SOAP PRODUCTION FROM QUALITY ASSESSED GINGERBREAD PLUM (NEOCARYA MACROPHYLLA) SEED OIL.

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1 Journal of Scientific Research in Pharmaceutical, chemical & Biological Sciences Volume (1) Issue (1) Year (2016) ISSN : SOAP PRODUCTION FROM QUALITY ASSESSED GINGERBREAD PLUM (NEOCARYA MACROPHYLLA) SEED OIL. Aliyu Ahmad Warra * Department of Biochemistry, Kebbi State University of Science & Technology, Aliero, Nigeria. ABSTRACT The physicochemical analysis of gingerbread plum (Neocarya macrophylla) formerly parinari macrophylla (Sabine) seed oil extracted using soxhlet apparatus with n- hexane solvent was carried out and the following results were obtained; Acid value 12.97± 0.01mgKOH/g, Saponification value ± 0.10, Iodine value ±0.01 I 2 /100g, Free fatty acid 15.10±0.10 ( % Oleic), Peroxide value (meq H 2 O 2 ) ± The % yield was 49.3, Color was golden yellow, odour was agreeable, and the oil was liquid at room temperature. Saponification was performed on the extracted seed oil.the ph of the prepared soap was 8.47, foam height was 4.3cm the soap was cream in colour and slightly soluble in distilled water. Justification of the use of the seed oil for home made and large scale industrial production of soap was made. Keywords: gingerbread plum, seed, oil extraction, analysis, saponification. Received: Accepted: Published: Corresponding author:

2 31 1. INTRODUCTION There are many areas where oils and fats are used for non-food purposes. Thus, detergents, soaps, glycerine and polymers, inks, lubricants, and biodiesel may be derived from fatty acids and their derivative [1]. Almost all plants contain fats or oils, mainly in their seeds. The amount varies from very little to as much as 70-80% [2]. For oilseeds, the oil is generally extracted from crushed seed by the Soxhlet procedure using hexane or a suitable hydrocarbon fraction such as that boiling between 40 and 60 o C. This method provides a sample of oil which can also be used for further tests [3]. Gingerbread plum (Neocarya macrophylla) trees grow in arid and semiarid regions mainly in the Western part of Africa and Central America particularly Panama. It is known in Hausa Language as Gawasa [4]; [ 5]. The plant is semi-cultivated [6]. Seed oils from such plants can be used to make soaps[7]. Soaps are residual sodium salts of fatty acids that arise from neutralization of an oil or fat with caustic soda [8]. This research work is aimed at oil extraction from Neocarya macrophylla Seed, quality control, saponification of the seed oil and justification of its application for industrial production of soap. 2. MATERIALS AND METHOD 2.1. Seed material Neocarya macrophylla seeds obtained from Gingerbread plum tree were collected in the Month of October from Junju town, Niger Republic. The other parts of the plant collected were the leaves, the fruits and the flowers for the purpose of identification. The plant was identified and authenticated by a Botanist at the Biological Sciences Department, Bayero University, Kano (BUK) Nigeria. Confirmation of taxonomic identity of the plant was achieved by comparison with voucher specimen (voucher No. 175) kept at the Herbarium of the Department of Biological Sciences and use of documented literature [9]. The seeds were selected and damaged ones were discarded. The seeds were cleaned, de-shelled and well dried and ground using laboratory plastic pestle and Mortar prior to extraction Oil extraction The repeated extraction of 10g of ground seeds of Neocarya macrophylla was conducted in a soxhlet extractor using n-hexane (boiling between C) for six hours until the desired quatity was obtained. The oil was obtained after the solvent was removed under reduced temperature and pressure and refluxing at 70 ºC to remove excess solvent used in the oil. Extracted seed oil was stored in freezer at 2 C for

