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

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

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Journal of Chemical & Engineering Data
modeling methods for the prediction of thermophysical
properties in the form of computer simulation 4 and
theoretical/empirical5 approaches. Nevertheless, even for
small- to medium-weight n-alkane systems, such predictive
methods can still often not be used for a reliable quantitative
estimation of viscosity and surface tension, as will be shown
later in this study, and can only be as accurate as the
experimental data used to verify the calculation results.
Surface light scattering (SLS) probes, as the name indicates,
the dynamics of thermal fluctuations on the surface of a liquid
or, in a more general formulation, at phase boundaries. Here,
measurements are performed in or close to macroscopic
thermodynamic equilibrium in a contactless way without the
need for any calibration. All these features allow for defining the
method as a quasi-primary method for the measurement of
viscosity.6 During the past two decades, our research activities
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
commercially available wax SX-70 with a defined composition
over a broad temperature range between 323 and 573 K close
to saturation conditions. After an introduction to the SLS
technique, the materials and sample preparation as well as the
experimental setup are described. Thereafter, a measurement
example and the data evaluation procedure are presented. The
main objectives of this work are to show the capability of SLS
for a simultaneous determination of liquid viscosity and surface
tension of selected n-alkane systems over a broad temperature
range in an accurate manner and to fill the existing gap in the
database for an industrially relevant class of working fluids.
Besides a critical analysis of the experimental uncertainties of
the present measurements and of the available scarce literature
data, simple correlations for the liquid viscosity and surface
tension of the studied systems are provided.
■ SURFACE LIGHT SCATTERING
For the present investigations of a phase boundary between the
corresponding liquid and vapor phases of the n-alkane systems,
an exact treatment of the capillary wave problem taking into
account the phase boundary is necessary to reliably determine
viscosity and surface tension with high accuracy. For a detailed
description of the fundamentals and methodological principles
of SLS, the reader is referred to specialized literature.18,19 In
this section, the main information on the SLS technique which
is relevant for the present study is provided.
In macroscopic thermal equilibrium, liquid surfaces exhibit
surface waves that are caused by the thermal motion of
molecules.20 The result of such fluctuations is a rough surface
which can be represented by a superposition of surface waves
with different amplitudes and wave vectors. Each Fourier
component of the rough surface scatters a small fraction of an
3320
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incident light in equally spaced directions around both the
reflected and refracted beams. Surface fluctuations observable in
the light scattering experiment typically cover a wavelength
range from about 0.1 to 1000 μm. The total root-mean-square
amplitude of the surface roughness integrated over all
wavelengths is typically between 1 and 100 nm. In the SLS
experiment, the dynamics of surface fluctuations in the form of
their frequency and damping is probed for a defined
wavelength. For the temporal decay of surface fluctuations,
two cases can be distinguished. In the case of large viscosity
and/or small surface tension, the amplitude is damped
exponentially, while, in the case of small viscosity and/or
large surface tension, the amplitude of surface fluctuations
decays in the form of a damped oscillation.
The scattering geometry used in this study is shown in Figure
1 where scattered light is observed in the forward direction near
Figure 1. Scattering geometry used for surface light scattering.
refraction. This arrangement has been chosen due to signal and
stability considerations21 and differs from the more commonly
employed scattering geometry where the scattered light is
observed close to the direction of the reflected beam. By choice
of the angle of incidence ΘE and the scattering angle ΘS, the
scattering vector q ⃗ = kI⃗ ′ − k S⃗ ′ is determined and, from this, the
wave vector and frequency of the observed surface vibration
mode. Here, kI⃗ ′ and k S⃗ ′ denote the projections of the wave
vectors of the reflected (kI⃗ ) and scattered (kS⃗ ) light to the
surface plane, respectively. In the special optical arrangement
illustrated in Figure 1, light scattered on the liquid−vapor
interface is detected perpendicular to the surface plane. In
addition, scattered light is observed within the irradiation plane
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
identities resulting in
2π
q = |kI⃗ ′ − k S⃗ ′| ≅ sin(ΘE)
λ0 (1)
where λ0 is the laser wavelength in vacuo. Each scattering vector
chosen solely from the adjusted angle of incidence corresponds
to a specific wavelength (2π/q) of surface vibration mode as it
is shown in Figure 1.
Based on classical hydrodynamic theory, the temporal decay
of a particular surface mode of the form exp[iq ⃗ r ⃗ + St/τ0], with
a wave vector q⃗ at a given point r,⃗ is obtained from the
dispersion equation for surface waves at the interface between
contacting liquid (′) and vapor (″) phases.22 By introducing the
dimensionless parameter
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ρ′ + ρ″ ⎛ g (ρ ′ − ρ ″ ) ⎞
Y= ⎜ σ + ⎟ surface waves, i.e., the frequency ωq and damping Γ at a defined
4(η′ + η″)2 q ⎝ q2 ⎠ (2)
with ρ′ and ρ″ being the densities of the liquid and vapor
phases, η′ and η″ the dynamic viscosities of the liquid and vapor
phases, respectively, σ the surface tension, and g the local
acceleration of free-fall, as well as introducing the reduced
frequency
ρ′ + ρ″
S = iατ0 , with τ0 =
2(η′ + η″)q2
the dispersion relation can be transformed into its reduced
form22
ρ′2 − ρ″2 + 2Rρ′ρ″ η′(M′ − 1) − η″(M″ − 1)
D(S) = Y + S
(ρ′ + ρ″)2 η′(M′ + 1) + η″(M″ + 1)
⎧ analysis of surface fluctuations showing an oscillatory behavior
ρ′ η′(M′2 + 1) + η″[M′ − 1 + M″(M′ + 1)]
⎪
+⎨
⎩ (ρ′ + ρ″) (M′ − 1)[η′(M′ + 1) + η″(M″ + 1)]
⎪
ρ″ η″(M″2 + 1) + η′[M″ − 1 + M′(M″ + 1)] ⎫ 2
+ ⎬S
(ρ′ + ρ″) (M″ − 1)[η′(M′ + 1) + η″(M″ + 1)] ⎭
In eq 4, the dimensionless properties R, M′, and M″ are given
by
η′ / ρ ′ − η″ / ρ ″
R=
(η′ + η″)/(ρ′ + ρ″)
ρ′ + ρ″
M′ = 1+2 S accounts for the deviations of the spectrum from the Lorentzian
ρ′ + ρ″ + Rρ″
ρ′ + ρ″
M″ = 1+2 S identical with the mean lifetime or the reciprocal of the
ρ′ + ρ″ − Rρ′
The reduced frequency S is related to the complex frequency α
(α = ωq + iΓ) and to the characteristic viscous time τ0.
