Vapor–liquid equilibria of N,N,N′,N′ tetramethylethylenediamine (TMEDA), tetramethylpropylenediamine (TMPDA) and their aqueous solutions

doi:10.1016/j.molliq.2014.11.012

Journal of Molecular Liquids

Volume 201, January 2015, Pages 83-89

https://doi.org/10.1016/j.molliq.2014.11.012 Get rights and content

Highlights

•
Experimental vapor pressures of pure TMEDA, TMPDA and their aqueous solutions are reported from 273 to 363 K
•
The two binary systems exhibit positive deviations in G^E values
•
The (TMEDA + water) system shows maximum azeotropic behavior over the whole temperature range
•
The (TMPDA + water) binary system shows maximum azeotropic behavior for T > 323 K
•
The NRTL and UNIQUAC models have been used.

Abstract

The vapor pressures of (N,N,N′,N′ tetramethylethylenediamine (TMEDA) + water), (tetramethylpropylenediamine (TMPDA) + water) binary mixtures, and of pure N,N,N′,N′ tetramethylethylenediamine and tetramethylpropylenediamine components were measured by means of a static device at temperatures between 273 and 363 K. The data were correlated with the Antoine equation. From these data excess Gibbs functions (G^E) were calculated for several constant temperatures and fitted to a three order Redlich–Kister equation using the Barker's method. The two binary systems show a positive azeotropic behavior. The TMEDA aqueous solution exhibits positive deviations in G^E for all investigated temperatures over the whole composition. The (TMPDA + water) system shows the same behavior except for T = 273.15 and 283.15 K where a sinusoidal shape is observed. Additionally, the NRTL and UNIQUAC models have been used for the correlation or prediction of the total pressure.

Introduction

Aqueous solutions of alkanolamines are widely employed in the industry for removal of acidic gases such as CO₂ and H₂S from natural gas and flue gas streams. In recent years the existing gas treating technology was getting increased attention due to its potential for carbon capture applications in the power generating industry [1].

Various amines including aliphatic diamines and polyamines, as well as their mixtures with ionic liquids are considered as promising candidates for CO₂ removal [2], [3]. Basic physical property information for this class of components is still under development among which vapor–liquid equilibria (VLE).

The present paper is part of a research program of VLE of aqueous mixtures of alkanolamines or amines [4], [5], [6]. The vapor–liquid equilibria of pure N,N,N′,N′ tetramethylethylenediamine (TMEDA), (tetramethylpropylenediamine (TMPDA) and their aqueous solutions were studied in the present work. The NRTL and UNIQUAC models were used to correlate the vapor pressures of pure and mixed liquids.

A survey of the literature shows that there is no data available on the open literature for the investigated binary systems.

Section snippets

Materials

The diamines were supplied by Aldrich Chem. (Milwaukee, WI, USA), Table 1. The mass fraction purity, tested by GLC, is better than 0.99. The water content in the amines (important in the case of pure amine study) was determined by the Karl Fischer method and it was less than 30 ppm. The aqueous mixtures were prepared by weighing. Deionized water was used (18 MΩ·cm) and the weighing balance uncertainty is ± 0.0004 g.

VLE measurements

The vapor pressure measurements for the pure components and aqueous solutions were

Results and discussion

The experimental vapor pressure data were fitted to the Antoine equation: ${log}_{10} P / Pa = A - \frac{B}{(C + T / K)} .$

The objective function Q was the sum of the squared relative deviations in pressure: $Q = \sum {(\frac{P_{calc} - P_{\exp}}{P_{\exp}})}^{2} .$

The overall mean relative deviation in pressure is: $\frac{δ P}{P} % = \frac{100}{N} \sum (\frac{P_{calc} - P_{\exp}}{P_{\exp}})$ where N is the total number of experimental values.

The explored temperature range, the coefficients A, B, and C of the Antoine equation and the overall mean relative deviation in pressure for the pure amines are listed in Table 1

Symbols

A, B, C

coefficients of Antoine equation

δP / P (%)

overall mean relative deviation in pressure of the Antoine equation

temperature

P_exp

pressure (experimental)

P_calc

pressure (calculated using Antoine equation)

x_i

mole fraction in the liquid phase of component “i”

y_i

mole fraction in the vapor phase of component “i”

γ₁

activity coefficient of components “i” in the liquid phase

G^E

excess Gibbs energy

G_i

Coefficients of the Redlich–Kister equation of component “i”

a₁₂, a₂₁, b₁₂, b₂₁

fitted parameters in the NRTL or

Acknowledgments

Z. B. gratefully acknowledges grant from the Algerian Ministry of High Education and Scientific Research (MESRS, Algeria).

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Vapor–liquid equilibria of N,N,N′,N′ tetramethylethylenediamine (TMEDA), tetramethylpropylenediamine (TMPDA) and their aqueous solutions

Highlights

Abstract

Introduction

Section snippets

Materials

VLE measurements

Results and discussion

Symbols

Acknowledgments

J. Chem. Thermodyn.

J. Chem. Thermodyn.

Atmos. Environ.

J. Fluid Phase Equilib.

J. Chem. Thermodyn.

Green Chem.

Ind. Eng. Chem. Res.