Article pubs.acs.org/jced
Viscosities of Some Saccharides in Aqueous Solutions of PhosphateBased Inorganic Salts Parampaul K. Banipal,* Neha Aggarwal, and Tarlok S. Banipal Department of Chemistry, Guru Nanak Dev University, Amritsar 143 005, India S Supporting Information *
ABSTRACT: The viscosities η of some monosaccharides, their methyl- and deoxy- derivatives, disaccharides, and trisaccharides have been measured in (0.25, 0.5, 1.0, and 1.25) mol·kg−1 aqueous solutions of potassium phosphate (KH2PO4) and (0.5, 1.0, 1.5, and 2.0) mol·kg−1 aqueous solutions of sodium phosphate (NaH2PO4) and ammonium phosphate (NH4H2PO4) monobasic salts, and potassium phosphate (K3PO4) tribasic salt over the temperature range (288.15 to 318.15) K and at atmospheric pressure, P = 0.1 MPa. The viscosity data have been utilized to calculate the Jones−Dole viscosity Bcoefficients and their corresponding coefficients of transfer, ΔtB. The ΔtB values were found to be positive and their magnitudes vary depending on the nature of solutes and cosolutes. The dB/dT coefficients and pair ηAB and triplet ηABB interaction coefficients have also been calculated and discussed in terms of solute−solvent/cosolute interactions. The results have been compared in phosphate-based salts on the basis of the nature of the cation and anion.
1. INTRODUCTION Saccharides and their derivatives are renewable raw materials that are highly important for life and energy. These play key roles in biological phenomena including DNA and RNA fingerprinting and engineering. Saccharides participate in many biological processes, for example, L-fucose (deoxyhexose) residues in the carbohydrate chains of glycoconjugates act as cell−cell recognition sites and as important antigenic determinants such as blood group antigens. Aqueous solutions of saccharides are useful in several food processes such as in crystallization and osmotic dehydration, etc.1−7 Their hydration behavior is involved in sweet taste chemoreception and environmental stress tolerance. Deoxy derivatives of saccharides, sugar phosphates, sulfates, carboxylates, and amino sugars occur in natural products. L-Rhamnose (6-deoxy mannopyranoside) is present as glycoside in plant pigments, gums and mucilages.8−11 Viscometric properties play a key role in process design, modeling, and evaluation. The data are quite useful in various industrial and physicochemical processes like pump sizing, extraction, filtration, extrusion, purification, and in the analyses of flow conditions in food processes, that is, pasteurization, evaporation, drying, and aseptic processing. The temperature dependent viscosity data are also useful in determining the molecular information, such as the pair interaction potential function.12−16 The saccharide−metal ion interactions have great importance in biological systems. Na+ and K+ ions are responsible for the striking difference in the composition of extra- and intracellular fluids in animals and sap fluids in plants. Phosphate-based inorganic salts have stabilizing and salting-out effects on proteins and macromolecules.5,13,17−25 Since the charge on the anion and cation plays a determinant role in © XXXX American Chemical Society
salting-in and salting-out behavior, we have tried to reconcile the effects of different salts on the viscometric properties of saccharides in terms of size, charge, and ionic strength of ions of phosphate salts. To the best of our knowledge, the viscometric study of saccharides and their derivatives in aqueous solutions of phosphate salts is missing in the literature. However, the literature of viscometric study in the binary systems that is, (saccharides + water)10,16,19,22,26,27,29−31 and (phosphate salts + water)5,13 is available and discussed in the present study. So, we hereby report the viscosities of some mono-, di-, and trisaccharides and the methyl- and deoxy-derivatives of some monosaccharides in aqueous solutions of potassium phosphate, sodium phosphate, and ammonium phosphate monobasic salts, and potassium phosphate tribasic salt over the temperature range (288.15, 298.15, 308.15, and 318.15) K and atmospheric pressure, P = 0.1 MPa. The viscosity B-coefficients and other parameters, such as viscosity B-coefficient of transfer, temperature dependent, that is, dB/dT coefficients, and pair and triplet interaction coefficients, were calculated and compared with the volumetric properties reported earlier.26,27
2. EXPERIMENTAL SECTION 2.1. Materials. The provenances of chemicals along with their abbreviations, mass-fraction purity, and CAS numbers are given in Table 1. Highest purity grade chemicals were dried over CaCl2(anhy) in a vacuum desiccator for 48 h at room temperature Received: October 3, 2015 Accepted: April 12, 2016
A
DOI: 10.1021/acs.jced.5b00845 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 1. Specifications of the Chemicals Used C,H,N,S analysis compound (abbreviations) [molecular formula]
molar mass g·mol−1
mass fraction puritya
source
CAS no.
