ENERGETICS AND MECHANISM OF HYDRONIUM ION FORMATION

BY ELECTRON IMPACT

D. VAN RAALTEAND A. G. HARRIS ON^

Depavt~nentof Chemistry, University of Toronto, Toronto, O~ztario
Received August 12, 1963

ABSTRACT
'The reactions leading to for~natioilof the hydroniurrl ion in the Inass spectra of a number
of alcohols and formate esters have been elucidated through a study of appearance potentials
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and nletastable transitions and by the use of deuterium labelling. The results lead to
JHr(H?O+) = 157+3 kcal/mole corresponding to a proton affinity of the gaseous water
rr~oleculeof 151z t 3 Ircal/mole.

ISTRODUCTION
The generally accepted value for the proton affinity of the gaseous water inolecule is
182 kcaljinole (1) based on calculations from crystal lattice energies by Sherman (2).
More recently Sokolov et al. (3) have recalculated P.A. ( H 2 0 ) from lattice energies and,
taking into account the effect of hydrogen bonding, have obtained P.A. (H,O) = 1 6 8 h 7
kcal/mole. This latter value is in essential agreement with an independent estimate
obtained by Tal'roze and Frankevich (4) from a study of gas-phase ion-molecule reactions
involving H 3 0 + as the product ion. The reaction
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was observed and therefore must be exothermic or therinoneutral. Therinocllemical

calculations led (4) to a maximuin value AHf(H30f) 5 141 kcalfmole. Using a more
recent varue (5) for AH,(HS) this upper limit is raised to 145 lrcal/mole, leading to a
ininimunl value P.A. (HZO) >
163 kcalfmole. On the other hand, the reaction

was not observed and was therefore assumed to be endothermic (4). On this basis
a minimum value AHf(H30f) 5 136 kcal/mole (P.X. ( H 2 0 ) 5 172 lrcal/mole) was
obtained. This limit must be accepted with reservation, since other factors may be
responsible for the non-occurrence of reaction [ 2 ] .
Although the hydronium ion has been observed as a rearrangement ion in the mass
spectra of alcohols (6, 7, S) and esters (9) no systematic investigation of the energetics
and mechanism of formation has been undertaken. An early study (10) of the appearance
potential of H 3 0 + from ethyl alcohol has been used (11) to derive AHf(HjOf) = 172 or
196 kcal/inole, depending on the mechanism of formation chosen. More recently,
Bernecker and Long (12) have measured the appearance potential of H30+ from ethyl
formate and have reported AHf(H30t) = 207 kcalfmole, corresponding to P.A. ( H 2 0 ) =
100 kcal/mole.
In view of the conflict in the reported values for AHf(H30+) and the paucity of data
concerning the inechanisn~of formation of this rearrangement ion in the mass spectra of
alcohols and esters, we have undertaken a detailed study of the energetics and mechanism
of formation of H30+by electron impact.
' A y ~ e dP. Sloan Research Fellow.
C a n a d ~ a nJournal of Chem~>try.
Volutne 41 (1963)
 \'AS R1ALTE A S D HARRISON HYDRONIUM ION FORhIATIOS 3119

EXPERI bIEXTXL
A11 results were obtained using a n Associated Electrical Industries MS-2 Illass spectrometer. The mass
spectra were obtained with 50 volts electron energy, 20 pamp ionizing current and 3 volts repeller (-7
volts/cm field strength). The appearance potei~tialswere obtained as previously described 113), using xeilon
or krypton as the calibrating gas.
T h e mass-to-charge ratios of the "low mass" metastables of interest in the present \vork were measured
by comparison with the C+ ion using electrostatic scanning and making accurate colnparison with the voltage
necessary to bring the txvo ion beams into focus. The necessary circuitry and poteiltiometer are built into
the inass spectrometer.
T h e non-deuterated co~~lpoullds were commercial sa~llpleswith the exception of the isopropyl formate
which was prepared by standard procedures. All samples were carefully dried and distilled before use to
remove traces of water. In all cases the peak attributable to H 2 0 impurity was scarcely above the ~lormal
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small instrument background.

The ethyl-1,l-ds alcohol, 2-propyl-1,1,1,3,3,3-ds alcohol, ethyl formate-d, aild isopropyl formate-d were
obtained from hlerck, Sharp, and Dohrne. The detailed mass spectra of the two esters have been presented
previously (14). The deuterated ethyl alcohol initially contained impurities thought to be acetone and diethyl
ether. These were removed by careful distillation. T h e isopropyl-de alcohol also showed diethyl ether impuri-
ties which were removed by gas chromatography. Low energy analysis of both alcohols indicated approxi-
mately 99yGisotopic purity.

