Article

pubs.acs.org/jced

Liquid Viscosity and Surface Tension of n‑Dodecane, n‑Octacosane,

Their Mixtures, and a Wax between 323 and 573 K by Surface Light
Scattering
Thomas M. Koller,*,† Tobias Klein,† Cédric Giraudet,† Jiaqi Chen,‡ Ahmad Kalantar,‡
Gerard P. van der Laan,‡ Michael H. Rausch,† and Andreas P. Fröba†
†
Department of Chemical and Biological Engineering (CBI) and Erlangen Graduate School in Advanced Optical Technologies
(SAOT), University of Erlangen-Nuremberg, Paul-Gordan-Straße 6, 91052 Erlangen, Germany
‡
Shell Global Solutions International B.V., Grasweg 31, 1031 HW Amsterdam, The Netherlands
*
S Supporting Information

ABSTRACT: The present contribution provides experimental

data for the liquid viscosity and surface tension of n-alkane
based model systems at temperatures up to 573 K. The
fundamental advantage of the used surface light scattering
(SLS) method lies in its application in thermodynamic
equilibrium without calibration in a contactless way. The
investigated systems comprise the pure fluids n-dodecane (n-
C12H26) and n-octacosane (n-C28H58), their binary mixture at a
n-C12H26 mole fraction of about 0.3, and the commercially
available hydrocarbon wax SX-70 representing a multicompo-
nent mixture of n-alkanes with a broad chain length distribution.
For the first time, it could be demonstrated that the SLS method can simultaneously access the liquid viscosity and surface
tension of such medium- to long-chained n-alkane systems close to saturation conditions over a broad temperature range from
323 to 573 K. Typical measurement uncertainties of 2% based on a coverage factor k = 2, i.e., a level of confidence of more than
95%, were obtained. Over the entire temperature range, a simple polynomial equation for the dynamic viscosity and a modified
van der Waals equation for the surface tension represent the measured data of the pure and binary systems well. The present
investigations improve the data situation for hydrocarbon systems in the high-temperature range where no measurement results
exist in literature.

■ INTRODUCTION
In the field of chemical and energy technology, the catalytic
For the thermophysical properties of short-chained n-alkanes
having carbon numbers between 1 and 12, there already exists
Fischer−Tropsch process used for the artificial production of an ensured reference database in the form of Refprop.3 Reliable
high-valued petroleum products from synthesis gas has data or models for medium- to long-chained n-alkanes and their
experienced strong revitalized interest in the most recent mixtures in the temperature range which is of interest for the
years.1,2 For product design and process modeling, reliable process are lacking. This issue seems to be related to the
information on the viscosity and surface tension of problems adherent to conventional, in most cases routine,
representative fluid systems is required. Of the different measurement methods used to determine viscosity and surface
transport properties, the viscosity is the central property as it tension of such systems at relatively large temperatures. Here,
affects heat as well as mass transfer processes and determines the adjustment of equilibrium conditions during the measure-
power requirements for mixers and pumps. The surface tension ment close to thermodynamic equilibrium is hardly possible.
is important in connection with mass transfer rates of gas This holds especially in connection with transport properties
absorption at contacting gas−liquid interfaces and the wetting such as viscosity where conventional techniques have to apply a
behavior at machineries or catalytic nanopores. Depending on relatively large shear rate to obtain a measurable effect, resulting
the reaction conditions for, e.g., Fischer−Tropsch processes in unavoidable disturbances of equilibrium. Any macroscopic
with temperatures between about 423 and 523 K as well as gradient subjected to the sample may falsify the results if not
pressures between about 2 and 4 MPa,2 a certain product considered in data evaluation. The fundamental limitations of
distribution of linear and branched alkanes as well as further conventional experiments motivated to use and develop
side products of various chain length is obtained. Thus,
knowledge on the thermophysical properties at elevated Received: April 18, 2017
thermodynamic states, especially in the conditions of high Accepted: June 30, 2017
temperatures above 423 K, is needed. Published: July 18, 2017

© 2017 American Chemical Society 3319 DOI: 10.1021/acs.jced.7b00363

J. Chem. Eng. Data 2017, 62, 3319−3333
Journal of Chemical & Engineering Data Article

modeling methods for the prediction of thermophysical incident light in equally spaced directions around both the
properties in the form of computer simulation 4 and reflected and refracted beams. Surface fluctuations observable in
theoretical/empirical5 approaches. Nevertheless, even for the light scattering experiment typically cover a wavelength
small- to medium-weight n-alkane systems, such predictive range from about 0.1 to 1000 μm. The total root-mean-square
methods can still often not be used for a reliable quantitative amplitude of the surface roughness integrated over all
estimation of viscosity and surface tension, as will be shown wavelengths is typically between 1 and 100 nm. In the SLS
later in this study, and can only be as accurate as the experiment, the dynamics of surface fluctuations in the form of
experimental data used to verify the calculation results. their frequency and damping is probed for a defined
Surface light scattering (SLS) probes, as the name indicates, wavelength. For the temporal decay of surface fluctuations,
the dynamics of thermal fluctuations on the surface of a liquid two cases can be distinguished. In the case of large viscosity
or, in a more general formulation, at phase boundaries. Here, and/or small surface tension, the amplitude is damped
measurements are performed in or close to macroscopic exponentially, while, in the case of small viscosity and/or
thermodynamic equilibrium in a contactless way without the large surface tension, the amplitude of surface fluctuations
need for any calibration. All these features allow for defining the decays in the form of a damped oscillation.
method as a quasi-primary method for the measurement of The scattering geometry used in this study is shown in Figure
viscosity.6 During the past two decades, our research activities 1 where scattered light is observed in the forward direction near
were devoted to developing a proper execution of SLS for a
routine measurement of surface tension and liquid viscosity
with high accuracy for fluids with relatively low viscosity, such
as refrigerants,7−9 hydrofluoroethers,10 or toluene,11 the latter
data which served as reference for the development of a low-
viscosity standard.12 In a second step, our investigations could
demonstrate that the SLS technique constitutes also a valuable
tool for thermophysical property research of high-viscosity
fluids in the form of ionic liquids13−16 or the reference
substance diisodecyl phthalate.17
In the present study, the SLS method is applied, for the first
time, to investigate n-alkane model systems containing n-
dodecane (n-C12H26), n-octacosane (n-C28H58), and their
binary mixture at a n-C12H26 mole fraction of about 0.3 as
well as a multicomponent system in the form of the Figure 1. Scattering geometry used for surface light scattering.
commercially available wax SX-70 with a defined composition
over a broad temperature range between 323 and 573 K close refraction. This arrangement has been chosen due to signal and
to saturation conditions. After an introduction to the SLS stability considerations21 and differs from the more commonly
technique, the materials and sample preparation as well as the employed scattering geometry where the scattered light is
experimental setup are described. Thereafter, a measurement observed close to the direction of the reflected beam. By choice
example and the data evaluation procedure are presented. The of the angle of incidence ΘE and the scattering angle ΘS, the
main objectives of this work are to show the capability of SLS
scattering vector q ⃗ = kI⃗ ′ − k S⃗ ′ is determined and, from this, the
for a simultaneous determination of liquid viscosity and surface
tension of selected n-alkane systems over a broad temperature wave vector and frequency of the observed surface vibration
range in an accurate manner and to fill the existing gap in the mode. Here, kI⃗ ′ and k S⃗ ′ denote the projections of the wave
database for an industrially relevant class of working fluids. vectors of the reflected (kI⃗ ) and scattered (kS⃗ ) light to the
Besides a critical analysis of the experimental uncertainties of surface plane, respectively. In the special optical arrangement
the present measurements and of the available scarce literature illustrated in Figure 1, light scattered on the liquid−vapor
data, simple correlations for the liquid viscosity and surface interface is detected perpendicular to the surface plane. In
tension of the studied systems are provided. addition, scattered light is observed within the irradiation plane

