CFC's and the Atmosphere - An Analysis
Chlorofluorocarbons (CFCs) are gases formed synthetically by replacing all hydrogen atoms in the methane [CH4(g)] or ethane [C2H6(g)] with chlorine and/or fluorine atoms. For example, CFC-12 [CF2Cl2 (g), dichlorodifluoromethane] is formed by replacing the four hydrogen atoms in methane with two chlorine atoms and two fluorine atoms.
Ozone reductions since the late 1970s correlate with increases in chlorine and bromine in the stratosphere. Molina and Rowland (1974) first recognised that chlorine compounds could destroy stratospheric ozone. Since then, scientists have strengthened the links among global ozone reduction, Antarctic ozone depletion, and the presence of chlorine and bromine containing compounds in the stratosphere.
Origins of CFCs and Halons
Thomas Midgley and his assistants in Ohio, USA, invented chlorofluorocarbons in 1928. Midgley and his assistants developed CFC-12 effectively on the same day that a representative of General Motor’ Frigidaire division asked Midgley to find a non-toxic, non-flammable substitute for an existing refrigerant, ammonia, a flammable and toxic gas. CFC-12 and subsequent CFCs were inexpensive, non-toxic, non-flammable, nonexplosive, insoluble, and chemically unreactive under tropospheric conditions; thus they became popular.
Midgley demonstrated the non-toxic and non-flammable properties of his invention to the American Chemical Society in April 1930 by inhaling CFC-12 then blowing it over a candle flame, extinguishing the flame. Along with the use as a refrigerant, CFCs and halogens were specifically used as propellants.
In 1943, Goodhue and Sullivan of the U.S. Department of Agriculture developed a method to use CFC-11 and CFC -12 as a propellant in spray cans. CFCs flowed out of the spray can’s nozzle, carrying with them a mist containing other ingredients. CFCs were used to propel hair spray, paints, deodorants, disinfectants, polishes and insecticides. They were also used marginally in air conditioners.
Through leakages in the spraying cans, refrigerants as well as general use, these CFC particles then escaped into the atmosphere and while they were, as stated, unreactive in tropospheric conditions, they however found their way into the stratosphere where they reacted violently with sunlight to destroy Ozone molecules.
Halons in the form of Bromofluorocarbons are also found in the atmosphere, they have been released from fire extinguishers where they were used extensively until the London Protocol of 1990. Halon 1211 (CClF2Br) as well as Halon 1301 (CF3Br) were extensively used in non-electrical related fires and were found to be extremely effective, however when they reacted under stratospheric conditions also formed free radicals and tended to cause disturbances to the ozone level, they have as such been limited in their usage.
Problems Associated with the use of CFCs
CFCl3 (g) UV CFCl2 (g)+ Cl(g)
CF2Cl2(g) UV CF2Cl(g) + Cl(g)
From the above equation it is seen that the unbonded Cl is a free radical, which then reacts with Ozone under UV light.
Cl (g)+ O3 (g) UV ClO (g)+ O2(g)
ClO(g) + O(g) UV Cl(g) + O2(g)
As can be seen this is a repetitive process. The Cl, which breaks the ozone in the first process, is then regenerated in the second process and the reaction keeps occurring. This is why just one molecule of Cl has the capacity to destruct over 1000 molecules of Ozone.
CFCs are extremely dangerous to the natural environment. This is because they have the tendency to break down ozone molecules in the stratosphere. This has direct consequences for living beings on earth.
In the absence of the stratospheric ozone layer, most UV-C radiation would penetrate to the surface of the earth, destroying bacteria, protozoa, algae, fungi, plants and animals in a short time. Fortunately, the ozone layer absorbs almost all UV- C radiation. Ozone also absorbs most UV-B radiation, but some of this radiation penetrates to the surface. UV-B radiation affects human and animal health, terrestrial ecosystems, aquatic ecosystems, biogeochemical cycles, air quality and materials.
Increases in UV-B radiation have potential to affect the skin, eyes and immune system of humans. They layers of skin affected by UV-B are the epidermis (the outer protective layer of skin) and often as a result cancerous cells form here, melanoma is a common problem.
To alleviate these problems the Montreal Convention of 1987 was set-up wherein all developed countries were banned from using CFCs. This is a good step however because CFC in the stratosphere has a cyclical process many of the CFCs released in the 1980’s and 1990’s are taking their effect now. The CFCs released by many countries even now do not have an immediate effect; it takes years before they react and then destruct the ozone.
