Diajukan untuk memenuhi salah satu tugas kelompok mata kuliah Kimia Anorganik I Jurusan Pendidikan Kimia Fakultas Tarbiyah dan Keguruan UIN Sunan Gunung Djati Bandung

Disusun Oleh: Leti Andriani (208 204 123) Leti Fitriyanti (208 204 124) Pipih Latipah (208 204 132) Rida Farida (208 204 133) Rismah Sholihah (208 204 134)

JURUSAN PENDIDIKAN KIMIA FAKULTAS TARBIYAH DAN KEGURUAN UIN SUNAN GUNUNG DJATI BANDUNG 2009Sulfur 1

KATA PENGANTARSegala puji bagi Allah yang telah memberikan nikmat kepada kita semua nikmat yang tiada bandingannya dan atas berkat nikmat rahmat dan hidayah-Nya, penyusun dapat menyelesaikan makalah ini. Shalawat serta salam semoga selalu tercurah limpahkan kepada Nabi Muhammad SAW, suri tauladan yang baik untuk kita semua. Makalah dengan judul Sulfur ini disusun untuk memenuhi salah satu tugas kelompok pada mata kuliah Kimia Anorganik I. Penyusun mengucapkan banyak terimakasih kepada dosen Kimia Anorganik I dan kepada semua pihak yang terlibat dalam penyusunan makalah ini. Besar harapan penyusun, adanya kritik dan saran yang sifatnya membangun dari berbagai pihak untuk menyempurnakan makalah ini. Mudahmudahan makalah ini dapat bermanfaat, khususnya bagi penyusun dan umumnya para pembaca.

Bandung, November 2009

Penyusun

ii

DAFTAR ISIi

KATA PENGANTAR......................................................................................i DAFTAR ISI ............................................................................................ii BAB I PENDAHULUAN.................................................................................1 BAB II PEMBAHASAN..................................................................................3 2.1 SUMBER SULFUR....................................................................................3 2.2 SIFAT-SIFAT SULFUR............................................................................3 2.2.1 Sifat-sifat Fisika.......................................................................................3 2.2.2 Sifat-sifat Kimia.......................................................................................6 2.3 SIKLUS SULFUR......................................................................................7 2.4 PEMBUATAN SULFUR DAN SENYAWANYA....................................9 2.4.1 Proses Frasch...........................................................................................9 2.4.2 Proses Kontak..........................................................................................10 2.5 SENYAWA-SENYAWA SULFUR...........................................................13 2.5.1 Hidrogen Biner........................................................................................13 2.5.2 Sulfida......................................................................................................14 2.5.3 Polisulfida Logam....................................................................................15 2.5.4 Oksida dan Asam Okso...........................................................................15 2.5.5 Asam Sulfat.............................................................................................18 2.5.6 Senyawa Tio............................................................................................21 2.6 KEGUNAAN DAN DAMPAK NEGATIF SULFUR SERTA SENYAWANYA..............................................................................................22 2.6.1 Kegunaan Sulfur......................................................................................22 2.6.2 Kegunaan Senyawa Sulfur.......................................................................26 2.6.3 Efek Negatif Senyawa Sulfur..................................................................28 BAB III PENUTUP..........................................................................................30 3.1 Simpulan.....................................................................................................30 DAFTAR PUSTAKA.......................................................................................32 Lampiran...........................................................................................................33

Sulfur 3

BAB I PENDAHULUAN Belerang atau sulfur sudah dikenal manusia sejak zaman purba dan hampir semua bahasa memiliki nama sendiri-sendiri untuk unsur ini. Sulfur berasal dari bahasa sanksekerta yaitu sulvere, dalam latin yaitu sulfur dan dalam bahasa arab yaitu sufra yang artinya warna kuning terang. Pada tahun 1770-an, Antoine Lavoisier menemukan Louisiana dan Texas. Belerang atau sulfur adalah unsur kimia dalam tabel periodik yang memiliki lambang S dan nomor atom 16. Termasuk kedalam periode ke-3 yang ditemukan di alam dalam bentuk unsur bebas. Belerang adalah unsur yang ditemukan dalam keadaan bebas dan sebagian dalam senyawa logam sulfida. Pada mulanya unsur ini disebut brimstone yang berarti batu yang mudah terbakar. Belerang juga terdapat dalam gas alam, minyak bumi, dan batu bara. (Syukri, 1999) Belerang ditemukan sebagai unsur bebas, maupun sebagai bijih sulfida, FeS2, PbS, ZnS, dan sebagai sulfat CaSO4.2H2O dan MgSO4.7H2O. Belerang sebagai unsur biasanya terdapat dalam lapisan kurang lebih 150 m di bawah batu karang, pasir atau tanah liat. Oleh karena itu belerang tidak dapat ditambang seperti pada pertambangan lainnya. Pada tahun 1904 Frasch berhasil mengembangkan cara untuk mengekstrak belerang yang dikenal dengan cara Frasch. Pada proses ini pipa logam berdiameter 15 cm yang terdapat 2 pipa konsentrik yang lebih kecil ditanam sampai menyentuh lapisan belerang. Uap air yang sangat panas dipompa dan dimasukkan melalui pipa luar, sehingga belerang meleleh. Kemudian dimasukkan udara bertekanan tinggi melalui pipa terkecil sehingga terbentuk busa belerang dan terpompa ke atas melalui pipa ketiga. Kemurnian belerang yang keluar mencapai 99,5%. Pada dewasa ini lima puluh persen belerang yang digunakan bahwa sulfur merupakan jenis unsur dan bukan suatu senyawa. Tahun 1867, sulfur ditemukan dalam bentuk endapan dibawah tanah di1

dalam industri diperoleh dengan proses Frasch. Selebihnya diperoleh dari gas alam dan minyak bumi. (Hiskia achmad, 2001)

Sulfur 5

BAB II PEMBAHASAN 2.1 SUMBER SULFUR Belerang adalah unsur keempat belas terbanyak dalam kerak bumi. Dalam bentuk unsur keempat belas, belerang terdapat dalam kawah gunung berapi dan endapan bawah tanah di daerah vulkanik. Sebagai senyawanya, belerang terdapat dalam berbagai mineral sulfat SO42- seperti gips (CaSO4.2H2O), garam epsom (MgSO4.7H2O), barit (BaSO4), celestit (SrSO4), dan sulfida2-, seperti Galena (PbS), pirit (FeS), seng blende (ZnS), tembaga pirite ((Cu, Fe)S2), cinnabar (HgS), stibnit (Sb2S3), serta dalam bentuk molekul-molekul pada beberapa bahan organik, mustard, telur, rambut, protein, dan bawang putih. Belerang juga dapat diperoleh dari minyak bumi dan batu bara. Belerang yang terkandung dalam minyak bumi dan batu bara menimbulkan masalah lingkungan, karena pembakaran bahan-bahan tersebut menghasilkan oksidaoksida belerang yang mencemari udara. Oleh karena itu, belerang tersebut dipisahkan terlebih dahulu dan proses ini menjadi salah satu sumber produksi belerang. (Ida farida, 2008) 2.2 SIFAT-SIFAT SULFUR 2.2.1 Sifat-sifat Fisika Belerang terdapat dalam dua bentuk alotrop (polimorf). Kedua alotrop ini adalah belerang rombik, berwarna kuning yang disebut belerang- (titik leleh 2 112,80C). Pada suhu 95,60C, belerang rombik berubah menjadi belerang monoklin yang disebut belerang- (119,250C). Unsur ini mendidih pada 444,60C. Satuan struktur kedua bentuk alotrop dalam keadaan cair, mengerut menjadi lingkar S8. Jika belerang cair dipanaskan, viskositasnya berubah karena perubahan struktur dalam molekul belerang. Pada suhu di atas titik leleh, terbentuk cairan berwarna3

kuning muda dan terdiri satuan S8. Jika suhu dinaikkan lagi, warna cairan menjadi gelap, dan pada kira-kira 1600C, berupa lingkar S8 putus menjadi rantai spiral panjang (belerang-) dengan beberapa satuan belerang S6 (belerang-). Antara 1600C dan 1800C,viskositas cairan mencapai maksimum dan dapat di tuang. Pada suhu di atas 2000C, cincin S8 terbuka sehingga membentuk rantai terbuka dan menjadi cair

