1

CALORIMETRY
LESSON 2.3

pb: solugena
2 OUTLINE CONTENT

 SPECIFIC HEAT AND HEAT CAPACITY

 CONSTANT VOLUME-CALORIMETRY
 CONSTANT PRESSURE-CALORIMETRY

pb: solugena
3

CALORIMETRY – the measurement of heat changes,

will depend on an understanding of specific heat and
heat capacity.

CALORIMETER – Is a closed container designed

specifically to measure heat changes in physical and
chemical processes.

pb: solugena
4 Specific Heat and Heat Capacity
 The Specific heat (s) of a substance is the amount of heat required to raise the
temperature of one gram of the substance by one degree Celsius. It has a units J/g
.oC.
 The heat capacity (C) of a substance is the amount of heat required to raise the
temperature of a given quantity of the substance by one degree Celsius. Its units are
J/oC.

 Specific heat is an intensive property, whereas heat capacity is an extensive

property.
 The relationship between heat capacity and specific heat of a substance is
C = ms
m = mass of the substance in grams

pb: solugena
5

Table 1: The Specific Heats of Some Common Substances

Substance Specific Heat (J/g.ºC)
Al (aluminium) 0.900
Au (gold) 0.129
C (graphite) 0.720
C (diamond) 0.502
Cu (copper) 0.385
Fe (iron) 0.444
Hg (mercury) 0.139
Pb (lead) 0.158
H2O (water) 4.184
C2H5OH (ethanol) 2.46

pb: solugena
6
Example 1. Comparison of Heat Capacity of
H2O and Iron

 The specific heat of water is 4.184 J/g.oC and the heat capacity of 60.0 g of
water is:
(60.0 g)(4.184 J/g.oC) = 251 J/oC

 The specific heat of Fe is 0.444 J/g. oC and the heat capacity of 60.0 g of Fe is:
(60.0 g)(0.444 J/g. oC = 26.64 J/oC

pb: solugena
7
Heat Change, q

 The equations for calculating the heat change are given by:
q = msΔt
q = CΔt
Where Δt is the temperature change: Δt = tfinal – tinitial
 The sign convention of q is the same as that for enthalpy change; q is
positive for endothermic process and negative for exothermic process.

pb: solugena
8

Sample problem 1

 A 466-g of water is heated from 8.50ºC to 74.60ºC.

Calculate the amount of heat absorbed (in kJ) by the
water.

pb: solugena
9 Constant-Volume Calorimetry

 Constant-volume Calorimeter is filled with oxygen at about 30 atm of

pressure that measures the heat of combustion by placing a known mass of
a compound in a steel container.

Fig. 1. A constant-volume bomb calorimeter.

The closed bomb calorimeter is immersed in a
known amount of water. The calorimeter is
filled with oxygen gas before it is placed in the
bucket. The sample is ignited electrically, and
the heat produced by the reaction can be
accurately determined by measuring the
temperature increase in the known amount of
surrounding water. The heat given off by the
sample is absorbed by the water and the
bomb.

pb: solugena
10

Fig. 2. Energy from food and

sweeteners are being measured
by bomb calorimeter

pb: solugena
11

 Because no heat enters or leaves the system throughout the process, the
heat change of the system (qsystem) must be zero and we can write:
qsystem = qcal + qrxn
=0
qcal = heat changes for the calorimeter
qrxn = heat changes of the reaction (or heat of combustion)

Thus: qrxn = -qcal

 To calculate qcal, we need to know the heat capacity of calorimeter (Ccal)
and the temperature rise, that is:
qcal = CcalΔt
 The quantity Ccal is calibrated by burning a substance with an accurately
known heat of combustion.

pb: solugena
12

Example 2
 The combustion of 1 g of benzoic acid (C6H5COOH) releases 26.42 kJ of
heat. If the temperature rise is 4.673oC, then the heat capacity of the
calorimeter is given by:
Ccal = qcal/Δt
26.42𝑘𝐽
Ccal = = 5.654 kJ/ºC
4.673°𝐶

 Note that because reactions in a bomb calorimeter occur under constant-

volume rather than constant-pressure conditions, the heat changes do not
correspond to the enthalpy change ΔH.

pb: solugena
13

Sample problem 2

 A quantity of 1.435 g of naphthalene (C10H8), a pungent-smelling

substance used in moth repellents, was burn in a constant-volume
bomb calorimeter. Consequently, the temperature of the water
rose from 20.28ºC to 25.95ºC. If the heat capacity of the bomb plus
water was 10.17 kJ/ºC, calculate the heat of combustion of
naphthalene on a molar basis; that is find the molar heat of
combustion.

