Sintesis dan penggunaan Tetramer Siklis seri Kaliksresorsinarena, Alkoksikaliksarena, dan Alkenilkaliksarena untuk adsorpsi kation logam berat

SARDJONO, Ratnaningsih Eko, Promotor Prof.Dr. Hardjono Sastrohamidjojo

2007 | Disertasi | S3 Ilmu Kimia

Disertasi ini meliputi sintesis dan karakterisasi kaliksarena-kaliksarena yang termasuk dalam seri kaliks[4]resorsinarena, alkoksikaliks[4]arena, dan alkenilkaliks[4]arena, serta penggunaan beberapa kaliksarena hasil sintesis tersebut untuk adsorpsi kation logam berat Cr(III), Cu(II), Pb(II), Cd(II), Hg(II), dan Ag(I) baik dengan sistem batch, maupun fixed bed column. Sintesis kaliksarena-kaliksarena dalam seri C-alkilkaliks[4]resorsinarena dilakukan melalui 1 atau 2 tahap reaksi dari resorsinol dan berbagai macam aldehida. Sintesis beberapa kaliksarena dalam seri kaliks[4]resorsinaril asetat dilakukan melalui asetilasi, sedangkan dalam seri alkilaminokaliks- [4]resorsinarena dilakukan melalui reaksi Mannich terhadap beberapa Calkilkaliks[ 4]resorsinarena. Tetramer siklis dalam seri alkoksikaliks[4]arena disintesis melalui rute alkoksibenzilalkohol yang terdiri dari 2 atau 3 tahap reaksi. Sintesis 4-allilkaliks[4]arena (AKA) dilakukan melalui rute 4-t-butilfenol yang terdiri dari 4 tahap reaksi, sedangkan sintesis polimonoalliloksikaliks[4]arena (PMAKA) dilakukan melalui 6 tahap reaksi. Senyawa-senyawa hasil sintesis dikarakterisasi menggunakan GC-MS, spektrometer IR, 1HNMR, dan/atau 13CNMR. Dalam adsorpsi sistem batch dilakukan variasi pH, waktu interaksi, dan massa adsorben untuk menentukan kondisi optimum, mempelajari kinetika dan kesetimbangan adsorpsi. Dalam sistem fixed bed column diturunkan kurva breakthrough untuk mengetahui kondisi operasional paling efisien, kapasitas adsorpsi, beberapa parameter transfer massa (HU, HUNB, dan Kca), dan kinetika adsorpsi. Pengaruh perbedaan laju alir dan konsentrasi awal juga dipelajari. Desorpsi dilakukan secara sikuensial menggunakan aquades yang dilanjutkan dengan HCl 1M. Dalam seri C-alkilkaliks[4]resorsinarena, kaliks[4]resorsinaril asetat, aminometilkaliks[4]arena telah dihasilkan masing-masing 6 kaliksarena (CMKR, CMFKR, CHFKR, CHMFKR, CBFKR, dan CEKMFKR), 4 kaliksarena (CMKRAS, CMFKRAS, CHFKRAS, dan CHMFKRAS), dan 5 kaliksarena (TDEACMKR, TDMACMKR, NPOCMKR, TDEACMFKR, dan NPOCMFKR). Dalam seri alkoksikaliks[4]arena telah dihasilkan 3 kaliksarena, yaitu TEK, TMK, dan TBK. Dalam seri alkenilkaliks[4]arena telah dihasilkan AKA, dan 5 kaliksarena perantara sintesis PMAKA. Rendemen hasil total bervariasi dari rendah, sedang, hingga tinggi. Terdapat 4 kaliksarena yang dipilih sebagai adsorben, yaitu CMKR, CMFKR, CHFKR, dan CHMFKR. Adsorpsi lebih dipengaruhi oleh tingkat keasaman larutan adsorbat, dibandingkan dengan pengaruh variasi waktu interaksi dan massa adsorben. Pada umumnya adsorpsi mencapai nilai optimum pada tingkat keasaman menengah (pH 4-6). Parameter yang terkait dengan hasil kesetimbangan adsorpsi, seperti kapasitas adsorpsi (q, dan Xm) baik dengan sistem batch maupun fixed bed column menunjukkan kecenderungan yang ditentukan oleh kesesuaian sifat keras-lunak asam-basa. Sebaliknya, parameter yang terkait dengan proses kinetika adsorpsi baik dengan sistem batch maupun fixed bed column, seperti laju adsorpsi, koefisien transfer massa, atau mekanisme adsorpsi, lebih dipengaruhi oleh kesesuaian ukuran rongga adsorben-adsorbat dan keberadaan gugus basa kuat (pendonor elektron kuat) hidroksil. Desorpsi pada umumnya dapat dilakukan dengan sempurna, dan menunjukkan adsorpsi didominasi oleh kemisorpsi. Adsorben-adsorben yang diuji bersifat tidak selektif terhadap adsorpsi logamlogam berat.

