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Volumetric and viscometric properties of aqueous solutions of sodium amino acids at T = (293.15 to 333.15) K
Accepted Manuscript Volumetric and viscometric properties of aqueous solutions of sodium amino acids at T = (293.15 to 333.15) K
Chunyan Chu, Chunying Zhu, Taotao Fu, Youguang Ma PII: DOI: Reference:
S0167-7322(17)34235-6 https://doi.org/10.1016/j.molliq.2018.01.058 MOLLIQ 8512
To appear in:
Journal of Molecular Liquids
Received date: Revised date: Accepted date:
12 September 2017 22 December 2017 9 January 2018
Please cite this article as: Chunyan Chu, Chunying Zhu, Taotao Fu, Youguang Ma , Volumetric and viscometric properties of aqueous solutions of sodium amino acids at T = (293.15 to 333.15) K. The address for the corresponding author was captured as affiliation for all authors. Please check if appropriate. Molliq(2017), https://doi.org/ 10.1016/j.molliq.2018.01.058
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ACCEPTED MANUSCRIPT Volumetric and viscometric properties of aqueous solutions of sodium amino acids at T = (293.15 to 333.15) K Chunyan Chu, Chunying Zhu, Taotao Fu, Youguang Ma* State Key Laboratory of Chemical Engineering, Collaborative Innovation Center of Chemical science and Engineering, School of Chemical Engineering and Technology,
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Tianjin University, Tianjin 300072, PR China
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ABSTRACT
The densities and viscosities of aqueous solutions of sodium glycinate, sodium
SC
L-alaninate, sodium L-valinate, sodium L-threoninate and sodium L-argininate were
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measured at T = (293.15 to 333.15) K under the atmospheric pressure. The effects of temperature and concentration on the densities and viscosities of binary solutions
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were investigated. The volumetric and viscometric properties such as the apparent molar volume (Vφ), the limiting partial molar volume (Vφ0), the viscosity B-coefficient (B) and the activation energy for viscous flow (Ea) were calculated by the
D
experimental density and viscosity data and analyzed based on the molecular structure
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and intermolecular interaction. Moreover, the group contribution method was utilized to study the limiting partial molar volume (Vφ0), and the contributions of the end
CE
group (-NH2,-COONa), CH- group, CH2- group, CH3- group, OH- group and CNHNHNH2- group to the limiting partial molar volume (Vφ0) were obtained. The
AC
results show that all these groups have positive contributions to the limiting partial molar volume (Vφ0). Keywords: Sodium amino acid; Density; Viscosity; Apparent molar volume; B-coefficient
1. Introduction In recent years, the global warming stemming from greenhouse effect has become one of the focuses of worldwide concerns. Among all kinds of greenhouse
Corresponding author. E-mail: [email protected] (C. Zhu). 1
ACCEPTED MANUSCRIPT gases, CO2 is the predominant contributor. Consequently, the capture and reuse of CO2 is an effective way to reduce the release of CO2 [1]. At present, chemical absorption method has been extensively applied for CO2 capture in which absorbent is one the key issues, thus the exploration of absorbent with excellent performance is of great importance. In industry, aqueous solutions of monoethanolamine (MEA),
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methyl-diethanolamine (MDEA) and other alcohol amine have been widely used for CO2 absorption [2]. However, the aqueous solutions of alcohol amine have the
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disadvantages of corrosion, solvothermal degradation and high regenerative energy
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consumption, greatly limiting the application in the large-scale capture and separation of CO2. Compared with traditional alcohol amines such as MEA and MDEA aqueous
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solutions, the amino acid salt solutions have these advantages such as low volatility, low toxicity, antioxidant degradation and good absorption performance, and have
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accordingly received increasing attention [3-6]. Besides, simple amino acid salts have catalytic ability on the asymmetric aldol reaction, Michael addition reaction, and
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cyanosilylation, thus they are widely used in the synthesis of organic compounds [7].
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Densities and viscosities are the basic data of physical property and indispensable for chemical design and process optimization. In addition, they are also necessary data for calculating thermodynamic properties, such as the apparent molar
CE
volume (Vφ) and the limiting partial molar volume (Vφ0), the viscosity B-coefficient (B) and the activation energy for viscous flow (Ea). These parameters are conducive to
AC
the understanding of the flow and transfer characteristics of fluid. Tirona et al. [8] measured the densities, viscosities, refractive indices and electrical conductivities of α-alanine (ALA) in aqueous solutions of sodium hydroxide and potassium hydroxide. Ziemer et al. [9] determined the densities of the aqueous solutions of sodium L-alaninate at T = (278.15 to 368.15) K under 0.35 MPa, and the apparent molar volumes (Vφ) were obtained, meanwhile, the effects of morphological and chemical relaxation on the apparent molar volumes (Vφ) were also analyzed according to Young's rule. Mondal et al. [10] measured the densities of aqueous 2
ACCEPTED MANUSCRIPT solutions of sodium glycinate, and studied the gas - liquid equilibrium of CO2 in aqueous solutions of sodium glycinate. Shaikh et al. [11] measured the densities, viscosities and refractive indices of aqueous solutions of sodium glycinate at T = (298.15 to 343.15) K and the experimental data were correlated. In addition, the volumetric properties of amino acids in salt solutions were also investigated
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experimentally. Rajagopal et al. [12] measured the densities and ultrasonic speeds of glycine, L-alanine, L-valine and L-leucine in aqueous solutions of sodium fluoride,
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and calculated a series of volumetric properties such as the apparent molar volume
SC
(Vφ) and the limiting partial molar volume (Vφ0). Siddique et al. [13] measured the densities of L-lysine, L-histidine and L-arginine in aqueous solutions of sodium
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acetate, potassium acetate and calcium acetate, and calculated the apparent molar volumes (Vφ) through the densities. Various interactions between amino acids and
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organic salts in these solutions were analyzed. Although the volumetric and viscometric properties of various amino acids in salt solutions have been widely
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investigated, the volumetric and viscometric properties of aqueous solutions of
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sodium amino acids remain still scarce, which motivates us to systematically study the volumetric and viscometric properties of different kinds of aqueous solutions of sodium amino acids.
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In this paper, the densities and viscosities of aqueous solutions of sodium glycinate, sodium L-alaninate, sodium L-valinate, sodium L-threoninate and sodium
AC
L-argininate were systematically studied at T = (293.15 to 333.15) K under the atmospheric pressure. The volumetric and viscometric properties such as the apparent molar volume (Vφ), the limiting partial molar volume (Vφ0), the viscosity B-coefficient (B) and the activation energy for viscous flow (Ea) were calculated through density and viscosity data. The limiting partial molar volume was analyzed by means of the group contribution method, and the contribution of each group to the limiting partial molar volume was obtained.
2. Experimental section 3
ACCEPTED MANUSCRIPT 2.1. Reagents Glycine, L-alanine, L-valine, L-threonine and L-arginine are analytical reagents, and the mass fractions of amino acids are ≥ 99% except L-arginine ≥ 98%, the mass fraction of sodium hydroxide is ≥ 99.44%. The details of reagents are summarized in Table 1. The deionized water was used to prepare solutions. All solutions were
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weighed by a FA2004B balance with precision of ± 0.0001 g. Aqueous solutions of sodium amino acids were prepared by dissolving the equimolar amino acid and
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sodium hydroxide in water as introduced in the literature [8,9]. The molalities of
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sodium amino acids are from 0.0 to 3.0 mol·kg-1 with an interval of 0.25 mol·kg-1 except for the sodium L-valinate and sodium L-argininate from 0.0 to 1.5 mol·kg-1
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due to their low solubility. The structures of the five kinds of sodium amino acids are shown in Fig. 1.
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Table 1 List of experimental reagents. CAS No.
Molar mass (g·mol-1)
Source
glycine
56-40-6
75.07
Aladdin Chemical Reagent Co., Ltd.
≥ 99%
L-alanine
56-41-7
89.09
Aladdin Chemical Reagent Co., Ltd.
≥ 99%
L-valine
72-18-4
117.15
Aladdin Chemical Reagent Co., Ltd.
≥ 99%
L-threonine
72-19-5
119.12
Aladdin Chemical Reagent Co., Ltd.
≥ 99%
L-arginine
74-79-3
174.20
Aladdin Chemical Reagent Co., Ltd.
≥ 98%
1310-73-2
40.00
Aladdin Chemical Reagent Co., Ltd
≥ 99.44%
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AC
CE
Sodium hydroxide
D
Chemical name
Fig. 1. Structures of five kinds of sodium amino acids. 4
Mass fraction purity
ACCEPTED MANUSCRIPT 2.2. Density Measurement The densities of aqueous solutions of sodium amino acids were measured by a vibrating tube density meter (Anton Paar DMA 4500 M, Austria) with an accuracy of ± 5 × 10-5 g·cm-3. The density meter was calibrated by the deionized water and dry air at 293.15 K under the atmospheric pressure. After each measurement, the density
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meter was automatically cleaned using the distilled water and anhydrous ethanol, respectively. The temperatures were automatically controlled by the instrument with
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an uncertainty of ± 0.03 K. The average value of the triplicate measurements was
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adopted as the final result of density for a given condition. In this work, the densities of pure water at different temperatures are in line with those in the literature [14,15]
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as shown in Table 2.
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2.3. Viscosity Measurement
The viscosities of aqueous solutions of sodium amino acids were measured using
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an iVisc capillary viscometer (LAUDA, Germany), and the viscometer was calibrated
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using viscosity standard fluids. The viscometer filled with experimental solution was vertically placed in the water thermostat (the LAUDA Eco Sliver Thermostats). The temperatures of the experimental water thermostat were separately set at T = (293.15,
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303.15, 313.15, 323.15, 333.15) K with an uncertainty of ± 0.05 K. The flow times of solutions in the capillary were automatically detected by the infrared with an
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uncertainty of ± 0.01 s. Each sample was measured at least three times with a deviation of 0.2 s. The average value of the flow times was used to obtain the final viscosity.
The viscosities of solutions were calculated by the following equation [16]: η / ρ Xt K / t
(1)
where η, ρ, t are viscosity, density and flow time of the solution, respectively, X and K are the viscometer constants. The uncertainty of the viscosity is ± 0.009 mPa·s. The viscosities of pure water at different temperatures in the experiment agree well with 5
ACCEPTED MANUSCRIPT those in the literature [14,17] as shown in Table 2.
