Thermochemistry

6.1 Energy and Its Units

6.2 Heat of Reaction
6.3 Enthalpy and Enthalpy
Change
6.4 Thermochemical Equations

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.

Energy
Types of Energy
1. Kinetic energy
2. Potential energy
3. Chemical energy
4. Heat energy
5. Electric energy
6. Radiant energy

Energy
There are three broad concepts of
energy:
Kinetic Energy is the energy associated with an
object by virtue of its motion.
Potential Energy is the energy an object has by
virtue of its position in a field of force.
Internal Energy is the sum of the kinetic and
potential energies of the particles making up a
substance.

We will look at each of these in detail.

Energy
Kinetic Energy: An object of mass m
and speed or velocity has kinetic
energy Ek equal to

Ek

1 mv 2
2

This shows that the kinetic energy of an object

depends on both its mass and its speed.

A Problem to Consider
Consider the kinetic energy of a person
whose mass is 130 lb (59.0 kg)
traveling in a car at 60 mph (26.8 m/s).

Ek

1 ( 59.0 kg ) ( 26.8 m / s ) 2
2
4
2
2

Ek 2.12 10 kg m / s
4

Ek 2.12 10 J
The SI unit of energy, kg.m2/s2, is given the name
Joule.

Energy
Potential Energy: This energy
depends on the position (such
as height) in a field of force
(such as gravity).
For example, water of a given
mass m at the top of a dam is at
a relatively high position h in the
gravitational field g of the earth.

Ep mgh

A Problem to Consider
Consider the potential energy of 1000 lb
of water (453.6 kg) at the top of a 300
foot dam (91.44 m).
2

Ep (453.6 kg) (9.80 m / s ) (91.44 m )

5

Ep 4.06 10 kg m / s
5

Ep 4.06 10 J

Energy
Internal Energy is the energy of the particles
making up a substance.
The total energy of a system is the sum of its
kinetic energy, potential energy, and internal
energy, U.

Etot Ek Ep U

Energy
The Law of Conservation of Energy:
Energy may be converted from one
form to another, but the total quantities
of energy remain constant.

Heat of Reaction
In chemical reactions, heat is often
transferred from the system to its
surroundings, or vice versa.
The substance or mixture of substances
under study in which a change occurs is
called the thermodynamic system (or
simply system.)
The surroundings are everything in the
vicinity of the thermodynamic system.

Heat of Reaction
Heat is defined as the energy that flows into
or out of a system because of a difference in
temperature between the system and its
surroundings.
Heat flows from a region of higher
temperature to one of lower temperature; once
the temperatures become equal, heat flow
stops.
(See Animation: Kinetic Molecular Theory/Heat Transfer)

Heat of Reaction
Heat is denoted by the symbol q.
The sign of q is positive if heat is absorbed
by the system.
The sign of q is negative if heat is evolved
by the system.
Heat of Reaction is the value of q
required to return a system to the given
temperature at the completion of the
reaction.

Heat of Reaction
An exothermic process is a
chemical reaction or physical
change in which heat is evolved
(q is negative).
An endothermic process is a
chemical reaction or physical
change in which heat is
absorbed (q is positive).

Heat of Reaction
Exothermicity
out of a system

Surroundings

Energy
System

q < 0

Endothermicity
into a system

Surroundings

Energy
System

q > 0

Enthalpy and Enthalpy Change

The heat absorbed or evolved by a reaction
depends on the conditions under which it
occurs.
Usually, a reaction takes place in an open vessel,
and therefore at the constant pressure of the
atmosphere.
The heat of this type of reaction is denoted q p,
the heat at constant pressure.

Enthalpy and Enthalpy Change

Enthalpy, denoted H, is an extensive
property of a substance that can be used to
obtain the heat absorbed or evolved in a
chemical reaction.
An extensive property is one that depends on
the quantity of substance.
Enthalpy is a state function, a property of a
system that depends only on its present state and
is independent of any previous history of the
system, or independent of path.

Enthalpy and Enthalpy Change

The change in enthalpy for a reaction at
a given temperature and pressure (called
the enthalpy of reaction) is obtained by
subtracting the enthalpy of the reactants
from the enthalpy of the products.

H H (products) H ( reactants )

Enthalpy and Enthalpy Change

The change in enthalpy is equal to the
heat of reaction at constant pressure.
This represents the entire change in
internal energy (U) minus any expansion
work done by the system.

H q p

Enthalpy and Enthalpy Change

Enthalpy and Internal Energy
The internal energy of a system, U, is precisely
defined as the heat at constant pressure plus the
work done by the system:

U qp w
(See Animation: Work vs. Energy Flow)
In chemical systems, work is defined as a change in
volume at a given pressure, that is:

w PV

Enthalpy and Enthalpy Change

Since the heat at constant pressure, q p,
represents H, then

U H P V
So H is essentially the heat obtained or absorbed
by a reaction in an open vessel where the work
portion of U is unmeasured.

