aminoethylethanolamine mixtures: Experimental measurements and thermodynamic modeling

aminoethylethanolamine mixtures: Experimental measurements and thermodynamic modeling

Accepted Manuscript Thermodynamic properties and CO2 solubility of monoethanolamine + diethylenetriamine/aminoethylethanolamine mixtures: Experimental...

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Accepted Manuscript Thermodynamic properties and CO2 solubility of monoethanolamine + diethylenetriamine/aminoethylethanolamine mixtures: Experimental measurements and thermodynamic modeling Mehrdad Moosavi, Caleb J. Sisco, Abbas Ali Rostami, Francisco M. Vargas PII:

S0378-3812(17)30250-9

DOI:

10.1016/j.fluid.2017.06.018

Reference:

FLUID 11513

To appear in:

Fluid Phase Equilibria

Received Date: 27 February 2017 Revised Date:

18 June 2017

Accepted Date: 19 June 2017

Please cite this article as: M. Moosavi, C.J. Sisco, A.A. Rostami, F.M. Vargas, Thermodynamic properties and CO2 solubility of monoethanolamine + diethylenetriamine/aminoethylethanolamine mixtures: Experimental measurements and thermodynamic modeling, Fluid Phase Equilibria (2017), doi: 10.1016/j.fluid.2017.06.018. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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Table of Contents Graphic

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“For Table of Contents Only”

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Thermodynamic Properties and CO2 Solubility of Monoethanolamine +

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Diethylenetriamine/Aminoethylethanolamine Mixtures: Experimental Measurements and

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Thermodynamic Modeling

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Mehrdad Moosavi1,2, Caleb J. Sisco2, Abbas Ali Rostami1, Francisco M. Vargas2*

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Faculty of Chemistry, University of Mazandaran, P.O. Box 453, Babolsar, Mazandaran, Iran

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Department of Chemical and Biomolecular Engineering, Rice University, Houston, Texas

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77005, United States

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Abstract

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The densities, viscosities, and refractive indices of monoethanolamine + diethylenetriamine /

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aminoethylethanolamine binary liquid mixtures were measured at atmospheric pressure and

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temperatures of 298.15, 303.15 and 308.15 K across the complete composition range. From the

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experimental data, several thermodynamic properties – including the excess volume, partial

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molar volume, partial molar volume at infinite dilution, excess Gibbs free energy of flow

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activation and excess refractive index – were calculated. Excess molar volume and excess

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refractive index data were correlated to the Redlich-Kister equation, and these properties were

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used to analyze molecular interactions in the binary mixtures. These volumetric properties were

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then predicted using the associating version of the PC-SAFT equation of state to test its

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applicability for amine systems, for which PC-SAFT showed promising results. Finally,

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viscosities were correlated using various models, including Arrhenius-like and McAllister.

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Keywords: Ethanolamine, Thermodynamic and Transport properties, PC-SAFT, CO2 solubility, Thermal expansion, Refractive index, Viscosity

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*

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E-mail: [email protected]

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Corresponding author: Tel: +1 (713) 348-2384

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1. Introduction

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Concerns over the role of greenhouse gases in climate change have motivated the development

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of technologies to reduce and capture these gases. Particular attention has turned to carbon

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dioxide (CO2), a greenhouse gas whose concentration in earth’s atmosphere has steadily

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increased since the Industrial Revolution, largely due to its production in industrial combustion

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reactions [1]. Among the various processes for CO2 removal from effluent process streams,

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embedding of amine scrubbing units has gained considerable popularity [2,3]. The most

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commonly used amine for CO2 capture is monoethanolamine because of its low price and fast

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reaction rate. However, low absorption capacity, high energy requirement for regeneration, and

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corrosion problems of monoethanolamine are among the main reasons for investigating other

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amines and amine mixtures [4-7].

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Both primary and secondary amines have been reported to have high reaction rates, absorption

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capacities and heats of reaction [8-10], whereas tertiary amines have lower heats of reaction and

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their absorption rates are somewhat limited [9-12]. Furthermore, primary and secondary amines

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capture significantly less CO2 per mole of amine than tertiary amines due to the formation of

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carbamate species that require two moles of amine per mole of CO2 captured [9,10]. The

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reactivity for CO2 in amines is in the order of primary > secondary > tertiary [13].

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To properly design the processes and equipment for CO2 absorption, a thorough understanding of

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the physicochemical properties of candidate solvent blends that determine reaction kinetics and

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transport properties is crucial. These solvents are often multi-component and strongly non-ideal,

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which makes the prediction of their properties challenging without extensive experimental data.

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Studies on phase behavior and viscosity are necessary for the determination of heat and mass

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transfer properties along with the calculation of the power and process requirements for unit

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operations. Many researchers have reported on the thermodynamic and transport properties of

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amine and amine-containing mixtures [14-31], but studies on amine mixtures like

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monoethanolamine + diethylenetriamine / aminoethylethanolamine are rare.

