CHEM 116 (LAB)

ARNOLD C. GAJE
INSTRUCTOR 4
DEPARTMENT OF CHEMISTRY
UP VISAYAS

POST-LAB DISCUSSION LECTURE

(EXPERIMENTS 5-9)

Experiment 5: Determination of Partial Molal Volume

Gibbs-Duhem Equation:

Partial Molar Volume for 2-component solution:

Importance of Partial Molar Volumes

Thermodynamically connected with other partial molar quantities such as
the chemical potential can be used to describe changes in equilibria
Used in Theory of solutions
- for binary mixtures of liquid components they are related to heat of mixing and
deviations from Raoults Law

Practice Problems
Gibbs-Duhem Equation
Example 5.1, Atkins and De Paula 2010, pp. 160-161.

Apparent Molal Volume

Molality
Molality (m) =

For solution composed of 1 kg (55.51 mol) H2O and m mol of solute:

Let be the molar volume of pure water ( 18.016 g mol-1/0.997044 g

cm-3 = 18.069 cm-3 mol-1 at 25.00oC). The apparent molal volume is
defined by the equation
where
and

Apparent molar volume

Expressing in terms of density and pycnometer measurements:

Methods of slopes
Mathematically,

Determining

:
= +

Intercept =

Slope =

Plot vs

Density measurements
Pycnometer

Density of solutions:

=

Volume of pycnometer:

=

Assignment:
Calculate the density values in your
experiment again using this
approach. Recalculate values of
other quantities accordingly.

Calculation of Molalities

Where M = molar concentration of solutions

M2 = molar mass of solute

Experiment 6

VAPOR PRESSURE OF A PURE LIQUID

Phases in Equilibrium
Equilibrium: (; p,T) = (; p,T)
or
d() = d()

Clapeyron
Equation

The T at a particular p where

the two phases are in
equilibrium is called the
transition temperature (e.g.,
boiling point, melting point,
sublimation point).

Clausius-Clapeyron Equation
During phase transition:

For vaporization:

For Ideal gas:

( )
=

Clausius-Clapeyron
Equation

Integrating the Clausius-Clapeyron Equation between two limits:

=
+
+

x +

Practice Problems
Clausius-Clapeyron Equation:
Problems 4.9 and 4.12, Atkins and De Paula 2010, pp. 154.

Experiment 7

TRANSITION TEMPERATURE

Phase Transitions
the spontaneous conversion of one phase into another phase
occurs at a characteristic temperature for a given pressure.

Transition temperature, Ttrs

is the temperature at which the two phases are in equilibrium and
the Gibbs energy of the system is minimized at the prevailing pressure.

G = - RTtrs ln K

Detecting Phase Transitions

Easy for vaporization (boiling is very obvious)
Not easy for other transition
Heat is evolved or absorbed during any transition
Other techniques:
1. Differential calorimetry
2. X-ray diffraction (for solid-solid transition)

T does not change

even q is supplied
or removed

Thermal
Analysis

Experiment 8

MISCIBILITY AND TEMPERATURE

Gibbs Phase Rule

gives the number of parameters that can be varied independently (at least
to a small extent) while the number of phases in equilibrium is preserved.
F=CP+2

where F = variance or number of degrees of freedom; C = number of

components; P = number of phases
For an evaporating pure liquid, C = 1, P = 1, and F = 2

2 parameters can be
varied without
changing P. In this
case they are T and p
as discussed earlier.

Liquid-Liquid Phase Diagrams

Used to describe partially miscible liquids

Partially miscible liquids are liquids that do not mix in all proportions at
all temperatures.
Lever Rule:

See Atkins and

De Paula 2010,
pp. 182.