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In champagne and carbonated beverages, bubble nucleation was mostly found to take place from tiny Taylor-
like bubbles trapped inside immersed cellulose fibers stuck on the glass wall. The present paper complements
a previous paper about the thorough examination of the bubble nucleation process in a flute poured with
champagne (Liger-Belair et al. J. Phys. Chem. B 2005, 109, 14573). In this previous paper, a model was built
that accurately reproduces the dynamics of these tiny Taylor-like bubbles that grow inside the fibers lumen
by diffusion of CO2-dissolved molecules. In the present paper, by use of the model recently developed, the
frequency of bubble formation from cellulose fibers is accessed and linked with various liquid and fiber
parameters, namely, the concentration cL of CO2-dissolved molecules, the liquid temperature , its viscosity
, the ambient pressure P, the course of the gas pocket growing trapped inside the fibers lumen before
releasing a bubble, and the radius r of the fibers lumen. The relative influence of the latter parameters on the
bubbling frequency is discussed and supported with recent experimental observations and data.
1. Introduction trapped inside the collection of fibers adsorbed on the glass wall
offer gas/liquid interfaces to CO2-dissolved molecules, which
In champagne and sparkling wines, carbon dioxide molecules cross the interface toward the gas pockets. In turn, gas pockets
in excess form together with ethanol when yeast ferments sugars.
grow inside the fibers lumen. When a gas pocket reaches the
They are responsible for producing gas bubbles as soon as the
tip of a fiber, a bubble is ejected, but a portion of the gas pocket
bottle is uncorked. In soda drinks and most of fizzy waters,
remains trapped inside the fibers lumen, shrinks back to its
industrial carbonation is the source of effervescence.1
initial position, and the cycle starts again until bubble production
Generally speaking, sparkling beverages are weakly super- stops through lack of dissolved gas molecules (see Figure 1).
saturated with CO2-dissolved gas molecules. In weakly super- The fiber displayed in Figure 1 is a sort of textbook case, the
saturated liquids such as carbonated beverages in general, bubble behavior of which was recently understood and modeled.8 The
formation and growth require preexisting gas cavities with radii fine mechanisms behind the regular production of bubbles from
of curvature large enough to overcome the nucleation energy those tiny hollow and cylindrical structures are indeed still under
barrier and grow freely.2,3 Jones et al. made a classification of progress.9
the broad range of nucleation likely to be encountered in liquids
supersaturated with dissolved gas.4 Bubble formation from Champagne and sparkling wine tasters often pay much
preexisting gas cavities larger than the critical size is referred importance to the allure of effervescence in the glass, and even
to as nonclassical heterogeneous bubble nucleation (type IV if there is no evidence yet to believe that bubbles confer any
bubble nucleation, following their nomenclature). other sensory advantage to the wine, it often is recognized that
bubbles play a major role in the assessment of champagne and
The close-up observation of glasses poured with carbonated
sparkling wines. For this reason, champagne makers and
beverages recently revealed that most of the bubble nucleation
champagne houses have spent much effort during the past few
sites were found to be located on preexisting gas cavities trapped
years to better detect, understand, and control the various
inside hollow and roughly cylindrical cellulose-fiber-made
parameters involved in the kinetics of effervescence and
structures on the order of 100 m long with a cavity mouth of
foaming. Actually, the average bubbling frequency of a single
several micrometers.5-7 The hollow cavity inside these fibers
cellulose fiber is a key parameter that determines the overall
where a gas pocket is trapped during the pouring process is
number of bubbles produced in a glass per second, and,
called the lumen. The mechanism of bubble release from a
therefore, the overall kinetics of gas discharging from the
fibers lumen already has been described and partly modeled
supersaturated liquid.
in recent papers.5-8 In short, after a bottle of champagne or
sparkling wine is opened, the thermodynamic equilibrium of The model developed in ref 8 accurately reproduces the
CO2 molecules dissolved in the liquid medium is broken. CO2- dynamics of this tiny Taylor-like bubble that grows inside the
dissolved molecules become in excess in comparison with what fibers lumen by diffusion of CO2-dissolved molecules. In the
the liquid medium can withstand. Therefore, CO2 molecules will present paper, by use of the model recently developed, the
escape from the liquid medium through every available gas/ frequency of bubble formation from cellulose fibers is accessed
liquid interface to reach a vapor phase. Actually, once the and linked with various liquid and fiber parameters, namely,
sparkling beverage is poured into a glass, the tiny gas pockets the concentration cL of CO2-dissolved molecules, the liquid
temperature , its viscosity , the ambient pressure P, the course
* Corresponding author. E-mail: gerard.liger-belair@univ-reims.fr. of the gas pocket growing trapped inside the fibers lumen before
Tel: (33)3 26 91 86 14. Fax: (33)3 26 91 33 40. releasing a bubble, and the radius r of the fibers lumen. The
10.1021/jp0640427 CCC: $33.50 2006 American Chemical Society
Published on Web 10/03/2006
21146 J. Phys. Chem. B, Vol. 110, No. 42, 2006 Liger-Belair et al.
[ )]
observations and data.
