Chapter 5

Principles of Chemical
Reactivity:
Energy and Chemical
Reactions
 Chapter Outline
5-1 Energy: Some Basic Principles

5-2 Specific Heat Capacity: Heating and Cooling

5-3 Energy and Changes of State

5-4 The First Law of Thermodynamics

5-5 Enthalpy Changes for Chemical Reactions

5-6 Calorimetry

5-7 Enthalpy Calculations

5-8 Product- or Reactant-Favored Reactions and Thermodynamics

 Energy & Chemistry
Questions that need to be addressed:
• How do we measure and calculate the energy changes
that are associated with physical changes and chemical
reactions?

• What is the relationship between energy changes, heat,

and work?

• How can we determine whether a chemical reaction is

product-favoured or reactant-favoured at equilibrium?

• How can we determine whether a chemical reaction or

physical change will occur spontaneously, that is, without
outside intervention?
 Energy & Chemistry
Some Basic Principles
•Energy has the capacity to do work or transfer heat (q).
•Energy is divided into two basic categories:
Kinetic energy (the energy associated with motion) thermal,
mechanical, electrical
Potential energy (‘stored’ energy that results from an object’s
position) gravitational, electrostatic, chemical, nuclear

• The law of conservation of energy states that energy can neither be

created nor destroyed. However, energy can be converted from one
form into another.

Note: Heat (q) is NOT temperature, temperature is a measure of kinetic energy.

 Energy & Chemistry
1 calorie = heat required to raise temp. of
1.00 g of H2O by 1.0 °C.
1000 cal = 1 kilocalorie = 1 kcal
1 kcal = 1 Calorie (a food “calorie”)

James Joule
1818-1889

SI units for energy: joule (J)

1 cal = exactly 4.184 J
Energy & Chemistry

SYSTEM
A system is defined as an object, or
collection of objects, being studied.

SURROUNDINGS
The surroundings include everything
outside the system that can exchange
energy and/or matter with the
system.

Energy flows between the system and

its surroundings.
 Directionality of Energy Transfer
•When energy leaves the system and goes into the surroundings, the
process is said to be EXOTHERMIC.
•In the case of thermal energy, the temperature of the system
decreases. (qsystem < 0). Hence, ∆Tsystem = (Tfinal – Tinitial) < 0

•When energy enters the system and from the surroundings, the process
is said to be ENDOTHERMIC.
•In the case of thermal energy, the temperature of the system increases.
(qsystem > 0). Hence, ∆Tsystem = (Tfinal – Tinitial) > 0
 Specific heat capacity: Heating and cooling
When an object is heated or cooled, the quantity of energy
transferred depends on three things:
• the quantity of material
• the magnitude of the temperature change
• the identity, including the phase (g, l, aq, or s) of the
material gaining or losing energy.
Specific heat capacity (C) is defined as the
energy transferred as heat that is required to
raise the temperature of 1 gram of a substance
by one Kelvin. It has units of joules per gram per
Kelvin (J/g ⋅ K).

Heat capacity can also be expressed on a per-mole basis. The amount of

energy that is transferred as heat in raising the temperature of one mole
of a substance by one Kelvin is the molar heat capacity (J/mol ⋅ K).
 Heat Capacity
The energy gained or lost as heat when a given mass of a
substance is warmed or cooled can be calculated using

∆T, is calculated as the final temperature minus the initial temperature.

 Specific Heat Capacity
How much energy must be transferred to raise the temperature of a
cup of coffee (250 mL) from 20.5 °C (293.7 K) to 95.6 °C (368.8 K)?
Assume that water and coffee have the same density (1.00 g/mL) and
specific heat capacity (4.184 J/g ⋅ K).
 Specific heat capacity

Let’s define the metal

and the water as the
system and the beaker
and environment as the
surroundings and
assume that energy as
heat is transferred only
within the system.

