A NOMOGRAPH FOR CORRECTION OF BOILING
POINTS
F O R laboratories which are located at any appreciable
elevation above sea level the correction of boiling points
because of decreased atmospheric pressure is frequently
a bot,hersome chore. As an example, most organic
chemistry laboratory manuals are written for low-
landers, and the cuts to be taken during fractionation of
a sample at high altitudes are not those given in the
laboratory manuals.
There are rather complex functions and nomographs
available for the correction of boiling points, such as
that of Hass and Newton,%hut for most purposes the
correction is not needed to an extreme degree of ar-
curacy. Further, the data for normal boiling points are
usually not sufficiently reliable to make highly accurate
corrections advisable.
A. suitable beginning for the correction is the Clapey-
ron equation in its differential form, where AH is the
heat of vaporization of tlie liquid at its normal boiling
point To, and R the gas constant.
dP AHP
dT = RTaP (1)
Pnsented the of Chemioal Education at the
129th Meeting of the Amerioan Chemical Society, April, 1956.
HGS, H. B., AND R. F . NEWTON,"Handbook of Chemistry
and Physics," 36th ed., Chemical Rubber Publishing Ca., Clew-
land, 1954, p. 2119.-
R. THOMAS MYERS'
Kent State University, Kent, Ohio
If the equation is assumed t,o hold for finite changes,
then
RT: Ap
AT = -
AHP. (2)
If Trouton's rule hold% then C' = AH/Tb in the above
equat,iO1l~
gives
When the temperature is expressed in degrees absolute
Kelvin and P in mm. of Hg., then C is 0.00012 for nor-
mal nonassociated liquids (Trouton's constant 21 cal./
mole/'K.), and 0.0010 for associated liquids (Trouton's
constant 25 c a I . / m ~ l e / ~ K . ) .hsociated
~ liquids are
those like water, alcohols, and organic acids, which con-
tain groups which are capable of hydrogen bonding.
Usually the temperature is expressed in centigrade de-
grees and the change in pressure in mm. of Hg.
At = C(273 f t)(760 - P ) (4)
The range of variables to be chosen depends on the
location and needs of the user. For our illustration 17-e
have chosen t between 30' and 230°C. and P betmeeu
JGLASSTONE, s., "Textbook of Physical Chemistry," 2nd ed.,
D. Van Nostrand Co., Inc., New York, 1946, p. 458.
JOURNAL OF CHEMICAL EDUCATION
760 mm. and 600 mm. This range of temperatures in-
cludes the great majority of compounds which can be
distilled without decomposition, and the pressure range
includes locations up to one mile, or slightly higher.
Using variables betreen these limits a nomograph can
be constructed by standard method^.^ The tempera-
ture change axis At will have two scales, since there
are two values for the constant C .
I t is of course not true that equation (4) will hold for
such low pressures as Tye have assumed, and so the
temperature corrections calculated by equation (1)!dl
be incorrect at the lowest pressures.
To get around this difficulty we proceed empirically.
The actual boiling poiuts of about ten each of asso-
ciated and normal liquids were compared with the
boiling points determined by use of the nomograph.
(In a few cases the boiline ~ o i n t were
s calculated bv use
' LEHOCZKY, P. N., "Alignment charts, their construction and
use," Ohio State Univ., Engr. Expt. Station, Circular No. 34,
rev. ed., (1947).
of t'he integrated Clausius-Clapeyron equation, using
the actual value for heat of vaporization instead of the
value assumed by Trouton's rule.) It is now possible
to make a graph of the actual boiling-point corrections
against the figures obtained from the nomograph. Now
the calibrations on the t scale are erased and the average
actual values substituted instead. The result is shown
in Figure 1. The use of the nomograph is illustrated by
the two examples. The corrections are accurate to
abont *0.3" at the lower pressures.
A useful variation of the nomograph is possible v-hen
it is to be used a t constant pressure. For example, at
Golden, Colorado, the pressure is almost always ~vithin
5 mm. of 617 mm. Figure 2 shows the boiling-point.
corrections a t 617 mm., obtained from the nomograph.
To use the chart one need only connect the normal boil-
ing point (on the two outside vertical lines) to obtain
the boiling-point correction for associated and normal
liquids on the two vertical lines in the middle of the
figure.

--200
-210
p-cymene a t 6 7 3 m m :
-
-190
175-5 = 170°C

-180

64.7-4.7 = 60°C 650

-120

--110
-
-100

- 60

Figur. 1. Nomowaph for Boiling-Point Correction to 760 mm. Cornaction of Boilin. Points at 817 to 760 rnm

VOLUME 34, NO. 2, FEBRUARY, 1957