3. Results and discussion 3.1. Volumetric properties The density data of the aqueous solutions of sodium amino acids in T = (293.15, 303.15, 313.15, 323.15, 333.15) K are shown in Table 2. The comparisons of the
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densities and viscosities of aqueous solutions of sodium glycinate between experimental data and literature values are shown in Fig. 2 and 3, respectively. From
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the figures, it could be clearly seen that the experimental densities of the aqueous
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solutions of sodium glycinate show a good agreement with the literature values [10,11] except for those at the high concentration. Both the experimental viscosities and
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literature values show that the viscosities increase with the rise of the concentration. The experimental viscosities are in accord with the literature values [10] except for
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those at the high concentration, but the experimental data are smaller than those values in the literature [11] in which the viscosities show a wave tendency with
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concentration. A routine Cannon-Fenske viscometer was used to measure the
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viscosities in literature [10]. A rolling ball type viscometer (Anton Paar, Lovis-2000 M/ME) was used to measure the viscosities in literature [11]. They are different from this work (iVisc capillary viscometer, LAUDA, Germany). Moreover, the mass
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fractions of glycinate sodium salt hydrate is ≥ 99% in literature [10], and the mass fractions of glycine and sodium hydroxide are ≥ 99% in literature [11], while the mass
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fraction of glycine is ≥ 99% and sodium hydroxide is ≥ 99.44% in this study. In addition, the solutions were prepared with mass fractions in the literature [10,11], but in this work the solutions were prepared with molality. The differences of the instrument, the impurities in the reagents and the operating process might result in the deviation between the experimental data and the values in literature.
6
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1.14 1.12
/(g·cm-3)
1.10 1.08 1.06 1.04
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1.02
0.0
0.5
1.0
1.5 2.0 2.5 m/(mol·kg-1)
3.0
3.5
SC
0.98
RI
1.00
Fig. 2. Comparisons of the densities of aqueous solutions of sodium glycinate between
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experimental data and literature data □, 313.15 K; ○, 323.15 K; Δ, 333.15 K; hollow symbols for literature values in ref [10]; cross-filled symbols for literature values in ref [11];
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solid symbols for experimental data, the lines are just a guide of experimental values.
1.6
D
1.2 1.0 0.8
CE
0.6
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/(mPa·s)
1.4
AC
0.4
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
-1
m/(mol·kg )
Fig. 3. Comparisons of the viscosities of aqueous solutions of sodium glycinate between experimental data and literature data □, 313.15 K; ○, 323.15 K; Δ, 333.15 K; hollow symbols for literature values in ref [10]; cross-filled symbols for literature values in ref [11]; solid symbols for experimental data, the lines are just a guide of experimental values.
7
ACCEPTED MANUSCRIPT
Table 2. The densities, ρ and viscosities, η, of aqueous solutions of sodium amino acids at T = (293.15 to 333.15) K under the atmospheric pressure. T/K = 293.15 ρ/( g·cm )
-1
-3
m/(mol·kg )
T/K = 303.15
η/( mPa·s)
ρ/( g·cm )
T/K = 313.15
η/( mPa·s)
-3
ρ/( g·cm )
I R -3
ρ/( g·cm )
η/( mPa·s)
[13]
0.5470[13]
sodium glycinate [13]
0.99564
[13]
0.99222
[13]
0.99821
0.0000
0.998211[14]
1.0020[15]
0.995656[14]
0.7975[15]
0.0000
0.99819
1.002
0.99564
0.798
0.99222
0.2500
1.01109
1.084
1.00840
0.871
1.00486
0.5000
1.02334
1.193
1.02048
0.946
0.7500
1.03497
1.276
1.03192
1.016
1.0000
1.04604
1.392
1.04279
1.100
1.2500
1.05659
1.486
1.05315
1.5000
1.06666
1.619
1.06304
2.0000
1.08556
1.860
1.08169
2.5000
1.10312
2.130
3.0000
1.11968
2.422
0.6532
SC
[13]
0.6532[15]
U N
ρ/( g·cm-3)
0.5471[15]
η/( mPa·s)
0.4666[15]
0.548
0.98320
0.466
0.710
1.00056
0.594
0.99570
0.502
0.772
1.01244
0.645
1.00754
0.547
1.02817
0.825
1.02371
0.688
1.01878
0.582
1.03895
0.894
1.03442
0.744
1.02947
0.631
1.187
1.04921
0.952
1.04462
0.789
1.03966
0.666
1.271
1.05902
1.035
1.05438
0.851
1.04939
0.716
1.470
1.07748
1.182
1.07272
0.972
1.06769
0.816
1.09918
1.681
1.09476
1.343
1.08984
1.099
1.08476
0.915
1.11595
1.932
1.11128
1.528
1.10611
1.243
1.10099
1.030
PT
D E
A M 1.01683
0.654
0.98805
T/K = 333.15
0.98803
E C
C A
0.7977
[13]
0.0000
sodium L-alaninate
1.0020
[13]
T P
T/K = 323.15
η/( mPa·s)
-3
0.0000
0.99819
1.002
0.99564
0.798
0.99222
0.654
0.98803
0.548
0.98320
0.466
0.2500
1.01065
1.118
1.00797
0.886
1.00441
0.722
1.00012
0.602
0.99527
0.518
0.5000
1.02228
1.239
1.01948
0.979
1.01583
0.796
1.01143
0.662
1.00656
0.560
0.7500
1.03318
1.371
1.03026
1.077
1.02654
0.871
1.02204
0.722
1.01712
0.610
1.0000
1.04342
1.526
1.04037
1.192
1.03660
0.960
1.03200
0.791
1.02704
0.663
8
ACCEPTED MANUSCRIPT
1.2500
1.05309
1.683
1.04990
1.305
1.04609
1.046
1.04139
0.859
1.03638
0.717
1.5000
1.06225
1.856
1.05891
1.436
1.05507
1.144
1.05027
0.935
1.04521
0.778
2.0000
1.07934
2.272
1.07569
1.726
1.07174
1.372
1.06678
1.100
1.06161
0.913
2.5000
1.09525
2.747
1.09127
2.062
1.08710
1.605
1.08202
1.286
1.07676
1.051
3.0000
1.11051
3.244
1.10614
2.399
1.10160
1.851
1.09644
1.477
1.09111
1.208
0.0000
0.99819
1.002
0.99564
0.798
0.99222
0.654
0.98803
0.548
0.98320
0.466
0.2500
1.01064
1.165
1.00771
0.919
1.00404
0.747
0.99972
0.621
0.99468
0.525
0.5000
1.02204
1.356
1.01884
1.057
1.01496
0.850
1.01038
0.702
1.00517
0.589
0.7500
1.03255
1.571
1.02917
1.214
1.02508
0.969
1.02023
0.793
1.01488
0.661
1.0000
1.04235
1.816
1.03882
1.382
1.03452
1.094
1.02948
0.889
1.02402
0.735
1.2500
1.05159
2.087
1.04791
1.573
1.04336
1.233
1.03833
0.994
1.03278
0.817
1.5000
1.06043
2.385
1.05656
D E
1.05171
1.387
1.04694
1.110
1.04133
0.907
0.798
0.99222
0.654
0.98803
0.548
0.98320
0.466
0.900
1.00774
0.734
1.00339
0.612
0.99839
0.517
1.02596
1.012
1.02216
0.821
1.01766
0.681
1.01253
0.579
I R
sodium L-valinate
sodium L-threoninate
1.786
C S U
N A
M
T P
1.439
T P E 1.03957
1.138
1.03558
0.914
1.03095
0.755
1.02573
0.633
1.636
1.05229
1.279
1.04811
1.024
1.04337
0.840
1.03807
0.701
1.856
1.06421
1.425
1.05985
1.132
1.05502
0.925
1.04966
0.767
1.07905
2.096
1.07542
1.594
1.07091
1.258
1.06598
1.021
1.06057
0.845
2.0000
1.09992
2.659
1.09612
1.993
1.09137
1.550
1.08622
1.242
1.08072
1.018
2.5000
1.11921
3.317
1.11507
2.414
1.11020
1.858
1.10480
1.482
1.09916
1.211
3.0000
1.13768
4.073
1.13292
2.986
1.12809
2.250
1.12234
1.767
1.11648
1.423
0.0000
0.99819
1.002
0.2500
1.01426
1.122
0.5000
1.02913
1.270
0.7500
1.04292
1.0000
1.05576
1.2500
1.06777
C C
1.5000
A
0.99564 1.01135
9
ACCEPTED MANUSCRIPT
sodium L-argininate 0.0000
0.99819
1.002
0.99564
0.798
0.99222
0.654
0.98803
0.548
0.98320
0.466
0.2500
1.01951
1.199
1.01646
0.963
1.01283
0.780
1.00841
0.645
1.00354
0.539
0.5000
1.03852
1.453
1.03507
1.149
1.03114
0.925
1.02647
0.759
1.02152
0.629
0.7500
1.05552
1.745
1.05177
1.361
1.04751
1.087
1.04257
0.881
1.03750
0.733
1.0000
1.07081
2.107
1.06681
1.615
1.06227
1.278
1.05711
1.033
1.05185
0.850
1.2500
1.08467
2.501
1.08047
1.907
1.07577
1.493
1.07044
1.201
1.06490
0.975
1.5000
1.09738
2.956
1.09299
2.248
1.08831
1.744
1.08289
1.384
1.07698
1.123
C S U
N A
D E
M
T P E
C C
A
10
I R
T P
ACCEPTED MANUSCRIPT The densities of five kinds of aqueous solutions of sodium amino acids have the same trend with the concentration and temperature, thus only the densities of aqueous solutions of sodium L-threoninate are shown in Fig. 4. It could be seen that the densities of aqueous solutions of sodium amino acids increase with the solution concentration, but decrease with the rise of temperature.
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Fig. 4. The densities of aqueous solutions of sodium L-threoninate ■, 293.15 K; ●, 303.15 K; ▲, 1.16 1.14
RI
1.12
SC
1.08
-3
ρ/(g·cm )
1.10
1.06
NU
1.04 1.02
MA
1.00 0.98 0.0
0.5
1.0
1.5
2.0
2.5
3.0
-1
D
m/(mol·kg )
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313.15 K; ▼, 323.15 K; ◆,333.15 K.