Thermochemical Equations
A thermochemical equation is the
chemical equation for a reaction
(including phase labels) in which the
equation is given a molar interpretation,
and the enthalpy of reaction for these
molar amounts is written directly after
the equation.

N 2 (g ) 3H 2 (g ) 2NH 3 (g ); H -91.8 kJ

Thermochemical Equations
In a thermochemical equation it is
important to note phase labels because
the enthalpy change, H, depends on
the phase of the substances.

2H 2 (g ) O 2 (g ) 2H 2O(g ) ; H o - 483.7 kJ
o

2H 2 (g ) O 2 (g ) 2H 2O(l ) ; H - 571.7 kJ

Thermochemical Equations
The following are two important rules for
manipulating thermochemical equations:
When a thermochemical equation is multiplied
by any factor, the value of H for the new
equation is obtained by multiplying the H in the
original equation by that same factor.
When a chemical equation is reversed, the value
of H is reversed in sign.

Thermochemistry
6.5 Applying Stoichiometry to
Heats of Reactions
6.6 Measuring Heats of
Reactions
6.7 Hesss Law
6.8 Standard Enthalpies of
Formation
6.9 FuelsFoods, Commercial
and Rocket Fuels

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
CH4?
CH 4 (g ) 2O 2 (g ) CO 2 (g ) 2H 2O(l );H o -890.3 kJ
1 mol CH 4
10.0 g CH 4 16.0g

890.3 kJ
1mol
CH 556 kJ
4

Measuring Heats of Reaction

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.
The heat required to raise the temperature
of a substance is its heat capacity.

Measuring Heats of Reaction

Heat Capacity and Specific Heat
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:

q CT

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 25.0oC to 35.0oC is:
o

q CT (6.70 J / C) ( 35.0 C 25.0 C)

q 67.0 J

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.
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, T.

q s m T

Specific Heats and Heat Capacities

A Problem to Consider
Calculate the heat absorbed when the
temperature of 15.0 grams of water is
raised from 20.0oC to 50.0oC. (The
specific heat of water is 4.184 J/g.oC.)

q s m T
q

o
J
(4.184 go C ) (15.0g ) (50.0 20.0 C)
3

q 1.88 10 J

Heats of Reaction:
Calorimetry
A calorimeter is a device
used to measure the heat
absorbed or evolved
during a physical or
chemical change.
The heat absorbed by the
calorimeter and its contents
is the negative of the heat of
reaction.

qcalorimeter q rxn

A Problem to Consider
When 23.6 grams of calcium chloride, CaCl2, was dissolved
in water in a calorimeter, the temperature rose from 25.0oC
to 38.7oC.
If the heat capacity of the solution and the calorimeter is 1258
J/oC, what is the enthalpy change per mole of calcium chloride?

Heats of Reaction: Calorimetry

First, let us calculate the heat
absorbed by the calorimeter.

q cal CT

o
o
J
(1258 o C ) ( 38.7 C 25.0 C)

q cal 1.72 10 J
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

(1 mol CaCl 2 )
( 23.6 g CaCl 2 )
0.212 mol CaCl 2
111 .1 g
Now we can calculate the heat per mole of
calcium chloride.

q rxn
17.2 kJ
H

81.1 kJ / mol
mol CaCl 2 0.212 mol

Hesss Law
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.
(See Animation: Hesss Law)

Hesss Law
For example, suppose you are given the
following data:
o

S(s ) O 2 (g ) SO 2 (g ); H -297 kJ
o

2SO 3 (g ) 2SO 2 (g ) O 2 (g ); H 198 kJ

Could you use these data to obtain the enthalpy
change for the following reaction?

2S(s ) 3O 2 (g ) 2SO 3 (g ); H o ?

Hesss Law
If we multiply the first equation by 2 and
reverse the second equation, they will
sum together to become the third.
o

2S(s ) 2O 2 (g ) 2SO 2 (g ); H (-297 kJ) (2)

2SO 2 (g ) O 2 (g ) 2SO 3 (g ); H o (198 kJ) (-1)

o

2S(s ) 3O 2 (g ) 2SO 3 (g ); H -792 kJ

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 25oC).
The enthalpy change for a reaction in which
reactants are in their standard states is denoted
Ho (delta H zero or delta H naught).

Standard Enthalpies of Formation

The standard enthalpy of formation of a
substance, denoted Hfo, 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.
o
o
o
H nH f (products ) mH f (reactants)
is the mathematical symbol meaning the sum
of, and m and n are the coefficients of the
substances in the chemical equation.

