New developments in differential ebulliometry: Experimental and theoretical

J. David Raal
a,
*
, Vivek Gadodia
a
, Deresh Ramjugernath
a
, R. Jalari
b
a
Thermodynamics Research Unit, School of Chemical Engineering, University of KwaZulu-Natal, Durban 4041, South Africa
b
AP Forensic Science Laboratory, Red Hills, Hyderabad, India
Available online 10 March 2006
Abstract
A new ebulliometer has been developed in which superheat is discharged from the vapour liquid mixture issuing from the Cottrell pump
before it impinges on an otherwise vacuum-insulated temperature sensor. The convoluted chamber through which the mixture passes should also
assist the attainment of phase equilibrium in binary mixtures. Measurements for several solvents showed unusually broad plateau regions with
slopes much smaller than those reported by other researchers. Vapour pressures for several solvents were in close agreement with literature values.
For the measurement of limiting activity coefficients, a new experimentally very simple procedure was developed for finding the difficult-to-
determine evaporation ratio, /, based on the steady-state macroscopic energy balance. Results are presented for two pure solvents, viz.
ethylacetate and cyclohexane. Exact equations, based on material balances and equilibrium relationships involving / then permit calculation of
limiting activity coefficients. Measured temperature-composition data are presented for the ethylacetate (1) toluene (2) and hexane (1)
ethylacetate (2) systems and the ebulliometer characterization procedure is illustrated for three binary systems. Exact differential equations for the
temperature and pressure derivatives with respect to composition, and incorporating the full Gibbs-Duhem equation, are derived. These can be
used to find the very useful temperaturepressure derivative (T/p)
x
1
at any composition and also form the basis for a new thermodynamic
consistency test.
D 2005 Elsevier B.V. All rights reserved.
Keywords: Ebulliometer; New design; Evaporation ratio; Consistency tests
1. Introduction
Ebulliometers have been widely used to measure equilibri-
um temperatures for both pure liquids (to determine saturation
temperatures) and for binary mixtures of dilute but increasing
concentrations of the solute to determine limiting activity
coefficients, c
i
V
. Basic elements of the ebulliometer, as first
developed by Swietoslawski [1], and based on the Cottrell tube
proposed by Cottrell [2] in 1919 have changed little in the
nearly 60 years since. In this presentation, we propose a new
development of the ebulliometer aimed principally at combat-
ting the undesirable effects of superheat on the measured
temperature, and also to broaden the plateau region and to
decrease its slope. Measurements are presented for several pure
solvents.
In differential ebulliometry, the principal problem has been
to find the true liquid equilibrium composition x
1
from the
accurately known charge composition x
S
1
. This is a multi-
faceted problem but a key quantity in finding x
1
is the difficult-
to-determine vapourization ratio / (=V/F). In previous
publications [35] new procedures were proposed and those
of other researchers reviewed. The methods for finding / were
generally still unsatisfactory, and a superior new method is
proposed below with a clear dependence on solvent properties.
The new procedure, experimentally very simple, produces
values of both / and /
S
, the vapourization ratio at the entrance
to the Cottrell tube. The rate of entropy generation (S
gen
) can
also be determined although it does not appear to have useful
practical significance.
An interesting question we have sought to answer is whether
a convincing test of thermodynamic consistency is possible
using the measured c
i
V
and the corresponding DT x
S
1
or
DT x
1
data. We believe this is possible using the system of
exact equations previously developed [3,4] and a new trial-and-
error free computation of the T x
1
or p x
1
profiles by a
marching procedure, based on newly developed exact equa-
0167-7322/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.molliq.2005.11.015
* Corresponding author. Tel.: +27 31 260 3124, +27 31 260 3128; fax: +27
31 260 1118.
E-mail addresses: raal@ukzn.ac.za (J.D. Raal), gadodiav@ukzn.ac.za
(V. Gadodia), ramjuger@ukzn.ac.za (D. Ramjugernath), sekharj@hotmail.com
(R. Jalari).
Journal of Molecular Liquids 125 (2006) 45 57
www.elsevier.com/locate/molliq
tions. These rigorous equations produce expressions for (T/
x
1
)
p
, (p/x
1
)
T
and (T/p)
x
1
in terms of liquid phase activity
coefficients and the derivative (lnc
1
/x
1
), and incorporate
exact forms of the Gibbs-Duhem equation. The equation for
(T/p)
x
1
can be used to correct measured p x
1
or T x
1
data
for small temperature or pressure fluctuations for isothermal or
isobaric measurements respectively. Results for several binary
systems are presented and discussed. Finally, we offer some
comments and calculations on the constancy of the dimen-
sionless vapour and reboiler static hold-ups (VV/SV) and (RV/
SV) (SV =moles of charge). These quantities are necessary for
calculating the equilibrium liquid composition x
1
since they
form part of the ebulliometer characterization parameter E.
2. Experimental
2.1. Experimental equipment
The problems associated with accurate measurement of
vapour pressures have been discussed in an excellent review
by Ambrose [6]. These include solubility of air or an inert gas
in the liquid at the liquidgas interface in the condenser at
high pressures, problems associated with bumping and
pressure measurement at very low pressures, and discharge
of superheat from liquid impinging on the thermometer well
where the temperature is measured. Our new ebulliometer
configuration was designed principally to alleviate the
superheat problem.
In a conventional ebulliometer, liquid discharging from the
Cottrell pump onto the thermowell is necessarily superheated
due to pressure effects and the top of the thermowell will
absorb this effect, i.e. it will tend towards the superheat
temperature. This can establish a temperature gradient of up to
0.2 K along the length of the thermowell (as measured in some
of our experiments). In the new design (see Fig. 1), the well
containing the temperature sensor is insulated from the outer
well by a concentric high-vacuum space. Superheated liquid/
vapour mixture discharges onto the solid glass spiral wrapped
around the outer surface of the vacuum tube. It then flows
around the small bulb before discharging onto the extended
lower surface of the inner thermo well, as shown. The
superheat discharge should therefore be essentially complete
before liquid impinges on the temperature-sensor well. The
extent to which superheat temperatures are compensated for by
evaporative effects is not known and may depend on flow-rate
and the solvent latent heat and thermal conductivity. With a
binary mixture, evaporation between the Cottrell tube exit and
the temperature-sensing element will cause composition
change (the extent depending on the mixture relative volatility),
and a corresponding temperature change along the saturation
line. The final temperature measured in our design, again,
should be closer to the desired equilibrium temperature than in
a conventional design.
To prevent superheating and bumping, i.e., to produce a
smooth boiling pattern, the reboiler has vigorous magnetic
stirring and the internal heater has roughened surfaces for
increased nucleation sites. The small holding chamber in the
downcomer tube is magnetically stirred, has a siphon break
and also a sample septum for sampling and analysing the
overall liquid composition z
1
, needed only for the initial
equipment characterization. The temperature at the entrance to
the Cottrell tube, T
S
, is measured in the top of the reboiler
chamber as shown. To make the application of the macro-
scopic energy balance (see below) more applicable, the
Cottrell tube was insulated with transparent Tygon tubing
and an air gap. In later runs the external heater was
disconnected and the reboiler was also insulated so that
essentially all the power dissipated in the internal heater
would be absorbed by the fluid in the reboiler.
Pressures were controlled with a commercial Bu chi con-
troller to T0.02 kPa, with a 20-l ballast tank in series. For the
measured data reported below only a single prototype
ebulliometer was used. To speed up data gathering for binary
systems, two more identical ebulliometers have now been
connected to the common pressure rail.
Construction of the inner vacuum chamber (particularly)
presents a challenge to the glass blower. The best procedure
was found by leaving a small communicating channel between
the inner and the outer vacuum chambers so that both could be
evacuated at the completion of the upper part of the
ebulliometer.
Pressures were measured with a SENSOTECH Super TJ
pressure transducer to T0.005 kPa, and temperatures from the
two Pt-100 sensors were read through a HP 52 digit multi-
meter model 34401A to T0.005 K. To test the new procedure
for finding the vapourization ratio /, ethylacetate and
cyclohexane were used. Measurements of the plateau region
(i.e. T vs. power input to reboiler) were made for acetone, 1-
Fig. 1. Schematic diagram of new ebulliometer.
J.D. Raal et al. / Journal of Molecular Liquids 125 (2006) 4557 46
propanol and 2-butanone. Measurements for limiting activity
coefficients are illustrated for the two systems, n-hexane (1)
ethylacetate (2) and ethylacetate (1) toluene (2).
The highest purity solvents commercially available (all
>99% purity) were analysed by gas chromatography. Since the
GC analyses showed no measurable impurity peaks the
solvents were used without further purification.
2.2. Experimental procedure
2.2.1. Vapour pressures and plateau regions
The ebulliometer was flushed with pure acetone, drained
and connected to the low-vacuum pump for Tone half hour,
and the procedure repeated several times. The ebulliometer was
flushed with pure solvent and drained a few times. The pure
solvent was brought to the boil with vigorous magnetic stirring
in the reboiler. DC power input to the internal heater was
increased and measured to test that the plateau region had been
reached for each solvent at the set pressure. Vapour pressure
curves were obtained by successive increases of the set
pressure and the extent of the plateau region(s) was noted by
successive increases of the power input. The pressure sensor
was calibrated against a Cole-Parmer model P 68037 standard
with traceability to NIST. The Pt-100 sensors were calibrated
using pure cyclohexane as a chemical standard.
2.2.2. Measurement of /
For the measurement of /, the equilibrium and superheat
temperatures T and T
S
are measured for the pure solvent at a
given pressure, preferably the same as that at which c
i
V
values
are later to be measured. The pressure is then increased at the
same power input so that the temperature T is increased by T2
K. The procedure is repeated for a few more pressure
increments. / values are then computed directly from an
equation derived from application of the steady-state macro-
scopic energy balance. Boil-up rates, and therefore also
evaporation ratios, were observed to have a strong inverse
relationship to system pressure. To solve simultaneously the
two equations containing / and /
S
(the latter being the
evaporation ratio at the entrance to the Cottrell pump) at two
different pressures, it was therefore found necessary to
introduce pressure-independent evaporation ratios, some-
what similar to the pressure-independent activity coefficients
proposed by Prausnitz et al. [7] for high-pressure phase
equilibria. The working equation for computing / in terms
of the reduced pressure functions f is then as follows:
/
C

