Article pubs.acs.org/jced
Volumetric Properties of Binary Mixtures of 3‑(Methylamino)propylamine with Water, N‑Methyldiethanolamine, N,N‑Dimethylethanolamine, and N,N‑Diethylethanolamine from (283.15 to 363.15) K Xiaopo Wang,* Kai Kang, Wei Wang, and Yuansi Tian Key Laboratory of Thermo-Fluid Science and Engineering, Ministry of Education, Xi’an Jiaotong University, Xi’an 710049, China ABSTRACT: Experimental density data of the binary mixtures of 3-(methylamino)propylamine with water, N-methyldiethanolamine, N,N-dimethylethanolamine and N,N-diethylethanolamine were reported at atmospheric pressure over the entire composition range at temperatures from (283.15 to 363.15) K. The densities were measured using an Anton Paar digital vibrating U-tube densimeter. Excess molar volumes of the mixture were calculated from the experimental densities and correlated as the Redlich−Kister equation. The optimized sets of parameters of the equation were obtained by the leastsquares method at each temperature. Infinite dilution partial molar volumes and the corresponding excess partial molar volumes at infinite dilution were calculated and discussed. Thermal expansivities for the binary mixtures were presented.
1. INTRODUCTION Fossil fuel burning has increased CO2 concentration in the atmosphere over the past 200 years. Researchers over the world have been investigating effective methods to manage CO2 emissions. In addition, in the petroleum and natural gas industry, the removal of CO2, H2S, or other acid constituents from process gas streams is also very important. Chemical absorption is known to be the most reliable and economical process for acid gas removal. Aqueous solutions of alkanolamines are of great interest as chemical absorbents. A wide variety of aqueous alkanolamines, such as monoethanolamine (MEA), diethanolamine (DEA), diisopropanolamine (DIPA), or N-methyldiethanolamine (MDEA) have been extensively studied for this purpose. In the past few years, different studies have proposed the use of aqueous blended amine solutions, such as a primary or secondary alkanolamine with a tertiary alkanolamine, as a substitute for the aqueous solutions of a single alkanolamine in industrial level applications for CO2 capture. Those solutions combine the advantages of each individual amine and can produce a considerable improvement in absorption characteristics. Very recently, 3-(methylamino)propylamine (N-methyl-1,3propane diamine, MAPA) has received increasing attention for CO2 capture.1 Because of its fast reaction rate and high CO2 solubility, it has been considered as a promoter to tertiary amines (such as N-methyldiethanolamine (MDEA), N,N-dimethylethanolamine (DMEA), or N,N-diethylethanolamine (DEEA)) or carbonate solutions for improving the process of CO2 removal. For example, investigation showed that the MAPA + DMEA + H2O system had faster kinetics and higher CO2 capacity than 30 mass % MEA.2 At the same time, this system was found to have a potential for both lower heat of regeneration and lower environmental impact than MEA.3 © 2013 American Chemical Society
To design and optimize CO2 capture facilities, knowledge of physicochemical properties like densities, vapor−liquid equilibrium, viscosities, and surface tensions of those solvents are essential. Bruder4 studied the vapor−liquid equilibrium of the CO2 + MAPA + DMEA system. Vapor pressure of pure MAPA and the vapor−liquid equilibrium of MAPA + H2O and MAPA + MDEA + H2O systems were measured by Kim.5 The vapor− liquid−liquid equilibrium of the MAPA + DEEA + CO2 + H2O system was calculated using the electrolyte NRTL model.6 In addition, enthalpies of absorption of CO2, equilibrium solubilities and volatility data of MAPA had also been reported.7−9 Densities of the binary mixtures of amines can be used to determine the physical solubility of CO2 in solvent, mass transfer, and solvent kinetics. The accuracy of the densities of the solvents affects the reliability of process design calculations for designing the equipment. The derived volumetric properties, such as excess molar volume and partial molar volume at infinite dilution from density data, can be used to extend our understanding of molecular interactions in mixtures. Unfortunately, to our knowledge, the density of pure MAPA and aqueous blended MAPA solutions are not found in the literature. Before thinking about modeling the ternary mixtures, such as MAPA + DMEA + H2O or MAPA + MDEA + H2O, it is important to perform accurate modeling of the concerned binaries. In this work, densities of the binary mixtures of MAPA with water, MDEA, DMEA, and DEEA have been measured for the whole composition range. The excess molar volumes, partial molar volumes, and thermal expansivities were obtained. Received: July 24, 2013 Accepted: November 2, 2013 Published: November 15, 2013 3430
dx.doi.org/10.1021/je400679k | J. Chem. Eng. Data 2013, 58, 3430−3439
Journal of Chemical & Engineering Data
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Table 1. Sample Descriptions abbreviated name
IUPAC name
CAS No.
source
initial mole fraction purity
MAPA MDEA DMEA DEEA
1,3-propanediamine, N-methylN-methyldiethanolamine 2-(N,N-dimethylamino)ethanol ethanolamine, N,N-diethyl-
6291-84-5 105-59-9 108-01-0 100-37-8
Sigma-Aldrich Aladdin Chemistry Sigma-Aldrich Aladdin Chemistry
≥ 0.98 ≥ 0.98 ≥ 0.995 ≥ 0.99
Figure 1. Curves of excess molar volumes VE as a function of MAPA mole fraction for the binary mixtures at 333.15 K: ■, H2O; ●, MDEA; ▲, DEEA; ▼, DMEA. Solid line: calculated results from Redlich−Kister equation.