(+)-D-xylose (Xyl) [C5H10O5]
150.13
0.99
Sigma Chemical Co.
58-86-6
(−)-D-ribose (Rib) [C5H10O5]
150.13
0.99
Sigma Chemical Co.
50-69-1
(−)-D-fructose (Fru) [C6H12O6]
180.16
0.99
Sigma Chemical Co.
57-48-7
(+)-D-glucose (Glc) [C6H12O6]
180.16
≥ 0.99
Sigma Chemical Co.
50-99-7
(+)-D-mannose (Man) [C6H12O6]
180.16
≥ 0.99
Fluka
3458-28-4
2-deoxy-D-ribose (2de-Rib) [C5H10O4]
134.13
0.99
Sisco Research Lab.
533-67-5
2-deoxy-D-glucose (2de-Glc) [C6H12O5]
164.16
0.99
Sisco Research Lab.
154-17-6
6-deoxy-D-mannose (6de-Man) [C6H12O5.H2O]
182.18
0.99
Sisco Research Lab.
6155-35-7
(+)-methyl α-D-mannopyranoside (Me α-Man) [C7H14O6]
194.18
≥ 0.99
Sigma Chemical Co.
617-04-9
(+)-methyl α-D-glucopyranoside (Me α-Glc) [C7H14O6]
194.18
≥ 0.99
Sigma Chemical Co.
97-30-3
sucrose (Suc) [C12H22O11]
342.30
≥ 0.99
Sigma Chemical Co.
57-50-1
(+)-cellobiose (Cel) [C12H22O11]
342.30
0.98
Sigma Chemical Co.
528-50-7
(+)-lactose monohydrate (Lac) [C12H22O11.H2O]
360.31
≥ 0.98
Sigma Chemical Co.
64044-51-5
(+)-maltose monohydrate (Mal) [C12H22O11.H2O]
360.31
0.99
Sigma Chemical Co.
6363-53-7
(+)-melezitose (Mel) [C18H32O16]
504.48
> 0.99
Sisco Research Lab.
207511-10-2
(+)-raffinose pentahydrate (Raf) [C18H32O16.5H2O]
594.53
≥ 0.99
Fluka
17629-30-0
potassium phosphate monobasic (KH2PO4)
136.09
≥ 0.99
7778-77-0
sodium phosphate monobasic (NaH2PO4)
119.98
≥ 0.99
ammonium phosphate monobasic (NH4H2PO4)
115.03
≥ 0.98
potassium phosphate tribasic (K3PO4)
212.27
≥ 0.98
Sigma Chemical Co. Sigma Chemical Co. Sigma Chemical Co. Sigma Chemical Co.
a
calculated %
observed %
C = 40.00 H = 6.71 C = 40.00 H = 6.71 C = 40.00 H = 6.71 C = 40.00 H = 6.71 C = 40.00 H = 6.71 C = 44.77 H = 7.51 C = 43.90 H = 7.37 C = 39.55 H = 7.74 C = 43.30 H = 7.27 C = 43.30 H = 7.27 C = 42.10 H = 6.48 C = 42.10 H = 6.48 C = 40.00 H = 6.71 C = 40.00 H = 6.71 C = 42.85 H = 6.39 C = 36.36 H = 7.12
C = 39.97 H = 6.69 C = 39.98 H = 6.69 C = 40.02 H = 6.74 C = 40.03 H = 6.69 C = 40.03 H = 6.68 C = 44.75 H = 7.54 C = 43.88 H = 7.39 C = 39.53 H = 7.77 C = 43.26 H = 7.30 C = 43.27 H = 7.25 C = 42.13 H = 6.46 C = 42.08 H = 6.49 C = 40.03 H = 6.69 C = 40.02 H = 6.69 C = 42.83 H = 6.36 C = 36.34 H = 7.15
7778-77-0 7722-76-1 7778-53-2
Declared by the supplier.
