How Green is your Fuel?

Creation and comparison of

automotive biofuels
Wagner, E.P., Koehle M.A., Moyle, T.M., and Lambert, P.D.

Objectives
In this experiment three alternative green fuels are created/synthesized and then evaluated for
energy content, viscosity (a significantly important physical property for automotive fuels), and
true environmental impact. The main goal is to determine which is the best alternative based on
experimental results and information found in literature.

Purpose
In recent years, biofuels have risen to the forefront of alternative fuel options. This lab intends to
educate you on the various alternative fuels that are being developed for automotive applications
and the advantages and disadvantages of each. You will replicate commercially available
alternative fuels, E85 (Ethanol) and Biodiesel, as well as create an experimental fuel blend of
waste vegetable oil and petroleum products referred to as “VeggieDiesel”. This type of
experimental fuel blend has been under development and evaluation for over 20 years (1-6).
Your goal is to evaluate the viscosity, energy content, production energy requirements, and
environmental impact (sustainability) of each alternative fuel. In addition, you will report on
what you believe is the best theoretical model for predicting viscosity of blended fuels. You will
also report on what you believe is the best theoretical model for predicting heat of combustion.
Finally, based on your laboratory results and literature findings, draw your own conclusion on
which fuel you believe is the best “alternative”.

Introduction
There is a list of standards and requirements, as outlined in the ASTM Standards, that a diesel
fuel must adhere to in order to become an EPA certified fuel (7-8). In addition, the fuel must
have physical properties that allow it to burn in the engine without detrimental effects. This lab
will focus on two of these properties: energy content and viscosity.

Viscosity is critical because the fuel needs to flow easily through the fuel lines and into the
engine cylinders to allow proper injector spray patterns and complete combustion of the fuel.
Viscosity is a temperature dependent physical property and is thus greatly affected by ambient
weather conditions.

Energy content is important because it correlates to engine performance and gas mileage. A fuel
with low energy content (heat of combustion in this lab) will have diminished horsepower,
torque and gas mileage.

Certainly many fuels could be created with appropriate physical properties. However, it is
important to also consider the overall life-cycle impact of the fuel on the environment. For
example, the life cycle of CO2 created through internal combustion engines is of major concern
today. If the start of the carbon life comes from sequestered oil deep underground it must return
there in a timely manner in order to have a “closed” lifecycle. This is referred to as
sustainability. As you probably know, CO2 from burning petroleum ends up in the atmosphere

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and can not return to its origin for over 200,000 years (9). Thus, petroleum fuels do not have a
closed lifecycle. Consequently, CO2 concentrations have been rising in the atmosphere at
alarming rates for the past 50 years. On the other hand, a fuel created from plants is far more
sustainable because plants sequester CO2 from the air. Keep in mind that production of a fuel
also requires energy, something you should consider while evaluating sustainability. For
example, if the fuel itself is carbon neutral, but requires significant production energy, then the
sustainability factor of the fuel is greatly diminished.

Background of the alternative fuels investigated in this experiment

E85 (Ethanol)
E85 is a mix of 85% ethanol and 15% gasoline (octane or isooctane) and is currently being used
in Flex-Fuel vehicles that may run on either gasoline or E85. Ethanol in the U.S. is typically
produced from corn, although can be made from any plant with sufficient amounts of sugar. The
sugar is first extracted from the plant and then yeast is introduced, which converts the sugar to
ethanol through a fermentation process. This typically creates a mixture of 20% ethanol and
80% water. Fuel grade ethanol must be nearly anhydrous so the water - ethanol mix is typically
distilled to about 95% ethanol. (Why can’t the ethanol be distilled to 99%?) The mixture is then
further purified to near 100% pure ethanol and mixed with gasoline to make E85. Current
research efforts focus on developing membranes with the ability to separate water and ethanol.
This, in turn, would significantly lower production costs. There is also research being conducted
to produce ethanol from cellulose, allowing for the use of switch grass instead of corn.

Corn ethanol does have drawbacks. The amount of heat and energy required to produce it is
significant. Harvesting the corn and then distilling the ethanol results in decreased energy yields.
Some estimates indicate that ethanol production has virtually no net energy gain (10). Since
ethanol comes from food sources, there are economical and ethical issues surrounding the use of
“food for fuel”. As the demand for ethanol fuel increases, both the price of ethanol and corn rise.
This has direct results on increasing the cost of corn-based food products as well as indirect
results of raising the cost of meats and dairy products due to the corn consumption of livestock.
Additionally, growing corn puts strain on farmland, resulting in the need for fertilizers.
Fertilizers are often derivatives from petroleum based products and their production requires
large amounts of energy. The runoff from these fertilizers has lead to eutrophication problems in
the Gulf of Mexico and other smaller bodies of water. Finally, because ethanol has fewer
chemical bonds than gasoline and other fuels, it has less energy content. Thus, one gallon of
ethanol is equivalent to 67% the energy content of a gallon of gasoline (11), resulting in a
significant reduction in fuel economy. The possibility of creating ethanol from non-food based
plants and wild grasses does exist and is potentially a very promising option for ethanol
production. Be sure to search literature to gain additional insight into these issues.

Biodiesel
Diesel engines are prevalent in our world. While most cars in the U.S. are not diesel engines,
larger trucks, construction/off road vehicles and machinery use diesel engines because of their
high torque, high power, and energy efficiency. The fundamental differences between a gasoline
engine and diesel are that a gasoline engine relies on a spark to ignite the fuel and the
compression ratio in the gasoline engine is lower than that of diesel engines (typically about 9:1).

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Diesel engines have a higher compression ratio (sometimes as high as 22:1), which allows the
fuel to detonate by the temperature increase resulting from gas compression. As a result
heavier/bigger fuel molecules (carbon chain lengths from 8 to 24) can be used, which means
higher energy content per volume of fuel compared to gasoline.

Biodiesel is a fuel made from vegetable oil through transesterification (Figure 1). Through this
process, the triglyceride molecule is broken into 4 separate molecules: three fatty esters and one
glycerol. In doing so, vegetable oil with a typical molecular weight of 900 g/mol is broken down
to three methyl ester molecules (the biodiesel) and glycerol (byproduct/waste). Glycerol is a
thick, viscous liquid, but the fatty esters can be separated from the glycerol and used as a fuel.
Breaking the molecule down into the fatty esters lowers viscosity and reduces the temperature at
which it solidifies.

Figure 1: The transesterification synthesis pathway for creating Biodiesel

The best and most sustainable way to make biodiesel is by using waste vegetable oil (WVO)
from deep fryers in restaurants. Yes, that is correct: cook your French fries and then use the oil to
make fuel. Biodiesel does have some drawbacks to its use. Methanol is a very flammable and
toxic reagent that must be handled with great care. Ethanol can be used instead, but makes it
much more difficult to achieve complete reaction. Sodium hydroxide is caustic and also very
dangerous. Another disadvantage is that some energy content of the neat vegetable oil is lost
through the breaking of bonds (exothermic reaction) and the removal of glycerol from the fuel
(glycerol has a heat of combustion of approximately 18 kJ/g). Finally, the production process
requires the use of energy, decreasing the net energy gain from production (12).

