Q3-1

Theory

English (Official)

Champagne! (10 points)

Warning: Excessive alcohol consumption is harmful to health and drinking alcohol below legal age is
prohibited.

Champagne is a French sparkling wine. Fermentation of sugars produces

carbon dioxide (CO2 ) in the bottle. The molar concentration of CO2 in the
liquid phase 𝑐ℓ and the partial pressure 𝑃CO2 in the gas phase are related
by 𝑐ℓ = 𝑘H 𝑃CO2 , known as Henry's law and where 𝑘H is called Henry's con-
stant.
Data
• Surface tension of champagne 𝜎 = 47 × 10−3 J ⋅ m−2
• Density of the liquid 𝜌ℓ = 1.0 × 103 kg ⋅ m−3
• Henry's constant at 𝑇0 = 20 °C, 𝑘H (20 °C) = 3.3 × 10−4 mol ⋅ m−3 ⋅ Pa−1
• Henry's constant at 𝑇0 = 6 °C, 𝑘H (6 °C) = 5.4 × 10−4 mol ⋅ m−3 ⋅ Pa−1
• Atmospheric pressure 𝑃0 = 1 bar = 1.0 × 105 Pa
Fig. 1. A glass filled with
• Gases are ideal with an adiabatic coefficient 𝛾 = 1.3
champagne.

Part A. Nucleation, growth and rise of bubbles

Immediately after opening a bottle of champagne at temperature 𝑇0 = 20 °C , we fill a glass. The pressure
in the liquid is 𝑃0 and its temperature stays constant at 𝑇0 . The concentration 𝑐ℓ of dissolved CO2 exceeds
the equilibrium concentration and we study the nucleation of a CO2 bubble. We note 𝑎 its radius and 𝑃b
its inner pressure.

A.1 Express the pressure 𝑃b in terms of 𝑃0 , 𝑎 and 𝜎. 0.2pt

In the liquid, the concentration of dissolved CO2 depends on the distance to the bubble. At long distance
we recover the value 𝑐ℓ and we note 𝑐b the concentration close to the bubble surface. According to
Henry's law, 𝑐b = 𝑘H 𝑃b . We furthermore assume in all the problem that bubbles contain only CO2 .
Since 𝑐ℓ ≠ 𝑐b , CO2 molecules diffuse from areas of high to low concentration. We assume also that any
molecule from the liquid phase reaching the bubble surface is transferred to the vapour.

A.2 Express the critical radius 𝑎c above which a bubble is expected to grow in terms 0.5pt
of 𝑃0 , 𝜎, 𝑐ℓ and 𝑐0 where 𝑐0 = 𝑘H 𝑃0 . Calculate numerically 𝑎c for 𝑐ℓ = 4𝑐0 .

In practice, bubbles mainly grow from pre-existing gas cavities. Consider then a bubble with initial radius
𝑎0 ≈ 40 µm. The number of moles of CO2 transferred at the bubble's surface per unit area and time is noted
𝑗. Two models are possible for 𝑗.
𝐷
• model (1) 𝑗 = (𝑐 − 𝑐b ) where 𝐷 is the diffusion coefficient of CO2 in the liquid.
𝑎 ℓ
• model (2) 𝑗 = 𝐾 (𝑐ℓ − 𝑐b ) where 𝐾 is a constant here.
Experimentally, the bubble radius 𝑎(𝑡) is found to depend on time as shown in Fig. 2. Here 𝑐ℓ ≈ 4𝑐0 , and
since bubbles are large enough to be visible, the excess pressure due to surface tension can be neglected
and 𝑃b ≈ 𝑃0 .
 Q3-2
Theory

English (Official)

A.3 Express the number of CO2 moles in the bubble 𝑛c in terms of 𝑎, 𝑃0 , 𝑇0 and ideal 1.2pt
gas constant 𝑅. Find 𝑎(𝑡) for both models. Indicate which model explains the
experimental results in Fig. 2. Depending on your answer, calculate numeri-
cally 𝐾 or 𝐷.

Fig. 2. Time evolution of CO2 bubble radius in a glass of champagne (adapted from [1]).

Eventually bubbles detach from the bottom of the glass and continue to grow while rising. Fig. 3. shows
a train of bubbles. The bubbles of the train have the same initial radius and are emitted at a constant
frequency 𝑓b = 20 Hz.

𝑢⃗𝑧 𝑧
𝑔0⃗ 1 mm
Fig. 3. A train of bubbles. The photo is rotated horizontally for the page layout (adapted from
[1]).

