ANNEX 2: Processing of Data

A. Density-Concentration Calibration Curve

20%, 40%, 60%, 80% and 100% ethanol solutions were prepared and their density was measured
through a densitometer to construct a Density-Concentration Calibration Curve as shown in Figure 1.

1.20

1.00

0.80
Density [g/mL]

y = -0.2128x + 1.0048
R² = 0.9919
0.60

0.40

0.20

0.00
0.00 0.20 0.40 0.60 0.80 1.00
w/w EtOH

Figure 1. Density vs. Ethanol Concentration Plot at 25 – 30 ℃

By getting the line of best fit, a general equation that describes the relationship between density and
concentration is obtained:

𝜌(𝑥𝐸𝑡𝑂𝐻 ) = −0.2128𝑥𝐸𝑡𝑂𝐻 + 1.0048 (1)

Where 𝜌 is the density and 𝑥𝐸𝑡𝑂𝐻 is the mass fraction of ethanol in the solution. The concentration (in
terms of mass fraction) of ethanol in the distillate and bottom samples can then be determined using
equation (1).

Sample:
𝑔 𝑔
𝜌 − 1.0048 0.7956 𝑚𝐿 − 1.0048 𝑚𝐿 𝑔 𝐸𝑡ℎ𝑎𝑛𝑜𝑙
𝑥𝐸𝑡𝑂𝐻 = = 𝑔 = 0.98308
−0.2128 −0.2128 𝑚𝐿 𝑔 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛
Table 1. Density and corresponding concentration of Distillate and Bottoms samples.

Distillate Bottoms
time
density [g/mL] xEtOH [g EtOH/g soln] density [g/mL] xEtOH [g EtOH/g soln]
0.0000 0.7956 0.9831 0.9503 0.2561
5.0000 0.7826 1.0442 0.9521 0.2477
10.0000 0.7852 1.0320 0.9513 0.2514
15.0000 0.7920 1.0000 0.9551 0.2336
20.0000 0.7945 0.9883 0.9554 0.2321
25.0000 0.7960 0.9812 0.9620 0.2011
30.0000 0.8013 0.9563 0.9631 0.1960
35.0000 0.8038 0.9445 0.9572 0.2237
40.0000 0.8028 0.9492 0.9595 0.2129
45.0000 0.8038 0.9445 0.9662 0.1814
50.0000 0.8068 0.9305 0.9615 0.2035
55.0000 0.8090 0.9201 0.9617 0.2025
60.0000 0.8140 0.8966 0.9635 0.1941

B. Determination of average distillate concentration

The mole fractions were first obtained by:

𝑥𝐵
𝑀𝑊𝐸𝑡𝑂𝐻
𝑋𝐵 = (2)
𝑥𝐵 1 − 𝑥𝐵
𝑀𝑊𝐸𝑡𝑂𝐻 + 𝑀𝑊𝐻2 𝑂
𝑥𝐷
𝑀𝑊𝐸𝑡𝑂𝐻
𝑋𝐷 = (3)
𝑥𝐷 1 − 𝑥𝐷
𝑀𝑊𝐸𝑡𝑂𝐻 + 𝑀𝑊𝐻2 𝑂

Whereas 𝑋𝐵 and 𝑋𝐷 are the mole fractions of the bottoms and distillate, respectively and the lower case
‘x’ represents their mass fractions. 𝑀𝑊𝐸𝑡𝑂𝐻 and 𝑀𝑊𝐻2 𝑂 are the molecular weight of ethanol and water
which is 18.02 g/mol and 46.04 g/mol. The mole fractions are presented in table 2.

Sample:
𝑔
0.9831 𝑔
𝑔
46.04 𝑔 𝑒𝑡ℎ𝑎𝑛𝑜𝑙
𝑋𝐷 = 𝑚𝑜𝑙
𝑔 𝑔 𝑔 = 0.96785 𝑔 𝑑𝑖𝑠𝑡𝑖𝑙𝑙𝑎𝑡𝑒
0.9831 𝑔 1 𝑔 − 0.9831 𝑔
𝑔 + 𝑔
46.04 18.02
𝑚𝑜𝑙 𝑚𝑜𝑙
 Table 2. Mole fractions of Distillate and Bottoms samples

time xD xB
0 0.957850146 0.11865929
5 1.121300784 0.11404431
10 1.08599261 0.11608848
15 1 0.10647583
20 0.970497894 0.10572731
25 0.953300011 0.08963032
30 0.895365139 0.08701461
35 0.869473163 0.10126741
40 0.879724601 0.09564547
45 0.869473163 0.07974267
50 0.839531062 0.09082549
55 0.81831659 0.09034696
60 0.772289878 0.08606808

Based on the Rayleigh equation,

𝑥1
𝐿1 𝑑𝑥 (4)
ln ( ) = ∫
𝐿2 𝑥2 𝑦 − 𝑥

Where 𝐿1 is the number of moles charged in the still at time zero, 𝐿2 is the moles left in the still after a
period of time, and 𝑥1 and 𝑥2 are the initial and final compositions of ethanol and the average
composition of the distillate, by mass balance is:

𝐿1 (5)
𝐿2 𝑥𝐵,𝑜 − 𝑥𝐵𝑓
𝑥𝐷,𝑎𝑣𝑒 =
𝐿1
𝐿2 − 1

Thus, an equilibrium curve of 1/(𝑥𝐷 − 𝑥𝐵 ) versus 𝑥𝐵 is plotted and by numerical or graphical integration
between 𝑥1 and 𝑥2 , 𝐿1 /𝐿2 is determined and subsequently, by equation (5), the average composition
of the distillate can also be obtained.

Integration of equation (4) was done by the trapezoidal rule which is given by the formula:
 𝑏
ℎ (6)
∫ 𝑓(𝑥)𝑑𝑥 = (𝑦 + 2𝑦1 + 2𝑦2 + 2𝑦3 … … . . +2𝑦𝑛−1 + 𝑦𝑛
𝑎 2 0

where h is the width of each trapezoid and y are the ordinates.

Figure 2. Visual Presentation of the 1/(𝒙𝑫 − 𝒙𝑩 ) versus 𝒙𝑩 and the application of the
trapezoidal rule

Sample:

𝑥𝐵,(𝑡=0) − 𝑥𝐵,(𝑡=5) 1 1
𝐴𝑟𝑒𝑎 (𝑎𝑡 𝑦1 ) = × [( )| − [( )|
2 𝑥𝐷 − 𝑥𝐵 𝑡=0 𝑥𝐷 − 𝑥𝐵 𝑡=5
0.1187 − 0.1140
= × (1.1916 − 0.9928) = 0.005041
2

Table 3. Determined area of the integral via Trapezoidal rule

time xD xB 1/(xD-xB) dx/(xD-xB)

0 0.957850146 0.11865929 1.1916 -
5 1.121300784 0.11404431 0.9928 0.005040529
10 1.08599261 0.11608848 1.0310 -0.00206852
15 1 0.10647583 1.1192 0.010334524
20 0.970497894 0.10572731 1.1564 0.000851648
25 0.953300011 0.08963032 1.1579 0.018626036
30 0.895365139 0.08701461 1.2371 0.003132228
35 0.869473163 0.10126741 1.3017 -0.01809266
40 0.879724601 0.09564547 1.2754 0.007244195
45 0.869473163 0.07974267 1.2663 0.020209575
50 0.839531062 0.09082549 1.3356 -0.01441816
55 0.81831659 0.09034696 1.3737 0.000648255
60 0.772289878 0.08606808 1.4573 0.006056623
Total Area under the curve 0.037564265
B0/Bf 1.0383
yD,ave 0.969604772