The Rayleigh Equation Revisited

What to Do When Alpha () Isnt Constant

Robert G. Kunz
RGK Environmental Consulting, L.L.C.
Hillsborough, North Carolina
Paper 118 b
2012 AIChE Spring Meeting
April 1-5, 2012
Houston, Texas

Abstract
Integration of the Rayleigh Equation for batch distillation in closed analytical form has
heretofore required that relative volatility () be assumed constant. A new technique
presented in this paper produces a continuous analytical function for the Rayleigh Equation
integral whether is constant or not. The newly developed equation reduces algebraically to
the traditional function when is absolutely constant.
Both the traditional expression at constant and the new equation are evaluated
against numerical integration for a number of ideal and non-ideal binary vapor-liquid
equilibrium (VLE) systems. The new method has proven especially useful for the non-ideal
systems investigated, in which varies widely with composition.
The method is then utilized successfully in a computer-simulated batch distillation of an
ethanol-water solution at 1 atm pressure, a popular student laboratory exercise and one of the
original systems studied by Lord Rayleigh. Results compare well with expected values.
A summary of VLE relationships for ideal and non-ideal systems plus temperaturedependent methods for analysis of constituent composition specific to the ethanol-water
system are discussed in separate appendices. These latter include, among others, refractive
index measurements assembled from various sources and estimates of liquid density for
ethanol-water mixtures extended beyond the range of published data.
The paper consists of new material supported by background information tutorial in
nature.
Keywords.
Alcohol Proof Levels; Boiling Point Curve; Density of Ethanol-Water Solutions;
Ethanol-Water Flash Points; Ethanol-Water Refractive Index; Gas Chromatography (GC);
Numerical Integration; Rayleigh Equation; Simpsons Rule; Systems: Acetone-Water, BenzeneToluene, Ethanol-Water, Ethylene Dichloride (EDC)-Toluene; Vapor-Liquid Equilibrium.

Disclaimer
(Some restrictions apply; batteries not included; your mileage may vary)
The following caveat applies: The information contained herein is offered in good faith
but without guarantee, warranty, or representation of any kind (expressed or implied) as to its
usefulness, correctness, completeness, or fitness for any particular purpose. The user
assumes all risk for its implementation and should seek independent professional verification
of its accuracy. The author assumes no responsibility and shall not be liable for any loss of
profit nor any special, incidental, consequential, or other damages which may result from the
use of any of the information contained in this presentation, be it oral or written. Any
statements concerning design, construction, operation, what constitutes regulatory
compliance, and/or how to achieve such compliance should not be construed as
recommendations on the part of the author and/or his organization.
Introduction
Distillation is a separation technique utilizing the difference in composition of a liquid
and the vapor in equilibrium with that liquid [1,2]. Simple, or differential, distillation employs
a single equilibrium stage to effect that separation. A batch distillation operates on an
unreplenished charge of material being boiled off from a still pot and then condensed as
product in another vessel. It is an unsteady-state process, where the amount and composition
of feed and product vary with time. The charge of feed material boils away and gradually
becomes richer in the less volatile/higher boiling component(s). The condensed vapor product
(distillate) increases in volume and is enhanced in the more volatile/lower boiling
component(s). These are also known as heavy and light components, respectively.
This paper discusses the simple, differential batch distillation of a two-component
(binary) system, in which none of the condensed vapor is returned, or refluxed, to the still pot,
a configuration referred to by one author as a Rayleigh Distillation [3]. A typical laboratory
setup is shown in Figure 1. It is a favorite student experiment in chemistry and engineering
laboratories throughout the world.
Simple batch distillation is not practiced extensively in industry. It is used commercially
for separating small quantities of high-value chemicals, when high purities are not required, as
a preliminary step to be followed by further processing, for separations where the equipment
requires frequent cleanout, or where the feed mixture is very easy to separate [1,2]. A rule of
thumb for ease of separation is that the feed components differ in atmospheric boiling point by
at least 25C [4, pp.167-168], 30-40C [5, p.61], or 75C [6, p.89; 7, p.89]. Whatever the
precise numerical value, the intent is that the lighter component be much more easily
vaporized in preference to the heavier component in order to distill a decent amount of highpurity product before too much of the feed material boils away.

Figure 1. Typical Laboratory Setup for Simple, Differential Batch Distillation

The Rayleigh Equation
Simple batch distillation without reflux is described by the Rayleigh Equation, first
advanced by Lord Rayleigh in 1902 [8]. In the derivation below [2; 9, p.580-581; 10; 11],
one begins with an overall mass balance:
F=W+D
where
and

F =
W =
D =

(1)

total moles of feed in the still pot/distilling flask at time (t) = 0

total moles left in still pot (bottoms)
total moles boiled off and condensed into the distillate at the same
point in time

and a component mass balance:

FxF = WxW + DxD
where

(2)

the mol fraction of the more volatile component (MVC) in the feed (F),
bottoms (W), and distillate (D).

Unsteady-state mass balance over a differential amount of time yields:

initial amt
in still

Wx

amt remaining
in still

(W dW) (x dx)

amt being
vaporized

ydW

(3)

in which y denotes the mol fraction of the more volatile component in the vapor
phase in equilibrium with its mol fraction in the liquid phase (x).
Expanding the equation above, one obtains:
Wx = Wx xdW Wdx + (dW) (dx) + ydW

(4)

Simplifying, rearranging, and neglecting the second order differential (dW) (dx) results in:
Wdx = ydW xdW

(5)

From which:
W

xW

dW/W = dx/(y x)
F

(6)

xF

and upon integration of the left-hand side between the stated limits, one obtains the Rayleigh
Equation:
xW
ln (W/F) =

dx/(y x)

(7)

xF
The integrand is not a simple function of x. At constant pressure, every value of x
corresponds to a different temperature and hence vapor pressure. Except for ideal systems
which follow Raoults Law in the liquid and the Ideal Gas Law and Daltons Law in the vapor, y
is also not related to x in a simple manner.
The standard procedure is to evaluate the integral numerically or graphically,* or to
come up with a suitable substitution in an attempt to produce an analytical solution in closed
mathematical form. Numerical integration involves repeatedly fitting the numerical values of
the integrand with a mathematical function over short ranges, integrating those functions
mathematically, and then summing. This numerical fitting and summing process results in a
series of discrete values, rather than a continuous function.
Relative Volatility
An analytical approach makes use of a parameter known as the relative volatility and
denoted by the symbol alpha ( ). It is defined as the ratio of the vapor-phase mol fraction of
the more volatile component, denoted as component 1, to its liquid-phase mol fraction, this
*

In previous times, in addition to counting boxes under the curve of the integrand or using a planimeter device
[12], the curve was drawn carefully on high quality graph paper of uniform density and then was weighed and
calibrated against a rectangular section of that same graph paper. This method is noted in Ref. [13, p.75].

ratio being divided by a similar ratio for the less volatile component 2.
separation by distillation, must be greater than 1.0. Mathematically:

For a successful

= (y1/x1) / (y2/x2) = (y1/x1) / [(1 y1) / (1 x1)]

(8)

The alternate expression above for comes about since y2= (1 y1) and x2 = (1 x1).
Rearranging Equation (8), one obtains for y1:
y1 = x1 / [1 + x1 ( 1)]

(9)

and for 1 / (y1 x1):

1
(y1 x1)

1 + ( 1) x1

( 1) x1 (1 x1)

( 1) x1 (1 x1)

(10)

(1 x1)

The relative volatility is evaluated at every point along the vapor-liquid equilibrium x-y
curve. In general, relative volatility is not absolutely constant across the entire range of x,
even for the most ideal of systems. However, in those cases where is considered to be
reasonably constant, it is taken outside the integral sign to allow the Rayleigh Equation
integral to be evaluated analytically by a closed-form mathematical function.
Now substituting the extreme right-hand side of Equation (10) into Equation (7) with
the assumption of a constant yields a new set of integrals for ln (W/F):
xW
ln (W/F) =

1
( 1)

xW

dx1
x1 (1 x1)

xF

xF

(12)

dx1
(1 x1)

in which each term can be integrated analytically [14, #40 and #29] to yield:
ln (W/F) =

1
{ ln [(1 xF)/(1 xW)] + ln (xW/xF) }
( 1)

(13)

A mathematically equivalent form [2] is:

ln (W/F) =

1
( 1)

ln

[ x(1 (1x) xx ) ] +
F

ln

(1 xF)
(1 xW)

] }

(14)

The percent of original charge remaining in the still pot is then given by:
100 (W/F) = 100 exp [ln (W/F)]

(15)

Relative Volatility from Vapor-Liquid Equilibrium (VLE) Relationships

Equations for low-pressure binary vapor-liquid equilibrium (VLE) are summarized in
Appendix A. Important variables are temperature (t), total pressure (PT), partial pressure (p),
vapor pressure (pvap), liquid-phase (x) and vapor-phase (y) mol fractions of each component,
plus so-called activity coefficients (s) when a given system cannot be considered to be ideal.
Pure-component vapor pressures are conveniently calculated using the Antoine
Equation:
log10 pvap (mmHg) = A B / [t (C) + C]

(16)

Antoine constants are listed in Table 1 for chemicals of interest in this paper.
By manipulation of these equations, the relative volatility () in Equation (8) can be
calculated at constant pressure for any temperature or the corresponding value of composition
along the VLE curves from a ratio of vapor pressures and, if necessary, activity coefficients:
= (y1/x1) / (y2/x2) = (p1vap 1) / (p2vap 2)

(17)

in which the subscript 1 denotes the more volatile component (MVC).