Figure 2. Comparison of excess molar volumes of various aqueous amine systems at 333.15 K: ■, MAPA; ●, MDEA;19 ★, DEEA;20 ▲, DMEA.16
Table 2. Comparison between the Experimental and Literature Data for Density Values of Pure Components at Different Temperatures ρ/g·cm−3 component
T/K
this work
lit. data
MDEA
293.15 303.15 313.15 323.15 333.15 343.15 353.15 303.15 313.15 323.15 333.15 343.15 353.15 363.15 293.15 303.15 313.15 323.15 333.15 353.15
1.040060 1.032468 1.024862 1.017212 1.009506 1.001732 0.993889 0.876155 0.866828 0.857388 0.847839 0.838157 0.828488 0.818597 0.886560 0.878059 0.869428 0.860655 0.851720 0.833288
1.04060,12 1.0315,10 1.03306,12 1.0249,10 1.02519,11 1.02545,12 1.0174,10 1.01699,11 1.0098,10 1.00960,11 1.0023,10 1.00183,11 0.994610 0.8752,13 0.8665,13 0.8657,14a 0.8555,13 0.8567,14a 0.8474,14a 0.8379,14a 0.8282,14a 0.8184,14a 0.88747,15 0.8875,17 0.87878,15 0.87835,16 0.8793,17 0.87025,15 0.86986,16 0.8692,17 0.8614,17 0.85189,16 0.83375,16
DEEA
DMEA
a
Figure 3. VE/(x1x2) as a function of MAPA mole fraction at atmospheric pressure and different temperatures: ■, 293.15 K; ●, 313.15 K; ▲, 333.15 K; ▼, 353.15 K.
using an analytical balance (model AB204-N, Mettler-Toledo) with an accuracy of ±0.1 mg. The uncertainty of the mole fraction was less than 2.0 × 10−4. Density measurements were performed by means of an Anton Paar digital vibrating U-tube densimeter (model DMA 5000 M). The temperature was determined with two integrated Pt 100 platinum thermometers, and the temperature in the cell was regulated to ±0.01 K. The densimeter was calibrated at atmosphere pressure with bidistilled and degassed water and dry air before and after measuring each sample. The uncertainty of density values was less than 5·10−6 g·cm−3 and the repeatability of density values is specified as 1.0·10−6 g·cm−3. During the measurement, the mixed sample density was measured at thermal
Calculated results.
2. EXPERIMENTAL SECTION Table 1 shows the sample descriptions used in the present work. All the solvents were used without further purification. Bidistilled water was used to prepare aqueous solutions. The binary mixtures under investigation in this work were prepared by mass 3431
dx.doi.org/10.1021/je400679k | J. Chem. Eng. Data 2013, 58, 3430−3439
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Table 3. Densities and Excess Molar Volumes for the Binary Mixtures from (283.15 to 363.15) K at Atmospheric Pressure (0.1 MPa)a x1b
ρ/(g·cm−3)
VE/(cm3·mol−1) 283.15 K
0.0000 0.0051 0.0200 0.0400 0.0599 0.0800 0.1001 0.1496 0.2001 0.2996 0.4001 0.4995 0.5998 0.6995 0.7976 0.9010 1.0000
0.999701 0.998237 0.994774 0.992840 0.991664 0.991853 0.990982 0.985446 0.975602 0.953237 0.932582 0.915228 0.900588 0.888711 0.879041 0.869652 0.860459
0.0000 0.0051 0.0200 0.0400 0.0599 0.0800 0.1001 0.1496 0.2001 0.2996 0.4001 0.4995 0.5998 0.6995 0.7976 0.9010 1.0000
0.992212 0.990476 0.985566 0.980873 0.976614 0.973774 0.970258 0.961197 0.950269 0.927601 0.906849 0.889428 0.874666 0.862629 0.852787 0.843170 0.833715
0.0000 0.0051 0.0200 0.0400 0.0599 0.0800 0.1001 0.1496 0.2001 0.2996 0.4001 0.4995 0.5998 0.6995 0.7976 0.9010 1.0000
0.977760 0.975769 0.969886 0.963394 0.957198 0.952467 0.947339 0.935674 0.923678 0.900476 0.879715 0.862344 0.847577 0.835508 0.825611 0.815925 0.806370
0.0000 0.1001 0.2003
1.040060 1.026934 1.012695
0.0000 −0.0452 −0.1890 −0.4275 −0.6748 −0.9542 −1.2074 −1.7228 −2.0636 −2.3721 −2.3920 −2.2299 −1.9441 −1.6016 −1.2268 −0.7088 0.0000 313.15 K 0.0000 −0.0529 −0.2056 −0.4338 −0.6543 −0.9000 −1.1191 −1.6003 −1.9543 −2.3204 −2.3864 −2.2582 −1.9925 −1.6592 −1.2855 −0.7503 0.0000 343.15 K 0.0000 −0.0585 −0.2218 −0.4498 −0.6600 −0.8909 −1.0952 −1.5560 −1.9155 −2.3152 −2.4148 −2.3104 −2.0551 −1.7240 −1.3451 −0.7915 0.0000 293.15 K 0.0000 −0.4516 −0.8221
ρ/(g·cm−3)
VE/(cm3·mol−1)
