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A Chemists View on Octane and Gasoline Brands

scottdk

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Ok everyone, this is worth a read and forum discusion. To start....I am not the author of this article. I was very intrigued by this article and I believe it's a nice perspective that I don't believe is captured in the forum yet. Some viewpoints and opinions have been expressed in other threads regarding gasoline brands, oil companies, and fuel additives and so on.

Here is an article that I received via email and I would like to share. Of course your opinions are welcomed and encouraged:D

A Chemists View on Octane and Gasoline Brands
From Tom Johnson, tjohnson@FLEX.NET
--------------------------------------------------------------------------------

Someone in the octane thread asked for a chemist's view on the subject, so here's mine. However, first a view necessities and background:


Credentials:



Ph.D. Organic chemist, 21 years as a practicing chemist, 28 US patents (many on gasoline additives), work for a major oil company that is a leading (by volume) retailer of gasoline in the world. I've had engine tests (meaning an engine on a fixed engine stand run by a computer) and road tests (meaning cars driven by humans -- some on a course, some not) run on gasoline additives I've invented (while employed at the oil company). These additives have been tested in the US, England, and France under a variety of conditions. Many of my additives have also been tested in the BMW test (10,000 miles). I'm still employed by said oil company.


Disclaimers:



The views expressed here are my own and not the company I work for (which is why I don't mention the company, although I realize any enterprising person could easily find out).


Copyright:



This entire note is copyrighted by the author. Participants in this mail group may store and make one copy for their own use. Participants may refer to, copy, send, and re-send to particpants of this mail group and post or re-post sections of this note as long as this copyright notice is attached. Except for these specific exceptions, this note may not be copied, quoted, or transmitted in any form for profit or non-profit, or used for any type of publication without written permission from the author.



Octane:
I've seen many consumer magazines tell their readers that they are wasting money to buy a higher octane gasoline if their car doesn't knock. If octane were not related to any other feature of the gasoline, I would agree. However, how companies get higher octane gasoline does make it different than regular and mid-grade gasoline. So the question to me then is, do these differences make a difference? The short answer is what do I use, and I use regular in all my cars and my truck. I use premium in my Corvette. Why? Because as any Corvette enthusiast (to separate us from people who merely own one -- no flames, please) knows, a Corvette is not a car, it's an experience. If you want to know the long answer keep reading.


Base gasoline:



Crude oil differs depending on where it's from, and consequently, what comes out of it when it's refined also differs. There are books on the subject and I can't possibly do the subject justice here. As the oil differs, what is available for blending and cutting is different. In the end, however, the refiner has to make economic choices, based on what's available to him from the oil he is refining, on how to get the required octane to sell (as well as meet MANY other criteria that make gasoline, gasoline -- again I can't do justice to it here). What I generally (but not exclusively) see is that BASE (no additive added to it -- you can't buy this, it isn't offered for sale) premium gasoline leaves less deposits behind than other grades. There are certain types of molecules in regular and mid-grade BASE gasoline's that simply do not exist in premium gasoline that cause much of this. Additives (see definition below) are added to the gasoline to help get rid of these deposits, and modern additives do a marvelous job of this. What you buy is additized gasoline.


Blending components vs additives:



MTBE (methyl tertiary butyl ether -- this is ether) and ethanol are blending components, not additives. However, you'll see them called additives in many places by many people. Blending components are part of base gasoline. The simplest differentiation between an additive and a blending component is that the former are added in ppm (parts-per-million) levels; whereas, the latter are added in percentage quantities.


Brand of gasoline:



Some of you probably know this, others may be shocked by it. Oil companies swap base gasoline all the time. Let's say I have a refinery in Houston and you have one in Dallas. It makes little sense for me to truck my Houston gasoline to Dallas and for you to truck your gasoline from Dallas to Houston when gasoline is a commodity product. So, I let you draw 100,000 gallons of base gasoline from my storage tank in Houston for your Houston gas stations, and you let me draw 100,000 gallons of base gasoline from your Dallas holding tanks for my Dallas gas stations. That way, we both save on shipping. Yup, Texaco gasoline may have come from a Shell refinery and vice-versa. At a gasoline terminal you may see trucks from up to six different companies all loading at the SAME terminal (that for example may be supplied exclusively by Shell). What comes next, however, is what makes Texaco Texaco and Shell Shell. Additive. Each company has its own additive and adds it to the base gasoline. So while the base gasoline may be the same, the additive is different, and hence the brand of gasoline you use is different because of the additive, not the base gasoline.


