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Whisky Science pp 323-365 | Cite as

The Spirit Matrix

  • Gregory H. Miller
Chapter

Abstract

The purpose of this chapter is to discuss the properties of whisky from a chemical physics point of view. Although our common experience leads us to think of water and ethanol as two perfectly compatible liquids, in fact they make a highly nonideal solution. The microscopic structure of this solution, sometimes referred to as the ‘spirit matrix’, is thought to have significant influence over congener solubility, mouth feel, and the mechanism of ‘mellowing’ with age. While sensory studies associated with the spirit matrix are relatively few, the literature on ethanol–water structures is quite large. This is because of the happy circumstance that ethanol is an amphiphile: it has a hydrophilic hydroxyl group, and a hydrophobic aliphatic end.

References

  1. 11.
    Akahoshi R, Ohkuma H (1984) NMR spectra of hydroxyl protons in aged spirits. Studies on aged spirits and their physiochemical characteristics. Part I. J Agric Chem Soc Jpn 58:357–365Google Scholar
  2. 12.
    Akahoshi R, Ohkuma H (1985) Partial pressure and concentration of ethanol in vapor phase. Studies on aged spirits and their physiochemical characteristics. Part III. J Agric Chem Soc Jpn 59:135–141Google Scholar
  3. 13.
    Akahoshi R, Ohkuma H (1985) Thermal properties of ethanol aqueous solutions and aged spirits at low temperature. Studies on aged spirits and their physiochemical characteristics. Part II. J Agric Chem Soc Jpn 59:1–9Google Scholar
  4. 45.
    Arrhenius S (1889) IV. Electrolytic dissociation versus hydration. Philos Mag 28(170):30–38CrossRefGoogle Scholar
  5. 46.
    Arrhenius S (1907) Theories of chemistry. Longmans, Green, and Co., New YorkGoogle Scholar
  6. 81.
    Benson GC, D’Arcy PJ, Kiyohara O (1980) Thermodynamics of aqueous mixtures of nonelectrolytes II. Isobaric heat capacities of water—n-alcohol mixtures at 25 C. J Sol Chem 9:931–938CrossRefGoogle Scholar
  7. 94.
    Boothroyd EL, Linforth RST, Cook DJ (2012) Effects of ethanol and long-chain ethyl ester concentrations on volatile partitioning in a whisky model system. J Agric Food Chem 60:9959–9966CrossRefGoogle Scholar
  8. 101.
    Box GEP, Draper NR (1987) Empirical model-building and response surfaces. Wiley, New YorkGoogle Scholar
  9. 105.
    Boyne JA, Williamson AG (1967) Enthalpies of mixing of ethanol and water at 5 C. J Chem Eng Data 12:318CrossRefGoogle Scholar
  10. 130.
    Butler JAV (1937) The energy and entropy of hydration of organic compounds. Trans Faraday Soc 33:229–236CrossRefGoogle Scholar
  11. 141.
    Callen HB (1985) Thermodynamics and an introduction to thermostatistics, 2nd edn. Wiley, New YorkGoogle Scholar
  12. 157.
    Chodzińska A, Zdziennicka A, Jańczuk B (2012) Volumetric and surface properties of short chain alcohols in aqueous solution-air systems at 293 K. J Solution Chem 41:2226–2245CrossRefGoogle Scholar
  13. 165.
    Coccia A, Indovina PL, Podo F, Viti V (1975) PMR studies on the structures of water-ethyl alcohol mixtures. Chem Phys 7:30–40CrossRefGoogle Scholar
  14. 174.
    Conner JM, Paterson A, Piggott JR (1994) Agglomeration of ethyl esters in model spirit solutions and malt whiskies. J Sci Food Agric 66:45–53CrossRefGoogle Scholar
  15. 175.
    Conner JM, Paterson A, Piggott JR (1994) Interactions between ethyl esters and aroma compounds in model spirit solutions. J Agric Food Chem 42:2231–2234CrossRefGoogle Scholar
