Atmospheric Environment xxx (2010) 1e17

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Atmospheric Environment
journal homepage: www.elsevier.com/locate/atmosenv

Atmospheric amines e Part II. Thermodynamic properties

and gas/particle partitioning
Xinlei Ge a, *, Anthony S. Wexler a, Simon L. Clegg a, b, **
a
Air Quality Research Center, University of California, Davis, CA 95616, USA
b
School of Environmental Sciences, University of East Anglia, Norwich NR4 7TJ, UK

a r t i c l e i n f o a b s t r a c t

Article history: Amines enter the atmosphere from a wide range of sources, but relatively little is known about their
Received 28 June 2010 atmospheric behavior, especially their role in gas/particle partitioning. In Part I of this work (Ge et al.,
Received in revised form 2010) a total of 154 amines, 32 amino acids and urea were identified as occurring in the atmosphere,
5 October 2010
based upon a survey of the literature. In this work we compile data for the thermodynamic properties of
Accepted 8 October 2010
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
Keywords:
dissociation constants of their nitrate and chloride salts. Prediction methods for boiling point, liquid
Amines
Amino acids
vapor pressure, acid dissociation constant and the solubility of the amines in water are evaluated, and
Vapor pressure used to estimate values of the equilibrium constants where experimental data are lacking. Partitioning of
Dissociation constant amines into aqueous aerosols is strongly dependent upon pH and is greatest for acidic aerosols. For
Thermodynamic model several common amines the tendency to partition to the particle phase is similar to or greater than that
Gas/particle partitioning 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.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction An accurate representation of the amines and their behavior in the

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., 2010). 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, rain-
water, 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 calcu-
lations 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.
atmosphere requires, first of all, a knowledge of the physical and
thermodynamic properties which control their gas/particle parti-
tioning. Here, we evaluate the Henry’s Law constants, vapor pres-
sures, 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 evalu-
ated, 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.

* Corresponding author.
** Corresponding author. School of Environmental Sciences, University of East
Anglia, Norwich NR4 7TJ, UK. Tel.: þ44 1603 593185; fax: þ44 1603 591327.
E-mail addresses: xlge@ucdavis.edu (X. Ge), S.Clegg@uea.ac.uk (S.L. Clegg).
2. Theory
The atmospheric partitioning of amines and aminium salts
between the gas phase, aqueous phase in particles and droplets,

1352-2310/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.atmosenv.2010.10.013

Please cite this article in press as: Ge, X., et al., Atmospheric amines e Part II. Thermodynamic properties and gas/particle partitioning,
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2 X. Ge et al. / Atmospheric Environment xxx (2010) 1e17

2.1. Gas/aqueous equilibrium

Gas Total: 187
In the atmosphere, the partitioning of gaseous amines into the
KH or po aqueous phase of aerosol is driven by the Henry’s Law reaction:
(po: 58; KH: 64 )
Rn NH3nðgÞ #Rn NH3nðaqÞ (2)

Gas/aqueous eql. Gas/solid eql. where n ¼ 1, 2 or 3 signifies primary, secondary or tertiary amine
and n ¼ 0 corresponds to ammonia.
Kp
(KH or p0) The Henry’s Law constant on a molality basis (KH, in
and Ka : 69 Gas/aqueous mol kg1 atm1) is given by:
/solid eql.

(KH or p0) KH ðRn NH3n Þ ¼ aRn NH3n =pRn NH3n (3a)

Ka , and Ks: 31 Ks: 71
Ka : 135
Solid/aqueous eql.
Ka and Ks:
Aqueous 63 Solid
Fig. 1. The equilibrium constants and physical properties that control equilibrium
between gas, aqueous and solid phases: KH e Henry’s Law constant (equation (3)), po e
vapor pressure of the pure liquid or subcooled amine, Ka e acid dissociation constant of
the amine cation (equation (8)), Ks e activity of the amine in an aqueous solution
saturated with respect to the solid (equation (12)), Kp e vapor pressure product of the
amine and HNO3 or HCl over the solid amine nitrate or chloride salt. The numbers of
amines for which measured values of each constant available are shown.
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:
lnðKðTÞÞ ¼ lnðKðTr ÞÞ  Dr Ho ð1=T  1=Tr Þ=R
þ Dr Cpo =R½Tr =T  1 þ lnðT=Tr Þ (1)
where K is the value of the equilibrium constant at the specified
temperature T (K), Tr is the reference temperature of 298.15 K, DrHo
(kJ mol1) is the enthalpy change for the reaction at the reference
temperature, Dr Cpo (J mol1 K1) is the change in heat capacity, and
R is the gas constant (8.3144 J mol1 K1). The above equation
assumes that Dr Cpo is invariant with temperature. Where this is not
the case, there are additional terms (Sandler, 2006).
In this work, equilibrium constants (K) that involve reactants or
products in the liquid phase are generally expressed on a molality
basis (moles per kg of the solvent, water). Conversions to a mole
fraction basis (xK) were carried out, where necessary, using
expressions given by Robinson and Stokes (1965).
Details of the key equilibria are given below:
¼ mRn NH3n $gRn NH3n =pRn NH3n (3b)
1
where prefix a indicates activity, m molality (mol kg ), and p
partial pressure (atm). The symbol gRn NH3n is the molality-based
activity coefficient. The product of the molality and activity coef-
ficient of the amine is its activity.
The Henry’s Law reaction can also be written on a mole fraction
basis:
x
KH ðRn NH3n Þ ¼ xRn NH3n $fR*n NH3n =pRn NH3n (4)
where xKH (atm1) is the mole fraction Henry’s Law constant, prefix
x indicates mole fraction, and fR*n NH3n is the mole fraction activity
coefficient relative to a reference state of infinite dilution in water,
so that fR*n NH3n /1:0 as xRnNH3n / 0.0 in pure water. The values
of KH and xKH are related by KH ¼ xKH$(1000/Mw), where Mw is the
molar mass of water in grams (Robinson and Stokes, 1965).
Gas/liquid equilibrium can also be expressed in terms of an
equation that includes the pure liquid vapor pressure of the
compound:
pRn NH3n ¼ xRn NH3n $fRn NH3n $po Rn NH3n (5)
where fRn NH3n is the mole fraction activity coefficient of RnNH3n
relative to the pure liquid reference state, so that fRn NH3n /1:0 as
xRnNH3n / 1.0, and poRnNH3n is vapor pressure of pure liquid
RnNH3n.. Considering the case of an infinitely dilute solution of
RnNH3n (for which fR*n NH3n ¼ 1:0), equations (4) and (5) yield the
relationship between the pure liquid vapor pressure and Henry's
Law constant:
. 
x
KH ðRn NH3n Þ ¼ 1 fRNn NH3n $po Rn NH3n (6)
where fRNn NH3n is the mole fraction activity coefficient of RnNH3n at
infinite dilution in water, relative to a reference state of the pure
liquid. The value of poRnNH3n should be evaluated for the subcooled
liquid if the normal melting point is above the temperature of interest.
2.2. Aqueous dissociation equilibrium

Amines are weak bases in aqueous solution, and the equilibrium

Table 1 with dissolved Hþ
ðaqÞ can be expressed as the acid dissociation of
Equilibrium constants required for atmospheric amines. aminium ions:

Rn NHþ þ
Equilibrium Constant Description
4nðaqÞ #Rn NH3nðaqÞ þ HðaqÞ (7)
Gas/aqueous KH or po Henry’s Law constant or pure liquid
equilibrium (or subcooled) vapor pressure
 
Ka Rn NHþ ¼ aRn NH3n $aHþ =aRn NHþ
Aqueous dissociation Ka (Ka1 First and second acid dissociation constants
4n 4n (8a)
and Ka2) in water
Solid/aqueous Ks Activity product of the amine in a solution
equilibrium saturated with respect to the solid   
Solid/gas equilibrium Kp Dissociation constant of solid aminium nitrate ¼ mRn NH3n $mHþ =mRn NHþ
4n gRn NH3n $gHþ =gRn NHþ 4n
or chloride (to form the gas phase amine
and HNO3 or HCl) (8b)

Please cite this article in press as: Ge, X., et al., Atmospheric amines e Part II. Thermodynamic properties and gas/particle partitioning,
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 X. Ge et al. / Atmospheric Environment xxx (2010) 1e17 3

where Ka (mol kg1) is the acid dissociation constant and prefix 2.5. Solid/aqueous equilibrium of aminium salts
a represents activity on the molality basis. The term in the first
parentheses in equation (8b) is sometimes referred as the stoi- The salt aerosols formed from reactions described above may be
chiometric dissociation constant (Ka* ). This involves only molalities, aqueous or solid depending on the ambient relative humidity and
and varies with solution composition (which affects the activity temperature. The equilibrium between the solid monovalent salt
coefficients). The equation for the base dissociation of an amine is: and aqueous ions is expressed as:

Rn NH3nðaqÞ þ H2 OðlÞ #Rn NHþ
4nðaqÞ þ OHðaqÞ (9) Rn NH4n XðsÞ #Rn NHþ 
4nðaqÞ þ XðaqÞ (17)

   .  
Kb Rn NHþ ¼ aRn NHþ 
aRn NH3n $aH2 O KS ðRn NH4n XÞ ¼ aRn NHþ
4n $aX

aRn NH4n X (18a)
4n 4n $aOH

(10a)   
¼ mRn NHþ
4n $mX

gRn NHþ4n $gX (18b)
 

¼ mRn NHþ
4n $mOH =mR n NH3n where KS(RnNH4nX) (mol2 kg2) is the activity product of the salt
   (and the activity of the pure solid is unity in equation (18a)). The
 gRn NHþ $gOH gRn NH3n $aH2 O (10b) values of ion activity coefficients in equation (18b) are functions of
4n

the concentration and composition of the aqueous phase, resulting

where Kb (mol kg1) is the base dissociation constant, for which the
in solubilities that may vary strongly depending on the type of
stoichiometric value (Kb* ) is the first term in parentheses in equa-
aerosol solution that the salt is dissolved in, and ambient condi-
tion (10b). Values of Ka and Kb are related to the dissociation
tions. The analogous equation for KS for an aminium sulfate is:
constant of water (Kw, in units of mol2 kg2, for the reaction
  2
H2 OðlÞ #Hþ
ðaqÞ þ OHðaqÞ ) by Ka$Kb ¼ Kw.   
KS ðRn NH4n Þ2 SO4 ¼ aRn NHþ
4n $aSO2
4 aðRn NH4n Þ2 SO4
2.3. Solid/aqueous equilibrium (19a)

Water soluble amines in atmospheric aerosols may form solids h 2 i h 2 i

from their saturated solutions at relative humidities below their ¼ mRn NHþ
4n $mSO2
4 $ gRn NHþ $gSO2 (19b)
4n 4

deliquescence points. In most cases these solids are anhydrous. The

where KS((RnNH4n)2SO4) has units of mol3 kg3.
equilibrium between the solid and the amine in a saturated
aqueous solution is:

Rn NH3nðsÞ #Rn NH3nðaqÞ (11) 2.6. Solid/aqueous/gas equilibrium

 To our knowledge, values of the solid/gas equilibrium constant

KS ðRn NH3n Þ ¼ aRn NH3nðaqÞ aRn NH3nðsÞ
¼ mRn NH3n $gRn NH3n (12)
where mRnNH3n is the solubility of the amine in water at the
temperature of interest, gRn NH3n is its activity coefficient, and
KS(RnNH3n) is the activity product of the solid amine. Note that the
activity of a pure solid phase (i.e., aRnNH3n(s)) is unity by
definition.
Kp of aminium chloride and nitrate salts have not been measured.
However, these can be estimated from the equilibrium constants
defined above by considering a system in which solid aminium salt,
a solution containing the dissolved salt and parent amine, and the
gas phase amine, are all at equilibrium.
First, we define the Henry’s law constant for the monovalent
strong acid HX (KH, in mol2 kg2 atm1) in terms of the equilibrium
between the gas phase molecule and aqueous ions:

2.4. Solid/gas equilibrium of aminium salts HXðgÞ #Hþ 

ðaqÞ þ XðaqÞ (20)

Besides their direct absorption into aqueous aerosols, gaseous  .

