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Heat Capacity of Liquids: Critical Review and Recommended Values Heat Capacity of Liquids: Critical Review and Recommended Values. Supplement I Cite as: Journal of Physical and Chemical Reference Data 30, 1199 (2001); https:// doi.org/10.1063/1.1407866 Submitted: 20 February 2001 . Published Online: 10 January 2002 Milan Zábranský, Vlastimil Růžička, and Eugene S. Domalski ARTICLES YOU MAY BE INTERESTED IN Heat Capacity of Liquids: Critical Review and Recommended Values. Supplement II Journal of Physical and Chemical Reference Data 39, 013103 (2010); https:// doi.org/10.1063/1.3182831 Estimation of the Heat Capacities of Organic Liquids as a Function of Temperature using Group Additivity. II. Compounds of Carbon, Hydrogen, Halogens, Nitrogen, Oxygen, and Sulfur Journal of Physical and Chemical Reference Data 22, 619 (1993); https:// doi.org/10.1063/1.555924 Heat Capacities and Entropies of Organic Compounds in the Condensed Phase. Volume III Journal of Physical and Chemical Reference Data 25, 1 (1996); https://doi.org/10.1063/1.555985 Journal of Physical and Chemical Reference Data 30, 1199 (2001); https://doi.org/10.1063/1.1407866 30, 1199 © 2002 by the U.S. Secretary of Commerce on behalf of the United States. All rights reserved. Heat Capacity of Liquids: Critical Review and Recommended Values. Supplement I Milan Za´bransky´, Vlastimil Ru˚ zˇicˇka, Jr.,a… and Eugene S. Domalskib… Department of Physical Chemistry, Institute of Chemical Technology, 166 28 Prague 6, Czech Republic ͑Received 20 February 2001; revised manuscript received 30 July 2001͒ A study was carried out in which new experimental data on heat capacities of pure liquid organic and some inorganic compounds were compiled, critically evaluated, and recommended values provided. Compounds included in the compilation have a melting point below 573 K. The bulk of the compiled data covers data published in the primary literature between 1993 and 1999 and some data of 2000. However, some data from older sources were also included. The data were taken from almost 1030 literature references. Parameters of correlating equations for temperature dependence of heat capacities of liquids were developed. This paper is an update of a two volume monograph entitled Heat Capacity of Liquids: Critical Review and Recommended Values ͑96ZAB/RUZ͒ that was published in 1996 in the Journal of Physical and Chemical Reference Data as Mono- graph No. 6 and was the product of the IUPAC Project No. 121/11/87. © 2002 by the U.S. Secretary of Commerce on behalf of the United States. All rights reserved. Key words: bibliography; correlating equations; critically evaluated data; heat capacity; liquids. Contents 6. References................................. 1213 7. Formula Index of Compounds................. 1232 1. Introduction................................ 1199 1.1. Definitions, Basic Relationships. .......... 1200 2. Calorimetric Techniques for Determining Heat List of Tables Capacities of Liquids........................ 1201 1. Criteria codes used for classification of 2.1. Terminology and Criteria for Classification calorimeters................................ 1202 of Calorimeters......................... 1201 2. Types of calorimeters used for determining heat 3. Methodology of Data Treatment; Establishment capacities of pure liquids. ................... 1202 of Recommended Data....................... 1207 3. Survey of calorimeters for determining heat 3.1. Data Base of Raw Values................. 1207 capacity of liquids referred to in this work....... 1203 3.2. Evaluation and Selection Process........... 1208 4. Division of compounds into groups. ........... 1210 3.3. Temperature Correlation and Establishment In the tabular part of the paper, a review of all primary of Recommended Values.................. 1209 sources of data, and results of correlation are summarized for 3.3.1. Representation of Data by each compound separately in one to four tables. Each table Polynomial͑s͒..................... 1209 is coded with three numbers. More information is given in 3.3.2. Representation of Data by a Sec. 4.2. The tabular information starts on page 104. Quasipolynomial Equation........... 1209 3.3.3. Types of Heat Capacities Presented. 1210 4. Guide to Tables............................ 1210 4.1. Division of Compounds into Groups........ 1210 4.2. Tables and Deviation Plot................. 1211 4.2.1. Experimental Heat Capacities........ 1211 1. Introduction 4.2.2. Correlated Heat Capacities........... 1212 4.2.3. Parameters of Polynomials........... 1212 Heat capacities belong among the basic thermophysical 4.2.4. Parameters of the Quasipolynomial and thermodynamic properties which characterize a liquid. Equation......................... 1213 They are directly linked with temperature derivatives of ba- 4.2.5. Deviation Plots.................... 