Chapter 6

Thermochemistry:
Energy Flow and Chemical Change

6-1

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Thermochemistry: Energy Flow and Chemical Change

6.1 Forms of Energy and Their Interconversion
6.2 Enthalpy: Heats of Reaction and Chemical Change
6.3 Calorimetry: Laboratory Measurement of Heats of Reaction
6.4 Stoichiometry of Thermochemical Equations
6.5 Hesss Law of Heat Summation
6.6 Standard Heats of Reaction (H0rxn)

6-2

Thermodynamics is the study of heat and its transformations

to and from other forms of energy.
Thermochemistry is a branch of thermodynamics that deals with
the heat involved with chemical and physical changes.
Fundamental premise
When energy is transferred from one object to another,
it appears as work and/or as heat.
We must define a system to study; everything else
then becomes the surroundings.
The system is composed of particles with their own internal energies (E or U).
Therefore, the system has an internal energy. When a change occurs, the
internal energy changes.

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Figure 6.1

Energy diagrams for the transfer of internal energy (E)

between a system and its surroundings.

A. E pf system decreasses

B. E of system increases

E = Efinal - Einitial = Eproducts - Ereactants

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Figure 6.2 A system transferring energy as heat only.

A E lost as heat

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B E gained as heat

Figure 6.3

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A system losing energy as work only.

6-7

Euniverse = Esystem + Esurroundings

Units of Energy
Joule (J)

1 J = 1 kgm2/s2

calorie (cal)

1 cal = 4.184 J

British thermal unit (Btu)

6-8

1 Btu = 1055 J

Sample Problem 6.1

PROBLEM:

PLAN:

Determining the Change in Internal Energy of a

System

When gasoline burns in a car engine, the heat released causes

the products CO2 and H2O to expand, which pushes the pistons
outward. Excess heat is removed by the cars cooling system.
If the expanding gases do 451 J of work on the pistons and the
system loses 325 J to the surroundings as heat, calculate the
change in energy (E) in J, kJ, and kcal.

Define system and surroundings, assign signs to q and w and calculate

E. The answer should be converted from J to kJ and then to kcal.

SOLUTION:

q = - 325 J

w = - 451 J

E = q + w = -325 J + (-451 J) = -776 J

-776 J x

6-9

kJ
10 J
3

= -0.776 kJ

-0.776 kJ x

kcal
4.184 kJ

= -0.185 kcal

Figure 6.4

6-10

Two different paths for the energy change of a system.

Figure 6.5

6-11

Pressure-volume work.

The Meaning of Enthalpy

w = - PV
H = E + PV

H E in
1. Reactions that do not involve gases.

where H is enthalpy

H = E + PV

qp = E + PV = H

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2. Reactions in which the number of

moles of gas does not change.
3. Reactions in which the number of
moles of gas does change but q is >>>
PV.

Figure 6.6

Enthalpy diagrams for exothermic and endothermic processes.

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Sample Problem 6.2

PROBLEM:

Drawing Enthalpy Diagrams and Determining

the Sign of H

In each of the following cases, determine the sign of H, state

whether the reaction is exothermic or endothermic, and draw an
enthalpy diagram.
1
(a) H2(g) +
O2(g)
H2O(l) + 285.8 kJ
2
(b) 40.7 kJ + H2O(l)

PLAN:

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Determine whether
heat is a reactant or a
product. As a
reactant, the products
are at a higher energy
and the reaction is
endothermic. The
opposite is true for an
exothermic reaction.

H2O(g)
SOLUTION:

6-15

Sample Problem 6.3

Finding the Quantity of Heat from Specific Heat Capacity

PROBLEM: A layer of copper welded to the bottom of a skillet weighs 125 g.

How much heat is needed to raise the temperature of the copper
layer from 25oC to 300.oC? The specific heat capacity (c) of Cu
is 0.387 J/gK.
PLAN: Given the mass, specific heat capacity and change in temperature, we
can use q = c x mass x T to find the answer. T in oC is the same as for
K.
SOLUTION:
q = 0.387 J/gK x 125 g x (300oC - 25oC) = 1.33 x 104 J

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Figure 6.7

Coffee-cup calorimeter.

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Sample Problem 6.4

Determining the Heat of a Reaction

PROBLEM: You place 50.0 mL of 0.500 M NaOH in a coffee-cup calorimeter at

25.00oC and carefully add 25.0 mL of 0.500 M HCl, also at 25.00oC.
After stirring, the final temperature is 27.21oC. Calculate qsoln (in J) and
Hrxn (in kJ/mol). (Assume the total volume is the sum of the individual
volumes and that the final solution has the same density and specific
heat capacity as water: d = 1.00 g/mL and c = 4.184 J/gK)

PLAN:

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We need to determine the limiting reactant from the net ionic equation.
The moles of NaOH and HCl as well as the total volume can be
calculated. From the volume we use density to find the mass of the water
formed. At this point qsoln can be calculated using the mass, c, and T.
The heat divided by the M of water will give us the heat per mole of water
formed.

