ENERGETICS

/THERMOCHEMISTRY
(AS)
• 1.Often chemical changes are
accompanied by changes in heat
content / enthalpy of the materials
reacting (H)
• 2. This change is shown by a change
in temperature.
• a. heat is lost to the surroundings
• Temperature of reaction mixture
rises / increases
• H is negative
• Exothermic reaction
• Enthalpy diagram / energy level
diagram

OR Reaction pathway/reaction
coordinate/extent of reaction
• b. heat is absorbed from the
surroundings , temperature of
reaction mixture decreases / falls
• H is positive
• Endothermic reaction
• 3. a. The value of H depends on
temp , pressure and concentrations
of reactants.
• b. H are measured under standard
conditions :
• Temperature = 298K ( 250 C )
• Pressure = 1 atm / 1.01 x 105 Pa
• Concentrations = 1 mol dm-3
• c. Any H measured under standard
conditions is described as standard
enthalpy change.
• Symbol : H
 STANDARD
ENTHALPIES
Definitions
State symbols must be
included in equations
 STANDARD
ENTHALPHY OF
FORMATION ( Hf )


Enthalpy change when 1 mole of a

compound is formed from its
elements in their standard states
, under standard conditions
temperature 298 K and pressure
of gases at 1 atm
• Steps in writing equations:
• 1. write formula of compound formed
• 2. identify elements required to form
the compound
• 3. balance equation to form 1 mole
of the compound
 Examples
• Mg (s) + ½O2 (g) → 1MgO (s)
-602 kJ mol-1
602 kJ evolved for every 1 mole of
MgO formed
• ½ H2 (g) + ½ Cl2 (g) → 1HCl (g)
- 92.3 kJ mol-1
 Examples

Notes :
1) Hf of elements is zero
Eg : Cu(s)  Cu(s) , Hf = 0
2) Hf are often theoretical only
• Exercise : Write the equation for
enthalpy of formation for : KMnO4 (s)
and H2O (l)

• K(s) + Mn(s) + 2O2(g) 1KMnO4(s)

• H2(g) + ½O2(g)  1H2O (l)

 STANDARD
ENTHALPY CHANGE
OF COMBUSTION
( Hc )


Enthalpy evolved when 1 mole of

the element or compound is
completely burned in excess
oxygen , under standard
conditions
• Steps in writing equations :
• 1. identify products formed from
burning of compound in excess
oxygen
• 2. balance equation for 1 mole of
compound burnt
 Examples
• 1 C (s) + O2 (g) → CO2 (g)
Hc = - 394 kJ mol-1
394 kJ evolved for every 1 mole of
carbon burnt
• 1 H2 (g) + ½O2 (g) → H2O (l)
•Exercise : Write an equation for the
enthalpy of combustion for C3H6 and
CH3OH
• 1C3H6 (g) + 9/2 O2 (g)  3CO2 (g)
+ 3H2O (l)

• 1CH3OH (l) + 3/2 O2 (g)  CO2 (g)

+ 2H2O (l)
 STANDARD ENTHALPY OF
ATOMISATION ( Hat )
• Enthalpy required/absorbed
• 1 mole of gaseous atoms formed
• From the element in its standard
state under standard conditions
• Examples :
• Fe (s)  1 Fe (g)
• Example :
• ½Cl2(g)  1 Cl (g) + 122 kJ mol-1
• molecules atoms

• Note : from Data Booklet

• Bond energy Cl-Cl = + 244 kJ mol-1
• Cl-Cl  2 Cl (g) 2 moles atoms
• Hat of Cl = ½ x bond energy Cl-Cl
 STANDARD BOND
DISSOCIATION ENTHALPY
• Also called bond energy

• Energy absorbed

• Separate the 2 atoms in a covalent

bond in gaseous state under
standard conditions , per mole of
bond.
 Examples
• 1) HCl (g) → H (g) + Cl (g) , +431 kJmol-1
• 2) CH4 contains 4 x C-H bond
• Total energy required to break all bonds in
CH4 = 1640 kJ
• ¼ CH4 = ¼ ( 4 C-H bond ) = one C-H
bond
• Average bond energy of one C-H bond
• = ¼ ( 1640 ) = +410 kJ
• ¼ CH4 (g)→¼ C (g) + H (g),+ 410 kJmol-1
 STANDARD ENTHALPY OF
NEUTRALIZATION
• Energy evolved
• Acid reacts with base to form 1 mole of
water , under standard conditions

• Examples :
• NaOH + HCl → NaCl + 1 H2O
• KOH + HCl → KCl + 1 H2O
• Ionic equation(strong acid + strong base:
H+(aq) + OH-(aq)  1 H2O (l),
H neutralisation = -57 kJ mol-1
• Generally,
• 1) Strong acid / strong alkali :
• H = - 57 kJ mol-1

• 2) Weak acid / base :

• H = -(<57) kJ mol-1 (eg. -54 kJmol-1)

• Reason : Certain amount of energy

required to ionise the weak acid or base
first
 STANDARD ENTHALPY OF
HYDRATION ( Hhyd )
• Energy evolved
• 1 mole of separate gaseous ions
dissolved in water under standard
conditions
• Exothermic as attraction/bond forms
between the ions and polar water
molecules
• Called ion dipole attraction
• Examples :
• 1 Na+ (g) → Na+ (aq) -406 kJmol-1
• 1 Cl- (g) → Cl- (aq) - 381 kJmol-1
• Hhyd for compounds =
• sum of Hhyd of constituent ions
Eg : Hhyd MgCl2 = Hhyd Mg2+ +
2 x Hhyd Cl-
= -1891 + 2(-381)
= - 2653 kJ
• H (hyd)  charge density of ions
• Charge density = charge/size
• Higher charge density , stronger ion
dipole attraction , more exothermic
H(hyd)
• Eg :
• H(hyd) Cl- > H(hyd) Br –
• -381 -351
 STANDARD ENTHALPY OF
SOLUTION ( Hsolution )
• Enthalpy change when 1 mole of a
substance dissolved in a stated
amount of solvent under standard
conditions
• Example :
• 1 KOH (s)  K+ (aq) + OH- (aq)
or KOH (aq)
- 57 kJ mol-1
STANDARD ENTHALPY CHANGE
OF REACTION ( Hr )
• Enthalpy change in a chemical
reaction , for the number of moles of
reactants as shown in a balanced
chemical equation under standard
conditions
• Example :
4 H2O + 3 Fe  Fe3O4 + 4 H2
 Hr = x kJ when 4 moles H2O
reacts with 3 moles Fe
 HESS’S LAW
“The enthalpy change is independent of the path taken”

How The enthalpy change going from

A to B can be found by adding the
values of the enthalpy changes for
the reactions A to X, X to Y and Y to B.

DHr = DH1 + DH2 + DH3

 HESS’S LAW
“The enthalpy change is independent of the path taken”

How The enthalpy change going from

A to B can be found by adding the
values of the enthalpy changes for
the reactions A to X, X to Y and Y to B.

DHr = DH1 + DH2 + DH3

If you go in the opposite direction of an arrow, you subtract the value of

the enthalpy change.

e.g. DH2 = - DH1 + DHr - DH3

The values of DH1 and DH3 have been subtracted because the route
involves going in the opposite direction to their definition.
 HESS’S LAW
“The enthalpy change is independent of the path taken”

Use applying Hess’s Law enables one to calculate enthalpy changes from
other data, such as...

changes which cannot be measured directly e.g. Lattice Enthalpy

enthalpy change of reaction from bond enthalpy

enthalpy change of reaction from DH°c

enthalpy change of formation from DH°f

 Enthalpy of reaction from bond enthalpies
Theory Imagine that, during a reaction, all the bonds of reacting species are broken
and the individual atoms join up again but in the form of products. The
overall energy change will depend on the difference between the energy
required to break the bonds and that released as bonds are made.

energy released making bonds > energy used to break bonds ... EXOTHERMIC
energy used to break bonds > energy released making bonds ... ENDOTHERMIC

Step 1 Energy is put in to break bonds to form separate, gaseous atoms

Step 2 The gaseous atoms then combine to form bonds and energy is released
its value will be equal and opposite to that of breaking the bonds

Applying Hess’s Law DHr = Step 1 + Step 2

 Enthalpy of reaction from bond enthalpies
Alternative view
Step 1 Energy is put in to break bonds ATOMS
to form separate, gaseous atoms.
SUM OFTHE BOND
Step 2 Gaseous atoms then combine ENTHALPIES OF SUM OFTHE
to form bonds and energy is THE REACTANTS BOND
released; its value will be equal ENTHALPIES OF
and opposite to that of breaking THE PRODUCTS
REACTANTS
the bonds
DH
DHr = Step 1 - Step 2

Because, in Step 2 the route involves PRODUCTS

going in the OPPOSITE DIRECTION
to the defined change of bond enthalpy,
it’s value is subtracted.

DH =  bond enthalpies –  bond enthalpies

of reactants of products
 Enthalpy of reaction from bond enthalpies
Calculate the enthalpy change for the hydrogenation of ethene
 Enthalpy of reaction from bond enthalpies
Calculate the enthalpy change for the hydrogenation of ethene

DH2 1 x C=C bond @ 611 = 611 kJ

4 x C-H bonds @ 413 = 1652 kJ
1 x H-H bond @ 436 = 436 kJ
Total energy to break bonds of reactants = 2699 kJ
 Enthalpy of reaction from bond enthalpies
Calculate the enthalpy change for the hydrogenation of ethene

DH2 1 x C=C bond @ 611 = 611 kJ

4 x C-H bonds @ 413 = 1652 kJ
1 x H-H bond @ 436 = 436 kJ
Total energy to break bonds of reactants = 2699 kJ

DH3 1 x C-C bond @ 346 = 346 kJ

6 x C-H bonds @ 413 = 2478 kJ
Total energy to break bonds of products = 2824 kJ

Applying Hess’s Law DH1 = DH2 – DH3 = (2699 – 2824) = – 125 kJ

 Enthalpy of reaction from enthalpies of formation

If you formed the products from their elements you should need the same
amounts of every substance as if you formed the reactants from their elements.

Enthalpy of formation tends to be an exothermic process

 Enthalpy of reaction from enthalpies of formation

Step 1 Energy is released as reactants

ELEMENTS
are formed from their elements.
SUM OFTHE
Step 2 Energy is released as products ENTHALPIES OF
are formed from their elements. FORMATION OF SUM OFTHE
THE REACTANTS ENTHALPIES
OF
DHr = - Step 1 + Step 2 REACTANTS
FORMATION
OF THE
PRODUCTS
or Step 2 - Step 1
DH
In Step 1 the route involves going in the
OPPOSITE DIRECTION to the defined
PRODUCTS
enthalpy change, it’s value is subtracted.

DH =  DHf of products –  DHf of reactants

 Enthalpy of reaction from enthalpies of formation

Sample calculation
Calculate the standard enthalpy change for the following reaction, given that the
standard enthalpies of formation of water, nitrogen dioxide and nitric acid are -286,
+33 and -173 kJ mol-1 respectively; the value for oxygen is ZERO as it is an element

2H2O(l) + 4NO2(g) + O2(g) ———> 4HNO3(l)

DH =  DHf of products –  DHf of reactants

By applying Hess’s Law ... The Standard Enthalpy of Reaction DH°r will be...

PRODUCTS REACTANTS
[ 4 x DHf of HNO3 ] minus [ (2 x DHf of H2O) + (4 x DHf of NO2) + (1 x DHf of O2) ]

DH°r = 4 x (-173) - 2 x (-286) + 4 x (+33) + 0

ANSWER = - 252 kJ
 Enthalpy of reaction from enthalpies of combustion

If you burned all the products you should get the same amounts of oxidation products
such a CO2 and H2O as if you burned the reactants.

Enthalpy of combustion is an exothermic process

 Enthalpy of reaction from enthalpies of combustion

Step 1 Energy is released as reactants REACTANTS

undergo combustion.
DH
Step 2 Energy is released as products
SUM OFTHE
undergo combustion. ENTHALPIES OF
PRODUCTS COMBUSTION
DHr = Step 1 - Step 2 OF THE
SUM OFTHE REACTANTS
ENTHALPIES OF
COMBUSTION OF
THE PRODUCTS
Because, in Step 2 the route involves
going in the OPPOSITE DIRECTION to the OXIDATION
defined change of Enthalpy of PRODUCTS
Combustion, it’s value is subtracted.

DH =  DHc of reactants –  DHc of products

 Enthalpy of reaction from enthalpies of combustion

Sample calculation
Calculate the standard enthalpy of formation of methane; the standard enthalpies of
combustion of carbon, hydrogen and methane are -394, -286 and -890 kJ mol-1 .

C(graphite) + 2H2(g) ———> CH4(g)

DH =  DHc of reactants –  DHc of products

By applying Hess’s Law ... The Standard Enthalpy of Reaction DH°r will be...

REACTANTS PRODUCTS
[ (1 x DHc of C) + (2 x DHc of H2) ] minus [ 1 x DHc of CH4]

DH°r = 1 x (-394) + 2 x (-286) - 1 x (-890)

ANSWER = - 76 kJ mol-1