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Cryst. Res. Technol. 44, No. 8, 883 – 888 (2009) / DOI 10.1002/crat.200900162

Temperature dependence of the density of some liquid crystals in

the alkyl cyanobiphenyl series

I. Zgura*1, R. Moldovan2, T. Beica1, and S. Frunza1

1
National Institute of Materials Physics, P.O. Box MG-7, Bucharest-Magurele, 077125, Romania
2
Romanian Academy Center for Advanced Studies in Physics, Calea 13 Septembrie no.13, Bucharest,
Romania

Received 20 March 2009, revised 18 May 2009, accepted 25 May 2009

Published online 12 June 2009

Key words liquid crystals, density, measurements.

PACS 61.30.-v, 64.70.Md, 06.30.Dr

Experimental results for the temperature dependence of the density of propyl - cyanobiphenyl (3CB), butyl -
cyanobiphenyl (4CB) and hexyl - cyanobiphenyl (6CB) are presented. The results are compared with previous
results for temperature dependence of other members of the alkyl cyanobiphenyl series (nCB). The deviation
of the density from linear temperature dependence is discussed in terms of the recently discovered
corresponding rule for nematic liquid crystals.

© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1 Introduction
Liquid crystals are intermediate states of matter (mesophases) between the isotropic liquid and the crystalline
solid. Their special thermodynamic, optical, rheological and anisotropic properties make them suitable for a
wide range of optoelectronic applications [1]. Among the wide variety of discovered liquid crystals, the liquid
crystals in the alkyl cyanobiphenyl series (nCB) was intensively studied as they present the nematic phase at
room temperature and they are stable over a large temperature range. In the liquid crystal study, the density and
volumetric measurements have been used to provide experimental evidence about the order of phase transition
in liquid crystal research. An increase of density on ordering can be related to several aspects of intermolecular
interactions, such as steric repulsions and van der Waals forces. Therefore accurate determinations of the
density of a liquid crystal about its transition temperatures are of great interest [2-5]. In literature [6-12] there
are a number of studies concerning the density measurements for members of alkyl cyanobiphenyl homologous
series. In this paper the results for the density vs. temperature in the nCB series are completed with new data
for the compounds 3CB in the isotropic phase and for 4CB and 6CB in the nematic and isotropic phases. The
density vs. temperature curves revealed non-linear temperature dependence not only in the vicinity of the
nematic – isotropic transition where it has an evident character, but also in the whole nematic range, and this
can be attributed to the temperature dependence of the nematic ordering. Starting with this idea, the rule of
corresponding states in nematic liquid crystals [13] was tested for the deviation from the linear behaviour of
the temperature dependence of density of 5CB – 7CB. This rule introduces a nematic temperature scale [13]:
T − TNC
t= (1)
TNI − TNC
where TNC is the crystalline – nematic transition temperature, TNI is the nematic – isotropic transition
temperature, and T is the actual temperature.
Using this temperature linear rescaling, it was shown [13] that the thermal behaviour of the order parameter
presents a common profile for the entire nematic phase and so do a number of anisotropic properties of liquid
____________________

* Corresponding author: e-mail: irina.zgura@infim.ro

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884 I. Zgura et al.: Temperature dependence of the density of some liquid crystals

crystals as dielectric and magnetic susceptibility anisotropy. In this paper we will show that this is also true for
the deviation of the density from a linear behaviour with temperature.

2 Experimental
The measurements were performed on propyl - cyanobiphenyl (3CB), butyl- cyanobiphenyl (4CB) and hexyl –
cyanobiphenyl (6CB), compounds from the 4-alkyl-4’-cyanobiphenyl homologue series. 3CB and 4CB were
obtained from Nemoptic and 6CB from Aldrich (98% purity), respectively and were used without
supplementary purification. An Anton Paar densimeter (model DMA 4500) was used to measure the liquid
crystal density in the nematic and isotropic phases with the precision of ±1·10-5g·cm-3. The apparatus is
equipped with a thermostating device that assures constant temperature of the sample with a precision of
±0.03 K. For the automation of the experiment and for the data acquisition on the computer, we made a
dedicated program. The program validates the results given by the instrument when the temperature becomes
constant, with the precision of ±0.01 K. The reaching of the thermic equilibrium was verified by the constancy
of the oscillating frequency of the measuring tube, a variation less than 5·10-6 Hz being allowed. We visually
observed at the transition temperature that there is a thermic gradient along the measuring tube of the order of
0.1 K. Phase transition sequences were determined by DSC, in heating and cooling, and by optic microscopy.
The transition temperatures, nematic-isotropic TNI and melting Tm, are given in table 1.

