Hess 1

Hess' law
Hess' law of constant heat summation, also known as Hess' law

(or Hess's law), is a relationship in physical chemistry named
after Germain Hess, a Switzerland-born Russian chemist and
physician who published it in 1840. The law states that the total
enthalpy change during the complete course of a chemical
reaction is the same whether the reaction is made in one step
or in several steps.
Hess' law is now understood as an expression of the principle of

conservation of energy, also expressed in the first law of
thermodynamics, and the fact that the enthalpy of a chemical
process is independent of the path taken from the initial to the
final state (i.e. enthalpy is a state function). Reaction enthalpy
changes can be determined by calorimetry for many reactions.
The values are usually stated for processes with the same initial
and final temperatures and pressures, although the conditions
can vary during the reaction. Hess's law can be used to
determine the overall energy required for a chemical reaction,
when it can be divided into synthetic steps that are individually
easier to characterize. This affords the compilation of standard
enthalpies of formation, that may be used as a basis to design
complex syntheses.
Definition :-
Hess's law states that the change of enthalpy in a chemical
reaction (i.e. the heat of reaction at constant pressure) is
independent of the pathway between the initial and final
states.
In other words, if a chemical change takes place by several

different routes, the overall enthalpy change is the same,
regardless of the route by which the chemical change occurs
(provided the initial and final condition are the same).
Hess's law allows the enthalpy change (ΔH) for a reaction to be

calculated even when it cannot be measured directly. This is
accomplished by performing basic algebraic operations based
on the chemical equations of reactions using previously
determined values for the enthalpies of formation.
Addition of chemical equations leads to a net or overall

equation. If enthalpy change is known for each equation, the
result will be the enthalpy change for the net equation. If the
net enthalpy change is negative (ΔHnet < 0), the reaction is
exothermic and is more likely to be spontaneous; positive ΔH
values correspond to endothermic reactions. Entropy also plays
an important role in determining spontaneity, as some
reactions with a positive enthalpy change are nevertheless
spontaneous.
Hess's law states that enthalpy changes are additive. Thus the
ΔH for a single reaction complex syntheses.
Where is an enthalpy of formation, and the o superscript
indicates standard state values. This may be considered as the
sum of two (real or fictitious) reactions:
Reactants → Elements
and Elements → Products
Extension to free energy and entropy:-

The concepts of Hess's law can be expanded to include changes
in entropy and in Gibbs free energy, which are also state
functions. The Bordwell thermodynamic cycle is an example of
such an extension which takes advantage of easily measured
equilibria and redox potentials to determine experimentally
inaccessible Gibbs free energy values. Combining ΔGo values
from Bordwell thermodynamic cycles and ΔHo values found
with Hess's law can be helpful in determining entropy values
which are not measured directly, and therefore must be
calculated through alternative paths.
For the free energy:
For entropy, the situation is a little different. Because entropy

can be measured as an absolute value, not relative to those of
the elements in their reference states (as with ΔH^o and ΔG^o),
there is no need to use the entropy of formation; one simply
uses the absolute entropies for products and reactants:
Applications:-
Hess's Law of Constant Heat Summation is useful in the
determination of enthalpies of the following:
 Heats of very slow reactions.

 Heats of formation of unstable intermediates like CO(g) and
NO(g).
Since,
 Heat changes in phase transitions and allotropic

transitions.
E.g.
According to Hess’s law this difference in the enthalpy of
reaction represents the change.
i.e.
Hence the enthalpy of transition in this case = -0.273 kcal.

 Lattice energies of ionic substances by constructing Born-
Haber cycles if the electron affinity to form the anion is
known, or
 Electron affinities using a Born-Haber cycle with a
theoretical lattice energy.
 Bond Energy:-
It may be defined as, “The quantity of heat evolved when a
bond is formed between two free atoms in a gaseous state
to form a molecular product in a gaseous state”. It is also
known as enthalpy of formation of the bond.
It may also be defined as, “The average quantity of heat
required to break (dissociate) bonds of that type present
in one mole of the compound”.
E.g.
According to definition, the average bond energy per mole

of C — H bond is -398 / 4 kcal = -99.5 Kcal.

Hess 1

Uploaded by

Copyright:

Available Formats

Hess 1

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Hess 1

Uploaded by

Copyright:

Available Formats

Hess' law

Hess' law of constant heat summation, also known as Hess' law

Hess' law is now understood as an expression of the principle of

In other words, if a chemical change takes place by several

Hess's law allows the enthalpy change (ΔH) for a reaction to be

Addition of chemical equations leads to a net or overall

and Elements → Products

Extension to free energy and entropy:-

For the free energy:

For entropy, the situation is a little different. Because entropy

 Heats of very slow reactions.

 Heat changes in phase transitions and allotropic

Hence the enthalpy of transition in this case = -0.273 kcal.

According to definition, the average bond energy per mole

You might also like