Furthermore, the real part of the complex frequency α
represents the frequency ωq and the imaginary part the
damping Γ of the observed surface vibration mode with the
corresponding wavenumber q.
At relatively small surface wavelengths, as it is relevant in this
work, the last term in eq 2, which arises from the force of
inertia, can be neglected without significant increase in
uncertainty. The solution of the dispersion relation in eq 4
shows that there exists a critical value for Y for which the
temporal behavior of the surface fluctuations changes depend-
ing on the thermophysical properties of the fluid and the
wavenumber selected. For Y < 1 associated with large liquid
viscosities and/or low surface tensions, surface fluctuations are
overdamped and do not propagate (ωq = 0). For Y > 1
associated with small liquid viscosities and/or large surface
tensions, surface fluctuations propagate and show an oscillatory
behavior. This case has been observed in all measurements
presented in this work, where the smallest Y value was 1.6, and
is only studied in the following. When Y ≫ 1 or Y ≪ 1, first-
order approximations11,18 for S can be used for an accurate
description of the dynamics of surface waves. For intermediate
values of Y, the dynamics of surface waves can no longer be
described with sufficient certainty by the first-order approx-
imation as it is often carried out in literature.23−25
For an accurate determination of liquid viscosity and surface
tension from the light scattering experiment, the dispersion
relation eq 4 must be considered in its complete form. For this,
Article
data obtained from the SLS experiment for the dynamics of
wavenumber q, have to be combined with reference data for the
dynamic viscosity of the vapor phase η″ and density data for
both phases ρ′ and ρ″ to get information on the liquid
kinematic viscosity ν′ or liquid dynamic viscosity η′ (η′ = ν′ρ′)
and surface tension σ. Details on the data evaluation are given
later in the corresponding section.
In SLS, scattered light emerging from the interaction
between incident light and the fluctuating surface structure
(3) can be analyzed using photon correlation spectroscopy. In this
type of detection, the time-dependent correlation function of
the scattered light intensity is measured at a point in the far
field. For heterodyne conditions, where the scattered light is
superimposed with coherent reference light of much higher
intensity, the normalized intensity correlation function for the
is described by22
g(2)(τ ) = a + b cos(ωq τ − ϕ) exp( −τ /τC) (8)
(4) The experimental constants a and b in eq 8 are essentially
determined by the total number of registered counts, the ratio
of scattered light to reference light, and the coherence
properties of the optical system. The time-dependent parts of
eq 8 are proportional to the correlation function of the surface
fluctuations, whose Fourier transform is, according to the
(5)
Wiener−Khintchine theorem, the corresponding power spec-
trum of the surface fluctuations. The phase term ϕ largely
(6) form and was used as a variable in the data evaluation
procedure. The correlation time τC and the frequency ωq are
(7) damping constant Γ (=1/τC) of the surface ripplons and their
frequency of propagation, respectively. The latter relate to the
fluid properties through the capillary wave dispersion equation;
see eq 4.
■ EXPERIMENTAL SECTION
In the following experimental section, the materials and sample
preparation as well as the experimental setup and procedure
relevant for the present investigations are summarized.
Materials and Sample Preparation. According to the
specifications of the manufacturer, the linear n-alkanes n-
dodecane (n-C12H26, molar mass M = 170.33 g·mol−1,
purchased from Merck GmbH) and n-octacosane (n-C28H58,
M = 394.77 g·mol−1, purchased from Alfa Aesar GmbH & Co.
KG) had both nominal purities in terms of mass fractions of w
> 0.99. The wax SX-70 (XTL heavy HPS paraffins) was
obtained from Shell Global Solutions B.V. and represents a
mixture of heavy n-alkanes. A detailed analysis of the
composition of the four different n-alkane systems investigated
in our SLS measurements was obtained by gas chromatography
(GC) and can be found in the Supporting Information in
Tables S1 and S2. The results are based on the analysis of
theoretical flame ionization detector response factors. These
factors have been calculated by the effective carbon number
method published by Sternberg et al.26 Besides the main
components, other groups commonly found in Fischer−
Tropsch related samples such as branched alkanes, aromatics,
or oxygenated compounds were categorized according to the
number of carbon atoms NC. The absolute uncertainty of the
mass fractions w measured by the GC method can be estimated
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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
95% (k = 2).
According to the GC results, the initial purities of w = 0.9945
for n-C12H26 and w = 0.9950 for n-C28H58 obtained before the
SLS experiments could confirm the specifications given by the
supplier. Referring to the mass distribution in Figure S1 in the
Supporting Information, the sample for the wax SX-70 analyzed
before the measurements shows a broad, slightly asymmetric
distribution of linear n-alkanes ranging between about n-icosane
(n-C20H42) and n-hexacontane (n-C60H122). The compound
mostly found in the wax is n-tritriacontane (n-C33H68) with w =
0.068.
At ambient conditions, the n-C28H58 and wax samples are
solid and start to melt at about 335 K. Due to the broader
distribution of heavy alkanes in the wax sample, the melting
temperature reaches up to about 373 K. Both liquefied samples
showed particle-like impurities presumably resulting from the
manufacturing process. To obtain ideally particle-free samples
as necessary for SLS experiments, samples of n-C28H58 and the
wax SX-70 were filtered with a syringe filter with 220 nm pore
size at about 373 and 423 K, respectively.
The binary n-alkane mixture consisting of mole fractions x of
about x1 = 0.30 of n-C12H26 and x2 = 0.70 of n-C28H58 (0.3n-
C12H26/0.7n-C28H58) was investigated in the temperature range
3322
between 373.15 and 573.15 K. Filtered n-C28H58 was liquefied
in a beaker at about 340 K before an appropriate amount of n-
C12H26 was added. To achieve the desired composition of the
n-alkane mixture, both liquid compounds were weighed before
and after filling with a balance (Sartorius BP110) with an
expanded uncertainty (k = 2) of 1 mg. From the weighing
procedure, an initial mass fraction ratio for n-C12H26/n-C28H58
of w1/w2 = 0.156/0.844, corresponding to a mole fraction ratio
of x1/x2 = 0.300/0.700, was adjusted. Here, the absolute
uncertainty (k = 2) in both the mass and mole fractions based
on the weighing procedure is supposed to be 0.001. Taking into
consideration the uncertainty of the GC results for the pure
substances of w = 0.001, the total expanded uncertainty (k = 2)
of the overall mass fraction of the binary mixture is estimated to
be w = 0.002.
