Kinetics Database Logo

Kinetics Database Resources

Simple Reaction Search

Search Reaction Database

Search Bibliographic Database

Set Unit Preferences

Feedback

Rate Our Products and Services

Help


Other Databases

NIST Standard Reference Data Program

NIST Chemistry Web Book

NDRL-NIST Solution Kinetics Database

NIST Computational Chemistry Comparison and Benchmark Database

The NIST Reference on Constants, Units, and Uncertainty

More...


Administrative Links

NIST home page

MML home page

Chemical and Biochemical Reference Data Division

MML home page

Chemical and Biochemical Reference Data Division

  NIST Logo Home
©NIST, 2013
Accessibility information
Author(s):   Schroden, J.J.; Teo, M.; Davis, H.F.
Title:   Dynamics of CO Elimination from Reactions of Yttrium Atoms with Formaldehyde, Acetaldehyde, and Acetone
Journal:   J. Chem. Phys.
Volume:   117
Page(s):   9258 - 9265
Year:   2002
Reference type:   Journal article
Squib:   2002SCH/TEO9258-9265

Reaction:   (CH3)2CO + YCO + Y(CH3)2
Reaction order:   2
Rate expression:   no rate data available
Category:  Other
Data type:   Other
Experimental procedure:   Molecular beam
Excitation technique:   Flash photolysis (laser or conventional)
Analytical technique:   Mass spectrometry
Comments:   No thermal rate data. Crossed molecular beam scattering study. Collision energies of >24 kcal/mol. Y(g) produced by 532 nm pulsed laser vaporization of Y(s). Products detected using 157 nms F2 excimer laser ionization TOF/MS.

Measured product channels and energies for Y plus R1R2C=O where R1, R2 was H and/or CH3 ?reactants CH2O, CH3CHO, CH3CHO-d4, and CH3C(O)CH3. Three possible reaction channels such as CH2O + Y goes to YH2 + CO or YCO + H2 or YCHO + H. Predominant channel is CO elimination with >95% for CH2O and CH3C(O)CH3 and >50% for CH3HO. Compared experimental potential energy product distribution with CCSD(T) ab initio calculations of potential energy surface calculated by Bayse JPCA 106, 4226 (2002). Found low lying intermediates and intermediate barriers (barrierless insertion and chemically activated rearrangements). Exothermic by about 25 kcal/mol with intermediates about 40-60 kcal/mol downhill and local barriers of about 10-30 kJ/mol below reactants.

View full bibliographic record.