This dissertation is an account of the synthesis and characterization of calix[4]resorcinarene, alkoxycalix[4]arene, and alkenylcalix[4]arene series, as well as their application for adsorption of Cr(III), Cu(II), Pb(II), Cd(II), Hg(II), and Ag(I) heavy metals, conducted in batch and fixed bed column systems. Synthesis of calixarenes in C-alkylcalix[4]resorcinarene series was conducted via 1 or 2 reaction stage(s) of resorcinol and various aldehydes. Synthesis of some calixarenes in calix[4]resorcinaryl acetate series was carried out via acetylation, whereas for aminomethylcalix[4]resorcinarene series, it was conducted via Mannich reaction toward some C-alkylcalix[4]resorcinarenes. Some calixarenes in alkoxycalix[4]arene series were synthesized through alkoxybenzyalcohol route consisted of 2 or 3 reaction stages. Synthesis of 4- allylcalix[4]arene (AKA) was conducted through 4-t-buthylphenol route consisted of 4 reaction stages, whereas polymonoallyloxycalix[4]arene (PMAKA) was synthesized via 6 reaction stages. All the synthesized calixarenes and their precursors were analyzed using IR spectrometer, GC-MS, 1HNMR and/or 13CNMR spectrometer. In batch system, the adsorption experiments were done in three conditions, i.e. variation of pH, shaking time, and mass of adsorbent. In addition to obtain optimum conditions of the adsorptions, the experiments were conducted to study kinetics and equilibrium of the adsorptions. In fixed bed column system, the experiments were conducted to establish breakthrough curve. Based on the breakthrough curve, column efficiency, adsorption capacity, some parameters of mass transfer (HU, HUNB, and Kca), and adsorption kinetics were then determined. The effect of flow rate difference and initial concentration of the feeding solution was studied as well. Desorption process was done sequentially using water and followed by 1M HCl solution. There were 6 (CMKR, CMFKR, CHFKR, CHMFKR, CBFKR and CEKMFKR), 4 (CMKRAS, CMFKRAS, CHFKRAS and CHMFKRAS), and 5 (TDEACMKR, TDMACMKR, NPOCMKR, TDEACMFKR and NPOCMFKR) calixarenes that had been synthesized in C-alkylcalix[4]resorcinarene, calix[4]resorcinaryl acetate, and aminomethylcalix[4]resorcinarene series, respectively. In the case of alkoxycalix[4]arene series, 3 calixarenes have been synthesized, namely TEK, TMK, and TBK. Furthermore, AKA has been synthesized through 4-t-buthylphenol route consisted of 4 stages. In the reaction route of PMAKA synthesis, 5 precursor calixarenes have been synthesized. The produced calixarenes varied in yield, from low to high. There were 4 selected calixarenes utilized as adsorbents, i.e. CMKR, CMFKR, CHFKR, and CHMFKR. The adsorption experiments in batch system figured out that acidity affected the adsorption significantly, compared with shaking time and mass of adsorbent. Generally, adsorptions reached their optimum condition at moderate acidity level (pH 4-6). The parameter that is related to adsorption equilibrium result in batch and fixed bed column systems, such as adsorption capacity (q and Xm), was determined by the suitability of hard-soft acid-base character. On the contrary, the parameters related to adsorption kinetics process, such as adsorption rate, coefficient of mass transfer, and adsorption mechanism, were affected by the suitability of size between adsorbent and adsorbate, and the existence of hydroxyl group, which was a strong electron donating (strong base). Based on the desorption test, adsorptions were dominated by chemisorptions. The tested adsorbents apparently did not adsorb the heavy metals selectively.

Kata Kunci : Adsorpsi Kation Logam Berat,Tetramer Siklis