Fractional Distillation of an Ethanol- water Mixture

Abstract
The purpose of this experiment is to understand the process of distilling a solution. Thesolution
of 50/50 ethanol-water was used in the experiment. Using fractional distillationapparatus
ethanol-water mixture was separated. The fractional use of copper sponge wasused in
distillation process which created the heat exchange area between the vapor of ethanol and
liquid water. The fractional distillation process yield 9.5 ml of ethanol incollecting flask, thus the
hypothesis was accepted.The purpose of this experiment is to understand the process of
distilling asolution. Distillation deals with a mixture, a solution composed of two or more
elements,that when boiled, will cause each element to vaporized at different temperatures
1
.Distillation is only effective if there is a significant difference between the boiling of the

two elements. Every element had a unique boiling point specific to the amount of bondsand
structure of that element.With that said, in this distillation lab the solution used was
50/50 ethanol-water.The normal boiling point of ethanol is 78°C while the normal boiling point of
water is100 °C. Theoretically, as the solution heated in a distillation apparatus, the
temperature begins to rise. The ethanol in 50/50 ethanol-water solution would initially vaporize
due toits lower boiling point if compared to water. This separates the ethanol from the water
inthis solution, channeling the vapors through the condenser. There, the vapor condensesinto a
liquid and collects into a collecting flask. In this specific solution, 50 percent of thesolution
leaves the heated flask to the collecting flask. Theoretically, at the end of theexperiment, the
collecting flask collects 50 percent of the originally volume. This type of distillation is known as
simple distillation
1
.Fractional distillation is more effective form of distillation because it moreaccurately separates
the ethanol from the water in 50/50 ethanol-water solution. This typeof distillation differs from
simple distillation because of the use of copper in thevaporizing process. Copper sponge is
used to create a heat exchange area between thevapors of ethanol to the liquid water. As the
vapor begins to form, it comes into contactwith the copper wires thus cooling the vapor and
condensing it to liquid.As the water heats, the liquid water releases energy in form of heat,
which acts asa catalyst in heating lower boiling point liquid ethanol. As the ethanol is
exposed thecopper wires, the heat from the water moves the ethanol gas upwards towards
thecondensing flask and the water drips back towards the heated flask. As the liquid
movesdown the tubing towards the heated flask, it comes into contact with the very hot vapor

once again. This continues many times and after multiple cooling and reheating sessionsthe
vapor is collected in the collecting flask in a theoretic pure form. Because of thisrepetitive phase
change, fractional distillation is the preferred method. It is hypothesizedthat using the fractional
distillation process in a solution of 50-50 ethanol-water, willyield equal portions of ethanol and
water.
Method/ procedure:
The procedure to perform this experiment can be found in the book
“MacroscaleA n d M i c r o s c a l e O r g a n i c E x p e r i m e n t s b y K e n n e t h L . W i l l i a m s o n ”
1
. Deviation thatoccurred while performing the experiment was that A
d e v i a t i o n t h a t o c c u r r e d w h i l e performing the experiment was that 20mL of Ethanol-
Water mixture was used instead of 30 mL. Also, the data for the temperature versus drops of
ethanol was not collected.
The result from the data shows the amount of Solution before heating anddistillate formed after
vaporization of the solution. In the distillation process, 10.5mL of 50/50 ethanol water solution
remained in the heating flask. In the collecting flask, 9.5mLof ethanol were collected after
the distillation process. According to the Figure 1, Graphfrom the book, as the temperature
increased, the amount of distillation per second shouldincrease. During the experiment, the
ethanol was removed from the 50/50 ethanol water solution and collected in a graduated
cylinder. According to the data, the amount of ethanol collected is correlated to the temperature
of the heated solution. As thetemperature increased and reached the lower boiling point of
ethanol, the amount of ethanol in collecting flask started to increase. According to Figure 1 it
shows that thetemperature of the vapor hovered around 79
o
C and then rapidly increased to the boiling
point of the diluted water. In this experiment the boiling point of water was found to89
o
C.The amount of time to heat the ethanol and vaporize the element was quick andfast because
of the copper sponge in the fractional distillation. Copper sponge acceptedheat because it is
a good electrical conductor. Using copper metal allowed fast cooling of the vapor thus cooling
the vapor and reheating it for re-distillation. The copper was usedin a sponge form so that the
increased surface area can allow a faster rate of heatexchange.Another important part of the
distillation was the open apparatus. The fractionaldistillation was only possible by the use of
vapor pressure, that once increased can givesignificant force on the walls of the apparatus thus
causing an explosion. The apparatus
should always be opened and allow even gas exchange to the environment in order to