Since then in the London, Copenhagen and again Montreal protocols more stringent measures have been taken to stop expulsion of CFCs as well as HCFCs. Research now indicates a lessening in the rate of depletion - which in effect accepts that much good work has gone into controlling and restricting the usage of CFCs. Buffer systems have also been set up but these tend to be very sporadic and not very effective, however they have caused an improvement in lessening the rate of Cl radicals available in the stratosphere.
In direct relation with humans, Sun Lotion is an accepted and necessary item that is used to block UV-B rays from affecting the skin and subsequently causing cancer; it has been extremely effective.
Changes in Atmospheric Ozone Concentrations
About 90% of all ozone molecules in the atmosphere reside in the stratosphere; most of the remaining molecules reside in the troposphere. Whereas ozone molecules near the surface harm humans, animals, plants and trees, and structures, the same ozone molecules, whether in the stratosphere or in polluted air, shield the Earth from harmful UV radiation.
A measure of the quantity of ozone in the air is the ozone column abundance, which is the sum of all ozone molecules above a square centimetre of surface between the ground and the top of the atmosphere. When this number is divided by a constant (2.7x1016), the result is the column abundance in Dobson Units (DU). Thus 1DU is equivalent to 2.7x1016 molecules of ozone per square centimetre of surface. Gordon Dobson also, in 1920, built the first instrument, now called the Dobson Spectrometer, to measure total ozone column abundance from the ground. In 2000, the globally averaged column abundance of ozone from 90S to 90N (in degrees) was 293.4DU.
The Dobson Spectrometer is an instrument, which determines the differences in atmospheric attenuation of solar UV radiation across spectral lines centred on 320nm. Satellite measurements are also being made of both total column ozone and vertical variation, using ultraviolet radiation back scattered from the atmosphere.
Ozone production is at a maximum in the tropical stratosphere. The Earth’s meridional circulation pattern then transports the ozone towards the Poles, with preference for the winter pole. Hence the latitudinal ozone distribution shows that total column amounts are higher towards the poles than in equatorial regions, and that the peak values are reached in March/April in the northern hemisphere and September/October in the southern hemisphere.
Between 1979 and 2000, the global stratospheric ozone column abundance decreased from 304DU to 293.4DU.
Between 1950 and 1980, no measurements from three ground stations in the Antarctica showed ozone levels less than 220 DU, a threshold for defining Antarctic ozone depletion. Every Southern Hemisphere spring since 1980, measurements of stratospheric ozone have shown depletion. In 1985 a 30% decrease was shown as compared to 1980 measurements. Since then, measurements over the South Pole have indicated depletions of up to 70% of the column ozone for a period of a week in early October. In September 2000, Antarctica recorded the largest depletion for the month with some 30.8% being wiped off in comparison to 1980’s figures. The large reduction of stratospheric ozone over the Antarctic in the Southern Hemisphere spring each year is Antarctic Ozone Hole. This area is now greater than the size of North America.
In effect, the greatening of these holes directly correlates with global warming (due to UV radiation) as well as health problems caused by UV-B rays which humans are now exposed to.
Alternatives to CFCs
As early as 1974 scientists were hypothesising that CFCs were destroying ozone and during late 1974 legislation was introduced to the US Congress to study the problem with greater depth and regulate usage of the CFCs. However the legislation was truncated without much thought. In 1975 a bill was passed to label all spray cans as to whether they contain CFCs or any other chemicals. With statistics coming in about the loss in stratospheric ozone, by about 1980, the US proposed limiting CFC use within its country but as a new president was coming in at the time this approach was also truncated.
In September 1987 a second international agreement (the first had been the Vienna conference) was signed by 27 countries limiting the use of CFCs and Halons in developed countries throughout the world. There have been modifications to allowances in 1990, 1992 and finally in 1997 once again at Montreal. The purposes were to wipe out use of CFCs.
Around 1980 scientists looked towards Hydrochlorofluorocarbons (HCFC). These compounds are easily attacked by free radicals but since they contain a C -H bond they are limited as to how much they can destroy the ozone. The decomposition of HCFCs is very little compared to what a CFC is capable of. Although the ozone destroying capabilities of CFCs is far less compared to CFCs, they still contain Cl atoms and as such still pose a significant threat. In the 1990 London Convention HCFCs were chosen as the temporary substitute for CFCs.