Table 1 Some properties of liquid crystals in the alkyl cyanobiphenyl series. M is the molar mass, V is the
molar volume at TNI, and ΔV is the discontinuity of the molar volume at TNI. Tm is the melting point.
Liquid Tm TNI M V ΔV ΔV
⋅ 103
crystal (°C) (°C) (g/mol) (cm3/mol) (cm3/mol) V
3CB 67.4 30.7 221.30 - - -
4CB 48.6 16.5 235.33 227 0.35 1.54
5CB 24 35.2 249.35 246.3 0.59 [12] 2.4
6CB 14.5 28.85 263.38 262 0.40 1.53
7CB 30 42.8 277.40 280.9 0.76 [12] 2.71
8CB 21.5 40.55 291.43 297 0.72 [12] 2.42

The compound 4CB is monotropic, so it had to be first heated at temperatures higher than 48.6°C when it melts
from crystalline to isotropic phase. The liquid crystal was degassed to remove gas bubbles from the liquid in
isotropic phase at about 65 °C. In cooling, at 16.5 °C it suffers a transition from isotropic to nematic phase. At
temperatures below 48.6 °C, the system is in a supercooling state, first in isotropic, and then, below 16.5°C, in
nematic phase and remains in the nematic phase until a small perturbation produces its crystallization.
Nevertheless, the transition temperature nematic – isotropic (16.5 °C) was checked in both increasing and
decreasing temperatures around this temperature and found in accordance.
The compound 3CB is also monotropic, so it had to be first heated at 75 ºC, a temperature higher than
67.4 °C when it melts from crystalline to isotropic phase. The compound was kept at 75 ºC at a pressure of 10-2
Torr for 24 h, in order to be deeply degassed. At temperatures below 67.4 °C, the system is in a supercooling
state, in isotropic phase and it remained in this state for temperatures higher than 34 °C when crystallized. It
crystallized before reaching the nematic to isotropic temperature of 30.7 °C (determined by observation under
polarized light in a thermostatated chamber, INSTEC). The same difficulties to obtain the nematic phase of
3CB were reported also by other researchers [14].
All the measurements were made in decreasing temperatures and we used small temperature steps for 4CB
and 3CB to avoid thermal shocks that could produce the crystallization of the monotropic compounds.

3 Results and discussion

The results for the density determinations of different nCB compounds in the nematic and isotropic phases are
given in figure 1, where the results for 5CB, 7CB and 8CB previously obtained by us [10] are also presented.

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Cryst. Res. Technol. 44, No. 8 (2009) 885

The values for 6CB are in good agreement with those previously reported [8, 12]. The density presents a jump
at the nematic to isotropic transition, as expected taking into account that the transition is first order. Due to the
high precision of determinations, some non-linearities in the density – temperature dependence were put in
evidence in the nematic and even in the isotropic phase, near the nematic to isotropic transition.

Fig. 1 Temperature dependence of the density of

some liquid crystals in the alkyl cyano biphenyl series
(nCB) in the nematic and isotropic phases. The results
for 5CB, 7CB and 8CB are reproduced from [10]. The
continuous lines are the fitting with equation (2).

The results for 3CB-8CB were fitted in the nematic and isotropic phases with the quadratic function:
ρ = 1 / ⎛⎜ A + B T − TNI + C T − TNI ⎞⎟ . (2)
⎝ ⎠
This form of the temperature dependence of the density is obtained from that of the specific volume
dependence given by the Landau de Gennes phenomenological theory of the phase transitions in nematic liquid
crystals [15,16]. It was also used by Dunmur and Miller [8] in the analysis of their volumetric studies of nCBs.
The values of the coefficients in the nematic (N) and isotropic (I) phase are given in table 2.
As one can be seen from figure 1, the density decreases with increasing aliphatic chain length for the
compounds in nCB series. An odd-even effect of the alkyl chain length can also be observed examining this
figure. In figure 2a it is presented the dependence of the molar volume V in the nCB series as function of the
aliphatic chain length in the nematic phase, at the nematic to isotropic transition (given in table 1), calculated
from density measurements. The values of the molar volumes are also listed in table 1. One observes that this
increase is well represented by a linear dependence.

