J. Chem.

Thermodynamics 186 (2023) 107142

Contents lists available at ScienceDirect

The Journal of Chemical Thermodynamics

journal homepage: [Link]/the-journal-of-chemical-thermodynamics

Equilibrium absorption of CO2 in aqueous solution of N-dimethylamino

ethanol and 2-(ethylamino)ethanol, measuring and
thermodynamic modeling
Mohammad Delavari a, Maryam Khajenoori a, Ali T. Zoghi b, *
a
Faculty of Chemical, Petroleum and Gas Engineering, Semnan University, Semnan 35131-19111, Iran
b
Gas Refining Technology Group, Gas Research Division, Research Institute of Petroleum Industry (RIPI), Tehran 14665-1998, Iran

A R T I C L E I N F O A B S T R A C T

Keywords: The equilibrium carbon dioxide solubility in aqueous solutions of N-dimethylaminoethanol (DMAE) 40 wt% + 2-
N-Dimethylaminoethanol (ethylamino) ethanol (EAE) 5 wt% and DMAE 30 wt% + EAE 5 wt% was measured at various temperatures
2-(ethylamino) ethanol (313.15, 328.15, 343.15, 358.15 K) in the range of pressures from 6.5 to 236 kPa. The enthalpy of absorption of
Equilibrium solubility of CO2
carbon dioxide was measured for the mixture of DMAE (40 wt%) + EAE (5 wt%), at 328.15 K. The Deshmukh-
Enthalpy of absorption
Deshmukh-Mather model
Mather model was used to correlate the equilibrium solubility of carbon dioxide data, and the model parameters
were optimized. The optimized model could correlate the vapor-liquid equilibrium with the 9.4 average absolute
percentage deviation (AAD%), and the obtained AAD% for enthalpy of absorption in aqueous solution of DMAE
(40 wt%) + EAE (5 wt%) was 24.0.

1. Introduction absorption method include the ability to cyclic absorption, high elimi­
nation efficiency, and could be used even in low carbon dioxide con­
Global warming and climate change are believed to be caused by the centrations. Therefore, the most common method used for gas
presence of greenhouse gases like carbon dioxide in the atmosphere. A processing on a large scale is the chemical absorption in aqueous alka­
greenhouse gas responsible for more than 60% of the climate change in nolamine solutions [2]. The alkanolamines were classified as primary,
the world is carbon dioxide. CO2 is released into the atmosphere due to secondary, or tertiary based on the number of hydrogens in the ammonia
the combustion of fossil fuels by humans [1]. So far, there have been molecule that are substituted with alkyl or hydroxyl group. These
three methods used for removing acid gases, such as membrane pro­ aqueous amine solutions are used to absorb acid gases such as CO2.
cesses, adsorption processes, and chemical absorption with aqueous Primary and secondary amines have higher rates of CO2 absorption and
amine solutions. Each of the mentioned methods has advantages and high enthalpy of absorption, but lower CO2 absorption capacities than
disadvantages. Membrane processes have low energy requirements. But, tertiary amines; For example, MEA (monoethanolamine) and DEA
because this process must be completed in several steps and there is (diethanolamine) are no longer used in industry due to the high corro­
noticeable hydrocarbon loss, it is costly. Adsorption processes are per­ sion, high enthalpy of absorption, and a high energy requirement for the
formed at higher temperatures while producing no liquid waste is regeneration. In comparison to primary and secondary types, tertiary
generated, and the excretion of solid waste is no longer a serious envi­ type amines, such as MDEA (N-methyldiethanolamine), have a low
ronmental concern; however, the adsorption has a lower capacity for enthalpy of absorption, low energy regeneration, a low absorption rate
carbon dioxide, particularly at low pressures. Operationally, it experi­ in CO2, and a high CO2 absorption capacity. As a result, the order of heat
ences problems like simultaneous water and gas adsorption, the high of the reaction between alkanolamines is: Primary amines > secondary
cost of raw materials, and slow kinetic rates. The chemical absorption amines > tertiary amines [3–5]. One of the major challenges in the
method has a high rate of equipment corrosion, at low CO2 loading chemical absorption approach is to use an alkanolamine solution with a
capacity, and amine degradation occurs in presence of SO2, NO2, and O2, low enthalpy of absorption, and higher CO2 absorption capacity,
high energy consumption during solvent regeneration is another chal­ resulting in quick absorption kinetics and a low energy penalty [6,7].
lenges of this method. However, the advantages of the chemical Numerous experiments have been carried out to determine how to

* Corresponding author.
E-mail address: zoghiat@[Link] (A.T. Zoghi).

[Link]
Received 28 December 2022; Received in revised form 1 August 2023; Accepted 1 August 2023
Available online 5 August 2023
0021-9614/© 2023 Elsevier Ltd.
M. Delavari et al. The Journal of Chemical Thermodynamics 186 (2023) 107142

Table 1
Materials used in this work.
Chemical name Source Puritya Analysis Method CAS number

Carbon dioxide (CO2) Alborz gas Co. 99.9(wt.%) GC [124–38–9]

N-Dimethylaminoethanol (DMAE) Merck Co. 99.5(wt.%), (contain 0.2 mass% H2O)b GC [108–01–0]
2-(ethylamino)ethanol (EAE) Merck Co. 97.0 (wt.%), (contain 2.9 mass% H2O)b GC [110–73–6]
Deionized Water Laboratory prepared 5.43 μS⋅cm− 1, TDSc <10 ppm Resistivity Measurement [7732–18–5]
a
The purities were provided by the suppliers and no further purification was done.
b
The water content is verified by using Karl Fischer Titration analysis (Metrohm 870 KF).
c
The total dissolved substance (TDS) has been measured by conductivity method(Mettler Toledo).

