黄铜矿吸附5-戊基-1,2,4-三唑-3-硫酮的热力学及机理
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摘要
以正己酸和氨基硫脲为原料,加热回流条件下得到己酰胺硫脲中间体,该中间体在碱溶液中成环并酸化制得5-戊基-1,2,4-三唑-3-硫酮(PETT),采用红外光谱和核磁共振氢谱及碳谱确认其结构。研究PETT对黄铜矿的浮选性能及其在黄铜矿表面的吸附热力学及机理。研究结果表明:PETT是黄铜矿的优良捕收剂,其吸附于黄铜矿表面的优选p H范围为4.0~9.0,吸附量随着温度的升高而增大,其等温吸附符合Langmuir模型,吸附焓变ΔH为54.27 k J/mol,熵变ΔS为278.82 J/(mol·K),吸附自由能变ΔG为-28.81 k J/mol(298 K)。PETT吸附于黄铜矿表面的过程可能为自发、吸热的单分子层化学吸附。PETT通过其三唑环内氮原子和环外硫原子与黄铜矿表面的铜原子成键而化学吸附于黄铜矿表面。
During refluxing, the intermediate, hexanamide thiourea was prepared by using hexanoic acid and thiosemicarbazide as raw materials. And then the intermediate was cyclized in alkaline solutions, and subsequently acidized to obtain 5-pentyl-1,2,4-triazole-3-thione(PETT). The structure of PETT was characterized by FTIR, 1 HNMR and 13 CNMR spectra. The flotation performance, adsorption thermodynamics and mechanism of PETT on to chalcopyrite were investigated. The results show that PETT is an excellent collector for chalcopyrite flotation and it prefers to adsorb on to chalcopyrite surfaces at p H 4.0-9.0, and its adsorption amount increases with the increase of temperature. PETT adsorption on to chalcopyrite surfaces is in line with Langmuir mode and the thermodynamic parameters ΔH, ΔS and ΔG(298 K) are 54.27 k J/mol, 278.82 J/(mol·K) and-28.81 k J/mol, respectively. This demonstrates that PETT adsorption is a spontaneous, endothermic and monolayer chemisorption. PETT chemisorbs on to chalcopyrite surfaces through bonding of its nitrogen atoms in the triazole ring and the exocyclic sulfur atom with the surface copper atoms.
During refluxing, the intermediate, hexanamide thiourea was prepared by using hexanoic acid and thiosemicarbazide as raw materials. And then the intermediate was cyclized in alkaline solutions, and subsequently acidized to obtain 5-pentyl-1,2,4-triazole-3-thione(PETT). The structure of PETT was characterized by FTIR, 1 HNMR and 13 CNMR spectra. The flotation performance, adsorption thermodynamics and mechanism of PETT on to chalcopyrite were investigated. The results show that PETT is an excellent collector for chalcopyrite flotation and it prefers to adsorb on to chalcopyrite surfaces at p H 4.0-9.0, and its adsorption amount increases with the increase of temperature. PETT adsorption on to chalcopyrite surfaces is in line with Langmuir mode and the thermodynamic parameters ΔH, ΔS and ΔG(298 K) are 54.27 k J/mol, 278.82 J/(mol·K) and-28.81 k J/mol, respectively. This demonstrates that PETT adsorption is a spontaneous, endothermic and monolayer chemisorption. PETT chemisorbs on to chalcopyrite surfaces through bonding of its nitrogen atoms in the triazole ring and the exocyclic sulfur atom with the surface copper atoms.
引文
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[26]ALBERTY R A.Standard Gibbs free energy,enthalpy,and entropy changes as a function of p H and p Mg for several reactions involving adenosine p Hosp Hates[J].Journal of Biological Chemistry,1969,244(12):3290-3302.
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[28]FAIN V M.Principle of entropy increase and quantum theory of relaxation[J].p Hysics-Uspekhi,1963,6(2):294-323.
[29]CHEN Minglian.Effects of microorganisms on surface properties of chalcopyrite and bioleaching[J].Transactions of Nonferrous Metals Society of China,2008,18(6):1421-1426.
[30]HE Zhiling.A novel surfactant,N,N-diethyl-N′-cyclohexylthiourea:Synthesis,flotation and adsorption on chalcopyrite[J].Journal of Industrial and Engineering Chemistry,2016,37:107-114.
