3 Enthalpy

Units SI unit = joule

1KJ = 1000J = 239.0 cal

1st law of Thermodynamics

The total energy of the universe is constant

i.e energy cannot be created or destroyed but can

be changed from one form to another.
Heat (or thermal energy) q is the energy transferred between
a system and its surroundings as a result of a difference
in temperature only.

All other forms of energy transfer (mechanical, electrical etc)

involve some type of work, w, the energy transferred
when an object is moved by a force.

State functions A state function is a property dependant on

the current state of the system (e.g. its composition,
volume, temp etc)
It is independent of the path the system took to reach that
state.
 Energy of a system is a state function

 So E is a constant for any given change but q and w

may vary

 (q and w are not state functions)

and E = q + w
Energy can be converted from one form to another
e.g. from mechanical  heat  electrical  light etc.

Energy is released when bonds are made

Energy is used when bonds are broken
Chemical reactions involve

Bond breaking
Bond forming
Energy changes for an exothermic reaction – one where
heat is released to the surroundings
Energy changes for an endothermic reaction – one
where heat is absorbed from the surroundings
Examples of exothermic reactions
neutralisation
burning hydrocarbons
respiration

Examples of endothermic reactions

photosynthesis
dissolving ammonium nitrate in water
The chemical energy which a system possesses is its
enthalpy. Enthalpy is the change in energy at constant
pressure

symbol H

And H = H products – H reactants

if energy is absorbed by a system H is positive

if energy is released by a system H is negative
 Energy changes for an endothermic reaction

A B C D
E

Bond Bond forming

breaking
A—C + B—D

Products
A—B + C—D Overall energy
change

Reactants

Products have more energy than reactants

Energy changes for an exothermic reaction
A B C D
E

Bond breaking Bond forming

A—B + C—D
Reactants
Overall energy A—C + B—D
change
Products

Products have less energy than reactants

 Energy Diagrams

Activation energy
Reactants

H
Products

Time

An exothermic reaction
Reactants
E
Activation energy

Products

H
Reactants

Time

An endothermic reaction
Standard enthalpy of formation is the heat absorbed when 1
mole of a substance is formed from its elements in their
standard state.

The standard state of a substance is 1 mole of the

substance in a specified state (solid, liquid, gas) at 1
atmosphere of pressure. The value of an enthalpy change
is quoted for standard conditions: gases at 1 atm,
solutions at unit concentration and substances in their
normal states at a specified temperature. (usually 273K or
00C)

All elements in their standard state are assigned an enthalpy

of formation of 0
Standard enthalpy of reaction is the heat absorbed in a
reaction at constant pressure between the number of
moles of reactant shown in the equation for the reaction.

Standard enthalpy of combustion is the heat absorbed when

1 mole of a substance is completely burned in oxygen at
constant pressure.

Standard enthalpy of solution is the heat absorbed when 1

mole of a substance is dissolved at constant pressure in a
stated amount of solvent. This may be 100g or 100ml or
an ‘infinite’ amount, i.e. a volume so large that on further
dilution there is no further heat change.
HrӨ depends only on the difference between the
standard enthalpy of the reactants and the standard
enthalpy of the products, not on the route by which the
reaction occurs.

This is Hess’s Law – If a reaction can proceed by more

than one route the overall enthalpy is the same
regardless of which route is followed.
Find the enthalpy change for the reaction
CH2= CH2(g + HCl(g)  C2H5Cl(g)

Given the following data

HfӨ = standard enthalpy change of formation
HfӨ CH2CH2 = +52.3 KJ mol-1
HfӨ HCl = - 92.3 KJ mol-1
HfӨ C2H5Cl = -105 KJ mol-1

H = HfӨ products - HfӨ reactants

HrӨ = -105 – (+52.3) + (-92.3)
= -65KJ mol-1
Note that the formula H = HfӨ products - HfӨ reactants
Applies when the data given is the enthalpy of formation.
If the data given is the enthalpy of combustion the following formula is
used H = HcӨ reactants - HcӨ products

It doesn’t matter what the reaction is called. It may be called a

combustion reaction but if the data given is the enthalpy of formation
use the formula H = HfӨ products - HfӨ reactants !
Calculate the standard enthalpy of reaction for the following

2C + 2H2(g) + O2  CH3CO2H(l)

Given the following enthalpies of combustion

C -394 KJ/mol
H2(g) -286 KJ/mol

CH3CO2H(l) -876 KJ/mol

r = (2x -394) + (2x-286) – (-876) KJ/mol = -484 KJ/mol