Kumar et al. [20] studied the solubility of CO2 in a mixture of DEEA and
AEEA. This mixture was examined for a total concentration of 1.0–3.0
kmol/m3, a mole fraction of AEEA in the range of 0.02–0.2, a loading of
0.412–0.843 (mol CO2/mol amine), and a temperature range of 303.14,
313.14, 323.15, and 333.15 K. The mixture of DEEA + AEEA exhibited a
high loading capability. Furthermore, in this mixture, the maximum
solubility of CO2 was at 0.2 mol fraction of AEEA. Zoghi et al. evaluated
the equilibrium solubility of CO2 in an aqueous solution of DMAE (40 wt
%) and N,3-(Methylamino)propylamine (MAPA) (5 wt%) at four
Fig. 1. Chemical structure of DMAE and EAE (a: DMAE, b: EAE). different temperatures (313.15, 328.15, 343.15, and 358.18 K). The
enthalpy of absorption of CO2 was measured at T = 328.15 K, at the
combine primary or secondary amines with tertiary amines to increase loading of CO2 equal to 0.5, the enthalpy of absorption was reported at
the absorption capacity, increase the absorption rate of CO2, and reduce − 49.9 (kJ. mol− 1CO2) [4].
the enthalpy of absorption [8–11]. Tertiary amines have slow kinetics in In the present work, according to the mentioned literature review,
CO2 absorption; therefore, other amines, such as cyclic and primary or the equilibrium solubility data of CO2 in blends of DMAE 40 wt% + EAE
secondary amines, could be added to improve their absorption perfor­ 5 wt% and DMAE 30 wt% + EAE 5 wt% were measured at temperatures
mance [6,12]. The combination of amines may improve absorption rate, of (313.15, 328.15, 343.15, and 358.15) K. The parameters of the
reduce enthalpy of absorption, and carbon dioxide absorption capacity Deshmukh-Mather model were correlated with the experimental data,
while reduces operational and capital costs [13–15]. 2-(ethylamino) and the interaction parameters were optimized. Additionally, for the
ethanol (EAE) is a secondary amine with a linear structure. Unlike MEA, concentration of DMAE of 40 wt% and EAE of 5 wt%, the heat of carbon
EAE corrodes at slower rate, even at higher concentrations [16]. dioxide absorption was determined at 328.15 K. The tuned model was
Furthermore, because EAE is forming moderate stable carbamate that applied to calculate the enthalpy of absorption at T = 328.15 K for
allows to increase absorption rates, regeneration requires lower energy aqueous solution of (DMAE 40 wt% +EAE 5 wt%) and aqueous solution
[16]. Therefore EAE is utilized as a solvent for CO2 capturing. Also, it is of (DMAE 30 wt% + EAE 5 wt%). The enthalpy of absorption was pre­
used as an additive of N,N-diethylethanolamine (DEEA) solution [16]. dicted by the Gibbs Helmholtz equation at T = 328.15 K.
Pandey et al. [17] investigated the CO2 solubility in a mixture of EAE
and 2(2-Aminoethylamine) ethanol (AEEA) in (303.15–323.15) K with 2. Experimental
the concentration of 21 wt% and 9 wt% at 313.15 K and loading up to
0.75 (mol CO2/mol amine). This mixture showed higher CO2 solubility, 2.1. Material
but the enthalpy of absorption was relatively high (-72.25 kJ. mol− 1
CO2) [17]. The solubility of CO2 in DEEA + EAE with a total concen­ The chemicals used in the present work are listed in Table 1. It should
tration of 3 mol/L with loading up to 0.62 (mol CO2/mol amine) at be note that the water content of the DMAE and EAE have been
313.15 K was investigated by Gao et al. [18]. The solubility of CO2 in a accounted for aqueous solution preparation. The aqueous amine solu­
mixture of N,N -diethylethanolamine (DEEA) + N,3-(methylamino) tions were prepared using deionized double distilled water. The mo­
propylamine (MAPA) was examined for different concentrations of 5 M lecular structure of DMAE and EAE is shown in Fig. 1. The aqueous
DEEA + 2 M MAPA with the loading of (0.74, 0.43 and 0.31 (mol CO2/ mixtures were prepared by using an analytical balance, Mettler model
mol amine)) and 5 M DEEA and 1 M MAPA with the loading of (0.90, AE 200, with an uncertainty of ±1.0×10− 5 kg.
0.46, 0.23 (mol CO2/mol amine)) at three temperatures of 313.15,
353.15 and 393.15 K by Arshad et al. [2]. According to the results, this
blend has a high cycle capacity and a high loading capacity for 2 M and 2.2. Equilibrium solubility apparatus
1 M MAPA. At 313.15 K, the enthalpy of absorption of CO2 in DEEA 5 M
+ MAPA 2 M and DEEA 5 M + MAPA 1 M were − 70.1 (kJ. mol− 1 CO2) Measurement of the equilibrium solubility of CO2 was performed in
and − 69.7 (kJ. mol− 1 CO2), respectively [2]. The results show that for 2 the autoclave. The setup is shown in Fig. 2 in details. The material of the
M and 1 M MAPA, this blend has a high loading capacity at low tem­ autoclave is stainless steel 304 with a volume of (4.75×10− 4 ± 1×10− 6)
peratures, a high cycle capacity, and a high enthalpy of absorption. Bong m3. The autoclave temperature is controlled with a water bath circu­
Keun Choi et al. examined the equilibrium solubility of CO2 in combi­ lator, model LAUDA P-12, with an accuracy of ±0.01 K. It is needed to
nations of diisopropanolamine (DIPA) and N-methyldiethanolamine have a homogenized phase; therefore, a magnetic stirrer was used to
(MDEA) [19], for different concentrations of DIPA 9 wt% + MDEA 21 wt obtain homogenization of the vapor and liquid phases. A calibrated Pt-
%, DIPA 15 wt% + MDEA 15 wt%, DIPA 21 wt%+ MDEA 9 wt% with the 1000 sensor, with an accuracy of ±0.01 K, coupled to a thermometer
loading of (0.88, 0.833 and 0.830 (mol CO2/mol amine)) at 323.15 K (Testo 735–2 model) was used to record the autoclave temperature; a
and 383.15 K. To predict the enthalpy of absorption of CO2, they used a pressure transmitter sensor with an accuracy of ±0.1 kPa was used to
tuned UNIQUAC model. Their modeling results revealed that in the record the gas container pressure. The gas container pressure trans­
range of 0.0 < xDIPA < 0.4; 0.0 < xMDEA < 0.4; 0.6 < xWater < 1.0 the CO2 mitter sensor has a pressure range of 0 to 10 MPa. A pressure transmitter
enthalpy of absorption was varied between − 65 to − 36 (kJ. mol− 1 CO2). sensor was used to measure the autoclave pressure with an accuracy of
±1.0 kPa. The autoclave pressure transmitter sensor has a pressure

2
M. Delavari et al. The Journal of Chemical Thermodynamics 186 (2023) 107142

Fig. 2. Schematic of experimental setup for measuring of equilibrium solubility: a) CO2 cylinder, b) CO2 feed gas, c) Data acquisition system, d) Water bath
circulator, e) Autoclave.

Fig. 3. Experimental apparatus schematic of the enthalpy of absorption of CO2: a) CO2 storage, b) Watt-meter, c) magnetic stirrer, d) heater, e) CO2 cylinder, f) CO2
tank. P1, P2, P3 are pressure sensors.

3
M. Delavari et al. The Journal of Chemical Thermodynamics 186 (2023) 107142

Table 2
Constants of Eq. (18) to calculate the equilibrium reaction constants and Henry’s law constant.
Reaction No. C1 C2 C3 C4 Ref.

10 K1 132.899 − 13455.9 − 22.4773 0.0 [44]

11 K2 231.465 − 12092.1 − 36.7816 0.0 [45]
12 K3 216.049 − 12431.7 − 35.4819 0.0 [4]
13 K4 140.8698 − 11972.4 − 20.7227 − 0.01179 [4]
14 K5 231.465 − 12092.1 − 36.7816 0.0 [45]
15 K6 8.8334 − 5274.4 0.0 0.0 [16]
− HCO2 94.4914 − 6789.04 − 11.4519 − 0.010454 [45]

Table 3 Vg = VAutoclave − Vsolution (4)