before use. The purity of the chemicals used was analyzed with C, H, N, and S analysis method using FLASH 2000 Organic Elemental Analyzer, USA. The carbon and hydrogen contents obtained in the analysis were similar to expected values from the molecular formula with zero percentage of nitrogen and sulfur (Table 1). The hydrogen and oxygen percentage obtained suggests that the samples were completely dried and the water content was negligible for anhydrous samples. However, it should be noted that the elemental analysis cannot reveal any impurities with same summary chemical formula such as, for example, isomers. 2.2. Equipment and Procedure. Ubbelohde-type capillary viscometer was employed for measuring the viscosities of solutions by measuring the efflux time with a digital stopwatch (resolution of ±0.01 s) for the average of at least four flow time readings. The viscometer was calibrated by measuring the efflux time of water from T = (288.15 to 318.15) K. The temperature of
the viscometer was maintained by a constant temperature bath (Julabo F-25) with thermal stability within ±0.01 K. Deionized water (specific conductance Mel > Mal > Lac > Suc > Cel, indicating that the α or β glycosidic linkage between the monomer units result in different hydration characteristics of these saccharides.15,18,21 In the cases of KH2PO4, NH4H2PO4, and K3PO4, the B-coefficients of derivatives are less than their parent saccharides
ηo = [hNA /V1,°ϕ]exp[Δμ1° # /RT ]
(4)
where NA, h, R, and T are the Avogadro’s number, Planck’s constant, universal gas constant, and temperature, respectively; V°1,ϕ is the average molar volume of salt solution calculated from density data26,27 at different temperatures. The values of Δμ1°# for water and aqueous solutions of phosphate salts are given in Table S3 at different molalities and studied temperatures. The activation Gibbs free energy, Δμ°2 # (Table S4) for viscous flow of the solute in aqueous and mixed aqueous solutions is related to the viscosity B-coefficient according to Feakins et al.33,34 as follows: C
DOI: 10.1021/acs.jced.5b00845 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 2. Viscosity B-Coefficients of Saccharides/Derivatives in Water and in Aqueous Solutions of Phosphate-Based Cosolutes over the Temperature Range (288.15 to 318.15) K at Pressure (p = 0.1 MPa)a B·103/m3·mol−1 solute
water
mB = 0.50
1.00
1.50
2.00
water
0.346 0.338b 0.339c 0.336d,e 0.314 0.317b 0.319c,d,e 0.454 0.449b 0.451d,g 0.456 0.460b 0.458c,g 0.461d 0.440e 0.450h 0.472 0.471b,d 0.469c 0.371 0.431 0.480 0.517 0.465 0.465d 0.995 0.995b 0.989c 0.996d 1.006f,g 0.878 0.878b,d 0.885f
mB = 0.50
1.00
1.50
2.00
T/K = 298.15 0.369 0.384
0.396
0.406
0.340
0.353
0.372
0.386
0.502
0.526
0.563
0.588
0.536
0.561
0.605
0.635
0.484
0.507
0.558
0.587
0.378 0.446 0.497 0.519 0.477
0.401 0.469 0.516 0.537 0.495
0.441 0.510 0.559 0.575 0.534
0.465 0.534 0.583 0.601 0.562
1.073
1.102
1.134
1.149
1.132
1.155
1.166
1.170
KH2PO4 (+)-D-xylose
(−)-D-ribose
(−)-D-fructose
(+)-D-glucose
(+)-D-mannose
