‘The Chemistry of Coconut Oil ‘Haji Ibrahim Haji Abd. Rahman. Department of Chemistry Introduction Coconut ol has been used extensively for edible and non-edible purposes all over the world. Detergent industries depend mainly on coconut and palm kernel ols for laurie acid. It is one of the world’s most desirable natural ols for confections, bakery goods, deep fit frying and for non-edible purposes. This is due to two ofits special characteristics, high degree of saturation and good stability. Physically, coconut oil is hard and brite at lower temperatures, but has a sharp melting point below 30°C. The cil is also hydrolysed commercially and the short chain faty acids are factonaly distilled into end products of ‘various degrees of purity, which in turn are transformed into alcohols, amides, and esters for a large ‘ariety of specialised end uses in detergents, plastics ete. However, the unrefined oil recovered from ‘copra has a disagreeable odour due to the volatiles, including free fatty acids and other impurities. 1s procedures have been caried out to purify the crude coconut il into an acceptable edible oil ‘These include both chemical treatments and physical separations. The traditional practice of crude coconut oil purification is the fourstage process of degumming, neutralisation, bleaching and ‘eodorsation, Ths traditional procedure has been modified to improve yield, eliminate the pollution pro- bem arising from the soapstock and reduce the cost ofthe whole operation. ‘The introduction of physical refining ona larg scale to refine palm ol low in gums and high i fee faty acids in Malaysia encouraged interest in applying this technique to other oils such as crude coconut oi ‘which bas a similar composition to palm kernel oil. Later studies have made it possible to substitute physical refining for chemical refining of other types ofa ‘The composition of crude coconut oll includes triacylglyeerols, free fty acid, partial lycerides, phospholipids, sterols, tocopherols, pigments, volatiles, trace metals and oxidised product. ‘The tracylplycerols of crude coconut oil constitute the major component (95 %). These are the components that we wish to purify without removing all of the useful minor components. The ‘objectionable materials to be removed include fee fatty acids, phospholipids, pigments, trace metals, products of oxidation and proteinaceous impurities. These impurities are unacceptable because they con- tribute colour to the ol, cause it to foam and smoke and precipitate when the ol is heated in subsequent processing operations. The important object inthe purification isthe removal of objectionable impurities ‘without considerable loss or damage to the neutral oil and the tocopherols which are the natural antioxidants, ‘Chemical and physical refining are the two common methods of crude coconut oil refining in most parts of the world. Chemical refining involves the removal of the free fatty acids and other impurities by means of chemical agents such as sodium hydroxide, This process causes considerable loss ‘of oll in the emulsion and inadequate separation by centrifugation as well as polation problems due to the salt remaining after acidification ofthe soapstack to recover fatty acids, Physical or steam refining offers a solution to these problems by the removal of free faty acids and other volatiles end odours by Stripping with steam in a single unit. Free faty acids can be recovered in pure form. However, ‘retreatment is required inthe physical refining process to remove some impurities. Physica refining has eplaced older chemical refining techniques forthe purification of erude coconut olin most refineries. Since crude coconut ol is still processed by physical and chemical refining, a comparison between the two methods will provide more information for the refineries to decide the best choice, because itis important to ensure that mild conditions are used inorder to avoid deleterious effets on oil ‘composition and chemical and physical properties.‘The authenticity of an edible oil can be established if we have knowledge of the composition and characteristics of the oil. Government departments and nuttionists rely on the latest information about the composition of vegetable oils when they want to consider consumers’ diets, Adulteration is ‘nother problem faced by the oil and fat trade, In order to detect adulteration itis necessary to develop certain tests to characterize olls and fats. Some characteristics, which help to identify the ofl and ft, include the iodine value, to give a measure of unsaturation of anol, saponification value, which gives 2 measure of the average molecular weight of the constituent fatty acids, fatty acid composition and triacylaiycerol carbon number distribution