scifinder scholar reference 23

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search for suitable ionic liquids for ion beam generation,we have measured the surface tension of a diversity of ionic liquids for which prior work had shown either high K (y 1 S m2 1 at room temperature) or low viscosity m. Due toits unusually high reported c (48.78 dyn cm 2 1 at 25 uC,according to ref. 2), we have also reexamined EMIEtSO 4,even though its considerable room temperature viscositycoefficient ( m/r = n = 102 mm 2 s2 1) makes a high electricalconductivity improbable.

2. Experimental

Surface tension measurement

The fact that only a few out of the hundreds of reported ionicliquids have known surface tensions is in part due to thecircumstance that conventional measurement methods userelatively large samples ( i.e. , 20 cm 3 in ref. 9). Yet, most of thematerials to be examined in this work were available only inrelatively small quantities. For this reason, we have selectedthe capillary rise method to measure surface tension, as it is

compatible with the use of very little sample. The method isnot new, and has even been used for IL characterization. 3

However, our present use of the technique offers certain newfeatures in terms of precision measurement and sampleconsumption, and will be described in some detail. It is basedon measuring the rise h of a liquid held inside a cylindrical

capillary tube of inner radius R above the level of the liquidreservoir. If c is the surface tension, r the density of the liquid, g the acceleration of gravity and h the contact angle at thepoint where the liquid, the inner capillary surface and the sur-rounding gas meet (Fig. 1), then a simple force balance yields

2p Rccos h = r p R2hg (1a)

where one assumes that the meniscus height d is much smallerthan the capillary rise h. This assumption is generally accurate,and holds to a precision better than 1% in all our measure-ments. The main problem involved in the use of eqn (1a) todetermine c/r according to eqn (1b) is the need to establishaccurately the wetting angle h

c/r = ghR /(2cos h). (1b)

h is generally unknown for a particular glassIL combination,as it is strongly dependent on the nature of the glass surface.h is also difficult to infer directly by looking at the meniscusdue to refraction from the curved glass. However, the height d

Fig. 1 Sketch of the capillary.

Table 1 Representative published surface tensions of imidazolium-based ionic liquids with measurement temperature (in uC) in parenthesis

Liquid c/dyn cm2 1 r /g cm

2 3 a m/cP K /S m2 1

BMII 54.7 (25) 1 1.08(25) 1 1110(25) 1 y 0.1(25) 11

EMIEtSO 4 48.79(25)2 1.2296(25) 2 126Merck (20)

EMITf 2N 41(20),3 39(25), 4 34.7(28) 10 1.52(25) 4,12,13 25(25), 4 32(25), 12 34(20) 13 0.90(25), 12 0.88(20) 13

C 3MITf 2N 38(25)4 1.475(25) 4 35(25) 4

BMITf 2N 37(25),4 31.5(30) 10 1.44(25), 4,12 1.43(19) 13 44(25), 4 50(25), 12 52(20) 13 0.39(25), 12 0.39(20) 13

C 5MITf 2N 36(25)4 1.403(25) 4 49(25) 4

C 6MITf 2N 35(25), 4 30.6(31) 10 1.37(25) 4,12 59(25), 4 68(25) 12 0.22(25) 12C 6MITf 2N 29.1(33)

10

BMIPF 6 48.8(25),1 47(25), 4 42.9(63), 5 44.7(40) 10 1.368(25), 4 1.37(30) 14 y 270(25), 4 312(30) 14 0.146(25) 14

C 8MIPF 6 32.8(63),5 34.3(40) 10 1.22(25) 1 585(25) 1

C 10 MIPF 6 30.7(28)10

C 12 MIPF 6 23.6(63)5

EMIBF 4 54.4(25) 8 1.2853 (25) 8 38 (25) 8 1.36(25) 8

BMIBF 4 46.6(25),1 38.4(63), 5 y 41(20), 5 39.7(40) 10 1.17(30), 14 1.21(25) 15 152(20) Merck , 180(25) 15 0.173(25), 14 0.35(25) 15

