Pressure and Temperature Dependence of Self-Diffusion

in Liquid Linear Hydrocarbons

F. Bachl and H.-D. L iidem ann
Institut für Biophysik und Physikalische Biochemie, Universität Regensburg,
Postfach 387, D -8400 Regensburg

Z. Naturforsch. 41 a, 9 6 3 -9 7 0 (1986); received April 28, 1986

The pressure and temperature dependence o f the self-diffusion coefficients D o f n-butane,

n-pentane, n-hexane, n-decane, trans-2-butene, cis-2-butene and 2-butyne were determ ined in the
liquid state by NM R -techniques at pressure up to 200 MPa and temperatures up to 450 K.
The results are taken as tests for the various dynamical models and compared to results
obtained by M D calculations. The activation parameters for translational transport and the
parameters for the RH S-m odel are derived and discussed.

Introduction densities and temperatures. In the work presented

here the self diffusion coefficients o f n-butane are
D uring the last years several groups studied the com pared to the corresponding quantities in n-pen­
tem perature and pressure dependence o f translational tane, n-hexane and n-decane in order to learn
diffusion in simple rigid m e thane derivatives [1, 2, 3, something about the influence o f the size, the mass
4], The data obtained for these com po unds have been and the multiple trans <=> gauche equilibria upon
used as tests for sim ple dynam ical models like the the results.
activation theories, the free volum e model [5] and 2 -butyne, 2 -trans- and 2 -cis-butene are included
the hard sphere model [6 , 7]. In addition the self in this study as conformationally rigid molecules of
diffusion coefficients were co m pared to results varying shape but almost identical mass.
obtained from M D sim ulations [8 , 9, 10].
F or the m ethane derivatives it can be shown that
the rough hard sphere model gives the best descrip­
Experimental
tion o f the data, though it still rem ains impossible
to extrapolate reliably with any o f the existing
T he self-diffusion coefficients were m easured in a
models into regions o f the q, T space not covered by
strengthened glass cell apparatus [14] by the spin
the experiments.
echo technique using a steady field gradient. They
In the present p ap e r several nonpolar hydro­
were measured at 100.1 M H z in a m odified Varian
carbons are investigated in order to learn whether
X L - 100-15 FT spectrometer. Details o f the experi­
the conformational flexibility o f these com pounds
mental setup and the filling procedures have been
introduces new com plications in the application of
given previously [3, 15]. The field gradient was
the dynamical models and w hether the shift of the
calibrated before the start o f each series o f experi­
trans <=> gauche equilibria which is predicted to
ments using the known self-diffusion coefficients o f
occur with increasing density in direction to the
water [16]. The tem peratures are accurate to
more com pact gauche forms [11, 12, 13], changes
± 1.5 K. The self-diffusion coefficients obtained
significantly the pressure dependence o f the self
were reproduced to ± 3%. They are jud g e d reliable
diffusion coefficients.
to ± 10%.
T he investigations started with this pape r are
aim ed at characterizing the intra- and intermolec-
ular dynamics o f n -butane in a w ide range of
Substances

Reprint requests to Prof. Dr. H.-D. Liidemann, Institut für

Biophysik und Physikalische Biochem ie der Universität Butane (99.5%), trans-2-butene (95%, 4% cis-2-
Regensburg, Universitätsstraße 31, D -8400 Regensburg. butene), cis-2-butene (95%, 3.5% trans-2-butene)

0340-4811 / 86 / 0700-0963 $ 01.30/0. - Please order a reprint rather than m aking your own copy.

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964 F. Bachl and H.-D. Liidemann • Pressure and Temperature D ependence o f Self-D iffusion

were purchased from E. Merck (D-6100 D armstadt).

2-butyne ( > 99%), pentane (99.8%) puriss., hexane
(99.7%) puriss.. decane (99.5%) puriss. were obtained
from Fluka (Buchs. Switzerland). T he gases were
stored in 5 L flasks over molecular sieve 3 A in
o rder to absorb residual moisture.
Prior to use all com pounds were degassed by
several freeze-pump-thaw-cycles to a final pressure
o f 5 mPa.

