Chemistry Kinetics

Reaction kinetics are an important component of chemical research in the laboratory and in the classroom. The concepts of kinetic analysis are the building blocks of many undergraduate chemistry courses as well as the basis for many research projects. Olis supports the monitoring of reactions by optical spectroscopy in the ultraviolet, visible, or near infrared spectral regions on timescales from microseconds to hours. Kinetic reactions can be triggered by a variety of methods including manual mixing, stopped flow mixing, or flash photolysis. However, any trigger that can be initiated by a TTL signal can be integrated into an Olis system.

Absorbance and Fluorescence

The most powerful and sophisticated Olis kinetic system is the RSM 1000, which can be easily configured for use in any wavelength range from deep ultraviolet to near infrared. Its patented ScanDisk technology supports the collection of up to 1000 spectral scans per second. For absorbance spectra at more modest rates, the HPDA 8452 collects spectra scans at a rate of up to 10 scans/second. The RSM 1000, DB 620, or HPDA 8452 can be utilized for single wavelength kinetic wavelengths.

The DM 45, DM 245, RSM 1000F, and SLM series fluorimeters provide the ability to monitor fluorescence reactions as well.

Stopped-flow, flash lamps, LEDs, Peltier TLC 45, Peltier TLC 50, and magnetic stirrers are popular accessories for these measurements.

Olis instruments include the software package GlobalWorks, which is a powerful tool in the elucidation of kinetic mechanisms. Spectral data can be globally fit using singular value decomposition (SVD). With this fitting option, spectra of each kinetic component are extracted. This additional information allows fitting to more complex mechanism and helps to characterize the reaction intermediates. Spectral information also proves helpful in eliminating incorrect mechanisms that require impossible spectra in order to be correct.

Client Publications
OA Babich and ES Gould. (2002). Electron transfer. Part 148. Reactions of corrin-bound cobalt(III) with s2?metal-ion reducing centers.
      Inorganica Chimica Acta 336, 80-86
Achieved using the OLIS Durrum-Gibson

MP Jensen and DP Riley. (2002). Peroxynitrate Decomposition Activities of Iron Porphyrin Complexes.
      Inorg. Chem. 41, 4788-4797
Achieved using the OLIS RSM 1000

RA Crowell, R Lian, MC Sauer Jr., DA Oulianov, IA Shkrob. (2003). Geminate recombination of hydroxyl radicals generated in 200 nm photodissociation of aqueous hydrogen peroxide.
      Chem Phys Lett 383, 481-485
Achieved using the OLIS Cary 14

JA Jee, S Eigler, N Jux, A Zahl, R van Eldik. (2007). Influence of an Extremely Negatively Charged Porphyrin in the Reversible Binding Kinetics of NO to Fe(III) and the Subsequent Reductive Nitrosylation.
      Inorg. Chem. 46, 3336-3352
Achieved using the OLIS Kinfit

X Shan, A Ellern, IA Guzei, JH Espenson. (2004). Ligand Displacement and Oxidation Reactions of Methyl (oxo)rhenium(V) Complexes.
      Inorg. Chem. 43, 3854-3862
Achieved using the OLIS RSM 1000

KS Haygarth, TW Marin, I Janik, K Kanjana, CM Stanisky, DM Bartels. (2010). Carbonate Radical Formation in Radiolysis of Sodium Carbonate and Bicarbonate Solutions up to 250 ?C and the Mechanism of its Second Order Decay.
      J Phys Chem A 114, 2142-2150
Achieved using the OLIS RSM 1000

CR Curz, R Kissner, T Nauser, D Perrin, WH Koppenol. (2003). Rapid scavenging of peroxynitrous acid by monohydroascorbate.
      Free Radical Biology and Medicine 35, 1529-1537
Achieved using the OLIS RSM 1000

JM Hodgkiss, CJ Chang, BJ Pistorio, DG Nocera. (2003). Transient Absorption Studies of the Pacman Effect in Spring-Loaded Diiron(III) u-oxo Bisporphyrins.
      Inorg. Chem. 42, 8270-8277
Achieved using the OLIS Cary 17

S Swavey, MC Ghosh, V Manivannon, ES Gould. (2000). Electron transfer. 143. Reductions of benzopyrazine derivatives with indium(I).
      Inorganica Chimica Acta 306, 65-69
Achieved using the OLIS Durrum-Gibson

