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. 2020 Dec 7;5(50):32357–32365. doi: 10.1021/acsomega.0c04292

Study of Thermodynamic and Acoustic Properties of Niacin in Aqueous Hexylene Glycol and Propylene Glycol at Different Temperatures

Nabaparna Chakraborty †, Kailash Chandra Juglan †,*, Harsh Kumar ‡,*
PMCID: PMC7758894  PMID: 33376872

Abstract

graphic file with name ao0c04292_0010.jpg

The densities and speed of sound for liquid mixtures containing vitamin B3 (niacin) at 0.01, 0.03, and 0.05 mol·kg–1 concentrations in aqueous propylene glycol and hexylene glycol at the variation of temperatures from 293.15 to 308.15 K have been measured using an Anton Paar DSA 5000 M. From volumetric experimental data, apparent molar volume (Vϕ), partial molar volume (Vϕ0), and partial molar volume of transfer (ΔVϕ) are calculated along with the apparent molar isentropic compression (Kϕ, S), partial molar isentropic compression (Kϕ, S0), and partial molar isentropic compression of transfer (ΔKϕ) using experimental acoustic data. The positive volumetric data (i.e., apparent molar volume and partial molar volume) indicates strong solute–solvent interactions inside the mixture. Along with these values, the empirical constants a, b, and c with the pair and triplet coefficients (VAB, VABB, KAB, KABB) are also calculated.

1. Introduction

The measurement of density and speed of sound for any liquid mixtures has become a valuable technique to analyze their state due to the close connections among the structure of liquid the macroscopic properties. The ultrasonic study has gained the stature of being an imperative tool for investigating the molecular structure of matter and their properties because of being a non-destructive technique. The acoustic study of the liquid mixtures is used for obtaining the thermodynamic characteristics of the compressed liquids, which are the key substances in various industries such as pharmaceutical, chemical, leather, cosmetic, etc.1,2

The present work comprises the comprehensive study of volumetric and acoustical properties of niacin at 0.01, 0.03, and 0.05 mol·kg–1 concentration in aqueous PG (propylene glycol)/HG (hexylene glycol) at the variation of temperatures. PG is an organic compound that is colorless, viscous, and almost odorless but possesses a mild sweet taste; it is classified as diol due to the presence of two alcohol groups. PG is miscible in the number of solvents and has low toxicity and volatility. It has wide applications in various industries such as pharmaceutical and cosmetics. It is used for producing unsaturated polyester resins, coffee-based drinks, soda, whipped dairy products, ice cream, and liquid sweeteners.3,4 HG is also a colorless and viscous compound with a typical sweet odor that is miscible with most of the common organic solvents. It is used in varnishing, printing ink, lacquers, pesticide formulation, automobile, textiles, chemical, and pharmaceutical industries.5,6 On the other hand, the organic compound niacin, also known as nicotinic acid, is one of the eight water-soluble B vitamins and is a form of vitamin B3, which is a key human nutrient. It is used as a dietary supplement to treat pellagra and nonmelanoma skin cancer and lower cholesterol.7

A remarkable number of work has been done on propylene and hexylene glycol; for example, Zarei et al8 has obtained the densities and viscosities of binary and ternary liquid mixtures of methanol + ethanol + 1,2-propendiol at various temperatures over the entire range of composition and thus calculated the excess molar volumes and refractive indices. In aqueous HG, the investigation of the acoustic and thermodynamic parameters for dispersed aluminum oxide nanoparticles has been done by Kumar et a.l9 At various temperatures, the velocity, viscosity, and density of these nanofluids have been measured. For niacin, an extensive amount of work has been done; for example, Pan et al10 had measured the electric conductance, viscosity, and density of a ternary solution containing water + polyethanol+ nicotinic acid. Orekhova el al11 had measured the volumetric properties and electrical conductance of aqueous nicotinic acid solution at different temperatures and molalities.

