464579 Volumetric and Viscometric Properties of a Binary Mixture of a Model Diesel Compound with a Biobased Additive

Monday, November 14, 2016
Grand Ballroom B (Hilton San Francisco Union Square)
Jesus Esteban, Tom Simons, Halina Murasiewicz, Serafim Bakalis and Peter J. Fryer, School of Chemical Engineering, University of Birmingham, Birmingham, United Kingdom

Introduction and background

As a consequence of ongoing regulations to avoid the depletion of fossil fuels as well as environmental concern about their use, renewable sources have gained increasing attention during the past two decades. Among them are biofuels, having biodiesel an increasing prominence.

One of the grand challenges of the biodiesel industry is to manage the surplus of glycerol generated as a by-product of its manufacturing process, whose price has steeply decreased in the past years [1]. Among the routes to exploit such compound, its chemical valorisation is on the spot as a way to obtain value-added products [2].

Among them are acetals, which derive from the reaction of glycerol with an aldehyde or ketone. Solketal (Sk) is the acetal that has attracted the most attention in terms of research [3], for its synthesis is made through the reaction of glycerol with widely available acetone [4]. Sk has proven its relevance as additive to fuels and biofuels by improving certain performance parameters [5-7].

Data on properties of fuels is important to the design of engines, due to the effect that they have on the combustion quality. Therefore, the determination of volumetric and viscometric properties is of relevance. N-hexadecane (also known as cetane) has typically been employed as a compound to model the behavior of diesel [8], so considering that Sk is a promising additive, this work intends to present the volumetric and viscometric properties of binary mixtures consisting of cetane and solketal.


N-hexadecane (purity > 99%) and Solketal (DL-1,2-Isopropylideneglycerol, purity > 98%) by Sigma-Aldrich Co Ltd were used for the the binary mixtures. To prepare samples of varying composition (intervals of 0.1 of molar fraction), a Kern and Sohn ABS 220-4 analytical balance with a 0.0001 g accuracy was used.

Viscosity was measured using a temperature controlled Malvern Bohlin rheometer using a cone (60 mm diameter, 2° angle, 52 μm truncation) and plate geometry. The uncertainties associated to the viscosity and temperature were ±0.001 mPa s and ±0.1 K.

The density measurements were performed in a Krüss K100 tensiometer heated by a temperature controlled Tecam TE-7 Tempette water bath, with an uncertainty in the measurement of ±0.001 mN/m and ±0.01 K, respectively.

Triplicate measurements were performed for each data point for both the properties.

Summary of results and conclusions

The values of density and viscosity of pure n-hexadecane and solketal were validated with already existing data at 293.15, 303.15, 313.15 and 323.15 K for viscosity and 298.15, 303.15, 313.15 and 323.15 K in the case of density. For solketal, whose use is novel, data are still very scarce and referred only to 298.15 K and purities around 95%. The data obtained for the pure n-hexadecane did not differ in more than 3.1% at most for viscosity 0.3% for density.

Fitting of the viscosity (μ) and density (ρ) as a function of temperature were made for the pure components according to equations 1 and 2, respectively:

 μ= μ0 e-k/T (1) 

ρ= a+bT (2)

The values of the fitting parameters therein included were as follows:

  • n-hexadecane: μ0= 6.24x10-6 and k=1846.20 for equation 1; a=0.9747 and b=-6.84x10-4 for equation 2.
  • solketal: μ0= 2.59x10-7 and k=3141.09 for equation 1; a=1.3102 and b=-8.30x10-4 for equation 2.

Then, viscosities and densities of the 9 binary mixtures consisting of increasing molar fractions of solketal in n-hexadecane were measured. From the observed data, the excess molar volumes (VE ), viscosity deviations (Δμ) and excess Gibb’s free energy of activation for viscous flow (ΔGE ) were computed following equations 3 to 5:

VE=(x1M1+x2M2)/ρ-(x1M11+x2M22) (3)

Δμ=μ-[x1μ1+(1-x11] (4)

ΔGE=RT[ln(μV)-(x1ln(μ1V1)+(1-x1)ln(μ2V2)] (5)

where xi and Mi represent the molar fractions and molecular weights of n-hexadecane (1) and solketal (2) in the mixture, V are the molar volumes and R is the ideal gas constant.

Finally, from the excess properties and deviations computed, correlation to a Redlich-Kister type equation was performed.

 P=x1(1-x1)ΣAi(1-x1)i (6)

in which P is the excess property or deviation and Ai are the fitting parameters in the equation.


1. Quispe, C.A.G., C.J.R. Coronado, and J.A. Carvalho, Jr., Glycerol: Production, consumption, prices, characterization and new trends in combustion. Renewable & Sustainable Energy Reviews, 2013. 27: p. 475-493.

2. Behr, A., et al., Improved utilisation of renewable resources: New important derivatives of glycerol. Green Chemistry, 2008. 10(1): p. 13-30.

3. Nanda, M.R., et al., Catalytic conversion of glycerol for sustainable production of solketal as a fuel additive: A review. Renewable and Sustainable Energy Reviews, 2016. 56: p. 1022-1031.

4. Esteban, J., M. Ladero, and F. Garcia-Ochoa, Kinetic modelling of the solventless synthesis of solketal with a sulphonic ion exchange resin. Chemical Engineering Journal, 2015. 269: p. 194-202.

5. Garcia, E., et al., New Class of Acetal Derived from Glycerin as a Biodiesel Fuel Component. Energy & Fuels, 2008. 22(6): p. 4274-4280.

6. Giraldo, S.Y., et al., Síntesis de Aditivos para Biodiesel a partir de Modificaciones Químicas de la Glicerina. Información tecnológica, 2009. 20(6): p. 75-84.

7. Mota, C.J.A., et al., Glycerin Derivatives as Fuel Additives: The Addition of Glycerol/Acetone Ketal (Solketal) in Gasolines. Energy & Fuels, 2010. 24: p. 2733-2736.

8. Wang, X., X. Wang, and J. Chen, Experimental investigations of density and dynamic viscosity of n-hexadecane with three fatty acid methyl esters. Fuel, 2016. 166: p. 553-559.

Extended Abstract: File Not Uploaded