C 8MIBF 4 29.8(63),5 30.6(40) 10 1.11(20) Merck 468(20) Merck

C 12 MIBF 4 25.2(63)5

C 8MIBr 32(63) 5

C 8MICl 30.5(63)5 1(25) 1 337(25) 1

EMIInCl 4 52.78(20)6 1.6413(20) 6

BMIFeCl 4 46.51(20) 7 1.369(20), 7 1.38(20) 16 34(25), 16 y 32(25) 17 0.89(25), 16 y 0.90(25) 17

BMIICl 2 54.6(RT)9 1.708(RT) 9 50(RT) 9 0.57(RT) 9

BMIBr 3 51.5(RT)9 1.702(RT) 9 93(RT) 9 0.89(RT) 9

BMIIBr 2 57.3(RT)9

1.547(RT)9

57(RT)9

0.61(RT)9

a Densities are given with fewer decimals than in the original references. Tf 2N = bis(trifluoromethylsulfonyl)imide; EMI = 1-ethyl-3-methylimidazolium; C 3MI = 1-propyl-3-methylimidazolium, etc ; BMI = C 4MI. RT = room temperature. Merck refers to the Merck home pageon ionic liquid properties (http://ildb.merck.de/ionicliquids/en/startpage.htm). Superscripts denote bibliographic references. b

Table 2 Typical surface tensions for inorganic molten salts, fromref. 10

Liquid AgNO 3 CdBr 2 GaCl 3 K2SO 4 LiBr LiCl LiF ZnBr 2

T /K 560 951 387 1383 923 979 1235 823c/dyn cm

2 1 145 63.5 23 139.4 104 121. 224.5 48.6

This journal is The Royal Society of Chemistry 2006 Green Chem. , 2006, 8 , 390397 | 391


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of the meniscus from its rounded bottom to the contact point(Fig. 1) is not affected by refraction, and can be measuredaccurately with a cathetometer.

When the capillary radius R is much smaller than thecapillary length l

l = (c/r g )1/2 , (2)

gravitational effects are negligible and the meniscus is almostspherical. The ratio d/R is then simply related to the wettingangle via

cosh~ 2 d=R

1z d=R 2 : (3)

Note that the error in cos h is much smaller than themeasurement error in d/R when d is close to R and cos happroaches unity. This is the limit of perfect wetting, which iswell met in all of our measurements (Table 3). Because eqn (1)may be rewritten hR = 2l 2cos h, when R % l and cos h is of order one, it also follows from eqn (1) that

R % l % h. (4)

This limit applies to all our experiments, based on R =0.273 mm (ACE glass microcapillary), where d is typically 100times smaller than h. This narrow section also leads to anegligible quantity of sample pulled up by the capillary. Theweakest point about operating in the spherical meniscuslimit eqn (4) is that d takes small values, and its accuratedetermination is difficult. In our case, the availability of acathetometer able (when used with high skill {) to resolve 2 mm,and the near perfect wetting of our capillaries by all our ILs

enabled use of eqn (3). Under less ideal circumstances it ispreferable to use wider capillaries and to drop eqn (3) in favorof the method discussed in the Appendix. This method is basedon the numerical solution of the equations governing the shapeof the meniscus, combined with the experimental determina-tion of R, d and h. The interpretation of our own measure-ments includes gravitational corrections, which were negligiblein all cases (the correction parameter l defined in the Appendixwas always smaller than 1%).

