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Determining the Validity of Hesss Law through Calorimetry


Mrs. Bhardwaj

By: Pooyan Sharifi

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According to Albert Einsteins equation (e=mc2) everything in the universe that has a
mass contains energy. The constant c which is directly proportional to energy (e), represents
the speed of light multiplied by itself indicating that even the smallest mass, contains
exponential amounts of potential energy (Ex. Nuclear fission, nuclear fusion). Although we do
not release energy to this scale in the experiment, the basis of releasing potential energy from
matter is still investigated as well as its relation with the laws of thermodynamics. The properties
and laws of energy dictate the flow of our everyday lives in the universe from the chemical
reactions that occur in our bodies, to the nuclear reactions in our sun that release energy in
order for life to exist on Earth.

Although it is impossible to measure the energy constant of matter, chemists can

measure the energy change or enthalpy (H) from a reaction. By using calorimetric based
experiments, one can measure the energy released (exothermic reaction) or energy absorbed
(endothermic reaction) in a thermodynamic system. When studying energy transfer from
chemical reactions it is important to distinguish between the substances undergoing change,
which is called the system, and the surrounding environment which is called the surroundings.
When energy is released/absorbed from a chemical reaction to its surroundings, it is in the form
of heat represented by q, measured in joules in the equation q=mcT. The variable m
represents the mass of the surroundings in grams that interacts with the energy transfer of the
chemical reagents. The variable c represents the heat capacity of the surroundings in
Joule/Gram Celcius), and T represents the change in temperature of the surroundings.
Through the use of this equation, the enthalpy of the system can be calculated by the equation
H = -q. Any energy gained by the surroundings, means energy has been released from the
system, thus it will be a negative value. The ideal system for conducting a calorimetric based
experiment is in an isolated system where energy and matter cannot escape. However, it is
impossible to simulate an isolated system; therefore it is important to understand that some
energy may escape the calorimeter. It is important to assume while calculating values from
calorimetric based experiments that dilute solutions have the same density (1g/1ml) and heat
capacity as water(4.18J/gC), no heat is transferred outside the calorimeter and any heat
transfer by the parts of the calorimeter are negligible. Certain elements and compounds have
indefinite enthalpy changes per quantity for each type of reaction. This is called molar enthalpy
and can be calculated from the equation H= nHx. The variable n represents the number of
moles of the compound, and the variable Hx represents the molar enthalpy by type of reaction
(x). Molar enthalpy of a substance can also be determined using Hesss law which states that
the sum of enthalpy change of a reaction only depends on the initial and final conditions of the
process, and is the sum of the steps. Hesss law also states that it does not matter how many
steps it takes for a reactant to become a product, the enthalpy change will remain the same.
The accepted molar enthalpy of the combustion of Magnesium is -601.6KJ/mol.


If Hesss law is used to calculate the molar enthalpy of combustion for magnesium using
experimentally determined enthalpy values, then the final result will be accurate and near to the
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accepted value (-601.6KJ/mol). This is because Hesss law states that the sum of the enthalpy
pages of the intermediate reactions, should equal the enthalpy change of the target reaction.

Table 1: Quantitative and Qualitative Data in the calorimetric study of the reaction of
1.00mol/L HCl with Mg and MgO in a Styrofoam calorimeter.

Mg (solid ribbon) and MgO (powder) was immersed into a beaker of HCl solution.

Reactant to be Mass Of Initial Final Qualitative

immersed in Reactant +/- Temperature Temperature Observations of HCl
50.0mL +/- 0.05 0.01g of HCl of HCl solution
of 1.00mol/L of solution +/- solution +/-
HCl 0.1C 0.1C
Magnesium 0.02g 22.1C 23.8C Before: Clear,
Ribbon (Mg) transparent solution of
HCl. Mg ribbon was
shiny, smooth and
formed around the Mg
Ribbon rising out of the
completely dissolved
into the solution. No
qualitative change of
Magnesium 0.4g 22.1C 26.1C Before: MgO powder
Oxide Powder is white soft and very
(MgO) fine. HCl solution is
clear and transparent.
During: -Powder
clumped at first.
Solution became
cloudy. While poured,
MgO dust escaped into
the air.
After: -Solution turned
transparent once
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Data Analysis and Calculations

b) Both reactions that occurred were exothermic as the final temperature of the HCl surrounding
was greater than its initial temperature. Therefore the T value would be a positive number in
the equation q=mcT meaning the q value would also be positive. With a q value that is
positive, this indicates that the heat was absorbed by the HCl solution from the release of heat
of the reaction. Ultimately, proving that the reaction was exothermic.

Sample Calculation to determine heat transfer using q=mcT.

T = Tf - Ti

Tf = 100.0C

Ti = 25.00 C

C= 4.18J/gC

m = 50.0g

q = (50g)(4.18J/g C)( 100.0C-25.0 C)


Tf > Ti, q value is positive and energy is released so it is exothermic.


Determine the heat transfer from the magnesium ribbon to the HCl solution.



m = 50.0mL * (1.00g/1.00mL) = 50.0g

c = 4.18J/g C

Tf = 23.8C

Ti = 22.1C

T = Tf - Ti = 23.8 - 22.1 = 1.70 C

q = (50.0g)(4.18J/g C)(1.70 C)

= +355.3J
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Energy absorbed from the surroundings that amount of energy has left the system and
enthalpy of system is negative.

H = -q

= -355.3J

= -0.3553KJ

Solve for Hr using the equation H= nHr rearranged to Hr = H / n

H = -0.3553KJ

mMg= 0.02g

MMg = 24.31g/mol

n = mM

n = (0.02g)/(24.31g/mol)

= 0.000822707 mol

Hr = (-0.3553KJ) / (0.000822707mol)

= -4.32 x 102KJ/mol

the enthalpy change per mole of Magnesium in this reaction is -4.32 x 102 KJ/mol.
d) Mg(s) + 2HCl(aq) H2(g) + MgCl2(aq) H = -432KJ


Determine the heat transfer from the magnesium oxide powder to the HCl solution.



m = 50.0mL * (1.00g/1.00mL) = 50.0g

c = 4.18J/g C

Tf = 26.1C

Ti = 22.1C

T = Tf - Ti = 26.1 - 22.1 = 4.00 C

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q = (50.0g)(4.18J/g C)(4.00 C)

= +836J

Solve for Hr using Hr = H / n

H = -q

= -836J


n = (0.4g) / (40.31g/mol)

= 0.0099231mol

Hr = (-0.836KJ) / (0.0099231mol)

= -84.2KJ/mol

the enthalpy change per mole of Magnesium Oxide in this reaction is -84.2 KJ/mol.
Thermochemical equation for the reaction of MgO in HCl

MgO(s) + 2HCl(aq) H2O(l) + MgCl2(aq) H = -84.2KJ


Reference Equations:

(A) Mg(s) + 2HCl(aq) H2(g) + MgCl2(aq) H = -432KJ

(B) MgO(s) + 2HCl(aq) H2O(l) + MgCl2(aq) H = -84.2KJ
(C) H2(g) + 1/2O2(g) H2O(l) H = -285.8KJ

Formula for the combustion of Magnesium:

Mg(s) + 1/2O2(g) MgO(s)

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1*(A): Mg(s) + 2HCl(aq) H2(g) + MgCl2(aq) H = -432KJ

-1*(B) H2O(l) + MgCl2(aq) MgO(s) + 2HCl(aq) H = 84.2KJ

Insert 1(C) to cancel out H2 and H2O: H2(g) + 1/2O2(g) H2O(l) H = -285.8KJ

Mg(s) + 2HCl(aq) + H2O(l) + MgCl2(aq) + H2(g) + 1/2O2(g)

H2(g) + MgCl2(aq) + MgO(s) + 2HCl(aq) + H2O(l)

Mg(s) + 1/2O2(g) MgO(s)

Hcomb = H 1(A) + H -1(B) + H 1(C)

= -432KJ + 84.2KJ + (-285.8KJ)

= -633.6KJ/mol (enthalpy change is per mole of Magenisum)

Table 2: Quantitative Results of Calculations from Experimental Data

Reaction Calculated Enthalpy Change per Mole of

Mg(s) + 2HCl(aq) H2(g) + MgCl2(aq) -432KJ/mol
MgO(s) + 2HCl(aq) H2O(l) + MgCl2(aq) -84.2KJ/mol
Mg(s) + 1/2O2(g) MgO(s) -633.6KJ/mol 5.32% error

Percent Error

= 100%

601.6 (633.6)
= 100%

= 5.32%
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Evaluation and Conclusion

The purpose of this lab was to determine the molar enthalpy of the combustion of
magnesium using experimental values from reactions between magnesium and magnesium
oxide in hydrochloric acid solution. The calculated molar enthalpy of the combustion of
magnesium from this experiment was -633.6KJ/mol. This result was determined by immersing a
known mass of magnesium metal as well as magnesium oxide powder into a known volume and
concentration of HCl (aq). Knowing the initial temperature of the solution, the final temperature
was measured and the change in temperature was calculated. The heat transfer between the
reactant and the solution was calculated using the equation q=mcT. The energy value also
represents the enthalpy change of the reaction which is H = -q. Finally the known mass of the
reactant was converted to moles to be used in the equation Hr = H / n. Once the enthalpy
change of the reference equations were calculated, Hesss law was used in order to calculate
the enthalpy change of the equation for the combustion of magnesium.

However, the value calculated was not exactly equal to the accepted molar enthalpy of
the combustion of magnesium. Referring to Table 2, the percent error was found to be 5.32% off
from the accepted value. The experiment demonstrated evidence that calculated values were
close to the accepted values. The procedure itself was generally simple to carry out and the
possible sources of error would have no significant effect on the data. Considering the lack of a
true calorimeter to prevent heat escape, as well as professional measuring instruments, the
percent error is relatively minimal.

This experiment did have some sources of error that resulted in the calculated value
being unequal to the accepted value for the molar combustion of magnesium. One reason why
the calculated value was inaccurate is because some heat may have transferred to the air in the
Styrofoam cup or to the cup itself. If this occurred during the experiment, then not all of the
energy released from the reaction would have been transferred to the solution. As a result, the
calculated energy change (q) would have been less. Therefore, the enthalpy of the reaction
would also be smaller than its true value. Ultimately, this would cause the molar enthalpy of
combustion to be greater than the accepted value after the use of Hesss law. This is seen in
Table 2, where the calculated value has a +5.32% percent error.

In addition, another source of error that affected the accuracy of the calculated value
was that the magnesium ribbon surface had a coating of magnesium oxide. When pure
magnesium is exposed to the air, it reacts oxygen to form magnesium oxide. Therefore, making
the reactant in its respective equation, impure and therefore will yield inaccurate results.
Impurity of the magnesium poses many problems in this experiment. For instance, because
magnesium oxide is heavier than magnesium by itself, it will add weight to the mass of the
ribbon. The measured 0.02g ribbon would not be purely 100% the mass of magnesium as the
oxygen atom would also contribute to the mass. Therefore, there will be less magnesium to
react and release energy so the enthalpy change of the reaction would be a smaller. The molar
enthalpy of combustion of magnesium would be above the accepted value.

Another source of error is from uncertainties from the imprecisions of lab equipment. In
the experiment, values were measured for temperature and mass using a simple alcohol based
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thermometer and a milligram balance. The thermometer was not digital and therefore
temperature had to be rounded to the nearest marking. By referring to Table 1 and Table 2, you
can see that the measures values are +/- 0.01 meaning they are not exact. Not having an exact
measurement of the reactants could cause the calculated values to be inaccurate whether by
measuring too much or too little. This could sway the final calculations in either direction.

As well, another source of error is due to the fact that the reactants cannot completely be
transferred from containers. In the experiment, hydrochloric acid was poured from a measuring
beaker to a 100mL graduated cylinder. Not all of the solution could have been transferred as it
would have remained on the measuring beaker as residue. Therefore there would be less
volume present in the reaction and as a result the amount of heat generated would have been
greater. This is because the less volume of a solution, the less energy is required to change its
temperature (specific heat capacity is the number of joules required to raise the temperature of
the substance by 1 degree Celsius). So the enthalpy change calculated for each equation would
be greater than its true value. Another example of this source of error was observed in Table 1
under the Qualitative Observations header. When magnesium oxide powder was poured into
the hydrochloric acid beaker, some of the powder escaped into the air in the form of dust.
Therefore less of the recorded mass is used and ultimately there would be a smaller enthalpy

Lastly, a source of error would be from the use of the stir rod. In the procedure, the
stirring rod used is not cleaned after its use in the first reaction. Therefore the second reaction
could have been contaminated with reactants or products from the first reaction. The effects of
this source of error could vary depending on the reaction of the contaminants in the solution. If
only hydrochloric acid residue was transferred, then more energy would have been required to
increase the temperature. Therefore, the calculated enthalpy change would have been less and
the molar enthalpy of combustion of magnesium would be a smaller negative number.

Based off the evidence gotten from this experiment, it is clear that Hesss law is an
acceptable method to calculate enthalpies of reactions. Despite the many sources of error that
potentially may have made the results inaccurate, Hesss Law still proved to provide a result
which was only 5.32% off from the accepted value. However, Hesss law remains theoretically
true and with accurate experimental data, the percent error could potentially be zero. Although it
is difficult to measure enthalpy change accurately between many intermediate steps (the more
steps the less accurate the result will be) Hesss law still remains an acceptable method to
calculate enthalpies of reactions.

Some improvements that could be made to the procedure of this lab for future use would
be to incorporate a step for rinsing the stirring rod and beakers used. This would prevent cross-
contamination from occurring and increase the accuracy of results. Another improvement would
be to use more professional equipment such as a digital thermometer and a true calorimeter.
Heat is more likely to escape the system in a Styrofoam cup rather than a calorimeter. Another
crucial improvement would be to have multiple trials of the reaction so that the average can be
taken for the calculations. This would improve the accuracy of the final result for this