2058 Notes
Acknowledgment. The authors wish to thank Dr.
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
Downloaded via UNIV ESTADUAL PAULISTA on August 15, 2020 at 01:30:01 (UTC).
Figure 1. Magnetic scan of mass regions 144 and 116
Fe(CO)e. The diffuse peaks correspond to the
metastable transitions noted.
of the metastable ions are summarized in Table II.
The two most abundant metastable transition patterns8
are shown in Figure 1. The sharp peaks at m/e
142 and 114 are Fe68(CO)3+ and Fe68(CO)2+, respec-
tively.
Each of the metastable transitions observed involves
the loss of a neutral carbon monoxide from the metal
carbonyl ions. In the case of the singly charged Fe-
(CO)z+ transitions, the decomposition scheme recently
proposed by Winters and Kiser,2 i.e., a series of con-
secutive unimolecular reactions
Fe(CO)s+ —Fe(CO)4+ Fe+
involving successive removal of neutral CO groups is
substantiated. Metastable transitions also were ob-
served for the loss of carbon monoxide from FeC302+
and FeC20+ions.
The metastables observed in the decomposition of
Fe(CO)z2+ suggest that the doubly charged transition
metal carbonyl ions also lose neutral CO groups in a
successive manner.9 Beynon, et al.,w have reported
similar transitions for the dissociation of doubly
charged ions in the mass spectrum of 2-hydroxyan-
thraquinone. Recent studies11·12 of the decomposi-
tion of C022+ ion indicate CO+ and 0+ as the product
ions. Evidence for this type of transition was sought
in this study but was not found.
The Journal of Physical Chemistry
D. A. Nicholson for purification of the iron penta-
carbonyl used in this study.
(7) Calculations of the apparent masses for the singly and doubly
charged transitions were made using the standard equation cited in
ref 6, p 124.
(8) Metastable transitions are observed for each of the four iron
isotopes. All calculations, however, were made using the major
isotope (56) of iron.
(9) A similar decomposition scheme has been suggested for W(CO)*2 +
breakdown (R. E. Winters and R. W. Kiser, J. Phys. Chem., 70, 1680
(1966)).
(10) J. H. Beynon, G. R. Lester, and A. E. Williams, ibid,., 63,
1861 (1959).
(11) A. S. Newton and A. F. Sciamanna, J. Chem. Phys., 40, 718
(1964).
(12) K. E. McCulloh, T. E, Sharp, and . M. Rosenstock, ibid., 42,
3501 (1965).
Mass Spectrometric Method for the
Determination of the Activity Coefficient of
for
Ammonia in Aqueous Salt Solutions1
by Richard A. Durst,2
Department of Chemistry, Boston College,
Chestnut Hill, Massachusetts 02167
Paul G. Schmidt,3 and Irwin Feldman3
Department of Chemistry, Pomona College, Claremont,
California 91711 (Received January 10, 1966)
Experimental techniques for the determination of
activity coefficients of nonelectrolytes have been
primarily limited to four methods: solubility, distri-
bution, cryoscopy, and vapor pressure.4 Solubility,
(1) while a simple and precise method, is easily applicable
only to nonelectrolytes having low solubilities. Dis-
tribution is also a relatively simple method, but it is
often difficult to find a reference solvent that is suf-
ficiently immiscible with water and for which the dis-
tribution ratio of the nonelectrolyte is such as to give
adequate accuracy in the activity coefficient determi-
nation. Although very precise, cryoscopy is more
complex and the temperature of the experiment is
(1) This work supported by the National Science Foundation under
Grant No. GE-6158.
(2) Visiting Assistant Professor of Chemistry, Pomona College
(1964-1965), and author to whom reprint requests should be directed.
(3) Supported by NSF Undergraduate Science Education Program
(GE-6158).
(4) F. A. Long and W. F. McDevit, Chem. Rev., 51, 119 (1952).
Notes
necessarily limited to the freezing point of the solution.
Finally, the use of the vapor pressure method is re-
stricted to volatile substances, and accurate measure-
ments often require a high concentration of the non-
electrolyte.
A new method is presented here for the determina-
tion of activity coefficients of ammonia in aqueous salt
solutions. It is a variation of the vapor pressure
method, but the need for a high concentration of the
nonelectrolyte has been eliminated and the procedure
greatly simplified. The mass spectrometer is used to
analyze quantitatively the ammonia vapor in equi-
