JOURNAL OF APPLIED PHYSICS 98, 066105 2005

A model for the pressure dependence of viscosity in liquids

Kamal Kapoor and Narsingh Dassa
Physics Department, College of Engineering Roorkee, Vardhman Puram, Roorkee 247667, India

Received 5 January 2005; accepted 5 August 2005; published online 22 September 2005 In the present paper, a model with two adjustable parameters is developed to study the viscosity of liquid as a function of pressure. The model so developed has been applied in 38 liquids. The computed results have been found to be in very good agreement with the experimental data in case of each liquid. The minimum and the maximum ranges of viscosity studied in the present paper are 0.054 0.515 cp in CO2 and 16.9 57 200.0 cp in 2-ethylhexyl-benzoate, respectively. It is interesting to note that the relation is found valid even in the liquid in which the viscosity varies by a factor of 3400, i.e., 2-ethylhexyl-benzoate. 2005 American Institute of Physics. DOI: 10.1063/1.2043253 From the point of view of liquid state, the viscosity is an important transport property of liquids because it is a structural sensitive property and may help to give an insight into the structure of liquids. However, no adequate theory is available so far for the viscosity of the liquids, which may explain its behavior as a function of pressure and is also universally valid for all liquids. At best what is known at present are a number empirical and semiempirical relations,1 which satisfactorily express the temperature dependence of viscosity in most of the liquids. Most noticeable among these are: a rate reaction theory2 and signicant structure theory by Eyring and co-workers,3,4 b free-volume theory by Doolittle5 and also by Cohen and Turnbull,6 c hybrid equation by Macedo and Litovitz,7 and d a relation given by Walther8 which has been applied successfully by Svrcek and Mehrotra9 and by Mehrotra.10 All these attempts, however, are set with difculties as reported by Hogenboom et al.11 Thus, it is clear that some relations are available for the study of the viscosity as a function of temperature. However, no relation is available to express it as a function of pressure. Though, Jhon et al.12 have applied the signicant structure theory to study the viscosity as a function of pressure in some selected liquid hydrocarbons but the error involved is as much as 20% or more. In view of the fact that no adequate theory or relation is available in the literature that can express the viscosity of liquids precisely as a function of pressure, there is a need of a model which is capable of expressing the pressure dependence of the viscosity in liquids universally. This is the basic aim of this paper. To achieve the desired aim, the relation is developed on the basis that the ratio of second to rst pressure derivative of the viscosity is a pressure-independent parameter, i.e., Successive integration of Eq. 1 gives

and

P, T P

= 0, TexpZP
T

P, T = 0, T +

0, T
Z

expZP 1 .

This relation has the following advantages: a b It is clear from Eq. 3 that the viscosity will increase with the increase in pressure and thus supports the experimental results. Higher pressure derivative of the viscosity can also be obtained with the help of the general relation

N PN

= ZN1
T

,
T

where N 2. The idea expressed in Eq. 1 is not new. Earlier, Kumari and Dass13 have used this type of the idea in the development of an equation of state wherein the second to rst pressure derivative of bulk modulus is taken as a pressureindependent parameter. Further, Kumar et al.14 have used it in representing the sound velocity in liquid metals wherein the second to rst pressure derivative of sound velocity is taken as a pressure-independent parameter. Therefore, it was thought t to apply the idea further and this time it has been applied to study the pressure dependence of viscosity of the liquids. In the present paper, Eq. 3 has been applied in 38 liquids. The computed results are found in very good agreement with the experimental data in case of each liquid as is evident from Table I. Table I also contains the values of the adjustable parameters and the root-mean-square deviation RMSD. RMSD value indicates the goodness of t. It becomes clear from Table I that the computed data of viscosity of the liquids with pressure are in very good agreement with the experimental values. It may be mentioned here
2005 American Institute of Physics

2 P , T P2 P, T P

= Z.

