The Vibrational Spectrum of Tetrachloroethylene

H. J. Bernstein

Citation: The Journal of Chemical Physics 18, 478 (1950); doi: 10.1063/1.1747664
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 THE JOURNAL OF CHEMICAL PHYSICS VOLUME 18, NUMBER 4 APRIL. 1950

The Vibrational Spectrum of Tetrachloroethylene

H. J. BERNSTEIN
National Research Council, Ottawa, Canada
(Received October 3, 1949)

The infra-red spectrum of C,Cl, through long paths has been obtained in the region 2.5-251'. As many
combination tones as possible were observed. An assignment of the fundamentals has been made which
interprets satisfactorily 16 lines in the Raman spectrum and 24 bands in the infra-red spectrum.

N OTWITHSTANDING the high symmetry of

tetrachloroethylene (D 2h ), there has been con-
C2Cl 4 was obtained with a Perkin-Elmer spectrometer
(Model 12(:) on a Brown recorder (see Fig. 1 and
siderable disagreement in the literature as to the proper Table II). It is worth emphasizing here that no funda-
assignment (see Table I). Primarily this is due to the mentals of appreciable intensity were found between
fact that the low lying infra-red active fundamentals 400-780 em-I.
have not as yet been observed. DISCUSSION
It was considered worth while to reinvestigate this
molecule using longer absorbing paths than have been The Raman spectrum has been obtained previouslyl
used hitherto in order to bring out as many of the and shows three strong polarized lines at 1571, 447, and
combination tones as possible. In particular, the region 237 cm-I which are Type A g. The spectrum also contains
> 1700 cm-I should be fruitful in tracing down some of two depolarized lines of medium intensity at 347 cm-1
the low lying fundamentals since, as can be seen from and 512 em-I. These could be both of Type BIg or one
BIg and the other B 2g • Of the bands in the infra-red
Table I, combinations of only 1'1 or 1'5 with the low fre-
quency fundamentals are most likely to appear in this spectrum the two very strong ones at 782 and 913 cm-I
region. are taken as fundamentals. The band at 913 cm-I is
taken as IIn(Bau) since a valence force calculation2 which
EXPERIMENTAL permits evaluation of the force constants of the Ag
The tetrachloroethylene used was the Eastman Kodak modes gives a solution for the Bau modes with these
product redistilled in a Stedman column @f about 30 constants and lin = 913 em-I, whereas with lin = 782
theoretical plates. The infra-red spectrum of liquid cm-1 the roots are imaginary. The band at 782 cm- I is
100
- LIQUID ~ 0.3 mm CELL
90
80 ---- LIQUID 0.025mm CELL
z
0
;::: 70 .. GAS 13 mm OF Hg IN 10 em CELL
"- 60
II:
0 50
Ul
CD
<I 40
~ 30
20
10
a

100 CELL LENGTH

90 j, "
II I,

:'

1
80 ,.. ::
,1'1'
~ 70
:\: :V
ii: 60 : U:::
a:
Ul
,
I

I
CD
o 40
50
<I
~ 30
20
10 ,r~
o~~~~~~~/~",,~---~~
900 1000 1100 1200

FIG. 1.

1 See Table II, reference a.

2 See Table I, reference e.
478

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 479

TABLE I. Assignment of the vibrational modes of C 2CI •. TABLE II. Vibrational spectrum of liquid C2Cl. in em-I.

