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Author Topic: Are we using the wrong refrigerants?  (Read 9684 times)

Offline CliffordK

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Are we using the wrong refrigerants?
« on: 19/12/2011 02:57:10 »
I was looking at this vapor pressure chart in Wikipedia.  Sorry it only has a few substances, but the idea is the same. 

http://en.wikipedia.org/wiki/Vapor_pressure


Looking at, say the difference in vapor pressure between -10°C (below freezing), and +20°C (room temperature).

If you choose, something like Propane (BP is -42°C), one goes from a vapor pressure from about 2.5 ATM to about 8.5 ATM, or a difference of about 6 ATM.

However, if one chooses a refrigerant like Diethyl-Ether, one goes from about 0.15 ATM up to about 0.6 ATM. 

So...
Theoretically, running the diethyl-ether in a vacuum, rather that under pressure, one should be able to force the phase change with an absolute difference of only about 0.5 ATM.

It would seem as if one should be able to design the diethyl-ether refrigerant to use less energy.  Although, I know that a vacuum pump in air, seems to have to work quite a bit to achieve a low pressure.
« Last Edit: 19/12/2011 03:00:15 by CliffordK »


 

Offline SeanB

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Re: Are we using the wrong refrigerants?
« Reply #1 on: 19/12/2011 17:45:25 »
You can use ether as a refrigerant, but a bad side effect is that any leaks will tend to allow oxygen into the system, which will make for a extremely explosive reaction.
 

Offline CliffordK

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Re: Are we using the wrong refrigerants?
« Reply #2 on: 19/12/2011 21:16:10 »
You can use ether as a refrigerant, but a bad side effect is that any leaks will tend to allow oxygen into the system, which will make for a extremely explosive reaction.
Good Point.
Heat, Pressure, a Volatile Organic, Plus a risk of adding Oxygen.
May not be the best combination.

One could, of course, choose heavier halocarbons.

My point was that the higher boiling point substances tended to have less of an overall pressure differential change in vapor pressure between the different temperatures, as long as they are operated at a vacuum to force the boiling/evaporation phase.

Of course, the freezing/triple point of a substance would be another limit.
 

Offline Bored chemist

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Re: Are we using the wrong refrigerants?
« Reply #3 on: 20/12/2011 14:51:22 »
I'm not certain, but I think the big issue is that with ether you have a relatively low pressure in the system- so there's not much mass of ether so it can't carry much heat.
Also I'm pretty sure you need to consider the latent heat of evaporation and other parameters.
It's complicated.
 

Offline CliffordK

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Re: Are we using the wrong refrigerants?
« Reply #4 on: 20/12/2011 19:16:10 »
I'm not certain, but I think the big issue is that with ether you have a relatively low pressure in the system- so there's not much mass of ether so it can't carry much heat.

Thanks BC,
That is very insightful. 
However, one could potentially design the system to only use the liquid phase for heating/cooling.



Also I'm pretty sure you need to consider the latent heat of evaporation and other parameters.
It's complicated.

I was thinking that the latent heat of evaporation was a bad thing.  But, perhaps it is actually a good thing, as it means more heat is removed when evaporating, especially if one is using the liquid phase for heating/cooling as above.
 

Offline SeanB

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Re: Are we using the wrong refrigerants?
« Reply #5 on: 20/12/2011 19:37:33 »
Refrigeration relies on a phase change to operate. You have a liquid that is hot and under high pressure, which then has the pressure reduced somehow ( either a capillary tube or an expansion valve) so that the boiling point is now lower than the temperature the liquid is at. It then evaporates, and draws the energy required for this phase change from the environment around it. This makes that side cooler. The cold gas is then compressed by some method ( turbine, vane pump, piston, scroll or other method) to give you a high pressure hot gas ( has had energy added to it) that is then allowed to cool to a lower temperature below it's boiling point and condense to a liquid.

Using the expansion to power the compression is not going to add much to the efficiency, and adds a lot more complexity as well. It will not be useful, if it had any benefit it would have been used in some application by now, as refrigeration has been around for nearly a century. There are still units that are in operation that have been running untouched for close to three quarters of a century.
 

