Documente Academic
Documente Profesional
Documente Cultură
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
W.C. P r i c e
King's College London
FOREWORD
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.
REFERENCES
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
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
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
Introduction
...
Contents Xlll
Determination of bond e n e r g i e s
Experimental methods
Theoretical and semi-empirical methods
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
xiv
DETERMINATION O F BOND ENERGIES
Experimental methods
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.
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 .
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.
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.
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 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.
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.
1s i O . O Z 0.1 eV. From this result and from the energy of the p r o c e s s
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 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.
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.
Snle note that a forrnuia similar to equation (19) has been obtained by
Vorvodskii for C - C bond energies in paraffinic hydrocarbons.
Electron affinity
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].
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.
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.
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.
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.
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+,
is not, we have
REFERENCES
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 .
, >
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 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 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
~ ~ 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
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
-
Mole-
cul e
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)
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
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
..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
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)
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
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)
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)
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
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
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
LiH Spectroscopic ( p r e d i s s o c i 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
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)
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
Mole.
cul e D," Method
- 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
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 )
-
-
Role- Met hod
cu e
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)
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)
'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
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).
REFEREUCES
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
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
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
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)
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
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
Bond
E l e c t r o n impact
n I
n n
R n
Q n
1 R
n n
R I
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.
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
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
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).
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
ditto
Table 3 (continued)
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)
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)
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
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
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
E l e c t r a n imoact
I1 18
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
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
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 )
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
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
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
+
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
PC1,F == PC1,+ F n
+
PClzF = PClF C1
+
PCIFz .= PClF F
+
PCIF, = PF2 Cl
POClF = POCl + F
T a b l e 3 (continued)
?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.
FClCO :FCO ) 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, -= 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)
+
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
-
T a b l e 3 (continued)
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
Estimated
.ale. from f a b l e s 6 and 4
j a t a o f Tablc 1
Estimated
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)
HgClBr = HgBr +
+ Cl
HgCl I = HgCI +1
HgCI I = H g l + Cl
HgBrI = HgBr +I
T a b l e 3 (continued)
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
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
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
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
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
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
ditto [l091
a [l091
Calc. from Tables 6 and 4
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)
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
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
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
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
ditto
Data o f Table 1
Calc. from Table 6
ditto
(BeO), = (BeO),
+ Be0
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)
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
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
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
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
ditto
?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)
(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
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
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
Vapour d e n s i t y measurements
T a b l e 3 (concluded)
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
REFERENCES
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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)
Atom Method
Atow Method
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)
-
Table 4 (continued)
Atom n e t hod
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)
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
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
REFERENCES
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
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
(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
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
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
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
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
Molecule
or Met hod Ref.
radical
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
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
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
Ge,C ditto
I
Ge,C
GeSi I
I
Ge,Si
Ge,Si n
GeSiC L
Ge,SiC I
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
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
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
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
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
-
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
TICI,
TiCI,
Molecule
or Method
radical
7 - -
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
HB0 Estimated
HBOz Analysis o f l i t e r a t u r e
HW3 n n
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
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
It
n
n
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
Analysis o f l i t e r a t u r e
MgBr 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
LiOH E a u i l i b r i a i n flames
( 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
(NW2 Table 3
NaCl Tables 1 and 4
(NaClh bble 3
NaBr I Tables 1 and 4
T a b l e s 7- 12
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
6.83 **
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 ***
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)
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)
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
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)
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 )
---
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)
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)
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)
F
CHF&N
t r a n s -N,F,
N2F4
CNCl
CH&lCN
CHCI&N
Table 11
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)
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 )
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 )
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)
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 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)
REFERENCES
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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)
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
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
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
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
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
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.
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T a b l e 15
PROTON AFFINITIES O F SOME ATOMS,
RADICALSAND MOLECULES
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)
Ion impact
Calculation
Ion iapact
Calculation
8
Calculation
I
Ion impact
Calculation
Ion impact
I I
I I
I I
e a
I I
I I
Notes
- 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
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