A system can be considered to be ideal when 1 = 2 = 1.0 for all values of x. Relative
volatilities for a number of systems some ideal, some non-ideal are listed in the second
column of Table 2. Alpha is not perfectly constant for any of these systems across the range
of interest. In general, shows a wider variation in a system exhibiting non-ideal behavior
than for an ideal system.
Other Quantities Are Determined by Material Balance
The Rayleigh Equation in whichever form for example, Equation (7), Equation (13), or
Equation (14) describes the relationship between W and xW for a given starting value of F.
The other quantities of interest are determined by material balance from Equations (1) and (2)
and Equation (18) below, derived from them:
xD = ( FxF WxW ) / ( F W )

(18)

The composition of the first drop of distillate, when W equals F and xW = xF and the
expression in Equation (18) becomes mathematically indeterminate, is provided by the x-y
equilibrium curve, as is the instantaneous composition of the distillate at every moment during
the distillation. The situation will become clearer by way of the following example.

Table 1. Antoine Equation Constants Used in the Analysis

Chemical Name
and Synonyms

Acetone

(a)

Formula

MW (b)

BP
(C) (c)

Applicable
Range(C)

H3CCOCH3

58.08

56.2

7.02447

1161.0

224

C6H6

78.12

80.1

8 to 103

6.90565

1211.033

220.790

C4H9OH

74.12

117.7

15 to 131

7.47680

1362.39

178.77

C2H5OH

46.07

78.3

8.04494

1554.3

222.65

C6H5C2H5

106.17

136.2

6.95719

1424.255

213.206

ClCH2CH2Cl

98.96

83.5

7.18431

1358.46

232.2

(CH3)2CHCH2OH

74.12

107.9

20 to 115

7.32705

1248.48

172.92

CH3OH

32.04

64.7

20 to +140

7.87863

1473.11

230.0

H3CCOC2H5

72.12

79.6

6.97421

1209.6

216

2-Propanone
Propanone
Dimethyl Ketone

Benzene
Benzol

1-Butanol
n-Butyl Alcohol
Butanol-1
n-Propyl Carbinol

Ethanol
Ethyl Alcohol
Grain Alcohol
Methyl Carbinol

Ethyl Benzene
Phenyl Ethane

Ethylene
Dichloride
(EDC)
Ethylene Chloride
1,2Dichloroethane

Isobutyl
Alcohol
Isobutanol
2-methyl-1propanol
2-methylpropanol-1
Isopropyl Carbinol

Methanol
Methyl Alcohol
Wood Alcohol
Carbinol

Methyl Ethyl
Ketone (MEK)
2-Butanone
Butanone

Table 1 (continued). Antoine Equation Constants Used in the Analysis

(a)

Chemical Name
and Synonyms

Formula

MW (b)

BP
(C) (c)

Applicable
Range(C)

1-Propanol

C3H7OH

60.11

97.2

7.99733

1569.70

209.5

H3CCH(OH)CH3

60.11

82.4

0 to 113

6.66040

813.055

132.93

C6H5C3H7

120.20

159.2

6.95142

1491.297

207.140

C6H5CH3

92.14

110.6

6 to 137

6.95464

1344.800

219.482

H2O

18.02

100.00

0 to 60
60 to 150

8.10765
7.96681

1750.286
1668.21

235.0
228.0

Propanol
Propanol-1
n-Propyl Alcohol
Ethyl Carbinol

2-Propanol
Propanol-2
Isopropanol
Isopropyl Alcohol
Dimethyl Carbinol

n-Propyl
Benzene
Propyl Benzene

Toluene
Methyl Benzene
Phenyl Methane

Water
Hydrogen Oxide

Notes:
(a) Antoine Constants from Langes Handbook of Chemistry, 11th Edition [15, Table 10-10], except
for toluene and the butanols, which are from the 12th Edition [16, Table 10-8].
(b) Molecular Weight (MW) from Handbook of Chemistry and Physics, 62nd Edition [17, pp. C-65 to
C-576], rounded for water [17, p.B-105] to 2 decimal places.
(c) Boiling point (BP) at 760 mmHg from Langes Handbook, 11th-13th Editions [15, p.4-59 and
Table 7-4; 16, p.4-59 and Table 7-4; 18] or Handbook of Chemistry and Physics, 62nd Edition [17,
pp. C-65 to C-576, p.B105], chosen to be the most consistent with boiling point calculated using the
Antoine Constants listed.

Illustrative Example. An illustrative example for batch/differential distillation is

presented in McCabe and Smith [11]. In this example, an ideal solution of 50 mol percent
benzene (MVC) and 50 mol percent toluene is subjected to batch distillation at 1 atm pressure.
(Refer again to Figure 1.) Instructions are to take 1/ as constant at 0.41 for this system over
the entire range of the distillation and to plot the calculated results for temperature and
benzene composition at various locations against the mol fraction of charge distilled (D/F).
Instantaneous mol fraction benzene is desired in the still (xW) and in the vapor leaving the still
(y1), along with the cumulative average benzene composition in the distillate (xD).
Temperatures and compositions newly calculated here via electronic spreadsheet and
plotted in Figures 2 and 3 reproduce the curves in the cited reference [11]. Calculations
performed here assume the familiar benzene-toluene system to be ideal, that is, to follow
Raoults Law. Pure component vapor pressures were computed using the Antoine Equation
with constants listed for benzene and toluene in Table 1. Any differences between the present
computations and the tabulated values accompanying the plotted curves in Ref. [11] are
Inconsequential and can be attributed to the graphical procedure employed there.

IN STILL ( C)

BOILING TEMPERATURE

110

100

90

80
0.0

0.2

0.4

0.6

0.8

1.0

MOLES DISTILLED / MOLES CHARGED

Figure 2. Calculated Temperature during Batch Distillation of 50-50 Mol Fraction

Benzene-Toluene Solution at 1 Atm Pressure
Atmospheric boiling temperature for an ideal mixture depends on the vapor pressures
and mol fractions of the pure components. The temperature in the still pot (Figure 2), initially
just above 92 C, approaches 110.6 C, the boiling point of toluene present by itself in the still
pot at the end of the distillation. Benzene concentration in the still pot (bottoms) approaches
zero as the distillation proceeds (Figure 3). The last drop in the bottoms is pure toluene,
although for safety reasons one would not want actually to distill the mixture to dryness.
Benzene in the distillate, highest at its initial instantaneous value, decreases somewhat in the

cumulative distillate as more toluene comes over. Instantaneous benzene concentration in the
vapor condensing into the distillate declines more rapidly as the benzene is boiled off, leaving
the still-pot composition richer in toluene.

MOL FRACTION BENZENE (MVC)

1.0
TOP CURVE: AVERAGE DISTILLATE
0.8

MIDDLE CURVE: INSTANTANEOUS VAPOR

0.6

0.4

BOTTOM CURVE: LIQUID IN STILL

0.2

0.0
0.0

0.2

0.4

0.6

0.8

1.0

MOLES DISTILLED / MOLES CHARGED

Figure 3. Calculated Compositions from Rayleigh Equation during Batch Distillation of

50-50 Mol Fraction Benzene-Toluene Solution at 1 Atm Pressure
Testing of Numerical Evaluation of the Integral
Using as the basis a starting value of 0.5 mol fraction in the distilling flask inspired by
the illustrative example discussed above, results from numerical integration of Equation (12)
by Simpsons Rule were compared with the exact values obtained from Equation (13). Since
Equation (13) with an absolutely constant value of is an exact analytical integration of
Equation (12), it becomes a primary standard against which to test the accuracy of a
numerical integration approximation.
Simpsons Rule for numerical integration [12]:
Area under Curve ( abscissa / 3) (ordinate 1 + 4 ordinate 2 + ordinate 3)

(19)

approximates a small section of a curve with a parabola and computes the area under that
parabola (an integral). Summing the areas from its repeated application to one adjacent
section after another produces a series of values for cumulative area. The process is
terminated when the final desired abscissa is attained.

In the present case, the area is negative since the integration is conducted from right (higher values of the
abscissa) to left (lower values). That makes sense because logarithms are negative when the argument, as here,
is a fraction less than 1.0.

10

It has been found here that repeated application of Simpsons Rule in steps of 0.02 mol
fraction and an interval size of 0.01 mol fraction (the abscissa above) reproduces the exact
integral for ln (W/F), even when exponentiated, to a degree better than can be measured
experimentally. This situation applies down to a mol fraction bordering on 0.02. Narrowing
the interval size at the lower end of the mol fraction range, where the integrand begins to
increase rapidly, maintains the accuracy of the numerical integration even further. Eventually,
however, the integrand grows without bounds as mol fraction remaining in the still pot
approaches zero.
Simpsons Rule numerical integration (the points) is compared with Equation (13) (the
curves) in Figures 4 and 5 for typical values of constant . The curves pass directly through
the points, and one cannot detect any difference between points and curve at the scale of the
figures. The same is true for even greater values of , although those curves are not shown
here. Note that the amount of bottoms remaining in the distilling flask drops steeply for the
smallest value of and begins to decline more slowly with each increase in . The conclusion
is that numerical integration with a properly chosen interval size is coincident with the results
of Equation (13), the exact solution of Equation (12) with a constant .

