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1970
The Dipole Moment of Cis- and Trans-ChloroiodoethyleneAshvin Gajendralal GajjarEastern Illinois UniversityThis research is a product of the graduate program in Chemistry at Eastern Illinois University. Find out moreabout the program.
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Recommended CitationGajjar, Ashvin Gajendralal, "The Dipole Moment of Cis- and Trans- Chloroiodoethylene" (1970). Masters Theses. 4023.https://thekeep.eiu.edu/theses/4023
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/L81861.C57XG1454>C2/
The Dipole Moment of Cis- and Trans-
Chloroiodoethylene (TITLE)
BY
Ashvin Gajendralal Gajjar B . Sc . (1960) M.Sc. (1962)
The Gujarat University, Ahmedabad ,
THESIS
India
SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS
FOR THE DEGREE OF
Master of Science
IN THE GRADUATE SCHOOL, EASTERN ILLINOIS UNIVERSITY
CHARLESTON, ILLINOIS
1970 /
I HEREBY RECOMMEND THIS THESIS BE ACCEPTED AS FULFILLING
THIS PART OF THE GRADUATE DEGREE CITED ABOVE
ADVISER
;; /' .., DATE DEPARTMENT HEAD
1ltE DIPOLE t«>MBNT OP
CIS- AND TRANS-
CHLOROIODOETHYLENE
By
Ashvin Gajondralal �jjar Bachelor of Sciellco
The Gujarat University Ahmadabad, India
April, 1960
Master of Science The Gujarat University
Ahmedabad, India April, 1962
Submitted in partial fulfillment of the requirements for the degree of Master
of Science in Chemistry at the Graduate School of Eastern Illinois University
Oi.ARLESTON, ILLINOIS 1970
nIB DIPOU: K>MENTS OF
CIS AND TltANS -
CHLOROIOlJOE'lliYLENE
Thesis Approved ·
Dr. 0. W. cbdon
ur� J • w. tl.u.1a
Dr. R. H
.' Dr. S. R. Steolo
(ii)
ACKNOWLEDGEMENT
The author expresses his sincere appreciation to Mr. Giles
Henderson for suggesting the problem and for providing guidance,
inspiration and assistance throughout the investigation.
The author would like to give thanks to other members of the
faculty for their active interest and help.
The author wishes to thank Dr. J. w. Ellis for his help in
modification of the dielectric cell, Mr. Walter Boyd for his
assistance with the mass and nmr spectra and Mrs. Terry Hawickhorst
for typing this manuscript.
Gxat6ful acknowledgement is also mad6 to the Easte111 Illinois
Univer5ity Research Grant Collllllittee for their support.
Also thG author wants to thank his parents for their patience
and encouragement during his study.
(iii)
Chapter
1
II
Ill
IV.
Taule of Contents
Page
Introduction . . . . . • . . . . . . . . . . . . . . . . . . . . . . . . . . . . . • . . 1
(a) Dipole Moment........ . . . . . . . . . • . . . . . . . . . . . . . . . l
(b) Dielectric Theory • • • • • • ••••••• • •• • •• • • •••• • • • • 8 (c) Measurements in Solution • •• • • • • •••••••• • • • • • • • 12 (d) Influence of Solvent on Polari�ation • • • • • • • • • • 15
(e) Dielectric Measurements •••••• • • • • • • •••• • • •• • • • 17
(f) Histor ical Preparation of C2H2Cll • • • • • • • • • •• • • 19
Experimental ....... � . . . . . . . . . . . . . . . . . . . . • • . . . . . . . . 21
(a) Measurements • • • • • •••••••• • • • • • • •• . • • • • • • • • • • • • 21
(b) Rosoarch Plan •••• , •• • ••••• , ••••• , ••••••••••••• 22
(c) Starting Materials for Synthesis and Primary S taridards . . . . . . . . . . . • . . • • • • . • • • . . • • . • • . . . . . . . . 25
(d) Purification of M�terials • • • • • • • • • • . • • • • . • . • • • 25
{e) Preparations . . . .. . . . . . ,. . . . . . . . . . . . . . . . . . 41 . . . . . 27
(f) Dielectric cell and Measurements • • • • • • . . . • • • • . 30
(g) Dielectr ic Calibration • • • • • • • • • • • • • • . • . . • • • • • • 31
(h) Dipole Moment Calculatlons • • • • • • • • . • . • • • • . • • • • 32
(a) Result and Discussion • • • • • • • •• • • • • • • • • • • • • • • • • 35
(b) Conclusion and Summary................... • • • • • 38
(c) Suggested Resear ch • • • • • • • • • • • • • • • • • • • • • • • • • • • • 39
Bibliography.. . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
(iv)
LIST OF PIGURHS Paa•
1 Dipole momont in els and trans isomors 3
2 Para-chloroiodoboniono 7
3 Induced charges in molecules, caus ing dis�ortion 8 polari&ation, re1ultin1 frolll the presence of charged plattts
4 Slock diagram of dielectric measurements 17 S Hotorodyno beat apparatus 41
6 Dielectric coll 43
7 Plot of nitrobonieno in cyclohoxane 44
8 PlQt of i)dobenzene in benzene 45
9 Plot of ch.loroiodoewylono in bcm�eno 46
10 Plot of c.hloroiodoethylone in cycloboxane 47
ll (a) & (b) Infrared spectrum of trans-chlorovinyl .. rcuric chloride
12 Vpc of trans -chloroiodoethylene
1.3 Vpc of cie-trana-chloroiodoethylene
14 (a) Nar of trans-chloroiodoothylene
(b) Expanded spectrum of trans-chloroiodoothylone
15 (a) & (b) Infrared spoctr.wn of trans-chloroiodoethylene
16 (a) ' (b) Infrared spectrum of cis-trans-chlorovinyl morcuric cbloriao
17 l�mr of cis-trans -chlorovinyl mercuric chloride
18 (a) � (b) Infrared spectrum of cia-trans-chloroiodoethylone
48-49
50
so
Sl
52
53-54
55-56
57
58-59
LIST OF FIGUJU:S (continued) Page
19 (a) Nmr of cis-trans-chloroiodoethylene mixture 60
(b) Expanded spectrum of cis and trans-chloroiodoethylene 61
20 Vpc of 87.s-aa.soc fraction 62
21 Vpc of 9l.6-94.o0c fraction
22 Nmr spectrum of 87.s-ss.s0c fraction
23 Nar spectrum of 93.6-94.0oC fraction
24 Vpc of crude product obtained froa ICl + HC•at
62
63
64
65
LISl' Of lAfsLES
l Illustration of tho Dipole Moments
2 Illustration of th• Uipole Rulo
l Influence of Solvent on Polarization
4 Physical Constants of Chloroiodoothyleno
S(a) Pnyaical Constants of the Dielectric Standards
(b) Dielectric Conatanta of Nitrobenieno in B�nzone
o Polynoaial Coef f icionta
7 Function £valuation and Standard Deviation
8 Oioloctric Calibration
9(a) Tho Dipole Mo .. nt of le><lobonzene in Benzene
(b) The Dipole Moment of Nitrobeniene in Cyclohexa."le
Page
s
6
16
20
34
34
66
67
69
70
71
(c) The Dipole Moment of Chloroiodoothylone in Cyclohexane 72
(d) The Dipole Moment of Chloroiodoothylono in Benzene 73
10 Masa Spoctrua of Chloroiodooth)lono 74
11 Physical Constanta of cis and �rans-Cl1loroiodoethyleno 40
Chapter 1
INTRODUCTIOO
The dipole moments ·o� £!.!_and trans-chloroiodoethyleno,
measured and reported by Errera (�OJ aro µ cis • 0.57 D and . -
µ trans • 1.27 D. In view of the olectronoaativity of chlorine and
iodine ono would expect the dipole moment of tho � isomer to be
groator than the corresponding trans isomer. The purpose of this
research is to reinvestigate the structure assignment and tho
dipole moments.
(a) Dipole Mo110nt: (1-S)
lbo interpretation of electric dipole moments is one of the
aost useful mothods for determining the structure of organic and
inorganic C011pounds. Molecules are composed of eloctrons and
nuclei in a stato of vibration about certain fixed points in space.
At any given instant the centers of action of the positive and
negative electrical charaos may not be coincident and the molecule
may aomentarily po1soss a dipole lllOllent.
If A and B represent the normal electrical centers of positive
and neaative charges, both of which are equa! to e since the
molecule as a whole is electrically neutral,
cl A •• .....__ __ .....,;_ __ �)------·· <3
e+ e-
then the "dipole moment" (µ) of the molecule is given by
).I. ed (1)
where ).I • dipole moment in Debye Units (D)
e • electronic charge in esu (4.8 x io-10 esu)
d • distance between two atoas in A0 (1 x l0-8 cm)
A molecule possesses a dipole moment whenever the center of
positive charge does not coincide with the center· of negative
charge. The dipole mOllents are vector quantities, since they have
magnitud� and direction. Dipole moments are the results of bonding
of ato1111 of different electronegativity.
The symmetry of a molecule will detet'lline the direction of the
dipole. The more symmetrical the molecule the smaller the dipole
mome�t. In an electric field all molecules have an induced dipole
moment (which is aligned approximately parallel to the field
direction) owing to distortion polarization. Molecules made of
atoms of different electronegativity and lacking symmetry will have
a permanent dipole 1110ment of constant magnitude � and a direction
which is fixed relative to the molecular skeleton. Molecules with a
permanent dipole will be influenced by an electric field such that
orientation polari�ation will be the major component. Tile sum of
tho orientation and distortion polarization is known as the molar
polarization.
It was suggested by van Arkel (6) that the boiling points of
the cis and trans isomers of isoaeric olef ins were in fact determined
by thoir dipolo moments. Since cis and trans olefins almost always
2
differ in dipole 11011ents, the dipole rule should apply, i.e. the
isoaer of high•r dipole aomont should have the higher physical
constants. Por an olefin of the type abC • Cba, where a and b aro
any substituents, tho cia isOllOr would have the greater dipole
moaent and consequently the higher boiling point, density and
refractive index. Consider an olefin of th• type aHC • Oil> where
C-a and C-b have appreciable bond moments and C-H doos not, the
trans isomer will always have the lower dipole JIOlllOnt. nds
phonoaenon is due to the cancellation of the dipole voctors, of tho
trans isoaor aa opposed to the aclciition of those vector forces in
tho cis isomer. On tho other hand if a is any electron withdrawing
group and b is any electron donating iroup, one would expect the
dipole 11e>aent (and boiling point) of the trans isome� always to bo
greater than tne corresponding cis isomer as illusi �ated in Tablo l
and Pig. 1. Examples are shown in Taule 2.
Cis Trans
Fig. 1
l
lt is found that the boiling point , density and refractive
index usually correlate well with the dipole moment (ClOi•QiI is
incongruent to the rule). Tilus whereas in the case of 1,2-dichloro
othylene, 2-butene, diethyl butenedioate , and cyclodocene , tho cis
isomer has the hieher constants, in the case of 1-chloro-l-propeno,
crotononitrile, and cyclooctene the trans iso .. r has the higher
constants.
4
Formal a
C2H2AsCl2
C2H2BrCl
C2tt2HgCl2
Table l (7) Illustration of �he Oipolo Moaents
Compound Nuo µ.D
Cis-2-Chlorovinyldich- 1.79. loroarsine 2.6lb'
Trans-2-Chlorovinyldi- 2.21b CliiOroarsine
Cis-1. 2-ChlorobrollO- 1.56 ethyl_!l}O _____
-------------·-·-- ------ ----- ---
State or
Solvent
Benzene Benzene
Benzene
Benzene .S�cified
t0c
20 25
25
Not
Trans-1.2-ChlorobrollO- O Benzene Not ethylene Specified
Cis-1,2-Dichloro-l- 2.76 Not Not Mercury_ etjlyl�_�o _ ___
_ -�- _ Sptl�Jfi�d_ __ m Specified
Trans-1.2·Dichloro-lMercury ethylene
1.64 Not Specified
Not S�cif ied
&i*>hler. K., Helv. Chia. Acta. 21, 789-92 (1938).
!olothod or Pa
\ of Pc
0 s
s
bMcUowell, c. A • • H. G. Eablea, and E. A. Moelwyn-ffughes, J. Chea. Soc·· • • 1206-8 (1948).
Ul
6
Table 2
Illustrations of tho Dipole Rule (8) Compound b.p.' 0c.
(760 JRDl) N�O 20 d4 g/al
OiCl•CHCl: cis 60.3 1.4486 1.2835 iiifta 48.4 1.4454 1.2565
ai3CH•QfCl: trans 37.4 1.4054 0.9350 cis 32.8 l.40SS 0.9347
Oi3CH1110l0i3: cis :s. 7 1.3931 0.6213 (-250)
trans 0.9 1.3848 0.6044 (-250)
Qi30i•Oi�: trans 122 1.4216 0.8239 C:lS 108 1.4182 0.8244
ft02COl•CHC02Et: cia 223 1.4415 1.067 trans 218 1.4411 1.052
Cyclooctene: trans 75 (78 •) 1.4741 0.8456 (25°) (2S0)
cla 74-75 (84 •) 1.4684 0.8448 (250) (250)
Cyc:lodecene: cis 194-195 1.4858 0.8760 (740 ma)
trans 194-195 1.4821 0.8674 (740 mm)
OiCl•CHia µ•l.27 D 113 1.5715 2.1048 (15°) l&•0.57 D 117 1.5829 2.2080 (150)
&sxception to the rule.
The anomaly of ClQi•CHl could be explained on arounds that the
iodine aay be electron donating rather than electron withdrawing: + I•Cll·Oi·Cl, however, the explanation ••ems unlikely, since the larger
of the two observed llOIMllta, 1.27 D is saallor than the JIOllent of
vinyl chloride Ot2•QiCl (1.44 D). Tho fact that tho 1.27 D moment
is about halfway botwMn that of cis ClCH-CHCl and � ICH•Otl,
rather aakes one believe that it should be assianed to the �
isoaer of ClQl-Qil. Tho reported values of dipole ae>11ents for
chlorobonzene and iodoben&ene aro 1.56 D and l.l8 D respectively.
If iodine is electron clonatina then th• expected dipole moaont for
para-chloroiodob•nzone ia 2.94 D. On the other hand if iodine is
electron withdrawing, tho expectod moaent is 0.32 o. Tho dipole
moll8nt of para-cbloroiodobenzene reported by Guryanova et. al,(9)
as 0.46 O, differs but slightly froa the difference of chlorobenzeno
and ioclobenieno Fig. 2. This also speaks against resonance forms
with positive iodine being of major importance.
