Preparation for

General
Chemistry
Prof. Darrin M. York
Rutgers, The State University of New Jersey
Thermochemistry:
Energy and
energy changes
Define thermochemistry and its relation to heat and work.
Describe the difference between an exothermic and endothermic chemical
processes in the context of a system and its surroundings.
Distinguish between an open system, closed system and isolated system.
Define a state function and provide several examples.
State the first law of thermodynamics and its relation to the law of
conservation of energy.
Relate internal energy change to heat and work.
Relate enthalpy change to internal energy, pressure and volume.
Energy is the capacity to do work.
Work (W) is a change in energy that results when a force (F) is exerted over a
distance (d): ! # $ !% "#$ &'( )'*+ #),+$ -#$./0 +1210 ! # &'!(3
There are three basic forms of energy:
Kinetic energy (E
K
energy due to motion)
Potential energy (V energy due to position in a force field)
Radiant energy (E
photon
energy due to radiation; i.e., photon energy)
For any process, the total energy is conserved (although one form of energy
may be transformed into another): !E
TOT
= 0
E
TOT
= E
K
+ V + E
photon
The system is a part of the universe that is of specific interest.
The surroundings constitute the rest of the universe outside the system.
Surroundings
Universe = System + Surroundings
System
There are three different types of
systems we will consider:
a) An open system can exchange
mass and energy with the
surroundings.
b) A closed system allows the
transfer of energy but not mass.
c) An isolated system does not
exchange either mass or energy
with its surroundings.
Thermochemistry is the study of energy transfer in chemical reactions.
Heat is the transfer of thermal energy (a form of kinetic energy).
Work is the transfer of mechanical energy (a form of potential energy).
Energy can also transferred in the form of radiant energy (i.e., the
emission of absorption of photons).
Henceforth, we assume that our system and surroundings do not
chemically react with one another, and the only mechanism for energy
transfer between them occurs through heat and/or work.
An exothermic process occurs when heat is transferred from the system
to the surroundings.
Feels hot!
Surroundings
heat
System
4Fe(s) + 3O
2
(g) ! 2Fe
2
O
3
(s)
An endothermic process occurs when heat is transferred from the
surroundings to the system.
Feels cold!
Surroundings
heat
System
NH
4
NO
3
+ H
2
O ! NH
3
+ NO
3
" + H
3
O
+
The first law of thermodynamics states that energy can be converted
from one form to another, but cannot be created or destroyed.
!U is the change in the internal energy.
sys and surr denote system and surroundings, respectively.
!U = U
f
U
i
; the difference in the energies of the initial and final states.
!U
sys
+ !U
surr
= 0
this implies that !U
sys
= !U
surr

The overall change in the systems internal energy is given by:
q is heat
q is positive for an endothermic process (heat absorbed by the system)
q is negative for an exothermic process (heat released by the system)
w is work
w is positive for work done on the system
w is negative for work done by the system
pressure-volume work is:
!U = q + w
w

= -P!V
w = #P!V
= #1.8 atm (6.0 L 4.0 L)
= # 3.6 atm$L
1 atm = 101.325 Pa, 1 Pa$L =1 J
1 atm$L = 101.325 J
w = #3.6 atm$L %101.325 J/(1 atm$L)
= # 0.365 kJ
4.0 L
6.0 L
1.8 atm
1.8 atm
!V = V
f
- V
i
= 6.0 L - 4.0 L
= 2.0 L
State functions are properties that are determined by the state
of the system, regardless of in which way the system acquired
that state (i.e., how the state was achieved).
Pressure
Volume
Temperature
Mass/particle number
Internal Energy
Enthalpy
Entropy
Free Energy

!U = q + w
Heat and Work ,
independently, are NOT
state functions, but their
sum is.
Ozone Depletion over the Antarctic
without catalyst O
3(g)
+ O
(g)
! 2 O
2(g)


