Calorimetry

Measuring Heats of Reactions

Skills to develop

Calculate amount of electric energy for heat capacity measurement

Perform experiments to measure heats of reactions

Calculate the heats of reactions from experimental results

Calculate internal energies of reactions from bomb calorimeter

experiments

Calculate enthalpies of reactions from bomb calorimetry experiments

Calorimetry - Measuring Heats of Reactions

Calorimetry, derived from the Latin calor meaning heat, and the
Greek metry meaning to measure, is the science of measuring the amount of heat. All
calorimetric techniques are therefore based on the measurement of heat that may be
generated (exothermic process), consumed (endothermic process) or simply dissipated
by a sample. There are numerous methods to measure such heat, and since
calorimetry's advent in the late 18th century, a large number of techniques have been
developed. Initially techniques were based on simple thermometric (temperature
measurement) methods, but more recently, advances in electronics and control have
added a new dimension to calorimetry, enabling users to collect data and maintain
samples under conditions that were previously not possible.

Any process that results in heat being generated and exchanged with the environment
is a candidate for a calorimetric study. Hence it is not surprising to discover that
calorimetry has a very broad range of applicability, with examples ranging from drug
design in the pharmaceutical industry, to quality control of process streams in the
chemical industry, and the study of metabolic rates in biological (people included)
systems. Indeed if the full range of applications were to be mentioned, the allocated
disk space on this site would soon be used up.
We discuss the basics of two types of calorimetry: measurements based on constant
pressure and measurement based on constant volume. The former involves pressure-
volume work, whereas the latter does no pressure-volume work.

Calorimeter
A calorimeter is a device used to measure heat of reaction. It can be sophisticated and
expensive or simple and cheep. In CHEM120 Labs, a styrofoam cup is used as a
calorimeter, because it is a container with good insulated walls to prevent heat
exchange with the environment. In order to measure heats of reactions, we often
enclose reactants in a calorimeter, initiate the reaction, and measure the temperature
difference before and after the reaction. The temperature difference enables us to
evaluate the heat released in the reaction. This page gives the basic theory for this
technique.

A calorimeter may be operated under constant (atmosphere) pressure, or constant

volume. Whichever kind to use, we first need to know its heat capacity. The heat
capacity is the amount of heat required to raise the temperature of the entire
calorimeter by 1 K, and it is usually determined experimentally before or after the
actual measurements of heat of reaction.

The heat capacity of the calorimeter is determined by transferring a

known amount of heat into it and measuring its temperature increase.
Because the temperature differences are very small, extreme sensitive
thermometers are required for these measurements. Example 1 shows
how it is done.

Example 1

The temperature of a calorimeter increases 0.10 K when 7.52 J of electric

energy is used to heat it. What is the heat capacity of the calorimeter?

Solution:
Dividing the amount of energy by the temperature increase yields the heat
capacity, C,

C = 7.52 / 0.10 = 75.2 J/K.

Discussion:
We often compare the heat capacity of a calorimeter to that of a definite amount
of water. The heat capacity of 75.2 J/K for the calorimeter is equivalent to the
 heat capacity of 1 mole (18 g) of water (18 g mol -1*1 cal (g K)-1*4.184 J cal-1 =
75.3 J (K mol)-1.

Do you know that the electric energy = q * dV = i * dt * dV, where q is

charge; dV, voltage; i, current; and t, time.

Measuring the Enthalpy by Calorimetry

By definition, dH is the energy (heat) released at constant pressure, whereas dE is the

energy released at constant volume. These two quantities are related by the equation.

dH = dE + (d(P V))
= dE + dn R T (applying the ideal gas law)
where
dn = number of moles of gas in the products - number of moles of gas in the
reactants.

The P-V work must be taken into consideration for the calculation of depends on the
extra amount (dn moles) of dH, if the calorimetry is performed at constant volume in a
bomb calorimeter. A cross-section diagram of the bomb is shown here. The wires are
for electric ignition, and the sample in the sample holder is in touch with the resistant
wire. The bomb's diameter is 10 cm, and its height is 15 cm.
The Bomb Calorimeter
For combustion reactions, we often enclose all reactants in
an explosive-proof steel container, called the bomb whose
volume does not change during a reaction. The bomb is
then submerged in water or other liquid that absorbs the
heat of reaction. The heat capacitor of the bomb plus other
things is then measured using the same technique as other
calorimeters. Such an instrument is called a bomb
calorimeter, and its application is called the bomb
calorimetry

The picture shows reading the sensitive thermometer

while working with the P6310 Bomb Calorimeter.
The bomb is inside the tank.

