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Masters Theses Student Theses and Dissertations

1960

Determination of vapor-liquid equilibrium data by continuous Determination of vapor-liquid equilibrium data by continuous

distillation distillation

David William Bunch

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Recommended Citation Recommended Citation Bunch, David William, "Determination of vapor-liquid equilibrium data by continuous distillation" (1960). Masters Theses. 5566. https://scholarsmine.mst.edu/masters_theses/5566

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DETERMlNATION OF VAPOR-LIQUID . EQUILIBRIUM DATA

BY CONTINUOUS DISTIIJATION

BY

DAVID .WILLIAM BUNCH

A

THESIS

submitted to the faculty of the

SCHOOL OF MINES AND METALLURGY OF THE UNIVERSITY OF MISSOURI

in partial fulfillment of the ~ork requir~d for the

Degree of .

MASTER OF s:::!IENCE IN CHEMICAL ENGINEERING

Rolla, Missouri

1960

TABLE .QE.. CONTENTS

Page

TITI.E PAGE • • ••••••••••••••• · •••••••••••••• ~ • • ••••••••• • • • 1

TAB~.OF CONTENTS••••••••••••••••••••••••••••••••••••••• 2

LIST OF ILLUSTRATIONS •••••••••••••••••••••••••••••••••••

LIST OF mBLES ••a•••••••••••••••••••••••••••••••••••••~•

6

7

I. INTRODUCTION ••••••oooQ•································· 8

II.. LITERATURE REVIEW' •••••••••• • ••••• o .....•••.•..•• • •. • •• • . 10

.... , ....................• Review of Current Methods

Circulation Method ••••••••••••••••••••••••••••

10

10

Bomb Method •••••••••o••••••••••••••••••••••••• 10

Dynamic FJ:ow-Method •• ~ •. !' .•••••••••••• • •• o. •••. • 10

Dew and Boiling Point Method•••••••••••••••••• ll

Dynamic Distillation Method••••••••••••••••••• 11

Continuous Distillation Method·~··•••••••••••• 11

Method of Tiller and R.amalho •••• o •·•...... • • • • • 12

Developnent of Equations•••••••••••••••••••••• 13

III. EXPERmE~L •• a •••• • -o .............................. 0 •••••• 15

Purpose of Investigation •••a••••~•••••••••••••••••• 15

Plan of ~eriment~tion-•••••••••••••••••••••••••••• 15 ·

Materials••••••••••••••····~······~··•••••••••••••• 16

Apparatus· .•••• ~ ... o• ............................... •. • • 16

Distillation Vessel •••••••• •.• •••••••• •. • • • • • • • 16

Temperature Measurement Devices••••••••••••••• 16

Feed Mechanism•••••••••••••••••••••••••••••••• 18

- 2 -

Condell.sex •••••• • ..................... •·•........ 18

Distillate Receiver····~···•••••••••••••••••• 18

Pressure Controlli~g System•••••••••••••••••• 18

Specific Gravity Determination.Apparatus ...... 19

Refractive Index Dete:rmination .Apparatus ••••• 19

Apparatus for Weighing Distillate•••••••••••• 19

Method of Procedure ••••••••••••••••••••••••••••••• 19

Binary-Systems 19

Texnary Systems•••••••••·•••••••••••••••••••• 20

Results • 11 •• • ••••••• • •••••••••••••••••• • ••• D a."..... 21

Sampl~ CalQUl.ations ••••••••••••••••••••••••••••••• 31

Binary Systems •oao•••••···············•••G••• 37

Calculation of Z ••••••••••••••••••••••••

Calculation of V ••••••••••••••••••••••••

Calaulation of W ......•...•.....•..•.... Calculation of xi·

Calculation of Wx

.... ~ ....•.•........... •••••••••••••••••••••••

37

37

38

38

38

Calculation of x ••• • •. •.• •••••••••••••• • •• 38

Calculation of y •••••••••••••••·•·~··••• 39

Calaulation of x •••••••••••••••••••••••• 39

n-Propy1 Alcohol-Water and Acetone-Methanol•• 39·

Tezna.:ry System••••••••••••••••••••••••••••••• 40

Calculation of Composition of Distillate 40

Calculation of Wx ··········~··········· 41 a

Calculation of x a ··~···················· 41

Calculation of·wx •••••••••••••••••••••• 41 m

- 3 -

- 4 -

Calculation of~•••••••••••••••••••••••• 41

Calculation of y a •••••••••••••••••••••••• 42

Calculation of y ••••••• p •••••••••••••••• 42 . m

Calculation of y · •••••••••••••••••o•••••• 42 w

·calculation of x ••••••••••••••••••••••••• 42 . .

Calculation o~ Equilibrimn Data from Least

Squares Equation. ••••••••••••••••a••••••••••• 43

Caloulation of Equilibrimn Temperature•••••••• 44

r;. DISC'Us:3ION • •••• • •. ••• ••••••••••••••.•••••••• ~ ••• •. ••• • • • • 46

Binary Systems••••••••••••••••••••••••••••••••••••• 46

Methanol-Water•••••••••••••••••••••••••••••••• 46

n-Propyl Alcohol-Water ••••••••••••••••••••• 0 •• 46

Acetone-Methanol •••••••••••••••••••••••••••••• 46

Ternary Systems•••••••••••••••••••••••••••••••••••• 47

Aoetone-Methanol-Water •••••••••••••••••••••••• 47

Discussion of Boiling Point Curves ••••••••••••••••• 48

Errors ••••o•o•••••••••••••••••···~··••••••••••••••• 49

Systematic Errors ···························••o•••• 49

Random Errors ••••••••••••••••••••••••••••••••••••••

Evaluation of Method of Calculation •••••••••••••••• 50

Evaluation of Experimental Method •••••••••••••o•••• 51

Time •o•••••••o•••••••••••••••••••••••••o•o•••• 51

Accuracy •••••••••••••••••••••••••••••••••••••a 52

Recommendations•••••••••••••••••••••••••••••••••••• 52

Limitations •••••• •••••o"• ................... ··~······ 53

-5-

V • CONCLtJSIONS o • • ct • a D • • • • a Do • ·• • • • o • • • • a • • o a a a • • o • • • o a o o • o • • 54

VI. SUMMARY••••••••••••••••••••••••••••••••••••••••••••••••• 55

VII. APPENDICES ••••••Q••••••••••••••••••••••o•••aoooaoaona••• 56

Appendix A, List of Materials

Appendix B1 Experimental Data •••••••••••••••••••• 0 •

57

58

VIII. BIBLIOGRAPHY ••••••••••-••••o•••••••••••••••••••••••••••• 68

IX. ACKNOWLEDGMENTS••••••••••••••••••••••••••••••••••••••••• 71

.x. VITA ......••.•...••...•.................•....••......•.. 72

- 6 -

~ .Q! ILLU8rRATIONS

Figure 1. Experimental Apparatus•••••••••••••••••••••••••••• 17

Figure 2. Vapor-Liquid Equilibrium ~or System Methanol-

Figure 3.

Figure 4.

Water •o•a•••••••••••••••••••••••••••••••~•·••••• 23

Boiling Point Curve for System Methanol-Water••••• 24

Vapor-Liquid Equilibrium for System n-Propanol-

Water •••••••••••••••••••••~a•••••••••••••••••••• 26

Figure 5. Boiling Point Curve for n-Propanol-Water •••••••••• 27

Figure 6. Vapor-Liquid Equilibrium for System n-Propanol-

Water from Least Squares Equation••••••••••••••• 29

Figure 7. Vapor-Liquid Equilibrium for System Acetone-

Figure 8.

Figure 9.

Methanol•••••••••••••••••••••••••••••••••••••••• 31

Boiling Point Curve for System Acetone-Methanol ••• 32

Vapor-Liquid Equilibrium for System Acetone-

Methanol-Water•••••••••••••••••••••••••••••••••• 35

Figure 10. Boiling Point Diagram for System Aceton~

Methanol-Water•••••••••••••••••••••••••••••••••• 36

- 7 -

LIST OF·TABLES

Table I. Vapor-Liquid Equili~ri'Uill Data for Methanol-

Table II. Vapor-Li~d Equilibrium Data for· n-Propyl Al-

cohol-Water at 760 mm Hg ••••••••••a.aooaaaaaooo• 25

Table.III. Vapor-Liquid Equilibrium. Data for n-Propyl Al­

cohol-Wa.ter at 760 mm Hg (L"east Square:;;}. ... a••••• 28

~able IV. Vapor-Liquid Equilibrium Data for Acetone-

Methanol at 760 nnn Hg •••••••••••a•••••••o•••••o 30

Table V. Vapor-Liquid Equilibrium Data for Aoetone­

Methanol-Wate.r at 760 ~JI]!Il Hg ••••• a a a O. a. 0 A. 0 fl •• 33

Table VI. Distillation Data .... :. Trial 1 (Methanol-Water) ••• o. 59

Table VII. Distillation Data: Trial 2 (n-Propyl Alcohol-

Wat er.l •.•• a O O · II O O II a a a •••••• 0 • • •••• 0 .. 0 a ••• Ill • D • Q • • • 61

Table VIII. Distillation Data .. : Trial 3 (Acetone-~ethano]J. OPO 63

Table IX. Distillation Data .. : Trial 4 (Acetone-Methanol-

Water). •• 0 •• 0 ~.a .. 0 a O •••• a O a a ••• ll o_ 0 II O II •• ll O II O O. ll II a': ·,54

Table X~ Distillation Data_; · Trial 5 · (Acetone-Methanol-

Table XI. Distillation Data: Trial 6 · (Acetone-Methanol-

Water)_ 0 Q Q O O O. 0. II. 0 ll. 0 ••••• 0 •••• 0 a~ .... 0 a~ • D. 0 0 •• · 66

Table XII. Distillation Data: Trial 7 (Acetone-Methanol-

W a. t er) a D O o It o a a a o a. a a o a o o o a a a a o a a o a a O ~ 11 0 O a o If O ll .o • o 6 7

- 8 ca

. I. !NTRODUc.rION

. The procur_ing of experimental .vapor-liquid equilibrium data

has been a.problem. of considerable importance to chemical engineers

for a number of years. Modern distillation theory and practice have

made accurate vapor-liquid equilibrium da~a practically a necessity.

Using conventi9nal methods for detennining vapor-liquid equil­

ibrium data~ ·an experimenter can obtain only a single vapor-liquid

equilibrium oom~sition per t~ial~ Ramalho {l) working with Tiller

has developed a new method which makes possible the detennination of

all values of the vapor and liquid concentrations in a single exper­

iment.

The work done by Ramalho indicated that the necessity for very

precise temperature measurements presented a serious obstacle bµt

that the method seemed to produce reau;I.ts_con~istent with the lit­

erature for the syst$ methanol-water. · It was deemed necessary to .

modify the method to eliminate the·need for precise temperature deter­

·minations for the method to become useful.· Rather. than analyze -the

mixtures by temperature data,. it was decided to use specific gravity

or refractive index. A limited amount of work was done .(2)~ by .

Ramalho toward this end but the data obtained were insufficient

for definite conclusions.

The work of this writer is an extension ot the modified

- 9 -

Ramalho-Tiller·method for detennination of vapor-liquid.equilibri1Dll.

data. Binary systems are first considered and then the method is

extended to include a ternary system. These systems are in all cases

systems which have been previously explored and reported. Thus, the

method may be checked against the conventional methods of vapor­

liquid equilibrium detenni~tions.

-10-

II. LITERATURE REVIEW

Review 5!!. Current Methods

A number of methods have been developed for the experimental

detennination of vapor-liquid-equilibrium data. Several .of the

methods in conunon use are described by Robinson and Gilliland (3)

in considerable detail. Xh.e distinguishing chara9teristics of these

methods are presented below.

Circulation Method. One conunon method for obtaining vapor­

liquid equilibr1um (4,-5,6,7,8,9,} is-by circulating the vapor through

a system and bringing it into repeated contact with the liquid

until no further change in composition takes place. In practice,

the apparatus consists of · a chamber in which part of the solution

is vaporized and a recirculation system which returns the vapors

to the original vessei. Provisions are.~de for the withdrawal

of liquid and vapor samples.

_ Bomb Method. In the bomb method {10;11,12,13,14), the liquid

sample. is placed in a closed evacuated vessel. It is then agitated

at constant tempera.ture until equilibrilllll is reached. Liquid and

vapor samples are then withdrawn and analyzed.