The apparent molar volumes (Vφ) of the aqueous solutions of sodium amino
CE
acids could be calculated from densities by the following equation [18,19]:
Vφ
M
0 m0
(2)
AC
where Vφ (m3·mol-1) is the apparent molar volume, ρ (kg·m-3) and ρ0 (kg·m-3) are the densities of the solution and the solvent, respectively, m (mol·kg-1) is the molality of the solution, and M (kg·mol-1) is the molar mass of the solute. The values of Vφ are shown in Table 3. It can been seen that the apparent molar volumes (Vφ) of the five kinds of sodium amino acids decrease in the order: Vφ(sodium L-argininate) > Vφ(sodium L-valinate) > Vφ(sodium L-threoninate) > Vφ(sodium L-alaninate) > Vφ(sodium glycinate) for the same concentration and temperature. Fig. 5 shows the trend of Vφ of aqueous solutions of sodium L-threoninate at different temperatures and 11
ACCEPTED MANUSCRIPT concentrations, and the trend of Vφ for other four kinds of aqueous solutions of sodium amino acids are the same with that of aqueous solutions of sodium L-threoninate. The apparent molar volumes (Vφ) nonlinearly increase with the increase of temperature and solution concentration. The increase of temperature could promote the molecular thermal motion and increase the intermolecular space, which
PT
would result in the increase of the apparent molar volume (Vφ). Table 3
pressure.
mol·kg-1
T/K = 293.15
SC
Vφ/(cm3·mol-1)
m/ T/K = 303.15
T/K = 313.15
0.5000
45.615
46.228
0.7500
46.317
46.981
1.0000
46.971
47.670
1.2500
47.577
1.5000
T/K = 323.15
45.887
46.311
46.423
46.687
47.080
47.196
47.426
47.794
47.913
48.105
48.453
48.576
48.296
48.723
49.057
49.183
48.134
48.858
49.281
49.606
49.736
2.0000
49.104
49.790
50.215
50.538
50.676
2.5000
49.879
50.907
51.251
51.396
3.0000
50.462
50.890
51.356
51.743
51.895
0.2500
60.555
61.072
61.658
62.132
62.264
0.5000
61.459
61.990
62.508
62.997
63.163
62.287
62.831
63.294
63.795
63.992
63.037
63.597
64.015
64.526
64.750
63.710
64.287
64.673
65.189
65.438
64.306
64.900
65.267
65.786
66.056
65.266
65.899
66.263
66.779
67.080
2.5000
65.917
66.594
67.004
67.504
67.822
3.0000
66.259
66.984
67.488
67.961
68.284
0.2500
88.322
89.960
91.115
91.870
92.943
0.5000
89.403
90.827
91.934
92.948
93.974
0.7500
90.314
91.575
92.662
93.795
94.772
1.0000
91.055
92.202
93.300
94.410
95.338
1.2500
91.624
92.709
93.848
94.792
95.672
1.2500 1.5000 2.0000
AC
1.0000
50.468
PT E
CE
sodium L-alaninate
0.7500
NU
45.411
D
44.864
T/K = 323.15
MA
sodium glycinate 0.2500
RI
Apparent molar volumes of aqueous solutions of sodium amino acids at T = (293.15 to 333.15) K under the atmospheric
sodium L-valinate
12
ACCEPTED MANUSCRIPT 1.5000
92.023
93.097
94.305
94.943
95.773
0.2500
75.667
77.135
77.951
78.696
79.467
0.5000
76.907
78.193
79.033
79.745
80.455
0.7500
78.034
79.164
80.021
80.706
81.362
1.0000
79.049
80.048
80.913
81.578
82.190
1.2500
79.951
80.846
81.711
82.362
82.938
1.5000
80.740
81.557
82.414
83.057
83.606
2.0000
81.980
82.719
83.536
84.182
2.5000
82.769
83.534
84.279
84.954
85.478
3.0000
83.107
84.002
84.643
85.373
85.934
0.2500
108.633
110.732
111.665
0.5000
111.108
113.023
0.7500
113.324
1.0000
84.701
112.729
113.036
114.188
115.345
115.760
115.082
116.378
117.587
118.132
115.283
116.909
118.236
119.456
120.152
1.2500
116.983
118.504
119.761
120.952
121.819
1.5000
118.424
119.867
120.954
122.074
123.133
-1
PT E
84
3
NU
MA D
86
V(cm ·mol )
SC
sodium L-argininate
RI
PT
sodium L-threoninate
82 80
CE
78
AC
76
0.0
0.5
1.0
1.5
2.0
2.5
3.0
-1
m/(mol·kg )
Fig. 5. The apparent molar volumes of aqueous solutions of sodium L-threoninate ■, 293.15 K; ●, 303.15 K; ▲, 313.15 K; ▼, 323.15 K; ◆,333.15 K.
The apparent molar volumes (Vφ) could be fitted by the following equation: V V0 Sv m bv m2
(3)
where Vφ0 is the limiting partial molar volume, Sv, bv are experimental parameters, and m is the molality of solution. The values of Vφ0 are obtained by the least-squares 13
ACCEPTED MANUSCRIPT regression analysis and listed in Table 4. The limiting partial molar volumes (Vφ0) of the five kinds of sodium amino acids decrease in the order: Vφ0 (sodium L-argininate) > Vφ0 (sodium L-valinate) > Vφ0 (sodium L-threoninate) > Vφ0 (sodium L-alaninate) > Vφ0 (sodium glycinate) at same temperature. The limiting partial molar volume (Vφ0) is an important parameter reflecting the solute-solvent interactions
PT
which includes electrostatic interaction and structural interaction. For the same cation of aqueous solutions of sodium amino acids, the electrostatic interaction depends on
RI
the amino acid anion. Previous study shows that the contribution of electrostatic
SC
interaction is quite small and negligible [20]. Thus, the limiting partial molar volume (Vφ0) mainly reflects the structural interaction [21] including hydrogen bond and
NU
hydrophobic hydration interactions for the studied solutions in this work. On the one hand, the stronger the hydrogen bond interaction between the polar
MA
group (-NH2) of the sodium amino acid and the hydroxyl bond of the solvent water is, the shorter the contact distance between the solute and the solvent becomes, which
D
leads to the smaller Vφ0 [22]. On the other hand, hydrophobic hydration of alkyl chain
PT E
of sodium amino acid also plays a significant role to volumetric properties. It is known that hydrophobic hydration interaction would result in an ice-like structure for water molecules around the hydrophobic group, which would lead to a larger volume
CE
and less compressibility [23]. The longest alkyl chain for the sodium L-argininate in five sodium amino acids has the strongest hydrophobic hydration interaction, while
AC
the shortest alkyl chain for the sodium glycinate results in the weakest hydrophobic hydration interaction. As we know that hydrogen bond and hydrophobic hydration interaction play the contrary roles for the volume properties. The hydrogen bond interaction has negative influence on Vφ0, while hydrophobic hydration interaction has positive influence on Vφ0. The experimental results show that hydrophobic hydration interaction is stronger than hydrogen bond interaction for the solutions studied in this work. Moreover, the limiting partial molar volumes show an increasing trend with the temperature. The increase in temperature could weaken the binding between the water 14
ACCEPTED MANUSCRIPT molecules and the terminal zwitterions of sodium amino acids, and release the solvent molecules into the bulk, which accordingly leads to an expansion in volume [24]. Table 4 The limiting partial molar volumes of aqueous solutions of sodium amino acids. Vφ0/(cm3·mol-1) T/K = 293.15
T/K = 303.15
T/K = 313.15
T/K = 323.15
T/K = 333.15
sodium glycinate
44.065
44.530
45.026
45.487
45.596
sodium L-alaninate
59.573
60.078
60.745
sodium L-valinate
87.069
88.973
90.205
sodium L-threoninate
74.314
75.990
76.774
sodium L-argininate
105.900
108.210
108.810
PT
sodium amino acid
61.295
90.559
91.679
RI
61.200
78.400
109.740
109.960
SC
77.559
NU
3.2. Viscometric properties
The measured viscosity data are shown in Table 2. The viscosity values of the
MA
solutions increase with the solution concentration and decrease with the increase of the temperature. The viscosities of five kinds of aqueous solutions of sodium amino
D
acids have the same trend with the concentration and temperature. Fig. 6 shows the
PT E
trend of viscosities of aqueous solutions of sodium L-threoninate at different temperatures and concentrations. It could be clearly seen that the viscosities of the solutions increase nonlinearly with the increase of the concentration of sodium amino
CE
acids. The increase of the solution concentration enhances the interaction between sodium amino acids and water molecules, which could decrease the distance of free
AC
movement between molecules and increase the probability of collision between molecules, consequently, leading to the loss of kinetic energy and the accumulation of molecules [25], thus the viscosities increase with the solution concentration. It could be easily found from Table 2 that the viscosities of the five kinds of aqueous solutions of sodium amino acids decrease in the order: η (sodium L-argininate) > η (sodium L-valinate) > η (sodium L-threoninate) > η (sodium L-alaninate) > η (sodium glycinate) at same temperature and concentration, which might depend on their structure and molecular weight. Moreover, the rise of temperature accelerates the 15
ACCEPTED MANUSCRIPT movement of molecules and thereby leads to the decrease of viscosity, which is consistent with the result in literature [11]. 4.0 3.5
2.5
PT
(mPa·s)
3.0
2.0
RI
1.5
0.5 0.0
0.5
1.0
1.5
SC
1.0
2.0
2.5
3.0
-1
MA
NU
m/(mol·kg ) Fig. 6. The viscosities of aqueous solutions of sodium L-threoninate ■, 293.15 K; ●, 303.15 K; ▲, 313.15 K; ▼, 323.15 K; ◆,333.15 K.
The relative viscosities (ηr) of the aqueous solutions of sodium amino acids could be correlated by the extended Jones-Dole equation [26]:
1 Bm Dm2 0
PT E
D
r
(4)
where ηr is the relative viscosity, m is the molality of solution, η and η0 are the
CE
viscosities of the aqueous solutions of sodium amino acids and the deionized water, respectively. Both B and D are the fitting parameters, B-coefficient represents the
AC
solute-solvent interaction and reflects the effects of solute size and structure, which is the main contributor to relative viscosity. D-coefficient accounts for the solute-solute interaction [27]. The standard deviation and the average deviation were calculated as follows:
n 2 SD (yexp,i ycal ,i / (n k 1 i1 AARD
1 n yexp,i ycal ,i y n i 1 exp,i 16
1/ 2
(5)
(6)
ACCEPTED MANUSCRIPT where n is the total number of experimental points and k is the number of parameters, yexp,i and ycal,i represent the experimental value and calculated value, respectively. The values of B-coefficient, D-coefficient and their deviations of SD and AARD are listed in Table 5. It could be seen that the B-coefficients of five kinds of sodium amino acids are all positive, indicating the strong solute-solvent interaction in
PT
the aqueous solutions of sodium amino acids. The B-coefficients of the five kinds of sodium amino acids decrease in the order: B (sodium L-argininate) > B (sodium
RI
L-valinate) > B (sodium L-threoninate) > B (sodium L-alaninate) > B (sodium
SC
glycinate). The sodium L-argininate with complex structure and large volume has the large B-coefficient, the sodium glycinate with simple structure has the small
NU
B-coefficient. It indicates that the B-coefficient is closely related to the structure and
MA
size of the solute molecule [28].
Table 5
B-coefficients, D-coefficients and their deviations of SD and AARD and the solvation numbers B/Vφ0 of aqueous solutions of
D/(kg2·mol-2)
100 AARD
SD/mPa·s
0.340
0.044
0.34
0.007
7.72
0.329
0.047
0.34
0.006
7.39
0.322
0.041
0.32
0.005
7.15
0.316
0.035
0.28
0.004
6.95
0.314
0.029
0.38
0.004
6.89
293.15
0.405
0.114
0.31
0.009
6.80
303.15
0.402
0.090
0.28
0.007
6.69
313.15
0.395
0.073
0.32
0.006
6.50
323.15
0.379
0.062
0.15
0.002
6.19
333.15
0.369
0.054
0.34
0.004
6.02
293.15
0.597
0.215
0.02
0.001
6.86
303.15
0.560
0.176
0.11
0.002
6.29
313.15
0.530
0.144
0.09
0.002
5.88
323.15
0.505
0.119
0.08
0.001
5.58
T/(K) sodium glycinate 293.15 303.15
323.15 333.15
CE
313.15
PT E
B/(kg·mol-1)
D
sodium amino acids.
