Article

pubs.acs.org/IECR

Modeling the Solubility of Nitrogen Dioxide in Water Using

Perturbed-Chain Statistical Associating Fluid Theory
Sugata P. Tan* and Mohammad Piri
Department of Chemical and Petroleum Engineering, University of Wyoming, Department 3295, 1000 E. University Avenue,
Laramie, Wyoming 82071, United States

ABSTRACT: NO2 is one of the important components in flue gas from combustion in power plants, which together with CO2
and SO2 pollute the atmosphere if released and cause the undesired acid rains. NO2 reacts immediately with H2O upon
dissolution, which prevents direct measurements on the physical phase equilibria of the chemical system. Modeling this reacting
system is a challenging task due to the complexities arising from the heterogeneous nature of the chemical reaction, the multiple
components that are involved in the phase equilibria, ionic dissociation in water, self- and cross-associations among the
molecules, and multiple chemical reactions that may occur before reaching the physicochemical equilibria. Therefore, efforts on
modeling this NO2/H2O system have been made so far with no satisfactory progress. In this work, we propose a complete model
of the system using Perturbed Chain Statistical Associating Fluid Theory (PCSAFT) equation of state (EOS). The model is
found to be able to calculate the solubility curves of NO2 in water at various pressures and temperatures, which provide a strong
foundation for a later application in flue gas sequestration into aquifers.

■ INTRODUCTION
Despite its importance in the removal efforts of NOx from the
must be indirectly inferred from kinetic studies, the results of
which have large uncertainties.1
flue gases for a clean environment, in the precipitation processes The buildup of the products in eq 2 complicates the situation.
in the atmosphere, and in the manufacture of nitric acid, the At high concentration, HNO3 will tend to dissociate accord-
absorption of NOx in water is perhaps the least understood in all ing to8
absorption operations.1 It is probably the most complex case of 4HNO3 ↔ 4NO2 + 2H 2O + O2 (3)
absorption due to the large number of species and reactions that
are involved in the process. NOx is in fact a mixture of all nitrogen which is dominant, for example, in the work series of Sage and
oxides (N2O, NO, NO2, N2O3, N2O4, and N2O5), most of which co-workers.9−14
react immediately with water upon dissolution resulting in The resulting oxygen may involve in another reaction with NO
HNO3 (nitric acid) and HNO2 (nitrous acid). Only N2O and NO2 following4
(nitrous oxide) and NO (nitric oxide) do not react with water 2NO + O2 ↔ 2NO2 (4)
and hardly dissolve in water. Dozens of chemical equilibria, both
in liquid and vapor phases, exist in the absorption and desorption According to this reaction, the availability of O2 is therefore
processes that occur simultaneously.2 Therefore, the knowledge required in the production of pure HNO3 using the absorption
of the process’s physicochemical data such as the solubility of process eq 2, i.e., to prevent the buildup of NO from halting the
those gases in water is still incomplete.1 formation of HNO3.
Among the species that react with water, N2O3 (nitrogen At moderate temperatures, the resulting NO or O2 from eq 2
trioxide) and N2O5 (nitrogen petoxide) are the anhydrate forms or eq 3, respectively, builds the system pressure to levels much
of nitrous and nitric acids, respectively, while NO2 (nitrogen higher than they would have been if the reactions did not occur.9
dioxide) and its dimer N2O4 (nitrogen peroxide or nitrogen Still to worsen the situation, the resulting NO in eq 2 may
tetroxide) coexist in equilibrium up to about 150 °C:3 associate with NO2 to form N2O3:1,2
NO + NO2 ↔ N2O3 (5)
2NO2 ↔ N2O4 (1)
N2O3 is unstable and reacts with water to form nitrous acid,7
Generally speaking, the term nitrogen dioxide is meant to include HNO2, which is often considered to involve in intermediate
both NO2 and N2O4. In this work we denote them with an reactions for the overall reaction of eq 2. Both acids, HNO2 and
asterisk to remind us of these duo species, i.e., NO2*. HNO3, in turn also dissociate into their constituting ions in
It is customary to summarize the overall chemical equilibrium water.2,7
in the absorption of NO2* in water as4−7 Furthermore, the overall reaction eq 1 is in fact a
heterogeneous equilibrium, in which the aqueous liquid phase
3NO2 * + H 2O ↔ 2HNO3 + NO (2)

The high reactivity of NO2* in water precludes direct Received: July 26, 2013
measurement of physical properties such as the Henry’s Revised: September 24, 2013
coefficient, the magnitude of which is customarily used in the Accepted: October 14, 2013
interpretation of kinetic processes.2 In this case, the coefficient Published: October 14, 2013