Dynamic Flow-Method. The dynamic flow method {15,16,17,18)

consists of passing the vapor through a seri.es of vessels containing

liquj.ds of a suitable composition. The vapor ent~~ing the first

vessel may be of a composition somewhat different from the equilibrium

vapor, · but as it passes through :the system it t.ends . to approach

equilibrium..

- 11 -

~ · and Boiling Point Method. In this method (19-,20,21,22,

23,24,25,26}, .a mixture of known composition is introduced into an

evacuated container.of variable velum~ and allowed to come to thennal

equilibrium. The volume is 'l@.ried and the pressure is observed at

which condensation conunences and is completed. The dew point and

bubble point curves of pressure versus temperature for a number of

these prepared samples are obtained and, ·by cross~plotting, conditions

of phase equilibrium may be found. by locating points at which sat­

urated liquid ~nd saturated vapor of different compositions exist

at the same temperature and pressure.

Dynamic Distillation Method. In this method (4 1 27,28,29,30,

31,32,33.), the distilling vessel is connected to a condenser and

a reoeiver. A small ~ample of distillate is taken, analyzed .and

the composition in th_e still is comp~ted by material balance.

During such a distillation the composit'ions change continually and -

the samples represent av~rage values. Because of this composition _

·variation, the quantity of liquid in the still is made large in.com­

parison to the quantity of distillate. This method involves the

assumption that vapors from a boiling l~quid are in equilibrium. ·with

the liquid. · This ~ssumption is not entirely justified but for most

cases, the differences are negligible.

Continuous Distillation Method. In this method (34,35,36,37,

38,39,401 41,.42)·, which has gained widespread use, · the liquid is

-12 -

distilled, and the vapor sample· is condensed and recyoled back to

the still. At the end of the distillation, the condensate is removed

and analyzed to detennine the yapor composition, and a separate sample

from the still is withdrawn and analyze_d to obtain the liquid. com-

position.

Method 2f Tiller ~ Ramalho. Using the conventional methods

outlined above, an experimenter can obtain only a single vapor~liquid

equilibrium composition per trial. These trials consume two to four

hours to reach an equilibrium state. Th.us a large number of experiments

must be carried out to obtain a complete picture of the variation

over the entire concentration range of vapor and liquid compositions.

·Ramalho (1) workingw~th T~ller has developed a new method by which

it is possible to obtain vapor and liquid concentrations over the

entire concentration range in a single experiment. This method

involves a continuous. distillation and depends on instantaneous

analysis of the residue liquid by measurement of _its boiling point.

The amount of ·liquid in the still at any time is detennined by a ·.

material balance. The relationship between the vapor and liquid com-

positi~ns may then be.9alculated by the familiar equation;

y s:= d(Wx) dW

{Eq. l)' ·

where: y ·= weight per cent of more volatile substance in vapor

x = weight per cent of.more volatile substance in liquid

W ::z weight of liquid in the still · ·

Equation (1) is commonly_ known qs the differential fonn of the

~ayleigh equation (~O).

- 1.3 -

Develo:gnent of Equations. A number of modifications can

be made in the experimental procedure, .including continuous feed

addition, batch feed addition, and simultaneous feed addition and

residue withdrawal. The most promising of these methods consists

of continuous addition of feed of constant composition at a constant

rate. The mathematical analysis of the process depends on application

of the material balance.

If at an arbitra:ry time during the operation an amount of

feed Z with concentration z of the more volatile component has

been added to the initial charge W, while an amount V has been 0

distilled,-an overall material balance yields,

W-W +Z-V 0

{Eq.2)

A material balance with respect to the more volatile component

gives,

Solving for y leads to

d(Wx) ·-= zdZ - y dV

Y -" -d{Wxl + dZ

dV . zd.V

(Eq. 3)

(Eq. 4)

This is the most general fonn of the equat1on used, for calculating

values of the vapor composition. A simplification can be made for

the case of binary·systems where nonnally the pure least volatile

component would be fed into the system. This leads to a value of

z equal to zero. For this case, equation (4) becomes,

d(Wx} YA- dV (Eq. 5)

-14 -

The work done by Ramalho .(1) indicated that the necessity for

very preoise temperatll!e measurements presented~ serious obstacle

but that the method seemed to produce results consistent with the

literature for the system methanol~-water. !t was · felt that the

method should be modified to eliminate the need for precise tem­

perature detenninations for the method to become useful. Thus it

was decided to analyze the distillate rather than the mixture in

the .still. This could be done by several physical or chemical means.

A limited amount of work was done by Ramalho (2} toward this end

but the data obtained was insufficient for definite conciusions.

Huckaba (43) h~s also perfonned some work using this method and the

results obtained by his work tend to substantiate the work of Ramalho.

In order to check the validity of the method, choices of

systems·have been limited to those which have been previously ex­

plored and reported •. For the system methanol-water, the data of

Cornell and Montanna ( 44} have been 'Q.sed for co~pa-rison. For the

system n-propyl alcohol-water1 the data were compared with the data

of Gadwa (45J. For the system acetone-meth9-nol, the work of Buford

and GrJswo~d (46)" and that of Fordyce (47} was used for. comparison.

The data of Buford and Griswold also provided the comparison for

the ternary system,. acetone-methanol-water.

- 15 -

III. EKPERIMENTAL

Purpose of ·Investigation

The work dorie by Ramalho indicated that the necessity for very

preoise temperature measurem~nts presented a serious obstacle to . .

the detennination of vapar-liquid equilibrium data by the Ra.roalho-

Tiller method. It was deemed neceff5ary .to modify the method to

elimin~~e the need for precise temperature determinations for the

method to becom~ usefula Ra~er .than analyze the mixtures by tem-. .

perature ·data, it was decided to ·xse specific gravity or refractive

index. A limited amount of work was done {"2_) by Ramalho toward

this end but the data obtained .were insufficient for de~inite con­

clusions. This work is an extension of the modified RamalhO-:.Tiller

method for dete.nnination of vapor-liquid equilibrium data.

~ 2f E:x:J2erimentation

In all ~ases, th~ systems selected.were those which have_been

previously· investigated and reported in the literature~ These re-

pori;ed values were. used to check the · validity of the experimental·

results obtained.

Two binary systems were first investigated: xnethanol-wate~ and

n-propyl alco~ol-water. Methanol-water comprises a much-studied section

of the literature; also, this was ' the system used .~Y Ram.alho in his

-16 -

work in which temperature was ,;i.sed as the key . variable. The system . .

n-propyl alcohol-water was used as it.was known to have an azeotrope~

The work was then e:x:tend~d to a ternary system, acetone-meth-

anol-water. Density and refractive· index were chosen as the vari-

ables to be measured. Because of discrepancies in the literature on

the reported vapor-liquid equilibrium data for the acetone-methanol

binary of this system, it was decided to also investigate this

binary.

Materials

All ma~erials used in this investigation-· are listed and

described in Appendix A, page 57.

Apparatus

The major e~µn.ent used for this investigation is illustrat~d

in Figure 1. Description of.· t!lis af>paratus -is given below:

Distillation Vessel. The dist!°llation vessel -µ.sed was a three

liter, three-neck Pyrex_ round-bottom flask_. The necks were removed

to w~thin one inch of the spherical portion of the flask to reduce

fractionation. To further reduce fractionation# the upper portion

of the flask was insulated and heated by means of electrical heating

tape.. The main squrce of heat was a Glas-Col heating mantle. All

outlets of the flask were closed by the use of rubber stoppers whi~h

were wrapped in aluminum. foil.

Temperature Measurement Devices~ The thermometer used was

A n

i l i ; : I. ; !

i ; : I

l i I! I,

·! i I

l l 1, I I

· . ~

LJ . I i

I • I

. i I I

[~] ,/

·" .. ..,.~'·

/

"\

A. Reservoir · B~ ~ts .. , o. Heat1ng·:-~t1a

-D. aottrell-Pamp E. ?1B,gnstic .~tirrer Fo fbamomater o .. oo~ _ H. lll.stillate .Raceiver . x~ Burge~.-J. Manometer. x. Manosta-t

Figure 1. Ea:perimental Apparatus

n=--·----. J . r-·1 ! I.

I, 1'

1l_ ..

I: . , ii ,, !I I

'· 1' : J I, 11 i , . q. I I

ll u 1:d=====I =====-.:!

. I

. . I! . -11 · I

· I

;1

I i

.. Drierite

calibrated in Oal~ intervals and had a range of .O'to· lOOoC,. Tem­

perature mea~em.ent was enhanced by the use of a Cottrell pump (4~l,

which was activated by a nichrQine heating ooil.

Feed Mechanism. The fe.ed was metered through two, 50 milli-

liter, self-zeroing burets. These ~ur~ts were filled from a reser-.. .

voir by gravity flow and were used alter;nately in order . that readings

might be taken and the burets refilled without disrupting the feed .

addition.

Condenser. The condenser was oori.struoted of stainless steel

tubing with copper tubing used to enclose the coolant annulus.

The tubing which connected the flask and the condenser was wrapped

with nichrome-heating wire to reduce fractionation. Water from the

laboratory tap was u~ed ~s the coolant.

Distillate Receiver. The distillate was collected from the

condenser in 250 milliliter Erlenmeyer flasks. This flask could be

isolated from the system by stopcocks. It was necessary to include.

a line dire~tly from· the manostat to ·the· reoeive~ to pro'V'd.de pressure·

equalization hetw'een the condenser and the receiver.

Pressure Controlling §zstem. The presmire was held at a con-

stant yalue of 760 millimeters mercury by _the use of a Cartesian

manostat.. Air wh~ch had been passed through easo4. (Dr~erite) to.

remove moisture was introduced to provide the differential between

barometric pressur~ and 760 millimeters mercury. This differential

was measured from a U-tube manometer whidh employed water as the man-

omet er fluid. ·

- l9 -

§peoific 9ravity Dete:rmination ApPa.Iatus • . -Specific gravities

of the samples were measured by the use of Weld pycnom.eters. These

·pycnometers were filled with the sample and immersed in a constant

temp~rature bath until they reached the desired temperature. They

were· then weighed on an analytical balance, which gave a reading

of+ 0.0001 gram.

Refractive Index. Dete:rmination AEparatus. The refractometer

used was of the dipping type and was manufactured by Bausch and Lomb.

It. could be read to ·:t 0.00000 refractive index units. Samples tested

were held at a constant temperature in a constant temperature bath

for the refractive index detennination.

ApParatus ~ Weighing Distillate. All samples and containers

weighing over 100 grams, ~uch as distillate samples and initial charge~

were weighed on an intermediate range beam balance. This balance

had a capacity of 750 grams and gave a reading of .:I: 0.01 grams.

Method 2f Procedure

Binary Systems. A weighed. quant_i ty of the more volatile com­

ponent was pl.aced in the still. The system was brought to stal).dard

atmospheric ·pressure. Heat was supplied to the still and the solution

was constantly stirred by a magnetic stirring device. The upper· . por­

tions of the still and the tube which delivered the vapor to the

condenser were heated to prevent condensation. The internal heater

. was turned on· to actuate the Cottrell pump.

20 -

When the first drop of condensate appeared in the receiver, the

addition of the less volatile component was started. When the proper

amount of distillate ~as collected, the fe~d was stopped from the

first buret and started from the second buret. The stopcocks on the

distillate line and the pressure ~al~~ing line·were closed and.the

temperature was recorded. An empty receiver was inserted onto the dis-.

tillate line and the stopcocks on the distillate line and the pressure

equalizing line were opened. The distillate was weighed and the weight

recorded. The volume of feed added was.determined and recorded.

This procedure was continued until the temperature approached the

nonnal boiling· Point of the less· volatile component at which time

the trial·was.concluded. The specific gravities of the distillate

samples were detennined by pycnometers and these values were used to

dete:rmine the compasition of the samples. Calculations were then made

to determine the vapor-liquid compositi~ns.

Ternary Sy:stems. The general procedure used in the ternary

system investigation was the same as ·that euip~oyed for the binary

system. However, the original liquid charged to the still was not

always the most volatile component but ~s. in_ some instances- a mix­

ture -of the most volatile compcnent with one of the other componen~s.

