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Chemical Physics 369 (2010) 126–137

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Chemical Physics
journal homepage: www.elsevier.com/locate/chemphys

Influence of the chain length on the dynamic viscosity at high pressure of some
2-alkylamines: Measurements and comparative study of some models
Masatoshi Yoshimura a,b, Christian Boned a,*, Guillaume Galliéro a, Jean-Patrick Bazile a,
Antoine Baylaucq a, Hideharu Ushiki b
a
Laboratoire des Fluides Complexes, Faculté des Sciences et Techniques, UMR CNRS 5150, Université de Pau et des Pays de l’Adour, BP 1155, 64013 Pau Cedex, France
b
Laboratory of Molecular Dynamics and Complex Chemical Physics, Department of Environmental and Natural Resource Science, Faculty of Agriculture,
Tokyo University of Agriculture and Technology, 3-5-8 Saiwai-cho, Fuchu-shi, Tokyo 183-8509, Japan

a r t i c l e i n f o a b s t r a c t

Article history: This work reports the dynamic viscosity data (a total of 93 points) of 2-alkylamines, which exhibit small
Received 24 December 2009 association, consisting of 2-aminobutane, 2-aminopentane, 2-aminoheptane and 2-aminooctane at four
In final form 12 March 2010 temperatures between 293.15 K and 353.15 K (every 20 K), and pressures up to 100 MPa (every
Available online 18 March 2010
20 MPa) which allows to study the influence of the chain length. A falling-body viscometer with an uncer-
tainty of ±2% was used to perform these measurements.
Keywords: The variations of dynamic viscosity are discussed with respect to their behaviour due to chain length.
2-Alkylamine
Seven different models, most of them with a physical and theoretical background, are studied in order to
Chain length
Modeling
investigate how they take the chain length effect into account through their required model parameters.
Pressure The evaluated models are based on the empirical Vogel–Fulcher–Tamman (VFT) representation (com-
Viscosity bined with a Tait-like equation), the rough hard-sphere scheme, the concept of the free-volume, the fric-
tion theory, a correlation derived from molecular dynamics, a model based on Eyring’s absolute rate
theory combined with cubic EoS. A scaling viscosity representation has also been considered. These mod-
els need some adjustable parameters except the molecular dynamics correlation that is entirely predic-
tive. Overall a satisfactory representation of the viscosity of these 2-alkylamines is found for the different
models within the considered T, p range taking into account their simplicity. Moreover, it has been ver-
ified that the viscosity is a unique function of TVc where the exponent c is generally related to the steep-
ness of the intermolecular repulsive potential (T: temperature and V: specific volume).
Ó 2010 Elsevier B.V. All rights reserved.

1. Introduction CH3CH2CH(NH2)CH3), 2-aminopentane (CH3(CH2)2CH(NH2)CH3),


2-aminoheptane (CH3(CH2)4CH(NH2)CH3), and 2-aminooctane
In a previous work by our group on some linear primary amines (CH3(CH2)5CH(NH2)CH3), has been measured up to 100 MPa be-
[1], it has been underlined that there is a lack of information on the tween 293.15 K and 353.15 K. The structure of these molecules is
thermophysical properties of aliphatic amines. Aliphatic amines shown in Fig. 1. To the best of our knowledge, concerning these
are used as a solvent, as a raw material in the manufacture of a 2-alkylamines, which have branching structure (i.e. amino group
variety of other compounds, including emulsifiers and pharmaceu- is located at the second carbon of alkyl chain), there are no exper-
tical products. An accurate database of thermophysical properties imental data of viscosity versus pressure. Mention here that the
of these fluids is of practical and fundamental value for the chem- density measurements for two 2-alkylamines (2-aminobutane
ical engineering application. and 2-aminooctane) have previously been performed with a
With the aim of completing a database relative to this chemical vibrating-tube densimeter as a function of temperature and pres-
family, we have published some experimental viscosity data con- sure [2]. In addition, the density of 2-aminopentane and 2-amino-
cerning linear amines (pentyl-, hexyl- and heptylamine) versus heptane measured as in Ref. [2] up to 100 MPa between 293.15 K
pressure up to 100 MPa in the temperature interval (293.15 K and 353.15 K are reported in this work.
and 353.15 K) [1]. From a theoretical point of view, an accurate experimental
In this work, the dynamic viscosity g (93 experimental data in database of dynamic viscosity is usable to investigate the appropri-
total) for four 2-alkylamines: 2-aminobutane (sec-butylamine, ateness of some viscosity models taking the chain length and
branching effect into account. In particular from the structural dif-
* Corresponding author. Tel.: +33 559 407 688; fax: +33 559 407 695. ference between two kinds of amines, linear 1-alkylamines and
E-mail address: christian.boned@univ-pau.fr (C. Boned). branched 2-alkylamines, it is possible to study how the difference

0301-0104/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.chemphys.2010.03.016
M. Yoshimura et al. / Chemical Physics 369 (2010) 126–137 127

