Lab 8: Styrofoam Cup Calorimetry

Calorimetry is an experimental technique to measure the heat released or taken

up during a chemical reaction. It can also be used to determine the atomic mass
of elements according to the Law of Dulong and Petit which states

Specific Heat x Atomic Weight = constant (1)

The specific heat is defined as the amount of energy required to increase the
temperature of one gram of a substance by one degree Kelvin (K). The constant
in formula (1) above has been determined as 6.26 cal/Mol x K or 26.21 J/Mol x K
in SI units.

A calorimeter is a well-insulated vessel equipped with a thermometer and filled

with a known volume of a medium of known specific heat capacity, typically water
whose specific heat capacity is 1.0 cal/g x K. When a hot object is added to this
vessel or when a reaction is conducted in the vessel, the increase/decrease of
the temperature of the water is measured until equilibrium is reached. With the
specific heat capacity of water and the volume of water in the calorimeter known,
the observed change in temperature can be related to the amount of heat
released/taken up after the object was added to the vessel or during the reaction,
as the case may be.

In today's experiment we will be using a relatively crude calorimeter constructed

from two nested styrofoam coffee cups. The outer cup and the air pocket
between the cups serve as the insulation. The inner cup is equipped with a lid to
reduce the amount of heat loss through evaporation (the energy required to
evaporate the water is drawn from the bulk liquid in the cup leading to its
cooling). We will be inserting a thermometer through the hole in the lid to
measure the temperature of the water. Lastly we need to ensure that the
temperature distribution of the water in the cup is homogeneous so that the
temperature that the thermometer reads is indicative of the entire content of the
calorimeter and not just of the water column in the immediate vicinity of the
thermometer bulb. This is important because in this experiment we will determine
the specific heat capacity of metallic objects. These sink to the bottom of the
calorimeter and if the thermometer bulb is situated close to the metal, in the
absence of stirring, the thermometer will read a different temperature than it
would if it were located at the water surface in the cup. We will be using a "loop
stirrer" to agitate the solution by moving a wire loop up and down in the water
column.

As you well know, coffee in a styrofoam cup will slowly but surely cool to room
temperature, particularly if you leave the lid off, while the thermal energy stored
in the hot coffee will be lost to the environment. This loss of energy will also
occur during the experiment you will be conducting. We therefore need to correct
our measurements for this heat loss due to the apparatus we are using. We
therefore will determine the "calorimeter constant", the amount of heat taken up
by the materials of calorimeter and the amount of heat lost to the environment.
All subsequent measurements will then have to be corrected for this amount of
heat.

Part I: Determination of the calorimeter constant

Place about 200 mL of deionized water in a 300 mL beaker and heat to about 50
oC on a hot plate. Place another 400 mL of deionized water in a 600 mL beaker

and let equilibrate to room temperature while you assemble your apparatus.

From the common desk by the entrance to the lab collect a loop stirrer (Fig. 1),
an electronic thermometer, two styrofoam cups and a cardboard lid.

(Photo to be inserted)

Fig. 1 Wire loop stirrer (top).

Place two nested styrofoam cups into a metal ring affixed to a ring stand. Place
the small rubber stopper into the clamp and push the end of the thermocouple
wire through the hole in the rubber stopper. Suspend the thermometer from a
clamp above the cups. Place the cardboard lid on the cups and lower the
thermometer into the cup, the loop of the stirrer should be placed around the
thermometer as shown in Fig. 2A and Fig. 2B (side view, lid removed for better
visibility) (top view, lid removed for better visibility).

Please do not poke additional holes in the lid, the holes there are large enough
for both the thermocouple and the loop stirrer to fit.
Fig. 2. A: Side view (lid removed); B: Top view (lid removed);

Your complete assembly should look as shown in Fig. 3:

Fig. 3. Fully assembled styrofoam cup calorimeter.