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In this work, densities, viscosities, and refractive indices of monoethanolamine (MEA) +

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diethylenetriamine (DETA) / aminoethylethanolamine (AEEA) binary mixtures were measured

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at atmospheric pressure and temperatures of 298.15, 303.15 and 308.15 K over the complete

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composition range. Various volumetric properties – including excess molar volume, partial

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molar volume and partial molar volume at infinite dilution – were obtained from density

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measurements. Excess molar volumes and excess refractive indices were correlated by the

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Redlich-Kister model, viscometric properties were correlated by several models, including the

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Arrhenius-like [32], Litovitz [33], Andrade [34] and McAllister [35] models, and refractive

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indices were predicted with different mixing rules [36,37] such as the Arago-Biot, Gladstone-

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Dale, Newton, Eyring–John, Edwards, Lorentz–Lorenz, Weiners, Eykman, Hellers, and Oster.

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Excess refractive indices were then used to analyze optical properties of the mixtures. Finally,

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the PC-SAFT equation of state was applied to predict densities, excess volumes, thermal

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expansion coefficients and CO2 solubility of the binary amine mixtures at various temperatures

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and compositions.

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2. Methodology

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2.1. Experimental

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2.1.1. Chemicals

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MEA and AEEA were purchased from Sigma-Aldrich. DETA was prepared from Merck. The

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purity of these chemicals was higher than 98% and their water content was around 0.2%. All

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chemicals were used without further purification. The water content of the chemicals was

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measured with a Kyoto Karl Fischer Moisture Titrator MKS-210 instrument. Table 1 shows the

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detailed specifications of the chemicals used.

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Table 1. Specifications of the chemicals used. Compound

CAS number

Supplier

Purity (supplier) (Mass fraction)

141-43-5

Sigma-Aldrich

≥98%

Diethylenetriamine

111-40-0

Merck

≥98% (GC)

Aminoethylethanolamine

111-41-1

Sigma-Aldrich

99%

Water content (supplier)

Water content (K.F.)a

(Mass fraction)

(Mass fraction)

<0.002%

0.06%

-

0.07%

-

0.08%

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Monoethanolamine

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a

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2.1.2. Experimental Procedures

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All binary solutions were prepared by mass using a single pan Mettler Toledo AG204 balance

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with a standard uncertainty of ± 0.1 mg. Liquid density measurements were performed using an

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Anton Paar oscillation U-tube densitometer (model: DMA 500) with a standard uncertainty of ±

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g.cm-3 and temperature standard uncertainty of 0.1 K calibrated at 293.15 K with ambient

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Water content determined by Karl Fischer method.

air and pure water.

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Dynamic viscosities were obtained using an Anton Paar Viscometer Lovis 2000 M rolling-ball

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automated viscometer with standard uncertainty in temperature of 0.02 K. Different capillaries

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with different diameters (1.59, 1.8, and 2.5 mm) with a percentage relative uncertainty 1 % were

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selected to allow measurement of viscosities from 0.7 to 1700 mPa.s. The calibration was

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completed using pure water and standard references prepared from CANNON including the S3,

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N7.5, N26, N100 and N415 standard oils with viscosities of 4, 12, 46, 230 and 990 mPa.s,

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respectively, at T = 298.15 K.

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Refractive index measurements were performed using an Abbe-2WAJ Refractometer coupled

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with a transparent thermostat water bath (Julabo F34 - Germany), which allows temperature

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stabilization with an uncertainty of 0.01 K. The standard uncertainty of the refractive index

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measurements was estimated to be less than ± 0.001 units.

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2.2 Theory

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2.2.1 Volumetric Properties

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To quantify the effect of temperature and composition on the interactions between amine

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mixtures using volumetric properties, the excess molar volumes of the mixtures

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determined from density measurements:

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where

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results can then be fit by a Redlich–Kister-type polynomial [38]:

are the pure component density and molecular weight, respectively. These

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are

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where

is a temperature-dependent adjustable parameter. The number of

parameters

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necessary for acceptable fitting depends on the molecular complexity of the solution, the number

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of data points available, and the quality of the measured data. Mixtures in which at least four

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parameters are required for an adequate fitting are categorized as highly complex systems. Partial

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molar volumes

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is known. Partial molar volumes for components in a binary are given as:

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can then be calculated once the dependence of excess volume on composition

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where

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respectively. In the limit of infinite dilution, solute-solute interactions disappear, so partial molar

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volumes at infinite dilution can provide information about solute-solvent interactions,

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independent of composition effects. By the Redlich-Kister equation, partial molar volumes at

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infinite dilution for components in a binary mixture are calculated by:

,

and

are partial molar volumes and molar volumes of components 1 and 2,

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are again the Redlich-Kister coefficients.

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Alternatively, volumetric properties of mixtures can be predicted by equations of state, which

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become especially useful when experimental data are unavailable. The most commonly used

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equations of state for fluid-phase modeling are the cubic-type first developed by van der Waals

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[39]. Unfortunately, the cubics are capable of predicting density to an acceptable degree of

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accuracy only for nonpolar fluids with low molecular weights. Thus, for this work, the PC-SAFT

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equation of state was chosen to capture the strong intermolecular forces that dominate in liquid

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mixtures containing alcohols and amines.

