bond acceptor-donor) solvents. Values of s in the solvatochromic equation, νmax = ν0 + sπ*, show logical variations with indicator structure, lending confidence that this new solvatochromic parameter will come to serve as a convenient and meaningful indicator of the interaction of a chromophore with its cybotactic environment. Poor correlation of νmax values for Dimroth's (1963) betaine, 4-(2,4,6-triphenylpyridinium)-2,6-diphenylphenoxide with the π* scale is rationalized in terms of differing polarity and polarizability contributions to overall solvent effects.
- 19Taft, R. W.; Kamlet, M. J. The solvatochromic comparison method. 2. The .alpha.-scale of solvent hydrogen-bond donor (HBD) acidities. J. Am. Chem. Soc. 1976, 98, 2886– 2894, DOI: 10.1021/ja00426a036Google Scholar19https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaE28XksVGrsbs%253D&md5=5f3142f773168067691dbbd36ac5b284The solvatochromic comparison method. 2. The α-scale of solvent hydrogen-bond donor (HBD) aciditiesTaft, R. W.; Kamlet, Mortimer J.Journal of the American Chemical Society (1976), 98 (10), 2886-94CODEN: JACSAT; ISSN:0002-7863.The solvatochromic comparison method is used to evaluate H-bonding contributions in HBD solvents to several commonly used dye indicator solvent polarity scales (Dimroth's ET30, Brooker's χR, Kosower's Z). H-bonding effects on other spectral properties, equil., and reaction rates are detd, and the results are used to construct an α-scale of solvent HBD acidities.
- 20Kamlet, M. J.; Abboud, J. L. M.; Abraham, M. H.; Taft, R. W. Linear solvation energy relationships. 23. A comprehensive collection of the solvatochromic parameters, .pi.*, .alpha., and .beta., and some methods for simplifying the generalized solvatochromic equation. J. Org. Chem. 1983, 48, 2877– 2887, DOI: 10.1021/jo00165a018Google Scholar20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL3sXkvVOgsbc%253D&md5=99b60c3cc817d5508b28d85f3ad6c8a1Linear solvation energy relationships. 23. A comprehensive collection of the solvatochromic parameters, π*, α, and β, and some methods for simplifying the generalized solvatochromic equationKamlet, Mortimer J.; Abboud, Jose Luis M.; Abraham, Michael H.; Taft, R. W.Journal of Organic Chemistry (1983), 48 (17), 2877-87CODEN: JOCEAH; ISSN:0022-3263.A generalized equation for linear solvation energy relations or complexation energy relations is developed which involves 6 terms: π* (a solvent dipolarity-polarizability term), α (solvent hydrogen-bond acceptor term), β (solvent hydrogen-bond donor term), δ (solvent polarizability correction term), δH (Hildebrand soly. parameter), and ξ. This equation is reduced to a more manageable form by a judicious choice of solvents and reactants or indicators. One-, two- or three-parameter LFER involving different combinations of the above parameters and various types of physicochem. properties are obsd. A comprehensive collection of π*, α, and β for 217 solvents is presented.
- 21ASTM E203-96 Standard Test Method for Water Using Volumetric Karl Fischer Titration. ASTM August 16, 2017.Google ScholarThere is no corresponding record for this reference.
- 22Muller, P. Glossary of Terms Used in Physical Organic Chemistry (IUPAC Recommendations 1994). Pure Appl. Chem. 1994, 66, 1077– 1184, DOI: 10.1351/pac199466051077Google ScholarThere is no corresponding record for this reference.
- 23Baker, S. N.; Baker, G. A.; Bright, F. V. Temperature-dependent microscopic solvent properties of “dry” and “wet” 1-butyl-3-methylimidazolium hexafluorophosphate: correlation with ET(30) and Kamlet-Taft polarity scales. Green Chem. 2002, 4, 165– 169, DOI: 10.1039/b111285fGoogle Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD38XivVakt7k%253D&md5=875f197ca2fee7f58ac85823870458d5Temperature-dependent microscopic solvent properties of 'dry' and 'wet' 1-butyl-3-methylimidazolium hexafluorophosphate: correlation with ET(30) and Kamlet-Taft polarity scalesBaker, Sheila N.; Baker, Gary A.; Bright, Frank V.Green Chemistry (2002), 4 (2), 165-169CODEN: GRCHFJ; ISSN:1463-9262. (Royal Society of Chemistry)As a result of heightened awareness of a wealth of potential in clean manufg. processes, room temp. ionic liqs. (RTILs) have been the target of increased investigation. As an integral part of the green chem. movement, RTILs have found application in synthesis, catalysis, polymn., industrial cleaning, liq./liq. extn., and sepns. While some groundwork has been laid, the optimal utilization and tailoring of these solvents has been hobbled by an incomplete understanding of their solvent properties, particularly at the mol. level. In this work, we use solvatochromic measurements to det. 'energy of transition' ET(30) values and Kamlet-Taft solvent parameters (α, β, π*) for the relatively hydrophobic RTIL 1-butyl-3-methylimidazolium hexafluorophosphate, [bmim]+[PF6]-, as a function of temp. (10-70°) and water content (50 ppm or less water, 'dry' or 2% water (vol./vol.), 'wet'). The results of these expts. demonstrate that dry [bmim]+[PF6]- exhibits a hydrogen bond donor strength on the order of short chain alcs. with a linear temp. dependence. Dry and wet [bmim]+[PF6]- exhibit hydrogen bond acceptor abilities, which are weak functions of temp., intermediate between that of water and acetonitrile. The π* parameter for wet and dry [bmim]+[PF6]- is higher than short chain alcs., but lower than water or dimethylsulfoxide at ambient conditions, and it exhibits a strong linear temp. dependence. Finally, the addn. of water to [bmim]+[PF6]- does not affect the β and π* values significantly.
- 24Katritzky, A. R.; Fara, D. C.; Yang, H.; Tämm, K.; Tamm, T.; Karelson, M. Quantitative Measures of Solvent Polarity. Chem. Rev. 2004, 104, 175– 198, DOI: 10.1021/cr020750mGoogle Scholar24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXksFegsg%253D%253D&md5=f990ec3a30409cb4544f3d5fd698f0a3Quantitative Measures of Solvent PolarityKatritzky, Alan R.; Fara, Dan C.; Yang, Hongfang; Taemm, Kaido; Tamm, Tarmo; Karelson, MatiChemical Reviews (Washington, DC, United States) (2004), 104 (1), 175-198CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review focused on available quant. measures of solvent polarity. It reviews the different individual solvent scales (developed using pure solvents and based on empirical parameters) and the interrelations among them. The last section summarizes briefly the present position and the potential for future development of the concept of solvent polarity.
- 25Marcus, Y. The Properties of Organic Liquids That Are Relevant to Their Use as Solvating Solvents. Chem. Soc. Rev. 1993, 22, 409, DOI: 10.1039/cs9932200409Google Scholar25https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2cXhtVKhu7k%253D&md5=5cbfd6e363ab32daba203f8e0fdcceaeThe properties of organic liquids that are relevant to their use as solvating solventsMarcus, Y.Chemical Society Reviews (1993), 22 (6), 409-16CODEN: CSRVBR; ISSN:0306-0012.Three mutually independent quantities contribute to exoergic solute-solvent interactions: solvatochromic α (for hydrogen bond donor), β (for hydrogen bond acceptor), and π* (for polarity/polarizability) of the solvent. The main endoergic contribution, cavity formation, is measured by the cohesive energy d.
- 26Wyatt, V. T.; Bush, D.; Lu, J.; Hallett, J. P.; Liotta, C. L.; Eckert, C. A. Determination of Solvatochromic Solvent Parameters for the Characterization of Gas-Expanded Liquids. J. Supercrit. Fluids 2005, 36, 16– 22, DOI: 10.1016/j.supflu.2005.03.009Google Scholar26https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXhtVSqs77K&md5=e16a203c41e4516da673b30a2e6bbb81Determination of solvatochromic solvent parameters for the characterization of gas-expanded liquidsWyatt, Victor T.; Bush, David; Lu, Jie; Hallett, Jason P.; Liotta, Charles L.; Eckert, Charles A.Journal of Supercritical Fluids (2005), 36 (1), 16-22CODEN: JSFLEH; ISSN:0896-8446. (Elsevier B.V.)Solvatochromic shifts of six probe indicators {4-nitroaniline, 4-nitroanisole, 4-nitrophenol, N,N-dimethyl-4-nitroaniline, 4-(2,4,6-triphenylpyridinium)-2,6-diphenylphenoxide and 2,6-dichloro-4-(2,4,6-triphenyl-1-pyridinio)phenolate} have been measured in binary mixts. of carbon dioxide with acetone and methanol at 35 and 40 °C over the entire range of solvent compn. The indicators were used to specify the solvatochromic solvent parameters (ET(30), α, β, and π*), which were calcd. from the solvatochromic shifts of the max. absorbance peak (νmax) obsd. by means of UV-vis spectroscopy.
- 27Laurence, C.; Nicolet, P.; Dalati, M. T.; Abboud, J.-L. M.; Notario, R. The Empirical Treatment of Solvent-Solute Interactions: 15 Years of .pi.*. J. Phys. Chem. 1994, 98, 5807– 5816, DOI: 10.1021/j100074a003Google Scholar27https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2cXjtlagt7o%253D&md5=42e02dac26f6da01798f8fb0bba3de25The Empirical Treatment of Solvent-Solute Interactions: 15 Years of π*Laurence, Christian; Nicolet, Pierre; Dalati, M. Tawfik; Abboud, Jose-Luis M.; Notario, RafaelJournal of Physical Chemistry (1994), 98 (23), 5807-16CODEN: JPCHAX; ISSN:0022-3654.The near-UV-visible spectra of 4-nitroanisole (OMe) and N,N-dimethyl-4-nitroanilline (NMe2) were obtained at 25.0 ± 0.1° in the gas phase and in a set of 229 solvents that includes non-hydrogen-bond donors such as hydrocarbons (aliph., alicyclic, ethylenic, and arom.), perfluorinated and other halogenated hydrocarbons (arom. and nonarom.), nitriles,ketones, esters, lactones, anhydrides, amides, ureas, phosphates, HMPA, sulfates, sulfites, sulfoxides, sulfones, pyridines, and tertiary amines as well as weak hydrogen-bond donors such as nitrocompounds and primary and secondary amines. The frequencies of the absorption max. of these spectra were used to refine and critically examine the π* scale of solvent effects. The dielec. consts. and refractive indexes of the solvents (mostly from this work) were used in an Oshika-Bayliss-McRae (OBM) treatment of these frequencies that led to the following results: (i) The partitioning of dipolarity and polarizability contributions to π*; (ii) the quant. assessment of more specific contributions to π* due to arom. solvents. This study also showed the limitations of the OBM treatment and the advantages of the empirical approach. General conclusions regarding the phys. meaning and the use of scales of solvent effects (excluding hydrogen bonding) were drawn.
