Solubility of Ferrocene in Organic Solvents

Walter R. May
SFA International, Inc.
Houston, TX
Of all metals with catalytic effects on the combustion of hydrocarbons, iron is one of the
best. In the literature, iron reduces particulate matter in boiler and engine exhausts
reaching as high as 50%.1 SFA International’s patented combustion catalyst technology
involves the use of iron combined with magnesium.2 One of the requirements of a fuel
additive is that metal compounds in the additive must be soluble in the fuel.
Ferrocene contains 30% iron by weight and can be used as a source of iron in fuel
additives. Ferrocene is sold as a fuel additive in liquid and solid forms. In solid form, it is
available as “crumbs” and “caplets.” The advantage of using the solid form of ferrocene
is that it is easy to ship and add to a fuel tank. Unfortunately, users of solid forms of
ferrocene as a combustion catalyst have reported a wide range of results that are
mostly negative.3 The purpose of this paper is to evaluate the chemistry of ferrocene
and solubility in organic solvents to find the reasons for generally negative results with
solid forms of ferrocene as a combustion catalyst.
Ferrocene
Sandwich compounds and ferrocene have been known since 1951 when Pauson and
Kealy reacted cyclopentadienyl magnesium bromide Grignard Reagent with ferric
chloride. They obtained a light orange powder of “remarkable stability.”4 It is stable to
400o without appreciable decomposition.5 Professor Mark M. Jones of Vanderbilt
University (the author’s Ph.D. advisor) wrote extensively on ferrocene in his book
Elementary Coordination Chemistry.6

1

Boiler Fuel Additives for Pollution Reduction and Energy Saving, Ed. R. C. Eliot, Noyes Data Corporation,
Park Ridge, NJ, 1978.
2
See SFA’s web site at www.SFAInternational.com for more information.
3
Sources for this statement are personal and confidential conversations with several people who have
had experience with using solid forms of ferrocene as a combustion catalyst. Results have been sporadic
and overwhelmingly negative.
4
http://en.wikipedia.org/wiki/Ferrocene
5
Inorganic Reactions and Structure, Edwin S. Gould, Henry Holt and Company, New York, NY., 1955.
6
Elementary Coordination Chemistry, Mark M. Jones, Prentice-Hall, Inc., Englewood Cliffs, NJ, 1964.

1

that hold Tier One testing and EPA Registration for on-road use.p. Ferrocene . Ed. 2 . dispersed at sub-micrometer size levels. A. Data. SFA’s FuelSpec® 118 and 119 catalysts are based on an iron colloidal dispersion. at a minimum. Eng.04. Therefore. Chem. Siddiqi.000 in an EPA acceptable laboratory. 51 (3).S. FuelSpec® 118-1502 has a median particle size of 0. there are a few importers of the product into the U. 249o b. Florida. we undertook an investigation of the solubility characteristics of solid forms of ferrocene in organic solvents to find out if this is the cause of observed anomalies in performance of the product as a combustion catalyst.Dicyclopentadienyl Iron(0) Ferrocene as a Fuel Additive While ferrocene is made only in China at this time. Ferrocene is 30. With this minimal information. B. ferrocene has been very attractive as a lowcost on-road EPA Registered fuel catalyst with a minimum of problems shipping and applying solid forms. 1092-1096. Weast. A number of companies have EPA registered re-branded products purchased from the holders of the original Tier One registration.007 micrometers.. hexane and 2. To be an effective combustion catalyst.. Robert C. They found ferrocene to be “only weakly soluble in these solvents” which included ethanol. toluene. ferrocene must also be soluble in naphtha (gasoline) and Diesel fuels. Most of these products are the solid form of ferrocene. CRC Press. It is notable that there are no data regarding solubility of ferrocene in polar or non-polar solvents.4-trimethylpentane (isooctane). Boca Raton.. The cost of Tier One registration testing is about $300. 2006. 1984-85.7 ferrocene has a molecular weight of 186. Metallic fuel additives can only be effective if dissolved at the molecular level in the fuel or.2. J. and 172.5o m.p. 7 8 Handbook of Chemistry and Physics.02% iron by weight. pp.” Siddiqi and Atakan8 studied the dynamic equilibrium between gas and liquid phases.According to the Handbook of Chemistry and Physics. The Wikipedia article states that ferrocene is “soluble in most organic solvents. SFA’s FuelSpec® 116 and 117 products are oil-soluble iron carboxylates (salts of organic acids) that are completely soluble in aliphatic hydrocarbon fuels. Inc. Atakan.

