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Discussion
Thermochemistry

This module deals with energy and heat, two terms used widely by both the general public and
scientists. Energy is very much a chemical topic. Almost all of the energy on which we depend
is derived from chemical reactions, such as the combustion of fossil fuels, the chemical
reactions occurring in batteries, or the formation of biomass through photosynthesis. If we are
properly understand chemistry, we must also understand the energy changes that accompany
the chemical change.
What is energy? Where does the energy we use come from? And how can a chemical reactions
result in the transfer of energy to from the surroundings?
Energy can be defined as the capacity to do work. There are many forms of energy, such as
heat energy, electrical energy and chemical energy .When one form of energy is converted into
another form, energy is neither nor destroyed. Heat is a particular form of energy that is
transferred from a body at a high temperature to one at a lower temperature when they are
brought into contact with each other. Two centuries ago, heat was believed to be a material fluid
(caloric); we still use the phrase “heat flow” to refer to heat transfer or to heat effects in general.
Thermochemistry refers to the study of the heat flow that accompanies chemical reactions.

The system is the part of the universe on which attention is focused. The surroundings, which
exchange energy with the system, make up in principle the rest of the universe. For all practical
purposes, however, they include only those materials in close contact with the system. The
surroundings would consist of the hot plate, the beaker holding the water sample, and the air
around it.
When a chemical reaction takes place, we consider the substances involved, reactants
and products, to be the system. The surroundings include the vessel in which the reaction takes
place (test tube, beaker and so on) and the air or other material in thermal contact with the
reaction system.

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Direction and Sign of Heat Flow

If the hot plate in turned on, there is a flow of heat from the surroundings into the system, 50.0 g
of water. This situation is described by stating that the heat flow, q, for the system is a positive
quantity.
q is positive when heat flows into the system from the surroundings.
Usually, when heat flows into a system, its temperature rises. In this case, the temperature of
50.0 g of water sample might increase from 50.0 ºC to 80.0 ºC. When the hot water gives off
heat tot the surrounding air. In this case, q for the system is a negative quantity.

q is negative when heat flows out of the system into the surroundings.

As is usually the case, the temperature of the system drops when heat flows out of it into the
surroundings. The 50.0 g of water sample might cool from 80.0 ºC back to 50.0 ºC.

This same reasoning can be applied to a reaction in which the system consists of the reaction
mixture (products and reactants). We can distinguish between
 An endothermic process (q > 0), which heat flows from the surroundings into the
reaction system. An example is the melting of ice:
H2O(s) H2O(l) q > 0

The melting of ice absorbs heat form the surroundings which might be the water in a glass of
iced tea. The temperature of the surroundings drops, perhaps from 25 ºC to 3ºC, as they give
up heat to the system.
 An exothermic process (q > 0), in which heat flows from the reaction system into
the surroundings. A familiar example is the combustion of methane, the major
component of natural gas.
CH4(g) + 2O2(g) CO2(g) + 2H2O(l) q < 0

This reaction evolves heat to the surroundings, which might be the air around a Bunsen burner
in the laboratory or a potato being baked in a gas oven. In either case, the effect of the heat
transfer is to raise the temperature of the surroundings.

Magnitude of Heat Flow

In any process, we are interested not only in the direction of heat flow but also in its magnitude.
We will express q in the units, joule and the kilojoule. The joule is named for James Joule (1818
– 1889), who carried out very precise thermometric measurements that established the first law
of thermodynamics.
In the past, chemists used the calorie* as an energy unit. This is the amount of heat
required to raise the temperature of one gram of water one degree Celsius. The calorie is a
larger energy unit than the joule:
1 cal = 4.184 J 1 kcal = 4.184 kJ

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We will focus on a simpler process in which the only effect of the heat flow is to change
the temperature of a system. In general, the relationship between the magnitude of the heat
flow, q, and the temperature change, ∆ t, is given by the equation
q = C x ∆t (∆ t = tfinal - tinitial)

The quantity C appearing in this equation is known as the heat capacity of the system. It
represents the amount of heat required to raise the temperature of the system 1ºC and has the
units J/ºC.
For a pure substance of a certain mass, the expression for q can be written
q = mass x c x ∆ t

The quantity c is called the specific heat or specific heat capacity. Specific heat is defined as
the amount of heat required to raise the temperature of one gram of a substance one degree
Celsius. When the mass of that substance is equal to its molar mass, then c is called the molar
heat capacity.
Specific heat, like density or melting point, is an intensive property that can be used to
identify a substance or determine its purity. Water has an unusually large specific heat, 4.18 J/g
ºC.

