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Instituto Politcnico Nacional.

Escuela Superior de Ingeniera Qumica e Industrias Extractivas.


Laboratory phase equilibrium thermodynamics
Professor : Miguel Snchez Pasten
Students :
Alvarez Gmez Mauricio Alexis
Gmez Vega Luz Yohaida
Gruop: 2IV31

Team: 3

Raoults law

Dew points refer to the temperature and pressure at which a condensed system . When, for
example , in a room they begin to tarnish the glass case that has reached the point of saturation
local moisture and temperature drop that moisture " rushes " , condensing on surfaces. Morning
dew on the leaves of plants is a similar example

Bubble points , temperature and pressure in turn, refer to conditions under which a system is started
boiling . In simply heating water, the time is the first bubble of steam formed , has reached bubble
conditions.

Vapor phase fits the behavior of an ideal gas , ie at


low to moderate pressures the liquid phase is an
ideal solution, provided they are similar chemical
species that must be met :
The enthalpy of solution ( enthalpy of mixing ) is
zero . No change in volume in the mix
The vapor pressure of the solution is adjusted to
Raoult's law .
activity coefficients for each component ( which is a
measure of the deviation from ideality ) are equal to
1

Expression of Raoult's Law


PA = xA .

Expression of the law of Dalton


PT = P A + P B P A = y A . P T y P B = y B . P T
Xi being the mole fractions of the components in the liquid phase
, yi mole fractions of components in the vapor phase Pi and the
vapor pressures of the components. That is generally an ideal
solution to have to :
yi . PT = xi . i
Application limitation : only one species whose applicable Vapor
P is known , para This requires that species are in the subcritical
range .

Case study This system has a pressure of 90 kPa , comprising water and ethyl alcohol . The
concentration of alcohol in the liquid mixture is 40 mol % , ie , about 1.705 grams of alcohol per gram of
water present . We wish to determine the temperature at which the solution , considering it as ideal,
boiled. Also determine the composition of both substances in the vapors formed .
Solution: Being an ideal system apply Equation Raoult Ideal :
yiP = xiPvap
where :
yi is the mole composition of the substance i in the gas phase
xi is the mole composition of the substance i in the liquid phase
P is the total pressure of the system
PVAP is the vapor pressure of the substance i First, the substance
i refers to any component of the mixture and in this case i = 1 = ethyl alcohol
; i = 2 = water.
Also, in our case ,
Xagua = xEtlico = 0.40 = 1 - 0.60 = xEtlico
and the system pressure ,
P = 90 kPa

The vapor pressure is defined as the tendency of a substance in liquid phase to volatilize and is a
function of temperature PVAP = f (T) . At higher temperatures , higher vapor pressure and a greater
tendency of the substance to volatilize since most easily accomplished overcome opposite total
system pressure. When the vapor pressure of the substance equals the total system pressure , the
substance begins to boil , i.e. , the rate of volatilization is maximized .
This trend is exemplified for water, in the following table :

With the system at a total pressure of one atmosphere ( 101.3 kPa ) , we note that for data at 20 is
difficult to volatilize water and boil less . As the temperature increases in turn increases the vapor
pressure , and to reach 100 equal the opposing pressure thereby establish a frank boiling . If the
temperature is above that point the tendency of the system is to completely change the
supersaturated vapor .

This is illustrated in the following diagram

To calculate the vapor pressure equations are several , but one of the most used is the Antoine
equation . This mathematical correlation provides very good approximations to the actual values. It
consists of three constants that incorporate the characteristic properties of each substance and the
temperature of the system :

wherein A, B and C constants specific Antoine for each substance T [ C ] and PVAP in [kPa ]
Continuing our case study, we have

Antoine correlation using vapor pressures for water at various temperatures were calculated as
shown in the following table . It also includes the margin of error introduced when applied . As can be
seen in Table No. 2, for the most commonly used substances accuracy is guaranteed .

In calculating bubble , as the temperature is unknown , we can not assess the vapor pressure .
However we can find the saturation temperature of each substance despejndola Antoine
equation and using the Total System Pressure.

Knowing the saturation temperatures can find a first value of the temperature of the system,
through a weighted formula or cast :

With this initial value the saturation pressures is calculated. Then he returns to the Raoult equation
applied to a selected species and compositions are evaluated in the vapor phase.
The process is repeated until the convergence temperature according to a set tolerance . Finally
concentrations are calculated on the volatile phase .

Experimentaci
n

RAOULTs LAW
PROCEDURE
A. Prepare solution of methanol
(1) and isopropanol ( 2) , in
which the concentration of
methanol (1) varies from 0.0 to
1.0 frac.mol .
B. Each solution Measure the
refractive index (n) and draw a
graph of n vs x1 ( calibration curve)
C.-Place the solution in the container
first team on the hot plate with a slow
stirring , heat to boiling , expected to be
steady and record ( temperature
bubble)

D.- Extrusion equipment that has coolant


foot , take a sample through a thin pipette
and a knob ( deposit in a pre-labeled tube
and cap ) , if the solution is pure is not
necessary
E.-Repeat steps for each solution C and D
F.-Wait for samples containing condensate
to reach room temperature to measure
the refractive index of each
G.- Using the calibration curve to
determine the mole fraction of methanol
vapors at the time of vapor - liquid
equilibrium

ARTICLE

Thermodynamics of mixtures strong negative deviations from


Raoults law. XIII. Relative permittivities for (1-alkanolt +
cyclohexylamine) systems, and dielectric study of (1- alkanol +
polar) compoud (amine, amide or ether) mixtures.

the joural of chemical Thermodyamics . February 2015. Vol.,91

Juan A. Gonzlez, Luis Sanz,, Jos C.