Adventures in Thermochemistry James S. Chickos * Department of Chemistry and Biochemistry University of Missouri-St. Louis Louis MO A portion of the Science Complex UMSL

Adventures in Thermochemistry Research Interests Phase Transitions and Their Properties Fusion Enthalpies Vaporization Enthalpies Sublimation Enthalpies Estimating vaporization enthalpies Estimating fusion enthalpies Estimating melting temperatures Estimating boiling temperatures Evaluating vapor pressures (liquid and solid) Estimating heat capacities (solid and liquid)

Hypothetical Thermodynamic Properties Phase change properties have been measured and studied for over 200 years. Many methods have been developed for measuring and estimated these properties. One of the major interests in my research group was focused on developing methods both experimental and computational that would allow studies of the properties of materials that can not measured directly because of their characteristics. For example, they decompose at the temperatures needed for measurement, they exist naturally as mixtures, or the property is experimentally inaccessible. Hypothetical thermodynamic properties: useful in constructing thermochemical cycles Vapor pressures of many solid polutants are relatively non-volatile and present in very low concentrations on particulate matter. The vapor pressures of these materials can be modeled by the vapor pressure of the sub-cooled liquid.

Fusion Enthalpies 1.Measurement 2.Their estimation

Measurements of Fusion Enthalpies Perkin Elmer DSC -7

Estimation of Thermodynamic Properties A measurement always results in a number. Estimations though only approximate offer a rational way of deciding on whether the result is reasonable or not. This is particularly useful to those of us that are training students.

Estimation of Fusion Enthalpies The direct estimation of fusion enthalpies is problematic for the following : The DSC heating curve of CCl 4: ∆H fus (251 K) 2.52 kJ  mol -1 ∆H trns (226 K) 4.58 kJ  mol -1

Fusion enthalpy does not seem amenable to a group additivity approach; neither does fusion entropy Waldon’s Rule: ∆H fus (T fus )/T fus ≈ 54.4 J  mol -1  K -1 ∆H fus (T fus ) T fus ∆S fus (T fus ) ∆S tpce dodecane tridecane tetradecane pentadecane Consider however the total phase change entropy from T = (0 to T fus ) K. Is total phase change entropy (∆S tpce ) treatable by group additivity?

Our Philosophy Regarding Estimation Methods There seem to be two philosophies regarding estimation methods including group additivity 1.Devise a simple and consequently approximate method 2.Devise a method that is as precise as possible Our experience has been that the simplest method wins out. It is used the most and misused the least. Methods that have numerous parameters are often improperly used and sometimes these parameters are simply parameterizing experimental error.

Estimating total Phase Change Entropy bbbbbb. b Used with function groups attached.

Alkanes∆S tpce = 1.31*7.1*n CH *n CH3 ∆H fus (T fus ) T fus /K ∆S tpce (exp) ∆S tpce (est) ∆H tpce (T fus ) est J  mol -1 J  mol -1  K -1 J  mol -1 dodecane tridecane tetradecane pentadecane tridecane ∆S tpce (exp) = 28490/ /255 = J  mol -1  K -1 ∆H tpce (exp) = = J  mol -1 pentadecane ∆S tpce (exp) = 34600/ /270.9 = J  mol -1  K -1 ∆H tpce (exp) = = J  mol -1 Some Simple Estimations

Aromatics ∆S tpce = [7.4]·n =CH- + [- 7.5] ·n =CR- + [-9.6]·n =CR’- + [17.6]·n CH3 R = sp 2 atom; R’ =sp 3 atom 1-methylnaphthalene [7.4]·7+[-7.5]·2 + [-9.6] +[17.6] = 44.9 (49.3) expt 2-methylnaphthalene = 44.9 (58.9) expt 1-methylnaphthalene ∆H tpce (T fus ) exp = 11930; ∆H tpce (T fus ) calc = methylnaphthalene ∆H tpce (T fus ) exp = 17740; ∆H tpce (T fus ) calc = Some Simple Estimations / J  mol -1

R = any atom

∆H fus (T fus ) = 11.0 kJ  mol -1 exp ∆H tpce (T fus ) = 13.6 calc T t = 116, 363, 262 K ∆H t = 1.4, 7.0, 11.0 ∆H tpce = ∆S tpce = 37.8 ∆S tpce = [33.4] + [3.7]·2 –[12.3]·3 – [1.6]·2 + [7.4]·6 – [7.5] = 37.8

= 45.4 = 48.0 = 22.1 (exp0 ∆H tpce (T fus ) = 23.5 calc ∆H fus (T fus ) = 8.55 exp

Exp ∆S fus (T fus ) = 84.7; ∆H fus (484.2; K) = 41000; two polymorphs Calc ∆S fus (T fus ) = 80.5; ∆H fus (484.2; K) = 38980; Values in [ ] are tentative assignments

Calc ∆S fus (T fus ) = 85.6 ∆H fus (499.2 K) = 42.7 Exp ∆S fus (T fus ) = 71.9 ∆H fus (499.2 K) = 35.9 [33.4] +3.7[3] + [1.2] +[-1.4] + [-14.7] + 2[-12.3] + [17.6] + 5[7.4] + [-9.6] + 4[-7.5] +3[20.3] +[4.7]

Why do some molecules have errors greater than ±3  ?

A series of compounds forming liquid crystals ∆S tpce = Σ ∆H i /T i On of the questions left to be answered is why do liquid crystals behave in this way?

The total phase change entropy is not very useful unless the fusion temperature is available. Our next adventure into trying to predict melting temperatures resulted in some surprises.

Reference and Acknowledgement Total Phase Change Entropies and Enthalpies. An Update on Fusion Enthalpies and Their Estimation. Chickos, J. S.; Acree Jr. W. E. Thermochim. Acta 2009, 495, 5-13 and references cited.