■ SURFACE LIGHT SCATTERING

For the present investigations of a phase boundary between the
and elastic scattering (i.e., kI ≅ kS) can be assumed. Based on
these conditions, the modulus of the scattering vector can be
deduced from Snell’s refraction law and simple trigonometric
corresponding liquid and vapor phases of the n-alkane systems, identities resulting in
an exact treatment of the capillary wave problem taking into 2π
account the phase boundary is necessary to reliably determine q = |kI⃗ ′ − k S⃗ ′| ≅ sin(ΘE)
λ0 (1)
viscosity and surface tension with high accuracy. For a detailed
description of the fundamentals and methodological principles where λ0 is the laser wavelength in vacuo. Each scattering vector
of SLS, the reader is referred to specialized literature.18,19 In chosen solely from the adjusted angle of incidence corresponds
this section, the main information on the SLS technique which to a specific wavelength (2π/q) of surface vibration mode as it
is relevant for the present study is provided. is shown in Figure 1.
In macroscopic thermal equilibrium, liquid surfaces exhibit Based on classical hydrodynamic theory, the temporal decay
surface waves that are caused by the thermal motion of of a particular surface mode of the form exp[iq ⃗ r ⃗ + St/τ0], with
molecules.20 The result of such fluctuations is a rough surface a wave vector q⃗ at a given point r,⃗ is obtained from the
which can be represented by a superposition of surface waves dispersion equation for surface waves at the interface between
with different amplitudes and wave vectors. Each Fourier contacting liquid (′) and vapor (″) phases.22 By introducing the
component of the rough surface scatters a small fraction of an dimensionless parameter
3320 DOI: 10.1021/acs.jced.7b00363
J. Chem. Eng. Data 2017, 62, 3319−3333
Journal of Chemical & Engineering Data Article

ρ′ + ρ″ ⎛ g (ρ ′ − ρ ″ ) ⎞ data obtained from the SLS experiment for the dynamics of

Y= ⎜ σ + ⎟ surface waves, i.e., the frequency ωq and damping Γ at a defined
4(η′ + η″)2 q ⎝ q2 ⎠ (2) wavenumber q, have to be combined with reference data for the
with ρ′ and ρ″ being the densities of the liquid and vapor dynamic viscosity of the vapor phase η″ and density data for
phases, η′ and η″ the dynamic viscosities of the liquid and vapor both phases ρ′ and ρ″ to get information on the liquid
phases, respectively, σ the surface tension, and g the local kinematic viscosity ν′ or liquid dynamic viscosity η′ (η′ = ν′ρ′)
acceleration of free-fall, as well as introducing the reduced and surface tension σ. Details on the data evaluation are given
frequency later in the corresponding section.
In SLS, scattered light emerging from the interaction
ρ′ + ρ″ between incident light and the fluctuating surface structure
S = iατ0 , with τ0 =
2(η′ + η″)q2 (3) can be analyzed using photon correlation spectroscopy. In this
type of detection, the time-dependent correlation function of
the dispersion relation can be transformed into its reduced the scattered light intensity is measured at a point in the far
form22 field. For heterodyne conditions, where the scattered light is
ρ′2 − ρ″2 + 2Rρ′ρ″ η′(M′ − 1) − η″(M″ − 1) superimposed with coherent reference light of much higher
D(S) = Y + S
(ρ′ + ρ″)2 η′(M′ + 1) + η″(M″ + 1) intensity, the normalized intensity correlation function for the
⎧ analysis of surface fluctuations showing an oscillatory behavior
ρ′ η′(M′2 + 1) + η″[M′ − 1 + M″(M′ + 1)]
is described by22
⎪

+⎨
⎩ (ρ′ + ρ″) (M′ − 1)[η′(M′ + 1) + η″(M″ + 1)]
⎪

ρ″ η″(M″2 + 1) + η′[M″ − 1 + M′(M″ + 1)] ⎫ 2 g(2)(τ ) = a + b cos(ωq τ − ϕ) exp( −τ /τC) (8)

+ ⎬S
(ρ′ + ρ″) (M″ − 1)[η′(M′ + 1) + η″(M″ + 1)] ⎭
(4) The experimental constants a and b in eq 8 are essentially
determined by the total number of registered counts, the ratio
In eq 4, the dimensionless properties R, M′, and M″ are given
of scattered light to reference light, and the coherence
by
properties of the optical system. The time-dependent parts of
η′ / ρ ′ − η″ / ρ ″ eq 8 are proportional to the correlation function of the surface
R= fluctuations, whose Fourier transform is, according to the
(η′ + η″)/(ρ′ + ρ″) (5)
Wiener−Khintchine theorem, the corresponding power spec-
ρ′ + ρ″ trum of the surface fluctuations. The phase term ϕ largely
M′ = 1+2 S accounts for the deviations of the spectrum from the Lorentzian
ρ′ + ρ″ + Rρ″ (6) form and was used as a variable in the data evaluation
procedure. The correlation time τC and the frequency ωq are
ρ′ + ρ″
M″ = 1+2 S identical with the mean lifetime or the reciprocal of the
ρ′ + ρ″ − Rρ′ (7) damping constant Γ (=1/τC) of the surface ripplons and their
The reduced frequency S is related to the complex frequency α frequency of propagation, respectively. The latter relate to the
(α = ωq + iΓ) and to the characteristic viscous time τ0. fluid properties through the capillary wave dispersion equation;
Furthermore, the real part of the complex frequency α see eq 4.
represents the frequency ωq and the imaginary part the
damping Γ of the observed surface vibration mode with the
corresponding wavenumber q.
■ EXPERIMENTAL SECTION
In the following experimental section, the materials and sample
At relatively small surface wavelengths, as it is relevant in this preparation as well as the experimental setup and procedure
work, the last term in eq 2, which arises from the force of relevant for the present investigations are summarized.
inertia, can be neglected without significant increase in Materials and Sample Preparation. According to the
uncertainty. The solution of the dispersion relation in eq 4 specifications of the manufacturer, the linear n-alkanes n-
shows that there exists a critical value for Y for which the dodecane (n-C12H26, molar mass M = 170.33 g·mol−1,
temporal behavior of the surface fluctuations changes depend- purchased from Merck GmbH) and n-octacosane (n-C28H58,
ing on the thermophysical properties of the fluid and the M = 394.77 g·mol−1, purchased from Alfa Aesar GmbH & Co.
wavenumber selected. For Y < 1 associated with large liquid KG) had both nominal purities in terms of mass fractions of w
viscosities and/or low surface tensions, surface fluctuations are > 0.99. The wax SX-70 (XTL heavy HPS paraffins) was
overdamped and do not propagate (ωq = 0). For Y > 1 obtained from Shell Global Solutions B.V. and represents a
associated with small liquid viscosities and/or large surface mixture of heavy n-alkanes. A detailed analysis of the
tensions, surface fluctuations propagate and show an oscillatory composition of the four different n-alkane systems investigated
behavior. This case has been observed in all measurements in our SLS measurements was obtained by gas chromatography
presented in this work, where the smallest Y value was 1.6, and (GC) and can be found in the Supporting Information in
is only studied in the following. When Y ≫ 1 or Y ≪ 1, first- Tables S1 and S2. The results are based on the analysis of
order approximations11,18 for S can be used for an accurate theoretical flame ionization detector response factors. These
description of the dynamics of surface waves. For intermediate factors have been calculated by the effective carbon number
values of Y, the dynamics of surface waves can no longer be method published by Sternberg et al.26 Besides the main
described with sufficient certainty by the first-order approx- components, other groups commonly found in Fischer−
imation as it is often carried out in literature.23−25 Tropsch related samples such as branched alkanes, aromatics,
For an accurate determination of liquid viscosity and surface or oxygenated compounds were categorized according to the
tension from the light scattering experiment, the dispersion number of carbon atoms NC. The absolute uncertainty of the
relation eq 4 must be considered in its complete form. For this, mass fractions w measured by the GC method can be estimated
3321 DOI: 10.1021/acs.jced.7b00363
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Journal of Chemical & Engineering Data Article

Table 1. Specification of the Used Chemicals

purification purity or composition before the purity or composition after the
system source method measurement measurement
n-C12H26 Merck GmbH none w = 0.9945a w = 0.9941a
n-C28H58 Alfa Aesar GmbH & Co. KG filtration w = 0.9950a w = 0.9832a
0.3n-C12H26/0.7n-C28H58 Merck GmbH/Alfa Aesar GmbH none/filtration x1/x2 = 0.300/0.700b (total w > 0.99) x1/x2 = 0.287/0.713a
& Co. KG (total w = 0.9957a)
wax SX-70 Shell Global Solutions B.V. filtration see Table S2 and Figure S1
helium Linde AG none ψ = 0.99999
a
Obtained from GC analysis. The expanded uncertainties U of the mass fractions w of the pure and binary systems of interest are U(w) = 0.001
(level of confidence = 0.95). bEstimated from the GC results for the pure substances and the weighing procedure. The expanded uncertainties U of
the overall mass fraction w of the binary system is U(w) = 0.002 (level of confidence = 0.95).

