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and Electron Affinities

V. I. VEDENEYEV, L. V. GURVICH,
V. N. KONDRAT'YEV, V. A. MEDVEDEV and
Ye. L. FRANKEVICH

T r a n s l a t e d from t h e R u s s i a n by
Scripta T e c h n i c a Ltd.

Foreword t o t h e E n g l i s h edition by
W. C . P R I C E , F.R.S.
P r o f e s s o r of P h y s i c s , King's College, London

LONDON.EDWARD ARNOLD (PUBLISHERS) LTD.


O ~ d w a r dArnold ( P u b l i s h e r s ) Ltd. 1966

Originally p u b l i s h e d under the t i t l e Energiya razryva


khimicheskikh svyazei: Potentsialy ionizatsii i srodstvo
k elektronu b y the Academy of S c i e n c e s , U.S.S.R., Moscow,
1962.

Printed in Great Britain by


Butler & Tanner Ltd., Frome and London
Professor W.C. P r i c e , F.R.S.

Chemical and physical behaviour i s largely controlled by the energetics


of molecular species. A compilation of the available data on dissoci-
ation energies, ionization energies, electron and proton affinities i s
indispensable to all chemists and to a large number of scientists in
other fields. This scholarly work by a group of Soviet scientists meets
this need for the f i r s t time and deserves to be warmly welcomed in the
%est.

The collection of this data which i s widely scattered throughout the


literature, and its arrangement in a systematic form i s a formidable
task but one which i s essential to scientific progress. Thermochemists,
photochemists, m a s s spectroscopists, kineticists and many others will
be grateful to the authors of this admirable book for presenting such
a large amount of infornlation in a readily accessible form. It covers
the literature up to the beginning of 1 9 6 2 giving the experimental values
of the relevant molecular parameters and an outline of the main methods
rlsed to obtain them.

The reduction of thermochemical data to an atomic level has been


frustrated until recently by lack ofknowledge of the heats of atomization
of the elements. It i s on15 in the l a s t decade that this information has
kecome available for some of the most important elements. In the past
much discussion of the character of the chemical bond has been in t e r m s
of mean bond energies and quantities which depend on the f i r s t de-
rivatix-e of the bond potential energy such a s bond distance, bond force
cvnstants etc. simply because these data were readily available. The
use of the actual energies cannot but lead to a greater clarification of
the nature of chemical binding and this compendium and guide to the
literature on molecular energetics will greatly help to strengthen and
facilitate the more direct approach a s well a s providing an invaluable
reference book f o r the research worker and technologist.

W.C. P r i c e
King's College London
FOREWORD

There i s a t present no reference text which covers adequately the


available data on the energy of chemical bonds and on such important
molecular characteristics a s ionization energies and electron affinities.
Individual papers and reviews a r e limited ta a relativel) narrow range
of compounds, so that the r e s e a r c h worker and the technologist a r e
often forced into a time-wasting s e a r c h through an enormous number
of periodicals, some of which a r e not easily available.

The present work i s intended to remedy this.

The book includes all currently knoun material relating to the bond
energies in organic and inorganic molecules (Chapter l ) , radicals
(Chapter 2 ) , and to the ionization energies andelectron affinities (Chap-
!t-rs 3 and 4). X brief summary of the available information concerning
t h r proton affinities i s also included in Chapter 4. Each chapter has
t2xpianatory notes outlining the principles according to which the data
~ r rset out in the corresponding tables. These notes a i m to help the
w d d e r find his way through the material.

There a r e also supplementary notes for the tabulated figures (indi-


ited IJ?nunihers in round brackets, for example (see l)]; these a r e
pirticularl) important in the cases where the values given by different
u > r k e r s andobtained by different methods do not agree. The values which
,rh :he opinion of the present authors, a r e t h e most reliable, a r e given in
'aid type.

n hen the values given i n t h ~ sh o a ~r e quoted without any alterations


'rorn a revieu o r collection, the r e a d e r i s referred to these sources
ilone, u h e r e he will find the original references. In all other c a s e s , the
lriginal papers a r e cited. Additional references to papers in which an
t)riginal Lalue has been discussed o r recalculated, for example: 1821
(5ee [83]), a r e given in round brackets.

The introduction provides a brief outline of the main methods used to


determine the values given in this book. This will help the reader to
a s s e s s the relative m e r i t s of these meth,ds and to judge the reliability
o f the results.

Tables 1 and 4 have been compiled by L.V.Gurvich, Tables 2 and 5 by


L .I.Vedeneev, Tables 3 and 6 by V.A.Medvedev, and Tables 7 and 1 2 by
F .L. Frankevich.

The following s u m m a r i e s and texts were used in the preparation of


f his book.
vii
...
Vlll
Foreword

REFERENCES

1. GURVICH, L.V., KHACHKURZOV, G.A.. MEDVEDEV, V.A., VEYTS, I.V.,


BERGMAN. G.A., YUNGhlAN. V S . . RTISHCHEVA, N.P.. and KURATOVA,
L . F . et al. (1962). Thermodynamic properties of individual s u b s t a n c e s Izd.
An SSSR, Moscow.
2. COTTRELL, T . L . (1958). The Strengths of Chemical B o n d s , London.
3 . KUBASHEWSKI, 0. and EVANS. E. L1. (1952). CIetallurgical Thermochemistry,
London.
4. BUCHEL'NIKOVA, N.S. (1958). l l s p e k h . fir. n a u k , 15, 351,
5. HERZBERG, G. 1950. Clolecular Spectra and Molecular Structure. I. Spectra
of Diatomic .Molecules. Second edition, Toronto. New-York- London.
6. GAYDON, A. 1953. Ilissociation Energies and Spectra of Diatomic Molecules,
Second Edition. London.
7. BICIIOWSKY, F.R., and ROSSINI, F.D. 1956. T h e Thermochemistry of Chem-
ical S u b s t u n c e s . N.Y.
8. ROSSINI, F.D..WAGMAN. D.D., EVANS, W.H., I.EVINE, S.. and J A F F E , V.
1952. S e l e c t e d V a l u e s of Chemical Thermodynamic Properties. Nat. Bur.Stan-
dards, Circ. 500. Washington.
9. T h e Chemistry and Metallurgy of Miscellaneous Materials. Thermodynamics.
N.Y., 1950.
10. STULI,, D.R.. and SINKE. G.C. 1956. T h e Thermodynamic Properties of the
E l e m e n t s , A d v a n c e s i n Chemistry, ser. 18. Washington.
11. KELLEY. K.K. 1935. U.S. Bur. o f M i n e s , Bull. 383. Washington.
12. BREWER, L. (1953). Chem. Rev., 52, 1.
13. SZWARC, M. (1950). Chem. R e v . , 47, 75.
14. SEHON, A.H.. and SZWARC, M. (1957). Ann. R e v . P h y s . Chem., 8 , 439.
15. GRAY, P,, and WILLIAMS, A. (1959). Chem. Rev., 59, 239.
16. FIELD, F.H., and FRANKLIN, J . L . 1957. Electron Impact Phenomena and
the Properties of G a s e o u s l o n s . N.Y.

Conversion f a c t o r s f o r energy u n i t s

cal /m01 e

ery/mol E

j /m01 e
c a l /m01 c

-1
eV/mol e
cm
LNTRODUCTION

Because of the development of new experimental techniques and owing


to the increased accuracy of theoretical calculations by using electronic
computers, our knowledge of the energies of chemical bonds has grown
considerably in recent y e a r s , particularly in mass-spectroscopic and
kinetic methods.

Therefore many bond energies known e a r l i e r have been recalculated


with g r e a t e r precision. \ l e can now consider that the problem of the
heats of dissociation of fluorine, nitrogen, and carbon monoxide and of
the bond energies in some simple compounds, has finally been solved.
The same is true of the sublimation energy of carbon, which has been a
longstanding object of dispute.

The energy of chemical bonds i s an important molecular constant. It


i s , in fact, one of the main characteristics of a molecule, determining i t s
structure and chemical properties. Bond energies a r e of particular
significance in thermodynamics and in chemical kinetics.

The number of bonds between individual atoms in a given molecule is


in the lowest energy state andone o r more of these bonds may be broken
a s the energy of the molecule i s increased. If the fission of a certain
bond leads to dissociation of the molecule into two p a r t s , the energy of
the bowl will be equal to the difference between the heats of formation
of the dissociation products and the heat of formation of the starting
undissociated molecule. Thus, the bond energy of the bond R I - R2 in
molecule R,R2 (in other words, the heat of dissociation of molecule
R I R s into R , and R 2 ) i s given by

where \FI;, a r e the respective heats of formation of R I , R 2 , and R , R 2


from the elements in their standard s t a t e s . ' )

The bond energy is frequently (although not always2) equal to the


minimum energy which must be supplied to the molecule to dissociate
it into the corresponding fragments.
1. Tbe f o l l o h r n g standard s + l t e s l a v a hren assumed, as i n t h e b a s i c thermodynamic
t e x t b o o k s : ( a ) f o r l i a u i d s o r s o l i d s , t h e pure suostance i n t h e thermodynamically
s t a b l e m o d i f i c a t i o u a t 1 atm a:]: 15. C; ( c ) f o r gases, an i d e a l gas a t 1 atm, u i t h
a '?eat cnn'aqt eqdal t o t h a t o f t h re21
~ gas a t t + e same temperature.
1. One o f t i l e n3ny ~ ~ c e p t i 3 1 i3s , f o r ~ x a m ~ l et ,h e decomposition o f N 0 into N
2 2
and 0; t h e qinimum energy i s -- !3 kcal/mole, and t h e N and 0 bond energy i n the
NqO m o l e c u l e i i 351.5 kcal/mole. 11 otr:-r cases, a n o l e c u l e may even d i s s o c i a t e
i
when an energv ssn3iler t h a n t h e e n e r g i e s o f t h e bonds t o be broken i s supplied.
T h i s o c c u r s v k n t h e r a d i c a l s formed a r e u n s t a b l e and decompose f u r t h e r i n t o l i g h t -
e r p a r t i c l e s ; s t a b i l i s a t i o n o c t h e d ? c o r ? o s i t i o n p r o d u c t s o c c u r s d u r i n g t h i s de-
c o n p o s i t i o n ( f o r example, b j a change o f valency).
X Introduction

If a molecule contains two o r more identical bonds, we must differ-


entiate between the energy required to break one of these bonds and the
mean bond energy. Thus the bond energy of HO-H in H 2 0 , i.e. the heat
of the reaction H 2 0 = H0 + H i s 118 kcal/molel while the mean bond
energy of H-H in H 2 0 i s equal toone-half of its heat of atomisation, i.e.
one-half of the heat of reaction H 2 0 = H + H + 0 (110 kcal). Similarly,
the energy required to split CH4 into H + CH3 i s 102 kcal, while the
mean C-H bond energy in methane i s only 99 kcal.
These differences a r e due to the fact that certain changes in the
electronic and atomic configurations occur when the molecule undergoes
dissociation, affecting energies of interaction of the remaining atoms.
Thus in the tetrahedral CH4 molecule the valency angles between the
four C-H bonds a r e 109.5", while the CH3 radical i s planar (or almost
planar) and the valency angles increase to about 120'.
For diatomic molecules which a r e gaseous under standard conditions
(for example, NZ o r F, ), the heats of formation AHl(R1) and A H ' ( R ~ )
appearing in equation (1) a r e expressed in terms of the heats of dis-
sociation of molecules RI R , and R 2R by the formulae

so that

Thus equation (2) can be used for the calculation of the heats of
dissociation (bond energies) from the heats of dissociation known for
other molecules. For example, for NO

This allows a calculat~onof Do(NO)with the same accuracy to which the


Do(Nz),1),(02) and A H (NO) a r e known. Exactly the same procedure can
be used to obtain the heats of dissociationof the hydrogen halides HX on
the basis of the well-known heats of formations of HX from gaseous H2
and X and the heats of dissociation of H2 and X2.

In the case of CO, equation (1) can be written in the form

D, (CO) = A H s o (C) + D. (0,)- A H;. (CO).


-- p- -

1.The u n i t kcallmole w i l l subsequently be w r i t t e n as kcal for the sake of brevity.

2.The t r a n s i t i o n from the pyramidal NH molecule w i t h valency angles o f 106.5"


3
t o t h e p l a n a r s t r u c t u r e i n v o l v e s an expenditure o f 6 kcal o f energy /l/.The
energy d i f f e r e n c e between t h e plarlar and pyramidal s t r u c t u r e s o f t h e CH radical
3
should be o f the same order.
Introduction xi

.here AH,,(C) represents the heat of sublimation of carbon. D,(CO)


, A V then be calculated from AH,, ( C ) . Do(O ) and AH;,(co). Since,
I lwever, ,!,H,, ( C ) could not be measured with the necessary accuracy,
- l i t x a b v e formula has been used to calculate the heat of sublimation of
artmn (uhich i s of fundamental importance in the calculation of the
ond energies in organic molecules) from an accurately determined
alue of Do(CO).At 0 " K IH,,(C, graphite) = 169.96 kcal.

'The heats of formation of monatomic g a s e s , important in thermo-


hemical calculations, can he derived for gaseous substances of the type
0 2 , K2 and so on, from the heats of dissociation of the diatomic mole-
ules of these elements. using the formula

For substances which a r e in the condensed state under standard


1:onditions and which v a p r i s e to give monatomic g a s e s , the heats of
formation a r e equal to their heats of sublimation:

while for substances which vaporise to give molecules X , (for example,


bromine o r phosphorus) the atomic heats for formation may be found
trom

If the heat of formation of a substance i s known at 0 " K , it may be


~*alculatedfor any other temperature 7' with the aid of the expression

in ehich C (.ABC ...) i s the molar heat capacity of the substance con-
sidered and i S 1, a r e the molar heat capacitiesof elements forming the
given suhstance, in their standard states.
?;
Modern textbooks generally give tabulatedvalues of L H ; -
0

= \ cpdr
0
These may be used to write (6) in the form

where l H , - H i s the difference in the change of enthalpy from 0 to


I K for the suhstance considered and for i t s elements in their standard
states.

The heats of formationof radicals can also be calculated from equation


(1). Thus, to calculate the heat of formation of the hydroxyl radical we
can use the heat of dissociation of OH and the atomic heats of formation
of H and 0
xii Introduction

This procedure gives 1 H , (OH) = 51.62 + 58.98 - 1.01.3 = 9.3 kcal.

The heats of dissociation a r e also used (incombination with the heats


of formation of the corresponding compounds in the gaseous state) to
calculate the energy required to break down a complex molecule into
i t s constituent atoms (heats of atomisation). The heats of atomisation
a r e in turn essential for the determination of the mean energies of
chemical bonds.
COSTESTS
Page
Foreword by Prof. W. C. P r i c e F.R.S. v

Foreword by t h e authors vii

Introduction
...
Contents Xlll

Determination of bond e n e r g i e s
Experimental methods
Theoretical and semi-empirical methods

Methods of determining the ionization potentials


of atoms, molecules and r a d i c a l s

Methods of determining electron and proton


affinities
Electron affinity
Proton affinity

I BOSD E N E R G I E S
T a b l e 1 Dissociation e n e r g i e s of diatomic
molecules

Table 2 Bond energies of organic a o l e c u l e s and


radicals

T a b l e 3 Bond e n e r g i e s in inorganic molecules


and r a d i c a l s

I1 tIEATS OF FORSIATIOY O F 4TOMS A N D RADICALS 114


T a b l e 4 H e a t s of formation of atoms
T a b l e 5 H e a t s of formation of organic radicals
T a b l e 6 H e a t s of formation of inorganic
radicals
...
Xlll
Contents
111 IONIZATION POTENTIALS

Table 7 Ionization potentials of atoms

Table 8 Ionization potentials of hydrocarbons,


molecules and radicals

Table 9 Ionization potentials of halogen-


containing organic molecules and
radicals

Table 10 Ionization potentials of nitrogen-


containing molecules and radicals

Table 11 Ionization potentials of oxygen-


containing molecules and radicals

Table 1 2 Ionization potentials of molecules and


radicals containing boron, silicon,
sulphur and other elements

IV ELECTRON AND PROTON AFFINITIES


Table 1 3 Electron affinities of atoms

Table 14 Electron affinities of molecules and radicals

Table 1 5 Proton affinities of some atoms,


radicals and molecules

xiv
DETERMINATION O F BOND ENERGIES

Experimental methods

Heats of dissociation and bond energies a r e most frequently determi-


ned by thermal methods. One group of such methods i s based on the
determination of equilibrium constants of chemical reactions. In i t s
simplest form one of these methods reduces basically to the determi-
nation of the pressure ofa heatedgas (in a closed volume), o r the meas-
urement of the concentration of the original g a s o r i t s dissociation pro-
ducts at different temperatures.

The heat of dissociation may be calculated from measured dissocia-


tion constants by two methods. The f i r s t method, which was usually em-
ployed in early work, i s based on the second law of thermodynamics
and in particular the van't Hoff equation
dln K , AH,
aT - RTa
(in the present c a s e A H T = DT ). In this method the magnitude of DT i s
found from
4.5758 1 ag K , =-
D, + const.
To determine the heat of dissociation from equation (9) it i s neces-
s a r y to know the dissociation constant a t a number of temperatures.
From the temperature-dependence of log K given by (9) one can then
determine Dr = A H r . The heat of dissociation D o a t 0" K can be calcu-
lated from this value of D, using equation (6) o r (7).

The second method, which has beenincreasingly used in recent years,


i s based on the calculation of Do from the equation

D, = T (A@; -4.57581 04 K,),

where T i s the temperature at which K, has been measured, and A@; is


the change (during the dissociation reaction) in the reduced thermo-
G O H"
dynamic potential CD; (CD; = - T- O where G; i s the thermodynamic
T
potential a t temperature 7°K and constant pressure. In o r d e r to calcu-
late D O from equation (10) it i s sufficient to measureJhe equilibrium
constants a t a single temperature and the values of @ T for the corre-
sponding substance and for the dissociation products l .

Calculations based on equation (10) have a number of important

1. I n o r d e r t o d e t e r m i n e t h e d i s s o c i a t i o n energy a t o 0 K f r o m e q u a t i o n ( 9 ) one must


know t h e v a l u e s o f C, o r H," - H: f o r a l l t h e components t a k i n g p a r t i n t h e
d i s s o c i a t i o n r e a c t i o n . The v a l u e s o f o;, HP - H: a n d C; a r e u s u a l l y
d e t e r s 1 fled simultaneous1 y.

1
advantages over those based on equation (9). In particular, the spread
of experimental data obtained in a limited temperature range prevents
an accurate determination of DT from equation (9) even when the coef-
ficients of this equation a r e found by the method of least squares,
and the corresponding e r r o r in DT may reach 10-20 kcal. At the same
time, an e r r o r amounting to a factor of 2 in the value of K,. a s found
from calculations of the dissociation energy using equation (10) leads
-
to an e r r o r of only 1.5 kcal if the equilibrium constant i s measured
a t 1000°K and - 3 kcal if the measurements a r e carried out at 2000°K.

When dissociation energies a t a given temperature a r e converted to


some other temperature, it must be remembered that the difference
DT-D, i s always positive and lies between 3RT/2 (vibrational degrees
of freedom not excitedj and RT/2 (vibrational degrees of freedom ex-
cited) at room o r higher temperatures.

At each given temperature the increase in pressure due to dissociation


increases with increasing equilibrium constant, i.e. decreasing heat of
dissociation. Since high-temperature measurements a r e difficult and lead
to considerable e r r o r s , the above method of determining the heats of
dissociation i s therefore found to give the most accurate results only
in the case of small D when the concentration of the dissociation products
i s quite large even at relatively low temperatures. This method has led
to satisfactory results in the case of Cl2 , Brz and 12. A s an example,
we may consider the measurements of the heat of dissociation of iodine
carried out by Perlman and Rollefson [21. They calculated the values
of Doofrom measurements at various temperatures and found them to
be: 35.757 (872"K), 35.583 (973'K), 35.528 (1073"K ) , 35.504 (1173°K)
and 35.515 kcal (1274°K). The weighted mean 35.514 kcal i s practically
the same a s the spectroscopic value 35.556 kcal [31.

In recent years, considerable improvements in measurements of the


temperature and concentration of substances in systems at high temper-
atures have led to the extension of the thermal method to temperatures
of the order of 3000°K, so that relatively large heats of dissociation can
now be measured by this method.

The shock wave method, which i s based on the relation between the
velocity of propagation of a shock wave in a gas and the state of the
latter, e.g. its temperature and pressure, can also be used to measure
large heats of dissociation. For example, Tennis and Green l41 have
compared the measured and calculated velocities of shock waves in
nitrogen and have shown that, of the two values for the heats of dissocia-
tion obtained spectroscopically, D o = 170.22 kcal and 225.09 kcal, only
the latter i s in agreement with the value calculated from the velocity
of propagation, and i s therefore the correct one.

The determination of the 0-H and HO-H bond energies can also serve
a s an example of the thermal method based on measurements of equili-
brium concentration of hydroxyl i n a mixture of H20and 0, at a temper-
ature T i s determined by the equilibrium 2H20+0,,+~OHand the corre-
sponding equilibrium constant
sc'here P 2. o and pc3 a r e the equilibrium partial p r e s s u r e s .

.Assuming that the heat Q,-of the reaction 4 0 H = 2 H 2 0 + 0 2 i s equal to


its mean in the temperature interval between T, and 7 , . we have,
from equation ( E ) ,

%here ( P - 4 and i , c o i l z a r e the equilibrium partial p r e s s u r e s of OH,


at the M O temperatures.

in the experiments of BoFoeffer and Reichardt [5] and other workers


who used this method ' 1 the p r e s s u r e s ri,;, were determined f r o m
the hydroxyl absorption spectrum. The heat of the reaction Q , reduced
u.ith the aid of Kirchhoff's equation to absolute zero, may be used to
i.slculate the 0 - H and HO-H bond energies from the formulae

u here D 1 H:I and D,i 0:)a r e the heats of dissociation of H2 and O2 and
\H H i s the heat of formation of water vapour from H the
elements at 0°K.

The va!ues of D-(OH) and D (HO-H) obtained by different w o r k e r s


using the above methodare found to lie in the ranges [D,(OH)=100.5-105.5
kcal and D (HO-H) = 113.9-113.5 kcal]. The accurate values of these
quantities obtained spectroscopically a r e respectively D,(OH) = 101.3
kcal and D - ( H O - H ) = 113.0 kcal uith an e r r o r o f f 0.3 kcal in each
:ase [ 91.

The above group of thermal methods also includes the detonation


method and the method based on measurements in flames under the
conditions of normal o r explosive combustion. The principle of the
combustion method i s a s follows.

The detonation of a gas initially at a temperature T o leads to an


increase in temperature to some maximum value 7 a t which the origi-
nal substances and the reaction products a r e in thermodynamic equili-
brium uith each other and with their dissociation products. The
temperature T and the corresponding equilibriym partial p r e s s u r e s of
all the substances in the region of detonationcan be calculated from the
12% of conservation of energy (on the assumption that the detonation is
adiabatic and that the composition of the gaseous mixture remains
unaltered) if the corresponding equilibrium constants, heats of formation
and specific heats of all the components a r e known. If one of these
quantities, for example the heat of formation of an atom o r a radical,
is not h o u n , then the equation necessary for i t s determination may be
obtained by measuring the maximum detonation pressure.

It should be noted that since the detonation process takes a finite


time, the conditions a r e never strictly adiabatic. In order to achieve
the required accuracy, it i s therefore necessary to introduce corrections
for energy losses. Moreover, it i s frequently also necessary to correct
for losses associated with the emission of energy by the heated gases.

In the case of hot flames, the reaction proceeds so that a thermo-


dynamic equilibrium i s set up at the temperature of the combustion
zone, i.e. the maximum temperature of the flame. This temperature may
be calculated from the thermal balance of the flame for which, as in the
case of the detonation method, one must know the corresponding
equilibrium constants, heats of formation and specific heats. When one
of these quantities i s unknown, it may be determined from additional
measurements of the maximum flame temperature (this can be done,
for example, spectroscopically).

Since the rate of propagation of a flame i s unambiguously related to


its maximum temperature, it i s in principle possible to determine
thernaochernical quantities from measurements of the rate of propagation
of flames. This refers both to normal and detonation combustion.

As an example of the first application ofthe thermal method based on


the determination of the rate of detonation, we may consider the work of
Zel'dovich [g] who showed that the observed rate of detonation in
mixtures of C2N2 and oxygen i s consistent only with a heat of dissociation
of CO in excess of 210 kcal. This excludes the first two of the following
three values of the heat of dissociationof CO obtained from spectroscopic
data: 159.55, 210.80 and 256.14 kcal.

Later, Kistiakowsky and Zinman [l01 found that the observed rate of
detonation in acetylene-oxygen mixtures agrees with the calculated
values only for a heat of dissociation of CO equal to 256 kcal.

Important results have also been obtained from spectroscopic studies


of combustion products in high temperature flames into which elements
(mainly metals) were introduced in small amounts. This method has
been used to determine the dissociation energy of some tens of diatomic
molecules and also of many triatomic metal hydroxides.

A very fruitful method of studying chemical equilibria i s that based on


m a s s spectrometric studies of the composition of saturated vapours.
for example vapours effusing through small apertures. This has led to
more accurate values for the heats of sublimation of a number of
substances including many elements [ l ] and also heats of reaction
between the individual components of the vapour when the vapour has
a complex compasition.

All the above thermal methods a r e based on measurements of the


thermodynamic equilibrium in heated gases. There a r e also thermal
methods, which may be described a s kinetic methods, where again one
i s concerned with the rates of the corresponding chemical processes.
Here we shall consider only the pyrolytic method which involves the
determination of the rate of thermal dissociation of the corresponding
substances.

It i s evident that in this case one can only be concerned with the
decomposition of molecules into radicals, i.e. with a monomolecular
process of the form

The activation energy E , which e n t e r s into the expression for the


r a t e constant for this process

i s in most c a s e s equal to the R - R 2 bond energy D . The latter can


therefore be obtained from measurements at different temperatures of
the r a t e constant for the monomolecular decomposition

The accuracy of the pyrolytic method depends on the absence of


parallel homogeneous o r heterogeneous reactions which could affect
measurements of the rate of the main reaction, and the absence of
secondary processes. particularly chain processes.

Contributions due to these fzctors have beenreduced to a minimum in


the modification of the pyrolytic method which was developed by
s z u a r c [ I l l . In this method, pyrolysis i s produced in s mixture of the
substance under investigation v.ith toluene vapour, the l a t t e r predomi-
nating. In the presence of toluene, which contains active H atoms in the
methyl group, the main secondary processes a r e

As a result, the presence of parallel processes involving the trans-


formation of the substance under investigation R I R z h a s no effect on
measurements of the rate of primary dissociationof R1 R2 if this r a t e i s
determined from the rate of formation of R1 H , R2H o r ( C 6 & CH2).
Moreover, the disappearance of the radicals R 1 and R 2 a s a result of the
interaction with the toluene, and the low activity of the resulting benzyl
radical, make the development of a chain reaction fairly improbable.

The toluene method has been widely used both by Szwarc himself and
by other workers. It should, however, be pointedout that, since the heat
of dissociation of toluene D ( C * H j C H 2 -H) is about 83 kcal [121, the
application of the toluene method i s limited in two ways: a t least one of
the radicals (R1 o r R2) should be quite active, i.e. the heat of dissoci-
-
ation of R: H o r R2H should be g r e a t e r than 83 kcal, while the R1 R2
bond energy should be appreciably smaller than 83 kcal (by not l e s s than
1 0 kcal) since only then can the dissociation of toluene itself be neg-
lected.

In addition to the above pyrolytic method of determining bond energies,


there i s also a simplified version of this method which i s frequently
used. It i s based on the fact that the coefficient A in equation (11)
frequently turns out to be of the order of 1013 sec -1. If this value i s in
fact assumed, and k i s measured at a particular temperature, the bond
energy may be calculated from

This simplified method was first used by Butler and Polanyi [l3] to
determine C-I bond energies in various organic. iodides. It has been
used by many workers, including Szwarc, who has also given a critical
review of the method.

We note that apart from the e r r o r s which may arise when the con-
ditions necessary for the applicability of the pyrolitic method a r e not
adequately satisfied, the above modification of the method i s subject
to other e r r o r s which a r e due to departures of the coefficient A from
the assumed value of 1013 sec - l . A change in A of one order of magni-
tude at a temperature of 1000°K leads to an e r r o r of 5 kcal.

The mass spectrometric method of determining bond energies has


been widely used in recent years. In principle, this method consists of
the bombardment of the molecules under investigation by electrons, and
the determination of the minimum electron energy at which ions of the
appropriate kind appear in the mass spectrum (i.e. the appearance
potential for the particular ions) and the energy of the s e ions. In bond
energy determinations one i s interested in the process

If the energy E of this process andthe ionization potential of the radical


R: a r e known, we can use the equation

to calculate the R I - R2(D) bond energy. The energy E i s found from


the appearance potential for the ion R;, i.e. the minimum energy AP of
the bombarding electrons which i s necessary for the appearance of these
ions. The energies E and AP a r e related by

where El and E2 a r e the excitation energies of the ion R; and the


radical R z , and K1 and Kz a r e the translational energies of these
particles.

Assuming that the +minimum value of AP corresponds to zero exci-


tation energies of R1 and R z , and since the translational energy i s
distributed between R: and R2 in accordance with the laws of con-
servation of energy and angular momentum, we can rewrite equation
(13) in the form
M , t M?
AP = E F-- K,,

where M* and M2 a r e the molecular weights of R; and R 2 .
It follows that if we determine the kinetic energy of the ion R; (for
example. by the method of retarding potential) we can use equation (14)
to find E , and equation (12) to determine the required bond energy
li

The ionization potential ot the radicai R , which e n t e r s into equation


(12) may be measured directl) by the electron impact method, which
was f i r s t done by Hipple and Stevenson [l51 in the c a s e of the CH and
CIH radicals. In the experiments of Hipple and Stevenson the s o u r c e s
3f these radicals were tetramethyllead (CH3 ) 4Pb and tetraethyllead
I C :H.) :Pb. The ionization potential l of the CH3 radical, [ I (CH,)],
i.e. the energq of the p r o c e s s

1s i O . O Z 0.1 eV. From this result and from the energy of the p r o c e s s

which i s E = 14.4 l 0 . i e t 7 ,H e find using equation (12), that D (CH3-H)=


4.4 0.2 e t . \ \ e note that subsequent and more accurate measure-
ments gave D(CH3 - H ) = 4.12 :0.04 eV [161.

U hen R . i s an atom, i t s ionization potential, which i s necessary for


the calculation of the bond energy, may be found spectroscop!cally.

itevenson has also put f o r u a r d another method f o r the determi-


nation of bond energies ~ \ h i c h d c e s not require a knowledge of the
potential of the resulting fragment. -4s an example. consider the CH3-H
hond. %hose energj was calculated above from the measured ionization
potential of the CH3 radical. On adding the equations

rherefore. h! determining the appearance potential for the RC ion


% h e n RH and RCH3 a r e bombarded by electrons, i.e. the quantities
A P ' ( R - ) and -1P ' ( R - ) , from k n o u ~heats of formation of methane
AH (CH:) , RH, RCH3 [ SH (RH). A H , (RCH3) ] and of atomic hydrogen
.1H, ( H ) , u e can use the above formula to find D (CH3 - H). In the
)riglnal experiments Stevenson used ( C 2 H (RH) and C3H8 (RCH,),
.
with R = C2H F r o m measuredvalues 3P"(R-) = 15.2 e V and AP'(R+) =
L 1 . 5 eT and known heats of formation
i t follows that D(CH3-H) = 4.4 + 0.2 eV, which i s identical with the
result obtained earlier.
We note that the kinetic energy of thedecomposition products was not
taken into account in the determination of D(CH3-H) by either of the
above methods, i.e. i t was assumed that A P = E). Since the two values
were found to be the s a m e , itappears that the kinetic energy was in fact
small, i.e. the minimum energies for decomposition processes which
occur in accordance with the Franck-Condon principle (Uvertical
energies of decompositionn) approach closely the dissociation limits of
the molecules under consideration.
The fact that the H3C-H bond energies obtained in different ways
a r e very nearly the s a m e indicates also that in the present c a s e the
products of the dissociative ionization a r e not in excited states (El. - 0 ) '
Since an analogous result i s obtained in many other c a s e s , i t follows
that the absence of excitation and of appreciable kinetic energy of the
dissociation products can apparently be regarded a s quite frequent.
This is of enormous importance in the m a s s spectroscopic determination
of bond energies.
Steiner, Giese and Ingram have developed a photo-ionization
method of determining bond energies which i s very similar to the m a s s
spectrometric method. In principle, i t inolves the determination of the
current of fragment ions of given m a s s a s a function of the energy of
incident photons when the substance under investigation (gas) i s illumi-
nated by a monochromatic beam of ultraviolet radiation (with a 7 8 o r
0.05 eV spread). The apparatus employed i s a combination of a m a s s
spectrometer and a monochromator.
Extrapolation of the linear part of the curve representing the ion
current a s a function of the photon energy until i t cuts the horizontal
axis gives the experimental appearance potential (AP) for ions of a
given type. This i s not the same a s the true potential because the
original molecules have some thermal energy, and the products of
dissociative photo-ionization receive additional translational and int-
ernal energies. However, assuming that this "kinetic shift" i s the same
for all substances, Steiner, Giese and Ingram have calculated bond
energy differences between different molecules from the experimental
appearance potentials. Absolute bond energies can be obtained by using
a known bond energy for one of the molecules (H2 was taken a s the
standard molecule).
To determine the K-H bond energy in the RH molecule, one must
therefore measure the appearance potentials for the R'+ ions produced
a s a result of the irradiation of R'H (AP1=hvl)and RR' (APz=hv2) If .
v, and v2 a r e known, we can add together the equations

' We a r e concerned here w i t h e l e c t r o n i c o r v i b r a t i o n a l e x c i t a t i o n .


to obtain:
D(R - H ) =: D(Hz) - h ~ -2 h ~ , +-
A H ; (RR') - A H ; (RH) -
-IH;(R'H I
D(R-Hlcan be calculated from this equation, the known heats of
formation of RH. R'H and RR' , and the heat of dissociation of hydrogen.