Since volume does not change, a bomb calorimeter

measures the heat evolved under constant volume, qv,

qv = C * dT,
where dT is the temperature increase. The qv so measured
is also called the change in internal energy, dE. Note that
dE = qv = C * dT

Example 2

When a 10.0-watt (J/s) heater is used to heat a

bomb calorimeter, its temperature increases by
3.0 K in 5.0 min. Calculate the heat capacity of
the calorimeter.

Solution:
formula:
dE = qv = C * dT
Energy used = 10 * 5 * 60 = 3000 J.
Thus, C = 3000 / 3.0 = 1000 J/K,
This is equivalent to (1000 J/K) / (75.2 J/(K mol))
= 13.3 moles of water.

The following related examples illustrate the application

of bomb calorimeter for the measurement of dE, and the
derivation of dH.
Example 3

A calorimeter with heat capacity equivalent to having 13.3 moles of water

is used to measure the heat of combustion from 0.303 g of sugar
(C12H22O11). The temperature increase was found to be 5.0 K. Calculate the
heat released, the amount of heat released by 1.0 g, and 1.0 mole of sugar.
formula:
dE = qv = s * m * dT
s, specific heat; m mass.
Solution:
Heat released, qv,

qv = 13.3 mol * 75.2 J/(K mol) * 5.0 K

= 5000 J
The amount of heat released by 1.0 g would be,
5000 J/0.303 g = 16.5 kJ / g
Since the molecular weight of sugar is 342.3 g/mol, the amount of heat released
by 1.0 mole would be
16.5 kJ / g * 342.3 g/mol = 5648 kJ/mol.

Example 4

The heat released by one mole of sugar from a bomb calorimeter

experiment is 5648 kJ/mol. Calculate the enthalpy of combustion per mole
of sugar.

Solution
The balanced chemical reaction equation is

C12H22O11(s) + 12 O2(g) = 12 CO2(g) + 11 H2O(l)

Since the total numbers of moles of gases (12) before the reaction is the same
as that after the reaction, dn = 0
dH = dE = 5648 kJ/mol

Discussion
This is the ideal amount of energy released when a mole of sugar is utilized by
a living creature such as a person.

Example 5
 A table of thermodynamic data gives dHf = -285.8 kJ/mol for water. A
bomb calorimeter measurement gives the heat of combustion for H2 as
-282.0 kJ/mol. Estimate the error of the enthalpy measurement.

Solution
Reinterpret the problem, we have

H2(g) + 0.5 O2(g) = H2O(l), dE = 282.0 kJ/mol.

Furthermore,
dn = -1.5
dH = dE + dn R T,
= - 282.0 + (-1.5 mol * 8.314 J/(mol K) * 298 K)
= (-282.0 - 3.72) kJ
= -285.7 kJ
The error is (285.8-285.7)/285.8 = 0.03%

Discussion
More heat is giving of if the reaction is carried out at constant pressure, since
the P-V work (1.5 R T) due to the compression of 1.5 moles of gases in the
reactants would contribute to dH.

If 1.0 mole water is decomposed by electrolysis at constant pressure, we must

supply an amount of energy equivalent to enthalpy change, dH, a little more
than internal energy, dE. More energy must be supplied to perform the P-
V work to be done by the products (H2 and O2).

The heat capacity of the calorimeter can also be determined by burning an exactly
known amount of a standard substance, whose enthalpy of combustion has been
determined. Benzoic acid, C7H6O2, is one such standard. The problem below
illustrates the calculations.

Example 6

When 0.1025 g of benzoic acid was burnt in a bomb calorimeter the

temperature of the calorimeter increased by 2.165 C. For benzoic
acid dHcomb = -3227 kJ mol-1. Calculate the heat capacity of the
calorimeter.

Solution:
The equation for the combustion is,

C7H6O2(s) + 7.5 O2(g) -> 7CO2(g) + 3H2O(l), dH = 3227 kJ

 Since 7.5 moles of O2 gas is needed, and 7 moles of CO2 is produced, some
pressure-volume work is done, to the calorimeter:
P V = dn R T, where dn = (7 - 7.5) = - 0.5 mol
dE = dH - dn R T
= - 3227 - (-0.5*8.314298*298)
= - 3226 kJ/mol (a small correction)
The amount of heat produced by 0.1025 g benzoic acid is
q = 0.1025/122.13 mol x 3226 (kJ/mol) = 2.680 kJ
Thus, the heat capacity is
C = q / dT = 2.680 / 2.165 = 1.238 kJ / K.
After the heat capacity is determined, the calorimeter is ready to be used to measure
the enthalpy of combustion of other substances.

