Enthalpy

• Standard Enthalpy H f
• The heat change that results when 1 mole of a
compound is formed from its elements at a
pressure of 1 atm
• The standard enthalpy of formation, of any
element in its most stable form is zero
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
 Thermodynamics
State functions are properties that are determined by the state
of the system, regardless of how that condition was achieved.
energy, pressure, volume, temperature

E = Efinal - Einitial
P = Pfinal - Pinitial

V = Vfinal - Vinitial
T = Tfinal - Tinitial

Potential energy of hiker 1 and hiker 2

is the same even though they took
different paths.
6.3
Energy can be converted from one form to another
e.g. from mechanical  heat  electrical  light etc.

Energy is released and absorbed when bonds are made or

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 )‫ (يمتص‬from the surroundings
Examples of exothermic reactions
neutralization
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
 Because there is no way to measure the absolute value of
the enthalpy of a substance, must I measure the enthalpy
change for every reaction of interest?

Establish an arbitrary scale with the standard enthalpy of

formation (H0f ) as a reference point for all enthalpy
expressions.

Standard enthalpy of formation (H0f) is the heat change

that results when one mole of a compound is formed from
its elements at a pressure of 1 atm.

The standard enthalpy of formation of any element in its

most stable form is zero.
H0f (O2) = 0 H0f (C, graphite) = 0
H0f (O3) = 142 kJ/mol H0f (C, diamond) = 1.90 kJ/mol
 To use this equation to determine
the standard enthalpy
• We must know the H f values of the
compounds that take place in the reaction
to use either the direct or indirect methods
 The Direct Method
• If we can directly synthesize a compound
from its elements, we have a direct
measurement of H f
• An example is:

C ( graphite )  O 2( g )  CO 2( g )  H rxn  393.5kJ / mol

 The Indirect Method

• If we can’t directly synthesize the product

we can use Hess’s law: When reactants
are converted to products, the change in
enthalpy is the same whether the reaction
takes place in 1 step or a series of steps.
• H is a state function
 Ex. Calculate the standard enthalpy of formation of CS2 (l)
given that:
C(graphite) + O2 (g) CO2 (g) H0rxn = -393.5 kJ
S(rhombic) + O2 (g) SO2 (g) H0rxn = -296.1 kJ
CS2(l) + 3O2 (g) CO2 (g) + 2SO2 (g) Hrxn
0 = -1072 kJ

1. Write the enthalpy of formation reaction for CS2

C(graphite) + 2S(rhombic) CS2 (l)

2. Add the given rxns so that the result is the desired rxn.
C(graphite) + O2 (g) CO2 (g) H0rxn = -393.5 kJ
2S(rhombic) + 2O2 (g) 2SO2 (g) H0rxn = -296.1x2 kJ
+ CO2(g) + 2SO2 (g) CS2 (l) + 3O2 (g) Hrxn
0 = +1072 kJ

C(graphite) + 2S(rhombic) CS2 (l)

H0rxn= -393.5 + (2x-296.1) + 1072 = 86.3 kJ
Ex. Benzene (C6H6) burns in air to produce carbon dioxide and
liquid water. How much heat is released per mole of benzene
combusted? The standard enthalpy of formation of benzene is 49.04 kJ/mol.
Hf0 CO2 = -393.5 KJ mol-1and Hf0 H2O = - 187.6 KJ mol-1

2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (l)

H0rxn = S nH0f (products) - S mHf0 (reactants)

H0rxn = [ 12H0f (CO2) + 6H0f (H2O)] - [ 2H0f (C6H6)]

H0rxn = [ 12x–393.5 + 6x–187.6 ] – [ 2x49.04 ] = -5946 kJ

-5946 kJ
H0 for one mole = = - 2973 kJ/mol C6H6
2 mol
 Ex. Find the standard heat of formation of (Fe2O3(s)). From
the following reactions.
C(s) + O2 (g) CO2 (g) H0 = - 94.05 Cal
3C (S) + 2 Fe2O3 (s) 4Fe (s) + 3CO2 (g) H0 = +110.8 Cal
1. Write the enthalpy of formation reaction for Fe2O3
2Fe + 3O Fe2O3 (s)

2. Add the given rxns after (2 \1-( ‫ والثانية‬2\3 ‫ضرب المعادلة االولي في‬
3/2C(s) + 3/2O2 (g) 3/2CO2 (g) H0 =3/2 * - 94.05 Cal

(-1/2)3C(S)+ (-1/2)2 Fe2O3(s) (-1/2)4Fe(s)+ (-1/2)3CO2(g) H0 =(-1/2)+110.8 Cal

3. Then:
3/2C(s) + 3/2O2 (g) 3/2CO2 (g) H0 = – 141.07 Cal
(-3/2) C(S – Fe2O3(s) -2 Fe(s) -3/2CO2(g) H0 =- 55.4 Cal

2Fe + 3O Fe2O3 (s) ΔH0 =- 196.47 Cal

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 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.

Standard enthalpy of formation is the heat absorbed when

1 mole of a substance is formed from its elements in
their standard state.
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.
The enthalpy of solution (Hsoln) is the heat generated or
absorbed when a certain amount of solute dissolves in a
certain amount of solvent.
Hsoln = Hsoln - Hcomponents

Which substance(s) could be

used for melting ice?

Which substance(s) could be

used for a cold pack?
 Hess’s Law
• For a particular reaction, the change in enthalpy
is the same whether the reaction takes place in
one step or a series of steps.
• Example:
N2(g) + 2O2(g)  2NO2(g H1 = 68 kJ
Ex. 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
 1- Solve this problem by another way Find the standard heat
of formation of (Fe2O3(s)). From the following reactions.
C(s) + O2 (g) CO2 (g) H0 = - 94.05 Cal
3C (S) + 2 Fe2O3 (s) 4Fe (s) + 3CO2 (g) H0 = +110.8 Cal

2- Calculate the ΔHfo of the Acetic acid (CH3COOH).from:

CH3COOH(l) + 2O2(g) 2H2O(l)+2CO2 (g) H0 = - 208.34 Ca
C(s) + O2 (g) CO2 (g) H0 = - 94.05 Cal
H2(g) + 1/2O2 (g) H2O (l) H0 = - 68.32 Cal
3-Calculate the ΔHfo of the reaction :
C2H6 + Cl2 C2H5Cl + HCl ΔHr= ? Kcal/mol
Given that:
C2H6 + 3.5O2 2CO2 + 3H2O ΔHr0= -341 Kcal/mol
4C2H5Cl + 13O2 8CO2 + 10H2O +2Cl2 ΔHr0= -1229.6 Kcal/mol
H2 + 1/2O2 H2O ΔHr0= -57.8 Kcal/mol
1/2H2 + 1/2Cl2 HCl ΔHr0= -2.1 Kcal/mol

4-Calculate the ΔHfo of the reaction :

C2H6 + Cl2 C2H5Cl + HCl ΔHr= ? Kcal/mol
Given that:
C2H6 + 3.5O2 2CO2 + 3H2O ΔHr0= -341 Kcal/mol
4C2H5Cl + 13O2 8CO2 + 10H2O +2Cl2 ΔHr0= -1229.6 Kcal/mol
H2 + 1/2O2 H2O ΔHr0= -57.8 Kcal/mol
1/2H2 + 1/2Cl2 HCl ΔHr0= -2.1 Kcal/mol
4-Calculate the heat of reaction:
Na2CO3(s) + 2HCl(g) 2NaCl(s) + CO2(g) +H2O(l) ΔHr0= ? cal/mol

Given: ΔHf0NaCl = -98.23 cal/mol, ΔHf0Na2CO3 = -270.3 cal/mol,

ΔHf0HCl = -22.06 cal/mol, ΔHf0CO2 = -94.05 cal/mol, and ΔHf0H2O = -68.32
cal/mol

5- Define:
Heat of formation-heat of combustion – heat of reaction-Hess
law – exothermic reaction – endothermic reaction