The experimental determination of the meniscus height hinvolves locating the meniscus bottom at the top of thecapillary, and the reservoir level at a point of relatively smallcurvature. The first position can be determined with negligiblerelative error. Accurate determination of the second requiresideally a large liquid reservoir, but this was precluded by thesmall samples available. The reservoir was made of glass, and

had the form of a cup with an inner diameter of 5.7 mm at itstop and a rapidly tapering shape towards its bottom. It wasmade by cutting the wide end of a pipette, and closing itsnarrow end near the neck with a propane torch. To avoidcontamination, a new reservoir was made for each liquidstudied. The sample liquid inside the cup wets both the outersurface of the capillary and the inner surface of the cup, risingslightly at both points. The level of liquid in the reservoir wasmeasured at the minimum level between these two contactpoints. However, the interface at this lowest position hasnonzero curvature and fails to provide an exact reference forthe origin of heights. The associated error is a fraction of l ,certainly smaller than the capillary rise seen on the side of the

cup or the outside of the capillary. This indeterminacy leads tothe largest error in our measurement. It can be estimated firstby ignoring the presence of the capillary inside the cup, anddetermining the capillary rise within the cup itself. We use forthis estimation the known formulae for a two-dimensionalproblem. 23 For the typical case c/r = 40 cm 3 cm

2 2 (l y 2 mm)and h = 0, the height at the center of the cup (5.7 mm id)is about 0.3 l , or 0.6 mm. Compared with a typical valueof h y 2 cm, this represents a 3% error. The presence of the capillary in the center of the system would worsen thesituation, so an error in the range of 5% is more realistic. Notethat the actual h is always larger than the measured value, sothe reported surface tensions are lower bounds for the actual

Table 3 Room temperature (2225 u C) surface tensions measured in the present study, together with other physical properties from the literature

Ionic liquid cos h h/mm c/dyn cm2 1 r /g cm

2 3 g/cP K /S m2 1

EMIBF 4 0.995 26.92 4 4.3 52(24)a 1.29(25) 8 38(25) 8 1.36(25) 8

EMITfO = EMICF 3SO 3 0.995 26.92 39.2 36(22)a 1.39(22) 13 45(20) 13 0.86(20) 13

EMITf 2Nc 0.950 16.50 35.2, 34.9 a 1.52(22) 13 34(20) 13 0.88(20) 13

DMIN(CN) 2 0.996 29.23 61.6 1.14(20)26 15(25) 26 3.6(25) 26

EMIN(CN) 2 0.997 29.43 42.6 1.08(20)25 16(25) 25 2.8(25) 25

EMIC(CN) 3 0.999 32.11 47.9 1.11(20)25 18(22) 25 2.2(25) 25

EMISCN 0.963 31.96 49 1.11(20) Merck 23(20) Merck , 21(RT) 30 y 0.4(25) 30EMIGaCl 4 0.850.99 50 1.53(20)

29 16(25) 29 2.2(25) 29

EMIFeCl 4 0.99 47.7 1.42(20)29 18(25) 29 2.0(25) 29

BMIGaCl 4 0.98 41.5 1.43(20)b 31(25) b 0.95(25) b

BMIFeCl 4 0.860.99 44.9 1.38(20)16 34(25) 16 , y 32(25) 17 0.89(25) 16 , y 0.90(25) 17

BMIAu(CN) 2 0.98 46.6 1.87(20)27 279(25) 27 0.12(25) 27

EMIEtSO 4 42.5 1.23(25) 2 126(20) Mercka Earlier measurements by I. Romero (Yale) without drying the meniscus. b Unpublished data from Yoshida and Saito. c Tf 2N =bis(trifluoromethylsulfonyl)imide.

{ High contrast can be obtained when the light source is perpendicularto the capillary and there is an angle of no more than 90 u between thelight source and the light aperture of the microscope. A mirror orreflective surface should also be placed in the back of the capillary toreflect the light from the source, thus illuminating it. Multiple verticallines (reflected rays from the source) then become obvious, along withthe meniscus itself contrasting against the reflective surface. Thebenefit of these lines is that some go for the length of the capillarywhile others begin where the meniscus ends. Therefore, by measuringthe height at which these rays start, one can consistently and accuratelymeasure the height of the top of the meniscus. Simply align thecrosshairs with these lines to measure the top of the meniscus.

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surface tension. This reservoir error is not inherent to thecapillary rise method, but is a consequence of our minimiza-tion of sample consumption by use of a cup of small diameter(5.7 mm).