Fi&. 2
7
In view of tho general accuracy of the dipole rule and many
dipole aiomont studies of cis and trans 110 .. ra of olefins, the
1eoaetric isomeric atructure assignment• of els and trans chloro-
i�thylene se .. incorrect.
(b) Dielectric Theory:
The concept of electric dipole moment was introduced into
dielectric theory in 1912 by Debye in order to accoWlt for the
effect of temperature. His theory (10) was based on P. Langevin•s
treatment of uanetic dipole moment. If a •diua contains electric
dipoles and is placed in a uniform electric field, tho dipoles will
tend to alian theaselv.s along th• field, so that all the positive
pole• point one way and all tho negative ones the other. This will
result in a separation of charges in the bulk of the material· and
hence in the appearance of surf ace charges of :such sign as to reduce
the applied field.
8888 8 8888 8 8888 8
Fig. l
Induced charges in molecules, causing distortion polarization,
resulting from tho presence of charged plates
8
If the applied field is generated by the original charges on the
plates of a condenser, then, because the field between them is
reduced, the potential difference will be loss than if there were a
vacuum between th• plates. Since the condenser will still hold the
original charges, its electrical capacity is said to be increased
by the presence of tho dielectric medium. If a vacuum separates the
plates, for eX&IQple, tho field strength may be designated by E0
for
a given charge, but when a wiiform material substance is present
this intensity is reduced to E for the saae charge. The ratio of
E0 to B is a constant, called the dielectric coiutant, e , of the
aedium between tho charged plates, thus the dielectric constant is
defined:
E. :.
The Clausius-Mosotti equation allows the calculation of either
the polarizability of a molecule a or the molar distortion polar-
ization PM from measurements of the dielectric constant of the
dielectric material for a pure substance.
Mosotti (1850) and Clausius (1879) deduced mathematically an
equation which · . .1.· be written in th'-" form
9
Where e: is the dielectric constant and M the molecular weight of
the substance constituting the medium, p its density and N0 the
Avogadro nwabor, a is a constant for the medium and is called the
"molecular polari1ability" (which is independent of field intensity
if the field is not so intense that dielectric saturation occurs.)
The quantity a is defined in terms of the equation . at • aF (4)
where 111 is the average dipole moment induced in "a molecul'e by a
field of strength F.
If the JDOlecules have no permanent dipole moment, only
distortion polarization takes place. Tho corresponding polariz-
ability is donotod by a0• If each molecule has a permanent dipole
DlOlllOnt of magnitude µ, there is a tendency for the moment to become
oriented parallel to the field direction, but this tendency is
almost random. If tho molecules were oriented with the axis of its
dipole in the direction of P, the potential energy of the molecule
would be V • -µP, but the axis will ordinarily make an angle with
the direction of P, so that
\J = - ( f c.o� B ) F ( S) which is small in comparison with kT W'lder ordinary expeTimental
conditions. By use of the Boltzmann distribution the average
moment per molecule in the direction of field is foWld to be
� ,..._::. [ u. tOS s e.-V /"'T J :. [ LLc.o�e e. f-"-F c.o�e/R.1] \ - P..V. 1- .. \t.
� u.[ c.os e ( 1 + �� c.o�-�) J I - P. T AV I
10
whore tno average is taken over �ll orientations in space. The
average of cos e vanishes. but the average of its square is 1/3 as
found uy i>el>ye
'fhe t.otal polarizabili ty h �iven by
- E � - <Ao � 3RT and the molar polarization can b� written as
E.-1 M E +2. 'f : PT"\ :.
PM : PcL -+ p� t..'i) where Pd is th� distortion polarization and Pµ is the orientation
polarizat..:.on. lmn edi.!:l.telr it is clear that a plot of PM vs. l/T
utilizing measurements of c: as a function of temperature will yield
both a0 and .,i. 'fhis tecimique is readily applicable to gases .
·rlle q�:ant:i ty 4 nNo ot.... is called the "molar polarization" due � to distortio11 or to induced uipoles, and given the symbol PM. i)y
substituting the known values for Avogadrc's number and n, the
expression tor Po reuuced to 2.54 x 10i4a.
M -
f The molar polarization PM for any substance may be calculated
from the dielectric constant and its molecular weight and aensity.
11
Since the dielectric constant is not easily determined, especially
as the values for gases arc not far from wlity, an alternative
method is frequently used. Howevor, it is known from electro-
magnetic theory that in the absence of hiah magnetic polar-
izability, the refractive index n of a medium is related to the
dielectric constant by the relation a, e. :.. 'Y'\, (. 1.0)
We then obtain from equation (9) the relation of Lorentz
and Lorens . M
f (.11) where Rtot is known as the "molar refraction". The measurement of
no can be made conveniently in an Abbe or othor type of refractometer.
Thus Pc can be measured independently from PM., and Pµ can be
determined by difference. By this means µ can be calculated from
measurements made at a single temperature.
(c) Measurements in Solution: (11) For a dilute solution of polar :nclecules 2 in non-polar solvent 1
the expression for the molar polar.izat30T' can be written as
� E. -1 . XJ..M 1 + )( � M 1 I 12) rM: X.1.Pi M + Xa. P1 M = E.+ J. f
'-where X's are mole fractions, M's are molecular weights and E and p
are dielectric constants and density of a solution respectively. All
P's are total polariiation. Thus PM can be calculated from density
and dielectric constant measurements on dilute solutions. Since a
nonpolar solvent has only distortion polarization, which is not
12
greatly affected by interactions between molecules, we can take
P1M to have the same value in solution as in the pure solvent:
!1-l M1. (. 1l) p1.rt\ = E.1+!1 . f1
We can then get the solutu �oiarization P2M by rearranging Eq. (12).
fiM =- t ( PM - pi"'l x1) 2. (.1'1)
Values of P2M calculated using Eq. (14) are found to vary with
X.2, generally increasing as X.2 decreases. This effect arises from
strong soluto-solute interactions due to permanent dipoles. This
difficulty can be eliminated by extrapolating P2M to infinite
dilution (X2•0) to obtain P2M0•
Procedures that do not rely strongly on measurements on the
pure solvent are therefore to be preferred.
Tho procedure of Halverstacit and Kumler (12) requires precise
measurements of solution densities and dielectric constants.
However, the procedu-ru lessens to some extent the need for high
absolute accuracy.
Another easier and ·more accurate procedur·e is that of
Hedostrand (13) which is given below.
In dilute solutions, the dielectric constant c and density
p are very nearly linear functions of solute concentrations X2.
E.=E1+Cl..�'l. �=fD1+bX.�
( 1S) ( .1C.)
13
From Eq. {3) �nd using Eqs. (13), (15), and (16). it is
possible to rearrange terms and obtain the limiting expression
( s.,)
By measuring the s�ope of £ vs. X2 and the slope of p vs. X2
enable us to calculate the limiting molar polarization of the solute
in solution. lf we assume that the molar distortion polarization in
an infinitely dilute solution is equal to that in the pure solute,
then
(1') fV'b. -
f 4
whore n2 is tho index of refraction and p 2 is the density measured
for the solute in the pure state. We can obtain the molar
orientation polarization of the solute at infinite dilution:
� � • ::. P2 M. - P. ct. = 4 lT N 0 • t£ f'-t � 3 ?>AT
By substituting numerical Values of the physical constant•, we
obtain
( l.�)
where P2µ is given in cubic centimeters per mole and T is given in
degrees Kelvin. The units io-18 esu-cm in which dipole moments are
conventionally given are called Debyes.
An alternative oxpre�sion for Piµ has been given by Smith (14), .
who improved a method of calculation fiTst suggested by
Guggenheim (15). lbis method requires a knowledge of the index of I
14
rofrac�ion n of th<t solution and assume that
a. � "\"\ : 'Vl. I + C. )( 2. ( 2.1)
where C, like a and b, is a constant dete1'11ined by experimont. It
follows that
This expression is an approximate one which holli� when
is small and M2 and l> are not too largo.
(d) Influence of solvent on polarization:
Until 1932 it was generally believed that, provided there was
no coapow1d fo:rmation, nur any change in the positions of the
electrons or in the configuration of the solute wider examination,
the solvent had uo influence on tlv.> polarization provi<lod tho
results were extrapolated to infinite dilution. In the same year
Muller {16) published accurate raeasuroments for chlorobenzeno in a
number of solvents, and theso have been folloW'ed by data for other
solutes, which show beyond a doubt that tho solvent does have an
appreciable effoc�. Somo of the polnrization values obtained for
chlorobonzeno and methylene chloride are listed in Table 3.
15
Table 3
lnfluonce of Sol vent on Polarization
of Chlorobeniene and Methylene Ch_l_o_ri_ d_ o _______ _
· Solvent c
Carbon disulphide 2 . �
Senzono 2.28
Carbon tetra.chloride 2 .25
Docalin 2 . 1 6
Cyclohexane 2 . (12
Hexane l.91
Polari&ation at 20°
Chlorobonzeno
75.S
81.0
81.0
83.0
84 . 0
86. 0
Methylene Chloride
62 68 70
69
71.5
16
It is appareni: from the r�sul ts that ·.1.;, t:lt� ,ueloct·ric constant
of the solvent is decreased the polnritation of the solute increases:
t��s implies that the effect is due to some kind of electric al inter-'
action and that tho correct valm� would be obtained by extrapolation
toe: •l which would correspond to a vact..&um. Muller (17) proposed
th• empirical formula
p 1-4- (.S � l\,t n·o..,) p� ( V�c.��W\)
• where k is constaHt f'o r all substances and is equal to 0.075 -
O.OOS. This rolationship is not satisfactory in all cases, but. it
is sufficient to show that the value of P\,I in a solvent having a
dielectric constant of about 2 should bo about 7 per cont lower than
the true value.
(e) Oiolectric Measurements:
The dieloctrometer employs a llC;)thod known as the heterodyn e
beat method. It 1ives reliable results foT solutions of low
conductance. A block diagram is given in Pig. 4.
C P.VS"'TA L osc.� LL ... TOf'.
VAfUASLI: rll.E.�tJNCV
L Osc.t U .. l\TOP. ..... -.. ........... .._,;_;i
Pig. 4
i7
Tho crystal oscillator aenerates a constant frequency signal
f0, which is usually about 2.6 mH:,. The frequency f of the variable
oscillator depends on the values of L and C in the circuit,
41f1f2L C. = l (.44)
The inductanco L is fixed. The capacitance C, will be the sum of
tho several capacities: Cx (tho coll capacitance), Cp (tho
capacitance of a variable precision air capacitor), er (tho internal
capacitor) and any stray capacitance due to leads. Tho output of
these two 01cillator1 is mixed in the mixer stage. Tho output of
the lllixer is given by f-f0, which is monitored bya.dotector. Tho
frequency at which f•fo is called the :.oro boat frequency. Sinco
capacitance 11 related to frequency by Eq. (24), wo can measure the
dielectric constant by a frequency method. By finding the beat
frequency at one reproducible point, t�e dielectric constant can bo
found froa the dielectric calibration table. A pair of headphones
may be used as a detector since tho output of the mixer is audible.
The Wlcortainity would be large as th� •ero beat frequency is
approached, since wo can hear '! a few cycles por second. An
oscilloscope may bo used in place of hoadphonos and tho accuracy will
bo increased gToatly. T'ne error in such a measurement will be less
than ! ono cycle per second. n,e beat frequency f-f0 is applied to
tho vertical plates of the cathode ray tube and a fixed audio
frequency fa is applied to the h�ri�ontal plates.
18
(f) Historical Preparation of C2tt2Cll
H. Van De Walle .and A. Henne (18) prepared the geometric
isomers of chloroiodoethylone by absorbing acetylene gas in a
solution of ICl in aqueous HCl. Crude QICl•OU was obtained and we.s
separated into it• isoaers by fractional distillation of the
aixture with an equal weight of n-propyl alcohol; tho a1eotropic
mixture of tho trans isoaer containing 4' alcohol h.is a boiling
point of &7.s-aa.s0• The aieotropic mixture of the cis i•o•r
containina 44.4\ alcohol has a boilin1 point of 93.6-94.0°. The
constants of the trans anci els iso•rs are illustrated in Table 4.
The configuration of the cia and trana-c:hloroiodoethylone has
been assigned by H. Van De Walle et al.1on the basis that one isome�
•liainat•• hydro1en iodide with alcoholic KOH about twice as fast as
the other. Since this elimination should ao more easily for trans
substituents (19) tho faster isomer should have the hydrogen and
iodine trans i.e. the chlorine and iodine cis:
OiCl•Oll + KOH---) CIC-CH + KI + H20
The dipole llOMnt of both isomers measured and reported by
Errera (20) for cbloroiodoothylone are µ� • 0.57 D and µtrans •
1.27 o.
19
Table 4
QiLOROIODOBTHYLENli
B.P. of azeotropic mixture with propyl alcohol
8oilin1 Point (760 am)
Pnezing Point
Densities d�
Index of (Na line) refraction
Molar Polari&ation *
Dielectric Constant *
Rate of reaction with alcoholic KOH
Trans
87.s-sa.soc
lll-114
• -41.0 -0.1
2.llSS
2.1048
1.57146
35.3
2.95
o.ss
*Determination by M. J. Errera (.10) •
Cis
116-117
0 • -36 .4 -0.l
2.2399
2.2080
1.58288
31.1
2.72
1.00
20
(a) Moasureaents:
Chapter II
Experimental
Vapor phase chromatograms (vpc)g unless otherwise indicated,
were obtained with a Carl basic gas chroaatograph using a "Heath
Built Servo Recorder" and 1/8 inch x S ft. colUtJn of 8\ di-n
nonylphthalate on 90-100 mesh Ankron ABS with a helium flow
rate of 20 al/min. Melting points were taken in capillary tubes on
a Thoaas-Hoover apparatus and are W\Corrected. The infrared (ir)
spectra were recorded on a Perkin-Elmer 337 infrared spectrometer.
The nuclear magnetic resonance (ruar) spectra wore recorded using
Varian models A 56/60 and A60 spectrometers in the usual manner.
Mass spectra were recorded on Consolidated Electrodynamic
Corporation (C.B.C.) 21-104 mass spectrometer. Indices of r�fraction
were measured with an Abbe rofractoaeter. All weight measurements
wore carried out using a Sartori\w Model 2743'. balance.� Ultraviolet
spectra were recorded using a Bockman Model DBG spectrophotometer.
