Chapter 17

Thermochemistry
Thermochemistry:

Study of energy changes that occur
during chemical reactions and
changes in state
Section 17.1: The flow of energy
energy changes can either occur
through heat transfer or work
heat (q), energy is transferred
from a warmer object to a cooler
object (always)
Adding heat increases
temperature
Section 17.1: The flow of energy
Kinetic energy vs. potential energy

17.1: Endothermic & Exothermic processes
energy due to
motion
energy due to a substance's
chemical composition
potential energy is determined by the strength of repulsive
and attractive forces between atoms

In a chemical reaction, atoms are recombined into new
arrangements that have different potential energies

change in potential energy: due to absorption and release of
energy to and from the surroundings


Two parameters crucial in Thermochemistry:

a) system--part of the universe
attention is focused

b) surroundings--everything else in the
universe
System + surrounding = universe
Fundamental goal of Thermochem.: study the
heat flow between the system and its
surroundings

17.1: Endothermic & Exothermic processes
If System (energy) Surrounding
(energy) by the same amount

the total energy of the universe does not
change

Law of conservation of energy
17.1: Endothermic & Exothermic processes
17.1: Endothermic & Exothermic processes
Direction of heat flow is given from the point
of view of the system
So, endothermic process: system absorbs heat
from the surroundings (system heats up)
Heat flowing into the system = +q
Exothermic process: heat is released into the
surroundings (system cools down, -q)
17.1: Endothermic & Exothermic processes
Example 1:

A container of melted paraffin wax is allowed to
stand at room temperature (r.t.) until the wax
solidifies. What is the direction of heat flow as
the liquid wax solidifies? Is the process
exothermic or endothermic?

Answer: Heat flows from the system (paraffin) to
the surroundings (air)

Process: exothermic
17.1: Endothermic & Exothermic processes
Example 2:

When solid Ba(OH)
2
8H
2
O is mixed in a beaker
with solid NH
4
SCN, a reaction occurs. The
beaker quickly becomes very cold. Is the
reaction exothermic or endothermic?

Answer: Endothermic

surrounding = beaker and air

System = chemicals within beaker
17.1: Units of heat flow
Two units used:

a) calorie (cal)amount of heat required to
raise the temperature of 1g of pure water by
1
o
C

b) joule (j)1 joule of heat raises the
temperature of 1 g of pure water 0.2390
o
C
Joule = SI unit of energy
17.1 Heat capacity & specific heat
Heat capacity is the quantity of heat needed to
raise the temperature of an object exactly 1
o
C
Heat capacity depends on:
a) mass
b) chemical composition
So, the greater the mass the greater the heat
capacity
eg.: cup of water vs. a drop of water
(cup of water = greater heat capacity)
17.1: Heat capacity & specific heat
Specific heat: amount of heat required to raise
the temperature of 1g of a substance by 1
o
C

Table 17.1 (p.508): List of specific heats of
substances
Specific heat calculation

C = q = heat (joules/calories)
m * T mass (g) * Temp. (
o
C)

T = T
f
T
i
(T
f
= final temperature)
(T
i
= initial temperature)

C = j or cal
(g *
o
C) (g *
o
C)
Example 1
1. The temperature of a 95.4 g piece of copper
increases from 25.0
o
C to 48.0
o
C when the
copper absorbs 849 j of heat. What is the
specific heat of copper?
unknown: C
cu
Know:
mass copper = 95.4 g
T = T
f
T
i
= (48.0
o
C 25.0
o
C)
= 23.0
o
C
q = 849 j
Example1
C = q
m * T

C = 849 j
95.4 g * 23.0
o
C

C = 0.387 j/g *
o
C
Sample problem 17.1, page 510
Example 2
2. How much heat is required to raise the
temperature of 250.0 g of mercury (Hg) 52
o
C?
unknown: q

Know:
mass Hg = 250.0 g
T = 52.0
o
C
C
Hg
= 0.14 j/(g *
o
C)

Example 2

C = q
m * T

q = C
Hg
* m * T

q = 0.14 (j/g *
o
C) * 250.0 g * 52
o
C

q = 1.8 x 10
3
j (1.8 kj)



Problem #4 page 510
Section 17.2
Measuring Enthalpy Changes
17.2: Enthalpy (measuring heat flow)
Calorimetry:
accurate measurement of heat flow
into or out of a system in chemical
and physical processes
In calorimetry, heat released by a system is
equal to the heat absorbed by its surroundings
and vice versa
Instrument used to measure absorption or
release of heat is a calorimeter
Two types of calorimeters:
a) Constant-Pressure calorimeter (eg. foam cups)
As most reactions occur at constant pressure we can say
that:
A change in enthalpy (H) = heat supplied (q)

So, a release of heat (exothermic) corresponds to a
decrease in enthalpy (at constant pressure)

An absorption of heat (endothermic) corresponds to an
increase in enthalpy (constant pressure)

17.2: Enthalpy (measuring heat flow)
17.2: Enthalpy (measuring heat flow)
b) Constant-Volume Calorimeters (eg. bomb

calorimeters)
Substance is burned (in the presence of O
2
) inside a
chamber surrounded by water (high pressure)
Heat released warms the water
Figure 17.6 (p. 512) Bomb calorimeter.
17.2: Thermochemical equations


CaO
(s)
+ H
2
O
(l)
Ca(OH)
2
+ 65.2 kJ
Heat released
A chemical equation that includes the enthalpy
change is called
a thermochemical equation

Reactants and products at their usual physical
state (at 25
o
C) given at standard pressure (101.3
kPa)

