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RALPHK. B~RDWHISTELL
University of West Florida
Pensscoia. FL 32504

On the Boiling Points of the Alkyl Halides

John Correia
Saint Mary's College, Moraga, CA 94575
Most introductory organic chemistry texthooks devote
some time to the discussion of the ~hvsicalproperties of
organic compounds and cn the way in which the-se properties
aredetermined hv the natureof the functional groups
. - within
the molecules. A; excellent opportunity is thus provided for
the presentation of a variety of concepts,
particularly
those
t h a t are of value in explaining attractive forces between
molecules.
Amone" several different kinds of nronerties and compounds, a number of the texts specifically examine the hoiling points of the alkyl halides. All of them note the general
increase in hoiling points of the halides relative to the alkanes from which they are derived, hut the reasons given for
this trend are varied and, in some cases, not convincing. For
example, some of the texts (I, 2) attribute the increase simply to the increase in molecular weight that takes place when
halogen is suhstituted for carbon or hydrogen.
Others (3-6)
emphasize dipole-dipole interactions as major contributors
to the higher hoiling points (particularly for fluorides and
chlorides). and there are those (4-7) that assien considerahle impo;tance to the surface area of the halogens and/or
their nolarizahilities. Which of these factors is reallv of major influence here? Is there perhaps a complex interplay
amone them that chanees from halogen to halogen?
~ e f ; l r eaddressing t i e matter of the halides, let us look
closelvat the wavin which the properties of molecules deterMany em$r;cal relationships exist hemine boiling
tween molecular weights of homologous compounds and
their twiling points, h;t theessential question iswhether the
mass of a molecule is important in this regard as opposed to
other properties that are related to molecular weight. The
simple kinetic theory of evaporation predicts that, other
things being equal, the vapor pressure ot a liquid should he
proportional to the inverhe square of the mass of its molecules (81;however, the experimental data do not bear this
out.
Comparison of nonpolar compounds that differ in molecular weight, yet have a shield of outer atoms with identical
polarizahilities, shows that their hoiling points vary less than
expected (9). For example, (CzHdaC (MW = 128) hoils a t
146 OC while (CsH6)aSi (MW = 144) boils a t 153 OC;
Mo(CO)S (MW = 264) has a hoiling point of 156 "C and
W(C0)6 (MW = 352) hoils at 175 "C;and so on.
When care is taken to compare compounds that not only
have outer atoms of identical polarizahilities hut that also
have identical surface areas, the surprising result is that
their hoiling points are not merely similar hut often the
lower molecular weight molecule hoils at a higher temperature (10).Consider, for example, NhFs (MW = 188) hoiling
at 235 "C and TaFn (MW = 276) boiling a t 229 "C. This
phenomenon is also known to exist in certain isotopic molecules, and it has been attrihuted to an increased translational entropy for the heavier molecule in the vapor state and,
hence, a greater probability of it vaporizing (11).
The fundamental effect of molecular weight on volatility
in complex organic molecules is undoubtedly not a simple
&

62

Journal of Chemical Education

one. However, it is safe to say that its effect is small and that
i t will he outweighed by such things as surface area and
polarizahility of molecules as well as other molecular properties that influence intermolecular attractions.
The focus of attention then should be on the cohesive
forces that exist in liquids. For polar, non-hydropen-bonded
s
are
molecules, these loosely termed van der ~ a a l forces
conventionally divided into three parts: (1) dipole-dipole
interactions (orientation attractions).
,, (2)
, , dinole-induced dipole interactions (induction attractions), and (3) induced
dipole-induced dipole interactions (dispersion attractions)
1\--,.
72)~
The approximate expressions for the potential energies of
the interactions between identical molecules are V(orientation) = -2p4/3kTR6, V(induction) = -2ap2/R6, and V(dispersion) = -3a21/4R6, where p is the dipole moment, k is the
Boltzmann constant, T is the absolute temperature, R is the
distance between the interacting portions of the molecules, a
is the polarizahility of the molecule, and I is its ionization
potential. I t should be noted that only the orientation energy
has a dependency on temperature, and i t is such that higher
temoeratures will decrease the average attractive enerev of
twohipoles. Thus, the relative contri!ktion of dipole-dipole
interactions to the total enerw
than a t
-.will he less at hieher
"
lower temperatures.
Furthermore, in those common organic molecules whose
polarity is due to the presence of a small polar functional
group
. . amid several methyl and methylene groups, the distance between interarting dipoles in neighboring molecules
should he relatively largeand dependent upon the sizeof the
molecule. Since the van der w a i l s energies show an inverse
dependency on the 6th power of R, one would expect the
orientation enerw then to fall off r a.~ i d.l vas the molecule
increases in size.
The induction enerw should also decrease with size in
these kinds of molec& since the dipole of one molecule
must effectivelv "contact" a neiehhorine molecule so that a
dipole can he iiduced. ow ever,;^ the interaction can occur
anywhere on the neighboring molecule (as opposed to dipole-dipole interactions), induction energies should not decrease as drastically as the orientation energies in larger
molecules.
By study of heats of vaporization, Meyer (13a, b) has
developed a method for estimating the percent contrihution
of each of the three types of interactions to the total cohesive
enerev for certain oreanic liauids (snecificallv. ketones. nitrileGand chlorides)."~riefl~;
he finds that thk'contribution
of the dispersion enerev is dominant in all cases, the induction energy makes asmall hut significant and persistent
contrihution as the molecules aet laraer, and the orientation
energy starts out small then r>pidl;he'comes insignificant.
For example, the contribution of dispersion, induction, and
orientation to the total energy of attraction is calculated to
he 73%, 21% and 6%, respectively, for methyl chloride; 8490,
1270, and 470, respectively, for 1-chloropropane; 91%,9%,and
070, respectively, for 1-chlorohexane; and 9570, 5'3, and 096,

respectively, for l-chlorododecane (13b).I t should be mentioned thaithese calrulations are done at different temperatures lor the different chlorides, paralleling roughly the decreased volatilitv with molecular size.
With all uf the above ideas in mind, let us return to the
consideration of the boiline points of the halides. The first
question to ask is, to whaishould the boiling points be
comoared? Because molecular weight effects are small and
dispersion effects paramount, it seems appropriate to make
comoarisons between halides and alkanes of similar size and
shape rather than between those of similar molecular weight
as is often done. The surface areas of the halide groups can
be estimated from their van der Waals radii, and, when this
is done, one finds that the chloro group is 19%smaller than
the methyl group, the hromo group is only 5% smaller, and
the iodo group 16% larger. On this basis, it would seem
helpful to compare the boiline- -points of these halides (R-X)
to those of R - ~ H ~ .
On the other hand. the small fluoro group has less than
but i t is only 25%
half of the surface area of a methyl
larger than hydrogen. In addition, fluorine and hydrogen
have similar group polarizabilities (14) so i t is more informative here to compare the boiling points of R-F to those of
R-H.
The hoiling points of the normal alkanes and the l-haloalkanesare given in Table 1.The figure illustrates their appropriate differences (i.e., R X compared to R-CH3 for X = CI,
Br. and I: and R-F comoared to R-H) as the number of
carbons in the halide increases.
The chlorides can be looked a t first since Mever's data are
directly applicable here. T o a good approximation, the cohesive energy of a liquid is equal to its energy of vaporization,
which is directly proportional to the hoiling point in absolute
temperature. Assuming that the percent contribution of
r
valid
each interaction calcul&d by ~ e ~is eapproximately
at the normal boilinn point, then, in a sense, the percent of
the hoiling point due t o that interaction can be estimated.
Thus, for l-chlorohexane boiling at 134 "C (407 K) and
having 91% dis)~ersionenergy and 9% induction energy at 56
O C , the percent contributionulinduction to the boilingpoint
w d~~-~~
d he
3-: "C. It is found that the difference between the
boiling points of l-chlorohexane and n-heptane is 36 OC. I t
seems that. in this case. the boiline point increase of the
halide is d i e essentially'to the induciion interactions that
are present in the halide and not in the alkane.
~

~~

~~

Table 1.

