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The Calorimetric Method of Determining The Integral

The calorimetric method is used to determine the integral heat of solution by: 1) Measuring the temperature change of a calorimeter when a salt is dissolved in it to calculate the heat released or absorbed by the solution process. 2) Calculating the heat capacity of the empty calorimeter by passing a known amount of electrical energy through it and measuring the temperature change. 3) Dividing the measured heat of the solution by the amount of salt dissolved to obtain the molar heat of solution.

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2K views3 pages

The Calorimetric Method of Determining The Integral

The calorimetric method is used to determine the integral heat of solution by: 1) Measuring the temperature change of a calorimeter when a salt is dissolved in it to calculate the heat released or absorbed by the solution process. 2) Calculating the heat capacity of the empty calorimeter by passing a known amount of electrical energy through it and measuring the temperature change. 3) Dividing the measured heat of the solution by the amount of salt dissolved to obtain the molar heat of solution.

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LoveFreequency
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© © All Rights Reserved
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The Calorimetric Method of Determining the Integral

Heat of Solution
Summary
The determination of the integral heat of solution consists of:
a) calculation of the heat capacity of the calorimeter;
b) measuring the temperature variation during the solution process in order to
calculate the thermal effect of solution of a salt in a solvent

Theoretical aspects
The quantitative study of the thermal effect which accompanies the dissolution of a solute
in a pure solvent or a solution has been systematized by introducing the concepts of
integral and differential heats of solution.
The integral heat of solution HIS at a particular concentration is the heat change at a
specified temperature and pressure when one mole of solute is dissolved in enough pure
solvent to produce a solution of the given concentration.
Thus HIS for KNO3 in water equals the enthalpy change for the process:
KNO3(s) +nH2O (l) [KNO3, nH2O]
For example, if one mole of solute is dissolved in 500g of water at constant T and P, the
heat change gives the value of the integral heat of solution at the concentration 2 molal.
The dissolution of one mole of KCl in 400 moles of water (which occurs with a
consumption of 4404 cal) can be formulated by the next thermochemical equation:
KCl(s) + 400H2O [KCl, 400H2O]
, HIS=4404 cal
For the interpretation of heat of solution data for some systems, it is instructive to
compare the results with the behavior predicted for ideal solutions. An ideals solution
may be defined as one whose properties could be calculated from the properties of its
pure components, or one which obeys Raoults law over the entire range of the studied
concentrations. The mixing, at constant T and P, of pure liquid solvent with such a
solution produces no change in enthalpy. From this it follows that for the case of a liquid
solute, dissolving to form an ideal solution, HIS =0.For the case of a solid solute which
dissolves to form an ideal solution, ,HIS equals the molar heat of fusion to give the super
cooled liquid at the temperature of the solution. Such behavior is approximated in some
actual cases which involve nonelectrolyte solutes and non polar solvents (e.g.:
naphthalene in benzene).For electrolyte solutes the actual behavior is very different from
the ideal case, because of
solute solvent and solute-solute interactions.
In order to determine the integral heat of solution the following items are necessary:
1) to establish the heat capacity of the calorimeter
2) to estimate the thermal effect of solution by measuring the temperature variation
in calorimeter during the process
Determination of the heat capacity of the calorimeter can be experimentally done either
by performing a chemical process with thermal effect in it or by passing a certain quantity
of electrical energy through the calorimeter and measuring the temperature variation.
From Joules law, the calorimetric constant is:

Qp
T

0.239 E I t
T

(eq 1), E = voltage (in V)

I= current intensity (in A)


T= interval of time (in s)
The heat capacity of the calorimeter W ( in cal/K) is the necessary heat to increase
calorimetric temperature by one degree.

Laboratory Setup
The calorimeter used in this experiment consists of a Dewar vessel fixed by an insulating
ring (to avoid the loss of heat by contact) into a plastic bottle which is also insulated
( with sawdust).A thermometer, a stirrer, a thermo resistance to heat the water and a test
tube obturated with paraffin which contains the sample( NH4Cl).The stirrer is actioned by
an electric motor whose speed can be fixed by a rheostat. A switch allows the connection
between the resistance and the d.c. power supply. The current intensity and the voltage at
the terminals of the thermo resistance will be measured during heating.

Thermometer
Stirrer
d.c. power supply

Calorimeter
Rectifier
Ampermeter
Voltmeter

Working procedure
Determination of the heat capacity f the calorimeter
This determination will be done by passing a certain quantity of electrical energy
through the calorimeter and by measuring the temperature variation due to this
heating.
2

Fill the calorimeter with 1 l of distilled water .Start the stirrer slowly ( the rotational
speed shouldnt be too high and also take care not to modify the speed during the
experiment) and fix the thermometer.
After about 10 minutes ( the necessary period of time to reach a constant temperature in
the calorimeter), the determination of the calorimeter constant may begin. Write down
this temperature, T1, and switch of the circuit. Start the chronometer. Read the voltage
and the intensity.After exactly 7 minutes switch on the circuit. Wait until the temperature
stabilizes and write it down, T2. Use eq 1 in order to compute the heat capacity of the
calorimeter, where T=T2-T1.
Measurement of the integral heat of solution
Without interrupting the stirring, read the constant value before dissolution, T1. Weight a
quantity of NH4Cl as to obtain a solution of one mole salt to 200 moles water and put it in
the calorimeter. Wait until the temperature stabilizes and write it down,T2.
The thermal effect of the solution of the considered amount of salt will be:
q ' W T ' (cal )
T ' T2' T1'

For one mole of salt the effect will be:


Q'

M
q'
m

(cal/mole) ,

where: M = molecular mass of the salt


m = amount of salt dissolved
q=thermal effect of solution

T ' ' T

1
T

2
t

th
f

where T is the temperature variation measured above


T

th

temperature variation in time before the electric heating


i

temperature variation in time after the electric heating


f

time of heating

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