The optimized βi,j that obtained from the Deshmukh-Mather model.
VAutoclave is the volume of the autoclave, and Vsolution is the volume of
A B C D
βij
the amine solution. Eq. (5) is used to compute the number of CO2 moles
β−+
DMAEH
-EAECOO 0.0724 − 0.1989 − 0.1187 0.5985 (n’CO2) absorbed in the amine’s aqueous solution. Finally, Eq. (6) is used
β+DMAEH
–CO2 − 0.1985 0.3111 0.5442 0.1000 to determine the CO2 loading of an aqueous amine solution:
β−+
DMAEH
–HCO3 0.0855 − 0.0394 0.2000 0.4300
β+DMAEH
-DMAE 0.1163 0.3072 0.4812 0.3000 n′CO2 = nCO2 − ngCO2 (5)
β+DMAEH
-EAE 0.0000 0.0000 0.0000 0.0000
β−+
EAEH
-EAECOO − 0.7227 − 1.5000 − 0.7052 1.3440
β+ − 0.1107 0.0001 0.4341 0.5000 n′CO2
EAEH
–CO2
α= (6)
β–+
-EAEH
HCO3 − 0.4153 − 0.4500 − 0.3729 0.4595 namine
β+ EAEH
-DMAE 0.4421 0.4088 0.1054 − 0.1766
+
β-EAE
EAEH 0.0000 0.0000 0.0000 0.0000 where namine is the number of amine moles. The CO2 loading uncertainty
β–CO2- HCO3 0.7296 0.3710 0.4754 0.8755
is obtained from Eq. (7) [25]:
β−–CO2
EAECOO − 0.2860 0.1100 0.3500 − 0.2142
β−-DMAE
EAECOO − 0.3754 − 2.6685 − 3.8194 0.1371 (( )2 ( )2 )0.5
u(α) u(n′CO2 ) u(namine )
=± + (7)
α n′CO2 namine
range of (0–1) MPa. All of the pressure sensors were Keller type PA-33X.
For measuring CO2 solubility in an aqueous amine solution, first, a The compressibility factors are determined by the NIST Databank
certain amount of solution with 50 cm3 was charged to the autoclave [26]. Validation of the equilibrium solubility measurement was per­
from the line at the top of the autoclave [4]. It should be noted that the formed in previous works by Najafloo et al. [27]. The absolute relative
air should be prevented from entering the autoclave. Therefore, before percentage deviation (ARD%) of the reported data is obtained by Eq. (8):
charging the solution, the pressure of the autoclave should be reduced to ⃒ ⃒
⃒Xref − Xexp ⃒
<0.1 kPa. This pressure reduction was achieved by a vacuum pump. The ARD% = × 100 (8)
Xref
circulator then changed the autoclave temperature (T) to the chosen
value. Following the solution was injected into the autoclave, the in Eq. (8), Xref is reference data and Xexp is experimental data.
maintained pressure is saturation vapor pressure of the solution (Psat).
According to the methodology already used by Park and Sandall [21],
Hosseini-Jenab et al. [22], and Zoghi et al. [23], the moles of CO2 2.3. Measurement of the enthalpy of absorption
absorbed by an aqueous amine solution were calculated.
Eq. (1) was used to calculate how many moles of CO2 were trans­ The enthalpy of absorption measurement apparatus is principally
ferred from the gas container to the autoclave: highly similar to the equilibrium solubility measurement apparatus,
which can be seen in Fig. 3. The Teflon material was used with a
nCO2 =
Vgc P1 Vgc P2
− (1) diameter of 1.0×10− 2 m as coverage in the inside of the autoclave to
Z1 RT1 Z2 RT2 reduce the heat loss, besides the setup was equipped with a temperature
The initial and final pressures before and after CO2 injection, as well controller with a heating element, and a fan was used to keep the outside
as the initial and final gas container temperatures, are represented in Eq. temperature constant. The autoclave has a volume of (1.60×10− 4 ±
(1) by the letters P1, P2, and T1, T2 respectively. R is the universal gas 4.7×10− 7) m3. The temperature of the autoclave is controlled by a water
constant. Z is the compressibility factor associated with P1, P2 and T1, T2. bath circulator, model LAUDA Eco Silver, with an accuracy of ±0.01 K.
The capacity of the gas container is Vgc. The pressure is unchanged three The autoclave temperature was measured using a calibrated Pt-1000
to four hours later. Pressure measurements are considered to be the sensor connected to a thermometer (Testo 735–2 model) with an accu­
equilibrium pressure. The equilibrium partial pressure of CO2 is given by racy of ±0.01 K. A pressure transmitter sensor (model Keller LEX 1) was
Eq. (2): used to measure the autoclave’s pressure with an accuracy of 0.1 kPa.
The pressure range of the autoclave transmitter sensor is (0–2) MPa. A
PCO2 = Pt − Psat (2) pressure transmitter sensor (model Keller LEX 1) with an accuracy of
in Eq. (2), Pt and Psat stand for, respectively, the autoclave’s total ±0.4 kPa was used to record the gas container pressure. The gas
pressure under equilibrium and vapor pressure of the amine solution container pressure transmitter sensor has a pressure range of 0 to 2 MPa.
[24]. Eq. (3) is used to determine the amount of CO2 in the gas phase of The amount of energy that is produced by chemical absorption or
the autoclave. electric heating is calculated by Eq. (9):

Vg PCO2 Q = (CAutoclave ΔT) + (msolution Cp,solution ΔT) (9)

ngCO2 = (3)
ZCO2 RT Where Q is the energy amount consumed or the heat released by the
in Eq. (3), T is temperature, and ZCO2 is the compressibility factor of absorption of CO2 by amine solution, CAutoclave is the autoclave’s heat
the gas phase dependent on T and PCO2. Vg is a gas-phase volume in the capacity; ΔT indicates the temperature difference between the solution
autoclave [24]. The Vg was calculated by Eq. (4). and the autoclave; mSolution indicates the mass of the solution; and Cp,
solution indicates a specific heat capacity for the injected solution. The

4
M. Delavari et al. The Journal of Chemical Thermodynamics 186 (2023) 107142

Table 4
The experimental data of equilibrium solubility of carbon dioxide and modeling results in a blend of DMAE 40.04 wt% + EAE 5.01 wt% + H2O 54.95 wt% (percentages
are on the CO2-free basis) at range Temperature (313.15, 328.15, 343.15, 358.15) K, xCO2 stands for the mole fraction of CO2 in the liquid phase, α stands for CO2
loading, and their expanded uncertainties with 95% level of confidence, U(xCO2), U(α),U(wt%), Pexp stands for total experimental pressure, Pcalc stands for total
pressure calculated from the model, PCO2,calc stands for the calculated CO2 partial pressure.
T/K Psat/akPa xCO2 ± U(xCO2) b Loadingc(α ± U(α)b) Pexp./kPa Pcalc./kPa PCO2,calc/kPa RDPd

313.15 6.6 0.015(±0.008) 0.108(±0.055) 9.2 7.8 1.9 − 15.1

0.017(±0.008) 0.120(±0.057) 9.8 8.2 2.3 − 16.3
0.025(±0.008) 0.180(±0.055) 12.4 11.0 5.1 − 11.5
0.032(±0.007) 0.230(±0.053) 14.5 13.8 7.9 − 4.6
0.035(±0.008) 0.253(±0.055) 15.6 15.1 9.2 − 3.1
0.050(±0.006) 0.367(±0.048) 21.7 21.1 15.2 − 2.6
0.050(±0.006) 0.370(±0.047) 21.8 21.2 15.3 − 2.6
0.056(±0.006) 0.420(±0.044) 24.7 24.1 18.2 − 2.5
0.059(±0.006) 0.440(±0.044) 26.0 25.5 19.6 − 2.1
0.066(±0.005) 0.500(±0.041) 30.0 30.4 24.5 1.4
0.070(±0.005) 0.530(±0.040) 32.6 33.7 27.8 3.3
0.073(±0.005) 0.551(±0.037) 34.8 36.3 30.4 4.4

MADd% 16.3
AADd% 5.77

328.15 14.7 0.034(±0.004) 0.251(±0.031) 30.4 33.5 19.5 − 12.8

0.041(±0.004) 0.300(±0.030) 34.5 41.2 27.2 –22.3
0.049(±0.004) 0.362(±0.029) 39.4 51.4 37.4 –33.2
0.050(±0.004) 0.370(±0.027) 40.8 52.6 38.6 − 31.8
0.056(±0.003) 0.420(±0.025) 46.1 61.8 47.8 − 36.7
0.060(±0.003) 0.450(±0.023) 50.5 68.2 54.2 − 37.8
0.066(±0.003) 0.500(±0.021) 60.8 80.9 66.9 − 35.7
0.071(±0.003) 0.534(±0.019) 72.4 92.0 78.0 − 29.4
0.071(±0.003) 0.540(±0.019) 73.3 93.9 79.9 − 30.4
0.073(±0.003) 0.550(±0.019) 77.3 97.7 83.7 − 28.7
0.074(±0.002) 0.560(±0.019) 81.6 101.7 87.7 − 27
0.083(±0.002) 0.640(±0.015) 133.0 145.9 131.9 − 11.5

MADd% 37.8
AADd% 28.1

343.15 29.4 0.033(±0.002) 0.237(±0.013) 66.7 57.5 29.1 12.2

0.034(±0.002) 0.250(±0.013) 69.7 61.6 33.2 9.9
0.038(±0.002) 0.280(±0.012) 77.7 73.6 45.2 3.5
0.040(±0.002) 0.290(±0.012) 80.7 77.1 48.7 2.7
0.041(±0.002) 0.300(±0.012) 83.7 80.7 52.3 1.8
0.051(±0.001) 0.380(±0.010) 114.1 110.9 82.5 1.1
0.056(±0.001) 0.420(±0.009) 134.4 124.6 96.2 5.7
0.058(±0.001) 0.430(±0.009) 140.1 127.6 99.2 7.4
0.060(±0.001) 0.450(±0.009) 152.4 134.2 105.8 10.5
0.063(±0.001) 0.472(±0.008) 170.1 141.2 112.8 15.6
0.066(±0.001) 0.500(±0.008) 188.8 149.7 121.3 19.4
0.069(±0.001) 0.523(±0.007) 206.6 156.6 128.2 23.0