E Solomon-Rapaport, A Masarwa, H Cohen, D Meyerstein. (2000). Catalyzed autoxidation of azide by cobalt(II) (2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene)2+.
      Inorganica Chimica Acta 307, 42-47
Achieved using the OLIS Kinfit

MR Filipovic, J Miljkovic, T Nauser, M Royzen, K Klos, TE Shubina, WH Koppenol, SJ Lippard, I Ivanic-Burmazovic. (2012). Chemical Characterization of the Smallest S-nitrosothiol, HSNO; Cellular Cross-talk of H2S and S-nitrosothiols.
      J.Amer. Chem. Soc. 134, 12016-12027
Achieved using the OLIS HPDA 8452

TV Duncan, PP Ghoroughchian, IV Rubstov, DA Hammer, MJ Therien. (2008). Ultrafast Excited-State Dynamics of Nanoscale Near-Infrared Emissive Polymersomes.
      JACS 130, 9773-9784
Achieved using the OLIS Cary 14

JE Jee, X Ribas, JM Lopez-Valbuena, L Gomez, M Corbella, A Llobet, J Mahia, J Benet-Bucholtz, M Costas, R van Eldik. (2007). Structural and Kinetic Study of Reversible CO2 Fixation by Dicopper Macrocyclic Complexes. From Intramolecular Binding to Self-Assembly of Molecular Boxes.
      Inorg. Chem. 46, 9098-9110
Achieved using the OLIS Kinfit

XL Cui and RS Brown. (2000). Mechanistic Evaluation of the Halocyclization of 4-Penten-1-ol by Some Bis(2-substituted pyridine) and Bis(2,6-disubstituted pyridine)bromonium Triflates.
      J. Org. Chem. 65, 5653-5658
Achieved using the OLIS Cary 17

WR Harris, Z Wang, C Brook, B Yang, A Islam. (2003). Kinetics of Metal Ion Exchange Between Citric Acid and Serum Transferrin.
      Inorg. Chem. 42, 5880-5889
Achieved using the OLIS Cary 14

JF Read, J John, J MacPherson, C Schaubel, A Theriault. (2001). The kinetics and mechanism of the oxidation of inorganic oxysulfur compounds by potassium ferrate.: Part I. Sulfite, thiosulfate and dithionite ions.
      Inorganic Chimica Acta 315, 96-106
Achieved using the OLIS Durrum 110

W Desloges, AA Neverov, RS Brown. (2004). Zn2+-Catalyzed Metholysis of Phosphate Triesters: A Process for Catalytic Degradation of the Organophosphorus Pesticides Paraxon and Fenitrothion.
      Inorg. Chem. 43, 6752-6761
Achieved using the OLIS Cary 17

D Schweitzer, J Shearer, DK Rittenberg, SC Shoner, JJ Ellison, R Loloee, S Lovell, D Barnhart, JA Kovacs. (2002). Enhancing Reactivity via Structural Distortion.
      Inorg. Chem. 41, 3128-3136
Achieved using the OLIS RSM 1000 SF

ZD Bugarcic, B Petrovic, E Zangrando. (2004). Kinetics and mechanism of the complex formation of [Pd(NNN)Cl]+?with pyridines in methanol: synthesis and crystal structure of [Pd(terpy)(py)](ClO4)2.
      Inorganica Chemica Acta 357, 2650-2656
Achieved using the OLIS Kinfit

AA Neverov, G Gibson, RS Brown. (2003). Europium Ion Catalyzed Methanolysis of Esters at Neutral pH and Ambient Temperature. Catalytic Involvement of Eu3+(CH3O)(CH3OH)x.
      Inorg. Chem. 42, 228-234
Achieved using the OLIS Cary 17

MJ Vasbinder and A Bakac. (2008). Kinetics and mechanism of the reactions of ozone with superoxo, hydroperoxo, and hydrido complexes of rhodium(III).
      Inorganica Chemica Acta 361, 3193-3198
Achieved using the OLIS RSM 1000

S Nisar and SA Kazmi. (2010). Spectrofluorometric study of iron removal from bovine lactoferrin by ethylenediamminetetraacetic acid?.
      Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 77, 933
Achieved using the OLIS HPDA 8452

JJ Scepaniak, CG Magarit, JN Harvey, JM Smith. (2011). Nitrogen Atom Transfer from Iron(IV) Nitrido Complexes: A Dual-Nature Transition State for Atom Transfer.
      Inorg. Chem. 50, 9508-9517
Achieved using the OLIS RSM 1000