B/Vφ0
AC
sodium L-alaninate
sodium L-valinate
17
ACCEPTED MANUSCRIPT 333.15
0.478
0.101
0.08
0.001
5.21
293.15
0.437
0.195
0.05
0.001
5.88
303.15
0.434
0.157
0.60
0.017
5.71
313.15
0.430
0.126
0.42
0.004
5.60
323.15
0.420
0.107
0.29
0.004
5.42
333.15
0.408
0.092
0.27
0.003
5.20
293.15
0.692
0.406
0.15
0.005
6.53
303.15
0.687
0.346
0.46
0.009
6.35
313.15
0.666
0.293
0.34
0.006
6.12
323.15
0.626
0.261
0.23
0.003
5.70
333.15
0.582
0.237
0.18
0.002
5.29
sodium L-threoninate
SC
RI
PT
sodium L-argininate
NU
It could be seen from the Table 5 that the B-coefficients of five kinds of aqueous solutions of sodium amino acids decrease with the increase of the temperature,
MA
implying that the temperature coefficients (dB/dT) are negative. In general, the positive and negative values of dB/dT could better reflect the structural action of
D
solute in the solvent. When the value of dB/dT is positive, the solute is more likely to
PT E
be structure-breaker in the solution, whereas the negative dB/dT demonstrates that the solute prefers to act as structure-maker [29-31]. Five kinds of sodium amino acids in this work act as structure-makers in aqueous solution.
CE
The phenomenon that the solute molecules are surrounded by solvent molecules in multicomponent solutions is called solvation effect. The solvation number (B/Vφ0)
AC
could be obtained by B-coefficient and the limiting partial molar volume [32]. The values of the solvation number (B/Vφ0) are shown in Table 5. The solvation number (B/Vφ0) decreases with the increase of temperature, which is consistent with the change of B-coefficient. The figures of lnη vs. 1/T for five kinds of aqueous solutions of sodium amino acids have the same trend with the concentration and temperature. Fig. 7 shows the trend of lnη vs. 1/T of aqueous solutions of sodium L-threoninate. It could be seen that lnη has a linear relationship with 1/T. The Arrhenius equation could be used to 18
ACCEPTED MANUSCRIPT calculate the activation energy for viscous flow (Ea) [33]: ln(η / mPa s) ln(η / mPa s) Ea / RT
(7)
where η∞ is the viscosity at infinite temperature, R is the gas constant and Ea is the activation energy for viscous flow which is the energy barrier that must be overcome in the flow [34]. The large Ea illustrates the more difficulty for the flow. The values of
PT
Ea could be calculated through the slope (Ea/R) of equation (7), which are listed in Table 6. Among the five kinds of aqueous solutions of sodium amino acids, the
RI
sodium L-argininate has the largest activation energy for the viscous flow, and the
SC
sodium glycinate has the smallest activation energy for the viscous flow. The increase of solution concentration leads to the decrease of the intermolecular distance and the
NU
increase of interactions in the solution [35], which results in the increase of Ea.
MA
1.5
1.0
D
PT E
ln(mPa·s)
0.5
0.0
CE
-0.5
0.0030
0.0031
0.0032
0.0033
0.0034
-1
(1/T)/(K )
AC
-1.0
Fig. 7. lnη vs. 1/T of aqueous solutions of sodium L-threoninate ■,0.0000 mol·kg-1; ●,0.2500 mol·kg-1 ▲,0.5000 mol·kg-1; ▼, 0.7500 mol·kg-1; ◆, 1.0000 mol·kg-1; ◀, 1.2500 mol·kg-1; ▶ 1.5000 mol·kg-1; ⊗ 2.0000 mol·kg-1; ★2.5000 mol·kg-1; * 3.0000 mol·kg-1; Table 6 Activation energies for viscous flow of aqueous solutions of sodium amino acids. m
Ea
η∞
Ea
η∞
Ea
η∞
Ea
η∞
Ea
η∞
mol·kg1
kJ·mol-1
mPa.s
kJ·mol-1
mPa.s
kJ·mol-1
mPa.s
kJ·mol-1
mPa.s
kJ·mol-1
mPa.s
sodium glycinate
sodium L-alaninate
sodium L-valinate
19
sodium L-threoninate
sodium L-argininate
ACCEPTED MANUSCRIPT 15.51
0.0017
15.51
0.0017
15.51
0.0017
15.51
0.0017
15.51
0.0017
0.2500
15.64
0.0018
15.67
0.0018
16.15
0.0015
15.72
0.0018
16.25
0.0015
0.5000
15.80
0.0018
16.12
0.0016
16.89
0.0013
16.01
0.0018
16.98
0.0014
0.7500
15.95
0.0018
16.44
0.0016
17.55
0.0012
16.70
0.0015
17.64
0.0012
1.0000
16.05
0.0019
16.88
0.0015
18.31
0.0010
17.19
0.0014
18.40
0.0011
1.2500
16.38
0.0018
17.29
0.0014
18.99
0.0009
17.89
0.0012
19.08
0.0010
1.5000
16.54
0.0018
17.64
0.0013
19.59
0.0008
18.40
0.0011
19.68
0.0009
2.0000
16.76
0.0019
18.49
0.0011
---
---
19.47
0.0009
---
---
2.5000
17.19
0.0018
19.48
0.0009
---
---
20.37
0.0008
---
---
3.0000
17.48
0.0019
20.03
0.0009
---
---
21.38
0.0006
---
---
RI
SC
NU
3.3. Group contribution method
PT
0.0000
For the structures of sodium glycinate, sodium L-alaninate and sodium
MA
L-valinate only contain the terminal group and the alkyl chain, the limiting partial molar volume of the three sodium amino acids could be expressed as follows:
D
Vφ0 Vφ0 (NH2 ,COONa) ncVφ0 (CH2 )
(8)
PT E
where nc is the number of carbon atoms in the alkyl chain of sodium amino acid molecule. The values of Vφ0 (NH2 ,COONa) and Vφ 0 (CH 2 ) could be obtained by
CE
equation (8). Besides, it is assumed that the following relationship exists between
AC
methyl, methylene and methine [36,37]:
V0 (CH3 ) 1.5V0 (CH2 )
(9)
V0 (CH) 0.5V0 (CH2 )
(10)
where Vφ 0 (CH 2 ) is the average of the contribution values of the CH and CH3 groups to the limiting partial molar volume (Vφ0). According to the group contribution method, the limiting partial molar volume could be regarded as the sum of the contribution of each group to the limiting partial molar volume:
20
ACCEPTED MANUSCRIPT n
0 V0 nV i (i )
(11)
i 0
where ni represents the number of the i-th groups, Vφ0(i) is the contribution of the i-th group to the limiting partial molar volume. The value of V0 (OH) of sodium L-threoninate and the value of V0 (CNHNHNH2 ) of sodium L-argininate could be
PT
calculated by the following equations [38]:
Vφ0 (OH) = Vφ0 ( sodium L-threoninate)- Vφ0 (NH2,COONa)-2 Vφ0 (CH)-Vφ0 (CH3)
RI
(12)
SC
Vφ0 (CNHNHNH2) = Vφ0 ( sodium L-argininate)- Vφ0 (NH2,COONa)-3 Vφ0 (CH2)-Vφ0 (CH) (13) The group contribution values calculated by equation (8-13) are listed in Table 7.
NU
The group contribution values of the limiting partial molar volume (Vφ0) decrease in
MA
the order: Vφ0 (NH2,COONa) > Vφ0 (CNHNHNH2) > Vφ0 (CH3) > Vφ0 (CH2) >
Vφ0 (OH) > Vφ0 (CH). The results show that these groups have positive contributions to
D
the limiting partial molar volume (Vφ0). The CNHNHNH2- group in the sodium
PT E
L-argininate molecule has a significantly large contribution, reflecting strong
interaction between the CNHNHNH2- group and the water molecules. The CH- group has a small contribution, reflecting weak interaction between the CH- group and the
CE
water molecules. Table 7
AC
The contribution values of different groups of sodium amino acids to the limiting partial molar volume. Vφ0/(cm3·mol-1)
groups
T/K = 293.15
T/K = 303.15
T/K = 313.15
T/K = 323.15
T/K = 333.15
NH2, COONa
30.32
30.08
30.30
30.81
30.40
CH
7.13
7.38
7.51
7.49
7.67
CH2
14.25
14.76
15.01
14.98
15.34
CH3
21.38
22.14
22.52
22.46
23.01
OH
8.37
9.01
8.94
9.31
9.66
CNHNHNH2
25.70
26.46
25.96
26.52
25.88
21
ACCEPTED MANUSCRIPT 4. Conclusions In this work, the densities and viscosities of aqueous solutions of sodium glycinate, sodium L-alaninate, sodium L-valinate, sodium L-threoninate and sodium L-argininate were measured at T = (293.15 to 333.15) K under the atmospheric pressure. The effects of temperature and concentration on the densities and viscosities
PT
of binary solutions were investigated. It could be found that the densities and viscosities of aqueous solutions of sodium amino acids increase with the increase of
RI
solution concentration, but decrease with the rise of temperature. The volumetric and
SC
viscometric properties such as the apparent molar volume (Vφ), the limiting partial molar volume (Vφ0), the viscosity B-coefficient (B) and the activation energy for
NU
viscous flow (Ea) were calculated according to the measured densities and viscosities. The limiting partial molar volumes (Vφ0) of the five kinds of sodium amino acids
MA
decrease in the order: Vφ0 (sodium L-argininate) > Vφ0 (sodium L-valinate) > Vφ0 (sodium L-threoninate) > Vφ0 (sodium L-alaninate) > Vφ0 (sodium glycinate) at same
D
temperature. The limiting partial molar volumes (Vφ0) were analyzed through
PT E
hydrogen bond and hydrophobic hydration interactions between molecules. The B-coefficients of five kinds of sodium amino acids are positive and decrease in the order: B (sodium L-argininate) > B (sodium L-valinate) > B (sodium L- threoninate) >
CE
B (sodium L-alaninate) > B (sodium glycinate). The values of temperature coefficients (dB/dT) of five kinds of sodium amino acids are negative, which means that they act
AC
as structure-makers in aqueous solution. The group contribution method was utilized to analyze the limiting partial molar volume (Vφ0), and the contribution values of the end group (-NH2,-COONa), CH- group, CH2- group, CH3- group, OH- group and CNHNHNH2- group were obtained, showing positive contributions to the limiting partial molar volume (Vφ0). Acknowledgments Supported by the National Nature Science Foundation of China (No. 21776200, 21576186, 91434204), the Tianjin Natural Science Foundation (13JCQNJC05500). 22
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PT
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RI
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SC
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D
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PT E
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AC
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PT
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RI
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NU
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MA
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D
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PT E
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ACCEPTED MANUSCRIPT temperature ionic liquids, J. Electroanal. Chem. 568 (2004) 167-181. [36] H. Shekaari, F. Jebali, Densities, viscosities, electrical conductances, and refractive indices of amino acid + ionic liquid ([BMIm]Br) + water mixtures at 298.15 K, J. Chem. Eng. Data 55 (2010) 2517-2523. [37] A. Ali, S. Sabir, H.S. Shahjahan, Volumetric and refractive index behaviour of
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Graphical abstract
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ACCEPTED MANUSCRIPT Highlights
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Densities and viscosities of sodium amino acids aqueous solutions were measured. Volumetric and viscometric properties were obtained from experimental data and analyzed through intermolecular interaction. Group contribution method was utilized to analyze limiting partial molar volume.
