补偿效应:一条化学/化工动力学基本定律的探讨
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摘要
补偿效应揭示了Arrhenius方程中反应速率常数k的指数项(-E/RgT)与指前因子(k0)项存在着相互补偿关系。不仅存在于催化与非催化,均相与非均相的反应体系及需要克服能垒的物理过程,而且也存在于生命与非生命、能源、环境与材料等许多领域。本文对补偿效应的定位、理论解释及适用范围进行了探讨,指出其在化学/化工动力学中占有重要位置,不仅是一条定律,而且是与质量作用定律、Arrhenius定律并列的又一条基本定律。本文从统计学角度对补偿效应进行了概率分析,试图对其给出更为广义的理论解释,并指出,均相反应体系和非均相反应体系本质上都是不均匀的。中间络合物生成具有耗散结构特征,在近平衡(准平衡)线性区进行,无序度减小伴随着能量及无序度的同向变化,这是补偿效应存在的根本原因。从而提出了反应速率常数中能量分布、无序度分布的概率因子。其对补偿效应的概率解释与能量指数分布说/焓熵补偿关系说是统一的而非对立的。进而还讨论了自然指数律/自然补偿律,指出补偿效应是自然界存在/运动所遵循的自然律在化学反应领域的具体体现。
The compensation effect reveals the compensative relationship between the pre-exponential factor( k_0) and the exponential factor(-E/R_gT) in the Arrhenius equation,which relationship exists not only in the heterogeneous,homogeneous catalytic reaction systems but also in noncatalytic reaction systems whose occurrence needs to overcome energy barrier. The compensative influences,in broader ways,can also be found in life science,biology,energy,environment and material sciences. The effort of this work is to explain the compensation effect as one of the laws beside the mass interaction and the Arrhenius equation. The paper attempts to explain the compensation effect based on the probability analysis,pointing out that the absolute ununiformity of the heterogeneous and homogeneous systems and the energy Bolzmann exponential distribution as well as the distribution of disorder degree are the basis of the general compensation effect. This explanation also agrees with that in the theory of enthalpy-entropy compensation. Additional efforts are made to look at the compensation phenomena or natural exponential distribution phenomena in nature,trying to conclude that the compensation effect in chemical kinetics is the law that more phenomena in nature may follow.
The compensation effect reveals the compensative relationship between the pre-exponential factor( k_0) and the exponential factor(-E/R_gT) in the Arrhenius equation,which relationship exists not only in the heterogeneous,homogeneous catalytic reaction systems but also in noncatalytic reaction systems whose occurrence needs to overcome energy barrier. The compensative influences,in broader ways,can also be found in life science,biology,energy,environment and material sciences. The effort of this work is to explain the compensation effect as one of the laws beside the mass interaction and the Arrhenius equation. The paper attempts to explain the compensation effect based on the probability analysis,pointing out that the absolute ununiformity of the heterogeneous and homogeneous systems and the energy Bolzmann exponential distribution as well as the distribution of disorder degree are the basis of the general compensation effect. This explanation also agrees with that in the theory of enthalpy-entropy compensation. Additional efforts are made to look at the compensation phenomena or natural exponential distribution phenomena in nature,trying to conclude that the compensation effect in chemical kinetics is the law that more phenomena in nature may follow.
引文
[1]F H constable.Proc.Roy.Soc.A,1925,108:355~378.
[2]吴小平,郑永飞.岩石学报.2003,19(4):729~738.
[3]D Kumar,S Kumar.Bull.Mater.Sci.,2004,27(5):441~444.
[4]O A Khakhel,T P Romashko,Y E Sakhno.J.Phys.Chem.B,2007,111(25):7331~7335.
[5]O A Khakhel',T P Romashko.J.Phy.Chem.A,2016,120(12):2035.
[6]L Liu,Q X Guo.Chem.Rev.,2001,101(3):673~695.
[7]A Corma,F LIopis,J B Monton et al.J.Catal.,1993,142:97~109.
[8]G Kemeny,B Rosenberg.Nature,1973,243(5407):400~401.
[9]H M J Boots,P K de Bokx.J.Phys.Chem.,1989,93(25):8240~8243.
[10]J B Patrick.Phys.Chem.,2012,14(1):327~336.
