vìi ιΤ»Αϋ.ΓΪ*>*ν >tíÀí.k *ΊιπίιΠ IFIULJ-V.!·» 'ft' Λ'. -låiiSiip ¡Ili^iilfeÉ COMMISSION OF THE EUROPEAN COMMUNITIES ■Mié LIQUID VISCOSITY AND CHEMICAL CONSTITUTION OF ORGANIC COMPOUNDS : A NEW CORRELATION mMW AND A COMPILATION OF LITERATURE DATA by D. VAN VELZEN (Euratom) R. LOPES CARDOZO (A.K.Z.O., Albatros Koninklijke Zout Organon, Hengelo, the Netherlands) H. LANGENKAMP (Euratom) 1972 Joint Nuclear Research Centre Ispra Establishment ­ Italy i Chemistry wmSËSS^gSSXÊÊ. m -li LEGAL NOTICE iiíliip mm•m' This document was prepared under the sponsorship of the CommissioM'Ai n of the European Communities. mr 'MÈwffi!mw-'< Neither the Commission of the European Communities, its contractors nor any person acting on their behalf: make any warranty or representation, express or implied, with respect to the accuracy, completeness, or usefulness of the information contained in this document, or that the use of any information, apparatus, method or process disclosed in this document may not infringe privately owned rights; or assume any liability.mtmmEEm with respect to the use of, or fo r damages resultin11.11g $ from the use of any information, apparatus, method or process disclosed in this document. «If ;-«Thi s report is on sale at the addresses listed on cover page iliPili4 i ¡Éill¡p^ ommission of the Europeanui upean Communitievjommunmes D.G. XIII ­ C.I.D. {VTI-f Ïm4w 29, rue Aldringen xembourg Jw i $m M ,**■ ii '.»■>« 'f f F* ■*[..-■: UI: J Uni f||i »sira This document was reproduced on the basis of the best available copy. mm ιΛ« EUR 4735 e LIQUID VISCOSITY AND CHEMICAL CONSTITUTION OF ORGANIC COMPOUNDS : A NEW CORRELATION AND A COMPILATION OF LITERATURE DATA by D. VAN VELZEN*, R. LOPES CARDOZO** and H. LANGENKAMP* * (Euratom) ** (Α.Κ.Ζ.O., Albatros Koninklijke Zout Organon, Hengelo, the Netherlands) Commission of the European Communities Joint Nuclear Research Centre - Ispra Establishment (Italy) Chemistry Luxembourg, July 1972 - 100 Pages - B.Fr. 225.— A new empirical relation between liquid dynamic viscosity, temperature and chemical constitution of organic compounds is proposed. The method is based on the De Guzman-Andrade equation and the introduction of a new property, the equivalent chain length of a compound, defined as the chain length (in carbon atoms) of the hypothetical η-alkane having a viscosity equal to 1 cP at the same temperature as the compound in question. EUR 4735 e LIQUID VISCOSITY AND CHEMICAL CONSTITUTION OF ORGANIC COMPOUNDS : A NEW CORRELATION AND A COMPILATION OF LITERATURE DATA by D. VAN VELZEN*, R. LOPES CARDOZO** and H. LANGENKAMP* * (Euratom) ** (Α.Κ.Ζ.O., Albatros Koninklijke Zout Organon, Hengelo, the Netherlands) Commission of the European Communities Joint Nuclear Research Centre - Ispra Establishment (Italy) Chemistry Luxembourg, July 1972 - 160 Pages - B.Fr. 225.— A new empirical relation between liquid dynamic viscosity, temperature and chemical constitution of organic compounds is proposed. The method is based on the De Guzman-Andrade equation and the introduction of a new property, the equivalent chain length of a compound, defined as the chain length (in carbon atoms) of the hypothetical η-alkane having a viscosity equal to 1 cP at the same temperature as the compound in question. EUR 4735 e LIQUID VISCOSITY AND CHEMICAL CONSTITUTION OF ORGANIC COMPOUNDS : A NEW CORRELATION AND A COMPILATION OF LITERATURE DATA by D. VAN VELZEN*, R. LOPES CARDOZO** and H. LANGENKAMP* * (Euratom) ** (Α.Κ.Ζ.O., Albatros Koninklijke Zout Organon, Hengelo, the Netherlands) Commission of the European Communities Joint Nuclear Research Centre - Ispra Establishment (Italy) Chemistry Luxembourg, July 1972 - 160 Pages - B.Fr. 225.— A new empirical relation between liquid dynamic viscosity, temperature and chemical constitution of organic compounds is proposed. The method is based on the De Guzman-Andrade equation and the introduction of a new property, the equivalent chain length of a compound, defined as the chain length (in carbon atoms) of the hypothetical η-alkane having a viscosity equal to 1 cP at the same temperature as the compound in question. Cumulative constitutional correction factors for the equivalent chain length and the slope of the log viscosity/temperature curve are proposed. With the aid of these data the viscosity between boiling and melting point of many compounds can be predicted. The method proves to be more accurate than the existing ones and it does not make use of any other physical property. In the Appendix of the report more than 4 000 viscosity data for more than 300 different compounds are compiled together with an appropriate index. Therefore, the Appendix may be used as a viscosity data handbook. Cumulative constitutional correction factors for the equivalent chain length and the slope of the log viscosity/temperature curve are proposed. With the aid of these data the viscosity between boiling and melting point of many compounds can be predicted. The method proves to be more accurate than the existing ones and it does not make use of any other physical property. In the Appendix of the report more