• Energy transfer (as heat) will occur spontaneously from an object at a

higher temperature to an object at a lower temperature.
• Transfer of energy (as heat) continues until both objects are at the
same temperature and thermal equilibrium is achieved.
• At thermal equilibrium, the object with a temperature increase has
gained thermal energy, the object with a temperature decrease has
lost thermal energy.
 Specific Heat Capacity
Because of the law of conservation of energy, in an isolated system the
sum of the energy changes within the system must be zero. If energy is
transferred only as heat, then

Since there are thermal energy changes associated with the two components
of the system, water and metal, qwater and qmetal; thus

Each of these quantities is related individually to specific heat capacities,

masses, and changes of temperature, as defined by

The specific heat capacity of the metal, Cmetal , is the unknown in this problem.
 Thermal Equilibrium
In an experiment, a 88.5 g piece of iron whose temperature is 78.8 °C
(352.0 K) is placed in a beaker containing 244 g of water at 18.8 °C
(292.0 K). When thermal equilibrium is reached, what is the final
temperature? (Assume no energy is lost to warm the beaker and its
surroundings.)

If we define the system as the iron and water, the sum of these two energy
quantities will be zero. The final temperature is the unknown in this problem.
 Energy and changes of state
A change of state is a change, for example, between solid and liquid or
between liquid and gas. When a solid melts, its atoms, molecules, or
ions move about vigorously enough to break free of the attractive
forces holding them in rigid positions in the solid lattice.

The temperature is constant throughout a change of state. During a change of

state, the added energy is used to overcome the forces holding one molecule
to another, not to increase the temperature.
Heating/cooling curve for water

exothermic

endothermic
 Heat & changes of state
The energy associated with a change of state is given by the Enthalpy or
Heat of the phase change.
Since there is no temperature change associated with the process, the
units are most often in J/g or J/mol.

Sublimation: ∆subH > 0 (endothermic)

Vaporization: ∆vapH > 0 (endothermic)
Melting or Fusion: ∆fusH > 0 (endothermic)
Deposition: ∆depH < 0 (exothermic)
Condensation: ∆conH < 0 (exothermic)
Freezing: ∆freH < 0 (exothermic)

Where ∆H refers to the “heat” of a phase change

 Heat & changes of state

Energy change (q) during heating or cooling

Heat absorbed or lost during a phase change:

C, specific heat capacity (J/g.K)

q, energy (J)
T, temperature (K or ◦C)
n, moles (mol) or m, grams (g)
H, heat (J/g or J/mol)
 Energy & Changes of State
Calculate the energy needed to convert 500. g of ice at −50.0 °C to
steam at 200.0 °C (Figure 5.7). The heat of fusion of water is 333 J/g,
and the heat of vaporization is 2256 J/g. The specific heat capacities are:
ice (2.06 J/g.K), liquid water (4.184 J/g.K), and water vapor (1.86 J/g.K).

Step 1. (to warm ice from −50.0 °C to 0.0 °C)

Step 2. (to melt ice at 0.0 °C)

Step 3. (to raise temperature of liquid water from 0.0 °C to 100.0 °C)
 Energy & Changes of State
Calculate the energy needed to convert 500. g of ice at −50.0 °C to
steam at 200.0 °C (Figure 5.7). The heat of fusion of water is 333 J/g,
and the heat of vaporization is 2256 J/g. The specific heat capacities of
ice, liquid water, and water vapour are given in Appendix D.

Step 4. (to evaporate water at 100.0 °C)

Step 5. (to raise temperature of water vapour from 100.0 °C to 200.0 °C)

The total energy transferred as heat is the sum of the individual energies.
 First Law of Thermodynamics
Thermodynamics is the science of heat and work.
Work done by a system or on a system will also affect the energy in the
system.