- 28Laurence, C.; Nicolet, P.; Helbert, M. Polarity and Basicity of Solvents. Part 2. Solvatochromic Hydrogen-Bonding Shifts as Basicity Parameters. J. Chem. Soc., Perkin Trans. 2 1986, 1081, DOI: 10.1039/p29860001081Google Scholar28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL28Xmt1Gksr8%253D&md5=d40a427717a64214063a49220cfd7082Polarity and basicity of solvents. Part 2. Solvatochromic hydrogen-bonding shifts as basicity parametersLaurence, Christian; Nicolet, Pierre; Helbert, MaryvonneJournal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999) (1986), (7), 1081-90CODEN: JCPKBH; ISSN:0300-9580.The solvatochromic H-bonding shifts of p-O2NC6H4OH (I) and p-O2NC6H4NH2 were measured by the thermosolvatochromic comparison method for an extended sample of O, N, C, halogen, and S bases. Their significance as a H-bonding parameter was tested by their correlation with formation consts., NMR shifts, vibrational shifts, and enthalpies for H-bonding formation. Family-dependent correlations are generally found between the above properties. The correlation of a H-bonding property for an OH donor vs. the same property for an NH donor is family dependent. The only significant family-independent correlation is for the solvatochromic shift of I vs. the enthalpy of H-bond formation of p-FC6H4OH. The β scale is mainly a scale of NH group H-bond acceptor basicity. The averaging process used to define β is criticized and it is recommended that correlation anal. of basicity be undertaken with clearly defined models.
- 29Wilson, A. D.; Orme, C. J. Concentration Dependent Speciation and Mass Transport Properties of Switchable Polarity Solvents. RSC Adv. 2015, 5, 7740– 7751, DOI: 10.1039/C4RA08558BGoogle Scholar29https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXitFOgtLnF&md5=a4d0ced116dc17eea37d54bac363f67fConcentration dependent speciation and mass transport properties of switchable polarity solventsWilson, Aaron D.; Orme, Christopher J.RSC Advances (2015), 5 (10), 7740-7751CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)Tertiary amine switchable polarity solvents (SPS) consisting of predominantly water, tertiary amine, and tertiary ammonium and bicarbonate ions were produced at various concns. for three different amines: N,N-dimethylcyclohexylamine, N,N-dimethyloctylamine, and 1-cyclohexylpiperidine. These amines exhibit either osmotic or non-osmotic character as obsd. through forward osmosis, which led to this study to better understand speciation and its influence on water transport through a semi-permeable membrane. For all concns., several phys. properties were measured including viscosity, mol. diffusion coeffs., f.p. depression, and d. Based on these measurements, a variation on the Mark-Houwink equation was developed to predict the viscosity of any tertiary amine SPS as a function of concn. using the amine's mol. mass. The phys. properties of osmotic SPS, which are identified as having an amine to carbonic acid salt ratio of ∼1 : 1, have consistent concn. dependence behavior over a wide range of concns., which suggests osmotic pressures based on low concns. f.p. studies can be extrapolated reliably to higher concns. The obsd. phys. properties also allowed the identification of soln. state speciation of non-osmotic SPS, where the amine to carbonic acid salts ratio is significantly greater than one. These results indicate that, at most concns., the stoichiometric excess of amine is involved in solvating a proton with two amines.
- 30McNally, J. S.; Noll, B.; Orme, C. J.; Wilson, A. D. Density Functional Theory Analysis of the Impact of Steric Interaction on the Function of Switchable Polarity Solvents. J. Phys. Chem. B 2015, 119, 6766– 6775, DOI: 10.1021/acs.jpcb.5b03167Google Scholar30https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXnslCqtrY%253D&md5=cd2eb0a7ea60af21663a56ba6c13d9a7Density Functional Theory Analysis of the Impact of Steric Interaction on the Function of Switchable Polarity SolventsMcNally, Joshua S.; Noll, Bruce; Orme, Christopher J.; Wilson, Aaron D.Journal of Physical Chemistry B (2015), 119 (22), 6766-6775CODEN: JPCBFK; ISSN:1520-5207. (American Chemical Society)A d. functional theory (DFT) anal. was performed to explore the impact of steric interactions on the function of switchable polarity solvents (SPS) and their implications on a quant. structure-activity relation (QSAR) model previously proposed for SPS. An x-ray crystal structure of the N,N-dimethylcyclohexylammonium bicarbonate (Hdmcha) salt was solved as an asym. unit contg. two cation/anion pairs, with a hydrogen bonding interaction obsd. between the bicarbonate anions, as well as between the cation and anion in each pair. DFT calcns. provide an optimized structure of Hdmcha that closely resembles exptl. data and reproduces the cation/anion interaction with the inclusion of a dielec. field. Relaxed potential energy surface (PES) scans were performed on Hdmcha-based computational model compds., differing in the size of functional group bonded to the nitrogen center, to assess the steric impact of the group on the relative energy and structural properties of the compd. Probably both the length and amt. of branching assocd. with the substituent impact the energetic limitations on rotation of the group along the N-R bond and NC-R bond, and disrupt the energy minimized position of the hydrogen bonded bicarbonate group. The largest interaction resulted from functional groups that featured five bonds between the ammonium proton and a proton on a functional group with the freedom of rotation to form a pseudo six membered ring which included both protons.
- 31Stephenson, R. M. Mutual Solubilities: Water + Cyclic Amines, Water + Alkanolamines, and Water + Polyamines. J. Chem. Eng. Data 1993, 38, 634– 637, DOI: 10.1021/je00012a041Google Scholar31https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK3sXlvV2msr0%253D&md5=9adda0b1cdfe4e5e3ed082cdca7e15d1Mutual solubilities: water + cyclic amines, water + alkanolamines, and water + polyaminesStephenson, Richard M.Journal of Chemical and Engineering Data (1993), 38 (4), 634-7CODEN: JCEAAX; ISSN:0021-9568.Reciprocal solubilities for water + cyclic amines, water + alkanolamines, and water + polyamines were measured. Of the 24 cyclic amines studied, only furfurylamine and cyclohexylamine were consolute with water. Of 31 alkanolamines studied, 26 were miscible with water in all proportions, 3 were partially miscible at 0-90°, and 2 had lower crit. soln. temps. of 13.6 and 30°. Of 27 polyamines studied, 24 were miscible with water in all proportions, only 1 was partially miscible at 0-90°, and 2 had lower crit. soln. temps. of 3 and 57°.
- 32Reta, M.; Cattana, R.; Silber, J. J. Kamlet–Taft’s Solvatochromic Parameters for Nonaqueous Binary Mixtures between n-Hexane and 2-Propanol, Tetrahydrofurane, and Ethyl Acetate. J. Solution Chem. 2001, 30, 237– 252, DOI: 10.1023/a:1005275432313Google Scholar32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3MXksVGmsb4%253D&md5=849ce1b5218012d0f8088561afc37d09Kamlet-Taft's solvatochromic parameters for nonaqueous binary mixtures between n-hexane and 2-propanol, tetrahydrofuran, and ethyl acetateReta, Mario; Cattana, Rosa; Silber, Juana J.Journal of Solution Chemistry (2001), 30 (3), 237-252CODEN: JSLCAG; ISSN:0095-9782. (Kluwer Academic/Plenum Publishers)The π*, α, and β Kamlet-Taft solvatochromic solvent parameters were detd. for nonaq. binary mixts. commonly used in normal-phase liq. chromatog. (NPLC), such as EtOAc n-hexane, THF n-hexane, and iso-PrOH n-hexane from spectroscopic data by using several UV-visible absorbing probes. Because preferential solvation is almost nonexistent for the π* probes in the different binary mixts., the measured values reflect quite well the dipolarity-polarizability of the bulk soln. However, strong preferential solvation for the different α and β probes in all mixts. studied here shows that the solvent parameters obtained reflect the properties of the solvation shell more than the bulk properties. This observation does not necessarily mean that the α and β values obtained will not be useful in multiple linear regressions (MLR), but results should be interpreted with care and will depend on the particular situation. Actually, results will make sense only if the particular solute under study preferentially solvates in a fashion similar to that of the α and β solvatochromic probes.
- 33Toma, H. E.; Takasugi, M. S. Preferential Solvation Effects in the Electrochemistry and Charge-Transfer Spectra of Cyanoiron(II) Complexes. J. Solution Chem. 1989, 18, 575– 583, DOI: 10.1007/BF00664238Google Scholar33https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL1MXlt1Wqu7Y%253D&md5=ae4c5b1f07416dd4e1244c007982fe30Preferential solvation effects in the electrochemistry and charge-transfer spectra of cyanoiron(II) complexesToma, Henrique E.; Takasugi, Maria S.Journal of Solution Chemistry (1989), 18 (6), 575-83CODEN: JSLCAG; ISSN:0095-9782.The energies of the charge-transfer bands and the redox potentials of substituted cyano iron(II) complexes are strongly influenced by preferential solvation effects in water-acetonitrile mixed solvents, exhibiting a linear dependence with respect to the acceptor no. scale. The dependence increases with the no. of cyanide ligands in the complexes.
- 34Anslyn, E. V.; Dougherty, D. A. Solutions and Non-Covalent Binding Forces. Modern Physical Organic Chemistry; University Science Books, 2006; p 147.Google ScholarThere is no corresponding record for this reference.
- 35Malmberg, C. G.; Maryott, A. A. Dielectric Constant of Water from 0 to 100 C. J. Res. Natl. Bur. Stand. 1956, 56, 1, DOI: 10.6028/jres.056.001Google Scholar35https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaG28XkslWlug%253D%253D&md5=6a08082a0f1dd99062259a9c5f4f4499Dielectric constant of water from 0° to 100°Malmberg, C. G.; Maryott, A. A.Journal of Research of the National Bureau of Standards (United States) (1956), 56 (), 1-8CODEN: JRNBAG; ISSN:0160-1741.Research Paper No. 2641. An equal-ratio arm capacitance-cond. bridge operated between 3 and 96 kc./sec. was used to det. the dielec. const. of H2O with an error of less than ±0.1% at 5° intervals. The value was 78.30 at 25°, 0.3% lower than that usually accepted. The data fit the equation ε = 87.740 - 0.40008t + 9.398 × 10-4t2 - 1.410 × 10-6t3 with a max. deviation of ±0.01 and the simpler expression log ε = 1.94315 - 0.0019720t with a max. deviation of ±0.02.