Figure 2. Scheme of the experimental setup.

to be U(w) = 0.001 based on a confidence level of more than between 373.15 and 573.15 K. Filtered n-C28H58 was liquefied
95% (k = 2). in a beaker at about 340 K before an appropriate amount of n-
According to the GC results, the initial purities of w = 0.9945 C12H26 was added. To achieve the desired composition of the
for n-C12H26 and w = 0.9950 for n-C28H58 obtained before the n-alkane mixture, both liquid compounds were weighed before
SLS experiments could confirm the specifications given by the and after filling with a balance (Sartorius BP110) with an
supplier. Referring to the mass distribution in Figure S1 in the expanded uncertainty (k = 2) of 1 mg. From the weighing
Supporting Information, the sample for the wax SX-70 analyzed procedure, an initial mass fraction ratio for n-C12H26/n-C28H58
before the measurements shows a broad, slightly asymmetric of w1/w2 = 0.156/0.844, corresponding to a mole fraction ratio
distribution of linear n-alkanes ranging between about n-icosane of x1/x2 = 0.300/0.700, was adjusted. Here, the absolute
(n-C20H42) and n-hexacontane (n-C60H122). The compound uncertainty (k = 2) in both the mass and mole fractions based
mostly found in the wax is n-tritriacontane (n-C33H68) with w = on the weighing procedure is supposed to be 0.001. Taking into
0.068. consideration the uncertainty of the GC results for the pure
At ambient conditions, the n-C28H58 and wax samples are substances of w = 0.001, the total expanded uncertainty (k = 2)
solid and start to melt at about 335 K. Due to the broader of the overall mass fraction of the binary mixture is estimated to
distribution of heavy alkanes in the wax sample, the melting be w = 0.002.
temperature reaches up to about 373 K. Both liquefied samples To avoid any change in the sample composition of the binary
showed particle-like impurities presumably resulting from the mixture and the wax SX-70 during sample preparation caused
manufacturing process. To obtain ideally particle-free samples by different evaporated amounts of the components, a fast
as necessary for SLS experiments, samples of n-C28H58 and the preparation procedure was necessary. The inevitable variation
wax SX-70 were filtered with a syringe filter with 220 nm pore in the composition of the liquid binary mixture over the
size at about 373 and 423 K, respectively. investigated temperature range could be estimated by mass
The binary n-alkane mixture consisting of mole fractions x of balance calculations detailed later on. Helium (M = 4.0026 g·
about x1 = 0.30 of n-C12H26 and x2 = 0.70 of n-C28H58 (0.3n- mol−1), which served as an inert gas for sample handling and
C12H26/0.7n-C28H58) was investigated in the temperature range control of the sample composition during the experiments, was
3322 DOI: 10.1021/acs.jced.7b00363
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Journal of Chemical & Engineering Data Article

supplied by Linde AG with a volume fraction purity ψ of length of 7 cm due to the larger total inner volume of about 105
0.99999. mL instead of 40 mL. A length of 7 cm corresponds to the same
All liquefied samples were transparent at the beginning of the value as that used in our former study on toluene11 and is
measurements. After the measurements up to 573 K in the case sufficient to avoid disturbing capillary effects of the liquid at the
of n-C12H26, n-C28H58, and 0.3n-C12H26/0.7n-C28H58, a slight edges of the cell on the probed region. Also due to this
yellowish coloration could be found. A further GC analysis was arrangement, line broadening effects could be suppressed
carried out to check if any thermal decomposition or completely. The four optical accesses, which are uniformly
oxygenation of n-alkanes27 occurred in the high-temperature distributed around the cell and where two of them are used to
range. The GC results obtained for the samples after the SLS guide the incident beam and collect the scattered light, were
measurements are also given in Table S1 in the Supporting made of quartz windows (Herasil, diameter 30 mm × length 20
Information and show no distinct change in the composition of mm).
the n-C12H26 (w = 0.9941) and n-C28H58 (w = 0.9832) samples. The temperature of the sample cell was controlled by
For the binary mixture of n-C12H26 and n-C28H58, the total resistance heating and measured by a calibrated Pt-100 Ω
fraction of both substances in the sample was w = 0.9957 resistance probe. This is integrated into the wall of the sample
according to the GC results. The reduction of the mole fraction cell close to the heating wire and connected to an AC bridge
ratio of n-C12H26/n-C28H58 from 0.300/0.700 to about 0.287/ (Anton Paar MKT 100). Given the large thermal conductivity
0.713 is caused by the larger volatility of n-C12H26 than n- of the cell material and the close proximity of the resistance
C28H58, resulting in a weak depletion of n-C12H26 relative to n- probe to the vapor−liquid interface, it can reliably be assumed
C28H58 in the liquid phase during the measurements. A that the temperature of the resistance probe corresponds to the
summary of the used chemicals is given in Table 1. temperature of the fluid. The uncertainty in the absolute
Experimental Setup and Procedure. The experimental temperature measurement is 15 mK (k = 2). The temperature
setup used for the investigation of a liquid−vapor interface of stability of the temperature probe used for temperature control
the studied n-alkane systems close to saturation conditions is and measurement was better than 5 mK during each
the same as that used in our former studies11,16,17 and shown in experimental run. The reported sample temperature data
Figure 2. The main information on the setup necessary for the stem from the average of the recorded readings of the sensor
present study is detailed below. A frequency-doubled for a given temperature point. Taking also the uncertainty and
continuous-wave Nd:YVO4-laser (Coherent, Verdi-V2) oper- position of the used resistance probe into account, the
ated in a single mode with a wavelength of λ0 = 532 nm serves expanded uncertainty for all reported temperatures is estimated
as a light source. The laser power was about 500 mW when to be 0.05 K (k = 2) over the entire temperature range.
working at temperatures T < 350 K and somewhat lower for Before each measurement series, a pressure test of the cell
higher temperatures. For the observation of light scattered by using helium at pressures of about 2 MPa was successfully
surface waves, the optical path has to be aligned in such a way performed. Thus, a tightness of the cell during the measure-
that the laser beam and the direction of detection intersect on ments could be ensured. For the filling of the sample cell, first
the liquid−vapor interface in the measurement cell. For large the liquefied samples were inserted into the cell via the upper
scattering intensities from the vapor−liquid interface, scattered window. The gas phase was then flushed by helium several
reference light from the cell windows is not sufficient to realize times in order to avoid any contamination of the sample with
heterodyne conditions. Here, an additional reference beam is air or other gases which may enable an oxygenation of the
added. For this, part of the incident laser light is split by a glass sample. After that, the system was closed by inserting and fixing
plate and superimposed with the scattered light behind the the upper window, and an initial partial pressure of about 0.1
sample cell. The time-dependent intensity of the scattered light MPa of helium could be adjusted. The pressure was not
is detected by two photomultiplier tubes (PMTs) operated in registered during the measurement in order to keep the system
cross-correlation in order to suppress after-pulsing effects. The volume and the disturbance of the thermodynamic equilibrium
signals are amplified, discriminated, and fed to a linear-tau small, but could be estimated to be smaller than 0.2 MPa in all
digital correlator featuring 256 equally spaced channels cases. Given the insignificant effect of pressure on the liquid
operated with a sample times down to 37.5 ns. viscosity and surface tension of n-alkane systems at relatively
The design of the optical arrangement is based on the small pressures below 0.2 MPa,3 all presented measurements
analysis of scattered light at variable and relatively high wave can be considered to be carried out close to saturation
numbers of capillary waves, whereby instrumental broadening conditions.
effects are negligible.11 According to eq 1, the wavenumber q For each temperature, six measurements at different angles of
can be adjusted as a function of the easily accessible angle of ΘE = 3.0°, 3.1°, and 3.2° were performed, where the laser was
incidence ΘE. To measure the latter property, the laser beam is irradiated from either side with respect to the axis of
first adjusted through the detection system consisting of two observation in order to check for a possible misalignment.
apertures (diameter 1 mm) at a distance of about 4 m. Then, Furthermore, line-broadening effects can be excluded for such a
the laser beam is set to the desired angle. For the experiment, choice of incident angles. The measurement times for a single
the angle of incidence ΘE was set between 3.0° and 3.2° and run were typically on the order of 20 min down to a couple of
was measured with a high-precision rotation table. The error in minutes for the highest temperatures in this study. During a
the angle measurement was determined to be approximately measurement series for each system, the temperature was
0.005° (k = 2). increased step by step. While for pure n-C12H26 the lowest
A sample cell consisting of stainless steel and having the same temperature was set to 323.15 K, larger temperatures of T =
outer dimensions as that employed in our previous light 398.15 K for n-C28H58 and T = 373.15 K for 0.3n-C12H26/0.7n-
scattering measurements from the bulk of fluids28−30 was used. C28H58 were required to suppress disturbing influences from
Compared to the latter investigations, the special feature of the scattering due to solid agglomerates which were not yet molten
cell used in this study is that it provides a larger effective surface below the stated temperatures. Temperature steps of 25 K were
3323 DOI: 10.1021/acs.jced.7b00363
J. Chem. Eng. Data 2017, 62, 3319−3333
Journal of Chemical & Engineering Data Article

used for the pure and binary systems. For the wax SX-70, a dynamic viscosity of the almost saturated vapor phase. Since the
limited temperature range between 473.15 and 523.15 K in systems investigated in this work are still relatively far away
steps of 10 K was studied in order to avoid any thermal from the critical point, the liquid phase is mainly dominating
decomposition of very long chained hydrocarbons at overly the dynamics of the surface waves. For the vapor properties,
large temperatures. For all studied systems, repetition measure- uncertainties of about 20% are sufficient enough to determine
ments were performed at least one time within the series and the liquid properties accessible by SLS within less than 1%. In
after the last measurement at the largest temperature of 523.15 the following, the sources used for the required input values for
or 573.15 K. This allowed checking of the stabilities of the the thermophysical properties of the studied systems are given
investigated samples. and discussed.

