I.

Title of Experiment : Equilibrium Phase Two Component

II. Date of Experiment : Friday, 19th May 2017
III. Purpose of Experiment :
a. Describing the two-component phase equilibrium liquid-liquid phase
(phenol-water)
b. Determine the equivalent point in the two-component phase
equilibrium liquid-liquid phase (phenol-water)
c. Determine the phase, component and degree of freedom of a two-
component phase equilibrium system liquid-liquid phase (phenol-
water)
IV. BASIC THEORY :
During the formation of mutual change between the three
states of matter focused on the liquid state. In other words, attention has
focused on changes in the liquid and solids, and between liquid and gas.
In discussing the substance of critical circumstances, it would be
appropriate to handle the three states of matter simultaneously, instead of
discussing two of the three substances. Phase diagram is an easy way to
show states of matter as a function of temperature and pressure. As a
typical example, the phase diagram of water. In the phase diagram is
assumed that these substances are well insulated and no other substances
that enter or exit the system.
Partially mixed fluids, is liquids that do not mix in all
proportions at all temperatures. Examples are hexane and nitrobenzene.
For example when adding a little liquid B in another liquid sample A at a
certain temperature T ', the liquid B dissolve completely and the binary
system remains one phase. With more and more the addition of B, when
the stage where B insoluble again. Now the sample consists of two
phases which are in equilibrium with each other. Phase which mostly
consist of A and B. saturated by the other phase is a little B and saturated
by A. the temperature diagram depicted composition. If more B added, a
little late in the composition B. The composition of the two phases in
equilibrium remains a 'and a ", but both increased with decreasing
saturated first phase. An equilibrium will be obtained if B such that
many, so it dissolves all A, and the system back into a single phase. The
addition of B more now will only dilute the solution and so the solution
was kept in a single phase.
Temperature affects the composition of the two phases at
equilibrium phase. For the case of hexane and nitrobenzene, the ability
to raise the temperature and increase the mixing. Therefore, the two-
phase system is not as widespread as each phase in equilibrium richer
one of two components: a phase which contains a more rich in B and
phase which contains B richer A. entire phase diagram can be created by
repeating the observations of various temperature and then draw the line
linking the two phases.
For a two-component system for single phase F = 2-1 + 3 = 3.
So there are three variables that must be determined, is temperature,
pressure and concentration. The graph thus form a three-dimensional
graphics are difficult to draw. For simplicity, taken one fixed variable,
usually taken p fixed, to obtain a diagram expressing the relation TC.
two-component system also rejuvenate by taking equilibrium separately-
equilibrium, is equilibrium
 Liquid-gas
 Solid-gas
 Liquid-liquid
 Solid-liquid

A binary system has two components; CC equals 22, and the number of
degrees of freedom is F=4−PF=4−P. There must be at least one phase, so
the maximum possible value of FF is 3. Since FF cannot be negative, the
equilibrium system can have no more than four phases (White, 1999).
We can independently vary the temperature, pressure, and composition of
the system as a whole. Instead of using these variables as the coordinates
of a three-dimensional phase diagram, we usually draw a two-
dimensional phase diagram that is either a temperature–composition
 diagram at a fixed pressure or a pressure–composition diagram at a fixed
temperature. The position of the system point on one of these diagrams
then corresponds to a definite temperature, pressure, and overall
composition. The composition variable usually varies along the
horizontal axis and can be the mole fraction, mass fraction, or mass
percent of one of the components, as will presently be illustrated by
various examples. The way in which we interpret a two-dimensional
phase diagram to obtain the compositions of individual phases depends
on the number of phases present in the system.

 If the system point falls within a one-phase area of the phase diagram, the
composition variable is the composition of that single phase. There are
three degrees of freedom. On the phase diagram, the value of
either TT or pp has been fixed, so there are two other independent
intensive variables. For example, on a temperature–composition phase
diagram, the pressure is fixed and the temperature and composition can be
changed independently within the boundaries of the one-phase area of the
diagram.
 If the system point is in a two-phase area of the phase diagram, we draw a
horizontal tie line of constant temperature (on a temperature–composition
phase diagram) or constant pressure (on a pressure–composition phase
diagram). The lever rule applies. The position of the point at each end of
the tie line, at the boundary of the two-phase area, gives the value of the
composition variable of one of the phases and also the physical state of
this phase: either the state of an adjacent one-phase area, or the state of a
phase of fixed composition when the boundary is a vertical line. Thus, a
boundary that separates a two-phase area for phases αα and ββ from a one-
phase area for phase αα is a curve that describes the composition of
phase αα as a function of TT or pp when it is in equilibrium with phase ββ.
The curve is called a solidus, liquidus, or vaporus depending on whether
phase αα is a solid, liquid, or gas.
 A binary system with three phases has only one degree of freedom and
cannot be represented by an area on a two-dimensional phase diagram.
Instead, there is a horizontal boundary line between areas, with a special
point along the line at the junction of several areas. The compositions of
the three phases are given by the positions of this point and the points at
the two ends of the line. The position of the system point on this line does
not uniquely specify the relative amounts in the three phases.
For binary mixtures of two chemically independent
components, C = 2 so that F = 4 − P. In addition to temperature and
pressure, the other degree of freedom is the composition of each phase,
often expressed as mole fraction or mass fraction of one component
(Atkins P.W, et all, 2006)