3 32 subsequent physicochemical analysis. The extraction was carried out in the Biochemistry Laboratory, Department of Biochemistry, Kebbi State University of Science & Technology, Aliero, Nigeria Oil Yield The oil which was recovered by complete distilling of most of the solvent on a heating mantle was then transferred to measuring cylinder. The measuring cylinder is then placed over water bath for complete evaporation of solvent for about 2-3 hours in accordance with the method reported [10] and weight of the oil was recorded and expressed as oil content(%) as follow Oil weight Oil content (%) = 100 Sample weight 2.4. Physiochemical analysis The acid value, iodine value and saponification value determinations were carried out using the methods reported [11], [12] and [13]. Free fatty acid Free fatty acid was determined according to the Official Method Ca 5a-40 [14] while peroxide value was determined using the method specified by International standard organization [15] Acid Value 100cm 3 of neutral ethyl alcohol was heated with 10g of the oil sample in a 250cm 3 beaker until the mixture began to boil. The heating was stopped and cooled, and was titrated with N/10 KOH solution, using two drops of phenolphthalein as indicator until a permanent pink color was obtained at the end point. Acid value was calculated using the expression; A.V =0.56x No. of ml. N/10 KOH Saponification Value 2g of the oil sample was added to a flask containing 30cm 3 of ethanolic KOH and was then attached to a condenser for 30minutes to ensure that the sample is fully dissolved. After sample has cooled, 1cm 3 of phenolphthalein was added and titrated with 0.5M HCl until a pink color indicates the end point. Saponification value was calculated using the expression; (S-B) x M x 56.1

4 33 SV = Sample weight (g) Where S = sample titre value B = blank titre value M = molarity of the Hcl 56.1 = molecular weight of KOH Iodine value 0.4g of the sample was weighed into a conical flask and 20cm 3 of carbon tetrachloride was added to dissolve the oil. Then 25cm 3 of Dams reagent was added to the flask using a safely pipette in fume chamber. Stopper was then inserted and the content of the flask was vigorously swirled. The flask was then placed in the dark for 2hours 30minutes. At the end of this period, 20cm 3 of 10% aqueous potassium iodide and 125cm 3 of water were added using a measuring cylinder. The content was titrated with 0.1M sodium thiosulphate solution until the yellow colour almost disappeared. Few drops of 1% starch indicator was added and titration continued by adding thiosulphate drop wise until blue coloration disappeared after vigorous shaking. The same procedure was used for blank test C (V 1 -V 2 ) I.V = M Where C = Concentration of sodium V 1 = Volume of sodium thiosulphate used for blank V 2 = Volume of sodium thiosulphate used for determination M = Mass of the sample Free fatty acid About 2 g of the extracted oil sample was weighed into a 250 ml Erlenmeyer flask using an analytical balance. 20 cm 3 of 95% neutralized ethanol was added to the flask. The solution was heated slightly at 20oC to aid the dissolution of the fat in the alcohol. 2 drops of phenolphthalein solution was added as indicator.

5 34 The obtained yellowish solution was titrated with 0.1N standard sodium hydroxide solution while shaking the solution vigorously. The colour of the solution turned pink and at the point when the pink colour persisted for 30 s was termed the end point. The percentage of free fatty acid in the oil was calculated as oleic as follows: % Free fatty acid (% Oleic) = V N 28.2 Weight of Sample where, V = average volume of NaOH (ml) N = normality of NaOH (0.1) Peroxide value 10cm 3 of chloroform was added to 2grams of the sample in a 500cm 3 conical flask and dissolve quickly by stirring.15cm 3 of glacial acetic acid was added followed by 1cm 3 freshly prepared saturated potassium iodide solution. The flask was closed and stirred for 1min. and kept in the dark for 5mins, 75cm 3 of water was added and shaken vigorously. 3 drops of starch solution was added as indicator. The liberated iodine was titrated against 0.01M sodium thiosulphate. Peroxide value was calculated using the expression; P.V (V 1 -Vo) x C x 1000 Where; Vo = volume of sodium thiosulphate V 1 = Volume of sodium thiosulphate solution used for determination of sample C= the concentration of sodium thiosulphate used M= mass of test sample M Saponification Procedure 20 grams of sodium hydroxide pellets was dissolved in 100cm3 volumetric flask and the volume made to the mark with distilled water. The required quantity of alkaline solution was mixed with Neocarya macrophylla seed oil (ratio 1:1 v/v). The oil was