Offline CliffordK

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Re: Are we using the wrong refrigerants?
« Reply #6 on: 20/12/2011 20:06:43 »
Ok,
So, what I've described will work.
But, it would be more or less a direct energy transfer based on the latent heat of vaporization.

Whereas, using the vapor phase, one can multiply the heating/cooling effects due to the enormous expansion between liquid/gas phases.
« Last Edit: 20/12/2011 20:08:51 by CliffordK »
 

Offline Geezer

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Re: Are we using the wrong refrigerants?
« Reply #7 on: 20/12/2011 22:46:18 »

Ok,
So, what I've described will work.


Alas, it won't. You'll simply end up having to do more work with the motor than the work produced by the expander, so you'll be wasting energy. If there was a net gain, you'd be breaking the law. You cannot avoid paying the entropy tax, and for that reason, you can only multiply heating and cooling effects by a number that is less than one.

Multiplying heating and cooling means that you are trying to make heat flow from a cold place to a hot place without doing the necessary work. The work (energy) required to push heat "uphill" is always greater than the amount of heat (energy) transferred. Trying to avoid that is like trying to make time run in the opposite direction.

Homer had something to say about this.

 

Offline CliffordK

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Re: Are we using the wrong refrigerants?
« Reply #8 on: 20/12/2011 23:22:23 »
I didn't mean to imply that the system would work with no energy added.  Obviously, even the vapor pressure will be higher on the warm side than on the cold side, so the vacuum pump still needs power.  I guess that does also mean more pressure on the warm return side to recover some of that added energy.  But, at least some energy would need to be expended, especially if the goal is to remove either warmth or cold from the system.  Otherwise the system would tend towards iso-thermal and stop.

We've already discussed that one could make ice by putting water into a vacuum chamber...  this is more or less using the same concept.
« Last Edit: 20/12/2011 23:25:34 by CliffordK »
 

Offline Geezer

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Re: Are we using the wrong refrigerants?
« Reply #9 on: 21/12/2011 22:06:34 »
I didn't mean to imply that the system would work with no energy added.  Obviously, even the vapor pressure will be higher on the warm side than on the cold side, so the vacuum pump still needs power.  I guess that does also mean more pressure on the warm return side to recover some of that added energy.  But, at least some energy would need to be expended, especially if the goal is to remove either warmth or cold from the system.  Otherwise the system would tend towards iso-thermal and stop.

We've already discussed that one could make ice by putting water into a vacuum chamber...  this is more or less using the same concept.

No, but you're still trying to get "free energy". It's a heat pump, so you can't get work from the thermal gradient because you are pumping heat "uphill". The energy to transport the heat is all coming from the motor, so if you produce work from the heat difference that results from work done by the motor, because of entropy, you'll get less work from the expander than you could have got directly from the motor.

I missed the bit about making ice with a vacuum. If the idea is to lower the pressure above the water to make it freeze, that does not make sense to me. The freezing temperature of water does not increase as pressure decreases.
 

Offline CliffordK

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Re: Are we using the wrong refrigerants?
« Reply #10 on: 21/12/2011 22:50:44 »
I missed the bit about making ice with a vacuum. If the idea is to lower the pressure above the water to make it freeze, that does not make sense to me. The freezing temperature of water does not increase as pressure decreases.

You're in luck.
It seems as if TNS also has a bit of amnesia.

Is vacuum-drying of clothes feasible?

Fortunately, Google doesn't seem to suffer from the same Amnesia problems that TNS seems to.  :)

http://webcache.googleusercontent.com/search?q=cache:LRoS6I3LC4gJ:www.thenakedscientists.com/forum/index.php%3Ftopic%3D25084.0+&cd=1&hl=en&ct=clnk&gl=us&client=firefox-a

Quote from: From Bored Chemist
"How did the discussion get to ice?"
Because some git posted a video of what happens when you connect a vacuum pump to a container of water.
[...]
Have a look at this.
Once the water freezes the vapour pressure drops even further. It's a good way of getting the clothes cold, but not so good at getting them dry.

