Calculating time to reduce alcohol in wine using heating method

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The discussion revolves around finding an effective method to reduce ethanol content in wine for cooking purposes while minimizing flavor degradation. The first-order reaction model is initially used to estimate alcohol removal, but it fails to account for the energy required for evaporation. Participants suggest that practical methods like simple heating or reverse osmosis might be more effective than theoretical calculations. Concerns are raised about the accuracy of the proposed calculations and the complexity of the process, with some advocating for straightforward cooking techniques instead. Ultimately, the consensus leans toward experimenting with heating wine to achieve the desired alcohol reduction without overcomplicating the approach.
  • #31
Chestermiller said:
You don’t know much about distillation,, do you? As a ChE, my advice to you as an EE is to stick to Ohm's law.
Chestermiller said:
Working with a phase diagram like this is very basic stuff to us Chemical Engineers.
One of the things I really like about PF is the ability to learn about subjects in which I lack expertise. I very much appreciate all of you that take the time to educate people outside of your area of expertise.

OTOH, you don't have to help others if you don't want to. But if you do want to teach, it's not a great approach to imply they shouldn't ask questions or shouldn't risk being wrong. It's not a crime to talk about "reverse distillation", even though that's not the description that ChEs would use.

In any case, we are aware we aren't Chemical Engineers, but thanks for the reminder.
 
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  • #32
DaveE said:
Hum... Now I'm confused. Isn't it true that at 1atm, 202F, EtOH concentration in the liquid can't fall below 7.5% in equilibrium?
Yes, that’s what I said. At 202, it is 7.5% in the liquid.
DaveE said:
Now, if you blew fresh air in you wouldn't be at equilibrium. Does that mean you can reduce the concentration lower, or are you just removing H2O and EtOH in proportion to maintain the same concentration?
This diagram is for the binary system water and alcohol; no air.
 
  • #33
Chestermiller said:
This diagram is for the binary system water and alcohol; no air.
Oh. Yes you're right, I didn't know that part.
At a basic level, what difference would a bunch of Nitrogen molecules make?
Can you treat vapor pressures separately (non-reactive, of course), like superposition in linear systems?
 
  • #34
Chestermiller said:
This diagram is for the binary system water and alcohol; no air.

DaveE said:
Oh. Yes you're right, I didn't know that part.

But if the purpose is to remove ethanol from the liquid why would you maintain the the alcohol vapor eqilibrium??? Take the lid off the boiling pot and let the ethanol diffuse away. Let the volume in the kettle decrease until 11% of the liquid is gone and/or the temperature has reached the value stipulated on the chart Equilibrium neither required nor requested.
I don't like to mix efficient engineering with physics pondering although I love them equally.
 
  • #35
hutchphd said:
But if the purpose is to remove ethanol from the liquid why would you maintain the the alcohol vapor eqilibrium??? Take the lid off the boiling pot and let the ethanol diffuse away. Let the volume in the kettle decrease until 11% of the liquid is gone and/or the temperature has reached the value stipulated on the chart Equilibrium neither required nor requested.
I don't like to mix efficient engineering with physics pondering although I love them equally.
Yes, which leads to my next/previous question.
At the liquid-vapor interface, is it always in equilibrium at the molecular level, no matter how much you try to blow fresh air onto it?
 
  • #36
Equilibrium case is one for which exact calculations are possible, so it gives a good reference point. As in every other practical case (be it in chemistry of physics) real world is more complicated, typically to the point where it is easier to measure than to calculate.

So yes, this is a spherical cow diagram. But it is the best thing we have to analyze the situation, and it will tell us what are limits, what is possible and what is not (just like energy conservation makes discussions about over unity engines a moot).
 
  • #37
Here is a simple model to begin to work with.

Let m be the total number of moles of ETOH and water in the tank at any time, let x be the mole fraction ETOH, and let ##\dot{m}_I## be the molar flow rate of inert gas (insoluble also) bubbled through the liquid. Assume the liquid is agitated enough and the depth of the liquid is sufficient for the bubbles too reach vapor-liquid equilibrium with the liquid currently in the tank. Assume also that heat is added to the system at such a rate that the liquid remains at constant temperature T throughout the process. Let the total pressure of the system by constant at ##P_T##, with the pure inert gas also furnished at this pressure and temperature T.