release the vapor pressure to the environment. Once this occurs, this can continue theheating
of the solution and create even vapor formation.The hypothesis in the experiment was to see if
the 50/50 ethanol-water yields 50 percent ethanol in collecting flask after heating the solution.
As the results depicts, thefractional distillation yield nearly 50 percent ethanol as expected.
Therefore, it shows thatdistillation is an effective way of separating the two elements in
a mixture.
Conclusion
Fractional distillation yield 9.5 ml of ethanol in collecting flask from 20 ml of ethanol-water. The
theoretical value of the separating should have yield 10ml of ethanol,which meant 5% error.
Therefore the results were reasonable and as expected. However,there was still some error
which could be improved when processing experiment nexttime. The error could have been
found due to improper heating and lack of temperaturecontrol. If the solution was continuously
reheated the percent of water in the solutionwould reduce. If the instrument was correctly
attached with tuning could allow proper removal of vapor form the instrument. Increasing
the number of trials would provide for more accurate results. Also, performing experiment with a
more precise graduatedcylinder. All in all, the process of distillation is a effective way of
separating two solutionin a mixture.
Executive Summary
The binary distillation of ethanol and water is made possible due to the differencein volatilities of
the components in the boiling liquid mixture. In this experiment, acontinuous distillation unit
consisting of a perforated-tray column filled with packing of IMTP #15

together with a partial reboiler and a total condenser. This column was used tofind the
specifications and optimum operating conditions needed to produce 100 barrelsof strong, 80%
mole of ethanol blend beverage from an 8% mole of ethanol mixtureeveryday.In the experiment,
all the feed, distillate, bottom, and reflux flow-meters werecalibrated, taking into consideration
that the flow meters provide accurate measurementsonly for water flows. The refractometer was
calibrated to enable the determination of theconcentration of ethanol in any given ethanol and
water mixture from the refractiveindex. The relationship between the mole composition of
ethanol, x
EtOH
in the mixture tothe density of the mixture, ρ was found to be: ρ = 155.3*exp(-3.1752* x
EtOH
) +843.4*exp(-0.05741*x
EtOH
). The relationship between the density of the mixture and thecomposition of ethanol is no
longer linear once it reaches higher concentration.Therefore, the equation:
)]*18)1822((1[
22
s XsVsV X Xs
O H O H diluted
ρ ρ
+++=
was used todetermine the initial ethanol composition of a diluted sample.The experiment was
done by varying the reflux ratio at 6.72 and 7.31, with havingthe feed come in the middle stage.
Then we kept the reflux ratio at 6.72 and varied thefeed stage which are the middle and the
bottom stage. The actual number of stages of thecolumn used in the lab is 5 stages. To find the
number of theoretical stages required for the stage, the results from the distillation process was
analyzed using the McCabe-Thielemethod. By comparing these values, the efficiency of the
column was found from theequation: Efficiency = (# Theoretical stages/# Actual stages).
Once up-scaling calculationwas done, we used the new theoretical number of stages to run a
simulation in Aspen for the binary distillation process. Data from the experiment were used as
process conditionsto find the heat duty of both the reboiler and the condenser.When the reflux
ratio was set to be 6.72, the purity of ethanol was extremely high,which shows that the column
has very high efficiency. However, because the value wasout of the range provided in the
ethanol/water equilibrium curve, it was impossible todetermine the percent efficiency. This high
purity gain might be due to the small amountof the distillate produced. This occurred because it
was difficult to maintain the flow rateof the distillate at the specified value gained from
Aspen.The data from the experiment shows that the optimum specification for the process is to
have the feed enter the column from the middle and a reflux ratio of 7.31.Even though a higher
mole fraction of ethanol was obtained when the feed was at the bottom, the amount of distillate
produced was lower compared to the one when it is fed inthe middle. Moreover, the
mole fraction gained from the latter was sufficient with what is