MAPA (1) + H2O (2) 293.15 K 0.998208 0.996630 0.992593 0.989571 0.987189 0.986200 0.984300 0.977467 0.967230 0.944826 0.924145 0.906757 0.892069 0.880119 0.870383 0.860902 0.851605 323.15 K 0.988140 0.986217 0.980949 0.975589 0.970587 0.967022 0.962871 0.952860 0.941571 0.918738 0.897972 0.880556 0.865773 0.853712 0.843839 0.834181 0.824673 353.15 K 0.971788 0.969700 0.963520 0.956509 0.949885 0.944681 0.939185 0.926784 0.914460 0.891074 0.870324 0.852997 0.838260 0.826212 0.816324 0.806659 0.797093 MAPA (1) + MDEA (2) 303.15 K 1.032468 1.019313 1.005007 3432
ρ/(g·cm−3)
VE/(cm3·mol−1) 303.15 K
0.0000 −0.0477 −0.1938 −0.4267 −0.6624 −0.9277 −1.1667 −1.6689 −2.0140 −2.3456 −2.3833 −2.2340 −1.9567 −1.6180 −1.2450 −0.7221 0.0000
0.995651 0.993985 0.989479 0.985557 0.982161 0.980175 0.977400 0.969396 0.958776 0.936290 0.915578 0.898165 0.883427 0.871429 0.861635 0.852078 0.842690
0.0000 −0.0531 −0.2094 −0.4370 −0.6529 −0.8921 −1.1045 −1.5779 −1.9345 −2.3142 −2.3929 −2.2738 −2.0122 −1.6805 −1.3057 −0.7644 0.0000
0.983197 0.981304 0.975762 0.969758 0.964115 0.959923 0.955236 0.944358 0.932714 0.909696 0.888926 0.871523 0.856742 0.844674 0.834781 0.825100 0.815559
0.0000 −0.0598 −0.2259 −0.4539 −0.6640 −0.8924 −1.0949 −1.5504 −1.9109 −2.3184 −2.4267 −2.3285 −2.0756 −1.7447 −1.3638 −0.8058 0.0000
0.965305 0.963045 0.956663 0.949281 0.942172 0.936552 0.930768 0.917665 0.905046 0.881470 0.860741 0.843475 0.828782 0.816767 0.806909 0.797262 0.787723
0.0000 −0.4744 −0.8620
1.024862 1.011658 0.997273
0.0000 −0.0503 −0.1996 −0.4294 −0.6564 −0.9106 −1.1385 −1.6294 −1.9780 −2.3296 −2.3827 −2.2446 −1.9732 −1.6380 −1.2651 −0.7365 0.0000 333.15 K 0.0000 −0.0571 −0.2179 −0.4445 −0.6570 −0.8913 −1.0987 −1.5653 −1.9237 −2.3141 −2.4036 −2.2920 −2.0339 −1.7030 −1.3261 −0.7784 0.0000 363.15 K 0.0000 −0.0594 −0.2298 −0.4603 −0.6684 −0.8951 −1.0976 −1.5474 −1.9092 −2.3225 −2.4382 −2.3458 −2.0947 −1.7635 −1.3810 −0.8167 0.0000 313.15 K 0.0000 −0.4964 −0.9009
dx.doi.org/10.1021/je400679k | J. Chem. Eng. Data 2013, 58, 3430−3439
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Table 3. continued x1b
ρ/(g·cm−3)
0.2999 0.3997 0.5000 0.5999 0.7001 0.8002 0.9000 1.0000
0.997588 0.981393 0.964134 0.944646 0.923928 0.900759 0.876717 0.851605
0.0000 0.1001 0.2003 0.2999 0.3997 0.5000 0.5999 0.7001 0.8002 0.9000 1.0000
1.017212 1.003953 0.989479 0.974031 0.957394 0.939738 0.919850 0.898494 0.874972 0.850467 0.824673
0.0000 0.1001 0.2003 0.2999 0.3997 0.5000 0.5999 0.7001 0.8002 0.9000 1.0000
0.993889 0.980415 0.965631 0.949783 0.932732 0.914593 0.894290 0.872517 0.848523 0.823509 0.797093
0.0000 0.0999 0.2000 0.3001 0.3997 0.5000 0.5998 0.7001 0.8000 0.8996 1.0000
0.894423 0.892458 0.890440 0.888023 0.885377 0.882338 0.878902 0.874969 0.870601 0.866062 0.860459
0.0000 0.0999 0.2000 0.3001 0.3997 0.5000 0.5998 0.7001 0.8000 0.8996 1.0000
0.866828 0.865456 0.863792 0.861601 0.859082 0.856105 0.852691 0.848689 0.844237 0.839530 0.833715
0.0000 0.0999
0.838157 0.837416
VE/(cm3·mol−1)
ρ/(g·cm−3)
293.15 K
VE/(cm3·mol−1)
ρ/(g·cm−3)
303.15 K −1.1274 −1.3607 −1.5298 −1.4870 −1.3542 −0.9793 −0.5339 0.0000
0.989787 0.973417 0.956077 0.936426 0.915360 0.892077 0.868035 0.842690
0.0000 −0.5189 −0.9403 −1.2794 −1.5297 −1.7157 −1.6751 −1.5069 −1.1116 −0.6210 0.0000
1.009506 0.996181 0.981607 0.966033 0.949272 0.931432 0.911414 0.889941 0.866238 0.841566 0.815559
323.15 K
313.15 K −1.1776 −1.4128 −1.5926 −1.5466 −1.3862 −1.0046 −0.5626 0.0000
0.981940 0.965391 0.947946 0.928152 0.907016 0.883714 0.859287 0.833715
0.0000 −0.5413 −0.9792 −1.3298 −1.5898 −1.7765 −1.7376 −1.5690 −1.1589 −0.6507 0.0000
1.001732 0.988342 0.973656 0.957953 0.941042 0.923056 0.902895 0.881277 0.857422 0.832576 0.806370
333.15 K
353.15 K 0.0000 −0.5876 −1.0602 −1.4335 −1.7097 −1.9069 −1.8693 −1.6916 −1.2593 −0.7122 0.0000 283.15 K 0.0000 −0.1073 −0.2211 −0.2933 −0.3487 −0.3727 −0.3635 −0.3159 −0.2375 −0.1657 0.0000 313.15 K 0.0000 −0.1945 −0.3562 −0.4529 −0.5160 −0.5358 −0.5143 −0.4396 −0.3305 −0.2177 0.0000 343.15 K 0.0000 −0.2936
363.15 K 0.985958 0.972409 0.957499 0.941523 0.924324 0.906038 0.885584 0.863668 0.839559 0.814342 0.787723 MAPA (1) + DEEA (2) 293.15 K 0.885356 0.883574 0.881665 0.879317 0.876712 0.873685 0.870252 0.866283 0.861885 0.857283 0.851605 323.15 K 0.857388 0.856219 0.854692 0.852583 0.850120 0.847171 0.843770 0.839765 0.835289 0.830547 0.824673 353.15 K 0.828488 0.827843 3433
VE/(cm3·mol−1) −1.2280 −1.4652 −1.6539 −1.6075 −1.4521 −1.0759 −0.5915 0.0000 343.15 K 0.0000 −0.5650 −1.0189 −1.3813 −1.6485 −1.8406 −1.8021 −1.6295 −1.2077 −0.6800 0.0000
0.0000 −0.6126 −1.1016 −1.4885 −1.7732 −1.9768 −1.9389 −1.7574 −1.3174 −0.7452 0.0000 303.15 K 0.0000 −0.1339 −0.2626 −0.3427 −0.4013 −0.4238 −0.4110 −0.3541 −0.2666 −0.1818 0.0000
0.876155 0.874574 0.872785 0.870463 0.867945 0.864940 0.861519 0.857522 0.853099 0.848439 0.842690
0.0000 −0.2255 −0.4060 −0.5109 −0.5773 −0.5950 −0.5683 −0.4848 −0.3634 −0.2368 0.0000
0.847839 0.846874 0.845474 0.843452 0.841042 0.838132 0.834751 0.830750 0.826265 0.821487 0.815559
0.0000 −0.3112
0.818597 0.818122
0.0000 −0.1634 −0.3083 −0.3894 −0.4570 −0.4782 −0.4620 −0.3953 −0.2979 −0.1992 0.0000 333.15 K 0.0000 −0.2576 −0.4556 −0.5695 −0.6383 −0.6550 −0.6233 −0.5312 −0.3984 −0.2568 0.0000 363.15 K 0.0000 −0.3406
dx.doi.org/10.1021/je400679k | J. Chem. Eng. Data 2013, 58, 3430−3439
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Table 3. continued x1b
ρ/(g·cm−3)
0.2000 0.3001 0.3997 0.5000 0.5998 0.7001 0.8000 0.8996 1.0000
0.836147 0.834206 0.831853 0.828978 0.825629 0.821629 0.817142 0.812342 0.806370
0.0000 0.0998 0.2000 0.3001 0.4000 0.4997 0.5993 0.6999 0.7990 0.9000 1.0000
0.894959 0.893869 0.892030 0.889578 0.886723 0.883310 0.879367 0.875276 0.871091 0.866659 0.860459
0.0000 0.0998 0.2000 0.3001 0.4000 0.4997 0.5993 0.6999 0.7990 0.9000 1.0000
0.869428 0.868337 0.866420 0.863872 0.860932 0.857442 0.853398 0.849183 0.844832 0.840193 0.833715
0.0000 0.0998 0.2000 0.3001 0.4000 0.4997 0.5993 0.6999 0.7990 0.9000 1.0000
0.842604 0.841562 0.839622 0.837042 0.834073 0.830555 0.826477 0.822212 0.817780 0.813022 0.806370
VE/(cm3·mol−1) 343.15 K −0.5098 −0.6312 −0.7024 −0.7165 −0.6805 −0.5780 −0.4335 −0.2772 0.0000 283.15 K 0.0000 −0.2729 −0.4635 −0.5846 −0.6585 −0.6673 −0.6123 −0.5415 −0.4506 −0.3342 0.0000 313.15 K 0.0000 −0.3050 −0.5135 −0.6461 −0.7298 −0.7451 −0.6897 −0.6143 −0.5119 −0.3768 0.0000 343.15 K 0.0000 −0.3385 −0.5652 −0.7100 −0.8030 −0.8230 −0.7666 −0.6866 −0.5734 −0.4200 0.0000
ρ/(g·cm−3)
VE/(cm3·mol−1)
353.15 K 0.826695 0.824829 0.822533 0.819712 0.816396 0.812413 0.807931 0.803118 0.797093 MAPA (1) + DMEA (2) 293.15 K 0.886560 0.885469 0.883599 0.881113 0.878225 0.874783 0.870800 0.866663 0.862415 0.857904 0.851605 323.15 K 0.860655 0.859574 0.857639 0.855069 0.852112 0.848606 0.844543 0.840300 0.835912 0.831218 0.824673 353.15 K 0.833288 0.832286 0.830357 0.827791 0.824830 0.821322 0.817252 0.812995 0.808563 0.803789 0.797093
ρ/(g·cm−3)
VE/(cm3·mol−1) 363.15 K
−0.5466 −0.6768 −0.7523 −0.7685 −0.7300 −0.6208 −0.4668 −0.2980 0.0000
0.817116 0.815306 0.813074 0.810325 0.807063 0.803095 0.798611 0.793772 0.787723
0.0000 −0.2837 −0.4800 −0.6052 −0.6823 −0.6933 −0.6382 −0.5659 −0.4710 −0.3481 0.0000
0.878059 0.876968 0.875071 0.872551 0.869634 0.866166 0.862148 0.857970 0.853666 0.849087 0.842690
0.0000 −0.3161 −0.5304 −0.6667 −0.7536 −0.7708 −0.7153 −0.6382 −0.5323 −0.3906 0.0000
0.851720 0.850654 0.848712 0.846131 0.843164 0.839647 0.835571 0.831314 0.826896 0.822163 0.815559
0.0000 −0.3510 −0.5839 −0.7335 −0.8292 −0.8506 −0.7936 −0.7126 −0.5962 −0.4365 0.0000
0.823754 0.822801 0.820903 0.818354 0.815413 0.811930 0.807876 0.803636 0.799198 0.794432 0.787723
