Transpor Cr(III), Cd(II), Pb(II), dan Ag(I) melalui membran cair ruah yang mengandung turunan karboksilat, ester, dan amida p-t-butilkaliks[4] arena sebagai pengemban ion

MAMING, Promotor Prof. Dr. Hardjono Sastrohamidjojo

2008 | Disertasi |

Disertasi ini merupakan hasil penelitian transpor Cr(III), Cd(II), Pb(II), dan Ag(I) melalui membran cair ruah kloroform yang mengandung senyawa 5,11,17,23-tetrakis(t-butil)kaliks[4]arena-25,26,27,28-tetrol (kaliks[4]arena 1), 5,11,17,23-tetrakis(t-butil)-25,26,27,28-tetrakis(karboksimetoksi)kaliks[4]arena (kaliks[4]arena 2), 5,11,17,23-tetrakis(t-butil)-25,26,27,28-tetrakis(etoksikarbonilmetoksi)kaliks[4]- arena (kaliks[4]arena 3), 5,11,17,23-tetrakis(t-butil)-25,26,27,28- tetrakis(dietilkarbamoilmetoksi) kaliks[4]arena (kaliks[4]arena 4), dan 5,11,17,23-tetrakis(t-butil)- 25,27-bis(hidroksi)-26,28-bis(fenilkarbamoilmetoksi)kaliks[4]arena (kaliks[4]arena 5) sebagai pengemban ion. Penelitian ini mencakup sintesis pengemban ion dan karakterisasi dengan metoda t.l., KLT, spektroskopi IR, 1H-NMR, dan 13C-NMR; transpor ion logam pada berbagai pH fasa sumber, konsentrasi pengemban ion dalam membran, jenis dan konsentrasi senyawa pendekompleksasi dalam fasa target, dan waktu transpor; transpor kompetisi ion; spektrometri kompleks menggunakan spektrometer UV, IR, 1H-NMR, dan XRD; pemodelan transpor ion logam. Konsentrasi ion logam yang tertranspor dianalisis dengan Spektrofotometer Serapan Atom. Proses transpor dilakukan dalam sel pipa gelas U pada temperatur 29 ± 1 oC. Kaliks[4]arena 1 berupa padatan putih (47%) dengan t.l. 338 – 343 oC (cone) diperoleh dari rangkaian reaksi antara p-t-butilfenol dengan formaldehida. Pada reaksi kaliks[4]arena 1 dengan etil-2-kloroasetat/KI diperoleh kaliks[4]arena 3 (70%) dengan t.l. 123-125 oC (cone) dan dengan N-fenil-2-kloroasetamida/KI diperoleh kaliks[4]arena 5 (37%) dengan t.l. 251-252 oC (cone). Hidrolisis basa kaliks[4]arena 3 menghasilkan kaliks[4]arena 2 (68 %) dengan t.l. 291oC (cone). Pada reaksi antara tionil klorida dengan kaliks[4]arena 2 yang dilanjutkan dengan reaksi menggunakan N,N-dietilamina diperoleh kaliks[4]arena 4 (47%) dengan t.l. 280 oC (campuran cone, partial cone, dan 1,2-alternate). Kaliks[4]arena 1 - 5 dapat berperan sebagai pengemban ion pada transpor keempat ion logam berat, kecuali terhadap Cr(III) sangat sulit ditranspor namun dapat diekstrak ke fasa membram. Pola perubahan efisiensi transpor ion-ion logam pada berbagai pH fasa sumber dengan pengemban ion kaliks[4]arena 1 - 5 identik, hanya dibedakan