■ MEASUREMENT EXAMPLE AND DATA

EVALUATION
For n-C12H26, the densities of the liquid and vapor phases
have been adopted from the equation of state of Lemmon and
Huber.31 Data for the dynamic viscosity of the vapor phase are
Figure 3 shows an example correlation function obtained from calculated from a pure fluid model according to Huber et al.32
scattering on the interface of liquid n-C28H58 close to saturation For n-C28H58, the liquid density was employed from a
correlation of Dutour et al.33 based on their experimental
data measured between 353.15 and 403.15 K at atmospheric
pressure with a U-tube densimeter. The uncertainty of the
measurement results is not specified but can be estimated to be
0.1%. The vapor viscosity of n-C28H58 was deduced from the
temperature-dependent correlation given by Yaws’ Handbook
of Thermodynamic and Physical Properties of Chemical
Compounds,5 a database which is freely available in the
Internet. Therein, it is stated that the tabulated values are based
on regression of experimental data and researched estimates.
The uncertainty of the apparently purely predictive estimations
for the vapor viscosity of n-C28H58 provided by Yaws’ handbook
is not specified but can be estimated with a value of 20% (k =
2). Even for the largest temperature studied (T = 573.15 K),
the vapor viscosity of pure n-C28H58 (η″ = 0.0051 mPa·s) is
about 80 times smaller than the corresponding liquid viscosity.
Similar vapor viscosities in the zero-density limit (e.g., η″ =
0.0058 mPa·s at T = 573.15 K), which applies well for the
current investigations, were calculated for n-C28H58 using the
Figure 3. Measurement example of a normalized correlation function recent prediction model of Riesco and Vesovic.34 For the
(upper graph) and the residuals (lower graph) for n-C28H58 at a saturated vapor of n-C28H58, no density data are available.
temperature of 498.15 K using an incident angle of 3°: □, Instead, Yaws’ handbook5 allows for estimations of the vapor
measurement data; −, fit according to eq 8. pressure of n-C28H58, which is more than 100 times smaller
than that of pure n-C12H26 over the entire temperature range
conditions at a temperature of 498.15 K and an incident angle studied.
ΘE = 3°. The experimental correlation function, eq 8, has to be The influence of the vapor properties of n-C28H58 on the
evaluated for the central quantities, ωq and τC, which is values for liquid viscosity and surface tension of pure n-C28H58
performed by a nonlinear regression based on a Levenberg− was exemplarily estimated at a temperature of 573.15 K where
Marquardt (LM) algorithm in which the squared sum of the effect of the vapor properties is the largest. In the two cases
residuals is to be minimized. Within the entire fit range, no where the vapor properties of n-C28H58 are considered or
systematic deviations or any disturbing signals in the long-time neglected, relative deviations between the final liquid dynamic
range of the correlation function can be observed. This is viscosities of 0.2% and surface tensions of 0.1% are obtained.
illustrated in the residual plot in Figure 3 and was confirmed for These differences are about an order of magnitude smaller than
all present measurements. The uncertainties (k = 2) obtained the experimental uncertainties of the measured properties.
from the fit are given in brackets and are below 0.4% for ωq and Thus, due to the very small impact of the vapor properties of n-
1.3% for τC. In most of the cases, uncertainties below 1% for ωq C28H58, the vapor phase for the liquid systems consisting of
and 2% for τC could be obtained. It is obvious that the error in pure n-C28H58 and of the binary mixture of 0.3n-C12H26/0.7n-
the determination of the frequency was generally smaller than C28H58 can sufficiently be modeled by estimating a gas phase
that of the decay time, especially at larger temperatures where consisting of pure helium and a binary mixture of helium and n-
more and more oscillations appeared in the correlation C12H26, respectively.
functions. The liquid density of the wax SX-70 was obtained based on
As discussed above and detailed in our former studies,11,18 a volumetric measurements of a given amount of sample at
reliable determination of surface tension and viscosity is only temperatures between 363.15 and 423.15 K in steps of 20 K.
possible by an exact numerical solution of the dispersion For the density data which are provided in the Supporting
equation, eq 4, where the frequency ωq, the decay time τC, and Information in Table S3, the uncertainty can be specified with a
the modulus of the scattering vector q are used as input values. value of 0.2% (k = 2). The experimental data were correlated by
This procedure has always been performed within the present a linear fit with respect to temperature which was used to
study. Further input data for solving the dispersion relation are extrapolate to the temperature range between 473.15 and
the density of the liquid phase as well as the density and 523.15 K studied in the SLS experiments. At these conditions,
3324 DOI: 10.1021/acs.jced.7b00363
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Journal of Chemical & Engineering Data Article

Table 2. Liquid Dynamic Viscosity η′ and Surface Tension σ of the Pure Substances n-C12H26 and n-C28H58 Close to Saturation
Conditions Obtained by Surface Light Scattering as a Function of Temperature T Using Corresponding Literature Data for the
Liquid Density ρ′, Vapor Density ρ″, and Vapor Viscosity η″a
T/K ρ′/(kg·m−3) ρ″/(kg·m−3) η″/(μPa·s) η′/(mPa·s) 100Ur(η′) σ/(mN·m−1) 100Ur(σ)
n-C12H26
323.15 727.2 0.14 19.7 0.9225 2.3 21.64 1.0
348.15 708.6 0.15 20.4 0.6763 1.8 19.91 1.5
373.15 689.9 0.15 21.4 0.5070 1.4 18.19 1.7
398.15 670.7 0.16 22.7 0.4003 1.5 16.22 0.8
423.15 651.0 0.20 23.5 0.3223 1.8 14.33 1.8
448.15 630.4 0.41 23.2 0.2595 1.7 12.38 1.9
473.15 608.8 1.03 21.7 0.2156 1.5 10.67 0.7
498.15 585.8 2.44 19.1 0.1821 1.5 8.95 1.8
523.15 560.9 5.20 16.5 0.1532 2.1 7.25 1.0
548.15 533.4 10.08 14.6 0.1277 1.4 5.64 1.2
573.15 502.4 18.07 13.8 0.1051 2.2 4.14 1.6
n-C28H58
398.15 738.5 0.15 24.2 1.8142 4.3 21.33 3.1
423.15 721.3 0.15 25.3 1.3609 2.8 19.53 2.5
448.15 704.0 0.15 26.3 1.0252 1.8 17.78 1.5
473.15 686.7 0.15 27.3 0.8318 1.7 16.57 2.8
498.15 669.6 0.15 28.3 0.6847 2.1 15.38 1.7
523.15 653.0 0.15 29.3 0.5675 2.2 14.18 1.6
548.15 637.0 0.15 30.2 0.4753 2.4 12.86 1.1
573.15 622.0 0.15 31.2 0.3995 1.5 11.51 1.3
a
The expanded uncertainties U are U(T) = 0.05 K, while the relative expanded uncertainties Ur(η′) and Ur(σ) are given in the table (level of
confidence = 0.95).