6 35 warmed gently and poured into the beaker followed by the alkali solution to form an intimate mix and then stirred frequently using stirring rod until reaction reached equilibrium this took 5 minutes. The saponification mixture was then poured into mould and allowed to dry (cure) for 24hours ph Determination The ph was determined using a ph meter (827 ph lab Model). 5g of the soap shavings was weighed and dissolved in distilled water in a 50cm 3 volumetric flask. This was made up to prepare 10% soap solution in line with literature report [16]. The electrode of the ph meter was inserted into the solution. The ph reading was recorded Foam ability Test 0.5g each of soap (shavings) was added to a 100cm 3 measuring cylinder containing 100cm 3 of distilled water. Vigorous mixing was done for 15 minutes using Votex mixer ( Model 3518 J-Kem Scientific England) The mixture was shaken vigorously so as to generate foams. After shaking for about 5 minutes, the cylinder was allowed to stand for about 15 minutes. The height of the foam in the solution was measured and recorded. 3. RESULTS Table 1: Chemical and quality characteristics of Neocarya macrophylla seed oil Parameter Result Acid value ( mgkoh/g) ± 0.01 Saponification value (mgkoh/g) Iodine value (gi 2 /100g) Free fatty acid (% oleic acid) Peroxide value (meq H 2 O 2 ) Oil content (%) ± ± ± ± % The values are mean and ± standard deviation of triplicates determinations.

7 36 Table 2: Physical characteristics of Neocarya macrophylla seed oil Parameter Colour Odour Physical state at room temperature Observation Golden yellow Agreeable Liquid Table 3: Physical and chemical characteristics of the Neocarya macrophylla seed oil soap. Prameter ph Foam height(cm) Colour of soap solution Solubility in water Results Cream Slightly soluble The values are mean of triplicates determinations. 4. DISCUSSION The physicochemical analysis of the gingerbread plum (Neocarya macrophylla) seed oil showed that it has saponification value of ± 0.10KOH/g which is lower than the saponification value of the the following seed oil; Nigerian cotton seed oil mgKOH/g [17], Neem seed oil 213mgKOH/g [18] Rubber seed oil mgKOH/g [19], African pear seed oil mgKOH/g [20], Hyptis spicigera seed oil mgKOH/g [21] Citrus lanatus mgKOH/g [22], Adansonia digitata linn seed oil mgKOH/g [23], Elaeis guineensis seed oil mgKOH/g [24], higher than the saponification value of the following oils; Nepoleana imperials seed oil 77.06mgKOH/g [ 23] African pear seed oil mgKOH/g [20], Castor seed oil123.3mgkoh/g [25], Polyalthia longifolia seed oil mgKOH/g [ 26], Cashew karnel oil 137mgKOH/g [27], Lagenaria siceraria seed oil [28]. High saponification value indicate or justify the usage of oil for soap making [29] The iodine value was ± 0.01g I 2 /100g which is lower than the iodine value of the following oils; Cashew karnel oil 41.3I 2 /100g [27], Polyalthia longifolia seed oil