To avoid any change in the sample composition of the binary
mixture and the wax SX-70 during sample preparation caused
by different evaporated amounts of the components, a fast
preparation procedure was necessary. The inevitable variation
in the composition of the liquid binary mixture over the
investigated temperature range could be estimated by mass
balance calculations detailed later on. Helium (M = 4.0026 g·
mol−1), which served as an inert gas for sample handling and
control of the sample composition during the experiments, was
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supplied by Linde AG with a volume fraction purity ψ of
0.99999.
All liquefied samples were transparent at the beginning of the
measurements. After the measurements up to 573 K in the case
of n-C12H26, n-C28H58, and 0.3n-C12H26/0.7n-C28H58, a slight
yellowish coloration could be found. A further GC analysis was
carried out to check if any thermal decomposition or
oxygenation of n-alkanes27 occurred in the high-temperature
range. The GC results obtained for the samples after the SLS
measurements are also given in Table S1 in the Supporting
Information and show no distinct change in the composition of
the n-C12H26 (w = 0.9941) and n-C28H58 (w = 0.9832) samples.
For the binary mixture of n-C12H26 and n-C28H58, the total
fraction of both substances in the sample was w = 0.9957
according to the GC results. The reduction of the mole fraction
ratio of n-C12H26/n-C28H58 from 0.300/0.700 to about 0.287/
0.713 is caused by the larger volatility of n-C12H26 than n-
C28H58, resulting in a weak depletion of n-C12H26 relative to n-
C28H58 in the liquid phase during the measurements. A
summary of the used chemicals is given in Table 1.
Experimental Setup and Procedure. The experimental
setup used for the investigation of a liquid−vapor interface of
the studied n-alkane systems close to saturation conditions is
the same as that used in our former studies11,16,17 and shown in
Figure 2. The main information on the setup necessary for the
present study is detailed below. A frequency-doubled
continuous-wave Nd:YVO4-laser (Coherent, Verdi-V2) oper-
ated in a single mode with a wavelength of λ0 = 532 nm serves
as a light source. The laser power was about 500 mW when
working at temperatures T < 350 K and somewhat lower for
higher temperatures. For the observation of light scattered by
surface waves, the optical path has to be aligned in such a way
that the laser beam and the direction of detection intersect on
the liquid−vapor interface in the measurement cell. For large
scattering intensities from the vapor−liquid interface, scattered
reference light from the cell windows is not sufficient to realize
heterodyne conditions. Here, an additional reference beam is
added. For this, part of the incident laser light is split by a glass
plate and superimposed with the scattered light behind the
sample cell. The time-dependent intensity of the scattered light
is detected by two photomultiplier tubes (PMTs) operated in
cross-correlation in order to suppress after-pulsing effects. The
signals are amplified, discriminated, and fed to a linear-tau
digital correlator featuring 256 equally spaced channels
operated with a sample times down to 37.5 ns.
The design of the optical arrangement is based on the
analysis of scattered light at variable and relatively high wave
numbers of capillary waves, whereby instrumental broadening
effects are negligible.11 According to eq 1, the wavenumber q
can be adjusted as a function of the easily accessible angle of
incidence ΘE. To measure the latter property, the laser beam is
first adjusted through the detection system consisting of two
apertures (diameter 1 mm) at a distance of about 4 m. Then,
the laser beam is set to the desired angle. For the experiment,
the angle of incidence ΘE was set between 3.0° and 3.2° and
was measured with a high-precision rotation table. The error in
the angle measurement was determined to be approximately
0.005° (k = 2).
A sample cell consisting of stainless steel and having the same
outer dimensions as that employed in our previous light
scattering measurements from the bulk of fluids28−30 was used.
Compared to the latter investigations, the special feature of the
cell used in this study is that it provides a larger effective surface
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length of 7 cm due to the larger total inner volume of about 105
mL instead of 40 mL. A length of 7 cm corresponds to the same
value as that used in our former study on toluene11 and is
sufficient to avoid disturbing capillary effects of the liquid at the
edges of the cell on the probed region. Also due to this
arrangement, line broadening effects could be suppressed
completely. The four optical accesses, which are uniformly
distributed around the cell and where two of them are used to
guide the incident beam and collect the scattered light, were
made of quartz windows (Herasil, diameter 30 mm × length 20
mm).
The temperature of the sample cell was controlled by
resistance heating and measured by a calibrated Pt-100 Ω
resistance probe. This is integrated into the wall of the sample
cell close to the heating wire and connected to an AC bridge
(Anton Paar MKT 100). Given the large thermal conductivity
of the cell material and the close proximity of the resistance
probe to the vapor−liquid interface, it can reliably be assumed
that the temperature of the resistance probe corresponds to the
temperature of the fluid. The uncertainty in the absolute
temperature measurement is 15 mK (k = 2). The temperature
stability of the temperature probe used for temperature control
and measurement was better than 5 mK during each
experimental run. The reported sample temperature data
stem from the average of the recorded readings of the sensor
for a given temperature point. Taking also the uncertainty and
position of the used resistance probe into account, the
expanded uncertainty for all reported temperatures is estimated
to be 0.05 K (k = 2) over the entire temperature range.
Before each measurement series, a pressure test of the cell
using helium at pressures of about 2 MPa was successfully
performed. Thus, a tightness of the cell during the measure-
ments could be ensured. For the filling of the sample cell, first
the liquefied samples were inserted into the cell via the upper
window. The gas phase was then flushed by helium several
times in order to avoid any contamination of the sample with
air or other gases which may enable an oxygenation of the
sample. After that, the system was closed by inserting and fixing
the upper window, and an initial partial pressure of about 0.1
MPa of helium could be adjusted. The pressure was not
registered during the measurement in order to keep the system
volume and the disturbance of the thermodynamic equilibrium
small, but could be estimated to be smaller than 0.2 MPa in all
cases. Given the insignificant effect of pressure on the liquid
viscosity and surface tension of n-alkane systems at relatively
small pressures below 0.2 MPa,3 all presented measurements
can be considered to be carried out close to saturation
conditions.