RESULTS AND DISCVSSION

The appearance potential of H30+ was measured from ethanol, n-propanol, s-propanol,
s-butanol, s-pentanol, 3-methyl-2-butanol, diethyl ether, ethyl formate, and isopropyl
formate. The measured appearance potentials, postulated neutral products, and the
resultant AH,(H30+) for each compound are given in Table I. The evidence leading to the
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assigninent of the neutral fragments, and thus the details of the ionization inecl13nisn1,
will be discussed below.

TABLE I
Appearance potentials and heats of formation of H 3 0 +

Postulated
neutral
Compound p~0dLictS

s-Propanol
s-Butanol
CH3
C2H0
++
C2H2
C2H3
s-Pentanol n-C3H,
i-CaH7
++
CzH2
C2H2
3-Me-2-butanol
Ethanol CaH,
n-Propanol
Diethyl ether
C3H3
C2H5
++
H2
C?Hz
Ethyl formate HCO +
C2H2
Isopropyl formate CH, + CO +
C2H2

The heats of formation of neutral species necessary for the cnlculations in Table I were
talcen from the recent compilations of Bernecker and Long (12) and Green (15) with a few
exceptions. T h e heats of formation of the propyl radiclls are in some doubt and the values
used were based on D(n-Pr-H) = 99 ltcal/mole (16) and D(i-Pr-H) = 96.5 kcaljmole,
an average of two values 94 kcal/mole (17) and 99 lcca1,'inole (18). AHf(C3H3)= 75
kcal/mole (19) was used in preference to the value quoted by reference (12). The heats of
forination of s-pentanol, 3-methyl-2-butanol, and isopropyl formate have not been re-
ported and were estimated by comparison with related coinpounds to be: -73.9, -76.2,
and -9s kcal/mole respectively. Calculations using group contributions (20) gave very
similar values for the two alcohols; the error for these cases is likely to be small, however
the value for isopropyl formate may be in error by & 3 kcal/mole.
 3120 CASADIAX JOURNAL O F CHEMISTRY. VOL. 41, 1963

Formatiolz of H30+from RCH(CH3)OH

The most extensive and conclusive evidence for the dissociation mechanism was
obtained for secondary alcohols RCH(CH3)OH where R = CH3, CzH5, n-C3H7, and
S-C3H7.The inass spectra of these alcohols all show (8) the largest peak a t mass 45*
(CH3CHOH+)corresponding to loss of the group R. For s-propanol (21,22) and s-butanol
(23) deuterium labelling has shown that the group R is lost without isotopic mixing. Each
of the four alcohols showed a pronounced metastable a t Inass 8.02 corresponding to the
transition
CH3CHOH++ H,O+ + CzH, m* = 1g2/45 = 8.02. [31
The intensity of the metastable was directly proportional to the sample pressure indicating
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that reaction [3] was not a collision-induced dissociation. These facts suggest a common
mechanism, reaction [4], for the four alcohols.

Calculations assuming this mechanism lead to mutually consistent values for AHf(H30+)
as summarized in the first four rows of Table I.
For s-propanol it has been suggested (24) that formation of H3Of would occur by
reaction [5] with C3H5(allyl) as the neutral fragment
(CH3)2CHOH --t C3Hs + H30+. [;I
The experimental appearance potential, 310 kcal/mole, leads to AH,(H30f) = 213
kcal/mole assuming reaction [5].This value is in disagreement with other values obtained
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in this work. Furthermore, reaction [5] does not lead to the observed metastable, nor does
it explain the observed deuterium labelling to be discussed below.
T o provide further information on the detailed mechanism of reaction [4] the mass
spectrum of 2-propyl-1,1,1,3,3,3-ds alcohol was examined. The spectrum obtained was in
good agreement with that previously reported (22). The intermediate mass 45 has moved
to mass 48 indicating the formula CD3CHOH+. The observed relative intensities for
H2DO+,HD20+,and D30+ are given in Table I1 and compared with relative intensities
calculated on the following four models:
(i) complete scrambling in parent ion,
(ii) retention of hydroxyl hydrogen and scrambling of remainder in parent ion,
(iii) complete scrambling in CDaCHOH+ intermediate,
(iv) retention of hydroxyl hydrogen and scrambling of remainder in CD3CHOH+
intermediate.
The results of Table I1 show that the only model which comes close to predicting the
TABLE I1
Relative intensities of labelled hydronium ions in (CD3)2CHOH

Relative intensity of:

Observed 0.492 0.472 0.036

Calculated
Model (i) 0.100 0 540 0.360
Model (ii) 0.286 0.714 0,000
Model (iii) 0.300 0.600 0.100
Model (iv) 0.500 0.500 0.000

*Since only singly charged ions will be discussed, the mass-to-charge ratio will be referred to as the mass.
 VAN RAALTE A N D HARRISON: HYDROSIUM ION FORMATION 3121

observed relative intensities is model (iv) involving retention of the hydroxyl hydrogen
and scrainbling of the remainder in the CDaCHOH+ intermediate. There does not appear
to be any reasonable model involving direct decomposition of the parent ion (reaction [ 5 ] )
whicll can explain the observed label distribution. A si~npleinterpretation of the label
distribution is the formation of a symmetrical protonated ethylene oxide intermediate
having the structures I and I1 for the unlabelled and labelled alcohols respectively.
H
' c c /H D\ C--C /D
H( \O/ \H D/\ /\H
o+
I 1
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Transfer of one hydrogen (or deuterium) from each carbon to the oxygen would explain
the product formation and the deuterium labelling. The small ion current for D30+
suggests a sinall amount of exchange of the hydroxyl hydrogen with the other hydrogens
in the intermediate ion. The appearance potentials of the HzDO+ and HDzO+ ions were
identical with the appearance potential of HaO+ from the unlabelled alcohol within
experimental error. The abundance of the D30+ ion was too low to permit appearance
potential measurements.
The deuterium labelling in s-butanol (23) provides results in good agreement with those
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obtained for s-propanol. Table I11 shows the abundance of the relevant ions, as percentage
TABLE I11
Partial mass spectra of secondary butanols*

Mass Ion s-Butanol-do s-Butanol-ds s-Butanol-ds

*From reference 23. Intensities as percentage of total ionization.

of total ionization, for 2-butyl alcohol, 2-butyl-1,1,1,3,3-dbalcohol, and 2-butyl-l,l,l,2,3,3-d6
alcohol. I t is obvious that the mass 45 intermediate is formed by loss of the ethyl group
without isotopic mixing, appearing as mass 48 in the d~ alcohol and mass 49 in the d6
alcohol. The relative intensities of the various labelled hydronium ions in the ds alcohol
TABLE IV
Comparison of observed and calculated intensities in s-butanol-d5

Relative intensity of:

Observed 0.500 0.460 0.040

Calculated
~ ~~ ..
- -.. -

Model (i)
Model (ii)
Model (iii)
Model (iv) 0.500 0.500 0.000
 3122 CANADIAN JOURXAL O F CHEMISTRY. VOL. 41, 1963

are compared in Table IV with relative intensities calculated on the following four models:
(i) complete scrambling in parent ion,
(ii) retention of hydroxyl hydrogen and scrambling of remainder in parent ion,
(iii) complete scrambling in CD3CHOHf intermediate,
(iv) retention of hydroxyl hydrogen and scrambling of remainder in CDjCHOHf
intermediate.
T h e experimental results are practically identical with the label distribution found for
the isopropanol-de and clearly are only in accord with model (iv). The formation of D 3 0 f
in low abundance again probably represents a stnall amount of hydroxyl hydrogen ex-
change in the interinediate I I.
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In s-butanol-d6 the intermediate CD$CDOH+ should lead only to I-ED20f by the

inechanism proposed. The partial spectrum in Table I11 shows, as expected, the largest
ion current a t mass 21, however, the ion current a t inass 22 (D30+) indicates again some
scrambling in the intermediate.
Formation of H30ffrom E t h y l Alcohol
Two reactions, [6] and [7], must be considered as possibilities for the formation of
1-130+from ethyl alcohol.
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T h e mass spectrum of ethyl alcohol shows an appreciable ion current for CH3CHOHf
and, in addition, a inetastable ion a t mass 5.02 (reaction [3]) corresponding to the second
step in the overall reaction [7].However, the measured appearance potential, 277 lical,/
mole, leads to AHf(H30+) = 115 kcal/mole assuming reaction [7] and 156 kcal/mole
assuming_reaction [B]. The agreement of this latter value with the values obtained froin
the secondary alcohols indicates quite conclusively that the lowest energy process occur-
ring is reaction [6]. Reaction [7], which is of higher energy requirement, is shown to occur
by the inetastable transition a t mass 5.02. Attempts were made to detect breaks in the
ionization efficiency curve by the method of JIorrison (25). Although a rather large
initial curvature was observed, no definite breaks could be identified.
In an attempt to obtain information on the relative importance of reactions [6] and [7]
the mass spectrunl of CH3CDZOH was examined. As has been found previously (26, 27),
the mass 45 moves exclusively to mass 46, indicating loss of the a-deuterium. The observed
spectrum in the region of the hydronium ion (Table V) is in reasonable agreement with

