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[GMCnet] Ethanol in gasoline [message #186303] Wed, 03 October 2012 13:32 Go to next message
emerystora is currently offline  emerystora   United States
Messages: 4442
Registered: January 2004
Karma: 13
Senior Member
We seem to go over and over this topic every year for the last several years.

Recently it was posted that ethanol in gasoline is really not bad and should not cause vapor lock because ethanol has a higher boiling point than gasoline.
This is incorrect and is typical reasoning that one who doesn't have training in chemistry can easily assume. Unfortunately this overlooks what happens when different chemicals are mixed. Mixtures often take on entirely different properties including boiling points.

Here is something that Larry Davick and I posted about a year ago referring to a post that I made in 2010.

>
> On Aug 24, 2011, at 6:43 PM, Larry Davick wrote:
>
>> From ask . com
>>
>> "Alcohol has a boiling point of 72 degrees C or 173 degrees F, which is only slightly lower than the boiling point of water."
>>
>> If we can assume that gasoline has a higher boiling point than alcohol, then we can be assured that blended gasoline will boil at some temperature above 173 degrees F, at sea level.
>>
>> But it need not boil to vaporize. You can dry your laundry on the line in winter - even ice evaporates - check out the old ice in your freezer. (My freezer has no old ice - I'm careful to rotate it through an alcohol bath from time-to-time.)
>>
>> Larry Davick
>> Fremont, California
>> The Mystery Machine
>> '76 (ish) Palm Beach
>
> Larry
>
> using the boiling point of Ethanol by itself to predict the boiling point of a mixture with gasoline can be very misleading.
>
> Here is something that I had posted in June of last year:
>
> ------------
> When it comes to predicting the boiling points of mixtures it get very complicated. Adding more ethanol doesn't necessarily mean that the boiling point will get closer toward the alcohol's boiling point.
> Mixtures of gasoline and ethanol deviates from Raoult's Law caused by variation in intermolecular forces in pure alcohol and in hydrocarbon solution.
>
> Most gasoline components follow Raoult's Law - that is their individual component vapor pressure is the product of their pure component vapor pressure times their mole fraction (or in other words - their percentage in the mixture). This Raoult 's Law behavior allows us to predict the vapor properties of most gasoline blends - each component will contribute according to its concentration in the final blend.
>
> But consider pure alcohol. At molecular weight 46 it has a boiling point of about 174 deg F. (only at sea level) , far above what we would predict of a material of that low molecular weight. Propane, with a molecular weight of 44, is a gas! One can explain the high pure ethanol boiling point and low vapor pressure by the intermolecular forces due to hydrogen bonding between ethanol molecules. The hydrogen of one molecule and the electron pair on oxygen on a second molecule attract each other and additional energy - more heat - is required to separate the molecules to form a gas - to boil. And ethanol has a high dipole moment - a skewed electron distribution that establishes an additional intermolecular attraction.
>
> Note that this boiling point stated above is only for anhydrous ethanol (without water). The ethanol that is used to blend gasoline is hydrous ethanol which contains 4 to 7 % water. Trying to get closer to anhydrous ethanol would make it much more expensive to manufacture.
> But in hydrocarbon solution, the ethanol molecules are separated from each other by the preponderence of nonpolar, hydrocarbon molecules. Ethanol is soluble, but each polar, hydrogen bonding molecule cannot find the ready association with another ethanol molecule that increases boiling point and lowers volatility. Its partial vapor pressure (and thus lower boiling point) is a lot higher than one would predict from Raoult's Law. This deviation from linear, "ideal" behavior that increases ethanol containing gasoline volatility, is a common phenomenon in chemistry.
>
> This is probably getting to be much more technical than most of the people on this site want to hear about or know so I would just suggest that we just drop this direction of this thread.
>
> Emery Stora
> 77 Kingsley
> Santa Fe, NM
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Re: [GMCnet] Ethanol in gasoline [message #186308 is a reply to message #186303] Wed, 03 October 2012 14:00 Go to previous messageGo to next message
hnielsen2 is currently offline  hnielsen2   United States
Messages: 1434
Registered: February 2004
Location: Alpine CA
Karma: 0
Senior Member

Yes and Please.
Its time to stop discussing the stuff we buy and put in our tanks.
It boils and is a PITA on hot days.
Thank You
Howard
Alpine Ca
26' Canyon Lands
Not Quite Stock.

> We seem to go over and over this topic every year for the last several
> years.
>
> Recently it was posted that ethanol in gasoline is really not bad and
> should not cause vapor lock because ethanol has a higher boiling point
> than gasoline.
> This is incorrect and is typical reasoning that one who doesn't have
> training in chemistry can easily assume. Unfortunately this overlooks
> what happens when different chemicals are mixed. Mixtures often take on
> entirely different properties including boiling points.
>
> Here is something that Larry Davick and I posted about a year ago
> referring to a post that I made in 2010.
>
>>
>> On Aug 24, 2011, at 6:43 PM, Larry Davick wrote:
>>
>>> From ask . com
>>>
>>> "Alcohol has a boiling point of 72 degrees C or 173 degrees F, which is
>>> only slightly lower than the boiling point of water."
>>>
>>> If we can assume that gasoline has a higher boiling point than alcohol,
>>> then we can be assured that blended gasoline will boil at some
>>> temperature above 173 degrees F, at sea level.
>>>
>>> But it need not boil to vaporize. You can dry your laundry on the line
>>> in winter - even ice evaporates - check out the old ice in your freezer.
>>> (My freezer has no old ice - I'm careful to rotate it through an alcohol
>>> bath from time-to-time.)
>>>
>>> Larry Davick
>>> Fremont, California
>>> The Mystery Machine
>>> '76 (ish) Palm Beach
>>
>> Larry
>>
>> using the boiling point of Ethanol by itself to predict the boiling point
>> of a mixture with gasoline can be very misleading.
>>
>> Here is something that I had posted in June of last year:
>>
>> ------------
>> When it comes to predicting the boiling points of mixtures it get very
>> complicated. Adding more ethanol doesn't necessarily mean that the
>> boiling point will get closer toward the alcohol's boiling point.
>> Mixtures of gasoline and ethanol deviates from Raoult's Law caused by
>> variation in intermolecular forces in pure alcohol and in hydrocarbon
>> solution.
>>
>> Most gasoline components follow Raoult's Law - that is their individual
>> component vapor pressure is the product of their pure component vapor
>> pressure times their mole fraction (or in other words - their percentage
>> in the mixture). This Raoult 's Law behavior allows us to predict the
>> vapor properties of most gasoline blends - each component will contribute
>> according to its concentration in the final blend.
>>
>> But consider pure alcohol. At molecular weight 46 it has a boiling point
>> of about 174 deg F. (only at sea level) , far above what we would predict
>> of a material of that low molecular weight. Propane, with a molecular
>> weight of 44, is a gas! One can explain the high pure ethanol boiling
>> point and low vapor pressure by the intermolecular forces due to hydrogen
>> bonding between ethanol molecules. The hydrogen of one molecule and the
>> electron pair on oxygen on a second molecule attract each other and
>> additional energy - more heat - is required to separate the molecules to
>> form a gas - to boil. And ethanol has a high dipole moment - a skewed
>> electron distribution that establishes an additional intermolecular
>> attraction.
>>
>> Note that this boiling point stated above is only for anhydrous ethanol
>> (without water). The ethanol that is used to blend gasoline is hydrous
>> ethanol which contains 4 to 7 % water. Trying to get closer to anhydrous
>> ethanol would make it much more expensive to manufacture.
>> But in hydrocarbon solution, the ethanol molecules are separated from
>> each other by the preponderence of nonpolar, hydrocarbon molecules.
>> Ethanol is soluble, but each polar, hydrogen bonding molecule cannot find
>> the ready association with another ethanol molecule that increases
>> boiling point and lowers volatility. Its partial vapor pressure (and
>> thus lower boiling point) is a lot higher than one would predict from
>> Raoult's Law. This deviation from linear, "ideal" behavior that increases
>> ethanol containing gasoline volatility, is a common phenomenon in
>> chemistry.
>>
>> This is probably getting to be much more technical than most of the
>> people on this site want to hear about or know so I would just suggest
>> that we just drop this direction of this thread.
>>
>> Emery Stora
>> 77 Kingsley
>> Santa Fe, NM
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All is well with my Lord
Re: [GMCnet] Ethanol in gasoline [message #186313 is a reply to message #186303] Wed, 03 October 2012 15:12 Go to previous messageGo to next message
James Hupy is currently offline  James Hupy   United States
Messages: 6806
Registered: May 2010
Karma: -62
Senior Member
Emery, I was thinking of the Reid vapour index the other day as I removed a
2 liter bottle of club soda from the fridge. My intentions were to pour
the contents down the drain, I swear. As I screwed the cap very slowly, the
clear liquid suddenly erupted, not unlike a pan on the stove would do when
it boils. I retightened the lid and the reaction ceased although there were
now bubbles attached to the inside of the bottle and to a lesser degree in
the remaing liquid. It occurred to me that a similar occurrence is what we
encounter with blended fuel. I know that C02 was the gas in the soda, but
what about butane and other aeromatic hydrocarbons blended into our present
day fuels coming out of suspension the same way? I suspect that when the
gas cap is opened quickly, that a similar effect occurs.
Jim Hupy
Salem, Or
78 GMC Royale 403
On Oct 3, 2012 11:32 AM, "Emery Stora" <emerystora@mac.com> wrote:

> We seem to go over and over this topic every year for the last several
> years.
>
> Recently it was posted that ethanol in gasoline is really not bad and
> should not cause vapor lock because ethanol has a higher boiling point than
> gasoline.
> This is incorrect and is typical reasoning that one who doesn't have
> training in chemistry can easily assume. Unfortunately this overlooks what
> happens when different chemicals are mixed. Mixtures often take on
> entirely different properties including boiling points.
>
> Here is something that Larry Davick and I posted about a year ago
> referring to a post that I made in 2010.
>
> >
> > On Aug 24, 2011, at 6:43 PM, Larry Davick wrote:
> >
> >> From ask . com
> >>
> >> "Alcohol has a boiling point of 72 degrees C or 173 degrees F, which is
> only slightly lower than the boiling point of water."
> >>
> >> If we can assume that gasoline has a higher boiling point than alcohol,
> then we can be assured that blended gasoline will boil at some temperature
> above 173 degrees F, at sea level.
> >>
> >> But it need not boil to vaporize. You can dry your laundry on the line
> in winter - even ice evaporates - check out the old ice in your freezer.
> (My freezer has no old ice - I'm careful to rotate it through an alcohol
> bath from time-to-time.)
> >>
> >> Larry Davick
> >> Fremont, California
> >> The Mystery Machine
> >> '76 (ish) Palm Beach
> >
> > Larry
> >
> > using the boiling point of Ethanol by itself to predict the boiling
> point of a mixture with gasoline can be very misleading.
> >
> > Here is something that I had posted in June of last year:
> >
> > ------------
> > When it comes to predicting the boiling points of mixtures it get very
> complicated. Adding more ethanol doesn't necessarily mean that the boiling
> point will get closer toward the alcohol's boiling point.
> > Mixtures of gasoline and ethanol deviates from Raoult's Law caused by
> variation in intermolecular forces in pure alcohol and in hydrocarbon
> solution.
> >
> > Most gasoline components follow Raoult's Law - that is their individual
> component vapor pressure is the product of their pure component vapor
> pressure times their mole fraction (or in other words - their percentage in
> the mixture). This Raoult 's Law behavior allows us to predict the vapor
> properties of most gasoline blends - each component will contribute
> according to its concentration in the final blend.
> >
> > But consider pure alcohol. At molecular weight 46 it has a boiling point
> of about 174 deg F. (only at sea level) , far above what we would predict
> of a material of that low molecular weight. Propane, with a molecular
> weight of 44, is a gas! One can explain the high pure ethanol boiling
> point and low vapor pressure by the intermolecular forces due to hydrogen
> bonding between ethanol molecules. The hydrogen of one molecule and the
> electron pair on oxygen on a second molecule attract each other and
> additional energy - more heat - is required to separate the molecules to
> form a gas - to boil. And ethanol has a high dipole moment - a skewed
> electron distribution that establishes an additional intermolecular
> attraction.
> >
> > Note that this boiling point stated above is only for anhydrous ethanol
> (without water). The ethanol that is used to blend gasoline is hydrous
> ethanol which contains 4 to 7 % water. Trying to get closer to anhydrous
> ethanol would make it much more expensive to manufacture.
> > But in hydrocarbon solution, the ethanol molecules are separated from
> each other by the preponderence of nonpolar, hydrocarbon molecules. Ethanol
> is soluble, but each polar, hydrogen bonding molecule cannot find the ready
> association with another ethanol molecule that increases boiling point and
> lowers volatility. Its partial vapor pressure (and thus lower boiling
> point) is a lot higher than one would predict from Raoult's Law. This
> deviation from linear, "ideal" behavior that increases ethanol containing
> gasoline volatility, is a common phenomenon in chemistry.
> >
> > This is probably getting to be much more technical than most of the
> people on this site want to hear about or know so I would just suggest that
> we just drop this direction of this thread.
> >
> > Emery Stora
> > 77 Kingsley
> > Santa Fe, NM
> _______________________________________________
> GMCnet mailing list
> Unsubscribe or Change List Options:
> http://temp.gmcnet.org/cgi-bin/mailman/listinfo/gmclist
>
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Re: [GMCnet] Ethanol in gasoline [message #186344 is a reply to message #186313] Wed, 03 October 2012 19:20 Go to previous messageGo to next message
jhbridges is currently offline  jhbridges   United States
Messages: 8412
Registered: May 2011
Location: Braselton ga
Karma: -74
Senior Member
It certainly did when I was driving my coach home from its point of purchase.  totally silent at the pump till you take the cap off, then you could hear it boil and feel the va[por coming outa the fill tube. 
never does this with gasline sans alcohol in the tanks,.
 