8 I 2 /100g [25], Avocado pear I 2 /100g [19], Detarium microcarpum 55.9I 2 /100g [24], Hypertis spicigera seed oil 81.22I 2 /100g [20], higher than the iodine value of Landolphia owariensis seed oil 15.10I 2 /100g [24], and Elaesis guineensis seed oil 18.30I 2 /100g [24] The iodine value that was obtained is below 100.Oils with iodine value below 100 are called Non - drying oils and they are good or useful in soap production [30]. The acid value obtained ± 0.01 mgkoh/g which is lower than the following value obtained from other seed oils; African pear seed oil mgKOH/g[20], Monodora myristica gaertin seed oil 14.31mgKOH/g [23], rubber oil 15.03mgKOH/g [19] The acid value is higher than the following seed oil; Hyptis spicigera seed oil 2.5mgKOH/g [21] Citrus lanatus seed oil 5.25mgKOH/g [23] Avocado pear seed oil 5.200mgKOH/g [21], Cashew karnel oil 10.7mgKOH/g [27] higher than mgKOH/g reported [20] for olive oil is useful in soap making. The free fatty acid obtained from the analysis ± 0.10 which is lower than the value of callophyllum inophyllum linn seed oil 160.3% [24 But the free fatty acid value of parinari macrophylla is higher than the following oil; polyalthia longifera seed oil 7.73% [26], monodora myristica gaeth dunat 7.20% [23], rubber seed oil 7.55% [19]. Free fatty acid can stimulate oxidative deterioration of oils by enzymatic and/or chemical oxidation to form off flavor component [23].. The peroxide value obtained which has a value of 45.48± 0.02 mgmeq/kg is lower than polyalthia longifera seed oil mgmeq/kg [26], butyrospermum parkii oil 77.5mgmeq/mg [31]. But higher than; dacroyodes edulis (G.Don) H.J lam seed oil 20.00mgmeq/kg [23], stercula setegera seed oil 35.0mgmeq/kg [31]. The high peroxide value indicate high level of oxidative rancidity of oil and also suggest low levels of anti oxidant [31] The ph of the prepared soap was 8.47, lower than 9.38 reported for cotton seed oil soap [32], comparably lower than the ph range of 9-11 but favourably higher than the ph range of 3-5, which are considered as high and low levels respectively by the National Agency for Food and Drug Administration and Control(NAFDAC) [33]. This could be due to incomplete alkali hydrolysis resulting from the saponification process. Addition of excess fat or oil or any other superfatting agent can to reduce the harshness of the soap and lower the soap ph. Superfattinfg with 10% excess fat and oil was reported [34]. Superfatting soaps with 1-2% neutral oils or glycerine also resulted in the better quality of soaps that were free of cracks [35]. The foam height of the soap was 4.5 cm lower than that of sesame oil soap, 4.8cm [36]. and higher than that of shea nut oil soap, 2.7cm [33]. The soap was cream in colour and slightly soluble in distilled water.

9 38 5. CONCLUSION From the results obtained after the chemical analysis of the oil it can be concluded that the selected oil is utilizable for industrial production of soap and other cosmetics. The physical properties exhibited by the seed oil indicated its purity at preliminary stage and therefore suitable for commercial production Acknowledgement I wish to acknowledge the maximum cooperation from Shehu Umar Acting Chief Technologist, Chemistry Laboratory, Department of Applied Chemistry, Kebbi State University of Science and Technology, Aliero, Nigeria. He has assisted maximally when I was carrying out some analysis in the Chemistry Laboratory. 6. REFERENCES [1] Shahidi, F. Industrial and Non edible Products from Oils and Fats in Bailey s Industrial Oil and Fat Products, 6 th Edition, Vol.6. New Jersey: John Wiley & Sons, Inc, p28. [2] Bockisch, M. Fats and Oils Handbook. Illinois: AOCS Press. Champaign, 1998, p174 [3] Gunstone, F.D. The Chemistry of Oils and Fats: Sources, Composition, Properties and Uses. 1 st Edition. Oxford: Blackwell Publishing Ltd, p.101 [4] Blench,RHausa names for plants and trees. Printout December 11, p.23. Accessed on 23/10/2011 at [5] Dalziel, J.M. A Hausa botanical vocabulary. London: T.Fisher Unwin, [6] Amza, T., et al., Nutritional and Functional characteristics of gingerbread plum (Neocarya macrophylla): an underutilized oil seed. Grasasy aceites (3): p [7] Warra, A.A. Extraction and Saponification of Gingerbread plum (Parinari macrophylla) Seed oil. Journal of Scientific Theory and Methods. Vol. 2012: p [8] [Gunstone, F.D. Structured and Modified Lipids. New York: Marcel Dekker, Inc., p.43 [9] Hopkins, B and Stanfield, D.P. Savanna trees of Nigeria. Ibadan: University Press, p.19