An accurate determination of the meniscus height d requiresvery careful optimization of the lighting to give high contrastand defining unambiguously the contact point. With good skill

and practice one can determine d within better than 2 mm, asestablished by repeated measurement. The associated error ind/R is better than 1%. The corresponding error in cos h isconsiderably smaller when d is close to R (cosh A 1), as is thecase in all our measurements. This happy circumstance permitsrelatively small errors in d/R, even with ordinary skill in the useof the cathetometer. We note that some of the glass capillariesshowed a markedly different wetting angle than most. This wasclearly seen in some experiments where up to four capillarieswere immersed simultaneously in the same cup, showingsubstantial differences in both the capillary rise and thewetting angle. For instance, BMIFeCl 4 gave values of 0.994,0.9985, 0.919 and 0.856 for cos h, though the ratio h/cos h

remained relatively fixed ( 1.5% change). A similar variationwas observed with EMIGaCl 4. The observed occasionalvariation in wetting angle merely shows the strong sensitivityof this parameter to the peculiarities of the glass surface. Theresulting variation in c (y h/cos h) is due to the greaterinaccuracy in the measurement of cos h associated with poorerwetting conditions, a problem that can be overcome by usingonly the data associated with the better wetting capillaries.

Careful avoidance of hydration of the interface by contactwith ambient air is extremely important. This is evident fromthe fact that the surface tension is a characteristic of thesurface rather than the bulk, and the interface is highlyaccessible by diffusion of water vapor in the atmosphere. The

effect is readily observed with hydrophilic ILs. Once thecapillary is loaded with a dry liquid sample, the meniscusheight is not steady but keeps increasing with a characteristictime of many minutes. This unsteadiness is not associated withthe well-known slow advance of the contact point whenmoving against a dry surface. This problem was avoided bypulling initially the liquid up inside the capillary beyond itsequilibrium height with a syringe, and releasing it, so that themeniscus moves on a wet capillary surface. The surfaceremains wet for a very long time due to the essentially nullvolatility of ILs. The observed unsteadiness is due to wateruptake from the atmosphere at the interface, as evident fromthe fact that it disappears as soon as the interface is bathed in a

slow flow of a dry gas. This was done by supplying the gasthrough a tube with an exit diameter of 2 cm, with the exit of the capillary being completely immersed inside the tube. Thegas flow exiting this tube was made uniform by means of alaminarization screen. The flow rate of gas was monitored witha flowmeter ( y 0.5 l min

2 1) in order to make it small enough toavoid modifying the pressure above the meniscus, though withthe assurance that it was nonzero.

As an example, a dry meniscus of EMIBF 4 reached itsequilibrium height in a few minutes ( cdry = 44.3 dyn cm

2 1). Onturning off the flow of dry gas sheathing the meniscus from theatmosphere, a noticeable height increase is seen in as little asten minutes (depending on the ambient humidity levels), and

eventually increases by a much as 20%. For EMIEtSO 4at ambient humidity we have found chumid = 52.4 dyn cm

2 1

(cdry = 42.5 dyn cm2 1). No unsteadiness was seen in the case of

the hydrophobic liquid EMITf 2N when the meniscus was leftin contact with the laboratory environment. In none of ourexperiments did we surround the cup with a dry medium.Hence, in the case of hydrophilic liquids, there is a slow uptake

of water at the liquidgas interface on the cup. However, thiscontamination from below takes a very long time to diffuse tothe top of the capillary. Another potential source of error is thevariability of the capillary radius R. All the measurementswere made with capillaries from the same batch of 100, usinga new capillary for each measurement in order to avoidcontamination. The capillary diameters were measured forseveral of them by cutting them at several axial positions. Thevariation in tube diameter from one capillary to another orfrom different cuts on a given capillary never exceeded 2 mm. Ris therefore known within better than 1%.

