Improving Thermodynamic Consistency Among Vapor Pressure Heat of PDF

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2017-12-01
Improving Thermodynamic Consistency Among

Vapor Pressure, Heat of Vaporization, and Liquid
and Ideal Gas Heat Capacities
Joseph Wallace Hogge
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Hogge, Joseph Wallace, "Improving Thermodynamic Consistency Among Vapor Pressure, Heat of Vaporization, and Liquid and Ideal
Gas Heat Capacities" (2017). All Theses and Dissertations. 6634.
https://scholarsarchive.byu.edu/etd/6634
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Vapor Pressure, Heat of Vaporization, and
Liquid and Ideal Gas Heat Capacities
A dissertation submitted to the faculty of

In partial fulfillment of the requirements for the degree of
Doctor of Philosophy
W. Vincent Wilding, Chair

Thomas A. Knotts
Dean Wheeler
Thomas H. Fletcher
John D. Hedengren
Department of Chemical Engineering

Copyright © 2017 Joseph Wallace Hogge

All Rights Reserved
ABSTRACT

Vapor Pressure, Heat of Vaporization, and
Liquid and Ideal Gas Heat Capacity

Department of Chemical Engineering, BYU
Doctor of Philosophy
Vapor pressure (𝑃𝑃vap ), heat of vaporization (Δ𝐻𝐻vap ), liquid heat capacity (𝐶𝐶𝑝𝑝𝑙𝑙 ), and ideal
𝑖𝑖𝑖𝑖
gas heat capacity (𝐶𝐶𝑝𝑝 ) are important properties for process design and optimization. This work
focuses on improving the thermodynamic consistency and accuracy of the aforementioned
properties since these can drastically affect the reliability, safety, and profitability of chemical
processes. They can be measured for pure organic compounds from the triple point, through the
normal boiling point, and up to the critical point. Additionally, Δ𝐻𝐻vap is proportional to the
derivative of vapor pressure with respect to temperature through the Clapeyron equation, and the
𝑖𝑖𝑖𝑖
difference between 𝐶𝐶𝑝𝑝𝑙𝑙 and 𝐶𝐶𝑝𝑝 is proportional to the derivative of heat of vaporization with
respect to temperature.
In order to improve temperature-dependent correlations, all the properties were analyzed

simultaneously. First, a temperature-dependent error model was developed using several versions
of the Riedel and Wagner 𝑃𝑃vap correlations. The ability of each correlation to match 𝐶𝐶𝑝𝑝𝑙𝑙 data was
determined for 5 well-known compounds. The Riedel equation performed better than the Wagner
equation when the best form was used. Second, the Riedel equation form was further modified,
and the best correlation form was found for about 50 compounds over 7 families. This led to the
development of a new vapor pressure prediction method using different Riedel equation forms to
fit 𝑃𝑃vap , Δ𝐻𝐻vap , and 𝐶𝐶𝑝𝑝𝑙𝑙 data simultaneously. Seventy compounds were tested, and the error
compared to liquid heat capacity data dropped from 10% with previous methods to 3% with this
new prediction method.
Additionally a differential scanning calorimeter (DSC) was purchased, and melting points
(𝑇𝑇𝑚𝑚 ), enthalpies of fusion (Δ𝐻𝐻fus ), and liquid heat capacities (𝐶𝐶𝑝𝑝𝑙𝑙 ) were measured for over twenty
compounds. For many of these compounds, the vapor pressure data and critical constants were
re-evaluated, and new vapor pressure correlations were recommended that were
thermodynamically consistent with measured liquid heat capacity data.
The Design Institute for Physical Properties (DIPPR) recommends best constants and
temperature-dependent values for pure compounds. These improvements were added to DIPPR
procedures, and over 200 compounds were re-analyzed so that the temperature-dependent
𝑖𝑖𝑖𝑖
correlations for 𝑃𝑃vap , Δ𝐻𝐻vap , 𝐶𝐶𝑝𝑝 , and 𝐶𝐶𝑝𝑝𝑙𝑙 became more internally consistent. Recommendations
were made for the calculation procedures of these properties for the DIPPR database.
Keywords: multi-property optimization, vapor pressure, heat capacity, heat of vaporization

ACKNOWLEDGEMENTS
I would like to thank all of the people who helped me in this project and made it possible.
I thank my wife, Julie, and our 2 kids, Louisa and Adelaide, for all of their unwavering support
and motivation. My gratitude goes out to my advisor, Dr. Wilding, along with Dr. Knotts, Dr.
Giles, and other members of my committee that helped bring this project to fruition. I would also
like to thank my father, Jeff, who talked me through my freshman writing class. Without his
encouragement, I would never have thought it possible to write this document. I thank my mother,
Kim, for instilling in me a desire to learn about the world around us.
TABLE OF CONTENTS
LIST OF TABLES ....................................................................................................................... viii

LIST OF FIGURES ..................................................................................................................... xvi
1 Introduction ............................................................................................................................. 1
2 Thermodynamic Relationships ................................................................................................ 4
3 Literature Review of Thermophysical Properties .................................................................... 7
3.1 Vapor Pressure ................................................................................................................. 7
3.1.1 Vapor Pressure Correlation Equations ............................................................. 7
3.1.2 Vapor Pressure Data Availability .................................................................... 9
3.2 Heat of Vaporization ........................................................................................................ 9
3.2.1 Heat of Vaporization Correlation Equations.................................................. 10
3.2.2 Heat of Vaporization Data Availability ......................................................... 10
3.3 Ideal Gas Heat Capacity ................................................................................................. 12
3.3.1 Ideal Gas Heat Capacity Correlation Equations ............................................ 12
3.3.2 Ideal Gas Heat Capacity Data Availability .................................................... 13
3.4 Liquid Heat Capacity ..................................................................................................... 17
3.4.1 Liquid Heat Capacity Temperature Behavior ................................................ 18
3.4.2 Liquid Heat Capacity Data Availability ........................................................ 20
3.5 Analysis of Experimental Data and Correlations ........................................................... 20
4 Multi-Property Optimization – Temperature Dependent Errors ........................................... 23
4.1 Weight Model ................................................................................................................. 23
4.2 Results/Discussion ......................................................................................................... 25
4.3 Conclusions .................................................................................................................... 29
5 Multi-Property Optimization – The Riedel Equation ............................................................ 31
5.1 Methods .......................................................................................................................... 31
5.2 Results ............................................................................................................................ 34
5.3 Conclusions .................................................................................................................... 44
6 New Thermodynamically Consistent Vapor Pressure Prediction ......................................... 46
6.1 Introduction .................................................................................................................... 47
iv
6.2 Overview of Vapor Pressure Prediction and Correlation Methods ................................ 48
6.3 Theory ............................................................................................................................ 51
6.3.1 Thermodynamic Relationships ...................................................................... 51
6.3.1 New Predictive Vapor Pressure Method ........................................................ 51
6.4 Methods .......................................................................................................................... 53
6.4.1 Regression of K and Xc as a Function of E .................................................... 53
6.4.2 E Training Method ......................................................................................... 56
6.5 Results ............................................................................................................................ 57
6.5.1 Optimized E by Family .................................................................................. 57
6.5.2 Comparison to Other Predictive Methods...................................................... 60
6.5.3 Testing the Methods with Compounds Not Used in the Training Set ........... 63
6.6 Conclusions .................................................................................................................... 64
7 Experimental Work................................................................................................................ 67
7.1 Compounds..................................................................................................................... 67
7.2 Calibrations/Verifications .............................................................................................. 70
7.3 Uncertainties................................................................................................................... 76
7.4 Property Selection for Thermodynamic Analysis .......................................................... 77
7.5 Results ............................................................................................................................ 77
7.5.1 Toluene Derivatives ....................................................................................... 81
7.5.2 Phenyl Propanols ........................................................................................... 86
7.5.3 Furans............................................................................................................. 88
7.5.4 Phenyl Acetates.............................................................................................. 90
7.5.5 n-Hexylcyclohexane ...................................................................................... 92
7.5.6 6-Undecanone ................................................................................................ 95
7.5.7 1H-Perfluorooctane ........................................................................................ 96
7.5.8 2,6-Dimethoxyphenol .................................................................................... 97
7.5.9 trans-Isoeugenol ............................................................................................ 99
7.5.10 1-Propoxy-2-Propanol................................................................................ 102
7.6 Conclusions .................................................................................................................. 103
8 Best Practices, Recommendations, and Incorporations into the Database .......................... 105
8.1 Introduction .................................................................................................................. 105
v
8.2 Ideal Gas Heat Capacity Database Fixes...................................................................... 105
8.3 Derivative vs. Integral Methods ................................................................................... 108
8.4 Compounds without Liquid Heat Capacity Data ......................................................... 113
8.5 Recommendation Summary ......................................................................................... 115
8.6 DIPPR Database Improvements ................................................................................... 117
8.7 Association ................................................................................................................... 118
8.7.1 Saturated Monomer Mole Fraction .............................................................. 120
8.7.2 Heat of Vaporization .................................................................................... 122
8.7.3 Future Work ................................................................................................. 123
9 Conclusions ......................................................................................................................... 124
9.1 Future Work ................................................................................................................. 126
9.1.1 Continue Liquid Heat Capacity Measurements ........................................... 127
9.1.2 Measure Vapor Pressure .............................................................................. 127
9.1.3 Improve the Multi-Property Optimization ................................................... 128
9.1.4 Measure the Solid Phase Properties ............................................................. 129
9.1.5 Measure Ideal Gas Heat Capacity ................................................................ 129
9.1.6 Improve Methods for Associating Compounds ........................................... 129
9.1.7 Reduce Heat of Vaporization Uncertainty ................................................... 130
References ................................................................................................................................... 131
Appendix A. Thermodynamic Derivations ............................................................................. 204
A.1 Clapeyron Equation Derivation ................................................................................... 204
A.2 Derivative Method Derivation ..................................................................................... 204
A.2.1 Saturation and Isobaric Heat Capacities ................................................................... 205
A.2.2 Vapor and Ideal Gas Heat Capacities ....................................................................... 206
A.2.2 The Derivative Method ............................................................................................. 207
A.3 Ideal Gas Heat Capacity Derivation using Statistical Mechanics ................................ 208
Appendix B. Data Used .......................................................................................................... 211
B.1 Vapor Pressure Data ..................................................................................................... 211
B.1.1 Vapor Pressure Data for Riedel Equation Analysis ..................................... 211
B.1.2 Vapor Pressure Data for New Predictive Riedel Equation .......................... 215
B.2 Heat of Vaporization Data............................................................................................ 223
vi
B.3 Liquid Heat Capacity Data ........................................................................................... 230
B.3.1 Liquid Heat Capacity Data for Riedel Equation Analysis ........................... 230
B.3.2 Liquid Heat Capacity Data for New Predictive Riedel Equation ................ 234
B.4 Compounds measured .................................................................................................... 241
Appendix C. Sample Calculation for Predictive Method ....................................................... 245
vii
LIST OF TABLES
Table 2-1: Calculation methods for properties in the Derivative method for finding 𝑪𝑪𝑪𝑪𝑪𝑪 ............. 6
Table 4-1: Summary of the sum squared errors used ................................................................... 24
Table 4-2: Optimized vapor pressure correlations with triple point pressures ............................. 29
Table 5-1: A list of hydrocarbons investigated in this study, grouped by chemical family ......... 32
Table 5-2: A list of non-hydrocarbons investigated in this study, ................................................ 32
Table 5-3: Absolute average deviation of Equation 5-1 fit to vapor pressure data ...................... 34
Table 5-4: Summary of triple point pressures (in Pa) from literature........................................... 42
Table 5-10: Summary of triple point pressure (in Pa) from literature .......................................... 44
Table 6-1: Compounds originally investigated by Riedel, ........................................................... 49
Table 6-2: Training set of compounds for the new ....................................................................... 55
Table 6-3: Summary of prediction constants for the original ....................................................... 55
Table 6-4: Average Pvap, ΔHvap, and Cpl absolute average deviations (AAD) for the
compounds in each chemical family using the best 𝑬𝑬 value for each compound......................... 58
Table 6-5: Recommended E values for each of the ...................................................................... 60
Table 7-1: Purities of compounds measured in this study ............................................................ 71
Table 7-2: Purities of verification compounds used in this study................................................. 71
Table 7-3: Temperature and heat verification of melting point (Tm/K) ........................................ 73
viii
Table 7-4 Summary of vapor pressure fitting techniques ............................................................. 77
Table 7-5: Summary of liquid heat capacity measurements with uncertainties ........................... 78
Table 7-6: Summary of experimental melting point measurements a ........................................... 80
Table 7-7 Summary of experimental enthalpy of fusion measurements a .................................... 81
Table 7-8: Summary of experimental melting points for the toluene derivatives ........................ 82
Table 7-10: Summary of enthalpy of fusion experimental results for the toluene
derivatives ..................................................................................................................................... 83
Table 7-11: Summary of best critical constants and vapor pressure coefficients ......................... 85
Table 7-12: Summary of experimental glass transition temperatures .......................................... 86
Table 7-13: Summary of experimental melting points for the phenyl propanols ......................... 87
Table 7-14: Summary of enthalpy of fusion experimental results for the phenyl propanols ....... 87
Table 7-15: Summary of experimental melting points for the furans ........................................... 89
Table 7-16: Summary of enthalpy of fusion experimental results for the furans ......................... 89
Table 7-17: Summary of best critical constants and vapor pressure ............................................ 90
Table 7-18: Summary of experimental melting points for the phenyl acetates ............................ 91
Table 7-19: Summary of enthalpy of fusion experimental results for the phenyl acetates........... 92
Table 7-21: Summary of experimental melting points for the alkylcyclohexanes ....................... 93
Table 7-22: Summary of enthalpy of fusion experimental results for the
alkylcyclohexanes ......................................................................................................................... 93
Table 7-24: Summary of experimental melting points for the di-n-alkyl ketones ........................ 95
ix
Table 7-25: Summary of enthalpy of fusion experimental results for the di-n-alkyl
ketones .......................................................................................................................................... 95
Table 7-27: Summary of experimental melting points for............................................................ 96
Table 7-28: Summary of enthalpy of fusion experimental results for .......................................... 97
Table 7-29: Summary of experimental melting points for............................................................ 98
Table 7-30: Summary of enthalpy of fusion experimental results for .......................................... 98
Table 7-32: Summary of experimental melting points for trans-isoeugenol .............................. 101
Table 7-33: Summary of experimental enthalpy of fusion for trans-isoeugenol........................ 101
Table 7-34: Summary of best critical constants and vapor pressure .......................................... 102
Table 8-1: Summary of best recommendations for achieving thermodynamic consistency ...... 116
Table B-1: Summary of vapor pressure data used in this work for the n-alkanes ...................... 212
Table B-2: Summary of vapor pressure data used in this work for the 2-methylalkanes ........... 212
Table B-3: Summary of vapor pressure data used in this work for the 1-alkenes ...................... 212
Table B-4: Summary of vapor pressure data used in this work for the n-aldehydes .................. 212
Table B-5: Summary of vapor pressure data used in this work for aromatic compounds .......... 213
Table B-6: Summary of vapor pressure data used in this work for the ethers ............................ 213
Table B-7: Summary of vapor pressure data used in this work for the ketones ......................... 213
Table B-8: Summary of vapor pressure data used in this work for alkanes and alkenes ........... 216
Table B-9: Summary of vapor pressure data used in this work for aromatic compounds .......... 216
Table B-10: Summary of vapor pressure data used in this work for the esters and ethers ......... 216
Table B-11: Summary of vapor pressure data used in this work for the gases ........................... 217
x
Table B-12: Summary of vapor pressure data used in this work for the halogenated
compounds .................................................................................................................................. 217
Table B-13: Summary of vapor pressure data used in this work for the ketones ....................... 217
Table B-14: Summary of vapor pressure data used in this work for alkanes ............................. 217
Table B-15: Summary of vapor pressure data used in this work for multifunctional
compounds .................................................................................................................................. 218
Table B-16: Summary of vapor pressure data used in this work for the 1-alkenes .................... 218
Table B-16: Summary of vapor pressure data used in this work for the 1-alkenes .................... 219
Table B-17: Summary of vapor pressure data used in this work for the n-aldehydes ................ 219
Table B-18: Summary of vapor pressure data used in this work for aromatic compounds ........ 219
Table B-19: Summary of vapor pressure data used in this work for the ethers .......................... 220
Table B-20: Summary of vapor pressure data used in this work for the ketones ....................... 220
Table B-21: Summary of vapor pressure data used in this work for the amines ........................ 220
Table B-22: Summary of vapor pressure data used in this work for the ringed alkanes ............ 221
Table B-23: Summary of vapor pressure data used in this work for the halogenated
compounds .................................................................................................................................. 221
Table B-24: Summary of vapor pressure data used in this work for the esters .......................... 221
Table B-25: Summary of vapor pressure data used in this work for the sulfides ....................... 221
Table B-26: Summary of vapor pressure data used in this work for the alkynes and
silanes.......................................................................................................................................... 222
Table B-80: Summary of heat of vaporization data used in this work for alkanes and
alkenes......................................................................................................................................... 224
xi
Table B-81: Summary of heat of vaporization data used in this work for the aromatic
compounds .................................................................................................................................. 224
Table B-82: Summary of heat of vaporization data used in this work for the esters and
ethers ........................................................................................................................................... 224
Table B-83: Summary of heat of vaporization data used in this work for the gases .................. 225
Table B-84: Summary of heat of vaporization data used in this work for the halogenated
compounds .................................................................................................................................. 225
Table B-85: Summary of heat of vaporization data used in this work for the ketones............... 225
Table B-86: Summary of heat of vaporization data used in this work for alkanes ..................... 225
Table B-87: Summary of heat of vaporization used in this work for the 1-alkenes ................... 226
Table B-88: Summary of heat of vaporization data used in this work for the n-aldehydes ....... 226
Table B-89: Summary of heat of vaporization data used in this work for the aromatic
compounds .................................................................................................................................. 227
Table B-90: Summary of heat of vaporization data used in this work for the ethers ................. 227
Table B-91: Summary of heat of vaporization data used in this work for the ketones............... 227
Table B-92: Summary of heat of vaporization data used in this work for the amines ............... 227
Table B-93: Summary of heat of vaporization data used in this work for the ringed
alkanes......................................................................................................................................... 228
Table B-94: Summary of heat of vaporization data used in this work for the halogenated
compounds .................................................................................................................................. 228
Table B-95: Summary of heat of vaporization data used in this work for the esters .................. 228
Table B-96: Summary of heat of vaporization data used in this work for the sulfides .............. 229
xii
Table B-97: Summary of heat of vaporization data used in this work for the alkynes and
silanes.......................................................................................................................................... 229
Table B-98: Summary of heat of vaporization data used in this work for multifunctional
compounds .................................................................................................................................. 229
Table B-46: Summary of liquid heat capacity data used in this work for the n-alkanes ............ 231
Table B-47: Summary of liquid heat capacity data used in this work for the 2-
methylalkanes ............................................................................................................................. 231
Table B-48: Summary of liquid heat capacity data used in this work for the 1-alkenes ............ 231
Table B-49: Summary of liquid heat capacity data used in this work for the n-aldehydes ........ 231
Table B-50: Summary of liquid heat capacity data used in this work for the aromatic
compounds .................................................................................................................................. 232
Table B-51: Summary of liquid heat capacity data used in this work for the ethers .................. 232
Table B-52: Summary of liquid heat capacity data used in this work for the ketones ............... 232
Table B-53: Summary of liquid heat capacity data used in this work for alkanes and
alkenes......................................................................................................................................... 235
compounds .................................................................................................................................. 235
Table B-55: Summary of liquid heat capacity data used in this work for the esters and
ethers ........................................................................................................................................... 235
Table B-56: Summary of liquid heat capacity data used in this work for the gases ................... 236
Table B-57: Summary of liquid heat capacity data used in this work for the halogenated
compounds .................................................................................................................................. 236
xiii
Table B-59: Summary of liquid heat capacity data used in this work for alkanes ..................... 236
Table B-60: Summary of liquid heat capacity data used in this work for the 1-alkenes ............ 237
Table B-61: Summary of liquid heat capacity data used in this work for the n-aldehydes ........ 237
compounds .................................................................................................................................. 237
Table B-63: Summary of liquid heat capacity data used in this work for the ethers .................. 238
Table B-65: Summary of liquid heat capacity data used in this work for the amines ................ 238
Table B-66: Summary of liquid heat capacity data used in this work for the ringed
alkanes......................................................................................................................................... 239
Table B-67: Summary of liquid heat capacity data used in this work for the halogenated
compounds .................................................................................................................................. 239
Table B-68: Summary of liquid heat capacity data used in this work for the esters .................. 239
Table B-69: Summary of liquid heat capacity data used in this work for the sulfides ............... 239
Table B-70: Summary of liquid heat capacity data used in this work for the alkynes and
silanes.......................................................................................................................................... 240
Table B-71: Summary of liquid heat capacity data used in this work for multifunctional
compounds .................................................................................................................................. 240
Table B-72: Summary of melting point and melting enthalpy literature data ............................ 241
Table B-73: Summary of vapor pressure literature data ............................................................. 242
Table B-74: Summary of heat of vaporization literature data .................................................... 244
Table B-75: Summary of liquid heat capacity literature data ..................................................... 244
Table C-1: Summary of compound constants for 2,2-dimethylpentane ..................................... 245
xiv
Table C-2: Summary of reduced properties for 2,2-dimethylpentane ........................................ 245
xv
LIST OF FIGURES
Figure 3-1: Pie chart of ΔHvap data labeled as “Experimental” in the DIPPR database ............... 11
Figure 3-2: ΔHvap calorimetric and derived data with the DIPPR correlation for propylene ....... 11
Figure 3-3: Pie chart of Cpig data labeled as “Experimental” in the DIPPR database .................. 14
Figure 3-4: Pie chart of measurement techniques used for actual experimental Cpig data in
the DIPPR database....................................................................................................................... 15
Figure 3-5: Quantum mechanical calculation error versus temperature for Cpig compared
to true experimental data in the literature ..................................................................................... 16
Figure 3-6: Error distribution for quantum mechanical values compared to experimental
Cpig data ......................................................................................................................................... 17
Figure 3-7: Cpl data and DIPPR correlations for butane, 1-butene, 1-propanol, and
ethylene glycol .............................................................................................................................. 19
Figure 3-8: Cpl Data and DIPPR correlation for propylene, along with the Derivative
method prediction from the start of this project............................................................................ 19
Figure 3-9: A qualitative look at the relative frequency of experimental data for vapor
pressure, heat of vaporization, and liquid heat capacity around the normal boiling point ........... 21
Figure 4-1: Temperature dependent weight model used in the multi-property optimization
for vapor pressure, heat of vaporization, and liquid heat capacity around the normal
boiling point .................................................................................................................................. 25
Figure 4-2: Average absolute deviation (AAD) for propylene across vapor pressure, heat
of vaporization, and liquid heat capacity data with the starting fit, the R1 fit, the R2 fit,
the R6 fit, the W2 fit, and the W3 fit with temperature dependent weights ................................. 27
xvi
Figure 4-3: Experimental data for propylene with the starting and optimized Riedel 2 fits
for (a) vapor pressure, (b) natural log of vapor pressure, (c) heat of vaporization, and (d)
liquid isobaric heat capacity.......................................................................................................... 28
Figure 4-4: The average AAD from Pvap, ΔHvap, and Cpl using the starting fit to Pvap data
only and the optimized R1, R2, R6, W2, and W3 fits for the five compounds studied................ 29
Figure 5-1: Heat of vaporization experimental data and Clapeyron equations using the
Riedel equation with E = 1 through 𝟔𝟔 with the temperature range of vapor pressure data
shown ............................................................................................................................................ 36
Figure 5-2: Liquid heat capacity data and Derivative method predictions from the Riedel
equation with E = 1 through 6 with the temperature range of vapor pressure data shown ........... 37
Figure 5-3: Absolute average deviation of a) vapor pressure data and b) liquid heat
capacity data of fits with the use of the Riedel equation with 𝑬𝑬 =0.5 through E=6 for the
n-alkanes ethane ( ), propane ( ), butane ( ), pentane ( ), hexane ( ),
heptane ( ), and octane ( ) ................................................................................................... 38
2-methylalkanes isopropane ( ), 2-methylbutane ( ), 2-methylpentane ( ), 2-
methylhexane ( ), and 2-methylheptane ( )......................................................................... 39
1-alkenes propylene ( ), 1-butene ( ), 1-pentene ( ), 1-hexene ( ), and 1-
heptene ( ) ................................................................................................................................ 39
xvii
capacity data of fits with the use of the Riedel equation with 𝑬𝑬 = 0.5 through E=6 for the
n-aldehydes butanal ( ), pentanal ( ), hexanal ( ), and heptanal ( ) .......................... 40
aromatic compounds benzene ( ), toluene ( ), m-xylene ( ), o-xylene ( ), p-
xylene ( ), ethylbenzene ( ), propylbenzene ( ), and butylbenzene ( ) .................... 40
ethers dimethyl ether ( ), diethyl ether ( ), ethyl propyl ether ( ), di-n-propyl
ether ( ), and methyl tert-butyl ether ( ) .............................................................................. 41
ketones methyl ethyl ketone ( ), methyl isopropyl ketone ( ), methyl isobutyl
ketone ( ), 2-pentanone ( ), 2-hexanone ( ), 3-hexanone ( ), 2-heptanone (
), and 2-octanone ( ) ........................................................................................................ 41
Figure 5-10: Triple point pressures versus carbon number for n-alkanes comparing
DIPPR values [44], REFPROP values [54], and values from this work ...................................... 44
Figure 6-1: Fitting parameters K and Xc as functions of E ........................................................... 55
Figure 6-2: Distribution of best E values using the new predictive Riedel Pvap method on
the test compounds ........................................................................................................................ 59
xviii
Figure 6-3: The distribution of Pvap AAD for 106 test compounds using Pvap prediction
methods: Riedel’s original method, Lee-Kesler, Vetere’s Wagner method, Vetere’s
Riedel method, and this work ....................................................................................................... 61
Figure 6-4: The distribution of ΔHvap for 106 test compounds using Pvap prediction
methods: Riedel’s original method, Lee-Kesler, Vetere’s Wagner method, Vetere’s
Riedel method, and this work ....................................................................................................... 62
Figure 6-5: The distribution of Cpl AAD for the test compounds using Pvap prediction
methods within the Derivative method: Riedel’s original method, Lee-Kesler, Vetere’s
Wagner method, Vetere’s Riedel method, and this work ............................................................. 63
Figure 6-6: Average Pvap, ΔHvap, and Cpl AAD for five sets of 40 compounds using
different Pvap prediction methods .................................................................................................. 64
Figure 7-1: Verification results for a) temperature and b) heat calibrations, with the
average difference for each compound from the DIPPR value [44] ( ) and 95%
confidence intervals on the measurements, and the uncertainties from this study ( ) ........... 74
Figure 7-2: Verification results for heat capacity of n-heptane with 95% confidence
intervals compared to the DIPPR correlation, DIPPR uncertainty, and literature data ................ 75
Figure 7-3: Verification results for heat capacity of sapphire with 95% confidence
intervals compared to the DIPPR correlation, DIPPR uncertainty, and literature data ................ 76
Figure 7-4 The toluene derivatives measured in this study .......................................................... 82
Figure 7-5 Melting points for xylenes ( ), tolualdehydes ( ), tolualcohols ( ), and toluic
acids ( ) with uncertainties contained within the size of the markers, open symbols
represent new data from this study ............................................................................................... 83
xix
Figure 7-6 Enthalpies of fusion for xylenes ( ), tolualdehydes ( ), tolualcohols ( ), and
toluic acids ( ) with uncertainties from DIPPR and this study, open symbols represent
new data from this study ............................................................................................................... 84
Figure 7-7 Liquid heat capacity measurements for m-tolualdehyde ( ), o-tolualdehyde (
), p-tolualdehyde ( ), m-tolualcohol ( ), and p-toluic acid ( ) with experimental
uncertainty from this study ........................................................................................................... 85
Figure 7-8: The phenyl propanols measured in this study ............................................................ 86
Figure 7-9 Liquid heat capacity measurements for 1-phenyl-1-propanol ( ), 1-phenyl-2-
propanol ( ), 2-phenyl-1-propanol ( ), and 2-isopropylphenol ( ) with experimental
uncertainty..................................................................................................................................... 88
Figure 7-10: The furans measured in this study............................................................................ 88
Figure 7-11: Comparison compounds for the furans .................................................................... 88
Figure 7-12: The phenyl acetates measured in this study ............................................................. 91
Figure 7-13: Comparison compounds for the phenyl acetates...................................................... 91
Figure 7-14: n-hexylcyclohexane ................................................................................................. 93
Figure 7-15: Liquid heat capacity data for n-ethyl- ( ) and n-butyl- ( ) with DIPPR
uncertainty, and n-hexyl- ( ) cyclohexane and experimental uncertainty ................................... 94
Figure 7-16: 6-undecanone ........................................................................................................... 95
Figure 7-17: 1H-perfluorooctane .................................................................................................. 96
Figure 7-18: 2,6-dimethoxyphenol ............................................................................................... 97
Figure 7-19: Compounds compared to 2,6-dimethoxyphenol ...................................................... 98
Figure 7-20: trans-isoeugenol ..................................................................................................... 100
Figure 7-21: Comparison compounds for trans-isoeugenol ....................................................... 100
xx
Figure 7-22: 1-propoxyl-2-propanol ........................................................................................... 102
Figure 8-1: The ideal gas heat capacity for methyl ethyl ketone with data and DIPPR
uncertainty and different basis sets, levels of theory, and scaling factors .................................. 107
Figure 8-2: Liquid heat capacity data for propylene with the derivative and integral
methods from the start of this project (2013).............................................................................. 110
methods with a better ideal gas heat capacity correlation (2014) ............................................... 110
Figure 8-4: Liquid heat capacity data for propylene with the Derivative and Integral
methods with the Derivative method extended above normal boiling point (2015)................... 112
Figure 8-5 The equation used to calculate coefficients for the integral method (2014) ............. 112
methods now (2017) compared to the start of this project (2013) .............................................. 113
Figure 8-7: Liquid heat capacity for trans-1-chloro-3,3,3-trifluoro-1-propene with several
prediction methods ...................................................................................................................... 114
Figure 8-8: The average absolute deviations for the vapor pressure and Derivative method
heat capacity fits before and after analysis ................................................................................. 118
Figure 8-9: The monomer mole fractions for n-alkanoic acids along the saturation curve ........ 121
Figure 8-10: Heat of vaporization experimental data and curves derived using the
Clapeyron equation for n-carboxylic acids with association ...................................................... 123
Figure 9-1: The experimental setup recommended by ASTM E1782-14 to measure Pvap
via DSC ....................................................................................................................................... 128
xxi
1 INTRODUCTION
The U.S. chemical process industry converts raw materials into more than 70,000
products worth about $760 billion dollars annually [1]. These products contribute to nearly every
object used by a modern society, which has come to rely on their consistent production.
Chemical processing plant design and operation require accurate values of thermophysical
properties. Some of the most important material properties include:
• Vapor pressure (𝑃𝑃vap ) – the pressure exerted by a saturated liquid
• Heat of vaporization (𝛥𝛥𝐻𝐻vap ) – the heat required to convert a liquid to a gas
• Isobaric heat capacities – the heat required to change a material’s temperature (𝐶𝐶𝑝𝑝𝑙𝑙 for liquids and
𝑖𝑖𝑖𝑖
𝐶𝐶𝑝𝑝 for ideal gases)
Vapor pressure is used to determine the size and pressure rating of materials needed for
process equipment, such as distillation columns. Heat capacities and heat of vaporization are
used to determine heat exchanger duties and other energy-dependent quantities. These properties
are functions of temperature and experimental data are often fit to correlations to facilitate design
calculations.
𝑖𝑖𝑖𝑖
𝐶𝐶𝑝𝑝𝑙𝑙 , 𝐶𝐶𝑝𝑝 , Δ𝐻𝐻vap , and 𝑃𝑃vap are related thermodynamically. Using these thermodynamic
relations, one of the properties can be exactly predicted if the other three are known. However,
using temperature-dependent correlations causes inaccuracies such that thermodynamic
predictions do not match experimental data. In temperature regions where measurements can be
1
easily and accurately made, the thermodynamic relationships can predict properties reasonably
well with well-known procedures. Hence, for compounds and regions without accurate
experimental data, the use of predictive thermodynamics in calculating these properties is less
reliable.
One of the reasons for this uncertainty is that the traditional process for data reduction is
to fit the data for each property independent of the others, without regard for the effect of the
regression on the other properties. Consider the following example. Data for vapor pressure and
liquid heat capacity are available for a compound. The former are usually found at temperatures
above the normal boiling point while the latter are taken below the normal boiling point.
Regression of the vapor pressure data is done solely to reduce the error between the higher-
temperature data and the correlation. This means the low-temperature behavior is not based on
experimental data. Likewise, the liquid heat capacity, low-temperature data are fit to the
correlating equation such that the high-temperature behavior is extrapolation. These two
properties are related by rigorous thermodynamic relationships, but because each was regressed
independently the expected relationship is not seen.
This project fixed this situation by improving agreement between experimental data and
thermodynamically predicted data for 𝑃𝑃vap , Δ𝐻𝐻vap , and 𝐶𝐶𝑝𝑝𝑙𝑙 by developing a regression scheme
that simultaneously optimizes the fit for each of the properties using the interproperty
relationships. This was be done by:
1. Gathering and evaluating data in the literature
2. Developing a correct understanding of the temperature dependent shapes of data correlations and
of interrelationships among these properties
3. Finding and recommending best practices
4. Experimentally measuring some properties to improve understanding and fill gaps in data
2
5. Implementing updated procedures into the Design Institute for Physical Properties (DIPPR)
compound review protocol
The remainder of this document is organized as follows. First, the thermodynamic
relationships between these properties are shown. Following this background, correlations and
general literature reviews are written for each property. Then, improvements made by this
project in the multi-property optimization scheme are given in Chapters 5 and 6. A new
prediction method for vapor pressure is described in Chapter 6. Experimental measurements are
supplied and analyzed in Chapter 7. After that, other database fixes and recommendations are
detailed in Chapter 8. Finally, conclusions formed in the course of this project are detailed, and a
list of recommendations for future work is given.
3
2 THERMODYNAMIC RELATIONSHIPS
𝑃𝑃vap and Δ𝐻𝐻vap both describe phase equilibrium between liquid and vapor. The
relationship between these two properties can by found by equating the changes in Gibbs energy
across phases as shown in the Appendix. This results in the famous Clapeyron equation which
relates the two properties. Specifically, assuming limited vapor association [2], the Clapeyron
equation is:
𝑑𝑑𝑃𝑃vap Δ𝐻𝐻vap
� �= (2-1)
𝑑𝑑 𝑇𝑇 𝑇𝑇(𝑉𝑉vap − 𝑉𝑉liq )
where 𝑃𝑃vap is vapor pressure, 𝑇𝑇 is the temperature, Δ𝐻𝐻vap is the heat of vaporization, 𝑉𝑉vap is the
vapor molar volume, 𝑉𝑉liq is the liquid molar volume. This equation may also be written in terms
of the compressibility of each phase according to:
𝑑𝑑ln(𝑃𝑃vap ) Δ𝐻𝐻vap
� �= (2-2)
𝑑𝑑 1/𝑇𝑇 (𝑍𝑍vap − 𝑍𝑍liq )
where 𝑍𝑍vap is the vapor compressibility factor and 𝑍𝑍liq is the liquid compressibility factor. This
project focused on using the first form, though the second form is often seen in literature.
Due to the equilibrium condition between pure vapor and liquid, another relationship may
be written that relates the heat of vaporization to the heat capacities of each phase, specifically:
𝑑𝑑Δ𝐻𝐻vap vap liq

� � = 𝐶𝐶𝜎𝜎 − 𝐶𝐶𝜎𝜎 (2-3)
𝑑𝑑 𝑇𝑇
4
vap liq
where 𝑇𝑇 is temperature and 𝐶𝐶𝜎𝜎 and 𝐶𝐶𝜎𝜎 refer to heat capacities along the saturation curve for
vap liq 𝑖𝑖𝑖𝑖

vapor and liquid, respectively. 𝐶𝐶𝜎𝜎 and 𝐶𝐶𝜎𝜎 differ from 𝐶𝐶𝑝𝑝 and 𝐶𝐶𝑝𝑝𝑙𝑙 (the values of most interest
to industry and most commonly encountered) in two ways: 1) they reflect the change in enthalpy
along the saturation pressure curve, and 2) vapor heat capacity differs from ideal gas heat
capacity due to molecular interactions present in the real gas that are neglected in the ideal gas
model. Correcting for these differences gives [2, 3]:

𝑉𝑉𝑉𝑉
vap 𝑖𝑖𝑖𝑖 𝜕𝜕 2 𝑉𝑉vap 𝜕𝜕𝑉𝑉vap 𝑑𝑑𝑃𝑃vap
𝐶𝐶𝜎𝜎 = 𝐶𝐶𝑝𝑝 − 𝑇𝑇 � � � 𝑑𝑑𝑑𝑑 + �𝑉𝑉
v ap − 𝑇𝑇 � � � (2-4)
𝜕𝜕𝑇𝑇 2 𝜕𝜕𝜕𝜕 𝑃𝑃 𝑑𝑑𝑑𝑑
0
liq 𝜕𝜕𝑉𝑉liq 𝑑𝑑𝑃𝑃vap

