Water-Phenol Miscibility Diagram

Purpose
Liquid water and phenol show limited miscibility below 70C. In this experiment,
miscibility temperatures of several waterphenol mixtures of !nown composition
will be measured. "he phase coexistence line #miscibility temperature versus
composition$ will be determined, and the critical composition and temperature
calculated. %n extension of the experiment will be to measure the effect of a third
component on the waterphenol critical point.
Introduction
&henol, also !nown as carbolic acid, hydroxyben'ene and phenyl alcohol, is produced at the rate of
millions of tons per year, mostly from isopropyl
ben'ene #(cumene($. &henol is a startin) material
in the manufacture of plastics and dru)s. It was
used an antiseptic be)innin) in the *+,0-s.
.owever, phenol is poisonous. "he phenolwater
mixtures used in this lab are concentrated and
dan)erous by contact or in)estion.
%queous phenol solutions have been used
pharmaceutically.
*
%s the dia)ram at ri)ht
indicates, at low and hi)h percenta)es of phenol,
water and phenol mix completely, formin) a
sin)le liquid phase. .owever, at intermediate
compositions #and below the critical
temperature$ mixtures of phenol and water
separate into two liquid phases. &oint (h( in the
fi)ure is the critical point. %bove the critical
temperature, phenol and water are completely
miscible.
"he waterphenol phase dia)ram contains a solid
phase at hi)h percent phenol, near and somewhat
above room temperature. "hat part of the dia)ram is not shown in the /i)ure 0 and will not be explored
in this experiment.
"he independent variable in the phase dia)ram is composition. Composition is sometimes )iven as
mass percent, as in /i)ure 0, especially in older literature. "his experiment will refer to composition as
mole fraction phenol. 1ecall the definition of mole fraction.
phenolwatersalt.odt *
Figure 2: "he liquidliquid phase dia)ram of phenol
and water. "his dia)ram is from Martin's Physical
Pharmacy and Pharmaceutical Sciences.
Figure 1: phenol
x
phenol
=
moles phenol
total moles
2hen only phenol and water are present, total moles means moles phenol plus moles water.
"he first part of the experiment use tubes that contain !nown masses of water and phenol. /or each
tube, from the masses the mole fraction x
phenol
can be calculated. #3ach tube also contains a little air
mixed with water and phenol vapor, but the )as phase is i)nored in this experiment.$
%t room temperature, a tube contains two liquid phases, one
more dense than the other. "he tube is heated in a water bath
until the two phases mer)e. "he temperature at which they
mer)e is the (clearin) temperature,( also !nown as the (cloud(
temperature, and lies on the liquidliquid coexistence line. 4y
usin) several sample tubes, one obtains several #x
phenol
, t$ points
on the coexistence line. 2e will fit a curve throu)h those
points, differentiate the curve to find its maximum, and use the
maximum as the critical temperature, t
c
.
3ven small concentrations of salts may have lar)e affects on phase separation and the critical
temperature. In aqueous solutions of or)anic molecules or polymers, salt may be added to ma!e the
or)anic material form a phase separate from the salty aqueous phase. "his procedure may be familiar as
(saltin) out.( "he miscibility of phenol and water is reduced by addition of many common salts such as
al!ali and al!alineearth halides.
0,5
"he ori)in of the effect is the tendency of water molecules to
associate with ions, hydratin) them. In that way, simple ions reduce the tendency of water to solvate
phenol. "he result of addin) salt is often an increased critical temperature and )reater x
phenol
on the
phenolrich side of the coexistence curve.
"he salt effect will be studied by preparin) a set of phenolwater samples of constant salt composition.
Clearin) temperatures observed in the water bath )ive a coexistence curve. /rom the coexistence curve,
t
c
and x
phenol
can be determined in the presence of salt. "he critical point with salt can then be compared
to that obtained with phenol and water only.
phenolwatersalt.odt 0
Figure 3: 6ample #x,t$ data and curve.
Chemicals and Apparatus
&henol is in the hood. 3ach )roup needs about *0 )rams of phenol. 2aste phenol must )o in the
phenolwater waste bottle. C%7"I89 from the :aterial 6afety ;ata 6heet #:6;6$< 2hen phenol
touches your s!in it can cause it to swell, burn, peel, and brea! out in hives. &henol can cause cold
sweats, convulsions, circulatory collapse, coma and even death.
763 =L8>36.
;8 98" I9=36" &.398L.
% water bath is set up in the lab.
%lso in the lab<
a di)ital thermometer
?mL sample vials for phenolwatersalt solutions
&"/3 tape for sealin) sample vials
6olid salts< formula mass #)@mol$
9aCl A+.?
