Energetics

Enthalpy: Energy contained in chemical bonds. Enthalpy change: Energy change in chemical reactions. The energy exchanged with the surrounding environment at constant pressure is called the enthalpy change of a reaction. A constant volume is not used since work is done expanding and contracting a gas. Exothermic: Heat energy given out. High energy to low energy: energy is lost to the surroundings. Negative enthalpy change. Enthalpy of the products is less than the enthalpy of the reactants, and they are more stable. Endothermic: Heat energy taken in from the surroundings. Low energy to high energy. Positive enthalpy change. Enthalpy of the products is greater than the enthalpy of the reactants, and they are less stable. Energy conversions:

Enthalpy (H) Internal chemical energy

Heat energy (E or Q)

Enthalpies cannot be measured, only enthalpy changes. (H) Q= -H An increase in heat energy is due to an equal decrease in enthalpy. (-H) Exothermic reactions result in negative enthalpy. Examples: Combustion, neutralization, condensation, freezing, and some dissolving and the majority of reactions.

Larger activation energies indicate stronger bonds between the reactants.

Endothermic reactions have a positive enthalpy change (+H) Example: photosynthesis, thermal decomposition, melting, evaporation, and some dissolving.

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Bond breaking is endothermic, and bond forming is exothermic. Thermochemical equations show H

H O : Standard conditions: Standard pressure: 1 atm: 101.3 Pa Standard temperature: 298 k: 25 C For one mole of reactant or product (depends on the reaction) HrO : standard enthalpy change of reaction. For 1 mole reactants under standard conditions. Hf O : standard enthalpy change for the formation of 1 mole of product from its elements in the standard states and standard conditions. Hc O : standard enthalpy change of combustion when 1 mole of reactant is completely burned in oxygen under standard conditions. Hnewt O : standard enthalpy change of neutralization when 1 mole of water is formed by the reaction of an acid and alkali at standard conditions. The change in heat during a chemical reaction depends on: The nature of the reactants The concentration The physical state of the reactants Temperature Pressure

Calculation of enthalpy change It is not possible to measure enthalpies, only enthalpy changes. In practice, the change in enthalpy is measured by measuring the change in temperature of the surroundings (calorimetry).

Where for one substance: H= Change in enthalpy Q = Change in heat energy M= Mass of what is being heated in g. Cp = Specific heat capacity jg-1 C-1 or jg-1k-1. T = Change in temperature in C or K. Eg: 1- Combustion: A fuel will burn and heat a container of water. M= Mass of water Cp = Specific heat capacity of water. You can also include the mass and Cp of the container. 2- Reactions in solution:

M= Mass of solution Cp = Specific heat capacity of water. (Ignore the Zn and CuSO4 present) To compare the experimental value to a textbook value: find the molar H

For combustion:

For reactions in solutions:

There will be a major error due to heat loss. For experiments, choose the container (calorimeter) carefully. Combustion: use copper to transfer the heat to water. Solutions: use polystyrene to minimize heat loss. Hesss law The enthalpy for a reaction only depends on the initial and the final states of the chemicals but is independent of the route taken.

A+B

H1

C+D
H3

H2

There are several ways to calculate

using Hesss law.

1- Constructing an enthalpy cycle like above, and adding the equations together. 2- Shortcut: Finding using Finding using data: data:

Bond Enthalpies Bond enthalpy: the energy change when 1 mol of a covalent bond in the gaseous state is formed from its gaseous atom. The overall enthalpy change of a reaction can be found using the bond enthalpies. Bond forming is exothermic (energy released-negative). Bond forming is endothermic (energy absorbed-positive). Average bond enthalpy: Some bonds bond enthalpies are affected by their surroundings in different compounds. The average bond enthalpy is the average bond enthalpy of a particular bond is different molecules.
_ _

Average bond enthalpies can be used to calculate the enthalpies of reactions.

Example:

)]

Sometimes, the number of bonds is simply too big to include each and every bond. For example:

Born-Haber Cycle: A Born-Haber cycle shows 2 ways to form an ionic compound from the elements. It can be used (indirectly) to calculate the lattice enthalpy of an ionic compound. The Born-Haber cycle for NaCl:

Na+(g) + Cl (g)

Na(g) + Cl (g)

Na+(g) + Cl- (g)

Na(g) + Cl2(g)

Na(s) + Cl2 (g)

NaCl (s)

= Enthalpy of atomization (to form 1m of gaseous atoms) endothermic. = Enthalpy change of ionization (1st IE= to remove the first electron from 1 mol of gaseous atoms) = Enthalpy of electron affinity (1st ea= to add the first electron to 1 mol of gaseous atoms. 1st ea is exothermic. The second is usually endothermic. = Lattice enthalpy (when gaseous ions form 1 mole of a solid ionic lattice- always exothermic)

Factors affecting 1. Higher charge on ions = bigger attraction = bigger 2. Smaller ions = closer together = bigger . Bigger charge density = bigger .

Uses of Born-Haber cycles: Calculating H using Hesss law Finding the amount of ionic character in a lattice (Born-Haber cycles assume 100% ionic character in a lattice) If (experimental) is close to (Born-Haber) then the percentage ionic character in the lattice is high. If they differ significantly then there is some covalent character.

Entropy Entropy is a measure of disorder in a system values of S can be measured but is more useful. Processes tend towards disorder increase. . Absolute

and all changes cause Suniverse to

As long as Suniverse is positive, a change can happen so a system can decrease as Ssurroundings increase more. Entropy increases if: i. ii. iii. iv. Gases are produced (solids have a lower S than liquids which is lower than gas) Particles are mixed (aqueous solution formed) Particles can be made to move more (by heating) Increasing number of particles (more moles of products)

Spontaneous reactions Spontaneous reaction: a reaction that will occur naturally when reactants are mixed. Some reactions are always spontaneous. Some reactions are never spontaneous. Some reactions are only spontaneous at high temperatures Some reactions are only spontaneous at low temperatures Spontaneity depends on the value of the Gibbs free energy (
Kjmol-1 Kjmol-1 K

JK-1mol-1: divide by 1000 to make units match (kJK-1mol-1)

, , , , , If If If

is always negative. is never negative. , is negative only if the temperature is high enough. , is negative only if the temperature is low enough.

is negative, the reaction is spontaneous. is equal to zero, the reaction is at equilibrium is positive, the reaction is not spontaneous.

A reaction may be spontaneous but extremely slow do to high activation energy or a slow rate. Spontaneity tells us nothing about kinetics.