CHAPTER 9

THERMOCHEMISTRY

Definition of terms:
Calorie - a unit of energy equal to the amount of energy required to raise the temperature.
Temperature - a measure of the average kinetic energy of the particles in a substance.
Reaction - a process in which one or more substances are transformed into one or more new
substances.

Objectives:
 Identify the different types of thermochemical changes
 Calculate the heat reaction, heat formation, and heat of combustion
 Use thermochemical data to solve problems.

Heat Energy

The basic unit commonly used by chemists to measure quantities of heat energy is the calorie.
The calorie is traditionally defined as the quantity of heat required to raise the temperature of 1 gram of
water through I Celsius degrees. Today, because the heat required to raise the temperature of 1 gram of
water through 1 Celsius degree varies slightly with the temperature of the water, the calorie is defined
more precisely in terms of a work unit, the joule. A joule is the unit of energy preferred by the SI system.
It is the energy equal to the force of one Newton(N) acting through a distance of one meter in the
direction of the force.
The calorie is a very small unit of heat and is sometimes inconvenient to use. A larger unit, the
kilocalorie (kcal) is traditionally the quantity of heat required to raise the temperature of one kilogram of
water through 1 Celsius degree.

1 kcal = 1000 cal 1 kcal = 4.184 J

1 kcal = 4.19 x 103 joules

The kilocalorie is the large Calorie used in dietetics.

The specific heat of a substance is the amount of heat required to produce a given change in
temperature for a given mass of the substance. In the metric system, this is usually expressed as the
number of calories to increase the temperature of one gram of a substance by one degree Celsius. Thus in
these units,
Specific heat (c) = cal/(q)°C

The heat evolved or absorbed (Q) in a reaction can be calculated from the equation:
Q = mass x specific heat x change in temperature = mc∆ t

Q is positive when there is an increase in temperature (heat is absorbed) while Q is negative when
there is a decrease in temperature (heat is evolved). In the International System of Units specific heat is
the number of joules required to raise the temperature of 1.00kg of a substance 1.00K. The table below
lists the specific heat of a few substances using both sets of units.

Specific Heat of Some Substance

Substance Specific Heat

(cal/g°C) (J/Kg K)
Water liquid 1.00 4.19 x 103
Aluminum 0.217 9.07 x 102
Lead 0.031 1.30 x 102
Sugar 0.299 1.25 x 103
Silver 0.056 2.34 x 102
Sodium chloride 0.204 8.53 x 102
Sample Problem: How many calories would require to raise the temperature of 45 g NaCl
from 25°C
to 85°C? The specific heat of NaCl is 0.204 cal/g°C.

Samples Problem: If 8.5 of metal, initially at 82°C is placed in 45 g of water at 20° C and the
final
The temperature of metal and water is 22°C, calculate the specific heat of
the
metal in cal/g°C.
Hint: The number of calories given off by the metal is equal to the number of
calories
absorbed by the water. The specific heat of water is 1.0 cal/g°C.

Sample Problem: Calculate the number of joules of heat energy required to raise the
temperature
of 125 g of silver from 100°C to 250°C. The specific heat of silver is 2.34 x
103
J/(kg)(K).
Hint: The temperature change of 150°C is equal to a temperature change of 150K
since the degree difference on both scales is the same.

Calorimetry

Heats of the reaction are measured in a calorimeter. There are several types of calorimeter. One of
the simplest is a Styrofoam cup that can be used to make approximate measurements such as the specific
heat of a metal or heat of neutralization of an acid with a base. More complex, and hence more accurate,
calorimeters consist of a well-insulated container with a reaction vessel of some type immersed in water
inside the container.

An accurately measured amount of water is placed in the calorimeter and the temperature is
measured. Then a reaction is allowed to take place in the reaction vessel, and the change in the
temperature of the water is measured. Using the specific heat of the water as 1.00 cal/g°C, the amount of
heat produced, or absorbed, can be measured. A correction must be made, however, for the substances
other than water in the calorimeter, such as the container, the stirring apparatus, and the thermometer
since all these will also absorb some heat. To make this correction, (calibrating the instrument) a reaction
for which AH, is the correction factor. It is called the water equivalent of the calorimeter.