Results and Discussion

Figures 1 to 3 collect the isotherms o f the self­

diffusion coefficients for all com pounds measured.
Figures 4 and 5 give in addition the data for butane,
butyne and decane in the form o f Arrhenius-plots.
Most isotherms reveal in the log D versus p plot a
curvature. Also in the Arrhenius-plots significant
deviations from linearity are seen.
It is thus obvious that the description of the self­
diffusion data with the concept o f the transition —► p (MPa)
state theory by means o f the activation energies EA
and activation volumes A V* does lead to activation Fig. 1. Isotherms o f the diffusion coefficients o f fluid
n-butane.
param eters that depend on tem p eratu re and pres­
sure. However, it is custom ary to derive such data
for an intercomparison o f various substances. For
all com pounds (EA)p defined by
Only for n-butane [ 1 7 -2 1 ] , n-pentane [17, 18, 19,
/ 0 ln D \ 2 2 - 2 6 ]. n-hexane [17, 18, 19, 23, 27, 28] and
(EA)p=COn si- = -R ^ JY Jfjp (1) n-decane [17, 18, 19. 29] there exist sufficient
pVT data in the literature to calculate also the
was calculated for the reduced te m p erature T • T ~ ]
activation energies at constant density. The iso­
= 0.56. where Tc is the critical tem perature, and also
chores of the self-diffusion coefficient constructed
the activation volumes A V*, given by
from these data show a slight curvature in the high
tem perature region. F ro m the slope o f the isochores
at their low te m p erature end one obtains the activa­
tion energies com piled in Table 1. In n-butane and
were evaluated at various tem peratures for a pres­ n-pentane the increase o f (EA) V with density is
sure of 120 MPa. It ap p e ared most meaningful to within the limits o f experimental error in the region
use this high pressure in order to m inimize the o f our experiments. H ow ever in hexane and decane
influence o f the changing density. The results for a significant increase with rising density is seen, and
the activation energies at constant pressure are it is thus to be expected that more precise m e asu re­
compiled in F igure 6 . It is apparent that for all ments or extension o f the data to higher pressures
conformationally flexible com pounds (EA)p increase would firmly establish a density dependence of
with rising pressure, the effect being most pro­ (E a) v for these com pou nds also.
nounced for n-decane. The sterically rigid sub­ Com parison of the activation energies derived at
stances show less pressure dependence. F or trans- constant pressure and constant density shows that
2 -butene and 2 -butyne (AEA)p appears to be the ratio [(£a)k] [ ( £ a )/>]_1 is close to 0.5, a value
constant in the region studied. typical for nonassociated liquids.

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 Pentane Hexane Decane

347K

2UK

174 K
d0
10 —f— —r~ —r~
0 50 100 "l5Ö" Wo 0 50 100 150 ~20Ö 0 50 "ioö" 150 200
p (MPa) p (MPa) p (MPa)
Fig. 2. Isotherms o f the self diffusion coefficients o f fluid n-pentane, n-hexane and n-decane.

Fig. 3. Isotherms o f the self diffusion coefficients o f fluid 2-butyne, c-2-butene, and t-2-butene.

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966 F. Bachl and H.-D. Lüdemann • Pressure and Temperature D ependence o f Self-Diffusion

Fig. 4. Arrhenius diagram o f the self

diffusion coefficient o f fluid n-butane.

as fu n ctio n o f te m p er a tu r e . A V* in c re a se s for all

p (MPa) p (MPa)
c o m p o u n d s w ith risin g tem p era tu re. A ll n -a lk a n es
reveal a fairly u n ifo r m c h a n g e w ith tem p era tu re.
The a c tiv a tio n v o lu m e s d e r iv e d for 2 -b u ty n e
c o in c id e u n d er th e c o n d itio n s c h o se n w ith th e Fig. 6. Pressure dependence o f the activation energies at
constant pressure for D at a com m on reduced temperature
resu lts o f c -2 -b u te n e . T h e se tw o c o m p o u n d s and
T ■ T ~ 1 = 0.56. ( Tc = critical temperature; Tc (C 4) = 425 K,
t-2 -b u te n e d o sh o w a sig n ific a n t stron ger te m p er a - Tc (C 5) = 470 K, Tc(C 6) = 507 K, Tc(C 10) = 618 K.)