Gambar Sifat belerang yang berubah ketika diberi panas

Terlihat bahwa atom S ujungnya mempunyai elektron tidak berpasangan dan dapat berikatan dengan ujung molekul lain, sehingga membentuk molekul S12, S24, dsb. Hal ini menyebabkan kekentalan cairan bertambah. Pada suhu yang tinggi, gerakan atom makin besar mengakibatkan rantai putus menjadi lebih pendek, sehingga kekentalan berkurang kembali. Unsur belerang berupa satuan S8, S6 ,S4, dan S2, komposisinya bergantung pada suhu. Jika cairan belerang (pada 250C 350C) dituang ke dalam air dingin, diperoleh belerang plastik, berupa serat yang terutama berbentuk . Jika dibiarkan, lama kelamaan akan berubah menjadi belerang rombik. (Achmad, 2001) Sifat-Sifat fisika belerang Sifat Fisika Spesifikasi dan nilai

Sulfur 7

4

Penampilan pada suhu kamar Rumus molekul biasa Titk leleh oC Titik didih oC Energi pengionan eV atom Energi pengionan kJ/mol Jari-jari kovalen Jari-jari ion (E2-), Struktur elektron Keelektronegatifan

Kuning, getas zat padat S8 115,2 444,6 10,4 1,000 1,02 1,82 1s2 2s2 2p6 3s2 3p4 2,5 (keenan, 1984)

Atom belerang membutuhkan dua elektron agar stabil dan dalam keadaan bebas adalah alotropi (mempunyai beberapa benruk kristal) dengan struktur dan sifat yang kompleks, dan belum sepenuhnya dipahami. Ada dua bentuk kristal yang umum, yaitu ortorombik dan monoklin bermolekul S8, yang berstruktur cincin. pada suhu 250C, belerang berbentuk ortorombik berwarna kuning, dan pada suhu 95,20C berubah menjadi monoklin.

Gambar struktur S8

(Syukri, 1999)

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Sulfur 9

5

00000000000000000000040000002d010000040000002d01000004000000020101 001c000000fb02f4ff0000000000009001000000000440002243616c69627269000 00000000000000000000000000000000000000000000000040000002d010100040 000002d010100040000002d010100050000000902000000020d000000320a0c000 00001000400000000000e01ca0020fb0700040000002d010000040000002d01000 0030000000000 Gambar Molekul siklik dari belerang padat (S )8

Dan

0100090000032a0200000200a20100000000a201000026060f003a03574d464301 0000000000010090ce000000000100000018030000000000001803000001000000 6c00000000000000000000001f000000420000000000000000000000f8200000b4 18000020454d460000010018030000120000000200000000000000000000000000 0000a00b0000240f0000d200000011010000000000000000000000000000503403 00682a0400160000000c000000180000000a000000100000000000000000000000 0900000010000000ab04000081030000250000000c0000000e000080250000000c 0000000e000080120000000c00000001000000520000007001000001000000c9fff fff000000000000000000000000900100000000000004400022430061006c006900 620072006900000000000000000000000000000000000000000000000000000000 00000000000000000000000000000000000000000000000000110078af11001000 0000dcb211005cb0110052516032dcb21100d4af11001000000044b11100c0b2110 024516032dcb21100d4af11002000000049642f31d4af1100dcb2110020000000fff fffff7ccf3d01d0642f31ffffffffffff0180ffff01800fff0180ffffffff0000030000080000 0008000078d1120001000000000000006801000025000000372e90010000020f05 02020204030204ef0200a07b20004000000000000000009f0000000000000043006 1006c0069006200720000000000000000009cb01100dee32e31e88d0832fcb31100 08b011009c382731040000000100000044b0110044b01100e8782531040000006c

b011007ccf3d016476000800000000250000000c00000001000000250000000c00 000001000000250000000c00000001000000180000000c00000000000002540000 005400000000000000000000001f000000420000000100000074cee1401263e140 0000000034000000010000004c000000040000000000000000000000ac04000080 03000050000000200020002000000046000000280000001c000000474449430200 0000ffffffffffffffffac0400008203000000000000460000001400000008000000474 4494303000000250000000c0000000e000080250000000c0000000e0000800e000 000140000000000000010000000140000000400000003010800050000000b02000 00000050000000c02ca000e01040000002e0118001c000000fb0204000200000000 00bc02000000000102022253797374656d00000000000000000000000000000000 00000000000000000000040000002d010000040000002d01000004000000020101 001c000000fb02f4ff0000000000009001000000000440002243616c69627269000 00000000000000000000000000000000000000000000000040000002d010100040 000002d010100040000002d010100050000000902000000020d000000320a0c000 00001000400000000000e01ca0020fb0700040000002d010000040000002d01000 0030000000000

2.2.2 Sifat-sifat Kimia Suatu sifat khas yang jelas pada belerang adalah atom belerang hanya memerlukan dua elektron lagi untuk mencapai konfigurasi s2p6 dari gas mulia. Oleh karena itu, belerang sering bereaksi sebagai zat pengoksida dengan mencapai keadaan oksida -2. Belerang dapat dioksidasikan oleh zat-zat pengoksida kuat, misalnya oksigen atau beberapa halogen. Bila teroksidasi, belerang cenderung ada dalam keadaan teroksidasi +2, +4, atau +6, contohnya adalah +2 (SCl2), +4 (SO2), dan +6 (SO3). Terhadap logam, belerang bertindak sebagai penerima 2 elektron, terhadap kebanyakan non logam, sebagai penyumbang (donor). Fakta bahwa belerang adalah zat pengoksid maupun zat pereduksi, menjelaskan mengapa ia bergabung dengan semua unsur kecuali emas, platina, dan gas mulia. Namun, belerang tidak sangat reaktif, selain jika dipanaskan di atas titik lelehnya. (Keenan, 1984)

Sulfur 11

6

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Sulfur 13

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Sulfur 15

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Sulfur 17

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Sulfur 19

00200000685c0400689c0400f40d68c48864cd27b82a21b64303a19bf41e346044b 038cb90e111e1674a52d6aa33311d9c4e03a9b6612467bac6adf9f9acbb8ce091b42 fb46e49895b21a134c5b1d2b7971c7eab7bb08db6f686083b7e138b00ea4da8803f3 5c9bbec843d13baf400b5a4d9c9e922ec151b9462531a626260a99c9863e0106304 9a313ed0ce472ca396db1d80cf45a81ac912d1a55421bcd244ad9ad44db8698768cd 626c36dc312dbb95521ae93a4ea53b7d200468ca26eb74ab4cfbb08fd56f7611b6de d0c1076fc271616ce19cbd245d82a372859ede759c692e2d968b965380e529bbdcaa 6959515b49bda04f14b1d714435b902c71d04609384c71e2b9b01b5175865a918d1 049c6c00e8c62e885cd8929c81b936bb6c9495b7ebd4a97384ce8c23f55bdd846db 7b43041dbf09c585b3e9099ce4459391f7275bf7d332b799112bb4a8bb25476f277a 908825b0aa826a22e075a9c6b069999938f0ea7345f63cc9a53030d2d0d120e332eb 5584199786b65ec95535d20f99659a0219331299f78c9f8a6b2a98aa83cc8b43da29 734064ad74e56ffba9073a2b59305c091ab4265b7d847ed50eb21d56f6ebb594d0fb dac6d9c52bf11b1a1932b884f75cfa6e50b7b19da75210a19375a4a315da2ec23f55b dd846db7b43041dbf09c585b3e978d5813b91461c88bafd483e2c69017db67226b6 1c4066e00c8a6b9eebb49477b7074b16d92bc2a6729ea28344a42cc4ca9eab1d25a2 4111509b6f5f1c43bf66941f0e748d698c732aa67a6f4e8915ae738faa2e55590e136 e6b4611faadeec236dbda1820edf84e2c2d9f484d33331616dfc8539a47df126465cc 9c08948ea52511bf9552f130816930c812c956c47922ee241825bdb464ccad64de71 0512987036a7d61932d7cb88936214c163984d8dd02c0a1e6e4516f25ea54b2adea 99f1a7c488e6b03ab6cf9419685beee5900e70dea43dc5368952c7365c89f4b1b98d cb3a2d283b7b871329e5c0e999b0a68c974a99f1c84932aa4b44a63de4f7aa4fb4e9 724f0b60b742610788a6b3595692552d121847eab7bb08db6f686083b7e138b0b67 f00f6ed0c3bd36721649b7b8a0d2667d17ef0a17bfe7e84ba569d28b0a25e2548bf1 47eab7bb08db6f686083b7e138b0b67f01fbfe7826f706855432d3c611b736fc12d2 9b55ef32015e15e15e15e15e15e10a6dca0a182657fcd5e15e15e15e15e15e15e10ae ab7534953f98c1369984d04daebb107eab7bb08db6f686083b7e138ad314998d470 59e99b1391d821d3558f9e45e880d7da5c666fd17c8f2a358327b6444f4d37a66780 299716bd2985d566baa99d33125f79955993085c09e75c09e75c09e75c09e75c09e 75c09e75c09e75c09e75c09e75c09e75c09e75c09e75c09e75c09e74d2611b0eb400 f6da799c1668a77c0f9cf890c865621b6dfcda53a886d61ca999e7ea554586da6baa9

