Density, Speed of Sound, Viscosity, and Surface Tension of

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Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Density, Speed of Sound, Viscosity, and Surface Tension of Hexamethylenetetramine Aqueous Solutions from T = (293.15 to 323.15) K Diego Gómez-Díaz,*,† José M. Navaza,† and Antonio Rumbo‡

J. Chem. Eng. Data Downloaded from pubs.acs.org by UNIV OF LOUISIANA AT LAFAYETTE on 09/27/18. For personal use only.

†

Departamento de Enxeñaría Química, ETSE, Universidade de Santiago de Compostela, Rúa Lope Gómez de Marzoa s/n, E-15786 Santiago de Compostela, Galicia ‡ Departamento de Química Orgánica,Facultade de Química, Universidade de Santiago de Compostela, Avenida das Ciencias s/n, E-15786 Santiago de Compostela, Galicia ABSTRACT: The present research work analyzes the behavior of aqueous solutions of hexamethylenetetramine, determining several physical properties such as density, speed of sound, viscosity, and surface tension. Besides the importance of these properties, they allow the type of interactions between solute and solvent molecules to be analyzed. The study consisted of the evaluation of the influence of amine concentration and temperature upon these properties. An increase in amine concentration causes an increase in density, viscosity, and speed of sound and a decrease in isentropic compressibility and surface tension. On the basis of experimental data of isentropic compressibility and surface tension the presence of temperature resistant structure has been determined.

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INTRODUCTION

The characterization of aqueous solutions of HMTA in relation with certain physical properties is interesting due to the high number of uses and applications of this compound. A low number of studies about certain properties have been carried out centered mainly in the solubility in some common solvents14 and the analysis of density and viscosity at low temperatures.15,16 The analysis of the influence of concentration and temperature upon several physical properties allows the type of interactions between solvent and solute, their influence upon transport properties, the aggregation processes, and the formation of rigid structures to be evaluated.

Hexamethylenetetramine (HMTA) is a very interesting molecule with chemical characteristics that allow its use in an important number of applications both from the point of view of research, fine chemical manufacturing, and chemical industrial processes. An important number of fine chemistry uses are related with the suitable characteristics to stabilize certain structures. This molecule is used in the formulation of layered double hydroxides to be used as catalysts.1 This role of stabilizer is based on the presence of very strong interactions (specifically hydrogen bonds). This type of behavior was employed in the synthesis of graphite oxide with a significant increase in the thermal stability.2 Another use of HMTA is the synthesis of phenolic gels to be used as precursors in the production of mesoporous carbons for electrodes for electric energy storage.3 Then HMTA can be employed as a multifunctional ligand due to the use of nitrogen atoms to form coordination complexes.4−7 The previously mentioned characteristics regarding strong interactions allow complexes to be prepared with metals; this molecule has increased its applications due to the simplicity of operation and the use of mild experimental/operation conditions and eco-friendly characteristics.8,9 At the industrial level this compound is involved in several processes such as an accelerant in vulcanization,10 in food preservatives,11 and in explosives12 because of its useful properties including high solubility in water and polar organic solvents.13 © XXXX American Chemical Society

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EXPERIMENTAL SECTION Materials. Table 1 shows data corresponding to the reagent used in the present work. HMTA has been employed without further purification. Distilled water has been used to prepare the amine aqueous solutions. Samples were prepared by mass using an analytical balance (Kern 770). Table 1. Sample Description Table

a

chemical name

CAS number

molecular weight

HMTAa

100-97-0

140.19 g·mol−1

source SigmaAldrich

initial mole fraction purity ≥0.99

Hexamethylenetetramine.

Received: June 14, 2018 Accepted: September 13, 2018

A

DOI: 10.1021/acs.jced.8b00492 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Methods. Density and Speed of Sound. The density (ρ) and speed of sound (c) of pure components and the mixtures of different compounds were measured with an Anton Paar DSA 5000 vibrating tube densimeter and sound analyzer. This equipment was calibrated with air and pure water. The transducer emits sound waves at a frequency of 3 MHz. The temperature range for all the properties determined in present work was 293.15−323.15 K. Viscosity. The kinematic viscosity (ν) was determined from the transit time of the liquid meniscus through capillary Ubbelohde viscosimeters supplied by Schott. Capillaries number 0c (K = 0.003164 mm2·s−2) and I (K = 0.01013 mm2·s−2) have been used connected to a Schott-Geräte AVS 350 Ubbelohde viscosimeter. Equation 1 was employed to calculate the viscosity from the transit time, ν = K · (t − θ )