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PC-SAFT has gained wide industrial acceptance due to its robust performance in predicting the

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phase behavior of strongly associating fluid mixtures. Various thermodynamic properties – such

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as density, isothermal compressibility, and saturation properties – can be calculated as

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derivatives of the residual Helmholtz function, which is expressed in PC-SAFT as a hard chain

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reference fluid (hc) with contributions from relatively weak London dispersion forces (disp) and

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strong associating forces due to permanent dipoles (assoc):

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129 The hard chain and dispersion contributions to the Helmholtz energy are described by Gross and

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Sadowski [40,41] and the association contribution by Chapman [42]. Five parameters, including

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the number of segments

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segments , the association energy between associating sites

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association

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for non-associating components in PC-SAFT. These parameters are fit so as to minimize the

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deviation between experimental values of saturation pressure and saturated liquid densities.

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2.2.2 Viscometric Properties

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For liquid mixtures, viscosity is largely dependent on temperature and composition while

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pressure dependence is usually negligible. Based on these dependencies, several equations have

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been proposed to estimate the viscosity of mixtures. Here, the Arrhenius-like [32], Litovitz [33],

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Andrade [34] and McAllister equations [35] were used. The Arrhenius-like equation can be

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expressed as:

, segment diameter , the energy of dispersion interactions between and the volume of ,

and

are required

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, are required for each associating component while only

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where

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of flow, and

is equal to viscosity in the high-temperature limit (T→ ∞), is the gas constant. The Litovitz equation is given as:

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and Andrade’s equation is: 7

is the activation energy

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148 ,

and

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equation is expressed as:

are adjustable parameters. The two-parameter McAlister

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where

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151 152

where ,

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and 2, and adjustable parameters, respectively.

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Another flow property of interest can be calculated based on Eyring’s absolute rate theory [43].

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According to this model, fluid motion is assumed to take place by an individual molecule in a

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plane (or layer) occasionally acquiring the activation energy necessary to slip over the potential

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barrier (arising from squeezing against its neighbors) to the next equilibrium position in the same

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plane. This requires energy which can either be assumed to activate the flow unit or to produce a

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hole of requisite size for particle translation to occur. The formation of the hole, or of this

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intermediate activated state, then becomes the rate determining process which can be treated by

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the theory of rate processes. From the Gibbs free energy of activation, the related excess

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parameters can be calculated as:

and

are kinematic viscosities of the binary mixture, pure components 1

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The magnitude of

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molecule must achieve for it to be activated for flow. It is indirectly a measure of the strength of

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interactions between the molecules in solution.

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2.2.3 Optical Properties

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The refractive index is defined as the ratio of the speed of light through a vacuum to the speed of

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light through a material of interest. These values convey information on the molecular

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arrangement in a material, as light is bent due to interactions with molecules comprising the

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material. It is then expected that refractive index results agree with measured densities. The

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refractive indices measured in this paper were correlated using different mixing rules [36,37]

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including Arago-Biot, Gladstone–Dale, Newton, Eyring–John, Edwards, Lorentz–Lorenz,

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Weiners, Eykman, Hellers, and Oster semi-empirical models. These models can only be applied

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if there are no chemical reactions in the mixture and if there are no changes in volume during

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mixing. The excess refractive index

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al. [44]:

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can also be calculated based on the definition of Reis et

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and

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respectively, and

are volume fraction and refractive index of components 1 and 2,

is the refractive index of the mixture. Volume fraction is calculated by:

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can be viewed as an energy barrier over the ground state energy that a

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3. Results and Discussion

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The densities , dynamic viscosities , and refractive indices

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experiment are compared with literature values reported in the NIST data archive [45] and shown 9

of pure amines measured from

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in Table 2. The relative standard uncertainties for measured densities, refractive indices and

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viscosities are 0.002 g.cm-3, 0.001 and 0.1 mPa.s, respectively, indicating good agreement

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between the experimental values reported in this paper and those found in the literature.

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The densities, viscosities, and refractive indices for MEA + DETA/AEEA binary mixtures at all

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studied temperatures are summarized in Tables 3 and 4. Partial molar volumes were calculated

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by fitting a polynomial to density as a function of composition and differentiating. Thermal

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expansion coefficients at 303.15 K were calculated by applying the central difference method to

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densities at 298.15 K and 308.15 K to obtain the derivative of density with respect to temperature

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at 303.15 K.

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Table 2. Densities , viscosities , and refractive indices

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literature values for T = (298.15, 303.15 and 308.15) K and P = 0.1 MPa.

1.0124 303.15 1.0084 1.0045

298.15 303.15

0.9458 0.9421

1.0120 1.0119 1.0121 1.0081 1.0080 1.0084 1.0040 1.0040

[20] [21] [15] [20] [21] [15] [20] [21]

0.9455 0.9317 0.9423 0.9370

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308.15

Ref

308.15

0.9378

of pure liquids with corresponding

Exp Lit Ref Monoethanolamine (MEA) 18.89 [15] 18.72 18.88 [15] 18.74 [15] 14.88 [15] 15.15 15.10 [22] 14.71 [24] 11.96 11.82 [24]

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Lit

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Exp

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[26] [26] [27] [26]

Diethylenetriamine (DETA) 5.63 5.627 [28] 4.50 4.512 [26] 4.804 [18] 3.85 3.830 [28]

Exp

Lit

Ref

1.4535

1.4540 1.4543

[22] [23]

1.4524 1.4527 1.4488

[22] [23] [25]

1.4519 1.4505

1.4822 1.4808 1.4793

Aminoethylethanolamine (AEEA) 1.0258 1.0252 [31] 98.62 98.60 [26] 1.4843 1.4845 [26] 298.15 1.0213 1.0215 [31] 70.57 70.50 [26] 1.4527 1.4826 [26] 303.15 1.0163 53.11 1.4811 308.15 Standard uncertainties are = 0.01 K, = 10 kPa, = 0.001 g.cm-3 and = 0.001; percentage relative standard uncertainty is = 10%.