𝐶𝐶𝜎𝜎 = 𝐶𝐶𝑝𝑝𝑙𝑙 + �𝑉𝑉liq − 𝑇𝑇 � � � (2-5)
𝜕𝜕𝜕𝜕 𝑃𝑃 𝑑𝑑𝑑𝑑
Derivations of these two equations are given in the Appendix.
Substituting these relationships into Equation 2-3 allows us to relate derivatives of vapor
pressure and heat of vaporization to the heat capacities. Specifically, the thermodynamically-
rigorous expression that relates 𝐶𝐶𝑝𝑝𝑙𝑙 to ideal gas heat capacity, heat of vaporization, and vapor
pressure is:
𝑃𝑃vap
𝑖𝑖𝑖𝑖 𝜕𝜕 2 𝑉𝑉vap 𝑑𝑑𝑑𝑑𝐻𝐻vap 𝜕𝜕Δ𝑉𝑉 𝑑𝑑𝑃𝑃vap
𝐶𝐶𝑝𝑝𝑙𝑙 = 𝐶𝐶𝑝𝑝 − 𝑇𝑇 � � � 𝑑𝑑𝑑𝑑 − + �Δ𝑉𝑉 − 𝑇𝑇 � � � (2-6)
𝜕𝜕𝑇𝑇 2 𝑑𝑑𝑑𝑑 𝜕𝜕𝜕𝜕 𝑃𝑃 𝑑𝑑𝑑𝑑
0
where Δ𝑉𝑉 is the difference between vapor and liquid molar volumes. This is the key equation
used in this work. This equation allows for each of the involved properties to be simultaneously
optimized when fitting experimental data. When used to calculate 𝐶𝐶𝑝𝑝𝑙𝑙 , this is called the
Derivative method.
The properties used to find 𝐶𝐶𝑝𝑝𝑙𝑙 in Equation 2-6 are calculated using the temperature-
dependent correlations listed (Table 2-1). The contribution of each of these properties and
5
respective calculation methods to the Derivative method has been investigated, and will be
given.
Table 2-1: Calculation methods for properties in the Derivative method for finding 𝑪𝑪𝒍𝒍𝒑𝒑
Symbol Property Primary Method
𝑖𝑖𝑖𝑖
𝐶𝐶𝑝𝑝 Ideal Gas Heat Derived from statistical mechanics and ab initio generated
Capacity vibrational frequencies
𝑉𝑉vap Vapor Volume Soave-Redlich Kwong [4] Equation of State using 𝑃𝑃vap
𝑉𝑉liq Liquid Volume Inverse of Rackett [5] fit to density experimental points
Δ𝐻𝐻vap Heat of Vaporization Watson fit to Clapeyron [2] and experimental points
𝑃𝑃vap Vapor Pressure Riedel [6] predicted or fit to experimental points
6
3 LITERATURE REVIEW OF THERMOPHYSICAL PROPERTIES
3.1 Vapor Pressure
𝑖𝑖𝑖𝑖
Of the properties investigated in this work (𝑃𝑃vap , Δ𝐻𝐻vap , 𝐶𝐶𝑝𝑝𝑙𝑙 , 𝐶𝐶𝑝𝑝 ), 𝑃𝑃vap is the most
commonly measured and the most commonly known. As shown in Chapter 2, the derivative of
the 𝑃𝑃vap correlation is used to obtain Δ𝐻𝐻vap , and the derivative of Δ𝐻𝐻vap is used to obtain 𝐶𝐶𝑝𝑝𝑙𝑙 .
Therefore, accurate representation of the true 𝑃𝑃vap behavior across the entire range of
temperatures (from melting point to critical point) is essential to obtaining the best
thermodynamically consistent derived values for Δ𝐻𝐻vap and 𝐶𝐶𝑝𝑝𝑙𝑙 . As such, care must be taken
when correlating 𝑃𝑃vap to data to select the proper functional form of the equation and obtain the
best regression.
3.1.1 Vapor Pressure Correlation Equations
Though there are numerous 𝑃𝑃vap equations in the literature, only a few have gained
traction over time. They will be described here with letters 𝐴𝐴 − 𝐷𝐷 as fitting coefficients, 𝑇𝑇 as
temperature, 𝑇𝑇𝑟𝑟 as reduced temperature, and 𝑃𝑃𝐶𝐶 as the critical pressure.
The first correlation form is the Antoine equation [7], which is the simplest equation
which will be described here. It is derived from an Arrhenius rate equation describing the
equilibrium between vapor and liquid:
7
𝐵𝐵
𝑃𝑃vap = exp �𝐴𝐴 + � (3-1)
𝑇𝑇 + 𝐶𝐶
At very narrow temperature ranges, the Antoine equation works well. In fact, it is common to
report Antoine coefficients with vapor pressure data.
The Cox equation is another vapor pressure correlation:
1
𝑃𝑃vap = 𝑃𝑃𝐶𝐶 exp ��1 − � exp(𝐴𝐴 + 𝐵𝐵𝑇𝑇𝑟𝑟 + 𝐶𝐶𝑇𝑇𝑟𝑟2 + ⋯ )� (3-2)
𝑇𝑇𝑟𝑟
The Riedel equation is the primary vapor pressure correlation within the DIPPR database,
and has been around since 1954 [6]:
𝐵𝐵
𝑃𝑃vap = exp �𝐴𝐴 + + 𝐶𝐶 ln(𝑇𝑇) + 𝐷𝐷 𝑇𝑇 6 � (3-3)
𝑇𝑇
It consists of an Antoine fit (parameters 𝐴𝐴 and 𝐵𝐵) with correction terms (𝐶𝐶 and 𝐷𝐷) to help the
vapor pressure curve extend out from a small temperature region to the whole temperature region
from the triple point to the critical point. Traditionally, 6 has been assigned as the exponent on
the final temperature term. Riedel also gave a predictive method when he introduced this
correlation which will be further detailed in Section 6.2 [6].
The Wagner correlation was introduced in 1973 [8] as:
𝐴𝐴(1 − 𝑇𝑇𝑟𝑟 ) + 𝐵𝐵(1 − 𝑇𝑇𝑟𝑟 )1.5 + 𝐶𝐶(1 − 𝑇𝑇𝑟𝑟 )3 + 𝐷𝐷(1 − 𝑇𝑇𝑟𝑟 )6

𝑃𝑃vap = 𝑃𝑃𝐶𝐶 exp � � (3-4)
𝑇𝑇𝑟𝑟
He developed this correlation form after analyzing the statistical significance of different terms
when compared to cryogenic data for argon and nitrogen. Others have used this form but with
2.5 and 5 as the last two exponents to fit measured vapor pressure data [9].
Sanjari gave a modified version of the Riedel equation with the exponent on the last
temperature term changed from 6 to 2 [10]:
8
𝐵𝐵
𝑃𝑃vap = exp �𝐴𝐴 + + 𝐶𝐶 ln(𝑇𝑇) + 𝐷𝐷 𝑇𝑇 2 � (3-5)
𝑇𝑇
He found that this form fit vapor pressure data better than Riedel’s original correlation form and
Wagner’s correlation form for 66 of 75 compounds tested. The nine remaining compounds were
light gases like H2 and Ne that were best fit by Wagner’s correlation.
Other 𝑃𝑃vap correlation forms exist, but none that have gained significant traction over the
correlations already given. Of the correlations above, the Riedel and Wagner equation forms
performed best in fitting vapor pressure data for well-known organic compounds.
3.1.2 Vapor Pressure Data Availability
As stated earlier, 𝑃𝑃vap is the most commonly measured property among those of interest
to this work. The most commonly measured point on the 𝑃𝑃vap curve is the normal boiling point
because it is the temperature at which the compound boils at atmospheric pressure. More
complex methods like ebulliometry and calorimetry may be used to measure 𝑃𝑃vap around and
including the normal boiling point. As such, most 𝑃𝑃vap data are concentrated around the normal
boiling point. Several studies have found that measurements at pressures below 1000 Pa
contained significant uncertainty [11, 12].
3.2 Heat of Vaporization
Heat of vaporization, a temperature dependent quantity, is the heat required to vaporize a
liquid. It is defined as a positive quantity here. Heat of vaporization decreases with increasing
temperature until it reaches zero at the critical temperature where the liquid and vapor phases
converge. The shape of the decreasing curve varies across chemical types. Functional groups that
hydrogen bond in the liquid phase increase the energy requirement for escape into the vapor
phase.
9
3.2.1 Heat of Vaporization Correlation Equations
A commonly used empirical, temperature-dependent form for Δ𝐻𝐻vap [13] is:
2
Δ𝐻𝐻vap = 𝐴𝐴(1 − 𝑇𝑇𝑟𝑟 )𝐵𝐵+𝐶𝐶𝑇𝑇𝑟𝑟+𝐷𝐷𝑇𝑇𝑟𝑟 +⋯ (3-6)
where 𝐴𝐴 − 𝐷𝐷 are fitting coefficients and 𝑇𝑇𝑟𝑟 is the reduced temperature. A must be positive since
Δ𝐻𝐻vap is defined as positive. The thermodynamically derived value of 0 at 𝑇𝑇𝐶𝐶 = 1 is used to
justify this otherwise empirical equation form. For some hydrogen bonding compounds, more
fitting coefficients are needed to fully capture the shape of a curve derived from vapor pressure.
Although experimental data exist for Δ𝐻𝐻vap , it is usually easier to calculate it from 𝑃𝑃vap , 𝑉𝑉liq , and
𝑉𝑉vap using the thermodynamically-exact Clapeyron equation than to perform experiments (See
Equations 2-1 and 2-2).
3.2.2 Heat of Vaporization Data Availability
Much of the Δ𝐻𝐻vap data in the literature were derived from other thermophysical
properties. Figure 3-1 shows the distribution of data points labeled “Experimental” in the DIPPR
database. About a quarter of the “Experimental” data were direct heat of vaporization
measurements, but nearly two thirds of the data were derived or secondhand. Direct calorimetric
Δ𝐻𝐻vap measurements, which are usually grouped around room temperature or the normal boiling
point, were most commonly gathered before the 1990’s using the adiabatic or bomb calorimetry
[14-17], or Tian-Calvet drop calorimetry [18]. Most of the data gathered within the past couple
of decades are derived. The transpiration method can be used to obtain a vapor pressure
correlation from which heat of vaporization is easy to derive [19-21]. Correlation gas
chromatography is another method often employed that also derives heat of vaporization from a
correlation of vapor pressure, but uses gas chromatography instead [22-24]. These derived or
10
secondary approaches are much more common today. Figure 3-2 shows the DIPPR heat of
vaporization data for propylene and separates calorimetric data from derived data in the DIPPR
database for propylene. Notice that derived data for propylene outnumber direct data nearly 10:1.
This is common for many compounds in the database.
ΔHvap "Experimental" Data in Database (6923)
Experimental (1627)
Clapeyron/Otherwise Derived (1455)
Cited Works (Books/Tables/etc.) (2868)
Other (973)
Figure 3-1: Pie chart of ΔHvap data labeled as “Experimental” in the DIPPR database
2.5
2
ΔHvap (kJ mol-1)
1.5
DIPPR Correlation
1
Calorimetric Data
Derived Data
0.5
0
50 100 150 200 250 300 350 400
T/K
Figure 3-2: ΔHvap calorimetric and derived data with the DIPPR correlation for propylene
11
3.3 Ideal Gas Heat Capacity
The “ideal gas” is a condition that assumes no intermolecular interaction and is useful for
estimating the behavior of compounds in the vapor phase. As with many properties for ideal
gases, heat capacity can be derived using statistical mechanics, as shown in the Appendix, giving
the result:
3𝑚𝑚−5
𝑖𝑖𝑖𝑖,linear 7 Θ𝑣𝑣𝑣𝑣 2 𝑒𝑒 Θ𝑣𝑣𝑣𝑣/𝑇𝑇
𝐶𝐶𝑝𝑝 = 𝑁𝑁𝑁𝑁 + � � � Θ𝑣𝑣𝑣𝑣 (3-7)
2 𝑇𝑇
𝑗𝑗 (𝑒𝑒 𝑇𝑇 − 1)2
for a linear molecule, and

3𝑚𝑚−6
𝑖𝑖𝑖𝑖,nonlinear Θ𝑣𝑣𝑣𝑣 2 𝑒𝑒 Θ𝑣𝑣𝑣𝑣/𝑇𝑇
𝐶𝐶𝑝𝑝 = 4𝑁𝑁𝑁𝑁 + � � � Θ𝑣𝑣𝑣𝑣 (3-8)
𝑇𝑇
for a nonlinear molecule where 𝑇𝑇 is temperature, 𝑚𝑚 is the number of atoms in a single molecule,
and Θ𝑣𝑣𝑣𝑣 is the 𝑗𝑗𝑡𝑡ℎ vibrational frequency for linear and nonlinear molecules with m atoms,
respectively [25]. The vibrational modes Θ𝑣𝑣𝑣𝑣 may be found from experimental vibrational
spectra or from quantum mechanical calculations using a program such as Gaussian [26]or
NWChem [27]. Once the vibrational modes are obtained, values for the heat capacity may be
generated at any temperature of interest using Equation 3-7 or 3-8.
3.3.1 Ideal Gas Heat Capacity Correlation Equations
Ideal gas heat capacity data may fit to the 4 parameter Aly-Lee correlation [28]:
2 2
𝐶𝐶 𝐸𝐸
� � � �
= 𝐴𝐴 + 𝐵𝐵 � 𝑇𝑇 𝑇𝑇
𝑖𝑖𝑖𝑖
𝐶𝐶𝑝𝑝 � + 𝐷𝐷 � � (3-9)
𝐶𝐶 𝐸𝐸
sinh � � cosh � �
𝑇𝑇 𝑇𝑇
where 𝐴𝐴 − 𝐸𝐸 are fitting coefficients. In essence, the Aly-Lee correlation simplifies the statistical
mechanical equations (Equations 3-7 and 3-8) to one internal rotational contribution A, one
12
vibrational characteristic temperature contribution C, and one electronic contribution E with
𝑖𝑖𝑖𝑖
fitting coefficients B and D. The maximum average deviation for the Aly-Lee correlation for 𝐶𝐶𝑝𝑝
at low temperatures should be <10% assuming the vibrational frequencies found for Equations
3-7 and 3-8 are well known [28].
𝑖𝑖𝑖𝑖
The 𝐶𝐶𝑝𝑝 derived data can also be fit to a 6 parameter equation:
𝐶𝐶 2 𝐶𝐶 𝐸𝐸 2 𝐸𝐸 𝐺𝐺 2 𝐺𝐺
� � exp � � � � exp � � � � exp � �
𝑖𝑖𝑖𝑖
𝐶𝐶𝑝𝑝 = 𝐴𝐴 + 𝐵𝐵 � 𝑇𝑇 𝑇𝑇 𝑇𝑇 𝑇𝑇 𝑇𝑇 𝑇𝑇 � (3-10)
2 � + 𝐷𝐷 � 2 � + 𝐹𝐹 � 2
𝐶𝐶 𝐸𝐸 𝐺𝐺
�exp � � − 1� �exp � � − 1� �exp � � − 1�
𝑇𝑇 𝑇𝑇 𝑇𝑇
where 𝐴𝐴 − 𝐺𝐺 are fitting coefficients. This correlation is an expanded version of the Aly-Lee
correlation that adds an extra vibrational frequency contribution. This correlation works better at
low temperatures compared to the Aly-Lee form because of the added flexibility of that
vibrational contribution.
Both of these correlations are simplified versions of Equations 3-7 and 3-8. Simple
𝑖𝑖𝑖𝑖
polynomials have also been used to fit DIPPR 𝐶𝐶𝑝𝑝 data [29]. However, polynomials are
susceptible to interpolation error and extrapolation error outside the temperature region of the
data when too many terms are used in the polynomial (“over-fitting” the data).
3.3.2 Ideal Gas Heat Capacity Data Availability
𝑖𝑖𝑖𝑖
The DIPPR database contains many 𝐶𝐶𝑝𝑝 data which were labeled as “Experimental” that
are not from experimental measurements. The 2805 data points labeled as “experimental” were
evaluated and the sources were assessed, with results given in Figure 3-3. Over half of the data
were from tables or books—which could not be traced to primary source experiments—and
about a quarter of the data were from a vibrational analysis from an ab initio computational
calculation as described previously. As shown, only 10% of the data were actually experimental,
13
and the experimental data can be broken down into three measurement techniques: calorimetric,
speed of sound, and hot wire.
Cpig "Experimental" Data in Database (2805)
Experimental (289)
Unable to Access (314)
Vibrational Analysis (751)
TRC/Books/Tables (1373)
Liquid (47)
Other (53)
Figure 3-3: Pie chart of Cpig data labeled as “Experimental” in the DIPPR database
Calorimetry, speed of sound, and hot wire techniques measure the heat capacity in three
different ways. In calorimetry, the heat capacity of a vapor is measured directly to determine
how much heat is needed to increase the temperature [30]. In speed of sound measurements,
ideal gas heat capacity is found indirectly. First, the ratio of constant pressure and constant
volume ideal gas heat capacities is defined:
𝑖𝑖𝑖𝑖
𝐶𝐶𝑝𝑝 1 𝑣𝑣𝑠𝑠2 𝜌𝜌
𝛾𝛾 ≡ = =
𝑖𝑖𝑖𝑖
𝐶𝐶𝑣𝑣 𝑅𝑅𝑔𝑔 𝑃𝑃 (3-11)
1− 𝑖𝑖𝑖𝑖
𝐶𝐶𝑝𝑝
𝑖𝑖𝑖𝑖
where 𝑅𝑅𝑔𝑔 is the universal gas constant, 𝐶𝐶𝑣𝑣 is the constant volume ideal gas heat capacity, 𝑣𝑣𝑠𝑠 as
the velocity of sound through the ideal gas, 𝜌𝜌 as the density of the gas, and 𝑃𝑃 as the pressure of
14
the system. Rearranging Equation 3-11 gives a method to calculate ideal gas heat capacity from
simultaneous speed of sound, density, and pressure measurements:
𝑣𝑣𝑠𝑠2 𝜌𝜌
𝑁𝑁𝑁𝑁
= 2 𝑃𝑃
𝑖𝑖𝑖𝑖
𝐶𝐶𝑝𝑝 (3-12)
𝑣𝑣𝑠𝑠 𝜌𝜌
−1
𝑃𝑃
Hot wire measurements combine a transport equation to identify both thermal conductivity and
ideal gas heat capacity simultaneously [31].
As shown in Figure 3-4, about half of the truly experimental data in the DIPPR database
were calorimetric, about 40% were from speed of sound measurements, and the remaining 10%
were hot wire measurements.
Breakdown of True Experimental Cpig Data (280)
Calorimetric (130)
Speed of Sound (126)
Hot Wire (24)
Figure 3-4: Pie chart of measurement techniques used for actual experimental Cpig data in the
DIPPR database
With these experimental data in hand, the performance of the predictive capabilities of
Equations 3-7 and 3-8 were checked. Ideal gas heat capacity values were generated using
quantum mechanical calculations for compounds at temperatures where experimental data exist,
15
and these values were compared to experimental data. Figure 3-5 shows the results with the %
errors plotted as a function of temperature. Most of the quantum mechanical values fell within
10% of the experimental values with a couple of exceptions, as circled in the figure. N2O4 had
the greatest deviation, but that was because the compound decomposed into two NO2 molecules.
C2F5H had the second greatest deviation, but another experimental data set covered the same
temperature range with less than 2% difference from the ab initio values. (CF2H)2O had the next
most error, followed by Cl2, HCN, and CF3H. Notice that for all of these, the ab initio values
were too high.
For further analysis, the erroneous data sets described for N2O4 and C2F5H were
removed, and a histogram of the remaining error values is given in Figure 3-6. The data skew
towards positive error, but 88% of the data were contained within the DIPPR assigned
uncertainty of 10%. This means that quantum mechanical calculations will generate values for
𝑖𝑖𝑖𝑖
𝐶𝐶𝑝𝑝 slightly larger than, but within 10% of, the real values.
80%
70%
60% N2O4
Quantum Mechanical Error
50%
40% C2F5H
30%
(CF2H)2O
20% HCN
Cl2
10% CF3H
0%
100 200 300 400 500 600
-10%
-20%
T/K
Calorimetric Data Hot Wire Data Speed of Sound Data
Figure 3-5: Quantum mechanical calculation error versus temperature for Cpig compared to true
experimental data in the literature
16
140
120
Number of Data Points
100
80
60
40
20
0
<-20% -20 - 15% -15 - 10% -10 - 5% -5 - 0% 0 - 5% 5 - 10% 10 - 15% 15 - 20% >20%
Quantum Mechanical Error Bins
Figure 3-6: Error distribution for quantum mechanical values compared to experimental Cpig data
3.4 Liquid Heat Capacity
Due partially to size and intermolecular interactions, some molecules absorb more heat
than others when exposed to heat and raised to the same temperature. 𝐶𝐶𝑝𝑝𝑙𝑙 describes this difference
by quantifying the amount of heat required to increase the temperature of 1 mole of a liquid-
phase compound by 1 K in temperature. As the temperature increases, the ability to absorb more
heat also increases since the population of excited states changes.
At the most basic mathematical level described above, heat capacity is defined by the
change in isobaric enthalpy for a change in temperature, or the slope of the enthalpy-temperature
curve, where enthalpy is the sum of internal energy and the product of pressure and volume. As a
convention, 𝐶𝐶𝑝𝑝𝑙𝑙 is defined at 101,325 Pa from the triple point to the normal boiling point, since
the correction of saturation pressure to atmospheric pressure is negligible (See Chapter 2). Above
the normal boiling point, 𝐶𝐶𝑝𝑝𝑙𝑙 is defined at the vapor pressure. As the temperature approaches the
critical temperature, 𝐶𝐶𝑝𝑝𝑙𝑙 approaches to positive infinity.
17
3.4.1 Liquid Heat Capacity Temperature Behavior
Liquid heat capacity exhibits a wide variety of temperature-dependent behavior. As such,
the liquid heat capacity curve shape can be difficult to predict in the absence of experimental
data. A corresponding states method has been developed that has been shown to work well [2] in
certain regions. Beyond that, the actual shape of the temperature-dependent liquid heat capacity
curve can vary widely.
Figure 3-7 shows the liquid heat capacity data and DIPPR correlations for n-butane, 1-
butene, 1-propanol, and ethylene glycol. All of these compounds are about the same size, but 1-
butene contains a double bond, 1-propanol contains an alcohol group instead of a carbon, and
ethylene glycol contains two alcohol groups in place of carbon atoms. Using n-butane as a
baseline for the curve shape, 1-butene curls up at its triple point (87.8 K), 1-propanol crosses
through all the other compounds’ data, and ethylene glycol contains a strong inflection point
around its normal boiling point (470.38 K) before curling up at its critical point (719 K).
Intermolecular interactions cause this change in shape since other alkenes, alcohols, and glycols
exhibit the same shapes [9, 32-37]. This is why it is important to understand where the
experimental data exist, and how to correctly predict liquid heat capacity in temperature regions
where there are no experimental data.
Experimental 𝐶𝐶𝑝𝑝𝑙𝑙 data are much more common from the triple point to the normal boiling
point than from the normal boiling point to the critical point. When such data are available, the
Derivative method should match the experimental data well in that temperature region. At the
start of this project, however, the Derivative method tended to undershoot experimental data as
shown in Figure 3-8 for propylene. In 2013, the Derivative method was not used above the
18
normal boiling point, so the Derivative method curve in Figure 3-8 stops before the end of the
DIPPR correlation. As is shown in later chapters, this research reconciled these differences.
Butane Correlation
3.5
1-Butene Correlation
1-Propanol Correlation
Cpl (J g-1 K-1)
3
Ethylene Glycol Correlation
Butane Data
2.5
1-Butene Data
1-Propanol Data
2
Ethylene Glycol Data
1.5
50 150 250 350 450 550 650
T/K
Figure 3-7: Cpl data and DIPPR correlations for butane, 1-butene, 1-propanol, and ethylene glycol
150
140 Experimental Data
130 DIPPR Correlation
120
Derivative Method (2013)
Cpl (J mol-1 K-1)
110
100
90
80
70
60
50
75 125 175 225 275 325 375
T/K
Figure 3-8: Cpl Data and DIPPR correlation for propylene, along with the Derivative method
prediction from the start of this project
19
3.4.2 Liquid Heat Capacity Data Availability
Liquid heat capacity is most commonly measured near the triple point. Adiabatic
calorimetry [38, 39] and differential scanning calorimetry [40, 41] are the most common
techniques for measuring liquid heat capacity. As with most experimental methods, these
techniques are most easily performed at atmospheric pressure. Above the normal boiling point,
the material vaporizes, so pressure needs to be added to the experimental setup, and the
compound in the vapor phase needs to be accounted for [42]. Since high temperature
measurement is difficult, it is much less common than measurements below the normal boiling
point. Above the normal boiling point, saturated heat capacity is measured instead of constant
pressure heat capacity. In order to compare these literature values to a Derivative method
prediction, the data must be converted to isobaric heat capacity using:
liq 𝜕𝜕𝑉𝑉liq 𝑑𝑑𝑃𝑃vap

𝐶𝐶𝑝𝑝𝑙𝑙 = 𝐶𝐶𝜎𝜎 + �𝑇𝑇 � � − 𝑉𝑉liq � (3-13)
liq
where 𝐶𝐶𝜎𝜎 is the data point from literature, 𝑉𝑉liq is the liquid volume, and 𝑃𝑃vap is the vapor
pressure. A derivation of Equation 3-13 is given in the Appendix within a derivation of the
Derivative method.
3.5 Analysis of Experimental Data and Correlations
A qualitative description of the data available for vapor pressure, heat of vaporization,
ideal gas heat capacity, and liquid heat capacity is given by Figure 3-9. In this figure, the x-axis
is the reduced temperature, and the y-axis indicates the frequency of data available at each
temperature. The vertical line represents the normal boiling point, and the other lines indicate
data-temperature availability of the vapor pressure, heat of vaporization, and liquid heat capacity.
20
Several important observations may be made from this figure. First, compounds most
frequently contain experimental vapor pressure data around the normal boiling point. Second,
enthalpy (or heat) of vaporization data occur with less frequency than vapor pressure data, but
are also centered near the normal boiling point. Third, most compounds have no experimental
ideal gas heat capacity data. Fourth, liquid heat capacity data are fairly common near the triple
point but less as the normal boiling point is approached.
The uncertainties for each property can be described as the inverse of Figure 3-9. Vapor
pressure contains the lowest uncertainty at the normal boiling point and increases in both
directions toward the triple point and critical point. Heat of vaporization is sometimes known
experimentally at the normal boiling point, but is zero by definition at the critical point.
Generally, heat of vaporization isn’t known very well away from the critical point. Ideal gas heat
capacity is generally derived with about 10% uncertainty at all temperatures. Liquid heat
capacity uncertainty is lowest below the normal boiling point and gradually increases until the
critical point, where liquid heat capacity is indeterminate.
More Frequent
Vapor Pressure
Heat of Vaporization
Liquid Heat Capacity
Normal Boiling Point
Less Frequent
0 Reduced Temperature 1
Figure 3-9: A qualitative look at the relative frequency of experimental data for vapor pressure,
heat of vaporization, and liquid heat capacity around the normal boiling point
21
These properties can be optimized in a couple of ways, both revolving around the vapor
pressure correlation. One way is to minimize an objective function with temperature dependent
weighting. This allows the user to build uncertainty in measurements into the optimization.
Another way is to find the best vapor pressure correlation form to fit the data, which can be done
easily using the Riedel equation. These two multi-property optimization methods will be
discussed in further detail in Chapters 4 and 5.
22
4 MULTI-PROPERTY OPTIMIZATION – TEMPERATURE DEPENDENT
ERRORS
This work has been published in Fluid Phase Equilibria and will be summarized here
[43]. As has been shown qualitatively in Figure 3-9, the availability and accuracy of
experimental data for the different thermophysical properties vary widely over the temperature
region from the triple point to the critical point. This perspective can be used are most likely to
be trustworthy, and which data are less reliable. Next, the mathematical methodology will be
discussed.
4.1 Weight Model
An optimization process was setup as a sum of weighted sum squared errors, with each
given by
2
𝐽𝐽(𝐴𝐴, 𝑇𝑇𝑖𝑖 ) − 𝐽𝐽𝑖𝑖
𝑆𝑆𝑆𝑆𝑆𝑆(𝐴𝐴) = � �𝑤𝑤𝑖𝑖 � (4-1)
𝐽𝐽𝑖𝑖
𝑖𝑖
with 𝑤𝑤𝑖𝑖 as the weight of data point 𝑖𝑖, 𝐽𝐽(𝐴𝐴, 𝑇𝑇𝑖𝑖 ) as the predicted property 𝐽𝐽 with optimization
parameters 𝐴𝐴 at temperature 𝑇𝑇𝑖𝑖 , and 𝐽𝐽𝑖𝑖 as the 𝑖𝑖 th experimental data point of property 𝐽𝐽. The choice
of 𝑤𝑤 can greatly affect the optimized fit. This weighting can be chosen to emphasize the fitting
of certain properties. For example, a large weight for 𝑃𝑃vap compared to the weights of Δ𝐻𝐻vap and
𝐶𝐶𝑝𝑝𝑙𝑙 would ensure that 𝑃𝑃vap data are fit well. However, using one constant weighting for each
property is not entirely reasonable when trying to find the multi-property optimal fit. For actual
23
measurements of small organic compounds, 𝑃𝑃vap is very well known at temperatures around the
normal boiling point. Likewise, at the critical point, 𝑃𝑃vap is generally known because of the
prediction methods that have been developed for compounds that do not thermally decompose.
For these temperature regions, 𝑤𝑤 for 𝑃𝑃vap should be large. However, at very low temperatures
and pressures, say 100 Pa, accurate measurements are much more difficult, so lower weight
should be given to those data.
Two schemes for 𝑤𝑤 were used for the optimizations done here: constant 𝑤𝑤 for each sum
of squared error, and temperature-dependent 𝑤𝑤 for each sum of squared error. Table 4-1
summarizes the constant 𝑤𝑤 scheme which places equal emphases on 𝑃𝑃vap and 𝐶𝐶𝑝𝑝𝑙𝑙 . The
temperature-dependent 𝜖𝜖rel models were given as Lagrange polynomials which run through
assigned 𝑤𝑤 at different temperatures, resulting in the curves given in Figure 4-1 which reflect the
true nature of the uncertainty in 𝑃𝑃vap , Δ𝐻𝐻vap , and 𝐶𝐶𝑝𝑝𝑙𝑙 from the triple point to the critical point. In
other words, 𝑃𝑃vap , Δ𝐻𝐻vap , and are 𝐶𝐶𝑝𝑝𝑙𝑙 are given larger weight in temperature regions where they
are known with higher certainty. For 𝑃𝑃vap and Δ𝐻𝐻vap , this is around the normal boiling point. For
𝐶𝐶𝑝𝑝𝑙𝑙 , this is below the normal boiling point.
Table 4-1: Summary of the sum squared errors used

in the multi-property optimization
J Method 𝒘𝒘
𝑃𝑃vap Data Fitting 100
Δ𝐻𝐻vap Clapeyron 33
𝐶𝐶𝑝𝑝𝒍𝒍 Derivative Method 100
24
150
100 Vapor Pressure

w Heat of Vaporization
50 Liquid Heat Capacity
Normal Boiling Point
0
0 1
Tr
Figure 4-1: Temperature dependent weight model used in the multi-property optimization for
vapor pressure, heat of vaporization, and liquid heat capacity around the normal boiling point
Propylene can be used as a case study. Below the normal boiling point, propylene has
very small vapor pressures, culminating in the triple point pressure recommended by DIPPR,
𝑃𝑃TP , of 0.00117 Pa. To be able to measure a vapor pressure within 20% of 10-4 Pa would be a
decided success. To echo this optimistic view, the weight at 𝑇𝑇TP for 𝑃𝑃vap was 100/20, or 5. Δ𝐻𝐻vap
is rarely directly measured, but if it is, it is measured around 𝑇𝑇NB with much more error away
from 𝑇𝑇NB . Hence, the weight at 𝑇𝑇NB is highest, and decreases towards both 𝑇𝑇TP and 𝑇𝑇c . 𝐶𝐶𝑝𝑝𝑙𝑙 is
commonly measured 𝑇𝑇TP to 𝑇𝑇NB , but above 𝑇𝑇NB , it must be converted from 𝐶𝐶sat , introducing
progressively larger potential error up to 𝑇𝑇c . Thus, the weight is around 100 up to 𝑇𝑇NB , and
shrinks to 40 towards 𝑇𝑇c .
4.2 Results/Discussion
The DIPPR 𝑃𝑃vap expression was used to predict Δ𝐻𝐻vap and 𝐶𝐶𝑝𝑝𝑙𝑙 through the Clapeyron
equation and the Derivative method, giving a “starting fit.” This prediction was compared to
optimizations of the Riedel and Wagner 𝑃𝑃vap expressions with the constant and temperature
dependent weightings given in the previous section. For convenience, these correlation forms are
given here with simplified symbols:
25
𝐵𝐵
R1: 𝑃𝑃vap = exp �𝐴𝐴 + + 𝐶𝐶 ln(𝑇𝑇) + 𝐷𝐷𝑇𝑇 1 � (4-2)
𝑇𝑇
𝐵𝐵
𝑇𝑇
𝐵𝐵
𝑇𝑇
𝐴𝐴(1−𝑇𝑇𝑟𝑟 )+𝐵𝐵(1−𝑇𝑇𝑟𝑟 )1.5 +𝐶𝐶(1−𝑇𝑇𝑟𝑟 )2.5 +𝐷𝐷(1−𝑇𝑇𝑟𝑟 )5

W2: 𝑃𝑃vap = 𝑃𝑃𝑐𝑐 exp � � (4-5)
𝑇𝑇𝑟𝑟
𝐴𝐴(1−𝑇𝑇𝑟𝑟 )+𝐵𝐵(1−𝑇𝑇𝑟𝑟 )1.5 +𝐶𝐶(1−𝑇𝑇𝑟𝑟 )3 +𝐷𝐷(1−𝑇𝑇𝑟𝑟 )6

W3: 𝑃𝑃vap = 𝑃𝑃𝑐𝑐 exp � � (4-6)
𝑇𝑇𝑟𝑟
where 𝐴𝐴 − 𝐷𝐷 are fitting coefficients. Note that R1, R2, and R6 only differ by the final exponent.
For future reference, this exponent will be symbolized as 𝐸𝐸 so that R1 can also be described as a
Riedel correlation with 𝐸𝐸 = 1, R2 as a Riedel correlation with 𝐸𝐸 = 2, and R6 as a Riedel
correlation with 𝐸𝐸 = 6. The data used in this process are referenced in [43]. For each 𝑃𝑃vap
correlation, the temperature dependent weight did better than the constant temperature weight
optimizations at matching the 𝐶𝐶𝑝𝑝𝑙𝑙 experimental data, even though the constant temperature weight
scheme gave 𝑃𝑃vap and 𝐶𝐶𝑝𝑝𝑙𝑙 equal weights.
To compare these fits, the average absolute deviation (AAD) was used as defined by:
1 𝐽𝐽𝑖𝑖 − 𝐽𝐽̂(𝑇𝑇𝑖𝑖 )
𝐴𝐴𝐴𝐴𝐴𝐴 = �� (4-7)
𝑁𝑁 𝐽𝐽𝑖𝑖
𝑖𝑖
where 𝐽𝐽𝑖𝑖 is the experimental value for the property (vapor pressure, heat of vaporization, or liquid
heat capacity), 𝐽𝐽̂(𝑇𝑇𝑖𝑖 ) is the model prediction for the property at temperature 𝑇𝑇𝑖𝑖 , and 𝑁𝑁 is the
number of experimental points for that property. The AAD’s of the “starting fit” and each
optimized correlation with the temperature dependent weight from experimental data were
compared in Figure 4-2. The R6 temperature dependent weight optimization did worse than R1
and R2, and the W2 and W3 temperature dependent weight optimizations performed about
equally for propylene.
26
14
12 Starting Fit
10 Riedel: E=1
AAD (%)
8 Riedel: E=2
6 Riedel: E=6
4 Wagner: 2.5,5
2 Wagner: 3,6
0
Vapor Pressure Heat of Vaporization Liquid Heat Capacity
Figure 4-2: Average absolute deviation (AAD) for propylene across vapor pressure, heat of
vaporization, and liquid heat capacity data with the starting fit, the R1 fit, the R2 fit, the R6 fit, the
W2 fit, and the W3 fit with temperature dependent weights
Of all the correlation forms, it appears that using the temperature dependent weight on
the R2 correlation gives the best fit for propylene. The optimized R2 𝑃𝑃vap correlation and
predicted Δ𝐻𝐻vap and 𝐶𝐶𝑝𝑝𝑙𝑙 correlations through the Clapeyron equation and Derivative method are
given for propylene in Figure 4-3. In this optimization, the 𝑃𝑃vap curve was allowed to deviate
from 𝑃𝑃vap data at low temperatures to accommodate 𝐶𝐶𝑝𝑝𝑙𝑙 data. This tradeoff can be justified when
the accuracy of low temperature 𝑃𝑃vap data are suspect and the uncertainties of 𝐶𝐶𝑝𝑝𝑙𝑙 data are low at
low temperatures. Additionally, the Δ𝐻𝐻vap curve changed significantly towards 𝑇𝑇TP (which
occurs as 𝑇𝑇𝑟𝑟 = 0.24) from the initial Clapeyron expression.
This optimization was done with the same temperature dependent weighting for four
other compounds (propane, pentane, hexafluoroethane, and ammonia) using the data given in
[43], and the averages of the absolute average deviations (AAD) as defined by:
𝐴𝐴𝐴𝐴𝐷𝐷Pvap + 𝐴𝐴𝐴𝐴𝐷𝐷ΔHvap + 𝐴𝐴𝐴𝐴𝐷𝐷Clp

