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Saturday, June 13, 2009

Lab experiment regarding CO2 “snow” in Antarctica at -113°F (-80.5°C) – not possible

Frozen CO2 at the poles of Mars - but not possible on Earth

Frozen CO2 at the poles of Mars - but not possible on Earth


A couple of days ago WUWT carried a story, talking about intense cold in Antarctica, carbon dioxide, and the icecap of Mars. This one passage stirred up a significant debate:

According to Weather Underground, Vostok, Antarctica is forecast to reach -113F on Friday. That is four degrees below the freezing point of CO2 and would cause dry (CO2) ice to freeze directly out of the air.

It seemed (at the time) a reasonable statement. The freezing point of CO2 is -109.3 degrees Fahrenheit (-78.5 degrees C). There’s been mentions of this supposed phenomenon of CO2 freezing out of the air before on other blogs and websites. One of the best examples was even an entry in the website “ask a scientist” where the question of CO2 freezing out of the air was posed, and the answer from an Argonne National Laboratory scientist seemed to indicate that CO2 could indeed precipitate as a solid from the air if the temperature was low enough at Earth’s South Pole, specifically Vostok Station, which holds the record for the lowest temperature recorded on Earth at −89.2°C (−128.6°F)

Certainly, at least some of the carbon dioxide in the atmosphere at the poles does freeze out during the winter. However, there is not enough frozen out to accumulate to any extent at the present.

David R. Cook
Atmospheric Research Section
Environmental Research Division
Argonne National Laboratory

So, it seemed possible. But as WUWT commenters soon pointed out, temperature is only part of the equation needed to deposit CO2 as a solid from the free atmosphere at that temperature.


Soon we were discussing gas laws, phase diagrams, and partial pressures. The debate mainly centered on whether or not this phase diagram for carbon dioxide applied to 1 atmosphere of pressure of pure CO2 versus simply 1 atmosphere of pressure independent of the purity of the gas.


The author of the post, Steven Goddard wrote:

The phase diagram shows unambiguously that the equilibrium state of CO2 at one atmosphere at 113F is solid. The freezing point of CO2 is -109F at 1 atmosphere.
http://www.chemicalogic.com/download/co2_phase_diagram.pdf

The PDF referenced doesn’t translate well to the blog size format, but this less detailed phase diagram for CO2 does fit and was mentioned in comments also:

CO2_phase_diagram

Since many of us know from experience that with ice, be it water ice or CO2 (dry) ice, that a phase change can occur directly from solid to gas (sublimation). It seemed reasonable to conclude that the reverse could be possible, going from a gas to a solid as long as the temperature was below the “triple point” of CO2 as well as the freezing point at 1ATM.


The freezing point/sublimation point of CO2 at 1ATM is at -78.5C (-109.3F). In the situation described in the forecast for Vostok station, the temperature was forecast to reach below the freezing point for CO2 at -80.5 C (-113F ). It seemed reasonable then to concludes that CO2 would freeze right out of the air, much like frost does from water vapor. Plus we had a statement from a scientist at a National Laboratory saying it was possible also. What’s not to like?


One small detail: partial pressure.


The concentration of CO2 in the free atmosphere is very small. Thus the partial pressure of CO2 in the atmosphere is about 0.0004 atmospheres. But wait there’s more. Vostok station is at a high elevation, 3288 meters above sea level (10,787 feet) and the atmosphere is thinner. Thus the partial pressure of CO2 is even lower.


Commenter George E. Smith summed it up pretty well with this paragraph:

At -78.5 deg C (-109F), that equilibrium occurs at a partial pressure of CO2 of 760 mm Hg, one atmosphere. Below that pressure, there isn’t enough abundance of CO2 molecules in the vapor phase for collisions with the solid surface to occur at a fast enough rate to make up for the ones that escaped; so the solid CO2; dry ice, will continue to sublimate.

Basically, there are so few CO2 molecules in the free atmosphere, sublimation rules over deposition as a solid. Yes some CO2 may deposit on a surface at at -80.5 C (-113F ), but it would quickly sublimate back into the free atmosphere, and thus accumulation would not occur.


Meanwhile WUWT reader Ric Werme had written to Dr. David Cook of Argonne National Lab to ask about his original opinion he wrote for “ask a scientist” web site. Ric reports he responded with this:

Ric,

You are correct. In my attempts at being simplistic I made a mistake in my answer to “Freezing CO2″ on the Ask-A-Scientist page. -57 C is the boiling point of CO2. The freezing point of CO2 at atmospheric pressure is -78.5 C (-109.3 F). If the temperature reaches -113 F at Vostok, Antarctica, some carbon dioxide might freeze out of the air, assuming that the carbon dioxide vapor pressure drops to its saturation vapor pressure.