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Table 3. Densities , viscosities , refractive indices

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expansion coefficient

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MPa.

,

partial molar volumes

, and thermal

of MEA (1) + DETA (2) for T = (298.15 to 308.15) K and P = 0.1

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5.63 8.28 10.37 12.15 13.87 15.47 16.82 18.22 19.23 19.31 18.72

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0.9458 0.9565 0.9646 0.9726 0.9794 0.9863 0.9927 0.9987 1.0051 1.0089 1.0124

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T = 298.15 K 55.642 109.082 0.0000 58.554 108.886 0.0989 59.173 108.711 0.2021 59.501 108.523 0.3013 59.722 108.328 0.4007 59.869 108.120 0.4984 59.958 107.916 0.6007 60.063 107.632 0.7027 60.176 106.958 0.8002 60.270 106.064 0.8987 60.331 104.075 1.0000 T = 303.15 K 0.0000 0.9421 4.50 55.0211 109.510 8.4917 0.0000 0.1619 0.9531 6.59 58.812 109.265 7.7641 0.0989 0.2973 0.9611 8.33 59.421 109.093 7.8036 0.2021 0.4258 0.9690 9.76 59.711 108.934 7.5335 0.3013 0.5307 0.9759 11.18 59.915 108.740 7.2753 0.4007 0.6308 0.9828 12.48 60.059 108.545 7.2243 0.4984 0.7174 0.9892 13.60 60.144 108.365 7.1775 0.6007 0.7980 0.9955 14.73 60.235 108.064 6.7303 0.7027 0.8790 1.0017 15.49 60.384 107.295 6.5888 0.8002 0.9336 1.0056 15.49 60.486 106.156 6.4638 0.8987 1.0000 1.0084 15.15 60.571 103.563 7.8342 1.0000 T = 308.15 K 0.0000 0.9378 3.85 54.085 110.012 0.0000 0.1619 0.9491 5.38 59.130 109.712 0.0989 0.2973 0.9571 6.68 59.548 109.600 0.2021 0.4258 0.9653 7.80 59.816 109.443 0.3013 0.5307 0.9723 8.89 60.104 109.180 0.4007 0.6308 0.9792 9.99 60.283 108.939 0.4984 0.7174 0.9856 10.89 60.341 108.817 0.6007 0.7980 0.9920 11.84 60.399 108.637 0.7027 0.8790 0.9985 12.42 60.549 107.848 0.8002 0.9336 1.0024 12.34 60.686 106.394 0.8987 1.0000 1.0045 11.90 60.806 102.665 1.0000 -3 Standard uncertainties are = 0.01 K, = 10 kPa, = 0.0002, = 0.001 g.cm and percentage relative standard uncertainties are = 10%, = 0.1% and = 5×10-4%. 0.0000 0.1619 0.2973 0.4258 0.5307 0.6308 0.7174 0.7980 0.8790 0.9336 1.0000

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1.4822 1.4815 1.4806 1.4794 1.4778 1.4758 1.4731 1.4696 1.4657 1.4608 1.4535 1.4808 1.4802 1.4791 1.4778 1.4764 1.4743 1.4717 1.4683 1.4643 1.4591 1.4519

1.4793 1.4791 1.4778 1.4765 1.4752 1.4729 1.4703 1.4670 1.4631 1.4577 1.4505 = 0.001;

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Table 4. Densities , viscosities , refractive indices

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expansion coefficient

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MPa.

,

partial molar volumes

59.399 59.757 59.833 59.912 60.023 60.101 60.149 60.239 60.269 60.315 60.331

0.0000 0.1005 0.1993 0.2990 0.4047 0.5033 0.5985 0.6981 0.7985 0.8996 1.0000

1.4843 1.4824 1.4799 1.4774 1.4742 1.4714 1.4683 1.4647 1.4611 1.4573 1.4535

0.0000 0.1005 0.1993 0.2990 0.4047 0.5033 0.5985 0.6981 0.7985 0.8996 1.0000

1.4827 1.4810 1.4785 1.4760 1.4728 1.4700 1.4668 1.4633 1.4598 1.4559 1.4519

0.0000 0.1005 0.1993 0.2990 0.4047 0.5033 0.5985 0.6981 0.7985 0.8996 1.0000 = 0.001 g.cm-3 and = 5×10-4%.