an uncertainty of 1% for the liquid density of the wax can be mated with the term surface tension referring to a liquid or
estimated. liquid mixture in equilibrium solely with their own vapor phase.
According to the composition of the wax SX-70 analyzed While for the liquid n-C28H58 and wax SX-70 samples, a pure
before the measurements (see Table S2 and Figure S1 in the helium gas phase can be considered, binary gas mixtures of
Supporting Information), predominantly heavy n-alkanes with helium and n-C12H26 are modeled for the liquid systems
chain lengths of more than 20 carbon atoms can be found. The containing pure n-C12H26 and the binary mixture of n-C12H26
mass fraction of alkanes having NC values smaller than 20 is and n-C28H58. For the latter system, the vapor phase
about 0.03%. According to estimations based on Yaws’ composition was calculated in an ideal approach in which the
handbook,5 the vapor pressure of n-alkanes decreases strongly partial pressures related to helium and n-C12H26 were added.
with increasing chain length and becomes negligible for NC > Here, the partial pressure related to n-C12H26 is calculated from
20 within the temperature range investigated in this study. Due the product of the vapor pressure of pure n-C12H26 and its
to the strong presence of barely volatile long-chained alkanes in corresponding mole fraction in the liquid phase.
the liquid mixture, a very low total vapor pressure originating For the binary liquid mixture 0.3n-C12H26/0.7n-C28H58, it is
from the liquid wax sample can be expected. Thus, the vapor assumed that only those two substances are present in the
phase for the wax system can be modeled solely by pure helium. liquid phase. Furthermore, the mole fraction ratio of 0.300/
0.700 is only valid for the initial temperature of 373.15 K
The vapor phase properties were determined from the vapor
studied in the experiment. Due to the strongly increasing vapor
pressures of the corresponding saturated liquids present in the
pressure of n-C12H26 with increasing temperature, more and
samples and the partial pressure from the helium used as inert
more n-C12H26 transfers from the liquid into the vapor phase,
gas in all cases. These data could be used to estimate the
while the amount of liquid n-C28H58 can be approximated as
composition of the partially saturated vapor phase for all constant at the various T states. To calculate the mole fractions
studied systems. For helium, the gas density and viscosity data of n-C12H26 and n-C28H58 in the liquid phase, mass balance
were obtained from the Helmholtz equation of state for helium calculations considering the volumes and densities of the two
published by Ortiz-Vega35 and the pure fluid model of Arp et phases were carried out. Based on this scheme, the mass
al.,36 respectively. The solubility of the inert gas helium in n- fraction w of n-C12H26 in the liquid phase varies between 0.156
dodecane can be estimated to be below x = 0.001, i.e., below w ± 0.002 at T = 373.15 K and 0.148 ± 0.002 at 573.15 K. The
= 0.00002 for low pressures of about 0.1 MPa and temperatures latter value corresponds to the value obtained by the GC
up to 573 K, and it rather decreases with increasing alkyl chain analysis performed after SLS measurements up to 573.15 K.
length.37,38 Thus, the effect of the helium gas on the liquid The detailed values for the composition in the liquid phase of
properties density, viscosity, and surface tension of the systems the binary mixture are tabulated in the next section. Based on
studied can reliably be neglected. In this context, thestrictly the procedure given above, the corresponding liquid density for
speakingcorrect property measured for the n-alkane systems the binary mixture 0.3n-C12H26/0.7n-C28H58 was modeled
close to saturation conditions by SLS, the interfacial tension according to a mixing rule developed by Assael et al.39 for
between the liquid−vapor interface, may reliably be approxi- linear liquid n-alkanes. This model requires only information on
3325 DOI: 10.1021/acs.jced.7b00363
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Journal of Chemical & Engineering Data Article

Table 3. Liquid Dynamic Viscosity η′ and Surface Tension σ of the Binary Mixture 0.3n-C12H26/0.7n-C28H58 Close to Saturation
Conditions Obtained by Surface Light Scattering as a Function of Temperature T Using Corresponding Literature Data for the
Liquid Density ρ′, Vapor Density ρ″, and Vapor Viscosity η″ as Well as Estimated Mass Fractions w of n-C12H26 in the Liquid
Phasea
T/K w/% ρ′/(kg·m−3) ρ″/(kg·m−3) η″/(μPa·s) η′/(mPa·s) 100Ur(η′) σ/(mN·m−1) 100Ur(σ)
373.15 15.6 744.3 0.15 22.4 1.9440 3.0 21.71 2.5
398.15 15.6 727.0 0.15 23.4 1.4119 2.7 19.80 2.4
423.15 15.6 709.4 0.17 24.5 1.0885 2.1 18.50 1.1
448.15 15.5 691.5 0.25 25.0 0.8604 2.0 17.07 1.2
473.15 15.5 673.4 0.51 24.4 0.6912 1.4 15.59 1.1
498.15 15.4 655.2 1.20 22.9 0.5671 1.9 14.15 1.1
523.15 15.2 637.0 2.78 20.9 0.4787 1.9 12.84 1.6
548.15 15.0 618.9 5.94 19.0 0.4075 2.1 11.56 1.2
573.15 14.8 600.9 11.74 17.5 0.3445 1.4 10.30 1.7
a
The expanded uncertainties U are U(T) = 0.05 K, while the relative expanded uncertainties Ur(η′) and Ur(σ) are given in the table (level of
confidence = 0.95).

Table 4. Liquid Dynamic Viscosity η′ and Surface Tension σ of the Wax SX-70 Close to Saturation Conditions Obtained by
Surface Light Scattering as a Function of Temperature T Using Corresponding Literature Data for the Liquid Density ρ′, Vapor
Density ρ″, and Vapor Viscosity η″a
T/K ρ′/(kg·m−3) ρ″/(kg·m−3) η″/(μPa·s) η′/(mPa·s) 100Ur(η′) σ/(mN·m−1) 100Ur(σ)
473.15 732.2 0.15 27.3 1.230 4.6 16.80 3.0
483.15 727.2 0.15 27.7 1.083 3.6 16.09 3.6
493.15 722.3 0.15 28.1 1.000 4.0 15.27 3.9
503.15 717.3 0.15 28.5 0.921 4.4 14.08 4.3
513.15 712.3 0.15 28.9 0.872 4.5 13.45 4.5
523.15 707.3 0.15 29.3 0.791 3.6 13.31 5.2
a
The expanded uncertainties U are U(T) = 0.05 K, while the relative expanded uncertainties Ur(η′) and Ur(σ) are given in the table (level of
confidence = 0.95).

the mass composition and the saturated densities of the pure Summary of Dynamic Viscosity and Surface Tension
liquids as a function of temperature. Such a mixing rule works Data. The results for the liquid dynamic viscosity η′ and
sufficiently well for binary combinations of linear n-alkanes surface tension σ of the four hydrocarbon systems n-C12H26, n-
having carbon numbers NC between 6 and 24 with relative C28H58, 0.3n-C12H26/0.7n-C28H58, and the wax SX-70 between
deviations between modeled and experimental data of less than 323.15 and 573.15 K obtained from SLS close to saturation
0.5% for various temperatures.39 conditions are summarized in Tables 2−4. The listed data are
To model the vapor density of the binary mixtures, a linear average values of at least six independent measurements with
mole-based mixing rule using the densities of helium gas and n- different angles of incidence ΘE. Furthermore, the used input
C12H26 vapor according to the corresponding data from the data for the liquid density ρ′, vapor density ρ″, and vapor
Refprop database3 was applied. Such a simple prediction viscosity η″ required for data evaluation as described in the
scheme can represent the density of gas mixtures at low previous section are tabulated.
pressures well within ±5%.3 To model the vapor viscosity, a Uncertainty Analysis. From the typical variation of liquid
more sophisticated model in the form of the Lucas method40 viscosity and surface tension of the studied systems with
was applied since the vapor viscosity has a stronger impact on temperature, the uncertainty in the temperature measurement
the properties of interest than the vapor density. The of 0.05 K leads to maximum relative uncertainties below 0.07%
corresponding-states model of Lucas40 requires information and 0.02% in the measured liquid dynamic viscosities and
on the mole composition, critical data of the pure compounds, surface tensions, respectively, over the entire temperature
and corrections for polarity and quantum effects, the latter data range. Estimated uncertainties in the liquid mass fraction of up
which were considered for helium. Using this model, the to 0.002 are adherent to uncertainties in the liquid density of up
viscosity of gas mixtures at low pressures can typically be to 1%. The latter uncertainties are taken into account in the
represented within ±10% compared to experimental data.41 following error analysis considering the uncertainties induced