of the position of amino-group, which affects intermolecular inter- is designed with a ratio between its diameter and the tube diame-
actions, influences the macroscopic transport property i.e. viscos- ter greater than 0.98, which is substantially above the recom-
ity. In this work, seven different viscosity models are studied. mended value of 0.93 in order to ensure a concentric fall and to
The considered models are the empirical Vogel–Fulcher–Tamman minimize eccentricity effects [21–23]. Since the density of the sin-
(VFT) [3–5] representation combined with a Tait-like equation, ker is about 9 times higher than the density of the fluids considered
the rough hard-sphere scheme [6,7], the model based on free-vol- in this work an error in the fluid density of 0.1% results in an error
ume concept [8–10], the model based on the friction theory of about 1/7000 for qS  qL (see relation (1)) and consequently a
[11,12], a model derived from molecular dynamics simulation very small error on viscosity. In this work, Ds corresponds to the
[13], the Eyring theory and cubic EoS model [14,15] and a scaling average value of six measurements of the falling time at thermal
viscosity representation [16,17]. and mechanical equilibrium with a reproducibility of 0.5%.
The calibration of the viscometer has been performed using
2. Experimental procedure accurate viscosity and density data for toluene and decane. The re-
quired reference viscosity and density data for toluene have been
The dynamic viscosity g under pressure was measured using a estimated by the correlation given for the viscosity and density
falling-body viscometer. This viscometer is of the type designed by Assael et al. [24]. The reported uncertainties for the calculated
by Daugé et al. [18]. The viscometer consists of two high-pressure density and viscosity values are 0.03% and 2%, respectively. For
cells, a measuring cell and a piston cell, which are connected by a n-decane, the viscosity data has been obtained by the correlation
capillary tube and a valve, see Fig. 1 in Ref. [18]. The piston cell is given by Huber et al. [25] using density values calculated by the
connected to a pneumatic oil pump, which is used to pressurize the expression given by Cibulka and Hnědkovský [26]. The reported
viscometer. The pressure of the sample within the viscometer is uncertainty for the calculated n-decane density and viscosity val-
measured by an HBM-P3M manometer connected directly to the ues are 0.1% and 2%, respectively. The apparatus parameters Ka
tube between the two cells, ensuring a measure of the real pressure and Kb are determined at each considered (T, p) condition by plot-
of the sample. The pressure is measured with an uncertainty of ting the reference viscosities of the two calibrating fluids as a func-
0.2 MPa. The temperature is measured inside the measuring cell tion of (qS  qL)Ds.
by a Pt100 probe connected to a classical AOIP thermometer with In this work, the densities of two 2-alkylamines (2-aminobu-
an uncertainty of 0.5 K. A circulating fluid supplied by an external tane and 2-aminooctane) were taken from Ref. [2], where they
thermostatic bath controls the temperature of the sample in the have been measured up to 140 MPa between 293.15 K and
measuring cell and the piston cell. The viscometer is placed in an 353.15 K with a vibrating-tube densimeter. The uncertainty re-
automated air-pulsed thermal regulator oven in order to ensure a ported for these density measurements is ±5  104 g cm3
homogeneous temperature surrounding the system. Since the flu- (around 0.05%). Taking into account the uncertainty due to the cal-
ids considered in this work are liquids at atmospheric pressure, the ibration, the temperature, the pressure and the density, the overall
filling procedure of the viscometer was done as described in Ref. uncertainty for the reported dynamic viscosities is of the order of
[19]. 2%. The accuracy of the device has been checked several times.
The basic principle of the falling-body viscometer is that a sin- For instance, recently in our group [19], the same instrument has
ker falls through a fluid of unknown viscosity under a given tem- been used to measure the dynamic viscosity of methanol between
perature and pressure (T, p) condition. It has been emphasized by 293.15 K and 353.15 K up to 100 MPa. These data have been fur-
Daugé et al. [18] that, for this type of viscometer and for fluids with ther used in a study about a new reference correlation [27] for
a low viscosity, a working equation of the functional form the viscosity of methanol, taking into account of many methanol
g(T, p) = f[(qS  qL)Ds] should be used. This working equation re- literature data. Our data agree with the reference correlation with
lates the dynamic viscosity to the difference between the density an average absolute deviation of 1.0%, which is very satisfactory.
of the sinker qS and of the fluid qL, and the falling time, Ds, be- At atmospheric pressure (0.1 MPa) the dynamic viscosity was
tween two detection sensors when the velocity of the sinker is con- obtained by measuring the kinematic viscosity, m = g/q, with a clas-
stant. For fluids with a very low dynamic viscosity, such as sical capillary viscometer (Ubbelohde). For this purpose several
methane, Daugé et al. [18] used a second-order polynomial in tubes connected to an automatic AVS350 Schott Geräte Analyzer
(qS  qL)Ds which implies the requirement of three reference flu- were used. The temperature of the fluid is controlled within 0.1 K
ids in order to perform the calibration of the viscometer. In this using a thermostatic bath. When multiplying the kinematic viscos-
work the lowest viscosity is 0.285 mPa s for 2-aminobutane at ity with the density, the dynamic viscosity is obtained with an
T = 353.15 K and p = 20 MPa, which is not too low, and conse- uncertainty less than 1%. Each capillary tube is provided with a cal-
quently it was found appropriate to use a linear relation for the ibration certificate but we checked the calibration of the capillary
working equation as follows: viscometer at several temperature using ‘‘Cannon Certified Viscos-
ity Standard” reference fluids.
gðT; pÞ ¼ K a ðT; pÞ þ K b ðT; pÞðqS  qL ÞDs; ð1Þ 2-aminobutane (sec-butylamine, C4H11N, molar mass M = 73.14
which relates the dynamic viscosity to two parameters Ka and Kb. A g mol1, boiling point at atmospheric pressure Tb = 336.15 K, CAS
similar working equation has recently been used by Pensado et al. number 13952-84-6), 2-aminopentane (C5H13N, M = 87.16
[20]. g mol1, Tb = 363.65  364.65 K, CAS number 63493-28-7), 2-ami-
The sinker used in this work is a solid stainless steel cylinder noheptane (C7H17N, M = mass 115.22 g mol1, Tb = 415.15 
with hemispherical ends and a density of 7.72 g cm3. The sinker 417.15 K, CAS number 123-82-0) and 2-aminooctane (C8H19N,

Fig. 1. Molecular structure of (a) 2-aminobutane, (b) 2-aminopentane, (c) 2-aminoheptane, and (d) 2-aminooctane.
128 M. Yoshimura et al. / Chemical Physics 369 (2010) 126–137

M = 129.24 g mol1, Tb = 438.15 K, CAS number 693-16-3) were ob-


tained from Sigma–Aldrich with purity of, respectively, 99%, 97%,
99% and 99% (with certificate of analysis by gas chromatography
of, respectively, 99.9%, 98.7%, 99.0% and 99.41%). These chemicals
were not subject to further purification and were directly injected
into the high-pressure cell as soon as the bottle was opened.

3. Experimental results

The values of density for 2-aminobutane and 2-aminootane ta-


ken from Ref. [2] and the values of viscosity and density measured
in this work for four 2-alkylamines are reported in Table 1. The
measurements have been performed at various temperatures
(293.15, 313.15, 333.15 and 353.15) K for pressures at (0.1, 20,
40, 60, 80 and 100) MPa. Note, however, that it was not possible
Fig. 2. Comparison with literature data of viscosity at atmospheric pressure for 2-
to measure viscosity or density at some conditions for 2-aminobu- aminobutane. }: Bai 2005 [29], s: Rao 2006 [28], h: Saleh 2001 [31], 4: Subha
tane (p = 0.1 MPa, T = 333.15 and 353.15 K) and 2-aminopentane 2004 [30], d: this work. Solid line is fitting curve for all the values from literature
(p = 0.1 MPa, T = 353.15 K) as temperature is near or over their Tb. and this work with quadratic polynomial function.
As we did not find in the literature viscosity values at high pres-
sure, the comparison was possible only at atmospheric pressure.
We found data only for 2-aminobutane (sec-butylamine) at amines from Ref. [2]. From Fig. 3, it can be seen that the viscosity
T = 303.15 K by Rao et al. [28], at T = 308.15 K by Bai et al. [29] decreases monotonically with increasing temperature. Fig. 4 shows
and Subha et al. [30], and at T = 298.15 up to 323.15 K (DT = 5 K) that the viscosity increases with increasing pressure. This behavior
by Saleh et al. [31]. Among these data, it is possible to do the quan- is the one generally observed in liquids. In fact, this is not surpris-
titative comparison only at T = 313.15 K with [31], and we obtained ing as primary amines exhibit a weak hydrogen bonding. Fig. 5
a deviation of 3.9%. Fig. 2 shows for 2-aminobutane our data and shows the variation of the viscosity versus density at p = 0.1 and
the various literature viscosity data versus temperature at atmo- 100 MPa. Fig. 6 shows the variation of the viscosity versus density
spheric pressure. The solid line corresponds to a polynomial qua- at T = (293.15 and 353.15) K. It is interesting to notice that, in the
dratic fitting obtained using all the data. For the other three 2- case of constant pressure (Fig. 5), the viscosity data points versus
alkylamines, viscosity data was not found even at atmospheric density are roughly on the same curve independently of the alkyl
pressure. chain length of amines, however, it is not the case at constant tem-
The variation of the viscosity versus temperature at p = 60 MPa perature (Fig. 6). This indicates that it is the density which mainly
for four 2-alkylamines of this work and two 1-alkylamines (pentyl- determines the viscosity amplitude, more than the temperature or
amine and heptylamine) from Ref. [2] is shown in Fig. 3. Fig. 4 the chain length.
shows the variation of the viscosity versus pressure at The difference between four 2-alkylamines (2-aminobutane, 2-
T = 313.15 K for four 2-alkylamines of this work and two 1-alkyl- aminopentane, 2-aminoheptane and 2-aminooctane) is the length

Table 1
Dynamic viscosity g (mPa s) and density q (g cm3) versus temperature and pressure for four 2-alkylamines (2-aminobutane, 2-aminopentane, 2-aminoheptane and 2-
aminooctane).