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Chunyan Chu, Chunying Zhu, Taotao Fu, Youguang Ma PII: DOI: Reference:
S0167-7322(17)34235-6 https://doi.org/10.1016/j.molliq.2018.01.058 MOLLIQ 8512
To appear in:
Journal of Molecular Liquids
Received date: Revised date: Accepted date:
12 September 2017 22 December 2017 9 January 2018
Please cite this article as: Chunyan Chu, Chunying Zhu, Taotao Fu, Youguang Ma , Volumetric and viscometric properties of aqueous solutions of sodium amino acids at T = (293.15 to 333.15) K. The address for the corresponding author was captured as affiliation for all authors. Please check if appropriate. Molliq(2017), https://doi.org/ 10.1016/j.molliq.2018.01.058
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ACCEPTED MANUSCRIPT Volumetric and viscometric properties of aqueous solutions of sodium amino acids at T = (293.15 to 333.15) K Chunyan Chu, Chunying Zhu, Taotao Fu, Youguang Ma* State Key Laboratory of Chemical Engineering, Collaborative Innovation Center of Chemical science and Engineering, School of Chemical Engineering and Technology,
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Tianjin University, Tianjin 300072, PR China
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ABSTRACT
The densities and viscosities of aqueous solutions of sodium glycinate, sodium
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L-alaninate, sodium L-valinate, sodium L-threoninate and sodium L-argininate were
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measured at T = (293.15 to 333.15) K under the atmospheric pressure. The effects of temperature and concentration on the densities and viscosities of binary solutions
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were investigated. The volumetric and viscometric properties such as the apparent molar volume (Vφ), the limiting partial molar volume (Vφ0), the viscosity B-coefficient (B) and the activation energy for viscous flow (Ea) were calculated by the
D
experimental density and viscosity data and analyzed based on the molecular structure
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and intermolecular interaction. Moreover, the group contribution method was utilized to study the limiting partial molar volume (Vφ0), and the contributions of the end
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group (-NH2,-COONa), CH- group, CH2- group, CH3- group, OH- group and CNHNHNH2- group to the limiting partial molar volume (Vφ0) were obtained. The
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results show that all these groups have positive contributions to the limiting partial molar volume (Vφ0). Keywords: Sodium amino acid; Density; Viscosity; Apparent molar volume; B-coefficient
1. Introduction In recent years, the global warming stemming from greenhouse effect has become one of the focuses of worldwide concerns. Among all kinds of greenhouse
Corresponding author. E-mail: [email protected] (C. Zhu). 1
ACCEPTED MANUSCRIPT gases, CO2 is the predominant contributor. Consequently, the capture and reuse of CO2 is an effective way to reduce the release of CO2 [1]. At present, chemical absorption method has been extensively applied for CO2 capture in which absorbent is one the key issues, thus the exploration of absorbent with excellent performance is of great importance. In industry, aqueous solutions of monoethanolamine (MEA),
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methyl-diethanolamine (MDEA) and other alcohol amine have been widely used for CO2 absorption [2]. However, the aqueous solutions of alcohol amine have the
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disadvantages of corrosion, solvothermal degradation and high regenerative energy
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consumption, greatly limiting the application in the large-scale capture and separation of CO2. Compared with traditional alcohol amines such as MEA and MDEA aqueous
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solutions, the amino acid salt solutions have these advantages such as low volatility, low toxicity, antioxidant degradation and good absorption performance, and have
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accordingly received increasing attention [3-6]. Besides, simple amino acid salts have catalytic ability on the asymmetric aldol reaction, Michael addition reaction, and
D
cyanosilylation, thus they are widely used in the synthesis of organic compounds [7].
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Densities and viscosities are the basic data of physical property and indispensable for chemical design and process optimization. In addition, they are also necessary data for calculating thermodynamic properties, such as the apparent molar
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volume (Vφ) and the limiting partial molar volume (Vφ0), the viscosity B-coefficient (B) and the activation energy for viscous flow (Ea). These parameters are conducive to
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the understanding of the flow and transfer characteristics of fluid. Tirona et al. [8] measured the densities, viscosities, refractive indices and electrical conductivities of α-alanine (ALA) in aqueous solutions of sodium hydroxide and potassium hydroxide. Ziemer et al. [9] determined the densities of the aqueous solutions of sodium L-alaninate at T = (278.15 to 368.15) K under 0.35 MPa, and the apparent molar volumes (Vφ) were obtained, meanwhile, the effects of morphological and chemical relaxation on the apparent molar volumes (Vφ) were also analyzed according to Young's rule. Mondal et al. [10] measured the densities of aqueous 2
ACCEPTED MANUSCRIPT solutions of sodium glycinate, and studied the gas - liquid equilibrium of CO2 in aqueous solutions of sodium glycinate. Shaikh et al. [11] measured the densities, viscosities and refractive indices of aqueous solutions of sodium glycinate at T = (298.15 to 343.15) K and the experimental data were correlated. In addition, the volumetric properties of amino acids in salt solutions were also investigated
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experimentally. Rajagopal et al. [12] measured the densities and ultrasonic speeds of glycine, L-alanine, L-valine and L-leucine in aqueous solutions of sodium fluoride,
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and calculated a series of volumetric properties such as the apparent molar volume
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(Vφ) and the limiting partial molar volume (Vφ0). Siddique et al. [13] measured the densities of L-lysine, L-histidine and L-arginine in aqueous solutions of sodium
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acetate, potassium acetate and calcium acetate, and calculated the apparent molar volumes (Vφ) through the densities. Various interactions between amino acids and
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organic salts in these solutions were analyzed. Although the volumetric and viscometric properties of various amino acids in salt solutions have been widely
D
investigated, the volumetric and viscometric properties of aqueous solutions of
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sodium amino acids remain still scarce, which motivates us to systematically study the volumetric and viscometric properties of different kinds of aqueous solutions of sodium amino acids.
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In this paper, the densities and viscosities of aqueous solutions of sodium glycinate, sodium L-alaninate, sodium L-valinate, sodium L-threoninate and sodium
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L-argininate were systematically studied at T = (293.15 to 333.15) K under the atmospheric pressure. The volumetric and viscometric properties such as the apparent molar volume (Vφ), the limiting partial molar volume (Vφ0), the viscosity B-coefficient (B) and the activation energy for viscous flow (Ea) were calculated through density and viscosity data. The limiting partial molar volume was analyzed by means of the group contribution method, and the contribution of each group to the limiting partial molar volume was obtained.
2. Experimental section 3
ACCEPTED MANUSCRIPT 2.1. Reagents Glycine, L-alanine, L-valine, L-threonine and L-arginine are analytical reagents, and the mass fractions of amino acids are ≥ 99% except L-arginine ≥ 98%, the mass fraction of sodium hydroxide is ≥ 99.44%. The details of reagents are summarized in Table 1. The deionized water was used to prepare solutions. All solutions were
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weighed by a FA2004B balance with precision of ± 0.0001 g. Aqueous solutions of sodium amino acids were prepared by dissolving the equimolar amino acid and
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sodium hydroxide in water as introduced in the literature [8,9]. The molalities of
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sodium amino acids are from 0.0 to 3.0 mol·kg-1 with an interval of 0.25 mol·kg-1 except for the sodium L-valinate and sodium L-argininate from 0.0 to 1.5 mol·kg-1
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due to their low solubility. The structures of the five kinds of sodium amino acids are shown in Fig. 1.
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Table 1 List of experimental reagents. CAS No.
Molar mass (g·mol-1)
Source
glycine
56-40-6
75.07
Aladdin Chemical Reagent Co., Ltd.
≥ 99%
L-alanine
56-41-7
89.09
Aladdin Chemical Reagent Co., Ltd.
≥ 99%
L-valine
72-18-4
117.15
Aladdin Chemical Reagent Co., Ltd.
≥ 99%
L-threonine
72-19-5
119.12
Aladdin Chemical Reagent Co., Ltd.
≥ 99%
L-arginine
74-79-3
174.20
Aladdin Chemical Reagent Co., Ltd.
≥ 98%
1310-73-2
40.00
Aladdin Chemical Reagent Co., Ltd
≥ 99.44%
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AC
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Sodium hydroxide
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Chemical name
Fig. 1. Structures of five kinds of sodium amino acids. 4
Mass fraction purity
ACCEPTED MANUSCRIPT 2.2. Density Measurement The densities of aqueous solutions of sodium amino acids were measured by a vibrating tube density meter (Anton Paar DMA 4500 M, Austria) with an accuracy of ± 5 × 10-5 g·cm-3. The density meter was calibrated by the deionized water and dry air at 293.15 K under the atmospheric pressure. After each measurement, the density
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meter was automatically cleaned using the distilled water and anhydrous ethanol, respectively. The temperatures were automatically controlled by the instrument with
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an uncertainty of ± 0.03 K. The average value of the triplicate measurements was
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adopted as the final result of density for a given condition. In this work, the densities of pure water at different temperatures are in line with those in the literature [14,15]
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as shown in Table 2.
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2.3. Viscosity Measurement
The viscosities of aqueous solutions of sodium amino acids were measured using
D
an iVisc capillary viscometer (LAUDA, Germany), and the viscometer was calibrated
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using viscosity standard fluids. The viscometer filled with experimental solution was vertically placed in the water thermostat (the LAUDA Eco Sliver Thermostats). The temperatures of the experimental water thermostat were separately set at T = (293.15,
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303.15, 313.15, 323.15, 333.15) K with an uncertainty of ± 0.05 K. The flow times of solutions in the capillary were automatically detected by the infrared with an
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uncertainty of ± 0.01 s. Each sample was measured at least three times with a deviation of 0.2 s. The average value of the flow times was used to obtain the final viscosity.
The viscosities of solutions were calculated by the following equation [16]: η / ρ Xt K / t
(1)
where η, ρ, t are viscosity, density and flow time of the solution, respectively, X and K are the viscometer constants. The uncertainty of the viscosity is ± 0.009 mPa·s. The viscosities of pure water at different temperatures in the experiment agree well with 5
ACCEPTED MANUSCRIPT those in the literature [14,17] as shown in Table 2.