The argument holds only insofar as the dispersion forces

in the alkane are the same as those in the chloride. This
appears to be reasonable. The surface area of l-chlorohexane issliehtlvsmaller than that oin-heptane,but the molerular pol&z&ility, as calculated from the refractive indices
via the Lorentz equation (15), is slightly larger for the chlomL) than for n-heptane (1.370 X 10W3
ride (1.377 X
mL). Furthermore, the ionization potentials of R-CH3 and
R-CI should he quite similar (e.g., they are 11.28 eV and
11.65 eV for CH3CI and CH3CH3, respectively (16)) so we
expect that the dispersion forces of the two compounds will
indeed not be very different.
Use of Meyer's data for other alkyl chlorides with similar
calculations shows that their higher hoiling points are also
due essentiallv to induction interactions except for the
smaller compounds where the orientation interartion makrs
a small contrihution. Even for methyl chloridr; hou,erer, it
appears to be responsible for only abbut 20% of the increase.
The other halides can be examined only in a qualitative
sense. Even though R-Br and R-I do not have appreciably
different dipole moments from R-C1(17), their polarizabilities are much greater (14). The induction energies in the
bromides and iodides will be greater than in the chlorides
but so also will he the dispersion energies. And since the
dispersion energy depends on the square of the polarizabilitv.
..its .percent contribution to the total cohesive enerav
-. is
greater as wellas itsabsolutevalue.'l'hus, the large increases
in boiling oointsuf It-Hrand R-I nredue toacombinatiunuf
an induciion contrihution (a very significant one by analogy
to the chlorides) and larger dispersion interactions. In this
sense, the high polarizabilities of Br and I can be said to he
responsible for the high boiling points of the bromides and
iodides.

Normal Bolllng Polnts of l-Haloalkanes (CJi2,,X)*

x=

Boiling Poim. 'C

F
Ci

Br

5
10
CARBONS I N
'Taken horn Oreisbaa. R. R. mysIcalP1opertiasofcbmica-lcompwnm: Amarican
chemical society washington. DC. 1959: VOI 2: and 1967, v o ~3. ~ o i ~ i npoints
g
are
rounded to the nearest degree.

15
20
HALIDES

Bailing point elevationsof 1-haloalkanes(i.e.. R-X compared to R-CHS for X =

CI, Br. and I; and R-F compared to R-H)asa function of me number of carbons
in the halides.

Volume 65 Number 1 January 1988

63

The alkyl fluorides show the most dramatic changes in

boiling point relative to their parent alkanes; they start out
boiling much higher than R-H and eventually boil a t a lower
temperature. I t is reasonsable to suppose that the high boiling point of CH3F relative to CH4 is probably due to several
factors-the larger size of F, the usual induction contribution, and a significant orientation energy. As the carbon
number increases, we expect the orientation contribution to
decrease as in R-Cl and the size differential to become less
important. The low polarizability of fluorine (somewhat less
than that of hydrogen) then becomes the key determinant of
the fluorides' behavior. This results in small induction energies and, eventually, smaller dispersion energies for R-F
than for R-H so that their boiling points become more alike.
It is important to note also that the low boiling point
increases of R-F provide evidence for the lack of dipoledipole interactions in the medium and large size alkyl halides. If, for example, these interactions were primarily responsible for the elevated boiling points of R-C1, then one
would certainly expect them to exert this effect for the fluorides and lead to comparable boiling point elevations.
Another way of demonstrating the absence of major orientation effects is to examine the boiling point differences of
isomeric halides and their parent alkanes. Table 2 shows
these differences for the isomeric chloropentanes and their
constancy is striking. The orientation energy in, for example,
(CH3)2CC1CH2CH3would be expected to be significantly
less than that in CH3(CH2)3CH2CI because the dipoles in
neighboring molecules of the tertiary compound must he
farther apart as a result of steric interferences. Since even a
10%increase in the average distance between dipoles would
nearly halve the orientation energy, large variations in the
boiling point elevations would be anticipated if dipole-dipole interactions played an important role in these compounds. The data do show small steric effects, and these are
consistent with either induction or small orientation contributions. A survey of other isomeric series of chlorides and
bromides (where their boiling points are available) shows
that their behavior is similar to the chloropentanes.
In conclusion, the higher boiling points of alkyl halides are
best explained in terms of induction and, for the bromides
and iodides, increased dispersion also. The often neglected
induction interactions play a major role here and undouhtedly in other polar organic molecules. They may he responsible for some of the effects uncritically attributed to dipole-

Table 2.