pL
0
T
S
0
T
0
C

pL
1
T
S
1
T
1

k
S
0
k
S
1
f
S
1
f
S
0
_ _
k
T
0
k
T
1
k
S
0
k
S
1
_ _
f
0
f
1
T
f
S
1
f
S
0
_ _ _ _ 1
where
f
i

p
i
p
c
_ _
0:6
and f
S
i

p
S
i
p
c
_ _
0:6
In Eq. (1), the subscripts 0 and 1 denote measurements at
two pressures p
0
and p
1
, respectively, and subscript S
denotes conditions at the entrance to the Cottrell tube (i.e.
superheated with respect to the discharge pressure).
In addition to the two (or more) pairs of measured T and T
S
values, the latent heats at these temperatures (k) and the
average liquid heat capacity of the solvent over the (T T
S
)
temperature range and particularly their temperature depen-
dence must be accurately known. Successive applications of
Eq. (1) at a few increased pressures will give values of / as a
function of the temperature increase with pressure, yT
(=T
0
T
1
or T
0
T
2
, etc.). Extrapolation of the linear plot of
/ vs. yT to yT=0 gives the desired / at the initial pressure
( p
0
). From the same data, values of / at higher pressures can
also be obtained, e.g. by designating T
1
and p
1
as the new (T
0
,
p
0
). The pressure dependence of / is discussed further in the
derivation of Eq. (1) in Section 3.2.
2.2.3. Measurement of E
Once / has been measured for a given solvent by the above
procedure, as a function of pressure and power input (i.e.,
/=/( p, I
2
R), characterization of the equipment to find the
ebulliometer parameter E proceeds as follows:
With a suitable dilute mixture, for which c
1
V
is known, in the
equipment, power is adjusted, at the selected (constant)
pressure to produce smooth boiling. When temperatures are
steady, the pressure, equilibrium temperatures T and T
s
and the
power input to the reboiler (KI
2
R) are noted. This permits
calculation of / as described above. The liquid in the
downcomer sampling chamber is sampled through the septum
with a syringe and GC analyses are performed to obtain a
satisfactory value for z
1
from replicate measurements. With
known or measured values of T, T
s
, p, c
1
V
, / and z
1
, the
ebulliometer constant is calculated by the iterative procedure
described below. E is defined by:
E VV=SV RV=SV / 2
and is required to find the equilibrium liquid composition x
1
from the exact equation [1]:
x
1

x
S
1
1 K
1
1 E
3
To find the dimensionless hold-up quantities in Eq. (2), a plot
of E vs. / is required. To obtain a series of E vs. / values for
plotting, the power input to the reboiler is increased several
times, at constant system pressure, with T, T
s
, z
1
and power
input measured each time. The slope and intercept of the E vs.
/ plot represent the reboiler and vapour hold-ups in Eq. (2),
respectively.
The constancy of (VV/SV) and (RV/SV) when going from one
system to another is examined in another section below.
2.2.4. Measurement of c
1
V
Once the ebulliometer has been characterized as described
above to obtain (VV/SV) and (RV/SV), limiting activity coeffi-
cients can be measured by conventional procedures.
With mixtures of dilute but increasing and accurately known
concentrations of solute (e.g. x
S
1
<0.02), equilibrium tempera-
tures are measured to obtain a smooth DT vs. x
S
1
plot. It is
J.D. Raal et al. / Journal of Molecular Liquids 125 (2006) 4557 47
important to fill the ebulliometer with the same volume of
charge as in the characterization experiments to maintain
constant values of (VV/SV) and (RV/SV) as discussed below. In all
experiments, the condenser temperature was kept at or below
10 -C (263 K).
3. Theoretical developments
3.1. Ebulliometer equations
In a previous publication [4] the most general form of the
equation relating the liquid equilibrium composition x
1
to the
charge composition x
S
1
was given:
x
1

x
S
1
1 K
1
1 E
RV
SV
_ _
Z
R
1
Z
1
x
1
_ _ 4
The last term in the denominator is a correction term which
accounts for a possible difference between the overall reboiler
composition at equilibrium Z
R
1
and the overall composition of
fluid in the Cottrell tube, Z
1
. If the Cottrell tube acts as a purely
mechanical pump, then (Z
R
1
Z
1
) should be zero and Eq. (4)
reduces to Eq. (3). We consider that, for practical purposes, Eq.
(3) should be satisfactory. The derivation of Eq. (4) is lengthy
and will not be given here. Eq. (4) is exact and is based only on
material balance and equilibrium relationships. K
1
is the
equilibrium constant y
1
/x
1
and E has been defined above in
Eq. (2).
To calculate E and to find x
1
, an additional equation is
required [3]. In its most convenient form, solved for (K
1
1),
this is:
K
1
1
1 x
S
1
=Z
1

