ThermodynamicsEnthalpy of Reaction and Hesss Law

November 16, 2011

Ryan Miller and Molly Brinser
Purpose
The purpose of this experiment is to verify Hesss Law.
Theory
Four main topics were covered during this experiment including enthalpy
of reaction, heat of formation, Hesss Law, and calorimetry.
Enthalpy of reaction, Hrxn, is the heat or enthalpy change for a chemical
reaction. This energy change is equal to the amount of heat transferred, at
constant pressure, in the reaction. This change represents the difference in
enthalpy of the products and the reactants and is independent of the steps in
going from reactants from products.
Heat of Formation (Hf), which is also known as standard enthalpy of
formation, is defined as the change in enthalpy that accompanies the
formation of one mole of a compound from its elements with all substances in
their standard states. The enthalpy change for a given reaction can be
calculated by subtracting the enthalpies of formation of the reactants from the
enthalpies of formation of the products. This can be illustrated in this equation:
(
)
(
).
During this experiment, Hesss Law was a major concept that the lab
concentrated on. Hesss Law states that if a reaction can be carried out in a
series of steps, the sum of the enthalpies for each step equals the enthalpy
change for the overall reaction. For example, the three chemical equations
used throughout the experiment were:
Equation 1: NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l)
Equation 2: NH4Cl(aq) + NaOH(aq) NH3(aq) +NaCl(aq) + H2O(l)
Equation 3: NH3(aq) + HCl(aq) NH4Cl(aq)
So, Equation 1 plus Equation 2(reversed) will equal Equation 3. In this case,
Hesss Law gave the H for Equation 3.
The last important concept covered in this lab is calorimetry. Calorimetry
is the science of measuring heat, and is based on observing the temperature
change when a body absorbs or discharges energy as heat. A calorimeter is
the device used experimentally to determine the heat associated with a
chemical reaction. During this experiment, a coffee cup calorimeter was used.
The equation
is associated with a calorimeter because it discovers the
amount of heat produced by multiplying the mass of the substance by the
specific heat and by the change in temperature. Since the coffee cup
calorimeter will absorb heat, the data must be corrected for that by solving for
qcal and ccal. The value of qcal will be the opposite of
, and in order to find
the value of ccal, the equation
must be used.

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Procedure
For Part 1, 50.0 mL of distilled water at room temperature will need to be
measured, its initial temperature recorded, and placed into the calorimeter.
Then, 50.0 mL of heated water will need to be measured, its initial temperature
record, and placed into the calorimeter with the room temperature water. With
the motor on and the magnet spinning, immediately insert the thermometer
probe and collect the data. For Part 2, get 50.0 mL of HCl and NaOH and
record their initial temperatures. Then add them to the calorimeter, cover the
calorimeter, insert the temperature probe, and start collecting the data. Do this
procedure for Reaction 2 and Reaction 3. Then, the heat change and enthalpy
of reaction are to be calculated. The value of H is to be found two ways,
through experimental data and using Hesss Law. These values are then
compared to find the percent error of the experiment.
Data
Part 1: Determination of the Heat Capacity of the Calorimeter
Initial Temperature
50.0 mL H2Oroom temperature:
22.4 C
50.0 mL H2Oheated:
68.8 C
Mixing Data
Time (seconds) Temperature (C)
20
44.1
40
43.9
60
43.7
80
43.5
100
43.4
120
43.4
140
43.4
160
43.2
180
43.0
Calculated Values
Tmix = 44.04 C
Tavg = 45.6 C
qcal = +652 J
Ccal = 30.1 J/C
Part 2: Determination of Heats of Reaction
Reaction 1
Initial Temperature
50.0 mL 2.0 M HCl
22.9 C
50.0 mL 2.0 M NaOH
22.7 C
Mixing Data
Time (seconds) Temperature (C)
20
35.8
40
35.8
60
35.8
80
35.8