Symmetry type This Infra-red Ramana

and activity' Herzbergb Wu' Duchesned Verleysen' work
429(w) 218(v.w.)
Ag 1571 1569 1569 1569 1571 VI 46O(w) 237(s)pol.
Raman active 447 445 445 445 447 V2 511(w) 347 (m)depol.
237 236 383 236 237 Va 562(w) 447(v.s.)pol.
642(w) 464(w)
A u (inactive in V4 673(w) 512(m)depol.
both Raman 715(w) 574(w)
and infra-red) 758(m) 631(v.w.)
Big 1000 512 512 [1429J 1000 V5 782(v.s.) 726(v.w.)
Raman active 347 341 341 [279J 347 V6 802(5) 784(v.w.)
913(v.s.) l000(v.w.)
B 1u (332) 288 V7 983(w) 1025(w)pol.
infra-red active 995(w) 1441 (w?)
1102(w) 1571 (5) pol.
B 2• 512 383 236 512 VB 1125(w) 1819(w)
Raman active 1143(w) 1998(w)
792 782 782 1172(w)
B 2u 913 Vg
1225(w)
infra-red active (332) 332 [173J 194 VIO 1254(w)
782 913 913 913 913 Vll 1360(w)
B a" 1771(w)
infra-red active (387) 345(calc.) 387 [361J 318 Vl2
1858(w)
1884(w)
• The notation and numhering of frequencies is the same as that employed
by G. Herzberg (see reference b). 2470(w)
b G. Herzberg. Infrared and Raman Spectra of Polyatomic Molecules
(D. Van Nostrand Company. Inc .• New York. 1945).
• T. Y. Wu. Vibrational Spectra and Structure of Polyatomic Molecules • K. W. F. Kohlrausch. Ramanspektren (Edwards Brothers. Ann Arbor.
(J. W. Edward. Ann Arbor. Micbigan. ,1946). Michigan. 1945).
d J. Duchesne. Physica 8. 144 (1941).
• A. Verleysen. Ann. Soc. Sci. Brux .• 287 (July. 1939). The figures in
square brackets are the results of a valence force calculation using four
interaction constants in the potential function.
Of the observed weak infra-red bands the following
interpretation can be given on the basis of this assign-
taken as v9(B 2u ) since v7(B 1u ), vlo(B 2u ), and VI2(B 3u ) are ment, viz.:
460= Vll-V2 = 466(Bau)
expected to have much lower frequencies than this. 673= Vll-Va = 676(Bau)
Without the use of combination and overtones the 983=758+va= 995*
following reasonable assignment can be made: 995 = va+vg = 1019(B 2u)
1102= 758+V6= 1105*
Vl = 1571 } 1125 = V9+V6 = 1129(Bau)
v6=347 1143= Va+vll = 1150(B au )
V2 = 447 Raman active 1172= 758+V2= 1205*
v8=512 1225 = V2+V9 = 1229(B 2u )
1254= V6+Vll = 1260(B 2u )
1/3= 237 1360= V2+Vll = 1360(Bau)
2470= VI+Vll = 2484(Bau).
1/9= 782 The bands not accounted for in the infra-red spectrum
}infra-red active.
are then 429w, 511w, 562w, 642w, 715w, 758m, 802m,
Vn = 913 1771w, 1858w, and 1884w.
The line at 347 cm-l is chosen for v6(B 1g ) rather than Of the remaining five fundamentals one would expect
512 cm- l since the calculations of Verleysen2 indicate a VIO, V12, 1/7, and 1/4 to be low2 and less than 500 em-I,
low frequency. whereas 1/6 may be high and in the vicinity of 1000 em-I.
Of the observed weak Raman lines several can be Since V6+V11 and V6+V9 are infra-red active, these
interpreted on the basis of the above assignment, combination tones would be above 1700 em-I. As a
v~z.: result, the infra-red bands over 1700 cm-l can be ac-
218= V2-Va= 210(Ag) counted for in two ways, either by combination with
464= 2va = 474(Ag) 1571 cm-l or by combination with 1/6.
574= Va+V6= 584(B1g)
726= Va+vB= 749(B 2g) For the first alternative, two of the infra-red active
784= V2+V6= 794(B1.) fundamentals are given by 1858-1571 = 287 cm-l and
1025= 2VB =1024(A g) 1884-1571 = 313 cm-I, and for the second, the following
1819= 2Vll = 1826(A.) choices for V6 are permitted:
1998= vI+v2=2018(A.).
1858-782= 1076 cm-l
The remaining weak Raman lines not accounted for 1858-913= 945 cm-l
are 631 em-I, 1000 cm-I,3 and 1441 cm-I.4 1884-782 = 1102 cm-l
1884-913= 971 em-I.
a This line is very weak. See Table II.
• This line is designated with a question mark (see Table II) * Since the bands at 758 cm-1 and 802 cm-l are of medium in-
indicating doubt as to its reality. tensity, triple tones are not unreasonable.

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 480 H. J. BERNSTEIN
TABLE III.