--johnny
'76 23' transmode norris
'76 palm beach

From: James Hupy <jamesh1296@gmail.com>
To: gmclist@temp.gmcnet.org
Sent: Wednesday, October 3, 2012 4:12 PM
Subject: Re: [GMCnet] Ethanol in gasoline

Emery, I was thinking of the Reid vapour index the other day as I removed a
2 liter bottle of club soda from the fridge.  My intentions were to pour
the contents down the drain, I swear. As I screwed the cap very slowly, the
clear liquid suddenly erupted, not unlike a pan on the stove would do when
it boils. I retightened the lid and the reaction ceased although there were
now bubbles attached to the inside of the bottle and to a lesser degree in
the remaing liquid. It occurred to me that a similar occurrence is what we
encounter with blended fuel. I know that C02 was the gas in the soda, but
what about butane and other aeromatic hydrocarbons blended into our present
day fuels coming out of suspension the same way? I suspect that when the
gas cap is opened quickly, that a similar effect occurs.
Jim Hupy
Salem, Or
78 GMC Royale 403
On Oct 3, 2012 11:32 AM, "Emery Stora" <emerystora@mac.com> wrote:

> We seem to go over and over this topic every year for the last several
> years.
>
> Recently it was posted that ethanol in gasoline is really not bad and
> should not cause vapor lock because ethanol has a higher boiling point than
> gasoline.
> This is incorrect and is typical reasoning that one who doesn't have
> training in chemistry can easily assume.  Unfortunately this overlooks what
> happens when different chemicals are mixed.  Mixtures often take on
> entirely different properties including boiling points.
>
> Here is something that Larry Davick and I posted about a year ago
> referring to a post that I made in 2010.
>
> >
> > On Aug 24, 2011, at 6:43 PM, Larry Davick wrote:
> >
> >> From ask . com
> >>
> >> "Alcohol has a boiling point of 72 degrees C or 173 degrees F, which is
> only slightly lower than the boiling point of water."
> >>
> >> If we can assume that gasoline has a higher boiling point than alcohol,
> then we can be assured that blended gasoline will boil at some temperature
> above 173 degrees F, at sea level.
> >>
> >> But it need not boil to vaporize. You can dry your laundry on the line
> in winter - even ice evaporates - check out the old ice in your freezer.
> (My freezer has no old ice - I'm careful to rotate it through an alcohol
> bath from time-to-time.)
> >>
> >> Larry Davick
> >> Fremont, California
> >> The Mystery Machine
> >> '76 (ish) Palm Beach
> >
> > Larry
> >
> > using the boiling point of Ethanol by itself to predict the boiling
> point of a mixture with gasoline can be very misleading.
> >
> > Here is something that I had posted in June of last year:
> >
> > ------------
> > When it comes to predicting the boiling points of mixtures it get very
> complicated.  Adding more ethanol doesn't necessarily mean that the boiling
> point will get closer toward the alcohol's boiling point.
> > Mixtures of gasoline and ethanol deviates from Raoult's Law caused by
> variation in intermolecular forces in pure alcohol and in hydrocarbon
> solution.
> >
> > Most gasoline components follow Raoult's Law - that is their individual
> component vapor pressure is the product of their pure component vapor
> pressure times their mole fraction (or in other words - their percentage in