Using a 100 mL graduated cylinder measure out 50.0 mL of the room

temperature water and pour carefully into the styrofoam cup calorimeter without
spilling. Adjust the clamp holding the thermometer so that the thermocouple at
the bottom is immersed in the water. Stir with the loop stirrer and measure the
temperature to 0.1 oC. Record this temperature on Line (1) in the data sheet.
When the water in the beaker of the hot plate has reached about 50 oC, pour
50.0 mL into the 100 mL measuring cylinder and stir. Using the thermocouple
measure the temperature of the water in the cylinder to 0.1 oC and enter it on line
(2) of your data sheet. Right away, quickly but carefully pour the water into the
calorimeter. Do not spill! Immediately close the lid and start stirring with the loop
stirrer. Read the temperature at 15 sec intervals entering values into the table
"Time Course A" in the data sheet, until the temperature starts to decline. Record
the maximum temperature reached on line (3) of your data sheet

Repeat this sequence. Empty the calorimeter into the sink and add 50.0 mL cool
water. Measure out 50.0 mL warm water, using the thermocouple measure its
temperature in the cylinder, not the beaker. Enter the temperature of the water in
the graduated cylinder on line (7) of the data sheet. Carefully pour the warm
water into the calorimeter and record the temperatures you read in 15 second
intervals into the table "Time Course A" until the temperature starts to decrease.
Enter the maximum temperature of the water in the calorimeter on line (8).

Part II: The Specific Heat of Metals

Fill the beaker on the hotplate to 300 mL with water and bring to a boil.

Weigh out samples of between 50 and 100 g of two of the metals on the common
table and carefully place each sample into an empty test tube (for less dense
metals tow test tubes may be required). Affix the test tube to a clamp on a
laboratory stand and insert the test tube into a beaker of boiling water. Continue
heating for a minimum of 10 min. The metal is supposed to reach the
temperature of the boiling water, so boiling longer is better. Do not fill the test
tube with water!

While the metal is heating up empty out the calorimeter, dry with a paper towel
and add 100 mL of the room temperature deionized water. As before immerse
the thermometer in the water. Measure the temperature to 0.1 oC and record the
values on Line ().

Take a moment now to discuss with your partner what has to happen next
and who will be doing what, because the next few steps have to happen
quickly:

Raise the test tube from the boiling water bath, quickly wipe the outside of the
test tube with a paper towel, remove the test tube from the clamp and gently
dump the metal into the calorimeter. Do not spill or splash!
Immediately place the lid onto the cup and start stirring with the loop stirrer. Read
the temperature in 15 sec intervals until the temperature starts to decline. Enter
your temperature reading in the table "Time Course B" on the Data Sheet.
Dump out the water into the sink. Place the metal on paper towels and return it to
the appropriate container when dry.

Repeat the procedure with the second metal you have chosen.

Calculations

One of the confusing aspects of these calculations that follow is the sign
convention. We say that a system gains thermal energy (q is positive) when T is
positive. A system loses energy (q is negative) when the temperature decreases,
i.e. T is negative.

It has been shown that q is proportional to T:

q T

The proportionality constant that links q and T is the heat capacity C measured
in Joule/Kelvin (J/K) in the SI system, although cal/oC can also be found. It
follows

q = CT (2)

We will be using water as our heat sink since it can absorb a large amount of
thermal energy with only a small increase in temperature (this is one reason why
it is used as coolant in combustion engines, e.g. car engines, for example). The
heat capacity C can be determined from the known specific heat capacity Cs of
water that one can look up in tables of physical data and the mass of water in the
system:

q = mCsT (3)

When we mix a certain volume of warm water with a known volume of cool water
in a calorimeter, the cool water and the calorimeter (!) take up the heat lost from
the warm water:

-qwarm water = qcold water + qcalorimeter (4)

We now substitute in the specific heat capacity of water, the masses of cold and
warm water used, respectively, and the observed temperature changes:

-(mCsT)warm water = (mCsT)cold water + CTcalorimeter (5)

How do we get Ccalorimeter?