[11]C B Geoffrey,M A Keane.Catal.Rev.,2000,42(3):323~383.
[12]G M Schwab.J.Catal.,1983,84(1):1~7.
[13]G M Schwab.Springer Berlin Heidelberg,1931.
[14]M布达,吉加-姆阿达苏.多相催化反应动力学上海:复旦大学出版社,1988:46,71~140.
[15]G C Bond.Handb.Heterogen.Chem.,1997,2:752.
[16]郭汉贤.应用化工动力学.北京:化学工业出版社,2003:88~96.
[17]胡荣祖,王胜利等.热分析动力学,北京:科学出版社,2001:209~229.
[18]G C Bond.Catalysis By Metals.London:Academic,1962,157~179.
[19]A K Galwey.Adv.Catal.,1977,26:247~315.
[20]金家骏.液相化学反应动力学原理.上海科学技术出版社,1984,37~41.
[21]A N Aleshin.Interf.Sci.,2002,10:5~12.
[22]李彦旭,李春虎,郭汉贤等.燃料化学学报,1999,27(6):529~534.
[23]W B Sing,Q P Kong,D A Molodor et al.Acta Mater.,2009,57:3327~3331.
[24]V PKatakov.Opt.spekrosk.XVlll.1965,54~57.
[25]B Rosenberg,G Kemeny,R C Switzer et al.Nature,1971,232(5311):471~473.
[26]B E C Banks,V Damjanovic,C A Vernon.Nature,1972,17:147~148.
[27]V Lai,C Li,W L Hung et al.Food Chem.,2000,68(3):319~325.
[28]R Dearnley.Mineral.Mag.,1993,57:337~348.
[29]I A Weinstein,A S Vokhmintsev,V S Kortov.Radiat.Meas.,2008,43(2):259~262.
[30]邢大立,赵祥臻,王睿泰.波谱学杂志.2000,17(3):217~222.
[31]J J M Ramos,J F Mano,B B Sauer.Polymer,1997,38(5):1081~1089.
[32]宋洪伟,郭守仁,胡壮麒.金属学报,1999,35(9):948~950.
[33]K B Catherine,K Krishnan,K N Ninnan.J.Therm.Anal.Calorim.,2000,59(1~2):93~100.
[34]谈世韶,李春虎,郭汉贤.催化学报,1999,(3):101~107.
[35]邹凤楼,李春虎,郭汉贤.分子催化,1994,8(4):305~311.
[36]梁美生.太原理工大学硕士学位论文,1991.
[37]H Wang,S Tan,H Guo.J.Fuel Chem.Tech.,1996,24(4):21~26.
[38]郭汉贤,樊惠玲,李彦旭.化学学报,2002,60(10):1806~1810.
[39]武增华,许玲,王立新.化学学报,2001,59(11):1914~1918.
[40]上官炬.太原理工大学博士学位论文,2006.
[41]李晓东.太原工业大学硕士学位论文,1990.
[42]郭汉贤,谈世韶.催化补偿效应-表面Arrhenius方程的探讨.第五届全国化学反应工程学术报告会文集.天津.1993.40~43.
[43]何德辉,刘惠云.化肥催化剂实用手册.北京:化学工业出版社,1992,268~271.
[44]陈五平.无机化工工艺学(一)合成氨.北京:化学工业出版社,1979:145,259.
[45]方鼎业.甲醇生产技术及进展.华东化工学院出版社,1990,182~195.
[46]冯丽娟.中国科学院山西煤炭化学研究所博士论文,1992.
[47]张永发,谢克昌.燃料化学学报,1991,19(4):359~364.
[48]魏兴海,沈平.燃料化学学报,1992,20(1):102~106.
[49]李淑芬,陈寿玲.天津大学学报,1996,29(2):259~264.
[50]M P Suárez,A Palermo,C M Aldao.J.Therm.Anal.,1994,41(4):807~816.
[51]R K Agrawal.J.Therm.Anal.,1986,31(1):73~86.
[52]王文钊,刘朝,唐经文.生物质化学工程,2008,42(4):13~16.
[53]P Budrugeac,E Segal.J.Therm.Anal.Calorim.,1999,56(2):835~842.
