THERMOCHEMISTRY

Thermochemistry is the study of the energy and heat associated with chemical reactions
and/or physical transformations. A reaction may release or absorb energy, and a phase change
may do the same, such as in melting and boiling. Thermochemistry focuses on these energy
changes, particularly on the system's energy exchange with its surroundings.

HESS'S LAW
G.H.Hess proposed a law regarding the heat or enthalpies of reaction in 1840 called the
Hess's law. This law states that "the heat change in a particular reaction is the same
whether it takes place in one step or several steps."

For example, a reactant 'A' changes to a product 'B' in one step and the heat change during
this process is DH. If the reaction is carried out in two steps where 'A' first changes to 'C' an
intermediate stage and then 'C' changes to 'B' in the following step then let the heat change
during the formation of 'A' to 'C' be DH 1 and that from 'C' to 'B' be DH 2. From Hess's law the
heat change for the reaction is given as

DH = DH1 + DH2

This means that the amount of heat evolved or absorbed in a chemical reaction depends only
upon the energy of the initial reactants and the final products. The heat change is independent
of the path or the manner in which the change has taken place.

The formation of carbon dioxide from carbon and oxygen can be illustrated as follows.
Carbon can be converted into carbon dioxide in two ways. Firstly solid carbon combines with
sufficient amount of oxygen to form CO2. The same reaction when carried out in the presence
of lesser amount of oxygen, gives carbon monoxide which then gets converted to CO 2 in step
two, in the presence of oxygen.
DH = DH1 + DH2

VARIOUS TYPES OF HEAT

1. HEAT OF COMBUSTION
The heat of combustion is the total energy released as heat when a substance undergoes
complete combustion with oxygen under standard conditions. The chemical reaction is
typically a hydrocarbon or other organic molecule reacting with oxygen to form carbon
dioxide and water and release heat. It may be expressed with the quantities:

 energy/mole of fuel (kJ/mol)

 energy/mass of fuel
 energy/volume of the fuel

The heat of combustion is conventionally measured with a bomb calorimeter. It may also be
calculated as the difference between the heat of formation ΔHo
f of the products and reactants (though this approach is purely empirical since most heats of
formation are calculated from measured heats of combustion

2. SENSIBLE HEAT

When an object is heated, its temperature rises as heat is added. The increase in heat is called
sensible heat. Similarly, when heat is removed from an object and its temperature falls, the
heat removed is also called sensible heat. Heat that causes a change in temperature in an
object is called sensible heat.

3. LATENT HEAT

All pure substances in nature are able to change their state. Solids can become liquids (ice to
water) and liquids can become gases (water to vapor) but changes such as these require the
addition or removal of heat. The heat that causes these changes is called latent heat.

Latent heat however, does not affect the temperature of a substance - for example, water
remains at 100°C while boiling. The heat added to keep the water boiling is latent heat. Heat
that causes a change of state with no change in temperature is called latent heat.
4. The HEAT OF REACTION (also known and Enthalpy of Reaction) is the change in
the enthalpy of a chemical reaction that occurs at a constant pressure. It is a
thermodynamic unit of measurement useful for calculating the amount of energy per mole
either released or produced in a reaction. Since enthalpy is derived from pressure,
volume, and internal energy, all of which are state functions, enthalpy is also a state
function.

ΔH, or the change in enthalpy arose as a unit of measurement meant to calculate the change
in energy of a system when it became too difficult to find the ΔU, or change in the internal
energy of a system, by simultaneously measure the amount of heat and work
exchanged. Given a constant pressure, the change in enthalpy can be measured as ΔH=q (see
enthalpy for a more detailed explanation).

The notation ΔHº or ΔHºrxn then arises to explain the precise temperature and pressure of the
heat of reaction ΔH. The standard enthalpy of reaction is symbolized by ΔHº or ΔHº rxn and
can take on both positive and negative values. The units for ΔHº are kiloJoules per mole, or
kj/mol.

ΔH and ΔHºrxn

 Δ = represents the change in the enthalpy; (ΔHproducts -ΔHreactants)

o a positive value indicates the products have greater enthalpy, or that it is an
endothermic reaction (heat is required)
o a negative value indicates the reactants have greater enthalpy, or that it is an
exothermic reaction (heat is produced)
 º = signifies that the reaction is a standard enthalpy change, and occurs at a preset
pressure/temperature
 rxn = denotes that this change is the enthalpy of reaction

The Standard State: The standard state of a solid or liquid is the pure substance at a pressure
of 1 bar ( 105 Pa) and at a relevant temperature. 

The ΔHºrxn is the standard heat of reaction or standard enthalpy of a reaction, and like ΔH also
measures the enthalpy of a reaction. However, ΔHºrxn takes place under "standard" conditions,
meaning that the reaction takes place at 25º C and 1 atm. The benefit of a measuring ΔH
under standard conditions lies in the ability to relate one value of ΔHº to another, since they
occur under the same conditions.

5. The STANDARD ENTHALPY OF FORMATION OR STANDARD HEAT OF

FORMATION of a compound is the change of enthalpy during the formation of 1 mole
of the compound from its constituent elements, with all substances in their standard states
at 1 atmosphere (1 atm or 101.3 kPa). Its symbol is ΔHo
f or ΔfH . The superscript theta (zero) on this symbol indicates that the process has
o

occurred under standard conditions at the specified temperature (usually 25 °C or

298.15 K).
ADIABATIC FLAME TEMPERATURE

In the study of combustion, there are two types of adiabatic flame temperature depending
on how the process is completed, constant volume and constant pressure, describing the
temperature the combustion products theoretically reach if no energy is lost to the outside
environment.

The constant volume adiabatic flame temperature is the temperature that results from a
complete combustion process that occurs without any work, heat transfer or changes in
kinetic or potential energy. The constant pressure adiabatic flame temperature is the
temperature that results from a complete combustion process that occurs without any heat
transfer or changes in kinetic or potential energy. Its temperature is lower than the constant
volume process because some of the energy is utilized to change the volume of the system
(i.e., generate work).