Going over basics:

Enthalpy symbol H, is stored energy, its not possible to measure enthalpy but enthalpy changes (ΔΗ), by measuring temperature
changes of reactions at constant pressure. Δ Pronounced ‘delta’ means ‘change of’
Enthalpy change, ΔΗ 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 ΔΗ 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 ΔΗ 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 ΔHlatt 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 ΔHa θ Enthalpy change for production of one mole of gaseous atoms from the element in its
standard state
Enthalpy of hydration ΔHfhyd θ 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 ΔHhyd 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
½Cl2(g) 🡪 Cl(g)
Write an equation which represents the change when the second electron affinity of oxygen is measured
O–(g) + e →O2−(g)
Elemen Ionisation Energy/kJ mol –1 Explain the trend in IE within the group 1 elements
t
Li +51 electron further away from nucleus
9
Na +49 inceased shielding effect inner shells
4 less energy needed to remove outer electron
K
+41
8
Rb +40
2
Cs +37
6

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
Questions required to make gaseous ions from the
Presenting an ionic solid, NaH Construct a elements
Born-Haber cycle and to obtain Hlatt of
ΔHf of SrCl2(s) -829 kJmol–1
Draw a Born-Haber cycle which could be used to determine SrCl2(s)
the electron affinity of hydrogen ΔHa of strontium +164 kJmol–1
The Born-Haber cycle involves the formation of
Na+(g) + H(g) + e – an
ΔHa of chlorine ionic compound from the reaction of a
+122 kJmol–1
st metal(often
1 IE of strontium +550 kJmol–1element) with a non-metal
a Group1/2
nd
2 IE of 104 kJmol–1
Na+(g) + H– (g) strontium All endothermic reactions shown by arrow
pointing upwards
ΕΑ of chlorine (vice versa)
-349 kJmol–1
Na(g) +
H(g)
Remember: Atomisation enthalpy of metal (in
2x EA of chlorine this case lithium)
used 2x Ha of Ionisation enthalpy of metal
Na(g) + 1/2 H2 chlorine used Atomisation enthalpy of non-metal
(g) (in this case fluorine)
Electron affinity of non-metal
Lattice enthalpy
Na(s) + 1/2 H2
(g)

Na
H(s
)
 Construct a Born-Haber cycle
And find 2nd electron affinity of oxygen

150 + ½(496) + 736 + 1450 + 602 + × = 142 + 3889 x = +845 k J mol–

1
½ × (496) is key point
Use the data below to calculate the first electron affinity of chlorine. -642 = 150 +736 +1450 +2(121) +2x +(-2493)
Enthalpy change Enthalpy 2x = 727
change x = –363 ± 1
ΔHat of magnesium +150 kJ mol–1
1st IE of magnesium +736 kJ mol–1
2nd IE of magnesium +1450 kJ mol–1
ΔHf of MgCl2 –642 kJ mol–1
ΔHat of chlorine +121 kJ mol–1
ΔHlatt of MgCl2 –2493 kJ mol–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
ο Strong attraction - Small ionic radius and high charge
Ο 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
οΟ ΟΟ 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:
 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
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
NaCl(s) is –771 kJ MgCl2 –2526 kJ
mol–1 MgO(s) is –3889 mol–1 CaCl2 –2237
kJ mol–1 kJ mol–1 SrCl2 –
Explain the difference in lattice energies 2112 kJ mol–1
BaCl2 –2018 kJ
• Lattice enthalpy depends on charges and the ionic radii mol–1
• Comparison of Na+/Mg2+ size and charge Explain why lattice energies become less exothermic
• Comparison of Cl– / O2– size and charge
• (High LE results from) higher interaction • 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:

M+ (g) + X– (g) Lattice enthalpy of sodium chloride =
-771 hydration enthalpy of Na+ =
ΔH Lattice -406
ΔH Hydration ΔH Hydration hydration enthalpy of Cl- = -364
Hsol = Hhyd (Na+) + Hhyd (Cl-) – Hlatt(NaCl)
= (-406) + (-364) – (-711) = +1kJmol-1
M+ X– (s) M+ (aq) + X–(aq)
ΔH
Solution