Electronic mail: ndass2@rediffmail.com

0021-8979/2005/986/066105/3/$22.50

98, 066105-1

Downloaded 18 Apr 2009 to 150.214.182.8. Redistribution subject to AIP license or copyright; see http://jap.aip.org/jap/copyright.jsp

066105-2

K. Kapoor and N. Dass

J. Appl. Phys. 98, 066105 2005

TABLE I. Viscosity parameters for some liquids along with RMSD. Pressure range kbar 03.0 03.0 03.0 03.0 03.0 03.0 03.0 03.0 02.6 03.4 03.4 02.2

Liquid 7-n-hexyltridecane 9-n-octylheptadeane 11-n-decylheneilsane 1,1-diphenylethane 1,1-diphenylheptane 92-cyclohexylethylheptadecane 92-phenylethylheptadecane 13-ndodecylhexalosane 1-1-diphnyltetradecane 1-alpha-decalylpentadecane 1-alpha-nathylpentadecane 1-1dialphadecalyl-hendecane 2-ethyhexylbenzoate n-C12 n-C15 n-C18 Cis-decahydronaphthalene Trans-decahydronaphtalene Spiro 4,5 decane Spiro5,5 decane cis-octahydroindene Transoctahydroindine Me4Si CH3OD Isovaleraldehyde Propionaldehyde Heptaldehyde Caprylic aldehyde Benzaldehyde Anisaldehyde Transcinnamaldehyde Methylalchol Water Mercury Carbon dioxide Acetaldehyde Butyraldehyde Isobutyraldehyde

T K 310.78 310.78 310.78 310.78 310.78 310.78 310.78 333.0 333.0 388.0 388.0 371.89

Viscosity range cp 3.5385.6 7.06187.0 12.1355.0 2.85139.0 7.98778.0 12.11030.0 7.92377.0 9.98217.0 7.91223.0 2.6467.9 2.5243.8 17.35340.0

0 , T cp/kbar
6.2181 13.0233 24.4190 1.8813 12.1939 29.3937 14.8906 17.4458 13.5067 4.1662 3.0323 33.0063

Z kbar1 0.8274 0.8484 0.8562 1.3480 1.5258 1.0715 0.9381 0.7762 1.1355 0.7490 0.6889 2.7756

RMSD 0.29 0.80 1.32 1.14 0.92 3.37 0.80 0.91 0.58 0.14 0.09 8.79

Reference 15 15 15 15 15 15 15 15 15 15 15 15

253.0 352.44 352.44 352.44 333.0 333.0 333.0 333.0 333.0 333.0 298.0 303.0 300.0 296.0 295.0 293.5 295.0 298.0 302.0 303.0 303.0 303.0 300.01 295.0 302.0 301.0

03.0 03.6 03.6 02.4 03.6 03.2 03.2 03.6 03.2 03.6 04.0 0.024.905 01.380 01.380 01.380 01.380 01.380 01.380 01.380 012.0 011.0 012.0 0.064.53 01.380 01.380 01.380

70.388 500.0 0.637.13 1.0111.16 1.4811.50 1.56956.5 1.11417.3 1.16520.3 1.53433.0 1.19322.0 0.88516.9 0.2142.989 0.8601.007 0.68231.304 0.42930.7408 0.95432.0240 1.25273.2659 1.3862.7842 3.371611.0780 3.605415.6853 0.5205.176 0.4881.126 1.5162.008 0.0540.515 0.34680.5368 0.54860.9638 0.53820.9580

226.34 0.7473 1.3087 2.0352 1.8830 1.3019 1.3728 1.7702 1.9429 1.0006 0.2983 0.1822 0.4257 0.1300 0.5440 0.9142 0.6880 2.1369 4.4288 20.141 0.0383 0.0347 0.1415 0.1845 0.3079 0.3149

2.2618 0.4313 0.4912 0.5411 0.9250 0.7151 0.6356 0.8777 0.7836 0.8909 0.3756 0.1446 0.0700 0.7706 0.4810 0.6331 0.5267 1.2114 0.9278 10.335 0.0751 0.0270 0.1761 0.4612 0.0329 0.0507

0.08 0.014 0.018 0.105 0.046 0.013 0.067 0.034 0.030 0.003 0.014 0.0096 0.012 0.0072 0.004 0.0036 0.021 0.052 0.033 0.012 0.0006 0.015 0.0059 0.0042 0.002

16 11 11 11 11 11 11 11 11 11 17 18 19 19 19 19 19 19 19 20 20 20 21 19 19 19

that the results obtained with Eq. 3 are much better than the results given by signicant structure theory.12 Further, it is interesting to note that the relation is capable of representing the viscosity of a liquid within the range of 16.9 57200 cp which seems not to be possible by any other model. Moreover, the present relation can also give higher-order derivative of viscosity

It is clear that a semiempirical formula based on the present model is valuable because in the long run it may provide a basis on which a more profound and basic theory of the viscosity of the liquids may be developed. Moreover, at present, it provides a convenient means for representing the experimental data including interpolation as well as extrapolation.

Downloaded 18 Apr 2009 to 150.214.182.8. Redistribution subject to AIP license or copyright; see http://jap.aip.org/jap/copyright.jsp

066105-3
1

K. Kapoor and N. Dass

13 14

J. Appl. Phys. 98, 066105 2005 M. Kumari and N. Dass, J. Phys.: Condens. Matter 2, 3219 1990. R. Kumar, P. Kuchhal, and N. Dass, J. Phys.: Condens. Matter 8, 10891 1996. 15 D. A. Lowitz, J. W. Spencer, W. Webb, and R. W. Schiessler, J. Chem. Phys. 30, 73 1959. 16 N. A. Walker, D. M. Lamb, S. T. Adamy, and J. Jonas, J. Phys. Chem. 92, 3675 1988. 17 P. T. Sharko, M. Besnard, and J. Jonas, J. Phys. Chem. 87, 5197 1983. 18 J. Jonas and J. A. Akai, J. Chem. Phys. 66, 4946 1977. 19 P. M. Chaudhuri, R. A. Stager, and G. P. Mathur, J. Chem. Eng. Data 13, 9 1968. 20 P. W. Bridgmann, Collective Experimental Papers Harvard University Press, Massachusetts, 1964, Vol. 4, p. 2043; Vol. 4, p. 2155. 21 P. S. van der Gulik, Physica A 238, 81 1997.

J. A. Partington, An Advanced Treaties on Physical Chemistry LongmansGreen, London, 1951, Vol. 2. 2 S. Glasstone, K. J. Laidler, and H. Eyring, The Theory of Rate Process McGraw-Hill, New York, 1941. 3 H. Eyring and R. P. Marchi, J. Chem. Educ. 40, 562 1963. 4 T. S. Ree, T. Ree, and H. Eyring, J. Phys. Chem. 68, 3262 1964. 5 A. K. Doolittle, J. Appl. Phys. 22, 1471 1951. 6 M. H. Cohen and D. Turnbull, J. Chem. Phys. 31, 1164 1959. 7 P. B. Macedo and T. A. Litovitz, J. Chem. Phys. 42, 245 1965. 8 C. Walther, Erdol Teer 7, 382 1931. 9 W. Y. Svrcek and A. K. Mehrotra, Chem. Eng. Res. Des. 66, 323 1988. 10 A. K. Mehrotra, Ind. Eng. Chem. Res. 30, 420 1991; 30, 1367 1991. 11 D. L. Hogenboom, W. Webb, and J. A. Dixon, J. Chem. Phys. 46, 2586 1967. 12 M. Jhon, W. L. Kllotz, and H. Eyring, J. Chem. Phys. 51, 3692 1969.

Downloaded 18 Apr 2009 to 150.214.182.8. Redistribution subject to AIP license or copyright; see http://jap.aip.org/jap/copyright.jsp