THERMO CHEMISTRY

The science of heat or energy flow in a chemical reaction is called thermo chemistry.
Enthalpy is the heat content of a system, or the amount of energy within a substance,
both kinetic and potential. Every substance possesses both stored energy, due to the
nature of the chemical (and nuclear) bonds holding the substance together, and kinetic
energy which arises from to the constant motion of the particles. This total amount of
energy is enthalpy.
It should be noted that this amount of energy depends on the physical conditions of the
substance. However, it is not possible to actually measure the heat content of a substance,
but one can only measure how much enthalpy changes during a reaction. We use the
symbol delta (Δ) to refer to represent change. Therefore, we will generally always refer to
the change in enthalpy, or ΔH. We also refer to the change in enthalpy as the Heat of
Reaction. The energy term as part of a chemical reaction is the "heat of reaction", or
enthalpy change.
Heat of Reaction, ΔHr
 Defined to be the heat change during a particular reaction.
 If heat is released during this process, then the reaction is exothermic ( = heat
given out)
 If heat is absorbed during this process, then the reaction is endothermic ( = heat
taken in)
ΔH = ∑ΔHproducts – ∑ΔHreactants

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Exothermic Reactions
During exothermic reactions, more energy is released during bond formation than is
required to break bonds. A typically exothermic reaction would be written like this:
Cu(s) + Cl2(g) → CuCl2(g) + 220.1 kJ
In this reaction, there is a net release of 220.1 kJ of energy, and the energy term (220.1
kJ) appears on the product side of the equation.
Exothermic reactions release energy because the heat content of the reactants is greater
than that of the products. We will think of this difference in terms of potential energy - in
exothermic reactions, the reactants have more potential energy than the products. The
"excess" energy is released to the surroundings during the reaction. When the amount of
enthalpy in a system decreases a negative sign is used to indicate the drop. Thus, we
could rewrite the equation shown above as:

Cu(s) + Cl2(g) → CuCl2(g) ΔH° = -220.1 kJ

Endothermic Reactions
During endothermic reactions, energy is absorbed from the surroundings. A typical
endothermic reaction is written with the energy term on the reactant side of the equation:
H2O(g) + C(s) + 132 kJ → CO2(g) + 2H2(g)
As with the exothermic reaction, we can remove the energy term from the equation and
record the enthalpy change with a positive value, indicating that enthalpy increased
during the reaction:

H2O(g) + C(s) → CO2(g) + 2H2(g) ΔH° = +132 kJ

Standard Heat of Reaction: is defined as the change in enthalpy resulting from the
procedure of the reaction under a pressure of 1atm, starting and ending with all materials
at a constant temperature of 250C.
Heat of Formation: Defined to be the heat released if one mole of a compound were
formed from its component elements in their standard state.
 These reactions can be either endothermic or exothermic processes.
Standard Heat of Formation ΔHof : the amount of energy gained or lost when 1 mole of
the substance is formed from its elements under standard conditions (25°C, 1 atm = 101.3
kPa)

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A special type of chemical reaction, one in which we form one mole of a compound
from its elements. We are interested in how much energy is either absorbed or released
during this synthesis reaction.
For example, the formation reaction for liquid water is described by the following
equation:
H2 (g) + ½O2 (g) → H2O(l) + 285.8 kJ
The amount of energy released during this reaction, 285.8 kJ, is referred to as the
standard heat of formation. Since the reaction is exothermic we would indicate the heat
of formation, ΔHof, as -285.8 kJ.

By definition, Hof (kJ/mol) = 0 for any element in its standard state at 25oC and 1 .
o
Hrxn , for any reaction for which the heats of formation of all reactants and products are
known:
o
Hrxn  n
produc ts
prod Hof ( prod)  n
reac tants
H of (react)
reac t

This equation tells us to sum the enthalpies of formation of each product multiplied by its
stoichiometric coefficient in the reaction equation and then to subtract the enthalpy of
formation of each reactant multiplied by its stoichiometric coefficient.

Showing relationship between elements, reactants and products.

∆H
Reactants----------->Products
\ /
\ /
∆HfR \ / ∆HfP
\ /
Elements
Laws of Thermo-chemistry:
At a given temperature and pressure the quantity of energy required to decompose a
chemical compound into its elements is precisely equal to that evolved in the formation
of that compound from its elements. This principle was formulated by Lavoisier and
Laplace in 1978. From this the first law of thermo-chemistry is developed.

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Hess's Law of Constant Heat Summation: The enthalpy change for any reaction
depends only on the energy states of the final products and initial reactants and is
independent of the pathway or the number of steps between the reactant and product. The
reaction proceeds all at once or in series of steps; the net energy change is the same. This
illustrates Hess's Law of Constant Heat Summation
Problem 1: the following reaction describes the burning (combustion) of carbon:
(1) C (s) + O2(g) → CO2(g) ΔH = -393.5 kJ
If not enough oxygen is present, CO rather than CO2 is produced:
(2) C (s) + ½ O2(g) → CO (g) ΔH = -110.0 kJ
If more oxygen is now added, CO will undergo further combustion with oxygen:
(3) CO (g) + ½ O2(g) → CO2 (g) ΔH = -283.0 kJ
if we add together the second and third reaction:
(2) C (s) + ½ O2(g) → CO (g)
(3) CO (g) + ½ O2(g) → CO2 (g)