So, after rigorous literature review, it is found that the acoustic volumetric study of the solution containing (PG/HG) and niacin has not been done and consequently, an efficient study of ultrasonic properties has been accomplished in the present study. To study the physicochemical nature and molecular interaction inside the mixture of niacin and PG/HG, their density and velocity in various temperatures have been measured to calculate the volumetric and acoustical parameters.12

2. Results and Discussion

2.1. Volumetric Properties

2.1.1. Density

In Table 1, the experimental density values for niacin + distilled water + glycols at different temperatures ranging from 293.15 to 308.15 K with concentrations of 0.01, 0.03, and 0.05 mol·kg–1 are mentioned. The density value for glycols + distilled water has been taken from our previous paper.13 It can be seen in the data that all the density values are decreasing along with the temperatures and increases with more concentration. The decrement of the density values with the temperatures indicates the low hydrogen bonding. Scheme 1 shows the increment of molecular and solute–solvent interactions inside the solution from PG to HG. The comparison between the experimental and literature14 density values at temperatures of 298.15 and 3098.15 K for the mixture niacin + distilled water is displayed in Figure 1. It is visible that both the experimental and literature values are showing the same trend and thus are in good agreement with each other.15

Table 1. Values of Densities, ρ, Apparent Molar Volumes, Vϕ of Glycols in Aqueous Solutions of Niacin at Different Temperatures.
  ρ × 10–3/(kg·m–3)
 Vϕ × 106/(m3·mol–1)
mA/(mol·kg–1)a T = 293.15 K T = 298.15 K T = 303.15 K T = 308.15 K T = 293.15 K T = 298.15 K T = 303.15 K T = 308.15 K
0.00 mol·kg–1 Niacin + PG
0.00000 0.99821 0.99704 0.99565 0.99403b        
0.09917 0.99847 0.99731 0.99593 0.99432 73.54 73.55 73.57 73.62b
0.19801 0.99872 0.99757 0.99619 0.99459 73.59 73.61 73.63 73.66
0.30136 0.99896 0.99782 0.99645 0.99486 73.65 73.66 73.68 73.72
0.39826 0.99918 0.99805 0.99668 0.99510 73.69 73.71 73.73 73.77
0.51059 0.99942 0.99830 0.99694 0.99536 73.74 73.75 73.77 73.81
0.01 mol·kg–1 Niacin + PG
0.00000 0.99861 0.99740 0.99600 0.99440        
0.09995 0.99890 0.99769 0.99631 0.99467 73.30 73.41 73.24 73.84
0.20005 0.99915 0.99797 0.99657 0.99495 73.44 73.41 73.48 73.72
0.30106 0.99941 0.99820 0.99684 0.99520 73.49 73.57 73.52 73.77
0.39996 0.99961 0.99844 0.99708 0.99545 73.61 73.61 73.59 73.80
0.50512 0.99984 0.99869 0.99732 0.99570 73.66 73.62 73.65 73.83
0.03 mol·kg–1 Niacin + PG
0.00000 0.99951 0.99821 0.99683 0.99519        
0.10024 0.99979 0.99849 0.99714 0.99545 73.31 73.34 73.29 73.83
0.19987 1.00004 0.99876 0.99741 0.99570 73.44 73.40 73.41 73.88
0.29998 1.00030 0.99901 0.99766 0.99599 73.45 73.47 73.52 73.74
0.40018 1.00056 0.99928 0.99795 0.99626 73.42 73.47 73.46 73.69
0.50113 1.00081 0.99955 0.99822 0.99650 73.43 73.43 73.46 73.74
0.05 mol·kg–1 Niacin + PG
0.00000 1.00044 0.99911 0.99763 0.99607        
0.09981 1.00070 0.99940 0.99792 0.99631 73.40 73.15 73.38 73.96
0.20212 1.00097 0.99968 0.99819 0.99655 73.39 73.27 73.47 73.95
0.29999 1.00125 0.99994 0.99846 0.99684 73.29 73.30 73.45 73.77
0.40004 1.00152 1.00021 0.99875 0.99709 73.27 73.32 73.39 73.74
0.50220 1.00179 1.00048 0.99904 0.99738 73.26 73.32 73.36 73.67
0.00 mol·kg–1 Niacin + HG
0.00000 0.99821 0.99704 0.99565 0.99403b        
0.09903 0.99840 0.99725 0.99587 0.99427 116.37 116.40 116.42 116.46b
0.20184 0.99860 0.99745 0.99609 0.99450 116.39 116.42 116.45 116.48
0.29963 0.99878 0.99764 0.99629 0.99472 116.41 116.45 116.47 116.50
0.39805 0.99895 0.99782 0.99648 0.99492 116.44 116.48 116.49 116.52
0.49538 0.99911 0.99799 0.99666 0.99512 116.46 116.50 116.51 116.55
0.01 mol·kg–1 Niacin + HG
0.00000 0.99861 0.99740 0.99600 0.99440        
0.09899 0.99881 0.99762 0.99621 0.99466 116.33 116.16 116.43 116.21
0.20067 0.99901 0.99784 0.99641 0.99490 116.27 116.18 116.53 116.29
0.30008 0.99918 0.99801 0.99663 0.99511 116.35 116.37 116.44 116.38
0.40023 0.99936 0.99822 0.99684 0.99532 116.35 116.30 116.42 116.40
0.50001 0.99954 0.99840 0.99701 0.99552 116.36 116.34 116.48 116.44
0.03 mol·kg–1 Niacin + HG
0.00000 0.99951 0.99821 0.99684 0.99520        
0.10055 0.99971 0.99848 0.99708 0.99548 116.17 115.62 116.10 115.89
0.19998 0.99990 0.99871 0.99731 0.99571 116.20 115.81 116.11 116.09
0.30034 1.00009 0.99890 0.99755 0.99593 116.20 115.98 116.09 116.19
0.40009 1.00030 0.99910 0.99778 0.99615 116.14 116.04 116.06 116.23
0.50210 1.00051 0.99931 0.99798 0.99642 116.10 116.04 116.11 116.13
0.05 mol·kg–1 Niacin + HG
0.00000 1.00044 0.99911 0.99764 0.99607        
0.09995 1.00065 0.99939 0.99792 0.99637 115.97 115.43 115.60 115.60
0.20002 1.00087 0.99961 0.99815 0.99662 115.90 115.71 115.82 115.83
0.30172 1.00105 0.99982 0.99842 0.99686 116.02 115.81 115.75 115.91
0.40059 1.00127 1.00001 0.99866 0.99714 115.94 115.93 115.77 115.84
0.50009 1.00150 1.00021 0.99892 0.99742 115.87 115.95 115.73 115.77
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a

