IPhO 2025 · Theory problem 3

Champagne!

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 (\(\mathrm{CO}_2\)) in the bottle. The molar concentration of \(\mathrm{CO}_2\) in the liquid phase \(c_\ell\) and the partial pressure \(P_{\mathrm{CO}_2}\) in the gas phase are related by \(c_\ell=k_{\mathrm H}P_{\mathrm{CO}_2}\), known as Henry's law and where \(k_{\mathrm H}\) is called Henry's constant.

Data

  • Surface tension of champagne \(\sigma=47\times10^{-3}\,\mathrm{J\cdot m^{-2}}\)
  • Density of the liquid \(\rho_\ell=1.0\times10^3\,\mathrm{kg\cdot m^{-3}}\)
  • Henry's constant at \(T_0=20^\circ\mathrm C\), \(k_{\mathrm H}(20^\circ\mathrm C)=3.3\times10^{-4}\,\mathrm{mol\cdot m^{-3}\cdot Pa^{-1}}\)
  • Henry's constant at \(T_0=6^\circ\mathrm C\), \(k_{\mathrm H}(6^\circ\mathrm C)=5.4\times10^{-4}\,\mathrm{mol\cdot m^{-3}\cdot Pa^{-1}}\)
  • Atmospheric pressure \(P_0=1\,\mathrm{bar}=1.0\times10^5\,\mathrm{Pa}\)
  • Gases are ideal with an adiabatic coefficient \(\gamma=1.3\)
Figure 1

Fig. 1. A glass filled with champagne.

Part A. Nucleation, growth and rise of bubbles

Immediately after opening a bottle of champagne at temperature \(T_0=20^\circ\mathrm C\), we fill a glass. The pressure in the liquid is \(P_0\) and its temperature stays constant at \(T_0\). The concentration \(c_\ell\) of dissolved \(\mathrm{CO}_2\) exceeds the equilibrium concentration and we study the nucleation of a \(\mathrm{CO}_2\) bubble. We note \(a\) its radius and \(P_{\mathrm b}\) its inner pressure.

A.1 — 0.2pt

Express the pressure \(P_{\mathrm b}\) in terms of \(P_0\), \(a\) and \(\sigma\).

In the liquid, the concentration of dissolved \(\mathrm{CO}_2\) depends on the distance to the bubble. At long distance we recover the value \(c_\ell\) and we note \(c_{\mathrm b}\) the concentration close to the bubble surface. According to Henry's law, \(c_{\mathrm b}=k_{\mathrm H}P_{\mathrm b}\). We furthermore assume in all the problem that bubbles contain only \(\mathrm{CO}_2\).

Since \(c_\ell\ne c_{\mathrm b}\), \(\mathrm{CO}_2\) 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 — 0.5pt

Express the critical radius \(a_{\mathrm c}\) above which a bubble is expected to grow in terms of \(P_0,\sigma,c_\ell\) and \(c_0\) where \(c_0=k_{\mathrm H}P_0\). Calculate numerically \(a_{\mathrm c}\) for \(c_\ell=4c_0\).

In practice, bubbles mainly grow from pre-existing gas cavities. Consider then a bubble with initial radius \(a_0\approx40\,\mu\mathrm m\). The number of moles of \(\mathrm{CO}_2\) transferred at the bubble's surface per unit area and time is noted \(j\). Two models are possible for \(j\).

  • model (1) \(j=\dfrac{D}{a}(c_\ell-c_{\mathrm b})\) where \(D\) is the diffusion coefficient of \(\mathrm{CO}_2\) in the liquid.
  • model (2) \(j=K(c_\ell-c_{\mathrm b})\) where \(K\) is a constant here.

Experimentally, the bubble radius \(a(t)\) is found to depend on time as shown in Fig. 2. Here \(c_\ell\approx4c_0\), and since bubbles are large enough to be visible, the excess pressure due to surface tension can be neglected and \(P_{\mathrm b}\approx P_0\).

A.3 — 1.2pt

Express the number of \(\mathrm{CO}_2\) moles in the bubble \(n_{\mathrm c}\) in terms of \(a,P_0,T_0\) and ideal gas constant \(R\). Find \(a(t)\) for both models. Indicate which model explains the experimental results in Fig. 2. Depending on your answer, calculate numerically \(K\) or \(D\).

Figure 2

Fig. 2. Time evolution of \(\mathrm{CO}_2\) 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 \(f_{\mathrm b}=20\,\mathrm{Hz}\).

Figure 3

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 \(\eta\) is given by Stokes' law \(F=6\pi\eta av\). Measurements show that at any moment in time, the bubble can be assumed to be travelling at its terminal velocity.

A.4 — 0.8pt

Give the expression of the main forces exerted on a vertically rising bubble. Obtain the expression of \(v(a)\). Give a numerical estimate of \(\eta\) using \(\rho_\ell\), \(g_0\) and quantities measured on Fig. 3.

The quasi-stationary growth of bubbles with rate \(q_a=\dfrac{\mathrm da}{\mathrm dt}\) still applies during bubble rise.

A.5 — 0.5pt

Express the radius \(a_{H_\ell}\) of a bubble reaching the free surface in terms of height travelled \(H_\ell\), growth rate \(q_a=\dfrac{\mathrm da}{\mathrm dt}\), and any constants you may need. Assume \(a_{H_\ell}\gg a_0\) and \(q_a\) constant, and give the numerical value of \(a_{H_\ell}\) with \(H_\ell=10\,\mathrm{cm}\) and \(q_a\) corresponding to Fig. 2.