  16. 176.
    Conner JM, Birkmyre L, Paterson A, Piggott JR (1998) Headspace concentrations of ethyl esters at different alcoholic strengths. J Sci Food Agric 77:121–126CrossRefGoogle Scholar
  17. 177.
    Conner JM, Paterson A, Birkmyre L, Piggott JR (1999) Role of organic acids in maturation of distilled spirits in oak casks. J Inst Brew 105:287–291CrossRefGoogle Scholar
  18. 178.
    Conner JM, Paterson A, Piggott JR (1999) Release of distillate flavour compounds in Scotch malt whisky. J Sci Food Agric 79:1015–1020CrossRefGoogle Scholar
  19. 187.
    Costigan MJ, Hodges LJ, Marsh KN, Stokes RH, Tuxford CW (1980) The isothermal displacement calorimeter: design modifications for measuring exothermic enthalpies of mixing. Aust J Chem 33:2103–2119CrossRefGoogle Scholar
  20. 244.
    Egashira K, Nishi N (1998) Low-frequency Raman spectroscopy of ethanol–water binary solution: evidence for self-association of solute and solvent molecules. J Phys Chem B 102:4054–4057CrossRefGoogle Scholar
  21. 275.
    Frank HS, Evans MW (1945) Free volume and entropy in condensed systems III. Entropy in binary liquid mixtures; partial molar entropy in dilute solutions; structure and thermodynamics of aqueous electrolytes. J Chem Phys 13:507–532CrossRefGoogle Scholar
  22. 276.
    Franks F, Ives DJG (1966) The structural properties of alcohol-water mixtures. Q Rev Chem Soc 20:1–44CrossRefGoogle Scholar
  23. 277.
    Franks F, Johnson HH (1962) Accurate evaluation of partial molar properties. Trans Faraday Soc 58:656–661CrossRefGoogle Scholar
  24. 282.
    Furusawa T, Saita M, Nishi N (1990) Analysis of ethanol-water clusters in whisky. In: Campbell I (ed) Proceedings of the third aviemore conference on malting, brewing and distilling. Institute of Brewing, London, p 431–438Google Scholar
  25. 298.
    Glushko V, Thaler MSR, Karp CD (1981) Pyrene fluorescence fine-structure as a polarity probe of hydrophobic regions: behavior in model solvents. Arch Biochem Biophys 210:33–42CrossRefGoogle Scholar
  26. 304.
    González B, Calvar N, Gómez E, Domínguez Á (2007) Density, dynamic viscosity, and derived properties of binary mixtures of methanol or ethanol with water, ethyl acetate, and methyl acetate at T = (293.15, 298.15, and 303.15) K. J Chem Thermodyn 39:1578–1588CrossRefGoogle Scholar
  27. 311.
    Grolier J-PE, Wilhelm E (1981) Excess volumes and excess heat capacities of water +  ethanol at 298.15 K. Fluid Phase Equilib 6:283–287CrossRefGoogle Scholar
  28. 351.
    Hirschfelder J, Stevenson D, Eyring H (1937) A theory of liquid structure. J Chem Phys 5:896–912CrossRefGoogle Scholar
  29. 365.
    Hu N, Schaefer DW (2010) Effect of impurity compounds on ethanol hydration. J Mol Liq 155:29–36CrossRefGoogle Scholar
  30. 366.
    Hu N, Wu D, Cross KJ, Schaefer DW (2010) Structural basis of the 1H-nuclear magnetic resonance spectra of ethanol–water solutions based on multivariate curve resolution analysis of mid-infrared spectra. Appl Spectrosc 64:337–342CrossRefGoogle Scholar
  31. 368.
    Hudson CS (1904) Die gegenseitige Löslichkeit von Nikotin in Wasser. Z Phys Chem 47:113–115Google Scholar
  32. 404.
    Kahlweit M, Busse G, Jen J (1991) Adsorption of amphiphiles at water/air interface. J Phys Chem 95:5580–5586CrossRefGoogle Scholar
  33. 410.
    Kalyanasundaram K, Thomas JK (1977) Solvent-dependent fluorescence of pyrene-3-carboxaldehyde and its applications in estimation of polarity at micelle-water interfaces. J Phys Chem 81:2176–2180CrossRefGoogle Scholar
  34. 412.
    Karlsson BCG, Friedman R (2017) Dilution of whisky—the molecular perspective. Sci Rep 7:6489CrossRefGoogle Scholar
  35. 423.
    Kiyohara O, Benson GC (1981) Thermodynamics of aqueous mixtures of nonelectrolytes III. Compressibilities and isochoric heat capacities of water—n-alcohol mixtures at 20 C. J Solut Chem 10:281–290CrossRefGoogle Scholar
  36. 427.
    Koga K, Yoshizumi H (1977) Differential scanning calorimetry (DSC) studies on the structures of water-ethanol mixtures and aged whiskey. J Food Sci 42:1213–1217CrossRefGoogle Scholar
  37. 429.
    Koga Y, Nishikawa K, Westh P (2004) “Icebergs” or no “icebergs” in aqueous alcohols? Composition-dependent mixing schemes. J Phys Chem A 108:3873–3877CrossRefGoogle Scholar
  38. 438.
    Lama RF, Lu BC-Y (1965) Excess thermodynamic properties of aqueous alcohol solutions. J Chem Eng Data 10:216–219CrossRefGoogle Scholar
  39. 440.
    Lang JC, Morgan RD (1980) Nonionic surfactant mixtures. I. Phase equilibria in C10E4-H2O and closed-loop existence. J Chem Phys 73:5849–5861CrossRefGoogle Scholar
  40. 441.
    Larkin JA (1975) Thermodynamic properties of aqueous non-electrolyte mixtures I. Excess enthalpy for water+ ethanol at 298.15 to 383.15 K. J Chem Thermodyn 7:137–148CrossRefGoogle Scholar
  41. 462.
    Liltorp K, Westh P, Koga Y (2005) Thermodynamic properties of water in the water-poor region of binary water +  alcohol mixtures. Can J Chem 83:420–429CrossRefGoogle Scholar
  42. 472.
    Maçatelli M, Piggott JR, Paterson A (2010) Structure of ethanol-water systems and its consequences for flavour. In: Walker GM, Hughes PS (eds) Distilled spirits. New horizons: energy, environment and enlightenment. Proceedings of the worldwide distilled spirits conference. Nottingham University Press, Nottingham, p 235–242Google Scholar
  43. 516.
    Matsumoto M, Nishi N, Furusawa T, Saita M, Takamuku T, Yamagami M, Yamaguchi T (1995) Structure of clusters in ethanol-water binary solutions studied by mass spectrometry and X-ray diffraction. Bull Chem Soc Jpn 68:1775–1783CrossRefGoogle Scholar
  44. 522.
    McEwen BC (1923) Studies in mutual solubility. Part II. The mutual solubility of glycerol and alcohols, aldehydes, phenols, and their derivatives. J Chem Soc Trans 123:2284–2288CrossRefGoogle Scholar
  45. 531.
    Mendeleev D (1887) The compounds of ethyl alcohol with water. J Chem Soc Trans 51:778–782CrossRefGoogle Scholar
  46. 538.
    Mijaković M, Kežić B, Zoranić L, Sokolić F, Asenbaum A, Pruner C, Wilhelm E, Perera A (2011) Ethanol-water mixtures: ultrasonics, Brillouin scattering and molecular dynamics. J Mol Liq 164:66–73CrossRefGoogle Scholar
  47. 578.
    Nishi N, Yamamoto K (1987) Conversion of liquids to cluster beams by adiabatic expansion of liquid jets: mass spectrometric analysis of molecular association in aqueous solution systems. J Am Chem Soc 109:7353–7361CrossRefGoogle Scholar
  48. 579.
    Nishi N, Koga K, Oshima C, Yamamoto K, Nagashima U, Nagami N (1988) Molecular association in ethanol-water mixtures studied by mass spectrometric analysis of clusters generated through adiabatic expansion of liquid jets. J Am Chem Soc 110:5246–5255CrossRefGoogle Scholar
  49. 582.
    Nishimura K, Ohnishi M, Masuda M, Koga K, Matsuyama R (1983) Reactions of wood components during maturation. In: Piggott JR (ed) Flavour of distilled beverages: origin and development. Ellis Horwood, Chichester, p 241–255Google Scholar