Normal Bolling Points of the Isomeric Chloropentanes

and Hexanesa
Boiling Points, 'C

Structure

CH3

X=

a See fonnote s In Table 1.

aTaken from We&. R. C. CRC m d b &
BDFB Raton. FL. 1984.

Boiling Polnt
CI

Elevation

of Chemiswand P h p b . 85lh ed.; CRC:

dipole interactions and they should be given wider exposure

in organic chemistry texts.
Acknowledgmeni
The author wishes to thank Kenneth Brown of Saint
Mary's College for reading and commenting on the manuscript.
Literature Cited

1. Fessenden, R. J.: Fpssenden.J. S. Organic Chemistry, 2nd ed.;Grant Boston, 1982;p

163.
2. Morrison, R. T.; Boyd, R. N. Organic Chemistry, 4th 4.;Allyn and Bacon: Boston,
1983:p 198.
3. Carey, F. A
. Orgonie Chemistry. MeGrsw-Hill: New York, 1987;p97.
4. Loudon.G. M. Organic Chemislry;Addison-Wesley: Reading, MA, 1984; pp 297-298.
5. Vollhardt, K. P. C. Organic Chemistry:W. H. Floeman: Ssn Randnm, 1987;p 190.
6. Wade, L. G. Orgonic Chsmlslry; Prentiee-Hsll:Englewmd Cliffs. NJ, 1987; pp 177178.
7. strcitrieser, A ; Hel~thmek,C. H. Introduecion to 0rg.nie ChmLltry, 3rd sd.; Macmillan: New York ,1985:p 112.
8. Partington, J. R. An: Aduoncod Tmotlse on Physieol Chemistry, longman's, Green:
New York. 1951:Val. 2. p 291.
9. Rich, R. J. Chom. Edue. 1962,39,45&
10. Bradley, D. C.Natura 1054.174.323.
11. Bradley, D. C. Nature 1954.173,26&261.
12. See, far sxample. Y d e r , C. H. J. Cham. Edur. 1977, 54, 402-408, or any standsrd
physieslehemietry text, suehssRramberg. J. P. PhysicolChrmisliy. 2nd ed.;Allyn
and Bamn: Baston, 1981'nn
,-- RSbRS7.
. . .~
~
~

13. (el Meye.. E. F.; Wlyner, II. E. J. Phys. Cham. 1966,70,3162%3168:(bl Moyer, E. F.;
v a Chem. 1971.75.15 4 2 4 8.
R e n>er.T.
r ~ . A. J. P h.
14. Ferguson,L. N. Organic Molecular ~ 1 m ~ t ~ r ~ ; G rBaston,
a n f : 1975;p 55.
15. See. for rramole. Brombere. J. P. Phwical Chemialrv, 2nd ed.: Allvn and Bacon:
Eioston.198k:i p 85m51:
16. Watanak, K. J. Cham. Phya. 1957.26.542517.
~

~~

17. Ingold, C. K. Structure ond Mechanism in O~ganicChemialry, 2nd ed.; Cornell

University: Ithsea, NY, 1969;p 123.

Simple Filter Cannula Construction

Air-sensitive solutions are easily filtered with a filter cannula. A simple and
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III. thl.d.
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(.,m i.l.Y~.
the longer part of the body are removed by filing, and the resultiugsurface ia polished
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i r 0. n.48.
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Michael A. Urbancic
Owens-Coming Fiberglas Corporation
Technical Center
Oranviile, OH 43023

64

Journal of Chemical Education