which are specific for each type af edible ol, Tocopherol and sterol content and composition may also be useful 19 tace the origin of an oi. Rossel eal (1985) studied purty characteristics of the major edible vegetable oils including coconut oil, from various countries of origin. They examined four hundred authentic ol samples obtained from reliable sources and analyzed for faty acid, triacylglycerol, sterol and tocopherol composition, They have established new Purity eiteria, which can be used as a standard to check the purity of suspected adulterated oil samples (Rossell etal, 1985 and Rossell et.al. 1983) Physical properties of an oll or ft are of critical importance in determining its use. This is Particularly tue of the large quantity and variety of oils and fats used in various forms as food. Oils and fats are inmate mixtures of liquid and solid phases consisting of wriacyllyeerols. The physical state Varies fom liquid to a viscous fuid to aplastic solid and to a brite solid, These features make their physical properties of particular interest and have resulted in their use in a wide range of special applications ‘Coconut oil or fat differs ffom non-Iaures in that t contains 46-50% laurie acid, together with smaller amounts of other medium- and short-chain faty acids. Akhough it melts below 30°C, it stays solid at cool ambient temperature. The short meting range of the natural (unmodified) oi, makes the eit suitable for the manufacture of variety of faty foods, However, the solid content at room temperature it a litle low for the production of confectionery coatings and couvertues. This shortcoming can be avercome by fractional crystallisation and separation ofthe harder stearin and the softer olein components. The harder stearin fraction could be ‘put to good use inthe couverture and coating industry The crystallization behavior of edible fats is important in a wide variety of food applications including confectionary, margarines, spreads and bakery producs. Coconut oil or modified coconut oil ‘commonly applied in several food produets suchas biscuit filling creams and chocolte-lavored coatings in which its erystallzation behavior i important. The effect of fatty acids on coconut il erytallization is dependent on the identity of faty acids. Oleic acid and laurie acid. were most effective at retarding ‘nucleation ofthe slid formation. Phospholipids which is alsa a minor component of coconut oil were {ound to extend the induction period for coconut oil crystallization st 15YC, with an increase in the induction period from 8 min to 27 min, Both te fee fity acid and phospholipids were removed during, refining and the effect ofthese minor components are undesirable as far asthe crystallization behavior is concerned. Coconut oil is very stable to oxidative deterioration when exposed to atmospheric oxygen. It Aiffers from other vegetable vil in that it contains a high degree (90%) of saturated fatty aids. However, Processing may have some influence on the stability of the oil. Phospholipids, which are minor ‘Components of crude coconut ol, are known to have a stabilizing effect on oils and fats (Dziedzic and Hudson 1984; Hudson and Ghavami 1984). The removal of phospholipids during intial stage of refining had reduced the stability ofthe coconut oil and confirmed the stabilizing effect ofthis minor component on the ol ‘The subility of coconut was decreased by the presence of contaminant such as copper and iron ‘The tocopherols had a stabilizing effet on the sabiliy of the coconut oil during processing. Some tocopherols were removed during processing and hence contributed to los of stability ofthe cocont oil due to oxidation, Citric acid and phosphoric acid had a stabilizing effect to coconut oil due to is chelating properties that reduce the pro-oxidant effect of metals such as eopper and iro, 10‘The Composition OF Crude Coconut Oil “The composition of erude coconut ol has been determined by various workers in diferent laboratories with several techniques, There are slight variations of composition in the reported data. The main ‘components of crude coconut oil, which are important and affect the characteristics of the ol, are as follows: 8) Triaeylalycerats by Fay acids ©) Phospholipids 4) Tocopherols| ©) Trace metals D Sterols 1) Volatiles '8) Mono~ and di-acylelycerols Most of the characteristics that distinguish coconut oil from ordinary ofls may be traced tothe high content of shor and moderately long chain fatty acids. Although referred to as an ol, coconut oil solidties at ambient temperatures intemperate countries ts melting point is usualy in the range of 24°- 27°C and its solidification point about S°C lower. The low melting point of coconut ol is not caused by & relatively high degree