[54]刘乃安,汪秉宏,范维澄.火灾科学,2002,11(2):63~69.
[55]P V Menacherry,G L Haller.J.Catal.,1997,167(2):425~437.
[56]ΒИМих еева,Гидриды Переходных Металлов,Изд.Акад:НаукСССР,1959.
[57]陈建国.条件哲学与互补原理,江西:江西人民出版社,2009:176~183.
[58]A K Galwey.Adv.Catal.,1977,26(2):247~322.
[59]E Cremer.Adv.Catal.,1955,7:75~91.
[60]W M C Conner Jr,J A Schwarz.Chem.Eng.Commun.,1987,55(1~6):129~138.
[61]罗东斯基著,郭燮贤译.催化剂基本原理.北京:科学出版社,1956:25~50.
[62]B H Kaye著,徐新阳译.分形漫步.沈阳:东北大学出版社,1994:41~81.
[63]A K Galwey,M E Brown.J.Catal.,1979,60(2):335~338.
[64]A.爱因斯坦,L.英费尔德.物理学的进化.上海:上海科学技术出版社,1962:219~221(附图).
[65]张挺芳.熵、自由能与功函.上海:华东师范大学出版社,1983:44~56.
[66]A K Galwey,M E Brown.Thermochim.Acta,1997,300:107~115.
[67]吴越,杨向光.化学进展,2003,15(2):81~91.
[68]吴越.催化化学(下).北京:北京科学出版社,1990:75~77,107~115,252~255.
[69]沈小峰,胡岗,姜路.耗散结构论.上海:上海人民出版社,1983:33~35.
[70]申维.耗散结构、自组织、突发理论与地球科学.北京:地质出版社,2008:1~18.
[71]赖国华,周仁贤,韩晓祥等.化学通报,2005,68(12):928~934.
[72]李浙生.倏忽之间:混沌与认识.北京:冶金工业出版社,2002.
[73]韩德刚,高盘良.化学动力学基础.北京:北京大学出版社,1987:145~151.
[74]R.P.H.加塞,W.G.理查兹著,曾实译,熵及能级.北京:人民教育出版社,1981:21~28.
[75]乌杰.系统辩证法.北京:人民出版社,1991:66~71,107~115,188~193.
[76]王琪.化学动力学导论.吉林:吉林人民出版社,1982:184~187.
[77]张士宪,李远刚,何小凤.湿法冶金,2007,26(4):169~173.
[78]自然律,中国百科网(www.Chinabaike.com),2017,互动百科,(www.baike.com),2017
[79][以]Eli Maor著.周昌智,毛兆荣译.e的故事,(e:The story of a Number).北京:人民邮电出版社,2010.
[80]丁深.堀场芳数.e的奥秘.北京:科学出版社,1998.
[81]百度知道:费希纳的定律.(zhidao.baidu.com).
[82]钟健夫.自然律-美学家和艺术家的瑰宝,人人网(blog.renren.com/share),1984.
[83]ghx(郭汉贤)自然律-螺线的奥秘.(PPS),文化传播网(www.52e-mail.com).
[84]法布尔.昆虫记-第34章.蜘蛛的几何学.北京:作家出版社,1997.
[85]方海泉,周铁军,桑宝祥等.数学理论与应用,2009,2(4):10~13.
[86]引力波.百度图片,(Image.baidu.com)2017.
[87]R K Agrawal.J.Therm.Anal.,1989,35:909~917.
[88]G Menteanu,P Budrageac,L Ilieva et al.J.Mater.Sci.,2003,38:1995~2000.
[89]刘旦初.化学世界,1998,7:389~391.
[90]戈革.自然杂志,1990,(06):374~375.
[91]程峰.西南民族学院学报-哲学社会科学版.2001,10:27~31.
[2]吴小平,郑永飞.岩石学报.2003,19(4):729~738.
[3]D Kumar,S Kumar.Bull.Mater.Sci.,2004,27(5):441~444.
[4]O A Khakhel,T P Romashko,Y E Sakhno.J.Phys.Chem.B,2007,111(25):7331~7335.
[5]O A Khakhel',T P Romashko.J.Phy.Chem.A,2016,120(12):2035.