The feed was in all cases a mixture -of the two less volatile com­

ponents_. The distillate samples were analyzed , the density being

detennined by the ·_use of pycnometers and the refract! ve index by

the use of the dipping refractometer.

- 21 -

Results

All data taken in the. laboratory are tabula~ ed in AppendJtx Ba

On the following page~.,. the oaloulated values of the vapor--liquid

equ;l.~~;dum data -~e presente,d.· in ~ables as_ ·well as QT<:tphioa+tYa.

Methanol-Watero 'The vapor-iiquid equilibrium data obtained . .

for the syatem·methanol-water are presented in Table ~o Xllese

data are shown graphioal.ly and oomPRX'ed wit.h the dat·a · of Cornell.

and Montanria ':(.44} in figure 2o The boiling point curve is ahown

in Figure 3s,

n-PropY~ Aloohol-Watera The vapor-liquid equilibtj.um data

as calo:ulated by numerical differentiation are g!°ven in Table II~

These values are presented graphically in Figure 4 and are compared

with_ the data of Gadwa ·(45) •. The boiling point cmrve is given in

Figure 5. The data as calculated by fitting a curve to the. e.xper­

. im.9ll:tal data by the method o:f least . squares and subsequent differ­

entiation are shown in Table III and in Figure. 6.o .

Aoetone-Methanola· The data obtained for 'the system ac~tC?ne­

methanol are presented. in Table IV and .. in Figure 7· where .they are. .

compared wit~ the da.ta-o:E Bu.ford and Gri~old (4?l and of Fordyce (~7}.

The boiling point curve is given in Figure 8.

Acetone-Methanol-Water,. The vapor-liquid equilibr~lllil. ~ta

obtained for the syst"em acetone-methanol-water are·presented in

Table V.., These data are_ rep~esented graphically in Figure 9 where

they ar~ compared-with the data ·or ·Buford··and Griswold (46)-,. The

boiling point ourve is presented in Figure .10,.

- 22 -

TABLE I

. Vapor-Liquid·· Equilibri 1lil1 Data

~ Methanol-Water !:!:!. 1§.Q ~ ll£!

· Methanol in ~ethanol i'n ..

Liquid, Va"f)Or, Temp Liquid, Vapor, Temp Weight% Weight% oc Weight% Weight% oc

'•

5.1 28.5 95.2 45 •. 7 79,7 77.6 6.0 32.2 . .

94.5 48.2 800,6 76.9 7.0 35.5 93 .• 7 50.7 ·81.9 76.2 8.2. 39.l 92.. 8 53.3 82.6 75.7 9.5 43.0 91.o 8 55.7 83.7 75.1

10.9 46.3 90.9 58 .. 2 84.9 74.6 12.4 50.l 90a0 60a16 85.4 74.0 14.0 52.8 89.l 63.l 86.,4 73.5 15.7 55.7 88,.2 65.6 a1.4 73.0 17 .. 5 58.4 87~2 68.0 88.l 72 .. 5 1s.·4 60.9 86 .• 5 70.5 89..2 71.9 21.3 62a9 85-a 5 73.l 90.0 71 .. 4 23.l 65.0 84 .. 7 75.6 90.8 70.8 25.0 66.7 83.9 78.1 92.2 . 70.1 27.2 68a6 a·3.1 80 .. 6 92.8 69 .. 6. 29.4 70a4 82.3 83 ... 2 93.,.7 69 .• l 31.5 72al 8la6 ~.5.6 94.2 68 .• 4

-'33.8 73.6 80.8 · 88.l ~S..4 67.8 36.2 75 .. 2 80 .. 1 90a7· 96o3 67, .. 2· 38. 5 °76.3 .79.4 93 .• 3 97a9 66.6 40.9. 77.7 78q8 95 •. 9 98.7 : '65.7 43.3 79,.7 77.6

o.a

,...

8. ~ ,:: 0.6 "" ,.... 0 s:: 1 ..... ~ a 0.4 ,-c

b ~ i 0.2 .... (I) ::: .

0

0

\ .

I . I

/ ~ I I

·!/ / 1

I I

I

-0.2 0.4 · 0.6 :o.s Waight Fraation Methanol in Liquid

FIGURE 2~ VAPOR-LIQUID EQUILIBRIUM OF SYSTEM METHANOL-WATER

- 23 ::-

1,0

u 0

100

I I • I

0.2 0.4 0.6 o.a Waight Fraction Methanol in Liquid.·

FIGURE 3~ BOILIW PODrr CURVE FOR SM'EM METHANOL-WATER-

:.· 24 --~-

1.0 ·

- 25 -

TABLE rr·

Vapor-Liquid .Equilihrimn. Data

!E£ n-P~opyl Aloohol-Water at 760 !!! ,!!<r

n-Propyl Alcohol in n-Propyl Alcohol in

Liquid1 Vapor1 Temp Liquid, Vapor,. Temp Weight% Weight % oc Weight "lo Weight % oc

:

5.8 46~3 94.1 49.l 68.7 87 .• 9 7 .• 3 51.8 93 .• 0 50.9 68a9 87 .• 9 8.9 55.9 92a0 s2 .• s 68.9 87 .• 9

10.7 · 58_ .. 8 91.2 54.9 69 .• 2 87-.9 12.6 61.5 90.4 57.0 69.2 87.8 14.5 63.l 89.8 59.0 69.3 87.8 16.3 63.3 89 .• 4 61.0 69.9 87.8 18.2 6·4.2 89.l 63.0 69.8 87.8 20 .. 2 65.3 88-. 9 65.0 70 .. 3 87.7 22.1 65.8 88.-7 67.l 70.6 87 .• 7 24.1 66.2 88.6 69.2 70.9 87 .• 6 26.l 66.6 88.5 71.3 71.3 87 .• 6 28.l 67.l 88a4 73.4 72.2 87 .• 6

.30.0 67.l 8$a3 75.6 72 .. 3 87.7 31.9 67 .• 5 88.3 77.8 73.3 87.7· 33.8 67u4 88.2 80.l 74.6 87.7 35. 8 67.9 88112 82.5 . 75.1 87.9 37.7 68.1 88.l ·84 .• 9 76-. 9 88.2 39.7 67.9 88al 87.~2 . 78 .• 3 88.7 · 41.6 68.l 88-QO 89.7 80 .. 7 89.2 43.4 68.s · 88.0 92.5 84.6 90.2 45.3 68.4 88 .• 0 95.4· 88.6 92.0 47.2 68.5 87.9

- 26 -

1.0 I l I : ·----~---·--:-· i . : , ! i · i i · : ! : i l ; .... -·· I L 0 ~ .... __ . ___ · --.--------~---··-----~ ______ '---·---~ · --~ .:._ I • ~ . , i • , .·• · 1 I °:'ta og~&.,a. : 1 • ; ! , 1 !

o.a ~---. + -----i---·- . . ----- -----·+·- . ... : -------+ ---+ . i ---+ ! i l . I I t . ! . . : : ... : ... . . i : , I i ! ,...· I I ! : '. ,,/ . i : ' o.6 1·· . --------=---- · :---·-- ·-·---·---:-., -;---------r----t-----1

J f>.1- . -!----'. . ------- ----.//·/ i__ ____ L _____ : -·---t-----1 I ' I / . · l I

~-- --- !. . ! i .,..: .. ·• ~-· . ...... .. ~ . . -, . ... .. ~--------~----.--J..·-----· _i·-··--····-J o.4: · · · · · I I · I

I ; 0.2 . ..! • •• ~ • i ·· . .. . .• , .. ·· ·-· ··- -1· .. . -·· ·

·- ·· ·- · -·· t . • .

o.o . , --~_J __ J ______ : ____ L ___ _ _L __ _ L. ___ _ ; _____ J ____ J ___ J

O.O 0.2 Oo4 Oo6 008 1.0 l!3ight Fra.o~on. n-Pl'opyl Alcoho1 in Liquid

FmOim 4o VAPOR-LIQUID EQUILIBRIUM OP SETEM n-PROPIL ALCOHOL-t-IA.TER

- 27_-

. . . I . .

6 ~ta o Ga (45), · : 1- 0 hpor ental I .

"---~-1--~--l---~- _:_=i=----+-t I , I . . . . I I I I

' 100

- --_ ---_ -- --~r-· -r-1--. i - . F-- ! ·· I· : .

~- ;

95

I I - 90 : __ . -~~-+---f-----+---+---~--t------t-

. I -· . -~ I

(. -·-· · . ~- ; ., i e .. as ~ .

m·· E-4 ' g

..... . ,..

...t

i . i i I

I

i I

· 1 I . ,:8 · . 80 -- _ --- ·- --·-

I . . ..

I

! . ;

: o I ______ ....__ · __ _____ , __ ___ . -------------~

0.2 . _ 0.4 · · · o.s . o.a . ·Waight . Fraotion n-Propyl Alcohol in Licruid

FIGURE 5o . . BOILING POINT CURVE . FOR SYSI'EM n-PROPYL. ALCOHOL-WATER ·

Where,

Liquid,

TllBLE III

Vapor-Liquid Equilibri'tlln ~

for n-Propyl Aloohol-Water at ~ ~ Hg

(Calculated from Least Squares Derived Equation}

Wx i:: A +Bv+cv2+nv3 + EV4 ·+ FVS + GV6·

A= 1.4367 x 10 3

-1 B = -9.3786 x 10 -4 C = 6~2230 x 10

. -7 D = -8.7885 x 10

E =. -10 7.0149 x 10 . -13

F ::c -2.9059 x 10 . -17

G ~ - 4.8823 x 10

n-Propyl Alcohol in

Vapor, Liquid, Vapor, Weight% Weigh~ 1o Weight '7o Weight "lo

96.9 89.6 48 .• 2 68 .• 7 93.8 85.6 44.4 68.4 91.1 83 .• 0 4.0.6 67.9 86.0 7-7.8 36.7 67.6 81.4 74 .• 6 :3°2·. 9 67.2 76.7 72.7 29.l .67.0 72·;.4 70.6 25.1 66.5 68.2 70o5 21.1 65.8 64.0 10.0 11 .• 2 64 .• 1 60.0 69.7 .13.6 61.6 55.9 69 .• 4 9.7 56 .• 7 51.9 69_.o 6.5 49.8

- 29 -

l.O ,---o.jPoint~ from-JNumer~al AtjproxiniationT-:--1 //. L~roint_'_f_r~ ~east_~=~~--~i~----~-----L--) _,.,/ __J

!,. I I I I I ! !~./ .... ,_.·· l 0 8 I I I i I i ! .,· I . r i . I i 1--r---:;--r-• _-. . . ·1

L _____ ·- __ ! _________ [ . . . ! . I . ;, i: <.:~J ___ · J ___ j ! j $Yt2~~'"f'~~d . _· . ' · ! I ! 13 0.6 0

2 i I .. -l----t·---1-l----··1··/··-··-1 ii 1 ·-- ---,---,

... : I ! I I I I ; il. I ! t :/ I j ! :

; 0,4 i ,--! ·--- -----, /-1--r-1-·-· ---r---·······-·1 t i ,i __ J.. ______ , ___ · .,f/·-1------t

1

• -- ----r--· -1

1

------- ----- ~---~

~ ! . l .· . i I I ; 0 • 2 i , :-- __ /-r,,,.~-- --1--- ---1--------------,-------i------ -----t----~ "" J / I I ' ' I I Cl) I / • ,

~ ::f--+--t----1 ·- ----·-··-·-+-----+---_ ___ . ./,,.,. I i i i I I ;

,/ . I I I I O O ----- 0. 2 0. 4 · 0. 6 0. 8

Weight Fraction n-Propyl Alcohol fn Liquid

Figure 1>. VAPOR-LIQUID EQUIUBRIUM FOR SYSTEM n-PROPYL ALCOHOi-WATER FROM t6

LEAST ~UARES EQUATION

1.0

- 30 ·-

TABLE IV

· Vapor-Liquid· Equilibrillill Data

!2E. Acetone-Methanol ,e! ~ ~ !!9:

Acetone in

Liquid, . Vapor, Temperature Weight '1o Weight 1o oc

40.7 57 .• 0 60a9 43.5 59.5 ·60.3 46.4 61.0 59.7 49.3 63.9 59.2 52.3 66 .• 0 58.6 55.3 68-. 5 58.l 58.4 70.5 57.7 61..4 72.3 57.4 64.3 74.3 57.2 67.2 76.1 57.0 70.0 77.8 56.7 73.0 79.2 56.5 75.9 81.0 56.4 78.7 83.0 56.2 .81.s 85.3 56.1 84.3 87.0 56.0 86.6 89 .. 0 56.0 88.6 89.9 56 .• 0

. 90.6 91.0 56.0 92.9 92-.0 56:.0 95.0 94.3 56.0 97.0 96.5 56.0 98.9 99.0 ••••

- 31 c:» "

i~o! - I . l - ! 1· O E:!lkrimeilta1 I I · I ,• 1 . ! • I i

0 •9 ·--£>Data ot~Oiu aiiin1pm,m~ --_ -1--. x tn·ia. o~ f orcy-c .. · I l o.a -- -- -----+------- -,· ... ··------- _________ _i_ _____ J --

1 - l r /I I I j ! : i // I I

k ' +- I _J_ ' i i/ I ~ I l o. 7 ~~--1 ---- . T-.. .. . . --- I -~---r--~,. -/->1--T I -~ ~ o.6 -- I I . ._· . : / i I i -

~ . , . , ~ 0. i /r · 1 ,· - . . 0 . I ·i. ! ! / I I . ~. r! I '. / l I "' Oo:.> r---- •· · 1

r::o _ . . 1- . - 1' . I , /1 I • < V-! . ' . ! . I 1 ,

r! Oo4r---__j_---- . .- · -- i ___ [ -~I t) I ~T . I ,/l ! !