■
by the primary measured variables and input data.
Although the approximate solution for the dynamics of
RESULTS AND DISCUSSION
surface waves given in ref 11 never allows for the determination
First, the temperature-dependent values for dynamic viscosity of viscosity and surface tension with high accuracy (for doing
and surface tension data of the investigated n-alkane systems this, the exact solution of the dispersion relation, eq 4, has
are presented. Then, an uncertainty analysis of the measure- always been used in this work), yet it can be applied to get a
ment results and a data correlation including an interpretation good estimate for the total uncertainty of our SLS results in an
of the data from a molecular point of view is performed. Finally, analytical manner. The direct quantity related to the liquid
the experimental results are compared with available literature kinematic viscosity ν̃ is determined by both vapor and liquid
data. properties, i.e., ν̃ = (η′ + η″)/(ρ′ + ρ″).11 Thus, the estimate for
3326 DOI: 10.1021/acs.jced.7b00363
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Journal of Chemical & Engineering Data Article

the uncertainty of the liquid dynamic viscosity values Δη′ (k =

2) results in
Δη′ ≈ [[(ρ′ + ρ″)Sν̃]2 + (νΔ
̃ ρ′)2 + (νΔ
̃ ρ″)2 + (Δη″)2 ]1/2
(9)
based on the double standard deviation Sν̃ of the measurement
values for the kinematic viscosity and on the uncertainty of the
reference data needed for the determination of the liquid
kinematic viscosity from the directly observable ν̃. Similarly, the
quantity directly accessible by the numerical solution of the
approximate solution, where only data obtained from the light
scattering experiment are used as input parameters, is the ratio
σ̃ = σ/(ρ′ + ρ″) of the surface tension to the sum of the
densities of the liquid and vapor phases.11 In an analogous way,
the uncertainty for the surface tension can be estimated
according to
Δσ ≈ [[(ρ′ + ρ″)Sσ̃]2 + (σ ̃Δρ′)2 + (σ ̃Δρ″)2 ]1/2 (10)
For the relative uncertainties of the vapor properties viscosity
Δη″/η″ and density Δρ″/ρ″ of all studied systems, values of
10% (k = 2) have been estimated. The relative uncertainty of Figure 4. Estimated relative total measurement uncertainties (k = 2)
the liquid density Δρ′/ρ′ was assumed to be 0.5% for n-C12H26 for the liquid dynamic viscosity Δη′/η′ (a) and the surface tension
and 1% for the other three systems. Δσ/σ (b) of n-C12H26 and individual contributions to those values.
As observed in many DLS applications,11,42 the standard The lines in both graphs indicate the upper limit for the estimated
deviation of individual measurements may be considered as a total uncertainties and should serve as guides for the eye. (a) Δx: □,
Δη′; + , (ρ′+ρ″)Sṽ; ○, ṽΔρ′; ◊, ṽΔρ′; △, Δη″. (b) Δx: □, Δσ; + ,
reasonable measure for the experimental uncertainty. The value
(ρ′+ρ″)Sσ̃; ○, σ̃Δρ′; ◊, σ̃Δρ″.
for Sν̃ is mainly determined by the uncertainty of the angle
measurement and the uncertainty associated with the
determination of the decay time from the correlation function. density data which are in most cases smaller than those related
The relative expanded measurement uncertainties (k = 2) with to Sσ̃, the value for Δσ/σ of between 0.7 and 1.9% can be
respect to the liquid dynamic viscosity, Ur(η′), and the surface regarded as a reliable estimate for the total uncertainty (k = 2)
tension, Ur(σ), of our values for n-C12H26 as estimated by eqs 9 of the surface tension of n-C12H26 over the entire temperature
and 10 are displayed in Figure 4a,b, respectively. Here, the range. For the systems n-C28H58 and 0.3n-C12H26/0.7n-C28H58,
individual contributions are shown relative to the values of η′ uncertainties (k = 2) of between 1.1 and 2.8% in the
and σ. temperature range between 423.15 and 573.15 K can be
As can be seen from Figure 4a, for the temperature range estimated. Due to the experimental complexity in connection
investigated in this study, the uncertainties in the reference data with weak oscillatory signals, the uncertainties Δσ/σ increase to
and correlations used have comparatively small influence on the 3.1% for n-C28H58 and 2.5% for 0.3n-C12H26/0.7n-C28H58 at
final results for liquid viscosities. Only at larger temperatures, low temperatures and amount to between 3.0 and 5.2% for the
the influence of the increasing vapor properties becomes more wax SX-70. The relative expanded uncertainties (k = 2) for the
important, especially for the systems containing the relatively desired properties liquid dynamic viscosity, Ur(η′), and surface
strongly volatile n-C12H26. The main factor determining the tension, Ur(σ), deduced from the procedure given above are
overall uncertainty of the liquid viscosity is given by Sν̃ which is provided in Tables 2−4.
typically between 1 and 2%. For n-C12H26, a total measurement In order to check our present data and also the stability of
uncertainty (k = 2) of between 1.4 and 2.3% in the temperature the systems, about two to three independent repetition
range between 323.15 and 573.15 K can be deduced. Following measurements were performed at a specific temperature in
the calculation procedure, total measurement uncertainties the lower temperature range after having investigated state
Δη′/η′ (k = 2) of between 1.5 and 2.4% at T between 448.15 points at larger temperatures. Especially for repeated measure-
and 573.15 K for n-C28H58 and between 1.4 and 2.1% at T ments after the study of the largest temperature of 523.15 or
between 423.15 and 573.15 K for 0.3n-C12H26/0.7n-C28H58 573.15 K, slightly lower viscosity and surface tension data were
were achieved. Only at lower temperatures, the uncertainties found which may indicate a slight sample decomposition at
increase to 4.3% at T = 398.15 K for n-C28H58 and 3.0% at T = high temperatures. Nevertheless, all results from the repetition
373.15 K for 0.3n-C12H26/0.7n-C28H58. The larger uncertainties measurements agreed with the presented data within combined
at lower temperatures are related to the weaker scattering uncertainties.
signals and the less pronounced oscillatory signal, causing larger Data Correlation. The temperature-dependent experimen-
uncertainties in τC and thus in Sν̃. The same reasons are also tal results for the liquid viscosity and the surface tension of the
responsible for the total uncertainties Δη′/η′ (k = 2) for the four studied n-alkane systems are shown in Figures 5 and 6,
wax SX-70 ranging between 3.6 and 4.6% for the temperatures respectively. For all systems except for the wax SX-70 where
between 473.15 and 523.15 K. only a limited temperature range was investigated by SLS, both
As visible in Figure 4b, the double standard deviation Sσ̃ of properties were correlated as a function of temperature.
the individual measurements for n-C12H26 was relatively To represent the dynamic viscosity of liquids at the
constant around 1% over the entire temperature range. In saturation line, usually a Vogel-type or Andrade-type equation
combination with the uncertainties introduced by the available can be used within a limited temperature range.41 Such
3327 DOI: 10.1021/acs.jced.7b00363
J. Chem. Eng. Data 2017, 62, 3319−3333
Journal of Chemical & Engineering Data Article

temperature range covered. Instead, an inverse polynomial

series of third order was used in the form
η′calc = η′0 + η′1T −1 + η′2 T −2 + η′3 T −3 (11)
in order to represent our experimental dynamic viscosity data η′
for the systems n-C12H26, n-C28H58, and 0.3n-C12H26/0.7n-
C28H58. In eq 11, T is the temperature in Kelvin and η′0, η′1,
η′2, and η′3 are fit coefficients given in Table 5. For the
correlation, each data point of a system was considered with the
same statistical weight. In Table 5, also the root-mean-square
deviation (rms) of our data relative to those calculated by eq 11
is reported and between 0.50 and 0.67%. It should be noted
that the residuals of the experimental data from the fit are
always smaller than the experimental uncertainties of the
individual data points; see the lower part in Figure 5.
As expected, the liquid viscosity of n-alkanes increases with
increasing alkyl chain length.3 Due to the stronger van der
Waals interactions and entanglement of long alkyl chains, a
larger density of n-C28H58 compared to n-C12H26 is found. This
Figure 5. Liquid dynamic viscosity of investigated n-alkane systems
is in accordance with an increased momentum transport and
close to saturation conditions from surface light scattering. □, n- thus a larger viscosity for n-C28H58. For the binary system 0.3n-
C12H26; ◊, n-C28H58; ○, 0.3n-C12H26/0.7n-C28H58; △, wax SX-70; −, C12H26/0.7n-C28H58, the viscosities are between the data for the
eq 11; --, eq 12. pure components and closer to the values for n-C28H58. The
larger η′ values of the wax SX-70 compared to those of n-
C28H58 may be due to fact that on average longer-chained n-
alkanes than n-C28H58 are found in the wax.
In literature,41 many mixing rules for the viscosity of liquids
were developed. Within the scope of this study, only simple
estimation methods were considered in connection with the
binary mixture of n-C12H26 and n-C28H58 investigated in this
study. The method of Grunberg and Nissan43 expresses the
natural logarithm of the mixture liquid viscosity in terms of the
sum of the natural logarithms of the viscosities of the pure
components weighted by the corresponding mole fraction, and
a residual part which includes a binary interaction parameter
G12. Based on the viscosity data correlated according to eq 11
between 398.15 and 573.15 K for the pure and binary systems,
the calculated G12 data vary strongly with temperature between
1.29 at T = 398.15 K and 0.34 at T = 573.15 K. Since usually
G12 should only vary weakly with temperature for non-
associating compounds such as n-alkanes, it seems that the
broad temperature range studied in this work does not allow for
a use of the method of Grunberg and Nissan.43 Instead, the
same form of mixing rule was employed using a mass fraction
Figure 6. Surface tension of investigated n-alkane systems close to weighted scheme and neglecting a binary interaction parameter
saturation conditions from surface light scattering. □, n-C12H26; ◊, n-
C28H58; ○, 0.3n-C12H26/0.7n-C28H58; △, wax SX-70; −, eq 13; --, eq
according to
14. ln η′ = w1 ln η′calc,1 + w2 ln η′calc,2 (12)
where the indices 1 and 2 refer to the substances n-C12H26 and
equations cannot describe the experimental viscosity data for n-C28H58, respectively. The prediction according to eq 12
the three pure and binary systems sufficiently over the broad represents the correlation for the mixture viscosity obtained