- 36Kolling, O. W. Dielectric Characterization of Binary Solvents Containing Acetonitrile. Anal. Chem. 1987, 59, 674– 677, DOI: 10.1021/ac00131a029Google Scholar36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL2sXkvFGntA%253D%253D&md5=2fd12afadefbf7546effd2200eca187dDielectric characterization of binary solvents containing acetonitrileKolling, Orland W.Analytical Chemistry (1987), 59 (4), 674-7CODEN: ANCHAM; ISSN:0003-2700.For electrochem. solvents contg. MeCN paired with a cosolvent having either a lower or higher dielec. const. (ε), the trend in εm vs. mole fraction is usually nonlinear at 25°. Max. or min. occur in the excess function (Δε) among representative systems and the magnitude of that deviation with respect to pure MeCN is governed by the dipolarity, polarizability, and any hydrogen bonding tendency from the added cosolvent. The empirical patterns in dielec. behavior for 10 solvent systems including MeCN-polar aprotic and MeCN-hydrogen bond donor pairs conform to rational correlation functions for εm = f(X1) over the complete mole fraction range.
- 37Góral, M.; Shaw, D. G.; Mączyński, A.; Wiśniewska-Gocłowska, B.; Oracz, P. IUPAC-NIST Solubility Data Series. 96. Amines with Water Part 3. Non-Aliphatic Amines. J. Phys. Chem. Ref. Data 2012, 41, 043108, DOI: 10.1063/1.4756039Google Scholar37https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhvFWgt7bI&md5=fce1081c518db98b4e2035c3ae548234IUPAC-NIST Solubility Data Series. 96. Amines with Water Part 3. Non-Aliphatic AminesGoral, Marian; Shaw, David G.; Ma[Phook]czynski, Andrzej; Wisniewska-Goclowska, Barbara; Oracz, PawelJournal of Physical and Chemical Reference Data (2012), 41 (4), 043108/1-043108/52CODEN: JPCRBU; ISSN:0047-2689. (American Institute of Physics)A review. The mutual solubilities and related liq.-liq. equil. of 36 binary systems of non-aliph. amines with water are exhaustively and critically reviewed. Reports of exptl. detn. of soly. that appeared in the primary literature prior to the end of 2010 are compiled. For 13 systems, sufficient data are available to allow crit. evaluation. All data are expressed as mass percent and mole fraction as well as the originally reported units. (c) 2012 American Institute of Physics.
- 38Cheong, W. J.; Carr, P. W. Kamlet-Taft .Pi.* Polarizability/Dipolarity of Mixtures of Water with Various Organic Solvents. Anal. Chem. 1988, 60, 820– 826, DOI: 10.1021/ac00159a018Google Scholar38https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL1cXhsV2rsbc%253D&md5=1880f5bfa1aa46be032c689aced21b7fKamlet-Taft π* polarizability/dipolarity of mixtures of water with various organic solventsCheong, Won Jo; Carr, Peter W.Analytical Chemistry (1988), 60 (8), 820-6CODEN: ANCHAM; ISSN:0003-2700.The Kamlet-Taft π* values of mixts. of water with four org. solvents over the entire range of compn. have been estd. by solvatochromic measurements with a series of carefully selected indicators. The measured π* value of each indicator is collinear with the av. π* value. The indicators sense the polarizability/dipolarity and not the hydrogen bond acidity of the solvent. Examn. of relationships between π* and ε and between ET and π* and excess properties of π*, ET, and ε with respect to vol. fraction of the org. cosolvent leads to the conclusion that the principal effect of changing the solvent compn. on the obsd. π* values operates through the dielec. properties of the local medium about the solute. This also supports the previous observation that solvatochromic shifts of the indicators used in this study are not very sensitive to solvent hydrogen bond acidity. The measured π* values together with literature ET values were used to est. α values, the hydrogen bond acidity parameter, of aq. org. solvents.
- 39Payne, R.; Theodorou, I. E. Dielectric Properties and Relaxation in Ethylene Carbonate and Propylene Carbonate. J. Phys. Chem. 1972, 76, 2892– 2900, DOI: 10.1021/J100664A019Google Scholar39https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaE38XlsVGitb0%253D&md5=77440f67c9d377ce409df848b6320653Dielectric properties and relaxation in ethylene carbonate and propylene carbonatePayne, Richard; Theodorou, Ignatius E.Journal of Physical Chemistry (1972), 76 (20), 2892-900CODEN: JPCHAX; ISSN:0022-3654.The dielec. properties of ethylene carbonate and propylene carbonate were studied by a pulse reflection technique and a.c. measurements at 1-9000 MHz. Equil. dielec. consts. for the pure liqs. and mixts. with other liq. dielecs. are consistent with the absence of specific intermol. forces. The dipole relaxation process is described by the Debye equations with relaxation times in the psec region at room temp. and the nsec region for supercooled propylene carbonate at -78°. The apparent limiting high-frequency dielec. const. in both liqs. is approx. 10, suggesting the existence of a 2nd dispersion region at >9000 MHz. The relaxation times and the viscosity of propylene carbonate are described by an empirical rate equation of the form previously applied by Davidson and Cole to their measurements for 1-propanol, propylene glycol, and glycerol.
- 40Ramana, C. V. V.; Kumar, A. B. V. K.; Kumar, A. S.; Kumar, M. A.; Moodley, M. K. Dielectric and Excess Dielectric Constants in Non Polar+polar Binary Liquid Mixtures of Toluene with Alcohols at 303, 313 and 323K. Thermochim. Acta 2013, 566, 130– 136, DOI: 10.1016/j.tca.2013.05.022Google Scholar40https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhtFChtLnN&md5=6be5649f627a5eacff876b831e6cfda8Dielectric and excess dielectric constants in non polar + polar binary liquid mixtures of toluene with alcohols at 303, 313 and 323 KRamana, C. H. V. V.; Kumar, A. B. V. Kiran; Kumar, A. Satya; Kumar, M. Ashok; Moodley, M. K.Thermochimica Acta (2013), 566 (), 130-136CODEN: THACAS; ISSN:0040-6031. (Elsevier B.V.)The dielec. consts. and excess dielec. consts. in non-polar + polar binary liq. mixts. of toluene with alkanols (Me alc., Et alc., Pr alc. and iso-Pr alc.) have been studied at 303, 313 and 323 K temps. and over the complete mole fraction range. The dielec. consts. for these mixts. were measured using a microcontroller based system. The results are neg. over the entire range of compn. Sym. curves were obsd. for the systems in which the min. occurs approx. at 0.5-mol fraction of toluene. The results are discussed in terms of intermol. interactions. In order to predict the dielec. data for non-polar + polar binary liq. mixts., five mixing rules were applied and the results indicate that the predictions of the five mixing rules are satisfactory. The investigation of dielec. const. of mixed solvents bearing alcs. aims at better comprehension of their biol., chem., pharmaceutical, technol. and lab. applications.
- 41Jessop, P. G.; Jessop, D. A.; Fu, D.; Phan, L. Solvatochromic Parameters for Solvents of Interest in Green Chemistry. Green Chem. 2012, 14, 1245– 1259, DOI: 10.1039/c2gc16670dGoogle Scholar41https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38Xmt1yhtrY%253D&md5=b78a10dbccc390d356b0953c59b4d090Solvatochromic parameters for solvents of interest in green chemistryJessop, Philip G.; Jessop, David A.; Fu, Dongbao; Phan, LamGreen Chemistry (2012), 14 (5), 1245-1259CODEN: GRCHFJ; ISSN:1463-9262. (Royal Society of Chemistry)A review. Solvatochromic data have been collected from the literature or newly measured for 83 mol. solvents, 18 switchable solvents, and 187 ionic liqs. that have been cited in the green chem. literature. The data include the normalized Reichardt's parameter (ENT), the Nile red λmax, and the Kamlet-Taft parameters (α, β, and π*). Disagreements within the literature about the properties of glycerol and poly(ethylene glycol) have been resolved with new data. The switching of a switchable-polarity solvent (also known as a reversible ionic liq.) by CO2 causes a significant increase in polarity/polarizability (π*) but no change in the basicity (β). A switchable-hydrophilicity solvent undergoes an even greater change in polarity because it merges with an aq. phase upon exposure to CO2. Trends obsd. from the data of ionic liqs. are presented, along with concerns about the best method for detg. the Kamlet-Taft parameters.
- 42Martins, M. A. R.; Silva, L. P.; Schaeffer, N.; Abranches, D. O.; Maximo, G. J.; Pinho, S. P.; Coutinho, J. A. P. Greener Terpene-Terpene Eutectic Mixtures as Hydrophobic Solvents. ACS Sustain. Chem. Eng. 2019, 7, 17414– 17423, DOI: 10.1021/acssuschemeng.9b04614Google ScholarThere is no corresponding record for this reference.
- 43Vanderveen, J. R.; Durelle, J.; Jessop, P. G. Design and Evaluation of Switchable-Hydrophilicity Solvents. Green Chem. 2014, 16, 1187– 1197, DOI: 10.1039/C3GC42164CGoogle Scholar43https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXivFOlur4%253D&md5=b4e47c21a23a313aa623c35e04a14929Design and evaluation of switchable-hydrophilicity solventsVanderveen, Jesse R.; Durelle, Jeremy; Jessop, Philip G.Green Chemistry (2014), 16 (3), 1187-1197CODEN: GRCHFJ; ISSN:1463-9262. (Royal Society of Chemistry)Switchable-hydrophilicity solvents (SHSs) are solvents that can switch reversibly between one form that is miscible with water to another that forms a biphasic mixt. with water. For these SHSs, we use CO2 at 1 bar as a stimulus for triggering the transformation to the water-miscible form and removal of CO2 to achieve the reverse. We now report the identification of 13 new SHSs, including the first secondary amine SHSs, and a comparison of all known SHSs in terms of safety and environmental impacts. Amines which include another functional group, esp. oxygen-contg. groups, are less hazardous than alkylamines. Secondary amines can have improved switching speeds relative to tertiary amines. The variety of SHSs identified suggests that amine SHSs can be designed to have ideal properties for a given application.
Cited By
This article is cited by 2 publications.