KH ðHXÞ ¼ aHþ $aX pHX (21a)
amines are able to react with gas phase acids, chiefly HNO3, HCl or
H2SO4, to form solid aminium salts in the particulate phase (s). The
  
equilibrium with a monovalent acid HX is given by: ¼ mHþ $mX =pHX gHþ $gX (21b)
Rn NH4n XðsÞ #Rn NH3nðgÞ þ HXðgÞ (13)
Combining equations (3), (8), (16) and (18), the solid/gas equi-
librium constant Kp for the amine salt RnNH4nX can be written as:
Kp ¼ pRn NH3n $pHX (14)
   .  
2
where Kp (atm ) is the solid/gas equilibrium constant (or dissoci- Kp ¼ KS Rn NH4n X $Ka Rn NHþ
4n KH ðRn NH3n Þ$KH ðHX
ation constant) of the aminium salt. In reactions with H2SO4 the
(22)
corresponding equations are:
It is clear from this equation that the only property of the salt
ðRn NH4n Þ2 SO4ðsÞ #2Rn NH3nðgÞ þ H2 SO4ðgÞ (15) that is needed to obtain Kp is its activity product in a saturated
solution (equation (18)). This is determined from its solubility in
water at the temperature of interest, and the activity coefficients of
Kp ¼ ðpRn NH3n Þ2 $pH2 SO4 (16) 
the ions Rn NHþ 4n and X . We note that activity coefficients in
3
where Kp has units of atm . Units of Pa (1 atm ¼ 101.325 kPa) are aqueous solutions of the aminium salts are rarely measured, in
also used in this work for Kp, in order to aid comparisons with the which case either the stoichiometric value of KS(RnNH4nX)
results of other studies. (the term in first parentheses in equation (18b)) can be used as

Please cite this article in press as: Ge, X., et al., Atmospheric amines e Part II. Thermodynamic properties and gas/particle partitioning,
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4 X. Ge et al. / Atmospheric Environment xxx (2010) 1e17
a first approximation, or some assumption must be made about
gRn NHþ and gX .
4n
3. Thermodynamic properties of amines
3.1. 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., 2010), 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), diethyl-
amine (C4H11N, DEA), and triethylamine (C6H15N, TEA), were taken
from the NIST Chemistry WebBook (http://webbook.nist.gov/
chemistry). Values from studies that also list the dependence of
KH on temperature were given preference in cases where experi-
mental values differed. Henry’s Law constants were also taken from
the International Critical Tables (1926e1930), Nirmalakhandan
et al. (1997), Brenna et al. (1998), Altschuh et al. (1999), and Yaws
(2008). Values are expressed in many different forms and units,
and were converted to units of mol kg1 atm1. In cases where large
differences were found between KH from different sources we did
not attempt to evaluate the data, but adopted the value measured
most recently.
Measured vapor pressures of the pure liquids (po) were taken
from the Dortmund Databank (2009). Some values were also
obtained from Yaws (2007) and/or the NIST Chemistry WebBook. In
both compilations the values of po are presented in the form of an
Antoine equation, log10(po) ¼ A  B/(T þ C).
Acid dissociation constants of the aminium ions, Ka (equation
(8)), were taken mainly from Lide (2009) and the International
Critical Tables (1926e1930), with some additional values from the
database of Advanced Chemistry Developments which is associated
with their ACD/pKa software (Version 12.01, May 27, 2009).
Experimental solubilities of the amines in water were collected
from Yalkowsky and He (2003), Yaws (2008), Lide (2009) and the
Advanced Chemistry Developments solubility database (Version
12.01, May 27, 2009).
Data for solid/gas dissociation constants Kp, and solubilities of
aminium salts, are discussed individually in section 5.
3.2. Data availability
The extent of the available data at or close to 298.15 K is shown
in Fig. 1 for each of the key equilibria. The equilibrium constants
governing gas/aqueous equilibrium indicated in Fig. 1 include
directly measured Henry’s Law constants (64 compounds), and
measured liquid vapor pressures (58 compounds) that can be
converted to Henry’s Law constants via equation (6). Dissociation
constants Ka have been quite extensively measured (135
compounds), while Ks data are sparse (only 71 compounds with
solubility data that can be used to obtain the Ks values).
It is clear from Fig. 1 that for only 31 compounds are Henry’s Law
constants, acid dissociation constants, and measured solubilities in
water all available. For practical atmospheric calculations in which
many more compounds may be of interest, it is necessary to use
estimation methods for properties that have not been measured. In
the following section we evaluate estimation methods for each of
the properties KH, Ka and Ks against available data.
4. Estimation methods
In this section, different methods for estimating pure liquid or
subcooled vapor pressures and infinite-dilution activity coefficients
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Atmospheric Environment (2010), doi:10.1016/j.atmosenv.2010.10.013
(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 by
1 X  Est  1 X Est 

MAE ¼ V  V Meas ; MBE ¼ V  V Meas
n i n i
(23)
o
where V represents a physical property, for instance p , Ka, activity
coefficient or solubility. “Est” and “Meas” refer to the estimated and
measured values, respectively. For this analysis, the total of 187
amines was divided into six categories: monoamine, diamine,
alcohol amine, amide, other amine (with other functional groups,
such as eCl, eNO2, etc.) and amino acids.
Estimation of po typically requires a normal boiling point (Tb),
which in many cases also needs to be estimated. Clegg et al. (2008b)
have shown that typical errors and uncertainties in Tb can result in
very large errors in predicted po values, up to factors about 20.
Methods of predicting Tb are also examined in this section.
4.1. Boiling points
A total of 111 measured boiling points were obtained from the
NIST Chemistry WebBook (some of which are given as the average
of two or more measurements), Lide (2009), and the International
Critical Tables (1926e1930). Fig. 2a and b compare the measured Tb
values to those predicted using the methods of Nannoolal et al.
(2004) and Stein and Brown (1994). In Fig. 2c we show results
obtained from the software package ACDLabs (Version 12.01, May
27, 2009, Advanced Chemistry Developments Inc.). This uses an
empirical additive-constitutive method which interpolates or
extrapolates, based on the compound’s structure, from a large
number of known values (Kolovanov et al., undated). Note that the
values plotted in Fig. 2c are true predictions, and are not drawn
from the ACD internal database which is likely to contain many of
the amines of interest here.
Results of the comparisons of measured and predicted boiling
points of the amines are listed in Table 2. The mean absolute error
(MAE) of the method of Nannoolal et al. (2004) is 9.51 K, which is
smaller than the MAE of 14.25 K for the method of Stein and Brown
(1994). The method of Nannoolal et al. also yields a smaller negative
bias (mean bias error, or MBE, equal to 0.90 K) compared to
3.32 K for the method of Stein and Brown (1994). The MAE of the
method of Stein and Brown (1994) is larger than the value of 9.5 K
reported by Camredon and Aumont (2006) for their group of
organic compounds, but much lower than the 28.9 K given by Stein
and Brown (1994) for a large and diverse set of 4280 compounds.
The results we obtained with the ACD method e MAE equal to
4.97 K, and MBE equal to 1.31 K e show that the ACD algorithm for
Tb estimation yields more accurate results than both of the other
methods.
Of the different kinds of amines listed in Table 2, the Tb of the
simple monoamines are predicted most accurately, except in
the case of the ACD model which yields slightly better results for
the diamines. This is to be expected, because it is likely that boiling
points of these simple compounds have been used to fit the
parameters in the model. For alcohol amines, ACD estimates are less
accurate than those of the method of Nannoolal et al. (2004), but
are much better for other kinds of amines.
In this study the ACD method is used to estimate Tb values for
compounds for which measured boiling points are not available.
 X. Ge et al. / Atmospheric Environment xxx (2010) 1e17 5

compounds with the low (1e103 Pa) and very low (<1 Pa) vapor
a 700
pressures that are typical of compounds that undergo significant
gas/particle partitioning in the atmosphere.
600 Camredon and Aumont (2006) have tested a number of struc-
ture-based predictive methods for boiling point (Tb), vapor pres-
sures (po), and enthalpies of vaporization (DHvap 0 , used to estimate
500
Tb (Est.) / K

vapor pressures at other temperatures). On the basis of tests using

compounds such as alcohols, ketones, and aldehydes, they rec-
400 ommended the UNIFAC e poL equation of Asher et al. (2002), and
equation of Myrdal and Yalkowsky (1997) coupled with the boiling
300 point predictor of Joback and Reid (1987) for predicting vapor
pressures. However, they note that the equation of Asher et al.
(2002) is not applicable to a wide range of compounds.
200 Recently, Barley and McFiggans (2010) have carried out
200 300 400 500 600 700
a broader evaluation, testing four equations for vapor pressures
Tb (Meas.) / K coupled with three different boiling point prediction methods. For
Tb estimation they recommend the method of Nannoolal et al.
b 700 (2004), and that of Stein and Brown (1994) as a second choice.
Their comparisons of measured and predicted vapor pressures
showed that the methods of Nannoolal et al. (2008) and Moller
600 et al. (2008) yielded comparable results, and were better than the
other po predictors studied when used with the Nannoolal et al.
Tb (Est.) / K

500 (2004) Tb predictor.

