1

THERMOCHEMISTRY
Engr. Edgie L. Estopace
School of Chemical Engineering and Chemistry
Mapua Institute of Technology

Outline
1. Principles of heat flow
2. Measurement of heat flow; calorimetry
3. Enthalpy
4. Thermochemical equations
5. Enthalpies of formation
6. Bond enthalpy
7. The first law of thermodynamics

Principles of Heat Flow
Definitions
The system: that part of the universe on which
attention is focused
The surroundings: the rest of the universe
Practically speaking, it is possible to consider only the
surroundings that directly contact the system
Figure 6.1 Systems and Surroundings
Chemical Reactions
When we study a chemical reaction, we
consider the system to be the reactants and
products
The surroundings are the vessel (beaker, test
tube, flask) in which the reaction takes place
plus the air or other material in thermal
contact with the reaction system
Forms of Energy
Two broad categories of energy: potential
energy and kinetic energy.

Potential energy - associated with the relative
position of an object.

Kinetic energy - associated with motion.

Kinetic energy =
1
2
mv
2
Forms of Energy
Internal energy - the combined kinetic and
potential energies of atoms and molecules that
make up an object or system.

Chemical energy - energy released or
absorbed during a chemical reaction.

Other forms of energy include radiant,
mechanical, thermal, electrical, and nuclear.

Thermochemistry - the study of the energetic
consequences of chemistry
Heat and Work
Heat is the flow of energy between two
objects because of a difference in
temperature.

Heat flows from the warmer object to the cooler
object.
Work is the transfer of energy accomplished
by a force moving a mass some distance
against resistance.

Pressure-volume work (PV-work) is the most
common work type in chemistry.
Releasing an inflated balloon before it is tied off
illustrates an example of PV-work.
State Properties
The state of a system is specified by
enumerating:
Composition
Temperature
Pressure
State properties depend only on the state of
the system, not on the path the system took to
reach the state
Mathematically for a state property X:
X is the change in X
X = X
final
X
initial

Direction and Sign of Heat Flow
Heat is given the symbol, q
q is positive when heat flows into the system
from the surroundings
q is negative when heat flows from the system
into the surroundings
Endothermic processes have positive q
H
2
O (s) H
2
O () q > 0
Exothermic processes have negative q
CH
4
(g) + 2O
2
(g) CO
2
(g) + H
2
O () q < 0
Exothermic and Endothermic Processes
Magnitude of Heat Flow
In any process, we are interested in both the
direction of heat flow and in its magnitude
q is expressed in joules (or kilojoules)
James Joule (1818-1889); calorimetry
Alternate unit: calorie
1 calorie = 4.184 J
1 kilocalorie = 4.184 kJ
Nutritional calories are kcal
The Calorimetry Equation
q = C x t
t = t
final
t
initial
C (uppercase) is the heat capacity of the system:
it is the quantity of heat needed to raise the
temperature of the system by 1 C
q = m x c x t
c (lowercase) is the specific heat: the quantity of
heat needed to raise the temperature of one gram
of a substance by 1 C
c depends on the identity and phase of the
substance
Heat Capacity and Specific Heat
The amount of heat energy absorbed can be quantified.











q = mcAT
q = nC
p
AT
Heat Capacity and Specific Heat
Specific heat and molar heat capacities for some
common substances.
Example Problem 2
Heating a 24.0 g aluminum can raises its
temperature by 15.0

C. Find the value of q for

the can.
Example Problem 3
The molar heat capacity of liquid water is 75.3
J/mol K. If 37.5 g of water is cooled from 42.0
to 7.0

C, what is q for the water?