(1)

Figure 1. Effect of HMTA concentration upon relative density ρ·ρo−1. White ○, data obtained from ref 17 at T = 298.15 K; black ●, data obtained from ref 15 at T = 301.88 K; ×, data obtained from ref 18 at T = 298.15 K; △, data obtained from ref 19 at T = 298.15 K; gray ●, this work, at T = 293.15 K.

where t is the efflux time; K is the characteristic constant of the capillary viscosimeter; and θ is a coefficient to correct end effects. Both parameters were obtained from the capillaries supplier (Schott). An electronic stopwatch with a standard uncertainty of 0.01 s was used to measure efflux times. The average value of five consecutive measurements was employed. The dynamic viscosity (η) was obtained from the product of the kinematic viscosity (ν) and the corresponding density (ρ) of the mixture, in terms of eq 2 for each mixture composition. η = ν·ρ (2) Surface Tension. The surface tension (σ) was determined by employing a Krüss K-11 tensiometer using the Wilhelmy plate method. The plate employed was a commercial platinum plate supplied by Krüss. The platinum plate was cleaned and flame-dried before each measurement. Each surface tension value reported came from an average of five measurements. The samples were thermostated in a closed stirring vessel before the surface tension measurements. The highest temperature used in this study was avoided for surface tension measures because evaporation processes could influence upon measure uncertainty.

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Figure 2. Influence of HMTA concentration upon relative viscosity η·ηo−1: white ○, data obtained from ref 17 at T = 293.15 K; black ●, data obtained from ref 15 at T = 301.88 K; gray ●, this work at T = 293.15 K. And speed of sound c: ×, data obtained from ref 18 at T = 293.15 K; +, data obtained from ref 18 at T = 303.15 K; △, this work at T = 293.15 K; ▲, this work at T = 303.15 K.

RESULTS AND DISCUSSION Figures 1 and 2 show comparisons between literature values for relative density and viscosity (relation between corresponding mixture and solvent values) with the values calculated in the present work on the basis of the experimental data of density and viscosity. Relative density and viscosity were employed to compare literature and experimental data. Literature values were determined at very specific temperatures and employing relative magnitudes. The comparison corresponding to density shows a suitable agreement with both literature papers analyzed.15,17−19 A monothonic increase in relative density is observed with HMTA concentration in the liquid phase. Table 2 shows the experimental data corresponding to the influence of HMTA molality (m) upon the different physical properties evaluated in present work (density, viscosity, speed of sound, and surface tension) in aqueous solutions at temperatures between 293.15 and 323.15 K. Regarding the influence of HMTA concentration upon density it shows a monotonic increase in the value of this property, but the influence of this variable decreases at large amine concentration. This behavior is similar for all the temperatures analyzed in the present work. The influence of

this variable (temperature) upon density shows a decrease in the value of this property with a linear behavior (with a slope average value of ∼4 × 10−4 g·cm−3·K−1). A comparison between experimental and literature data for relative viscosity has been also carried out using our experimental values and the same studies previously employed in the comparison of density.15,17 For this property, a suitable agreement between experimental and literature viscosity data is observed with low deviations. Experimental data included in Figure 2 indicate that an increase in HMTA concentration causes also an increase in viscosity value. Figure 3 shows a more complete analysis about the influence of concentration and temperature upon viscosity. The HMTA concentration causes a notable effect with an increase in viscosity value. Regarding the influence of temperature, a typical behavior was found with an Arrhenius type influence upon viscosity (solid lines correspond to the B



Article

Table 2. Density ρ, Speed of Sound c, Dynamic Viscosity η, and Surface Tension σ of HMTA (1) + Water (2) from T = (293.15 to 323.15) K at p = 105 Paa m1/ mol·kg−1 0.000 0.207 0.425 0.654 0.897 1.164 1.449 1.748 2.068 2.412 2.779 3.181 3.617 4.088 4.609 5.155 0.000 0.207 0.425 0.654 0.897 1.164 1.449 1.748 2.068 2.412 2.779 3.181 3.617 4.088 4.609 5.155 0.000

T/K = 293.15 0.9982 1.0043 1.0105 1.0166 1.0229 1.0295 1.0361 1.0429 1.0496 1.0563 1.0633 1.0704 1.0776 1.0849 1.0923 1.0998 1482.7 1493.6 1504.9 1516.5 1528.8 1541.8 1555.9 1569.3 1583.3 1597.1 1611.8 1626.9 1642.5 1658.4 1674.7 1691.4 0.993