The equation of Moller et al. (2008) includes terms for interactions
between multiple functional groups present in a molecule and was
400 found to yield improved predictions, relative to the earlier equation of
Nannoolal et al. (2008), for compounds with very low vapor pres-
300 sures. However, it has been shown that the way in which these group
interactions are expressed in the equation of Moller et al. (2008) can
lead to large errors in predicted vapor pressures for molecules con-
200 taining multiple functional groups (Barley, personal communication).
200 300 400 500 600 700
The equation has recently been modified to correct for this (Moller
Tb (Meas.) / K et al., 2010). The Myrdal and Yalkowsky (1997) equation for vapor
pressure, coupled with boiling points predicted by either the Stein
c 700 and Brown (1994) or Nannoolal et al. (2004) methods, was also
found to yield good results by Barley and McFiggans (2010).
600 Neither of the sets of vapor pressures used as test data by
Camredon and Aumont (2006) and Barley and McFiggans (2010)
include amines. Accordingly, we have tested the equations of
Tb (Est.) / K

500 Moller et al. (2008), Nannoolal et al. (2008) and Myrdal and
Yalkowsky (1997), coupled with the Stein and Brown (1994),
400 Nannoolal et al. (2004) and ACD boiling point predictors, against
datasets of measured vapor pressures of a range of amines. The
results are described below, and summarized in Table 2.
300 Vapor pressures of 58 amines predicted using measured boiling
points and the equations of Moller et al. (2008), Nannoolal et al.
200 (2008) and Myrdal and Yalkowsky (1997) are shown in Fig. 3. The
200 300 400 500 600 700 three equations yield quite similar estimates, with relatively low
Tb (Meas.) / K MAEs of 0.104e0.120 in log10(po) (corresponding to factors of
1.27e1.32). Predicted po values tend to be high, but with only
Fig. 2. Measured (Tb(Meas.)) and estimated (Tb(Est.)) boiling points. Symbols: C,
a small positive systematic bias of 0.032e0.072 in log10(po). The
monoamine; þ, diamine; 7, alcohol amine; , other amine; ,, amide. Estimation
methods, numbers of values (N) and overall errors: (a) Nannoolal et al. (2004)  N ¼ 105, performance of all three methods is poorest for the alcohol amines,
MAE ¼ 9.51 K, MBE ¼ 0.90 K; (b) Stein and Brown (1994)  N ¼ 102, MAE ¼ 14.25 K, as shown in Table 2. This is consistent with general experience that
MBE ¼ 3.32 K; (c) ACD (2009)  N ¼ 111, MAE ¼ 4.97 K, MBE ¼ 1.31 K. the vapor pressures of compounds containing polar functional
groups, such as eOH and eCOOH, are the most difficult to predict.
Camredon and Aumont (2006) found that vapor pressures
4.2. Vapor pressure predicted using the equation of Myrdal and Yalkowsky (1997) did
not show significant systematic bias and concluded that it was
Amines identified in the atmosphere cover a wide range of suitable for extrapolation to very low vapor pressures. Our results
carbon numbers and their pure liquid or subcooled vapor pressure using the Myrdal and Yalkowsky (1997) method for amines in the
(po) values at 298.15 K vary commensurately, from above 1 atm to range of po < 104 atm (Fig. 3c) are generally consistent with this,
below 105 atm. However, the vast majority of reliable experi- although there are only 6 compounds with these very low vapor
mental po data e measured mainly for applications in the chemical pressures. We note that vapor pressure of the compound subject to
industry e are for compounds with intermediate values of about the largest overestimates in Fig. 3, glycolamine, was obtained using
103e105 Pa (1 atm ¼ 101.325 kPa). There are very few data for the Antoine equation (Yaws, 2007) and may be too low: the

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Table 2
The mean absolute error (MAE) and mean bias error (MBE) of boiling points (Tb) and vapor pressures of the pure liquids (po) calculated by different methods.

Properties Estimation methods

MAE MBE MAE MBE MAE MBE

Tb Nannoolal et al. (2004) a Stein and Brown (1994) b ACD (2009)
Overall 9.51 0.90 14.25 3.32 4.97 1.31
Monoamine (61) 8.83 1.31 11.09 1.82 3.91 0.63
Diamine (16) 10.98 4.97 17.82 9.29 3.86 0.70
Alcohol amine (10) 9.39 3.66 21.42 17.06 11.06 9.03
Other amine (15) 9.28 2.11 13.49 2.06 6.28 1.83
Amide (9) 12.38 6.22 23.61 21.87 5.21 0.02

log10(po) Moller et al. (2008) Nannoolal et al. (2008) Myrdal and Yalkowsky (1997)
Overall 0.113 0.032 0.104 0.072 0.120 0.062
Monoamine (46) 0.088 0.038 0.081 0.061 0.096 0.043
Diamine (3) 0.079 0.041 0.043 0.028 0.093 0.093
Alcohol amine (4) 0.552 0.202 0.596 0.556 0.608 0.501
Other amine (3) 0.025 0.008 0.020 0.020 0.027 0.002
Amide (2) 0.146 0.146 0.099 0.078 0.039 0.039

Note: The numbers in parentheses are the numbers of data values in each category, except as noted.
a
Numbers of data values for diamine, alcohol amine and other amine are 13, 9 and 13, respectively.
b
Numbers of data values for monoamine, diamine, alcohol amine and other amine are 59, 13, 9, and 12.

measured po of 3.948  102 atm at 405.31 K (Dortmund Databank, same or very similar values. If there are large differences, the data
2009) is close to estimates of 4.2538  102, 4.5052  102 and published later were preferred. Estimates were obtained using the
4.7799  102 atm by the three methods, while the value of equation of Moller et al. (2008). For compounds without measured
1.2832  102 atm at 405.31 K from Yaws (2007) is much lower. enthalpies of vaporization, these estimates were adopted. For cases
The vapor pressure equations of Moller et al. (2008) and where heat capacity measurements were lacking, values were
Nannoolal et al. (2008) both predict po more accurately than the predicted by the method of Myrdal and Yalkowsky (1997).
equation of Myrdal and Yalkowsky (1997). Of the 58 compounds
tested, the equation of Nannoolal et al. (2008) predicted the vapor
pressures of 34 compounds more accurately than the equation of 4.3. Acid dissociation constants
Moller et al. (2008). However, the latter yields a smaller overall
MBE (0.032 versus 0.072). Values of the acid dissociation constants of the amine cations,
How do results differ when predicted rather than measured Tb equation (8), are often expressed as the pKa, defined as:
values are coupled with the vapor pressure prediction equations?  
Table 3 lists the overall mean absolute and bias errors for the three pKa ¼ log10 aRn NH3n $aHþ = aRn NHþ
4n (24a)
vapor pressure equations when used with the different Tb predic-
tors. All the mean absolute errors (MAE) in log10(po) obtained by h  
using different Tb predictors are larger than the values using ¼ log10 mRn NH3n $mHþ mRn NHþ
4n
measured boiling points, as expected. The MAE for the three vapor   i
pressure equations are quite similar for each boiling point
 gRn NH3n $gHþ gRn NHþ (24b)
4n

predictor, with the ACD method yielding the lowest values by

Similarly, pKb is negative log10 of the equilibrium constant
a small margin. In the case of the mean bias error (MBE), the vapor
defined by equation (10), and the two values are related by:
pressure equation of Moller et al. (2008) yields smaller values than
pKa þ pKb ¼ log10(Kw).
that of Nannoolal et al. (2008) which is consistent with the results
For amines with two NH3n groups, such as 1,4-butanediamine
in Table 2 for measured vapor pressures. This result does not
(C4H12N2), we define two stepwise dissociation constants:
change our conclusions about the relative merits of the different
equations, but does emphasize the importance of a reliable Tb for H2 NðCH2 Þ4 NHþ þ
3ðaqÞ #H2 NðCH2 Þ4 NH2ðaqÞ þ HðaqÞ (25a)
the accurate prediction of po.
The vapor pressures of amines at 298.15 K that have been
adopted in this work were selected in the following order of pref-
þ
H3 NðCH2 Þ4 NHþ þ þ
3ðaqÞ #H2 NðCH2 Þ4 NH3ðaqÞ þ HðaqÞ (25b)
erence: (i) measurements from the Dortmund Databank (2009); (ii)
values calculated from Antoine parameters provided by Yaws where the first dissociation constant, Ka1 (mol kg1), for the reac-
(2007) and the NIST Chemistry WebBook; (iii) estimates using tion (25a) is analogous to that defined in equation (24). The second
the equation of Moller et al. (2008) and measured Tb; (iv) estimates stepwise dissociation constant is, for the reaction (25b), given by:
using the equation of Moller et al. (2008) and Tb predicted by the  
model of Advanced Chemistry Developments. Ka2 ¼ aH2 NðCH2 Þ4 NHþ þ
3 $aH =a
þ
H3 NðCH2 Þ4 NHþ
3 (26)
We note that common amino acids can sublime or decompose at
We note that it is also possible to express the dissociation to
450e600 K, so that measurements of boiling temperature are not
obtain the divalent cation in a single step:
available. Calculated po for amino acids at 298.15 K are typically
below 105 atm. þ
H3 NðCH2 Þ4 NHþ þ
3ðaqÞ #H2 NðCH2 Þ4 NH2ðaqÞ þ 2HðaqÞ (27)
A total of 65 enthalpies of vaporization at 298.15 K were
collected from the Dortmund Databank (2009), the NIST Chemistry The equilibrium constant for this reaction, which we denote Kd2
WebBook and Lide (2009). Generally, the three sources provide the (mol2 kg2) is equal to Ka1$Ka2.

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 X. Ge et al. / Atmospheric Environment xxx (2010) 1e17 7

Table 3
a 0 The mean absolute error (MAE) and mean bias error (MBE) of different vapor
pressure (po) estimation methods coupled with different boiling point (Tb)
-1 predictors.