2-deoxy-D-ribose 2-deoxy-D-glucose 6-deoxy-D-mannose (+)-methyl α-D-mannopyranoside (+)-methyl α-D-glucopyranoside sucrose
(+)-cellobiose
(+)-lactose monohydrate
(+)-maltose monohydrate
(+)-melezitose (+)-raffinose pentahydrate
(+)-D-xylose
(−)-D-ribose
(−)-D-fructose
T/K = 288.15 0.360 0.393 0.368b 0.371c 0.370d 0.338 0.375 0.331b 0.332d 0.495 0.556 0.485b 0.482d 0.494 0.583 0.497b 0.493c 0.498d
0.511 0.511b 0.508c,d 0.391 0.453 0.511 0.543 0.495 0.496d 1.032 1.032b 1.036c 1.035d 1.031f 0.913 0.913b 0.912d 0.901f 1.086 1.086b 1.090d 1.080f 1.128 1.128b,d 1.127c 1.121f 1.432 1.434b 1.542 1.543b,d
0.408
0.427
0.437
0.388
0.407
0.428
0.583
0.621
0.646
0.612
0.661
0.687
0.532
0.566
0.606
0.637
0.403 0.475 0.532 0.554 0.518
0.427 0.499 0.556 0.574 0.538
0.472 0.544 0.600 0.614 0.579
0.502 0.574 0.629 0.641 0.609
1.129
1.161
1.191
1.211
1.198
1.218
1.224
1.229
1.275
1.302
1.342
1.366
1.048 1.045b 1.048d
1.199
1.240
1.259
1.301
1.312
1.362
1.401
1.421
1.251
1.292
1.333
1.361
1.542
1.598
1.677
1.718
1.453
1.515
1.595
1.642
1.706
1.766
1.840
1.870
1.091 1.088b 1.081c 1.086d 1.384 1.379b 1.478 1.477b 1.479d
1.617
1.671
1.747
1.770
0.350
0.372
0.375
T/K = 318.15 0.318 0.325
0.341
0.347
0.323
0.342
0.352
0.291
0.302
0.316
0.332
0.491
0.526
0.552
0.396
0.415
0.453
0.473
T/K = 308.15 0.327 0.339 0.327b 0.323c 0.324d 0.294 0.311 0.291b 0.292d 0.436 0.471
D
0.311 0.311b 0.310c 0.309d 0.283 0.282b 0.280d 0.373
DOI: 10.1021/acs.jced.5b00845 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 2. continued B·103/m3·mol−1 solute
(+)-D-glucose
(+)-D-mannose
2-deoxy-D-ribose 2-deoxy-D-glucose 6-deoxy-D-mannose (+)-methyl α-D-mannopyranoside (+)-methyl α-D-glucopyranoside sucrose
(+)-cellobiose
(+)-lactose monohydrate
(+)-maltose monohydrate
(+)-melezitose (+)-raffinose pentahydrate
water
mB = 0.50
T/K = 308.15 0.422b 0.420d 0.427 0.485 0.432b 0.436c 0.433d 0.440 0.446 0.440b 0.444c,d 0.349 0.345 0.407 0.413 0.451 0.463 0.491 0.483 0.443 0.440 0.443d 0.956 1.023 0.955b 0.952c 0.960d 0.970f 0.842 1.074 0.843b 0.845d 0.850f 1.022 1.135 1.027b 1.025d 1.053 1.193 1.053b 1.049c 1.051d 1.322 1.366 1.325b 1.431 1.549 1.430b 1.428d
1.00
1.50
2.00
water
mB = 0.50
1.00
1.50
2.00
T/K = 318.15
0.510
0.554
0.582
0.467
0.512
0.534
0.368 0.435 0.477 0.503 0.466
0.408 0.475 0.521 0.541 0.504
0.432 0.499 0.541 0.560 0.530
1.046
1.072
1.086
1.091
1.101
1.112
1.167
1.195
1.223
1.226
1.273
1.295
1.437
1.518
1.564
1.594
1.665
1.689
0.377b 0.381d 0.406 0.410b 0.412c 0.409d 0.418 0.418b 0.415c,d 0.330 0.384 0.421 0.466 0.413 0.412d 0.918 0.918b 0.916c,d 0.911f
0.434
0.462
0.503
0.531
0.420
0.435
0.472
0.499
0.310 0.386 0.426 0.448 0.401
0.336 0.402 0.439 0.469 0.425
0.374 0.438 0.479 0.507 0.463
0.401 0.466 0.500 0.525 0.481
0.977
0.989
1.005
1.018
0.807 0.807b,d 0.796f
0.997
1.016
1.027
1.032
0.991 0.976b 0.980d 1.007 1.006b 1.009c 1.005d 1.279 1.279b 1.364 1.367b 1.365d
1.049
1.074
1.109
1.146
1.121
1.148
1.190
1.211
1.295
1.355
1.444
1.489
1.457
1.496
1.559
1.580
0.521 0.494 0.608 0.663 0.596 0.565 0.626 0.602 0.766 0.674 1.321 1.196 1.403 1.470 1.682 1.834