 Boiling Point Diagram

As an example, consider the system of two completely miscible liquids
such as toluene and benzene, in equilibrium with their vapours. This
system may be described by a boiling-point diagram which shows the
composition (mole fraction) of the two phases in equilibrium as functions
of temperature (at a fixed pressure). Four thermodynamic variables which
may describe the system include temperature (T), pressure (p), mole
fraction of component 1 (toluene) in the liquid phase (x1L), and mole
 fraction of component 1 in the vapour phase (x1V). However since two
phases are in equilibrium, only two of these variables can be independent
(F = 2). This is because the four variables are constrained by two relations:
the equality of the chemical potentials of liquid toluene and toluene
vapour, and the corresponding equality for benzene.
 For given T and p, there will be two phases at equilibrium when the
overall composition of the system (system point) lies in between the two
curves. A horizontal line (isotherm or tie line) can be drawn through any
such system point, and intersects the curve for each phase at its
equilibrium composition. The quantity of each phase is given by the lever
rule (expressed in the variable corresponding to the x-axis, here mole
fraction).
 For the analysis of fractional distillation, the two independent variables are
instead considered to be liquid-phase composition (x1L) and pressure. In
that case the phase rule implies that the equilibrium temperature (boiling
point) and vapour-phase composition are determined.
 Liquid–vapour phase diagrams for other systems may
have azeotropes (maxima or minima) in the composition curves, but the
application of the phase rule is unchanged. The only difference is that the
compositions of the two phases are equal exactly at the azeotropic
composition (Gibbs, J.W. 1961).

Partially mixed fluid pair can be divided into four types:

Type I: mix with maximum critical solubility temperature (maximum

critical solution temperature)

 Examples of this type:

a. System water-aniline
b. Phenol-water system
c. Aniline system-hexane
d. Methanol-cyclohexane system
e. System methanol-carbon disulfide
Type II: mix with minimum critical solubility temperature (minimum
critical solution temperature)

 Examples of this type:

a. System water-trimethyl amine

Type III: critical solubility temperature of the mixture with the

maximum and minimum

 Examples of this type:

b. Water system-methyl ethyl ether
c. System water-mikotin
d. Water system-methyl piperidine

Type IV: the mixture does not have the critical solubility temperature.
Critical temperature above Tuc is the upper limit temperature at which
phase separation occurs. Above the upper temperature limit, the two
components completely mixed. Temperature is there because of the
larger thermal movement produces a greater ability to mix the two
components. Some systems exhibit lower critical temperature Tic,
where below this temperature the two components mixed in any ratio
and above the temperature of the two components form two phases.
One example is water and triethylamine. In this case, the low
temperature of both components can be mixed because of the
components that form weak complexes, at higher temperatures the
compound decomposes and the second component is less miscible.
Some systems have a critical temperature above and below the critical
temperature. Why after a weak complex decomposes, so that both
components can mixed partially, at high temperature, thermal
movements create a homogeneous mixture back, as is the case in most
ordinary liquids. The most famous example is the nicotine and water
that mixed partly at temperatures between 61oC and 210oC.
 References

Atkins, P.W, de Paula, J. 2006. Physical Chemistry. London : Oxford University

Press
Bahl, Arun.2002.Essential of Physical Chemistry. New Delhi: S.Chand Company
Ltd.
Gibbs, J.W. 1961. Scientific Papers. New Work: Dover.
Tim Dosen Penyusun Panduan Praktikum Kimia Fisika .2017. Panduan
Praktikum Kimia Fisika II. Surabaya: Jurusan Kimia FMIPA Unesa
White, Mary Anne. 1999. Properties of Materials “Thermodynamis Aspects of
Stability”. London : Oxford University Press.