Errors po method Tb method

log10 p (Est.) / atm

-2 ACD, 2009 Nannoolal Stein and

et al., 2004 Brown, 1994
-3 MAE Moller et al., 2008 0.142 0.164 0.267
Nannoolal et al., 2008 0.153 0.183 0.263
o

-4 Myrdal and Yalkowsky, 0.166 0.187 0.280

1997

-5 MBE Moller et al., 2008 0.063 0.0025 0.041

Nannoolal et al., 2008 0.097 0.02 0.076
Myrdal and Yalkowsky, 0.087 0.029 0.063
-6 1997
-6 -5 -4 -3 -2 -1 0
o
log10 p (Meas.) / atm

b 0 For these compounds, the first dissociation of the amine cation,

with equilibrium constant Ka1, involves the carboxylic acid group:
-1 þ
H3 NRCOOHðaqÞ #þ H3 NRCOO þ
ðaqÞ þ HðaqÞ (28)
log10 p (Est.) / atm

-2 The second dissociation (Ka2) is that of the amine group:

-3 þ
H3 NRCOO  þ
ðaqÞ #H2 NRCOOðaqÞ þ HðaqÞ (29)
o

-4 Further acid dissociation constants (Ka3, Ka4 etc.) are assigned to

any dissociating groups present in the side chain, R.
-5 Although pKa values are the most widely available measured
property for the amines (Fig. 1), there is still a need to estimate
-6 values for some compounds. In order to do this, we have used the
-6 -5 -4 -3 -2 -1 0 Advanced Chemistry Development ACD/pKa module (Version 12.01,
o
log10 p (Meas.) / atm May 27, 2009). This module uses the Hammett equation, a param-
eterization that covers the most common functional groups, each of
which is characterized in the algorithm by several equations
c 0
involving different types of substituent constants. The method has
recently been used for pKa predictions of the amines used in CO2
-1
post-combustion capture (Puxty et al., 2009).
log10 p (Est.) / atm

Fig. 4 illustrates the performance of the ACD/pKa predictor for

-2 atmospheric amines. Comparisons are shown only for the first and
second pKa values. The estimated pKa1 for both amines and amino
-3 acids generally agree well with measurements, with an overall MAE
o

of 0.184 (a factor of 1.53), and show no significant systematic bias

-4
-5
-6
-6 -5 -4 -3 -2 -1
o measurements, e.g. a factor of two for 2,4-dimethylaniline (an
log10 p (Meas.) / atm
Fig. 3. Measured (po(Meas.)) and estimated (po(Est.)) vapor pressures. Symbols: C,
monoamine; þ, diamine; 7, alcohol amine; , other amine; ,, amide. Estimation
methods, numbers of values (N) and overall errors: (a) Moller et al. (2008) e N ¼ 58,
MAE ¼ 0.113, MBE ¼ 0.032; (b) Nannoolal et al. (2008) e N ¼ 58, MAE ¼ 0.104,
MBE ¼ 0.072; (c) Myrdal and Yalkowsky (1997) e N ¼ 58, MAE ¼ 0.120, MBE ¼ 0.062.
Amino acids are molecules that contain an amine group,
a carboxylic acid group and a side chain (R) that may contain other
dissociating functional groups. They are amphoteric and are
internal salts, existing as dipolar ions in the solution (zwitterions)
which carry both a positive and a negative charge located on
different groups of the same molecule (Greenberg, 1951). The
concentration of the undissociated form (NH2RCOOH) in water can
be neglected, since it is almost completely converted to the ionic
species (Greenberg, 1951; Tseng et al., 2009).
(MBE of 0.001). Of the different kinds of amines, the pKa1 of the
diamines are predicted least accurately.
The performance degrades somewhat for prediction of pKa2
values, with a larger MAE of 0.31 (within a factor of 2.04) and MBE
of 0.060. Considering the significant uncertainty in the
0
average value is used for this compound), the estimated pKa2 values
are satisfactory.
Note the alcohol group usually does not dissociate, but for a few
alcohol amines, there are available measured Ka2 values for the
equilibrium: H2NROH 4 H2NRO þ Hþ, which are also shown in
Fig. 4b.
The ACD/pKa model only predicts dissociation constants at
298.15 K. In order to obtain values at other temperatures, an esti-
mate of DrHo for the dissociation reaction is required. For some
common atmospherically-relevant amines, including MA and DMA,
we have been able to determine DrHo from experimental dissoci-
ation constants at different temperatures (see “Supplementary
data”). The dissociation constants increase with temperature. The
DrHo values for the first dissociation of simple straight-chain
amines lie in the range 55e60 kJ mol1, while those of secondary
and tertiary amines are lower (from about 40 to 50 kJ mol1). The
variation of the dissociation constants with temperature is

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8 X. Ge et al. / Atmospheric Environment xxx (2010) 1e17

determined from literature data over many years. In this work,

a 12
parameters reported by Hansen et al. (1991), Wittig et al. (2003),
Balslev and Abildskov (2002) and Peng et al. (2001) are used. For
molecules that contain functional groups that are not present in
8 UNIFAC, an activity coefficient of unity is assumed.
Infinite-dilution activity coefficients f N are useful for the esti-
pKa1 (ACD)

mation of Henry’s Law constants from pure liquid vapor pressures

using equation (6). In Fig. 5 we compare some UNIFAC-calculated
4 f N with measured values, mainly for 298.15 K but with several
values at 293.15 K. Data are scarce: only 22 monoamine measure-
ments were collected from the Dortmund Databank (2009),
Christie and Crisp (1967), Mitchell and Jurs (1998), Sherman et al.
0 (1996), and Giralt et al. (2004). On average, UNIFAC estimates
correlate well with the measurements, with a MAE of 0.246 in
0 4 8 12 log10(fN). However, sometimes there is substantial disagreement.
pKa1 (Meas.) For example, for tripropylamine the estimated f N of 5881 is much
less than the measured value of 19869 (Dortmund Databank, 2009).
This may not be entirely due to the model because measurements
b
are sometimes discordant: tributylamine (10705 and 17135 at
12 293.15 K) and 1-heptanamine (429 and 1593.1 at 298.15 K)
(Dortmund Databank, 2009).
pKa2 (ACD)

8 4.5. Solubility and activity product

There are few solubility data, and the Advanced Chemistry

4 Development ACD/Solubility module (Version 12.01, May 27, 2009)
has therefore been used to predict amine solubilities in pure
(unbuffered) water. Fig. 6 compares measurements to these
0 predictions. There is a high degree of scatter, even for compounds
0 4 8 12 with quite high solubilities, and predictions for the amino acids are
pKa2 (Meas.) particularly poor. However, because amines will usually be present
in atmospheric aerosols at very low concentrations, and neutralized
Fig. 4. Values of the pKa at 298.15 K predicted by the ACD/pKa module plotted against to cationic form, solubilities are only of limited relevance to the gas/
measured values for the following compound types: C, monoamine; ﹢, diamine; 7, particle partitioning of amines. In the absence of other suitable
alcohol amine; , other amine; 7, amino acid; ,, amide. (a) pKa1. Total number of methods, we have used the ACD module to predict solubilities for
amines (N) ¼ 131, MAE ¼ 0.184, MBE ¼ 0.001 (N (monoamine) ¼ 52, MAE ¼ 0.132,
amines for which there are no measurements.
MBE ¼ 0.004; N (diamine) ¼ 16, MAE ¼ 0.349, MBE ¼ 0.094; N (alcohol amine) ¼ 12,
MAE ¼ 0.240, MBE ¼ 0.045; N (other amine) ¼ 16, MAE ¼ 0.178, MBE ¼ 0.038; N (amino By using UNIFAC to estimate the activity coefficient at the
acid) ¼ 28, MAE ¼ 0.174, MBE ¼ 0.045; N (amide) ¼ 7, MAE ¼ 0.164, MBE ¼ 0.139). (b) saturation point of the solution, the activity product of the solid
pKa2. Total number of amines (N) ¼ 39, MAE ¼ 0.310, MBE ¼ 0.060 (N (diamine) ¼ 8, amine can be calculated according to equation (12). All the calcu-
MAE ¼ 0.419, MBE ¼ 0.119; N (alcohol amine) ¼ 3, MAE ¼ 0.120, MBE ¼ 0.040; N (amino lated values of Ks are listed in the “Supplementary data”.
acid) ¼ 28, MAE ¼ 0.299, MBE ¼ 0.113).

potentially important because of the very large contribution of

dissociation to the total solubility of the amines (see section 5.1).
The average values noted above can be used as a first approxima-
tion where the temperature dependencies of other dissociation
constants are needed.

4.4. Activity coefficients

Activity coefficients of uncharged amines in the aqueous aerosol

affect their gas/particle partitioning in the atmosphere via equa-
tions (3) or (12). The activity coefficients of the aminium cations are
also of interest, because the association of the amines with Hþ to
form aminium cations (equations (8) and (9)) may greatly increase
partitioning to the particle phase, just as NH3 is ionized to NHþ
4 . The
activity coefficients of aminium cations are here assumed to have
the same values as the ammonium cation. This assumption is dis-
cussed in detail in Section 5.2 and Appendix 1. For the uncharged
amines, structure-based activity coefficient models such as UNIFAC
(Fredenslund et al., 1975, 1977) can be employed. In UNIFAC, mole
fraction based activity coefficients are calculated based on the Fig. 5. Infinite-dilution activity coefficients (fN) of amines in water at 298.15 K or
functional group compositions of the solution components present. 293.15 K estimated using UNIFAC (fN(UNIFAC)) plotted against measured values (
Parameters describing the interactions of these groups have been fN(Meas.)). Total number of values (N) ¼ 22, MAE ¼ 0.246, MBE ¼ 0.107.

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 X. Ge et al. / Atmospheric Environment xxx (2010) 1e17 9

pH as well as temperature. The definition is straightforwardly

1 extended to diamines, with acid dissociation constants Ka1 and Ka2:
h   
ðtot:Þ
KH ðH2 NRNH2 Þ ¼ KH ðH2 NRNH2 Þ$ 1 þ mHþ Ka1 H2 NRNHþ
-1

0
log10 S(ACD) / mol kg

3
 2 .  
-1 þ mHþ Ka1 H2 NRNHþ 3 $Ka2
 i
 þ H3 NRNHþ 3 (32)
-2
Similarly, the total Henry’s Law constant for an amino acid that
-3 also contains a carboxylic acid group is given by:

ðtot:Þ
-4 KH ðH2 NRCOOHÞ ¼ KH ðH2 NRCOOHÞ$
-4 -3 -2 -1 0 1 h 
-1
1 þ mHþ Ka1 ðþ H3 NRCOOHÞ
log10 S(Meas.) / mol kg  . i
þ Ka2 þ H3 NRCOO mHþ (33)
Fig. 6. Solubilities of amines in water at 298.15 K estimated using the ACD/solubility
module (S(ACD)) plotted against measured values (S(Meas.)). Symbols: C, mono- where the dissociation constants Ka1 and Ka2 are the equilibrium
amine; þ, diamine; 7, alcohol amine; , other amine; 7, amino acid; ,, amide. Total
constants of reactions (28) and (29), respectively.
number of values (N) ¼ 59, MAE ¼ 0.376, MBE ¼ 0.023 (N (monoamine) ¼ 19,
MAE ¼ 0.295, MBE ¼ 0.064; N (diamine) ¼ 3, MAE ¼ 0.189, MBE ¼ 0.024; N (alcohol The total Henry’s Law constants for the amines with measured
amine) ¼ 3, MAE ¼ 0.130, MBE ¼ 0.015; N (other amine) ¼ 6, MAE ¼ 0.220, KH and Ka at 25  C (and 0  C for some amines), for pH ranging from 9
MBE ¼ 0.220; N (amino acid) ¼ 24, MAE ¼ 0.445, MBE ¼ 0.101; N (amide) ¼ 4, to 1, are listed in Table S5 of the “Supplementary data”. Since
MAE ¼ 0.908, MBE ¼ 0.233). amines are bases, the total Henry’s Law constants increase sharply
with a decrease of aerosol pH, so that acidic particles have a strong
5. Partitioning of amines to the aerosol propensity for uptake of amines from the gas phase. Also, for small
amines, such as MA, DMA, EA and DEA, low temperatures favor
Like ammonia, amines can be expected to partition into aqueous partitioning to the aqueous phase.
aerosols. Reactions with gas phase acids such as HNO3 and HCl to Acid dissociation constants, Ka, of the common amines are
form solid aminium nitrate and/or chloride salts are also a possi- typically very small d for example 1010.66 mol kg1 for MA, and
bility. Formation of solid nitrates and sulfates has been examined 109.80 mol kg1 for TMA. Consequently, in acidic aerosols for
by Murphy et al. (2007), who demonstrate that amines can undergo which pH < 7, the value of mHþ =Ka ðRn NHþ 4n Þ >> 1 and equation
similar acidebase reactions as ammonia to form atmospheric (31) can be written as:
nitrate and sulfate salts in the presence of HNO3 or H2SO4. Below, h  i
we first predict the total solubility of amines in aqueous aerosols at
ðtot:Þ
KH ðRn NH3n ÞzmHþ $ KH ðRn NH3n Þ=Ka Rn NHþ
4n
different pH values and compare the results to those for ammonia.
(34)
Second, we estimate Kp values for a large number of aminium
nitrate and chloride salts, from which the likelihood of the forma- or
tion of particles in the atmosphere can be assessed. h   i
log10 ðtot:Þ KH ðRn NH3n Þzlog10 KH ðRn NH3n Þ Ka Rn NHþ
4n
5.1. Aqueous aerosols
 pH
The total molality of an amine present in an aqueous solution, and (35)
at equilibrium with the gas phase, is equal to the sum of the molalities This logarithmic form of the total KH expression represents
of the undissociated amine and the amine cation (analogous to the a simple linear relationship with pH, with a slope of 1 and an
sum of NH3 and NHþ 4 in the case of ammonia). Assuming a fixed intercept of log10 ½KH ðRn NH3n Þ=Ka ðRn NHþ
4n Þ. A larger value of KH/
solution pH, and activity coefficients equal to unity, the total molality Ka indicates a stronger partitioning to the aqueous particle phase.
of a simple amine (mRnNH3n(tot.)) containing a single amine group Fig. 7a shows the calculated total KH for six common aliphatic
is given by: amines and ammonia. Except for TMA, values for MA, DMA, EA,
DEA and TEA are all larger than that of ammonia at the same pH,
mRn NH3n ðtot:Þ ¼ mRn NH3n þ mRn NHþ
4n (30a) indicating that under these conditions they preferentially partition
to the aqueous phase.
h  i The total number of moles of the amine in the aqueous aerosol is
¼ pRn NH3n $KH ðRn NH3n Þ$ 1þmHþ =Ka Rn NHþ
4n (30b) given by:

The above expression was obtained by combining equations (3) nRn NH3nðaqÞ ¼ mRn NH3n ðtot:Þ$ðgw =1000Þ (36)
and (8). We define the total Henry’s Law constant of the amine,
(tot.) 3
KH(RnNH3n) as: for the monoamines. Here, gw (g m ) is the amount of liquid water
in the aqueous aerosol phase per m3 of atmosphere. The number of
ðtot:Þ moles of the amine in gas phase, per m3, is:
KH ðRn NH3n Þ ¼ mRn NH3n ðtot:Þ=pRn NH3n (31a)

h  i nRn NH3nðgÞ ¼ pRn NH3n $ð273:15=TÞ$ð1=0:022414Þ (37)

¼ ðtot:Þ
KH ðRn NH3n Þ$ 1 þ mHþ =Ka Rn NHþ
4n (31b)
where 0.022414 m3 mol1 is the molar volume of an ideal gas at
where (tot.)KH(RnNH3n) relates the total molality of dissolved STP. The mole fraction in the particle phase, n(aq)/[n(aq) þ n(g)], can
amine to its equilibrium partial pressure, and is now a function of be written as:

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10 X. Ge et al. / Atmospheric Environment xxx (2010) 1e17

methylaminium nitrate as an example, and writing KS(CH3NH3NO3)

a 12 explicitly in terms of molalities and activity coefficients, equation
-1

(22) yields:
KH / mol kg atm

10
  .
-1

Kp ðCH3 NH3 NO3 Þ ¼ Ka CH3 NHþ

3 ½KH ðCH3 NH2 Þ$KH
8
 

ðHNO3 Þ $ mCH3 NHþ
3 $mNO3
6

gCH3 NHþ $gNO3
tot.

(39)
4 3
log10

This equation includes the molalities and activity coefficients of the

2 CH3NHþ 
3 and NO3 ions in the saturated solution. The value of mNO3


0 2 4 6 8 10 is known from the measured solubility of the salt, while that of

pH CH3NHþ 
3 is reduced (relative to that for NO3 ) by the equilibrium
with Hþ to form the uncharged molecule CH3NH2. The molalities of
b clouds individual species can be estimated as follows. First, we define the
Aerosol fogs total aminium cation molality, mCH3NHþ þ
100 3 (tot.) and total H ion
molality, mHþ(tot.):
n(aq)/ n(aq)+ n(g) (%)

80 pH=3
mCH3 NHþ þ
3 ðtot:Þ ¼ mCH3 NH3 þ mCH3 NH2 (40a)

60 pH=5.6 
mHþ ðtot:Þ ¼ mHþ þ mCH3 NHþ
3  mOH (40b)

40 The values of the two total molalities in equation (40) are both
pH=7 equal to the solubility of the salt in the saturated solution
20 (48.46 mol kg1 in this case). The equation for mHþ(tot.) can be
written in terms of the dissociation constant of the amine and that
of water:
0
.  . 
-6 -5 -4 -3 -2 -1 0 1 mHþ ðtot:Þ ¼ mHþ þmCH3 NHþ
3 ðtot:Þ 1þKa* CH3 NHþ
3 mHþ
-3
log10 gw / g m 
Kw =mHþ ð41Þ
Fig. 7. (a) Total Henry’s Law constants (tot.KH) at 298.15 K for some amines and ammonia where the two stoichiometric dissociation constants are given by:
as a function of pH. (b) Fractions of amines and ammonia present in the aqueous aerosol
    . 
phase as a function of atmospheric liquid water content (gw) at 298.15 K. The assumed
aerosol and fogwater pH values are indicated on the plot for each set of partitioning
Ka* CH3 NHþ
3 ¼ Ka CH3 NHþ
3 $gCH3 NH
þ gHþ $gCH3 NH2 (42)
3
curves. Lines (both plots): Solid (d), ammonia; dash (d d), TMA; dotted (- -), TEA; dot-
dash (- d -), DEA; dot-dot-dash (– – dd – –), MA, DMA and EA.
. 

Kw ¼ Kw $aH2 O gHþ $gOH (43)
.h i h 
nðaqÞ nðaqÞ þnðgÞ ¼1= 1þð273:15=TÞ$ð1=0:022414Þ
 . i Equation (41) can be solved for the free hydrogen ion molality,
ðgw 1000Þ$ðtot:Þ KH ðRn NH3n Þ (38) mHþ, but requires values of the activity of water (aH2O) and the
activity coefficients of the ions Hþ, CH3NHþ 
3 , OH and uncharged
In Fig. 7b, calculated values of n(aq)/[n(aq) þ n(g)] (%) for six
CH3NH2. These were estimated by assuming that the ion CH3NHþ 3
common aliphatic amines and ammonia are plotted against
(and all other aminium cations) behaves in the same way as NHþ 4,
atmospheric liquid water content. With the exception of TMA, all
and using the model of the HþeNHþ 
4 eNO3 eH2O system developed
the amines partition into the aqueous phase more strongly than
by Clegg et al. (1998a) to obtain gHþ , gCH3 NHþ (set equal to gNHþ ),
ammonia. In the range of gw < 102 g m3 for aerosol particles at 3 4
gNO3 and aH2O. The calculated values of Kp were found to be
pH ¼ 7, the ammonia and TMA are almost entirely present in the
insensitive to gCH3 NH2 which could be set to a value of 1.0.
gas phase, and no more than 1% of TEA, 4% of MA, DMA and EA, and
Finally, having solved equation (41) for mHþ, the value of
18.2% of DEA in the aqueous aerosol phase at the highest liquid
mCH3NHþ 3 can be obtained from equation (40a) and then the value
water content. At a lower pH of 3.0, much greater fractions of all the
of Kp calculated. It was found in all cases that the difference
amines and ammonia exist in the aqueous aerosol phase, even for
between the total amine cation concentrations in the saturated
very low atmospheric liquid water contents. In the gw range of
solutions, and those of the free cations was extremely small. For
0.02e0.5 g m3 for fogs, and 0.03e3 g m3 for clouds, at the
example, for methylaminium nitrate mCH3NHþ 3 (tot.) in the satu-
“natural” acidity of rainwater (pH 5.6, Seinfeld and Pandis, 2006)
rated solution at 298.15 K was 48.46 mol kg1, and the molality of
substantial partitioning to the aqueous phase also occurs.
the free cation (from which Kp is calculated) was
48.459987 mol kg1. The activity coefficient term gCH3 NHþ $gNO3 in
3
5.2. Solid or aqueous aminium salt aerosols the expression for Kp was 7.89  103 and will vary with both the
concentration of the saturated solution and the nature of the amine
As noted in section 2, Kp can be estimated from the solubilities of cation. In our calculations of the Kp of methylaminium nitrate, the
the salts in water, their Henry’s law constants and acid dissociation values of this term ranged from 4.46  103 to 1.25  102 from
constants, and the Henry’s law constant of the acid containing the 273.15 to 323.15 K, and the solubilities varied from 22.20 to
anion (NO 
3 or Cl ) from which the aminium salt is formed. Taking 90.68 mol kg1. The solubilities of the aminium nitrates change

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 X. Ge et al. / Atmospheric Environment xxx (2010) 1e17 11

Table 4 greatly with temperature (as does ammonium nitrate), which has
Solid/gas equilibrium dissociation constants (Kp) of aminium chlorides.a a significant influence on the activity and thus the Kp values.
Chlorides Formula T/K Solubilityb/mol kg1 Kp/Pa2 Furthermore, as shown in equation (39), changes in Ka, KH(CH3NH2)
Ammonia NH4Cl 263.15 4.74i1
8.54E-11j and the activity product also affect the Kp value. From 273.15 K to
273.15 5.56 [1] 1.25E-09 298.15 K, the variations in Ka(CH3NH2), KH(CH3NH2), and the solu-
293.15 7.01 [1] 2.40E-07 bility of CH3NH3NO3 (reflected in the activity product) result in
298.15 7.39[1] 7.98E-07
changes in Kp by factors of 7.08, 2.22, and 1.75 respectively. In this
313.15 8.58 [1] 2.61E-05
323.15 9.42 [1] 2.19E-04 case the acid dissociation constant Ka has the greatest influence on
Methylamine CH5N$HCl 263.15 18.12i2 8.20E-11j the change of Kp with temperature.
273.15 20.30 [2] 1.39E-09 The procedure described above was also used to estimate Kp of
293.15 22.27 [2e8] 1.35E-07 aminium chloride salts from 263.15 to 323.15 K, using the model of
298.15 23.76 [9,10] 3.81E-07c1
1.54E-07c2
Clegg et al. (1998b) for the HþeNHþ 
4 eCl eH2O system to simulate
9.80E-08c3 the aqueous solution of aminium chloride and obtain estimates of
313.15 26.34 [2e8] 8.94E-06 the activity coefficients. In this calculation, the activity coefficients
323.15 28.38 [9,10] 6.00E-05 obtained at 298.15 K were applied without alteration over the range
Dimethylamine C2H7N$HCl 263.15 38.86i3 1.72E-10j
of 263.15e323.15 K. Results are listed in Table 4.
273.15 42.21 [2] 1.83E-09
293.15 47.58 [3,4,6,7,11,12] 1.97E-07 For temperatures of 273.15 K and 293.15 K, the Kp values of some
298.15 44.80 [12e15] 6.22E-07d1 aminium chlorides (such as those of MA, DMA and TEA) are close to
3.45E-07d2 or even higher than that of ammonium chloride. However, at
313.15 52.31 [4,6,8,11] 1.32E-05 temperatures above 298.15 K, the corresponding values are typi-
323.15 57.84 [10,15] 9.28E-05
Trimethylamine C3H9N$HCl 263.15 15.02i4 2.32E-08j
cally smaller than that of ammonium chloride, indicating that at
273.15 20.31 [2,12] 1.65E-07 a higher temperature amines are competitive with ammonia for the
293.15 27.61 [4e8,12] 5.72E-06 formation of the solid chlorides. Because the Kp of trimethylamine
298.15 30.19 [10,16] 1.33E-05 (TMA), aniline and N-methylaniline hydrochlorides are found to be
313.15 31.41 [4,6e8,12,17] 1.26E-04
2 or more orders of magnitude greater than that of ammonium
323.15 33.16 [10,12,16] 5.39E-04
Ethylamine C2H7N$HCl 298.15 34.34 [14] 5.67E-07e1 chloride and the atmospheric concentration of ammonia is also
2.48E-07e2 orders of magnitude higher, formation of these aminium chlorides
1.99E-07e3 in the presence of ammonia is improbable. On the other hand,
Diethylamine C4H11N$HCl 263.15 16.31i5 1.05E-12j diethanolamine and triethanolamine hydrochlorides, whose Kp
273.15 17.34 [17] 2.51E-10
283.15 17.81 [18] 5.09E-10
values are much smaller than those of ammonium chloride, are
293.15 19.14 [12,17,19e21] 9.59E-09 more likely to be formed.
298.15 20.52 [13,14,22] 4.20E-08f1 The Kp values of some aminium nitrate salts in the temperature
1.40E-07f2 range of 263.15e323.15 K are shown in Table 5. Most of these Kp are
3.64E-07f3
at least one order of magnitude smaller than that of ammonium
313.15 23.48 [12,17,19e21] 2.37E-06
323.15 24.69 [22] 3.11E-05
Triethylamine C6H15N$HCl 263.15 5.31i6 3.20E-10j
293.15 9.49 [20,21,23e25] 1.80E-07
298.15 9.96 [13,14] 4.15E-07
303.15 10.86 [24] 1.18E-06
(pKw) at different temperatures are taken from Lide (2009): 273.15 K, 14.92;
313.15 10.64 [12,19e21,24] 5.41E-06
293.15 K, 14.1669; 298.15 K, 14; 313.15 K, 13.5348; 323.15 K, 13.2617. The Henry’s
323.15 10.04 [24] 2.17E-05
Law constant of HCl is 2.04  106 mol2 kg2 atm1 at 298.15 K, and values of other
Propylamine C3H9N$HCl 298.15 29.19 [13,14] 3.32E-07g1
temperatures except 263.15 K can be calculated from ln(KH) ¼ 4.61871 þ 5977.5014/
2.71E-07g2
T  0.03401 T (Brimblecombe and Clegg, 1989). The Henry’s Law constant for
Butylamine C4H11N$HCl 293.15 6.09 [26] 9.35E-09
ammonia was calculated from ln(KH) ¼ 8.09694 þ 3917.507/T  0.00314 T (Clegg
298.15 6.48 [26] 2.87E-08h1
and Brimblecombe, 1989).
2.48E-08h2 b
Sources of data for aminium chloride solubilities in water are as follows: 1 e
323.15 7.29 [26] 2.26E-06
Lide (2009); 2 e Tereshchenko (1975); 3 e Zhuravlev et al. (1980b); 4 e
Isobutylamine C4H11N$HCl 298.15 21.82 [13,14] 5.26E-07
Shamsutdinova and Nurgalieva (1978); 5 e Zhuravlev et al. (1975); 6 e Zhuravlev
Dibutylamine C8H19N$HCl 298.15 3.04 [26] 7.32E-09
et al. (1976b); 7 e Zhuravlev et al. (1972); 8 e Zhuravlev et al. (1979); 9 e
Diethanolamine C4H11O2N$HCl 298.15 3.15 [19] 7.87E-13
Zhuravlev and Kadantseva (1971); 10 e Zhuravlev et al. (1980a); 11 e Zhuravlev
313.15 4.67 [23] 1.70E-11
et al. (1973a); 12 e Dortmund Databank (2009); 13 e Stephen and Stephen
Triethanolamine C6H15O3N$HCl 293.15 2.28 [23] 4.69E-14
(1979); 14 e Peddle and Turner (1913); 15 e Kadantseva and Zhuravlev (1973);
298.15 2.60 [23] 1.30E-13
16 e Zhuravlev and Kadantseva (1970); 17 e Zhuravlev et al. (1973b); 18 e Mazunin
313.15 3.75 [23] 1.72E-12
et al. (2001); 19 e Zhuravlev et al. (1974a); 20 e Zhuravlev et al. (1978a); 21 e
Isopentylamine C5H13N$HCl 298.15 15.56 [13,14] 2.35E-07
Zhuravlev et al. (1978b); 22 e Kadantseva (1972); 23 e Zhuravlev et al. (1974b); 24
Piperidine C5H11N$HCl 298.15 18.75 [27] 1.59E-08
e Lupeiko et al. (1989); 25 e Volkov et al. (1982); 26 e Gaiutdinova et al. (1992); 27
293.15 16.71 [27] 3.53E-09
e Yurkevich and Zhuravlev (1975); 28 e Zhuravlev (1971); 29 e Kadantseva and
313.15 21.16 [27] 8.19E-07
Zhuravlev (1974).
Dipropylamine C6H15N$HCl 298.15 12.02 [13,14] 1.04E-07 c-h
The following Henry’s Law constants of amines at 298.15 K were taken from the
1-Hexanamine C6H15N$HCl 298.15 62.80 [17] 2.88E-07
NIST Chemistry Webook (in units of mol kg1 atm1): c1 e 36.48; c2 e 90.18; c3 e
Aniline C6H7N$HCl 293.15 6.90 [27,28] 1.48E-03
141.86; d1 e 31.41; d2 e 56.74; e1 e 35.46; e2 e 81.06; e3 e 101.33; f1 e 131.72; f2
298.15 8.33 [12e14,29] 2.37E-03
e 39.52; f3 e 15.20; g1 e 66.87; g2 e 81.06; h1 e 57.76; h2 e 66.87.
313.15 9.87 [27,28] 5.03E-02 i
Solubilities at 263.15 K were extrapolated using the experimental solubility data
323.15 12.98 [29] 3.14E-01
at other temperatures listed in this table, fitted as follows: i1, i2 e linear function of
Benzylamine C7H9N$HCl 298.15 3.53 [13,14] 3.08E-07
temperature (data from 273.15 K to 323.15 K); i3 e as for i1 and i2, except the
N-Methylaniline C7H9N$HCl 298.15 26.37 [13,14] 1.14E-01
solubility at 298.15 K was omitted; i4, i5 e quadratic function of temperature (data
a
Henry’s Law constants for the amines are listed in “Supplementary data”. Where from 273.15 K to 323.15 K); i6 e linear function of temperature (data for 293.15 K,
the enthalpy change ΔrHo(KH) is not available, KH is assumed to be the same at all 298.15 K and 303.13 K).
j
temperatures. Dissociation constants Ka, and the associated enthalpy change for the The Henry’s Law constant of HC1 at 263.15 K was calculated using equation 22
reaction are also listed in “Supplementary data”, and dissociation constants of water of Carslaw et al. (1995), converted to units of mol2 kg2 atm1.