Table 1.0 Specific Heats of a Few Common Substances

c (J/g · ºC) c (J/g · ºC)
Br2(l) 0.474 Cu(s) 0.382
Cl2(g) 0.478 Fe(s) 0.446
C2H5OH(l) 2.43 H2O(g) 1.87
C6H6(l) 1.72 H2O(s) 4.18
CO2(g) 0.843 NaCl(s) 0.866

EXAMPLES
1. What is the heat capacity of the 100g of water?

Given: 100 g of water

Asked for: Heat capacity

SOLUTION

C = mass x c
= 100 g x 4.184 J/ g · ºC
= 418.4 J/ ºC

Answer: 418.4 J/ ºC

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2. How many kilojoules of heat will raise the temperature of 2.00 kg of water from 21.10 ºC
to 38.00 ºC?

Given: 2.00 kg of water

Asked for: q (kJ)

SOLUTION

q = m x c x ∆t
= 2000 g x 4.184 4.184 J/ g · ºC x (38.00 – 21.10) ºC
q = 141,419.2 J = 141 kJ

Answer: 141 kJ

3. Compare the amount of heat given off by 1.40 mole of liquid water when it cools from
100.0 ºC to 30.0 ºC to that given off when 1.40 mol of steam cools from 200.0 ºC to
110.0 ºC.

Given: H2O(l) : mols (1.40), tfinal (30.0 ºC), tinitial (100.0 ºC)
H2O(g) : mols (1.40), tfinal (110.0 ºC), tinitial (200.0 ºC)
Asked for: q for both water and steam

SOLUTION

For H2O(l):
1. ∆ t ∆ t = tfinal – tinitial = 30.0 ºC – 100.0 ºC = – 70.0 ºC
2. mass 1.40 mol x 18.02 g = 25.2 g
1 mol
3. c from the table 1.0, c = 4.18 J/g · ºC.
4. q q = mass x ∆ t x c = (25.2 g)(4.18 J/g • ºC)( – 70.0 ºC)
= – 7.37 x 103 J
For H2O(g):
1. ∆ t ∆ t = tfinal – tinitial = 110.0 ºC – 200.0 ºC = – 90.0 ºC
2. mass 1.40 mol x 18.02 g = 25.2 g
1 mol
3. c from the table 1.0, c = 1.87 J/g ºC.
5. q q = mass x ∆ t x c = (25.2 g)(4.18 J/g • ºC)( – 70.0 ºC)
= – 4.24 x 103 J

1. The negative sign indicates that heat flows from the system (water and steam) to the
surroundings.
2. Be careful when deciding on initial and final temperatures. The higher temperature is not
necessarily the final temperature.

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? SAQ 1
1. What is the heat capacity of 250 g of water?

2. How many kilojoules of heat will raise the temperature of 1.50 kg of water from 22.00 ºC
to 25.00 ºC?

3. What is the specific heat of ethyl alcohol if 129 J of heat is required to raise the
temperature of 15.0 g of ethyl alcohol from 22.70 ºC to 26.20 ºC?

4. The specific heat of lead is 0.129 J / g · ºC. How many joules of heat is required to raise
the temperature of 207 g of lead from 22.25 ºC to 27.65 ºC?

5. The specific heat of nickel is 0.444 J / g · ºC. If 50.0 J of heat is added to a 32.3 g
sample of nickel at 23.25 ºC, what is the final temperature of the sample?