T (K) p (MPa) 2-Aminobutane 2-Aminopentane 2-Aminoheptane 2-Aminooctane


g q g q g q g q
293.15 0.1 0.460 0.7253a 0.622 0.7478 0.903 0.7642 1.159 0.7720a
293.15 20 0.557 0.7412a 0.731 0.7625 1.083 0.7777 1.389 0.7848a
293.15 40 0.648 0.7545a 0.864 0.7748 1.294 0.7893 1.699 0.7961a
293.15 60 0.738 0.7661a 1.001 0.7855 1.540 0.7994 2.068 0.8060a
293.15 80 0.830 0.7763a 1.141 0.7951 1.819 0.8085 2.493 0.8150a
293.15 100 0.921 0.7855a 1.285 0.8038 2.148 0.8167 3.005 0.8232a
313.15 0.1 0.360 0.7050a 0.469 0.7293 0.661 0.7477 0.829 0.7558a
313.15 20 0.440 0.7234a 0.551 0.7457 0.793 0.7627 0.981 0.7704a
313.15 40 0.512 0.7382a 0.644 0.7594 0.950 0.7753 1.187 0.7825a
313.15 60 0.584 0.7508a 0.742 0.7712 1.118 0.7863 1.417 0.7932a
313.15 80 0.657 0.7619a 0.845 0.7816 1.300 0.7961 1.673 0.8027a
313.15 100 0.730 0.7718a 0.953 0.7909 1.494 0.8049 1.955 0.8114a
333.15 0.1 –b –b 0.364 0.7099 0.511 0.7302 0.630 0.7396a
333.15 20 0.350 0.7052a 0.432 0.7290 0.610 0.7473 0.740 0.7555a
333.15 40 0.409 0.7220a 0.504 0.7443 0.727 0.7612 0.887 0.7690a
333.15 60 0.469 0.7358a 0.578 0.7571 0.852 0.7732 1.048 0.7806a
333.15 80 0.529 0.7480a 0.653 0.7685 0.986 0.7839 1.228 0.7909a
333.15 100 0.593 0.7586a 0.730 0.7784 1.129 0.7934 1.426 0.8000a
353.15 0.1 –b –b –b –b 0.411 0.7132 0.496 0.7232a
353.15 20 0.285 0.6871a 0.348 0.7120 0.485 0.7322 0.596 0.7416a
353.15 40 0.336 0.7058a 0.410 0.7290 0.576 0.7477 0.708 0.7562a
353.15 60 0.386 0.7212a 0.471 0.7430 0.673 0.7607 0.825 0.7687a
353.15 80 0.436 0.7342a 0.531 0.7552 0.778 0.7721 0.949 0.7797a
353.15 100 0.488 0.7457a 0.590 0.7659 0.891 0.7822 1.080 0.7895a
a
The values for 2-aminopentane and 2-aminoheptane are taken from Ref. [2].
b
Viscosity and density cannot be measured on the condition in empty columns as temperature is near or over Tb (p = 0.1 MPa).
M. Yoshimura et al. / Chemical Physics 369 (2010) 126–137 129

Fig. 3. Dynamic viscosity versus temperature at p = 60 MPa for four 2-alkylamines Fig. 6. Dynamic viscosity versus density at T = 293.15 K (j: 2-aminobutane, : 2-
(j: 2-aminobutane, : 2-aminopentane, N: 2-aminoheptane and d: 2-aminooc- aminopentane, N: 2-aminoheptane and d: 2-aminooctane) and T = 353.15 K (h: 2-
tane) and two 1-alkylamines (}: pentylamine and 4: heptylamine) [2]. aminobutane, }: 2-aminopentane, 4: 2-aminoheptane and s: 2-aminooctane).

mine which has longer alkyl chain tends to form denser, less com-
pressible liquid than other 2-alkylamines which have shorter alkyl
chain at a given pressure.
From the viewpoint of the difference in the position of amino
group, Figs. 3 and 4 indicate that 1-alkylamines, which have linear
structure, show higher viscosity than 2-alkylamines, which have
branching structure, in the temperature and pressure range con-
sidered here. The same tendency was observed in the measure-
ment of density [2].
Generally, when a fluid is brought under pressure (compressed),
the flexibility and mobility of the molecules are reduced, since the
distance and space between the molecules become shorter, result-
ing in a reduction of the fluid mobility and an increase in the vis-
cosity. Kioupis and Maginn [32] explained the fact that the
viscosity increases with pressure as a result of a reduction in the
Fig. 4. Dynamic viscosity versus pressure at T = 313.15 K for four 2-alkylamines (j: liquid void volume coupled with the molecular structure, resulting
2-aminobutane, : 2-aminopentane, N: 2-aminoheptane and d: 2-aminooctane) in a lower motion of the molecules, because the motion is related
and two 1-alkylamines (}: pentylamine and 4: heptylamine) [2]. either to molecules jumping or forcing adjacent molecules into
these voids. Therefore, when the number of voids decreases with
increasing pressure, complex molecules with a low flexibility will
have difficulties of making these jumps or forcing other molecules
into these voids, resulting in the trapping of the molecules and a
higher viscosity.
For the four amines considered in this work, a slightly sharper
increase of dynamic viscosity against pressure has been found for
2-aminooctane than for 2-aminoheptane, -pentane and -butane
(Fig. 4) due to the increase of the alkyl chain length, which results
in an important reduction of the fluid mobility (higher viscosity)
when brought under pressure.

4. Discussion

Since these molecules have a different chain length, it is inter-


esting to investigate how the effect of the chain length is taken into
account by some viscosity models. First we consider an empirical
Fig. 5. Dynamic viscosity versus density at p = 0.1 MPa (j: 2-aminobutane, : 2-
aminopentane, N: 2-aminoheptane and d: 2-aminooctane) and p = 100 MPa (h: 2-
model based on Vogel–Fulcher–Tamman’s (VFT) viscosity repre-
aminobutane, }: 2-aminopentane, 4: 2-aminoheptane and s: 2-aminooctane). sentation [3–5] combined with Tait-like equation. Second, six more
or less recently derived models with a physical and theoretical
background are considered: rough hard-sphere scheme [6,7],
of alkyl chain in their molecular structure (Fig. 1) which affects the free-volume scheme [8–10], friction theory [11,12], correlation
dynamic viscosity for a given temperature and pressure. As ex- based on molecular dynamics simulation of Lennard–Jones fluid
pected the viscosity increases with the chain length for a given [13], a scaling viscosity model [16,17], and model based on the Eyr-
set of T and p (Figs. 3 and 4), but notice that it is less sensitive to ing theory combined with a cubic EoS [14,15]. For the models using
the chain length for a given set of p and q or T and q (Figs. 5 and experimental density values, they are taken from Ref. [2] and from
6). Further, as observed in the density measurement [2], 2-alkyla- this work (Table 1).
130 M. Yoshimura et al. / Chemical Physics 369 (2010) 126–137

In order to make a comparative study of the performance of dif- that the worse overall MD, found for 2-aminooctane at T = 353.15 K
ferent viscosity models to represent the viscosity, the following and p = 0.1 MPa, is of the same order of magnitude as the experi-
definitions are used. mental error.