[6]L Liu,Q X Guo.Chem.Rev.,2001,101(3):673~695.
[7]A Corma,F LIopis,J B Monton et al.J.Catal.,1993,142:97~109.
[8]G Kemeny,B Rosenberg.Nature,1973,243(5407):400~401.
[9]H M J Boots,P K de Bokx.J.Phys.Chem.,1989,93(25):8240~8243.
[10]J B Patrick.Phys.Chem.,2012,14(1):327~336.
[11]C B Geoffrey,M A Keane.Catal.Rev.,2000,42(3):323~383.
[12]G M Schwab.J.Catal.,1983,84(1):1~7.
[13]G M Schwab.Springer Berlin Heidelberg,1931.
[14]M布达,吉加-姆阿达苏.多相催化反应动力学上海:复旦大学出版社,1988:46,71~140.
[15]G C Bond.Handb.Heterogen.Chem.,1997,2:752.
[16]郭汉贤.应用化工动力学.北京:化学工业出版社,2003:88~96.
[17]胡荣祖,王胜利等.热分析动力学,北京:科学出版社,2001:209~229.
[18]G C Bond.Catalysis By Metals.London:Academic,1962,157~179.
[19]A K Galwey.Adv.Catal.,1977,26:247~315.
[20]金家骏.液相化学反应动力学原理.上海科学技术出版社,1984,37~41.
[21]A N Aleshin.Interf.Sci.,2002,10:5~12.
[22]李彦旭,李春虎,郭汉贤等.燃料化学学报,1999,27(6):529~534.
[23]W B Sing,Q P Kong,D A Molodor et al.Acta Mater.,2009,57:3327~3331.
[24]V PKatakov.Opt.spekrosk.XVlll.1965,54~57.
[25]B Rosenberg,G Kemeny,R C Switzer et al.Nature,1971,232(5311):471~473.
[26]B E C Banks,V Damjanovic,C A Vernon.Nature,1972,17:147~148.
[27]V Lai,C Li,W L Hung et al.Food Chem.,2000,68(3):319~325.
[28]R Dearnley.Mineral.Mag.,1993,57:337~348.
[29]I A Weinstein,A S Vokhmintsev,V S Kortov.Radiat.Meas.,2008,43(2):259~262.
[30]邢大立,赵祥臻,王睿泰.波谱学杂志.2000,17(3):217~222.
[31]J J M Ramos,J F Mano,B B Sauer.Polymer,1997,38(5):1081~1089.
[32]宋洪伟,郭守仁,胡壮麒.金属学报,1999,35(9):948~950.
[33]K B Catherine,K Krishnan,K N Ninnan.J.Therm.Anal.Calorim.,2000,59(1~2):93~100.
[34]谈世韶,李春虎,郭汉贤.催化学报,1999,(3):101~107.
[35]邹凤楼,李春虎,郭汉贤.分子催化,1994,8(4):305~311.
[36]梁美生.太原理工大学硕士学位论文,1991.
[37]H Wang,S Tan,H Guo.J.Fuel Chem.Tech.,1996,24(4):21~26.
[38]郭汉贤,樊惠玲,李彦旭.化学学报,2002,60(10):1806~1810.
[39]武增华,许玲,王立新.化学学报,2001,59(11):1914~1918.
[40]上官炬.太原理工大学博士学位论文,2006.
[41]李晓东.太原工业大学硕士学位论文,1990.
[42]郭汉贤,谈世韶.催化补偿效应-表面Arrhenius方程的探讨.第五届全国化学反应工程学术报告会文集.天津.1993.40~43.
[43]何德辉,刘惠云.化肥催化剂实用手册.北京:化学工业出版社,1992,268~271.
[44]陈五平.无机化工工艺学(一)合成氨.北京:化学工业出版社,1979:145,259.
[45]方鼎业.甲醇生产技术及进展.华东化工学院出版社,1990,182~195.
[46]冯丽娟.中国科学院山西煤炭化学研究所博士论文,1992.
[47]张永发,谢克昌.燃料化学学报,1991,19(4):359~364.
[48]魏兴海,沈平.燃料化学学报,1992,20(1):102~106.
[49]李淑芬,陈寿玲.天津大学学报,1996,29(2):259~264.
[50]M P Suárez,A Palermo,C M Aldao.J.Therm.Anal.,1994,41(4):807~816.
[51]R K Agrawal.J.Therm.Anal.,1986,31(1):73~86.
[52]王文钊,刘朝,唐经文.生物质化学工程,2008,42(4):13~16.
[53]P Budrugeac,E Segal.J.Therm.Anal.Calorim.,1999,56(2):835~842.
[54]刘乃安,汪秉宏,范维澄.火灾科学,2002,11(2):63~69.
[55]P V Menacherry,G L Haller.J.Catal.,1997,167(2):425~437.
[56]ΒИМих еева,Гидриды Переходных Металлов,Изд.Акад:НаукСССР,1959.
[57]陈建国.条件哲学与互补原理,江西:江西人民出版社,2009:176~183.
[58]A K Galwey.Adv.Catal.,1977,26(2):247~322.
[59]E Cremer.Adv.Catal.,1955,7:75~91.
[60]W M C Conner Jr,J A Schwarz.Chem.Eng.Commun.,1987,55(1~6):129~138.
[61]罗东斯基著,郭燮贤译.催化剂基本原理.北京:科学出版社,1956:25~50.
[62]B H Kaye著,徐新阳译.分形漫步.沈阳:东北大学出版社,1994:41~81.
[63]A K Galwey,M E Brown.J.Catal.,1979,60(2):335~338.
[64]A.爱因斯坦,L.英费尔德.物理学的进化.上海:上海科学技术出版社,1962:219~221(附图).
[65]张挺芳.熵、自由能与功函.上海:华东师范大学出版社,1983:44~56.
[66]A K Galwey,M E Brown.Thermochim.Acta,1997,300:107~115.
[67]吴越,杨向光.化学进展,2003,15(2):81~91.
[68]吴越.催化化学(下).北京:北京科学出版社,1990:75~77,107~115,252~255.
[69]沈小峰,胡岗,姜路.耗散结构论.上海:上海人民出版社,1983:33~35.
[70]申维.耗散结构、自组织、突发理论与地球科学.北京:地质出版社,2008:1~18.
[71]赖国华,周仁贤,韩晓祥等.化学通报,2005,68(12):928~934.
[72]李浙生.倏忽之间:混沌与认识.北京:冶金工业出版社,2002.
[73]韩德刚,高盘良.化学动力学基础.北京:北京大学出版社,1987:145~151.
[74]R.P.H.加塞,W.G.理查兹著,曾实译,熵及能级.北京:人民教育出版社,1981:21~28.
[75]乌杰.系统辩证法.北京:人民出版社,1991:66~71,107~115,188~193.
[76]王琪.化学动力学导论.吉林:吉林人民出版社,1982:184~187.
[77]张士宪,李远刚,何小凤.湿法冶金,2007,26(4):169~173.
[78]自然律,中国百科网(www.Chinabaike.com),2017,互动百科,(www.baike.com),2017
[79][以]Eli Maor著.周昌智,毛兆荣译.e的故事,(e:The story of a Number).北京:人民邮电出版社,2010.
[80]丁深.堀场芳数.e的奥秘.北京:科学出版社,1998.
[81]百度知道:费希纳的定律.(zhidao.baidu.com).
[82]钟健夫.自然律-美学家和艺术家的瑰宝,人人网(blog.renren.com/share),1984.
[83]ghx(郭汉贤)自然律-螺线的奥秘.(PPS),文化传播网(www.52e-mail.com).
[84]法布尔.昆虫记-第34章.蜘蛛的几何学.北京:作家出版社,1997.
[85]方海泉,周铁军,桑宝祥等.数学理论与应用,2009,2(4):10~13.
[86]引力波.百度图片,(Image.baidu.com)2017.
[87]R K Agrawal.J.Therm.Anal.,1989,35:909~917.
[88]G Menteanu,P Budrageac,L Ilieva et al.J.Mater.Sci.,2003,38:1995~2000.
[89]刘旦初.化学世界,1998,7:389~391.
[90]戈革.自然杂志,1990,(06):374~375.
[91]程峰.西南民族学院学报-哲学社会科学版.2001,10:27~31.