Measurement of Heat Flow; Calorimetry

The measure the heat flow in a reaction, a device known as a calorimeter is used. The
apparatus contains water and/or other materials of known heat capacity. The walls of the
calorimeter are insulated so that there is no exchange of heat with the surrounding air. It follows
that the only heat flow is between the reaction system and the calorimeter. The heat flow for the
reaction system is equal in magnitude but opposite in sign to that of the calorimeter:
qreaction = – qcalorimeter

Notice that if the reaction is exothermic (qreaction < 0), qcalorimeter must be positive; that is, heat flows
from the reaction mixture into the calorimeter. Conversely, if the reaction is endothermic, the
calorimeter gives up heat to the reaction mixture.
The equation just written is basic to calorimetric measurements. It allows you to
calculate the amount of heat absorbed or evolved in a reaction if you know the heat capacity,
Ccal and the temperature change, ∆ t, of the calorimeter.
qcal = Ccal x ∆ t

Coffee-Cup Calorimeter
The figure shows a simple coffee-cup calorimeter used in
the general chemistry laboratory. It consists of two nested
Styrofoam cups partially filled with water. The cups have
a tightly fitting cover through which an accurate thermo-
-meter is inserted. Because Styrofoam is a good insulator, there is
very little heat flow through the walls of the cups.
Essentially all the heat evolved by a reaction taking place within the calorimeter

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is absorbed by the water. This means that, to a good degree of approximation, the heat capacity
of the coffee-cup calorimeter is that of the water:

Ccal = masswater x cwater = masswater x 4.18 J_

g • ºC
and hence,
qreaction = – masswater x 4.18 J_ x ∆ t
g • ºC

EXAMPLE 1

Calcium chloride, CaCl2, is added to canned vegetables to maintain the vegetables’ firmness.
When added to water, it dissolves:
CaCl2(s) Ca2 (aq) + 2Cl- (aq)

A calorimeter contains 50.0 g of water at 25.00 ºC. When 1.00 g of calcium chloride is added to
the calorimeter the temperature rises to 28.51 ºC. Assume that all the heat given off by the
reaction is transferred to the water.

a) Calculate q for the reaction system.

Given: mass of water (50.0 g); mass of CaCl2 (1.00 g)

initial temperature (25.00 ºC); final temperature (28.51 ºC)
Asked for: qreaction

SOLUTION

1. ∆ t ∆ t = tfinal – tinitial = 28.51 ºC – 25.00 ºC = 3.51 ºC

2. qH2O qH2O = mass x ∆ t x c = (50.0g)(4.18 J/g • ºC)(3.51 ºC) = 734 J
3. qreaction qreaction = – qH2O = – 734 J

b) How much CaCl2 must be added to raise the temperature of the solution 9.00 ºC?

Given: mass of water (50.0 g)

from part (a), qreaction for 1.00 g of CaCl2 used (–734 J).
∆ t (9.00 ºC)
Asked for: Mass CaCl2 to be added

SOLUTION

1. qwater qH2O = mass x ∆ t x c = (50.0g)(4.18 J/g • ºC)(9.00 ºC) = 1.88 x 103 J

2. qreaction qreaction = – qH2O = – 1.88 x 103 J

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3. Mass CaCl2 – 1.88 x 103 J x 1.00 g CaCl2 = 2.56 g

needed –734 J

4. Mass CaCl2 2.56 – 1.00 = 1.56 g

to be added

Since the final temperature is larger than the initial temperature after the addition of CaCl 2, the
reaction must be exothermic. Thus qreaction must be negative. It is!

? SAQ 2
1. Sodium chloride is added in cooking to enhance the flavor of food. When 10.00 g of
NaCl are dissolved in 200.0 mL of water at 25.0 ºC in a coffee-cup calorimeter, 669 J of
heat are absorbed. (You can make the following assumptions about the solution: volume
= 200.0 mL, density = 1.00 g/mL, specific heat = 4.18 J/g · ºC)
a) Is the solution process exothermic?
b) What is qH2O?
c) What is the final temperature of the solution?

EXAMPLE 2

Hydrogen chloride is used in etching semiconductors. It can be prepared by reacting hydrogen

and chlorine gases.
H2(g) + Cl2(g) 2HCl(g)

It is found that when 1.00 g of H2 is made to react completely with Cl2 in a bomb calorimeter with
a heat capacity of 5.15 kJ/ºC, the temperature in a bomb rises from 20.00 ºC to 29.82 ºC. the
calorimeter can hold 1.000 kg of water. How much heat is evolved by the reaction?