mA is the molality of glycols in the aqueous solution niacin; standard uncertainties u are u(m) = 2 × 10–5 mol·kg–1, u(T) = 0.03 K, u(ρ) = 0.06 (kg·m–3), u(p) = 0.01 MPa, u(c) = 0.6 m·s–1, and u(Vϕ) = ±(0.05–0.07)×106/(m3·mol–1).

b

Values of densities for PG + water and HG + water at temperatures of 293.15 and 308.15 K have been taken from our previous paper.13

Scheme 1. PG/ HG and Niacin Interactions.

Scheme 1

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Figure 1.

Figure 1

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Variation of experimental and literature density values14 of (niacin + water) corresponding to the molality (mB) of aqueous niacin at T = 298.15 and 308.15 K.

2.1.2. Apparent Molar Volume

The values apparent molar volume have been described in Table 1 and is graphically represented in Figure 2, were calculated using the molar mass (M) of the solute, molality (mA) of the solute per 1 kg of solvent (niacin + distilled water), and the density of solvent (ρ0) and solution (ρ) in the following equation22

2.1.2. 1
Figure 2.

Figure 2

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Variation of apparent molar volume, Vϕ, corresponding to the molality (mA) of glycols in niacin. (a) 0.01 niacin, (b) 0.03 niacin, and (c) 0.05 niacin against molality at different temperatures (red, propylene glycol and blue, hexylene glycol).

The calculated Vϕ values are all positive, which is because of the broad intrinsic volume of solute that suggests the existence of strong solute–solvent interactions inside the ternary mixture.16 With niacin concentration, the values of apparent molar volumes tend to increase, which is due to the association of the water molecules in the hydration shell with the OH groups of niacin. This leads to strengthening the hydrogen bond in the solvent due to the constructive interaction of niacin with water.17,18 Also, it is observed that with the increase in the molar mass of the glycols from PG to HG, the Vϕ also increases to all the concentration of niacin and all temperatures. This increase is responsible for factors such as hydrophilic effect, hydrophobic hydration in a water-rich region, and physical forces such as dipole–dipole and dipole-induced dipole interactions.5,19 The extent of the molecular interaction from PG to HG is displayed in Scheme 1.

