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    Literatur U3 Kimfis Aul

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    Adela Try Agusdi

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    2/7 Effect of solvent polarity on the extraction of components of pharmaceutical plastic containers Iqbal Ahmad’, Arif Sabah?*, Zubair Anwar’, Aysha Arif’, Adeel Arsalan! and Kiran Qader! ‘Baga institute of Pharmaceutical Sciences, Bagai Medical University. Toll Plaza, Super Highway, Gadap Road, Karachi, Pakistan 2Facuky of Pharmacy, Ziauddin Medical University, 4/B, Shahrab-e-Ghalib, Block 6, Clifton, Karachi, Pakistan ‘Abstract:A study of the extraction of polymeric material and dyes from the pharmaceutical plastic containers using various organic solvents was conducted to evaluate the effect of polarity on the extraction process. The plastie containers used included semi-opaque, opaque, transparent and amber colored and the solvent used were acetonitrile, methanol, ‘ethanol, acetone, dichloroethane, chloroform and water. The determination of extractable material was carried out by gravimetric and spectrometric methods. The yield of extractable materials from containers in 60 h was 0.10-1.29% (w') and the first-order rate constant (kay) for the extraction of polymeric material ranged from 0.52-1.50 x 10° min’ and for the dyes 6.43- 6.74 x10" min". The values of (Kay) were found to be an inverse function of solvent dielectric constant and decreased linearly with the solvent acceptor number. The extractable polymeric materials exhibited absorption in the 200-400 nm region and the dyes in the 300-S0Onm region. The rates of extraction of polymeric material and dyes from plastic containers were dependent on the solvent dielectric constant. The solvents of low polarity were more effective in the extraction of material indicating that the extracted material were of low polarity or have non-polar character. The dyes were soluble in acetone and chloroform, No plastic mate ‘aqueous solution was found to be extracted from the containers in Keywords: Plastic containers, extractives, dyes, polarity, kinetics. INTRODUCTION Plastic containers are among the most widely used containers for the storage of solid and liquid pharmaceutical products. These containers are ‘manufactured to possess the prescribed performance characteristics of chemical inertness; air, moisture and light protection and minimum interaction between the plastic material and the pharmaceutical products (British Pharmacopoeia, 2016; Unites States Pharmacopeia, 2016). The interaction’ may result in the release of the polymeric material and dyes from the plastic containers into the pharmaceutical product affecting its quali safety and efficacy. Two factors are important to consider in connection with the polymeric material used to ‘manufacture the plastic containers (Jenke, 2007) Estractables Substances that can be extracted from a plastic ‘materialsystem using extraction solvents and/or ‘extraction conditions are expected to be more aggressive than the condition of contact between the material/ system and a finished drug product Leachables Substances that are present in the finished drug product because ofits interaction with a plastic material or system during its intended use. In view of the importance of these phenomena several workers have conducted studies on the leaching, extraction and determination of components ponding author: e-mail: dari_bips |@yahoo com of the plastic material from the containers and tubing 10 evaluate the contents (Bennanet af2002; Berg et al 1993; Green, 2005; Jenke,1997, 2002, 2004, 2005; Jenke, 2001, 2005, 2006; Kim ef ai 1990; Nicholas, 2006; Reifer al 1996; Sarbachet al 1996; Snell, 1993; Weitzman, 1997; Wang, 2005) and their harmful effects on the products ‘Genke, 2007; Kauffman, 2006; Northup, 2005; Osterberg, 2005). An important consideration in the study of the ‘extractable from the plastic material is the nature of the solvent and its polar character. Organic solvents affect the rates of chemical reactions such as the degradation of drugs including riboflavin and analogs (Ahmed er al. 2006), louroquinolones (Ahmad er al 2013, 2014; Bilskiet al, 1998), steroids (Khataket al, 2013) and polymerization reactions (Ahmad et al, 2013) on the basis of their polar character. ‘The kinetics of extraction and extraction efficiency depends on the nature of the extractable components and the polarity of the solvent employed (Spiro and Siddiqui, 1981). Materia/water equilibrium interaction constants have been determined for several organic models solutes. and the material used in pharmaceutical plastic containers (n0n-PYC polyolefin). The interaction constants have been related to the polarity of the aqueous/organic solvent mixtures used (Jenke, 2006). The rate of a reaction between dipolar molecules depends on the dielectric constant, c, (a measure of solvent polarity) of the medium (Sinko, 2011). Pak. J Pharm. Sei, Vol30, No.l (Supplh, January 2017, pp 247-252 247 Dipindai dengan CamScanner Polarity effect on extractables from containers Ink = Ink. = K (We) ro) Where ka. is the rate constant in a medium of infinite dielectric constant, The € of the medium is approximately equal to the ¢ of the solvent in dilute solutions. An increase in ¢ tends to increase the rate and a decrease in ¢ 10 a decrease in the rate. The rate constant ofa reaction can be related to the € of the solvent, ‘The aim of this work is to study the kinetics of extraction of polymeric material and dyes from different pharmaceutical plastic containers using a number of organic solvents and to develop a correlation between the rate constants and the polarity of the organic solvents used. It is also intended to determine the spectral characteristics of the extractable material and the dyes present MATERIALS AND METHODS, Materials The following plastic containers of pharmaceutical grade were used in this study (white semi-opaque and white ‘opaque, high density poly ethylene (HDPE); transparent and amber colored, low density polyethylene (LDPE). The containers were obiained from Friends Plastic Containers and Closures Manufacturer, Karachi. All the organic solvents used were of the purest form available from Merck & Co (Germany): Methanol (99.9%), ethanol (99.9%), acetonitrile (99.8%), acetone (99.5%), dichloroethane (99.8%) and chloroform (99.8%). The water used was freshly glass distilled water Extraction procedure and determination Six samples each of the plastic containers were filled with 100 mi of the solvent and placed in a thermostat bath maintained at 25: 1°C for a petiod of 60 b. The samples of containers with different solvents were withdrawn at 10 h intervals. The solvent were evaporated to dryness under reduced pressure at room temperature (25°C). The residues of the semi-opaque, opaque and transparent containers appeared as a whitish mass and those of the amber containers as a reddish yellow mass. All the residues were carefully weighed and the percentage contents (w/w) calculated. Each experiment was performed in triplicate and the results were determined in averages. Absorption spectra ‘The absorption spectra of the polymeric material and dyes extracted from the containers were determined on Shimadzu UV- visible recording —spectrophotometer (model UV-160, Japan) using quartz cells of 10-mm path length. RESULTS. Extractable material The amount of chemical extractable polymeric material ‘and dyes from the plastic containers was determined at different time intervals during the extraction with various solvents, The overall amount of the extractable material from the containers ranged from 0.10-1.29% (wiw). The results of atypical experiment for the extractable material ‘obiained from the opaque containers using different solvents are given in table 1. The concentration values in different solvents vary, with time, and change with the solvent indicating the effect of the solvent characteristics ‘on the extent of extraction ofthe chemical components of the containers. The LDPE containers (wansparent and amber color) showed a greater amount of extractable ‘materials than the HDPE containers (semi-opaque and ‘opaque) probably due to ease of extraction with the ‘organic solvents as indicated by the rates of extraction described under the kinetics