100

PERCENT OF ORIGINAL
CHARGE REMAINING

PARAMETER: RELATIVE VOLATILITY (ALPHA)

80

60

2.2

40

1.7
20

0
0.00

1.2

0.10

0.20

0.30

0.40

0.50

MOL FRACTION OF MVC IN BOTTOMS

Figure 4. Comparison of Numerical Integration with Exact Solution of Rayleigh Equation at

Constant (Lines Analytical, Points Numerical) Low Values of

11

100

PERCENT OF ORIGINAL
CHARGE REMAINING

80

PARAMETER: RELATIVE VOLATILITY

(ALPHA)
TOP CURVE 8.0
MIDDLE CURVE 5.0
BOTTOM CURVE 3.5

60

40

20

0
0.00

0.10

0.20

0.30

0.40

0.50

MOL FRACTION OF MVC IN BOTTOMS

Figure 5. Comparison of Numerical Integration with Exact Solution of Rayleigh Equation at

Constant (Lines Analytical, Points Numerical) Higher Values of
A New Twist
Alpha need not necessarily be constant to come up with a solution to Equation (7) as a
closed-form analytical expression. A less restrictive condition is that the factor 1/( 1) can
be fitted by a quadratic function of mol fraction (x):
1 / ( 1) = a x2 + b x + c

(20)

over the range of interest, in much the same way as the expression of gaseous heat capacities
by an empirical power series in temperature. With 1/( 1) so represented, the integrand of
Equation (10) becomes a new series of terms in the second equation below, each having an
analytical solution upon integration term by term [14, #32, #29, #40]:

xW
ln (W/F)

xF

xW
2

(a x1 + b x1 + c) dx1
X1 (1 x1)

12

xF

dx1
(1 x1)

(21)

xW
ln (W/F)

xF

xW
a x1 dx1
(1 x1)

xF

xW
(1 + b) dx1
(1 x1)

xF

c dx1
x1(1 x1)

(22)

When the smoke clears and the dust settles, one is left with the following:
ln (W/F) = a (xF xW) + (1 + a + b + c) ln [(1 xF) / (1 xW)] + c ln [ xW / xF ]

(23)

This form too is an exact solution to Equation (7). The only source of error is the goodness of
fit of the quadratic function in Equation (20). When is constant for all values of composition,
a = b = 0, c = 1/ ( 1) identically, and Equation (23) reduces to Equation (13).
Testing of the New Function against Numerical Integration
A number of real vapor-liquid equilibrium systems were chosen to test how well
Equation (23) works in practice. These are broken up in Table 2 between Systems Taken to
Be Ideal and Non-Ideal Systems, where coefficients are tabulated for Equation (20) over the
range of from x1 = 0.02 to x1 = 0.5. Chemical synonyms for the individual constituents of
these systems can be found in Table 1.
Here, the previously validated Simpsons Rule integration is the standard, using the
same interval size found suitable for the numerical integration of Equation (12) with constant
. The overall conclusion is that agreement of the newly derived Equation (23) with numerical
integration is as good as in the previous graphs where is constant (Figures 4 and 5). In
addition, one has a continuous function in Equation (23) as opposed to numerical integration,
which is valid only at discrete points. Results are discussed separately below for the Ideal and
the Non-Ideal systems.
Ideal Systems. The system ethylene dichloride (EDC)-toluene, midway down the
listing in Table 2, is representative of the ideal systems investigated. Percent of initial charge
remaining in the still pot on a molar basis is plotted in Figure 6 against mol fraction EDC. The
discrete points trace the numerical integration of Equation (7) or Equation (12) with a variable
1/( 1) inside the integral sign. The continuous curve through the points is the integrated
Equation (23) with values of a, b, and c for this system from Table 2.
The upper and lower curves represent the integrated Equation (13) with two different
constant alphas bracketing the range of values in Table 2. The range has been expanded a bit
to widen the difference between the curves. In this case, inserting the arithmetic average of
the upper and lower alphas into the integrated Equation (13) for constant would result in a
curve virtually coincident with the middle curve calculated from Equation (23), passing through
the points from numerical integration of Equation (21). Results from averaging of are better
for the Ideal Systems above EDC-toluene in Table 2 and not quite so good for those following.
However, Equation (23) using proper values of a, b, and c was found to work regardless.

13

Table 2. Coefficients of 1/ ( 1) Function

System

1/(-1) = ax12 + bx1 + c

b
c

Range of from
x1 = 0.02 to 0.5

Benzene(1) EDC(2)

1.108 1.110

0.0249847

0.414753 9.26702

Ethanol(1) 2-Propanol(2)

1.163 1.167

0.00895551

0.344138 6.15889

Methanol(1) Ethanol(2)

1.66 1.71

0.077259

0.251001 1.51560

Ethanol(1) 1-Propanol(2)

2.03 2.11

0.0549304

0.172904 0.977133

Acetone(1) MEK(2)

2.09 2.17

0.0564870

0.168884 0.924787

EDC(1) Toluene(2)

2.20 2.26

0.0381021

0.112977 0.838362

Benzene(1) Toluene(2)

2.36 2.49

0.072534

0.178451 0.741501

Methanol(1) 1-Propanol(2)

3.16 3.65

0.125203

0.241046 0.466673

Ethanol(1) 1-Butanol(2) (a)

4.0 4.6

0.090100

0.162840 0.338006

Benzene(1) Ethyl Benzene(2)

4.3 5.3

0.138854

0.210900 0.302701

Methanol(1) Isobutyl Alcohol(2)

4.4 5.5

0.129731

0.215647 0.297965

Benzene(1) n-Propyl Benzene(2)

7.1 10.7

0.183439

0.217725 0.167047

Methanol(1) Water(2)

7.6 3.6

0.228138

0.363189

Ethanol(1) Water(2)

9.8 2.0

3.5716

0.07977

Systems Taken as Ideal:

Non-ideal Systems: (b)

0.144093
0.136641
.

Acetone(1) Water(2)

28.6 5.0

0.91519

0.04840

0.039525

Notes:
(a) May not be strictly ideal, but the ideal x-y curve is bracketed by the data of two different
investigators [19,20].
(b) Coefficients A1-2 and A2-1 of van Laar Equations for Methanol-Water and Acetone-Water given
in Perrys 3rd Edition [9, p.528] are 0.36, 0.22, and 0.89, 0.65, respectively (log10 based) or 0.83,
0.51 and 2.05, 1.50 (ln based). For the Ethanol-Water system, coefficients of 0.68381, 0.41724
(log10 based) or 1.5745, 0.9607 (ln based) were determined [21] by fitting the azeotrope of 89.43
mol % ethanol and 10.57 mol % water at 78.15C [9, pp.631,633] using vapor pressures calculated
from the ethanol and water Antoine Constants of Table 1.

14

Non-Ideal Systems.

Of the three non-ideal systems evaluated, acetone-water

displays the widest variation in . Accordingly, this system has been picked to illustrate how
Equation (23) can deal with a widely varying . Amount of solution remaining in the distilling
flask (W) is shown in Figure 7 as a function of acetone concentration (xW). As in Figure 6, the
points represent the results of numerical integration.
The middle curve drawn through those points is calculated from Equation (23) using the
a, b, and c constants from Table 2 for this system. The curve provides an excellent fit to the
numerically integrated points even though the 1/( 1) fit itself is not quite so good as any of
those obtained for the ideal systems. The fit of 1/( 1) tends to improve for shorter ranges
of xW. If a better fit of 1/( 1) is needed, the range of xW can be subdivided into smaller
sections to piece together the integration all the way from the starting point to the desired
final composition. Alternatively, a cubic term can be added in the fit of 1/( 1) against
composition. In that case, Equation (22) would then contain an additional term, whose
integrated form can be found in Ref. [14, #36]. That exercise is left to the reader.
The upper and lower curves in the figure depict the analytically integrated function of
Equation (13) with constant at each of its extreme values. Clearly neither one of these
curves falls anywhere near the middle curve and the points from numerical integration, and it
is not clear a priori how to average the values to achieve such a fit. In addition, with values
of so far apart, it turns out that even the best average utilized in Equation (13) does not
reproduce the correct track of the middle curve and its associated points. Once again, use of
Equation (23) with proper values of a, b, and c is the method of choice to obtain an analytical
expression relating total moles remaining in the distilling flask with molar composition.

100
LEGEND:

PERCENT OF ORIGINAL
CHARGE REMAINING

80

60

TOP CURVE ALPHA = 2.4

MIDDLE CURVE VARIABLE ALPHA
BOTTOM CURVE ALPHA = 2.1

POINTS FROM NUMERICAL INTEGRATION

40

20

0
0.00

0.10

0.20

0.30

0.40

0.50

MOL FRACTION EDC (MVC) IN BOTTOMS

Figure 6. Newly Derived Function vs. Numerical Integration EDC-Toluene at 1 Atm

15

Testing of the New Function in Simulated Laboratory Experiment

To demonstrate the ease of use of the newly developed technique, batch distillation of
a pure ethanol-water solution was simulated at a standard atmospheric pressure of 760 mmHg
(1.013 bar). This is a favorite system employed in batch distillation as a student laboratory
exercise and one of the systems studied by Lord Rayleigh [8].