We will temporarily assume that the liquid solution is ideal such that Raoult's law is obeyed:$$p_{A}=xP^*_A(T)$$$$p_{W}=(1-x)P^*_W(T)$$where the ##P^*(T)##'s are the equilibrium vapor pressures of pure water and ETOH at temperature T,, and the p's are the partial pressures iii the vapor.

Based on these considerations, the rate of change of the total number of moles of liquid in the tank any time is. $$\frac{dm}{dt}=-\frac{(p_A+p_W)}{P_T-(p_A+p_W)}\dot{m}_I\tag{1}$$The rate of change of the number of moles of ETOH in the tank is $$\frac{d(mx)}{dt}=m\frac{dx}{dt}+x\frac{dm}{dt}=-\frac{p_A}{P_T-(p_A+p_W)}\dot{m}_I$$or $$\frac{dx}{dt}=x(1-x)\frac{(P^*_W-P^*_A)}{P_T-(p_A+p_W)}\frac{\dot{m}_I}{m}\tag{2}$$Eqns. 1 and 2 can be integrated with respect to time, subject to the imposed initial conditions.
 
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  • #38
It ends up a rate problem but be aware that the atoms in the gas move roughly at the speed of sound. As for diffusion rates they are typically ##cm^2 /s## for atmospheric gasses. some small amounts will return, There a various laws of diffusion, but the rate at a rolling boil will not be significant here I believe.

Edit: Of course @Chestermiller knows the answer which would have taken me an hour at least!!. Notice how rate gets very large near the boiling point T of ethanol.
 
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  • #39
Chestermiller said:
Here is a simple model to begin to work with.
Thanks! I need to think about this some.

So if I were to add a third inert substance can I just extend these equations like this:

$$\frac{dm}{dt}=-\frac{(p_A+p_W+p_C)}{P_T-(p_A+p_W+p_C)}\dot{m}_I\tag{1}$$
 
  • #40
DaveE said:
Thanks! I need to think about this some.

So if I were to add a third inert substance can I just extend these equations like this:

$$\frac{dm}{dt}=-\frac{(p_A+p_W+p_C)}{P_T-(p_A+p_W+p_C)}\dot{m}_I\tag{1}$$
That would apply only if the 3rd component were present in the wine or soluble in the wine. Otherwise, I have already assumed that an insoluble gas, such as N2, is being bubbled through the wine.

I'm wondering what a good temperature would be for the operation. I was thinking of something like 78.5 C, such that, at 1 atm. total pressure, the initial partial pressures of A, W, and N2 in the exit gas would be about 0.15 atm, 0.4 atm., and 0.45 atm. Thoughts?
 
  • #41
Chestermiller said:
That would apply only if the 3rd component were present in the wine or soluble in the wine. Otherwise, I have already assumed that an insoluble gas, such as N2, is being bubbled through the wine.
OK, so molecules that won't transition across the liquid-vapor barrier can be ignored, except for their effect on the total pressure. That makes sense.
 
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  • #42
Hey folks, seems that by chipping at this, there is possibly a closed form analytical solution in the works. I will still move forward with the experimental approach. I mentioned earlier that I purchased a hydrometer.

The downside to the hydrometer is that it requires a 250mL volume of the wine to determine the ABV. That is disruptive during the heating process and will not provide accurate results since I would like to test for ABV during heating at 10 minute? intervals. Today, I purchased a Digital Refractometer for Wine/Grape Measurements (% Brix & Potential Alcohol). The Brix scale is used to measure sugar content.

https://www.thomassci.com/Instrumen...rape-Measurements-Brix-And-Potential-Alcohol#

This device will allow me to pipette a small quantity (2-3 drops) into the instrument to get the ABV at my desired sampling intervals.

Since the rain is clearing here, and the temperatures outside are starting to be seasonal, I can thinking about setting this experiment up on my patio. (don't want to smell up the house) I have a single burner butane stove that should work fine as the heat source.

The vessel will be a 12" diameter, 4.5 quart stock pot. I'll use my fast response K thermocouples for T measurement. The downside is that the meter resolution for temperature is only 1C. Before I start this, I'll pop over to Lab Pro and purchase appropriate small sample containers for this experiment.

I am still thinking of using a process temperature of ~83C. Any guesses on the time to reduce the Shaoxing wine from a C0 = .15 to a Cf =. 04? Any bets on the time? My guess from my now discredited calculations is ~ 50 minutes.

 
  • #43
ArtZ said:
Hey folks, seems that by chipping at this, there is possibly a closed form analytical solution in the works. I will still move forward with the experimental approach. I mentioned earlier that I purchased a hydrometer.

