Going over basics:

Enthalpy symbol H, is stored energy, its not possible to measure enthalpy but enthalpy changes (AH), by measuring temperature
changes of reactions at constant pressure. A Pronounced delta means change of
Enthalpy change, AH 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 AH 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 AH 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 AH
latt
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 AH
a

Enthalpy change for production of one mole of gaseous atoms from the element in its
standard state
Enthalpy of hydration AH
fhyd

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 AH
hyd
is exothermic: M
+
(g) + aq M
+
(aq))

Understand that:
Enthalpy of formation AH
f
Enthalpy change when one mole of a compound is formed from its elements
Na
(s)
+ (1/2)Cl
2(g)
NaCl
(s)

1
st
Ionisation Energy M(g) M
+
(g) + e

2
nd
Ionisation Energy M
+
(g) M
2+
(g) + e

1
st
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
2
nd
Electron affinity Enthalpy change per mole for the process, X

(g) + e

X
2
(g) O

(g) + e O
2
(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
Cl
2
(g) Cl(g)
Write an equation which represents the change when the second electron affinity of oxygen is measured
O

(g) + e O
2
(g)

Explain the trend in IE within the group 1 elements

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
Element Ionisation Energy/kJ mol
1
Li
Na
K
Rb
Cs
+519
+494
+418
+402
+376

A Born-Haber cycle calculates the lattice enthalpy
by comparing the AH
f
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 non-metal (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

Construct a Born-Haber cycle and to obtain AH
latt
of SrCl
2
(s)
AH
f
of SrCl
2
(s)
-829 kJmol
1

AH
a
of strontium
+164 kJmol
1

AH
a
of chlorine
+122 kJmol
1

1
st
IE of strontium
+550 kJmol
1

2
nd
IE of strontium
104 kJmol
1

EA of chlorine
-349 kJmol
1


Remember:
2x EA of chlorine used
2x AH
a
of chlorine used

Na(g) + H(g)
NaH(s)
Na (g) + H(g) + e
+
Na (g) + H (g)
+

Na(s) + H (g) /
1
2
2
Na(g) + H (g) /
1
2
2
Construct a Born-Haber cycle
And find 2
nd
electron affinity of oxygen
AH / kJ
mol
1

Enthalpy of atomisation of
magnesium
+150
Bond energy of O == O in
oxygen
+496
1st ionisation energy of
magnesium
+736
2nd ionisation energy of
magnesium
+1450
Ist electron affinity of
oxygen
142
Lattice enthalpy of
magnesium oxide
3889
Enthalpy of formation of
magnesium oxide
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.
Enthalpy change Enthalpy change
AH
at
of magnesium
1st IE of magnesium
2nd IE of magnesium
AH
f
of MgCl
2

AH
at
of chlorine
AH
latt
of MgCl
2

+150 kJ mol
1

+736 kJ mol
1

+1450 kJ mol
1

642 kJ mol
1

+121 kJ mol
1

2493 kJ mol
1


-642 = 150 +736 +1450 +2(121) +2x +(-2493)
2x = 727
x = 363 1


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
o Strong attraction - Small ionic radius and high charge
O 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
oO OO 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 AH
latt
MgCl
2
is 2326 kJ mol1
Experimental AH
latt
MgCl
2
is 2526 kJ mol1
Explain why this difference occurs
MgCl
2
has (a degree of ) covalent character
due to polarisation of the anion
Theoretical AH
latt
MgI2, is 1944 kJ mol1
Experimental AH
latt
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
F

ion is small Mg
2+
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, MgF
2
, is more exothermic than that of calcium chloride.
smaller size of cation smaller size of anion greater attraction between (oppositely charged) ions
Lattice energies
NaCl(s) is 771 kJ mol
1

MgO(s) is 3889 kJ mol
1

Explain the difference in lattice energies

Lattice enthalpy depends on charges and the ionic radii
Comparison of Na
+
/Mg
2+
size and charge
Comparison of Cl

/ O
2
size and charge
(High LE results from) higher interaction
Lattice energies
MgCl2 2526 kJ mol1
CaCl2 2237 kJ mol1
SrCl2 2112 kJ mol1
BaCl2 2018 kJ mol1
Explain why lattice energies become less exothermic

As group descended, radius of M 2+ (ion) increases
Charge on ions remains the same
(down group) weaker forces of attraction between ions



Find enthalpy of solution of NaCl:
Lattice enthalpy of sodium chloride = -771
hydration enthalpy of Na+ = -406
hydration enthalpy of Cl- = -364

H
sol
= H
hyd
(Na
+
) + H
hyd
(Cl
-
) H
latt
(NaCl)
= (-406) + (-364) (-711) = +1kJmol
-1

Understand how AH
latt
and AH
hyd
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: AH
soln
= AH
latt
(M
+
X

) + AH
hyd
(M
+
) + AH
hyd
(X

)
(Always small because they almost cancel out)
To dissolve, AH
hyd
AH
lattice
so enough hydration energy needed to overcome breaking the lattice

When an ionic substance dissolves enthalpy change depends on AH
latt
of the solid AH
hyd
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, AH
soln
becomes more exothermic(-) (more soluble)
- Sulphates become less soluble
The hydration enthalpy falls faster the AH
soln
becomes more endothermic(+) (less soluble)
Because sulphate ion is bigger, change in ionic radius of Group 2 cations doesnt have as much affect on AH
latt


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 Relative solubility 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 AHsol exothermic
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
MgSO
4
1
CaSO
4
10
2

SrSO
4
10
4

BaSO
4
l0
6

M (g) + X (g)
M (aq) + X (aq) M X (s)
+
+ +

AH AH
AH
AH
Hydration Hydration
Lattice
Solution
AH /kJ mol
1

AH
hydration
of Sr
2+
1480
AH
hydration
of Ba
2+
1360
AH
hydration
of OH

460
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 Sr
2+
< Ba
2+
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.
AH
sol
= AH
hyd
AH
lattice

AH
latt
and AH
hydr
decrease down Group 2 (Barium lower than Strontium)
AH
latt
decreases more than the AH
hydr

AH
soln
Ba(OH)
2
more exothermic (than for Sr(OH)
2
,
(so more soluble))
AH
soln
= AH
latt
+ AH
hydr
M
2+
ion + 2 AH
hydr
OH

ion or = AH
latt
+ AH
hydr
ions
AH
soln
Sr(OH)
2
= ( 1894) + ( 1480) + 2 ( 460) = 506 kJ mol
1

AH
soln
Ba(OH)
2
= ( 1768) + ( 1360) + 2 ( 460) = 512 kJ mol
1

Enthalpy of hydration of Mg2+ 1890 kJ mol1
Enthalpy of hydration of Ba2+ 1275 kJ mol1
Enthalpy of hydration of OH 550 kJ mol1
Lattice energy of Mg(OH)2 2995 kJ mol1
Lattice energy of Ba(OH)2 2320 kJ mol1

Draw a labelled Hesss law cycle for Mg(OH)2(s)

Calculate AH
soln
of Mg(OH)2
AH
soln
= -1890 -550 -550 +2995 = 5kJ mol1

Use the data to explain how the solubility of Ba(OH)2
compares with Mg(OH)2
AH
latt
down but AH
hyd
down by less
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 AH
lattice
and AH
hydration
of the ions AH
sol
= AH
hyd
AH
lattice


Further:
Formation of MgCl
2
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