(1) C (s) + O2(g) → CO2(g)

Now compare the total energy released in the second and third reactions with the amount
of energy released in the original reaction:

ΔHReaction 2 + ΔHReaction 3 = ΔHReaction 1

-110.5 kJ + (-283.0 kJ) = -393.5 kJ

-393.5 kJ = -393.5 kJ

Problem 2: Calculate the heat change for the formation of 1.00mol of strontium
carbonate from it's elements. Given the following experimental information:

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We are trying to make SrCO3. It is formed from Sr, C and O2. Therefore, the balanced
equation is:

Problem 3: Given:
B2O3(s)+3H2O(g 3O2(g)+B2H6(g) ΔH =2035KJ
2H2O(l) 2H2O(g) ΔH =88KJ
H2(s)+(1/2)O2(g) H2O(l) ΔH =-286KJ
2B(s)+3H2(g) B2H6(g) ΔH =36KJ
Calculate change in enthalpy for
2B(s)+(3/2)O2(g) B2O3(s)
After multiplication and reversing of the equation
B2H6(g)+3O2(g) B2O3(S)+3H2O(g) ΔH =-2035KJ
3H2O(g) 3H2O(l) ΔH =-132KJ
3H2O(l) 3H2(g)+(3/2)O2(g) ΔH =858KJ
2B(s)+3H2(g) B2H6(g) ΔH =36KJ
Adding and canceling out common terms,
2B(s)+(3/2)O2(g) B2O3(s) ΔH =-1273KJ

HEAT OF COMBUSTION
The heat of combustion of a substance is the heat of reaction resulting from the oxidation
of the substance with molecular oxygen
 Defined to be the heat released when one mole of a compound undergoes
complete combustion in O2.

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  This will usually be an exothermic process, as shown in the example below.
 When drawing these diagrams, it is important to make sure they are balanced.
 Note that for heats of combustion, the organic compound is a starting material
for the reaction.

.
The Standard Heat of Combustion of a substance (ΔHoc) is the heat of the combustion
of that substance with oxygen to yield specified products, with both the reactants and
products at the reference (standard) state.
Standard heats of reactions that involve only combustible substances and combustion
products can be calculated from tabulated standard heats of combustion. These calculated
values are found with the following assumptions:
1) all carbon in the fuel forms CO2(g)
2)all hydrogen forms H2O(l)
3)all sulfur forms SO2(g)
4)all nitrogen forms N2(g)
The standard heat of reaction can be calculated using heats of combustion with the
equation
ΔHor = ∑i vi(ΔHoc)i = ∑reactants |vi|(ΔHoc)i - ∑products |vi|(ΔHoc)i
If any of the reactants or products are combustion products such as CO2 or H2O(l) their
ΔHoc values are equal to 0.
Example:
Calculate the standard heat of reaction for the dehydrogenation of ethane:
C2H6 C2H4 + H2
Using tabulated values of heats of combustion:
(ΔHoc)C2H6 = -1559.9 kJ/mol

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(ΔHoc)C2H4 = -1411.0 kJ/mol
(ΔHoc)H2 = -285.84 kJ/mol
Therefore:
ΔHor = (ΔHoc)C2H6 - (ΔHoc)C2H4 - (ΔHoc)H2 = 136.9 kJ/mol
To prove this formula using Hess's Law, the combustion reactions are as follows:
1. C2H6 + 7/2 O2 2CO2 + 3H2O
2. C2H4 + 3O2 2CO2 + 2H2O
3. H2 + 1/2 O2 H2O
By manipulating these equations, taking equation(1) - equation(2) - equation(3) we come
up with the desired equation:
C2H6 C2H4 + H2

Effect of Pressure on Heat of Reaction

 For ideal gases ΔHrxn is not a function of pressure
 For real gases ΔHrxn the enthalpies of reactants and products must be calculated as
described earlier
 For solids and liquids ΔHrxn is independent of pressure over small ranges. The
deviation is given below for incompressible materials and is usually quite small

Adiabatic Flame Temperature

For a combustion process that takes place adiabatically with no shaft work, the
temperature of the products is referred to as the adiabatic flame temperature. This is the
maximum temperature that can be achieved for given reactants. Heat transfer, incomplete
combustion, and dissociation all result in lower temperature. The maximum adiabatic
flame temperature for a given fuel and oxidizer combination occurs with a stoichiometric
mixture (correct proportions such that all fuel and all oxidizer are consumed). The
amount of excess air can be tailored as part of the design to control the adiabatic flame
temperature. The considerable distance between present temperatures in a gas turbine
engine and the maximum adiabatic flame temperature at stoichiometric conditions is
shown in Figure based on a compressor exit temperature of (922 K).

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The Adiabatic Case – assumptions
An adiabatic reaction is one where there is no heat flow (i.e. q = 0).
• Give idea of maximum temperature that a reactor will reach under the conditions of
enthalpy in = enthalpy out
• Assumes no effect of pressure
• Assumes basis of heat of reaction at 25ºC after which the products are heated to the
final T
• Must take into account all components including inerts. Extent of reaction must be
taken into account.

Needs to be solved by trial and error