Article

pubs.acs.org/jced

Solubility of Hydrogen Sulfide in N‑Methylacetamide and N,N-

Dimethylacetamide: Experimental Measurement and Modeling
Mohammad Shokouhi,* Hadi Farahani, Masih Hosseini-Jenab, and Amir Hossein Jalili
Research Institute of Petroleum Industry (RIPI), P.O. Box 14665-137, Tehran, 0098, Iran

ABSTRACT: The solubility of hydrogen sulfide in N-methylacetamide and N,N-

dimethylacetamide were experimentally measured. Gas concentrations were
systematically measured by the isochoric saturation method at temperatures from
(303.15 to 363.15) K and pressures from the vapor pressure of solvent up to about
2.2 MPa. Results show that H2S solubility in N,N-dimethylacetamide is more than
that in N-methylacetamide. The experimental data were correlated using (1) the
Krichevsky−Ilinskaya equation and (2) a generic Redlich−Kwong (RK) cubic
equation of state. Using the solubility data, the partial molar thermodynamic
properties of solution such as Gibbs free energy, enthalpy, and entropy at infinitely
diluted solution, and also the enthalpies of absorption of loaded solutions were
calculated using the Gibbs−Helmholtz equation.

■ INTRODUCTION
Acid gases solubility in physical organic solvents is important
for industrial application, particularly, for the treatment of
natural gas as well as for the development of correlations and
prediction methods in molecular thermodynamics.1−5 Among
the amides group, the solubility of CO2 in dimethylformamide
(DMF) is extensively reported6−11 in literature. Also the phase
behavior measurements of binary carbon dioxide/N,N-
dimethylacetamide and the carbon dioxide/N,N-diethylaceta-
mide system at high pressure are reported by the Byun research
group.12 Yet except for the solubility of hydrogen sulfide in
DMF13 and also the solubility of SO2 and H2S in DMA14 at
only one gas partial pressure equal to 0.101 MPa and
temperatures 268.15 K, 298.15 K, and 333.15 K, we have not
found any experimental data on the solubility of hydrogen
sulfide in physical solvents with an amide functional group.
In our ongoing research on the solubility of acid gases in
physical organic solvents, in this work, solubility measurements
of hydrogen sulfide in N-methylacetamide (NMA) and N,N-
dimethylacetamide (DMA) are experimentally investigated.
All experimental trials are carried out via the isochoric
saturation method at the temperature range from (303.15 to
363.15) K and pressures from the vapor pressure of solvent up
to 2.2 MPa. The solubility data are modeled using two distinct
correlations related to two theoretical approaches: the new
version of the Redlich−Kwong cubic equation of state
proposed by Shiflett and Yokozeki for gas−ionic liquid
systems15−17 known as the generic Redlich−Kwong (GRK)
cubic equation of state, and the Krichevsky−Ilinskaya (KI)
equation. Some characteristic partial molar thermodynamic
properties of H2S dissolved at infinite dilution in those solvents
and also the enthalpy of absorption of loaded solutions were
calculated using the Gibbs−Helmholtz equation.
■ EXPERIMENTAL SECTION
Materials. The specifications and sources of the chemicals
used in this work are summarized in Table 1.
All the materials were reagent grade and used without further
purification. All solvents were prepared by calibrated balance
(Mettler model AE 200) with an uncertainty of ± 0.0001 g.
Apparatus and Procedure. The details of the exper-
imental method for the measurement of gas solubility have
previously been presented18,19 and only a short description will
be provided here.
The double wall equilibrium cell was connected to a water
recirculation bath (model T 2500 PMT Tamson) with
temperature stability within ± 0.02 K, and the temperature
was measured using a model TM-917 Lutron digital
thermometer with a 0.01 K resolution equipped with a Pt-
100 sensor inserted into the cell. The equilibrium cell pressure
was measured using a model PA-33X KELLER pressure
transmitter sensor in the range of (0 to 25) bar, which was
accurate to within 0.01 % of full scale, and that of the gas
container was measured using a Baroli type BD SENSORS
digital pressure gauge in the range of (0 to 25) bar, which was
accurate to within 0.01 % of full scale.
One can calculate the total number of moles of acid gas
injected into the equilibrium cell using the procedure adopted
by Park and Sandall20 and Hosseini Jenab et al.:19
Vgc ⎛ Pi P⎞
nag = ⎜ − f⎟
RTa ⎝ Z i Zf ⎠ (1)
Received: May 28, 2014
Accepted: January 6, 2015