section, ‘The UV absorption spectra of the material extracted from the containers in different solvents have been determined and the absorption maxima recorded (Table 2). These absorption maxima are in the range of 200-400 nm and represent a mixture of polymeric components present in ferent plastic containers. The polymeric material may include compounds with phenyl rings and conjugated double bond residue (Klevens, 1953) being extracted in various organic solvents with broad absorption in the UV region Extractable dyes ‘Two reddish pink dyes were also extracted from the amber colored containers using chloroform and acetone, “The absorption spectra of the dyes were determined and ‘are shown in fig. 1. The dyes extracted in chloroform ‘exhibited absorption maxima at 420 and 444 nm and that in acetone at 369 and 442 nm in the visible region. The removal of the dyes showed 8 litle change in the color of the containers. These dyes could be extracted into the product during the slorage. Pigment orange and ‘chromophthal brown absorbing in the 400-500 nm region have been used to give light-protecting properties to the plastic containers (Beyrich and Tibussek, 1981). Kinetics of extraction The various techniques used for the extraction of active ‘components of plant materials have been reviewed (Azmi et al 2013), The extraction of drugs from the plant material has been shown to follow afirst-order kinetics process (Spiro and Siddiqui, 1981). In[C]-In (C= Ait In [C] = 2303 log vw [CF it @ or ‘ky = 2.3034 * log 10 [C°/C] «) @ 28 Pak J Pharm. Sci, Vol30, No.1(Suppl), January 2017, p-247-252 Dipindai dengan CamScanner Jurnal Kimia Valensi, Vol 5(2), November 2019, 185-193, ‘Available online at Website: Mip/joural uinjkt.ac.id'index,phyvalensi Haiensi UNIFAC Model for Liquid-Liquid Phase Equilibrium of Penicillin G and 6-APA System Lienda Aliwarga*, Herri Susanto, Reynard Reynard, Agnes Veronica Victoria Chemical Engingering Department, Bandung lasttue of Technology “Corresponding author: lienda@che.ith.ac.id Received: November 2018; Revision: Jamary 201 Abstract ‘This study investigated the effect of pH and type of solvent on liquid-liquid phase equilibrium in the system of pare penicillin G and mixed penicillin G with 6-APA. Penicillin G extraction was carried out in a pH range of 2.0-5.0 at 4 °C using several types of solvents. The liquid-liquid phase equilibrium mathematical model was prepared by assuming that a single stage of thermodynamic equilibrium occurs in a batch process of liquid tiquid extraction. The coefficient of activity was calculated by the UNTFAC method. From the experiment, it was found that the extraction process of penicillin G was strongly influenced by pH of the solution. The highest yield of ‘extraction was achieved with different solvents in the two types of solution. For pure penicillin G system, the highest yield was obtained in n-butyl acetate solvent (95.51%) while for penicillin G mixtured with 6-APA. it ‘was obtained in methyl iso-buty! ketone solvent (92.6%). The UNIFAC model has been tested against five three- ‘component liquid-liquid phase equilibrium systems at pH 2.0 and 2.5. It was able to estimate the concentration of penicillin G inthe organic phase with a relatively average error between experiment and calculation of 8.32%. Keywords: Extraction, penicillin G, 6-APA, UNIFAC, DOI: 10.15408jhv.»5i2.9869 1, INTRODUCTION The use of semi-synthetic penicillin as a natural penicillin derivative product is now increasingly widespread due to the nature of pathogenic microorganisms that are starting to be resistant to natural penicillin, The advantage of semi-synthetic penicillin is that itis resistant to beta-lactamase, broad-spectrum, and stable in acidic conditions (Singh and Goyal, 2014). ‘This component is produced from the hydrolysis of penicillin G and V using the enzyme penicillin acylase or from a chemical reaction (Dhal, 2018; Haagensen, 2018; Sheldon and van Pelt, 2013; Szewczuk, 2018). Commercially, semi-synthetic penicillin is produced from 6-aminopenisilic acid (6-APA) through an enzymatic equilibrium reaction with penicillin acylase which yields in a mixture of 6-APA components, penicillin G, and phenylacetic acid (PAA) (Carleysmith and Lilly, 2018; Deo and Gaucher, 2018; Haagensen, 2018; Harvey, 2018; Park, 2018: Warburton, 2018). Purification of 6-APA resulting from enzymatic conversion from penicillin G is carried out by extracting penicillin G which is nat converted at taw pH. ‘6-APA in the phase of raffinate is concentrated and followed by crystallization in the isoelectric pH region (Deo and Gaucher, 2018; Haagensen, 2018; Karlsen and Villadsen, 2018). Separation of penicillin G with liquid- liquid extraction is conducted by utilizing the solubility difference of penicillin G in the phase and in the organic phase. Previously, the effect of pH and ype of solvent on the solubility of pure penicillin G at 25 °C hhas been studied (Reschke and Schigerl, 19843). ‘The thermodynamic model is assumed for one stage of equilibrium in liquid-tiquid extraction of penicillin G in batches and is arranged to obtain operating conditions and lypes of solvents suitable for the extraction of penicillin G and a mixture of penicillin G with 6-APA. The liquid-liquid phase equilibrium is expressed in terms of the similarity of the activity coefficients in both phases. The activity coefficient is a quantity that cannot be (Copyright ©2019, Published by Jummal Kimia Valensi ASSN: 2460-6065, EASSN: 2548-3013 Dipindai dengan CamScanner UNIFAC Model for Liquid-Liquid Phase Equilibrium of Penicillin G and 6-APA System integrator by calibration outside the standard penicillin G peak. ‘Table 1. Operation conditions for HPLC Parameters Value Column temperature 38C Detector UV Q=220 om) Sample volume é phosphate Mobile phase buffer (0.025 M) pH 7 = 2:8 Flowrate ofthe satin mobile phase 3. RESULTS AND DISCUSSION Determination of Stirring Time Stirring time is the minimum time required to obtain the phase equilibrium, which indicated by the concentration of penicillin G. The residual in the raffinate phase has not changed with the variation of the stirring time. Based on observati irring time does not significantly affect the — extraction percentage (Figure 1). 1000 2 & 2 gee é Extraction percentage (%) = 5 3 0 18 30 48 60 75 90 105 120 ‘Stirring time (second) Figure 1. The extraction percentage at a various stirring time ‘The extraction percentage price is in the range of 94.5-95.5%. When the stirring time is less than 60 seconds, the extraction percentage tends to increase. This might be due to the contact between the organic phase ‘and the aquatic phase is still not perfect and the extraction conditions have not reached equilibrium. The residual concentration of penicillin G in the raffinate phase is relatively Aliwarga eta constant during the stirring time of 60 seconds. Afier 60 seconds, the addition of the stirring time did not significantly affect the concentration of penicillin G in the raffinate phase and the conditions had reached ‘equilibrium. Therefore, the stirring time used in this study was 60 seconds (1 minute). Partition Coefficient and Extraction Percentage of Pure Penicillin G System The partitioning coefficient of penicillin G in various solvents shown in Table 2 is obtained from the optimum pKa which is the result of optimization of the difference in the smallest square between the distribution coefficient of the experimental data with the distribution coefficient of the calculated results. ‘The experimental results show that the largest panition coefficient of penicillin G was ‘obtained in the solvent n-butyl acetate (21.47) and the lowest partition coefficient in chloroform (5.885). ‘Table 2. Partition coefficient of penicillin G in pure penicillin G system (pKa = 3.015) Ka (Reschike Solvent ka & Schugert, 1984b) Nebutylacetate 2147 B isobutyl ncetate 13.62 37 Isoamyl acetate 12.05 2 ‘Methyl isobutyl ers 8.017 - Chloroform, 5.885 125 A noticeable difference between the experimental results. and the partition coefficient data were obtained by (Reschke and Schigerl, 1984b). This may be influenced by a decrease in temperature, causing the penicillin G solubility to get smaller. In the literature, experiments were carried out at 8 °C, whereas in this study, 4 °C was chosen, was supported