Infra-red Ramana Infra-red Rarnan a

Assignment (liquid) (liquid) Assignment (liquid) (liquid)

V2- va(A.) 218(v.w.) v7+ vs(B a,,) 802(s)

va 237(s)pol. V11 913(v.s.)
V7 288(s)b (v2+vd+vs(Bsu) 983(w)
V12 318(s)b va+ v9(B 2u) 995(w)
V6 347 (m) depol. v. l000(v.w.)
? 404(?)b 2vs(A g) 1025(w)pol.
v.+ JlIO(B 2u) 429(w)c (V2+ V12) + v6(B. u) 1102(w)
V2 447 (v.s.)pol. V6+ V9(Bsu) 1125(w)
V11- Jl2(Bau) 460(w) v,+v11(B au ) 1143(w)
2va(Ag) 464(w) (V2+ v,,) + v2(B au ) 1172(w)
va+ v7(B lu) 511 (v.w.) V2+ Jl9(B2u) 1225(w)
Vs 512 (m)depol. V6+ Vll(B 2u) 1254(w)
va+ v12(B au) 562(w) V2+ vlI(B au ) 1360(w)
va+ v6(Blg) 574(w) v2+ v.(Blg) ? 1441(w?)
2VI2(Ag) 631(v.w.) VI 1571 (s)po!.
V2+ vlo(B 2u ) 642(w) VI+VIO(B 2u ) 1771(w)
VlI - va(B au) 673(w) 2vll(A g) 1819(w)
V2+ V7(B lu ) 715(w) VI+V7(B lu) 1858(w)
vs+vs(B2g) 726(v.w.) vl+vdBau) 1884(m)
V2+ vI2(B au) 758(m) vl+v2(A .) 1998(w)
V9 782(v.s.) vl+vlI(B au ) 2470(w)
V2+ V6(Blg) 784(v.w.)

• See Table II. reference a.

b Observed by E. K. Plyler. see reference S.
, Observed by E. K. Plyler (reference 5) at 431 cm -1.

Since VB is Raman active and none of the above following interpretations are possible:
choices for it are present as a line in the Raman spec-
511= v.+v7=525(B 1u)
trum, it seems probable that the bands above 1700 cm-I 802= vs+v7=800(Bau)
are to be accounted for only by combination with 1571 715= V,+V7= 735(Blu).
em-I. It would seem therefore that 1858 cm-I is to be
explained by combination with a fundamental around In the Raman spectrum then, only 1000wand 1441?
287 em-I and 1884 cm- I by combination with the are not explained and in the infra-red spectrum the
fundamental at 313 cm-I.5 bands at 1771, 642, and 429 cm-I are still unexplained.
Since Vl1 has combined with VI, V2, and Va to give bands To interpret some of these bands the unobserved
in the infra-red spectrum, one might expect to observe infra-red active fundamental VIO is at our disposal. If VIO
combination tones of V12 with VI, V2, and Va. Choosing is taken as 194 cm-I, then
the observed value5 of 318 cm-I for VI2 rather than the VI+VIO= 1765(B 2u )
value 313 cm- I obtained by difference, the observed V2+VIO= 641(B 2u )
bands at 1884, 758, and 562 cm-I may be interpreted as va+vlQ= 431(B 2u );
VI2+Vl, VI2+V2, and V12+Va, respectively. Choice of 288
cm- I as V12 on the other hand gives combination tones of all of which are observed, viz., 1771,642, and 429 em-I.
which only one is observed. This choice for VIO is not unreasonable since the valence
This seems to justify choosing the band at 318 cm-I force calculations6 indicate a low frequency for this
as the fundamental V12. This choice is supported further fundamental.
by a valence force calculation.6 The only choice left for the line at 1000 cm-I ap-
I
The band at 288 cm- is taken as V7 rather than VIO pearing in the Raman spectrum is to assign it as v•.
since valence force calculations6 indicate that VIO is The line at 1441 cm-I may then be V6+V2= 1447 (Big).
lower than 200 em-I. Table III gives the complete assignment of the
The line at 631 cm-I in the Raman spectrum may now observed Raman and infra-red spectra. This assignment
be interpreted as 2v12=636(Ag). Of the bands in the though plausible must still be regarded as tentative
infra-red spectrum hitherto not accounted for, the inasmuch as VIO and VB are uncertain and V4 is not
estimated.
• E. K. Plyler of the National Bureau of Standards, Washington, On the basis of this assignment an estimate of V4 could
D. C., has obtained a spectrum of our sample of C 2Cl. in the region be made if the specific heat of the gas were known at one
251-'-401-' with a thallium bromide prism. His results, which he has
kindly allowed to be quoted, are obtained in a 1.6-mm cell and are temperature. 7 This might prove of interest since the
288s, 318s, 404?, and 431w em-I. torsional constant could be estimated thus enabling an
The agreement between the expected and observed funda-
mentals is quite good.
6 See Table I, column 5. 7 See Table I, reference b, p. 512.