36fab250e604d8596d97694c348192eae5a4cc4b00fd56f7611b6ded0c1076fc27d1 4b12fc784fe50a13bf2e0939ed075138927098bff0421d2590bb49a23c3258735f8a3 f55bdd846db7b43041dbf09c5b2efc013ec19a2cf61d8213b5821413f907e15b05b7 0c9400b8628fd56f7611b6ded0c1076fc270c4f70f8a8ac959be36c5140d0fee1f807 b3da124e846ca87c4606bbd97268f6491f847443ea84fdd0fd1f338c1fbdbe9df1b95 4d9846db7b43041dbf09c2ee56fcd44da678946e518ae786971689c8694c67d9f38c b3e7dca0bab23ff002c836e8a9c8ef0d7b5e6e2e013aa6efe00a8e82026bdb7384c63 ef8dd75841c2e36a88cd2458a242d7941171d0a9e29a2d0c2657fe05bb9d9cae4c87 a74f2e2359a5c0954178a8e841c5d7cbe288df1b36df6a9b1c1c3890db6f686083b7 e1387f705fb87c9ca3f237bf1458ae570c16a366388a2f67c9506f8767bb06a655f02 8b75a261b5a26252405965c74b7d18b273324321d51d0b511610acc0e88ed170d69 dba22da1a67efc563e1b9a0b663282add13d60ed3a13088ac752d686903519f72338 9ed7c54474f3ccfe086db7b43041dbf09c236c268d76a8bb215514cbbd0234a30586 a70132742aa21e41a4a2225364af3fe4138e4556fadfe7dc9c4d355b7badedf721451 3e277f99f9261c8ab26795fe7ddcc86f74dc67233f11c72d75c6c2a97e6e69e4d7804 66decb0f2213ce66495406ce5c69ce0c9b1b799ab89e4f45212e437140b489ead083 aa139ccd98093600843859beaf9a6c365c31a4c9358738ced3c4aa842a853b413846 db7b43041dbf09c2cfd4ee299ef4e731b5173656e845d11d538e94d87c1b036475b9 54c683925bc42e45f11d538e95137a0f37669ff20a21944a64ed27ff00bee4e2d0fa3 2ae3676fb902f112998bcff0099f928465129c895a758fcfddcc99be878b1d2a8f27e6 3e837e60ca65fc8b7b71cb87f108b5d6837a93b833f10ac78a1dc53e645a1d263af12 4e33bfd2cc9900b78dce0967694dd6c475e718bde64020d6d8c177104d632c0dc23 6dbda1820edf84e0fe9c759f44d6ef4194baace9a6ad0b42d0b42d08ca9b75b01f9aa 722dff00adbe4a9c9f7b1a4f3c94b27dcc68ee41b9167fd6df25ea8e4601f25741e89f 3459103254cf24638890b32f6f921119a7e0a46c70cd2becdba7244ec2747a69c574 b50d255109b4c3ff006f565af37bb18bde640210a1034e86aa45ae39c7106db7b430 41dbf09c1fd40eafeabfa81d5fd57f503abfaaa7ed2d9df2a3ea811ba9b2371a3ea80fb 63266ec9faab3748eafeabfa81d5fd553f6d8755d2a7eaa677481fb3eaaddd23abfaac 9dd4d3c8cfaafea0757f55fd40eafea9e1f12ba8b4e6cae334f8c1c4d73b354ccf1cb1f 715275ad3fc820f86660af65e2e72deb7434ba1e8fa29c2783c580b279404e58f6ab6 2071d4db551b92191c7795be6ec792754d52c68681a0634a75bfd90a57f1680b5bc

Sulfur 21

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8349c09e2d5f8bdb4d493137a86e6d4b0141715853c4d4812a45493137a91266d43 1204c66ae64dab021e2d5a5841c6b74369ff0bcf7ff00f2294a0ae01c2c0d155282a7 3593e2cc70a8ef85b59c1be6a383e729320da800e5e95c19ddf0a62cb09266519c1ef 5168d810a9d27bd33757d97d1148f0066e195e0da9b5ced5fdca668431841a08784 49e956d48b74dc34e8235d29cb6c1902d6b03454ed865d97c5d98e1571d0320323e 62629522ae92df6a4722e091c2f82d82ac18297508cc44e6ad31df3243485e840624 27816458c559312eba83b7f7fc2f3dfff00ecaf3dff00fe03089463d0599c560161873 82f78338a41a40ed1f8a700c91210cf8de9dc499dc26635a8fe0e5187b0a6ad439466 cc2cff002a1129cba0b338a8e212c6268921281322b18725f34159c22a11168977a3 80be2f281bc19a255b33d837948df7a043ac0412c5aa63f1c79eff00f819913b914c4 740305743e3ae87c75d0f8eba1f1d743e3ae87c75b9fb8af4a10c069a7195161427e0 f67d29231a8b8cc0f3acd90c34044d33b200a0c82103664f5b50b0cc0b3ad2901267 801a7dd0c448543a250db83897bd737c4af199a429bac0d92ae5a902bab5a9f64838 8e8a07c1712d5bc088cda245fd2956dccb3caa031608bc6668362094636451e0513c 1d0510948c825c70a49a5860b48d4a0d64e4651156894bb92f47e479effde4e91a55 a54c006032f08ae3ee2ab02e1e01df1dad6b5a42944ac7d917b4fcd5ee0cb4b04608e b351ed0e18b0e5518de0b68d436f76852b7082e74a0a55943bf5a61e2b6f5b6a19a7 961747c53e7b61a502523c2f457dbabedd5f6eafb757dbabedd5f6eafb757dbabedd5 f6eafb757dbabedd5f6eafb757dbabedd5f6eafb757dbab52fc66ae63c41fb8a08a86d 1f5abcf19bafef79e7bff7990bb01d5055aa1f52387e641109b0d879f0eea222647f06 aef01d39a9d88564caa326d5f5db3510d90c2fd93665e347e347c78d3c2a7f233ae3b 3466a0b271dfbaf3dff00bac75a0f1362ad24acff00b7f3f87bf7fe7f117227162adf40 0465ecf52791ccd059113bc5b8246f7cb450292968aac8d5916a23d802b30dbd3eca 2fa4831711cf7a32ae897fbaac1c30b7ad056ac2a4fc5a36eed9d28c5b481d1d3ae3d d79effdd629fe03fb5a3b6af16fcff3f9b6f51df464b85580a4df2b5fd54789c107a73a 4252ea14cbb2d9a1e55a0c90f5b542711995e68c16a65b8d2b3e6804aed38d0b203 834808491d2a1248d826a457aead8a63941b0f9e0d0dfc2c95bccd28fe1b248fe13c2 27f5479f75e7bff7598fbe3d6841c08fcd319884d78589efdece23872aa7960dbd4d6 881f85a7e6ac8bc09009bd78c10dda9d8824372b2a5e8d586637a74769a699978b6 a0284986b1431604d71dc826afec3c69736ed2aae20b7dde268d4f1c19727e5c9e7b ff00f91860ee0fd1472eeccaeab6baa7660f04a0a08fdfc7b2d2196d53253d1e9e1da9