/ x
S
1
=Z
1
E
: 5
3.2. Equations for calculating /
Application of the steady-state macroscopic energy balance
across the Cottrell tube from a point below its entrance (where
T
S
is measured) to the point where T is measured is readily
shown to give:
/
C

pL
T
S
T /
S
k
S
gDZ
eff
M V 1 bT p
S
p
k
T
6
In the derivation of Eq. (6) kinetic energy effects (usually
negligible) and heat loss to the environment (eliminated by
insulation) have been neglected. C

pL
is the average solvent heat
capacity over the temperature interval (T
S
T), usually around
1.5 K, / is the vapourization ratio at the entrance to the Cottrell
tube, k =solvent latent heat, V=liquid molar volume and
b =liquid thermal expansivity.
The third term in the numerator represents the hydrostatic
head, found to be negligible for the systems studied. The last
term in the numerator represents the effect of pressure on
liquid-phase enthalpy and can also safely be neglected at low
pressures. With these simplifications Eq. (6) becomes:
/
C

pL
T
S
T k
S
/
S
k
T
6a
Eq. (6a) contains two unknowns, /, and the vapourization ratio
(V
S
/F) at the entrance to the Cottrell tube, /
S
( F=total molar
flow-rate). Attempts to eliminate /
S
by writing Eq. (6a) for two
different conditions of temperature and pressure (at constant
power input) and assuming / and /
S
to be constant over the
interval were not successful, due to the surprisingly strong
pressure dependence of the evaporation ratios. Since the
evaporation ratio is proportional to the boil-up rate, a solution
to the conundrum was sought in nucleate pool boiling heat
transfer theory. The complex phenomenon of nucleate boiling
is still not fully understood and earlier empirical correlations
for the heat transfer rate q/A in terms of dimensionless groups
have been brought into disfavour by subsequent measurements,
which themselves often display considerable contradiction. A
good review of boiling heat transfer has been given by Hewitt
et al [8]. Correlations by Mostinskii [9] and Bier et al [10]
suggest q/A to be inversely proportional to the reduced
pressure, p
r
, raised to an exponent, e.g. ( p
r
)
0.45
. Pressure-
independent / ratios were therefore defined by e.g.
/
p
=/f( p
r
) with f =( p
r
)
0.60
. Solving Eq. (6a) with /
p
and
/
S
p
held constant then gives Eq. (1). Plots of / vs. p, obtained
from Eq. (1) for a few different, (increasing) pressures were
exactly linear, although still of non-zero slope, perhaps due to
temperature effects. Once / is found, /
S
can be calculated
immediately from Eq. (6a).
3.3. Entropy generation
Entropy generation in the Cottrell tube during the fluid
transport and due to evaporative effects can be obtained quite
accurately from the macroscopic entropy balance once / and
/
S
are both known. Applied over the Cottrell tube, as for the
macroscopic energy balance, this gives:
/k
T
TS
gen
TC

pL
ln T=T
S
/
S
k
S
T=T
S
bVT p
S
p
7
The last term on the RHS of Eq. (7) represents the effect of
pressure on liquid-phase entropy and, again, can be safely
neglected. All terms are on a J/mol basis. S
gen
values in this
study, for a variety of systems, ranged fromabout 220 J/mol K.
3.4. Constancy of holdups (VV/SV) and (RV/SV)
Accurate determination of the dimensionless vapour and
reboiler holdups (VV/SV) and (RV/SV) requires considerable effort
and careful analysis. It is therefore important to determine
whether these quantities will remain constant when a new
system is measured in the ebulliometer to determine its limiting
activity coefficients. Should these holdups not be constant, for
example when the ebulliometer is filled with the same volume
of charge, the utility of the general method for finding x
1
and
J.D. Raal et al. / Journal of Molecular Liquids 125 (2006) 4557 48
c
i
V
would be much reduced. The holdups reflect the amounts of
vapour (VV moles) of equilibrium composition y
1
in the upper
part of the apparatus and the total moles in the reboiler (RV) at
any instant when equilibrium conditions have been achieved.
In the derivation of the governing equations containing the
holdups [3,4] the physical location of these quantities was not
specified or required, i.e., the equations are general and apply
to any ebulliometer. As will be seen in the results presented in
the section below, (RV/SV) remains almost exactly constant for
two hypothetical systems of widely differing properties, and
(VV/SV) satisfactorily so.
3.4.1. Variation of (RV/SV) from system to system
Let subscripts 1, 2 refer to different chemical systems or
more particularly, two solvents of different properties such as
density and molecular weight (q, M), and let m =volume with
subscripts R, L and g denoting reboiler, liquid and gas,
respectively.

RV=SV
2
RV=SV
1

v
R
q
R
M
R
_ _
2
=
v
S
q
S
M
S
_ _
2
v
R
q
R
M
R
_ _
1
=
v
S
q
S
M
S
_ _
1
8
For pure solvent or very dilute solutions, q
R
;q
S
and M
S
;M
R
.
With m
S
2
=m
S
1
(Operating procedure),
RV=SV
2
RV=SV
1

v
R
2
v
R
1
;1
3.4.2. Variation of (VV/SV) from system to system
The total moles of vapour holdup at a given instant (VV) will
be partly in the vapour phase (n
g
) and partly liquid (n
L
).The
moles of condensed vapour of composition y
1
will be only a
small part of the total liquid moles in the upper region of the
apparatus, i.e. let VV =n
g
+n
L

VV=SV
2
VV=SV
1

v
L
q
L
M
L

pv
g
RT
_ _
2
=S
2
V
v
L
q
L
M
L

pv
g
RT
_ _
1
=S
1
V
for ideal vapour phase
9
Also,
S
2
V
S
1
V

v
S
2
q
S
2
=M
S
2
v
S
1
q
S
1
=M
S
1

q
S
2
M
S
1
q
S
1
M
S
2
since m
S
2
m
S
1
10
Thus from (9) and (10),
VV=SV
2
VV=S
1

m
L
2
q
L
2
M
L
2
_ _
q
S
1
M
S
2
q
S
2
M
S
1

p
2
m
g
2
q
S
1
M
S
2
RT
2
q
S
2
M
S
1
m
L
q
L
M
L

pm
g
RT
_ _
1
11
To make estimates of the holdup ratio simpler, several
reasonable approximations can be made, e.g. for very dilute
solutions, M
L
;M
S
and q
L
;q
S
(subscript S denotes charge
molar volume or density).
Also, for convenience, let m
L
=km
g
and assume k to be the
same for both systems (m
g
will be the actual volume of the
apparatus filled with vapour). With these simplifications Eq.
(11) reduces to:
VV=SV
2
VV=SV
1
;
k
p
2
RT
2
M
S
2
q
S
2
k
p
1
RT
1
M
S
1
q
S
1
11a
Example: Suppose M
S
2
/M
S
1
=100/40 =2.5, k =m
L
/m
g
=3/
50=0.06,
p
2
=p
1
100=40 2:5; q
S
2
=q
S
1
1:4=0:8 1:75
T
2
=T
1
300=360 0:833:
For these widely different properties and operating conditions,
we estimate
VV=SV
2
VV=SV
1