- Kinnari M. Shah, Ian H. Billinge, Elizabeth Dach, Ngai Yin Yip. Advancing the Productivity-Selectivity Trade-off of Temperature Swing Solvent Extraction Desalination with Intermediate-Step Release. Environmental Science & Technology Letters 2023, 10
(10)
, 949-954. https://doi.org/10.1021/acs.estlett.3c00616
- Kinnari M. Shah, Elizabeth Dach, Robert Winton, Hanqing Fan, Ngai Yin Yip. Phase equilibria insights into amine-water-NaCl interactions in liquid-liquid biphasic systems for temperature swing solvent extraction desalination. Desalination 2023, 548 , 116259. https://doi.org/10.1016/j.desal.2022.116259
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- 1Jessop, P. G. Searching for Green Solvents. Green Chem. 2011, 13, 1391, DOI: 10.1039/c0gc00797h1https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXntV2mtLk%253D&md5=046d119a68acff95f1b5277bd20d6260Searching for green solventsJessop, Philip G.Green Chemistry (2011), 13 (6), 1391-1398CODEN: GRCHFJ; ISSN:1463-9262. (Royal Society of Chemistry)Academic research in the area of green solvents is focused on neither the industries that use solvents most nor the types of solvents that the research community believes have the best hope of reducing solvent-related environmental damage. Those of us who are primarily motivated by a desire to reduce such damage would do well to look at the major uses of solvents, to det. the problems that currently make those applications less-than-green and focus our research efforts on potential solns. to those problems. As a contribution to such efforts, I present four grand challenges in the field of green solvents: finding a sufficient range of green solvents, recognizing whether a solvent is actually green, finding an easily-removable polar aprotic solvent and eliminating distn.
- 2Jessop, P. G.; Mercer, S. M.; Heldebrant, D. J. CO2-triggered switchable solvents, surfactants, and other materials. Energy Environ. Sci. 2012, 5, 7240, DOI: 10.1039/c2ee02912j2https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38Xnslans7k%253D&md5=9dd7d5e2e22f04028420aca2a2ee1be7CO2-triggered switchable solvents, surfactants, and other materialsJessop, Philip G.; Mercer, Sean M.; Heldebrant, David J.Energy & Environmental Science (2012), 5 (6), 7240-7253CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)A review. Waste CO2 at atm. pressure can be used to trigger dramatic changes in the properties of certain switchable materials. Compared to other triggers such as light, acids and oxidants, CO2 has the advantages that it is inexpensive, nonhazardous, non-accumulating in the system, easily removed, and it does not require the material to be transparent. Known CO2-triggered switchable materials now include solvents, surfactants, solutes, catalysts, particles, polymers, and gels. These have also been described as "smart" materials or, for some of the switchable solvents, "reversible ionic liqs.". The added flexibility of switchable materials represents a new strategy for minimizing energy and material consumption in process and product design.
- 3Soh, L.; Eckelman, M. J. Green Solvents in Biomass Processing. ACS Sustain. Chem. Eng. 2016, 4, 5821– 5837, DOI: 10.1021/acssuschemeng.6b016353https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhsFakur7P&md5=da1e68dee5ffe165bd15a52874e38451Green Solvents in Biomass ProcessingSoh, Lindsay; Eckelman, Matthew J.ACS Sustainable Chemistry & Engineering (2016), 4 (11), 5821-5837CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)A review. As new applications expand in the field of biomass refining and valorization, appropriate solvent development and usage will aid in viable implementation. This work presents an overview of green solvent applications within biomass prodn. Particular solvent needs for biomass fractions to produce fuels and value-added products are presented. Green solvent metrics with respect to functionality, and environmental, safety, and health impacts from a process and life cycle view are also addressed and applied to conventional and neoteric solvents. Current and potential applications of various solvents for extns. and conversions are provided for consideration in a biorefinery setting with discussion of future needs.
- 4Cheremisinoff, P. N. Waste Reduction. In Waste Minimization and Cost Reduction for the Process Industries; Elsevier, 1995; pp 1– 51.There is no corresponding record for this reference.
- 5Jessop, P. G.; Phan, L.; Carrier, A.; Robinson, S.; Dürr, C. J.; Harjani, J. R. A Solvent Having Switchable Hydrophilicity. Green Chem. 2010, 12, 809, DOI: 10.1039/b926885e5https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXlvVGhs7c%253D&md5=9ead3a27c9e72c8694db956b2cc6c012A solvent having switchable hydrophilicityJessop, Philip G.; Phan, Lam; Carrier, Andrew; Robinson, Shona; Duerr, Christoph J.; Harjani, Jitendra R.Green Chemistry (2010), 12 (5), 809-814CODEN: GRCHFJ; ISSN:1463-9262. (Royal Society of Chemistry)A new kind of switchable solvent, a switchable-hydrophilicity solvent, is hydrophobic and has very low miscibility with water when in air but is hydrophilic and has complete miscibility with water when under an atm. of CO2. We report here the first example of such a solvent, N,N,N'-tributylpentanamidine. Solvents such as these could be used for the extn. of low-polarity org. products, such as vegetable oils, followed by the removal of the solvent from the product by carbonated water. Carbonated water is able to ext. the solvent from the product because the CO2 converts the solvent to its hydrophilic form. The solvent can then be sepd. from the carbonated water upon removal of the CO2, because this removal triggers the conversion of the solvent back to its hydrophobic, water-immiscible form. Importantly, distn. is not required for removal of the solvent from the product.
- 6Boyd, A. R.; Champagne, P.; McGinn, P. J.; MacDougall, K. M.; Melanson, J. E.; Jessop, P. G. Switchable Hydrophilicity Solvents for Lipid Extraction from Microalgae for Biofuel Production. Bioresour. Technol. 2012, 118, 628– 632, DOI: 10.1016/j.biortech.2012.05.0846https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38Xps1Ggt7c%253D&md5=da14fb53df329951a5ed837a25981577Switchable hydrophilicity solvents for lipid extraction from microalgae for biofuel productionBoyd, Alaina R.; Champagne, Pascale; McGinn, Patrick J.; MacDougall, Karen M.; Melanson, Jeremy E.; Jessop, Philip G.Bioresource Technology (2012), 118 (), 628-632CODEN: BIRTEB; ISSN:0960-8524. (Elsevier Ltd.)A switchable hydrophilicity solvent (SHS) was studied for its effectiveness at extg. lipids from freeze-dried samples of Botryococcus braunii microalgae. The SHS N,N-dimethylcyclohexylamine extd. up to 22 wt.% crude lipid relative to the freeze-dried cell wt. The solvent was removed from the ext. with water satd. with carbon dioxide at atm. pressure and recovered from the water upon de-carbonation of the mixt. Liq. chromatog.-mass spectrometry (LC-MS) showed that the extd. lipids contained high concns. of long chain tri-, di- and mono-acylglycerols, no phospholipids, and only 4-8% of residual solvent. Unlike extns. with conventional org. solvents, this new method requires neither distn. nor the use of volatile, flammable or chlorinated org. solvents.
- 7Samorì, C.; López Barreiro, D.; Vet, R.; Pezzolesi, L.; Brilman, D. W. F.; Galletti, P.; Tagliavini, E. Effective Lipid Extraction from Algae Cultures Using Switchable Solvents. Green Chem. 2013, 15, 353, DOI: 10.1039/c2gc36730k7https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhsVOntrg%253D&md5=72b55a18ad52c18ced4aa2de5522e9f8Effective lipid extraction from algae cultures using switchable solventsSamori, Chiara; Lopez Barreiro, Diego; Vet, Robin; Pezzolesi, Laura; Brilman, Derk W. F.; Galletti, Paola; Tagliavini, EmilioGreen Chemistry (2013), 15 (2), 353-356CODEN: GRCHFJ; ISSN:1463-9262. (Royal Society of Chemistry)A new procedure based on switchable polarity solvents (SPS) was proposed for lipid extn. of wet algal samples or cultures, thereby circumventing the need for an energy intensive drying step and facilitating easy recovery of the lipids from the extn. liq. Lipids were extd. by using N,N-dimethylcyclohexylamine (DMCHA) and recovered by adding CO2, thereby switching DMCHA into a hydrogen carbonate ammonium salt and resulting in the formation of a sep. liq. lipid phase.
- 8Davidson, R. R.; Smith, W. H.; Hood, D. W. Structure and Amine-Water Solubility in Desalination by Solvent Extraction. J. Chem. Eng. Data 1960, 5, 420– 423, DOI: 10.1021/je60008a005There is no corresponding record for this reference.
- 9Boo, C.; Winton, R. K.; Conway, K. M.; Yip, N. Y. Membrane-Less and Non-Evaporative Desalination of Hypersaline Brines by Temperature Swing Solvent Extraction. Environ. Sci. Technol. Lett. 2019, 6, 359– 364, DOI: 10.1021/acs.estlett.9b001829https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXosF2gtLo%253D&md5=c4151f81615c3bf5cd584ed459143c3aMembrane-less and non-evaporative desalination of hypersaline brines by temperature swing solvent extractionBoo, Chanhee; Winton, Robert K.; Conway, Kelly M.; Yip, Ngai YinEnvironmental Science & Technology Letters (2019), 6 (6), 359-364CODEN: ESTLCU; ISSN:2328-8930. (American Chemical Society)Hypersaline brines are of growing environmental importance but are technol. under-served by today's desalination methods. Temp. swing solvent extn. (TSSE) is a radically different desalination technol. that is membrane-less and not based on evaporative phase change. TSSE utilizes low-temp. heat and a low-polarity solvent with temp.-dependent water soly. for the selective extn. of water over salt from saline feeds. This study demonstrates TSSE desalination of high-salinity brines simulated by NaCl solns. with three amine solvents: diisopropylamine (DIPA), N-ethylcyclohexylamine (ECHA), and N,N-dimethylcyclohexylamine (DMCHA). We show that TSSE can desalinate brines with salinities as high as ≈234000 ppm total dissolved solids (i.e., 4.0 M NaCl) and achieve salt removals up to 98.4%. Among the solvents, DIPA exhibited the highest water extn. efficiency whereas ECHA and DMCHA produced water with the lowest salt content and solvent residue content, resp. Lastly, a high water recovery of >50% was demonstrated for TSSE desalination of 1.5 M NaCl brine using DIPA in semibatch expts. with multiple extn. cycles. This study underscores the unique capabilities of TSSE for the desalination of hypersaline brines.