The system is the CO2; initially a solid and later a gas

The surroundings are the plastic bag, the book, the table-top, and the surrounding air

An energy balance for the system will include both quantities, energy
transferred as heat and energy transferred as work.
 First Law of Thermodynamics
For any system, we can identify energy transfers both as heat and as
work between the system and surroundings.
From the first law of thermodynamics: When a system undergoes a physical or
chemical change, the change in internal energy is given by the heat added to or
absorbed by the system plus the work done on or by the system:
Change in internal Energy transferred as
energy content work to or from the
system
Energy transferred
as heat to or from
the system
The equation tells us how to determine ∆U: Measure the energy transferred as
heat and work to or from the system.

NOTE: The sign conventions for the equation are important.

 Sign conventions for q and w of the system

energy transfer in energy transfer out

(endothermic), (+q) (exothermic), (-q)

SYSTEM

work transfer in (+w) work transfer out (-w)

 Pressure–Volume (PV) Work
Consider the work done by a system on its
surroundings (or vice versa) when the volume of a
system changes.

A gas is sealed in a cylinder with a movable piston. If

the gas in the cylinder is heated, it expands, pushing
the piston upward until the internal gas pressure
equals the (constant) downward external pressure
applied by the piston and the atmosphere.

Ideally, the piston moves without friction, so that

none of the work done by an expanding gas is lost.
 Pressure–Volume (PV) Work
The work required to move the piston is calculated
using w = F × d

Pressure is defined as a force divided by the area over

which the force is applied: P = F/A

Substituting P × A for F in the equation for work gives

w = (P × A) × d

The product of A × d is equivalent to the change in the

volume of the gas in the cylinder, and, because ∆V =
Vfinal − Vinitial, this change in volume is positive when
the gas expands.

Finally, because work done by a system on the

surroundings is defined as negative, this means that w
= −P∆V.
 Pressure–Volume (PV) Work
Work is calculated using the SI units of pressure and volume. The SI unit
of pressure is pascal (1 Pa = 1 kg/m ⋅ s2), which when multiplied by the
volume change in m3, gives energy in joules (1 J = 1 kg ⋅ m2/s2).

w = -P × ∆V
Work (at constant pressure) pressure Change in volume

If energy is transferred in a constant-volume process, ∆V = 0. This means the

energy transferred as work will also be zero. Thus, the change in internal
energy of the system under constant-volume conditions is equal only to the
energy transferred as heat (qv).
∆U = qv + wv (at constant volume)

∆U = qv+ 0 when wv= 0 because ∆V = 0

and so ∆U = qv
 Enthalpy
Enthalpy, “H” is the heat transferred between the system and
surroundings under conditions of constant pressure.
Under conditions of constant pressure;
If the only type of work that occurs is P–V work, then;
Rearranging,
Introducing the Enthalpy term gives;
The change in enthalpy for a system at constant pressure can be calculated
from the following equation:
if no “PV” work is done by
the system, the change in
Then, enthalpy is the change in
internal energy at constant
pressure.

∆H < 0: energy is transferred as heat from the system to the surroundings.

∆H > 0: energy is transferred as heat from the surroundings to the system.
 Enthalpy & work
Nitrogen gas (1.50 L) is confined in a cylinder under constant atmospheric
pressure (1.01 × 105 pascals). The gas expands to a volume of 2.18 L when
882 J of energy is transferred as heat from the surroundings to the gas.
What is the change in internal energy of the gas?
Convert liters (L) to cubic meters m3

The work done by the system is

The change in internal energy is calculated.

 State functions
Internal energy and enthalpy share a significant characteristic, namely,
changes in these quantities depend only on the initial and final states.
There are many ways to climb a
A quantity that has this property is called a
mountain, but the change in
state function. They do not depend on the altitude from the base of the
path taken on going from the initial state to mountain to its summit is the
the final state. No matter how you go from same.
reactants to products in a reaction the values
of ∆H and ∆U are always the same.
∆H = Hfinal - Hinitial
∆U = Ufinal - Uinitial
∆T = Tfinal - Tinitial

The change in altitude is a state

function.
The distance traveled to reach the
summit is not.
 Enthalpy conditions

• Since enthalpies are state functions, one must

specify the conditions at which they are measured.

• H(T,P): enthalpy is a function of temperature and

pressure.

• H° indicates that the enthalpy is taken at Standard

State conditions.

• Standard state conditions are defined as:

1 atm = 760 mm Hg or 760 torr & 298.15 K or 25 °C
 Enthalpies & chemical reactions: ∆rH
Enthalpy changes accompany chemical reactions.
The standard reaction enthalpy, ∆rH °, for the decomposition of water vapour
to hydrogen and oxygen at 25 °C is +241.8 kJ/mol-rxn (moles of reaction).

The reverse reaction represents the combination of hydrogen and oxygen to

form 1 mol of water. The magnitude of the enthalpy change for this reaction is
the same as that for the decomposition reaction, but the sign of ∆rH° is
reversed.
 Enthalpies & chemical reactions: ∆rH
Suppose you want to know the energy transferred to the surroundings
as heat if 454 g of propane, C3H8, is burned (at constant pressure),
given the equation for the exothermic combustion and the enthalpy
change for the reaction.

First, find the amount of propane present in the sample:

Use ∆rH° to determine ∆H° for this amount of propane:

 Calculating the enthalpy change for a reaction
Problem: Sucrose (table sugar, C12H22O11) can be oxidized to CO2 and
H2O, and the enthalpy change for the reaction can be measured.
C12H22O11(s) + 12 O2(g) → 12 CO2(g) + 11 H2O(l) ∆rH° = −5645 kJ/mol-rxn
What is the enthalpy change when 5.00 g of sugar is burned under conditions
of constant pressure?
Solution:
Balance equation and calculate the amount of 5g of sucrose (in moles)
.
 Calorimetry: constant pressure calorimetry,
Measuring ∆H
Styrofoam (an insulator) minimizes energy transfer
as heat between the system and the surroundings. If
the reaction is exothermic, energy is released as
heat to the solution, increasing the solution
temperature. If the reaction is endothermic, energy
is absorbed as heat from the solution, decreasing
the solution temperature.

Knowing the mass and specific heat capacity of the

solution and the temperature change, the enthalpy
change for the reaction can be calculated.
The constant-pressure “coffee-cup
calorimeter” is used in chemistry
The chemicals and solution is the system; the laboratories. This device consists of
surroundings are the cup and everything beyond the two nested Styrofoam coffee cups
cup. We assume there is no energy transfer to the with a loose-fitting lid and a
cup or beyond and that energy is transferred only as thermometer which measures any
temperature changes. The reaction is
heat within the system. carried out in solution in the cup.
 Calorimetry: constant pressure calorimetry,
Measuring ∆H
Two energy changes occur within the system.
Firstly, the change that takes place as the
chemical reaction occurs, either releasing the
potential energy stored in the reactants or
absorbing energy and converting it to potential
energy stored in the products; this energy is qr.
Secondly, the energy change gained or lost as
heat by the solution (qsolution). Based on the law of
conservation of energy,

qr + qsolution = 0

The value of qsolution is calculated from the specific

heat capacity, mass, and change in temperature
of the solution. The quantity of energy evolved or
absorbed as heat for the reaction (qr) is the
unknown in the equation.
 Using a coffee-cup calorimeter
Suppose you place 0.0500 g of magnesium chips in a coffee-cup calorimeter
and then add 100.0 mL of 1.00 M HCl. The reaction that occurs is
Mg(s) + 2 HCl(aq) → H2(g) + MgCl2(aq)
The temperature of the solution increases from 22.21 °C (295.36 K) to 24.46 °C (297.61
K). What is the enthalpy change for the reaction per mole of Mg? Assume that the
specific heat capacity of the solution is 4.20 J/g · K and the density of the HCl solution
is 1.00 g/mL.
Step 1. Calculate the amount of Mg.