For each temperature, six measurements at different angles of
ΘE = 3.0°, 3.1°, and 3.2° were performed, where the laser was
irradiated from either side with respect to the axis of
observation in order to check for a possible misalignment.
Furthermore, line-broadening effects can be excluded for such a
choice of incident angles. The measurement times for a single
run were typically on the order of 20 min down to a couple of
minutes for the highest temperatures in this study. During a
measurement series for each system, the temperature was
increased step by step. While for pure n-C12H26 the lowest
temperature was set to 323.15 K, larger temperatures of T =
398.15 K for n-C28H58 and T = 373.15 K for 0.3n-C12H26/0.7n-
C28H58 were required to suppress disturbing influences from
scattering due to solid agglomerates which were not yet molten
below the stated temperatures. Temperature steps of 25 K were
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used for the pure and binary systems. For the wax SX-70, a
limited temperature range between 473.15 and 523.15 K in
steps of 10 K was studied in order to avoid any thermal
decomposition of very long chained hydrocarbons at overly
large temperatures. For all studied systems, repetition measure-
ments were performed at least one time within the series and
after the last measurement at the largest temperature of 523.15
or 573.15 K. This allowed checking of the stabilities of the
investigated samples.
■ MEASUREMENT EXAMPLE AND DATA
EVALUATION
Figure 3 shows an example correlation function obtained from
scattering on the interface of liquid n-C28H58 close to saturation
Figure 3. Measurement example of a normalized correlation function
(upper graph) and the residuals (lower graph) for n-C28H58 at a
temperature of 498.15 K using an incident angle of 3°: □,
measurement data; −, fit according to eq 8.
conditions at a temperature of 498.15 K and an incident angle
ΘE = 3°. The experimental correlation function, eq 8, has to be
evaluated for the central quantities, ωq and τC, which is
performed by a nonlinear regression based on a Levenberg−
Marquardt (LM) algorithm in which the squared sum of
residuals is to be minimized. Within the entire fit range, no
systematic deviations or any disturbing signals in the long-time
range of the correlation function can be observed. This is
illustrated in the residual plot in Figure 3 and was confirmed for
all present measurements. The uncertainties (k = 2) obtained
from the fit are given in brackets and are below 0.4% for ωq and
1.3% for τC. In most of the cases, uncertainties below 1% for ωq
and 2% for τC could be obtained. It is obvious that the error in
the determination of the frequency was generally smaller than
that of the decay time, especially at larger temperatures where
more and more oscillations appeared in the correlation
functions.
As discussed above and detailed in our former studies,11,18 a
reliable determination of surface tension and viscosity is only
possible by an exact numerical solution of the dispersion
equation, eq 4, where the frequency ωq, the decay time τC, and
the modulus of the scattering vector q are used as input values.
This procedure has always been performed within the present
study. Further input data for solving the dispersion relation are
the density of the liquid phase as well as the density and
3324
Article
dynamic viscosity of the almost saturated vapor phase. Since the
systems investigated in this work are still relatively far away
from the critical point, the liquid phase is mainly dominating
the dynamics of the surface waves. For the vapor properties,
uncertainties of about 20% are sufficient enough to determine
the liquid properties accessible by SLS within less than 1%. In
the following, the sources used for the required input values for
the thermophysical properties of the studied systems are given
and discussed.
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
calculated from a pure fluid model according to Huber et al.32
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
recent prediction model of Riesco and Vesovic.34 For the
saturated vapor of n-C28H58, no density data are available.
Instead, Yaws’ handbook5 allows for estimations of the vapor
pressure of n-C28H58, which is more than 100 times smaller
than that of pure n-C12H26 over the entire temperature range
studied.
The influence of the vapor properties of n-C28H58 on the
values for liquid viscosity and surface tension of pure n-C28H58
was exemplarily estimated at a temperature of 573.15 K where
the effect of the vapor properties is the largest. In the two cases
where the vapor properties of n-C28H58 are considered or
neglected, relative deviations between the final liquid dynamic
viscosities of 0.2% and surface tensions of 0.1% are obtained.
These differences are about an order of magnitude smaller than
the experimental uncertainties of the measured properties.
Thus, due to the very small impact of the vapor properties of n-
C28H58, the vapor phase for the liquid systems consisting of
pure n-C28H58 and of the binary mixture of 0.3n-C12H26/0.7n-
C28H58 can sufficiently be modeled by estimating a gas phase
consisting of pure helium and a binary mixture of helium and n-
C12H26, respectively.
The liquid density of the wax SX-70 was obtained based on
volumetric measurements of a given amount of sample at
temperatures between 363.15 and 423.15 K in steps of 20 K.
For the density data which are provided in the Supporting
Information in Table S3, the uncertainty can be specified with a
value of 0.2% (k = 2). The experimental data were correlated by
a linear fit with respect to temperature which was used to
extrapolate to the temperature range between 473.15 and
523.15 K studied in the SLS experiments. At these conditions,
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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
estimated.
According to the composition of the wax SX-70 analyzed
before the measurements (see Table S2 and Figure S1 in the
Supporting Information), predominantly heavy n-alkanes with
chain lengths of more than 20 carbon atoms can be found. The
mass fraction of alkanes having NC values smaller than 20 is
about 0.03%. According to estimations based on Yaws’
handbook,5 the vapor pressure of n-alkanes decreases strongly
with increasing chain length and becomes negligible for NC >
20 within the temperature range investigated in this study. Due
to the strong presence of barely volatile long-chained alkanes in
the liquid mixture, a very low total vapor pressure originating
from the liquid wax sample can be expected. Thus, the vapor
phase for the wax system can be modeled solely by pure helium.
The vapor phase properties were determined from the vapor
pressures of the corresponding saturated liquids present in the
samples and the partial pressure from the helium used as inert
gas in all cases. These data could be used to estimate the
composition of the partially saturated vapor phase for all
studied systems. For helium, the gas density and viscosity data
were obtained from the Helmholtz equation of state for helium
published by Ortiz-Vega35 and the pure fluid model of Arp et
al.,36 respectively. The solubility of the inert gas helium in n-
dodecane can be estimated to be below x = 0.001, i.e., below w
= 0.00002 for low pressures of about 0.1 MPa and temperatures
up to 573 K, and it rather decreases with increasing alkyl chain
length.37,38 Thus, the effect of the helium gas on the liquid
properties density, viscosity, and surface tension of the systems
studied can reliably be neglected. In this context, thestrictly
speakingcorrect property measured for the n-alkane systems
close to saturation conditions by SLS, the interfacial tension
between the liquid−vapor interface, may reliably be approxi-
3325
mated with the term surface tension referring to a liquid or
liquid mixture in equilibrium solely with their own vapor phase.