- 10Boo, C.; Billinge, I. H.; Chen, X.; Shah, K. M.; Yip, N. Y. Zero Liquid Discharge of Ultrahigh-Salinity Brines with Temperature Swing Solvent Extraction. Environ. Sci. Technol. 2020, 54, 9124– 9131, DOI: 10.1021/acs.est.0c0255510https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXht1WmsrzN&md5=d79168eeb4ebc1aeb2a1a0e5f9a761e1Zero liquid discharge of ultrahigh-salinity brines with temperature swing solvent extractionBoo, Chanhee; Billinge, Ian H.; Chen, Xi; Shah, Kinnari M.; Yip, Ngai YinEnvironmental Science & Technology (2020), 54 (14), 9124-9131CODEN: ESTHAG; ISSN:0013-936X. (American Chemical Society)Zero liq. discharge (ZLD) of hypersaline brines is tech. and energetically challenging. This study demonstrates ZLD of ultrahigh-salinity brines using temp. swing solvent extn. (TSSE), a membrane-less and nonevaporative desalination technol. TSSE utilizes a low-polarity solvent to ext. water from brine and then releases the water as a product with the application of low-temp. heat. Complete extn. of water from a hypersaline feed, simulated by 5.0 M NaCl soln. (≈292 g/L TDS), was achieved using diisopropylamine solvent. Practically all of the salt is pptd. as mineral solid waste and the product water contains <5% of NaCl relative to the hypersaline feed brine. Consistent ZLD performance of high salt removals and product water quality was maintained in three repeated semibatch TSSE cycles, highlighting recyclability of the solvent. The practical applicability of the technique for actual field samples was demonstrated by ZLD of an irrigation drainage water conc. This study establishes the potential of TSSE as a more sustainable alternative to current thermal evapn. methods for zero liq. discharge of ultrahigh-salinity brines.
- 11Boo, C.; Qi, H.; Billinge, I. H.; Shah, K. M.; Fan, H.; Yip, N. Y. Thermomorphic Hydrophilicity Base-Induced Precipitation for Effective Descaling of Hypersaline Brines. ACS EST Eng. 2021, 1, 1351– 1359, DOI: 10.1021/acsestengg.1c00160There is no corresponding record for this reference.
- 12Guan, X.; Huang, Z.; Lu, H.; Sun, D. Microheterogeneity and CO2 Switchability of N,N-Dimethylcyclohexylamine-Water Binary Mixtures. J. Phys. Chem. B 2019, 123, 3096– 3102, DOI: 10.1021/acs.jpcb.8b1206012https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXltFCis7k%253D&md5=6323b0cddb868b3e91a458a28a0d4320Microheterogeneity and CO2 Switchability of N,N-Dimethylcyclohexylamine-Water Binary MixturesGuan, Xueqian; Huang, Zhiyu; Lu, Hongsheng; Sun, DejunJournal of Physical Chemistry B (2019), 123 (14), 3096-3102CODEN: JPCBFK; ISSN:1520-5207. (American Chemical Society)Binary mixts. of water and org. solvents are described as the aq. solns. of org. solvents, which are usually spatially heterogeneous on the scale of a few mol. sizes but homogeneous on longer length scales, i.e., microheterogeneity. For the water-org. solvent binary mixts. with microheterogeneity, most org. solvents are miscible with water at any ratio. Interestingly, some slightly water-miscible org. solvents can also be used to prep. binary mixts. with microheterogeneity. In this study, N,N-dimethylcyclohexylamine (DMCHA) was used to prep. binary mixts. with microheterogeneity and CO2 switchability. With the help of cond., Fourier-transform IR spectroscopy, UV-visible spectroscopy, and dynamic light scattering measurements, we found that water mols. are hydrogen-bonded together to form clusters over the water content range of 9 to 27 wt. %, exhibiting microheterogeneity in the binary mixt. The size of the water clusters increases slightly with increasing water content. What is more, the DMCHA-water mixts. can be reversibly split into two phases by alternate bubbling of CO2 and N2, exhibiting excellent CO2 switchability. The binary mixts. can be used as reaction media for the synthesis of CaCO3 nanoparticles. Binary mixts. with microheterogeneity can also be formed under high salinity or high temp. conditions or be prepd. using other slightly water-miscible org. solvents, opening up more interesting possibilities for binary mixts. with microheterogeneity.
- 13Wilson, A. D.; Stewart, F. F. Structure-function study of tertiary amines as switchable polarity solvents. RSC Adv. 2014, 4, 11039– 11049, DOI: 10.1039/C3RA47724J13https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXivFWmsbw%253D&md5=02289ac2cedbc3e0eba9375dcb533971Structure-function study of tertiary amines as switchable polarity solventsWilson, Aaron D.; Stewart, Frederick F.RSC Advances (2014), 4 (22), 11039-11049CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)A series of tertiary amines have been screened for their function as switchable polarity solvents (SPS). The relative ratios of tertiary amine and carbonate species as well as max. possible concn. were detd. through quant. 1H and 13C NMR spectroscopy. The viscosities of the polar SPS solns. were measured and ranged from near water in dil. systems through to gel formation at high concns. The van't Hoff indexes for SPS solns. were measured through f.p. depression studies as a proxy for osmotic pressures. A new form of SPS with an amine:carbonate ratio significantly greater than unity has been identified. Tertiary amines that function as SPS at ambient pressures appear to be limited to mols. with fewer than 12 carbons. The N,N-dimethyl-n-alkylamine structure has been identified as important to the function of an SPS.
- 14Pasham, F.; Jabbari, M.; Farajtabar, A. Solvatochromic Measurement of KAT Parameters and Modeling Preferential Solvation in Green Potential Binary Mixtures of N-Formylmorpholine with Water, Alcohols, and Ethyl Acetate. J. Chem. Eng. Data 2020, 65, 5458– 5466, DOI: 10.1021/acs.jced.0c0058914https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhvFKltb3M&md5=861ddc8391c6bb96359433ebab1d883bSolvatochromic Measurement of KAT Parameters and Modeling Preferential Solvation in Green Potential Binary Mixtures of N-Formylmorpholine with Water, Alcohols, and Ethyl AcetatePasham, Fatemeh; Jabbari, Morteza; Farajtabar, AliJournal of Chemical & Engineering Data (2020), 65 (11), 5458-5466CODEN: JCEAAX; ISSN:0021-9568. (American Chemical Society)Kamlet-Abboud-Taft (KAT) solvatochromic parameters (α, β, and π*), as well as the Reichardt's polarity scale (ET(30)), were measured from UV-visible (UV-vis) absorption spectral shift of three indicator solutes namely 4-nitroaniline, N,N-dimethyl-p-nitroaniline, and the betaine dye 4-(2,4,6-triphenylpyridinium-1-yl)-2,6-diphenylphenolate. These measurements were done within the whole mole fraction range of the binary mixt. of green solvents N-formylmorpholine with water, ethanol, 1-propanol, 2-propanol, 1-butanol, and Et acetate at room temp. (298.15 ± 0.1 K). The Redlich-Kister model was employed to demonstrate the effect of solvent compn. on the solvatochromic parameters obtained in the mixts. understudy. The data of ET obtained for the indicator dyes in different mole fractions (0.0-1.0) of the binary mixts. were analyzed to investigate their preferential solvation in terms of both the solute-solvent and the solvent-solvent interactions. The solvent exchange model was successfully utilized to calc. preferential solvation parameters. The solvation shell of the dyes is mainly affected by the solvent-solvent interactions, and all studied systems showed the nonideal behavior.
- 15Sarijloo, M. M.; Jabbari, D. M.; Farajtabar, D. A. Solvatochromism in some cosolvent mixtures of sulfolane and aliphatic alcohols: a tool to predict preferential solvation. Can. J. Chem. 2020, 98, 5458, DOI: 10.1139/cjc-2019-0369There is no corresponding record for this reference.
- 16Lagalante, A. F.; Spadi, M.; Bruno, T. J. Kamlet–Taft Solvatochromic Parameters of Eight Alkanolamines. J. Chem. Eng. Data 2000, 45, 382– 385, DOI: 10.1021/je990212f16https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3cXotl2isA%253D%253D&md5=9c7afc85856a5e6fd5195cf7b2f3c9c2Kamlet-Taft Solvatochromic Parameters of Eight AlkanolaminesLagalante, Anthony F.; Spadi, Melanie; Bruno, Thomas J.Journal of Chemical and Engineering Data (2000), 45 (2), 382-385CODEN: JCEAAX; ISSN:0021-9568. (American Chemical Society)The frequency maxima of four solvatochromic probes were measured (25, 50, and 75 °C) in eight liq. alkanolamine solvents. Addnl., the indexes of refraction of the alkanolamine solvents were measured. The frequency maxima were used to calc. solvatochromic interaction parameters. The values of the solvatochromic parameters did not vary greatly from one alkanolamine to another; however, the values of the solvatochromic parameters were high, indicating strong interaction abilities in these solvents.
- 17Kamlet, M. J.; Taft, R. W. The solvatochromic comparison method. I. The .beta.-scale of solvent hydrogen-bond acceptor (HBA) basicities. J. Am. Chem. Soc. 1976, 98, 377– 383, DOI: 10.1021/ja00418a00917https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaE28XovFeqtA%253D%253D&md5=d5dbfaf6ec62e2a1380ae9d5cb190045The solvatochromic comparison method. I. The β-scale of solvent hydrogen-bond acceptor (HBA) basicitiesKamlet, Mortimer J.; Taft, R. W.Journal of the American Chemical Society (1976), 98 (2), 377-83CODEN: JACSAT; ISSN:0002-7863.The solvatochromic comparison method was outlined. Magnitudes of enhanced solvatochromic shifts in HBA (H-bond acceptor) solvents were detd. for 4-nitroaniline relative to N,N-diethyl-4-nitroaniline and for 4-nitrophenol relative to 4-nitroanisole [-ΔΔυ(3-4)B←HO]. The values for the HBD (H-bond donor) substrates in corresponding HBA solvents proportional to one another, proportional to limiting 19F NMR shifts of H-bonded complexes of 4-fluorophenol with the same HBA's, and linear with log association consts. of H-bonded complexes between 4-fluorophenol and PhOH and the same HBA mols. A scale of solvent HBA basicities was detd.