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F. Bachl and H.-D. Lüdemann • Pressure and Temperature D ependence o f Self-D iffusion 967

the rough hard sphere model (RH S-m odel) intro­

duced by D ym ond [6 ] and C han dler [7] proved most
useful for the correlation o f self-diffusion data.
C om po unds like the chloro- and fluorom ethane
derivatives C H 3C1, C H 2C12, CHC13, C F 3H, C H 3F
[4], benzene [30], methanol [31] and even water [32]
can be described quantitatively by this model.
In this model, results o f the gas kinetic C ha pm a n-
Enskog theory [33, 34] are com bined with the
molecular dynamics sim ulations o f the hard sphere
model fluid [35],
T he diffusion coefficient D 0 for a dilute gas
composed o f hard spheres is given by [33]

kT 1/2
Dn = (3)

— T (K) with n the n u m b e r density and a the hard sphere

diameter. F or dense gases Enskog [34] scaled this
Fig. 7. Temperature dependence o f the activation volum es
for D at 120 MPa derived from the data in Figs. 1 to 3. The expression with the radial distribution function g (a)
A V* for 2-butyne coincide in the temperature range where
it could be measured (2 8 5 -4 5 0 K) with the A V * for D E = D 0/ g ( a ) . (4)
c-2-butene.
C om p u ter sim ulations on h ard sphere model sys­
tems by Alder and his group [35] revealed the
existence of correlations between the m olecular
velocities of nearest neighbour molecules. Accord­
Table 1. Density dependence o f the activation energies at
constant volum e ( £ A) i '- const (error ± 10%). ing to these results, D can be expressed after intro­
duction of the self-diffusion coefficient for a smooth
Substance D ensity range (£ A) V-c o n s t
hard sphere D SHS by
(kg • m ~ 3) (kJ • m ol-1 )
Dc\ D SHS
Butane 6 0 0 -7 3 5 2 .7 -3 .1 D= (5)
Pentane 6 2 5 -7 2 5 3 .3 -3 .9 g {o ) \ de
Hexane 6 5 0 -7 5 0 3 .2 -4 .3
Decane 7 0 0 -8 0 0 5 .5 -7 .7 T he quotient (Z)SHS/Z)E) is derived from a fit to
A ld er’s simulation data. D ym ond [6 ] gives for D SHs
the equation
1r t V /2
109 £>shs = 2.527 F0- 2/3( K - 1 .3 8 4 K o) (6)
ture dependence o f A V* than n-butane. It appears
impossible to correlate A V* or its tem p eratu re
which is valid in the density range 1.5 ^ V/V0 ^ 2,
dependence quantitatively with any geometrical
with V0 the m olar volume o f a hard sphere at close
features o f these sim ple molecules. T he three activa­
packing:
tion parameters derived above show clearly, that
their variation with te m p eratu re and pressure p ro ­ a3
hibits the use of these param eters as well as their p ^0 = N a - r - .
|/2
and T dependence for the extrapolation o f transport
data into regions not covered by experim ent. There exist in the literature various empirical
These activation d ata can only be used for a equations [7, 36] which lead in the density range of
qualitative intercom parison o f the transport p ro ­ the experiments given here to identical results.
cesses in different substances. A m ong the sim ple According to Chandler, translation-rotation cou­
models in use for the description o f d ynam ic data pling should lead to a lowering o f the experimental

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968 F. Bachl and H.-D. Lüdemann • Pressure and Temperature D ependence o f Self-Diffusion

diffusion coefficients in real, polyatomic liquids. Table 2. Comparison o f the molar volum es V0 calculated
The experim ental diffusion coefficient Z)exp should by application o f the RHS model with the same quantity
calculated from melting point densities.
thus correspond to the diffusion coefficient o f a
rough hard sphere Z)RHS given by Molar volum e Substance

