MODULE 5 – ENERGY RELATIONSHIPS IN CHEMICAL CHANGES

All chemical and most physical changes produces energy changes. Usually the energy is
manifest as heat energy.

2 kinds of energy change:

1. Exothermic change – those changes in which heat is evolved.

2. Endothermic change – changes in which heat is absorbed.

Energy change of a given chemical change is termed the heat of reaction or enthalpy of that
change, and is usually designated by the symbol ΔH. Its calorific value may be determined in a
calorimeter.

Calorimeter – the apparatus used for measuring the amount of heat involved in a chemical
reaction.

The usual type of a calorimeter is an insulated container of water, equipped with a thermometer
and a stirrer. Reactants in stoichiometric amounts are placed in a reaction vessel inserted into
the water bath. When the reaction proceeds, the heat energy evolved or absorbed either warms
or cools the water. The temperature before and after the chemical change is recorded. Once we
know the weight of water present, the temperature change, and the specific heat of the reaction
vessel and its contents, we can calculate the heat energy of the reaction.

Other types of calorimeters may be employed, depending upon the reactions to be carried out.
For example, in a reaction of gases where the reaction may occur with explosive violence, the
reactants are enclosed in a heavy steel container or “bomb”.

EXAMPLE 1: The following reaction using Hydrogen and oxygen is carried out in a bomb
calorimeter:

2H2(g) + O2(g) → 2 H2O(l)

The following data are recorded:

Weight of water in calorimeter ꞊ 2.650 kg
Initial temp. of water ꞊ 24.442 oC
Final temp. of water after reaction ꞊ 25.635 oC
Weight of reaction vessel ꞊ 1.060kg
Specific heat of reaction vessel ꞊ 0.200kcal/oC-kg
Specific heat of water ꞊ 1.00 kcal/oC-kg

Calculate the heat of reaction? Assuming that 0.050 mole of water was formed in this
experiment, calculate the heat of reaction per mole of liquid water formed. Neglect the specific
heat of the thermometer and stirrer.
ΔH ꞊ mass of substance x specific heat of substance x (ΔT)

ΔH (Heat of reaction) ꞊ heat absorbed by the system

꞊ heat absorbed by water + heat absorbed by reaction vessel

Heat absorbed by water ꞊ mass of substance x specific heat x (ΔT)

꞊ 2.650 kg x (1.0 kcal/oC-kg) x (25.635oC – 24.442oC)

Heat absorbed by water ꞊ 3.161 kcal

Heat absorbed by reaction vessel ꞊ 1.060 kg x (0.200kcal/oC-kg) x (25.635oC – 24.442oC)

꞊ 0.253 kcal

ΔH (Heat of reaction) ꞊ heat absorbed by the system

꞊ 3.161 kcal + 0.253 kcal ꞊ 3.414 kcal

For 0.050 mole of water, heat absorbed ꞊ 3.414 kcal

Therefore, for each mole of water ꞊ 3.414kcal/0.05mol ꞊ 68.3 kcal

2H2(g) + O2(g) → 2 H2O(l) ; ΔH ꞊ -136.6 kcal

H2(g) + 1/2O2(g) → H2O(l) ; ΔH ꞊ - 68.3 kcal

A more frequent convention is to record the value of ΔH for the reaction apart from the equation
with ΔH having a negative value for an exothermic reaction and a positive value for an
endothermic process. In an exothermic process the products possess less energy than the
reactants, and hence a negative value for ΔH is indicated.
HEATS OF FORMATION or ENTHALPY OF FORMATION (ΔH 0f) - the energy change
involved in the formation of one mole of a compound from its elements in their normal state.

(Heats of formation of elementary substances are assigned a zero value.)

No
HEATS OF REACTION:

These may be calculated from heats of formation by simply subtracting the sum of the
heats of formation for all reactants from the sum of the heats of formation of all products.

Example 2: Determine ΔH0 for the following reaction of burning ethyl alcohol in oxygen:

C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(l)

Solution:

ΔHo ꞊ ΔHof (products) - ΔHof (reactants)

ΔHof (products): ΔH of (reactants):

CO2(g) ꞊ - 94.1 kcal/mol C2H5OH(l) ꞊ -65.9 kcal/mol

H2O(l) ꞊ -68.3 kcal/mol O2 ꞊ 0

ΔHo ꞊ ΔHof (products) - ΔHof (reactants)

꞊ [ 2( -94.1) + 3(-68.3)] - [ -65.9 + 0]

꞊ ( -188.2 - 204.9) – (-65.9)

꞊ -393.1 kcal/mol + 65.9 kcal/mol

ΔHo ꞊ - 327.2 kcal/mol

ΔHo in this case may be termed the heat of combustion of C2H5OH(l).