© XXXX American Chemical Society A DOI: 10.1021/je500478t

J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 1. Specifications and Sources of Chemicals Used in This Work

chemical name molecular formula/ CAS registry number purity source
hydrogen sulfide H2S 7783-06-4 99.95 % Roham Gas Company
N-methylacetamide C3H7NO 79-16-3 > 99 % Merck
N,N-dimethylacetamide C4H9NO 127-19-5 > 99.9 % Aldrich Chemical

where Vgc denotes the volume of the gas container, Zi and Zf ⎛ + wsolvent ⎞⎟
mag wsolvent
are the compressibility factors corresponding to the initial and nagg
⎜
= ρag ⎜Vauto −
( 1000 )
final pressures, Pi and Pf, respectively, in the gas container ⎜ ρcharged solution ⎟⎟
before and after transferring gas, and Ta is the ambient ⎝ ⎠ (7)
temperature, which is equal to that in the gas container. where mag is the molality of acid gas obtained from the iteration
Compressibility factors were calculated using NIST.21 Equili- technique or as an approximate estimation obtained from the
bration between liquid and vapor phases inside the cell were molality calculated with eqs 3 through 6.

normally achieved within about 2 h after the start of stirring,
and the partial pressure of gas at equilibrium in the equilibrium
cell, Peag, was calculated as follows:
Page = PT − PVP
(2)
where PT and PVP denote the total pressure and vapor pressure
of solution. A key issue is the determination of the vapor
pressure of the mixture solution since this value must be
subtracted from the total pressure to obtain the partial acid gas
pressure.
The moles of remaining acid gas in the gas phase, ngag, was
determined from
■
RESULTS AND DISCUSSION
Validation of the experimental apparatus and accuracy of data
were recently investigated for CO2/dimethylformamid and also
CO2/MDEA aqueous solution in a previous work.13
The liquid phase molar volume for DMA was taken from the
density data reported by Scharlin.22 Those data are correlated
using a linear equation, and for the case of NMA, the liquid
phase molar volume was obtained from linear correlation
equation fitted through experimental data reported in the
literature.23−25 Both density and temperature equations along
with their correlation coefficients (R2) are reported in Table 2.

VgPage Table 2. Antoine Constants for the Equation ln(p/kPa) = A

nagg = = Vgρag + B/(T/K + C), and Linear Correlation Equation for Density
ZagRT (3) with Correlation Coefficient, R2
where Vg is the gas phase volume, T is the equilibrium chemical temperature range
name (K)
temperature of the cell, and Zag and ρag are the compressibility
factor and density of acid gas at Peag and T, respectively. The Antoine Constants
number of moles of gas in the liquid phase was then NMA 313.2−443.15 A= B= C=
18.3951 −6431.73 −9.41471
determined from
DMA 298.15−439.3 A= B= C=
15.5415 −4398.40 −36.6354
nagl = nag − nagg (4) Density Equations
NMA 303.15−363.15 ρNMA (g/cm3) = −(8.102 × 10−4)·T/K +
The molality and mole fraction of the loaded gas in the liquid 1.1956 (R2 = 0.9991)
phase is defined as DMA 277.13−363.15 ρDMA (g/cm3) = −(8.800 × 10−4)·T/K +
1.1979 (R2 = 0.9995)
charged 303.15−353.15 ρCharged DMA (g/cm3) = −0.02654·mH2S −
nagl (mole) DMA (8.800 × 10−4)·T/K + 1.1979
mag = 1000
wsolvent(g) (5)