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is in equilibrium with the vapor phase above it.1 Therefore, the Whereas K is thermodynamically a function of temperature
system has the physical equilibrium of the phases and only21 as evident in eq 9, it is not the case with K1. Upon
simultaneously the chemical reaction equilibrium in eq 2. substituting the fugacities given by eq 8 into eq 7, K1 in the vapor
In summary, the complexity makes the modeling of this phase may be calculated as
reacting system more difficult. In this work, we attempt to derive ̂ )3 (ϕ ̂ ) y
a model for the physical and chemical equilibria of NO2 in water, (ϕNO2 H2O H2O K
K1 = 2 2
which is needed to describe the absorption of NO2 into aqueous ̂ ) (ϕ ̂
(ϕNO ) y P (10)
HNO3 HNO3
solutions. This study will also be the initial step for a later
application of the model in flue gas sequestration into aquifers. Therefore, without a reliable EOS, it is not possible to connect
We apply an equation of state (EOS), namely the perturbed- the experimentally derived value of K1 with the equilibrium
chain statistical associating fluid theory (PCSAFT),15 which has constant K. In this work, we couple eq 9 for K with PCSAFT to
been widely used in petrochemical industries due to its reliable calculate K1 and match it with the literature data, and thus
accuracy and predictability.16 The kinetics is not considered, as establish the EOS validity before making predictions on the
we are only concerned with the equilibrium state of the system. solubility of NO2 in water at various conditions relevant to flue
To the best of our knowledge, it is the first attempt to model the gas geologic sequestration.
physicochemical equilibria of this reacting system using a Physical Equilibrium. The heterogeneous nature of the
statistical-mechanics based EOS such as PCSAFT. reaction in eq 1 also requires the system to be in vapor−liquid

■ THEORY
Chemical Equilibrium. The most widely used property of
phase equilibrium (VLE), where the fugacity of component i in
the mixture is the same throughout all phases, in this case vapor
(V) and liquid (L) phases:
the reacting system of NO2 in water or in aqueous nitric acid fi ̂
V
= fi ̂
L
solutions is the partial equilibrium constant of reaction eq 2 (11)
defined as4,5 The equality of the fugacities in eq 11 must be solved
(yNO ) 1 simultaneously with mass-balance equations to find the
(PNO) equilibrium compositions in both vapor and liquid phases:
K1 = 3
=
(PNO2) (yNO2 )3 P 2 (6) lxi + (1 − l)yi = zi (12)
which is actually a factor of the reaction equilibrium constant:
Here, l is the mole fraction of the liquid phase, and zi is the overall
( f ̂ /f 0 )( f ̂ 0
/f HNO3 )2 mole fraction of component i. It is also important to realize that
K = NO NO0 HNO3 all mole fractions must sum up to unity:
( f ̂ /f
NO2
)3 ( f ̂ /f 0 )
NO2 H2O H2O (7)
∑ xi = ∑ yi = 1 (13)
In eq 6, y and P are the gas mole fractions and the total pressure,
respectively, while f ’s with hats in eq 7 are the fugacities in Physicochemical Equilibrium. The VLE of the overall
mixtures and those with superscripts 0 are the fugacities at reaction eq 2 has 4 chemical components: H2O, HNO3, NO2*,
standard states, which are the ideal gas at 1 bar in vapor phase, or and NO. As we will show in the model, NO2* may be treated as a
the pure-component fugacities at 1 bar and the system component instead of two in SAFT framework. Therefore, upon
temperature in the liquid phase. The fugacity and the mole bookkeeping we have 9 independent equations to solve for 9
fraction of component i are related through variables: {xi}, {yi}, and l. However, the compositions must also
satisfy the chemical equilibrium represented by the reaction
̂
fi ̂ = yi ϕiP constant K, eq 7, and, consequently, the mass balance of the
(8)
chemical reaction, where the overall mole fractions {zi} in fact
where ϕ is the fugacity coefficient, which is calculated using an result from the chemical reaction and are calculated through
EOS, in our case the PCSAFT. The fugacities in mixtures in eq 7
n0, i + ενi
may be calculated in either phase because the vapor and liquid zi =
phases are in equilibrium, where the fugacities are equal in both ∑ (n0, i + ενi) (14)
phases. However, as indicated in eq 7, the value of K still depends
on the standard states of the phases. In this work, the vapor phase In eq 14, {n0,i} is the initial moles before the reaction occurs, νi is
is chosen for convenience because the reaction equilibrium the stoichiometric coefficient of species i in the reaction, and ε is
constant has been determined in the vapor phase,17 which can be the extent of reaction. An effective algorithm for this
expressed in temperature in the range of interest 293 K < T < 400 physicochemical equilibrium was adopted from Sanderson and
K as Chien.22
To know what inputs are needed for the equilibrium
log K = − 8.847 85 + 2045.883 56T −1 (9) calculations, we must first determine the degree of freedom of
the reacting system, which follows the Gibbs rule21
The value of K in eq 9 was determined using the experimental
F=N−π+2−r (15)
entropy of nitric acid gas and the known thermodynamic
properties of the other reactants,17 but it has never been verified where N, π, and r are the number of components, phases, and
in applications due to the lack of reliable EOS in calculating the chemical reactions, respectively; in our case, they are 4, 2, and 1,
fugacity coefficients. Instead, K1 is often used to represent this leading to a degree of freedom of 3. This means that, besides the
system and estimated through eq 6, i.e., the partial pressures of temperature (T) and pressure (P), we still need another entity as
NO2 and NO in the vapor phase, which may be derived from a known variable in order to have the information of the system
experimental measurements.4,5 Some models for K1 were complete. We may choose, for example, the loading of NO2
proposed using empirical equations18,19 and nomograms.19,20 in water, which can be defined as moles of NO2 injected per
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Figure 1. Association schemes used in the model: (a) NO2 and NO molecules, stars and triangles are the associating sites (star, dimer type; triangle,
proton-acceptor type). The dimer forms are shown on the right next to them. (b) HNO3 molecule, open triangle is the associating site of proton-donor
type (hydrogen atom).