Sulfur 23

83002ddc6baded569a22b9676ec15f011e2b7797bf6cf1fd96f52212f974dbb1c8884 23ad4c90bd9bc3b9c2a16e0db8a0a4cb1318a1924a11c7e1c9e7bff007515b027de8 db819b2fb6b52002127cf89f28a05646f59bff5f93a0ed5d238f70d11c3c91e1e34fe7 c9fd5e344acb0077214ace1df46a06e79e6cf644e4444262619cef58e204b216b46cd ca176d7896d9f6acf121478f62c12d19ccc1c356b1a6e7777ee2266dc72547cec0378 b9c0a5b11da2907b6858855a26955f6c63f03279eff00dd7de3f7daa0414c31f93a0e d5d238d20c269a26b3f2e5e065592778150295acb1673ca994934dd1e768ee8ab27 094b5959364f3ec898da134004160ee4a17140d54ea366971dd6c369ab47c181560f 6a73445c1adafd71a9592aaf06242c479456aaeb4b97e0c9e7bff0075f78fdfe467950 271c79beea27636d94cce8db150381180cf5fda3246795406a61cce3421ea32beb41 56994c17597d34a839233f519df9625d5317535fed5a0231ae065bb8d2a455dd38c8 1eb1ef4a02c4cd23575cef7287380030d0acf3279545056ac06f9cce693f2ab6373dc d1f0470c2d80bd000515a19bb79cd2c9e3661190a4862275d9cb59bfa7725a0eeca8 bcdc784fcd6008418cdf0be7153a0716f0abb8e1e2fc193cf7feebef1fbfc8b92274ac3 8a4dc04e60cd0866aff005506f07fba26491606ae852e154e19ec35ad668638bbcaad 68b853662b8d911dcc54185e6ab3363c68a928361a4e20004fa55e4924cd1888d5e 8925e344861860921d3da86388b1e143e184369c561ce9769eb432498ed92416a81 a4d850a6b416ca57c4cdbdfda857c2cb1e6a77a004bf8bf83279effdd7de3f7f904313 82d70c18af1990f3374fa529985a9f95219318a7359e54f9a8417d1a8560b6447854 0b98ac72514acc611ba9ab4ac96f9f5ee4205195130dea6557db37658f7a4912dc16 29c70a1c552ec4621924efa94422db8df9fed62c0033b44b6996af25e60130cc478fa 52bc329b4c4065899ceb142ca931e387b756a9a26583c9c590b79d22cc8bb64c2e3 c1bed5300b80671131c15601660604d0f44ed52c446da4b4bdb8ada6335e024fad4 25a6fb5071060fc193cf7feebef1fbff0788df45fe76a7ba6ebf802a25d17675fc58ba2 cd747c7f845875b556aa987669018b1a17f164f3dffbafbc7eff00c07813fabfbd8754 18177a8e45d967ce8748277314209191c2544264850e1d3461725dd71afb2afb2afb 2afb2afb2afb2a2021622fa346a9182f157d957d957d957d957d957d957dd5638080 6e8b060de8c44c3b83e8f6649049f061a8a2240ded3f87279eff00dd468460b15a56 553473346494a05d8a11c3d90b5cbd406249efc88dbd37f9432498a762d25640871 3e3490a0d5bd88585f74e029bd98818c95ee4c947408499b02399a35c432d7f8435 7ef0808d0e15f54f9afaa7cd7d53e6bea9f35f54f9afaa7cd7d53e6bea9f35f54f9afaa7

cd7d53e6bea9f35f54f9afaa7cd12902b66fe359833c9a1f629ac48e1a098ded56590 7862dd3bf1a97ca6f059954971cca59f254d76d8741326fbe22905b316a125bda7bf 93cf7fee26e0bb576f52c44d4c629572cf64b25ab14c62dab86159655006ddebe7c5e 5ceb74923e259ec93c44c01a1924ed1032413b9fe2b800d99cce543532652638fe2c 9e7bff006ae2994b8d5a5586ca165286905a84c02f56f8d115f3404168ae17e18eb21 cbcea6a6e96e0dfe7b23fe347fb5be2c9e9fe577f0f99baf5b51870101f8b279eff00da b8e37bc4a8080d76367e2a0080940ff0048e17d54990a23a38f640b9f6de8adf4e7bc ffc98c593c6afacc81df275c7bc716990565b5eebcf7fed6de3fead2b5a4ded4563c4f 6eea8a48cdc156a68e458e314558a44cb13c20a18d3841c73437299b159c56173cd b3df684b238dbfbcd23323078543c4c9f1172a05683f43ca8b00a111bb90a8261c11 169e19ff000cda966037d0eb85069827c6cf719e3007c23e687138a77a2e716a3640 3e17a518414e80cd5fb844aed79eff00dabbcdff007d28637a456389d3cbba9444c6d 4b1084385038f43b11807c6828098dbbf116edfc5d157eaff00c1d9d63a8e557329a 49248339a3248825262d9fc73492881ab4ab4bc69b06b42ec289192a61a388febb3 821371a15ac901d7f9f8ee94e5811198d9e1454168e40b0922634cb34745b0b31dd 7a3f7520bcbc169823deb3a2086d00e5daf3dff00b576f7a21eb80fcd280dff007bf35 6f5e865f01418d092a64e64c21089def56539c174e052c2c84233afceb670458ceb1d 579d6d43a0382d0e9ad26e4989681aa0d04e49ea3907d45b7b3aede7df1da4e0e14b b592f163f47b203742f7fdd43575a34ac2b0a445f035a98004c8b66d4329c0996864 3f091d45c6780d18299c2c18b1e952c6072c5c7e8ec74c04aba5018c581fb540459c eeefde96160f4028cc7b08e1f0a2e6ddc79eff00dafb7506ef0a019804aca75a428689 7e8d8abcf000743574385497a906d23f0a6219cbf46c540e05d21bedcfa710d3b6b2 cf55e7487f0b9777074d680db21d286569b568751c99205e0fbb97e7f8232d08e3fe 2b45c45fc8a3221c075291c8d95f77c4abdb04750e2b4abb08725be619a4bcbeff00 9519812ab628ab83162ebe2ad53c95c0ef1b81cab405bfde9e34494283baf3dffb108 91346bce0cd64d8de9960b0d7069c1a7069c1a7068e01eae566ae61096edf8dd4ac0 6337f542542d0437df52558242119edc6e79d21bd823e2c5394142f1ca543086eefd e404491c8d4af49f91560f32355b558b5decbf14ce7186a3f159fcb108b47f454f60b 89b1c55788f0e5b778a1e72d10b4fc6e2d19d41bafc779e7bff6218111da11e4b4a9b 98de92e88e0b1a68bd91aca8050384ec081a149e14ced15689d89634408032b45fd 8337749f62769040a03b55e31cd24f34207f03be6fcea6a3b94e435e69b871afd41d7