oleh pH optimum masing-masing yang berada pada kisaran 4 - 5, begitu pula pola perubahan efisiensi transpor ion logam pada berbagai konsentrasi pengemban ion dalam fasa membran juga identik dengan kondisi optimum dalam rentang 0,5–3,0 × 10-4 M. Pengaruh pH sedikit berbeda pada transpor Ag(I) dengan pengemban ion kaliks[4]arena 4 dan 5 yaitu optimum pada dua pH (sekitar 0 dan 5). Perbedaan pH optimum tersebut berhubungan dengan sifat keasaman/kebasaan ion logam dan pengemban ion serta mekanisme transpor. Di samping itu, transpor ion logam dengan pengemban ion kaliks[4]arena 3, 4, dan 5 diefektifkan terutama oleh kebasaan anion pendekompleksasi sedangkan dengan kaliks[4]arena 1 dan 2 diefektifkan terutama oleh konsentrasi H+ dalam fasa target. Transpor Ag(I) dan Cd(II) efektif dengan pendekompleksasi basa lunak, sementrara transpor Cr(III) dan Pb(II) lebih efektif dengan pendekompleksasi basa agak keras.Transpor ion logam dengan mengemban ion kaliks[4]arena 1 dan 2 mengikuti pola nonequilibrium, sedangkan kaliks[4]arena 3, 4, dan 5 mengikuti pola equilibrium. Secara umum, efisiensi transpor Ag(I)>Pb(II)> Cd(II)>>Cr(III) oleh semua pengemban ion, kecuali oleh kaliks[4]arena 2 menyebabkan efisiensi transpor Pb(II)>Ag(I). Efisiensi transpor masing-masing Cr(III), Pb(II), Cd(II), dan Ag(I) oleh kaliks[4]arena 1 adalah 0, 3, 11, dan 38%; kaliks[4]arena 2 adalah 6, 80, 84, dan 81%; kaliks[4]arena 3 adalah 0, 9, 9, dan 49%; kaliks[4]arena 4 adalah 12, 26, 36, dan 42%; kaliks[4]arena 5 adalah 3, 9, 16 dan 28%. Selain itu, pengemban ion lebih selektif terhadap ion tertentu, yaitu kaliks[4]arena 1 dan 2 terhadap Pb(II) dan Ag(I), kaliks[4]arena 3 terhadap Ag(I), kaliks[4]arena 4 terhadap Cd(II), dan kaliks[4]arena 5 terhadap Ag(I) dalam suasana pH fasa sumber sedang. Selektivitas luar biasa terjadi pada transpor Ag(I) dengan pengemban ion kaliks[4]arena 4 (43%, bAg/Cd = bAg/Pb = bAg/Cr = ~ ) dan 5 (20%, bAg/Cd = 20,2, bAg/Pb = bAg/Cr = ~ ) dalam suasana pH fasa sumber sangat rendah. Selektivitas transpor ion logam tersebut sangat ditentukan oleh sifat HSAB pendekompleksasi, kestabilan dan kepolaran kompleks, serta mekanisme transpor. Transpor ion logam dengan pengemban ion kaliks[4]arena 2 umumnya berlangsung lebih cepat dibanding dengan pengemban ion lainnya, menyusul dengan kaliks[4]arena 4, 5, 3, dan paling lambat adalah dengan kaliks[4]arena 1, kecuali pada transpor Ag(I) dengan pengemban ion kaliks[4]arena 3 dan 4 yang nampak lebih cepat. Fenomena kinetika yang lain adalah difusitas kompleks Cr(III)<