(
Table 2 Fitting parameters for the regression ρ = 1/ A + B T − TNI + C T − TNI ) of the density dependence
-3
on the relative temperature, in the isotropic (I) and nematic (N) phase. ρ in g·cm .
Fitting parameters
Liquid Nematic phase Isotropic phase
crystal A B⋅105 C⋅106 A B⋅105 C⋅106
g-1cm3 g-1cm3K-1/2 g-1cm3K-1 g-1cm3 g-1cm3K-1/2 g-1cm3K-1
3CB - - - 0.96338±4⋅10-5 10.7±2.2 726.5±2.5
4CB 0.96649±6⋅10-5 -95.1±3.8 -657.9±10.4 0.96750±3⋅10-5 22.4±1.1 698.4±2.4
5CB 0.98858±6⋅10-5 -140.1±3.3 -647.6±6.3 0.99018±3⋅10-5 30.7±1.5 733.9±2.3
6CB 0.99646±4⋅10-5 -134.0±2.4 -628.5±4.4 0.99744±3⋅10-5 32.8±1.7 740.2±3.2
7CB 1.01490±8⋅10-5 -174.6±4.0 -633.0±7.1 1.01670±4⋅10-5 45.7±2.2 757.4±3.5
8CB 1.02090±7⋅10-5 -139.3±4.9 -773.6±12.3 1.02280±4⋅10-5 44.8±2.2 782.4±4.8

In figure 2b the relative volume changes (ΔV/V) at the nematic – isotropic transition are plotted as function of
alkyl chain length and, as already experimentally observed by Dunmur and Miller [8], a significant odd-even
effect is apparent, namely the odd members of the series having larger values than the even members.

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886 I. Zgura et al.: Temperature dependence of the density of some liquid crystals

Fig. 2 Molar volume (V) in the nematic phase

at the nematic to isotropic temperature (a) and
its relative jump (ΔV/V), at the same
temperature (b), for different members of the
alkyl cyanobiphenyl series. Continuous curve in
(a) represents the fit with the liniar dependence
y=ax+b with a=17.50±0.30; b=157.60±1.85.

The Landau de Gennes theory of phase transitions [17] introduces a separation of the Gibbs free energy of the
system (F) in a first part independent of ordering (F0), and a second part dependent of it and represented as an
expansion in terms of the order parameter, Q:
3 1 9
F ( p, T , Q) = F0 (T , p) + a(T − T * )Q 2 + BQ 3 + CQ 4 + ... , (3)
4 4 16
where p is the pressure, T is the temperature, T* is a temperature a little higher than the transition temperature,
and a, B, C are phenomenological coefficients independent of temperature, but dependent of pressure. As a
consequence, the volume of the system V (T , p, Q) = ( ∂F ∂p )T is also split in a sum of a term independent of
the order parameter (isotropic) V0 (T , p) = ( ∂F0 ∂p )T , and a term dependent of it. In the isotropic phase of the
system, far enough from the transition temperature, it is expected that the temperature dependence of the
volume to be linear V0 (T ) = V01 [1 + α (T1 − T ) ] with α, the expanding coefficient and V01 the volume
corresponding to T1. Supposing that the expanding coefficient α of V0 is roughly the same in the nematic and
isotropic phases, we can separate the part of volume that depends of order parameter. The same split has to be
true for the density.

Fig. 3 Temperature dependence of Δρ = ρ − ρlin in

the nematic and isotropic phase of nCB (n=3-8).

In figure 3 we present the difference Δρ = ρ − ρlin between the density values (ρ) in the nematic and isotropic
phases and those calculated from a hypothetical linear dependence ( ρlin ) for nCB (n=3-8), as function of
relative temperature T − TNI . The linear dependence of temperature ( ρlin ) was obtained in isotropic phase at

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Cryst. Res. Technol. 44, No. 8 (2009) 887

temperature far from TNI (at ΔT = 20 K) by fitting the interpolation curve given by equation (2), with a linear
regression on a 0.3 K temperature range. The trend of the temperature dependence curve Δρ = ρ − ρlin shows
that the degree of ordering of the liquid crystal is important in the temperature dependence of its density, as
already suggested by the Landau – de Gennes theory. Some influence of the liquid crystal ordering is still
present in the isotropic phase near the transition as one can also be seen from Figure 3. This influence of the
pre-nematic fluctuations-heterogeneities in the isotropic phase on the volume changes was also analyzed in
terms of the Landau – de Gennes theory [5, 8] and the resulted quadratic form dependence given by the
equation (2). The fitting of our experimental results in the isotropic phase using equation (2) gives a good
agreement, as one can be seen from table 2.
The broadband dielectric spectroscopy results also indicate the significant role of pre-nematic fluctuations-
heterogeneities in the isotropic phase [14].
As the ordering in the nematic phase is important in the temperature dependence of Δρ, we tested in
figure 4 the corresponding state rule [13] for this quantity for three liquid crystals for which the nematic
temperature scale given by eq.(1) can be defined. We observe that the nematic temperature scale cannot be
defined for 8CB which has not a direct transition from nematic to crystalline phase. Unfortunately, as the
nematic domain for 4CB cannot be specified taking into account that the nematic phase is obtained only in
supercooling the isotropic liquid, such a plot cannot be obtained for 4CB. In figure 4 the Δρ values were
normalized so that to obtain the value equal to 1 at t=0.