Sample Problem 6.4

Determining the Heat of a Reaction

continued
SOLUTION:

HCl(aq) + NaOH(aq)
H+(aq) + OH-(aq)

NaCl(aq) + H2O(l)
H2O(l)

For NaOH

0.500 M x 0.0500 L = 0.0250 mol OH-

For HCl

0.500 M x 0.0250 L = 0.0125 mol H+

HCl is the limiting reactant.

0.0125 mol of H2O will form during the

reaction.
total volume after mixing = 0.0750 L

0.0750 L x 103 mL/L x 1.00 g/mL = 75.0 g of water

q = mass x specific heat x T
= 75.0 g x 4.184 J/goC x (27.21oC - 25.00oC)
= 693 J
(693 J/0.0125 mol H2O)(kJ/103 J) = -55.4 kJ/ mol H2O formed

6-19

Figure 6.8 A bomb calorimeter.

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Sample Problem 6.5

PROBLEM:

PLAN:

Calculating the Heat of a Combustion Reaction

A manufacturer claims that its new dietetic dessert has fewer

than 10 Calories per serving. To test the claim, a chemist at the
Department of Consumer Affairs places one serving in a bomb
calorimeter and burns it in O2 (the heat capacity of the
calorimeter = 8.151 kJ/K). The temperature increases 4.937oC.
Is the manufacturers claim correct?

- q sample = qcalorimeter

SOLUTION:

qcalorimeter

(First Law of Thermodynamics)

= heat capacity x T
= 8.151 kJ/K x 4.937 K = 40.24 kJ

1 Calorie = 1 kcal = 4.184 kJ

10 Calorie = 41.84 kJ
The manufacturers claim is true.

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Figure 6.9

6-22

Summary of the relationship between

amount (mol) of substance and the heat
(kJ) transferred during a reaction.

Sample Problem 6.6

PROBLEM:

PLAN:

Using the Heat of Reaction (Hrxn) to Find

Amounts

The major source of aluminum in the world is bauxite (mostly

aluminum oxide). Its thermal decomposition can be represented by
3
Al2O3(s)
2Al(s) + O2(g) Hrxn = 1676 kJ
2
If aluminum is produced this way, how many grams of aluminum can
form when 1.000 x 103 kJ of heat is transferred?
SOLUTION:
1.000 x 103 kJ x

2 mol Al
1676 kJ

26.98 g Al
1 mol Al
= 32.20 g Al

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Sample Problem 6.7

PROBLEM:

PLAN:

Two gaseous pollutants that form in auto exhaust are CO and

NO. An environmental chemist is studying ways to convert them
to less harmful gases through the following equation:
1
CO(g) + NO(g)
CO2(g) +
N (g) H = ?
2 2
Given the following information, calculate the unknown H:
1
Equation A: CO(g) +
O (g)
CO2(g) HA = -283.0 kJ
2 2
Equation B: N2(g) + O2(g)
2NO(g) HB = 180.6 kJ

Equations A and B have to be manipulated by reversal and/or

multiplication by factors in order to sum to the first, or target, equation.

SOLUTION:

Multiply Equation B by 1/2 and reverse it.

1
CO(g) + O2(g)
CO2(g) HA = -283.0 kJ
2
1
1
NO(g)
N2(g) +
O (g) HB = -90.3 kJ
2
2 2

CO(g) + NO(g)

6-24

Using Hesss Law to Calculate an Unknown H

CO2(g) + 1 N2(g)
2

Hrxn = -373.3 kJ

6-25

Sample Problem 6.8

PROBLEM:

Writing Formation Equations

Write balanced equations for the formation of 1 mol of the following

compounds from their elements in their standard states and include
Hof.
(a) Silver chloride, AgCl, a solid at standard conditions
(b) Calcium carbonate, CaCO3, a solid at standard conditions
(c) Hydrogen cyanide, HCN, a gas at standard conditions

PLAN: Use the table of heats of formation for values.

SOLUTION:
(a) Ag(s) + 1/2Cl2(g)

(b) Ca(s) + C(graphite) + 3/2O2(g)

(c) 1/2H2(g) + C(graphite) + 1/2N2(g)

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Hof = -127.0 kJ

AgCl(s)
CaCO3(s)
HCN(g)

Hof = -1206.9 kJ
Hof = 135 kJ

Figure 6.10

The general process for determining Horxn from Hof values.

6-27

Sample Problem 6.9

PROBLEM:

Calculating the Heat of Reaction from Heats of

Formation

Nitric acid, whose worldwide annual production is about 10 billion

kilograms, is used to make many products, including fertilizer, dyes,
and explosives. The first step in the industrial production process is
the oxidation of ammonia:
4NH3(g) + 5O2(g)

4NO(g) + 6H2O(g)

Calculate Horxn from Hof values.

PLAN:

Look up the Hof values and use Hesss law to find Hrxn.

SOLUTION:

Hrxn = mHof (products) - nHof (reactants)

Hrxn = {4[Hof NO(g)] + 6[Hof H2O(g)]} - {4[Hof NH3(g)] + 5[Hof O2(g)]}

= (4 mol)(90.3 kJ/mol) + (6 mol)(-241.8 kJ/mol) [(4 mol)(-45.9 kJ/mol) + (5 mol)(0 kJ/mol)]
Hrxn = -906 kJ

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Figure 6.11

The trapping of heat by the atmosphere.

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