Step 2. Calculate qsolution. The mass of the solution is the mass of the 100.0 mL
of HCl plus the mass of magnesium.
 Using a coffee-cup calorimeter
Suppose you place 0.0500 g of magnesium chips in a coffee-cup calorimeter
and then add 100.0 mL of 1.00 M HCl. The reaction that occurs is
Mg(s) + 2 HCl(aq) → H2(g) + MgCl2(aq)
The temperature of the solution increases from 22.21 °C (295.36 K) to 24.46 °C (297.61
K). What is the enthalpy change for the reaction per mole of Mg? Assume that the
specific heat capacity of the solution is 4.20 J/g · K and the density of the HCl solution
is 1.00 g/mL
Step 3. Calculate qr. qr + qsolution = 0

qr + 945 J = 0

qr = −945 J
Step 4. Calculate the value of ∆rH per mole of Mg. The value of qr found in Step
2 resulted from the reaction of 0.00206 mol of Mg. The enthalpy change per
mole of Mg is therefore;
Constant volume calorimetry. Measuring ∆U
The two types of calorimetry (constant volume and constant pressure)
highlight the differences between enthalpy and internal energy. The
energy transferred as heat at constant pressure, qp, is, by definition, ∆H,
whereas the energy transferred as heat at constant volume, qv , is ∆U.

Heats of combustion (∆rUcombustion) are

measured using a device called a Bomb
Calorimeter.

A combustible sample is burned in pure oxygen in a sealed

metal container or “bomb.” Energy transferred as heat from
the reaction warms the bomb and the water surrounding it.
By measuring the increase in temperature, the energy
transferred as heat in the reaction can be determined.
Constant volume calorimetry. Measuring ∆U
The bomb, its contents, and the water are defined as the system.
Assessment of energy transfers as heat within the system shows that;
qr + qbomb + qwater = 0
-qr = qbomb + qwater
where qr is the energy released as heat by
the reaction, qbomb is the energy involved in
heating the calorimeter bomb, and qwater is
the energy involved in heating the water in
the calorimeter.

Since the volume does not change in a

constant-volume calorimeter, energy
transfer as work does not occur. Therefore,
the energy transferred as heat at constant
volume (qv) is equal to the change in
internal energy, ∆U.
 Using the bomb calorimeter
Octane, C8H18, a primary constituent of gasoline, burns in air:
C8H18(l) + 25/2 O2(g) → 8 CO2(g) + 9 H2O(l)
A 1.00 g sample of octane is burned in a constant-volume calorimeter containing 1.20 kg of
water. The temperature of the water and the bomb rises from 25.00 °C (298.15 K) to 33.20 °C
(306.35 K). The heat required to raise the bomb’s temperature (its heat capacity), Cbomb , is 837
J/K. (a) What is the heat of combustion per gram of octane? (b) What is the heat of combustion
per mole of octane?
(a)

(b) Heat of combustion per mole of octane = (−48.1 kJ/g)(114.2 g/mol) = −5.49 × 103 kJ/mol
 Enthalpy calculations: Hess’s law
Not all enthalpy changes in chemical processes can be measured directly
using calorimetry. For example, consider the oxidation of carbon to form
carbon monoxide.
C(s) + 1/2 O2(g) → CO(g)
•The primary product of the reaction will be CO2, even if a deficiency of oxygen
is used. As soon as CO is formed, it will react with O2 to form CO2.

•It is not possible to measure the change in enthalpy for this reaction by
calorimetry because, the reaction cannot be carried out in a way that allows
CO to be formed.

•The enthalpy change for the reaction forming CO(g) from C(s) and O2(g) can
be determined indirectly, from enthalpy changes for other reactions for which
values of ∆rH° can be measured.

•The calculation is based on Hess’s law, which states that if a reaction is the
sum of two or more other reactions, ∆rH° for the overall process is the sum of
the ∆rH° values of those reactions.
 Enthalpy calculations: Hess’s law
The oxidation of C(s) to CO(g) can be determined indirectly from
thermochemical data obtained from two reactions that can be studied by
calorimetry.
These reactions are the oxidation of CO(g) and the oxidation of C(s), both of
which form CO2(g) as the sole product.