  50. 591.
    Noskov SY, Lamoureux G, Roux B (2005) Molecular dynamics study of hydration in ethanol-water mixtures using a polarizable force field. J Phys Chem B 109:6705–6713CrossRefGoogle Scholar
  51. 606.
    Onori G, Santucci A (1996) Dynamical and structural properties of water/alcohol mixtures. J Mol Liq 69:161–181CrossRefGoogle Scholar
  52. 608.
    Osborne NS, McKelvy EC, Bearce HW (1913) Density and thermal expansion of ethyl alcohol and of its mixtures with water. Bull Bur Stan 9(3):327–474CrossRefGoogle Scholar
  53. 611.
    Ott JB, Stouffer CE, Cornett GV, Woodfield BF, Wirthlin RC, Christensen JJ (1986) Excess enthalpies for (ethanol+ water) at 298.15 K and pressures of 0.4, 5, 10, and 15 MPa. J Chem Thermodyn 18:1–12CrossRefGoogle Scholar
  54. 612.
    Ott JB, Sipowska JT, Gruszkiewicz MS, Woolley ST (1993) Excess volumes for (ethanol+ water) at the temperatures (298.15 and 348.15) K and pressure (0.4, 5, and 15) MPa and at the temperature 323.15 K and pressure (5 and 15) MPa. J Chem Thermodyn 25:307–318CrossRefGoogle Scholar
  55. 639.
    Pečar D, Doleček V (2005) Volumetric properties of ethanol-water mixtures under high temperatures and pressures. Fluid Phase Equilib 230:36–44CrossRefGoogle Scholar
  56. 651.
    Pirie G, Graham B, Kubie J (2000) Membrane filtration of whisky. In: Food & drink 2000: processing solutions for innovative products. Chemical Engineers, UK, p 9–11Google Scholar
  57. 670.
    Price WS, Ide H, Arata Y (2003) Solution dynamics in aqueous monohydric alcohol systems. J Phys Chem A 107:4784–4789CrossRefGoogle Scholar
  58. 720.
    Sakurai M, Nakamura K, Takenaka N (1994) Apparent molar volumes and apparent molar adiabatic compressions of water in some alcohols. Bull Chem Soc Jpn 67:352–359CrossRefGoogle Scholar
  59. 726.
    Sato T, Chiba A, Nozaki R (1999) Dynamical aspects of mixing schemes in ethanol-water mixtures in terms of the excess partial molar activation free energy, enthalpy, and entropy of the dielectric relaxation process. J Chem Phys 110:2508–2521CrossRefGoogle Scholar
  60. 750.
    Shinoda K, Yamaguchi T, Hori R (1961) The surface tension and the critical micelle concentration in aqueous solution of β-D-alkyl glucosides and their mixtures. Bull Chem Soc Jpn 34:237–241CrossRefGoogle Scholar
  61. 780.
    Staveley LAK, Hart KR, Tupman WI (1953) The heat capacities and other thermodynamic properties of some binary liquid mixtures. Discuss Faraday Soc 15:130–142CrossRefGoogle Scholar
  62. 800.
    Tauler R, Smilde A, Kowalski B (1995) Selectivity, local rank, three-way data analysis and ambiguity in multivariate curve resolution. J Chemometr 9:31–58CrossRefGoogle Scholar
  63. 850.
    Vázquez G, Alvarez E, Navaza JM (1995) Surface tension of alcohol +  water from 20 to 50 C. J Chem Eng Data 40:611–614CrossRefGoogle Scholar
  64. 906.
    Withers SJ, Piggott JR, Leroy G, Conner JM, Paterson A (1995) Factors affecting pungency of malt distillates and ethanol–water mixtures. J Sens Stud 10:273–283CrossRefGoogle Scholar
  65. 923.
    Zana R, Eljebari MJ (1993) Fluorescence probing investigation of the self-association of alcohols in aqueous solution. J Phys Chem 97:11134–11136CrossRefGoogle Scholar

Copyright information

© Springer Nature Switzerland AG 2019

Authors and Affiliations

  • Gregory H. Miller
    • 1
  1. 1.University of California, Professor of Chemical EngineeringDavisUSA

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