JD Soper, IJ Rhile, AG DiPasquale, JM Mayer. (2004). Oxidation of TpOsIII(NH2Ph)Cl2?to TpOsIV(NHPh)Cl2?by O2.
      Polyhedron 23, 323-329
Achieved using the OLIS RSM 1000

AK Gupta and WB Tolman. (2010). Copper/?-Ketocarboxylate Chemistry With Supporting Peralkylated Diamines: Reactivity of Copper(I) Complexes and Dicopper?Oxygen Intermediates.
      Inorg Chem 49, 3531-3539
Achieved using the OLIS GlobalWorks

A Theodoridis and Rvan Eldik. (2004). The role of positively charged meso-substituents on the kinetics of the reductive nitrosylation of iron(III)-porphyrins: The catalytic role of nitrite.
      J Mol Catalysis A: Chemical 224, 197-205
Achieved using the OLIS Kinfit

BM Alzoubi and R van Eldik. (2004). Mechanistic Elucidation of the Substitution Behavior of Alkyl Cobaloximes in Water and Methanol as Solvents.
      Inorg. Chem. 43, 6093-6100
Achieved using the OLIS Kinfit

J Sun and DM Stanbury. (2002). Trace metal-ion catalysis of oxidation of aqueous hydrogen sulfide by outer-sphere oxidants.
      Inorganica Chimica Acta 336, 39-45
Achieved using the OLIS RSM 1000

JH Espenson, X Shan, Y Wang, R Huang, DW Lahti, J Dixon, G Lente, A Ellern, IA Guzei. (2002). Synthesis and Characterization of Dimetallic Oxorhenium (V) and Dioxorhenium (VII) Compounds, and a Study of Stoichiometric and Catalytic Reactions.
      Inorg. Chem. 41, 2583-2591
Achieved using the OLIS RSM 1000

I Ivanovic-Burmazovic, MSA Hamza, R van Eldik. (2002). A Detailed Mechanistic Study of the Substitution Behavior of an Unusual Seven-Coordinate Iron (III) Complex in Aqueous Solution.
      Inorg. Chem. 41, 5150-5161
Achieved using the OLIS Kinfit

T Egawa, A Tsuneshige, M Suematsu, T Yonetoni. (2007). Method for Determination of Association and Dissociation Rate Constants of Reversible Bimolecular Reactions by Isothermal Titration Calorimeters.
      Anal. Chem. 79, 2972-2978
Achieved using the OLIS RSM 1000

MJ Hynes and M O'Coinceanainn. (2001). The kinetics and mechanisms of the reaction of iron(III) with gallic acid, gallic acid methyl ester and catechin.
      J Inorganic Chemistry 85, 131-142
Achieved using the OLIS KinFit

A Brausam and R van Eldik. (2004). Further mechanistic Information on the Reaction between Fe(II)(EDTA) and Hydrogen Peroxide: Observation of a Second Reaction Step and Importance of pH.
      Inorg. Chem. 43, 5351-5359
Achieved using the OLIS Kinfit

JE Lee and R van Eldik. (2006). Mechanistic Studies on the Nitrite-Catalyzed Reductive Nitrosylation of Highly Charged Anionic and Cationic Fe(III) Porphyrin Complexes.
      Inorg. Chem. 45, 6523-6534
Achieved using the OLIS Kinfit

A Wu, EA Mader, A Datta, DA Hrovat, WT Borden, JM Mayer. (2009). Nitroxyl Radical Plus Hydroxylamine Pseudo Self-Exchange Reactions: Tunneling in Hydrogen Atom Transfer.
      JACS 131, 11985-11997
Achieved using the OLIS RSM 1000

MY Udugala-Ganehenege, MJ Heeg, LM Hryhorczuk, LE Wenger, JF Endicott. (2001). Electron/Atom Transfer in Halo-Bridged Homobimetallic Complexes. Structure and Donor-Acceptor Properties of Face to Face Dicopper Complexes with Terazamacrocyclic Ligands.
      Inorg. Chem. 40, 1614-1625
Achieved using the OLIS Cary 14

T Schneppensieper, A Wanat, G Stochel, R van Eldik. (2002). Mechanistic Information on the Reversible Binding of NO to Selected Iron(II) Chelated from Activation Parameters.
      Inorg. Chem. 41, 2565-2573
Achieved using the OLIS Kinfit

