Viscosity Measurement and Correlation of Unloaded and CO2-Loaded

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

Viscosity Measurement and Correlation of Unloaded and CO2‑Loaded 3‑Amino-1-propanol Solution Zulkifli Idris,†,‡ Nithin B. Kummamuru,† and Dag A. Eimer*,†,‡ †

Faculty of Technology, Natural Sciences and Maritime Sciences, University College of Southeast Norway, Kjølnes Ring 56, Porsgrunn 3918, Norway ‡ SINTEF Tel-Tek, Kjølnes Ring 30, Porsgrunn 3918, Norway S Supporting Information *

ABSTRACT: This paper reports new viscosity data for unloaded and CO2-loaded aqueous 3-amino-1-propanol (3A1P) solutions. For the unloaded system, experiments were performed over the whole concentration range at temperatures between 298.15 and 373.15 K. In the case of a CO2-loaded system, measurements were performed at five different CO2-loadings ranging from 0.13 to 0.54 mol of CO2/mol of 3A1P at 0.30 and 0.50 3A1P mass fractions. The experimental data were also regressed using available methods from the literature.

1. INTRODUCTION Chemical absorption using an aqueous solution of alkanolamines is regarded as the matured available technology for the removal of carbon dioxide (CO2) from industrial gas streams.1,2 Among commercially available alkanolamines, monoethanolamine (MEA, IUPAC name: 2-aminoethanol) has been studied and utilized extensively due to its advantages such as fast chemical kinetics and high absorption rates. However, reaction of aqueous MEA with CO2 produces chemically stable carbamate that requires a high temperature to regenerate. This increases the energy requirement for such a process. Over the years, a number of other amines have been suggested as potential candidates for CO2-capture.3,4 The amine of interest in this study, 3-amino-1-propanol (3A1P), is a primary alkanolamine, and its schematic structure is shown in Figure 1. It is in the same class as MEA with the main difference being

The studied 3A1P solvent also showed a stable capture capacity after a number of cycles of absorption and regeneration processes, albeit loss of capture capacity was observed initially. Before this amine can be used industrially, information on chemical and physical properties is required. One of the important properties is viscosity which plays a key role in design and sizing of CO2-capture equipment.8 Previously reported experimental data on the viscosity of 3A1P are tabulated in Table 1. These studies mostly concern the viscosity changes in a nonaqueous solution of 3-amino-1-propanol. In continuation of our research, this present paper reports new viscosity data for aqueous 3A1P in unloaded and CO2-loaded systems. Experimental data on the viscosity of CO2-loaded solutions for other amines such as ethanolamine, methyl diethanolamine, and piperazine can also be found in the literature.9−14 Correlating experimental data with suitable equations is important alongside measuring accurate new data. As such, a number of methods are available in the literature. In this work, a semiempirical equation as reported by Heric and Brewer15 was employed to represent the viscosity of aqueous 3A1P solution. In the case of carbonated 3A1P solution, the modified Setschenow equation was used.16

Figure 1. Structure of 3-amino-1-propanol (3A1P) studied in this work.

that 3A1P exhibits an extra alkyl group. It has been claimed to have a high reaction rate with CO2 which is attractive when dealing with low CO 2 partial pressure gas streams. 5 Quantitative 13C-nuclear magnetic resonance (NMR) spectroscopy experiments reported by Perinu et al.6 also revealed that 3A1P forms a less stable carbamate upon reaction with CO2 in comparison to MEA. In a recent paper by Bentes et al.,7 the overall CO2 absorption process in 3A1P solution was evaluated. © XXXX American Chemical Society

Received: November 29, 2017 Accepted: April 20, 2018

A

DOI: 10.1021/acs.jced.7b01035 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 1. Details of Previous Viscosity Work on Pure 3-Amino-1-propanol (3A1P) as Reported in the Literature source

instrument used

concentration covered (mass %)

temperature covered (K)

CO2-loaded

Omrani et al.17 Kermanpour and Niakan18 Kermanpour et al.19 Blanco et al.20

Schott-Gerate AVS 400 viscometer Ubbelohde viscometer Ubbelohde viscometer Schott’s capillary Ubbelohde viscometer

