33 5 2014 5 ENVIRONMENTAL CHEMISTRY Vol 33 No 5 May 2014 DOI 10 7524 /j issn 0254-6108 2014 05 004 * 1,2 郭广亮 1,3** 王崇臣 王 1 鹏 1 100044 2 100044 3 100022 298 303 308 313 318 K Langmuir Freundlich Dubinin-Radushkevish Web-Morris Gibbs!G 0!H 0!S 0 Langmuir Gibbs!G 0 0!H 0!S 0 0 k 2 0 089 g mg - 1 min - 1 Web-Morris Adsorption of acid fuchsin on biopottery Kinetic and thermodynamic studies GUO Guangliang 1 2 WANG Chongchen 1 3** WANG Peng 1 1 Key Laboratory of Urban Storm Water System and Water Environment Beijing University of Civil Engineering and Architecture Beijing 100044 China 2 Beijing Climate Change Response Research and Education Center Beijing University of Civil Engineering and Architecture Beijing 100044 China 3 The College of Materials Science and Engineering Beijing University of Technology Beijing 100022 China Abstract In order to investigate the dye adsorption properties of biopottery acid fuchsin was chosen as the sorbate The data obtained from different temperature 298 303 308 313 318K were fitted with Langmuir Freundlich and Dubinin-Radushkevish models to describe the equilibrium isotherms The kinetics rates were modeled using pseudo-first-order and pseudo-second-order kinetic equations Using web-morris model to explore mechanisms for adsorption kinetics The Gibbs free energy!g 0 enthalpy change!h 0 and entropy change!s 0 were calculated The results revealed that the equilibrium adsorption amount increased with the increase of temperature The adsorption could be well depicted by the Langmuir adsorption isotherm The Gibbs free energy!g 0 was negative while enthalpy change!h 0 and entropy change!s 0 were both positive indicating that the adsorption was a spontaneous endothermic and increasing entropy process The adsorption kinetics followed pseudo-second-order kinetic equation the rate k 2 was 0 089 g mg - 1 min - 1 Web-Morris model can well explain the mechanism of adsorption kinetics and the intra-particle diffusion controls the adsorption rate 2013 5 9 * 2013M540831 - CIT&CD201404076 2013D005017000004 B KZ201410016018 ** Tel 010-68322124 E-mail chongchenwang@ 126 com
806 33 Keywords biopottery acid fuchsin adsorption thermodynamics kinetics 1 70 2 3 9 698 nm 20 998 m 2 g - 1 0 0508 ml g - 1 4 1 1 1 722S SHZ-82 Spectrum-100 - SEM Zetasizer Nano C 20 H 17 N 3 Na 2 O 9 S 3 585 54 100 1 2 Spectrum 100 4000 400 cm - 1 KBr SEM 0 02 g 20 ml 10 min 200 Zetasizer Nano Zeta 1 3 250 ml 0 6 g L - 1 200 ml 100 150 200 mg L - 1 308 K 150 r min - 1 0 45 μm 545 nm A 1 2 5 q = C 0 - C e V W 1 η = C 0 - C e 100% 2 C 0 q mg g - 1 C 0 mg L - 1 C e mg L - 1 V L W g η 1 4 0 6 g L - 1 150 mg L - 1 308 K 0 45 μm 3 0 ml
5 807 A Langergren 3 6 4 6 Weber-Morris 5 6 ln( q e - q ) t = ln q e - k 1 t 3 t = 1 + 1 t 4 q t k 2 q 2 q e e q t = k 3 t 1 /2 + b 5 q e q t t mg g - 1 k 1 min - 1 k 2 g mg - 1 min - 1 k 3 mg g - 1 min - 1 /2 b 1 5 250 ml 150 200 250 300 350 mg L - 1 1 g L - 1 298 303 308 313 318 K 150 r min - 1 q e 5 298 303 308 313 318 K Langmuir Freundlich Dubinin-Radushkevish 6 8 5 C e q e = 1 q max K L + C e q max 6 lnq e = lnk F + 1 n lnc e 7 ( ) e lnq e = lnq max - K DR ε 2 ε = RTln 1 + 1 C q e mg g - 1 q max mg g - 1 K L Langmuir L mg - 1 K F L mg - 1 n L g - 1 C e mg L - 1 ε polenyi K DR L mg - 1 E E = ( 2K ) - 1 2 DR 1 6 9 10 7 ΔG 0 ΔH 0 ΔS 0 8 ΔG 0 = - RTlnK L 9 lnk D = ΔS 0 /R - ΔH 0 /RT 10 R 8 314 J mol - 1 K - 1 T K K L Langmuir L mg - 1 9 ΔG 0 10 K D = q e /C e lnq e /C e q e q e 0 lnk D lnk D 1 /T ΔH 0 ΔS 0 2 2 1 2 1 1 1 1 3431 cm - 1 OH NH 14 cm - 1 3445 cm - 1 OH 1417 cm - 1 1 cm - 1 1416 cm - 1 1026 cm - 1 1006 cm - 1 OH 1000 cm - 1 8 2 1 2 2
808 33 Fig 1 1 Infrared spectra of biopottery before and after acid fuchsin adsorption Fig 2 2 SEM SEM photograph of biopottery 2 1 3 Zeta ph Zeta - 19 7 mv - 19 6 mv 2 2 T = 308 K 100 150 200 mg L - 1 0 6 g L - 1 t q η 3 q q q η η Fig 3 3 0 6 g L - 1 The removal efficiency of acid fuchsin with different initial concentration as a function of adsorption time the biopottery amount is fixed to 0 6 g L - 1 2 3 Langergren Weber-Morris 5
5 809 4 5 4 R 2 = 0 9989 K 2 = 0 089 g mg - 1 min - 1 q e 154 84 mg g - 1 q e 174 78 mg g - 1 9 Fig 4 4 a b Kinetics equation fitting curve a Pseudo-first order kinetics b Pseudo-second order kinetics 5 q t t 1 /2 t 1 /2 100 200 mg L - 1 k 3 8 16 31 71 mg g - 1 min - 1 /2 Fig 5 5 Intra-particle diffusion plots for the adsorption of acid fuchsin on biopottery 2 4 5 Langmuir Freundlich Dubinin-Radushkevish D-R 6 Langmuir 2 1 Langmuir 1 Langmuir R 2 0 982 Langmuir K L q max
810 33 R L R L = 1 / 1 + K L C 0 11 K L Langmuir C 0 mg L - 1 R L 0 1 R L 1 R L = 1 R L = 0 10-11 R L 0 1 Fig 6 6 Langmuir Langmuir isotherms for the adsorption of acid fuchsin on biopottery Table 1 1 Langmuir Freundlich D-R Fitting parameters of Langmuir Freundlich and D-R isotherms for acid fuchsin adsorption by biopottery powder at different temperatures T /K q max / K L / mg g - 1 L mg - 1 Langmuir Freundlich D-R R 2 K F / K 1 /n R 2 DR / q max / L mg - 1 L mg - 1 mg g - 1 298 224 49 0 018 0 998 25 278 0 394 0 891 188 31 0 051 0 954 303 224 49 0 027 0 996 41 181 0 312 0 973 63 38 0 087 0 819 308 229 88 0 050 0 998 57 133 0 261 0 954 42 09 0 106 0 921 313 236 75 0 124 0 997 92 835 0 178 0 959 7 74 0 241 0 819 318 256 43 0 128 0 995 101 472 0 188 0 892 5 16 0 291 0 890 R 2 Freundlich Freundlich Freundlich n 1 /n 0 1 0 5 2 11 1 /n 0 1 0 5 D-R 2 5 9 10 ΔG 0 ΔH 0 ΔS 0 lnk D 1 /T R 2 = 0 908 ΔH 0 ΔS 0 2 Table 2 2 Values of thermodynamic parameters for the adsorption of acid fuchsin by biopottery /K K L / L mg - 1 ΔG 0 / kj mol - 1 ΔS 0 / J mol - 1 K - 1 ΔH 0 / kj mol - 1 298 8963 96-22 55 303 13627 99-23 98 308 23856 30-25 81 612 99 177 99 313 54845 71-28 39 318 72165 41-29 58
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