A Problem to Consider
Large quantities of ammonia are used
to prepare nitric acid according to the
following equation:

4NH 3 (g ) 5O 2 (g ) 4NO(g ) 6H 2O(g )

What is the standard enthalpy change for this
reaction? Use Table 6.2 for data.

A Problem to Consider
You record the values of Hfo under the
formulas in the equation, multiplying them by
the coefficients in the equation.

4NH 3 (g ) 5O 2 (g ) 4NO(g ) 6H 2O(g )

4( 45.9)

5( 0)

4(90.3)

Table 6.2

Table 6.2

Table 6.2

6( 241.8)
Table 6.2

You can calculate Ho by subtracting the values

for the reactants from the values for the
products.

A Problem to Consider
Using the summation law:
H
o

o
nH f (products )

o
mH f (reactants )

H [4(90.3) 6( 241.8)] kJ [4( 45.9) 5(0)] kJ

o

H 906 kJ
Be careful of arithmetic signs as they are a
likely source of mistakes.

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

Syngas

Fuels
Food fills three needs of the body:
It supplies substances for the growth and repair of
tissue.
It supplies substances for the synthesis of
compounds used in the regulation of body
processes.
It supplies energy. About 80% of the energy we
need is for heat. The rest is used for muscular
action and other body processes

Fuels
A typical carbohydrate food, glucose (C6H12O6)
undergoes combustion according to the following
equation.

C6 H12O 6 (s ) 6O 2 (g )

6CO 2 (g ) 6H 2O(l ); H o -2803 kJ

One gram of glucose yields 15.6 kJ (3.73 kcal)
when burned.

Fuels
A representative fat is glyceryl trimyristate,
C45H86O6. The equation for its combustion is:

C45 H 86O 6 (s ) 127

2 O 2 (g )
o

45CO 2 (g ) 43H 2O(l ); H -27,820 kJ

One gram of fat yields 38.5 kJ (9.20 kcal)
when burned. Note that fat contains more
than twice the fuel per gram than
carbohydrates contain.

Metabolic Energy
The complex of biochemical reactions that make food energy
available for use by living organisms is called metabolism.
A kilocalorie (4.2kj) is the amount of heat needed to change the
temperature of 1 kg of water by 1 C; it is equal to one dietary
"calorie."
Food
kcal
1 raw onion
5
1 dill pickle
15
1 gum drop
35
1 poached egg
75
1 banana
120
1 cupcake
130
1 broiled hamburger patty 150
1 glass of milk
165
1 cup bean soup
190
1 cup tuna salad
220
1 ice cream soda
325
broiled chicken
350
1 lamb chop
420

Energy of a Snickers Bar

There are 311 Cal in a Snickers
Bar. If you added this much heat to
a gallon of water at 22oC what
would be the final temperature?
311 Cal = 311,000 cal

1 gallon of water weighs 3960.4 g

311,000 cal = 1.000 cal/goC x 3960.4g x ?oC

Solving for the change of temperature gives us 78.5oC
Add this to the 22oC to get 100.5oC which is above the
boiling point of water (100oC)

Fuels
Fossil fuels account for nearly 90% of the
energy usage in the United States.
Anthracite, or hard coal, the oldest variety of
coal, contains about 80% carbon.
Bituminous coal, a younger variety of coal,
contains 45% to 65% carbon.
Fuel values of coal are measured in BTUs
(British Thermal Units).
A typical value for coal is 13,200 BTU/lb.
1 BTU = 1054 kJ

Fuels
Natural gas and petroleum account for nearly
three-quarters of the fossil fuels consumed per
year.
Purified natural gas is primarily methane, CH4, but
also contains small quantities of ethane, C2H6,
propane, C3H8, and butane, C4H10.
We would expect the fuel value of natural gas to be
close to that for the combustion of methane.

CH 4 (g ) 2O 2 (g ) CO 2 (g ) 2H 2O(g ) ; H 802 kJ
o

Fuels
Petroleum is a very complicated mixture of
compounds.
Gasoline, obtained from
petroleum, contains
many different
hydrocarbons, one of
which is octane, C8H18.

C8 H18 (l ) 252 O 2 (g )
o

8CO 2 (g ) 9H 2O(g ); H -5,074 kJ

This value of Ho is equivalent to 44.4 kJ/gram.

Fuels
With supplies of petroleum estimated to be 80%
depleted by the year 2030, the gasification of coal
has become a possible alternative.
First, coal is converted to carbon monoxide using
steam.

C(s ) H 2O(g ) CO(g ) H 2 (g )

The carbon monoxide can then be used to produce a
variety of other fuels, such as methane.

CO(g ) 3H 2 (g ) CH 4 (g ) H 2O(g )