Calorimetry - Experiment A Enthalpy of Formation of Magnesium Oxide
Calorimetry - Experiment A Enthalpy of Formation of Magnesium Oxide
Calorimetry - Experiment A Enthalpy of Formation of Magnesium Oxide
CALORIMETRY – EXPERIMENT A
ENTHALPY OF FORMATION OF MAGNESIUM OXIDE
INTRODUCTION
This experiment has three primary objectives:
BACKGROUND
Calorimetry measures the energy that a reaction produces or consumes. For example, the
major difference between gasoline grades is the octane number. Unleaded gas has an
octane of 86, while Super Unleaded gas has a higher octane. Calorimetry could be used to
measure the heat or energy produced when gasoline is burned. More heat (energy) would
be produced by the super unleaded gas so it would have a higher enthalpy compared to
just unleaded gas. Calorimetry could be used to see if a gasoline station is selling the
grades of gasoline it advertises.
The calories in food have also been measured by calorimetry (hence the term calories).
Usually this is a measurement of calories (cal) per gram of food. Remember that calories
are easily convertible to joules (J) and grams can be converted to moles if it is a pure
chemical.
Enthalpy, represented by the symbol H, is a property chemists use to describe the heat
flow into or out of a system in a constant-pressure process. This is often the case since
most processes that are carried out are exposed to the atmosphere as are the reactions
carried out in this course. The enthalpy of a reaction, Hrxn, is defined as the difference
between the enthalpies of the products and the enthalpies of the reactants. In other words,
it is the change in energy for a given amount of a given reaction. The enthalpy of
formation, Hf is defined as the enthalpy or heat change that results when one mole of a
compound is formed from its elements. The standard enthalpy of formation is defined
as the enthalpy of formation measured at 1 atm such that the elements are in their
standard state.
If a reaction is exothermic, heat will be released, and the temperature of the system or
reaction mixture will rise. (In this experiment the heat and temperature rapidly increase
and then slowly decrease as heat is lost to the surroundings.) For endothermic reactions
heat will be absorbed or used and the temperature will decrease. In this experiment we
will use the experimentally measured enthalpy of reaction for a series of exothermic
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reactions and Hess' Law to determine the heat of formation for magnesium oxide (MgO).
We will also determine the enthalpy of reaction for an unknown metal oxide with an acid.
For this experiment pressure will be constant so Enthalpy of Reaction and Heat of
Reaction (Hrxn) are assumed to be the same.
The enthalpy of reaction, Hrxn, can be calculated using the equation:
𝑘𝐽
−(𝐶𝑝)(∆𝑇) −( )(℃) −𝑘𝐽
℃
∆𝑯𝒓𝒙𝒏 = = = A-1
𝑛 𝑚𝑜𝑙 𝑚𝑜𝑙
Where n is the moles of limiting reagent, T (C) is the change in temperature in of the
calorimeter’s contents, and Cp (kJ/C) is the heat capacity of the calorimeter. The value
for n can be determined knowing the amounts of starting material. The T for a reaction
can be calculated using the temperatures before and after the reaction or the initial and
final temperatures. The heat capacity, Cp, of the calorimeter has to be experimentally
determined by doing a reaction where the Hrxn is known. The heat capacity of the
calorimeter is primarily due to the solution in the cup.
Heat capacity (Cp) has units of kJ/C. Physically, this means that it takes the value of the
Cp in energy to raise the calorimeter by 1C. For example, if a calorimeter has a Cp of
0.200 kJ/C, the calorimeter, including its contents, must absorb 0.200 kJ of energy to
increase 1C. A 20 kJ/C calorimeter increases 1C with one hundred times more energy,
or 20 kJ. Cp varies depending on the substance or system and describes how much energy
is needed to change the temperature of that substance or system. The Cp of an ocean is
huge (compared to a drop of water) such that the oceans of the world maintain the earth
at temperatures that support life.