nagl (mole)
xag = wsolvent(g)
nagl + Msolvent(g)
where nlag is the number of acid gas mole in the liquid phase,
wsolvent is the weight of solvent in g, and Msolvent is molar mass of
pure solvent in g.
As mentioned above the amount of dissolved gas is
calculated from the amount of gas charged to the cell by
subtracting a correction for the amount of gas that is still
present in the vapor phase. That correction is calculated
assuming that the volume of the vapor phase is the difference
between the cell volume and the volume of the unloaded
solvent (which is known from the preparation of the solvent).
However, that procedure neglects a volume change (mostly a
volume expansion) when a gas is dissolved in a liquid.
In this case, eq 3 may be corrected as
Vapor pressures of pure NMA are obtained from Gopal et
al.26 and Manczinger et al.,27 and those of pure DMA are
(6) obtained from Nasirzadeh et al.28 and Ishiguro et al.29 for which
those data correlated with Antoine equation. The Antoine
equations for vapor pressure with the set of constants for the
two liquids are reported in Table 2.
Experimental solubilities of H2S in both solvents are reported
in Tables 3 and 4. Temperature and pressure dependency of
H2S solubility, graphically have been shown in Figures 1 and 2.
As expected H2S solubility in both solvents increases with
increasing pressure and decreases with increasing temperature.
In Figure 3, H2S solubility in DMA, NMA, and also two other
typical organic solvents such as sulfolane (SFL)1 and
dimethylformamide13 have been compared at T = 313.15 K.
As may be seen, the solubility of H2S in DMA is higher than it
is in others.
B DOI: 10.1021/je500478t
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 3. Experimental Solubility of H2S in DMAa

T Pt ± 0.003 PH2S ΔHabs(GH)
K MPa MPa xH2S ± ΔxH2S (xH2S ± ΔxH2S)Cor. kJ/mol
303.15 Pt −3.9 × 10−4
0.041 0.041 0.047 ± 0.003 0.047 ± 0.003 −16.51
0.121 0.121 0.123 ± 0.003 0.124 ± 0.003 −16.07
0.191 0.191 0.181 ± 0.003 0.182 ± 0.003 −15.76
0.335 0.335 0.279 ± 0.004 0.280 ± 0.004 −15.27
0.458 0.458 0.349 ± 0.004 0.350 ± 0.004 −14.97
0.586 0.586 0.409 ± 0.004 0.411 ± 0.004 −14.72
0.734 0.734 0.472 ± 0.004 0.474 ± 0.004 −14.50
313.15 Pt −6.8 × 10−4
0.053 0.053 0.046 ± 0.003 0.046 ± 0.003 −17.64
0.150 0.150 0.121 ± 0.003 0.121 ± 0.003 −17.20
0.238 0.238 0.178 ± 0.003 0.178 ± 0.004 −16.89
0.415 0.415 0.275 ± 0.004 0.276 ± 0.004 −16.41
0.564 0.564 0.344 ± 0.004 0.346 ± 0.004 −16.10
0.719 0.719 0.404 ± 0.004 0.406 ± 0.004 −15.86
0.903 0.903 0.467 ± 0.004 0.470 ± 0.004 −15.63
323.15 Pt −1.16 × 10−3
0.065 0.064 0.045 ± 0.003 0.045 ± 0.003 −18.81
0.184 0.183 0.119 ± 0.003 0.119 ± 0.003 −18.37
0.289 0.288 0.175 ± 0.003 0.175 ± 0.004 −18.07
0.501 0.500 0.270 ± 0.004 0.271 ± 0.004 −17.59
0.681 0.680 0.339 ± 0.004 0.340 ± 0.004 −17.28
0.863 0.862 0.398 ± 0.004 0.400 ± 0.004 −17.03
1.084 1.083 0.461 ± 0.004 0.464 ± 0.004 −16.80
333.15 Pt −1.98 × 10−3
0.081 0.079 0.044 ± 0.003 0.044 ± 0.003 −20.01
0.219 0.217 0.116 ± 0.003 0.116 ± 0.003 −19.58
0.343 0.341 0.171 ± 0.004 0.172 ± 0.004 −19.28
0.594 0.592 0.265 ± 0.004 0.266 ± 0.004 −18.80
0.806 0.804 0.333 ± 0.004 0.335 ± 0.004 −18.49
1.021 1.019 0.392 ± 0.004 0.394 ± 0.004 −18.24
1.279 1.277 0.455 ± 0.004 0.458 ± 0.004 −18.01
343.15 Pt −3.27 × 10−3
0.094 0.091 0.043 ± 0.003 0.043 ± 0.003 −21.24
0.257 0.254 0.113 ± 0.003 0.113 ± 0.003 −20.82
0.404 0.401 0.167 ± 0.003 0.168 ± 0.003 −20.52
0.696 0.693 0.260 ± 0.004 0.261 ± 0.004 −20.05
0.941 0.938 0.327 ± 0.004 0.329 ± 0.004 −19.74
1.194 1.190 0.386 ± 0.004 0.388 ± 0.004 −19.49
1.490 1.486 0.449 ± 0.004 0.452 ± 0.004 −19.25
353.15 Pt −5.19 × 10−3
0.115 0.110 0.041 ± 0.003 0.041 ± 0.003 −22.52
0.299 0.294 0.110 ± 0.003 0.110 ± 0.003 −22.11
0.469 0.464 0.162 ± 0.004 0.161 ± 0.004 −21.81
0.806 0.801 0.252 ± 0.004 0.253 ± 0.004 −21.34
1.086 1.081 0.319 ± 0.004 0.321 ± 0.004 −21.03
1.380 1.375 0.377 ± 0.004 0.380 ± 0.004 −20.78
1.715 1.710 0.440 ± 0.004 0.443 ± 0.004 −20.53
a
T is temperature, Pt is total pressure, PH2S is partial pressure of H2S, xH2S and ΔxH2S are mole fraction and uncertainty of mole fraction of H2S,
(xH2S)Cor is corrected mole fraction of loaded gas using density of charged solution and Habs is enthalpy of absorption. Standard uncertainties (u) are
u(T) = ± 0.01 K and u(Pt) = ± 0.003 MPa (standard uncertainties in table are reported with 0.95 level of confidence).

The error propagation theory was used to estimate the The measured quantity q is dependent upon the variables r... u
uncertainties of final results.30 In the base of this theory, the which fluctuates in a random and independent manner.
uncertainty δq of the interest variable q(r... u) is given by eq 8: The experimental gas solubility data were evaluated to
⎡⎛ ∂q ⎞ ⎤2 ⎡⎛ ∂q ⎞ ⎤2 determine the Henry’s constant on the molality or mole
δq = ± ⎢⎜ ⎟dr ⎥ + ... + ⎢⎜ ⎟du⎥ fraction scale for the solubility of gas in solvents at zero
⎣⎝ ∂r ⎠ ⎦ ⎣⎝ ∂u ⎠ ⎦ (8) pressure, h(0) (0)
H,m or hH,x.

C DOI: 10.1021/je500478t
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article
a
Table 4. Experimental Solubility of H2S in NMA
T ± 0.01 Pt ± 0.003 PH2S xH2S ±ΔxH2S ΔHabs(GH)
K MPa MPa xH2S ± ΔxH2S kJ/mole
−5
303.15 Pt −3.2 × 10
0.050 0.050 0.024 0.002 −14.13
0.179 0.179 0.089 0.003 −13.91
0.318 0.318 0.151 0.004 −13.72
0.511 0.511 0.228 0.005 −13.50
0.705 0.705 0.296 0.005 −13.32
0.867 0.867 0.348 0.006 −13.19
0.978 0.978 0.383 0.006 −13.11
313.15 Pt, −6.2 × 10−5
0.060 0.060 0.023 0.002 −15.08
0.214 0.214 0.086 0.003 −14.87
0.385 0.385 0.146 0.004 −14.68
0.613 0.613 0.220 0.005 −14.46
0.855 0.855 0.287 0.005 −14.29
1.043 1.043 0.338 0.006 −14.16
1.175 1.175 0.373 0.006 −14.08
323.15 Pt −1.22 × 10−4
0.069 0.069 0.022 0.002 −16.06
0.251 0.251 0.082 0.003 −15.86
0.449 0.449 0.141 0.004 −15.67
0.722 0.722 0.213 0.005 −15.46
1.001 1.001 0.278 0.005 −15.29
1.222 1.222 0.328 0.006 −15.16
1.360 1.360 0.364 0.006 −15.07
333.15 Pt −2.29 × 10−4
0.079 0.079 0.021 0.002 −17.08
0.289 0.289 0.079 0.003 −16.88
0.515 0.515 0.136 0.004 −16.70
0.832 0.832 0.205 0.005 −16.49
1.151 1.151 0.270 0.005 −16.31
1.405 1.405 0.319 0.006 −16.19
1.589 1.589 0.353 0.006 −16.10
343.15 Pt −4.16 × 10−4
0.089 0.089 0.020 0.002 −18.12
0.326 0.326 0.076 0.003 −17.93
0.582 0.582 0.130 0.004 −17.75
0.941 0.941 0.198 0.005 −17.55
1.306 1.306 0.261 0.005 −17.37
1.593 1.593 0.310 0.006 −17.24
1.798 1.798 0.344 0.006 −17.16
353.15 Pt −7.29 × 10−4
0.100 0.100 0.019 0.002 −19.20
0.364 0.364 0.072 0.003 −19.01
0.650 0.650 0.124 0.004 −18.84
1.053 1.053 0.188 0.005 −18.64
1.462 1.462 0.249 0.006 −18.47
1.785 1.785 0.296 0.006 −18.34
2.023 2.023 0.329 0.006 −18.26
363.15 Pt, −1.24 × 10−3
0.112 0.111 0.018 0.002 −20.30
0.402 0.401 0.070 0.004 −20.12
0.721 0.720 0.121 0.004 −19.95
1.165 1.164 0.185 0.005 −19.75
1.621 1.620 0.244 0.006 −19.58
1.981 1.980 0.291 0.006 −19.45
2.260 2.259 0.323 0.007 −19.36
a
It should be noted that the vapor pressure of NMA at the practical temperature range in this work is 3 × 10−5 MPa at T = 303.15 K through 1.2 ×
10−3 MPa at T = 363.15 K, values which all are lower than the uncertainty of pressure sensor (0.003 MPa). T is temperature, Pt is total pressure, PH2S

D DOI: 10.1021/je500478t
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 4. continued
is the partial pressure of H2S, xH2S and ΔxH2S are mole fraction and uncertainty of mole fraction of H2S and Habs is enthalpy of absorption. Standard
uncertainties (u) are u(T) = ± 0.01 K and u(Pt) = ± 0.003 MPa (standard uncertainties in table are reported with 0.95 level of confidence).

Figure 1. Experimental data for H2S−DMA system at different temperatures and pressure (points) compared with GRK EoS (dashed lines) and KI
model (solid lines). The solid point (◆) in the figure is extracted from Hayduk et al. which shows a deviation of about 9% from our result.

Figure 2. Experimental data for H2S−NMA system at different temperatures and pressure (points) compared with GRK EoS (dashed lines) and KI
model (solid lines).

E DOI: 10.1021/je500478t
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Figure 3. Comparison of solubility of H2S in DMA, NMA, DMF, and sulfolane (SFL) at that given temperature.

(0) f (T , p) Table 5. Thermodynamic Properties of H2S Solubility in

hH, m (T ) = lim 0 DMA and NMAa
m / m0 → 0 m/m (9)

f (T , p) T ± 0.01 h(0)
H,x ΔsolG∞
m ΔsolH∞
m ΔsolS∞
m v∞
H2 S
(0)
hH, x (T ) = lim K MPa kJ/mol kJ/mol J/mol cm3/mol
x→0 x (10)
NMA−H2S
where m is the molality of gas in the solvent, m0 = 1 mol·kg−1 303.15 1.858 ± 0.020 1.68 −14.12 −52.13 34.0 ± 0.3
IL and f is the fugacity of pure gas at temperature T and 313.15 2.345 ± 0.029 2.22 −15.07 −55.20 34.8 ± 0.3
pressure p. The fugacities were calculated using the software 323.15 2.909 ± 0.031 2.79 −16.05 −58.27 35.7 ± 0.4
package Thermofluids.31 For H2S, that software is based on the 333.15 3.441 ± 0.032 3.38 −17.05 −61.35 36.6 ± 0.4
equation of state by Lemmon and Span.32 The procedure of 343.15 4.087 ± 0.033 4.01 −18.09 −64.42 37.5 ± 0.5
Henry’s constant evaluation was adopted by Jalili et al.;33 353.15 4.838 ± 0.038 4.67 −19.16 −67.49 38.5 ± 0.5
therefore, it is not described here. The obtained h(0)H,x and the 363.15 5.425 ± 0.041 5.36 −20.26 −70.57 39.5 ± 0.6
estimated uncertainty δh(0)
H,x are given in Table 5. The influence DMA−H2S
of temperature on Henry’s constant was described by 303.15 0.809 ± 0.015 −0.44 −16.66 −53.52 33.5 ± 0.9
(0)
ln(hH, = Ah,x (T /K) + B h,x + C h,x /(T /K) 313.15 1.044 ± 0.020 0.11 −17.78 −57.15 34.6 ± 1.0
x /MPa) (11)
323.15 1.311 ± 0.025 0.70 −18.94 −60.77 35.7 ± 1.0
Henry’s constant in mole fraction scale and molality scale are 333.15 1.617 ± 0.026 1.33 −20.13 −64.40 36.9 ± 1.1
correlated with 343.15 1.958 ± 0.025 1.99 −21.35 −68.02 38.8 ± 1.1
353.15 2.354 ± 0.028 2.69 −22.62 −71.65 39.5 ± 1.1
(0) −1 (0) Msolvent a ∞
hH, m/MPakg = hH, x /MPa T, temperature; h(0)H,x, Henry’s law constant; v , partial molar volume
1000 (12) ∞
at infinite dilution obtained from GRK; ΔsolGm,x, Gibbs free energy of
where Ah,x, Bh,x, and Ch,x are adjustable parameters reported in solution; ΔsolH∞ ∞
m,x, enthalpy of solution; ΔsolSm,x, entropy of solution at
Table 6. The correlation eq 11 was used to estimate the infinite dilution.
∞
changes of the partial molar Gibbs energy ΔsolGm,x , the partial
molar enthalpy ΔsolHm,x, the partial molar entropy ΔsolS∞
∞
m,x of
Table 6. Numerical Values of the Parameters of eq 11, h(0)
H,x/
gas when it is transferred from the ideal gas state at temperature MPa (Henry’s Law Constant on Mole Fraction Scale)
T and standard pressure p = p0 = 0.1 MPa to its reference state DMA−H2S NMA−H2S
in the liquid solvent, and these properties are also given in
Ah,x Bh,x Ch,x Ah,x Bh,x Ch,x
Table 5.

■
0.02181 −6.7865 −0.0559 0.01848 −4.9349 −0.03481
MODELING
Two models are used to correlate the experimental results for to correlate the solubility of gases in an ionic liquid. For a pure
the solubility of a single gas in DMA and NMA. component the RK EoS is
The Generic Redlich−Kwong Cubic Equation of State a(T )
RT
(EoS). A generic Redlich−Kwong (GRK) type of cubic P= −
equation of state, was proposed by Shiflett and Yokozeki15−17 υ−b υ(υ + b) (13)

F DOI: 10.1021/je500478t
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

R2TC2 Table 8. Optimal Binary Interaction Parameters in GRK and

a(T ) = 0.427480 α(T ) KI Equation, and also ARD % and MRD % of Both Models
PC (14)
H2S/NMA H2S/DMA
RT
b = 0.08664 C l12 0.091946 0.042165
PC (15) l21 0.29908 0.0049459
The mathematical form of α(T) as used by Shiflett and τ12 = τ21 0 0
Yokozeki is m12 = m21 −0.04846 0.07939
A0 0.21799 0.62971
≤3
A1 −219.05 −440.93
α (T ) = ∑ λk(Tr−1 − Tr)k ARD % (GRK) 1.43% 1.11%
k=0 (16) MRD % (GRK) 4.01% 7.51%
Pc and Tc are the critical pressure and critical temperature of the ARD % (KI) 2.99% 2.38%
pure component, respectively, υ is the molar volume, Tr = T/Tc MRD % (KI) 8.72% 6.50%
is the reduced temperature, and λk values are adjustable
parameters.
The critical properties for pure H2S were taken from the
NIST database,21 those for DMA were calculated with the the average relative deviation, ARD %, and the maximum
group contribution method34 and those for NMA were taken relative deviation, MRD %, defined at eqs 21 and 22. The
from the literature.35 All critical properties of H2S, DMA, and results of the RK correlation have been graphically shown in
NMA are listed in Table 7. The parameters λ0 through λ3 were Figures 1 and 2 as well.

100
N
picor (T , m) − piexp (T , m)
Table 7. Parameters of GRK EoS for Pure Compounds Used ARD% = ∑
in the Present Study N i=1
piexp (T , m) (21)
H2S NMA DMA
⎛ pcor (T , m) − pexp (T , m) ⎞
molar mass 34.08 73.09 87.12
MRD% = max⎜⎜ i exp
i
100⎟⎟
Tc/K 373.60 718 617.15
⎝ pi (T , m) ⎠ (22)
Pc/MPa 9.008 5.00 3.60
λ0 0.99879 1.0 1.0 Krichevsky−Ilinskaya equation. The solubility of a single
λ1 0.33206 0.453143 0.35819 gas in a pure NMA and DMA is described by the Krichevsky−
λ2 −0.049417 0 0 Ilinskaya (KI) equation38 on the mole fraction scale
λ3 0.0046387 0 0
⎛ f (T , p) ⎞ vH∞2S(P − P s)
ln⎜⎜ 2 ⎟ = ln(hH,
HS (0)
⎟ x ( T )) + + ln(γx)
⎝ x ⎠ RT
taken from Shiflett and Yokozeki36 for H2S, whereas for DMF
and DMSO, they were considered as adjustable parameters and (23)
either set to zero (λ2 and λ3) or were obtained through a fit where γx is the activity coefficient of gas on the mole fraction
together with the binary parameters of the model to the new scale and vH∞2S is the molar volume of dissolved gas at infinite
gas solubility data (see below). Table 7, shows all pure dilution.
component parameters. The activity coefficient, γx, was calculated from the two-suffix
The EoS was extended to mixtures by applying the modified Margules equation39 on the mole fraction scale
van der Waals−Berthelot mixing rule proposed by Yokozeki:37
N ln γm = A(xs 2 − 1) (24)
a(T ) = ∑ aiaj fij (T )(1 − kij)xixj where A is binary parameters and xs is mole fraction of solvent.
i,j=1 (17) The influence of temperature on the binary interaction
N parameter is approximated by
1
b= ∑ (bi + bj)(1 − mij)(1 − kij)xixj A = A 0 + A1/(T /K) (25)
2 i,j=1 (18)
39
Prausnitz et al. have discussed that the application of that type
τij ∞
fij (T ) = 1 + of equation needs to have information about h(0) H,x and v .
(19) 40 41
T Bender et al. and also Deshmukh−Mather have presented
the connection of the (KI) equation and the Peng−Robinson
lijl ji(xi + xj) EoS to obtain the parameters of the KI equation from the EoS.
kij =
l jixi + lijxj (20) The Henry’s law constants h(0)
H,x were calculated from eq 10 at
low pressure limit, and the partial molar volumes of solutes at
where τij = τji, τii = 0, mij = mji, mii = 0, and kii = 0. There are infinite dilution were calculated by the GRK EoS and listed in
four interaction parameters per binary system: lij, lji, mij, and τij. Table 5. As observed in Table 5, the obtained values of vH∞2S are
These interaction parameters were adjusted to the experimental positive and linearly increase when temperature increases.
gas solubility data, and the pure component parameters (λ0 and
λ1) of DMA and NMA were adjusted to the vapor pressure of vH∞2S ‐ NMA(cm 3/mole) (R2 = 0.998)
pure solvent. Table 8 gives the numerical values of the binary
interaction parameters and also the quality of correlation, using = 6.3794 + 0.0908T (K) (26)

G DOI: 10.1021/je500478t
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data

■
Article

vH∞2S ‐ DMA(cm 3/mole) (R2 = 0.998) ACKNOWLEDGMENTS

= −2.7857 + 0.1194T (K) (27) We are thankful to the Research Council of the Research
Institute of Petroleum Industry (RIPI) and the Research and
Parameters A0 and A1 were adjusted to minimize the sum of Development of the National Iranian Oil Company (NIOC)
ARD % between the calculated and the experimental results for for their support of this work.

■
the pressure of the gas. The results of the correlations
(interaction parameters) are given in Table 8. The quality of
the correlation is reported using the average relative deviation
ARD % and the maximum relative deviation MRD % as defined
by eqs 21 and 22 in Table 8 as well, and graphically have been
shown in Figures 1 and 2.
The volume expansion or compression caused by dissolving
an acid gas in liquid phase has been investigated using the
sensitivity test on volume. It is empirically found out that if the
ratio of uncharged injected liquid to the equilibrium cell volume
is lower than one-third, the fluctuation of charged solution
volume makes an error lower than that given for the solubility
uncertainty.
To further confidence and for a more realistic estimate,
solubility data were recalculated using densities of the charged
solutions obtained by the EoS for DMA and reported in Table
3, (xH2S)Cor, and also the densities of charged solutions were
correlated by linear equations in terms of temperature and
molality and reported in Table 2.
Comparisons of data in columns 4 and 5 in Table 3 show
that volume expansion causes the solubility increase with the
deviations lower than 2% which is comparable with the
uncertainty values of solubility.
Enthalpy of Absorption. Using experimental pressure-
solubility data of acid gases in solvent, one may be able to
calculate the enthalpy of absorption via Gibbs−Helmholtz
equation ΔHabs(GH),
⎛ ∂ ln pH S ⎞ ΔHabs(GH)
⎜⎜ 2
⎟⎟ = −
RT 2
⎝ ∂T ⎠ P , x (28)
ΔHabs(GH) is the enthalpy of absorption which is normally
referred to as differential enthalpy in the literature. Enthalpies
of absorptions were calculated using eq 28 and reported in
Tables 3 and 4.
LIST OF SYMBOLS
NIST = National Institute of Standards and Technology
NMA = N-methylacetamide
DMA = N,N-dimethylacetamide
KI = Krichevsky−Ilinskaya equation
RK EoS = Redlich−Kwong equation of state
GRK = generic Redlich-Kowang equation of state
R = universal gas constant
Vgc = volume of the gas container (or gas sample)
Vg = gas-phase volume in the equilibrium cell
Vauto = volume of the autoclave (equilibrium cell)
Zi and Zf = compressibility factors of the initial and final state
in the gas container
Ta = ambient temperature
P0 = initial pressure of solution
PT = total absolute pressure
PVP or Ps = vapor pressure of pure solvent
PH2S = partial pressure of H2S at equilibrium state
Peag = partial pressure of acid gas at equilibrium state
ngag = amount of acid gas in the gas phase at equilibrium state
nlag = amount of acid gas in the liquid phase at equilibrium
state
nag = total number of moles of acid gas injected to
equilibrium cell
Msolvent = molar mass of pure solvent
δ ni = uncertainty of amount of species i
mj = molality of component j, mol. kg−1
wsolvent = weight of solvent charged into cell in g
ρag = density of acid gas in gas phase at equilibrium state
ρNMA = density of pure liquid N-Methylacetamide (g/cm3)
ρDMA = density of pure liquid N,N-Dimethylacetamide (g/
cm3)
ρcharged solution = density of charged solution (g/cm3)
xH2S = mole fraction of loaded gas
xs = mole fraction of solvent

■
(xH2S)Cor = corrected mole fraction of loaded gas using
CONCLUSION density of charged solution
Tr = reduced temperature
In this investigation, we have measured the solubility of H2S as
Tc = critical temperature
a function of partial pressure of acid gas in N,N- Pc = critical pressure
dimethylacetamide and N-methylacetamide over a wide α(T) = temperature dependent parameter in RK equation of
temperature range (between 303.15 K and 363.15 K) and state
pressure from vapor pressure of solvent up to about 2.0 MPa. b = RK covolume constant
The experimental data were correlated by using the (1) R2 = correlation coefficients
Krichevsky−Ilinskaya equation and (2) a generic Redlich− ARD = average of relative deviations
Kwong (GRK) cubic EoS. Results in Figures 1 and 2 and ARD MRD = maximum relative deviation
% and MRD % in Table 8 show that both models have h(0)
H,x = Henry’s law constant on mole fraction base
comparable abilities in the prediction of gas pressure. h(0)
H,m = Henry’s law constant on molality base

■ AUTHOR INFORMATION
Corresponding Author
f H2S(T,p) = fugacity of H2S in gas phase
γx = activity coefficient of gas on the mole fraction scale
vH∞2S = molar volume of dissolved gas at infinite dilution
λk′, lij, lji, mij, τij = adjustable parameters in GRK EoS
*E-mail: shokouhim@ripi.ir, shokouhi110@gmail.com. Tel: 98 ∞
ΔsolGm,x = partial molar Gibbs free energy of solubility at
21-48252467.
reference state
∞
Notes ΔsolHm,x = partial molar enthalpy of solubility at reference
The authors declare no competing financial interest. state
H DOI: 10.1021/je500478t
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
ΔsolS∞
m,x = partial molar entropy of solubility at reference state
GH = Gibbs−Helmholtz
ΔHabs(GH) = enthalpy of absorption calculated using
Gibbs−Helmholtz equation
A(A0,A1) = adjustable parameters in KI equation
■
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J DOI: 10.1021/je500478t
J. Chem. Eng. Data XXXX, XXX, XXX−XXX