2.1.3. Partial Molar Volume

Using the undermentioned equation,22 the partial molar volume at infinite dilution has been calculated

2.1.3. 2

Here, Vϕ0 is partial molar volume, SV is the experimental slope, and mA is the molality of solute per solvent. By utilizing the method of least square fitting, the values of partial molar volume and their experimental slope are calculated from apparent molar volume. In Table 2, the Vϕ0 and SV values are provided along with their standard errors. It can be seen that all the Vϕ0 values are all positive and rise with the concentration of niacin as shown in Figure 3. These positive values indicate the presence of strong solute–solvent interaction as well as the existence of ion–hydrophobic and hydrophobic–hydrophobic interaction in the mixture, which is preponderated by the ion–hydrophilic interactions. As per the co-sphere overlap model,20,21 the hydration co-spheres of two ionic spices superimpose on each other and results in an increase in the volume, but when ion-hydrophobic groups overlap on hydrophobic–hydrophobic groups, a decrease in the volume is observed. In Table 3, it is noticed that Vϕ values increase with the molar mass of glycols due to two additional −CH3– groups and HG as compared to PG, thus implying the influence of hydrocarbon chain in the molecular interaction. The calculated SV* values are positive, and few are negative in magnitude, which proves the presence of weak solute–solute interaction in the liquid system; also, the irregular pattern suggests the impact of additional parameters on the solute–solute interaction.12,22

Table 2. Limiting Apparent Molar Volumes, Vϕ0, and Experimental Slopes, SV, of Glycols in the Aqueous Solution of Niacin at Different Temperatures.
  Vϕ0 × 106/(m3·mol–1)
 SV* × 106/(m3·kg·mol–2)
mB/(mol·kg–1)a T = 293.15 K T = 298.15 K T = 303.15 K T = 308.15 K T = 293.15 K T = 298.15 K T = 303.15 K T = 308.15 K
PG
0.00000 73.49 (±0.005) 73.51 (±0.010) 73.53 (±0.008) 73.57 (±0.005)b 0.51 (±0.014) 0.49 (±0.030) 0.49 (±0.025) 0.48 (±0.016)b
0.01000 73.23 (±0.032) 73.34 (±0.047) 73.22 (±0.068) 73.77 (±0.057) 0.89 (±0.098) 0.61 (±0.142) 0.92 (±0.206) 0.08 (±0.172)
0.03000 73.35 (±0.056) 73.35 (±0.045) 73.31 (±0.074) 73.89 (±0.062) 0.22 (±0.169) 0.25 (±0.137) 0.38 (±0.223) –0.37 (±0.187)
0.05000 73.44 (±0.028) 73.15 (±0.045) 73.44 (±0.051) 74.05 (±0.045) –0.40 (±0.086) 0.40 (±0.137) –0.12 (±0.155) –0.77 (±0.137)
HG
0.00000 116.35 (±0.001) 116.37 (±0.001) 116.40 (±0.001) 116.43 (±0.001)b 0.22 (±0.005) 0.25 (±0.005) 0.22 (±0.002) 0.24 (±0.005)b
0.01000 116.29 (±0.031) 116.12 (±0.066) 116.46 (±0.054) 116.17 (±0.024) 0.14 (±0.094) 0.49 (±0.200) –0.01 (±0.164) 0.58 (±0.074)
0.03000 116.22 (±0.023) 115.57 (±0.081) 116.11 (±0.028) 115.91 (±0.106) –0.20 (±0.099) 1.08 (±0.245) –0.04 (±0.084) 0.63 (±0.319)
0.05000 115.99 (±0.062) 115.38 (±0.085) 115.67 (±0.091) 115.68 (±0.127) –0.17 (±0.188) 1.27 (±0.257) 0.21 (±0.274) 0.36 (±0.382)
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a

mB is the molality of aqueous niacin, standard uncertainties u are u(m) = 2 × 10–5 mol·kg–1, u(T) = 0.03K, u(ρ) = 0.06 (kg·m–3), u(p) = 0.01MPa, u(c) = 0.6 m·s–1, u(Vϕ0) = ±0.01×106/(m3·mol–1), and u( SV) = ±0.03×106/(m3·mol–2).

Figure 3.

Figure 3

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Variation of partial molar volumes, Vϕ0, corresponding to the molality (mB) of niacin. Propylene glycol (color pink) and hexylene glycol (color olive) in different concentrations of aqueous niacin solutions at different temperature.