Table 5. Liquid Dynamic Viscosity Data from the Correlation for the Studied Pure and Binary n-Alkane Systems
n-C12H26 n-C28H58 0.3n-C12H26/0.7n-C28H58
η′0/(mPa·s) −1.439199 −9.896327 −6.734002
η′1/(mPa·s·K) 2059.310 15616.33 10504.53
η′2/(mPa·s·K2) −1.00160 × 106 −8.31603 × 106 −5.53216 × 106
η′3/(mPa·s·K3) 1.88305 × 108 1.57478 × 109 1.05233 × 109
rmsa/% 0.50 0.67 0.64
T range/K 323−573 398−573 373−573

a
Standard percentage deviation of η′ to the fit.

3328 DOI: 10.1021/acs.jced.7b00363

J. Chem. Eng. Data 2017, 62, 3319−3333
Journal of Chemical & Engineering Data Article

from the experimental data based on eq 11 within ±5% over smaller surface tension enriches at the surface in terms of
the temperature range between 398.15 and 573.15 K. The surface energy minimization. This causes the mixture surface
correlation according to eq 12 is also shown in Figure 5 as a tension to be less than the mole fraction average of the surface
dashed line. tension of the pure compounds.40 Using the surface tensions
The experimental data for the surface tension of the three measured for the pure systems n-C12H26 and n-C28H58, a mole
investigated pure and binary systems can be represented by a fraction based mixing rule for the system 0.3n-C12H26/0.7n-
modified van der Waals equation, which is suitable for C28H58 would result in between −2 and −8% lower surface
extrapolations up to the critical point,44 according to tensions than the data correlated by eq 13 over the temperature
range between 398.15 and 573.15 K, with a different
σcalc = σ0(1 − TR )1.26 [1 + σ1(1 − TR )0.5 + σ2(1 − TR )] temperature-dependent trend. Thus, the surface region seems
(13) to be enriched by n-C28H58 having a larger surface tension than
where TR (=T/TC) denotes the reduced temperature. In eq 13, n-C12H26. According to that, a mixing rule based on the mass
σ0, σ1, and σ2 represent fit parameters and are given in Table 6. fraction of the two components in the form of
σ = w1σcalc,1 + w2σcalc,2 (14)
Table 6. Coefficients of Equation 13 and Root-Mean-Square
(rms) Deviation of the Experimental Surface Tension Data was applied. As illustrated in Figure 6 as a dashed line, the
from the Correlation for the Studied Pure and Binary n- mixing rule based on eq 14 represents the measured surface
Alkane Systems tension data within 2% over the entire temperature range
between 398.15 and 573.15 K, which is within most of the
n-C12H26 n-C28H58 0.3n-C12H26/0.7n-C28H58 uncertainties of the experimental data for the binary mixture.
σ0/(mN·m−1) 48.5580 114.8963 104.6797 Comparison with Literature. A data comparison with
σ1 0.466141 −1.659485 −1.482824 experimental literature data for the systems studied in this work
σ2 −0.559672 1.185501 1.023485 can only be performed for the pure substances n-C12H26 and n-
TC / K 658.65b 828.3b 788.59c C28H58. No experimental data are available for the systems 0.3n-
rmsa/% 0.77 0.88 0.43 C12H26/0.7n-C28H58 and the wax SX-70.
T range/K 323−573 398−573 373−573 In Figure 7, our values for the dynamic viscosity of n-C12H26
a
Standard percentage deviation of σ to the fit. bEmployed from ref 45. measured close to saturation conditions are shown in
c
Calculated according to ref 46, using the data from ref 45.

In this table, also the critical temperatures TC are listed which

were directly used from literature45 for the systems n-C12H26
and n-C28H58. For the critical temperature of the binary mixture
0.3n-C12H26/0.7n-C28H58, the mixing rule according to Lee and
Kesler46 was employed taking into consideration the TC values
of the pure substances and assuming a constant mole fraction
ratio of 0.3/0.7 over the entire temperature range. The present
correlation which assumes the same statistical weight of each
data point of the temperature-dependent measurement sets
represents the experimental values of the surface tension with a
rms deviation of between 0.43 and 0.88%. Except for two single Figure 7. Data comparison for dynamic viscosity of liquid dodecane.
data points, the relative deviation of the experimental data from ■, this work; −, eq 11; --, Huber et al.;32 △, Dymond and Young;47 ◊,
the data correlated by eq 13 is smaller than their uncertainties. Knapstad et al.;48 ▽, Knapstad et al.;49 ○, Caudwell et al.50
The surface tensions of the n-alkanes n-C12H26 and n-C28H58
show the expected trend of increasing values with increasing comparison with literature data. Deviations between our results
carbon number.3 The larger density of longer-chained n-alkanes from SLS and the literature values are plotted using our
also allows for forming more dispersive interactions at the correlation, eq 11, as a basis. For the reference fluid n-C12H26,
liquid surface, causing a larger surface energy and thus surface the Refprop database3 refers to the pure fluid model from
tension. In a manner similar to that observed for the liquid Huber et al.,32 which represents the dynamic viscosity as the
viscosity, the surface tensions of the binary mixture are closer to sum of a dilute gas contribution and a residual part containing
the values for the pure n-C28H58. Interestingly, the surface higher order density terms. For this model representing the
tension data for the wax SX-70 are between the data for the considered experimental data in the temperature range between
pure n-C28H58 and for the binary mixture 0.3n-C12H26/0.7n- 262 and 473 K with an absolute average deviation of 0.95%, the
C28H58. It seems that the liquid surface of the wax is rather estimated uncertainty in viscosity along the saturated liquid line
enriched by short-chained n-alkanes with a carbon number is specified to be 0.5%.32 As shown in Figure 7, agreement
below 30, which results in a minimization of the surface energy. between our experimental data and the correlation of Huber et
This may also explain the relatively large liquid viscosity of the al.32 within ±2% and thus within the experimental uncertainty
wax in comparison with n-C28H58. of our data can be found for the temperature range between
A correlation for the surface tension of a binary liquid 323 and 523 K. At larger temperatures up to 573 K, the
mixture is usually not a simple function of the composition correlation gives slightly lower values compared to our values
because the composition in the bulk can be different from that outside combined uncertainties. This seems to be related to the
at the surface. This issue could already be observed from the limited temperature range of the data used to develop the
aforementioned behavior of the viscosity and surface tension correlation which takes the character of an extrapolation at
data for the wax SX-70. Typically, the component with the higher temperatures.
3329 DOI: 10.1021/acs.jced.7b00363
J. Chem. Eng. Data 2017, 62, 3319−3333
Journal of Chemical & Engineering Data Article