Given: mass of H2 (1.00 g); mass of water (1.000 kg = 1.000 x 103 g)

Ccal (5.15 kJ/ºC)
tfinal (29.82 ºC), tinitial (20.00 ºC)
Implied: specific heat (c) of water
Asked for: q for the reaction

SOLUTION

1. qH2O qH2O = cH2O x massH2O x ∆ t

= 4.18 _ J _ x 1.000 x 103 g x (29.82 – 20.00)ºC
g • ºC
= 4.10 x 104 J = 41.0 kJ

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2. qcal qcal = Ccal x ∆ t = (5.15 kJ/ºC)(29.82 -20.00)ºC = 50.6 kJ

3. qreaction qreaction = –(qcal + qH2O) = –(41.0 + 50.6)kJ = –91.6 kJ

? SAQ 3
1. In earlier times, ethyl ether was commonly used as an anesthetic. It is, however, highly
flammable. When five milliliters of ethyl ether, C4H10O(l) (d = 0.714 g/mL), are burned in
a bomb calorimeter, the temperature rises from 23.5 ºC to 39.7 ºC. The calorimeter
contains 1.200 kg of water and has a heat capacity of 5.32 kJ/ ºC.
a) What is qH2O?
b) What is qcal?
c) What is q for the combustion of 5.00 mL of ethyl ether?
d) What is q for the combustion of one mole of ethyl ether?

Enthalpy
We have referred several times to the “heat flow for the reaction system,” symbolized as qreaction.
At this point, you may well find this concept a bit nebulous and wonder if it could be made more
concrete by relating qreaction to some property of reactants and products. This can indeed be
done; the situation is particularly simple for reactions taking place at constant pressure. Under
that condition, the heat flow for the reaction system is equal to the difference in enthalpy (H)
between products and reactants. The enthalpy change is designated as ∆ H . That is,

qreaction at constant pressure = ∆ H = Hproducts – Hreactants

Enthalpy is a type of chemical energy, sometimes referred to as “heat content.” Reactions that
occur in the laboratory in an open container or in the world around us take place at a constant
pressure, that of the atmosphere. For such reactions, the equation just written is valid, making
enthalpy a very useful quantity.

In general, the following relations apply for reactions taking place at constant pressure.

exothermic reaction: q=∆H <0 Hproduct < Hreactants

endothermic reaction: q=∆H >0 Hproduct > Hreactants

The enthalpy of a substance, like its volume, is a stae property. A sample of one gram of liquid
water at 25.00ºC and 1 atm has a fixed enthalpy, H. In practice, no attempt is made to
determine absolute values of enthalpy. Instead, scientists deal with changes in enthalpy, which
are readily determined. For the process

1.00 g H2O (l, 25.00ºC, 1 atm) 1.00 g H2O (l, 26.00ºC, 1 atm)

∆ H is 4.18 J because the specific heat of water is 4.18 J/g • ºC.

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Thermochemical Equations
A chemical equation that shows the enthalpy relation between products and reactants is called
a thermochemical equation. This type of equation contains, at the right of the balanced
chemical equation, the appropriate value and sigh for ∆ H .

To see where a thermochemical equation comes from, consider the process by which
ammonium nitrate dissolves in water:

NH4NO3(s) NH4+(aq) + NO3-(aq)

A simple experiment with a coffee-cup calorimeter shows that when one gram of NH 4NO3
dissolves, qreaction = 351 J. The calorimeter is open to the atmosphere, the pressure is constant,
and
∆ H for dissolving 1.00 g of NH4NO3 = 351 J = 0.351 kJ

When one mole (80.05 g) of NH4NO3 dissolves, ∆ H should be 80 times as great:

∆ H for dissolving 1.00 mol of NH4NO3 = 0.351 kJ x 80.05 g = 28.1 kJ

g

These thermochemical equations are typical of those used throughout this text. It is important to
realize that

 the sign of ∆ H indicates whether the reaction, when carried out at constant pressure, is
endothermic (positive ∆ H ) or exothermic (negative ∆ H ).
 in interpreting a thermochemical equation, the coefficients represent numbers of moles (∆ H
is – 185 kJ when 1 mol H2 + 1 mol Cl2 2 mol HCl).
 the phases (physical states) of all species must be specified, using the symbols (s), (l), (g),
or (aq). The enthalpy of one mole of H2O(g) at 25 ºC is 44 kJ larger than that of one mole of
H2O(l); the difference, which represents the heat of vaporization of water, is clearly
significant.
 The value quoted for ∆ H applies when products and reactants are at the same temperature,
ordinarily taken to be 25 ºC unless specified otherwise.

