Thermodynamic properties of S-(−)-nicotine

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Highlights

Abstract

In this work, a reliable and reciprocal set of thermodynamic properties of nicotine has been formed using the experimental and theoretical methods. The values of the enthalpies of combustion and formation of the substance in liquid state have been measured using combustion calorimetry. The temperature dependence of the vapor pressure of nicotine within the low temperature interval 289–373 K has been obtained via transpiration method along with calculation the value of enthalpy of vaporization. The analysis of the substance vapor pressure measurements available in the published sources has been performed, the set of nicotine vapor pressure values in the wide temperature interval has been formed. The enthalpy of formation in the gas state of the substance was determined using the experimental data. Quantum chemical calculation reaffirmed its reliability. The method of statistical thermodynamics has been used to calculate the values of thermodynamic functions of the compound in the ideal gas state within the interval 298.15–1500 K.

Introduction

Nicotine is an alkaloid of the pyridine series. It is found mainly in the leaves and stems of tobacco, which in turn is used in the production of cigarettes and cigars [1]. Smoking is a complex thermochemical process where the knowledge of physico-chemical and transport properties of the main component of tobacco, nicotine, is necessary to enable its description and modeling. These properties, in addition to others, include vapor pressure in a wide temperature range and the values of the thermodynamic properties (enthalpies of formation, enthalpies of phase transitions, absolute entropy and free Gibbs energy).

Nicotine is an optically active compound having two enantiomeric forms. The naturally occurring form of nicotine: S-(−)-nicotine is levorotatory. The dextrorotatory form, R-(+)-nicotine, is physiologically less active than S-(−)-nicotine. The observations show that S-(−)-nicotine exhibits more toxic properties than R-(+)-nicotine [2].

The analysis of published data shows that thermodynamic properties of S-(−)-nicotine have not been fully studied. The enthalpy of combustion and formation of the liquid substance were measured only once in 1899 in Berthelot [3]. The vapor pressures of the substance have been measured many times [4], [5], [6], [7], [8], [9], [10] and are in satisfactory agreement with each other. However, prevailing majority of measurements was performed at temperatures higher than 373.15 K and the enthalpies of vaporization of the substance referenced to the temperature 298.15 K vary significantly. For instance, ref. [10] contains the compilation of the collected and analyzed measurements of the temperature dependences of nicotine vapor pressures available in the literature [4], [5], [6], [7], [8], [9]. The obtained enthalpies of vaporization at 298.15 K based on these values fall within the interval 61.8 ÷ 68.5 kJ·mol−1 [10]. The heat capacity and entropy of the compound have not been measured before.

The aim of this study is obtaining a reliable set of thermodynamic properties of S-(−)-nicotine. To reach this goal, the vapor pressure of the substance was measured in close proximity to the temperature 298.15 K by transpiration method. The enthalpy of vaporization was determined. The enthalpy of formation of liquid S-(−)-nicotine was obtained using the highly precise combustion calorimetry. Based on this data, the value of enthalpy of formation in the gaseous state of substance has been derived. The conformational analysis of compound was performed. A set of the most stable conformers was established. The values of the thermodynamic functions of nicotine over a wide temperature range were estimated by employing methods of statistical thermodynamics using experimental and computed data.

Section snippets

Sample

A commercial sample of S-(-)-nicotine (Acros Organics, 99+%, CAS 54-11-5) was additionally purified by fractional distillation under reduced pressure. The water content in the sample was determined using Karl Fisher titration and it was equal to 358 ppm. The final purity of the substance was determined by the method of gas chromatography (chromatograph Hewlett Packard 3390A, a carrier gas – nitrogen, capillary column SE-30 30 m long) and it reached at least 99.9%.

Combustion calorimetry. Enthalpy of formation measurements

The combustion energy of

Enthalpies of formation in the condensed state

The standard specific energies of combustion Δc(liq) of S-(−)-nicotine have been used to derive the standard molar enthalpy of combustion ΔcHm(liq) and the standard molar enthalpy of formation in the liquid state ΔfHm(liq). Values of Δc and ΔfHm are referenced to reaction:C10H14N2(liq)+13.5O2(g)=10CO2(g)+7H2O(l)+N2(g)

The obtained values of ΔcHmand ΔfHm of compound in liquid state are given in Table 4. The enthalpy of formation of nicotine was measured only during research conducted by

Conclusion

The thermodynamic properties of nicotine have been measured in this study. The comparison of the vapor pressures of the substance has been performed. A reliable and inter-correlating set of enthalpy properties of nicotine has been presented. The methods of statistical thermodynamics and quantum chemical calculations have been used to derive thermodynamic functions of the substance in the ideal gas phase at 298.15–1500 K. The value of free Gibbs energy in a condensed state has been obtained.

Acknowledgements

The authors express special gratitude to Prof. S.P. Verevkin (University of Rostock, Germany) for the help in discussion of obtained results. This work has been partly supported by the Russian Government Program of Competitive Growth of Kazan Federal University.

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