The downside to the hydrometer is that it requires a 250mL volume of the wine to determine the ABV. That is disruptive during the heating process and will not provide accurate results since I would like to test for ABV during heating at 10 minute? intervals. Today, I purchased a Digital Refractometer for Wine/Grape Measurements (% Brix & Potential Alcohol). The Brix scale is used to measure sugar content.

https://www.thomassci.com/Instrumen...rape-Measurements-Brix-And-Potential-Alcohol#

This device will allow me to pipette a small quantity (2-3 drops) into the instrument to get the ABV at my desired sampling intervals.

Since the rain is clearing here, and the temperatures outside are starting to be seasonal, I can thinking about setting this experiment up on my patio. (don't want to smell up the house) I have a single burner butane stove that should work fine as the heat source.

The vessel will be a 12" diameter, 4.5 quart stock pot. I'll use my fast response K thermocouples for T measurement. The downside is that the meter resolution for temperature is only 1C. Before I start this, I'll pop over to Lab Pro and purchase appropriate small sample containers for this experiment.

I am still thinking of using a process temperature of ~83C. Any guesses on the time to reduce the Shaoxing wine from a C0 = .15 to a Cf =. 04? Any bets on the time? My guess from my now discredited calculations is ~ 50 minutes.

Are you counting the amount of time it takes to heat up a gallon of wine from 20 C to 83 C?
 
  • #44
In a former life, I designed, built, and calibrated 'Breath Interlocks' - a device added to vehicles for those convicted of drunk driving (in many U.S. states). The calibration process used a 'wet-bath' simulator - air was bubbled through a defined ethanol/water solution at a controlled temperature. The product gas was used to calibrate the devices.
From that experience, I can say with confidence that Raoult's Law is of limited utility in the case of low concentration ethanol/water solutions. The inter-molecular forces (in solution) make a mess of the 'expected' ethanol fraction in the gas at a given solution concentration and also cause non-linear (WRT ethanol concentration) behavior over a range of ethanol concentrations.

Caveat: This is true for low ethanol/water concentrations - it is entirely possible that elevated ethanol concentrations behave in a more 'ideal' manner.
 
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  • #45
Dullard said:
In a former life, I designed, built, and calibrated 'Breath Interlocks' - a device added to vehicles for those convicted of drunk driving (in many U.S. states). The calibration process used a 'wet-bath' simulator - air was bubbled through a defined ethanol/water solution at a controlled temperature. The product gas was used to calibrate the devices.
From that experience, I can say with confidence that Raoult's Law is of limited utility in the case of low concentration ethanol/water solutions. The inter-molecular forces (in solution) make a mess of the 'expected' ethanol fraction in the gas at a given solution concentration and also cause non-linear (WRT ethanol concentration) behavior over a range of ethanol concentrations.

Caveat: This is true for low ethanol/water concentrations - it is entirely possible that elevated ethanol concentrations behave in a more 'ideal' manner.
Does this more ideal behavior include the region of the azeotrope?
 
  • #46
I don't know. My (worthless) guess is 'yes.' My (perhaps) more useful guess is that empirical data for ethanol/water is available (CRC, Perry's...)
 
  • #47
Chestermiller said:
Are you counting the amount of time it takes to heat up a gallon of wine from 20 C to 83 C?
I guess that I should. Under more controlled conditions, I could rely on E = m *Cp * T2-T1. Since a Joule = W*s, I could calculate that time. Since I don't have a hotplate with a known output power (a butane burner) I'll have to include the ramp time in the total time.
 
  • #48
Dullard said:
I don't know. My (worthless) guess is 'yes.' My (perhaps) more useful guess is that empirical data for ethanol/water is available (CRC, Perry's...)
The azeotrope is a non-ideal solution effect.
 
  • #49
Aaah... my CRC Handbook. I may have given it away. Good thought. It has tables for binary and ternary mixtures. Maybe I can locate a copy online.
 
  • #50
Engineering toolbox site has plenty of tables, I will be surprised if they don't have ethanol/water data.
 
  • #51
If it were me I'd look at this from a volume perspective. That is, approximately how much reduction of the wine volume by boiling will result in a reduction of the alcohol concentration to, say, 25% of it's original value. I suspect you'd have to reduce the wine by quite a bit.