100 100 100 100

298.15−308.15 293.15−333.15 293.15−333.15 293.15−323.15

no no no no

Table 2. Chemicals Used in This Worka

a

chemical name

mole fraction puritya

source

purification

3-amino-1-propanol (3A1P) carbon dioxide (CO2) nitrogen (N2) sodium hydroxide (NaOH) hydrochloric acid (HCl) barium chloride dihydrate (BaCl2·2H2O)

≥0.995 0.99999 0.99999

Sigma-Aldrich AGA Norge AS AGA Norge AS Merck KGaA Merck KGaA Merck KGaA

no no no no no no

≥0.99

As stated by the supplier.

AMD (mPa ·s) = MAX|ηi E − ηiC|

2. MATERIALS AND METHODS The chemicals used in this work are listed in Table 2. They were used without any purification, apart from degassing. Aqueous 3A1P solutions were prepared gravimetrically using an analytical balance from Mettler Toledo XS-403S with a resolution of 1 mg. The Milli-Q water (resistivity 18.2 MΩ· m) was also degassed before being used. The CO2-loaded solutions were prepared by bubbling CO2 gas at a flow rate of 0.15 L·min−1 into the unloaded 3A1P solution. By varying the time of the CO2 bubbling process, five different CO2-loaded samples (between loading values of 0.13 and 0.54 mol of CO2/ mol of MEA) were prepared for each 3A1P concentration studied in this work. Past work shows that there is no significant change in loading when following this procedure. In order to determine the actual CO2-loadings in the prepared solutions, an acid−base titration method as discussed previously was employed.21 Dynamic viscosity was measured using an Anton-Paar Physica MCR 101 rheometer with a double-gap pressure cell XL (DG35.12/PR, measuring cell serial number 80462200) at T = 298.15−373.15 K. A detailed explanation on viscosity measurement in our laboratory has been published recently.22 Viscosity values reported in this work are average values from at least 50 different readings with each set of experiments repeated three times. The experimental data were also corrected against the calibrated values from General Purpose Viscosity Reference Standard S3S as supplied by Paragon Scientific Ltd.

ηEi ,

where N, and refer to the number of data, the experimental viscosity, and the calculated viscosity, respectively. 4.1. Viscosity of Unloaded 3A1P Solutions. In order to validate the measurement system, the viscosity of pure 3A1P was measured at different temperatures and compared with available literature data. These are tabulated in Table S1 of the Supporting Information, and a graphical representation is shown in Figure 2. The calculated AAD values between this

Figure 2. Comparison of the viscosity of pure 3A1P η between this work and data from the literature at different temperatures T. The data from this work are labeled as ▷, while the data from the work of Omrani et al.,17 Kermanpour and Niakan,18 Kermanpour et al.,19 and Blanco et al.20 are shown as ●, ■, ▼, and ○, respectively.

3. EXPERIMENTAL UNCERTAINTY The error propagation estimates are 0.10 and 0.15 mPa·s for unloaded and CO2-loaded systems, similar to our recent publication.22 The present systems are not significantly different in this respect.

work and Omrani et al.,17 Kermanpour and Niakan,18 Blanco et al.,20 and Kermanpour et al.19 are 0.11, 0.01, 0.01, and 0.08 mPa·s, respectively. The low AAD values indicate that our data agree well with the literature, and our measuring system is reliable. Table 3 lists the viscosity of aqueous 3A1P solution determined in this work. Viscosities for the unloaded 3A1P solutions were measured at different 3A1P mass fractions ranging from 0.1 to 1.0 at T = 298.15−373.15 K. As can be seen, the viscosity of aqueous 3A1P decreases as temperature increases, as expected. The change in viscosity as a function of 3A1P mole fraction is displayed in Figure 3. In general, viscosity increases with the

4. RESULTS AND DISCUSSION This section will discuss the viscosity of aqueous 3A1P followed by the viscosity of CO2-loaded 3A1P solutions. In order to evaluate models used for representing the viscosity data, absolute average and maximum deviation (AAD and MD) values were determined using eqs 1 and 2 AAD (mPa· s) =

1 N

N

∑ |ηi E − ηiC| i=1

(2)