The experimental data sources used for the development of correlation based on eq 11 to lower temperatures, relative
the correlation of Huber et al.32 are discussed below and only deviations between the data of Mazee58 and our correlated data
considered here. The data of Dymond and Young47 were ranging from +16.0 to +26.4% can be found. These deviations
measured with a suspended level viscometer at saturation are outside the combined uncertainties considering the
pressure between 283 and 393 K using a sample with mole uncertainty of the experimental data of Mazee58 of 0.2% and
fraction purity of more than 0.99. Knapstad et al.48 determined the uncertainty intervals of the extrapolated correlated data
the viscosity of a sample with a purity w > 0.9966 using an based on a confidence level of more than 95% (k = 2). One
oscillating cylinder viscometer at atmospheric pressure for possible reason for the discrepancies may be the limited
temperatures between 293 and 425 K. Both aforementioned applicability of the correlation to lower temperatures close to
sets have an estimated uncertainty of 0.5%. Knapstad et al.49 the melting point where typically a strong increase in the liquid
later reported further measurements on n-C12H26 of the same viscosity is observed.
sample purity (w > 0.9966) at atmospheric pressure from 289 An estimation of the liquid viscosity of n-C28H58 can be
to 343 K, stating estimated uncertainties of between 0.4 and carried out using the database in Yaws’ handbook.5 The
0.6%. Caudwell et al.50 performed the most recent viscosity correlation based on the regression of unstated experimental
measurements, which were made with a vibrating-wire data and researched estimates provides viscosity values which
instrument operated between 298 and 473 K in the compressed are distinctly lower than our measured data. The relative
liquid phase at a pressures of 0.1 MPa with a reported deviation increases with increasing temperature and covers a
uncertainty of 2%. The data obtained by Lyusternik and range between −6.5% at 398.15 K and −56.3% at 573.15 K.
Zhdanov51 in the gaseous region between 503 and 681 K as Hence, the reliability of viscosity estimations or extrapolations
well as by Giller and Drickamer52 near the freezing point of as those used in the database of Yaws’ handbook5 is highly
about 262 K up to 293 K cannot be used for data comparison questionable, especially for weakly characterized substances
here. More recent experimental viscosity data for n-C12H26 at or such as n-C28H58.
close to saturation conditions are generally determined only The surface tensions of n-C12H26 obtained from SLS are
around ambient temperature below 323 K53,54 or agree with plotted in Figure 8 together with available experimental
our present results within combined uncertainties.55 Further
recently published experimental data from Yang et al.56 were
obtained over an extended temperature range from 303 to 673
K in the compressed liquid phase at 5 MPa. For temperatures
between 323 and 573 K studied in our measurements, the
relative deviations between the data of Yang et al.56 measured
by a thermal expansion method and the correlation according
to eq 11 increase from +4.2% at 323.2 K to +16.4% at 573.2 K.
The larger viscosities for the data of Yang et al.56 compared to
our data are reasonable due to the larger pressure in their
measurements, and are in agreement with the correlation of
Huber et al.32 within combined uncertainties.
In Figure 7, only those literature data points which fit to the Figure 8. Data comparison for surface tension of dodecane. ■, this
temperature range and conditions at or close to saturation as work; −, eq 13; --, Mulero et al.;59 △, Jasper;61 ◊, Körösi and
studied in this work are shown. All experimental data points Kováts;62 ○, Cumicheo et al.63
described above agree with our present data within combined
uncertainties, with relative deviations of the data sets below
±2.5%. The aforementioned discrepancy between our data and literature data covering the temperature range investigated in
the correlation of Huber et al.32 at temperatures above 523 K this work. Our correlation according to eq 13 serves as a
may be related in that the latter correlation is strongly reference. The Refprop database3 recommends the use of the
influenced by the temperature-dependent trend of the surface tension model of Mulero et al.59 The correlation
experimental data of Caudwell et al.50 represents the 60 experimental data points measured in a
For the liquid viscosity of n-C28H58, only two data sources temperature range between 273.15 and 473.15 K and used for
providing experimental results could be found. In 1951, the development of the model with an absolute average
Doolittle and Peterson57 performed measurements at atmos- deviation of 0.49%. Both the data sources considered and the
pheric pressure for a temperature range between 263 and 573 K uncertainty of the model are not defined. According to Figure
employing a Ubbelohde capillary viscometer with a claimed 8, the model of Mulero et al.59 yields between 2.4 and 4.6%
uncertainty of between 1.2 and 1.5%. No information on the larger values than our correlation over the entire temperature
purity of the sample is given. Compared to our correlation in range between 323 and 573 K. Assuming an uncertainty of 2%
the temperature range developed from our measurements, the for the correlation of Mulero et al.,59 both data sets would be
liquid viscosity data of Doolittle and Peterson57 show larger within combined uncertainties in most cases, even for the
values outside combined uncertainties with deviations between extrapolated data at temperatures above 473 K.
+8.2% at 373.15 K and +4.4% at 548.15 K. Such deviations Most experimental σ data for n-C12H26 are generally
might be related to the different sample purities, which is likely determined only around ambient temperature below 323
to be possible for long-chained alkane systems. The other data K53,55,60 and are thus not used for data comparison here. In
set measured by Mazee58 with an Ostwald-type viscometer total, three data sources providing surface tension data of n-
reports viscosity values in a temperature range between 343.15 C12H28 above 323 K were found and are discussed below.
and 363.15 K, which is outside the temperature range Jasper61 applied the capillary rise method for measuring the
investigated in the present study. By extrapolating our surface tension under isobaric conditions with an atmosphere
3330 DOI: 10.1021/acs.jced.7b00363
J. Chem. Eng. Data 2017, 62, 3319−3333
Journal of Chemical & Engineering Data Article

consisting of nitrogen and dodecane vapor at temperatures other long-chained alkane systems, theoretical estimations in
between 283.15 and 393.15 K. A low uncertainty of 0.01 mN· literature for n-octacosane show distinct discrepancies from our
m−1, i.e., smaller than 0.1%, is claimed by the authors. The measurements, especially for the liquid viscosity with deviations
capillary rise method was also used by Körösi and Kováts62 for of more than 50%. In this connection, the experimental data
temperatures of 293.15 and 353.15 K, without specifying the obtained in this work can improve the data situation for
ambient conditions. The uncertainty of their surface tension viscosity and surface tension of medium- to long-chained n-
data is below 0.3%. Cumicheo et al.63 determined the surface alkane systems in the high-temperature regime. Furthermore,
tension at ambient pressure and a single temperature of 344.15 they can be used to develop modeling approaches by serving as
K with the help of the pendant drop method with an reference values for theoretical and empirical models as well as
uncertainty of 0.01 mN m−1. Except for Jasper,61 who provides molecular simulations.
no purity specification, the mass fraction purity of the samples
was specified to be better than w = 0.999.
Figure 8 shows that all literature data are comparable to each
■
*
ASSOCIATED CONTENT
S Supporting Information
other and by trend larger than our data. Furthermore, the The Supporting Information is available free of charge on the
temperature-dependent data of Jasper61 converge with the ACS Publications website at DOI: 10.1021/acs.jced.7b00363.
present measurement results at larger T values. Discrepancies in
Composition analysis of the systems investigated by SLS
published surface tension values are not uncommon because
the determination of this property may be affected by two and liquid density data of the wax SX-70 (PDF)
factors which may not be easily controlled experimentally. First,
values for surface tension are strongly influenced by
contamination and/or impurities. Second, if surface tension is
■ AUTHOR INFORMATION
Corresponding Author
measured for liquid−air systems, as in most cases cited above, *Tel.: +49-9131-85-23279. Fax: +49-9131-85-25851. E-mail:
the surface temperature may be somewhat below the thomas.m.koller@fau.de.
temperature in the bulk of the fluid, a fact which may rather ORCID
increase the surface tension. An influence of this error can be Thomas M. Koller: 0000-0003-4917-3079
excluded for the present investigation, which has been carried
out inside a closed sample cell close to saturation conditions in
Cédric Giraudet: 0000-0003-2051-7042
thermodynamic equilibrium. Jiaqi Chen: 0000-0002-2591-0073
Since no experimental surface tension data are available for n- Andreas P. Fröba: 0000-0002-9616-3888
C28H58, estimated data were derived from Yaws’ handbook.5 Funding
The calculated results, which are based on a simple van der This work was financially supported by the German Research
Waals equation, deviate between +2.4 and +6.1% from our data Foundation (Deutsche Forschungsgemeinschaft, DFG) by
correlated via eq 13 within the temperature range between funding the Erlangen Graduate School in Advanced Optical
398.15 and 573.15 K. The source of the parameters used in the Technologies (SAOT) within the German Excellence Initiative.
model and the reliability of the model itself, which is applied for Financial support from Shell Global Solutions International
a broad temperature range here but theoretically only valid B.V. through a contracted research agreement is gratefully
close to the critical region, is debatable. acknowledged.

■ CONCLUSIONS
Notes
The authors declare no competing financial interest.
The present investigations on a horizontal liquid−vapor
interface of four different n-alkane systems containing pure n-
dodecane and n-octacosane, their binary mixtures at a mole
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3333 DOI: 10.1021/acs.jced.7b00363

J. Chem. Eng. Data 2017, 62, 3319−3333