Very Slow
with catalyst Cl
(g)
+ O
3(g)
! O
2(g)
+ ClO
(g)
Very Fast
ClO
(g)
+ O
(g)
! O
2(g)
+ Cl
(g)

P
o
t
e
n
t
i
a
l

E
n
e
r
g
y

Reaction progress

O
3(g)
+ O
(g)
! 2 O
2(g)

The change in internal energy given only pressure-volume work, w = -P!V, is:



Which, under conditions of constant volume (!V=0) leads to:
!U = q P!V = q
V

The internal energy change, "U, of a reaction is the
heat evolved in a reaction at constant volume, q
V
.
!U = q + w = q - P!V
q
V
= !U
The enthalpy, H, of a system is the sum of the internal energy of the system and
the product of pressure and volume:


!H = !U + !(PV)=(U
f
- U
i
)+(P
f
V
f
- P
i
V
i
)
Under conditions of constant pressure:
!H = !U + P!V
= q - P!V + P!V =q
P

The enthalpy change, "H, of a reaction is the heat
evolved in a reaction at constant pressure, q
P
.
!U = q ! P"V
H = U+PV
q
P
= !H
H
2
O(s) ! H
2
O(l) CH
4
(g) + 2O
2
(g) ! CO
2
(g) + 2H
2
O(g)
!H = H(products) H(reactants)
E
n
t
h
a
l
p
y
,

H

H
2
O(l)
H
2
O(s)
H
(reactants)

H
(products)

heat in
"H > 0
(endothermic)
Endothermic process
E
n
t
h
a
l
p
y
,

H

CH
4
+ 2O
2

CO
2
+ 2H
2
O
H
(reactants)

H
(products)

heat out
"H < 0
(exothermic)
Exothermic process
The following guidelines are useful when considering
thermochemical equations:
1) Always specify the physical states of reactants and products
because they help determine the actual enthapy changes.
CH
4
(g) + 2O
2
(g) !H = "802.4 kJ CO
2
(g) + 2H
2
O(g)
CH
4
(g) + 2O
2
(g) !H = -890.4 kJ CO
2
(g) + 2H
2
O(l)
different
states
different
enthalpies
2H
2
O (g) 2H
2
O(l)
!H = -88.0 kJ
2) When multiplying an equation by a factor (n), multiply the !H value by same
factor.
CH
4
(g) + 2O
2
(g)
!H = " 802.4 kJ
CO
2
(g) + 2H
2
O(g)
2CH
4
(g) + 4O
2
(g)
!H = " 1604.8 kJ
2CO
2
(g) + 4H
2
O(g)
3) Reversing an equation changes the sign but not the magnitude of !H.
CH
4
(g) + 2O
2
(g)
!H = " 802.4 kJ
CO
2
(g) + 2H
2
O(g)
CO
2
(g) + 2H
2
O(g) !H = +802.4 kJ CH
4
(g) + 2O
2
(g)
Thermochemistry is the study of energy change in chemical reactions, and
can occur through heat and work.
Reactions that release heat to the surroundings are exothermic whereas ones
that absorb heat from the surroundings are endothermic.
Systems can be either open (can exchange mass with the surroundings),
closed (cannot exchange mass with the surroundings) or isolated (cannot
exchange either mass or energy with the surroundings).
A state function, such as internal energy, enthalpy, pressure and volume, are
properties that depend only on the state of the system, and changes in these
properties require knowledge only of the initial and final states and not on
how the change actually occurred.

The first law of thermodynamics states that the total internal energy of the
universe remains constant (i.e., is conserved), therefore for any process, the
change in internal energy of a system is equal in magnitude and opposite in
sign to the resultant change in internal energy of the surroundings.
The internal energy change (!U) is equal to the sum of heat (q) and work
(w).
The enthalpy (H) is equal to the internal energy plus pressure (P) times
volume (V).
Thermochemical equations allow one to track enthalpy along with chemical
species in the reaction.

H = U+PV
!U = q + w
q
P
= !H
q
V
= !U
Constant V:
Constant P: