Nickel peroxide: A more probable intermediate in the Ni(II)‐catalyzed decomposition of peroxomonosulfate

International Journal of Chemical Kinetics - Tập 39 Số 6 - Trang 320-327 - 2007
P. Thendral1, S. Shailaja1, M. Ramachandran1
1School of Chemistry, Madurai Kamaraj University, Madurai-625 021, India

Tóm tắt

AbstractThe Ni(II) ion catalyzed thermal decomposition of peroxomonosulfate (PMS) was studied in the pH range 3.42–5.89. The rate is first order in [PMS] and Ni(II) ion concentrations. At pH greater than or equal to 5.23, the reaction becomes zero order in [PMS] and this changeover in the order of the reaction occurs at a higher concentration of nickel ions. The first‐order kinetics in PMS can be explained as a rate‐limiting step and is the transformation of nickel peroxomonosulfate into nickel peroxide. This peroxide intermediate reacts rapidly with another PMS to give oxygen and Ni(II). The formation of nickel peroxide is associated with a small negative or nearly zero entropy of activation. The zero‐order kinetics in [PMS] can be explained by the fact that the hydrolysis of aquated nickel(II) ions into hydroxocompounds is the rate‐limiting step. The turnover number is 2 at pH 3.42 and increases with pH. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 320–237, 2007

Từ khóa


Tài liệu tham khảo

10.1021/ja01587a011

Goodman J. F., 1963, J Chem Soc, 2871

10.1021/j150561a024

10.1007/BF00625524

Csanyi L. S., 1962, Acta Chim Acad Sci Hung, 34, 383

10.1071/CH9700641

10.1021/ic50218a012

10.1071/CH9900321

Gilbert B. C., 1990, J Chem Soc, Perkin Trans 2, 1281

10.1039/ft9908603261

Bennet J. E., 1991, J Chem Soc, Perkin trans 2, 1105

Marsh C., 1989, Prog React Kinet, 15, 35

10.1021/ic00043a007

10.1016/0020-1693(95)90039-9

10.1021/ja952518m

Steenken S., 1988, Free Radicals: Chemistry, Pathology and Medicine, 51

10.1016/j.apcatb.2003.12.018

10.1016/S1010-6030(03)00293-4

10.1016/j.apcatb.2004.05.025

10.1021/es035121o

10.1021/es0263792

10.1021/jp052166y

10.1021/ie0401511

10.1002/kin.20168

10.1007/978-1-4613-4577-0_10

Biondini D., 2005, Eur J Org Chem, 3060

Nicholls D., 1973, Comprehensive Inorganic Chemistry, 1159

Baes C. F., 1976, The Hydrolysis of Cations

Shriver D. F., 2002, Inorganic Chemistry

10.1063/1.555808

10.1021/cr00033a006

10.1016/S0020-1693(96)05272-3

10.1021/ja963701y

10.1021/ic981342x

10.1021/ic035034x

10.1021/bi982587o

10.1021/ja00143a002

10.1021/ja9720218

Alipazaga M. V., 2005, Dalton Trans, 3738

10.1021/cr960421s

Lide D. R., 1997, CRC Hand book of Chemistry and Physics, 27

Thông tin
Thông tin xuất bản

International Journal of Chemical Kinetics

Tập 39 Số 6

320-327

Thông tin tác giả