Table 3. Values of the Speed of Sound, c, and Apparent Molar Isentropic Compression, Kϕ, s, of Glycols in Aqueous Solutions of Glycerol at Different Temperatures.
  c/(m·s–1)
 Kϕ, s×1015/(m3·mol–1·Pa–1)
mA/(mol·kg–1)a T = 293.15 K T = 298.15 K T = 303.15 K T = 308.15 K T = 293.15 K T = 298.15 K T = 303.15 K T = 308.15 K
0.00 mol·kg–1 Niacin + PG
0.00000 1481.0 1495.0 1508.0 1519.0b        
0.09917 1486.0 1500.0 1513.0 1523.0 –42.62 –44.25 –43.49 –42.90b
0.19801 1490.0 1504.0 1516.0 1526.0 –42.86 –44.49 –43.72 –43.13
0.30136 1493.0 1507.0 1520.0 1529.0 –42.95 –44.58 –43.81 –43.22
0.39826 1496.0 1510.0 1522.0 1532.0 –42.99 –44.62 –43.86 –43.27
0.51059 1499.0 1513.0 1525.0 1534.0 –43.03 –44.66 –43.89 –43.30
0.01 mol·kg–1 Niacin + PG
0.00000 1483.6 1497.2 1509.4 1519.9        
0.09995 1488.2 1502.1 1514.4 1524.2 –44.99 –44.18 –43.47 –42.86
0.20005 1492.2 1506.1 1517.6 1527.4 –45.23 –44.41 –43.70 –43.09
0.30106 1495.3 1509.5 1521.7 1530.3 –45.32 –44.50 –43.78 –43.18
0.39996 1498.4 1512.8 1523.9 1533.4 –45.36 –44.55 –43.83 –43.22
0.50512 1501.5 1515.6 1526.7 1535.1 –45.40 –44.58 –43.86 –43.26
0.03 mol·kg–1 Niacin + PG
0.00000 1485.6 1498.8 1511.1 1521.5        
0.10024 1490.4 1503.7 1515.9 1525.8 –44.87 –44.09 –43.37 –42.78
0.19987 1494.4 1507.8 1519.1 1528.8 –45.11 –44.32 –43.60 –43.00
0.29998 1497.5 1511.4 1523.1 1531.9 –45.19 –44.41 –43.68 –43.09
0.40018 1500.7 1514.9 1525.9 1535.1 –45.24 –44.45 –43.73 –43.14
0.50113 1503.8 1517.6 1528.5 1536.9 –45.28 –44.49 –43.77 –43.17
0.05 mol·kg–1 Niacin + PG
0.00000 1487.3 1500.6 1512.8 1523.2        
0.09981 1492.0 1505.5 1517.6 1527.6 –44.77 –43.98 –43.27 –42.68
0.20212 1496.3 1509.8 1520.9 1530.8 –45.01 –44.22 –43.51 –42.91
0.29999 1499.4 1513.4 1524.8 1533.9 –45.10 –44.30 –43.59 –42.99
0.40004 1502.7 1517.0 1527.7 1536.8 –45.15 –44.35 –43.64 –43.04
0.50220 1506.1 1519.6 1530.4 1538.7 –45.18 –44.38 –43.67 –43.07
0.00 mol·kg–1 Niacin + HG
0.00000 1481.0 1495.0 1508.0 1519.0b        
0.09903 1490.0 1504.0 1515.0 1525.0 –45.13 –44.25 –43.49 –42.90b
0.20184 1500.0 1512.0 1523.0 1533.0 –45.38 –44.49 –43.72 –43.13
0.29963 1508.0 1520.0 1531.0 1539.0 –45.46 –44.57 –43.80 –43.21
0.39805 1517.0 1528.0 1537.0 1545.0 –45.50 –44.61 –43.85 –43.26
0.49538 1523.0 1535.0 1543.0 1551.0 –45.53 –44.64 –43.88 –43.29
0.01 mol·kg–1 Niacin + HG
0.00000 1483.6 1497.2 1509.4 1519.9        
0.09899 1492.5 1505.9 1517.0 1526.1 –44.98 –44.17 –43.46 –42.86
0.20067 1502.4 1514.1 1525.0 1534.2 –45.23 –44.41 –43.69 –43.09
0.30008 1511.1 1522.2 1533.2 1540.1 –45.31 –44.49 –43.78 –43.17
0.40023 1519.9 1530.3 1539.1 1546.2 –45.36 –44.54 –43.82 –43.22
0.50001 1525.6 1537.4 1545.1 1552.4 –45.39 –44.57 –43.85 –43.25
0.03 mol·kg–1 Niacin + HG
0.00000 1485.6 1498.8 1511.1 1521.5        
0.10055 1494.7 1507.2 1519.1 1527.5 –44.87 –44.09 –43.37 –42.78
0.19998 1504.7 1515.2 1526.5 1535.4 –45.10 –44.32 –43.60 –43.01
0.30034 1513.6 1523.4 1534.8 1541.5 –45.19 –44.40 –43.68 –43.09
0.40009 1522.6 1531.3 1540.5 1547.8 –45.24 –44.45 –43.73 –43.14
0.50210 1528.9 1539.3 1547.3 1553.9 –45.27 –44.48 –43.76 –43.17
0.05 mol·kg–1 Niacin + HG
0.00000 1487.3 1500.6 1512.8 1523.2        
0.09995 1496.4 1508.5 1520.7 1529.4 –44.77 –43.98 –43.27 –42.68
0.20002 1505.9 1516.7 1528.3 1537.6 –45.01 –44.21 –43.50 –42.91
0.30172 1515.2 1524.9 1536.9 1543.6 –45.09 –44.30 –43.59 –42.99
0.40059 1523.9 1532.5 1542.7 1549.9 –45.14 –44.34 –43.64 –43.04
0.50009 1530.4 1540.4 1549.4 1555.7 –45.17 –44.37 –43.67 –43.08
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a