BCl 7?.,
B4r **C
CaCl
0
D0.
0
8 ***E5,F*?7 #9ote that addin) this salt will also sli)htly increase moles water.$
:ass data for the prepared and numbered sample tubes<
Sample tube phenol (grams) water (grams)
00 0.AA5 5.?,*
0* 0.,0? 5.57C
00 0.+7, 5.*07
05 *.00, 0.+*5
0? *.?5* 0.,0A
0A *.,*, 0.5C?
0, 0.0?7 *.CA?
07 0.05, *.7A+
0+ 0.?0* *.,*5
phenolwatersalt.odt 5
!perimental Procedure
6tart with the water bath below ?0C. "he bath
temperature should not have to exceed +AC durin) the
experiment. "urn on the di)ital thermometer and
immerse the end of its thermocouple in the water bath.
"urn on the heaterstirrer to raise the bath temperature.
6everal numbered sample tubes should be in the plastic
rac! in the water. &lace the rac! in the water bath. "he
water level should be at or near the bottoms of the tubes-
caps. %dd water to the bath if necessary. 3ach of the
tubes will initially show two phases. "he lower layer is richer in phenol, the upper is richer in water.
%s the sample tubes warm, their caps may loosen. "i)hten the caps once or twice durin) the
experiment, to prevent phenol from lea!in) out into the water bath. If a cap will not ti)hten sufficiently,
or if lea!a)e occurs, then prepare a replacement sample tube. "o do that< measure similar masses of
phenol and water into a fresh sample tube, wrap its threads twice around with &"/3 tape, and write a
new sample number on its cap. 1ecord the phenol and water masses in the laboratory so future lab
)roups will !now them.
1aise the temperature of the water bath. %s the temperature rises, watch for sample tubes approachin)
miscibility. Gou may notice cloudiness in the tube, or a blurrin) of the phase boundary. &ic! each of
the tubes in turn. 7se a testtube holder to immerse the tube completely and sha!e it to stir the contents.
#"his is the point at which the tube-s cap must seal ti)htly.$ 1ecord the temperature, to the nearest
0.*C, at which the two liquid phases mix. Gou may want to lower the bath-s temperature at times, to
chec! or better locate a clearin) temperature. "hat is easily done by runnin) cold water throu)h the
coolin) coils of the heater@stirrer.
%fter recordin) the clearin) temperature for all of the small tubes, remove the rac! of tubes from the
water bath. &lace the tubes securely in a container in the refri)erator.
Choose a salt to study. Choose a mole fraction salt. /or a *<* salt, x
salt
F0.0000F0H*0
?
mi)ht be )ood.
/or a *<0 salt #e.)., CaCl
0
$ x
salt
should be smaller, perhaps *H*0
?
.
:a!e several #e.)., five$ sample vials of phenol and water, with mole fraction phenol runnin) between
0.00A and 0.0A. .ere is a method to ma!e a vial.
Choose a tar)et mole fraction phenol, x
p
.
&lan to fill each vial to a total mass of ?.0 )rams.
9ote that
x
p
=
m
p
/ C?.**
m
p
/ C?.**?.0m
p
/ *+.00
, where C? and *+ are formula masses of phenol
and water, and m
p
is the mass phenol to put in the tube. 6olve for m
p
. #% sample calculation is
below.$
phenolwatersalt.odt ?
"are an empty sample vial on the balance.
%dd m
p
)rams of phenol to the empty vial.
%dd water to the vial until the total mass of the contents is ?.0 )rams.
/rom the actual masses of water and phenol in the vial, calculate the moles of phenol and the
moles of water.
Calculate the moles of salt to add<
n
salt
x
salt
n
phenol
n
water

.
/rom moles salt, calculate the mass of salt to add, m
salt
Fn
salt
H:
salt
, where :
salt
is the formula
mass of the salt.
"are the vial a)ain, then add the calculated mass of salt.
2rap &"/3 tape twice around the threads of the vial. 6crew the cap securely into place.
4earin) in mind the poisonous nature of phenol, wipe up any spills near or on the balance.
6ample calculation<
If a vial is to have x
phenol
F0.*0 and x
salt
F 0.0000, with the salt bein) B4r, then
If the actual mass of phenol added is *.?7 )rams, then n
p
F *.?7@C?.* F 0.0*A,.
If the actual mass of water added is ?*.?7 F 0.A5 ), the n
w
F 0.A5@*+.0 F 0.*?0,.