0.548 0.539 0.668 0.761 0.627 0.611 0.680 0.644 0.852 0.781 1.414 1.218 1.464 1.552 1.713 1.887
0.418 0.405 0.497
0.464 0.468 0.563
NaH2PO4 (+)-D-xylose (−)-D-ribose (−)-D-fructose (+)-D-glucose (+)-D-mannose 2-deoxy-D-ribose 2-deoxy-D-glucose 6-deoxy-D-mannose (+)-methyl α-D-mannopyranoside (+)-methyl α-D-glucopyranoside sucrose (+)-cellobiose (+)-lactose monohydrate (+)-maltose monohydrate (+)-melezitose (+)-raffinose pentahydrate (+)-D-xylose (−)-D-ribose (−)-D-fructose
T/K = 288.15 0.360 0.467 0.338 0.455 0.495 0.613 0.494 0.643 0.511 0.563 0.391 0.526 0.453 0.607 0.511 0.563 0.543 0.711 0.495 0.657 1.032 1.185 0.913 1.180 1.086 1.292 1.128 1.372 1.432 1.607 1.542 1.774 T/K = 308.15 0.327 0.392 0.294 0.371 0.436 0.521
0.504 0.499 0.642 0.681 0.619 0.567 0.643 0.608 0.791 0.702 1.296 1.236 1.401 1.498 1.695 1.889
0.558 0.542 0.673 0.709 0.648 0.614 0.690 0.644 0.848 0.752 1.383 1.264 1.483 1.566 1.754 1.948
0.602 0.594 0.721 0.839 0.679 0.654 0.756 0.681 0.916 0.831 1.501 1.283 1.567 1.646 1.811 2.028
0.346 0.314 0.454 0.456 0.472 0.371 0.431 0.480 0.517 0.465 0.995 0.878 1.048 1.091 1.384 1.478
0.432 0.424 0.546
0.480 0.457 0.579
0.516 0.495 0.637
0.311 0.283 0.373
E
T/K= 298.15 0.426 0.474 0.409 0.452 0.554 0.586 0.583 0.621 0.517 0.562 0.483 0.528 0.555 0.591 0.522 0.561 0.658 0.714 0.607 0.621 1.121 1.232 1.119 1.177 1.210 1.319 1.283 1.407 1.543 1.623 1.688 1.778 T/K = 318.15 0.354 0.383 0.339 0.374 0.446 0.469
DOI: 10.1021/acs.jced.5b00845 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 2. continued B·103/m3·mol−1 solute
water
mB = 0.50
T/K = 308.15 0.427 0.534 0.440 0.474 0.349 0.444 0.407 0.517 0.451 0.486 0.491 0.599 0.443 0.561 0.956 1.031 0.842 1.055 1.022 1.147 1.053 1.214 1.322 1.458 1.431 1.613 ±
(+)-D-glucose (+)-D-mannose 2-deoxy-D-ribose 2-deoxy-D-glucose 6-deoxy-D-mannose (+)-methyl α-D-mannopyranoside (+)-methyl α-D-glucopyranoside sucrose (+)-cellobiose (+)-lactose monohydrate (+)-maltose monohydrate (+)-melezitose (+)-raffinose pentahydrate
T/K = 288.15 0.338 0.372 0.494 0.547 0.511 0.573 0.453 0.495 0.495 0.531 0.543 0.554 1.032 1.146 0.913 1.036 1.128 1.131 1.542 1.696 T/K = 308.15 0.294 0.368 0.427 0.521 0.440 0.553 0.407 0.486 0.443 0.525 0.491 0.532 0.956 1.191 0.842 1.053 1.053 1.099 1.431 1.746
(−)-D-ribose (+)-D-glucose (+)-D-mannose 2-deoxy-D-glucose (+)-methyl α-D-glucopyranoside (+)-methyl α-D-mannopyranoside sucrose (+)-cellobiose (+)-maltose monohydrate (+)-raffinose pentahydrate (−)-D-ribose (+)-D-glucose (+)-D-mannose 2-deoxy-D-glucose (+)-methyl α-D-glucopyranoside (+)-methyl α-D-mannopyranoside sucrose (+)-cellobiose (+)-maltose monohydrate (+)-raffinose pentahydrate
(−)-D-ribose (+)-D-glucose 2-deoxy-D-glucose (+)-methyl α-D-glucoside (+)-maltose monohydrate (+)-raffinose pentahydrate T/K= 308.15 (−)-D-ribose (+)-D-glucose 2-deoxy-D-glucose (+)-methyl α-D-glucoside (+)-maltose monohydrate (+)-raffinose pentahydrate
1.00 0.558 0.515 0.486 0.546 0.525 0.652 0.583 1.167 1.109 1.254 1.317 1.533 1.694
1.50 0.599 0.549 0.528 0.584 0.552 0.695 0.624 1.257 1.136 1.336 1.383 1.583 1.746 NH4H2PO4
2.00
water