- 18Kamlet, M. J.; Abboud, J. L.; Taft, R. W. The solvatochromic comparison method. 6. The .pi.* scale of solvent polarities. J. Am. Chem. Soc. 1977, 99, 6027– 6038, DOI: 10.1021/ja00460a03118https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaE2sXlsVajurs%253D&md5=fd2206ba578969a27b790e4c709af2ffThe solvatochromic comparison method. 6. The π* scale of solvent polaritiesKamlet, Mortimer J.; Abboud, Jose Luis; Taft, R. W.Journal of the American Chemical Society (1977), 99 (18), 6027-38CODEN: JACSAT; ISSN:0002-7863.Seventy solvents are arranged in a π* scale of solvent polarities, so named because it derives from and best correlates solvatochromic effects on p → π* and π → π* electronic spectral transitions. Solvent effects on νmax values of 7 primary indicator compds. are employed in the initial construction of the π* scale, and correlations with 40 addnl. spectral indicators are used to expand and refine the data base. Std. deviations in the 47 correlation equations of νmax with solvent π* values av. 0.11 kK, which compares well with the 0.10 kK precision limit of the solvatochromic comparison method. A no. of stratagems are employed to exclude or minimize H bonding effects in detg. π* values of HBA (H bond acceptor) and amphiprotic HBA-D (H bond acceptor-donor) solvents. Values of s in the solvatochromic equation, νmax = ν0 + sπ*, show logical variations with indicator structure, lending confidence that this new solvatochromic parameter will come to serve as a convenient and meaningful indicator of the interaction of a chromophore with its cybotactic environment. Poor correlation of νmax values for Dimroth's (1963) betaine, 4-(2,4,6-triphenylpyridinium)-2,6-diphenylphenoxide with the π* scale is rationalized in terms of differing polarity and polarizability contributions to overall solvent effects.
- 19Taft, R. W.; Kamlet, M. J. The solvatochromic comparison method. 2. The .alpha.-scale of solvent hydrogen-bond donor (HBD) acidities. J. Am. Chem. Soc. 1976, 98, 2886– 2894, DOI: 10.1021/ja00426a03619https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaE28XksVGrsbs%253D&md5=5f3142f773168067691dbbd36ac5b284The solvatochromic comparison method. 2. The α-scale of solvent hydrogen-bond donor (HBD) aciditiesTaft, R. W.; Kamlet, Mortimer J.Journal of the American Chemical Society (1976), 98 (10), 2886-94CODEN: JACSAT; ISSN:0002-7863.The solvatochromic comparison method is used to evaluate H-bonding contributions in HBD solvents to several commonly used dye indicator solvent polarity scales (Dimroth's ET30, Brooker's χR, Kosower's Z). H-bonding effects on other spectral properties, equil., and reaction rates are detd, and the results are used to construct an α-scale of solvent HBD acidities.
- 20Kamlet, M. J.; Abboud, J. L. M.; Abraham, M. H.; Taft, R. W. Linear solvation energy relationships. 23. A comprehensive collection of the solvatochromic parameters, .pi.*, .alpha., and .beta., and some methods for simplifying the generalized solvatochromic equation. J. Org. Chem. 1983, 48, 2877– 2887, DOI: 10.1021/jo00165a01820https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL3sXkvVOgsbc%253D&md5=99b60c3cc817d5508b28d85f3ad6c8a1Linear solvation energy relationships. 23. A comprehensive collection of the solvatochromic parameters, π*, α, and β, and some methods for simplifying the generalized solvatochromic equationKamlet, Mortimer J.; Abboud, Jose Luis M.; Abraham, Michael H.; Taft, R. W.Journal of Organic Chemistry (1983), 48 (17), 2877-87CODEN: JOCEAH; ISSN:0022-3263.A generalized equation for linear solvation energy relations or complexation energy relations is developed which involves 6 terms: π* (a solvent dipolarity-polarizability term), α (solvent hydrogen-bond acceptor term), β (solvent hydrogen-bond donor term), δ (solvent polarizability correction term), δH (Hildebrand soly. parameter), and ξ. This equation is reduced to a more manageable form by a judicious choice of solvents and reactants or indicators. One-, two- or three-parameter LFER involving different combinations of the above parameters and various types of physicochem. properties are obsd. A comprehensive collection of π*, α, and β for 217 solvents is presented.
- 21ASTM E203-96 Standard Test Method for Water Using Volumetric Karl Fischer Titration. ASTM August 16, 2017.There is no corresponding record for this reference.
- 22Muller, P. Glossary of Terms Used in Physical Organic Chemistry (IUPAC Recommendations 1994). Pure Appl. Chem. 1994, 66, 1077– 1184, DOI: 10.1351/pac199466051077There is no corresponding record for this reference.
- 23Baker, S. N.; Baker, G. A.; Bright, F. V. Temperature-dependent microscopic solvent properties of “dry” and “wet” 1-butyl-3-methylimidazolium hexafluorophosphate: correlation with ET(30) and Kamlet-Taft polarity scales. Green Chem. 2002, 4, 165– 169, DOI: 10.1039/b111285f23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD38XivVakt7k%253D&md5=875f197ca2fee7f58ac85823870458d5Temperature-dependent microscopic solvent properties of 'dry' and 'wet' 1-butyl-3-methylimidazolium hexafluorophosphate: correlation with ET(30) and Kamlet-Taft polarity scalesBaker, Sheila N.; Baker, Gary A.; Bright, Frank V.Green Chemistry (2002), 4 (2), 165-169CODEN: GRCHFJ; ISSN:1463-9262. (Royal Society of Chemistry)As a result of heightened awareness of a wealth of potential in clean manufg. processes, room temp. ionic liqs. (RTILs) have been the target of increased investigation. As an integral part of the green chem. movement, RTILs have found application in synthesis, catalysis, polymn., industrial cleaning, liq./liq. extn., and sepns. While some groundwork has been laid, the optimal utilization and tailoring of these solvents has been hobbled by an incomplete understanding of their solvent properties, particularly at the mol. level. In this work, we use solvatochromic measurements to det. 'energy of transition' ET(30) values and Kamlet-Taft solvent parameters (α, β, π*) for the relatively hydrophobic RTIL 1-butyl-3-methylimidazolium hexafluorophosphate, [bmim]+[PF6]-, as a function of temp. (10-70°) and water content (50 ppm or less water, 'dry' or 2% water (vol./vol.), 'wet'). The results of these expts. demonstrate that dry [bmim]+[PF6]- exhibits a hydrogen bond donor strength on the order of short chain alcs. with a linear temp. dependence. Dry and wet [bmim]+[PF6]- exhibit hydrogen bond acceptor abilities, which are weak functions of temp., intermediate between that of water and acetonitrile. The π* parameter for wet and dry [bmim]+[PF6]- is higher than short chain alcs., but lower than water or dimethylsulfoxide at ambient conditions, and it exhibits a strong linear temp. dependence. Finally, the addn. of water to [bmim]+[PF6]- does not affect the β and π* values significantly.
- 24Katritzky, A. R.; Fara, D. C.; Yang, H.; Tämm, K.; Tamm, T.; Karelson, M. Quantitative Measures of Solvent Polarity. Chem. Rev. 2004, 104, 175– 198, DOI: 10.1021/cr020750m24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXksFegsg%253D%253D&md5=f990ec3a30409cb4544f3d5fd698f0a3Quantitative Measures of Solvent PolarityKatritzky, Alan R.; Fara, Dan C.; Yang, Hongfang; Taemm, Kaido; Tamm, Tarmo; Karelson, MatiChemical Reviews (Washington, DC, United States) (2004), 104 (1), 175-198CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review focused on available quant. measures of solvent polarity. It reviews the different individual solvent scales (developed using pure solvents and based on empirical parameters) and the interrelations among them. The last section summarizes briefly the present position and the potential for future development of the concept of solvent polarity.
- 25Marcus, Y. The Properties of Organic Liquids That Are Relevant to Their Use as Solvating Solvents. Chem. Soc. Rev. 1993, 22, 409, DOI: 10.1039/cs993220040925https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2cXhtVKhu7k%253D&md5=5cbfd6e363ab32daba203f8e0fdcceaeThe properties of organic liquids that are relevant to their use as solvating solventsMarcus, Y.Chemical Society Reviews (1993), 22 (6), 409-16CODEN: CSRVBR; ISSN:0306-0012.Three mutually independent quantities contribute to exoergic solute-solvent interactions: solvatochromic α (for hydrogen bond donor), β (for hydrogen bond acceptor), and π* (for polarity/polarizability) of the solvent. The main endoergic contribution, cavity formation, is measured by the cohesive energy d.
- 26Wyatt, V. T.; Bush, D.; Lu, J.; Hallett, J. P.; Liotta, C. L.; Eckert, C. A. Determination of Solvatochromic Solvent Parameters for the Characterization of Gas-Expanded Liquids. J. Supercrit. Fluids 2005, 36, 16– 22, DOI: 10.1016/j.supflu.2005.03.00926https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXhtVSqs77K&md5=e16a203c41e4516da673b30a2e6bbb81Determination of solvatochromic solvent parameters for the characterization of gas-expanded liquidsWyatt, Victor T.; Bush, David; Lu, Jie; Hallett, Jason P.; Liotta, Charles L.; Eckert, Charles A.Journal of Supercritical Fluids (2005), 36 (1), 16-22CODEN: JSFLEH; ISSN:0896-8446. (Elsevier B.V.)Solvatochromic shifts of six probe indicators {4-nitroaniline, 4-nitroanisole, 4-nitrophenol, N,N-dimethyl-4-nitroaniline, 4-(2,4,6-triphenylpyridinium)-2,6-diphenylphenoxide and 2,6-dichloro-4-(2,4,6-triphenyl-1-pyridinio)phenolate} have been measured in binary mixts. of carbon dioxide with acetone and methanol at 35 and 40 °C over the entire range of solvent compn. The indicators were used to specify the solvatochromic solvent parameters (ET(30), α, β, and π*), which were calcd. from the solvatochromic shifts of the max. absorbance peak (νmax) obsd. by means of UV-vis spectroscopy.
- 27Laurence, C.; Nicolet, P.; Dalati, M. T.; Abboud, J.-L. M.; Notario, R. The Empirical Treatment of Solvent-Solute Interactions: 15 Years of .pi.*. J. Phys. Chem. 1994, 98, 5807– 5816, DOI: 10.1021/j100074a00327https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2cXjtlagt7o%253D&md5=42e02dac26f6da01798f8fb0bba3de25The Empirical Treatment of Solvent-Solute Interactions: 15 Years of π*Laurence, Christian; Nicolet, Pierre; Dalati, M. Tawfik; Abboud, Jose-Luis M.; Notario, RafaelJournal of Physical Chemistry (1994), 98 (23), 5807-16CODEN: JPCHAX; ISSN:0022-3654.The near-UV-visible spectra of 4-nitroanisole (OMe) and N,N-dimethyl-4-nitroanilline (NMe2) were obtained at 25.0 ± 0.1° in the gas phase and in a set of 229 solvents that includes non-hydrogen-bond donors such as hydrocarbons (aliph., alicyclic, ethylenic, and arom.), perfluorinated and other halogenated hydrocarbons (arom. and nonarom.), nitriles,ketones, esters, lactones, anhydrides, amides, ureas, phosphates, HMPA, sulfates, sulfites, sulfoxides, sulfones, pyridines, and tertiary amines as well as weak hydrogen-bond donors such as nitrocompounds and primary and secondary amines. The frequencies of the absorption max. of these spectra were used to refine and critically examine the π* scale of solvent effects. The dielec. consts. and refractive indexes of the solvents (mostly from this work) were used in an Oshika-Bayliss-McRae (OBM) treatment of these frequencies that led to the following results: (i) The partitioning of dipolarity and polarizability contributions to π*; (ii) the quant. assessment of more specific contributions to π* due to arom. solvents. This study also showed the limitations of the OBM treatment and the advantages of the empirical approach. General conclusions regarding the phys. meaning and the use of scales of solvent effects (excluding hydrogen bonding) were drawn.