There are \(N_{\mathrm b}\) nucleation sites of bubbles. Assume that the bubbles are nucleated at a constant frequency \(f_{\mathrm b}\) at the bottom of a glass of champagne (height \(H_\ell\) for a volume \(V_\ell\)), with \(a_0\) still negligible. Neglect diffusion of \(\mathrm{CO}_2\) at the free surface.

A.6 — 1.1pt

Write the differential equation for \(c_\ell(t)\). Obtain from this equation the characteristic time \(\tau\) for the decay of the concentration of dissolved \(\mathrm{CO}_2\) 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 \(v_{\mathrm f}\) (Fig. 4. right). The film outside the rim remains still, with constant thickness \(h\).

Figure 4

Fig. 4. (Left) \((\alpha)\) Bubble at the surface: (1) liquid, (2) air at pressure \(P_0\) and (3), \(\mathrm{CO}_2\) at pressure \(P_{\mathrm b}\), \((\beta)\) and \((\gamma)\) retraction of the liquid film, where the rim is in dark blue, \((\delta)\) 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 \(\mathrm dt\) the rim accumulates nearby liquid (dotted).

Due to dissipative processes, only half of the difference of the surface energy between \(t\) and \(t+\mathrm dt\) 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 — 1.1pt

Express \(v_{\mathrm f}\) in terms of \(\rho_\ell,\sigma\) and \(h\).

Figure 5

Fig. 5. (Left) a Helmholtz resonator. (Right) a bubble as an oscillator.

When the film bursts, it releases internal pressure and emits a sound. We model this acoustic emission by a Helmholtz resonator: a cavity open to the atmosphere at \(P_0\) through a bottleneck aperture of area \(S\) (Fig. 5. left). In the neck, a mass \(m_{\mathrm p}\) makes small amplitude position oscillations due to the pressure forces it experiences as the gas in the cavity expands or compresses adiabatically. The gravity force on \(m_{\mathrm p}\) is negligible compared to pressure forces. Let \(V_0\) be the volume of gas under the mass \(m_{\mathrm p}\) for \(P=P_0\) as \(z=0\).

B.2 — 1.1pt

Express the frequency of oscillation \(f_0\) of \(m_{\mathrm p}\). Hint: for \(\varepsilon\ll1\), \((1+\varepsilon)^\alpha\approx1+\alpha\varepsilon\).

The Helmholtz model may be used for a bubble of radius \(a\). \(V_0\) is the volume of the closed bubble. From litterature, the mass of the equivalent of the piston is \(m_{\mathrm p}=8\rho_{\mathrm g}r^3/3\) where \(r\) is the radius of the circular aperture and \(\rho_{\mathrm g}=1.8\,\mathrm{kg\cdot m^{-3}}\) is the density of the gas (Fig. 5. right). During the bursting process, \(r\) goes from \(0\) to \(r_{\mathrm c}\), given by \[ r_{\mathrm c}=\frac{2}{\sqrt3}a^2\sqrt{\frac{\rho_\ell g_0}{\sigma}}. \] At the same time, the frequency of emitted sound increases until a maximum value of \(40\,\mathrm{kHz}\) and the bursting time is \(t_{\mathrm b}=3\times10^{-2}\,\mathrm{ms}\).

B.3 — 1.1pt

Find the radius \(a\) and the thickness \(h\) of the champagne film separating the bubble from the atmosphere.

Part C. Popping champagne

In a bottle, the total quantity of \(\mathrm{CO}_2\) is \(n_{\mathrm T}=0.2\,\mathrm{mol}\), either dissolved in the volume \(V_{\mathrm L}=750\,\mathrm{mL}\) of liquid champagne, or as a gas in the volume \(V_{\mathrm G}=25\,\mathrm{mL}\) under the cork (Fig. 6. left). \(V_{\mathrm G}\) contains only \(\mathrm{CO}_2\). The equilibrium between both \(\mathrm{CO}_2\) phases follows Henry's Law. We suppose that the fast gaseous \(\mathrm{CO}_2\) expansion when the bottle is opened, is adiabatic and reversible. Ambient temperature \(T_0\) and pressure \(P_0=1\,\mathrm{bar}\) are constant.

Figure 6

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]).

C.1 — 0.4pt

Give the numerical value of the pressure \(P_{\mathrm i}\) of gaseous \(\mathrm{CO}_2\) in the bottle for \(T_0=6^\circ\mathrm C\) and \(T_0=20^\circ\mathrm C\).

Another step of champagne production (not described here) leads to the following values of \(P_{\mathrm i}\) that we will use for the next questions: \(P_{\mathrm i}=4.69\,\mathrm{bar}\) at \(T_0=6^\circ\mathrm C\) and \(P_{\mathrm i}=7.45\,\mathrm{bar}\) at \(T_0=20^\circ\mathrm C\).

During bottle opening, two different phenomena can be observed, depending on \(T_0\) (Fig. 6. right).

  • either a blue fog appears, due to the formation of solid \(\mathrm{CO}_2\) 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 \(\mathrm{CO}_2\) solid crystals.

