EXPERIMENT #6: THERMOCHEMISTRY

INTRODUCTION
Overview
Thermodynamics is the study of the energy changes that accompany chemical and
physical transformations. In this laboratory, we will explore the first law of
thermodynamics. A general statement of the first law that the energy of the universe is
constant. How do chemists use the First Law? They use it to relate observed external
changes in energy to equal-but-opposite internal changes. In particular, atoms and
molecules – the ‘stuff’ of chemistry – release heat, light, sound and motion in the course
of chemical reactions. These ‘external’ forms of energy can all be measured, and we then
assert, in the spirit of the First Law, that the ‘internal energy’ of the atoms and molecules
(the ‘system’ in thermodynamic language) must have changed by an equal and opposite
amount. The concept of ‘internal energy’ or ‘chemical energy’
The idea that energy is conserved carries with it the thought that if we have a set of atoms
and molecules in a known physical state, they will always have the same amount of
internal energy no matter how they arrived in this state. Consider, for example, a glass of
water sitting on a table. The water in that glass has a certain total internal energy that
does not depend on how the molecules were produced. Some, perhaps, came from an
ancient star in which H and O atoms reacted with each other, while others were created in
the cells of living plants and animals as a by-product of very complicated reactions.
According to the First Law, however, their history doesn’t matter: the total internal
energy depends only on the current state (Pressure, Temperature, electric & magnetic
fields, etc.) of the system.
Calorimetry
A calorimeter is a device that is used to measure the heat evolved or absorbed ( q p )
accompanying a chemical reaction or physical transformation (the calorie is an old unit
of heat, equal to 4.184 J). In this experiment, the calorimeter consists of a stoppered
thermos bottle partially filled with water and a temperature probe. The purpose of the
thermos is to keep heat from being lost to the room, while the purpose of the water is to
absorb the heat produced by the chemical or physical change under investigation. (Water
is good for this since it has a high heat capacity, explained below.) In addition to the
water, of course, some of the heat is absorbed by the calorimeter (thermos bottle and the
temperature probe), and some (a negligible amount in this case) is ‘lost’ through the walls
of the thermos bottle to the room. Using the First Law, we can write:
∆H system = q p = - q surrondings

where ∆H system is the enthalpy change of the system (the heat transferred at constant
pressure), q p is heat evolved or absorbed in the system, and q surroundings is the heat
absorbed by the calorimeter (the water + thermos bottle + temperature probe), which is
what we measure.
But how, exactly, do we measure the heat absorbed by the calorimeter? When you think
about measuring heat, you probably think of using a thermometer. But thermometers
measure temperature, which is related to the intensity of the random motion associated
with heat, not the amount of heat itself. (The analogy is the speedometer of your car,
which tells you how fast you are going, but not how much kinetic energy you have.)
What we need is the ‘connection’ between changes in temperature and the corresponding
changes in ‘internal’ (thermal) energy. It seems reasonable that these two things should
be proportional to each other*, so let us write q = C∆T , where ‘C’ is called the heat
capacity of the object whose temperature change we measure. Note that the constant ‘C’
connects ‘heat’ and ‘temperature’, which makes it conceptually as well as numerically
important!
The phrase ‘heat capacity’ suggests the ability of an object to ‘hold heat’, and that is
exactly what it is. Every substance has its own particular set of internal motions (since
every substance has a different set of atoms, joined in different ways); thus every
substance has a different ‘heat capacity’. Indeed, different amounts of the same
substance have different heat capacities, so when discussing the heat capacity of a pure
substance it makes sense to specify the ‘heat capacity per gram’ or ‘per mole’.
(Physicists and engineers usually think in terms of mass, while chemists think in terms of
moles!) The heat capacity per gram is different for every different substance, but the heat
capacity per mole of similar materials (all noble gases and most metals) turns out to be
very similar. This is one piece of evidence supporting the idea that ‘heat’ is just energy
associated with the internal motion of the atoms in the substance. You will check this
idea in Part III of the experiment.
The units of heat capacity are ‘energy per degree’, i.e. J/˚C, or J/˚K (Celsius and Kelvin
have the same size degrees so it doesn’t matter which one you choose). The heat
capacity tells us how much the temperature changes for a given amount of heat – for
example, if an object has a heat capacity of 20 J/˚K, then adding 20 Joules will raise the
temperature 1˚K. The heat capacity per gram is called ‘s’ (the ‘specific heat’), thus
C = m ⋅ s , where ‘m’ is the mass in grams. The heat capacity per mole is called c (read
‘c-bar’), hence C = n ⋅ c , where ‘n’ is the number of moles of the substance. Values for s
and c can be found in reference books, for example the CRC Handbook of Chemistry
and Physics. ‘s’ can be converted to ‘ c ’ by multiplying by the molar mass; for example,
‘s’ for water is 4.184 J/g-˚C (something you should remember!), thus ‘ c ’ is
18.015g/mol ∗ 4.184J/g.˚C = 75.38 J/mol.˚C.
Purpose
This part of the experiment has three main parts:

*
Note: it is possible to have heat absorbed without a temperature change if the object
undergoes a 'phase transformation', for example, ice absorbs heat when it melts, but
∆T = 0 . This is a 'special case' which involves only changes in potential energy
(separating molecules from each other), rather than kinetic as well as potential energy.
'Temperature' only measures the kinetic energy component of heat.
 Determine the heat capacity of the calorimeter.
Measure the heat of fusion of ice.
Measure the heat of neutralization of HCl & NaOH.
Heat Capacity of the Calorimeter
The heat capacity of the calorimeter ( C cal ) is equal to the heat capacity of 200 ml of
water and the heat capacity of the thermos bottle:
C cal = C thermos + probe + C water

C cal is determined by measuring the temperature change that occurs when a known
amount of hot water is added to the calorimeter. The heat lost by the hot water is equal to
the heat gained by the calorimeter. (We assume no heat is lost to the laboratory.) For
example, if Tc equals the temperature of the calorimeter (200 ml of cool water in a
thermos bottle with at temperature probe), if Th equals the temperature of 200 ml of hot
water added to it, and if Tf equals the temperature after mixing, then the heat lost by hot
water is equal to the heat gained by the calorimeter (the specific heat of water is 4.184
joules/g-˚C, and the density of water is 1.00 ):
q lost = q cal = (Th - Tf ) × 200g × 4.184 joules/g ⋅ °C
The heat capacity of the calorimeter is therefore the heat gained by the calorimeter
divided by the temperature change of the calorimeter:
C cal = q cal /(Tf - Tc )
Once we have determined the value of C cal , we can use the calorimeter to measure
unknown q’s produced from a variety of physical and chemical changes that are
commonly encountered in the lab.
Heat of Fusion of Ice
In this case the water in the calorimeter cools off as the ice melts, and the ‘First Law’
equations are a bit more complicated. The heat of fusion is the energy required to
convert H2O(s) into H2O( A ), i.e. it is the energy of the phase transition. Once the ice has
melted, however, the cold water (at 0˚C) mixes with the warm water in the calorimeter,
causing further cooling. In order to find the heat of fusion ( ∆H fusion ) we need to separate
these two effects:
heat lost by calorimeter = - C cal ∆Tcal = heat to melt ice + heat to warm water from ice
heat gained (ice, water) = (m ice )(s fusion ) + (m ice )(4.184 J/g ⋅ °C)( ∆Twater from ice )
∆Tcal = Tfinal - Tinitial ∆Twater from ice = Tfinal - Tice cube

The two ‘unknowns’ in these equations are: s fusion and m ice . The latter can be obtained
by weighing the contents of the calorimeter after the ice has melted. The heat of fusion
obtained by solving these equations is ‘per gram’, which can be converted to the molar
heat of fusion in the usual way. For an interesting piece of ‘trivia’ be sure to compare the
change in temperature with the mass of the ice!
Heat of Neutralization of HCl & NaOH
The net ionic equation for the neutralization reaction is:
H+(aq) + OH-(aq) Æ H2O( A )
This is an exothermic reaction so heat is released upon mixing and the temperature of the
solutions increase. Use q=C∆T to calculate the heat absorbed or released. One question
is what value should you use for C? The previous measurements have all had pure water
in the calorimeter. Here, however, you end up with a 0.25 M NaCl solution, rather than
pure water. Given the modest concentration of NaCl, we can assume that C is the same
for a NaCl solution as it is for water.
 PROCEDURE
Check out a LabPro Calculator with a temperature probe from the stockroom.
Read the appendix to learn how to operate the LabPro calculator and configure it to
show a constant temperature reading on the screen.
A thermos bottle with a #12 stopper will be supplied in the laboratory to serve as the
calorimeter. The stopper will have a mercury thermometer inserted into a center
hole to offer a check on the metal temperature probe that comes with the calculator.
There is a side groove in the stopper into which the metal temperature probe is to be
inserted to take temperature readings.
A. Temperature Measurements
1. This section gives general directions on how to make temperature measurements
that will be needed in Parts B., C., & D.
2. Refer to the Appendix for instructions on how to use the LabPro system and
prepare the temperature probe for data collection. Once setup is complete,
temperature readings will be continually displayed on the calculator (in the main
screen). Alternately, a thermometer can be used to make temperature
measurements.
3. Tinitial is equal to the average of the temperature measurements prior to mixing the
solutions. After mixing, the temperature of the solution will rise to a maximum
value and then will start to cool towards room temperature. Tfinal is equal to the
maximum value. If the temperature of the solution drops after mixing, Tfinal is
equal to the minimum value.