- 28Laurence, C.; Nicolet, P.; Helbert, M. Polarity and Basicity of Solvents. Part 2. Solvatochromic Hydrogen-Bonding Shifts as Basicity Parameters. J. Chem. Soc., Perkin Trans. 2 1986, 1081, DOI: 10.1039/p2986000108128https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL28Xmt1Gksr8%253D&md5=d40a427717a64214063a49220cfd7082Polarity and basicity of solvents. Part 2. Solvatochromic hydrogen-bonding shifts as basicity parametersLaurence, Christian; Nicolet, Pierre; Helbert, MaryvonneJournal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999) (1986), (7), 1081-90CODEN: JCPKBH; ISSN:0300-9580.The solvatochromic H-bonding shifts of p-O2NC6H4OH (I) and p-O2NC6H4NH2 were measured by the thermosolvatochromic comparison method for an extended sample of O, N, C, halogen, and S bases. Their significance as a H-bonding parameter was tested by their correlation with formation consts., NMR shifts, vibrational shifts, and enthalpies for H-bonding formation. Family-dependent correlations are generally found between the above properties. The correlation of a H-bonding property for an OH donor vs. the same property for an NH donor is family dependent. The only significant family-independent correlation is for the solvatochromic shift of I vs. the enthalpy of H-bond formation of p-FC6H4OH. The β scale is mainly a scale of NH group H-bond acceptor basicity. The averaging process used to define β is criticized and it is recommended that correlation anal. of basicity be undertaken with clearly defined models.
- 29Wilson, A. D.; Orme, C. J. Concentration Dependent Speciation and Mass Transport Properties of Switchable Polarity Solvents. RSC Adv. 2015, 5, 7740– 7751, DOI: 10.1039/C4RA08558B29https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXitFOgtLnF&md5=a4d0ced116dc17eea37d54bac363f67fConcentration dependent speciation and mass transport properties of switchable polarity solventsWilson, Aaron D.; Orme, Christopher J.RSC Advances (2015), 5 (10), 7740-7751CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)Tertiary amine switchable polarity solvents (SPS) consisting of predominantly water, tertiary amine, and tertiary ammonium and bicarbonate ions were produced at various concns. for three different amines: N,N-dimethylcyclohexylamine, N,N-dimethyloctylamine, and 1-cyclohexylpiperidine. These amines exhibit either osmotic or non-osmotic character as obsd. through forward osmosis, which led to this study to better understand speciation and its influence on water transport through a semi-permeable membrane. For all concns., several phys. properties were measured including viscosity, mol. diffusion coeffs., f.p. depression, and d. Based on these measurements, a variation on the Mark-Houwink equation was developed to predict the viscosity of any tertiary amine SPS as a function of concn. using the amine's mol. mass. The phys. properties of osmotic SPS, which are identified as having an amine to carbonic acid salt ratio of ∼1 : 1, have consistent concn. dependence behavior over a wide range of concns., which suggests osmotic pressures based on low concns. f.p. studies can be extrapolated reliably to higher concns. The obsd. phys. properties also allowed the identification of soln. state speciation of non-osmotic SPS, where the amine to carbonic acid salts ratio is significantly greater than one. These results indicate that, at most concns., the stoichiometric excess of amine is involved in solvating a proton with two amines.
- 30McNally, J. S.; Noll, B.; Orme, C. J.; Wilson, A. D. Density Functional Theory Analysis of the Impact of Steric Interaction on the Function of Switchable Polarity Solvents. J. Phys. Chem. B 2015, 119, 6766– 6775, DOI: 10.1021/acs.jpcb.5b0316730https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXnslCqtrY%253D&md5=cd2eb0a7ea60af21663a56ba6c13d9a7Density Functional Theory Analysis of the Impact of Steric Interaction on the Function of Switchable Polarity SolventsMcNally, Joshua S.; Noll, Bruce; Orme, Christopher J.; Wilson, Aaron D.Journal of Physical Chemistry B (2015), 119 (22), 6766-6775CODEN: JPCBFK; ISSN:1520-5207. (American Chemical Society)A d. functional theory (DFT) anal. was performed to explore the impact of steric interactions on the function of switchable polarity solvents (SPS) and their implications on a quant. structure-activity relation (QSAR) model previously proposed for SPS. An x-ray crystal structure of the N,N-dimethylcyclohexylammonium bicarbonate (Hdmcha) salt was solved as an asym. unit contg. two cation/anion pairs, with a hydrogen bonding interaction obsd. between the bicarbonate anions, as well as between the cation and anion in each pair. DFT calcns. provide an optimized structure of Hdmcha that closely resembles exptl. data and reproduces the cation/anion interaction with the inclusion of a dielec. field. Relaxed potential energy surface (PES) scans were performed on Hdmcha-based computational model compds., differing in the size of functional group bonded to the nitrogen center, to assess the steric impact of the group on the relative energy and structural properties of the compd. Probably both the length and amt. of branching assocd. with the substituent impact the energetic limitations on rotation of the group along the N-R bond and NC-R bond, and disrupt the energy minimized position of the hydrogen bonded bicarbonate group. The largest interaction resulted from functional groups that featured five bonds between the ammonium proton and a proton on a functional group with the freedom of rotation to form a pseudo six membered ring which included both protons.
- 31Stephenson, R. M. Mutual Solubilities: Water + Cyclic Amines, Water + Alkanolamines, and Water + Polyamines. J. Chem. Eng. Data 1993, 38, 634– 637, DOI: 10.1021/je00012a04131https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK3sXlvV2msr0%253D&md5=9adda0b1cdfe4e5e3ed082cdca7e15d1Mutual solubilities: water + cyclic amines, water + alkanolamines, and water + polyaminesStephenson, Richard M.Journal of Chemical and Engineering Data (1993), 38 (4), 634-7CODEN: JCEAAX; ISSN:0021-9568.Reciprocal solubilities for water + cyclic amines, water + alkanolamines, and water + polyamines were measured. Of the 24 cyclic amines studied, only furfurylamine and cyclohexylamine were consolute with water. Of 31 alkanolamines studied, 26 were miscible with water in all proportions, 3 were partially miscible at 0-90°, and 2 had lower crit. soln. temps. of 13.6 and 30°. Of 27 polyamines studied, 24 were miscible with water in all proportions, only 1 was partially miscible at 0-90°, and 2 had lower crit. soln. temps. of 3 and 57°.
- 32Reta, M.; Cattana, R.; Silber, J. J. Kamlet–Taft’s Solvatochromic Parameters for Nonaqueous Binary Mixtures between n-Hexane and 2-Propanol, Tetrahydrofurane, and Ethyl Acetate. J. Solution Chem. 2001, 30, 237– 252, DOI: 10.1023/a:100527543231332https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3MXksVGmsb4%253D&md5=849ce1b5218012d0f8088561afc37d09Kamlet-Taft's solvatochromic parameters for nonaqueous binary mixtures between n-hexane and 2-propanol, tetrahydrofuran, and ethyl acetateReta, Mario; Cattana, Rosa; Silber, Juana J.Journal of Solution Chemistry (2001), 30 (3), 237-252CODEN: JSLCAG; ISSN:0095-9782. (Kluwer Academic/Plenum Publishers)The π*, α, and β Kamlet-Taft solvatochromic solvent parameters were detd. for nonaq. binary mixts. commonly used in normal-phase liq. chromatog. (NPLC), such as EtOAc n-hexane, THF n-hexane, and iso-PrOH n-hexane from spectroscopic data by using several UV-visible absorbing probes. Because preferential solvation is almost nonexistent for the π* probes in the different binary mixts., the measured values reflect quite well the dipolarity-polarizability of the bulk soln. However, strong preferential solvation for the different α and β probes in all mixts. studied here shows that the solvent parameters obtained reflect the properties of the solvation shell more than the bulk properties. This observation does not necessarily mean that the α and β values obtained will not be useful in multiple linear regressions (MLR), but results should be interpreted with care and will depend on the particular situation. Actually, results will make sense only if the particular solute under study preferentially solvates in a fashion similar to that of the α and β solvatochromic probes.
- 33Toma, H. E.; Takasugi, M. S. Preferential Solvation Effects in the Electrochemistry and Charge-Transfer Spectra of Cyanoiron(II) Complexes. J. Solution Chem. 1989, 18, 575– 583, DOI: 10.1007/BF0066423833https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL1MXlt1Wqu7Y%253D&md5=ae4c5b1f07416dd4e1244c007982fe30Preferential solvation effects in the electrochemistry and charge-transfer spectra of cyanoiron(II) complexesToma, Henrique E.; Takasugi, Maria S.Journal of Solution Chemistry (1989), 18 (6), 575-83CODEN: JSLCAG; ISSN:0095-9782.The energies of the charge-transfer bands and the redox potentials of substituted cyano iron(II) complexes are strongly influenced by preferential solvation effects in water-acetonitrile mixed solvents, exhibiting a linear dependence with respect to the acceptor no. scale. The dependence increases with the no. of cyanide ligands in the complexes.
- 34Anslyn, E. V.; Dougherty, D. A. Solutions and Non-Covalent Binding Forces. Modern Physical Organic Chemistry; University Science Books, 2006; p 147.There is no corresponding record for this reference.
- 35Malmberg, C. G.; Maryott, A. A. Dielectric Constant of Water from 0 to 100 C. J. Res. Natl. Bur. Stand. 1956, 56, 1, DOI: 10.6028/jres.056.00135https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaG28XkslWlug%253D%253D&md5=6a08082a0f1dd99062259a9c5f4f4499Dielectric constant of water from 0° to 100°Malmberg, C. G.; Maryott, A. A.Journal of Research of the National Bureau of Standards (United States) (1956), 56 (), 1-8CODEN: JRNBAG; ISSN:0160-1741.Research Paper No. 2641. An equal-ratio arm capacitance-cond. bridge operated between 3 and 96 kc./sec. was used to det. the dielec. const. of H2O with an error of less than ±0.1% at 5° intervals. The value was 78.30 at 25°, 0.3% lower than that usually accepted. The data fit the equation ε = 87.740 - 0.40008t + 9.398 × 10-4t2 - 1.410 × 10-6t3 with a max. deviation of ±0.01 and the simpler expression log ε = 1.94315 - 0.0019720t with a max. deviation of ±0.02.