Specific Heat
The specific heat of a substance, like the
density or melting point, is an intensive
property that can be used to identify a
substance or determine its purity
Water
Water has an unusually large specific heat
A large quantity of heat is required to raise the
temperature of water
Climate is moderated by the specific heat of water
Only two states in the US have never recorded
temperatures over 100 F one is Alaska (cold North)
and the other is Hawaii (moderated by water)
Table 6.1
Example 6.1
Measurement of Heat Flow:
Calorimetry
A calorimeter is a device used to measure the
heat flow of a reaction
The walls of the calorimeter are insulated to
block heat flow between the reaction and the
surroundings
The heat flow for the system is equal in
magnitude and opposite in sign from the heat
flow of the calorimeter
q
reaction
= - q
calorimeter
q
reaction =
- C
cal
t
Calorimetry
Heat flow is measured using a calorimeter.

A calorimeter measures the heat evolved or
absorbed by the system of interest by
measuring the temperature change in the
surroundings.
q
system
= q
surroundings
q
gained
= q
lost
Example Problem 9.4
A glass contains 250.0 g of warm water at
78.0

C. A piece of gold at 2.30

C is placed in
the water. The final temperature reached by
this system is 76.9

C. What was the mass of

gold? The specific heat of water is 4.184
J/g

C, and that of gold is 0.129 J/g

C.
Calorimetry
There are two steps in a calorimetric
measurement.

Calibration - the calorimeter constant, C
calorimeter
,
is determined by dividing the known amount of
heat released in the calorimeter by the
temperature change of the calorimeter.

Actual Measurement - heat released or absorbed
in a reaction of known quantity of material is
measured.

q = C
calorimeter
AT
Calorimetry
Actual Measurement - temperature change for
the calorimeter and the calorimeter constant
are used to determine the amount of heat
released by a reaction.
q
calorimeter
= C
calorimeter
AT
calorimeter
q
reaction
= q
calorimeter
Calorimetry
Diagram of a bomb calorimeter and standard
choice for system and surroundings in a bomb
calorimetry experiment.
Example Problem 9.5
In the calibration of a calorimeter, an
electrical resistance heater supplies 100.0 J of
heat and a temperature increase of 0.850

C is
observed. Then, 0.245 g of a particular fuel is
burned in this same calorimeter and the
temperature increases by 5.23

C. Calculate the
energy density of this fuel, which is the
amount of energy liberated per gram of fuel
burned.
Figure 8.2
Coffee-cup Calorimeter
For a reaction performed in a coffee-cup calorimeter
t
C g
J
m q
water reaction
A

=

18 . 4
Example 6.2
Example 6.2, (Contd)
Figure 6.3
Bomb Calorimeter
The bomb calorimeter is more versatile than
the coffee-cup calorimeter
Reactions involving high temperature
Reactions involving gases
The bomb is a heavy metal vessel that is
usually surrounded by water
q
reaction
= -q
calorimeter
q
reaction
= -C
cal
t
C
cal
is a function of the calorimeter and can be
measured experimentally
Example 8.3
Enthalpy
The heat flow at constant pressure is equal to
the difference in enthalpy (heat content)
between products and reactants
The symbol for enthalpy is H
We measure changes in enthalpy using a
calorimeter and a reaction run at constant
pressure:
H = H
products
H
reactants
The sign of the enthalpy change is the same as
for heat flow:
H > 0 for endothermic reactions
H < 0 for exothermic reactions
Enthalpy is a state variable
Enthalpy
The conditions under which heat flow, q,
occurs will have an impact on the
measurement that is made.

Combustion of octane releases 5.45 x 10
3
kJ
under constant volume conditions, represented as
q
v
.
Combustion of octane releases 5.48 x 10
3
kJ
under constant pressure conditions, represented as
q
p
.
Defining Enthalpy
The internal energy change for a reaction
equals the sum of the heat flow and the work.

During an expansion, w = PAV.


Under constant volume conditions, AV = 0, and
AE = q
v.