~ o.11!-------- / L,~-/-i--~--- r--··:---t------ --_ i. ' _____ J_: . °' )( ! _/ . I l - ; ~ '0 2· . i/ I \ . -=- •

1

r-·--_- 1---1---1-----i-1--~-i I • I I

o.1~ ! . ! I _:__· __,· . !,______.._._-. --+-----:i

o.sloO _J_ r _I _~~lr_Ln~I c----.....____--.rr-'

0;2 Ooh O.o v. oO

W:light Fraction ~cetone · in Liquid·

fIGURE 7o . VAPOR~i.r.QUID EQUILIBRIUM OF SYSTEM ACE'TO:NE-METHA.1'IOL

0 o· .. 0

~ -1-J e i E-t

"' ,:: .,.... r-4 .,.... 0 ~

10

. I I

······-· :--- .-. ___ .., l I

I 65 ------·· i···- ··---------

-1- - 1 i I

. . -----i-·-_ --,..--1 . . . b

---- j - ---t ---- j ___ : --'O=-· -0-,-: 0----------'-

I I , 0 I '

60

i I

i

55 I ----------;.

. ! . !

50

0

I. I i .. I

I I i ! . i

f

0.2 0.4 o.s o.a Weight Fraotion Acetone _in Liquid

FIGURE 80 BOILING. POINT CURVE FOR SYSTEM ACETONE-METHANOL

- 32 ca

1.0

- 33 -

TABLE v·

·Vapor-LiquidEquilibritlIIl Data

for Acetone-Methanol-Water at 760 mm Hg .._...... _,._,. ------- ....._... ~

. . Wei.ght % ~n Liquid. Weight "lo in Vapor Temp

oc

Acetone Methanol Water Acetone Methanol .Water

98.5 . o.4 1.1 98.5 o.s 1.0 .... 95.4 1.1 3.5 97.4 0.6 2.0 56.5 92.2 1.8 s ... o 96.6 1. 3, 2 .• 2 57.1 88.9 2 ... 5 8.5 95.4• 0.3 4.3 57 .. 6 85.6 .3.4 11.0 94.9 006 4.5 58.l 82.2 4.3 13,.5 95.1· Oa3 4 ... 6 58 .• 6 78a5 ·4 .• 9 16 .• 6 94.8 0 .. 5 4 .• 7 59.l 74.8 5.8 19 .• 4 95.0 0116 4.4 59. 5 . 70.9 · 7.0 22.1 94.8 a.. 5 ~ .. 7 60.0 67.6 a.a 22 .• 4 94.0 1.1 4,.9 60.5 · 62.0 9 .• 1 2·8. 9 93.5 lo3 5.2 61.0 57.4 10~2 32.4 93.l l.l 5.8 61.6 52.2 lL,4 36,.4 92.5 1.6 5.9 62.3 46.6 12.7 40.7 90.5 :·i3.0 6.5 63.0 41.0 13,.9 . 45.l 90 .. 0 3a3 6.7 63.8 35.l 15.2 49 .• 7 87.9 4o0 8.1 65.2 28.4:. 16 .• 6 55.0 86.0 5.6 8.4 66 .. 7 21.5 17 .• 7 60~8 78.0. 12.6 9.4 68 ... 9 98.5 o .. 8 0.7 ·98.7 Oa2 1.1 O a Cl O

· 95.4 2 .• 7 1 .• 9 97~2· lo6 t .. 2 56.9 92.2 5..0 2 .. a 9.5.l 3.4 1-. 5 .57.0 89.0 7Q2 s.8 93. 8 4 .• 5 ]... 7 57.1 85.8 9.,.4 4 .• 8 93.1· 4-1i8 2-.1 57 .• 3 82.5 . ll-116 5.9 91.8 5-..9 2 . .,3 57 .• 5 79.0: 14.1 6.9 90a6 6 .. 8 2 .. 6 57.8 75 .. 3 1606 8 .. 1 89.9 7.7 2.4 58 .• 2 71.7 19.]. 9,113 88 .• l 8a8 3.1 58.5 68 ... 0 21 .. 6 10114 87.0 . 9.3 3.7 58.8 64.2 24.2 11.6 85~4 11.0 3.6 59.2 60.3 26.8 12 .• 9 83. 8 12,.2 4.Q 59.8 56.3 29 .. 5'. 14 .• 2 82.3 13 .• 3 4.4 60.3 52.3 32.2 15-.5 80.4 15.0 4.6 60.8 48 .. 2 ·34.9 16.9 78a8 16.4 4.8 61.4 44 .. l 37.6 18 .. 3 76.0 18.8 5 .. 2 62.0

- .34 -

TAJ34E! V (CONT'D)

:Vapor-Liqu.id'Eguilibrlum Data

!!:?£ Acetone-Methanol-Water at 760 ~ !!q_

Weight % in :Liquid· Weight% in Vapor Temp r~ oc --

Acetone Methanol Water Acetone Methanol Water

46.3 Oa4 53.3 92.8 Oll3 6.9 66.0 ~2.4 0.7 56.9 92.6 0.3 7111 66.8 38-.4 loO 60.6 92.5 o.s 7.0 67.7 34.4 L.4 64 .• 2 91.3 o.s 8.2 68.6 30.4 1.7 67 .• 9 90.3 o.a 8-.9 69.7 26.6 .2110 71.4 89.5 1.0 9.5 71~2 23.l 2a2 74.7 85.9 2.4 Ll..a7 73.4 .· 19 .• 5 2.s 78110 83.0 2 .• 5 L4.5 76.5 16-.0 2.6 81..4 79.4 4a0 16-.6 78.9 12.6 2.1 84.7 76.2 4.0 19.8 a1.1·

9.6 2,.8 87.6 68.2 5.9 25 .. 9 85.3 6.8 2.8 90.4 58.3 8.2 33.·5 89.4 4.6 2.8 92.6 44.6 g .• 5 45.9 91.7

35.0 62.4 2.6 53.0 46a5 0.5 62.l 32.7 63.3 4 .• 0 52.i 46.9 1 .• 0 63.0 30.5 64.2 5.3 49.6 48.9 1 .. 5 · '64.0 28.4 65.l 6.5 47-.5 .5.0.3 2.2 64.9 26.3 65.9 7.8 44.7· 53 .• 0 2 .• 3 65.6 24.2 66.6 9 .• 2 43 .• 4. 53.6 3.0 66.4 .· 22;.3 . 67.3 l0a4 40.3 56.0 3 .• 1 .67a2 20.5 67-.9 11. .. 6 38._8 57 .• 2 4.0 · 6.7 .8 18.9 68.4 12-. 7 36.9 58.7 4 .. 4 -68.2 17.2 68.8 14.0 34.9 60.3 4.8 68.7 15._6 69-a3 15.l 33.l 61.9 s.o 69.0 14 .• 0- 69a7 16.3 31.9 62 .• 9 5.-2 69.4 12.s 69 .. 9 17 .• 6 30.0 64 .• 6 5.4 69.9 11.0 72a0 18.8 26.7 66.8 6.5 10.2

. ·WATER LEGEND ·

Vapor Composition (Weight :Per Cent) Ac_etone Methanol~ Water Acetone Methanol Water 1 98.5 o.s LO 46 . 58.3. 8.2 33 _.s 2 · 97.4 0.6 2.0 47 44,6 9.5 ·45,9 3 96.6 1.3 2.2 48 53.0 46,5 o.-s 4 95.4 0.3 4.3 49 52.l 45.9 1.0

. 5 94.9 o.s 4.5 50 49,6 . 48~9 1,5 · 6 95.l o.s 4.6 51 47.S 50,3 2.2

7 94.8 0~5 4,7 52 44.7 53.0 2.s I 8 95.0 0.6 4.4 53 . 4S,4 53 .s 3.0

4.'11 9 94.8 0.5 4.7 54 40.3 56.0 . 3. 7 10 94.0 1,1 4.9 55 38.8 57.2 4,0 11 93.5 · 1.3 5.2 ss· 36.9 sa·. 7 4.4

"µ 12 9S.l 1.1 5,8 51 34.9 60.3 4,8 I

~ 13 92.5 1.6 5.9 58 33.1 61,9 s.o -~ 14 90.5 3.0 6,5 59 :n.9 62.9 s.2

cit 15 90.0 3,3 6.7 60 30.0 64.6 5,4 .0

'et. 16 87.9 4.0 8~1 61 26.7 66.8 6,5 ·

~ 0 . 17 86.0 5.6 8.4 q; . 'cit 18 78.0 12.6 9.4 a 68.6 · 26.9 4,5

""" '§: i 19 98. 7 . 0.2 1.1 b 67.9 23.S 8.8 ~ 20 97.2 <'o \ 1.6 1.2 0 ·66.l 20.a 13.1 ~ 21 95.l 3.4 1,5 d 35.5 21.2 43,3 . .

\ -~ 22 93.8 4.5 1.1 · e 51.9 26. 7 . . 21.4 : ~ ~3 93,l 4.a 2.1 f 52.8 41,3 5,9 91 .

~ 24 91.8 5.9 2.3 g 49,5 39.S 11.0 25 90.6 6,8 2.6 h 47.7 37,1 15.2

' ./.s 26 89,9 1.1 2.4 i . 26.3 67.S . 6.2

' \ 27 88.l 8.8 3.1 j 25.0 "63. 5 . 11.s \ .· 28 81.0 9.3 3.7 k 22.7 60.2. 17.1

- '\_ .. · --·-- · · 29 85.4 11.0 3.6 m 86.0 9.7 4.3 / \ 30 -83.8 12.2 4.0 . n . 84.4 7.1 · · 7.9

I \ ·, 31 · 82,S 13.3 · 4_,4 0 a·o.3 8.6 11.1 . '. \

! 32 80.4 15.0 ·4.6 p 93.1 : · 1.9 ·s.o \ / ,.1' 33 78.8 : 16.4 4.8 q 92.7 0.9 6.4

:,4 76.0 18.8 · .s·. 2 r 89.7 1.6 ·. a.1 ·35 92.8. 0.3 6.9 s 82.7 3.5 ·13.a 36 92.6 0.3 7.1 t 52.1 10.s 36.8 .37 92.5 - o.s 7.0 u 96.9 1.s 1,8 '38 91.S o.s . 8. 2 . v 9S.8 . 4.2 . 2.2 3·9 90.3 a.a 8.9 w 80.2 · 5.8 u.o .

'\. I

· '. 40 89.5 1.0 9.5 x 45.3 23.4 ·31.S 41 85.9 2.4 11.7 . y· 62.9 17.0 20.1

·y 42 as.o 2.s . 14.5 . z 11.0 21.0 2·.o 43 · 79.~ 4,0 16,6 A · 79.2 ·1.0 13.8·

~ ~ R ~ , , . 0 44 76.2 4 .0 19,8 B 87.0 · 1.9 11 • .1

. . . It)

VAPOR-LIQUID EQt1IL~IUM FOR ~ -. .,45 68.2 5.9 25.9 c· 67.9 S.4 26.7

ACETONE-METHANOL-WATER . : : · . ~ ·' .

a Exr.>edmental ·

!). Data of Buford and Griswold (46)

Compositions .in Weight i>or Cent Figure 10 • . BOnINS. POINT DIAGRAM FOR SYSTEM . .