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12 X. Ge et al. / Atmospheric Environment xxx (2010) 1e17

Table 5 Murphy et al. (2007) report Kp values for ammonium nitrate and
Solid/gas equilibrium dissociation constants (Kp) of aminium nitrates.a six aliphatic amine nitrates at 298.15 K, estimated using the inte-
Nitrates Formula T/K Solubilityb/mol kg1 Kp/Pa2 grated form of the Van’t Hoff equation. For ammonium nitrate,
Ammonia NH4NO3 263.15 11.33 [18] 2.14E-11d Murphy et al. (2007) report values of 1.916  107 Pa2 and
273.15 15.04 [1] 4.97E-10 7.14  107 Pa2 at 293.15 K and 298.15 K respectively, compared to
293.15 23.72 [1] 1.26E-07 our results of 1.26  107 Pa2 and 4.48  107 Pa2 (Clegg et al.,
298.15 26.33 [1] 4.48E-07
1998a). For aminium nitrates, their method requires values of the
313.15 35.38 [1] 1.55E-05
323.15 43.22 [1] 1.35E-04 heat of formation, entropy of formation and heat capacity, which
Methylamine CH5N$HNO3 263.15 21.12c1 3.59E-12d are either lacking or quite uncertain. This results in large uncer-
273.15 22.2 [2] 6.80E-11 tainties in Kp e up to several orders of magnitude e and the
293.15 38.5 [2] 1.38E-08 uncertainty may preclude gaining meaningful insights into the
298.15 48.46 [3] 4.54E-08
313.15 60.28 [2] 1.28E-06
formation of some important salts, such as the nitrates of MA, DMA
323.15 90.68 [3] 1.01E-05 and TEA. However, Murphy et al. (2007) determined experimen-
Dimethylamine C2H7N$HNO3 298.15 103.66 [4e6] 6.27E-08 tally a Kp of 1.85  107 Pa2 for TEA nitrate at 293.15 K, which is
323.15 237.65 [5,6] 1.34E-05 about twice of our estimate of 9.64  108 Pa2. Compared with the
Trimethylamine C3H9N$HNO3 263.15 32.00c2 1.67E-09d
results of Murphy et al. (2007) (listed in Table A2), our values in
298.15 88.24 [5] 1.65E-06
323.15 128.41 [5] 8.96E-05 Tables 4 and 5 appear to be more consistent with one another, and
Ethylamine C2H7N$HNO3 298.15 23.15 [7] 2.83E-08 therefore appear more reasonable. Uncertainties in the Henry’s law
Diethylamine C4H11N$HNO3 263.15 8.37c3 2.58E-14d constants of the amines affect the calculated Kp values, as can be
273.15 15.27 [5] 1.17E-12 seen for the chlorides of MA, EA and DEA in Table 4, but typically Kp
293.15 26.85 [8] 9.31E-10
298.15 33.50 [4e6,9] 7.01E-09
values remain in the same order, and are still substantially smaller
313.15 41.67 [8] 3.19E-07 than that of ammonium chloride. An evaluation of our estimated Kp
323.15 66.18 [6,9] 5.31E-06 values involving the measured and estimated activity coefficients
Triethylamine C6H15N$HNO3 263.15 39.64c4 2.12E-10d can be found in Appendix 1.
293.15 54.88 [8] 9.39E-08
Aminium salts in the atmosphere should be present as solids up
323.15 70.12 [8] 1.60E-05
Isobutylamine C4H11N$HNO3 293.15 120.52 [10,11] 2.78E-08 to their relative humidities of deliquescence. At higher relative
323.15 237.75 [10,11] 8.44E-07 humidities the salt aerosol will exist as a solution and the value of
Ethanolamine C2H7ON$HNO3 293.15 43.35 [12] 1.41E-12 the equilibrium vapor pressure product pRnNH3n$pHX, which we
313.15 156.05 [12] 8.61E-11 denote Kps, is reduced relative to that over the solid. We have
Diethanolamine C4H11O2N$HNO3 293.15 21.73 [12] 9.14E-13
313.15 45.81 [12] 5.60E-11
calculated the temperature and relative humidity dependence of
Triethanolamine C6H15O3N$HNO3 293.15 21.49 [12] 2.13E-13 Kps, and the solid/gas dissociation constant Kp, for the chlorides and
313.15 36.30 [12] 5.52E-11 nitrates of six common amines. Results are shown in Figs. 8 and 9.
Aniline C6H7N$HNO3 293.15 1.71 [13,14] 4.43E-05 Ammonium nitrate and ammonium chloride have been used as
298.15 1.86 [15e17] 1.01E-04
analogues of the aminium salts in the aqueous solutions in order to
313.15 3.60 [13,14] 2.13E-03
323.15 6.28 [15] 1.60E-02 estimate water activities (i.e., equilibrium relative humidity) and
a
ion activity coefficients. For some aminium salt solutions, measured
Data sources for KH (for amine and ammonia), Ka and Kw are the same as
described in note a of Table 4. The Henry’s Law constant of HNO3 is
mean activity coefficients of the salts are available and calculated
2.45  106 mol2 kg2 atm1 at 298.15 K, and and values of other temperatures Kps based on these values are also shown. There is good agreement.
except 263.15 K can be calculated from ln(KH) ¼ 2.70104 þ 6137.3984/T  0.02876 T In the figures it is clear that both Kp and Kps values increase
(Brimblecombe and Clegg, 1989). steeply with temperature, by close to an order of magnitude for
b
Sources of data for solubilities of the salts in water are as follows: 1 e Clegg et al.
a 10 K change. Low temperatures are therefore generally favorable
(1998a); 2 e Nakamura et al. (1982); 3 e Zhuravlev and Kadantseva (1972); 4 e
Mininkov et al. (1976); 5 e Gorshunova and Zhuravlev (1970b); 6 e Dortmund for aminium salt aerosol formation. However, the Kp of trimethy-
Databank (2009); 7 e ACD (2009) e Solubility database 8 e Zhuravlev et al. laminium nitrate, for example, is much larger than that of ammo-
(1974c); 9 e Khisaeva (1986); 10 e Boeva et al. (1977); 11 e Gaiutdinova et al. nium nitrate at low temperatures (see Table 5). Considering that
(1992); 12 e Starikova et al. (1975); 13 e Kuznetsova and Zhuravlev (1977); 14 e the typical concentration of ammonia in the atmosphere is also
Zhuravlev et al. (1976a); 15 e Gorshunova and Zhuravlev (1970a); 16 e Gorshunova
and Zhuravlev, (1970a); 17 e Mininkov and Zhuravlev (1970); 18 e Clegg et al.
orders of magnitude higher, it is expected that formation of the
(1998a). trimethylaminium nitrate salt is unlikely under such conditions.
c
Solubilities at 263.15 K were extrapolated using the experimental solubility data This is consistent with results of smog chamber experiments by
at other temperatures listed in this table, fitted as follows: c1 e quadratic function of Silva et al. (2008), which indicate that secondary oxidation chem-
temperature (data from 273.15 K to 323.15 K); c2 e linear function of temperature
istry may dominate over acidebase chemistry as a source of
(data at 298.15 K and 323.13 K); c3 e linear function of temperature (data from
273.15 K to 313.13 K); c4 e linear function of temperature (data at 293.15 K and particles from amine (TMA) precursors. Experiments demon-
323.13 K). strating reactive uptake of TMA onto ammonium nitrate particles
d
The Henry’s Law constant of HNO3 at 263.15 K was calculated using equation 20 (Lloyd et al., 2009) appear to have been carried out at room
of Carslaw et al. (1995), converted to units of mol2 kg2 atm1. temperature, at which the Kp of the two nitrate salts differ by only
about a factor of 5 (Table 5). This is qualitatively consistent with the
fact that a measurable exchange was observed.
nitrate at the same temperature. The exceptions are TMA and Ion peaks from 58(C3H8N)þ, 59(C3H9N)þ, 86(C5H12N)þ,
aniline. Ambient concentrations of gas phase HNO3 and HCl vary 100
(C6H14N)þ, and 101(C6H15N)þ associated with amines have been
widely, although consideration of sources and sinks, and available found in particles in Toronto wintertime (Tan et al., 2002), or in
measurements, suggests the levels of HNO3 are generally likely to Logan, Utah (the most common one was 58(C3H8N)þ, Silva et al.,
be higher, except for circumstances that favor HCl formation such 2007). Angelino et al. (2001) attribute them to TMA, DEA, TEA or
as displacement of HCl from acidified seasalt aerosols (Warneck, their corresponding cations. The possibility of formation of some
2000). Since the Kp values of aminium nitrates are typically much aminium chlorides and nitrates at a low temperature, 263.15 K, can
smaller than those for aminium chlorides, the formation of the be assessed using the values of Kp listed for this temperature in
solid nitrate salts is more likely in the ambient atmosphere. Tables 4 and 5. Because measured solubilities, pKa and KH values for

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Atmospheric Environment (2010), doi:10.1016/j.atmosenv.2010.10.013
 X. Ge et al. / Atmospheric Environment xxx (2010) 1e17 13

a d 1E-5
1E-4 323.15 K
298.15K

1E-6 298.15 K
1E-7
2

2
Kp , Kps / Pa

Kp , Kps / Pa
1E-8
273.15 K

1E-10 1E-9

1E-12
1E-11
0.2 0.4 0.6 0.8 1.0 0.2 0.4 0.6 0.8 1.0
Relative Humidity Relative Humidity

b e 1E-3
323.15 K 323.15 K
1E-4
1E-5
1E-6 298.15 K
298.15 K
2

1E-7

2
Kp , K p s / Pa

Kp , Kps / Pa
1E-8 273.15 K 1E-9
273.15 K
1E-10 1E-11

1E-12 1E-13

1E-14 1E-15
0.2 0.4 0.6 0.8 1.0 0.2 0.4 0.6 0.8 1.0
Relative Humidity Relative Humidity

c 0.01 f 1E-3
323.15 K
323.15 K
1E-4
298.15 K 1E-5
2
Kp , Kps / Pa
2
Kp , Kps / Pa

298.15 K
1E-6 273.15 K
1E-7

1E-8
1E-9
1E-10
1E-11
0.2 0.4 0.6 0.8 1.0 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Relative Humidity Relative Humidity

Fig. 8. The temperature and relative humidity dependence of the equilibrium vapor pressure product (pAmine$pHCl) over solid aminium chloride (to the left of each dashed line)
and over aqueous aminium chloride solutions (to the right of each dashed line). (a) Methylaminium chloride (CH5N$HCl), (b) dimethylaminium chloride (C2H7N$HCl), (c) trime-
thylaminium chloride (C3H9N$HCl), (d) ethylaminium chloride (C2H7N$HCl), (e) diethylaminium chloride (C4H11N$HCl), and (f) triethylaminium chloride (C6H15N$HCl). Open circles
are values based upon activity coefficients measured by Macaskill and Bates (1986), and the lines were obtained using activity coefficients of NH4Cl at 298.15 K as an analogue.
Dashed lines show the phase transition between solid salts and aqueous solutions.