In this experiment, the calorimeter is defined as two nested styrofoam cups, the lid,
magnetic stir bar, and the temperature probe tip, plus the 60.0 mL of the reaction mixture
(mainly water). In order for the heat capacity of the calorimeter to remain constant, all of
these must be present.
Figure A-1 Calorimeter Apparatus (ignore B-1)
NOTE: If less than 60 mL of reaction mixture was added, it would take less energy to increase the
calorimeter and contents by 1C. In other words, the heat capacity would decrease. If more than 60 mL of
the mixture was added, more energy would be needed to increase the calorimeter and contents by 1C. The
heat capacity is then increasing.
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Most importantly the volume of reaction mixture must remain constant because of
the large heat capacity of water. We want the Cp to remain constant because it is the
standard by which we can calculate unknown Hrxn values in reactions 1, 2, and 4. The
Cp is determined in the reaction of HCl with NaOH, using the known enthalpy
(energy/mole) for a strong acid/strong base reaction:
kJ
H+ (aq) + OH- (aq) H2O (l); Hrxn = -55.90 ( mol ) at 25C A-2
Rearranging equation A-1 we can use this Hrxn to solve for Cp.
𝑘𝐽
−(∆𝐻𝑟𝑥𝑛 )(𝑛) (55.90 )(𝑚𝑜𝑙) 𝑘𝐽
𝑚𝑜𝑙
𝑪𝒑 = = = A-3
∆𝑇 ℃ ℃
A value for T in C can then be determined for a known amount of moles (n). Once the
Cp is known we can use it to calculate Hrxn for other reactions where T has been
experimentally determined. Please look in your textbook under calorimetry or
thermodynamics for more information on these concepts. The explanation to determine
T is in the experimental section below.
EXPERIMENTAL
This experiment essentially has three parts. In the first lab period, the data to determine
the enthalpy of reaction for Mg + HCl and MgO + HCl will be collected (one trial on
each). During the second lab period, data will be collected to calculate the Cp using the
reaction of NaOH with HCl (two trials). Also, the enthalpy of reaction for the Exp. An
unknown reacting with HCl will be determined (two trials). The trials for the Cp and
unknown should be run in the same lab period.
Be sure to label each graph carefully with your name, section, date, reaction & trial, mass
of reactant, etc. Note that the Hrxn is not done until after Cp is determined the second
week. Tape graphs into your notebook as you print them.
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CHEMICALS:
SAFETY CONCERNS:
EXPERIMENTAL PROCEDURE:
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NOTE: Only one trial is Clean a teflon stir bar, 50 mL beaker, 25mL and 50mL
needed for this reaction. graduated cylinder and wash bottle.
Add 25.0 mL of 3.0 M HCl (use pump dispenser, ok to
check volume with 25mL graduated cylinder) and 35.0 mL
of pure water to the calorimeter.
Put the temperature probe in through the lid and place the
lid on the calorimeter. Secure the probe with a clamp so
that its tip is in the water and off the calorimeter
Avoid adding extra heat bottom. Don’t allow the stir bar to hit the probe tip (see
from hands, hot plate- fig.A-1).
stirrer; make sure the hot Stir the solution with a teflon stir bar (Do not heat.) Set
plate heat is turned off. stirrer so the solution is mixed vigorously but slow enough
so that it is not splashed.
Put between 0.15 to 0.20 g (not 1.5) of Mg metal turnings
into a clean, dry 50 mL beaker. Record both the beaker’s
mass and the mass of the beaker and Mg.
Click the "Collect" button at the top of your screen to start
graphing the temperature. Do not add Mg turnings yet.
After about one minute, add the metal Mg turnings without
removing the temperature probe from the solution. (Crack
the lid open, add Mg (s), and then close the lid, it is ok if
residual Mg sticks to the inside of the beaker since you will
reweigh it later to see how much Mg was added to the
calorimeter). If any Mg is stuck on the sides of the
Why should you measure calorimeter above the liquid carefully swirl the solution
the mass of Mg this way?
(holding the cup in your hand) to dissolve it.
Reweigh and record the mass of the beaker that
contained the Mg turnings. Subtract this mass from the
mass of the beaker and Mg to get the mass of Mg used.
