1. Topics for Today  From Soap to Biodiesel!

2. Topics for Today  Why biodiesel?  How are soap and biodiesel different? No text readings 

3. Topics for Friday EXAM 4!!!!

4. For Monday  Connecting the amino acids…

5. Topics  Amines (review)  Amides (review)  Nylons (review)  Amino Acids  Proteins

6. Readings for Monday  11.6 Proteins: First among equals  11.7 Good nutrition and alternative diets: Getting enough protein

7. Topics for Today  From Soap to Biodiesel!!

8. Review - Soap  Generic term for the soluble salt of a fatty acid

9. Sopanification  The process of making soap –1) Hydrolysis of the fat (water is used) –2) Neutralizing the fatty acid (water is produced)

10. When soaps DON’T work… What is hard water?

11. Water with lots of Ca 2+ and Mg 2+ ions

12. Review  Dissolving a salt… 2HCl+Na 2 CO 3 H 2 CO 3 2NaCl + Why the “2”?

13. Review  Dissolving a salt… 2HNO 3 + CaCO 3  Ca(NO 3 ) 2 + H 2 CO 3 H 2 CO 3  H 2 O + CO 2 A lot of limestone in our area… tend to have very hard water

14. Soluble in water “Separates” into ions Soap in soft water

15. C O-O- O Na + C O-O- O C O-O- O C O-O- O

16.  Soap interacts with the Mg 2+ and Ca 2+ ions. Soap in hard water NOT soluble!!!!

17. Soap in hard water Mg 2+ C O-O- O C O-O- O C O-O- O C O-O- O Na + Soaps form complexes with Mg 2+ and Ca 2+ !! So what?

18. Soap in hard water Mg 2+ C O-O- O C O-O- O C O-O- O C O-O- O Na + Insoluble in water (soap scum)!!!

19.  Soap (soluble)  SCUM (insoluble) Falls out of the water

20. C O-O- O Na + C O-O- O + Ca 2+ (or Mg 2+ )

21. C O-O- O Mg 2+ (or Ca 2+ ) C O-O- O + 2Na + SCUM

22. How do you prevent soap scum? 1) Use soft water 2) Use detergents Why detergents?

23. Detergents  Same as soaps, but a different polar end. Usually a sulfate or a phosphate!!

24. Non-polar hydrocarbon chain Polar ionic group, soluble in water Soap sodium stearate H 3 C(CH 2 ) 16 C O O Na +

25. H 3 C(CH 2 ) 16 C O O Na + Non-polar hydrocarbon chain Polar ionic group, soluble in water Detergent Sodium Lauryl Sulfonate 10 S O ─ Why don’t detergents make scum?

26. H 3 C(CH 2 ) 16 C O O Na + H 3 C(CH 2 ) 16 C O O Na + 10 S O S O Mg 2+ ─ ─ Soluble!

27. Soap on the Web  Cator.hsc.edu/~kmd/caveman/proje cts/soap  History of soap making www.alcasoft.com/soapfact/history. html www.alcasoft.com/soapfact/history. html

28. Topics for Today  From Soap to Biodiesel!! Review

29. M. King Hubbert 1903 - 1989 "Our ignorance is not so vast as our failure to use what we know."

32. August, 2005: Chevron Full Page Magazine Adds willyoujoinus.com It took us 125 years to use the first trillion barrels of oil. We’ll use the next trillion in 30. So why should you care?

33. Review Where does gasoline come from?

34. Liquified Petroleum Gas (LPG) Gasoline Kerosene and Diesel Fuel Heating Oil and Diesel Fuel Lubricating Oil Solids (Paraffin, Asphalt, etc) Gasoline?

35. Gasoline

36. Liquified Petroleum Gas (LPG) Gasoline Kerosene and Diesel Fuel Heating Oil and Diesel Fuel Lubricating Oil Solids (Paraffin, Asphalt, etc) Diesel?

37. Diesel Fuel

38. Rudolf Diesel Invented the diesel engine in 1892

39. - Rudolph Diesel “The use of plant oil as fuel may seem insignificant today. But such products can in time become just as important as today’s kerosene and coal-tar-products”

40. - Rudolph Diesel “The use of plant oil as fuel may seem insignificant today. But such products can in time become just as important as today’s kerosene and coal-tar-products”

41. Biodiesel! How do we use plant oil as a fuel? What is biodiesel?

42. Chemically speaking…  The (methyl) ester of a fatty acid! How is it different from a soap??

43. Review - Soap  The soluble salt of a fatty acid!

44. C O O-O- Na + Soap – Salt of a fatty acid C O OCH 3 Biodiesel – Methyl Ester of a fatty acid

45. Where can we get the plant oils from?

46. Biodiesel Feedstocks Canola Soybeans Sunflower Linseed Safflower Corn oil Rapeseed Which is best?

47. Plants utilize photosynthesis to convert solar energy into chemical energy. Different plants produce usable oil at different rates. For Example: Soybean : 40 to 50 US gal/acre (35 to 45,000 L/km²) Rapeseed : 110 to 145 US gal/acre (100 to 130,000 L/km²) Mustard : 140 US gal/acre (130,000 L/km²) Jatropha : 175 US gal/acre (160,000 L/km²) Palm oil : 650 US gal/acre (580,000 L/km²) Algae : 10,000 to 20,000 US gal/acre (9,000,000 to 18,000,000 L/km²) http://www.biodiesel.org/resources/reportsdatabase/default.asp Q? How much energy goes into growing and harvesting these feedstocks? Q? What are the fertilizer requirements for each of these feedstocks?

