Bond Dissociation Energies In Simple Molecules

60 Pages·1970·3.595 MB·English

by  B. deB. Darwent

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Bond Dissociation Energies
In Simple Molecules
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U.S. DEPARTMENT OF COMMERCE
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UNITED STATES DEPARTMENT OF COMMERCE
Maurice H. Stans, Secretary
NATIONAL BUREAU OF STANDARDS • Lewis M. Branscomb, Director
Bond Dissociation Energies in Simple Molecule
B. deB. Darwent
Department of Chemistry
The Catholic University of America
Washington, D.C. 20017
NSRDS-NBS 31
Nat. Stand. Ref. Data Ser., Nat. Bur. Stand. (U.S.), 31, 52 pages (Jan. 1970)
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hi
Contents
Page
Foreword Ill
Introduction 1
References 2
Table of bond dissociation energies 9
IV
B
Bond Dissociation Energies in Simple Molecules
B. deB. Darwent
Bond dissociation energy values (kcal/mol) and (kj/mol) of simple compounds are tabulated
from a literature reviewcoveringtheyears 1962—1966inclusively. Someselected valueswhichappeared
in the years 1956-1962 are also included—. Organic compounds are excluded except those containing
one carbon atom. The groups > CO and CN are not considered to be organic.
The values are quoted Usually at 0 K or 298 K and refer to the gaseous state. They represent
the energy required to break a bond at the specified temperature with all substances in the zero vibra-
tional state of the ground electronic state. The experimental method for the energy value listed is
given and referenced in the table. A value recommended by the author is listed as the final value for
each reaction.
Key words: Bond dissociation energy; gaseous state; inorganic simple compounds; recommended
value; zero vibrational state ofthe ground electronic state.
Introduction
This review of bond dissociation energies of between H and other elements, which are given
simple compounds includes values published, gen- under the other element. Thus data on O—H, H—Cl,
erally, between 1956 and 1966 inclusive. The etc., are found under O, Cl, etc.
period from 1956 to 1962 was covered less thoroughly The bond dissociation energy D° for a bond A—
than that of 1962 to 1966. Cottrell’s book [3]1 which is broken through the reaction
appeared in 1958 and is assumed to have covered AB~> A+B
the literature up to and including 1955; the com-
pilation of Vedeneyev et al. [6] covered the field
to 1962, but they did not attempt a complete cov- is defined here as the standard-state enthalpy
erage of the literature. In the present review all change for the reaction at a specified temperature.
values appearing between 1962 and 1966, and se- That is,
lheacvteedbeveanlugeisveanpipneatrhiengtabblee,tweeveenn i1f9s5o6meanodf t1h9e6m2 D°= WfS(A)+ Atf/?(B)-AtffflAB)
may now be considered to be inaccurate or com-
pletely untrustworthy. This approach is of some where AHfo is the standard-state heat of formation.
value, especially for bonds on which only a few All values of D° refer to the gaseous state, and are
measurements have been made, since opinions of given at either 0 K or 298 K, and in some cases at
relative merit often change with time. The efficiency both temperatures. The few exceptions are noted
of retrieval of information, within the stated period, under “Remarks ’. The value of D° at 0 K is equal
is estimated to be approximately 80 percent. to the energy required to break the A—B bond under
Organic compounds have been excluded, in view the stipulated conditions that the reactant and
of Kerr’s excellent review [8] of 1966, although product molecules are in their electronic and vi-
compounds containing one carbon atom have been brational ground states. Thus it has a clearer phys-
included; the groups > CO and — CN are not re- ical interpretation than the dissociation energy at
garded as being organic. other temperatures. In the simplest case where the
Very recent data on thermochemical properties bond of a diatomic molecule is broken, D° at 298 K
have been published by the National Bureau of is greater then D° at 0 K by an amount which lies
SditsasnodcairatdisonaseTneecrhgniiecsalhaNvoetebe2e7n0-r3ec[a9l]c;umlaatneyd bfornodm bInetwpeoelynatRoTmiacndmo(l3e/2c)ulReTs (ti.hei.s, 0d.i6ffteor0e.n9cekcamla/ymolb)e.
those data. It should be pointed out that the data somewhat greater.
in Ref. [9] often include input from spectroscopic The values of D° are listed in both kcal/m=ol and
and other types of measurements. Thus a dissocia- kj/mol. The conversion factor is 1 kcal/mol 4.184
tion energy labeled “Thermochemical; based on kj/mol.
[9]” in this tabulation is not necessarily derived No attempt will be made here to describe or
solely from conventional thermochemical measure- discuss the many methods used to measure bond
ments. dissociation energies since that has already been
The bonds are listed alphabetically under the done [1 to 8]. It is well known that individual
more electropositive elements except for bonds methods are useful and reliable only for limited
types of molecules and over limited ranges of
1Figuresin bracketsindicatetheliteraturereferenceson page2. conditions. Thus the classic static manometric
1
method gives excellent results for I2, N2O4, etc. At this stage the only safe conclusion is that much
but not for dibenzyl; the spectroscopic method more research is required.
gives values of the highest precision for simple The estimated uncertainties of individual meas-
molecules, especially when the dissociation prod- urements are those given by the original authors or
ucts are unequivocal and a clear convergence can reviewers. Recommended values are listed in bold
be obtained, but it is much less useful for more type with estimated uncertainties. Those estimates
complex molecules. are based on the extent of agreement between dif-
Many determinations of bond dissociation en- ferent measurements, more weight being given to
ergies have recently appeared using high tempera- the results from the more reliable method, when the
tures chemistry techniques, e.g., effusion from a datum results from a direct measurement. For
Knudsen cell and the use of mass spectrometry to thermochemically calculated values consideration
identify and measure the concentrations ofthe effus- is given to the precision of each of the thermochem-
ing materials. Most of the measurements on the ical quantities involved in the calculation. No at-
oxides of the Group IIA elements have been made tempt has been made at a statistical evaluation of
by that technique and by flame photometry. In uncertainties. They are to some extent the result of
theory both methods are capable of giving values of my own prejudice, though often tempered by the
at least modest precision for the bond dissociation advice of experts.
energies. Although in some cases the data so ob-
tained are often consistent and fairly precise, in
other instances, e.g. CaO, there is considerable dis-
agreement, not only between the two methods but The author is grateful to the Catholic University
also between values obtained by the same method. of America for leave of absence and sabbatical
There has been much controversy on the relative leave and to the National Bureau of Standards for
merits of these two techniques. The high tempera- space and technical and financial assistance. The
ture mass-spectrometry results are suspect [55] space was provided by the Physical Chemistry
because of the possibility of fragmentation of the Division and the financial assistance by the Office of
molecule under electron impact. In another review Standard Reference Data, National Bureau of
[190] it is claimed that Drowart and Goldfinger Standards. It is indeed a pleasure to acknowledge
[10] had already refuted that suggestion. Actually, the help and advice given by Dr. D. Garvin of the
Drowart and Goldfinger did not really disprove the Elementary Processes Section and Dr. S. A.
claim but rather stated that interaction with the Rossmassler of the Office of Standard Reference
alumina container is likely to be a more important Data. The author is greatly indebted to Dr. W. H.
source of uncertainty. On the other hand, there does Evans for many discussions and advice about
appear to be doubt concerning both the nature of thermochemical measurements and to Dr. H. M.
the emitter and the possibility of interference by Rosenstock for information on many matters,
other substances in the flame photometric work. mostly scientific.
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