Experiment No.

4
DETERMINATION OF THE ENTHALPY OF FUSION OF A PURE SUBSTANCE (WATER)

I. OBJECTIVES:
a. To determine the enthalpy of fusion of a pure substance (water) using calorimetric
techniques (constant pressure calorimetry).
b. To determine whether the starting temperature of the water inside the calorimeter will
have an effect on the value of heat of fusion.

II. THEORY:

Experiments that quantitatively measure heat exchange (between the defined system and
surroundings) during chemical reactions, phase changes, formation of solutions and other
related physical and chemical processes are collectively referred to as calorimetry
experiments and the measurement device utilized is called a calorimeter. There are two
important types of calorimetry experiments extensively employed for heat exchange
determination: constant – pressure calorimetry (also known as coffee – cup calorimetry) and
constant – volume calorimetry (also known as bomb calorimetry) (s-owl.cengage.com,
2013). We have already been acquainted with constant – volume or bomb calorimeters.
Whereas bomb calorimeters are inherently rigid (constant volume) and tightly closed to
isolate the materials under study from the external effects of the atmosphere, constant –
pressure calorimeters essentially operate under the atmosphere’s influence (open) and hence
result to the more or less constant pressure conditions (~1atm) (www.chem.ufl.edu, 2013).

In laboratories, the most commonly encountered constant – pressure calorimeters consist

of two Styrofoam cups nested together covered with a Styrofoam lid (or cork stopper) with
two small holes or perforations provision for a thermometer, to measure temperature changes
in the course of a process and for a stirring rod, to ensure thorough mixing of the calorimeter
contents (s-owl.cengage.com, 2013).

Fig. 1 – Coffee – cup calorimeter.

 In a constant-pressure calorimetry experiment, the system consists of the substance or
substances undergoing change and the surroundings consist of the other contents of the
calorimeter, the calorimeter itself and all materials outside the calorimeter. However, the
calorimeter is assumed to minimize energy transfer since the second cup serves as an
insulating material (making the process approximately adiabatic and hence no heat exchange
with the environment outside the cup) and that the heat absorbed by the cup assembly itself is
negligibly comparable to that absorbed by the calorimeter content. Also, heat capacity of the
Styrofoam cups is very small compared to that of water. Hence, it is common practice to
assume that the surroundings consist only of the contents of the calorimeter (s-
owl.cengage.com, 2013). In this experiment, we will facilitate determination of the latent
heat of fusion of water (ice) using the method of mixtures through several trials at two
different temperature levels using a coffee – cup calorimeter and determine whether the
starting temperature of the water in the calorimeter will have an effect on the values
subsequently obtained. Comparison of such values then will be made with the theoretical
value for latent heat of fusion of water as obtained from Perry’s Chemical Engineers’
handbook.

When ice (system), at 0 0C, is added to water (surroundings) of higher temperature, the
ice melts with subsequent temperature increase as it absorbs heat from the water.
Consequently, the water temperature decreases due to the heat lost and transferred to the ice.
There comes a time that the water temperature does not change anymore. It is at this state
that the water and ice are said to have reached thermal equilibrium. Hence, water and ice
with different initial temperatures will have at the end of the process the same final
temperature. Since the coffee – cup calorimeter is assumed to be approximately adiabatic, all
of the heat gained by the ice is just then equal to the heat lost by the water inside the
calorimeter (chemistry.about.com, 2013). That is,

Qice = - Qwater (1)

Where: Qwater = mwaterCp,water△Twater (sensible heat) (2)

Thus, by measuring the temperature change of water in the course of the process, the
amount of heat lost by water as sensible heat (heat released or absorbed as a result of
temperature change without any phase changes involved) can be determined. This quantity of
heat is then equal to the heat absorbed or gained by the ice (www.phy-astr.gsu.edu, 2013).

When a substance is undergoing a phase transition, that is, changing from one physical
state to another, it will gain or lose heat without a change in temperature until the phase
transition is complete. This heat gained or lost is known as the latent heat of the substance
and is calculated as Q = m△H. The amount of heat necessary to melt a substance from solid
to liquid at its melting point (or freeze a liquid to solid at its freezing point) is called the
latent heat of fusion, normally expressed either in a unit mass or mole basis of the material
undergoing the phase change (global.britannica.com, 2013). In the experiment, some of the
heat lost by the water will be consumed to melt the ice (at 0 0C), and the rest will be
responsible for raising the temperature of the melted ice to the final temperature of the water,
or in other words, raising the temperature of the ice from 0 0C to Tf. Therefore,
 Qice = - Qwater (1)
Where: Qice = mice△Hfus + miceCp,ice△Tice (3)
△Hfus is the latent heat of fusion of water (ice)