48. Making biodiesel – green refineries of the future? 100 g soybean oil 100.4 g biodiesel  + 10.9 g methanol + 10.4 g glycerol

49. Soybeans More than 50% of the fatty acids are linoleic acid!

50. A polyunsaturated fatty acid C 18 H 32 O 2 How does this compare with diesel fuel?

51. Diesel Fuel

52. Biodiesel products are similar to conventional petrodiesel Cetane (C 16 H 34 ) Methyl Linolenate (C 19 H 32 O 2 ) A fatty acid methyl ester (FAME) BIODIESEL COMPONENT An unbranched alkane (paraffin) PETERODIESEL COMPONENT

53. NEW!! Biodiesel Roadmap EsterAlcohol+EsterAlcohol+ NEW Reactive Species Heat

54. Biodiesel Roadmap OilMethanol+ Biodiesel!Glycerol+ Reactive Species Fat What do we start with? Heat

55. - + Sodium methoxide salt H2OH2O CH 3 OH NaOH CH 3 O-O- Na + H2OH2O + + Sodium Hydroxide MethanolWater Step 1 Create the “reactive species” Don’t need to memorize this!

56. - + Soduim methoxide salt Step 3: Active species regenerated H2OH2O CH 3 OH NaOH CH 3 O-O- Na + H2OH2O + +

57. Biodiesel Roadmap OilMethanol+ Biodiesel!Glycerol+ Reactive Species Fat Heat

58. COH CO OCH H H H C O C O C O + CH 3 O - Na + heat Step 2! Making Biodiesel Oil Fat Reactive Species

59. COH CO OCH H H H C O C O C O + 2CH 3 O - Na + heat Step 2! Making Biodiesel Oil Fat Reactive Species

60. COH CO OCH H H H C O C O C O + 3CH 3 O - Na + heat Step 2! Making Biodiesel Oil Fat Reactive Species

61. Step 2! CH C O - Na + CH H H H O C + CH 3 O Making Biodiesel O - Na + 3

62. CH C CH H H H Step 3! Regenerate the reactive species!! + CH 3 OH heat Methanol O - Na + 3

63. CH C OHCH H H H + CH 3 O - Na + Step 3! Reactive Species OH 3 Glycerol!

64. Once for each fatty acid chain! Overall Reaction?

65. Triglyceride Alcohol HEAT COH CO OCH H H H C O C O C O CH 3 OH + CHO CH 2 O O H H H + C OCH 3 O 3 OH - Glycerol

66. Transesterification  Forming one ester from another ester!!!

67. Why is there no water in this reaction?

68. Sopanification HEAT / H 2 O COH CO OCH H H H C O C O C O 3NaOH + CHO CH 2 O O H H H + C O-O- O CH 3 (CH 2 ) 16 3 Na + We get soap!!!

69. Review… O H H.. Water O CH 3 H.. Methanol versus

70. - + OK O O R O O R O R O CH 3 fatty acid methyl ester + diglyceride salt

71. Steps 2-3 repeat for remaining glycerides Step 4: Catalyst regenerated from the active species H2OH2O

72. Benefits of biodiesel?

73. Reduced criteria air pollutants!

74. Criteria Pollutants Defined by the EPA –CO –SO 2 –NO x –PM2.5 and PM10 –O 3 (ozone) –lead 12% 20% 2% 12%

75. Extremely low sulfur content!

76. Compatible with current diesel engines!

77. Where is biodiesel being used?

79. Environmental group works to run cars on Culver’s old frying oil

83. One of the first uses of transesterified vegetable oil (biodiesel) was powering heavy duty vehicles in South Africa before World War II. The name "biodiesel" has been given to transesterified vegetable oil to describe its use as a diesel fuel. It was patented in the US in the 1940s by Colgate (and other) scientists. The 1940s researchers were looking for a method to produce glycerin more readily, in order to produce explosives for World War II. Many of the methods used today by producers and home brewers have their origin in the original 1940s research.

84. Glycerol!

85. Where is biodiesel produced?

86. Much of the commercially sold biodiesel, including most of Red Carpet's, is domestically made from soy beans and shipped from the Midwest http://www.biodiesel.org/

87. Can I find a pumping station near me? Depends where you live!