By determining the appearance threshold for ions of a given type a t two


different temperatures (for example 150' and 28"C, which we can
denote by A P Ijo and A P 2 * ) and calculating the thermal energy of the
original molecules L ' l j o and L.28 from the specific heat, Steiner, Giese
and Ingram found the appearance potential at O°K from the formula

which provides us with a means of finding the bond energy a t absolute


zero.

The disadvantage of the photo-ionization method is the assumption


that the %netic shift* of the threshold of dissociative ionization i s the
same for molecules of different structure. This can hardly be justified
theoretically.

Finally, there a r e spectroscopic methods for the determinationof the


heats of dissociation and bond energies. In the relatively r a r e cases
when vibrational bands in the ground o r excited states of a molecule may
he recorded right up to the convergence limit, and when the quantum
state of the dissociation products of the molecule i s known, the spectro-
scopic method based on the determination of the band convergence limit
gives accurate values for the heats of dissociation.

This method has been used to determine the heats of dissocietion of


the diatomic molecules H2, 02, ClZ, Br2 and I z . However, for most of
the diatomic molecules the convergance limit of vibrational levels
1 v r i can only be obtained by extrapolation. If the vibrational frequency

(ov and the anharmonicity constant X corresponding to the ground


state of the molecule a r e known, it i s usual to employ the extrapolation
formula
Experiment shows that this formula will a s a rule give the heats of
dissociation to within 10-20%.
When the absorption spectrum is continuous its long-wave boundary
may be used to find the upper limit for the band convergence limit, which
in turn gives the upper limit for the dissociation energy.
h isolated cases (for example in the case of nitrogen and carbon
monoxide molecules) the dissociation energy can be accurately de-
termined from the predissociation limit. This i s possible when the
spectrum cuts off o r exhibits a spread (as a result of predissociation)
a t rotational lines in different bands of a given series. It can be used
to find the dissociation level (decomposition energy) of the molecule
to a high degree of accuracy by extrapolation. Since, however, the nature
of the electronic states of the dissociatiw products cannot usually be
established unambiguously, additional measurements a r e necessary in
order to determine the relationship between the decomposition energy
and the heat of dissociation. Since this ambiguity exists also in the case
of predissociation of N Z and CO, the problem of the true value of the
heats of dissociation of these molecules cannot be resolved by the
spectroscopic method alone.
As regards polyatomic molecules, the band convergence limit in the
spectrum of such molecules has apparently been detectedonly in CIOz .
The determination of this limit by extrapolating the formulae for
polyatomic molecules leads to even greater e r r o r s than in the case of
diatomic molecules. On the other hand, predissociation in the spectra of
polyatomic molecules i s a relatively common phenomenon. Since the
predissociation limit i s not sharp, apart from a few very r a r e ex-
ceptions, the predissociation method may be used to determine only
the upper limit for the heat of dissociation. The only exception among
the known substances i s nitrogen dioxide, whose ultraviolet spectrum
exhibits a sharp predissociation limit. The NO-O bondenergy calculated
from this limit i s very nearly the same a s the heat of the reaction
NO + 0 = NO2 obtained from thermochemical data.

Theoretical and serni - empirical methods


The bond energy of, say, the R 1 - F? 2 bond in the R 1 I i z molecule may
be calculated theoretically a s the difference between the energies of the
two particles R 1 and R 2 and the molecule R 1 K 2 . The mean bond
energy may be found from the heat of atomization calculated a s the
difference between the sum of the energies of all atoms making up the
molecule and the energy of the molecule. Therefore, theoretical calcu-
lations of bond energies can in the final analysis be reduced to determi-
nation of the energy of the molecules, i.e. determination of their
structure.
This involves the solution of the quantum mechanical problem of the
interaction between a given number of electrons and nuclei, which i s
mathematically difficult even for the simplest diatomic molecules. Here
it will be sufficient to consider the hydrogen molecule, i.e. a system
consisting of only two electrons and two nuclei. Even in this relatively
O t h e r methods f o r the d ~ t e r m i w t i o ~s ki bond e n e r g i e s and h e a t s o f d i s s o c i a t i o n
a r e c r i t i c a l l y reviewed t o g e t h a r w i t h t h e methods desct-ibed above i n C o t t r e l l ' s
book 1201.
simple case the 1 7 t h order approximationwas necessary before the heat
of dissociation gave satisfactory agreement with experimental data
[211 ( D = 1 0 3 . 2 1 0.3 kcal. D = 103.24 + 0.02 kcal). The heats
- X :

of dissociation of certain other simple diatomic molecules have also


been calculated to a lower degree of accuracy.

Important new results may be expected inthis field in connection with


the development of computer techniques. Oxygen and nitrogen molecules
were the first to be treated in this svay. The heat of dissociation of 02,
a s calculated by Neckler 1221, u a s found to be smaller by 293 than the
true value (116 instead of 1 1 8 kcal). Bruchner [23] used two methods
(the variational method and the so-called electrostatic method) to
determine the heat of dissociation of nitrogen, which was found to be
227.07 and 227.95 kcal respectively. These differ from the true value
(225.09 kcal) by approximately 1-.

The calculations a r e , of course, more difficult in the c a s e of triatomic


and more complicated molecules. Boys e t al. 1241 have recently shown
(also using an electronic computer) that this i s possible in principle by
considering the water molecule.

The various semi-empirical methods which make partial use of


experimental data, and therefore s i m lify the calculations, a r e also of
interest. For e x a m p l e Mulliken 1 used the so-called 'magic
formulan for the atomization energ) ahich he obtained from quantum
mechanical calculations. According to this formula the atomization
energy may be r e g a r d e d a s the sum ofa number of components, the most
important of u hich a r e functions of the so-called overlap integrals for
electron clouds corresponding to isolated p a i r s of atoms in the molecule
and of the atomic ionizationpotentials u h i c h a r e known from experiment.
3 n c e man!, of the parameters Lshich determine the "weight" of the
indindual components in the magic formula a r e inaccurate, this formula
does not l i e i d satisfactory heats of atomization for specific molecules.
Houever , comparison of the atomization energies calculated from the
magic formula (for various values of these parameters) with the
experimental results has led to the discovery of certain important
properties of the chemical bond.

In particular, it was sho\\n that the exchange repulsion between the


inner electron shells of atoms plays a more important role than was
assumed before. It was also shown that insovalent hybridization, i.e.
hybridization u hich does not lead to a change in the valency states plays
an important role in molecular stability. Mulliken has also used the
magic formulz in the case of the molecules X 2 . 0 2 ,F:!, C H 4 , C z H s ,
CzH;, Ci:H?, the ions H:. He- and the CH radical.

Heitler 1261 has calculated the bond energies of simple hydrocarbon


molecules. Using the quantum mechanical rnethod of spin invariants,
together uith a number of simplifying assumptions, he succeeded in
calculating the energy necessary to remove the hydrogenatom f r o m the
molecules CHI, C2H. and C 2 H 2 . and also the atomization energy of
ethylene. To do this, he usedthe experimental values for the atomization
energies of CH$,C2 H. and C: H2 .

,\mong other semi-empirical methods for the determination of the


chemical bond energies we shall consider only the following. When the
heat of formation of a substance AB i s known, the heat of dissociation
of the AB molecules can occasionally be determined from the postulate
of the additivity of energies of simple covalent bonds developed by
Pading and Jost [271. They deduced from experimental data that the
energy of a normal covalent bond betwen different atoms A and B i s
equal to the arithmetical mean of the two energies D ( A z ) and D(B2) .
However, it was found later that this postulate must be replaced by an
analogous postdate involving the geometric mean. This states that the
energy of the normal covalent bond between atoms A and B i s equal to
.
I / D ( A ~ ) D ( B ~ )At the same time the difference between the true
dissociation energy and the result obtained from the geometric mean
should decrease with decreasing difference in the electronegativity of
A and B, i.e. a s the bond in the molecule AB becomes more and more
covalent.

It i s easy, however, to verify that this method of determining the


dissociation energy i s suitable only for rough calculations. In point of
fact, by estimating, say, the heats of dissociation of a mixture of NO
and OH molecules from the formula

we obtain 163 instead of 156 kcal for NO and 111 instead of 101 kcal for
OH, i.e. numbers which exceed the true values by 7-9%. The discrepancy
i s even greater in the case of hydrogen halides and the values of D
calculated from equation (14) a r e lower by 14-54% a s compared with
the true values. Even in the case of the molecules of mixed halides the
values of D calculated from the heats of dissociation of molecules
X2 differ from the true values by 2-9%, while the discrepancy in the
case of molecules containing fluorine atoms i s 20%.

Franklin [281 has put forward the following simplified method of


calculating the heats of formation of hydrocarbon molecules, which he
later extended to free radicals and ions in the gaseous phase [291. The
principle of this method, which may be described a s the method of
equivalent groups, i s a s follows. The hydrocarbon molecule may be

-CH3 ,>CH2 ,?CH, -c-,


regarded a s consisting of a number of characteristic groups such a s
and so on. Each of these groups i s ascribed a
definite fraction A H , of the heat of formation AH; of the molecule, and
these group contributions remain constant on passing from one molecule
to another. Thus, in order to calculate the heat of formation of a hydro-
carbon molecule, all that i s necessary i s to add the A H i corresponding
to the characteristic groups making up the given molecule.

The numerical values of A H i a r e found from the heats of formation


of the corresponding molecules. For example, the magnitude of AHi for
the CH3 group i s give by
A H;(CZ H,) - 20.2
AH (CH,) = --P ---= - 10.1 kcal.
2 2

Franklin puts forward the following general formula for the heats of
formation of molecules
+
AH; = Z A H , AH'+ AH+ R, + (18)
In addition to l H , ,this formula includes components corresponding t o
the group which c a r r i e s the free valency ( 1 ~ 'o)r the positive charge
I L H - ) and the conlugation energy which must be taken into account in
UIS case of radicals and ions containing conjugated bonds (R) The .
numerical values of A H , and JH' for different groups have been
tabulated by Franklin. It i s assumed that R = 20 kcal.

IVe shall not reproduce these tables, but will take the calculation
of the heat of formation of certain simple radicals a s an example. Thus,
Franklin assumes L H , = -10.1 kcal and AH' = 34 kcal for the groups
- C H 3 and -CH,, from which the heat of formation of the ethyl radical is
found to be 23.9 kcal. This i s close to the result obtained by Gray
1301 which i s 24.5 kcal. For the alkyl radical, H 2 C = C H - C H 2 , it follows
from IH.I H.C =CH-, = 15 kcal and >H"I--?H~) = 34 kcal, taking the
conjugation energy into account, that ~ h '= 29 kcal instead of 30 kcal a s
given by Gray.

It follows from these examples, and also from the calculations of


Franklin, that heats of formation of radicals calculated by the method
of equivalent groups differ from the results obtained by other methods
by a few kcal (usually 1 o r 2 ) . Thus the e r r o r in the calculated heats of
formation of radicals i s practically the same a s that which Is i n h e r e ~ t
in any of the currently employed experimental methods.

.A detailed critical review of Franklin's method i s given in Vedeneev's


dissertation [311.

Franklin's method can in particular be used to calculate the chemical


bond energies in homologous series. Another semi-empirical methodof
calculatinf: these quantities has been put forward by Voevodskii 1321.

On the basis of general considerations, following from the usual


assumptions onthe mutual interactions of atoms andgroups in molecules,
it may be concluded that, a s a variable radical in molecules forming a
homologous s e r i e s becomes more complex (for example the alkyl
radical 2,=C,Hh-, in s e r i e s RX, where X = H , OH, halogen, C 6 H S , and
so on) the energy of the R, - X bond shouid tend to some constant
value. This result i s also obtained from experimental data, for example
by calculating from tabulated values the heats of formation of successive
members of th? homologo;~ s e r i e s R ,!; (where X H , CH3,C2H3 and
C H: ) , i.e. l H & - I X ) - A H ~ ( R , X I , it i s possible to verify that even for
relatively small n ( < 1 < 7 1 this difference assumes a constant value
independent of X. Comparison of this result with the equation

obtained on the basis of equation (1)will show that the heats of formation
of neighbouring members of the homologous s e r i e s will be independent
of the nature of the radical X only if

at sufficiently large n
Analysis of the experimental data for normal and iso-paraffinic
hydrocarbons, c a r r i e d out by Voevodskii E331 shows that the CH ,+I --H
bond energy i s 77.6 kcal. The reduction in the C - H bond energy on
passing from methane to ethane and other higher hydrocarbons i s
explained by Voevodskii by the inductive effect of the CH3 group.

F r o m this assumption about the C - H bond energy, Voevodskii


deduces the semi-empirical formula

where k , i s the number of carbon atoms in each of the three radical


chains RI, R.? and R 3 in R 2 R 3 CII . For example, in the case of

The energies necessary to remove the hydrogen atoms, a s calculated


from Voevodskii's formula for different hydrocarbons, a r e in good
agreement with the measured results.

Snle note that a forrnuia similar to equation (19) has been obtained by
Vorvodskii for C - C bond energies in paraffinic hydrocarbons.

Vecleneev !S41 vuhsequently put forward a more general empirical


formula for the a p p r o x i m a t ~determination ofthe C - H bond energies in
hydro,:arhons of different structures. This was based onthe assumption
that the I? - 13 bond energy was largely determined by the stabilisation
energy of the radical R, Vedeneer's formula becomes identical with
equation (19) in the speciai w s e of paraffinic hydrocarbons.
METHODS O F DETERMINING
THE IONIZATION POTENTIALS O F
ATOMS, MOLECULES AND RADICALS

The basic method of determining the ionization potentials of atoms i s


the s p -ctroscopic method, in which the ionization potential i s deduced
from the position of the s e r i e s limit in atomic spectra. In the case of
simple spectra, such a s , for example, those of the alkali metals, which
have only one electron in the outer shell, the spectrum includes the
Rydberg s e r i e s which converges to a limit whose position can be
determined accurately. In the case of atoms with a large number of
electrons in the outer shell, such s e r i e s a r e not available. This
complicates determination of the position of the limits, and hence also
of the ionization potentials. However, practically all the difficulties
involved in the interpretation of atomic spectra have now been resolved.
The only ionization potentials which have not been reliably determined
by the spectroscopic method a r e those of the r a r e earth and transuranic
elements.

Ioncv et a1 13.51 have developed an experimental method for determi-


ning the ionization potentials of the r a r e earthelements and of uranium.
This method is based on the surface ionization of these atoms a t a hot
tungsten surface. If the ionization potential i s much g r e a t e r than the
maximum local work function of tungsten, the logarithm of the ion
current emitted from the hot surface i s a linear function of the reciprocal
of the temperature of the surface. h l e n the atoms of two elements a r e
iontzed at the hot surface, the variation in the ratio of the ion currents
with temperature i s determined only by the difference between the
ionization potentials of the two elements.

Atomic ionization potentials can often be improved and in many cases


determined by interpolation of known ionization potentials of neighbouring
elements 1361. The interpolation i s based on the fact that changes in the
screening constant Z - Zs from element to element occur monotonically
throughout the periodic table. Interpolation thus leads to values f o r
unknown screening constants, from which the ionization potentials can
be calculated.

In specrroscopic determinations of the ionization potentials of


molecules, these a r e found from the Rydberg s e r i e s limit in band
spectra. U3en it is reliably established that this limit corresponds to
transiticns between the zero vibrational levels of the electronic ground
states of the ion and molecule, the resulting ionization potentials may be
referred to a s the adiabatic potential. A considerable number of ioniz-
ation potentials of complicated organic molecules has been found by
studying the absorption spectra of molecular complexes (in the visible
region). These spectra a r e associated with transitions of electrons
from donor to acceptor molecules. Transitions of this kind require
an energy which, on the first approximation, may be written in the form

where I istheionizationpotentialof the donor molecule, Eil i s the elec-


tron affinity of the acceptor molecule, @/, i s the Coulomb interaction
between the charges, and B represents all other interactions.

Comparative studies of the absorption spectra of molecular complexes


consisting of identical acceptor molecules and different donor molecules
permit the determination of ionization potentials of the donor molecules.
A large number of molecular complexes of various organic compounds
have been investigated [ W , and the ionization potentials of complex
molecules have been obtained a s a result. The accuracy of this method i s
not very high (0.3 - 0.4 eV) but the method enables one to investigate
compounds whose ionization potentials a r e difficult to determine in other
ways. Since, however, spectroscopic methods can only be used in
relatively r a r e cases, because it i s difficult to interpret molecular
spectra, the principal methods a r e the electron-impact and photo-
ionization methods.

When an electron o r photon of sufficient energy collides with a


molecule, the latter becomes ionized. The transitions between electronic
states produced by an electron o r a photoncan be described in terms of
the Franck-Condon principle, according to which an electronic transition
has no direct effect on the position of the nuclei. Therefore, in the case
of ionization by electron o r photon impact, there i s a change only in the
potential energy of the system. Ionizationofthe H2 molecule by electron
impact can be described by a vertical transition of a point at the
rxinimum of the lower potential curve ( the ground state 1C+g of the
H2 molecule) to the upper potential curve (the ground state 28; of the
H.$ ion).
However, in the case of the vertical transition, the H$ ion does not
end up on the zero vibrational level (because the equilibrium distance
between the nuclei for the 25; state of the H$ ion i s greater than for
the IZ: state of the H2 molecule. The electron energy at which the
Hzt ions a r e produced i s therefore greater than the ionization potential
determined spectroscopically (the adiabatic ionization potential) which i s
equal to 15.427 eV. It i s usually stated that this energy i s equal to the
vertical ionization potential of the molecule and differs from the
adiabatic potential by the vibrational excitation energy of the ion.
The vertical ionization potential of hydrogen i s approximately 16.0 eV.

It should be noted that the vertical transition requiring about 16.0 eV


i s the most probable but not the only possible one, since in practice
the observed transitions rna) occur in a finite range of inter-nucleus
distances (the Franck-Condon region). The width of this region i s
usually about 0.2 '9,

With increasing sensitivity of recording of H$ ions their appearance


potential will become smaller and will tend to the adiabatic ionization
potential (an increase In the sensitivity i s equivalent to an extension of
the Franck-Condon region).
Accordingly, only the most sensitive methods of detection of ions have
led to results approaching the spectroscopic (adiabatic) ionization
pctentials. For example, zccording to Hagstrum and Tate [371, i~~ =
15.5 5 0.1 eV.

The appearance potential of molecular ions determined by the method


of electron impact i s the same a s the adiabatic potential if the equili-
brium distances between the nuclei a r e the same in the molecule and in
the molecular ion. In the maiority of cases the equilibrium distance in
molecular ions i s in fact g r e a t e r , and therefore the corresponding
vertical ionization potentials a r e greater than the adiabatic potentials.

For complicated polyaton~icmolecules the potential curves (surfaces)


a r e unknown. However, the concept of one-dimensional potential curves
may be retained for the purposes of qualitative description of the
ionization processes. It i s convenient to regard the polyatomic molecule
a s consisting of two p a r t s , e.g. a s a combination of radicals R I and R2.
There a r e three possible cases inthe ionizationof molecules of the type
R I K 2 . The first of these occurs when the potential energy curves of the
molecule and ion have minima ~t the same equilibrium distances, and
the vertical ionizatior. potential i s the s a m e a s the adiabatic potential.
In the second case, the potential energy curve for the ion has a minimum
which i s at a somewhat greater equilibrium distance and the vertical
ionization potential i s greater than the adiabatic potential. The tail of the
ion appearance curve, how e v e r , reaches, the adiabatic ionization po-
tential. In the third case, when the potential curves of the molecule and
of the ion a r e displaced relative to each other so much that the most
probable transitions take place to very high-lying levels, the vertical
(measured) ionization potential may be much greater than the adiabatic
potential. In transitions to points on the potential curve for the ion which
lies above the dissociation limit, tne molecular ions dissociate into
the fragments R; and R ? .

Most of the measured ionization potentials of molecules have been


obtained hy the electron impact method, using a m a s s spectrometer for
the identification and recording of ions. In this method the ion current i s
measured a s a function of the voltage acceierating the electrons. This
yields to the so-called ion appearance curves from which the ionization
potentials a r e determined.

The main difficulty in the determination of the ionization potentials


i s due to the fact thatthe ionizingelectrons do not all have precisely the
sxme energj. The determination of the ionization potential from the
initial part of the ion appearance curve i s then,exceedingly subjective.
The proredure adopted in early work, in which the ion current was
extrapolated lineariy to z e r o , cannot be justified theoretically, and is now
used only in the case of very small ion currents. It provides an upper
Hmit for the ionization potential.

Various methoas have been developed to ensure that the determination


of the ionimtion potential is more objective. They give satisfactory
results only when the dependence of the probability of ionization on the
electron energy i s the s a m e both for the molecules under investigation
and the calibration molecules '.
The ionization potential difference i s then determined directly from
the distance along the energy axis between the appearance curves plotted
so that their straight line sections a r e parallel. If, however, the de-
pendence of the probability of ionization on the electron energy i s not
the same for the two ions which a r e compared, this procedure cannot
be adopted, although it i s used in a modified form a s described in [381.

The development of the electron impact method has led to analytical


evaluations of the correction which must be introduced in order to allow
for the effect of the electron energy spread on the form of the appearance
curve [391. Under certain simplifying assumptions about the energy
dependence of the ionization probability near the ionization potential,
it i s possible to establish the point on the appearance curve which
corresponds to the true ionization potential. This method has been used
by uonig l401 and a similar method by Lossing et al 1411. Such methods
can be used to determine the ionization potentials of molecules having
appearance curves similar to those for the calibration ions to an
accuracy of up t3 0.1 eV.

Another method of determining the ionization potential i s to use


monochromatic electrons. Magnetic and electric filters i42.431 have not
been successful because of the complexity of the necessary apparatus
and the attendant reduction in the electron current. A better way i s to
employ an electric filter and use the phenomenon of dispersion for
particles entering at an angle of 45" to the electric field between two
plates [441.

The method of quasi-monochromatization put forward by Fox et al.


deserves particular attention. It has been used in recent years to
obtain the most reliable information on the ionization potentials of a
number of molecules. The principle of the method is a s follows.
The electron beam i s passed through a diaphragm which lets through
only those electrons whose energy i s sufficient to overcome the potential
difference between the diaphragm and the cathode, The increase in the
ton current when the potential of the diaphragm V i s changed by
4b' i s determined. This increase is cIearly due to electrons whose
energy distribution has a width of A V and, what i s particularly im-
portant, does not have an exponential tail. This removes the effect of the
electron energy spread. The effect of the electric field which penetrates
into the ionization chamber is minimized by the fact that the ionization
of the molecules and the extraction of the ions which a r e produced a s a
result i s carried out successively and not simultaneously. During the
ionization process the extracting field is zero, while during the ex-
traction process the electron heam i s cut off. The appearance curves
' The v i e c t r o n e r l e r y i s a f ~ ~ r i c t i oni lf b o t h t h e a p p l i w i a c c e l e r 3 t i n g p o t e n t i a l
and t h e c o n t a c t p o t e n t i a l b e t w ? s l t i : c~i L i ; n i l 2nd t h i , i w i z a l i o n chamber, w5icii
canrlnt be c o n t r o l l e d d i r s c t i v , i t i,,t h ? r i ? i s r ~n e c e : s b ~ j ili a l l cases t o conioare
t h e measured i o n i z a t i o n p o t s n t i n l w i i h t h c k w u n i o n i z a i i o n p o t e n t i a l o f a ca-
l i b r a t i o n gas ( w a l l y a n o b l ~,qas) u!:icl7 i s i n t r o d l i c i j d i f i t o t r e chamber t o g e t h e r
wfth t h e gas u n d e r i n v z s t i g a t i o ~ .
obtained by Fox's method do not exhibit the asymptotic tail and the
ionization potential i s determined from the foot of the curve which r i s e s
sharply from the energy axis. The difference A V i s usually taken to be
in the range of 0.5-0.1 eV and i s a measure of the limits of accuracy
of the ionization potentials determined in this way.

Photoionization measurements of ionization potentials of molecules


usi a m a s s spectrometer have been regularily reported since 1956
[ 4 6 2 8 1 . In this method the ionizing beam can be much more monochm-
matic, and therefore the accuracy of the ionization potentials is higher
(0.01 eV). Studies of the appearance curves recorded with high resolution
by the photoionization method have led to the conclusion that the proba-
bility of ionization of molecules with an ionizationpotential I by a photo
of energy F: can be represented by a step function: it is equal to zero
for E<I and i s constant for E>I.

All the considerations which apply to transitions induced by electron


impact in accordance with the Franck-Condon principle a r e also valid
for photoionization. The adiabatic ionization potential cannot be de-
termined from the appearance curve when the potential energy curves
for the molecule and the ion a r e highly displaced.

When radicals can be admitted a s individual particles into the ioniza-


tion chamber, their ionization potentials can be determined by the same
method a s the ionization potentials of molecules. The radicals a r e
usually obtained by pyrolysis of halogen-substituted molecules which
lose the halogen quite easily. The pyrolysis i s c a r r i e d out in the im-
mediate neighbourhood of the region of ionization, s o that the radicals
enter it practically without collisions. A method has recently been
developed which enables one to investigate radicals through dissociation
of molecules by electron impact. They can then be studied by ionizing
the resulting radicals again [so].

If a Ugas* of f r e e radicals cannot be produced for one reason o r


another, it i s possible to determine the ionization potential by a n
indirect method. If the ionization of the molecule RlRz also involyes the
dissociation process in accordance with the equation R1R2+ e +R R2++
+ 211 the appearance potential for the R; ion i s given by

where D i s the dissociation energy of the molecule, K is the kinetic


energy and t' the excitation energy of the fragments.

It follows f r ~ mthe expression for the appearance potential of the


fragment ion R 1 th+at the ionization potential of the radical R, may be
calculated if AP(R l), D(R1-R2). K and E a r e known. The quantity
A P ( R ; ) is measured experimentally from the initial part of the appearance
curve by the same method a s the ionization potentials of the molecule.

The quantities K and E require special consideration. This was


given above in connection with the m a s s spectrometric method of
determining the dissociation energies. While the initial kinetic energy
of the fragments can still be measured, there a r e no experimental
methods for the determination of E , and i t i s usually assumed that i t
i s zero. Therefore, in principle this method giv;; the upper limit for the
ionization potential.

Stevenson (511 has compared a large number of appearance potentials


of fragment ions and has shown that in dissociative ionization the sum
E + K i s very nearly z e r o when the ion i s a fragment with a lower
ionization potential, i.e. when I ( R 1 )< / ( R z )

There a r e a number of semi-theoretical and semi-empirical methods


for the determination of the ionizationpotentials of molecules. Lennard-
Jones and Hall 1521 have developed methods for the calculation of
ionization potentials. They a r e based on the theory of equivalent molecu-
l a r orbits. Hall developed a general formula for the ionization
potentials of normal paraffins:

where s i s the number of C-C bonds in the molecule.

Hall used known ionization potentials of the f i r s t members of a


homologous s e r i e s to determine the constants a , 6 , c, d and e , and
calculated the ionization potentials of other molecules. The agreement
between the calculated and the experimental values was fo&d to be
satisfactory. Hall's method has been used to calculate the ionization
potentials of various molecules [S41 and f r e e radicals [ss].
METHODS O F DETERMINING ELECTRON
AND PROTON AFFINITIES

Electron affinity

Detailed reviews of the methods available for the determination of


electron affinities a r e given in Massey's monograph 156] and also in
Pritchard's review [S?]. The formation of negative ions has been
reviewed by Buchel'nikova [S81. Below, these methods will only be
listed and very briefly discussed.

There i s no universal m a s s spectroscopic method a t t h e present time


for the determination of electron affinities over a reasonably extensive
range of atoms and molecules. The most accurate method of determining
E -l i s based on the phenomenon of surface ionization at hot tungsten
[SgI. This method i s particularly reliable when the ions produced a r e
investigated with the aid of a mass spectrometer. It can be shovm that
the ratio of the electron emission o, to the emission of negative ions
\ - at the hot tungsten surface i s given by

where i i s the number of neutral atoms reaching the hot surface per
second, e i s the electronic charge, E-l i s the electron affinity and
1 i s a constant. By measuring \,,'v_ a s a function of T one can de-
termine E.4. This method has been used to determine the electron
affinity for a number of halides and for oxygen [Go].

Another method i s based on the surface ionization on hot tungsten of


vapours of the alkali metal halides [611. In this case the ratio of the
current of the positive ions of the metal to the current of negative ions
i s given by

where I i s the iordzation potential of the metal and cp i s the work


function of tungsten. This method has beenused to determine the electron
affinity of halides.

In principle, E 4 can also be determined by the electron impact


method. The collision of an electron with a molecule may lead to the
dissociation of the molecule and the formation of a negative fragment
ion. By measuring the appearance potential of this ion and the initial
kinetic efiergy of the fragments, it i s possibleto determine the electron
affinity of the fragment. Thus, for example, a measurement of the
appearance potential of Br' ions produced in the reaction
Br, f e -+ Br + Br-,
can be used to determine the electron affinity from the equation

EA (Br) =D(Brz)-AP(Br-) +K(Br) + K @ - ) , (22)


where D(Br2) i s the dissociation energy of Br2 and K i s the kinetic
energy.

This method of determining EA involves the measurement of very


small ion currents, which reduces the accuracy of the method very
considerably.

A further method which involves the determination of equilibrium


electron density i s based on the investigation of the equilibrium X+ e~r?
X-,
which occurs in space near a hot wire containing the electronegative
particles X and electrons. The equilibrium constant of this reaction
i s determined by the electron affinity, and i s given by

The variation in the electron density with temperature may be


determined by measuring the electrical conductivity (or, in the case
of flames, by measuring the electric permeability at ultra-high fre-
quencies).

A very accurate and more direct method of determining the electron


affinity i s to find the minimum energy of a photon which i s necessary
to remove an electron from the negative ion [62]. This energy i s equal
to the electron affinity. In practice, one measures the current of
electrons produced a s a result of the irradiation of negative ions
produced in a separate ion source. This method has led to the most
accurate value for the electron affinity of oxygen(EA = 1,465 F0,005 eV).

So far we have confined our attention to direct experimental methods


for the determination of electron affinities. The next group of methods
can be used to calculate the electron affinity of atoms and molecules
from various thermochemical data (either theoretical o r experimental).

The following circular process may be used to determine the electron


affinity of an atom Y if all the thermochemical quantities characterizing
the following reactions a r e known:

It follows from this process that

E.4 (Y) =:D(XY) -D(X+--Y-) -I-I(X1.


Since the dissociation energy I1 ( X L ' ) of diatomic molecules and the
ionization potentials I (X) of the atoms a r e known in most c a s e s , it i s
possible to determine E.1 ( Y ) if the dissociation energy D (X+ - Y-) i s
known. The latter quantity may be calculated from the heat of subli-
mation L of the molecules XY and the energy U of the crystal lattice
consisting of the X+ and Y- ions. In that case the circular process
x-+Y--+xY[ c r , s ? d > ) +- L:,
- D ( S + - - l'-j,
S-+l'--+S'f(:a;j

The energy &l can be calculated, whereas L can be measured. The main
method of verifying the accuracy of E.4 found i n this way i s to compare
the results obtained for the same anion Y- with different cations.

The electron affinities of organic radicals can in many c a s e s be


determined from the polarographic discharge potential of the ions on a
mercury electrode. Thus, for example, it was shown in L571 that the
reduction on a mercury cathode of the molecules RHgX (where R i s an
aikyl radical and X i s z halogen) proceeds in the following two stages:

RHg'Le-rRHg
In this process the radical RHg i s absorbed on the surface of mercury,
where i t i s converted into the radical R The latter i s reduced in
accordance uith the scheme
R I 2 - L 1 - c -R-.
Comparisons of the discharge potential for ions corresponding to this
reaction with the discharge potential in the c a s e of high dilution may be
used to determine the electron affinity of the radical R. The method
based on the investigation of electrode processes can also be used to
determine the electron affinity of hydrocarbon molecules [631.

