In the Laboratory
edited by
Computer Bulletin Board
Integrating Computers into the First-Year Chemistry
Laboratory: Application of Raoults Law
to a Two-Component System
R. Viswanathan and G. Horowitz
Department of Chemistry, Yeshiva College, 500 W. 185th Street, New York, NY 10033
Integration of computers into undergraduate chemistry
education is becoming increasingly common owing to the
availability of high-speed computers and user-friendly software.
Spreadsheet calculations are used extensively in analytical and
physical chemistry. We have introduced a laboratory experi-
ment for the first-year chemistry course that uses spreadsheet
calculations to prepare students for these latter courses. In a
typical first-year chemistry course, students are introduced
to the ClausiusClapeyron equation and use it to predict the
vapor pressure of pure liquids as a function of temperature.
Later in the course, Raoults law is discussed and is used to
determine vapor pressures of components in solution. To-
gether these two concepts can be used to predict the boiling
point of two-component mixtures containing a volatile solute.
The use of a spreadsheet program greatly facilitates the
calculations. Students calculate theoretical boiling points,
which are then compared with experimental measurements.
The two-component system used is a mixture of methanol
and water. This experiment also serves as an introduction to
the principles of fractional distillation, a technique commonly
used in the organic chemistry laboratory for separation of
mixtures.
Background
The equilibrium vapor pressure for each component as
a function of temperature is calculated using the Clausius
Clapeyron equation (1), assuming that the compounds behave
ideally in the gas phase and that the enthalpies of vaporization
are constant:
pi = p i*e (1)
where = (Hvapi/R)(1/Ti 1/Ti*); i = A or B; Ti* is the boil-
ing point of component i at a pressure of pi*; H vapi is the
enthalpy of vaporization of component i at its boiling point;
R is the gas constant in J/K mol; and pi is the equilibrium
vapor pressure at a temperature Ti. Students are provided
with the enthalpies of vaporization of methanol (35.3 kJ/mol)
and water (40.7 kJ/mol) at their normal boiling points. The
spreadsheet program Excel is used to calculate the vapor
pressure of the two components as a function of tempera-
ture (eq 1). By requiring students to perform these calculations
during a recitation period, we make sure that ample help is
available to them.
The theoretical boiling point of the two-component
system for various compositions is calculated as follows.
According to Raoults law (1), the partial pressures of the
1124 Journal of Chemical Education Vol. 75 No. 9 September 1998 JChemEd.chem.wisc.edu
Steven D. Gammon
University of Idaho
Moscow, ID 83844
components at a given temperature are
p A = x A p A ; p B = x B p B (2)
Experiments have been conducted to verify Raoults law
by measuring vapor pressure as a function of composition
(2). However, in the present experiment, the Clausius
Clapeyron equation and Raoults law are combined to determine
the boiling points of solutions as a function of composition.
The total vapor pressure of the two-component solution
is thus given by
p tot = xA pA + xB pB = x A pA + (1 x A )p B (3)
where pA and pB are the equilibrium vapor pressures of the
pure components at a given temperature, and xA and xB are
the mole fractions of methanol and water respectively. Using
eq 1, pA and pB are calculated for temperatures ranging from
the normal boiling point of pure methanol to that of pure
water. By setting ptot equal to the atmospheric pressure in the
laboratory, the composition of the two-component system
that boils at a particular temperature can be calculated. The
calculation is performed over the temperature range of in-
terest and a plot of theoretical boiling point vs mole fraction
is constructed.
Experimental Procedure
The boiling point of a given mixture is experimentally
measured by placing 15 mL of solution in a 25-mL round-
bottom flask equipped with a magnetic stir bar and reflux
condenser. The flask is then heated in a sand bath and stir-
ring is maintained. When the solution begins to boil vigor-
ously, the temperature of the solution is measured using a
thermocouple. The experiment has been repeated using a
sump pump to circulate ice water through the reflux con-
denser to minimize the loss of methanol vapors. The boiling
point measured using a cold-water-filled condenser agreed
within 0.2 C with that measured using an ice-water-filled
condenser.
Solutions of varying compositions (that span the entire
range of mole fractions) are prepared prior to the beginning
of the laboratory. Each student measures the boiling points
of two of these solutions.
Students pool their experimental boiling points for solu-
tions of different mole fractions and plot this data against the
theoretical results (Fig. 1). For all compositions, the experimen-
tal boiling points are observed to be lower than the theoretical
boiling points. Students are asked to interpret their results
in terms of differences in intermolecular forces.
 In the Laboratory

Discussion 370

This experiment enables comparison of experimental 365

results to the results predicted by assuming ideal behavior in
the vapor phase (ClausiusClapeyron equation) and in the 370
liquid phase (Raoults law). The theoretical calculations are made

Boiling Point / K
easy by the availability of spreadsheet programs like Excel. 360
Assuming that the ideal gas assumption and the constancy
of the enthalpy of vaporization are valid approximations, the 355
deviation of experimental results from theoretical values can
be attributed to differences in the strengths of intermolecular 350
forces. For the entire composition range, the experimental
boiling points are lower than those predicted. Within the 345
accuracy of the present experimental measurements, this
implies that the methanolwater system exhibits a positive 340
deviation from Raoults law, and that the vapor pressure of
the solution is greater than predicted. It is interesting to see 335
0.0 0.2 0.4 0.6 0.8 1.0
that in this two-component solution, where one expects the
nature of the intermolecular forces to be similar, significant Mole Fraction of Methanol
deviation from ideal behavior is observed. It is also observed Figure 1. Comparison of experimental boiling points ( ) with those
that a methanol-rich solution behaves more ideally than a predicted theoretically ( ), as a function of mole fraction of methanol
methanol-poor solution. in methanolwater mixtures. P ext = 753.1 mm Hg.

Literature Cited
2. Koubek, E.; Elert, M. L. J. Chem. Educ. 1982, 59, 357. Koubek, E.;
1. See for example: Atkins, P. Physical Chemistry, 5th ed.; Freeman: Paulson, D. R. J. Chem. Educ. 1983, 60, 1069. Burness, J. H. J.
New York, 1996. Chem. Educ. 1996, 73, 967.

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