Thermodynamics

Jerry

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Definitions
Standard molar enthalpy of formation

The standard molar enthalpy of formation is the enthalpy change when

one mole of a compound is formed from its constituent elements under
standard conditions, all reactants and products in their standard states

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Definitions
Standard molar enthalpy change of combustion

The standard molar enthalpy change of combustion is the enthalpy

change when one mole of substance is completely burnt in oxygen.

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Definitions
Standard molar enthalpy of atomization

The standard enthalpy of atomisation is the enthalpy change which

accompanies the formation of one mole of gaseous atoms from the
element in its standard state under standard conditions.

This is given per mole of chlorine or bromine atoms and not per mole of
chlorine or bromine molecules.
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Definitions
Standard molar enthalpy of ionization energy

First ionisation energy (first IE) is the standard enthalpy change when one
mole of gaseous atoms is converted into a mole of gaseous ions each with
a single positive charge.

The second ionisation energy (second IE) refers to the loss of amole of
electrons from a mole of singly positively charged ions.

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Definitions
Standard molar enthalpy of electron affinity

The first electron affinity the standard enthalpy change when a mole of
gaseous atoms is converted to a mole of gaseous ions, each with a single
negative charge.

The second electron affinity the enthalpy change when a mole of electrons
is added to a mole of gaseous ions each with a single negative charge to
form ions each with two negative charges.

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Definitions
Standard molar lattice enthalpy of formation/ dissociation

Lattice enthalpy of formation is the standard enthalpy change when one

mole of solid ionic compound is formed from its gaseous ions.

Lattice enthalpy of dissociation is the standard enthalpy change when one

mole of solid ionic compound dissociated into its gaseous ions.

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Definitions
Standard molar enthalpy of hydration

Enthalpy of hydration is the standard enthalpy change when water

molecules surround one mole of gaseous ions.

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Definitions
Standard molar enthalpy of solution

Enthalpy of solution is the standard enthalpy change when one mole of

solute dissolves completely in sufficient solvent to forma solution in which
the molecules or ions are far enough apart not to interact with each other.

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Definitions
Standard molar mean bond enthalpy

Mean bond enthalpy is the enthalpy change when one mole of gaseous
molecules each breaks a covalent bond to form two free radicals, averaged
over a range of compounds.

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Enthalpy changes on forming ionic compounds

Step1

Step2

Step3

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Born-Haber cycles
Definition

A Born-Haber cycle is a thermochemical cycle that includes all the enthalpy

changes involved in the formation of an ionic compound.

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Born-Haber cycles
Steps

1 Start with elements in their standard states. This is the energy zero of the
diagram
2 Add in the atomisation of sodium. This is positive, so it is drawn uphill
3 Add in the atomisation of chlorine. This too is positive, so drawn uphill.
4 Add in the ionisation of sodium, also positive and so drawn uphill
5 Add in the electron affinity of chlorine. This is a negative energy change and
so it is drawn downhill.
6 Add in the lattice enthalpy of formation of sodium chloride, also negative and
drawn downhill
7 The final unknown quantity is the lattice formation enthalpy of sodium chloride.
The size of this is 788 kJ/mol from the diagram. Lattice formation enthalpy is the
change from separate ions to solid lattice and you must therefore go downhill.
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Exercice

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Enthalpy in the solution

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Lattice enthalpies and bonding

This distortion means there are more electrons than expected concentrated between the Zn
and Se nuclei, and represents a degree of electron sharing or covalency which accounts for
the lattice enthalpy discrepancy (difference). The Se2- ion is said to be polarized.

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Why do chemical reactions take place
Feasible or spontaneous

Definition: Describe reactions which could take place of their own accord.

Entropy or randomness

系统的混乱程度

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The Gibbs free energy change
two factors govern the feasibility of a chemical reaction

the enthalpy change 系统倾向于能量最底

the entropy change 系统倾向于更混乱

Gibbs free energy

G positive, not feasible

G negative, feasible

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Thank you

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