Thermochemistry

Almost all chemical reactions are accompanied by a gain or loss of heat. Thermochemistry is the
branch of thermodynamics devoted to the study of heat changes in chemical reactions. A reaction that
produces heat is called an exothermic reaction, while one that requires heat is called an endothermic
reaction. The amount of heat either absorbed or released in a reaction is called the heat flow, designated
as Q.
For any thermodynamic system, if heat is given off by the system (exothermic reaction), the
energy of the surroundings is increased due to the heat given off, and the heat of the system has
decreased; therefore, the heat flow is negative. If heat is absorbed by the system (endothermic reaction),
the system is increasing in heat energy and thus Q is positive.

The thermochemical equation is a chemical equation that includes the amount of energy in the
form of heat that is transferred in the reaction. This heat, usually expressed in kilocalories (kcal) or
kilojoules (kJ), can be considered as a product or a reactant in the balanced equation.
Thermochemical equations are like any other chemical equations in that the heat flow is simply
part of the total equation, like other products and reactants. Therefore, the amount of the heat is handled
in calculations stoichiometrically just like the other reactants and products from the balanced equation.
Also, thermochemical equations can be handled like algebraic equations. For example, from the equation

2H2(g) + O2(g)  2H2O(l) + 136 kcal

The following relationship can be derived.

1. For the forward reaction, 136 kcal is released (exothermic reaction).
 2. For the reverse reaction, 136 kcal of heat is absorbed (an endothermic reaction).
3. If the total equation is divided by 2, the following equation is obtained.
H2(g) + ½ O2(g)  H2O(l) + 68 kcal
The above equation may also be written as

H2(g) + ½ O2(g)  H2O(l) ∆ Hr = -68 kcal

sign of ∆ Hr is negative since heat is produced.

Enthalpy of Reaction

Enthalpy of reaction is the heat change, or change in the heat content in a chemical reaction. This
is designated by the notation ∆ H (delta "H") which indicates a change of heat flow (Q) in a reaction at
constant pressure. This is called the heat of reaction of AH, which can be calculated using the heat of
formation, ∆ Hf

∆ Hr = ∑ ∆Hf products - ∑ ∆Hf reactants

The symbol ∑ means the sum of

Heat Formation

Heat formation of a compound (∆ Hf) is defined as the ∆ Hr, or the formation of one mole of the
compound from its elements at standard state. The standard state is defined as the most stable form of an
element, such as O2(g)) for oxygen. The heat content of a free element in its standard state is taken as zero.

For example to find the heat of formation ((∆ Hf) of CO2, we can measure the heat of reaction (∆
Hr) for the reaction:

C(s) + O2(g)  CO2(g)

At 25°C and 1 atm pressure, this is experimentally found to be -94.1 kcal or -393 kJ; that is 94.1
kcal of heat is given off in this reaction. Therefore, the (∆ Hf) of Co2 is -94.1 kcal/mol.

Hf Hr
Compound kcal/mol KJ/mol Compound Kcal/mol

H2O(g) -57.8 -24.2 H2SO4(l) -907

H2O(l) -68.3 -285 CO(g) -110

NO(g) 21.5 89.9 CO2(g) -393

NO2(g) 8.0 33.4 CH3OH(l) -238

NH3(g) -11.0 -46.0 C12H22O11(S) -2215

NH4NO3(s) -87.3 -365 C2H2(g) 227

HNO3(aq) -41.4 -173 C2H4(g) 52.2

SO2(g) -71.0 -297 C2H6(g) -84.4

SO3(g) -94.5 -395

Sample Problems:

1. Given: 2C2H6(g) = 7O2(g)  4CO2(g) + 6H2O(l) = 750 kcal or 3135 kJ

 a. Is the reaction exothermic or endothermic?
b. What is the ∆ Hr for the reaction as written?
c. What is the ∆ Hr for the reverse reaction?
d. What is the Q for the forward reaction if the equation is divided by 2?
e. Calculate the amount of heat produced from the combustion of 10.0 g of C2H6 and
oxygen according to the above equation.
2. Calculate the ∆ Hr for the following reaction,

2CH3OH(l) + 3O2(g)  2CO2(g) + 4H2O(l)

Using the values of heats of formation from the table.