T/K = 303.15

T/K = 313.15

ρ/g·cm−3 0.9959 0.9923 1.0016 0.9980 1.0077 1.0041 1.0138 1.0101 1.0199 1.0161 1.0264 1.0225 1.0329 1.0289 1.0394 1.0354 1.0460 1.0418 1.0529 1.0483 1.0597 1.0550 1.0666 1.0618 1.0736 1.0687 1.0808 1.0756 1.0880 1.0827 1.0950 1.0898 c/m·s−1 1509.4 1529.1 1519.0 1538.0 1529.4 1546.6 1539.3 1555.4 1550.0 1565.0 1561.1 1574.7 1573.6 1585.8 1585.0 1595.6 1597.4 1606.6 1609.3 1616.0 1622.1 1627.1 1635.2 1638.5 1648.7 1650.1 1662.4 1661.9 1676.5 1674.0 1690.9 1687.2 η/mPa·s 0.802 0.661

m1/ mol·kg−1

T/K = 323.15

0.207 0.425 0.654 0.897 1.164 1.449 1.748 2.068 2.412 2.779 3.181 3.617 4.088 4.609 5.155

0.9881 0.9939 0.9997 1.0056 1.0110 1.0180 1.0243 1.0307 1.0371 1.0435 1.0501 1.0568 1.0635 1.0704 1.0773 1.0842

0.000 0.207 0.425 0.654 0.897 1.164 1.449 1.748 2.068 2.412 2.779 3.181 3.617 4.088 4.609 5.155

1541.5 1549.2 1557.4 1566.1 1574.4 1583.0 1593.1 1601.3 1611.1 1620.0 1629.6 1639.4 1649.3 1659.4 1669.7 1680.2

T/K = 293.15 1.075 1.168 1.287 1.419 1.579 1.711 1.911 2.142 2.477 2.777 3.217 3.698 4.214 4.991 5.869 72.6 69.2 67.4 66.2 65.4 64.8 64.4 64.0 63.7 63.5 63.3 63.2 63.1 63.0 62.9 62.9

T/K = 303.15

T/K = 313.15

T/K = 323.15

0.880 0.718 0.942 0.761 1.025 0.806 1.085 0.870 1.193 0.936 1.309 1.017 1.472 1.158 1.631 1.260 1.875 1.441 2.094 1.597 2.402 1.820 2.743 2.063 3.092 2.296 3.635 2.687 4.210 3.084 σ/mN·m−1 71.1 69.2 67.5 66.3 66.1 64.7 65.0 63.5 64.2 62.8 63.5 62.1 62.9 61.5 62.5 61.1 62.2 60.7 61.9 60.5 61.7 60.3 61.5 60.2 61.4 60.1 61.3 60.0 61.2 59.9 61.2 59.9

0.596 0.635 0.671 0.716 0.755 0.819 0.908 0.985 1.131 1.233 1.387 1.569 1.770 2.027 2.327 67.7 65.1 63.4 62.1 61.2 60.5 60.1 59.7 59.5 59.2 59.0 58.9 58.8 58.7 58.6 58.6

a Standard uncertainties u are u(T) = 0.01 K, u(p) = 2 kPa, and u(m) = 0.002 mol·kg−1, and the combined expanded uncertainties Uc (level of confidence = 0.95, k = 2) are Uc(ρ) = 2 × 10−3 g·cm−3, Uc(c) = 0.6 m·s−1, Uc(η) = 0.05 mPa·s, and Uc(σ) = 0.4 mN·m−1.

0.555

Arrhenius model), with a clear decrease in this property with temperature. The influence of temperature is higher when amine concentration in the mixture increases. Figure 4 shows the experimental data corresponding to speed of sound data for aqueous solutions of HMTA that allow the influence of temperature and concentration to be analyzed upon this property. This physical property has been employed in previous works in order to evaluate the molecular interactions in this type of aqueous mixtures.20 Experimental data included in Figure 4 show an increase in the value of speed of sound with HMTA concentration for the entire temperature range. In order to carry out a deeper analysis of this behavior it must be taken into account the change in the influence of temperature upon speed of sound at high and low HMTA concentrations. In fact, the experimental data series at different temperatures cross (close to 4 mol·kg−1) when amine concentration increases. Specifically at low amine concentrations an increase in temperature causes also an increase in the value of the speed of sound, but the opposite behavior is observed at high HMTA concentrations.