Understand how ΔHlatt and ΔHhyd 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: ΔHsoln = − ΔHlatt (Μ+X–) + ΔHhyd(Μ+) + ΔHhyd(X–)
(Always small because they almost cancel out)
To dissolve, ΔHhyd ≥ ΔHlattice so enough hydration energy needed to overcome breaking the lattice

When an ionic substance dissolves enthalpy change depends on • ΔHlatt of the solid • ΔHhyd 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, ΔHsoln becomes more exothermic(-) (more soluble)
- Sulphates become less soluble
The hydration enthalpy falls faster the ΔHsoln becomes more endothermic(+) (less soluble)
Because sulphate ion is bigger, change in ionic radius of Group 2 cations doesn’t have as much affect on ΔHlatt

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
MgSO4 1 enthalpies of hydration.
CaSO4 10–2 • salt likely to be more soluble if ΔHsol exothermic
SrSO4 10–4 • both lattice energy and hydration enthalpies become less exothermic
l0–6 • as cations increase in size
BaSO4
• but lattice energy changes less so enthalpy of solution less exothermic
 ΔH /kJ mol–1
ΔHhydration of Sr
2+ –1480
ΔHhydration of Ba
2+ –1360
ΔHhydration 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 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.
• ΔHsol = ΔHhyd – ΔHlattice
• ΔHlatt and ΔHhydr decrease down Group 2 (Barium lower than Strontium)
• ΔHlatt decreases more than the ΔHhydr
• ΔHsoln Ba(OH)2 more exothermic (than for Sr(OH)2,(so more soluble))
ΔHsoln = –ΔHlatt + ΔHhydrM2+ion + 2 × ΔHhydr OH– ion or = –ΔHlatt + ∑ΔHhydr ions
ΔHsoln Sr(OH)2 = – (– 1894) + (– 1480) + 2 ×(– 460) = – 506 kJ mol–1
ΔHsoln Ba(OH)2 = – (– 1768) + (– 1360) + 2 ×(– 460) = – 512 kJ mol–1

Enthalpy of hydration of Mg2+ –1890 kJ Calculate ΔHsoln of Mg(OH)2

mol–1 Enthalpy of hydration of Ba2+ –1275
kJ mol–1 Enthalpy of hydration of OH– –550
kJ mol–1 Lattice energy of Mg(OH)2 –2995
kJ mol–1 Lattice energy of Ba(OH)2 –2320
kJ mol–1
Draw a labelled Hess’s law cycle for Mg(OH)2(s)
ΔHsoln = -1890 -550 -550 +2995 = 5kJ mol–1
Use the data to explain how the solubility of
Ba(OH)2 compares with Mg(OH)2
• ΔHlatt down but ΔHhyd down by less
• ∴ ΔHsolution 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 – ΔHlattice and ΔHhydration of the ions ΔHsol = ΔHhyd – ΔHlattice

ΔH /
kJ
mol–
1
Enthalpy of atomisation of +150
magnesium
Bond energy of O == O in +496
oxygen
1st ionisation energy of +736
magnesium
2nd ionisation energy of +1450
magnesium
Ist electron affinity of –142
oxygen
Lattice enthalpy of –3889
magnesium oxide
Enthalpy of formation of –602
magnesium oxide
Theoret T
ically h
ΔHlatt e
MgCl2 o
is – r
2326 kJ e
mol–1 t
Experi i
mental c
ΔHlatt a
MgCl2 l
is –
2526 kJ Δ
mol–1 H
Explain l
why a
t
this t
differen
ce
M
occurs
g
• MgCl2 has (a degree of )
covalent character I
2
• due to polarisation of the
,
anion
i
s

–
1
9
4
4

k
J

m
o
l
–
1

E
x
p
e
r
i
m
e
n
t
a
l

Δ
H
l
a
t
t

M
g
I
2
,

i
s

–
2
3
2
7

k
 J

m
o
l
–
1

E
x
p
l
a
i
n

w
h
y

t
h
i
s

d
i
f
f
e
r
e
n
c
e

o
c
c
u
r
s
• magnesi
um ion
is small
and
highly
charged
• leading
to
polarisat
ion of
the
(large)
iodide
ion
• and
(causing
)
covalen
cy (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• 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

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