So, the heat of reaction (or H) for the above
equation is -65.2 kJ

17.2: Thermochemical equations
So, rewrite the equation as
follows:
CaO
(s)
+ H
2
O
(l)
Ca(OH)
2(s)
AH = 65.2 kJ
Other reactions absorb heat from the surroundings, eg.:
Rewrite to show heat of reaction
2 NaHCO
3(s)
Na
2
CO
3(s)
+ H
2
O
(g)
+ CO
2(g) + 129 kJ
AH = 129 kJ
NaHCO
3(s)
Na
2
CO
3(s)
+ H
2
O
(g)
+ CO
2(g) 2
Amount of heat released/absorbed during a
reaction depends on the number of moles of
reactants involved

eg.:


17.2: Thermochemical equations
AH = 129 kJ
NaHCO
3(s)
Na
2
CO
3(s)
+ H
2
O
(g)
+ CO
2(g) 2
AH = 258 kJ
NaHCO
3(s)
Na
2
CO
3(s)
+ H
2
O
(g)
+ CO
2(g) 4
Enthalpy Diagrams
CaO
(s)
+ H
2
O
(l)
AH = -65.2 kJ
Ca(OH)
2(s)
Exothermic Reaction
Na
2
CO
3(s)
+ H
2
O
(l)
+ CO
2(g)
AH = 129 kJ
2 NaHCO
3(s)
Endothermic Reaction
Diagram A:
Enthalpy of reactants greater
than of products
Diagram B:
Enthalpy of reactant less
than of products

Physical states of reactants and products must be
stated:


17.2: Thermochemical equations
H
2
O
(l)
H
2(g)
+ 1 O
2(g)

2
AH = 285.8 kJ
H
2
O
(g)
H
2(g)
+ 1 O
2(g)

2
AH = 241.8 kJ
Difference = 44.0 kJ
Vaporization of H
2
O
(l)
requires more heat (44.0 kJ)
Example1


AH = 129 kJ
NaHCO
3(s)
Na
2
CO
3(s)
+ H
2
O
(g)
+ CO
2(g) 2
1. Calculate the amount of heat in (kJ) required to decompose 2.24 mol
NaHCO
3(S)

Known:
2.24 mol NaHCO
3
decomposes
H = 129 kJ (2 mol NaHCO
3
)
Unknown:
H = ?
Solve:

129 kJ = H
2 mol NaHCO
3(s)
2.24 mol NaHCO
3(s)

H = (129 kJ) * 2.24 mol NaHCO
3(s)

2 mol NaHCO
3(s)


H = 144 kJ




Sample problem 17.3; p. 516
Example 2
2. When carbon disulfide is formed from its
elements, heat is absorbed. Calculate the
amount of heat in (kJ) absorbed when 5.66 g of
carbon disulfide is formed.


C
(s)
+ 2 S
(s)
CS
2(l)
AH = 89.3 kJ
Known:
5.66 g CS
2
is formed
H = 89.3 kJ (1 mol CS
2(l)
)
Molar mass: CS
2(l)
: C = 12.0 g/mol
2 *S = 32.1 g/mol = 64.2 g/mol
76.2 g/mol

Unknown:
H = ?
Example 2
Solve:
1. Moles CS
2(l)
= 5.66g CS
2 =
0.0743 mol CS
2(l)

76.2 g/mol CS
2(l)

2. 89.3 kJ = H
1 mol CS
2(l)
0.074 mol CS
2(l)


H = (89.3 kJ) * 0.074 mol CS
2(l)

1 mol CS
2(l)


H = 6.63 kJ



17.3: Heat in changes of state
Objective:

-Heats of Fusion and Solidification

-Heats of Vaporization and Condensation

-Heat of solution
The temperature remains constant when a
change of state occurs via a gain/loss of energy
Heat absorbed by 1 mole of a solid during
melting (constant temperature) is the molar
heat of fusion (H
fus
)
Molar heat of solidification (H
solid
) is the heat
lost by 1 mole of liquid as it solidifies
(constant temperature)
So, H
fus
= H
solid

17.3: Heat of fusion and solidification
Figure 17.9: Enthalpy changes and changes of
state
17.3: Heat of fusion and solidification
H
2
O
(s)
AH
fus
= 6.01 kJ/mol
H
2
O
(l)
H
2
O
(l)
AH
solid
= 6.01 kJ/mol
H
2
O
(s)
17.3: Heat of fusion and solidification
17.3: Heats of Vaporization and Condensation
Molar heat of vaporization (H
vap
): Amount of
heat required to vaporize one mole of a liquid
at the liquids normal boiling point
H
2
O
(l)
AH
vap
= 40.7 kJ/mol
H
2
O
(g)
Molar heat of condensation (H
cond
): heat released
when 1 mole of vapor condenses


So, H
vap
= -H
cond
H
2
O
(l)
AH
cond
= 40.7 kJ/mol
H
2
O
(g)
Figure 17.10: Heating curve of water
17.3: Heat of vaporization and
condensation
17.3: Heat of solution
There is heat released/gained when a solute
dissolves in a solvent
The enthalpy change due to 1 mole of a
substance dissolving: molar heat of solution
(H
soln
)

NaOH
(s)
AH
soln
= 445.1 kJ/mol Na
+
(aq)
+ OH
-
(aq)
H
2
O
(l)
Applications: hot/cold packs

Hot pack:

17.3: Heat of solution
CaCl
2(s)
AH
soln
= 82.8 kJ/mol Ca
2+
(aq)
+ 2Cl
-
(aq)
H
2
O
(l)
Cold pack:
NH
4
NO
3(s)
AH
soln
= 25.7 kJ/mol NH
4
+
(aq)
+ NO
3
-
(aq)
H
2
O
(l)