S Herold. (2004). Nitrotyrosine, dityrosine, and nitrotryptophan formation from metmyoglobin, hydrogen peroxide, and nitrite.
      Free Radical Biology and Medicine 36, 565-579
Achieved using the OLIS RSM 1000

MT Caudle and VL Pecoraro. (2000). Mechanism for the Reduction of the Mixed-Valent Mn(III)Mn(IV)[2-Ohsalpn]2+ Cmplex by Tertiary Amines.
      Inorg. Chem. 39, 5831-5837
Achieved using the OLIS RSM 1000

MM Shoukry and AA El-Sherif. (2011). The palladium(II)-picolylamine promoted hydrolysis of amino acid esters; kinetic evidence for inter- and intramolecular mechanisms.
      Progress in Reaction Kinetics and Mechanism 36, 215-226
Achieved using the OLIS Kinfit

VN Nemykin and P Basu. (2005). Oxygen Atom Transfer Reactivity from a Dioxin Mo(VI) Complex to Tertiary Phosphines: Synthesis, Characterization, and Structure of Phosphoryl Intermediate Complexes.
      Inorg. Chem. 44, 7494-7502
Achieved using the OLIS Cary 14

M O'Coinceanainn and MJ Hynes. (2001). The kinetics and mechanisms of the reactions of aluminium(III) with gallic acid, gallic acid methyl ester and adrenaline.
      J Inorganic Biochemistry 84, 1-12
Achieved using the OLIS Kinfit

AG Cregan, NE Brasch, R van Eldik. (2001). Thermodynamic and Kinetic Studies on the Reaction btween the Vitamin B12 Derivative beta-(N-Methylimidazolyl) Cobalamin and N-Methylimidazole: Ligand Displacement at the alpha Axial site of Cobalamins.
      Inorg. Chem. 40, 1430-1438
Achieved using the OLIS Kinfit

AF Vanin, AA Papina, VA Serezhenkov, WH Koppenol. (2004). The mechanisms of S-nitrosothiol decomposition catalyzed by iron.
      Nitric Oxide 10, 60-73
Achieved using the OLIS RSM 1000

JS de Melo, J Pina, HD Burrows, S Brocke, O Herzog, E Thorn-Csanyi. (2004). The effect of substitution and isomeric imperfection on the photophysical behaviour of?p-phenylenevinylene trimers.
      Chem. Phys. Lett. 388, 236-241
Achieved using the OLIS Cary 14

JL Bourassa and PC Ford. (2000). Flash and continuous photolysis studies of Roussin?s red salt dianion Fe2S2(NO)42?in solution.
      Coordination Chemistry Reviews 200, 887-900
Achieved using the OLIS Cary 118

JE Lee, S Eigler, F Hampel, N Jux, M Wolak, A Zahl, G Stochel, and R van Eldik. (2005). Kinetic and Mechanistic Studies on the Reaction of Nitric Oxide with a Water-Soluble Octa-Anionic Iron(III) Porphyrin Complex.
      Inorg. Chem. 44, 7177-7731
Achieved using the OLIS Kinfit

KT Moore, IT Horvath, MJ Therien. (2000). Mechanistic Studies of (Porphinato) Iron-Catalyzed Isobutane Oxidation Comparative Studies of Three Classes of Electronic-Deficient Porphyrin Catalysts.
      Inorg. Chem. 39, 3125-3139
Achieved using the OLIS Cary 14

JF Read, SA Bewick, CR Graves, JM MacPherson, JC Salah, A theriault, AEH Wyland. (2000). The kinetics and mechanism of the oxidation of?s-methyl-l-cysteine,?l-cystine and?l-cysteine by potassium ferrate.
      Inorganica Chemica Acta 303, 244-255
Achieved using the OLIS Durrum 110

MSA Hamza, X Zou, KL Brown, R van Eldik. (2001). Equilibrium and Kinetic Studies on the Reactions of Alkylcobalamins with Cyanide.
      Inorg. Chem. 40, 5440-5447
Achieved using the OLIS Kinfit

N Koshino, Y Cai, JH Espenson. (2003). Kinetic Study of the Phthalimide N-Oxyl (PINO) Radical in Acetic Acid. Hydrogen Abstraction from C?H Bonds and Evaluation of O?H Bond Dissociation Energy of N-Hydroxyphthalimide.
      J. Phys. Chem A 107, 4262-4267
Achieved using the OLIS RSM 1000 SF