3. Results and discussion 3.1. Volumetric properties The density data of the aqueous solutions of sodium amino acids in T = (293.15, 303.15, 313.15, 323.15, 333.15) K are shown in Table 2. The comparisons of the
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densities and viscosities of aqueous solutions of sodium glycinate between experimental data and literature values are shown in Fig. 2 and 3, respectively. From
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the figures, it could be clearly seen that the experimental densities of the aqueous
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solutions of sodium glycinate show a good agreement with the literature values [10,11] except for those at the high concentration. Both the experimental viscosities and
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literature values show that the viscosities increase with the rise of the concentration. The experimental viscosities are in accord with the literature values [10] except for
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those at the high concentration, but the experimental data are smaller than those values in the literature [11] in which the viscosities show a wave tendency with
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concentration. A routine Cannon-Fenske viscometer was used to measure the
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viscosities in literature [10]. A rolling ball type viscometer (Anton Paar, Lovis-2000 M/ME) was used to measure the viscosities in literature [11]. They are different from this work (iVisc capillary viscometer, LAUDA, Germany). Moreover, the mass
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fractions of glycinate sodium salt hydrate is ≥ 99% in literature [10], and the mass fractions of glycine and sodium hydroxide are ≥ 99% in literature [11], while the mass
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fraction of glycine is ≥ 99% and sodium hydroxide is ≥ 99.44% in this study. In addition, the solutions were prepared with mass fractions in the literature [10,11], but in this work the solutions were prepared with molality. The differences of the instrument, the impurities in the reagents and the operating process might result in the deviation between the experimental data and the values in literature.
6
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1.14 1.12
/(g·cm-3)
1.10 1.08 1.06 1.04
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1.02
0.0
0.5
1.0
1.5 2.0 2.5 m/(mol·kg-1)
3.0
3.5
SC
0.98
RI
1.00
Fig. 2. Comparisons of the densities of aqueous solutions of sodium glycinate between
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experimental data and literature data □, 313.15 K; ○, 323.15 K; Δ, 333.15 K; hollow symbols for literature values in ref [10]; cross-filled symbols for literature values in ref [11];
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solid symbols for experimental data, the lines are just a guide of experimental values.
1.6
D
1.2 1.0 0.8
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0.6
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/(mPa·s)
1.4
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0.4
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
-1
m/(mol·kg )
Fig. 3. Comparisons of the viscosities of aqueous solutions of sodium glycinate between experimental data and literature data □, 313.15 K; ○, 323.15 K; Δ, 333.15 K; hollow symbols for literature values in ref [10]; cross-filled symbols for literature values in ref [11]; solid symbols for experimental data, the lines are just a guide of experimental values.
7
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Table 2. The densities, ρ and viscosities, η, of aqueous solutions of sodium amino acids at T = (293.15 to 333.15) K under the atmospheric pressure. T/K = 293.15 ρ/( g·cm )
-1
-3
m/(mol·kg )
T/K = 303.15
η/( mPa·s)
ρ/( g·cm )
T/K = 313.15
η/( mPa·s)
-3
ρ/( g·cm )
I R -3
ρ/( g·cm )
η/( mPa·s)
[13]
0.5470[13]
sodium glycinate [13]
0.99564
[13]
0.99222
[13]
0.99821
0.0000
0.998211[14]
1.0020[15]
0.995656[14]
0.7975[15]
0.0000
0.99819
1.002
0.99564
0.798
0.99222
0.2500
1.01109
1.084
1.00840
0.871
1.00486
0.5000
1.02334
1.193
1.02048
0.946
0.7500
1.03497
1.276
1.03192
1.016
1.0000
1.04604
1.392
1.04279
1.100
1.2500
1.05659
1.486
1.05315
1.5000
1.06666
1.619
1.06304
2.0000
1.08556
1.860
1.08169
2.5000
1.10312
2.130
3.0000
1.11968
2.422
0.6532
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[13]
0.6532[15]
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ρ/( g·cm-3)
0.5471[15]
η/( mPa·s)
0.4666[15]
0.548
0.98320
0.466
0.710
1.00056
0.594
0.99570
0.502
0.772
1.01244
0.645
1.00754
0.547
1.02817
0.825
1.02371
0.688
1.01878
0.582
1.03895
0.894
1.03442
0.744
1.02947
0.631
1.187
1.04921
0.952
1.04462
0.789
1.03966
0.666
1.271
1.05902
1.035
1.05438
0.851
1.04939
0.716
1.470
1.07748
1.182
1.07272
0.972
1.06769
0.816
1.09918
1.681
1.09476
1.343
1.08984
1.099
1.08476
0.915
1.11595
1.932
1.11128
1.528
1.10611
1.243
1.10099
1.030
PT
D E
A M 1.01683
0.654
0.98805
T/K = 333.15
0.98803
E C
C A
0.7977
[13]
0.0000
sodium L-alaninate
1.0020
[13]
T P
T/K = 323.15
η/( mPa·s)
-3
0.0000
0.99819
1.002
0.99564
0.798
0.99222
0.654
0.98803
0.548
0.98320
0.466
0.2500
1.01065
1.118
1.00797
0.886
1.00441
0.722
1.00012
0.602
0.99527
0.518
0.5000
1.02228
1.239
1.01948
0.979
1.01583
0.796
1.01143
0.662
1.00656
0.560
0.7500
1.03318
1.371
1.03026
1.077
1.02654
0.871
1.02204
0.722
1.01712
0.610
1.0000
1.04342
1.526
1.04037
1.192
1.03660
0.960
1.03200
0.791
1.02704
0.663
8
ACCEPTED MANUSCRIPT
1.2500
1.05309
1.683
1.04990
1.305
1.04609
1.046
1.04139
0.859
1.03638
0.717
1.5000
1.06225
1.856
1.05891
1.436
1.05507
1.144
1.05027
0.935
1.04521
0.778
2.0000
1.07934
2.272
1.07569
1.726
1.07174
1.372
1.06678
1.100
1.06161
0.913
2.5000
1.09525
2.747
1.09127
2.062
1.08710
1.605
1.08202
1.286
1.07676
1.051
3.0000
1.11051
3.244
1.10614
2.399
1.10160
1.851
1.09644
1.477
1.09111
1.208
0.0000
0.99819
1.002
0.99564
0.798
0.99222
0.654
0.98803
0.548
0.98320
0.466
0.2500
1.01064
1.165
1.00771
0.919
1.00404
0.747
0.99972
0.621
0.99468
0.525
0.5000
1.02204
1.356
1.01884
1.057
1.01496
0.850
1.01038
0.702
1.00517
0.589
0.7500
1.03255
1.571
1.02917
1.214
1.02508
0.969
1.02023
0.793
1.01488
0.661
1.0000
1.04235
1.816
1.03882
1.382
1.03452
1.094
1.02948
0.889
1.02402
0.735
1.2500
1.05159
2.087
1.04791
1.573
1.04336
1.233
1.03833
0.994
1.03278
0.817
1.5000
1.06043
2.385
1.05656
D E
1.05171
1.387
1.04694
1.110
1.04133
0.907
0.798
0.99222
0.654
0.98803
0.548
0.98320
0.466
0.900
1.00774
0.734
1.00339
0.612
0.99839
0.517
1.02596
1.012
1.02216
0.821
1.01766
0.681
1.01253
0.579
I R
sodium L-valinate
sodium L-threoninate
1.786
C S U
N A
M
T P
1.439
T P E 1.03957
1.138
1.03558
0.914
1.03095
0.755
1.02573
0.633
1.636
1.05229
1.279
1.04811
1.024
1.04337
0.840
1.03807
0.701
1.856
1.06421
1.425
1.05985
1.132
1.05502
0.925
1.04966
0.767
1.07905
2.096
1.07542
1.594
1.07091
1.258
1.06598
1.021
1.06057
0.845
2.0000
1.09992
2.659
1.09612
1.993
1.09137
1.550
1.08622
1.242
1.08072
1.018
2.5000
1.11921
3.317
1.11507
2.414
1.11020
1.858
1.10480
1.482
1.09916
1.211
3.0000
1.13768
4.073
1.13292
2.986
1.12809
2.250
1.12234
1.767
1.11648
1.423
0.0000
0.99819
1.002
0.2500
1.01426
1.122
0.5000
1.02913
1.270
0.7500
1.04292
1.0000
1.05576
1.2500
1.06777
C C
1.5000
A
0.99564 1.01135
9
ACCEPTED MANUSCRIPT
sodium L-argininate 0.0000
0.99819
1.002
0.99564
0.798
0.99222
0.654
0.98803
0.548
0.98320
0.466
0.2500
1.01951
1.199
1.01646
0.963
1.01283
0.780
1.00841
0.645
1.00354
0.539
0.5000
1.03852
1.453
1.03507
1.149
1.03114
0.925
1.02647
0.759
1.02152
0.629
0.7500
1.05552
1.745
1.05177
1.361
1.04751
1.087
1.04257
0.881
1.03750
0.733
1.0000
1.07081
2.107
1.06681
1.615
1.06227
1.278
1.05711
1.033
1.05185
0.850
1.2500
1.08467
2.501
1.08047
1.907
1.07577
1.493
1.07044
1.201
1.06490
0.975
1.5000
1.09738
2.956
1.09299
2.248
1.08831
1.744
1.08289
1.384
1.07698
1.123
C S U
N A
D E
M
T P E
C C
A
10
I R
T P
ACCEPTED MANUSCRIPT The densities of five kinds of aqueous solutions of sodium amino acids have the same trend with the concentration and temperature, thus only the densities of aqueous solutions of sodium L-threoninate are shown in Fig. 4. It could be seen that the densities of aqueous solutions of sodium amino acids increase with the solution concentration, but decrease with the rise of temperature.
PT
Fig. 4. The densities of aqueous solutions of sodium L-threoninate ■, 293.15 K; ●, 303.15 K; ▲, 1.16 1.14
RI
1.12
SC
1.08
-3
ρ/(g·cm )
1.10
1.06
NU
1.04 1.02
MA
1.00 0.98 0.0
0.5
1.0
1.5
2.0
2.5
3.0
-1
D
m/(mol·kg )
PT E
313.15 K; ▼, 323.15 K; ◆,333.15 K.
The apparent molar volumes (Vφ) of the aqueous solutions of sodium amino
CE
acids could be calculated from densities by the following equation [18,19]:
Vφ
M
0 m0
(2)
AC
where Vφ (m3·mol-1) is the apparent molar volume, ρ (kg·m-3) and ρ0 (kg·m-3) are the densities of the solution and the solvent, respectively, m (mol·kg-1) is the molality of the solution, and M (kg·mol-1) is the molar mass of the solute. The values of Vφ are shown in Table 3. It can been seen that the apparent molar volumes (Vφ) of the five kinds of sodium amino acids decrease in the order: Vφ(sodium L-argininate) > Vφ(sodium L-valinate) > Vφ(sodium L-threoninate) > Vφ(sodium L-alaninate) > Vφ(sodium glycinate) for the same concentration and temperature. Fig. 5 shows the trend of Vφ of aqueous solutions of sodium L-threoninate at different temperatures and 11
ACCEPTED MANUSCRIPT concentrations, and the trend of Vφ for other four kinds of aqueous solutions of sodium amino acids are the same with that of aqueous solutions of sodium L-threoninate. The apparent molar volumes (Vφ) nonlinearly increase with the increase of temperature and solution concentration. The increase of temperature could promote the molecular thermal motion and increase the intermolecular space, which
PT
would result in the increase of the apparent molar volume (Vφ). Table 3
pressure.