AE = q + w
AE = q PAV
AE = q
v
Defining Enthalpy
Enthalpy is the heat flow under conditions of
constant pressure.
The enthalpy change can be expressed as
H = E + PV
AH = AE + A(PV)
AH = q
p
AH = (q PAV) + A(PV)
AH = q PAV + PAV
Defining Enthalpy
When a system releases heat, the process is
said to be exothermic.
The value of AH is less than zero; the sign on AH
is negative
When a system absorbs heat, the process is
said to be endothermic.
The value of AH is greater than zero; the sign on
AH is positive.
AH of Phase Changes
Phase changes occur under constant pressure
conditions.
The heat flow during a phase change is an enthalpy change.
During a phase change, temperature does not change with heat flow
due to formation or breaking of intermolecular attractive forces.
H of Phase Changes
The heat required to convert a liquid to a gas is the
heat of vaporization, AH
vap
.
AH
vap
is endothermic with a positive value.
The heat released to convert a gas to a liquid is the
heat of condensation, AH
cond
.
AH
cond
is exothermic with a negative value.
AH
cond
= AH
vap

The values of enthalpy changes in opposite directions
have equal numeric values and differ only in their
signs.
The magnitude of enthalpy change depends on the
substance involved.

H of Phase Changes
Standard molar enthalpies and temperatures for
phase changes of water.
H of Phase Changes
The value of AH for a phase change is
compound specific and has units of kJ/mol.

The heat flow can be calculated using the number
of moles of substance, n, and the value of the
enthalpy change.
AH = n AH
phase change
H of Phase Changes
Heat curve for the heating of 500-g of ice at -50
o
C
to 200
o
C.
Example Problem
Calculate the enthalpy change when 240. g of
ice melts.
Bonds and Energy
The enthalpy change for a reaction can be estimated
using bond energies.
During a chemical reaction, reactant bonds are
broken and product bonds are made.
Breaking bonds requires energy.
Making bonds releases energy.
If the amount of energy released making product
bonds is greater than the amount of energy required
to break reactant bonds, the reaction is exothermic. If
the energy released is less than the energy required,
the reaction is endothermic.
Bonds and Energy
The combustion of methane breaks 4 C-H bonds
and 2 O=O bonds. 2 C=O bonds and 4 O-H bonds
are made.
CH
4
+ 2O
2
CO
2
+ 2H
2
O
Bonds and Energy
The accuracy of enthalpy changes calculated from
tabulated bond energies is not very good.
The bond energies used are averages.
Bond energy method used to estimate enthalpy changes
for reactions involving compounds with no available
thermochemical data.
A thermochemical equation summarizes the overall
energetics for a chemical reaction.
The sign on the AH indicates whether the reaction is
endothermic or exothermic
CH
4
(g) + 2O
2
(g) CO
2
(g) + 2H
2
O(l )
AH = 890.4 kJ
Bonds and Energy
The combustion of methane is an exothermic reaction and
releases 890.4 kJ of heat energy when 1 mole of methane
reacts with 2 moles of oxygen.






For thermochemical equations, if the stoichiometric
coefficients are multiplied by some factor, the heat of reaction
must also be multiplied by the same factor.
CH
4
(g) + 2O
2
(g) CO
2
(g) + 2H
2
O(l )
AH = 890.4 kJ
2CH
4
(g) + 4O
2
(g) 2CO
2
(g) + 4H
2
O(l )
AH = 1780.8 kJ
Heats of Reaction for Some Specific Reactions
Some classes of chemical reactions are given
their own labels for heats of reactions.
Heat of combustion, AH
comb

Heat of neutralization, AH
neut
Heat of formation, AH
f
, is the heat of reaction for
formation of substances.


Fractional coefficients are allowed for formation reactions
because only one mole of product can be formed.

C(s) +
1
2
O
2
(g) CO(g)
Heats of Reaction for Some Specific Reactions
A formation reaction is the chemical reaction
by which one mole of a compound is formed
from its elements in their standard states.

The standard state is the most stable form of
an element at room temperature, 25
o
C, and
pressure, 1 atm, indicated with a superscript
o
.