> the mixture). This Raoult 's Law behavior allows us to predict the vapor
> properties of most gasoline blends - each component will contribute
> according to its concentration in the final blend.
> >
> > But consider pure alcohol. At molecular weight 46 it has a boiling point
> of about 174 deg F. (only at sea level) , far above what we would predict
> of a material of that low molecular weight. Propane, with a molecular
> weight of 44, is a gas!  One can explain the high pure ethanol boiling
> point and low vapor pressure by the intermolecular forces due to hydrogen
> bonding between ethanol molecules. The hydrogen of one molecule and the
> electron pair on oxygen on a second molecule attract each other and
> additional energy - more heat - is required to separate the molecules to
> form a gas - to boil. And ethanol has a high dipole moment - a skewed
> electron distribution that establishes an additional intermolecular
> attraction.
> >
> > Note that this boiling point stated above is only for anhydrous ethanol
> (without water).  The ethanol that is used to blend gasoline is hydrous
> ethanol which contains 4 to 7 % water.  Trying to get closer to anhydrous
> ethanol would make it much more expensive to manufacture.
> > But in hydrocarbon solution, the ethanol molecules are separated from
> each other by the preponderence of nonpolar, hydrocarbon molecules. Ethanol
> is soluble, but each polar, hydrogen bonding molecule cannot find the ready
> association with another ethanol molecule that increases boiling point and
> lowers volatility.  Its partial vapor pressure (and thus lower boiling
> point) is a lot higher than one would predict from Raoult's Law. This
> deviation from linear, "ideal" behavior that increases ethanol containing
> gasoline volatility, is a common phenomenon in chemistry.
> >
> > This is probably getting to be much more technical than most of the
> people on this site want to hear about or know so I would just suggest that
> we just drop this direction of this thread.
> >
> > Emery Stora
> > 77 Kingsley
> > Santa Fe, NM
> _______________________________________________
> GMCnet mailing list
> Unsubscribe or Change List Options:
> http://temp.gmcnet.org/cgi-bin/mailman/listinfo/gmclist
>
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Foolish Carriage, 76 26' Eleganza(?) with beaucoup mods and add - ons. Braselton, Ga. I forgive them all, save those who hurt the dogs. They must answer to me in hell
Re: [GMCnet] Ethanol in gasoline [message #186359 is a reply to message #186344] Wed, 03 October 2012 22:12 Go to previous message
Ken Burton is currently offline  Ken Burton   United States
Messages: 10030
Registered: January 2004
Location: Hebron, Indiana
Karma: 10
Senior Member
About 2 months ago I posted about the EPA RVP requirements on summer blended fuels sold at retail between May 1 and Sept 15th. Basically the RVP requirements seemed adequate in the summer for all areas of the country. The one big exception was that the EPA allowes a 1 point increase in RVP when ethanol was mixed in with real gasoline. I believe this one point variance is causing most of our boiling / vapor lock problems. If the EPA were to revise this one point variance probably very few of us would have major boiling / vapor lock problems.

Ken Burton - N9KB
76 Palm Beach
Hebron, Indiana
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