100

PERCENT OF ORIGINAL
CHARGE REMAINING

80

60

40

LEGEND:
TOP CURVE ALPHA = 28.6
MIDDLE CURVE VARIABLE ALPHA
BOTTOM CURVE ALPHA = 5.0

20

POINTS FROM NUMERICAL INTEGRATION

0
0.00

0.10

0.20

0.30

0.40

0.50

MOL FRACTION ACETONE (MVC) IN BOTTOMS

Figure 7. Newly Derived Function vs. Numerical Integration Acetone-Water at 1 Atm

The Laboratory Experiment. An initial 200-mL charge of a pure ethanol-water solution,

20% ethanol by volume (at 60 F, 15.56 C) in an apparatus similar to Figure 1 at standard

atmospheric pressure (760 mmHg, 1.013 bar) is typical [6,7,22]. Volume of the distilling flask
is some 500 millimeters (mL). Boiling stones are added to prevent bumping [4, pp.146,170].
Samples of distillate and perhaps still bottoms are taken as every 5 mL of distillate is
collected, and temperature is read at such times. The experiment is over when 50 mL of
distillate has been collected. Sometimes the total collected distillate is subjected to further
purification in a second step using a separate refluxed fractionating column. This experiment
has also been conducted using denatured alcohol and water, fermented sugar solutions, and
wine being distilled into brandy.
The student is cautioned to wait to read the temperature until droplets condense on the
thermometer bulb [4, p.172].
The experiment then proceeds drop by drop.
The
recommended distilling rate varies, but numbers in the range of 2 [6,7] to 10 [4, p.171] drops
per minute are stated. At an average 6 drops per minute (1 drop every 10 seconds), and 20
drops to the millimeter, collection of 50 mL would take just under 3 hours, exclusive of

16

analytical time. This would allow completion of the first step of the experiment within a typical
standard laboratory period.
Quantitative analysis is done by refractive index, density, or possibly gas
chromatography. A qualitative analysis for ethanol in the distillate is often conducted by
attempting to ignite several drops of solution on a watch glass, since ethanol and its aqueous
solutions greater than about 50 % by volume are combustible at room temperature [23].
These methods are reviewed in some detail in Appendix B. Whatever the method of analysis,
it is good practice to prepare ones own calibration curve(s) using the materials and analytical
equipment employed rather than relying exclusively on literature data.
The Simulation. To demonstrate the ease of use of the technique, a computer
simulation of the batch distillation laboratory experiment described above was conducted. The
simulated experiment is valid only for a binary mixture of pure ethanol and water, with an x-y
VLE curve as in Figure A3. It does not apply quantitatively to denatured alcohol containing
methanol and other ingredients, fermented sugar solutions, or wine being distilled into brandy.
The simulation begins when equilibrium becomes established as the temperature in the
laboratory experiment stabilizes and the first drop of liquid falls into the receiving vessel. The
simulation also assumes that the distillation takes place slowly enough so as to maintain true
vapor-liquid equilibrium with a drop of liquid condensed on the thermometer at all times.
Results are summarized in Table 3. Distilling flask temperature, amount of bottoms
remaining and distillate formed, plus composition of bottoms and distillate are recorded at
every 5 mL of liquid distillate collected at 20 C. There are two ways to conduct such an
experiment: save each 5-mL increment separately for individual analysis, or let the distillate
accumulate as a composite sample. In the latter case, the distillate composition would follow
the trend of the relationship depicted in Figure 3 for benzene-toluene in the illustrative
example above, but with different chemicals. Results from the simulation are listed both ways
in Table 3.
Gram moles of bottoms (W) and mol fraction of ethanol in the bottoms (xW) are related
by Equation (23), using a function for 1/( 1) from Equation (20) fitted from xW of 0 and 0.2
(a = 1.73317, b = 0.511067, c = 0.103302). As one might expect, these different constants
provide a better fit for1/( 1) over the limited range of xW in this experiment than the
coefficients listed in Table 2 for a larger span of xW.
Moles of distillate (D) and mol fraction of ethanol in the distillate (xD) are computed
from material balances [Equations (1) and (2), rearranged]. Moles are converted to grams
using a molecular weight of 46.07 for ethanol and 18.02 for water from Table 1:
Grams ethanol = 46.07 moles of ethanol

(24)

Grams water = 18.02 moles of water

(25)

Mol fraction (m.f.) ethanol is converted to wt % ethanol by

wt % = 100 (m.f.) (46.07) / [(m.f.) (46.07) + (1 m.f.) (18.02)]

17

(26)

to make use of weight-percent dependent density relationships for ethanol-water mixtures,

either at an assumed laboratory temperature of 20 C or as estimated for the solution
remaining in the distilling flask (Appendix B).
Mass is converted to volume by means of density at known temperature and
composition. Tables in Ref. [24, Tables 6.22 and 6.36], interpolated if necessary, relate wt %
and % by volume at the standard temperature of 60 F (15.56 C).
Table 3. Summary of Simulated Batch Distillation Experiment
Temp
(C)

89.1
89.6
90.0
90.5
91.0
91.6
92.2
92.8
93.5
94.2
94.9

Bottoms
(W)
g moles
mass (g)

Distillate
(D)
g moles
mass (g)

mL @ 20 C
mL @ temp

mL @ 20 C

9.7367
194.6994
200.0 209.5
9.5787
190.2358
195.2 204.2
9.4180
185.7561
190.3 199.0
9.2542
181.2583
185.4 193.7
9.0871
176.7406
180.5 188.5
8.9161
172.2004
175.6 183.3
8.7409
167.6352
170.7 178.0
8.5607
163.0420
165.8 172.8
8.3750
158.4176
160.8 167.5
8.1830
153.7584
155.8 162.3
7.9839
149.0609
150.8 157.0

0.0000
0.0000
0
0.1581
4.4636
5
0.3188
8.9433
10
0.4825
13.4410
15
0.6496
17.9588
20
0.8206
22.4989
25
0.9959
27.0641
30
1.1760
31.6573
35
1.3618
36.2818
40
1.5538
40.9410
45
1.7529
45.6385
50

Ethanol in
Bottoms (xW)
mol fract

Cumulative

Individual

Instantaneous

mol fract

mol fract

mol fract

wt %
% vol

wt %
% vol

wt %
% vol

wt %
% vol

0.0706
16.269
20.0
0.0658
15.26
18.8
0.0609
14.22
17.5
0.0560
13.17
16.3
0.0511
12.11
15.0
0.0463
11.04
13.7
0.0415
9.96
12.3
0.0367
8.88
11.0
0.0321
7.82
9.7
0.0276
6.77
8.3
0.0233
5.76
7.2

18

Ethanol in Distillate (xD)

0.3704
60.07
67.8
0.3645
59.46
67.2
0.3578
58.76
66.5
0.3508
58.04
65.8
0.3432
57.20
65.0
0.3352
56.32
64.1
0.3265
55.36
63.2
0.3174
54.31
62.2
0.3075
53.10
61.0
0.2971
51.94
59.8
0.2859
50.59
58.4

0.3704
60.07
67.8
0.3645
59.46
67.2
0.3513
58.07
65.8
0.3370
56.51
64.3
0.3214
54.78
62.6
0.3045
52.83
60.7
0.2863
50.63
58.5
0.2665
48.17
56.0
0.2454
45.40
53.1
0.2228
42.29
49.8
0.1909
38.84
46.1

0.3704
60.07
67.8
0.3577
58.74
66.5
0.3439
57.27
65.0
0.3289
55.63
63.5
0.3128
53.79
61.6
0.2952
51.72
59.6
0.2763
49.40
57.2
0.2559
46.79
54.5
0.2341
43.87
51.5
0.2109
40.61
48.0
0.1867
36.99
44.0

The boiling temperature curve relates still-pot composition and the temperature at
which it boils. The boiling temperature curve is predicted from the VLE relationship described
in Appendix A. The complete curve, including the entries in Table 3, Columns 1 and 4, is
plotted in Figure 8 against weight fraction (wt %/100) ethanol as in Ref. [24, p.251].
Experimental data from three different sources judged to be reliable [24, p.251; 25,26] are
shown for comparison. Although the data are better correlated by the broken-line curve in the
figure, agreement with the predicted (solid) curve is within several tenths of a degree Celsius
for the vast majority of the 78 data points plotted. Difference equals or exceeds 1.0 C for
only 3 of those points, with a maximum temperature difference of 1.3 C. Maximum deviations
occur in the range of 0.05 to 0.3 weight fraction ethanol. These differences in the boilingpoint curve highlight the minor imperfections in the activity-coefficient model fitted solely on
the azeotropic point (Appendix A).

SOLID CURVE CALCULATED USING VAN LAAR CONSTANTS

FITTED TO THE AZEOTROPE

EQUILIBRIUM BOILING TEMPERATURE ( C)

100

95

90

MINIMUM-BOILING AZEOTROPE AT 78.15 oC

0.956 WT FRACT ETHANOL
0.044 WT FRACT WATER

85

EMPIRICAL BROKEN-LINE CURVE

FROM A FIT TO THE EXPERIMENTAL DATA SHOWN

80

DATA FROM SOURCES CITED IN THE TEXT

75
0.0

0.2

0.4

0.6

0.8

1.0

WEIGHT FRACTION ETHANOL (MVC) IN LIQUID

Figure 8. Boiling Temperature Curve for Ethanol-Water at 1 Atm Pressure

Plotting the temperature values in Table 3 against cumulative distillate collected results
in the expected s-shaped curve of Fig. 5.8 of Refs. [6 & 7]. The simulated experiment has
been extended to collect an extra 50 mL of distillate and provide additional temperature data
points in Figure 9. Those temperatures are not listed in Table 3.
The density function developed to prepare Figure B1 in Appendix B can be used to
estimate the hot liquid remaining in the still pot during distillation. Estimated bottoms volume
is listed in Table 3, Column 2. Liquid volumes shown in the table at each boiling temperature
are 4-5 % greater than the volume of the same liquid at 20 C. Change in volume remaining
in the distilling flask is therefore not accounted for exactly by subtracting the volume of
distillate removed, measured at 20 C. Even when bottoms and distillate volumes are both