Table 1. Pure-Component Parameters

m σ (Å) ε/kBa (K) associating sitesb εA/kB (K) κ ref
H2O 1.2190 c 213.5741 (2, 2, 0) 1851.9773 0.052 246 31
NO2* 1.7202 2.793 41 203.6308 (0, 4, 1) 6596.2014 4.335 × 10−6 this work
HNO3 2.5859 2.817 49 287.8668 (1, 2.5, 0) 652.6610 0.049 890 this work
NO 1.4388 2.768 06 112.0302 (0, 2, 1) 1504.8371 0.000 185 this work
N2 1.2414 3.299 20 89.2230 (0, 0, 0) 32
a
kB: Boltzmann constant. bThe first digit is the number of proton-donor type of associating sites, the second digit is the number of proton-
acceptor type of associating sites, and the third digit is the number of type-1A associating sites. cσH2O = 2.798 384 + 120.733 275T−1 −71 515.85T−2 +
11 052 303T−3 (Å).

1000 mol of water. We will use this entity to calculate the molecules, in this case also known as hydrogen bonding,
solubility of NO2 in water. occurs between two sites of different types. The proton-
In some previous studies, this additional entity was chosen to donor sites in water molecules belong to the hydrogen atoms,
be the amount of nitric acid in the liquid phase that is in while the other type belongs to the electron lone-pairs in
equilibrium with the gases in the vapor phase.4,5 However, the the oxygen atoms. Such association scheme is known as
experiments were carried out using an inert background gas, i.e., type 4C.23
nitrogen, to dilute NO2 before passing it through the aqueous Four electron lone-pairs that are also present in the oxygen
liquid phase. Though this gas does not participate in the chemical atoms of NO2 contribute four associating sites of proton-
reaction, its presence affects the concentrations in the equilibria acceptor type in the molecule. These sites enable NO2 to cross
in two ways: first, its mole must be added to the denominator of associate with water molecules, but do not associate among
eq 14, and second, it participates in the physical phase equilibria, themselves. However, NO2 molecules are capable of forming
i.e., eqs 11 and 12. Therefore, instead of 4 components, in this dimers N2O4 through eq 1, which is in fact dominant at low
case we have 5 components, and thus 12 variables ({xi}, {yi}, ε, temperatures particularly in liquid phase.24 In the SAFT
and l) to solve for from 12 equations, i.e., eqs 11−13 and eq 7 framework, the dimerization is modeled as an association
with K from eq 9, after applying eq 14 to find {zi} as described bonding through a site, in this case on the nitrogen atom, that
elsewhere.22 Such usage of a background gas increases the is neither proton-donor nor proton-acceptor type, known as type
system’s degrees of freedom by one, so that the reacting system 1A,23 which can associate between themselves but not with other
of NO2 in water now has a degree of freedom of 4, which types of associating sites. This approach provides us with an
means we need two known entities in addition to T and P to have advantage that we do not need to consider N2O4 as an
the system information fixed. In reproducing their data, we independent species, so that NO2 is actually NO2* in SAFT
choose the concentration of HNO3 in liquid phase (xHNO3) and framework exactly as in the overall reaction eq 2. This treatment
the mole fraction of NO in vapor phase (yNO) to accompany the has been proven to be effective.25 Dimerization also occurs for
pressure and temperature as the inputs of the calculations. NO molecules,26 but they do not cross associate with water