All new capillaries were cleaned first with acetonitrile andthen acetone, followed by a few high pressure bursts from

clean pressurized gas. The solvents were introduced into thecapillary with a clean 27 gauge needle.

Ionic liquids

EMIEtSO 4 and EMISCN were purchased from Sigma-Aldrich (both Basf quality, with reported purity >95%.Warning: these two materials are unstable and emit poisonousvapors). These as well as all other samples were used withoutfurther purification, other than drying under vacuum at roomtemperature. The water content remaining after this treatmentwas not measured. EMIBF 4 was a special order from SolventInnovations Inc., with the rather modest undefined purity

required for its use as an ion source in vacuo. The presence of impurities was evident from its yellowish color. EMITf 2Nwas from Covalent Associates (electronic grade). This liquid ishydrophobic and showed no increase in capillary height afterrelatively long exposure of the meniscus to the laboratoryenvironment. EMITfO was from Fluka (purity >98%). Allother liquids were prepared by Dr Yoshida at Professor Saitoslaboratory, according to established protocols, and their puritywas confirmed by elemental analysis (C, H, N, halogen) and1H NMR. EMIN(CN) 2 was first prepared by MacFarlaneet al. by metathesis of EMII and AgN(CN) 2 in water.

24

Judging from the elemental analysis data, however, theproduct is not pure, possibly due to the use of the starting

material NaN(CN) 2 as received. EMIN(CN) 2 and EMI C(CN) 3 were prepared using the procedure of Yoshida et al. ,25

where the commercial NaN(CN) 2 (starting purity 96%) wasrecrystallized. The synthesis and properties of DMIN(CN) 2will be described elsewhere, 26 as will those of BMIAu(CN) 2.

27

EMIFeCl 4 was first prepared by Katayama et al. ,28 who also

reported its density and electrochemical properties at 130 uC.Its viscosity and ionic conductivity have been given byYoshida et al. ,29 who also report the synthesis and physicalproperties of EMIGaCl 4. The viscosity and ionic conductivityof BMIFeCl 4 were first measured by Angells group,

17 andhave been confirmed by new data. 16 The still unpublished dataon BMIGaCl 4 are from Yoshida and Saito. All these salts are



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liquid at room temperature, except for DMIN(CN) 2.The surface tension of this salt was also studied at roomtemperature, since, after melting, it remains as a supercooledliquid for long periods.

A much larger sample of EMIN(CN) 2 (y 5 cm3) wasprepared at Prof. John Wilkes laboratory by metathesisof EMICl and AgN(CN) 2. The small precipitate of white

AgCl crystals that formed after a few days was removed bydecanting. The corresponding surface tension was indistin-guishable from that of the Japanese sample.

3. Results and discussion

Table 3 shows our surface tension measurements, includingthe cosine of the wetting angle cos h on the glass capillary[computed from eqn (3)], and the capillary rise h (Fig. 1). Asnoted earlier, cos h is fairly close to unity in most measure-ments, a useful circumstance to reduce the error in c/rresulting from errors in the measurement of d. c/r includesthe gravitational correction of the Appendix, which was in all

cases negligible. The tabulated c is based on c/r given by thecapillary measurement, and the density r taken from theliterature, and reported in the table.

Previous measurements are available for four of thematerials studied here: EMITf 2N, EMIBF 4, BMIFeCl 4and EMIEtSO 4.

EMITf 2 N . Our datum (35.2 dyn cm2 1) is in approximate

agreement with ref. 10 {34.7(27)}, and is substantially lowerthan reported in ref. 3 and 4 {41(20); 3 39(25) 4}. We believethese two high values are incorrect. We see almost no ambienthumidity effect on the surface tension of EMITf 2N.

EMIBF 4 . Our datum for EMIBF 4 (44.3 dyn cm2 1) is

substantially lower than reported in ref. 8 {54.4 (25) 8}. The

prior high value is consistent with our own measurementsin a humid atmosphere (52 dyn cm

2 1 in Table 3), and is alsoprobably attributable to insufficient drying precautions.

EMIEtSO 4 . Our datum for EMIEtSO 4 (42.5 dyn cm2 1) is

substantially lower than reported in ref. 2 {48.79(25) 2}. Theprior high value is more consistent with our own measure-ments under ambient (humid) conditions (52.4 dyn cm

2 1), andappears to be similarly attributable to insufficient dryingprecautions.

BMIFeCl 4 . Our datum for BMIFeCl 4 (44.9 dyn cm2 1)

agrees within experimental error with that in ref. 7{46.51 (20) 7}.

Several earlier studies on the effect of water addition on the

physical properties of ionic liquids are worth discussing. Sunget al. 31 have measured the surface tension of mixtures of waterand the hydrophilic ionic liquid BMIBF 4. They report analmost fixed c y 43 dyn cm

2 1 from the neat IL up to sub-stantial water content, with a shallow peak ( c y 44 dyn cm 2 1)between 90% and 95% molar fraction of water. At increasingwater content there is a sharp drop to a minimum ( c y

40 dyn cm2 1) at 98.3% molar fraction of water, and then a

rapid rise to the surface tension of pure water ( y 72 dyn cm 2 1).The absence of an increase in the surface tension uponslight hydration of the pure salt is noteworthy. In contrast,Fitchett et al .32 have seen large variations on the electricalconductivity and viscosity in 1-alkyl-3-methylimidazolium

bis(perfluoroalkylsulfonyl) imide salts, following from themodest levels of hydration possible in these hydrophobicliquids. For instance, water-equilibrated C 6MITf 2N contains1.2% (w) water (22% molar fraction), but shows 70% of theviscosity and 112% of the electrical conductivity of the dry IL.These authors rationalize those effects on viscosity by the idealmixing rule m = j 1m1+ j 2m2, where the j i are component molar

fractions. Noteworthy is the fact that, due to the largedisparity in the molecular weight of water and the ionicliquids studied, the water-equilibrated ILs contain very littlemass but a substantial molar concentration of water. Finally,Table 7 in ref. 1 includes c data on water-equilibrated salts.Almost no effect of hydration is seen in BMIPF 6 and BMI Tf 2N, while C 6MIPF 6 and C 8MIPF 6 exhibit a retrogradeeffect, which is substantial in the case of C 6MIPF 6 (chumid =36.8 dyn cm

2 1; cdry = 43.4 dyn cm2 1).

We have studied neither BMIBF 4, nor PF 6 salts, but thereis an evident conflict between our finding of a strong effect of slight hydration on c for all hydrophilic liquids investigated,and the opposite conclusion for BMIPF 6 in ref. 31. Possible

explanations for this discrepancy are that (i) either BMIBF 4 isfar less hydrophilic than EMIBF 4, or (ii) that the surface of the dry BMIBF 4 was contaminated by atmospheric watervapor at a concentration almost independent of the watercontent of the bulk liquid. This surface concentration isprobably fixed by slow diffusion of the surface water into thebulk. This would explain qualitatively the surprising slighteffect of water concentration on surface tension, becausediffusion of water through the gas into the surface is surelymore effective than diffusion away from the surface into the(drier) bulk liquid. There is no mention in ref. 31 of any dryingprecautions taken during the surface tension measurement.The study was based on a DuNuoy Tensiometer (Surface

Tensionmat, Fisher) with a platinum ring with a meancircumference of 6 cm, and this apparatus is not readilyhandled inside a glove box. Furthermore, the c value reportedof 43 dyn cm

2 1 is almost as high as what we find for dry EMI BF 4, while the larger cation in BMI would lead one to expectsmaller c values. Prior literature gives both high and low valuesfor the surface tension of BMIBF 4, as shown in Table 1. Thelower value obtained by Law and Watson 5 (c y 41 dyn cm

2 1

at 20 uC) was also based on a surface tensiometer, but theyintroduced it into a metal cell, and noted that The cell insulated the sample from variations in the laboratoryenvironment. Their low measured value therefore supportsthe hypothesis (ii) that the dry sample of ref. 31 was not

completely dried, but also indicates only a minor variationfrom a fully dried sample ( c y 41 dyn cm

2 1 at 20 uC in ref. 5)to a less perfectly dried sample ( c y 43 dyn cm 2 1 at 20 uC inref. 31) for the case of BMIBF 4.

Prior work of Bueno and Fernandez de la Mora 33 has shownthat Taylor cones of ionic liquids with electrical conductivitiesK near or above 1 S m

2 1 act as sources of pure ions in avacuum provided their room temperature surface tensionreaches a threshold value of about 40 dyn cm 2 1 (the value forEMITfO). Liquids such as EMITf 2N with comparable K butlower c tend to emit a mixture of drops and ions, with a massflux dominated by the drops and a comparable current fordrops and ions. As shown in Fig. 2, all the liquids investigated



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here except for EMITf 2N fall above this critical surfacetension, and are therefore expected to be pure ionic emitters.The number of potential candidates to exhibit this interestingbehavior has therefore increased from just two (EMIBF 4 andEMITfO) up to 11 (though the Taylor cones of EMIEtSO 4and BMIAu(CN) 2 may need to be operated above roomtemperature in view of their limited ambient electricalconductivity 34 ).

Fig. 2 collects all of our surface tension data as a function of molar volume v. The selection of this horizontal variable isrelatively arbitrary, but not entirely so. Corresponding stateprinciple considerations 35 indicate that cvc2/3 /kT = F (T /T c),where vc and T c are the critical values for the molar volumeand the temperature, respectively. F is a function of the singlevariable T /T c for which several expressions have beenproposed. 10,35 Given empirical information on the temperaturedependence of c for the various substances examined togetherwith information on their critical volumes, one could attempt amuch better correlation than attained in Fig. 2. However, theeffort of assembling such information is particularly challeng-ing in the case of ionic liquids, whose negligible volatilitymakes it rather difficult to determine vapor liquid equilibria. 10

As long as v/vc and T /T c take equal or similar values at roomtemperature for all the substances studied, it would make senseto expect a collapse of all our data into a single curve in Fig. 2.We cannot hope this equality to hold, so, it is not surprising tosee several groups of points instead of a single curve. Mostnoticeable is the series of all salts containing the cyanide groupand having molar volumes below 180 cm 3. They all lie in asingle curve, which includes also approximately the threesubstances studied having the lowest surface tensions: EMI TfO, EMIEtSO 4 and EMITf 2N (far to the right). The twosalts containing cyanide groups whose volumes exceed 180 cm 3[EMIC(CN) 3 and BMIAu(CN) 2] exhibit anomalouslyhigh surface tensions for their large molar volume. They fallapproximately in line with the group of salts with metaltetrachloride cations, all of which also exhibit both large molarvolumes and large surface tensions.

4. Conclusions

The room temperature surface tension of several highly con-ducting ILs has been characterized with relatively little sampleconsumption by the capillary rise method. It is important tokeep the interface dry, as y 20% increases in c may result from

atmospheric water uptake in the case of hydrophilic ILs. Wehave not quantified bulk water content following our vacuumdrying procedure at room temperature. The bulk ILs mayaccordingly retain some traces of water, which are known tohave significant electrochemical and other bulk effects. In spiteof this uncertainty about the bulk, we have argued that thesurface is dry because the gas surrounding it is completely dry,

while diffusion rates of water from the surface into the gas aremuch faster than from the liquid (perhaps imperfectly dried)into the surface. Our surface tension measurements correspondtherefore to a perfectly dry surface.

A number of materials have been identified enjoying surfacetensions in excess of that of EMIBF 4 (c = 44.3 dyn cm

2 1),with a record high corresponding to DMIN(CN) 2 (c =61.6 dyn cm 2 1).

Many of the materials studied enjoy both high electricalconductivity and high surface tension, and appear as first-ratecandidates for ion generation from Taylor cones in vacuo .