of unsaturation, asin the case of most vegetable oils, but by the low average molecular weight ofits glycerides. ‘The mos significant physicel property of coconut oll i that, unlike most fas, both natural and hydrogenated, it does not exhibit a gradual softening with increasing temperature, but passes rather abruptly from a brite solid to lguid, within @ narrow temperature range. In this respect, it resembles ‘cocoa butter, The characteristic melting behaviour of coconut oil is a consequence ofits fatty acid and triacylalyeerol composition. About 90% of the fatty acids of coconut oil are saturated and consist mainly of laurie, mystic and palmitic acid with laurie acid predominating (47.5%), as shown in table 1 (Rossel 1985). These acids melt at 4°, 54°, and 63°C, respectively. Hence there is a difference of only 19°C between the ‘melting point of the main aids present. On the other hand, the major fatty acids ofthe high molecular ‘weight fats are usually linolee, oleic, palmitic and stearic acids, which melt between -7°C and 70°C with ‘difference of 77°C. The relatively narrow melting range ofthe coconut fatty acids is reflected in the narrow melting range ofthe triacylglycerols and accounts primarily for te limited plastic range ofthe later. le 1 Fatty Acid Composition of Coconut Oil (wi) (Rossel 1985) Fattyacid © Caproie ca 04-06 Caprylic C80 69-94 Capric C100 62-78 Laurie ci20 459-503 Myristic ciao 168-192 Palmitie cleo 77-99 Stearic cis 23-32 Oleic cis: sa. 74 Linoleic c1s2 13.21 ‘Triacylglyeerols ae the major components of covonut oil comprising up to about 95% of the ol “They are esters of elyoerol with three fly acids, Fractionation of the triacylglyeerol by gas liquid chromatography (GLC) revealed 14 groups based on the even carbon numbers from 28 to $4 (Rossell 1985), With the fatty acid composition ofeach group, it was possible to calculate the composition of 79 types of triacylglycerls, Each group has one major type of triacylglycerol, For example, the group with ncarbon number 36 has 52% of trilaurin (Bezard 1971). Table 2 shows the triacylglycerol composition in terms of carbon number for coconut oil (Rssell 1985). Apparently the major triseylgyeerols of coconut oil ate trilaurin (C36, about 19%), followed by dilauryleapryiglycerol (C34) and dilauryimyristylglyeerol (C28) each about 16% and Jauryldicaprylglycerol (C 32) and lauryldimyristylgiyeerol (C 40) at about 10% each, Table 2 Triacylglycerol Composition (wit) by Carbon Number for Coconut Oil Rossell 1985) [Carbon Number(CN) ‘Range % Means (N28 07-10 08 N30 28-41 34 ONS? 11s- 144 129 N34 156-176 165 N36 183-198 188 N38 Is-177 163 Nao 92-11 102 Naa 65-80 13 Naa 36-45 42 CN a6 21-30 26 nas 16-26 23 nso 08-20 7 ens? 04-20 16 NSS ole 1s 12 Crude coconut oil has a relatively low content of phospholipids (0.296) when compared with the typical range of other vegetable oils of 1-3%. The major components of the phospholipids are Phosphatidylcholine (34.6%. total phospholipids), phosphatidylethanolamine’ (24.6%) and phosphatidylinostal (19.0%6).as shown in Table 3. Phospholipids are found in most natural fats but the ‘amount and composition differs depending on the source of the fat. Phospholipids are normally removed during vegetable ol refining. The phospholipids of soya bean oil 2-39) ae useful by-product ‘obiained during degumming step. They are found as a good emulsifier and sold as commercial lecithin {common name for phosphatidylcholine) that are used in margarines, confections, and shorienings ‘where a fat-soluble emulsifier is required, ‘Tocopherols are the natural antioxidants found in most vegetable ols. Their presence in crude coconut il stabilizes the oil to oxidation by air. Coconut ail is comparatively low in tocopherols, containing about 50 ppm (Taylor 1981). Young, (1983) reported that the combined tocopherol and {ocotrenol content of erude coconut oil ranges between 40 -100 ppm, but they are nevertheless of importance for protection. There is confusion inthe literature about the major tocopherols present in cocont ol Table 3_Phospholipid Composition of Coconut Oil (Krishnamurthy 1983) “Phospholipids —__% of total Phospholipids Phosphatidyicholine (Lecithin) Phosphatilthanolamine Phosphati inositol PPhosphatid serine Lysophosphatidyleholine Lysophosphatidlethanolamine Phosphatiie acid According to Taylor (1981), the major tocopherols present are gamma-tocotrienol 80%, ‘gamma-tocopherol (10%) and alpha-tocopherol (10% teal tocopherols). Mulle-Mulot (1976) however found thatthe concentrations of gamma tocopherol and alpha-tacotrienol in coconst oil were 2 4 and 20, pm, respectively. The ow level of tocopherol found in coconut il reflets the low degree of protection 2requires by coconut ol. This is evident when analysis of fatty