ACETONE-METHANOL-WATER

\ 1 -~ ~ ~

1~ '¢cir

0 0

Bs

Sam))le . m,· ..

l · a

3 4 5 6 7 8 9

10 11 12 lS 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 so 31 32

·ss S4 85 36 37 sa 39 4s0 41 . 42 43 4~ 45

LE SUD -Tonporatura ~le . Temperature oc :· mo. oc

•••• 46 89.~ •• 56.5 47 91.7 57.1 48 62.1 . 51.6 .49 ss;o .58.1 . so 64 .• 0 58.6 . 51 64.9 59.1 . 52 · 65.6 59.S 53 66.4 60.0 54 6'1.2 60.S 55 67.8 61.0 56 68.2 61.6 57 68.7 82.S 58 69.0 63.0 · 59 69.4 63.8 60 69.9 -65.2 61 70.2 66.1 68,9 a ·59.6 •••• b 60,9 56,9 0 61.3 57.0 d ' 65.0 57,l · e 60.0 57.3 f 58.7 57.5 _g 95,0 57.8 h 82.9 58.2 i 79.0 58.5 j 70,6 58.8 k 68.7 59.2 m 11.2 sg.·a n 78.1-.-60,S 0 66,5 60.8 p 64,4 61.4 q ,~.2 62.0 r · 67.4 66.0 s 62,8 66.8 t 64.8 61.1 u · 66.4 68,6 v ·. · 81,7 69.7 'W 57.9 11.2 . x 61.S 73.4 · y 64.8 75.5 · z s4a 1.8. 9 81.l

· 85,S

- 37' -

S:unple Calculations

Binary Systems. Equation (Sf was used as the basic equation

for calculation of .vapor compositions. Sampl°e number one from the

system. methanol-water {See Table VI, .p. 59} is · used to indicate the

method of calculation. These values are tabulated for ease of

reference.

Initial weight of solution in flask= 1451~0 g

Feed Density= 0.99505 g/ml

Feed Volume~ 40.45 ml

Weight Distillate+ ·Flask= 139.54 g

Weight Flask= 111.40 g

Specific Gravity .25/25°C = 0.79001

Calculation ~ b {Amount of Feed}.

z1

= (Feed_ .Volum.el{Feed D.ensity)

z1

s:i {4o .. 45l(0~99sos}

.Zi = 40.25 g

Z ~ E(Z1J =-Z~ + z .1 Z ;:: 0 . + 40.250

Z · ;::& 40.25 g

Cal~ulation El Y., (Amount of Distillate)·

Di · = .{weight distillate + flask) · ~ weight flask

D1 = 139.54 - 111.40

D1 =. 28.14 g

V ~ ·1:(D1t = D0 ~ D1

V = 0 + 28.14

··v · = 28.14 g

Calculation tl !· From Equation (2),

w~w +z-v 0

W = weight of residue in flask, g

W0

= initial _charge, g

W = 1451.0 + 40.25 - 28.14

W = 1463.l g

- .38 Q

Calculation!?!.._~-, (Composition of Distillate). Values

of the composition of the distillate were interpolated from.

tables of specific ~vity as a function of temperature from

the data . of Carr and Riddick (SO). For sample one, the specific

gravity was 0.79001. Interpolation from the above-mentioned

.table yields a composition of 99.66 weight per cent.

Calculation Ef !fb (Amount of Volatile Component in Residue).

From a material balance for the more volatile component,

Wx = W0x

0 ~ ~{Di~i)

Therefore, for the first sample ·taken;

Wx=Wx -Dx.. 0 0 1 J.

Wx = . ( 14 51. 0) ( 1. 0) - ( 2 8 • 14 )( 0. 9 9 6 6 )

Wx = 1428.0 g

Calculation_2!,!, (Composition of Residue)

W:x: ·x =-

l-1

x = 1423 • 0 -~ 0 9726 1463.l •

- 39 -

Calculation .5?! Zt: (Composition of Vapor}-. From Equa­

tion {5.).#"

d(Wx) yi:r- dV

If a sufficiently small interval of -the curve is chosen,_ this

value will be the slope of the straight line connecting the

end points of the interval. The asslDilption is made that

suocessive samples satisfy this condition. Therefore•

1423.Q - 1451 .. 0 y i:;i -

28ol4 - 0

y ~ Oa995

where, y represents the average value of the distillate sample

taken.

Calculation .2£.~ (Average Liquid Composition Corresponding

toy).

x + ~ X i:i.. 0 J.. ----2

loOOO + 069726 x= 2

x i::i Oa986

Therefo:r:-e, one pair of vapor-liquid equilibrium data, is

establish~ namely x ~ 0.986t ya 0.995.

n-Propyl ~cohol-Water ~ Acetone-Methanol. Calcul·ations

for the syst~s n-propyl aloohol-water and for acetone-methanol

are identical to those given for methanol-water. Analytical data are

- 40 -

given for n-propyl alcohol-water in the International Critical Tables

(51) and for aoetone-methanol by Buford and Griswoid .(46t.

Terna;z S,stem .. Equation (4} was used as the basic equation

for c:aloulation of vapcr oomposi tions for ternary systems. Sample

number one from the system acetone-methanol-water (See Table X1

p. 6S )- is used to indicate the method of calculation. These

values are tabulated for ·ease ·of reference.

Initial weight of solution in flask= 1435.3 g

Feed Density= 0.9581 g/ml

Composition of Charge= 99.64% Acetone 0.36% Water

Composition of Feed = 23.1010 Methanol 76. 9C°t, Water

Volume of Feed= 47.41 ml

Weight Distillate+ Flask= 182.6 g

Weight· Flask .= 112.0 g

Speoifio Gravity 25/25°C = 0.79019

25 Refr~otive Index nd = 1•35689

Calculation of z, V, a_nd W are identical to the calculation of the.se

values for the binazy system and lead to the foll<:>wing values_:

Z = 45.42 g

V = 74.2 g

W i:i 1406.5 g

Calculation ,2! Composition !2! Distillate. Values of the

composition of the distillate were obtained from the analytical

curve obtained for the system acetone-methanol-water by Buford

- 1A -

and Griswold (46)a ·For sample one, the specific gravity

was O. 78854 and the refract! ve index was 1.35610. Inter-

polation from the above-mentioned curve yielded a com-

position of 980 7 per cent a.cetone, Oo 2 per~cent methane+

"and 1.1 per cent water.

Calculation .£t. ~, ·(Amount of Acetone in Residue'}.

From a material balance for the more volatile component,

Wx = W x - ~(Dix it a ·o ao a

Therefore, for sample one,

Wx = W x - D1xa1 . a o o . ·

Wx = {1435.S )(Oa 9964,) - (74.2 l-(O. 987) · a

Wxa = 1362.2 g

Calculation of x 6 (Weight Fraction Acetone in Residue}. -~ Wx x = a

a W 1362 .. 2

xa = 1406.5

x = 0.970 · a

Caloulation 2£. ~, ·(Amoun·t of Methanol :in Residue).

Calculations for the amount of methanol in the residue ·are

identical to those for acetone with the exception that meth-

anol oo~centrations are used in the place of acetone concen-

trai:ions. The resulting ·value of Wx = lOal g. m

Calculation of x 1 (Weight Fraotion Methanol in Residue)a --m

Wx ~a__.!!.

w

10.1 xm = 1406.5

x = 0.007 m

- 42 ..

Calculation~ Ia.~ {Weight Fraction Acetone in Vapor).

From Equation {4)~

d(Wx) dZ Y a:i - dY + zdY

But since z =.. 0 1 the second term drops from the expression.

Using the same assumptions made for binary systems,

1362.2 - {1435.Sl(0.9964) Ya= - 74.2 - 0

ya= 0.985

Calculation of y 1 (Weight Fraction Methanol in Vapor)• -------------~ W 411 -Wx + z ~ - z =-11 omo 0 Ym

Vl - Vo Vl - Vo

10.1 - (1435.3)(0} + Y. ;:i -m 74.2 - 0 .

Y. = o.005 m

(0. 2310} 45.42 - 0

74.2 - 0

Calculation of y 1 (Weight Fraction Water in Vapor).· ----- - ::..:w

Y. = l - y - y w a m

y = l - 0.985 - O.CXJ5 w

y s:: 0.010 w

Calculation of b (Average Liquid Composition).

x a

x + x = ao · a1 . 2

0,,9964 + 0.970 x = a 2

x J::; 00985 a

~::. xmo + 4nl 2

Oa'OOO + Qp007 ~ =:. 2

x = Oa004 m

x =1-x -x w a m

x = 1 - 0.985 - 0.004 w

x = 0.011 w

Therefore6 one pair of vapor-liquid equilibril.UJl data is

established, namely,

x ,:::: 0.985 a

x = 0.004 m

x = 0~011 w

y = 0.985 a

Y. i: 0.005 m

Y. = 0.010 w

- 43 -

Caloulation ~ Eguilibrium ~ ~ Least Sq,uares Equation.

Using the digital computer to derive an equation relating Wx and V

for the system n-propanol-w&ter1 the following equation was estab-

lished:

where,

Wx = A + BV + cv2 + nv3 + EV4 + vv5

o§o gv6

A= 1.4367 x 103

-1 Ba -9.3786 x 10

CC 6a2230 X 10-4

D -7 = -8.7885 x 10

- h4 -

Upon differentiating with respect to V, the following result is ob­

tained:

Values of Wx and V are calculated -in the same manner as was illus-

trated above. Using these methods, the following values were obtained:

Wx = 1403.6 g

W = 1448.4 g

V :=.::::; 36.25 g

Substituting these values into the equation for y

y = -B - 2C{36.25) -. 3D(36.25}2

- 4.E.(36.25)3

- 5F(36.25)4

6G(36,.25) 5

y = 0.896

Wx x =w

1403.6 :x: = 1448.4

x = 0.938

Therefore, one pair of vapor-liquid equilibrimn data is established,

namely, x ~ 0.938, y ~ Oa896.

Calculation of Equilibrium Temperature. _Samples number one

and two from the system methanol-water (See Table VI., p. 59) are

used to indicate-the method of calculation. These values are 64.9°C

for sample one and 65.8°C for sample two.

T ~ Tl + T2. 2

T = 64.9 + 65.8 2

TR 65.4°C

- 45 -

A ·stem correction was applied using the equation _ suggested by Daniels~

et. al. (52),

S = 0.00016n(t1 - - t)

where1

s = stem _correction"· ac

n = length of exposed merQury column, °C

t 1 · ~ temperature of bath, °C

t = ambient_ temperature, °C

Taking t as room temperature#

S = (O.CXX)l6}(52)(65.4 - 32.0}

S = 0.3°C

T il. = T + S equ -

T = 65.4 + 0.3 equil

Tequii i.; 65.7

- 46 -

J:V. · DISCUSSION

Binary Wstems

Methanol-Water. The data obtained in this work are compared

-with that of Cornell and Montanna ( 44} in Figure 2 • The agreement

of the two sets of data may. be rea~ily seen. Most of the points

obtained in this work are slightly higher, i.e., the corresponding

vapor compositions are slightly higher.than those ·of Cornell and

Montanna. However, this discrepancy is only approximately one

per dent by weight or less.

n-Prapyl Alcohol-Water. The data of Gadwa (45} provide the .

accepted literature · values for this system.· This system yielded

perhaps the lbest data that was obtained in this research, as may

be seen from Figure 4. · The system is of particular interest _because

of :I. ts distinct minimum boiling aze~:f:rope. The many points of· data

obtained ne~r this azeotrope fix its ·location ve-ry well. ·

Acetone-Methanol. · The system acetone-methanol was chosen·

because of discrepanoi'es existing in the litera~ure,. particularly

in the data of Fordyce ( 4 7) and of Buford and Griswold ( 46).

Consideralble difficulty was encountered in purifying the acet~ne.

The method of purification suggested by Vogel (48) seemed to be

the most satisfactory~ but it is felt that the purity of this

oom.pcnent may be a critical variable and.may provide an explanation

for some of the discrepancies existing: in the literature.