Consideration of the solution of the gaseous ions H+ and X- in water,


In accordance uith the scheme
EfLtguc, --X-(:
c)J ~ ~ ~ c r - + H t t ~ y c r . ) + \ - ( I?.)
h~

may be used to express the heat of formation of the negative ion in t e r m s


of the heat of formation of fully dissociated molecule H X in water and
the hests of hydration of the H ion. If H X i s a strong acid, then the f i r s t
quantity i s in most c a s e s known: i t can also be determined for weak
acids. The heat of formation of the negative ion X- (and, when the
heat of formation of X i s known. the electron affinity also) i s therefore
determined only by the heat of hydration of H+. For a heat of hydration
of H+ = 260 kcal, the heats of formation of negative ions a r e in good
agreement uith the values obtained from the energy of the crystalline
lattice.

Comparisons of the ionization potentials of isoelectronic atomic ions


has shown that they depend quadratically on the nuclear charge. G l o c ~ l e r
1641 has put forward the following extrapolation formula relating the
nuclear charge and the ionization potential of the isoelectronic ions:

This formula may be used to determine the ionization potential of a


negative ion, i.e. the electron affinity of the atom. The constants a , P,
and a r e found from known values of the ionization potential, and Z i s
the nuclear charge. Various attempts have been reportedin recent years
to improve Glockler's formula [65, 661,

Proton affinity
In addition to the ionization potentials of atoms and molecules and
the electron affinities, the proton affinity P, i.e. the energy released
when the ion H+ i s attached to the molecule under consideration, i s
also for particular importance in the calculation of the energetics of
ion reactions and of ionization equilibria at high temperatures.

The mass spectroscopic determination of the appearance potentials of


ions produced in the dissociative ionization by electrons of hydrogen-
containing saturated compounds can in many cases be used to find the
proton affinity P of the corresponding unsaturated compounds, for
example olefins. In order to determine the proton affinity of ethylene, i t
i s necessary to find the heat of the reaction

The CzH5 ion appears when ethane i s bombarded by electrons of


energy equal to 12.80 2 0.1 eV [541. The proton affinity of ethylene i s
then found from the circular process

However, this method can only be used without additional studies when
the dissociative ionization does not lead to the formation of excited
products o r to products having a kinetic energy which i s high compared
with the thermal energy.

roton affinities of simple molecules such a s H2 167, 681 and


CH4The P
169 have been calculatedusing hypothetical models of the molecule-
plus-proton system. For example, Hirschfelder 681 has considered
two configurations of the ~ t i o n namely,
, the linear and the triangular
configuration. Calculations have shown that the triangular configuration
i s the more stable and the ground state energy of i in the form of a
right-angled triangle i s lower than in the case of an equilateral triangle.
According to Hirschfelder's calculations the energy of the ~ e i o ins
equal to 184 kcal, but the more accurate calculations of Eyring and
Barker 1701 have led to a value of 180.2 kcal, Since the dissociation
energy of hydrogen i s 103.2 kcal, the protonaffinities of H2 and D2 a r e ,
according to these data, respectively equal to 81 and 7 7 kcal.

Studies of the scattering of protons in hydrogen, carried out by


Simons e t al. [711, have made i t possible to find the energy of inter-
action between H+ and He. In accordance with Hirschfelder's calculations,
these workers assumed that the equilibrium distance of the third
hydrogen atom of H; from the line connecting the two other H atoms is
1.5 '3, and using the experimental law of interaction found that P(H2) =
69.2 kcal.

Studies of the elastic scattering of H+ ions in water vapour have also


led to the determination of the energy of interaction between the H20
molecule and the proton. If it i s assumed that the equilibrium distance
of the proton from the oxygen in HQO+i s the same a s of the hydrogen in
H20 (1.013.1) then the proton affinity of water i s found to be 6.5 eV o r
150 kcal. The assumed equilibrium distance i s probably too high, since
H30+ i s a very stable ion and the distance between the atoms may be
smaller than in a water molecule. This would lead to a higher value for
the proton affinity.
The quantity P(H20) has also been calculated on the assumption that
the energies of the isomorphous crystals NH4C10, and H ~ o ' c ~ o ~ -
a r e the same [72, 731, With P(NH3) = 211.3 kcal with the appropriate
correction for the difference between the interatomic distances in
S H 4 C 1 0 4 and H30fC10s-, it was found that P(H20) = 188.6 kcal. It
should be noted that the reference quantity P(NH3)was obtained i n this
calculation indirectly (using the lattice energies of ammoniumchloride,
bromide and iodide, the electron affinity of the halogens and the heats
of formation of the halogen atoms; hydrogen bonding in the crystals
was neglected 1741).
A m a s s spectrometric method has been developed in recent years for
the determination of the proton affinity of saturated molecules 1759 761.
This method (the method of ion impact) i s based on the fact that second-
a r y processes with hydrogen atom o r proton transport a r e detectable
in the m a s s spectrometer when they a r e exothermic and a r e not
detectable when they a r e endothermic.

Assuming that the process

i s observed, while the process

i s not, (where R1H and RzH a r e the hydrogen-containing molecules, R1


and R2 a r e radicals, and hl i s the molecule whose proton affinity is to
h determined), we have

where D(R* - H) and D(R2 - H) a r e the RI-H and Rz-H bond energies,
/ ( M ) i s the ionization potential, and P(M) i s the proton affinity of the
molecule hI.
Similarly, when the process

RIH++M=RI +MH+,

i s observed, whereas the process

is not, we have

D (RI-H) + I (H) -I (RIH)<P(M) ,<D (R,-H) + I (H) --I (R2H). (27)


By choosing the most suitable R I H and R2H i t i s thus possible in
many cases to estimate P(M) with a high accuracy,

It should be noted that an analogous procedure can be used to estimate


any thermochemical quantity entering into the expression for the heat
of the corresponding reactions. Thus for example i t i s possible to
estimate D(R-H) o r I ( M ) if all the remaining parameters entering into
the inequality a r e h o w n . In this process i t i s important to know the
molecule whose ionization potential i s equai to the appearance potential
of the secondary ion. Consequently, the ion appearance potentials must
be measured in the ion impact method. Methods available for the
determination of the appearance potentials were discussed above.

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1 4 . HUTCHISSOS, D..4. (1956). 1. C h e m . P i ? s . , 24, 628.
45. FOX, R . E . , HICK4\1, a , \ l . , KJELDAAS, T . , and GROVE, D . J . (1951).
P ' i ~ s .R e r . , 84, 859.
46. LOSSLUG, F . P . , and TAN.AKA, J . (1956). l. C h e m . P h ? s . , 25, 1031.
47. \'ISELOV, F.I., and T E R E N I S , A . S . (1957). D o k l . 1 V SSSR, 115, 744.
48. U T . k U B E , K. (1957). 1. C i e m . P h \ s . , 26, 542.
49. BRIEGLEB, G., and CZEK.ALL.4, J . (19591. Z.E l e k t r o c h e m . , 63, 6.
50. BECK, D., and OSBERGHAUS, 0. (1960). Z. P h y s . , 160, 406.
51. STEVENSOS, D.P. (19531. D ~ s c .Farad. j o c . , 49. 867.
52. L E n 4 R D - J O N E S . J . , and H - I L L , G.G. (1951). D i s c . F a r a d . S o c . , 10, 1 8 .
53. K 4 L L , G.G. (1951). P r o c . R o v . S o c . A205, 541.
54. F I E L D , T . H . , and FR.ASKLIS, J . L . 1957. Electron Impact Phenomena.
Acadernlc P r e s s , S . Y .
55. K-\RRISOS, .\.G., and LOSSING, F . P . (1960). l. 4 m . C h e m . S o c . , 82, 1052.
56. \l.ASSEY, H.S.W., 1938. . Y e g a t i r e I n n s . Cambridge.
57. PRITCHARD, H.O. (1953). C h e m . R e c . , 52, 529.
58. BUCHEL'NIKOVA, S . S . (1958). L ' s p e k h . f i z . n a u k , 6 5 . 351.
59. VIER, D.T., and \L4YER. J . E . (1944). 1. C h e m . P h y s . , 12, 28.
60. McCALLUM, K.J., and MAYER, J.E. (1943). 1. Chem. P h y s . , 11, 56.
61. IONOV, N.I. (1948). Zh. e k s p e r . teor, fir., 18, 174.
62. BRANSCOMB, L.M. (1958). e t . at. P h y s . Rev., 11 1 , 504.
63. LYONS, L.E. (1950). Nature, 166, 193.
64. GLOCKLER, G. (1934). P h y s . R e v . , 46, 111.
65. JOHNSON, H.R., and:RO HRLICH, F . (1959). 1. Chem. P h y s . , 30, 1608.
66. ELDEN, B. (1960). 1. Chem. P h y s . , 33, 98.
67. HIRSCHFELDER, J.O. (1937). 1. Chem. P h y s . , 5, 695.
68. HIRSCHFELDER, J.O. (1938). 1. Chem. P h y s . , 6, 795.
6 9 . HIGUCHI JIRO, J . (1959). 1. Chem. P h y s . , 31, 563.
70. BARKER, R.S., and EYRING, H. (1954). 1. Chem. P h y s . , 22, 2072.
71. SIMONS, J.H. (1943). e t al. 1. Chem. P h y s . , 11, 312; 1. Chem. P h y s . , 11,
316.
72. SHERMAN, J. (1932). Chem. R e v . , 11, 93.
73. KONDRAT'EV, V.N., and SOKOLOV, N.D. (1955). Zh. fiz. khim., 29, 1265.
74. KONDRATIEV, V. (1960). Roy. I n s t . Chem., N 3.
75. TAL'ROZE, V.L., and FRANKEVICH, E.L. (1956). Dokl. AN SSSR, 111,
376.
76. TAL'ROZE, V.L., and FRANKEVICH, E.L. (1959). Zh. fir. khim., 33,
955.
I. BOKD E S E R G I E S

Table 1
DISSOCI.ATION EKERGIES O F DIATOhIIC MOLECULES
(kcal/mole)

T h e t a b l e g i v e s the :i!ssociarlun e n e r q i e s of d i a t o m i c m o l e c u l e s
l i s t e d i n a l p h a t ~ e r i c a lo r d e r .

T h e second anti t h i r d c o l u n i r i ~ g!ve the vdiues of the d i s s o c i n t i o n


e n e r g y :lt 0 and 298.15 'K. T h e c o n v e r s i o n f r o m one t e m p e r a t u r e to t h e
o t h e r u a s c a r r i e d out oii the t).i,is o i the iorn;u;,i

, >
with the e x i e p t i o n oi v.iluei taken i r o ~ i : re:. l i ! , \%hichgive, the c!ata
n e c e s s a r y for the i o n v e r i ~ ~ )using
n the e u c t equation ( 7 ) on p, i x .

T h e fourth ~ o l i l r n ngives the method u s e d to d e t e r m i n e the d i s s o c i a t i o n


energ!.. i l h e r i e v e r the . i p p r a p r i a t e r e s u l t 2 couiti not be tieternlined f r o m
d i r e c t o r i n t i l r e c t experimenLi1 d n t d the? -+.ere found hy e x t r a p o l a t i o n of
t h e v i ! ~ r a t i o n ~ i l! e v e l s of the p a r t i c u l . i r niolccule. T h e fourth column
then g i v e s thc extr.?pol;it!on niethotl (graphic-tll, using the g r o u n d - o r
e x c i t e d - s t a t e c o n s t a n t s , o r l i n e a r !I-iiig !he Burge-Sponer f o r m u l a .

T i r o s e r l e . of v ~ r l u e sof c!ibsoci.!tinn e n e r g i e s of d i a t o m i c n i o l e c u l e s
'Ire given i n the l i t e r ~ t u r e ,ot)tdined in the f i r s t c a b ? by l i n e a r e x t r a -
poi8tion using t h e Burge-Sponer forniuln ( t h i s i s r e f e r r e d to a s t h e
L.B.S. m e t h o d ) : x a l u e s i r e ~ d l i l u l ~ t e cdi i r e c t i f r o m t h e f o r m u l a
'
:,C
- - - - - Q
- 4w,r, 2 (26)

AS recommended, f o r e x a m p l e . by H e r r i ~ e r gi 2 3 :\nd, in the s e c o n d c a s e


f r o m the v.l!ues reconiniendeti Ga>tion [3! ~ h i c h: 7 r ~l o ~ e by r 20%.

Recent s t u t l l e s lead to the L s n c l u s i o n t h i t the r e d u c t i o n in the values


ccilculatetl t ~ yI i n e d r extrapoi.itlo!i cannnt he justified. T h e v a l u e s given
in the t < i l ~ l e.Ire t h e r e f o r e :is .I r u l e t h o s e founc! d i r e c t l y f r o m equat,ion
( 2 6 ) . In iso1,itecI c a s e s i n u hich e x p ~ r t n i e n t adl a t a s u g g e s t that the L.B.S.
method le,~tl.-to v a l u e s irhich :irp too high. the t a h l e g i v e s f i g u r e s r e d u c e d
h. 20'g. T h c iifth c o l u m n g i v e s the r e f e r e n c e to the o r i g i n a l s o u r c e in
which the c i ~ r r e s p o n c l i n g iiissori;ition e n e r g h a s b e e n obtained o r
reconl!mentletl,

As a r u l e . t h e e r r o r s in the d i s s o c i a t i o n e n e r g i e s a r e t h o s e given i n
the o r i g i n ~ ls o u r c e s . D i s s o c i a t i o n e n e r g i e s est:rnated \ + i t hthe aid o f t h e
l i n e a r e x t r a p o l a t i o n in a c c o r o a n c e rvith Gaycion's r e c o m m e n d a t i o n
a r e given e r r o r s of 20'&
Table I

L.B.S. f o r t h e ground s t a t e
Nass s p e c t r a m e t r i c ( s e e Note 1)
d l tto
Thenochemicai c a l c u l a t i o n

ditto
M a s ~spect rometri c
L.8.b. f o r the g r o u l d s t a t e
E x t r a p o l a t i o n ~f X I \ _ l e v e l s
Calc from heats o f formation and
su61imation
Spectroscopic ( f r o m convergence o f
bands)
L.E.S. f o r the ground s t a t e ( u s i n g
data i n /13/)
L.B.S. f o r tne 821 s t a t e
Mass spectrometric
Mass spectrometric (using data i n / i l / )

A n a l y s i s o f v a r i o u s data
Table 1 (co~tinued)

Yol e-
cule

.4 !C L.5.~ f c r tc; gr3Und s t a t e ( u s i n q d a t a i n


.:l; see i s t e ?
!?!C1 L ~ ' c ~ ' a t i o zased
n sn o a t a on r e a c t i o n
e?ui!ioria
i n a ' y s i s ,? ?hermochemical ana
scect roscoai c ~ e a s u r e n e n t s
3.11- E a u ~ l i ~ r '3 fu ~t h e r e a c t i o n
k i F; , 2A1 L 3AlF
L n a , r a i s o f t r e n o c h e m i c a ; and
s a e c t r o s c o p i c measurements
ilH ~ p e c t r o s c o o i cj p r e d i s s o c l a t ~ o ni n ~ 1 1 1
s t a t e , ; L.;.). (using data i n I N / )

~ ~ e c t r o s c o o i(cp r e a i s s o c i a t i o n i n A1 I I
state!
Xl I w e c t r o s c o p i c (convergence o f bands)

AlX istimatec
A!O Pass s a e c t r o m e t r i c
Ci s s o c i a t l an e a u i l i b r i a i n f l a m e s

,A 15 ~ ~ 9 . 3 .f o r t h e ground s t a t e
~ ~ e c t r o s c o p i(cp r e d i s s o c i a t i o n i n the
E?\ state,
.l': > p e c t r o s c o p i c r re dissociation i n the B
and C s t a t e s ; see Note 3)
.\S, L.a.>. f o r the x2\ state
AsY L.B.?. f o r t h e XI\-s t a t e
.?i 5 ' 3 > ~ e c t r o s c o ~I ~p rce d i s s o c i a t i o n i n the
3 state]
A5n+ ~ ~ 6 . s f.o r t t e X ' \ _ s t a t e ( u s i n g data
i n /'?l)
.A :l Mass s p e c t r o m e t r i c ! s e e Note 4 )
1.6.2. f o r t h e XI\ s t a t e
'AUAI ditto
l' I
AuCl
AuCr Kass s p e c t r o m e t r i c
.\ucu P,ass s p e c t r o n e t r i c
i.3.S. f o r t h e ground s t a t e
Table 1 (continued)

Hole-
-
CU e Method

AufI Evaporation o f Au; e x t r a p o l a t i o n o f


l e v e l s o f t h e upper 371 6 s t a t e

AuMp L.B.S. f o r t h e x12 s t a t e


AuPd Mass spectrometric
AuSn n
B2 Mass s p e c t r o a e t r i c
BBr A n a l y s i s o f v a r i o u s data
BC1 E x t r a p o l a t i o n o f AlTT s t a t e
BC1 Calc. from D ( B C l ) , i (BC1) and I (B)
BF E x t r a p o l a t i o n o f hlTI l e v e l s
BH bpectroscopic ( p r e d i s s o c i a t i o n i n t h e
A l r I states)
Anal y s i S o f data on p r e d i ssoci a t i o n
RHt Calc. from D (EH), I (BH) and I (B)
BY L.B.S. f o r the ground and e x c i t e d
1 s t a t e s (see Note 5)
B0 L.B.S. f o r the X22 , ~ 2 1 1, B 2 ~
and c211 s t a t e s (mean value)
Studies o f reaction e q u ~ l i b r ~ a
BS L.S.S. f o r t h e ground s t a t e
BaBr ditto
BaCl n U

BaF
BaIH Spectroscopi c ( p r e d i ssoci a t i on i n the
C28 s t a t e )
BaO Mass spectrometric; d i s s o c i a t i o n
e q u i l i b r i a i n flames

BaS L.B.S. f o r t h e ground s t a t e


Sc, Estimated
BeC1 txtrapolation o f the x ~ X and A2n
l e v e l s ( u s i n g data ~n 1251; N o t e 6)
BeF E x t r a p o l a t i o n o f the x*E and A211
l e v e l s ( u s i n g data i n 1261; Note 7)
BeH Graphical e x t r a p o l a t i o n o f t h e
and A211 l e v e l s (see Note 8 )
B&+ G r a ~ h i c a l e x t r a p o l a t i o n o f t h e X) E
1eve1 S
-
T a b l e 1 (continued)

-
Mole-
cul e

Be0 'ass s:ectrometric


L.R.S. f c r tLle b l ~ l s t a t e( h o t e 9 )
B!? hracbical extrapolation o f 3 levels
( s e e 'late 1 2 )
S r a i ~ i c a le x t r a p o l a t i o n o f t h e X~I
'tvels
)ass spectrometric
Calc. from r8eat o f e v a p o r a t i o n o f B i 2
BIB: iS29 b j o t e , l l )
> p $ c f r o s c o p i c (convergence o f bands;
\ s e e 'tote 1 2 )
BiC! L.3.>. f o r t h e ground and e x c i t e d
states
E q u i l i b r i u m o f 2 3 i t 9iC13 2 3BiC1

B:F G r a l h i c a l e x t r a p o l a t i o n o f ground
state levels
B.I1 L.3.S. f o r t i e xll: and A~IT s t a t e s
B:! L.3.S. f o r t h e ground s t a t e
R,i! E x t r a p o l a t i o n (see Note 2)
EIS~ Mass s p e c t r o m e t r i c
II
Bi Te
B:z S c e c t r o s c o p i c (convergence o f bands)

B:, Calc. from D ( a r z ) , i ( b r 2 ) and l ( B r )


BrCi Calc. from l~,,(BrCl)
RrF ~ p e c t r 3 s c o p i c (convergence o f bands;
see k o t e l ? )
3r0 E x t r a p o l a t i o n o f A? 11 l e v e l s ( N o t e 1 4 )
C2 Yass s p e c t r o m e t r i c
c: h l c . frm D ( C ? ) , I ( C 2 ) and i (C)
CC! b a i ysis o f various data
.3.S. f o r t n e ground s t a t e
CF j r a p h ~ c a lextrapolation o f B 2 1 levels
( s e e Mote 1 5 )
CF+ :ale. fro^ D(CF), l ( C F ) and [ ( C )
CH > p ~ c t r o s c o p i c( p r e d i s s o c i a t i o n i n t h e
E?\_ s t a t e ; see Note 1 6 )
Table 1 (continued)

N aep
CU

CH' Spectroscopic ( o r e d i s s o c i a t i on i n t h e
l i s t a t e ; see Note l')
CN A n a l y s i s o f v a r i o u s data
,jeasure;lent o f gas d e n s i t y I n a shock
wave i n h r t C$:
CN+ Lalc. from r l ( C k ) , I(CEu)and I (C)
CO A n a i y s i s o f v a r i o u s data
CO + Calc. from ~ ( C O ) , 1(CO) and I ( C )
CP L.8.S. f o r t h e x22 s t a t e (reduced
by analogy w i t h CN)
CS Calc. from Ifo(CS,
L.0.h. f o r tile ~ 1 2 : s t a t e
CS + Calc. from D ( C S ) , I ( C S ) and [(C)
csc I.i3.Sa f o r the X12 state
Ca2
CaBr L.9.S. f o r t h e X ~ Xs t a t e
CaCI ~ o e c t r o s c o p i c( p r e d i s s o c i a t i o n i n t h e
uoper 2: state
L.d.S, f o r t h e X72 s t a t e
CaF ~ p e c t r o s c oi c ( p r e d i s s o c i a t i o n i n t h e
excited 1 state)
Cat1 ipectroscopic (predissociation i n the
C 2 2 s t a t e ; see Nate 18)
Ca l L.B.S. for the X 2 2 state
CaO A n a l y s i s o f d a t a on d i s s o c i a t i o n equi-
l i b r i a i n flames and 1sO(CaO)
CaS Calc. from l i m i t o f the c o n t ~ n u o u s
a b s o r p t i o n spectrum
Mass spectrometri c
Cd,
CdBr L.U.S. f o r t h e ground and e x c i t e d s t a t e s

Estimated (see Table 3 )


CdCl L.5.S. f o r t h e X? 2 s t a t e
Cd H Graphical e x t r a p o l a t i o n o f t h e x22:
and ~ 2 1 1l e v e l s
CdHt Graphical e x t r a p o l a t i o n of t h e X' 2:
levels
Cd I L.B.S. f o r the X'Y s t a t e
T a b l e 1 (continued)

Mole- Method
cule

CsH
CSI 2alc. from data on atomic fluorescence and
h e a t s o f s u b l i m a t i o n o f Csl
Thermochemical c a l c u l a t i o n
D i s s o c i a t i o n e q u i l i b r i a i n flames

cuz .B.S. f o r t h e ground s t a t e


Yass s p e c t r o m e t r i c (see Note 20)
CuBr -.B.S. f a r t h e XI ': s t a t e , calc. from
d a t a on the heat o f s u b l i m a t i o n o f
CuBr
CuCl L.B.h. f o r t h e X ~ Xs t a t e
CuF ditto
CuH D i s s o c i a t i o n e q u i l i b r i a i n flames

Cu l L.B.S. f o r the X ~ Z ; state


cuo Cal c. from thermochemi c a l data
Estimated (see Table 3 )
CuSn Mass s p e c t r o m e t r i c
F2 D i s s o c i a t i o n equi l i b r i a o f F2

Calc. from D o ( ~ F )and AH,,(HF, gas)


(see Note 21)
:F Calc. from D ( F 2 ) , !(F2) and [ ( F )
F0 Calc. on t h e assumption t h a t
DdFO) - Do!F20)
FO+ Calc. from I)(FO), I (FO) and ! ( O )
FeBr L.B.S. f o r t h e ground s t a t e
( u s i n g d a t a i n 1411)
FeCl Thermochemical c a l c u l a t i o n u i t h
~H,,(Fecl) t a k e n from 1421
Fe0 D i s s o c i a t i o n e q u i l i b r i a i n flames

..B.S.
Gas lass spectrometric
GaBr i x t r a p o l a t i o n o f A~ 11 l e v e l s (Note 22)
l i s s o c i a t i o n e q u i l i b r i a i n flames
T a b l e l (continued)

;it
- Met hod

GaCl Extraoolation 31 A I 1 1 l e v e l s
C i s s s c i a t i o n e s ~ i l i b r i ai n f l a m e s

GaF E x t r a ~ c l a t i o no f ~ ' 1 1 l e v e l s
Ga I A n a l y s i s o f v a r i s u s :ata ( h o t e 23)
Cl s s o c i a t i o n e q u i l i o r i a i n f l z m e s

GaO i.9.S. for t h e round s t a t e


see h o t e 24)
dltt0
Estlma!ed ( s e e T a b l e 3 )
GdO L.B.S. ( s e e h o t e 21

Ge, scectrometric
GeBr j r a ~ h i c a l extrapolation o f levels of
e
excit d state 2 1 1 ,,
( b e ( C) l ~ m i t !
GeC vass s3ectrometric
GC1 E x r r a p o l a t ~ o no f l e v e l s o f the 2_1
excited state j~e(lt7))
GeF L.3.S. f o r t h e ~ 2 1 1s t a t e (using
d a t a i n 1451)
GeH Calc. w i t h LH,,, t a k e n f r o m 1461
GeO L.3.S. f o r t h e X 1 1 s t a t e
Thermochemical c a l c u l a t i o n
GeS Extra olation o f levels o f the
E & a t e see h o t e 25
GeSe Extraoolation o f levels o f the
E s t a t e ( s e e Note 2 6 )
GeSl pass s p e c t r o ~ e t r i c
GeTe Extrapolation o f levels o f the
E s t a t e ( s e e Note 2 7 )
H? ~ p e tcr o s c o p i c
HD n

D?
HT Calc. f r o m D n ( ~ 2 ()s e e Note 28)
DT ditto
n
T,
H: Calc. f r o m n(H2),! (H?) and I ( H )
T a b l e 1 (continued)

D," Methn6 Ref.


-
4.f Quantum mechanl c a l c a l c u l a t 1 on
37.6 Calc. from .M,, (ii6r-l
12.7 ~ a l c , from n ( ~ B r ) , I ( H B ~ dno
) I (Er)
j3.11 Cdlc. from LH,,, I
19.:3 Calc. from P ( H C l ) , I (HC1) and I ( C i )
35 .:3 E x t r a p o l a t i o n of X 1 2 l e v e l s
)5.9 Calc. from D(PF), I ( d F 1 and l ( H )
i1.3 Lalc. from .ltf,,,,'H I
72.7 Calc. from D(Hl1, l (HI) and / ( l )
72 L.B.S.
2.3 ~ p t ? croscopi
t c
-. i p e c t r o s c o p l c ( w i t h allowance f o r
r o t a t i o n a l e f f e c t s on the form o f t h e
p o t e n t i a l curve f o r t h e X ] 1 s t a t e )
17.4 E x t r a p o l a t i o n o f ground s t a t e l e v e l s

24 L.B.S. f o r t h e ground s t a t s
40.8 ditto
9.6 Spectroscopic ( p r e d i s s o c i a t i on)

54 L.B.S. f o r t h e ground s t a t e
9.2 E x t r a p o l a t i o n o f ground s t a t e l e v e l s

65 >pectroscopic ( f r o m l i m i t o f t h e
ccntinuous a b s o r p t i o n spectrum);
thermochemical calc111ation
47 Spectroscopic (from l i m i t o f t h e
c o n t i nunus a b s o r p t i o n spectrum)
23.3 Pass spectromet r i c
93 Thermochemical c a l c u l a t i o n ( h o t e 29)
- D i s s o c i a t i o n e q u i l i b r i a i n flames

03.2 Thermochemical c a l c u l a t i o n (Note 30)


-- D i s s o c i a t i o n equi lib r i a i n flames

26.8 Extrapolation o f A] 1I l e v e l s
-- D i s s o c i a t i o n e q u i l i b r i a i n flames
Table 1 (continued)

Mole-
cule

~ o e c t r c s c a p i c( ~ r e dsi s o c i a t i o n )

A n a l y s i s o f v a r i e u s d a t a ( N o t e 31)
Cisspciation e q u i l i b r i a i n flames

L.S.S. f o r t h e ground s t a t e
( s e e Rote 2 4 )
E s t i m a t e d ( s e e T a ~ l e3 )
,Vass s p e c t r o v e t r i c
~ p e c t r o s c o p i c( f r o m convergence bands)

t a l c . f r o m /)(i:), I (lij and / ( l )


S o e c t r o s c o p i c ( s e e k o t e 32)
i a l c . from D ( l B r ) , i ( 1 3 r ) and !( l )
S p e c t r o s c c q i c i f r o m l i m i t o f convergence
c f bands; see Note 3 3 )
Calc. from D ( l C l ) , / ( l C l ) and I ( 1 )
S r a c h i c a l e x t r a o o ~ a t i a n o f 83 11 3
l e v e l s ( s e e h o t e 34)
!.@.S. f o r t h e X ~ I [ and A ~ I Ts t a t e s
( s e e i o t e 35)
S i s s c c i a t i o n e o u i l i b r i a i n flames

E x t r z p o l a ? i o n o f 01 11 l e v e l s
Thermochemical c a l c u l a t i o n ;
spectroscopic (atomic fluorescence)

Dissociation equilibria i n flares

Calc. f r o m i k , ~ r m o c h e m i c a l data;
scectroscopi c
J i s s o c i a t i o n e q u i l i b r i a i n flames

Caic. from thermochemical d a t a


(see hote 36)
Dissociation e q u i l i b r i a i n flames

2 r a o C i c a l e x t r a p o l a t i o n o f A;T l
state l e v e l s
Table 1 (continued)

Mole- Method
cule

KJ Calc. from t h ~ r n ichemical d a t a /5b/.


s p e c t r o s c o p ~c [from atomlc f l uoreicence)

O i s s o c i a t i o n e q u i l i b r i a i n flames

La0 Nass s p e c t r o m e t r i c
1

Li, A n a l y s i s o f v a r i o u s data
LiRr C a l c u l a t a d from t h e n o c h e m i c a l d a t a
D i s s o c i a t i o n equi l i b r i a i n flames

LiCl Cal from th~rmochernical d a t a ( w i t h


a f ~ o w a n c e f o r d i m e r i s a t i o n o f molecules
i n t h e vapour phase)
D i s s o c i a t i o n e q u i l i b r i a i n flames

LiF Calc from thermoci~cmical, d a t a ( w i t h


allowance f o r d l m e r l s a t i o n o f molecules
i n t h e vapour phase; see Note 37)
D i s s o c i a t i o n e q u i l i b r i a i n flames

LiH Spectroscopic ( p r e d i s s o c i a t i o n )

Li I Calc. from thermochemical data w i t h


A H ~ ~ ( IL) ~from 1601; s p a c t r o s c o p i c
(long-wave l i m i t o f c o n t i n u o u s
a b s o r p t i o n ssectrum)

D i s s o c i a t i o n e q u i l i b r i a i n flames

LiO Mass s p e c t r o m e i r i c ( d i s s o c i a t i o n
e q u i l i b r i u m f o r LiO i n L i 2 0 vdPour)
LuO L.B.S. f o r t h e ground s t a t e
M
,&
!
MgRr L.B.S. f o r t h e ground s t a t e
MgCl Extrapolation o f and ~2 1 1 l e v e l s ;
comparison u i t h d a t a f o r 3eC1 and MgF;
e s t i m a t e d from t h e mean bond energy
i n MqC12
MgF t x t r a p o l a t i o n o f x2? , A ? 11 and
B?\; (see Note 38)
T a b l e 1 (continued)

Het hod Ref.