−0.5976 −0.7317 −0.8107 −0.8298 −0.7897 −0.6710 −0.5038 −0.3179 0.0000 303.15 K 0.0000 −0.2945 −0.4968 −0.6257 −0.7061 −0.7194 −0.6641 −0.5904 −0.4917 −0.3628 0.0000 333.15 K 0.0000 −0.3272 −0.5477 −0.6881 −0.7781 −0.7967 −0.7408 −0.6627 −0.5527 −0.4051 0.0000 363.15 K 0.0000 −0.3635 −0.6039 −0.7572 −0.8556 −0.8789 −0.8206 −0.7378 −0.6157 −0.4510 0.0000
Standard uncertainties u are u(x1) = 2.0·10−4, u(T) = 0.01 K, u(ρ) = 5·10−6 g·cm−3, and u(VE) = 2.0·10−3 cm3•mol−1. bx1: the mole fraction of MAPA.
a
equilibrium after changing the temperature following successive increments.
range from (283.15 to 363.15) K at atmospheric pressure, are given in Table 3. Table 3 also includes the density data of the MAPA + MDEA system at the temperature range from (293.15 to 363.15) K. Excess thermodynamic properties are of great importance in understanding the nature of molecular interaction existing in the binary mixtures. The density values were used to calculate excess molar volume VE using the following equation:
3. RESULTS AND DISCUSSION To check the purities of the components in this work, comparisons between the experimental data and literature values of densities of pure MDEA, DMEA, and DEEA are presented in Table 2. It can be observed that results in this work agree well with the literature. The experimental data of the binary mixtures, MAPA + H2O, MAPA + DMEA, and MAPA + DEEA, over the temperature
V E = (x1M1 + x 2M 2)/ρ − (x1M1/ρ1 + x 2M 2 /ρ2 ) 3434
(1)
dx.doi.org/10.1021/je400679k | J. Chem. Eng. Data 2013, 58, 3430−3439
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Table 4. Redlich−Kister Coefficients and Standard Deviations for the Binary Mixtures at (283.15 to 363.15) K T
A0
A1
A2
A3
A4
A5
A6
σ
K
cm3·mol−1
cm3·mol−1
cm3·mol−1
cm3·mol−1
cm3·mol−1
cm3·mol−1
cm3·mol−1
cm3·mol−1
283.15 293.15 303.15 313.15 323.15 333.15 343.15 353.15 363.15
−8.861 −8.865 −8.897 −8.941 −9.023 −9.068 −9.142 −9.216 −9.311
4.346 4.224 4.125 4.028 3.971 3.868 3.795 3.721 3.703
−3.890 −4.181 −4.378 −4.628 −3.979 −4.692 −4.539 −4.423 −3.588
−7.634 −6.520 −5.514 −4.767 −3.542 −3.408 −2.879 −2.539 −1.511
7.268 3.921 1.288 −1.153 −0.177 −3.898 −4.296 −4.673 −2.312
0.014 0.014 0.014 0.015 0.011 0.015 0.015 0.014 0.010
293.15 303.15 313.15 323.15 333.15 343.15 353.15 363.15
−6.033 −6.260 −6.502 −6.763 −7.014 −7.270 −7.534 −7.810
−1.471 −1.381 −1.510 −1.512 −1.566 −1.626 −1.682 −1.755
0.984 0.998 0.823 0.837 0.775 0.714 0.650 0.568
283.15 293.15 303.15 313.15 323.15 333.15 343.15 353.15 363.15
−1.463 −1.682 −1.896 −2.129 −2.366 −2.605 −2.851 −3.059 −3.302
0.051 0.030 0.061 0.160 0.237 0.303 0.381 0.408 0.421
−0.038 0.003 −0.056 −0.126 −0.187 −0.261 −0.356 −0.376 −0.429
283.15 293.15 303.15 313.15 323.15 333.15 343.15 353.15 363.15
−2.599 −2.701 −2.802 −2.902 −3.003 −3.105 −3.207 −3.315 −3.425
0.532 0.510 0.489 0.471 0.452 0.439 0.431 0.422 0.419
−0.898 −0.943 −0.995 −1.041 −1.090 −1.143 −1.197 −1.267 −1.316
MAPA (1) + H2O (2) 3.244 −2.779 2.168 0.156 1.241 2.383 0.571 4.495 −0.384 2.999 −0.552 6.522 −0.949 6.579 −1.211 6.631 −1.900 3.826 MAPA (1) + MDEA (2) 1.501 1.365 1.417 1.387 1.395 1.427 1.417 1.425 MAPA (1) + DEEA (2) −0.665 −0.423 −0.330 −0.354 −0.338 −0.308 −0.256 −0.314 −0.201 MAPA (1) + DMEA (2) −1.430 −1.428 −1.434 −1.440 −1.439 −1.453 −1.479 −1.509 −1.516
where ρ is the measured density of the binary mixtures, x1, M1, and ρ1 are the mole fraction, molar mass, and density of pure MAPA, x2, M2, and ρ2 are the mole fraction, molar mass, and density of the second pure component (H2O, MDEA, DMEA, and DEEA). The VE values of the binary mixtures are also given in Table 3. The uncertainty of the excess molar volumes was estimated to be less of 2.0·10−3 cm3·mol−1. Excess molar volume results in this work were correlated as the Redlich−Kister equation,18 which has the following expression:
i=0
(2)
Ai are adjustable parameters, n is the number of the coefficients in the equation which was determined by standard deviation, σ. The standard deviation was calculated by E σ = [∑ (V E − Vcal )/(Nexp − n)]1/2
