1/29/2018 Calorimetry - Measuring Heats of Reactions

CAcT HomePage

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.

http://www.science.uwaterloo.ca/~cchieh/cact/c120/calorimetry.html 1/7
1/29/2018 Calorimetry - Measuring Heats of Reactions

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,
http://www.science.uwaterloo.ca/~cchieh/cact/c120/calorimetry.html 2/7
1/29/2018 Calorimetry - Measuring Heats of Reactions

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:
Energy used = 10 * 5 * 60 = 3000 J. dE = qv = C * dT
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.

Solution: formula:
Heat released, qv, dE = qv = s * m * dT
s, specific heat; m mass.
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

http://www.science.uwaterloo.ca/~cchieh/cact/c120/calorimetry.html 3/7
1/29/2018 Calorimetry - Measuring Heats of Reactions

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 dH°comb = -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

http://www.science.uwaterloo.ca/~cchieh/cact/c120/calorimetry.html 4/7
1/29/2018 Calorimetry - Measuring Heats of Reactions

= - 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 1.602°C. The heat capacity of the calorimeter is 1.238
kJ/K. Calculate dH°comb.

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 dH°f 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,

dH°f (CO2(g)) = -393.5 kJ/mol

dH°f (H2O(l)) = -285.8 kJ/mol

Since

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

dH°comb = 2 dH°f(CO2(g)) + dH°f(H2O(l)) - dH°f(oxalic acid)
-250.6 = 2 * (-393.5) + (-285.8) - dH°f(oxalic acid)

Therefore

http://www.science.uwaterloo.ca/~cchieh/cact/c120/calorimetry.html 5/7
1/29/2018 Calorimetry - Measuring Heats of Reactions

dH°f(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 NH3 (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 NH3.

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.

http://www.science.uwaterloo.ca/~cchieh/cact/c120/calorimetry.html 6/7
1/29/2018 Calorimetry - Measuring Heats of Reactions

When 0.1234 g of oxalic acid (C2O4H2) is burnt in the calorimeter under the same conditions as
Example 6, the temperature increased by 2.314°C. 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 dH°comb. Hint . . .

Skill:
Measure the enthapy of combustion by bomb calorimetry.
© cchieh@uwaterloo.ca

http://www.science.uwaterloo.ca/~cchieh/cact/c120/calorimetry.html 7/7