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BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE PILANI

Pilani Campus, Chemistry Department


Chemical Experimentation - II, CHEM F341, Semester II, 2016 - 17
Laboratory Manual

Experiment No. 08

Determination of the mixing enthalpy of binary fluid mixtures (Acetone and


water)

Theory and evaluation


The change in enthalpy observed when two liquids are mixed. It is the sum of the changes in
enthalpies of the mixing substances during the mixing process. The mixing enthalpy Mh is
influenced by the attractive and repulsive interactions between the molecules involved, which in turn
are dependent on the mixing ratio and is a measure of non-ideality of the mixtures . The interactions
between two liquids can cause endothermic effects (decreasing supra-molecular assemblies) or
exothermic effects (formation of supra-molecular assemblies of different molecules). The quantity of
heat exchanged by mixing nA moles of the component A with nB moles of component B is termed the
integral mixing enthalpy MhI. If a substance is successively added to another one until a certain
mixing ratio is reached, the integral mixing enthalpy is obtained by adding the individual enthalpy
values:

Texp Texp
M h I = Qexp = Qcal = Wel = M hAI + M hBI 1
Tcal Tcal

The molar integral mixing enthalpy (referred to 1 mol of the mixture) is calculated as follows:

M h I
M H I = (2)
n A +n B

The mixing ratio can be measured in terms of mole-fraction of one of the two components.

At constant pressure, the integral mixing enthalpy changes with respect to the composition according
to

M h I M h I
d ( M h I )= dn A+ dn B= M H A dn A+M H B dn B ( 3)
n A nB

On solving and simplifying, one can show that

M h I M h I
M H A= dx B +M H I ; M H B= dx A +M H I ( 4)
xA xB

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BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE PILANI
Pilani Campus, Chemistry Department
Chemical Experimentation - II, CHEM F341, Semester II, 2016 - 17
Laboratory Manual

Procedure
For the first measurement, fill 432 g water into the calorimeter. Insert the oval magnetic
stirrer bar in the calorimeter and switch the magnetic stirrer ON (Caution: Do not switch on the
heating unit by mistake!). Insert the heating coil and the temperature probe into the lid of the
calorimeter and fix them in position. Weigh 154 g of acetone in a 250 ml Erlenmeyer flask. Cut a
rubber stopper with hole lengthwise, put the second temperature probe through the hole and close the
Erlenmeyer flask before hanging it into the temperature-controlled bath. Adjust the immersion
thermostat to the temperature of the water in the calorimeter and wait until the temperature
difference between the acetone in the bath and the calorimeter becomes negligible (0.02 K or less).
Start the measurement with <Start measurement> button. Wait for a few minutes and then pour the
acetone into the water in the calorimeter. The temperature of the mixture will change and reach
equilibrium. After a new temperature equilibrium has been reached, perform electrical calibration for
the determination of the total heat capacity of the calorimeter. To do this, supply 10 V AC to the
work and power meter for the electric heating. Push the <Reset> button and then put the free ends of
the heating coil connection cables into the output jacks. The system is now continuously heated and
the quantity of energy supplied is measured. When the temperature increase in the calorimeter
induced by the electrical heater is approximately equal in size to the temperature change resulting
from mixing the two liquids, switch off the heating and read the exact quantity of electrical energy
supplied. Continue the temperature recording for three minutes, and then stop the recording by <Stop
measurement>.

In a second experiment, add an additional portion of acetone (194 g) to the mixture in the
calorimeter (see Table 1). Perform the experiment completely analogously to the first measurement
and pay attention that the temperature of the mixture in the calorimeter and of the acetone is the
same. In a further series of experiments, successively add the 5 portions of water listed in Table 1 to
the 464 g of acetone in the calorimeter. Carry out this series in the same manner as in the first set of
measurements, after carefully cleaning and drying the calorimeter. It is important that the calorimeter
is re-calibrated after each addition, as the heat capacity of the system is different after each
temperature change. Plot the integral and differential molar enthalpies of mixing as a function of
mole-fraction of acetone.

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BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE PILANI
Pilani Campus, Chemistry Department
Chemical Experimentation - II, CHEM F341, Semester II, 2016 - 17
Laboratory Manual

Calculations:

T exp Tcal Wel MHI x acetone

Results and discussion:

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