Hdiss 1 1
2. Experimental Section
kH() ) k298K exp - (
R 298
- (2)
2.1. Material. A standard commercial champagne wine was where k298 K ) 1.21 10-5 kg m-3 ps-1 is the Henrys law
poured in a classical crystal flute that was first rinsed using constant at 298 K, Hdiss -24 800 J/mol is the dissolution
distilled water and then was air-dried. Some physicochemical enthalpy of CO2 molecules in champagne (in J/mol), and R
parameters of champagne were already determined at 20 C is the ideal gas constant (8.31 J mol-1 K-1).
with a sample of champagne first degassed.5 The static surface 2.2. Set-up Used to Observe Bubble Nucleation in Close-
tension of champagne was found to be on the order of 47 up. The dynamics of bubble nucleation was captured with a
mN/m, its density F was measured and found to be 998 kg/m3, high-speed digital video camera (Speedcam+, Vannier Photelec,
and its dynamic viscosity was found to be on the order of 1.5 Antony, France) that was able to film up to 2000 frames per
10-3 kg m-1 s-1. In the range of temperature in which second and was fitted with a microscope objective (Mitutoyo,
champagne and sparkling wine tasting is concerned (ap- M Plan Apo 5, Japan). The champagne was first poured into
proximately 5-15 C), their surface tension and density do not the flute, which was placed between the objective and a cold
drastically vary. However, in this range of champagne-tasting source light (Fiber-Lite, PL-900, dc regulated illuminator). A
Kinetics of Bubble Nucleation in Champagne J. Phys. Chem. B, Vol. 110, No. 42, 2006 21147
Figure 3. Scheme (a) and photographic detail (b) of the workbench used to observe bubble nucleation sites in close-up.
1 1
f) (4)
T ln[(zf + A)/(z0 + A)]
2RDc
f (5)
r(P + 2/r) ln[(zf + 10r)/(z0 + 10r)]
{
pertinent parameters involved may be rewritten as follows (in
z(t) (z0 + A) exp(t/) - A the MKSA system):
(P + 2/r)r 4RD0c (3)
with ) , and A ) 2[cL - kH(P + 2/r)]
2RDc (P + 2/r) f 2.4 10-14 (6)
r(P + 2/r) ln[(zf + 10r)/(z0 + 10r)]
where z is the length of the gas pocket, z0 is the initial length
of the gas pocket before it starts its growth through the lumen The boundary layer thickness was indirectly approached
at each cycle of bubble production (see Figure 1, panel 1), P is in a recent paper and found to be on the order of 20 m.8
the ambient pressure, D0 is the diffusion coefficient of CO2- Let us apply the latter equation to the standard textbook case
dissolved molecules in the liquid bulk, D is the diffusion fiber displayed in Figure 1 and modeled in Figure 4 (i.e., r
5 m, z0 20 m and zf 100 m). Equation 6 may be
coefficient of CO2-dissolved molecules through the fiber wall
rewritten as the following by replacing the fibers parameters
(and, therefore, perpendicular to the cellulose microfibrils), c
r, z0, zf, and by their numerical values:
) cL - cB ) cL - kHPB ) cL - kH(P + 2/r) is the difference
in CO2-dissolved concentrations between the liquid bulk and
-8
2[cL - kH(P + 0.2)]
the close vicinity of the gas pocket surface in equilibrium with f 5.2 10 (7)
the gaseous CO2 in the gas pocket, and is the boundary layer (P + 0.2)
thickness where a linear gradient of CO2-dissolved concentration
is assumed. In the latter expression, cL is expressed in g/L, kH is expressed
in g/L/atm, P is expressed in atm, and is expressed in kg/m/s
In a previous work, the transversal diffusion coefficient D
to fit the standards used in enology.