Which additive is better?:



Given the above discourse, it's obvious that we all want the gasoline with the best additive. Unfortunately, it's not that simple. Additives respond differently in different base gasoline's (even of the same grade). Also, some additives work better with gasoline's used in a carbureted car vs one that uses fuel injection. On a practical level, additives are going to be developed today for today's cars -- meaning fuel injected cars. For Corvette owners who have carbureted Vettes (like me), this is unfortunate. Carbureted engines leave a LOT more deposits behind than fuel injected cars. From a regulatory stand point, California was the first to call for all gasoline's to pass the BMW test (port-fuel-injected engine) in all grades of gasoline. Like all regulations, this one had various massages put to it, but the net effect was that all oil companies went to work developing additives that are a LOT better today than 10 years ago AND they are used in all grades (not just premium -- hence the argument to use premium to get a better additive went out the window).


Insider's trick on gasoline additives:



No matter what you do or what you drive, this trick will help you keep down deposits inside your engine. You see, additives themselves will make deposits and/or create a deposit that is different from the one made by base gasoline alone. If you think about this for a moment, you'll come to realize that your engine will build some kind of deposit based upon what additive you are using. Yes, it will build at a slower rate, but it will build deposits. At some level this will taper off (but this is maximum deposits and what Corvette owner wants that!). So what do you do? Simple, switch to a different brand of gasoline (this will almost assure you of getting a different additive but not always. Some companies buy additives from other companies, so it could be the same. More on this later). What this will do, is the new additive will look at the deposit formed from the old additive as foreign and begin removing it. Now after 5000 miles, you'll be rid of this deposit but you'll have a new one from your most recent additive, so switch back and start the process all over again. As an analogy, this is like building an immune response to an anti-biotic, so your doctor gives you a new one. I know of absolutely no additive that will work as well as switching back and forth between additives. On a molecular level this makes perfect sense.


So what's an savvy owner to do?:



(1) Whether you buy regular, mid-grade, or premium, use one brand for about 5000 miles, then switch to another brand for 5000 miles. I use Shell, then Chevron, then Exxon, then back to Shell, etc. (this is not an endorsement). These companies have historically had there own additive research groups/companies, so they'll likely use their own additive and not something they bought from each other. It is completely possible, however, to use a sequence like Amoco, Shell, Texaco and still come out fine. (Again these are not endorsements). I use three companies and 5000 miles based on what I've observed working in the research area. 7,000 miles and two different brands will still do wonders. As an aside, it takes most vehicles 7-13,000 miles to build their maximum deposit levels.
 
very interesting read, i use shell exclusively as i was told stick to 1 brand and your car will respond better then switching brands. There is so much info out there it's hard to know who is right or wrong
 
how can one EFFECTIVELY increase the research octane in the tank with a handy garage/or parts store type additive?
 
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Great information. I don't mind stopping at unknown stations because it usually all comes from the same place.
 
My sister just purchased a new GM car, and it states that for the best performance, use "Top Tier" Gasolines. (I think that was the words used). Says that Top Tier gas will have a sign on the pump stating it is Top Tier.

Well, I have purchased a lot of gas, both local in Florida, New York and New Mexico, plus at many stations on the open road, and I've never seen any gas pump that said their gas was "Top Tier".
 
My sister just purchased a new GM car, and it states that for the best performance, use "Top Tier" Gasolines. (I think that was the words used). Says that Top Tier gas will have a sign on the pump stating it is Top Tier.

Well, I have purchased a lot of gas, both local in Florida, New York and New Mexico, plus at many stations on the open road, and I've never seen any gas pump that said their gas was "Top Tier".

Well I have to say I never heard of Top Tier gas, so I found an article on Wikipedia regarding it.


According to the link, the benefits are:

Improved fuel efficiency
Reduced driving upsets (rough idle, stalling and surge)
Improved acceleration
Increased engine power
Reduced emissions

http://en.wikipedia.org/wiki/Top_Tier_Detergent_Gasoline
 
Well I have to say I never heard of Top Tier gas, so I found an article on Wikipedia regarding it.