Solubility ranged from a high of 5. We found a slow dissolution rate for ferrocene at 1% iron level (3. There are no polar areas for attraction to electron acceptors or donors.. An examination of the structure of ferrocene (given on page two) indicates some aromaticity from the two sets of double bonded carbons in each cyclopentadienyl ring. The compound has weak aromatic character and a lack of non-polar areas commensurate with aliphatic properties.. (6) Nov. toluene and xylene. There is no reason to expect ferrocene to be especially soluble in any solvent.0 to 1.”9 This paper includes experimental data on ferrocene in forty-six organic solvents compared with theoretical calculations for solubility based on mobile order theory. M. 2 (Diesel) fuel.5% ranges. alcohols. SFA Solubility Results SFA recently undertook an evaluation of ferrocene solubility in a highly aromatic naphtha solvent and ultra low sulfur No.59% Fe for benzene to 0. We were able to dissolve 2% iron (6. We attribute this to the fact that aromatic fuels are better solvents for ferrocene than highly aliphatic fuels.5 to 4. esters.33% ferrocene) in heavy aromatic naphtha and an even slower dissolution rate in Diesel fuel. The experimental data are presented in Table I. The following time-dated photographs show the results.Solubility of Ferrocene in Organic Solvents A study was carried out at the University of North Texas on the “Solubility of Ferrocene in Organic Nonelectrolyte Solvents. The product was vigorously shaken one time per day over a thirteen day period. Figure 1 is a picture of the sample immediately following addition of the ferrocene to LED and 9 DeFina. E. Jr. 2001. aromatic compounds including benzene. However. 39.66% concentration to yield 2% iron in the solution. W.0% range. Ezell. Ferrocene was added to dyed off-road LED fuel at a 6. Acree. Comparison of Observed versus Predicted Values Based upon Mobile Order Theory.66% ferrocene) in heavy aromatic naphtha with vigorous mixing over about 3 days. Aliphatic solvents dropped off to the 1. Chlorinated hydrocarbons were high as well as carbon disulfide and pyridine. This eliminates oxygenated solvents.. Ferrocene has no solubility in water and inorganic electrolyte solutions. 3 . Xylene isomers had relative high solubility’s in the 3. ketones and organic sulfur compounds. Physics and Chemistry of Liquids. Pages 699710. The solvents included a number of aliphatic compounds. polar or non-polar. those pi bonds are directed toward the strongly Lewis acid iron atom between the rings. Oxygenated compounds were the poorest solvents.. C. K. This indicates that solvents with higher levels of aromaticity were better solvents than non-polar aliphatic solvents.09% for 1-Butanol.

Although ferrocene will dissolve with time in a static system due to thermal convection. Solid ferrocene has a higher density than fuel and. 2 distilled fuels including LED fuels contain water that settles from the fuel and accumulates on the bottom of fuel tanks. a dosage rate of one part additive to 2. It should be pointed out that iron is generally added to a fuel at 5 to 50 ppm whereas the samples evaluated in this study were at 1% and 2% or 10. 2. All ASTM No. The resulting lower dosage rates yield much higher flexibility in application of the product and more 4 . The practical limit is 2% iron in highly aromatic solvents. Figure 2 shows un-dissolved ferrocene twelve days later. 3. localized concentration in the area of the solid material exceeding solubility limits will result in slowing or stopping dissolution of ferrocene in the fuel.000 ppm iron. “Caplets” have a much smaller surface area to weight ratio than “crumbs” greatly reducing rate of dissolution. Vigorous agitation plus heating will help dissolution. immediately settles to the bottom of the tank in the water phase.000 parts fuel by weight is required. Figure 3 shows material clinging to the bottom of the bottle after it was inverted on the 13th day. a highly aromatic solvent must be used. Ferrocene would be expected to dissolve in aliphatic fuels at additive dosage levels with time and vigorous agitation. To achieve 10 ppm iron in fuel with a 2% iron solution. 1. Because of low solubility and slow dissolution rates of ferrocene in typical LED aliphatic fuels. There are three things to consider with the use of solid forms of ferrocene as a fuel additive. Ferrocene is insoluble in water and this material will never dissolve. when added to a tank. Solid forms of ferrocene should never be put in fuel without thorough mixing which is generally not available in small contained tanks in vehicles and other equipment. “Caplets” and large compressed forms of ferrocene should never be used and sales of these products should cease. SFA International has developed iron products with up to 9% iron in an oil soluble form and 18% iron in a colloidal dispersion for industrial applications. An eventual result can be plugging fuel filters. Ferrocene Solutions A limiting factor on the use of dissolved ferrocene as a fuel additive is the maximum concentration of iron that can be achieved in these solutions. addition to a tank with minimal mixing is almost certain to result in poor results. Our work with ferrocene indicates that to dissolve the material in a solvent at percent levels.000 and 20.vigorous shaking.