AH
f
o
= 0 for an element in its standard state.
Hesss Law and Heats of Reaction
Direct calorimetric determinations of some reactions
may be too difficult or dangerous to perform.
An indirect method is needed to obtain heats of reaction.
Hesss law: the enthalpy change for any process is
independent of the particular way the process is
carried out.
Enthalpy is a state function.
A state function is a variable whose value depends only
on the state of the system and not its history.
Hesss Law
Conceptual diagram representing Hesss law.
Enthalpy is a state function, so any convenient
path can be used to calculate the enthalpy change.
Hesss Law
Enthalpy diagram for the combustion of methane. The
CH
4
is converted to CO, then the CO is converted to CO
2
.
The AH for each step is used to calculate the AH for the
overall reaction. The AH will be the same for both paths.
Example Problem
One origin of SO
3
is the combustion of sulfur,
which is present in small quantities in coal,
according to the following equation.



Given the thermochemical information below,
determine the heat of reaction for this
reaction.
S(s) +
3
2
O
2
(g) SO
3
(g)
S(s) + O
2
(g) SO
2
(g) AH
o
= 296.8 kJ
2SO
2
(g) + O
2
(g) 2SO
3
(g) AH
o
= 197.0 kJ
Formation Reactions and Hesss Law
Conceptual diagram showing how to use tabulated
enthalpies of formation to calculate the enthalpy
change for a chemical reaction.
Formation Reactions and Hesss Law
The enthalpy change for a reaction can be
calculated using Hesss law and heats of
formation.
AH
o
= v
i
AH
f
o
i

(products)
i
v
j
AH
f
o
j

(reactants)
j
Example Problem 9.8
Use tabulated data to find the heat of
combustion of one mole of propane, C
3
H
8
, to
form gaseous carbon dioxide and liquid water.
Example Problem 9.9
Ethanol, C
2
H
5
OH, is used to introduce oxygen
into some blends of gasoline. It has a heat of
combustion of 1366.8 kJ/mol. What is the
heat of formation of ethanol?
Energy and Stoichiometry
A thermochemical equation allows for the
stoichiometric treatment of energy.
For an exothermic reaction, energy is treated as a product.
For an endothermic reaction, energy is treated as a
reactant.
The thermochemical equation is used to convert
between the number of moles of a reactant or
product and the amount of energy released or
absorbed.
The stated value of AH for a thermochemical equation
corresponds to the reaction taken place exactly as written,
with the indicated numbers of moles of each substance
reacting.
Energy and Stoichiometry
Flow chart detailing the sequence of steps needed to
calculate the amount of energy released or absorbed
when a chemical reaction is carried out using a given
amount of material.
Thermochemical Equations
A thermochemical equation is a chemical equation with the H
for the reaction included
Example
NH
4
NO
3
(s) NH
4
+
(aq) + NO
3
-
(aq)
Experiment gives qreaction = 351 J for one gram of ammonium
nitrate
For one mole, this is



The thermochemical equation is
NH
4
NO
3
(s) NH
4
+
(aq) + NO
3
-
(aq) H = +28.1 kJ


kJ J X
mol
g
g
J
1 . 28 10 81 . 2
1
05 . 80
00 . 1
351
4
= =
Conventions for Thermochemical
Equations
1. The sign of H indicates whether the reaction
is endothermic or exothermic
2. The coefficients of the thermochemical
equation represent the number of moles of
reactant and product
3. The phases of all reactant and product species
must be stated
4. The value of H applies when products and
reactants are at the same temperature, usually 25
C
Rules of Thermochemistry
1. The magnitude of H is directly proportional
to the amount of reactant or product
2. H for the reaction is equal in magnitude but
opposite in sign for H for the reverse of the
reaction
3. The value of H is the same whether the
reaction occurs in one step or as a series of
steps
This rule is a direct consequence of the fact that H
is a state variable
This rule is a statement of Hesss Law
Example 6.4
Example 6.4, (Contd)
Enthalpy of Phase Changes
Phase changes involve enthalpy
There is no change in temperature during a phase change
Endothermic: melting or vaporization
Exothermic: freezing or condensation
Pure substances have a value of H that corresponds to melting
(reverse, fusion) or vaporization (reverse, condensation)
Example 6.5
Example 6.6
Example 6.6, (Contd)
Recap of the Rules of Thermochemistry
H is directly proportional to the amount of
reactant or product
If a reaction is divided by 2, so is H
If a reaction is multiplied by 6, so is H
H changes sign when the reaction is
reversed
H has the same value regardless of the
number of steps
Enthalpies of Formation
The standard molar enthalpy of formation, , is equal to the
enthalpy change
For one mole of a compound
At constant pressure of 1 atm
At a fixed temperature of 25 C
From elements in their stable states at that temperature and
pressure
Enthalpies of formation are tabulated in Table 8.3 and in Appendix
1 in the back of the textbook

f
H A
Table 6.3
Table 6.3, (Contd)
Table 6.3, (Contd)
Enthalpies of Formation of Elements and of H
+
(aq)
The enthalpy of formation of an element in its standard state at 25
C is zero


The enthalpy of formation of H
+
(aq) is also zero






0 ) ( ) (
2 2
= A = A l O H H l Br H
f f

Calculation of H



The symbol refers to the sum of
Elements in their standard states may be
omitted, as their enthalpies of formation are
zero
The coefficients of reactants and products in
the balanced equation must be accounted for
reactants H products H H
f f
A A = A

Example 6.7
Example 6.7, (Contd)
Example 6.8
The First Law of Thermodynamics
Thermodynamics
Deals with all kinds of energy effects in all kinds
of processes
Two types of energy
Heat (q)
Work (w)
The Law of Conservation of Energy
E
system
= - E
surroundings
The First Law
E

= q + w
The total change in energy is equal to the sum of the
heat and work transferred between the system and
the surroundings
Conventions
q and w are positive
When the heat or work enters the system from the
surroundings
q and w are negative
When the heat or work leaves the system for the
surroundings
Energy Transformation and Conservation of Energy
For a system or surroundings, the only
possible forms of energy flow are heat, q, and
work, w.

The delta, A, means change in and is
defined as the difference in the final and
initial states.

AE = q + w
AE = E
final
E
initial
Example Problem
If 515 J of heat is added to a gas that does 218
J of work as a result, what is the change in the
energy of the system?
Energy Transformation and Conservation of Energy
The sign resulting from the difference in the
final and initial states indicates the direction
of the energy flow.

Negative values indicate energy is being released.

Positive values indicate energy is being absorbed.
Energy Transformation and Conservation of Energy
First law of thermodynamics states that
energy can be transformed from one form to
another but cannot be created or destroyed.
AE
universe
= AE
surroundings
+ AE
system
= 0
Figure 8.10
Example 6.9
Heat
Ordinarily, when a chemical reaction is
carried out in the laboratory, energy is
evolved as heat
CH
4
(g) + 2O
2
(g) CO
2
(g) + H
2
O () E = -
885 kJ
The combustion of methane in a Bunsen burner
produces nearly 885 kJ of heat per mol
The decrease in volume that takes place is a 1%
work effect
Work
In an internal combustion engine, a significant
fraction of the energy of combustion is
converted to useful work
The expansion of the combustion gases produces
a volume and a pressure change
The system does work on its surroundings
Propels the car forward
Overcomes friction
Charges battery
Like H, E is a state variable
q and w are not state variables
Figure 6.11 Pressure-Volume Work
H and E
Constant pressure
Coffee-cup calorimeter
H = q
p
Constant volume
In a bomb calorimeter, there is no pressure-
volume work done
E = q
v


H and E, (Contd)
H = E + PV
H = E + PV
The PV product is important only where gases are
involved; it is negligible when only liquids or
solids are involved
H = E + n
g
RT
n
g
is the change in the number of moles of gas
as the reaction proceeds
Example 8.10
96
End of Chapter 15
Fireworks are beautiful exothermic
chemical reactions.
97
THERMOCHEMISTRY
Engr. Edgie L. Estopace
School of Chemical Engineering and Chemistry
Mapua Institute of Technology