Thin layer chromatograms (tlc) were run on silica gel G with methanol
as a solvent and detection was made with iodine vapor, the azeotropic
mixture of the two isomers was separated using semi-micro. spinning
band distillation column (stainless steel band). The dipole
moments were obtalned from dielectric measurements made with a
21
dielectrometor constructed in our laboratorya. 11lis instrument
utilizes a circuit similar to that reported b y Chain (21) (Fig. 5) and a modified dielectric cell b purchased from Balsbau�h
Laboratories, Uuxbury, Massachusetts (Pig. 6).
(b) Researcll Plan
I. Prepare �is and trans-chloroiodoethylene by absorbing acetylene
gas in mercuric chloride solution and then react the resultin�
vinylmercul"ic chloride (22} ""ith iodine as reported by
Beletskaya et al., (24) according to Scheme I.
II. Prepare cis and trans-ehloroiodoethylene by absorbing acetylene
gas in iodine inonoc1,1oride solution and then separate both the
isom3rs by forming an azeotropic mixture with propyl alcohol
and distilling as descriue<j by Van de Walle et al., in Scheme II.
III. Obtain correct structure assignment for both isomers from
deta:i l �d s;Jectroscopic studies such as -C-11 out of plane bending
in the infrared S)>ectrum and the chemical shift and coupling
cons tan Ls in the nucltHll' 1nagnetlc resonance spect�um.
8This instrument was constructed by Mr. James Belcher.
bcoll modified by Or. J. W. Ellis.
22
23
Scheme 1
S"tN'niBSlS OF CHLOROIODOETiiYLENE PROM MERCURIC QiLORIDB
\-\C ==. C. 4
(i) 6N Hydrochloric Acid (22)
\-\<:j c I�
Cl l
(iv) 12 in ether (24) CdI2 Elevated temperature
(ii) Isomerization (23) Bz202 and E_-xylene
;H -=- c + Hqcl I
.._I t�CltYIS c ""' o �1 l"l ' T • /50... 1:,.p 114-llSC..
Irradiation with (18) Uv light
CI / 1-1'3 c I -c. =- c.
�/ ..........._ H
12 in ether Cdl2
Cl /I Elevated temperature
.11 · 5 °/o
+ '--c. = c. \-1/ ............. I-{
'2>� · S 0/o C..I /I
'<::. C. +.Hae.II �/ -H -..)
0
PrOH (18) Azeotropic mixture
distilled
l'Yl·P.1sc:l
Cl /H -c.. -=- c.. • P-2.o 11
\1 / ......... I B· P. <31 ·S-- � ·s·ec.. 1 E.1d·1Ga.<l- a.lcoho I .
Pure trans isomer
C.l /I. 'c.. ::. c . P-z. o 1-f
H/ '- H .,
l B .. P.�3·� -qL\·O c
E.1<.b.�- o...\coho \ Pure cis isomer
Scheme II
SYNTitESlS OP QlLOROIODOBTHYLBNE PROM IODINBK>NOCiLORIDE
�c. =:.CH
J. 6N Hydrochloric Acid (18)
r <:.I
Pr OH Azootropic mixture
distilled
I Two additional Product
Cl .1 t -c.. :::=. c. . P'GO H
\.i"' ........._H :1·5' -'b'b·SoC. �- P. C\ �-<O - q l..\ ·c>°
Extract alcohol
j Extract alcohol
Pure trans Pure cis isomer
24
IV. Obtlliu tile inaices of refraction, donsities1 and boiling points
for both the isomers and compare with the values reported oy
H . Van de Walle.
V. Obtain the dipole monents from dielectric measurements Md
compare with the value report�d by ETTera.
(c) Starting Materials for Synthesis and Primary Standards
The bonzene, chloroform, chlorobenzene, iodobenzene, carbon
tetrachloride, cyclohexano, nitrobeniene. toluene, propyl alcohol,
bon%oyl puroxi<le, cadmium iodide (crystal) a.&'"ld sodium metal, �Mrf}
'Baker Analys�d' reagent gra.de. Para-xylene was purchased fror•
tiastman J<odilk Company. The arL'>iydr0>1!: diethyl ethe1·, analytic.il
grade, was purchased from Eastman ur.:anic Chemical�. Iodine
monochloride was purchased from Alfa Inorganics, Vcntron, ncv�::.·ly,
Mass. Her.curie chloride �ms A.<..:.S. code 1964 reagent �ra<le as
supplied by Speciali ty Chemical� f\i vision. The Mc-leculc::r Si(;Vcs 'M 514' Type 4A, grade 514 as suppli�d by Fisher Scientific. Co.
Acetylene was purchased from local suppliers.
(d) Purification of Mate�inls (25-26):
Benzene:
Rctagent grade benzene (500 ml) was boiled for 10 hours with 40 g of �mhydrous aluminWil Chlorid:? ;m.c' then distillc<!. Tiic
distillate was wuhed several times wi tu water an<l fine.Uy rcfluxud
for 2 hours with acetic acid and mercuric oxide. After wasin ng wit!:
water and sodium hydroxide it was rcfluxe� over sodium metal for
12 hours o.n<l then fractionally distilled over sodium.
25
Cyclohexane:
Cyclohexane wu puaed through an alU11ina colUlln 3 ca. in
diameter and 30 ca. long and fractionally distilled through a 30 ca.
fractionatin& coluan after refluxing over P4010 for twelve hours.
Only th• aiddlo fraction was saved.
Chloroform:
Cblorofora was washed three ti .. 1 vith concentrated sulfuric
acid, neutralized with NaHC03 and washed with water. After drying
over Maso4, it was fractionally diatillod under a nitroaen
atmosphere, aavin& only tho Id.dell• fraction.
Toluene:
Toluene waa purified according to Mathews (27), succosaive
shaking with sulfuric acid, 1odiua hydroxide and mercury followed
by dryin1 over phosphorus pentoxido and then fractionally distilled.
lodobon1ene:
lodobenzene was purified by drying over anhydrous calcium
chloride and distilled saving only the middle fraction.
Para-xylenec
P-xylene was dried over anhydrous calciua chloride, then
refluxed over socliWR ••t•l for 6 hours and fractionally distilled.
Nitroben1ene:
Nitroben1ene wa.s fractionally distilled after refluxing over
P4010 for 12 hours. The aiddlo fraction waa fractionally crystall
i1ed four tiaea and finally vacuua diatilled shortly before the
measureaents wore made.
26
Carbon Tetrachloride:
Carbon totrachlorido was fractionally distilled after refluxing
over P4010 for 12 hours. Only tho aiddlo fraction was saved.
Chlorobenzene:
Commercial chlorobenzene was purified according to McAlpine
et, al.,(28), by shaking repeatedly with portions of sulfuric acid
undl the acid no longer became color•d. It was washed with water
and then with dilute potas1iua bicarbonate solution, dried with
calcium chloride and distilled. After refluxing over P40lO for
12 hours it was fractionally distilled, and only the 11liddle
fraction was saved.
All these liquids were stored in the dark over Linde 4A
molecular sieves and under nitrogen.
(•) Preparations
(i) Trans 2-Cblorovinyl Mercuric Chloride:
The procedure is very si•ilar to that of Nesmeyanov as
described in Scho .. I (1). Seventy-two grams (0.28 mole) of mercuric chloride was added
to a 250 ml two-necked roW\d bottomed flask and dissolved in
hydrochloric acid. Acetylene gas was first purified by bubbling
throu&h a 25 al solution containing 7.2 g (0.028 110le) of mercuric
chlorido and then bubbled through the above solution. Tho reaction
aixturo was cooled in a salt ice bath to maximize tho yield. A
whit• precipitate of chlorovinyl mercuric chloride was formed. After
27
passing acetylene 1as for eigh hours, the white precipitate was
filtered throuah a auction funnel and dried in a vacuua desicator
over anhydrous calcium chloride for three to four days. The
filtrate was saved aud acetylene gas was bubbled through it until
further precipitation was complete. The resulting chlorovinyl
mercuric chloride was recrystallized from chloroform by using a
Soxhl•t extractor. The melting point of the needle shaped crystals
was fowid to be 121-122° (Nesaeyanov (22) reports 123-1240, Wells
et. al (29) reports 122-1230, Matsuda et. al (30) reports
123.2-124.S) . This isomer was characteriaed by tlc and also by
infrared and ultraviolet spectra.
(ii) lsaaeriaation. of tho trana-chlorovinyl norcuric chloride to
tho cis isomor using benioyl peroxide and dry �yleno as described
in Scheme 1 (ii).
lao•rization of the trans to the .£!!_ isomer has boon reported
by Nesmeyanov et al.,(22) to occur by the action of peroxides
(AG202 , 8&202, or Na202) in solution (xylene, MePh, dioxane or
CCl4) and a conversion of 90\ has boon claime d � Repetition o f the
aue procedure by Wells, ot al.,(29) using sodiWD dry xylene and
dry ben&oyl peroxide claimed 65\ conversion as indicated by the nmr
spectrum.
Tho procedure employed was substantially that of Well s , ot al .?
A mixture of 10.0 g. (O.Ol mole) trana-chlorovinyl mercuric:
chloride and 0.2 & of dry benzoyl peroxide in 25 ml of xylene , which
had boen dried over Na, was stirred for 10 hours in an oil bath at
28
90-95°
. The resulting mixture was filtered while hot and the
filtrate cooled to give 8 . 5 g (75%) of product . An additional
1 . 5 g could be obtained by concentrating the mother liquid. The
material was recrystallized from carbon tetrachloride; m . p. 74 . 5°
(reports 76-7 (31) , 78-9 (32) ) .
(111) Cis-chloroiodoethylene from i•o .. rize compound as described
in Scheme I (iii) .
Ten grau of the "cis" isomer (obtained from isomeriiation of
trans chlorovinyl aercuric chloride a . p . 78°) and 8 . 6473 g (0 .034
mole) iodine � n diethyl ether in the presence of O.S g cadmium iodide
was stirred for about two hours at 34-35° using an oil bath, water
condenser, and a mechanical stirrer . A pink precipitate of HgCll
was immediately formed . The resulting reaction mixture was distilled
under reduced pres•ure leaving HgCll in the distilling flask and
the pro�uct separated from ether by ordinary distillation.
'nle resulting product was characterized by vpc, nmr, and ir
analysis. The result of these analyses suggested that the presumed
� isomer (m.p. 78°) was actually a stochiometric mixture of cis
and trans isomers. (See discussion)
After removal of ether, th'e reaction mixture was treated with
n-propanol and subjected to spinning band distillation to resolve the
geometric isomers as reported by H . Van do Walle et . al . , (Scheme I
(iv) ) . The distillate fractions with boiling point ranges 87.S-88.S
and 93.6-94 .00C were collected and analysed by vpc and nmr .
29
(v) Cbloroiocloethylene froa iodine monochloride and acetylene as
�•cri.,.d in Scbomo II (v). Ten al of iodine .,nochloride was added to a 250 ml two-necked
round bottoaed flask and dissolved in 40 al of 6 M hydrochloric
acid. Acetylene gas was fint purified by bubbling through a
solution of 7 . 2 g (0.028 mole) of mercuric chloride in 25 al of
H20 and then throueh the iodine aonochloride solution which vas
cooled by a salt-ice bath. A colorless oily solution formed as a
second layer. This layer was extracted with diethyl other and the
etherial solution subjected to distillation using a spinning band
column. 'nle fraction boiling at 114-5° was collected.
Th• vpc, ir and nar spectra of tho product mixture were
critically compared with those of obtained in reaction (iv).
(f) Dielectric cell and measurements :
A llOdel 2TN20LV dielectric cell purchased from Balsbaugh
Laboratories , Duxbury, Ma.ssachusett•� was modified in our
laboratory (Pi&. 6) . This cell permits dielectric 11ea1ureaents
up to c •l.O and uses 1 2 . 0 to 15.0 ml solution. Capacitance changes
were measured uaina the tunine aechanisa of a war surplus model
BC.l21N frequency aoter, in place of the u.ual precision linear
capacitor. Althoueh the BC221N provides a hi&h quality gear train
and vernier dial .. chanisa, the capacitance 1• non-linear with
respect to dial readin1s, hence an accurate calibration technique
i• required. 'nlo solution used in these studies in general bad
JO
concentrations in the range l o-2 to 10-3 mole fraction (x) of soluto .
The solutions are introduced into and removed fr<>11 the cell by raoans
of a vacuum from a wator aspirator. The total volume of solution
u.sod for each dielectric aeasuroment was 25 Ill . All of the air that
entered the cell first passed through a drying tubo containina
indicating Driorite . Generally four or five solutions of varying
coucontrations wore used in obte.ining the plots of mole fraction
Cx) vs . dielectric constant Cc ) and the density i> ) for a given
compowid . Because of the high stability of this instrument, each
samplo was allow�d to thermally equilibrate in the cell for five
JAinutos before a reading was aado . In order to maintain a wiifora
temperature thouahout a measurement, the portion of the cell
containina tho solution was i1111Dersed in a constant temperature
+ bath at 25.00 - o.osoc.
(g) Dielectric Calibration : l3J) Tho dielectrometer could be calibrated either in terms of
capacitance or directly in dielectric constant as a function of
dial readina. Although the capacitance calibration method is more
convenient and faster, tht1 latter method was elect�d because of its
higher accuracy.
A di1ital calibration of this instrument was achieved by a
nonlinear least-squares fit of the dielectric constants of a series
of standard materials as a function of dial settings . The physical
constants of the dielectric standards are illustrated in Table S (a)
and S(b) .
ll
Tilo parameters of the calibration function (an orthogonal
polynomial) wero obtained by the use of l'rogram numbe;r l . (Table 6)
lbis program is written in Fortran IV for tho IBM 360 Operating
Systeia . This proiTam calculates the calibration parameters
for polynomials ranging from third order to sixth order. (Table 7)
The standard deviation of each polynomial was calculated by
program number 2 . The polyn01t!al of minimwa standard devistion
was selected for tho calibration function . These parameters were
used in program number l, to obtain a calibration table (soo Table 8
in results) .
(h) Dipole moment calculat ions �
The dipole 11oment of nitrobenzene was calculated using the
Gugeonhoilll (15) p:rocedure by plotting dielectric constant (e ) vs.
mole fraction (x) , and indices of refraction square of the solutions
(n2)· vs. mo lo fractions (x) , and using Eqs . (15) , (21) , (22) and
('O) (Fig. 7(a) and 7(b) .
The dipole momont of iodobenzone was calculated by the
Hodestra.nd (13) procedure by plotting dielectric constant (& ) vs .
mole fraction (x.) and clensi ty of the solutions � ) vs . mole
fraction (x) and using Eqs. (15) , (16) , (17) , (18) , (19) and {20)
(Fig. 8(a) and 8(b) ) .
The dipole moments of cr,loroiodoethylene are measured in benieno
(Pig. 9 ( a) and (b)) and cyclohexane (Pia. lO(a) and (b)) solvents .
Tho dipole moment was ootained by tho use of computer program 4.
32
This program is written in Fortran IV for tho IBM 360 Operating
System. This program calculates the least-squares paraaeters
(slope and intercept) and utiliies thea in tho calculation of the
dipole 1!0meat.
The results obtained for iodobenzono, nitrobonzene, and
chloroiodoethylono aro lllualrated in Table 9 (a) , (b) , (c) and (d) .
33
34
Table 5 (a)
Phlsical constant:> of the dielectric standards
Formula Compow1d Dielectric 25 no B.P. Nau Constant
t
C6Hl2 Cyclohexano 2.015 l . 4236 80.2 (740 u) CCl4 Carbon tetra- 2 . 228 1 . 4580 76.4 (750 am)
chloride
'6116 Ben1ene 2 . 274 1.4979 79 . 6 (743 llllD) ct,HsO!l Toluene 2 . 379 1.5215 llO. 0 ( 745 mm) Qi(;l3 Chloroform 4.720 1.4423 61.0 (750 DID) C6HsCl Chlorobonzeno 5 . 708 1 . 4942 109.0 (742.2 mm)
Tablo S (b)
Oielectric const&nts of nitrobenzene in benzene
Compow1d Mole fraction Dielectric Cx> Constant
c O.b402 2.750 21.522
o . �891 3.000
l . 7123 3.500
laonzene Solution
2vanclenbroucke , A. C . et al . , "The Review of Scientific Inst. 11 Vol . 39, S58-S62 (1968).
Chapter III
(a) Results and 1:>1scus11011:
(i) Trans-Chlorovinyl Mercuric Chloride
Thin layer chromatography shows a single component (Rf o.52 cm) . The infrared spectrua shows "C-H in the region between lOSo-.:uoo cm-1
which indicates olofinic C·H s tretching, "C•C at 1570 cm-1 which
indicates wisaturation and �C_H at 940 cm-1 which indicate� out of
plane C-H bending vibration£ for olefins (Fig. 11 (a) a (b) . Tho
strong band at 940 cm-1 is clearly assigned to the trans isomer (34 , 35) .
Tb� compound exhibits ultraviolet absorption with �StoH 212 which is in max
excellent agrHment with the vs.lues reportod by Friedlina e t . al (l6)
(212 mµ) .
{ii) The iodination of trans-chlorovinyl mercuric chloride
Tho product obtained from the iodination of tran!ii-c!llorovinyl
morcuric chloride was ch&racterized by vpc at 115°. The chromatogram
shows one major peak with a retention time of 1 . 12 min (Pig. 12) .
The proton nar spectl'Wll shows an AB pattern with JAB •ll . S cps and
6AB•l0 . 7 cps which cl•arly indicates the trans configuration (Pig. 14
(a) 6 (b) ) . Tho infrared spectl'Wll shows vc-H at 3080 cm-1 which
indicates olofinic C-H stretching, vc.c at 1545 c:m-1 , which indicates
wisaturation and ac-H at 902 c:a-1 which indicates olefinic c-H out
of plane bending. The strong band at 902 ca-1 is characteristic of
trans configuration (Fig. 15 (a) & (b) ) . Tho mus •pec:trua shows a
base peak P-127, in conjunction with an isotopic clust•r at (P + 2)-
3..>
127, characteristic of chlorine with m/o • 6 1 . Tho parent peak has
a/o • 1B8. wi'tl1 a prominant P .... .! z.t ro./e • 190, c:haractoristic of
chlorine. Other spectral feature� may be fowid in Table 10. 11\e
boiling point and refractivo index are fowid to be 115° (750 ma) and n55 1 . 5831 respectively. Tne dipole moments measured in benieno
and cyclohoxane solvents are founu to bo 0 . 549 D ! o . os U and 0 . 5 19 O + - o.vs D respectively (Table 9c & 9d) .
(iii) lsomerization of the trans-chlorovinyl mercuric chloride
The thin layer chroutogl"am of the product shows one major
component (Rf o . 73 cm) . The infrared spectrum shows vc.H in the
region b@twoen 3000 to 3075 ClJl-l which indicatos olefinic C-H
stretching, vc•C at lSSS c;m-l which indicates unsaturation and
vc .. u at 930 cm-l and 692 c1rl which indicates out of plano C-H
bendina vibrations for an olefin. 11\e two strong bands at 930 c1rl
and 692 Clll-1 seem to correspond to th• trans and cis isomers
rospoctively (Fi&. 16 (a) & (b) ) . This indicatos that this compoWld
is probably a mixture of £!.!.. anti trans isomers. A detu.ile4.l 1unr
investigation by Wells et al.,(37) revealed that indood this product
is a coordinate complex of l : l .£!.!_ and trans isomers . The nmr
spectrum of this compouno is identical with that reported by Wells
et al.,(Fig . 17) . The compoWld t)xilibits ultraviolet absorption
with A=H ;n1 11µ.
(iv) Isolation of cis-<:hlorovinyl mercuric chloride from the cis
trans llixtun of chlorovinyl mercuric chloride
The cis-trans mixture of chlorovinyl 11ercuric chloride, was
36
treated with pyridine giving the lmowu complex of tho trans chloride
with pyridine , 111 . p . a•0, leavtnz l� rotdduo of pure =!!_-chlorovinyl
urcuric chloride a.p. ss0 (38) . £.�:-chlorovinyl •rcuric chloride
does not fora a complex with pyridine . The cis iso.er obtained by
this •thod was very poor in yield,
(v) Iodination of cis·trans aixture
The product obtained from tho iodination of the cis-tzans mixture
wu characterized by vpc at uso . The chromatogram shows three
major peaks with retention ti.mos of l , 12 , 1 . 36 , and 2 . 00 ain. respect
ively (Pig. 13) . '111• first peak h .. t � tho samo retention time as
that of pure trans- chloroiodoothylO'lle . The second peak corresponds
to the cis isomer which wu identified by nmr. The third peak
corTetponda to some new co11p0Wld. The infrared spectra of the
product mixture reveals both geometric isoaors a.s well as a new
compowid exhibits vc-H at 2925 ca-1, characteristic of saturated
hydrocarbon (Pia. 18) . The nmr spectra of the product mixture has
two Al patterns centered at 5•392 cps and 6•409 cps corresponding
to tho trans and � iso•r• respectively . The absorption at 6•419.
and 6•135 cps, correspond to tho olefin and methylene proton of
tho third component (Pig. 19 (a) g (b) ) .
(vi) Isolation of cis and trans is01Mtrs of chloroiodoethylene
The three component aixturo, as described in (iii) was treated
with oqual voluae of propyl alcohol and fractionally distilled using
a spinnina band column. The two fractions · with boiling ranges from
37
87.s-sa.s0 , shows JAB•ll.S cps and 4AB•l0 . 7 cps which clearly indicates
tho trans i1omer (Pig. 22) and the fraction collected between 93Q6-
�4.o0 ahowa JAB•S.8 and 4AB•4 . 4 , correapondina to the £!.!_ isomer
(Pig. 23) . The reaainin1 third coaponent was not identified due to
poor yield,
(vii) Chloroiodoethylene froa iodine 110nochloride
The cruel• product wu characterized by vpc at 11so . The
chro11&to1r• show• four peaks with retention •iMa of 0. 18, 1 . 12,
1.�6, and 4 . 12 min (Pig. 24) . The peak at 0 . 1 8 ain. is probably due
to Cili�Cl2 (18) • The 1ec:ond peat. has the same retention times as
that of pure trans chloroiodoethylene obtained froa trans chlorovinyl
mercuric chloride. Tbe third peak i• very saall in intensity and
corresponda to !:.!!_ chloroiodoethylone as identified by its nar
1pectl'\lll. tt. Van de Walle et al.,reports that this iso•r was
obtained a.s a aajor product by this method. Tile fourth peak with a
retention tillo Ari- 4 , 12 min . is du. to SOiie higher boiling now
product. Physical constants for the trams isomer· with those reported
by H . Van de Walle et al . , are listed in Table 11 .
Conclusion and Sumary
H. Van de Wall• ' • and A . Henn• ' • structure assian-nts for £!.!_
and trans chloroiodoethyl��me are conoct. The di polo moment measure
ments Md• by l:rnra were :aiauaiped and iisaccuTate. The correct
dipole llOllent for trans isomer ii 0.549 D t 0 . 005 D in benione and
O . Sli D ! 0 .005 D in cyclohexano . 'nle io4ination of trans chloro-
38
vinyl mercuric chloride proceeds with retention of confiauration .
A possible aocbanisa is the S5i typo
C l / H ' c. :: c.
/ ">... _, c- l H � · Hs :r. �
c. I / H 'c. = C. + H ca ' ' I
M / "- .t
Tho chloroiodoethylene does not exhibit any ultraviolet
induced isomerization. The ir, nmr and mass spectra for the
chloroiodoothylene are reported for tho first time.
(c) Su11ested Research :
1 . Oeteraine the structure of the cia-trana coordinated species
obtained from isomerization of trans-chlorovinyl 11ercuric
chloride by x-ray diffraction .
2 . Develop synthesis and aeuure the dipole moment of cis
chlorovinyl lllercuric chloride ., The dipole aoaent reported by
Neameyanov et . al .,(39) for £!.!_ and trans-chlorovinyl mercuric
chloride as 2 . 76 O and 1 .64 D respectivoly. The dipole moment
of cia isomer is incorrect because it is not the pure cis isomer - -
but it is a coordinated species of cis and trans 11omor1.
Recently Nesaoyanov et . al.�40) reported a now method to synthesize
the pure cis isoaer.
l . When trans-chlorovinyl mercuric ·chloride was treated with iodine,
at room teaporature , in diothyl ether without catalyst, it gives
five additional products . Isolate all these products and
39
detersaine their structures .
4 . The iodination of the stochiomotric mixture of the cis-trans
chlorovinyl mercuric cnlori<Je in the presence of diethyl ether
a.ud cadmium ioaido at elovateu te1!'1porature gives a third now
compow1d. lsolatE' t110 product ana <letermin" its :s t ructure.
S . Confir11 the kinetics of dehydrohalogonntion of ch loroiodoethylone.
6 . Determine the mechanism o f the iodination o f chlorovinyl mercuric
chiorid�.
Table 11
Chloroiodo��_!l_ylene
tt. Van ue Wal le • s Value
cis trans aVpc CollJ:>Onent --ICl + hC•Ch --
B . P . of az�o- 9:5.6-94 . 0 87 . 5 -�IJ . 5 8 7 . S - �8 . S tl'Opic mixture with propyl alcohol
B . P . 116-117 lll-114 114-1 15°
n5s 1 .58288 1 . 57146 1 . 5831
" 0 . 5 7 D 1 . 27 !} o . ss I>
8Trans conformation a$ determined oy nmr and ir spectra
2 of
40
/\/V·--� o10_T_(:r- ; ·:)"�-- -;;1 . �� - "( ::.::.: :.:: . - -·p . (1' - C::JA - · -
N ·-
_ _ --·- ·· ··1
r0 (ij � ; : i ce· (( 111 - - - · · · - - - - .r-,11- - - -· - · · - · · -· - · f
I
> - - �,: : !=---,vv·-1i ' r - - - ··-· N
I
: '-:-:[· I : <?._J '--··-Il l· � I
I : I '---vA./v"-- :1· I <._0 (1) l 1 1 I I '['' • :-:::
I u (( --·-- - -- ---
' (C: I -.../\/\/'- ---·-----! i � L: �R-�" :"c-���:
1·;:-:�-==:?,I,,
.:-:" :·. TH--
� I ,-- --- - "
I -- - -- - ---1 I i.._ I I - - -· - - -
I I Cc� r - - - - -....,_; - - -- -
·
I I I lO -·- "° I (.)
1P11, . : I : t•1 r r-11 I : cc Lr. I I : ·---./VV' - '-\
I I I
--;; I I I �
I I I
X I
I 1 1
I I : r· OL _ I : I I I .: . 111· : :
0, N I I 81 CY. II• I I I
I I 1 1 I I .JI
I 11 �I
I �I
I I ><I I I I I I I
I I I I I
r() I 1 ·I
J I I
r--: (_" I I I .. I "
I (•- -· --··· .L. , ,-- , ... j I I
� I ./ r' I ; <( bj�1liJ fd i I
I I
' --0- 111· J -�- � n C\J f.-1� f,''�' ' 'r.- [�F - _111, > 1--�,, 1. �- - ,. . .. ,, --·-.
�-0)_ I cc (\j UL 0- (.t') - ---- --..;:::./ (•_
I .. - -· ... . . _ r
I .. .. -- ·- - · - -· .. -L . - - - -- -· - · ·- . . l . . .... . . . . . -· · · .. . · -
l{) c�
I -1 I
I I I I I I r I I I I I I
I 1 I I I I I I I I
0 I v.: I > I
I I
( ( ( <.. r'
c.: C' L <' L. (rJ :.1 -�-CJ �� lJ 0. (•.
< .-; ... (.I () (1) I 0 �: :..-..... "(} 0 � . 0 -e .