A n a l y s i s o f v z r i o u s d a t a (Note 39)

e
Gra h i c a l e x p r e s s i o n o f
X 1 levels
S i s s o c i a t i o n e q u i l i b r i a i n flames
(see Note 40)
L.2.S. f o r t h e ground s t a t e
ditto
D i s s o c i a t i o n e a u i l i b r i a i n flames

L.B.S. f o r t h e ground s t a t e
D i s s o c i a t i o n e a u i l i b r i a i n flames

L.0.i. f o r t h e ground s t a t e
Spect r o s c o p i c ( p r e d i s s o c i a t i o n )

L.B.S. f c r t h e ground s t a t e u s i n g
c o n s t a n t s from /110/

D i s s o c i a t i o n e a u i l i b r i a i n flames

ditto
Mass s p e c t r o m e t r i c
A n a l y s i s o f s p e c t r o s c o p i c measurements and
studies o f dissociation e q u i l i b r i a

Calc. from (NZ), I ( N Z ) and I ( N )


L.B.S. f o r t h e ground s t a t e
Spect r o s c o p i c
E s t i m a t e d from ean N-H and N-F bond
e n e r g i e s I n N ! ~ and NF3 and from t h e
magnitude o f D,(NH)
L.0.i .for t h e ~ 3 s1t a t e ; e l e c t r o n
colllslons
Calc. from AH,, (NO)
Analysis o f rotational structure o f p
and 7 -bands o f h0 ( s e e Vote 41)
-
~ a l c . from D O ( N O ) = 150, I (NO) and I kO.
Lalc. from D o ( ~ 0 ) = 1 5 ? . 3 , l (NO) and I (NI
L.B.S. f o r t h e ground s t a t e
Table 1 (continued)

Mole.
cul e D," Method

Na, 18.J Graphical e x t r a p o l a t i o n of 9' T T l e v e l S;


c a l c u l a t e d from data on equi l i brium
d i s s o c i a t i o n o f Nap
-- Oalc. fron data on s a t u r a t i o n vapour
pressure on sodium
NaRr 88.5 Thermochemical c a l c u l a t i o n and atomic
fluorescence (mean value)

NaCl 08.5 k l c . from thermochemical data


(see Note 42)
NaF 1.1 Calc. from thermochemical data
- l i s s o c i a t i o n e a u i l i b r i a i n flames

Nall 48 ..8.b. f o r t h e ground s t a t e ;


g r a p h i c a l e x t r a p o l a t i o n of A1 I 1 l e v e l s

Na l 71.6 Thernocb,emical c a l c u l a t i o n and atomic


fluorescence (mean value)

- l i s s o c i a t i o n o f e q u i l i b r i a i n flames

Nali 15.2 i r a p h i c a l e x t r a p o l a t i on o f C1 I I levels

N nR b 14.0 ..b.S. f o r t h e x12 and A' l l s t a t e s


NbO 81 ..B.$. f o r the a r o t ~ n ds t a t e [ u s i n g
aata i n /b8/)
NdO 56 l a s s spectromet r i c
NlRr 86 I i s s o c i d t i o n e q u i l i b r i a i n flames

NICI Ih~rmochemical c a l c u l a t i o n u i t h
AF{,,( Ni Cl ) from 1421
80 I i s s o c i a t i o n e q u i l i b r i a i n flames

NI I jitto
NIH ;pectroscopic ( p r e d i s s o c i a t i o n )

61 i r a p h i c a l e x t r a p o l a t i o n o f 2~ l e v e l s
(see Note 4 3 )
N10 98 i i s s o c i a t i o n e q u i l i b r i a i n flames

o2 l!)
1; i t r a p o l d i o n of ~ 3 2 , l e v e l s
T a b l e 1 (continued)

no1 e- Fief.
cule
-
0; ~ 2 1 ~f r .c m 0 1 0 2 1 , 1 (02) and i (0) Ill
OH E x t r a p o l a t i o a o f 8'11 and 6 2 2 l e v e l s 1 , 7 2 , 961
OH- Calc. f r o m D ( 3 ) , I ( ~ and P ) I(D) [l1
OH Calc. from D ( ? H ) , E A ( O H )and ~ 4 ( 0 ) Ill
p2 Srectroscopic (predissociation i n the Ill
a l l s t a t e ( s e e Note 44); g r a p h i c a l
e x t r a p o l a t i o n o f XI'; levels
PC I E s t i m a t e d from D ( N ) and mean bond I11
e n e r g i e s i n NH3 and PC13
PF E s t i m a t e d from D ( ~ Hand ) mean bond l11
e n e r g i e s i n Nb3 and PF3
PH i s t i m a t e d i r o n D ( M H ) and mean bond Ill
e n e r g i e s i n HH? and pH3
P\ Calc. f r o m 1 H ..,(PN) ['l
PO Calc. f r o m convergence o f 02 L l e v e l s [I1
and r o t a t i o n a l s t r u c t u r e c u t - o f f
f o r F-x2 i 1 ( s e e Note 45)
Pb2 Fass s p e c t r o m e t r i c 1241
PoBr L.B.>. f o r t h e grcund s t a t e ; l741
s p e c t r o s c o p i c ( ~ r e dsi s o c i a t i o n )

P-Cl ditto V41


PSF Spectroscopic ( p r e d i ssoci a t i o n i n t h e [:;l
8 2 1 state)
PbH ditto I31
I
I21
PS1 (31
Pb 0 Calc. from thermochemical d a t a 'l
ditto 1701
P bS W
[31
PbSe Mass s p e c t r o m e t r i c [751
P bTe n
C751
Pd (113j
PO- E x t r a p o l a t i o n o f ground s t a t e l e v e l s 1761

Calc. f r o m AH,,(PO~); vapour ["l


p r e s s u r e measurement
Pro Mass s p e c t r o m e t r i c [ 108)
T a b l e 1 (continued)

-
-
Role- Met hod
cu e

R ba Graphical e x t r a o l a t i o n o f ground and


two e x c i t e d s!ate l e v e l s

RbBr Calc. from thenochemical data


D i s s o c i a t i o n e q u i l i b r i a i n flames

RbCl Calc. from thenochemical data u i t h


A H S o (RbCl) from 1771
D i s s o c i a t i o n e q u i l i b r i a i n flames

R bF Calc. from thermochemical data w i t h


LW,, (RbF) from 1391
D i s s o c i a t i o n e q u i l i b r i a In flames

R bH L.B.S. f o r the X1B s t a t e


RbI Calc. from thermochemical data w i t h
AH,,(R~I) from 1561; atomic
fluorescence
D i s s o c i a t i o n equi lib r i a i n flames

Sa b l c . from A H ~ , ( S ~ ) and AH,~(S)


SF Estimated
SH E x t r a p o l a t i o n o f ~ 2 8l e v e l s (Note 46)
so Spectroscopic (predissocfation f n the
band system C 3 8 - X ~ Z; Note 47)

sbz Mass spectrometric


SbBi L.B.S. f o r the ground s t a t e
SbCl L.B.S. f o r a number o f s t a t e s
(mean value)
S bF L.B.S. f o r a number o f states
SbN L.B.S. f o r the ground s t a t e
SbO L.B.S. f o r the ground s t a t e (using data
from 1791)
ScF L.B.S. f o r two s t a t e s
sco L.B.S. f o r the ground s t a t e
Sez E x t r a p o l a t i o n f o r the excited s t a t e
(see Note 48)
Seo Estimated from e x t r a p o l a t i o n o f v i b r a t i o n a l
l e v e l s o f oxides o f elements i n group V I
Table 1 (continued)

K o l e- Ref.
cule

SI: Fass s e c t r o m e t r i c ( d i s s o c i a t i o n
e q u l y i b r i u m o f ,12 l n JI and SIC
V2r3UT
SlBr L . .".;or the ground s t a t e
Si C %ss s p e c t r o m ~ t r i c
sic1 1.3.2. f o r t h e ground s t a t e ;
e s t ~ m a t e o from t h e mean bond energy
i n Sic14
SIF Extrapolation o f various l e v e l s
(mean v a l u e )
SIP Caic. from D ( s ~ F ) , I( s ~ F )and I ( S i )
S>Il E x t r a p o l a t i o n o f 2 1 l e v e l s ( N o t e 49)
S1 S G r a p h i c a l e x t r a p o l a t i o n o f a22:
l e v e l s ( s e e Aote 50)
S!O E x t r a ~ o l a t i o no f v a r i o u s l e v e l s ;
t a l c . from l H , , ( S i S )
S10- Calc. f r o m D ( j i 3 ) . I( S i c ) and I ( S i )
SiS > p e c t r o s c o p i c (convergence o f bands
~ n t h e system E - X ~ Zw!th a
common d i s s o c i a t i o n l i n i t f o r t h e
tuo states]
S ISe Extrapolation o f various l e v e l s
SiTe ditto
Sn? "ass s p e c t r o m e t r i c
SnBr L.a.>. f o r t h e ground s t a t e
SnCl L.S.A. f o r t h e X 2 1 1 and states
SnF L.B.S. f o r the X211 s t a t e
SnH j p e c t r o s c o p i c ( ~ r e dsis o c i a t 1 on)

'in(? E q i i i l i b r i u n o f >nc2 + Sn 2 2Sn0


( s e e i o t e 51)
SnS Calc. from thermochemical d a t a w i t h

SnSe L.5.b. I
1H,,, ( i n s f r o m / 8 6 / ( ~ o i e 52)
f o r t h e X L and E s t a t e s
SnTe 1.3.5. f o r tbe x l l state
SrBr L.S.S. f o r t h e ground s t a t e
SrCi ditto
if
SrF
SrH ~ p e c t r o s c o p i c( p r e d i s s o c i a t i o n i n t h e
C22 s t a t e (see Note 53)
Table 1 (continued)

Mole- Met hod


cule

Sri L.R.S. f o r t h e ground s t a t e


SrO b i ssoci a t i on eqhi lib r i a i n flames (see
Note 5 4 )
Srs j p e c t r o s c o p i c ( l ong-uave l i m i t o f
r o n t i nuous a b s o r p t i o n spectrum)

TaO E v a p o r a t i o n o f La203 and Y203 from


t a n t a l u m b o a t s accompanied by f o r m a t i o n
a: !a@
Mass s p e c t r o m e i r i c ( e q u i l ib r i um f o r m a t i o n
o f Tall i n t h n system Tap05 + Ta)

Te, Mass s o e c t r m e t r i c (see h o t e 55)


TeC) S ~ e c t r ~ s c o p i(cI I V J t o f band
convergence; see Note 56)
TeSe h s s spectromeiri c
Ti:O E q u i l i b r i u m f s r m a t i o n o f ThO i n
ThOi 4 Th
TIC Mass s p c c t r o m e t r i c
TIC[ G r a p b i c a l e x t r a p o l a t i o n o f ground s t a t e
leve1 S
Estimated (see Table 3 )
T iO Nass S e c t r o m e t r i c ( d i s s o c i a t i o n
e " u l f l b r i u m i n the system
Ti%u3 r ii, see Note 57)
Tlp Estimated
TlBr Calc. from thermochcmical d a t a
(see Note 58)
3 i s s o c i a t i o n e q u i l i h r i a i n flames

TIC1 Thermochemical c a l c u l a t i o n (Note 59)


G i s s o c i a t i o n e q u i l i b r i a i n flames

TLF A n a l y s i s o f v a r i o u s d a t a (see Note 60)


Ci s s o c i a t i o n e q u i l i b r i a i n flames

'l- l H dltt@
TI I l a l c . from thermochemical d a t a
( s e e Note 61)
D i s s o c i a t i o n e q u i l ib r i a i n flames
T a b l e 1 (concluded)

.
V.1
, e-
cule Ref.
i i, W1
v0 Yasr s r e c t r m e t r i c d e t e r m i n a t i o n o f n e a t P31
:+ e v a o ~ . a + i 3 n -i92 ( h c t e 62)
\Y9 qasr sc?ctrseetric (dissociation 1651
? c ; i l i o r i u m i c d t AlzSj )
"as5 s ~ e c t r o m s t r i c ( d i s s o c i a t i o n P71
?2ui z i b r i u n i n 4 + sec)
Yc' "ass scectr0me;ric ! d i s s o c i a t i o n W1
e : - i . i a r i d ~ i?,Y + Y 2 O j )
YL€: L.3.i. '3- t ~ ge r c u n g s t a t e ( h o t ? 2) PI
Z&
131
ZcCI fa1
:issacia!lsn ~ q u i l i b r i ai n f l a m e s PI
LPH (31
ZrW L.3.S. &or t h i ground s t a t e I31
Zr:I 5pect r o s c o p i c PI
ZnO 5;c. from tnermochemical data [3. 701
Zr, C21c. f r a n l i m i t o f c o n t i n u o u s I31
a c s o r a i i z r s p e c t r a and f r o m
t h e r m o c ~ e m i c a ld a t a
ZrTe Ca:c. f r o m l i m i t o f c o n t i n u o u s [31
a ~ s o r ; t i o n spectrum
% f' ,-;5s ~ ; i c t r o n e r r i c , s i s s o c i a t i o n
.. 111
e;*i b::r7m i n Zr + Zr37

Notes

1. In r e f s . [ l ] and [ 8 ] an analogous method has k e n used to show


that D,OIC,) i s equal t 0 4 1 . 0 ~2.5 and 39 2 2, respectively. Ackerman
e t a1 16) have shown that the discrepancy between these r e s u l t s and
the value of 37.6 2 2 . 2 i s due to inaccuracies in the analysis of
experimental data i n [ 7 ] and !8].
2. The s t a t e f o r which the extrapolation was c a r r i e d out may not
have been the ground state.
3. On the assumption that the predissociation limit corresponds to
\>('S I f As(zD).Graphicai extrapolation for the s t a t e X ' L yields 90.6.
4. An analogous method has been used in [ 7 ] and (81 to show that
D : I A I I ~ i) s 53 2 3 and 50 2 0.8. Ackerman e t a1 [6] have shown that
the discrepancy between these r e s u l t s and the value 5 1 . 5 2 2.2 i s due
largely to inaccuracies in the analysis of the experimental data in
171 and [ B ] .
It i s assumed that the dissociation limit for the upper state corre-
sponds to €3 ( V ) + N ( 2 D ) .
It i s a s s u m e d in ref. [25] that I),,(BrCI) = 1 3 6 , which has been
obtained on the assunlption that the A21 l state of this molecule has
the s a m e clissociation limit a s the X", state corresponding to
Be(%) +CI('P).
It i s assumed in 1261 that ~ I ~ ( B c l '=) 1 8 4 , obtained on the zs-
sumption that the state A211 of this molecule has a common dissoci-
ation limit with the state XIZ, which corresponds to U e ( ' S ) +I'(21').
It i s assumed that the dissociation limit of the A T I state c o r r e -
sponds to B e ( 3 P )+ H ( ? S )
It i s assumed that the dissociation limit corresponds to B e i ' S ) t
+ O('D).
It i s a s s u m e d that the dissociation limit corresponds to Ui ('S) +
!-Ui(2D. ) ,
It i s assumed that . \ t ~ f u ( B i , . g a s=) 5 2 . 5 5 2. The value Do(Bil) =
4 7 2 1 i s in good agreement with the result'obtained by graphical
extrapolation of the levels on the assumption that the dissociation
+
limit of the B-state corresponds to Bi ('S) Bi ('D+,).
+
It i s assumed that this limit corresponds to ni ('S) l%r(2['312 ) L.B.S.
for the ground s t a t e gives 67.
It i s assumed that the band convergence limit in the s y s t e m s
A", - X I \ ' and Bill,+ -- S12: corresponds to F(2P3/,) +Br(2P3,2) and
F('[%,,) + Br (2P respectively.
It i s assumed that the dissociationlimit corresponds to Br (2P3/,) +
+O(lD).
It i s assumed that the dissociation limit corresponds to C ( ' S ) +
-I-F(~PII~).
D,,(Cl-I) = 8 0 2 1 i s in agreement with predissociation data f o r the
A2A t~ C2C states.
A s i m i l a r value ( - 8 4 ) i s obtainedfrom known D ( C H ) , [(CH) u /(C).
+
It i s a s s u m e d that the predissociation limit corresponds to Ca ( 3 P )
+ t1(2S)
It i s assumed that the s t a t e 3n,+ h a s a limit corresponding- to
Cl ('P + ) F (2P .
If the dissociation limit of the 3no, state corresponds to C1 (2P31, )
+ F(2P11z ) , D,(CIF) = 60.35; no unambiguous choice betwee; the&;
values i s possible a t present, s i n c e for molecules of some of the
interhalogen compounds ( B r F ) the dissociation in the 3na+ state
o c c u r s to a n excited s t a t e of the heavy element and the ground
state of the lighter element while in o t h e r s (ICI) the opposite situ-
ation obtains. T h e value of 5 9 . 0 was assumed in the light of data on
the heat of formation of CIF.
In (71 and [ 8 ] an analogous method was used f o r Cut and the
result was 5 1 and 4 6 , respectively. Ackerman e t a1 [6]have shown
that a discrepancy between these values i s due to inaccuracies in
the analysis of the experimental data.
D,(F,) and D,(HF) a r e related bythe equation /),,(F2) = L'l)o(HF)
+ .AHIo (HF') - &(H?) = L ) I ~ I ( H F ) - ~ A(HF)-103.257.
H~~ T h e value
accepted in [ l ] i s 110(1'2) = 3 7 . 0 2 1 . 0 , and i s based on studies of the
dissociation of F? (97-991, recalculated with the aid of improved
values of the thermodynamic functions f o r fluorine. Up to 1 9 5 9 the
value of Do(HFI could be determined directly only with the aid of
extrapolation oh the vibrational levels of this molecule, and was
.
t h e r e f o r e usually computed f r o m A H t ([IF) and DO IF^) However, in
1959 Johns and Barrow (511 investigated transitions to higher
vibrational levels in the X ' Z s t a t e in the emission spectrum of HF
and, a s a result of short extrapolation, found that D,(HF) = 135.1.
If i t i s assumed that the heat of formation of HF i s A H ~ z ~ ~ ~=H F J
- 6 4 . 2 . which i s recommended in modern thermochemical handbooks,
the corresponding value of D O Fzi I turns out to be 38.5 + 0.6. It
should be noted that the accuracy of thegiven value of AHtzU(HF)is
not very high, since i t has been determined from experiments on
the combustion of hydrogen in fluorine under conditions in which
association of the HF molecules was possible. An unambiguous
choice between the values of I I , ~ F zgiven
I in Table 1 i s , therefore,
impossible at the present time.
Extrapolation for the states I n 0 and 3nl yields 98.6 and 99.9,
respectively. Studies of the atomic fluorescence yield > 84 whereas
photoionization yields < 99.3 (121.
Calculations from the long-wave limit of the continuous absorption
spectrum yield < 90.9; extrapolation for the "10 and states
leads to 81.5 and 80.4, respectively. Studies of atomic fluorescence
and photoionization yield > 66.5 and < 80.7, respectively.
A higher value, apparently i n c o r r e c t , was obtained in [l51 a s a
r e s u l t of studies of dissociation equilibria in flames.
It i s assumed that the dissociation limit corresponds to G e ( 3 P )+
1S ($1')
It i s assumed that the dissociation limit corresponds to Ge(3P) +
+ Se (3P)
It i s assumed that the dissociation limit corresponds to G e w ) +
+ Tr (3P)
T h e dissociation energies of the two isotopic modifications (AB'
and A B 1 ' \ of the molecule AB a r e related by & ( A B 1 ) = Do(ABL1)+
+ G ~ Q 0 - (OI, where G ( 0 ) = f ~ ~ - f ~ ~81 ~ ~ +i s-t hye ~ ~ r -
zero-point vibrational energy of the given isotiopic modification
of AB.
Extrapolation of A ' n , 3no.3n,,leads to 96.8. 92.8, and 92.9. re-
spectively; studies of atomic fluorescence yield >86.5 while
photoionization leads to values < 92.7.
Extrapolation of the A'n levels yields 102.2; measurements of
the energy of the upper level of the A ' n state yield 101.2, predis-
sociation yields 6 107.2 and fluorescence studies 104.6.
Thermochemical measurements yield 80.6, extrapolation of A ' n
and 3 n ~levels yields 73.7, extrapolation of 3n, gives 78, atomic
fluorescence gives > 78.4 and photoionization < 79.2.
A very s i m i l a r result i s obtained f r o m data on the equilibrium
?.lt3rZ.12+ Br2
A very s i m i l a r result i s obtained f r o m data on the equilibrium
ZJC~=J,+C\~.
It i s assumed that the dissociation limit corresponds to F(2Pi12) +
+ J ( ' h . , ) If i t corresponds to F(2P3,2)+ J ('Pii), then D,(JF) = 45.7.
It i s assumed that the dissociation limit corresponds to J ('P3/>) +
+ 0('D)
A practically identical result ( - 117) i s obwained f r o m studies of
dissociation equilibria in flames [571.
T h i s r e s u l t i s in agreement with studies of the dissociation
equilibria of L i F in flames.
It i s assumed that the dissociation limit of the XtB state Corm-
sponds to , $ \ g ( ' S ) + F(*I'I, while the limit of the !12n and B a r s t a t e s
corresponds to 3\!:ISP) - c F ( ' P ) .

l
L.B.S. for the X'?: state yields - 46; predissociation in the
state leads to G58. Thezero-pointenergy of the H2C level
which has a common dissociation limit with X2C i s -47.5.
A much lower result I l ~ i ~ j \ g O( )< X ) ) i s obtained f r o m studies of
the evaporation of MgO with mass-spectrometric recording to
determine the concentration of MgO and Mg in the vapour phase
(1001. Apparently, this may be explained by thelow stability of the
MgOC ion s o that mass-spectrometric determination of the MgO
concentration leads to values which a r e too low (ionization of the
MgO molecules i s accompanied by dissociation of the corresponding
ions [ l o l l ) .
Up to 1959 there were no d i r e c t experimental data on the magni-
tude of D,(NO) and i t was calculated f r o m the formula D,(NO)=
= ; D ~ ( N )t ,'~D,(O,) .
SHI,(NO) It should be noted that the
value A H , 29,(N0)=-21.6, recommended in all thermochemical hand-
books, i s based on the measurements of Berthelot and Thomson
c a r r i e d out at the end of the nineteenth century and cannot be re-
garded a s sufficiently reliable ( s e e [ l ] )In1960 . Deezsi 1661 investi-
gated the cut-off in the rotational s t r u c t u r e of and bands in the
emission spectrum of NO and found that D , , ( S O ) = 152.3 2 0.9.
which corresponded to \ H / p ~ ( S 0 )= 19.3 + 0.9. The discrepancy
between these quantities i s outside the limits of e r r o r and shows
that the \ / i f p.,(hO), which i s a t present accepted in the l i t e r a t u r e ,
i s incorrect.
Similar values were obtained f r o m analysis of the spectrum and
dissociation equilibria of NaCI in flames.
It i s assumed that the dissociation limit corresponds to \1('1)) -;
4- H P S ) ,
It i s assumed that the dissociation limit corresponds to 1'(4S) 1
P(W)
It i s a s s u m e d that the dissociation limit corresponds to
+ 0(3P).
It i s assumed that the dissociation limit corresponds to S ( ' l ) ) 1
11 ('S). Predissociation yields 92.7 Z D, 2 70.9.
Up to the publication of [78] i t was assumed in the l i t e r a t u r e that
( 0 ) = 119.5 on the b a s i s of an i n c o r r e c t numeration of the bands
in the (?X - S-ystem.
It i s assumed that the dissociation limit corresponds to L
t Se('D).
It i s assumed that the dissociation limit corresponds to S i ( ' D ) +
+ f-1 ( ? S ) .
It i s assumed that the dissociation limit corresponds to S i ( ' D ) 4-
-P N('S)
T h i s i s i n good agreement with data obtained by extrapolation of
ground- and excited-state levels ( - 129 1841, and - 132 (851,
respectively).
T h i s i s in good agreement with the result obtained by extra-
polation of the vibrational levels ( - 110 (471).
A very s i m i l a r value i s obtained by extrapolationof D29 levels.
A s i m i l a r although l e s s a c c u r a t e r e s u l t may be obtained f o r
Da(SrO) f r o m data on the latent heat of evaporation of S r O found
without m a s s - s p e c t r o m e t r i c recording. The use of such recording
f o r determination of the concentration of SrO and S r in strontium-
oxide vapour led to a very much lower value ( < 86 [1001). T h e
e r r o r s in these measurements were due to dissociationof SrO+ ions
I1011 as in the c a s e of MgO ( s e e note 40 above).
This i s in good agreement with the value estimated f r o m the
convergence of R 2 levels on the assumption that the dissociation
l i m i t c o r r e s p o n d s to T e ( V ) + Te('1)).
It i s a s s u m e d that the dissociation limit corresponds to T e ( ' D )
+ O('P).
A practically identical r e s u l t i s obtainedwith L.B.S. f o r the ground
state ( - 159 and f r o m studies of the evaporation of titanium oxide
( - 159.9
The long-wave boundary of the continuous absorption s p e c t r u m
yields c; 83.8; extrapolation of the levels f o r WO gives 73.9.
The photoionization method gives < 100; extrapolation of
A ' I I . ' f l o and 3 r l , levels yields 88.4, 89.6 and 90.0, respectively.
Predissociation gives 90.8.
Extrapolation of l levels yields 110 (the energy of 107.4
c o r r e s p o n d s t o the upper levels of this state); predissociation leads
to f 128.7, while e a r l y thermochemical data give 112.
Extrapolation of Ain l e v e l s gives 72,2; the method of atomic
fluorescence l e a d s to 65.8, while photoionization gives 67.5.
F o r 'AH,,= 133 with AHf, (VO, cryst.) --99.5and AtI,, (V) = 122.
An identical r e s u l t i s obtained with L.B.S. f o r the ground state.
It i s a s s u m e d that the dissociattoz! limtt corresponds to Zn(3P)
+ H (2S).
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Table 2
BOND ENERGIES O F ORGANIC MOLECULES AND RADICALS
(kcal/mole)

Data on bond energies of polyatomic molecules obtained up to the


middle of 1953 a r c collected in Cottrell's monograph [ l ] . The values of
I ) taken f r o m this monograph a r e given the reference [ l ] in the table.
In all other c a s e s , the number in the last column of the table r e f e r s to
the uriginal papers o r reviews.

Whenever a number of values for the bond energy a r e available in the


l i t e r a t u r e , they a r e all listed, except for those known to be unreliable.
T h e value which, in o u r opinion, i s the most reliable i s printed bold.

A s a r u l e , published values of D a r e not reduced to 0 ° K . T h i s i s due


to the absence in most c a s e s of data n e c e s s a r y for this conversion, and
secondly to the fact that e r r o r s in the determination of 1 ) for polyatomic
molecules a r e too high for such conversion to be significant. An estimate
of the magnitude of the correction may be obtained f r o m the following
approximate expression (11
I), - U, S -, j+ l /R7 kcal

where D r and I),, a r e the bond e n e r g i e s r e f e r r e d to the temperature of


the experiment, 7 , and to O°K, respectively, and n i s the number of
new translational and rotational d e g r e e s of freedom which a r i s e s ss a
r e s u l t of the breakdown of the molecule l ? - X to H and X

In s o m e p a p e r s , and particularly in review p a p e r s , the authors do not


quote the t e m p e r a t u r e s to which i) refers. Such c a s e s a r e indicated by
the dash in the third column. T h e dash i s also used to indicate those
c a s e s where 1 ) was obtainedwith the aid of thermochemical caiculations,
using data r e f e r r i n g to different temperatures.

T h e majority of the bond energies given in the table were obtained


either by the pyrolysis method o r by the electron-impact method.

In the pyrolysis method, the activation energy, whichis identified with


the bond energy, i s determined within a certain temperature interval
(usually not m o r e than 100"). In such c a s e s the table gives the mean
temperature.

In many p a p e r s concerned with determination of bond energies of


polyatomic molecules with the aid of the electron impact method, the
authors do not quote the t e m p e r a t u r e s a t which the m e a s u r e m e n t s a r e
c a r r i e d out. In such c a s e s the temperature i s assumed t o be that of the
ionization c h a m b e r s of standard m a s s s p e c t r o n i e t e r s , i.e. - 400 -
500 ' K .

T h e values given in the table withouta reference were obtained by the


p r e s e n t authors with the aid of thermochernical calculations with the
heats of forrnatior, of radicals taken f r o m Table 5.

T h e bonds a r e listed In the following sequence: C H , C - C , C - -


halogen, C - 0 C - K , C - S . C - r n e t a 1 , O - 0 , O - N , N - N . S - S .
and c e r t a i n other bonds.

Method

L - 1 bonds
C-H ioectroscooic
(,?redissociation)
Analysis of experimental
data
ditto
* n

E l e c t r g n impact
P y r a l y s i s o f CH3!
?hotobromi n a t i o n
Analysis o f experimental
data
ditto

I G charge
~ transfer

Analysis o f ex~erimental
data
ditto
n n

E l e c t r o n impact
II I n

P y r o l y s i s o f C2H31
Anai s i s o f e x p e r i m e n t a l
d a
P y r o l y s i s o f (C2~3)2Hg
Table 2 (continued)

-
Ref.
Method
-
97+1 A n a l y s i s o f experimental data 1491

05.2 Photobrominati on l681


CH2= C-CH-H ~81.2 E l e c t r o n impact [701
11 It
CH E CCH2- W ~82.8 [701
CH2-CHCH2-H 77 P y r o l y s i s o f 1-C4H8 [71
rK,H,-H 95 P y r o l y s i s o f n-C3H71 [l1
100 P y r o l y s i S o f CghjCH2-C3H7 If1
09.S*0.9 E l e c t r o n impact [l1
100 P h o t o i oni z a t i on l81
-95 Thermal d i s s o c i a t i o n o f 9,10,
n-C3H7 711
95 ( h a t e 1 :
9412 E l e c t r o n impact l11
-80 P y r o l y s i s o f iso-C3H71 [l1
76 Pyrolysis [71
E l e c t r o n impact I611
n
U
W1
P y r o l y s i s o f n-CqHgl [l1
E l e c t r o n impact PI
Photoi oni z a t i on l81

Photobromi n a t i on 1121
E l e c t r o n impact t11
Photobromi n a t i o n [l1
It
[131
Thenochemical c a l c u l a t i o n
E l e c t r o n impact 1141
A n a l y s i s o f experimental d a t a (521

Py r o l y s i S [l1
I
[II
n
111
Table 2 (continued)

Method
-
Ref.

- 76 111

-76 Ill

n
8 (Note 3 : Ill
I
8 ( N o t e 3: 111
I
8 (Note 3 , 111
10354 E l e c t r o n impact (15 l
98 Photochlori nation 1851
i 9 .G 5 5 E l e c t r o n impact 1161
95 Photochlorination F351
9052 Photobromination 111
8913 E l e c t r o n impact (15 l
93 Photochl o r i n a t i on 1851
11
94.7 1851
R
96.1 I851
I
93.4 1851
97.8 n
P51
R
95.6 L85 l
-9'3 Photobromi n a t i on (11
96 Thermochemical c a l c u l a t i o n
93-52 Photobromination 1171
90 Thermochemical c a l c u l a t i o n
CO-H 30.452.: E l e c t r o n impact 1181
C HO- H <78 Photolysis (11
--
1.352 E l e c t r o n impact 18,191
G92 Fhotobromination 1791
I
t 88 I801

79 E l e c t r o n impact I201
I I
77 I21l
Table 2 (continued)

Temper-
Band ature, Method
OK
h'C--15 111lG Thermochemical c a l c u l a t i o n
NCCtI, - H G79 'I00 -500 E l e c t r o n impact
a-C,I I,NCH,-H I (Note 3 1100 Pyrolysis
P-C,II,NCH2-H I (Note 3 1100 n
yC,H4NCHa-H ' (Note 3 1100 R

C - C bonds
CH G CH 230f 2 Thennochemical c a l c u l a t i o n
CtIr-CH2 120f10 - I I

C,H5--CH, 80.5 -- Photoionization


C&-C, H, 79.5 -- n
CnH2n+i - CrnH2n:i 1
(see Note 4 )
CH =CCH2-CH, G67.5 i00-50u E l e c t r o n impact
6833 - Fyrolysis
G68.2 100-500 L l e c t r o n impact
67*2 - Yyrolysis
I
61.5 D50
R
63*1.5 950
n
57.5 950
I
65 950
I
-61 900
I
-59.5 900
- 60 900 I

G97523 i00-500 E l e c t r o n impact


-83 i00-500 I I

LOO-500 I R
69
72 1050 Py r o l y s i S
1050 R
70.9
71k3 i00-500 E l e c t r o n impact
68 1050 Pyrolysis
80 Photolysis
74 i00-500 E l e c t r o n impact
100-500 U I
,<69*4. f
68 Thermochemi c a l c a l c u l a t i o n
Table 2 (continued)

Bond Method

6 9 7 ji Electron i ~ p a c t
662-4.6 I I

68555.3
zS7.613.7
CH,CO-C=CH 84*3
C,H,CO-CH3 -7aik~e5 Py r o l y s i S
C,H,CO-CF3 ,74 ( 0 0 . I

C,HsCO-C,H5 N 34 \ G V .
C,H,CH,CO-CH,C,W, - 7 1 iac.
CH3-CN 102 E l e c t r o n impact
CH,F-CN -111) I I

CHF2-CP.: 116 I I

CF,-CN 120 I I

NC-CN 104 I I

1451-8 Calc. f r o r d a t a o f thermal


d i s s o c i a t i o n o f C212
i n shock uaves
12558 ditto
NC,-CN 211 (Cote 6 Electron i ~ p a c t
C - halogen bonds
CH,-F -118 I N y A n a l y s i s o f experimental d a t ,

115+3 Ihermochemical c a l c u l a t i o n
121-+'t E l e c t r o n impact
12152.5 I 8

102&7 I I

98 I I

so.5*3
60.4*3
5913 Pyrolysis
73.352.3 Electron i ~ p a c t
60.424 I I

6812 Py r o l y s i s
56 I

48 I
T a b l e 2 (continued)

lerper-
-
Bond ature, Method Ref.
OK
-
10-500 Electron impact [l51
10-500 a n [l61
10-500 R I
It61
10-500 I I L621
00-5r,o I a F71
30-500 n I
[l51
rhern,octiemical calcui a t i o n
Pyrolysis 1341
00-500 Electron impact 1211
1050 Py r o l ysi s 1551
1000 I
111
00-500 Electron impact [an]
00-500 I a [32]
00-500 I I W1
800 Pyrolysis [52]
1050 I
111
800 [52]
00-500 Electron impact I301
1070 Pyrolysis [*l
1070 a [l1
1070 n
I11
800 111
800 Ill
800 111
1050 111

1050 111

1070 111
1070 U1
1070 [l1
T a b l e 2 (continued;

Temper-
ature,
OK
lU3J
Fyrolysis

111x1

8,1.P
-

- n

IUilJ n
l i ' jl R

iljl-l n
85i) I

400-50Ll E l e c t r o n impact
8oki Pyrolysis
'Jjil n

it l1 l-XI0 E l e c t r o n impact
85'1 Pyrolysis
i l >lI - ~ I J ~ l E l e c t r o n impact
" -
131) Py r o l y s i s
40(1-500 E l e c t r o n impact
Table 2 (continued)

--
eaper-
Bond ure, OK Method

yrolysis
I

n
n
n
n
n
n
R

n
lectron impact
yrolysis
n
n
n
I

n
I

n
I

n
Table 2 (continued)

Bond Method Raf.