The vapor pressure must reach the saturation vapor pressure for dew or frost to form. This happens at the dew point or frost point temperature, which is dependent on atmospheric pressure and the absolute amount of vapor in the air. As atmospheric temperature increases, the dew/frost point temperature increases. As atmospheric pressure increases, the vapor pressure increases. At very low temperatures, the dew/frost point temperature is very low.


When the temperature of the surface (whether grass or a car window) is below freezing, frost will usually form instead of dew, although water can be super-cooled and not produce dew, fog, or clouds in some cases. Surfaces on the Earth cool off sooner than the air, so dew/frost will normally form on them before fog (water or ice) forms in the air.


The temperature being at “freezing” or below does not imply that frost will form on surfaces or in the air. The vapor pressure must be high enough (saturation vapor pressure) and the temperature low enough (the frost point temperature) for frost to form.

So it seems, Dr. Cook (and our own Steve Goddard) made the basic and simple error of not taking vapor pressure into account. Given our human experience with the everyday freezing of water, we don’t often think about it. I didn’t catch it either initially, nor did some WUWT commenters.


It does demonstrate though, how little CO2 there is in our atmosphere, we can’t even precipitate it to solid under any natural condition of earth.


But, even with the debate apparently settled, the CO2 freezing question was still all in the realm of opinions and phase diagrams. Some people really wanted to see some empirical proof. Some thoughts on experiments were tossed about.


Enter WUWT reader Dr. Thomas Thatcher of the University of Rochester who had not only an idea for an experiment, but the means with which to carry it out. He had a lab freezer which would “maintains -80˚C (-112˚F) in my lab, and it can be set as low as -86˚C (-122˚F).”.


He proposed that he could use that freezer to do a test with dry ice:

The argument, as far as I can tell, is that at the atmospheric partial pressure of CO2, dry ice at -113F will sublimate faster than it forms (which may be different than how a pure CO2 atmosphere would behave). I am in a position to test this, as described above.

Based on the arguments presented here, the two postulated outcomes are,
1) significant loss of mass, as the sublimation rate exceeds the deposition rate
2) no change, or negligible gain in mass.


(I suspect that any gain in mass will evaporate on the short walk from the freezer to the balance.)


It’s admittedly an imperfect experiment. But I expect the outcome will be rather obvious; the dry ice will be gone in the morning. We’ll see.

He conducted his experiment overnight between Thursday and Friday, and writes:

The freezer is a VWR brand ultralow temperature upright freezer, similar to models shown here.
http://www.vwrsp.com/catalog/product/index.cgi?catalog_number=14230-120&inE=1&highlight=14230-120


It is set to -86C, the temperature typically rises 1-3C when opened, and recovers in about 30 minutes. (Factory temperature calibration was NIST-traceable but it has not been recalibrated since it was installed here.) The samples were loaded at 4:30 pm and removed at 9:30 am, so the freezer will have been largely undisturbed during that time.


The interior is mostly filled with stainless steel racks that hold cardboard boxes for storing biological samples. I placed the test samples in two boxes on the bottom shelf at the rear of the freezer, the coldest zone and closest to the temperature probe.


One sample was placed in an open box with extra holes cut to allow air circulation. The other sample was placed in small zip top plastic bag inside a cardboard box. The samples were weighed by difference before being placed in the freezer and after removal in the morning. Additional weighings were taken to estimate the amount of sublimation during the weighing procedure and the amount of water that might condense on the boxes, but these amounts proved insignificant next to the overall results.


The samples were placed in the freezer at 4:30pm (reading -82C) and removed at 10:00am (reading -83C).


Open container, start weight 36.5g dry ice, end weight 0g, amount sublimated 100%.
Zip-top bag, start weight 27.6g dry ice, end weight 25.3g, amount sublimated 8.3%


Proving, I think, that CO2 will freeze and remain frozen at below -78.5C if the partial pressure of CO2 is near 1 ATM, but the CO2 will rapidly sublimate is the partial pressure of CO2 is near atmospheric normal.

And he concludes:

Bottom line, 40g of dry ice placed in an open container at -82C completely sublimated overnight, while 27g of dry ice placed in a zip top bag retained 90% of its mass. This proves two things, first, that the temperature of the freezer did not exceed -78.5C for any appreciable period of time, and second that yes indeed, the partial pressure of CO2 is the key to the problem.

Best of all, he sent photos of the experiment he conducted:

Interior of the freezer showing sample box racks
The placement of the two sample boxes for the CO2 sublimation experiment
The two sample boxes with dry ice of equal weights, enclosed on the left, open on the right, just before they were placed into the freezer for the night.
The sample boxes immediately after removal the next morning.
With the plastic bag removed, showing the leftmost sample still about 90% intact.

Thanks to everyone who participated in the debate, including Ric Werme for his correspondence help and especially Tom Thatcher for conducting the experiment and taking photos.


We all learned something, we had a little fun, some online yelling occurred, and some egos were bruised. Overall though it was worthwhile that this myth of “CO2 snow at Vostok station” was finally put to rest.

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