It was noticed by scientists that HCFCs only reduce the problem but the problem still exists so in 1992 at the Copenhagen Convention HCFCs were also rejected in favour of Hydrofluorocarbons (HFCs). HFCs do not contain any Cl molecules and as such do not contain any properties, which could cause destruction to the ozone layer. They contain C-H bonds but not C-Cl bonds. HFCs are used in all aspects where CFCs and HCFCs had previously been used. HFCs are generally more expensive than CFCs or HCFCs and as such have not had great success in developing countries. In Australia only HFCs are used conclusively as the next generation CFC. As such it is used as refrigerant, a propellant and even used in the production of some plastics.
HFCs are a viable and environmentally friendly alternative to CFCs. They present all the benefits and uses of CFCs and HCFCs without providing any drawbacks in terms of ozone destruction. They are priced similarly; if a little higher, than ordinary CFCs and as such do not have many financial or economic limitations on manufacturers and consumers.
References
1. Jacobson M (2002). Atmospheric Pollution. Cambridge, United Kingdom
2. Colls J (1997). Air Pollution. E&FN, Spain
3. Smith R (2001). Conquering Chemistry HSC Course. McGraw Hill, London
4. Bach W (1972). Atmospheric Pollution. McGraw Hill, London
5. http://www.ttgv.org.tr/tur/02_ttgv_hakkinda/cfc.gif
6. http://en.wikipedia.org/wiki/Haloalkane
7. http://en.wikipedia.org/wiki/Ozone_depletion
8. http://www.epa.gov/ozone/ USA Environmental Protection Agency (2002)
Ozone reductions since the late 1970s correlate with increases in chlorine and bromine in the stratosphere. Molina and Rowland (1974) first recognised that chlorine compounds could destroy stratospheric ozone. Since then, scientists have strengthened the links among global ozone reduction, Antarctic ozone depletion, and the presence of chlorine and bromine containing compounds in the stratosphere.
Origins of CFCs and Halons
Thomas Midgley and his assistants in Ohio, USA, invented chlorofluorocarbons in 1928. Midgley and his assistants developed CFC-12 effectively on the same day that a representative of General Motor’ Frigidaire division asked Midgley to find a non-toxic, non-flammable substitute for an existing refrigerant, ammonia, a flammable and toxic gas. CFC-12 and subsequent CFCs were inexpensive, non-toxic, non-flammable, nonexplosive, insoluble, and chemically unreactive under tropospheric conditions; thus they became popular.
Midgley demonstrated the non-toxic and non-flammable properties of his invention to the American Chemical Society in April 1930 by inhaling CFC-12 then blowing it over a candle flame, extinguishing the flame. Along with the use as a refrigerant, CFCs and halogens were specifically used as propellants.
In 1943, Goodhue and Sullivan of the U.S. Department of Agriculture developed a method to use CFC-11 and CFC -12 as a propellant in spray cans. CFCs flowed out of the spray can’s nozzle, carrying with them a mist containing other ingredients. CFCs were used to propel hair spray, paints, deodorants, disinfectants, polishes and insecticides. They were also used marginally in air conditioners.
Through leakages in the spraying cans, refrigerants as well as general use, these CFC particles then escaped into the atmosphere and while they were, as stated, unreactive in tropospheric conditions, they however found their way into the stratosphere where they reacted violently with sunlight to destroy Ozone molecules.
Halons in the form of Bromofluorocarbons are also found in the atmosphere, they have been released from fire extinguishers where they were used extensively until the London Protocol of 1990. Halon 1211 (CClF2Br) as well as Halon 1301 (CF3Br) were extensively used in non-electrical related fires and were found to be extremely effective, however when they reacted under stratospheric conditions also formed free radicals and tended to cause disturbances to the ozone level, they have as such been limited in their usage.
Problems Associated with the use of CFCs
CFCl3 (g) UV CFCl2 (g)+ Cl(g)
CF2Cl2(g) UV CF2Cl(g) + Cl(g)
From the above equation it is seen that the unbonded Cl is a free radical, which then reacts with Ozone under UV light.