Fig. 4 Corresponding states rule for the deviation of the

density of 5CB (□), 6CB (∇) and 7CB (•) from the linear
behaviour. The continuous line is the best fitting curve
using eq.(4).

For the normalized Δρ values of 5CB, 6CB and 7CB it can be observed that power law behaviour dominates
the curve form. Although the rule could be tested only for these liquid crystals in the series, a weak odd-even
effect could also be observed.
The normalized Δρ values were fitted with the exponential curve:
y = A(1 − t / t *)β , (4)
which is of the type of Haller expression for the order parameter profile [18] and we obtained A=1.008±0.006,
t*=1.034±0.007 and β=0.233±0.009, in enough good concordance with the results for the fitting of normalized
order parameter for nematic liquid crystals obtained in [13].

4 Conclusions
The results for the temperature dependence of the density of 3CB and 4CB monotropic liquid crystals in the
alkyl cyanobiphenyl series and that for 6CB liquid crystal harmonize well with previous determinations of the
same quantity for other compounds of the series [10].

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888 I. Zgura et al.: Temperature dependence of the density of some liquid crystals

The high precision of these measurements put in evidence deviations from the linear dependence of the density
vs. temperature curves, both in the whole nematic phase range and in the isotropic one at temperatures a little
higher than the phase transition. In the nematic domain, these deviations from linearity for the compounds
5CB, 6CB and 7CB are well described by the corresponding states rule [13], showing that they are due to the
thermal behavior of the order parameter in the nematic phase.

Acknowledgements I. Zgura, T. Beica and S. Frunza thank for the financial support of Romanian Ministry of Education
and Research COMAFI Core Program. R. Moldovan thanks to Romanian Academy for its financial support.

References
[1] L.Vicari, Optical Applications of Liquid Crystals, (Institute of Physics Publishing, Bristol and Philadelphia, 2003),
p. 27
[2] D. Demus, J. Goodbye, G. W. Gray, and H.-W. Spiess (eds.), Handbook of liquid crystals, Vol.1 (V. Vill, Wiley –
VCI, Weinheim, New York, Chiche, Brisbane, Singapore, Toronto, 1998), p. 335.
[3] S. Torza and P. E. Cladis, Phys. Rev. Lett. 32, 1406 (1974).
[4] E. Gulari and B. Chu, J. Chem. Phys. 62, 795 (1975).
[5] D. Armitage and F. P. Price, Phys. Rev. A 15, 2496 (1977).
[6] A. J. Leadbetter, J. L. A. Durant, and M. Rugman, Mol. Cryst. Liq. Cryst. Lett. 34, 231 (1977).
[7] G. J. Gannon and T. E. Faber, Philosoph. Mag. A 37, 117 (1978).
[8] D. A. Dunmur and W. H. Miller, J. Phys. Coll. (Paris) 40, C3-14 (1979).
[9] H. R. Zeller, Phys. Rev. A 26, 1785 (1982).
[10] T. Beica, R. Moldovan, I. Zgura, and S. Frunza, J. Opt. Adv. Mater. 11, 3624 (2007).
[11] J. Deschamps, J. P. M. Trusler, and G. Jackson, J. Phys. Chem. B 112, 3918 (2008).
[12] G. A. Oweimreen, J. Phys. Chem. B 105, 8410 (2001).
[13] M. Simoes and D. S. Simeao, Phys. Rev. E 73, 062702 (2006); Phys. Rev. E 74, 051701 (2006).
[14] A. Drozd-Rzoska, S. Rzoska, S. Paulus, and J. Ziolo, Phys. Rev. E 72, 031501 (2005).
[15] H.Imura and K.Okano, Chem. Phys. Lett. 17, 111 (1972).
[16] W. Klement and L. H. Cohen, Mol. Cryst. Liq. Cryst. 27, 359, (1974)
[17] P.-G. de Gennes and J. Prost, The Physics of Liquid Crystals, 2nd edition, Vol 1 (Oxford University Press, Oxford,
1993), p. 76.
[18] I. Haller, Progr.Solid State Chem. 10, 103 (1975).

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