Pyrolysis
E l e c t r o n impact
R 3

Fyrolysis
n

E l e c t r o n impact
a m

Fyrolysis
I

Electron inpact
Thermochemical c a l c u l a t i o n
E l e c t r o n impact
I I

pyrolysis
R

Thermochemical c a l c u l a t i o n
4nal y s i s o f experimental data

'yrolysis
i n a l y s i s o f experimental data

Iyrolysis
I l e c t r o n impact
h a l y s i S o f experimental data
'y r o l y s i s
. l e c t r o n impact
'yrolysis
I

n a l y s i s o f experimental data

C - 2 bonds
CH,--OH hotodissociation
l e c t r o n impact
h o t o d i s s o c i a t i on
Table 2 (continued)

Temper-
Bond ature, Method
OK

HCO-OH - hotodi s s o c i a t i o n
CH,CO-OH - n

-
C N bonds
CH:,-NH2 i00-5UO le c t r o n impact
CHx-NI ICH:, It n
tU0-500
CH3-N(CH3), too-500
C8H6CH2--NH2 l000 yrolysis
CH3-NO, n a l y s i s o f experimental data

C2H5-NO2 - itto
(CH&N-CH0 i1M-500 l e c t r o n impact
(CH3)zN-CH&O 100-300 n n
CH3N=N-CH3 700 yrolysis
i00-500 l e c t r o n impact
j so-CzHSN-
N-C2Ha It n
100-500
pC,H,N=N- iso-C3H, '100- 500
CF3N=N-CFS 730
NCP--N WO-500 l e c t r o n impact
NCS-N ~t n
i00-500
NC,-N n II
4130-500
NC6-N 100-500
C -S bonds
n n
CH3-SH 400-5U0
2050 'y r o i y s i S
400-500 l e c t r o n impact
900 'yrolysis
400-500 Zlectron impact
400-503 i? n
850 'yrolysi s
400-500 I e c t r o n impact
W-500 n t

i00-500 n n
400-500 n II

850 'yrolysis
298 n
Table 2 (continued)

'yrolysis
"

yrillysis
yrolysis
yrolysis
I

II

a
n
II

n
n
n
I!

n
n
n
n

(CF,),;ls-CF, 0

-
G O bonds
HO-OH ralysis o f experimental data

DO-OD

RO-OH
Table 2 (continued)

Bond Method

RO-OH Py rol ysi S


Anal ysi S o f experimental
data
Py rol vsi s
n

knalysi S o f experimental
data
C2H50-OCzH, ditto
n- C,H70-OC,H, H

1.- C4H00-0C2H5
t.-C4HB0-OCIHB

0 0
l1 I1
CH,CO-OCCH, Pyrolysis
0 0
/l l
C2H6CO-OCC2H6
0 0
1l II
n C,H7CO-OCC3H7
O - N bonds
CH30-NO Analysis of experimental
data
C2H60-NO ditto
n -C3H70-NO il

iS ~ - C ~ H ~ O - N O
n-C,HOO-NO
CH30-NO2
C2H,0-NOZ
n -CsH70-NO,
-
N N bonds
HzN-NH2 Py rol ysi S
Electron impact
n n

Calc. from data on equi-


librium o f NF2-NF2 =
2NF2
Electron impact
T a b l e 2 (continued)

Bond

E l e c t r o n impact
n I
n n
R n
Q n
1 R
n n
R I

Calc. from equi librium data

ditto

S -5 bonds
W-SH E l e c t r o n impact
CH3S-SCH, n R

n n
C,HSS-SCH;
n n
&H,S-SCJI,
I'ther bonds

N-H A n a l y s i s o f e x p e r i a e n t a l data

NH-H ditto
U
NH,-H
R
N-F
R
NF-F
I
NF,--F
0,-Ii E l e c t r o n impact
n n
H@?-H
n n
N3-H
NO-H Spectroscopic ( p r e d i s s o c i a t i o n )

NO- D ditto
NO-Cl lalc. from e q u i l i b r i u m data
E l e c t r o n impact
T a b l e 2 (concluded)

Temper-
Bond ature,
OK
Nethod
- Ref.

NO-N - hermochemical data


N1-0 NO-500 lectron impact [W
(100-500 U n
1641
298 hermochemical data
- 1 n [54]
n II
1541
- n I [M]
- 11 n 1341
- yrolysis 1521
- n 111
'100-500 l e c t r o n impact v371
R \l
iO0-500 1871
'100-500 1! II
1871
iU0-500 n n
[W

Notes

1. -
Cottrell (11 a s s u m e s f o r C H in the methyl group of propane a
D value of - 100 kcal, which was calculated by Szwarc from his
-
data on the pyrolysis of n butylbenzene and was a l s o obtained by
Stevenson, who investigated ionization and dissociation spectra of
hydrocarbons with a m a s s spectrometer. Analysis of Stevenson's
data shows that they do not directly l e a d t o D(n- C 3 H 7 H) ==l00 -
kcal, but that the interpretation of these r e s u l t s itself depends on
-
the t r u e value of I) (C H) f o r propane [Sol. In analysing his r e s u l t s ,
Stevenson based his argument on Szwarc's data.
-
T h e r e s u l t I1 ( C H) - 100 f o r propane w a s calculated f r o m the
activation energy f o r the dissociation of R-butylbenzene CsH5CH2 -
C 3 H 7 , which i s equal to - 65, providedthat I)(C,H,CH?
kcal. Recently, however, Szwarc h a s tended t o a s s u m e that D(C H)
-
H) 1-78
-
f o r the methyl groupof toluene i s equal t o 8 3 I521. If this is assumed,
i t follows f r o m data on the -pyrolysis
- - of n-butylbenzene that I1 ( n -
-
C 3 H , H) = 96.
Collin [l1] has measured the appearance potentials of the NO? L

ions f r o m a number of nitroparaffins. ~ s s & n i that n ~ the ionization


potential of NO2 i s equal to 11 e V , h e h a s calculated the C N bond -
e n e r g i e s to be (in Kcal):
CH3 - NO2 ... -62
C2N5 - NO2 ... -62
n-C3H7 - NO2 ... -60
iso-C3H7 - NOz ... -58
T h e a b s o l u t e v a l u e s of !l (C - K ) a r e c l e a r l y too high, and only
the d i f f e r e n c e s between t h e m a r e of i n t e r e s t .
By u s i n C o l l i n ' s d a t a and the h e a t s of f o r m a t i o n of R i N O z
-
m o l e c u l e s 751, i t i s p o s s i b l e to c a l c u l a t e the c o r r e s p o n d i n g D ( A H)
-
d i f f e r e n c e s , and by a s s u m i n g that D ( C H) = 102 in m e t h a n e one
obtains the following values: D(C2Hs - H) 9 8 , D (iso-C,H7 - H)
2 8 9 and D(n-C3H, - H) z 95. T h e f i r s t two v a l u e s a g r e e well

be c o n s i d e r e d t h a t the r e s u l t D (n-C3H: -H)


t r u e value.
-
with the r e s u l t s reliably e s t a b l i s h e d a t p r e s e n t . It m a y t h e r e f o r e
9 5 i s c l o s e to the

Dam on the t h e r m a l d i s s o c i a t i o n of n-C3Hi a p p a r e n t l y l e a d t o


t h e r e s u l t D ( n - C 3 H - - H) 95 1°. 711. Kinetic d a t a on the
reactions
N a + F : C i - r r < a C : ~R
show that the activation e n e r g i e s d e c r e a s e r n o n o t o n i c ~ ~ l liyn the
s e q u e n c e CH3C1, C , H - C l , n - C 3 H - C l , n-C4HgC1, and s o on. T h i s
s h o w s that the s t ength of the C - C1 bond g r a d u a l l y d e c r e a s e s i n
t h i s s e q u e n c e [ j 6 f If t h i s i s in f a c t the c a s e i t i s p o s s i b l e t o show
thermochernically t h a t in the s e q u e n c e CH3 - H, C 2 H S - H, n - C 3 H 7
- H and n-C,H9 - H the s t r e n g t h of t h e C - H bonds a l s o d e c r e a s e s
nionotonically, which i s i n a g r e e m e n t with Il(n-C3H7 - H) -95.
Available d ~ t aa r e . ~ pt r e s e n t insufficient to rtllow us to conclude
that the d i s s o c i a t i o n e n e r g y f o r the C - H hond i n p r o p a n e is 1 0 0 ,
a s w a s n s s u m e d by C o t t r e l l ; the p r e s e n t a u t h o r s a r e inclined to
conclude t h a t 9 5 i s c l o s e r to t h e t r u e value.
2, T h e r e s u l t D ( n - C 4 H S - H) - 1 0 1 , w h i c h w a s a s s u m e d by C o t t r e l l
[ l ] ,w a s taken f r o m the s a m e p a p e r by Stevenson in which I)(n-C3H,
- H) u c l s a s s u m e d to he 100 ( s e e note 1 above). It i s t h e r e f o r e
r e a s o n a b l e to s u p p o s e that 2(n-C4Hs - H) \(D(n-C3H7 - H ) , i.e.
that D (n-CbHr - H ) 94. T h e r e s u l t D(n-CIH., H)
[ B ] i s thought to he unreliable by t h e a u t h o r s t h e m s e l v e s .
- - 105 in

3. .An e x p e r i m e n t a l d e t e r m i n a t i o n w a s m a d e of the d i f f e r e n c e

-
w h e r e D ( R H ) 1s t h e b o n d e n e r g y g i v e n i n the t a b l e , while D ( C 6 H j
CH: - H) = 78 kcal.
1i D ( C - H) f o r the methyl g r o u p in toluene i s t a k e n to be 8 3 ( a s
s u g g e s t e d hy S z u a r c [ 5 2 ] ) , a l l D ( R - H) v a l u e s m u s t be i n c r e a s e d
by 5 kcal,
4. hlany of the C -C bond e n e r g i e s i n paraffin h y d r o c a r b o n s have
been d e t e r m i n e d f r o m d a t a on t h e photoionization of a l k a n e s [81 (in
kcal)

7 -C311;
s e c -C3H:
ri -CjHq
n -c3[{?
s e c -C31i7
- -C4Hq
n -C3H7
sec -C3ll7
* -C,Hs
n -C41iq

T h e above s e t of v a l u e s f o r 9 ( C - C) i s t h e r m o c h e m i c a l l y
c o n s i s t e n t with D (n-C H - H ) h 1 0 0 and D (ri-C4H, -
H) >, 105.
All t h e s e q u a n t i t i e s a r e h i g h e r by a few kcal than t h e g e n e r a l l y
a c c e p t e d values,
5. T h e bond e n e r g i e s w e r e obtained a s the activation e n e r g i e s of
t h e r m a l d i s s o c i a t i o n s of t h e s e compounds i n t h e p r e s e n c e of
toluene. T h e pre-exponential f a c t o r s i n the A r r h e n i u s equation
turned out to be anomalously l a r g e (10''' -
10" s e c - l ) which
indicated that the activation energy might be too high by a few kcal.
T h e point of fission i s indicated b the present author.
T h e electron-impact method 1 3 4 was used to determine the heats
of formation of the radicals CN, C 2 N , C3N. C J N . C5N and C,;N

molecules N C - (C C),-
( s e e T a b l e 5) and a thermochemical calculation was then c a r r i e d

C
-
out to determine the C - C and C N bond energies in a s e r i e s of
-- - N . (where I ? = 0, 1 , 2 , 3 , 4 , 5 , 6)
and radicals produced a s a result of the dissociation of these
molecules (in kcal). T h e r e s u l t s w e r e (in kcal):
C - K .. 193 C , , - N . . . 162
C? - N ... 185 KC - CN . 104 ..
C3 - N ... 169 NC, - Ch' . : . 1 2 0
C, - N . . .
173 XC, - C S ... !)l
C $ - N . . . 129 C - S . , . 118
NC? - N ... 161 K C 5 - C > ... 128
NC3 - K . . . 157 NC', - C 2 S . . . 109
NC4 - N . . . 153 C - C . . . 79
and certain others.
Analysis of the effect of fluorine atoms a s substituents on the
strength of various bonds in organic molecules enables us to
e s t i m a t e (approximate values a r e given) the strength of C - F
bonds in a number of monofluoroalkanes [281 (in kcal):
CliJ - F .. . llb
I - I . .. 114
e -C31i, - E' ... il2
IS0 -C;li, - I.' ... l06
t. -C4111 -- '.l ... 104
Rabinowitsch and Reed l331 investigated reactions between Na
vapour and CF3 C l , CF2HCl, CFHz Ci and CH3C1, and found that the
activation energy f o r all these reactions w a s the s a m e within the

the elementary p r o c e s s Na + R C1 -
experimental e r r o r . T h i s s q g e s t s , with the s a m e mechanism of
NaCl + R, and in accordance
with Polanyi relation (661, that the C - C1 bond energy i s constant.
T h e r e f o r e D(CFa
-
D(CH3 Cl)= 80.
- Cl)- 3(CFzH Cl)- - l ) ( C F H z - Cl) -
T h e s e quantities a r e thought by Cottrell to be unreliable. Com-
parison with later data shows that the e r r o r s i n them can hardly
exceed, by any g r e a t amount, the usual e r r o r in the determination
of bond e n e r g i e s of polyatomic molecules (2 - 5 kcal).
T h e h e a t s of formation of the corresponding organolithium com-
pounds w e r e determined i n r e f e r e n c e s 74 and 86, and the strengths
-
of C Li bonds were then calculated.
The activatlon energy of the monomoleculo~ decompoxlsition of
d i n ~ e t h y l m e r c u r yinto CH3 and HgCH3 i s equal to 51.3 with the pre-
exponential factor in the Arrhenius equationequal to 3 X 1013 s e c -' .
T h i s enables u s to identify the experimental activation energy of
51.3 with the strength of the C -
Hg bond in dimethylmercury.
Thermochemical calculations lead to D(CH, - HgCH,) + D (Hg -
-
CH,) = 57.3. Since D (CH3 HgCH3) = 51.3, it follows that D (Hg -
CH3) = 6. Similarly, i t i s found that 11(C2% HgC2H,) = 41 and -
D (Hg - C2H,) = 6 . Hence, i t follows that D(Hg R), where H i s a -
hydrocarbon radical, i s always equal to -6, whatever the s t r u c t u r e
of the radical. Therefore, for many compounds of the form R ,HgRz
i t i s possible tc, calculate thermochemically the magnitude of the
-
s u m D ( R , - HgR2) + D (Hg R 2 ) and then, by assuming Ll(Hg -
-
R2) = 6 , to e s t i m a t e r) ( R , HgR2). This method was used to
calculate the C - Hg bond energies f o r di-n-propylmercury, di-iso-
propylmercury and diphenylmercury. The heats of formation of the
r a d i c a l s were taken from Table 5 of the present compilation. The
o t h e r n e c e s s a r y data a r e given in reference 38.
12. It w a s found f r o m the p y r o l y s i s of dimethylzinc. u s i n g the toluene
m e t h o d , t h a t the activation e n e r g y f o r the rnonornolecular decom-
position of t h i s compound into CH Z n and CH w a s equal to
1 7 . 2 . If t h i s i s identified h i t h !'(CH Zn -
CH ) , t h e r m o c h e m i c a l
-
c a l c u l a t i o n s yield :( Z n - CH j '
35 [ 3 9 ] .

REFERENCES

1 . C O T T R E L L , T . L . (1956). T h e S t r e n g t h s o j Ciremrcal B o n d s , 11-, A l .


2 . GURVICH, L.V., KHACHKURUZOV, G..4., \ i E D V E D E V , V . 4 . . VEITS. I.V.,
BERGl1.43. G..%., YLWG\lAN, V.S. RTISHCHEV.4, N.P.. and KURATOVA.
L . F . e f a l . (1962). Thermod?narnic properties o! i n d i v i d u a l s u b s t a n c e s ,
I z d . AN SSSR. \loscow.
3 . FR4NKKE\'ICH. Ye.?. and T h L ' R O Z E , V . L . (1957). l z c . 4 k a d . ?;auk S S S R ,
o t d e i . k n i n . rrauk, 50.12, !501.
4 . L?\1PE, F.U., and F I E L D , F . H . (1959). 1. 4 m . C h e m . Soc., 8 1 , 3238.
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6 . SHILOV. \.Ye. and S.4BLROV.4, R.D. K i n e t i c s and C a t a l y s i s
(printing).
7 . SZ1,V.4RC, \l. (1950). C h e m . R e r . , 47, 75.
5 . S T E I N E R , 5.. G I E S E , C . C . , and INGHR.4\1, \!.G. (1961). 1. C h e m . P h y s . ,
34, 189.
9. C A L V E R T , J.G., and S L E P P Y , \$.C. (1959). 1. .In. C h e m . S o c . , 81, 1544.
10. K E R R , J . 1 . . a n d TROT\I.AN-DICKENSON A.F. (1959). T r a n s . Farad. S o c . ,
5 5 , 572.
11. C O L L I N , J . (1954). S o c . ro,. s c l . ~ ~ e ' 2~3 , e191.
,
12. F E T T I S , C.C., and TROT\I.4N-DICKENSON. . F . (1959). 1. 4rn. Chern.
' o c . , 81, 5260.
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Table 3
BOND ENERGIES IN INORGANIC MOLECULES AND RADICALS
( i n kcal/mole)

T h e table gives the bond energles in polyatomic inorganic molecules.


T h e f i r s t column shows the dissociation reaction (all the substances a r e
a s s u m e d to be in the ideal g a s state in their electronic ground states).

T h e second column gives the heat of dissociation a t O°K and the third
the s a m e quantity a t 298.15"K (the abbreviated figure of 298 i s quoted
to s a v e space in the table).

T h e fourth coiumn gives an indication of the method used to determine


the bond energy. Some of the values were obtained by d i r e c t measure-
ments (for example, by the electron-impact method). However, many
m o r e were found indirectly (for example, from measurements of
equilibrium constants) o r by calculation f r o m known heats of formation
of the components of the particular reaction. When the dissociation
energy was calculated f r o m the heats of formation of the reaction
components, reference i s made to Tables 6 and 4 , which give the heats
of formation of inorganic radicals and a t o m s , respectively. Most of the
methods used to determine the bond energies lead to values r e f e r r i n g
to temperatures different f r o m O'K o r 298.15'K. In those c a s e s when
the conversion to 0 o r 298.15"K could not be c a r r i e d out, o r could only
be c a r r i e d out approximately, the third column gives the directly
measured values with an indication of the temperature a t which they
were obtained. References to published papers a r e given in the last
column.

F o r convenience of comparison of the bond energies in polyatomic


inorganic molecules with dissociation energies of related diatomic
molecules, the latter a r e also included in Table 3 with reference to
Table 1.

It should be noted that some of the dissociation energies given in the


tahle do not correspond to the disruption of any particular bond (for
example, the dissociation energy of the associated molecules: Na 2 C1 2 =
2NaC1, and s o on). Some of the dissociation energies correspond to
p r o c e s s e s in which the fragments which appear after the reaction not
only change t h e i r geometric p a r a m e t e r s but a l s o exhibit changes in the
disposition of the a t o m s , for example
0
11) such c a s e s , the tabulated values provide onl) limited information
about the individual bond energies. T h i s , however, does not mean that
the dissociation energy of such reactions has no physical meaning,
since the equilibrium constants determine the composition of the
dissociation products.

Most of the values a r e given with an indication of the e r r o r s involved.


T h e latter were assumed in accordance with the recommendations of the
original a u t h o r s , o r w e r e estimated. If t h e q u o t e d e r r o r was obtained by
combining a number of independent quantities (for example, e r r o r s in
the determination of the heat of formation of a given compound in the
crystalline s t a t e , i t s heat of sublimation, heat of formation of the atom,
and s o o n ) , i t was obtained by taking the root mean square. It i s much
m o r e difficult to determine the e r r o r s in quantities estimated by the
original authors; in many c a s e s , the values a r e given without e r r o r .

P a r t i c u l a r attention h a s been paid to the compilation of the tables to


e n s u r e that the values given a r e consistent with the heats of formation
of inorganic r a d i c a l s (Table 6 ) , the atomic heats of formation (Table 4)
and the dissociation energy of diatomic molecules (Table 1).

T h e compounds a r e listed in the table in the s a m e o r d e r a s in most


modern thermodynamic handbmks (for example, s e e r e f e r e n c e s 21,
154). T h e table begins with oxygen, continues with hydrogen and i t s
oxygen-containing compounds, then goes on to fluorine and i t s com-
pounds, including oxygen and hydrogen, and s o on.
Table 3

Reaction Method

Data of Table 1
Calc. from Tables 6 and 4

Data o f Table 1
Studies o f
Fe4+ 4 Fe4*' + H202
E l e c t r o n impact
n n
HO, = OH +- O Calc. frnm Tables 6 and 4
H,O = OH + H P h o t o l y s i s o f water vapour
(see Note I)
Detonation method
n n
n II

Spectrometric d e t e r m i n a t i o n
o f concentration o f
hydroxyl
ditio
n
E l e c t r o n impact
Calc. from l a b l e s G and 4
Photochemical d i s s o c i a t i o n

E l e c t r o n impact
Kinetic
Calc. from Table 6
E l e c t r o n impact
Calc, from Tables 6 and 4
ditto
Calculated
Calc. from Tables G and 4

C21c. from Table 6


Calc. from Tables G and 4

ditto
Table 3 (continued)

Reaction Method Ref.

HDO? - 011 7 OD Calc. from T a b l e s b and 4

HDOI - SO, D ditto


I-IDO? DO, H 11

OT-0 -T n
T 2 0 OT - T I1

H T 0 O!I ,T n

HTO OT - F1 II

DTO OD T R

D 1 0 OT
- 11 !I

F? -- 3- IiCtP7 ,
FO F C, lata of iable 1
F20 F 0 - 0 I l e c t r o n impact
Istimared
Zalc. f r o m T a b l e 6
:ale. from Tahlps b and 4

litto

:ale. f r o m c r y s t a l - l a t t i c e
energy
leasurement o f band in t e n s i t i e s
o f dimeric ~cilecules
'apour p r e s s u r e measurement
T a b l e 3 (continued)

Reaction Method

Data o f Table 1
Calc. from Tables 6 and 4
S~ectroscooic(predissociation)

Calc. from Tables 6 and 4

ditto
n
Data o f Table 1
Calc. from thermochemical
data
Calc. from Tables 6 and 4

ditto
It

Equilibrium studies
l a t a o f Table 1
Estimated
3ata o f Table 1
Calc, from thermochemical
data
Calc. from Tables 6 and 4

Data o f Table l
jitto
;ale, from thermochemical
data
.ale. frsm Tzbles 6 and 4
l a t a o f Table 1
:ale. from Tables b and 4
S, :-S,
- S +
Ss--S, i .C
S, =- S, +s
S., - XS,
/apour pressure
m~asursnent
Table 3 (continued)

Yeacti on Net hod

Vapour pressure
measurement
Calc. from Tables 6 and 4
Vapour pressure
measurement
Calc. from Tables 6 and 4

3ata o f Table i
Calc. from Tables 6 and 4
Yass soectrometric
Calc. from T a b l e s 6 and 4

Speetroscopi c ( p r e d i ssoci a t i on)

:ale. from Tables 6 and 4


l a t a o f Table 1
:ale. from Tables 6 and 4
t l e c t r o n impact
tinetic
:ale. from Tables 6 and 4

littc
.lectraa impact
;ale. from Tables 5 and 4
litto
n
n

I a t a of Tabie !
k l c . from Tables 6 and 4

l+ t t o
n
)1

lata o f Tabie 1
T a b l e 3 (continued)

I
I
Ket h o d

Calc. from Tables G and 4

NO - +
N ~(hibie
NO: - NO 4 0 i(ecalcu1ated e q u i l i brium
data
E l e c t r o n impact
NO, NO, -I
:-0 Calc. frcm Taoles b and 4

N,O -= NO '-N Electron inoact


Calc. fram Tables 6 and 4

E l e c t r a n imoact
I1 18

Calc, from Tahles t and 4

Estimated
Calc. from i a b l e s 6 and 4

Equilibrium studies
fiecalculated e q u i l i b r i u m
data
Calc, from Tables b and 4

Equilibrium studies
Recalculated e q u i l i b r i u m
data

Equilibrium studies
N,O, - N,O, + 0 Calc. from Tables 6 and 4

NZ05 NO, + NO, Studies o f e q u i l i b r i a i n


a shock tube
N,05 NL04 +0 Calc. from Tables b and 4
NH - N I1 l a t e o f Table 1
NH, - NI1 ' 11 analysis o f l i t e r a t u r e
i l e c t r o n impact
:ale. from Tables 6 and 4
T a b l e 3 (continued)

Reaction

Spectroscopic ( p r e d i ssoci a t i o n )

Soectroscopic ( p r e d i s s o c i a t i on)

Spectroscopic (atomic
fluorescence
E l e c t r o n impact

Calc. from a c t i v a t i o n energy


o f r e a c t i o n CH3 + NH3

Electron i m a c t
Calc. f r o * Tables 6 and 4
jitto
E l e c t r o n impact
(inetics o f the pyralysis
o f N2H4
E l e c t r o n impact

N O I I - 90 l1 Spectroscopic ( p r e d i s s o c i a t i o n )

:henil uminescence f o r t h e
r e a c t i o n H + NO
:ale. from Tables 6 and 4
jitto
jpectroscopic ( p r e d i s s o c i a t i o n )

:ale. from Tables 6 and 4


fitto
I

n
I

Data o f Table 1
Calr. from Tables 6 and 4
Table 3 ( c o n t i n u e d )

Reaction Method

NF, - NF, F + ;ale. from Tables 6 and 4


N2F4 ?NF2 Electron impact

Electron impact and


teaperature dependence of
i n t e n s i t y o f spectrun
lass spectrometric
4ean o f 156, 1651

:ale. froa Tables 6 and 4

ditto
:ale. from d i s s o c i a t i o n
a c t i v a t i o n energy
NCI =N + Cl Zalc. f r o a Tables 6 and 4

:ale. from e q u i l i brium


constants i n 1611

:ale. from Tables 6 and 4


litto

I a t a o f Table 1
:ale. f r o n e q u i l i b r i u m
constants i n /62/

I a t a o f Table 1
i q u i l i b r i u n studies

lass spectroret r i c
lnalysis of literature
Table 3 (continued) 83

-
Reaction Method Ref.

Data o f Table 1
Estimated 1661
Data o f Table 1
Calc. from Tables 6 and 4

pH3 = PH, + H ditto


PF=PTF Data o f Table 1
PF,=PF+F Calc. from Tables 6 and 4

+
PF3 = PFZ F ditto
POF=PO+F t

POF=PF+O
POFz = POF $- F
+
POF, = PFz O
+
POFs = POFz F
POFB= PF, + O Estimated l671
Measurements o f heat o f 1681
o x i d a t i o n o f PF3
Data o f Table 1
Calc. from Tables 6 and 4

+
PCI3 = PCI, Cl ditto
POCl = PO + C l I

+
PoCl = PC1 0
POClz = POCI +C1
+
P0Clz = PC12 0
P0Cls=POClz+ Cl
+
P0Cls = PCI, 0 Estimated 1671
Calc. from Tables 6 and 4

PClF= PC1 L - F ditto


PClF = PF 4- C1 R

PC1,F == PC1,+ F n
+
PClzF = PClF C1
+
PCIFz .= PClF F
+
PCIF, = PF2 Cl
POClF = POCl + F
T a b l e 3 (continued)

Reaction AH", He1hod Ref.


-

POCIF = POF t C Calc. f r o m Tables O and 4

POCIF = I'CIF $- ( ditto


POClTF = POC!, i- n
-+F
POCI?F = POCIFi
-1- Cl
POCI,F == PC1,F +
+O
POCIFz = POCIF 4
+F
POC!F, = POF, -+
+ c1
POCIF, = PCIF2 +
+O
POBr, =. PUr, O +
Asz = 2As .ata o f Table 1
As, = 2Asz wl l i h r l u m s t u d i e s

?ata o f Table l
. a l c u l a t e d from Table h
lass s p e c t r o m e t r i c
l a t a o f Table 1
h l c . froia Tables G and 4

:itto
lata o f Table 1
.alc. f r o m Tables 6 and 4

lethod o f atomic o r b i t s
a?c. f r o m Tables 6 and 4

Iethcd o f a t o m i c o r b i t s
a!c. frm T a b l r s 6 and 4

C, -
C 7 = C,,
Cg + C
-1 C
Table 3 (continued)

Method

Cg=C7--c M e t h o i o f a t o m i c orol I s
Cp = c * -j- C oittc
C, =: C, $- C
C,, = C1o -:-C
C,, = C,, C+
CI3 C,:
=X C
Cl, -- C,, +C
C:, = C:, +C
=Cn rC
Cl, : C18 2- c
c .
=.-l
= Cm - c
CO - C to Cata of Table 1
CO,-= CO - 0 b l c . f r o m l z b l e s 6 and 4

i q u i l i b r l o a studies

C a l c ~ l a t e dfrm la:le h
C a t a o f Table i
Calc. f r o m Tables b anc 4

IiCO; CH--(? ~ i i t o
CF C - I- D a t a o f I a b l ~1
FCO CO r F - Calc. f r o m T a b l e s b and 4

FCO=CF+O
F,CO -- FCO F +
FLCO= CF, 0 +
IJFCO HCO + F
5

l)

Cata o f [ a b l e l
Kinetic

Calc. f r c m Tables b a r d 4
Table 3 ( c o n t i n u e d )

-
Reaction Method Ref.

CI2C0 -- ClCO 4-Cl Calc. from Tables 6 and 4


CI,CO -
CCI1 - 1 0 ditto
FClCO = CICO 4-F I

FClCO :FCO ) Cl n

(NaCN), =- ZNaCN Mass s p e c t r o c e t ric

Si, = ~ S I Data o f Table l


Si? = Si, -1 Si Eass s p e c t r o m e t r i c [ r e c a l -
c u l a t e d t o 0% u s i n g /73/)
Mass s p e c t r n m e t r i c
Si, = Si, j-Si n II

SiO -:Si $ 0 Data o f Table 1


SiOp =- SiO 0 + Calc. f r o c i a b l e s b and 4

SiII = Si -f H Data o f Tabia 1


SiH, -SiH t l -+ Calc, fro. Tables 6 and 4

SiH, -- Sill, 3-H ditto


Sili, Sit13 H
~ L
n
SiJI, ZSiH,
-;
Kinetic
SiF Si -i- F
- D a t a o f Table 1
SiF, -- Sir i' + Calc, from Tables b and 9

SiF, - S1F2 -I'; ditto


s i p4 --
- - h"l r 3$- F n
SiCl = Si -1- Cl J a t a o f Tabie l
SiClp -- SiCi -; Cl Calc. from Tables 6 and 4

SiC1, -- SiCI, + Cl ditto


SiCI, =Z SiCI, +Cl n

S i c = Si C + Data o f Table !
Sic2 -- SIC 1- C Yass s p e c t r o m e t r i c
t a l c . from I s ? l e s 6 and 4
Table 3 (continued)

Reaction

Rass s p e c t r o m e t r i c
Laic. f r o m Tables 6 and 4

Mass s p e c t r o m e t r i c
Calc. from Tables 6 and 4

Si,C, = ?SIC Mass s p e c t r o m e t r i c


S;I& -
= S i c L SiC
n n

Si?C, -= Si,C -; C, I! n

Si2CJ= Si, - C, n n
Si,C = Si, ;S i c II n
Ge, = ?G? D a t a o f Table l
Ge,= Ge? L Ge 1:ass s n e c t r a m e i r i c
Ge, - XI., n n
Ge, Ge, -GE ; Calc. from Tables 6 and 4

Cata o f Table 1
Calc. from Tables 6 and 4

Czlc. f r o m t h e p y r o l y s i s
a c t i v a t i o n energy
GeC = Ge + C I a t a o f Table 1
GeC, = GeC - C 'lass s ~ e c t r o m e t rci
GeCP = Ge - C2 P n

Ge,C - GeC -- Ge U It

Ge,C = G C , - C
Ge,C = GtlC - Ge
GC& = GeC Gep
Ge,C - GC, C
-
-

GeSi Gr 51
G c S i = GeS1 - Ge
Ge,Si .- GC, ' Si
Ge,Si = (;c,.51 t Ge
GesS.i = GeSl -,
Ge,
Ge3Si-GP, Si
( k S i C == GeSl - - C
Table 3 (continued)

Reaction AN",, Method Ref.