"hen the total moles of phenol and water is n
total
F 0.0*A,E0.*?0, F 0.*A,.
6uppose the mole fraction of salt is x
salt
F0.000*. "hen the mass of B4r to add is
0.0000 H0.*A, mol H **C )@mol F 0.0057 )rams B4r.
phenolwatersalt.odt A
m
p
= ?.0)rams
C?
C?*+

* x
p
x
p

=
?.0C?
C?*+ 0.C/ 0.*
= *.?7g
Calculation Procedure
%naly'e the clearin)temperature data from the small vials of phenol and water as follows.
Calculate mole fraction phenol, x
phenol
, for each of the several tubes. :a!e a table of mole fraction and
clearin) temperature. =raph the clearin) temperature versus mole fraction, as in /i)ure 5.
/it a cubic equation
t = a b x
phenol
c x
phenol
0
d x
phenol
5
#*0$
throu)h the data points. "his can be done usin) 3xcel-s re)ression, which is under the data analysis
menu. 1e)ression is an 3xcel (addin,( so it may have to be added in before it can be used. "o do a
cubic fit usin) re)ression, first prepare columns of x, x
0
, x
5
and t values. /or example,
t x
x
2
x
3
53.0 0.0270 7.29E-04 1.97E-05
58.9 0.0350 1.24E-03 4.36E-05
66.8 0.0690 4.80E-03 3.33E-04
67.8 0.1050 1.10E-02 1.16E-03
64.4 0.1500 2.26E-02 3.39E-03
59.9 0.1960 3.84E-02 7.52E-03
54.5 0.2230 4.98E-02 1.11E-02
2hen doin) the re)ression calculation, the t column contains the (y( values. "he (x values( consist of
all three columns< x, x
0
and x
5
. 7se your own data, of course, not the sample data tabulated above.
"o find the critical temperature, differentiate the cubic equation and set the derivative to 'ero, to find
its maximum. "hat is, ta!e the derivative of t, equation *0. 6et the resultin) quadratic equation to 'ero.
6olve for its roots. 7se the roots to calculate the maximum t. "he maximum t is the critical
temperature, t
c
. "he x
phenol
at which t is maximum should be the critical mole fraction.
"he main result of this experiment is the critical point, #x
phenol
, t
critical
$. /ind literature values of the
critical temperature and composition and compare your results to the literature values. Literature values
are available from sources such as references 07.
%naly'e data from the phenolwatersalt sample vials
%naly'e the data as you did for the pure phenolwater sample vials. =raph clearin) temperature versus
x
phenol
. /it a cubic equation throu)h the data. /ind the critical temperature and the critical mole fraction.
:a!e a )raph of clearin) temperature versus x
phenol
, showin) both waterphenol and waterphenolsalt
data on the same )raph. Gour discussion should describe and discuss the effect of salt added to the
phenolwater mixture.
phenolwatersalt.odt ,
"e#erences
*. 6in!o, &atric! I., Martin's Physical Pharmacy and Pharmaceutical Sciences, Ath ed., Lippincott
2illiams J 2il!ins, 000A. pa)e A*.
0. 6in)h, :an (7pper critical solution temperatures for immiscible solvent systems with halide
salts, carboxylic acids, surfactants and polynuclear aromatic compounds and ben'ene
derivatives,( ournal o! "hemical #hermodynamics, $%, 0?00?,, 0007.
5. =hi'ellaoui, 6K :eniai, %... (3xperimental study and modelin) of the salt effect on phase
equilibria for binary hydroxylic liquid systems,( $esalination, &'(, ?A7?70, 000A.
?. %nternational "ritical #ables o! &umerical $ata' Physics' "hemistry and #echnology, published
for the 9ational 1esearch Council by the :c=raw.ill 4oo! Company, Inc.< 9ew Gor! and
London, *C0+K >olume III, pa)e 5,A. "he table shows mass percent phenol.
A. 4owden, 6.". #he Phase (ule and Phase (eactions, :ac:illan, *CA0, p.*0A.
,. Campbell, %lan 9.K Campbell, %. Iean 1. (Concentrations, total and partial vapor pressures,
surface tensions and viscosities, in the systems phenolwater and phenolwater?L succinic
acid,( ournal o! the )merican "hemical Society, (%#*0$, 0?+*0?++, *C57. &ercents and x in
this paper are by mass, not by mole.
7. 6in)h, :. (7pper consolute temperature of waterphenol systems with some additives,(
ournal o! the %ranian "hemical Society, $#?$, 55?55C, 000,.
phenolwatersalt.odt 7