Unfortunately You-Tube doesn't like my router.  So, I'm taking this on faith.

The same idea as the human body sweating.

A low vapor pressure causes the substance to evaporate. 
The Latent Heat of Vaporization is essentially transferred from the liquid to the vapor.
And, one ends up with ICE.
 

Offline Geezer

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Re: Are we using the wrong refrigerants?
« Reply #11 on: 21/12/2011 23:53:21 »
Ah, but then you are doing work on the water vapor when you compress it to remove it (and heat) from the vacuum chamber.  If you inject water into a vacuum, there is no heat loss.
 

Offline Bored chemist

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Re: Are we using the wrong refrigerants?
« Reply #12 on: 22/12/2011 01:07:46 »
" The freezing temperature of water does not increase as pressure decreases."
What's your second guess?
At best, it depends on what temperature / pressure you start at.
 

Offline CliffordK

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Re: Are we using the wrong refrigerants?
« Reply #13 on: 22/12/2011 01:34:54 »
The freezing temperature of water does not increase as pressure decreases.
What's your second guess?
At best, it depends on what temperature / pressure you start at.
Ahh...
Yes.
The phase diagram of Water.


For pressures around 1 ATM, Temperatures around 0 to +100 °C
As the pressure increases, the freezing point decreases.
As the pressure decreases, the freezing point increases.

Although, the actual difference in freezing point of water between pressures of 101KPA (1ATM) and .6KPA is only 0.01 °C

The point is that by forcing a liquid to evaporate under low pressure, you can decrease the temperature of the liquid, potentially to the point of turning it into a solid.  However, that operation wouldn't be particularly efficient.  Perhaps an energy efficiency of 1:1.  One needs to also use the rarefied vapor phase to further improve heating/cooling efficiency, to higher efficiency ratings, perhaps 2:1 up to 5:1.

My original question was whether one could use the lower vapor pressure of the heavier liquids to one's advantage.  Operating a refrigeration unit under vacuum rather than under pressure, and thus having a lower difference in vapor pressures between the cold and hot liquid phases.

BC's comments were helpful. 
1: The gas produced under a vacuum would be at a lower density.  It might be cooler, but may not have high enough density for effective heat transfer.
2: The latent heat of vaporization may be a problem.  While it does lead to cooling of the liquid phase, such a process likely is not too energy efficient compared to cooling with the rarefied vapor phase.

I never intended to imply a goal of ZERO energy consumption in this process, but was rather exploring potential efficiency gains through the use of lower pressures.

I do find it interesting that one can get 2 to 5 times the heat gain by using a heat pump vs direct electric resistance heating, but that is a different topic.
« Last Edit: 22/12/2011 01:48:39 by CliffordK »
 

Offline Geezer

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Re: Are we using the wrong refrigerants?
« Reply #14 on: 22/12/2011 02:31:36 »

Although, the actual difference in freezing point of water between pressures of 101KPA (1ATM) and .6KPA is only 0.01 °C


Precisely. BC was using a highly pedantic accurate thermometer.
 

Offline Geezer

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Re: Are we using the wrong refrigerants?
« Reply #15 on: 22/12/2011 02:54:28 »
I'm not saying you are trying to get the process to work with zero energy input, but I don't believe that adding the expander can do anything to reduce the energy input from a thermodynamic point of view.
 

Offline Geezer

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Re: Are we using the wrong refrigerants?
« Reply #16 on: 22/12/2011 07:15:57 »
I think I figured it out.

The "heat pump" (call it a refrigerator, reverse heat engine or whatever) is a closed system. The mass of working fluid is constant. The only variables are the ambient temperatures surrounding the hot and cold heat exchangers, and the amount of heat pumped.

Thermodynamics insists that the net amount of heat leaving the system must equal the net work done on the system - no exclusions, no rain checks.

Changing the working fluid will affect the heat transfer rate to and from the heat exchangers, and it will change the work done by the compressor, but it can't alter the relationship between the work input and the heat transferred without breaking the second law.

Therefore, different fluids will influence the amount of heat that can be pumped for a given set of conditions and equipment, but they cannot alter the thermal efficiency of the cycle for that set of conditions. That was previously determined by thermodynamics.

 

Offline CliffordK

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Re: Are we using the wrong refrigerants?
« Reply #17 on: 22/12/2011 11:51:52 »


Ok, here is the general heat pump (or AC/Refrigerator) schematic.

You talk about thermodynamics.  However, this can effectively BREAK the law of thermodynamics...  well, at least crack it a bit. :)

The reason is that one can treat the ambient temperature as an infinite heat sink.

In a closed system, yes, it would obey thermodynamics, and you would have a net energy loss, primarily due to friction and systemic inefficiencies. 

However, in an open system, using the ambient heat sink, one gets an extreme increase in efficiency.

The Cold tank, and the vapor coming off of it will be essentially isothermic.  The temperature will be determined by a few things including the vapor pressure above the tank and whether it is allowed to reach equilibrium.  The lower practical limit on the temperature would be the triple point of the liquid.

The thermal efficiency of the heat pump has to do with the multiplicative factor of the ambient heat that is added.

If 1cc of liquid at 290K --> 10cc of vapor.
Essentially the ideal gas law would give you that Volume is proportional to Temperature, and you get the equivalent of the 10cc at 29K, or the energy transfer equivalent of that.

If you heat that back up to ambient temperature, you get 10cc at 290K --> 1cc at 2900K.  Whew!!!

Hmmm, somehow this has to be symmetrical.  The heat gain per cc would be (290-29)*10 + 290 = 2900K.

So, that is the heat equivalent that you are adding at ambient temperature in the cold radiator...  and would need to be removed in the warm radiator.

Perhaps rather than thinking in degrees, I should consider this in calories.  So, that 1:10 evaporation cycle essentially transferred 2610 Calories from the environment into the system.

Now, you will astutely notice that I left out part of the Ideal Gas Law  PV=nRT.  And, the reason is that at the liquid/vapor boudary, one gets a disjoint in the PV relationship.  Compressing and rarefying an "Ideal" gas like Helium would be much less efficient.

I'll have to re-read about the Latent Heat of Vaporization, as that will likely come into play.  While technically that energy is not lost, it is one of the aspects that gets transferred directly from the cold side to the hot side, and thus would likely not give you any "gain".

As far as whether this 2610 calorie gain from the environment could actually generate more power than what it took to generate it...  I don't know.  Since you are adding energy from the environment, you're not truly breaking any laws of physics. 

That is beyond the question of this topic anyway.  I was simply asking if higher Boiling Point molecules would be better for heat pumps or refrigeration.
« Last Edit: 22/12/2011 11:53:44 by CliffordK »
 

Offline Bored chemist

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Re: Are we using the wrong refrigerants?
« Reply #18 on: 22/12/2011 13:31:48 »
An unscientific answer is that if higher boiling liquids worked better, the manufacturers would hardly have chosen things like SO2 and NH3 in the first place.

Incidentally, WRT the 0.01C change in freezing point, it's not size that's important- it's which direction it's pointing that matters.
 

Offline Geezer

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Re: Are we using the wrong refrigerants?
« Reply #19 on: 22/12/2011 18:54:00 »
 Nice try, but what you are describing is still a closed system. The only things that cross the sytem boundaries are heat and work. The mass of the working fluid remains constant. The net work must be equal to the net heat.
 
You are not adding energy from the environment to your system. You are doing work to transport energy from one part of the environment to a different part of the environment. There is no net change in the energy in the universe outside the heat pump.
« Last Edit: 22/12/2011 18:56:06 by Geezer »
 

Offline Escorpiuser

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Re: Are we using the wrong refrigerants?
« Reply #20 on: 02/01/2012 01:40:55 »
I think that there is a point to take into account: an ideal gas is not ideal anymore when it is compressed. Then begin to arise other atomic/molecular factors that change the general expression PV=nRT.