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NOTE: If data gathering Continue graphing data until a linear line (part 3 in Figure
stops before reaching 350- A-2) is made. (At about 350 to 400 seconds.)
400 seconds click on
“Collect” and then
Adjust graph scale (autoscale) and then do a linear fit (refer
“Append to Latest” to to Figure A-3). Generate line 2 by selecting the linear part
restart collecting data. Do of the graph and doing a linear fit. Under analyze use the
not move the calorimeter interpolate tool to find the starting time of the reaction and
or delete or stop the the corrected temperature at this time. The time could also
program! You can also
get help from your TA!
be used for x in y=mx+b to determine the final temperature
(Tf). The following graphs explain this process.
Point the cursor at the flat part of the graph before the
reaction starts to determine Ti and subtract this from Tf to
determine the change in temperature, Tf - Ti = T.
Calculate these values for every graph done for exp. A.
Label the graph by clicking on the graph title. Edit the title
to include your last name, experiment title-Reaction Mg
+ HCl, date, section letter, and exact mass of Mg used.
Save the graph on your “Z” drive, my documents, or a
thumb drive using a logical file name and print it.
Write the values for Tf, Ti, and T directly on this printed
graph.
Clean and dry the calorimeter, temperature probe, and the
50 mL beaker.
Explanation of the Graph: Below is a general temperature vs. time graph representative
for all reactions trials done for this experiment. (Figure A-2) It is divided into three parts.
Part 1. This is the initial temperature. Only one reactant is in the solution
and so our reaction is not happening. (For example, for Mg, only 25.0 mL
of HCl and 35.0 mL of water are in the solution.) Between part 1 and part
2 the reactants are mixed together.
Part 2. The temperature is changing rapidly. Both reactants are now in the
solution and are reacting to give off heat. (For example, for Mg, this is
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because the Mg turnings are added to the solution.) Somewhere within the
blocked out region the reaction stops.
Part 3. The reaction has already stopped. Since the calorimeter isn’t a
perfect insulator, heat is lost to the environment and, as a result, the
temperature decreases. The temperature should be constantly decreasing.
(For example, for Mg, all of the Mg has been converted to Mg2+.)
Line 1. This line represents the time when the reactants were mixed and so the
start of the reaction.
Line 2. This line helps us model what the final temperature would be if the
reaction and temperature measurement were instantaneous. It compensates
for the heat lost from the calorimeter so that we can determine the final
temperature if the reaction and temperature measurement were
instantaneous. This line is important because it compensates for heat lost
to the environment while temperature is measured during and after the
reaction.
Line 3. This line is drawn at a right angle to line 1 to intersect the point
where lines 1 and 2 meet. It is there to help read the final temperature, Tf,
at the y-axis. The interpolate function can also be used to get Tf.
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Calculations:
g MgO
n mol MgO A-5
MM of MgO
NOTE: Check the Determination of the Cp and Hrxn of an unknown with HCl
calibration of
temperature probe and NaOH + HCl Reaction. Determination of Cp:
calibrate if needed.
NaOH (aq) + HCl (aq) H2O (l) + NaCl (aq)
Remember: 10.00 mL is
more precise than
Clean a 25 mL graduated cylinder, 10 mL volumetric pipet, a
25.0 mL. (cont.)
spatula, a 50 mL beaker, and a wash bottle.
Add 25.0 mL pure water and 10.00 mL of NaOH to the
calorimeter and measure its temperature.
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(cont.) What kind of Put the temperature probe in the calorimeter and stir the
glassware should you solution with a teflon stir bar. (Do not heat)
use for this? _______ Click the Collect button at the top of the screen to start
_________________
graphing the temperature probe. Do not add HCl solution yet.