19

expressed at 20 C, those volumes are not additive because of the difference in density with
ethanol concentration.
Density of the residual liquid at each temperature and composition for the simulated
experiment summarized in Table 3 is plotted against temperature as the points in Figure 10.
As before, additional points were obtained by extending the simulation to collect another
50 mL of distillate (again not shown in the table). The point at the extreme upper right is the
liquid density of pure water boiling at 100 C and 1 atm. Experimental points extrapolate
smoothly to this datum along the curve drawn in the figure.
100

TEMPERATURE IN

DISTILLING FLASK ( C)

98

96

94

92

90

88
0

10

20

30

40

50

60

70

80

90

100

CUMULATIVE ML OF DISTILLATE COLLECTED

Figure 9. Still-Pot Temperature vs. Cumulative Volume of Distillate for Simulated

Ethanol-Water Batch Distillation at 1 Atm Pressure
The empirical curve-fit function, forced to pass through the 100 C point:

BOTTOMS

= 0.958380 + 1.35444 10 3 (t 100 C) 8.1550 10 5 [(t 100 C)] 2

3.23156 10 7 [(t 100 C)] 4

(27)

reproduces the points of the simulation with a correlation coefficient (r2) of 100 % and a
standard deviation (s2) of 0.00002. This function allows one to estimate the bottoms density
(and therefore the volume of solution left in the distilling flask), from temperature alone when
batch-distilling without reflux a 20 % by volume (60 F, 15.56 C) solution of pure ethanol and
water. Division of mass by density gives volume.
Composition of the distillate is enumerated in the last three columns of Table 3. Three
versions of distillate collection are shown. In Column 5, data are recorded at every 5 mL as
the distillate is allowed to accumulate in the receiving vessel. In Column 6, the receiving
vessel is changed as soon as each 5 mL of distillate is collected, and the individual distillate

20

samples are kept separate for analysis. Column 7 represents the instantaneous composition
at each temperature and distillate volume noted. For the first drop of distillate (0 mL
accumulated), all three columns are exactly the same. Composition is also the same, but at a
different value, in Columns 5 and 6 for the first 5 mL of accumulated sample. For other
entries, compositions show a regular progression from top to bottom and from left to right in
Columns 5, 6, and 7.

ESTIMATED DENSITY OF
STILL BOTTOMS (g/mL)

0.96

0.95

0.94

0.93

0.92
88

90

92

94

96

98

100

TEMPERATURE ( C)

Figure 10. Estimated Density of Solution Remaining in the Still Pot at Boiling Temperature
for Simulated Ethanol-Water Batch Distillation at 1 Atm Pressure
In the laboratory, distillate solutions cooled to a standard temperature of perhaps 20 C
would be analyzed quantitatively by any of the methods discussed in Appendix B. For
example, densities at laboratory temperatures are well known. Any samples extracted from
the distilling flask should also be cooled to laboratory temperature before analysis by density.
On a qualitative basis, unheated distillate samples of about 50 % by volume or more
would light off at laboratory temperature with a small flame and leave no residue on the watch
glass (Appendix B). This qualitative ignition test should produce positive results at every 5 mL
increment for the cumulative samples and for most of the individual samples.
In some versions of the experiment, the composite ethanol-rich distillate is saved and
further purified using a separate refluxed fractionating column. In a properly designed
column, composition will approach pure water in the bottoms and the azeotrope in the
overhead. A sample of that distillate would ignite on the watch glass as well, burning more
vigorously with a brighter flame and again leaving no visible residue.
Wrap-up. The newly developed equation has successfully facilitated the simulation of
an unrefluxed batch distillation experiment; however, modeling of any further purification of
distillate samples in a fractionating column is beyond the scope of the present investigation.

21

Summary and Conclusions

Batch, or differential, distillation without reflux is described by the Rayleigh Equation:

+ Relates composition and amount of material remaining in distilling flask
+ Other quantities determined by material balance
+ Illustrative example from the literature presented.
Numerical integration is required for the Rayleigh Equation in its basic form.
Substitution of relative volatility () allows analytical integration for constant .
New equation derived here allows analytical integration whether is constant or not.
Analytical integration utilizing has been evaluated here against numerical integration:
+ For constant or nearly constant
+ For a number of real vapor-liquid systems, where varies with composition.
For ideal systems, with not varying widely, use of an average is adequate.
For non-ideal systems, only the new equation follows the track of numerical integration.
The new function was used in simulation of batch distillation of pure ethanol and water.
Ethanol-water results compare favorably with expectations, for example:
+ Boiling point vs. composition curve
+ Still pot temperature vs. cumulative volume of distillate collected
+ Density of solution remaining in still pot.
Methods to analyze liquid composition are discussed for the ethanol-water system:
+ Gas chromatography (GC)
+ Refractive index data compiled from various sources
+ Densities of ethanol-water solutions extended beyond range of published data
+ Qualitative ignition test / flash points of ethanol-water solutions.
About The Author

Robert G. Kunz was an environmental engineering manager at Air Products and

Chemicals, Inc., Allentown, PA before retiring after 26+ years of service. He then joined
Cormetech, Inc., Durham, NC as Technical Project Manager in support of sales and marketing
efforts in the petroleum refining and petrochemical industries. He held engineering positions
previously at Esso Research and Engineering Company, Florham Park, NJ and The M.W.
Kellogg Company, New York, NY and is currently an independent environmental consultant.
Dr. Bob has earned a BChE degree in Chemical Engineering from Manhattan College, a PhD
in Chemical Engineering from Rensselaer Polytechnic Institute, an MS in Environmental
Engineering from Newark College of Engineering, and an MBA from Temple University. He has
contributed numerous publications to the technical literature, including topics in phase
equilibria, and is a recipient of the Water Pollution Control Federations Harrison Prescott Eddy
Medal for noteworthy research in wastewater treatment. He is author or co-author of two
books and holder of one U.S. patent. He is a member of the American Institute of Chemical
Engineers (AIChE), the American Chemical Society (ACS), and the Air & Waste Management
Association (A&WMA) and is a licensed professional engineer in several states.
Acknowledgement
The author is grateful to Roberta Kunz Fox, AIA, of fox2 design for help with Figure 1.

22

References
1. Kroschwitz, J.I. and M. Howe-Grant, editors, Kirk-Othmer Encyclopedia of Chemical
Technology, 4 ed., Vol. 8, pp.311-322, Wiley, New York (1993).
2. Coulson, J.M. and J.F. Richardson with J.R. Backhurst and J.H. Harker, Chemical
Engineering, 4 ed., Vol. 2, pp.436-440, Butterworth-Heinemann, Oxford (1999).
3. Treybal, R.E., A Simple Method for Batch Distillation, Chem. Eng., 77(21), 95-98
(Oct. 5, 1970).
4. Zubrick, J.W., The Organic Chem Lab Survival Manual, 7 ed., 350 pp., Wiley,
Hoboken, NJ (2008).
5. Mayo, D.W., R.M. Pike, and D.C. Forbes, Microscale Organic Laboratory with Multistep
and Multiscale Syntheses, 5 ed., p.61, Wiley, Hoboken, NJ (2011).
6. Williamson, K.L., R. Minard, and K.M. Peters, Macroscale and Microscale Organic
Experiments, 5 ed., pp.88-104, Houghton Mifflin Company, Boston, MA (2007).
7. Williamson, K.L., R. Minard, and K.M. Peters, Macroscale and Microscale Organic
Experiments, Selected Material Special Edition for University of Massachusetts,
Amherst, 5 ed., pp.88-104, Houghton Mifflin Company, Boston, MA (2007).
8. Lord Rayleigh, Phil. Mag., On the Distillation of Binary Mixtures, Series 6, 4(23),
521-537 (Nov. 1902).
9. Perry, J.H., editor, Chemical Engineers Handbook, 3 ed., 1942 pp., McGraw-Hill,
New York (1950).
10. Badger, W.L. and J.T. Banchero, Introduction to Chemical Engineering, pp. 245-258,
McGraw-Hill, New York (1955).
11. McCabe, W.L. and J.C. Smith, Unit Operations of Chemical Engineering, 3 ed.,
pp. 484-487, 535-540, 606, McGraw-Hill, New York (1976).
12. Thomas, G.B., Jr., Calculus and Analytic Geometry, 3 ed., pp.385-387, AddisonWesley Publishing Company, Inc., Reading, MA (1960).
13. Shoemaker, D.P., C.W. Garland, and J.W. Nibler, Experiments in Physical Chemistry,
5 ed., 890 pp., McGraw-Hill, New York (1989).
14. Hodgman, C.D., editor-in chief, Mathematical Tables from Handbook of Chemistry and
Physics, p.249, Chemical Rubber Publishing Co., Cleveland, OH (1958).