Average AAD = (4-8)
3
27
are given for the 𝑃𝑃vap expressions in Equations 4-2 through 4-6. For each of these compounds,
the “starting fit” refers to the vapor pressure correlation fit using only 𝑃𝑃vap experimental data.
Generally, the optimized 𝑃𝑃vap correlations did not fit 𝑃𝑃vap data as closely as the “starting fits,”
but when used with the Clapeyron equation and Derivative method, the 𝑃𝑃vap correlations fit
Δ𝐻𝐻vap and 𝐶𝐶𝑝𝑝𝑙𝑙 much better.
5 20
a)
4 15 b)
ln(Pvap) (ln(Pa))
Data
Pvap (MPa)
3 10
Starting Correlation
2 5
Optimized 0
1
Correlation -5
0
-10
0 0.5 1
0 2 4 6
Tr 1/Tr
30 250
25 c) (d)
ΔHvap (kJ mol-1)
200
Cpl (J mol-1 K-1)
20
15 150
10
5 100
0
50
0 0.5 1 0 0.5 1
Tr Tr
Figure 4-3: Experimental data for propylene with the starting and optimized Riedel 2 fits for (a)
vapor pressure, (b) natural log of vapor pressure, (c) heat of vaporization, and (d) liquid isobaric
heat capacity
Notably, the R6 expression did the worst of any of the expressions for each of the
compounds studied. The choice of final exponent in the Riedel correlation, 𝐸𝐸, greatly affects the
ability of the vapor pressure curve to be consistent with the other properties. The 𝑃𝑃vap correlation
used must be flexible enough to accommodate 𝐶𝐶𝑝𝑝𝑙𝑙 data at low temperature, so the type of
28
correlation chosen will influence the ability of 𝑃𝑃vap to be thermodynamically consistent with
Δ𝐻𝐻vap and 𝐶𝐶𝑝𝑝𝑙𝑙 data. The predicted triple point pressures are given for the optimized correlation
with the lowest average AAD for each of these compounds in Table 4-2.
7
Start Riedel: E=1
6
Riedel: E=2 Riedel: E=6
5
Average AAD (%)
Wagner: 2.5,5 Wagner: 3,6

4
0
Propylene Propane Pentane Hexafluoroethane Ammonia
Figure 4-4: The average AAD from Pvap, ΔHvap, and Cpl using the starting fit to Pvap data only and
the optimized R1, R2, R6, W2, and W3 fits for the five compounds studied
Table 4-2: Optimized vapor pressure correlations with triple point pressures
Compound 𝑻𝑻𝑻𝑻𝑻𝑻 (𝑲𝑲) 𝑷𝑷𝑻𝑻𝑻𝑻 (𝑷𝑷𝑷𝑷) Correlation A B C D
Propylene 87.89 6.72×10-4 R2 63.335 -3550.3 -6.7797 1.3053×10-5
Propane 85.47 1.70×10-4 R2 59.477 -3498.8 -6.1377 1.1167×10-5
Pentane 143.42 7.51×10-2 W3 -7.5454 2.1047 -3.6957 -1.0530
Hexafluoroethane 173.1 2.64×104 W2 -7.3650 1.8621 -2.2999 -2.7328
Ammonia 195.41 6.07×103 R2 69.276 -4343.7 -7.3461 1.0858×10-5
4.3 Conclusions
A multi-property optimization was created that enhanced the shape of the 𝑃𝑃vap curve to
be more thermodynamically consistent with Δ𝐻𝐻vap and 𝐶𝐶𝑝𝑝𝑙𝑙 data. The motivation for developing
an optimization was introduced with the 𝐶𝐶𝑝𝑝𝑙𝑙 of propylene. The weight model used in the
29
optimization was discussed, with the best results coming from a temperature dependent model
for each property that quantifies the degree to which each property is accurate at each
temperature.
Three forms of the Riedel 𝑃𝑃vap expression and two forms of the Wagner 𝑃𝑃vap expression
were optimized for five compounds: propylene, propane, pentane, hexafluoroethane, and
ammonia. Of the Riedel expressions, R6 performed the worst, and R2 seemed to perform the
best, leading to a discussion of the 𝐸𝐸 parameter in the Riedel equation. The two Wagner
expressions performed about as well as R2. The best optimized Δ𝐻𝐻vap curve for propylene
changed significantly towards the triple point temperature. These optimizations changed the 𝑃𝑃vap
expression for each compound to fit more accurate data, whether it be 𝑃𝑃vap , Δ𝐻𝐻vap , or 𝐶𝐶𝑝𝑝𝑙𝑙 based
on the temperature for propylene, propane, pentane, hexafluoroethane, and ammonia. From these
optimizations, new thermodynamically consistent triple point pressures and 𝑃𝑃vap expressions
were found that can be used in process design with these chemicals.
30
5 MULTI-PROPERTY OPTIMIZATION – THE RIEDEL EQUATION
Upon completing the previous work comparing the Riedel correlation with the 𝐸𝐸
coefficient set to 1, 2, or 6, the overall effect of the 𝐸𝐸 coefficient on the vapor pressure fit was
further investigated. The Riedel correlation was generalized to the form:
𝐵𝐵
𝑃𝑃vap = exp �𝐴𝐴 + + 𝐶𝐶ln(𝑇𝑇) + 𝐷𝐷𝑇𝑇 𝐸𝐸 � (5-1)
𝑇𝑇
and the 𝐸𝐸 parameter was changed in integer steps from 1 to 6. The ability of those vapor pressure
expressions to predict liquid heat capacity data for many compounds was assessed.
5.1 Methods
The multi-property optimization proposed here involves fitting experimental data for
vapor pressure and liquid heat capacity to Equations 2-1 and 2-6, respectively, using the
generalized Riedel equation with different 𝐸𝐸 values. The experimental data were obtained from
the DIPPR database [44]. Seven different chemical families were used — n-alkanes, 2-methyl
alkanes, 1-alkenes, n-aldehydes, aromatics, ethers, and ketones, with specific compounds listed
in Table 5-1 for the hydrocarbons and Table 5-2 for the non-hydrocarbons. By changing 𝐸𝐸, the
heat of vaporization derived through the Clapeyron equation was changed at low temperatures.
However, there exist few experimental heat of vaporization data in the low temperature range to
provide sufficient insight because most heat of vaporization values are derived through the
31
Clapeyron equation from a fit of experimental vapor pressure data. Therefore, vapor pressure and
liquid heat capacity data were used to determine the best fit for 𝐸𝐸.
Although the thermodynamic procedure is rigorous, preliminary analysis showed that
alcohols and other strongly hydrogen bonding families were not well identified using this
particular method. Previous studies have shown that extra terms can be added to the Riedel form
to improve the fit of alcohols [45], or that another equation form should be used altogether [46].
Other studies suggest changes to the cubic equation of state for compounds that dimerize in the
vapor phase [47-49]. Due to these complications, strongly hydrogen bonding families were
omitted from the current study.
Table 5-1: A list of hydrocarbons investigated in this study, grouped by chemical family
n-Alkanes 2-Methyl Alkanes 1-Alkenes n-Aldehydes Aromatics
Ethane Isobutane Propylene Butanal Benzene
Propane 2-Methyl Butane 1-Butene Propanal Toluene
Butane 2-Methyl Pentane 1-Pentene Pentanal Ethylbenzene
Pentane 2-Methyl Hexane 1-Hexene Hexanal Propylbenzene
Hexane 2-Methyl Heptane 1-Heptene Butylbenzene
Heptane m-Xylene
Octane o-Xylene
p-Xylene
Table 5-2: A list of non-hydrocarbons investigated in this study,

grouped by chemical family
Ethers Ketones
Dimethyl Ether Methyl Ethyl Ketone
Diethyl Ether Methyl Isopropyl Ketone
Ethyl Propyl Ether Methyl Isobutyl Ketone
Di-n-Propyl Ether 2-Pentanone
Methyl t-Butyl Ether 2-Hexanone
2-Heptanone
2-Octanone
32
A summary of the data for the vapor pressure and liquid heat capacity data for these
compounds are detailed in the Appendix.
The number of vapor pressure data points was usually more than double that of the heat
capacity data points for each compound. However, the vapor pressure data were composed
mostly of higher-temperature data while the heat capacity data were usually in the lower
temperature range, and often extended down to the triple point. Herein lies the strength of this
analysis—the liquid heat capacity data can be used to influence the second derivative of the
vapor pressure curve in a region where there is little to no experimental vapor pressure data.
Alternatively, if 𝐸𝐸 is known for a chemical family, then the ability to predict liquid heat capacity
from vapor pressure would be more accurate.
Another advantage of the method is also related to the data. Experimental vapor pressure
data are limited and uncertain at subambient pressures [50, 51]. It has been repeated that
uncertainty in vapor pressure experimental data increases from as low as 0.00001% at 105 Pa to
at least 100% at 1 Pa. To circumvent the dearth and uncertainty of vapor pressure data, Perkins
et. al. [52] measured heat capacity to influence the vapor pressure equation for propane. Duarte-
Garza and Magee [50] used internal energy changes in the two phase region to derive vapor
pressure for three refrigerants. They even checked the thermodynamic consistency of a
previously published equation of state and re-evaluated the uncertainties of previously reported
subambient vapor pressures. Poling [45] also checked the efficacy of different vapor pressure
equation forms using vapor pressure and calorimetric data simultaneously, finding that heat
capacity data dominate the lower temperature region and vapor pressure data dominate the high
temperature region.
33
This project sought to use available heat capacity data to influence the vapor pressure fit,
since heat capacity can be measured with a comparatively high degree of accuracy. Low
temperature liquid heat capacity data were used to select the vapor pressure correlation form.
For each compound, the vapor pressure data were fitted to Equation 5-1 by a least squares
regression for a given value of 𝐸𝐸 ranging from 1 to 6 in integer values and for 𝐸𝐸 = 0.5. This
correlation was then used to obtain the heat of vaporization through Equation 2-1, which was
then used in Equation 2-6 to generate a correlation for liquid heat capacity. The resulting liquid
heat capacity correlations obtained with each value of 𝐸𝐸 were then compared to liquid heat
capacity experimental data.
As stated previously, the vapor volumes were calculated with the Soave-Redlich-Kwong
(SRK) equation of state [4], and the liquid volumes were calculated from the liquid density
correlations given in the DIPPR database [44]. The ideal gas heat capacities used in Equation 2-6
were calculated from vibrational frequencies generated by ab initio methods with appropriate
scaling factors for the basis sets and levels of theory used.
5.2 Results
As mentioned above, the first step in the optimization was to fit the vapor pressure data to
Equation 5-1 with different values of 𝐸𝐸. Table 5-3 shows the absolute average deviation between
the resulting correlations and the data for n-butane for 𝐸𝐸 = 1 through 6. Notice that changing 𝐸𝐸
has little effect on the absolute average deviation (𝐴𝐴𝐴𝐴𝐴𝐴) of the fit.
Table 5-3: Absolute average deviation of Equation 5-1 fit to vapor pressure data
for n-butane while varying E
n-Butane E=1 E=2 E=3 E=4 E=5 E=6
Pvap AAD 0.340% 0.328% 0.326% 0.331% 0.345% 0.367%
34
Next, heat of vaporization was derived using the Clapeyron equation for each value of 𝐸𝐸,
which are shown in Figure 5-1 for n-butane as temperature-dependent lines. The triple point
occurs at 𝑇𝑇𝑟𝑟 = 0.33. Even for a compound such as n-butane, there exist few actual experimental
heat of vaporization data points, with one point given in Figure 5-1 [53].
In the case of n-butane, the lowest experimental vapor pressure data point was at 𝑇𝑇𝑟𝑟 =
0.45. Below this temperature, the different predictions of heat of vaporization fan out
considerably. As 𝐸𝐸 increases, the heat of vaporization curves dip lower at low temperatures.
Specifically, from 𝑇𝑇𝑟𝑟 = 0.33 to 𝑇𝑇𝑟𝑟 = 0.5, the higher the value of 𝐸𝐸 the lower the value of the
heat of vaporization at a given temperature. However, this difference does not occur in the
temperature range where experimental heat of vaporization data exist. In this instance, there was
only one calorimetrically determined heat of vaporization data point for n-butane. Other n-
alkanes, 2-methylalkanes, n-aldehydes, 1-alkenes, ethers, ketones, and aromatics tested in this
work gave similar results and had few experimental heat of vaporization data points. Therefore,
comparing heat of vaporization data to the Clapeyron derived curves provided little insight in
choosing the best value for 𝐸𝐸.
Finally, liquid heat capacity was derived from vapor pressure and heat of vaporization
using the Derivative Method (Equation 2-6) for each value of 𝐸𝐸, as shown in Figure 5-2 for n-
butane as temperature-dependent lines. Experimental data from multiple sources are depicted as
points. As 𝐸𝐸 increases, the predicted liquid heat capacity curves dips lower at low temperatures.
Specifically, from 𝑇𝑇𝑟𝑟 = 0.33 to 𝑇𝑇𝑟𝑟 = 0.6, the higher the value of 𝐸𝐸, the lower the value of the
heat capacity at a given temperature. The best fit to the data occurs for 𝐸𝐸 = 2.
35
30
28 temperature range of vapor pressure data

ΔHvap (kJ mol-1)
26 E=1
E=2
24 E=3
E=4
E=5
22 E=6
Experimental Data
20
0.3 0.4 0.5 0.6 0.7 0.8
Tr
Figure 5-1: Heat of vaporization experimental data and Clapeyron equations using the Riedel
equation with E = 1 through 𝟔𝟔 with the temperature range of vapor pressure data shown
Also depicted in Figure 5-2 is an indication of the temperature range for the experimental
vapor pressure data. In the case of n-butane, the lowest experimental vapor pressure data point
was for 𝑇𝑇𝑟𝑟 = 0.45. Below this temperature, the different predictions of liquid heat capacity fan
out considerably. However, the fanning out actually begins at higher temperatures
(approximately 𝑇𝑇𝑟𝑟 = 0.6) where adequate experimental data exist. Other n-alkanes,
2-methylalkanes, n-aldehydes, 1-alkenes, aromatics, ethers, and ketones tested in this work gave
similar results. This is evidence that using the incorrect value for 𝐸𝐸, even if experimental data for
the vapor pressure are available, can drastically affect properties based on vapor pressure despite
the vapor pressure correlation itself appearing statistically accurate (See Table 5-3 for n-butane).
In order to determine if an optimal 𝐸𝐸 value exists, an analysis similar to what was just
presented for n-butane was performed for all of the n-alkanes, 2-methylalkanes, 1-alkenes, n-
aldehydes, aromatics, ethers, and ketones listed in Table 5-1 and Table 5-2. The results are
contained in Figure 5-3 through Figure 5-9. Figure 5-3a through Figure 5-9a contain the absolute
36
average deviations (𝐴𝐴𝐴𝐴𝐴𝐴) between the experimental vapor pressure data and the fit to the Riedel
equation for 𝐸𝐸 = 0.5 − 6. Similarly, Figure 5-3b through Figure 5-9b give the 𝐴𝐴𝐴𝐴𝐴𝐴’s between
the experimental values for liquid heat capacity and those predicted using Equation 2-6. Figure
5-3 is for the n-alkanes, Figure 5-4 for the 2-methylalkanes, Figure 5-5 for the 1-alkenes, Figure
5-6 for the n-aldehydes, Figure 5-7 for the aromatics, Figure 5-9 for the ketones, and Figure 5-8
for the ethers.
160
150 temperature range of vapor pressure data
140
Cpl (J mol-1 K-1)
130 Experimental Data

E=1
120 E=2
E=3
110
E=4
100 E=5
E=6
90
0.3 0.4 0.5 0.6 0.7 0.8
Tr
Figure 5-2: Liquid heat capacity data and Derivative method predictions from the Riedel equation
with E = 1 through 6 with the temperature range of vapor pressure data shown
While the best 𝐸𝐸 values for the vapor pressure fits vary from 0.5 to 6, the best 𝐸𝐸 values
for the liquid heat capacity range from 1 to 3, with 2 as the overall best performer for n-alkanes,
2-methyl alkanes, 1-alkenes, aromatics, and ether. For the n-aldehydes and ketones, an 𝐸𝐸 value
from 1 to 3 generally gives the best heat capacity fit. Additionally, the absolute average
deviations do not increase by more than 0.5% for the vapor pressure fit, but the absolute average
deviations for the liquid heat capacity fit increase by as much as 10% suggesting that the 𝐸𝐸 value
37
affects the liquid heat capacity fit more than the vapor pressure fit. This shows that liquid heat
capacity data should be considered when trying to determine the best value of 𝐸𝐸.
Another test of the low-temperature performance of the vapor pressure correlation is its
ability to predict the triple point pressure (𝑇𝑇𝑇𝑇𝑇𝑇) of the compound. This test was applied to
validate the multi-property optimization approach to fitting the Riedel equation presented above.
Specifically, the vapor pressure fit with the best 𝐸𝐸 value for each compound was extrapolated to
the triple point temperature, which was approximated as the melting points for these pure
compounds, to predict the triple point pressure.
1.2% 16%
14%
1.0%
12%
0.8%
10%
Pvap AAD
Cpl AAD
0.6% 8%
6%
0.4%
4%
0.2%
2%
0.0% 0%
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7
E Value E Value
Figure 5-3: Absolute average deviation of a) vapor pressure data and b) liquid heat capacity data
of fits with the use of the Riedel equation with 𝑬𝑬 =0.5 through E=6 for the n-alkanes ethane ( ),
propane ( ), butane ( ), pentane ( ), hexane ( ), heptane ( ), and octane ( )
38
0.5% 14%
12%
0.4%
10%
0.3%
8%
Pvap AAD
Cpl AAD
6%
0.2%
4%
0.1%
2%
0.0% 0%
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7
E Value E Value
Figure 5-4: Absolute average deviation of a) vapor pressure data and b) liquid heat capacity data of
fits with the use of the Riedel equation with 𝑬𝑬 =0.5 through E=6 for the 2-methylalkanes isopropane
( ), 2-methylbutane ( ), 2-methylpentane ( ), 2-methylhexane ( ), and 2-methylheptane
( )
1.0% 20%
0.9% 18%
0.8% 16%
0.7% 14%
0.6% 12%
Pvap AAD
Cpl AAD
0.5% 10%
0.4% 8%
0.3% 6%
0.2% 4%
0.1% 2%
0.0% 0%
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7
E Value E Value
of fits with the use of the Riedel equation with 𝑬𝑬 =0.5 through E=6 for the 1-alkenes propylene
( ), 1-butene ( ), 1-pentene ( ), 1-hexene ( ), and 1-heptene ( )
39
1.6% 16%
1.4% 14%
1.2% 12%
1.0% 10%
Pvap AAD
Cpl AAD
0.8% 8%
0.6% 6%
0.4% 4%
0.2% 2%
0.0% 0%
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7
E Value E Value
of fits with the use of the Riedel equation with 𝑬𝑬 = 0.5 through E=6 for the n-aldehydes butanal
( ), pentanal ( ), hexanal ( ), and heptanal ( )
1.8% 8%
1.6% 7%
1.4%
6%
1.2%
5%
Pvap AAD
1.0%
Cpl AAD
4%
0.8%
3%
0.6%
2%
0.4%
0.2% 1%
0.0% 0%
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7
E Value E Value
fits with the use of the Riedel equation with 𝑬𝑬 =0.5 through E=6 for the aromatic compounds
benzene ( ), toluene ( ), m-xylene ( ), o-xylene ( ), p-xylene ( ), ethylbenzene ( ),
propylbenzene ( ), and butylbenzene ( )
40
1.4% 20%
18%
1.2%
16%
1.0% 14%
12%
0.8%
Pvap AAD
Cpl AAD
10%
0.6%
8%
0.4% 6%
4%
0.2%
2%
0.0% 0%
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7
E Value E Value
of fits with the use of the Riedel equation with 𝑬𝑬 =0.5 through E=6 for the ethers dimethyl ether
( ), diethyl ether ( ), ethyl propyl ether ( ), di-n-propyl ether ( ), and methyl tert-butyl
ether ( )
3.0% 16%
14%
2.5%
12%
2.0%
10%
Pvap AAD
Cpl AAD
1.5% 8%
6%
1.0%
4%
0.5%
2%
0.0% 0%
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7
E Value E Value
fits with the use of the Riedel equation with 𝑬𝑬 =0.5 through E=6 for the ketones methyl ethyl ketone
( ), methyl isopropyl ketone ( ), methyl isobutyl ketone ( ), 2-pentanone ( ), 2-
hexanone ( ), 3-hexanone ( ), 2-heptanone ( ), and 2-octanone ( )
The resulting values are given in Table 5-4 for the n-alkanes, Table 5-5 for the
2-methylalkanes, Table 5-6 for the 1-alkenes, Table 5-7 for the n-aldehydes, Table 5-8 for the
41
aromatics, Table 5-9 for the ethers, and Table 5-10 for the ketones along with the database values
from DIPPR [44] and REFPROP [54]. These tables also give the number of coefficients in
Equation 5-1 fit to vapor pressure data. In all cases, the 𝑇𝑇𝑇𝑇𝑇𝑇 of this work are consistent to that in
the literature. The n-alkane data also follow the characteristic saw-tooth pattern as seen in Figure
5-10. These results further increase confidence in the method – specifically that optimizing the
value of 𝐸𝐸 does not compromise the correlation’s ability to predict 𝑇𝑇𝑇𝑇𝑇𝑇.
Table 5-4: Summary of triple point pressures (in Pa) from literature
and this work for the n-alkanes
DIPPR DIPPR [44] RefProp [54] Fitting This Work
Carbon # Source 𝑻𝑻𝑻𝑻𝑻𝑻 𝑻𝑻𝑻𝑻𝑻𝑻 𝑬𝑬 Coefficients 𝑻𝑻𝑻𝑻𝑻𝑻
2 Cited [55] 1.13 1.14 3 4 1.13
3 Cited [56] 1.69E-04 1.72E-04 2 4 2.20E-04
4 Cited [57] 0.674 0.666 2 4 0.653
5 Predicted 6.86E-02 7.63E-02 2 4 6.88E-02
6 Predicted 0.902 1.28 2 4 1.12
7 Predicted 0.183 0.175 2 4 0.187
8 Predicted 2.11 1.99 1 4 2.17
and this work for the 2-methylalkanes
3 Predicted 1.21E-02 2.29E-02 2 4 2.65E-02
4 Predicted 1.21E-04 8.95E-05 2 4 1.26E-04
5 Predicted 2.07E-05 3 4 7.50E-06
6 Predicted 4.30E-03 2 4 2.01E-03
7 Predicted 1.06E-03 1 4 9.96E-04
and this work for the 1-alkenes
3 Predicted 1.17E-03 7.47E-04 2 4 5.83E-04
4 Predicted 6.94E-07 2 2 8.24E-07
5 Predicted 3.70E-05 3 2 1.76E-05
6 Predicted 5.16E-04 2 2 2.51E-04
7 Predicted 1.86E-03 2 2 1.30E-03
42
and this work for the n-aldehydes
DIPPR DIPPR [44] Fitting This Work
Carbon # Source 𝑻𝑻𝑻𝑻𝑻𝑻 𝑬𝑬 Coefficients 𝑻𝑻𝑻𝑻𝑻𝑻
4 Predicted 0.697 3 2 0.341
5 Predicted 1.16 2 2 0.241
6 Predicted 1.86 3 2 1.365
7 Predicted 2.56 2 2 0.671
and this work for the aromatics
Compound Source 𝑻𝑻𝑻𝑻𝑻𝑻 𝑻𝑻𝑻𝑻𝑻𝑻 𝑬𝑬 Coefficients 𝑻𝑻𝑻𝑻𝑻𝑻
Benzene Predicted 4760 4790 2 4 4770
Toluene Predicted 0.0475 0.0406 2 4 0.0478
Ethylbenzene Predicted 4.39E-03 2 4 3.99E-03
Propylbenzene Predicted 1.814E-04 2 2 1.98E-04
Butylbenzene Predicted 1.54E-04 2 2 1.47E-04
m-Xylene Predicted 3.14 2 4 3.08
o-Xylene Predicted 23.8 2 4 22.6
p-Xylene Predicted 586 2 4 574
and this work for the ethers
Compound Source 𝑻𝑻𝑻𝑻𝑻𝑻 𝑬𝑬 Coefficients 𝑻𝑻𝑻𝑻𝑻𝑻
Dimethyl Predicted 3.05 1 2 2.50
Diethyl Predicted 0.395 2 2 0.639
Ethyl Propyl Predicted 1.61E-03 1 2 2.33E-03
Di-n-Propyl Predicted 7.63E-04 2 2 3.32E-04
Methyl t- Predicted 0.494 2 2 0.385
Butyl
43
Table 5-10: Summary of triple point pressure (in Pa) from literature
and this work for the ketones
Compound Source 𝑻𝑻𝑻𝑻𝑻𝑻 𝑬𝑬 Coefficients 𝑻𝑻𝑻𝑻𝑻𝑻
Methyl Ethyl Ketone Predicted 1.42 2 2 1.02
Methyl Isopropyl Predicted 0.214 1 2 0.145
Ketone
Methyl Isobutyl Predicted 0.0672 5 2 0.0636
Ketone
2-Pentanone Predicted 0.752 1 2 0.749
2-Hexanone Predicted 1.45 2 2 1.44
3-Hexanone Predicted 2.22 1 2 1.88
2-Heptanone Predicted 3.55 0.5 2 3.29
2-Octanone Predicted 4.68 0.5 2 3.46
2.5
DIPPR
Triple Point Pressure (Pa)
2 RefProp
This Project
1.5
0.5
0
0 2 4 6 8 10
Carbon Number
Figure 5-10: Triple point pressures versus carbon number for n-alkanes comparing DIPPR values
[44], REFPROP values [54], and values from this work
5.3 Conclusions
Liquid heat capacity data for several n-alkanes, 2-methylalkanes, 1-alkenes, n-aldehydes,
ketones, ethers, and aromatics were used to determine the selection of the Riedel 𝐸𝐸 coefficient
for vapor pressure via the Derivative Method for predicting liquid heat capacity. This analysis
showed that an 𝐸𝐸 of 2 fits these families much better than the traditional 𝐸𝐸 of 6. Additionally,
44
this method increased confidence in vapor pressure extrapolation to the triple point temperature,
resulting in new triple point pressures comparable to those in the literature.
45
6 NEW THERMODYNAMICALLY CONSISTENT VAPOR PRESSURE
PREDICTION
This work has been published [58] and will be summarized here. Although vapor
pressure is the most commonly measured property of those discussed here, many compounds do
not have any 𝑃𝑃vap data outside of the normal boiling point. Since 𝑃𝑃vap is an important property
for a variety of chemical processes, and other properties can be derived from it, predicting vapor
pressure well as a function of temperature could drastically improve the reliability, safety, and
profitability of chemical processes.
For many years, the Riedel equation has been considered an excellent and simple choice
among vapor-pressure correlating equations [59], but this work shows that it requires modification
of the final coefficient to provide thermodynamic consistency with thermal data [60]. Specifically,
Riedel’s prediction method sets the final coefficient to a constant value of 6, but this restricts the
shape of the correlation at low temperatures, which in turn severely restricts the ability of the
model to produce accurate liquid heat capacity values below the normal boiling point.
This chapter will: 1) explain newly created predictive correlations where this final
coefficient is changed from 1 to 6 in integer steps and 2) demonstrate how these correlations give
improved prediction of vapor pressures for compounds with limited or no experimental data. The
methodology followed is that originally proposed by Riedel [6] but the last coefficient was chosen
based on its ability to simultaneously represent vapor pressure and liquid heat capacity. This
46
procedure improves the average absolute deviation of the fit to the liquid heat capacity data from
9% to 3%, while maintaining the fit to vapor pressure and heat of vaporization data similar to other
prediction methods. This procedure also greatly improves the ability to predict low-temperature
vapor pressure by using liquid heat capacity data.
6.1 Introduction
The Riedel equation [6] for fitting and predicting the temperature dependence of vapor
pressure is
𝐵𝐵
𝑃𝑃vap = exp �𝐴𝐴 + + 𝐶𝐶ln(𝑇𝑇) + 𝐷𝐷𝑇𝑇 𝐸𝐸 � (6-1)
𝑇𝑇
where 𝐴𝐴 − 𝐸𝐸 are fitting coefficients. Recently, it has been found that changing the 𝐸𝐸 value – the
5th parameter – can improve both the vapor pressure fit [10] and the thermodynamic consistency
with other properties—specifically heat of vaporization and liquid and ideal gas heat capacities
[60]. The Riedel equation was originally published with a method to predict vapor pressure for
compounds without experimental data [6]. However, this method restricted the ability of the
prediction of liquid heat capacity by keeping 𝐸𝐸 at 6. This study created a series of new predictive
vapor pressure equations with 𝐸𝐸 =1,2,3,4,5, and 6 to improve the flexibility of the correlation
and increase thermodynamic consistency with liquid heat capacity data while increasing the
training set to include a more diverse group of compounds. Only integer values were selected
because the data rarely justified increasing the precision on 𝐸𝐸. Then, a larger set of compounds
was tested to see which 𝐸𝐸 value works best for each chemical family. The previous chapter
shows best 𝐸𝐸 values for alkanes, alkenes, aldehydes, aromatics, ethers, and ketones families [60].
This report expanded this analysis into alkynes, esters, light gases, halogenated compounds,
multifunctional compounds, ring alkanes, silanes, and sulfides as well. Using this prediction
47
along with methods established in Chapter 2 extends the prediction into heat of vaporization and
liquid heat capacity as well, effectively turning one predictive correlation into three.
The rest of this chapter will go as follows. First, existing vapor pressure prediction
methods will be introduced from the literature. Then, the theory linking vapor pressure, heat of
vaporization, and ideal gas and liquid heat capacities will be explained along with the theory
behind this new predictive method. After that, the steps used to create the new method are
outlined along with the compounds used to train the method. Finally, the new method is
compared to other prediction methods and tested using a different set of compounds with
favorable results.
6.2 Overview of Vapor Pressure Prediction and Correlation Methods
Several 𝑃𝑃vap prediction methods are in use today. Riedel’s original prediction method,
established in 1957 [6], has the form:
𝐵𝐵
ln(𝑃𝑃𝑟𝑟 ) = 𝐴𝐴 + + 𝐶𝐶ln(𝑇𝑇𝑟𝑟 ) + 𝐷𝐷𝑇𝑇𝑟𝑟 6 (6-2)
𝑇𝑇𝑟𝑟
where 𝑇𝑇𝑟𝑟 and 𝑃𝑃𝑟𝑟 are reduced temperature and vapor pressure, respectively, 𝐴𝐴 − 𝐷𝐷 are fitting
parameters, and 𝐸𝐸 of Equation 6-1 is set to 6. This value of 𝐸𝐸 was chosen because it appeared to
give a favorable shape towards the critical point compared to enthalpic data [6, 61]. Coefficients
𝐴𝐴 − 𝐶𝐶 are found using the following three constraints:
1. force Equation 6-2 to give 1 atm at the normal boiling point (𝑇𝑇𝑁𝑁𝑁𝑁 )
2. force Equation 6-2 to give the critical pressure (𝑃𝑃𝑐𝑐 ) at the critical temperature (𝑇𝑇𝑐𝑐 )
3. set the slope of the Riedel parameter to zero at the critical point
The Riedel parameter, 𝛼𝛼, is defined as:
48
𝜕𝜕ln𝑃𝑃𝑟𝑟 𝐵𝐵
𝛼𝛼 ≡ = − + 𝐶𝐶 + 6𝐷𝐷𝑇𝑇𝑟𝑟6 (6-3)
𝜕𝜕ln𝑇𝑇𝑟𝑟 𝑇𝑇𝑟𝑟
The last coefficient is found from fitting to experimental data. Specifically, the 𝐷𝐷 parameter is
constrained to relate to the Riedel parameter (α), evaluated at the critical point, according to:
𝐷𝐷 = −𝐾𝐾(𝑋𝑋𝑐𝑐 − 𝛼𝛼𝑐𝑐 ) (6-4)
where 𝐾𝐾 and 𝑋𝑋𝑐𝑐 were found to be 0.0838 and 3.758, respectively, from a fit of 𝑃𝑃vap data for the
compounds listed in Table 2-1.
Unfortunately, this formulation, where the 𝐸𝐸 parameter is fixed at 6, has been shown to
cause the liquid heat capacity (𝐶𝐶𝑝𝑝𝑙𝑙 ) curve obtained from the Derivative method (See Chapter 2) to
dip too low at the triple point temperature (𝑇𝑇𝑇𝑇𝑇𝑇 ) [60]. To correct for this, the Derivative Method
can be paired with a corresponding states method (explained below) to predict 𝐶𝐶𝑝𝑝𝑙𝑙 [2]. The
former is used at higher temperatures and the latter at lower temperatures. Unfortunately, this
does not ensure thermodynamic consistency between 𝑃𝑃vap and 𝐶𝐶𝑝𝑝𝑙𝑙 .
Table 6-1: Compounds originally investigated by Riedel,

grouped by chemical family
Training Set Family Number of Compounds
Alkane 4
Alkene 2
Ester 5
Ether 1
Gas 5
Halogenated 3
Lee and Kesler introduced a corresponding states 𝑃𝑃vap prediction method (Lee-Kesler) in
1975 [62] of the form:
ln(𝑃𝑃𝑟𝑟 ) = ln𝑃𝑃0 (𝑇𝑇𝑟𝑟 ) + 𝜔𝜔ln𝑃𝑃1 (𝑇𝑇𝑟𝑟 ) (6-5)
49
where 𝜔𝜔 is the acentric factor predicted using the normal boiling point, and ln𝑃𝑃0 (𝑇𝑇𝑟𝑟 ) and
ln𝑃𝑃1 (𝑇𝑇𝑟𝑟 ) are empirically fit equations with the same form as the Riedel predictive method with
𝐸𝐸 = 6. This method was proposed as a thermodynamically robust correlation and drew favorable
comparisons to previous methods.
Citing a need for a better 𝑃𝑃vap predictive form, Vetere published a method using the
Wagner correlation (Vetere-Wagner) in 1991 [63]. This approach related the temperature to the
vapor pressure according to:
1
ln(𝑃𝑃𝑟𝑟 ) = [𝐴𝐴(1 − 𝑇𝑇𝑟𝑟 ) + 𝐵𝐵(1 − 𝑇𝑇𝑟𝑟 )1.5 + 𝐶𝐶(1 − 𝑇𝑇𝑟𝑟 )3 ] (6-6)
𝑇𝑇𝑟𝑟
where the coefficients 𝐴𝐴 − 𝐶𝐶 were calculated using the following constraints:
1. Forcing Equation 6-6 to give 1 atm at the normal boiling point
2. Fitting a predicted Riedel parameter, defined in Equation 6-3, at the critical point
3. Fitting a predicted Riedel parameter, also defined in Equation 6-3, at the normal boiling point
These Riedel parameters were predicted using correlations from an empirical study of different
chemical families. The authors admitted, at the time of its publication, that this method was only
an initial attempt to make the Wagner correlation fully predictive [63], but no other major
improvements have been made since.
Seeking to improve on the Riedel predictive method, Vetere [61] kept Equation 6-2 with
𝐸𝐸 at 6 but changed how the empirical constant 𝐾𝐾 was calculated. Instead of using only vapor
pressure data to fit Equation 6-4, he used the normal boiling point, critical point, acentric factor,
reduced temperature, and chemical family. Initially, the selected families were nonpolar
compounds, acids, alcohols, glycols, and other polar compounds [61]. Fifteen years later in 2006,
Vetere improved upon his previous method by segregating the chemical families further and
increasing the mathematical complexity of the 𝐾𝐾 parameter calculations [64]. This Vetere-Riedel
50
method gave better results when predicting the vapor pressures of saturated and branched
hydrocarbons, olefins and aromatic compounds, alcohols, and other compounds [64] compared
to the original Riedel prediction and the Lee-Kesler prediction.
These methods predict vapor pressure well. However, none of them could adequately
replicate liquid heat capacity data below the normal boiling point, where the majority of heat
capacity data exist. At these temperatures, few experimental vapor pressure data typically exist,
and when they do, they suffer from high uncertainties [50, 51]. Therefore, liquid heat capacity
data can be used to formulate a better vapor pressure prediction at low temperatures. A new
prediction is necessary to achieve thermodynamic consistency by matching both 𝑃𝑃vap and 𝐶𝐶𝑝𝑝𝑙𝑙
data.
6.3 Theory
6.3.1 Thermodynamic Relationships
In order to overcome the limitations explained in the previous section, a new 𝑃𝑃vap
prediction method was created in order to predict both 𝑃𝑃vap and 𝐶𝐶𝑝𝑝𝑙𝑙 correctly. 𝑃𝑃vap is related to
𝐶𝐶𝑝𝑝𝑙𝑙 through rigorous thermodynamic equations involving the first and second temperature
derivatives of 𝑃𝑃vap as shown by the Clapeyron equation and Derivative method in Equations 2-1
and 2-6.
6.3.1 New Predictive Vapor Pressure Method
The new predictive method for 𝑃𝑃vap was created using the same methodology laid out by
Riedel with one crucial exception: the exponent on 𝑇𝑇𝑟𝑟 in the final term, 𝐸𝐸 of Equation 1, was
changed from 6 to other integer values. Specifically, the general Riedel equation was used in the
linearized and reduced form
51
𝐵𝐵
ln(𝑃𝑃𝑟𝑟 ) = 𝐴𝐴 + + 𝐶𝐶ln(𝑇𝑇𝑟𝑟 ) + 𝐷𝐷𝑇𝑇𝑟𝑟 𝐸𝐸 (6-7)
𝑇𝑇𝑟𝑟
where 𝑃𝑃𝑟𝑟 is the reduced pressure, 𝑇𝑇𝑟𝑟 is the reduced temperature, 𝐴𝐴 − 𝐷𝐷 are fitting parameters, and
𝐸𝐸 is changed from 1 to 6 in integer steps. Changing 𝐸𝐸 has been found to improve the ability of
the 𝑃𝑃vap correlation to successfully predict 𝐶𝐶𝑝𝑝𝑙𝑙 using the Derivative method for compounds with
𝑃𝑃vap and 𝐶𝐶𝑝𝑝𝑙𝑙 data in the previous chapter. Therefore, the best 𝐸𝐸 will be determined by the
predictive correlation’s ability to fit 𝑃𝑃vap and 𝐶𝐶𝑝𝑝𝑙𝑙 data.
Four constraints are necessary to calculate coefficients 𝐴𝐴 − 𝐷𝐷. Three constraints are the
exact same as Riedel’s original prediction method:
1. force Equation 6-7 to give 1 atm at the normal boiling point (𝑇𝑇𝑁𝑁𝑁𝑁 )
2. force Equation 6-7 to give the critical pressure (𝑃𝑃𝑐𝑐 ) at the critical temperature (𝑇𝑇𝑐𝑐 )
3. set the slope of the Riedel parameter to zero at the critical point (See Equation 6-10)
Solving 𝐴𝐴 − 𝐶𝐶 in terms of 𝐷𝐷 gives:
ln(𝑇𝑇𝑟𝑟 ) ln(𝑇𝑇𝑟𝑟 )
ln(𝑃𝑃𝑟𝑟 ) = ln(𝑃𝑃𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 ) � � + 𝐷𝐷 �𝜙𝜙(𝑇𝑇𝑟𝑟 ) − 𝜙𝜙(𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 ) � �� (6-8)
ln(𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 ) ln(𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 )
where
𝐸𝐸 2
𝜙𝜙(𝑇𝑇𝑟𝑟 ) = 𝐸𝐸 2 − 1 − − 𝐸𝐸(𝐸𝐸 + 1) ln(𝑇𝑇𝑟𝑟 ) + 𝑇𝑇𝑟𝑟𝐸𝐸 (6-9)
𝑇𝑇𝑟𝑟
and 𝑃𝑃𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 and 𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 are the reduced atmosphere the reduced normal boiling point, respectively.
To obtain the fourth constraint, the Riedel parameter 𝛼𝛼 is defined:
𝜕𝜕ln𝑃𝑃𝑟𝑟 𝐵𝐵
𝛼𝛼 ≡ = − + 𝐶𝐶 + 𝐷𝐷𝐷𝐷𝑇𝑇𝑟𝑟𝐸𝐸 (6-10)
𝜕𝜕ln𝑇𝑇𝑟𝑟 𝑇𝑇𝑟𝑟
which is the same as Riedel’s predictive method, except it has been generalized for all values of
𝐸𝐸. At the critical point, the Riedel parameter reduces to:
52
𝛼𝛼𝑐𝑐 = −𝐵𝐵 + 𝐶𝐶 + 𝐷𝐷𝐷𝐷 (6-11)
or
ln(𝑃𝑃𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 ) 𝜙𝜙(𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 )
𝛼𝛼𝑐𝑐 = − 𝐷𝐷 (6-12)
ln(𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 ) ln(𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 )
when 𝐵𝐵 and 𝐶𝐶 are substituted using Constraints 1-3. 𝐷𝐷 is found following Riedel’s original
methodology by fitting Equation 6-4 to experimental data to find 𝐾𝐾 and 𝑋𝑋𝑐𝑐 , fitting parameters
describing a corresponding states analysis. Substituting Equation 6-12 into Equation 6-4 and
rearranging allows 𝐷𝐷 to be rewritten in terms of 𝐾𝐾 and 𝑋𝑋𝑐𝑐 according to:
ln(𝑃𝑃𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 ) + 𝐾𝐾𝑋𝑋𝑐𝑐 𝜙𝜙(𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 )

𝐷𝐷 = 𝐾𝐾 � − 𝑋𝑋𝑐𝑐 � (6-13)
ln(𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 ) + 𝐾𝐾𝐾𝐾(𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 )
Substitution of Equation 6-13 into Equation 6-8 yields the desired predictive correlation:
ln(𝑇𝑇𝑟𝑟 ) ln(𝑃𝑃𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 ) + 𝐾𝐾𝑋𝑋𝑐𝑐 𝜙𝜙(𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 ) ln(𝑇𝑇𝑟𝑟 )

ln(𝑃𝑃𝑟𝑟 ) = ln(𝑃𝑃𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 ) � � + 𝐾𝐾 � − 𝑋𝑋𝑐𝑐 � �𝜙𝜙(𝑇𝑇𝑟𝑟 ) − 𝜙𝜙(𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 ) � �� (6-14)
ln(𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 ) ln(𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 ) + 𝐾𝐾𝐾𝐾(𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 ) ln(𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 )
where each value of 𝐸𝐸 requires a unique set of 𝐾𝐾, 𝑋𝑋𝑐𝑐 , and 𝜙𝜙. The parameter 𝜙𝜙 is defined as:
𝐸𝐸 2
𝜙𝜙(𝑇𝑇𝑟𝑟 ) = 𝐸𝐸 2 − 1 − − 𝐸𝐸(𝐸𝐸 + 1) ln(𝑇𝑇𝑟𝑟 ) + 𝑇𝑇𝑟𝑟𝐸𝐸 (6-15)
𝑇𝑇𝑟𝑟
6.4 Methods
6.4.1 Regression of K and Xc as a Function of E
Recall (See Section 6.2) that Riedel set 𝐸𝐸 = 6 and found 𝐷𝐷 by fitting Equation 6-8 to
experimental data. He then found 𝐾𝐾 and 𝑋𝑋𝑐𝑐 (0.0838 and 3.758, respectively) that satisfied
Equation 6-4 so that the method could be predictive. The same procedure was followed here
using Equation 6-13 with 𝐸𝐸 = 1, 2, 3, 4, 5, and 6.
The training set in this study, used to fit the 𝐷𝐷 coefficient, consisted of 37 compounds
from the eight chemical families listed in Table 6-2. These compounds were selected because: 1)
53
they contained considerable 𝑃𝑃vap data over a wide temperature range, and 2) they were a
chemically diverse set. Summaries of the data used for these compounds are given in the
Appendix. In each case, the 𝐷𝐷 coefficient was fit to experimental 𝑃𝑃vap data for a training set of
compounds and the corresponding 𝐾𝐾 and 𝑋𝑋𝐶𝐶 were found. Thus, six sets of 𝐾𝐾 and 𝑋𝑋𝐶𝐶 values were
obtained—one set for each 𝐸𝐸 value.
Table 6-3 contains the results. Notice that 𝐾𝐾 decreases rapidly (orders of magnitude) with
increasing 𝐸𝐸 values. 𝑋𝑋𝐶𝐶 also decreases with increasing 𝐸𝐸, but much more slowly.
The dependence of 𝐾𝐾 and 𝑋𝑋𝐶𝐶 on 𝐸𝐸 is displayed graphically in Figure 6-1. The behavior of
𝐾𝐾 is exponential in nature, while that of 𝑋𝑋𝐶𝐶 is quadratic. Thus, the behavior of each can be fit
reliably (𝑅𝑅2 = 0.9990 for both) to the following correlations (displayed as lines on the figure).
𝐾𝐾 = 4.96465𝐸𝐸 −2.29195 (6-16)
𝑋𝑋𝑐𝑐 = 4.14524 − 0.0818433𝐸𝐸 + 0.00310685𝐸𝐸 2 (6-17)
With these equations, non-integer values of 𝐸𝐸 may be chosen to fit vapor pressure data when the
𝑃𝑃vap and 𝐶𝐶𝑝𝑝𝑙𝑙 data quantity and quality merit. A sample calculation using this predictive method is
given in the Appendix.
The last two rows of
Table 6-3 are significant. These show the 𝐾𝐾 and 𝑋𝑋𝐶𝐶 values for 𝐸𝐸 = 6 for the new method
and Riedel’s original method. Notice that when 𝐸𝐸 = 6, 𝐾𝐾 and 𝑋𝑋𝑐𝑐 for the new method are nearly
identical to those from Riedel’s original work. Even though the training set for the new method
contains nearly double the number of compounds as Riedel’s original training set, the results are
similar.
54
Table 6-2: Training set of compounds for the new
predictive Pvap correlation, grouped
by chemical families
Training Set Family Number
Alkane 11
Alkene 1
Aromatic 5
Ester 3
Ether 1
Gas 5
Halogenated 4
Ketone 7
Table 6-3: Summary of prediction constants for the original

Riedel Pvap prediction and this new Pvap prediction
Source 𝑬𝑬 K Xc
This 1 5.0398 4.065
Work 2 1.0048 3.996
3 0.3931 3.928
4 0.2045 3.867
5 0.1244 3.812
6 0.0836 3.767
Riedel [6] 6 0.0838 3.758
6 4.10
5 4.05
4.00
4
3.95
3
Xc
K
3.90
2
3.85
1 3.80
0 3.75
1 2 3 4 5 6
E Value
Figure 6-1: Fitting parameters K and Xc as functions of E
55
6.4.2 E Training Method
As is apparent from Figure 6-1, 𝐸𝐸 must be selected before the vapor pressure can be
predicted. It was hypothesized that an optimal 𝐸𝐸 value could be found for families of
compounds. This was tested using a set of 106 compounds from the families listed in Table 6-4
which includes the 36 compounds used to generate 𝐾𝐾 and 𝑋𝑋𝑐𝑐 in Figure 6-1. Summaries of the
data used for these compounds are given in the Appendix. The best 𝐸𝐸 value was found for each
compound by minimizing the average absolute deviation (𝐴𝐴𝐴𝐴𝐴𝐴) of the predictions from the
experimental data for 𝑃𝑃vap and 𝐶𝐶𝑝𝑝𝑙𝑙 simultaneously. Heat of vaporization could also have been
used, but most Δ𝐻𝐻vap data in the literature were derived from vapor pressure fits using the
Clapeyron equation. When calorimetric data were present in the literature, they were usually at
temperatures where vapor pressure data were plentiful with low uncertainty. Therefore, Δ𝐻𝐻vap
was not used to find the best 𝐸𝐸 in this analysis. Specifically, 𝐴𝐴𝐴𝐴𝐴𝐴 for the property was defined
as:
1 𝐽𝐽𝑖𝑖 − 𝐽𝐽̂(𝐸𝐸, 𝑇𝑇𝑖𝑖 )

𝐴𝐴𝐴𝐴𝐴𝐴 = �� (6-18)
𝑁𝑁 𝐽𝐽𝑖𝑖
𝑖𝑖
where 𝐽𝐽𝑖𝑖 is the experimental value for the property (vapor pressure, heat of vaporization, or liquid
heat capacity), 𝐽𝐽̂(𝐸𝐸, 𝑇𝑇𝑖𝑖 ) is the model prediction for the property for a certain 𝐸𝐸 and temperature
𝑇𝑇𝑖𝑖 , and 𝑁𝑁 is the number of experimental points for that property. The “best” value of 𝐸𝐸 was
defined as the value that minimized the average of 𝑃𝑃vap and 𝐶𝐶𝑝𝑝𝑙𝑙 𝐴𝐴𝐴𝐴𝐴𝐴 for each compound.
Although propyl formate was used to create this 𝑃𝑃vap prediction method, it was omitted
from this analysis because it did not have sufficient experimental 𝐶𝐶𝑝𝑝𝑙𝑙 data. Only one alkyne and
one silane were included because few compounds in those families contained 𝑃𝑃vap and 𝐶𝐶𝑝𝑝𝑙𝑙 data.
Of noticeable omission are the alcohols and acids, families where self-association has been well
56
documented [49, 65-67]. For these compounds, more data are necessary along with a separate
analysis scheme that may require a different 𝑃𝑃vap correlation form and a modified equation of
state to calculate the vapor volumes. Due to these complications, strongly hydrogen bonding
families will not be discussed here.
6.5 Results
6.5.1 Optimized E by Family
The last two columns of Table 6-4 contain the average 𝐴𝐴𝐴𝐴𝐴𝐴’s for all of the compounds
tested in each chemical family using the best 𝐸𝐸, which was found by minimizing the average of
the 𝑃𝑃vap and 𝐶𝐶𝑝𝑝𝑙𝑙 𝐴𝐴𝐴𝐴𝐴𝐴 for each compound. The 𝐴𝐴𝐴𝐴𝐴𝐴 for Δ𝐻𝐻vap was not used in the optimization
scheme because only 74 of the compounds contained experimental Δ𝐻𝐻vap data (see the
Appendix). When Δ𝐻𝐻vap data did exist, changing the 𝐸𝐸 value did not change the ability of the
𝑃𝑃vap correlation to follow the experimental Δ𝐻𝐻vap values. The new predictive method predicts
𝑃𝑃vap for all families below 5% 𝐴𝐴𝐴𝐴𝐴𝐴, and predicts 𝐶𝐶𝑝𝑝𝑙𝑙 for all but the light gases below 5% 𝐴𝐴𝐴𝐴𝐴𝐴 on
average. Members of the light gas group include several noble gases and diatomic compounds
with triple point temperatures between 10 and 70 K, and critical temperatures between 30 and
160 K. The triple point temperatures for nearly all the other compounds were above 200 K, so it
appears that this method works better at temperatures above about 150 K. The other predictive
methods gave similar results for the light gases as well.
57
Table 6-4: Average Pvap, ΔHvap, and Cpl absolute average deviations (AAD) for the compounds in
each chemical family using the best 𝑬𝑬 value for each compound
Family Number of Compounds Avg 𝑷𝑷𝐯𝐯𝐯𝐯𝐯𝐯 𝐴𝐴𝐴𝐴𝐴𝐴 (%) Avg 𝚫𝚫𝑯𝑯𝐯𝐯𝐯𝐯𝐯𝐯 𝐴𝐴𝐴𝐴𝐴𝐴 (%) Avg 𝑪𝑪𝒍𝒍𝒑𝒑 𝐴𝐴𝐴𝐴𝐴𝐴 (%)
Aldehyde 4 1.42 1.35 4.21
Alkane 15 1.06 1.72 3.23
Alkene 9 4.43 0.91 4.64
Alkyne 1 1.52 0.92 2.84
Amine 8 3.18 0.82 2.18
Aromatic 12 4.73 0.52 2.58
Ester 6 4.46 0.45 1.64
Ether 5 1.97 1.26 3.70
Light Gases 5 0.59 1.43 6.81
Halogenated 8 1.65 0.95 3.62
Ketone 8 1.52 1.15 2.64
Multifunctional 14 2.26 0.44 2.43
Ring Alkane 5 2.41 2.22 2.10
Silane 1 2.49 -- 2.38
Sulfide 5 0.95 1.27 2.78
Figure 6-2 shows the distribution of best 𝐸𝐸 values for the 106 test compounds separated
into chemical families. The majority of compounds were best optimized using 𝐸𝐸 = 3 or 𝐸𝐸 = 4,
though amines seem to do best with 𝐸𝐸 = 2 and aromatics seem to favor 𝐸𝐸 = 4 and above.
The best integer 𝐸𝐸 value for each family was chosen by finding the integer that best fits
the most compounds in each family. These recommended 𝐸𝐸 values are summarized in Table 6-5.
The five light gases showed a spread in best 𝐸𝐸 value, with a much larger average 𝐶𝐶𝑝𝑝𝑙𝑙 𝐴𝐴𝐴𝐴𝐴𝐴 than
the other families. In this case, a value of 𝐸𝐸 was chosen as it was closest to the average best 𝐸𝐸
value. For compounds outside of the families listed, 𝐸𝐸 should be set to 3 or 4, unless the
compounds strongly self-associate. As was explained in Section 4 above, alcohols and acids
were not included.
58
50
Aldehyde (4)
45 Alkane (15)
40 Alkene (9)
Alkyne (1)
35
Number of Compounds
Amine (8)
30 Aromatic (12)
Ester (6)
25
Ether (5)
20
Gas (5)
15 Halogenated (8)
Ketone (8)
10
Multifunctional (14)
5 Ring Alkane (5)
0 Silane (1)
1 2 3 4 5 6 Sulfide (5)
Best E
Figure 6-2: Distribution of best E values using the new predictive Riedel Pvap method on the test
compounds
In general, the best 𝐸𝐸 values used to predict 𝑃𝑃vap are 3 or 4 for all but the amine and gas
families.
Contrast these results to a previous study that found that a value of 2 should be used for
these same exact families [60]. The key difference here is that the previous article did not use the
Riedel parameter constraint (Constraint 3), while this prediction does. Adding an additional
constraint at the critical point changed the shape of the 𝑃𝑃vap curve in a way that the best
correlations required a larger 𝐸𝐸 value. For compounds with extensive 𝑃𝑃vap data, Constraint 3 is
not needed. In those cases, a smaller 𝐸𝐸 value works better. However, for compounds with limited
or no 𝑃𝑃vap data, an 𝐸𝐸 value one integer larger works better.
59
Table 6-5: Recommended E values for each of the
chemical families tested
Family Best 𝑬𝑬
Aldehyde 4
Alkane 3
Alkene 3
Alkyne 3
Amine 2
Aromatic 4
Ester 4
Ether 3
Gas 5
Halogenated 4
Ketone 3
Multifunctional 3 or 4
Ring Alkane 4
Silane 3
Sulfide 3
6.5.2 Comparison to Other Predictive Methods
The new prediction method was compared to Riedel’s original method [6], the Lee-
Kesler corresponding states method [62], Vetere’s Wagner correlation prediction method [63],
and Vetere’s newest Riedel correlation prediction method [64]. The recommended 𝐸𝐸 values in
Table 6-5 were applied to each of the 106 compounds analyzed. The 𝑃𝑃vap 𝐴𝐴𝐴𝐴𝐴𝐴 distribution of the
test compounds is given in Figure 6-3 for the five prediction methods. This bar chart shows the
number of compounds on the y-axis for each range of 𝑃𝑃vap 𝐴𝐴𝐴𝐴𝐴𝐴 on the x-axis and each
prediction method, shown with different color bars. The red, orange, yellow, and green bars
show the results for the Riedel, Lee-Kesler, Vetere-Wagner, and Vetere-Riedel methods,
respectively. The blue dotted bars show the results for this new predictive method. For example,
this chart shows that 70 compounds were predicted with a 𝑃𝑃vap 𝐴𝐴𝐴𝐴𝐴𝐴 in the range 0-2% using this
60
new predictive method. This new method performs at least as well as the other methods since the
𝑃𝑃vap 𝐴𝐴𝐴𝐴𝐴𝐴 distribution for this method is bunched slightly more toward zero than the other
prediction methods. The 𝑃𝑃vap 𝐴𝐴𝐴𝐴𝐴𝐴 distribution for the new method is not discernably different
from the best of other methods (Riedel). Therefore, this new method retains but does not
noticeably improve the fit of 𝑃𝑃vap where the 𝑃𝑃vap data are located. 𝑃𝑃vap 𝐴𝐴𝐴𝐴𝐴𝐴 is greater than 10%
using this work for three compounds: 1,3-trans-pentadiene, pyrene, and octyl acetate. In these
cases, the majority of 𝑃𝑃vap data are under 1000 Pa where uncertainty in 𝑃𝑃vap measurements
grows [50, 51].
80
70 Riedel
Number of Compounds
60 Lee-Kesler
50
Vetere-Wagner
Vetere-Riedel
40
This Work
30
20
10
0
0-2% 2-4% 4-6% 6-8% 8-10% 10-12% 12-14% 14-16% 16-18% 18-20% >20%
Pvap 𝐴𝐴𝐴𝐴𝐷𝐷
Figure 6-3: The distribution of Pvap AAD for 106 test compounds using Pvap prediction methods:
Riedel’s original method, Lee-Kesler, Vetere’s Wagner method, Vetere’s Riedel method, and this
work
The Δ𝐻𝐻vap 𝐴𝐴𝐴𝐴𝐴𝐴 distribution of the test compounds is given in Figure 6-4. Notice that the
x-axis extends to 10% instead of 20% as shown in Figure 6-3. Although the scale is different, the
message is the same: these 𝑃𝑃vap prediction methods are not discernible when looking at Δ𝐻𝐻vap
61
data. However, the Δ𝐻𝐻vap 𝐴𝐴𝐴𝐴𝐴𝐴 distributions for the Riedel prediction and this prediction (solid
red and blue dotted bars, respectively) are slightly bunched closer to zero than the other three
methods. Although looking towards Δ𝐻𝐻vap does not give much new information, the Δ𝐻𝐻vap 𝐴𝐴𝐴𝐴𝐷𝐷
distribution indicates that the original Riedel prediction and this work may do slightly better for
Δ𝐻𝐻vap .
35
30 Riedel
Number of Compounds
Lee-Kesler
25
Vetere-Wagner
20
Vetere-Riedel
15 This Work
10
0
0-1% 1-2% 2-3% 3-4% 4-5% 5-6% 6-7% 7-8% 8-9% 9-10% >10%
Δ𝐻𝐻vap 𝐴𝐴𝐴𝐴𝐷𝐷
Figure 6-4: The distribution of ΔHvap for 106 test compounds using Pvap prediction methods:
Riedel’s original method, Lee-Kesler, Vetere’s Wagner method, Vetere’s Riedel method, and this
work
The 𝐶𝐶𝑝𝑝𝑙𝑙 𝐴𝐴𝐴𝐴𝐴𝐴 distribution of the test compounds is given in Figure 6-5 and demonstrates
how the new method excels. This 𝐶𝐶𝑝𝑝𝑙𝑙 𝐴𝐴𝐴𝐴𝐴𝐴 distribution for this new method (again, the blue
dotted bars) is bunched much closer to 0% than any of the other 𝑃𝑃vap prediction methods. Only
one compound has an 𝐴𝐴𝐴𝐴𝐴𝐴 greater than 12% for the new method compared to 11 for Vetere-
Wagner, 18 for Vetere-Riedel, 21 for the original Riedel method, and 24 for Lee-Kesler. The
62
method developed in this work does a much better job predicting thermodynamically consistent
𝑃𝑃vap and 𝐶𝐶𝑝𝑝𝑙𝑙 data than the other 𝑃𝑃vap prediction methods found in the literature.
50
45 Riedel
40
Number of Compounds
Lee-Kesler
35
Vetere-Wagner
30
25 Vetere-Riedel
20 This Work
15
10
5
0
0-2% 2-4% 4-6% 6-8% 8-10% 10-12% 12-14% 14-16% 16-18% 18-20% >20%
Cpl 𝐴𝐴𝐴𝐴𝐷𝐷
Figure 6-5: The distribution of Cpl AAD for the test compounds using Pvap prediction methods
within the Derivative method: Riedel’s original method, Lee-Kesler, Vetere’s Wagner method,
Vetere’s Riedel method, and this work
6.5.3 Testing the Methods with Compounds Not Used in the Training Set
To fully test the applicability of the method, five sets of 40 compounds were randomly
chosen from the 70 compounds not used to train the 𝐾𝐾 and 𝑋𝑋𝑐𝑐 values, and the average 𝑃𝑃vap ,
Δ𝐻𝐻vap , and 𝐶𝐶𝑝𝑝𝑙𝑙 𝐴𝐴𝐴𝐴𝐴𝐴’s were found for the five prediction methods (four previous methods and
that of this work). Only 70 compounds were used for this analysis because the 36 other
compounds were used to fit the 𝑃𝑃vap correlations, and including these would bias the 𝑃𝑃vap 𝐴𝐴𝐴𝐴𝐷𝐷
results in favor of the new method.
The average 𝑃𝑃vap , Δ𝐻𝐻vap , and 𝐶𝐶𝑝𝑝𝑙𝑙 absolute average deviations (𝐴𝐴𝐴𝐴𝐴𝐴) of the five sets of
compounds for the five 𝑃𝑃vap prediction methods are given in Figure 6-6 with 95% confidence
intervals. The values are ordered on the X-axis by chronological order of publication. The new
63
method significantly decreased 𝐶𝐶𝑝𝑝𝑙𝑙 𝐴𝐴𝐴𝐴𝐴𝐴 from around 7% to 3% without significantly increasing
𝑃𝑃vap and Δ𝐻𝐻vap 𝐴𝐴𝐴𝐴𝐴𝐴. Since almost all of the 𝐶𝐶𝑝𝑝𝑙𝑙 data in the literature are just above the triple
point temperature (𝑇𝑇𝑇𝑇𝑇𝑇 ) and most of the 𝑃𝑃vap data in the literature are bunched around 𝑇𝑇𝑁𝑁𝑁𝑁 for
each compound, an improvement in 𝐶𝐶𝑝𝑝𝑙𝑙 𝐴𝐴𝐴𝐴𝐴𝐴 corresponds to an improvement in the 𝑃𝑃vap and
Δ𝐻𝐻vap correlations near the 𝑇𝑇𝑇𝑇𝑇𝑇 where it is difficult to measure 𝑃𝑃vap accurately [50, 51].
Therefore, this new method predicts vapor pressure at lower temperatures with lower uncertainty
than any other prediction method tested.
12
Vapor Pressure AAD
10 Heat of Vaporization AAD
Liquid Heat Capacity AAD
8
AAD (%)
0
Riedel (1954) Lee-Kesler (1975) Vetere-Wagner (1991) Vetere-Riedel (2006) This Work (2017)
Pvap Prediction Method
Figure 6-6: Average Pvap, ΔHvap, and Cpl AAD for five sets of 40 compounds using different Pvap
prediction methods
6.6 Conclusions
Predictive methods for the Riedel equation with different final coefficient values were
created. In summary, the coefficients 𝐴𝐴 − 𝐶𝐶 for Equation 6-7 are calculated using 𝐷𝐷, 𝐸𝐸, and 𝛼𝛼𝑐𝑐
as follows:
64
𝐴𝐴 = (𝐸𝐸 2 − 1)𝐷𝐷 (6-19)
𝐵𝐵 = −𝐸𝐸 2 𝐷𝐷 (6-20)
𝐶𝐶 = 𝛼𝛼𝑐𝑐 − 𝐸𝐸(𝐸𝐸 + 1)𝐷𝐷 (6-21)
The coefficient 𝐷𝐷 and the Riedel parameter at the critical point 𝛼𝛼𝑐𝑐 are calculated from the
reduced normal boiling point (𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 ), 𝐾𝐾, 𝑋𝑋𝑐𝑐 , and 𝐸𝐸:
ln�𝑃𝑃atm,𝑟𝑟 � + 𝐾𝐾𝑋𝑋𝑐𝑐 𝜙𝜙(𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 , 𝐸𝐸)

𝐷𝐷 = 𝐾𝐾 � − 𝑋𝑋𝑐𝑐 � (6-22)
ln(𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 ) + 𝐾𝐾𝐾𝐾(𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 , 𝐸𝐸)
ln�𝑃𝑃atm,𝑟𝑟 � + 𝐾𝐾𝑋𝑋𝑐𝑐 𝜙𝜙(𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 , 𝐸𝐸)

𝛼𝛼𝑐𝑐 = (6-23)
ln(𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 ) + 𝐾𝐾𝐾𝐾(𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 , 𝐸𝐸)
where 𝑃𝑃atm,𝑟𝑟 is the reduced atmosphere (or, 1 atmosphere divided by the critical pressure), 𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛
is the reduced normal boiling point, and 𝜙𝜙 is given as:
2
𝐸𝐸 2 𝐸𝐸
𝜙𝜙(𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 , 𝐸𝐸) = 𝐸𝐸 − 1 − − 𝐸𝐸(𝐸𝐸 + 1) ln(𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 ) + 𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 (6-24)
𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛
Equations 6-16 and 6-17 are used to calculate 𝐾𝐾 and 𝑋𝑋𝑐𝑐 , respectively. Equations 6-19 through
6-24 provide a set of 𝑃𝑃vap predictive correlations with 𝐸𝐸 values from 1 to 6 in integer steps.
These correlations were compared to experimental vapor pressure and liquid heat
capacity data. Vapor pressure and liquid heat capacity data for aldehydes, alkanes, alkenes,
alkynes, amines, aromatics, esters, ethers, gases, halogenated compounds, ketones,
multifunctional compounds, ringed alkanes, silanes, and sulfides were used to determine the
selection of the Riedel 𝐸𝐸 coefficient for vapor pressure via the Derivative Method for predicting
liquid heat capacity. In this procedure, families such as alcohols and acids were not included
because they may require modifications to the vapor pressure correlation form and the equation
of state to account for self-association. This analysis showed that an 𝐸𝐸 of 2-5 fits these families
much better than the traditional 𝐸𝐸 of 6. This method fit vapor pressure as well as other predictive
65
methods, but it fit liquid heat capacity much better than other vapor pressure predictive methods
using randomized samples of the compounds with data. Since most liquid heat capacity data are
at temperatures close to the triple point, this method improves the shape of the 𝑃𝑃vap and Δ𝐻𝐻vap
curves at low temperatures where they are difficult to measure. Therefore, this method predicts
thermodynamically consistent vapor pressure temperature-dependent correlations over wider
temperature ranges than any currently available correlation.
66
7 EXPERIMENTAL WORK
Many chemical processes operate at the saturation curve of the involved compounds
including distillation, condensation, and boiling. Optimal design of such operations requires
accurate, pure-component, thermodynamic data describing the physical phenomena. In order to
more fully understand these thermophysical properties and to fill gaps in data, experimental
measurements were performed throughout the course of this project. These measurements have
been submitted for publication.
7.1 Compounds
Nineteen industrially important compounds were investigated via DSC to determine
melting temperature, enthalpy of melting, and liquid heat capacity. These measurements can be
used to derive heat of vaporization and vapor pressure [43]. This work reports the results of DSC
experiments performed on nineteen industrially important compounds to determine melting
temperature, enthalpy of fusion, and liquid heat capacity. The compounds studied are members
of the DIPPR database,[44] which selects compounds based on the needs of leading industrial
companies (url: https://www.aiche.org/dippr) in fields such as energy, pharmaceuticals,
chemicals, semiconductors, oil and gas, and risk management.
Some of these compounds are found in the energy industry. o-Tolualdehyde,
m-tolualdehyde, and p-tolualdehyde are all auto exhaust pollutants [68, 69]. 2,5-Dimethylfuran
has been identified as a cheap alternative liquid fuel [70-72]. 5-Methylfurfural is also an
67
important biofuel intermediate [73], but is also used in pharmaceutical synthesis [74, 75] and
may have anti-tumor properties [76]. n-Hexylcyclohexane is a pyrolysis product of certain oils
[77]. 2,6-Dimethoxyphenol is a byproduct of the pulp and paper industry [78] that could be used
to improve renewable energy storage materials [79].
Other compounds are important to biological systems. m-Tolualcohol is a metabolite of
xylene [80] and a precursor to amides, which are biologically important [81].
1-Phenyl-2-propanol is a useful pharmaceutical intermediate [82]. 2-Phenyl-1-propanol is an
ingredient in fragrances and food flavorings [83] that has been used as a representative drug in
new characterization method studies [84]. 2-Isopropylphenol is an important biochemical [85,
86]. Phenyl acetate is a biochemical that has been linked to depression [87]. Ethyl 2-
phenylacetate is naturally occurring in both rice wine and grape wine [88, 89].
1H-Perfluorooctane is a member of the perfluorinated compound family, which are
environmentally persistent and important to understand [90-92]. trans-Isoeugenol can be found
naturally in plants [93] and has been used as a precursor to antioxidants [94] and biovanillin, a
synthetic flavor [95].
The rest of the compounds studied have miscellaneous uses. p-Toluic acid is an OECD
high production volume chemical that serves as an intermediate for polyethylene terephthalate
production. It also serves as an anticorrosion additive [96]. 1-Phenyl-1-propanol is used as a test
compound for racemic mixture separation techniques [97, 98]. 1-Propoxy-2-propanol is used as a
cleaner for its quick evaporation and non-polar solvation [99, 100].
There exist few data in the literature about these compounds. Table B-72 through B-75
summarize the data with sources for melting point and enthalpy of fusion, vapor pressure, heat of
68
vaporization, and liquid heat capacity, respectively. A summary and analysis of the existing data
appear below.
• Melting Point (𝑇𝑇𝑚𝑚 ): Extensive melting point data exist for 2,6-dimethoxyphenol and p-toluic acid.
Two of these melting point data sets are 100 K apart for p-toluic acid, while the data for 2,6-
dimethoxyphenol differ by 4 K at most. Several melting point data exist for p-tolualdehyde, n-
hexylcyclohexane, 6-undecanone, and trans-isoeugenol. The data for p-tolualdehyde range from
320.15 K to 512.15 K, while the data for 6-undecanone only differ by several degrees. The data
for trans-isoeugenol span 8 K, including room temperature. Only one melting point was found in
the literature for 2-phenyl-1-propanol, 2-isopropylphenol, and ethyl 2-phenylacetate.
• Enthalpy of Fusion (Δ𝐻𝐻fus ): Of all 19 compounds, only p-toluic acid has experimental enthalpy
of fusion data, which range from 165 to 208 J g-1.
• Vapor Pressure (𝑃𝑃vap ): Fifteen of the 19 compounds have experimental vapor pressure data,
consistent with the idea that vapor pressure is the most commonly measured of these properties.
Of these, 1-phenyl-1-propanol, 2-phenyl-1-propanol, 2-isopropylphenol, 2,5-dimethylfuran, 5-
methylfurfural, phenyl acetate, ethyl 2-phenylacetate, n-hexylcyclohexane, and 1-propxy-2-
propanol contain several sets of independent data. m-Tolualdehyde, p-tolualdehyde, p-toluic acid,
6-undecanone, 1H-perfluorooctane, and trans-isoeugenol only have a few vapor pressure data
points, while o-tolualdehyde, m-tolualcohol, 1-phenyl-2-propanol, and 2,6-dimethoxyphenol did
not have any data.
• Heat of Vaporization: 5-Methylfurfural and n-hexylcyclohexane each contain one calorimetric
heat of vaporization data point around room temperature.
• Liquid Heat Capacity: Ethyl 2-phenylacetate, 2,5-dimethylfuran, and p-toluic acid each have one
liquid heat capacity experimental data point.
Vapor pressure literature data will be fit to a correlation, and the resulting derived heat of
vaporization and liquid heat capacity will be compared to both those in literature and new values
69
measured in this report. Literature melting points and enthalpies of melting will be compared to
new values reported here.
Table 7-1 lists the compounds (with CAS number) examined in this study. Also found in
the table are the molecular weight of the compounds, the supplier, the supplier-stated purity,
measured purities, and the expected compounds comprising any impurities (when known). All
samples were used “as is” without further purification. The data found in the Measured Purities
column were measured “in-house” to verify the supplier impurities. These experiments were
performed using an Agilent Technologies 7890A gas chromatograph system coupled with a
7683B series injector and 5975C inert XL EI MSD. Each compound ran through the GCMS
multiple times, with the results converted to mass fractions and compared to the supplier lot
analyses (See Table 7-1). The solid samples were dissolved in acetone before running through
the GCMS. Besides n-hexylcyclohexane, all of the compounds were above 98.0% pure. Eleven
of the nineteen compounds were above 99.0% pure. Eight compounds used for verification are
similarly listed in Table 7-2. All of these compounds were above 99.0% pure.
7.2 Calibrations/Verifications
The melting points, enthalpies of fusion, heat capacities, and glass transition temperatures
were measured using a TA Instruments Q2000 MDSC (Modulated Differential Scanning
Calorimeter). The temperature can range from 183 K to 823 K. The accuracy on temperature
measurement was ± 0.1 °C, while the precision of temperature appears to be within ± 0.01 °C.
This DSC takes advantage of patented Tzero technology, which incorporates cell resistance and
capacitance characteristics, therefore pinpointing heat flow with greater sensitivity and flatter
baselines.
70
Table 7-1: Purities of compounds measured in this study
Compound CAS No. MW Supplier Supplier Measured Main Impurity
o-Tolualdehyde 529-20-4 120.15 Sigma Aldrich 98.9% 98.3% m-, and p- tolualdehyde
m-Tolualdehyde 620-23-5 120.15 Sigma Aldrich 98.9%
p-Tolualdehyde 104-87-0 120.15 Sigma Aldrich 98.8%
m-Tolualcohol 587-03-1 122.17 Sigma Aldrich 98.9% 99.7% Benzylalcohol
p-Toluic Acid 99-94-5 136.15 Sigma Aldrich 99.5% 98.9% 2,2-dimethoxypropane
1-Phenyl-1-propanol 93-54-9 136.19 TCI America 99.4% 99.8% Propylbenzene
1-Phenyl-2-propanol 698-87-3 136.19 TCI America 99.9% 99.98% 1,2-ethanediol-1,2-diphenyl
2-Phenyl-1-propanol 1123-85-9 136.19 TCI America 99.8% 99.7% 2-cyclohexyl-1-propanol
2-Isopropylphenol 88-69-7 136.19 TCI America 99% 99.2% m-, and p- isopropylphenol
2,5-Dimethylfuran 625-86-5 96.13 Sigma Aldrich 99.8%
5-Methylfurfural 620-02-0 110.11 Sigma Aldrich 99.5% 99.5% 5-methyl-2(3H)furanone
Phenyl acetate 122-79-2 136.15 Sigma Aldrich 99.8%
Ethyl 2-phenylacetate 101-97-3 164.20 Sigma Aldrich 99.8%
n-Hexylcyclohexane 4292-75-5 168.32 TCI America 98.6% 97.9% 3-methylpentylcyclohexane
1H-Perfluorooctane 335-65-9 420.07 Aldrich 99.9%
2,6-Dimethoxyphenol 91-10-1 154.17 Sigma Aldrich 99.1%
trans-Isoeugenol 5932-68-3 164.20 Sigma Aldrich cis+trans: trans:
99.3% >98.5%
1-Propoxy-2-propanol 1569-01-3 118.18 Sigma Aldrich 99.8% 98.6%
6-Undecanone 927-49-1 170.29 Sigma Aldrich 98.6%
Table 7-2: Purities of verification compounds used in this study

Chemical Name CAS no. Supplier Supplier Measured Main Impurity
Naphthalene 91-20-3 Fluka Analytical 99.9% 99.84% thionaphthene
Toluene 108-88-3 Sigma Aldrich 99.96% 99.93% ethylbenzene
1-Octanol 111-87-5 Fischer Scientific 99.8% 99.2% other alkanols
n-Eicosane 112-95-8 Alfa Aesar 98.7%
n-Decane 124-18-5 Alfa Aesar 99.3% 98.9% branched decanes
n-Heptane 142-82-5 Sigma Aldrich 99.9% 99.86% methylcyclohexane
1,6-Hexanediol 629-11-8 Aldrich Chemistry 99.7% 99.92% water
n-Pentacosane 629-99-2 Alfa Aesar 99.4%
71
Several calibrations were performed to ensure low uncertainty measurement. The
baseline was calibrated using sapphire disks. The temperature was calibrated using indium,
water, and adamantane with ASTM standard E967-08, through which the measured melting
temperatures were compared to literature values, and a cubic spline was fit to the calibration
curve over that range. The heat flow was calibrated using indium with ASTM standard E968-02,
through which the measured enthalpy of fusion was compared to literature enthalpy of fusion
values, and the measured heat flow was scaled. The temperature and heat flow calibrations were
verified by comparing melting points and enthalpies of fusion of several well-known compounds
to that in the literature, with results given in Table 7-3 and shown graphically in Figure 7-1 [44].
Each compound was taken to at least 15 °C below the literature melting point, then heated at 2
°C/min to at least 15 °C above the literature melting point. The melting temperatures and
enthalpies of fusion were determined graphically from the melt endotherm using TA
Instruments’ Universal Analysis toolkit in conjunction with ASTM standards E793-06 and E794-
06.
Table 7-3: Temperature and heat verification of melting point (Tm/K)

and enthalpy of fusion (ΔHfus/J g-1)
Chemical Name Literature Tma Experimental Tmb Literature ΔHfusa Experimental ΔHfusb
n-Decane 244±2.4[101] 243.03±0.04 202±2.0[102] 196.66±0.70
1-Octanol 257.7±0.5[103] 256.5±0.2 174±1.7[104] 176±4.4
n-Eicosane 309.6±0.6[102] 308.7±0.1 247±2.5[102] 243±4.8
1,6-Hexanediol 315±3.2[102] 312.6±0.4 206±6.5[105] 208±4.3
n-Pentacosane 327±3.3[106] 326.6±0.5 164±4.9[106] 157±3.0
Naphthalene 353±3.5[107] 353.0±0.4 148±1.5[107] 146±3.9
a
Uncertainty based on the DIPPR uncertainty
b
Uncertainty given as the 95% confidence interval
73
3 10
8
2
Measured - Literature ΔHfus (J g-1)

Measured - Literature Tm (K) 6
4
1
2
0 0
220 270 320 370 120 170 220 270
-2
-1
-4
-6
-2
-8
-3 -10
Literature Melting Point (K) Literature Enthalpy of fusion (J g-1)
Figure 7-1: Verification results for a) temperature and b) heat calibrations, with the average
difference for each compound from the DIPPR value [44] ( ) and 95% confidence intervals on the
measurements, and the uncertainties from this study ( )
The MDSC heat capacity was calibrated using toluene and naphthalene with ASTM
standard E2716-09. The modulation frequency was lengthened to accommodate the slow thermal
reaction of the liquid samples. Additionally, the isothermal time was increased from 20 to 30
minutes to allow the heat capacity to equilibrate. Each day before heat capacities were measured,
the heat flow and heat capacity were calibrated by indium and toluene or naphthalene, depending
on the temperature of the heat capacity measurement. Toluene was used to calibrate below 363
K, and naphthalene was used to calibrate 363 K to 473 K. This ensured that no calibration was
performed too close to the normal boiling point. The calibration method was verified by
measuring the heat capacity of n-heptane at -25, 25, and 75 °C as shown in Figure 7-2 with the
DIPPR correlation, DIPPR uncertainty, and literature data. This gave a bias of -0.05% with an
average 95% confidence interval of 1.59%. The high temperature calibration method was
verified by measuring the heat capacity of sapphire at 100, 140, 180, and 200 °C as shown in
74
Figure 7-3 with the DIPPR correlation, DIPPR uncertainty, and literature data. This gave a bias
of -0.34% with an average 95% confidence interval of 1.19%. Note that DIPPR gives two
correlations for the solid heat capacity of sapphire that meet at 400 K, giving a discontinuity in
the correlations that doesn’t appear in the literature. The average 95% confidence intervals for
both the low and high temperature verifications are within the 3.2% mean repeatability value
given in ASTM 2716-09.
2.6
DIPPR Correlation
2.5
1% Uncertainty
2.4
Verification Data
Cpl (J g-1 K-1)
2.3
Literature Data
2.2
2.1
2.0
1.9
175 225 275 325 375
T/K
Figure 7-2: Verification results for heat capacity of n-heptane with 95% confidence intervals
compared to the DIPPR correlation, DIPPR uncertainty, and literature data
A glass transition was observed for several of the compounds. In these cases, ASTM
standard E1356-08 was followed with a 2 °C/min heating rate. Since these compounds have low
molecular weights compared to polymers, and the measured glass transition temperatures were
sub-ambient, it is assumed that no other reactions occurred.
75
1.10
1.05
1.00
Cpl (J g-1 K-1)
0.95
DIPPR Correlation
0.90 Literature Data
0.85 3% Uncertainty
Verification Data
0.80
350 400 450 500
T/K
Figure 7-3: Verification results for heat capacity of sapphire with 95% confidence intervals
compared to the DIPPR correlation, DIPPR uncertainty, and literature data
7.3 Uncertainties
Based on the stated purities (see Table 7-1), and the calibration/verification tests
described in the previous section, the process uncertainty in melting point and glass transition
temperature measurements were determined to be ± 1.0 K each, and the process uncertainty in
the enthalpy of fusion measurements was determined to be ± 5 J/g. The uncertainties were found
by comparing the measured values and 95% confidence intervals to experimentally verified
DIPPR values and uncertainties. For the compounds measured in this study, enough melting
point and enthalpy of fusion replicates were performed so that the 95% confidence intervals were
smaller than the process uncertainties from the verification results. The impurities measured via
GCMS were estimated to affect the melting point and enthalpy of fusion to within the
uncertainties found in the verification. These uncertainties were used to fit experimental data that
allows thermodynamic analysis for each compound, for vapor pressure, heat of vaporization, and
liquid heat capacity.
76
7.4 Property Selection for Thermodynamic Analysis
For the compounds in this study, there are not enough vapor pressure experimental data
points to fit all four parameters in the Riedel equation (Equation (5-1). The three techniques used
to fit the data are summarized in Table 7-4, and will be explained here. When there exist reliable
data over a wide temperature range, two of the fitting coefficients are fit using the normal boiling
point and the critical point, leaving two coefficients to fit to data. When there exist only a couple
of vapor pressure data points, the derivative of the Riedel parameter (explained in Chapter 6) is
set to zero as well, leaving only one coefficient to fit to data. When no reliable experimental data
exist, the fully predictive correlation from Chapter 6 is used.
Table 7-4 Summary of vapor pressure fitting techniques

Technique Name Coefficients Fit to Data When Used
Riedel 3 2 Reliable data over a wide temperature range
Riedel 2 1 Few data over a small temperature range
Predictive 0 No reliable experimental data
7.5 Results
Melting point, enthalpy of melting, and liquid heat capacity results of these compounds
were compared to similar compounds not measured in this report, with values and uncertainties
from the DIPPR database. Liquid heat capacity was measured at discrete temperatures and
repeated as often as time allowed, resulting in average 95% confidence intervals of ±0.031 J g-1
K-1 or 1.52% over all temperatures and compounds. Enough melting point and enthalpy of
melting replicates were performed so that the 95% confidence intervals were smaller than the
process uncertainties from the verification results. Some compounds were unable to freeze
within the temperature range of the DSC, so their melting points were not measured. Compounds
that were solid at room temperature were pre-melted before melting point and enthalpy of fusion
77
measurements were taken. Liquid heat capacity was measured at discrete temperatures and
replicated as time permitted until the 95% confidence intervals shrunk to within 3% of the
average value. All liquid heat capacity measurements were done below the DIPPR-assigned
normal boiling point for each compound so that vapor heat capacity could be ignored. For
convenience, all the liquid heat capacity, melting point, and enthalpy of fusion measurements are
summarized in Table 7-5, Table 7-6, and Table 7-7, respectively. The compounds measured are
given below, grouped by common functional groups.
Table 7-5: Summary of liquid heat capacity measurements with uncertainties

Compound T/K Cp/(J g-1 K-1) Replicates
o-Tolualdehyde 238.16 1.535±0.027 15
293.16 1.661±0.027 7
348.15 1.813±0.020 15
403.13 1.920±0.023 9
458.11 2.173±0.038 16
m-Tolualdehyde 273.17 1.577±0.032 10
313.16 1.714±0.041 11
353.15 1.829±0.023 11
393.14 1.961±0.035 9
453.11 2.148±0.043 12
p-Tolualdehyde 273.17 1.593±0.016 16
313.16 1.700±0.020 17
353.15 1.800±0.023 12
393.14 1.934±0.027 16
453.11 2.089±0.032 8
m-Tolualcohol 266.15 1.819±0.019 6
306.15 2.053±0.031 5
356.15 2.301±0.022 16
406.15 2.417±0.022 12
456.15 2.522±0.015 18
p-Toluic acid 458.15 2.433±0.044 10

473.15 2.485±0.016 8
488.15 2.553±0.029 9
503.15 2.600±0.020 8
523.15 2.659±0.019 5
78
Table 7-5: continued
1-Phenyl-1-propanol 273.15 2.053±0.055 13
323.15 2.349±0.046 13
373.15 2.482±0.067 13
423.15 2.589±0.058 12
473.15 2.709±0.080 16
1-Phenyl-2-propanol 273.15 2.071±0.033 10
323.15 2.284±0.027 11
373.15 2.418±0.042 11
423.15 2.537±0.023 17
473.15 2.605±0.065 6
2-Phenyl-1-propanol 273.15 2.007±0.037 10
323.15 2.210±0.054 13
373.15 2.393±0.051 19
423.15 2.511±0.066 6
473.15 2.583±0.029 16
2-Isopropylphenol 273.15 2.070±0.026 9
323.15 2.257±0.039 11
373.15 2.361±0.022 8
423.15 2.481±0.057 14
473.15 2.602±0.047 9
5-Methylfurfural 250.15 1.639±0.008 12
300.15 1.748±0.017 9
350.14 1.839±0.008 9
400.13 1.992±0.022 10
450.10 2.121±0.019 13
2,5-Dimethylfuran 213.15 1.657±0.019 12
253.15 1.706±0.024 8
293.15 1.775±0.018 8
333.15 1.924±0.017 9
Phenyl acetate 253.15 1.619±0.015 14
293.15 1.651±0.027 13
333.15 1.763±0.012 16
373.15 1.876±0.025 13
413.15 1.979±0.034 11
Ethyl 2-phenylacetate 253.15 1.655±0.019 13
293.15 1.759±0.051 11
333.15 1.783±0.021 12
373.15 1.869±0.024 12
413.15 1.987±0.024 12
n-Hexylcyclohexane 228.16 1.735±0.020 14
288.16 1.962±0.031 15
348.14 2.146±0.044 22
408.13 2.429±0.032 19
468.09 2.755±0.042 8
79
6-Undecanone 293.16 2.136±0.039 9
343.16 2.241±0.027 16
373.15 2.363±0.025 9
423.13 2.481±0.021 12
473.10 2.719±0.022 12
1H-Perfluorooctane 258.16 1.062±0.015 9
273.16 1.092±0.011 11
298.16 1.143±0.009 7
323.16 1.178±0.018 11
373.14 1.254±0.008 11
2,6-Dimethoxyphenol 333.16 2.058±0.031 8
373.15 2.190±0.049 9
413.14 2.163±0.056 9
453.12 2.252±0.042 10
493.10 2.318±0.052 9
trans-Isoeugenol 298.15 1.991±0.064 7
323.15 2.049±0.058 8
373.15 2.122±0.028 20
423.15 2.324±0.031 8
473.15 2.358±0.041 17
1-Propoxy-2-propanol 193.19 2.009±0.018 7
223.15 2.098±0.011 10
273.16 2.294±0.013 11
323.16 2.455±0.019 12
373.15 2.663±0.018 17
Table 7-6: Summary of experimental melting point measurements a

Chemical Name Tm/K Replicates
o-tolualdehyde 233.4 6
m-tolualdehyde 224.7 3
p-toluladehyde 263.1 5
m-tolualcohol 264.3 10
p-toluic acid 452.1 10
1-phenyl-1-propanol 262.6 3
2-isopropylphenol 285.0 8
5-methylfurfural 240.5 20
phenyl acetate 266.0 4
ethyl 2-phenylacetate 244.0 3
hexylcyclohexane 224.9 23
6-undecanone 286.0 5
1H-perfluorooctane 254.3 8
2,6-dimethoxyphenol 326.4 5
trans-Isoeugenol 294.7 12
a
Uncertainty of 1 K
80
Table 7-7 Summary of experimental enthalpy of fusion measurements a
Chemical Name ΔHfus /(J g-1) Replicates
o-tolualdehyde 84.8 11
p-toluladehyde 91.9 5
m-tolualcohol 111 28
p-toluic acid 158 9
2-isopropylphenol 80.6 8
5-methylfurfural 105 20
phenyl acetate 94.1 4
ethyl 2-phenylacetate 110 3
hexylcyclohexane 122 23
6-undecanone 184 5
1H-perfluorooctane 23.5 8
2,6-dimethoxyphenol 326 5
trans-Isoeugenol 71.3 13
a
Uncertainty of 5 J/g
7.5.1 Toluene Derivatives
The melting points, enthalpies of fusion, and liquid heat capacities of several phenolic
compounds were measured. These included toluenes with alcohol, aldehyde, or acid groups on
the meta-, ortho-, or para- positions, as pictured in Figure 7-4. Table 7-8 and Figure 7-5 show
the experimental melting points obtained in this work with the values from chemically-similar
compounds, like the xylenes. The uncertainties are also depicted. The values for the similar
compounds came from the DIPPR database. Notice that the meta- compounds all melt at lower
temperatures for each family (alcohol, aldehyde, acid). Also note that for each of the group
positions (meta-, ortho-, para-) the melting point order is tolualdehyde, xylene, tolualcohol,
toluic acid. Of particular note is the melting point for p-toluic acid. This study places the value at
452.1 K, within several degrees of some studies [108-112] but 100 K lower than others [113,
114]. The value measured was about 70 K above that for m-toluic acid, which is close to the
same difference between the melting points of p- and m- xylene. It therefore appears that the
higher values [113, 114] are in error.
81
O O O
m-tolualdehyde o-tolualdehyde p-tolualdehyde
p-toluic acid m-tolualcohol
Figure 7-4 The toluene derivatives measured in this study
Table 7-8: Summary of experimental melting points for the toluene derivatives
Chemical Name Tm/K (Reps) Type Source
o-xylene 247.98±0.5 Experimental DIPPR
m-xylene 225.3±0.45 Experimental DIPPR
p-xylene 286.40±0.57 Experimental DIPPR
o-tolualdehyde 233.4±1.0(6) Experimental This Report
m-tolualdehyde 224.7±1.0(3) Experimental This Report
p-toluladehyde 263.1±1.0(5) Experimental This Report
o-tolualcohol 309.15±3 Experimental DIPPR
m-tolualcohol 264.3±1.0(10) Experimental This Report
p-tolualcohol 332.65±3.3 Experimental DIPPR
o-toluic acid 377±11 Experimental DIPPR
m-toluic acid 384.15±3.8 Experimental DIPPR
p-toluic acid 452.1±1.0(10) Experimental This Report
82
500
450
400
Tm (K)
350
300
250
200
ortho- meta- para-
Figure 7-5 Melting points for xylenes ( ), tolualdehydes ( ), tolualcohols ( ), and toluic acids ( )
with uncertainties contained within the size of the markers, open symbols represent new data from
this study
Table 7-9: Summary of enthalpy of fusion experimental results for the toluene derivatives
Chemical Name ΔHfus /(J g-1) (Reps) Type Source
o-xylene 128.16±0.26 Experimental DIPPR
m-xylene 109.7±1.1 Experimental DIPPR
p-xylene 161.2±1.6 Experimental DIPPR
o-tolualdehyde 84.8±5(11) Experimental This Report
m-tolualdehyde 90±23 Predicted [115] DIPPR
p-toluladehyde 91.9±5(5) Experimental This Report
o-tolualcohol 106±26 Predicted [116] DIPPR
m-tolualcohol 111.0±5(28) Experimental This Report
p-tolualcohol 98±25 Predicted [115] DIPPR
o-toluic acid 148.1±1.5 Experimental DIPPR
m-toluic acid 115.3±1.1 Experimental DIPPR
p-toluic acid 158.3±5(9) Experimental This Report
Figure 7-7 shows the newly-measured experimental liquid heat capacity data for the
toluenes. The position of the aldehyde group on the tolualdehydes does not clearly affect heat
capacity, which is the same conclusion drawn from a review of m-, o-, and p- xylene heat
83
capacities. The tolualcohol heat capacity shows a curve shape reminiscent of other alcohols [32,
117], and the heat capacity for p-toluic acid fell within 5% of the literature value [118].
180
160
140
ΔHfus (J g-1)
120
100
80
60
ortho- meta- para-
Figure 7-6 Enthalpies of fusion for xylenes ( ), tolualdehydes ( ), tolualcohols ( ), and toluic acids
( ) with uncertainties from DIPPR and this study, open symbols represent new data from this
study
Table 7-10 gives vapor pressure curve summaries. The vapor pressure data and critical
constant prediction methods were re-evaluated, and best fits were found that went through the
newly-measured heat capacity data when the Derivative method was used. Each of the vapor
pressure curves had Riedel E values of 3, which is consistent with the results of Chapters 5 and
6. Of note, the average absolute errors (AAD’s) of the vapor pressure fits to data for m-
tolualdehyde and o-tolualdehyde were above 10%. However, the DIPPR vapor pressure
correlations for these two compounds both gave AAD’s above 10% as well, so this large number
was a result of scatter in the data.
84
2.8
2.6
2.4
Cpl (J g-1 K-1)
2.2
1.8
1.6
1.4
200 250 300 350 400 450 500 550
T/K
Figure 7-7 Liquid heat capacity measurements for m-tolualdehyde ( ), o-tolualdehyde ( ),

p-tolualdehyde ( ), m-tolualcohol ( ), and p-toluic acid ( ) with experimental uncertainty from
this study
Table 7-10: Summary of best critical constants and vapor pressure coefficients
for the tolualdehydes
Property m-Tolualdehyde o-Tolualdehyde p-Tolualdehyde
Tc Method Lydersen [119] Lydersen [119] Lydersen [119]
Tc/K 691.2 694.2 703.3
Pc Method Lydersen [119] Lydersen [119] Lydersen [119]
Pc/MPa 3.671 3.671 3.671
Tnb Method DIPPR DIPPR DIPPR
Tnb/K 472.15 474.15 480.4
Fitting Method Riedel 2 Riedel 2 Riedel 3
Ptp/Pa 0.96 0.11 2.0
Pvap(A) 87.605 112.37 82.487
Pvap (B) -9133 -10409 -9074
Pvap (C) -9.2902 -12.922 -8.4971
Pvap (D) 4.445E-9 6.8329E-9 3.553E-9
Pvap (E) 3 3 3
Pvap AAD 18.1 10.2 3.19
ΔHvap AAD -- -- --
Cpl AAD 2.3 0.94 0.61
85
7.5.2 Phenyl Propanols
The structures of four of the measured compounds—1-1-Phenyl-1-propanol, 1-phenyl-2-
propanol, 2-phenyl-1-propanol, and 2-isopropylphenol—are found in Figure 7-8. 2-
Isopropylphenol froze and melted like other compounds in this study, but the other phenyl
propanols each formed an amorphous glass, similar to glycerol [120]. As in other studies, these
glass transitions were identified by a step change in the baseline, or heat capacity [40, 121].
These glass transition temperatures were measured, and are given in Table 7-11.
OH HO
OH
1-phenyl-1-propanol 1-phenyl-2-propanol 2-phenyl-1-propanol
HO
2-isopropylphenol
Figure 7-8: The phenyl propanols measured in this study
Table 7-11: Summary of experimental glass transition temperatures

for the phenyl propanols
Chemical Name Tg/K (Reps) Type Source
1-phenyl-1-propanol 198.8±1.0(5) Experimental This Report
glycerol 190 Experimental [122]
86
The melting point of 1-phenyl-1-propanol was measured using methodology similar to
glycerol which will be described here [123]. The DSC was cooled at a rate of 0.1 °C/min to just
above the glass transition temperature at 203.15 K and held 3 hours. Then, it was heated at a rate
of 1 °C/min to 218.15 K and held for 6 hours. Finally, the cell was heated at a rate of 0.5 °C/min
to 288.15 K to observe the exothermic freezing and endothermic melting peaks. Unfortunately,
the data produced from these runs were not sufficiently consistent to repeat for the other phenyl
propanols.
Melting point results for 1-phenyl-1-propanol and 2-isopropylphenol are given in Table
7-12. When the alcohol group is moved from the propane chain to the benzene as in
2-isopropylphenol, no glass is observed, and melting point can be easily determined. The
measured heat capacities are plotted in Figure 7-9 showing that the placement of the phenyl and
alcohol groups had little effect on the measured values.
Table 7-12: Summary of experimental melting points for the phenyl propanols
glycerol 291.33±2.9 Experimental DIPPR
2-isopropylphenol 285.0±1.0(8) Experimental This Report
Table 7-13: Summary of enthalpy of fusion experimental results for the phenyl propanols
1-phenyl-1-propanol -- -- --
glycerol 198.5±6.0 Experimental DIPPR
2-isopropylphenol 80.6±5.0(8) Experimental This Report
87
2.7
2.5
Cpl (J g-1 K-1)

2.3
2.1
1.9
260 310 360 410 460
T/K
Figure 7-9 Liquid heat capacity measurements for 1-phenyl-1-propanol ( ), 1-phenyl-2-propanol

( ), 2-phenyl-1-propanol ( ), and 2-isopropylphenol ( ) with experimental uncertainty
7.5.3 Furans
2,5-Dimethylfuran and 5-methylfurfural (Figure 7-10) were measured to help
understanding of the furan family. These were compared to existing data for furan and furfural
whose structures are shown in Figure 7-11.
O O
O
2,5-dimethylfuran 5-methylfurfural
Figure 7-10: The furans measured in this study
O O O
furan furfural
Figure 7-11: Comparison compounds for the furans
88
Table 7-14 summarizes the experimental data (from both DIPPR and this study) for the
four furans mentioned above. The measured melting point for 5-methylfurfural fell within the
DIPPR assigned uncertainty of the melting point for furfural. Unfortunately, the melting point
for 2,5-dimethylfuran was too low for the DSC to measure, so the reported value in the table is
the DIPPR value.
Table 7-14: Summary of experimental melting points for the furans

5-methylfurfural 240.5±1.0(20) Experimental This Report
2,5-dimethylfuran 210.4±2.1 Experimental DIPPR
furfural 236.65±7.1 Experimental DIPPR
furan 187.55±0.38 Experimental DIPPR
Table 7-15 lists the enthalpy of fusion results for the four furans. The value for 2,5-
dimethylfuran is listed as predicted because, as just explained, the melting point was too low for
the DSC to measure. This predicted value came from the DIPPR database. The enthalpy of
fusion for 5-methylfurfural was measured to be 105.22 ± 5 J g-1 which is much lower than
furfural. This would indicate that the methyl group makes it difficult for the compound to pack
into a crystal lattice structure, so less energy would be needed to move to the liquid phase.
Table 7-15: Summary of enthalpy of fusion experimental results for the furans
Chemical Name ΔHfus /(J g-1) (Reps) Uncertainty/(J g-1) Source
5-methylfurfural 105.22±5.0(20) Experimental This Report
2,5-dimethylfuran 83±21 Predicted [115] DIPPR
furfural 149.9±4.5 Experimental DIPPR
furan 55.87±0.56 Experimental DIPPR
Table 7-16 shows the results of the thermodynamic analysis using the reported liquid heat
capacity data for 5-methylfurfural and 2,5-dimethylfuran. In particular, the critical temperature,
89
critical pressure, normal boiling point, and Riedel E value were selected in order to
simultaneously fit vapor pressure and newly-measured heat capacity data. Both of these
compounds used the same E value of 3, which follows the idea that compounds in the same
family are best fit using the same E values.
Table 7-16: Summary of best critical constants and vapor pressure

coefficients for the furans
Property 5-Methylfurfural 2,5-Dimethylfuran
Tc Method WJ 2nd Order [2] Joback [2]
Tc/K 692.5 558.2
Pc Method WJ 2nd Order [2] Joback [2]
Pc/MPa 4.407 4.173
Tnb Method DIPPR DIPPR
Tnb/K 460.15 366.8
Fitting Method Riedel 3 Riedel 2
Ptp/Pa 0.285 7.96
Pvap(A) 91.042 83.895
Pvap (B) -9452.27 -6995.96
Pvap (C) -9.67447 -9.09288
Pvap (D) 3.54388E-9 8.00850E-9
Pvap (E) 3 3
Pvap AAD 1.64 0.068
ΔHvap AAD 0.89 --
Cpl AAD 0.53 2.082
7.5.4 Phenyl Acetates
The structures of the two phenyl acetates measured are shown in Figure 7-12. Figure 7-13
shows benzyl acetate and methyl benzoate, which are chemically similar to the phenyl acetates
measured.
90
O O O
phenyl acetate ethyl 2-phenylacetate
Figure 7-12: The phenyl acetates measured in this study
O O
O O
benzyl acetate methyl benzoate

Figure 7-13: Comparison compounds for the phenyl acetates
Table 7-17 summarizes the experimental melting point data (from both DIPPR and this
study) for the four esters mentioned above. The measured melting point for ethyl 2-phenylacetate
is higher than the DIPPR value for benzyl acetate, which would be consistent with a molecular
weight argument. The measured melting point for phenyl acetate is slightly higher than the
DIPPR value for methyl benzoate, which means that the ester group packs better into a crystal
lattice when the carbonyl group is moved away from the phenyl group. Table 7-18 shows the
experimental enthalpy of fusion data for these esters. Both of the measurements by this study are
higher than the DIPPR values for benzyl acetate and methyl benzoate.
Table 7-17: Summary of experimental melting points for the phenyl acetates
phenyl acetate 266.0±1.0(4) Experimental This Report
ethyl 2-phenylacetate 244.0±1.0(3) Experimental This Report
benzyl acetate 221.65±2.2 Experimental DIPPR
Methyl benzoate 260.75±2.6 Experimental DIPPR
91
Table 7-18: Summary of enthalpy of fusion experimental results for the phenyl acetates
phenyl acetate 94.1±5.0(4) Experimental This Report
ethyl 2-phenylacetate 110±5.0(3) Experimental This Report
benzyl acetate 79±19 Predicted [115] DIPPR
Methyl benzoate 71.5±0.715 Experimental DIPPR
Table 7-19 shows the results of the thermodynamic analysis done using the vapor
pressure and liquid heat capacity data to find the best vapor pressure curve fit. Both of the
compounds measured were best represented using a Riedel E value of 3, which has been a
common result for many of these organic compounds.

coefficients for the phenyl acetates
Property Phenyl Acetate Ethyl Phenyl Acetate
Tc Method Lydersen [119] Joback [2]
Tc/K 687.1 702.4
Pc Method Lydersen [119] Joback [2]
Pc/MPa 3.587 2.947
Tnb Method DIPPR DIPPR
Tnb/K 468.85 498.55
Fitting Method Riedel 3 Riedel 2
Ptp/Pa 2.9 0.023
Pvap(A) 91.709 115.462
Pvap (B) -9642.6 -11507.2
Pvap (C) -9.7509 -13.1213
Pvap (D) 3.4375E-9 5.2518E-9
Pvap (E) 3 3
Pvap AAD 2.5 8.4
ΔHvap AAD -- --
Cpl AAD 0.70 2.69
7.5.5 n-Hexylcyclohexane
Recently, DIPPR performed a family review of the n-alkyl cyclohexanes. To help bolster
that review, n-hexylcyclohexane, pictured in Figure 7-14, was measured. The experimental
92
melting point of this compound along with the accepted DIPPR values for ethyl-, butyl-, and
octylcyclohexane are found in Table 7-20. Table 7-21 contains the values for the enthalpy of
fusion for the same compounds. Notice that the experimental melting point and enthalpy of
fusion for n-hexylcyclohexane found in this work follows the family trends. Specifically, melting
point appears to increase 20-30 K and enthalpy of fusion increases 20-30 J g-1 for every two
carbons added to the alkyl chain.
n-hexylcyclohexane
Figure 7-14: n-hexylcyclohexane
Table 7-20: Summary of experimental melting points for the alkylcyclohexanes

Ethylcyclohexane 161.5±0.5 Experimental DIPPR
Butylcyclohexane 198.42±0.4 Experimental DIPPR
Hexylcyclohexane 224.9±1.0(23) Experimental This Report
Octylcyclohexane 252.75±2.5 Experimental DIPPR
Table 7-21: Summary of enthalpy of fusion experimental results for the alkylcyclohexanes
Ethylcyclohexane 74.3±0.7 Experimental DIPPR
Butylcyclohexane 101.0±0.2 Experimental DIPPR
Hexylcyclohexane 122.1±5.0(23) Experimental This Report
Octylcyclohexane 153.4±7.7 Experimental DIPPR
Figure 7-15 shows the experimental liquid heat capacity data as a function of temperature
for ethyl-, butyl-, and hexylcyclohexane. (No experimental values exist for octylcyclohexane.)
The family trends also hold for the newly-measured data. The magnitudes of the values for n-
hexylcyclohexane are comparable to those of the other to alkylcyclohexanes on a mass basis.
93
Table 7-22 summarizes the best vapor pressure fit that meets the newly-measured liquid heat
capacity data using the Derivative method. A Riedel E value of 3 did the best job at fitting not
just the data for n-hexylcyclohexane, but for the other alkyl cyclohexanes as well.
2.8
2.6
2.4
Cpl (J g-1 K-1)
2.2
1.8
1.6
1.4
150 200 250 300 350 400 450 500
T/K
Figure 7-15: Liquid heat capacity data for n-ethyl- ( ) and n-butyl- ( ) with DIPPR uncertainty,
and n-hexyl- ( ) cyclohexane and experimental uncertainty

coefficients for n-hexylcyclohexane
Property n-Hexylcyclohexane
Tc Method Lydersen [119]
Tc/K 686.6
Pc Method Lydersen [119]
Pc/MPa 2.154
Tnb Method DIPPR
Tnb/K 497.93
Fitting Method Riedel 2
Ptp/Pa 4.06E-3
Pvap(A) 108.850
Pvap (B) -1075.1
Pvap (C) -12.301
Pvap (D) 5.3750E-9
Pvap (E) 3
Pvap AAD 0.981
ΔHvap AAD --
Cpl AAD 2.729
94
7.5.6 6-Undecanone
The di-n-alkyl ketone family required more data to bolster a DIPPR family review, so
6-undecanone (or dipentyl ketone, as shown in Figure 7-16) was measured. Table 7-23 and Table
7-24 show that the measured melting point and enthalpy of fusion followed family trends of
about 15-20 K and 10 J g-1 increments, respectively. The vapor pressure data were re-evaluated,
and the most thermodynamically consistent fit is summarized in Table 7-25. Once again a Riedel
E value of 3 gave the best vapor pressure fit for not just this compound, but the other compounds
in the family.
6-undecanone
Figure 7-16: 6-undecanone
Table 7-23: Summary of experimental melting points for the di-n-alkyl ketones
3-Pentanone 234.2±2.3 Experimental DIPPR
4-Heptanone 240.7±2.4 Experimental DIPPR
5-Nonanone 267.3±2.7 Experimental DIPPR
6-Undecanone 286.0±1.0(5) Experimental This Report
Table 7-24: Summary of enthalpy of fusion experimental results for the di-n-alkyl ketones
3-Pentanone 134.5 Experimental DIPPR
4-Heptanone 163±41 Predicted [115] DIPPR
5-Nonanone 175.3 Experimental DIPPR
6-Undecanone 184±5.0(5) Experimental This Report

coefficients for 6-undecanone
Property 6-Undecanone
Tc Method Experimental [124]
Tc/K 678.5
95
Property 6-Undecanone
Pc Method Lydersen [119]
Pc/MPa 2.052
Tnb Method DIPPR
Tnb/K 500.55
Ptp/Pa 2.6
Pvap(A) 133.55
Pvap (B) -12,486
Pvap (C) -15.754
Pvap (D) 6.729E-9
Pvap (E) 3
Pvap AAD 1.88
ΔHvap AAD --
Cpl AAD 1.04
7.5.7 1H-Perfluorooctane
Few data exist for the 1H-perfluoro family in the DIPPR database, so 1H-perfluorooctane
(as shown in Figure 7-17) was purchased and measured. It gave a slightly higher melting point
than perfluorooctane, as shown in Table 7-26. The enthalpy of fusion measurement was the same
as perfluorooctane, within the experimental uncertainty, as shown in Table 7-27.
F2 F2 F2
C C C CF3
HF2C C C C
F2 F2 F2
1H-perfluorooctane
Figure 7-17: 1H-perfluorooctane
Table 7-26: Summary of experimental melting points for

1H-perfluorooctane and related compounds
1H-perfluorooctane 254.3±1.0(8) Experimental This Report
perfluorooctane 250±2.5 Experimental DIPPR
1H-perfluorohexane 180.15±18 Not Specified [125] DIPPR
96
Table 7-27: Summary of enthalpy of fusion experimental results for
1H-perfluorooctane and related compounds
1H-perfluorooctane 23.5±5.0(8) Experimental This Report
perfluorooctane 21.87±0.22 Experimental DIPPR
1H-perfluorohexane 16±8 Predicted [116] DIPPR
7.5.8 2,6-Dimethoxyphenol
2,6-Dimethoxylphenol (Figure 7-18) was measured because no liquid heat capacity data
exist in the literature for it nor chemically-similar compounds such as guaiacol or ethyl vanillin
(Figure 7-19). The measured melting point of 2,6-dimethoxyphenol was 326.4 K (see Table
7-28) and was within 1-2 K of other melting points for 2,6-dimethoxyphenol in the literature
[126-130]. Moreover, its value was between that of guaiacol and ethyl vanillin, which
relationship is reasonable considering the trends in molecular weight.
OH
O O
2,6-dimethoxyphenol
Figure 7-18: 2,6-dimethoxyphenol
Table 7-29 shows the measured enthalpy of fusion with that of the similar compounds.
Unfortunately, the uncertainties in the predicted DIPPR enthalpy of fusion values for the
comparison compounds were too high to make a worthwhile comparison, though they do lie in
the vicinity of the new experimental point for 2,6-dimethoxyphenol.
97
OH
O
OH
O H
guaiacol ethyl vanillin
Figure 7-19: Compounds compared to 2,6-dimethoxyphenol
Table 7-28: Summary of experimental melting points for

2,6-dimethoxyphenol and related compounds
2,6-dimethoxyphenol 326.4±1.0(5) Experimental This Report
guaiacol 304.65±9.1 Not Specified [131] DIPPR
ethyl vanillin 350.65±3.5 Not Specified [132] DIPPR
Table 7-30 gives the parameters for the best vapor pressure correlation that meets the
measured liquid heat capacity data. Although there exist a couple of vapor pressure data points
for 2,6-dimethoxyphenol, they vary from DIPPR’s current vapor pressure expression by an
average of 60% error [127, 133, 134]. However, fitting these data did not produce a correlation
that was consistent with the newly-measured liquid heat capacity data. Using the new prediction
for vapor pressure described in Chapter 6 with an E value of 3 helped improve the consistency of
the vapor pressure curve to within the error in the heat capacity data without significantly
increasing the average vapor pressure error.
Table 7-29: Summary of enthalpy of fusion experimental results for

2,6-dimethoxyphenol and related compounds
2,6-dimethoxyphenol 113.7±5.0(5) Experimental This Report
guaiacol 100±50 Predicted [116] DIPPR
ethyl vanillin 113±28 Predicted [115] DIPPR
98
coefficients for 2,6-dimethoxyphenol
Property 2,6-Dimethoxyphenol
Tc Method Nannoolal [135]
Tc/K 752.2
Pc Method Nannoolal [135]
Pc/MPa 3.785
Tnb Method DIPPR
Tnb/K 534.15
Fitting Method Predictive
Ptp/Pa 7.0
Pvap(A) 140.96
Pvap (B) -14490
Pvap (C) -16.4103
Pvap (D) 5.02938E-9
Pvap (E) 3
Pvap AAD --
ΔHvap AAD --
Cpl AAD 1.63
7.5.9 trans-Isoeugenol
trans-Isoeugenol (Figure 7-20) was selected for measurements due to lack of
experimental data which caused a thermodynamic consistency problem when the compound was
being initially reviewed for addition to the DIPPR database. No experimental melting point was
used for the compound prior to this work, and the initial strategy for obtaining a value was to use
the prediction method of Constantinou [136]. This gave a melting point value of 324.55 K
meaning the compound was a solid at the standard state temperature of 298.15 K. The DIPPR
researchers knew that this was unlikely based on the melting temperatures of comparison
compounds—specifically eugenol and anethole—whose structures are found in Figure 7-21 and
which were known to be liquids at room temperatures.
99
OH
trans-isoeugenol
Figure 7-20: trans-isoeugenol
OH
O O
eugenol anethole
Figure 7-21: Comparison compounds for trans-isoeugenol
The experiments performed on trans-isoeugenol found a melting temperature more in
line with expections. Table 7-31 contains the melting point measurements for all three
compounds. Notice that the melting point of trans-isoeugenol is 294.7 K, which means it is a
liquid at the standard state condition of 298.15 K. This was especially important when
calculating the standard state Gibb’s energy of the compound. Without this experimental value,
the incorrect prediction using the Constantinou method resulted in a thermodynamically-
100
inconsistent Gibb’s energy of formation and standard state Gibb’s energy. The new experimental
value yielded Gibb’s energies that were consistent with other data.
Table 7-31: Summary of experimental melting points for trans-isoeugenol

and related compounds
trans-isoeugenol 294.7±1.0(12) Experimental This Report
eugenol 264±2.64 Experimental DIPPR
anethole 294.5±8.8 Not Specified [137] DIPPR
Table 7-32 shows that the measured enthalpy of fusion for trans-isoeugnol was much
lower than that of eugenol and anthole. This would indicate that the addition of the alcohol group
from anethole to trans-isoeugenol makes it more difficult for the molecule to pack well in a
lattice structure.
Table 7-32: Summary of experimental enthalpy of fusion for trans-isoeugenol

and related compounds
trans-isoeugenol 71.3±5.0(13) Experimental This Report
eugenol 114±29 Predicted [115] DIPPR
anethole 108.0±3.2 Experimental DIPPR
Table 7-33 gives the most thermodynamically consistent vapor pressure curve
information. Note that although the vapor pressure absolute average deviation (AAD) seems a bit
high at 8.10%, the current DIPPR vapor pressure curve (that is not thermodynamically
consistent) gives an AAD of 7.27%. However, using the current DIPPR vapor pressure curve to
predict liquid heat capacity gives a 𝐶𝐶𝑝𝑝𝑙𝑙 AAD of 4.7%. This means that a small sacrifice in vapor
pressure—𝑃𝑃vap AAD increased from 7.27% to 8.10%—led to a significant improvement in its
ability to fit liquid heat capacity data—𝐶𝐶𝑝𝑝𝑙𝑙 AAD decreased from 4.7% to 1.56%.
101
coefficients for trans-isoeugenol
Property trans-Isoeugenol
Tc Method Nannoolal [135]
Tc/K 751.9
nd
Pc Method WJ 2 Order [2]
Pc/MPa 3.007
Tnb Method DIPPR
Tnb/K 539.15
Ptp/Pa 0.615
Pvap(A) 155.72
Pvap (B) -14206
Pvap (C) -19.122
Pvap (D) 8.355E-6
Pvap (E) 2
Pvap AAD 8.10
ΔHvap AAD --
Cpl AAD 1.56
7.5.10 1-Propoxy-2-Propanol
1-Propoxy-2-propanol was also measured because the liquid heat capacity was not well
known. Unfortunately, the thermodynamic analysis techniques developed within the course of
this project were insufficient to provide a vapor pressure curve that could predict liquid heat
capacity through the Derivative method. The alcohol group seems to influence the shape of the
vapor pressure curve to the point that the Riedel equation equipped with SRK vapor volume
calculations is inadequate.
OH
1-propoxy-2-propanol
Figure 7-22: 1-propoxyl-2-propanol
102
7.6 Conclusions
New melting point, enthalpy of fusion, and liquid heat capacity experimental data for
nineteen industrially important compounds were measured via DSC. The compounds were:
• o-tolualdehyde (CAS 529-20-4)
• m-tolualdehyde (CAS 620-23-5)
• p-tolualdehyde (CAS 104-87-0)
• m-tolualcohol (CAS 587-03-1)
• p-toluic acid (CAS 99-94-5)
• 1-phenyl-1-propanol (CAS 93-54-9)
• 2-isopropylphenol (CAS 88-69-7)
• 2,5-dimethylfuran (CAS 625-86-5)
• 5-methylfurfural (CAS 620-02-0)
• phenyl acetate (CAS 122-79-2)
• ethyl 2-phenylacetate (CAS 101-97-3)
• n-hexylcyclohexane (CAS 4292-75-5)
• 6-undecanone (CAS 927-49-1)
• 1H-perfluorooctane (CAS 335-65-9)
• 2,6-dimethoxyphenol (CAS 91-10-1)
• trans-isoeugenol (CAS 5932-68-3)
• 1-propoxy-2-propanol (CAS 1569-01-3).
The melting points and enthalpies of fusion were replicated enough times to yield 95%
confidence intervals below 1 K and 5 J g-1, respectively, which values are below the process
uncertainties determined by a verification study. Liquid heat capacity was measured at discrete
103
temperatures and repeated as needed to reduce the average 95% confidence intervals to ±0.031 J
g-1 K-1 or 1.52% over all temperatures and compounds. Vapor pressure data and critical point
pressure and temperature were chosen so that the Riedel vapor pressure correlation was able to
successfully predict liquid heat capacity for fourteen of the compounds through the Derivative
method to within the liquid heat capacity experimental error for several of the compounds. All of
the compounds’ properties were compared to similar compounds with favorable results. In
particular, family plots for the toluene-like compounds, alkylcyclohexanes, and di-n-alkyl
ketones increased confidence in the experimental results. Additionally, a method for freezing and
melting 1-phenyl-1-propanol was developed and used for DSC. These measurements represent a
step forward in understanding these industrially important chemicals so they can be more
effectively used in process design.
104
8 BEST PRACTICES, RECOMMENDATIONS, AND INCORPORATIONS INTO
THE DATABASE
8.1 Introduction
This chapter will detail several improvements made to the thermodynamic calculation
procedure based on the findings in previous chapters. First, improvements in the ideal gas heat
capacity calculation procedure will be explained. Then, two calculation methods for liquid heat
capacity (the derivative and integral methods) will be discussed. Next, a methodology will be
given for the thermodynamic analysis procedure when a chemical does not have heat capacity
data. Best recommendations are then given as a result of these improvements, which were then
used to improve the DIPPR 801 project database. Finally, some work has also been done for
associating compounds, especially carboxylic acids, will be described herein.
8.2 Ideal Gas Heat Capacity Database Fixes

𝑖𝑖𝑖𝑖
In order to calculate ideal gas heat capacity, 𝐶𝐶𝑝𝑝 , the vibrational frequencies for each
molecule are calculated by solving Schrodinger’s Equation. Doing so requires selection of a level
of theory to account for electron correlation and a basis set which is used to approximate the
unknown wave function. Systematic errors are associated with each level of theory and basis set
selection, but scaling factors have been determined to account for these systematic errors in
certain cases. These scaling factors are found empirically with up to 3 significant figures [138]
and are readily available in the literature [139].
105
For some compounds, the vibrational frequency scaling factors needed to be updated. The
main basis sets and levels of theory used by DIPPR are HF/6-31G(d), BLYP/6-311G(df,p), and
B3LYP/6-311+G(3df,2p). When this work began, DIPPR procedures used with scaling factors of
0.8953, 0.9986, and 0.9986, respectively. This work has shown these factors was cause for
𝑖𝑖𝑖𝑖
concern because BLYP and B3LYP give different 𝐶𝐶𝑝𝑝 correlations with the same scaling factor.
The CCCBDB database from the National Institute of Standards and Technologies
(NIST) [140] indicate scaling factors around 0.90 for the HF level of theory, 0.99 for the BLYP
level of theory, and 0.965 for the B3LYP level of theory with comparable basis sets [140]. This
means that the BLYP and B3LYP scaling factors should be different—with the BLYP scaling
factor much closer to 1 and the B3LYP closer to 0.967 as given in the CCBDB database—than
what the DIPPR procedures indicate.
The difference between the old and new B3LYP correlations are shown for methyl ethyl
ketone with data and the BLYP correlation in Figure 8-1. Depicted is the ideal gas heat capacity
obtained from experiment and that predicted by quantum mechanical calculations and Equation
3-8. The predictions for BLYP using a scaling factor of 0.9986 (BLYP NIST f), B3LYP using a
scaling factor of 0.9986 (B3LYP old f), and B3LYP using a scaling factor of 0.967 (B3LYP
NIST f) are shown. Notice that using the incorrect scaling factor of 0.9986 with B3LYP (B3LYP
old f) results in heat capacities that are outside of the experimental data in certain cases and is not
consistent with the BLYP prediction. Using the correct factor of 0.967 remedies both problems.
This error was probably a remnant of a DIPPR programmer switching from BLYP to B3LYP
without using a new scaling factor.
106
150
140
Cpig (J mol-1 K-1)
130
120 BLYP (NIST f)

B3LYP (old f)
110 B3LYP (NIST f)

Experimental Data
100
325 345 365 385 405 425 445 465
T/K
Figure 8-1: The ideal gas heat capacity for methyl ethyl ketone with data and DIPPR uncertainty
and different basis sets, levels of theory, and scaling factors
𝑖𝑖𝑖𝑖
When incorrect scaling factors are used, the absolute error in 𝐶𝐶𝑝𝑝 is directly translated to
the calculation of 𝐶𝐶𝑝𝑝𝑙𝑙 . This means that if the old scaling factor was used to calculate the ideal gas
𝑖𝑖𝑖𝑖
heat capacity of methyl ethyl ketone, the 𝐶𝐶𝑝𝑝 curve would be about 5 J mol-1 K-1 lower than the
𝑖𝑖𝑖𝑖
𝐶𝐶𝑝𝑝 with the NIST scaling factor, as shown in Figure 8-1. From this, the calculated 𝐶𝐶𝑝𝑝𝑙𝑙 would be
about 5 J mol-1 K-1 lower than it should, which would correspond to a 2.8% error at 400 K. In
order to reduce these errors, the NIST scaling factors were used for all of the compounds
analyzed through the course of this project.
𝑖𝑖𝑖𝑖
A couple of group contribution methods have been developed for 𝐶𝐶𝑝𝑝 [141, 142]. These
methods used experimental data down to 298.15 K to regress the groups. However, the triple
point temperatures for smaller organic compounds extend much lower. Therefore, extrapolation
error has been inadvertently introduced into the 𝐶𝐶𝑝𝑝𝑙𝑙 Derivative method. Therefore, group
107
contribution methods were not recommended for compounds with low triple point temperatures.
𝑖𝑖𝑖𝑖
The DIPPR policy was changed to use ab initio as the primary method for 𝐶𝐶𝑝𝑝 calculation.
𝑖𝑖𝑖𝑖
Fortunately, these 𝐶𝐶𝑝𝑝 calculation improvements were found relatively early in this
𝑖𝑖𝑖𝑖
project, so the results given in the previous chapters utilize these improvements. Since the 𝐶𝐶𝑝𝑝
calculation methodology was improved and uncertainties reduced, it became easier to evaluate
the effectiveness of the 𝐶𝐶𝑝𝑝𝑙𝑙 calculation methods, which will be explained next.
8.3 Derivative vs. Integral Methods
At the start of this project, two methods existed to connect heat of vaporization with heat
capacities: the Derivative and the Integral method. The Derivative method was introduced in
Chapter 2, and the Integral method was first implemented by DIPPR researchers within the last
decade. The Integral method first assumes a correlation form for 𝐶𝐶𝑝𝑝𝑙𝑙 :
𝐵𝐵
𝐶𝐶𝑝𝑝𝑙𝑙 (𝑇𝑇) = 𝐴𝐴 + + 𝐶𝐶𝐶𝐶 + 𝐷𝐷𝜏𝜏 2 + 𝐸𝐸𝜏𝜏 3 (8-1)
𝜏𝜏
where 𝐴𝐴 − 𝐸𝐸 are fitting coefficients and 𝜏𝜏 is defined as:
𝑇𝑇
𝜏𝜏 = 1 − (8-2)
𝑇𝑇𝐶𝐶
This correlation form is plugged into the integral of the Derivative method from temperature 1
(𝑇𝑇1 ) to temperature 2 (𝑇𝑇2 ):

𝑇𝑇2 𝑇𝑇2 𝑃𝑃vap (𝑇𝑇)
𝑖𝑖𝑖𝑖
𝑇𝑇2 𝜕𝜕 2 𝑉𝑉vap (𝑇𝑇, 𝑃𝑃vap (𝑇𝑇)
� 𝐶𝐶𝑝𝑝𝑙𝑙 (𝑇𝑇) 𝑑𝑑𝑑𝑑 = � 𝐶𝐶𝑝𝑝 (𝑇𝑇) 𝑑𝑑𝑑𝑑 + Δ𝐻𝐻vap (𝑇𝑇1 ) − Δ𝐻𝐻vap (T2 ) − � 𝑇𝑇 � � � 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑
𝑇𝑇1 𝜕𝜕𝑇𝑇 2
𝑇𝑇1 𝑇𝑇1 0
(8-3)
𝑇𝑇2 𝑑𝑑𝑃𝑃vap (𝑇𝑇)
𝜕𝜕Δ𝑉𝑉(𝑇𝑇)
+ � �Δ𝑉𝑉(𝑇𝑇) − 𝑇𝑇 � � � 𝑑𝑑𝑑𝑑
𝑇𝑇1 𝜕𝜕𝜕𝜕 𝑃𝑃 𝑑𝑑𝑑𝑑
The coefficients for Equation 8-1 are calculated numerically by fitting the integral of Equation 8-
1 to the right hand side of Equation 8-3.
108
At the time of its introduction, the Integral method was touted as the computationally
quicker of the two methods and superior because it relied less on derivatives of data. The Integral
method was also said to be more accurate since the slope of the Δ𝐻𝐻vap curve goes to infinity with
the Derivative method. These 𝐶𝐶𝑝𝑝𝑙𝑙 calculation methods were both improved through the course of
this project, which will be shown with propylene as an example compound.
At the start of this project in 2013, the Derivative and Integral method calculations varied
from one another, as shown in Figure 8-2 for propylene. As depicted, both the Derivative (red
curve) and Integral (purple curve) methods undershoot the liquid heat capacity data (black
points). The Derivative method increased smoothly but stopped at the normal boiling point,
while the Integral method showed a slight inflection point around the normal boiling point before
increasing towards the critical point. Since the methods undershot by almost a constant value, it
was hypothesized that something was wrong with the ideal gas heat capacity.
By taking a closer look at the ideal gas heat capacity, it was found that, similarly to what
was discussed in Section 8.1, the ideal gas heat capacity was predicted with a group contribution
method that was extrapolated below 298.15 K. To correct this, a quantum mechanical calculation
was used with experimental data to create a new ideal gas heat capacity correlation using the 6
parameter form in Equation 3-10. The new Derivative and Integral methods are given in Figure
8-3. Unfortunately, a better ideal gas heat capacity correlation slightly worsened the liquid heat
capacity predictions.
109
150
140
Experimental Data
130
120 Derivative Method (2013)
Cpl (J mol-1 K-1)
110 Integral Method (2013)
100
90
80
70
60
50
75 125 175 225 275 325 375
T/K
Figure 8-2: Liquid heat capacity data for propylene with the derivative and integral methods from
the start of this project (2013)
150
140
Experimental Data
130
Cpl (J mol-1 K-1)

100
90
80
70
60
50
75 125 175 225 275 325 375
T/K
Figure 8-3: Liquid heat capacity data for propylene with the derivative and integral methods with a
better ideal gas heat capacity correlation (2014)
110
Upon further inspection, some differences appeared in the implementation of the
Derivative and Integral methods. First, the temperature ranges for each method were different, so
the Derivative method was extended up past the normal boiling point to a reduced temperature of
0.96 in order to match the temperature range of the integral method. Doing so revealed that the
two methods differed at high temperatures, as shown below in Figure 8-4.
The reason for this difference was found by investigating the computational form of the
Integral method. Figure 8-5 shows the pieces of the form used by the Integral method in 2014 to
calculate the fitting coefficients of Equation 8-1 with the units displayed. Since these pieces
came from the integral in Equation 8-3, they should have units of J mol-1. However, two of the
pieces (Δ𝐶𝐶𝑝𝑝𝑣𝑣 𝑡𝑡𝑡𝑡 𝑖𝑖𝑖𝑖 – a correction to change an ideal gas heat capacity to a vapor heat capacity,
and Δ𝐶𝐶𝑝𝑝𝐿𝐿 – a correction to change a saturated liquid heat capacity to isobaric heat capacity) were
implemented with inconsistent units compared to the other terms. The methods used to calculate
these corrections were corrected by double-checking them against rigorous thermodynamics.
Another problem was that only 40 temperature points were being generated for the
Integral method parameter fitting process, causing the curve to dip at high temperatures. When
the number of points was increased to 250, the Integral method came in line with the Derivative
method at high temperatures where the corrective terms – labeled as Δ𝐶𝐶𝑝𝑝𝑣𝑣 𝑡𝑡𝑡𝑡 𝑖𝑖𝑖𝑖 , Δ𝐶𝐶𝑝𝑝𝑉𝑉 , and Δ𝐶𝐶𝑝𝑝𝐿𝐿
in Figure 8-5 – have the greatest effect. However, increasing the number of parameter fitting
points also increased the calculation time for the Integral method coefficients, so it is
recommended that the Derivative method be used instead.
111
150
140
Experimental Data
130
Cpl (J mol-1 K-1)
100
90
80
70
60
50
75 125 175 225 275 325 375
T/K
Figure 8-4: Liquid heat capacity data for propylene with the Derivative and Integral methods with
the Derivative method extended above normal boiling point (2015)
𝑖𝑖𝑖𝑖 J 𝑑𝑑Δ𝐻𝐻vap J J J J
𝑦𝑦 = 𝐶𝐶𝑝𝑝 � �− � � + Δ𝐶𝐶𝑝𝑝𝑣𝑣 𝑡𝑡𝑡𝑡 𝑖𝑖𝑖𝑖 � � + Δ𝐶𝐶𝑝𝑝𝑉𝑉 � � − Δ𝐶𝐶𝑝𝑝𝐿𝐿 � 3 �
mol 𝑑𝑑𝑑𝑑 mol mol K mol m
Figure 8-5 The equation used to calculate coefficients for the integral method (2014)
With the Derivative and Integral methods in line, the multi-property optimization
described in Chapter 5 could be performed for propylene. After looking over different vapor
pressure correlation forms, it was found that a Riedel correlation fit to vapor pressure data with
𝐸𝐸 = 2 gave a more thermodynamically consistent fit (2017) with liquid heat capacity data, as
shown in Figure 8-6 along with the original derivative and integral method fits (2013). This
represents a drop in AAD from 27% to 2.8%, a full order of magnitude. These improvements
gave the Derivative and Integral methods the ability to predict 𝐶𝐶𝑝𝑝𝑙𝑙 more effectively, which will be
discussed in the next section.
112
150
140
Experimental Data
Cpl (J mol-1 K-1) Derivative Method (2017)
110
Integral Method (2017)
100
90
80
70
60
50
75 125 175 225 275 325 375
T/K
Figure 8-6: Liquid heat capacity data for propylene with the derivative and integral methods now
(2017) compared to the start of this project (2013)
8.4 Compounds without Liquid Heat Capacity Data
It is common for niche chemicals to lack 𝐶𝐶𝑝𝑝𝑙𝑙 data. In these instances, the best
recommendation is to try to match the shape and/or absolute 𝐶𝐶𝑝𝑝𝑙𝑙 values of the corresponding
states 𝐶𝐶𝑝𝑝𝑙𝑙 prediction given in [2], and shown as:
1
⎡ 𝑇𝑇 3 ⎤
0.49 ⎛ 6.3 �1 − � 0.4355 ⎞
𝑖𝑖𝑖𝑖 ⎢ 𝑇𝑇𝑐𝑐 ⎥
𝐶𝐶𝑝𝑝𝑙𝑙 (𝑇𝑇) = 𝐶𝐶𝑝𝑝 (𝑇𝑇) + 𝑅𝑅𝑔𝑔 ⎢1.586 + + 𝜔𝜔 ⎜4.2775 + + (8-4)
𝑇𝑇 𝑇𝑇 𝑇𝑇 ⎟⎥
⎢ 1− 1−
𝑇𝑇𝑐𝑐 𝑇𝑇𝑐𝑐 𝑇𝑇𝑐𝑐 ⎥
⎣ ⎝ ⎠⎦
where 𝑅𝑅𝑔𝑔 is the universal gas constant, 𝑇𝑇𝑐𝑐 is the critical temperature, and 𝜔𝜔 is the acentric factor
for a given compound. Though not thermodynamically consistent, the corresponding states
prediction has proven better than the Ruzicka-Domalski method [143] time and again, especially
above 𝑇𝑇𝑁𝑁𝑁𝑁 .
113
As an example, consider the compound trans-1-chloro-3,3,3-trifluoro-1-propene, whose
vapor pressure has been measured but lacks liquid heat capacity data. The vapor pressure data
were fit using Riedel correlations with 𝐸𝐸 values of 1, 2, 3, and 6 for comparison. These 𝑃𝑃vap
correlations were used to predict liquid heat capacity with the derivative method. These four
predictions were compared to the corresponding states method (CSP) and the Ruzicka-Domalski
method (RD) in Figure 8-7. The vapor pressure correlation with 𝐸𝐸 = 3 seems to agree with the
CSP curve the best, so an 𝐸𝐸 value of 3 was selected as the best option. This chemical is
representative of other compounds that lack 𝐶𝐶𝑝𝑝𝑙𝑙 data. When a compound does not have 𝐶𝐶𝑝𝑝𝑙𝑙 data,
the corresponding states method can be used to identify an appropriate curve shape for the
Derivative or Integral methods. This has been shown to work when fitting the Riedel equation to
vapor pressure data, and when predicting vapor pressure by the method described in Chapter 6.
300
CSP
Der. E=1
Der. E=2
Cpl (J mol-1 K-1)
Der. E=3
Der. E=6
200 RD
100
150 200 250 300 350 400 450
T/K
Figure 8-7: Liquid heat capacity for trans-1-chloro-3,3,3-trifluoro-1-propene with several

prediction methods
114
8.5 Recommendation Summary
This work developed tools to improve the correlations and thermodynamic consistency of
vapor pressure, heat of vaporization, and liquid heat capacity for individual compounds. Section
𝑖𝑖𝑖𝑖
8.2 showed improvements made in 𝐶𝐶𝑝𝑝 calculations. Since Section 8.3 reconciled the differences
between the Derivative and Integral methods, it is recommended that the Derivative method be
used in favor of the Integral method because the improved Integral method is more
computationally expensive. Section 8.4 laid out a methodology for compounds without 𝐶𝐶𝑝𝑝𝑙𝑙 data.
Chapters 4 and 5 explained how changing the Riedel correlation form to increased
thermodynamic consistency from 𝑃𝑃vap to 𝐶𝐶𝑝𝑝𝑙𝑙 . Chapter 6 gave a new prediction method that allows
the same flexibility when 𝑃𝑃vap data do not exist. All of these updates lead to a new
recommendation for a thermodynamic consistency analysis procedure.
As compounds are investigated for addition to the DIPPR database, the following
procedure should be followed:
1. Select normal boiling point, critical temperature, and critical pressure based on
DIPPR policy and procedure recommendations
2. Loop on the following:
a) Vapor pressure: select data and pick correlation 𝐸𝐸 value
b) Heat of vaporization: evaluate shape and compare Clapeyron derived
curve to literature data.
c) Ideal gas heat Capacity: verify that the quantum mechanical calculations
𝑖𝑖𝑖𝑖
(ab initio) are fit correctly from 𝑇𝑇𝑇𝑇𝑇𝑇 to 𝑇𝑇𝐶𝐶 . This includes fitting 𝐶𝐶𝑝𝑝
experimental data when available.
115
d) Liquid heat capacity: check shape of Derivative method curve and
compare to literature data and the shape of the corresponding states
method
Also, compounds will contain varying amounts of data. Table 8-1 summarizes the recommended
methodology for all levels of 𝑃𝑃vap and 𝐶𝐶𝑝𝑝𝑙𝑙 data. Generally, the amount of Δ𝐻𝐻vap data available
does not directly affect the methodology since Δ𝐻𝐻vap data usually occur in temperature regions
where 𝑃𝑃vap is already well-known. However, Δ𝐻𝐻vap curves should still be compared and fit to
experimental data, when available, in order to create correlations that give the best values
through the whole temperature range. By following this methodology, the most
thermodynamically consistent correlations can be developed.
Table 8-1: Summary of best recommendations for achieving thermodynamic consistency

𝑷𝑷𝐯𝐯𝐯𝐯𝐯𝐯 Data 𝑪𝑪𝒍𝒍𝒑𝒑 Data Section Recommendation
Select the best 𝐸𝐸 value that minimizes 𝑃𝑃vap and 𝐶𝐶𝑝𝑝𝑙𝑙
Extensive Yes Chapter 5
AAD while fitting 2 or 4 𝑃𝑃vap coefficients
Select the best 𝐸𝐸 value that minimizes 𝑃𝑃vap and 𝐶𝐶𝑝𝑝𝑙𝑙
Sparse Yes Chapter 5
AAD while fitting 1 𝑃𝑃vap coefficient
Select the best 𝐸𝐸 value while fitting 2 or 4 𝑃𝑃vap
Extensive No Section 8.4 coefficients, guided by the corresponding states
correlation shape for 𝐶𝐶𝑝𝑝𝑙𝑙
Select the best 𝐸𝐸 value while fitting 1 𝑃𝑃vap coefficient,
Sparse No Section 8.4 guided by the corresponding states correlation shape
for 𝐶𝐶𝑝𝑝𝑙𝑙
Use new predictive Riedel equation with 𝐸𝐸 value that
No Yes Chapter 6
minimizes 𝐶𝐶𝑝𝑝𝑙𝑙 AAD
Use new predictive Riedel equation with 𝐸𝐸 value
No No Chapter 6
selected according to family in Table 6-5
116
8.6 DIPPR Database Improvements
The improvements found through the course of this project were implemented into the
DIPPR 801 database project. Unfortunately, 116 compounds were previously added to the
DIPPR database with the incorrect integral method liquid heat capacity correlations. Samples of
five of those compounds were purchased for measurements. The correlations and recommended
values for the other 111 compounds were updated and re-added to the database. Thermodynamic
analyses were performed following Table 8-1 to find the best Riedel equation form for 41
additional compounds in Chapter 5. An additional 70 compounds were analyzed in Chapter 6 in
order to create a new predictive vapor pressure calculation method. Fourteen of the 19
compounds measured and described in Chapter 7 were analyzed, and thermodynamically
consistent fits to vapor pressure were recommended. In all, over 200 compounds were directly
influenced as a result of this project.
The DIPPR vapor pressure correlations and subsequent Derivative method liquid heat
capacity curves were compared to these new correlations for 121 compounds. Figure 8-8 shows
the average absolute deviations for vapor pressure and Derivative method heat capacity fits
before and after analysis. Each point represents one compound. Red circles represent prior
DIPPR vapor pressure and Derivative method AAD’s. Blue diamonds represent vapor pressure
and Derivative method AAD’s as a result of this project. The red and blue squares represent the
average over all the compounds for DIPPR and this project, respectively. The x-axis shows the
AAD’s of the vapor pressure fits, while the y-axis gives the AAD of heat capacity fit when the
vapor pressure correlation is used to get a Derivative method curve. The red and blue squares are
at about the same x-position, but the blue square is about 4% lower than the red square on the y-
axis. This means that on average, the compounds analyzed became more thermodynamically
117
consistent through the Derivative method compared to liquid heat capacity data without
sacrificing the vapor pressure correlation fit to data.
30%
Derivative Method Cpl AAD
DIPPR
DIPPR Avg
20%
This Project
This Project Avg
10%
0%
0% 10% 20% 30% 40% 50% 60% 70% 80%
Pvap AAD
Figure 8-8: The average absolute deviations for the vapor pressure and Derivative method heat
capacity fits before and after analysis
8.7 Association
Self-associating compounds, such as carboxylic acids, provide a major obstacle to
improving thermodynamic consistency because they constitute a mixture of “mers,” instead of a
single molecule. The association reaction for such compounds (e.g. carboxylic acids) can be
represented as follows:
2𝑀𝑀 ↔ 𝐷𝐷 (8-5)
where 𝑀𝑀 stands for monomer with the RCOOH functional group, and 𝐷𝐷 stands for dimer where
the RCOOH for each functional group has hydrogen bonded. The degree of association varies
with temperature and pressure, meaning that the fractions of monomer and dimer shift along the
saturation curve. It is often assumed that the liquid phase consists solely of dimer because the
molecules interact with one another. For the vapor phase, however, the mole fractions of
118
monomer and dimer need to be known in order to effectively represent the thermodynamic
properties along the saturation curve. For this purpose, an equilibrium constant is defined from
the fugacities of the mixture as:

2
𝐾𝐾𝑇𝑇 Φ𝑀𝑀
𝐾𝐾𝑃𝑃 = (8-6)
Φ𝐷𝐷
where 𝐾𝐾𝑇𝑇 is the temperature-dependent equilibrium constant, and Φ𝑀𝑀 and Φ𝐷𝐷 are the fugacity
coefficients of the monomer and dimer, respectively. The fugacity coefficients are calculated
using an equation of state with critical constants of the theoretical pure monomer and pure dimer,
respectively. These critical constants are taken from estimates in the literature [65], but the
fugacity coefficients are insensitive to these values.
The temperature-dependent equilibrium constant is:
Δ𝐺𝐺 −Δ𝐻𝐻 Δ𝑆𝑆

𝐾𝐾𝑇𝑇 = exp � � = exp � + � (8-7)
𝑅𝑅𝑔𝑔 𝑇𝑇 𝑅𝑅𝑅𝑅 𝑅𝑅𝑔𝑔
where 𝑅𝑅𝑔𝑔 is the universal gas constant, 𝑇𝑇 is the temperature, and Δ𝐺𝐺 is the Gibb’s energy of
association, which can be separated into Δ𝐻𝐻, the enthalpy of association, and Δ𝑆𝑆, the entropy of
association.
At this point, the monomer mole fraction given can be identified. The equilibrium
constant given in Equation 8-6 can also be defined in terms of the partial pressures of the
components:
𝑃𝑃𝐷𝐷
𝐾𝐾𝑃𝑃 = (8-8)
𝑃𝑃𝑀𝑀2
where 𝑃𝑃𝑀𝑀 and 𝑃𝑃𝐷𝐷 are the partial pressures of monomer and dimer, respectively. These can be
related to the mole fractions using Dalton’s law:
𝑃𝑃𝑖𝑖 = 𝑦𝑦𝑖𝑖 𝑃𝑃 (8-9)
119
where 𝑃𝑃𝑖𝑖 and 𝑦𝑦𝑖𝑖 are the partial pressure and mole fraction of the 𝑖𝑖 th component in the vapor
phase with total pressure 𝑃𝑃. Combining Equations 8-8 and 8-9 with the summation of the
monomer and dimer mole fractions gives the following expression:

2
1 = 𝑦𝑦𝑀𝑀 + 𝐾𝐾𝑃𝑃 𝑃𝑃𝑦𝑦𝑀𝑀 (8-10)
where 𝑦𝑦𝑀𝑀 is the monomer mole fraction, which can be isolated using the quadratic formula as:
−1 + �1 + 4𝐾𝐾𝑃𝑃 𝑃𝑃
𝑦𝑦𝑀𝑀 = (8-11)
2𝐾𝐾𝑃𝑃 𝑃𝑃
The monomer mole fraction can be used to adjust the volume from an equation of state to
that of an associating fluid found via experiment:
𝑍𝑍exp 𝑅𝑅𝑇𝑇exp 𝑉𝑉𝐸𝐸𝐸𝐸𝐸𝐸 𝑉𝑉𝐸𝐸𝐸𝐸𝐸𝐸

𝑉𝑉exp = = = (8-12)
𝑃𝑃exp 2𝑦𝑦𝐷𝐷 + 𝑦𝑦𝑀𝑀 2 − 𝑦𝑦𝑀𝑀
where 𝑉𝑉exp is the experimental volume at an experimental temperature, 𝑇𝑇exp , and pressure, 𝑃𝑃exp .
The volume using an equation of state, 𝑉𝑉𝐸𝐸𝐸𝐸𝐸𝐸 , is adjusted to fit the experimental compressibility
factor, 𝑍𝑍exp . In this process, the enthalpy and entropy of association from Equation 8-7 are used
to calculate 𝐾𝐾𝑇𝑇 , which is then used to calculate 𝐾𝐾𝑃𝑃 using Equation 8-6. 𝐾𝐾𝑃𝑃 is used in conjunction
with pressure in Equation 8-11 to calculate the monomer mole fraction. In the end, the monomer
mole fraction in Equation is fit to P,V,T data by adjusting the enthalpy and entropy of
association in Equation 8-7.
8.7.1 Saturated Monomer Mole Fraction
Using Wiltec data [65], supplemented by DECHEMA equilibrium constant correlations
[144] where necessary, the monomer mole fractions were calculated along the saturation curve
by using the supplied equilibrium constant equation and saturation pressure from a fit of vapor
pressure data. The temperature dependent results are given in n-carboxylic acids from formic
120
(C1) to octanoic acid (C8) in Figure 8-9, with curves spanning the triple point to the critical point
for each compound. As expected, the smaller acids experience the most dimerization, and
therefore have the smallest monomer mole fractions. As the acids increase in length, the
vibrations in the hydrocarbon tails overcome the strength of the hydrogen bond, resulting in
higher monomer mole fractions.
1
0.9 y.C1
0.8 y.C2
0.7 y.C3
y(Monomer)
0.6
y.C4
0.5
y.C5
0.4
y.C6
0.3
y.C7
0.2
y.C8
0.1
0
200 300 400 500 600 700
T/K
Figure 8-9: The monomer mole fractions for n-alkanoic acids along the saturation curve
It would seem intuitive that as the temperature increases, the fraction of monomer would
also increase because the thermal energy would overcome any hydrogen bonding. For acids
above 3 carbons in length, the mole fraction of monomer actually goes through a shallow
minimum with respect to temperature. This can be explained by examining Equation 8-11 for the
monomer mole fraction. In this equation, the equilibrium constant is multiplied by the pressure,
which is the temperature dependent vapor pressure equation in this case. At a given temperature,
the pressure – representing the ability of molecules to interact with each other – and the
121
equilibrium constant – representing the affinity of molecules to hydrogen bond upon interaction
– are in competition. As temperature increases, the vapor pressure increases, but the equilibrium
constant decreases. This balance determines the fraction of monomer and dimer in the mixture.
For large acids at low temperatures, the vapor pressures are too small for the molecules to
interact, resulting in mostly monomer. This explains the shallow minima with temperature in
Figure 8-9 for larger compounds.
8.7.2 Heat of Vaporization
Using these temperature dependent mole fractions, the heat of vaporization can be
derived from a fit of vapor pressure and P,V,T data as:
𝑉𝑉𝐸𝐸𝐸𝐸𝐸𝐸 (𝑇𝑇) 1 𝑑𝑑𝑃𝑃vap

