Thermochemistry

Chapter 6
Suggested problems for Ch. 6:

33, 35, 37, 39, 41, 43, 45, 47, 49, 51, 55, 59, 63, 65, 67, 69, 71,

73, 81, 83, 87, 89, 91, 103
Thermochemistry
Thermodynamics is the science of the
relationship between heat and other forms of
energy.

Thermochemistry is the study of the quantity of
heat absorbed or evolved by chemical reactions.
The following are two important rules for
manipulating thermochemical equations:

Thermochemical Equations
When a thermochemical equation is multiplied
by any factor, the value of DH for the new
equation is obtained by multiplying the DH in
the original equation by that same factor.
When a chemical equation is reversed, the
value of DH is reversed in sign.
Applying Stoichiometry and
Heats of Reactions
Consider the reaction of methane, CH
4
, burning
in the presence of oxygen at constant pressure.
Given the following equation, how much heat
could be obtained by the combustion of 10.0
grams CH
4
?
4
4
CH mol 1
kJ 3 . 890
g 0 . 16
CH mol 1
4
CH g 0 . 10


kJ 556
); l ( O H 2 ) g ( CO ) g ( O 2 ) g ( CH
2 2 2 4

kJ -890.3 H
o
D
To see how heats of reactions are measured,
we must look at the heat required to raise the
temperature of a substance, because a
thermochemical measurement is based on the
relationship between heat and temperature
change.

Measuring Heats of Reaction
The heat required to raise the temperature of a
substance is its heat capacity.
The heat capacity, C, of a sample of substance
is the quantity of heat required to raise the
temperature of the sample of substance one
degree Celsius.
Changing the temperature of the sample
requires heat equal to:
Measuring Heats of Reaction
Heat Capacity and Specific Heat
T C q
Figure 6.11:
Coffee-cup
calorimeter.
Figure
6.12: A
bomb
calorimeter.
A Problem to Consider
Suppose a piece of iron requires 6.70 J of
heat to raise its temperature by one degree
Celsius. The quantity of heat required to
raise the temperature of the piece of iron
from 25.0
o
C to 35.0
o
C is:
) C 0 . 25 C 0 . 35 ( ) C / J 70 . 6 ( T C q
o o o
D
J 0 . 67 q
Measuring Heats of Reaction
Heat capacities are also compared for one gram
amounts of substances. The specific heat capacity
(or specific heat) is the heat required to raise
the temperature of one gram of a substance by
one degree Celsius.


T m s q
To find the heat required you must multiply the
specific heat, s, of the substance times its mass
in grams, m, and the temperature change, DT.

A Problem to Consider
Calculate the heat absorbed when the
temperature of 15.0 grams of water is
raised from 20.0
o
C to 50.0
o
C. (The
specific heat of water is 4.184 J/g
.o
C.)
T m s q
) C 0 . 20 0 . 50 ( ) g 0 . 15 ( ) 184 . 4 ( q
o
C g
J
o


J 10 88 . 1 q
3

Energy
Energy is defined as the capacity to move
matter.
Energy can be in many forms:
>Radiant Energy -Electromagnetic radiation.
>Thermal Energy - Associated with random
motion of a molecule or atom.
>Chemical Energy - Energy stored within the
structural limits of a molecule or atom.

A Problem to Consider
Calculate the heat absorbed when the
temperature of 15.0 grams of water is
raised from 20.0
o
C to 50.0
o
C. (The
specific heat of water is 4.184 J/g
.o
C.)
T m s q
) C 0 . 20 0 . 50 ( ) g 0 . 15 ( ) 184 . 4 ( q
o
C g
J
o


J 10 88 . 1 q
3

Heats of Reaction: Calorimetry
A calorimeter is a device used to measure
the heat absorbed or evolved during a
physical or chemical change. (see Figure
6.11)
The heat absorbed by the calorimeter and its
contents is the negative of the heat of reaction.
rxn r calorimete
q q
A Problem to Consider
When 23.6 grams of calcium chloride, CaCl
2
, was
dissolved in water in a calorimeter, the
temperature rose from 25.0
o
C to 38.7
o
C.

If the heat capacity of the solution and the calorimeter
is 1258 J/
o
C, what is the enthalpy change per mole
of calcium chloride?
Heats of Reaction: Calorimetry
First, let us calculate the heat absorbed
by the calorimeter.
) C 0 . 25 C 7 . 38 ( ) 1258 ( T C q
o o
C
J
cal
o
D
J 10 72 . 1 q
4
cal

Now we must calculate the heat per mole of
calcium chloride.
Heats of Reaction: Calorimetry
Calcium chloride has a molecular mass of
111.1 g, so
2
2
2
CaCl mol 212 . 0
g 1 . 111
) CaCl mol 1 (
) CaCl g 6 . 23 (
mol / kJ 1 . 81
mol 212 . 0
kJ 2 . 17
CaCl mol
q
H
2
rxn

D
Now we can calculate the heat per mole of
calcium chloride.
Hesss law of heat summation states that
for a chemical equation that can be written
as the sum of two or more steps, the
enthalpy change for the overall equation is
the sum of the enthalpy changes for the
individual steps.
Hesss Law
Figure 6.13: Enthalpy diagram
illustrating Hesss law.
Figure 6.7: Campsite to illustrate altitude.
For example, suppose you are given the
following data:
Hesss Law
kJ -297 H ); g ( SO ) g ( O ) s ( S
o
2 2
D
kJ 198 H ); g ( O ) g ( SO 2 ) g ( SO 2
o
2 2 3
D
Could you use these data to obtain the enthalpy
change for the following reaction?
? H ); g ( SO 2 ) g ( O 3 ) s ( S 2
o
3 2
D
If we multiply the first equation by 2 and
reverse the second equation, they will sum
together to become the third.
Hesss Law
(2) kJ) -297 ( H ); g ( SO 2 ) g ( O 2 ) s ( S 2
o
2 2
D
(-1) kJ) 198 ( H ); g ( SO 2 ) g ( O ) g ( SO 2
o
3 2 2
D
kJ -792 H ); g ( SO 2 ) g ( O 3 ) s ( S 2
o
3 2
D
Standard Enthalpies of
Formation
The term standard state refers to the
standard thermodynamic conditions chosen
for substances when listing or comparing
thermodynamic data: 1 atmosphere pressure
and the specified temperature (usually 25
o
C).
The enthalpy change for a reaction in which
reactants are in their standard states is denoted
DH
o
(delta H zero or delta H naught).
Standard Enthalpies of
Formation
The standard enthalpy of formation of a
substance, denoted DH
f
o
, is the enthalpy
change for the formation of one mole of a
substance in its standard state from its
component elements in their standard
state.
Note that the standard enthalpy of formation for
a pure element in its standard state is zero.
Standard Enthalpies of
Formation
The law of summation of heats of
formation states that the enthalpy of a
reaction is equal to the total formation
energy of the products minus that of the
reactants.
S is the mathematical symbol meaning the
sum of, and m and n are the coefficients of the
substances in the chemical equation.
) reactants ( H m ) products ( H n H
o
f
o
f
o

D D D
A Problem to Consider
Large quantities of ammonia are used to
prepare nitric acid according to the
following equation:
- What is the standard enthalpy change for this
reaction? Use Table 6.2 for data.
) g ( O H 6 ) g ( NO 4 ) g ( O 5 ) g ( NH 4
2 2 3

A Problem to Consider
You record the values of DH
f
o
under the
formulas in the equation, multiplying them
by the coefficients in the equation.
- You can calculate DH
o
by subtracting the values
for the reactants from the values for the
products.
) 9 . 45 ( 4
) 0 ( 5 ) 3 . 90 ( 4 ) 8 . 241 ( 6
) g ( O H 6 ) g ( NO 4 ) g ( O 5 ) g ( NH 4
2 2 3

A Problem to Consider
Using the summation law:
- Be careful of arithmetic signs as they are a
likely source of mistakes.
) reactants ( H m ) products ( H n H
o
f
o
f
o

D D D
kJ )] 0 ( 5 ) 9 . 45 ( 4 [ kJ )] 8 . 241 ( 6 ) 3 . 90 ( 4 [ H
o
D
kJ 906 H
o
D
Fuels
A fuel is any substance that is burned to
provide heat or other forms of energy.
In this section we will look at:
- Foods as fuels
- Fossil fuels
- Coal gasification and liquefaction