23

15. Dean, J.A., editor, Langes Handbook of Chemistry, 11 ed., McGraw-Hill, New York
(1973).
16. Dean, J.A., editor, Langes Handbook of Chemistry, 12 ed., McGraw-Hill, New York
(1978).
17. Weast, R. C. and M. J. Astle, CRC Handbook of Chemistry and Physics, CRC Press,
Inc., Boca Raton, FL (1981).
18. Dean, J.A., editor, Langes Handbook of Chemistry, 13 ed., p.4-59 (water) and
Table 7-15 (organics), McGraw-Hill, New York (1985).
19. Brunjes, A.S. and M.J.P. Bogart, Vapor-Liquid Equilibria for Commercially Important
Systems of Organic Solvents, Ind. Eng. Chem., 35(2), 255-260 (Feb. 1943).
20. Hellwig, L.R. and M. Van Winkle, Vapor-Liquid Equilibrium for Ethyl Alcohol Binary
Systems, Ind. Eng. Chem., 45(3), 624-629 (Mar. 1953).
21. Kunz, R.G., Environmental Calculations A Multimedia Approach, pp.41-52, Wiley,
Hoboken, NJ (2009).
22. Fleser, L.F. and K.L. Williamson, Organic Experiments, 7 ed, pp.64-68, D.C. Heath and
Company, Lexington, MA (1992).
23. Anon., Ethanol, [Link]/ma/enwiki/en/Ethanol (accessed on 3/8/2011).
24. Flick, E.W., editor, Industrial Solvents Handbook, 5 ed., 994 pp., Noyes Data
Corporation, Westwood, NJ (1998).
25. Jones, C.A. E.M. Schoenborn, and A.P. Colburn, Equilibrium Still for Miscible Liquids,
Ind. Eng. Chem., 35(6), 666-672 (June 1943).
26. Otsuki, H. and F.C. Williams, Effect of Pressure on Vapor-Liquid Equilibria for the
System Ethyl Alcohol-Water, CEP Symposium Series No. 6, 49, 55-67 (1953).
27. Ballard, L.H. and M. Van Winkle, Vapor-Liquid Equilibria at 760 Mm. Pressure,
Ind. Eng. Chem., 44(10), 2450-2453 (Oct. 1952).
28. Othmer, D.F., M.M. Chudgar, and S.L. Levy, Binary and Ternary Systems of Acetone,
Methyl Ethyl Ketone, and Water, Ind. Eng. Chem., 44(8), 1872-1881 (Aug. 1952).
29. Kesselman, W.D., G.E. Hollenbach, A.L. Meyers, and A..E. Humphrey, Vapor-Liquid
Equilibrium Data for Benzene-Alkylbenzene Systems, J. Chem. Eng. Data, 13(1), 34-36
(Jan.1968).

24

30. Albert, N. and P.J. Elving, Vapor-Liquid Equilibria in Binary Systems, Ind. Eng. Chem.,
41(12), 2864-2867 (Dec. 1949).
31. Gmehling, J., U. Omken., and W. Arlt Vapor-Liquid Equilibrium Data Collection
Chemistry Data Series, Vol. 1, Part 7 (Aromatic Hydrocarbons), p.382, DECHEMA,
Frankfurt (1980), citing Rollet, A.P., P. Toledano, G. Elkaim, and M. Senez, Alger Sci.
Phys., 2, 403 (1956).
32. Gmehling, J. and U. Omken., Vapor-Liquid Equilibrium Data Collection Chemistry Data
Series, Vol. 1, Part 7a (Aromatic Hydrocarbons Supplement 1), p.241, DECHEMA,
Frankfurt (2000), citing Rivenq, F., Bull. Soc. Chim. Fr., 0, 2427 (1974).
33. Carlson, H.C. and A.P. Colburn, Vapor-Liquid Equilibrium of Nonideal Solutions
Utilization of Theoretical Methods to Extend Data, Ind. Eng. Chem., 34(5), 581-589
(May 1942).
34. Eduljee, H.E., V.N. Kumarkrishnarao, and M.N. Rao, Correlation of Vapor-Liquid
Equilibrium Data for Acetone-Water System, Ind. Eng. Chem. Chem. Eng. Data Series,
3(1), 44-50 (1958).
35. York, R., Jr., and R.C. Holmes, Vapor-Liquid Equilibria Data of the System AcetoneAcetic Acid-Water, Ind. Eng. Chem., 34(3), 345-350 (Mar. 1942).
36. Othmer, D.F. and R.F. Benenati, Compositions of Vapors from Boiling Binary
Solutions, Ind. Eng. Chem., 37(3), 299-303 (Mar. 1945).
37. Ju Chin Chu, Distillation Equilibrium Data, p.24, Reinhold, New York (1950), citing
unpublished paper by D.F. Othmer, D. Friedland, and E.G. Schiebel.
38. Gmehling, J. and U. Omken., Vapor-Liquid Equilibrium Data Collection Chemistry Data
Series, Vol. 1, Part 1c (Aqueous Systems Supplement 3), p.338, DECHEMA, Frankfurt
(2003), citing Sugiyama, K. and K. Saka, Kagaku Kogaku, 33, 470 (1969).
39. Gmehling, J. and U. Omken., Vapor-Liquid Equilibrium Data Collection Chemistry Data
Series, Vol. 1, Part 1c (Aqueous Systems Supplement 3), p.345, DECHEMA, Frankfurt
(2003), citing Wohland, R. and T. Roscher, Fiz Report, 4273 (1973).
40. Beebe, A.H., Jr., K.E. Coulter, R.A. Lindsay, and E.M. Baker, Equilibria in Ethanol-Water
System at pressures Less Than Atmospheric, Ind. Eng. Chem., 34(12), 1501-1504
(Dec. 1942).
41. Othmer, D.F., W.P. Moeller, S.W. Englund, and R.G. Christopher, Composition of
Vapors from Boiling Binary Solutions, Ind. Eng. Chem., 43(3), 707-711 (Mar. 1951).

25

42. Dean, J.A., editor, Analytical Chemistry Handbook, p.9.1, McGraw-Hill, New York
(1995).
43. Andrews, L.W., The Refractive Indices of Alcohol-Water Mixtures, J. Am. Chem. Soc.,
30(3), 353-360 (1908).
44. Doroschewsky and Dvorsehantschik, J. Russ. Phys. Chem. Soc., 40, 908-931 (1908);
Chem. Zentr., 2, 1569-1571 (1908), as cited in Simmonds, C., Alcohol, Its Production,
Properties, Chemistry, and Industrial Applications, Macmillan, London (1919).
45. Speight, J.G., editor, Langes Handbook of Chemistry, 16 ed., p.1.95 and p.2.294,
McGraw-Hill, New York (2005).
46. Department of Commerce, Bureau of Standards, Standard Density and Volumetric
Tables Circular No. 19, 6 ed., 72 pp., U.S. Government Printing Office,
Washington, DC (Oct. 31, 1924).
47. Washburn, E.W., editor-in-chief, International Critical Tables of Numerical Data,
Physics, Chemistry and Technology, 1 ed., Vol. III, 444 pp., McGraw-Hill, New York
(1928).
48. The New Encyclopdia Britannica, Vol. 13, p.525, Encyclopdia, Inc., Chicago, IL
(2002).
49. Schweppe, J.L. and J.R. Lorah, Ternary System Ethyl Alcohol n-Heptane Water at
30 C, Ind. Eng. Chem., 46(11), 2391-2392 (Nov. 1954).
50. Gray, D.E., editor, American Institute of Physics Handbook, pp.2-142,2-152,2-153,2157, McGraw-Hill, New York (1957).
51. Ethyl Alcohol Handbook, 6 ed., Lyondell Chemical Company, Houston. TX,
[Link]/pdf/Ethyl_Alcohol_Handbook_Equistar.pdf (accessed on 3/8/2011).
52. Anon., Alcoholic Proof, [Link] (accessed on
3/3/2011).
53. U.S. Census Bureau, Foreign Trade Statistics, 2011 Schedule B Chapter 22,
[Link] (accessed 3/8/2011).
54. Anon., At What Proof Will Spirits Burn? Alcohol Fire Chemistry,
[Link] (accessed on 3/8 2011).
55. Spencer, A.B. and G.R. Colonna, editors, Fire Protection Guide to Hazardous Materials,
13 ed., p.325-57 (ethanol-water), p.497-8 (pure ethanol), NFPA, Quincy, MA (2002).

26

APPENDIX A

Summary of Vapor-Liquid Equilibrium (VLE) Relationships

Ideal Systems

Equations. Low-pressure binary vapor-liquid equilibrium for an ideal system is

described by the following relationships involving partial pressure (p), vapor pressure (pvap),
and liquid-phase mol fraction of each component. The total pressure is denoted as PT.
p1 = p1vap x1

(A1)

p2 = p2vap x2

(A2)

and

PT = p1 + p 2

(A3)

with

x1 + x2 = 1

(A4)

Equations (A1) and (A2) are known as Raoults Law.

If the Ideal Gas Law and Daltons Law are assumed to apply to the vapor phase, vaporphase mol fractions (y1 and y2) can be calculated from:

with

y1 = p1 / PT = p1vap x1 / PT

(A5)

y2 = p2 / PT = p2vap x2 / PT

(A6)

y1 + y2 = 1

(A7)

Vapor pressures for any system, ideal or non-ideal, are conveniently calculated using
the Antoine Equation:
log10 pvap (mmHg) = A B / [t (C) + C]

(16)

Antoine constants are listed in Table 1 of the main text for chemicals of interest in this paper.
By combining and rearranging the equations above, one obtains:
x1 = (PT p2vap) / (p1vap p2vap)

(A8)

Chiefly by means of this equation, the entire x-y equilibrium curve and temperaturecomposition curves at constant pressure for ideal systems can be mapped out in a
straightforward manner. One first chooses a temperature, computes vapor pressures from
Equation (16), then calculates x1 from Equation (A8) and y1 from Equation (A5). Only if a
specific value of x1 is desired, does the calculation become trial and error, in which a new

27

value of t is repeatedly chosen until the desired value of x1 is obtained to within whatever
tolerance is satisfactory.
Relative Volatility. The relative volatility () in Equation (8) can be calculated for
any temperature or the corresponding value of x1 along the VLE curves from a ratio of vapor
pressures:
= (y1/x1) / (y2/x2) = p1vap / p2vap

(A9)

Relative volatilities for a number of systems some ideal, some non-ideal are listed in the
second column of Table 2. Alpha is not perfectly constant for any of these systems across the
range of interest. In general, shows a wider variation in a system exhibiting non-ideal
behavior than for an ideal system following Raoults Law.
The systems considered as ideal [9, p.526;25;27-29] are listed in the top section of
the table in order of increasing . The higher the , the more the bulge between the x-y
equilibrium curve and the y=x, 45 line. EDC-toluene, midway down the listing, is
representative of the ideal systems investigated, and its x-y curve is drawn in Figure A1 along
with experimental data from several investigators [25,30-32]. Similar plots for methanolethanol and benzene-toluene have been published previously [21]. The other ideal systems
noted here have also been verified with real data. However, those additional data-enhanced
x-y diagrams are not shown since the curves are easily calculated and look largely the same.