GeSiC = GeC -1 Si Pass spectramet r i c [751


Ge,SiC = GeSiC + 11 n 1751
+ Ge
I8
It [75]
Ge,SiC = Ge,C +Si
Ge,SiC = GePSi -1 - C 11 It
1751
+
SnCl = Sn C1 Data o f T a b l e 1
SnClz = SnCl + Cl Calc. from Tables 6 and 4

+
SnBr = Sn Br Data o f T a b l e 1
SnBra = SnBr -tKr Calc. f r o m T a b l e s b and 4

PbF = P b -t F Data o f T a b l e 1
PbF, = PbF F + Calc. from Tables G and 4

P b C l = P b $ Cl Oata o f Table 1
PbClz = PbCl $- Cl Calc. f r o m Tables 6 and 4

+
PbBr = P b Br Oata o f Table 1
PbBrz = PbRr 1R r Calc. f r o m Tables 6 and 4

PbI=Pb-F1 Data o f T a b l e 1
+
FbI* = P b I I Calc. f r o m Tables b and 4

GaO = Ga 4 - 0 (Note51
-
GaOH Ga -S OH [lane photometry V71
GaOH = GaO - 1 - I1
( s e e Note 5 )
GaCl = Ga -1 Cl Data o f Table 1
GaCI, = GaCl -1C l Calc. from Tables 6 and 4

GaC13 = GaCI2 C! + ditto


Ga,CI, = 2GaC!, Measuren!nts o f v a p o u r (781
r r e s s u r e and d ~ n s i t y
d1tto 1791
is e
atso
[m)
C a l c u l a t t d from T a b l e 6
Data o f T a b l e 1

-
T a b l e 3 (continued)

Reaction Met hod

Calc. from Taoles G and 4


ditto
MC asurements o f v a p o u r
p r e s s u r e and d e n s i t y
C a l c u l a t e d from T a b l e b
Data o f T a b l e l
Calc. from Tables 6 and 4

GaI,=GaI,+ I ditto
Ga, l, =-- 2Ga I, Measurements o f v a p o u r
p r e s s u r e and d e n s i t y
C a l c u l a t e d from T a b l s 6
(Nete
In0 -; 1114-0 5 )
InOH = In OH + Flame p h o t o m e t r y
In0F1 : In0 f H
( s e e Note 5'
InCI = In C]+ Data o f Table 1
IiiClz = InCl + Ci Estimated

Cslc. f r o m T a b l e s 5 and 4

Estimated
C ~ l c . f r o m Tables 6 and 4

4ata o f Table 1
Estimated

Calc. from Tables b and 4

Estimated
.ale. from f a b l e s 6 and 4
j a t a o f Tablc 1
Estimated

Zalc. f r o m Tables b and 4


Table 3 (continued)

Reaction 1H"m Method

59 Estimated
%&l0 Calc. from Tables 6 and 4

+
InSb = In Sb 36.3 Data o f Table 1
+
lnSba = InSb Sb - Mass spectrometri c
+
lnSb, = In Sbz - n n

Zn,F,- 2ZnFz
+
ZnCl = Zn Cl
6.4
49
Analysis o f l i t e r a t u r e
Data o f Table 1
+
ZnCla = ZnCl C1 04&15 Calc. from Tables 6 and 4

9655 Analysi S o f l i t e r a t u r e
6.4 R n
8.4 II n
33 Data o f Table 1
7158 Calc. from Tables 6 and 4

5.3_i,i5 E s t i ~ a t e d
ZnzL -;2Zn 6.4 Analysisofliterature
Cd2F4 = 2CdF2 2.8 I n
+
CdCl = Cd Cl 65 Data o f Table I
CdClz = CdCl Cl+ 694113 Calc. from Tables 6 and 4

Cd2C14= 2CdClp
+
CdBr = Cd Br
84&5
2.8 IEstimated
Analysis o f l i t e r a t u r e

(bee hrote 6 )
CdBr, = CdBr Br+ 60 Icalc. from Tables 6 and 4

7%!30 Estimated
CdzBr4 = 2CdBr2 2.8 Analysis o f l i t e r a t u r e
CdI=Cd+ I 38 . Data o f Table 1
+
Cd12 = CdI I 54510 Calc. from Tables 6 and 4

57j 1 0 Analysis o f l i t e r a t u r e
Cdz G 2Cd Ja 2.8 I n
HgF=Hg+F 40.8 Data o f Table 1
&Fe = HgF $ F !.8f $ 2 Calc. from Tables 6 and 4
Table 3 (continued)

Reaction AH", Method

Hg,F, = 2HgF2 nalysis o f literature


HgCl = Hg Cl+ Data o f Table 1
HgCl, = HgCl + C Calc. from Tables 6 and 4

Calc. from photochemical and


thermochemical data
Hg,CI, = 2HgC12 analysis of l i t e r a t u r e
HgBr = Hg Br+ Jata o f Table 1
HgBr, = HgBr B1 + :ale. from Tables 6 and 4
Estimated
halysis of literature
l a t a o f Table 1
:ale. from Tables 6 and 4
istimated
Istimated

Hg,I4 = 2Hgla halysis of literature


HgCIBr = HgCl + istimated
+ Br

HgClBr = HgBr +
+ Cl

HgCl I = HgCI +1

HgCI I = H g l + Cl

HgBrI = HgBr +I
T a b l e 3 (continued)

Reaction Het hod


-
Ref.

HgBrI = Hgl + Br Estimated 1861


(sse
182,
601)
CuO=Cu + O (Note 7
CuOH = Cu OH + Flame photometry 1871
CuOH = CuO $ H Calc. from Tables G and 4

NiCl = Ni Cl+ 3ata o f Table 1


NiCl, = NiCl +
C1 Calc. from Tables 6 and 4

NiCI3 = NiCl, + Cl Equilibrium studies [W


Ni,C14 = BNiCI, Rnalysis o f l i t e r a t u r e [ W

NiBr = Ni -F Br Data o f Table 1


NiBr, = NiBr-+ Br Calc. from Tables G and 4

Ni,Br4 = PNiBr, Lnalysis o f l i t e r a t u r e [S81

CnCI, = CoClz t C1 Equilibrium studies [W,


1621
C0,Cl4 = 2coc1, Yass s p e c t r o m e t r i c [ W
I I
Co,Br4 = 2CoBr2 [W

FeF, = FeF, -F F Rnalysis o f l i t e r a t u r e 1901


FeCl = Fe - \ Cl Data o f Table 1
FeClz = FeCl Cl + Calc. from Tables G and 4

I;eCI3 = FeCI, 4-Cl ditto


Rnalysis o f l i t e r a t u r e W1
Equi lib r i m s t u d i e s [88,91l

Analysis o f l i t e r a t u r e [@l
+
FeBr .=. Fe Br Data o f Table 1
FeBrz = FeBr + Br Calc. from Tables G and 4

-
Table 3 (continued)

Reaction Method

ditto
Analysis o f l i t e r a t u r e

Equi l i b r i um s t u d i e s

Analysis o f l i t e r a t u r e

C a l c u l a t e d from Table 6
FeI, = FeI, +I Equilibrium studies

Fez I4 = 2Fe l2 Mass s p e c t r o m e t r i c

Fez 4 = 2Fe l3 Equi lib r i um s t u d i e s

MnO = Mn O + Oata o f Table 1


MnOH = Mn O H + Flame photometry
MnOH = MnO $ H Calc. from Tables 6 and 4

MnF=Mn+F Data o f Table 1


MnF, = MnF F + Calc. from Tables 6 and 4

MnF, = MnF, F -, ditto


MnCl = Mn - C1 Oata o f i a b l e 1
MnC1, = MnCI+ Cl Calc. from Tables 6 and 4

MnCI, = MnCI, L Equilibrium studies


+Cl
MnQ, = 2MnC1, Mass s p e c t r o m e t r i c

MnSr = Mn Br + Data o f Table 1


MnBr, = MnBr + Calc, from Tables 6 and 4
- Br
Mn,Br, = 'MnBr, Mass s p e c t r o m e t r i c

MnI=Mn+l Data o f Table 1


MnG = Nnlt l Calc. from Tables 6 and 4
CrO - C r & O Data o f Table 1
CrO, = CrO -L O Mass s p e c t r o m e t r i c
CrO, = CrO, 0 + W R
Table 3 (continued)

Reaction Met hod

h l c . from Tables h and 4

lass s ~ e c t r o m e t r i c

:qui lib r i um s t u d i e s
lass s ~ e c t r o m e t rci

: s t imated

lata o f Table l
lass s p e c t r o m e t r i c
n I

n II

easurement o f vapour pressure


l e c a l c u l a t e d from data i n
1981
ass spectrometric
R n

q u i l ibrium s t u d i e s

I( n

a t a o f Table ;
ass s p e c t r o m e t r i c
n n
l1 II

II U

qui lib r i urn s t u d i e s


D n
Table 3 (continued)

Peacti on Method Ref.

iouilibrium studies [l041

Oata o f Table 1
Yass-specironet r i c j 1051
Oata o f Table 1
Mass-spectrometri c
Data o f Table 1
Calc. from Tables 6 and 4

Calc. from Tables 6 and 4

ditto
U

Data o f Table 1
Calc, f r o a Tables 6 and 4

D a t a o f Table 1
Calc. from Tables 6 and 4

Calc. from Table 6


Calc, from Tables 6 and 4

ditto
Calc. from Table 6
Data o f Table l
Heat o f r e a c t i o n o f diborane
with dimethylarine

Extrapolation o f vibrational w91


constants

ditto [l091
a [l091
Calc. from Tables 6 and 4

HBO = BH 1-0 ditto


Table 3 (continued)

Method

BOH = R + O H rstiwated
HB02 = HBO 0 + :ale. f r o r Tables 6 and 4
)itto
:ale. from Table 6
istirated

h l c . from Table 6

lata o f Table 1
ialc, f r o r Tables 6 and 4

litto
a l c . froa Table 6
h l c . from Tables 6 and 4

itto
a t a o f Table 1
,ale. from Tables 6 and 4
+
BC& = BCla Cl
B2C14= 2BClz
ClBO BC1 O
=I +
+
ClBO = B 0 C1
+
BFCl = BC1 F
+
BFCl = RF C1
RFZCI = BCIF 4-F
+
BFZCI = BF2 C1
BFC12 = BFCl+ C1
+
BFCI, =. BClz F
BS=B+S ata o f Table 1
BS2 = BS f S ale. froa Tables .6 and 4
B& = 2BS itto
+
B&, = BS2 R n
+
-
B& = B& S I

B& +
BS, BS II
T a b l e 3 (continued)

Roacti on Net hod


-
Ref.

Calc. from Tables 6 and 4

Oata o f Table 1
Calc. from Tables b and 4

Mass-spectrometri c Il'ol
Calc. from Tables 6 and 4

ditto
Oata o f Table 1
Estimated (591
n [59j
Data o f Table 1
Calc. from Tables b and 4

AIF, = AIF, ' - F ditto


A12F6 = 2.41F3 Mass-spectrometri c Ill11

LiAIF, -- AIF, c 11111


4-LiF
Calc. from Tables G and 4

AIOF = AIF 0 + ditto


AlCl = AI 1-C,I Oats o f Table 1
AIC I, = A!CI 7 Cl Calc. from Tables 6 and 4

ditto
Spectroscopic (long-wave 1115
spectrum l i m i t ) 113]

Vapour d e n s i t y measurements
Y2114:
1251
AIOCI == AI0 -;- Cl Calc. from Tables 6 and 4
-
AIOCl AiCl - ; 0 ditto
AlFCl = AIF / - C1 II

AIrCI - AlCl +F 11

AIF,CI = AIF2 +Cl X

AIF2CI = AlFCl + n
+Cl
Table 3 ( c o n t i n u e d )

-
Calc. from Tables E and 4
-
jitto
-~
Estimated
AIC- AI { - C 43&8 I a t a o f Table 1
AIICz = 2AlC 287 :ale. from Table 6
rJ0 = U 0 + 179f 17 3ata o f Table l
uo, = rlo + o Itil lass-spectrometric
uo3= 1.0, + 0 99 It

uzO* = X'0, lapour pressure aeasurement


.-
:ale. from Tables G and 4
11C14= UCIJ Cl+ .-

I cl5= [ U , +-C] -

+
I Cl,, = 1 Cls C1 .-

UOCI = rlo c l+ -
UOCls llOCl C ~.
+ -

Cl
UOCI, - l Ci, f 0
UOCI", = 1 0C12 1 -.
+ Cl
-

UOCI,
-F C1
-1,OCI, + ~-~

--
--
--

--
--

--
.-
Table 3 (continued)

Reaction Method

Calc. from Tables 6 and 4

ditto

Data o f Table 1
Calc. from Table 6
ditto

(BeO), = (BeO),
+ Be0
4-

BeF= Be F + Data o f Table 1


BeF, - ReF F -
Calc. from Tables 6 and 4

Uata o f Table 1
Calc. from Tables 6 and 4

-
MgO Mg + O Uata o f Table 1
MgOH = Mg OH , Flame photometry
MgOH -- MgO f H Calc. from Tables 6 and 4

3ata o f Table 1
Table 3 (continued)

Reaction AH", Method

MgF2 = MgF+F Calc. from Tables b and 4

MgCl = Mg + Cl Data o f Table 1


MgClz = MgCl 4 Calc. from Tables 6 and 4
i-Cl
MgBr =- Mg $ Br Oata o f Table 1
MgBr, =- MgBr+Br Calc. from Tables G and 4

CaF = Ca 4-F Data o f Table 1


CaF, = CaF f F Calc. from Tables 6 and 4

CaC1, -
CaCl = Ca $- Cl
CaCl 4-Ci
Data o f Table 1
Calc. from Tables 6 and 4

-
CaBr Ca Br+
CaBrz = CaBr $ Br
Oata o f Table 1
Calc. from Tables 6 and 4

Data o f Table l
Calc. from Tables G and 4

SrF = Sr F+ I a t a o f Table 1
SrF, = SrF $- F :ale. from Tables 6 and 4
+
SrCl = Sr Cl l a t a o f Table 1
+
SrCI, = SrCl Cl :ale. from Tables 6 and 4
-
SrBr Sr Br+
+
SrBr? = SrBr Br
3ata o f Table 1
h l c . from Tables 6 and 4

3ata o f Table 1
:ale. from Tables 6 and 4
I a t a o f Table 1
lass-spectrometric

Ba,O -. BaO 4- Ba n

+
BaF -- Ba F I a t a o f Table 1
BaFz = BaF f F laic. from Tables 6 and 4
Table 3 (continued)

Reaction Method

BaCl = Ba C1 + Data o f Table 1


BaClz = BaCl $ Cl Calc. from Tables 6 and 4
BaBr = Ba Br + Data o f Table 1
BaBrz = BaBr Br + Calc. from Tables 6 and 4
LiO = Li 0 + Data o f Table 1
LizO = LiO Li + Vapour pressure measurement
Calc. from heat o f
sublimation
ditto

dynamic f u n c t i o n s f o r
l i t h i um oxide being used
i n the a n a l y s i s )

Mass-spectromet r i c

-
LiH Li H +
LiOH = Li OH+
Data o f Table 1
E q u i l i b r i a i n flames

ditto

LiOH = LiO +H Calc. from Tables 6 and 4


(LiOH)Z= 2LiOH Mass-spectrometric
(LiOD)2 -- 2 i i O D n

LiF = Li +F Data o f Table 1


fr. L C: I- - ,:a
Ew
-. -.
a-

X
,l
L;
-. -- .
j
9
.;
.
-7
g-5 811
=y.
BT/-- ELY
l _m*.. I= 22 ,;
a
1 , ' l
Table 3 (continued)

Reaction Method

Velocity diszribution i n
a m o l e c u l a r beam

M a s s - s p e c t romet r i c

L!Er Li - Rr+ Oata o f T a b l e l


(LiBr), = 2LiBr Velocity d i s t r i b u t i o n i n
(see Note 9 ) a m o l e c u l a r beam

Recalc. f r o m d a t a i n / l 3 0 1
u s i n c a l c u l a t e d AS
f o r ?he r e a c t i o n
Mass-spectrometric

Calc. f o r a s i m p l e i o n i c
model
Velocity distribution i n
a m01 e c u l ar beam

Li! - Li +I
(Li I)? = 2 ~I i k S e e
Oata o f T a b l e 1
Mass-spectrometric
kote 9)
n

Calc. f o r a s i m p l e i o n i c
model
Mass-soectromet r ic

Calc. f r o m T a b l e s 6 and 4

ditto
n

Mass-soectromet r i c

Iial((OH)2-NaOH~
T K O H (see
h i d e 10)
Table 3 (continued)

Reaction Method

NaF = Na $- F Data of Table 1


(NaF), = 2NaF Velocity distribution i n a
(see Note 9) m01ecul a r beam

ditto

Recalc. d a t a from /130/


u s i n g c a l c u l a t e d AS
f o r the reaction
Mass-spectrometri c
Calc. f o r a simple i o n i c
model
NaLiF, -- NaF L Mass-spectrometric
t L I F ( ~ o t e1 1 )
(NaF), =- (NaF), 4- Velocity distribution i n a
+ NaF m o l e c u l a r beam
NaCl = Na Cl + Data o f Table l
(NaCl), = 2NaCI Velocity distribution i n a
(5ee Note 9 ) m o l e c u l a r beam
ditto

Recalc. data from /130/


u s i n g c a l c u l a t e d AS
f o r the reaction
Yass-spectrometric

?eteraination o f molecular
weight o f vapour
litto

Calc. f o r a simple i o n i c
model
iitto
i a l c . f o r an i o n i c model w i t h
allouance f o r polarization
T a b l e 3 (continued)

Reaction Method Ref.

(NaCI),=(NaCI),
+ NaCl
+

Na2CI+ = Na+
+ NaCl
+
NaBr = Na Br+ ;aka o f Table 1
(NaBr)z = ?NaBr l e t e r n i n a t i o n o f molecular
(Note 9 ) u e i g h t o f vapour
Calc. f o r a simple i o n i c
model
NaI=Na+ 1 l a t a o f Table 1
(Na l), = 2Na I Velocity d i s t r i b u t i o n i n a
(Note 9 ) molecular beam

~ e c a l c . from data i n /l301


using c a l c u l a t e d AS
f o r the r e a c t i o n
; e t e m i n a t i o n o f molecular
weight o f vapour
Calc. f o r a simple i o n i c
model
KOH= K +OH ;ale. from Tables 6 and 4
(KOH), = 2KOH 4ass-sped romet r i c

KF=K+F l a t a o f Table 1
(KF), = 2YF Velocity d i s t r i b u t i o n i n a
(Note 9 ) m01ecul a r beam

'ass-spec t r o m e t r i c

2alc. tor a simple i o n i c


model
;ata o f Table 1
Velocity d i s t r i b u t i o n i n a
m01 e c u l a r beam

;ecalc. from data i n / l 3 0 1


using c a l c u l a t e d AS
f o r the r e a c t i o n
l e t e r m i n a t i o n o f molecular
u e i g h t o f vapour
jitto
Table 3 (continued)

Reaction Method

(KCI),= 2KCI
(Note 9)
Calc. f o r a simple i o n i c
model
Calc; f o r i o n i c model wi t h
allowance f o r p o l a r i z a t i o
K&I+ = KC1 K+ + Mass-spectrometri c
+
YBr = U Br Data o f Table 1
(KBr), = 2KBr Calc. f o r a simple i o n i c
(Note 9 ) model
K2Brf = KBr K' + Mass-spectrometri c
KI=K+I Data o f Table 1
(KI)z = 2K1 Velocity distribution i n a
(Note 9 ) m01 ecul a r beam
Calc. from data i n 11301
u s i n g c a l c u l a t e d AS
f o r the reaction
Determination o f molecular
weight o f vapour
Calc. f o r a simple i o n i c
model
(RbOH), = 2RbOH Mass-spectrometric
(Note 1 )
RbF= Rb F+ Data o f Table 1
(RbF), = 2RbF Velocity distribution i n a
(Note 9) m01ecul a r beam

Mass-spectromet r i c

Calc. f o r a simple i o n i c
model
RbCl = Rb Cl+ Data o f Table 1
(RbCI), = 2RbCI Velocity d i s t r i b u t i o n i n a
(Note 9 ) molecular beam

Recalc. from data i n /130/


u s i n g c a l c u l a t e d AS
f o r the reaction
Mass-spectromet r i c

Vapour d e n s i t y measurements
T a b l e 3 (concluded)

Reactf on AH ",g, Method


(RbCI)z=2RbCI 44.6 Calc. f o r a simple i o n i c
(Note 9 ) qndel
AHm= Calc. f o r i o n i c model w i t h
=32.7 allouance f o r p o l a r i z a t i o n

RbzClf=RbC1+CI+ Mass-spect romet ric


(OOH), = 2CsOH AHesz= n
540.2
(Note 13)
+
CsF = C S F 116 Data o f Table 1
(CsF), = 2CsF AH97~= Velocity distribution i n a
z39.5
(Note 9 ) molecular beam

39.0 Calc. f o r a simple i o n i c


model
102.5 Data o f Table 1
H 8 1 ~ 3 8M
, ~a ~ ~ - ~ p e ~ t r ~ m e f r i ~
U
AHs1o=
=34j1.3
H,.00=35.7j-0.2 n
~ i H ~ 3 0 0 =Vapour density measurements
=37.3

II
41.5 Calc. f o r a simple i o n i c
model
AH8,,=34. 1 Calc. f o r i o n i c model w i t h
a1 louance f o r p o l a r i z a t i o n
100.5 Data o f Table 1
CsBr = CS Br + AH848= ass-spectronetric
(CsBr), = 2CsBr =32.9@.6
(Note 9 )
iHtooO=32.6r0.6
41.2 Calc. f o r a simple i o n i c
model
Csl=Cs+ I 84.6 '
a t a o f Table 1
(Cs1),=2CsI (Note
g)

39.5

l
Calc. f o r a simple i o n i c
model
Notes

1. The dissociation energy for H 2 0 = OH + H given below was calcu-


lated 141 except for those taken from r e f e r e n c e s 7, 8 , 12, 27. The
values given in 4 were modified by introducing s m a l l c o r r e c t i o n s
based on the heats of formation of the 0 and H a t o m s given in the
p r e s e n t handbook.
2. T h e a s s u m e d value Do ( F 2) = 37 + 1 i s based on studies of the
dissociation equilibrium of fluorine (this subject i s reviewed 1211).
T h e value Do ( F 2 ) = 38.5 + 0.6 given in Table 1, whlch was calcu-
lated f r o m Do (HF), AH; (HF) and Do (H2) i s consistent with this
r e s u l t to wlthin experimental e r r o r .
3. T h e a s s u m e d value Do (HF) = 134.3 + 0.7 Is based on the heat of
formation of H F (Table 6 ) , the heat of formation of hydrogen a t o m s
(Table 4) and of fluorine ( s e e note 2 above). The value a s s u m e d in
Table 1 [ Do (HF) = 135.1 + 0.31 was obtained by extrapolation of
the vibrational constants of the H F molecule. The two values a g r e e
to within experimental e r r o r .
4. The value Do (NO) = 150 + 1 was deduced f r o m the heat of for-
mation of NO (Table 6). T h e o t h e r possible value Do (NO) = 152.3 +
0.9 (Table 1) i s based on spectroscopic m e a s u r e m e n t s and a g r e e s
with the f o r m e r r e s u l t to within experimental e r r o r .
5. It i s v e r y difficult to s e l e c t the c o r r e c t values of D (GaO H) -
and D ( I n 0 - H) and the related values of D (GaO) and D (InO).
It i s commonly a s s u m e d that D, (Ga0) = 5 8 a n d DO (InO) = 23 11561
but t h i s l e a d s to Do (GaO-H) = 147 and Do ( I n 0 - H) = 165, which
a r e c l e a r l y too high [the calculation was b a s e d o n values of DO(GaO
- OH) and Do (In - OH) given in Table 31. The higher values
D, (GaO) = l 1 6 and Do (InO) = 1 0 3 given in r e f e r e n c e 157 lead to
DO (GaO - -
H ) = 87 and Do ( I n 0 H) = 84. which a r e apparently
-
too low in comparison with Do (Ga OH) and Do (In - OH), and
a r e in p o o r agreement with the analogous values for LiOH and NaOH.
The values f o r the atomisation e n e r g i e s ( D,,,. ) and bond e n e r -
gies f o r LiOH. NaOH, GaOH and InOH a r e given below:

Li OH 205 103.8 127


NaOH 193 90 109
GaOH 203 102 (120)
In OH 187 86 (112)

A s c a n be s e e n , t h e r e is a g e n e r a l analogy between the bond


e n e r g i e s in LiOH and GaOH on the one hand, and NaOH and InOH.
on the other. T h e figures in brackets give the estimated values of
- -
Do (GaO H) and Dn ( I n 0 H ) which correspond to D , (GaO)= 83
and / J P (InO) = 7 5 . In addition to the analogy between LiOH and
NaOH, which was used in the e s t i n > a t e s , it was a l s o assunied that
the following relationships must he satisfied for GaOH and InOH:
(a) - -
D,, ( M e 0 H ) > D o (Me OH) s i n c e , otherwise, the experi-
m e n t s described in r e f e r e n c e 156 would show the existence of
-
dissociauon equllibria f o r the M e 0 H bond r a t h e r than Me OH.
@) D., (-0)
-
>Do (InO) s i n c e t h i s i s usually observed in o t h e r
g r o u p s of the periodic tahle.
+
T h e r e s u l t DO (CdBr) = 7 3 15, recommended in r e f e r e n c e 156,
i s too high by comparison with the correspondingdata f o r CdCl and
CdI. It l e a d s t o DO (CdBr - B r ) = 4 7 , which i s a l s o in conflict with
the corresponding values for CdC12 and Cd12. In o r d e r t o achieve
better agreement between the dissociation energies of cadmium
halides it i s assunied in the p r e s e n t compilation that D, (CdBr B r ) -
= 60, which c o r r e s p o n d s t o D , (CdBr) = 58.
+
T h e r e s u l t DO (CuO) = 113 1 0 , given in reference 155, l e a d s to
-
the fact that the corresponding r e s u l t I ) , (Cu OH) = 50 i s l e s s
+
than DO (Cu - OH) = 61 4 , which s e e m s unlustifiable. Such a low
value for i), (CuO - H) also conflicts with existing data for the
hydroxides of other lnetals ( s e e note 5). It i s a s s u m e d in the present
tables that D, (CuO) = 80, which leads to a better agreement be-
-
tween the Cu - OH and CuO H bond energies.
T h e r e s u l t D, (Tic]) = 25 _+_ 5 reported in r e f e r e n c e 156 leads to
-
D, (TIC1 Cl) = 217, w h i c h i s c l e a r l y incorrect. In o r d e r to c o r r e l a t e
th bond energy data in compounds of titanium with chlorine, It i s
a s s u m e d that 1)" (TiC1) = l 0 0 20. +
T h e various reported values f o r the heat of dimerisation a t differ-
ent ten:peratures w e r e reduced t o Oo and 298.15 OK in accordance
with the equation given in r e f e r e n c e 129. The frequencies of the
normal vibrations of the molecules of alkali metal halides w e r e
a s s u m e d on the b a s i s of the recommendntions in r e f e r e n c e 2 1 and
the measurements reported in r e f e r e n c e s 148-150.
Calculated, using the value A H , : ~ , =I 0 reported in reference 138
for the reaction: (KOH)? + (NaOH):: = 2NaK(OH)?.
Calculated. using the r e s u l t A H ~ I ; ,= 0 reported in reference 125
for the reaction: (NaF):! + ( L i F ) : = 2NaLiF2.
Calculated using the difference between the e n e r g i e s of d i m e r i s -
ation of CsOH and HbOH. reported in r e f e r e n c e l 4 6 (L\ti,;i3 = -4.5 2 3)
and the assunled value for the dinierisation energy of CaOH.
Calculated using the difference in the dimerisation e n e r g i e s of
CsOH ana KOH, AH,.,,: = -6.3 + 0.2. reported in reference 146, and
the assumed value for the dimerisation energy of KOH.

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11. HEATS O F FORMATION O F ATOMS AND RADICALS

Table 4
HEATS O F FORMATION O F ATOMS
(kcal/g.atom)

T h e table gives the heats of formation of monatomic g a s e s from


elements in standard states. Practically all the elements up to element
96 in the periodic table a r e included, although data on the heats of
sublimntion and therefore on the heats of formationof the corresponding
monatomic g a s e s a r e not available for certain lanthanides and trans-
uranic~.

T h e f i r s t column of the cable lists the elements in alphabetical o r d e r ;


the second and third columns give the heats of formation of monatomic
g a s e s a t 0 and 298.15"K. T h e heats of formation a t one temperature
w e r e conve;rtecl to the o t h e r , using equation ( 7 ) on p. i x . The values
of HI,,.Y, . n e c e s s a r y for the conversion were a s a rule taken, [ l , 21
while in those c::ses where the c o ~ r e s p o n d i n gdata were not a w i l a -
ble in the handbooks they w e r e taken f r o m the periodical literature,
o r estimated approximately. T h e fourth column indicates the method
used to determine the heats of formation. F o r elements in the gaseous
s t a t e under standard conditions the corresponding quantities were
e i t h e r z e r o (inert g a s e s ) o r w e r e calculated from the dissociation
e n e r g i e s for the corresponding diatomic g a s e s (H2 , 0 2 , etc.). For
the remaining elements the heats of formation of monatomic g a s e s were
obtained f r o m measurements of the saturated vapour p r e s s u r e and the
composition of the vapour under experimental conditions. As a r u l e ,
preference i s given to values calculated f r o m the experimental data,
using equation (10) on p. 1 . In isolated c a s e s . the n e c e s s a r y calcu-
lations w e r e repeated using the thermodynamic functions given [l, 21.
T h e l a s t column gives the references where the corresponding value of
the heat of sublimation o r dissociation w a s given o r recommended.

T h e e r r o r s a r e those obtained o r recommended in the original sources.


It should be notedthat original papers a s a r u l e quote e r r o r s charac-
t e r i s i n g only the spread of the individual measurements but do not allow
for systematic e r r o r s .
Table 4

Atom Method

Analysis o f vapour pressure data


ditto
Vapour pressure measurements
ditto
D

Analysis o f vapour pressure data


ditto
Vapour pressure measurements
ditto
m

Analysis o f vapour pressure data


ditto
I

Vapour pressure measurements


Analysis o f vapour pressure data
Vapour pressure measurements
d i t t o (see Note 1 )
Vapour pressure measurements
ditto

Analysis o f vapour pressure data


ditto
Calc. f r o n vapour pressure data
assuming diatomic vapour

Vapour pressure measurements


ditto
Table 4 (continued)

Atow Method

Br Vapour pressure data and D,, ( e r Z )

C Vapour pressure data f o r graphite


and AH, (CO) and D,, (CO)

Ca Analysis o f vapour pressure data


Cd ditto
I

Vapour pressure measureaents


ditto
n
Ce n

Cl Calc. from D,, (Cl2)


Cm
CO Analysis o f vapour pressure data
Vapour pressure measurements (Note 2:
ditto
Cr Analysis of vapour pressure data
ditto
Vapour pressure aeasurements
ditto
I

CS Analysis o f vapour pressure data


Cu ditto
Vapour pressure measurements
ditto
I
DY
I

I
Er
Eu
F Data on e q u i l i b r i u m d i s s o c i a t i o n o f
F2 (see Note 21, Table 1)

Calc. from D, (HF) and


AH,JHF, gas)
le Vapour pressure measurements
ditto
II
Fr

-
Table 4 (continued)

Atom n e t hod

Ga A n a l y s i s o f vapour pressure data


Calc. from data on anomalous
dispersion o f l i g h t i n gallium
vapour /30/ u s i n g new d a t a on
s p e c i f i c heat o f l i q u i d g a l l i u m
Vapour pressure measurements
Gd Estimated
Vapour p r e s s u r e measurements
Ge A n a l y s i s o f vapour pressure d a t a
Mass-spectrometri c
Vapour pressure measurements
1.1 Calc. from Table 1
He
Hg A n a l y s i s o f vapour pressure d a t a
HI Calc. from b o i l i n g p o i n t
H0 Vapour pressure measurements
In ditto
Calc. from anomalous d i s p e r s i o n o f
l i g h t i n indium vapour

Vapour p r e s s u r e measurements
ditto
n
Ir Calc. from h o i l i n g p o i n t
Vapour pressure measurements
I A n a l y s i s o f vapour pressure d a t a
K ditto
Kr
La Calc. from data i n 1381
Vapour p r e s s u r e measurements
ditto
Li A n a l y s i s o f vapour pressure d a t a
l. U Vapour pressure measurements
A\ g A n a l y s i s o f vapour p r e s s u r e d a t a
Rl n ditto
Vapour pressure measurements
d i t t o (see Note 3 )

-
T a b l e 4 (continued)

Atoa Method Ref.

