Isotope effects on isotope effects. Equilibrium nitrogen isotope effects on the basicity of pyridine in protium and deuterium oxides

Journal Article · Thu Jan 26 04:00:00 EST 1989 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100339a076· OSTI ID:5439098

Kurz, J L; Nasr, M M ^[1]

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1. Washington Univ., St. Louis, MO (USA)

The {sup 14}N/{sup 15}N isotope effect on the pK{sub a} of pyridinium ion is 18% larger in D{sub 2}O than in H{sub 2}O: pK{sub a}{sup 14} {minus} pK{sub a}{sup 15} = {minus}0.0090{sub 7} {plus minus} 0.0001{sub 6} in H{sub 2}O and {minus}0.0107{sub 2} {plus minus} 0.0001{sub 5} in D{sub 2}O. Valence mode cutoff models for pyridinium ion and pyridine account for both values and suggest the following: (1) The value of pK{sub a}{sup 14} {minus} pK{sub a}{sup 15} for C{sub 5}H{sub 5}NH{sup +} would be near {minus}0.0136 in the absence of hydrogen bonding. (2) The C{sub 5}H{sub 5}NH{sup +}{hor ellipsis}OH{sub 2} and C{sub 5}H{sub 5}N{hor ellipsis}HOH hydrogen bonds reduce the magnitude of pK{sub a}{sup 14} {minus} pK{sub a}{sup 15}by about 0.0031 and 0.0014, respectively. (3) The H{sub 2}O/D{sub 2}O isotope effect on pK{sub a}{sup 14} {minus} pK{sub a}{sup 15} is a consequence of the reduced masses for the C{sub 5}H{sub 5}ND{sup +} vibrational modes being more sensitive to the {sup 14}N/{sup 15}N mass difference than are the reduced masses for the C{sub 5}H{sub 5}NH{sup +} modes; contributions from differences between C{sub 5}H{sub 5}N{hor ellipsis}HOH and C{sub 5}H{sub 5}N{hor ellipsis}DOD hydrogen bonds are very small. In general, H/D isotope effects on other equilibrium isotope effects are expected to be significant whenever two conditions are satisfied: (1) The two isotopic atoms are in separate reactant molecules but in the same product molecule. (2) Motion of both isotopic atoms occurs in at least one vibrational mode of the product for which hv/k{sub b}t has a value significantly greater than 2.

• OSTI ID: 5439098
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 93:2; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400202* -- Isotope Effects
Isotope Exchange
& Isotope Separation
AZINES
DATA
DEUTERIUM
ENERGY LEVELS
EQUILIBRIUM
EXCITED STATES
HEAVY WATER
HETEROCYCLIC COMPOUNDS
HYDROGEN 1
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
LIGHT NUCLEI
MATHEMATICAL MODELS
NITROGEN 14
NITROGEN 15
NITROGEN ISOTOPES
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
PYRIDINE
PYRIDINES
STABLE ISOTOPES
THEORETICAL DATA
THERMODYNAMIC PROPERTIES
VALENCE
VIBRATIONAL STATES
WATER