_q _1_
F:i.t,�l:Ce 1 o C:i_j.'Ctti·t of t,hc Hotrod.j,..j1.:_: ... �3u.·:;. l•?i:;�i�.:tt\�5 for Dicloctric"c.�,ns·::.:-�nt :-�s.;.cu1·c��.:.0rt"c
C i � c;, c5 , C7 C9 c10. C't 1 C1 2 C1 4 c1 5 c16
�1
C1 J, C1 a. C20
Cl7
:=�. P.10, 11 7, ::.1 9 RJ, :t7, n.s, �1u, rrzo :::>'• ·'"" as ?.5, R1 J �j, R1 5 �:1 1 :12 R; 4 �13 �1 �3 �l�
VI V2 . VJ Vl} :c .. ''• 51 I � J') - · J � ). p--.c .::> 1
p�? ..,_
l� 13
1 L!·O·J�::·t�:':. tl·:o-g<:.!1g \:'�r:f.�blE: 0, 1 .. ;:'.f � 600 volt �;, 1;.::1· . 4 �
O .. 30.v�·1t::. ft :i.r t�i:-!:·:!el'
33.5-·:::.:nf. \·c.1·i�.':ile 0 • 0� ';�:.!f • ?.Ii CJ.. 0.01 -:·!.f, 60•J ... 1.rolt. r:t:p,.!:;,."' 8-r.1.£'. !;.50 •. volt eJ.a·::t.;:.·o1;rt:l.c: 0. 002 ... r-,f. :i:ic a I' . 0 . 25�.;1).fe oOO-•.rolt p-1:::01" II p I , "'."'\ l ' l ' ') I • t.;-... !:�- . · ;·:;....1 · -·,T'J ·c z e:c 1�2'0.l.y�::.c 1 On:n.f. 25 .. ";.roJ.t� �lt3(; LroJ.�:-·l:,ic
500 .. 0�:!:1 1 .-.-:·: .. 1 ... ::, t "t'f'\l'."I '"'''"1 �- • . ,. •. .:. vu ... ,l-..,'-' �· ··· '"':iu,·.:. t..i l, 1 5 , 000 .. o:�:i 1 • . ::.-;.t·� 25 ""0 ,...!,,. • • ·- � . .!. t '-' '-' ... ... ...... . . , ...... � � 0 . 1 -:�:c��:"'.::l t-�;:.:.t".: 1 5v'\ '"l'"'vi 1 . ,. , .:. � �· ... :.- .. , : • • -,,. 'J .,,
75, COO-ch:1 1 ..:.-.ltt 2000.:..obr-;. 1 -·.::-. tt
'!\.�bes, �tc .
6SJ7 6!P"" • • v\J
. . 6sA7 6J5 Cri·zt:.1 0 .. 5: :��. . :-:;; t & •• 7irbe �:.::.:; : t '1.�11 ··:,·.:v-;:.��.:; s ·.·ri tc:�: Pi:on'� J:-..�1� Scc:·:�t fv;· cv:::·:i .. :;.:!. :-:i:·e cor;:1'1=t-:-r to
(liel�c �ric c8l.1-Scc1���t f:>1 .. co::.::}.�] .. t:i!'·3 <.:0:1::r.:� to� to
C0�_J4 .. 2 : � . . c : C:i:�1.;2 . 6. :� �
42
3 . 1
3 . 0
2 . 9
2 . 8
2 . 7
2 . 6
2 . 5
2 . 4
2 . 3
2 . 2
2 . 1
2 . 0
1 . 9
r I I � · t I I i r : i i i.. I ! I l ' i
i . ! � l I ' ! r I i ' l l L � l ' .
r . . ! ,,' ' .
,,, .·
,.
· .... I
--- ·- . .. --a
,'
·'
'\.
,/
N c
,..... Q) 1-t C1l ::l cr' (/) c 0 •rl .µ u ro 1-t 4-1 <J) 1-t
4-1 0 >< <J) -0 c H '-....J
--·' ·�� ....... ��---���---��....,���· 1 2 3
Mole Fraction x x io-2
t a)
4
2 . 037
2 . 036
2 . 035
2 . 034
2 . 033
2 . 032
2 . 03 1
2 . 030
2 . 02 9
2 . 028
2 . 02 7
[ I I j
r I ; I .. I ' t r ' I I j l ' I ,-! l r ' I -
r I ' , i ' . , 2 . 026 i:l
i
.. 0 ' , I I ' , I
2 . 025 l '--·'------1----'--
1 2 3
Mole Fraction x x 10-2 (b)
4
NITROBENZENE IN CYCLOHEXANE
..;::.. ..;::..
2 . 39 r 2 . 38 1.
I
2 . 37 ,_
I 2 . 36 l-
. , 2 . 35 I I '
2 . 34 l·-2 . 33
I I ' I
2 . 32 I
I J· I . l
2 . 31 I r I
l-'
2 . 30
2 . 29
2 . 2 8
2 . 27
, , • , I ,
I I �- I '
I I .'
I
I I -- I ' , ' ·' ..
\.f I ' ---£--• •• ,._,,., - ., .,a-
1 .
I/
2 3
Mole Fraction x x lo - 2
(a) , 4
a.
>µ 'M C/) i:: v
Cl
0 . 92 0
0 . 91 0
0 . 900
0 . 890
0 . 880
0 . 870
0 . 860
t � � ,P I , I , r/./ y' t
IODOBENZENE IN BENZENE
Fig . 8
1 2 3
Mole Fraction x x l o-2
(b)
4
+:Vl
' t 2 . 296 ! .
i . 2 . 294
2 . 292 I . .
2 . 290 I '.-j I
2 . 288 � l i
2 . 286 ·•
2 . 284
2 . 282
a. � µ •r1 Vl � (!) a
2 . 280 .· p . // ' .
2 . 278
2 . 276
. .
r ,,'
): , ,, � �.
(_".- -·�· . . �� ...... ��--��.._�__,---�__,...____.... 1 2 3
MoJe Fraction x x 10- 2
(Cl)
4
0 . 91 0
0 . 900
0 . 890
0 . 880
0 . 870
0 . 860
�
t _/ r. I-
i· r r r- // I ; tr r
1 2 3 4 Mole Fraction x x i o-2
(b)
CllLOROIODOETHYLENE IN BENZENE
Fig . 9 .::.. °'
2 . 054 i.
2 . 052 l l_ ' I i 2 . 050 '· ! i
2 . 0� 8 � ' .
2 . 046 '-i I j
2 . 04'1 I
. . I '
2 . 042 l r I I
2 . 040 !_ ' I I ! 2 . 038 l.
! ' i
2 . 036 '� I t
I 2 034 I • 1-l I 2 . 032 l . 2 . 030 '/ '- -
' I ' , , ,
' ' ' '
I
I ' , ,
c
I
1 2 3
Mol0 Fraction x x 10-2 (a)
a. >. µ ..... (/) s:: <!) 0
' -_ .. 4
0 . 83 [ I I 0 . 82 r L
0 . 81 � � 0
o . so r / o . 79 t
I /o /0
I ,0 0 . 78 [ ,//
' ,// 0 . 77 (.·:::· �-_!_---1..---..L---:--
1 2 3 4
Mole Fraction x x 10-2 (b)
OiLOROIODOETHYLENE IN CYCLOHEXANE
Fig. 1 0
A '-.!
-. . I J i . . I ! 60: i" i
I I I J 40t !
i I 201 f I I I I
O ' ...___ _____ _ _ _ _ _ , --4000
------ ---
----------- .
--------------··
·
--
--\--· -· ·----.. - ·- . -·"·-·--·
--
- ··--- -_ .... -----·-
·-
__.
. '
.(l " i
Jl---
I
I I I I l i
I ! j l
I I l
. 3500 3000 2500 ·------: 2000 1500
Frequency (CM- 1 )
TRANS CHLOROVINYL MERCURIC CHLORIDE
Fig. 1.'l (q ) .+::>. 00
j I
60 I r �----\ t '
40 I r I i I ! I
20 L I I '-'---1- -.-�
1300
[ �
... ____ ...._ __ _
1200
I I
llOO
\
\ � i �
\ (\,. lJ l
I (
·-- - L --------L·--------• - r • , I 1000 900 800 700 600 500 400
Frequency (CM- 1)
TRANS CHLOROVINYL MERCURIC CHLORIDE
Fig . '.11. (b) � \D
t I
L. __ ---'J L__ VPC OF TRr\J\S CllLOP..OIODOET!�Y. : . :E
F i g . 1 :2 --·-- ... --· ' • ... \ • I ' - ·-� d .\ t V 1· ._.
1- i g . 1 3
so
I\ :I I
r
J
400
f
fig. 14 (a)
51 300
I . --r ,�----·· -· - --�--·------"'-.,._ ... _ .. •- •: ,.•:,. I •
I , , · .. '
j •
. �., -r:.::::; ":> c::=::::::=::_ --. ,
-· - .��·----------
------------------ ----·------ -------
52
r.l -
.
i ,, I . �· r I I
. 1
1 . 20 l I I I J j ) . ::.. ! � ; f . l ) . 301 J -. I ,. I
. 40 � I . so � I
. t-0 l .j 4000
-- -350()
' 3000 2500
Frequency (cM- 1)
TRANS CHLOROIODOETHYLENE
Fig . 15 (a)
i
2000 1500
(/1 vi
�
�· c
i
54 0 0 � 0 0 LI) 0 0 \() 0 0 I' 0 0 00 0 0 0) 0 0 0 rl
0 0 N rl
u.l z u.l .....:l >--� U.l 0 Cl 0 H 0 � 0 .....:l ::i:: u U) � � E-<
-·--J � --------· -----··- -- · .. ·--------:::> 0 0 0 0 0 .�
,..... .0 ..._,
LI) rl
� ·rl ii.
r
40 l � 20
I o_.
4000 3500 3000 2500
Frequency JCM-1)
CIS-TRANS CHLOROVINYL MERCURIC CHLORIDE
Fig . 1. b (Ci )
l ii
..
2000 1500
1 , t l
i
Ul Ul
80
\ / 60 I I /
40 :_
. .
20
ll !1 u
-'·-----..... . --- -
1300
\ I
\ I
t�i ! :
�
I -------- - ·---- '*'�, .... _ .. ___ ... __ ...... t .. -----...... - .,_ ............ _ _ ' . -·---·--··-_ ... , _ ...... \----··-· .. -·--... •---------1200 l lOO 1000 900 800
Frequency (CM- 1)
CIS-TRANS CHLOROVINYL MERCURIC CHLORIDE
Fig . 1.{,(b)
700
I I I I j
600 500 400 (Jl °'
\ I
4.0 5.0
400
I I I T" "
r-1"°: _ .... . I I ,-, -. 'l 11 57 I\
300 ! , I
l ;j !I I
I I\ l , ------i
l
I · I I I
I I .
\ ! �----. .' t j , 1�'f' '.!j \
· ·. ' ;
• 11 I I :I j : ji f
1 _J __ ..- - -
I I :1 I
� 1, � � � _,, , '11 } ·1 1 · i
j • . I , / /' I . I? I ; 1 "j I ' ! ".\ .. � l \ . I '· � • \ :�\ \ I \ l..} I, ' ' I ·' ,.I ' I .• . ' ·'""" J ' ·' • 1., • ·' • '/ • ;· • • . , · '. •· . _. • • 1 i !.J-··.' j I " ; . 1 r • , .1 •'I •t '1 t I '1 I • ·,. •I • • '...-• I ' I f ' . { .. " • I I . ' l ' '· . . . , . · -- I . I I . "' 1 -·-,·,--.1 -•""' ' I I
I. ·-___ .. ___ -·-· ... _ _....,..,,,
1i, \ , ""� l ' ' "" ' " ' I . "A. J j\,)11,t .. '·, i I . . ' • ( I . ' • \ ,"ii . . . ·1-;J\:'. f , .,I I 1 1 1 ' . , j'j J . • '; ' "
: l .; : f . .. J y ., ' '
·' •I I 1' I •I I . I I I. I f I } I
�:.:x OF CIS-TR .. \.'.!$ Cl!LO:<.Ov!;·:�T.:::;�cURIC c. 'UD!D.2 : :J '.(Tl:;<::
Fig. 1 7
·� .r.-.. �-W••"'-"• '� .... ...,., l,._.,�.__._,..•_.��..._..-.I__.,.,,.-.,.�..,....._, • •• • r :--r. � . ... • .• - :..?;:11• '.., • ... ·� • .. _..
C:::..J ·-,..�--· _.l ..... � .... ,!.,, ___ _ • _ • .t .,._ l.-.-• .... _;_,,,.._.:,.,,__ ...... l ....... 1 •• �- .,. ' .. 1n .... ! .. , . .. .',
0
0
<:: . :: .. _
0 .-i
� n_ ..,, ... _... �
·----�L-----__;L-.----t......-L--• 0 N
0 LI)
0 0 LI) .-i
0 0 0 N
0 0 LI) N
0 0 0 I"')
0 0
r I
0 0 0 .q-
58
U.l z U.l � >-
r-.. � "' rl t..t.l � I 0 � Cl u 0 � ...._, H M
0 >. a: eo (.) 0 -� s:: � t.t.. <I) :i:: ;:3 u er' <I) (/) H
� t.t..
E-< I
(/) H u
0
0
----
�
(----�-- -·-·-
- - ------ --- ______ ;.:;::..-:-.. -::-. ---·.;-.:..�.
__C ______ � �����,���---'-��� ....... ��-\�--'L-� \.
0 M
0 N
:::> ..,.., 0 :::> If)
0 -a 0 "
I
I
1 ·.
I
J 0
M
59
0 0 �
· o 0 I.I)
0 0 '°
0 0 "
0 0 00
0 0 °'
0 0 0 M
0 0 M M
0 0 N M
0 0 t'") M
[..U z t.Ll ....:l
,..._ >--::i:: E- ,..,.
M Ul .J. I 0 \.. � Cl u 0 c( ........ ....... ....
0 >- c:::::: OJ 0 0 "M s:: ....:l u.. (1.) :I: ;:s u er (1.) V) $-t � u..
E-I
V) H u
. -. I I I I I I I I I ' I I ' I --, --r-·-�-.,---r----r----r----· .... , --·-, .-....... --...--.,.._� . ., ... --· _,_, --f'1·, �--r'-_..,..-�-,....... .... ---,r----.-···
400
I I 1 · I 1 , :
' I , 'J • I �
60
300
' ... ;,.
1v\) I AJ . f \._} r r ij 1( v----�-------------:1 I I I ·
I W·I:<. OF ,SIS-TRPJ'IS CHLO:;.'.)IQDOJ:Tf-l';'Ll!�:E �·:I XTU!<.E
.. t • ..,. -· '· • I Fi� . 19 (r,) J t t I • I . ... ., .... . � .•• , ,...__ ..... . �� .. ., . .. ......... ...... - · tr • • .•
_I __ ·' · ..... .. _ . . _ .......... ...... t. ____ .... ...... ..! .... ...... -;............. . ..... . '·� ... .. ...... •
-�
-·-·----
J :r II\
�r r-f{)
!!l ,, en t?<
l Toi
rf" l{l
r? rt)
;) .s ,,
� V\>
\JI Of �
er ... 0
�
� � 0
1 .::r
r:-,.... 0 .:r
�
-3" � ,, " vo
� T 1� ---.. ______
o:J I th " dl r,,.-<
.J�-0
,�- ...... :h ·-- , -�) � --�
61
i:..Ll z i:..Ll -:i >--:i:: � i:..Ll 0 Cl 0 H 0 Ct:: 0 -:i :i:: u
U)
� �
Cl ,....... � ,.0
.._,
� I (j) .-l
t.t.. tl/) 0 ·r-i
:::E: :=i
t.t..