While for the liquid n-C28H58 and wax SX-70 samples, a pure
helium gas phase can be considered, binary gas mixtures of
helium and n-C12H26 are modeled for the liquid systems
containing pure n-C12H26 and the binary mixture of n-C12H26
and n-C28H58. For the latter system, the vapor phase
composition was calculated in an ideal approach in which the
partial pressures related to helium and n-C12H26 were added.
Here, the partial pressure related to n-C12H26 is calculated from
the product of the vapor pressure of pure n-C12H26 and its
corresponding mole fraction in the liquid phase.
For the binary liquid mixture 0.3n-C12H26/0.7n-C28H58, it is
assumed that only those two substances are present in the
liquid phase. Furthermore, the mole fraction ratio of 0.300/
0.700 is only valid for the initial temperature of 373.15 K
studied in the experiment. Due to the strongly increasing vapor
pressure of n-C12H26 with increasing temperature, more and
more n-C12H26 transfers from the liquid into the vapor phase,
while the amount of liquid n-C28H58 can be approximated as
constant at the various T states. To calculate the mole fractions
of n-C12H26 and n-C28H58 in the liquid phase, mass balance
calculations considering the volumes and densities of the two
phases were carried out. Based on this scheme, the mass
fraction w of n-C12H26 in the liquid phase varies between 0.156
± 0.002 at T = 373.15 K and 0.148 ± 0.002 at 573.15 K. The
latter value corresponds to the value obtained by the GC
analysis performed after SLS measurements up to 573.15 K.
The detailed values for the composition in the liquid phase of
the binary mixture are tabulated in the next section. Based on
the procedure given above, the corresponding liquid density for
the binary mixture 0.3n-C12H26/0.7n-C28H58 was modeled
according to a mixing rule developed by Assael et al.39 for
linear liquid n-alkanes. This model requires only information on
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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
liquids as a function of temperature. Such a mixing rule works
sufficiently well for binary combinations of linear n-alkanes
having carbon numbers NC between 6 and 24 with relative
deviations between modeled and experimental data of less than
0.5% for various temperatures.39
To model the vapor density of the binary mixtures, a linear
mole-based mixing rule using the densities of helium gas and n-
C12H26 vapor according to the corresponding data from the
Refprop database3 was applied. Such a simple prediction
scheme can represent the density of gas mixtures at low
pressures well within ±5%.3 To model the vapor viscosity, a
more sophisticated model in the form of the Lucas method40
was applied since the vapor viscosity has a stronger impact on
the properties of interest than the vapor density. The
corresponding-states model of Lucas40 requires information
on the mole composition, critical data of the pure compounds,
and corrections for polarity and quantum effects, the latter data
which were considered for helium. Using this model, the
viscosity of gas mixtures at low pressures can typically be
represented within ±10% compared to experimental data.41
Summary of Dynamic Viscosity and Surface Tension
Data. The results for the liquid dynamic viscosity η′ and
surface tension σ of the four hydrocarbon systems n-C12H26, n-
C28H58, 0.3n-C12H26/0.7n-C28H58, and the wax SX-70 between
323.15 and 573.15 K obtained from SLS close to saturation
conditions are summarized in Tables 2−4. The listed data are
average values of at least six independent measurements with
different angles of incidence ΘE. Furthermore, the used input
data for the liquid density ρ′, vapor density ρ″, and vapor
viscosity η″ required for data evaluation as described in the
previous section are tabulated.
Uncertainty Analysis. From the typical variation of liquid
viscosity and surface tension of the studied systems with
temperature, the uncertainty in the temperature measurement
of 0.05 K leads to maximum relative uncertainties below 0.07%
and 0.02% in the measured liquid dynamic viscosities and
surface tensions, respectively, over the entire temperature
range. Estimated uncertainties in the liquid mass fraction of up
to 0.002 are adherent to uncertainties in the liquid density of up
to 1%. The latter uncertainties are taken into account in the
following error analysis considering the uncertainties induced

■
RESULTS AND DISCUSSION
First, the temperature-dependent values for dynamic viscosity
and surface tension data of the investigated n-alkane systems
are presented. Then, an uncertainty analysis of the measure-
ment results and a data correlation including an interpretation
of the data from a molecular point of view is performed. Finally,
the experimental results are compared with available literature
data.
3326
by the primary measured variables and input data.
Although the approximate solution for the dynamics of
surface waves given in ref 11 never allows for the determination
of viscosity and surface tension with high accuracy (for doing
this, the exact solution of the dispersion relation, eq 4, has
always been used in this work), yet it can be applied to get a
good estimate for the total uncertainty of our SLS results in an
analytical manner. The direct quantity related to the liquid
kinematic viscosity ν̃ is determined by both vapor and liquid
properties, i.e., ν̃ = (η′ + η″)/(ρ′ + ρ″).11 Thus, the estimate for
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Journal of Chemical & Engineering Data
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
the liquid density Δρ′/ρ′ was assumed to be 0.5% for n-C12H26
and 1% for the other three systems.
As observed in many DLS applications,11,42 the standard
deviation of individual measurements may be considered as a
reasonable measure for the experimental uncertainty. The value
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.
The relative expanded measurement uncertainties (k = 2) with
respect to the liquid dynamic viscosity, Ur(η′), and the surface
tension, Ur(σ), of our values for n-C12H26 as estimated by eqs 9
and 10 are displayed in Figure 4a,b, respectively. Here, the
individual contributions are shown relative to the values of η′
and σ.