librium with the solutions, giving activity data over
a wide range of salt concentrations. The range of
sensitivity of the mass spectrometer is such that the
ammonia concentration limits in both directions
extend well beyond any previously studied. The high
sensitivity also permits the study of substances not
volatile enough for the usual vapor pressure methods.
Experimental Section
For each salt studied, six or seven 100-ml solutions
containing approximately 0.1 mole of ammonia and
salt concentrations covering a molality range of 0 to 6
were prepared and placed in 250-ml erlenmeyer flasks.
Each flask was fitted with a two-hole rubber stopper.
A short piece of glass tubing was inserted into one of
the holes in order that a rubber balloon, which served
as a pressure compensator, could be fastened inside the
flask. A ground glass joint was inserted into the other
hole and stoppered with a cork. All solutions were
allowed to equilibrate for a minimum of 12 hr.
A Hitachi Perkin-Elmer RMU-6D mass spectrometer
was used for the vapor analyses. Samples were taken
with a 50-ml glass sample bulb which was evacuated to
a pressure of 10~2 mm and fitted over the glass joint
in the equilibration flask. As the valve on the sample
bulb was opened, the balloon, which was open to the
atmosphere, expanded, thus avoiding a large reduction
in pressure inside the flask. The vapor sample was
then analyzed with the mass spectrometer. Inlet
system pressures were reproduced to within ±0.05%.
The NH3+ peak (m/e 17.0265) and the OH+ peak (m/e
17.0027) were completely separated by using a narrow
collector slit width and a slow mass scanning speed.
The NH3+ peak was scanned every 10 sec following the
introduction of the sample into the analyzer. Maxi-
mum peak height occurred approximately 1 min after
sample introduction and remained constant for about
seven readings before tapering off. This height,
after correcting for the background, was used for cal-
culating the ammonia activity coefficient. Aliquot
samples of the solutions in the flasks were then titrated
2059
with standard HC1 to determine the ammonia concen-
tration.
For two solutions of a nonelectrolyte, the relation
between the activities of the solutions and their partial
vapor pressure is given by the equation
fC_ =
p
fC° p°
where f° is the activity coefficient, C° is the concentra-
tion, p° is the partial pressure of the nonelectrolyte
in pure water, and /, C, and p represent the respective
values in the salt solution. Since the peak heights,
P° and P, recorded by the mass spectrometer are di-
rectly proportional to the partial pressures, the equa-
tion can be rewritten
/ JVC
=
f pyc°
The activity coefficient ratio of ammonia in salt solu-
tions is then calculated using the ammonia in pure
water as the reference solution. However, since the
activity coefficient of ammonia in pure water can be
determined by another method (described below),
the ratio measured mass spectrometrically can be used
to calculate the ammonia activity coefficient in the
salt solutions.
In order to check the validity of this technique, the
mass spectral data were compared with data obtained
by an independent method, i.e., activity measurements
made cryoscopically.5 Solutions of various concentra-
tions of ammonia were mixed with crushed ice and
allowed to come to equilibrium. The temperature
at equilibrium was recorded as the freezing point of
the solution. Simultaneously, a sample of the solu-
tion was taken and titrated to determine its molar
concentration. Using values for the densities of
aqueous ammonia solutions,6 the concentration terms
were converted from molarity to molality. The activ-
ity could then be calculated from the relationship7
In (a/m) =
—2j
where the activity, m is molality, and ,7
a is = 1 —
At/mKs; At is the freezing point depression and =
1.855°/molal =
cryoscopic constant for water. The
resulting data are given in Table I.
(5) D. P. Shoemaker and C. W. Garland, “Experiments in Physical
Chemistry,” McGraw-Hill Book Co., Inc., New York, N. Y., 1962,
p 143.
(6) “International Critical Tables,” Vol. Ill, E. W. Washburn, Ed.,
McGraw-Hill Book Co., Inc., New York, N. Y., 1928, p 59.
(7) J. M. Wilson, et al., “Experiments in Physical Chemistry,"
Pergamon Press, New York, N. Y., 1962, p 150.
Volume 70, Number 6 June 1966
2060 Notes