M0 A n a l y s i s o f vapour pressure data


N Calc. from Table 1
Na A n a l y s i s o f vapour pressure data
Nb Calc. from r a t e s o f evaporation
Vapour pressure measurements
Nd A n a l y s i s o f vapour pressure data
Vapour pressure measurements
ditto
Ne
Ni A n a l y s i s o f vapour pressure data
Vapour pressure measurements (Note 4)
NP
0 Calc. from D,,( 0 2 )
0S
P A n a l y s i s o f vapour pressure data
Pa
Pb A n a l y s i s o f vapour pressure data
Pd Estimated
Vapour pressure measurements
P0 A n a l y s i s o f vapour pressure data
Pr Calc. from data i n 1381
Vapour pressure measurements
Pt A n a l y s i s o f vapour pressure d a t a
Vapour pressure measurements
ditto
Pu

Ra
Rb A n a l y s i s o f vapour pressure data
Re Calc, from data i n 1471
R11 Estimated
Vapour pressure measurements
Rn
Ru Estimated
S Vapour pressure data and values o f
I), (SO), AH, (SO) and A H , ( S ~ )
Table 4 (concluded)

Atoa Method

Sb ditto
Sc tstimated
Vapour pressure measurements
Se A n a l y s i s o f vapour pressure data
Si A n a l y s i s o f vapour pressure data
ditto
Srn Estimated
Vapour pressure measurements
Sn A n a l y s i s o f vapour pressure d a t a
Sr ditto
Ta Vapour pressure measurements
Tb ditto
Tc Estimated
Te A n a l y s i s o f vapour pressure data
Th Vapour pressure measurements
Ti ditto
T1 A n a l y s i s o f vapour pressure d a t a

Calc. from data on anomalous


dispersion o f l i g h t i n
t h a l lium vapour
Tu Vapour pressure measurements
U ditto
P

v
W A n a l y s i s o f vapour pressure data

Xe
Y Estimated
Yb Vapour pressure measurements
Zn A n a l y s i s o f vapour pressure data
ditto
Vapour pressure measurements
ditto
Zr n

-
Notes

l. I t h a s Ijeen found (131 t h a t a H z ( B ) . d e t e r t l l i n e t l f r o m e f f u s i o n


m e a s u r e m e n t s , d e p e n d s on t h e s i z e of t h e e f f u s i v e a p e r t u r e . a n d
v a r i e s f r o m 100.6 t o 1 2 4 . 5 .
2. T h e v a p o u r p r e s s u r e of C o [ 2 1 j i s a p p a r e n t l y s u b j e c t t o s y s t e m a t i c
errors. T h i s i s i n d i c a t e d b y t h e c h a n g e i n m a g n i t u d e of AH," ( C O )
c a l c u l a t e d f r o m e q u a t i o n ( 1 0 ) o n p. 1 , w h i c h r a n g e s f r o m 83.1
a t 1 3 4 5 " K t o 8 4 . 3 a t 1 5 4 1 " K , a n d by t h e s u b s t a n t i a l d i s c r e p a n c y
b e t w e e n t h e v a l u e of 83.7 o b t a i n e d f r o m e q u a t i o n ( 1 0 ) a n d t h e v a l u e
9 2 . 5 o b t a i n e d f r o m e q u a t i o n (9).
3. T h e v a l u e s q u o t e d w e r e c a l c u l a t e d f r o m e q u a t i o n ( 9 ) o n p. 1 ,
a p p a r e n t l y o n t h e b a s i s of i n c o r r e c t v a l u e s f o r c o n v e r s i o n t o 2 9 8 "K.
T h e u s e of HI.- H?98. a s g i v e n i n r e f e r e n c e 2 g i v e s AHr29R = 68.5.
4. A s i n t h e case of C O ( s e e N o t e 2 a b o v e ) t h e m e a s u r e m e n t s of t h e
v a p o u r p r e s u r e of N i [ 2 1 ] a r e a p p a r e n t l y s u b j e c t to e r r o r .

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38. DAANE, A.H. 1950. U S A E C AEDC-3209.
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58. WHITE, D., WALSH, P.N., GOLDSTEIN, H.W., and DEVER, H.W. (1961).
I . P h y s . Chem., 65. 1404.
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212, 379.
Table 5
HEATS O F FORMATION O F ORGANIC RADICALS
(kcal/mole)

T h e majority of the values given in the table a r e those of the most


reliably established heats of formation of organic radicals. The values
indicated by an a s t e r i s k were calculated f r o m the formula

where the heats of formation I N and X r e f e r to 29.8 " K , whereas


Dr ( H - X) r e f e r to the tenlperature during the experiment ( s e e Table 2).
T h e heats of formation of r a d i c a l s , taken f r o m original papers, a r e
accompanied by the corresponding references. The absence of a refer-
ence indicates that the particular quantity has been calculated by the
present authors f r o m bond e n e r g i e s (Table 2 ) , heats of formation of
a t o m s (Table 4 ) and heats of formation of molecules ( 1 2 151. -
T h e radicals in the table a r e s e t out a s follows. T h e hydrocarbon
radicals a r e given in the o r d e r of increasing number of C and H atoms.
They a r e followed by substituted compounds with the substituents given
in the o r d e r : halogens, oxygen, nitrogen, sulphur.

Ref.
Table 5 (continued)

Radical

i so,-C4H,
t. -C,H,

(3
C,H,CH,
o-CH,C,H4CH2
m -CH3CeH4CH2
p -CH3C,H4CH2
CF
CHF
CF2
CH,F
CHFz
CF,
C2F
CC1
CCI,
CCI,
C,H,CI
CZI~I3CI,
C2H2C13
C,HCI,
c2c13
CH2Br
CHBr,
CBr,
H0
H02
Table 5 (continued)

Radical
T a b l e 5 (concluded)

Radical

CH:lC00
CzEf,COO
n C,H,COO
C2H,0
FCO
ClCO
NH
NH?
REFERENCES

1. GURVICH, L.V.. KHACHKUROZOV, G.A.. MEDVEDEV. V.A., VEITZ.


I.V., BERGMAN. G.A., YUNGMAN, V.S., RTISHCHEVA, N.P., and
KURATOVA, L.F. et al. (1962). Thermodynamic properties of individual
s u b s t a n c e s , Izd. AN SSSR, Moscow.
2. McDOWELL, C.A., LOSSING. F . P . , HENDERSON, I.H.S., and FARMER,
J.B. (1956). Can. I . Chem., 34. 345.
3. FIELD, F.H., and FRANKLIN, J.L. 1957. Electron Impact Phenomena
and the Properties of G a s e o u s Ions, N.Y., p. 129.
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416.
8. GALLEGOS, E.J., and KISER, R.W. (1961). 1. Am. Chem. Soc., 83, 776.
9. DILBELER, V.H., REESE, R.M., and FRANKLIN, J.L. (1961). 1. Am.
Chem. Soc., 83, 1813.
10. SEHON, A.H., and DARWENT, B. (1954). 1. Am. Chem. Soc., 76,4806.
11. FRANKLIN, J.L., and LUMPKIN, H.E. (1952). 1. Am. Chem. Soc., 73, 1023.
12. KOROBOV, V.V., and FROST, A.V. (1949). Free energies i n organic com-
pounds, Glavpoligrafizdat, Moscow.
13. ROSSINI. F.D.. WAGMAN, D.D., EVANS, W.H.. LEVINE, S., and J A F F E - V .
1952. S e l e c t e d V a l u e s of Chemical Thennodynamics Properties. Natl.
Bur. Standards. Circ. 500, Washington.
14. ROSSINI, F.D. 1953. S e l e c t e d V a l u e s of P h y s i c a l and Thermodynamic
Properties of Hydrocarbons and R e l a t e d Compounds. Pittsburgh.
15. MORTIMER, C.T., PRITCH.4RD. H.O., and S I ~ T W E R H.
, (1952). Trans.
Farad. Sos., 48, 220.
16. DIBELER, V.H., FRANKLIN, J.L., and REESE, R.M. (1959). 1. Am. Chem.
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17. GOWENLOCK, B.D., JONES, P., and MAJER, J.R. (1961). Trans. Farad.
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18. BERNECKER, R.R., and LONG, F.A. (1961). 1. P h y s . Chem., 65, 1565.
19. BUSTFIELD, W.K., M N , K.J., MACKLE, H., and O'HARE, P.A.G. (1961).
Trans. Farad. Soc., 57, 1064.
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22. KNIGHT, H.T., and RINK, J.P. (1961). 1. Chem. Phys., 35, 199.
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24. GOLDFINGER, P., and MARTENS, G. (1961). Trans. Farad. Soc., 57. 2220.
Table 6
HEATS O F FORMATION O F INORGANIC ~ D I C A L S
(kcal/mole)

T h i s table gives the heats of formationof radicals and some inorganic


molecules. T h e inclusion of the heats of formationof saturated molecules
i s due to the fact that they a r e n e c e s s a r y f o r the calculation of the bond
e n e r g i e s in T a b l e 3. Moreover, many of the values included in the table
have been estimated by the present a u t h o r s , and a r e not available else-
where.

T h e f i r s t c o l u n ~ nof the table gives the chemical formulae (all these


substances a r e a s s u m e d to be ideal gases). The second and third columns
give the heats of formation of the compounds from their elements in
standard s t a t e s a t 0 and 298.15 ' K , respectively (the figure of 298 O K i s
given instead of 298.15 " K in the heading to save space). T h e fourth
column indicates the method used to determine the heat of formation.
If the heat of formation h a s been calculated using the dissociation energy
a s s u m e d in this handhook, the fourth column gives the reference to the
corresponding table. T h e heats of formation of diatomic molecules given
in this tahle a r e hased on values calculated f r o m the dissociation
e n e r g i e s of these molecules (Table l ) , and the heats of formation of the
corresponding atoms (Table 4). T h e standard states accepted in this
handbook % r e discussed in the introduction. The fifth column gives the
references.

T h e e r r o r s indicated in the table a r e either those given by the original


a u t h o r s o r estimated values. T h e e r r o r s , including those of a number of
independent m e a s u r e m e n t s , were ohtained hy taking the r.m.s. value.

T h e handbooks and reviews listed in the introductionwere freely used


in compiling this table. Particular attention was paid to the consistency of
the chtn in this tahle with that given in other tables. T h e o r d e r in which
the coinpountis , i r p listed is the s a m e a s that in the thermodynamic
! ~ : ~ n c l l ) o 14,
o k ~l ] .
Table 6

Molecule
Ref.
radqral

0 3 Analysis of l i t e r a t u r e 111
OH Calc. from Tables 1 and 4
OD Analysis o f l i t e r a t u r e Ill
OT a Ill
H02 111
DO, Estimated 121
H,O Analysis o f l i t e r a t u r e [l1
D,O n 111
HDO 111
~ W 2 111
D202 I*]
HDO, 11
Ill
a 111
T2O
HT0 I1
[l1
I1
DTO 111
F0 Calc. from Tables 1 and 4

F20 Analysis of l i t e r a t u r e Ill


F, 0, Heat o f d i s s o c i a t i o n 131

F,03 ditto 131


HF Analysis o f l i t e r a t u r e 1l
W ) , Calc. from Table 3
( W , ditto
(HF), a

(IWs
(HFh
( W 7

(HF),
OIFh
Cl3 halysis nf literature 111
C10 :ale, from Tables l and 4
CIOz inalysis o f literature Ill
Cl03 l!
141
Table 6 (continued)

Molecule Method
rad?Lal
Cl20 Lnalysis o f l i t e r a t u r e
HCI m
ClOH
C103F Yeasurements o f heats o f
hydrolysis
CIF3 4nalysis o f l i t e r a t u r e
ClzFe Calc. from Table 3
BrO 4nalysis o f l i t e r a t u r e
BrO, Calc. from Tables 3 and 4

HBr Rnalysis o f l i t e r a t u r e
BrOH Calc. from Tables 3 and 4

I0 Calc. from Tables 1 and 4


HI ditto
IOH Calc. from Tables 3 and 4
S Data o f Table 4
S2 Calc. from Tables 1 and 4
S3 Estimated
S4 Rnalysis o f l i t e r a t u r e
S6 Estimated
Sa Analysis o f l i t e r a t u r e
11
Se
SO Calc. from Tables 1 and 4
so2 Analysis o f l i t e r a t u r e
I
so3
s2o Calc. from Tables 3 and 4

SH Tables 1 and 4
Hzs Analysi S o f l i t e r a t u r e
HzSa Measurements o f heats o f
f o m a t i o n and evaporation
H& ditto
I
H&
T a b l e 6 (continued)

Method

Measurements o f heats o f
formation and evaporation
Estimated
Calc. from Tables 1 and 4
Analysis o f l i t e r a t u r e
ditto
I

Measurements o f heats o f
hydrolysis and evaporation
ditto
Calc. from energy o f c r y s t a l
lattice
Jhalysis o f l i t e r a t u r e
Calc. from Tables 3 and 4
Calc. from ~ ( N 2 0 5 )(Table 3 )

Analysis o f l i t e r a t u r e
Calc. from Table 3
ditto
II

Equi lib r i um studies


Calc. from Tables 1 and 4
Calc. from D (N2H4) (Table 3 )

Analysis o f l i t e r a t u r e
Electron impact
Estimated
Calc. from Tables 3 and 4
Analysis o f l i t e r a t u r e
Calc. from thenochemical data

Estimated

Recalc. from e q u i l i b r i u m data

Analysis o f l i t e r a t u r e
T a b l e 6 (continued)

Molecule
or
radical
Method

N0,OW Analysis o f l i t e r a t u r e
NH,OH n
NF n
NFz Calc. from Table 3
K F, Analysis o f l i t e r a t u r e
NZFZ n
NF, Measured heats of formation

FNO Analysis o f l i t e r a t u r e
NCI Estimated
NClz n

NCI, n
NOCl Calc. from Tables 3 and 4

NO&I E q u i l i b r i u m s t u d i e s and
c a l o r i m e t r i c measurements

NBr Calc. from Tables 3 and 4

NOBr ditto
P Data o f Table 4
P2 Calc. frcm Tables 1 and 4

p4 Analysis o f l i t e r a t u r e
PO Calc. from Tables 1 and 4

PO,? " Tables 3 and 4


PH Tablesland4
pH2 Estimated
pH3 Equilibrium studies

PF Calc. from Tables 1 and 4


PF, Estimated
l!
PF3
11
PF5
POF Estimated
I1
POF,
Table 6 (continued)

Molecule
or Met hod Ref.
radical

POF3 Calc. frnm Table 3


PC1 Tables 1 and 4
PClp Estimated
PCI, Measurement o f h e a t s o f
h y d r o l y s i s and e v a p o r a t i o n
PC16 Analysis o f l i t e r a t u r e
POCI Estimated
P0Clp n
POCI, Analysis o f l i t e r a t u r e
PClF Estimated
PCl,F n
PCIF,
POCIF
i'OCI,F
POCIF,
PBr, Measurements o f heat o f
hydrol y s i s
POBr, ditto
A S, Calc. from Tables 1 and 4

As, Table 3
Sb, " " T a b l e s 1 and 4
Sb4 Analysis o f l i t e r a t u r e
BiCl Calc. from Tables 1 and 4

BlCI, Estimated
BiCIS Measurement o f heats o f f o r m a t i o n
and sub1 i m a t i o n
C Analysis o f l i t e r a t u r e
(1, ditto
It
C,
Calc. by method o f atomic
orbits
C4 Mass-spectromet r i c
Calc. by method o f atomic
orbits
CS Mass-s e c t r o m e t r i c
Calc. Ey
method o f atomic
orbits
T a b l e 6 (continued)

mo ar r
radical
-
Ref.

ditto 1291
I
1291
I
1291
I
1291
I
1291
I
1291
I
1291
n 1291
I
1291
I
1291
n 1291
I 1291
Analysis of l i t e r a t u r e 111
I I 111
I I 111
I
I
111
I I 111
I I 111
n I
111
m n 111
n I 111
I I 111
n n 111
n I 111
I I
111
I I
111
I I Iil
I I 1'1
I I
111
I I 111
I I
111
Calc. from Tables 3
and 4

-
Table 6 ( c o n t i n u e d )

Molecule
Method Ref.
rasfcal

ClzC0 Analysis o f l i t e r a t u r e
FClCO I I

Si Data o f Table 4
Si2 Calc. from Tables 1 and 4
Sis Tables 3 and 4
SiO Analysis o f l i t e r a t u r e
SiOz Calc. from heats o f
formation and sublimation
SiH Calc. from Tables 1 and 4

Analysis o f l i t e r a t u r e
SiHa Estiaated
SiHI I

SiH, leasurerents o f heat o f


dissociation
leasurements o f heat o f
combustion
SiF Calc. from Tables 1 and 4

SiF, Estimated
SiF, I

SiF, Analysis o f l i t e r a t u r e
SiCl Calc. from Tables 1 and 4
SiC12 Equilibrium studies o f
Si(c st.) * SiC14(gas)z
=$icl2[ as)
Equi ibrium .&dies o f
silcryst.) CI2(gas)~
2 SiC12(gas)
SiCI, Estimated
SiCl, Anal y s i S o f l i t e r a t u r e
Sic Calc. from Tables 1 and 4
Sicz Mass-spect rometri c
Table 6 (continued)

Molecule
or Ref.
radical

SieC

Si& Calc. from Table 3


Si,C, " Tables 3 and 4

SkC ditto
Ge Data o f Table 4
Gez Calc. from Tables 1 and 4
Ge3 " T a b l e s 3 and 4

Ge4 ditto
GeO Calc. from Tables 1 and 4

GeO, Analysis o f l i t e r a t u r e
GeC Calc. from Tables 1 and 4

GeC, Tables 3 and 4

Ge,C ditto
I
Ge,C
GeSi I

I
Ge,Si
Ge,Si n

GeSiC L

Ge,SiC I

SnCl Calc, from Tables 1 and 4

SnCI, Calc. from heats o f


f o r m a t i o n and s u b l i m a t i o n
SnBr Calc. from Tables 1 and 4

SnBr, Calc. from heats o f


f o r m a t i o n and s u b l i m a t i o n
Sn I, Estimated
Calc. from heats o f
formation and sub1 i m a t i o n
PbF Calc. from Tables 1 and 4
Table 6 (continued)

Molecul~

- or
radi ca'

PbFz Analysis o f l i t e r a t u r e
PbCl Calc. from Tables 1 and 4

PbCI.: Calc. f r o a heats o f


formation and sublimation
P bBr . Calc. from Tables l and 4

PbBrl Calc. from heats o f


formation and sublimation
Pb l Calc. from Tables l and 4

Pbl, Calc. from heats o f


formation and sublimation
GaO Calc. from Tables 1 and 4
GaOH Tables 3 and 4
GaCl '
Tables 1 and 4
GaCIS Estimated
GaCI, Calc. from heats o f
formation and s u b l i n a t i o n
Ga2CI, ditto
GaBr Calc. from Tables 1 and 4

GaRr, Estimated
GaBr, Calc. from heats o f
formation and sublimation
Ga,Br, ditto
Ga l Calc. from Tables 1 and 4

Gal, Estimated
Gal, Calc. from heats o f
formation and sublimation
Ga, 1; ditto
In0 Calc. from Tables 1 and 4
lnOH H Tables 3 and 4
InCI ' Tables 1 and 4
InCI, Estimated
InCI, Calc. from heats o f
formation and sublimation
Table 6 (continued)

InRr
Method

Calc. from Tables 1 and 4


-Ref.

InBr, Estimated
InBr, Calc. from heats o f
formation and sublimation
In l Calc. from Tables 1 and 4

l n Iz Estimated
In IS Calc. from heats o f 137,411
fonnati on and subl imation
InSb Calc. from Tables 1 and 4

InSb, " Tables 3 and 4


ZnF, Calc. from heats o f 1361
formation and sublimation
Zn,F, Calc. from Table 3
ZnCl Tables 1 and 4
ZnCIP Calc. from heats o f 14,421
formation and sublimation
ZnzC14 Calc. from Table 3
ZnBrz Calc. from heats o f 1371
formation and sublimation
7nJ3r4 Calc. from Table 3
Zn I Tables 1 and 4
z n l, Calc. from heats o f 1371
formation and sublimation
Znz 14 Calc. from Table 3
GF, Calc. from heats of 1361
formation and sublimation
CdP4 Calc. from Table 3
CdCl Tables 1 and 4
CdCI, Calc. from heats o f
1371
formation and sublimation
a&I4 Calc. from Table 3
CdBr " Tables 1 and 4
GiBrz Calc. from heats o f I371
fonnation and subl imation
CdzBr4 Calc. from Table 3
Table 6 (continued)

No1e c u l e
or Method
radical
Cd I Calc. from Tables 1 and 4
12 Calc. from heats o f
f o r m a t i o n and s u b l i m a t i o n
Cdz 4 Calc. from Table 3
HgF " Tables 1 and 4
HgFz Calc. from heats o f
f o r m a t i o n and s u b l i m a t i o n
H~2F4 Calc. from Table 3
HgCl " Tables 1 and 4
HgCh Calc. from h e a t s o f
f o r m a t i o n and s u b l i m a t i o n
HgzCI, Calc. from Table 3
HgBr " Tables 1 and 4
Calc. from heats o f
f o r m a t i o n and subl i m a t i o n
HgzBr4 Calc. from Table 3
Hg I " Tables 1 and 4
Hg Ja Calc. from heats o f
formation and s u b l i m a t i o n
H& 14 Calc. from Table 3
cuo " Tables 1 and 4
CuOH Tables 3 and 4
NiF, Calc. from heats o f
f o r m a t i o n and subl i m a t i o n
NiCl Calc. from Tables 1 and 4

NiCI, Calc. from heats o f


f o r m a t i o n and s u b l i m a t i o n
NiBr Calc. from Tables 1 and 4
NiBr, Calc. from heats o f
formation and s u b l i m a t i o n
CoCI, ditto
FeCl Calc. from Tables 1 and 4
FeCI, Calc. from heats o f
f o r m a t i o n and s u b l i m a t i o n
FeCI, Analysis o f l i t e r a t u r e
Table 6 (continued)

No1ecule
or
radical
Fe2CI,
Method
- -Ref.

Analysis o f l i t e r a t u r e 1481
Equilibrium studies (491
FeBr Calc. from Tables 1 and 4
FeBr, Calc. from heats o f (4,471
formation and subl i m a t i on
FeBr, Equilibrium studies 1481
Fe2Br, a n 1481
Fe Iz Calc. from heats o f 14,471
formation and sublimation
MnO Calc. from Tables 1 and 4
MnOH Tables 3 and 4
MnF M Tables l and 4
MnF, Calc. from heats o f (361
formation and sublimation
MnF, ditto (361
MnCl Calc. from Tables 1 and 4
MnCl, Calc. from heats o f formation, [46,44
subl imation and fusion 371
MnBr Calc. from Tables 1 and 4

MnBr, Calc. from heats o f (361


formation and sublimation
Mn I Calc. from Tables 1 and 4
Mn 1% Calc. from heats o f (361
formation and sublimation
Cl0 Calc. from Tables 1 and 4
CrO, "Tables 3 and 4
ditto
CrCI, Analysis o f l i t e r a t u r e (501
CrCl, n n 1501
CrCI, I501
CrBrl Calc. from heats o f 36,511
formation and sublimation
CrzBr, Calc. from Table 3

-
Table 6 (continued)

E'olecule
ur
radlcal
Cr I, Calc. from h e a t s o f
f o r m a t i o n and s u b l i m a t i o n
AI00 Calc. from Tables 1 and 4

MOO,

Moo3 ditto
(MoO3)2 Calc. from Table 3
(h1003)3 ditto
WO Calc. from Tables l and 4

WO, "h ~ l e s3 and 4


WO3 ditto
1.0 Calc. from Tables 1 and 4

VO, '" Tables 3 and 4

TaO " Tables 1 and 4

TaO, Tables 3 and 4


TiO " Tables 1 and 4
TiO, Calc, from h e a t s o f
f o r m a t i o n and s u b l i m a t i o n
ditto
TiCl Calc. from Tables 1 and 4
Tic!, Analysis o f l i t e r a t u r e

TICI,

TiCI,

ZrO Calc. from Tables 1 and 4

ZrO, liapour p r e s s u r e nteasurements


T a b l e 6 (continued)

Molecule
or Method
radical
7 - -

B0 Calc. from Tables l and 4

BO, Analysis o f l i t e r a t u r e
B&, 11 11

B,O:, II n
BH Calc. from Tables 1 and 4

BH, " Table 3


W, Measurement o f heats o f thermal
d i s s o c i a t i o n o f diborane

HB0 Estimated
HBOz Analysis o f l i t e r a t u r e
HW3 n n

WO,), Equilibrium studies


Mass-spectrometri c
BF Calc. from Tables 1 and 4

BFz Estimated
BF3 Analysis of l i t e r a t u r e
B,F, Calc. from thermochemical data

FBO Estimated
RC1 Calc. from Tables 1 and 4

BCI, Estimated
BCI, Analysis of l i t e r a t u r e
B,CI, Thermochemi c a l
ClBO Estimated
BFCI n

BF&I n
0
RFCI,
BS Calc. from Tables 1 and 4

BS2
BeSz
T a b l e 6 (continued)

Holrculc
-
or Method Ref.
radical
BOCN Estimated
A10 Calc. from Tables 1 and 4

A120 Analysis o f l i t e r a t u r e
A1202 Calc. from Table 3
ALOs Analysis o f l i t e r a t u r e
AIF Calc. from Tables 1 and 4

AIFl Estimated
AIF, analysis o f l i t e r a t u r e
AlOF Estimated
AlCl Calc. from Tables 1 and 4

AlC12 Estimated
AICI, Analysis o f l i t e r a t u r e
A12CI, Estimated
AlOCl m
AlFCl U

AlF2Cl m
II
AIFClz
AIC Calc. from Tables l and 4

AI& Mass-spectrometri c
U0 Calc. f r o a Tables 1 and 4

uo, Tables 3 and 4

U03 ditto
UClz Analysis o f l i t e r a t u r e

UCI, ditto
UC1, I

UCI, I

UCI,
UOCl
T a b l e 6 (continued)

Method

Analysis o f l i t e r a t u r e

ditto
n
n
il

11

I1

Calc. from Tables 1 and 4

It

n
n

Calc. from Tables 1 and 4

Analysis o f l i t e r a t u r e
Calc. from Tables 1 and 4

Analysis o f l i t e r a t u r e
Calc. from Table 3
Tablesland4
R I a b l e s 3 and 4
" Tables l and 4
A n a l y s i s o f 1i t e r a i u r e
T a b l e 6 (continued)

Holecul I
0r Method
radical

MgCl Calc. from Tables 1 and 4

Analysis o f l i t e r a t u r e
MgBr Calc. from Tables 1 and 4

MgBr, Calc. from h e a t s o f


f o r m a t i o n and sub1 i m a t i o n
Mg 12 ditto
CaF Calc. from Tables 1 and 4

CaF, Calc. from hears o f


f o r m a t i o n and s u b l i m a t i o n
CaCl Calc. from Tables 1 and 4

CaCI, Calc, from heats o f


f o r m a t i o n and s u b l i m a t i o n
CaBr Calc. from Tables 1 and 4

CaBrp Calc. from heats o f


f o r m a t i o n and s u b l i m a t i o n
Ca l Calc. from Tables 1 and 4

Ca l, Calc. from heats o f


f o r m a t i o n and s u b l i m a t i o n
SrF Calc. from Tables 1 and 4

SrF, Calc. from heats o f


f o r m a t i o n and s u b l i m a t i o n
SrCl Calc. from Tables 1 and 4

SrCI, Calc. from heats o f


f o r m a t i o n and s u b l i m a t i o n
SrBr Calc. from Tables 1 and 4

SrBrz Calc. from heats o f


f o r m a t i o n and s u b l i m a t i o n
Srl Calc. from Tables 1 and 4

Sr lz Calc. from h e a t s o f
f o r m a t i o n and s u b l i m a t i o n
T a b l e 6 (continued)

Molecul e
Method Ref.
raSFcal
BaO Calc. from Tables 1 and 4

BaF ditto
BaF, Calc. from heats o f
formation and s u b l i m a t i o n
BaCl Calc. from Tables 1 and 4

BaCI, Calc. from heats o f


formation and s u b l i m a t i o n
BaBr Calc. from Tables 1 and 4

BaBrz Calc. from heats o f


formation and s u b l i m a t i o n
LiO Calc. from Tables 1 and 4

Li,O Calc. from heats o f


f o r n a t i o n and sub1 i m a t i o h
ditto
D

LiH Calc. from Tables 1 and 4

LiOH E a u i l i b r i a i n flames

L Calc. from Tables 1 and 4

( L a l" T a ~ l e3
LiCl "'Tables l and 4
(LiCI), "Table 3
LiBr "Tables 1 and 4
(LiBr)? "Table 3
Li I " " T a b l e s 1 and 4
(Li I), " "Table 3
NaO Vapour pressure measurements
Na,O ditto
M
Table 6 (concluded)

Molecul
0r Method
radical

NaOH Calc. from heats o f


formation and s u b l i m a t i o n
NaF Calc. f r o @ Tables 1 and 4

(NW2 Table 3
NaCl Tables 1 and 4
(NaClh bble 3
NaBr I Tables 1 and 4

(NaBr), " Table 3


Na I R Tables 1 and 4
(Na I), Table 3
KOH Calc. from heats o f
f o r n a t i o n and s u b l i m a t i o n
KF Calc. from Tables 1 and 4
(K% "Table 3
KC1 " T a b l e s 1 and 4
(KCIh Table 3
KBr "ables 1 and 4
(KWZ Table 3
KI Tables 1 and 4
(K U, Table 3
R bF " T a b l e s 1 and 4
(Rbb Table 3
RbCl Tables 1 and 4
(RbCI), Table 3
CsF R Tables 1 and 4
(CsF)z Table 3
CsCl Tables 1 and 4
(CsCI), Table 3
CsBr Tables 1 and 4
(CsBrh * Table 3
CSl " T a b l e s 1 and 4
(CS I), "Table 3
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111. IONIZATION POTENTIALS

T a b l e s 7- 12

T a b l e s 7 - 1 2 give the ionization potentials (at 0 O K ) of a t o m s , n ~ o l e c u l e s


and radicals investigated to the beginning of 1962. The method used to
d e t e r m i n e the ionization potential i s indicated in all c a s e s . T h e fre-
quent differences between the ionization potentials determined spectro-
scopically and by the electron impact method on the one hand, and
photoionization on the o t h e r , must he explained by the fact that in the
f i r s t c a s e the ionization potentials a r e adiabatic, whereas in the second
they a r e the vertical potentials. T h e photoionization method gives in
m o s t c a s e s ionization potentisls close to the adiabatic potentials.

T h e e r r o r s in the ionization potentials, whenever they a r e indicated


by the original authors, r e p r e s e n t only the experimental s p r e a d of the
values, and do not include systematic e r r o r s connected with extra-
polation.

In Table 7 the elements a r e listed in the o r d e r of increasing atomic


number. The ionization potentials given in this table have been determi-
ned spectroscopically, and a r e published in r e f e r e n c e s 1 and 143. T h e
n ~ o l e c u l e s(Tables 8-12) a r e divided into the following c l a s s e s : hydro-
c a r b o n s , halogen-substituted hydrocarbons, nitrogen-containing com-
pounds, oxygen-containing compounds and s o on. Within each c l a s s the
molecules a r e arranged in the o r d e r of increasing number of H and C
a t o m s (for example, C:, C ? H , C ? H ? and s o on); the halogens a r e
introduced in the o r d e r of increasing atomic nurnher ( F , Cl, B r , I).

T h e radicals a r e included in the s a m e tables a s the molecules. They


a r e placed before the compounds f r o m which they a r e formed.

T h e ionization potentials obtained by photoionization and spectro-


scopic methods a r e distinguished i n T a b l e s 8-12 by one and two a s t e r i s k s
respectively. T h r e e a s t e r i s k s indicate the values obtained from the
s p e c t r a of complexes with c h a r g e transfer. All the remaining values
w e r e obtained using electron impact.
Table 7

I o n i z a t i o n p o t e n t i a l s o f a t o m ( i n eV)

Atom
Ionization
potential
I Iltom Ionization
potential

As 9.81
Se 9.75
Br 11.8'1
Kr 13.906
Rb 4.176
Sr 5.692
Y 6.38
Zr 6.84
Nb 6.88
MO 7.10
Tc 7.28
Ru 7.364
Rh 7.46
Pd 8.33
Ag 7.57't
Cd 8.091
In 5.785
Sn 7 . :342
Sb 8.639
Te 9.01
I 10.454
Xe 12.127
CS 3.893
Ba 5.210
La 5.61
Ce -6.91
5.60+0.05'Note 1)
Pr 5.76
~ . 4 2 ~ 0 . 0 4 ( ~ j f j ~ )
Nd -6.31
5 . 5 1 j 0 . 0 2 (Note 2)
Pm -
Sm
Table 8

l oni z a t i o n p o t e n t i a l s o f hydrocarbons, r o l e c u l e s
and r a d i c a l s ( i n eV)
Uol pules
8
rad c a l s Ionization potential Ref.

1.5,427**
15.44 *0.03
11.13 50.22**
11.82 f 0.05
10.396:'
9.86 _+0.02
9.95 1 0 . 0 3
9.84 1 0 . 0 1
9.84**
9.95 Ifi0.03
12.99 Ifi0.01:
13.07 (Note 5 )
13.12
13.14
13.18
13.25
12.0 -&0.6
11.3 (Note 6 )
11.40 f0.03**
11.41 &0.01*
11.40
11.39
9.45 Ifi0.05
9.35 f 0 . 1 5
10.51 &0.11**
10.516~0.01*
10.60
10.52**
10.59
8.80 k 0 . 0 5
8.4*
11.65
11.65*
11.70
Table 8 (continued)

Nole ules
4
radicals
Ionization potential Ref.

9.73&0.01*
9.65+0.2**
9.84
CH, - CH, 10.06*0.02*
\ / 10.23
CH,
10.53
8.69+0.05
7.3% ( N o t e 7 )
sec. -C& 7.90&0,05
7.20, (Note 7 )
11.21
11.08*
11.22
10.2 1 0 . 1
10.74**
9.9 _+0.09
8.59*0.1 (Note 8 )
10.18+0.01*
10.34_t0.01
9.85,j-0.07
9.2440.04
9.07$0.01*
9.57
T a b l e 8 (continued)

Holecul es
I o n i z a t i o n potential Ref.
radOEals
c i s -CH,=CH-CH=CI12
trans - C H 2 = C H - C H X H ,
CH,- C(CH3)-CH,
CH,--CH=CH-CH,
CHz-CH
l l
CH,-CH,
CH,-CH,
l I
CH2-CH2
CH2=CHC2H, 9.6150.02* (Note 9 )
9.72
9.58*
9.23'
8.95
9.35
9.13*
9.29
t r a n s -CH,CH=C(CH,)H 9.13*
9 . 2 5 5 0.02**
9.27
n-C,HQ 8 . 6 4 5 0 .05
i so -C,H, 8.35+0.05
sec. -C,H, 7.9310.05
t. -C.~HB 7.42hO .07
n-CJJ,n 10.80
10.63*0.03*
10.79
10.55*
Table 8 (continued)

Hol ecul es
or Ionization potential Ref.
radicals

10.2+0.2
9.27
9.01%
10.39t0.01
10.35&0.03
9.08k0.04
9.42
9.26
8.68
9.58

7.7910.03

11.1 j 0 . 2
10.92
10.53*
8.80**
8.85
8.68*
9.66
9.50+0.02*
9.60
9.51*
9.20
9.2*
9.11
9.06
10.55
10.60
10.30*
10.29
10.23,1,-0.1
(Note 6 )
Table 8 (continued)

Molecules
'?P Ionization potential Ref.
radicalS

C,H5

C H , CHC,HQ
T a b l e 8 (continued)

Molecules
or Ionization potential Ref.
radicals

CH,-CH,
2"," CH-CH,
/
CH,-CH,
Table 8 (continued)

Molecules
radPEals Ionization potential Ref.
T a b l e 8 (continued)

Molecules
or Ionization potential
radicals
Table 8 (continued)

Holecul es
or Ionization potential Ref.
radicals
T a b l e 8 (continued)

Molecules
or Ionization potential Ref.
radicals

-6.5 (Note 10)

6.83 **
7.15 **.'

7 ***

8.2 ***

7.13 **

7.42 **

6.23
Table 8 (concluded)

Molecules
Qr Ionization potential Ref.
radicals

7.35 **

7.43 **

5.42 '*

7.4 ***

7.50 **
7.6 ***

10.15 (Note 11)


2.8 (Note 12)
4.39 ( N o t e 13)
Table 9

I o n i z a t i o n p o t e n t i a l s o f halogen-containing organic molecules


and r a d i c a l s ( i n eV)
Yolecules l oni z a t i o n
or p o t e n t i a1 Ref.
r a d . ~ c aSl

Q"
9.3*

9.37*

&F

OF
F f.'
9.55*

9.61%

F
F

9.39%
F

:q
F
9.84%
10.0

I-

CIF, 9.93*0.2
9.9710.02
10.0

C6CIF5 10.4
CBBrF6 9.6
CJFI 9.5
T a b l e 9 (continued)

Moieculss Ionization Ionization


OY potential potential Ref.
raoicals

9.68**
10.0

9. G9*

9.6
9.P

10.4
9.6'

10.G

12.84**
12.74f0.01*
12.56f 0.1
13.0+0.2
11.47**
11.48f 0.01*
11.63f 0.04
12.9f0.10
13.10~0.08
9.70+0.09
(NO& 6)
9.32
9.3
9.54f 0.1
( N o t e 6)
Tabie 9 (continued)

Molecules lonizatiun Nnlecul es lonizatiun


or potential or potential
radicals radical S

CCln
CII:,CI
0 O./tL+Cl.iI/,
O.Ui+iI lILX

CF,CI

CCIF

CClzF

CCI:,

CCI,,
B l
Cl
8.95+0.02*

CH,

0
CI-12C12
7.Q550.1
CF,CI,
CHCI:, C1
CJ!CI:,

C,H,CI

(:lzC- CH,
c i s~CIHC-=CIICI

trans-CIHC -CHC HBr


6
Cl
8.hY+0 02'

12 .l,%**
11.69
II.(i2+0.01*
CaFeClp Er2 10.58+0.08
C2F,CI 10.55+0.02*
BrCl 11.1+0.2
C2C1,
CBr 11.43*0.02
C,HnC! CBrp 10.11*0.09
CI12Br 8.34+0.11
(Note 6 )
CH,C:CCI 9.3
n-C,H7CI CHBr2 8.13
CH2=CHCCI =CH CH,Br 10.54&0.01*
.
t -C,H&I 10.53f 0.02
Table 9 (concluded)

Molecules onization
potential

i so -C,H,Br
sec. -C,f 1,Br
C,H,Br,
T a b l e 10

I o n i z a t i o n p o t e n t i a l s o f n i trogen-containing molecules
and r a d i c a l s ( i n eV)

Molecules o r r a d i c a l S loqization Potential

NW
NHn
NW3

ND,IH
ND3
CN

HCN
CH,NIH2
C,N
CH2CN
CHJN

CHc-CHL
'N/
CH2--CHJ
\ /
NI1
(CH:,),NH

C,H,NH,

C2H:,CN
C211,CN
CJ'J
CJIN
CHJCHCN
CII2CH2CN
CH2--CH,
I I
CH2-NH
C3H,NH,
T a b l e 10 ( c o n t i n u e d )

---

Hol ecul es or Radicals Ionization p o t e n t i a l

CH, -CH,,
1 N,W
CH,- CH,

n-C4HeNH,
i so- C,HoNH,
sec- C,HsNH2
(C~H6)2hH

Cd

CH,-CH,
/ \
CH, NH
\
CH,--CH<
1 SLK&H,,NH,

CaN
T a b l e 10 (continued)

Molecules or r a d i c a l s Ionization poter~tial Ref.


T a b l e 10 (continued)

Molecules or radicals Ionization p o t e n t i a l Ref.

7.7 (Note 16)


Table 10 ( c o n t i n u e d )

Molecules or r a d i c a l s Ionization potential Ref.

7.7 ( N o t e 1 6 )

7.5 ***

7.5***

NH,
7.30k0.03 *
7.4 ***

7.25*0.03 *
7.5***

7.5 ***

7.15***

7.45 ***

7.5 ***

7.4 ***
7.45 ***
7.5*"*
T a b l e 10 (continued)

bol ecul es or r a d i c a l s Ionization potential

7.15***

7.78t0.03 *

7.45 ***
7.5 ***
7.5***
7.15***
7.5 "**
7.5 ***
7.1 ***
7.5 ***
7.5 ***
7.1 ***
7.1 ***
7.1 ***
15.5850.02 **
15.60~0.01
9.85*0.1
7.8810.2
9.56*0.03 *
9.0 f 0 . l
5.12 [ N o t e 6)
5.07 (Mote 6)
8.6350.1
13.8**
13.57k0.02
(CHB)ZN-NHZ 8.12*0.1
(CH&N-NH 5.29 (Note 6)
CH,HN-NHCH, 7.75
(CH&Nz 4.95 ( N o t e 6)
CH3HN-N(CH& 7.9310.1
NC-EC-CN 11.410.2
10.01~0.02
T a b l e 10 (continued)

Nolecules o r radicals Ionization potential Ref.


T a b l e 10 ( c o n c l u d e d )

Molecules o r r a d i c a l s Ionization potential Ref.

F
CHF&N
t r a n s -N,F,
N2F4
CNCl
CH&lCN
CHCI&N
Table 11

Ionization p o t e n t i a l s o f oxygen-containing molecules


and r a d i c a l s ( i n eV)

Molecules or r a d i c a l s Ionization p o t e n t i a l Ref.

13.18 f O . l
12.61 *'
12.60 &0.01
12.59 k 0 . 0 1 *
14.009 **
14.01 +0.01*
14.1
9.88 & 0 . E
10.88 **
10.90 t 0 . 0 3 *
10.87 5 0 . 0 1
g.2 (Note 6 )
8.2 (Note 6 )
10.95 j O . 1 0
10.85 *0.02*
9.60 +0.02 **
9.4 10.3
8.08 +0.09
10.1811~0.0007**
10.i5 +0.03*(Nate 18)
10.28 k0.09
10.20 &0.03*
10.88 k O . 0 8
10.81 **
10.565 1 0 . 0 1 *
10.65 1 0 . 1
9.2 ( N o t e 6)
7.0 (Note 6 )
10.65 5 0 . 0 5
10.50 &0.06*
10.00 f0.02 *
10 15
9.85 *O. 15
Table 1 1 (continued)

Molecules o r r a d i c a l s Ionization potential

8.9,
10.14~0.10
9.98 *
8.1 ( N o t e 6 )
10.42~0.10
10.5 &O.i* (note 18)
10.20
10.27&0.10
10.15&0.05 *
9.06 **
9.00f0.10
8.8950.01*
9.9150.04
9.81k0.05
9.73f 0.01 *
9.9;
9.74*
Table 1 1 ( c o n t i n u e d )

Nolecules o r r a d i c a l s Ionization potential Ref.


T a b l e 1 1 (continued)

Molecules o r r a d i c a l s Ionization potential Ref.

HCOO
COOH
HCOOH

CHOCHO
(H&%
CHsCOOH

CD,COOH
HCOOCH,
CH,COCHO
CH,=CHCOOH
C2H6COOH
Table 1 1 ( c o n t i n u e d )

Mol~cdles or radicals Ionization p o t e n t i a l Ref.

10.27*
10.0;
9.4 5 0 . 3
9.60+0.02
9.25+0.03*
9.1;
10.22
10.1:
10.~;
10.15*
10.54*
9.97
10.n9~n.02 -
9.52

9.68-0.03"

9.86k0.02

9.34*0.03*

111.7%

8.8 1 0 . 2
9.1 j 0 . 2
13.0 ( N o t e 6 )
13.7 9 . 2
11.4"
11.82 **
Table 1 1 (concluded)

holecules o r radicals Ionization potential Ref.

ln.4 ( N o t e 6 )
11.77&0.04
11.7,**
9.91&0.02*
10.12&0.03 *
11.1 (/vote 6 )
11.7 (Note 6)
13.6 k 0 . 2
9.2510.02
9.2550.02*
9.258**
10.16j0.03 *
10.3910.05
9.65k0.03 *

9 . 4 3 5 0.02

12.72**
12.9 5 0 . 5
12.90j0.01*
12.6350.05
9.78*
9.91 (Note 6)
ilk1
CHZONO 10.7:
CH3NOa 11.34&0.09*
8.56jO.l

0""
NO,
T a b l e 12

Ionization ~ o t e n t i a l so f molecules and radicals containing boron,


s i l i c o n , sulphur and other elements ( i n eV)

Ionization No1ecul es
potential radfgal s

10.06 (Note
8 ~~(Notei
1 0 . 0 ~(Note i
9.28 (Note'
8.73 j N c t ~i
6.44 (9oieE
8.8k0.2
5.9qldote E
9.0j0.2
12.1
11.9
12.1
10.8j0.5
11.0j0.5
9.0f 0.5
15.510.5
10.4 (Note 6
7.20(NoteG)
10.91
9.25+10.1
(Note G)
7.06 (NoteE
9.7
8.96(Nctet
7.13(NoteG
9 .0
11.1k0.5
9.711.0
8.9k0.2
12.2*0.3
9.8tO. 3
9.8*0.15
7.Z6**
Table 12 ( c o n t i n u e d )

Rolecules Ionization
- Ionization
radygal s potential Ret.
potential

12.3420.02'
12.05*
13.4 5 0 . 3
8.5550.15
8.8 5 0 . 3
11.7 3 0 . 2
9 +l0
7.7 5 0 . 2
10.0 5 0 . 2
12.3
8.3 1 0 . 2
7.62(dote 6
7.76f 0.1
11.7 5 0 . 2
6.63(Note 6
7.5650. 1

8.90(Note 6
6.9150.2
14.0 k 0 . 2
12.6 5 0 . 3
7 . d ~ o t eI
7.2550.1
9 . 7 d ~ o t el
7.05f0.1
10.05(Note f
6.2 1 0 . 3
9.3dNote f
7.0650.1
11.7 +0.3
(Note 20)
8.25k0.15
7.04 **
22.3 +0.3
Table 12 (concluded)

Molecules o r r a d i c a l s Ionization p o t e n t i a l
Notes (Tables 7 - 12)

T h e ionization potential was determined by the surface-ionization


method 11481.
T h e ionization potential was determined by the surface-ionization
method [1471.
T h e r e s u l t 5.48 + 0.01 11471 i s corrected a s suggested [1471,
T h e ionization potential was determined by the surface-ionization
method [1461.
T h e value 13.07 eV i s slightly too high; i t i s given for comparison
with the ionization potentials of different deuteromethanes ,determi-
ned under the s a m e conditions.
T h e ionization potential was calculated f r o m m a s s - s p e c t r o m e t r i c
data.
T h e ionization potential of C 3H 7 was calculated f r o m the energy
necessary to produce the C,H,+ ions obtained by the photoionization
method and the dissociation energy for C 3 H ? - H. The value
obtained a s a r e s u l t i s said in reference 149 to be the adiabatic
ionisation potential of the propyl radical.
T h e ionization potential was calculatedfrom the energy necessary
to produce C4H4+ ions formed during the ionization of benzene.
The adiabatic ionization potential was reliably identified on the
production curve.
Estimated value.
The ionization potential of polymethylene was determined by
extrapolating the ionization potentials of saturated hydrocarbons.
T h e ionization potential was determined by extrapolation of the
ionization potentials of condensed aromatic compounds.
The given result i s the work function of graphite, determined
photo-electrically.
T h i s result was obtained by comparing various available data.
T h e s e values a r e probably too high since they lead to dissoci-
ation energies D (C-halogen) [1351, CF3Cl, C F 3 B r and CF31 which
a r e too low.
T h e electron energy scale was calibrated using the ionization
potential of benzene with I ( C s H 6 )= 9.5 eV.
T h e ionization potential was determined by extrapolating the
ionization potentials of halogen molecules.
The ionization potentials determined by photoionization [431 a r e
the vertical ionization potentials.
Comparison of the ionization pot.entia1 of (C2H5)3N (determined
in reference 53), with the m o r e accurate result in reference 50
shows that the method used in reference 53 gives r e s u l t s which a r e
too high.
The relative intensity of the molecular ions SnH4+ in the m a s s
spectrum of SnH4 i s very small. The ionization potential of SnHd
was determined by extrapolation of the energies necessary for the
a p p e a r a n c e of t h e f r a g m e n t i o n s .
21. The i o n i z a t i o n p o t e n t i a l w a s d e t e r m i n e d by t h e m e t h o d of s u r f a c e
ionization.

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IV. ELECTRON AND PROTON AFFINITIES

T a b l e 13
ELECTRON AFFINITIES O F ATOMS
(in eV)

T a b l e 14
ELECTRON AFFINITIES O F MOLECULES AND RADICALS
(in eV)

T h e s e tables give the electron affinities of a t o m s , moleculeg and


r a d i c a l s (at 0 O K ) measured o r calculated by various methods up to the
beginning of 1962. Where the values a r e taken f r o m published review
p a p e r s the l a t t e r a r e quoted a s the source. In all other c a s e s the
original papers a r e indicated. As a r u l e , the e r r o r s r e p r e s e n t the
experimental s p r e a d , and a r e not absolute e r r o r s . T h e atoms a r e
a r r a n g e d in increasing atomic number.

T h e hydrocarbon m o l e ~ u l e sand radicals a r e a r r a n g e d in increasing


number of C and H atoms. They a r e followed by halogen-containing
hydrocarbons, oxygen-containing compounds, nitrogen-containing com-
pounds and s o on.
T a b l e 13

Atom Electron
affinity

Quantum-mechanical c a l c u l a t i o n
E x t r a o o l a t i o n from i s o e l e c t r o n i c series

ditto
I

Comparison o f various data


Thernochemical c a l c u l a t i o n based on
E A ( O ) = 1.465 eV
E x t r a p o l a t i o n from i s o e l e c t r o n i c s e r i e s

ditto
Photoi oni z a t i on
E x t r a p o l a t i o n from isoelectronic s e r i e s

Surface i o n i z a t i o n (Note 1 )
Surface . i o n i z a t i o n
E x t r a p o l a t i o n fro^ i s o e l e c t r o n i c s e r i e s

ditto
R

Quantum-mechanical c a l c u l a t i o n
E x t r a p o l a t i o n from i s o e l e c t r o n i c s e r i e s

ditto
n
n

Photoi oni z a t i on
Surface i o n i z a t i o n (Note 1 )
E x t r a p o l a t i o n from i s o e l e c t r o n i c s e r i e s

Surface i o n i z a t i o n (Note 1)
Surface i o n i z a t i o n
E x t r a p o l a t i o n from i s o e l e c t r o n i c s e r i e s
Table 13 (concluded)

Atom
Electron
affinity I Method Ref.

Quantun-mechanical c a l c u l a t i o n
Calc. from e l e c t r o n e g a t i v i t y
Calc. from l a t t i c e energy
E l e c t r o n impact
Comparison o f v a r i o u s data
Surface i o n i z a t i o n (Note 2)
Surface i o n i z a t i o n
Calc, from e l e c t r o n e g a t i v i t y
E l e c t r o n impact
Calc. from l a t t i c e energy
Surface i o n i z a t i o n (Note l )
Calc. from e l e c t r o n e g a t i v i t y
Formati nn o f n e g a t i v e i o n s
Calc. from e l e c t r o n e g a t i v i t y
E l e c t r o n impact
T a b l e 14

Molecules o r r a d i c a l S
ilectron
affinity
-0.72
Method

Quantum-mechani c a l
-
[l1
Ref.

'Note 31 calculation
-1 .fi3 i l e c t r o n impact [l1
--l).95 ditto [I1
-1 .OS lomparison o f v a r i o u s L (:l
data
1.8 Cuantum-mechanical 171
calculation
:3 , 1 E l e c t r o n impact Ill
-1.81 Quantum-mechanical [I l
calculation
l.
't C a l c u l a t e d from Pi
e l ectronegati v i t y
1.8 E l e c t r o n impact [l1
2.1 Kinetics o f electrode 111
processes
1 .o C a l c u l a t e d from 181
electronegativity
-1 .o ditto [XI

t r a m -H,C=CH -CH-=cH, --0.3'1 Quantum-mechanical [jl


calculation
-L). 53 Kinetics o f electrode ['l
processes
1.8 ditto [l1
-0.29 Quzntum-mechanical [l1
calculation

0.65 Kinetics o f electrode 111


Drocesses

1.6 ditto [!I

0.41 ditto 1'1


T a b l e 14 ( c o n t i n u e d )

Electron
-
b!olecules o r r a d i c a l s affinity Method Ref.

rantum-mechani c a l
calculation

inetics o f electrode
processes

ltto

easurements o f
p h o t o e l e c t r i c work
fu ctioo
c 1% le$!ron ~ m p c t
CCI,
stimated
It

leasurements o f e l e c t r o
d e n s i t y i n flames

h p a r i s o n o f various
data
stimated
:omparison o f v a r i o u s
data
I e c t r o n impact
ialc. from heat o f
hydration
T a b l e 14 ( c o n t i n u e d )

Electron
Molecules o r r a d i c a l s affinity Method

Calc. from l a t t i c e
energy

Calc. from heat o f


hydration
oitto
n

Calc. from l a t t i c e energy

ditto
Comparison o f v a r i o u s dati

Surface i o n i z a t i o n
(Note 1)
E l e c t r o n impact
Pi 0 Formation o f negative
ions
NO? Calc. from l a t t i c e energy
Formation o f n e g a t i v e
ions
Calc. from l a t t i c e energy

E l e c t r o n impact
Calc. from heat o f
hydration

Estimated from i o n i z a t i o n
and e x c i t a t i o n
potentials

Calc. from l a t t i c e energy


E l e c t r o n impact
Formation o f n e g a t i v e
ions
E q u i l i b r i a i n flames
Formati on o f negat ~ v e
ions
SeH Calc. from l a t t i c e energy
T a b l e 14 ( c o n c l u d e d )

Molecules o r r a d i c a l s Method

SeO, E q u i l i b r i a i n flames
Sic Estimated from p h o t o e l e c t r i c
data
SiClz E l e c t r o n impact
BF3 Formation o f n e g a t i v e i o n s
Estimated from thermochemical
data
MOO, E q u i l i b r i a i n flames
AgCl Calc. from l a t t i c e energy

AgBr ditto
R
Ag I

Notes (Tables 13- 14)

T h e d i f f e r e n c e b e t w e e n t h e e l e c t r o n a f f i n i t i e s of F a n d B r a t o m s
w a s d e t e r m i n e d b y t h e m e t h o d of s u r f a c e i o n i z a t i o n . T h e e l e c t r o n
a f f i n i t i e s i n F , Cl, I , S a n d CN w e r e o b t a i n e d , a s s u m i n g t h a t
E A ( B r ) = 3.56 e V .
T h e r e s u l t L A ( B r ) = 3.56 e V .was o b t a i n e d o n t h e a s s u m p t i o n t h a t
EA (S) = 2.33 e V .
T h e m o l e c u l e H2 h a s a p o s i t i v e " v e r t i c a i " e l e c t r o n a f f i n i t y . T h i s
i s e x p l a i n e d b y t h e f a c t t h a t t h e p o t e n t i a l c u r v e f o r H - H2 is
displaced towards large internuclear distances, and the minimum
of t h i s c u r v e l i e s i n t h i s r e g i o n b e l o w t h e w t e n t i a l c u r v e f o r H..
T h e H2- i o n s w e r e o b t a i n e d m a s s - s p e c t r o m e t r i c a i l y 12!.

REFERENCES
1. BUCHEL'NIKOVA, N.S. (1958). U s p . fiz. nauk, 65, 351.
2. KHVOSTENKO, V.I., and DUKEL'SKN, V.M. (1958). Zh. eksper. teoret.
fiz., 34,1026.
3. LYONS, L.E., (1950). Nature. 166, 193.
4. PAGE, F.M., and SUGDEN, T.M. (1957). Trans. Farad. Soc., 53, 1092.
5. BRIEGLEB, G., and CZEKALLA, J. (1955). 2. Elektrochem., 59, 184.
6. PRITCHARD, H.O., (i953). Chem. R e v . , 52, 529.
7. SKLAR, A.L. (1939). 1. Chem. P h r s . , 7 , 984.
8. MATSEN, F.A., ROBERTSON, W.W., and SHUOKE, R.I. (1947). Chem. R e v . ,
41, 273.
9. MULLIKEN, R.S. (1948). P h y s . R e v . , 74, 736.
10. BAKULINA' I.N., and IONOV, N.I. (1959). Zh. fiz. khim. 33, 2063.
1 1 . HERRON, J.T., and DIBELER, V.H. (1960). 1. Am. Chem. Soc., 8 2 , 1555.
12. POTAPOV' V.K., and VASIL'YEV. V.G. (1961). Materials from a confer-
ence on problems of the structure of matter, chemical kinetics and reaction
potentials, Riga (printing).
13. PHILLIP. H.R. (1958). P h y s . Rev., 111. 4407.
14. SKEWER, H A . 1952. Proc. Conf. Univ. Coll. North Staffordshire, Engl.,
28, Publ. 1953.
15. KLAUS, D. (1955). Z. anorg. allg. Chem., 281, 212.
16. BAKULINA, I.N., and IONOV, N.I. (1957). Dokl. Akad. Nauk S S S R , 116, 41.
17. BAILEY, T.L. (1958). 1. Chem. Phys., 28, 797.
18. EDLEN, B. (1960). 1. Chem. P h y s . , 33, 98.
19. BRANSCOMB, L.M., BURCH, D.S., SMITH, S.J., and GELTMAN. S. (1958).
P h y s . R e v . , 111, 504.
20. FLENGAS, S.N., and RIDEAL, E . (1956). Proc. Roy. Soc., A, 233,443.
21. KNEWSTUBB, P.F., and SUGDEN, T.M. (1960). Proc. Roy. Soc. A, 255,520.
22. CURRAN, R.K. (1961). 1. Chem. Phys., 35, 1849.
23. CURRAN, R.K. (1961). 1. Chem. Phys., 34, 2007.
24. GRAY, P., and WADDINGTON, T.C. (1956). Proc. Roy. Soc., A235, 481.
25. CURRAN, R.K. (1962). P h y s . R e v . , 125, 910.
26. KRAUS. K. (1961). 2 . Naturforsch, 16a. 1378.
27. KRAUS, K., MULLER-DZYSING, W., and NEUERT, H. (1961). Z. Natur-
forsch., 16a, 1385.
T a b l e 15
PROTON AFFINITIES O F SOME ATOMS,
RADICALSAND MOLECULES

'The tahle gives the proton affinities of a number of atoms, molecules


and r a d i c a l s , calculated o r measured by the ion-impact method. Some
of the values w e r e calculated by the authors from thermochemical data.
and r e f e r e n c e s to these data a r e given in each case.

T h e molecules a r e a r r a n g e d a s follows: hydrocarbonsaregiven in the


o r d e r of increasing numbers of C and H atoms. They a r e followed by
halogen-containing, oxygen-containing, nitrogen-containing and other
compounds.
\

T a b l e 15

Atoa finity
rad'ca 'or
moI ecul e Method
k c a l /m01 e

70+9 I o n impact
70 L c a t t e r i n g o f protons i n
hydrogen
140 ~hermochemical calc. (Note 1)

118 Thermochemical calc. (Note 2)


120 Thermochemical calc. (Note 3)
117.4 Thermochemical calc. (Note 4)
122f 7 E l e c t r o n impact
157f 8 P n
156 Thermochemical calc. (Note 5)
153 Thermochemical calc. (Note 6)
172 Ttlermoche~ical calc. (Note 7)
>l45 I o n impact
>l47
85.6 Thermochemical calc. ( b o t e 8)
124.1 Thennochemical calc. (Note 9)
3120 I o n impact
133.5 Thennochemical calc. (Note 10)
146.4 Thermochemical calc. (Note 11)
T a b l e 15 (concluded)

Thenochemical calc. (Note 12)


Thenochemical calc. (Note 13)
l on iapact
Calculation
R

Ion impact
Calculation
Ion iapact
Calculation
8

Scattering o f protons i n NH3

Calculation
I

Ion impact
Calculation

Ion impact
I I

I I

I I

e a
I I

I I
Notes

1. A N ; ( C H ) = 142.1, / ( C H ) = 11.13 eV, l ( H ) = 13.59eV. Pc=


AH; ( C H )C 1 (CH)- I ( H )-- AH; (C)- AII; ( H ) .
=
2. AH; (C&) = 66: AH; ( C H ) = 142.1, 1 (CH,) 1 1.82 eV; I (H) -=-
= 13.59e'i! P,, = AH; (CH,)-AI-I~(CH)+I (cl-I,)-I (CH)-AI!; (H).

= 13.59eV P,,,, - A H ~(CH,) - AH: (Ci4,j


-
3. AH;(CI I,) -= 33, AI( (CII,) !6. I (CH,) =-9.85eV, i (H)
+
-
I (CIH,) - I ( C H ) -
A H ; (H).
-
4, dfI;(CH,) - 17.9, A:I; (CH,)
= 13.53e\< PcI,8= A H ; (C&) - ~ 1 1(CH,) ;
-
33, 1 (CH,) -z 18.0eV; /(F-!) =
+ I (CH3)-- f (bi) .- AH;(H).
5. See page 2 4 .
G. AH; (n-C&) == 18, AI{; (C3&) .= 4.88, I ( n X 3 H 7 )=
= 8.69 eV, !(l 1) === 13.59 eV. Pn.c,Hs= A ~ J(C&) ; +
---Aff; ( c ~ H ~ )
-+1 (n-C&) - I ( H ) - AH; ( H ) .
7. A H ; ( i s o -C,N,) = 17, A H ~ ( C , H , := ~ ) 4.88, l ( i s 3 -C3H7) =
-7.90 eV, I (H)-=13.59 eV. P - L W ; ( i s n - c,H,)--AH~(c,H,)+
~,,~,~1,8

+ I (c,H,) - I (H) - A H ; (H).


8. A F I ~ ( H F )--64.2,
-= 13.59eV
- ~ 1 1 i ( F f-. 18.3. f (W) = 15.77eV, ((1-1)
-= A H (~I F ) ;- !(HF')- !( H ) - AH; ( F ) -- AH; (H).
-
-
9. H ( l 1 = - 22.06. ~ i I (fC ! ) 29.0, ! ( M C ] ) 12.74eV,
,-
I (fl) =- 13.59 eV. Pc, ==AH; (1-ICl) I (HCI) - /(H)- AH;(CI) -
-2

- Z H ; (I-:).
10. CIH~(I~!H~) 8.66, b f f i ( ~ r-) 26.7, f (HBr)
= -- 11.62 = eV,
I (H) 3.5.3 e V .
-= ! pBr AHi (HBr) 4. (IHBr)
~- AH; (H)
i - !(13)- -
-A f q
=:
l
(Eh).
I . A:Jj (H.1)-= 6.2, - 25.5. I (IJJ)A M ;(10.38eV
13.53 eV I),, A H ~(HJ) + I(11.1) i
=
(.I!
- (11) --
=
11).
I (H)
l ( 0= 3.3, H ) - 59.16, i (OH) -: 13.18eV, [ ( H ) =
.+
:-= 13.59eK Pc) -= AIJ; (0fI) i (OH) - l ( H ) - AH; ( H ) .
! 3 . AH; (H,()) = - 57.8, AN; ( O H ) =: 9.3, I (H20)= 12.60 eV,
--
i (H) !3.59 eV. Poll ~ 1 ~(1~120)
-- M ; ( H ) .
7
:1 ; -- A H (011)
~ +
f ( H Q - I ( H )-
REFERENCES
1. TAL'ROZE, V.L., and FRANKEVICH, E . L . (1958). 1. Am. Chern. Soc.,
80, 2344.
2. BRIEGLEB, G. (1949). Z. f. Elehtrochem., 53, 350.
3. KONDRAT'YEV, V.N., and SOKOLOV, N.D. (1955). Zh. fir. khirn., 29,
1265.
4. SIMONS, J.H.,FONTANA, C.M., MUSCHLITZ, E.E., and JACKSON. S.R.
Jr., (1943). 1. Chern. P h y s . , 11, 312.
5. RUSSELL, A.S., FONTANA, C.M., and-SIMONS. J.H. (1941). 1. Chem. P h y s .
9. 381.
6. STEVENSON, D.P.,and SHISSLER. D.O. (1955). 1. Chern. Phys., 23, 1353
7 . E V E T T , A.A. (1956). 1. Chern. Phys., 24, 150.
8. STERMAN, J . (1932). Chern. Rev., 11, 93.
9. SHISSLER, D.O., and STEVENSON, D.P. (1956). 1. Chem. Phys., 24, 926.
10. F I E L D , F.H., and FRANKLIN, F .W. (1958). I. Am. Chern. Soc., 80, 1583.
11. FRANKLIN. J.L., LAMPE. F.W., and LUMPKIN, H.E. (1959). 1. Am. Chem.
Soc., 81, 3152.
12. KAUL, W., LAUTERBACH, U., and TAUBERT, R. (1961). Z. Naturforsch. a,
16, N 6, 624.

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