As can be seen from Figure 4a, for the temperature range
investigated in this study, the uncertainties in the reference data
and correlations used have comparatively small influence on the
final results for liquid viscosities. Only at larger temperatures,
the influence of the increasing vapor properties becomes more
important, especially for the systems containing the relatively
strongly volatile n-C12H26. The main factor determining the
overall uncertainty of the liquid viscosity is given by Sν̃ which is
typically between 1 and 2%. For n-C12H26, a total measurement
uncertainty (k = 2) of between 1.4 and 2.3% in the temperature
range between 323.15 and 573.15 K can be deduced. Following
the calculation procedure, total measurement uncertainties
Δη′/η′ (k = 2) of between 1.5 and 2.4% at T between 448.15
and 573.15 K for n-C28H58 and between 1.4 and 2.1% at T
between 423.15 and 573.15 K for 0.3n-C12H26/0.7n-C28H58
were achieved. Only at lower temperatures, the uncertainties
increase to 4.3% at T = 398.15 K for n-C28H58 and 3.0% at T =
373.15 K for 0.3n-C12H26/0.7n-C28H58. The larger uncertainties
at lower temperatures are related to the weaker scattering
signals and the less pronounced oscillatory signal, causing larger
uncertainties in τC and thus in Sν̃. The same reasons are also
responsible for the total uncertainties Δη′/η′ (k = 2) for the
wax SX-70 ranging between 3.6 and 4.6% for the temperatures
between 473.15 and 523.15 K.
As visible in Figure 4b, the double standard deviation Sσ̃ of
the individual measurements for n-C12H26 was relatively
constant around 1% over the entire temperature range. In
combination with the uncertainties introduced by the available
3327
Article
Figure 4. Estimated relative total measurement uncertainties (k = 2)
for the liquid dynamic viscosity Δη′/η′ (a) and the surface tension
Δσ/σ (b) of n-C12H26 and individual contributions to those values.
The lines in both graphs indicate the upper limit for the estimated
total uncertainties and should serve as guides for the eye. (a) Δx: □,
Δη′; + , (ρ′+ρ″)Sṽ; ○, ṽΔρ′; ◊, ṽΔρ′; △, Δη″. (b) Δx: □, Δσ; + ,
(ρ′+ρ″)Sσ̃; ○, σ̃Δρ′; ◊, σ̃Δρ″.
density data which are in most cases smaller than those related
to Sσ̃, the value for Δσ/σ of between 0.7 and 1.9% can be
regarded as a reliable estimate for the total uncertainty (k = 2)
of the surface tension of n-C12H26 over the entire temperature
range. For the systems n-C28H58 and 0.3n-C12H26/0.7n-C28H58,
uncertainties (k = 2) of between 1.1 and 2.8% in the
temperature range between 423.15 and 573.15 K can be
estimated. Due to the experimental complexity in connection
with weak oscillatory signals, the uncertainties Δσ/σ increase to
3.1% for n-C28H58 and 2.5% for 0.3n-C12H26/0.7n-C28H58 at
low temperatures and amount to between 3.0 and 5.2% for the
wax SX-70. The relative expanded uncertainties (k = 2) for the
desired properties liquid dynamic viscosity, Ur(η′), and surface
tension, Ur(σ), deduced from the procedure given above are
provided in Tables 2−4.
In order to check our present data and also the stability of
the systems, about two to three independent repetition
measurements were performed at a specific temperature in
the lower temperature range after having investigated state
points at larger temperatures. Especially for repeated measure-
ments after the study of the largest temperature of 523.15 or
573.15 K, slightly lower viscosity and surface tension data were
found which may indicate a slight sample decomposition at
high temperatures. Nevertheless, all results from the repetition
measurements agreed with the presented data within combined
uncertainties.
Data Correlation. The temperature-dependent experimen-
tal results for the liquid viscosity and the surface tension of the
four studied n-alkane systems are shown in Figures 5 and 6,
respectively. For all systems except for the wax SX-70 where
only a limited temperature range was investigated by SLS, both
properties were correlated as a function of temperature.
To represent the dynamic viscosity of liquids at the
saturation line, usually a Vogel-type or Andrade-type equation
can be used within a limited temperature range.41 Such
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temperature range covered. Instead, an inverse polynomial

Figure 5. Liquid dynamic viscosity of investigated n-alkane systems
close to saturation conditions from surface light scattering. □, n-
C12H26; ◊, n-C28H58; ○, 0.3n-C12H26/0.7n-C28H58; △, wax SX-70; −,
eq 11; --, eq 12.
Figure 6. Surface tension of investigated n-alkane systems close to
saturation conditions from surface light scattering. □, n-C12H26; ◊, n-
C28H58; ○, 0.3n-C12H26/0.7n-C28H58; △, wax SX-70; −, eq 13; --, eq
14.
equations cannot describe the experimental viscosity data for
the three pure and binary systems sufficiently over the broad
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
is in accordance with an increased momentum transport and
thus a larger viscosity for n-C28H58. For the binary system 0.3n-
C12H26/0.7n-C28H58, the viscosities are between the data for the
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
weighted scheme and neglecting a binary interaction parameter
according to
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
n-C28H58, respectively. The prediction according to eq 12
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.

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Journal of Chemical & Engineering Data
from the experimental data based on eq 11 within ±5% over
the temperature range between 398.15 and 573.15 K. The
correlation according to eq 12 is also shown in Figure 5 as a
dashed line.
The experimental data for the surface tension of the three
investigated pure and binary systems can be represented by a
modified van der Waals equation, which is suitable for
extrapolations up to the critical point,44 according to
σcalc = σ0(1 − TR )1.26 [1 + σ1(1 − TR )0.5 + σ2(1 − TR )]
(13)
where TR (=T/TC) denotes the reduced temperature. In eq 13,
σ0, σ1, and σ2 represent fit parameters and are given in Table 6.
Table 6. Coefficients of Equation 13 and Root-Mean-Square
(rms) Deviation of the Experimental Surface Tension Data
from the Correlation for the Studied Pure and Binary n-
Alkane Systems
n-C12H26 n-C28H58 0.3n-C12H26/0.7n-C28H58
σ0/(mN·m−1) 48.5580 114.8963 104.6797
σ1 0.466141 −1.659485 −1.482824
σ2 −0.559672 1.185501 1.023485
TC / K 658.65b 828.3b 788.59c
rmsa/% 0.77 0.88 0.43
T range/K 323−573 398−573 373−573
a
Standard percentage deviation of σ to the fit. bEmployed from ref 45.
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
data points, the relative deviation of the experimental data from
the data correlated by eq 13 is smaller than their uncertainties.