Sulfur 25

0abd2cad7e9e14635e1b1c5cab8a03a8f13b0529bc6a8dfbe0ca00d5a94a42b969b3f 8152622e992f8b4331883bc23e32e3c5d28999da6c7bd5bb1a6bd8e1df79effdd405 ded46d763f47aa969ae280308835199ea0990a369eedbabd5be64cb32b331eb36c14 60e8cd60d044c63522a3918315e22bd27177d60480ae6270056196b0de46a25beba 7650d876f3b8b278fb7e36920d0656e5482c4b3d7d9a382df6bf96f4d1c721346867 712c7839ac337bf22f45a8204b7f26ad285c10d289d4222e4416376866c8e8b8d92d 3052ee85d284b66e7ba9cdb8744107471a9409cb3a5d6a4bc524a6150eae3987a15 c31a08eee63b66ef4a9d19df0f9f6ad1c36b3e79a74936dcfcb4a91f17cac0e4545894 4970cbd5c2815c589d0ded490b938f37baf3dfff00d4b3cb6091a61c5cd8f06a21dd1 69f3a341f22fbe2a2406ea69bc4f94ab7f3ec9e821786044f188a44886217d7e5eb51 c13134545fd8f6a943252819818f48a2e8328a91bdea78950dbf34ef1e5f9ad53f107 3ad75f1872a67bc1f856198f3be69cd23a28fa357203c655755f62ca8b7130bbe7d80 2104d9a5a40ec8ac562d8e1de79eff00fec7c0eb29995f41ad4c43c45cabcf6b0e2719 a3c3cf3178e31340c83c27084c32b8e5a7d880c9678166681c22432c88f1b7aa9590 2989b43af11a373256bd9c2a48952d4032f9ab0c3cdb9d62fcd9d7b2287e779eff00f ef57c029715ff0053cf7fec55420f16beebb15424f8d0ec0de7ff004de7bff638f7dca2 68d335d1ab4c52120aec685004888ac7e1ff0049e7bff639c3ca1caa02a98eba5425b 3044d29162f0395281b26f3e541006dff00148e0331430cfc0914be49180d822966e 263518a4df08c51c6198321137bac0d1847820c0212b636333017073e1673176332 ed97d70a6a3ab514d715c35776b26814b3290792870477e62624704de4220ddd24f 6e6251060cb84c55ce8689090683164de5dee2d5b98e6ef3371ade3da79efff00f4d4 ec2ca013e5de7860cc924431c2bac39d75873aeb0e75d61cebac39d75873aeb0e75d 61cebac39d75873aeb0e75d61cebac39d75873aeb0e75d61cebac39d75873aeb0e75 d61cebac39d75873aeb0e75d61cebac39d75873aeb0e75d61cebac39d75873aeb0e7 5d61cebac39d75873aeb0e75d61cebac39d75873aeb0e75d61cebac39d75873aeb0e 75d61cebac39d75873aeb0e75d61cebac39d75873aeb0e75d61cebac39d75873a06e 30cc053e0bd9ffda000c03010002000300000010e72cb2cb2cb2cb2cb2cb2cb2cb2c b2cb2cb2cb2ca7f29041041041041078c45a55370e29d4604104104157ca4104104 104104104104104138110620f043041055f290413971cf3fc4c3cb88c2090c118110 4008124157ca411a10410410410c10410410d8ff83810410632d5f2905520104104 104b041088055e86c82a0004106157ca41404201041041f410208d326ba411811f7

a01055f290430400410412749198011641426ad055a3c04157ca410c1041041011c 175c1042d04660c084caa81055f2904304104104105316c00a0c308a0c31c210904 157ca41503eb01490414518f30c10410410418f34c3055f291a7e420e30410500620 4104104104104724104357ca5580107854604107c5d60410410463431e20436b4f 295868f4f2e5010411d53008410410800c10416c357ca7f6fcd445efe81051a9c143 04104256b0415e1055f290538634e3041041050428020b15d290d3085de357ca410 410410410410410418b4082890883041041055f296442410410410410410410410 4104104104104157ca610530410410410410410410410410414e10d0495f3cff00ff 00ff00ff00ff00ff00ff00ff00ff00ff00ff00ff00ff00ff00ff00ff00ff00ff00ff00f87cffc4 00291100010204060202030101000000000000010011213161711020415191f0a1 b181c13040d1f1e1ffda0008010301013f101e2d887903a91a8a2b5d28ad74a2b5d2 8ad74a2b5d28ad74a2b5d28ad74a2b5d28ad74a2b5d28ad74a2b5d28ad74a2b5d28 ad74a2b5d28ad74a2b5d28ad74a2b5d28ad74a2b5d28ad74a2b5d28ad74a2676624 0b86df9001c0174371400eb819bab907077459aa281daa106cfe33d8fd2010100867 faff0061be8a240776b9eeec8a703167ef6a6084144d36d2fc4e48696d21cf7565080 170647442633db56767e7e689c364f19ec65000e982828286000c0c64f39b876632 627844218b4892f566f14f28406337b069af7608462796e6bb37f51098260a41d7fd d774031082d98ef7fd4593943af7aa6e5f446775decd57774b5249826c5e33d8c800 1d12d9c676dcaa264d941c1e33d8c80991ce3101d3360ef346c226826029d02a688 6caf19ec6501a5c8e805e510f2462966d3001d491281d110ca0e50191ae12c02d12c a39a041d7e90ddd1c0af19ec6404d8124e42980e9f6053744605fc6d111882f03e10 00cd3b2c00704004d48847844dd3ab4be3bb5812f803944ca7a7a0688cf83772930 9a90806bf1fcc0af19ec6404d986622d0ef6488f026d6d06223105e16c054b381610 000026060f002220574d4643010000000000010000000000000025000000002000 00683c0400689c04000c0583693f9f89b266a00171228cc24eee3896e24832743e00 35299ba66e99ba60d355110c867250c82e97c3b1449c6351dcdc91815e33d8c809b f00403ad47637277f7fe001326c42393714247a26c0af19ec6401223052cd35a7157 a683920091c6640b93d17fe1000c449391722bc67b1881a021876964e6923a01447 7448cf20c1a7e3391e33d8c411dc0a3347d623713724428842ee5a0826200da3fdc9 3082669b456d1bed00723ace9ff65e66726b013c821f16e2b24436280d512f800354 db978cf63107988c39171f48360999d1032c783541c140ee8371e4aa051233d6990

Sulfur 27

1522a274357ea764060661a46329beb376865282604484926268384022710895e3 3d8c407a238bcd0249de8553f057462a72068555162804b80df05006ad8b9dc6868 f926a888cac9991388089c3c67b1900189c8bf44f52b660594d4902893365249453 1c00328689b0f4404824d183ca71bb98eedc109caf19ec7e801d028354eec8994e9f 3f8cf63100169a8b8c94347f63c67b1901c814e7f4ea0ad56a020607851ec6021813 0aaaee55772abb955dcaaee55772abb955dcaaee55772abb955dcaaee55772abb955 dcaaee55772abb955dcaaee55772abb955dcaaee557728bf37387ffc4002911000102 0502060203010000000000000001001121314161f01051207191a1c1d181b13040 e1f1ffda0008010201013f10139d64e564e564e564e564e564e564e564e564e564e5 64e564e564e564e564e564e564e564e564e564e564e564e564e564e564e564e5088 47d9d2bca0fc4e9d3a74e9d13a1d3a078e7e95e507e83c1c2633a2a229a02359d002 817e09fa57941a990080993208c294acf310b13d1667a2ccf44f322067677f8a6fed1 2481a902d28df19267727509da166f2ad7abdab5eaf6acbafdab4ebf68968ebf699a3 afdab0eaf6acbabdab4ebf6ad7abda10a27b86f29fc037044693f4af283498c12c9abe d32eabe78e309cee373d68da4e48cc0651d0c1a2e601c7cfcec8f3179b84708e5314e 68449a88e454fd2bca0d02fa8e7a028c62a49e32e481dcea0e372504164bce3735b0 78a9ce5147416c3608099385990010181453004444113c939c8b9b392391311c06 490edf0a7e95e5069172be8516b1307e28799f6d1b039d94d78a2766dcf24c881239 2ad64d8e77e6855c427a14711686d86e1b0c875d0f8d2aab5ec3bf34740610e0816a b983d13410404417322297d3b1f853f4af2834ec4fd713374e19775f608898912cf9 40e162248d9a73b06d1c9022610984020010adca74ea0c3b17628fa79ed6d224882 892c8a08209dc90108c34ec7e14fd2bca0d3b13f5c4c1d07192eb4774781144ee02d 9350b768e9d0101c9d901081884fac59125ccd065e0d3b1f853f4af2834ec4fd7e00b f99e9fee8d1118e8420701926d89b62020e455012c8ff429b626d89b628143054d7b 1f853f4af283471ec77e0f1c9026ba84272023cf8462b42dd1399ca6427700de9988f 95947daca3ed651f6b28fb5947daca3ed0423eef69937d468e309b264032ec7e14fd2 bca04601d10240d2d4c4dc162c84fb128baff5d407507dff003f11040894290823ccc f5750ec2a7e95e50290a28396b12011cc8980d1700b3cff0093c7541bb10ce630221 3092327e112c1ca024b040ba1a0ecde8531925f52e0b15374af2814e460012804531 9d008964ca28840a1c1b505f34ce48f7e2ea3fa173971e4211c784870da521013340 14a149b9df39eb23e79265fee6c805001f679dd4fd2bca0404e1126b40618154dd5d