For the range of velocities studied here, the drag force 𝐹 on a bubble of radius 𝑎 moving at velocity 𝑣 in a
liquid of dynamic viscosity 𝜂 is given by Stokes' law 𝐹 = 6𝜋𝜂𝑎𝑣. Measurements show that at any moment
in time, the bubble can be assumed to be travelling at its terminal velocity.

A.4 Give the expression of the main forces exerted on a vertically rising bubble. 0.8pt
Obtain the expression of 𝑣(𝑎). Give a numerical estimate of 𝜂 using 𝜌ℓ , 𝑔0 and
quantities measured on Fig. 3.

The quasi-stationary growth of bubbles with rate 𝑞𝑎 = d𝑎

d𝑡
still applies during bubble rise.

A.5 Express the radius 𝑎𝐻ℓ of a bubble reaching the free surface in terms of height 0.5pt
travelled 𝐻ℓ , growth rate 𝑞𝑎 = d𝑎
d𝑡
, and any constants you may need. Assume
𝑎𝐻ℓ ≫ 𝑎0 and 𝑞𝑎 constant, and give the numerical value of 𝑎𝐻ℓ with 𝐻ℓ = 10 cm
and 𝑞𝑎 corresponding to Fig. 2.
 Q3-3
Theory

English (Official)

There are 𝑁b nucleation sites of bubbles. Assume that the bubbles are nucleated at a constant frequency
𝑓b at the bottom of a glass of champagne (height 𝐻ℓ for a volume 𝑉ℓ ), with 𝑎0 still negligible. Neglect
diffusion of CO2 at the free surface.

A.6 Write the differential equation for 𝑐ℓ (𝑡). Obtain from this equation the charac- 1.1pt
teristic time 𝜏 for the decay of the concentration of dissolved CO2 in the liquid.

Part B. Acoustic emission of a bursting bubble

Small bubbles are nearly spherical as they reach the free surface. Once the liquid film separating the
bubble from the air thins out sufficiently, a circular hole of radius 𝑟 forms in the film and, driven by
surface tension, opens very quickly (Fig. 4. left). The hole opens at constant speed 𝑣f (Fig. 4. right). The
film outside the rim remains still, with constant thickness ℎ.

𝐴 (2) ℎ 𝑣f d𝑡
𝑣f⃗
𝑟𝑐 (1)
(3) 𝑟(𝑡)
𝑎
𝐴
(𝛼) (𝛽)

𝐴
𝑟(𝑡)
𝑧
𝑅m
ℎ
𝐴
𝑟(𝑡) 𝑣f⃗
𝑣f d𝑡
(𝛾) (𝛿)

Fig. 4. (Left) (𝛼) Bubble at the surface: (1) liquid, (2) air at pressure 𝑃0 and (3), CO2 at pressure
𝑃b , (𝛽) and (𝛾) retraction of the liquid film, where the rim is in dark blue, (𝛿) bubble collapse.
(Right) Retraction of the liquid film at time 𝑡. Top: sketch of the pierced film seen from above.
Bottom: cross-section of the rim and the retracting film. During d𝑡 the rim accumulates nearby
liquid (dotted).

Due to dissipative processes, only half of the difference of the surface energy between 𝑡 and 𝑡 +d𝑡 of the
rim and the accumulated liquid is transformed into kinetic energy. We further assume that the variation
of the surface of the rim is negligible compared to that of the film.

B.1 Express 𝑣f in terms of 𝜌ℓ , 𝜎 and ℎ. 1.1pt

 Q3-4
Theory

English (Official)

When the film bursts, it releases internal

𝑃0 𝑧 pressure and emits a sound. We model
2𝑟
this acoustic emission by a Helmholtz res-
𝑚P 𝑧 onator: a cavity open to the atmosphere
0 at 𝑃0 through a bottleneck aperture of
𝑆
𝑎 area 𝑆 (Fig. 5. left). In the neck, a mass
𝑚p makes small amplitude position oscil-
𝑃(𝑡) lations due to the pressure forces it expe-
riences as the gas in the cavity expands
or compresses adiabatically. The grav-
ity force on 𝑚p is negligible compared to
Fig. 5. (Left) a Helmholtz resonator. (Right) a bubble as pressure forces. Let 𝑉0 be the volume of
an oscillator. gas under the mass 𝑚p for 𝑃 = 𝑃0 as 𝑧 = 0.

B.2 Express the frequency of oscillation 𝑓0 of 𝑚p . Hint: for 𝜀 ≪ 1, (1 + 𝜀)𝛼 ≈ 1 + 𝛼𝜀. 1.1pt

The Helmholtz model may be used for a bubble of radius 𝑎. 𝑉0 is the volume of the closed bubble. From
litterature, the mass of the equivalent of the piston is 𝑚𝑝 = 8𝜌𝑔 𝑟 3 /3 where 𝑟 is the radius of the circular
aperture and 𝜌𝑔 = 1.8 kg ⋅ m−3 is the density of the gas (Fig. 5. right). During the bursting process, 𝑟 goes
2 2 𝜌ℓ 𝑔0
from 0 to 𝑟c , given by 𝑟c = 𝑎  . At the same time, the frequency of emitted sound increases until
√3 𝜎
a maximum value of 40 kHz and the bursting time is 𝑡𝑏 = 3 × 10−2 ms.

B.3 Find the radius 𝑎 and the thickness ℎ of the champagne film separating the 1.1pt
bubble from the atmosphere.

Part C. Popping champagne

In a bottle, the total quantity of CO2 is 𝑛T = 0.2 mol, either dissolved in the volume 𝑉L = 750 mL of liquid
champagne, or as a gas in the volume 𝑉G = 25 mL under the cork (Fig. 6. left). 𝑉G contains only CO2 .
The equilibrium between both CO2 phases follows Henry's Law. We suppose that the fast gaseous CO2
expansion when the bottle is opened, is adiabatic and reversible. Ambient temperature 𝑇0 and pressure
𝑃0 = 1 bar are constant.

𝑃0 } (1)

ℓ0 𝑑 } (2)

𝑃i , 𝑉 G
} (3)

𝑐ℓ = 𝑘H 𝑃i
𝑉L }(4)
Fig. 6. Left: traditional bottleneck: (1) surrounding air, (2) cork stopper, (3) headspace, (4)
liquid champagne. Right: Two phenomena observed while opening the bottle at two different
temperatures (adapted from [2]).
 Q3-5
Theory

English (Official)

C.1 Give the numerical value of the pressure 𝑃i of gaseous CO2 in the bottle for 0.4pt
𝑇0 = 6 °C and 𝑇0 = 20 °C.

Another step of champagne production (not described here) leads to the following values of 𝑃𝑖 that we
will use for the next questions: 𝑃i = 4.69 bar at 𝑇0 = 6 °C and 𝑃i = 7.45 bar at 𝑇0 = 20 °C.
During bottle opening, two different phenomena can be observed, depending on 𝑇0 (Fig. 6. right).
• either a blue fog appears, due to the formation of solid CO2 crystals (but water condensation is
inhibited);
• or a grey-white fog appears, due to water vapor condensation in the air surrounding the bottleneck.
In this latter case, there is no formation of CO2 solid crystals.
CO
𝑃sat 2 𝐵
The saturated vapor pressure 𝑃sat 2 for the CO2 solid/gas transition follows : log10 ⒧ with
CO
⒭=𝐴−
𝑃0 𝑇 +𝐶
𝑇 in K, 𝐴 = 6.81, 𝐵 = 1.30 × 103 K and 𝐶 = −3.49 K.

C.2 Give the numerical value 𝑇f of the CO2 gas at the end of the expansion, after 0.7pt
opening a bottle, if 𝑇0 = 6 °C and if 𝑇0 = 20 °C, if no phase transition occured.
Choose which statements are true (several statements possible):
1. At 𝑇0 = 6 °C a grey-white fog appears while opening the bottle.
2. At 𝑇0 = 6 °C a blue fog appears while opening the bottle.
3. At 𝑇0 = 20 °C a grey-white fog appears while opening the bottle.
4. At 𝑇0 = 20 °C a blue fog appears while opening the bottle.

During bottle opening, the cork stopper pops out. We now determine the maximum height 𝐻c it reaches.
Assume that the friction force 𝐹 due to the bottleneck on the cork stopper is 𝐹 = 𝛼𝐴 where 𝐴 is the area
of contact and 𝛼 is a constant to determine. Initially, the pressure force slightly overcomes the friction
force. The cork's mass is 𝑚 = 10 g, its diameter 𝑑 = 1.8 cm and the length of the cylindrical part initially
stuck in the bottleneck is ℓ0 = 2.5 cm. Once the cork has left the bottleneck, you can neglect the net
pressure force.

C.3 Give the numerical value of 𝐻c if the external temperature is 𝑇0 = 6 °C. 1.3pt

[1] Liger-Belair et al, Am. J. Enol. Vitic., Vol. 50, No. 3 (1999).
[2] Liger-Belair et al., Sc. Reports 7, 10938 (2017).