ηCi

(1) B

DOI: 10.1021/acs.jced.7b01035 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 3. Viscosity η of Aqueous 3A1P Solutionsa w1

0b

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

0.90

1.00

x1

0

0.026

0.057

0.09

0.14

0.19

0.26

0.36

0.49

0.68

1.00

12.17 9.64 7.69 6.25 5.17 4.34 3.69 3.17 2.74 2.39 2.09 1.85 1.68 1.51 1.37 1.26

18.56 14.50 11.48 9.21 7.50 6.17 5.14 4.33 3.67 3.15 2.72 2.37 2.09 1.86 1.66 1.49

26.23 20.98 15.73 12.52 10.09 8.24 6.81 5.68 4.79 4.08 3.51 3.03 2.70 2.40 2.13 1.91

29.26 22.76 17.96 14.36 11.60 9.47 7.78 6.47 5.43 4.61 3.93 3.39 2.93 2.56 2.24 1.98

30.43 23.87 19.07 15.27 12.36 10.22 8.54 7.12 6.05 4.84 4.17 3.63 3.19 2.73 2.52 2.25

η (mPa·s)

T (K) 298.15 303.15 308.15 313.15 318.15 323.15 328.15 333.15 338.15 343.15 348.15 353.15 358.15 363.15 368.15 373.15

0.89 0.80 0.72 0.65 0.60 0.55 0.50 0.47 0.43 0.40 0.38 0.36 0.33 0.32 0.30 0.28

1.27 1.14 1.01 0.89 0.81 0.75 0.72 0.66 0.61 0.58 0.57 0.55 0.41 0.39 0.37 0.35

1.84 1.62 1.41 1.25 1.12 1.01 0.92 0.84 0.76 0.73 0.70 0.67 0.54 0.49 0.47 0.44

2.95 2.50 2.15 1.82 1.59 1.40 1.24 1.10 0.99 0.90 0.82 0.75 0.69 0.65 0.63 0.59

4.76 3.97 3.34 2.82 2.42 2.11 1.86 1.66 1.47 1.32 1.20 1.08 0.99 0.93 0.88 0.82

7.58 6.18 5.10 4.23 3.59 3.07 2.65 2.31 2.03 1.81 1.64 1.46 1.32 1.25 1.16 1.05

a Experiments were performed at different 3A1P mass fractions w1 and temperatures T. The pressure during experiments was maintained by N2 gas (p = 5 bar). Standard uncertainties u are u(w1) = 0.01, u(T) = 0.03 K, and u(p) = 0.002 bar. The combined standard uncertainty for viscosity measurement uc(η) is 0.10 mPa·s. The corresponding 3A1P mole fraction x1 is also shown. bThe viscosities of water at different temperatures were taken from Kestin et al.28

complex formation. Negative deviation on the other hand may indicate that dispersion forces are primarily responsible for molecule interaction. The change in viscosity deviation from negative in the water-rich region to positive in the amine-rich region was also reported in other aqueous alkanolamine systems such as in ethanolamine, diisopropanolamine, and methyl diethanolamine.24−27 Our recent publication compared four different semiempirical methods for correlating the viscosity of aqueous alkanolamine,22 and in this paper, the method based on the work of Heric and Brewer15 was chosen. In this method, the viscosity of the mixture ηmix is calculated using an equation as follows ln ηmix = x1 ln η1 + x 2 ln η2 + x1 ln M1 + x 2 ln M 2

Figure 3. Viscosity of aqueous 3A1P η against the mole fraction of 3A1P x3A1P at different temperatures. Symbols: 298.15 K (■), 303.15 K (○), 308.15 K (▲), 313.15 K (▽), 318.15 K (◆), 323.15 K (◁), 328.15 K (▶), 333.15 K (⬟), 338.15 K (□), 343.15 K (●), 348.15 K (△), 353.15 K (▼), 358.15 K (◇), 363.15 K (◀), 368.15 K (▷), 373.15 K (⬢). Dotted lines refer to the calculated viscosity values using the Heric−Brewer equation.

⎡ i ⎤ − ln(x1M1 + x 2M 2) + x1x 2⎢∑ Ai (x1 − x 2)i ⎥ ⎢⎣ i = 0 ⎥⎦ (4)

where x, η, M, and A refer to the mole fraction, the viscosity of the pure component, the molecular weight, and the Heric− Brewer parameter, respectively. Integers 1 and 2 represent 3A1P and water. The viscosities of pure water were taken from Kestin et al.28 The number of parameters Ai may be chosen with a minimum value of i of zero, implying one parameter. Several attempts at optimizing the predicted 3A1P viscosity were made by varying the order of i, and we have concluded that, in the case of aqueous 3A1P, a first order Heric−Brewer equation yields a satisfactory outcome. Values of A0 and A1 at different temperatures are listed in Table 4. The regressed Heric−Brewer parameters were then subjected to a second order temperature dependent polynomial, as shown in eq 5.

increase in 3A1P mole fraction. In order to represent deviation from a linear dependency on mole fraction, viscosity deviation Δη was calculated using the formula below i

Δη = ηmix −

∑ xiηi i=1

(3)

where ηmix, xi, and ηi represent the viscosity of the mixture, the mole fraction, and the viscosity of pure component i, respectively. Values of Δη are tabulated in Table S2. At lower temperatures and mole fractions of 3A1P, there are small negative deviations from a linear dependency on mole fraction, with larger deviations elsewhere. According to Fort and Moore,23 positive deviation may be observed in the case of a strong specific interaction such as a hydrogen bond that causes

Ai = Ai0 + Ai1·T + Ai2 ·T 2

(5)

Values of Ai0, Ai1, and Ai2 are tabulated in Table 5. On the basis of the temperature-dependence parameters, the calculated C

DOI: 10.1021/acs.jced.7b01035 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 4. Heric−Brewer First Order Parameters A0 and A1 at Different Temperatures T (eq 4) T (K)

A0

A1

298.15 303.15 308.15 313.15 318.15 323.15 328.15 333.15 338.15 343.15 348.15 353.15 358.15 363.15 368.15 373.15

7.51 7.24 6.86 6.58 6.33 6.07 5.81 5.60 5.39 5.34 5.16 4.98 4.85 4.71 4.56 4.45

−4.95 −4.72 −4.57 −4.30 −4.15 −4.04 −4.00 −3.92 −3.86 −3.75 −3.81 −3.81 −3.53 −3.65 −3.81 −3.84

solution at 0.3 and 0.5 3A1P mass fraction are listed in Tables 6 and 7, respectively. As expected, the viscosity of the solution Table 6. Viscosity η of CO2-Loaded Aqueous 3A1P Solutions at 0.30 3A1P Mass Fraction at Different Temperatures T, CO2-Loading Values α, and CO2 Mole Fractions x3a α (mol of CO2/mol of 3A1P)

0.13

0.25

0.34

0.44

0.54

x3

0.012

0.023

0.031

0.039

0.048

298.15 303.15 308.15 313.15 318.15 323.15 328.15 333.15 338.15 343.15 348.15 353.15 358.15 363.15 368.15 373.15

Table 5. Heric−Brewer Temperature Dependent Parameters (eq 5) parameters A00 = 9.29 A10 = −6.21

A01 = −0.08 A11 = 0.06

A02 = 0.0003 A12 = −0.0004

η (mPa·s)

T (K)

AMD = 0.25 mPa·s AAD = 0.09 mPa·s

3.22 2.77 2.38 2.03 1.79 1.59 1.40 1.25 1.13 1.03 0.94 0.86 0.79 0.74 0.70 0.69

3.51 3.02 2.61 2.26 2.00 1.78 1.60 1.44 1.31 1.19 1.09 1.00 0.93 0.87 0.80 0.76

3.76 3.22 2.79 2.42 2.15 1.92 1.76 1.57 1.42 1.28 1.16 1.06 0.98 0.92 0.86 0.81

4.02 3.48 3.04 2.64 2.32 2.06 1.85 1.66 1.51 1.38 1.26 1.16 1.09 1.02 0.96 0.92

4.14 3.58 3.11 2.70 2.38 2.12 1.89 1.71 1.55 1.40 1.28 1.17 1.08 1.01 0.95 0.90

a

The pressure during experiments was maintained by N2 gas (p = 5 bar). Standard uncertainties u are u(w1) = 0.01, u(x3) = 0.002, u(T) = 0.03 K, and u(p) = 0.002 bar. The combined standard uncertainty for viscosity measurement uc(η) is 0.15 mPa·s.