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100
35.7
120
35.7
140
35.6
160
35.6
180
35.6
Calculated values
Tmix = 35.87 C
qrxn = -6020 J
Reaction 2
Initial Temperature
50.0 mL 2.0 M NH4Cl
23.0 C
50.0 mL 2.0 M NaOH
22.8 C
Mixing Data
Time (seconds) Temperature (C)
20
23.8
40
23.8
60
23.8
80
23.8
100
23.8
120
23.8
140
23.8
160
23.8
180
23.8
Calculated Values
Tmix = 23.77 C
qrxn = -401 J
Reaction 3
Initial Temperature
50.0 mL 2.0 M NH3
22.8 C
50.0 mL 2.0 M HCl
22.4 C
Mixing Data
Time (seconds) Temperature (C)
20
44.1
40
43.9
60
43.7
80
43.5
100
43.4
120
43.4
140
43.3
160
43.2
180
43.0
Calculated Values
Tmix = 27.42 C
qrxn = -2160 J

Page 3

H = -60 kJ/mol

H = -4.0 kJ/mol

H = -22 kJ/mol

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Calculations
Part 1
1. Tmix = 44.04 C (from graph)
2.
3.

(
(

4.

)
)(

(
(
(

)(

)
)

Part 2
Reaction 1
1. Tmix = 35.87 C (from graph)
2.
[ (
)
(
[(

)(
(

3.

)(

)]

)(

)
)]

Reaction 2
*See calculation answers in the Data section
Reaction 3
*See calculation answers in the Data section
Part 3
1. The net ionic equations of the three chemical equations used throughout
the experiment
Equation 1:
NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l)
Na+(aq) + OH-(aq) + H+(aq) + Cl-(aq) Na+(aq) + Cl-(aq) + H2O(l)
*OH-(aq) + H+(aq) H2O(l)*
Equation 2:
NH4Cl(aq) + NaOH(aq) NH3(aq) +NaCl(aq) + H2O(l)
NH4+(aq) + Cl-(aq) + Na+(aq) + OH-(aq) NH3(aq) + Na+(aq) + Cl-(aq) + H2O(l)

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*NH4+(aq) + OH-(aq) NH3(aq) + H2O(l)*

Equation 3:
NH3(aq) + HCl(aq) NH4Cl(aq)
NH3(aq) + H+(aq) + Cl-(aq) NH4+(aq) + Cl-(aq)
*NH3(aq) + H+(aq) NH4+(aq)*
***Equation 1 Equation 2(reversed) = Equation 3
2. Equation 1 H = -60. kJ/mol
Equation 2 H = -4.0 kJ/mol
OH-(aq) + H+(aq) H2O(l)
H = -60. kJ/mol
+
NH3(aq) + H2O(l) NH4 (aq) + OH (aq)
H = +4.0 kJ/mol
NH3(aq) + H+(aq) NH4+(aq)
H = -56 kJ/mol
Error Analysis

)|

There were many errors that could have affected our results in this
experiment but three main errors were all of the initial temperatures were
different, the group had to assume the densities of the solutions, and the group
had to assume that the molarity of all solutions was 2.0 M.
The first error was that the initial temperature measurements for all
solutions were not the same. For example, in the first reaction of Part 2, the initial
temperature of hydrochloric acid was 22.9 C and the initial temperature of
sodium hydroxide was 22.7 C. In order to find the initial temperature, the
average of these two numbers had to be taken, which could have caused the
calculations to be slightly higher or slightly lower than what they should have
been. However, this error would have a negligible effect on the data since
there is not a large difference between the numbers.
The second error that occurred in the experiment was that the group had
to assume the densities of the solutions. In the calculation selection of the lab
handout, it stated to assume the density of the solutions is 1.03 g/mL. Instead of
assuming this value, the group could have calculated it to have a more
accurate answer. Like the error before, it would have a small effect on the data
that was produced.
The third error that occurred in the experiment was that the group
had to assume that the molarity of all of the solutions were 2.0 M.
All of these solutions were student prepared and could have been
made improperly since they were the first solutions the class made.
Mixing solutions that are not close to 2.0 M would have reduced the
overall molarity of the mixed solutions. If the solutions molarity was
less than 2.0 M, then it would increase the final answer, but if the
solutions molarity was greater than 2.0 M, then the final answer
would have decreased. This error would have been the biggest
concern during the lab since it had the largest effect on the data.