■ MODELING
Molecular Association. To make all calculations in the
molecules as inferred from molecular simulations.27 The
monomer and dimer structures of NO2 and NO in our model
are depicted in Figure 1a.
previous section, we apply an EOS, the input of which needs For nitric acid molecules, the presence of a proton-donor site
some modeling for the molecules in the system. Because NO2, on the hydrogen atom and some proton-acceptor sites at the
H2O, NO, and HNO3 are associating molecules, the model for oxygen atoms makes both the self-association and cross-
the molecular association is pivotal in this work. association with water molecules possible. There are six electron
As is commonly done, we model the water molecule to have lone-pairs at three oxygen atoms in the molecule, but only some
two associating sites of proton-donor type and two associating of them are effective as proton-acceptor sites due to the steric
sites of proton-acceptor type. The association between effects arising from crowded configuration of the oxygen atoms.
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A similar situation has been found in alcohols, in which the system. The EOS calculates the residual Helmholtz free energy of
presence of the alkyl group allows only one effective site on the the chemical system, as follows.
oxygen atom.28 Therefore, one associating site may be assigned
on each oxygen atom in HNO3 as shown in Figure 1b. However, Ã res = Ã hs + Ã chain + Ã disp + Ã assoc (16)
this assignment does not give adequate representation of binary Here, the superscripts of the free energy terms on the right-hand
phase equilibria data, particularly that of H2O/HNO3, which is side of eq 16 are hard-sphere, chain, dispersion, and association,
dominant in the investigated chemical systems. It may be caused respectively. These refer to the molecular interactions in the
by the presence of the proton-donor site on the hydrogen atom system: the hard-core repulsion, the chain-forming covalent
that introduces steric shielding to the neighboring proton- bond, the van der Waals type of dispersive attraction, and the
acceptor site. The fact that HNO3 undergoes ionic dissociation in highly directed associating interaction through hydrogen bonds
water provides an estimate of the number of proton-acceptor sites to or dimerization, respectively.
be between 2 and 3, corresponding to molecular and ionic structures, For each associating species in the system, the EOS has five
respectively. We choose the average value of 2.5 for this number, parameters: the segment number m, the segment diameter σ, the
which is quite unusual being a noninteger, but justifiable as it turns segment energy ε, the association volume κ, and the association
out to represent the binary H2O/HNO3 very well as discussed later energy εA. Nitrogen, which is the only nonassociating molecule
in the paper. The direct benefit of this assignment is that there is no in the system, does not have the latter two parameters. In a strict
need to explicitly treat the ionic dissociation of the acid in the SAFT sense, the number of associating sites may be considered as a
framework, which makes the calculation tasks much simpler. parameter that may be fitted from experimental phase-equilibria
Cross associations occur between HNO3 and H2O, HNO3 and data, but as shown earlier in the previous section it may also be
NO2, as well as NO2 and H2O. The association between HNO3 estimated from the molecular structures. This estimation helps
and H2O is made asymmetric, in which the site on the hydrogen the other EOS parameters with more physical values.
atom of HNO3 does not cross associate with oxygen atoms of The details of the EOS can be found in the original work,15
water. Cross association occurs only between hydrogen atoms of while the whole association scheme can be handled using the
H2O and sites on oxygen atoms of HNO3. This asymmetric generalized approach.29 As a note, the dimerization of NO2 and NO,
assignment is needed to make the model work in representing as well as the cross association between NO2 and NO, is not of
the azeotropic binary mixture of HNO3/H2O. In addition to the donor−acceptor type, and therefore needs caution and modification
aforementioned cross associations, the NO2 and NO molecules explained in the generalized approach.29 We apply an assumption
are also allowed to cross associate each other through their type- here that this non-donor−acceptor association occurs independ-
1A associating sites to account for the fact that the molecules may ently from that of the hydrogen-bond type of association. In other
combine as N2O3 through eq 5.1,2 words, an occurrence of one cross-association type does not affect
the occurrence probability of the other type.

■
To validate the model against the experimental K1, where
nitrogen is used as the background gas, the nitrogen molecule is
to be included. But because nitrogen is a nonassociating RESULTS AND DISCUSSION
molecule, it does not have any association sites. Parameter Derivation. The pure-component parameters of
PCSAFT EOS. In the following, we will briefly introduce the all species in the system are tabulated in Table 1. They are derived
PCSAFT EOS that we use to apply the model for this particular from fitting the literature vapor pressure and saturated-liquid

Table 2. Fitting of the Pure-Component Parameters Table 4. Cross-Association Parametersa

fitting range H2O NO2* HNO3 NO
AADa AAD H2O 900.00 2340.00b
T (K) Psat (bar) ref Psat vL,sat NO2* 0.05 881.0923 5450.437c
NO2* 294−388 1−31.28 DIPPR30 0.09% 0.07% HNO3 0.05b 0.049 89
HNO3 233−373 0.0007−1.783 DIPPR30 1.23% 0.24% NO 0.000 15c
NO 110−172 0.24−43.93 DIPPR30 0.47% 0.53% a
The diagonally upper-right entries are the cross-association energy
a
Average absolute deviation = (βexp − βcalc)/ βexp × 100% (exp = εAij/kB (K) and the lower-left entries are the cross-association volume
experimental; calc = calculated); β is the vapor pressure Psat or the κij. bOnly between proton-donor sites in H2O and proton-acceptor
saturated liquid volume vL,sat. sites in HNO3 (see text). cType 1A cross association.

Table 3. Coefficients of Binary Interaction Parameters in Equation 18 and the References of the Experimental Data Used To
Derive Them
binary a b c d data ref T range (°C)
H2O−HNO3 −0.264 16 5.097 0 0 34 24.6−120.6
H2O−NO −1.1144 64.235 −8.5220 0 37 0−100
H2O−N2 −0.892 15 40.205 −4.316 0 35 5−89.8
HNO3−NO2* 75.486 75 −6911.961 94 2114.659 23 −2.1614 38 21.5−76.6
HNO3−NO 0 0 0 0
HNO3−N2 0 0 0 0
NO2*−NO 2.345 −141.6 20.57 0 40 37.7−104.4
NO2*−N2 0 0 0 0
NO−N2 0.04 0 0 0 39 (−159.4)−(−153.6)
H2O−NO2* kij = 0.33743 − 4.827 × 107 × exp(−0.060 92T) 33 20−80

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specific volume data.30 The fitting properties, references, and the The binary interactions are generally functions of temperature,
qualities of fit are tabulated in Table 2. As defined before, NO2* is which are in the form of polynomials
in fact a mixture of NO2 and its dimer N2O4. The parameters of
H2O and N2 are directly taken from previous studies.31,32 kij(T ) = a + b × 10−4T + c × 10−6T 2 + d × 10−6T 3
In mixtures, where interactions between unlike species occur, (18)
binary interaction parameters kij are needed and derived from binary
VLE data for interactions between species. The binary interaction where the coefficients a, b, c, and d are listed in Table 3. The
parameters are used to correct the molecular interactions and are exception is for H2O−NO2*, which is also given in the last row of
implemented in the combining rule of the energy parameters: the table. The use of a high-order polynomial in the parameter
correlation is necessary in our case to obtain acceptable
εij = εiεj (1 − kij) (17) accuracies for several binary mixtures due to the limited
availability of their experimental data as described later.
Moreover, as our applications fall within the correlation
temperature range, the use of eq 18 is safe and justified for our
model. Greater data availability in the future will definitely
improve the correlation quality and extend the applicability to a
wider temperature range.
Among the binary parameters, the kij between H2O and NO2*
is the only one that was derived from the experimental physical
VLE of ternary mixture, which is in this case H2O/HNO3/
NO2*,33 because the data of physical VLE of the binary H2O/
NO2* do not exist due to the high reactivity of the system. There
are three binary mixtures that do not have experimental data, i.e.,
NO/HNO3, N2/HNO3, and NO2*/N2, the binary parameters of
which could fortunately be set to zero. This fortunate fact is
justified in parameter sensitivity tests of the quinary mixture of
N2/H2O/HNO3/NO2*/NO discussed later in this paper.
The cross-association parameters, which are commonly
derived from mixing rules, have to be directly fitted from the
experimental data due to the high complexity of the reacting
system. The parameters are listed in Table 4. No cross
association occurs between NO and H2O or HNO3.
EOS Performance. The EOS performance is presented here
for both the correlations in deriving the parameters and their
extrapolations to independent data, not included in the correlations,
Figure 2. VLE of H2O/HNO3: experimental data,34 open symbols are using the derived parameters without additional adjustments.
the dew points; filled symbols are the bubble points. Curves are The most important binary mixture is H2O/HNO3, which
PCSAFT correlations. contains the dominant species in the liquid phase. Although

Figure 3. EOS extrapolation on the behavior of dilute HNO3 aqueous solutions: symbols are experimental data;4 curves are PCSAFT calculation.