One final point to be aware of is the supply of vegetable oil is quite limited in comparison to the
amount of diesel fuel used in the United States. The U.S. uses 62 billion gallons of diesel fuel
each year, but only makes approximately 650 million gallons of soybean oil per year (11,12). So
it seems that there is not enough vegetable oil to replace 100% of our diesel fuel needs. In fact
most biodiesel in commercial use today is 5% biodiesel mixed with petroleum diesel. The
maximum amount of biodiesel allowed in diesel fuel by the EPA is 20%.

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VeggieDiesel
Given that there is not a sufficient supply of vegetable oil or plants to completely replace
petroleum fuel, all biofuels need to be mixed with petroleum products. Since this is the case,
another viable method to lower viscosity of vegetable oil (instead of transesterification) is to
simply blend it with lower viscosity components, such as petroleum diesel and gasoline. In
doing so, the viscosity of the vegetable oil can be reduced down to an acceptable value for
operation in a diesel engine. Further, the production energy requirements are minimized. The
idea of using pure or straight vegetable oil (SVO) as a fuel is not new. In fact, Rudolph Diesel in
the very early 1900s first developed the diesel engine to run on 100% peanut oil. Even in
today’s diesel engines, it is possible to operate on 100% SVO or WVO, but it does require
significant vehicle retrofitting to install a heated fuel supply system to lower the oil viscosity.
This retrofitting includes separate fuel tanks for diesel and vegetable oil, fuel tank heaters and
inline fuel heaters. The main challenge of running SVO or WVO is its high viscosity. By
incorporating these heating elements, it is possible to start a car on diesel fuel and then, once the
vegetable oil has been heated and its viscosity has decreased, switch the vehicle to run on WVO.
This retrofitting is relatively expensive and actual savings are not realized until driving
approximately 25,000 miles on WVO.

Another solution to the “two tank” retrofitting is to lower the viscosity to an acceptable level by
blending with petroleum diesel and other low viscosity components. Diesel fuels created
through this blend method are referred to as “VeggieDiesel”. For example, if a 50/50 blend was
created with diesel and vegetable oil, the resulting viscosity would roughly be an average of the
two components (see Figure 2). In order to effectively run a fuel in a diesel engine, the starting
fuel viscosity should be less that 15 cSt. As the engine warms, the fuel will naturally heat up and
decrease in viscosity. ASTM standards indicate that diesel fuel must have a viscosity around 5
cSt or less at 40oC (104oF). As you can see in figure 1, mixing only diesel with oil will make it
difficult to obtain the proper viscosity at ambient temperatures. Certainly there are many
blending ratio possibilities as well as potential components to add. Based on research

Figure 2: Temperature dependent viscosity curves for diesel fuel, vegetable oil and a 50/50 v/v
blend of both.

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conducted at the University of Pittsburgh the best bulk components that can be used to modify
the viscosity are diesel, kerosene (aka diesel #1) and gasoline (13). It will be your job in this lab
to use viscosity data to first model/theorize a VeggieDiesel blend (see the following viscosity
section) and then create and test your VeggieDiesel blend in the lab for its actual viscosity as
well as energy content. In doing so, you can determine how well your modeled viscosity
matches the actual viscosity. You will also model the energy content, which will allow
experiment to theoretical model comparisons. Keep in mind that energy content is a separate
issue from production energy requirements. For example, VeggieDiesel does not involve the
transesterification process. Therefore its total production energy requirements are 35% lower
than biodiesel. In addition, VeggieDiesel requires 50% less fossil fuels in the production process
compared to biodiesel (11,12).

Viscosity
Viscosity is a measurement of a fluid’s resistance to flow. Kinematic viscosity is the ratio of a
fluid’s absolute viscosity to its specific gravity and is usually measured in centistokes (cSt) (14).
A common method of measuring kinematic viscosity is with a capillary viscometer, in which a
volume of liquid is timed for how fast it runs through a vertical capillary tube. This method is
based on Poiseuille’s law, or

V r 4 P1  P2
 (1)
t 8v L

where V is the volume of liquid that flows through a cross section of the capillary tube in time t,
r is the radius of the tube, v is the viscosity of the liquid, P1-P2 is the difference in pressure from
the top and bottom of the cross section, and L is the length of the cross section (14).

You will be taking viscosity measurements in this experiment with calibrated Cannon-Fenske
glass capillary viscometers. With these viscometers, the time it takes for a sample to flow
through a certain volume is measured. This is referred to as the efflux time and is related to the
sample’s viscosity through the viscometer constant. This constant is different for each
viscometer and is linearly related to temperature.

Temperature-Viscosity Correlation
The viscosity data from two different temperatures of a sample may be used to correlate
viscosity to temperature according to the equation
ln  = -B(T) + A (2)
where v is the viscosity in centistokes, and A and B are the intercept and slope, respectively, of
the straight line formed when ln v is plotted against temperature (T), in Kelvin (Figure 2)
(14,15). The range of temperatures we are most concerned with for a fuel blend is 250-330 K.
The viscosity of some fuels is quite low and controlled at the time of production, and thus, does
not vary significantly. The A and B coefficients for the viscosity-temperature correlation
(Equation 1) of the petroleum products and ethanol used in this lab are provided in Tables 1 and
2. However, the viscosity of biodiesel and waste vegetable oil can vary greatly due to the type of
vegetable oil used, which is why you will need to measure these viscosities at two different
temperatures and then determine the A and B coefficients.

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Table 1: Physical Properties of Fuels
Fuel Molecular Weight Density Viscosity curve coefficients
(g/mol) (g/mL) A B
Diesel 230 0.885 9.12 0.0264
Kerosene 165 0.817 6.44 0.0191
Gasoline 114 0.737 3.51 0.0135
Ethanol 46.0 0.789 5.69 0.0177
Biodiesel 247 0.880 * *
WVO 878 0.926 * *
* Values to be determined through your experiments

Table 2: Typical composition of soybean oil triglyceride groups

Triglyceride % by mass Formula
Palmitic 12 (C15H31CO2)3C3H5
Stearic 5 (C17H35CO2)3C3H5
Oleic 25 (CH3(CH2)7CH=CH(CH2)7CO2)3C3H5
Linoleic 52 (CH3(CH2)4CH=CHCH2CH=CH(CH2)7CO2)3C3H5
Linolenic 6 (CH3(CH2CH=CH)3(CH2)7 CO2)3C3H5

Predicting Blend Viscosity

Based on the viscosities of individual fuel components and the ratio of the components in a
blend, one may predict a fuel blend viscosity. As stated before, viscosity is a temperature
dependent. Thus, before you can begin predicting the viscosity of your blend, you must know
how the viscosity of each blend component corresponds to temperature.