Example 7

When 0.7022 g of oxalic acid (C2O4H2) is burnt in the calorimeter under

the same conditions as Example 6, the temperature increased by 1.602C.
The heat capacity of the calorimeter is 1.238 kJ/K. Calculate dHcomb.

Solution:
The balanced equation and various quantities calculated are given in a logical
order below:

C2O4H2(s) + 0.5 O2(g) -> 2 CO2 (g) + H2O(l)

dn = 1.5 q = C dT = 1.238*1.602 = 1.984 kJ
n of oxalic acid = 0.7022/90 = 0.00780 mol
dE = -1.984 / 0.00780 = -354.4 kJ/mol
dH = dE + dn R T
= -254.4 kJ + 1.5 mol * 0.008314 kJ/(K mol)* 298 K
= -250.6 kJ/mol

Discussion:
Can the standard enthalpy of formation dHf for oxalic acid be calculated?
What additional data are required?

Example 8

Calculate the enthalpy of formation of oxalic acid, for which the enthalpy
of combustion is -251 kJ/mol.

Solution:
The following data were looked up from thermodynamic data,
 dHf (CO2(g)) = -393.5 kJ/mol
dHf (H2O(l)) = -285.8 kJ/mol
Since
C2O4H2(s) + 0.5 O2(g) -> 2 CO2 (g) + H2O(l)
dHcomb = 2 dHf(CO2(g)) + dHf(H2O(l)) - dHf(oxalic acid)
-250.6 = 2 * (-393.5) + (-285.8) - dHf(oxalic acid)
Therefore
dHf(oxalic acid) = 2 * (-393.5) + (-285.8) - (-250.6)
= -822.2 kJ/mol

Discussion:
It's important to know what additional data is required for problem solving. It's
equally important to know where to look for them.

We have given an introduction to calorimetry here, and for a detailed laboratory

instruction, consult the CHEM120L manual and the Oxygen Bomb Calorimetry which
has several pages giving the details of the measurement. In particular, how to measure
the temperature difference is given in Calorimetry Data Analysis.

Confidence Building Questions

A microwave oven operates at 500 watt for 2 minutes. How much electric
energy (J) is consumed?
Hint . . .

Skill:
Calculate amount of electric energy for heat capacity measurement.
Review Skills.

A cup of (200 g) water heated in a microwave oven had a temperature

increase of 60 K. How much energy (in kJ) was absorbed by the water?
Recall that heat capacity of water is 4.184 J/(g K).
Hint . . .
 Skill:
Calculate the amount of energy when the heat capacity and temperature
increase is known, a preparation for enthalpy evaluation.

The temperature of a calorimeter increased 0.25 K when 50.0 J of energy

was absorbed. What is its heat capacity (kJ/K)?
Hint . . .

Skill:
Measure the heat capacity of a calorimeter.

When 100 mL of 0.50 M NH3 is neutralized by 300 mL of a solution

containing excess HCl, the solution temperature increases 1.6 K. The
experiment is performed in a styrofoam cup, and there is no energy loss.
Calculate the heat of reaction, dH.
Hint . . .

Discussion:
2678 J was generated by 0.05 mol NH3 (0.100 L * 0.5 mol/L)

How much heat (kJ) should be generated if 1.0 mole NH3 is neutralized by
dilute HCl solution, if 2675 J was generated when 0.05 mol NH 3 (0.100 L *
0.5 mol/L) was neutralized as described in the previous
problem?
Hint . . .

Discussion:
In fact, 53.6 kJ/mol is called the molar heat of neutralization of NH 3.

 Combustion of 0.92 g toluene, C7H8 in a bomb calorimeter (Cv equivalent

to 1003 g of water) raised its temperature by 9.3 K.
Estimate dH
Hint . . .

Some details
q = 39040 J; dE = 3904 kJ; dH = -3909 kJ/mol.

When 0.1234 g of oxalic acid (C2O4H2) is burnt in the calorimeter under

the same conditions as Example 6, the temperature increased by 2.314C.
Calculate the heat capacity of the calorimeter.
Hint . . .

Skill
Using a standard to determine the heat capacity of a calorimeter.

When 0.2006 g of oxalic acid (C2O4H2) is burnt in the calorimeter whose

heat capacity is 1.238 kJ/K. the temperature increased by 0.4577 K.
Calculate dHcomb.
Hint . . .

Skill:
Measure the enthapy of combustion by bomb calorimetry.