Table I: Cryoscopic Data for the Aqueous Ammonia Activity

Molarity Molality® Activity

0.097 0.097 0.18 0.097
0.246 0.246 0.47 0.261
0.352 0.352 0.69 0.395
0.508 0.508 0.84 0.409
0.540 0.540 1.05 0.594
0.612 0.612 1.19 0.673
0.654 0.654 1.20 0.640
0.687 0.687 1.30 0.714
0.709 0.710 1.47 0.897
0.879 0.880 1.55 0.795
0.999 1.02 1.84 0.965
1.037 1.07 2.05 1.14
1.151 1.18 2.14 1.12
1.21 1.25 2.4 1.34 Figure 1. Activity coefficient ratio of
1.26 1.30 2.5 1.39 ammonia in aqueous salt solutions.
1.69 1.77 3.4 1.90
1.86 1.99 3.8 2.11
2.50 2.68 5.3 3.05
2.65 2.86 5.6 3.19
3.07 3.35 6.7 3.92
3.74 4.15 8.4 4.97
3.97 4.43 9.0 5.35
“
Calculated from molarity and density data.

Another set of activity determinations was then

made using the mass spectrometer. The method
used was the same as that discussed for the salt effects,
except that varying concentrations of ammonia were
used, and no salt was added.
Results and Discussion
Data obtained for the activity coefficient ratio of
ammonia in the NaCl, NaCKX, and LiBr systems are
listed in Table II, and these results are shown in Figure
1. Since differing concentrations of ammonia were
used in the three sets of determinations, the data are
reported in terms of the ratios to facilitate intercom-
parison of the results. However, it should be re-
Figure 2. Comparison of mass spectrometric
emphasized that by using the activity data for ammonia and cryoscopic data for the activity of ammonia.
from Figure 2, it is possible to evaluate the activity
coefficient ratios for the particular reference solution
and obtain the actual activity coefficient for ammonia Abegg and Riesenfeld,8 who studied the effects of
in the salt solutions. The graph of the activity of several salts over a much smaller concentration range
ammonia vs. molality of ammonia (Figure 2) from 0.5 to 1.5 m. Ammonia activity data for NaCl
shows the good correlation between the cryoscopic and LiBr concentrations above 1.5 m have not been
method (at approximately 0°) and the mass spectromet- previously reported, nor have data (at any concentra-
ric method (22°). In addition, it can be seen that the tion) for NaCICX solutions. The activity coefficient
mass spectral data are considerably more consistent, ratios of ammonia vs. the salt molality appear to be
particularly in the more dilute solutions (less than 1.5 linear within the deviation limits, although the pos-
m) where the precision of the cryoscopic data is low. sibility of some curvature cannot be ruled out. How-
The data obtained for the NaCl and LiBr solutions
are in excellent agreement with results obtained by (8) R. Abegg and H. Riesenfeld, Z. Physik. Chem., 40, 84 (1902).