TA4BLEV
Partial mass spectra of CHBCHzOH and CH,CD,OH*

CH3CDzOH CHaCD,OH
Mass Ion CH3CH20H (this work) (ref. (26))

*Intensities as percentage of total ionization.

that reported by hlomigny (26). The appearance potentials for H30f and H2DOf mere
273f3 and 274*3 kcal/mole respectively, in good agreement with the value of 277
 VAX RAALTE A N D HARRISON: HI'DRONIUM ION FORMATION 3123
lical/mole obtained for the undeuterated alcohol. The relative intensities for H 3 0 + and
H2DO+ are close to that expected for decoinposition of the CH3CDOHf intermediate;
the sinall amount of DzHOf must originate by reaction [GI. No significant variation of
the ratio H30+/H2DO+ was observed as the electron energy was decreased to near the
threshold. This probably means that the label distributions obtained from reactions [GI
and [7] do not differ significantly. On the basis of the present evidence we cannot assess
the relative inlportance of the two reactions.
Formation of H30+from n - P r o p y l Alcohol
T h e mass spectruin of n-propyl alcohol shows only a very small ion current for Inass 45
and no metastable corresponding to reaction [3]. The following three reactions must be
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considered.

The measured appearance potential, A%(H30f)= 292+3 kcal/mole leads to AHf(H30+)=

199 lical/mole assuming [S], 144 kcal 'mole assuming [9] and 155 kcal/mole assuming [lo].
Although reaction [lo] appears rather unlikely, it gives the best fit for AHf(H30+)and is,
accordingly, the reaction chosen.
Formation of H30+from Dietlzyl Etlzer
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The H3Of ion is of moderate abundance (0.8% of total ionization) in the mass spectrum
of diethyl ether. A sizeable ion current a t mass 43 and a inetastable a t mass 8.02 (reaction
131) suggested decomposition through the inass 45 intermediate. A(H30+) = 304 kcal/
mole leads to AHf(H30+)= 164 kcal/mole assuming reaction [ l l ] .

If this reaction is the only one contributing to H30+ formation it must be responsible for
the inetastable transition, thus suggesting that the-mass 43 is C2H60+formed with CsHS
as the neutral fragment. I t is probable, however, that the majority of the mass 43 ions are
formed by the rearrangement reaction indicated below (28).

The appearance potential of mass 45 was found to be 2 7 2 f 3 kcal/mole in the present

work, which leads t o an ionic heat of formation of 1 4 7 f 3 kcal/mole, assuming reaction
[12], in excellent agreement with best estimates of AHf(CH3CHOH+) = 14.5 kcal/mole
derived from simple alcohols. This indicates that reaction [12] is the lowest energy process
producing mass 45 and, since decomposition of CH3CHOHf is known to produce H30+
(see above), we conclude that reaction [13], which is of higher energy requirement than
reaction [12], also contributes to H30+ formation.

Formation of H30+from E t h y l Formate

The H 3 0 + ion is approximately 1.2% of the total ionization in ethyl formate. In the
present work A(1-130f) was found to be 302&3 kcal/mole, considerably lower than the
value of 334 kcal/mole reported by Bernecker and Long (12). Reactions [14] to [I61 must
be considered in a discussion of these results.
 3124 CANADIAX JOURNAL O F CHEMISTRY. VOL. 41, 1963

HCOOCzH -+ C2H3 + CO +
-+ CzHz + H C O + H30'
-+ C y H 2 + H + C O f H3Of

Table VI records the values calculated for AHf(H30+) for each of these reactions using

TABLE VI
Appearance potential and calculated AH*(H30+) in ethyl formate

A H f ( H 3 0 f ) (kcal/mole)
A (H 3 0 ' )
(kcal/mole) Reaction [14] Reaction [l5] Reaction [16]
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This work 302 175 159 133