[() + () ]
Ccalorimeter = -Cs (6)

Now we use a little trick: the change in temperature of the cool water, Tcool water,
is equal to the change in temperature of calorimeter:

Tcalorimeter = Tcold water

[ +() ]
Ccalorimeter = (7)

If mass mcool water = mass mwarm water (as in our case, 50.0 mL each), you can use:

[ + ]
Ccalorimeter =

= ( + 1) (8)

This is the formula for the computation of the calorimeter constant in Part A of
today's experiment.

With the calorimeter constant determined, you can now compute the heat
capacity of the metals. It is important that the total mass of water in the
calorimeter is the same as the total volume you used during the determination of
the calorimeter constant. The calorimeter constant is valid only for one specific
volume!

= +

The specific heat capacities of metals can then be calculated on the basis of the
following considerations:

= ( + )

( ) = -[(m T) + () ] (9)

From this the specific heat capacity of the metal can be computed using the
following set of equations:

[( ] +() ]
= ()
(10)
Here we do a little trick again as we did for equation (7) above: the change in
temperature of the water is the same as that of the calorimeter:

[( ) + ]
= (11)
()

You have determined Ccalorimeter in Part A of today's lab according to formula (8),
the mass and specific heat capacity of water are known as is the mass of the
metal you used. The Tcalorimeter you measured when you followed the
temperature over time after adding the metal to the calorimeter. How do we
obtain a value for Tmetal? You know with which temperature of the metal you
started, e.g. 100 oC, the temperature of boiling water at sea level. You end up
with the peak temperature of the water in the calorimeter after addition of the
metal, which you measured. The difference is Tmetal. So you have all the data
you need.

Part C: A check-up on the Law of Dulong and Petit

These two Frenchmen recognized that metals in the lattice can oscillate in three
dimensions:

3
Atomic massmetal =

where R = gas constant (8.314 J Mol-1K-1 or 1.987 calMol-1K-1) and Cs metal is

the specific heat capacity you have just determined for two metals.

Using your experimentally determined value for Cs metal, compute the atomic mass
of metals I and II which you used in your experiment. Compare your results to the
data in the table below.

Table 1 Tabulated specific heats of metals used in the lab

Metal Specific Heat Specific Heat Atomic weight
(calg K )
-1 -1 (Jkg K )
-1 -1

Cr (Chromium) 0.107 448 51.996

Mn (manganese) 0.114 479 54.940
Fe (Iron) 0.108 449 55.845
Zn (Zinc) 0.0922 388 65.409
Cd (Cadmium) 0.0552 230 112.41
Sn (Tin) 0.052 217 118.71
Data Sheet

Part A

Time Course A. Temperature development in the calorimeter for Part A

Experiment 1 Experiment 2
Time (sec) T (oC) Time (sec) T (oC)
0 0
30 30
60 60
90 90
120 120

Part B

Time course B. Temperature development in the calorimeter for Part B

Metal I Metal II

Time after addn. Tcalorimeter (oC) Time after addn. of Tcalorimeter (oC)
of metal (sec) metal (sec)
0 0
30 30
60 60
90 90
120 120
Data Table Part A
Parameter Value Units Line #
Temperature of cool water in calorimeter K (1)

Temperature of warm water in cylinder K (2)

Max. Temp. reached in calorimeter (from K (3)

Experiment 1

Time Course A, Experiment 1)

Tcalorimeter (Line (3) - Tcool water (Line (1)) K (4)

Twarm water (Line (2) - Line (3)) K (5)

Specific Heat Capacity of water, Cs 4.186 JgK-1 (6)

Ccalorimeter (according to eqn. 8) JK-1 (7)

Temp. of cool water in calorimeter K (8)

Temp of warm water in measuring cylinder K (9)

Max. temp reached in calorimeter (from Time K (10)

Experiment 2

Course A, Experiment 2)
Tcalorimeter (Line (3) - Tcool water (Line (1)) K (11)

Twarm water (Line (2) - Line (3)) K (12)

Specific Heat Capacity of water, Cs 4.186 JgK-1 (13)

Ccalorimeter (according to eqn. 8) JK-1 (14)

Average value for Ccalorimeter ((Line (7)+ Line (14))/2: ______________JK-1 (15)
Part B
Name of metal I: ____________ Name of metal II: __________

Data Table for Part B

Parameter Value Unit Line #
Mass of metal I g (16)

Initial Temp. of metal I K (17)

Initial Temp. of water in calorimeter K (18)

Metal I

Highest Temp. after addition of metal I K (19)

to calorimeter (from Time Course B)
Tcalorimeter (Line (19) - Line (18)) K (20)

Tmetal (Line (17) - Line (19)) K (21)

mmetalTmetal (Line (16) Line (21)) gK (22)

masswater Cs water JK-1 (23)

Line (23) + Line (15) JK-1 (24)

Line (24) Line (20) J (25)

Cs metal I (Line (25) / Line (22)) Jg-1K-1 (26)

Mass of metal II g (27)

Initial Temp. of metal II K (28)

Initial temp of water in calorimeter K (29)

Metal II

Highest Temp. after addition of metal II K (30)

to calorimeter (from Time course B)
Tcalorimeter (Line (30) - Line (29)) K (31)

Tmetal (Line (28) - Line (30)) K (32)

mmetalTmetal (Line (27) Line (28)) gK (33)

masswater Cs water JK-1 (34)

Line (34) + Line (15) JK-1 (35)

Line (35) Line (31) J (36)

Cs metal II (Line (36) / Line (33)) Jg-1K-1 (37)

Post Lab Questions:

Submit brief answers typed. Attach spreadsheet printout for question 5.

1. Why is it important that you measure the temperature of the warm water
you are using in the determination of the calorimeter constant in the
measuring cylinder rather than in the beaker on top of the hot plate?

Hint: Why do you rinse the tea pot with hot water before you add the tea
leaves and pour in the hot water to make tea? (I apologize that this
question may be difficult to answer if you do not prepare your
caffeinated beverages yourself and just go to Starbucks)

2. a) By how much would the value for the heat capacity of metal II change if
you had spilled 5 mL of water during the addition of the metal to the
calorimeter?

b) Let's assume you noticed that you spilled some water during the
addition of the metal to the calorimeter. What simple thing could you do at
the end of the experiment to account for the loss of water and thereby get
as much of a correct value as possible?

3. If you combined equal volumes of water of temperatures 20 oC and 80 oC,

what temperature would you expect the resulting water to have, assuming
no loss of heat to the vessel in which you mix the two batches?

4. The instructions for Part B state that you are supposed to heat the metals
in air ("dry") and to not have water inside the test tubes. Looking at the
specific heats of water vs. that of the metals, i.e. Line (13) vs. data in
Table 1. (Note: Look carefully at the dimensions of these values. Don't
confound data given in J with those in cal), why do you think this is
important for the quality of data you obtain?

5. Using spreadsheet software (Excel, Google Sheets or iWork Numbers are

the only acceptable packages) enter the data in Table 1 and compute
1/Cs in the spreadsheet. (See the "Instructions on How to Work with
Spreadsheet Software" on Laulima (Email archive) in case you have
forgotten. Plot 1/Cs (with Cs in calgK-1) on the x-axis and the atomic
mass on the y-axis. Determine the slope of the resulting line in the
spreadsheet. Which value previously mentioned in this instruction does
this value represent?

6. Using the specific heats for metal I and II you determined experimentally,
compute the atomic weight of these metals using the formula in Part C.
What are the values? How do they agree? How large is the error? Any
suggestions for explaining the error?