Home A double-pass optical beam deflection instrument for the measurement of diffusion, thermodiffusion and Soret coefficients in liquid mixtures and its application to polymer analysis
Article
Licensed
Unlicensed Requires Authentication

A double-pass optical beam deflection instrument for the measurement of diffusion, thermodiffusion and Soret coefficients in liquid mixtures and its application to polymer analysis

  • Roman Reh , Mareike Hager and Werner Köhler EMAIL logo
Published/Copyright: April 24, 2024

Abstract

We have developed a new double-pass optical beam deflection instrument for the measurement of diffusion, thermodiffusion and Soret coefficients in liquid mixtures. The increased sensitivity of the instrument results from a second passage of the readout laser beam through the Soret cell containing the sample. An elegant description of the total beam deflection is achieved by means of a transfer matrix formalism. The higher sensitivity allows for a reduction of the length of the detection arm and a compact and stiff design of the instrument. The performance of the new apparatus is demonstrated by its application to polymer analysis for the determination of the molar mass distribution of the polymer from the distribution of diffusion rates by means of the CONTIN algorithm.


Corresponding author: Werner Köhler, Physikalisches Institut, Universität Bayreuth, D-95440 Bayreuth, Germany, E-mail:

Funding source: Deutsches Zentrum für Luft- und Raumfahrt

Award Identifier / Grant number: (DLR, Grant 50WM2147)

Funding source: Deutsche Forschungsgemeinschaft

Award Identifier / Grant number: (DFG, Grant No. DFG, KO1541/13-1)

  1. Research ethics: Not applicable.

  2. Author contributions: The authors have accepted responsibility for the entire content of this manuscript and approved its submission. RR and MH built the instrument and performed the measurements, WK wrote the manuscript. All authors participated in the data evaluation.

  3. Competing interests: The authors state no competing interests.

  4. Research funding: This work was supported by Deutsches Zentrum für Luft- und Raumfahrt (DLR, Grant 50WM2147) and by Deutsche Forschungsgemeinschaft (DFG, Grant No. DFG, KO1541/13-1).

  5. Data availability: The raw data can be obtained on request from the corresponding author.

References

[1] K. Thyagarajan and P. Lallemand, “Determination of the thermal diffusion ratio in a binary mixture by forced Rayleigh scattering,” Opt. Commun., vol. 26, no. 1, pp. 54–57, 1978. https://doi.org/10.1016/0030-4018(78)90340-1.Search in Google Scholar

[2] W. Köhler, “Thermodiffusion in polymer solutions as observed by forced Rayleigh scattering,” J. Chem. Phys., vol. 98, no. 1, p. 660, 1993.10.1063/1.464610Search in Google Scholar

[3] W. Köhler and P. Rossmanith, “Aspects of thermal diffusion forced Rayleigh scattering: heterodyne detection, active phase tracking, and experimental constraints,” J. Phys. Chem., vol. 99, no. 16, pp. 5838–5847, 1995. https://doi.org/10.1021/j100016a018.Search in Google Scholar

[4] S. Wiegand, H. Ning, and H. Kriegs, “Thermal diffusion forced Rayleigh scattering setup optimized for aqueous mixtures,” J. Phys. Chem. B, vol. 111, no. 51, pp. 14169–14174, 2007. https://doi.org/10.1021/jp076913y.Search in Google Scholar PubMed

[5] R. Rusconi, L. Isa, and R. Piazza, “Thermal-lensing measurement of particle thermophoresis in aqueous dispersions,” J. Opt. Soc. Am. B, vol. 21, no. 3, pp. 605–616, 2004. https://doi.org/10.1364/JOSAB.21.000605.Search in Google Scholar

[6] N. Arnaud and J. Georges, “On the analytical use of the Soret-enhanced thermal lens signal in aqueous solutions,” Anal. Chim. Acta, vol. 445, no. 2, pp. 239–244, 2001. https://doi.org/10.1016/s0003-2670(01)01260-0.Search in Google Scholar

[7] A. Mialdun and V. Shevtsova, “Measurement of the Soret and diffusion coefficients for benchmark binary mixtures by means of digital interferometry,” J. Chem. Phys., vol. 134, no. 4, p. 044524, 2011. https://doi.org/10.1063/1.3546036.Search in Google Scholar PubMed

[8] A. Mialdun and V. Shevtsova, “Digital interferometry as a powerful tool to study the thermodiffusion effect,” C. R. Mec., vol. 339, no. 5, pp. 362–368, 2011. https://doi.org/10.1016/j.crme.2011.04.001.Search in Google Scholar

[9] D. Katoshevski, B. Zhao, G. Ziskind, and E. Bar-Ziv, “Experimental study of the drag force acting on a heated particle,” J. Aerosol Sci., vol. 32, no. 1, pp. 73–86, 2001. https://doi.org/10.1016/s0021-8502(00)00057-4.Search in Google Scholar

[10] M. Giglio and A. Vendramini, “Soret-type motion of macromolecules in solution,” Phys. Rev. Lett., vol. 38, no. 1, pp. 26–30, 1977. https://doi.org/10.1103/physrevlett.38.26.Search in Google Scholar

[11] H. Williams and C. Moe, “Optical measurement of the Soret coefficient of ethanol/water solutions,” J. Chem. Phys., vol. 88, no. 10, pp. 6512–6524, 1988. https://doi.org/10.1063/1.454436.Search in Google Scholar

[12] R. Piazza, S. Iacopini, and B. Triulzi, “Thermophoresis as a probe of particle–solvent interactions: the case of protein solutions,” Phys. Chem. Chem. Phys., vol. 6, no. 7, pp. 1616–1622, 2004. https://doi.org/10.1039/b312856c.Search in Google Scholar