Performance of a combustion catalyst containing iron (or iron plus magnesium) requires sufficient dosage.000 ppm sulfur that yielded 10% in switcher duty and 5% in road duty improvement with a ferrocene solution catalyst.” 11 Diesel Engine Emissions reduction Conference. Although an analysis of the fuel used in this test was not given in the report.11 SFA measured 12. There are better approaches to adding iron to a fuel exemplified by SFA’s higher concentration product line. Our conclusion from this evaluation is that solid forms of ferrocene such as crumbs should be avoided. Southern Research Institute. Without mitigating circumstances such as EPA Registration requirements for onroad use.12 It is estimated that SFA’s iron-magnesium catalyst yields 50% better fuel economy than iron alone. Conclusion Sporadic results from the use of ferrocene as a combustion catalyst can be explained by observations on the solubility of ferrocene in organic solvents. Inc. Lawrence and Atlantic Railroad (Division of Genese & Wyoming) 3.500 HP road engine. These types of observations are common with ferrocene based catalysts. 10 May. 12 Verification Report was prepared by Greenhouse Gas Technology Center. The test was run on a St.1 A study was carried out on a railroad locomotive using kerosene fuel with about 3. boilers and process heaters. E.000 HP EMD GP-40-3 locomotive. 11 Note the 100% variation in the two measurements that could be attributed to mixing in the fuel. 5 . Ferrocene can be used in combustion catalyst or fuel additive formulations when dissolved in a solvent so that it will disperse thoroughly into the fuel.8% savings in a 1. for EnviroFuels. opportunities for the material to remain in solid form remain. SFA discovered a synergistic combination of iron and magnesium that is a superior combustion catalyst to iron alone. In boiler and combustion turbine exhaust measurements. Lower dosage rates based on economic considerations are ill advised and will not produce desired results. August 21-25. Optimum dosage levels are 10 ppm iron in compression-ignited reciprocating engines and 50 ppm iron in continuous firing equipment such as combustion turbines. Chicago. This test was run in 2005 in the state of Maine.. “Catalyst for Improving the Combustion Efficiency of Petroleum Fuels in Diesel th Engines. SFA’s iron-magnesium catalyst yields 90% reduction in particulate matter in exhausts10 compared with 50% expected from the literature.com. W and Hirs. While crumbs can dissolve under ideal conditions. Research Triangle Park. it is estimated that the fuel was similar to that used in Lincoln and Plymouth Railroad tests with SFA’s iron-magnesium catalyst in new Hampshire in the same year. 2005. the user would be well advised to use SFA International’s much higher performing iron and magnesium combinations. The complete test is available at www.envirofuelsllc. Caplets with even poorer dissolution rates should be avoided and sales of these products should be stopped.economically effective results.0% fuel savings with the same fuel in 600 HP switch engine and 12. IL. NC.

6 . Immediately following addition of ferrocene to off-road dyed Diesel fuel.Figure 1. 12-Apr-09.

Undissolved ferrocene after 12 days. 24-Apr-09 7 .Figure 2.