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Figure 4. VLE of N2/H2O: (a) solubility of N2 in liquid phase, curves are PCSAFT correlation; (b) mole fraction of water in vapor phase, curves are
PCSAFT extrapolation. Symbols are experimental data.35,36

Figure 5. Solubility of NO in H2O: symbols are experimental data;37 Figure 6. Phase equilibria of HNO3/NO2*: symbols are experimental
curves are PCSAFT correlation. data;38 curves are PCSAFT correlation.

many authors have discussed this particular system,9−11 most of solubility in the aqueous phase. While the experimental data for
them did not provide the physical equilibria data that we need to N2/H2O are abundantly available in the literature, for example,
derive the binary interaction parameter. The performance of those shown in Figure 4,35,36 there is only one set of data available
PCSAFT correlation for this binary, which has an azeotropic for NO/H2O.37 It is also the case for HNO3/NO2*, for which
behavior, is shown in Figure 2 at various T and P along with the only one set of physical equilibrium data is available,38 while
experimental data.34 The performance is then extrapolated to the many others are physicochemical data at high concentration of
dilute HNO3 aqueous solutions at atmospheric pressure and HNO311−14 that follow the dissociation reaction of eq 3
compared with the data of Burdick and Freed4 in Figure 3. irrelevant to flue gas geologic sequestration. The EOS perform-
Figures 4 and 5 show the EOS performance in N2/H2O and ance for HNO3/NO2* is shown in Figure 6, where it exhibits
NO/H2O systems, respectively, both of which have small gas liquid−liquid equilibrium (LLE) at low temperatures.
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Figure 7. Binary VLE: (a) N2/NO; (b) NO2*/NO. Symbols are experimental data;39,40 curves are PCSAFT correlation.

Figure 8. VLE of H2O/HNO3/NO2*: (a) data used to derive the binary parameter of NO2*/H2O; symbols are experimental data,33 curves are PCSAFT
correlation. (b) EOS extrapolation examples at other compositions compared with experimental data.33

The VLE of the gases, N2/NO and NO2*/NO, are well represented experimental data of which are not available in the literature. We ran
along with the experimental data39,40 in Figure 7a,b, respectively. parameter sensitivity tests over the quinary mixtures N2/H2O/
Due to the unavailability of physical VLE data as mentioned before, HNO3/NO2*/NO, from which we conclude that those remaining
the binary parameter of NO2* in water was derived from the NO2*/ three binary parameters have very small effects on the phase equilibria
H2O/HNO3 ternary. Since we already have the binary parameters for calculations. Therefore, we safely set them to zero for simplicity.
NO2*/HNO3 and H2O/HNO3, the derivation of that of NO2*/ EOS Validation. Now, using the parameters listed in Tables 1,
H2O from the ternary data is straightforward. Caution must be taken 3, and 4, along with the equilibrium constant K in eq 9, the
for this ternary, however, because most of the data in the literature are logarithm of K1 can be calculated and matched with the
physicochemical rather than physical VLE. The physical VLE data33 experimental data. The available data were all obtained by varying
are shown in Figure 8 together with the EOS representation. the temperature and liquid concentration of HNO3 (xHNO3) at
Up to this point, all parameters have been derived, except for atmospheric pressures. Due to the use of N2 as the background gas,
the binary parameters of N2/HNO3, NO/HNO3, and N2/NO2*, the as discussed before, the degree of freedom of the chemical system is
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Figure 9. Logarithm of partial equilibrium constant K1 versus nitric acid concentration at P = 1 atm: (a) Tereshchenko et al.;5 (b) Burdick and Freed.4
Symbols with connecting curves are calculated using the EOS.

Figure 10. Calculated values of log K1 at 25 °C based on the choice of yNO: (a) comparison with Burdick and Freed,4 dotted curve from Figure 9b, dash-
dotted curve for quaternary H2O/HNO3/NO2*/NO, solid curve for quinary with yNO from part b. (b) The corresponding choices of yNO (for the
quaternary, yNO is fixed by the experimental conditions, not by choice).

in fact 4, not 3, so that the data were not measured systematically as the determination of gas concentration in the vapor phase is
they should have been if another property was fixed in the inaccurate in some cases, particularly when the gas exists in small
experiments in addition to the system P, T, and xHNO3. The quantities, i.e., at low concentration of HNO3 (<10 wt %) for
researchers assumed that the presence of the background gas could NO2* and at high concentration of HNO3 (>55 wt %) for NO.4
safely be neglected due to the small N2 solubility in water as well as Figure 9 shows the comparison between the EOS-calculated log K1
the inert nature of the N2 in the chemical reaction eq 2. with that of Burdick and Freed,4 as well as that of Tereshchenko et al.5
Unfortunately, this assumption produced experimental data We calculated log K1 at the original experimental conditions (P, T,
with obvious scattered distribution, as can be seen in the original xHNO3) and one of the published mole fractions of NO that was
paper,4 in which experiments at the same condition (P, T, xHNO3) experimentally derived in the vapor phase (yNO) to satisfy the system
give very different concentrations in the vapor phase. Even worse, degree of freedom of 4. In Figure 9a, the data of Tereshchenko et al.5
16039 dx.doi.org/10.1021/ie402417p | Ind. Eng. Chem. Res. 2013, 52, 16032−16043
Industrial & Engineering Chemistry Research Article

Figure 11. Prediction of solubility curves of NO2* in water: (a) bubble pressure vs NO2* loading at different temperatures, (b) bubble pressure vs
temperature at different NO2* loadings.

are well reproduced except at low temperature (20 °C) and high acid
concentration, where the resulting NO in the vapor phase is so small
that may be buried in the uncertainty of the measurements.
As shown in Figure 9b for the data of Burdick and Freed,4 a
similar symptom occurs at 25 °C and high HNO3 concentration,
as well as at 75 °C, the very reason why no data was measured at
57.8 wt % of HNO3. Considering the omission of some data
before averaging the values of log K1, the apparent order of the
logarithm of K1 data in Figure 9b may be deceptive.
Regarding the deviation observed above at high acid
concentrations, particularly at low temperatures, we recalculated
the log K1 at 25 °C at the same conditions (P, T, xHNO3) as that in
Burdick and Freed, but now with a systematic choice of yNO. In
addition, we also calculated log K1 at the conditions for
quaternary H2O/HNO3/NO2/NO, in which we have a degree
of freedom of 3, so that the input (P, T, xHNO3) is sufficient to fix the
system properties; in this case log K1 does not depend on yNO. The
results are shown in Figure 10a with the corresponding yNO used in
the calculations in Figure 10b. The yNO curve for the quaternary in
Figure 10b is not by choice, but fixed by the conditions (P, T, xHNO3).
As seen in Figure 10a, the values of Burdick and Freed at high acid
concentration can be reproduced (solid curve) only if we use much
smaller yNO (solid curve) as shown in Figure 10b. In other words,
Figure 12. Predicted portion of injected NO2* that dissolves in water at
the experimentally derived yNO is inaccurate due to the diminishing
25 and 75 °C for ζ = 0.001.
amount of NO in the gas phase. The dependency of log K1 on yNO
can be clearly observed if the acid concentration is lowered while
yNO is increased as we track the solid curves upward in Figure 10a,b. Predictions on the Solubility of NO2* in Water. The total
When yNO is larger than that of Burdick and Freed, log K1 gets lower NO2* that dissolves in water also includes the reaction products
approaching the fixed value given by the quaternary system, where (HNO3 and NO), and can be calculated through the mole
NO is the dominant gas in the vapor phase replacing N2. From this balance:
discussion, we learn that the presence of N2 cannot be neglected in
calculating K1, particularly at low and high acid concentrations. total NO2 * mole dissolved
The calculated K1 values matching with that derived from = nNO2 (liquid) + nHNO3(liquid) + nNO(liquid)
* (19a)
experiments provide us with two pieces of information. First, the
literature values of K in eq 9 are verified for use in the main reaction l ∑ (n0, i + ενi)
of eq 2. Second, the EOS is validated that allows us to proceed with =(x NO2 * + x HNO3 + x NO)
calculations predicting the solubility of NO2* in water. n0,NO2 * (19b)

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Industrial & Engineering Chemistry Research Article

Figure 13. Predicted composition of the dissolved portion of NO2* in water: (a) at 25 °C, (b) at 75 °C for ζ = 0.001.

