Elsevier

Atmospheric Environment

Volume 45, Issue 3, January 2011, Pages 561-577
Atmospheric Environment

Atmospheric amines – Part II. Thermodynamic properties and gas/particle partitioning

https://doi.org/10.1016/j.atmosenv.2010.10.013Get rights and content

Abstract

Amines enter the atmosphere from a wide range of sources, but relatively little is known about their atmospheric behavior, especially their role in gas/particle partitioning. In Part I of this work (Ge et al., 2011) a total of 154 amines, 32 amino acids and urea were identified as occurring in the atmosphere, based upon a survey of the literature. In this work we compile data for the thermodynamic properties of the amines which control gas/particle partitioning (Henry’s Law constant, liquid vapor pressure, acid dissociation constant, activity coefficient and solubility in water), and also estimate the solid/gas dissociation constants of their nitrate and chloride salts. Prediction methods for boiling point, liquid vapor pressure, acid dissociation constant and the solubility of the amines in water are evaluated, and used to estimate values of the equilibrium constants where experimental data are lacking. Partitioning of amines into aqueous aerosols is strongly dependent upon pH and is greatest for acidic aerosols. For several common amines the tendency to partition to the particle phase is similar to or greater than that of ammonia. Our results are presented as tables of values of thermodynamic equilibrium constants, which are also incorporated into the Extended Aerosol Inorganics Model (E-AIM, http://www.aim.env.uea.ac.uk/aim/aim.php) to enable gas/aerosol partitioning and other calculations to be carried out.

Research highlights

► Thermodynamic data of amines that controls gas/particle partitioning are compiled. ► Data includes HLC, vapor pressure, activity coefficient and aqueous solubility. ► Partitioning of amines into aqueous aerosols is strongly dependent upon pH. ► Amines can partition into the aerosol, similar to or greater than that of ammonia.

Introduction

Amines are emitted as gases into the atmosphere from a variety of sources, for example the low molecular weight aliphatic amines from animal husbandry operations and the ocean, and aromatic amines from various industrial operations, as summarized in Part I of this work (Ge et al., 2011). There is considerable interest in the use of amines as absorbers of CO2 from power generation (Vaidya and Kenig, 2007, Rivera-Tinoco and Bouallou, 2010). Amines are found in atmospheric condensed phases including aerosols, rainwater, and fogwater. Two pathways contribute to amine gas-to-particle conversion: direct dissolution due to their aqueous solubility, and acid-neutralizing reactions owing to their role as bases. However, amines are not usually incorporated as individual species, or as a class, into the atmospheric models used for calculations of gas/particle partitioning. Consequently, little is known about the role of amines in aerosol formation and behavior or the atmospheric conditions for which they may be important.

An accurate representation of the amines and their behavior in the atmosphere requires, first of all, a knowledge of the physical and thermodynamic properties which control their gas/particle partitioning. Here, we evaluate the Henry’s Law constants, vapor pressures, activity coefficients, aqueous dissociation constants and solubilities of a large number of amines which are known to occur in the atmosphere. Predictive methods for these properties are evaluated, and used to estimate values for the many compounds for which there are no data. Since amines are among the few atmospheric bases, their competition with ammonia for acidic molecules may be important, and we therefore estimate the dissociation constants (for gas/solid equilibrium) of atmospherically-relevant aminium nitrate and chloride salts and compare them with those of the corresponding ammonium salts. The results are being incorporated into the Extended Aerosol Inorganics Model (E-AIM) of Clegg and co-workers (Wexler and Clegg, 2002, and references therein) so that researchers can both interpret the results of laboratory experiments involving amines and investigate their probable atmospheric behavior.

Section snippets

Theory

The atmospheric partitioning of amines and aminium salts between the gas phase, aqueous phase in particles and droplets, and solid particles, is presented in Fig. 1. The system involves gas/aqueous, aqueous dissociation, solid/aqueous and solid/gas equilibria. The types of data needed to specify these equilibria are listed in Table 1.

Equilibrium constants vary with temperature according to the equation:ln(K(T))=ln(K(Tr))ΔrHo(1/T1/Tr)/R+ΔrCpo/R[Tr/T1+ln(T/Tr)]where K is the value of the

Data sources

The thermodynamic properties described in the previous section, for the total 187 amines in Tables 1 and 8 of Part I of this work (Ge et al., 2011), were collected from sources described below.

Experimental Henry’s Law constants of some common amines, such as methylamine (CH5N, MA), dimethylamine (C2H7N, DMA), trimethylamine (C3H9N, TMA), ethylamine (C2H7N, EA), diethylamine (C4H11N, DEA), and triethylamine (C6H15N, TEA), were taken from the NIST Chemistry WebBook (//webbook.nist.gov/chemistry

Estimation methods

In this section, different methods for estimating pure liquid or subcooled vapor pressures and infinite-dilution activity coefficients (for calculation of KH), aqueous acid dissociation constants (Ka), and solubility (for calculation of Ks) were evaluated, and then employed to estimate the properties for amines where measured values are not available.

The reliability of the methods is represented by the mean absolute error (MAE) and the mean bias error (MBE), defined byMAE=1ni|VEstVMeas|,MBE=1n

Partitioning of amines to the aerosol

Like ammonia, amines can be expected to partition into aqueous aerosols. Reactions with gas phase acids such as HNO3 and HCl to form solid aminium nitrate and/or chloride salts are also a possibility. Formation of solid nitrates and sulfates has been examined by Murphy et al. (2007), who demonstrate that amines can undergo similar acid–base reactions as ammonia to form atmospheric nitrate and sulfate salts in the presence of HNO3 or H2SO4. Below, we first predict the total solubility of amines

Summary

In this work the Henry’s Law constant, vapor pressure, activity coefficient, aqueous acid dissociation constant and solubility of atmospheric amines (154 amines, 32 amino acids and urea) have been evaluated and compiled. The available measurements are quite sparse, and a number of widely used estimation methods for vapor pressure, dissociation constant and solubility have been tested and then used to complete the data set. The results have been included in the Extended Aerosol Inorganics Model,

Acknowledgements

The work was supported by the Electric Power Research Institute.

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