The Science of Oil

What IS your oil?

So obviously something happens to it between the time it gets pumped out of a well and the time it gets poured into your engine. I hadn't put a lot of thought into it before I took an machinery lubrication class for my work about 15-years ago.

Think of your oil as being two components... the base stock, and the additives. For grease there is a third component, the thickener, but this post is about oil, not grease. Let me address each component separately.

Base Stock: This is the oil part of the oil... that is to say the petroleum that we begin with to make motor oil. There are two general starting places for oil, mineral oils and synthetic oils. The mineral variety which is the original, is essentially a refined component of crude oil. API (the American Petroleum Institute) categorizes oil into Groups 1 through 5. Groups 1-3 would be this kind where the origin is crude. In most cases the oil has gone through a hydrocracking process to further refine and create a stable and robust base stock. Group 4 oil is polyalphaolefin (or PAO) or what is commonly referred to as a Synthetic oil. That, however, is a bit controversial as the API considers Group 3 (mineral) to be a synthetic as it has a higher amount of refining and hydrocracking to produce a very high quality base. That said, PAO oils are superior in almost every aspect. PAO's come from a process that uses natural gas to synthesize the liquid. They are also very expensive. So due to this you could conceivably buy a synthetic oil in the US with no PAO. In fact no oil manufacturer will tell you the precise formulation of base stocks, but I prefer to use Mobil 1 as my synthetic of choice for the following reasons:

1. Even though they don't tell you the formula, Mobil 1 does claim to contain PAO. 
2. The formulation of the original hasn't changed in many years. 
3. The overall performance is outstanding regardless of base stock formula. 
4. So much so that they have a high percentage of use in race cars. 
5. I have personally had very good results. 

Additives: There are many kinds of additives.... I will address three primarily. Viscosity Index Improvers (VI), Anti-wear (AW), and Extreme Pressure (EP). VI improvers are a class of polymer that react with temperature to improve the thermal performance of the oil viscosity. That is to say that oil viscosity changes with temperature (shocking I know), and this polymer expands and contracts to make the viscosity change less dramatic. VI improvers are the reason some oils are labeled multi-wight vs single weight. An oil labeled for example as SAE-30W is a single wight and has no VI improvers. An oil labeled SAE 5W-30 would have VI improvers and have the effect of making the oil behave like a 10-weight at low temperatures and a 30-weight at high (operating) temps. There is considerable confusion on this topic, so hope this part helps.

EP additives include mostly Calcium Sulfonates which has the effect of helping the oil withstand very high pressure. An oil labeled as heavy duty, or extreme duty would have more of this.

AW additives are mostly Molybdenum Disulfate which actually has lots of benefits including reducing friction, bonding with metal, and preventing wear.

In addition to the above, motor oil manufacturers often include other additives such as detergents and dispersants to help keep the engine clean by minimizing sludge buildup, corrosion inhibitors, and alkaline additives to neutralize acidic oxidation products of the oil.

One thing I want to emphasis here is that last part. Modern engines use motor oil as part of the emission control systems, and thereby builds up acidic compounds in the oil over time. The counteraction to this would be including a alkaline component in the additives to prevent damage from acidic oxidation. So new oils are always more alkaline than used.

As you can see above, automotive engine oil can be a tremendously complex system, and this is a very simple introduction to the interesting world (I think) of oil.

Nitrogen Filled Tires

For anyone who has known me for any length of time, you might have heard me occasionally rant about nitrogen-filled tires.  I personally think that its the biggest scam inflicted upon the driving public in a generation... right up there with undercoating. My problem is not necessarily with the benefit of using nitrogen to inflate your tires, but more so with the overstatement of that benefit. First let me talk a bit about whats happening with the "air" that comes stock in your tire then I'll talk about how that's different with an all-nitrogen fill.

"Air" is actually about 78% nitrogen already, then 20.9% of it is oxygen, the last 1.1% or so is other gasses like argon. One of the characteristics of this mix of gasses is that it behaves pretty much according to the ideal gas law... which is the following description:

PV=nRT

where:

• P is the pressure of the gas 
• V is the volume of the gas 
• n is the amount of substance of gas (in moles) 
• R is the ideal, or universal, gas constant (just a number) 
• T is the temperature of the gas 

So not only does air behave according to this description, but each one of the components of air individually do also. One point to make here is that your tire pressure is directly related to temperature... so think about that when trying to figure out if you've "lost" air in you tire or its just colder. This is why you should check tire inflation when the tires are cold.

So now lets talk about the purported benefits of a nitrogen-only fill. The sellers of this service claim that it:
1. Reduces oxidation on the wheel and tires
2. Reduces molecular seepage and thereby under-inflation (which has lots of other effects)
3. Reduces moisture in the tire.

There are actually lots of other benefits that are claimed but all of them basically are derived from these three. So let me address them individually. Yep, it probably does reduce oxidation of the tire and of the wheel itself.  But that is almost never the cause of failure of a tire or wheel.  Molecular seepage also probably happens... but the claims are that it is "normal" for a tire to loose 1-3 psi per month due to permeation (seepage)!  However it has been shown that the more-realistic rate is more like 0.3 psi per month according to this ARPN Journal study.  Finally, yes it does actually reduce the moisture in the air... but again the amount of moisture in the air is already minuscule.  First off the air can only get into the tire as vapor so assuming 100% humidity there could only be a few ounces of water total in there.  Furthermore, most air compressors have the effect of drying the air used because of the over-compression and then precipitating out of water in the compressor.  This is why all air compressors have water drain systems.  Plus the effect of water in the tire is not that significant either.  It still behaves like an ideal gas.

Here is some math on the moisture content:

Let's first examine how much water is actually in the air that is used to fill tires. Generally the tire shop (or home shop) uses a piston air compressor and a pressure tank to source the compressed air for the tires. If we assume that the air compressed is 100-degrees f and 100% relative humidity starting at atmospheric temperature.… sort of a worst-case scenario. In terms of how much actual water is in the air, the moisture in this case works out to be 4.3% of the air mass. If we compress that mix up to 100 psi (what most shop compressors run at) then using standard psychometric charts, we see that the capacity for the air to hold water is reduced substantially. In fact the air can only then hold 0.53% mass of water.  In practicality we see that in shop compressors because you have to drain water out of the air tank periodically.  So then taking that air and cooling back down to 75-degrees (or basically the temperature of a normal shop), the water holding capacity goes even further down to 0.24% mass. This is also why industrial air compressors have dryers… because when the air cools down there will be more moisture dropped out. Luckily in a shop environment this happens mostly in one tank. The last step then is for the air to be inserted into tires. The pressure then changes back down to about 30 psi. So using the final mass of water in our air, the relative humidity of air in the tire will be 39% (remember starting at 100%), and the dew point will be 48 degrees.

But lets be real for a moment here… when was the last time your wheel rusted out? Or when was the last time you had a tire fail due to internal corrosion? The reason it doesn’t is because the air in you tire is already far dryer than the atmosphere. This is a simple case of saving drivers from a risk that is exceptionally low.

Pressure Variation Theory:

As noted above, pressure inside your car tires can be modeled using the ideal gas law.  In that law the relationship between pressure and temperature is identified as being a linear relationship. Using a 30 PSI tire, the relationship shows that for every 10 degree change in temperature, pressure changes by about 0.9 PSI. However, in this model, it doesn’t matter what gas is used. Air, nitrogen, water vapor all can be modeled with this formula to a reasonable level of accuracy. However, the nitrogen purveyors have constructed an interesting argument. That is that they assume that the water contained in the tire air is in a liquid state at normal temperatures and then goes to gas state at driving temperature. To figure out how much this effects the tire pressure, lets do the math. Using the data above you can see that is clearly is possible to have some liquid water in the tire assuming ambient temperature is below 48 degrees and you filled up at 100-degrees and 100% humidity. So how much does that effect pressure? Lets take our 0.24% water derived above and convert that to actual amounts. Assuming the air volume in a tire is about 12-gal, that would equate to about 0.368 Oz of water.  Using steam charts at 35-psi, the specific volume change in water is 696 times.  So our .368 Oz of water would be .01Kg which equates to 10 milliliters in liquid form.  Using our steam chart (and that assume that the water changes from 100% liquid to 100% vapor) the new volume would be 6,960 milliliters or 1.8 Gal.  But remember that it now complies with the ideal gas law so in order for the change so we compress that to 35 psi it becomes 0.5 gal or 4% of the compressed air volume. Using the fact that proportionality applies to pressure mass relationships this would increase or decrease pressure about 1.4 psi.  So even in the most extreme example I can think of the state-change theory of nitrogen promoters has a very small effect.

1. There probably is a benefit to having only nitrogen in you tires vs "just" 78% nitrogen.

2. The benefits however are way too small to matter especially if you're paying upwards of $70 per tire for this service.

3. You would be far better served by just checking the pressure on your tire regularly.

Don't be afraid of your car

Technology can be scary, but fear not.

I cant tell you the number of times I've heard the complaint from car owners that modern cars are too high tech these days and that it's too complicated for the average home mechanic to effectively fix things.  I disagree to an extent.  First lets review the historical perspective of the technological advances of cars.  When I was in high-school (late 1980's) I took several years of auto shop.  At that time computers were beginning to be more common in cars but we were trained to tune and maintain cars that were truly without computers.  That is to say we adjusted points, timing, carburetors, and a variety of other analog adjustments.  However even then, there were things that were just out-of-scope for the average mechanic.  For example if you spun a bearing, it would have been very unlikely that the average mechanic would have the equipment and knowledge to repair that themselves.

Fast forward a few years and in the early 1990's I started working on cars that had actual computers in them.  That's when I discovered the wonders of the diagnostic trouble codes (DTC).  The earliest versions of these required the home-mechanic to jumper the diagnostic port and record the number of times the "check engine" light flashed.  It would translate to any stored error codes that the car recorded (most likely a sensor of some sort).

Well things have gotten much easier these days, and I would argue even better than before computerization.  This has a lot to do with the OBD2 standard that all modern cars now comply with and governs how computer error codes are communicated to the mechanic.  It is possible to plug in a code reader or computer to your car and not only view all the trouble codes, but also see in real time dozens of individual sensor measurements in real time.  The reality is that you cant set timing or dwell on a modern car and that's a good thing.  Let the computer figure out the best operating parameters.  I'm not saying that every thing that goes wrong with your car can be understood by your computer interface, but diagnosing a car problem is much different today that in used to be... but it still requires diagnostic skills.  For example when I look at a error code generated by my car, I also reference the factory service manual and in fact online discussions of the same issues... experience still matters.

The car companies sure don't make it easy.  Most of the time when you pop the hood of your car the first thing that you see is usually a large plastic engine cover.  Its there mostly to keep the owner from seeing and fiddling with the engine.  That said don't be afraid of plugging in and figuring out what's going on.  There still will be a time and place for bringing it to your mechanic.  I have no problem taking my car in for an alignment, recalls, and plenty of other things that I don't have the equipment or knowledge to do myself... however jumping in and working with technology doesn't scare me and it shouldn't deter you either.