0:06 0:00286
0:06 0:000668
1:036
Eq. (11a) and the example above suggest that it is reasonable
also to assume that the vapour holdup (VV/SV) remains constant
from one system to another and, once accurately determined
can then remain an equipment constant. The least attractive
approximation, in going from Eq. (11) to Eq. (11a), is that the
ratio of condensed equilibrium vapour volume to equilibrium
liquid volume (i.e. k) will be constant from system to system.
Changes in boiling rate, in the condenser coolant temperature
or in the volatility of the solvent for example, may change the
condensation level in the condenser and so affect the k value.
The actual amount of condensed vapour (m
L
) is not amenable to
measurement since it is mixed with a much larger volume of
liquid exiting from the thermowell.
3.5. Equations for (T/x
1
)
p
, (p/x
1
)
T
and (T/p)
x
1
Eqs. (1) (2) (3) (4) (5) (6) (6a) (7) (8) (9) (10) are specific to
ebulliometer operation. More general equations, generally
applicable but useful in isobaric or isothermal ebulliometry,
can however be derived for the above partial derivatives.
Numerical integration of the first two partial derivatives
produces T x
1
or p x
1
profiles consistent with an assumed
c
1
V
value (and in accordance with the Gibbs-Duhem equation)
and can be compared with experimentally measured values.
The derivative (T/p)
x
1
can serve two purposes:
(a) For any given binary system for which an estimate of c
1
V
is available, the derivatives value will indicate the
sensitivity of measured temperature to control pressure
fluctuations (for isobaric operation) or the inverse for
isothermal operation, at finite concentrations. It can thus
dictate the preferred choice of equipment or mode of
operation, e.g. isothermal or isobaric.
(b) At any desired concentration, x
1
, for which the controlled
pressure has a small deviation from the set value, the
derivative can be evaluated from a known or estimated
J.D. Raal et al. / Journal of Molecular Liquids 125 (2006) 4557 49
c
1
V
to correct the measured temperature. For isothermal
operation, similarly, variations in the controlled temper-
ature can be corrected for in the measured pressure. Since
the derivative (T/p)
x
1
contains system properties
(including the deviation from ideality in the liquid
phase), it should be useful in sophisticated schemes for
automatic pressure control, once the generally short time-
lag is taken into account.
3.5.1. Derivation of equation for (T/x
1
)
p
In a previous publication [5] an expression was derived for
(T/x
1
)
p
, valid for an ideal vapour phase. In the derivation the
co-existence equation of Van Ness [11] was used. In the
derivation below, however, we use a more direct method
(following a suggestion by C.J. Brouckaert) and also incorpo-
rate vapour phase non-ideality.
The basic equation for VLE relating vapour and liquid
compositions ( y
i
, x
i
) is:
y
i
x
i
c
i
p
sat
i
=pU
i
12
The correction factors U
i
, incorporating the Poynting correc-
tion and correction for vapour non-ideality based on the virial
EOS truncated after the second term, are given for a binary
system by
U
1
exp
B
11
v
L
1
_ _
p p
sat
1
_ _
py
2
2
d
12
RT
_ _
exp E
1
f g; say
12a
and
U
2
exp
B
22
v
L
2
_ _
p p
sat
2
_ _
py
2
1
d
12
RT
_ _
exp E
2
f g
d
12
2B
12
B
11
B
22
12b
Thus
p

y
i
p

x
i
c
i
p
sat
i
=U
i
_ _
13
For isobaric conditions,
dp 0
x
1
c
1
U
1
dp
sat
1

x
1
p
sat
1
U
1
dc
1
x
1
c
1
p
sat
1
d 1=U
1

c
1
p
sat
1
U
1
dx
1

x
2
c
2
dp
sat
2
U
2

x
2
p
sat
2
dc
2
U
2
x
2
c
2
p
sat
2
d 1=U
2

c
2
p
sat
2
dx
2
U
2
14
The terms containing dx
1
(=dx
2
) are gathered and divided by
dT at constant pressure. The second and sixth terms on the
RHS, containing dc
1
and dc
2
can be rewritten and their sum
identified as the LHS of the Gibbs-Duhem equation for isobaric
conditions,

x
i
dlnc
i
H
E
=RT
2
dT 15
Details are given in the Appendix A. We obtain finally,
BT
Bx
1
_ _
p

c
2
p
sat
2
U
2

c
1
p
sat
1
U
1
_ _
1 x
1
Blnc
1
Bx
1
_ _
p
_ _
x
1
c
1
U
1
dp
sat
1
dT
_ _

x
2
c
2
U
2
dp
sat
2
dT
_ _

c
2
p
sat
2
U
2
H
E
RT
2
b
1
b
2
16
where
b
1
x
1
c
1
p
sat
1
B
BT
1=U
1

p
16a
b
2
x
2
c
2
p
sat
2
B
BT
1=U
2

p
16b
Eq. (16) is exact, satisfies the full isobaric Gibbs-Duhem
equation, and applies at any liquid concentration x
1
.
The derivatives of the inverse U
i
functions can be obtained
by straightforward procedures but lead to lengthy expressions
(see Appendix A). For practical purposes they can either be
deleted from Eq. (16) or evaluated by numerical integration
(when computing a T x
1
, profile by a marching procedure).
The latter procedure is relatively simple since the U
i
must in
any case be evaluated if corrections for a non-ideal vapour
phase are to be included. In the dilute regions, H
E
is readily
found from the Gibbs-Helmholtz relationship.
The limiting activity coefficient can be solved for from Eq.
(16) at x
1
=0, where
c
V
2
1 U
2
and p p
sat
2
_ _
0; H
E
0
For a vapour phase obeying the truncated virial EOS
c
V
1
U
V
1
p
sat
2
p
sat
1
1 b
BT
Bx
1
_ _
V
p
_ _
17
where
b 1 p
sat
2
B
22
v
L
2
RT
_ _ _ _
dp
sat
2
dT
17a
U
V
1
exp
B
11
v
L
1
_ _
p p
sat
1
_ _
pd
12
RT
_ _
17b
Eq. (17) is in agreement with that of Dohnal and Novotna [12]
and Pividal et al. [13].
3.5.2. Derivation of equation for (p/x
1
)
T
Starting from Eq. (13) and now differentiating with respect
to x
1
one obtains:
Bp
Bx
1
_ _
p
sat
1
c
1
U
1

x
1
U
1
Bc
1
Bx
1
_ _
T
x
1
c
1
B
Bx
1
1=U
1

T
_ _
p
sat
2
c
2
U
2

x
2
U
2
Bc
2
Bx
1
_ _
T
x
2
c
2
B
Bx
1
1=U
2

T
_ _
18
J.D. Raal et al. / Journal of Molecular Liquids 125 (2006) 4557 50
Using the activity coefficient derivative terms (terms 2 and 5
on the RHS), the isothermal Gibbs-Duhem equation can again
be introduced. One obtains finally (see Appendix A):
Bp
Bx
1
_ _
T

c
1
p
sat
1
U
1

c
2
p
sat
2
U
2
_ _
1 x
1
Blnc
1
Bx
1
_ _
T
_ _
b
3
b
4
1
c
2
U
2
p
sat
2
V
E
RT
19
The terms b
3
and b
4
are the counter parts of terms b
1
and b
2
in
Eq. (16) but now involve derivatives with respect to x
1
:
b
3
x
1
c
1
p
sat
1
B
Bx
1
1=U
1