Ct:: � u i:..Ll 0... U)
Ct:: :::E: z
Cl i:..Ll Cl
� 0... >< i:..Ll
I I . i l
I I 1 l •
. .
\ I i
_L ___ l l _______ J Vpc of 8 7 . 5 - 88 . S0c Fraction Vpc of 9 3 . 6- 94 . 0°c Fraction
F i g . 20 Fi� . 2 1
62
63
400 300
Ni-iR SPECTRUM OF 8 7 . S - 8 8 . S0c FRr'\CTION
,..'.--J__.__.1 , F�.g1• 22 '.-J.-...'----'-··4··..:-�. --.!..--·--··· .. --·· ··�-�J .. --!.-.---·�..l--1..,__:._...1--_J __ ...._:." . .. :. _ _ ' t-......-1--LJ- ' .-!.-....?..-.J_.,,�-··-·....!--'-v-L _ _ . ____ ··-- :···-··--·· !, ___ .__ ! . • ..
�. I, r-'
-�-'
--a ·� f r- I r -r--" r== 1 ,.
64
400 300
NMR SPECTRU'.' ! OF 9 3 . 6 - 9 4 . o0c FRACTION
Table 6
Polynomial Coefficients
1HE POLYNOMIAL OF ORDER 3 THAT BEST FITS THE CURVE IS
POWER OF X
· o 1 2 3
1HE POLYNOMIAL OF ORDER
POWER OF X
0 1 2 3 4
1HE POLYNOMIAL OF ORDER
THE
POWER OF x 0
. 1 2 3 4 5
POLYNOMIAL OF ORDERS
POWER OF X
0 1 2 3 4 5 6
4
s
6
COEFFICIENT
- • 2 7 1 1 7939E 01 0 . 45721270E-02 - . 95992527E-06 0 . 10751020E-09
THAT BEST FITS THE CURVE IS
COEFFICIENT
- . 44698534E 01 0 . 86278394£-02 - . 42467873E-OS 0 . 12202466E-08 - . 1336Jl854E-12
THAT BEST FITS THE CURVE IS
COEFFICIENT
- . 62134361E 01 0 . 136618SOE-01 - . 9 7969305E-OS 0 . 41478820E-08 - . 87395922E-12 ·o . 71985545E-16
THAT BEST FITS THE CURVE
COEFFICIENT
0 . 12427124E 04 - . 43289852E 01 0 . 60851015E-02 - . 44207636E-OS 0 . 1 7529069E-08 - . 35986025E-12 0 . 29895988E-16
IS
66
Table 7
Function Evaluation and Standard Deviation
v "
1 0 0 0 . 0
y F U 1\lC T I Oi·l · -
1 . 0 0 0 l . 0 0 8
1 3 64 . 8 2 . 0 1 5 2 . 0 1 3
1-'t.4.6 • 3 . . . ··-- -. . .
14·61 . 3
1 50 5 . 2
- 1-669 . 9 --·
1 7 9 5 . 0
2040 . 0
2.666 . 1 .. - - · · - - - · -
32 59 . 4
?. . 2 2 8 2 ·. 2 1 8
2 . 2 74 2 . 2 5 5
2 . 3 7 9 2 . 3 6 2
·- ··- . 2 . 7 5 0 -----·---· 2 . • 7 4 7 ..
3 . 0 0 0 3 . 0 2 '�
3 . 5 00 3 . 5 3 3
4 . 7 2 0 -- - ·- - . 4 • 6 9 2
5 . 7 0 8 5 . 7 1 5
S TA N D A R D D E V I A T I O N = 0 . 0 1 9
" . --·--- -A --·- - ·- - -- y _ --- - ·- -
1 0 0 0 . 0 l . o o o
1 3 64 . 8 2 . 0 1 5
_ l 446 . 3 -- - 2 . 22 8
1 4 6 1 . 3 2 . 2 74
1 50 5 . 2 2 . 3 7 9
.. 1 .6 6 9 ._9 ______ --·· . - - .. --· ·- ·- -. .. 2 • 7 5 0
1 7 9 5 . 0 3 . 0 0 0
2 0 40 . 0 3 . 5 00
F U i\J C T I 0 f\I .
0 . 9 9 8
2 . o 3 3
.2 . 2 3 2 -
2 . 2 6 8
2 . 370
- --- ··---------· - - 2 .7 3 8.
3 . 0 0 4
3 . 5 0 3
.. 2. 6 6 6 . l.._ - - - · -···-- -- . ---·-·- . -�� . 72 0. - - -·- _ _ _ : ___ --·-· · - - · - __ 4 . 7 2 0 ____ _ - -
3 2 5 9 . 4 5 . 7 0 8 5 . 7 0 8
.;) ' ·· I ! L• ,-• " " � - � .; - ; .. ' - ...... - ...... , ... . \.,." . .... - ..)
··---_x···· ·-- -�---·-- --·-- -- __ y -·-··- --- - --- - · -- - - -----F. U N C T I O h! - ·--··.--
1 0 0 0 . 0
1. 3 :)l;. 0 ��;
1 {.}/( 6 . 3
l '� 6 1 . 3
l 50 � . 2
1
/'.
0 0 0 0
"� J J. :J
2 0 22 c:
2 • ?. 7 t,
2 . �7 9
0 . 9 9 8
2 . (• : q
?. " 2 3 :.;
2 . 2 6 8
2 . 3 7 C
67
1 669 . 9 2 . 7 50 2 . 7 6 5
. 1 7 9 5 • 0 - - . - - - -· - -- - 3 . 0 0 0 3 . 00 1
2 0 40 . o 3 . 5 00 3 . 5 0 7
.. • -- -·
2 6 6 6 . 1 L; • 72 0
5 . 7 0 8 ·· - - --· · - · ---·-·-- - -5 . 7 0 3
S TA ND A R D D E V I A T I ON = 0 . 01 0
x y
- 1 0 0.0 . 0 - - · --··· ------·-·-- ·- ----1 . • 00 0 -
1 3 64 . 8 2 . 0 1 5
1 44 6 . 3 2 . 22 8
. 2 . 2 74
1 50 5 . 2 2 . 3 7 9
1 669 . 9 2 . -r 50
J_ 7.9 5 . • 0 ·---- - --·--- --- . . 3 . 00 0
2040 . 0 3 . 5 0 0
2 66 6 . l 4 . 7 2 0
3 2 5.9 .• 4 -- - - - ---.5 • -, 0 8
S TA NDARD D E V I A T I O N = 8 . 547
F U NC T I ON
-- ·-- -� 0 • 8 9 L� -·
1 . 3 3 6
1 . 840
1 . 8 9 1
2 . 00 4
1 . 8 4 0
1 . 45 7
1 . 344
- 3 . 9 2 6
...... ...... ...... J, ..... ... ... - - - - - - . - _._ .. , .. .. , .. .. £ ..... ..... "'li ... _ -· •• -
68
1 I .\I . • _ , ' T ' · 1 1 (' �\, � • . ) l (" 0 '\ . ·1 l c l '" . . : 1 r. 1 ') • \ I ,, '.>' \ • i I 1 0 2 �� . • • � l /' ·:, I :': . . 1 r� .ti I: • '
I r. tt . • • ; > J " L1 '> • r )
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I • • ., ' 1 , , j ' l l .' 1 l l 1 l '• •
I 1 I •
l ! l I l l ' i ) I ' ·, •
l I 1, I •
I I I, •
: I ' . '
� I •
1 ' • . . 1 l ' \ •
l. 1 7 •-: . ( \ I 1
! l 1 .
. ") .. . , 1_ ' .. i "
J:·! �_:4L-·--• • • '"1 1 1 H l • '. ! l 't·
·1 • 'j ."�fl_ .. _:_. . I • ':'1 i� f> ' . {) �) /. l . '1 �1.L ...... 1 . 1 1 () {� l . l l') l • l ? .1,_ - •
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) �1 '-\ ! • 't ) ,· ) I • 'J. l '• ' . '+:> "} : • ;I t 3. 1 • 1, :; '�
• �'t ., ? 1 ·' • � 1 . . . .
I • '1• l I 1 • '5 I 11 J. . j5 2'�, 1 • () lj ;·� 1 • ') 1-, i l
1' , ") .. t I : • � 1 \ h 1 • .:.,1) ·)
] • :) LfL-..,-1 • . ) ,, 7 J • J G1 l
----- -----1 -.� 1 . n l ._'\ ·�l I..> • I� t •q l . ;) . . -·
' .1 1 fJ • t') 1 1 1 ? I • " ] 1 ) 2� . 0 .. ! '1 � 1 . n ! 136 . 1) I Vtl . ll .�
I ) t1 (, • O 1 · 1 c; i . 0 i ') �.r. • C•
) 6 I • 0 1 ') (,�, . (' i ' : I . n 1 :'j 7 f., • ·) I <) ;;, 1 • (I I · I <� ��-� I l l • .1(} 1 . �! t ·)f)f • • (t 1 1 .'.,�.J • '. I 1 I ,I 11 • ') 1 1 1 1 . n I I l '• • . ; I 1 ? 1 • 1) 1 1 ? :) • :) ' l ".I 1 • i ) l l � (1 • . ') 1 l 1, l • l) 1 .!. 1. :) • ') 1 1 '� 1 . n I J. l) f, . (1 ' I I� J • !'! l 1 (,f.i . () 1 1 1 1 . n L l 76 •. 0 .. .. 1 1 Q' ! • (I' ! J :.rt . • f'l ! I n l ·• ,.,
l I '"1 f> • Cl I .> tl l • () 1 2 L) 6. • .() ' .' l l . () I -, 1 ', • I '
--
--------· ------l . tl•H , 1 00 ? . 0
l • ( l ), 7 .> l ,., {'\'7 • I) L . ,.,�{ '-\ .... _ ..:.- . __ l n l ?.�. n l , l ! "i () l f1 l 7 . () 1 . •)6f> 1 0 ? 2 . t)
1 . C ��2. ·- :. ... __ 10 2.7 • I_' _
1 . 0 0:\ 1 1)3 ? . 0 J . l l �-' ) '11 7 . 0 l • 1 ?.0 . .... . .1 tV+2 . n l . J L� 5 1 ')4 7 . t) I . 1 6 l
· � 1 . 1.- 1 �) J. • 1 ( \? l . ? d 7 1_ . ? ? ..,, 1 . :> r n l . ?. •) � 1 • ' '-, ll I • � ,, '-1 • ? 19 1 • .? 1 It l • ·3 % '1 1 • i. 1,1, 1 • < '> r. l • ".>. 7 .., I • � '.� n 1 • ! .. . , .,, 1 . • 1t J 7 1 . 4 1 ?.
.. 1 • .r, '• r, 1 • 1t 6 1 1 . t, ·1·5 1 • 't •J " � 1 • c; !) 4 I • ':i l 0 1 • r, �.? J • Lj 4 (.
1 , 1),.,() 1 • �' ., " I • c; g q
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1 ,.,h 2 . n 1 l)f., 7 . 0 } ') 7 ? . 0 1 " 7 7 . 0
1 f) Sl ? . 0 l r,� 7 . n l ,, (', � • !j l ;)O 7 . ·"' J t n ? . n 1 1 (: 7 . ,., 1 1 1 -z • .:) 1 1 1 7 • 1) 1 1 " :? . 0 l l ? 7 . ') 1 1 3 ' · "' l t ?, 7 . (\ 1 1 1. 2 . 0 l 1 1• 7 . () 1 1 52 . ') 1 J 5 7 . 0 " 1 1 6 � . 7) l H> 7 . f'
1 1 7 ? . ()
1 t 7 � . n 1 1 H 2 . i} 1 ' ':1 7 . 0 1 1 c. ? • ;)
l 1 ° 7 . f) l , f- t'\.? 1 ? 1)?. . i::i
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1 . nrJ i+ l . '.) 2 l 1 . 1) 1 7 l • ') 5"3 1 • . 'II, (")
. - 1 . �3.5. . . .. . , J . 1 0 } l . l l 7 J . 1 ·- p l . 1 4 1 l • 1 h 4 1 • 1. 7<) 1 . 1 0 5 l . � l l) 1 • � 2 '> ] • ? 11 1 l . ?. 5 6 J . :?. 7 1 1 • g 8 7 l . l<' ? 1 . ? �.?-1 . �. ] ;> 1 • "\ 4 h 1 • 1,f, 1 1 • 'l. 7 {) 1 • lQ 1 l . . 4 0 11 J . 1. 2 1) 1 . 4 � 5 J . tt 4 0 l '• 1-t Ei 4 1. • It 7 q 1 • 1t9 ? t . :i ri 7
l =) •13 • n l 1 . ')()A . � l 00 4 . 0 . l • 0 1 l 1 001 . 0 . 1 . 0 ? 4 1 0n q . o . 1 . 02 1 1 o U , r!. .. . ... �- _ l.. 0 .'t .o --�- . . .l .O .\A. 0 . __ _:_: __ _ :..1 • 0 4 3 J O J ·i . 1 1 1 . 0 56 l O l q . o t . 0 59 i n z � . � t . 0 7 ' 1 0? 4 . o 1 . 0 75 i o 2 t' . • ·-� --·- -· l . o 3..s _____ 1.029 •. o __ --1 . 0 9 1 J :: ? ':\ . (J l • 1 0 It ,. l o ·-1 �) • o 1 • 1 .� n
l OVt . O l . 1 0 7 1 0'.3 9 . 0 1 . 1 2 3
--·-:-:�
l ;; .1, ·� , 1) --- .... :.... l . 1 ? 5 _ _ ,·: l O/t 4: •. () ... ---- l_. 1 3 q •.. -· .
l. !)lt<l . 'j . 1 . 1 5 1 1 0 5 3 . n 1 . 1 6 7 ' l !'J ') t:, . · 1 l �' (� "\ . •.) 1 n A� . o
-- .. ... J . 'l 'l ' 1 . 1 ·).C�
l . ?. l 1 l 1)7 � • 'I -· _ ____ l • ? '? 9 1 d 7 H • I ) } . :� It 4 l C q � . 0 l . ? 5 '1
. ...
