Thermochemistry: An Ice Calorimeter Determination of Reaction

Enthalpy
James E Ciapa
Partner Sergio Castillo
Prof. Sophie Ung
June 7, 2018
Abstract: To determine the reaction enthalpy of H2SO4(aq)+Mg(s)MgSO4(aq)+H2(g) an ice
calorimeter was operated. Through repeated trial runs, the experimental molar enthalpy of
-267.9 kJ/mol was determined as being lower than theoretical at -470.9 kJ/mol.
Introduction
Through the conceptual understanding of the first law of Thermodynamics one
understands that energy is neither created nor destroyed, much rather transferred. One
way in which energy is transferred is through reactions, providing results to create
products or emit energy to its surroundings. To determine the amount of energy
transferred throughout the completion of the reaction, certain variables must stay
constant; with the ice calorimeter created in this lab the temperature will be the controlled
variable. This isothermal, due to no temperature change, reaction will create an instance of
volume change in the apparatuses used allowing for the calculations to determine energy
transferred.
In this lab the point of our calculations will be to understand whether the reaction
H2SO4(aq)+Mg(s)MgSO4(aq)+H2(g) is an endothermic, when energy is absorbed by the
reaction, or exothermic, when the energy is released by the reaction into the surroundings
and how much energy correlates to the reaction type. As we will later, the procedures show
an expectation of an exothermic reaction as the isothermal ice calorimeter is designed to
keep the temperature constant in order for the volume to be measured, in this case the
volume will lower meaning the ice melted. The difference in volume from the final to initial
will provide the data to determine how much energy was provided in the reaction for the
products to be created. The amount of energy is referred to as the molar enthalpy of a
reaction.

Safety Hazards
In order to practice proper laboratory safety, the chemicals created from the elements used
have potential dangers that must be carefully abided to. According to Flinn Science Inc, the
used chemicals and created products in the lab create the following risks1.
The aqueous solution of H2SO4 is warned of causing serious eye damage, with eye and face
protection being precautionary. If in eyes, warned to rinse for several minutes, if any
contact corrective lenses are being worn at time of exposure, the contact lenses are to be
removed. The LD50 orally is around 2140 mg/kg and with no known skin corrosion due to
immediate contact.
The solid of magnesium ribbon poses the risk of a fire hazard, requiring special attention to
any intense heat, open sparks or smoking. There has been no determined LD50 or LC50 for
any skin or oral irritations.
The product of the reaction MgSO4 may be harmful when directly inhaled or in contact with
non-covered skin. The acute toxicity warns as this product targets the central nervous
system, requiring protective clothing and correct eye protective. While the oral LD50 and
LC50 is not available, protective caution should be used.
The created product of hydrogen gas is an extremely flammable gas that may form
explosives with available mixtures in the environment. While may cause eye irritation, the
inhalation is the key caution while the gas is odorless, in large amount is required to be
1
Flinn Scientific Inc, . Flinn Scientific. https://www.flinnsci.com/sds/ (June 6, 2018)
handled under the caution of a fume hood and disposed of correctly. The gas is extremely
flammable when in the presence of an oxidizing agents. Do not place this gas in any high
level of pressure as the compressed gas may explode.

Procedure
To begin the experiment, we must make sure to clean and dry fully the equipment used
including the reaction beaker (100 mL). The provided magnesium ribbon (provided by the
stockroom) needs to be cleaned to prevent any waste or contamination by steel wool. The
measurement of magnesium ribbon after being cut into one to two-centimeter pieces weigh
out to between 0.20 grams and 0.25 grams. All while the magnesium ribbon was being
prepared, the other partner is preparing the environment; a bucket of crushed ice was
collected to provide the environment of the calorimeter to create an isothermal
surrounding. The reaction beaker was filled with crushed ice and adequate amount of
deionized water to make sure there is no air bubbles interfering. As the stopper was closed
we examined if there were any slow leaks, besides the possible heat being delivered to the
tube, and made sure the volume stayed constant without reaction.
The prepared magnesium ribbon was then placed inside the reaction tube in order to bring
the metal to the surrounding’s temperature, which we measured with a mercury-based
thermometer which recorded around 2.1°C. The ribbon was left to acclimate for ten
minutes, then we placed the H2SO4 into the tube initiating the reaction. The volume being
measured was the deionized water filled to around .900 mL in the inverted volumetric
pipette. When the reaction started the timer app in an iPhone was used to measure the
volume of the pipette for every 30 seconds, until the reaction brought the pipette to volume
changes of only 0.1 mL ever 2 minutes.
Some brief details of precautions taken however error still present includes the ability to
contain and control the constant of the environment’s temperature including manual
handling of the apparatuses which transfers human hand heat to the instruments. Another
non-confirmed used of elements is the molarity of the H2SO4 at 1.0 M and the magnesium
ribbon used in the reaction.

Data One Reaction of H2SO4(aq)+Mg(s)MgSO4(aq)+H2(g) in respect of Volume vs. Time

Time (sec) Trial 1 (mL) Trial 2 (mL) Time (sec) Trial 1 (mL) Trial 2 (mL)
0 0.900 0.855 450 0.862 0.341
30 0.900 0.850 480 0.855 0.301
60 0.900 0.842 510 0.850 0.270
90 0.900 0.840 540 0.849 0.249
120 0.900 0.839 570 0.840 0.238
150 0.900 0.837 600 0.839 0.211
180 0.900 0.834 630 0.832 0.199
210 0.895 0.830 660 0.829 0.189
240 0.895 0.830 690 0.179
270 0.895 0.751 720 0.167
300 0.890 0.649 750 0.165
 330 0.880 0.552 780 0.165
360 0.878 0.475 810 0.159
390 0.875 0.423 840 0.155
420 0.870 0.375 870 0.155

Graph From Data Gathered for Trial Two, Collected Above

Calculations
The reaction releases energy to the environment so this will melt the ice of the calorimeter.
The ice used will take up more space than the water, so the volume per gram is higher2

2Thermochemistry:An Ice Calorimeter Determination of Reaction Enthalpy lab document,

Mesa Community College CHM152LL website. https://docs.google.com/document/d/1MH
CZe1vrRfrw633d9ITbEKyXmT_Vh6HSkSBE7K3h6Fc/edit. Accessed 06/10/2018
which is the reasoning behind the pipette’s volume changing. According to the provided lab
manual, the density of water and ice at 0°C is:
0.9164 𝑚𝑙 1.000 𝑔 1.0912 𝑚𝐿 𝑖𝑐𝑒
dice = so for this lab the specific volume is = =
1.000 𝑔 0.9164 𝑚𝑙 1.000 𝑔 𝐻2 𝑂
0.9999 𝑔 1.000 𝑚𝐿 1.0001 𝑚𝐿
dwater = 1.000 𝑚𝐿 so for this lab the specific volume is = =
0.9999 𝑔 1.000 𝑔

Using these two specific volumes, the difference between ice and water is calculated at
(1.0912 mL/g – 1.0001 mL/g) equaling 0.091mL/g.
Utilizing the data from Table 1 seen above, the change in volume (or ice melted) for
different trials are:
ΔVTrial n = ((slope before reaction – slope after reaction) x elapsed time) + (V1-V2)
(0.895 𝑚𝐿− .900 𝑚𝐿) (0.829𝑚𝐿−0.839𝑚𝐿)
ΔVTrial 1 = ( )−( ) × 660𝑠𝑒𝑐𝑜𝑛𝑑𝑠 + (0.900𝑚𝐿 − 0.829𝑚𝐿)
240 𝑠𝑒𝑐 60 𝑠𝑒𝑐

ΔVTrial 1 = 0.02975 mLice melted

(0.830 𝑚𝐿− 0.855 𝑚𝐿) (0.149𝑚𝐿−0.179𝑚𝐿)
ΔVTrial 2 = ( )−( ) × 990𝑠𝑒𝑐𝑜𝑛𝑑𝑠 + (0.855𝑚𝐿 − 0.149𝑚𝐿)
240 𝑠𝑒𝑐 300 𝑠𝑒𝑐

ΔVTrial 2 = 0.702 mLice melted

To find the amount in grams of melted ice, we convert using the specific volume of ice:
1.000 𝑔
Mass of Ice MeltedTrial One = 0.02975 mL melted × 0.0911 𝑚𝐿/𝑔 = 0.327 g
1.000 𝑔
Mass of Ice MeltedTrial Two = 0.702 mL melted × 0.0911 𝑚𝐿/𝑔 = 7.706 g

We know the enthalpy of fusion for the melting ice at 0°C which is 334 J/g and this is used
in order to calculate the energy of the of the reaction. Since we were able to complete two
trials there will be an averaged amount.
0.334 𝑘𝐽
Energy RequiredTrial One = 0.327 g × = 0.109 kJ/g
1.000 𝑔
0.334 𝑘𝐽
Energy RequiredTrial Two= 7.706 g × = 2.57 kJ/g
1.000 𝑔

From here, to determine the molar enthalpy of the reaction the limiting reagent must be
determined. When looking at the reaction’s equation, we find the stoichiometry ratio as 1:1
for Magnesium and H2SO4 from H2SO4(aq)+Mg(s)MgSO4(aq)+H2(g) . The limiting reagent is
calculated by:
1 𝑚𝑜𝑙 𝐻2 𝑆𝑂4
0.005 L H2SO4 × = 0.00500 moles H2SO4
1 𝐿 𝑜𝑓 𝐻2 𝑆𝑂4

1 𝑚𝑜𝑙 𝑀𝑔
Trial 1 = 0.2497 g Mg × 24.31 𝑔 𝑜𝑓 𝑀𝑔 = 0.10 moles of Mg
 1 𝑚𝑜𝑙 𝑀𝑔
Trial 2 = 0.2397 g Mg × 24.31 𝑔 𝑜𝑓 𝑀𝑔 = 0.0098 moles of Mg

According to these calculations the limiting reagent is found to be H2SO4. This is then
placed into the equation in order to find the
𝑒𝑛𝑒𝑟𝑔𝑦 𝑓𝑟𝑜𝑚 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑡𝑟𝑖𝑎𝑙 n
ΔH°reaction = 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑙𝑖𝑚𝑖𝑡𝑖𝑛𝑔 𝑟𝑒𝑎𝑔𝑒𝑛𝑡
0.109 𝑘𝐽
ΔH°Trial One = 0.005 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐻 = 21.8 kJ/mol
2 𝑆𝑂4

2.57 𝑘𝐽
ΔH°Trial Two = 0.005 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐻 = 514. kJ/mol
2 𝑆𝑂4

With these two trials the average experimental molar enthalpy would be calculated at
(514.0+21.8)kJ/mol
= -267.9 kJ/mol, with the answer being negative because we determined
2 𝑡𝑟𝑖𝑎𝑙𝑠
that the reaction released heat to it’s environment. To calculate the percent error, we use
the formula:
|𝑚𝑒𝑎𝑠𝑢𝑟𝑒𝑑 𝑣𝑎𝑙𝑢𝑒−𝑎𝑐𝑡𝑢𝑎𝑙 𝑣𝑎𝑙𝑢𝑒|
Error (%) = × 100%
𝑎𝑐𝑡𝑢𝑎𝑙 𝑣𝑎𝑙𝑢𝑒
|267.9−470.9|
Experimental Error (%) = × 100% = 43.1 %
470.9

While our averaged experimental molar enthalpy is extremely inaccurate, largely due to
the first trial in which we will expand upon further as we speak in the discussion about our
errors, if trial 2 is the used trial our percent error would shrink to around nine percent.
This shows our execution was accurate as long as the proper precautions were followed
tediously.

Discussion
The lab’s purpose was to find the molar enthalpy of the reaction
H2SO4(aq)+Mg(s)MgSO4(aq)+H2(g) through utilization of an ice calorimeter. The reaction
went through three successive phases in which the rate of the change in volume varied.
This is found in the graph distinctively through slopes that can be broken down into before
reaction, during reaction and after reaction. These slopes provide determination of the
change in volume giving feedback for how much energy is being absorbed by the
environment when the H2SO4 was added to magnesium. While the determined
experimentally value of molar enthalpy was off as compared to the theoretical, the
reasoning behind why was thoughtfully determined from human error (trial one and two
compared to theoretically respectively: -21.8 kJ/mol, -514.0 kJ/mol and -470.9 kJ/mol).
While the reaction provided the results we assumed from an exothermic reaction, such as
energy being released into the environment noticed by the volume decreasing as time
passed, the reasons as why the molar enthalpy didn’t match the experimental include
multiple issues from lack of chemists’ effectiveness and careful practices. The first error in
the experimental process was that when the pipette was initially filled with deionized
water for the initial volume reading, the stopcock was in the open position. This caused the
volume and pressure to not stay constant when exposed to the chemical reaction. This
allowed for any energy to not be calculated carefully as the heat may have been escaping
through other venues in the instrument. When the first minute examination was concluded,
the test for leaks did not show any abnormally excessive decrease in volume however
when further tested with an actual reaction the stopcock needed to be placed in the closed
position.
One of the other reasons in which allowed for error was the early cutoff of the reaction.
While the time for trial two did surpass 900 seconds to ensure slowing reaction, the
volume readings could have changed after the experiment ending. To be fully sure the
reaction needed to be allowed to continue until the advised 1250 seconds. This would have
allowed for conclusive evidence that the reaction was finished.
Final available decided error that may have caused error was the lack of attentive
awareness to the environment’s starting temperature for trial two in comparison to trial
one. If the temperature was too warm for trial two as the bucket was not refilled with
crushed ice and steps reattempted, then the volume may have decrease quicker due to
starting temperature starting at a higher Celsius reading. Though not in calculations as the
reaction ensured isothermal reaction, the starting temperature of the environment should
have been as close as possible to 0°C.