- 47 -

With reference to the pc~ion of the curve :representing low

concentrations of acetone, Othmer (36)- postulates.that there may

be two distinct azeotropic compositions, one minimum boiling and

the other maxinn:nn. boiling. He considers the alternative to be

the coincidence of the ·equilibrium curve with the 45-degree line.

The latter of 'these possibilities seems more likely from the data

of this work.

It may be seen from Figure 7 that the data obtained for this

system do ·not check the literature values as closely as do the data.

for the systems methanol-water and n-propyl alcohol-water. However,

it should be pointed out that the data obtained lie between the values

of Fordyce and of Buford and Griswold.

Ternary System

Acetone-Methanol-Water. The data obtained for this ternary ·

are sufficiently similar to Buford · and Griswold~-s ( 46) to lead· this

writer to oonolude that this method may be used for ~ernary syst(;mls.

The order of accuracy is not as good as that .for the binary·systeins,

however. Much of the error derives from the analytical curves used

to determine the compositions of the distillate samples. The ana-

lytica~ diagram of Buford and Griswold was used throughout the work

on this system. It is estimated that this method is accurat-e to

no more than one weight per oent. As eao~ successive point cal­

culated is dependent upon the preceding point, it is a.pparent that - -

this may introduce considerable error.· Furthennore, the vapor-

- la8 -

liquid equilt}>rium ourves oonstructed from the data ·obtained are

probably aoou.rate to no more . than three weight per cent in same

regions of the curve_.

However, it is felt that with the above errors taken into

conside:ration~ the data obta.ined _froni this experimentation is suf­

ficiently accurate to consider this method adaptable to most ter­

nary systems. It is also of interest that Robinson and Silliland (3}

state nthere· is real question concerning a large amount of the pub­

lished experimental vapor-liquid equilibrium ~ta. When results

for the same system are compared •• Pit is not unconnnon to find

deviations of ±10 per cent between different investigators em­

ploying essentially the same techniques. 0

Discussion of Boiling Point Curves

As mentioned earlier, the measurement of temperature was con­

ducted only to provide a oheok for the data obtained and was not

used in the calculation of the eqUilib;dum. data. The boiling point

curves are shown in Figures 3~ 5.1 8 an~ 10. It may be seen that the

curves for methanol-water and n-propyl alcohol-water indicat~ a

close correlation with the literature values. The boiling point ·

curve for the acetone-methanol system indicates considerable ~s~

crepancies with the observed temperature differing from the liter­

ature value by a-s much as 2°C. This is also -true for some of the ·

points in tlie acetone-methanol-water system. This may be explained

by the breaking of the Cottrell pump at this phase of experimentation.

- 49 -

It · is felt that the temperature :measurement no longer represented

the equilibrium temperature but was affected by vapor superheating.

However, a small d~gree of superheat does not materially affect the

vapor-liQ\lid equilibrium and it i~ felt that though the temperat\U"es

were not equilibrium. temperatures, the data taken still represented

the true vapor-liquid equilibrium •.

Errors

Systematic Errors. The most important oauses of error in

the _detennination of vapor-liquid equilibrium data are the followi~g:

. 1. During the p:r;ogress of distillation, part of the vapor

condenses if the upper parts of the still and delivery tube are not

protected from ·heat losses • . This condensed vapor may in turn be

vapo~ized and the vapor which is evolved from it would not have the

same composition as that first evolved from the liqu,id in the still.

In other words, fractionation has t _aken place·::::- and that will affeot

. the composi~ion of the condensate.

2. If the ·heating is not carefully done, entrainment will ·

ocour, i.e •. , liquid bubbles will be carried out_ by the vapor, thus

leading to erroneous results.

3. The composition of the boiling ·solution is gradua~ly

changed as the vapor, richer in the· most volatile fraction is evolv~dG

~is change also· affects the composition of the vapors. The sub­

sequent analysis of the condensate from ·the vapor gives the average

composition of the va:por, but analysis of the sample of the liquid

- 5o -

taken e:i.ther·before or after distillation of the cond,ensate sample

analyzed will give a value respectively too high or too low in

the more volatile fraction. This error will be referred to as time­

of-sampling error.

·In the me-f;hod used, fractionation was held at a minimllill by

heating the upper portion of the flask. This may have superheated

the vapor to some extent~ ·The use of the Cottrell pump allowed tem­

perature measurement which was unaffected by superheating effects.

The time-of-sampling error was reduce~ by analrzing essentially

instantaneous- samples and by applicat~on of the differential Ray­

leigh equation in the calculations.

As the equipnent was not completely constructed of glass,

there was in some instances the possibi~ity of interaction between

the systems used and the equipn.ent.

Random Errors. · In addition to.the errors mentioned above~

there were random errors involved in each of the physical measure­

ments that were taken. These errors. are considered qui t _e small

when it is remembered that the :vapor-~iquid equilibrium. data is

reported to_ only three significant figures and all of the exper­

imental.data contained four or five significant figures.

Evaluation!:!.£ Method of Calculation

It was felt that the approximation of -assuming the slope

of the curve of Wx ~ V at a point to be equal to the slope of

the straight line between that point and a successive·point was

- 51 -

a _:poor approximationa In order to check the reliability of this

approximation.q it was decided to fitan equation . to the curve of

Wx 'J:.§.. V by the method of least squares and then to differentiate

the resulting equation with ·respect to V an·d evaluate the slopes.

This computation was perfonned on·a digita; computer~ but it was not

possible to fit . curves to all the data obtained in the time avail-

able. It was decided to take the data from the system n-propyl al-

cohol-water ·to check the method. The least_ squ.ares program used was

the one w~ich is on file in the Misso~i Schoo~ of Mines Computer

Center (LGP-30 Subroutine 37.0). A power series was ohosen as th~

desired representationa It was found that a sixth degree equation

represented.the data wit~Jl). the desired accuracy. This equation was

differentiated. and ·values of V were substituted into it in order to

calculate the vapor compositions. These were plotted as a function . .

of liquid co~posi tions and resulted in the curve shown in Figure 6.

It may be no~ed that the values obtained are not materially dif­

ferent ·from those "obtained by the. method involving the appp:oximation .

of straight lines from point to point.

Evaluation .of E,xperimental Method

Time. Conventional methods used for the ·determination ·of ·

vapor-liquid equilibrium data ~equi_re approximately two to three.

hours . to establish a single equilibrium. point. No:rmally, about

·ten points. are needed to construct a suitable curve for a binary

system and thi1ty to fifty points are neede~ for a ternary-system.

W:f:.·:th the Ramalho-Tiller method, approximately 3"0 ppints may be estab-

lished in a three hour perio_d of operat~on. ~oweve:r-, an a~ditional

six to eight hours is required for filla.lysis of the samples obtained

and caloulation .-of the results. Therefore,; it niay be seen that

using oonvention~l methods. an experimenter can obtain about one

point for three hours of experimental work. Using the Ramalho-

Tiller method he might qbtain about three points per ~our.

Accuraoz. It has already been point.ed out that the accuracy

obtained py the Ramalho-Tiller method is at le~st equivalent to

that of conventional methods. It is f_elt that with further refin~-. .

ments to the equipnent, the accuracy of this method may actually ·

exceed that.of many of the.conventional .methods.

Expense. Mc;>st ·of the conventional methods for the deter-

mination of vapor-liquid equilibrilllll data ·require very sp~aialized . .

and expensiv~ laborato;ry glassware. The Ramalho-Tiller method

requires no highly.specialized equipnerit, but if the equi:r;:anent were . . . .

I?erfeoted.. it would require certain mod.if !cations in the standard

glassware.

Reoonnnendations

As a result of the work done. and the results obtained1

the following reoormnendations ~re made for use of this method of

obtaii:ting vapor..:.liquid equilibrium data_:

1 •. The still should be placed. in.a thermostatted inclosure.

This would ininimiz.e air currents and heat l_oss · fluctuations.

2. The still should be construeted completely of glass

to insure its .inertness to corrosive. systems µnder study.

Limitations

- 53 -

.. The systems studied in this work were limited to three binary

systems and one ternary system. These systems were; methanol-water ..

n-propyl alcohol-water, ~oetone-methanol, and acetone--:,-methanol­

water. All exper!Jnentation was conducted a1: 760 mill:bn.eters mercury.

All systems chosen were completely miscible th;-oughout the entire

range of concentrations.

- 54 -

V. CONCLUSIONS

The detennination of vapor-liquid equilibrillID. data by the

met~od of Rama~ho.and Tiller using. oontinuous f~ed addition and

distillate withdrawal for the binary syst~s, methanol~water, n-propyl

alcohol-water and acetone-methanol and for the ternary system acetone­

methanol-water led to the f9llowing conclusions:

1.. The res:iµ ts obtained for th~ binary systems were within

· two weight per cent of those given in the literature.

2. The results obtained for the ternary system-were within

five weight per cent of those given in the literature~

3. The method used was. found to be approximately ten times

as rapid as conventional methods.

- 5S -

VI. SUMMRRY

A method has been developed with which it .is possible to

reduce the time_. requ.ired to .obtain isobaric vapor-liquid equili­

bril.Dll .data. With other methods,. only one poin·t in the vapor-liquid ·

equilibrii.nn diagram can be obtained in an· individual ·experiment,

thereby necessitating a large nmnber of runs if a complete picture

of the entire concentration range of vapor and liquid compositions

·is to be obtained. In the new method a continuous distillation

was· performed, which enabled qalculations to be made for all values

of the vapor concentration· in ·a single experiment.

Several different procedures may be adopted in connection

'with the proposed method. Th.is work was confined to a continuous

distillation with the addition of feed and simultaneous withdrawal

of distillate. The concentration of .the liquid was found from

analysis of the dlstillate and application of the material balance.

Results for methanol-water,. n-propyl alcohol-water, acetone-meth­

ano.l, and acetone-methanol-water are shown to comp~re favorablr

with data reported in the literature.

- 56 -

VII. APPENDICES

.Two appendices are included in this paper. · Appendix A

contains a list· ·of the ·materials .used in the experimental work

and the specifications of these materials_. Appendix .B consists

of all the exJ)erimental data which was taken during the experi­

mental work.

- 51 -

APPENDIX A

!4.2.i ~ Materials

Methanol. Mart.ufaatured and distrib~ted by Cofmnercial~

Solveri-f:s Corpo~ation. Methanol used was ~edistiiled .and the heart

cut was taken whioh yielded the following specifioatioµs:. Refrac-. ""

tive index, n!5 = 1.32740;· Specific gravity 25/25°C = 007886 • .

n-Propyl Alcohol. Manu£actµred and distributed by East-

in.an Kodak Company. Alcohol used was redisti11·ed and the heart cut

was taken which yielded the fo;Llowing· ·specifications __ : · Specific

gravity. 30/30~C ~ Oa7994J Boiling temperature r::i 97«2~C • . .

Acetoneo ·Man'Ufactured and distrib~ted by Conuneroial

Sol vents Co;rpo·ration. Acetone was purified according to the method

of Vogel (48} which consisted of pe:rmanganate oxidation, drying and

filtering, and subsequent fractionation. The resulting acetone had

the following specificationSJ Refractive indEric;,. n!5= 1 .. ·~5606}'

. Specific grayity 25/25°C = 0078700

Water, Distilled. Obtained· ·from the laboratory ~upply·.

- 58 -

APPENDIX B

Experimental Data

On the following pages is.a tabulation of the experimental

data that was taken in this wo;rk. Table VI contains the data from

the methanol...:.water system~ Table VII the data from n-propyl aloohol­

water. Table VIII the data from acetone-methanol. The experimental

work for the sys-I;~ acetone-met!tanol-water ·was done in four separate

pa.rts. The data for each of these trials are·recorded in Tables

IX:, X, XI, and XII.

TABLE VJ:

Distillati·on Data_: Trl.al° .!

. Syst an_~ Methanol-Wat er

- 59 -

Initi.al weight of solution charged in distilling flask- • · a • a a a o 1451 .. 0 g ·

Feed Temperature l;l p . Q O O a II D a fl ~ O a a a o 32o0 °C .

Feed Density a o a O O A

Satpple .No.