According to the link, the benefits are:

Improved fuel efficiency
Reduced driving upsets (rough idle, stalling and surge)
Improved acceleration
Increased engine power
Reduced emissions

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

Thanks for the post Scott. Now we only need for them to post something on the pumps, so we know if it is Top Tier. Should be easy to do, because they already have those "10% Ethanol" signs on the pumps.
 
ill start being brand loyal when they advertise "infused with nitro methane"
 
Top Tier Detergent is not the same characteristic as top octane in gasoline. Gasoline with the same octane but different detergent additive will not improve:
Improved fuel efficiency
Reduced driving upsets (rough idle, stalling and surge)
Improved acceleration
Increased engine power
Reduced emissions

Unless the car has ping sensors in the ignition timing and can vary timing to take advantage of the octane increase none of the above is true. Regular gas has more energy in it than high test and will give you better cold weather starts than high test because it has a lower "falsh point". If you remember they used lead in days gone by to INCREASE octane rating and lead does not burn. In affect the lead lowered the "flash point" to improve pre-ignition. All things being equal regular gas will give you better mileage than high test. If you don't have a knock sensor in your car and/or don't care about a few extra horse power regular gas is the way to go and save you lots of money.
 
Top Tier Detergent is not the same characteristic as top octane in gasoline. Gasoline with the same octane but different detergent additive will not improve:
Improved fuel efficiency
Reduced driving upsets (rough idle, stalling and surge)
Improved acceleration
Increased engine power
Reduced emissions

Unless the car has ping sensors in the ignition timing and can vary timing to take advantage of the octane increase none of the above is true. Regular gas has more energy in it than high test and will give you better cold weather starts than high test because it has a lower "falsh point". If you remember they used lead in days gone by to INCREASE octane rating and lead does not burn. In affect the lead lowered the "flash point" to improve pre-ignition. All things being equal regular gas will give you better mileage than high test. If you don't have a knock sensor in your car and/or don't care about a few extra horse power regular gas is the way to go and save you lots of money.

For the past few weeks, I have switched from anyone's 87 octane to strictly Mobil 93 octane (R+M/2). What I've found is that the car does drive better, engine smoother, and faster with the 93 Octane, however the gas milage is no different. I.E., I go just as far on a gallon of 87 as I do with a gallon of 93.
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For the past few weeks, I have switched from anyone's 87 octane to strictly Mobil 93 octane (R+M/2). What I've found is that the car does drive better, engine smoother, and faster with the 93 Octane, however the gas milage is no different. I.E., I go just as far on a gallon of 87 as I do with a gallon of 93.

I knew I was going to get replies as the one above. Let me be clear. If your car has a knock sensor you can expect better car peformance by the lower energy, lower flash point, higher octane 93 gas and your car will respond as you've described. If you car does not, there is no explanation from a scientific controlled blind study that can be duplicated . Also again all things being equal there is NO super duper additive being put into high test gas to explain physical performance improvement such as cleaning additives.

I'm not going to get into a debate or question your results. Having said that I will also stand by my evaluation of octane expectations. I just ask the naysayers to explain how cars without a knock sensor can perform better by just adding lead to the gas? I use lead when discussing this issue because it's easier from a comprehensive perspective no more or no less. Other non performance additives like cleaning additives are excluded.
 
Engine combustion is a very tough task: you want the air+fuel to burn rapidly but not explosively (too rapid!). A rapid burn creates high pressure in the cylinders while the piston is still just starting the power stroke... a "slow burn" looses efficiency because the cylinder pressure builds up slower, giving the piston time to be moving downwards: as it moves down, the volume in the cylinder is expanding so the pressure increase from the burn is somewhat canceled because it has more volume to pressurize.

The speed of the burn is affected by all sorts of parameters:
* air:fuel ratio: too little fuel leads to a hotter burn actually (because the heavy/huge gas molecules that haven't yet burned absorb some thermal energy... lean engines have less gas to absorb the early combustion energy)

* air-fuel mixing: ideally the air and gas molecules are perfectly mixed and the gas is perfectly atomized into a fine mist - not a few big droplets. Gas in the middle of a droplet is isolated from oxygen so it can't burn until the outer gas molecules are burned off.

* density of the air:fuel mix. If you're driving at high altitude, the lower atmospheric air pressure means there are fewer air & fuel molecules in the cylinder (compared to drivers at sea level altitudes). When the piston moves up on the compression stroke, compressing the air+fuel mix, it not only causes the pressure to rise but the temperature also rises - a consequence of basic thermodynamics. Over-compress the air:fuel mix and it'll hit the flash point temperature and the engine will have problems. At high altitudes, since there is less air to start with, the final pressures will be lower so high-altitude engines have a lot less risk of reaching the flash point. Driving at part-throttle (instead of foot-to-the-floor throttle) is similar to high altitude driving: the cylinders start with less air. Also, with less air+fuel at the top of the compression stroke, the air & fuel molecules are ever so slightly further apart from each other... so when the burn starts, it takes a fraction of a second longer for the flame front to travel from the spark plug to the edges of the cylinder. That's why engines have variable ignition timing: the spark is introduced a little earlier to make up for altitude or part-throttle conditions.