Δ𝐻𝐻vap = 𝑇𝑇 � − �� (8-13)
2 − 𝑦𝑦𝑚𝑚 (𝑇𝑇) 2𝜌𝜌𝐿𝐿 (𝑇𝑇) 𝑑𝑑𝑇𝑇
where 𝜌𝜌𝐿𝐿 (𝑇𝑇) is the temperature dependent liquid molar density correlation given by DIPPR [44].
Because most of the liquid is associated into dimers, the liquid molar density is multiplied by 2
since the DIPPR correlation is per moles of monomer. The vapor volume is divided by 2 −
𝑦𝑦𝑚𝑚 (𝑇𝑇) to account for the volume of the mixture of monomers and dimers as shown by Equation
8-12. The association enthalpy and entropy from Equation 8-7 can be fit using vapor pressure
and heat of vaporization data in Equation 8-13. In this analysis, monomer mole fractions from
Figure 8-9 were fit to P,V,T data using Equation 8-12. Those mole fractions, along with DIPPR’s
liquid density correlations and vapor pressure correlations fit to data, were used in Equation 8-13
to calculate Δ𝐻𝐻vap for n-propanoic (C3) to n-heptanoic (C7) acids in Figure 8-10. These curves
matched Δ𝐻𝐻vap data for n-propanoic (C3) to n-hexanoic (C6) acids [65] well.
122
90
C3 Associated Clapeyron
80
70
C3 Data
60
C4 Data
ΔHvap (kJ mol-1)
C5 Data
50
C6 Data
40
30
20
10
0
250 300 350 400 450 500 550 600 650
T/K
Figure 8-10: Heat of vaporization experimental data and curves derived using the Clapeyron
equation for n-carboxylic acids with association
8.7.3 Future Work
Furthering this analysis, the slope of the Δ𝐻𝐻vap curve can be used to relate the ideal gas
heat capacity and the liquid heat capacity. The Derivative method, Equation 2-6, can be modified
for association, and the results can be compared to 𝐶𝐶𝑝𝑝𝑙𝑙 data to help improve thermodynamic
consistency for associating compounds. However, this analysis procedure has yet to be
adequately performed. Eventually, alcohols and amines, which weakly associate, will also be
considered in like manner.
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9 CONCLUSIONS
𝑖𝑖𝑖𝑖
The thermodynamic consistency among 𝑃𝑃vap , Δ𝐻𝐻vap , 𝐶𝐶𝑝𝑝 , and 𝐶𝐶𝑝𝑝𝑙𝑙 has been improved as a
result of this project. A survey of the literature helped shape this story. It was found that vapor
pressure, although the most commonly measured of the four properties, is generally not known
well at temperatures far below the normal boiling point. On the other hand, liquid heat capacity
is commonly measured at low temperatures, but not above the normal boiling point.
Thermodynamic relations were used to link these properties along the temperature region from
the triple point to the critical point. In so doing, both low temperature 𝑃𝑃vap and high temperature
𝐶𝐶𝑝𝑝𝑙𝑙 correlations were dramatically improved. Several methods were used to improve the
thermodynamic consistency of these properties.
The most obvious way to improve these properties was to optimize them simultaneously.
This was done by changing the fitting coefficients of the Riedel vapor pressure correlation to fit
𝑃𝑃vap and 𝐶𝐶𝑝𝑝𝑙𝑙 data, weighted by temperature. This allowed the vapor pressure curve to fit vapor
pressure data at high temperatures, and liquid heat capacity data at low temperatures. This
project used property uncertainties to inform the temperature dependent correlations.
Another way to improve the correlations for these properties is to change the vapor
pressure equation form. The exponent on the final temperature term of the Riedel correlation
(denoted as 𝐸𝐸) was changed from the traditional value of 6 to other integer values between 1 and
124
6. By so doing, the thermodynamic consistency from vapor pressure to liquid heat capacity for
41 compounds over 7 families was improved. In particular, the different 𝐸𝐸 values changed the
𝑃𝑃vap shape below the normal boiling point so that the thermodynamically-derived Derivative
method 𝐶𝐶𝑝𝑝𝑙𝑙 calculations went through 𝐶𝐶𝑝𝑝𝑙𝑙 data. This formed a manual optimization that was
simple to implement into DIPPR procedures.
For compounds without experimental vapor pressure data, a state-of-the-art 𝑃𝑃vap
prediction method was developed by taking advantage of the findings discussed in the previous
paragraph. Riedel’s corresponding states methodology was used in conjunction with 37 well-
known compounds to generate 𝑃𝑃vap predictive correlations with 𝐸𝐸 values ranging from 1 to 6.
These correlations were checked against 106 compounds, and thermodynamic analyses were
performed to determine which 𝐸𝐸 values worked best for which chemical families. This prediction
performed as well as other predictions from the literature for vapor pressure and heat of
vaporization. However, the average error for 𝐶𝐶𝑝𝑝𝑙𝑙 dropped from 8% using predictions from the
literature, to around 3% using this new prediction. This better agreement with 𝐶𝐶𝑝𝑝𝑙𝑙 corresponded
to an improvement in the low temperature vapor pressure prediction, precisely the temperature
region where previous prediction methods had been inadequate.
A differential scanning calorimeter (DSC) was purchased in order to measure
thermophysical properties for pure compounds. Calibrations and verifications showed
uncertainties of 1 K for melting point, and 5 J g-1 for enthalpy of fusion. Adjustments to the
American Society for Testing and Materials (ASTM) methods for measuring heat capacity
reduced the uncertainty from 3.2% to 1.52% on average across all compounds and temperatures.
In the end, melting point was measured for 13 compounds, enthalpy of fusion for 12 compounds,
125
and liquid heat capacity for 19 compounds. These new experimental data were combined with
the analysis procedures described in previous paragraphs to recommend improved,
thermodynamically consistent vapor pressure expressions for 14 of the compounds. In particular,
𝑃𝑃vap , Δ𝐻𝐻vap , and 𝐶𝐶𝑝𝑝𝑙𝑙 correlations for the tolualdehyde, furan, phenyl propanol, n-alkyl
cyclohexane, phenyl acetate, and di-n-alkyl ketone families were improved in this process.
In this project, the calculation methods for the thermodynamic relations linking these four
𝑖𝑖𝑖𝑖
properties--𝑃𝑃vap , Δ𝐻𝐻vap , 𝐶𝐶𝑝𝑝𝑙𝑙 , and 𝐶𝐶𝑝𝑝 —were also improved. Ideal gas heat capacity uncertainty
was reduced by correctly implementing the scaling factor within the statistical mechanics
derivation. Also, extrapolation error was avoided by not using group contribution methods to
𝑖𝑖𝑖𝑖
calculate 𝐶𝐶𝑝𝑝 below 298 K. Also, the Derivative and Integral liquid heat capacity calculation
methods were brought into alignment by careful mathematical investigation. These
improvements decreased the uncertainty in the Derivative method so that a) more successful 𝐶𝐶𝑝𝑝𝑙𝑙
predictions could be made, and b) more thermodynamically consistent vapor pressures curves
could be found. A review of 121 compounds with all of the improvements from this project
dropped the average liquid heat capacity absolute average deviation by 4%. These improvements
triggered a full database review, which in turn increased the value of the DIPPR database.
9.1 Future Work
Although this project was able to improve the thermodynamic consistency among 𝑃𝑃vap ,
𝑖𝑖𝑖𝑖
Δ𝐻𝐻vap , 𝐶𝐶𝑝𝑝 , and 𝐶𝐶𝑝𝑝𝑙𝑙 , it also introduced more topics that could be explored, as given in this list.
126
9.1.1 Continue Liquid Heat Capacity Measurements
There exist many more compounds in the DIPPR database that do not have 𝐶𝐶𝑝𝑝𝑙𝑙 data.
Continuing these measurements could help improve the current understanding of the correlation
forms for more chemical families similarly to the analyses done in Chapter 7 of this report.
Chemically similar compounds to 1H-perfluorooctane, 2,6-dimethoxyphenol, trans-isoeugenol,
and 1-propoxy-2-propanol could be measured to improve the family trends and verify the results
of the experiments listed in Chapter 7. To do this, octanal, 1,4-pentanediol, cyclopentyl acetic
acid, 2-(5H)-furanone, 1-chloro-3-propanol, N-methylpiperidine, vanillin, guaiacol, and eugenol
have been purchased, and melting points, enthalpy of fusions, and liquid heat capacities will be
measured by future lab researchers.
9.1.2 Measure Vapor Pressure
The standards established by ASTM E1782-14 give a useful guideline to measuring 𝑃𝑃vap
via DSC. This will include a couple of additions to the current setup (TA Instruments’ Q20
DSC). Figure 9-1 shows the recommended setup, including A) the DSC, B) a pressure
transducer, C) a pressure or vacuum source, D) a pressure stabilizer, E) a pressure regulator, and
F) a relief value. The pan lids would need holes added—in the form of either smaller pinholes
made by laser according to ASTM standards, or larger holes with a metal ball on top—to ensure
slow mass release [145, 146]. The Q20P DSC pressure can range from 1 to 7,000,000 Pa with a
vacuum pump attached. To make the measurement, pressure is held constant, and temperature is
increased at a constant rate. As temperature increases, an endothermic peak appears as the
material boils for the solid to liquid phase transition. With more 𝑃𝑃vap measurements done at low
pressures, current understanding of the low pressure portion of the 𝑃𝑃vap curve could be further
improved.
127
Figure 9-1: The experimental setup recommended by ASTM E1782-14 to measure Pvap via DSC
9.1.3 Improve the Multi-Property Optimization
As was mentioned in Chapter 4 and touch on in the conclusions, a multi-property
optimization was developed with temperature-dependent weightings. Although some work has
shown promising results, this procedure has not been adapted for use in DIPPR policies and
procedures. The multi-property optimization could be adapted to include the Riedel 𝐸𝐸 coefficient
as one of the parameters. Doing so would require subtle mathematical manipulation of the
optimization, since the 𝐸𝐸 value changes other Riedel fitting parameters by many orders of
magnitude. Furthermore, optimization constitutes a major research area, with many techniques
and strategies that could be used to improve the procedures started in Chapter 4. If an automated
regression scheme could be developed, the time needed to perform these thermodynamic
analyses would plummet.
128
9.1.4 Measure the Solid Phase Properties
The experimental setup and procedure for measuring 𝐶𝐶𝑝𝑝𝑠𝑠 does not differ from that of 𝐶𝐶𝑝𝑝𝑙𝑙 .
The Q2000 DSC could be an incredible tool in improving the 𝐶𝐶𝑝𝑝𝑠𝑠 data in the DIPPR database.
While measuring 𝐶𝐶𝑝𝑝𝑠𝑠 , a project could be used to improve the consistency in solid-vapor properties
the same way this project improved the consistency in solid-liquid properties. This could help
improve agreement among solid vapor pressure, heat of sublimation, and solid heat capacity.
9.1.5 Measure Ideal Gas Heat Capacity
Although ideal gas heat capacity can be derived via statistical mechanics, a complete
understanding of especially low temperature behavior has not yet been achieved. Following
experimental procedures for calorimetric [147], speed of sound [148], or thermal conductivity
[149] measurements could produce data necessary to fill gaps in data within the DIPPR database.
Also, the ab initio methods used to calculate ideal gas heat capacity require further attention.
Current DIPPR methods calculate vibrational frequencies for the torsion of dihedral angles and
treat them the same as other vibrational frequencies – constant through temperature. However, at
high temperatures, those torsional vibrations turn into internal rotations, commonly for
compounds with terminal methyl groups [150, 151]. This changes the contribution of the torsion
to the ideal gas heat capacity. Torsion calculations combined with the combinatorics for
configurational probabilities [152, 153], mean that ideal gas heat capacity prediction could use
some improvement.
9.1.6 Improve Methods for Associating Compounds
For the purposes of this discussion, associating compounds can be broken into two
groups: alcohols and acids. Alcohols strongly associate in the liquid phase, but only slightly
associate in the vapor phase. Even so, the Riedel equation does not seem to be the correct form to
129
predict heat capacity through the derivative method. For alcohols, a different vapor pressure
correlation should be used. A wider range of vapor pressure correlations in the literature could be
tested, or a new correlation form could be created. Acids strongly associate in the liquid phase,
and also associate in the vapor phase. This causes problems when trying to calculate vapor
volume from a cubic equation of state. As shown in Section 8.3, P,V,T measurements were used
to modify the equation of state to account for dimerization while using the Clapeyron equation.
Before vapor pressure, heat of vaporization, and ideal gas heat capacity can be used to
successfully predict liquid heat capacity, the temperature limits of the P,V,T measurements (and
subsequent equilibrium constant) need to be skillfully expanded to low temperatures where
liquid heat capacity data are common. Therefore, new P,V,T measurements or a careful
extrapolation technique guided by thermodynamic principles will be needed. Currently, there do
not exist enough data to understand the acid dimerization equilibrium over the whole
temperature range from the triple point to the critical point.
9.1.7 Reduce Heat of Vaporization Uncertainty
Although heat of vaporization was discussed here, it is still a topic for future work. As
shown in Figure 5-1 for n-butane, changing the vapor pressure correlation has a dramatic effect
on the heat of vaporization curve. Few experimental heat of vaporization data exist near the triple
point temperature, so they could not be used to check the results of this work. An analysis of
measurements in this temperature region could prove useful in trying to determine the best vapor
pressure curve. Measurements could be done in this region at low pressures to verify this
thermodynamic consistency procedure.
130
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203
APPENDIX A. THERMODYNAMIC DERIVATIONS
A.1 Clapeyron Equation Derivation
Start with the relationship between Gibb’s energy, enthalpy, and entropy from elementary
thermodynamics:
Δ𝐺𝐺 = Δ𝐻𝐻 − 𝑇𝑇Δ𝑆𝑆 (A-1)
At equilibrium, the Gibb’s energy is the same in the liquid and vapor phases, so Δ𝐺𝐺 is zero,
resulting in:
Δ𝐻𝐻 = 𝑇𝑇Δ𝑆𝑆 (A-2)
From the partial derivative game,
Δ𝑆𝑆 Δ𝑃𝑃
= (A-3)
ΔV Δ𝑇𝑇
Substituting Δ𝑆𝑆 from Equation A-3 into Equation A-2 gives the Clapeyron equation:
Δ𝑃𝑃
Δ𝐻𝐻 = 𝑇𝑇Δ𝑉𝑉 (A-4)
Δ𝑇𝑇
A.2 Derivative Method Derivation
First, start by recognizing that heat of vaporization is defined as the difference in
enthalpies of the liquid and vapor phases:
𝛥𝛥𝐻𝐻vap ≡ 𝐻𝐻vap − 𝐻𝐻liq (A-5)
Take the temperature derivative of the previous equation along the saturation curve:
𝛥𝛥𝐻𝐻vap 𝐻𝐻vap 𝐻𝐻liq

� � =� � −� � (A-6)
𝑑𝑑𝑑𝑑 𝜎𝜎 𝑑𝑑𝑑𝑑 𝜎𝜎 𝑑𝑑𝑑𝑑 𝜎𝜎
204
where 𝜎𝜎 signifies the slope along the saturation curve. The two terms on the right hand side of
the previous equation are the liquid and vapor saturation heat capacity, respectively:
𝛥𝛥𝐻𝐻vap 𝜎𝜎 𝜎𝜎
� � = 𝐶𝐶vap − 𝐶𝐶liq (A-7)
𝑑𝑑𝑑𝑑 𝜎𝜎
From this point, each saturation heat capacity needs to be changed to an isobaric heat capacity,
and the vapor must be transformed to ideal gas in order to compare the properties in question.
A.2.1 Saturation and Isobaric Heat Capacities
To derive the connection between saturation and isobaric heat capacity, first recognize
that for a closed system:
𝑑𝑑𝑑𝑑 = 𝑄𝑄 + 𝑊𝑊 = 𝑇𝑇𝑇𝑇𝑇𝑇 + 𝑉𝑉𝑉𝑉𝑉𝑉 (A-8)
where 𝑄𝑄 is heat, 𝑊𝑊 is work, 𝑆𝑆 is entropy, 𝑉𝑉 is volume, and 𝑃𝑃 is pressure. Since pressure, volume,
and temperature can be measured, they are often picked as the independent variables instead of
entropy. It would be useful to have an expression linking 𝑑𝑑𝑑𝑑 to 𝑑𝑑𝑑𝑑 and 𝑑𝑑𝑑𝑑. Write 𝑆𝑆 as a function
of 𝑇𝑇 and 𝑃𝑃:
𝑆𝑆 = 𝑆𝑆(𝑇𝑇, 𝑃𝑃) (A-9)
Then, use the chain rule of partial differentiation to obtain:
𝜕𝜕𝜕𝜕 𝜕𝜕𝜕𝜕
𝑑𝑑𝑑𝑑 = � � 𝑑𝑑𝑑𝑑 + � � 𝑑𝑑𝑑𝑑 (A-10)
𝜕𝜕𝜕𝜕 𝑃𝑃 𝜕𝜕𝜕𝜕 𝑇𝑇
𝜕𝜕𝜕𝜕 𝜕𝜕𝜕𝜕
Substitute � � = − � � from the Maxwell relation in for the second partial derivative of
𝜕𝜕𝜕𝜕 𝑇𝑇 𝜕𝜕𝜕𝜕 𝑃𝑃
Equation A-10:
𝜕𝜕𝜕𝜕 𝜕𝜕𝜕𝜕
𝑑𝑑𝑑𝑑 = � � 𝑑𝑑𝑑𝑑 − � � 𝑑𝑑𝑑𝑑 (A-11)
𝜕𝜕𝜕𝜕 𝑃𝑃 𝜕𝜕𝜕𝜕 𝑃𝑃
Now, break down the first partial derivative of Equation A-10 into parts:
205
𝜕𝜕𝜕𝜕 𝜕𝜕𝜕𝜕 𝜕𝜕𝜕𝜕
� � =� � � � (A-12)
𝜕𝜕𝜕𝜕 𝑃𝑃 𝜕𝜕𝜕𝜕 𝑃𝑃 𝜕𝜕𝜕𝜕 𝑃𝑃
𝑑𝑑𝑑𝑑 1
From Equation A-8 obtain: � � = , and from the definition of isobaric heat capacity obtain:
𝑑𝑑𝑑𝑑 𝑃𝑃 𝑇𝑇
𝜕𝜕𝜕𝜕
𝐶𝐶𝑃𝑃 = � � . Use these relationships in Equation A-11 to get:
𝜕𝜕𝜕𝜕 𝑃𝑃
𝐶𝐶𝑃𝑃 𝜕𝜕𝜕𝜕
𝑑𝑑𝑑𝑑 = 𝑑𝑑𝑑𝑑 − � � 𝑑𝑑𝑑𝑑 (A-13)
𝑇𝑇 𝜕𝜕𝜕𝜕 𝑃𝑃
Plugging this equation into Equation A-8 gives:
𝜕𝜕𝜕𝜕
𝑑𝑑𝑑𝑑 = 𝐶𝐶𝑃𝑃 𝑑𝑑𝑑𝑑 + �𝑉𝑉 − 𝑇𝑇 � � � 𝑑𝑑𝑑𝑑 (A-14)
𝜕𝜕𝜕𝜕 𝑃𝑃
At this point, take the partial derivative of enthalpy with respect to temperature at saturation to
get:
𝑑𝑑𝑑𝑑 𝜕𝜕𝜕𝜕 𝑑𝑑𝑑𝑑

𝐶𝐶𝜎𝜎 = � � = 𝐶𝐶𝑃𝑃 + �𝑉𝑉 − 𝑇𝑇 � � � � � (A-15)
𝑑𝑑𝑑𝑑 𝜎𝜎 𝜕𝜕𝜕𝜕 𝑃𝑃 𝑑𝑑𝑑𝑑 𝜎𝜎
or:
𝜕𝜕𝜕𝜕 𝑑𝑑𝑃𝑃vap
𝐶𝐶𝜎𝜎 = 𝐶𝐶𝑃𝑃 + �𝑉𝑉 − 𝑇𝑇 � � �� (A-16)
which is the relationship needed between saturation and isobaric heat capacity.
A.2.2 Vapor and Ideal Gas Heat Capacities
Adjusting between vapor and ideal gas heat capacity is simply an adjustment from vapor
pressure to zero pressure. To do so, the pressure dependence of isobaric heat capacity needs to be
found. Start with the commutative property of Equation A-14:
𝑑𝑑 𝑑𝑑𝑑𝑑 𝑑𝑑 𝑑𝑑𝑑𝑑
� � � � =� � � � (A-17)
𝑑𝑑𝑑𝑑 𝑇𝑇 𝑑𝑑𝑑𝑑 𝑃𝑃 𝑑𝑑𝑑𝑑 𝑃𝑃 𝑑𝑑𝑑𝑑 𝑇𝑇
and substitute partial derivatives on both sides of the equation to get:
206
𝑑𝑑 𝑑𝑑 𝜕𝜕𝜕𝜕
� 𝐶𝐶𝑃𝑃 � = � �𝑉𝑉 − 𝑇𝑇 � � �� (A-18)
𝑑𝑑𝑑𝑑 𝑇𝑇 𝑑𝑑𝑑𝑑 𝜕𝜕𝜕𝜕 𝑃𝑃 𝑇𝑇
or
𝑑𝑑 𝜕𝜕 2 𝑉𝑉
� 𝐶𝐶𝑃𝑃 � = −𝑇𝑇 � 2 � (A-19)
𝑑𝑑𝑑𝑑 𝑇𝑇 𝜕𝜕𝑇𝑇 𝑃𝑃
when simplified. Now, integrate from zero pressure to the vapor pressure on both sides to get:
𝑃𝑃vap
vap 𝑖𝑖𝑖𝑖 𝜕𝜕 2 𝑉𝑉
𝐶𝐶𝑃𝑃 − 𝐶𝐶𝑃𝑃 = � −𝑇𝑇 � � 𝑑𝑑𝑑𝑑 (A-20)
0 𝜕𝜕𝑇𝑇 2 𝑃𝑃
Solving for the isobaric vapor heat capacity shows:

𝑃𝑃vap
vap 𝑖𝑖𝑖𝑖 𝜕𝜕 2 𝑉𝑉
𝐶𝐶𝑃𝑃 = 𝐶𝐶𝑃𝑃 − � 𝑇𝑇 � � 𝑑𝑑𝑑𝑑 (A-21)
0 𝜕𝜕𝑇𝑇 2 𝑃𝑃
which is the needed relationship.
A.2.2 The Derivative Method
The pieces required to derive the derivative method are given by Equations AA-7,
AA-16, and AA-21. Plugging Equations AA-16 and AA-21 into Equation AA-7 gives:
𝛥𝛥𝐻𝐻vap 𝜕𝜕𝑉𝑉liq 𝑑𝑑𝑃𝑃vap

� � = −𝐶𝐶𝑃𝑃𝑙𝑙 + �𝑉𝑉liq − 𝑇𝑇 � � ��
𝑑𝑑𝑑𝑑 𝜎𝜎 𝜕𝜕𝜕𝜕 𝑃𝑃 𝑑𝑑𝑑𝑑
(A-22)
𝑖𝑖𝑖𝑖
𝑃𝑃vap 𝜕𝜕 2 𝑉𝑉vap 𝜕𝜕𝑉𝑉vap 𝑑𝑑𝑃𝑃vap
+ �𝐶𝐶𝑃𝑃 − � 𝑇𝑇 � 2
� 𝑑𝑑𝑑𝑑 + �𝑉𝑉vap − 𝑇𝑇 � � ��
0 𝜕𝜕𝑇𝑇 𝑃𝑃
This can be rearranged into the form given by Equation 2-6:

𝑃𝑃vap
𝑖𝑖𝑖𝑖 𝜕𝜕 2 𝑉𝑉vap 𝑑𝑑𝑑𝑑𝐻𝐻vap 𝜕𝜕Δ𝑉𝑉 𝑑𝑑𝑃𝑃vap
𝐶𝐶𝑝𝑝𝑙𝑙 = 𝐶𝐶𝑝𝑝 − 𝑇𝑇 � � � 𝑑𝑑𝑑𝑑 − + �Δ𝑉𝑉 − 𝑇𝑇 � � � (A-23)
𝜕𝜕𝑇𝑇 2 𝑑𝑑𝑑𝑑 𝜕𝜕𝜕𝜕 𝑃𝑃 𝑑𝑑𝑑𝑑
0
207
A.3 Ideal Gas Heat Capacity Derivation using Statistical Mechanics
As with most properties for ideal gases, heat capacity can be derived, starting with the
definition of isobaric heat capacity:
𝑑𝑑𝑑𝑑
𝐶𝐶𝑝𝑝 ≡ � � (A-24)
𝑑𝑑𝑑𝑑 𝑃𝑃
with 𝐶𝐶 p as the isobaric heat capacity, 𝑇𝑇 as the temperature, 𝑃𝑃 as the pressure, and 𝐻𝐻 as the
enthalpy of the fluid. Enthalpy can be broken down into parts:
𝐻𝐻 ≡ 𝑈𝑈 + 𝑃𝑃𝑃𝑃 (A-25)
with 𝑈𝑈 as the internal energy, 𝑃𝑃 as the pressure, and 𝑉𝑉 as the molar volume. Substituting this
definition into Equation AA-24 gives:
𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑
𝐶𝐶𝑃𝑃 = � � + 𝑃𝑃 � � (A-26)
𝑑𝑑𝑑𝑑 𝑃𝑃 𝑑𝑑𝑑𝑑 𝑃𝑃
From statistical mechanics,

𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚
𝑈𝑈 = � 𝑈𝑈𝑖𝑖 (A-27)
𝑖𝑖
with the modes of internal energy being translational, rotational, vibrational, and electronic. For
each of these modes,
𝑑𝑑ln(𝑞𝑞𝑖𝑖 )
𝑈𝑈𝑖𝑖 = 𝑘𝑘𝑇𝑇 2 � � (A-28)
𝑑𝑑𝑑𝑑 𝑁𝑁,𝑉𝑉
where 𝑘𝑘 is the Boltzmann constant, 𝑁𝑁 is the number of molecules, 𝑉𝑉 is the volume, and 𝑞𝑞𝑖𝑖 is the
contribution of mode 𝑖𝑖 to the partition function. Putting all of these concepts together gives a
form for heat capacity:
208
𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑑𝑑 �𝑘𝑘𝑇𝑇 2 � � �
⎛ 𝑑𝑑𝑑𝑑 𝑁𝑁,𝑉𝑉 ⎞ 𝑑𝑑𝑑𝑑
𝐶𝐶𝑃𝑃 = � ⎜ ⎟ + 𝑃𝑃 � � (A-29)
𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑 𝑃𝑃
𝑖𝑖
⎝ ⎠𝑃𝑃
The ideal gas law,
𝑃𝑃𝑃𝑃 = 𝑁𝑁𝑁𝑁𝑁𝑁 (A-30)
with 𝑃𝑃 as pressure, 𝑉𝑉 as molar volume, 𝑇𝑇 as temperature, 𝑁𝑁 as Avogadro’s number, and 𝑘𝑘 as the
𝑖𝑖𝑖𝑖
Boltzmann constant, simplifies Equation AA-29 for 𝐶𝐶𝑝𝑝 :
modes 𝑑𝑑 �𝑘𝑘𝑇𝑇 2 � � �
𝑖𝑖𝑖𝑖 ⎛ 𝑑𝑑𝑑𝑑 𝑁𝑁,𝑉𝑉 ⎞ 𝑖𝑖𝑖𝑖
𝐶𝐶𝑝𝑝 = � ⎜ ⎟ + 𝑁𝑁𝑁𝑁 = 𝐶𝐶𝑣𝑣 + 𝑁𝑁𝑁𝑁 (A-31)
𝑑𝑑𝑑𝑑
𝑖𝑖
⎝ ⎠𝑃𝑃
The partition function, 𝑞𝑞𝑖𝑖 in Equation AA-31, can be derived with statistical mechanics [154],
giving:
3𝑚𝑚−5
𝑖𝑖𝑖𝑖,linear 7 Θ𝑣𝑣𝑣𝑣 2 𝑒𝑒 Θ𝑣𝑣𝑣𝑣/𝑇𝑇
𝐶𝐶𝑝𝑝 = 𝑁𝑁𝑁𝑁 + � � � Θ𝑣𝑣𝑣𝑣 (A-32)
2 𝑇𝑇
for a linear molecule, and