[13] A. Königer, B. Meier, and W. Köhler, “Measurement of the Soret, diffusion, and thermal diffusion coefficients of three binary organic benchmark mixtures and of ethanol–water mixtures using a beam deflection technique,” Philos. Mag., vol. 89, no. 10, pp. 907–923, 2009. https://doi.org/10.1080/14786430902814029.Search in Google Scholar

[14] K. J. Zhang, M. E. Briggs, R. W. Gammon, and J. V. Sengers, “Optical measurement of the Soret coefficient and the diffusion coefficient of liquid mixtures,” J. Chem. Phys., vol. 104, no. 17, pp. 6881–6892, 1996. https://doi.org/10.1063/1.471355.Search in Google Scholar

[15] A. Mialdun, et al., “A comprehensive study of diffusion, thermodiffusion, and Soret coefficients of water-isopropanol mixtures,” J. Chem. Phys., vol. 136, no. 24, p. 244512, 2012. https://doi.org/10.1063/1.4730306.Search in Google Scholar PubMed

[16] M. Gebhardt, et al., “Diffusion, thermal diffusion, and Soret coefficients and optical contrast factors of the binary mixtures of dodecane, isobutylbenzene, and 1,2,3,4-tetrahydronaphthalene,” J. Chem. Phys., vol. 138, no. 11, p. 114503, 2013.10.1063/1.4795432Search in Google Scholar PubMed

[17] K. J. Zhang, et al., “Thermal and mass diffusion in a semidilute good solvent-polymer solution,” J. Chem. Phys., vol. 111, no. 5, p. 2270, 1999.10.1063/1.479498Search in Google Scholar

[18] S. Wongsuwarn, et al., “Giant thermophoresis of poly(N-isopropylacrylamide) microgel particles,” Soft Matter, vol. 8, no. 21, p. 5857, 2012. https://doi.org/10.1039/c2sm25061f.Search in Google Scholar

[19] M. Giglio and A. Vendramini, “Thermal-diffusion measurements near a consolute critical point,” Phys. Rev. Lett., vol. 34, no. 10, pp. 561–564, 1975. https://doi.org/10.1103/physrevlett.34.561.Search in Google Scholar

[20] M. Gebhardt and W. Köhler, “Contribution to the benchmark for ternary mixtures: measurement of the Soret and thermodiffusion coefficients of tetralin+isobutylbenzene+n-dodecane at a composition of (0.8/0.1/0.1) mass fractions by two-color optical beam deflection,” Eur. Phys. J. E, vol. 38, no. 4, p. 24, 2015. https://doi.org/10.1140/epje/i2015-15024-5.Search in Google Scholar PubMed

[21] M. V. Klein, Optics, New York, Wiley, 1970.Search in Google Scholar

[22] B. Meier, Aufbau einer Beam Deflection-Apparatur zur Messung von Transportkoeffizienten in Flüssigkeiten, Diploma thesis, Bayreuth, Germany, Universität Bayreuth, 2007.Search in Google Scholar

[23] A. Becker, W. Köhler, and B. Müller, “A scanning michelson interferometer for the measurement of the concentration and temperature derivative of the refractive index of liquids,” Ber. Bunsenges. Phys. Chem., vol. 99, no. 4, pp. 600–608, 1995. https://doi.org/10.1002/bbpc.19950990403.Search in Google Scholar

[24] J. Rauch and W. Köhler, “Collective and thermal diffusion in dilute, semidilute, and concentrated solutions of polystyrene in toluene,” J. Chem. Phys., vol. 119, no. 22, pp. 11977–11988, 2003. https://doi.org/10.1063/1.1623745.Search in Google Scholar

[25] P. Rossmanith and W. Köhler, “Polymer polydispersity analysis by thermal diffusion forced Rayleigh scattering,” Macromolecules, vol. 29, no. 9, pp. 3203–3211, 1996. https://doi.org/10.1021/ma9516302.Search in Google Scholar

[26] M. Schraml, et al., “Measurement of non-isothermal transport coefficients in a near-eutectic succinonitrile/(d)camphor mixture,” J. Chem. Phys., vol. 150, no. 20, p. 204508, 2019. https://doi.org/10.1063/1.5098879.Search in Google Scholar PubMed

[27] K. B. Haugen and A. Firoozabadi, “On the unsteady-state species separation of a binary liquid mixture in a rectangular thermogravitational column,” J. Chem. Phys., vol. 124, no. 5, p. 054502, 2006. https://doi.org/10.1063/1.2150431.Search in Google Scholar PubMed

[28] M. Gebhardt and W. Köhler, “What can be learned from optical two-color diffusion and thermodiffusion experiments on ternary fluid mixtures?,” J. Chem. Phys., vol. 142, no. 8, p. 084506, 2015.10.1063/1.4908538Search in Google Scholar PubMed

[29] S. W. Provencher, “A constrained regularization method for inverting data represented by linear algebraic or integral equations,” Comput. Phys. Commun., vol. 27, no. 3, pp. 213–227, 1982. https://doi.org/10.1016/0010-4655(82)90173-4.Search in Google Scholar

[30] S. W. Provencher, “CONTIN: a general purpose constrained regularization program for inverting noisy linear algebraic and integral equations,” Comput. Phys. Commun., vol. 27, no. 3, pp. 229–242, 1982. https://doi.org/10.1016/0010-4655(82)90174-6.Search in Google Scholar

Received: 2023-11-06
Accepted: 2024-04-09
Published Online: 2024-04-24
Published in Print: 2024-10-28

© 2024 Walter de Gruyter GmbH, Berlin/Boston

Downloaded on 24.9.2025 from https://www.degruyterbrill.com/document/doi/10.1515/jnet-2023-0104/html
Scroll to top button