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t . 1 1 1 .:; -· - - l -· '.\ -� ; ) -.--··-
1 . ·p 5 1 . 1 �, q 1 .-� :�I�-···
l . � 7 9 1 : 1 'f /. 1 . /ti) q l . '+ ?. � 1 . 4 ':\ q
J t 4 -:i • ''··- ---- L . '• '.l ? ___ _
1 1 5 � . o L 4 f.. 7 l l �j ., • l) " .. l • 'ts l l l b'" · " 1 1 r,r; Ji 1 1 7 3 . P
1 • 't- <l 5 i . s 1 n 1. ') ?. !_. L . �33 ... ___ _
l . '1 5 2
l 0 4 q . o i . 1 5 4 1 0 '1 1t . 0 1 . 1 1 0 1 0 '1 9 . (l .. .. . _ . . 1 . J. 8 5 .... - - - ·
l or ... '+ . o 1 . ?.O l l c r ... <1 . 0 1 . 2 1 6
1 0 7 4 . 0 - - 1 . 2.3 2 1 "1 7 9 . 0 l . ?'t 7
l C R 4 . 0 1 . 26 2 1 01-\ 9 . () -'-.'. .. __ l . 2 7 7
� � ..... c
1 00 4 . 0 1 . 2 9 3 00 l •)O 9 • (' 1 • 3 0 8 l l 0 4 ._ 0 -- - 1 . 3 2 3 l l O Q . O 1 . 3 1 A 1 1 1 4 ., 0 1 . 3 5 2 l l l C?�>() . ... 1 • 1 6.7
1 1 2 4 ;-'0 l . 3 8 7 l 1 2 9.� 0 l • 3 9 7 l � � 4 •
. 0 l . 4 1J
• l l 1Q . Q l . 4 2 6 t 1 '+ 4 . 0 1 • 44 1 1 l '• .9. 0 --· - J • � c:; 5 . -·-
1 l ':i It . 0 '.. 1 • 4 6 9 1 1 1; 9 . 0 l . Li- 8 4 1 1 (� It • 0 .. ·-' .1 . 4 9 A 1 1 6 ° . o ! . 5 1 2 1 1 74 . 0 1 . 5 ? 7 1 1 7 9 -· () ..,. . _ J. • 5 4 l 1 1 � 4 . • 0 1 . 5 5 5
1 . 132 1 l . '> 3 " l •. r.; 4 'J 1 • I)(, 1 l . ')1 '1 l • 1)0 1 l • �) 0 '1 J . '., 1 0 J • f11 3. 1 . r-. 1 .. 7
1 1 7;3 • .o._, __
�" J i H 1 . 0 ) l l !1'1 , () 1 . 5 6 f> 1 . 5 <' 0
i 1 w � . o . t . 5ti9 l l '> � . 0 1 1 t;:1 . (· 1 : q ?. . 1: l '.? 1) 11 . �) ! :? J 'i . 0 l ? J 1\ • 1:
1 . 5 � 4 l • !,L) g 1 . 0 2 2. -� ..
l • ,., A. (1 l • ',I�!)
1 1 <)4 . 0 . l . 5 '3 3 l l Q 9 . 0 1 . 597 � 1 2 8 � . 0 1 . 6 1 1 1 2 0 Q • () - -···· .. l • 6 2 i;. .. ·_ · .... l ? 1. 4 • 0 . 1 • t'-. � 8 ' t 2 1 9 . o t . 6 5 '
Table 9 (a)
THE D I P O L E � O � E N T OF I O D U 6 E N Z E N E I N B EM Z E N E
E
2 . 30 5
2 . 32 8
2 . 3 3 5
2 . 3 5 7 ·-
2 . 3 8 3
D
0 . 8 8 0 2
0 . 89 0 1
0 . 8 9 3 3
0 . 9 02 5
.o . 9 1 2 2
X 2
0 . 00 9 7 0
0 . 0 1 8 1 9
0 . 0 2 1 5 8
0 • 0 2 8 5 7 -----
0 . 0 37 5 2
0.I E L EC T R I C C Oh�S T.L\NT O F S O L V E�H = 2 . 2 7 7
A= o . z E q E 0 1
D E N S I T Y OF S O L VE � T = 0 . 86 8 9
B = 0 . 1 1 6 E 0 1
i"i 0 LA R P 0 L A R I Z A T I U i'. = 0 . 7 5 7 E 0 2
D I S TO RT I U f\: POL/ :. R I Z A T I 01\! = 0 . 3 9 3 1: CJ 2
O R I E N TA T I O N P O L A R I Z A T I O� = 0 . 3 6 4 E 0 2
0 I POL E l-i01·1 Ei\iT = l . 3 3 4 O E B Y E S
TIGANIK, (41) REPORTS 1 . 39 AT 20°c MURTY , c . R. , e t . al (42) REPORTS 1 . 29 AT 30°c
70
E
2 . 193
2 . 355
2. 5).9
2 . 6 85
Table 9 (h)
The Dipole !1lome11t of Nitrobenzcne in Cyclohexane
2 n
1 . 4242
1 . 4258
1 . 4268
1 . 4273
DIELECTRIC CONSTAl'iT OF SOLVENT :::: 2 . 028
A = 0 . 1639E 02
x2
0 . 0099980
0 . 0199604
0 . 0299985
0 . 0399676
INDEX OF REFRACTION OF SOLVENT SQUARE = 0 . 2026E 01
B :.: 0 . 3002E 00
ORIENTATION POLARIZATION = 0 . 321412 03
DIPOLE ��)ffiNT = 3 . 96 D
BrO\m ( 43) reports 3 . 96 D
Jenkins (44 ) reports 4 . 00 D
71
Table 9 (c)
E I)
2 . 0 3 6 o . 1 r: 2 6
2 . 0 3 9 0 . 7 8 5 1
2 . 0 4 2 0 . 7 9 2 2
2 • Q L;- 8 0 . 8034
2 . 0 5 l� 0 . 8 1 4 8
- - · . ... ··�-X 2
0 . 0 1 0 B 8
0 • ( ) l 4L�3
0 . 0 2 0 1 1
0 . 03066
0 . 0 l:·l 0 7
D I E L EC T R I C C Oi,I S T A i H O F .S O L V f f\'T = 2 . 0 30
A= 0 . 5 80 E (10
0 E i\I S n- Y 0 F S 0 L V b'! T = 0 • 7 7 0 3
H = 0 . 1 0 8 E O J.
;., 0 L 1'.f·� P 0 Ll \ R I Zt.\T I U i\1 = O . 3 � () I:: O 2
D ! S T O R T I UI'! POU.'.l\ I Z AT I O,"= li . 2 9t�E 0 2
O f U !:: NT i J.T I C1'� P O L ;.\ � -(1 2.h T l Ui'l= 0 . � 5 2 t O J.
D I POL E i·tOl, . Hl T = 0 . 5 1 9 0 E i3 Y E S
7 2
Table 9 (d)
11iE DIPOLE MOMENT OF CHLOROIODOETHYLENE IN BENZENE
E
2 . 280
2 . 282
2 . 286
2 . 290
2 . 293
D
0 . 8781
0 . 8831
0 . 8906
0 . 9027
0 . 9095
X2
0 . 00980
0 . 01429
0 . 02037
0 . 03080
0. 03630
" DIELECTRIC CONSTANT OF SOLVENT = 2 . 276
A= 0 .469E 00
DENSITY OF SOLVENT = 0 . 8663
B= 0 . 119E 01
MOLAR POLARIZATION= 0 . 3SOE 02
DISTORTION POLARIZATION= 0 . 288E 02
ORIENTATION POLARIZATION= 0 . 616E 0 1
DIPOLE MOMENT= 0 . 549 DEBYES
73
7<1
Tal.Jle 10
�lass Spectrum of Chloroj odoethylene
Compound m/e
c2H2c137 r p + 2 190
c2112 c 1 3 s r 1 8 8
rc137 164
rc135 162
CzH2I 153
CzHI 152
HI 1 2 8
I 12 7
c13 7cH=cu 63
c135C! l=CH 6 1
F O R T t� /\ i ·! I V
O Q O l 0 0 0 2
00 0 3
0 0 0 4
0 0 0 5 0 0 0 6
00 0 7
0 0 0 8
0 0 0 9
0 0 1 0
00 1 1 0 0 1 2 00 1 3
00 l 'i-_00 1 5
0 0 1 6
00 1 7
O O J. 8 0 0 1 9
0 0 2 0 00 2 1
0 0 2 � 00 2 3 0 0 2 L�
0 0 2 � 0 0 2 6
00 2 7
0 0 2 8 0 0 2 9
0 0 3 0
0 0 3 1 0 0 3 2
0 0 3 3 0 0 3 Li·
0 0 3 5
_0 0 3 6
0 0 3 7
0 0 3 8
0 0 3 9
0 0 40
0 0 4 1
_00 ':- 2 0 0 4 3
0 0 4 4
UI) L.-?
0 0 4 6
0 0 4 7
. � ·- -
-- - -
l:· U : V E L
c
2 0
3 0
1+0
� o 6 0
7 0
8 0
9 0 1 0 0
1 1 0
1 2 0
1 3 0 l '�O 1 5 0
1 60
1 7 0
1 b()
1 90 2 0 0
2 1 0
2 2 0 2 3 0 2 1;0 2 50 2 60
2 70
?. ti(; 2 9 0
300
3 1 0
3 2 0
3 3 0 3 !.:·0 3 5 0 3 60
3 7 0
3 80
3 9 0
400
4 1 0
4 2 0
430 t,1�0
'� :> v lt·bO 4 7 0
Program 1
1 8
75
D/'. T t = 70 2 0 2
L EA S -f S O U i\ R E S C U KVE F n··ni\lG i3Y O R T H OG01·�:\ L P O L Yl!O;·. I /:1 L S l) I i-i E i'! s I 0:\1 p ( 1 5 ' 1 L:- ) ' f\ ( 1 5 ) ' x ( 1 0 0 ) ' y ( l () 0 ) ' \·! ( l 0 0 ) k E i\ D ( 5 , 1 0 0 0 Hl X , 1'1 , M , K
. I F ( ,:, - h! ) 4 0 7 L;. 0 , 5 0
1·l=1·i- l
I F ( i( l 1 l 0 , 7 0 , 1 1 0
DO 90 I = l , r·i R E t; 0 ( 5 , 1 0 0 1 ) X ( I ) , Y ( I ) , \·J ( I ) C Of\!T I i\!U E
GO T O 1 5 0
0 CJ J. I.� O I = 1 , i-1 R. E f-\ 1) ( 5 , 1 00 1 l X ( I l ,_y ( I l � ' J( l ) = l . O
C OfH r1,l U E
DU l G O I = l , 1 5 U O l &O J = 1 , 1 1., P ( l , J ) :.:O o O C Oi :·J° l i'l U E
P ( l , l ) = l . O
X S U1·1 =O . O YSU1·i=O . O u 0 2 50 J ::: l ' i-i xsu; . = xs ui.; -:- x ( J l :::i-· 1 J l Y S U,·: =Y SU:-. +'.·! ( J ) C Oi'IT H ! U E P ( 2 , 2 l = l . O P ( 2 , J. ) = -i�S Ui-, / Y S lf·I
l)O SL;. 0 I = 3 ' 1"fr·1 I I = I - 1 I X = I - 2 X S U i l =O . 0
Y S U i•i= O . O
U S Ui·. =O . O Z S Ui·i= O . O
0 0 4 70 K = l , i!i su;·i Y = O . O SU,·!)�=O . O DO 42 0 L = l , I S U ;· i Y = S U :··1 Y + P ( I I , L ) :;: X ( K ) �:� :;: ( L - l )
SU: i X = SU ,•l X -:-P ( I ;� , L ) ::: X ( K ) :;: :;: ( L - 1 }
>:SU: . = X S u: \ + X ( K } ::: SU :.j Y ::: :;: 2 ::: ·. i ( K )
Y S U = Y S U.·1 + S 1..J, • • Y ::::;: z:::. ( :<. )
C O i\ T I 1':U E
) L; S � 4 9 , 50 0 5 1 . ::. z i 5 3 ) 5lL ) 5 5
1 5 6 ) 5 7
)58 J59 J60
l61
162
l63
164
l65 J66 167 !68 J6 9 70 171 72 B ·74
7 5 7 6 7 7 7 8 79 80 8 1 82 83
84 85 86
- l� 80 i::� 9 0
5 0 0
5 1 0
5 2 0
530 5 i::,.o
5 5 0 5 6 0
5 70
F.:. = X S U i,i/ Y S U H G =- U S U i·:/ Z S U i:i
P ( I , l ) = -13 ':' P ( I I , l > + G ::: P ( l X , l )
DO 5 1.�o J =2 , I ,JJ = J - 1 P ( I , J } = P ( I I , J J ) - B ':' P ( I I , J l + G ,;, P ( I X , J ) C 01,J ·1· I ;\JU E D O 6 7 O I = 1 , 1,Ji,! X S U i··1 = 0 . 0
Y S U M =O . O
5 8 0 D O 6 5 0 K = l , f.i
5 90 S Ui-IZ =O • 0 6 0 0 DO 6 2 0 L = l , I 6 1 0 S Ui'iZ = S Ui'i Z + P ( I , L ) ':'X ( K ) ,:,,;, ( L - 1 ) 6 2 0 C O M T HJU E
6 3 0 x s un = x s u H -:- y ( [,Z )::: s Ui·i z ::: �·! ( K ) 64 0 YS U H = YS u;,\ -:· S U11: Z ::::;: 2 ,;, \·! ( K l
6 5 0 C O l' ! T I i ,J U t:
6 6 0 IJ.. ( I ) = XS Ui.\/ YS Uf·1
6 1 0 c 01·rr H! U c
6 8 0 D O 7 9 0 I = l , N N
6 90 0 0 -1 l 0 ,J = 1 , I 7 0 0 P ( l 5 , J l = P ( l 5 , J ) +P ( l , J ) * A ( I )
7 1 0 C O!H Ii'WE
7 2 0 I F ( l - N X l 7 9 0 , 7 3 0 , 7 3 0
7 3 0 L = I - 1
740 W R I T E ( 6 , 1 0 0 3 ) L
7 5 0 IJ 0 7 �3 0 K = l , I
7 6 0 K K = f:- J.