Y1 MOL FRACTION EDC IN VAPOR

1.0

0.8

0.6

0.4

0.2

0.0
0.0

0.2

0.4

0.6

0.8

1.0

X1 MOL FRACTION EDC IN LIQUID

Figure A1. Vapor-Liquid Equilibrium Diagram for EDC-Toluene at 1 Atm Pressure

Because of the close similarity in between EDC-toluene and the adjacent benzene-toluene,
the resulting material balance relationships for EDC-toluene would closely resemble the curves

28

of the illustrative example above for benzene-toluene (Figure 3). Since the pure component
atmospheric boiling point is not quite the same for EDC and for benzene, the temperature
graph analogous to Figure 2 would differ.
Non-Ideal Systems

Equations. For these systems, a so-called activity coefficient () is introduced into

Raoults Law to yield:
p1 = p1vap 1 x1

(A10)

p2 = p2vap 2 x2

(A11)

and

PT = p1 + p 2

(A3)

with

x1 + x2 = 1

(A4)

Under the Ideal-Gas and Daltons Law assumptions, vapor phase mol fractions are given by:

again with

y1 = p1 / PT = p1vap 1 x1 / PT

(A12)

y2 = p2 / PT = p2vap 2x2 / PT

(A13)

y1 + y2 = 1

(A7)

As in ideal systems, the Antoine Equation [Equation (16)] can be used to calculate vapor
pressures. Selected Antoine constants are listed in Table 1.
Activity Coefficients. Activity coefficients (s) account for deviations from ideality.
They are back calculated as point values from experimental data and then fitted to a special
type of continuous function for use in VLE calculations. There are several empirical activitycoefficient formulations in widespread use; for any given application, some fit the deviations
better than others across the range of data. The van Laar equations [1; 9, p.527, 33], for
example:

and

log10 1

A1-2
[1 + ( A1-2 x1) / ( A2-1 x2)]

log10 2

A2-1
x2) / ( A1-2 x1)]

[1 + ( A2-1

(A14)

(A15)

fit the data well for the non-ideal systems considered here. These particular equations are also
written in terms of natural logarithms (base e), using constants 2.302585 A1-2 and A2-1.

29

Relative Volatility. Examples of non-ideal systems are contained in the last three
entries of Table 2. These systems were selected to demonstrate the effect on as the
behavior becomes more and more non-ideal. The relative volatility () in Equation (8) for
these and other non-ideal systems can be calculated by adding activity coefficients to the
vapor-pressure ratio in Equation (A9) as shown below:
= (y1/x1) / (y2/x2) = (p1vap 1) / (p2vap 2)

(17)

Additional comments on the three example systems follow.

Methanol-Water and Acetone-Water. Activity coefficients for methanol-water and
acetone-water at 1 atm pressure derived from experimental data are given in Ref. [9, p.528]
and reproduced here in a footnote to Table 2 of the main text. The methanol-water x-y curve
with accompanying experimental data from a number of investigators is shown elsewhere
[21]. It resembles the curves for the ideal systems. It uses the van Laar constants listed in
the Table 2 footnote, Antoine constants from Table 1, and a trial- and-error procedure to
compute each point on the continuous curve at the chosen total pressure.

1.0

Y1 MOL FRACTION
ACETONE IN VAPOR

0.8

0.6

0.4

0.2

0.0
0.0

0.2

0.4

0.6

0.8

1.0

X1 MOL FRACTION ACETONE IN LIQUID

Figure A2. Vapor-Liquid Equilibrium Diagram for Acetone-Water at 1 Atm Pressure

Constant-pressure calculations for non-ideal systems are always trial and error since the activity coefficients are
functions of liquid composition. An efficient method to map out the x-y equilibrium curve is to select a value of x1
and total pressure and then vary the temperature until the calculated total pressure from Equation (18) agrees as
closely as desired with the total pressure selected.

30

The acetone-water system (Figure A2) is distorted somewhat but does not exhibit
azeotropic behavior. The curve in Figure A2, prepared in a similar manner to the x-y curve for
methanol-water, correlates the data of several investigators [19,28,34-39] reasonably well.
Ethanol-Water. The classic example frequently cited to illustrate an azeotrope is the
ethanol-water system. This system is well investigated in the literature and is a favorite
student exercise in college/university laboratories throughout the world. Its predicted x-y
diagram at atmospheric pressure, shown without data points (Figure A3), was drawn by using
the same trial-and-error procedure described above for methanol-water and acetone-water.
It exhibits an azeotrope composed of 95.6 wt % ethanol and 4.4 wt % water at 1 atm
pressure (760 mmHg, 1.013 bar) and 78.15 C [9, pp.631,633]. This corresponds to 89.43
mol % ethanol and 10.57 mol % water [9, p.633]. The azeotropic point is different at other
total pressure levels [9, p.631]; water content decreases with decreasing pressure, and at
least in theory becomes zero when distillation pressure is reduced low enough [9, p.631;40].
In the special case of an azeotrope, one can obtain the van Laar constants for use in
Equations (A14) and (A15) from the composition of the azeotropic point alone [21]. Since
the fitting technique to obtain them involves only the azeotropic point, agreement with other
experimental values along the curve is not guaranteed. Although the fit is not perfect, the
myriad of accompanying data points from multiple investigators (shown elsewhere [21]) are,
however, so numerous as to obscure the calculated x-y equilibrium curve almost completely.
Furthermore, the ethanol-water system at constant pressure has been investigated
from below atmospheric pressure [40] up to at least 300 lbf/in2 absolute (psia) [26,41]. It is
well described in Ref. [26] by van Laar constants only slightly different from those obtained
here and differing among themselves but little for huge changes in pressure. Therefore, small
day-to-day variations in barometric pressure encountered in the laboratory would alter only PT
in simulation calculations, and not require modification of the 760-mmHg van Laar constants.
1.0
NOTE:
THIS CURVE, COVERED WITH DATA POINTS,
APPEARS IN THE REFERENCE CITED IN THE TEXT.

Y1 MOL FRACTION

ETHANOL IN VAPOR

0.8

0.6

0.4

AZEOTROPE AT 78.15 oC
89.43 mol % ETHANOL,
10.57 mol % WATER;
95.6 wt % ETHANOL,
4.4 wt % WATER

0.2

0.0
0.0

0.2

0.4

0.6

0.8

1.0

X1 MOL FRACTION ETHANOL IN LIQUID

Figure A3. Predicted Vapor-Liquid Equilibrium Diagram for Ethanol-Water at 1 Atm Pressure

31

APPENDIX B

ANALYTICAL METHODS FOR ETHANOL-WATER SOLUTIONS

This appendix reviews several ways to analyze for chemical composition in the ethanolwater system. These include at least three quantitative methods and one qualitative
technique. Quantitative analysis is done by refractive index, density, or possibly gas
chromatography (GC). A qualitative analysis for ethanol in the distillate is often conducted by
attempting to ignite several drops of solution on a watch glass since ethanol and its aqueous
solutions greater than about 50 % by volume are combustible at room temperature [33].
These are discussed in turn below.
Analysis Using Refractive Index
Refractive index data for mixtures of ethanol and water at various temperatures (nDt)
are summarized in Table B1, assembled from a number of sources. Refractive index can
theoretically be determined to 1 part in 10,000 [4, p.319; 6, p.299] but is more likely to agree
with literature values to 1 part in 1,000 because of the presence of impurities [6, p.279].
Refractive index is commonly measured at 20 C (nD20) [17, pp.D-200,D207]. Minor
excursions from 20 C are corrected for by adding a mean value of 0.00045 refractive index
units for every C above 20 C [6, p.299;42].
nD20 = nDt + 0.00045 (t 20 C)

(B1)

As seen in Table B1, differences in refractive index for more appreciable differences in
temperature are not exactly accounted for by the general factor.
Refractive index for ethanol-water solutions passes through a maximum point when
plotted against composition. This occurs at 79.3 wt % ethanol and 25 C, as reported by
Andrews [43], and in the vicinity of 79-80 wt % ethanol at 60 F (15.56 C), as determined by
curve-fitting the data in Ref. [24, p.250] combined with differential calculus. A less rigorous
inspection of the other entries in Table B1 detects maxima occurring somewhere in a wider
range between 70-80 wt % ethanol. In the affected range, therefore, more than one value of
ethanol composition corresponds to the same refractive index when used as the independent
variable in a calibration curve.
Determination of refractive index requires only two or three drops of sample [6, p.300].
Once the procedure is set up and the proper technique is developed [4, pp.247-251], it is
possible to analyze a new sample every minute [13, p.237]. Refractive index should be
measured as soon as possible after sampling lest the samples decompose on standing [6,
p.300]. Analysis by refractive index does, however, require specialized equipment [6, p.300].

