Chemical Engineering Science, 1969, Vol. 24, pp. 113- 117.

Pergamon Press.

Printed in Great Britain.

Relations between true boiling point and ASTM distillation curves

E. J. HOFFMAN
Natural Resources Research Institute, College of Engineering,
Universityof Wyoming,
P.O. Box 3038, University Station, Laramie, Wyoming 82071
(First received 14 December 1967; in revisedform 1 Jury 1968)
Abstract-The distribution curve determined by an ASTM distillation may be transformed to a true
boiling point distribution curve. The usual slope relations and initial boiling point relations found in the
literature are used to effect the transformation. The inverse may also be carried out: the transformation
of the true boiling point curve to the ASTM curve.

boiling point (TBP) curve of a complex mixture, ideally, represents the boiling point
of each composition element of the mixture. Such
is recorded as volume distilled over against
overhead or distillate temperature. The procedure involves batch distillation in an efficient
column with reflux.
At the other extreme is differential vaporization, in which the vapor product is assumed in
equilibrium with the liquid residue. This batch
operation is more of a theoretical limit than one
obtainable in practice.
Intermediate in degree of resolution are such
batch procedures as ASTM or Engler distillations. Analysis is carried out according to prescribed procedures to insure uniformity. Even
though carried out in a flask without packing,
there is an effect of reflux and vapor-liquid
contact, and some degree of resolution occurs.
Due to simplicity, the latter mentioned types of
analyses are preferred for more routine testing
and control. However, for more precise evaluations it is desirable to convert the ASTM type
of curve to a TBP curve. The mathematical
procedures for doing so are to be derived and
reported, for converting an ASTM analysis to
a true boiling point distribution curve.
THE TRUE

THE DISTRIBUTION

CURVE

reproducing the curve have been previously

discussed [ 11.
Substitution of the integrated ClausiusClapeyron relation into Raoults and Daltons
laws for mixtures gives
aje-bdT*
AYi
&=hx,- -- p,

i= 1,2,...,k

where
& = equilibrium vaporization ratio for a
component i
mole
fraction of component i in the
AYt=
vapor phase
Ax*= mole fraction in the liquid phase
T, = temperature of the system
P, = system pressure
ai, bt = constants.
If a pure component boils at temperature Tj at
pressure PO,
PO= aje-btTo

or
bj=

TjlnF.
0

Substituting,

Ti In (at/PO)
.
T
A true boiling point curve (or an ASTM curve
I
#
as well) possesses the shape of a cumulative
Gaussian distribution or ogive. The means of In the limit, dropping subscripts
113
C.ES.Vd.UNo.

I-H

(1)

E. J. HOFFMAN

dy
dy/dT
K=z=bc/dT=T;b:exp-

T ln (a/PO)

T,

and
(2)

A=

T m =T+Ip
2h
K =

Ae-BT-To)

At the end point, T = T,and M = IV,.

Expressingthe integralusingtheerrorfunction,

(3)

where
a

{erf [dh(T-

T,)]

B=E1nE
A = ae-

-erf[dh(T,-TT,)]].

(T~/T~)ln(a/Po)

p.3

-!!

eBCTs

The constants are ordinarily evaluated from

the TBP curve itself. Here, however, we wish
to evaluate the constants from the corresponding
ASTM curve.

- To)

P,

For hydrocarbons, log,, (a in mm Hg) is 7.5 to

8.5. If PO= 14.7 psia
1,;

- 8-10.
0

The form of the K-function is preserved

dy

dT

dx
- =
dT

(y&W-To)+(

T)

(r&W-To)+(

T)

if

such that a/& = A and (p -@) = -B.

The function 4(T) has been found to be of the
form[ l]
4(T) = ,-MT-To).
(5)
The cumulative distribution curve for either
a liquid or vapor phase is then found by integration. Thus, for instance,
z=

1;

$T

=j;

e-~T-Tm2dT

I T0

where
To= initial boiling point
M = moles of vapor distilled over
Mf = total moles of sample

EVALUATION

OF TBP CONSTANTS
THE ASTM CURVE

FROM

The ASTM curve is ordinarily plotted as

temperature
(F) as ordinate vs. volume percent distilled over as abscissa. The lo-70 per
cent or 20-80 per cent region tends to be a
straight line, or better still, the 40-60 per cent
region is a straight line, representing the slope at
the median or 50 per cent point.
Correlations have been developed for relating
the ASTM slope to the TBP slope[2]. Analytically this relation is
TBP slope = 1.15 (ASTM slope) + O-4
where the slopes are in F/per cent. Multiplication by 100 converts the TBP slope to F/fraction: the slopes are convertible to a molar basis,
but for the most purposes are considered equal.
The 50 per cent boiling points are approximately equal [2]:
TBP 50% pt. = ASTM 50% pt.

,es(T-Toe-h(T-T,)dT

= A

(7)

(6)

The final or end points may also be considered

equal. However, the initial boiling points are not
equal. Correlations have been made by Geddes
[3], Edmister[4],
and others[2], but extreme
caution should be used in applying them. There
may or may not be low boiling material present
which is not registered on the ASTM initial
boiling point.
For all practical purposes, the derivative
114

Relations between true boiling point and ASTM distillation curves

d(M/W) =

h would be evaluated in a similar manner. In

fact, the ASTM-TBP
correlation can be used
to relate the constants between the two different
curves. If the TBP curve was known, the inverse of the procedure outlined would yield the
ASTM curve.