Assuming that Cp,water is approximately independent of temperature for small temperature

changes, substituting equations (2) and (3) to (1) and manipulating the resulting equation, the
final equation for determining the latent heat of fusion of water (ice) becomes:

Qice = - Qwater
mice△Hfus + miceCp,ice△Tice = - mwaterCp,water△Twater ; Cp,ice = Cp,water
mice△Hfus + miceCp,water△Tice = - mwaterCp,water△Twater;
Ti,ice = 0 0C and Tf,ice = Tf,water = Tf at thermal equilibrium

hence,
mice△Hfus + miceCp,water(Tf – 0) = - mwaterCp,water(Tf – Ti,water)
mice△Hfus + miceCp,water(Tf) = - mwaterCp,water(Tf – Ti,water)
[− mwater Cp,water (Tf – Ti,water ) − mice Cp,water (Tf )]
△ Hfus = (4)
mice

III. MATERIALS AND APPARATUS:

a. Materials:
Distilled water
Ice cubes
Coffee cups and cover (Styrofoam cups and cover)

b. Apparatus
Hot plate
Mass – measuring device/ Analytical balance/ Top – loading balance
Thermometer
Stirrer (Magnetic stirrer)
Graduated cylinder
Beakers

IV. PRE – LABORATORY ACTIVITIES

a. Preparation of a data table for this laboratory experiment.
b. Determination of the equation for calculating the heat lost by a substance.
c. Calculation of the specific heat capacity of water in calories and in joules.

V. PROCEDURE:
a. Precautions
a.1 Be careful in handling hot water to avoid spills which may cause burns.
a.2 Take caution in handling glasswares to avoid breakage and injuries.

b. Experiment Procedure
b.1 For each trial, prepare approximately 100 mL of hot water at approximately
70 0C placed in a beaker.
b.2 Weigh the coffee cup (two conjoined cups) with the stir bar. (Note: The
Styrofoam cover/ lid should not be included on the weighing process)
b.3 Pour 90 mL of hot water into the graduated cylinder. Record the exact
volume. Let it air cool to 60 0C in the graduated cylinder.
b.4 Pour the water into the coffee cup calorimeter containing the stir bar. Weigh
the filled coffee cup. Using a thermometer, make sure that the water
temperature is between 55 - 60 0C.
b.5 Turn on the hot plate. Let the contents of the cup be stirred for a while.
b.6 Start recording the temperature.
b.7 Dry a cube of ice with a cloth or towel.
b.8 Leaving the thermometer to touch the water, take off the Styrofoam lid of the
cup and add the ice to the water. Place the lid on the cup as quickly as
possible. Continue temperature measurement, whereby temperature for every
minute passed will be recorded for 10 minutes or until the thermometer
reading has stopped decreasing, whichever is faster, while stirring the
contents.
b.9 Detach the coffee cup cover with the thermometer from the coffee cup. Weigh
the coffee cup (with the contents being the magnetic stir bar, water and of
course the melted ice). Record the mass obtained.
b.10 Repeat procedure for one more trial.
b.11 Repeat the above procedure twice with the temperature of the warm water
approximately equal to 30 0C.
b.12 Perform calculations and find the value of enthalpy of fusion of water (ice).
VI. ILLUSTRATION OF SET – UP

Fig. 2 – Preparation of hot water. Fig. 3 – Coffee – cup, stir bar, and the lid.

Fig. 4 – Weighing of the coffee – cup with the stir bar.

Fig. 5 – Measuring volume of hot water Fig. 6 – Weighing of the water – filled
in a graduated cylinder. coffee – cup (with stir bar).
Fig. 7 – Initial stirring of the calorimeter Fig. 8 – Addition of ice in the water.
content (water without ice).

Fig. 9 – Temperature measurement Fig. 10 – Weighing of the coffee – cup and

for 10 minutes. its contents (stir bar, water and melted ice).

Fig. 11 – Calculating for enthalpy of fusion of water

and the percentage errors.
VII. DATA, ANALYSES AND RESULTS

Table 1 – Measurements and calculated values for determination of the enthalpy of fusion
of water.