EXAMPLE

Indicate whether each of the following reactions is exothermic or endothermic:

a) Br2 (l) + Cl2 (g) 2 BrCl (g) ∆ H = + 29.4 kJ endothermic
b) NH3 (g) + HCl (g) NH4Cl (s) ∆ H = – 176 kJ exothermic
c) N2O4 (g) 2 NO2 (g) ∆ H = + 58.0 kJ endothermic
d) CS2 (l) + 3 Cl2 (g) CCl4 (l) + S2Cl2(l) ∆ H = – 112 kJ exothermic

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? SAQ 4
1. Indicate whether each of the following reactions if exothermic or endothermic:
a) 2 NaN3 (s) 2 Na (s) + 3 N2 (g) ∆ H = + 42.7 kJ
b) 2 KClO3 (s) 2 KCl (s) + 3 O2 (s) ∆ H = – 89.4 kJ
c) SnCl2 (s) + Cl2 (s) SnCl4 (l) ∆ H = – 195.4 kJ
d) 2 HgO (s) 2 Hg (l) + O2 (g) ∆ H = + 181.4 kJ

Bond Energies
Atoms are held together in molecules by chemical bonds. The energy required to break the
bond that holds two atoms together in a diatomic molecule is called the bond dissociation
energy. These values are reported in kilojoules per mole of bonds. In the following equations,
which illustrate this process, dashes are used to represent the bonds between atoms; H 2, for
example, appears as H – H:

H – H(g) 2 H(g) ∆ H = +435 kJ

Cl – Cl(g) 2 Cl(g) ∆ H = +243 kJ
H – Cl(g) H(g) + Cl(g) ∆ H = +431 kJ

Each of these ∆ H values is positive, which indicates that energy is absorbed in each process.
The bond in the H2 molecule is the strongest of the three. It takes the most energy to pull the
atoms of the H2 molecule apart.
If one of these equations is reversed, the sign of the ∆ H value must be changed:

H(g) + Cl(g) H – Cl(g) ∆ H = –431 kJ

When a bond forms, energy is released – the same amount that is required to break the bond.
Bond dissociation energies may be used to determine some ∆ H values. Consider the
reaction:

H(g) + Cl(g) 2HCl(g) ∆ H = 2∆ H ° f = –184.6 kJ

The ∆ H values for this reaction is twice the enthalpy of formation of HCl(g), since the equation
indicates the formation of two moles of HCl(g). We can derive this ∆ H value from the bond
dissociation energies in the following way. The enthalpy change is the sum of the ∆ H values for
the energy required to break 1 mol of H – H bonds, the energy required to break 1 mol of Cl – Cl
bonds, and the energy evolved by the formation of 2 mol of H – Cl bonds:

H – H(g) 2 H(g) ∆ H = +435 kJ

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Cl – Cl(g) 2 Cl(g) ∆ H = +243 kJ

2H(g) + 2 Cl(g) 2 H – Cl(g) ∆ H = 2(–431 kJ) = – 862 kJ

The sum of these equations is:

H – H(g) + Cl – Cl(g) 2 H – Cl(g) ∆ H = –184 kJ

In this example, the total energy evolved by bond formation (∆ H = – 862 kJ) exceeds the total
energy required for bond breaking (∆ H = +435 kJ + 243 kJ = +678 kJ). The reaction,
therefore, is exothermic.
In endothermic reactions, the reverse is true. More energy is required to break bonds
than is released when new bonds form. Consider the reactions:

N2(g) + O2(g) 2 NO(g) ∆ H = 2∆ H ºf = +180.74 kJ

None of the bonds in these molecules is a single bond, and we will not use dashes to indicate
them. The bond dissociation energies for the three diatomic molecules indicated in the equation,
however, have been determined and can be used to find the ∆ H for the reaction.
The total energy required to break the bonds in the N 2(g) and O2(g) molecules is the sum
of the bond dissociation energies of the two molecules:

N2(g) 2 N(g) ∆ H = +941 kJ

O2(g) 2 O(g) ∆ H = +494 kJ_
total energy to break bonds = +1435 kJ

The ∆ H for the energy evolved by the formation of 2 mol of NO(g) is obtained by multiplying the
bond dissociation energy of the NO(g) molecule by 2 and changing the sign:

2 NO(g) + 2 O(g) 2 NO(g) ∆ H = 2(– 627 kJ) = – 1254 kJ

Total energy to form bonds = – 1254 kJ

The ∆ H value for the reaction is derived by adding the ∆ H values for the bonds broken and
the bonds formed. Since more energy is required to break bonds than is released by bond
formulation, the reaction is endothermic:

∆ H = +1435 kJ – 1254 kJ = +181 kJ

N2(g) + O2(g) 2 NO(g) ∆ H = +181 kJ

This method would be extremely limited if we were restricted to the use of bond dissociation
energies for diatomic molecules. Instead, the system is extended by deriving approximate bond
energy values for the bonds found in other types of molecules.
A molecule that contains more than two atoms, such as H2O, is called a polyatomic
molecule. There are two H – O bonds in the H 2O molecule, and dissociation of the H2O
molecule into atoms involves breaking these two H – O bonds. The ∆ H for the reaction:

H – O – H(g) 2 H(g) + O(g) ∆ H = +926 kJ

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Table A: Average bond energies (kJ/mol) a

Bond Average Bond Bond Average Bond
Energy Energy
Br – Br 193 H–I 297
C–C 347 I–I 151
C=C 619 N – Cl 201
C C 812 N–H 389
C – Cl 326 N–N 159
C–F 485 N=N 418
C–H 414 N N 941
C–N 293 O – Cl 205
C=N 616 O–F 184
C N 879 O–H 463
C–O 335 O–O 138
C=O 707 Ob2 494
Cl – Cl 243 P – Cl 326
F–F 155 P–H 318
H – Br 364 S – Cl 276
H – Cl 431 S–H 339
H–F 565 S–S 213
H–H 435
Reactants and products in gaseous state.
Double bond of molecular oxygen.

refers to a process in which two moles of H – O bonds are broken. The average bond energy
of the H – O bond, therefore, is +926 kJ/(2 mol), or +463 kJ/mol.
In the H2O molecule, the H – O bonds are equivalent. If the bonds were broken one at a
time, however, at the ∆ H values would not be the same.

H – O – H(g) H(g) + O – H(g) ∆ H = +501 kJ

O – H(g) O(g) + H(g) ∆ H = +425 kJ

In general, the second of a molecule such as H2O is easier to break than the first. The fragment
remaining after one H has been removed (O – H) is not so stable as the original molecule (H –
O – H). The ∆ H values for the individual steps given above are not important to us. The
average of the ∆ H values for the steps is +463 kJ/mol, which is the average bond energy and
the value used in calculations involving the H – O bond.
The strength of a bond in a molecule depends upon the structure of the entire molecule.
Consequently, the bond energy of a given type of bond is not the same in all molecules
containing that bond. For example, the H – O bond energy in the H – O – Cl molecule. The
values listed in Table A for diatomic molecules are bond dissociation energies. The other values
listed are average bond energies, and each of these values is an average derived from a large
number of cases. Since many bond energies are approximations, a ∆ H value obtained by use
of these values must be regarded as an estimate.
In some molecules, two atoms are bonded together by multiple bonds. Two nitrogen
atoms, for example, can be joined by a single bond (N – N), a double bond (N =N), or a triple
bond (N N), depending on the molecule. Multiple bonds are indicated in Table A. Notice that

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the bond energy increases in the order: single bond < double bond < triple bond in a series of
this type:

N – N +159 kJ/mol C – C +347 kJ/mol C – N +293 kJ/mol

N = N +418 kJ/mol C = C +619 kJ/mol C = N +616 kJ/mol
N N +941 kJ/mol C C +812 kJ/mol C N +879 kJ/mol

Three factors should be kept in mind when bond energies are used to determine a ∆ H for
a reaction.

1. The method as presented should be used only for reactions in which all reactants and
products are gases.*
2. The results of calculations for this type should be regarded as estimates because the
values for many bond energies are approximations.
3. At times, the bond energies for certain bonds that cannot be simply defined do no fir into
the general pattern of average bond energies.

