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CHEMICAL ENERGETICS

ENTHALPY & ENTHALPY CHANGES

The total chemical energy of a substance is called its enthalpy (heat content).
It is an indication of the energetic stability and not kinetic stability.
Chemical energy consists of kinetic energy and potential energy. The potential energy, due to
electrostatic force of attraction between the particles, is usually the main component of the
total chemical energy.
E.g. A + B C + D
Enthalpy change: Hreaction = () ()
= HC + HD (HA + HB)
ACTIVATION ENERGY

The activation energy of a reaction (Ea) is the minimum energy which the reacting particles must
possess in order to overcome the energy barrier before becoming products.

STANDARD CONDITIONS & STANDARD STATES

Temperature = 298K
Pressure = 1 atm
Concentration of solution = 1.0 mol dm-3
Elements in their standard states under standard conditions are assigned zero enthalpy (H=0).
A substance in its most stable physical state at 298 K and 1 atm is in its standard states.
*C(s) refers to the graphite allotrope since graphite is energetically more stable than diamond.
When a substance exists as allotropes, state the allotrope referred to.
STANDARD ENTHAPHY CHANGE OF REACTION

The enthalpy change when molar quantities of reactants as specified by the chemical equation react
to form products at 1 atm and 298K (standard conditions).

STANDARD ENTHAPHY CHANGE OF FORMATION


The enthalpy change when 1 mole of a substance is formed from its constituent elements in their
standard states at 298K and 1 atm.

STANDARD ENTHAPHY CHANGE OF COMBUSTION


The energy released when 1 mole of a substance is completely burnt in excess oxygen at 298K and
1 atm.

C(s) + 2O2 (g) CO (g) H is not Hco(C) but Hfo(CO), since CO is produced via incomplete
combustion of carbon.
CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l)
Note water is in liquid state and not gaseous state because water exists as liquid under
standard conditions.
Always exothermic
The more exothermic the reaction, the higher the energy value of the fuel.
STANDARD ENTHALPY CHANGE OF NEUTRALIZATION

The heat evolved when 1 mole of water is formed in the neutralization reaction between an acid
and a base, at 298K and 1 atm.

Exothermic since it involves the attraction of H+ and OH- ions to form an O H bond
Enthalpy change of neutralization of a strong acid and a strong base is almost the same for
all strong acids and bases (-57.0 kJ mol-1).
Explanation: Strong acids and strong bases ionize completely in dilute aqueous solution.
Reaction between them is effectively the reaction between aqueous H+ and OH- ions.

Enthalpy change of neutralization involving a weak acid or a weak base is slightly less
exothermic than -57.0 kJ mol-1.
Explanation: Weak acids/bases do not ionize completely in dilute aqueous solutions. During
neutralization, energy is absorbed to ionize the unionized weak acid/base. Ionization,
which involves bond breaking, is an endothermic process. Less energy is released and the
resulting Honeutralisation is less exothermic.
STANDARD ENTHALPY CHANGE OF ATOMIZATION

Hoatom for an element is the energy required when 1 mole of gaseous atoms is formed from the
element at 298K and 1 atm.

E.g. Na (s) Na (g) Hoatom = +107 kJ mol-1


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Br2
2

(g) Br (g) Hoatom = +112 kJ mol-1

Noble gases have enthalpy change of atomization of 0.

Hoatom for a compound is the energy required to convert 1 mole of the compound into gaseous
atoms at 298K and 1 atm.

Hoatom is always positive as atomization involves breaking bonds.


Depending on the type of substance, atomization is associated with different processes.
E.g. Na (s) Na (g) Hoatom = Hofusion + Hovapourization
Br2 (l) 2 Hoatom = Hovapourization + B.E. (Br Br)
CH4 (g) C (g) + 4H (g)

BOND DISSOCIATION ENERGY


Bond dissociation energy is the energy required to to break 1 mole of a particular covalent bond in a
specific molecule in the gaseous state.

Always positive
It is a measure of the strength of covalent bonds.
In molecule like methane, the successive bond dissociation energies of each of the C H
bonds are different.
Bond dissociation energy of the same type of bond in different molecules may differ.
BOND ENERGY

Bond energy is the average energy required to break 1 mole of a covalent bond in the gaseous
state.

Note that when bond energy is used, all reactants and products are in their gaseous states.

LATTICE ENERGY
The energy evolved when 1 mole of solid ionic compound is formed from its constituent gaseous
ions.

Always negative
It is a measure of the strength of ionic bonds and the stability of the ionic compounds.
There is always a difference between theoretical lattice energy and experimental lattice
energy, as one refers to the value found from experimental results using the Born-Haber
cycle while the latter refers to the value calculated based on a model which assumes that
the compound is completely ionic.
A small difference shows that the ionic model is a good one for the compound while a large
difference shows that there is covalent character in the ionic bond.
IONIZATION ENERGY

The first ionization energy is the energy required to remove 1 mole of electrons from 1 mole of
gaseous atoms to form 1 mole of singly charged gaseous cations.

Always positive
ELECTRON AFFINITY

The first electron affinity is the enthalpy change when 1 mole of electrons is added to 1 mole of
gaseous atoms to form 1 mole of singly charged gaseous anions.

1st EA is usually negative due to the attraction between the incoming electron and the atom.
(electron is added to a neutral atom and there is attraction between them)
2nd and subsequent EA are always positive because energy is required to overcome the
electrostatic repulsion between the incoming electron and the anion. (electron is added to a
negatively charged anion and repulsion needs to be overcome)
STANDARD ENTHALPY CHANGE OF HYDRATION

The energy evolved when 1 mole of free gaseous ions is dissolved in an infinite volume of water at
298K and 1 atm.

Hohydration is always negative (for both cation and anion) as heat energy is evolved in
forming ion-dipole interactions between the ions and the polar water molecules.
Magnitude of Hohydration depends on its charge density:
|()|

STANDARD ENTHALPY CHANGE OF SOLUTION


The enthalpy change when 1 mole of solute is completely dissolved in an infinite volume of solvent
at 298K and 1 atm.

Hosolution can be either positive or negative.


If it is highly positive, the salt is likely to be insoluble.
If it is negative, the salt is likely to be soluble.
Some salts with positive Hosolution are soluble e.g. NaCl, KCl, NH4NO3 due to a positive
entropy change.

RELATIONSHIP BETWEEN LATTICE ENERGY, ENTHALPY CHANGE OF HYDRATION & ENTHALPY


CHANGE OF SOLUTION

The dissolution of an ionic solid MX(s) can be divided into 2 processes:


1. Breaking up the solid ionic lattice to form isolated gaseous ions. The process is endothermic and
the enthalpy change is LE.
2. Hydration of the gaseous ions. Process is exothermic (forming ion-dipole interactions between ion
and water).
M+ (g) + X- (g) + aq M+ (aq) + X- (aq)

H = Hohydration (M+) + Hohydration (X-)

Overall: MX(s) M+ (aq) + X- (aq)


Hosolution =

sum of Hohydration - L.E.

HESSS LAW
The enthalpy change H of a reaction is determined only by the initial and final states of the system
and is independent of the reaction pathway taken.

CALCULATIONS OF ENTHALPY CHANGES


Calculation of Enthalpy Change of Reaction
1. Construct a balanced chemical equation for the reaction. Label it as equation (1).
2. Inspect the given enthalpy changes of the reactions and write down the chemical equations
for these reactions in such a way that
i.
Reactants appear on the left
ii.
Products appear on the right
3. Add the equations by canceling out the same substances.
4. Enthalpy change of reaction is equal to the algebraic sum of the given enthalpy changes of
the reactions that have been added.
Example:
Find the standard enthalpy change of formation of CO if the standard enthalpy changes of the
combustion of C and CO are 393 kJ mol-1 and 283 kJ mol-1 respectively.
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Equation (1): C (s) + 2O2 (g)

CO (g)

Hfo (CO) = ?

Given reactions:
Equation (2): C (s) + O2 (g)
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Equation (3): CO (g) + 2O2 (g)

Hco (C) = - 393 kJ mol-1

CO2 (g)

Hco (CO) = - 283 kJ mol-1

CO2 (g)
1

Reversing equation (3), CO2 (g) CO (g) + 2O2 (g)

-Hco (CO) = + 283 kJ mol-1

Equation (1) = Equation (2) + Reverse of equation (3)


Hence, Hfo (CO) = - 393 + 283 = -110 kJ mol-1
Determine Enthalpy Change Using Standard Enthalpy Change of Formation & Standard Enthalpy
Change of Combustion
Horeaction = Hfo (products) - Hfo (reactants)

Horeaction = Hco (reactants) - Hco (products)

ENTROPY CHANGES

A spontaneous process is one that in the absence of any barrier such as activation energy,
take place naturally in the direction stated. The change occurs without a need for
continuous input of energy from outside of the system.
It is irreversible as it cannot be brought back to its original state again under the same
condition.
Sign of H by itself does not predict if a reaction is spontaneous.

Entropy
Entropy S is a measure of the randomness/disorder of a system, reflection in the number of ways
that the energy of a system can be distributed through the motion of its particles. SI units: J mol-1K-1

For a spontaneous change, the total entropy must increase. Processes with positive entropy
change can occur spontaneously even though they may be endothermic.
FACTORS CAUSING ENTROPY CHANGES

Change in
temperature

As temperature increases, the average kinetic energy of the particles and the
range of the energies increase. There are more ways to disperse the energy
among the particles and entropy increases.

Change in phase

During melting, heat is absorbed so kinetic energy increases. The order in the
solid is destroyed and the particles move more freely and are further away
from each other. There are more ways the particles and their energies can be
distributed. Entropy increases.
In vaporizing, heat is absorbed so the kinetic energy increases. There is also a
large increase in volume and the particles move more freely and they are
further away from each other resulting in many more ways that the particles
and the energy can be distributed. Entropy increases.
Note: mention more way both the particles and their energies can be
distributed.

Change in number
of particles (for
gases only)

When there is an increase in the number of gas particles, there is a large


increase in entropy as the gases are the most disordered so the number of
ways that the particles and the energy can be distributed increase greatly.
If there is no change in the number of gas particles, entropy may increase or
decrease but will be relatively small numerically.

Mixing of particles When gases are mixed, each gas expands to occupy the whole container under
same constant pressure. The volume available for each gas is increased. There
are more ways the particles and their energies can be distributed. Entropy
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increases.
However, when the gases are mixed at constant volume, the entropy does
not change.
When a gas expands (due to removal of external pressure), the volume
available increases so entropy increases as there are more ways that the
particles and the energy can be distributed. Liquid with similar polarities (e.g.
benzene and hexane) mix together spontaneously.
Dissolution of an
ionic solid

Entropy increases because the ions in the solid are free to move in solution.
Entropy also decreases because water molecules that were originally free to
move become restricted by the hydration of the ions.
The overall entropy change depends on which of the above factors is more
significant. For ions with a single charge, the overall entropy is usually
positive.

GIBBS FREE ENERGY


G = H - TS

G < 0

The reaction is feasible and takes place spontaneously.


Reaction is exergonic.

G = 0

The system is at equilibrium. There is no net reaction in the forward or


backward direction.
G = 0 during melting and boiling.

G > 0

The reaction is not feasible and cannot take place spontaneously.


It is spontaneous in the reverse direction.
Reaction is endergonic.

G is dependent on temperature.
It is not incorrect to assume that H and S remain roughly constant regardless of
temperature. However, this assumption would be incorrect when there is a change in phase
of one of the reactants or products as the temperature is increases. In such cases, H and S
change significantly.
While Gibbs free energy can be used to determine the feasibility of a reaction, it does not
take into account the kinetics of the reaction.
Some reactions are thermodynamically favourable but kinetically not feasible.

G
H

-T S
At Low Temperature

At High Temperature

Always < 0
A

Temperature
independent
cases

<0

>0

<0
Spontaneous at temperatures
Always > 0

>0

<0

>0
Non-spontaneous at temperatures

Temperature
dependent
cases

>0

<0

>0

<0

>0

<0

Non-spontaneous

Spontaneous

<0

>0

Spontaneous

Non-spontaneous

<0

>0

MISCONCEPTIONS & REMARKS

Always take note of the limiting reagent. For enthalpy change of neutralization for example,
if NaOH is the limiting reagent, doubling the concentration of H+ ions (e.g. using sulfuric acid
of same concentration and volume instead of HCl) will not cause the temperature of the
solution to go higher. This is because the same amount of water is produced, since OH- ions
are the limiting reactant. [T5 Q2]
Enthalpy change of the reaction between aqueous HCl and solid NaOH is higher than that of
the reaction between aqueous HCl and aqueous NaOH. This is because enthalpy change of
solution of NaOH is exothermic. [T5 Q2]
Always use the term more/less endothermic/exothermic rather than higher and lower.
When explaining why some reactions occur (e.g. why N2 (g) reacts with O2 (g) to produce NO
in car engines), state that the high temperature (condition) provides sufficient energy to
overcome the activation energy. [T5 Q4]
Note that the equation of G = H TS can be in the form of y = mx + c, where G = y and
H = c. Gradient obtained from a G temperature graph gives S. [T5 Q12]
Take note of the standard conditions, 1. 298K, 2. 1 atm, 3. Concentration of solution is 1 mol
dm-3. This is important as some of these conditions have to be inferred as they are not
explicitly stated. [T5 Q12] [Class Test Q2]
Horeaction = Hfo (products) - Hfo (reactants) is also applicable to entropy changes
of formation.
E.g. Soreaction = Sfo (products) - Sfo (reactants) [T5 Q13]
ZnCO3 (s) + 2 HCl (aq) ZnCl2 (aq) + H2O (l) + CO2 (g)
Given that 192 J of heat was liberated from the reaction and that HCl is the limiting reagent
(0.01 mol), the enthalpy change is given by:
1
2

H =

192
0.0100

= -19200 J mol-1

H = -19200 2 = -38.5 kJ mol-1


This is because

192
0.0100

gives the enthalpy change for 1 mol of HCl. However, 2 mol of HCl

were stated in the equation. Multiplication by 2 is therefore necessary. [Class Exercise 2 Q2]

1
O2
2

(g) O (g) is a process of atomization. Note that oxygen now exists as atoms rather

than molecules. The 2 are hence different and enthalpy change of atomization must be
factored into calculation. [Class Exercise 3 Q2]
When making calculations involving bond energy, besides noting the all reactants and
products must exist in gaseous state, also take note that all bonds of reactants and
products must be taken into account as it is common to miss out some of them. [Class
Exercise 3 Q1]
Note that ion-dipole interaction is different from permanent dipole permanent dipole
interactions. Ions such as OH- carries a full negative charge is not a partial negative charge
and hence the delta minus sign should not be labelled on hydroxide ions. Also, take note
that it is the O that carries the negative charge and this has to be taken note of in drawing
the ion-dipole interactions. [Class Exercise Q2]
Take note of the terms energy released and energy required in the definition of some
enthalpy terms. [Class Test Q1]

When drawing energy level diagrams for Born Haber cycle, note that ionization of cations
comes before ionization of anions. This is because cations must lose the electrons first and
they can be gained by the other atoms to become anions. [Class Test Q1]
Always label "energy/kJ mol-1" on y-axis and "0" energy level for elements in their standard
states in an energy level diagram. [Class Test Q1]
When calculating a specific enthalpy change from an energy level diagram, e.g. first E.A. of O,
make it the subject of the equation and conduct the calculation. [Class Test Q1]

When reasoning if a reaction is feasible, compare the absolute values of H and TS


E.g. For a feasible reaction, G is negative only when |TS| < |H|. [Class Test Q2]
Hfo (O2(g)) and Hfo (Cl2(g)) are zero as they are elements in their standard states. Hence do
not wrongly use bond energy for these enthalpy changes. [Class Test Q2]
Relationship of equation Hosolution = sum of Hohydration - L.E.
When making a comparison in terms of solubility (e.g. down a group), compare the change
in magnitude of LE and the magnitude of enthalpy change of hydration for cation and/or
anions. From there it is possible to determine if enthalpy change of solution is becoming
more/less positive. [TP5 Q8 (c)]
When making comparison between enthalpy changes involving calculation using bond
energy (e.g. and enthalpy change of combustion), take note of the assumption made when
using bond energies. 1. The bond energies are calculated average values. 2. Reactants and
products are all in the gaseous state. [TP5 Q4]
Understanding energetics by comparing the enthalpy change of combustion/formation
between reactants and products:
In order to attain a more negative enthalpy change of combustion, the products
must have been placed at a higher energy level than the reactants to reach the same
energy level after combustion (visualize through an energy level diagram).
Similarly, in order to attain a more negative enthalpy change of formation from the
elements (at energy level 0) the products must have been placed at a lower energy
level than the reactants.
[BT 2013 Paper 1 Q19]

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Alternative way of deducing entropy change: if a reaction takes place without external
assistance, its Gibbs Free Energy is negative, if the enthalpy change is also given, entropy
change can be determined. [BT 2014 Paper 2 Q2]

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