Figure 3. Effect of HMTA concentration and temperature upon viscosity η. ○, T = 293.15 K; ●, T = 303.15 K; □, T = 313.15 K; ■, T = 323.15 K. Inner plot: ▲, m = 1.164 mol·kg−1; ◇, m = 2.779 mol· kg−1; *, m = 5.155 mol·kg−1; and , Arrhenius model. C



Article

modified. The presence of this type of structure is supported by previous studies that confirm the strong interactions of HMTA and water by X-ray analysis, observing the formation of clathrate structure.22 This type of behavior has been previously observed for other amine aqueous solutions.23 The last physical property analyzed in present work was surface tension of aqueous solutions of HMTA at different temperatures. This property can be generally used to analyze aggregation phenomena, and for this reason these data can contribute suitable information for this system. Previous studies that analyze surface tension of aqueous solutions using amines24,25 conclude that the presence of this type of substance causes a decrease in the value of this property. In this case, Figure 6 shows a slight decrease in the value of

Figure 4. Influence of HMTA concentration and temperature upon speed of sound c. ○, T = 293.15 K; ●, T = 303.15 K; □, T = 313.15 K; ■, T = 323.15 K.

When this type of behavior is observed, the formation of temperature-resistant structures must be considered, such as clathrates.21 In order to analyze in detail the presence of this type of structure, isentropic compressibility data have been employed. This property can be calculated using eq 3 employing experimental data of density and speed of sound. 1 κs = ρ ·c 2 (3) The calculated data for isentropic compressibility using eq 3 are shown in Figure 5. A decrease in isentropic compressibility Figure 6. Effect of HMTA concentration and temperature upon surface tension σ. ○, T = 293.15 K; ●, T = 303.15 K; □, T = 313.15 K; ■, T = 323.15 K.

surface tension when the HMTA concentration increases. Some amines have shown dramatic decreases in the value of surface tension with low amine additions.25 The last behavior can be related with the presence of nonpolar parts in the solute that causes an important accumulation of molecules at the interface. The decrease in surface tension is produced until a plateau is reached that is related with the molecular aggregation that maintains a constant concentration of molecules at the interface. This behavior agrees with the experimental data for the HMTA + water system showed in Figure 6. Regarding the influence of temperature upon surface tension, the commonly observed behavior is shown also in Figure 6: a decrease in the value of surface tension with temperature with a linear trend. Figure 6 also shows a plot of surface tension against the decimal logarithm of amine concentration. This type of plot is generally used to determine the concentration of solute that generates the aggregation phenomenon. The plot included in Figure 6 allows this concentration to be determined by a change in the slope. This critical aggregation concentration reaches a medium value of 2.5 mol HMTA·kg−1. This value is lower than the previously calculated one using the isentropic compressibility data. The critical aggregation concentrations determined using the influence of solute concentration upon surface tension can be slightly lower than the corresponding values determined using the speed of sound. This fact is due to

Figure 5. Influence of HMTA concentration and temperature upon isentropic compressibility κS. ○, T = 293.15 K; ●, T = 303.15 K; □, T = 313.15 K; ■, T = 323.15 K.

is observed with HMTA concentration. When the influence of temperature is analyzed, a change in the effect of this variable upon isentropic compressibility is observed again as in Figure 4. At low amine concentration an increase in temperature causes a decrease in isentropic compressibility. The opposite behavior is observed at high amine concentration range. The change in this behavior is reached at an HMTA concentration close to 3 mol·kg−1 due to the formation of a temperatureresistant structure. This type of structure does not allow the change in the value of this property when temperature is D



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the influence of a very small amount of impurities upon the value of surface tension.

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CONCLUSIONS The present work characterizes the influence of the presence of hexamethylenetetramine in aqueous solution through the evaluation of several physical properties (density, viscosity, speed of sound, and surface tension). Aqueous solutions of HMTA have a large application in several processes, and for this reason these properties can be suitable information for the understanding and development of reaction or separation processes. Experimental data have shown relatively common behaviors for density and viscosity than other amine-based systems, increasing their values with HMTA concentration. An increase in temperature causes a decrease in these values. The analysis of the influence of concentration and temperature upon the other properties (speed of sound and surface tension) showed a more complex behavior that is in agreement with the formation of temperature-resistant structures and specifically a clathrate type. The concentration that allows this type of structure to be generated was determined using isentropic compressibility data and confirmed by surface tension.

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AUTHOR INFORMATION

Corresponding Author

*(D.G.-D.) E-mail: [email protected]. ORCID

Diego Gómez-Díaz: 0000-0002-3271-1638 Notes

The authors declare no competing financial interest.

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REFERENCES

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