mA is the molality of glycols in the aqueous solution niacin; standard uncertainties u are u(m) = 2 × 10–5 mol·kg–1, u(T) = 0.05 K, u(ρ) = 0.06 (kg·m–3), u(p) = 0.01 MPa, u(c) = 0.6 m·s–1, and u(Kϕ, S) = ±0.25×106/(m3·mol–1·GPa–1).

b

Values of speed of sound for (PG + water and HG + water) at temperatures of 293.15 and 308.15 K have been taken from our previous paper.13

2.2. Ultrasonic Properties

2.2.1. Ultrasonic Speed

The experimentally obtained speed of sound data at 293.15, 298.15, 303.15, and 308.15 K for niacin + water as well as niacin + water + PG/HG for 0.01, 0.03, and 0.05 mol·kg–1 concentrations are described in Table 3. The speed of sound values for PG/HG + water is taken directly from our previous paper.14 The experimental speed of sound values are compared with the literature values16 for temperatures of 298.15 and 308.15 K and are graphically presented in Figure 4. The experimental values are in the same trend as the literature values, i.e., increasing along with the temperatures and the concentrations of niacin from 0.01 to 0.03 to 0.05 mol·kg–1. This is due to the 3D network water structure in which there exist 3D networks of hydrogen bonds, and the acceleration of the speed of sound values for the glycol and vitamin mixture is due to the intermolecular hydrogen bonding in solute–solvent molecules and intramolecular hydrogen bonding in solute molecules, therefore implying the high combination rate of the molecules inside the solutions. The increment in the values of speed of sound along with the molality of PG/HG is due to the hydrogen bond network insolvent with the aqueous niacin molecule. The hydrogen bond formed between the water and niacin molecules get reduced corresponding to the increase in the molar mass of the glycol from PG to HG, and finally, this bond abolished, but concurrently fresh H-bonds are created amid niacin and glycol molecules.17,23−25

Figure 4.

Figure 4

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Variation of experimental and literature speed of sound values14 of (niacin + water) corresponding to the molality (mB) of aqueous niacin at T = 298.15 and 308.15 K.

2.2.2. Apparent Molar Isentropic Compression

By the means of following mathematical equation,22 the apparent molar isentropic compression of (PG/HG) in the aqueous and mixed aqueous solution of niacin at different temperatures has been calculated

2.2.2. 3

utilizing the values of experimental densities of solution (ρ), densities of solvent (ρ0), molality (mA) values of (PG/HG) in niacin, and the molar mass of the solute (M) in the equation. The calculated Kϕ, S values are presented in Table 3 and are graphically represented in Figure 5.

Figure 5.