T
19a
b
4
x
2
c
2
p
sat
2
B
Bx
1
1=U
2

T
19b
For the most precise calculation of (p/x
1
)
T
and from it, the
p x
1
profile by a marching procedure, the derivatives in Eqs.
(19a) and (19b) will need to be evaluated. Numerical
differentiation using, e.g. a backward difference formula
should be sufficiently accurate for most purposes if the vapour
phase is considered non-ideal.
Formal differentiation of 1/U
i
(Kexp(E
i
)) however intro-
duces a complexity in that more terms multiplied by (p/x
1
)
T
are obtained! Taking these into account and neglecting the
excess volume (V
E
), one obtains after tedious derivation (see
Appendix A)
Bp
Bx
1
_ _
T

p
sat
1
c
1
U
1

p
sat
2
c
2
U
2
_ _
1 x
1
Blnc
1
Bx
1
_ _
T
_ _
1
x
1
c
1
p
sat
1
U
1
A
1

x
2
c
2
p
sat
2
U
2
A
2

20
with
A
1
B
11
v
L
1
d
12
y
2
2
2pd
12
y
2
By
1
=Bp
T
20a
A
2
B
22
v
L
2
d
12
y
2
1
2pd
12
y
1
By
1
=Bp
T
20b
For a vapour phase obeying the truncated virial EOS and for
negligible excess volume, Eq. (20) is exact, obeys the
isothermal Gibbs-Duhem equation and applies at any x
1
.
As for Eq. (16), Eq. (20) can be evaluated for any assumed
value of c
1
V
. An equation for c
1
=f(x
1
) is required, such as the
one-constant Margules or one-constant Wilson equation. Since
y
1
=x
1
c
1
p
1
sat
/U
1
, the derivative (y
1
/p)
T
is readily evaluated
numerically in the marching procedure. To evaluate the U
i
mild
iteration is required since they contain the vapour compositions
y
i
. These can be determined initially from y
i
=x
i
c
i
p
i
sat
/p.
In the limit, for x
1
=0, ( p p
2
sat
) =0 and c
2
V
=1=U
2
V
, one
obtains:
c
V
1

U
V
1
p
sat
1
p
sat
2
b
Bp
Bx
1
_ _
T
_ _
21
with
b 1
p
sat
2
RT
B
22
v
L
2
_ _
: 21a
3.5.3. Evaluating (T/p)
x
1
Once (T/x
1
)
p
and (p/x
1
)
T
have been found from Eqs.
(16) and (19), or their simplifications, e.g. for an ideal gas, at
any x
1
, (T/p)
x
1
is readily evaluated at the same x
1
using the
triple product relationship:
BT=Bp
x
1

BT=Bx
1

p
Bp=Bx
1

T
: 22
3.5.4. Thermodynamic consistency check
Integration of Eq. (16) by a marching procedure gives the
theoretically correct T x
1
curve consistent with an assumed
or reported c
1
V
. The only limitation is that, in the dilute
regions (e.g. x
1
0.02), the activity coefficients be satisfacto-
rily represented by a one-constant equation, e.g. the 2-suffix
Margules or (preferably) the one-constant Wilson equation
(see e.g. Raal and Ramjugernath [4]), hardly a stringent
requirement. With a known or assumed c
1
V
at a given
temperature, the curvature of the computed T x
1
curve must
match the experimentally determined one and the deviation
between the two curves will constitute a test of consistency.
Since the temperature decrease with concentration, DT
(=T
o
T) is frequently well-represented by a quadratic in
the dilute region [14], e.g.,
DT a
0
x
1
b
0
x
2
1
23
The consistency test can be represented schematically as in
Fig. 2.
The area between the two curves, readily determined, is a
quantitative indication of thermodynamic inconsistency but
should not depend on the extent of the data, i.e. x
1
f
. A suggested
criterion that meets this requirement is thus:
e
1
x
f
1
_ _
2
j
_
x
f
1
0
DT=x
1

exp
dx
1

_
x
f
1
0
DT=x
1

calc
dx
1
j
24
f
1
x
1
x 0
-T
1
x
( )
Fig. 2. Schematic diagram of consistency test for measured and calculated
T x
1
sets.
J.D. Raal et al. / Journal of Molecular Liquids 125 (2006) 4557 51
A similar criterion is proposed for isothermal data, with Dp
replacing DT. Results obtained from testing isothermal and
isobaric data sets in the literature or from our own
measurements will be reported in a future publication.
4. Results and discussion
4.1. Vapour pressures and plateau region
Using measured and literature values [16] for cyclohexane
to calibrate the Pt-100 sensors gave the vapour pressures for
ethyl-acetate shown in Fig. 3. The average deviation in
measured vapour pressure is 0.042 kPa. The deviation from
the literature values if correct (represented by an Antoine type
equation [16]) may be due in part to small pressure fluctuations
around the mean caused by the on/off operation of the
commercial Bu chi pressure controller. A pressure control
strategy via a PC program, such as that of Joseph et al. [15],
is planned. There is nevertheless a small systematic deviation
from the Poling et al. [16] values. Similar pressure deviations,
scattered around the literature values, were obtained for other
solvents.
A desirable characteristic for an ebulliometer is to have a
wide plateau region in which the measured temperature
remains invariant with increased boil-up rate (as reflected by
the power input to the reboiler). Kneisl et al. [17] measured the
slope and width of the plateau regions for a large number of
solvents at atmospheric pressure for an ebulliometer of
conventional design. Similar measurements from our new
design are shown in Figs. 4 and 5. The considerable width of
the plateau regions for acetone (18132 W) and 1-propanol
(53130 W) may be noted. The slopes of the plateau regions in
Figs. 4 and 5 are 31.6 AK/W and 2.2 AK/W, respectively.
These are much smaller than the corresponding values reported
by Kneisl et al. [17] viz. 200 AK/W and 70.4 AK/W,
respectively. The slopes were computed by linear regression
assuming errors to reside only or mainly in the measured
temperatures, and that these are normally distributed. For 2-
butanone, our measurements gave a slope of 0 AK/W for the
region 91.9 W to 106.2 W (cf Kneisl et al. [17], 96.3 AK/W).
4.2. Measured evaporation ratios, /
Evaporation ratios were measured by noting pairs of
temperatures T and T
S
as the pressure was increased at constant
power, as explained in Section 2.2.2 These temperatures,
together with the corresponding latent heats k
T
, k
S
, and the
average liquid heat capacity C

pL
, were entered into Eq. (1) and
the / corresponding to a given yT (=T
0
T
1
, etc.) was
calculated. Plots of / vs. yT are shown in Fig. 6 for two
solvents. Liquid heat capacities were taken from the compila-
tion of Reklaitis [18]. Latent heats were carefully computed
0
200
400
600
800
1000
1200
30 35 40 45 50 55 60 65 70 75 80
Temperature, C
P
r
e
s
s
u
r
e
,

m
b
a
r
Experimental
Literature: Dechema
Fig. 3. Vapour pressure curve for ethylacetate.
55.5
55.55
55.6
55.65
55.7
55.75
55.8
0 20 40 60 80 100 120 140
Power, W
T
e
m
p
e
r
a
t
u
r
e
,

