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Introduction

Thermochemistry is a branch of chemistry that studies relationships between chemical


actions and the heat that is generated or absorbed by the action and includes calculations as the
heat capacity, heat of combustion, heat of formation, etc. In thermochemistry the system is a
specific part of the universe that is studied and often is a chemical reaction. The surroundings are
the other parts of the universe that are not in the system, typically outside of the system. The
systems can be: open when both energy and matter can be exchanged with the surroundings (a
full glass of water), closed when only the energy can be transferred (a sealed wine bottle) and
isolated when neither the energy nor the mater can be exchanged (an sealed thermos bottle).
An important aspect of thermochemistry is the First Law of Thermodynamics that states the
energy cant be created or destroyed. In other words when a system releases or absorbs energy the
total energy of the universe will be constant and it will not change, and therefore the energy will be
transferred. This concept can be mathematically expressed as:

where is the difference in energy, q is heat and w is work. From this equation there are few
conventions that apply: when q is positive the heat is absorbed by the system, when q is negative
the heat is lost by the system, when w is positive work is done on the system and when w is
negative the work is done by the system.
Enthalpy, notated with H, is a state function that describes the heat change that occur in a reaction.
If a reaction is termed exothermic, it has a negative value of H and if it is endothermic, it has a
positive value of H. This flow of heat is the enthalpy exchange notated with The enthalpy
change is measured in Kj/mol. H is dependent upon three quantities:
The mass, m, of the system: the more massive an object the more heat needed to
raise its temperature.
The change in temperature, (T): the larger the temperature change in a system
the more heat exchanged.
The heat capacity of the substance(s) making up the system. The specific heat capacity is
defined as the quantity of heat needed to raise 1 gram of the substance by 1 degree Celsius.
The three quantities combine to give the quantity of heat gained, or lost, by a system:
H = mass x Specific Heat Capacity x T
T = Tfinal Tinitial (the final temperature minus the initial temperature.)
In order to measure the amount of heat a reaction, a calorimeter (container with insulating
walls, made so that no heat is exchanged between the contents of the calorimeter and the
surroundings) is often used. Calorimetry determines how much heat is absorbed or released by the
difference of the initial and the final temperature of the process. By determining the temperature
difference, energy was absorbed or released can be calculated. From the known properties of the
calorimeter (mass, heat capacity and temperature change) the quantity of heat exchanged can be
determined using the conservation of energy:
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H(system) = H(calorimeter) = (mass x specific heat capacity x T)
These theoretical elements will be used to determine the specific heat capacity of a metal, then to
determine the enthalpy changes in several chemical reactions.

Experiment 1
Determination of the specific heat capacity of a metal
The specific heat of a metal is determined using the proprieties of the calorimeter. The
calorimeter consists in a Styrofoam Coffee Cup and it is used to accurately determine the specific
heat capacity of a known metal. The metal mass is measured and then metals temperature is raised
to a high temperature in a hot bath. It is placed in the Styrofoam Coffee cup that is filled with a
known mass of water. The heat accumulated in the metal (the system) flowes to the water (the
surrounding) until the temperature of both elements is equal. The temperature change, for both the
calorimeter and the metal is calculated and with the data gathered the enthalpy change can be
calculated using the equations:
H(calorimeter) = (mass water)(specific heat of water)(T water)
H(metal) = (mass metal)(specific heat metal)(T metal)
The law of thermodynamics states that no energy is created or destroyed, but it is transferred.
Therefore the heat absorbed by the metal is released in to the water.
H(metal) = H(calorimeter)
Therefore,
(mass metal)(specific heat metal)(T metal) = (mass water)(specific heat water)(T water)
Specific heat metal =



Determination of the approximate atomic masses from specific heat capacities: The
Law of DuLong and Petit(see chart attached)
The atomic mass of an element is one of the primordial proprieties learned in Chemistry
because it is a very important chemical. Atomic masses can be approximated using the Law of
DuLong and Petit that states the product of specific heat capacity and the approximate atomic mass
is 24.9 J.mol
-1
. C
-1
.
Atomic mass x Specific heat = 24. 9 J.mol
-1
.C
-1



The specific heat capacity of the metal was used to determine the atomic mass using the Law of
DuLong and Petit. The data from the whole class was used to create a graph of the inverse of the
atomic masses vs specific heat capacities. The slope value was 24.9.
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Experiment 2
Determination of the Enthalpy of solution of a salt
When ionic compounds dissolve, the enthalpies of the solid and the aqueous ions are rarely
the same. Heat is transferred from the solid to the solvent, either absorbed or evolved. The enthalpy
change was measured in a simple Styrofoam cup calorimeter.
Ammonium nitrate was dissolved in water and change in heat was determined.
NH4NO3(s) NH4(aq)+ NO3(aq)
As the ammonium nitrate dissolves, heat that is lost or gained is transferred to the water:
H (NH4NO3) = H (water)
H (NH4NO3) = (mass water)(water specific heat capacity)(T water)
Molar Enthalpy can be calculated dividing the difference in enthalpy with the number of
moles in the reaction. The number of moles is the stoichiometric coefficient of that specific
compounds or elements in the reaction.

= n

(products) - n

(reactants)
Hmolar =



Experiment 3
Enthalpy of Neutralization of a Strong Acid with a Strong Base
The enthalpy of the chemical process can be measured as the enthalpy difference between
reactants and products and it appears in the form of heat gained or lost by the reaction. The heat
exchange can be read in a Styrofoam calorimeter.
Solution of hydrochloric acid and solution of sodium hydroxide are combined and the
enthalpy change for the neutralization, can be calculated using the temperature difference, the mass
and the specific heat capacity; since the difference between specific heat capacity of water and the
specific heat capacity of NaCl solution is negligible, the specific heat capacity of water is used.
HCl(aq) + NaOH(aq) NaCl (aq) + H2O(l)
Since both HCl and NaOH are strong acids and bases, they completely dissociate to form ions in
aqueous solution. The net ionic equation for the reaction is:
H
+
(aq) + OH
-
(aq) H2O(l)

As the reaction progressed and the neutralization completed, the heat lost or gained was
transferred to the water.
4

H (neutralization) = H (water)
H (neutralization) = (mass water)(water specific heat capacity)(T water)
The mass of water can be determined from the volume of the whole solution using a density for
water (1.0 g/ml), and the specific heat of the reaction solution can be assumed to be approximately
that of water.
Experiment 4
Enthalpy of Neutralization of a Weak Acid with a Weak Base
Weak acids dont completely dissociate in the solution when reacted with weak bases. The
reaction is a 2 step process. The first step is the dissociation and the second is the neutralization.
1. NH4OH(aq) + HC2H3O2(aq)

(aq) +

(aq) +

(aq)+ C2H3O2(aq) (dissociation)


2.

(aq) +

(aq) 2O (l) (neutralization)


Net NH4OH(aq) + HC2H3O2 (aq)

(aq) + C2H3O2(aq) + H2O(l)


The net enthalpy for the reaction is the inverse enthalpy of the calorimeter and also because it has 2
steps is the sum of the enthalpy of dissociation and the enthalpy of the neutralization.
H (reaction) = H (water)
H (reaction) = (mass water)(water specific heat capacity)(T water)
and
H (reaction) = H (dissociation) + H (neutralization)
The neutralization has the same ionic equation as in the previous section. The results are the same.
The H (dissociation) can be calculated once H (reaction) has been determined.
H (dissociation) = H (reaction) - H (neutralization)

Experiment 5
Enthalpy of a Solution of a Gass: Hesss Law
This experiment is performed in two different ways to demonstrate Hesss Law that
states:If a process occurs in stages, or steps, the enthalpy change for the overall process is the
summation of enthalpy changes for the individual steps. The reaction between aqueous ammonia
and the hydrochloric acid would first be performed combining the reactants in aqueous form and
the second time one of the reactants would be a gas combined with aqueous solution. However,
since the reaction has the same reactants, the enthalpy change should be the same.

The reaction for this experiment is:
NH3(aq) + HCl (aq) NH4Cl(aq)
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The enthalpy change can be calculated from the reaction of aqueous ammonia and aqueous
hydrochloric acid.
The second part of the experiment has 2 steps:
1. NH3(aq) NH3(g)
2. NH3(g) + HCl (aq) NH4Cl(aq)
The heat of solution of a gas is the enthalpy change, obtained by dissolving one mole of gas in a
solvent, the enthalpy change for the first step will be the negative of the heat of solution of
ammonia. The enthalpy change for the overall reaction, H(net) will be given by adding the
enthalpy change each step. In both cases the net reaction is the same, therefore the enthalpy change
should be the same.

H (net) = [- H (bottle)] + [- H (cup)]
Procedure
Experiment 1
Materials needed: 1l beaker, stand, iron ring, metal mesh, Bunsen burner, 10 inch test
tube, 2 thermometers, graduated cylinder, Styrofoam cup, the metal and a balance to
measure the mass of the metal.
Procedure: A metal was assigned in order to determine its specific heat capacity. 1 L
beaker was filled with 900 ml water it was heated to boiling using a stand, an iron ring, a metal
mesh and a Bunsen burner. 10.00 g of the metal was placed in a large, 10 inch test tube, a
thermometer was inserted into the center of the metal. The test tube was placed in the boiling
water without touching the beaker and the level of the water outside is above the metal in the test
tube. The metal was left in the boiling water for 10 minutes. While the metal was heated, 50 ml of
water were poured into a Styrofoam coffee cup. The mass of water was determined using the
density of the water.
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The temperature of the metal was recorded and the value was 99.8C, a separate thermometer was
used to record the temperature of the water in the cup and the value was 26.4. The hot metal was
transferred quickly into the water in the cup. The water and metal were vigorously stirred with the
thermometer. When the temperature stopped rising, the temperature of 29.8 C was recorded. The
final temperature recorded was for of both the water and the metal. The equations bellow were
used to determine the specific heat capacity of the metal.
H(calorimeter) = (mass water)(specific heat of water)(T water)
H(metal) = (mass metal)(specific heat metal)(T metal)
H(metal) = H(calorimeter)
Therefore,
(mass metal)(specific heat metal)(T metal) = (mass water)(specific heat water)(T water)
Specific heat metal =



Part 2 of the first experiment consisted in determining the approximate atomic masses from
specific heat capacities and it was performed to test the Law of Dulong and Petit. The specific heat
capacity of metal utilized in the experiment was used to determine its approximate atomic mass.
The class data was employed to graphically verify the Law of DuLong and Petit. A plot of the inverse
of the atomic masses (x axis) vs specific heat capacities (y axis) should yield a slope of 24.9. The
graph was created using the data from the class and after all the information was plugged in a tread
line was created and the slope of the line was calculated. The result was compared with the value
specified in the Law of DuLong and Petit.
Experiment 2
Materials needed: Styrofoam cup, thermometer, balance, graduated cylinder.
Procedure: 30 ml of water were poured into a Styrofoam coffee cup. The mass of water was
determined using the density of water. (1.0 g/ml). 2.00 grams ammonium nitrate were measured.
The temperature of the water in the coffee cup was measured and the value was 27.4C. The
ammonium nitrate was added to the water and it was stirred vigorously with the thermometer. The
change in temperature was observed and when it stopped changing, it was recorded to 22.9C. The
solution was disposed down the drain and the cup was rinsed with water.
The enthalpy of dissolution of ammonium nitrate sample was determined using the equations:
H (NH4NO3) = H (water)
H (NH4NO3) = (mass water)(water specific heat capacity)(T water)



The molar enthalpy of dissolution of ammonium nitrate was calculated using the equations:
7

= n

(products) - n

(reactants)
Hmolar =



The enthalpy of formation data from the book was used to determine the expected value for the
molar enthalpy of dissolution of ammonium nitrate.
Experiment 3
Materials needed: Styrofoam cup, pipette, 150ml beaker, 2 thermometers, balance, and
graduated cylinder.
Procedure: 20 ml of 1.0 M HCl was poured into a Styrofoam cup. 5 drops of
phenolphthalein indicator were added to verify the neutralization of the acid. 20.0 ml of 1.1 M
NaOH were poured into a small beaker. The temperature of both solutions were brought to the
same value of 26C. The NaOH solution was combined with the HCl solution in the Styrofoam cup.
They were mixed with the thermometer, and the final temperature was observed and recorded
when it stopped changing to 31C. The solution was disposed down the drain and the cup was
rinsed with water.
As the reaction progressed and the neutralization completed, the heat lost or gained was
transferred to the water. The following equations were used to calculate the enthalpy.
H (neutralization) = H (water)
H (neutralization) = (mass water)(water specific heat capacity)(T water)
The mass of water was determined from the volume of the whole solution and density for water
(1.0 g/ml) was used. The specific heat of the reaction solution was be assumed to be approximately
that of water.
Experiment 4
Materials needed: Styrofoam cup, pipette, 150ml beaker, 2 thermometers, balance, and
graduated cylinder.
Procedure: 20 ml of 1.0 M HC2H3O2 was poured into a Styrofoam cup. 5 drops of
phenolphthalein indicator were added to verify the neutralization of the acid. 20.0 ml of 1.1 M
NH4OH were poured into a small beaker. The temperature of both solutions was brought to the
same value of 20.2C. The NH4OH solution was combined with the HC2H3O2 solution in the
Styrofoam cup. They were mixed with the thermometer, and the final temperature was observed
and recorded when it stopped changing to 27.3C. The solution was disposed down the drain and
the cup was rinsed with water.
The enthalpy of neutralization of NH4OH sample was determined using the equations:
H (NH4NO3) = H (water)
H (NH4NO3) = (mass water)(water specific heat capacity)(T water)
8

The stoichiometry of the reaction was used to determine the moles of water formed, and the
enthalpy of neutralization per mole of water formed was calculated. The molar enthalpy of reaction
and the molar enthalpy of neutralization were used to determine the enthalpy of dissociation:
H (reaction) = H (dissociation) + H (neutralization)
The H (dissociation) was calculated once H (reaction) was determined.
H (dissociation) = H (reaction) - H (neutralization)

Experiment 5
Materials needed: gas generating bottle, graduated cylinder, pipette, 2 1/2 inch hoses, 2
thermometers, source of compressed air, Styrofoam cup,
Procedure: 100 ml of concentrated ammonia solution was placed into the gas generating bottle.
The process was carried in the hood. A graduated cylinder was used to measure out 100 ml of 1.00
M hydrochloric acid, and it was placed into a large Styrofoam cup. 3 drops of methyl red indicator to
the acid were added to the acid. The apparatus as shown in the diagram was already assembled.


The temperatures of the hydrochloric acid and the ammonia solution were recorded and the
hydrochloric acid was at 20C and the ammonia solution was at 21C. Compressed air was bubbled
at a moderate rate through the ammonia solution. The compressed air containing ammonia gas was
bubbled through the hydrochloric acid. When the methyl red indicator in the acid changed color,
the compressed air was shut down, the temperature of the ammonia solution was recorded at 15C
and the neutralized hydrochloric temperature was recorded at 38.5C. The neutralized solution in
the cup, was poured down the drain. The remaining ammonia solution in the bottle was placed in
the waste bottle in the hood.

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The enthalpy change for the process in the bottle was determined as H(bottle) and the enthalpy
change for the process occurring in the cup was determined as H(cup). The net enthalpy is given
by the relationship:
H(net) = [H(bottle)] + [H(cup)].
Since 0.1 moles of HCl were in the cup, 0.1 moles of ammonia were used in the reaction because the
stoichiometric ratio is 1:1. H(net), H(bottle), and H(cup) per mole HCl used, were determined.
For the second part of experiment 5
Materials needed: Styrofoam cup, pipette, funnel, thermometer, balance, and graduated
cylinder.
Procedure: 50.0 ml of 1.00 M hydrochloric acid was poured into a Styrofoam cup. 4
drops of methyl red indicator were added to the acid. The temperature of the acid was recorded to
21C. 4 ml concentrated (15 M) ammonia solution were added to the acid though a funnel, with the
end of the funnel immersed in the acid. The resulting solution was stirred, the temperature of
31.5C was recorded. The solution was disposed down the drain and the cup was rinsed with water.
As the reaction progressed and the neutralization completed, the heat lost or gained was
transferred to the water. The following equations were used to calculate the enthalpy.
H (reaction) = H (water)
H (reaction) = (mass water)(water specific heat capacity)(T water)
The molar enthalpy of the reaction was calculated using the equations:

= n

(products) - n

(reactants)
Hmolar =



Note: Only 0.05 moles of ammonia was used in this part.
The net enthalpy H (net) was compared for the direct and indirect methods.
Discussion:
Determination of the specific heat capacity of a metal
In Chemistry a material can be identified based on its chemical and physical properties. One
physical property of a substance is the specific heat capacity, which is defined as the amount of heat
energy required to raise the temperature of 1 g of that substance by 1C. Some materials like water
have high heat capacities and require a significant amount of heat to raise their temperatures. Other
substances like lead have very low heat capacities and require significantly less heat to raise their
temperatures. For example, 4.184 J of heat will raise 1 gram of waters temperature by 1C whereas
only 0.13 J of heat is required to raise 1 gram of leads temperature by 1C. Based on this data, the
specific heat of water is equal to 4.184 J/g. C and the specific heat of lead is 0.13 J/g. C.
The specific heat of a metal can be determined using the proprieties of the calorimeter. The
calorimeter consists in a Styrofoam Coffee Cup and it was used to accurately determine the specific
heat capacity of a known metal. The heat that accumulates in the metal (the system) is transferred
10

to the water (the surrounding) until the temperature of both elements was equal. The difference
between the final temperature and the initial temperature, the mass of the metal and the mass of
the water, the specific heat capacity of the water are proprieties that are known. The equations
used and the values are listed below:
Mass water = 50g
Mass metal = 10.00 g
T initial of water = 26.4C
T initial of metal = 99.8C
T final = 29.8C
T water = -3.4C
T water = -70C
H(calorimeter) = (mass water)(specific heat of water)(T water)
H(metal) = (mass metal)(specific heat metal)(T metal)
The law of thermodynamics states that no energy is created or destroyed, but it is transferred.
Therefore the heat absorbed by the metal is released in to the water.
H(metal) = H(calorimeter)
Therefore,
(mass metal)(specific heat metal)(T metal) = (mass water)(specific heat water)(T water)
Specific heat metal =



Plugging in the values to calculate the specific heat of the metal:
H(calorimeter) = (50g)( 4.184 J/g. C)( 3.4C)
H(metal) = (10g)(specific heat metal)( 70C)
H(metal) = H(calorimeter)
(10g)(specific heat metal)( 70C)= [(50g)( 4.184 J/g. C)( 3.4C)]
Specific heat metal =


= 1.015 J/g. C
Error Analysis: The experiment was repeated 2 times due to errors acquired during the
process. One error was caused by the hot metal transfer to the calorimeter. The time dedicated to
this process was too long and the temperature of the metal was not accurate. The final result was
more than 10% error margin and it was rejected. Another error could be caused by the rate of
steering of the water and the metal. A slow speed of steering would not facilitate the heat transfer
efficiently.
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In the second part of the experiment the determination of the approximate atomic masses
from specific heat capacities: The Law of DuLong and Petit, based on the equation:
Atomic mass x Specific heat = 24. 9 J.mol
-1
.C
-1

the class values rendered a different slope value. From the plot of the inverse of atomic
mass vs specific heat capacity of metals (attached), the slope value is 17.8. This error is too big
compared with the value stated in the law of DuLong and Petit. The difference in error can be
caused by variance in temperatures due error factors discussed previously: metal transfer time, the
rate of steering and possibly the insulation of the calorimeters used.

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