About if the today refrigerants are wrong, what I remember from the College is that some liquids were discarded because they were flammable/explosive. Others, because were chemically corrosive/agresive, especially for the pipes, but also for humans. The candidates had also to be chemically stable. All these limits drove to elect the known CFCs, that now are being replaced by others (¿fluorocarbons?) less harmful to the ozone layer. Maybe they are not the best in terms of efficiency, but there are other factors that make them the most suitable in the state of art.
 

Offline SeanB

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Re: Are we using the wrong refrigerants?
« Reply #21 on: 02/01/2012 07:19:01 »
The best refrigerant is ammonia, at least for large cold stores and freezers. Cheap, non corrosive ( or at least not terribly corrosive provided you keep water out of it) and works at sane pressures. Newest is CO2, used at insane pressures in commercial fridges, and doing a good job at it, though leaks are a little problem, pressures being up there with high pressure hydraulics - AKA making artificial diamonds, and failures are loud and announce themselves.
 

Offline Bored chemist

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Re: Are we using the wrong refrigerants?
« Reply #22 on: 03/01/2012 18:53:34 »
" Newest is CO2, used at insane pressures in commercial fridges, and doing a good job at it, though leaks are a little problem, pressures being up there with high pressure hydraulics - AKA making artificial diamonds, and failures are loud and announce themselves."
In a very real sense.
According to this
http://www.scribd.com/doc/36474478/CO2-Refrigerant-for-Industrial-Refrigeration-1
The typical pressures are more like 60 bar
Those in hydraulic systems are more like 200 to 400 bar
http://www.omega.com/Green/pdf/HFP_Series.pdf

 and those for making artificial diamonds are about 50,000 bar (I may have lost track of a zero or two converting units on that one).
 

Offline SeanB

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Re: Are we using the wrong refrigerants?
« Reply #23 on: 03/01/2012 19:30:27 »
The pressures are high compared to older refrigerants, who top out at around 20 bar. you have to use special connectors and piping, most of which is both expensive to buy and expensive to get the tooling to use it. Hydraulics are able to cope with slow leaks, the CO2 systems do not tolerate any weakness at all. They have been known to burst piping and parts in fault conditions.
 

Offline gotoluc

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Re: Are we using the wrong refrigerants?
« Reply #24 on: 02/10/2014 05:42:15 »
I was looking at this vapor pressure chart in Wikipedia.  Sorry it only has a few substances, but the idea is the same. 

newbielink:http://en.wikipedia.org/wiki/Vapor_pressure [nonactive]


Looking at, say the difference in vapor pressure between -10°C (below freezing), and +20°C (room temperature).

If you choose, something like Propane (BP is -42°C), one goes from a vapor pressure from about 2.5 ATM to about 8.5 ATM, or a difference of about 6 ATM.

However, if one chooses a refrigerant like Diethyl-Ether, one goes from about 0.15 ATM up to about 0.6 ATM. 

So...
Theoretically, running the diethyl-ether in a vacuum, rather that under pressure, one should be able to force the phase change with an absolute difference of only about 0.5 ATM.

It would seem as if one should be able to design the diethyl-ether refrigerant to use less energy.  Although, I know that a vacuum pump in air, seems to have to work quite a bit to achieve a low pressure.

Hi CliffordK,

I just joined this site because of the topic you started.
I was searching the net for a gas that would expand and contract at temperatures found in the environment (weather) and found that diethyl-ether seems to fit the bill and also found this topic.

Let me tell you what I have in mind. I'm building a self sustained houseboat to which I'm considering to propel with solar electric as I have enough surface area for 2kw of photovoltaic panels. However, I'm always thinking of alternatives as my boat build is far from complete and was considering a heat engine and also thinking of using a gas in it.
I have a great source of heat (sun) and a great heat sink (river) I'm sure there could easily be a 50 degree Celsius difference between the two temperatures.
You seem to be open minded and interested in new ideas, so what would you think of using this great free energy temperature differences to expand and contract a gas in a piston heat engine?

Thanks for your time

Luc
« Last Edit: 02/10/2014 05:46:45 by gotoluc »
 

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Re: Are we using the wrong refrigerants?
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