The Journal of Physical Chemistry

Notes 2061

activity determination of water. Since the peak

Table II: Activity Coefficient Ratio of Ammonia
in Aqueous Salt Solutions height ratio between OH+ and H20+ is constant after
correcting for contributions from other sources, the
Number Std dev OH+ peak is a direct measure of the water vapor
Salt Ammonia /NHj/ of observa- of the
molality molarity /°NHi tions mean
partial pressure. Because of the adsorption problem,
measurements of the water activity were not made in
LiBr this study, but there should be no difficulty once the
0.0 1.034 1.00 4
direct capillary inlet is constructed. Since the mass
0.50 1.050 0.936 3 0.015
1.046 0.892 0.020 spectrometer can both quantitatively and qualitatively
1.00 3
2.00 1.053 0.810 4 0.012 analyze the vapor sample, this technique should be
3.00 1.054 0.718 4 0.014 applicable to the simultaneous determination of
4.00 1.050 0.606 4 0.018 activity of several volatile species in complex multi-
6.00 1.026 0.404 4 0.020
component systems.
NaCl
0.0 0.806 1.00 3
0.505 0.838 1.049 3 0.004
1.02 0.831 1.107 3 0.010
2.09 0.805 1.220 2 0.019 Free Radical Addition of Perfluoroacetonitrile
3.77 0.774 1.361 3 0.016
5.59 0.783 1.520 3 0.002 to Vinyl Fluoride
NaC10«
0.0 0.988 1.00 3 by G. J. Janz and J. B. Flannery
0.50 0.982 0.993 3 0.015
1.00 0.981 0.993 2 0.015 Department of Chemistry, Rensselaer Polytechnic Institute,
Troy, New York (Received February 11, 1966)
2.00 0.978 1.003 3 0.049
3.00 0.982 0.997 3 0.037
4.00 0.984 0.992 3 0.015
6.00 1.000 1.005 2 0.006 In the free-radical addition of perfluoroalkylnitriles
and propylene, two isomeric products are formed.
Correspondingly, with vinyl fluoride and CF3CN,
one would predict two possible structures for the
ever, the present data do not justify any such curve
compound, CF3CH2CHFCN (I) and CF3CHFCH2CN
fitting.
The wide range of sensitivity of the mass spectrom- (II), resulting from the equimolar addition reaction.
The results of a series of experiments are reported in
eter makes it ideal for the measurement of ammonia
this note for the addition reaction CF3CN and CH2CHF.
activities over a large range of ammonia and salt con-
centrations. The precision obtained (2-3%) was Only one of the two possible isomeric compounds,
somewhat reduced by minor instrumental difficulties, namely, CF3CH2CHFCN, is apparently formed. A
but the major source of error was due to the adsorp- precise kinetic study was found impossible since the
formation of higher telomeric compounds could not
tion of water on the glass walls of the inlet system of
be suppressed to less than 13%. These results are
the mass spectrometer. Ammonia, with its affinity
examined relative to related studies1·2 with C2Hí and
for water, was probably absorbed to some extent.
This difficulty was minimized by allowing the system propylene.
to reach equilibrium during each mass spectral de-
termination. More precise results could be obtained Experimental Details and Results
by introducing the sample directly into the ion source The reactants, CF3CN (95% nr ', bp —64°, Peninsu-
through a fine capillary inlet. With this modification lar Chemresearch, Inc.) and CH2CHF (bp —51°,
and with higher instrument stability, a precision of E. I. du Pont de Nemours and Co., Inc.) were de-
better than 1% could be expected. The effect of gassed three times under high vacuum at —195°.
changes in the hydrolysis of ammonia in the different Analysis by gas chromatography showed the purity
salt solutions is not included in the present study. of both reactants to be better than 99%.
However, it is expected that this factor will not have a
significant effect on the observed activity results. (1) G. J. Janz, N. A. Gac, A. R. Monahan, and W. J. Leahy, J. Org,
Furthermore, indications are that the mass spectrom- Chem., 30, 2075 (1965).
eter can be successfully applied to the simultaneous (2) N. A. Gac and G. J. Janz, J. Am. Chem. Soc., 86, 5059 (1964).

Volume 70, Number 6 June 1966