Maybe a better tack is to either dilute the wine into 3 parts water or simply use one fourth as much wine in your recipes. It won't be the same, for sure, but wine cooked for however long you'll need to reduce the alcohol by 3/4 isn't going to be the same either.
 
  • #52
Borek said:
Engineering toolbox site has plenty of tables, I will be surprised if they don't have ethanol/water data.
Lots of good info on Engineering re: thermophysical properties, thanks. However nothing about EtOH evaporation from a water mixture during heating.
 
  • #53
JT Smith said:
If it were me I'd look at this from a volume perspective. That is, approximately how much reduction of the wine volume by boiling will result in a reduction of the alcohol concentration to, say, 25% of it's original value. I suspect you'd have to reduce the wine by quite a bit.

Maybe a better tack is to either dilute the wine into 3 parts water or simply use one fourth as much wine in your recipes. It won't be the same, for sure, but wine cooked for however long you'll need to reduce the alcohol by 3/4 isn't going to be the same either.
The Shaoxing wine that I want to do the EtOH reduction has a very distinctive bouquet. If a recipe that I would use the Shaoxing already calls for a large amount of liquid, your your strategy may work. For a stir fry though, adding a tablespoon of Shaoxing as the stir fry cooks may result in a residual alcohol taste.
 
  • #54
This is an attempt to map out a math model for the system of liquid wine in a pot open to the atmosphere at 1 bar, with a horizontal liquid surface of area A. The entire wine is assumed to have been brought to the operating temperature T, and the air above in the pot is also at T. So the time to preheat to the operating temperature is not included.

All the wine is assumed to be at constant water and ethanol concentrations spatially, except, possibly, in close proximity to the interface with the air (see below). The overall mass balances for the wine, and the mass balance for the ethanol component are written as follows:
$$\frac{dm}{dt}=-\left(k_W\frac{p_W}{RT}+k_E\frac{p_E}{RT}\right)A\tag{1}$$
$$\frac{d(mx)}{dt}=-k_E\frac{p_E}{RT}A\tag{2}$$where m is the total moles of wine in the tank, x is the mole fraction ethanol, the k's are the mass transfer coefficients of ethanol and water (cm/sec) to the air, the p's are the partial pressures of ethanol and water at the interface. Implicit in these equations is that the partial pressures of ethanol and water in the far-field air are negligible. The mass transfer coefficients are the largest uncertainties in this analysis, since I have not yet found correlations for these as a function of the operating conditions.

If we subtract Eqn. 1 from Eqn. 2, we obtain $$m\frac{dx}{dt}=-k_E\frac{p_E(1-x)}{RT}A+k_W\frac{p_Wx}{RT}A\tag{3}$$Eqns. 1 and 3 are our starting equations.

Let's next next turn to the Vapor-Liquid Equilibrium behavior which applies at the interface between the liquid and vapor. The first thing I wan to call attention to is the relationship between the equilibrium vapor pressure of pure ethanol and pure water. Over the temperature range of interest (60 C to 100 C), the equilibrium vapor pressure is almost exactly equal to 2.2 times the equilibrium vapor pressure of water: $$P^*_{E}(T)=2.2P^*_W(T)\tag{4}$$
@Dullard has pointed out that the VLE behavior of the ethanol-water system does not satisfy Raoult's Law. However, in the present region of system operation, at law mole fractions of ethanol (x < 0.1), the VLE behavior of this non-ideal system will approach: $$p_w=P^*_W(1-x)\tag{5}$$$$p_E=\gamma P^*_Ex\tag{6}$$where #\gamma# is the infinite dilution activity coefficient of ethanol in water. Experimental values of ##\gamma## reported in the literature (http://www.ddbst.com/en/EED/ACT/ACT Ethanol;Water.php) are approximately 3.2. Therefore, combining Eqns. 5 and 6 gives: $$p_E=7.0P^*_Wx\tag{7}$$The figure below shows observed VLE behavior for the binary system ethanol-water at combined pressures ranging from 1/8 bar to 1/2 bar.

1678964745335.png

Eqns. 4 and 7 describe this behavior very accurately at ethanol mole fractions < 0.1. Therefore, we can confidently use these equations in our model calculation.