Figure 3. 25-Apr-09 8 . Undissolved ferrocene shown sticking to bottom of bottle.

43% 1.097 74.76% 0.98% 1.14% 2.009215 0.012630 0.178 102. 4.077850 0.22% 3.20% 0.041200 0.71% 0.124 74.88% 2.61% 15.168 106.55% 3.232 154.36% % Fe 1.232 88.178 102.57% 2.016670 0.63% 2.151 88.178 100.50% 4. Solubility of Ferrocene in Organic Non-Electrolyte Solvents Solvent n-Hexane n-Heptane n-Octane n-Nonane n-Decane n-Hexadecane Cyclohexane Methylcyclohexane Cyclooctane 2.286 226.49% 12.87% 2.008917 0.15% 4.38% 2.36% 3.32% 18.97% 0.232 Mole Fraction Solubility 0.232 158.033000 0.030970 0.016670 % Sol.051070 0.087586 0.124 74.07% 5.68% 0.63% 2.28% 6.97% 0.84% 0.50% 4.24% 12.007078 0.24% 3.34% 4.080140 0.043 46.72% 3.005976 0.71% .124 74.24% 2.068300 0.024890 0. Wt.54% 2.79% 0.012250 0.30% 2.42% 7.013520 0.98% 3.020500 0.033720 0.34% 12.83% 3.021790 0.01% 3.37% 2.027130 0.036120 0.71% 0.151 88.16% 0.32% 1.31% 13.189 113.014260 0.168 106.70% 3.4-Dioxane Methanol Ethanol 1-Propanol 2-Propanol 1-Butanol 2-Butanol 2-Methyl-1-propanol 2-Methyl-2-propanol 1-Pentanol 2-Pentanol 3-Methyl-1-butanol 2-Methyl-2-butanol 1-Hexanol 2-Methyl-1-pentanol 4-Methyl-1-pentanol 1-Heptanol 1-Octanol 2-Ethyl-1-hexanol 1-Decanol 2-Ethyl-1-hexanol Solvent Mol.97% 0.59% 4.070 60.205 114.151 88.141 106.65% 0.25% 1.114 92.30% 1.168 106.124 88.027670 0.039630 0.81% 2.259 142.28% 2.097 60.65% 3.82% 1.192 114.083210 0.81% 0.009621 0.224 109.022150 0.77% 0.074360 0.36% 1.71% 0.94% 0.232 130.003298 0.297 78.015540 0.448 98.57% 0.108 32.178 116.73% 0.017350 0.40% 1.232 128.029010 0.13% 2.168 130.077030 0.52% 4.286 130.76% 13.94% 0.022600 0.75% 4.010270 0.11% 2.001181 0.77% 0.09% 0.205 130.14% 8.046800 0.2.151 88.71% 2.4-Trimethylpentane t-Butylcyclohexane Benzene Toluene Ethylbenzene o-Xylene m-Xylene p-Xylene Dibutyl ether Methyl t-butyl ether 1.151 102.013430 0.05% 1.Table I.02% 0.42% 3.89% 7.30% 5. 86.

960 92.13% % Fe 0. 3.60% 2.027670 0.24% 3.162 88.017740 0.140 79.823 95. Wt.043000 0.30% 7.48% 1.569 148.34% 3.37% 1.01410 0.29% 14.34% 4.550 41.108 74.61% 11.80% 13.00% 0.055800 0.02400 0.99% 4.050 78.47% 8.13% 2.032580 0.60% 2.07048 % Sol.059620 0.67% 7.39% 2.135 116.677 153.286 86.06690 0.Table I Continued Solvent 1-Decanol Cyclopentanol Butyl acetate Ethyl acetate Methyl acetate 2.65% 8.100 Mole Fraction Solubility 0.54% .91% 15.077350 0.48% 4.57% 3.06920 0.081 98.97% 1.00756 0.25% 4.130 76.060620 0. 158.75% 8.3-Dichloroethane 1-Chlorobutane 1-Chlorooctane Tetrachloromethane 2-Propanone Acetonitrile Dimethyl sulfoxide Carbon disulfide Pyridine Solvent Mol.24% 2.09% 3.