acid composition reveal that the unsatured fay acid of coconut oils only about 10% of total fatty acid, Another report stated thatthe tol tocopherol content of crude coconut oil was 28 ppm, which consisted of 21 ppm of alpha-tocopherol (75% of total (Lambertsen eta, 1962). The differences inthe values reported by different workers could be due to diferent methods of analysis. However, the latest tnd most accurate methods for the analysis of tocopherols are based on high performance liquid chromatography (HPLC) (Taylor 1981) ‘Trace levels of metal ins in edible oils are well known to have serious deleterious effects on the stability ofthe ols, The presence of metal ions, such as copper and iron which are highly pro- ‘oxidative, will greatly reduce the stability of the ol. Copper and iron may originate from natural sources for be introduced during processing of the copra for oll extraction. The levels of trace metals vary ‘depending on the source and the origin of the oll. Normally values not greater than 0.2 ppm and 2 ppm. for copper and iron, respectively, were found in crude coconut oll (Young, 1983). Expected concentrations of copper and iron in good quality oil usually range from 0.02 to 0:2 ppm and 2 to 5 ppm, respectively (Salleh eal. 1988) ols Cholesterol trace 2.0 B-Sitosterol 434-704 ‘Stigmasterol 130-200 8-Avenasterol 47-256 ‘Campesterol 71-84 A7-Stigmasterot ‘rave -6.0 0 trace ie “The sterol content of erude Goconut ol was reported by Masson (1981) to be 100 mg/100g. “This value is lower than the typical range of 150-700 mg/100g of some other fats and oils (Masson 1981). The major sterols present in crude coconut ol are shown in Table 4 (Kochhar 1983; Itoh etal 1973), B-Sitosterol was the major sterol present, sometimes being as high as 70.4% of the total peak. area of the sterol fraction, It was also observed that significant percentages of stigmasterol, A°- ‘avenastrol and campesterol were preset in the sterol faction. Fedli (1966) confirmed the presence of Bsitosterol, stigmasterol and eampesterol. Cholesterol level is only found as trace amount in coconut oil Crude coconut oil contains about 900 ppm of volatile compounds, Two series of volatiles were idemified in 1965 by Allen in untreated crude coconut ol. They were the methyl Ketones of odd carbon hnumber (CN) from CN-7 to CN-15 and even carbon number_f-lactones from CN6 to CN-14 (Table 5). “The ketones inthe erude oll were the result of microbiological decomposition ofthe fatty acids ofthe oil that had occurred before the oil was pressed or extracted (Stokoe 1928). This was confirmed ‘when the analysis of the oil from fresh coconut showed the absence of the ketones (Table 5). The Tactones in rude coconut oil were believed to be responsible fr most of the coconut flavour and aroma ‘Table 5 shows the presence of significant amounts of lactones in similar quantities in both oils which had been obiained from old and from fesh copra, However, when the crude coconut oil was heated under vacuum, the amount of these volatiles (ketones and lactones) increased (Pai 1979).‘Table § Volatile Components in Crude Coconut Oil (Allen 1965) Volatile Component ‘Crude Coconut O Oil from fresh watt (O14) ppm oe 5m) Ketones | Heptan-2-one 40 ‘Nonan-2-one B Undecan-2-one 290 <1 Tridecan-2-one 138 4 Pentadecan-2-one 65 : B-Lactones| Hexalactone 2 2 ctaactone si 64 Decalactone 37 88 Dodecalactone 0 6 Tetradecalactone 30 20, thas been reported that partial glycerides, such as monoacylglycerls and diaeylglycerols, can influence the physical characteristics of edible oils, Interesterfiation of palm oil with glycerol, which Produced a mixture of wriaeylglycerols and diacylglycerols, resulted in an increased solids content at 20°C and a marked tendency fo form &-phase crystals (Okiy 1978). The effect of partial glycerides on the exystal structure of edible fats was further elucidated by Hemquist (1981). The 1 2-diaylglyeerols stabilise the 8-erystal structure of rapeseed ol (Hemquist ea. 1981), ‘The partial glycerides were present in a measurable amount in crude coconut cil. ‘The ™monoaeylglyeerol and diacylglycerol content ranged between 2.9 ~ 7.2% and 1.0 - 7.0%, respectively (Gopalakrishnan 1987), Conclusion Coconut oil is a versatile commodity. The oil is used both in edible and non-edible products. The chemistry of the oil has been studied intensively and a lot of studies are still carried out in vazies countries. Coconut oil possesses good properties such as stability to oxidation due to high degree of saturation ofits fatty acids. Caconut oil contains low level of cholesterol and high composition of ‘medium chain fatty acids References ‘Allen R.R (1965). Volatile flavour constituents in coconut cil. 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