Deviationi ¼ 1  gcalc;i =gexp;i ;


4.2. The rough hard-sphere scheme
1 X NP
AAD ¼ jDeviationi j;
NP i¼1 The second viscosity model employed is based on the fact that a
ð2Þ corresponding states relationship exists [6,7] between the experi-
MD ¼ MaximumjDeviationi j;
mental transport properties of rough non-spherical molecules
1 X NP
and the smooth hard-sphere values (subscript shs):
Bias ¼ Deviationi ;
NP i¼1 gexp ¼ Rg gshs ; ð4Þ
where NP is the number of data points, gexp the experimental vis- where the proportionality factor Rg, described as the roughness fac-
cosity and gcalc the calculated viscosity. The AAD (average absolute tor, accounts for the roughness and non-spherical shape of the mol-
deviation) indicates how close the calculated values are to the ecule. The roughness factor is related to the non-spherical shape of
experimental values, and the quantity Bias indicates how well the the molecule (see e.g. [35]) and Rg = 1 corresponds to a spherical
experimental points are distributed around the calculated points. molecule. Dymond and Awan [6] derived the following expression
If Bias is equal to AAD, then all of the calculated values are below relating the reduced smooth hard-sphere viscosity gshs to the exper-
the experimental values. Further, the quantity MD refers to the imental value gexp:
absolute maximum deviation. rffiffiffiffiffiffiffiffiffiffi
gexp 1 gexp v 2=3
gshs ¼ ¼ 6:035  108 ð5Þ
4.1. Vogel–Fulcher–Tamman–Tait representation Rg MRT Rg
with v the molar volume, M the molar mass and R the gas constant.
The first viscosity model considered in this work is one already
In order to determine Rg and v0, the close packing molar volume, for
proposed and described more precisely in a previous work of our
a given temperature a plot of log10 ðgexp Þ versus log10(m) from the
team [33]:
  experiment is superimposed on a universal plot of log10 ðgshs Þ versus
EðTÞ þ p log10(m/m0) from the hard-sphere theory by vertical and horizontal
gðp; TÞ ¼ A exp½B=ðT  CÞ exp D ln ; ð3Þ
EðTÞ þ 0:1MPa adjustments. The empirical expression for this curve is:
  X  i
where D was assumed to be temperature independent and E(T) is a gexp 7
1
second-order polynomial as E(T) = E0 + E1T + E2T2. This equation is log10 ¼ ag;i : ð6Þ
Rg i¼0
vr
derived from a Tait-like equation combined with the empirical Vo-
gel–Fulcher–Tamman’s model [3–5] which can be considered as The ag,i coefficients [7] are universal, independent of the chemical
Andrade’s modified equation [34]. nature of the compound. This has been verified by Baylaucq et al.
Experimental viscosity data have been fitted with Eq. (3) by [36,37]. Further, it is generally assumed that v0 is temperature
Levenberg–Marquardt algorithm and the obtained coefficients dependent, whereas Rg is temperature independent [35].
are shown in Table 2 for four 2-alkylamines. In order to use them, The estimated hard-core volume v0 for each temperature
p is in MPa, T in K, M in kg m3 and the viscosity is in mPa s. Notice and the roughness factor Rg are given in Table 3 for the four

Table 2
Values of coefficients and results obtained with the Vogel–Fulcher–Tamman’s representation (Eq. (3)).

2-Aminobutane 2-Aminopentane 2-Aminoheptane 2-Aminooctane Overall


A 0.00017525 0.017364 0.011448 0.047302
B 4941.2 835.53 1213.6 561.81
C 334.21 59.182 14.627 116.71
D 0.93693 1.5163 3.5456 7.1394
E0 17.154 165.64 1491 2517
E1 0.58743 1.8448 10.84 17.388
E2 0.0011376 0.002501 0.015464 0.021993
AAD (%) 0.250 0.410 0.541 0.736 0.484
Bias (%) 0.000514 0.00411 0.0338 0.0539 0.0228
MD (%) 0.76 0.97 1.16 2.64 2.64

Table 3
Adjusted values of the roughness factor Rg and the hard-core volume v0 (m3 mol1) in the rough hard-sphere viscosity scheme (Eqs. (5) and (6)).
2-Aminobutane 2-Aminopentane 2-Aminoheptane 2-Aminooctane Overall
Rg 1.261 1.287 1.241 1.290
v0 (293.15 K) 6.445E05 7.730E05 1.049E04 1.190E04
v0 (313.15 K) 6.378E05 7.621E05 1.036E04 1.174E04
v0 (333.15 K) 6.301E05 7.506E05 1.025E04 1.160E04
v0 (353.15 K) 6.198E05 7.394E05 1.014E04 1.147E04
AAD (%) 1.033 0.631 0.628 1.092 0.846
Bias (%) 0.086 0.036 0.053 0.050 0.005
MD (%) 2.07 1.50 1.34 2.77 2.77
M. Yoshimura et al. / Chemical Physics 369 (2010) 126–137 131

2-alkylamines. The calculation has been done in order to minimize dense supercritical states. Recently [10], the model has been gener-
MD for all the data. The modeling for the four compounds resulted alized to the simultaneous modeling of the self-diffusion coefficient
in an AAD of 0.85% with a MD of 2.77% close to the magnitude of and dynamic viscosity at high pressure (up to 500 MPa).
the experimental error. The obtained v0 is increasing with molar The dilute gas viscosity term g0 can be obtained by any appro-
mass and is decreasing with temperature. The obtained Rg is not priate model, for instance the model by Chung et al. [40] which is
regular against molar mass but as the values are comprised be- able to predict the dilute gas viscosity of several polar and non-po-
tween 1.24 and 1.29 this fact is perhaps not significant. Compared lar fluids within an uncertainty of 1.5%. The model is an empirical
with the case of 1-alkylamines [1], it seems that Rg is less impor- correlation derived from the Chapman–Enskog theory [41] and the
tant for 2-amines than for 1-amines (1.394 for 1-heptylamine reduced collision integral expression for the Lennard–Jones 12-6
and 1.241 for 2-aminoheptane). This result is probably due to the potential of Neufeld et al. [42]. This model is related to the critical
branching effect. temperature Tc, the critical molar volume vc and the acentric factor
In order to make an analysis of the influence of the molecular x.
structure, the next modeling step is to represent the variation of Unfortunately, experimental critical property data of organic
the dynamic viscosity as a function of molecular mass. As the var- compounds are limited due to the fact that many compounds be-
iation of Rg is not simple, the parameter v0 has only been corre- come unstable during measurements near or even far from the
lated, by expressing it with a simple linear function, on the vicinity of the critical point. We found some experimental and rec-
overall data set (93 points). The correlation used for (m0(T, M) is ommended values in Marsh et al. [43], which is a part nine of re-
the following: view series for vapor–liquid critical properties of elements and
compounds. For 2-aminobutane (i.e. sec-butylamine)
m0 ðT; MÞ ¼ ða1 M þ a0 ÞT þ ðb1 M þ b0 Þ: ð7Þ
Tc = 514.3 ± 0.3 K (recommended value is 514 ± 1 K) and
This expression allows a reduction of the total number of parame- pc = 5.0 MPa (recommended value is 5.0 ± 0.5 MPa), and for 2-ami-
ters from 20 to 8. Table 4 shows parameters and result of re-estima- noheptane Tc = 598.0 ± 0.3 K (recommended value is 598.0 ± 0.6).
tion using the value of Rg obtained in Table 3. This parameter In such conditions, mathematical models can be used to provide
reduction resulted in an AAD of 4.37% with a MD of 8.80%. Both a reasonable estimate of these properties. A variety of estimation
AAD and MD have increased and are higher than the magnitude methods for critical property data are available in the open litera-
of experimental uncertainty. There seems to be branching effect, ture. A broad overview of these methods together with a detailed
which cannot be described very well with the simple linearization discussion of their reliability was given by Poling et al. [44]. Re-
of parameters against temperature and molar mass. This model, cently, Nannoolal et al. [45] developed a new group contribution
with the development of parameters Rg and v0, has already been method for the prediction of critical properties and their method
successfully applied in the case of 1-alkylamines [1] and in some has been compared with 10 well-known estimation methods from
other previous works [38,39]. literature. More recently, a position group contribution method,
which requires only the knowledge of their chemical structure,
4.3. Free-volume viscosity model for the prediction of critical temperature Tc [46], critical pressure
pc [47] and critical volume vc [48] have been proposed. Their meth-
Based on the free-volume concept, an approach has recently od, owing to the utilization of the position compensation factor,
been proposed in order to model the viscosity of Newtonian fluids demonstrates significant improvements compared to the previ-
in the gaseous and dense states [8,9]. In this approach, the total vis- ously used first- or second- order method, especially in the capabil-
cosity g can be separated into a dilute gas viscosity term g0 and an ity of distinguishing between isomers. In order to evaluate the
additional term Dg, in the following way: dilute gas viscosity term g0, in this work, the critical properties
were estimated by the position group contribution method [46–
g ¼ g0 þ Dg: ð8Þ
48]. In addition, the acentric factor was estimated by the method
The term Dg characterizes the passage in the dense state and is con- recommended in Ref. [44], in which the estimated critical proper-
nected to the molecular structure via a representation of the free ties Tc and pc and the experimental Tb were used with the recom-
volume fraction. The general expression of the free-volume viscos- mended equation:
ity model is [8]:
"  lnðPc =1:01325Þ þ f ð0Þ ðT br Þ
   # x¼ ; ð10Þ
aq þ pM=q aq þ pM=q 3=2 f ð1Þ ðT br Þ
g ¼ g0 þ q‘ pffiffiffiffiffiffiffiffiffiffiffiffiffi exp B ; ð9Þ
3RTM RT
where T br ¼ T b =T c ; f ð0Þ and f ð1Þ : analytical expressions developed by
where ‘ corresponds to a characteristic molecular length. a is linked Ambrose and Walton [49]. Table 5 shows the values of Tb described
to the barrier energy E0 = aq, which the molecules have to exceed in as material specification by Sigma–Aldrich and estimated values of
order to diffuse. B is characteristic of the free-volume overlap. This critical properties and acentric factor. As Tb of 2-aminopentane and
equation involves three physical parameters ‘, a and B, which are 2-aminoheptane are described as ranged value, we used the middle
characteristic of the molecule. This model has been shown to accu- value of the range. By the comparison with experimental value, we
rately represent the viscosity behavior of various hydrocarbons over found deviations for 2-aminobutane of Tc and pc are 1.4 and 9.1%,
wide ranges of temperature and pressure in the gaseous, liquid and and a deviation for 2-aminoheptane of Tc is 0.70%.