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 TRITIUM HALIDE EQUILIBRIA 481

approximation of the torsional frequency in ethylene to
be made.
Note added in proof: The recent paper on the vibrational spec-
trum of tetrachloroethylene by P. Torkington [Trans. Farad. Soc.
45,445-7 (1949) ] has just come to the attention of the author. On
the basis of the early experimental data listed in column 2 of
Table I, Torkington suggests the following assignment:
A g = 1571,447,237; Au= 135 (estimated from the torsional fre-
quency in ethylene); B 1g =512, 347; B 1u = 185; B 2g = 215; B lu =913,
332; Bsu= 782,387.
ACKNOWLEDGMENT
Thanks are due Dr. E. K. Plyler for permission to use
his results on the far infra-red spectrum of C 2Cl 4 and
Miss E. Miller for reduction of the spectra.

THE JOURNAL OF CHEMICAL PHYSICS VOLUME 18, NUMBER 4 APRIL, 1950

Dissociation and Exchange Equilibria of the Tritium Halides*

JACOB BIGELEISEN
Brookhaven National Laboratory, Upton, N e'"dI York
(Received October 3, 1949)

The ratios of the partition functions of the tritium halides to their respective protium halides have been
calculated. These are combined with one another to give the exchange equilibria between the six pairs of
tritium and protium halides. The exchange equilibria with water are calculated. From the exchange equi-
libria between the tritium halides and protium and the free energy of dissociation of the protium halides, the
dissociation equilibria of the tritium halides have been calculated.
The experimental data on the dissociation of HI are reviewed and it is shown that the data of Taylor and
Crist on DI and HI are self-consistent as well as in good agreement with theory. The heat of formation of HI
at absolute zero, tJ.Hoo, is found to be -1007±1O calories per mole.

INTRODUCTION
THE availability of the hydrogen isotope of mass
three, tritium, for experimental purposes makes
it desirable and important to have available the thermo-
dynamic properties of different chemical compounds of
this nuclide. Libbyl has calculated the exchange equi-
libria between the isotopic water and the isotopic
hydrogen molecules. Urey2 has calculated these same
equilibria as well as the partition function ratios of the
various pairs of isotopic water molecules and the iso-
topic hydrogen molecules. Jones3 has calculated the
thermodynamic functions for tritium and tritium
hydride. From these and the free energy function of
protium he has calculated the equilibrium between
tritium, protium, and tritium hydride. In addition, he
has calculated the dissociation of the isotopic hydrogen
molecules into atoms.
This paper reports the calculations of the partition
function ratios of the tritium to protium halides. The
partition function ratios of the four isotopic hydrogen
halides are then combined to give the six exchange
equilibria between the various tritium and protium
halides.
TX+HXl=TXl+HX. (1)
The ratios are also combined with the partition function
ratios of the tritium water molecules and the protium
water molecules to give the exchange equilibria between
* Research done at the Brookhaven National Laboratory under
the auspices of the AEC.
1 W. F. Libby, J. Chern. Phys. 11, 101 (1943).
• H. C. Urey, J. Chern. Soc. 562 (1947).
s W. M. Jones, J. Chern. PhI'S. 16, 1077 (1948/.
the tritium halides and water. From the calculated ex-
change equilibria between the tritium halides and
protium and the known free energies of formation of
the protium halides,4 the dissociation equilibria of the
tritium halides have been calculated. By means of
suitably chosen exchange equilibria, which can be
calculated directly from partition function ratios, it is
possible to calculate all the thermodynamic equilibrium
constants for gaseous tritium compounds from the
experimental and theoretical values for the correspond-
ing protium compounds. This is the most rapid pro-
cedure for such calculations and the precision and ac-
curacy attained are generally limited by the accuracy
of the protium determinations.
PARTITION FUNCTION RATIOS
The formulas and method for the calculation of the
partition function ratios have been published pre-
viously.s Both chlorine and bromine each have two
stable isotopes. The partition function ratios TCl/HCI
and TBr/HBr are calculated for the normal isotopic
abundance of the halogens. The procedure used was to
calculate the spectroscopic properties of the tritium
chloride and bromide as though they were each mono-
isotopic. The mass of the halogen taken was the
weighted masses of the isotopes. This simplification
over the procedure of calculating the ratios for each of
the halogen isotopes and weighting the ratios introduces
an error of less than one tenth of one percent for the
4 "Selected values of chemical thermodynamic properties," Na-
tional Bureau of Standards, June 30, 1948.
•J. Bigeleisen and M. G. Mayer, J. Chern. Phys. 15, 261 (1947).

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