0.708 0.579 0.558 0.623 0.588 0.788 0.713 1.340 1.147 1.417 1.474 1.629 1.807
0.406 0.418 0.330 0.384 0.421 0.466 0.413 0.918 0.807 0.991 1.007 1.279 1.364
0.392 0.580 0.619 0.525 0.559 0.585 1.237 1.094 1.179 1.862
0.414 0.592 0.665 0.546 0.581 0.656 1.333 1.242 1.396 2.009
0.445 0.628 0.738 0.580 0.623 0.791 1.453 1.435 1.608 2.163
0.314 0.456 0.472 0.431 0.465 0.517 0.995 0.878 1.091 1.478
0.402 0.562 0.616 0.531 0.561 0.586 1.287 1.136 1.173 1.918
0.426 0.599 0.679 0.556 0.597 0.718 1.399 1.283 1.424 2.072 K3PO4
0.461 0.677 0.767 0.592 0.660 0.845 1.538 1.526 1.676 2.252
0.283 0.406 0.418 0.384 0.413 0.466 0.918 0.807 1.007 1.364
T/K = 288.15 0.338 0.419 0.494 0.630 0.453 0.534 0.543 0.593 1.128 1.341 1.542 1.835
0.430 0.681 0.568 0.618 1.437 1.904
0.448 0.701 0.589 0.639 1.504 1.954
0.294 0.427 0.407 0.491 1.053 1.431
0.359 0.578 0.498 0.532 1.319 1.740
0.375 0.596 0.518 0.557 1.371 1.786
0.346 0.536 0.470 0.514 1.248 1.666
0.453 0.314 0.736 0.456 0.622 0.431 0.660 0.517 1.540 1.091 2.018 1.478 T/K = 318.15 0.389 0.283 0.614 0.406 0.548 0.384 0.577 0.466 1.438 1.007 1.843 1.364
mB = 0.50
1.00
1.50
2.00
0.564 0.506 0.484 0.529 0.510 0.635 0.564 1.180 1.073 1.265 1.304 1.504 1.631
0.658 0.536 0.514 0.578 0.536 0.710 0.628 1.272 1.090 1.357 1.391 1.557 1.693
0.415 0.579 0.666 0.550 0.579 0.684 1.359 1.265 1.415 2.022
0.446 0.639 0.757 0.585 0.621 0.805 1.492 1.472 1.659 2.223
0.439 0.626 0.703 0.553 0.592 0.729 1.430 1.311 1.455 2.126
0.477 0.707 0.793 0.598 0.661 0.863 1.563 1.555 1.745 2.279
T/K = 298.15 0.378 0.391 0.581 0.625 0.503 0.533 0.550 0.571 1.291 1.376 1.745 1.812
0.406 0.640 0.551 0.590 1.437 1.859
0.416 0.667 0.584 0.612 1.488 1.923
0.324 0.492 0.434 0.469 1.193 1.579
0.353 0.547 0.486 0.509 1.308 1.693
0.369 0.579 0.516 0.534 1.371 1.750
T/K = 318.15 0.489 0.520 0.440 0.469 0.397 0.439 0.460 0.481 0.451 0.477 0.542 0.595 0.509 0.516 0.993 1.069 0.996 1.045 1.086 1.171 1.125 1.226 1.373 1.457 1.521 1.578 T/K= 298.15 0.365 0.391 0.542 0.569 0.559 0.612 0.493 0.531 0.522 0.558 0.542 0.583 1.171 1.261 1.040 1.117 1.104 1.165 1.713 1.868 T/K = 318.15 0.377 0.414 0.518 0.574 0.563 0.632 0.483 0.524 0.518 0.557 0.526 0.589 1.212 1.326 1.066 1.156 1.068 1.179 1.758 1.950
0.335 0.530 0.467 0.487 1.258 1.650
Standard deviation for fitting in eq 2 lies in the range of (0.001 to 0.008)·103 m3·mol−1. bReference 16. cReference 22. dReference 19. eReference 10. fReference 29. gReference 30. hReference 31. a
Δμ2° # = Δμ1° # + (RT /V1,°ϕ)[1000B − (V1,°ϕ − V 2°)]
B = [(V1,°ϕ − V 2°)/1000] #
#
+ V1,°ϕ[(Δμ2° − Δμ1° )/1000RT ]
(5)
(6)
According to the transition-state theory, every solvent molecule in one mole of solution must pass through the transition-state F
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Figure 2. Plots of viscosity B-coefficients of transfer ΔtB vs molalities mB of KH2PO4 for (a) (−)-D-ribose, (b) (+)-methyl α-D-glucopyranoside, (c) 2deoxy-D-glucose, (d) (+)-maltose monohydrate; of NaH2PO4 for (e) (−)-D-fructose, (f) 6-deoxy-D-mannose at ⧫, 288.15 K; ■, 298.15 K; ▲, 308.15 K; ×, 318.15 K.