Equation 1: CO(g) + ½ O2(g) → CO2(g) ∆rH°1 = −283.0 kJ/mol-rxn

Equation 2: C(s) + O2(g) → CO2(g) ∆rH°2 = −393.5 kJ/mol-rxn
The equations above can be manipulated so that when added together they
yield the desired net equation. Decomposition rxn
Equation 1′: CO2(g) → CO(g) + ½ O2(g) ∆rH°1′ = +283.0 kJ/mol-rxn
Equation 2: C(s) + O2(g) → CO2(g) ∆rH°2 = −393.5 kJ/mol-rxn
_______________________________________________________________
Equation 3: C(s) + ½O2(g) → CO(g) ∆rH°3 = −110.5 kJ/mol-rxn

Hess’s law tells us that the enthalpy change for the overall reaction (∆rH°3) will
equal the sum of the enthalpy changes for reactions 1′ and 2 (∆rH°1′ + ∆rH°2).
 Enthalpy Calculations: Hess’s Law
Hess’s law also applies to physical processes.

The enthalpy change for the reaction of H2(g) and O2(g) to form 1 mol of H2O
vapour is different from the enthalpy change to form 1 mol of liquid H2O. The
difference is the negative of the enthalpy of vaporization of water, ∆rH°2 (=
−∆vapH°).

Equation 1: H2(g) + ½O2(g) → H2O(g) ∆rH°1 = −241.8 kJ/mol-rxn

Equation 2: H2O(g) → H2O(l) ∆rH°2 = −44.0 kJ/mol-rxn

_______________________________________________________________
Equation 3: H2(g) + ½ O2(g) → H2O(l) ∆rH°3 = −285.8 kJ/mol-rxn
 Energy level diagrams
The enthalpy change for a reaction is a state function; that is, the
enthalpy change from reactants to products does not depend on the
path taken.

Both liquid and gaseous water have lower enthalpies, with the difference
between the two being the enthalpy of vaporization.
 Enthalpy calculations: Hess’s law
Problem:
Suppose you want to know the enthalpy change for the formation of methane,
CH4, from solid carbon (as graphite) and hydrogen gas:
C(s) + 2 H2(g) → CH4(g) ∆rH° = ?

The enthalpy change for this reaction cannot be measured in the laboratory
because the reaction is very slow. We can, however, measure enthalpy changes
for the combustion of carbon, hydrogen, and methane.

Equation 1: C(s) + O2(g) → CO2(g) ∆rH°1 = −393.5 kJ/mol-rxn

Equation 2: H2(g) + 1⁄2 O2(g) → H2O(l) ∆rH°2 = −285.8 kJ/mol-rxn
Equation 3: CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(l) ∆rH°3 = −890.3 kJ/mol-rxn

Use this information to calculate ∆rH° for the formation of methane from its
elements.
 Enthalpy calculations: Hess’s law

C(s) + 2 H2(g) → CH4(g) ∆rH° = ?

Equation 3′: CO2(g) + 2 H2O(l) → CH4(g) + 2 O2(g)

∆rH°3′ = −∆rH°3 = +890.3 kJ/mol-rxn

Next, you see that 2 mol of H2(g) is on the reactant side in our desired equation.
Equation 2 is written for only 1 mol of H2(g) as a reactant. Therefore, multiply the
stoichiometric coefficients in Equation 2 by 2 and multiply the value of its ∆rH° by 2.

Equation 2′: 2 H2(g) + O2(g) → 2 H2O(l)

∆rH°2′ = 2 ∆rH°2 = 2 (−285.8 kJ/mol-rxn) = −571.6 kJ/mol-rxn
 Enthalpy calculations: Hess’s law
You now have three equations that, when added together, will give the
equation for the formation of methane from carbon and hydrogen. In this
summation process, O2(g), H2O(l), and CO2(g) all cancel.