Cl (g)+ O3 (g) UV ClO (g)+ O2(g)
ClO(g) + O(g) UV Cl(g) + O2(g)
As can be seen this is a repetitive process. The Cl, which breaks the ozone in the first process, is then regenerated in the second process and the reaction keeps occurring. This is why just one molecule of Cl has the capacity to destruct over 1000 molecules of Ozone.
CFCs are extremely dangerous to the natural environment. This is because they have the tendency to break down ozone molecules in the stratosphere. This has direct consequences for living beings on earth.
In the absence of the stratospheric ozone layer, most UV-C radiation would penetrate to the surface of the earth, destroying bacteria, protozoa, algae, fungi, plants and animals in a short time. Fortunately, the ozone layer absorbs almost all UV- C radiation. Ozone also absorbs most UV-B radiation, but some of this radiation penetrates to the surface. UV-B radiation affects human and animal health, terrestrial ecosystems, aquatic ecosystems, biogeochemical cycles, air quality and materials.
Increases in UV-B radiation have potential to affect the skin, eyes and immune system of humans. They layers of skin affected by UV-B are the epidermis (the outer protective layer of skin) and often as a result cancerous cells form here, melanoma is a common problem.
To alleviate these problems the Montreal Convention of 1987 was set-up wherein all developed countries were banned from using CFCs. This is a good step however because CFC in the stratosphere has a cyclical process many of the CFCs released in the 1980’s and 1990’s are taking their effect now. The CFCs released by many countries even now do not have an immediate effect; it takes years before they react and then destruct the ozone.
Since then in the London, Copenhagen and again Montreal protocols more stringent measures have been taken to stop expulsion of CFCs as well as HCFCs. Research now indicates a lessening in the rate of depletion - which in effect accepts that much good work has gone into controlling and restricting the usage of CFCs. Buffer systems have also been set up but these tend to be very sporadic and not very effective, however they have caused an improvement in lessening the rate of Cl radicals available in the stratosphere.
In direct relation with humans, Sun Lotion is an accepted and necessary item that is used to block UV-B rays from affecting the skin and subsequently causing cancer; it has been extremely effective.
Changes in Atmospheric Ozone Concentrations
About 90% of all ozone molecules in the atmosphere reside in the stratosphere; most of the remaining molecules reside in the troposphere. Whereas ozone molecules near the surface harm humans, animals, plants and trees, and structures, the same ozone molecules, whether in the stratosphere or in polluted air, shield the Earth from harmful UV radiation.
A measure of the quantity of ozone in the air is the ozone column abundance, which is the sum of all ozone molecules above a square centimetre of surface between the ground and the top of the atmosphere. When this number is divided by a constant (2.7x1016), the result is the column abundance in Dobson Units (DU). Thus 1DU is equivalent to 2.7x1016 molecules of ozone per square centimetre of surface. Gordon Dobson also, in 1920, built the first instrument, now called the Dobson Spectrometer, to measure total ozone column abundance from the ground. In 2000, the globally averaged column abundance of ozone from 90S to 90N (in degrees) was 293.4DU.
The Dobson Spectrometer is an instrument, which determines the differences in atmospheric attenuation of solar UV radiation across spectral lines centred on 320nm. Satellite measurements are also being made of both total column ozone and vertical variation, using ultraviolet radiation back scattered from the atmosphere.
Ozone production is at a maximum in the tropical stratosphere. The Earth’s meridional circulation pattern then transports the ozone towards the Poles, with preference for the winter pole. Hence the latitudinal ozone distribution shows that total column amounts are higher towards the poles than in equatorial regions, and that the peak values are reached in March/April in the northern hemisphere and September/October in the southern hemisphere.
Between 1979 and 2000, the global stratospheric ozone column abundance decreased from 304DU to 293.4DU.
Between 1950 and 1980, no measurements from three ground stations in the Antarctica showed ozone levels less than 220 DU, a threshold for defining Antarctic ozone depletion. Every Southern Hemisphere spring since 1980, measurements of stratospheric ozone have shown depletion. In 1985 a 30% decrease was shown as compared to 1980 measurements. Since then, measurements over the South Pole have indicated depletions of up to 70% of the column ozone for a period of a week in early October. In September 2000, Antarctica recorded the largest depletion for the month with some 30.8% being wiped off in comparison to 1980’s figures. The large reduction of stratospheric ozone over the Antarctic in the Southern Hemisphere spring each year is Antarctic Ozone Hole. This area is now greater than the size of North America.
