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F.6 Chemistry
PART 3: ENERGETICS
6.1 What is Energetics
Energy Changes In Chemical Reactions
I. Thermochemistry
Thermochemistry is concerned with the heat changes that accompany chemical changes
and /or phase changes.
Notes:
1. Energy is a measure of capacity to do work. It exists in many different forms, e.g. chemical
energy, light energy, electrical energy and heat.
2. In most chemical and physical changes, there is an associated energy change. The study of
these energies is known as energetic.
3. The energy changes occurring in chemical reactions are usually reflected as heat changes.
I. Conservation of Energy
The first law of thermodynamic ( or law of conservation of energy ) states that energy may be
converted from one form to another, but it is never created nor destroyed.
For a reaction carried out at constant pressure (usually at atmospheric pressure in an open
container ), and if no other work is involved, the heat absorbed or evolved is called the enthalpy
change.
The enthalpy change of reaction is the heat exchange ( either absorption or release )
with the surroundings at constant pressure before and after the reaction.
In an exothermic reaction, the energy released from the reacting system flows into the
surroundings. According to the law of conservation of energy, this same amount of energy is gained by
the surroundings. This is because energy can be neither be created or destroyed but can be transferred.
The energy of the universe is constant.
6.2 Endothermic and Exothermic Reactions related to the Breaking and Forming of Bonds
Nearly all of the heat energy released or absorbed in a chemical reaction can be accounted in terms
of the forming and breaking of bonds.
Note:
1. All the important forces between atoms, including those that hold atoms together in
molecules, are electrical in nature. This electrical forces are mostly attractive.
L.S.T. Leung Chik Wai Memorial School Ch.6 : p.3
F.6 Chemistry
2. To separate the atoms, work must be done against this attractive force, i.e. energy must be
done against this attractive force, i.e. energy must be applied.
3. The energy required to separated atoms is released when they join together again.
Any chemical reaction involved a rearrangement of atoms. Chemical bonds in the reactants are
broken and new bonds are formed in the products.
- Bond breaking is an energy absorbing process. It takes in energy from the surroundings.
- Bond forming is an energy releasing process. It gives out energy to the surroundings.
Note:
1. Chemical reaction results in an overall enthalpy change because
the energy required to break the bonds in reactants to form the free atoms is
NOT EQUAL TO
the energy given out when the free atoms recombine to form different bonds in the
products.
2. As a result, the heat content of the reactants is not equal to the heat content of the products in
a chemical reaction.
3. Exothermic and endothermic reactions are related to bond breaking and formation in the
following way:
Exothermic reactions are reactions in which
the energy required to break the bonds in the reactants is smaller than the energy liberated in
forming the bonds in the products.
They give out heat to the surroundings.
Note:
Average Bond Enthalpy values can be used to calculate the enthalpy change in a reaction.
The enthalpy change when the molar quantities of reactants shown in a balanced
chemical equation completely react to from products under standard conditions.
When one mole of hydrogen and half mole of oxygen react to form one mole water,
285.9 kJ of heat are evolved under standard conditions. This is an exothermic reaction, H being
negative.
Note:
1. All the substance involved must be in their normal physical states under standard conditions.
2. The enthalpy of all elements in their most stable form and standard state is conventionally
taken as zero. For example,
H0298 [O2(g)] = 0 , H0298 [Na(s)] = 0
Therefore, the standard enthalpy of formation of a compound represents the enthalpy content
of the compound.
3. The precise physical state and allotropic form, if any, must clearly specified. This is because
changes in state and allotropic form, involve energy changes even at a fixed temperature. A
examples:
(a) Change of State:
H2(g) + 1/2 O2(g) H2O(g) H0 = -242.0 kJ mol-1
H2(g) + 1/2 O2(g) H2O(l) H0 = -285.9 kJ mol-1
i.e. H2O(g) H2O(l) H0 = -44 kJ mol-1
Standard Enthalpy of Neutralization , H0n,298 is the enthalpy change when an acid and a
base neutralize to form one mole of water under standard conditions.
When one mole of sodium hydroxide reacts with one mole of hydrochloric acid to give
one mole of water under standard conditions, 57.3 kJ of energy are released to the
surroundings.
Note:
1. Neutralization is carried out in infinitely dilute solution.
2. The enthalpy of neutralization is always negative because neutralization is exothermic.
3. The value of H0n,298 involving strong acids and bases is quite constant ( -57.3 kJ mol-1)
The heat producing reaction is essentially
H+(aq) + OH-(aq) H2O(l) H0n,298 = -57.3 kJ mol-1
4. If either the acid or alkali is weak, the enthalpy of neutralization is less negative. (i.e. less
exothermic ) Energy is required to complete the dissociation of the weak acid or base as
reaction proceeds. The ionization process consumes some heat produced during
neutralization, thereby reducing the magnitude of H0n,298 .
H = C x T
where heat capacity means the amount of heat per degree temperature change.
L.S.T. Leung Chik Wai Memorial School Ch.6 : p.6
F.6 Chemistry
- the heat capacity of the calorimeter and the contents can be found by measuring the electrical
energy needed to raise the temperature by a certain degrees.
- Specific heat capacity ( J g-1 K-1 ) is defined as the amount of energy needed to raise the
temperature of 1g (or 1 kg) of a substance by 1K .
Experiment I Experiment II
Procedure 50 cm3 of 2.0 M NaOH solution were 50 cm3 of 2.0 M NaOH solution were
added to 50 cm3 of 2.0 M added to 50 cm3 of 2.0 M RCOOH
hydrochloric acid solution in a solution in a polystyrene cup.
polystyrene cup.
Maximum Temp. 13.0 10.5
rise 0C
Equation H+(aq) + OH-(aq) H2O(l) RCOOH(aq) + OH-(aq)
RCOO-(aq) + H2O(l)
a) Calculate the standard enthalpy of neutralization for the two experiments. Account for the
differences in these two values.
b) Calculate the standard enthalpy of dissociation of RCOOH.
(Given at 298 K and 1 atm : specific heat capacity of solution = 4.2 J g-1 K-1,
density of final solution = 1.0 g cm-3 )
( 8 marks )
L.S.T. Leung Chik Wai Memorial School Ch.6 : p.8
F.6 Chemistry
III. Standard Enthalpy of Solution and its Experimental Determination
Standard enthalpy of solution, H0soln,298 is the enthalpy change when 1 mole of a substance
is completely dissolved in an infinite amount of solvent (usually water) under standard
conditions.
Note: The solution should be dissolved in such a large excess of solvent that further
addition of solvent produces no further enthalpy change.
Example: An experiment determining the approximate value for the enthalpy of solution of copper
(II) sulphate.
8 g of anhydrous copper (II) sulphate are added to 100 cm3 water in the polystyrene cup.
There is a temperature rise of 8 0C in the solution.
(a) Calculate the molar enthalpy of solution of anhydrous copper (II) sulphate.
(b) Assumptions which are made in calculating the molar enthalpy of solution (a)
1. the thermal capacities of polystyrene cup and the thermometer are negligible.
2. the specific heat capacity of copper (II) sulphate solution is similar to that of water.
3. anhydrous copper (II) sulphate dissolves quickly such that heat losses are negligible.
4. further addition of the solution would cause no further heat change.
5) The copper (II) sulphate solution may not be sufficiently dilute to eliminate further heat
change on addition of water. Use smaller quantities of copper (II) sulphate in powder
form.
When one mole of ethanol is formed from its constituent elements ( in their normal
physical state ). 277 kJ of energy are released.
Note:
1) Elements in the standard state have zero enthalpy of formation.
2) Standard enthalpies of formation can sometimes be measured directly by using
calorimeter experiments. However, in many cases, the elements do not combine under
the experimental conditions. Their enthalpies of formation are measured indirectly,
using Hess’s Law.
Standard enthalpy of Combustion, H0c,298 is the enthalpy change when one mole
substance undergoes complete combustion ( being oxidizing by oxygen ) in the
standard state.
Note: All enthalpies of combustion have a negative sign since combustion is exothermic and
always involves the evolution of heat.
L.S.T. Leung Chik Wai Memorial School Ch.6 : p.10
F.6 Chemistry
6.4 Experimental Determination of Enthalpy of Combustion
The enthalpies of combustion of gases or volatile liquids can be measured using a flame
calorimeter.
Method: Oxygen is passed through the combustion chamber. The energy evolved by combustion
heat the surrounding water bath. The temperature produced by the combustion of a
known mass of the compound is measured.
Example 1:
Pure oxygen is pumped into the calorimeter and 0.7 g of pure ethanol is burnt. Once ethanol starts
burning , it is enclosed to reduced heat loss. The heat produced raises the temperature of 250 cm3
of water by 20K.
(a) Suggest why the heat exchanger is made of copper in the calorimeter.
(b) Assume that the heat capacity of calorimeter is negligible and there is no loss,
determine the enthalpy of combustion of ethanol.
(c) Apart from the neglecting of heat capacity of the calorimeter and heat losses,
suggest two sources of experimental error.
( specific heat capacity of water = 4.18 J g-1 K-1 , density of water = 1.0 g cm-3 )
L.S.T. Leung Chik Wai Memorial School Ch.6 : p.11
F.6 Chemistry
6.5 Hess’s Law
The law of conservation of energy states that energy can be neither be created or destroyed ,
though one form of energy can be converted to another form.
This law therefore implies that the total energy content ( in the system ) is constant. Based on it,
Hess’s law arises.
I. Hess’s Law
The standard enthalpy change of reaction depends only on the difference between the standard
enthalpy of the reactants and the standard enthalpy of the products, and not no the route by which
the reaction occurs.
Hess’s Law
The total enthalpy change accompanying a chemical change is independent of the route by
which the chemical change takes place. Therefore, the overall change in enthalpy is the
same, whichever route is followed.
In other words, for processes involving several stages, the enthalpy change for the reaction is
equal to the algebraic sum of the enthalpy change for each intermediate stage.
H2
H3
H1
H4
H5
Example:
The enthalpy change for the oxidation of carbon (graphite) to carbon dioxide is the same
whether it is carried out Route A ( 1 stage ) or Route B ( 2 stages)
C(s) + O2(g)
Hc[C(s)]
H2 = -283.0 kJ mol-1
-393.5 kJ mol-1
m CO2(g)
Hc[C(s)]
CO(g)
Example 1:
It is difficult to determine the enthalpy change for
C(s) + 1/2 O2(g) CO(g) H1
because some graphite may oxidized completely to CO2(g)
This enthalpy change should be determined indirectly by calorimetry experiments using Hess’s
Law. Since
CO(g) + 1/2 O2(g) CO2(g) H2 = - 283 kJ mol-1
C(s) + O2(g) CO2(g) Hcomb = -393.5 kJ mol-1
These two values can be determined relatively easily in calorimetry experiments. The enthalpy
change for
C(s) + 1/2 O2(g) CO(g)
H1 can be determined indirectly from these two values, using Hess’s Law
Hcomb. [C(s)] = H1 + H2
H1 = Hcomb. [C(s)] - H2
= (-393.5) – (-283)
= -110.5 kJ mol-1
<1> Reagents: Calcium, Calcium carbonate, a strong acid (e.g. HCl) , water
<2> Data Given: the enthalpy of formation of carbon dioxide gas the enthalpy change of
formation of water
<3> Description:
(a) Equation for the formation of calcium carbonate from its constituents:
Ca(s) + C(s) + 3/2 O2(g) CaCO3(s)
-
Units: kJ mol-1
-
Sign : to indicate an exothermic or endothermic reaction
Example 1:
Find the standard enthalpy of the following reaction
CO(g) + 1/2 O2(g) CO2(g)
Given that H0f [CO(g)] = -110.5 kJ mol-1 , H0f [CO2(g)] = -393.5 kJ mol-1
Example 2
Find the standard enthalpy of the following reaction
2SO2(g) + O2(g) 2SO3(g)
Given that H0f[SO2(g)] = -297.0 kJ mol-1 and H0f[SO3(g)] = -395.0 kJ mol-1
L.S.T. Leung Chik Wai Memorial School Ch.6 : p.16
F.6 Chemistry
(B) Calculating Standard Enthalpy of formation from enthalpy of Combustion
When a compound is completely burnt, the combustion products are the same as those produced
when its constituent elements undergo complete combustion.
From Hess’s Law
H0f, 298
Elements Compounds
H1
H2
Combustion Products
Example 1
The standard molar enthalpies of combustion at 298 K for graphite , hydrogen , ethanol are –393.1
kJ mol-1 , -285.8 kJ mol-1 , and –1367 kJ mol-1 respectively.
From the above thermochemical data, calculate the standard molar enthalpy of formation for
ethanol at 298 K .
L.S.T. Leung Chik Wai Memorial School Ch.6 : p.17
F.6 Chemistry
Example 2
Given the following thermochemical data:
Reaction H0298 / kJ mol-1
C (graphite) + 2H2(g) CH4(g) -75
C(graphite) + O2(g) CO2(g) -393.5
H2(g)+ 1/2 O2(g) H2O(l) -285.9
a) Calculate the standard enthalpy change for the reaction given below:
CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
b) Calculate the enthalpy change of vaporization of water at 298 K, given that the enthalpy
change is –801.7 kJ mol-1 for the reaction given below:
CH4(g) + 2O2(g) CO2(g) + 2H2O(g)
L.S.T. Leung Chik Wai Memorial School Ch.6 : p.18
F.6 Chemistry
(C) Calculating Standard Enthalpy of formation from Standard Enthalpy of Solution
In practice, enthalpies of solution are easily measured and may be used to determine the standard
enthalpy of formation.
Note that on dilution of a solution which is not infinitely dilute, a further enthalpy change results.
This is referred to as the enthalpy of dilution.
Example 1
Given the following thermochemical data:
Standard enthalpy of solution of potassium hydroxide = -55 kJ mol-1
Standard enthalpy of formation of water = -286 kJ mol-1
Standard enthalpy change for the reaction between potassium and water = -195 kJ mol-1
Calculate the standard enthalpy of formation of potassium hydroxide.
Example 2:
Given the following thermochemical data:
H0soln[CuSO4 5H2O(s)] = + 8 kJ mol-1
H0soln[CuSO4(s)] = -66 kJ mol-1
H0f[CuSO4(s)] = -773 kJ mol-1
H0f[H2O(l)] = -286 kJ mol-1
Calculate H0f[CuSO4 5H2O(s)] from the above data.
L.S.T. Leung Chik Wai Memorial School Ch.6 : p.19
F.6 Chemistry
(D) Calculating Standard Enthalpy of Formation from Standard Enthalpy of Reaction
According to Hess’s Law, whether a compound is formed in one step or through many
intermediate steps, the enthalpy change is the same. This is because the enthalpy change depends
on the difference in the enthalpy contents of the reactants and the products.
From Hess’s Law,
Example 1:
Calculate the enthalpy of formation of NaCl(s) from the following data
The sign of the enthalpy change for a reaction is an indication of its feasibility.
As a chemical reaction proceeds, the change in enthalpy of the system can be illustrated by an
enthalpy profile. Enthalpy profiles for an exothermic and an endothermic reaction are shown
below:
The more negative the H value for a reaction, the more likely the reaction is
feasible.
Alternatively, reactions with high positive H values are not likely to be
feasible.
However, kinetic factors should also be considered in determining whether a reaction is feasible or
not.
1. Any reaction (exothermic or endothermic ) requires a certain minimum amount of energy
called activation energy to occur. It represents the energy barrier that the reactants
must overcome before they can combine to form products.
2. In the absence of this activation energy, a reaction does not occur, despite the magnitude
or sign of the enthalpy change evolved.
3. Therefore,
if the activation energy is very high, the reactants will be kinetically stable. It is
unlikely that a reaction occurs.
if the activation energy is very low, the reactants will be kinetically unstable. It is likely
that a reaction occurs.
L.S.T. Leung Chik Wai Memorial School Ch.6 : p.21
F.6 Chemistry
Example: Both allotropes of carbon, graphite and diamond have highly negative enthalpies of
combustion:
C(graphite) + O2(g) CO2(g) H = -393.5 kJ mol-1
1. Both graphite and diamond are energetically unstable with respect to the carbon dioxide.
Based on enthalpy of combustion only, it is likely that carbon would be oxidized readily, i.e.
combustion is highly feasible.
2. However, such a high activation energy is required to start combustion that diamond and
graphite appear inert. They are said to be kinetically stable.
In conclusion,
A reaction is more likely to occur if the reactants are both energetically and kinetically
unstable relative to the products.
The value of the standard enthalpy of formation of a compound gives a good indication of its
energetically stability.
Compounds with high negative enthalpy of formation is very stable, so far as decomposition
into its elements is concerned.
This is because the enthalpy change for its decomposition would be highly positive, and therefore
unlikely to occur.
Compounds with high positive enthalpy of formation is very unstable and tend to
decompose into its elements.