10 39 [10] Pant,K.S., et al., Seed oil content variation in Jatropha curcas Linn. in different altitudinal ranges and site conditions in H.P. India. Lyonia : p [11] AOAC. Official Methods of analysis of the Association of Official Analytical Chemists, 16 th Edition, vol.2 Gaithersburg: AOAC, [12] Akpan, U. G., Jimoh, A. and Mohammed, A. D. Extraction and characterization and Modification of Castor seed. Leonardo Journal of Science : p [13] Bassir,O. Handbook of Practical Biochemistry. Ibadan: University Press, 1978.p.143 [14] American Oil Chemists Society, AOCS Official Methods and Recommended Practices of the American Oil Chemists Society. Washington, DC: AOC Press, [15] International Standard Organization Animal and vegetable fats and oils. Determination of peroxide value. (ISO 3960). First edition p.1-3. [16] Dalen, M.B. and Mamza, P.A. Some Physico-Chemical Properties of Prepared Metallic Soap-Driers of Aluminium, Copper and Zinc. Science World Journal (3): p.7-9 [17] Warra, A.A., et al., Extraction and Physicochemical Analysis of some selected Northern Nigerian Industrial oils. Archives of Applied Science Research. 2011a. 3 (4): p [18] Akpan, U.G Extraction and characterization of neem seed oil: In: (Ed) Eyo, A.A, Aluko, P.O, Garba, S.A, Ali, U.D, Lamai, S.L and Olufeagba, S.O Biotechnology and Sustainable development in Nigeria, Proceedings of the 12th Annual Conference of the Biotechnology [19] Jumat, S.and Bashar, M. A. A. Study on the thermal properties and solid fat content of Malaysia rubber seed oil. The Malaysian Journal of. Analytical Science : p.1-7. [20] Ikhuoria,E.U. and Maliki, M. Characterization of Avocado pea (persea americana) African Pear ( Dacryodes adulis) extracts. African Journal of Biotechnology (7):p [21] Ladan. Z., et al., Physicochemical properties and fatty acid profile of hyptis spicigera seeds oil. Research Journal of Applied Science :p [22] Anhwange, B. A., et al., Chemical Analysis of CitrullusLanatus (Thunb.), Cucumeropsis Mannii (Naud.) and Telfairia Occidentalis (Hook F.) Seeds Oils. Journal of Applied Science Research (3): p [23] Ibironke A. A. Physicochemical attributes of oils from seeds of different plants in Nigeria.Bulletin of Chemical Society of Ethiopia : p

11 40 [24] Akububugwo I.E, and Ugbogu A.E. Physicochemical studies on oils from five selected plant seeds. Pakistan Journal of Nutrition : p [25] Warra, A.A., et al., Extraction and Physicochemical Analysis of some selected Northern Nigerian Industrial oils. Archives Applied Science Research (4): p [26] Oyedeji F.O., Adeleke B.B., and Akintola C.B. Physicochemical and fatty acid profile analysis of polyalthia longifolia seed oil. Trends in Applied Science Research. 2011d. 6:p [27] Akinhanmi T.F, Atasie V.N,and Akintokun P.O. Chemical composition and physicochemical properties of cashew nut (Anacardium occidentale), Journal of Agriculture,Food and Environmental Science : p [28] Hassan L.G, and Sani N.A. Comparative studies on the physicochemical properties of bottle goard (lageneria siceraria), seed oils extracted by two methods. Nigerian Journal of Basic of Applied Science :p [29] Warra, A.A., et al., Soap preparation from Soxhlet extracted Nigerian Cotton seed oil. Advances in Appied. Science Research. 2011b. 2 (5): p [30] Kochhar, S. L. Economic Botany in the tropics, 2 nd ed. Delhi: Macmillan India Ltd, 1998 p 547 [31] Kyari M.Z Extraction and characterization of seed oils. International Agrophysics : [32] Warra, A.A., Wawata, I.G, Gunu, S.Y and Atiku, F.A. Soap preparation from soxhlet extracted Nigerian Cotton seed oil. Advances in Appl. Sci. Res. ( 2011b). 2 (5): [33] Umar, M. A. Paper presented at a Training workshop for small and medium scale Enterprises organized by UNDP/JCSL and Ministry of Commerce and Industry, Maiduguri,Borno State, Nigeria p.1-4 [34] Warra, A.A Hassan, L.G. Gunu, S.Y and Jega, S.A. Cold- Process Synthesis and Properties of Soaps Prepared from Different Triacylglycerol Sources. Nigerian Journal of Basic and Applied Science (2): p [35] Kuntom, A., et al., Effects of Superfatting Agents on Cracking Phenomena in Toilet Soap. Journal of Surfactants and Detergents ( 3): p [36] Warra, A.A Suraj, L.G.and Jega, S.A. Production of Soap from Northern Nigerian Sesame (Sesamum indicum,l.) Seed oil. Bayero Journal of Pure and Applied Science. 2011c. 4(1):

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