Table 4
Parameters and results of the rough hard-sphere viscosity scheme with the linearization of parameter v0 by Eq. (7).
v0 (m3 mol1) a0 a1 b0 b1
6.463E09 4.970E07 4.225E06 1.108E03

2-Aminobutane 2-Aminopentane 2-Aminoheptane 2-Aminooctane Overall


AAD (%) 7.01 6.53 1.72 2.22 4.37
Bias (%) 7.01 6.53 1.72 2.09 1.07
MD (%) 8.70 8.80 3.88 8.80 8.80
132 M. Yoshimura et al. / Chemical Physics 369 (2010) 126–137

Table 5 can also be seen on the characteristic molecular length ‘, which


Experimental boiling point (at atmospheric pressure) and evaluated values of critical is smaller for 2-aminooctane (0.04085 nm) than for 2-aminobu-
properties by the position group contribution method [46–48] and acentric factor by
the method in Ref. [44].
tane (0.06391 nm). This is related to the molecular structure that
is longer for 2-aminobutane molecule (Fig. 1). According to [8],
Tb (K) Tc (K) pc (MPa) vc (cm3 mol1) x in Eq. (9), ‘ ¼ L2 =bf , where L2 is an average characteristic molecular
2-Aminobutane 336.15 521.4 4.547 274.0 0.2757 quadratic length, and bf is the dissipation length of the energy
2-Aminopentane 364.15 547.5 4.190 333.1 0.3683 E = E0 + pM/q where the term pM/q = pv is related to the energy
2-Aminoheptane 416.15 593.8 3.671 455.6 0.5654
2-Aminooctane 438.15 615.3 3.466 518.0 0.6307
necessary to form the vacant vacuums available for the diffusion
of the molecules. Certainly as L2 seems to increase with the length
of alkyl chain, the decrease of ‘ means that bf increases with alkyl
chain length more than L2. Finally, it has to be mentioned that it is
It is important to notice that, as the compounds studied here are the value for the molecular energy which has a more important
in the dense state, the value of g0 is low compared to the total vis- contribution to the total viscosity in excess of the dilute gas viscos-
cosity. For the four compounds the maximum value for dilute gas ity. This is confirmed by the fact that 2-aminobutane, which has
viscosity is g0 = 0.008 mPa s for 2-aminobutane at T = 353.15 K (to- lowest experimental viscosity in the four compounds, shows lower
tal viscosity of 2-aminobutane at p = 20 MPa and T = 353.15 K is value for the energy parameter a than the other compounds,
g = 0.285 mPa s). We noticed also that g0 is not very sensitive to though it shows higher value of ‘ and B than the other compounds.
small variations of the critical parameters and acentric factor. Compared with the case of 1-alkylamines [1], no particular effect
The three characteristic parameters in Eq. (9) have been esti- appears that could clearly be related to the branching effect.
mated by minimizing MD for each of the four amines. The esti- The procedure presented for the rough hard-sphere scheme can
mated parameters are presented in Table 6 with the deviation also be used to reduce the number of the parameters. Each main
results. The dynamic viscosity is obtained in (Pa s), when all vari- parameter ‘; a and B has then been correlated against the number
ables and properties are inserted in SI units. It should be noticed of carbon atoms n of the alkyl chain with linear equations as
that the AAD for each of the compounds are lower than the exper- A = A1M + A0 (with A ¼ ‘; a or B) so that only six parameters are
imental uncertainty with MD lower than 3.30% (obtained for 2- used, for the four amines. The results and parameters obtained
aminooctane at p = 20 MPa and T = 313.15 K). The overall results, by this correlation are shown in Table 7. Compared with the previ-
with an AAD of 1.01%, can be considered very satisfying because ous result (Table 6), AAD shows a little bit worse result (1.62% for
the calculations involve only three parameters for each one of all the data instead of 1.01%) but it is still lower than the experi-
the four amines. A comparison of the specific energy parameter a mental uncertainty. For the maximum deviation the result is
shows that it increases with the number of CH2 groups. By multi- 3.68% for the 2-aminobutane (T = 293.15 K, p = 0.1 MPa) and 2-
plying the specific energy parameter with the density, an influence aminooctane (T = 293.15, p = 100 MPa). It should be noticed that
on the energy barrier, E0 = aq, due to the chain length effects can a increases with M, and that ‘ and B decrease when M increases,
be seen, since the energy barrier E0, which the molecules has to ex- as already observed in Table 6.
ceed in order to diffuse, is approximately 73–78% higher for 2-ami- In Eq. (9) the density appears explicitly and for the calculation
nooctane than for 2-aminobutane. The larger energy will result in a we used the experimental density data. It is important to under-
lower mobility of the molecules in 2-aminooctane and conse- line, however, that the model could be applied even if the density
quently in a higher viscosity. In case of the B parameter, which is is not known by using an efficient equation of state along with Eq.
related to the free-volume overlap of molecules, a pronounced ef- (9). Of course the parameters obtained in such way are partially
fect due to the chain length effect is also found: it decreases with linked to the chosen equation of state. Notice that this remark is
the chain length. The obtained B value of 2-aminooctane is signif- valid for all the models where density appears explicitly. In this
icantly lower than for 2-aminobutane. The effect of chain length aim, recently the free-volume model has been successfully coupled

Table 6
Results obtained on the four compounds with the free-volume viscosity model.