1.4811 1.4796 1.4771 1.4745 1.4715 1.4685 1.4652 1.4620 1.4585 1.4545 1.4505 = 0.001;

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98.62 95.09 90.58 78.29 64.72 53.12 44.75 27.93 22.36 17.18 18.72

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1.0258 1.0257 1.0252 1.0244 1.0234 1.0225 1.0217 1.0194 1.0182 1.0152 1.0124

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of MEA (1) + AEEA (2) for T = (298.15 to 308.15) K and P = 0.1

T = 298.15 K 101.530 101.515 101.498 101.458 101.347 101.233 101.139 100.889 100.744 100.328 99.8699 T = 303.15 K 0.0000 1.0213 70.57 59.264 101.977 0.1072 1.0214 69.25 59.972 101.947 0.2634 1.0209 67.59 60.064 101.933 0.4233 1.0202 59.50 60.124 101.894 0.5481 1.0193 48.92 60.255 101.775 0.6305 1.0184 39.84 60.334 101.658 0.6851 1.0176 32.81 60.375 101.571 0.7988 1.0155 20.04 60.452 101.351 0.8459 1.0143 15.94 60.487 101.207 0.9377 1.0114 12.82 60.546 100.645 1.0000 1.0084 15.15 60.571 99.863 T = 308.15 K 0.0000 1.0163 53.11 59.327 102.479 0.1072 1.0166 52.77 60.145 102.441 0.2634 1.0162 52.68 60.306 102.418 0.4233 1.0157 46.92 60.348 102.384 0.5481 1.0149 38.49 60.466 102.270 0.6305 1.0141 31.01 60.549 102.157 0.6851 1.0134 25.15 60.600 102.060 0.7988 1.0114 14.71 60.689 101.791 0.8459 1.0103 11.31 60.723 101.627 0.9377 1.0075 9.55 60.777 101.084 1.0000 1.0045 11.96 60.806 100.416 Standard uncertainties are = 0.01 K, = 10 kPa, = 0.0002, percentage relative standard uncertainties is = 10%, = 0.1% and 0.0000 0.1072 0.2634 0.4233 0.5481 0.6305 0.6851 0.7988 0.8459 0.9377 1.0000

, and thermal

9.3019 8.9093 8.8158 8.5273 8.3881 8.2482 8.1560 7.8779 7.7886 7.6132 7.8342

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3.1. Volumetric Properties

205

The variation of

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Kister correlations, are shown in Figure 1, and the corresponding fitting parameters

207

Redlich-Kister equation, along with their standard deviations, are given in Table 5.

against MEA composition for various isotherms, along with the Redlich-

12

of the

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208 Fig. 1. Excess molar volume (

) as a function of MEA mole fraction ( ) for

210

MEA (1) + AEEA/DETA (2) for T = (298.15 to 308.15) K. Dashed lines represent the

211

corresponding Redlich–Kister correlations.

212

Table 5. Coefficients

213

(

M AN U

209

) of the Redlich-Kister equation for excess molar volume

298.15 K 303.15 K 308.15 K

-1.354 -1.963 -3.649 -0.296 -0.708 -0.924

298.15 K 303.15 K 308.15 K 298.15 K 303.15 K 308.15 K

-0.206 -0.185 -0.274

MEA+DETA

-0.762 -0.938 -0.338 -0.028 0.032 0.051

0.011 0.007 0.004

0.003 0.004 0.007

0.001 0.002 0.003

0.002 0.003 0.002

-0.003 -0.002 -0.002

0.001 -0.001 0.001

AC C

0.048 -0.009 -0.047

-2.730 -2.846 -3.046

0.0045 0.0040 0.0049

-0.970 -1.034 -1.087

0.0017 0.0021 0.0016

0.032 0.031 0.031

0.00006 0.00006 0.00007

0.011 0.010 0.010

0.00004 0.00008 0.00003

MEA+AEEA

0.080 0.038 0.093

EP

298.15 K 303.15 K 308.15 K

along with their standard deviations .

TE D

) and excess refractive index

-0.445 -0.442 -0.458

MEA+DETA 0.011 0.011 0.010

MEA+AEEA -0.001 -0.001 -0.001

214

Negative values of

for binary mixtures are often attributed to strong chemical or specific

215

interactions between the components present in the mixtures. These effects can also be attributed

216

in part to structural contributions arising from the geometrical fitting of one component into the 13

ACCEPTED MANUSCRIPT

other due to differences in the molar volumes and free volume between unlike molecules

218

(packing effect). The presence and position of NH, amine and hydroxyl groups in both amine

219

mixtures – and the strong association forces from hydrogen-bonding that accompany – produce

220

the highly negative excess molar volumes. Excess molar volumes for MEA + DETA are more

221

negative than those of MEA + AEEA, indicating relatively stronger interactions in MEA +

222

DETA.

223

The variation of partial molar volumes

224

DETA/AEEA are tabulated in Tables 3 and 4 and plotted in Figure 2. Partial molar volumes of

225

MEA in both mixtures increase nonlinearly with increasing MEA composition, while the inverse

226

behavior is seen for the partial molar volumes of DETA and AEEA.

227

The calculated values of

228

298.15, 303.15 and 308.15 K are listed in Table 6. The partial molar volumes of species at

229

infinite dilution were smaller than the corresponding molar volumes of pure components. These

230

values show the strong intermolecular interactions between unlike molecules and the contraction

231

in volume upon mixing. The excess partial molar volumes at infinite dilution are negative and

232

have

SC

M AN U

from Redlich-Kister for all studied binary mixtures at

TE D sign

EP

same

with MEA mole fraction for binary mixtures of MEA +

as

AC C

the

and

RI PT

217

14

the

excess

molar

volumes.

SC

RI PT

ACCEPTED MANUSCRIPT

TE D

M AN U

233

234

Fig. 2. Partial molar volume (

) as a function of MEA mole fraction ( ) for T =

236

(298.15 to 308.15) K. A: MEA and B: DETA in a binary mixture of MEA (1) + DETA (2). C:

237

MEA and D: AEEA in a binary mixture of MEA (1) + AEEA (2).