B. Finding the Heat Capacity of the Calorimeter

1. Put exactly 200 ml of room temperature deionized water into the thermos bottle
and put the #12 stopper with thermometer into the mouth of the thermos. Insert
the metal temperature probe through the side grove as far as it will go to monitor
the temperature of the liquid. Allow this system (now called the calorimeter) to
stand until the temperature remains constant. Record this temperature (Tc =
Tinitial ) to the nearest 0.2˚C.
2. Put exactly 50 ml of deionized water into a 250 ml beaker and cover with a cover
glass. Heat the water to ~ 90˚C using a hotplate. Use the mercury thermometer in
the bench drawer to monitor the progress of heating.
3. Measure and record the temperature ( Th ), of this hot water with the LabPro
temperature probe and immediately transfer all of the hot water into the
calorimeter containing the room temperature water. Stir the solution with either
the thermometer in the #12 stopper being careful not to break the thermometer
bulb, or stir it with the metal temperature probe to ensure good mixing. After 60
 seconds, take a temperature reading to 0.2 degree. Record this value as Tf ( Tf =
Tfinal ).
4. Calculate Ccal:
The heat lost ( q lost ) by the hot water is gained by the calorimeter (qcal):
q lost = q cal = (Th - Tf ) × 50g × 4.18 joules/g - °C
The heat capacity of the calorimeter is therefore the heat gained by the
calorimeter divided by the temperature change of the calorimeter:
C cal = q cal /(Tf - Tc )
5. Repeat the above procedure twice and determine an average Ccal.
C. Heat of Fusion of Water
1. Fill the calorimeter with 200 ml of room temperature water and record the initial
temperature, Tinitial (water).
2. Obtain ice cubes from the TA. The TA will say how many cubes are necessary.
(Note: Crushed ice is not suitable because it contains appreciable surface water;
therefore, do not used crushed ice for this part of the experiment).
3. Dry the ice cube off with a piece of paper towel and immediately add the dried ice
cube to the calorimeter. {It is important to minimize the amount of thawed ice
(water) added so that only the heat of fusion is measured and not also the cooling
due to cold water on the surface of the ice.} Stir until all the ice melts, indicated
by the temperature reaching a constant value, Tfinal (water+ice). If the temperature
is decreasing, the ice is still melting, and you need to continue stiring the contents
of the calorimeter.
4. Tare an empty Styrofoam cup. Pour the contents of the calorimeter into the cup
and reweigh it. Weigh the calorimeter, mass (water + ice), to determine the mass
of the ice cube(s). Repeat this procedure twice more. Prepare a table similar to
that below in your notebook.
5. Measure the temperature of an ice bath (crushed ice in water) and record this
value as the initial temperature of the ice cube, Tinitial (ice cube).

o
Ccal (J/ C)
Mass of calorimeter contents
(100mL water), g
Mass of calorimeter contents+
mass of added ice
Temperature of water before ice
o
addition, C
Temperature of ice before
o
addition to the calorimeter, C (=
T crushed ice in water)
Temperature of the calorimeter
o
after addition of ice, C
D. Heat of Neutralization of HCl and NaOH
1. Using the 400 ml and 600 ml beakers, obtain approx. 350 ml of 0.5 M HCl and 0.5 M
NaOH.
2. Measuring with the graduated cylinder put 100.0 ml of 0.50 M NaOH into the
calorimeter. Record the temperature of this solution as Tinitial (NaOH).
3. Rinse the cylinder with deionized water and measure 100.0 ml of 0.50 M HCl into a
250 ml beaker. Record the temperature of this solution as Tinitial (HCl). Ideally, the
acid and base will be at the same temperature but if not, you should use the average
temperature of the two as the value of Tinitial .
4. Mix the HCl and NaOH and stir the solution with the temperature probe. Determine
Tfinal .
5. Check the pH of the solution with pH paper. If the pH is greater than 12 add some
HCl to bring it down. If it is less than 6 add some sodium bicarbonate to raise it.
Once the pH is between 6 and 12 it may be poured down the drain.
6. Repeat this procedure twice more. Prepare a table similar to that below in your
notebook..
Run 1 Run 2 Run 3
C cal (J/˚C)
Tinitial (HCl), ˚C
Tinitial (NaOH), ˚C
Tinitial (average), ˚C
Tfinal , ˚C
∆T, ˚C
Report:

Use the proper number of significant figures based on the least precise measuring
instrument used in this experiment. After each reported result, include the tables used to
collect data along with the calculations used for each determination.