required. With this, the cost is saved, where we have a smaller amount of feed needed
to produce the same amount of the beverage.In conclusion, a higher reflux ratio results in
a higher production rate, and theoptimum stage feed is at the middle of the column. To obtain a
concentration of 80%mole ethanol in the distillate, the number of stages was found to be 8
stages, based on theefficiency gained from the data (RR:7.31, feed stage: 3), which was 80%.
The distillationcolumn was calculated to be 12.8 meters, which is an appropriate measurement
for a realtime operating reactor.

Reflux Ratio
Reflux is the liquid condensed from the rising vapor which returns to the pot flask.

The Reflux ratio is the ratio between the boil up rate and the take-off rate. Or in other words, it is
the ratio between the amount of reflux that goes back down the distillation column and the
amount of reflux that is collected in the receiver (distillate).

If 5 parts of the reflux go back down the distillation column and 1 part is collected as distillate
then the reflux ratio is 5:1. In the case where all the reflux is collected as distillate the reflux ratio
would be 0:1. If no distillate is collected then a reflux ratio is not assigned. Instead we call this
"total reflux" or equilibration.

The higher the reflux ratio, the more vapor/liquid contact can occur in the distillation column. So
higher reflux ratios usually mean higher purity of the distillate. It also means that the collection
rate for the distillate will be slower.

Introduction
Distillation is the most widely-used method of separating fluid mixtures on a commercial scale, it
is thus an important part of many processes in the oil and chemical industries.
Many of the tall, thin towers which may be seen in an oil refinery or chemical plant are distillation
columns. The most common column diameter is about 2.5 m, but 6 m diameter is commonplace
and towers of 12 m dia have been built. Column heights may be as much as 30 m.
The advantages of distillation are: a) High purity products; b) Economies of scale; c) Well-
established technology and competitive supply of equipment; d) Use of low temperature, low cost
energy; e) Well suited for energy integration into the surrounding process.
It is generally-accepted that if it is possible to achieve a separation by distillation, then distillation
will be the most economical method to use. Unless azeotropes are formed (see below), this
means that nearly all mixtures where all components have a molecular weight between 140 and
40 will be separated by distillation. Low molecular weight fluids with a critical temperature below
50°C may not be condensed by cheap cooling water, and the additional costs associated with
refrigerated or cryogenic distillation may mean that another separation process will be cheaper,
at least for small-scale operation. Large molecular weight materials may thermally decompose or
polymerize at their boiling temperature even when distilled under a high vacuum. Within the 40 to
140 molecular weight range, distillation is used. In 1992, Darton estimated the world-wide
throughput of distillation columns as Oil Refining, 5 billion tonnes per year and petrochemicals,
130 million tonnes per year.
This article describes how distillation columns work, what they contain and how they are designed.
VAPOR LIQUID EQUILIBRIA
The separation of a mixture by distillation depends on the difference between the compositions
of a boiling liquid mixture and the vapor mixture in equilibrium with the liquid. For example, the
equilibrium line in Figure 1a correlates the mole fraction of benzene in the vapor, y, in equilibrium
with x, the mole fraction of benzene in the liquid for a binary mixture of benzene and toluene.
Benzene is more volatile than toluene (i.e., it has a higher vapor pressure at the same
temperature) thus at equilibrium, y is greater than x. A distillation column with a boiler at the
bottom and a condenser at the top provides a means of countercurrent contact between the rising
vapor and the descending liquid, such that at all levels the benzene moves from the liquid into the
vapor and the toluene moves from the vapor into the liquid. Thus, benzene concentrates at the
top of the column and toluene at the bottom.