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Conclusion
The purpose of this experiment was not met because the group was
unable to verify Hesss Law. From the calculations, H3 was found to be -22
kJ/mol, but when Hesss Law was used, H3 was found to be -56 kJ/mol. The
percent error calculated from these values ended up being -61%. Since the
calculated answers were not nearly as close as they should have been, the
group was unable to verify Hesss Law.
Questions
1. The direct method worked better to find H3 than the indirect method
because in order to use Hesss Law, the data had to be nearly error free.
If the group does have an error in the calculations, than the Hesss Law
answer will not match the answer the group calculated. The Hesss Law
answer had a -61% error compared to the calculated answer. Therefore,
the direct method worked better than the indirect method.
2. Hesss Law states that if a reaction is carried out in a number of steps, H
for the overall reaction is equal to the sum of the Hs from each
individual step.
3. H means the heat or enthalpy change for a chemical reaction. This
energy change is equal to the amount of heat transferred, at constant
pressure, in the reaction. This change represents the difference in
enthalpy of the products and the reactants and is independent of the
steps in going from reactants to products.
4. The true initial temperature is found by using a modified linear fit because
when excluding any points that are skewed, it is giving the results a more
accurate reading. The first couple points that were skewed are due to
incomplete mixing and lack of equilibrium with the thermometer.
5. All of the solutions did not have the same initial temperature because
they were not contained in the same area of the room. These areas
could have a slightly different temperature causing the different initial
temperatures. Also, transfer of heat from holding the graduated cylinder
could have increased the initial temperature, and depending on how
long the graduated cylinder was held, could have determined how high
the initial temperature rose.

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Calculations:
Part 1
5. Tmix = 44.5 C (from graph)
6.
(

7.

8.

)(

(
(
(

)(

Part 2
Reaction 1
4. Tmix = 36.82 C (from graph)
5.
[ (
)
[(

)(
(

6.

)(

)]

)(

)
)]

Reaction 2
*See calculation answers in the Data section
Reaction 3
*See calculation answers in the Data section
Part 3
3. The net ionic equations of the three chemical equations used throughout the experiment
Equation 1:
NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l)
Na+(aq) + OH-(aq) + H+(aq) + Cl-(aq) Na+(aq) + Cl-(aq) + H2O(l)

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Hrxn & Hesss Law

*OH-(aq) + H+(aq) H2O(l)*

Equation 2:
NH4Cl(aq) + NaOH(aq) NH3(aq) +NaCl(aq) + H2O(l)
NH4+(aq) + Cl-(aq) + Na+(aq) + OH-(aq) NH3(aq) + Na+(aq) + Cl-(aq) + H2O(l)
*NH4+(aq) + OH-(aq) NH3(aq) + H2O(l)*
Equation 3:
NH3(aq) + HCl(aq) NH4Cl(aq)
NH3(aq) + H+(aq) + Cl-(aq) NH4+(aq) + Cl-(aq)
*NH3(aq) + H+(aq) NH4+(aq)*
***Equation 1 Equation 2(reversed) = Equation 3
4. Equation 1 H = -60. kJ/mol
Equation 2 H = -4.0 kJ/mol
OH-(aq) + H+(aq) H2O(l)
H = -60. kJ/mol
+
NH3(aq) + H2O(l) NH4 (aq) + OH (aq) H = +4.0 kJ/mol
NH3(aq) + H+(aq) NH4+(aq)
H = -56 kJ/mol

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