Report the average heat capacity value determined for the calorimeter along with the
standard deviation of the three trials.

Report the average heat of fusion value determined for the water along with the standard
deviation of the three trials.

Report the average heat of neutralization value determined for mixing HCl with NaOH
along with the standard deviation of the three trials.
 APPENDIX
OPERATION OF THE LABPRO SYSTEM
General Instructions
The LabPro System consists of a LabPro unit, a TI-83 graphing calculator, and up to 4
analog & 2 digital probes. Each probe will collect a particular kind of data such as
temperature, pressure, absorbance, pH, etc. The following instructions will guide you
through the process of setting up the LabPro system for the probes that you will be using.
1. Make sure the TI-83 Graphing Calculator is attached to the cradle on top of the
LabPro unit and that the link cables connecting the two are firmly inserted in the
cable ports.
2. Plug the AC adapter into an outlet and attach it into the LabPro unit. The unit will
turn on automatically and run a self test (accompanied by beeping noises).
3. Turn on the TI-83 calculator (refer to Appendix C for some general instructions for
operating the TI-83 calculator).
4. Start the DATAMATE program on the TI-83 calculator. Press PRGM , then select the
DATAMATE program from the menu. [Note: To select an item from TI-83 menus, use
to highlight the menu item and press ENTER or simply press the number of the
menu item on your calculator (in this case, you would press 1 )]. Press ENTER to
run the program.
5. After the program begins, an introductory screen will appear and the calculator will
try to communicate with the LabPro unit and check for auto-ID sensors. If this
communication is successful, the main screen will appear; otherwise, there will be an
error message and you will have to make sure the connections are tight before
continuing.
6. Prepare the probes that you will be using for data collection by plugging them into
one of the numbered channels on the LabPro unit. Note: You should always plug the
probes in AFTER turning on the program.
7. Newer sensors that are attached to the LabPro unit (such as the gas pressure sensor,
temperature probe, and colorimeter) will be automatically identified and the main
screen will display the channels they are connected to and the current readings.
8. Older sensors (such as the pH probe) will have to be manually specified in the
program, using the following instructions.
Temperature Probe
The temperature probe is composed of a thermistor whose resistance changes in response
to temperature. The built-in calibration is automatically selected so no calibration steps
are required. If you get a reading of "-999.9", remove the probe from the LabPro, wait 10
seconds, and then reinsert the probe while the program is running.
Gas Pressure Sensor
The gas pressure sensor is composed of a pressure-sensitive membrane. As the pressure
changes, there is a change in the voltage across the membrane. While a manual
calibration can be done using the pressure sensor, in practice it is difficult to do and the
built-in calibration provides adequate results so no calibration steps are required. If you
get a reading of "-999.9", remove the probe from the LabPro, wait 10 seconds, and then
reinsert the probe while the program is running.
pH Probe
The pH Probe consists of a pH amplifier and a pH electrode. The pH amplifier should be
plugged into one of the channels of the LabPro. Also, verify that the pH electrode is
plugged into the amplifier. The pH probe is not auto-detected and will therefore need to
be calibrated manually.
To perform a manual calibration:
1. After you have selected the pH probe on the calculator (see the General Instructions
above), select 2:CALIBRATE. A calibration menu will appear
2. Select 2:CALIBRATE NOW.
3. Rinse the tip of the electrode with distilled water and blot the excess water. The
electrode is extremely delicate so use Kimwipes and be careful.
4. Immerse the electrode in standard pH = 4.0 buffer solution so that the liquid level is
above the white line on the electrode. Stir briefly and gently with the electrode to
remove bubbles from the electrode surface.
5. When the voltage reading stabilizes, press ENTER on the calculator and enter “4”
when prompted for a value.
6. Repeat steps 3 through 5 with the standard pH = 10.0 buffer solution. You should
enter “10” instead of “4” when prompted.
7. Select 1:OK to return to the setup menu and select 1:OK again to return to the main
screen.