the amines are not available at 263.15 K, these values had to be
extrapolated from the very limited data at higher temperatures,
thus increasing the uncertainty of their Kp. Based on our calcula-
tions, the chloride of DEA and the nitrates of MA, DEA are favored to
form because their Kp values are much lower than those of the
corresponding ammonium salts, but the chloride and nitrate of
TMA remain unlikely. The presence of a TMA peak, 59(C3H9N)þ, in
Toronto wintertime ambient particles, may be due to the following:
(1) TMA was present as the amine, not the salt; (2) at high relative
humidity and especially for acidic particles, the vapor pressure
product Kps, is much lower than Kp (see Figs. 8c and 9c), thus
formation of dissolved TMA salts becomes possible; and (3) TMA
might associate with sulfate (since ammonium was found to
associate with nitrate or sulfate in the observations of Tan et al.
(2002)).
6. 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

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14 X. Ge et al. / Atmospheric Environment xxx (2010) 1e17

a 1E-4 d 1E-6
323.15 K

1E-6 298.15 K
298.15 K
2

1E-8
Kp , Kps / Pa

2
Kp , Kps / Pa
1E-8

273.15 K
1E-10 1E-10

1E-12
1E-12
0.2 0.4 0.6 0.8 1.0 0.4 0.6 0.8 1.0
Relative Humidity Relative Humidity

b e 1E-4
323.15 K 323.15 K
1E-5
1E-6

298.15 K

2
2

Kp , Kps / Pa
Kp , Kps / Pa

298.15 K 1E-8
1E-7

1E-10
1E-9 273.15 K
1E-12

1E-11 1E-14
0.0 0.2 0.4 0.6 0.8 1.0 0.2 0.4 0.6 0.8 1.0

Relative Humidity Relative Humidity

1E-3
c 323.15 K
f
1E-4 323.15 K
1E-5
2

298.15 K
Kp , Kps / Pa
2
Kp , Kp s / Pa

1E-6 298.15 K
1E-7

1E-8 1E-9

1E-10 1E-11
0.2 0.4 0.6 0.8 1.0 0.2 0.4 0.6 0.8 1.0
Relative Humidity Relative Humidity
Fig. 9. The temperature and relative humidity dependence of the equilibrium vapor pressure product, pAmine$pHNO3, over solid aminium nitrate (to the left of each dashed line)
and over aqueous aminium nitrate solutions (to the right of each dashed line). (a) Methylaminium nitrate (CH5N$HNO3), (b) dimethylaminium nitrate (C2H7N$HNO3), (c) trime-
thylaminium nitrate (C3H9N$HNO3), (d) ethylaminium nitrate (C2H7N$HNO3), (e) diethylaminium nitrate (C4H11N$HNO3) and (f) triethylaminium nitrate (C6H15N$HNO3). Open
circles are values based upon activity coefficients measured by Bonner (1981), the lines were obtained using activity coefficients of NH4NO3 as an analogue of the amine salt. Dashed
lines show the phase transition between solid salts and aqueous solutions.

tested and then used to complete the data set. The results have
been included in the Extended Aerosol Inorganics Model, see
Appendix 2.
Vapor pressures of the amines were estimated by combining
a measured or predicted boiling point with a predicted enthalpy of
vaporization. Boiling points predicted by the ACD method were
found to be more accurate than those calculated by the equations of
Nannoolal et al. (2004), and of Stein and Brown (1994). Pure liquid
vapor pressures predicted using the methods of Moller et al. (2008)
and Nannoolal et al. (2008) (with measured boiling points)
generally agreed well with the data, but the equation of Moller et al.
yields a smaller systematic bias error. The ACD/pKa predictor was
found to yield good results for the acid dissociation constants at
room temperature of the amine cations. The UNIFAC activity coef-
ficient model and the ACD/solubility module were found to provide
reasonable, though less accurate, estimates of activity coefficients
at infinite dilution and solubility, respectively.
Dissociation constants of solid aminium nitrates and chlorides
(yielding the gas phase amine and inorganic acid) were estimated
from available aqueous solubility measurements and other data.

Please cite this article in press as: Ge, X., et al., Atmospheric amines e Part II. Thermodynamic properties and gas/particle partitioning,
Atmospheric Environment (2010), doi:10.1016/j.atmosenv.2010.10.013
 X. Ge et al. / Atmospheric Environment xxx (2010) 1e17 15

Our results are comparable to those of Murphy et al. (2007). In the
atmosphere it is possible that a number of the salts may be formed
preferentially to solid ammonium chloride and nitrate. However,
chlorides of TMA, aniline and N-methylaniline and nitrates of TMA
and aniline are unlikely to occur in the presence of ammonia
because their dissociation constants are much larger than those of
the ammonium salts.
Simple calculations of gas/particle partitioning of amines, as
a function of atmospheric liquid water content and pH, confirm that
their behavior is comparable to that of ammonia and that aerosol
pH is a key property determining partitioning into the aerosol.
Acknowledgements
The work was supported by the Electric Power Research
Institute.
solution. This uses three adjustable parameters, b, S and n, for each
electrolyte. For the nitrates of MA, DMA and TMA, Ge et al. (2008)
obtained values of the parameters by fitting to the data of Bonner
(1981). Values for chlorides of MA, DMA and TMA are derived here
from the measurements by Macaskill and Bates (1986) (b ¼ 14.3300,
S ¼ 197.9141, n ¼ 0.0178 for methylaminium chloride; b ¼ 1.7286,
S ¼ 50.0294, n ¼ 0.4012 for dimethylaminium chloride; and
b ¼ 1.6306, S ¼ 35.9945, n ¼ 0.5262 for trimethylaminium chloride).
Mean activity coefficients of the salts at the maximum measured
molality, and the corresponding Kps values over the solution, are
listed in Table A1 together with estimates obtained by E-AIM using
aqueous NH4NO3 and NH4Cl as analogues. The values of Kps
determined using these activity coefficients agree with those based
upon the measurements to within an (average) factor of only 1.6,
and the difference becomes larger as the size of the aminium cation
increases.

Table A1
Measured and estimated mean activity coefficients (g) in concentrated aqueous solutions of aminium salts at 298.15 K, and corresponding vapor pressure products (Kps).

Salts m/mol kg1 g Kps/Pa2

Measured TCPC E-AIM Measured TCPC E-AIM

Methylaminium chloride 20.0a 0.532a 0.535 0.510 3.33E-07 3.37E-07 3.06E-07
Dimethylaminium chloride 17.0a 0.688a 0.714 0.533 3.98E-07 4.29E-07 2.39E-07
Trimethylaminium chloride 15.0a 0.857a 0.884 0.546 1.33E-05 1.42E-05 5.41E-06
Methylaminium nitrate 9.5b 0.275b 0.271 0.230 1.67E-08 1.62E-08 1.17E-08
Dimethylaminium nitrate 6.0b 0.357b 0.325 0.284 1.23E-08 9.19E-09 7.22E-09
Trimethylaminium nitrate 8.5b 0.307b 0.291 0.242 4.58E-07 4.12E-07 2.93E-07
a
Macaskill and Bates, 1986.
b
Bonner, 1981.

Appendix 1 Activity coefficients extrapolated up to the saturation

The estimation of Kp values for aminium chlorides and nitrates
requires the activity coefficients of the aminium cation and Cl or
NO 3 . If the experimental activity coefficients at the saturation point
of the salt are known, Kp values can be obtained from equation (39).
Activity coefficients are only available for a small number of ami-
nium salt solutions, and at low concentrations. Nevertheless, those
data are valuable since (i) they provide a test for the estimates of
the activity coefficients made using ammonium salts as analogues,
(ii) extrapolations based on those data up to the saturation point
can yield an estimate of Kp which can be used as a partial test of our
estimates in Tables 4 and 5.
Ge et al. (2007) have proposed a modified three-characteristic-
parameter correlation (TCPC) model for activity coefficients in aqueous
molality using the TCPC model, and the corresponding Kp
values and estimates based upon E-AIM are listed in Table A2
together with values reported by Murphy et al. (2007). The
values of Kp estimated using the two different sets of activity
coefficients agree to within an average factor of 1.6. For
methylaminium chloride, solubilities were measured to
20 mol kg1, which is close to the saturation point of
23.76 mol kg1. In this case, Kp equal to 4.69  107 Pa2 (based
upon only a slight extrapolation of the TCPC fitted model) is
quite close to the E-AIM-based estimate of 3.81  107 Pa2.
These small differences are encouraging, though it is difficult
to draw conclusions about the applicability of our assumptions
regarding activity coefficients to a broader range of amine
salts.

Table A2
Estimated mean activity coefficients (g) in saturated aqueous solutions of aminium salts at 298.15 K, and vapor pressure products (Kp).

Salts Solubility/mol kg1 g Kp/Pa2

b
E-AIM TCPC E-AIM TCPC Murphy et al. (2007)
Methylaminium chloride 23.76 0.479 0.532 3.81E-07 4.69E-07
Dimethylaminium chloride 44.80 0.327 1.513a 6.22E-07
Trimethylaminium chloride 30.19 0.426 2.350a 1.33E-05
Methylaminium nitrate 48.46 0.089 0.106 4.54E-08 6.49E-08 7.90E-06 8.56E-09
Dimethylaminium nitrate 103.66 0.049 0.055 6.27E-08 7.88E-08 1.01E-05 3.95E-09
Trimethylaminium nitrate 88.24 0.056 0.097 1.65E-06 4.93E-06 2.27Eþ00 5.29E-07
Ethylaminium nitrate 23.15 0.143 2.83E-08 3.29E-06 9.56E-07
Diethylaminium nitrate 33.5 0.107 7.01E-09 3.11E-10 3.30E-11
a
Values are very uncertain due to the large degree of extrapolation.
b
Two series of values, based upon different heats of formation, from their Table A1.

Please cite this article in press as: Ge, X., et al., Atmospheric amines e Part II. Thermodynamic properties and gas/particle partitioning,
Atmospheric Environment (2010), doi:10.1016/j.atmosenv.2010.10.013
16 X. Ge et al. / Atmospheric Environment xxx (2010) 1e17
Appendix 2
The E-AIM model for gas/particle partitioning is described by
Wexler and Clegg (2002) for systems containing inorganic elec-
trolytes, and by Clegg et al. (2008a) for extensions to include
organic compounds. Users of the online model can either select
from a list of “built in” organic compounds, or to define their own
compounds by entering basic physical properties and values of KH
or po, dissociation constants, the activity coefficient model to be
used, and the activity product KS of the compound in a saturated
solution. As a part of this project we are adding to the model the
most common atmospheric amines and their thermodynamic
properties from Tables S2 to S4 of the “Supplementary data”. We
are also extending the input page for thermodynamic data in the
model to include the acid dissociation constants of amine cations
(equation (8)). This allows users to alter assigned properties of the
amines, for sensitivity tests for example, or to add amines not
included in our database.
Appendix. Supplementary data
Supplementary data associated with this article can be found in
the online version at doi:10.1016/j.atmosenv.2010.10.013.
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