1 · 2

3 4 5. 6 7 8 9

10 ll 12 13 14 15 16 17 18 19 · 20 21 22 23 24 25 26 27 28

Volume Weight Feed · · Distillate

.+ Flask ml

40045 40a98 38g()3 41a26 38 .• 63 37a63· 40.40 4lal9. 4lc,07 42a-S5 4la7l 4lu94 43a73 S7o.3l 42-a 79 37.59 45.64 4l:a6l 44.86 48a07 45.06 46.84 45-a 74 47 .• 35 45.13 47a57 48a-96 46a46

g

139.54 143.27 15lc,90 146a9l 155.13 l50es81 l48al0 145 .• 59 l4la 73 151~_72 153a32 l60a86 149a37 154 .. 58 160075 l57a88 146.33 156.31 152.04 158a95 158094 l58a.52 150~25 155al4 156.28 15la96 · 155 •. 30 150a89

• IS Cl Oa99505 g/ml ·

Weight .-Temperature Specific Flask Gravity

g

llio40 111~24 llla66 l~h31 109.64 lllc,.38 l).Oa73 llla77 ll0al6 llla98 ;q.2a31 :1.12~10 111,.59 l+Oa06 110075 ll0a'46 107a 21 · llla4l l08a35 1141137 111.65 ll4-al3 109~81 112.ss l07cs29 107.93 108043 108.31

oc

64a9 65.8 6605 67ol 67a7 68 .. 3 69a0 69o5 70 •. 0 70a7 71.c,2 ''?l~ 8 72o3 72a8 73a3 . 73a8 74a4 74.9 75~4· 76o0 76:.7 77o3 77,.9 78.,.5 79-o2 79-.9 8006 8La3

25/25

0p7900l Oa79292 Oo796l0 Ou79977 Oa80256 Oa8053). Oa80809 Oo8l0;.l.7 Oa81278 Ocs8l55'l Oa.81~31 Oo8~064

·oe,82294 00825.51 Oa828il 0~8302~ 0483244 Oa83509 0q83794· Oa.84022 Oe184313· Ocs84556 Oa84868 Oa85099 Oa85454 OQ85718 Oa861~9 · 0p86507

- 6o -

2aBLE VI (Continued)

Distillation~: Trial 1

· System: Methanol-Water

.Sample Volume Weight Weight Temperature Speoifio No. Feed Distillate Flask oc Gravity

+ Flask ml ' g g 25/25

29 47 .. _10 . 158-.15 112.44 82.0 0.86908 30 42.98 164-. 22 112.17 82 •. 9 o. 87340 31 40.40 157-.08 llL106 83.6 0.87774 32 42.99 154.17 112.01 84.·4 0.88210 33 45.75 151.33 112.20 8Sa2 0.88663 34 46 .. 86 157 .. 73 109.95 86.l Oi:i89l66 35 46.]36 156,.06 110.00 87.0 Oa89'709 36 46.18 159.83 110.83 87.9 0.90298 37 49.89 i52a97 112.27 88.8 0.90888 38 49 .• 19 158.03 110.55 89 .. 7 0.91495 39 48.48 15$.88 111.39 90a6 0~92198 40 49. 58· 156.34 - 109.78 91 .• 5 0.92891 41 49.26 l57-a57 111.75 92-.4 0.93563 42 48.86 152.65 108.17 93.3 o. 94237 43 49.59 154.39 111. _57 94.0 0.94837 44 49.29 is5sa84 108.86 94.7 Oa9543l

TABLE VII

Distillation Data: Trial 2

Syste:I\~ n-Propyl Alcohol-Water

- 6l. -

Initial·weight of solution charged in distiiling flask. • • • • . . .• . • • • 1439.7 g

Feed Temperature ........... . . . . 31.0 °C

Feed Density • • • • • • • • • • • • • • • • • • 0.9954 g/ml

Charge Composition· • • • • • • • • • • • • • • • • 99 .• 90% n-Propanol 0.107o Water

Sample .No.

1 2 3 4

6 7 8 9

10 11 12 13 14 15 16 17 18 19 20 21 22 23

voiume Feed

ml

45.18 50.37 45.56 49.19 44.27 44-.93 46.11 47-.96 45.58 45 .• 91 45.62 44.42 46.50 46.09 46.34 46. 21. 45.43 41.35

·49.49 46.46 47.21 4S.66 42.02

Weight Distillate

+ Flask g

147.60 152.~ 28 143.58 148.77 155.68 151.23 149.13 146.93 144 .• 17 153.77 150.70 152.75 149-.47 146.77 153.87 149 .• 12 153.41 159.60 151.00 154.66 156.48 156.81 147.36

Weight Flask

g

111.35 111.29 111.66 111~37 109.68 111.42 110.78 111.79 llO.i9 111.98 112~32 112.10 · 111.65 110.08 110.77 110.45 107.20 111.42 108.37 114.35 111.63 114.13 .. 109.81

Temperature oc

92.3 90.0 88.7 88.0 87.6 87.3 .86.9 ·86.9 86.9 86.8 . 86.8 86.8 86.9 86.9 86.9 87.0 87.0 87.0 87.0 87.1 . 87 .• 1 87.1 87.1

Specific Gravity .·

30/30

0.80979 0.82494 0.83337 0.84142 0.84649 0.84973 0.85275 0.85470 0.85688 0.85884 0.85975 0.86080 0.86168 0.86268 0.86304 0.86396 0.86420 0.86489 0.86534 · 0.86537 0.86575 0.86620 0.86631

Sample Volume No,. Feed.

ml,~;

24. .41 .• 10. 25 40.78

·26 40.70 27 ·40.50 28 · 41.79 29 44 .. 42 30 40,;77 ·31 4la08 32 42·.16 33 40.82 34 47.98 35 48.37 36 48.65 37 48.71 38 47.52 39 46~73 40 48.85 41 45.75 42 47.80 43 · 4f;3-.18 44 47.55 45 49.35 46 47 .. 68

TAB~ VII (Continued)

Distillation Data: Trial 2

Syste!I\.: n-Propyl Alcohol-Water

Weight .Weight Tempera t_ure Distillate Flask

+ Flask g g oc

165.71 112.ss 87.2 154.35 107._28 87 .• 2 153.17 107.95 87.2 153.66 108.·43 87 .. 3 156.21 108.33 87 .. 3 156.50 112.44 87.4 159 .• 17 112.11 87.4 157.97 111.06 87.5 159~47 112.04 87.5 153. 9·5 112.25 a1 .•. 5 152.75 109.96 87 .• 6 154. 59· 110~03 87.7 157 .• 49 110.81 87.8 154.04 112.26 88.0 i56.l4 110.53 88.2 159.96 111.39 88.4 151.30 109 .. 78 88.8 155.99 111 .. 75 89.2 l59a82 ·111. 55 89.9 158.98 108.86 90.7 161,. 55 114 .• 86 91.6 155.00 110.98 92.6 ·157.10 109.3~ 93,.9

- 62 -

Specific Gravity

30/30

0.86670 Oa86713 0.86714 0.86737 . 0.86790 0.86785 0.86820 Oa86877 0.86876 0.86912 o. 86971 0.86985 0.87054 0.87138 Oa87210 o. 873 52 o. 87555 . 0.87783 0.88150 0.88Q88 0.89308 0.90163 o. 91315

TABLE VIII . .

Distillation Data: Trial 3 -- -Szstem_: · Acetone-Methanol

Initial weight of _solution charged in distilling flask. . . . . ~ . . • 1206.36 g

Feed Temperature . . . . . . .• . . . . . . 24.0_

Feed Density •• • • • • • • . . 0.7877 g/ml

Sample Volume Weight Weight Tempe;rature Refractive No. Feed Distillate Flask 0 Index

+ Flask 25 ml g g.· oc nd

1 31·.90 160.18 111.16 . -55. 7 1.35573 2 29.40 159.32 111.48 55.7 l.35522 3 32.61 16·2 .02 111. 20 55.7 1.35483 4 33.09 164.63" 109.55 55.7 1.35439 5 34.84 163.48 111. 26 55.7 1.35406 6 26.73 161.82 109.43 55.7 1.35379 7 30.01 160.13 110~ 63 55.7 l.35348 8 38~93 l60.22 111. 63 55.7 1.35305 9 40.51 161.85 110.02 55.9 1.35260

10 40.80 161.53 111.82 . 56.0 1.35205 11 42.57 1ss. ?a· 112 .15 56.2 1.351"50 12 ·43.01 156.56 lli. 96 56.3 1.35110 13 40.53 · 168.76 111. 50 56.6 l.35058. 14 41.25 161. 98 109~88 56.8 l.35010 15 41.20 161.35 110.65 57.0 1.34966 16 41.31 157.96 110.30 · 5_7. 3 .l.3.4906 lT 43.68 157.98 110. 48 57.6 1.34851 18 44.41 159.97 107.12 58.1 l;.34802 19 44.93 162.88 114.15 58.6 1.34742 20 40.91 167.71 111.44 59.2 l.:3"4676 21 43.42 158.77 ll3. 93· 59.7 1.34608 22 .41. 89 156.58 109.61 60.3 1.34560 23 41.64 156.33 107.75 61.0 1.34493

~ <

TABLE IX

Distillation~: Trial 4

83:stem.,,:. Aaetone-Methanol-Water

Initial weight of solution charged in distilling flask. . . . . . . . . . • • 1435.3 . g

Feed Temperature • • • • • • • • • • • . • • • • • • · 26. 5 °C

Feed Density • • " • • • · • ,, . . . . . . . . . . . 0.9581 g/ml

Composition of Charge. •. . . . . . . . Composition of Feed • .. • • • • • • ...

Sample Volume Weight Weight No. F~ed Distillate Flask

+ Flask ml g g

l 47.41 182.6 112.0 2 46 .. 30 185.2 111.7 3 46 .• 88 175.2 110.0 4 47 .• 22 . 178. 5 111.7 5 47.46 175.2 109.9 6 45 .• 45 182 .• l 111.1 7 47.54 173 ... 9 112.1· 8 48.62 174.2 110 •. 5 9 44.74 193.7 il2.3

. . . . • •

. . . . 99. 64% Acetone o.sei·water

23.101o Methanol 76. 90% Water·

Temp Specific Refraot. Index Gravity

°C 25/25 25 nd

55.9 o.79019 l.35689 56. 5 o.79393 1.35732 57 .• 1 o. 79~,0l. l.35757 57.5 0.79865 1.35782 58.0 o.79984 l.35800 sa.s· 0.80061 1.35808 59.0 0.80179 i.ssaps 59.5 0.80234 l.35808 60.0 0.80049 · 1.35800

10 47.29 201.9 112.6 · . 60.4 0.80422 1.35797 11 46.00 192.1 112.4 60.9 0.80540 1..35822 12· · 48.08 191 .• 5 112..0 61.7 o. 80616 1 .• 3579:r 13 47 .• 20 197~0 110.4 62.4 0.-80757 1.35797 14 47.91 196.3 111.1 63.0 0.8088S 1.35779· 15 47 .• 02 186-.6 110.s 64.0 0.81019 1.357'75 16 46.43 l9S.O 110.~ 65.3 0.81263 1.35761 17 41.10 200.6 107.5 67.3 0.81579 1.35761 18 42.30 198.7 111.7 69. 7 o. 82040 1.35732

- 65 -

TABLE X

Distillation Data: Trial 5 ---------i Sy:ste.m: Acetone-Methanol-Water ...

Initial weight of solution charged in distilling flask. . . . • • G a 1479.56. g

Feed Temperature aaoo•••••••.•a••a• ·25.0

Feed Density • .. o o •• ·11 • • • .. • Ill • p • • • a.

Composition of Charge. a •• •••• a,. •• o ~.