AAD and AMD values are 0.09 and 0.32 mPa·s, respectively. A deviation plot between the experimental and calculated data is shown in Figure 4. The low absolute deviation values suggest

containing CO2 is higher than the nonloaded solution.9−12 This is because there is an increase in the intermolecular forces between water, amine, CO2, and reaction products. The Table 7. Viscosity η of CO2-Loaded Aqueous 3A1P Solutions at 0.50 3A1P Mass Fraction at Different Temperatures T, CO2-Loading Values α, and CO2 Mole Fractions x3a α (mol of CO2/mol of 3A1P)

0.13

0.24

0.32

0.42

0.52

x3

0.025

0.044

0.058

0.075

0.091

9.34 7.62 6.30 5.23 4.41 3.76 3.25 2.83 2.49 2.21 1.97 1.77 1.61 1.47 1.35 1.25

11.61 9.40 7.75 6.47 5.48 4.69 4.06 3.54 3.12 2.77 2.47 2.21 2.00 1.84 1.69 1.56

15.29 12.35 10.17 8.51 7.22 6.20 5.37 4.69 4.11 3.64 3.25 2.93 2.67 2.45 2.27 2.12

18.07 14.74 12.18 10.16 8.59 7.33 6.32 5.49 4.82 4.27 3.81 3.43 3.12 2.87 2.66 2.49

η (mPa·s)

T (K) 298.15 303.15 308.15 313.15 318.15 323.15 328.15 333.15 338.15 343.15 348.15 353.15 358.15 363.15 368.15 373.15

Figure 4. Average deviations [ηexpt − ηcalc] between experimental and calculated values from the Heric−Brewer equation at different 3A1P mole fractions x3A1P. Symbols: 298.15 K (■), 303.15 K (○), 308.15 K (▲), 313.15 K (▽), 318.15 K (◆), 323.15 K (◁), 328.15 K (▶), 333.15 K (⬟), 338.15 K (□), 343.15 K (●), 348.15 K (△), 353.15 K (▼), 358.15 K (◇), 363.15 K (◀), 368.15 K (▷), 373.15 K (⬢).

that the method of Heric−Brewer is able to correlate the viscosity of aqueous 3A1P satisfactorily, and the AAD is lower than the estimated standard uncertainty. The calculated viscosities are also shown as dotted lines in Figure 3. 4.2. Viscosity of CO2-Loaded 3A1P Solutions. The second part of this paper investigates the viscosity of CO2loaded 3A1P solution. Two 3A1P concentrations were selected for evaluation. Measurements were performed at five different CO2-loadings ranging from 0.13 to 0.54 mol of CO2/mol of 3A1P at T = 298.15−373.15 K. Viscosities of CO2-loaded

13.14 10.74 8.89 7.44 6.32 5.41 4.69 4.01 3.62 3.21 2.87 2.58 2.34 2.14 1.97 1.84

a

The pressure during experiments was maintained by N2 gas (p = 5 bar). Standard uncertainties u are u(w1) = 0.01, u(x3) = 0.002, u(T) = 0.03 K, and u(p) = 0.002 bar. The combined standard uncertainty for viscosity measurement uc(η) is 0.15 mPa·s.

D

DOI: 10.1021/acs.jced.7b01035 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Setschenow equation was used in this work. The regressed parameters are shown in Table 8 for the two 3A1P mass

relationship between viscosity and temperature for the carbonated solution is illustrated in Figure 5; panel A shows the viscosity of CO2-loaded solution for the 0.3 3A1P mass fraction, while panel B shows the viscosity for the 0.5 3A1P mass fraction.

