Thermochemistry

Introducti
on
• Broad category of everything
existing in the universe:
• Matter – “stuff”
• Energy – which moves the
“stuff”
• Energy
• primary source: sunlight
(inexhaustible)
• can be transferred in two ways:
• cause motion of an object against
a force (work)
Energy Changes in
Chemical Reactions
•Changes in matter are
accompanied by:
• absorption; or
• evolution of energy
•Causes of energy change:
• breaking; or
• formation of bonds
•Heat Processes:
• Exothermic – heat is evolved
• Endothermic – heat is
absorbed
System and Surroundings
• System – focused subject
• Closed system – exchange of
energy, not matter with its
surroundings
c
• Open system – exchange of
energy and matter with its
surroundings
• Isolated system – no exchange
of energy and matter with its
surroundings
• Surrounding – everything
System and Surroundings
Endothermic and
Exothermic Processes
• Endothermic
• Heat flows into the system
from the surroundings
• Heat is generally transferred
from a hotter to a colder one
• Exothermic
• Heat flows out of the system
into the surroundings
• Water poured into acid
(dangerous) VS acid poured
into water (safer)
Endothermic and
Exothermic Processes
First Law of
Thermodynamics
Thermodynamics
• “thermes” (greek) – heat
• “dynamo” – power
• study of energy and its
transformation
• understanding the
relationship between heat
and work in all living and
nonliving things
• understanding energetics
and direction of reactions
Law of Conservation of Energy
• Energy can neither be created
nor destroyed = it is conserved
• Energy may be transformed from
one form to another
• Any energy lost by the system
must be gained by the
surroundings (vice versa)
• Energy can be transferred back
and forth between the system
and the surroundings in the
form of heat and work
Internal Energy (E)
• Energy contained within the system
• Kinetic + potential energy of all components
of the system
• Is a state function - path independent
• Depends only in the initial and final states of
the system
• Does not depend on how and where the change is
carried out
• If a system transformed from A to B, ΔE is
• ΔE = EB – EA
• If the transformation is carried out by
exchange of heat and performance of work, ΔE
is
• ΔE = q + w
 ΔE = q + w
• Heat absorbed or evolved by the system, q
• Work performed by or done on the system, w
• Q and w are path dependent
• Changing q and w, their sum is still a state
function

Igniting methane ΔE w q

Bunsen burner - 885 kJ +5 kJ - 890 kJ

Engine - 885 kJ - 220 kJ - 665 kJ

ΔE = q + w
 ΔE = q + w

Heat added to the system   Heat evolved by the system

(+q) System (-q)
Work done on the system   Work done by the system
(+w) (-w)
3.2: First Law of
Thermodynamics
• Sample Problem:
1. Calculate ΔE when 175 J of work is done on a system
that evolves 50 J of heat to the surrounding.
• The loss of heat decreases the energy of the system by 50 J,
but doing work on a system increases the energy of the
system by 175 J.
• Given: • Solution:
q = -50 J ΔE = q + w
w = +175 J = - 50 J + 175 J
• Required: = 125 J
ΔE value
3.2: First Law of
Thermodynamics
• Sample Problem:
1. Calculate ΔE if 100 kJ of heat energy is absorbed
by the system and 30 kJ of work is done on the
surroundings.
• The addition of heat increases the energy of the system by
100kJ, but doing work decreases the energy of the system by
30kJ.
• Given: • Solution:
q = +100kJ ΔE = q + w
w = -30 kJ = 100 kJ + (-30 kJ)
= 70 kJ
• Required:
ΔE value
3.2: First Law of
Thermodynamics
• Sample Problem:
2. A gas in a closed container is heated with 10J of
energy, causing the lid of the container to rise 2m
with 3N of force. What is the total change in
energy of the system?
• The addition of heat increases the energy of the system by 10J.
There is no work given so we need to find it using the given
information to get it. W = Fd

• Given: • Solution:
q = +10J W = 3N x 2m = - 6J
F = 3N ΔE = q + w
d = 2m = 10 J + (-6 J)
= 4J
• Required:
W value, ΔE value