The saturated vapor pressure \(P_{\mathrm{sat}}^{\mathrm{CO}_2}\) for the \(\mathrm{CO}_2\) solid/gas transition follows: \[ \log_{10}\left(\frac{P_{\mathrm{sat}}^{\mathrm{CO}_2}}{P_0}\right) =A-\frac{B}{T+C} \] with \(T\) in \(\mathrm K\), \(A=6.81\), \(B=1.30\times10^3\,\mathrm K\) and \(C=-3.49\,\mathrm K\).

C.2 — 0.7pt

Give the numerical value \(T_{\mathrm f}\) of the \(\mathrm{CO}_2\) gas at the end of the expansion, after opening a bottle, if \(T_0=6^\circ\mathrm C\) and if \(T_0=20^\circ\mathrm C\), if no phase transition occured.

Choose which statements are true (several statements possible):

  1. At \(T_0=6^\circ\mathrm C\) a grey-white fog appears while opening the bottle.
  2. At \(T_0=6^\circ\mathrm C\) a blue fog appears while opening the bottle.
  3. At \(T_0=20^\circ\mathrm C\) a grey-white fog appears while opening the bottle.
  4. At \(T_0=20^\circ\mathrm C\) a blue fog appears while opening the bottle.

During bottle opening, the cork stopper pops out. We now determine the maximum height \(H_{\mathrm c}\) it reaches. Assume that the friction force \(F\) due to the bottleneck on the cork stopper is \(F=\alpha A\) where \(A\) is the area of contact and \(\alpha\) is a constant to determine. Initially, the pressure force slightly overcomes the friction force. The cork's mass is \(m=10\,\mathrm g\), its diameter \(d=1.8\,\mathrm{cm}\) and the length of the cylindrical part initially stuck in the bottleneck is \(\ell_0=2.5\,\mathrm{cm}\). Once the cork has left the bottleneck, you can neglect the net pressure force.

C.3 — 1.3pt

Give the numerical value of \(H_{\mathrm c}\) if the external temperature is \(T_0=6^\circ\mathrm C\).

[1] Liger-Belair et al, Am. J. Enol. Vitic., Vol. 50, No. 3 (1999).

[2] Liger-Belair et al., Sc. Reports 7, 10938 (2017).

General Data Sheet

Constant Notation Value Unit
Speed of light in vacuum \(c\) \(2.997\,924\,58\times10^8\) \(\mathrm{m\cdot s^{-1}}\)
Planck constant \(h\) \(6.626\,070\,15\times10^{-34}\) \(\mathrm{kg\cdot m^2\cdot s^{-1}}\)
Reduced Planck constant \(\hbar=\dfrac{h}{2\pi}\) \(1.054\,571\,818\times10^{-34}\) \(\mathrm{kg\cdot m^2\cdot s^{-1}}\)
Boltzmann constant \(k_{\mathrm B}\) \(1.380\,649\times10^{-23}\) \(\mathrm{kg\cdot m^2\cdot s^{-2}\cdot K^{-1}}\)
Avogadro constant \(N_{\mathrm A}\) \(6.022\,140\,76\times10^{23}\) \(\mathrm{mol^{-1}}\)
Molar gas constant \(R\) \(8.314\,462\,618\,153\,24\) \(\mathrm{kg\cdot m^2\cdot s^{-2}\cdot mol^{-1}\cdot K^{-1}}\)
Elementary charge \(e\) \(1.602\,176\,634\times10^{-19}\) \(\mathrm{A\cdot s}\)
Universal constant of gravitation \(G\) \(6.674\,30(15)\times10^{-11}\) \(\mathrm{m^3\cdot kg^{-1}\cdot s^{-2}}\)
Standard acceleration due to gravity \(g\) \(9.806\,65\) \(\mathrm{m\cdot s^{-2}}\)
Stefan Boltzmann constant \(\sigma\) \(5.670\,374\,419\times10^{-8}\) \(\mathrm{kg\cdot s^{-3}\cdot K^{-4}}\)
Vacuum permeability (magnetic constant) \(\mu_0\) \(1.256\,637\,061\,27(20)\times10^{-6}\) \(\mathrm{kg\cdot m\cdot A^{-2}\cdot s^{-2}}\)
Vacuum permittivity (electrical constant) \(\epsilon_0\) \(8.854\,187\,818\,8(14)\times10^{-12}\) \(\mathrm{A^2\cdot s^4\cdot kg^{-1}\cdot m^{-3}}\)
Rydberg constant \(R_\infty\) \(1.097\,373\,156\,815\,7(12)\times10^7\) \(\mathrm{m^{-1}}\)
Mass of the electron \(m_{\mathrm e}\) \(9.109\,383\,713\,9(28)\times10^{-31}\) \(\mathrm{kg}\)
Mass of the proton \(m_{\mathrm p}\) \(1.672\,621\,925\,95(52)\times10^{-27}\) \(\mathrm{kg}\)
Mass of the neutron \(m_{\mathrm n}\) \(1.674\,927\,500\,56(85)\times10^{-27}\) \(\mathrm{kg}\)
Atomic mass constant \(m_{\mathrm u}\) \(1.660\,539\,068\,92(52)\times10^{-27}\) \(\mathrm{kg}\)
Electronvolt \(\mathrm{eV}\) \(1.602\,176\,634\times10^{-19}\) \(\mathrm{kg\cdot m^2\cdot s^{-2}}\)

Official English text of the problem.

Answers

Here \(\Delta c=c_\ell-c_0\), and \(g_0\) is the gravitational acceleration given in the data sheet.

  • A.1 \[ \boxed{P_{\mathrm b}=P_0+\frac{2\sigma}{a}}. \]

  • A.2 \[ \boxed{a_{\mathrm c}=\frac{2\sigma c_0}{P_0(c_\ell-c_0)}}. \] For \(c_\ell=4c_0\), \[ \boxed{a_{\mathrm c}=3.1\times10^{-7}\,\mathrm m=0.31\,\mu\mathrm m}. \]

  • A.3 \[ \boxed{n_{\mathrm c}=\frac{4\pi P_0a^3}{3RT_0}}, \] \[ \boxed{a_{(1)}(t)=\sqrt{a_0^2+\frac{2DRT_0\Delta c}{P_0}t}}, \qquad \boxed{a_{(2)}(t)=a_0+\frac{KRT_0\Delta c}{P_0}t}. \] Model (2) fits the approximately linear growth: \[ \boxed{q_a\approx2.4\times10^{-4}\,\mathrm{m\,s^{-1}}}, \qquad \boxed{K\approx1.0\times10^{-4}\,\mathrm{m\,s^{-1}}}. \]

  • A.4 Buoyancy \(4\pi\rho_\ell g_0a^3/3\) acts upwards; Stokes drag \(6\pi\eta av\) and the negligible bubble weight act downwards. \[ \boxed{v(a)\simeq\frac{2\rho_\ell g_0a^2}{9\eta}}, \qquad \boxed{\eta\approx2.7\times10^{-3}\,\mathrm{Pa\,s}} \] from approximate measurements of Fig. 3.

  • A.5 \[ \boxed{a_{H_\ell}\simeq \left(\frac{27\eta q_aH_\ell}{2\rho_\ell g_0}\right)^{1/3} \approx4.5\times10^{-4}\,\mathrm m=0.45\,\mathrm{mm}}. \]

  • A.6 \[ \boxed{\frac{\mathrm dc_\ell}{\mathrm dt} =-\frac{18\pi\eta K H_\ell N_{\mathrm b}f_{\mathrm b}} {\rho_\ell g_0V_\ell}(c_\ell-c_0)}, \qquad \boxed{\tau=\frac{\rho_\ell g_0V_\ell} {18\pi\eta K H_\ell N_{\mathrm b}f_{\mathrm b}}}. \]

  • B.1 \[ \boxed{v_{\mathrm f}=\sqrt{\frac{2\sigma}{\rho_\ell h}}}. \]

  • B.2 \[ \boxed{f_0=\frac{1}{2\pi} \sqrt{\frac{\gamma P_0S^2}{m_{\mathrm p}V_0}}}. \]

  • B.3 \[ \boxed{a\approx5.3\times10^{-4}\,\mathrm m=0.53\,\mathrm{mm}}, \qquad \boxed{h\approx3.8\times10^{-6}\,\mathrm m=3.8\,\mu\mathrm m}. \]

  • C.1 \[ \boxed{P_{\mathrm i}(6^\circ\mathrm C)\approx4.81\,\mathrm{bar}}, \qquad \boxed{P_{\mathrm i}(20^\circ\mathrm C)\approx7.76\,\mathrm{bar}}. \]

  • C.2 Using the replacement pressures specified for this part: \[ \boxed{T_{\mathrm f}(6^\circ\mathrm C)\approx195.4\,\mathrm K \;(-77.7^\circ\mathrm C)}, \] \[ \boxed{T_{\mathrm f}(20^\circ\mathrm C)\approx184.4\,\mathrm K \;(-88.7^\circ\mathrm C)}. \] The true statements are 1 and 4: grey-white fog at \(6^\circ\mathrm C\), blue fog at \(20^\circ\mathrm C\).

  • C.3 \[ \boxed{H_{\mathrm c}\approx7.7\,\mathrm m}. \]

Solution

A.1

The Young–Laplace law gives the pressure jump across a curved liquid–gas interface: \[ P_{\mathrm b}-P_0 =\sigma\left(\frac1{R_1}+\frac1{R_2}\right). \] For a spherical bubble, both principal radii are \(a\). Thus \[ \boxed{P_{\mathrm b}=P_0+\frac{2\sigma}{a}}. \] There is one liquid–gas interface around the submerged bubble.

A.2

Henry's law at the bubble surface gives \[ c_{\mathrm b}=k_{\mathrm H}P_{\mathrm b} =k_{\mathrm H}\left(P_0+\frac{2\sigma}{a}\right) =c_0+\frac{2\sigma c_0}{P_0a}. \]

Gas diffuses into the bubble, making it grow, when \(c_\ell>c_{\mathrm b}\). The threshold therefore satisfies \[ c_\ell-c_0=\frac{2\sigma c_0}{P_0a_{\mathrm c}}, \] so \[ \boxed{a_{\mathrm c}=\frac{2\sigma c_0}{P_0(c_\ell-c_0)}}. \] For a supersaturated liquid, bubbles with \(a>a_{\mathrm c}\) grow, whereas smaller bubbles tend to dissolve.

With \(c_\ell=4c_0\), \[ a_{\mathrm c}=\frac{2\sigma}{3P_0} =\frac{2(47\times10^{-3})}{3(1.0\times10^5)} =3.13\times10^{-7}\,\mathrm m. \] Hence \[ \boxed{a_{\mathrm c}\approx0.31\,\mu\mathrm m}. \]

A.3

Under the stated approximation \(P_{\mathrm b}\simeq P_0\), the ideal gas law gives \[ P_0\frac{4\pi a^3}{3}=n_{\mathrm c}RT_0, \] and therefore \[ \boxed{n_{\mathrm c}=\frac{4\pi P_0a^3}{3RT_0}}. \]

The molar influx through the bubble surface is \[ \frac{\mathrm dn_{\mathrm c}}{\mathrm dt}=4\pi a^2j. \] Differentiating the ideal-gas expression at constant \(P_0,T_0\), \[ \frac{4\pi P_0a^2}{RT_0}\frac{\mathrm da}{\mathrm dt} =4\pi a^2j, \] which reduces to \[ \frac{\mathrm da}{\mathrm dt}=\frac{RT_0}{P_0}j. \]

For the short growth experiment, take the bulk concentration as constant and use \(c_{\mathrm b}\simeq c_0\).

For model (1), \[ \frac{\mathrm da}{\mathrm dt} =\frac{DRT_0(c_\ell-c_0)}{P_0a}. \] Integrating with \(a(0)=a_0\), \[ \boxed{a(t)= \sqrt{a_0^2+\frac{2DRT_0(c_\ell-c_0)}{P_0}t}}. \] This predicts a decreasing growth rate and an asymptotic \(t^{1/2}\) dependence.

For model (2), \[ \frac{\mathrm da}{\mathrm dt} =\frac{KRT_0(c_\ell-c_0)}{P_0}=q_a, \] so \[ \boxed{a(t)=a_0+\frac{KRT_0(c_\ell-c_0)}{P_0}t}. \]

Figure 2 shows an approximately constant slope, supporting model (2). Reading roughly \(a=40\,\mu\mathrm m\) at \(t=0\) and \(a=270\,\mu\mathrm m\) at \(t=0.95\,\mathrm s\), \[ q_a\approx\frac{(270-40)\times10^{-6}}{0.95} \approx2.4\times10^{-4}\,\mathrm{m\,s^{-1}}. \]

At \(20^\circ\mathrm C\), \[ T_0=293.15\,\mathrm K,\qquad c_0=k_{\mathrm H}P_0=33\,\mathrm{mol\,m^{-3}}, \] and \(c_\ell-c_0\simeq3c_0=99\,\mathrm{mol\,m^{-3}}\). Hence \[ K=\frac{P_0q_a}{RT_0(c_\ell-c_0)} \approx \frac{10^5(2.4\times10^{-4})} {8.31446(293.15)(99)}. \] Thus \[ \boxed{K\approx1.0\times10^{-4}\,\mathrm{m\,s^{-1}}}. \]

A.4

Let \(\mathbf u_z\) point vertically upwards. The forces are buoyancy, \[ \mathbf F_{\mathrm B} =\rho_\ell\frac{4\pi a^3}{3}g_0\,\mathbf u_z, \] Stokes drag, \[ \mathbf F_{\mathrm D}=-6\pi\eta av\,\mathbf u_z, \] and the bubble's weight, \[ \mathbf W=-\rho_{\mathrm g}\frac{4\pi a^3}{3}g_0\,\mathbf u_z. \]

At terminal velocity their sum vanishes: \[ 6\pi\eta av =(\rho_\ell-\rho_{\mathrm g})\frac{4\pi a^3}{3}g_0. \] Since \(\rho_{\mathrm g}\ll\rho_\ell\), \[ \boxed{v(a)=\frac{2(\rho_\ell-\rho_{\mathrm g})g_0a^2}{9\eta} \simeq\frac{2\rho_\ell g_0a^2}{9\eta}}. \]

Adjacent bubbles follow the same trajectory with an age difference \[ \Delta t=\frac1{f_{\mathrm b}}. \] Their centre-to-centre separation \(\Delta z\) therefore gives \[ v\simeq\frac{\Delta z}{\Delta t}=f_{\mathrm b}\Delta z, \] evaluated approximately at the mean radius of the pair.

Using the scale in Fig. 3, the two bubbles near the right-hand end give approximately \[ a\simeq0.24\,\mathrm{mm},\qquad \Delta z\simeq2.3\,\mathrm{mm}. \] Consequently, \[ v\simeq20(2.3\times10^{-3}) =4.6\times10^{-2}\,\mathrm{m\,s^{-1}}, \] and \[ \eta\simeq\frac{2\rho_\ell g_0a^2}{9f_{\mathrm b}\Delta z} =\frac{2(10^3)(9.80665)(0.24\times10^{-3})^2} {9(20)(2.3\times10^{-3})}. \] This gives the graphical estimate \[ \boxed{\eta\approx2.7\times10^{-3}\,\mathrm{Pa\,s}}. \]

A.5

Combine the terminal rise speed with the constant radial growth rate: \[ \frac{\mathrm dz}{\mathrm dt} =\frac{2\rho_\ell g_0}{9\eta}a^2, \qquad \frac{\mathrm da}{\mathrm dt}=q_a. \] Eliminating time, \[ \frac{\mathrm dz}{\mathrm da} =\frac{2\rho_\ell g_0}{9\eta q_a}a^2. \] Integrating from the bottom to the free surface, \[ H_\ell =\frac{2\rho_\ell g_0}{27\eta q_a} \left(a_{H_\ell}^3-a_0^3\right). \]

Thus the expression retaining the initial radius is \[ a_{H_\ell} =\left(a_0^3+\frac{27\eta q_aH_\ell}{2\rho_\ell g_0}\right)^{1/3}. \] With \(a_{H_\ell}\gg a_0\), \[ \boxed{a_{H_\ell}\simeq \left(\frac{27\eta q_aH_\ell}{2\rho_\ell g_0}\right)^{1/3}}. \]

Using \(H_\ell=0.10\,\mathrm m\), \(q_a\simeq2.4\times10^{-4}\,\mathrm{m\,s^{-1}}\), and the viscosity estimated above, \[ \boxed{a_{H_\ell}\approx4.5\times10^{-4}\,\mathrm m =0.45\,\mathrm{mm}}. \]

A.6

Use the quasi-stationary description of the bubble train on the concentration-depletion timescale. The liquid is represented by a uniform bulk concentration \(c_\ell(t)\), and changes in the gas inventory of bubbles still rising are neglected in the loss balance.

Each bubble reaching the surface carries \[ n_{\mathrm{out}} =\frac{4\pi P_0}{3RT_0}a_{H_\ell}^3. \] The result of A.5, with negligible \(a_0\), gives \[ n_{\mathrm{out}} =\frac{4\pi P_0}{3RT_0} \frac{27\eta q_aH_\ell}{2\rho_\ell g_0} =\frac{18\pi\eta H_\ell P_0}{\rho_\ell g_0RT_0}q_a. \]

As the liquid loses dissolved gas, model (2) gives \[ q_a(t)=\frac{KRT_0}{P_0}\bigl(c_\ell(t)-c_0\bigr). \] Therefore \[ n_{\mathrm{out}} =\frac{18\pi\eta K H_\ell}{\rho_\ell g_0} (c_\ell-c_0). \]

There are \(N_{\mathrm b}f_{\mathrm b}\) bubbles emitted per unit time. Conservation of \(\mathrm{CO}_2\) gives \[ V_\ell\frac{\mathrm dc_\ell}{\mathrm dt} =-N_{\mathrm b}f_{\mathrm b}n_{\mathrm{out}}, \] hence \[ \boxed{ \frac{\mathrm dc_\ell}{\mathrm dt} =-\frac{18\pi\eta K H_\ell N_{\mathrm b}f_{\mathrm b}} {\rho_\ell g_0V_\ell}(c_\ell-c_0) }. \]

The solution is \[ c_\ell(t)=c_0+\bigl[c_\ell(0)-c_0\bigr]e^{-t/\tau}, \] where \[ \boxed{\tau= \frac{\rho_\ell g_0V_\ell} {18\pi\eta K H_\ell N_{\mathrm b}f_{\mathrm b}}}. \] It is the excess concentration above \(c_0\) that decays exponentially.

B.1

During \(\mathrm dt\), the retracting rim sweeps out an annulus of area \[ \mathrm dA=2\pi r v_{\mathrm f}\,\mathrm dt. \] The film has two liquid–gas surfaces, so the decrease in surface energy is \[ -\mathrm dE_{\mathrm s}=2\sigma\,\mathrm dA. \] By the stated dissipation rule, half of this becomes kinetic energy: \[ \mathrm dE_{\mathrm k}=\sigma\,\mathrm dA. \]

The newly accumulated mass is \[ \mathrm dm=\rho_\ell h\,\mathrm dA. \] Since the rim speed remains constant, its kinetic-energy increase is \[ \mathrm dE_{\mathrm k} =\frac12v_{\mathrm f}^2\,\mathrm dm =\frac12\rho_\ell h v_{\mathrm f}^2\,\mathrm dA. \] Equating the two expressions, \[ \frac12\rho_\ell h v_{\mathrm f}^2=\sigma, \] so \[ \boxed{v_{\mathrm f}=\sqrt{\frac{2\sigma}{\rho_\ell h}}}. \]

B.2

An upward displacement \(z\) of the piston changes the enclosed gas volume to \[ V=V_0+Sz. \] For reversible adiabatic compression or expansion, \[ PV^\gamma=P_0V_0^\gamma. \] Thus \[ P=P_0\left(1+\frac{Sz}{V_0}\right)^{-\gamma}. \] For \(|Sz|\ll V_0\), \[ P\simeq P_0\left(1-\gamma\frac{Sz}{V_0}\right). \]

Neglecting the piston weight as specified, its equation of motion is \[ m_{\mathrm p}\ddot z=(P-P_0)S =-\frac{\gamma P_0S^2}{V_0}z. \] This is simple harmonic motion with \[ \omega_0^2=\frac{\gamma P_0S^2}{m_{\mathrm p}V_0}. \] Therefore \[ \boxed{f_0=\frac{1}{2\pi} \sqrt{\frac{\gamma P_0S^2}{m_{\mathrm p}V_0}}}. \]

B.3

For the bubble, \[ S=\pi r^2,\qquad V_0=\frac{4\pi a^3}{3},\qquad m_{\mathrm p}=\frac{8\rho_{\mathrm g}r^3}{3}. \] Substitution into B.2 gives \[ f_0^2 =\frac{1}{4\pi^2} \frac{\gamma P_0\pi^2r^4} {\left(8\rho_{\mathrm g}r^3/3\right) \left(4\pi a^3/3\right)} =\frac{9\gamma P_0r}{128\pi\rho_{\mathrm g}a^3}. \]