The spark is triggered BEFORE the piston reaches its maximum upward travel in a car engine. Why? Because it does take a fraction of a second for the flame front to work its way across the whole combustion volume. So the spark is triggered slightly early so that the peak of the combustion happens when the piston is just starting its downward power stroke. Getting this "spark advance" incorrect leads to problems:
* too much advance = piston isn't quite ready to start going down when the combustion pressures build up. This leads to knock/detonation.
* too little advance = burn is initiated later when piston is already moving down... so the combustion pressure is late and thus less effective at pushing the piston down. The engine looses power and efficiency.

Octane affects how rapidly the flame front moves... high octane fuels take a tad longer to "light off" than lower octane fuels. That's why "old" engines without computer controls don't benefit from high octane fuels: if their ignition timing systems were designed for regular grade fuel, they won't "know" to add a tad more ignition advance to compensate for the higher octane. Conversely, older "performance" engines designed & tuned for high octane fuel will probably knock/ping/detonate if driven with low octane fuel... especially when you "mash the gas" and ask for power.

Modern engines with oxygen sensors (used to measure the quality of the air:fuel ratio after the burn so the computers can adjust it for the next burn) and knock sensors can continually adjust ignition timing advance to optimize for whatever octane gas is used.

Old engines, since they didn't have feedback (i.e. oxygen sensors in the exhaust) had to be tuned "on the safe side": slightly rich, less than optimal ignition advance... so that normal variation in fuel quality, mechanical drift in the tune-up settings, etc. wouldn't lead to dangerously lean air:fuel ratios.

As long as this post was, in reality it barely scratches the surface of engine combustion, air:fuel ratios, ignition timing, etc. There is a LOT to the story. For this thread though it comes down to:
* non-computer controlled engines are generally tuned for a particular octane rating - and tuned "on the safe side" so they're really tuned for even less octane - and generally won't "recognize" higher octane fuel to adjust to it. A mechanic can re-tune the engine though for higher octane.

* with computer controlled fuel injection and computer controlled ignition timing (and a knock sensor for feedback) the engine can somewhat tune for various octanes. To REALLY take advantage of higher octane fuels though engines would also need to be able to vary their compression ratios.

mike c.
 
Being in the refining industry for 37 yrs, I see this in a somewhat different context.

1) Only about 10% (nominally; depends on crude source/type) of the gas in ones tank occurs naturally in the typical barrel of crude oil...

2) The remaining 90% (or so...) of gasoline in ones tank has been synthesized via various 'cracking' processes whereby molecules have been strategically rearrainged for the refiner to end up with marketable products instead of unmarketable products; or in this case, more gasoline. (BTW, this selective molecular rearraingment from 'organic' base stock is also where '$ynthetic' [not so] oil comes from...)

3) Most refiners (especially independents, whether company x, y, or z) on nearly a daily basis process crude oils from various different sources from around the world...Their process units run continously (e.g. meaning not seperate batches/slates), and sometimes different crudes are blended together as one crude slate. Downstream operating unit operating targets are monitored constantly and processes adjusted continually to maintain targeted specs.

4) Naturally occuring gasoline (the 10%) is called straight run, and is easily removed from the crude oil via simple distillation or 'fractionation' processes. Prior to WWII this was sufficient in scope to meet the gasoline needs of America. After WWII, the demand for gasoline(s) began to skyrocket, while the demand for gas oils sharply declined (e.g. became mostly unmarketable).

5) Cracking processes were developed (pre & post WWII) to convert unmarketable products into those more marketable (e.g. mostly gasoline and later more diesel)

6) Most of the remaining synthesized gasoline stocks come from units called platformers 'platformate', reformers 'reformate', Hydrocrackers 'hydrocrackate(s)', alky-plants, etc.

7) Along with 'straight run', these all make up the blend stocks (excluding oxygenates; MTBE or ethanol) that ultimately end-up being blended into whats the typical gallon of any companies gasoline.

8) All gasolines contain certain additives (primarily anti-varnish agents for fuel injectors), and as a practical matter (e.g. other than 'marketing mojo') these additives are very nearly equivalent.

9) It can be difficult to say where a particular service stations gasoline (or diesel) was refined at (or by who) but generally speaking, 'branded' gasolines end-up using their own proprietary additives (again read as marketing).

As Always Best Regards,

3 tons
 
Personally, I think we are all being hosed by the oil companies. Til last year, Mid grade was 10 cents more per gallon than Regular and Premium was 10 cents per gallon more than mid grade. Somewhere in the dark of night, they decided to charge us 15 cents more for Mid grade and 30 cents more for Premium. I've found a couple of stations that haven't don't this yet and that is where I shop. I use Premium as that is what is recommended for both of my vehicles.
 
I'll brave the waters a moment to buck the tide of this popularist hate oil company retorical mind set...

1) Consider that the typical gallon of anybodys gasoline cost less than a gallon of milk or bottled water product, and you begin to see the bargain at the pump.

2) The raw material (crude oil) is very expensive to procure and the cost is passed along to the end user (think consumer).

3) The extreme amount of processing (think technologies, unit maintenance cost, et al) required to produce a single gallon of fuel, far costlier than any dairy operations.

4) The extreme amount of often reduntant environmental regulations/mandates/permitting at federal, state, county levels (and often cities) by a mirad of governmental agencies, all cost passed along to the end user (think consumer).

5) The tax in California on a gallon of gasoline (at todays prices) fed, state, county is about 85 cents per gallon. All cost passed along to the end user (think consumer).

6) Did I mention logistics or payrolls?

7) If some hate America wing-nut sets off a bomb somewhere on the other side of the world, a gallon of gasoline may likely go up about 10 cents due to uncertainties in crude supply.

8) Gasoline prices tend to react (think increase>) quicker than they decline because the downline logistics stream is trying to adjust for having to aquire their next bulk purchase (think free markets).

9) Gasoline cost are much cheaper in America than almost any other western country.

10) The 'real' cost (e.g. if adjusted for 50 yrs of inflation) for gasoline would likely exceed $8-9 per gallon.

11) The D.O.E. which was created in the 70's to formulate a national energy policy, to prevent the reoccurrence of gas lines has cost the country billions of dollars yet has failed to produce a single barrel of crude oil or a national energy policy (think foreign entanglements...).

12) The 'refining' industry in America is financially nearly in the tank...Money that is being made is not being made on the costly refining side of the business, but on the production side (think crude oil). No new refineries are being built and in fact many have been shutdown or sold (from major to independent refiner) for this reason. With present trends, our refined petroleum operations will eventually be outsourced offshore to third parties, likely places like India and China (think end of self reliance).

13) American 'producer' oil companies (not independent refiners which own no oil)own only about .06% of the crude oil in the world. When crude cost go up mostly foreign dictators, cartels, governments prosper - not oil companies.

14) In spite of all these uncertainties somehow a gallon of motor fuel finds its way to the retailer (think incentivism at work). Any government would be inept at doing this (think gas line$). Though the temptation exist, this should not be taken for granted.

Thinking caps Required,

3 tons

p.s. as far as tracking a particular theoretical 'higher-value' octane molecule thru this process to the pump, I wish you well my friend!!
 
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I'm not an oil man and I DON'T hate the oil companies, but when pricing for mid grade and premium go from a dime to 15 cents for no apparent reason other than they can charge for it and we will pay it, I think we are hosed. I've got a very good friend who does work in the oil industry and he has some eye opening stories and information that he oftentimes share with me. As far as logistics, you cannot rationalize price differences within a specific locale as the logisitics of delivery are essentially the same. I take exception when people say we pay less for gas than Europe. We pay less because we pay less taxes than they do. The pay the same for the barrel as we do.

I come from an era that the price of gas was stable and stayed the same for months at a time. If oil was no longer treated as a commodity, pricing would stabilize and stay the same. But when people trade on it's future and going long or short, nothing is stable. I am used to daily price changes, but I still have problems with dime raises and penny reductions. We need to change over to natural gas.
 
If oil was no longer treated as a commodity, pricing would stabilize and stay the same......We need to change over to natural gas.

Good points...I would submit, one of the imperfections/nuances of the free markets. Still (e.g. with it's imperfections), the best system yet devised by mankind.

I fully agree that natural gas is the way to go...(though I'd likely have to find a new line of work!!)

Vast quanities of natural gas are readily available; the distribution systems to a large degree are already in place; clean burning/less environmental impact; free of OPEC cartels, Hugo Chavez, foreign entanglements; revised strategic alliances and objectives (bring some troops home), etc. This would all be some very good news!

The only thing preventing us from making this wise move is ourselves. But to do so would require multi-dimensional thinking, the will, leadership and formulation of a national energy policy. This is why the D.O.E. was formed and what the D.O.E's. congressional mandate is all about (since the 70's), yet no cohearant effort is afoot or in any way near to make this sensible, relatively easy conversion occur, or America [finally] energy independent in this way!! So much for leadership solutions from our national policy makers...

Respectfully,

3 tons
 
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