Parameters 2-Aminobutane 2-Aminopentane 2-Aminoheptane 2-Aminooctane Overall


‘ (nm) 0.0639102 0.0442546 0.0469946 0.0408502
a (J m3 kg1 mol1) 93.766 125.364 140.117 160.181
B 0.00827095 0.00675202 0.00657969 0.00613258
AAD (%) 0.90 0.56 0.77 1.82 1.01
Bias (%) 0.051 0.217 0.071 0.555 0.090
MD (%) 1.81 1.46 1.53 3.30 3.30

Table 7
Results obtained on the four compounds with the free-volume viscosity model and the correlated parameters (A = A1  M + A0 with M in kg mol1).

A1 A0
‘ (nm) 0.0428623 0.0526912
a (J m3 kg1 mol1) 613.256 67.3793
B 0.00112600 0.00688086
2-Aminobutane 2-Aminopentane 2-Aminoheptane 2-Aminooctane Overall
AAD (%) 2.08 1.13 1.32 1.94 1.62
Bias (%) 1.506 0.913 1.191 0.177 0.263
MD (%) 3.68 3.55 3.15 3.68 3.68
M. Yoshimura et al. / Chemical Physics 369 (2010) 126–137 133

with the statistical associating fluid theory (SAFT model) [50]. By suggesting that the critical viscosity is a linear function of
Moreover in this latter work the authors successfully demonstrate the molar mass and assuming that the third order friction constant
that it is possible to correlate and predict simultaneously the vis- is a constant independent of the 2-aminohydrocarbon, the three
cosity of n-alkanes using the free-volume model with SAFT theory, adjustable parameters were obtained and reported in the table
with parameters that are universal for the whole series of caption of Table 9. The deviation results obtained are reported in
n-alkanes with only six parameters. In the data-pool fitting, they Table 9. The overall AAD = 3.08% with Bias = 0.35% and
assumed, like in the present work, that the parameters of the MD = 10.4%, which is a satisfactory result.
free-volume model scale linearly with molecular weight, and this It is important to note that when accurate and reliable viscosity,
simple assumption has been effective. density and phase behaviour predictions can be achieved, then
accurate models for these properties can be linked and connected.
In this sense, as already underlined above, the free-volume model
4.4. f-Theory model
has been successfully coupled with the statistical associating fluid
theory for pure compounds [50]. The friction theory has also been
Starting from basic principles of mechanics and thermodynam-
coupled to different types of SAFT models [50,54]. In the f-theory
ics, the friction theory (f-theory) for viscosity modeling has been
the density does not appear explicitly, but it is necessary to know
introduced [11]. In the f-theory the total viscosity can be written
the attractive pressure and the repulsive pressure. In a recent pa-
as:
per it is shown how the f-theory can be linked to practically any
g ¼ g0 þ gf ð11Þ type of EoS [55] ranging from highly theoretical EoS to highly accu-
rate empirical reference EoS. However, the adjustable parameters
where g0 is the dilute gas viscosity and gf the residual friction con- in this model are linked to the equation of state chosen for the
tribution. The friction contribution is related to the van der Waals calculation.
attractive and repulsive pressure terms, pa and pr, of an equation
of states (EoS), such as the Peng and Robinson (PR) [51] or the 4.5. Molecular dynamics viscosity model
Soave–Redlich–Kwong (SRK) [52] ones. Based on this concept, a
general f-theory model [12] valid for hydrocarbons has been intro- Recently, a predictive viscosity approach has been introduced
duced with 16 constants identical for all hydrocarbons. In this work, for simple pure fluids and mixtures over a wide range of tempera-
the f-theory approach in conjunction with the PR EoS, as described ture and pressure [13]. This approach is derived from molecular
in our previous work [53] has been used. In this approach there are dynamics simulations using a corresponding state scheme, where
two adjustable parameters, a ‘‘characteristic” critical viscosity gc the Lennard–Jones (LJ) fluid is taken as the reference compound
and a ‘‘third order constant” d2. The required dilute gas viscosity and a one-fluid approximation is applied to mixtures. A simple cor-
of the pure compounds has been obtained by the Chung et al. model relation has been developed in order to accurately reproduce re-
[40], as for free-volume theory. cent molecular dynamics results on the LJ fluid over a large
The two adjustable parameters, the estimated critical viscosity range of thermodynamic states [13].
gc and the third order friction constant as well as the deviation re- In this model, the reduced viscosity g* has been expressed ver-
sults are shown in Table 8. The obtained results are satisfactory sus reduced temperature T* and reduced density q* (see [13] for
taking into account that they are obtained in conjunction with a details) as a sum of a classical Chapman–Enskog dilute density
simple cubic EoS with only two adjustable parameters. In compar- contribution g0 and of a residual viscosity contribution Dg [13] as
ison with the two previous other models with a physical back- in a free-volume and f-theory approaches:
ground (rough hard-sphere scheme and free-volume theory) g ðT  ; q Þ ¼ g0 ðT  Þ þ Dg ðT  ; q Þ: ð12Þ
Table 8, shows that the overall values of AAD and MD found for this
model are slightly higher. In this model the dilute density contribution is defined as
Plotting the critical viscosity reported in Table 8 as a function of pffiffiffiffiffi
T
the molar mass reveals that the critical viscosity is nearly a linear g0 ðT  Þ ¼ 0:17629Ac ; ð13Þ
Xv
function of the molar mass (of the form gc = gc1M + gc0) The third
order friction constant reported in Table 8 cannot be represented where Ac = 0.95, and Xv is the collision integral. Neufeld et al. [42]
by a linear relationship with the molar mass. have derived expressions for different collision integrals. In Ref.

Table 8
Results obtained with the f-theory viscosity model in conjunction with the PR EOS by adjusting the critical viscosity gc and the third order friction constant d2.

2-Aminobutane 2-Aminopentane 2-Aminoheptane 2-Aminooctane Overall


gc (lP) 346.14 331.71 301.41 297.309
d2 (lP/bar3) 4.69969  109 5.21001  109 3.58445  109 3.81666  109
AAD (%) 1.61 1.09 3.43 3.97 2.56
Bias (%) 0.04 0.02 0.15 0.21 0.11
MD (%) 4.75 3.50 7.45 8.22 8.22

Table 9
Results obtained with the f-theory viscosity model in conjunction with the PR EOS by correlating the critical viscosity gc = gc1  M + gc0 with M in kg mol1 [gc1 = 1173.36
(lP mol kg1) and gc0 = 437.693 (lP)] and the third order friction constant d2 = 4.26789  109 (lP/bar3).

2-Aminobutane 2-Aminopentane 2-Aminoheptane 2-Aminooctane Overall


AAD (%) 1.68 2.06 4.44 3.99 3.08
Bias (%) 0.70 1.27 3.00 1.07 0.35
MD (%) 6.26 4.89 10.4 8.74 10.4
134 M. Yoshimura et al. / Chemical Physics 369 (2010) 126–137

Table 10
Results obtained with the molecular dynamics viscosity model.