CHEMICAL THERMODYNAMICS

Chemical thermodynamics is concerned with the relationships between all forms of energy and
includes a number of concepts in addition to enthalpy of reaction.
It is the study of the interrelation of heat and work with chemical reactions or with physical
changes of state within the confines of the Laws of thermodynamics.

Laws of Thermodynamics:

1. First Law of Thermodynamics: Energy maybe converted from one form to another but
may neither be created nor destroyed.
Expressed mathematically:

ΔE ꞊ q - w
Where: ΔE ꞊ change in internal energy
q ꞊ ΔH ꞊ heat absorbed in the change
w ꞊ work done by the system on the surroundings
but w ꞊ PΔV

ΔE ꞊ ΔH - PΔV
ΔH ꞊ ΔE + PΔV , but PΔV ꞊ ΔnRT
ΔH ꞊ ΔE + ΔnRT
Where: Δn ꞊ no. of moles of gaseous products – no. of moles of gaseous reactants
R ꞊ molar gas constant ꞊ 1.99 cal/oK-mol
T ꞊ absolute temperature or oK temp.

Example 3: Calculate ΔH for the reaction at 250C.

CO(g) + ½ O2(g) → CO2(g) ; ΔE ꞊ -67.4 kcal

Solution:

ΔH ꞊ ΔE + ΔnRT
Given: Δn ꞊ 1 – (1+ 0.5) ꞊ -0.5 mole
T ꞊ 25oC + 273 ꞊ 298oK
ΔH ꞊ -67.4 kcal + ( - 0.5moles x 1.99 cal/oK-mol)(298oK)
꞊ -67.4 kcal + (-296.51 cal)
꞊ -67.4 kcal – 0.29651kcal
꞊ -67.7 kcal

2. Second Law of thermodynamics: A spontaneous process occurs only if there is an

increase in entropy of a system and its surroundings.

Entropy (S) – is a measure of the disorder or randomness of a system.

 The entropy of a gas is greater than that of a liquid which in turn is greater than that of a solid;
that is, there is more disorder in a gas than a liquid, in a liquid than in a solid.

When an equilibrium process occurs at constant temperature, the change in entropy, ΔS, is equal
to the heat absorbed divided by the absolute temperature at which the change occurs.

ΔS ꞊ ΔH/T
Example 3: Calculate ΔS for the conversion of one mole of liquid water to vapour at 100oC.

Heat of vaporization ꞊ 540 cal/g ; Molecular weight of H2O – 18 g/mole

Given: ΔH ꞊ 540 cal/g x 18g/mol ꞊ 9720 cal/mol

T ꞊ 100oC + 273 ꞊ 373oK

ΔH 9720 cal/mole
ΔS ꞊ --------- ꞊ ------------------------ ꞊ 26.1 cal/K-mol
T 373oK
Free energy (G) is the energy of a system which is available for useful work. The change in
free energy , ΔG, of a system is related to ΔH, ΔS, T by the
equation:
ΔG꞊ ΔH -TΔS
3. Third Law of thermodynamics: this law states that the entropy of a perfectly ordered
system at OoK is zero. Such a system is a perfect crystalline substance where the units
making up the crystals are arranged in a very definite pattern. There is no disorder or
randomness and hence such a substance may be regarded as having a minimum value of
entropy which is zero. A few standard entropy values are recorded in Table 12.3.

Example 4: Determine ΔS, ΔH and ΔG for the following reactions at 25oC.

CO(g) + Cl2(g) → COCl2 (g)

Solution: Obtain S and ΔHof values from Table 12.1 and 12.3.

S ꞊ S(COCl2) - [S(CO) + S(Cl2)]

꞊ 69.1 – (47.3 + 53.3) ꞊ -31.5 cal/K-mol ꞊ -0.0315 kcal/K-mol

ΔH ꞊ ΔHof(COCl2) - [ΔHof(CO) + ΔHof(Cl2)]

꞊(-53.3) – (-26.4 + 0)

꞊ -26.9 kcal

ΔG꞊ ΔH –TΔS ꞊ (-26.9 kcal) – (298oK)(-0.0315 kcal/K)

ΔG꞊ -17.513 kcal