Thus \(f_0\propto\sqrt r\), and the maximum frequency occurs at \(r=r_{\mathrm c}\). Using the given expression for \(r_{\mathrm c}\), \[ f_{\max}^2 =\frac{9\gamma P_0}{128\pi\rho_{\mathrm g}a^3} \frac{2a^2}{\sqrt3} \sqrt{\frac{\rho_\ell g_0}{\sigma}} =\frac{3\sqrt3\,\gamma P_0}{64\pi\rho_{\mathrm g}a} \sqrt{\frac{\rho_\ell g_0}{\sigma}}. \] Therefore \[ \boxed{ a=\frac{3\sqrt3\,\gamma P_0} {64\pi\rho_{\mathrm g}f_{\max}^2} \sqrt{\frac{\rho_\ell g_0}{\sigma}} }. \]

With \(f_{\max}=4.0\times10^4\,\mathrm{Hz}\), \[ a= \frac{3\sqrt3(1.3)(10^5)} {64\pi(1.8)(4.0\times10^4)^2} \sqrt{\frac{10^3(9.80665)}{47\times10^{-3}}} =5.33\times10^{-4}\,\mathrm m. \] Hence \[ \boxed{a\approx0.53\,\mathrm{mm}}. \]

The final aperture radius is \[ r_{\mathrm c} =\frac{2}{\sqrt3}a^2 \sqrt{\frac{\rho_\ell g_0}{\sigma}} \approx1.50\times10^{-4}\,\mathrm m. \] Because the aperture opens at constant speed, \[ v_{\mathrm f}=\frac{r_{\mathrm c}}{t_{\mathrm b}}, \qquad t_{\mathrm b}=3\times10^{-2}\,\mathrm{ms} =3\times10^{-5}\,\mathrm s, \] so \[ v_{\mathrm f}\approx5.0\,\mathrm{m\,s^{-1}}. \]

Finally, B.1 gives \[ h=\frac{2\sigma}{\rho_\ell v_{\mathrm f}^2} =\frac{2\sigma t_{\mathrm b}^2}{\rho_\ell r_{\mathrm c}^2} \approx3.77\times10^{-6}\,\mathrm m. \] Thus \[ \boxed{h\approx3.8\,\mu\mathrm m}. \]

C.1

The amounts of dissolved and gaseous \(\mathrm{CO}_2\) are, respectively, \[ n_{\mathrm L}=k_{\mathrm H}P_{\mathrm i}V_{\mathrm L}, \qquad n_{\mathrm G}=\frac{P_{\mathrm i}V_{\mathrm G}}{RT_0}. \] Conservation of the total amount gives \[ n_{\mathrm T} =P_{\mathrm i}\left(k_{\mathrm H}V_{\mathrm L} +\frac{V_{\mathrm G}}{RT_0}\right). \] Consequently, \[ \boxed{ P_{\mathrm i} =\frac{n_{\mathrm T}} {k_{\mathrm H}V_{\mathrm L}+V_{\mathrm G}/(RT_0)} }. \]

Use \[ V_{\mathrm L}=7.50\times10^{-4}\,\mathrm{m^3}, \qquad V_{\mathrm G}=2.50\times10^{-5}\,\mathrm{m^3}. \]

At \(6^\circ\mathrm C\), \(T_0=279.15\,\mathrm K\): \[ P_{\mathrm i} =\frac{0.2} {(5.4\times10^{-4})(7.50\times10^{-4}) +(2.50\times10^{-5})/(8.31446\times279.15)} \approx4.81\times10^5\,\mathrm{Pa}. \]

At \(20^\circ\mathrm C\), \(T_0=293.15\,\mathrm K\): \[ P_{\mathrm i} =\frac{0.2} {(3.3\times10^{-4})(7.50\times10^{-4}) +(2.50\times10^{-5})/(8.31446\times293.15)} \approx7.76\times10^5\,\mathrm{Pa}. \]

These are absolute pressures: \[ \boxed{P_{\mathrm i}(6^\circ\mathrm C)\approx4.81\,\mathrm{bar}}, \qquad \boxed{P_{\mathrm i}(20^\circ\mathrm C)\approx7.76\,\mathrm{bar}}. \]

C.2

For this part, the problem specifies the replacement pressures \[ P_{\mathrm i}(6^\circ\mathrm C)=4.69\,\mathrm{bar}, \qquad P_{\mathrm i}(20^\circ\mathrm C)=7.45\,\mathrm{bar}. \]

For reversible adiabatic expansion of an ideal gas, \[ PV^\gamma=\text{constant}, \qquad TV^{\gamma-1}=\text{constant}. \] Eliminating \(V\), and taking the final pressure to be \(P_0\), \[ \boxed{ T_{\mathrm f}=T_0 \left(\frac{P_0}{P_{\mathrm i}}\right)^{(\gamma-1)/\gamma} }. \]

Thus \[ T_{\mathrm f}(6^\circ\mathrm C) =279.15\left(\frac1{4.69}\right)^{0.3/1.3} \approx195.4\,\mathrm K, \] and \[ T_{\mathrm f}(20^\circ\mathrm C) =293.15\left(\frac1{7.45}\right)^{0.3/1.3} \approx184.4\,\mathrm K. \]

To determine whether solid \(\mathrm{CO}_2\) forms, find the sublimation-equilibrium temperature at \(P_0\). Setting \(P_{\mathrm{sat}}^{\mathrm{CO}_2}=P_0\), \[ 0=A-\frac{B}{T_{\mathrm s}+C}, \] so \[ T_{\mathrm s}=\frac BA-C =\frac{1300}{6.81}+3.49 \approx194.4\,\mathrm K. \]

For the initially cold bottle, \[ 195.4\,\mathrm K>T_{\mathrm s}. \] Indeed, the given vapor-pressure expression yields \[ P_{\mathrm{sat}}^{\mathrm{CO}_2}(195.4\,\mathrm K) \approx1.09\,\mathrm{bar}>P_0. \] The gas does not reach solid–gas saturation during this expansion. According to the stated alternatives, grey-white fog forms.

