APPLIED PHYSICS LETTERS 94, 051103 共2009兲

A thermal lens model including the Soret effect

Humberto Cabrera,1,a兲 Eloy Sira,2 Kareem Rahn,2 and Máximo García-Sucre1,2
1
Departamento de Física Aplicada, Instituto Venezolano de Investigaciones Científicas (IVIC),
Mérida 5101, Venezuela
2
Centro de Física, Instituto Venezolano de Investigaciones Científicas (IVIC), Caracas 1020-A, Venezuela
共Received 17 September 2008; accepted 14 January 2009; published online 2 February 2009兲
In this letter we generalize the thermal lens model to account for the Soret effect in binary liquid
mixtures. This formalism permits the precise determination of the Soret coefficient in a steady-state
situation. The theory is experimentally verified using the measured values in the ethanol/water
mixtures. The time evolution of the Soret signal has been used to derive mass-diffusion times from
which mass-diffusion coefficients were calculated. © 2009 American Institute of Physics.
关DOI: 10.1063/1.3078287兴

The basic principle of the thermal lens method is the along the z axis with a light beam of Gaussian intensity
measurement of the amount of heat deposited in a medium I共r , z兲 = 关2Pe / ␲␻2e 共z兲兴exp关−2r2 / ␻2e 共z兲兴, in the limit of small
after the absorption of light. The heat generated from nonra- absorbencies, the temperature distribution is given by5

冕 冋 册
diative relaxation processes leads to a temperature rise in the
medium in which the absorbing compound is contained. 2Pe␣ t
1 2r2
⌬T共r,z,t兲 = exp − dt⬘ ,
When the radial energy distribution of the excitation beam
has a Gaussian profile, the temperature within the sample
␲␳C p␻2e 0
t⬘
1 + 2 tc 共
␻2e 1 + 2 tt⬘c 兲
will also follow a similar profile. Therefore, a refractive in- 共2兲
dex gradient is produced and the sample behaves like an where Pe is the excitation power and ␣, ␳, and C p are the
optical lens. In practice the thermal lens effect is probed by a absorption coefficient, the density, and the specific heat of
second laser, the probe beam, by measuring the far-field the medium. The quantity ␻e共z兲 = ␻0e关1 + 共z − ae兲2 / z2e 兴1/2 is the
variation in the beam center intensity. excitation beam radius at the sample cell, with ae, ␻0e, ze
Giglio and Vendramini1 noticed that the effect of thermal = ␲␻0e 2
/ ␭e, and ␭e as the waist position, the radius at the
lens in a binary mixture was noticeably larger than in the two waist, the Rayleigh parameter, and the excitation wave-
pure components. In a binary liquid mixture an applied tem- length. The coordinate z is the sample position and tc共z兲
perature gradient generally induces net mass flows which
= ␻2e 共z兲 / 4Dth is the characteristic thermal time constant with
lead to the formation of a concentration gradient. The result-
Dth = k / ␳C p and k as the thermal diffusivity and thermal con-
ing steady-state thermally induced concentration gradient is
ductivity, respectively.
known as thermal diffusion or the Ludwig–Soret effect.2
If the refractive index n of the liquid mixture satisfies the
Giglio and Vendramini1 suggested that the thermal lens effect
condition ⌬n / n Ⰶ 1,6 it changes with temperature and con-
could be used as a proper technique for studying this effect.
centration as7,8
In a stationary state where the mass flows vanish, the
magnitude of the effect is described by the Soret coefficient ⳵n ⳵n
ST,2 ⌬n共r,z,t兲 = ⌬T共r,z,t兲 + ⌬c共r,z,t兲. 共3兲
⳵T ⳵c
DT 1 ⵱c The concentration change can be given by7–9
ST ⬅ =− , 共1兲
D c0共1 − c0兲 ⵱T
⌬c共r,z,t兲 = − STc0共1 − c0兲⌬T共r,z,t兲⌫共z,t兲, 共4兲
where D is the mass-diffusion coefficient, DT is the thermal
diffusion coefficient, T is the temperature, c is the mass frac- with
tion of component 1 共the heaviest component兲, and c0 is its
equilibrium value. The Soret coefficient has a positive sign
when component 1 migrates to the cold side and a negative
⌫共z,t兲 = 1 − 兺
⬁

i=1
4
共2i − 1兲␲
sin
2
冋
共2i − 1兲␲
册
sign otherwise.
There are very few experiments which use the thermal
lens effect to measure the Soret coefficient. Arnaud and
冋
⫻exp − 共2i − 1兲2
t
tD共z兲
, 册 共5兲

Georges3,4 studied in several papers the influence of the Soret
effect on thermal lens, but their working equations lead only
to a qualitative understanding of the Soret effect. In this let-
ter, we present an accurate thermal lens model that allows
qualitative and quantitative descriptions of the Soret effect.
In the mode-mismatched dual-beam thermal lens experi-
ment when an infinite medium is illuminated at time t = 0
a兲
Electronic mail: hcabrera@ivic.ve.
where tD共z兲 = ␻2e 共z兲 / 4D is the mass-diffusion time.4
The summation in Eq. 共5兲 converge rapidly. In order to
obtain an accuracy better than 1% it is sufficient to retain
terms up to i = 4. When t Ⰷ tD the exponential term vanishes
and ⌫ = 1, therefore Eq. 共4兲 reduces to Eq. 共1兲.
The change in the refractive index acts as an optical
element producing a phase shift ⌽ on the wave fronts of the
probe beam. Inserting Eq. 共4兲 into Eq. 共3兲 and then using
again Eq. 共3兲, we obtain10

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051103-2 Cabrera et al. Appl. Phys. Lett. 94, 051103 共2009兲

2␲
⌽共r,z,t兲 = l关⌬n共r,z,t兲 − ⌬n共0,z,t兲兴
␭p

= l 冋
2␲ ⳵ n ⳵ n
− STc0共1 − c0兲⌫共z,t兲
␭p ⳵ T ⳵ c
册
⫻ 关⌬T共r,z,t兲 − ⌬T共0,z,t兲兴, 共6兲
where l is the sample cell length and ␭ p is the wavelength of
the probe field. Substituting Eq. 共2兲 into Eq. 共6兲, ⌽ can be
written as5,10
␾s⌫共z,t兲 − ␾th
⌽共g,z,t兲 =
2

⫻ 冕 1

共1 + 2t⬘/tc兲−1
关1 − exp共− 2m共z兲g␶兲兴
␶
d␶ , 共7兲

where ␾s = 共⳵n / ⳵c兲关Pe␣lSTc0共1 − c0兲 / k␭ p兴 is the induced con-
centration phase shift amplitude and ␾th = 共⳵n / ⳵T兲
⫻共Pe␣l / k␭ p兲 is the induced thermal lens phase shift ampli-
tude. In the above equation the ratio m共z兲 = 关␻ p共z兲 / ␻e共z兲兴2
accounts for the level of the mode matching between the
beams, g = r / ␻ p共z兲 is a dimensionless parameter, and ␻ p共z兲
= ␻0p关1 + 共z − ae兲2 / z2p兴1/2 is the probe beam radius at the
sample cell with a p, ␻0p, and z p = ␲␻0p2
/ ␭ p as the waist posi-
tion, the radius at the waist, and the Rayleigh parameter.
The main difference between Eq. 共7兲 and the expression
given in Ref. 10 is that the former includes the influence of
the Soret effect.
The total signal can be expressed as the relative change
in the transmission of the probe beam10
T共z,t兲 − T0
Stotal共z,t兲 = , 共8兲
T0
where T0 is the value of T共z , t兲 for ␾th = ␾s = 0.
Using this definition and following the same lines in
Ref. 10, the total signal is given by
Stotal共z,t兲 = Sth − Ss = ␾thK共z,t兲 − ␾sK共z,t兲⌫共t兲, 共9兲
with
FIG. 1. Total signal for an ethanol mass fraction in water c0 = 0.3912
共in 1 cm quartz cuvette兲.
value is used for the Soret coefficient determination when-
ever the rest of the parameters are known.
The experimental setup was described in Ref. 11. A
10 mW helium-neon laser generates the probe beam, which
is collimated in 6 mm diameter through the sample. The
resultant power at the sample position was reduced to
0.2 mW. The excitation beam is provided by the second har-
monic of a diode pumped neodymium yttrium aluminum gar-
net 共Nd:YAG兲 cw laser 共Intelite, GSF32–200兲, which is fo-
cused onto the sample with an 18 cm achromatic lens
resulting in a Rayleigh parameter of 1 cm. We use a shutter
for mechanical modulation of the excitation beam. The shut-
ter 共846, Newport兲 is set for a period of 35 s, then it is turned
off for another 35 s to allow the system to relax. For each
weight fraction the signal was averaged 128 times at the
digital oscilloscope 共Textronix TDS 3052兲.
Thermal lens measurements were carried out with cobalt
nitrate as solute. A cobalt nitrate was chosen because it is not
fluorescent and the absorption at the probe wavelength is
lower than at the excitation wavelength.3 Solutions of appro-

K共z,t兲 = arctan 再 4m␯t/tc

␯ + 关1 + 2m兴 + 关1 + 2m + ␯2兴2t/tc
2 2 , 冎 priate absorbencies were prepared by weighing the required
amount of cobalt nitrate in ethanol/water mixtures 共ethanol
purity ⬎99.8%, water was distilled and de-ionized兲, and then
共10兲 the absorption coefficient was measured with a conventional
Ocean Optics 共USB 2000兲 spectrophotometer.
where ␯共z兲 = 共z − a p兲 / z p + 共z p / L − z兲关1 + 共z − a p兲
2
/ z2p兴
is the geo-
Figure 1 shows the time evolution of the total signal for
metrical parameter of the probe beam and L is the detector
ethanol mass fraction c0 = 0.3912 共at 298 K兲 processed with
plane position.
Eq. 共8兲. The thin line represents the best fit to the experimen-
The expression 共9兲 can be simplified by assuming t
tal data using Eq. 共9兲 and the parameters ␭e = 532.8 nm, ␭ p
→ ⬁, z = 0, and z p Ⰷ L Ⰷ ze. Under these conditions K共z , t兲
= 632.8 nm, z p = 10 000 cm, ze = 1 cm, ae = 0, a p = 0, L
= ␲ / 2,11 ⌫ = 1, and Eq. 共9兲 simplifies to
= 140 cm, D = 1.19⫻ 10−3 cm2 s−1, and ␾th = −0.0278, with
␲ ␲ ␾s = −0.003 05 and tD = 1.6 s as fitting parameters.
Stotal = Sth − Ss = ␾th − ␾s , 共11兲 In order to calculate the thermal lens phase shift ampli-
2 2
tude 共␾th = −0.0278兲, we have used the values of the photo-
where thermal parameters ⳵n / ⳵T = 2.58⫻ 10−4 K−1 and k = 3.80

Ss = ␾s
␲
2
=
⳵c
冉 冊
⳵ n Pe␣lSTc0共1 − c0兲 ␲
k␭ p 2
. 共12兲
⫻ 10−3 W cm−1 K−1 reported by Arnaud and Georges,3 and
the rest of the parameters are ␣ = 共4.80⫾ 0.06兲 ⫻ 10−2 cm−1,
Pe = 0.54 mW, l = 1 cm, and ␭ p = 632.8⫻ 10−7 cm. The ther-
We have obtained an accurate expression that provides a mal diffusivity was calculated using the value of the thermal
simple relation between the total, the thermal lens, and the conductivity reported in Ref. 3 and assuming that ␳ and C p
Soret signals. Measuring the total signal and calculating the are both linear functions of the mass fractions of water and
thermal lens signal, the Soret signal can be obtained whose ethanol.
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051103-3 Cabrera et al. Appl. Phys. Lett. 94, 051103 共2009兲

TABLE I. Soret coefficient 共ST兲 and diffusion coefficient 共D兲 of mixtures of where each value represents an average of five runs.
ethanol and water in mass fraction of ethanol at T = 298 K. The errors for ST The results presented in Table I illustrate the role of the
corresponding to the five cases illustrated are, from left to right, 0.15, 0.05,
0.07, 0.25, and 0.3, respectively.
ethanol concentration. Positive Soret coefficients are ob-
served for low ethanol contents. With increasing ethanol con-
c0 0.166 0.350 0.3912 0.540 0.760 tent, the Soret coefficient decays and changes sign. In a mix-
ture with high ethanol content ST is negative 共ethanol
ST共10−3 K−1兲 a
4.60 ⫺2.20 ⫺3.21 ⫺4.60 ⫺3.90
molecules migrate to the hot side兲, whereas at low ethanol
D共10−6 cm2 s−1兲 a
7.30 4.80 4.60 4.20 4.50
content, ST is positive 共ethanol molecules migrate to the cold
ST共10−3 K−1兲 4.70b ⫺2.16b ⫺3.21c ⫺4.80d ⫺4.30d
D共10−6 cm2 s−1兲 7.60b 4.70b 4.55c 4.30d 4.60d
side兲.
In summary, we have presented a generalized thermal
a
From this work. lens model that allows the precise determination of the val-
b
From Reference 12.
c ues of the Soret coefficient and the mass-diffusion coefficient
From Reference 9.
d
From Reference 13. in binary liquid mixtures. The experimental results were
compared with the existing data in the literature and good
From the adjusted value ␾s = −0.003 05, we have calcu- agreement is achieved.
lated the Soret coefficient 关ST = 共−3.19⫾ 0.08兲 ⫻ 10−3 K−1兴
by means of Eq. 共12兲 and using 共⳵n / ⳵c兲 = 3.72⫻ 10−2.3,12 We 1
M. Giglio and A. Vendramini, Appl. Phys. Lett. 25, 555 共1974兲.
2
have also obtained the mass-diffusion coefficient 关D H. Tyrell, Diffusion and Heat Flow in Liquids 共Butterworths, London,
1961兲.
= ␻2e 共z兲 / 4tD = 共4.6⫾ 0.2兲 ⫻ 10−6 cm2 s−1兴 with tD = 1.6 s and 3
N. Arnaud and J. Georges, Spectrochim. Acta, Part A 57, 1295 共2001兲.
␻e = 共54⫾ 5兲 ⫻ 10−4 cm. 4
J. Georges, Spectrochim. Acta, Part A 69, 1063 共2008兲.
5
Alternatively, we have determined the Soret coefficient J. Shen, R. D. Lowe, and R. D. Snook, Chem. Phys. 165, 385 共1992兲.
using the total signal 共Stotal = −0.0388兲 given in Fig. 1, and by
6
J. P. Gordon, R. C. C. Leite, R. S. Moore, S. P. S. Porto, and J. R.
means of Eq. 共11兲 we have obtained the Soret signal 共Ss = Whinnery, J. Appl. Phys. 36, 3 共1965兲.
7
J. A. Bierlein, J. Chem. Phys. 23, 10 共1955兲.
−4.8⫻ 10−3兲 from which, using Eq. 共12兲, the Soret coeffi- 8
M. Giglio and A. Vendramini, Phys. Rev. Lett. 38, 26 共1977兲.
cient was calculated 关ST = 共−3.21⫾ 0.07兲 ⫻ 10−3 K−1兴. The 9
K. J. Zhang, M. E. Briggs, R. W. Gammon, and J. V. Sengers, J. Chem.
Soret coefficients obtained using these two procedures are Phys. 104, 6881 共1996兲.
10
generally very close with a difference less than 0.65% and A. Marcano, C. Loper, and N. Melikechi, J. Opt. Soc. Am. B 19, 119
also in good agreement with the values reported by Zhang et 共2002兲.
11
A. Marcano, H. Cabrera, M. Guerra, R. A. Cruz, C. Jacinto, and T. Ca-
al.9 ST = −3.21⫻ 10−3 K−1 and Kolodner et al.12 ST = −3.16 tunda, J. Opt. Soc. Am. B 23, 1408 共2006兲.
⫻ 10−3 K−1. 12
P. Kolodner, H. Williams, and C. Moe, J. Chem. Phys. 88, 6512 共1988兲.
We have measured and compared the Soret coefficient 13
R. Kita, S. Wiegand, and J. L. Strathmann, J. Chem. Phys. 121, 3874
over the entire range of concentrations, as shown in Table I, 共2004兲.

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