9 CALORIMETRY

Theory
The word calorimetry is derived from Latin word “calor”, that means the heat. It refers to
the measurement of the heat of chemical reactions and/or thermodynamic phase changes.
This heat does not contribute to the temperature change but it is rather used for changes in
the molecular structure of matter. It is often called a latent heat, because it causes no apparent
change. Temperature of an object at its melting temperature tm does not respond to further
heating until the object melts throughout its entire volume. Heat that is consumed by the
melting object follows the equation:
Q  ml m (J) (1)
where lm is a specific heat of melting (melting heat)
Numerically lm corresponds to a heat that turns 1 kg solid object at its melting temperature
tm into a liquid without the change in temperature. It is expressed in units of J kg-1.
On the other hand, temperature of a matter that is away from phase transition region changes
from tA to temperature tB upon matter's heating. This process follows the equation:
Q  mc(t B  t A ) (J) (2)
where c is a specific heat capacity (specific heat) of a particular matter
Numerically, it represents a heat that is consumed by 1 kg of matter for temperature increase
of 1 °C. Its units are J kg-1.K-1. In a case of object, that consists of several substances, we
define a heat capacity (C) as a heat consumed by the entire object for the temperature
increase of 1 °C.
Q  C (t B  t A ) (J) (3)
Heat capacity (C) is expressed in units of J K-1.
Calorimetric determination of the specific melting heat of ice
A simple calorimeter consists of a thermometer attached to an insulated container. For
example, a thermos with electric mixer and thermometer is going to be used in this
assignment. We fill this calorimeter, which is characterized by the heat capacity C, with
water of the weight m1 and temperature t1.
If we add an ice of the weight m and temperature 0 °C, temperature inside calorimeter
continuously decreases down to the value t > 0 °C. Steady temperature means the completion
of ice melting and homogeneous distribution of temperature through the entire system. Now,
let's have a closer look at the whole process in detail. The heat Q1 was necessary to melt the
ice (see equation 1):
Q1  ml m (J) (4)
where lm is a specific melting heat of ice, that we are going to determine.
After absorbing this heat, added ice changed itself into liquid water of the same weight m
and temperature 0 °C. However, the final temperature t > 0 °C indicates that this water
received additional heat Q2 (see equation 2):
Q2  mc(t  0)  mct (J) (5)
where c = 4,18 kJ K-1⋅kg-1 is a specific heat capacity of water. At the same time, water of
the weight m1, that was filling the calorimeter at the beginning, released the heat Q3 while
its temperature decreased from t1 to t (see equation 2):
Q3  m1c(t1  t ) (J) (6)
In addition to temperature change of water, calorimeter underwent the same temperature
change and thus released the heat Q4 (see equation 3):
Q4  C (t1  t A ) (J) (7)
where C = 79 J K-1 is a heat capacity of calorimeter.
Since the whole system is insulated from the surroundings, released heat is equal to the
received one:
Q1  Q2  Q3  Q4 (8)
Combining equations (4-7) yields:
ml m  mct  m1c(t1  t )  C (t1  t ) (9)
and equation for calculation lm is then expressed as:
(m1c  C )(t1  t )
lm   ct (J kg-1) (10)
m
where m1 is mass of water on calorimeter (kg), c is specific heat capacity of water
(J kg-1.K-1), t1 is initial temperature water and calorimeter (°C), t is final temperature of
system (°C), C is heat capacity of calorimeter (J K-1).

Aim of exercise
Determine specific heat capacity of the ice from calorimetric measurements.
Equipment
Calorimetric container with an electric mixer and thermometer, balance, ice, graduated
cylinder, beaker
Experimental procedure
1. Using graduated cylinder, fill the calorimeter with 500 ml of water which
temperature is about 30 °C.
2. Calculate the water weight m1, supposing its density is 1 g cm-3.
3. Close the container and turn on the mixer. Wait until the temperature becomes steady
for at least 3 minutes and write down the final temperature t1.
4. Weight out about 50-100 g of ice (m) and add it quickly to the calorimeter.
5. Close the container and turn on the mixer. Wait until the temperature becomes steady
for at least 3 minutes and write down the final temperature t.
6. Pour water out of the calorimeter, dry it and repeat the measurement two more times.
7. Use the equation (10) to calculate specific melting heat of ice for each measurement.
8. Determine average value and compare it to the value listed in the handbook of
physics (lm theor = 332,43 kJ kg-1).
9. Calculate standard deviation of lm according equation:

(X i  X )2
sx  i
(kJ kg-1) (11)
n 1
where Xi is lmi i = 1, 2 and 3
n is number of measuremnts (n = 3)

Table 1 Measured and calculated values for determine specific heat capacity of the ice
maesurement m1 (kg) m2 (kg) t1 (°C) t (°C) lm (J kg-1)
1
2
3
lm = J kg-1
 References
1. Kopecký, F.: Physics for Students of Pharmacy I. Bratislava, UK 1999. 184 s. (in
Slovak)
2. Edition of Department of Physical Chemistry: Laboratory Practice in Physics for
Students of Pharmacy. Faculty of Pharmacy, Comenius University, Bratislava, UK
1991.
3. Oremusová J., Vojteková M., Sarka K.: Fyzika – laboratórne cvičenia pre
farmaceutov UK Bratislava 2009 (in Slovak).

Manual written
RNDr. Alexander BÚCSI, PhD., doc. RNDr. Jana GALLOVÁ, CSc., Ing. Jarmila
OREMUSOVÁ, CSc., prof. RNDr. Daniela UHRÍKOVÁ, CSc.