A Treatment of Chemical Kinetics with Special Applicability to Diffusion Controlled Reactions

Noyes, Richard M.

doi:10.1063/1.1740394

A Treatment of Chemical Kinetics with Special Applicability to Diffusion Controlled Reactions

Journal Article · Wed Nov 11 00:00:00 EST 1953 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.1740394· OSTI ID:4405887

Noyes, Richard M. ^[1]

Columbia Univ., New York, NY (United States)

If a molecule is produced in a medium containing molecules able to react with it, its instantaneous reactivity is a function of the time since its formation. At very short times the reactivity is determined by the conventional ``true'' rate constant k, which is the product of the rate constant for encounters and the probability of reaction during an encounter. At long times (10—9 sec or greater in many liquids), the reactivity falls to a value determined by the ``long-time'' rate constant k'. The constants k and k' differ by the factor 1 — β', where β' is the probability that a specific pair of molecules separating from a nonreactive encounter will ultimately react with each other. If β' is small either because there is little chance of reaction per encounter (activation control), or because there is little chance the specific pair will undergo a subsequent encounter (as in gas phase), the two rate constants are virtually identical and conventional kinetics apply.

View Accepted Manuscript (DOE)

Research Organization:: Columbia Univ., New York, NY (United States)

Sponsoring Organization:: US Atomic Energy Commission (AEC)

NSA Number:: NSA-08-000731

OSTI ID:: 4405887

Report Number(s):: CU-2-53-AEC-314-Chem; NYO--3882

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 8 Vol. 22; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (18)

Probability that two diffusing molecules will collide Wijsman, Robert A. The Bulletin of Mathematical Biophysics, Vol. 14, Issue 2 https://doi.org/10.1007/BF02477710	journal	June 1952
Diffusion-controlled reaction rates Collins, Frank C.; Kimball, George E. Journal of Colloid Science, Vol. 4, Issue 4 https://doi.org/10.1016/0095-8522(49)90023-9	journal	August 1949
On the problem of random flights Quenouille, M. H. Mathematical Proceedings of the Cambridge Philosophical Society, Vol. 43, Issue 4 https://doi.org/10.1017/S0305004100023835	journal	October 1947
Diffusion-Controlled Reactions in Liquid Solutions Collins, Frank C.; Kimball, George E. Industrial & Engineering Chemistry, Vol. 41, Issue 11 https://doi.org/10.1021/ie50479a040	journal	November 1949
Self-diffusion and Structure of Liquid Water. III. Measurement of the Self-diffusion of Liquid Water with H ² , H ³ and O ¹⁸ as Tracers ¹ Wang, Jui Hsin; Robinson, Charles V.; Edelman, I. S. Journal of the American Chemical Society, Vol. 75, Issue 2 https://doi.org/10.1021/ja01098a061	journal	January 1953
Kinetics of the Polymerization of Methyl Methacrylate with Aliphatic Azobisnitriles as Initiators¹ Arnett, L. M. Journal of the American Chemical Society, Vol. 74, Issue 8 https://doi.org/10.1021/ja01128a048	journal	April 1952
Vinyl Polymerization with Radioactive Aliphatic Azobisnitrile Initiators¹ Arnett, L. M.; Peterson, J. H. Journal of the American Chemical Society, Vol. 74, Issue 8 https://doi.org/10.1021/ja01128a049	journal	April 1952
Experimental Measurement of the Effect of a Solvent on the Rate of a Very Fast Bimolecular Reaction Curme, H. G.; Rollefson, G. K. Journal of the American Chemical Society, Vol. 74, Issue 15 https://doi.org/10.1021/ja01135a015	journal	August 1952
II. The Efficiency of the Primary Photochemical Process for Halogens in Water. The Photochemical Reaction of Mn(II) and Br₂ Rutenberg, Aaron C.; Taube, Henry Journal of the American Chemical Society, Vol. 73, Issue 9 https://doi.org/10.1021/ja01153a115	journal	September 1951
Azo-Bis Nitriles. V.¹ Mechanism of the Decomposition of Azo Nitriles. Decomposition Products Overberger, C. G.; Berenbaum, M. B. Journal of the American Chemical Society, Vol. 73, Issue 10 https://doi.org/10.1021/ja01154a121	journal	October 1951
I. The Efficiency of the Primary Photochemical Process for Halogens in Water. The Photochemical Reaction of Mn(II) and Cl₂¹ Rutenberg, Aaron C.; Taube, Henry Journal of the American Chemical Society, Vol. 72, Issue 12 https://doi.org/10.1021/ja01168a054	journal	December 1950
Absolute Quantum Yields for Dissociation of Iodine in Inert Solvents Lampe, Frederick W.; Noyes, Richard M. Journal of the American Chemical Society, Vol. 76, Issue 8 https://doi.org/10.1021/ja01637a029	journal	April 1954
The collison mechanism and the primary photochemical process in solutions Rabinowitch, E.; Wood, W. C. Transactions of the Faraday Society, Vol. 32 https://doi.org/10.1039/tf9363201381	journal	January 1936
Collision, co-ordination, diffusion and reaction velocity in condensed systems Rabinowitch, E. Transactions of the Faraday Society, Vol. 33 https://doi.org/10.1039/tf9373301225	journal	January 1937
Diffusional Processes in the Growth of Aerosol Particles. II Frisch, H. L.; Collins, F. C. The Journal of Chemical Physics, Vol. 21, Issue 12 https://doi.org/10.1063/1.1698803	journal	December 1953
The Primary Quantum Yield of Dissociation of Iodine in Hexane Solution Zimmerman, Joseph; Noyes, Richard M. The Journal of Chemical Physics, Vol. 18, Issue 5 https://doi.org/10.1063/1.1747721	journal	May 1950
The Recombination of Iodine Atoms in Solution Noyes, Richard M. The Journal of Chemical Physics, Vol. 18, Issue 8 https://doi.org/10.1063/1.1747898	journal	August 1950
Stochastic Problems in Physics and Astronomy Chandrasekhar, S. Reviews of Modern Physics, Vol. 15, Issue 1 https://doi.org/10.1103/RevModPhys.15.1	journal	January 1943

Cited By (1)

Reaction rate in an evanescent random walkers system Ré, Miguel A.; Bustos, Natalia C. arXiv https://doi.org/10.48550/arxiv.1510.02069	text	January 2015

Figures / Tables (2)

Figure 1(p. 15)

TABLE I(p. 19)

Similar Records

Simple quantum model of ultracold polar molecule collisions

Journal Article · Sun Aug 15 00:00:00 EDT 2010 · Physical Review. A · OSTI ID:21448414

Vibrational deactivation on chemically reactive potential surfaces: An exact quantum study of a low barrier collinear model of H + FH, D + FD, H + FD and D + FH

Journal Article · Thu Feb 14 23:00:00 EST 1980 · J. Chem. Phys.; (United States) · OSTI ID:5484876

Flow reactor nitrations using dinitrogen pentoxide

Conference · Thu Nov 30 23:00:00 EST 1995 · OSTI ID:126578

Related Subjects

ACTIVATION
CHEMICAL REACTIONS
Chemistry
DIFFUSION
EQUATIONS
FLUORESCENCE
GASES
LIQUIDS
MEASURED VALUES
MOLECULES
PHOTOCHEMISTRY
PRODUCTION
REACTION KINETICS
REACTIVITY

A Treatment of Chemical Kinetics with Special Applicability to Diffusion Controlled Reactions

Citation Formats

References (18)

Cited By (1)

Figures / Tables (2)

Similar Records

Related Subjects