Design of Distillation Columns

The procedure is introduced by first considering a binary mixture; Figure 2 shows a distillation
column. Some of the liquid from the condenser at the top of the column, Lc, is returned as reflux.
The reflux ratio is defined as the ratio of the liquid returned to the column divided by the liquid
removed as product, i.e., R = Lc/D. Figure 2 also shows the column as a series of theoretical
plates. A theoretical plate is defined as a vapor-liquid contacting device such that the vapor leaves
it in equilibrium with the liquid which leaves it. The first stage of column design is to calculate a)
the column reflux ratio; and b) the number of theoretical plates.
 Figure 2.
The theoretical plates in Figure 2 are numbered from the top of the column, and streams leaving
a plate (in equilibrium) have the number of that plate. Thus, stream V2 leaving plate 2 has vapor
concentration y2 and L2 has liquid concentration x2. If y2 and x2 refer to benzene in the benzene-
toluene binary mixture, then y2 and x2 are each located at the same point on the equilibrium curve
of Figure 1a.

A mass balance may be used to obtain a relationship between the concentrations of any
component in the streams passing each other countercurrently between the plates and the
product streams leaving the ends of the column. Thus for the column section above the feed
in Figure 2, between plates 1 and 2,
(2)

(2a)

In general, a heat balance is also required to allow for changes in L and V as the composition
changes, but in most cases, it is reasonable to assume that the molar latent heats of all
components of the mixture are approximately equal and that as much liquid evaporates as vapor
condenses. That is, L and V are assumed to be constant between the top of the column and the
feed, and constant (but different) between the feed and the bottom of the column. Thus for the
section above the feed, the mass balances becomes:

(3)

Below the feed, in a similar way, the following equations may be derived

(4)

Note that for all sections of a particular column that (xDD/V) and (xB B/V) remain constant, the
component mass balance Equations (3) and (4) maybe drawn as straight lines (Operating Lines)
below the Equilibria Line (Figure 1). Each has a slope equal to its' (L/V).
The flow rate ratios are related to the reflux ratio so that Equation (3) may be written as:
(5)

In general, the calculation of the number of theoretical plates required for a given separation at a
given reflux ratio proceeds as follows: from a known vapor composition leaving a plate (say plate
1 where y1 = xD), use the theoretical plate concept and V.L.E. data to calculate the composition
of the liquid leaving the plate (say x1); then use a mass balance [say Equation (3)] to calculate
the composition of the vapor leaving the plate below (y2 from plate 2). Repeat the calculation
using theoretical plate-mass balance to get the composition of vapor leaving the next plate (say
y3 from plate 3) until the composition matches that of the feed. Then adjust the mass balance
equations and deal with the section of the column below the feed.
These same principles are applied for multicomponent mixtures, and for changes in flow rates
caused by taking off product at intermediate positions (e.g., sidestreams) or multiple feeds. They
are well-described in many text books [Coulson and Richardson (1978) and Treybal (1981)]. The
case of a binary mixture may be used to explain the meaning of Total Reflux and Minimum Reflux
Ratio. Note that for a binary mixture, the process may be represented graphically as
in Figure 1 and the number of theoretical plates obtained by stepping off plates between the
Operating Lines and the Equilibrium Line (known as the McCabe–Thiele method).
Total Reflux is the operating condition where vapor and liquid are passing each other in the
column but no product is removed (i.e., D = 0 and R = L/D = ∞ ). The slopes of the Operating
Lines are then L/V = 1.0, that is by mass balance, between each plate y = x. At total reflux, the
number of theoretical plates required is a minimum. As the reflux ratio is reduced (by taking off
product), the number of plates required increases. The Minimum Reflux Ratio (R min) is the
lowest value of reflux at which separation can be achieved even with an infinite number of plates.
It is possible to achieve a separation at any reflux ratio above the minimum reflux ratio. As the
reflux ratio increases, the number of theoretical plates required decreases.
The Optimum Reflux Ratio (R0) is that at which the total cost of the distillation is a minimum, taking
into account the capital cost of the column (which depends on the number of theoretical plates)
and running cost, which depends on the reflux ratio. Note that the capital costs of the reboiler and
condenser also depend on the reflux ratio. Thus, usually for very low energy costs R 0/Rmin = 1.3,
and for high energy cost R0/Rmin = 1.1 (it is best not to use R0/Rmin < 1.1 to allow for possible errors
in the V.L.E data).
Column Internals, Trays and Packings
Examples of trays and packings are shown in Figures 3a and b. Trays (or plates) consist of
horizontal plates across which the descending liquid flows through streams of the ascending
vapor, which is distributed across the column by various sorts of perforations (holes, valves,
bubblecaps) in the plates.