42b12e00c3a3e8f79228dc063f92dc6795bd5904bf898990e034e89b0408376c897a 4785aa099e6750d2a8b9f1ed0e81bbc773a4fd2bca0d084c99326e2183b1080e3932 479e7c842a036883cc67342b738112034e846c6aa224ea2640583779f7409724f723 c945876f31f4ea7c2b089cf8422c9bc65dfd280930d84bfa8102ee80653f4af283f31e 8a2d4e92415c4833b757dec99326501bbc54c87c9441c9f8a7e95e50696139fb13f4 af281351028003f4d9326442640c7a124485695a5695a5695a5695a5695a5695a56 95a5695a5695a5695a5695a5695a5695a56b4fffc4002b1001010002010302050403 0101000000000111002131415161718110203091a1b1c1f0f140d1e15060ffda000 8010100013f1071cd6820e19b38f3d72e69734b9a5cd2e69734b9a5cd2e69734b9a 5cd2e69734b9a5cd2e69734b9a5cd2e69734b9a5cd2e69734b9a5cd2e69734b9a5c d2e69734b9a5cd2e69734b9a5cd2e69734b9a5cd2e69734b9a5cd2e69734b9a5cd2 e697344050db1645726dc3c7ff001e808208dbae205c8a1dc5864b434b2ee77ce1cc a5253be79304a188144f4423ef92b6cc20dcea80a00e2258392177c648b02285db9a d740d3787b66a060162fa640dd7102e3263b9759d2da597730930f2a3ac1c88c204 5ed928dd74bd7b6240fbc00679c22c433cdd9a2fdbff1482007082bc1ba070c674ca c69fc862a1881d484cef77b21e68ce83c4eb857c125ab35203c7a71977e90cb141b8 06f571852eeb5246a700be58e664b702542f434df1d31560152c581051ae4dd32921 a6e2cb2918fb3c4c441c3418464db58f865e5f6bb9927208f1ac26544cb6e80f02028 796a221de224aea1e319eae8408546c48b70f4c4bfe5b4ab64e67a87a6438eab9bbef 2c369d41c044ee90225c3c885bd6625bcb0e98fa670b30d0a220c35f176d3d872a79 7162e10d0ad290ca7929260ce4b5a4066dbd99d35ff00d49040410272df87d1a6769 e79fb64334156bdc90858a3dfb38b42d3748a0476b8a363799870ad6e8044a88f24e 38de09001af540002fb190c49b92a565aed011e0ef8b9b6d522ec60e942ba6fb246ee 93d9a2769e79fb6121247a84a1befadf9c8168907e6a304513f396e736c20a54b127 a4e3082560d03bd260e86f0eed2c610760a069e1bf183f0c8218c2547692bc5c40cc 3ad9b3d97fc32083b1f20afddcb3b7c27dd3e7c71c71c71fd82c2d733ce104bd9d01f c13f822d14a483b53ca47d58166201550037bd1c32546434763ea7e8e1be9562165 0415141e7d318838148a334aa269f3db2190cf9545e6ebfdb086635308adb3a311a0 4415112947db08f050bbeb2f83afb1d7e6516754b7ff005e3ae6d434d21d246449ef bc52eaea2d953df49aef85ca2ee0682840e515e758115a1601aa88eb7c63d02472c0 089d8592cc5c7789aed9cf3b965e9801f535bffaf103ef4800854276b8455fa7aae8a0

Sulfur 29

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178d3bb9611d0b514b14e6597c7c011000aaf4cbde1db36dbebb6f60ed85270eb9e6 5795afc8942b2c45b43babaf74c26520c76c3d52deda3a9b838ef86d48bb8743a189 c8a949c8a22edfe706fe9868d0707fdf8ff0011dfea88200393b9014f47ea7f11df9fc2 f6c3e5a44247ef8c90b8da2801c5a5be71a0dd8009fbe1dd8d1094dbd45ed9b01e44 2928a968ee78f9411beeea39dc82c3008f5e0c2ec9c7c1a364a40cf0e0200100201f2 1e60d02ae41d578d7772b7d5c0176a3c2a7d8f3f2b10a01605b8af819b00f17657d7 be35f383cada751427b3b60c2570550b6d144372658a6991a93a72b3937f1fe23bff 8c20800adb60d562782f326d46081dd14ef256d11c496f5c57c92115b4e08803d70 862a30f7e40940a4601aedc64608091afad45f6c2db63008a7442a69eb8c6525058f 0a29e01e3b60000103a7cc06183161dcda25823474d68b53008aa060508215b5e4c d2e480689b6a863ee38c438ad76c25486960a88045c50b863b8af56486e52c6f0a01 b639408c3bb473753541b613d1aa57b05fdc640a5b2f2f56eb865a2579ca59b711b4 0461ddb664db77023b084bbf5c769616d241f73ecd3915f8a4b30a554e35e4a7fdc6 46329b35cc32a5fcb05c91d538877a9a0c1aa9d9ad35a759b5c46902cdda36ef8d3f 9f8ff0011dffc610400000bb079f6c75161c597154fba80af3df97179f0cbe566d6384 eba7fdf1eb41c93b03df1e822b7c42e916af83ab890b33a929c37907be0839133228 55f019d1c1f1db3f47e453921d311442c88dbdb3cd496262b71829eb89b3db005e8 c689a7db20d20a2ec3bb92379a236e08438508ae74bcd80d50251fdd3ae42252040 06a78c0fc34ccf33d7209cc35d21b3b3a60020a289d7e33652eed54d079d7e319b9f 453a07a6ca75cbe2bd074113883bf0c58394c03a0aff3ce5fdc414fa50bc73274f8ff0 011dffc610400249702010f1a4e1b11b06e1d0af58b4d19e03ba009d3102b7ab5225 6537b75d26200a8a38d63c109a9e8b0ee2053a6b2f12c91b56509d5e3be35b50e55 6d86dc75c75787b49a53637afdb0c2cc00161341c0743e496e99a00a2c632cf39306 430c80ba21d053a650d1e6a163606acd282ac15e54dc01011df2dd19f102f36f2feac 9029c5000773eaa01347108461f4230355be65e98272dd0eee8da9a010ef76a75188 4c479aa41413bb4e9b803a02762ab5edc0e3dcef9006a8b5c82843e8662df8b1844a 002000006a498e489c091776809d24f8dfc7af3bfed3f8b8beaeb40a1a76e1eb83035 743834bed951490102f9d5fce706973e3fc477ff002841000ba4e8f8ea7c49ba0e962 a8a7aaf7c732b2c9d9a85e8587f88c3109d9eada01cfb1934c9bda363f7c4c20d5b1a d3d74bf2ff0011dffca104003e5e5f8f85a0404cb0b0f61fb6574745c11c91ce255a01 f08efb691c366054513b98b195cbb420bed1f7c1802ab14a0f805abfef3fa3e7f47cfe