C
Fig. 4. Plateau region for acetone, measured at 101.1 kPa.
95.8
95.85
95.9
95.95
96
96.05
96.1
96.15
96.2
40 50 60 70 80 90 100 110 120 130 140
Power, W
T
e
m
p
e
r
a
t
u
r
e
,

C
Fig. 5. Plateau region for n-propanol, measured at 100.5 kPa.
Ethylacetate
Cyclohexane
y = -0.0062x + 0.0896

o
= 0.0896 @ 15.22 kPa
y = -0.0032x + 0.0352

o
= 0.0352 @ 15.05 kPa
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.1
0 1 2 3 4 5 6
Ti - T, K
V
a
p
o
r
i
z
a
t
i
o
n

R
a
t
i
o
,

Fig. 6. Evaporation ratio, / (using Eq. (1)), vs. temperature increment, yT, for
ethylacetate and cyclohexane at constant power inputs.
J.D. Raal et al. / Journal of Molecular Liquids 125 (2006) 4557 52
from the Clapeyron equation taking into account liquid molar
volume and vapour non-ideality via the Virial EOS. In
calculating k
S
, the saturation pressure at T
S
(temperature at
the entrance to the Cottrell pump) should be used even
though this pressure correction is small. The excellent
linearity of the plots permits accurate extrapolation to
yT=0, to obtain the desired / at the initial pressure, p
0
.
The selected exponent for the reduced pressure, 0.60 gave
good agreement for / with values previously determined for
dilute mixtures by more complex iterative procedures [4].
This exponent, as noted in Section 3.1, is higher than that
proposed in nucleate boiling heat transfer correlations and a
goal of the present study is to find a more soundly-based
criterion for selecting the exponent value.
4.3. Measurement of E and hold-ups (VV/SV) and (RV/SV)
Characterization of the ebulliometer shown in Fig. 7 was
performed as described in Section 2.2.3. This required analysis
of the stream F in the downcomer to obtain z
1
for systems of
known phase equilibrium behaviour, i.e., c
1
V
. Three binary
systems were used, viz. n-hexane (1) ethylacetate (2), ethyla-
cetate (1) toluene (2) and cyclohexane (1)-ethylacetate (2). All
GC detector calibrations were performed using the area ratio
method of Raal and Mu hlbauer [19]. Vapourization ratios, /
were obtained or available for the pressure and power input.
From the measured T, p, and z
1
the desired E values for each
power input were obtained by iteration as follows:
(i) Assume a realistic value for E.
(ii) Calculate (K
1
1) from Eq. (5).
(iii) Calculate c(x
1
) from K
1
using c
1
(x
1
) =(K
1
pU
1
)/
( p
1
sat
) ;(K
1
p)/( p
1
sat
).
(iv) From c
1
(x
1
) calculate x
1
from a one-constant equation for
the activity coefficient, e.g. lnc
1
(x
1
) =Ax
2
2
=(lnc
1
V
)x
2
2
.
Since c
1
V
is known, x
2
2
and hence x
1
are immediately
found. (For greater accuracy the more flexible one-
constant Wilson equation [4] can be used but this is
seldom necessary for the very small concentration range,
0<x
1
0.02.
(v) Compare x
1
from step (iv) with that calculated from
Eq. (3).
x
1

x
S
1
1 K
1
1 E
3
If there is close agreement, accept the value for E (and x
1
).
Results for three binary systems obtained by the above
procedure are shown in Fig. 7 and given in Tables 1 and 2.
The slopes, representing (RV/SV) are in close agreement for
all three systems, viz. 0.901, 0.907 and 0.884, i.e., the
dimensionless reboiler holdup is essentially constant (as
indicated in the analysis of Section 3.4.1) For the hexane
(1) ethylacetate (2) system the intercept was appreciably
larger than for the other two systems for unknown reasons
and characterization of the ebulliometer was based on the lower
two lines using averages for the slope and intercept values, i.e.
E 0:892/ 0:0548: 25
4.4. Measurement of c
1
V
With (VV/SV) and (RV/SV) known and fixed, limiting activity
coefficients can be measured as described in Section 2.2.4,
using dilute but increasing concentrations of solute in the
ebulliometer. For the chosen pressure and power input the
parameter / is strongly dependent on solvent properties, as
shown in Fig. 6. For a system with a new solvent, measurement
of / will precede measurements with finite concentrations
(merely by raising the controlled pressure a few times and
reading T and T
S
).
To calculate x
1
for the DT x
1
plot, an iterative procedure is
required since neither x
1
nor (K
1
1) is known in Eq. (3). The
calculation procedure is nearly similar to that above for finding
E. The steps are:
(i) Assume a realistic value for c
1
V
and keep this constant for
now.
(ii) Assume a value for Z
1
, e.g. slightly smaller than the
charge composition x
S
1
.
hexane (1) -
ethylacetate (2)
cyclohexane (1) -
ethylacetate (2)
ethylacetate (1) -
toluene (2)
y = 0.9075x + 0.0851 y = 0.9008x + 0.0576
y = 0.8843x + 0.052
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
0.18
0 0.02 0.04 0.06 0.08

0.1 0.12 0.14

E
Fig. 7. Ebulliometer parameter E vs. / for n-hexane (1) ethylacetate (2),
ethylacetate (1) toluene (2), and cyclohexane (1) ethylacetate (2).
Table 1
Measured data for the system n-hexane (1) ethylacetate (2)
x
S
1
x
1
p (kPa) T (K) DT (K) /
0 0 32.77 319.47 0
0.003349 0.002455 32.76 319.31 0.16 0.083
0.005581 0.004168 32.80 319.18 0.29 0.063
0.007112 0.005566 32.80 319.08 0.39 0.042
c
1
V
=2.631 (cf. literature [14] c
1
V
=2.85).
Table 2
Measured data for the system ethylacetate (1) toluene (2)
x
S
1
x
1
p (kPa) T (K) DT (K) /
0 0 27.11 342.73 0
0.00301 0.002561 27.11 342.56 0.17 0.0186
0.006495 0.005491 27.12 342.36 0.37 0.0248
0.008816 0.007502 27.11 342.21 0.52 0.0219
c
1
V
=1.165 (cf. literature [14] c
1
V
=1.16).
J.D. Raal et al. / Journal of Molecular Liquids 125 (2006) 4557 53
(iii) Calculate (K
1
1) from Eq. (5):
K
1
1
1 x
S
1
=Z
1