mol·kg-1
T/K = 293.15
SC
Vφ/(cm3·mol-1)
m/ T/K = 303.15
T/K = 313.15
0.5000
45.615
46.228
0.7500
46.317
46.981
1.0000
46.971
47.670
1.2500
47.577
1.5000
T/K = 323.15
45.887
46.311
46.423
46.687
47.080
47.196
47.426
47.794
47.913
48.105
48.453
48.576
48.296
48.723
49.057
49.183
48.134
48.858
49.281
49.606
49.736
2.0000
49.104
49.790
50.215
50.538
50.676
2.5000
49.879
50.907
51.251
51.396
3.0000
50.462
50.890
51.356
51.743
51.895
0.2500
60.555
61.072
61.658
62.132
62.264
0.5000
61.459
61.990
62.508
62.997
63.163
62.287
62.831
63.294
63.795
63.992
63.037
63.597
64.015
64.526
64.750
63.710
64.287
64.673
65.189
65.438
64.306
64.900
65.267
65.786
66.056
65.266
65.899
66.263
66.779
67.080
2.5000
65.917
66.594
67.004
67.504
67.822
3.0000
66.259
66.984
67.488
67.961
68.284
0.2500
88.322
89.960
91.115
91.870
92.943
0.5000
89.403
90.827
91.934
92.948
93.974
0.7500
90.314
91.575
92.662
93.795
94.772
1.0000
91.055
92.202
93.300
94.410
95.338
1.2500
91.624
92.709
93.848
94.792
95.672
1.2500 1.5000 2.0000
AC
1.0000
50.468
PT E
CE
sodium L-alaninate
0.7500
NU
45.411
D
44.864
T/K = 323.15
MA
sodium glycinate 0.2500
RI
Apparent molar volumes of aqueous solutions of sodium amino acids at T = (293.15 to 333.15) K under the atmospheric
sodium L-valinate
12
ACCEPTED MANUSCRIPT 1.5000
92.023
93.097
94.305
94.943
95.773
0.2500
75.667
77.135
77.951
78.696
79.467
0.5000
76.907
78.193
79.033
79.745
80.455
0.7500
78.034
79.164
80.021
80.706
81.362
1.0000
79.049
80.048
80.913
81.578
82.190
1.2500
79.951
80.846
81.711
82.362
82.938
1.5000
80.740
81.557
82.414
83.057
83.606
2.0000
81.980
82.719
83.536
84.182
2.5000
82.769
83.534
84.279
84.954
85.478
3.0000
83.107
84.002
84.643
85.373
85.934
0.2500
108.633
110.732
111.665
0.5000
111.108
113.023
0.7500
113.324
1.0000
84.701
112.729
113.036
114.188
115.345
115.760
115.082
116.378
117.587
118.132
115.283
116.909
118.236
119.456
120.152
1.2500
116.983
118.504
119.761
120.952
121.819
1.5000
118.424
119.867
120.954
122.074
123.133
-1
PT E
84
3
NU
MA D
86
V(cm ·mol )
SC
sodium L-argininate
RI
PT
sodium L-threoninate
82 80
CE
78
AC
76
0.0
0.5
1.0
1.5
2.0
2.5
3.0
-1
m/(mol·kg )
Fig. 5. The apparent molar volumes of aqueous solutions of sodium L-threoninate ■, 293.15 K; ●, 303.15 K; ▲, 313.15 K; ▼, 323.15 K; ◆,333.15 K.
The apparent molar volumes (Vφ) could be fitted by the following equation: V V0 Sv m bv m2
(3)
where Vφ0 is the limiting partial molar volume, Sv, bv are experimental parameters, and m is the molality of solution. The values of Vφ0 are obtained by the least-squares 13
ACCEPTED MANUSCRIPT regression analysis and listed in Table 4. The limiting partial molar volumes (Vφ0) of the five kinds of sodium amino acids decrease in the order: Vφ0 (sodium L-argininate) > Vφ0 (sodium L-valinate) > Vφ0 (sodium L-threoninate) > Vφ0 (sodium L-alaninate) > Vφ0 (sodium glycinate) at same temperature. The limiting partial molar volume (Vφ0) is an important parameter reflecting the solute-solvent interactions
PT
which includes electrostatic interaction and structural interaction. For the same cation of aqueous solutions of sodium amino acids, the electrostatic interaction depends on
RI
the amino acid anion. Previous study shows that the contribution of electrostatic
SC
interaction is quite small and negligible [20]. Thus, the limiting partial molar volume (Vφ0) mainly reflects the structural interaction [21] including hydrogen bond and
NU
hydrophobic hydration interactions for the studied solutions in this work. On the one hand, the stronger the hydrogen bond interaction between the polar
MA
group (-NH2) of the sodium amino acid and the hydroxyl bond of the solvent water is, the shorter the contact distance between the solute and the solvent becomes, which
D
leads to the smaller Vφ0 [22]. On the other hand, hydrophobic hydration of alkyl chain
PT E
of sodium amino acid also plays a significant role to volumetric properties. It is known that hydrophobic hydration interaction would result in an ice-like structure for water molecules around the hydrophobic group, which would lead to a larger volume
CE
and less compressibility [23]. The longest alkyl chain for the sodium L-argininate in five sodium amino acids has the strongest hydrophobic hydration interaction, while
AC
the shortest alkyl chain for the sodium glycinate results in the weakest hydrophobic hydration interaction. As we know that hydrogen bond and hydrophobic hydration interaction play the contrary roles for the volume properties. The hydrogen bond interaction has negative influence on Vφ0, while hydrophobic hydration interaction has positive influence on Vφ0. The experimental results show that hydrophobic hydration interaction is stronger than hydrogen bond interaction for the solutions studied in this work. Moreover, the limiting partial molar volumes show an increasing trend with the temperature. The increase in temperature could weaken the binding between the water 14
ACCEPTED MANUSCRIPT molecules and the terminal zwitterions of sodium amino acids, and release the solvent molecules into the bulk, which accordingly leads to an expansion in volume [24]. Table 4 The limiting partial molar volumes of aqueous solutions of sodium amino acids. Vφ0/(cm3·mol-1) T/K = 293.15
T/K = 303.15
T/K = 313.15
T/K = 323.15
T/K = 333.15
sodium glycinate
44.065
44.530
45.026
45.487
45.596
sodium L-alaninate
59.573
60.078
60.745
sodium L-valinate
87.069
88.973
90.205
sodium L-threoninate
74.314
75.990
76.774
sodium L-argininate
105.900
108.210
108.810
PT
sodium amino acid
61.295
90.559
91.679
RI
61.200
78.400
109.740
109.960
SC
77.559
NU
3.2. Viscometric properties
The measured viscosity data are shown in Table 2. The viscosity values of the
MA
solutions increase with the solution concentration and decrease with the increase of the temperature. The viscosities of five kinds of aqueous solutions of sodium amino
D
acids have the same trend with the concentration and temperature. Fig. 6 shows the
PT E
trend of viscosities of aqueous solutions of sodium L-threoninate at different temperatures and concentrations. It could be clearly seen that the viscosities of the solutions increase nonlinearly with the increase of the concentration of sodium amino
CE
acids. The increase of the solution concentration enhances the interaction between sodium amino acids and water molecules, which could decrease the distance of free
AC
movement between molecules and increase the probability of collision between molecules, consequently, leading to the loss of kinetic energy and the accumulation of molecules [25], thus the viscosities increase with the solution concentration. It could be easily found from Table 2 that the viscosities of the five kinds of aqueous solutions of sodium amino acids decrease in the order: η (sodium L-argininate) > η (sodium L-valinate) > η (sodium L-threoninate) > η (sodium L-alaninate) > η (sodium glycinate) at same temperature and concentration, which might depend on their structure and molecular weight. Moreover, the rise of temperature accelerates the 15
ACCEPTED MANUSCRIPT movement of molecules and thereby leads to the decrease of viscosity, which is consistent with the result in literature [11]. 4.0 3.5
2.5
PT
(mPa·s)
3.0
2.0
RI
1.5
0.5 0.0
0.5
1.0
1.5
SC
1.0
2.0
2.5
3.0
-1
MA
NU
m/(mol·kg ) Fig. 6. The viscosities of aqueous solutions of sodium L-threoninate ■, 293.15 K; ●, 303.15 K; ▲, 313.15 K; ▼, 323.15 K; ◆,333.15 K.
The relative viscosities (ηr) of the aqueous solutions of sodium amino acids could be correlated by the extended Jones-Dole equation [26]:
1 Bm Dm2 0
PT E
D
r
(4)
where ηr is the relative viscosity, m is the molality of solution, η and η0 are the
CE
viscosities of the aqueous solutions of sodium amino acids and the deionized water, respectively. Both B and D are the fitting parameters, B-coefficient represents the
AC
solute-solvent interaction and reflects the effects of solute size and structure, which is the main contributor to relative viscosity. D-coefficient accounts for the solute-solute interaction [27]. The standard deviation and the average deviation were calculated as follows:
n 2 SD (yexp,i ycal ,i / (n k 1 i1 AARD
1 n yexp,i ycal ,i y n i 1 exp,i 16
1/ 2
(5)
(6)
ACCEPTED MANUSCRIPT where n is the total number of experimental points and k is the number of parameters, yexp,i and ycal,i represent the experimental value and calculated value, respectively. The values of B-coefficient, D-coefficient and their deviations of SD and AARD are listed in Table 5. It could be seen that the B-coefficients of five kinds of sodium amino acids are all positive, indicating the strong solute-solvent interaction in
PT
the aqueous solutions of sodium amino acids. The B-coefficients of the five kinds of sodium amino acids decrease in the order: B (sodium L-argininate) > B (sodium
RI
L-valinate) > B (sodium L-threoninate) > B (sodium L-alaninate) > B (sodium
SC
glycinate). The sodium L-argininate with complex structure and large volume has the large B-coefficient, the sodium glycinate with simple structure has the small
NU
B-coefficient. It indicates that the B-coefficient is closely related to the structure and
MA
size of the solute molecule [28].
Table 5
B-coefficients, D-coefficients and their deviations of SD and AARD and the solvation numbers B/Vφ0 of aqueous solutions of
D/(kg2·mol-2)
100 AARD
SD/mPa·s
0.340
0.044
0.34
0.007
7.72
0.329
0.047
0.34
0.006
7.39
0.322
0.041
0.32
0.005
7.15
0.316
0.035
0.28
0.004
6.95
0.314
0.029
0.38
0.004
6.89
293.15
0.405
0.114
0.31
0.009
6.80
303.15
0.402
0.090
0.28
0.007
6.69
313.15
0.395
0.073
0.32
0.006
6.50
323.15
0.379
0.062
0.15
0.002
6.19
333.15
0.369
0.054
0.34
0.004
6.02
293.15
0.597
0.215
0.02
0.001
6.86
303.15
0.560
0.176
0.11
0.002
6.29
313.15
0.530
0.144
0.09
0.002
5.88
323.15
0.505
0.119
0.08
0.001
5.58
T/(K) sodium glycinate 293.15 303.15
323.15 333.15
CE
313.15
PT E
B/(kg·mol-1)
D
sodium amino acids.