Measurements/Calculated Temperature (~ 60 0C) Temperature (~ 30 0C)

Values Trial 1 Trial 2 Trial 1 Trial 2
mcup+stir bar (g) 10.5738 10.5738 10.5738 10.5738
(mcup+stir bar+water)i (g) 98.53 99.82 100.8084 100.4936
mwater (g) 87.9562 89.2462 90.2346 89.9198
Ti,hot water (0C) 57.5 55 31.5 31.5
Tf (0C) 33.5 16.75 17.75 13.75
(mcup+stir bar+water)f (g) 116.7785 136.2053 113.3974 118.3613
mice (g) 18.2485 36.3853 12.5890 17.8677
Vwater in graduated cylinder (mL) 90 90 90 90
Theoretical △Hfus,water
6008.224
(J/mol)
Theoretical △Hfus,water (J/g) 333.51230
△Hfus,water (J/mol) 6013.24551 5717.40553 5821.35456 5507.66068
△Hfus,water (J/g) 333.79104 317.36917 323.13930 305.72638
% error 0.083577 4.84034 3.11023 8.33130

Table 2 – Temperature readings for the 10 – minute water temperature – stabilization

period.

Temperature (0C)
Time (min)
Trial 1 Trial 2 Trial 1 Trial 2
0 57 54.5 31 31
1 39 17 17.75 13.75
2 34 16.75 17.75 13.75
3 33.5 16.75 17.75 13.75
4 33.5 16.75 17.75 13.75
5 33.5 16.75 17.75 13.75
6 33.5 16.75 17.75 13.75
7 33.5 16.75 17.75 13.75
8 33.5 16.75 17.75 13.75
9 33.5 16.75 17.75 13.75
10 33.5 16.75 17.75 13.75
 Temperature vs. Time Graph
60

50

Temperature (0C)
40
(~ 60 C, Trial 1)
30
(~ 60 C, Trial 2)
20
(~ 30 C, Trial 1)
10 (~ 30 C, Trial 2)
0
0 2 4 6 8 10 12
Time (min)

Calculations:

1. Determination of Cp,water at T = 298.15K

From Table 2 – 158, p. 2 – 170 of the handbook,

CpL (J/kmol.K) = C1 + C2T + C3T2 + C4T3 + C5T4
where:
C1 = 276,370 C2 = -2090.1 C3 = 8.125 C4 = -0.014116 C5 = 9.3701 x 10-6

CpL = 276,370 + (-2090.1)(298.15) + 8.125 (298.15)2 + (-0.014116)(298.15)3 +

(9.3701 x 10-6)(298.15)4 = 75384.20367 J/kmol.K
CpL = 75.38420367 J/mol.K x (1 mol/18.015g) = 4.184524211 J/g.K
CpL = 4.184524211 J/g.K x (1 cal/4.184 J) = 1.00012529 cal/g.K

2. Determination of △Hfus,water at 0 0C (theoretical △Hfus,water value):

From Table 2 – 147, p. 2 – 145 of the handbook,

△Hfus,water (at 0 0C, cal/mol) = 1436 cal/mol
△Hfus,water = 1436 cal/mol x (4.184 J/1 cal) = 6008.224 J/mol
△Hfus,water = 6008.224 J/mol x (1 mol/18.015 g) = 333.5122953 J/g

3. Calculation of experimental △Hfus,water values:

Qice = - Qwater
mice△Hfus + miceCp,ice△Tice = - mwaterCp,water△Twater; Cp,ice = Cp,water
mice△Hfus + miceCp,water△Tice = - mwaterCp,water△Twater;
Ti,ice = 0 0C and Tf,ice = Tf,water = Tf at thermal equilibrium
mice△Hfus + miceCp,water(Tf – 0) = - mwaterCp,water(Tf – Ti,water)
mice△Hfus + miceCp,water(Tf) = - mwaterCp,water(Tf – Ti,water)
 [− mwater Cp,water (Tf – Ti,water ) − mice Cp,water (Tf )]
△ Hfus =
mice

For temperature ~ 60 0C:

Trial 1:
mwater = (mcup+stir bar+water)i – (mcup+stir bar)
= 98.53 g – 10.5738 g = 87.9562 g
mice = (mcup+stir bar+water)f - (mcup+stir bar+water)i
= 116.7785 g – 98.53 g = 18.2485 g

△ Hfus =
J J
[− 87.9562g(4.184524211 )(33.5 – 57)K − 18.2485g(4.184524211 )(33.5)K]
g. K g. K
18.2485g
J g J
= 333.791036 x 18.015 = 6013.245514
g mol mol
J J
△ Hfus ≈ 333.79104 ≈ 6013.24551
g mol