/ x
S
1
=Z
1
E
5
(iv) From K
1
(c
1
p
1
sat
/p), calculate c
1
(x
1
) (vapour phase
non-ideality can be taken into account through the
correction factor U
1
if desired, particularly when the
iteration procedure is nearly converged).
(v) From c
1
(x
1
) calculate x
1
from a one-constant correlating
equation (as for the E calculation described above).
(vi) Compare x
1
from step (v) with that calculated from
Eq. (3). If there is close agreement, accept the value from
Eq. (3).
(vii) Repeat steps (ii) to (vi) for the points measured at
increasing concentrations. Steps (ii) to (vii) represent an
inner computation loop from which, by plotting DT vs.
x
1
, c
1
V
can be obtained from Eq. (17) and the limiting
slope (T/x
1
)
V
.
(viii) In the outer computational loop, compare c
1
V
obtained
in the above step with that assumed in step (i) and
repeat the iterative procedure till convergence. Non-
ideal gas corrections can be introduced in the final
stages.
The procedure is admittedly demanding computationally,
but is based on exact equations and, we believe, a sound
procedure for finding c
1
V
.
4.4.1. Alternative calculation procedure
The iterative calculation procedure outlined above requires
a correlating equation for c
1
(x
1
) which necessitates the inner
and outer loop sequence listed. Another exact equation is
however available [3] which relates / to the overall
composition Z
i
:
/
Z
2
K
1
1

Z
1
K
2
1
26
Implicit in Eq. (26) is the constraint that ~x
i
=1.0.
It was found that Eq. (26) could be used in a simpler
procedure which does not require estimates of c
1
V
or of a
correlating equation for c
1
(x
1
).
The sequence consists of steps (ii) to (iii). For the next step,
Eq. (26) is used to check whether the calculated value of /
corresponds to the measured value. If not, a new value for Z
1
is
assumed and the steps repeated until /
calc
=/
exp
.
From the converged value for K
1
, the correct x
1
is then
again found from Eq. (3). Avalue for K
2
is readily found since
in the dilute regions c
2
=1.0.
For the systems studied, the two procedures gave virtually
identical results.
4.4.2. A direct procedure for calculating c
1
V
from the charge
composition, x
S
1
In the later stages of this project, it occurred to us that c
1
V
could be calculated directly from the limiting gradient for the
charge composition (T/x
S
1
)
V
. It is readily shown that if the
vapourization ratio / is constant for all measured points, c
1
V
is
given by
c
V
1

p
sat
2
p
sat
1
U
V
1
1 b
BT
Bx
S
1
_ _
V
p
1 E
_ _
1 b
BT
Bx
S
1
_ _
V
E
27
If the vapour phase is ideal, Eq. (27) simplifies to:
c
V
1

p
sat
2
p
sat
1
1 BT=Bx
S
1

V
dlnp
sat
2
=dT
_ _
1 E
_ _
1 dlnp
sat
2
=dT
_ _
E BT=Bx
S
1

V
28
An equation for c
1
V
in terms of (T/x
S
1
)
V
was also derived by
Ochi and Lu, in a much earlier publication [20] but involving
the parameter VV/L, i.e. the ratio of static vapour hold-up to
liquid circulation rate. This ratio was considered constant but
the conditions justifying this assumption were not examined in
detail.
Measured and calculated data for the systems ethylacetate
(1) toluene (2) and n-hexane (1) ethylacetate (2) are shown
in Tables 1 and 2, and in Figs. 8 and 9 we show the DT x
S
1
and DT x
1
profiles.
Fitting of quadratic equations to the temperature profiles
gave (T/x
S
1
)
V
and (T/x
1
)
V
from which the c
1
V
values were
calculated from either Eq. (17) or Eq. (27). For the ethylacetate
(1) toluene (2) system there is good agreement between the
0
0.1
0.2
0.3
0.4
0.5
0.6
0 0.002 0.004 0.006 0.008 0.01
x
1
, x
s1
-

T

(
K
)
x
1
x
s1
Fig. 8. Temperature depression (DT) vs. equilibrium liquid composition x
1
and charge composition x
S
1
for ethylacetate (1) toluene (2).
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0 0.002 0.004 0.006 0.008
x
1
, x
s1
-

T

(
K
)
x
1
x
s1
Fig. 9. Temperature depression (DT) vs. equilibrium liquid composition x
1
and charge composition x
S
1
for hexane (1) ethylacetate (2).
J.D. Raal et al. / Journal of Molecular Liquids 125 (2006) 4557 54
values of c
1
V
from both Eq. (17) and Eq. (27), and also with
c
1
V
=1.165 from literature [14].
5. Conclusion
A new ebulliometer design is proposed in which superheat
from the expanding two-phase flow issuing from the Cottrell
pump is largely discharged before impinging on the vacuum-
insulated temperature sensor. Measured vapour pressures for
several solvents are in close agreement with literature values,
(which themselves may differ, in some cases by more than
0.3 kPa). Particularly encouraging for the new design is the
breadth of the plateau region, in some cases extending from
less than 20 to more than 120 W. The plateau slopes appear
to be consistently much lower than those measured by Kneisl
et al. [17] in their extensive study.
The advantages of differential ebulliometry for measuring
limiting activity coefficients have, in the past, been partly
nullified by the remarkably persistent problem of finding,
without composition measurement, the true liquid equilibrium
composition x
1
from the accurately known charge composi-
tion, x
S
1
. Equations of sufficient rigour are now available to
relate these compositions but their evaluation requires
characterization of the ebulliometer by an equipment param-
eter, E. This quantity depends not only on the dimensionless
static holdups of vapour and reboiler (VV/SVand RV/SV) but
also on the dynamic vapourization ratio, /. A new procedure
for finding /, based on the steady-state macroscopic energy
balance, is proposed. The most desirable aspect of the
procedure is that it is experimentally quite simple. It consists
of no more than merely raising or lowering the system
pressure (with pure solvent) around the desired value, and in
each case measuring the equilibrium and superheat
temperatures, T and T
S
. / (and hence also /
S
) can then be
computed from Eq. (1) which requires accurate physical
properties. The surprisingly strong dependence of the boil-up
rate q(W) on pressure (and thus also of the vapourization
ratios to which it is proportional) necessitated the incorpora-
tion of a reduced pressure function f( p
r
). The value of the
exponent, for f (0.60) gave excellent linear plots of / vs. the
temperature increment yT and / values in good agreement
with those found previously by more cumbersome iterative
procedures from measurements on mixtures [4]. A more
analytical procedure for finding the correct or optimum value
of the exponent is however desirable and presently the subject
of further study. In our most recent experiments, with further
equipment improvements, best results were obtained with
n =0.4.
Finally, we have developed exact equations for the
temperature or pressure derivatives with respect to composi-
tion. These equations are of general validity (i.e. not equipment
dependent) and satisfy the full Gibbs-Duhem equation for all
compositions. They can be used in a trial-and-error-free
computation to find the temperaturepressure sensitivity (T/
p)
x
1
, which has several uses. We also propose a quantitative
thermodynamic consistency criterion, ( for isothermal or
isobaric c
1
V
(T x
1
) or ( p x
1
) data sets. A satisfactory
application of this test (Eq. (24)) should indicate the extent to
which a reported c
1
V
is consistent with the measured
temperature or pressure profile.
Acknowledgements
The authors are indebted to glass blower P. Siegling for his
expert craftsmanship, and to the National Research Foundation
for financial assistance.
Appendix A
A.1. Derivation of Eq. (16) for (T/x
1
)
p
To introduce the isobaric Gibbs-Duhem equation (Eq. (11))
into Eq. (16) for (T/x
1
)
p
, we proceed as follows:
Collecting terms with dx
1
from Eq. (14):
dx
1
c
2
p
sat
2
U
2

c
1
p
sat
1
U
1
_ _

x
1
c
1
dp
sat
1
U
1

x
2
c
2
dp
sat
2
U
2
x
1
c
1
p
sat
1
d 1=U
1
x
2
c
2
p
sat
2
d 1=U
2

x
1
p
sat
1
U
1
c
1
dlnc
1

x
2
p
sat
2
U
2
c
2
dlnc
2
A1
The sum of the last two terms may be written as:
c
2
p
sat
2
U
2
x
2
dlnc
2
x
1
dlnc
1
f g
c
2
p
sat
2
U
2
x
1
dlnc
1

c
1
p
sat
1
U
1
x
1
dlnc
1

A2
The first term is recognized as proportional to the isobaric G-D
equation, i.e.,
c
2
p
sat
2
U
2
H
E
=RT
2
dT
_ _
Dividing by dT at constant pressure and inserting the terms in
Eq. (A2) into Eq. (A1) gives:
Bx
1
BT
_ _
p
c
2
p
sat
2
U
2

c
1
p
sat
1
U
1
_ _

x
1
c
1
U
1
dp
sat
1
dT

x
2
c
2
U
2
dp
sat
2
dT
x
1
Blnc
1
Bx
1
_ _
p
Bx
1
BT
_ _
p

c
2
p
sat
2
U
2

c
1
p
sat
1
U
1
_ _

c
2
p
sat
2
U
2
H
E
RT
2
x
1
c
1
p
sat
1
B
BT
1=U
1

x
2
c
2
p
sat
2
B
BT
1=U
2
A3
i.e.,
c
2
p
sat
2
U
2

c
1
p
sat
1
U
1
_ _
1 x
1
Blnc
1
Bx
1
_ _
p
_ _
Bx
1
BT
_ _
p

x
1
c
1
U
1
dp
sat
1
dT

x
2
c
2
U
2
dp
sat
2
dT

c
2
p
sat
2
U
2
H
E
RT
2
b
1
b
2
A4
The terms b
1
and b
2
, involving differentials of 1/U
i
, are given
in Eqs. (16a) and (16b).
J.D. Raal et al. / Journal of Molecular Liquids 125 (2006) 4557 55
Solving for (T/x
1
) from Eq. (A4) gives Eq. (16). As
explained in Section 3.5.1, the derivative (/T)[exp(E
1
)]
and (/T)[exp(E
2
)] (proportional to b
1
and b
2
respectively)
can be most easily evaluated for small temperature increments
by numerical differentiation. They can also be evaluated by
formal differentiation.
It can be shown for example that
BE
1
BT
_ _
p

p p
sat
1
_ _
RT
B
11
v
L
1
T

dB
11
dT

dv
L
1
dT
_ _

B
11
v
L
1
_ _
RT
dp
sat
1
dT

py
2
2
RT
dd
12
dT

d
12
T
_ _

2pd
12
y
2
RT
By
2
BT
_ _
p
A5
Similarly, for ([E
2
]/[T])
p
we obtain:
BE
2
BT
_ _
p

p p
sat
2
_ _
RT
B
22
v
L
2
T

dB
22
dT

dv
L
2
dT
_ _

B
22
v
L
2
_ _
RT
dp
sat
2
dT

py
2
1
RT
dd
12
dT

d
12
T
_ _

2d
12
py
1
RT
By
1
BT
_ _
p
A6
The terms b
1
and b
2
in Eq. (16) or in Eq. (A4) become:
b
1
b
2

x
1
c
1
U
1
BE
1
BT
_ _
p

x
2
c
2
p
sat
2
U
2
BE
2
BT
_ _
p
: A7
A.2. Derivation of Eq. (19) for (p/x
1
)
T
From Eq. (18), by a slight regrouping of terms, we obtain:
Bp
Bx
1
_ _
T

p
sat
1
c
1
U
1

p
sat
2
c
2
U
2
b
3
b
4

p
sat
1
c
1
U
1
x
1
Blnc
1
Bx
1
_ _
T
_ _

p
sat
2
c
2
U
2
x
2
Blnc
2
Bx
1
_ _
T
_ _
: A8
From the isothermal Gibbs-Duhem equation,
x
2
Blnc
2
Bx
1
_ _
T

V
E
RT
Bp
Bx
1
_ _
T
x
1
Blnc
1
Bx
1
_ _
T
: A9
Substitution for x
2
([lnc
2
]/[x
1
])
T
in Eq. (A8) by the RHS
of Eq. (A9) and collecting terms multiplied by (p/x
1
)
T
, we
obtain:
Bp
Bx
1
_ _

c
1
p
sat
1
U
1

c
2
p
sat
2
U
2
_ _
1 x
1
Blnc
1
Bx
1
_ _
T
_ _
b
3
b
4
1
c
2
p
sat
2
U
2
V
E
RT
19
with
b
3
x
1
c
1
p
sat
1
B
Bx
1
exp E
1

T
19a
b
4
x
2
c
2
p
sat
2
B
Bx
1
exp E
2

T
19b
In differentiation of the exponential terms, we get:
BE
1
Bx
1
_ _
T

Bp
Bx
1
_ _
T
RT
B
11
v
L
1
d
12
y
2
2
2pd
12
y
2
By
1
Bp
_ _
T
_ _
A10

Bp=Bx
1

T
RT
A
1
f g A10a
and
BE
2
Bx
1
_ _
T

Bp
Bx
1
_ _
T
RT
B
22
v
L
2
d
12
y
2
1
2pd
12
y
1
By
1
Bp
_ _
T
_ _
A11

Bp=Bx
1
RT
_ _
T
A
2
f g: A11a
Thus, from Eq. (19) by grouping all the terms containing
(p/x
1
)
T
we obtain:
Bp
Bx
1
_ _
T
1
c
2
U
2
p
sat
2
V
E
RT

x
1
c
1
p
sat
1
U
1
RT
A
1

x
2
c
2
p
sat
2
U
2
RT
A
2

_ _

c
1
p
sat
1
U
1

c
2
p
sat
2
U
2
_ _
1 x
1
Blnc
1
Bx
1
_ _
T
_ _
:
A12
Solving for (p/x
1
)
T
then gives Eq. (20) ( if V
E
=0):
Bp
Bx
1
_ _
T

p
sat
1
c
1
U
1

p
sat
2
c
2
U
2
_ _
1 x
1
Blnc
1
Bx
1
_ _
T
_ _
1
x
1
c
1
p
sat
1
U
1
A
1

x
2
c
2
p
sat
2
U
2
A
2

: 20
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