by (Jing, 2010) that reported data on the solubility of penicillin sulfoxide in various solvents with the temperature range of 273.15- 29R.55K, the solubility decreased in a lower temperature due to the differences in solvent polarity, intermolecular interactions, hydrogen ‘bonds, and others, Furthermore, the number of solvent mole fractions can also determined the solubility of penicillin, where the higher the mole fraction of water, the solubility of Penicillin G in the aquatic phase will increase Dipindai dengan CamScanner Kimia Dasar: Konsep-konsep Init Aid 1 Edis Ketga Raymood Chang Siabul Asti: General Chemisirs: The Ecrenial Concepts ‘Third Edition Raymond Chang Copyright © 2003 by The McGraw-Hill Companies, Translation copyright © 2008 bby Penerbit Erlangga, All rights reserved. Authorized translation from English longusge edition published by McGraw-Hill, ‘ak verjemahan dataun bshasa Indonesia pods Pemerbit Erlangga ‘berdasarkan perjanjian resmi tanggal 30 Januari 2004, Ath Balsa Departemen Kimia, Institut Teknologi Rendung: ‘Muhamad Abdulkadir Martoprawiro, Ph.D. Indra Noviandri, Ph.D, Deana Wahyuningrum, M.S De, Huchari Ismunandar, PhD, Drs, Hiskia Achmad De. I Nyoman Marsihy Drs. Hidayat Muchsinuddin Editor: ‘Lemeda Simarmata, $.T. Bats in ise don diby-ow oleh Baan Produks}Pencri Erlangga ‘dengan Maciniosh GS. dengon menggunatan hurt Times 10. Seting och ; Divisi Peri Dep Setting Percetakan: IT, Gelora Aksorn Pratama 0 6 OS 6 84 gan Dero heras meng. ment, menfotoop xox m banyak dl am “Peres hon kee i akin sere meng ‘ona Ih tel dari Penerbit Erlanga, ‘ OAK CITA DILINDUNG! OLEH UNDANG-UNDANG. Dipindai dengan CamScanner Dipindai dengan CamScanner Dipindai dengan CamScanner CA Re 90 ‘Bab 4 Reaksi dalam Laruian Berair 4.1 Sifat Umum Larutan Berair rcabsi kimia dan hampir semua proses biologs belangsung paces ‘arena itu merupakan hal yang pening untuk memahamy Feel sat yang bebeda dla nan dengan medium ait, Sebaaipermulsn, ar ay yong dimaksud dengan tartan? Larwan adalah crmpuran yong ae Ie st at yn jumahnye lebih slit ised sat teraa, edo eu Janey i bono ise pl. Lrn isa Brodspec (pe type loam) to a (ily hPa a iti pe tmembshs arate ear. mana ze telert evclna ela er yg 8S pelaruinya adolah air. fa Elektrolit versus Nonelektrolit Sera za ea yeg rt dtm seman ke dl ash 3 i pon, berikut: elekuolit dan nonclektolit. Elekirolit adalah suat zar, vane keiite dalam air akan menghasiln larutan yang dapat menghartarkan aruslistrit. Non tdok menghanarkan aru sri ett dilken dalam oc Gamba 4. menpeiaey Suatu metode yong mudsh dan langsung untuk membedskan antaralauan elena Iaruan norelektolit. Sepasang elektroda platina dicelupkan ke dalam gels Lnig ‘ers air, Untok menyalakan bola lampu pija, ars listrik harus mengalir dai sa elem te clelirdsIninya, sehingga menyempurnakan rangkaionVsrik. Ait marti meng Penghantarlstrik yang sangat buruk, Walaupun demikia,jika Kita menambablan sed ‘atrivm Klorida (NaC). bola fampu pijar akan menyala sogerasetelah garam lana daa ait. Padatan NaCl, suaty senyaveaionik, erurai menjadi ion-ion No* dan CY pda ay tarut dalam ait. fon Na" akan tcrtarik he elekirods negatif dan ion CI* akse meas serous posit, Pergcrakan ini menghasian aruslisrik yang setara dengan alia tres sepanjang kabel lozam. Oleh Karena larutan NaC dapat menghantarkan ams list la NaCI merupakan suatyelekrolit Air muni hanya mengardane sedikit ion, ching ik dapat menghantarkan aru list Feceet 4:1 Sua ronlaton la ana meted entre fran ei on me Aerereuan larson nant menghoterton ura ll rpomun pode unk bn 28 ee ay tenaantin tnccinit at mengandg lon eng del it C42 ATA oe tr acy nd ea meng sii dan ets lamp pr meni ‘oath tl mensrans lon dea jonah bese don hel lamp jr eo {mela st terlart yong ert ela sama dation tga ksu dat Dipindai dengan CamScanner Dipindai dengan CamScanner Dipindai dengan CamScanner IS FATIMAH UE FISIKA Mt U Dipindai dengan CamScanner deepublish| publisher JL.Rajawali, G. Elang 6, No 3, Drono, Sardonoharjo, Ngaglik, Sleman [LKaliurang Km.9,3 - Yogyakarta 55581 ‘Telp/Faks: (0274) 4533427 Website: www deepublish.co.id ‘www.penerbitdeepublish.com E-mail: cs@deepublish.coid Katalog Dalam Terbitan (KDT) FATIMAH, Is Kimia Fisika/oleh Is Fatimah.Ed.1, Cet. 1-Yogyakarta: Deepublish, Desember 2017. xii, 198 him; Uk: 2026 em ISBN 2 978-602-401-034-8 ISBN Elektronis : 978-602-475-568-3 1. Kimia Fisike 1. judul S413 Cetakan Pertama : Oktober 2015 Desain cover: Unggul Pebri Hastanto Penata letak = tha Fatria Iriyanti PENERBIT DEEPUBLISH Penesbitan CV BUDI UTAMA) Anggota IKAPI (076/DIY/2012) Copyright © 2015 by Deepublish Publisher All Right Reserved Dipindai dengan CamScanner ‘Kimia Fisika adalah bidang ilma dalam kimia yang mempelajari aspek fisika dari materi dan energi Serta mekanisme perubahannya. Pada umumnya pembahasan di dalam perguruan tinggi membagi kimia fisika menjodi bidang termodinamika, kinetika, dan kuantum. Termodinamika kimia ‘mempelajari materi dan energi yang menyertainya yang pada intinya mempelajari hukum-bukum ddasar termodinamika. Sementara itu kinetika merupakan bidang yang mempelajari aspek proses Perubahan suatu materi dalam sebuah reaksi atau interaksi lain. Di dalam kinetika juga dipelajari ‘beberupa teknik penentuan mekanisme dalam suatu reaksi, Subjek dalam kajian Kinetika kimia, khususnya berkaitan dengan pengukuran dan penafsiran tingkat (orde) suatu reaksi kimia. Hal ini sangat berbeda dari termodinamika kimia yang berkaitan hanya dengan keadaan energi awal dari reuktan (sebelum reaksi dimulai) dan keaduan akhir sistem ketika heveimbungan tercapai. Apa yang ‘erjadi antara awal dan akhir negara reaksi dan tepat bagaimana, dan seberapa cepat, transisi dari satu ke lain terjadi adalah menjadi bagian dalam kajian kinetika kimia Pada tingkat molekuler, kinetika berusaha untuk menggambarkan perilaku dari molekul pads saat mereka berbenturan atau mengalami umbukan antar molekul schingga membentuk spesies baru, kemudian mengalami transformasi menjadi produk. ‘Termodinamika membahas mengenai arah spontanitas suatu reaksi kimia dan aspek energi yang berpengaruh di dalamnya, tetapi perubahan detail yang terjadi dalam suatu reaksi tidak dapat dijelaskan. Dengan kata lain, termodinamika tidak tergantung pada detail proses reaksi kimia, dalam hal kekompleksan yang terjadi dalam suatu reaksi, termodinamika hanya mengambil data pada bagian keadaan awal atau keadaan akhir reaksi, Padahal, reaksi yang secara tcori termodinamikit dapat berlangsung spontan dapat kita cegah upabila kita mengetabui bagaimana reaksi (mekanisme) berlangsung. Dalam tingkat yang lebih fundamental kimia kuantum menguraikan interaksi antar wom dan struktur atom serta molekul dalam kuitunnya dengan beberupa aspek aplikasi mutakhir seperti spektroskopi. Hukum termodinamika pertama adalah salah satu topik di dalam kimia fisika dan menjadi dasar bagi hukum-hukum selanjutnya. Hukum pertama juga kits kenal sebagai hukum kekekalan ‘energi. Energi tidak dapat diciptakan dan tidak dopat dimusnahkan. Konsep tersebut tentunya merupakan konsep yang dapat diterima dalam segala aspek Keilmwan dan aplikasi, termasuk di dalamnya untuk pengembangan keilmuan saat yang sedang marak saat ini yakni energi terbarukan. Suatu konversi energi terbarukan misalnya harus memenuhi kaidah hukum ini, Reberapa parameter lukuran perubuhan termodinamika seperti perubahan (ungsi Gibbs (4G), perubuhan energi internal (AU) serta entropi misalnya, menjadi penting sebagai rujukan perhitungan teoritis. Termodinamika akan menjawab apakah suatu proses dapat berlangsung, tidak dapat bertangsuag atau berada pada kkondisi kesetimbangan. Sementara itu selama proses atau reaksi berlangsung beberapa faktor yang mempengaruhi cepal stay lambutnya proses terseut merupakan aspek dari kinetika. Dulam hal ini kita akan menemui adanya reuksi yang berjalan sangat cepat misalnya reuksi oksidasi dalam bom dan reaksi sangat lambat misalnya proses korosi logam, Sebagai contoh peranan kinetika dalam proses evaluasi pangan. Kinetika dapat digunakan untuk mengendalikan dan memprediksi masa kadaluwarsa dari produk pangan berdasarkan kajian sifat reaksi dan Pengendalian laju reaksi apabila detail proses yang terjadi di dalamnya diketahui dengan baik. Dengan kata lain termodinamika memberitahukan kepada kita apa yang alam kehendaki, sedangkan kinctika kimia dapat memberitahukan kepada kita bagaimana membuat alam berlaku sebagaimana ‘apa yang kita kehendaki (Thermodinamic tell us what nanure wants to do, chemicals kinetics can Dipindai dengan CamScanner Prosiding Nasional Rekayasa Teknologi Industri dan Informasi XV Tahun 2020 (ReTII) Oktober 2020, pp. 007-012, ISSN: 1907-5995 oa 7 Koefisien Perpindahan Massa dan Karakteristik Gelatin Dengan Proses Leaching ABSTRAK Kolit dan tulang merupakan bahan yang banyak mengandung kolagen alami, salah satunya adalah tulang ikan tenggiri. Ikan tenggiri termasuk jenis ikan laut yang bertulang keras yang mengandung kolagen berkisar antara 15-17%, Pemisahan gelatin dalam tulang ikan tenggiri dilakukan dengan metode ckstraksi padat-cair (leaching). Gelatin dalam tulang ikan tenggiri sebelum di ekstraks mengalami proses demineralisasi yang bertujuan untuk mengurangi kandungan garam-garam mineral yang terdapat dalam tulang ikan tenggiri. Proses ‘demineralisasi pada penelitian ini menggunakan ckstrak belimbing wuluh. Belimbing wuluh mengandung. sam sitrat sebesar 92,6-133,8 per 100 gram total padatan . Lalu dianalisis koefisien perpindahan massa yang, berlangsung pada proses ekstraksi padat —cair (leaching) untuk mengambil gelatin dalam tulang ikan tenggiri Sebelum penelitian dimulai, maka dilakukan analisa kadar asam sitrat yang terkandung dalam ekstrak belimbing wuluh sebagai bahan perendam dan diperoleh konsentrasinya 1,7 M dan pH 2. Proses penelitian dilakukan pada temperatur 500C, 600C, 700C, 800C, 900C, dan massa 50-gr, 100gr, 150 gr, 200 gr dan 250 gr selama wakru ekstraksi 1, 2, 3 jam, sebagai pelarut digunakan aquades. Gelatin yang diperoleh dianalisa karakteristiknya yaitu kadar protein, kadar air, kadar abu, viscositas, kekuatan gel dan kandungan logam, kemudian dilakukan analisis terhadap koefisien perpindahan massa pada proses ekstraksi nya. Hasil analisa penelitian diperoleh kateristk sifat fisik dan kimia gelatin yaitu kadar abu 3,73%, kadar air 8,83%, kadar protein 76,38%, kekuatan gel 60,5365 bloom, viscositas 30,8368 cps, kadar seng (Zn) 98,23 mg/kg, kadar ‘Tembaga (Cu) 27,37 mg/kg. Sedangkan nilai koefisien perpindahan massa yang diperoleh sebesar 7,843 (jam), Kata Kunci ;Gelatin, Koefisien Perpindahan Massa, Leaching ABSTRACT ‘Skin and bones are ingredients that contain lots of natural collagen, one of which is mackerel fish bones. ‘Mackerel is a type of sea fish with hard bones containing collagen ranging from 15-17%. Separation of the ‘gelatin in mackerel fish bones was carried out by the solid-liquid extraction method (leaching). Before ‘extraction, gelatin in mackerel fish bones undergoes a demineralization process which aims 10 reduce the ‘content of mineral salts contained in mackerel fish bones. The demineralization process in this study used starfruit extract. Starfruit contains citric acid of 92.6-133.8 per 100 grams of total solid. Then analyzed the ‘mass transfer coefficient that takes place in the solid - liquid extraction process (leaching) to extract gelatin in ‘mackerel fish bones. Before the research began, an analysis of the levels of citric acid contained in the starfruit ‘extract as a soaking material was obtained and the concentration was 1.7 M and a pH of 2. The research process was carried out at temperatures of S00C, 600C, 700C, 800C, 900C, and a mass of 50 gr. 100gr, 150 ‘87, 200 gr and 250 gr during the extraction time of 1. 2, 3 hours. aquades were used as a solvent. The ‘characteristics of the gelatin obtained were analyzed, namely protein content, moisture content, ash content, viscosity, gel strength and metal content, then an analysis of the mass transfer coefficient in the extraction process was carried out. The results of the research analysis showed that the physical and chemical ‘characteristics of gelatin were ash content 3.73%, water content 8.83%, protein content 76.38%. gel strength {60.5365 bloom, viscosity 30.8368 cps, zinc content (Zn). 98.23 mg / kg, levels of copper (Cu) 27.37 mg / kg. While the mass transfer coefficient value obtained is 7.843 (1 / hour). Keywords: Gelatin, Mass Transfer Coefficient, Leaching 1. PENDAHULUAN Gelatin adalah produk berprotein tinggi yang banyak digunakan baik dalam industri makanan maupun farmasi. Dalam industri makanan antara lain sebagai agen pembentuk gel, pengental, pengemulsi, pembentuk busa, sedangkan dalam industri farmasi digunakan sebagai bahan pembuat kapsul{1}. Kulit dan tulang ‘merupakan bahan yang banyak mengandung kolagen alami(2). Diantaranya adalah tulang ikan tenggiri, kan tenggiri termasuk jenis ikan laut yang bertulang keras,tulang keras ikan tenggir tersebut mengandung kolagen Prosiding homepage: htips://journal.itny.ac.id/index.php/ReTI/ Dipindai dengan CamScanner wo oO ISSN: 1907-5995 pH 6 Dari tabel 2, dapat dilihatnilai kekuatan gel dari gelatin yang dibasitkan dari hasil penclitian yaitu sebesar 61,0468 bloom, nilai ini masuk dalam nila standar British Standard : 757 Tahun 1975 yaitu ($0 ~ 300) bloom. Kekuatan ge! menunjukkan kemampuan dari gelatin untuk mengubah fase gel menjadi fase sol dan sebaliknya Sedangkan nilai viskositas dari hasil penelitian yaitu sebesar 29,8208 cps, nila ini jauh melampani nilai batas yang dipersyaratankan British Standard:757 Tahun 1975 yaitu (1,5 - 7) eps. Hal ini disebabkan arena asam dalam belimbing wuluh yang digunakanpada proses démineralisasi berkonsentrasi lemah dan ‘waktu perendaman juga singkat, Proses pencucian yang sempurna setelah perendaman dengan asam akan imenghasilkan nilai pH yang netral, sehingga kandungan asam dalam ossein menjadi berkurang. Nilai pH berpengaruh terhadap produk gelatin yang dihasilkan, Gelatin yang memiliki pH netral akan bersifat stabil 003}, 3.2. Analisis 32.1 Pengaruh Suhu Terhadap Koefisien Perpindahan Massa Koefisien perpindahan massa merupakan konstanta laju difusi yang berkaitan dengan laju perpindshan massa.Laju perpindahan massa berbanding lurus dengan driving force dan berbanding terbalik dengan tahanan, Hubungan koefisien perpindahan massa terhadap subu pada berbagai waktu dapat dilthat pada Gambar 1. beRT EGGS Gambar 1 Hubungan Kia Terhadap Suh pada Berbagai Waktu Dari Gambar | dapat dilihat bahwa nilai koefiien perpindahan massa yang paling besar terdapat pada suhu yang 500C dan waktu | jam yaita 7,843(/jam), Pada sub SO0C proses difusi gelatin menuju permukaan padatan sudah mencapai kondisi yang maksimum schingga peluang terjadinya proses perpindahan massa dari gelatin ke pelarut menjadi besar, Menurat Montero {12} pemanasan yang dilakukan untuk melarutkan gelatin sekurang-kurangnya pada subu 490C atau biasanya pada suhu (60 ~ 70)0C. Menurut Wiyono [13] pada proses demineralisasipenggunaan asam lebih disukai dari pada basa, karena prendaman dalam larutan_asam ‘memerlukan waktu lebih singkat. 32.2 Pengaruh Subu Terhadap Koefisien Perpindahan Massa Nilai koefisien perpindahan massa menunjukkan kecepatan difusi suatu zat yang dapat terlarut ke dalam pelarut. Hubungan koefisien perpindahan massa terhadap massa ossein pada berbagai waktu dapat dilihat pada Gambar 2 berikut ini: ReTil Oktober 2020; 007012 Dipindai dengan CamScanner ‘Am J Physiol Heart Cre Physiol 29S: W1234-H1242, 2008, First published July 25, 2008; doi 10.1152/ajphear 00429 2008, Cardiac magnetic resonance imaging of myocardial contrast uptake and blood flow in patients affected with idiopathic or familial dilated cardiomyopathy Michael Jerosch-Herold,'? David C. Sheridan,? Jessica D. Kushner," Deirdre Nauman,' Donna Burgess,! Diana Dutton,' Rami Alharethi,' Duanxiang Li,? and Ray E. Hershberger? ' Division of Cardiology. Department of Medicine, and Advanced Imaging Research Center, Oregon Health and Science University, Pordand. Oregon: and *Cardiovascular Division, Department of Medicine. University of Miami Miller Schoo of Medicine, Miami, Florida ‘Submited 24 April 2008; accepted in final form 17 July 2008 Jerosch-Herold M, Sheridan DC, Kushner JD, Nauman D, Burgess D, Dutton D, Atharethi R, Li, Hershberger RE. Cardiac magnetic resonance imaging of myocardial contrast uptake and blood flow inpatients affected with wiopathic oF fama dilated candiony- ‘pathy. Am J Physiol Heart Cie Physiol 295: H1234-H1242, 2008 Firat published July 25, 2008; doi0.11S2/ajphear.00429 2008. — iiopathc diated caniomyopathy (IDC) is characterized by left ven ticular (LY) enlargement with systolic dysfunction, other causes ‘excluded. When inherited, it represents familial dilated cardhomyop- athy (FDC). We hypothesized that IDC or FDC would show with ‘ardiac magnetic resonance (CMR) increased myocardial accumla- tion of gadolinium contrast al scady sate and decreased baseline myocardial blood flow (MBF) due to structural alterations of the ‘extracellular matrix compared with normal myocardium CMR was performed in nine persons affected with IDC/FDC. Healthy controls ‘ame from the general population (n = 6) or were unaffected family members of FDC patients (n = 3) without signs or symptoms of IDCIFDC or any structural cardiac abaormaliies. The myocardial partion coeiciet for gadolinium contrast (how) was determined by ‘TI measurements LV shape and function and MBF were assessed by standard CMR methods. Nos was elevated in IDC/FDC patients vs ‘ealthy controls (hs = 0.56 + 15 vs. O41 * 0.06: P = 0.002), and somrelated with LY (F = 061 for Aas vs. endediastobic ‘volume indexed by height: P < 0.01) and with ejection fraction (r = =0.80; P < 0.001). The extracellular volume fraction was higher in IDC patients than in heathy controls (0.31 = 005 vs. 0.24 = 003; P = 0.002). Resting MBF was lower in IDC patents (0.64 = 0.13 vs 091 = 0.22; P = 0.01) than unaffected controls and correlated with ‘both the partition coefficient (r = 057: P = 0012) and the ‘extracellular volume fraction (r = ~0 56; P = 0.019). The expansion fof the extracellular space corelated with reduced MBF and ventnc- ‘lar dilation. Expansion of the extracellular matrix may be a key ‘contributor to contractile dysfunction in IDC patients. idiopathic dilated cardiomyopathy: partition coefficient; myocardial blood flow ImioPATWC DILATED CARDIOMVORATHY (IDC) is characterized by left ventricular enlargement (LVE) and impaired contractility ‘of unknown cause, In many cases, the disease is inherited and termed familial dilated cardiomyopathy (FDC; Ref. 4) and accounts for approximately 20 to 50% of IDC cases (2), with ‘an autosomal dominant mode of inheritance predominating (4). ‘Screening. in particular in first degree relatives of FDC-posi- tive patients, and early detection are important because FDC is ‘amenable to medical therapy (4, 6). The diagnosis of IDC is based on the presence of reduced LV global function by fractional shortening or ejection fraction, ventricular enlarge- ‘ment, and clinical exclusion of other etiology. Pathological features of IDC include increased levels of interstitial and perivascular fibrosis(7) and decreased capillary density (17). The histological evidence from imaging and 21, 29, 38). Currently, myocardial biopsy is primarily recom- mended to identify patients with new onset disease resulting from myocarditis or other rare conditions and is seldom indi- ‘cated for those with an established diagnosis of IDC (5). Also, an endomyocardial biopsy is an invasive procedure and only yields information at the selected biopsy sites. For the devel- ‘opment of novel therapies that could benefit IDC patients, it ‘will be important to develop imaging based markers to monitor structural remodeling in the myocardium. For example, treat- ‘ment with an angiogenic factor in a hamster model of inherited dilated cardiomyopathy showed by histological analysis that an increase of capillary density was accompanied by a decrease of ‘myocardial fibrosis compared with placebo-treated controls (23). Cardiac magnetic resonance (CMR) imaging of myocardial ‘contrast enhancement after intravenous administration of a ¢gadolinium-based contrast agent has been useful for the detec- tion of myocardial infarction (18) and fibrosis (33, 41). We ‘contrast at steady state due to structural alterations of the ‘extracellular matrix compared with those without myocardial disease. As interstitial and perivascular fibrosis may be asso- ciated with a decrease of capillary density, we also hypothe- sized that expansion of the extracellular space would be asso- ‘ciated with a reduction of baseline myocardial blood flow (MBF). To test these hypotheses, we measured MBF during the first pass of an injected gadolinium contrast bolus. Once the ‘contrast attained an equilibrium distribution between blood and tissue, we measured the blood-tissue partition coefficient to ‘determine the distribution volume for the extracellular contrast agent (9, 20). METHODS ‘The study population comprised 18 participants (9 males and 9 females) that were recruited through the Oregon Health and Science University (OHSU) FDC research project (24) and the general pop- ‘Address for ropnat regucss and ther corespondence M Jeroxh Hero Beigham and Women’s Hospital, Radiology Box #22. 7 Prancis St, Boson, ‘MA 02115 (e-mail: mjrosch-Rero@ partners. or) nM (0363-613908 $8.00 Copyright © 2008 the American Physiological city “The cous of puiicatio of ths aucle were defrayed n part by the payment [page charges The aricle mant therefore he hereby marke “adhertemen!” in scoondance with 18 USC. Section 1734 solely to indicate this fat. ap tow siphon ore ‘Downloaded fram journals physiology ory/joumal/apbeart (182,001,200 185) on Apel 13, 22. Dipindai dengan CamScanner ‘MYOCARDIAL CONTRAST ENHANCEMENT IN DILATED CARDIOMYOPATHY ‘lation. FDC was diagnosed according 10 established citria as, previously published (6, 12, 32) and without the use of magnetic resonance imaging (MRI) findings. IDC was defined as LVE with systolic dysfunction (ejection fraction <00), with other causes of ‘ventricular dilation excluded. The sample included 9 participants who had been with IDC. Thee of the nine patients were ‘members ofa family affected by FDC hase onthe previous diagnosis ‘of IDC during clinical evaluation and thei famuly history. Three further patients from a different family diagnosed with FDC were siblings. The remaining patients represented sporadic cases of IDC. Study panicipants classified as unaffected (n = 9) had no evidence of any canhovascular abaormalities and had venticular volume and function parameters within the normal anges. They were recruited as volunteers from the general population (a = 6) or were unaffected relatives of FDC patients (n = 3) without the pathogenetic mutation found in their relatives and with normal LY function and no signs of LV’ dilatation. The study protocol was approved by the Human Subjects Protection Commitice of OHSU. All study participants gave ‘written, informed consent for study participation. ‘MRI protocol. MRI was performed with a 3 Tesla Scanner (itera 3, Philips Medical Systems) using a dedicated phased-array cardiac col. A respiratory bellows was placed on the patient's shdomen. Cine MRI images were obtained in the short axis view for 10-12 slices from base o apex to assess LV volumes and function. An ECG-gated {radient echo toquence with steady-state fee "eas used foe Cine MRI to acquire images for 20 phases of the cardiac cycle daring breath holding [repetition time per phase encoding (TRVecho time (TEYfip angle = 3.9/2.0 m5”: slice thickness = 6 mm; 192 X 170, ‘matrix; field of view (FOV) = 380 X 320- to 380-mm; sensitivity encoding factor of 2), Tl measurements were performed with & ‘Look-Locker technique (27), which was based ona gradient-echo cine sequence with a temporal resolution of 40 ms, using a nonslice Selective inversion pulse applied after the detection of an R-wave, followed by a segmented gradient-echo acquisition for 15-30 phases of the inversion recovery (IR) (TR/TE/Mip angle = 3.4/1.7 mall?" slice thickness = 8 mm; 176 X 140 matrix; 40 ms per segment: FOV = 380 x 320- to 380-mm; SENSE factor of 2). ECG and respiratory gating were used forthe Look-Locker acquisitions witha respiratory gating delay of 2 or larger. 1 measurements were made im one slice atthe midventricular level before contrast administration, and for two or more time points after contrat administration with, ‘measurements spaced at least $-10 min apart and starting. no earlier than 45 min ater a bolus injection of contrast. “Myocardial perfusion imaging with the patient at rest was per- formed during the frst contrast administration with a low-dosage bolus of gadolinium 0.03 mmoVkg body wt) injected intravenously in the antecubital fossa at a rate of 2 mils, Perfusion images were quired for three slice levels during cach heartbeat witha single-shot radient echo pulse sequence with nonslice selective. saturation: ecovery magnetization preparation lip angle: 2.40198 msl 207: 160 x 140 matix: FOV ~380 mm and 80% rectangular FOV. factor). The frst postcontrast TI measurements were made about 4-8 ‘min after imaging the first pass of the contrast bolus based on model-based estimates of the time it would take to reach contrast, cequilibeium between blood and tissue after a contrast bolus injection. This was followed by injection of the remaining balance of contrast {for a total of 0.1 mmoVkg body wt in each participant. Further ‘one-to-four TI measurements were made after this last contrast injection. depending on the remaining time available “image analysis. Images of LY cines, TI measurements, and resting perfusion were analyzed with the MASS CMR software (Laboratory {for Clinical and Experimental Image Processing, Leiden University, The Netherlands). Global function parameters. were determined by segmenting all cine images along the endo- and epicardial border and, summing of the cavity and myocardial volumes in each slice. End> systole and end-diastole were identified by the minimum and maxi ‘um on the volume vs. cardiac phase curve, Images for T1 measue- 1235 ments and ‘measurements were manually segmented along ‘the endo- and epicardial borders. The gray-scale windowing was adjusted for each cardiac phase to achieve optimal conspicuity of the LLY borders. The anterior LV-RY junction was used as landmark, and ‘eight myocardial sectors were defined for each cardiac phase such that ‘they had equal circumferential extent on a center line between endo- ‘and epicardial borders, with the first sector starting at said landmark. For the TI measurements, the mean signal intensity (SI) in each ‘sector was plotted against the delay after the inversion pulse. The SL ‘data points were fit in MATLAB (The MathWorks, Natick, MA) with ‘a nonlinear least-squares algorithm, using the analytical expression for ‘the magnitude of a monoexponential IR, SI = lm0 ~ ml -exp(—delay/ ‘TI*)L where |. represents the magnitude operation and m0, m1. and ‘Ti* are adjustable’ model parameters. ‘of model fits 10 ‘experimental inversion-recovery data for one myocardial sector and a region in the center of the LV are shown in Fig. 1. TI values were ‘derived from the IR fit parameters, using previously validated meth- ‘ods (3, 37). The gadolinium contrast partition coefficient (ho) in ‘myocardium was calculated for each patient from the change of ‘relaxation rate (RI = 1/T1) in myocardium and blood after contrast injection (9). In this study, multiple T1 measurements were used to ‘calculate the partition coefficient from the slope ofthe linear regression Tine for the measured values of R1 = 1/T1 (myocardium) vs. RI (blood) ‘as shown in Fig. 2C. For quantification of MBF, SI curves were generated from the mean SI in each myocardial sector and plotted as a function of time. ‘The initial SI, before the appearance of the contrast in the LV, was subtracted from all SI values for a baseline correction of the curves. MBF in milliliters per minute per gram was determined from the ‘initial amplitude of the myocardial impulse response calculated by ‘customized software 10 perform a model-independent deconvolution for the SI curves with the arterial input function measured in the LV ‘center. This method was previously Validated in animal models using labeled microspheres (14, 15) and has been applied in patent studies G6, 39). To adjust for differences in cardiac workload, the resting MBF was divided by the participant's (hear-)rate-pressure product (RPP). The MBF normalized by the RPP is referred to here as ‘Model simulations. The myocantial partition coefficient foe gadolin- jum contrast (Ac) is defined as the ratio of concentration of contrast in tissue (C), divide by the contrast concentration in blood (Cy): ci sheers o ° where p represents the specific density of myocardial tissue (~ 1.05 sm/g). It is assumed that the concentration of contrast reaches an state where the concentration ia the extravascular extra: cellular space (C.) equals the plasma concentration (C,): C= CM = Hed = C, @ ‘and Ht represents the blood hematocrit. If V_ and Vp, denote the volume fractions of the extravascular extracellular and the plasma spaces, respectively, one can express the tissue concentration as the weighted average of the concentrations in these spaces. with weight factors corresponding to the respective volume fractions, V,, and V.: CAG + VG @ By combining the above equations and assuming an equilibrium state (ie, C. = Cy), one can derive at the following expression for the ‘Parition coefficient (11), expressed in terms of the volume fractions land the blood hematocrit (Het): uty, ee roe” (= Hed ‘Acrcial aspect of any measurement protocol for determination of ‘the partition coefficient is the time one has 10 allow after contrast “o AIP-Heart Cire Physiol VOL 298 SEPTESUER 308 www pheat ng ‘Downloaded from journals physiology rpjournal'iphea (182.001.200.188) on Apel 13, 2022. Dipindai dengan CamScanner ) ee ‘ Pp 2 ORL ISISESSSS Scanned by CamScanner Dipindai dengan CamScanner Peepustataan Nasional: Katalog Dalam Terbitan (KDT) KHOPKAR, SM Konscp Dasar KiminAnalitik/S.M. Khopkar; penerjemah; A. Saptorahardjo, Pendamping: Agus Nurhadi, ~ Cet. 1. ~ Jakarta : Penerbit Universitas Indonesia 1990. mm; 23 om. Basic Concepts of Analytical Chemistry, Indeks. jsek 979-456-066-9. <1, Kimia analitik 1. Judul. Ui, Saptorahardjo, A. 543 © Hak penerjemah dan penerbit dilindungi Undang-Undang Cetakan 2010 Pengarang: S.M. Khopkar . Pendamping: Agus Nurhadi Dicetak oleh: Penerbit Universitas Indonesia (UI-Press) Penerbit: Penerbit Universitas Indonesia (UI-Press) JI, Satemba 4, Jakarta 10430, Telp. 31935373, Fax. 31930172 website: www.penerbit-ui.com; ¢-mail: info@penerbit-ui.com Scanned by CamScanner Dipindai dengan CamScanner Dipindai dengan CamScanner 9. EkstraksI Pelarut Di antara berbagai jenis metode pemisahan, ekstraksi pelarut arg,’ discbut juga ckstraksi air merupakan metode pemisahan yang paling bay dan populer. Alasan utamanya adalah bahwa pemisahan ini dapy dilakukan baik dalam tingkat makro ataupun mikro, Sescorang tidy memerlukan alat yang khusus atau canggih kecuali corong pemisa, Prinsip metode ini didasarkan pada distribusi zat terlarut dengan pe, bandingan tertentu antara dua pelarut yang tidak saling bercampur, sepen, benzen, karbon tetraklorida atau kloroform. Batasannya adalah 2 terlarut dapat ditransfer pada jumlah yang berbeda dalam kedua fas pelarut. Teknik ini dapat digunakan untuk kegunaan preparatif, pemumia: memperkaya, pemisahan scrta analisis pada semua skala kerja. Mule raula metode ini dikenal dalam kimia analisis, kemudian berkembany' menjadi metode yang baik, sederhana, cepat dan dapat digunakan unt, ion-ion logam yang bertindak sebagai ‘racer (pengotor) dan ion-ion logan dalam jumiah makrogram. 9.1 Prinsip Dasar dari Ekstraksi Pelarut Hukum fase Gibb’s menyatakan bahwa: P+V=C+2di mana P = fase, C= komponen V = derajat kebcbas Pada ekstraksi pelarut, kita mempunyai P = 2. yaitu fase air dan organ C=1, yaitu vat terlarut di dalam pelarut dan fase air pada tempera! dan tckanan tetap, sehingga V’= |. Jadi kita akan dapatkan:” 2+1=1+2, yaituP + V=C+2 | istribusi Nernst: | Menurut Hukum distribusi data fase | dan 1X adsl! Jika [X,] adalah konsentrasi zat terlarut l konsentrasi zat terlarut dalam fase 2, maka pada kesetimbang®| «| X,,% didapat: K, = (X31 | Ss 1X,] | Scanned by CamScanner Dipindai dengan CamScanner Dipindai dengan CamScanner Ekstraksi Pelarut 91 dj mana, K,, = koefisien partisi, Partigi . - tergantung pada konsentrasi Ghat tan i atau koefisien distribusi ini tidak : . " n distribusi (D) dengan memper- nitungkan konsentrasi total zat di lam kedi i gistrbusi dinyatakan sebagai berieut, "Kea fase. Perbanding ie Korisentrasi total zat pada fase organik Konsentrasi total zat Pada fase air Jika tidak terjadi asosiasi, disosiasi atau polimerisasi - polimerisasi fase-fase tersebut dan keadaan yang kita punyai adalah ideal, me harga K,, sama dengan D. Untuk tujuan praktis sebagai ganti harga K,, atau D, lebih sering digunakan istilah persen ekstraksi (E). Ini berhubungan dengan perbandingan distribusi dalam Persamaan sebagai berikut: v, wi Dud 2 di mana V, = volume fase air (100 - E) Vi= volume fase organik Bila volume fase organik dan air sama, yaitu V,= V,, D diubah menjadi: o-| al Ekstraksi dianggap kuantitatif bila: E = 100 berarti 100 100 : ; D=| ——— |= — == tidak terhingga (jika V) = Vy.) [ae | 0 B82 Gi o™ wl 9.2 Klasifikasi Ekstraksi Beberapa cara dapat mengklasifikasikan sistem ekstraksi. Cara klasik adalah mengklasifikasi berdasarkan sifat zat yang diekstraksi, sebagai khelat atau sistem ion berasosiasi. Akan tetapi klasifikasi sekarang didasarkan pada hal yang lebih ilmiah, yaitu proses ekstraksi. Bila ekstraksi ion logam berlangsung, maka proses ekstraksi berlangsung dengan mekanisme tertentu. Berarti jika ekstraksi berlangsung melalui / pembentukan khelat atau struktur cincin, ekstraksi dapat diklasifikasikan Dipindai dengan CamScanner ISSN 0854-5561 Hasil-Hasil Penelitian EBN Tahun 2018 PEMISAHAN DAN ANALISIS Nd, Ce DALAM LARUTAN PEB UsSiz-Al PRA IRADIASI MENGGUNAKAN METODE KROMATOGRAFI PERTUKARAN KATION Rosika Kriswarini, Erlina Noerpitasari, Noviarty, Sutri Indaryati Pusat Teknologi bahan Bakar Nuklir Pemisahan Nd Ce dalam larutan bahan bakar dilakukan karena Nd digunakan sebagai indikator bu up. Isotop Nd dan Ce merupakan produk fisi bahan bakar nuklir setelah mengalamai radiasi di reaktor. Kedua isotop tersebut mempunyai sifat fisik dan kimia yang mirip sehingga perlu dilakukan pemisahan untuk memperoleh isotop Nd yang mumi.Sebelum dilakukan pemisahan maka ditentukan faktor pisah (a) antara Nd dan Ce menggunakan larutan standar spex. Standar Nd dan Ce dengan konsentrasi 10000 ppm.setelah diencerkan menjadi 500 ppm masing-masing dilarutkan dalam media HNOs dan campuran HNOs dan methanol dengan perbandingan 1 : 9. Selanjutnya dilakukan proses pertukaran kation menggunakan resin dowex 5OW-X8 secara batch. Setelah dilakukan ‘dan pemisahan, tase cait dianalisis kandungan Nd dan Ce menggunakan UV-Vis dan XRF. ‘Berdasarkan perhitungan nilai koefisien distribusi (KD) No dan Ce, diperoleh nilai ‘a dalam media HNO dan metanol lebih besar dibanding media HNOs tanpa metanol. Nilai faktor pisah _menggunakan media HNO: maksimal sebesar 1,63, sedangkan menggunakan media ‘campuran HNOs-metanol (1:9) maksimal sebesar 12,28. Kata kuncl : pemisahan, anaiisis, Nd, Ce, PEB UsSiz, pra irradiasi, kromatografi. PENDAHULUAN Isotop Nd dan Ce merupakan bagian dari produk fisi bahan bakar nuklir UsSio-Al setelah mengalami proses iradiasi di reaktor. Proses reaksi fisi bahan bakar nuklir berbasis ‘uranium menghasilkan produk fisi ditunjukkan pada Gambar 1. Dipindai dengan CamScanner Hasil-Hasil Penelitian EBN Tahun 2018 ISSN 0854-5561 Berdasarkan hasil evaluasi pengujian Ce dan Nd menggunakan UV-Vis dan XRF maka dapat dinyatakan bahwa larutan campuran HNOs dengan variasi konsentrasi dari 0,25 sampai dengan 6 N belum mampu mengelusi Ce dan Nd yang terikat dalam resin. Hal ini disebabkan Ce dan Nd masih terikat kuat dalam resin. ‘Sebagai percobaan lanjutan maka akan dilakukan elusi menggunakan eluen dengan ‘campuran HNO; : MeOH (1 : 9) berdasarkan pustakal"!, ‘Tabel 3. Nilai Kd dan faktor pisah Nd, Ce menggunakan campuran (HNO; + MeOH) variasi konsentrasi (1:9) Keasaman HNOs (M) KdNd | KdCe| a 0,25 450 | 7718 | 1.50 | 05 1701 | 1576 | 0,93 1 203 267 | 1,31 2 30 36 17 | L 4 3 4 1,38 6 o a 1,83 Nilai faktor pisah (a) yang tercantum pada Tabel 1 kurang dari 10. Hal ini dapat dinyatakan bahwa pada kondisi keasaman HNO dari konsentrasi 0,25M sampai dengan 6M Ce dan Nd belum terpisah secara sempuma. Selanjutnya dicoba menggunakan eluent campuran HNOs dan MeOH dengan konsentrasi HNO: yang lebih pekat yaitu 2 M. Penentuan Kd pada Tabel 3 menggunakan UV-Vis. Untuk mengurangi proses preparasi sampel yang terlalu panjang, maka dicoba melakukan peenentuan Kd menggunakan teknis tetes menggunakan XRF": Hasil penentuan Kd Nd dan Ce menggunakan XRF tercantum dalam Tabel 4. 102 Dipindai dengan CamScanner ISSN 0854-5561 Hasil-Hasil Penelitian EBN Tahun 2018 Tabel 4. Nilai Kd dan faktor pisah Nd, Ce menggunakan campuran HNOs + MeOH (1:9) variasi konsentrasi Keasaman HNO;(M) | KdNd | Kd Ce a 0,25 729,37 | 8956,07 | 12,28 0,50 862,22 | 4147.69 481 1,00 389,36 | 915,45 2,35 2,00 86,14 94,76 1,10 4,00 19,19 13,36 0,70 6,00 860 458 0,53 Berdasarkan Tabel 3 dan 4 maka nilai faktor pisah antara Ce dan Nd pada keasaman HNO; 0,25 N memberikan perbedaan yang signifikan. Hal ini menunjukkan bahwa ‘campuran HNO dan MeOH dengan perbandingan 1:9 diasumsikan mampu memisahkan Ce dan Nd. Proses elusi Ce dan Nd untuk mendapatkan profil pemisahan Ce dan Nd dilakukan menggunakan eluen HNO; dan MeOH dengan perbandingan 1:9, tetapi hasil elusi belum ‘menujukkan profil yang diharapkan. Hal ini ditunjukkan pada Gambar 4. Aeretens Metter Sur ins os aan Gambar 4. Spektrum efluen dengan menambahkan standar pembanding La 103 Dipindai dengan CamScanner 1n Masyarokat LPPM UMJ -php/semneskat EASSN: 27146286 Website: Hip: /jumal.um.acid/ir TINJAUAN TERMODINAMIKA DAN KESETIMBANGAN KIMIA DALAM HUBUNGAN PERUBAHAN SUHU TERHADAP KONVERSI REAKSI EPOKSIDASI ASAM OLEAT BERBASIS SAWIT Maisarob", Wahyu Purwanto* "Pusat Teknologi Agroindustri, Kedeputian Teknologi Agroindustri dan Biotcknotogi, Badan Pengkajian dan Penerapan Teknologi (BPPT) Gedung 610 LAPTIAB, Kawasan PUSPIPTEK, Serpong, Tangerang Selatan 19314 *maisaroh@hppl.goid ABSTRAK, ‘Termodinamika adalah suatu tool yang sanget berguna dalam memabami kesetimbangan kimia yang terjadi secara alami, Energi Bebas Gibbs adalah salah satu dari parameter termodinamika yang menyatakan apakah kelangsungan suatt reaksi terjadi secara spontan alau tidak spontan, Komposi setimbang reaksi ditentukan oleh AG* dan K. Nilai G akan berubah seiring dengan perubatan komposisi kimia reaktan menjadi produk, Kesetimbangan reaksi atau pergeseran reaksi Kimia antara lain Gipengarvhi oleh suku reaksi. Epoksidesi asam oleat merspakan reaksi eksotermis reversible. Pada reaksi cksotermis reversible, bila suhu dinaikkan (Ts lebih besr dari Ty), maka nilai K akan menurun (Ke lebih kecil dari Kx) sehingga X2 lebih kecil dari X1, Penelitian ini bertujuan untuk mengetahui fubungan antara perubahan suhu terhadap Konversi reaksi ditinjau secara termodinamika dan fesetimbangan kimia. Metode penelitian ini menggunakan metode reaksi epoksidasi dalam suatu sistem Jatalis padat. Epoksidasi asam oleat dengan asam performat yang dibentuk secara in situ dalam suatu sistem reaksi katalis padat. Pengolahan data dilakukan berdasarkan hasil analisa bilangan iodin pada produk epoksi asam oleat. Konversi maksimum terjadi pada suhu reaksi 65°C. Berdasarkan tinjavan termodinamika dan kesetimbangan kimia, pengaruh suhu reaksi terhadap konversi epoksidasi asam oleat sesuai dengan persamaan Van't Hoff dan prinsip Le Chatelicr. Kata kunci: Termodinamika, Kesetimbangan kimia, Konversi reaksi, Epoksidasi ABSTRACT Thermodynamics is a useful tool in order to understand chemical equilibrium. Free energy Gibbs is one of thermodynamic parameters that indicates whether a chemical reaction occurs spontaneously oF not. The equilibrium composition of reaction is determined by G and K. The value of G changes in accordance with the change of the composition of reactants into products. The reaction equilibrium or chemical reaction shift is affected by temperature of the reaction. Epaxidation of oleic acid is a reversible exothermic reaction. In such a reaction if the temperature of the reaction is raised (T2>T1). the K value will decrease (K2 >). maka nilai K akan menurun (K2 < Ki) sehingga X2 < X), Pada reaksi eksotermis reversibel, semakin tinggi suhu konversi setimbang akan semakin kecil (Pri ‘Le Chatelier). Kecepatan reaksi epoksida: dinyatakan dengan konversi bilangan iodit (Campanella, 2005), Pada penelitian ini dilakukan proses epoksidasi asam oleat untuk melihat pengaruh suhu terhadap Konversi reaksi berdasarkan injavan termodinamika dan kesetimbangan Kimia, 2, METODE Bahan dan Alat ‘Asam oleat dengan kemumian 77% diperoleh dati PT. Cisadane Raya Chemical, asam format dari PT. Barco, larutan hydrogen peroksida 50 b/b% dari PT. Peroksidas Indonesia Pratama, sedangkan bahan kimia in Maxyarckat LPPM UMJ ASSN: 2714-6286 Jainnya yang digunakan untuk Analisa bilangan iodin diperoleh dari PT. Merck Indonesia Tbk. Poralatan utama yang digunakan dalam penelitian ini adalah reaktor volume 500 mL. Pemisahan produk menggunakan sentrifuse “Centurion Scientific, Benchtop Centrifuges Serial No. 213778-2, spektrofotometer FTIR Spectrum 1000, analisa bilangan iodin dan bilangan oksiran melalui metode titrasi ‘menggunakan Buret Eppendrof Top Buret H”. Proses Epoksidasi Asam Oleat Metode Epoksidasi yang digunakan pada penelitian ini adalah Metode Epoksidasi fn-Situ, menggunakan pereaksi asam format dan hidrogen peroksida. Mala-mula sejumlah asam leat dimasukkan ke dalam reaktor. Dilanjutkan dengan penambahan asam format dan katalis padat sambil dilakukan pengadukan, Kemudian sejumlah H:03 encer ditambabkan tetes demi totes, Waktu reaksi dihitung mulai sclesainya penambahan H:0; dan subu stabil mencapai subu yang ditetapken. Perbandingan mol reaktan dibust berdasarkan perbandingan mol asam oleat : asam format : bidrogen peroksida, Kemmudian terhadap produk epoksi dilakukan pencucian, dun pemisuhan produk. Reaksi epoksidasi dilakukan dengan variasi temperatut reaksi dan waktu reaksi untuk melihat pengaruhnya terhadap bilangan iodin dan bilangan oksiran epoksi asam oleat. Prosedur Analisa ‘Analisa —kualitatif’ —_-menggunakan spekirofotometer FTIR dilakukan untuk mengetahui struktur molekul dan ikatan yang terdapat pada asam oleat, produk epoksi asam oleat. Analisis struktur pada bahan yang berbentuk —cairan— menggunakan ala speltrofotometer FTIR Spectrum 1000. Daci hasil uji FTIR dilakukan pembacaan terhadap spektrum FTIR schingga akan diketahui keberadaan gugus molekul ikatan rangkap pada asam oleat, dan cincin oksiran pada epoksi asam leat Analisa bilangan iodin (iodine value/IV) menggunakan standar AOCS Official Method Ca ld -92. Pethitungan Bilangan Todin (IV g 1/100 g sampel): (0 V5) 12.69 400g 520 = WOT 81269 N09 5303 Bilangan lod ey @ Dipindai dengan CamScanner Indo. J. Chem, Se. 7(3)(2018) Indonesian Journal of Chemical Science Intp://journal.unnes.acid/sju/index.php/ies Validasi Metode Penetapan Kuantitatif Metanol dalam Urin Menggunakan Gas Chromatography-Flame Ionization Detector Elyta Mariana", Edy Cahyono’, Endah Fitriani Rahayu', dan Bowo Nurcahyo? ‘Jurusan Kimia, Fakultas Matematika dan lImu Pengetahuan Alam, Universitas Negeri Semarang Gedung D6 Kampus Sekaran Gunungpati Telp. (024)8508112 Semarang 50229 *Laboratorium Forensik POLRI Cabang Semarang, Kompleks AKPOL JI. Sultan Agung, Candi Baru, Telp (024) 8312742 Semarang 50232 Info Artikel ‘Abstrak “ela Takuan wi valiias waaay ia meio prepara aS meTROT dal Bi espana a8 ‘urin dengan distilasi, ekstraksi cair-cair dan ekstraksi fase padat menggunakan gis DenjeiOtutes2018 happy, Met Ges Chemung Fame entation Detector (GF dapat taklan Nowenier -6unakan Unik menentuan ladar” metnel alam urns ase uh ade Dae nstee November gtambahan andar ineral propanol. Uj wldtas yang yang dlatansoelipa ot linearis, ara, presi sera penenuan lini of deveton (LaD) an Bont of Ran ‘hanttton (LQ), Lear har andar dengan GCTID dipersiehscbear 09994 marl engin nila LoD sebesar 0,0743% dan nial LoO sear 0.24774. Uj. aka rdronsconply Gaakan dengan meaghitung persen meoery yaa 95.36% unk metodo, Sipe (62.40% untuk metode ekstraksi cair-cair dan 66,55% untuk metode ekstraksi fase adat. Hasil uji presisi dengan metode distlasi diperoleh %RSD sebesar 2,03%. Sedangkan "6RSD metode ekstraksi cair-cair 3,00% dan 6,77% dengan ekstraksi fase ‘padat. Berdasarkan hasil analiss uj validitas disimpulkan bahwa metode distilasi lebih balk daripada metode ekstraksi cair-cair dan ekstraksi fase padat. ‘using gas chromatography. The method of Gas Chromatography-Flame lonization Detector (GC-FID) can be used to determine the levels of methanol in urine. In the validation test an internal standard of n-propanol was added, Validity tests included Linearity test, accuracy and precision test, and determining the Emit of detection (LoD) ‘and limit of quantitation (LoQ). The linearity of the standard curve obtained by GC. FID is 0.9998 with LoD value of 0.0743% and LoO value of 0.2477% Accuracy test 's done by calculating the percent recovery, which is 95.56% for distillation method, 62.40% for the liquid liquid extraction method and 66.55% for the solid. phase extraction method. The result of precision test by distillation method acquired %4RSD of 2.03%, Meanwhile, %RSD by liquid Liquid extraction is 3.00% and 677% by sold Phase extraction. Based on the results of the validity test analysis concluded that distillation method is better than liquidsiquid extraction and solid phase extraction ‘method. (© 2018 Universitas Negeri Semarang GAD Karespondense Gedung D6 Lantai 2 Kampus Sekaran, Gunungpati, Semarang $0229 ISSN 2252-6951 Email elytamarianal3@ gmail com ‘eISSN 250048 Dipindai dengan CamScanner Elyta Mariana a al. / Indonesian Journal of Chemical Science 7 (3) (2018) Penyiapan larutan standar metanol dengan mengencerkan larutan induk metanol sehingga diperoleh lanutan metanol konsentrasi 0,1; 0,3; 0,5; 1; 1,5; 2; 2,5 dan 3,5%. Sampel urin yang digunakan sebagai sampel penelitian ditambahkan metancl 2%. Masing-masing larutan standar metanol dan sampel urin ditambahkan dengan n-propanol 2% sebagai internal standar. Sampel urin dipreparasi dengan distilasi, ekstraksicair-cair dan ekstraksi fase padat. Preparasi dengan distilasi didasarkan prosedur Sudhaker & Jain (2016) termodifikasi. 1 mL, sampel urin diletakkan dalam labu destilat dan diikuti penambahan 10 mL aquades. Campuran didistilasi dengan kondensor refluks dengan penjagaan suhu 97,5°C. Preparasi dengan ekstraksi cair-cair digunakan pelarut kloroform dan perbandingan volume sampel:pelarut yaitu 1:1. Sedangkan preparasi dengan ckstraksi fase padat didasarkan pada modifikasi prosedur Hernanz et al. 2008) dan Martinelli era, (2013). Sampel urin 1,5 mL dimasukkan ke ‘cartridge forisil yang telah dikondisikan dan dielusi dengan 1,3 mL kloroform. Hasil dari masing-masing preparasi diinjeisikan ke GC-FID sebanyak 1 pL. ‘Analisis dengan GC-FID dilakukan pada suhu injektor 250°C, subu detektor 300°C, dengan split rasio 1:50. Suhu awal kolom 50°C ditahan dua menit pada suhu tersebut, ditingkatkan secara bertahap sebesar 10°C/menit sampai suhu mencapai 200°C dan ditahan selama lima meni. Lajualir dari kolom yang terpilih adalah 0,8 mL./menit. Laju alirgas helium 1,2 ml./menit,laju alir drogen 35 mL/menit, aju alir nitrogen 30 mL/menit dan laju udara sebagai pengoksida 350 mL./menit (Suaniti eral, 2012). Parameter validasi yang diuji yaitu uji linearitas, LoD, loQ, akurasi dan presisi. Uji linearitas dilakukan dengan menginjeksikan larutan standar metanol yang telah dibuat sebanyak 1 pL. ke dalam injektor kromatografi gas. Data yang diperoleh berupa luas puncak dibuat persamaan regresilinier y=bx+a dan ditentukan koefisien determinasinya. 1? >0,997 maka metode tersebut memenuhi parameter linearitas (Handayani & Lestari, 2012). Nilai LoD dan loQ ditentukan dari persamaan regresilinier yang diperoleh. Uji akurasi dilakukan dengan metode perolehan kembali yaitu dengan menambahkan spike 1 (1,6 ml. 2%), spike 2 (1,7 mL 2%), dan spike 3 (1,8 mL 2%) ke dalam sampel urin sebelum dipreparasi. Dilakukan juga uji sampel tanpa’penambahan ‘larutan standar, Masing-masing metode preparasi dilakukan pengulangan sebanyak 3 kali ‘Uji presisidilakukan dengan metode repeatability atau keterulangan dalam kondisi yang sama, peneliti yang sama dan waktu yang singkat. Preparasi sampel diulang masing-masing sebanyak 3 kali. Data hasil izomatogram dihitung simpangan bakunya. Hasil dan Pembahasan Sampel urin yang digunakan diperolch dari sukarclawan yaitu mahasiswa lak-laki dengan umur 21 tahun, Menurut WHO tahun 2011, umur 15 tahun ke atas biasanya mengonsumsi alkohol dan puncak konsumsi alkohol terjadi pada kelompok dewasa berumur 21-60 tahun (Hamidah & Yulianti, 2017). Pengambilan sampel dilakukan pada pagi hari yaitu pada saat bangun tidur. Penggunaan urin pagi dikarenakan urin pagi cenderung lebih bersih, konsentrasinya lebih tinggi, dan jumlahnya lebih banyak. Untuk memisahkan pengotor/senyawa pengganggu dari analit diperlukan metode preparasi sebelum dianalisis dengan instrumen, Sampel urin dipreparasi dengan tiga metode preparasi yatu distlasi ekstraksi cair-cair, dan ekstraksi fase padat. Metode distlasi didasarkan pada perbedaan titik didih eairan pada tekanan tertentu, Tingkat penguapan (volatilitas) masing-masing komponen berbeda-beda pada suhu yang sama. Pada pemisahan metanol dalam urin, metanol akan menguap pada suhu 64,5°C, Dikarenakan paéa sampel urin

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