Chapter Five Learning Objectives

define and classify energy

apply the first law of thermodynamics
define and understand enthalpy
use Hesss law to determine enthalpies of
reaction
use standard enthalpies of formation to calculate
standard enthalpies of reaction

Chemistry 1A

Thermochemistry

Definition of Energy
The energy found in all matter can be used to
achieve two basic types of tasks: transfer heat or
accomplish work.
Define heat:
Define work:
What are the terms for the energy an object
possesses because of its motion? its position?
Chemistry 1A

Thermochemistry

Classification of Energy
Perhaps the most convenient
form in which to store energy
is chemical energy: a form of
potential energy that is holding
together atoms in molecules.
Decomposition of Nitrogen Triiodide

What form of energy is associated with vibration

and movement of molecules within a substance?
Chemistry 1A

Thermochemistry

Units of Energy
SI unit of energy = J (1 J = 1 kgm2/s2)
A joule (pronounced jool) is not a large amount of
energy so often kilojoules (kJ) are used when discussing
the energies associated with chemical reactions.
older unit of energy = cal
1 cal = 4.184 J (exactly)
unit of nutritional energy = Cal
1 Cal = 1000 cal = 1 kcal

Chemistry 1A

Thermochemistry

Conservation of Energy
When studying the energies associated with
chemical reactions, we are determining energy
transfer (a relative change) not energy content
(an absolute value).
Any change in the internal energy of the system
(the chemical reaction) is accompanied by an
opposite change in the surroundings.
Define a closed system:
Chemistry 1A

Thermochemistry

First Law of Thermodynamics

The change in internal energy (E) of a system is
the sum of the heat (q) transferred to or from the
system and the work (w) done on or by the system:

E = q + w

Chemistry 1A

Thermochemistry

Key Concept
The contents of the box in each of the following illustrations
represent a closed system, and the arrows show the
changes to the system during some process. The lengths
of the arrows represent the relative magnitudes of q and w.
Which of these processes, if any, have a E < 0?

Chemistry 1A

Thermochemistry

Pressure-Volume Work
The most common type of work encountered in
chemical systems is pressure-volume (P-V)
work: the work involved in the expansion or
compression of gases.
At constant external pressure (P), work can be
done on the system (+w) during compression
(V) or work can be done by the system (w)
during expansion (+V):

w = P V
Chemistry 1A

Thermochemistry

Enthalpy
Most chemical reactions are
carried out in open containers
at constant pressure out of
convenience.
The heat transferred to or from
a system at constant pressure
is called the enthalpy change
(H) of the reaction and is
easily measured as a change
in temperature.
Chemistry 1A

Thermochemistry

Key Concept
Consider the following gaseous reaction:

(a) Has any work been done on or by the system? If so,

then what is the sign of w?
(b) Has there been an enthalpy change? If so, then what is
the sign of H?
Chemistry 1A

Thermochemistry

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Energy, Enthalpy, and P-V Work

E = q + w = q P V or q = E + P V
The change in internal The change in
energy measures the
enthalpy measures
heat transfer at
the heat transfer at
constant volume:
constant pressure:

V = 0 so q v = E

qp = E + P V = H

The difference between E and H is the

amount of P-V work, if any, done on or by the
system at constant pressure.
Chemistry 1A

Thermochemistry

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Key Concept
The following reaction was carried out in a closed
container (at constant volume):
C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (g) E = 2045 kJ

If the same reaction was carried out in an open

container (at constant pressure), then what is the
sign and approximate magnitude of H?

Chemistry 1A

Thermochemistry

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Enthalpy Changes and

Chemical Equations
An enthalpy change associated with a specific balanced
chemical equation depends on both the molar amounts and
the physical states of the reactants and products:
CH4 (g) + 2 O2 (g) CO2 (g) + 2 H2O (l)

H = 890 kJ

2 CH4 (g) + 4 O2 (g) 2 CO2 (g) + 4 H2O (l)

H = ? kJ

CO2 (g) + 2 H2O (l) CH4 (g) + 2 O2 (g)

H = ? kJ

CH4 (g) + 2 O2 (g) CO2 (g) + 2 H2O (g)

H = ? kJ

Chemistry 1A

Thermochemistry

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Practice Exercise
The combustion of sucrose, commonly known as
sugar, is a highly exothermic process:
C12H22O11 (s) + 12 O2 (g) 12 CO2 (g) + 11 H2O (l)
H = 5645 kJ

(a)What is the enthalpy change (kJ) for the

oxidation of 0.015 mol (1 teaspoon) of sugar?
(b)If 725 kJ of heat are released, then what is the
mass (g) of water produced in the process?
Chemistry 1A

Thermochemistry

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Practice Exercise
Consider the following decomposition reaction:
2 NaHCO3 (s) Na2CO3 (s) + H2O (g) + CO2 (g)

When 0.0150 mol of NaHCO3 are decomposed,

1.15 kJ of heat are absorbed in the process. What
is the enthalpy change (kJ) associated with the
above chemical equation?