Bernecker and Long 334 207 191 166

both our result and that of Bernecker and Long. I t is apparent that the present result
gives a satisfactory ionic heat of formation only if reaction [15] is assumed to be the lowest
energy process occurring. Reaction [14], which was assumed by Bernecker and Long, does
not give results in agreement with other estimates in the present: work. The ionization
efficiency curve showed a rather large tailing, suggesting that more than one reaction was
occurring, and it is possible that Bernecker and Long's appearance potential corresponds
to reaction [16].
The mass spectrum of ethyl formate shows a large mass 45 ion current and a metastable
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a t mass 8.02 (reaction [3]).The mass spectrum of ethyl formate-d (14) shows that approxi-
mately f1.57~ of the mass 46 ion incorporates the formyl hydrogen to give CH3CHOD+.
In addition, in ethyl formate-d a metastable was observed a t mass 8.70 indicating the
transition
DOCHCHaf -+ HzDO' + CzH2. 1171
Since the mass spectrum of ethyl formate-d shows predominantly H2DO+ formation
(1.270 compared to 0.3y0 H30+), and since it-has been established (14) that the ion
CH3CHOD+ is formed with H S C O as the neutral fragment, it was thought that the
D H 2 0 + formation should give a measure of the fraction of the reaction proceeding by
reaction [16]. However, the appearance potential of DHzOf was found to be 306f3
kcal/mole compared to 302rt3 kcal/mole for H 3 0 + from the undeuterated ester. One
must therefore assume HCO+CZHz (reaction [lb]) as the neutral fragments. Obviously,
incorporation of the formyl hydrogen in the H3O+ ion with formation of HCO as one of
the neutrals must involve considerable hydrogen scrambling in the parent ion. The
mechanism by which this occurs is unknown.
Formation of H 3 0 ffrom Isopropyl Formate
The largest peak in the mass spectrum of isopropyl formate is mass 45. In isopropyl
formate-d the peak moves to mass 46 indicating retention of the formyl hydrogen (14).
The rearrangement is given by reaction [IS]:
HCOOCH(CH)z -+ C O + C H 3 + HOCHCH3+ 1181
The mass spectrum of isopropyl formate also shows a metastable a t mass 8.02, moving
to mass 8.70 in the formate-d. The complete reaction for formation of H 3 0 + would thus
appear to be reaction [19] proceeding through the CH3CHOH+ intermediate.
HCOOCH(CH3) -+ CO + CH3 + CzHz + H a o f [19I
 VAN RAALTE A S D HARRISON: H Y D R O S I U M ION FORMATION 3125

A (H30+) = 3 1 7 f 3 kcal/mole leads to AHf(H30+) = 159 kcal/mole assuming this mech-

anism, in good agreement with other results obtained in this work.
In isopropyl formate-d the intermediate hydroxycarbinyl ion contains the formyl
deuterium probably attached to the oxygen, i.e. DOCHCH3f. The labelling results for the
secondary alcohols were explained on the basis of retention of the hydroxyl hydrogen in
the decomposition of this intermediate. In the present case this should lead exclusively
to DH20- formation. The mass spectrum of isopropyl formate-d shows (14) the relative
intensities inass 20:mass 19 = 1.86:0.34. I t is clear that the major part of the hydronium
ion does incorporate the deuterium label as required. The small amount of H30+ probably
again represents a small amount of scrambling in the intermediate ion.
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SUMMARY
The present results lead to an average value AHf(H30+)= 157&3 kcal/mole yielding
a value of 151&3 kcal/mole for the proton affinity of water. The value of 157 kcal/mole
for AHf(H30+)is considerably higher than the maximum value of 145 kcal/mole indicated
by the reported occurrence (4) of the ion-molecule reaction
HzSf + HsO --t H3Of + HS. [I1
The reason for this discrepancy is not obvious. T h e mechanisms proposed for most of the
decomposition reactions in the present work appear to be well substantiated by metastable
and labelling evidence. The appearance potentials and resultant ionic heats of formation
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are therefore not likely to be in error unless excess energy is involved in each ionization
process. This u~ouldnecessitate the same amount of excess energy in each case, and thus
appears unlikely. T h e ion-molecule reactions occurring in the high-pressure mass spectrum
of H20-H2S mixtures are numerous and include (4) reactions [20] and [21] in addition t o
reaction [I].
HzO+ + H2S --+ H30' $- HS [201

In these circumstances it is not clear that it has been clearly established that reaction [I]
involves an HZS+ ion in the ground state. Reaction of an HzSf ion with a minimum of
12 kcal/mole excitational energy could lead to H30+ formation even if reaction of a ground
state ion were endothermic.
In any event, the present results combined with the results of Tal'roze and Frankevich
(4) clearly indicate that AHf(H30+) is in the range 145-157 kcal/mole rather than 207
kcal/mole, as had been suggested by previous electron impact work (12).

ACKNOWLEDGMEKTS
The authors are indebted t o the Advisory Committee on Scientific Research, University
of Toronto, and to the National Research Council of Canada for financial support.

REFERENCES
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