NOTE: Never click on After about one minute, add the 3.0 M HCl without removing
“New Graph” to start the temperature probe from the solution. (Crack the lid open,
a new trial. Instead add HCl(aq), and close the lid.)
just close the program After about 10 seconds, briefly swirl the solution.
and then reopen it. If
you do click on “New
Continue graphing data until a linear line (Figure A-2: see
Graph” the time scale part 3 of this figure) is made. (At about 350 to 400 seconds.)
will decrease to 200 Adjust scale of graph, do a linear fit, and find the T as was
seconds. Do not move done before.
the calorimeter or Label the graph by clicking on the graph title as before. Enter
delete or stop the
program if it does stop your last name, experiment title, date, section letter, and
early! Get help from NaOH with HCl, Trial 1 or 2, and molarity of NaOH.
your TA! Save the run on your “Z” drive, my documents, or a thumb
drive and print it.
NOTE: Be sure to
Clean, rinse, and dry the calorimeter and temperature probe.
record the exact NaOH
molarity of the carboy. Repeat this once.
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Calculation: Cp
The calibration of the calorimeter is now complete! Cp can now be calculated and
used for all other calculations. First solve for the moles of NaOH (limiting reagent).
(mol/L NaOH) * (L NaOH) = mol NaOH = n
Where M is molarity (exact molarity on carboy) and L is liters of NaOH that was
used. (You need to convert from mL). Now that we have n (mol of NaOH) plug it into
equation A-3. Also called the enthalpy of neutralization (Hrxn) of a strong base by a
strong acid is a constant –55.90 kJ/mol at 25C. This is shown by reaction A-2.
H+ (aq) + OH- (aq) H2O (l); Hrxn = -55.90 (kJ/mol) at 25C A-2
With this value, the moles of limiting reactant (n), and after determining T from
your graphs by extrapolation, the equation A-3 becomes a simple plug and chug.
𝑘𝐽
−(∆𝐻𝑟𝑥𝑛 )(𝑛) (55.90 )(𝑚𝑜𝑙) 𝑘𝐽
𝑚𝑜𝑙
𝑪𝒑 = = = A-3
∆𝑇 ℃ ℃
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Repeat this calculation for the second trial and calculate the median, range, and
relative percent range (see p. I-18) for your Cp.
Now repeat this calculation using the data for MgO to determine the Hrxn of MgO.
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𝑔 𝑢𝑛𝑘𝑛𝑜𝑤𝑛
𝑛= = 𝑚𝑜𝑙 𝑢𝑛𝑘𝑛𝑜𝑤𝑛
𝑔 𝑢𝑛𝑘𝑛𝑜𝑤𝑛
120.0
𝑚𝑜𝑙 𝑢𝑛𝑘𝑛𝑜𝑤𝑛
Now use the value for n (mol of unk), the T determined from the graph, the Cp and the
equation below to calculate the enthalpy of reaction for the unknown with HCl:
𝑘𝐽
−(𝐶𝑝)(∆𝑇) −( )(℃) 𝑘𝐽
℃
∆𝑯𝒓𝒙𝒏 = = = A-1
𝑛 𝑚𝑜𝑙 𝑚𝑜𝑙
Calculate this value for each trial and report the median, range, and relative % range.
Fill out the unknown report sheet at the end of this experiment making sure to put
the unknown number list on the unknown vial that you used (A-xxxx where xxxx is you
unknown number). DO NOT use the hazard code at the bottom of the label (HC-1012).
Make sure that all calculations are done in your laboratory notebook using dimensional
analysis and that the report sheet is complete. Be sure to complete a calculation check!
When doing the calculation check, be aware that the heat of reaction is the same as
enthalpy of reaction and that these values are negative numbers for exothermic reactions.
Get a printout of the calculation check and staple it to the unknown report sheet. Points
will be taken off for incomplete report sheets or resubmission/repeats of the unknown.
Have your regular TA review the report sheet, sign and date it and give it to them for
grading. The report sheet for the unknown must be turned in by the deadline listed in the
syllabus to avoid late points. This same process will be used for the unknowns done in
experiments D, E and F.
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CALORIMETRY - EXPERIMENT A
CHM 152L REPORT SHEET FOR UNKNOWN A-XXXX
____________ kJ/mol
____________ kJ/mol
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