Appendix: Gravitational corrections in the capillaryrise method

We consider the case of wide enough capillaries where themeniscus is not necessarily spherical and eqn (3) does not hold.One can then compute the meniscus shape, and from it derivemore general expressions relating s /r to measurable quantities(s is the surface tension in the notation of this Appendix).

Let po be the pressure at the gas, and p that in the liquid. p = po 2 r gz, where the level z = 0 is chosen at the liquidlevel in the large container. The reason for this choice is that,at this free surface, there is almost no curvature, and henceno pressure jump between liquid and gas. Using now theexpression relating the pressure jump across the meniscus andthe curvature:

1r

ddr

rz 0

1z z02 1=2~

r gzs

, (g1)

where z is understood as a function of r, z(r), giving themeniscus shape, and z9 = d z/dr. Note that z and r arecylindrical coordinates (vertical coordinate and radial distanceto the axis). For the purpose of minimizing the number of independent variables, we introduce dimensionless variables

j ~rL

(g2)

y~z{ h

L (g3)

L~s

r gh (g4)

l ~s

r gh2 (g5)

where the characteristic length L is chosen such as to make thevalue of the right hand side of eqn (g1) equal to unity ineqn (g6), eqn (g3) chooses the origin of the variable y to beright at the minimum of the meniscus ( z = h), and y9 = d y/d j :

1j

dd j

j y0

1z y02 1=2~ 1z l y (g6a)

Fig. 2 Surface tension versus molar volume for the ILs investigated.



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This equation needs to be solved numerically with initialconditions

y9 = y = 0 at j = 0. (g7)

Generally the meniscus height d is of the order of thecharacteristic length ( s /r g )1/2 , while h is much larger. Hence, l

will typically be small (unless one uses wide capillaries). In thelimit when l = 0, eqn (g6) can be integrated once into:

j y0

1z y02 1=2~ j 2=2, (g6b)

and once more (after expressing y9 as a function of j ) to yieldthe known spherical shape

y/2 = 1 2 (1 2 j 2/4)1/2 (l = 0). (g8)

In general, eqn (g6b) can be integrated numerically to yield afunction

y = y(j , l ) (g9)

One could compare this function with experimental values,and the simplest approach is to use just the value of thefunction at the edge of the capillary r = R , where y = d/L andj = R/L. Then, the experimental quantity d/R is giventheoretically as

d/R = y(j , l )/j (g10)

It is hence convenient to make a graph of the function y(j , l )/j vs. j for several l values y(j , l )/j = F (j , l ).

Similarly we know experimentally the quantity h, and onecan easily see that

R/h = lj (g11)

Now, from the experimentally known quantities d/R and R/hwe can determine the two parameters j , l , and from them thesurface tension as

s ~r gRh

j (g12)

This must be done iteratively. First one assumes l = 0, andreads j from the graph d/R = F (j , l ). With this value andeqn (g11) one finds l and enters again into the graph d/R =

F (j , l ) to read a new value of j . Two such iterations willgenerally suffice, fixing j and therefore allowing the deter-mination of the surface tension from eqn (g12). It is clear thatthe first iteration ( l = 0) gives exactly the same thing we wouldhave obtained by ignoring gravitational effects, so that theratio of the final j value to this initial value is the gravitationalcorrection.

Acknowledgements

We thank Mr Sergio Castro and Mr Carlos Bueno for theirmany contributions to this study. Financial support from theUS AFOSR through contract F-49620-01-1-1416 at Yale

University is gratefully acknowledged. This work was inpart supported by a COE Research on Elements Science(No.12CE2005), and a Grant-in-Aid (21st Century COEprogram on Kyoto University Alliance for Chemistry) fromthe Ministry of Education, Culture, Sports, Science andTechnology, Japan. YY and GS also acknowledge thefinancial support from the Grants-in-Aid for Scientific

Research (No. 15205019) by JSPS.

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