32

Table B1. Refractive Index (nD) Values of Ethanol-Water Solutions

at Various Temperatures (C)

Ethanol
(wt %)

nD15

nD15.56

nD20

1.33345

1.33336

1.33300

10

1.34020

1.3402

20

1.34778

30

nD25

nD30

nD40

nD50

nD55

1.33250

1.3318

1.3306

1.3290

1.3281

1.3395

1.3389

1.3384

1.3368

1.3349

1.3339

1.3479

1.3469

1.3462

1.3450

1.3429

1.3406

1.3393

1.35470

1.3542

1.3535

1.3520

1.3510

1.3481

1.3452

1.3435

40

1.35948

1.3590

1.3583

1.3565

1.3550

1.3518

1.3484

1.3468

50

1.36290

1.3626

1.3616

1.3598

1.3578

1.3543

1.3506

1.3488

60

1.36505

1.3650

1.3638

1.3620

1.3597

1.3560

1.3522

1.3501

70

1.36645

1.3662

1.3652

1.363038

1.3608

1.3570

1.3528

1.3505

80

1.36690

1.3665

1.3658

1.36331

1.3611

1.3569

1.3525

1.3502

90

1.36626

1.3659

1.3650

1.36239

1.3603

1.3561

1.3515

1.3491

100

1.36332

1.36316

1.3614

1.35941

1.3573

1.3531

1.3487

1.3465

Notes:
(a)

Values at 15C, 30C, 40C, 50C, and 55C from Ref. [44].

(b)

Values at 15.56C (60F) for pure water and ethanol from Ref. [24, p.250]. Other
entries at 15.56C from regression of Ref. [24, p.250] values at other compositions.

(c)

Values at 20C from Ref. [17, p.D-200 (water) and p.D207].

(d)

Values at 25C either reported by Andrews [43], assembled from entries on p.1.95,
p.2.294, and Tables 10-71 and 10-72 of Langes Handbook [45], or curve-fitted to
interpolate between those values.

33

Analysis by Density
Published densities of ethanol-water solutions [9,15-18, 45-47] facilitate ethanol
analysis by careful measurement of density at constant temperature. Unlike the refractive
index of ethanol-water solutions, for the most part, solution density at a given temperature
corresponds to a single value for composition. The simplest technique employs a pycnometer,
or specific gravity bottle, a piece of calibrated glassware of precisely known volume [13,
pp.191-193]. It is weighed first empty and then full of solution, and density is calculated by
dividing solution weight by solution volume. Pycnometer volume is typically about 10 mL
[48]. Related studies used a 10-mL [25,40] or 5-mL [49] pycnometer to analyze by density.
Analysis by density has the advantage of using simple laboratory equipment in
widespread use. It takes a minimum of time and provides a unique value for ethanol
composition at a constant known temperature. However, in some cases, required sample size
may be greater than the amount of distillate collected.
Density-Composition Plot. Density data for ethanol-water mixtures across the entire
gamut of compositions and sample temperatures are difficult to find. This is not so much of a
problem for analysis by density, but rather for converting from mass to volume at any given
temperature and vice versa. Density data (g/mL) for liquid water (0-102 C) and ethanolwater mixtures are tabulated in NBS Circular 19 [46] and handbooks reproducing said tables.
For pure ethanol, density or its reciprocal, specific volume, is listed in various tables up to
80 C [47, p.41], and tabular entries and correlating equations are provided for density from
0-78 C [50]. Density data in lbm/gal is plotted either against C [24, p.286] or F [51, p.62]
from 5 to 60 C, parametric in vol % ethanol. Density data for liquid solutions outside this
temperature range could not be found in the published literature.
However, the parametric plots [24,p.286; 51,p.62] appear to be well behaved,
consistently spaced, and fairly linear at the upper temperatures, suggesting that missing
values might be interpolated or extrapolated with some degree of success. To that end, the
density plot has been reconstructed here in units of g/mL between 0 and 100 C, with wt %
ethanol as parameter (Figure B1).
The newly developed curves of Figure B1 are based on the data from NBS Circular 19
[46], the equations of Ref. [50], and the aforementioned graph [24, p.286]. The fit is exact
for all values for pure water, for pure ethanol up to 78 C, and for tabulated mixture data from
10-40 C [46], and in reasonable agreement with values read with difficulty from the curves of
Ref. [24, p.286] from 5 to 60 C. Two different methods produce the same extrapolated pure
ethanol curve from 78 to 100 C.
The top curve (0 % ethanol, 100 % water) contains the actual maximum point in the
density for pure water at about 4 C. Curve fitting predicts a maximum in density for 20 wt %
ethanol at about 2 C, which may or may not be the case. As drawn in Figure B1, the other
curves exhibit a continuous decrease in density with increasing temperature.
Estimated densities for pure ethanol beyond 80 C and for mixtures below 5 C and
above 60 C are not based on data and should be used with caution, since extrapolated
densities are most likely not exact. Furthermore, although values are shown in Figure B1 for
pure ethanol and for some mixture compositions above their atmospheric boiling points, these
solutions do not exist as stable liquids at 1 atm pressure. In that case, the predicted densities

34

correspond to whatever slightly elevated pressure is necessary to maintain the solution in the
liquid state. This slight difference in pressure should have a negligible effect on density since
enormous pressure increases are necessary to effect a significant change in liquid density
[47, pp.40-42]. Finally, while estimated values of density may be useful to calculate volume
from mass or vice versa, density values outside the range of data should not be used for
analytical purposes to determine solution composition.
1.05

DENSITY OF SOLUTION (g/mL)

1.00

0
20

0.95

40
0.90
60
0.85

80

0.80

100

0.75
0.70

PARAMETER: ETHANOL COMPOSITION IN WT %

0.65
0

10

20

30

40

50

60

TEMPERATURE (oC)

70

80

90

100

Figure B1. Estimated Liquid Density of Ethanol-Water Solutions

Analysis by Gas Chromatography (GC)
Gas chromatography is a well-documented separation and analysis technique used in a
chemical laboratory. When a liquid sample is injected into the gas chromatograph instrument,
it is picked up by a carrier gas, usually helium but possibly nitrogen, and passed through a
heated column packed with adsorbent material, where different chemicals are adsorbed and
desorbed at different rates. The chemicals being analyzed for arrive at a detector downstream
as a series of peaks traced on a strip chart recorder. The time for the arrival of a peak is
indicative of each particular chemical in the mixture. The width of each peak, or more
properly the area under the peak, represents the amount of that chemical present. More
information to supplement this highly simplified explanation is contained in the cited
references [4, pp.255-274; 6, pp.215-223; 7, pp.165-173; 13, pp.149-151].
Advantages: A gas chromatograph can detect extremely low concentrations in an
unknown sample. It requires a sample size on the order of 1-25 micro liters (L), smaller or
much smaller than the several drops (20 drops = 1 mL) needed for a refractive index
determination.

35

Disadvantages: The GC instrument is exceptionally expensive to purchase and may

have to be shared with other investigators, if it is available at all. It needs an hour or so
warm-up time, and requires experience it setting its temperature controls for the particular
system being analyzed and some technique/practice in handling the micro-liter syringe to
pierce the septum at the instruments injection port. Residence time for each sample to pass
through the column and show up as peaks at the detector may be several minutes or longer.
Analytical-Qualitative
A qualitative analysis for ethanol in the distillate is often conducted by attempting to
ignite several drops of solution on a watch glass. Like hydrogen, ethanol burns with a bluish
flame not easily visible in ordinary daylight [51, p.101]. Ethanol and its aqueous solutions
greater than about 50 % by volume are combustible at room temperature [23]. These will
ignite and burn to CO2 and water without leaving any residue.
Alcohol Proof. In former times, this phenomenon formed the basis of a test of the
alcoholic spirits given to members of the British Royal Navy as part of their rations [52]. In
that test, a sample lighting off with gunpowder constituted proof that the alcohol had not
been watered down. In the U.S. today, proof is defined as exactly twice the alcoholic content
by volume, measured at 60 F (15.56 C) [24, Table 6.36; 51, p. 108; 53].
Anecdotal evidence suggests that a certain brand of vodka at 100 proof (50 % ethanol
by volume) lights off, whereas this same vodka at 80 proof (40 % ethanol by volume) does
not [54]. That this should be so is explained by the flash point of ethanol-water solutions
(Table B2, prepared from a single source [55]); flash point is plotted vs. temperature in
Ref. [24, p.254]. The flash point is the lowest temperature at which just enough liquid is
evaporated at the surface to create a combustible concentration in air of gas that will catch
fire if an ignition source is present. The table shows that an ethanol-water solution is
combustible at room temperature at about the stated 50 % by volume. Heating the solution
first, which generates additional combustible ethanol vapor (and thereby lowers the flash
point), allows solutions of lesser ethanol content to ignite at the same room temperature [54].
Table B2. Flash Points of Ethanol-Water Solutions [55]
Ethanol
Volume %
5
10
20
30
40
50

Temperature
F
C
144
62
120
49
97
36
85
29
79
26
75
24

Ethanol
Volume %
60
70
80
95
96
100

Temperature
F
C
72
22
70
21
68
20
63
17
62
17
55
13

The autoignition temperature, for which no external ignition source is necessary, is much higher (for example,
363 C for 100 % ethanol [55]). Degrees F for pure ethanol in table and footnote calculated from entries in C.

36