https://www.scribd.com/doc/1018197/Fractional-Distillation-of-an-Ethanol-water-Mixture
http://www.solvent--recycling.com/reflux%20ratio.html
http://www.thermopedia.com/content/703/

drying

file:///C:/Users/Asus/Downloads/CHE504_-_Lab_Report_on_Tray_Dryer_L1_201.pdf

and

Lesson 28
CONSTANT RATE PERIOD AND FALLING RATE PERIOD DEHYDRATION
28.1 Introduction
Drying process can be divided into two period

(a) Constant rate period

(b) Falling rate period

Fig. 28.1 General rate of drying curve for solid material

In a constant drying rate period, a material or mass of material contain so much water
that liquid surface exists will dry in a manner comparable to an open faced body of
water. Diffuion of moisture from within the droplet maintains saturated surface
conditions and as long as these lasts, evaporation takes place at constant rate. When a
solid is dried under constant drying conditions, the moisture content x t typically falls as
shown in the graph A in the figure.

The graph is linear at first, then curves and eventually levels off. Graph B shows the
drying rate : it is horizontal at first indicating that the drying rate is constant, then it
curves downward and eventually falls. When the material has reached its equilibrium
moisture content, reaches zero.

Constant rate drying period will proceed until free moisture appears from the surface,
the moisture removal rate will then become progressively less. The moisture content at
which the drying rate ceases to be constant is known as the critical moisture content.
During the constant rate period, the moisture from interior migrates to the surface by
various means and is vapourised. As the moisture content is lowered, the rate of
migration to the surface is lowered. If drying occurs at too high temperatures, the
surface forms the layer of closely packed shrunken cells which are sealed together. This
presents a barrier to moisture migration and tends to keep the moisture sealed within.
This condition is known as ‘case hardening’.

The constant rate period is characterized by a rate of drying independent of moisture

content. During this period, the solid is so wet that a continous film of water exists over
the entire drying surface, and this water acts as if solids were not there. As long as the
rate of surface evaporation continues, the rate of drying is governed by equation:

The constant rate period ends when the migration rate of water from the interior of the
surface becomes less than the rate of evaporation from the surface. The period
subsequent to the critical point is called ‘the falling rate period’. Beyond this point, the
surface temperature rises, and the drying rate falls off rapidly. The falling rate period
take a far longer time than the constant rate period, even though the moisture removal
may be much less. The drying rate approaches zero at some equilibrium moisture
content.

Drying in falling rate period involves two processes:

a) movement of moisture within the material to the surface

b) removal of the moisture from the surface.

The method used to estimate drying rates and drying times in the falling rate period
depends on whether the solid is porous or non porous. In a non porous material, once
there is no superficial moisture, further drying can occur only at a rate governed by
diffusion of internal moisture to the surface. In a porous material other mechanism
appears, and drying may even takes place inside the solid instead of at the surface.

AND
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