2-Aminobutane 2-Aminopentane 2-Aminoheptane 2-Aminooctane Overall


AAD (%) 42.3 33.9 21.7 17.7 28.9
Bias (%) 42.3 33.9 21.7 17.7 28.9
MD (%) 46.4 39.5 29.9 30.8 46.4

vious methods, but this model is the only one purely predictive as
there is no parameter to adjust. Nevertheless, it is important to no-
tice that the model predicts correctly an increase of the viscosity
when the pressure increases and a decrease of the viscosity when
the temperature increases. Moreover the viscosity increases from
2-aminobutane to 2-amoinooctane (see Fig. 7 which correspond
to p = 60 MPa). From the viewpoint of the difference of molecular
structure, the overall results for branching amines of this work
are approximately twice worse than the ones for linear amines
studied in previous work [1]. The increase of the difference from
the theory value is thought to be due to the branching effect,
namely, this suggests the insufficiency of this method in order to
predict the structural isomers.
It is possible to improve the results with adjustment of the
molecular parameter r, but in this case the model is no more pre-
dictive. In fact, it should be mentioned that Eq. (16) in conjunction
Fig. 7. Molecular dynamics based correlation: comparison between the experi-
mental (closed symbols) and the estimated (open symbols) dynamic viscosity at with the critical molar volume vc is efficient only for simple com-
p = 60 MPa for 2-aminobutane (j, h), 2-aminopentane (h, }), 2-aminoheptane (N, pounds [13]. For more complex molecules, vc (i.e. r, see Eq. (16))
4) and 2-aminooctane (d, s). should be adjusted on viscosity data. The values of vc adjusted by
minimizing MD and the results are shown in Table 11. By perform-
ing this adjustment in order that MD would be minimum, we
[13] the expression for the 12-6 collision integral is used. The resid- found, for 2-aminobutane, -pentane, -heptane and -octane, respec-
ual viscosity contribution is expressed as: tively, the adjusted values vc = 295.50, 350.75, 468.47 and
529.29 cm3 mol1 instead of the estimated values vc = 274.0,
Dg ðT  ; q Þ ¼ b1 ½expðb2 q Þ  1 þ b3 ½expðb4 q Þ  1 333.1, 455.6 and 518.0 cm3 mol1 (Table 5). The AAD, Bias and
þ b5 ½expðb6 q Þ  1ðT  Þ2 ; ð14Þ MD have been significantly improved in comparison with the ones
in Table 10. This direct estimation of vc for the four compounds
where the bi coefficients have been regressed against molecular using experimental viscosities clearly indicates that the model is
dynamics simulations results on the LJ pure fluid [13]. very sensitive to the LJ parameter rii as previously shown [13].
In order to apply this approach to real fluids, the two LJ molec- Finally we have supposed that the molecular length r has the
ular parameters (rii: molecular length and eii: energy parameter) relationship with molar mass as r = r1M + r0. The correlated
that are supposed to represent the real compound, are required. parameters for r, the values of vc calculated by Eq. (16) and results
These molecular parameters have been related to the critical tem- are presented in Table 12. The AAD, Bias and MD are worse than
perature Tc in K and the critical molar volume vc in m3 mol1, the ones obtained by the estimation of vc for each compounds (Ta-
through ble 11), however, they are still much better than the ones obtained
by the purely predictive method (Table 10).
kB T c As already underlined, in a predictive way this scheme provides
eii ¼ ; ð15Þ
1:2593 a reasonable estimation of the viscosity of these compounds. The
 
v c 1=3 overall results can be considered satisfactory compared to the sim-
rii ¼ 0:302 ; ð16Þ
plicity of this scheme. An improvement is obtained with only 1 ad-
NA
justed molecular parameter per compound (or 2 for the four
Eq. (15) has been proposed by Chung et al. [40] and Eq. (16) has compounds taken simultaneously), the critical molar volume of
been proposed by Galliéro et al. [13]. The unit for eii is (J), and for the pure fluids (or the molecular size).
rii is (m).
It is worth to underline that this model is entirely predictive, 4.6. Eyring theory and cubic EoS model
contrary to the models described in previous sections, as no
parameter adjustment has to be done to the experimental viscosity On the basis of the Eyring’s Absolute Rate Theory [56], Lei et al.
database. Using the critical properties given in Table 5 we found [57] derived the following two-parameters model for correlating
the results indicated in Table 10. The model underestimates the the viscosity of pure liquids under saturated conditions:
viscosity. The results are much worse than the ones from the pre-

Table 11
Results obtained with the molecular dynamics viscosity model with the adjusted critical molar volumes.

2-Aminobutane 2-Aminopentane 2-Aminoheptane 2-Aminooctane Overall


vc (cm3 mol1) 295.50 350.75 468.47 529.29
AAD (%) 4.24 2.94 3.90 5.05 4.03
Bias (%) 2.27 0.83 3.06 3.59 1.30
MD (%) 8.44 6.07 5.95 8.88 8.88
M. Yoshimura et al. / Chemical Physics 369 (2010) 126–137 135

Table 12
Results obtained with the molecular dynamics viscosity model and the correlated parameters (r = r1M + r0 with M in kgmol1).

r (nm) r1 r0
2.023440 0.381871

2-Aminobutane 2-Aminopentane 2-Aminoheptane 2-Aminooctane Overall


vc (cm3 mol1) 296.65 346.89 463.87 531.06
AAD (%) 4.08 8.60 6.79 8.02 6.87
Bias (%) 0.90 8.60 6.79 7.50 1.75
MD (%) 13.0 12.7 13.0 13.0 13.0

 
RT 1 DU v ap with overall AAD values of 0.94% using Eyring-PR model, whose va-
g¼ exp a exp ðZ L Þ; ð17Þ
VL c RT lue is within experimental uncertainty. For the maximum devia-
tion, the result is 5.45% for 2-aminooctane (T = 293.15 K,
where c (s1) represents the frequency of activated molecule flow
p = 100 MPa). In addition, the influence of the molar mass on
to vacancy site, the reciprocal of which can be considered the mean
parameters was modeled supposing that the parameters are linear
free residence time as sR = 1/c, a is the proportionality factor be-
function of the molar mass as A = A1M + A0 (with A = a or b or c). As
tween the activation energy DG– and the internal energy of vapor-
shown in Table 14, AAD shows a little bit worse result compared
ization DUvap, VL is the volume of the liquid, and ZL is the
with the previous result (overall 1.29% instead of 0.94%) but it is
compressibility factor of the liquid, respectively. On the other hand,
still within experimental uncertainty. For the maximum deviation,
in order to extend the applicability of Eq. (17) to a wider tempera-
the result is 6.00% for 2-aminooctane (T = 293.15 K, p = 100 MPa).
ture range, Macías-Salinas et al. [14,15] adopted successfully
The overall results of this model shown in Tables 13 and 14 are
power-law dependence between DG– and DUvap and their three-
very well, compared to other viscosity models used in this work.
parameters viscosity model is written as
From the viewpoint of the estimated values of characteristic
"   #
RT 1 DU v ap b parameters, taking into account of the results of Lei et al. [57]
g¼ exp a expðZ L Þ: ð18Þ and Macías-Salinas et al. [14,15], there is no clear correlation be-
VL c RT
tween molecular shape and the value of the parameters. In addi-
In this work we use a slightly different equation than Eq. (18). tion, even if it is the same fluid, the values of the parameters are
The viscosity model of the Eyring type for pure liquids is written different depending on the model expression and the type of EoS
as: used to calculate the equilibrium properties. However, as a satis-
  factory result was obtained in this work by linearizing the param-
RT 1 DU v ap
g¼ exp a expðbZ L Þ: ð19Þ eters against molar mass, it is possible to consider that the value of
VL c RT parameters reflects the difference of the molecular motion that
This equation has still 3 adjustable parameters, but keep the linear originates in the difference of the molecular structure (length of
variation of ln(g) versus DUvap. It is worthwhile to say here that this the carbon chain). Focusing on the parameter c for the four 2-alkyl-
relation has been privately suggested to us by Prof. Macias-Salinas amines used here, the molecule which has the longer carbon chain
et al. [14,15]. The equilibrium properties VL, DUvap = Uvap  UL and shows lower value of c, i.e., lower frequency of the activated mol-
ZL in Eq. (19) at given temperature and pressure are computed from ecule displacement to the vacancy site. Notice that when applied to
a cubic PR EoS [51]. linear amines, pentylamine, hexylamine and heptylamine [1] this
The three parameters of Eq. (19) were estimated for the four 2- model gives also a very good representation. The worst case is
alkylamines considered in this work. The correlating results are for heptylamine : AAD = 1.26%, Bias = 0.64% and MD = 4.0%. No par-
summarized in Table 13. The performance of Eq. (19) in correlating ticular effect appears that could clearly be related to the branching
saturated liquid viscosity of associated fluids was remarkably good effect.

Table 13
Results obtained with the model based on Eyring theory and PR EoS.

2-Aminobutane 2-Aminopentane 2-Aminoheptane 2-Aminooctane Overall


a 0.26408 0.26399 0.22006 0.22040
b 0.11446 0.10304 0.10160 0.09770
c  1011 (s1) 9.1115 9.2957 6.3074 6.2322
AAD (%) 1.01 0.51 0.56 1.69 0.94
Bias (%) 0.020 0.001 0.010 0.043 0.019
MD (%) 2.69 1.56 2.40 5.45 5.45

Table 14
Results obtained with the model based on Eyring theory and cubic EoS and the correlated parameters (A = A1M + A0 with M in kg mol1).

A1 A0
a 1.5028 0.39482
b 0.21405 0.12609
11 1
c  10 (s ) 115.67 19.5938
2-Aminobutane 2-Aminopentane 2-Aminoheptane 2-Aminooctane Overall
AAD (%) 1.44 1.10 0.740 1.87 1.29
Bias (%) 0.162 0.278 0.324 1.46 0.393
MD (%) 5.16 3.24 1.85 6.00 6.00
136 M. Yoshimura et al. / Chemical Physics 369 (2010) 126–137

4.7. Roland model for viscosity scaling flexibility also increases, and that softens the intermolecular po-
tential, namely, the value of c decreases.
Recently [16], it has been put into evidence the phenomenon of In our previous work [1], where we have estimated the values of
superposition of the relaxation times, s, for various glass-forming c for three 1-alkylamines in the same way, the same tendency of c
liquids and polymers when expressed as a function of TVc (V: spe- to decrease with the increase of carbon atoms has been observed.
cific volume V = 1/q, and c a constant characteristic of the mate- From the viewpoint of the difference of molecular structure, it is
rial). Roland et al. [17] have extended this thermodynamic worse to compare the value of c among the structural isomers of
scaling to the viscosity of several real fluids. For a given compound 1-alkylamines and 2-alklamines. 2-alkylamines that have branch-
the viscosity g is only a functional of the quantity TVc ing molecular structure show lower scaling factor than 1-alkyl-
amines that have linear molecular structure, namely,
gðT; VÞ ¼ gðT; qÞ ¼ f ðTV c Þ ¼ f ðT qc Þ: ð20Þ pentylamine (c = 8.17) versus 2-aminopentane (c = 7.77) and hep-
tylamine (c = 7.53) versus 2-aminoheptane (c = 7.24). These differ-
According to Refs. [16,17,58] the parameter c reflects the mag- ences of c suggest that, in the comparison of molecules that have
nitude of the intermolecular forces. It links the thermodynamic to the same number of carbon atoms, molecules with the branching
the transport property (here viscosity). In Ref. [17], Eq. (20) has structure have a lower intermolecular potential than the ones with
been verified for several liquids. Eq. (20) has been later verified the linear structure.
by other authors. In particular in Refs. [59,60] the superposition
is very clearly observed for several pentaerythritol ester lubricants,
for linear and branching alkanes, polar liquids, ionic liquids, and 5. Conclusion
alcohols.
We have estimated the exponent c for the four 2-alkylamines A total of 93 experimental dynamic viscosity measurements are
considered in this work. In order to model the influence of the mo- reported for 2-aminobutane, 2-aminopentane, 2-aminoheptane
lar mass in this narrow molar mass interval, we made fitting and 2-aminooctane, for temperatures between 293.15 K and
imposing c = c1M + c0. The function f(TVc) in Eq. (20) is not speci- 353.15 K and up to 100 MPa. At atmospheric pressure
fied, however, using polynomial function of (TVc) we obtained a (p = 0.1 MPa) the dynamic viscosity was measured by a classical
very satisfactory scaling result as c = 0.018852  M + 9.411908 capillary viscometer (Ubbelohde) with an experimental uncer-
(M in g mol1). For each 2-alkylamine the viscosity data collapse tainty of 1%, whereas the viscosity under pressure was measured
onto a single master curve. In fact as shown in Fig. 8, there is a sin- with a falling-body viscometer with an experimental uncertainty
gle master curve identical for the four amines (c = 8.03, 7.77, 7.24 of 2%.
and 6.98 for 2-aminobutane, 2-aminopentane, 2-aminoheptane The experimental data for these systems have been used in or-
and 2-aminooctane, respectively). Fig. 8 shows really a very good der to evaluate the performance of one empirical correlation (Vo-
superposition of these four 2-alkylamines, which have branching gel–Fulcher–Tamman representation combined with Tait-like
structure. It is then clear that Roland et al. [16,17] scaling relation equation; seven adjustable parameters for each compound) as well
can be used to determine the volume and temperature dependence as six models with a more or less developed physical and theoret-
of viscosity, over broad temperature and pressure range. Neverthe- ical background: the rough hard-sphere scheme (five adjustable
less, for some strongly hydrogen-bonded materials (water, low parameters), a viscosity model based on the free-volume concept
molecular weight polypropylene glycol), the superpositioning fails (three adjustable parameters), the f-theory model based on friction
[17]. Despite the small association of these branching amines, the consideration (two adjustable parameters), a correlation derived
representation makes sense as Eq. (20) reproduces the experimen- from molecular dynamics (one adjustable parameter), a model
tal viscosity very well. According to Eq. (20), scaling factor c corre- based on Eyring theory combined with cubic EoS (3 adjustable
sponds to the weight on V = 1/q, the magnitude of the c value parameters) and a viscosity representation based on thermody-
means the magnitude of a relative influence of the density on the namic scaling (one adjustable parameter). This evaluation shows
viscosity in comparison with the temperature. For linear alkanes, that some simple models can represent the viscosity of these sys-
c decreases (13 for n-hexane and 6.3 for octadecane) with the mo- tems within an acceptable and satisfactory uncertainty. Further, by
lar mass [60]. Our result for 2-alkylamines suggests that, as for al- performing the linearization of characteristic parameters on molar
kanes, when the number of carbon atoms increases the molecular mass, and by comparing with the results of 1-alkylamines obtained
in previous work, the way different models take into account the
effect of molecular structure (carbon chain length and position of
amino group) has been revealed.
The free-volume model, the f-theory model, the molecular
dynamics viscosity model and the Eyring-PR EoS model are all
applicable to gases, liquids, and dense fluids. Because of this, these
four models are suitable for industrial processes involving different
phases or phase changes. Moreover, from a fundamental point of
view, the rough hard-sphere scheme, the free-volume model, the
molecular dynamics model, and Eyring-PR EoS model provide
some insight on the microstructure of these complex systems. Fi-
nally, it should be underlined that the four 2-alkylamines consid-
ered here and also the three 1-alkylamines reported in previous
work [1] show a pressure and temperature viscosity behaviour
compatible with the superposition and scaling viscosity scheme,
providing one single master curve.

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