238

Table 6. Partial molar volumes at infinite dilution (

239

components (

AC C

EP

235

T/K 298.15 303.15 308.15

) and molar volume of pure

) for T = (298.15 to 308.15) K.

MEA (Pure)

MEA+DETA

MEA+AEEA

DETA (Pure)

MEA+DETA

AEEA (Pure)

MEA+AEEA

60.331 60.571 60.806

55.325 54.628 53.450

58.670 58.457 58.481

109.082 109.510 110.024

104.392 103.956 103.312

101.530 101.977 102.479

100.598 100.671 100.883

Standard uncertainties are

= 0.01 K,

= 10 kPa,

15

= 0.0002 and

= 0.005.

ACCEPTED MANUSCRIPT

In cases where experimental data have not been collected, as is required to do fitting for the

241

Redlich-Kister equation, the most reliable method for generating volumetric property predictions

242

is by an equation of state. The PC-SAFT equation of state is used in this work, and the

243

parameters for the studied components are listed in Table 7. These values were fit to density and

244

vapor pressure correlations reported in the DIPPR database [46]. CO2 was treated as non-

245

associating in this work and its PC-SAFT parameters were reported by Gross and Sadowski [40].

246

PC-SAFT predictions for density and excess molar volume for both binary mixtures are shown in

247

Figures 3 and 4, respectively, and compared to experimental measurements. Values of

248

fit to minimize deviations between the excess molar volumes predicted and those measured.

249

Table 7. PC-SAFT parameters of studied pure components.

250

M AN U

SC

RI PT

240

.

and

Associating

(-)

3.5892

104.15

5.0467

45.01

2.0729

169.00

0.178696

TE D

103.16

2.6870

1982.5

4C

2.52

0.75

273-500

3.4692

237.15

0.535593

1952.9

2B

1.19

0.86

273-500

3.0673

225.94

0.051951

2277.2

4C

0.61

0.50

273-500

2.7852

169.21

0

0

-

2.78

2.73

216-304

EP

251

4.1833

range

Scheme

(-)

AC C

CO2

61.08

were

16

SC

RI PT

ACCEPTED MANUSCRIPT

M AN U

252 253

Fig. 3. Density (

254

DETA/AEEA (2) compared with calculated results from PC-SAFT for T = 298.15 K.

AC C

255

EP

TE D

) as a function of MEA mole fraction ( ) for MEA (1) +

256

Fig. 4. Excess molar volume (

) as a function of MEA mole fraction ( ) for T =

257

(298.15 to 308.15) K. A: MEA + DETA, B: MEA + AEEA compared with calculated results

258

from PC-SAFT.

259

Thermal expansion coefficients, given as:

260 17

ACCEPTED MANUSCRIPT

were calculated for pure MEA, DETA and AEEA using the PC-SAFT model and compared with

262

correlated values from the literature [47,30,31]. These results are shown in Figure S1 in

263

Supporting Information. Thermal expansion coefficients for MEA + DETA/AEEA binaries as a

264

function of MEA mole fraction are shown in Figure 5.

265

The maximum AAD for density predictions with PC-SAFT were 0.36% and 0.25% for MEA +

266

DETA and MEA + AEEA, respectively. Good liquid density predictions should be expected, as

267

the PC-SAFT parameters were fit to match experimental saturation pressures and saturated liquid

268

densities. Excess volume showed maximum AAD of 15.61% and 6.73% for MEA + DETA and

269

MEA + AEEA, respectively. For the thermal expansion coefficients calculated at 303.15 K and

270

0.1 MPa, AAD values were 13.62% for MEA + DETA and 9.05% for MEA + AEEA. Pure

271

component thermal expansion coefficients showed AAD values of 10.71%, 5.50% and 9.87% for

272

MEA, DETA and AEEA, respectively.

273

Finally, predictions for CO2 solubility in MEA + DETA/AEEA at 298.15 K and 0.1 MPa are

274

reported in Figure 6. Solubility data for CO2 in MEA + DETA/AEEA have not been found in the

275

literature and there is only sparse data on CO2 solubility in amine mixtures. Various studies with

276

SAFT modeling of CO2 solubility in alkanes [48], polymers [49], ionic liquids [50], and aqueous

277

amines [51] have shown promising results. PC-SAFT predicts that CO2 solubility decreases with

278

increasing MEA composition in both binary mixtures, and CO2 is more soluble in MEA + DETA

279

than in MEA + AEEA.

AC C

EP

TE D

M AN U

SC

RI PT

261

18

SC

RI PT

ACCEPTED MANUSCRIPT

280 Fig. 5. Thermal expansion coefficient (

) as a function of MEA mole fraction ( ) for

282

MEA + DETA (red) and MEA + AEEA (blue) at T = 303.15 K compared with calculated results

283

from PC-SAFT.

TE D

M AN U

281

AC C

284

MEA + DETA

EP

MEA + AEEA

285

Fig. 6. PC-SAFT predicted CO2 solubility as a function of MEA mole fraction ( ) for MEA (1)

286

+ DETA/AEEA (2) for T = 298.15 K and P = 0.1 MPa.