The surface tensions of the n-alkanes n-C12H26 and n-C28H58
show the expected trend of increasing values with increasing
carbon number.3 The larger density of longer-chained n-alkanes
also allows for forming more dispersive interactions at the
liquid surface, causing a larger surface energy and thus surface
tension. In a manner similar to that observed for the liquid
viscosity, the surface tensions of the binary mixture are closer to
the values for the pure n-C28H58. Interestingly, the surface
tension data for the wax SX-70 are between the data for the
pure n-C28H58 and for the binary mixture 0.3n-C12H26/0.7n-
C28H58. It seems that the liquid surface of the wax is rather
enriched by short-chained n-alkanes with a carbon number
below 30, which results in a minimization of the surface energy.
This may also explain the relatively large liquid viscosity of the
wax in comparison with n-C28H58.
A correlation for the surface tension of a binary liquid
mixture is usually not a simple function of the composition
because the composition in the bulk can be different from that
at the surface. This issue could already be observed from the
aforementioned behavior of the viscosity and surface tension
data for the wax SX-70. Typically, the component with the
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smaller surface tension enriches at the surface in terms of
surface energy minimization. This causes the mixture surface
tension to be less than the mole fraction average of the surface
tension of the pure compounds.40 Using the surface tensions
measured for the pure systems n-C12H26 and n-C28H58, a mole
fraction based mixing rule for the system 0.3n-C12H26/0.7n-
C28H58 would result in between −2 and −8% lower surface
tensions than the data correlated by eq 13 over the temperature
range between 398.15 and 573.15 K, with a different
temperature-dependent trend. Thus, the surface region seems
to be enriched by n-C28H58 having a larger surface tension than
n-C12H26. According to that, a mixing rule based on the mass
fraction of the two components in the form of
σ = w1σcalc,1 + w2σcalc,2 (14)
was applied. As illustrated in Figure 6 as a dashed line, the
mixing rule based on eq 14 represents the measured surface
tension data within 2% over the entire temperature range
between 398.15 and 573.15 K, which is within most of the
uncertainties of the experimental data for the binary mixture.
Comparison with Literature. A data comparison with
experimental literature data for the systems studied in this work
can only be performed for the pure substances n-C12H26 and n-
C28H58. No experimental data are available for the systems 0.3n-
C12H26/0.7n-C28H58 and the wax SX-70.
In Figure 7, our values for the dynamic viscosity of n-C12H26
measured close to saturation conditions are shown in
Figure 7. Data comparison for dynamic viscosity of liquid dodecane.
■, this work; −, eq 11; --, Huber et al.;32 △, Dymond and Young;47 ◊,
Knapstad et al.;48 ▽, Knapstad et al.;49 ○, Caudwell et al.50
comparison with literature data. Deviations between our results
from SLS and the literature values are plotted using our
correlation, eq 11, as a basis. For the reference fluid n-C12H26,
the Refprop database3 refers to the pure fluid model from
Huber et al.,32 which represents the dynamic viscosity as the
sum of a dilute gas contribution and a residual part containing
higher order density terms. For this model representing the
considered experimental data in the temperature range between
262 and 473 K with an absolute average deviation of 0.95%, the
estimated uncertainty in viscosity along the saturated liquid line
is specified to be 0.5%.32 As shown in Figure 7, agreement
between our experimental data and the correlation of Huber et
al.32 within ±2% and thus within the experimental uncertainty
of our data can be found for the temperature range between
323 and 523 K. At larger temperatures up to 573 K, the
correlation gives slightly lower values compared to our values
outside combined uncertainties. This seems to be related to the
limited temperature range of the data used to develop the
correlation which takes the character of an extrapolation at
higher temperatures.
DOI: 10.1021/acs.jced.7b00363
J. Chem. Eng. Data 2017, 62, 3319−3333
Journal of Chemical & Engineering Data
The experimental data sources used for the development of
the correlation of Huber et al.32 are discussed below and only
considered here. The data of Dymond and Young47 were
measured with a suspended level viscometer at saturation
pressure between 283 and 393 K using a sample with mole
fraction purity of more than 0.99. Knapstad et al.48 determined
the viscosity of a sample with a purity w > 0.9966 using an
oscillating cylinder viscometer at atmospheric pressure for
temperatures between 293 and 425 K. Both aforementioned
sets have an estimated uncertainty of 0.5%. Knapstad et al.49
later reported further measurements on n-C12H26 of the same
sample purity (w > 0.9966) at atmospheric pressure from 289
to 343 K, stating estimated uncertainties of between 0.4 and
0.6%. Caudwell et al.50 performed the most recent viscosity
measurements, which were made with a vibrating-wire
instrument operated between 298 and 473 K in the compressed
liquid phase at a pressures of 0.1 MPa with a reported
uncertainty of 2%. The data obtained by Lyusternik and
Zhdanov51 in the gaseous region between 503 and 681 K as
well as by Giller and Drickamer52 near the freezing point of
about 262 K up to 293 K cannot be used for data comparison
here. More recent experimental viscosity data for n-C12H26 at or
close to saturation conditions are generally determined only
around ambient temperature below 323 K53,54 or agree with
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
temperature range and conditions at or close to saturation as
studied in this work are shown. All experimental data points
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
the correlation of Huber et al.32 at temperatures above 523 K
may be related in that the latter correlation is strongly
influenced by the temperature-dependent trend of the
experimental data of Caudwell et al.50
For the liquid viscosity of n-C28H58, only two data sources
providing experimental results could be found. In 1951,
Doolittle and Peterson57 performed measurements at atmos-
pheric pressure for a temperature range between 263 and 573 K
employing a Ubbelohde capillary viscometer with a claimed
uncertainty of between 1.2 and 1.5%. No information on the
purity of the sample is given. Compared to our correlation in
the temperature range developed from our measurements, the
liquid viscosity data of Doolittle and Peterson57 show larger
values outside combined uncertainties with deviations between
+8.2% at 373.15 K and +4.4% at 548.15 K. Such deviations
might be related to the different sample purities, which is likely
to be possible for long-chained alkane systems. The other data
set measured by Mazee58 with an Ostwald-type viscometer
reports viscosity values in a temperature range between 343.15
and 363.15 K, which is outside the temperature range
investigated in the present study. By extrapolating our
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correlation based on eq 11 to lower temperatures, relative
deviations between the data of Mazee58 and our correlated data
ranging from +16.0 to +26.4% can be found. These deviations
are outside the combined uncertainties considering the
uncertainty of the experimental data of Mazee58 of 0.2% and
the uncertainty intervals of the extrapolated correlated data
based on a confidence level of more than 95% (k = 2). One
possible reason for the discrepancies may be the limited
applicability of the correlation to lower temperatures close to
the melting point where typically a strong increase in the liquid
viscosity is observed.