1213 sic thermodynamic functions and are therefore indispensable 5. Acknowledgments.......................... 1213 for the calculation of differences in these functions between different temperatures. This information is widely used in ͒ a Electronic mail: [email protected] chemical engineering for establishing energy balances, in b͒ Also at National Institute of Standards and Technology, Gaithersburg, thermodynamics for obtaining entropy and enthalpy values, Maryland 20899. © 2002 by the U.S. Secretary of Commerce on behalf of the United States. and in thermochemistry for calculating changes in reaction All rights reserved. enthalpies with temperature. A knowledge of heat capacities Õ Õ Õ Õ Õ 0047-2689 2002 30„5… 1199 491 $35.001199 J. Phys. Chem. Ref. Data, Vol. 30, No. 5, 2002 1200 ZA´ BRANSKY´ ,RU˚ Zˇ ICˇ KA, AND DOMALSKI is also required for evaluating the effect of temperature on An annotated bibliography is given in Sec. 4 of Mono- phase and reaction equilibria. Variations in heat capacities graph No. 6 ͑96ZAB/RUZ͒ which lists compilations contain- serve as a sensitive indicator of phase transitions and are an ing reported values for the heat capacities of organic and important tool for understanding changes in the structure of some inorganic compounds from 1897 through 1991. Over liquid solutions. the period from 1991 through 2000, only one large compila- Since 1993 when compilation of data published in Mono- tion by Palczewska-Tulinˇska et al. ͑97PAL/WYR͒ was pub- graph No. 6 ͑96ZAB/RUZ͒ was ended a considerable lished which contains data on the heat capacity of organic amount of new data appeared in literature. In addition, some compounds in the condensed phase. Palczewska-Tulinska data published before 1993 that were omitted from Mono- et al. selected 610 sets of experimental data for 480 com- graph No. 6 were found. First the new data entail heat ca- pounds which were obtained from 350 literature sources. pacities for about 350 compounds not included in Mono- From this selection, the authors usually chose one or two sets graph No. 6. Second, new data that either extend the of experimental data which they considered the most reli- temperature range of recommended data for compounds al- able. Their compilation did not reveal any further critical ready presented in Monograph No. 6 or improve the overall assessment of the data. uncertainty of the recommended data by supplying new data In this paper we utilized some paragraphs from the textual ͑ ͒ that have a lower error of measurement were added for more part of Monograph No. 6 96ZAB/RUZ which are necessary than 320 compounds. Third, references to new data for about for describing the compilation, critical assessment, and cor- 50 compounds are presented in the form of a review of pri- relation of data as well as for understanding the tables. The mary sources only as the data for such compounds do not text was updated where needed and/or new information was extend or improve the previously developed recommended added. data. 1.1. Definitions, Basic Relationships The objectives of the present study were as follows: Heat capacity C is defined by the differential equation ͑1͒ To provide an exhaustive survey of the literature for ͒ ͑ ͒ ץ ץϭ͑ all isobaric and saturation heat capacities for pure or- C Q/ T x, 1 ganic and inorganic compounds in the liquid state where Q indicates the amount of heat exchanged between the which were published in the primary literature mainly system studied and the surroundings when the temperature T between 1993 and 1999 and some data of 2000. The changes under conditions specified by x. These conditions starting date, 1993, denotes the year when the compi- have to be specified as the heat, Q, is not a state function or lation of data presented in Monograph No. 6 was quantity, and C varies according to different paths along ended. which Q is exchanged. The corresponding intensive quanti- ͑2͒ To compile newly published heat capacities supple- ties are related to the unit amount of mass—specific heat mented by data omitted in the previous stage of a capacity c, or to one mole—molar heat capacity Cm . Some- project that ended in 1993 and appeared in Mono- times, heat capacities are also denoted as thermal coeffi- graph No. 6. To extend a computer readable database cients. of raw experimental data established in the previous Several different temperature gradients of thermodynamic project. Only data for well-defined compounds in the functions are encountered in the literature: isotropic liquid state, obtained by calorimetric mea- the isochoric heat capacity or heat capacity at constant surements were considered. The criterion for inclusion volume of a compound in the compilation required the com- T2͒ ͑2͒ץ/2AץT͒ ϭϪT͑ץ/UץT͒ ϭ͑ץ/SץC ϭT͑
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