This dissertation represents a research on Cr(III), Cd(II), Pb(II), and Ag(I) transport through chloroform bulk liquid membrane containing 5,11,17,23-tetrakis-(tert-butyl)calix[4]arene-25,26,27,28-tetrol (calix[4]arene 1), 5,11,17,23-tetrakis-(tert-butyl)-25,26,27,28-tetrakis(carboxymethoxy)calix[4]arene (calix[4]arene 2),5,11,17,23-tetrakis(tert-butyl)-25,26,27,28-tetrakis(ethoxycarbonilmethoxy)calix[4]- arene (calix[4]arene 3), 5,11,17,23-tetrakis(tert-butyl)-2This dissertation represents a research on Cr(III), Cd(II), Pb(II), and Ag(I) transport through chloroform bulk liquid membrane containing 5,11,17,23-tetrakis- (tert-butyl)calix[4]arene-25,26,27,28-tetrol (calix[4]arene 1), 5,11,17,23-tetrakis- (tert-butyl)-25,26,27,28-tetrakis(carboxymethoxy)calix[4]arene (calix[4]arene 2), 5,11,17,23-tetrakis(tert-butyl)-25,26,27,28- tetrakis(ethoxycarbonilmethoxy)calix[4]- arene (calix[4]arene 3), 5,11,17,23-tetrakis(tert-butyl)-25,26,27,28-tetrakis(diethylcarbamoylmethoxy) calix[4]arene (calix[4]arene 4), and 5,11,17,23-tetrakis- (tert-butyl)-25,27-bis(hydroxy)-26,28-bis(phenylcarbamoylmethoxy)calix[4]arene (calix[4]arene 5) as ion carriers. This research includes syntheses of the ion carriers; transport processes of the metals ions with variation of source phase pH, concentrations of the ion carrier in membrane, nature and concentrations of decomplexants in target phase, and transport times; metal ion transport competitions; complex spectrometry; and transport modeling. The products of syntheses were characterized using m.p., TLC, UV, IR, 1H-NMR, 13C-NMR methods, while the products of complexes were characterized using UV, IR, 1H-NMR, and XRD methods. Concentrations of the metal ions transported were determined by means of atomic absorption spectrophotometer. All of the transport experiments were carried out using a bulk type membrane in U glass tube at 29 ± 1 oC. Calix[4]arene 1, which is white crystal with m.p. of 340 – 344 oC (47%, cone), was prepared through reaction of p-tert-butylphenol wih formadehyde. Reaction of calix[4]arene 1 with ethyl-2-chloroacetate/KI gave calix[4]arene 3 (70%, m.p. 123- 125 oC, cone) and with N-phenyl-2-chloroacetamide/KI afforded calix[4]arene 5 (37%, m.p. 251-252 oC, cone). Base hydrolysis of calix[4]arene 3 produced calix[4]arene 2 (68%, m.p. 291oC, cone). On treatment with thionyl chloride followed by N,N-diethylamine, calix[4]arene 1 was converted to calix[4]arene 4 (47%, m.p. 280 oC, cone, partial cone, and 1,2-alternate). Calix[4]arene 1 - 5 behaved as ion carrier on transport of the heavy metal ions, except for Cr(III) which was very difficult to be transported, but it was extractable to membrane phase. The relation of the metal ions transport efficiency to the source phase pH in the presence of calix[4]arene 1 - 5 are identical, and distinguished only by the optimum pH in range 4 - 5, except for Ag(I) transport in the presence of calix[4]arene 4 and 5, which gave optimum pH of about 0 and 5 respectively. Relations of the metal ion transport efficiency to the concentration of ion carrier in membrane phase were also identical, and distinguished by the optimum concentration in range 0,5 - 3,0 × 10-4 M. These facts relate to the hardness of the metal ions/ion carriers and transport mechanism. Moreover, the metal ions transports using both calix[4]arene 1 and 2 were effected by H+ concentration in source phase while the metal ions transports using calix[4]arene 3, 4, and 5 as ion carrier were effected by the hardness of the decomplexant anion. Decomplexation of both Ag(I) and Cd(II) complexes were facilitated by soft base decomplexant, while decomplexation of both of Cr(III) and Pb(II) complexes were strengthened by the hard or moderate base decomplexant. The metal ion transport using calix[4]arene 1 and 2 as ion carriers are nonequilibrium systems and those using calix[4]arene 3, 4, and 5 as ion carriers are equilibrium systems. In general, the transport efficiency of 5,26,27,28-tetrakis(diethylcarbamoylmethoxy) the metal ions was as follows Cr(III)<Ag(I). Transport efficiency of Cr(III), Cd(II), Pb(II), and Ag(I) by each of the ion carriers is as follows: 0, 3, 11, and 38 % respectively by calix[4]arene 1; 6, 80, 84, and 81 % respectively by calix[4]arene 2; 0, 9, 9, and 49% respectively by calix[4]arene 3; 3, 12, 26, 36 and 42% respectively by calix[4]arene 4; 3, 9, 16, and 28% respectively by calix[4]arene 5. In addition, an ion carrier was certainly more selective for a metal ion, such as calix[4]arene 1 and 2 for Pb(II)/Ag(I), calix[4]arene 3 for Ag(I), calix[4]arene 4 for Cd(II), and calix[4]arene 5 for Ag(I), where transport processes were conducted in moderate pH of source phase. The remarkable selectivity of transport which was conducted in very low pH of source phase, was shown by Ag(I) in the presence of calix[4]arene 4 (43%, bAg/Cd = bAg/Pb = bAg/Cr = ~ ) or calix[4]arene 5 (20%, bAg/Cd = 20,2, bAg/Pb = bAg/Cr = ~ ). Transport selectivity of metals ions strongly depends on HSAB of decomplexant, both stability and polarity of complexes, and transport mechanism. In general, the metal ions were transported by calix[4]arene 2 faster than by the others ion carriers, except for transport Ag(I) by calix[4]arenes 3 and 4 in very low source phase pH which gave the highest transport rate, and the metal ion transport by calix[4]arene 1 was the slowest rate. The other fact, diffusities of the metal ions complexes are as follows: Cr(III)<

Kata Kunci : Transpor,Membran cair,Ion logam berat,Pengemban ion,Kaliks[4]arena,Model transpor, transport, liquid membrane, heavy metal ion, calix[4]arene, ion carrier, efficiency, selectivity, and transport model