Table 8. Parameters k and Deviations AAD Based on the Modified Setchsenow Equation (eq 6) 30 mass % 3A1P k1,0 = −1.147 k2,0 = 2.134

k1,1 = 0.007 k2,1 = −0.028 50 mass % 3A1P

AAD = 0.03 mPa·s

k1,0 = 2.597 k2,0 = −1.473

k1,1 = −0.002 k2,1 = 0.004

AAD = 0.07 mPa·s

fractions studied in this work. The calculated viscosity values are also represented as dotted lines in Figure 5. Average absolute deviations of 0.03 and 0.07 mPa·s were calculated for the CO2-loaded (0.30 and 0.50) 3A1P mass fraction systems. These AAD deviations are smaller than the estimated standard uncertainty. In view of this, the propagated errors calculated seem to be pessimistic, and the AAD deviations derived are used as the basis for significant digits reported. A comparison of average deviations between the experimental and predicted data is shown in Figure 6. It is evident from both figures that the

Figure 5. Viscosity of CO2-loaded 3A1P solution η as a function of temperature T. Panel A shows plots of viscosity against temperature for 0.30 3A1P mass fraction at different CO2-loading values of 0.13 (■), 0.25 (●), 0.34 (▲), 0.44 (▼), and 0.54 (◆). Panel B shows the viscosity of 0.50 3A1P mass fractions at different CO2-loadings of 0.13 (□), 0.24 (○), 0.32 (△), 0.42 (▽), and 0.52 (◇). The dotted lines represent the calculated values from the modified Setschenow equation.

Figure 6. Average deviations [ηexpt − ηcalc] between experimental and calculated values from the modified Setschenow equation at different temperatures T. Calculated values from 0.30 3A1P mass fraction are shown as ■, ●, ▲, ▼, and ◆ for CO2-loadings of 0.13, 0.25, 0.34, 0.44, and 0.54, respectively. Calculated values from 0.50 3A1P mass fraction are shown as □, ○, △, ▽, and ◇ for CO2-loadings of 0.13, 0.24, 0.32, 0.42, and 0.52, respectively.

In this work, the viscosity of CO2-loaded 3A1P solutions was correlated using the modified Setschenow equation.16 This equation was originally used to explain the salting effects in liquid mixture systems but has also been used to represent physical property relationships of aqueous amine mixtures.29−31 We have recently applied this equation to represent the viscosity of CO2-loaded concentrated MEA solutions.22 This equation was used, as it yielded better data fitting and minimal standard deviation as compared to other tested techniques. The modified Setschenow equation that correlates the viscosity and CO2 concentration is

⎛η⎞ ln⎜⎜ ⎟⎟ = ⎝ ηr ⎠

modified Setschenow equation is able to correlate the viscosity of CO2-loaded 3A1P solution. Larger deviations, albeit lower than 8%, were observed for several data points especially for measurements at higher temperatures.

5. CONCLUSION This work presents new viscosity data for both unloaded and CO2-loaded aqueous 3A1P solutions. Experiments were conducted at different mass fractions and T = 298.15−373.15 K. At all temperatures studied, viscosity decreases with an increase in temperature. The viscosity deviations from linear dependency on mole fraction were similar to previously studied aqueous alkanolamine systems at the water-rich region and at the amine-rich region. A first order Heric−Brewer equation was found to correlate the unloaded 3A1P viscosity satisfactorily. The viscosity of the CO2-loaded solutions was measured at 0.30 and 0.50 3A1P mass fractions at five different CO2-loadings.

n

∑ k j· α j j=1

(6)

where η/ηr and α are the ratio between the viscosity of CO2loaded and unloaded aqueous 3A1P solution at a corresponding temperature. The Setschenow parameter kj has been shown to be linearly dependent on temperature.30 A second order E

DOI: 10.1021/acs.jced.7b01035 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

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The values are higher than that of an unloaded solution. A modified version of the Setschenow equation was utilized to represent the viscosity of CO2-loaded solution.



ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.7b01035. Viscosity of pure 3A1P and viscosity deviations at different temperatures (PDF)



AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Phone: +47 3557 4000. ORCID

Zulkifli Idris: 0000-0001-7905-9686 Funding

This work was supported by The Research Council of Norway (Grant No. 199890). Notes

The authors declare no competing financial interest.



REFERENCES

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DOI: 10.1021/acs.jced.7b01035 J. Chem. Eng. Data XXXX, XXX, XXX−XXX