International Tables of the Surface Tension of Water N.B. Vargaftik, B.N. Volkov, and L. D. Voljak Moscow Aviation Institute, Moscow, USSR. ‘This paper presents a table for the surface tension of water from 0.01 to 374°C and an interpolating equation whivk scpreseula Uy values de tablet well within cs cot ‘ed uncertainties. The table of values and the interpolating equation are those recommend- ‘edby the International Association for the Properties of Steam (IAPS) in its recent oficial ‘release. The experimental measurements of the surface tension of water and their uncer- ‘ainties are discussed, as is the development ofthe IAPS tables, Key words:critically evaluated daa; internationally agreed-upon dats; surface tension as function of temperature; surtace tension of water. 1. Introduction ‘The International Association for the Properties of ‘Steam (IAPS) has approved an international table of values for the surface tension (o} of water in equilibrium with its ‘vapor over the entre liquid range. Given below is an analysis ‘of the most important experimental studies of the surface tension of water, the results of which have served asthe basis {or the recommended values 2. Experiments on Water Surface Tension ‘The total number of experimental studies of efor water is large. They have been carried out to different levels of accuracy, and the majority of them cover the region of tem- peratures below de wrmal buling point. A survey of the carly low-temperature investigations is given in Ref. 1, Some experiments at high temperature are also considered in Ref. 2, however, the moet important of thean wore earsied cnt after Ref. 2 was writen. We shall deal with the most careful- Iy carried out works on o for water. ‘The work of Richards and Coombs? was of great impor- tance in the development ofthe capillay-rse technique. It ives a thorough analysis ofthe factors affecting the accura- cy with which o can be measured using the capillay-rise technique. The following factors were investigated: (a) the sensitivity of the results to the accuracy with ‘hich the radius ofthe capillary was measured; (b) the diameter which wae nececeary forthe voce into ‘which the capillary was dipped in order thatthe surface of the water in the vessel could be considered plane; (c) the influence of the size ofthe contact angle; (4) the estimations of the weight of liquid in the menis- cus and (c}the arrangement of lighting to permit the most accu- rate measurement of the height of the mensscus above the plane surface ofthe water in the containing vessel ‘As a result of their measurements, Richards and © 1983 bythe US. Secretary of Commerce on behalf ofthe United Stats. ‘This copyright i asigned to the American Isis of Physics and he lable om ACS; see Reprint List at back ise. Repri 47-26897097020017-047405.00 817 Coombs recommend the value for water: Grow 2.62 10-?N/m. “The work of Richards and Carver‘ is a continuation of that of Richards and Coombs. These investigators observed Gitte eomtace angle (@ OF wated vi glass wt KN tures zero, desived a more accurate method for estimating the weight of liquid in the meniscus, and studied the infa- cece of air and the ellipticity of the capillary section on the ‘measurement of They obtained the value opr = 72.73 10-'N/m. ‘They also re-evaluated the data of Richards and Coombs? and obtained 09.0 = 72.72% 10~’N/m. Harkins and Brown,” using the capillary-rise method, ‘madecareful measurements of the surface tension of waterin ‘equlibriuis wit its vapor and with saturated ait. In both cases, they obtained the value 039 = 72.80% 10-?N/m. In these experiments they used several different samples of wa tor and several different rapilarine Tha imncertninty in the results obtained can be estimated to be about 0.1%. ‘Asa result of investigations” the capillary-rise meth- od was considerably improved and is, at present, one ofthe ‘most reliable methods available for determining the surface tension of ids over a range of temperatures, Moreover, a sound mathematical basis has been developed for determin- ing o trom the capiiary rive. Gross used a capillary method to measure for water ‘over the temperature interval 0-60 °C. He obtained six val tae for & which are of elficient accuracy for considers here. ‘Warren’ has investigated the surface tension of water cover the temperature range 0-90°C using the maximum- bubble-pressure method. The author estimates the uncer- tainty of his measurements to be 0.01%. The measurements, hhowever, were relative values based on Os = 79.03.410 "N/m. Ir hese values ave 1evaleulated wi ‘o,sx¢ = 73.50% 10°N/m which is accepted in this paper, they appear to be acceptable for use. Moser? made three series of quite accurate measure- ‘ments ofthe surface tension of waterin the range of tempera- tures 0-100°Cusing a ring-detachment method. The depen dence of o on temperature found in this work agrees with that obtained by Warren, 4. Phys. Chem. Ret. Data, Vo. 12, No.3, 1988Ramsey and Shiclds? have investigated o for water over the temperature range 0-130°C by the capillary method. ‘The glass tube containing the capillary had an inside diame- ter of ~10 mm, The surface of the water in the annular region between the capillary and the container has a consid- «rable curvature for such a narrow container. The authors attempted to correct for this curvature but underestimated its effect. The values were recalculated later by Sugden. The results ofa large numberof investigations of o for water at low temperatures were compiled and evaluated in Ref, 11; recommended values are given forthe temperature range ~ 910 140°C. In Ref. 11 the surface isin equilibrium with airsaturated with water vapor at atmospheric pressure for temperatures below 100 K and with saturated water va- poraboveit. Surface tensions measured under these two.con- ditions using the capillary technique could be expected to ier because ofthe greater density of the saturated air and possible adsorption of components ofthe sir at theinterface. For water at pressures of about 1 atm, the differences are mall (co Ref. 4) and fall within the overall reliability ofthe ‘measurements, and can be neglected. Below 0 K the surface of the supercooled water is referred to. As will be shown Iter, these values for the surface tension of water ean only be considered accurate below 100°C. Heyks and co-workers" investigated the region of tem- peratures higher than the normal boiling point. The mea- Surements were made by the capllary-rise method over the ‘temperature range 101-224 °C. The authors estimate the un- certainty in their data to range from 0.3% to0.7%, however, icy id wot take the incomplete Wetting of te sapllan int account in their calculations. Ifthese results were tobe recal- culated using the currently accepted values forthe contact angle of water on quart, the results could be used in prepar- ing eritically evalusted data for water. Watanabe and co-workers have measured o for water by a capillary-rise method over the temperature range 20- 200°C. Unfortunately the data are only shown in a diagram, ‘More detailed investigations of the surface tension for water in the temperature range above the normal boiling point have been carried out atthe Physics Cir of te Mose cow Aviation Insitute (MAI) Voljak" has used a dfferen- tial capillary method. The apparatus consisted of two quartz capillaries sealed into a thick-walled quartz ampule. The ‘method suggested by the author for selecting capillaries with ‘uniform inner eross section permitted selection of capillar- is with a uniformity within + 0.596. Both uniformity of radius along a capillary and ellipticity of eross section were considered. Measurements were made over the temperature range 20-354°C, and the uncertainty was estimated to be (0.49% at 150°C and 5% at 340°C. There was a systematic error resulting from the temperature-measurement tech- nique and the seater ofthe experimental poins was relative ly large—up to 196 at temperatures below 280 °C and 3% at 350°C, ‘The same method was used for succeeding experiments ccarciad ant at MAT.!527 fut the meparimental anparat wae improved. The control ofthe thermostat was more accurate and temperature was measured with a platinum-resistance thermometer with an uncertainty of 4 0.05 K. Capillaries with a uniformity of inner section of 0.05% were used, their 4. Phys. Chem. Ret. Data, Vol 12, No. 8, 1983 VARGAFTIK, VOLKOV, AND VOLJAK radii were determined with an uncertainty of 0.19%. The re- sults of the first set of measurements on this apparatus were processed assuming the contact angle of water on ‘quartz to be zero. Soon investigation" showed that the con- tact angle of water on quartz increases with temperature from a value of ~4" at 0°C to a value of ~28° near the critical point. the ucceeaing measurements oto Yor water” were processed using the results of the measurements of 8 ‘The results published in Ref. 16 were recalculated to take {nto account the temperature dependence ofthe contact ‘le and also published in Ref, 17 The ranges of temperature investigated in Refs. 16 and 17 -are"mutually-overlapping. the results obtained-areir agreement within 0.2 10~?N/m at low temperatures and “01x 10~°N/m at high ones. The calculated uncertainty of ‘these experiments varies from 0.3% at 20°C to 1.7% at '360°C, the greatest contribution coming from the uncertain- ty in the values ofthe contact angles. In the range of tem- peratures greater than 360°C, the uncertainty was not srcater thon 0.07><10-°¥4/a ‘The results of Refs. 16 and 17 in the range of tempera tures upto 100°C agree well with the most reliable measure- ‘ments in this range of temperature. It should also be noted that the value for the surface tension at 20°C, 72.14X10°N/m practically coincides with the values from the very precise measurements at this temperature.”* “he values obtained from Refs. 16 and 17 also agree ‘with tote from the high-temperature measurements" within their uncertainties. 3. Tables of Values for the Surface Tension of Water As the results ofan evaluation ofthe known investiga- tions of the surface tension of water, Young and Harkins gave a table of values of c for water over the temperature ange — 8 to 140 Cin Ref. I. On the bass of Ref. 3, 4,5, and 6, they recommended o = 72.75X10~°N/m, for the surface tension of water at 20°C as a reference value, which ‘nce tas und Wide UME tn Use callbraton Of taserUsLEN. ‘An analysis shows, however, that the selection of data ‘made in preparing the tables" was not always justified. The values for @ at temperatures higher than 80°C could only hhavebeen obtained by relying on the measurements on Ref. 9 as recalculated by Sugden."® However, as Sugden himself noted, the recalculated values are only reliable at moderate temperatures. Perhaps tha is why one of the authors of Ref. 11, Harkins, only presented a table of recommended values for water covering the temperature range 0 to 60°C in his monograph.” Also, m Ket, 20 recommended values for the surface tension of water are only given forthe temperature range — 10 to 100°C; the values given are in close agree- scat with those in Ref. 11. Thus for many years relatively reliable values for the surface tension of water have only been Available upto the normal boiling point, ‘Apparently. tables fr the surface tension of water cov- ering the entire liquid range were ist given by Fritz.” The data on which these tables are based are not cited. For tem- peratures up to 100°C these tables differ slightly from those given in Refs 11 and 20. At higher temperatures, especiallyINTERNATIONAL TABLES OF THE SURFACE TENSION OF WATER, those approaching the critical, the values in Ref. 21 differ considerably from measured values obtained late." ‘Values for the surface tension of water for the tempera- ture range 0-374°C, given in Vargaftik’s reference book” ‘and in Ref. 23 have been widely used in recent years. How- ‘ever, thoes tables are based on the values in Ref. 16 which were calculated without allowance for the incomplete wet- ting of quartz by water. international Tables for the Surface Tension of Water ‘the General Meeting of the Eighth amvernattonal Con- {erence on the Properties of Steam held in Giens, France in 1974 instructed the International Association for the Prop- erties of Steam to preparsintemnational tables on the ourfaos, tension of water. Two papers presenting titles on surface tension were presented during the Conference,** and three N/m oor 736 38 ‘oor 1 395 on ‘00 5 7a9s as 000 198, Saaz on 000 0 as a37 001 20 58 on 001 » ns 036 210 ssa o2 =o 2s 198 036 as sas 02 Soo. » 20 036 20 x10 on =oa o or 035 20 x07; 022 ~002 ‘s en om 2s Bw 02 002 50 98 03s 20 ase on 002 5s en10 036 0.00 24s ms on Sao @ 624 033 00 250 2606 022 Coor 6 6236 035 a0 2s 2481 oat oot 70 ous ox 002 20 2307 o2t 003 7 ase os oot 265 nas oat 008 2 tus? ost oor 20 2130 005 5 615 oat oot ms ao 0.05 0 on 030 0.00 a0 1596 006 95 387 030 oot 2s ww 207 10s 596 028 oor 23s 545 oor 110 5696 028 00 20 1430 aor us, 5397 028 oot us wir 005 Bs 5395 027 01 ais 109 016 0.05 10 283 026 oot m0 oa 016 oor Bs 5139 025 02 us 3 as 2.06 us 30 025 oor BS esi on 0s 10 4878 02 oot wo 539 on 00s 155 ae om 201 ais so on 08 10 638 025 on 30 Bs 10 ons 165 $508 033 oo iss 2s 10 000 10 30 on 201 30 190 010 =010 M5 330 on 01 365, 13 o10 00 10 a2 01 370 oss 10 006 mS a7 2 oor Stoo 000 00 4 Phys. Chem. Ret. Data, Vo. 12, No.3, 1963FFicuRe 1, Deviation experimental points fom theinterationa valves of| ‘0 Varga and ober Refs. 6nd 17; + Vollak (Ret 14 (Clerks and others (Ref 121A. Ramsey and Shiels Ref 9). ‘their uncertainties estimated from the reliability of the ex- pesluvental dat ‘As is evident from Fig. 1, most of the experimental points from the works used in evaluating the surface tension ‘over a wide range of temperature fall within the eetimated uncertainty of . The results of Refs. 3-8 fall well within ‘these limits. ‘The values in the table are well represented by Ea. (1) with T, = 647.15 K and this equation is recommended for use as an interpolating equation LTV, (Lat 140(Z=2)), The 9 where B = 235.8% 10-°N/am, b = — 0.695, nd yp = 1.256. “able also gives the divergences (Bo) ofthe values (23) calculated using Bq, (I) from the values recommended inthe table. 67 =, — 0. As is evident from the table, the diver- ‘gence lies well within the estimated uncertainties. 5. References ‘mB, Weinberg, Zh. Ross. Fi-Khim. O-a, 24,44 (1892), Gmelin’ Handbuch der Anorganschen Chem, Auf, Sytem nummer 3, Bedi, 1963, OT, W. Richards snd L. Coombs, J. Am. Chem Soe 37, 1686(1915) ‘TW Richards and EK. Carer, J, Am. Chem, Sc. 48,827 (1921) -W.D. Harkins and. E-Brown, J Atm, Che Soe. 4,49 (1919) ‘4. Phys. Chem. Re. Data, Vol 12, No, 3, 1083 \VARGAFTIK, VOLKOV, AND VOLJAK P-L. K. Gross, The Theory of Atomic Collisions, the Determination of ‘Standard for Surface Tension Measurements, PLD. ths, University of (Chicago, 1926. See abo Ref 19 TEL, Warrea, Phos. Mag 4, 338 1927, "HL Moser, An. Phys. 82, 983 (1927) oW.R. Ramsey and J. Shields, J. Chem. Soe. 63-64, 1-89 (1893, °S, Sugden, J. Chem Soe. 125,32 (192) ‘TF Young and W.D.Uaeking in aternainal Creal Table of Max ‘merical Dat, Physic, Chemistry ond Technology (McGraw-Hill, New ‘York, 1925}, Vol. 4 1.8 Heyl MK. Barnett, LV. Jone, and E Orban, J Phy. Chem. 8, 8054) A. Watanabe, H, Watanabe, an K. 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