of CO2 molecules through the fiber wall was approached and
3.3. Relative Influence of Several Parameters on the
was properly bounded by D/D0 0.1 and D/D0 0.3.7 For
Average Bubbling Frequency. We will discuss the relative
modeling purposes, an intermediate value of about D 0.2D0 influence of the following parameters on the average bubbling
was proposed and will be used hereafter. frequency: (i) the concentration cL of CO2-dissolved molecules,
3.2. Modeling the Average Bubbling Frequency. As seen (ii) the liquid temperature , and (iii) the ambient pressure P.
in Figure 1, the whole process leading to the production of a (i) Through the use of eq 6 with every other parameter being
bubble from a cellulose fibers tip can be coarsely divided in constant, the dependence of the theoretical average bubbling
two main steps: (i) the growth of the gas pocket trapped inside frequency f with the CO2-dissolved concentration cL is in the
the fibers lumen, and (ii) the bubble detachment as the gas form f ) acL - b. By use of the high-speed video camera, a
pocket reaches the fibers tip. Actually, it is clear from the few cellulose fibers that act as bubble nucleation sites on the
numerous close-up time sequences taken with the high-speed wall of a glass poured with champagne were followed with time
video camera that the time scale of the bubble detachment is during the whole gas discharging process, which lasted several
always very small (1 ms) when compared with the relatively hours. For each given nucleation site, the experimental bubbling
slow growth of the gas pocket (several tens to several hundreds frequency fexp was directly accessed simply by measuring the
of milliseconds). Therefore, the whole cycle of bubble produc- time Texp needed by the nucleation site to release a bubble
tion seems to be largely governed by the growth of the gas (therefore, fexp ) 1/Texp). The concentration cL of CO2-dissolved
pocket trapped inside the fibers lumen. The period of bubble molecules was indirectly accessed by using the growth rate of
formation from a single cellulose fiber is therefore equal to the bubbles just released from the nucleation site as a CO2-probe.
total time T required by the tiny gas pocket to grow from its This method is developed in minute detail in ref 6 (see
initial length, denoted z0, to its final length, denoted zf, as it Appendix). The dependence of the experimental bubbling
reaches the fibers tip (see Figure 5). By retrieving eq 3, it is frequency fexp with cL is displayed in Figure 6 for four different
Kinetics of Bubble Nucleation in Champagne J. Phys. Chem. B, Vol. 110, No. 42, 2006 21149
3.4. A Comparison with the Model by Uzel et al.9 The terms of CO2 release, which we would like to both theoretically
model developed here is not the only one in the literature. The and experimentally evaluate in the future.
one recently developed by Uzel et al. makes different assump-
tions about the way in which the bubbles form.9 Contrary to Acknowledgment. The authors thank the EuropolAgro
the present model, which assumes that the dominant time scale institute and the Association Recherche Oenologie Champagne
that controls bubble release is the growth of the gas pocket Universite for financial support and Champagne Pommery and
growing trapped inside the fibers lumen, Uzels model es- Arc International for their collaborative efforts.
sentially assumes that the dominant mechanism is seeding at
the top of the fiber, the bubble detachment being controlled by Appendix
a balance between buoyancy and capillarity. Seeding at the The general equation concerning the mass transfer of
fibers tip necessarily involves unfavorable wetting conditions molecules from the bulk of a supersaturated liquid to a bubble
of the fibers wall. Actually, because cellulose is a highly surface with time is
hydrophilic material, aqueous liquids such as champagne and
carbonated beverages forbid the establishment of a triple contact dN
) KAc (A1)
line at the fibers tip. Therefore, a gas bubble released after the dt
breaking of the gas pocket growing trapped inside the fibers
lumen (Figure 1, panel 5) should be unable to seed at the fibers where N is the number of transferred CO2 moles, K is the mass
tip (as a droplet of water would do). However, some nucleation transfer coefficient, A is the bubble area, and c ) cL - c0 is
sites could eventually experience transitions from wetting to the difference in CO2 concentration between the bulk of the
nonwetting conditions (due to lipid contamination, for example). liquid and the bubble surface in equilibrium with the CO2 gas
In such conditions, a bubble could definitely grow anchored to into the bubble.
the fibers tip before detaching because of buoyancy. In such Assuming the gas into the rising bubble as ideal (PBV )
conditions, the total time needed to release a bubble from a NR), the number of CO2 moles transferred into the bubble is
nucleation site would be the sum of two characteristic times: connected with the variation of its radius R with time as follows
(1) the time required by the gas pocket to grow from its initial
dN PB dV PB dR
length, z0, to its final length, zf, as it reaches the fibers tip ) ) A (A2)
(modeled in the present paper), and (2) the time required for dt R dt R dt
the bubble to grow until it detaches because of buoyancy
where V is the bubble volume, and PB is the pressure inside the
(modeled in the paper by Uzel et al.9). This is the reason why
rising bubble assumed to be equal to the atmospheric pressure
these two extreme models are highly complementary. They focus
P0, because both the hydrostatic pressure (FgH < 10-2P0) and
on both steps of the bubble release, the best model probably
the Laplace pressure (2/R < 10-1P0) inside the rising bubble
being a combination of the two models. Mixing these two
are negligible.
models could be the purpose of future work.