than 4 000 viscosity data for more than 300 different compounds are compiled together with an appropriate index. Therefore, the Appendix may be used as a viscosity data handbook. Cumulative constitutional correction factors for the equivalent chain length and the slope of the log viscosity/temperature curve are proposed. With the aid of these data the viscosity between boiling and melting point of many compounds can be predicted. The method proves to be more accurate than the existing ones and it does not make use of any other physical property. In the Appendix of the report more than 4 000 viscosity data for more than 300 different compounds are compiled together with an appropriate index. Therefore, the Appendix may be used as a viscosity data handbook. EUR 4735 e COMMISSION OF THE EUROPEAN COMMUNITIES LIQUID VISCOSITY AND CHEMICAL CONSTITUTION OF ORGANIC COMPOUNDS : A NEW CORRELATION AND A COMPILATION OF LITERATURE DATA by D. VAN VELZEN (Euratom) R. LOPES CARDOZO (Α.Κ.Ζ.O., Albatros Koninklijke Zout Organon, Hengelo, the Netherlands) H. LANGENKAMP (Euratom) 1972 Joint Nuclear Research Centre Ispra Establishment - Italy Chemistry ABSTRACT Λ new empirical relation between liquid dynamic viscosity, temperature and chemical constitution of organic compounds is proposed. The method is based on the Dc Guzman-Andrade equation and the introduction of a new property, the equivalent chain length of a compound, defined as the chain length (in carbon atoms) of the hypothetical η-alkane having a viscosity equal to 1 el' at the same temperature as the compound in question. Cumulative constitutional correction factors for the equivalent chain length and the slope of the log viscosity/temperature curve are proposed. With the aid of these data the viscosity between boiling and melting point of many compounds can be predicted. The method proves to be more accurate than the existing ones and it does not make use of any other physical property. Γη the Appendix of the report more than 4 000 viscosity data for more than 300 different compounds are compiled together with an appropriate index. Therefore, the Appendix may be used as a viscosity data handbook. KEYWORDS VISCOSITY BENZOPHENONE LIQUIDS CYCLOHEXANE ORGANIC COMPOUNDS KETONES TEMPERATURE COEFFICIENT ALCOHOLS BINDING ENERGY ETHERS MOLECULAR STRUCTURE AROMATICS FUNCTIONS AMINES EQUATIONS ISOMERS ALKANES ESTERS ALKENES POLYPHENYLS ORGANIC ACIDS TABLES CHLOROFORM MEASURED VALUES CONTENTS Page 1. Introduction 5 2. Effect of temperature and chemical constitution ¡- on liquid viscosity 3. Proposed relation for the homologous series of the alkanes 7 4. General relation o. 5. Discussion 12 References ­j η Appendix I A 1 Appendix II A 155 ­ 5 ­ 1. INTRODUCTION *) The literature dealing with liquid viscosity is very extensive and many attempts have been made to correlate the vis­ cosity of liquids to temperature and chemical constitution on a theoretical hasis as well as purely empirically. Truly theoretical efforts have met with little success. Brush [1] summarizes the state of the art as follows: "The statement that (liquid) viscosity is due to inter­ atomic forces by no means constitutes a scientific theory. It is necessary to show that the assumption óf some specific type of force law, not too different from the laws assumed in other successful theories, leads to correct predictions of the value of the viscosity coefficient over the entire range of temperatures and pressures. We are certainly nowhere near having achieved this, at least if one judges by the standards applicable to gas theory. Instead we have a large number of competing "theories of viscosity", ranging from those which do no more than suggest explanations for the factors introduced into empirical formulas, to those which subject the unfortunate reader to hundreds of complex mathematical equations without rewarding him any real solution to the problem,,," At present there is no theory which allows liquid vis­ cosities to be calculated by simple equations, and thus empiri­ cal estimation techniques must be used. 2. EFFECT OF TEMPERATURE AND CHEMICAL CONSTITUTION ON LIQUID VISCOSITY The best known relation to correlate liquid viscosity and temperature is : B/T η L ­ Ae Eq. 1 where A and Β are positive, Eq, 1 was originally proposed by De Guzman [2] and has since become known as the Andrade equation, because Andrade suggested this form as a result of an analysis of the mechanism of liquid viscosity [3] · The equation repre­ sents the viscosity­temperature relation fairly well within the temperature range which extends from the normal boiling point to the freezing point. *) Manuscript received on November 3, 1971 For associated liquids and hydrocarbon mixtures of higher viscosity the relationship between log 9L and l/T is no longer a linear one, but becomes slightly curved. Consequently, in these cases the De Guzman-Andrade relation fails. To overcome this diffi­ culty, a large number of modifications of the original equation have been proposed, generally introducing, in one way or another, a third constant to correct the equation for the curvature.