If we now substitute Eqns. 4 and 7 into Eqns. 1 and 3, we obtain:
$$\frac{dm}{dt}=-(k_W(1-x)+7k_Ex)A\frac{P^*_W}{RT}\tag{8}
$$$$m\frac{dx}{dt}=-(7k_E-k_W)Ax(1-x)\frac{P^*_W}{RT}\tag{9}$$
In Eqn. 9, if we neglect the value of x compared to 1, and neglect the change in m (as described In Eqn. 8) relative to its initial value ##m_0##, the equation reduces to $$\frac{d\ln{x}}{dt}=-\frac{1}{\tau}\tag{10}$$where the characteristic decay time ##\tau## is given by$$\tau=\frac{m_0}{(7k_E-k_W)A\frac{P^*_W}{RT}}\tag{11}$$

Based on this final approximate equation, the only thing left to do now is to estimate values of the mass transfer coefficients and provide an initial value for the initial number of moles ##m = m_0##. I will continueue unless there are substantial objections to the development I have presented. @ArtZ, what is the initial volume of wine you intend to put in the 4.5 quart stock pot? Are you sure that stock pot is 12" in diameter?
 
  • #55
Since the Shaoxing comes wine is sold in 750 mL bottles, I was thinking the sample volumes would be two 250mL samples tested at different temperatures with the other third acting as the taste control sample. The third would remain unheated. Alcohol measurement should be easy as the digital refractometer only requires 2-3 drops of test sample.
 
  • #56
ArtZ said:
Since the Shaoxing comes wine is sold in 750 mL bottles, I was thinking the sample volumes would be two 250mL samples tested at different temperatures with the other third acting as the taste control sample. The third would remain unheated. Alcohol measurement should be easy as the digital refractometer only requires 2-3 drops of test sample.
You’re using a 12” diameter pot to heat 250 cc wine?
 
  • #57
ArtZ said:
The Shaoxing wine that I want to do the EtOH reduction has a very distinctive bouquet. If a recipe that I would use the Shaoxing already calls for a large amount of liquid, your your strategy may work. For a stir fry though, adding a tablespoon of Shaoxing as the stir fry cooks may result in a residual alcohol taste.

I am saying use the same amount of liquid, just dilute the wine. Or, alteratively, use less liquid. Either of these has the unfortunate effect of reducing not just the alcohol but also the other flavor components. But cooking the wine for a long period in advance will also affect the flavor, particularly the volatile aromatics that likely make up most of the bouquet.

You're going to be forced to live with some sort of compromise in quality. Aside from the fun of doing the physics I think that ultimately you'll simply have to try it and see if it's acceptable. So compare that to the alternate method I'm suggesting: using less wine. See how it goes. It's an easy test.
 
  • #58
Chestermiller said:
You’re using a 12” diameter pot to heat 250 cc wine?
I was just thinking about that too. The original plan was to use the entire 750mL. Also, I was thinking about surface area figuring that more SA is better. You are right, and will reduce the size and diameter of cooking pan.

Also was thinking about the thermocouple placement. A couple years ago I was working on recipe for a food product and needed a reliable way to hold the thermometer in the pan.

Created a crude fixture that clipped on the side of the pan. Worked fine. In this experiment I think that it's important to keep the thermocouple away from the side of the pan to prevent erroneous temperature measurements.

What I will do is add a short arm to the clip and attach the thermocouple (TC) to the arm and attach the TC to a small float whereby the TC will remain at a constant depth below the wine surface as the wine volume is reduced.
 
  • #59
ArtZ said:
I was just thinking about that too. The original plan was to use the entire 750mL. Also, I was thinking about surface area figuring that more SA is better. You are right, and will reduce the size and diameter of cooking pan.

Also was thinking about the thermocouple placement. A couple years ago I was working on recipe for a food product and needed a reliable way to hold the thermometer in the pan.

Created a crude fixture that clipped on the side of the pan. Worked fine. In this experiment I think that it's important to keep the thermocouple away from the side of the pan to prevent erroneous temperature measurements.

What I will do is add a short arm to the clip and attach the thermocouple (TC) to the arm and attach the TC to a small float whereby the TC will remain at a constant depth below the wine surface as the wine volume is reduced.
I’m thinking a 500 ml beaker 3” in diameter.
 
  • #60
Chestermiller said:
I’m thinking a 500 ml beaker 3” in diameter.
Experiment design always requires iterations. I've worked in research labs my entire career that were well equipped both in instrumentation and labware. Now, being retired, I have no labware access and generally have to make do with what I can scrounge around the house. Your suggestion is a good one. I do plan to hobble over to the local Labpro to get some sample retention bottles with caps for later tasting.

I'll have to rethink the thermocouple positioning; I am sure I can find a way to position the TC that will be acceptable.
 

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