Trial 2:
mwater = (mcup+stir bar+water)i – (mcup+stir bar)
= 99.82 g – 10.5738 g = 89.2462 g
mice = (mcup+stir bar+water)f - (mcup+stir bar+water)i
= 136.2053 g – 99.82 g = 36.3853 g

△ Hfus =
J J
[− 89.2462g(4.184524211 g. K)(16.75 – 54.5)K − 36.3853g(4.184524211 g. K)(16.75)K]
36.3853g
J g J
= 317.3691661 x 18.015 = 5717.405527
g mol mol
J J
△ Hfus ≈ 317.36917 ≈ 5717.40553
g mol

For temperature ~ 30 0C:

Trial 1:
mwater = (mcup+stir bar+water)i – (mcup+stir bar)
= 100.8084 g – 10.5738 g = 90.2346 g
mice = (mcup+stir bar+water)f - (mcup+stir bar+water)i
= 113.3974 g – 100.8084 g = 12.5890 g

△ Hfus =
J J
[− 90.2346g(4.184524211 g. K)(17.75 – 31)K − 12.5890g(4.184524211 g. K)(17.75)K]
12.5890g
 J g J
= 323.1393038 x 18.015 = 5821.354557
g mol mol
J J
△ Hfus ≈ 323.13930 ≈ 5821.35456
g mol

Trial 2:
mwater = (mcup+stir bar+water)i – (mcup+stir bar)
= 100.4936 g – 10.5738 g = 89.9198 g
mice = (mcup+stir bar+water)f - (mcup+stir bar+water)i
= 118.3613 g – 100.4936 g = 17.8677 g

△ Hfus =
J J
[− 89.9198g(4.184524211 g. K)(13.75 – 31)K − 17.8677g(4.184524211 g. K)(13.75)K]
17.8677g
J g J
= 305.7263771 x 18.015 = 5507.660684
g mol mol
J J
△ Hfus ≈ 305.72638 ≈ 5507.66068
g mol

4. Calculating for the percentage error:

For temperature ~ 60 0C:

Trial 1:

|theoretical value − experimental value|

% error = x100
theoretical value
J
|6008.224 − 6013.224514|
% error = mol x100
J
6008.224
mol
% error = 0.08357734695% ≈ 0.083577%

Trial 2:

|theoretical value − experimental value|

% error = x100
theoretical value
J
|6008.224 − 5717.405527|
% error = mol x100
J
6008.224
mol
% error = 4.84034005% ≈ 4.84034%
 For temperature ~ 30 0C:
Trial 1:

|theoretical value − experimental value|

% error = x100
theoretical value
J
|6008.224 − 5821.354557|
% error = mol x100
J
6008.224
mol
% error = 3.11022763% ≈ 3.11023%

Trial 2:

|theoretical value − experimental value|

% error = x100
theoretical value
J
|6008.224 − 5507.660684|
% error = mol x100
J
6008.224
mol
% error = 8.331302496% ≈ 8.33130%

Analyses:

The value for the enthalpy of fusion will depend on different variables such as the
mass of water within the calorimeter, the mass of ice added, the final temperature of
the mixture and the initial temperature of hot water.
Based on the data obtained, with the mass of water kept approximately constant
(which is the purpose of measuring approximately 90 mL of water for both trials of
both temperature levels) and with initial water temperature kept as much as possible
close for both trials for each temperature level (54.5 0C and 57 0C, 31 0C), the
variable with the greatest effect on the value of △Hfus for water is the mass of the ice.
The mass of ice inherently dictates the final temperature attained by the mixture and
hence affects the values obtained for △Hfus. The larger the mass of ice, the lower is
the △Hfus value as directly seen from equation (4) which suggests the inverse
proportionality relationship existing between the two mentioned quantities. Another
way to look at this scenario is that a greater mass of ice requires greater amount of
heat for it to change phase or melt and for its temperature to be raised to the
equilibrium temperature. Consequently, greater amount of heat is lost by the water
such that the final temperature for the water (and ice) is low and hence, greater value
for the first term while smaller value for the second term are obtained. This makes the
numerator of equation (4) large. However, this value is compensated by the large
mass of ice in the denominator of equation (4), thus leading to a smaller value for
△Hfus.
From the temperature vs. time graph for each trial obtained, the greater mass of
ice led to a greater temperature drop. For instance, as seen from trial 1 and 2 of ~ 60
0
C temperature level, trial 2 exhibited a drastic temperature drop as compared to the
first trial. This observation really attests that the larger mass of ice will undeniably
 lead to a greater △T or temperature drop and hence greater amount of heat lost by the
hot water to make the ice melt and raise its temperature to the equilibrium value.
In terms of the effect of initial temperature of hot water in △Hfus values, we can
deduce that if we keep everything else constant such as the final temperature of the
mixture, mass of the water and mass of the ice utilized, increasing the initial hot water
temperature consequently increases the value of △Hfus. However, the assumption that
the final temperature of the mixture is unrealistic. Say for example that two trials of
differing initial hot water temperature with the same mass of water and mass of ice
were utilized. Since the last two quantities are constants, we expect that there will be
a proportional decrease in the final temperature of both trials leading to equal
temperature drops or △T. However from equation (4), we can see that though the first
term for both trials will be equal, the second terms are not. If we input numerical
values into the equation with equal mass of ice and mass of water and with differing
initial and final temperatures (but equal △T), we obtain a lower value △Hfus value for
the trial with a higher initial hot water temperature. So, we can say that in general, the
relationship existing between △Hfus and Ti, of hot water is an inverse relationship,
provided mass of water and ice are equal for both trials or set – up.
In the experiment, it is important to stir the water and ice mixture to ensure that
the temperature throughout the water is uniform. Not stirring the ice and water
mixture causes the final temperature to be too warm and gives an experimental value
of the latent heat of fusion that is too low. The thermometer also should not come into
contact with the styrofoam calorimeter. This contact causes the final temperature to
be too warm and will as well give an experimental value of the latent heat of fusion
that is too low. Lastly, if the ice is not dried before adding it to the water, there will be
water at 0 0C on the ice. The added water will contribute to the final mass of liquid
but it will not gain the amount of heat that an equivalent amount of ice would gain.
The initial temperature of the water in the calorimeter hence will not have to drop as
far as it should have. Hence the final temperature will be too high. The result will be
an experimental value of the latent heat of fusion that is too low.

VIII. CONCLUSIONS:

From the experiment, we can conclude that a variety of factors affect the value of
the △Hfus of water such as the mass of the water in the calorimeter, mass of the ice
added, initial temperature of the hot water and the final temperature of the mixture of
melted ice and hot water. From the experiment, we can say that the magnitude of heat
lost by the water (gained by the ice) is dependent on the mass of ice assuming that the
mass and initial temperature of the hot water are constants between trials. That is, the
greatest contributing factor in the determination of the enthalpy of fusion of water is
the mass of ice since it inherently dictates the final temperature of the final mixture.
That is, the greater amount of ice added, the smaller is the final temperature while the
smaller the amount of ice added, the greater its value. Also, in general, the
relationship existing between △Hfus and Ti, of hot water is an inverse relationship
provided that the mass of water and that the mass of ice are constants. If both
quantities are not constant, then the effect of the initial hot water temperature on the
value of △Hfus cannot be certainly determined or established.
 Several errors may have contributed to the differing values of △Hfus value for
water. Most of them are human errors. The mass of water used for each trial should
have been equal because equal volumes (90 mL) have been measured out. However,
the transfer of water from the graduated cylinder may have caused accidental spills or
water was not completely transferred from it to the calorimeter. Temperature
measurements also depend on the bias of the person reading the thermometer.
Continuous stirring of the calorimeter contents should also be done. Also, the
thermometer should not be in contact with the calorimeter or the cups during the
process and that drying the ice before addition to the hot water is necessary. These
three errors should be avoided so as the final temperature will not be too high and
hence the experimental value of the latent heat of fusion of water will not be too low.

IX. REFERENCES:

http://chemistry.about.com/od/thermodynamics/a/coffee-cup-bomb-calorimetry.htm

http://global.britannica.com/EBchecked/topic/331406/latent-heat

http://s-owl.cengage.com/ebooks/vining_owlbook_prototype/ebook/ch5/Sect5-4-
c.html

http://www.chem.ufl.edu/~itl/4411/lectures/lec_9.html

http://www.phy-astr.gsu.edu/butler/labs/physics2211/11SpecificHeat2211.pdf

Perry, R.H. & Green, D.W. 2008. Perry’s Chemical Engineers’ Handbook, 8th ed.,
China: McGraw – Hill, pp. 2-145, 2-170.

Prepared by:

STEPHEN G. ABELADA Group No.: 1

BS ChE V Section No.: 2

Evaluated by:
ENGR. JOHN MARVIN C. MALONES ENGR. HILDA LUZELLE S. MEDRANO
Instructor Instructor

Comments:

Rating: