Going over basics:

Enthalpy symbol H, is stored energy, its not possible to measure enthalpy but enthalpy changes (, by measuring temperature
changes of reactions at constant pressure. Pronounced delta means change of
Enthalpy change, is the measure of the transfer of energy into or out of a reacting system at constant pressure
Exothermic reaction Energy given out by reactants as they form products
Energy exits in exothermic reactions is negative, enthalpy(stored energy) decreases, temperature increases
Bond making, amount of heat released is greater than the amount of heat used to start the reaction
Endothermic reaction Energy is taken in by reactants to form products
Energy enters in endothermic reactions is positive, enthalpy(stored energy) increases, temperature decreases
Bond breaking, energy continues to be absorbed as long as the reaction continues

Definitions to remember:

Lattice Enthalpy Hlatt Energy released per mole for exothermic process M+(g) + X
(g) M+X-(s)
(Enthalpy/heat energy released when gaseous ions come together to form 1 mole of solid)
Standard enthalpy of atomisation Ha Enthalpy change for production of one mole of
gaseous atoms from the element in its standard state
Enthalpy of hydration Hfhyd Enthalpy change per mole for dissolving the gaseous ions,
with enough water to form an infinite dilute solution.
(When water is used as the solvent, the dissolving process is called hydration)
(For a unipositive cation Hhyd is exothermic: M+(g) + aq M+(aq))
Understand that:
Enthalpy of formation Hf Enthalpy change when one mole of a compound is formed from its elements
Na(s) + (1/2)Cl2(g) NaCl(s)
1st Ionisation Energy M(g) M+(g) + e
2nd Ionisation Energy M+(g) M2+(g) + e

1st Electron affinity Enthalpy change per mole for the process, X(g) + e X(g)
- Negative(exothermic), since the electron is attracted by the positive charge on the atoms
nucleus
2nd Electron affinity Enthalpy change per mole for the process, X(g) + e X2(g)
O
(g) + e O2(g)
- Positive(endothermic), since energy needed to overcome repulsion between the electron
and negative ions
Questions
Write the equation, with state symbols, for the enthalpy of atomisation of chlorine
Cl2(g) Cl(g)
Write an equation which represents the change when the second electron affinity of oxygen is measured
O(g) + e O2(g)
Explain the trend in IE within the group 1 elements
I o n is a tio n E n e r g y /k J m o l 1
E le m e n t
L i

+ 519

N a

+ 494

+ 418

R b

+ 402

C s

+ 376

electron further away from nucleus

inceased shielding effect inner shells
less energy needed to remove outer electron

Construct a Born-Haber cycle and carry out associated calculations

A Born-Haber cycle calculates the lattice enthalpy

by comparing the Hf of the ionic compound (from
the elements) to the enthalpy required to make
gaseous ions from the elements
The Born-Haber cycle involves the formation of an
ionic compound from the reaction of a metal(often
a Group1/2 element) with a non-metal
All endothermic reactions shown by arrow pointing
upwards (vice versa)

1. Atomisation enthalpy of metal

(in this case lithium)
2. Ionisation enthalpy of metal
3. Atomisation enthalpy of nonmetal (in this case fluorine)
4. Electron affinity of non-metal
5. Lattice enthalpy
Questions
Presenting an ionic solid, NaH
Draw a Born-Haber cycle which could be used to determine the
electron affinity of hydrogen
N a +(g ) + H (g ) + e

N a + (g ) + H (g )
N a (g ) + H (g )

N a ( g ) + 1/ 2 H 2 ( g )

Construct a Born-Haber cycle and to obtain Hlatt

of SrCl2(s)
Hf of SrCl2(s) -829 kJmol1
Ha of
+164 kJmol1
strontium
Ha of
+122 kJmol1
chlorine
1st IE of
+550 kJmol1
strontium
2nd IE of
104 kJmol1
strontium
of chlorine -349 kJmol1
Remember:
2x EA of chlorine used
2x Ha of chlorine used

N a ( s ) + 1/ 2 H 2 ( g )

N a H (s)

Construct a Born-Haber cycle

And find 2nd electron affinity of oxygen
H / kJ mol
1

Enthalpy of atomisation of
magnesium
Bond energy of O == O in
oxygen
1st ionisation energy of
magnesium
2nd ionisation energy of
magnesium
Ist electron affinity of
oxygen
Lattice enthalpy of
magnesium oxide
Enthalpy of formation of
magnesium oxide

+150
+496
+736
+1450
142
3889
602

150 + (496) + 736 + 1450 + 602 + = 142 + 3889 x = +845 k J mol 1

(496) is key point
Use the data below to calculate the first electron affinity of chlorine.
-642 = 150 +736 +1450 +2(121) +2x +(-2493)
2x = 727
Enthalpy change
Enthalpy change
x = 363 1
+150 kJ mol1
Hat of magnesium
1
+736
kJ
mol
1st IE of magnesium
+1450 kJ mol1
2nd IE of magnesium
642 kJ mol1
Hf of MgCl2
+121 kJ mol1
Hat of chlorine
2493 kJ mol1
Hlatt of MgCl2
Understand the factors that influence the value of the lattice energies
Factors affecting theoretical value of lattice enthalpy/energy Radius/size of ions Charges on ions
Strong attraction - Small ionic radius and high charge
Weak attraction Large ionic radius and small charge
Lattice energy is the measure of the strength of bonds in that ionic compound. It is the equivalent to the amount of energy required
to separate a solid ionic compound into gaseous ions (always negative, exothermic)
- When lattice energy increases it becomes more negative
- Lattice energies increase when ions are smaller with high charge
- Strong attraction between ions because their ionic radii are small
Less attraction between ions because their ionic radii are larger
Understand that values of lattice energies calculated from the Born-Haber cycle may differ from those calculated from a purely
ionic model - limited to the radius and charge of the ions
- Experimental lattice energies are from Born-Haber cycles
- Theoretical lattice energies are from equations, assumes ionic lattice is totally ionic, when actually it has covalent
character(electron sharing)
If the metal cation is small and/or highly charged, it will distort the electron cloud of the anion , more polarising
If the non metal anion is larger it is more polarisable
This polarisation of the negative ion leads to partial covalency
Questions:
Theoretically Hlatt MgCl2 is 2326 kJ mol1
Experimental Hlatt MgCl2 is 2526 kJ mol1
Explain why this difference occurs
MgCl2 has (a degree of ) covalent character
due to polarisation of the anion

Theoretical Hlatt MgI2, is 1944 kJ mol1

Experimental Hlatt MgI2, is 2327 kJ mol1
Explain why this difference occurs
magnesium ion is small and highly charged
leading to polarisation of the (large) iodide ion
and (causing) covalency (into the lattice)
The theoretical and actual values of the lattice enthalpy of magnesium fluoride are very similar because magnesium fluoride is
almost completely ionic. Explain why magnesium fluoride is almost completely ionic
Fion is small Mg2+ ion does not have a high enough charge density to polarise F
Magnesium iodide compound. Radius of magnesium ion is 0.072 nm, iodide ion is 0.215 nm.
(i) Describe the effect that the magnesium ion has on an iodide ion next to it in the magnesium iodide lattice - The electrons

around the iodide ion are drawn towards the magnesium ion
(ii) What TWO quantities must be known about the ions in a compound in order to calculate a theoretical lattice energy?
Radius/size of ions Charges on ions
(iii) Suggest how the value of the theoretical lattice energy would compare with the experimental value from a Born-Haber Cycle
for magnesium iodide. - Less (exothermic) - covalent character (strengthens lattice)
Why is the lattice energy of magnesium hydroxide more exothermic than that of barium hydroxide?
as magnesium has a much smaller ion (than barium ion)
and has same charge
so stronger attraction between ions
charge density scores 1 (out of first 2 marks)
Explain why the lattice enthalpy of magnesium fluoride, MgF2, is more exothermic than that of calcium chloride.
smaller size of cation smaller size of anion greater attraction between (oppositely charged) ions
Lattice energies
Lattice energies
MgCl2 2526 kJ mol1
NaCl(s) is 771 kJ mol1
CaCl2 2237 kJ mol1
MgO(s) is 3889 kJ mol1
SrCl2 2112 kJ mol1
Explain the difference in lattice energies
BaCl2 2018 kJ mol1
Explain why lattice energies become less exothermic
Lattice enthalpy depends on charges and the ionic radii
Comparison of Na+/Mg2+ size and charge
As group descended, radius of M 2+ (ion) increases
Comparison of Cl / O2 size and charge
Charge on ions remains the same
(High LE results from) higher interaction
(down group) weaker forces of attraction between ions

M
H

X (s)

(g )

L a ttic e

X (g )

H y d r a tio n

(a q ) +

X (a q )

H y d r a tio n

Find enthalpy of solution of NaCl:

Lattice enthalpy of sodium chloride = -771
hydration enthalpy of Na+
= -406
hydration enthalpy of Cl= -364
Hsol = Hhyd (Na+) + Hhyd (Cl-) Hlatt(NaCl)
= (-406) + (-364) (-711) = +1kJmol -1

S o lu tio n

Understand how Hlatt and Hhyd vary the solubilities of the hydroxides and sulphates of Group 2
Enthalpy change of solution - Enthalpy change when one mole of a substance is dissolved completely in a large volume of a
solvent at constant pressure. Remember: Hsoln = Hlatt +X + Hhyd +HhydX
(Always small because they almost cancel out)
To dissolve, Hhyd Hlattice so enough hydration energy needed to overcome breaking the lattice
When an ionic substance dissolves enthalpy change depends on Hlatt of the solid Hhyd of the ions
Energy has to be supplied to break up the lattice of ions
Energy is released when these ions form bonds with water molecules
Trends in solubility depend on how fast both enthalpy terms fall relative to each other.
- As you go down a Group:
Energy needed to break up the lattice falls because, bigger ions, larger distance between ions, less attraction between +
and - ions
Hydration enthalpies falls - bigger ions, less charge density, reduces the attraction of water, the less exothermic the
hydration enthalpy.
- Hydroxides become more soluble
The lattice enthalpy falls faster than the hydration enthalpy, Hsoln becomes more exothermic(-) (more soluble)
- Sulphates become less soluble
The hydration enthalpy falls faster the Hsoln becomes more endothermic(+) (less soluble)
Because sulphate ion is bigger, change in ionic radius of Group 2 cations doesnt have as much affect on Hlatt
The greater the charge density the easier it is for the Group 2 cation to hydrate and hence dissolve in water due to greater
attraction with the polar water molecules.
Salt
MgSO4
CaSO4

Relative solubility
1
102

Explain the reasons for this trend in solubility in terms of changes of lattice energies and
enthalpies of hydration.
salt likely to be more soluble if Hsol exothermic

SrSO4
BaSO4

104
l06

both lattice energy and hydration enthalpies become less exothermic

as cations increase in size
but lattice energy changes less so enthalpy of solution less exothermic

H /kJ mol1
1480
Hhydration of Sr2+
2+
1360
Hhydration of Ba

460
Hhydration of OH
Lattice enthalpy of Sr(OH)2
1894
Lattice enthalpy of Ba(OH)2
1768
(i) Explain why the lattice enthalpy of strontium hydroxide is different from that of barium hydroxide.
charge density of Sr2+ < Ba2+ stronger force of attraction between ions
(ii) Explain why the hydration enthalpy of a cation is exothermic.
Negative part of water attracted to (+ ion) and forms bond bond formation releases energy
(iii) Use the lattice enthalpy and hydration enthalpy values to explain why barium hydroxide is more soluble in water than
strontium hydroxide.
Hsol = Hhyd Hlattice
Hlatt and Hhydr decrease down Group 2 (Barium lower than Strontium)
Hlatt decreases more than the Hhydr
Hsoln Ba(OH)2 more exothermic (than for Sr(OH)2,(so more soluble))
Hsoln = Hlatt + HhydrM2+ion + 2 Hhydr OH ion or = Hlatt + Hhydr ions
Hsoln Sr(OH)2 = ( 1894) + ( 1480) + 2 ( 460)
= 506 kJ mol1
Hsoln Ba(OH)2 = ( 1768) + ( 1360) + 2 ( 460)
= 512 kJ mol1
Enthalpy of hydration of Mg2+ 1890 kJ mol1
Calculate Hsoln of Mg(OH)2
Enthalpy of hydration of Ba2+ 1275 kJ mol1
Hsoln = -1890 -550 -550 +2995 = 5kJ mol1
Enthalpy of hydration of OH 550 kJ mol1
Lattice energy of Mg(OH)2 2995 kJ mol1
Use the data to explain how the solubility of Ba(OH)2
Lattice energy of Ba(OH)2 2320 kJ mol1
compares with Mg(OH)2
Hlatt down but Hhyd down by less
Draw a labelled Hesss law cycle for Mg(OH)2(s)
Hsolution is more exothermic
solubility is greater

Explain why magnesium oxide is insoluble in water.

not enough energy generated by hydration to overcome breaking the lattice
solubility due to balance between Hlattice and Hhydration of the ions

Hsol = Hhyd Hlattice

Further:

Formation of MgCl2 is energetically favoured because of its higher lattice enthalpy than MgCl, which is almost never
formed
High lattice enthalpy more than compensates for the additional energy that has to be supplied for the 2 nd ionisation of
magnesium