Figure 5

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Variation of apparent molar isentropic compression, Kϕ, s, corresponding to the molality (mA) of glycols in niacin. (a) Propylene glycol and (b) hexylene glycol in aqueous solutions of pink (0.01 niacin), blue (0.03 niacin), and black (0.05 niacin) against molality at different temperatures (inverted triangle, 308.15 K; triangle, 303.15 K, circle 298.15 K; square, 293.15 K).

Using Laplace–Newton’s equation, the isentropic compressibility is expressed26

2.2.2. 4

where ρ is the density of the solution and c is the speed of sound. The Kϕ, S values are all negative, and with the increase in the temperature, the values become less negative, but with the molality of glycols, the negativity of Kϕ, S values increases. It is also observed from the table that with the upsurge of niacin concentration in the mixture, the negativity of the apparent molar isentropic compression decreases. This trend of Kϕ, S values indicates that the water molecules are less compressible around ionic charge groups of solute as compared to the bulk solution. This reveals the arrangement of water in a specific pattern throughout the solute.22,27,28 Also, the negative values show more aligning effect due to solute on solvent resulting in a larger loss of structural compressibility of water.

2.2.3. Partial Molar Isentropic Compression

Using the undermentioned equation,22 the partial molar isentropic compression at infinite dilution has been calculated

2.2.3. 5

Here, Kϕ, S0 is partial molar isentropic compression, Sk is the experimental slope, and mA is the molality of solute per solvent. By utilizing the method of least square fitting, the values of partial molar isentropic compression and their experimental slope are calculated from apparent molar isentropic compression. In Table 4, the Kϕ, S0 and Sk values are provided along with their standard errors. It can be seen that all the Kϕ, S0 values are negative, and the negativity reduces with the concentration of niacin, as shown in Figure 6. This trend refers to the presence of attractive interactions between water and glycols.29 With the increase in the temperature, the values become less negative, but with the molality of glycols, the negativity of Kϕ, S values increases, thus suggesting the discharge of water molecules to bulk. Moreover, the desiccation of glycol molecules occurs due to the attractive interactions between niacin and water. As a consequence, with the increase in the niacin concentration, the water molecules around glycols become more compressible. The Sk* values in the table are all negative and refer to the presence of weak solute–solute interaction in the solution.10,15,30

Table 4. Limiting Apparent Molar Isentropic Compression, Kϕ, s0, and Experimental Slopes, Sk, of Glycols in the Aqueous Solution of Glycerol at Different Temperatures.
  Kϕ, s0× 1015/(m3·mol–1·Pa–1)
 Sk*×1015/(kg·m3·mol–2·Pa–1)
mB/(mol·kg–1)a T = 293.15 K T = 298.15 K T = 303.15 K T = 308.15 K T = 293.15 K T = 298.15 K T = 303.15 K T = 308.15 K
PG
0.00000 –44.98 (±0.08) –44.24 (±0.08) –43.48 (±0.08) –42.89 (±0.08) –0.93 (±0.23) –0.93 (±0.22) –0.92 (±0.22) –0.91 (±0.23)
0.01000 –44.98 (±0.07) –44.16 (±0.07) –43.45 (±0.07) –42.85 (±0.07) –0.94 (±0.23) –0.93 (±0.23) –0.92 (±0.22) –0.91 (±0.22)
0.03000 –44.85 (±0.07) –44.07 (±0.07) –43.35 (±0.07) –42.76 (±0.07) –0.95 (±0.23) –0.94 (±0.23) –0.93 (±0.22) –0.92 (±0.22)
0.05000 –44.75 (±0.07) –43.97 (±0.07) –43.26 (±0.07) –42.66 (±0.07) –0.96 (±0.23) –0.94 (±0.23) –0.93 (±0.22) –0.92 (±0.22)
HG
0.00000 –45.12 (±0.08) –44.23 (±0.08) –43.47 (±0.08) –42.88 (±0.08) –0.94 (±0.24) –0.93 (±0.24) –0.93(±0.23) –0.92 (±0.23)
0.01000 –44.97 (±0.07) –44.16 (±0.07) –43.45 (±0.07) –42.84 (±0.07) –0.93 (±0.23) –0.92 (±0.23) –0.92 (±0.23) –0.91 (±0.23)
0.03000 –44.86 (±0.07) –44.08 (±0.07) –43.35 (±0.07) –42.77 (±0.07) –0.92 (±0.22) –0.91 (±0.22) –0.91 (±0.22) –0.90 (±0.22)
0.05000 –44.76 (±0.07) –43.97 (±0.07) –43.26 (±0.07) –42.67 (±0.07) –0.93 (±0.23) –0.91 (±0.22) –0.92 (±0.22) –0.92 (±0.22)
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a