MADd% 23.0
AADd% 9.4

358.15 55.1 0.021(±0.002) 0.150(±0.011) 79.3 78.3 24.3 − 0.5

0.022(±0.002) 0.160(±0.011) 83.0 83.9 29.9 − 2.9
0.024(±0.001) 0.170(±0.011) 87.7 89.9 35.9 − 4.4
0.025(±0.001) 0.180(±0.010) 93.2 96.3 42.3 − 5.1
0.026(±0.001) 0.190(±0.010) 99.9 103.0 49.0 − 4.9
0.028(±0.001) 0.200(±0.010) 107.5 110.1 56.1 − 4.2
0.029(±0.001) 0.210(±0.009) 116.1 117.6 63.6 − 3
0.030(±0.001) 0.220(±0.009) 127.6 125.5 71.5 − 0.1
0.032(±0.001) 0.230(±0.009) 136.2 133.8 79.8 0.1
0.033(±0.001) 0.240(±0.009) 147.8 142.5 88.5 1.9
0.034(±0.001) 0.250(±0.009) 160.2 151.5 97.5 3.8
0.036(±0.001) 0.260(±0.006) 173.6 161.0 107.0 5.8

MADd% 5.8
AADd% 3.1
a
the measured saturation of vapor pressure of solution with Expanded uncertainties U at 95% confidence interval of U(Psat.) = 1.0 kPa.
b
Expanded uncertainties U at 95% confidence interval are U(T) = 0.02 K; U(Pexp.) = 1.0 kPa; U(DMAE wt%) = 0.39 wt%; U(EAE wt%) = 0.29 wt%.
)
c
( mole CO2
Loading = .
d mole DMAE + mole EAE
RDP%, AAD% and MAD% are relative deviation percent, average absolute percent deviation and maximum absolute deviation, respectively.

5
M. Delavari et al. The Journal of Chemical Thermodynamics 186 (2023) 107142

Table 5
The experimental data of carbon dioxide equilibrium solubility, and modeling results in a mixture of DMAE 30.02 wt% + EAE 5.01 wt% + H2O 64.97 wt% (percentages
are on the CO2-free basis) at range Temperature (313.15, 328.15, 343.15, 358.15), xCO2 indicates the mole fraction of CO2 in the liquid phase, α indicates CO2 loading
and their expanded uncertainties with 95% level of confidence, U(xCO2), U(α), U(wt%), Pexp indicates total experimental pressure, Pcalc indicates total pressure
calculated from the model, PCO2,calc indicates the calculated CO2 partial pressure.
T/K Psat/akPa xCO2 ± U(xCO2) b Loadingc(α ± U(α)b) Pexp./kPa Pcalc./kPa PCO2,calc/kPa RDPd

313.15 6.5 0.024(±0.005) 0.246(±0.056) 10.8 10.1 4.0 − 6.5

0.027(±0.004) 0.280(±0.049) 10.9 11.1 5.0 1.8
0.029(±0.003) 0.308(±0.048) 12.7 12.0 5.9 − 5.8
0.032(±0.003) 0.337(±0.046) 13.4 13.0 6.9 − 3.3
0.035(±0.002) 0.372(±0.043) 14.5 14.2 8.1 − 1.8
0.042(±0.001) 0.442(±0.036) 17.8 17.0 10.9 − 4.6
0.045(±0.001) 0.480(±0.033) 19.3 19.0 12.9 − 1.7
0.047(±0.001) 0.500(±0.031) 19.9 20.1 14.0 0.8
0.048(±0.001) 0.511(±0.030) 21.7 20.9 14.8 − 3.5
0.051(±0.001) 0.550(±0.026) 23.8 23.8 17.7 0.0

MADd% 6.5
AADd% 3.0

328.15 14.9 0.023(±0.002) 0.243(±0.033) 22.9 20.5 6.1 − 10.4

0.029(±0.001) 0.303(±0.028) 26.4 27.0 12.6 2.1
0.031(±0.001) 0.328(±0.027) 28.0 30.4 16.0 8.7
0.035(±0.001) 0.366(±0.025) 30.2 34.1 19.7 12.9
0.041(±0.001) 0.434(±0.021) 35.9 42.9 28.5 19.6
0.046(±0.001) 0.490(±0.016) 45.7 51.9 37.5 13.5
0.052(±0.001) 0.562(±0.013) 60.8 67.3 52.9 10.8
0.057(±0.001) 0.618(±0.011) 75.7 84.6 70.2 11.8
0.060(±0.001) 0.65(±0.008) 88.1 97.4 83.0 10.6
0.062(±0.001) 0.675(±0.007) 99.4 109.5 95.1 10.1

MADd% 19.6
AADd% 11.1

343.15 29.3 0.023(±0.001) 0.236(±0.014) 47.2 37.5 8.9 − 20.5

0.028(±0.001) 0.292(±0.012) 55.7 44.5 15.9 − 20.1
0.031(±0.001) 0.321(±0.011) 58.6 56.3 27.7 − 4.0
0.033(±0.001) 0.350(±0.010) 63.8 61.5 32.9 − 3.6
0.036(±0.001) 0.380(±0.009) 71.2 67.8 39.2 − 4.8
0.039(±0.001) 0.414(±0.008) 78.9 75.1 46.5 − 4.8
0.041(±0.001) 0.430(±0.008) 83.3 78.5 49.9 − 5.8
0.044(±0.001) 0.470(±0.006) 95.3 87.6 59.0 − 8.1
0.047(±0.001) 0.500(±0.005) 105.0 95.3 66.7 − 9.3
0.050(±0.001) 0.533(±0.004) 119.8 109.1 80.5 − 9.0

MADd% 20.5
AADd% 9.0

358.15 55.9 0.036(±0.001) 0.381(±0.010) 153.5 146.6 91.8 − 4.5

0.038(±0.001) 0.400(±0.009) 163.3 157.7 102.9 − 3.4
0.039(±0.001) 0.410(±0.009) 169.1 164.0 109.2 − 3.0
0.040(±0.001) 0.428(±0.008) 181.5 175.4 120.6 − 3.3
0.041(±0.001) 0.430(±0.008) 181.6 176.7 121.9 − 2.7
0.042(±0.001) 0.450(±0.008) 195.4 189.5 134.7 − 3.0
0.043(±0.001) 0.460(±0.007) 202.8 195.8 141.0 − 3.4
0.044(±0.001) 0.470(±0.007) 210.6 202.0 147.2 − 4.1
0.045(±0.001) 0.480(±0.007) 218.7 208.1 153.3 − 4.9
0.047(±0.001) 0.500(±0.006) 236.0 219.5 164.7 − 7.0

MADd% 7.0
AADd% 3.9
a
the measured saturation of vapor pressure of solution with Expanded uncertainties U at 95% confidence interval of U(Psat.) = 1.0 kPa.
b
Expanded uncertainties U at 95% confidence interval are U(T) = 0.02 K; U(Pexp.) = 1.0 kPa; U(DMAE wt%) = 0.29 wt%; U(EAE wt%) = 0.29 wt%.
)
c
( mole CO2
Loading = .
d mole DMAE + mole EAE
RDP%, AAD% and MAD% are relative deviation percent, average absolute percent deviation and maximum absolute deviation, respectively.

heat capacity of the autoclave is required to calculate the enthalpy of solution. The intersection of two curves yields the corrected temperature
absorption. The measured value of ΔHabs(the enthalpy of absorption) change. In earlier work by Zoghi et. al [4], the details of the enthalpy of
corresponds to dissolution from zero to the reported loading of CO2 in absorption (ΔHabs) and CP measurements procedure and validation were
the aqueous phase. The Santos et al. [28] approach was used to estimate disclosed.
the adjusted temperature change between the autoclave and the