0.8688 g/ml

99a3% Acetone 0.7% Water

(.;omposition or Feed • a. o o a ~ ,. o ,, .a • 11 • • • o 69lJ44% Methanol

Sample Volume Weight Weight Noa Fe.ed Distillate Flask

-+ :?lask-ml g g

1 37.90 172.;.65 111.44 2 56.02 175.35 111.20 · 3 53.96 176.17 111.13 4 54.56 . 175. 90 111.64 5 53.11 179..27 111.33 6 52.84 18h96 109'..68 7 59.67 191..47 111.39 8 57.68 184.12 109.56 9 51.60 187..61 11.0.77·

10 55.95 188.75 111.76 11 57.-59 l8la32 110.15 12· · 55".07 189.19 · 111.96 13 60.23 185,.01 112.30 14 53.39 188~86 112~10 15 57.80 184 .. 59 llL.64 16 58.64 181"77 110.04·

30a56% Water·

Temp Specific Refract. Gravity

· 0 c - 25/25

56.6 0.78854 56.6 0.79020 56.7 0.79195 56.9 0079330 57.2 0.19432 57.,.3 · 01179540 57.7 0.79630 58.0 o. 79749 58.4 o.79831

· .58.7 0079956 59.2 0.80038 59..7 0,80159 60o2 0.80253 60.8 0.80348 61.4 0 .. 80440 62.0 Q,.80569

Index·

25 nd

l.035610 1.,35587 1.35569 1 .• 35555 1.35540 l.35522 1.35504 1.354.83 l_.35457 1.35439 1.35414 1.35388• 1.35359 1,.35327• 1.35294 1.35249

- 66 ~

TABLE XI

Distillation Data: Trial 6 -Szst em: Acetone-Methanol-Water •

Initial weight of ·solution charged in distilling flask • D • • . .. • • • a • 1506.25 g

Feed Temperature • a • • .. • • • • • • • • • • .a • 25.0 · 0 c

Feed Density •••• o · " •

Composition·of ·charge • • • •

Composition of Feed •• a • •

Sample Volume Weight No. Feed Di:;ltillate

+ Flask ml g

l 62.03 170_ ... 25 2 71 .. 43 .169.08 3 68.79 173 .. 21 4 68 .. 98 173 ... 75 5 73.59 178,.~0 6 66_. _51 173.89 7 68.90 172.{3 8 7la 98 · -170. 94 9 80.16 179..59

10 41070 18~58" 11 74.35 177 .• 77 12 66.90 179.53 13 72.34 178-,. 92 14 41.73 172.13

• • • • • • • • • • . o. 9847 g/ml

• • • • •

a • " • •

Weight Flask

g

111.13-lll-a64 111.33 109 •. 68 111.39 109.56 110.77 111~76· 110.15 · 111 .• 96 112-.30 112 .• 10 111.64 110.04

. .. • • • •

• • • • • •

52 .<:J'/o Acetone 48.0% Water

7.33% Methanol 92.67% Water

Temp Specific Refract. -Gravity Index

oc 25/25 25

nd

65.3 o. 80773 1-.35898 66.0 0.80966 1 •. 3589_8 66.8 0.81008 l,,35905 · 67 .• 8 . 0.81170 1.35912 68 .. 7- .·o .. a134s 1.3.5919 69.9. Oa81615 1 .• 35937 71.6 Oa81~66 1.35962 74.3 0.82398 1 .• 36002 " 77~5 0083168 1.36067 79 .. l o. 83697 1.36088 82.2 Ch"844·93 l.36116 81.2 0~86167 1.36145 90.2 0.88058 1.36095 9l.3 o. 90833 1.35854

TABLE ·XII

Distillation Data: Tria1·7 ---System: Acetone-Methanol-Water

... ·--Initial weight of solution charged in dist~lling flask. Q. 0 •

Feed Density .• o a o •• o • • • • • • • •

• • 1276.91 g

• • . . 0.8721 g/ml

Composition of Charge •. a ·• • • • • • • • • • • • • · 3 7. 9% Acetone 60a0% Methanol 2.11, Water

Compositi.on of Feed • O a O a D a a . . . . . .. 69.3% Methanol 30.7% Water

Sample Volume Weight Weight Temp Specific Refract. No. Feed Distillate Flask Gravity Index·

.·+ Flask 25 ml g g oc 25/25 nd

1 64.92 172 .. 18 111.13 61.5 o.79314 1.34489 2 69 .• 64 166.02 111.64 · 62.2 o.79448 ln34470 3 70.25 162.97 111.33 63.2 0.79522 1.34478 4 62.51 165 .• 87 lll.39 64.2 o. 79738 1.34433· 5 64-.94 167.~4 109.56 65.0 Oa79816 1-.3:4407 6 67.87 170.06 110.77 65.7· · · o. 79986 l.34369 7 72.79 165 .• 90 111. 76 66.4 0.80107 1.34358 8 62.39 173. 51 110.15 67.2 0.80232 1.34305 9 6lo48 · 169 .• 26 111.96. 67.6 0.80352 ~--3426.4

10 62 .• 29 171-a 52 112 .30 · . 68 .1 01180461 1.34214 11 58 .. 88 1soa6 112.19 68.5 01180537 1.3·4173 12· 67 .. 09 174.:32 116.64 68.8 o.·ao6'57 l.34124 13 65.24 181..26 110.04 69.3 0.80749 laS4082 . 14 56.40 180.,03 ·110.66 69.7 0.80902 1-.34029 15 75.75 178.37 107.17 70.0 0.81038 1.33972

- 68 -

VIIl.. BIBLIOGRAPHY_

1.. Ramalho, R.S.~z Ph.D. Thesis, · Vanderbilt University, 1954.

2. Ra.malho; ~.S.~t Personal Communication, 30 September, 1957.

3. ~binson, C.So and E.R. Gilliland: ~lements of Fractional

Distillation". p. 3-14, McGraw-Hill Book Company, Inc.,

New Yor}; N. y.; .1950. 4 ed.

4. Dodge, B.F. and A.K. Dunbar: J.Am. Chem. Soc. 49, 591 (i927) • . .

5. Inglis, J.K.H.: Phil. Mag. {VI), ll., 64~ (1906) ..

6. Quinn: . Sc.D .. Thesis, Mass. Inst. of Tech., 1940.

7. Rosanoff, M.A., A. B. · Lamb and F. E. Brei thut: J. Am. Chem. Soc•.•

48, 2055 _ {1909)~

8. Torochesnikov# N.S.: Tech .. Phys., U.S~S.R., i, 337 (1937)-.

9. Ferguson~ J.B. and w.s. Funnell: J. Phys. Chem., 33_, 1 (1929).

10. Boomer, E.It. and C.A. Johnson: ·Can. J. Research, 16B, 328 (1938).

il. Freeth, F.Ao ·and T.T.H. Versohoyle: Proc. Royal Soc. (London),

Al30,453 (1931).

12. Fedoritenko, A. and M. Ruhemann: Tech. Phys • .r U.S.S.R • ., .!, .

l (1937).. ·.

13· • . Bergantz: Sc.D •. Th.eds, Mass. Inst. of Tech.,' 1941.

14. Verschoyl~, T.T.H • .,: · . Trans. Roy. Soc. {London) 1 A230, 189 (1931) •

15. Dobson, H.J.E. _: J. Chem._ Soc~; 127, 2866 {1925}.

16. Orndorff, W.R. and H.G. Carrell: J. Phys. Chem., 1., 753 (1897) •

. 17. Rignault: Ann. chim. et. phys. (3),., 151 129 (1845}.

- 69 -

18. Will, W. and G. Bredi~: Ber., 22, 1084 .(1899·).

19. Calingaert, G. and L.B. Hitchcock: J. Am. Chem. Soc., 49,

750. (1927).

20. Caudet, I~_: Compt. rend., 130, 828 . (1900).

21. Curmnings, -L.W.T ... : Ind. Eng. Chem., 23, 900 (1931:.

22. Holst, G. and L. H.axnburg ... : z. physik. Chem., 91, 513 (1919).

23. Kay~: w.~: Ind. Eng. · Chem., ~' 459 (1938).

24. Kuenen, J.P~, T.T.H. Verschoyle and A.T. van Urk: Conmmns.

Phys. Lab., Univ. Leiden, No. 161, ·(1922).

25. Meyer, L._: A. physik. ~em., Al 75, 275 (1936). ·

· 26. Sage, B.H. and W.N. Lacey: Ind. Eng. Chem., 26, 100 (1934).

27. Ealy, E,.C._: Phil. Mag., {V), 49, 517 (1900).

28. Brown: Trans. Chem. Soc., 35, 547 (1879).

29. Lehfeldt, R.A.i Phil. Mag. {Vl~ .!§., 42, (1898).

30. Rayleigh, o.M.: Phil. Mag. {VI), .!, 521 (1902).

31. Rosanoff, M.A., c.w. Bacon an_d R.H. White: J. Am. Chen.

_Soc., 36, 1803 (1914}.

32. Taylor, A.E._:= J. Phys. Chem., ·!, 290 (1900).·

33. Zawidsk:i, J ... : z. physik. Chem., ·35 1 129 .{1900).

34. Adey: · s.~ Thesis._ Mass. Inst.· of Tech., 1941.

35. Colburn, A.P., C.A. Jones and E.M. Schoenborn: Ind. Eng.

Chem., 351 666 (1943).

36. othmer, D.F ... t Ind. Eng. Chem., 20, 743 (1928.).

37. Scatchard, G,C.L. Raymond and ·H.H.· Gilmann_: J. Am. Chem.

Soc., 60, 1275 {1938).

'"88. Soheeline, HQW. and E •. Ro Gilliland: · .Ind • . Eng. Chem • .,_ ~l,

1050 .(193 9).

3.9. Sims: So.J.?o Thesis._ ~ss. Inst. of .Tech._, 1933 • . .

- 70 .._

40. Snyth, .C.P. and E.W. Engel_: J. Am.· Chem. Soc., 51, ~646 (1929}..

41111 Same shima~ J" : J a Am. Chem. Soc•, .40, 1482, 1503 {1918). . -

42,. Yamaguchi: J. Tokyo Chem. ~o.,. 341 ·69.l ff.;g'13l.-

43. Huckaba, C.E.; "A New Method for Obtaini~g Vapor-Liquid Equi­

libria"• Unpublished Report, Lamar Research Center (1954}.

44. Cornell~ L.W. and R.E. Montanna·: . .

Ind. ·Eng,. Chem. 25,. 1331 ·

(.1933 )-.

45. Gadwa;r T.A._: · "Chemical Engineers' Handhookn. (JaH. Perry,

Editor), P• 1367, McGraw-Hill Bo~k _Company, Inc., New

York, N.Y .. , 1941~ 2 ed.

46 •. Griswold, J. and C.B. Bufor<l:: · Ind. Eng. Chem., 41~ · 2347 (1949).

47. Fordyce, .C.~· and D.R. Simonson: Ind. Eng. Chem., 41; 104

(1949) •.

48. Vogel, A.I._: .''Practical Organic Chemistry". P• 110, Lo;ngmans,

Green and _Co." New York, N. Y._, .1951. 2 ed.

49. Cottrell, F.C ... : J,. Am.a Chem. Soc., -41, 72i (~9191.

so. Carr, J.C. and J.A .. Riddick_; Ind. Eng. Chem., ~. 6.92 (1951).

51. International ·Critical Tables,. Vol. III, p. 119, McGraw-Hill

Book . Cc;>mpany I Inc· • .,. New York, No Y. 1 1928.

52. ···Daniels, F." J .. H,.,. Williams, P. · Bender,. G.W. Murphy and R.A~

~lberty__: UExperimental Physical Chemistryl'. P• 398,

McGraw-Hill Book Company,. ·Ina., New York, N.Y._. 1949. 4 ed.

-n-

IX. ACKNOWLEDGMENTS ..

The author wishes to ·express ·his apprec;dat'ion to Dr. R.S.

Rama~~o for his.suggestion of this project. ·He also supplied a

great many useful. suggestions for accomplishing the ·research.

Appreoia1:ion is al_so extended to Dr. W.J. Jani.es ·whose many

timely suggestions ·and ca.pable direction contributed greatly to

the project ..

A further word of appreciation .is extended to Mr. O.IC. Lay.

His aid in construqtion o~ much of the equiµnent was of great value •.

- 72 -

The writ~r of this thesis, David William Bunch, was born at

Eldon, Missouri, January 20~ 1936. ·After attending the public schools

of Eldon and: Mexico, Missouri, he enrolled in the Missouri School

of Mines at Rolla in ~ptember1 1953. He reoeived the Bachelor of

Science degree in Chemical Engineering in -!\.ugust, 1957.

In September, 1957, he enrolled as a candidate for the Master

of .Science q.egree in Chemical Engineering. Sinoe that date he ha,s

been employed as ·an instruotor in chemical engineering at the Missouri

School of Mines, w~th the_e.xoeption of six months duringwh!ch he

served as a second li-eutenant in the United .States Anny Corps of

Engineers.