3𝑚𝑚−6
𝑖𝑖𝑖𝑖,nonlinear Θ𝑣𝑣𝑣𝑣 2 𝑒𝑒 Θ𝑣𝑣𝑣𝑣/𝑇𝑇
𝐶𝐶𝑝𝑝 = 4𝑁𝑁𝑁𝑁 + � � � Θ𝑣𝑣𝑣𝑣 (A-33)
𝑇𝑇
for a non-linear molecule with 𝑇𝑇 as temperature, 𝑚𝑚 as the number of atoms in a single molecule,
and Θ𝑣𝑣𝑣𝑣 as the 𝑗𝑗𝑡𝑡ℎ vibrational frequency for linear and nonlinear molecules with m atoms,
respectively [25].
209
APPENDIX B. DATA USED
Vapor pressure, heat of vaporization, and liquid heat capacity literature data were used
throughout the course of this project. Chapters 4, 5, 6, and 7 were all published separately, but
much of the literature data overlapped. Here, the data were separated by property, and then
further separated into whichever chapter they were used.
B.1 Vapor Pressure Data
Vapor pressure data are summarized below. These tables are categorized into data used in
Chapter 5, and data used in Chapter 6.
B.1.1 Vapor Pressure Data for Riedel Equation Analysis
The following data were used to analyze which forms of the Riedel equation worked for
which families, as described in Chapter 5.
211
Table B-1: Summary of vapor pressure data used in this work for the n-alkanes
Carbon # # Pvap Data Pvap Low T Pvap High T Data Sources
2 278 92 K 305.42 K [55, 155-165]
3 120 163.15 K 368.75 K [164, 166-178]
4 200 195.1 K 425.07 K [53, 164, 169, 179-214]
5 108 223.05 K 468 K [147, 215-223]
6 228 239.55 K 503.15 K [223-260]
7 406 185.3 K 540 K [159, 214, 223, 229, 230, 233, 239, 241, 242, 246, 253, 255, 261-292]
8 162 263.15 K 568.74 K [187, 214, 223, 233, 244, 269, 272, 292-299]
Table B-2: Summary of vapor pressure data used in this work for the 2-methylalkanes
3 159 238.98 K 407.5 K [168, 180-182, 189, 190, 195, 199, 202, 203, 210-212, 300-318]
4 55 217.19 K 448.15 K [213, 214, 223, 319-321]
5 48 285.91 K 359.7 K [223, 260, 322-324]
6 34 273.13 K 530.3 K [244, 325]
7 50 233.15 K 559.56 K [223, 244, 326, 327]
Table B-3: Summary of vapor pressure data used in this work for the 1-alkenes
3 188 151.72 K 364.5 K [162, 174, 187, 247, 328-345]
4 143 198.15 K 420.37 K [174, 180, 182, 189, 190, 195, 202, 247, 315, 318, 334, 346-355]
5 88 218.35 K 463.4 K [247, 271, 356-360]
6 64 249.97 K 374.15 K [262, 278, 285, 361-364]
7 40 255.46 K 374.15 K [362-366]
Table B-4: Summary of vapor pressure data used in this work for the n-aldehydes
4 30 303.86 K 353.15 K [250, 367-375]
5 34 242.15 K 377.65 K [376-380]
212
Table B-4: continued
6 19 322.27 K 402.17 K [381-385]
7 30 310.15 K 453.15 K [379, 386, 387]
Table B-5: Summary of vapor pressure data used in this work for aromatic compounds
Compound # Pvap Data Pvap Low T Pvap High T Data Sources
Benzene 143 283.1 K 553.15 K [361, 388-393]
Toluene 98 247.15 K 591.7 K [361, 388-394]
Ethylbenzene 165 288.1 K 618 K [223, 271, 361, 389, 395-399]
Propylbenzene 31 266.35 K 433.39 K [223, 271, 400]
n-Butylbenzene 27 268.45 K 500.97 K [36, 400, 401]
m-Xylene 123 273.15 K 617.05 K [223, 271, 288, 389, 397, 402-414]
o-Xylene 145 273.15 K 630.2 K [223, 235, 271, 389, 402-404, 407, 410-422]
p-Xylene 83 293.15 K 616.1 K [223, 271, 318, 397, 402, 403, 407, 410-414, 423-428]
Table B-6: Summary of vapor pressure data used in this work for the ethers
Dimethyl- 20 261.37 K 335.66 K [257, 301, 370, 429-437]
Diethyl- 55 250.05 K 466.85 K [296, 297, 316, 438-442]
Ethyl propyl- 139 171.63 K 400.38 K [443, 444]
Di-n-propyl- 40 299.74 K 323.15 K [378, 441, 445-448]
Methyl tert-Butyl 250 273.15 K 496.4 K [214, 245, 247, 370, 446, 449-452]
Table B-7: Summary of vapor pressure data used in this work for the ketones
Methyl Ethyl 175 265.15 K 536.78 K [214, 398, 453-476]
Methyl Isopropyl 77 276.25 K 549.82 K [457, 458, 477-487]
213
Methyl Isobutyl 149 283.15 K 415.82 K [458, 479, 483, 487-495]
2-Pentanone 99 203.61 K 558.15 K [445, 477, 480, 496-500]
2-Hexanone 36 298.15 K 427.76 K [453, 483, 498, 501-504]
3-Hexanone 93 292.85 K 422.25 K [361, 396, 453, 503, 505, 506]
2-Heptanone 119 274 K 452.42 K [396, 453, 500, 507-510]
2-Octanone 52 260 K 630 K [453, 500, 501, 511-515]
214
B.1.2 Vapor Pressure Data for New Predictive Riedel Equation
The following data were used to generate and analyze the predictive Riedel equation as
described in Chapter 6.
215
Table B-8: Summary of vapor pressure data used in this work for alkanes and alkenes
Ethane 278 92 K 305.42 K [55, 155-165]
Propane 120 163.15 K 368.75 K [164, 166-178]
Butane 200 195.1 K 425.07 K [53, 164, 169, 179-214]
Pentane 108 223.05 K 468 K [147, 215-223]
Hexane 228 239.55 K 503.15 K [223-260]
Octane 162 263.15 K 568.74 K [187, 214, 223, 233, 244, 269, 272, 292-299]
Isopropane 159 238.98 K 407.5 K [168, 180-182, 189, 190, 195, 199, 202, 203, 210-212, 300-318]
Isobutane 55 217.19 K 448.15 K [213, 214, 223, 319-321]
2-Methylhexane 34 273.13 K 530.3 K [244, 325]
2-Methylheptane 50 233.15 K 559.56 K [223, 244, 326, 327]
Cyclohexane 109 280.05 K 560.07 K [223, 516-521]
Ethylene 97 110 K 282.34 K [361, 522-526]
Benzene 143 283.1 K 553.15 K [361, 388-393]
Toluene 98 247.15 K 591.7 K [361, 388-394]
m-Xylene 123 273.15 K 617.05 K [223, 271, 288, 389, 397, 402-414]
o-Xylene 145 273.15 K 630.2 K [223, 235, 271, 389, 402-404, 407, 410-422]
p-Xylene 83 293.15 K 616.1 K [223, 271, 318, 397, 402, 403, 407, 410-414, 423-428]
Table B-10: Summary of vapor pressure data used in this work for the esters and ethers
Methyl Formate 62 198.95 K 487.15 K [361, 527, 528]
Ethyl Acetate 272 229.75 K 523.3 K [187, 233, 248, 250, 288, 318, 401, 445, 529-543]
Propyl Formate 87 302.43 K 370.61 K [544, 545]
Diethyl Ether 55 250.05 K 466.85 K [296, 297, 316, 438-442]
216
Table B-11: Summary of vapor pressure data used in this work for the gases
Hydrogen 23 15.1 K 33.18 K [361, 546]
Neon 62 24.54 K 44.49 K [361, 527, 547-549]
Argon 22 83.8 K 150.86 K [361, 445, 550]
Oxygen 77 54.36 K 154.58 K [361, 526, 551]
Carbon Monoxide 53 68.08 K 132.92 K [361, 548, 552-554]
Table B-12: Summary of vapor pressure data used in this work for the halogenated compounds
Chlorotrifluoromethane 78 92.16 K 302 K [12, 555, 556]
Carbon tetrachloride 84 252.65 K 556.3 K [361, 445, 528, 557]
Hexafluoroethane 94 173.7 K 292.22 K [558-562]
Fluorobenzene 33 255.3 K 560.07 K [445, 529, 563]
Methyl Ethyl 175 265.15 K 536.78 K [214, 398, 453-476]
Methyl Isobutyl 149 283.15 K 415.82 K [458, 479, 483, 487-495]
2-Pentanone 99 203.61 K 558.15 K [445, 477, 480, 496-500]
2-Hexanone 36 298.15 K 427.76 K [453, 483, 498, 501-504]
3-Hexanone 93 292.85 K 422.25 K [361, 396, 453, 503, 505, 506]
2-Heptanone 119 274 K 452.42 K [396, 453, 500, 507-510]
2-Octanone 52 260 K 630 K [453, 500, 501, 511-515]
Table B-14: Summary of vapor pressure data used in this work for alkanes
Heptane 406 185.3 K 540 K [159, 214, 223, 229, 230, 233, 239, 241, 242, 246, 253, 255, 261-292]
2-Methylpentane 48 285.91 K 359.7 K [223, 260, 322-324]
2,2-Dimethylpentane 43 285.34 K 453.15 K [223, 271, 364, 564]
217
3-Ethylpentane 49 294.28 K 540.57 K [244, 271, 565]
3-Methylheptane 19 315.85 K 563.6 K [223, 244]
2,3,3-Trimethylpentane 41 309.9 K 573.49 K [223, 244]
Table B-15: Summary of vapor pressure data used in this work for multifunctional compounds
2-Aminobiphenyl 36 350 K 623.56 K [566]
Aniline 53 343.16 K 498.85 K [36, 567-570]
Dibenzofuran 34 358.15 K 602.59 K [571]
Dimethyl isophthalate 32 349.98 K 607.23 K [34]
Furan 42 275.7 K 483.15 K [572-574]
Indane 57 284 K 482.44 K [575-578]
Methyl Acrylate 17 278.15 K 353.15 K [574, 579]
2-Methylpyridine 61 295.24 K 441.52 K [580-582]
3-Methylpyridine 42 314.03 K 457.7 K [582-584]
Piperazine 17 418 K 655 K [585, 586]
Pyridine 50 310.64 K 616.48 K [573, 587-589]
Pyrrole 77 338.15 K 615.15 K [235, 573, 589-591]
Styrene 44 298.1 K 635.2 K [169, 592-594]
Tetrahydrofuran 120 275.99 K 538.71 K [214, 283, 573, 595-600]
Propylene 188 151.72 K 364.5 K [162, 174, 187, 247, 328-345]
Butylene 143 198.15 K 420.37 K [174, 180, 182, 189, 190, 195, 202, 247, 315, 318, 334, 346-355]
1-Pentene 88 218.35 K 463.4 K [247, 271, 356-360]
1-Heptene 40 255.46 K 374.15 K [362-366]
trans-2-Pentene 30 273.15 K 343.15 K [601, 602]
1,3-Butadiene 50 193.1 K 423.1 K [180, 186, 196, 318, 370, 603, 604]
218
trans-1,3-Pentadiene 21 213.14 K 315.96 K [605]
2-Methyl-1,2-Butadiene 23 213.14 K 319.19 K [606]
Propylene 188 151.72 K 364.5 K [162, 174, 187, 247, 328-345]
Butylene 143 198.15 K 420.37 K [174, 180, 182, 189, 190, 195, 202, 247, 315, 318, 334, 346-355]
1-Pentene 88 218.35 K 463.4 K [247, 271, 356-360]
1-Heptene 40 255.46 K 374.15 K [362-366]
trans-2-Pentene 30 273.15 K 343.15 K [601, 602]
1,3-Butadiene 50 193.1 K 423.1 K [180, 186, 196, 318, 370, 603, 604]
Table B-18: Summary of vapor pressure data used in this work for the n-aldehydes
Propanal 29 231.15 K 373.15 K [213, 250, 367, 371, 470, 607-611]
Butanal 30 303.86 K 353.15 K [250, 367-375]
Pentanal 34 242.15 K 377.65 K [376-380]
Hexanal 19 322.27 K 402.17 K [381-385]
Heptanal 30 310.15 K 453.15 K [379, 386, 387]
Ethylbenzene 165 288.1 K 618 K [223, 271, 361, 389, 395-399]
p-Cymene 35 263.15 K 633.15 K [543, 612, 613]
219
Ethylbenzene 165 288.1 K 618 K [223, 271, 361, 389, 395-399]
p-Cymene 35 263.15 K 633.15 K [543, 612, 613]
Naphthalene 100 353.33 K 745.9 K [586, 614-623]
Phenanthrene 32 373.15 K 667.74 K [606, 624]
Pyrene 8 425.65 K 458.15 L [625]
Table B-20: Summary of vapor pressure data used in this work for the ethers
Dimethyl- 20 261.37 K 335.66 K [257, 301, 370, 429-437]
Ethyl propyl- 139 171.63 K 400.38 K [443, 444]
Di-n-propyl- 40 299.74 K 323.15 K [378, 441, 445-448]
Methyl tert-Butyl 250 273.15 K 496.4 K [214, 245, 247, 370, 446, 449-452]
Methyl Isopropyl 77 276.25 K 549.82 K [457, 458, 477-487]
Table B-22: Summary of vapor pressure data used in this work for the amines
Ethylamine 28 211.86 K 456.35 K [626, 627]
Propylamine 13 296.12 K 350.74 K [299, 628]
Butylamine 12 297.09 K 349.3 K [629, 630]
Pentylamine 13 322.61 K 377.93 K [631]
Isobutylamine 18 289.18 K 373.76 K [628]
N,N-Diethylmethylamine 9 308.15 K 444.61 K [632-634]
Triethylamine 36 273.04 K 423.15 K [214, 629, 635-637]
220
Isopropylamine 11 213.08 K 334.13 K [628]
Table B-23: Summary of vapor pressure data used in this work for the ringed alkanes
Ethylcyclopentane 29 301.93 K 566.48 K [271, 638]
Methylcyclohexane 113 298.74 K 443.15 K [214, 223, 288, 516, 639-642]
Ethylcyclohexane 17 324.56 K 405.89 K [223]
Propylcyclohexane 11 345.66 K 430.86 K [223]
Table B-24: Summary of vapor pressure data used in this work for the halogenated compounds
1,2-Dichloroethane 75 293.15 K 560.3 K [261, 636, 643-649]
n-Butyl chloride 77 256.45 K 367.05 K [249, 364, 470, 650-658]
Trifluoromethane 164 133.69 K 298.15 K [659-665]
Perfluoro-n-heptane 72 271.26 K 473.94 K [666-670]
Table B-25: Summary of vapor pressure data used in this work for the esters
Butyl Acetate 94 326.19 K 410.04 K [445, 671-676]
Pentyl Acetate 75 274.2 K 508.85 K [9, 401, 677-682]
Hexyl Acetate 21 274.5 K 380.55 K [679, 683-686]
Octyl Acetate 21 274.5 K 484.95 K [683-686]
Table B-26: Summary of vapor pressure data used in this work for the sulfides
Methyl mercaptan 8 221.88 K 288.16 K [687, 688]
Ethyl mercaptan 33 273.15 K 373.15 K [169, 689-691]
221
Diethyl sulfide 54 283.15 K 395.58 K [182, 692-694]
Methyl-n-butyl sulfide 30 346.9 K 435.83 K [690, 695]
Methyl isopropyl sulfide 38 275 K 550 K [690, 696, 697]
Table B-27: Summary of vapor pressure data used in this work for the alkynes and silanes
Ethylacetylene 35 204.23 K 353.15 K [636, 698, 699]
Tetramethylsilane 34 208.94 K 450.4 K [700-702]
222
B.2 Heat of Vaporization Data
Heat of vaporization data were used in Chapter 6 to determine how well the new
predictive vapor pressure method does with the Clapeyron equation. Those data are listed here.
223
Table B-28: Summary of heat of vaporization data used in this work for alkanes and alkenes
Compound # ΔHvap Data ΔHvap Low T ΔHvap High T Data Sources
Ethane 18 133.15 K 301.3 K [703, 704]
Propane 25 277.6 K 361 K [705-707]
Butane 1 273.7 K 273.7 K [552]
Pentane 56 259.54 K 455.37 K [147, 706, 708-711]
Hexane 21 298.15 K 444.26 K [710, 712-715]
Octane 4 298.2 K 298.2 K [14, 16, 17, 716]
Isopropane 11 261.4 K 383.71 K [717, 718]
Isobutane -- -- -- --
2-Methylhexane 5 298.15 K 353.15 K [325, 715]
2-Methylheptane 5 298.15 K 353.15 K [710, 715]
Cyclohexane 20 310.93 K 537.04 K [719-723]
Ethylene -- -- -- --
Table B-29: Summary of heat of vaporization data used in this work for the aromatic compounds
Benzene 24 273.1 K 553.1 K [714, 724-726]
Toluene 26 298.15 K 521.13 K [425, 727, 728]
m-Xylene -- -- -- --
o-Xylene -- -- -- --
p-Xylene 11 298.15 K 509.27 K [728]
Table B-30: Summary of heat of vaporization data used in this work for the esters and ethers
Methyl Formate 3 293.3 K 313.5 K [723]
Ethyl Acetate 8 320.57 K 363.4 K [729, 730]
Propyl Formate* -- -- -- --
Diethyl Ether 5 293.15 K 313.15 K [731-733]
224
Table B-31: Summary of heat of vaporization data used in this work for the gases
Hydrogen 20 13.96 K 32.87 K [546, 734]
Neon -- -- -- --
Argon -- -- -- --
Oxygen 1 90.13 K 90.13 K [735]
Carbon Monoxide -- -- -- --
Table B-32: Summary of heat of vaporization data used in this work for the halogenated compounds
Chlorotrifluoromethane -- -- -- --
Carbon tetrachloride 5 298.15 K 358.15 K [736]
Hexafluoroethane 8 179.96 K 195.21 K [559]
Fluorobenzene -- -- -- --
Table B-33: Summary of heat of vaporization data used in this work for the ketones
Methyl Ethyl 13 298.15 K 370.57 K [275, 454, 471, 737]
Methyl Isobutyl 5 298.15 K 358.15 K [454, 737]
2-Pentanone 7 298.15 K 358.15 K [737-739]
2-Hexanone 17 298.15 K 368.15 K [737, 738, 740, 741]
3-Hexanone 5 298.15 K 368.15 K [737]
2-Heptanone 2 298.15 K 298.15 K [738, 742]
2-Octanone 1 298.15 K 298.15 K [738]
Table B-34: Summary of heat of vaporization data used in this work for alkanes
Heptane 20 273.15 K 373.15 K [710, 714, 715, 743, 744]
225
2-Methylpentane 7 293.15 K 353.15 K [713, 745]
2,2-Dimethylpentane 9 298.15 K 368.15 K [746]
3-Ethylpentane 7 298.15 K 348.15 K [746]
3-Methylheptane 1 298.15 K 298.15 K [710]
2,3,3-Trimethylpentane 9 298.15 K 368.15 K [746]
Table B-35: Summary of heat of vaporization used in this work for the 1-alkenes
Propylene 13 227.6 K 355.4 K [747]
Butylene 20 202.31 K 377.59 K [346, 748, 749]
1-Pentene 15 283.96 K 410.93 K [358, 750]
1-Heptene -- -- -- --
trans-2-Pentene -- -- -- --
1,3-Butadiene 3 247.07 K 295.67 K [604]
trans-1,3-Pentadiene -- -- -- --
2-Methyl-1,2-Butadiene -- -- -- --
Table B-36: Summary of heat of vaporization data used in this work for the n-aldehydes
Propanal 4 286.25 K 321.21 K [751, 752]
Butanal 2 298.15 K 347.9 K [752, 753]
Pentanal -- -- -- --
Hexanal -- -- -- --
Heptanal -- -- -- --
226
Table B-37: Summary of heat of vaporization data used in this work for the aromatic compounds
Ethylbenzene -- -- -- --
Propylbenzene -- -- -- --
n-Butylbenzene 3 343.15 K 368.15 K [754]
p-Cymene -- -- -- --
Naphthalene -- -- -- --
Phenanthrene -- -- -- --
Pyrene -- -- -- --
Table B-38: Summary of heat of vaporization data used in this work for the ethers
Dimethyl- 1 248.3 K 248.3 K [429]
Ethyl propyl- -- -- -- --
Di-n-propyl- 10 298.15 K 363.22 K [441, 731, 755]
Methyl tert-Butyl 5 298.15 K 343.15 K [731, 756]
Table B-39: Summary of heat of vaporization data used in this work for the ketones
Methyl Isopropyl 6 298.2 K 367.48 K [505, 737]
Table B-40: Summary of heat of vaporization data used in this work for the amines
Ethylamine -- -- -- --
Propylamine 3 298.15 K 328.15 K [629]
Butylamine 6 298.15 K 358.15 K [629, 757]
Pentylamine 1 298.15 K 328.15 K [757]
Isobutylamine 4 298.15 K 298.15 K [629, 757]
227
N,N-Diethylmethylamine -- -- -- --
Triethylamine 7 298.15 K 362.15 K [629, 757]
Isopropylamine 2 298.15 K 313.15 K [629]
Table B-41: Summary of heat of vaporization data used in this work for the ringed alkanes
Ethylcyclopentane 5 313.15 K 368.15 K [758]
Methylcyclohexane 11 298.2 K 493.15 K [710, 715, 727]
Ethylcyclohexane 6 298.2 K 368.15 K [710, 758]
Table B-42: Summary of heat of vaporization data used in this work for the halogenated compounds
1,2-Dichloroethane 7 298 K 358.15 K [736, 759, 760]
n-Butyl chloride 11 298.15 K 358.15 K [752, 759, 761-763]
Trifluoromethane 2 190.97 K 191.15 K [659, 764]
Perfluoro-n-heptane 1 298.15 K 298.15 K [728]
Table B-43: Summary of heat of vaporization data used in this work for the esters
Butyl Acetate 6 298.15 K 358.15 K [765-767]
Pentyl Acetate -- -- -- --
Hexyl Acetate -- -- -- --
Octyl Acetate -- -- -- --
228
Table B-44: Summary of heat of vaporization data used in this work for the sulfides
Methyl mercaptan 1 279.11 K 279.11 K [688]
Ethyl mercaptan 3 281.15 K 281.16 K [689]
Diethyl sulfide 4 286 K 365.26 K [22, 692]
Methyl-n-butyl sulfide 1 298.15 K 298.15 K [695]
Methyl isopropyl sulfide 4 298.15 K 357.98 K [697, 768]
Table B-45: Summary of heat of vaporization data used in this work for the alkynes and silanes
Ethylacetylene 6 262.53 K 282.52 K [698]
Tetramethylsilane -- -- -- --
Table B-46: Summary of heat of vaporization data used in this work for multifunctional compounds
2-Aminobiphenyl -- -- -- --
Aniline 3 298.15 K 333.2 K [769-771]
Dibenzofuran -- -- -- --
Dimethyl isophthalate -- -- -- --
Furan 3 279.15 K 304.51 K [572]
Indane 51 284 K 500 K [577, 578, 772]
Methyl Acrylate -- -- -- --
2-Methylpyridine 6 298.15 K 368.15 K [773]
3-Methylpyridine 6 298.15 K 368.15 K [773]
Piperazine -- -- -- --
Pyridine 9 298.15 K 388.4 K [587, 773]
Pyrrole 3 362.11 K 402.91 K [590]
Styrene -- -- -- --
Tetrahydrofuran 3 301.8 K 339.1 K [774]
229
B.3 Liquid Heat Capacity Data
Liquid heat capacity data are summarized below. These tables are categorized into data
used in Chapter 5, and data used in Chapter 6.
B.3.1 Liquid Heat Capacity Data for Riedel Equation Analysis
The following data were used to analyze which forms of the Riedel equation worked for
which families, as described in Chapter 5.
230
Table B-47: Summary of liquid heat capacity data used in this work for the n-alkanes
Carbon # # Cpl Data Cpl Low T Cpl High T Data Sources
2 33 91.59 K 290 K [55, 775]
3 21 89.66 K 229.75 K [776]
4 99 138.61 K 316.75 K [777]
5 17 148.6 K 302.87 K [778]
6 58 180 K 366.48 K [779-784]
7 47 182.55 K 370 K [325, 783-790]
8 50 222.61 K 386.09 K [779, 782, 784, 785, 791-795]
Table B-48: Summary of liquid heat capacity data used in this work for the 2-methylalkanes
3 27 113.55 K 380 K [796]
4 22 113.36 K 300 K [320, 797-800]
5 20 121.16 K 303.27 K [780, 801]
6 37 154.9 K 300 K [325, 501, 799]
7 26 164.19 K 370 K [710, 799]
Table B-49: Summary of liquid heat capacity data used in this work for the 1-alkenes
3 32 93.9 K 223.4 K [496, 802, 803]
4 128 88.5 K 299.83 K [346, 804, 805]
5 114 108.78 K 308.44 K [806-808]
6 55 136.19 K 308.16 K [809-811]
7 22 157.13 K 299.61 K [809]
Table B-50: Summary of liquid heat capacity data used in this work for the n-aldehydes
4 72 176.8 K 330.53 K [375, 812, 813]
5 2 270 K 298.2 K [814, 815]
231
Carbon # # Cp Data Cpl Low T
l
Cpl High T Data Sources
6 11 214.94 K 330 K [816]
7 8 230 K 300 K [375]
Table B-51: Summary of liquid heat capacity data used in this work for the aromatic compounds
Compound # Cpl Data Cpl Low T Cpl High T Data Sources
Benzene 37 278.68 K 500 K [361, 394]
Toluene 52 278.15 K 503.15 K [790, 817-825]
Ethylbenzene 37 184.4 K 373.15 K [826-834]
n-Butylbenzene 45 193.81 K 640 K [36, 831, 833, 835]
m-Xylene 39 231.4 K 540.15 K [405, 411, 817, 825, 831, 834]
o-Xylene 17 251.99 K 413.18 K [415]
p-Xylene 29 290 K 410.65 K [411, 825, 827, 834, 836, 837]
Table B-52: Summary of liquid heat capacity data used in this work for the ethers
Dimethyl- 11 140 K 240 K [429]
Diethyl- 42 164.39 K 300 K [501, 529, 838, 839]
Ethyl propyl- 21 145.65 K 320 K [756]
Di-n-propyl- 22 158.36 K 330 K [501, 755]
Methyl tert-Butyl 65 168.32 K 325.15 K [756, 840-842]
Table B-53: Summary of liquid heat capacity data used in this work for the ketones
Methyl Ethyl 69 186.47 K 335 K [814, 843-847]
Methyl Isopropyl 21 184.43 K 440 K [496, 843]
Methyl Isobutyl 6 190 K 450 K [496]
2-Pentanone 37 196.35 K 364.11 K [501, 843, 848-850]
232
l
Compound # Cp Data Cpl Low T Cpl High T Data Sources
2-Hexanone 63 217.69 K 460 K [361, 496, 501, 849, 851]
3-Hexanone 39 220 K 460 K [496, 815, 851]
2-Heptanone 7 240 K 490 K [496, 500]
2-Octanone 25 252.86 K 500 K [361, 496, 848]
233
B.3.2 Liquid Heat Capacity Data for New Predictive Riedel Equation
The following data were used to analyze the predictive Riedel equation as described in
Chapter 6.
234
Table B-54: Summary of liquid heat capacity data used in this work for alkanes and alkenes
Ethane 33 91.59 K 290 K [55, 775]
Propane 21 89.66 K 229.75 K [776]
Butane 99 138.61 K 316.75 K [777]
Pentane 17 148.6 K 302.87 K [778]
Hexane 58 180 K 366.48 K [779-784]
Octane 50 222.61 K 386.09 K [779, 782, 784, 785, 791-795]
Isopropane 27 113.55 K 380 K [796]
Isobutane 22 113.36 K 300 K [320, 797-800]
2-Methylhexane 37 154.9 K 300 K [325, 501, 799]
2-Methylheptane 26 164.19 K 370 K [710, 852]
Cyclohexane 37 279.99 K 366.48 K [781, 838, 853]
Ethylene 27 103.97 K 252.7 K [361, 854]
Benzene 37 278.68 K 500 K [361, 394]
Toluene 52 278.15 K 503.15 K [790, 817-825]
m-Xylene 39 231.4 K 540.15 K [405, 411, 817, 825, 831, 834]
o-Xylene 17 251.99 K 413.18 K [415]
p-Xylene 29 290 K 410.65 K [411, 825, 827, 834, 836, 837]
Table B-56: Summary of liquid heat capacity data used in this work for the esters and ethers
Methyl Formate 12 213.15 K 304.15 K [361, 501, 855, 856]
Ethyl Acetate 25 189.3 K 330 K [813, 857]
Propyl Formate* -- -- -- --
Diethyl Ether 42 164.39 K 300 K [501, 529, 838, 839]
235
Table B-57: Summary of liquid heat capacity data used in this work for the gases
Hydrogen 20 14 K 32 K [546]
Neon 9 24.6 K 40 K [858]
Argon 6 83.8 K 130 K [526, 838]
Oxygen 57 54.36 K 142 K [526, 735, 859]
Carbon Monoxide 31 70 K 128 K [361, 553, 860-862]
Table B-58: Summary of liquid heat capacity data used in this work for the halogenated compounds
Chlorotrifluoromethane 1 243.15 K 243.15 K [555]
Carbon tetrachloride 6 293.15 K 333.15 K [850, 863-865]
Hexafluoroethane 12 174.88 K 195 K [552, 559]
Fluorobenzene 18 239.99 K 454.95 K [866, 867]
Methyl Ethyl 69 186.47 K 335 K [814, 843-847]
Methyl Isobutyl 6 190 K 450 K [496]
2-Pentanone 37 196.35 K 364.11 K [501, 843, 848-850]
2-Hexanone 63 217.69 K 460 K [361, 496, 501, 849, 851]
3-Hexanone 39 220 K 460 K [496, 815, 851]
2-Heptanone 7 240 K 490 K [496, 500]
2-Octanone 25 252.86 K 500 K [361, 496, 848]
Table B-60: Summary of liquid heat capacity data used in this work for alkanes
Heptane 47 182.55 K 370 K [325, 783-790]
2-Methylpentane 20 121.16 K 303.27 K [780, 801]
2,2-Dimethylpentane 17 154.68 K 298.36 K [325]
236
l
3-Ethylpentane 7 250 K 300 K [361]
3-Methylheptane 28 157.2 K 376 K [710, 852]
2,3,3-Trimethylpentane 6 280 K 320 K [361]
Table B-61: Summary of liquid heat capacity data used in this work for the 1-alkenes
Propylene 32 93.9 K 223.4 K [496, 802, 803]
Butylene 128 88.5 K 299.83 K [346, 804, 805]
1-Pentene 114 108.78 K 308.44 K [806-808]
1-Heptene 22 157.13 K 299.61 K [809]
trans-2-Pentene 35 134.98 K 301.68 K [806, 868]
1,3-Butadiene 16 164.24 K 300 K [604]
Table B-62: Summary of liquid heat capacity data used in this work for the n-aldehydes
Propanal 2 298.2 K 298.2 K [814]
Butanal 72 176.8 K 330.53 K [375, 812, 813]
Pentanal 2 270 K 298.2 K [814, 815]
Hexanal 11 214.94 K 330 K [816]
Heptanal 8 230 K 300 K [375]
Ethylbenzene 37 184.4 K 373.15 K [826-834]
n-Butylbenzene 45 193.81 K 640 K [36, 831, 833, 835]
237
l
p-Cymene 20 205.25 K 300 K [613, 870]
Naphthalene 23 355 K 434.98 K [871-873]
Phenanthrene 4 383.27 K 408.64 K [874]
Pyrene 7 423.81 K 480 K [875]
Table B-64: Summary of liquid heat capacity data used in this work for the ethers
Dimethyl- 11 140 K 240 K [429]
Ethyl propyl- 21 145.65 K 320 K [756]
Di-n-propyl- 22 158.36 K 330 K [501, 755]
Methyl tert-Butyl 65 168.32 K 325.15 K [756, 840-842]
Methyl Isopropyl 21 184.43 K 440 K [496, 843]
Table B-66: Summary of liquid heat capacity data used in this work for the amines
Ethylamine 2 293.15 K 293.15 K [627, 876]
Propylamine 20 189.96 K 334.56 K [877, 878]
Butylamine 2 298.15 K 298.15 K [878, 879]
Pentylamine 1 298.15 K 298.15 K [878]
Isobutylamine 1 298.15 K 298.15 K [877, 879, 880]
N,N-Diethylmethylamine 2 283.15 K 298.15 K [881]
Triethylamine 11 298.15 K 393.15 K [878, 882]
Isopropylamine 25 177.99 K 353.15 K [877, 879, 880]
238
Table B-67: Summary of liquid heat capacity data used in this work for the ringed alkanes
Ethylcyclopentane 50 140.23 K 301.82 K [529]
Methylcyclohexane 14 155.09 K 298.15 K [883, 884]
Ethylcyclohexane 32 167.35 K 560 K [885, 886]
Table B-68: Summary of liquid heat capacity data used in this work for the halogenated compounds
1,2-Dichloroethane 37 284.16 K 353.14 K [821, 865, 888]
n-Butyl chloride 30 284.15 K 353.15 K [889]
Trifluoromethane 15 117.97 K 240 K [659, 890]
Perfluoro-n-heptane 20 221.87 K 470 K [666, 669]
Table B-69: Summary of liquid heat capacity data used in this work for the esters
Butyl Acetate 25 193.15 K 373.15 K [891-895]
Pentyl Acetate 15 300 K 580 K [9]
Hexyl Acetate 6 193.15 K 423.15 K [895]
Octyl Acetate 23 310.03 K 420.02 K [818]
Table B-70: Summary of liquid heat capacity data used in this work for the sulfides
Methyl mercaptan 13 160 K 280 K [688]
Ethyl mercaptan 21 130.04 K 315.25 K [689]
Diethyl sulfide 15 181.95 K 322.08 K [692]
Methyl-n-butyl sulfide 23 186.9 K 358.01 K [695]
Methyl isopropyl sulfide 45 171.65 K 360 K [697]
239
Table B-71: Summary of liquid heat capacity data used in this work for the alkynes and silanes
Ethylacetylene 14 150 K 280 K [698]
Tetramethylsilane 28 174.79 K 290 K [701, 896, 897]
Table B-72: Summary of liquid heat capacity data used in this work for multifunctional compounds
2-Aminobiphenyl 44 322.28 K 800 K [566]
Aniline 51 275.7 K 700 K [36, 857, 880, 898]
Dibenzofuran 17 361.98 K 520.28 K [571]
Dimethyl isophthalate 20 360 K 740 K [34]
Furan 14 190.99 K 299.08 K [572]
Indane 6 240 K 320 K [899]
Methyl Acrylate 12 196.21 K 300 K [900]
2-Methylpyridine 70 209.9 K 570 K [580, 582]
3-Methylpyridine 70 257.52 K 595 K [582, 584]
Piperazine 13 384.6 K 505 K [585, 901]
Pyridine 30 231.49 K 560 K [587, 588, 902]
Pyrrole 19 249.74 K 400 K [590]
Styrene 6 250 K 300 K [903]
Tetrahydrofuran 22 164.76 K 320 K [904-906]
240
B.4 Compounds measured
Below is a compilation of the data in the literature for the compounds that were measured
in Chapter 7.
Table B-73: Summary of melting point and melting enthalpy literature data
Formula Compound Cas No. Tm/K ΔHm/(J g-1) Source
C8H8O o-Tolualdehyde 529-20-4 -- --
C8H8O m-Tolualdehyde 620-23-5 -- --
C8H8O p-Tolualdehyde 104-87-0 356.65 -- [907]
356.65 -- [908]
320.15 -- [909]
512.15 -- [910]
C8H10O m-Tolualcohol 587-03-1 -- --
C8H8O2 p-Toluic acid 99-94-5 455.15 -- [911]
555.1 -- [912]
555.1 165.9 [113]
452.34±0.22 165.11±0.81 [110]
450.15±1 -- [108]
452.75 166.9 [118]
455.15 -- [913]
453.65 -- [109]
452.75 -- [112]
456.70 208.6 [111]
C9H12O 1-Phenyl-1-propanol 93-54-9 -- --
C9H12O 2-Phenyl-1-propanol 1123-85-9 399.15 -- [914]
C9H12O 2-Isopropylphenol 88-69-7 288.65 -- [527]
C6H8O 2,5-Dimethylfuran 625-86-5 -- --
C6H6O2 5-Methylfurfural 620-02-0 -- --
C8H8O2 Phenyl acetate 122-79-2 -- --
C10H12O2 Ethyl 2-phenylacetate 101-97-3 243.75 -- [915]
C12H24 n-Hexylcyclohexane 4292-75-5 225.64 -- [916]
225.64 -- [917]
C11H22O 6-Undecanone 927-49-1 285.65 -- [918]
287.65±0.5 -- [919,
920]
287.15 -- [126]
C8HF17 1H-Perfluorooctane 335-65-9 -- --
C8H10O3 2,6-Dimethoxyphenol 91-10-1 328.65±0.1 -- [127]
328.65±0.6 -- [128]
326.15±1.5 -- [129]
241
Formula Compound Cas No. Tm/K ΔHm/(J g-1) Source
C8H10O3 2,6-Dimethoxyphenol 91-10-1 328.65±0.5 -- [130]
324.95±0.7 -- [921]
327.65 [130]
C10H12O2 trans-Isoeugenol 5932-68-3 298.15 -- [922]
303.33 -- [923]
306.05 -- [924]
304.65 -- [925]
C6H14O2 1-Propoxy-2-propanol 1569-01-3 -- --
Table B-74: Summary of vapor pressure literature data

Formula Compound CAS No. T range /K Pvap range /kPa Source
C8H8O o-Tolualdehyde 529-20-4 -- -- --
C8H8O m-Tolualdehyde 620-23-5 468.15 99.3 [926]
357.15 1.9 [927]
C8H8O p-Tolualdehyde 104-87-0 373.62-374.62 1.93? [928]
383.13 2.67? [929]
389.13 101.3 [930]
C8H10O m-Tolualcohol 587-03-1 -- -- --
C8H8O2 p-Toluic acid 99-94-5 775 3800 [931]
C9H12O 1-Phenyl-1-propanol 93-54-9 383.13 101.3 [930]
380.15 2 [932]
378.65 2.27 [933]
380.15 2.40 [934]
401.44 5.33 [935]
378.65 1.87 [936]
371.15 1.33 [937]
C9H12O 1-Phenyl-2-propanol 698-87-3 -- -- --
C9H12O 2-Phenyl-1-propanol 1123-85-9 405.63 4.47 [938]
375.15 0.8 [939]
342.15 0.09 [940]
383.65 1.3 [941]
373.65 0.7 [942]
C9H12O 2-Isopropylphenol 88-69-7 329.73-487.66 0.133-101.3 [527]
375.09-493.28 2.014-118 [943]
379.13 2.67 [944]
486.16 101.3 [945]
486.16 99.3 [946]
486.16 101.3 [947]
486.16 101.3 [948]
486.66 101.3 [949]
C6H8O 2,5-Dimethylfuran 625-86-5 283.16-366.7 3.01-101.3 [950]
313.15-393.15 5.88-114 [951]
272.7-299.1 1.5-6.8 [952]
242
Formula Compound CAS No. T range /K Pvap range /kPa Source
C6H8O 2,5-Dimethylfuran 625-86-5 331.46-366.83 30.01-101.33 [953]
345.24-364.37 50-94 [954]
345.24-364.37 50-94 [955]
C6H6O2 5-Methylfurfural 620-02-0 303.15-453.15 0.10-83.40 [956]
359.95-450.19 2.93-79.1 [957]
362.65 3.5 [958]
337.15 0.93 [959]
298.15 0.08 [960]
C8H8O2 Phenyl acetate 122-79-2 465.8-685.2 93.08-3593 [961]
349.15 1 [962]
468.95 101.0 [963]
348.65 1 [964]
372.15 3.3 [965]
C10H12O2 Ethyl 2-phenylacetate 101-97-3 393.23-475.15 3.13-52.5 [966]
288.2-328.2 0.0033-0.084 [967]
501.16 100 [968]
415.15 8 [969]
388.65 2.9 [970]
381.65 2 [971]
356.9 0.53 [972]
C12H24 n-Hexylcyclohexane 4292-75-5 264.7-467.26 7.5E-4-47.38 [973]
497.94 101.3 [916]
497.94 101.3 [917]
497.86 101.3 [974]
375.12, 494.16 2.13, 101.3 [975]
C11H22O 6-Undecanone 927-49-1 388.35-531.93 2.608-201.7 [453]
496.16 101.3 [976]
418.83 3.9 [918]
C8HF17 1H-Perfluorooctane 335-65-9 298.15-413.15 0.24-75.0 [90]
346.15 6 [977]
330.65 2.7 [978]
C8H10O3 2,6-Dimethoxyphenol 91-10-1 -- -- --
C10H12O2 trans-Isoeugenol 5932-68-3 414.15 2 [979]
359.45-515.45 0.13-53.3 [527]
414.15 2.13 [980]
C6H14O2 1-Propoxy-2-propanol 1569-01-3 298.15-413.15 0.341-74.983 [981]
298.15-323.15 0.355-1.755 [982]
330.65 2.66 [978]
605.1 3051 [983]
421.93 97.3 [984]
243
Table B-75: Summary of heat of vaporization literature data
Formula Compound CAS No. T range /K ΔHvap range /(J mol-1) Source
C8H8O p-Tolualdehyde 104-87-0 -- --
C8H8O2 p-Toluic acid 99-94-5 -- --
C9H12O 2-Isopropylphenol 88-69-7 -- --
C6H8O 2,5-Dimethylfuran 625-86-5 -- --
C6H6O2 5-Methylfurfural 620-02-0 298.15 55 800 [985]
C8H8O2 Phenyl acetate 122-79-2 -- -- --
C10H12O2 Ethyl 2-phenylacetate 101-97-3 -- --
C12H24 n-Hexylcyclohexane 4292-75-5 298.14 56 500 [986]
C11H22O 6-Undecanone 927-49-1 -- -- --
C8H10O3 2,6-Dimethoxyphenol 91-10-1 -- --
C10H12O2 trans-Isoeugenol 5932-68-3 -- --
Table B-76: Summary of liquid heat capacity literature data

Formula Compound Cas No. T range /K Cpl range /(J mol-1 K-1) Source
C8H8O p-Tolualdehyde 104-87-0 -- --
C8H8O2 p-Toluic acid 99-94-5 452.75 321 [118]
C9H12O 2-Isopropylphenol 88-69-7 -- --
C6H8O 2,5-Dimethylfuran 625-86-5 298.15 149 [952]
C6H6O2 5-Methylfurfural 620-02-0 -- --
C8H8O2 Phenyl acetate 122-79-2 -- --
C10H12O2 Ethyl 2-phenylacetate 101-97-3 298.15 338 [967]
C12H24 n-Hexylcyclohexane 4292-75-5 -- --
C11H22O 6-Undecanone 927-49-1 -- --
C8H10O3 2,6-Dimethoxyphenol 91-10-1 -- --
C10H12O2 trans-Isoeugenol 5932-68-3 -- --
244
APPENDIX C. SAMPLE CALCULATION FOR PREDICTIVE METHOD
The vapor pressure of 2,2-dimethylpentane will be calculated at 285.34 K, where there
exists a reliable data point to check the method [271]. The DIPPR critical constants and normal
boiling point are given in Table C-1, from which the reduced properties can be calculated, given
in Table C-2.
Table C-1: Summary of compound constants for 2,2-dimethylpentane

Constant Symbol Value Unit
Critical Temperature 𝑇𝑇𝑐𝑐 520.5 K
Critical Pressure 𝑃𝑃𝑐𝑐 2.77E6 Pa
Normal Boiling Point 𝑇𝑇𝑁𝑁𝑁𝑁 352.34 K
Table C-2: Summary of reduced properties for 2,2-dimethylpentane

Reduced Property Symbol Value
𝑻𝑻/𝑻𝑻𝒄𝒄 𝑇𝑇𝑟𝑟 0.54820
𝑻𝑻𝑵𝑵𝑵𝑵 /𝑻𝑻𝒄𝒄 𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 0.67693
𝒂𝒂𝒂𝒂𝒂𝒂/𝑷𝑷𝒄𝒄 𝑃𝑃𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 0.03658
Start by selecting 𝐸𝐸 = 3, the recommended 𝐸𝐸 value for alkanes in Table 5-2. From this,
calculate 𝐾𝐾 and 𝑋𝑋𝑐𝑐 using Equations 18 and 19, respectively:
𝐾𝐾 = 4.96465 ∗ 3−2.29195 = 0.400268
𝑋𝑋𝑐𝑐 = 4.14524 − 0.0818433 ∗ 3 + 0.00310685 ∗ 32 = 3.92767
With 𝐾𝐾, 𝑋𝑋𝑐𝑐 , 𝐸𝐸, and 𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 , calculate 𝜙𝜙 at the normal boiling point using Equation 6-24:
32
𝜙𝜙(𝑇𝑇𝑛𝑛𝑛𝑛𝑛𝑛 , 𝐸𝐸) = 32 − 1 − − 3 ∗ (3 + 1) ∗ ln(0.67693) + 0.676933 = −0.30288
0.67693
From these values, calculate 𝐷𝐷 and 𝛼𝛼𝑐𝑐 using Equations 6-22 and 6-23, respectively:
245
ln(0.03658) + 0.400268 ∗ 3.92767 ∗ (−0.30288)
𝐷𝐷 = 0.400268 � − 3.92767� = 1.3898
ln(0.67693) + 0.400268 ∗ (−0.30288)
ln(0.03658) + 0.400268 ∗ 3.92767 ∗ (−0.30288)

𝛼𝛼𝑐𝑐 = = 7.3998
ln(0.67693) + 0.400268 ∗ (−0.30288)
Now calculate correlation coefficients 𝐴𝐴 − 𝐶𝐶 using Equations 6-19 through 6-21:
𝐴𝐴 = (32 − 1) ∗ 1.3898 = 11.118
𝐵𝐵 = −32 ∗ 1.3898 = −12.508
𝐶𝐶 = 7.3998 − 3 ∗ (3 + 1) ∗ 1.3898 = −9.2778
We now have a temperature dependent correlation for the vapor pressure of 2,2-dimethylpentane
by substituting these coefficients into Equation 9:
−12.508
ln(𝑃𝑃𝑟𝑟 ) = 11.118 + − 9.2778 ∗ ln(𝑇𝑇𝑟𝑟 ) + 1.3898 ∗ 𝑇𝑇𝑟𝑟 3
𝑇𝑇𝑟𝑟
or:
−12.508
𝑃𝑃vap = 𝑃𝑃𝑐𝑐 ∗ exp �11.118 + − 9.2778 ∗ ln(𝑇𝑇𝑟𝑟 ) + 1.3898 ∗ 𝑇𝑇𝑟𝑟 3 �
𝑇𝑇𝑟𝑟
Plugging in the reduced temperature for 314.86 K gives: 𝑃𝑃vap = 7645 𝑃𝑃𝑃𝑃. This agrees to within
1 % of experimental data from the literature at 7700 Pa.
246

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Brigham Young University

Improving Thermodynamic Consistency Among

Follow this and additional works at: https://scholarsarchive.byu.edu/etd

BYU ScholarsArchive Citation

Joseph Wallace Hogge

A dissertation submitted to the faculty of

W. Vincent Wilding, Chair

Department of Chemical Engineering

Copyright © 2017 Joseph Wallace Hogge

Improving Thermodynamic Consistency Among

Joseph Wallace Hogge

In order to improve temperature-dependent correlations, all the properties were analyzed

Keywords: multi-property optimization, vapor pressure, heat capacity, heat of vaporization

LIST OF TABLES ....................................................................................................................... viii

Table 4-1: Summary of the sum squared errors used ................................................................... 24

Table 5-2: A list of non-hydrocarbons investigated in this study, ................................................ 32

Table 6-1: Compounds originally investigated by Riedel, ........................................................... 49

Table 6-2: Training set of compounds for the new ....................................................................... 55

Table 6-3: Summary of prediction constants for the original ....................................................... 55

Table 6-5: Recommended E values for each of the ...................................................................... 60

Table 7-1: Purities of compounds measured in this study ............................................................ 71

Table 7-2: Purities of verification compounds used in this study................................................. 71

Table 7-6: Summary of experimental melting point measurements a ........................................... 80

Table 7-7 Summary of experimental enthalpy of fusion measurements a .................................... 81

Table 7-12: Summary of experimental glass transition temperatures .......................................... 86

Table 7-22: Summary of enthalpy of fusion experimental results for the

Table 7-27: Summary of experimental melting points for............................................................ 96

Table 7-28: Summary of enthalpy of fusion experimental results for .......................................... 97

Table 7-29: Summary of experimental melting points for............................................................ 98

Table 7-30: Summary of enthalpy of fusion experimental results for .......................................... 98

Table 7-33: Summary of experimental enthalpy of fusion for trans-isoeugenol........................ 101

compounds .................................................................................................................................. 217

compounds .................................................................................................................................. 218

compounds .................................................................................................................................. 221

compounds .................................................................................................................................. 224

ethers ........................................................................................................................................... 224

compounds .................................................................................................................................. 225

compounds .................................................................................................................................. 227

compounds .................................................................................................................................. 228

compounds .................................................................................................................................. 229

methylalkanes ............................................................................................................................. 231

compounds .................................................................................................................................. 232

compounds .................................................................................................................................. 235

ethers ........................................................................................................................................... 235

compounds .................................................................................................................................. 236

compounds .................................................................................................................................. 237

compounds .................................................................................................................................. 239

compounds .................................................................................................................................. 240

Table B-73: Summary of vapor pressure literature data ............................................................. 242

Table B-74: Summary of heat of vaporization literature data .................................................... 244

Table C-1: Summary of compound constants for 2,2-dimethylpentane ..................................... 245

the DIPPR database....................................................................................................................... 15

to true experimental data in the literature ..................................................................................... 16

Cpig data ......................................................................................................................................... 17

ethylene glycol .............................................................................................................................. 19

method prediction from the start of this project............................................................................ 19

boiling point .................................................................................................................................. 25

liquid isobaric heat capacity.......................................................................................................... 28

n-alkanes ethane ( ), propane ( ), butane ( ), pentane ( ), hexane ( ),

heptane ( ), and octane ( ) ................................................................................................... 38

2-methylalkanes isopropane ( ), 2-methylbutane ( ), 2-methylpentane ( ), 2-

methylhexane ( ), and 2-methylheptane ( )......................................................................... 39

1-alkenes propylene ( ), 1-butene ( ), 1-pentene ( ), 1-hexene ( ), and 1-