6
M. Delavari et al. The Journal of Chemical Thermodynamics 186 (2023) 107142

HCO−3(aq) ⇆k3 CO−3(aq)

2 +
+ H(aq) (12)

Dissociation of protonated DMAE:

+
DMAEH(aq) ⇆k4 DMAE(aq) + H(aq)
+
(13)

Dissociation of protonated EAE:

+
EAEH(aq) ⇆k5 EAE(aq) + H(aq)
+
(14)

formation of EAE carbamate:

EAE(aq) + CO2(l) + H2 O(l) ⇆k6 EAECOO−(aq) + H3 O+

(aq) (15)

The dissociation of water is explained by reaction (10). Bicarbonate

is created in the reaction (11); the bicarbonate ion dissociates in the
reaction (12). The dissociation of protonated DMAE occurs in reaction
(13). Dissociation of protonated EAE is represented by reaction (14). The
Formation of EAE carbamate is shown in the reaction (15). Thus, the
species that are present in the liquid phase include; DMAE, DMAEH+,
EAE, EAEH+, H+, EAECOO− , H2O, OH–, CO2, CO−3 2, and HCO–3. The
Equilibrium constant in reactions (10–15) is shown in Eq. (16):
∏ ϑi,j
Kj = ai (16)
i
Fig. 4. Equilibrium solubility of CO2 curve for DMAE 40 wt% + EAE 5 wt%; (▴:
T = 313.15 K; ■: T = 328.15 K; ◊: T = 343.15 K; ○: T = 358.15 K, and line: in Eq. (16), υij symbolizes the stoichiometry of species i, and ai
modeling results). symbolizes the species activity determined from Eq. (17). Equilibrium
constants and Henry’s law constant follow Eq. (18).

αi = γ(m)
i mi (17)

C2
ln(k or HCO2 ) = C1 + + C3 lnT + C4 T (18)
T
in Eq. (17), γ (m)
i is the activity coefficient on the base of the molality
of species i, and mi symbolizes the molality weight of species i. Equations
(19)-(22) should be solved simultaneously to determine the molality of
species. The mass balances of DMAE, EAE, CO2 balance, and also the
electroneutrality balance of species are shown in Eqs. (19) to (22):
DMAE mass balance:
mt,DMAE = mDMAE + mDMAEH+ (19)

EAE mass balance:

mt,EAE = mEAE + mEAEH + + mEAECOO− (20)

CO2mass balance:
mCO2 ,t = mCO2 + mHCO−3 + mCO−3 2 + mEAECOO− (21)

Electroneutrality balance:
mH+ + mDMAEH + + mEAEH + = mOH− + mHCO−3 + 2mCO−3 2 + mEAECOO− (22)
Fig. 5. Equilibrium solubility of CO2 curve for DMAE 30 wt% + EAE 5 wt%; (▴:
T = 313.15 K; ■: T = 328.15 K; ◊: T = 343.15 K; ○: T = 358.15 K, and line: Eqs. (16), (17), and Eqs. (19) to (22) were solved simultaneously
modeling results). with the approach proposed by Smith et al. [29].

3. Thermodynamic framework 3.2. Phase equilibria modeling

3.1. Chemical equilibria VLE calculations were used to evaluate the molecular species in the
vapor and liquid phases. Amines (DMAE, EAE) have a low vapor pres­
Reactions (10)–(15) depict the chemical reactions that occur in the sure in the vapor phase; Therefore, they cannot exist in the vapor phase
liquid phase for the system of H2O –DMAE–EAE–CO2: [30]. Therefore, the phase equilibrium calculation should be performed
Dissociation of water: for the remaining species (CO2, H2O). The results in the articles show
that this is a reasonable assumption [31–34]. The vapor-liquid equilib­
H2 O(l) ⇆k1 H(aq)
+ −
+ OH(aq) (10)
rium for CO2 and H2O is presented in Eqs. (23) and (24):
Formation of bicarbonate:
yCO2 Pt φCO2 = xCO2 HCO2 γ *CO2 (23)
CO2(aq) + H2 O(l) ⇆ k2
HCO−3(aq) +
+ H(aq) (11)
yH2 O Pt φH2 O = xH2 O Psat *
H2 O γ H2 O (24)
Dissociation of bicarbonate ion:
where y stands as the molar fraction of the vapor phase and x

7
M. Delavari et al. The Journal of Chemical Thermodynamics 186 (2023) 107142

Table 6
The experimental data for the enthalpy of carbon dioxide absorption (ΔHabs, exp) in a mixture of DMAE 40.04 wt% + EAE 5.01 wt% + H2O 54.95 wt% (percentages are
on the CO2-free basis) at T = 328.15 K*, where Pexp stands for the total pressure, xCO2 stands for the CO2 mole fraction in an aqueous phase, αexp stands for CO2 loading,
and CP stands for the heat capacity of the loaded solution. U(α), U(xCO2), U(ΔHabs, exp), U(wt%), and U(CP) are of uncertainties with 95% level of confidence. ΔHabs,exp
stands for the experimental enthalpy of absorption of CO2; ΔHabs,cal stands for the calculated enthalpyof absorption of CO2.
Pexp./kPa xCO2 ± U(xCO2) αa ± Ub(α) Cp c ± U(Cp)/kJ⋅kg− 1⋅K− 1 1
− ΔHexp ± U(ΔHexp.)/kJ⋅mol−CO2 1
− ΔHcal/kJ⋅mol−CO2 RDPd
**
28.2 0.025(±0.002) 0.177(±0.011) 3.099(±0.135) 47.4(±3.0) 41.9 11.7
31.7 0.035 (±0.002) 0.258(±0.014) 3.038(±0.120) 52.0(±3.4) 44.6 14.2
47.5 0.054 (±0.003) 0.402(±0.020) 2.858(±0.114) 46.4(±1.6) 48.9 − 5.3
57.4 0.063(±0.003) 0.470(±0.022) 2.750(±0.106) 42.1(±1.6) 39.3 6.6
67.2 0.070(±0.003) 0.528(±0.025) 2.745(±0.103) 39.1(±1.6) 33.4 14.7
78.5 0.074 (±0.003) 0.562(±0.026) 2.689(±0.100) 37.6(±1.6) 24.6 34.6
132.0 0.083 (±0.004) 0.639(±0.029) 2.628(±0.099) 34.8(±1.6) 6.7 80.7
AADd% 24.0
*
The measured value enthalpy of absorption corresponds to dissolution of CO2 from zero to the reported loading of CO2 in the aqueous phase.
**
The initial solution state is the fresh solution (i.e loading = 0.0).
)
a
( mole CO2
α = .
b mole DMAE + mole EAE
Expanded uncertainties U at 95% confidence interval are U(T) = 0.02 K; U(P) = 0.4 kPa; U(DMAE wt%) = 0.39 wt%; U(EAE wt%) = 0.29 wt%.
c
the measured Cp in the present work, the measured Cp of fresh solution is 3.208 kJ⋅kg− 1⋅K− 1, with U(Cp) = 0.135 kJ⋅ kg− 1⋅ K− 1, under the solution vapor pressure
Psolution*=14.7 kPa, expanded uncertainties U at 95% confidence interval U(Psolution*) = 0.4 kPa.
d
RDP% and AAD% are relative deviation percent, average absolute percent deviation, respectively.

Fig. 6. Enthalpy of absorption of CO2 in DMAE 40 wt% + EAE 5 wt% at T = 328.15 (line: calculated data,□: experimental data).

represents the liquid phase’s molar fraction. Pt is the autoclave’s overall

Table 7 pressure. Equation of State (EoS) describes the fugacity coefficient as φ,
The enthalpy of absorption of CO2 prediction in DMAE 30 wt% + EAE 5 wt and the liquid phase’s activity coefficient is γ. The Henry’s law constant
%. is HCO2, and the water vapor pressure is PsatH2O.
α (mole CO2/mole amine) − ΔHcal/kJ⋅ mole− 1
CO2 Several approaches in the literature have demonstrated the non-
0.2 45.5 ideality of the liquid phase for modeling systems [35]. There are three
0.3 47.4 approaches: empirical and semi-empirical models, such as the modified
0.4 48.8 Kent Eisenberg model [36] and the Kent-Eisenberg model [37], and the
0.5 50.3 activity coefficient model. The extended UNIQUAC [38] and e-NRTL
0.6 50.6
models use the activity coefficient model and the equation of state (EoS)
0.7 50.3
0.8 40.0 to describe the liquid and vapor phases nonideality, respectively [16].
0.9 27.7 Since in electrolyte solutions activity coefficients are estimated for both
molecular and ionic species, these models usually consist of two or three
terms. [35]. The third category is the equation of state (EoS)-based
models. These models, to model vapor and liquid phases, use the same
equation of state. These models include the emPR-CPA EoS [35], eSAFT-

8
M. Delavari et al. The Journal of Chemical Thermodynamics 186 (2023) 107142

√̅̅
AZi2 I ∑
lnγi = − √̅̅ + 2 βi,j mj (25)
1+B I j∕
=w

B is considered a constant in this study; it is assumed to equal 1.2

[39], and βij is the binary interaction parameter of components with
each other in the aqueous phase. In Eq. (25), where A is constant and
depends on density, the solvent’s dielectric constant, and temperature.
Zi is the ionic charge of component i, and mj is the molality of component
j. I is ionic strength of the solution, which may be found in Eq. (26).
1∑
I= mi Zi2 (26)
2
The equilibrium constants of the Reaction (10)-(15) and Henry’s law
can be shown in Eq. (18) is given in Table 2.
Table 2. Constants of Eq. (18) to calculate the equilibrium reaction
constants and Henry’s law constant.
The equilibrium solubility data or tuned model, as stated in Eq. (27),
can be used to determine the enthalpy of absorption of CO2.
( )
ΔHabsorption dlnP
− = (27)
R d(1/T) α
Fig. 7. The enthalpy of absorption of CO2 in DMAE 30 wt% + EAE 5 wt% curve
(■: -ΔHabs predicted).
3.3. Data regression
HR EoS [39], and ePC-SAFT EoS [40]. The Deshmukh-Mather model
As explained in the previous section, there are eleven species in the
[41], because of being quick in calculating, accurate in correlating the
aqueous phase; Thus, the number of βi,j is 121. It was tried to reduce the
concentration of different species, and requiring fewer optimization
number of binary interaction parameters based on the following as­
parameters, was chosen to account for the non-idealities of the liquid
sumptions: 1) Self-interaction parameters are considered equal to zero
phase in the current study’s second category [42]. The Deshmukh-
(βii = 0); 2) βi,j is equal to βj,i; 3) Species that have low concentrations are
Mather model used the Debye-Hückel model to describe the long-
not considered except for interactions; The low concentration compo­
range interactions and a simplified version of the Pitzer model to
nents are H+, CO−3 2, OH–; 4) Ionic species with the same electric charge
explain the short-range interactions [42]. Peng-Robinson equation of
do not have interaction. 5) The interactions between the molecular
state represents the non-ideality of the vapor phase [43]. The activity
species are equal to zero. According to these assumptions and the
coefficient of species is defined from Guggenheim’s theory [41] and
sensitivity analysis, the number of parameters is reduced to 13. The
obtained from Eq. (25). In this model, water’s activity coefficient is
number of parameters was lowered to 10 with additional sensitivity
taken to be one.
analysis. The optimization’s objective function is given in Eq. (28). The

Fig. 8. Main Species of aqueous Solution of DMAE and EAE- CO2 loading at T = 313.15 K; symbols; ◆: DMAEH+; ×: HCO−3 ; ■: DMAE; △: EAECOO− ; ▴: CO2−
3 ; +:
CO2; ○: EAE.

9
M. Delavari et al. The Journal of Chemical Thermodynamics 186 (2023) 107142

relationship between βi,j and temperature is shown in Eq. (29). is 24.0. The study’s findings demonstrate that the Deshmukh-Mather
2
model is capable of making precise correlations about the CO2 equilib­
∑ (Pt,exp − Pt,cal )
OF = × 100 (28) rium solubility in an aqueous amine solution.
Pt,exp
5. Conclusion
βi,j = AT 3 + BT 2 + CT + D (29)