B/Vφ0
AC
sodium L-alaninate
sodium L-valinate
17
ACCEPTED MANUSCRIPT 333.15
0.478
0.101
0.08
0.001
5.21
293.15
0.437
0.195
0.05
0.001
5.88
303.15
0.434
0.157
0.60
0.017
5.71
313.15
0.430
0.126
0.42
0.004
5.60
323.15
0.420
0.107
0.29
0.004
5.42
333.15
0.408
0.092
0.27
0.003
5.20
293.15
0.692
0.406
0.15
0.005
6.53
303.15
0.687
0.346
0.46
0.009
6.35
313.15
0.666
0.293
0.34
0.006
6.12
323.15
0.626
0.261
0.23
0.003
5.70
333.15
0.582
0.237
0.18
0.002
5.29
sodium L-threoninate
SC
RI
PT
sodium L-argininate
NU
It could be seen from the Table 5 that the B-coefficients of five kinds of aqueous solutions of sodium amino acids decrease with the increase of the temperature,
MA
implying that the temperature coefficients (dB/dT) are negative. In general, the positive and negative values of dB/dT could better reflect the structural action of
D
solute in the solvent. When the value of dB/dT is positive, the solute is more likely to
PT E
be structure-breaker in the solution, whereas the negative dB/dT demonstrates that the solute prefers to act as structure-maker [29-31]. Five kinds of sodium amino acids in this work act as structure-makers in aqueous solution.
CE
The phenomenon that the solute molecules are surrounded by solvent molecules in multicomponent solutions is called solvation effect. The solvation number (B/Vφ0)
AC
could be obtained by B-coefficient and the limiting partial molar volume [32]. The values of the solvation number (B/Vφ0) are shown in Table 5. The solvation number (B/Vφ0) decreases with the increase of temperature, which is consistent with the change of B-coefficient. The figures of lnη vs. 1/T for five kinds of aqueous solutions of sodium amino acids have the same trend with the concentration and temperature. Fig. 7 shows the trend of lnη vs. 1/T of aqueous solutions of sodium L-threoninate. It could be seen that lnη has a linear relationship with 1/T. The Arrhenius equation could be used to 18
ACCEPTED MANUSCRIPT calculate the activation energy for viscous flow (Ea) [33]: ln(η / mPa s) ln(η / mPa s) Ea / RT
(7)
where η∞ is the viscosity at infinite temperature, R is the gas constant and Ea is the activation energy for viscous flow which is the energy barrier that must be overcome in the flow [34]. The large Ea illustrates the more difficulty for the flow. The values of
PT
Ea could be calculated through the slope (Ea/R) of equation (7), which are listed in Table 6. Among the five kinds of aqueous solutions of sodium amino acids, the
RI
sodium L-argininate has the largest activation energy for the viscous flow, and the
SC
sodium glycinate has the smallest activation energy for the viscous flow. The increase of solution concentration leads to the decrease of the intermolecular distance and the
NU
increase of interactions in the solution [35], which results in the increase of Ea.
MA
1.5
1.0
D
PT E
ln(mPa·s)
0.5
0.0
CE
-0.5
0.0030
0.0031
0.0032
0.0033
0.0034
-1
(1/T)/(K )
AC
-1.0
Fig. 7. lnη vs. 1/T of aqueous solutions of sodium L-threoninate ■,0.0000 mol·kg-1; ●,0.2500 mol·kg-1 ▲,0.5000 mol·kg-1; ▼, 0.7500 mol·kg-1; ◆, 1.0000 mol·kg-1; ◀, 1.2500 mol·kg-1; ▶ 1.5000 mol·kg-1; ⊗ 2.0000 mol·kg-1; ★2.5000 mol·kg-1; * 3.0000 mol·kg-1; Table 6 Activation energies for viscous flow of aqueous solutions of sodium amino acids. m
Ea
η∞
Ea
η∞
Ea
η∞
Ea
η∞
Ea
η∞
mol·kg1
kJ·mol-1
mPa.s
kJ·mol-1
mPa.s
kJ·mol-1
mPa.s
kJ·mol-1
mPa.s
kJ·mol-1
mPa.s
sodium glycinate
sodium L-alaninate
sodium L-valinate
19
sodium L-threoninate
sodium L-argininate
ACCEPTED MANUSCRIPT 15.51
0.0017
15.51
0.0017
15.51
0.0017
15.51
0.0017
15.51
0.0017
0.2500
15.64
0.0018
15.67
0.0018
16.15
0.0015
15.72
0.0018
16.25
0.0015
0.5000
15.80
0.0018
16.12
0.0016
16.89
0.0013
16.01
0.0018
16.98
0.0014
0.7500
15.95
0.0018
16.44
0.0016
17.55
0.0012
16.70
0.0015
17.64
0.0012
1.0000
16.05
0.0019
16.88
0.0015
18.31
0.0010
17.19
0.0014
18.40
0.0011
1.2500
16.38
0.0018
17.29
0.0014
18.99
0.0009
17.89
0.0012
19.08
0.0010
1.5000
16.54
0.0018
17.64
0.0013
19.59
0.0008
18.40
0.0011
19.68
0.0009
2.0000
16.76
0.0019
18.49
0.0011
---
---
19.47
0.0009
---
---
2.5000
17.19
0.0018
19.48
0.0009
---
---
20.37
0.0008
---
---
3.0000
17.48
0.0019
20.03
0.0009
---
---
21.38
0.0006
---
---
RI
SC
NU
3.3. Group contribution method
PT
0.0000
For the structures of sodium glycinate, sodium L-alaninate and sodium
MA
L-valinate only contain the terminal group and the alkyl chain, the limiting partial molar volume of the three sodium amino acids could be expressed as follows:
D
Vφ0 Vφ0 (NH2 ,COONa) ncVφ0 (CH2 )
(8)
PT E
where nc is the number of carbon atoms in the alkyl chain of sodium amino acid molecule. The values of Vφ0 (NH2 ,COONa) and Vφ 0 (CH 2 ) could be obtained by
CE
equation (8). Besides, it is assumed that the following relationship exists between
AC
methyl, methylene and methine [36,37]:
V0 (CH3 ) 1.5V0 (CH2 )
(9)
V0 (CH) 0.5V0 (CH2 )
(10)
where Vφ 0 (CH 2 ) is the average of the contribution values of the CH and CH3 groups to the limiting partial molar volume (Vφ0). According to the group contribution method, the limiting partial molar volume could be regarded as the sum of the contribution of each group to the limiting partial molar volume:
20
ACCEPTED MANUSCRIPT n
0 V0 nV i (i )
(11)
i 0
where ni represents the number of the i-th groups, Vφ0(i) is the contribution of the i-th group to the limiting partial molar volume. The value of V0 (OH) of sodium L-threoninate and the value of V0 (CNHNHNH2 ) of sodium L-argininate could be
PT
calculated by the following equations [38]:
Vφ0 (OH) = Vφ0 ( sodium L-threoninate)- Vφ0 (NH2,COONa)-2 Vφ0 (CH)-Vφ0 (CH3)
RI
(12)
SC
Vφ0 (CNHNHNH2) = Vφ0 ( sodium L-argininate)- Vφ0 (NH2,COONa)-3 Vφ0 (CH2)-Vφ0 (CH) (13) The group contribution values calculated by equation (8-13) are listed in Table 7.
NU
The group contribution values of the limiting partial molar volume (Vφ0) decrease in
MA
the order: Vφ0 (NH2,COONa) > Vφ0 (CNHNHNH2) > Vφ0 (CH3) > Vφ0 (CH2) >
Vφ0 (OH) > Vφ0 (CH). The results show that these groups have positive contributions to
D
the limiting partial molar volume (Vφ0). The CNHNHNH2- group in the sodium
PT E
L-argininate molecule has a significantly large contribution, reflecting strong
interaction between the CNHNHNH2- group and the water molecules. The CH- group has a small contribution, reflecting weak interaction between the CH- group and the
CE
water molecules. Table 7
AC
The contribution values of different groups of sodium amino acids to the limiting partial molar volume. Vφ0/(cm3·mol-1)
groups
T/K = 293.15
T/K = 303.15
T/K = 313.15
T/K = 323.15
T/K = 333.15
NH2, COONa
30.32
30.08
30.30
30.81
30.40
CH
7.13
7.38
7.51
7.49
7.67
CH2
14.25
14.76
15.01
14.98
15.34
CH3
21.38
22.14
22.52
22.46
23.01
OH
8.37
9.01
8.94
9.31
9.66
CNHNHNH2
25.70
26.46
25.96
26.52
25.88
21
ACCEPTED MANUSCRIPT 4. Conclusions In this work, the densities and viscosities of aqueous solutions of sodium glycinate, sodium L-alaninate, sodium L-valinate, sodium L-threoninate and sodium L-argininate were measured at T = (293.15 to 333.15) K under the atmospheric pressure. The effects of temperature and concentration on the densities and viscosities
PT
of binary solutions were investigated. It could be found that the densities and viscosities of aqueous solutions of sodium amino acids increase with the increase of
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solution concentration, but decrease with the rise of temperature. The volumetric and
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viscometric properties such as the apparent molar volume (Vφ), the limiting partial molar volume (Vφ0), the viscosity B-coefficient (B) and the activation energy for
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viscous flow (Ea) were calculated according to the measured densities and viscosities. The limiting partial molar volumes (Vφ0) of the five kinds of sodium amino acids
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decrease in the order: Vφ0 (sodium L-argininate) > Vφ0 (sodium L-valinate) > Vφ0 (sodium L-threoninate) > Vφ0 (sodium L-alaninate) > Vφ0 (sodium glycinate) at same
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temperature. The limiting partial molar volumes (Vφ0) were analyzed through
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hydrogen bond and hydrophobic hydration interactions between molecules. The B-coefficients of five kinds of sodium amino acids are positive and decrease in the order: B (sodium L-argininate) > B (sodium L-valinate) > B (sodium L- threoninate) >
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B (sodium L-alaninate) > B (sodium glycinate). The values of temperature coefficients (dB/dT) of five kinds of sodium amino acids are negative, which means that they act
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as structure-makers in aqueous solution. The group contribution method was utilized to analyze the limiting partial molar volume (Vφ0), and the contribution values of the end group (-NH2,-COONa), CH- group, CH2- group, CH3- group, OH- group and CNHNHNH2- group were obtained, showing positive contributions to the limiting partial molar volume (Vφ0). Acknowledgments Supported by the National Nature Science Foundation of China (No. 21776200, 21576186, 91434204), the Tianjin Natural Science Foundation (13JCQNJC05500). 22
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ACCEPTED MANUSCRIPT Highlights
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Densities and viscosities of sodium amino acids aqueous solutions were measured. Volumetric and viscometric properties were obtained from experimental data and analyzed through intermolecular interaction. Group contribution method was utilized to analyze limiting partial molar volume.
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