transition-state is less favorable for the solutes in phosphatebased salts. Activation entropy, ΔS2°# and enthalpy, ΔH2°# for the viscous flow of solutes have been calculated in water and mixed aqueous solutions as
and also interact more or less strongly with the solute molecules. Hence, the Gibbs free energy of transfer of a solute from the ground-state to transition-state solvents, ΔG°2 (1 → 1′) is the first contribution and the Gibbs free energy of the solute through its own viscous transition state, ΔG2°(2 → 2′) which is equal to Δμ1°#, is the second contribution to Δμ2°#. The ΔG2°(1 → 1′) values thus obtained from Δμ°2 # and ΔG°2 (2 → 2′) values are found to increase with concentration of salt and decrease with rise of temperature in all the cases (Table S5). The ΔG°2 (1 → 1′) values follow the order: K3PO4 > NaH2PO4 > KH2PO4 > NH4H2PO4, due to high ionic charge and ionic strength of PO43− ion as compared to H2PO4− ion. The ΔG2°(1 → 1′) values also increase with complexity of the solute. The large positive values of Δμ°2 # and ΔG°2 (1 → 1′) suggest that the formation of
ΔS2° # = −d(Δμ2° # /dT )
(7)
ΔH2° # = Δμ2° # + T ΔS2° #
(8)
It is evident from the data (Tables S6 and S7) that ΔH°2 # and TΔS2°# values are positive and further ΔH2°# > TΔS2°#. This suggests that the formation of transition-state is associated with bond breaking and a decrease in structural order. Hence it G
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Figure 3. Plots of viscosity B-coefficients of transfer ΔtB vs molalities mB of NaH2PO4 for (a) methyl α-D-glucopyranoside, (b) (+)-cellobiose; of NH4H2PO4 for (c) methyl α-D-glucopyranoside, (d) methyl α-D-mannopyranoside; of K3PO4 for (e) 2-deoxy-D-glucose, (f) (+)-raffinose pentahydrate at ⧫, 288.15 K; ■, 298.15 K; ▲, 308.15 K; ×, 318.15 K.
with rise of temperature, except for a few cases in NH4H2PO4. The B/V2° values follow the order: Glc > 2de-Glc > Me α-Glc; Man > Me α-Man > 6de-Man, indicating that saccharides are more solvated than their respective derivatives. 3.3. Interaction Coefficients. The viscometric interaction coefficients were calculated using the McMillan-Mayer theory37,38 in order to study the solute−cosolute interactions as follows:
indicates that for the studied saccharides/derivatives, the solute− solvent interactions are nearly complete in the ground state. 3.2. Solvation. The ratio of viscosity B-coefficient to partial molar volume, V°2 at infinite-dilution, that is, B/V°2 helps in understanding the solvation of solutes. B/V°2 values lie between zero and 2.5 for unsolvated spherical species and the values higher than 2.5 indicate spherical solvated species.35,36 B/V°2 values in the present study are greater than 2.5 (Table S8), and the values are more in the presence of salts as compared to those in water, hence indicating that saccharides/derivatives are more solvated in the presence of studied phosphate salts. The B/V°2 values increase with increase in molalities of salts, but decrease
Δt B = 2ηABmB + 3ηABBmB 2
(9)
where A and B represent solute and cosolute. Generally, the pair η AB interaction coefficients are positive and triplet η ABB H
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interaction coefficients are negative for the studied solutes (except for Me α-Man and Mal in NH4H2PO4) (Table S9). The plot (Figure 4) clearly shows that the contribution of pair
Article
AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. Tel.: +91 183 2451357. Fax: +91 183 2258819/20. Funding
Neha Aggarwal is grateful for the award of fellowship to the Council of Scientific and Industrial Research (09/254(0228)/ 2011-EMR-I) New Delhi, India. Notes
The authors declare no competing financial interest.
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(1) Cevoli, C.; Balestra, F.; Ragni, L.; Fabbri, A. Rheological Characterization of Selected Food Hydrocolloids by Traditional and Simplified Techniques. Food Hydrocolloids 2013, 33, 142−150. (2) Abdulagatov, I. M.; Zeinalova, A. B.; Azizov, N. D. Viscosity of Aqueous Electrolyte Solutions at High Temperatures and High Pressures. Viscosity B-coefficient. Sodium Iodide. J. Chem. Eng. Data 2006, 51, 1645−1659. (3) Danon, B.; Van der Aa, L.; De Jong, W. Furfural Degradation in a Dilute Acidic and Saline Solution in the Presence of Glucose. Carbohydr. Res. 2013, 375, 145−152. (4) Vaňková, K.; Gramblička, M.; Polakovič, M. Single-Component and Binary Adsorption Equilibria of Fructooligosaccharides, Glucose, Fructose, and Sucrose on a Ca-Form Cation Exchanger. J. Chem. Eng. Data 2010, 55, 405−410. (5) Zafarani-Moattar, M. T.; Sarmad, S. Apparent Molar Volumes, Apparent Isentropic Compressibilities, and Viscosity B-coefficients of 1Ethyl-3-Methylimidazolium Bromide in Aqueous Di-potassium Hydrogen Phosphate and Potassium Di-hydrogen Phosphate Solutions at T = (298.15, 303.15, 308.15, 313.15 and 318.15) K. J. Chem. Thermodyn. 