[31]GHAHREMANINEZHAD A,DIXON D G.Asselin.Electrochemical and XPS analysis of chalcopyrite(Cu Fe S 2)dissolution in sulfuric acid solution[J].Electrochimica Acta,2013,87:97-112.
[32]NAVA D,GONZáLEZ I,LEINEN D,et al.Surface characterization by X-ray photoelectron spectroscopy and cyclic voltammetry of products formed during the potentiostatic reduction of chalcopyrite[J].Electrochimica Acta,2008,53(14):4889-4899.
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[35]YIN M,WU C K,LOU Y,et al.Copper Oxide Nanocrystals[J].Journal of Amercian Chenmical Society,2005,127:9506-9511.
[36]BRION D.Photoelectrons spectroscope study on the surface degradation of Fe S2,Cu Fe S2,Zn S and Pb S in air and water[J].Applications of Surface Science,1980,5(2):133-152.
[37]BEST S A,BRANT P,FELTHAM R D,et al.X-ray p Hotoelectron spectra of inorganic molecules.18.Observations on sulfur 2p binding energies in transition metal complexes of sulfur-containing ligands[J].Inorganic Chemistry,1977,16(8):1976-1979.
[38]FAIRTHORNE G A,FORNASIERO D,RALSTON J.The interaction of thionocarbamate and thiourea collectors with sulfide mineral surfaces:a flotation and adsorption study[J].International Journal of Mineral Processing,1997,50(4):227-242.
[39]VON OERTZEN G U,HARMER S L,SKINNER W M.XPS and ab initio calculation of surface states of sulfide minerals:pyrite,chalcopyrite and molybdenite[J].Molecular Simulation,2006,32(15):1207-1212.
[2]SUMANGALA V,POOJARY B,CHIDANANDA N,et al.Facile synthesis,cytotoxic and antimicrobial activity studies of a new group of 6-aryl-3-[4-(methylsulfonyl)benzyl]-7H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazines[J].European Journal of Medicinal Chemistry,2012,54:59-64.
[3]MAVROVA A T,WESSELINOVA D,TSENOV Y A,et al.Synthesis,cytotoxicity and effects of some 1,2,4-triazole and 1,3,4-thiadiazole derivatives on immunocompetent cells[J].European Journal of Medicinal Chemistry,2009,44(1):63-69.
[4]ALMASIRAD A,TABATABAI S A,FAIZI M,et al.Synthesis and anticonvulsant activity of new 2-substituted-5-[2-(2-fluorop Henoxy)p Henyl]-1,3,4-oxadiazoles and 1,2,4-triazoles[J].Bioorganic&Medicinal Chemistry Letters,2004,14(24):6057-6059.
[5]AMIR M,SHIKHA K.Synthesis and anti-inflammatory,analgesic,ulcerogenic and lipid peroxidation activities of some new 2-[(2,6-dichloroanilino)p Henyl]acetic acid derivatives[J].European Journal of Medicinal Chemistry,2004,39(6):535-545.
[6]ABDEL-WAHAB B F,ABDEL-LATIF E,MOHAMED H A,et al.Design and synthesis of new 4-pyrazolin-3-yl-1,2,3-triazoles and 1,2,3-triazol-4-yl-pyrazolin-1-ylthiazoles as potential antimicrobial agents[J].European journal of medicinal chemistry,2012,52:263-268.
[7]陆咏,袁少波.噻吩及其衍生物[J].精细与专用化学品,2002,10(22):5-8.LU Yong,YUAN Shaobo.Thiop Hene and its derivatives[J].Fine and Specialty Chemicals,2002,10(22):5-8.
[8]CHIBA M,CHERNIAK E A.Kinetic study of reversible conversion of methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate(benomyl)to methyl2-benzimidazolecarbamate(MBC)and butyl isocyanate(BIC)in organic solvents[J].Journal of Agricultural and Food Chemistry,1978,26(3):573-576.
[9]杨双花.新型含1,2,4-三唑类化合物的合成、表征及生物活性研究[D].青岛:青岛科技大学化工学院,2006:12-26.YANG Shuanghua.Studies on synthesis,characterization and biological activities of novel compounds containing1,2,4-triazole[D].Qingdao:Qingdao University of Science and Technology.School of Chemical Engineering,2006:12-26.
[10]于观平.含均三唑或噁二唑的三唑类化合物的合成及生物活性研究[D].青岛:青岛科技大学化工学院,2006:5-15.YU Guangping.Studies on synthesis and biological activities of triazole compounds containing mean triazole or oxadiazole group[D].Qingdao:Qingdao University of Science and Technology.School of Chemical Engineering,2006:5-15.
[11]OUICI H B,BENALI O,HAREK Y,et al.Inhibition of mild steel corrosion in 5%HCl solution by 5-(2-hydroxyp Henyl)-1,2,4-triazole-3-thione[J].Research on Chemical Intermediates,2013,39(6):2777-2793.
[12]ZHANG Y Y,ZHOU C H.Synthesis and activities of nap Hthalimide azoles as a new type of antibacterial and antifungal agents[J].Bioorganic&Medicinal Chemistry Letters,2011,21(14):4349-4352.
[13]ELDAKAR N,NOBE K E N.Electrochemical and corrosion behavior of iron in presence of substituted benzotriazoles[J].Corrosion,1977,33(4):128-130.
[14]LIU C,LU G,JIANG L,et al.Study on the electrochemical behavior of dopamine and uric acid at a2-Amino-5-mercapto-[1,3,4]triazole self-assembled monolayers electrode[J].Electroanalysis,2006,18(3):291-297.
[15]SINGH B,SINGH R.Transition metal complexes of3-(4-pyridyl)-triazoline-5-thione[J].Journal of Inorganic and Nuclear Chemistry,1972,34(11):3449-3454
[16]SCOZZAFAVA A,CAVAZZA C,SUPURAN C T,et al.Complexes with biologically active ligands,Part 11:Synthesis and carbonic anhydrase inhibitory activity of metal complexes of4,5-disubstituted-3-mercapto-1,2,4-triazole derivatives[J].Metalbased Drugs,1998,5(1):11-18.
[17]PERGOLESE B,BIGOTTO A.Study by SERS spectroscopy of the adsorption of 1H-1,2,4-triazole-3-thione on silver sols[J].Journal of Molecular Structure,2003,651/652/653:349-352.
[18]O'NEIL R M,PHILLIPS E.Corrosion inhibition[P].GB2182030A,1987-05-07.
[19]WILLEMS J F,VANDENBERGHE A.The preparation of5-substituted 1,2,4-triazoline-3-thiones and of alkylene and arylene 5,5'-bis-l,2,4-triazoline-3-thiones[J].Bulletin des Sociétés Chimiques Belges,1966,75(5/6):358-365.
[20]刘广义,钟宏,戴塔根,等.中碱度条件下乙氧羰基硫脲浮选分离铜硫[J].中国有色金属学报,2009,19(2):389-396.LIU Guangyi,ZHONG Hong,DAI Tagen,et al.Flotation separation of Cu/Fe sulfide minerals by ethoxycarbonyl thiourea under middle alkaline conditions[J].The Chinese Journal of Nonferrous Metals,2009,19(2):389-396.
[21]曲肖彦,刘广义,刘胜义,等.3-己基-4-氨基-1,2,4-三唑-5-硫酮在黄铜矿表面的吸附动力学与热力学[J].中国有色金属学报,2015,25(7):2006-2014.QU Xiaoyan,XIAO Jingjing,LIU Guangyi,et al.Investigation on the flotation behavior and adsorption mechanism of3-hexyl-4-amino-1,2,4-triazole-5-thione to chalcopyrite[J].The Chinese Journal of Nonferrous Metals,2015,25(7):2006-2014.
[22]肖静晶,狄宁,刘广义,等.N-丁氧丙基-N′-乙氧羰基硫脲对硫化矿物的浮选行为与吸附机理[J].中国有色金属学报,2014,24(2):561-568.XIAO Jingjing,DI Ning,LIU Guangyi,et al.Adsorption mechanism and flotation behaviors of N-butoxypropylN’-ethoxycarbonyl thiourea with sulfide minerals[J].The Chinese Journal of Nonferrous Metals,2014,24(2):561-568.
[23]BELTON G R.Langmuir adsorption,the Gibbs adsorption isotherm,and interracial kinetics in liquid metal systems[J].Metallurgical Transactions B,1976,7(1):35-42.
[24]UMPLEBY R J,BAXTER S C,BODE M,et al.Application of the Freundlich adsorption isotherm in the characterization of molecularly imprinted polymers[J].Analytica Chimica Acta,2001,435(1):35-42.
[25]刘广义,张慧丽,任恒,等.N,N′-二异丙氧基丙基-N″,N''-氧二乙氧羰基硫脲在黄铜矿表面的吸附动力学和热力学[J].中南大学学报(自然科学版),2015,46(5):1588-1594.LIU Guangyi,ZHANG Huili,REN Heng,et al.Adsorption kinetics and thermodynamics of N,N′-dipropoxypropyl-N″,N′′′-oxydiethylenedicarbonyl bis(thiourea)with chalcopyrite[J].Journal of Central South University(Science and Technology),2015,46(5):1588-1594.
[26]ALBERTY R A.Standard Gibbs free energy,enthalpy,and entropy changes as a function of p H and p Mg for several reactions involving adenosine p Hosp Hates[J].Journal of Biological Chemistry,1969,244(12):3290-3302.
[27]TSAI C J,DEL SOL A,NUSSINOY R.Allostery:absence of a change in shape does not imply that allostery is not at play[J].Journal of Molecular Biology,2008,378(1):1-11.
[28]FAIN V M.Principle of entropy increase and quantum theory of relaxation[J].p Hysics-Uspekhi,1963,6(2):294-323.
[29]CHEN Minglian.Effects of microorganisms on surface properties of chalcopyrite and bioleaching[J].Transactions of Nonferrous Metals Society of China,2008,18(6):1421-1426.
[30]HE Zhiling.A novel surfactant,N,N-diethyl-N′-cyclohexylthiourea:Synthesis,flotation and adsorption on chalcopyrite[J].Journal of Industrial and Engineering Chemistry,2016,37:107-114.
[31]GHAHREMANINEZHAD A,DIXON D G.Asselin.Electrochemical and XPS analysis of chalcopyrite(Cu Fe S 2)dissolution in sulfuric acid solution[J].Electrochimica Acta,2013,87:97-112.
[32]NAVA D,GONZáLEZ I,LEINEN D,et al.Surface characterization by X-ray photoelectron spectroscopy and cyclic voltammetry of products formed during the potentiostatic reduction of chalcopyrite[J].Electrochimica Acta,2008,53(14):4889-4899.
[33]GOH S W,BUCKLEY A N,LAMB R N,et al.The oxidation states of copper and iron in mineral sulfides,and the oxides formed on initial exposure of chalcopyrite and bornite to air[J].Geochimica et Cosmochimica Acta,2006,70(9):2210-2228.
[34]LIU G,QIU Z,WANG J,et al.Study of N-isopropoxypropyl-N’-ethoxycarbonyl thiourea adsorption on chalcopyrite using in situ SECM,To F-SIMS and XPS[J].Journal of Colloid and Interface Science,2015,437:42-49.
[35]YIN M,WU C K,LOU Y,et al.Copper Oxide Nanocrystals[J].Journal of Amercian Chenmical Society,2005,127:9506-9511.
[36]BRION D.Photoelectrons spectroscope study on the surface degradation of Fe S2,Cu Fe S2,Zn S and Pb S in air and water[J].Applications of Surface Science,1980,5(2):133-152.
[37]BEST S A,BRANT P,FELTHAM R D,et al.X-ray p Hotoelectron spectra of inorganic molecules.18.Observations on sulfur 2p binding energies in transition metal complexes of sulfur-containing ligands[J].Inorganic Chemistry,1977,16(8):1976-1979.
[38]FAIRTHORNE G A,FORNASIERO D,RALSTON J.The interaction of thionocarbamate and thiourea collectors with sulfide mineral surfaces:a flotation and adsorption study[J].International Journal of Mineral Processing,1997,50(4):227-242.
[39]VON OERTZEN G U,HARMER S L,SKINNER W M.XPS and ab initio calculation of surface states of sulfide minerals:pyrite,chalcopyrite and molybdenite[J].Molecular Simulation,2006,32(15):1207-1212.
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