R Kirgan, M Simpson, C Moore, J Day, L Bui, C Tanner, DP Rillema. (2007). Synthesis, Characterization, Photophysical, and Computational Studies of Rhenium (I) Tricarbonyl Complexes Containing the Derivatives of Bipyrazine.
      Inorg. Chem. 46, 6464-6472
Achieved using the OLIS HPDA 8452

M Hirasawa, LM Rubio, JL Griffin, E Flores, A Herrero, J Li, S-K Kim, JK Hurley, G Tollin, DB Knaff. (2004). Complex formation between ferredoxin and?Synechococcus?ferredoxin:nitrate oxidoreductase.
      BBA Bioenergetics 1608, 155-162
Achieved using the OLIS DSM 10

JSW Tsang, AA Neverov, RS Brown. (2003). La3+-Catalyzed Methanolysis of Hydroxypropyl-p-Nitrophenyl Phosphate as a Model for the RNA Transesterification Reaction.
      JACS 125, 1559-1566
Achieved using the OLIS Cary 17

Y Cai, N Koshino, B Saha, JH Espenson. (2005). Kinetics of Self-Decomposition and Hydrogen Atom Transfer Reactions of Substituted Phthalimide N-Oxyl Radicals in Acetic Acid.
      J. Org. Chem. 70, 238-243
Achieved using the OLIS RSM 1000 SF

AA Neverov and RS Brown. (2001). La3+-Catalyzed Methanolysis of Phosphate Diesters: Remarkable Rate Acceleration of the Methanolysis of Diphenyl Phosphate, Methyl p-Nitrophenyl Phosphate, and Bis(p-nitrophenyl) Phosphate.
      Inorg. Chem. 40, 3588-3595
Achieved using the OLIS Cary 17

JJA Cooney, MD Carducci, AE McElhaney, HD Selby, JH Enemark. (2002). New Oxovanadium Bis(1,2-dithiolate) Compounds that Mimic the Hydrogen-Bonding Interactions at the Active Sites of Mononuclear Molybdenum Enzymes.
      Inorg. Chem. 41, 7086-7093
Achieved using the OLIS Cary 14

Y Han, J Harlan, P Stroessel, BJ Frost, JR Norton, S Miller, B Bridgewater, Q Xu. (2001). Rhenium Oxo Complexes of a Chelating Diyne Ligand. Sythesis and Study of the Kinetics of Protonation.
      Inorg. Chem. 40, 2942-2952
Achieved using the OLIS RSM 1000

G Bodemer, LM Ellis, PJ Lace, PE Mooren, NK Patel, MP ver Haag, AA Pacheco. (2004). Photochemically-induced reduction and rearrangements of?N,N?-bis-(carboxymethyl)-N,N?-dinitroso-1,4-phenylenediamine.
      J Photochemistry and Photobiolog A: Chemistry
Achieved using the OLIS RSM 1000

L Xia, AG Cregan, LA Berben, NE Brasch. (2004). Studies on the Function of Glutathionylcobalamin: Any Free Intracellular Aquacobalamin is Likely to be Rapidly and Irreversibly Converted to Glutathionylcobalamin.
      Inorg. Chem. 43, 6848-6857
Achieved using the OLIS Kinfit

JE Jee, A Comas-Vives, C Dinoi, G Vjaque, R van Eldik, A Lledos, R Poli. (2007). Nature of Cp*MoO2+ in Water and Intramolecular Proton-Transfer Mechanism by Stopped-flow Kinetics and Density Functional Theory Calculations.
      Inorg. Chem. 46, 4103-4113
Achieved using the OLIS Kinfit

O Pestovsky and A Bakac. (2006). Aqueous Ferryl(IV) Ion: Kinetics of Oxygen Atom Transfer to Substrates and Oxo Exchange with Solvent Water.
      Inorg. Chem. 45, 814-820
Achieved using the OLIS RSM 1000

DC Crans, B Baruah, E Gaidamauskas, BG Lemons, BB Lorenz, MD Johnson. (2008). Impairment of ascorbic acid?s anti-oxidant properties in confined media: Inter and intramolecular reactions with air and vanadate at acidic pH.
      J Inorganic Biochem. 102, 1334-1347
Achieved using the OLIS RSM 1000