In effect, the greatening of these holes directly correlates with global warming (due to UV radiation) as well as health problems caused by UV-B rays which humans are now exposed to.
Alternatives to CFCs
As early as 1974 scientists were hypothesising that CFCs were destroying ozone and during late 1974 legislation was introduced to the US Congress to study the problem with greater depth and regulate usage of the CFCs. However the legislation was truncated without much thought. In 1975 a bill was passed to label all spray cans as to whether they contain CFCs or any other chemicals. With statistics coming in about the loss in stratospheric ozone, by about 1980, the US proposed limiting CFC use within its country but as a new president was coming in at the time this approach was also truncated.
In September 1987 a second international agreement (the first had been the Vienna conference) was signed by 27 countries limiting the use of CFCs and Halons in developed countries throughout the world. There have been modifications to allowances in 1990, 1992 and finally in 1997 once again at Montreal. The purposes were to wipe out use of CFCs.
Around 1980 scientists looked towards Hydrochlorofluorocarbons (HCFC). These compounds are easily attacked by free radicals but since they contain a C -H bond they are limited as to how much they can destroy the ozone. The decomposition of HCFCs is very little compared to what a CFC is capable of. Although the ozone destroying capabilities of CFCs is far less compared to CFCs, they still contain Cl atoms and as such still pose a significant threat. In the 1990 London Convention HCFCs were chosen as the temporary substitute for CFCs.
It was noticed by scientists that HCFCs only reduce the problem but the problem still exists so in 1992 at the Copenhagen Convention HCFCs were also rejected in favour of Hydrofluorocarbons (HFCs). HFCs do not contain any Cl molecules and as such do not contain any properties, which could cause destruction to the ozone layer. They contain C-H bonds but not C-Cl bonds. HFCs are used in all aspects where CFCs and HCFCs had previously been used. HFCs are generally more expensive than CFCs or HCFCs and as such have not had great success in developing countries. In Australia only HFCs are used conclusively as the next generation CFC. As such it is used as refrigerant, a propellant and even used in the production of some plastics.
HFCs are a viable and environmentally friendly alternative to CFCs. They present all the benefits and uses of CFCs and HCFCs without providing any drawbacks in terms of ozone destruction. They are priced similarly; if a little higher, than ordinary CFCs and as such do not have many financial or economic limitations on manufacturers and consumers.
References
1. Jacobson M (2002). Atmospheric Pollution. Cambridge, United Kingdom
2. Colls J (1997). Air Pollution. E&FN, Spain
3. Smith R (2001). Conquering Chemistry HSC Course. McGraw Hill, London
4. Bach W (1972). Atmospheric Pollution. McGraw Hill, London
5. http://www.ttgv.org.tr/tur/02_ttgv_hakkinda/cfc.gif
6. http://en.wikipedia.org/wiki/Haloalkane
7. http://en.wikipedia.org/wiki/Ozone_depletion
8. http://www.epa.gov/ozone/ USA Environmental Protection Agency (2002)
This entry was posted by Blogpur, on
Tuesday, November 15, 2005.
You can leave your response.
7:15 PM
Interesting writeup Venkat.
Do you know that Thomas Midgely another contribution for environment degradation was adding lead in petrol to reduce 'knocking'?
Also, James Lovelock suggested the idea of releasing CFCs into the atmosphere to track air currents. This got both Sherry Rowland and Mario Molina interested in CFCs and ozone and the rest is history
8:26 PM
No, I didn't know that. Thats very interesting, especially about Midgely adding lead to petrol. I'll do some net research.
7:55 AM
Very informative read Venkat. That must've taken quite a bit of time to compile. I learnt a lot stuff about CFC's and HFC's that I didn't know. Thanks
11:05 AM
Very well written and researched.
One thing that caught my eye though was this statement "one molecule of Cl has the capacity to destruct over 1000 molecules of Ozone."
The digit is actually 100 000!
Better to have under exaggerated though.
Thanks.
4:43 PM
that was the best article I have found about CFCs!! It compiles all of the necessary information in a range of related area... that is it covers a lot of questions about CFCs they ask in my HSC!!! Thanks heaps. You've definately helped me!!
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