The solubility of NO2* in water is calculated from the

quaternary system of H2O/HNO3/NO2*/NO with P, T, and the
NO2* loading as the input, which makes more sense for absorption
purposes rather than xHNO3. The NO2* loading ζ is defined here as
moles of NO2* injected into every 1000 mol of water:
n0,NO2 *
ζ=
1000 mol H 2O (20)

We assume that there is no product species (HNO3 and NO)

in the system before the chemical reaction eq 2 as it should be in
the absorption of NO2 in water. The results are presented as
solubility curves in bubble-point diagrams in Figure 11a,b. The
bubble-point pressure is the pressure above which all the gas
dissolves in water. In Figure 11a, the solubility curve can also be
interpreted as the maximum loading below which all injected
NO2* dissolves in water. In Figure 11b, it can be understood as
the maximum temperature above which some of the gas escapes
to the vapor phase.
It is clear from Figure 11b that the bubble pressure
dramatically increases at temperatures between 25 and 40 °C.
Consequently, the solubility of NO2* hugely drops from 25 to
40 °C.
The percentage of dissolved NO2* relative to the injected Figure 14. Predicted concentration of HNO3 in liquid phase at bubble
amount, i.e., the dissolved species for every 1000 molecules of pressures: ζ = 0.001 (right vertical axis) and ζ = 0.006 (left vertical axis).
H2O on the right-hand side of eq 19a divided by 1000 × ζ, is
presented in Figure 12 as a function of pressure for loading ζ = complete according to eq 2 even at atmospheric pressure. It also
0.001. The percentage reaches 100% at the bubble pressures. The confirms that the reaction in eq 2 does occur in the liquid phase.
corresponding composition of the dissolved portion of NO2* is The completion of the reaction is the cause of the dramatic
presented in Figure 13a,b. The top lines in these figures are the increase of the bubble pressure at 25−40 °C in Figure 11, as
same as those in Figure 12. demonstrated in Figure 14 where the acid concentration quickly
It can be seen in Figure 13a,b that most of the dissolved NO2* approaches 66.67% (xHNO3 = 0.004 for ζ = 0.006, and xHNO3 =
is in the form of HNO3. The acid concentration decreases with 0.000 67 for ζ = 0.001) in this range of temperature. The
pressure as the amount of unreacted NO2* increases, which corresponding maximum weight fraction of the resulting HNO3 is
doubles from atmospheric pressure to the bubble pressure at 1.38% and 0.23%, respectively. The curves in Figure 14 were
25 °C. At 75 °C, this behavior is not obvious in Figure 13b due to calculated at their bubble pressures; the behavior at other pressures
the minute amount of unreacted NO2*. The percentage of the is very similar to that at bubble pressures.
resulting HNO3 at 75 °C approaches 66.67% at all pressures, The compositions of vapor and liquid phases at different
which means the reaction of NO2* with H2O is practically pressures corresponding to the conditions in Figure 12 are given
16041 dx.doi.org/10.1021/ie402417p | Ind. Eng. Chem. Res. 2013, 52, 16032−16043
Industrial & Engineering Chemistry Research Article

Figure 15. Predicted compositions of NO2*/H2O system at 25 and 75 °C for ζ = 0.001: (a) vapor phase, (b) liquid phase.

in Figure 15a,b, respectively. The calculations start at vapor phase, while HNO3 trails water in dominating the liquid
atmospheric pressure up to the bubble pressure at each phase.

■
temperature. Since the aqueous liquid phase consists of mostly
water (more than 99.9 mol %) at both temperatures, water mole AUTHOR INFORMATION
fraction in liquid is not included in Figure 15b for clarity.
Corresponding Author
The order of abundances is NO, H2O, NO2*, and HNO3 in
the vapor phase, and H2O (not shown in Figure 15b), HNO3, *E-mail: [email protected].
NO, and NO2* in the liquid phase. At 25 °C and lower pressure Notes
region, however, NO2* is more than NO in the liquid phase. As The authors declare no competing financial interest.

■
the pressure increases, the concentrations of NO and NO2*
increase in both phases; the increase is not so obvious at 75 °C in ACKNOWLEDGMENTS
the vapor phase due to the scale of Figure 15a. On the contrary,
This work was supported by DOE Financial Assistance
the concentrations of water and HNO3 in the vapor phase Agreement DE-FE0004832. The authors also acknowledge the
decrease with pressure, while they are relatively constant in the financial support of the School of Energy Resources and the
liquid phase. Enhanced Oil Recovery Institute at the University of Wyoming.

■ CONCLUSIONS
The model using PCSAFT is found capable of describing the
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