For the initially warmer bottle, \[ 184.4\,\mathrm K<T_{\mathrm s}, \] and \[ P_{\mathrm{sat}}^{\mathrm{CO}_2}(184.4\,\mathrm K) \approx0.422\,\mathrm{bar}<P_0. \] The phase-change-free expansion would produce supersaturated \(\mathrm{CO}_2\), so solid crystals form, giving blue fog.

Therefore \[ \boxed{\text{Statements 1 and 4 are true.}} \] The calculated \(T_{\mathrm f}\) values are the requested hypothetical temperatures without phase change; solid formation modifies the actual thermal evolution in the warm-bottle case.

C.3

Use the specified pressure at \(6^\circ\mathrm C\): \[ P_{\mathrm i}=4.69\times10^5\,\mathrm{Pa}. \] Let \(x\) be the upward displacement of the cork from its initial position, and let \[ S=\frac{\pi d^2}{4} \] be its cross-sectional area.

While \(0\le x\le\ell_0\), the contact area is \[ A(x)=\pi d(\ell_0-x), \] so the friction force is \[ F_{\mathrm{fr}}(x)=\alpha\pi d(\ell_0-x). \]

Initially, the net pressure force nearly balances friction: \[ (P_{\mathrm i}-P_0)S\simeq\alpha\pi d\ell_0. \] The cork's weight is only \(0.098\,\mathrm N\), compared with an initial net pressure force of about \(94\,\mathrm N\), so it can be neglected when estimating \(\alpha\). Hence \[ \boxed{ \alpha\simeq\frac{(P_{\mathrm i}-P_0)d}{4\ell_0} } \approx6.64\times10^4\,\mathrm{Pa}. \]

The rapid expansion involves the gas initially in the headspace. Its volume and pressure during the cork's motion are \[ V(x)=V_{\mathrm G}+Sx, \qquad P(x)=P_{\mathrm i} \left(\frac{V_{\mathrm G}}{V_{\mathrm G}+Sx}\right)^\gamma. \] When the cork leaves the neck, \[ V_{\mathrm e}=V_{\mathrm G}+S\ell_0. \]

The work done by the internal gas is \[ W_{\mathrm{gas}} =\int_0^{\ell_0}P(x)S\,\mathrm dx =\int_{V_{\mathrm G}}^{V_{\mathrm e}} P_{\mathrm i}\left(\frac{V_{\mathrm G}}V\right)^\gamma\mathrm dV, \] giving \[ W_{\mathrm{gas}} =\frac{P_{\mathrm i}V_{\mathrm G}}{\gamma-1} \left[ 1-\left(\frac{V_{\mathrm G}}{V_{\mathrm e}}\right)^{\gamma-1} \right]. \]

The work against atmospheric pressure is \[ W_{\mathrm{atm}}=P_0S\ell_0, \] and the energy dissipated by friction is \[ W_{\mathrm{fr}} =\int_0^{\ell_0}\alpha\pi d(\ell_0-x)\,\mathrm dx =\frac12\alpha\pi d\ell_0^2 \simeq\frac12(P_{\mathrm i}-P_0)S\ell_0. \]

After the cork exits, the net pressure force is neglected as instructed. Neglecting air resistance, all the remaining mechanical energy becomes gravitational potential energy at the highest point. Taking \(H_{\mathrm c}\) from the initial cork position, \[ mg_0H_{\mathrm c} =W_{\mathrm{gas}}-W_{\mathrm{atm}}-W_{\mathrm{fr}}. \] Therefore \[ \boxed{ H_{\mathrm c}= \frac{1}{mg_0} \left\{ \frac{P_{\mathrm i}V_{\mathrm G}}{\gamma-1} \left[ 1-\left(\frac{V_{\mathrm G}} {V_{\mathrm G}+S\ell_0}\right)^{\gamma-1} \right] -P_0S\ell_0 -\frac12(P_{\mathrm i}-P_0)S\ell_0 \right\}. } \]

Numerically, \[ S=2.5447\times10^{-4}\,\mathrm{m^2}, \qquad V_{\mathrm e}=3.1362\times10^{-5}\,\mathrm{m^3}, \] and \[ W_{\mathrm{gas}}\approx2.570\,\mathrm J,\qquad W_{\mathrm{atm}}\approx0.636\,\mathrm J,\qquad W_{\mathrm{fr}}\approx1.174\,\mathrm J. \] Thus \[ H_{\mathrm c} \approx\frac{2.570-0.636-1.174}{0.010(9.80665)} \approx7.75\,\mathrm m. \] To sensible precision, \[ \boxed{H_{\mathrm c}\approx7.7\,\mathrm m}. \]

If the height is measured from the cork's position when it clears the neck, subtract \(\ell_0=0.025\,\mathrm m\); the rounded answer remains \(7.7\,\mathrm m\).

The solution was checked against the official solution.