287

3.2. Viscometric Properties

288

Dynamic viscosities for the studied amine mixtures are reported in Tables 3 and 4 and shown

289

graphically in Figure 7. Viscosities were shown to decrease with increasing temperature for both

290

mixtures. The composition dependence of viscosity was more complicated; the viscosities of 19

ACCEPTED MANUSCRIPT

MEA + DETA mixtures increased up to a mole fraction of about 0.9 MEA and then shifted

292

down, whereas, for MEA + AEEA solutions, viscosities decreased up to a mole fraction of about

293

0.9 MEA and then shifted up.

294

In fluid systems at constant temperature, molecular weight and intermolecular forces are the two

295

main factors affecting viscosity. These two factors can often complement each other in their

296

effect on viscosity but may also compete in some scenarios. For example, both DETA and

297

AEEA have nearly identical molecular weights, but the viscosity of pure AEEA is twenty times

298

more than the viscosity of DETA. The discrepancy in viscosity can be attributed to stronger

299

interactions between AEEA molecules than between DETA molecules. Comparison between the

300

viscosity and density results of pure MEA and AEEA shows that interactions between molecules

301

in AEEA are stronger than in MEA.

302

AC C

EP

TE D

M AN U

SC

RI PT

291

303

Fig. 7. Dynamic viscosity (

) as a function of MEA mole fraction ( ) for T = 298.15 K

304

compared with various viscosity models. A: MEA + DETA, B: MEA + AEEA.

305

All calculated adjustable parameter values along with the corresponding standard deviations in

306

the viscosity models are listed in Table 8. Among the three-examined temperature-dependent

307

viscosity models, the Arrhenius-like model produced the lowest AAD%. The McAlister model

20

ACCEPTED MANUSCRIPT

predicted the viscosities of MEA + DETA/AEEA binary mixtures with absolute average

309

deviations less than 0.21% and 14.40%, respectively.

310

Table 8. Adjustable parameters of investigated viscosity models along with their AAD% for

311

MEA (1) + DETA/AEEA (2) binary mixtures.

Andrade

Arrhenius

Litovitz

0.107 -13.6 44.99 0.79 -1.70 1.38 0.57 1.56 245.8 -238 0.31

0.263 -12.2 41.40 0.78 -1.25 1.27 0.56 2.38 207.7 -241 0.15

MEA + DETA 0.425 0.530 -11.1 -11.0 33.85 33.96 0.27 0.50 -2.20 -2.08 1.04 1.04 0.43 0.65 0.002 0.001 2274 33.51 -36.2 62.3 4.89 7.71 MEA + AEEA 0.423 0.548 -11.4 -11.8 39.11 39.70 0.64 0.69 -1.07 -1.35 1.20 1.22 0.44 0.51 1.76 1.73 242.7 215.7 -234 -238 0.07 0.10 McAllister

0.630 -10.7 33.39 0.33 -1.90 1.02 0.50 0.003 23.20 -21.9 5.27

0.717 -10.5 33.19 0.34 -1.78 1.02 0.52 0.004 23.25 -14.3 5.23

0.798 -10.3 32.87 0.27 -1.66 1.01 0.42 0.001 3132 11.63 3.96

0.879 -10.4 33.30 0.23 -1.67 1.02 0.40 0.003 2274 -39.1 3.93

0.933 -10.8 34.19 0.31 -1.78 1.05 0.48 0.005 2092 -40.2 5.03

1.000 -10.8 34.17 0.72 -1.81 1.05 0.86 0.002 3738 122.9 8.66

0.630 -12.6 41.11 0.61 -1.74 1.26 0.42 0.79 285.3 -230 0.18

0.685 -13.9 44.03 0.78 -2.32 1.35 0.56 0.81 238.3 -238 0.30

0.798 -16.4 48.95 0.28 -3.47 1.50 0.04 0.41 246.8 -239 0.89

0.845 -17.8 52.07 0.34 -4.12 1.59 0.60 0.01 888.9 -180 3.18

0.937 -15.2 44.84 0.25 -3.38 1.37 0.51 0.002 1623 -115 4.61

1.000 -10.8 34.17 0.72 -1.81 1.05 0.86 0.002 3738 122.9 8.66

SC

0.000 -14.4 47.29 0.88 -1.98 1.45 0.66 1.61 232.3 -241 0.11

EP

Andrade

0.297 -11.2 33.63 0.19 -2.33 1.03 0.33 0.003 1645 -94.6 2.24

M AN U

Litovitz

0.161 -11.1 32.95 0.37 -2.47 1.01 0.20 0.12 360.8 -211 0.24

TE D

Arrhenius

0.000 -10.0 29.06 1.32 -2.32 8.90 1.17 1.54 31.02 -274 0.22

RI PT

308

AC C

MEA + DETA

298.15 K 303.15 K 308.15 K

19.60 15.88 13.25

12.59 10.12 7.61

MEA + AEEA 2.08 1.88 1.98

36.38 22.43 14.94

152.3 134.5 122

9.62 11.93 14.40

312

The Gibbs free energy of flow activation, calculated from equation 10, is indirectly a measure of

313

the strength of interactions between the molecules in solution. Figure 8 shows the excess Gibbs

314

free energy of flow activation at 298.15, 303.15 and 308.15 K for binary mixtures of MEA +

315

DETA/AEEA. Excess Gibbs free energy of flow activation for MEA + DETA is positive for all

21

ACCEPTED MANUSCRIPT

temperatures and compositions with extrema around 0.5 mole fraction of MEA.

is negative

317

in the MEA rich region for MEA + AEEA binary mixture. Positive values of

show that

318

specific interactions between unlike molecules are dominant in the studied binary mixtures.