- 36Kolling, O. W. Dielectric Characterization of Binary Solvents Containing Acetonitrile. Anal. Chem. 1987, 59, 674– 677, DOI: 10.1021/ac00131a02936https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL2sXkvFGntA%253D%253D&md5=2fd12afadefbf7546effd2200eca187dDielectric characterization of binary solvents containing acetonitrileKolling, Orland W.Analytical Chemistry (1987), 59 (4), 674-7CODEN: ANCHAM; ISSN:0003-2700.For electrochem. solvents contg. MeCN paired with a cosolvent having either a lower or higher dielec. const. (ε), the trend in εm vs. mole fraction is usually nonlinear at 25°. Max. or min. occur in the excess function (Δε) among representative systems and the magnitude of that deviation with respect to pure MeCN is governed by the dipolarity, polarizability, and any hydrogen bonding tendency from the added cosolvent. The empirical patterns in dielec. behavior for 10 solvent systems including MeCN-polar aprotic and MeCN-hydrogen bond donor pairs conform to rational correlation functions for εm = f(X1) over the complete mole fraction range.
- 37Góral, M.; Shaw, D. G.; Mączyński, A.; Wiśniewska-Gocłowska, B.; Oracz, P. IUPAC-NIST Solubility Data Series. 96. Amines with Water Part 3. Non-Aliphatic Amines. J. Phys. Chem. Ref. Data 2012, 41, 043108, DOI: 10.1063/1.475603937https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhvFWgt7bI&md5=fce1081c518db98b4e2035c3ae548234IUPAC-NIST Solubility Data Series. 96. Amines with Water Part 3. Non-Aliphatic AminesGoral, Marian; Shaw, David G.; Ma[Phook]czynski, Andrzej; Wisniewska-Goclowska, Barbara; Oracz, PawelJournal of Physical and Chemical Reference Data (2012), 41 (4), 043108/1-043108/52CODEN: JPCRBU; ISSN:0047-2689. (American Institute of Physics)A review. The mutual solubilities and related liq.-liq. equil. of 36 binary systems of non-aliph. amines with water are exhaustively and critically reviewed. Reports of exptl. detn. of soly. that appeared in the primary literature prior to the end of 2010 are compiled. For 13 systems, sufficient data are available to allow crit. evaluation. All data are expressed as mass percent and mole fraction as well as the originally reported units. (c) 2012 American Institute of Physics.
- 38Cheong, W. J.; Carr, P. W. Kamlet-Taft .Pi.* Polarizability/Dipolarity of Mixtures of Water with Various Organic Solvents. Anal. Chem. 1988, 60, 820– 826, DOI: 10.1021/ac00159a01838https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL1cXhsV2rsbc%253D&md5=1880f5bfa1aa46be032c689aced21b7fKamlet-Taft π* polarizability/dipolarity of mixtures of water with various organic solventsCheong, Won Jo; Carr, Peter W.Analytical Chemistry (1988), 60 (8), 820-6CODEN: ANCHAM; ISSN:0003-2700.The Kamlet-Taft π* values of mixts. of water with four org. solvents over the entire range of compn. have been estd. by solvatochromic measurements with a series of carefully selected indicators. The measured π* value of each indicator is collinear with the av. π* value. The indicators sense the polarizability/dipolarity and not the hydrogen bond acidity of the solvent. Examn. of relationships between π* and ε and between ET and π* and excess properties of π*, ET, and ε with respect to vol. fraction of the org. cosolvent leads to the conclusion that the principal effect of changing the solvent compn. on the obsd. π* values operates through the dielec. properties of the local medium about the solute. This also supports the previous observation that solvatochromic shifts of the indicators used in this study are not very sensitive to solvent hydrogen bond acidity. The measured π* values together with literature ET values were used to est. α values, the hydrogen bond acidity parameter, of aq. org. solvents.
- 39Payne, R.; Theodorou, I. E. Dielectric Properties and Relaxation in Ethylene Carbonate and Propylene Carbonate. J. Phys. Chem. 1972, 76, 2892– 2900, DOI: 10.1021/J100664A01939https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaE38XlsVGitb0%253D&md5=77440f67c9d377ce409df848b6320653Dielectric properties and relaxation in ethylene carbonate and propylene carbonatePayne, Richard; Theodorou, Ignatius E.Journal of Physical Chemistry (1972), 76 (20), 2892-900CODEN: JPCHAX; ISSN:0022-3654.The dielec. properties of ethylene carbonate and propylene carbonate were studied by a pulse reflection technique and a.c. measurements at 1-9000 MHz. Equil. dielec. consts. for the pure liqs. and mixts. with other liq. dielecs. are consistent with the absence of specific intermol. forces. The dipole relaxation process is described by the Debye equations with relaxation times in the psec region at room temp. and the nsec region for supercooled propylene carbonate at -78°. The apparent limiting high-frequency dielec. const. in both liqs. is approx. 10, suggesting the existence of a 2nd dispersion region at >9000 MHz. The relaxation times and the viscosity of propylene carbonate are described by an empirical rate equation of the form previously applied by Davidson and Cole to their measurements for 1-propanol, propylene glycol, and glycerol.
- 40Ramana, C. V. V.; Kumar, A. B. V. K.; Kumar, A. S.; Kumar, M. A.; Moodley, M. K. Dielectric and Excess Dielectric Constants in Non Polar+polar Binary Liquid Mixtures of Toluene with Alcohols at 303, 313 and 323K. Thermochim. Acta 2013, 566, 130– 136, DOI: 10.1016/j.tca.2013.05.02240https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhtFChtLnN&md5=6be5649f627a5eacff876b831e6cfda8Dielectric and excess dielectric constants in non polar + polar binary liquid mixtures of toluene with alcohols at 303, 313 and 323 KRamana, C. H. V. V.; Kumar, A. B. V. Kiran; Kumar, A. Satya; Kumar, M. Ashok; Moodley, M. K.Thermochimica Acta (2013), 566 (), 130-136CODEN: THACAS; ISSN:0040-6031. (Elsevier B.V.)The dielec. consts. and excess dielec. consts. in non-polar + polar binary liq. mixts. of toluene with alkanols (Me alc., Et alc., Pr alc. and iso-Pr alc.) have been studied at 303, 313 and 323 K temps. and over the complete mole fraction range. The dielec. consts. for these mixts. were measured using a microcontroller based system. The results are neg. over the entire range of compn. Sym. curves were obsd. for the systems in which the min. occurs approx. at 0.5-mol fraction of toluene. The results are discussed in terms of intermol. interactions. In order to predict the dielec. data for non-polar + polar binary liq. mixts., five mixing rules were applied and the results indicate that the predictions of the five mixing rules are satisfactory. The investigation of dielec. const. of mixed solvents bearing alcs. aims at better comprehension of their biol., chem., pharmaceutical, technol. and lab. applications.
- 41Jessop, P. G.; Jessop, D. A.; Fu, D.; Phan, L. Solvatochromic Parameters for Solvents of Interest in Green Chemistry. Green Chem. 2012, 14, 1245– 1259, DOI: 10.1039/c2gc16670d41https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38Xmt1yhtrY%253D&md5=b78a10dbccc390d356b0953c59b4d090Solvatochromic parameters for solvents of interest in green chemistryJessop, Philip G.; Jessop, David A.; Fu, Dongbao; Phan, LamGreen Chemistry (2012), 14 (5), 1245-1259CODEN: GRCHFJ; ISSN:1463-9262. (Royal Society of Chemistry)A review. Solvatochromic data have been collected from the literature or newly measured for 83 mol. solvents, 18 switchable solvents, and 187 ionic liqs. that have been cited in the green chem. literature. The data include the normalized Reichardt's parameter (ENT), the Nile red λmax, and the Kamlet-Taft parameters (α, β, and π*). Disagreements within the literature about the properties of glycerol and poly(ethylene glycol) have been resolved with new data. The switching of a switchable-polarity solvent (also known as a reversible ionic liq.) by CO2 causes a significant increase in polarity/polarizability (π*) but no change in the basicity (β). A switchable-hydrophilicity solvent undergoes an even greater change in polarity because it merges with an aq. phase upon exposure to CO2. Trends obsd. from the data of ionic liqs. are presented, along with concerns about the best method for detg. the Kamlet-Taft parameters.
- 42Martins, M. A. R.; Silva, L. P.; Schaeffer, N.; Abranches, D. O.; Maximo, G. J.; Pinho, S. P.; Coutinho, J. A. P. Greener Terpene-Terpene Eutectic Mixtures as Hydrophobic Solvents. ACS Sustain. Chem. Eng. 2019, 7, 17414– 17423, DOI: 10.1021/acssuschemeng.9b04614There is no corresponding record for this reference.
- 43Vanderveen, J. R.; Durelle, J.; Jessop, P. G. Design and Evaluation of Switchable-Hydrophilicity Solvents. Green Chem. 2014, 16, 1187– 1197, DOI: 10.1039/C3GC42164C43https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXivFOlur4%253D&md5=b4e47c21a23a313aa623c35e04a14929Design and evaluation of switchable-hydrophilicity solventsVanderveen, Jesse R.; Durelle, Jeremy; Jessop, Philip G.Green Chemistry (2014), 16 (3), 1187-1197CODEN: GRCHFJ; ISSN:1463-9262. (Royal Society of Chemistry)Switchable-hydrophilicity solvents (SHSs) are solvents that can switch reversibly between one form that is miscible with water to another that forms a biphasic mixt. with water. For these SHSs, we use CO2 at 1 bar as a stimulus for triggering the transformation to the water-miscible form and removal of CO2 to achieve the reverse. We now report the identification of 13 new SHSs, including the first secondary amine SHSs, and a comparison of all known SHSs in terms of safety and environmental impacts. Amines which include another functional group, esp. oxygen-contg. groups, are less hazardous than alkylamines. Secondary amines can have improved switching speeds relative to tertiary amines. The variety of SHSs identified suggests that amine SHSs can be designed to have ideal properties for a given application.
Supporting Information
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acssuschemeng.2c00293.
α, β, and π* values for all solvents measured in this work, sample UV–vis spectra for dry and wet DMCHA, and dielectric constants for dry and wet DMCHA (PDF)
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