Experiment 6: Calorimetry

In this experiment you will calibrate and use a constant pressure (coffee cup) calorimeter to measure
heat transfer for 3 different processes. After calibrating the calorimeter to determine its heat capacity,
you will then use the calorimeter to measure the specific heat of a metal, the heat of fusion of ice, and
the heat of neutralization reaction.

According to the First Law of Thermodynamics, the total Energy change for a process is the sum of the
heat and the work

ΔE = q + w (1)

When no gasses are involved w = 0 (or is very close to 0 because ΔV = 0 or ≈ 0) and

ΔE = q (2)

Heat can be easily measured by knowing the change in temperature (ΔT).

q = mCsΔT (3)

where Cs is the specific heat of the object and m is its mass. Specific heat has units if J/g °C. It
measures how much energy (heat) is required to change (raise) the temperature of the object by 1°C.
An object with a high specific heat, then, is “difficult” to heat. (It takes more energy to get it to warm
up.)

Since energy (heat) cannot be created or destroyed (also embedded in the First Law), the heat lost by a
one object must be equal to the heat gained by another object. Recall that we use sign conventions to
show direction of heat flow where a negative sign (–) shows heat lost and a positive sign (+) shows he
gained.

– qlost = qgained (4)

We will perform our experiments in a coffee cup calorimeter which consists of two nested Styrofoam
coffee cups containing a measured amount of water. A coffee cup is a good insulator so, most of the
heat should go only into the water, and not much into the coffee cup. But to be sure, we will calibrate
the calorimeter so we know exactly how much heat it absorbs.

In Part 1, calibrate the calorimeter you will combine equal masses of hot and cold water together in
your calorimeter. The amount of heat lost by the hot water (– (mCsΔT)hot ) is equal to the heat gained
by the cold water and the calorimeter [(mCsΔT)cold +(CΔT)calorimeter] . (The specific heat of water, Cs,
is 4.184 J/g °C). Assume the density of water to be 1.00 g/mL.

– (mCsΔT)hot = [(mCsΔT)cold +(CΔT)calorimeter] (5)

You will solve for Ccalorimeter and use this value for the calculations in the rest of the lab and next weeks
lab as well.

Remember ΔT is always Tfinal – Tintital. This is very important to make the direction of heat flow
correct.
The temperatures are all measured data as part of the experiment. The calorimeter temperature can be
reasonably assumed to be the same as the water temperature.

In Part 2 you will find the specific heat of an unknown metal. The metal loses heat to the
surroundings which are the calorimter (both the water and the coffee cup.)
– (mCsΔT)metal = [(mCsΔT)water + (CΔT)calorimeter] (6)

Since you now know Ccal, you will use that number and the unknown will be the specific heat of the
metal (Smetal). (You will use equation (7) again, but are solving for a different piece of information).

Part 3 of the experiment involves finding the heat required to melt an ice cube. This number is called
the molar enthalpy of fusion of ice (or the molar enthalpy of melting) and has symbol ΔHfusion.
Remember that at constant pressure (like on a lab bench, where the atmospheric pressure is constant,
and the system is not enclosed [like a bomb calorimeter]), enthalpy = heat ( q = ΔHp), so the words
heat and enthalpy are often used interchangeably (since we usually operate at constant pressure).

When an ice cube melts, it is absorbing heat from the surroundings. That heat goes into not only
melting the ice cube, but also into warming the resulting “water from ice” to the temperature of the
surroundings. (This analysis also assumes that the ice cube is at 0oC, and not less than 0. If it were less
that 0oC, then first the ice has to warm to 0 before can it melt…). The phase change from ice to water
(melting) is a constant temperature process, meaning all the melting happens at 0oC. The energy is
going in to the ice cube to separate the atoms (melt) rather than warm them up. You’ll learn more
about this in Chem 162. Then once the ice cube is melted there is a “puddle” of cold water that must
absorb more energy to get to the final temperature of the surroundings. (So Tfinal is the same for
everything)

Modifying equation (6) for this process gives

– qlost by surroundings = (qgained by ice cube to melt + qgained by water from ice) (8)

– [(mCsΔT)water + (CΔT)calorimeter] = (9)

[( ΔHfusion x moles ice)+ (mwater from ice x Cswater x (Tfinal water from ice – Tinitial water from ice)]

Some hints and questions:

• The water in the calorimeter and the calorimeter both lose heat, that’s why there are two terms
on the left side of the equation. You should know all the values there.
• the mass of “water from ice” is the mass of the ice cube (the water came from the ice!)
• what is the initial temperature of the water from ice? (Once the ice melts, what temperature do
you think the resulting water should be)
• The final temperature of the water in the calorimeter, the final temperature of the calorimeter
and the final temperature of the water from ice is the same number (everything ends up at the
same final temperature)
• You are trying to calculate the ΔHfusion

Finally, in part 4 and 5 of the experiment you will measure the heat released when

(a) KOH (s) dissolves in water

(b) KOH reacts with HCl

Heat of solution is the heat released or required when a solid dissolves in water, and it is reported as
kJ/mole. KOH (s) has an exothermic heat of solution (some salts have endothermic heats of
solution…can you think of one?). Again the same principles apply as in the previous parts of the
experiment. The heat lost by the salt will be gained by the water and the calorimeter:

qrxn = – qcal

where

qcal = [(mCsΔT)water + (CΔT)calorimeter]

since qcal is positive qrxn will be negative as expected for an exothermic reaction.

To determine ΔHsolution per mole convert the heat of solution in joules to kJ and divide by the number of
moles of KOH.

KOH and HCl also react exothermically. To report kJ per mole for this reaction convert the heat of
solution in joules to kJ and divide by the number of moles of whichever is the limiting reactant (KOH
or HCl).

Procedure:

The procedure for this experiment is very simple, and all the parts have more or less the same
procedure. The general idea is to measure the change in temperature for each process. Do each part 3
times.

Part 1
Add 100 mL of room temperature water to the calorimeter. Record the temperature. This is your cold
water.
Measure 100 mL of hot water between 60 and 80 °C. Record this temperature.
Add the hot water to the cold water in the calorimeter. Measure the temperature immediately after the
solution reaches a stable value.

Part 2
Use 50 – 100 mL of room temperature water (record the volume). Less water generally gives a larger
change in temperature which gives a better result. Record the initial temperature. This is Ti for both
the water and the calorimter.
Record the mass of the metal.
Heat the metal in a boiling water bath for 5 min. Record the initial temperature of the metal in the
water bath.
Add a stir bar to the calorimeter to and place it in a stir plate. Turn on the stirring and add the hot
metal. Measure the temperature change. Be careful not to measure the temperature spike (if there is
one.) Wait until the temperature is somewhat settled before you decide on Tf. You decide how long
that is.

Part 3
Use 100 mL of room temperature water (record the volume). Record the initial temperature. This is
Ti for both the water and the calorimter.
For the mass of the ice, it’s best to weigh the calorimeter (with the water and stir bar) before and after
and calculate the mass of ice by difference.
Part 4
Use 100 mL of room temperature water (record the volume). Record the initial temperature. This is
Ti for both the water and the calorimter.
For part 4, use about 2.5-5 grams of KOH pellets. Don’t forget to stir. Monitor the temperature for a
consistent reading.

Part 5
For part 5, use about 50 mL of each 1.0 M KOH and HCl, so total will be about 100 mL.
Don't use exactly 50 mL of each.
You will not add any additional water.
Make sure you record how much volume you used of each solution. You will need these numbers to
find (a) the limiting reagent and (b) the total volume of solution.
Assume the solution has a density of 1g/mL.
Again monitor temperature change with swirling.

Data
Make sure you have tables ready before you come to lab. You will be collecting data including
temperatures and masses of substances. Think about what needs to be in your data table.

Analysis and Calculations

Show sample calculations in your notebook. You are calculating

(1) Ccal
(2) Csmetal
(3) ΔHfusion of ice
(4) ΔHsolution for KOH
(5) ΔHreaction for KOH + HCl

Determine a percent error for each of the values you determined in the lab. Except for part (1) {there is
no true value for Ccal}, you can look all the numbers up. For part 5, this is called the enthalpy of
neutralization. The net ionic reaction is H+ (aq) + OH- (aq) → H2O (l). You can use this to find the
literature (true) value.

Results
See the lab report format for a description of the results table.

Discussion
The discussion is a qualitative and quantitative description of the experiment. Describe what you did
(qualitative) and what the result was (quantitative – number). For each value where you determined a
percent error indicate a possible source of error (indicate if it was random or systematic) and describe
exactly how it affected your data. You should make sure the error is quantifiable and actually relates to
your data.