M AN U

SC

RI PT

316

319

Fig. 8. Excess Gibbs free energy of flow activation (

) as a function of MEA mole

321

fraction ( ) for T = (298.15 to 308.15) K. A: MEA + DETA, B: MEA + AEEA.

322

3.3. Optical Properties

323

The refractive indices of MEA + DETA/AEEA binary mixtures at temperatures of 298.15,

324

303.15 and 308.15 K are reported in Tables 3 and 4 and shown graphically in Figure S2 in

325

Supporting Information. At all temperatures, the refractive indices for both amine mixtures

326

decrease non-linearly with increasing MEA composition. The refractive index values for the pure

327

chemicals vary in the order of AEEA > DETA > MEA and decrease as temperature increases.

328

The refractive indices were correlated using various models, including Arago-Biot, Gladstone–

329

Dale, Newton, Eyring–John, Edwards, Lorentz–Lorenz, Weiners, Eykman, Hellers, and Oster

330

semi-empirical models. The absolute average deviations of these models are shown graphically

AC C

EP

TE D

320

22

ACCEPTED MANUSCRIPT

in Figure 9. All studied models can predict the refractive index values of MEA + DETA/AEEA

332

binary mixtures with maximum AAD of less than 0.8% and 0.3%, respectively. The deviations

333

of these models for MEA + DETA decrease with increasing temperature, while for MEA +

334

AEEA the opposite trend is seen.

M AN U

SC

RI PT

331

335

Fig. 9. Comparison between AAD% from experimental and calculated refractive indices for T =

337

298.15 K. (red) MEA + DETA, (blue) MEA + AEEA.

338

The excess refractive index

339

function of MEA mole fraction are shown in Figure 10. Excess refractive index values are

340

positive for both amine mixtures with a maximum at MEA mole fractions of 0.6 and 0.5 for

341

MEA + DETA and MEA + AEEA, respectively. Positive values of

342

values and vice versa, and both

343

Therefore, a more positive

344

light velocity in the medium, and a lower refractive index than the ideal solution.

TE D

336

AC C

EP

, calculated based on the definition of Reis et al. [44], as a

and

correspond to negative

shift to zero values with increasing temperature.

value is indicative of more free volume in the solution, higher

23

345

SC

RI PT

ACCEPTED MANUSCRIPT

Fig. 10. Excess refractive index (

) as a function of MEA mole fraction ( ) for MEA (1) +

347

DETA /AEEA (2) for T = (298.15 to 308.15) K.

348

4. Conclusions

349

Thermophysical properties of the monoethanolamine (MEA) + diethylenetriamine (DETA) /

350

aminoethylethanolamine (AEEA) binary mixtures – including densities, viscosities, and

351

refractive indices – were measured at atmospheric pressure for 298.15, 303.15 and 308.15 K.

352

Negative excess molar volumes and positive excess refractive indices were obtained that

353

indicated stronger interactions between unlike components in the mixtures than like components.

354

Excess parameter values of all studied systems shift toward zero when temperature increases,

355

showing that solutions approach ideality in the high-temperature limit.

356

The Redlich-Kister model satisfactorily correlated the values of

357

standard deviations of 0.0049 and 6 x 10-5, respectively, for MEA + DETA and 0.0021 and 8 x

358

10-5, respectively for MEA + AEEA.

359

Experimental viscosities were well correlated with Arrhenius-like, Litovitz, Andrade and

360

McAlister models, with maximum AAD% of 1.32, 1.17, 7.71 and 2.08, respectively, for MEA +

361

DETA and 0.88, 0.86, 8.66 and 14.40, respectively, for MEA + AEEA.

AC C

EP

TE D

M AN U

346

24

and

, yielding maximum

ACCEPTED MANUSCRIPT

Refractive indices were correlated satisfactorily using Lorentz-Lorenz, Eykman and Edwards

363

semi-empirical models with maximum AAD% equal to 0.2.

364

PC-SAFT predictions for density, excess molar volume, thermal expansion coefficient and CO2

365

solubility were presented. Density predictions for both binaries were excellent, while excess

366

molar volumes and thermal expansion coefficients showed more deviation. Excess volume

367

predictions showed maximum AAD% of 15.61 and 6.73 for MEA + DETA and MEA + AEEA,

368

respectively, and thermal expansion coefficients calculated at 303.15 K and 0.1 MPa showed

369

AAD% of 13.62 and 9.05 for MEA + DETA and MEA + AEEA, respectively.

370

Acknowledgment

371

The experimental support from University of Mazandaran is gratefully acknowledged.

AC C

EP

TE D

M AN U

SC

RI PT

362

25

ACCEPTED MANUSCRIPT

372

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373

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Highlights

Density, viscosity and refractive index of amines mixtures were measured



Different excess properties were calculated from the experimental measurements



PC-SAFT models were used to calculation of volumetric properties and CO2 solubility



Different models were used to reproduce the viscosities and refractive indices data

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