-MT-T.)

Xe

dT
is equal to A at the 50 per cent point:
T = l&=

T,.

Hence, A is equal to the reciprocal

fraction TBP slope:

of the molar

EXAMPLE

1
TBP slope in F/volume fraction

h-

As a first approximation,
to Tf yields
14;

>

integration

from To

{l-(-l)}.

The error functions will be very nearly equal to

1 and-l. Thus
h=,rrX2

from which
/3=2h(T,--T,,)

A petroleum naphtha has the ASTM and true

boiling point data as indicated in Table 1. This
information corresponds to Sample 2 of Reference [3]. In both instances the data represents
volume per cent distilled over vs. temperature.
The ASTM curve will be converted to a TBP
analysis and compared with the experimental
values.
The ASTM curve has a midpoint slope of
O-67+ F/per cent (20-80 per cent slope). Conversion yields a TBP slope of l.lSF/per cent or
1WF/fraction (the experimental
value is l-2).
The TBP initial boiling point is 95F.
Accordingly,

and

To = 95F or 555R.

A
(Y=eh14(8/h)l

The midpoint is T, = 203F or 663R.

The TBP distribution constants calculate out
as follows:

It follows that

1
A = 118 = 04085.
As a second approximation
1 = A!Ld(i)

(2(-) e&h1

(To -

Table 1. ASTM and true boiling point

distillation data for a naphtha cut

LJI I

from which
z/h2=

drA{(-)

erfdh,

(To -T,)}

and
Xf

?T=
4 h>

0.50
(-) et-f [qhl(T,-

Tdl

Substitution of these values into the distribution

equation will then yield the TBP curve.
It should be noted that the ASTM curve could
also have been fitted to a distribution-type
curve of the same form. The constants A, j3 and
115

ASTM (F)

TBP (F)

IBP
1
10
20
30
40
50
60
70
80
90
95
98
EP

158

95
103
137
160
176
190
203
214
227
242
258
268
282

181
186
192
198
203
210
217
226
242

283

E. J. HOFFMAN

For the fkst estimate,

h = ~(0~0085)* = 0.000227
v/h = dr

(04085)

= O-0151- erf[O-0151(555- 663)]

= - erf[- l-631 = 0979.

For the second estimate,
h = r (O~ooS5)z(O+79)2
g/h = dr

(0~0085)(0979) = O-0147
0.50
m
= O-512.

The TBP distribution equation becomes

zf=

0~512{erf[0~0147(T-663)]
-erf[O-0147(555-663)]}.

Substituting,

Fig. 1. Comparison of experimental and calculated true

boiling point curves for a petroleum naphtha.

M
j-g= 0~512{erf[0~0147(T-663)] - (-0.975)).

The value of Tf may be estimated by solving

1=

0~512{erf[O~0147(T,-663)]

- (-0975)).

The solution is

Table 2. Calculation of the TBP curve

T,= 771Ror311F.

WR) I/h(T-663)

The experimental ASTM and TBP curves are

represented by the points in Fig. 1. The calculated TBP curve is drawn in for comparison.
Considering the difficulties in obtaining reliable
ASTM or TBP data, especially at the initial
and final boiling ranges, the calculated TBP
curve shows good agreement with the experimental data. A closer fit requires adjustment of
T, and A. The ASTM data is generally not
precise enough, however, to warrant any step in
this direction.

95
137
160
176
190
203
214
227
242
258
268
282

555
597
620
636
650
663
674
687
702
718
728
742

REFERENCES
[l] HOFFMAN E. J.,Azeotropic and Extractiue Distillation. Interscience 1964.
[2] NELSON W. L., Petroleum Rejinery Engineering McGraw-Hill 1958.
[3] GEDDES R. L., Ind. Engng Chem. 194133 795-801.
141 EDMISTER W. C., Chem. Engng Prog. 1948 44 905.

116

-159
-097
-0.63 1
-0.397
-0.191
0
+O. 162
+0*353
+0*575
+0.81
+0*955
+1.16

erf
-0975
-0.830
-0.628
-0.426
-0.213
0
0.181
0.382
0.584
0.748
0.823
0.899

M/MA- VW,)
0%
7.4
17.8
28.1
39.0
50.0
60.1
69.4
79.8
88.4
92.0
96.4

Relations between true boiling point and ASTM distillation curves

R&I&- La courbe de distribution dCtermin6e par une distillation ASTM peut Lre transform& en
une v&table courbe de distribution du point d%bullition. Les relations habituelles de pente et les
relations du point d%bullition initial rencontr6es dans la litt&ature, servent B effectuer la transformation. On peut aussi faire linverse: la transformation de la courbe v&itable du point dCbullition en
courbe ASTM.
Zmammenfassung-Die
mittels einer ASTM-Destillation bestimmte Verteihmgskurve kann in eine
Wahre Siedepunkts-Verteihmgskurve
umgewandelt werden. Zur Durchfiihnmg der Umwandlung
werden die n der Literature gefundenen. tiblichen Neigungsverhiitnisse der Kurve sowie die Anfangssiedepunkts-Verhaltnisse
verwendet. Der umgekehrte Vorgang, das heisst die Umwandhmg der
wahren Siedepunktskurve in die ASTM-Kurve, kann ebenfalls ausgefuhrt werden.

117