Many models have been developed for predicting viscosity of a blend (16). The Arrhenius
equation, as discussed by Grunberg and Nissan (17), is the most fundamental and uses mole
fractions of each blend component to determine the overall viscosity.

ln blend = N1ln 1 +N2ln 2 (3)

where N1and v1 are the mole fraction and viscosity of component 1, and N2 and v2 are the mole
fraction and viscosity of component 2 at the same temperature. For example, if a 50/50 mole
blend of gasoline and diesel were created, the viscosity at 40oC (313K) is theoretically calculated
to be:
blend, 313 K = exp((0.500*(-0.0102*313 + 2.54))+(0.500*(-0.0264*313 + 9.12))) = 1.11 cSt (4)

The equation may be extended to include more than two components. While originally written
for mole fractions, this equation has also been used successfully with mass and volume fractions.
In this lab you will investigate which ratio method is most accurate and then provide an
explanation to your findings.

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Energy Content (Bomb Calorimetry)
The chemical equation for combustion of organic compounds with air at atmospheric
temperatures is:

CxHyOz + aO2(g) + (a*0.79/0.21)N2  CO2(g) + H2O (l)+ N2(g)

This equation assumes that the products include CO2, H2O (l), and N2(g). For vehicles, NO and
NO2 (grouped as NOx) are a large concern in the emissions of a vehicle. Why is NOx not
included? Hint: Find the Gº, Hº and Sº and K for the following reaction. What will
happen with these thermodynamic measures as the temperature increases from atmospheric
conditions to that found inside an internal combustion engine (~2500K)?

N2 + O2 2 NO

In this experiment you will use pure O2(g) to charge the bomb. Therefore the combustion
equation is simplified to that found in most general chemistry textbooks. The heat released (q) is
equal to the enthalpy change, H (if your experiment is at constant pressure), or the internal
energy change, U (if your experiment is at constant volume). In a bomb calorimeter q is
measured at constant volume (U) which is used to calculate H through the equation below.

H = U + (pV) (5)

Because the bomb calorimeter is separated from the rest of the universe, it is possible to define
the sample and oxygen to be the system and the bomb, water and calorimeter jacket to be the
surroundings. The internal energy (U) of the reactants can then be calculated from

q=U = Usurr = m*Ccal*T (6)

Ccal is the heat capacity of surroundings (i.e. the water, the oxygen bomb and the calorimeter
jacket) and T is its temperature change. It may be assumed that Ccal is nearly independent of
temperature over the relatively small range you will be using (19ºC to 35ºC). Thus, the energy
of combustion is relatively easy to measure by recording the temperature increase during
combustion of a sample in a calorimeter with known heat capacity (Ccal). The heat capacity of
the bomb calorimeter can be determined by burning a sample with known heat of reaction.
Typically benzoic acid combustion with U = - 26.454 kJ/g is used for this purpose. For this lab
experiment, the heat capacity of the bomb calorimeter has already been determined for you and
the value is given in the bomb calorimetry calculation data section.

Predicting Energy Content

Heat of combustion for any fuel can be calculated using heats of formation or bond enthalpies. If
you can not find a heat of formation value, you can use molecular modeling software such as
CAChe to calculate it. Which ever way you choose, be clear in your report about how you
obtained the information.

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To predict the energy content of a blended fuel, a simple fraction addition can be completed
through the equation Q = Xi qi, where Xi is the component fraction (what is the fraction base?)
and qi is the component’s heat of combustion.

Provide theoretical energy content data for all three fuels studied here: E85, Biodiesel, and
VeggieDiesel.

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Laboratory Procedures
This lab will span over two lab periods and below is a chart of the order in which you will be
performing the individual experiments. Please note that it is important to obtain viscosity data
for the WVO in the first lab. You will need this information to theorize your VeggieDiesel blend
before the second lab meeting.

Between lab
Lab Period 1 Time Lab Period 2 Time
periods
Make E85 and Biodiesel 1 hr Make VeggieDiesel 1 hr
Viscosity of Use viscosity data Viscosity of
1 hr to theorize & 2 hrs
WVO and E85 Biodiesel, and VeggieDiesel
determine your
Bomb Calorimetry of Bomb Calorimetry of
2 hrs VeggieDiesel blend 1 hr
E85 and Biodiesel VeggieDiesel
component ratios
Total 4 hrs Total 4 hrs

Creating the Biofuels

E85
Make approximately 100 mL E85 ethanol (85% ethanol, 15% gasoline by volume) with the
available starting materials of pure ethanol and pure gasoline. You will use this sample for
various experiments latter in the lab.

Biodiesel
1. Measure 100 mL of waste vegetable oil (WVO) and place it into a 250 mL Erlenmeyer flask
with a stir bar. Heat the WVO on low with the stir bar set to 75% of the maximum value until the
temperature is approximately 55ºC. Once this temperature is reached, adjust the hot plate to
maintain that temperature. Keep the stir bar set to 75% of the maximum value.

2. Measure out enough methanol for a 30% excess and add it to a second 250 mL Erlenmeyer
flask with a stir bar (remember there is a 3:1 mole ratio of methanol to WVO). Obtain several
pieces of sodium hydroxide and crush them with the mortar and pestle (the mortar and pestle
should already be clean and dry). Weigh approximately 1 gram of the crushed NaOH and add it
to the methanol. Put the methanol and NaOH on a stir plate and stir them until all the NaOH has
dissolved in the methanol (this may take up to 30 minutes depending on how well you crushed
the NaOH). Do not heat the methanol during this process. Clean out the mortar and pestle
with water and then rinse with acetone.

3. Once all the NaOH has dissolved in the methanol and formed methoxide, add the WVO to the
methoxide and continue stirring without heat for at least an hour to ensure the reaction has
reached completion. During this hour, you should move on to other parts of the experiment and
come back later to finish the following steps of the biodiesel synthesis.

4. After the reaction is complete, fill six mini test tubes with the products carefully making sure
the outside of the tubes remains clean. The easiest way to do this is to use a separatory funnel.
Fill the separatory funnel with your products and then fill each test tube by opening and closing

9
the stopcock. Place these into the centrifuge for ten minutes allowing the glycerol and any soap
that was generated to separate from the biodiesel.

Note: One aspect of biodiesel production you will not investigate here is the standard method of
separating biodiesel from glycerol. In the interest of time, you separated small amounts with the
help of a centrifuge. Typically in large batch biodiesel production, the products are allowed to
gravity separate for 1-2 days. After separating the glycerol, the biodiesel is washed several times
with water to remove sodium hydroxide and excess methanol.

5. After centrifuging, decant the biodiesel off the top of all six tubes into a beaker. The top
should pour off easily while the bottom portion will be semi solid. To clean out the test tubes,
fill a 250 mL beaker with water and place it on a hot plate. Once the temperature reaches about
70 ºC, put the six test tubes in the water and wait until their contents are hot enough to pour out
into the waste container (about 5 minutes).

VeggieDiesel
1. Use the viscosities you obtained for the WVO along with Equation 1 to model the WVO
viscosity over the temperature range of 250-330 K and obtain the A & B viscosity curve
coefficients.

2. Use Excel to layout a worksheet template that uses the viscosity curve data (A & B) from
each individual fuel component (Table 1) and Equations 2 and 3 to calculate the viscosity of a
VeggieDiesel blend over the 250-330 K temperature range. Design the template so you can
model various VeggieDiesel blends by simply changing the blend component ratios. Your
worksheet should also create a graph like that in Figure 1. Make sure to create the viscosity curve
model three times, once for each type of fraction base: moles, volume and mass. Use the data in
Table 1 to help you convert between fraction bases.

3. Design a VeggieDiesel blend comprised of WVO, diesel, kerosene, and gasoline using the
following guidelines:
- Conduct all your VeggieDiesel theoretical modeling in either mass or volume fractions.
This will make it easier for you to actually create your blend in the lab.
- Your “theorized” VeggieDiesel blend must be at or below 15 cSt at 32oF and at or below
5 cSt at 104oF (ASTM standard).
- The blend must maximize WVO content (needs to be at least 50%)
- The blend must have no more than 10% gasoline
- The percentage of kerosene in the blend can not exceed the percentage of diesel
- Energy content of the blend should be at least 90% of petroleum diesel (the higher, the
better).
Note: In creating a fuel blend, viscosity and energy content are the biggest issues but there
are many other factors to be considered, including lubrication properties, cetane rating,
octane rating, emissions, and energy that goes into its production. The further
reading/references section provides many resources that may be helpful in devising a
successful blend.

4. Make 100 mL (or 100 grams if you used mass based fraction) of your VeggieDiesel.

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Viscosity Measurements
Viscosity measurements for a sample must be taken at two temperatures in order to determine
the temperature dependent viscosity curve coefficients (A & B). You will use a cool water bath,
roughly around 5 °C, and then a heated water bath at a higher temperature, around 35 °C.

1. For the cold bath, use a 4 L beaker on a stir plate and fill with cold tap water. Place the
viscometer (see Table 2 for selecting the appropriate viscometer size) in the bath by clamping the
large arm (arm L) to a ring stand positioned outside of the water bath. Be sure the viscometer is
perpendicular throughout the experiment. Add ice as needed to get the temperature to around
5 °C (stay above 0 °C). It does not need to be exactly 5 °C, but be certain to accurately record
your actual temperature and make sure the bath stays at a constant temperature (± 2 °C or better)
throughout your measurements.

2. Create the warm water bath the same way as above, but be certain to use a stir/heat plate.
Heat as needed to get the temperature to approximately 35 °C. It does not need to be exactly 35
°C, but be certain to accurately record your actual temperature and make sure the bath stays at a
constant temperature (± 2 °C or better) throughout your measurements.

3. Pour enough sample into a 50 mL beaker for it to be taken up by a syringe (~20 mL).

4. Take up 10 mL of sample into a syringe and inject into arm L of

viscometer.

5. Allow 5 minutes for the sample to come to temperature in the

bath before starting your experiment. Don’t forget to record the
temperature.

6. Using two pipette bulbs, one for sucking up fluid in arm N and
one on arm L to assist by pressurizing, raise the fluid level in arm N
to the top reservoir. It does not need to be completely filled, but be
certain that the fluid has no entrapped air bubbles and that the level
is above the timing mark E. Also make sure the water bath level is
higher than the viscometer fluid level to keep constant temperature.

7. The sample will begin to flow back down the tube. Begin Figure 3: Cannon-Fenske
stopwatch when the meniscus reaches line E. viscometer

8. Stop timing when the meniscus reaches line F (line below bulb).
Record the efflux time.

9. Repeat steps 6-8, to collect at least two measurements for each sample. Certainly if you have
poor precision, you need to conduct more measurements.

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10. Calculate the viscosity of the sample by multiplying the efflux time (in seconds) by the
viscometer constant at your measurement temperature. The viscometer constants given in
Table 2 are likely not at your measurement temperature. Therefore, you will need to calculate
the constants at your measurement temperature by linear extrapolation.

11. Dispose of sample appropriately and clean viscometer first with soapy water and then with
acetone.

Choosing a viscometer size

Use literature values of viscosity as a guide to pick an appropriate viscometer for each fuel;
ethanol, gas, diesel, WVO, and biodiesel (aka. yellow grease methyl ester). Choose the largest
viscometer size possible to save time. For your VeggieDiesel blend, use your theoretical
viscosity to select the appropriate viscometer.

Table 2: Viscometer Sizes, viscosity ranges and constants

Viscometer Viscometer Recommended Viscometer Viscometer
ID Number Size Viscosity Range Constant at 40 °C Constant at 100
°C
G250 25 .5 – 2 cSt 0.001963 cSt/s 0.001956 cSt/s
R816 75 1.6 – 8 cSt 0.008249 cSt/s 0.008209 cSt/s
M619 150 7 – 35 cSt 0.03355 cSt/s 0.03339 cSt/s
N884 150 7 – 35 cSt 0.03495 cSt/s 0.03480 cSt/s
M972 200 20 – 100 cSt 0.1047 cSt/s 0.1042 cSt/s
M296 200 20 – 100 cSt 0.1090 cSt/s 0.1085 cSt/s
G666 300 50 – 250 cSt 0.2366 cSt/s 0.2354 cSt/s

Compare experimental and predicted temperature dependent viscosity curves with

statistical analysis
A correlation coefficient may be calculated as follows:
SSE
R2  1 (3)
SST
where SSE is the sum of squared error, or
SSE   (a  b) 2 (4)
and
( a ) 2
SST  ( a ) 
2
(5)
n
where a is the experimental value, b is the predicted value, and n is the number of data points.
Average absolute deviation (AAD%) may also be calculated to determine the deviation of
experimental values from predicted values. The percent deviations of experimental data points
are calculated by the equation
ab
d  100  (6)
a

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where a is the experimental value, and b is the predicted value. AAD% is the sum of the percent
deviations, divided by the number of data points. This analysis should be completed for both the
VeggieDiesel and the E85

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Bomb Calorimetry Measurements
In the interest of saving time you will actually be running two oxygen bombs in one calorimeter
jacket. While one bomb is in the calorimeter and you are collecting temperature data, the second
bomb can be prepared for detonation. It is important to keep the oxygen bombs with their
corresponding oval buckets because the heat capacities of the two bombs may be different.
Set up the oxygen bomb, steps 1 through 6. Once one bomb is ready for detonation, that group
should complete steps 7 through 16. However, once you are finished with step 12 the second
bomb can be put in the calorimeter and detonated. Continue this cycle of alternating between
preparation and detonation of the two bombs until all of your runs for biodiesel and E85 are
finished. Bomb calorimetry of your created VeggieDiesel blend will be performed during the
second lab period. Keep in mind that a minimum of two runs for each fuel sample (Biodiesel,
E85, and your VeggieDiesel blend) need to be completed to establish consistency.

Note: E85 is highly volatile and is difficult to weigh precisely. Thus you will need to use a
gelatin capsule to contain the sample. Follow the procedure given below to prepare and fill a gel
capsule. You will be placing the filled capsule into the basket and then have the ignition wire
pressed against the top of the capsule. Be sure to weigh the capsule empty so you can subtract
the gelatin’s heat of combustion (3.53 kJ/g).

To fill the capsule with E85, pour a reasonable amount into a small beaker. It is important not to
touch the capsule with your bare hands so be sure to wear rubber gloves for this portion. Pull the
two parts of the capsule apart. Submerge both ends below the E85 line in the beaker trying to
remove as much air as possible. Place the two parts of the capsule back together below the E85
level in the beaker to minimize the amount of air in the capsule. It is sometimes easier to do this
with two sets of twisters if they are available. Remove the capsule from the beaker and press the
two ends fully together. Finally dry off the outside of the capsule with a kimwipe. Weigh the
basket empty and then again with the capsule recording the weights each time. Remember when
setting up the ignition wire to have it rest on top of the capsule.

During the calculations, remember to subtract the heat of combustion from the total heat
released. Additionally, most if not all of the carbon residue in the basket at the end of the run
will be from the gelatin and thus the residue mass should be subtracted from the starting weight
of the capsule, not the sample fuel.

Because E85 is a more complicated sample preparation, it is recommended that you test the
biodiesel first to gain some practice and experience.

14
The following bomb calorimeter instructions are adapted from the Parr Instruments’ 1431
Bomb Calorimeter Instructions supplied with the equipment.

1. Getting Started Disconnect the stirrer and motor pulleys. Take off the calorimeter cover and
remove the oxygen bomb and the oval bucket.

Note: Do not lay the cover on the tabletop. Always set it in the supporting ring on the stand to
protect the thermometer and stirring shafts.

2. Disassemble Oxygen Bomb Make sure the pressure release valve (Figure 4) is open (counter-
clockwise). Once you are sure the bomb is depressurized, unscrew and remove the outer locking
ring. Remove the top bomb cover and place in the holder as shown below.

Note: If bomb is pressurized and outer locking ring is removed rapid decompression of oxygen
bomb can occur resulting in serious injury.

Figure 4: Oxygen Bomb. (Figure taken from the Parr 1341 bomb calorimeter instruction
manual.)

3. Preparing the Sample Clean and fully dry the sample basket (Figure 5). Weigh the basket
without your sample and record in your lab notebook. Add approximately one gram of your
sample into the basket. Record the exact weight.

Note: Once the basket is clean, try not to touch the basket with your hands. You can get oils on
the basket that can affect the weight and alter your results.

4. Setting the Fuse Place the basket back into the holding arm of the top bomb cover (Figure 5).
Lift the wire covers on the top bomb cover to expose two holes the ignition wire must be
threaded through. Use 10 cm of wire and form it in the same manner as shown in Figure 5
making sure the wire dips into the sample without touching the sample cup. Move the wire
covers back down over the ignition wire holes to secure the wire in place.

15
Figure 5: Sample basket and fuse setup for bomb. (Figure taken from the Parr 1341 bomb
calorimeter instruction manual.)

5. Charging the Bomb Add 1 mL of deionized water to the bottom of the oxygen bomb outer
case. Place the top bomb cover back on the oxygen bomb outer case and screw the outer
locking ring back on making sure it is fully tightened. Close the pressure release valve. Open
the adjacent oxygen tank with the regulator fully off. Place the gold filing valve onto the
pressurizing valve of the oxygen bomb. Slowly open the regulator on the oxygen take allowing
the bomb to pressurize. Once the pressure reaches 15 atm. turn off the regulator and open the
pressure release valve slowly. The venting process should take at least one minute. Vent the
bomb in this manner 2 more times to ensure only oxygen is in bomb. Once venting is complete,
pressurize the bomb to 30 atm. and remove the gold filing valve by first releasing the line
pressure with the release switch on the tank regulator then pulling the gold fitting straight up.
Close the oxygen tank. Be sure not to shake or tip the bomb or your sample will spill, ruining
your results.

6. Fill the calorimeter bucket Replace the oval bucket noting the three dimples in the bottom of
the bucket which rest on supporting pins in the bottom of the jacket (Figure 6). The single dimple
must always face forward when setting the bucket in the jacket. Place the bomb into the oval
buck on the resting indentation on the bottom of the bucket. This is facilitated by holding tongs
that fit into holes on the side of the outer locking ring. Connect the two ignition wire pins (6) to
the electrical ignition ports on the oxygen bomb. Using a 2 L volumetric flask fill the oval
bucket with 2.0 L of deionized water. It is best to use water that is about 20 ºC. If necessary,
place the volumetric flask on top of ice in the ice bucket for a short period of time. Be careful not
to over chill the water because the thermometer on the calorimeter only goes down to 19 ºC.
Make sure there are no bubbles leaking from the bomb when it is under water. If there are
try tightening the fittings or ask your TA. Place the top back onto the calorimeter jacket and

16
reconnect the stirrer and motor pulleys. Turn the motor for the stirrer on with the black knob on
the top of the motor.
At this point the bomb experiment is ready to begin. While taking data on the first experimental
run, coordinate efforts and have your lab partner set up the second oxygen bomb so that it is
ready to go when the first run is completed.

Figure 6: Complete bomb calorimeter schematic and setup. (Figure taken from the Parr 1341
bomb calorimeter instruction manual.)

7. Let the stirrer run for 5 minutes This allows the system to reach equilibrium before starting
a measured run.

8. Connect the Ignition Unit Connect the disconnected wire with screw clamp to the 10 cm
screw on the ignition system (white square box next to calorimeter).

9. Read and Record Temperatures Record the initial temperature before firing the bomb and
then at 15 second intervals (using a stopwatch) after detonation.

10. Detonating the Bomb Hold the ignition button on the ignition system for 5 seconds. After
firing disconnect the wire with the screw clamp that was attached to the 10 cm screw on the
ignition system to avoid electric shock.

Caution: Do not have your head, hands or any parts of your body over the calorimeter
when firing the bomb.

17
11. The bucket temperature will start to rise. This rise will be rapid during the first few
minutes; then it will become slower as the temperature approaches a stable maximum.
Remember to record temperature readings every 15 seconds. Accurate time and temperature
observations must be recorded to identify certain points needed to calculate the calorific value of
the sample. Continue recording temperature readings until the temperature has stabilized at a
single temperature for 5 minutes. Usually the temperature will reach a maximum; then drop very
slowly. But this is not always true since a low starting temperature may result in a slow
continuous rise without reaching a maximum. If the temperature of the water fails to rise within
the first minute of detonation, the sample has failed to detonate and you will need to reset the
bomb (see following steps).

12. After the last temperature reading, stop the motor, remove the belt and lift the cover from
the calorimeter. Wipe the thermometer and stirrer with a clean cloth and set the cover on the
support stand. Remove the ignition leads and lift the bomb out of the bucket.

13. Open the pressure release valve on the bomb head to release the gas pressure before
attempting to remove the outer locking ring. This release should proceed slowly over a period of
not less than one minute to avoid entrainment losses. After all pressure has been released,
unscrew the outer locking ring; lift the top bomb cover out of the oxygen bomb housing case and
place it on the support stand. Examine the interior of the bomb for soot or other evidence of
incomplete combustion. If such evidence is found, the test will have to be discarded.

14. Remove all unburned pieces of fuse wire from the bomb electrodes; straighten them and
measure their combined length in centimeters. Subtract this length from the initial length to
obtain the net amount of wire burned.

15. Reweigh the basket This is to determine the amount of unburned fuel.

16. Clean Up Wipe down all parts of the bomb. Wash out the sample cup. Dispose of the oval
bucket water. If you have another run to complete then start back over at step 3. If you are
finished with the bomb, thoroughly clean the bomb (especially the sample cup), and reassemble.

Bomb Calorimetry Calculations

Q = m*Ccal*T (general form of equation solve for Q)
Q - (Qw - Qwu) =net energy of sample (equation corrected for heat released by fuse wire)
Qw - Qwu = Qwb (equation for Qwb)
Q - Qwb =net energy of sample (equation with Qwb as the wire correction)
(Q - Qwb)/[m] = Energy content of the sample fuel per mass unit.

Equation For Capsule Use

[Q - Qwb – Qcap*(mcap) ] = [m*Ccal*(TF - TI)]
[Q - Qwb – Qcap*(mcap)] /m = Energy content of the sample fuel per mass unit.

18
Variables
Ccal - Calorimeter heat capacity Qcap - Gelatin capsule
Ccal = 10.1 kJ/(ºC*g) size 000 (1.4 mL) = 3.53 kJ/g
Q- Heat of combustion Qwu - Unburned wire
m- Mass of sample Qw - Ignition wire (1 cm = 2.3 cal)
mcap - Mass of gelatin capsule (if used) Qwb - Burned wire
TI - Initial temperature of bath TF - Final temperature of bath

Lab Report
Data to include in your lab report:
1. Excel graph of biodiesel viscosity vs. temperature (250-330 K)
2. Excel graph of WVO viscosity vs. temperature (250- 330 K)
3. Excel graph of VeggieDiesel blend viscosity vs. temperature (250-330 K)
a. Experimental data
b. Moles prediction
c. Mass prediction
d. Volume prediction
4. Excel graph of E85 viscosity vs. temperature (250-330 K)
a. Experimental data
b. Moles prediction
c. Mass prediction
d. Volume prediction
5. Table of data used in the graphs above
6. Statistical analysis of theoretical viscosity deviation from experimental results.
7. Experimental heat of combustion data (energy content per mass) of all three fuels.
8. Theoretical heat of combustion calculations for all E85, biodiesel and VeggieDiesel
Be sure to include a sample calculation for each type of calculation you used in this experiment

Answer the following questions in your short lab report

1. What three kinds of standard automotive specifications can be related to heat of
combustion values?
2. If the biodiesel reaction is exothermic, why is the oil heated prior to the reaction?
3. Instead of methanol, ethanol can be used to produce biodiesel. Why is ethanol harder to
fully react and harder to recover excess amounts?
4. In commercial production of biodiesel, there is a significant amount of excess methanol
from the chemical reaction. What do you think industry does with this excess/un-reacted
methanol recovered in water washings?
5. Why should the blend not be more than 10% gasoline?
6. Why should the blend not have more kerosene than diesel?
7. Include an explanation of the error in theoretical vs. experimental results for energy
content.
8. When using the Arrhenius method to predict blend viscosity, which fraction basis (mole,
mass, or volume) provided the best predictions? Why?

19
Include these additional questions in your long version of the lab report

9. NO and NO2 (grouped as NOx) are a large concern in vehicle emissions because they lead
to an increase in ground level ozone. However, the atmosphere has an abundance of
nitrogen and oxygen, but NO2 formation is not a concern at ambient conditions. Why is
this the case?

10. Sustainability looks at the impact of a product over its entire life cycle and its ability to
be produced indefinitely with little or no harm to the environment. Explain the beneficial
aspects of each alternative fuel as well as the drawbacks with regards to sustainability
(Use literature to help you).

11. Based on your experience of making biodiesel and VeggieDiesel and your knowledge of
petroleum diesel, which do you feel is the best option for use in diesel vehicles? Keep in
mind the physical properties of the fuels (their viscosities) and the difficulties of their use
in winter conditions. Additionally, consider the energy and resources required to make
each fuel.

12. Based on your knowledge and the information given in the further reading articles, do
you feel gasoline or E85 is the best option for use in gasoline vehicles? Keep in mind the
physical properties of the fuels (their energy content) and the amount of energy required
to produce the fuel.

13. If all diesel fuel used in the United States in a year was blended with all the vegetable oil
produced in the same year, what would be the content ratios of this simple VeggieDiesel
blend? Based on your blending experience, is this a viable fuel to be used? Would this
method be better economically and environmentally than using the oil to make a
petroleum diesel - biodiesel blend?

14. What are the exact stoichiometric amounts of sodium hydroxide and methanol needed to
make the vegetable oil the limiting reagent? Based on your answer, why did you use
excess methanol and insufficient sodium hydroxide?

20
References
1. Huzayyin A.S.; Bawady A.H.; Rady M.A.; Dawood A. Experimental Evaluation of Diesel
Engine Performance and Emission Using Blends of Jojoba Oil and Diesel Fuel. Energy
Conversion and Management. 2004, 45, 2093-2112.
2. Forson F.K.; Oduro E.K.; Hammond-Donkoh E. Performance of Jatropha Oil Blends in a
Diesel Engine. Renewable Energy. 2004, 29, 1135-1145.
3. Herchel T.C.; Machacon S.S.; Karasawa T.; Nakamura H. Performance and Emission
Characteristics of a Diesel Engine Fueled with Coconut Oil-Diesel Fuel Blend. Biomass and
Bioenergy. 2001, 20, 63-69.
4. Rakopoulos, C.D. Olive Oil as a Fuel Supplement in DI and IDI Diesel Engines. Energy
1992, 17, 787-790.
5. Rakopoulos, C.D.; Antonopoulos K.A.; Rakopoulos D.C.; Hountalas D.T.; Giakoumis E.G.
Comparative Performance and Emissions Study of a Direct Injection Diesel Engine Using
Blends of Diesel Fuel with Vegetable Oils or Bio-diesels of Various Origins. Energy
Conversion and Management. 2006, 47, 3272-3287.
6. Wang Y.D.; Al-Shemmeri T.; Eames P.; McMullan J.; Hewitt N.; Huang Y.; Rezvani S. An
Experimental Investigation of the Performance and Gaseous Exhaust Emissions of a Diesel
Engine Using Blends of a Vegetable Oil. Appl. Thermal Eng. 2006, 26, 1684-16912.
7. ASTM D975, Standard Specification for Diesel Fuel Oils; American Society for Testing
and Materials, Philadelphia, 2007.
8. ASTM D6751-09, Standard Specification for Diesel Fuel Oils; American Society for
Testing and Materials, Philadelphia, 2007.
9. Archer, D. Fate of fossil fuel CO2 in geologic time. Journal of Geophysical Research 2005,
110: C09S05.
10. Bourne, J.K. Green Dreams, National Geographic. 2007, 10:38-59.
http://ngm.nationalgeographic.com/2007/10/biofuels/biofuels-text/1 (accessed August
2009).
11. U.S. Department of Agriculture and U.S. Department of Energy NREL/SR-580-24089 UC
Category 1503, May 1998.
12. Energy Information Administration, http://www.eia.doe.gov (accessed August 2009).
13. Wagner, E.P.; Koehle, M.A.; Moyle, T.M.; Lambert, P.D; Predicting Temperature
Dependent Viscosity for Unaltered Waste Soybean Oil Blended with Petroleum Fuels. J.
Am. Oil Chem. 2009, DOI: 10.1007/s11746-009-1512-2.
14. Levine, I. N. Physical Chemistry, 6th ed. McGraw-Hill, New York: 2002.
15. Menon, E.S. Piping Calculations Manual. McGraw-Hill, New York: 2005.
16. Baird C.T. Guide to Petroleum Product Blending. HPI Consultants Inc., Austin, TX: 1989.
17. Grunberg, L.; Nissan A.H. Mixture Law for Viscosity, Nature. 1949, 164, 799-800.

21
Further Reading & References
Balat M.;, Balat, H. A critical review of bio-diesel as a vehicular fuel. Energy Conversion and
Management. 2008, 49, 2727-2741.
Carraretto, C.; Macor, A.; Mirandola, A.; Stoppato, A.; Tonon, S. Tallow Biodiesel: Properties
Evaluation and Consumption Tests in a Diesel Engine. Energy Fuels. 2008, 22, 1949–1954.
DeOliveira E., Quirino, RL, Suarez, PAZ, Prado, AGS. Heats of combustion of biofuels obtained
by pyrolysis and by transesterification and of biofuel/diesel blends, Thermochimica Acta. 2006,
450, 87-90.
Erhan, S.Z., Asadauskas, S., Adhvaryu, A., Correlation of Viscosities of Vegetable Oil Blends
with Selected Esters and Hydrocarbons, Journal of the American Oil Chemists’ Society 2002, 79,
1157-1161.
Kours, R.A., Jo, J., A Rapid Engine Test to Measure Injector Fouling in Diesel Engines Using
Vegetable Oil Fuels, Journal of the American Oil Chemists’ Society. 1985, 62, 1563-1564.
McDonnell, K., Ward, S, Leahy, JJ, McNulty, P. Properties of rapeseed oil for use as a diesel
fuel extender, Journal of the American Oil Chemists’ Society. 1999, 76, 539-543.
Ozaktas, T, Cigizoglu, KB, Karaosmanoglu, F, Alternative Diesel Fuel Study on Four Different
Types of Vegetable Oils of Turkish Origin, Energy Sources. 1997, 19, 173-181.
Peterson, CL, Auld, DL, Korus, RA, Winter Rape Oil Fuel for Diesel Engines: Recovery and
Utilization, Journal of the American Oil Chemists’ Society. 1983, 60, 1579-1587.
Rakopoulos, CD, et al, Comparative performance and emissions study of a direct injection Diesel
engine using blends of Diesel fuel with vegetable oils or bio-diesels of various origins, Energy
Conversion and Management. 2006, 47, 3272-3287.
Yuan, W, Hansen, AC, Zhang, Q, Tan, Z, Temperature-Dependent Kinematic Viscosity of
Selected Biodiesel Fuels and Blends with Diesel Fuel, Journal of the American Oil Chemists’
Society. 2005, 82, 195-199.

Websites to explore (verified June 2009)

Alternative Fuels
http://epa.gov/OMS/consumer/fuels/altfuels/altfuels.htm
http://ngm.nationalgeographic.com/2007/10/biofuels/biofuels-text/1
http://www.popularmechanics.com/science/earth/2690341.html
http://www.whitehouse.gov/stateoftheunion/2006/energy/index.html
http://www.ahs.dep.state.pa.us/newsreleases/default.asp?ID=3855&varQueryType=Detail
Biodiesel
http://www.biodiesel.org/pdf_files/fuelfactsheets/Weight&Formula.pdf
http://www.biodiesel.org/pdf_files/Biodiesel_Technical_Manual.pdf

Ethanol
http://www.ncga.com/ethanol/main/index.asp
http://www.eere.energy.gov/afdc/e85toolkit/equip_processes.html
http://www.foodbeforefuel.org/
http://www.ethanolrfa.org/

22
Mixing Fuels
Gas-Diesel
http://www.turbodieselregister.com/mixing_gasoline_and_diesel.htm
http://www.dieselpage.com/art0100gd.htm

Vegetable Oil
http://www.vegetablecar.org/
http://www.biodiesel.org/pdf_files/fuelfactsheets/clean_cities_SVOpaper.pdf
http://www.jrc.es/home/report/english/articles/vol74/TRA1E746.htm

GREET
http://www.transportation.anl.gov/modeling_simulation/GREET/index.html
GREET is a program designed to evaluate energy and emissions in the “wells-to-wheels” life
cycle of transportation fuels. This may be helpful in evaluating the alternative fuels in this lab.
The following are technical reports about the life cycle of fuels based on GREET analysis:
Advanced Fuel/ Vehicle Systems (Gasoline, Diesel, Ethanol):
http://www.transportation.anl.gov/pdfs/TA/339.pdf
Soybean-Derived Bio-diesel and Renewable Fuels:
http://www.transportation.anl.gov/pdfs/AF/467.pdf

23
Instructor notes and useful information.

Required equipment not commonly found in a teaching laboratory

1. Bomb Calorimeter (Parr 1431 adiabatic calorimeter)
2. Gelatin capsules for volatile bomb calorimetry sample
3. Viscometers (Cannon-Fenske used here, although other types of kinematic viscometer
can be used)
4. 1 mg or better precision balance

Required Chemicals and CAS

1. Soybean oil (if WVO, be sure to filter before use) (8001-22-7)
2. Petroleum Diesel (64742-81-8)
3. Gasoline (8006-61-9)
4. Kerosene (8008-20-6)
5. Ethanol (anhydrous) (64-17-5)
6. Sodium hydroxide (1310-73-2)

Typical VeggieDiesel blend

WVO 50%, Kerosene 20%, Diesel 20%, Gasoline 10%
This should have a viscosity around 5 to 6 cSt at 104oF.

Typical energy content of fuels

Fuel Heat of Combustion
Diesel 45.8 kJ/gram
Gas (87 octane) 51.6 kJ/gram
Kerosene 46.3 kJ/gram
Ethanol 28.5 kJ/gram
Biodiesel 38.1 kJ/gram
Soybean oil 41.9 kJ/gram

Typical composition of soybean oil triglyceride groups

Triglyceride % by mass Formula
Palmitic 12 (C15H31CO2)3C3H5
Stearic 5 (C17H35CO2)3C3H5
Oleic 25 (CH3(CH2)7CH=CH(CH2)7CO2)3C3H5
Linoleic 52 (CH3(CH2)4CH=CHCH2CH=CH(CH2)7CO2)3C3H5
Linolenic 6 (CH3(CH2CH=CH)3(CH2)7 CO2)3C3H5

Bond energies
Bond Type Energy kJ/mol Bond Type Energy kJ/mol
C-C 347 C=O 749 (esters)
C=C 615 C=O 803.3 (CO2)
C-H 414 H-O 464
C-O 360 O=O 498

24
Gelatin Capsules
It is important to completely fill the capsule because during the pressurizing and depressurizing
of the bomb during venting the capsule will expand or contract away from the ignition wire thus
failing to ignite the sample. Also, do not put the ignition wire under the capsule. This causes the
initial burn hole to be on the bottom of the capsules, which then propels it out of the cup
resulting in an incomplete burn.

Answers to Questions

1. Can be related to horsepower, torque and miles per gallon

2. The oil needs to be less viscous for the reaction to proceed quickly.

3. Steric hindrance and ethanol forms azeotrope with water so it is harder to recover.

4. They recover it through distillation.

5. With too much gasoline in a blend, the cetane rating of the fuel decreases. A blend with too
much gasoline will also not provide enough lubrication in a diesel engine, and may cause
damage to the injector pump and/or fuel pump (discussed below).

6. While kerosene has properties more similar to diesel than gasoline, it still causes the same
problems gasoline does concerning cetane rating and lubrication. Kerosene also does not give as
much power as diesel. Additionally, kerosene does not have the lubrication properties that diesel
fuel does. Because diesel cars are designed to have the fuel lubricate the fuel pump, excessive
kerosene will cause the bearings in your fuel pump to wear more quickly and require
replacement.

7. Answers will vary, but should include a discussion that bond enthalpies are approximate and
average values. The exact triglyceride groups of the vegetable oil are not known , so the typical
composition and molecular weights are used in both the biodiesel and VeggieDiesel calculations.
E85 error comes from the assumption that gasoline is all C8H18.

8. Volume (maybe mass) predictions are closest to experimental values. Viscosity is more
directly a function of the molecule shape. TA note: There are many texts discussing this point.
Experimental Physical Chemistry by Halpern and McBane as well as Experiments in Physical
Chemistry by Garland, Nibler, and Shoemaker both give a good basic introduction to the topic.

9. The equilibrium constant for the formation of NO2 from O2 and N2 is very small at
atmospheric temperatures (K = 1 x 10-9). However, at the high temperature inside an engine, the
equilibrium constant and the formation becomes significant (K = 0.015).

10 & 11. Answers vary, but student should provide literature sources to their explanations and
opinions.

25
12. Ethanol uses corn that needs fertilizers that require petroleum to produce, Biodiesel needs
dangerous solvents and caustic chemicals and Veggie-Diesel still uses petroleum products.

13. The ratio is approximately 93% Diesel and 7% WVO. This is an acceptable blend and would
be better then making biodiesel. (2.9 billion gallons of WVO produced and 40 billion gallons of
diesel used).

14. Approximants:

Density weight MW
Amount (g/mL) (g) (g/mol) Moles Consumed Excess
WVO 100 mL 0.92 92.30 812.00 0.11 0.11 0.00
Methanol 20 mL 0.79 15.82 32.00 0.49 0.34 0.15
NaOH 1g n/a 1.00 40.00 0.03 0.34 -0.32

Excess methanol was used to ensure that the reaction went to completion. Insufficient sodium
hydroxide was used because it is a catalyst and not consumed in the reaction.

Bond Enthalpy Calculations

Biodiesel (Assume all Linoleic Methyl esters)
Energy Energy
Number kJ/mol Products kJ/mol Reactants: 35176.94
C-C 15 347 0 0 Products: 46302.54
C=C 2 615 0 0
C-H 34 414 0 0 Heat of Combustion -11125.6
C-O 2 360 0 0
C=O 1 748.94 38 803.33
H-O 0 464 34 464 Calculated 11125 kJ/mol
O=O 26.5 498 0 0 Measured 11642.4 kJ/mol
C19H34O2 + 26.5 O2 --> 17H2O + 19CO2 39.6 KJ/g 294 g/mol %Error= 4.44

Ethanol
Energy Energy
Number kJ/mol Products kJ/mol Reactants: 4618
C-C 2 347 0 0 Products: 5997.32
C=C 0 615 0 0
C-H 5 414 0 0 Heat of Combustion -1379.32
C-O 1 360 0 0
C=O 0 748.94 4 803.33
H-O 1 464 6 464 Calculated 1379 kJ/mol
O=O 3 498 0 0 Measured 1311 kJ/mol
C2H6O + 3 O2 --> 3 H2O + 2 CO2 28.5 KJ/g 46 g/mol %Error= 5.19

26
 Gasoline
Energy Energy
Number kJ/mol Products kJ/mol Reactants: 16106
C-C 7 347 0 0 Products: 21205.28
C=C 0 615 0 0
C-H 18 414 0 0 Heat of Combustion -5099.28
C-O 0 360 0 0
C=O 0 748.94 16 803.33
H-O 0 464 18 464 Calculated 5099 kJ/mol
O=O 12.5 498 0 0 Measured 5882.4 kJ/mol

C8H18 + 12.5 O2 --> 9 H2O + 8 CO2 51.6 KJ/g 114 g/mol %Error= 13.32

E85
Calculated 1937 kJ/mol
Measured 1996.7 kJ/mol
(calc) through volume fractions
%Error= 3.0%

Additions

Consider also putting difference between delta H and delta U into the lab report

Consider increasing Organic Chemistry aspect including methanol recovery, biodiesel washings,
NMR, GC and IR analysis.

27