pb: solugena
14 Constant-Pressure Calorimetry

 Constant-pressure calorimeter – a simpler device than the constant-volume

calorimeter, which is used to determine the heat changes for non-combustion
reactions.
 A crude constant-pressure calorimeter can be constructed from two Styrofoam
coffee cups.
 This device measures the heat effects of a variety of reactions, such as
 acid-base neutralization
 heat of solution
 heat of dilution.
 Because the pressure is constant, the heat change for the process (qrxn) is equal
to the enthalpy change, ΔH

pb: solugena
15

Fig. 3. A constant-pressure calorimeter made of two

Styrofoam coffee cups. The outer cups helps insulate
the reacting mixture from the surroundings. Two
solutions of known volume containing the reactants at
the same temperature are carefully mixed in the
calorimeter. The heat produced or absorbed by the
reaction can be determined by measuring the
temperature change.

pb: solugena
16

Table 2. Heats of Some Typical Reactions Measured at Constant Pressure

Types of Reaction Example ΔH (kJ/mol)

Heat neutralization HCl(aq) + NaCl(aq) NaCl(aq) + H2O(l) -56.2
Heat of ionization H2O(l) H+(aq) + OH-(aq) 56.2
Heat of fusion H2O(s) H2O(l) 6.01
Heat of vaporization H2O(l) H2O(g) 44.0*
Heat of reaction MgCl2(s) + 2Na(l) 2NaCl + Mg(s) -180.2

*Measured at 25ºC. At 100ºC, the value is 40.79 kJ.

pb: solugena
17
Sample problem 3
 A lead (Pb) pellet having a mass of 26.47 g at 89.98 ºC was placed in a
constant-pressure calorimeter of negligible heat capacity containing
100.0 mL of water. The water temperature rose from 22.50ºC to 23.17ºC.
What is the specific heat of the lead pellet?

pb: solugena
18

Sample problem 4
 A quantity of 1.00x10^2 mL of 0.500 M HCl was mixed with 1.00 x 10^2 mL of
0.500 M NaOH in a constant-pressure calorimeter of negligible heat capacity.
The initial temperature of the HCl and NaOH solutions was the same, 22.50ºC,
and the final temperature of the mixed solution was 25.86ºC. Calculate the
heat change for the neutralization reaction on a molar basis:
HCl(aq) + NaCl(aq) NaCl(aq) + H2O(l)
Assume that the density and specific heats of the solutions are the same as for
water (1.00 g/mL and 4.184 J/g. ºC, respectively).

pb: solugena
19
Different Types of Calorimeter

pb: solugena
20 Practice Exercises
 1. An iron bar of mass 869 g cools from 94ºC to 5ºC. Calculate the heat released
(in kJ) by the metal.
 2. A quantity of 1.922 g of methanol (CH3OH) was burned in a constant-volume
calorimeter. Consequently, the temperature of the water rose by 4.20 ºC. If the
heat capacity of the bomb plus water was 10.4 kJ/ºC, calculate the molar heat
of combustion of methanol.
 3. A 30.14-g stainless steel ball bearing at 117.82ºC is placed in a constant-
pressure calorimeter containing 120.0 mL of water at 18.44ºC. If the specific heat
of ball bearing is 0.474 J/g. ºC, calculate the final temperature of the water.
Assume the calorimeter to have negligible heat capacity.
 4. A quantity of 4.00x10^2 mL of 0.600 M HNO3 is mixed with 4.00x10^2mL of 0.300
M Ba(OH)2 in a constant-pressure calorimeter of negligible heat capacity. The
initial temperature of both solutions is the same at 18.46 ºC. What is the final
temperature of the solution? (use the result in sample problem 4 for your
calculation.)

pb: solugena
21 References

 P. W. Atkins, J. de Paula. Physical Chemistry. Oxford University Press.

 R. Chang, and K. Goldsby. (2016) Chemistry, 12th Ed. McGraw-Hill, Inc., USA
 l. Levine. Physical Chemistry. McGraw-Hill Company.
 K. Laidler. Physical Chemistry. Houghton Mifflin Company.
 R. J. Silbey, R. A. Albertyand, M. G. Bawendi. Physical Chemistry. John Wiley.
 A. M. Halpern and J. H. Reeves. Experimental Physical Chemistry —A Laboratory
Textbook. Scott, Foresman and Co.
 D. P. Schoemaker, C. W. Garland and J.W. Nibler. Experiments in Physical
Chemistry. McGraw-Hill.
 F. A. Bettelheim. Experimental Physical Chemistry. W. B. Saundeers.
 R. J. Sime. Physical Chemistry: Methods, Techniques and Experiments. Saunders
College Publications.

pb: solugena
22

pb: solugena