Example
Use average bond energies to calculate the value of ∆ H for the reactions:
H
|
2 H – N – H(g) + 3 Cl – Cl(g) N N(g) + 6 H – Cl(g)

Solution
We can imagine the reaction to take place in a series of steps. Energy is absorbed ( ∆ H is
negative) when a bond is formed. Six moles of N – H bonds are broken:
H
|
2 H – N – H(g) 2 N(g) + 6 H(g) ∆ H = 6(+389 kJ) = +2334kJ

Three moles of Cl – Cl bonds are broken:

3 Cl – Cl(g) 6 Cl(g) ∆ H = 3(+243 kJ) = +729 kJ

One mole of N N bonds is formed:

2 N(g) N N(g) ∆ H = –941 kJ

Six moles of H – Cl bonds are formed:

6 H(g) + 6 Cl(g) 6 H – Cl(g) ∆ H = 6(–431 kJ) = –2586 kJ

The sum of these steps is the answer to our problem:

2 NH3(g) + 3 Cl2(g) N2(g) + 6 HCl(g) ∆ H = –464 kJ

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The solution to this problem can be indicated in a briefer manner. We list all of the bonds
that are broken (∆ H values will be positive) and all of the bonds that are formed (∆ H values
will be negative). The answer is the of the list. Thus,

Bonds broken: ∆ H:
6 mol of N – H bonds 6 mol(+389 kJ/mol) = +2334 kJ
3 mol of Cl – Cl bonds 3 mol(+243 kJ/mol) = +729 kJ

Bonds formed:
1 mol of N N bonds 1 mol(–941 kJ/mol) = –941 kJ
6 mol of H – Cl bonds 6 mol(–431 kJ/mol) = –2586 kJ
Results: –464 kJ
The value obtained in this way (–461 kJ) is more than reliable value than the one derived from
bond energies (–464 kJ).

? SAQ 5
1. Use average bond energies (Table A) to calculate ∆ H for the reaction:

H H
| |
H – C = C – H(g) + H – H(g) H – C – C – H(g)
| | | |
H H H H

2. Use average bond energies (Table A) to calculate ∆ H for the reaction:

4 H – Cl(g) + O2(g) 2 H – O – H(g) + 2 Cl – Cl(g)

3. Use average bond energies (Table A) to calculate ∆ H for the reaction

H H
| |
H–C N(g) + 2 H – H(g) H – C – N(g)
| |
H H

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Summary
Bond energy. The energy required to break a bond between two atoms in a molecule. This
general term includes two types of measurements. A bond dissociation energy refers to the
energy required to break a specific bond that holds two atoms together in a particular diatomic
molecule. An average bond energy, however, pertains to the bonds found in polyatomic
molecules and is an average value based on a number of cases.

Calorimeter. A device used to measure the heat transferred in chemical reactions and physical
changes.

Energy. The capacity to do work.

Enthalpy. The heat content of a sample of matter; for a reaction run at constant pressure, the
change in enthalpy, ∆ H , is the heat transferred (liberated or absorbed).

Heat. The form of energy that flows spontaneously from a body at a higher temperature to a
body at a lower temperature.

Heat capacity. The amount of heat required to raise the temperature of a given mass by 1 ºC.

Specific heat. The amount of heat required to raise the temperature of 1 g of a substance by 1
ºC.

Temperature. Degree of hotness or coldness; that property of matter that determines the
direction in which heat flows spontaneously.

Thermochemistry. Study of the energy changes that accompany chemical and physical
changes.

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References

Brown, Le May and Bursten, Burdge, 2004, Chemistry The Central Science (9 th edition),
Pearson Education (Asia) Pte Ltd.

Cengage Learning Asia Ltd., 2019, General Chemistry 2 (Philippine edition),

Rex Book Store Inc.

Malone, Leo J., Dolter, Theodore D., 2010, Basic Concepts of Chemistry (8 th edition),
John Wiley and Sons, Inc.

Masterton, William L., Hurley, Cecile H., Peterson, James F., Sack, Dorothy. Gabler,
Robert E., 2018, Chemistry for Engineering Students (Philippine edition),
C & E Publishing, Inc.

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Answer of Self-Assessment Questions (ASAQ)

SAQ 1
1) 1046 J/ ºC
2) 18.8 kJ
3) 2.46 J/g · ºC
4) 144 J
5) 26.74 ºC

SAQ 2
1) No
2) – 669
3) 24.2 ºC

SAQ 3
1) a. 81.3 kJ
b. 86.2 kJ
c. – 167.5 kJ
d. – 3.48 x 103 kJ/mol.

SAQ 4
1) a. endothermic
b. exothermic
c. exothermic
d. endothermic

SAQ 5
1) ∆ H = – 121 kJ
2) ∆ H = – 120 kJ
3) ∆ H = – 150 kJ

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THERMOCHEMISTRY
MASTERY TEST
Multiple Choice:
1) What mass of water has a heat capacity of 379 J/ ºC?
a. 91.48 g
b. 81.38 g
c. 90.58 g
d. 80.68 g
2) How many kilojoules of heat will raise the temperature of 21.3 kg of water from 21.00 ºC
to 25.71 ºC?
a. 410.75 kJ
b. 329.55 kJ
c. 310.65 kJ
d. 419.75 kJ
3) What is the specific heat of iron if 186 J of heat is required to raise the temperature of
165 g of iron from 23.20 ºC to 25.70 ºC?
a. 0.451 J/g · ºC
b. 0.541 J/g · ºC
c. 0.145 J/g · ºC
d. 0.345 J/g · ºC
4) Gold has a specific heat of 0.129 J/g · ºC. When a 5.00 g piece of gold absorbs 1.33 J of
heat, what is the change in temperature?
a. 3.26 ºC
b. 1.36 ºC
c. 4.16 ºC
d. 2.06 ºC
5) Mercury was once used in thermometers and barometers. When 46.9 J of heat are
absorbed by 100.0 g of mercury at 25.00 ºC, the temperature increases to 28.35 ºC.
What is the specific heat of mercury?
a. 0.204 J/g · ºC
b. 0.140 J/g · ºC
c. 2.041 J/g · ºC
d. 2.104 J/g · ºC

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6) Chromium has a specific heat of 0.450 J/ g · ºC. How much heat is absorbed by 35.0 g
of chromium if the temperature increases from 45 ºF to 88 ºF?
a. 370 J
b. 460 J
c. 190 J
d. 280 J
7) Ethyl alcohol, C2H5OH, is the intoxication agent in liquor. Burning 1.00 g of ethyl alcohol
in an excess of oxygen at 23.28 ºC and constant volume releases 29.52 kJ of heat.
When 7.40 g of ethyl alcohol is burned in oxygen under the same conditions in a bomb
calorimeter, the temperature of the bomb ad water rises from 23.28 ºC to 48.04 ºC. The
bomb holds 0.750 kg of water.
a. What is q for the combustion of the ethyl alcohol in the bomb calorimeter?
a) – 318 kJ
b) – 418 kJ
c) – 218 kJ
d) – 518 kJ
b. What is qH2O?
a) 82.6 kJ
b) 59.4 kJ
c) 68.3 kJ
d) 77.6 kJ
c. What is qcal?
a) 110 kJ
b) 120 kJ
c) 130 kJ
d) 140 kJ
d. What is the heat capacity of the calorimeter?
a) 4.69 kJ/ ºC
b) 6.24 kJ/ ºC
c) 5.67 kJ/ ºC
d) 3.29 kJ/ ºC

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8) Write the thermochemical equation for the reaction between one mole of nitrogen oxide
(NO) and oxygen (O2) to give the brown gas NO 2. When one mole of NO reacts with
oxygen 57.0 kJ of heat are evolved.
a. 2 NO + O2 2 NO2 ∆H = – 57.0 kJ
b. NO + ½ O2 NO2 ∆H = + 57.0 kJ
c. NO + ½ O2 NO2 ∆H = – 57.0 kJ
d. 2 NO + O2 2 NO2 ∆H = + 57.0 kJ
9) Use the bond energies to calculate the value of ∆ H for the reaction:
H
|
H–C–H + 2O–O O=C=O + 2H–O–H
|
H

a. – 1330 kJ
b. + 1330 kJ
c. – 1130 kJ
d. + 1130 kJ
10) Use the bond energies to calculate the value of of ∆ H for the reaction:
H
|
3H–H + N N 2H–N–H.

a. – 88 kJ
b. + 88 kJ
c. – 98 kJ
d. + 98 kJ

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