Elementary Thermochemistry

Thermochemistry focuses on the relationship between heat and chemical reactions.

It describes the change that occurs during chemical reactions. It is a branch in
thermodynamics, which deals with the relations between heat and all other forms
of energy such as mechanical, electrical or chemical energy. Thermodynamic
explains the relationship between all energy forms. For a better understanding of
thermochemistry which is an aspect of thermodynamics, thermodynamics should
be properly understood for better assimilation of thermochemistry aspect. The
main idea of thermodynamics is the association of heat with work done by or on a
system. There are several important terminology in thermodynamics.
 System: It is the part of the universe under study in which change occurs or
that is under investigation.
 Surrounding: It is the entire universe other than the system.
 System boundary: A hypothetical boundary which separates the system
from the surrounding.
There are basically three types of system: the open, closed and
isolated system. The open system exchanges energy and matter in the
environment, the closed system exchanges only energy, while the isolated
system cannot exchange energy or matter with the environment.
 Enthalpy: The total energy content of a thermodynamic system,
 Entropy: It is a thermodynamic expression that explains the inability of a
thermodynamic system to convert its thermal energy into mechanical
energy.
 Thermodynamic state: It is the state of a system at a given temperature.
 Thermodynamic equilibrium: It is the state of a thermodynamic system
being in equilibrium with one or more other thermodynamic system.
 Work: It is the amount of energy that is transferred to the surrounding from
a thermodynamic system.
 Internal energy: This is the total energy of a thermodynamic system that is
caused by the motion of molecules or atoms in that system.
Laws of thermodynamic
 Zeroth law of thermodynamics: when two thermodynamic systems are in
thermal equilibrium with a third thermodynamic system, all three systems
are in thermal equilibrium with each other.
  The first law of thermodynamics: It states that the energy of the universe
is constant. The change in the internal energy of a system is the sum of
heat transferred and the work done.
 Second law of thermodynamics: Heat cannot flow from a colder location
to a hotter area spontaneously. In other words, entropy or a measure of
disorder of the universe is always increasing.
 Third law of thermodynamics: as a system approach absolute zero, all
processes cease and the entropy of the system becomes minimum.
Now, with respect to thermodynamics explained above, thermochemistry can
better be assimilated.
Thermochemistry
It is the study and measurement of heat energy associated with chemical reactions.
It can also be said to be the branch of chemistry that qualitatively and
quantitatively describes the energy changes that occurs during chemical reactions.
All forms of energy can be interconverted. Three things can change the energy of
an object; the transfer of heat, work performed on or by an object, or some
combination of heat and work. During chemical reactions, energy can either be
absorbed or released and this is due to chemical bond cleavage and formations that
takes place in reactions. To break down a chemical bond, energy should be
absorbed from outside and then when a chemical bond forms, energy is released to
the surroundings. According to these heat transfer mechanism, there are two types
of chemical reactions in thermochemistry;
1. Exothermic reaction
2. Endothermic reaction
Exothermic reaction
This type of reaction releases energy by light or heat to the surrounding e.g.
neutralization, burning a substance, reactions of fuels, respiration, solution of
sulfuric acid in water etc. an exothermic reaction releases heat causing the
temperature of the immediate surroundings to rise e.g. combustion the burning of
carbon containing compounds using oxygen from air and producing carbon dioxide
water and lots of heat.
Endothermic reaction
This reaction describes a reaction where the system absorbs the energy from the
surrounding in the form of heat. An endothermic process absorbs heat and cools
the surroundings e.g. phototosynthesis, plants absorbs heat energy from sunlight to
convert carbon dioxide and water into glucose and oxygen.
Calorimetry
This is the field of science that deals with the measurement of the state of a body
with respect to the thermal state so as to examine its physical and chemical
changes.
Calorimeter
A calorimeter is used to measure the thermal changes of a body such as calculating
the enthalpy, stability of heat, capacity etc.

The heat of reaction or enthalpy of reaction

The amount of heat change when moles of reactant present in the thermochemical
reaction has completely reacted is called the heat of react or enthalpy of reaction. It
can also be said to be heat change deltaH that takes place when reactants go to
products. If heat is absorbed during the reaction, deltaH is positive (endothermic
reaction); if heat is released, then deltaH is negative (exothermic reaction).
Enthalpy in thermodynamic quantity is equivalent to the total heat content of a
system as earlier stated. The enathlpy (deltaH) is equal to the internal energy of the
system plus the product of pressure (P) and volume (V).
deltaH = E + PV
Using enthalpies of different chemical species, the heat of reaction and many other
parameters can be determined. The heat of reaction is the change in enthalpy that is
given by the difference between the enthalpy of product and enthalpy of reactant.
deltaH = deltaH (product) - delta H (reactant)

Hess law of constant summation

In physical or chemical processes heat of reaction remains the same whether it
takes place in one step or multistep.
Types of heat of reaction
 The heat of combustion or enthalpy of combustion
 The heat of formation or enthalpy of formation
 Enthalpy of neutralization
 Enthalpy of solution
 Enthalpy of hydration
 Enthalpy of transition
 Enthalpy of vaporization
 Enthalpy of sublimation
 Lattice energy
 Enthalpy of hydrogenation
 Heat of atomization
 Bond dissociation energy
 Bond energy
In thermochemical reaction it is important to note that;
1. If conditions are not given then change in enthalpy is considered to be delta
H0.
2. If the thermochemical reaction is multiplied by some coefficient then the
change in enthalpy is also multiplied by the cell coefficient.
3. If the thermochemical reaction is reversed, then the numerical value of
change in enthalpy remains the same but the sign is changed.
Calculating enthalpies of reaction from enthalpies of formation
Standard enthalpy of formation: this is the enthalpy change that occurs associated
when one mole of a substance is formed from its element in their standard state
under standard conditions (standard condition; 298k and 101.3kpa).
DeltaH = deltaHf0(product) - delta Hf0 (reactant)

Calculating enthalpies of reaction from enthalpies of combustion

The standard enthalpy change of combustion is the enthalpy change when one
mole of substance burns completely in oxygen under standard conditions.
DeltaH = deltaHcomb0(reactant) - delta Hf0 (product)