0.011 0.009 0.011 0.010 0.010 0.010 0.011 0.011 0.013 0.017 0.017 0.018 0.018 0.019 0.019 0.016 0.017 0.018
where Nexp is the number of experimental points, VEcal is the calculated results from eq 2. The Redlich−Kister coefficients, Ai, were determined with the least-squares method at each temperature and are given in Table 4 along with the standard deviations of the fit. Figure 1 shows the dependence of VE on concentration at 333.15 K for the binary mixtures, the solid lines represent results calculated from eq 2. From Table 1 and Figure 1, we can see that all VE values are negative. Negative VE values indicate that packing effects become dominant in the mixture compared to the pure components. The negative values of VE for the studied mixtures follow the order H2O > MDEA > DMEA > DEEA. The minimum value of VE of the mixture MAPA + H2O occurs at x1 = 0.4, however for the MAPA + DEEA system the value shifts to x1 = 0.5. The magnitude of VE reflects the compactness. The large negative VE is a consequence of a complex formation through very strong molecular interactions between the −OH group of the four components (H2O, MDEA, DMEA, and DEEA) and −NH2 group of MAPA molecules. MDEA has two −OH groups, DEEA and DMEA has one −OH group, so the volume contraction between
n
V E = x1x 2 ∑ Ai (x1 − x 2)i
0.017 0.019 0.016 0.016 0.016 0.016 0.016 0.016
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hydrophobic solutes in water, VE/(x1x2) will generally go through a minimum in the water rich region. Coquelet et al.22 investigated VE/ (x1x2) for several of aqueous amine solutions, such as 3(dimethylamino)propylamine + water and isopropanolamine + water, and found the existence of the expected minimum at high water concentrations or dilute amine concentrations. In this work, for the binary mixture of MAPA + water, the quantities VE/(x1x2) were also calculated to see the intermolecular interactions at low MAPA concentrations, and the results are presented in Figure 3. It shows that there exists a prounced minimum at about 0.15 mol fraction of MAPA. MAPA has two amine groups. Interactions between the amine group and water make the existence of the minimum, which means there is a breakup of the intermolecular interactions between water and MAPA at high water concentration. The partial molar volume of MAPA at infinite dilution in water, MDEA, DMEA, or DEEA (x1|→ 0), V1∞, and the partial molar volume of water, MDEA, DMEA, or DEEA at infinite dilution in MAPA (x2 → 0), V 2∞, were obtained using the method proposed by Maham et al.23
Table 5. Partial Molar Volumes V i∞and Excess Partial Molar Volumes ( ViE )∞ at Infinite Dilution as a Function of Temperature for the Binary Mixtures T
V1∞
V 2∞
( V1E )∞
( V2E )∞
K
(cm3·mol−1)
(cm3·mol−1)
(cm3·mol−1)
(cm3·mol−1)
283.15 293.15 303.15 313.15 323.15 333.15 343.15 353.15 363.15
94.23 94.67 95.15 95.67 96.67 97.04 97.95 98.94 100.23
293.15 303.15 313.15 323.15 333.15 343.15 353.15 363.15
98.43 99.36 100.15 101.09 102.02 102.96 103.97 104.99
283.15 293.15 303.15 313.15 323.15 333.15 343.15 353.15 363.15
101.75 102.23 102.92 103.67 104.44 105.22 105.98 107.06 107.95
283.15 293.15 303.15 313.15 323.15 333.15 343.15 353.15 363.15
99.85 100.78 101.75 102.76 103.78 104.85 105.96 107.09 108.26
MAPA (1) + H2O (2) 9.71 −8.22 8.95 −8.84 8.34 −9.46 7.76 −10.06 8.10 −10.22 7.10 −11.04 6.99 −11.36 6.83 −11.65 7.57 −11.68 MAPA (1) + MDEA (2) 109.55 −5.08 110.14 −5.25 110.50 −5.59 111.09 −5.80 111.63 −6.07 112.20 −6.36 112.74 −6.62 113.28 −6.91 MAPA (1) + DEEA (2) 128.86 −0.70 130.29 −1.29 131.53 −1.68 132.75 −2.06 134.03 −2.45 135.35 −2.86 136.74 −3.33 138.11 −3.53 139.65 −3.95 MAPA (1) + DMEA (2) 95.21 −2.60 95.98 −2.73 96.78 −2.85 97.62 −2.97 98.49 −3.11 99.40 −3.23 100.34 −3.36 101.31 −3.50 102.37 −3.64
−8.31 −9.10 −9.75 −10.40 −10.13 −11.23 −11.43 −11.71 −11.09 −5.02 −5.28 −5.77 −6.05 −6.41 −6.75 −7.15 −7.57
n
V1∞ = V1* +
∑ Ai(−1)i i=0
(4)
n
V 2∞ = V 2* +
∑ Ai i=0
(5)
where V1* and V2* are the molar volumes of the pure compounds. The corresponding excess partial molar volumes at infinite dilution, ( V1E )∞ and ( V2E )∞ are calculated from:
−2.16 −2.07 −2.22 −2.45 −2.65 −2.87 −3.08 −3.34 −3.51
n
(V1E)∞ =
∑ Ai(−1)i i=0
(6)
n
(V2E)∞ =
∑ Ai i=0
−4.40 −4.56 −4.74 −4.91 −5.08 −5.26 −5.45 −5.67 −5.84
(7)
The partial molar volumes at infinite dilution and the excess partial molar volumes at infinite dilution are given in Table 5. All values of the partial molar volume at infinite dilution V1∞ and V 2∞ were smaller than the corresponding molar volumes of pure components. This can be explained by the packing effect between different molecules. For example, the existence of hydrogen bonding can create an “empty” volume in liquid water, and the MAPA molecule partially fills up the open or empty space in liquid water. The thermal expansivities α of the studied binary mixtures were calculated as follows:
MAPA and MDEA is more compact than MAPA with DEEA or DMEA. In addition, water is a solvent with extended hydrogenbond framework and with cavities in the structure, this makes the volume of the MAPA+H2O mixture contract more. Figure 2 shows comparison of the excess molar volumes of (MAPA+H2O), (MDEA+H2O), (DEEA+H2O), and (DMEA+H2O) mixtures against the mole fraction of amines at 333.15 K. It clearly indicates the effect of the −NH2 group presented in MAPA resulting in high negative VE; however, the effect of the −OH group results in less negative values. The excess molar volume of DMEA and DEEA are similar which indicates that the addition of the two −CH2 groups to the DEEA has no obvious effect on the excess molar volume. As the suggestion from Desnoyers and Perron,21 the quality E V /(x1x2) is more appropriate to give information on interactions at low concentrations. At the same time, they also noted that, with
α = −ρ−1(∂ρ /∂T )p , x
(8)
The density was fitted with polynomial of the third degree as a function of temperature at a specified concentration. The (∂ρ/∂T)p,x values can be determined by differentiation of the ρ = f(T)p,x function. Table 6 presents the values of thermal expansivities of MAPA + H2O, MAPA + MDEA, MAPA + DMEA, and MAPA + DEEA at different temperatures. Figure 4 shows the dependence of thermal expansivities of the MAPA + water mixture on the MAPA concentration at different temperatures. All values of thermal expansivities at all temperatures have almost the same trend. And at lower MAPA concentrations α values are increasing sharply, especially at low temperatures. At higher concentrations α values increase more 3436
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Table 6. Thermal Isobaric Expansivities for the Binary Mixtures at Temperatures of (283.15 to 363.15) K α·103/K−1 x1
283.15
293.15
303.15
0.0000 0.0051 0.0200 0.0400 0.0599 0.0800 0.1001 0.1496 0.2001 0.2996 0.4001 0.4995 0.5998 0.6995 0.7976 0.9010 1.0000
0.10 0.12 0.18 0.30 0.42 0.55 0.66 0.80 0.85 0.87 0.90 0.92 0.94 0.96 0.98 1.00 1.03
0.20 0.22 0.27 0.37 0.48 0.59 0.69 0.82 0.87 0.90 0.92 0.94 0.96 0.98 1.00 1.02 1.04
0.30 0.31 0.35 0.44 0.53 0.63 0.72 0.83 0.89 0.92 0.94 0.96 0.98 1.00 1.02 1.04 1.06
0.72 0.74 0.76 0.78 0.79 0.80 0.82 0.83 0.84 0.85 1.04
0.73 0.75 0.77 0.79 0.82 0.85 0.88 0.93 0.96 1.00 1.06
0.0000 0.1001 0.2003 0.2999 0.3997 0.5000 0.5999 0.7001 0.8002 0.9000 1.0000 0.0000 0.0999 0.2000 0.3001 0.3997 0.5000 0.5998 0.7001 0.8000 0.8996 1.0000
1.01 0.99 0.98 0.97 0.97 0.98 0.98 0.99 1.00 1.01 1.03
1.03 1.01 1.00 0.99 0.99 1.00 1.00 1.01 1.02 1.03 1.04
1.06 1.04 1.02 1.01 1.02 1.02 1.02 1.03 1.03 1.05 1.06
0.0000 0.0998 0.2000 0.3001 0.4000 0.4997 0.5993 0.6999 0.7990 0.9000 1.0000
0.94 0.94 0.94 0.94 0.95 0.97 0.97 0.98 1.00 1.01 1.03
0.96 0.96 0.96 0.96 0.97 0.99 0.99 1.00 1.02 1.02 1.04
0.98 0.98 0.99 0.98 0.99 1.01 1.01 1.02 1.04 1.04 1.06
313.15
323.15
MAPA (1) + H2O (2) 0.38 0.46 0.39 0.47 0.43 0.50 0.51 0.57 0.59 0.64 0.68 0.72 0.75 0.78 0.85 0.88 0.91 0.93 0.95 0.97 0.97 1.00 0.99 1.02 1.01 1.03 1.03 1.05 1.04 1.07 1.06 1.08 1.08 1.10 MAPA (1) + MDEA (2) 0.74 0.75 0.76 0.78 0.78 0.79 0.80 0.82 0.83 0.85 0.86 0.88 0.89 0.91 0.94 0.95 0.97 0.99 1.02 1.04 1.08 1.10 MAPA (1) + DEEA (2) 1.08 1.11 1.06 1.08 1.05 1.07 1.03 1.06 1.04 1.06 1.04 1.06 1.04 1.06 1.05 1.07 1.05 1.08 1.07 1.09 1.08 1.10 MAPA (1) + DMEA (2) 1.00 1.03 1.01 1.03 1.01 1.04 1.01 1.03 1.02 1.04 1.03 1.06 1.03 1.06 1.04 1.06 1.06 1.08 1.06 1.08 1.08 1.10
slowly. The greater α values growth at low MAPA concentration is connected with the H-bonds network existing in water. Figure 4 also indicates that temperature and MAPA concentration influence α values identically. For the binary mixture of
333.15
343.15
353.15
363.15
0.52 0.54 0.57 0.63 0.69 0.76 0.81 0.90 0.96 1.00 1.03 1.04 1.06 1.08 1.09 1.11 1.12
0.59 0.60 0.63 0.69 0.74 0.80 0.85 0.93 0.99 1.03 1.06 1.07 1.09 1.10 1.12 1.13 1.15
0.64 0.66 0.69 0.74 0.79 0.84 0.88 0.97 1.02 1.07 1.09 1.11 1.12 1.13 1.15 1.16 1.17
0.68 0.71 0.74 0.79 0.83 0.88 0.92 1.00 1.06 1.10 1.12 1.14 1.15 1.16 1.17 1.18 1.20
0.76 0.79 0.81 0.83 0.86 0.90 0.93 0.97 1.01 1.06 1.12
0.77 0.80 0.82 0.85 0.88 0.91 0.95 0.99 1.03 1.08 1.15
0.79 0.82 0.84 0.87 0.90 0.93 0.97 1.01 1.05 1.11 1.17
0.80 0.83 0.85 0.88 0.92 0.95 0.99 1.04 1.08 1.13 1.20
1.13 1.11 1.10 1.08 1.09 1.09 1.09 1.09 1.10 1.11 1.12
1.16 1.14 1.12 1.11 1.11 1.11 1.11 1.12 1.12 1.13 1.15
1.18 1.16 1.15 1.14 1.14 1.14 1.14 1.14 1.15 1.16 1.17
1.21 1.19 1.18 1.17 1.17 1.17 1.16 1.17 1.17 1.18 1.20
1.06 1.06 1.07 1.06 1.07 1.08 1.08 1.09 1.10 1.11 1.12
1.10 1.10 1.10 1.09 1.10 1.11 1.11 1.11 1.13 1.13 1.15
1.13 1.13 1.13 1.12 1.13 1.14 1.14 1.14 1.16 1.16 1.17
1.17 1.17 1.17 1.16 1.16 1.17 1.17 1.17 1.18 1.18 1.20
MAPA + MDEA, MAPA + DMEA, and MAPA + DEEA, the dependences of thermal expansitivies on MAPA concentration are shown in Figure 5. It can be seen that the composition of MAPA have no obvious influence on α values for the mixture of 3437
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Notes
The authors declare no competing financial interest. Funding
The authors are grateful to acknowledge financial support for the work by National Natural Science Foundation of China (Grant No. 51006083) and the Fundamental Research Funds for the Central Universities.
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Figure 4. Thermal expansivities, α, as a function of MAPA mole fraction at atmospheric pressure and different temperatures: ■, 293.15 K; ●, 313.15 K; ▲, 333.15 K; ▼, 353.15 K.
Figure 5. Thermal expansivities, α, for the binary mixtures as a function of MAPA mole fraction at atmospheric pressure and at 333.15 K: ■, MDEA; ●, DEEA; ▲, DMEA.
MAPA + DMEA, and MAPA + DEEA. This may be contributed to the one −OH group of DEEA and DMEA. For the MAPA + MDEA system, α values are increasing as the MAPA concentration growth.
4. CONCLUSION New experimental results for densities of binary mixtures of MAPA + H2O, MAPA + MDEA, MAPA + DMEA, and MAPA + DEEA were presented at temperatures (283.15 to 363.15) K and at atmospheric pressure in the whole composition range. Excess volumetric properties of the binary systems were then derived using the Redlich−Kister equation. The excess molar volumes VE for all of the investigated mixtures are negative, and the values of VE follow the order H2O > MDEA > DMEA > DEEA. The deduced partial molar volumes at infinite dilution are smaller than the corresponding molar volumes of pure components.
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REFERENCES
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