By combining eqs A1 and A2, one obtains the rate of
expansion of the bubble radius
4. Conclusions and Prospects
dR R
The dynamics of bubble nucleation from the lumen of ) Kc (A3)
immersed cellulose fibers stuck on the wall of a glass poured
dt P0
with champagne were accurately observed, in situ, from high-
Generally speaking, heat and mass transfers are functions of
speed video recordings. We used a previously developed model
two dimensionless numbers, the Sherwood and Peclet numbers,
that utilized the dynamics of the tiny gas pockets responsible
Sh ) 2KR/D0 and Pe ) 2RU/D0, respectively, with U being
for the repetitive production of bubbles to access the theoretical
the velocity of ascending bubbles. In the case of small and large
frequency of bubble release. The theoretical frequency of bubble
Pe, asymptotic solutions have been derived in the literature.
release was found to depend on various fiber and liquid
Most of them are listed in the book by Sherwood et al.15 During
parameters. The main parameters likely to significantly influence
ascent, champagne bubbles cover a range of high Pe between
the frequency of bubble formation were found to be (i) the CO2-
approximately 102 and 105. At large Pe, Sh becomes proportional
dissolved concentration cL, (ii) the liquid temperature , and
to Pe1/3, with a numerical prefactor very close to unity.
(iii) the ambient pressure P.
Therefore,
In the future, we plan to organize at a large-scale champagne
( )
and sparkling wine tasting under a controlled atmosphere by KR 21/3 RU 1/3 U1/3
artificially modifying the intensity of effervescence through the w K 0.63D02/3 2/3 (A4)
D0 2 D0 R
ambient pressure parameter. We could eventually better under-
stand the role played by the intensity of effervescence on flavor Combining eqs A3 and A4 leads to
release without modifying the intrinsic aromatic properties of
the liquid (such as changes in the temperature would do). dR R U1/3
Actually, the continuous flow of ascending bubbles through the ) 0.63 D02/3 2/3 c (A5)
dt P0 R
liquid drains flavors and aromas with the result of continuously
renewing the layer at the liquid surface, thus providing a better By combining the empirical rising velocity U of ascending
release of the numerous volatile organic compounds above the champagne bubbles5 with eq A5, the rate of increase of the
liquid surface. However, bubbles bursting at the liquid surface ascending bubble radius becomes
also release a sudden and abundant quantity of CO2 above the
liquid surface with the result of irritating the nose during the dR R 2Fg 1/3
evaluation of aromas. From an enological point of view, there
k)
dt
0.63 D02/3
P0 9 ( )c (A6)
should therefore be a sort of ideal intensity of effervescence
that enhances flavor release without being too aggressive in where is a numerical prefactor close to 0.7.
Kinetics of Bubble Nucleation in Champagne J. Phys. Chem. B, Vol. 110, No. 42, 2006 21151
Equation A6 was found to be in very good agreement with K ) mass transfer coefficient, m/s.
the order of magnitude of experimental bubble growth rates in N ) number of CO2 moles.
champagne and beer glasses.5,6 Therefore, the good agreement P ) ambient pressure, N/m2.
between experimental and theoretical bubble growth rates gave P0 ) atmospheric pressure, 105 N/m2.
us the idea to use the experimental rising bubble growth rate as PB ) pressure inside a bubble, N/m2.
a probe for measuring c in the liquid medium. Finally, by Pe ) Peclet number, 2RU/D.
retrieving eq A6 in reverse order, c may be linked to the rising r ) radius of aperture of the lumen of a cellulose fiber acting
bubble growth rate k and some liquid parameters as follows: as a bubble nucleation site, 1-5 m.
R ) bubble radius, m.
P0 9 1/3 R ) ideal gas constant, 8.31 J K-1 mol-1.
c ) cL - c0
0.63R
D0-2/3 ( )
2Fg
k (A7) Sh ) Sherwood number, 2KR/D.
t ) time, s.
where c0 ) kHP0 is the molar concentration of CO2-dissolved T ) period of bubble production, s.
molecules in equilibrium with the CO2 gas into the bubble. Texp ) experimental period of bubble production, s.
Finally U ) bubble velocity, m/s.
V ) bubble volume, m3.
P0 9 1/3 z ) length of the gas pocket growing trapped inside a fibers
c L c0 + D -2/3
0.63R 0 ( )
2Fg
k (A8) lumen.
z0 ) initial length of the gas pocket growing trapped inside
It is worth noting that in eq A8, each parameter is expressed a fibers lumen.
in the MKSA system. In particular, cL and c0 are expressed in zf ) final length of the gas pocket growing trapped inside a
mol/m3. fibers lumen, when it reaches a fibers tip.