mB is the molality of aqueous niacin, standard uncertainties u are u(m) = 2 × 10–5 mol·kg–1, u(T) = 0.03 K, u(ρ) = 0.06 (kg·m–3), u(p) = 0.01 MPa, u(c) = 0.6 m·s–1, u(Kϕ, s0) = ±0.01×106/(m3·mol–1·GPa–1), and u(Sk) =±0.24×106/(m3·mol–2·GPa–1).

Figure 6.

Figure 6

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Variation of partial molar isentropic compression, Kϕ, s0, corresponding to the molality (mA) of glycols in niacin. (a) Propylene glycol and (b) hexylene glycol in aqueous niacin solutions at different temperatures.

3. Conclusions

For the liquid combination of [propylene glycol (PG)/hexylene glycol (HG) + niacin+ water], the volumetric and acoustic properties have been studied through the calculations of various thermodynamic parameters at the temperature variations of 293.15, 298.15, 303.15, and 308.15 K over the solvent concentrations of 0.01, 0.03, and 0.05 mol·kg–1 at atmospheric pressure. Significant information regarding the interactions in the present ternary liquid combination has been revealed through the calculated parameters. The existence of strong solute–solvent interactions along with dipole–dipole interactions, dipole-induced dipole interactions, hydrophilic effect, and hydrophobic hydration has been confirmed from volumetric properties. The domination of ion–hydrophilic interaction over hydrophobic–hydrophobic interaction, strong ion–ion interaction of glycols and niacin, and solute–solvent interactions are revealed from the acoustic properties.

The values of Eϕ0 indicates the structure making ability of the molecules inside the mixture. The formation of the hydrogen bond network insolvent with the aqueous niacin molecule, the strong attractive interactions among the molecules of water and molecules of glycols, and the dominance of pairwise interaction are also observed, which is justified from the experimental speed of sound values and pair and triplet coefficients.

4. Experimental Procedure

4.1. Materials Used

PG (IUPAC name propane-1,2-diol) and HG (IUPAC name 2-methyl-2,4-pentanediol) with niacin (IUPAC name pyridine-3-carboxylic acid) are used in the current study. All the chemicals are obtained from Loba Chemicals as mentioned in Table 5 along with their CAS no. and method of purification. The niacin mixture was composed using degassed and triple-distilled water. Without any further purification, the chemicals were vacuum dried for 48 h and then deposited over P2O5.

Table 5. Specification of Chemicals.

4.1.

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4.2. Apparatus and methods Used

The experiment was carried out using Anton Paar DSA 5000 M, with which the density and speed of sound of the solution containing niacin and (PG/HG) were obtained at 293.15, 298.15, 303.15, and 308.15 K over 0.01, 0.03, and 0.05 mol·kg–1 concentration of niacin. A weighing balance with a precision of ±10–5 was used for preparing the solution mixtures, and for the triple-distilled and degassed water, the specific conductance is less than ±10–6 S·cm–1. The standard uncertainties in the density and speed of sound were approximately ±0.06 kg·m–3 and ±0.6 m·s–1, respectively. For molality, the precision was found to be ±2 × 10–5 mol·kg–1. The apparatus operates at 3 MHz frequency in which the mixture of glycol and vitamin B3 was inserted using a syringe. There exist two separate cells inside the instrument, which measure the two independent parameters, i.e., density and speed of sound, simultaneously at different temperatures, which is governed by the built-in Peltier thermostat.

Acknowledgments

The authors are thankful to Department of Chemistry, Dr. B R Ambedkar NIT, Jalandhar, for providing necessary laboratory facilities.

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.0c04292.

  • Equations and tables for partial molar volume of transfer, temperature-dependent partial molar volume, partial molar isentropic compression of transfer, and pair and triplet interaction coefficients (PDF)

The authors declare no competing financial interest.

Supplementary Material

ao0c04292_si_001.pdf (170.8KB, pdf)

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Supplementary Materials

ao0c04292_si_001.pdf (170.8KB, pdf)

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