An estimation of the liquid viscosity of n-C28H58 can be
carried out using the database in Yaws’ handbook.5 The
correlation based on the regression of unstated experimental
data and researched estimates provides viscosity values which
are distinctly lower than our measured data. The relative
deviation increases with increasing temperature and covers a
range between −6.5% at 398.15 K and −56.3% at 573.15 K.
Hence, the reliability of viscosity estimations or extrapolations
as those used in the database of Yaws’ handbook5 is highly
questionable, especially for weakly characterized substances
such as n-C28H58.
The surface tensions of n-C12H26 obtained from SLS are
plotted in Figure 8 together with available experimental
Figure 8. Data comparison for surface tension of dodecane. ■, this
work; −, eq 13; --, Mulero et al.;59 △, Jasper;61 ◊, Körösi and
Kováts;62 ○, Cumicheo et al.63
literature data covering the temperature range investigated in
this work. Our correlation according to eq 13 serves as a
reference. The Refprop database3 recommends the use of the
surface tension model of Mulero et al.59 The correlation
represents the 60 experimental data points measured in a
temperature range between 273.15 and 473.15 K and used for
the development of the model with an absolute average
deviation of 0.49%. Both the data sources considered and the
uncertainty of the model are not defined. According to Figure
8, the model of Mulero et al.59 yields between 2.4 and 4.6%
larger values than our correlation over the entire temperature
range between 323 and 573 K. Assuming an uncertainty of 2%
for the correlation of Mulero et al.,59 both data sets would be
within combined uncertainties in most cases, even for the
extrapolated data at temperatures above 473 K.
Most experimental σ data for n-C12H26 are generally
determined only around ambient temperature below 323
K53,55,60 and are thus not used for data comparison here. In
total, three data sources providing surface tension data of n-
C12H28 above 323 K were found and are discussed below.
Jasper61 applied the capillary rise method for measuring the
surface tension under isobaric conditions with an atmosphere
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J. Chem. Eng. Data 2017, 62, 3319−3333
Journal of Chemical & Engineering Data
consisting of nitrogen and dodecane vapor at temperatures
between 283.15 and 393.15 K. A low uncertainty of 0.01 mN·
m−1, i.e., smaller than 0.1%, is claimed by the authors. The
capillary rise method was also used by Körösi and Kováts62 for
temperatures of 293.15 and 353.15 K, without specifying the
ambient conditions. The uncertainty of their surface tension
data is below 0.3%. Cumicheo et al.63 determined the surface
tension at ambient pressure and a single temperature of 344.15
K with the help of the pendant drop method with an
uncertainty of 0.01 mN m−1. Except for Jasper,61 who provides
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
other and by trend larger than our data. Furthermore, the
temperature-dependent data of Jasper61 converge with the
present measurement results at larger T values. Discrepancies in
published surface tension values are not uncommon because
the determination of this property may be affected by two
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
measured for liquid−air systems, as in most cases cited above,
the surface temperature may be somewhat below the
temperature in the bulk of the fluid, a fact which may rather
increase the surface tension. An influence of this error can be
excluded for the present investigation, which has been carried
out inside a closed sample cell close to saturation conditions in
thermodynamic equilibrium.
Since no experimental surface tension data are available for n-
C28H58, estimated data were derived from Yaws’ handbook.5
The calculated results, which are based on a simple van der
Waals equation, deviate between +2.4 and +6.1% from our data
correlated via eq 13 within the temperature range between
398.15 and 573.15 K. The source of the parameters used in the
model and the reliability of the model itself, which is applied for
a broad temperature range here but theoretically only valid
close to the critical region, is debatable.
■ CONCLUSIONS
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
fraction for n-dodecane of about 0.3, and a commercially
available hydrocarbon wax have shown that surface light
scattering can be used to reliably determine the liquid viscosity
and surface tension over a broad temperature range between
323 and 573 K close to saturation conditions. Based on the
recorded light scattering signals as well as literature data and
correlations for the liquid densities, vapor densities, and vapor
dynamic viscosities, an expanded measurement uncertainty (k =
2) of less than 2% for the liquid dynamic viscosity and less than
1.5% for the surface tension could typically be achieved. Over
the entire temperature range, a simple polynomial equation for
the liquid viscosity and a modified van der Waals equation for
the surface tension can represent the measured data of the pure
and binary systems mostly within experimental uncertainties.
For the reference fluid n-dodecane, agreement between our and
the current reference data exists for the liquid viscosity in the
low-temperature region, but deviations are found at higher
temperatures where extrapolations are used in the case of the
reference data. Our measured surface tensions are in general
lower than the available sources of reference data within relative
deviations below 5%. Due to a lack of experimental data for the
3331
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other long-chained alkane systems, theoretical estimations in
literature for n-octacosane show distinct discrepancies from our
measurements, especially for the liquid viscosity with deviations
of more than 50%. In this connection, the experimental data
obtained in this work can improve the data situation for
viscosity and surface tension of medium- to long-chained n-
alkane systems in the high-temperature regime. Furthermore,
they can be used to develop modeling approaches by serving as
reference values for theoretical and empirical models as well as
molecular simulations.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jced.7b00363.
Composition analysis of the systems investigated by SLS
and liquid density data of the wax SX-70 (PDF)
■ AUTHOR INFORMATION
Corresponding Author
*Tel.: +49-9131-85-23279. Fax: +49-9131-85-25851. E-mail:
thomas.m.koller@fau.de.
ORCID
Thomas M. Koller: 0000-0003-4917-3079
Cédric Giraudet: 0000-0003-2051-7042
Jiaqi Chen: 0000-0002-2591-0073
Andreas P. Fröba: 0000-0002-9616-3888
Funding
This work was financially supported by the German Research
Foundation (Deutsche Forschungsgemeinschaft, DFG) by
funding the Erlangen Graduate School in Advanced Optical
Technologies (SAOT) within the German Excellence Initiative.
Financial support from Shell Global Solutions International
B.V. through a contracted research agreement is gratefully
acknowledged.
Notes
The authors declare no competing financial interest.
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3333 DOI: 10.1021/acs.jced.7b00363

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