Equation 1: C(s) + O2(g) → CO2(g) ∆rH°1 = −393.5 kJ/mol-rxn

Equation 2′: 2 H2(g) + O2(g) → 2 H2O(l) ∆rH°2′ = 2 ∆rH°2 = −571.6 kJ/mol-rxn

Equation 3′: CO2(g) + 2 H2O(l) → CH4(g) + 2 O2 (g)

∆rH°3′ = −∆rH°3 = +890.3 kJ/mol-rxn
Net Equation: C(s) + 2 H2(g) → CH4(g)
∆rH°net = ∆rH°1 + ∆rH°2′ + ∆rH°3′

∆rH°net = (−393.5 kJ/mol-rxn) + (−571.6 kJ/mol-rxn) + (+890.3 kJ/mol-rxn)

= −74.8 kJ/mol-rxn

Thus, for the formation of 1 mol of CH4(g) from the elements, ∆rH° = −74.8 kJ/mol-rxn.
 Standard enthalpy of formation
When 1 mole of compound is formed from its elements, the enthalpy
change for the reaction is called the enthalpy of formation, ∆fHo
(kJ/mol).
These enthalpies are always reported at standard conditions:
1 atm and 25 °C (298 K).
The standard enthalpies of formation of the most stable form of any element is
zero: ∆fH (element) = 0
∆fH° O2(g) = 0 ∆fH° O(g) ≠ 0
(elemental form) (Not the elemental form)

Enthalpy is a state function, thus enthalpy values depend on the reaction

conditions in terms of the phases of reactants and products.
H2(g) + ½ O2(g) → H2O(g) ∆rH˚ = -242 kJ

H2(g) + ½ O2(g) → H2O(liq) ∆rH˚ = -286 kJ

Same reaction, different phases, different enthalpies.

 Enthalpy change for a reaction
A chemical reaction that describes the formation of one mole of a
compound from its elements at standard state conditions is known as
a “formation reaction”.
Using standard molar enthalpies of formation it is possible to calculate the
enthalpy change for a reaction using the following equation:

To find ∆rH°, add up the molar enthalpies of formation of the products, each
multiplied by its stoichiometric coefficient n, and subtract from this the sum of
the molar enthalpies of formation of the reactants, each multiplied by its
stoichiometric coefficient.
 Enthalpy change for a reaction
Nitroglycerin, C3H5(NO3)3, is a powerful explosive that forms four different
gases when detonated:
2 C3H5(NO3)3(l) → 3 N2(g) + ½O2(g) + 6 CO2(g) + 5 H2O(g)
Calculate the enthalpy change that occurs when 10.0 g of nitroglycerin is detonated.
The standard enthalpy of formation of nitroglycerin, ∆f H°, is −364 kJ/mol.
The ∆fH° values for the other compounds are; ∆fH°[CO2(g)] = −393.5 kJ/mol, ∆f
H°[H2O(g)] = −241.8 kJ/mol, and ∆f H° = 0 for N2(g) and O2(g).
 Standard enthalpy of formation

Now calculate the enthalpy change for 10 grams of nitroglycerin.

The enthalpy change for the detonation of 0.0440 mol nitroglycerin is.
 Product- or reactant-favoured reactions and
thermodynamics
At the beginning of this chapter, we noted that thermodynamics would provide
answers to four questions:

•How do we measure and calculate the energy changes associated

with physical changes and chemical reactions?
•What is the relationship between energy changes, heat, and work?
•How can we determine whether a chemical reaction is product
favoured or reactant-favoured at equilibrium?
• How can we determine whether a chemical reaction or physical
process will occur spontaneously, that is, without outside
intervention?

The first two questions were addressed in this chapter, but the other two
important questions still remain. They will be considered in detail in Chapter
18. We can, however, set the stage for consideration of these issues.