Sulfur 31

8f9fd1f3fa3e7f47cb74756a7833728e884f1b9fd1f3fa3e7f47cfe8f9fd1f3fa3e0c80e fa73768043802b02a00f386f91a1ee2013dcf80db9d126d393c89958c532d097a685 dfc9fc477fa420813a64ca85bd471429758428032b9d70075c4039e9db28801d5c16 82787140ab030e1761be71110762efe793914c9de59024a8a275c58fb6b59de1e47d f3601301024113040282b40e8a05477068097451df20279b074c3a8577b612749a9 53adb7c457b49c17be7b4281d41bc8bb3cdddbf5f56ad5ab56ad5ab56ad5ab56a5fb 49c202e0ed15959fb8465de1589199a5d9789f6c1d47dca2bd2ec3b99800d718b2c4 175dde3828b9a43f09892922f66fbe72f1cc922526e00208ed6a2b7bd71590bb04af 1675f87f11dfe88820545a7bf1885751657be28128705c12a91f18bd4f53f05cad2d0 c1508a79cde07a3272f785c425f5a9bc23553a9f9a21744fd9c2ead44ee1fa83f0071 1090778bc69fb600208944ebf10ad102c4a27647fc2872d548c1583414d3ebda1ddd d604526d49c32f7ee7c9fc477fa0208144f6317d4ba9835471dd5c2d10f53a629627 ae1e63d99a2ea9e2f1812531b6e21e1e3ae98a01d2735c0000e0fa10b51f3b5afc27d b366861d9a9f9f874cf51f41cd65a0af201fc8ff008b618b73813ec8c1a028dd0081f2 ff0011dfe8082010b2343bf25e37865090252a4e3bfdb1c4ac0816c07b5f7c4122530 00810c85b37f55fb05ef684b95353afb967dbe193a8abd811fce039151f79fc1ff121f df2b2ba1eec3df292b513ba5ec3f30d1f7a306dd2423bf1f4082060de4e7b3fe8389b 1a4de51fd8c3ddd937aa2fe3f1f2dcea8540a083cfa3869d5ea4163a1a0dbb34382d3 ab04017bdc04e2064bf90dcd7703a859a4bce1f8272c9ab404f12f9ca66b208c04fc3 f3ead070d6cebee3d8e16b345d5147ed9b2c10effbc060bdd88bd9fdcfb30a15850e7 6cfdf16bc37824b262824afe00da6889b0efdbfc166f21bd55fefb3ce20c3733aecfb3 8f40f91d0041c06ebf6e72d8e08b564f42e3dadb715f72a1bed8f78684b227c0f3db1 a87d28060c7d91f73e62080863b09e757f41c1d98b6770a7ea6719d157aa7e5239a2 aa37ac07c401d0c4289f03e13b4bc45980c61220d6be76a071fcb01fb3f939cce26dd 557f4a7b1f079deabb1fbdb7df02b802152928f1ed88840bdeed50dfa75c2d4c74680 9aef16b397935f4c163858141795034381abb6d2a014ac9b24777d7048f70aa46335 c23ae898e0a0a7fd07e10658da8af07f381701253934fb03c72f1f29a0560a78893f5 e11a8d44c21d7290116741179fa9d34c2b746499ce6af491bcba08303ab11700e89c 47cf57bfcc41010c7630efcbfa0e346d26bb43fcf8c3af144ef3f8bd71874a995760daf e9d665a79edcc4a6415506d83b9478b3aef59d8a03f82ea7e8754c6611845d365bf1 dbd9d595dcf534741bf427835cd01d82c012e89fb4dfd3a8ea0cd603ae87fe38cb99c

837eed9b9a5bc3bbd580d0450b134b23cbf77a3e6126da3aa2263ba9b468587d8fd4 304411a66fb38c36b74fb2fcb02c0451db0fc87e471eca102cf56e8f53b6439bcccb8 c9dc47aee386f887403d676ca2894b1e4fa2c83970ec487b8dee18e068898da4ad01 09efade84aeef04069be8017d7e0f0c8f401b55cacc77e89fb23d83bf3c15028df5979 5f9b51f72c57a1cc957c78b4ce6aeb66dbe135bfbf84828a4e1e4f9c820604bb6277d 9fb66ac777ec7fbcbc13f0206f524ba39ee738d3b4b4c3b1c780fd7065a174c018750 74e7abd329e97b42850da47a39ee739ae3f7467638f018aeb1c3fd17f67ecea75da75 10da35e8df26b9a4f23a0c0d681ef77f4eafb1e162e93fe38c78f9d0a6e99a9b49c3a9 d58f344499b4d1e9fc27cfb34890df77ddf85ed82561366f857b70fb77c0fe8f14844 ce8dde2d1d0fe1a4eb8e9bbc6421cb362363bde147b86e4a98a5af22ed9e15cccb12 2474f4040f4faa86b91c0755e99a3d45ab75f039fcbe184308f07f4bbbd5f43e6742ce 180ca700876577e66bf079c9f753ebe57caedf9c82080102559650476ba5e7adb7a6 2ced874f8f39fd03fef3fa07fde7f40ffbcfe81ff79fd03fef35201c0e5e34b9e996d6a0 bdeacd4e75126a4861e420ec0e763d3bd74c42c823a4f8df9605d675b3425ed05abc 86d7076fa0828cb76b825e3ddc5a35e864638bfab19b63f6fcc45810144ed88e04a2 a89fd2f48f3890e88ee872bc98e7732cf69f2ebf7e9847a2ea93c2f7f23d2de1d08046 8f09f568a83a8f43f77193904b63f337b1f61e72844d0fb7c0e8fe3f31eb7bfa23bbe0 c54a64397fb66fb064638e3f68f0e9ff007e8104130a215599fee59d9767af2222c55c 64a11bca25f1803c8a88bc23ab7a4cd7104615982750ba3bb83d30504478473fdcb2 bce1a2d2e7917c66fab9a355815eb50f7c1e9ca8001d573030d8700a00cd763d11eb 9fdcb3fdcb3af744e4f1ba1c1e35924bfa240a4ec80f9e4dd687a24e898b87846acd2 741f8e3870b213dd754744c0f24216cf075fd1d32e79ea6f93813ca4f19aed0b49eb9 b3e114b54f2e88ea53e738cd5481ef91c47c9fb9a3dd3142dd0e1fbcfd4beb9548ff0 0d1b3e85f530bd17001fedf3f33a80f1cc7d8fd5e309a836fee4edeaedfc61b2537ecfe 87eafa84104552acd012d905c74b82823210229af5069e218d3f382890de1a8beaf7 539d11009120413b4a0c0d2a796b1249f29c2365734dec84ecbd7141d74d61fba1b b440a6b78a9c68482fe65c8363682752e36f29104ead736f702b68fd475231a9de19 b8451447a03f72f65304bc34db75ae8f4df70ce381601ff00be72cb05753c3a7bdcf0 bba013bafeae2371a32ab0d8eec989004cbb0ee613a5ea8d3ca2a61eb954dd1a0110 300b3917c623d4d2b9a38bcb88c11ca9b51ba99a446273be3347821160cd35a00f6 c12752d0590e38f390c66e7ef27dd7081df071f8f94d41e59efd393f6c9a9cd45fddc1

Sulfur 33

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Sulfur 35

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Sulfur 37

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Sulfur 39

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Sulfur 41

bff6bff67ff6bff6bff6bff67ff6bff6bff6bff67ff6bff6bff6bff67ff6bff6bff6bff67ff6bff 6bff6bff67ff6bff6bff6bff67ff6bff6bff6bff67ff6bff6bff6bff67ff6bff6bff6bff67ff6bf f6bff6bff67ff6bff6bff6bff67ff6bff6bff6bff67ff6bff6bff6bff67ff6bff6bff6bff67ff6b ff6bff6bff67ff6bff6bff6bff67ff6bff6bff6bff67ff6bff6bff6bff67ff6bff6bff6bff67ff6 bff6bff6bff67ff6bff6bff6bff67ff6bff6bff6bff67ff6bff6bff6bff67ff6 Siklus belerang relatif kompleks dimana melibatkan berbagai macam gas, mineral-mineral yang sukar larut dan beberapa spesi lainnya dalam larutan, seperti: (1) mineral tanah, (2) gas belerang dalam atmosfer, dan (3) bahan organik. Pada dasarnya, siklus belerang terdiri dari 50% SO2 yang ada di atmosfer diseluruh dunia terjadi secara alami, misalnya dari letusan gunung berapi maupun kebakaran hutan secara alami, dan 50% lainnya berasal dari kegiatan manusia, misalnya akibat pembakaran bahan bakar fosil (BBF), peleburan logam dan pembangkit listrik. Waktu BBF di bakar, belerang tersebut beroksidasi menjadi belerang dioksida (SO2) dan lepas di udara. Oksida belerang itu selanjutnya berubah menjadi asam sulfat. (Otto Soemarwoto 1992) Belerang yang dihasilkan dari pemakaian batu bara sebagai bahan bakar pada beberapa kegiatan industri yang mengarahkan terbentuknya SO2. Polutan yang berasal dari asap industri yang reaksinya antara gas SOx dengan uap air yang terdapat di udara (atmosfer) akan membentuk asam sulfat maupun asam sulfit. Apabila asam sulfat dan asam sulfit turun ke bumi (tanah) bersama-sama dengan jatuhnya hujan, terjadilah apa yang dikenal dengan Acid Rain atau hujan asam. Hujan secara alami bersifat asam karena karbondioksida 8 2) di udara yang larut (CO dengan air hujan memiliki bentuk sebagai asam lemah. Jenis asam dalam hujan ini sangat bermanfaat karena membantu melarutkan mineral dalam tanah yang dibutuhkan oleh tumbuhan/tanaman dan binatang. Secara biologi, belerang berperan penting bagi pertumbuhan maupun metabolisme tanaman, asam amino sistin maupun sistein, dan metionin mengandung belerang dan penting untuk pembentukan, struktur, dan fungsi protein. (Anderson, 1975; Blair, et al., 1979) Belerang juga berperan dalam enzim tanaman, dan reaksi oksidasi-reduksi. Menurut Anderson (1975), protein sel memenuhi reaksi oksidasi-reduksi dan7

protein sel memenuhi dua fungsi utama bagi kehidupan, yakni: (a) enzim mengkatalis reaksi biosintetik dan katabolik yang diperlukan untuk pertumbuhan dan pengembangan sel-sel organisme, serta (b) protein struktural merupakan penyusunan berbagai membran. Setelah belerang merupakan unsur penyusun protein, tumbuhan mendapat sulfur dari dalam tanah dalam bentuk sulfat (SO4) kemudian tumbuhan tersebut dimakan hewan sehingga sulfur berpindah ke hewan, lalu hewan dan tumbuhan mati diuraikan dengan beberapa jenis bakteri, antara lain Desulfomaculum dan Desulfibro yang akan mereduksi sulfat menjadi sulfida dalam bentuk gas hidrogen sulfida (H2S) atau menjadi sulfat lagi, kemudian H2S digunakan bakteri fotoautotrof aerob seperti Chromatium dan melepaskan sulfur dan oksigen. Sulfur dioksida menjadi sulfat oleh bakteri kemolitotrof seperti Thiobacillus. Secara alami, belerang terkandung dalam tanah dalam bentuk mineral tanah. Belerang dari daratan cenderung terbawa air ke laut. Setelah itu hidrogen sulfida menuju ke atmosfer melalui penguapan laut. Didalam laut, tumbuhan laut yang memiliki sel-sel sederhana yang berusaha hidup dengan menahan masuknya garam (NaCl) ke dalam selnya. Ini dilakukan dengan membentuk senyawa penahan yang berbahan baku belerang, karena pasokan belerang di laut banyak sekali, datang dari daratan. Waktu sel mereka terurai, senyawa penahan ini pecah dan menghasilkan gas dimetil sulfida (DMS) yang lepas ke atmosfer. Setiap saat, sejumlah besar senyawa ini dilepas ke atmosfer, dan senyawa ini mampu menjadi inti kondensasi uap air. Pada gilirannya, terbentuk awan, yang menjadi hujan. Saat hujan jatuh di darat, senyawa belerang ini dikembalikan ke daratan untuk dimanfaatkan makhluk daratan. Lalu ampasnya, dalam dibuang lagi ke laut, untuk diolah oleh alga-alga. (Kuncoro. 2007) 2.4 PEMBUATAN SULFUR 2.4.1 Proses Frasch Proses Frasch merupakan suatu proses pengeboran yang ditunjukan untuk mendapatkan kembali simpanan belerang yang terkandung di dalam tanah, pompa

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frasch dirancang oleh Herman Frasch dari Amerika Serikat tahun 1904. Deposit belerang ditambang menurut proses Frasch dilakukan dengan cara membuat lubang ke bawah tanah yang mengandung belerang. Belerang dicairkan dengan mengalirkan uap air panas (1600C) melalui sebuah pipa yang berdiameter 15 cm dengan tekanan sekitar 16 atm. Belerang yang sudah mencair itu, kemudian dipaksa keluar dengan memompa udara panas (tekanan 20-25 atm) melalui pipa kedua. Belerang cair mengalir melalui pipa letiga. Selanjutnya belerang dibiarkan membeku. Belerang yang diperoleh dengan cara ini mempunyai kemurnian sekitar 99,6%.

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. Pada dewasa ini 50% belerang yang digunakan dalam industri diperoleh dengan proses frasch. Belerang juga dapat diperoleh dari minyak bumi dan batu bara. Belerang yang terkandung dalam minyak bumi dan batu bara menimbulkan masalah lingkungan, karena pembakaran bahan-bahan tersebut menghasilkan oksidaoksida belerang yang mencemari udara. Oleh karena itu, belerang tersebut dipisahkan terlebih dahulu dan proses ini menjadi salah satu sumber produksi

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belerang. (Ida Farida, 2008) 2.4.2 Proses kontak Hampir semua asam sulfat dibuat dengan proses kontak. Proses ini berlangsung dalam tiga tahap yaitu produksi SO2, konversi SO2 menjadi SO3 dan konversi SO3 menjadi H2SO2. 1. Produksi SO2 Belerang dibakar dalam udara kering di ruang pembakar pada suhu 10000C. S(s) + O2(g) SO2(g) H = -297 kJ mol-1

Gas yang dihasilkan mengandung kurang lebih 10% volume sulfur dioksida, kemudian setelah didinginkan sampai 4000C, dimurnikan dengan cara pengendapan elektrostatik. 2. Konversi SO2 menjadi SO3 Dengan menggunakan katalis, (biasanya vanadium (V) oksida), sulfur dioksida direaksikan dengan udara bersih yang berlebih. Oleh karena reaksi adalah reaksi eksoterm, gas-gas ini direaksikan pada 4500C- 4740C. 2 SO2 (g) +O2 (g) 2 SO3 H = -98 kJ mol-1

Gas yang panas ini dialirkan melalui sebuah converter yang terdiri dari empat lapisan yang dicampur dengan katalis vanadium (V) oksida. Pada lapisan pertama 70% SO2 dapat diubah menjadi SO3. Oleh karena reaksinya adalah reaksi endoterm, gas harus didinginkan dahulu sebelum mengalami konversi pada lapisan kedua. Pekerjaan ini diulangi sehingga sampai pada lapisan keempat, 98% sulfur dioksida diubah menjadi belerang trioksida. Agar dapat mencapai 99,5% konversi, sulfur trioksida yang dihasilkan didinginkan kemudian dilarutkan dalam Sulfur 45

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asam sulfat 98% sampai 99%. 3. Konversi SO3 menjadi H2SO4 Sulfur trioksida yang dihasilkan didinginkan kemudian dilarutkan dalam H2SO4 98% sehingga menghasilkan asam 98,5% yang kemudian diencerkan dengan air. SO3 (g) + H2SO4 (l) H2S2O7 (l) + H2O (l) Reaksi keseluruhannya adalah H2O + SO3 (g) H2SO4 (l) H = -130 kJ mol-1 (Hiskia achmad,2001) H2S2O7 (l) H2SO4 (l)

Bagan proses kontak

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Pertama-tama belerang padat dimasukan kedalam drum berputar lalu dibakar dengan oksigen dari udara dan hasilnya gas SO2 dimurnikan dengan pengendap elektrostatika ( kawat-kawat bertegangan tinggi ) partikel-partikel debu dan kotoran lain menjadi bermuatan dan tertarik oleh kawat yang muatannya berlawanan, sehingga debu-debu itu jatuh kelantai ruangan. Campuran gas SO2 dan udara kemudian dialirkan kedalam ruangan yang dilengkapi katalis serbuk V2O5. Disini berlangsung proses kontak yaitu kontak antara campuran gas-gas dengan katalis. Gas SO2 bereaksi dengan oksigen dengan udara untuk membentuk gas SO3. 2SO2 (g)+ O2(g) 2SO3(g) H = -90 kJ

Agar reaksi ini bergeser kekanan gas SO3 yang terbentuk segera direaksikan dengan air untuk menghasilkan H2SO4 SO3(g)+ H2O(l) H2SO4(aq)

Gas SO3 direaksikan dengan H2SO4 untuk membentuk asam pirosulfat, Sulfur 47

H2S2O7 kemudian barulah asam pirosulfat direaksikan dengan air untuk membentuk as