Butane Pentane Hexane Decane

Dr ^RHS - ^SHS (^ D = lh
where A D characterizes the extent of rotation-trans-
52.6 64.2 75.7 129.0
lation coupling. This leaves two free param eters for
the description of self diffusion data as function of
density and tem perature: the diam eter o f the hard ivl ^ L I j ^ L . i o j 52.9 64.5 76.0 129.2
sphere d and the p ara m ete r A. O ur previous experi­ |/2 \ mol /
ments showed that the data obtained between the
melting pressure curves of various substances at
450 K and at pressures up to 200 MPa can be fitted
n-alkanes, though the concept o f a hard sphere
with a temperature independent RHS-diameter rfRHS
dia m eter for this flexible prolonged molecules is
and an ^ - p a ra m e te r that increases with rising
certainly questionable. F igure 8 gives the t/RHs
temperature.
derived. They increase monotonically from a value
For theoretical reasons one would expect that
o f 0.5 nm for n-butane to a value o f 0.67 nm for
c/Rh s should also reveal a slight decrease with te m ­
n-decane. The m olar volumes calculated from the
perature. Within the accuracy of our data for
R H S -diam eter correspond quantitatively to the
m ethane derivatives m entioned above and also for
molar volumes o f the solid com pou nds at the atm o ­
2 ,2 -dim ethylpropane, 2 ,2 -dimethylpropionitrile and
spheric pressure melting tem perature, an observa­
2-methylpropanol-2 [37] d RHS is constant. The same
tion that has been m a d e for other com pounds also.
is derived from the evaluation o f the results for the
T he data are collected in Table 2. The only free
quantity in the fitting procedure is thus the rotation
translation coupling p ara m ete r A.
F igure 9 collects the ^ -p a ra m e te rs of the four
n-alkanes. In general they increase from a value
around 0.3 above the melting point to about 0.8
around the critical temperature. F or the three lighter
co m pound s no systematic variation o f A with chain
length is seen, within the limits o f accuracy they
seem to coincide. C o m p ared to butane, pentane and
Fig. 8. Rough hard sphere diameter d for the n-alkanes
C4, C5, C 6 and CIO as derived from application o f (6) to hexane, the /4-parameter of decane is significantly
the experimental data. lower at the corresponding reduced temperature.

Fig. 9. Temperature dependence o f the

.4-parameter o f the RHS model charac­
terizing the extent o f rotation-translation
T/ T r coupling for the four n-alkanes.

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F. Bachl and H.-D. Lüdemann • Pressure and Temperature D ependence o f Self-D iffusion 969

Table 3. Comparison o f the self diffusion coefficients simulations by W. J. Jorgensen et al. [38], The
obtained experimentally and by M D sim ulations.
dynam ic properties of butane as functions of
pressure and tem perature where calculated with
T P
m olecular dynamics sim ulations by W eber [39]
using a simplified skeleton alkane model and a
(K) (MPa) ^MD ^cxp
sim plified Lennard-Jones 6 - 9 interaction potential.
n-Butane 397.83 4.2 4.91 * 2.5 Ryckaert et al. [40. 41] used a sim ilar approach
406.04 15.42 3.36 * 1.52 applying a 6 - 1 2 Lennard-Jones potential to derive
314.86 8.97 1.74* 0.76
416.42 39.61 2.19* 1.26 the therm o dynam ic and dynam ic beh aviour o f
407.27 101.96 1.50* 0.78 liquid n-butane and n-decane close to their boiling
291.5 S. P. 6.1/6.9** 6.7
points at atm ospheric pressure. Table 3 compares
199.9 S.P. 2.1/2.4** 1.97
their calculated self diffusion coefficients with our
n-Decane 481 S.P. 7.5/7.7** 7.6
interpolated experimental results.
* Weber. Ref. [39]. - ** Ryckaert, Ref. [40, 41], While the Ryckaert’s results agree with our data
w ithin the limits of experimental error, W e b e r’s
Inspection o f the Figs. 8 and especially 9 reveals treatm ent yields self diffusion coefficients that are
clearly that the interpolation o f D for unknow n approxim ately a factor of two larger than our
homologues could only be achieved with some results. Considering the similarity of the two co m ­
degree of reliability if a theoretical concept for the putational approaches this large difference is sur­
tem perature dependence o f the ^ -p a ra m e te r would prising. However, one should check experim entally
be available. The present state o f the art makes various other properties before any attem pt is m ade
extrapolations into unknow n ranges o f the q, T- to evaluate the merits and shortcomings o f the two
space as well as interpolation o f the data to cover approaches.
unknown intermediate homologues equally h a z a r d ­
ous.
Acknowledgements

Financial support by the D F G and the Fonds der

Comparison with Computer Simulations
C hem ie is gratefully acknowledged.
The most recent calculations concerning the p r o p ­ The expert technical assistance by R. Knott,
erties o f liquid hydrocarbons are the Monte Carlo S. Heyn, and E. Treml was essential for the success.

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