Chemistry 1A

Thermochemistry

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Hesss Law
If a reaction is the sum of two or more other
reactions, then the H for the overall process is
the sum of the H values of those reactions:
CH4 (g) + 2 O2 (g) CO2 (g) + 2 H2O (l)
2 H2O (l) 2 H2O (g)

H1 = 890 kJ
H2 = +88 kJ

CH4 (g) + 2 O2 (g) CO2 (g) + 2 H2O (g)

Hnet = 802 kJ

H1 + H2 = Hnet
Chemistry 1A

Thermochemistry

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Practice Exercise
Use Hesss law to calculate the enthalpy change
for the formation of CS2 (g) from C (s) and S (s)
given the following thermochemical data:
C (s) + O2 (g) CO2 (g)

H1 = 393.5 kJ

S (s) + O2 (g) SO2 (g)

H2 = 296.8 kJ

CS2 (g) + 3 O2 (g) CO2 (g) + 2 SO2 (g) H3 = 1103.9 kJ

C (s) + 2 S (s) CS2 (g)
Chemistry 1A

Hnet = ? kJ

Thermochemistry

17

Standard Enthalpies of Formation

The most efficient way to manage with the
smallest number of experimental measurements
is to use standard enthalpies of formation (Hf),
where the superscript indicates an enthalpy
change measured under standard conditions.
Define Hf:

Chemistry 1A

Thermochemistry

18

Practice Exercise
Write a balanced
chemical equation that
depicts the formation of
one mole of aluminum
bromide from its
elements in their
standard states:

Chemistry 1A

Thermochemistry

19

Integrative Exercise
For the reaction 4 CO (g) + 2 NO2 (g) N2 (g) + 4 CO2 (g),
use Hesss law to calculate Hrxn (kJ) given the following
thermochemical data:
Hf [NO (g)] = +90.2 kJ/mol
2 NO (g) + O2 (g) 2 NO2 (g)

Hrxn = 114.0 kJ

2 CO (g) + O2 (g) 2 CO2 (g)

Hrxn = 566.0 kJ

Chemistry 1A

Thermochemistry

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10

Standard Enthalpies of Reaction

If Hf values are known for all of the reactants
and products in a reaction, then the standard
enthalpy change for the reaction (Hrxn) can be
determined by applying Hesss law.
For the reaction
aA + bB cC + dD

H o rxn = [cH o f (C) + dH o f (D)] [aH o f (A) + bH o f (B)]

or H o rxn =
nH o f (products)
mH o f (reactants)

Chemistry 1A

Thermochemistry

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Worked Example
Calculate Hrxn for the fermentation of glucose:
C6H12O6 (s) 2 C2H5OH (l) + 2 CO2 (g)
Hrxn = [2 Hf (C2H5OH) + 2 Hf (CO2)] [Hf (C6H12O6)]
= (2 mol)(277.7 kJ/mol) + (2 mol)(393.5 kJ/mol)
(1 mol)(1273.02 kJ/mol)
Hrxn = 69.4 kJ

Chemistry 1A

Thermochemistry

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11

Practice Exercise

Calculate Hrxn for the highly

exothermic thermite reaction:

Fe2O3 (s) + 2 Al (s) 2 Fe (s) + Al2O3 (s)

0
0
Hf (kJ/mol) 822.16
1669.8
Chemistry 1A

Thermochemistry

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Integrative Exercise
The combustion of C10H8 (s) to yield H2O (g) and CO2 (g)
releases 5156.1 kJ of heat per mole of C10H8 (s).
(a) Write a balanced thermochemical equation for the
reaction:
(b) Calculate Hf (kJ/mol) for C10H8 (s) using the following
additional thermochemical data:
Hf [H2O (g)] = 241.8 kJ/mol
Hf [CO2 (g)] = 393.5 kJ/mol
Chemistry 1A

Thermochemistry

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