The optimized βi,j as a function of temperature are shown in Table 3. In the blends of DMAE + EAE, the experimental equilibrium solu­
bility of carbon dioxide was measured in the present investigation. At a
4. Results and discussion variety of temperatures (313.15, 328.15, 343.15, and 358.15) K, the
solubility of carbon dioxide was measured in solutions of DMAE 40 wt%
The equilibrium solubility apparatus was used to determine the + EAE 5 wt% and DMAE 30 wt% + EAE 5 wt%. The tuned model was
solubility of CO2 for two concentrations of DMAE 40 wt% + EAE 5 wt% used for the calculation of the enthalpy of absorption at 328.15 K for an
and DMAE 30 wt% + EAE 5 wt% in aqueous solutions at a temperature aqueous solution of (DMAE 40 wt% + EAE 5 wt%). The enthalpy of
range of (313.15–358.15) K with a 15 K step. Tables 4 and 5 show the absorption was predicted for an aqueous amine solution of (DMAE 30 wt
data, while Figs. 4 and 5 show the relative graphs. In a mixture of DMAE % + EAE 5 wt%) from the Gibbs Helmholtz equation at 328.15 K. The
(40 wt%) + EAE (5 wt%), the enthalpy of absorption of CO2 was enthalpy of absorption measurement results shows that the aqueous
measured at 328.15 K. Since DMAE and EAE have the same molar mass, solution of DMAE 40 wt% + EAE 5 wt% has about 28.6% lower enthalpy
similar structure, and similar properties like heat capacity. The of absorption in comparison to an aqueous solution of DMAE (40 wt%)
measured vapor pressure of the aqueous mixture of DMAE + EAE could and N,3-(Methylamino)propylamine (MAPA) (5 wt%) (at loading equal
be compared with those vapor pressures obtained by Chiali-Baba- to 0.5) which has been measured in our previous work [4]. Using the
Ahmed et al. [46]. The sum of mole fractions of amines in aqueous Deshmukh-Mather model, the experimental results were correlated, and
mixtures of DMAE (40 wt%) + EAE (5 wt%) and DMAE (30 wt%) + EAE the interaction parameters were optimized. For concentrations of
(5 wt%) are 0.142 and 0.098, respectively which could be considered as (DMAE 40 wt% + EAE 5 wt%) and (DMAE 30 wt% + EAE 5 wt%), the
equal to mole fraction of aqueous DMAE solution. Therefore, at T = average absolute percent deviations (AAD%) of CO2 solubility were 11.6
313.15 K, the values of vapor pressure obtained by Chialio-Baba-Ahmed and 6.7, respectively.
et al. [46] by interpolation are 6.48 for xAmine = 0.142 and 6.71 kPa for
xAmine = 0.098. If these values compare with those vapor pressure ob­ Declaration of Competing Interest
tained in Tables 4 and 5, the obtained errors% are 2.4 and 3.1. at T =
343.15 K, the reported vapor pressures by Chialio-Baba-Ahmed et al. The authors declare that they have no known competing financial
[46] by interpolation are 28.8 for xAmine = 0.142 and 29.7 kPa for xAmine interests or personal relationships that could have appeared to influence
= 0.098, respectively and if these vapor pressures compared with those the work reported in this paper.
are reported in Tables 4 and, the obtained errors% are 1.9 and 0.5,
respectively. Data availability
The heat capacity of fresh solution (loading CO2 = 0.0) of aqueous
solution of DMAE which was measured by Mundhwa and Henni [47] Data will be made available on request.
could be compared with the aqueous solution of DMAE (40 wt%) + EAE
(5 wt%), at T = 328.15 K and equal mole fraction xAmine = 0.142, the Acknowledgement
measures Cp by Mundhwa and Henni [47] is 3.283 J.g− 1.K− 1 and the
reported measures Cp of fresh solution is 3.208 J.g− 1.K− 1 which the The authors greatly appreciate the financial support for this research
relative error% is 2.3. The comparison of the properties of DMAE + provided by the Research Institute of Petroleum Industry.
water from the literatures and DMAE + EAE + water from this work at
the same amounts of amine gives enough confidence in the accuracy of References
the measurements which were done in the present work.
[1] B. Metz, O. Davidson, P. Bosch, et al. IPCC AR4. Climate Change 2007: Mitigation.
In the final step, the enthalpy of absorption was calculated by the
Contribution of Working Group III to the Fourth Assessment Report of the
tuned Deshmukh-Mather model for the aqueous solution of (DMAE 40 Intergovernmental Panel on Climate Change. 2007.
wt% + EAE 5 wt%) and is shown in Table 6 and Fig.6; besides, the [2] M.W. Arshad, H.F. Svendsen, P.L. Fosbøl, N. von Solms, K. Thomsen, Equilibrium
enthalpy of absorption was predicted for the aqueous solution of (DMAE Total Pressure and CO2 Solubility in Binary and Ternary Aqueous Solutions of 2-
(Diethylamino)ethanol (DEEA) and 3-(Methylamino)propylamine (MAPA), Journal
30 wt% + EAE 5 wt%) from Eq.(27) and it’s been shown in Table 7 and of Chemical & Engineering Data 59 (2014) 764–774, [Link]
Fig. 7. je400886w.
The mole fractions of the main species in the liquid phase are ob­ [3] M. Wang, A. Lawal, P. Stephenson, J. Sidders, C. Ramshaw, Post-combustion CO2
capture with chemical absorption: A state-of-the-art review Chem, Eng. Res. Des.
tained by the tuned model and can be seen in Fig. 8. Mole fractions of 89 (2011) 1609–1624, [Link]
molecular amines reduce an increase in CO2 loading. The protonated [4] A.T. Zoghi, A. Rahimi, F. Feyzi, A.H. Jalili, Measuring and modeling equilibrium
DMAE mole fraction is increased with increased CO2 loading and HCO–3 solubility of carbon dioxide in aqueous solution of dimethylaminoethanol and 3-
methylaminopropylamine Thermochimica Acta 686 (2020) 178565. 10.1016/j.
will increase with high CO2 loading. Based on the calculations, EAE tca.2020.178565.
protonated mole fraction is meager, and the stable form of EAE is [5] A.L. Kohl, R. Nielsen, Gas purification, Elsevier, 1997.
EAECOO− and other ionic species, EAECOO− mole fraction increases [6] A. Adeosun, M.R.M. Abu-Zahra. Evaluation of amine-blend solvent systems for CO2
post-combustion capture applications. Energy Procedia. 37. (2013). 211-218.
with increased CO2 loading.
10.1016/[Link].2013.05.104.
The parameters of the Deshmukh-Mather model were correlated to [7] N. El Hadri, D.V. Quang, E.L.V. Goetheer, M.R.M. Abu Zahra, Aqueous amine
experimental data, and the interaction parameters were optimized. The solution characterization for post-combustion CO2 capture process Appl, Energy
185 (2017) 1433–1449, [Link]
enthalpy of absorption for the aqueous solution of (DMAE 40 wt%+ EAE
[8] L. Rodier, K. Ballerat-Busserolles, J.-Y. Coxam, Enthalpy of absorption and limit of
5 wt%) was calculated by the tuned model at 328.15 K and it was pre­ solubility of CO2 in aqueous solutions of 2-amino-2-hydroxymethyl-1,3-propane­
dicted for (DMAE 30 wt% + EAE 5 wt%) at 328.15 K from Eq. (27). The diol, 2-[2-(dimethyl-amino)ethoxy] ethanol, and 3-dimethyl-amino-1-propanol at
AAD% for CO2 solubility data in DMAE 40 wt% + EAE 5 wt%, and T=(313.15 and 353.15)K and pressures up to 2MPa, The Journal of Chemical
Thermodynamics 42 (2010) 773–780, [Link]
DMAE 30 wt% + 5 wt% EAE are 11.6 and 6.7, respectively, according to [9] M.W. Arshad, N. von Solms, K. Thomsen, H.F. Svendsen, Heat of Absorption of CO2
Tables 4 and 5. The AAD% for the enthalpy of absorption data in Table 6 in Aqueous Solutions of DEEA, MAPA and their Mixture, Energy Procedia 37
(2013) 1532–1542, [Link]

10
M. Delavari et al. The Journal of Chemical Thermodynamics 186 (2023) 107142

[10] H. Arcis, L. Rodier, J.-Y. Coxam, Enthalpy of solution of CO2 in aqueous solutions [29] W.R. Smith, R.W. Missen, Strategies for solving the chemical equilibrium problem
of 2-amino-2-methyl-1-propanol, The Journal of Chemical Thermodynamics 39 and an efficient microcomputer-based algorithm, CJCE 66 (1988) 591–598,
(2007) 878–887, [Link] [Link]
[11] H. Arcis, L. Rodier, K. Ballerat-Busserolles, J.-Y. Coxam, Enthalpy of solution of [30] I. Kim, H.F. Svendsen, E. Børresen, Ebulliometric Determination of Vapor− Liquid
CO2 in aqueous solutions of methyldiethanolamine at T=322.5K and pressure up Equilibria for Pure Water, Monoethanolamine, N-Methyldiethanolamine, 3-
to 5MPa, The Journal of Chemical Thermodynamics 40 (2008) 1022–1029, (Methylamino)-propylamine, and Their Binary and Ternary Solutions, Journal of
[Link] Chemical & Engineering Data 53 (2008) 2521–2531, [Link]
[12] E.B. Rinker, S.S. Ashour, O.C. Sandall, Absorption of Carbon Dioxide into Aqueous je800290k.
Blends of Diethanolamine and Methyldiethanolamine Ind, Eng. Chem. Res. 39 [31] A.T. Zoghi, F. Feyzi, S. Zarrinpashneh, Equilibrium solubility of carbon dioxide in a
(2000) 4346–4356, [Link] 30wt.% aqueous solution of 2-((2-aminoethyl)amino)ethanol at pressures between
[13] I.M. Bernhardsen, A.A. Trollebø, C. Perinu, H.K. Knuutila, Vapour-liquid atmospheric and 4400kPa: An experimental and modelling study, The Journal of
equilibrium study of tertiary amines, single and in blend with 3-(methylamino) Chemical Thermodynamics 44 (2012) 66–74, [Link]
propylamine, for post-combustion CO2 capture, The Journal of Chemical jct.2011.08.011.
Thermodynamics 138 (2019) 211–228, [Link] [32] J. Xia, Á.-P.-S. Kamps, G. Maurer, Solubility of H2S in (H2O + Piperazine) and in
jct.2019.06.017. (H2O + MDEA + Piperazine), Fluid Phase Equilibria 207 (2003) 23–34, https://
[14] B. Zhao, F. Liu, Z. Cui, C. Liu, H. Yue, S. Tang, Y. Liu, H. Lu, B. Liang, Enhancing the [Link]/10.1016/S0378-3812(02)00331-X.
energetic efficiency of MDEA/PZ-based CO2 capture technology for a 650MW [33] Á.-P.-S. Kamps, A. Balaban, M. Jödecke, G. Kuranov, N.A. Smirnova, G. Maurer,
power plant: Process improvement Appl, Energy 185 (2017) 362–375, [Link] Solubility of Single Gases Carbon Dioxide and Hydrogen Sulfide in Aqueous
org/10.1016/[Link].2016.11.009. Solutions of N-Methyldiethanolamine at Temperatures from 313 to 393 K and
[15] R. Ramezani, S. Mazinani, R. Di Felice, S. Darvishmanesh, B. Van der Bruggen, Pressures up to 7.6 MPa: New Experimental Data and Model Extension, Industrial
Selection of blended absorbents for CO2 capture from flue gas: CO2 solubility, and Engineering Chemistry Research 40 (2001) 696–706, [Link]
corrosion and absorption rate Int, J. Greenhouse Gas Cont. 62 (2017) 61–68, 10.1021/ie000441r.
[Link] [34] A. Wangler, G. Sieder, T. Ingram, M. Heilig, C. Held, Prediction of CO2 and H2S
[16] P. Biernacki, W. Brehm, Experimental Measurements and Thermodynamic solubility and enthalpy of absorption in reacting N-methyldiethanolamine/water
Modelling of Carbon Dioxide Capture with use of 2-(Ethylamino) Ethanol, J. Fun systems with ePC-SAFT FluidPh, Equilibria 461 (2018) 15–27, [Link]
Ren. Energy App. 05 (2015), [Link] 10.1016/[Link].2017.12.033.
[17] D. Pandey, M. Kumar Mondal, Thermodynamic modeling and new experimental [35] A.T. Zoghi, F. Feyzi, M.R. Dehghani, Modeling CO2 Solubility in Aqueous N-
CO2 solubility into aqueous EAE and AEEA blend, heat of absorption, cyclic methyldiethanolamine Solution by Electrolyte Modified Peng-Robinson Plus
absorption capacity and desorption study for post-combustion CO2 capture Chem, Association Equation of State Ind, Eng. Chem. Res. 51 (2012) 9875–9885, https://
Eng. J. 410 (2021), 128334, [Link] [Link]/10.1021/ie2026053.
[18] H. Gao, B. Xu, H. Liu, Z. Liang, Effect of Amine Activators on Aqueous N, N- [36] H. Suleman, A.S. Maulud, A. Syalsabila, Thermodynamic modelling of carbon
Diethylethanolamine Solution for Postcombustion CO2 Capture, Energy & Fuels 30 dioxide solubility in aqueous amino acid salt solutions and their blends with
(2016) 7481–7488, [Link] alkanolamines, Journal of CO2 Utilization 26 (2018) 336–349, [Link]
[19] B.-K. Choi, S.-M. Kim, K.-M. Kim, U. Lee, J.H. Choi, J.-S. Lee, I.H. Baek, S.C. Nam, 10.1016/[Link].2018.05.014.
J.-H. Moon, Amine blending optimization for maximizing CO2 absorption capacity [37] R.L. Kent, B. Eisenberg, Better Data for Amine Treating Hydrocabon Proc. 55
in a diisopropanolamine – methyldiethanolamine – H2O system using the (1976) 87–90.
electrolyte UNIQUAC model Chem, Eng. J. 419 (2021), 129517, [Link] [38] N. Sadegh, E.H. Stenby, K. Thomsen. Thermodynamic modeling of CO2 absorption
10.1016/[Link].2021.129517. in aqueous N-Methyldiethanolamine using Extended UNIQUAC model Fuel. 144.
[20] S. Kumar, M.K. Mondal, Equilibrium Solubility of CO2 in Aqueous Blend of 2- (2015). 295-306. 10.1016/[Link].2014.12.002.
(Diethylamine)ethanol and 2-(2-Aminoethylamine)ethanol, Journal of Chemical & [39] A. Najafloo, F. Feyzi, A.T. Zoghi, Modeling solubility of CO2 in aqueous MDEA
Engineering Data 63 (2018) 1163–1169, [Link] solution using electrolyte SAFT-HR EoS, Journal of the Taiwan Institute of
jced.7b00544. Chemical Engineers 58 (2016) 381–390, [Link]
[21] M.K. Park, O.C. Sandall, Solubility of Carbon Dioxide and Nitrous Oxide in 50 mass jtice.2015.06.016.
Methyldiethanolamine, Journal of Chemical & Engineering Data 46 (2001) [40] M. Uyan, G. Sieder, T. Ingram, C. Held, Predicting CO2 solubility in aqueous N-
166–168, [Link] methyldiethanolamine solutions with ePC-SAFT, Fluid Phase Equilibria 393 (2015)
[22] M. Hosseini Jenab, M. Abedinzadegan Abdi, S.H. Najibi, M. Vahidi, N.S. Matin, 91–100, [Link]
Solubility of Carbon Dioxide in Aqueous Mixtures of N-Methyldiethanolamine + [41] R.D. Deshmukh, A.E. Mather, A Mathematical Model for Equilibrium Solubility of
Piperazine + Sulfolane, Journal of Chemical & Engineering Data 50 (2005) Hydrogen Sulfide and Carbon Dioxide in Aqueous Alkanolamine Solutions
583–586, [Link] Chemical Engineering Science 36 (1981) 355–362, [Link]
[23] A.T. Zoghi, F. Feyzi, S. Zarrinpashneh, Experimental investigation on the effect of 2509(81)85015-4.
addition of amine activators to aqueous solutions of N-methyldiethanolamine on [42] R.H. Weiland, T. Chakravarty, A.E. Mather, Solubility of Carbon Dioxide and
the rate of carbon dioxide absorption Int, J. Greenh. Gas Control 7 (2012) 12–19, Hydrogen Sulfide in Aqueous Alkanolamines Ind, Eng. Chem. Res. 32 (1993)
[Link] 1419–1430, [Link]
[24] M. Afkhamipour, M. Mofarahi, Experimental measurement and modeling study on [43] D.-Y. Peng, D.B. Robinson, A New Two-Constant Equation of State Ind, Eng. Chem.
CO2 equilibrium solubility, density and viscosity for 1-dimethylamino-2-propanol Fundam 15 (1976) 59–64, [Link]
(1DMA2P), Fluid Phase Equilibria 457 (2018) 38–51. [44] M.L. Posey, G.T. Rochelle, A Thermodynamic Model of Methyldiethanolamine CO2
[25] M. Shokouhi, A.H. Jalili, A.T. Zoghi, Experimental investigation of hydrogen and H2S Water Ind, Eng. Chem. Res. 36 (1997) 3944–3953, [Link]
sulfide solubility in aqueous sulfolane solution, The Journal of Chemical 10.1021/ie970140q.
Thermodynamics 106 (2017) 232–242, [Link] [45] T.J. Edwards, G. Maurer, J. Newman, J.M. Prausnitz, Vapor-Liquid Equilibria in
jct.2016.11.025. Multicomponent Aqueous Solutions of Volatile Weak Electrolytes, AIChE Journal
[26] P.J. Linstrom, W.G. Mallard, The NIST Chemistry WebBook: A Chemical Data 24 (1978) 966–976, [Link]
Resource on the Internet, Journal of Chemical & Engineering Data 46 (2001) [46] N. Chiali-Baba-Ahmed, F. Dergal, L. Negadi, I. Mokbel, Measurement and
1059–1063, [Link] correlation of the (vapor+liquid) equilibria of pure 4-ethylmorpholine, 1,2-
[27] A. Najafloo, A.T. Zoghi, F. Feyzi, Measuring solubility of carbon dioxide in aqueous dimethylisopropylamine and N, N-dimethylethanolamine, and their binary
blends of N-methyldiethanolamine and 2-((2-aminoethyl)amino)ethanol at low aqueous solutions, The Journal of Chemical Thermodynamics 63 (2013) 44–51,
CO2 loadings and modelling by electrolyte SAFT-HR EoS, The Journal of Chemical [Link]
Thermodynamics 82 (2015) 143–155, [Link] [47] M. Mundhwa, A. Henni, Molar Heat Capacity of Various Aqueous Alkanolamine
[28] L.M.N.B.F. Santos, M.T. Silva, B. Schröder, L. Gomes, Labtermo: Methodologies for Solutions from 303.15 K to 353.15 K, Journal of Chemical & Engineering Data 52
the calculation of the corrected temperature rise in isoperibol calorimetry, Journal (2007) 491–498, [Link]
of Thermal Analysis and Calorimetry 89 (2007) 175–180, [Link]
10.1007/s10973-006-7509-2.

11