Unit 5 - Chemical Energetics

Energy is the ability to do work, and in chemical reactions, heat is the medium through which
energy is transferred. In chemical reactions, energy is conserved.
Enthalpy (H): a measure of the amount of heat energy inside of a substance. It is stored in the
chemical bonds and intermolecular forces in the form of potential energy. (∆H)
- When heat is added to the system, the enthalpy increases.
- When heat is lost from the system, the enthalpy decreases.
Bond enthalpy: energy change when one mole of covalent bonds, in a gaseous molecule, is
broken under standard conditions.
System: region or place where the chemical reaction is happening (e.g. a test tube)
- Open system: system can exchange both mass and energy with the surroundings.
- Closed system: system can exchange only energy with the surroundings.
Surroundings: Everything outside the system (e.g. the universe)
Average bond enthalpy: energy change when one mole of covalent bonds, in a gaseous
molecule, is broken under standard conditions, averaged over similar compounds.

Important Formulae

- Q (energy, kJ) = m (mass in kg) x c (specific heat capacity) x ∆T (temperature change)

- ∆H (enthalpy change) = Q (energy in kJ) / n (number of moles)
- ∆H (enthalpy change) = BER (enthalpy of react., kJ/mol) - BEP (enthalpy of prod., kJ/mol)
- Density of water = 1g/cm3

Exothermic and Endothermic reactions

Chemical reactions involve:
- Endothermic Reactions (bond breaking, absorbing energy) (+∆H)
- Exothermic Reactions (bond making, releasing energy) (-∆H)
Heat change can be measured using Q = mc∆T
Specific heat capacity is given by c = Q / m∆T

Measuring the enthalpy change of reactions using water

- In reactions, we often have the substances in aqueous form, which means that they are
dissolved in water. From this, we can assume that any heat gained or lost by the
reactants during the reaction is consequently gained or lost by the water, which means:
∆Hwater = -∆Hwater
- Using Qwater = mwater x cwater x ∆Twater, then using -Q/n(limiting reagent), we can deduce ∆H
of the reaction
- To insulate the system and avoid heat loss, two styrofoam or polystyrene cups are
nested inside each other, such as in the coffee cup calorimeter example

Standard enthalpy of combustion (∆HC) is the enthalpy change for the complete combustion
of one mole of a substance in its standard state, in excess oxygen in standard conditions.
Hess’ Law states that regardless of the route through which a chemical reaction proceeds, the
enthalpy change will always be the same, provided the initial and final states of the system
remain the same

The standard enthalpy of formation of a substance (∆Hf) is the enthalpy change that occurs
when one mole of the substance is formed from its elements in their standard states and
under standard conditions.The ∆Hf of a substance tells us how stable the substance is
compared to its elements, and allows us to find the enthalpy change of all reactions related to
the substances and its elements.

As you cannot directly obtain the lactic enthalpy, the Born-Haber cycle (based on Hess’ Law)
essentially splits up the formation of a lattice into several steps, and adds the enthalpy changes
of each step to calculate the overall enthalpy.

Entropy

Entropy (S) refers to the distribution of available energy among particles. It is a way of
measuring the degree of disorder of a system. The more ways energy can be distributed in a
system, the more disordered the system is, and the greater the entropy
- Entropy: Gases > Liquids > Solids
 - Changes in state and the number of moles (more atoms = more randomness) are the
two key factors used while predicting changes in entropy.
- Standard values of entropy can be calculated for each substance at standard
temperature and pressure. This is called absolute entropy (Sº)
- A perfectly ordered solid at absolute zero (-273 K) has zero entropy. All other states
have greater, positive entropies. Therefore, entropies become more and more positive
as we move from solid to liquid to gas. Entropy cannot be negative.

- Total entropy change of a reaction takes into account both the entropy change of the
surroundings and the entropy change of the system.

- Exothermic reactions increase the entropy of the surroundings as heat is dispersed

into the surroundings. This clearly allows for ΔS(total) to be greater than zero, as entropy
increases.
- In the case of endothermic reactions, there is a decrease in the entropy of the
surroundings, but this is compensated for by a greater increase in the entropy of the
system, once again allowing for ΔS(total) to be greater than zero.

Gibbs Free Energy

Gibbs free energy (G) relates the energy that can be obtained from a chemical reaction to the
change in enthalpy (ΔH), change in entropy (ΔS), and absolute temperature (T).
- It can be used to reliably determine the spontaneity of a reaction
- spontaneous: -∆G
- non-spontaneous: +∆G
Temperature has a large effect on ∆G
- At low temperatures, T∆S ≈ 0 and ∆G ≈ ∆H
- At high temperatures, T∆S has a large enough value to make ∆H negligible, and
∆G ≈ -T∆S
- at low temps only exothermic reactions are spontaneous, whereas at high temps, any
reaction (exothermic or endothermic) that has a positive ΔS value will be spontaneous.
At STP (298 K), ∆G can be calculated from ∆Gf, using:

For reactions at other temperatures, the following equation can be used:

Lastly, ∆G can be used to predict the position of equilibrium