7 7 0 :·rn I T i ( 6 , 1 00t.:. ) i� K , P ( l 5 , K )
.. . . 7 8 0 C O i'� T i r,�U t: 7 90 C Ol'H Il-!U E
8 0 0 GO T O 2 0
1 0 0 0 F 0 RH t\ T ( Lr J 5 )
100 1 FO Ri·'.A T ( 3 F l 0 . 8 l
1 0 0 3 F O Ri·i.iq ( / / / l Z X , ' T HE P O L Y�! O H I A. L CF O R DER 1 , u� , 1 T 1-11:; T B E S T . 1 c u R v E I s I I I 2 6 x ' I p 0 �·! E R. 0 F x 1. ' 1 2 x ' ' c 0 E F F I c I E N T I )
1 O 0 4 F 0 RH AT ( 2 9 X , I �- , 1 0 X , E l l� • 8 ) R E T U R N
76
F I T S T H f-:
0 0 0 1 0 0 0 2 0 0 0 �� 0 0 0 4 0 0 0 5 0006 0 0 0 7 0 0 0 8 0 0 0 9 00 1 0 0 0 1 1 00 1 2 0 0 1 3 00 1 4 0 0 1 5 0 0 1 6 0 0 1 7 00 J. B 0 0 1 9
00 2 0 0 0 2 1 00 27-0 0 2 3 00 2 4 0 0 2 5 0 0 2 6
0 0 2 7 00 2 <J
0 0 2 9 0030
c
c
Program 2 77
1 ., ... , ..
r U !' :c ·l° J. lJ;': i-\/1\ L l J f:.·f l (ii·: :'.1i,Jf) S T:\ 1 .U:\:�U u1:\ v 1 ·1·.( ( Ji'i F O !'l. L E1� Sl CUR V E f.'. i rr 1 1,•G D I H i: i'IS l Oi'! X ( l OO ) , Y ( J. 00 ) , F ( J. 0 0 )
I� E ,:, D ( 5 , 1 0 ) i·1 , L
l O F lt �;I ; A ., ( 2 1 5 )
DO 30 I = l , 1·. !-{ E J� () ( '.'> � ?. G ) X ( J ) , Y ( l )
2 0 � O n 1·if1 T ( 2 F l 0 . 0 )
::SO C 01H I 1•JUt D 0 l 0 0 I\ = 1 , l :u: 1\ !) ( 5 , '+ 0 ) i1 l , IA 2 1 A 3 , /.'.I� , A 5 , A 6 , /\ 7 , / H5
4 o r o H 1 , i• ·i < c r: i o • o )
S D=O . O
D O 50 i = J , i··1 Z l =A l + A 2 *X ( l ) + A 3 *X ( I l ** 2 + A 4 * X ( l ) ** 3 Z 2 = t\ 5 ::: X ( I } ::: ::: Lr • :- /.\ 6 ::: X ( I } ::: ::: 5 + A 7 ::: X ( I } ::":' 6 + t\ :·1 ::: X ( I l ::: ::: ·r F C i l =Z l + Z 2 S iJ = S tJ + ( F ( I ) -Y ( I l ) :::::: 2
S O = S C..JK T ( S U/ ( Xi·� - J . • ) } ':i R I .i f ( 6 , 6 0 )
6 o F u f{ . .• Ar ' 1 o • s )� � 1 �� 1 , 1 ::> x , 1 v 1 , 1 5 �< , 1 F u t'K r 1 n ,,, ' l DU 80 I = 1 , r·1 \ I R I T E ( 6 , 7 O ) X ( I ) , Y ( I ) 1 F ( I l
7 o F o r..; i'/\ ·r 1 • <J • ; F 7 • 1 , i 5 ;( , 1- ti • 3 ,J. :::> x , F 6 • 3 l e 0 C rn-.1 T J : i U E
U� i i t ( 6 , 9 0 l S!j 90 F U f�, ·i:\T 1 1 o • , 5 ;z : ' S T £, ... 1)�!-, D D E v r ;.. ·f r u;·i = • , F -t . 3 )
1 0 () C U 1,- ·1· i 1'.l J c R E T U l�1'l E N D
.::- . I '' .
Program 3
FORTRAN IV G LEVEL 18 MAIN
C DIELECTRIC CALIBRATION FUNCTION DIMENSION D(S) , E (S) WRITE (6, 19)
10 FORMAT (! HO, ' DIAL ' 2X, ' DIEL, CONST . ' ) READ ( 5 , 2 0) DMAX
20 FORMAT (FlO . O) READ(S , 30)Al , A2 , A3 , A4 , AS
30 FORMAT(6El0 . 0) X=999 . 0
40 po S S I = l , S X=X+ l . O D ( I) =X Zl=Al+A2*D ( I ) +A3*D ( I ) **2+A4*D ( I ) **3 Z2=AS *D(I) **4
S O E ( I ) =Zl+Z2 SS CONTINUE
78
WRITE (6,60) D ( l ) , E (l) , D (2) , E (2) , D (3) , E (3) , D (4) , E (4 ) ,D(S) , E (S ) . .
60 FORMAT (F7 . l , 4XF6 . 3 , 4XF7 . l , 4XF6 . 3 , 4XF7 . l ,4XF6 . 3 , 4 X 1 F7 . 1 , 4XF6 . 3 , 4 XF 7 . l , 4XF6 . 3 )
l F (DMAX-X) 80, 8 0 , 4 0 8 0 RETURN
END
()()() l
0 0 0 2
0 0 0 3
0 0 0 4
0(10 5
0 0 0 6
0 0 0 7
0 0 0 8
0 0 0 9
0 0 1 0
00 1 1
0 0 1 2
00 1 3
0 0 1 4
0 0 1 5
0 0 1 6
00 J. 7
00 1 8
00 1 9
0 0 2 0
0 0 2 1
0 0 2 2
00 2 3
0 0 2 l� 0 0 ? 5
0 0 2 6
00 2 7
0 0 2 8
0 0 2 9
0 0 3 0
e) O 3 1
0 0 3 2
0 0 33
0 0 3 4
00 3 5
0 0 3 6
0 0 3 7
0 0 3 8
0 0 3 9 . O O l�O
00 '�l 0 0 4 2
0 0 l;lt
0 0 4 5
O O .!t6
OOLt 7
c
1 0
2 0
30
40 ':· 5 5 0
6 0
7 0
1 0 0
1 2 0
Program 4 79
D I PC!L E i" o;.: E1 · ·T C: ii L\.lJ U\ T E 0 F R O ;·i D I l:L E C TH I C C Ul·JS T l·. 1,:T S
IJ i i 1 cr · S i tl1.! S 1�f.i P L F { 2 0 )
R E f1 0 ( 5 , l 0 ) S .1\ 1-1 P L E
F O H i·i/\ T ( 2 0 A 2 )
\·J R I T c ( 6 , 2 0 ) S A i 1 P l F FURl .. A T ( J.1 -: 0 , J. O X , 1 T f-! t: D I P O L E :-:C);·I F. l,·T oi-: 1 J. X , 2 t'/\ 2 )
�-: R I T E ( 6 , 3 O )
F O R l 1J\ T { 1 H0 , 1 3 X , ' E I ' 1 5 X , ' D ' , 1 5X , ' X 2 1 )
X 2 S U1 ·1 = 0 o 0
E S lJi·1 = 0 . 0
X 2 l:S Ud = O . 0
X X S Ui·:1 =0 . O
E E S U i•;=O·. 0
X2 IJS U t i = O . 0 D US U 1 ·1 = 0 . O
RE JH ) ( 5 ' Li-0 ) x l·l l ' x i·l 2 ' v ' 0 2 ' x l\I 2 ' T
r C I P.•iAT ( 6 F J. O . O l
1 -. l: ,i\ !) ( 5 � s () ) I I l 2 � 1, I "f
F O n.1-1.c� ·f ( 2 f l 0 . 0 ) I F ( �·iT 2 ) 6 O , } 7- O , 6 O r- E /\ i) ( 5 , 7 O l C: F O R i l.l\ T l i-: 1 0 . 0 )
1:1 T 1. = 1• ! T - 1:"!T 2
L>= �·I T I V x ? ;;;; ( l·'T 2 I )(: '? ) I ( I I T 2 1 x ], 2 + l '!T l I x f 1 l )
Y.?. S U1·1 =X 2S U : 1 + �� ?.
l: S l J1·1 = t S U i i + F.
X X S Ur·: = X X S U 1 1 + X 2 :::)�2
E E: S U 1·1 = E E S u;.i + E ::: E X2 E SlH= X2 E S l J h + X2 :;: E
u s UH =I) s lJ i·1 ·:-(J l.)0 S LJi-1 = D O S U h + D :;' D
X 2 DS U1·l ;;; X ?. fJS U H + X 2 :::o X l = X I + l . O
W R I T E ( 6 , 1 0 0 ) E , O , X 2
FO �t i t, T { 1 H 0 , 1 0 ;q: 6 • 3 , 1 0 X f 7 • l; � 1 ') X F 8 • 5 )
GO T U L:-5 X D = X I :::xx s u'.-X? Sl�; .. ::: ;� 2 SU :·i
f\ = ( X I :;: ;(2 E S Ui-!-X?. SU.·i':' t: SU ,.I ) I X D A A = A P, S { A )
E 1 = ( xx S Ui·! ::: E S Ul·i-X 2 S U i'·i =::x Zc s Ui·I ) I X O B = ( :< I ::;: X 2 D S U ; ·: - X ?. SU ;:; ::: D S U ; ·, l I X D
... -· ' • ' r - . . . . . . .. . - � '· \ . . , . ·- - �- . . . . . . ..
Pt\ = 3 • O :;: X :-i 1 ::: A A I ( ( E l + 2 • O ) ::: ( E 1 + 2 • Cl ) ::: D 1 )
P B = ( E 1 - 1 • 0 ) I ( ( t 1 + 2 . 0 ) :::r n ) PC = X 1·12 - ( X h 1 ::: B B ) I D 1 f' = ? t.\ -:- PS ::: P C
80
F O RT Rf'. M I V G L E V E L u; f·i A I I'-! D t\ T E = 7 0 2 0 L;.
0 Q L� S 004-9 0 0 5 0
0 0 5 1
00 5 2 J. .!1·0 0 0 5 3
0 0 5 4 1 50
0 0 5 5
0 0 5 6 l 6 0
0 0 5 7
00 5 8 1 7 0
0 0 5 9
0 0 6 0 J. 80
0 0 6 1
0 0 6 2 1 9 0
0 0 6 3
00 61'.� 200 0 0 6 3
0 0 66 2 1 0 00 6 7
0 0 6 8
P 2 = ( X f1lZ '::x;,� 2 - 1 . r) ) 'n�f·i 2 / ( ( Xi,! 2 ,:= x i1 !2+ 2 . 0 ) ::: 0 2 )
P 1 :..: P--P 2
u = o . 0 1 2 s':' s o 1zT ( P J. ':' T )
vi R r T E ( 6 , l L:O ) E l F O f�i-!.6. T ( l H O / / l l X ' D i t: L E C T R I C c o 1-..;S T A i°'! T O F S O L VF. h- T = 1 , J. XF 6 Q 3 ) \·! r<. I T c C 6 , l 5 0 ) /.\ F O R i.:;/\ T ( J. H O , J. OX , 1 A = 1 7 E l l . 3 )
\·.!R I T E ( 6 , 1 6 0 ) D l F o n, 1- 11\ T ( J. H CJ , J. ox , 1 D E i'l s I T v o F s o L v E 1,1 T = 1 , 1 x F 7 • 'i· l
':·! R I T E ( 6 , 1 7 0 ) B F O R h .i'.\ T ( l H 0 , 1 ox , 1 B = 1 , 1 x , E J. l . 3 )
l-J R I T E ( 6 , 1 8 0 l P F O ki·it\ T ( l H O ' 1 ox ' I !'! O L A R P O L! \ f{ I Z A'f I CJ/\:= I ' E 1.1 . 3 )
· H R I T E ( 6 , 1 9 0 ) P 2 F O F�i"°iA T ( l H O , J. OX , ' O J S T O R T I OI\! P O U\ R I Z .l \T ! O i-.i= ' , t: J. 1 . 3 ) \·! R I T E ( 6 , 2 0 0 ) P 1 F 0 � i·I /'.\ T ( l H 0 ' J_ 0 x ' I 0 R I Ef',i T t\ T I 0 j\i p 0 u .. R I z /), "I I ON::: I ' E 1 l 0 3 ) \·: R I T t ( 6 , 2 l O l U F ::..P<i, !-\ T ( J. H u , 1 ox , ' U i PO L E i·•lli . . E i,J T = 1 , F 6 . 3 , l. X , 1 D E ::,Y tS 1 ) R E T U Kt'l EN D
Chapter IV
Bibliography
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7. McLellan, A. L. , "Tables of Bxperimental Dipole Moments", W. H . Freeman and Co. , San Prancisco, (1963).
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Voa•l, A . I . , "A Test Book of Practical 0Tgan1c Chemistry" John Wiley g Sons . Inc . , New York , 3rd . ed. ( 1 966) .
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83
v lta.
Name : Ashvin Gajondralal Gajjar
Permanent Address : Shiva Nivas , Athwa Line5 , Surat, Guj arat �tate, India
uegree and Date to be Conferred ; M . S . (Chemistry) August 1970
!>ate of Birth: Septemb(Jr H, 193.S
Place of Birth : Surat, India
S@condary Education : Matriculation from tho T . &T . V . Sarvajanik High School , Nanpura, Surat . March 1956
Collegiate Institutions Attendod
M . T . ll . College (The Gujarat University)
Sarvajauik College of Science (The Gu;arat University)
S�t•rn Illinois University
Major: Organic Chomir.try
Minor: Physics
Positions held:
Positions
Part-time demonstrator
Tutor-Lecturer
Tutor-Lecturer
Graduato Assistant
Dato Degree Date of Degree
1956- B.Sc. Apr�l 1960
1960
t�60- M.Sc. Apri l !Q62
1962
1968 .. 1970
Date
Oct � 1960�
Marcil 1961
H . S .
September 1962-
June 1964
JWle 1964-August 19i>8
Docember 1969-August 1970
A>1gusl 1970
In5titutions
Sarvajanik Col!o�e of Science , Surat
J. 6P. Arts an<l Science College, Broach
Bhavan • s College Dakor
Eastern Illinois University, Charlu�ton