2012, 54, 192−203. (6) Cardoso, M. V. C.; Carvalho, L. V. C.; Sabadini, E. Solubility of Carbohydrates in Heavy Water. Carbohydr. Res. 2012, 353, 57−61. (7) Pal, A.; Chauhan, N. Volumetric, Viscometric and Acoustic Behaviour of Diglycine in Aqueous Saccharide Solutions at Different Temperatures. J. Mol. Liq. 2009, 149, 29−36. (8) Jozwiak, M.; Tyczynska, M.; Bald, A. Viscosity of Urea in the Mixture of N,N-Dimethylformamide and Water. J. Chem. Eng. Data 2013, 58, 217−224. (9) Gaida, L. B.; Dussap, C. G.; Gros, J. B. Variable Hydration of Small Carbohydrates for Predicting Equilibrium Properties in Diluted and Concentrated Solutions. Food Chem. 2006, 96, 387−401. (10) Zhuo, K.; Liu, Q.; Wang, Y.; Ren, Q.; Wang, J. Volumetric and Viscosity Properties of Monosaccharides in Aqueous Amino Acid Solutions at 298.15 K. J. Chem. Eng. Data 2006, 51, 919−927. (11) Kumar, K.; Patial, B. S.; Chauhan, S. Interactions of Saccharides in Aqueous Glycine and Leucine Solutions at Different Temperatures of (293.15 to 313.15) K: A Viscometric Study. J. Chem. Eng. Data 2015, 60, 47−56. (12) Tyrrell, H. J. V.; Kennerley, M. Viscosity B-coefficients Between 5° and 20 °C for Glycolamide, Glycine, and N-Methylated Glycines in Aqueous Solution. J. Chem. Soc. A 1968, 0, 2724−2728. (13) Ameta, R. K.; Singh, M. Surface Tension, Viscosity, Apparent Molal Volume, Activation Viscous Flow Energy and Entropic Changes of Water + Alkali Metal Phosphates at T = (298.15, 303.15, 308.15) K. J. Mol. Liq. 2015, 203, 29−38. (14) Shekaari, H.; Kazempour, A. Density and Viscosity in Ternary DXylose + Ionic Liquid (1-Alkyl-3-Methylimidazolium Bromide) + Water Solutions at 298.15 K. J. Chem. Eng. Data 2012, 57, 3315−3320. (15) Galema, S. A.; Engberts, J. B. F. N.; Blandamer, M. A. Stereochemical Aspects of the Hydration of Carbohydrates. Kinetic Medium Effects of Monosaccharides on a Water-Catalyzed Hydrolysis Reaction. J. Am. Chem. Soc. 1990, 112, 9665−9666. (16) Banipal, P. K.; Singh, V.; Chahal, A. K.; Banipal, T. S. Effect of Sodium Acetate on the Rheological Behaviour of Some Mono-, Di-, and
Figure 4. Contributions of viscometric interaction coefficients to ΔtB at various molalities mB of K3PO4 for (−)-D-ribose at (⧫,∗) 288.15 K, (■,●) 298.15 K, (▲,+) 308.15 K, (×,−) 318.15 K [⧫,■,▲,× (ηAB) and ∗,●,+,− (ηABB)].
interaction coefficients to ΔtB at various molalities of K3PO4 for (−)-D-ribose varies linearly while that of triplet coefficients varies nonlinearly. Both coefficients increase systematically from mono- to di- to trisaccharides. The magnitude of ηAB coefficients is large compared to that of ηABB values suggesting the pairwise interactions among solute and cosolute. Similar results were obtained for the volumetric studies for these solutes in phosphate-based salts.26,27
4. CONCLUSIONS The viscometric properties have been studied for various monoand di-, trisaccharides and methyl- and deoxy-derivatives of monosaccharides in aqueous solutions of potassium, sodium, and ammonium phosphate monobasic and potassium phosphate tribasic salts at different temperatures. The viscosity Bcoefficients are positive and increase with the molalities of the cosolutes, indicating an increase in kosmotropicity of solutes in the presence of phosphate-based cosolutes. Similarly, the viscosity B-coefficient of transfer, ΔtB are positive in all the studied cosolutes except for 2de-Rib, Me α-Glc and Me α-Man at mB = 0.25 mol·kg−1 KH2PO4 at (308.15 and 318.15) K. The dB/ dT values are negative for the solutes in all the cosolutes except in case of NH4H2PO4. Overall, the results suggest that saccharides/ derivatives exhibit more kosmotropic behavior in K3PO4 as compared to other phosphate-based salts. This has been attributed to high charge and ionic strength of PO43− anion compared to H2PO4− anion.
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REFERENCES
ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.5b00845. Viscosities, η (Table S1), dB/dT values (Table S2), activation parameters (Tables S3−S7), B/V2° values (Table S8) and interaction coefficients (Table S9) of saccharides/derivatives in water and in aqueous solutions of phosphate-based cosolutes (PDF) I
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