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Born-Haber Cycles Calculations

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Chemistry

Now you know how to draw a Born-Haber cycle like the one shown below, what's next? Well, you can use it to calculate the lattice enthalpy of an ionic solid, or any other unknown enthalpy change shown in the cycle. How? Remember, Hess’ Law states that the enthalpy change of a reaction remains the same regardless of the route taken. This allows us to calculate the enthalpy change for any part of the cycle as long as we start and end at the same places.

This means:

If we rearrange this equation we can use it to calculate lattice enthalpy:

Born-Haber Cycles Calculations | Potassium Chloride | StudySmarterBorn Haber cycle for potassium chloride, Olive [Odagbu] StudySmarter Originals

  • In this article, you will practice calculating lattice enthalpies using Born-Haber calculations.
  • We will look at how you can compare the lattice enthalpies of different substances and the factors that affect lattice enthalpy.
  • At the end, we will see how physicists calculate lattice energy theoretically, and why these values sometimes differ from their corresponding experimental values.

Examples of Born-Haber calculations

You need to practice to get the hang of lattice enthalpy calculations, so let us try a few example calculations together!

Use the information on the table below to calculate the lattice formation enthalpy of potassium chloride (KCl).

K+90+418
Cl+122-349
KCl-437

Step 1

Draw the Born-Haber cycle for KCl as shown below.

Born-Haber Cycles Calculations, Potassium Chloride, StudySmarterBorn-Haber KCl, Olive [Odagbu] StudySmarter Originals

Step 2

Apply Hess’ Law to the diagram.

Step 3

Fill in the values from the table above.

Make sure to use brackets when calculating the lattice enthalpy since the signs will affect your answer.

Use the information in the table below to calculate the lattice formation enthalpy of magnesium oxide (MgO).

Mg+148+736 +1450
O+248-142 +770
Mg-602

Step 1

Draw the Born-Haber cycle for MgO as shown below.

Born-Haber Cycles Calculations | Magnesium oxide | StudySmarterBorn-Haber cycle MgO, Olive [Odagbu] StudySmarter Originals

Step 2

Apply Hess’ Law to the diagram.

Step 3

Fill in the values from the table above

Comparing lattice enthalpies

For your chemistry exams, you must be able to explain the differences between lattice enthalpies of different substances. You will also be expected to give a reason for the differences between the theoretical and experimental values of lattice enthalpy. Not to worry- we’ve got you covered!

Factors that affect lattice enthalpy

Two factors that affect lattice enthalpy are:

  • The charges on the ions
  • The radius of the ions

The charge on the ion

Compare the lattice enthalpies of sodium chloride and magnesium oxide below. Their crystal lattices have the same geometry, so why are their enthalpies different?

Born-Haber cycles calculations, Lattice Enthalpies, StudySmarterLattice enthalpies of magnesium oxide and sodium chloride. chemguide.co.uk

Have a look now at their ions. Can you see a reason for the difference in their lattice enthalpies?

Born-Haber Cycles Calculations, Sodium chloride and magnesium oxide ions, StudySmarterThe ions of sodium chloride and magnesium oxide. Olive [Odagbu] StudySmarter Originals

Magnesium and oxygen ions have larger ionic charges than sodium and chloride ions. Ions with larger ionic charges have stronger electrostatic attraction between the ions. More energy is needed to overcome the attraction between the ions and break up the lattice. So the lattice dissociation enthalpy of magnesium oxide (MgO) is larger than that of sodium chloride (NaCl).

The radius of the ion

Magnesium ions and oxide ions are smaller than sodium and chloride ions. This means the ions in the magnesium oxide lattice are closer together. The strength of ionic attraction depends on the closeness of the centres of the attracted ions, so there is a stronger attraction between the magnesium and oxygen ions.

Ions with larger radii tend to have smaller lattice enthalpies, because the electrostatic attraction between larger ions is weaker.

You can observe this effect as you go down a group on the periodic table. As an example look at Group 1. As their positive ions get bigger, the lattice enthalpies of their chloride salts decrease.

Born-Haber cycles calculations, Trends in lattice enthalpies, StudySmarterLattice enthalpies get smaller as you go down a group. chemguide.co.uk

Theoretical values for lattice enthalpy

Physicists use a theoretical method to calculate lattice enthalpies. This is based on the assumption that the substance is highly ionic with only electrostatic attraction between the ions. In other words, they consider the ions as point charges that bond together to make a lattice. They also take into account the geometry of the lattice and the distance between the atoms.

What physicists actually calculate is the theoretical lattice energy and not lattice enthalpy. It is possible to do a calculation that converts one to the other, but you won’t need to know how to do this for your exams! However, you will need to talk about the differences in their values.

The table below shows the difference between lattice enthalpies calculated using this theoretical method and enthalpies calculated using Born-Haber cycles. Can you see much of a difference between the values?

CompoundExperimental Lattice Energy/ Theoretical Lattice Energy/
NaF-918-912
NaCl-780-770
NaBr-742-735
AgF-958-920
AgCl-905-833
AgBr-891-816
  • A small difference, as in the case of NaCl, suggests that the assumption the compound is ionic is fairly accurate.
  • A large difference, as in the case of AgCl, suggests that the compound is not purely ionic. Instead, the bonds show a covalent character.

We say Born-Haber cycles are experimental because they use enthalpy changes that can be measured to calculate lattice enthalpy. On the other hand, the physics-style calculations are based on the assumption that an ionic compound is completely ionic. So the lattice enthalpy values that you get with the second method are theoretical.

A covalent character means that the electrons in an ionic bond behave a little like those in a covalent bond. This happens when there is not enough electronegativity between the atoms for a complete electron transfer. The anion (negative ion) then becomes polarised.

Essentially, a cation (positive ion) attracts the electrons on an anion (negative ion). This attraction makes the electrons on the anion overlap the electron cloud of the cation and distorts the anion’s electron density (shown below).

Born-Haber cycles calculations, Covalent character, StudySmarterCovalent character. Olive [Odagbu] StudySmarter Originals

The anion becomes polarised because its electrons are no longer evenly distributed in the orbitals. Instead, some electrons become clustered between the cation and the anion- a little bit like a shared pair of electrons in a covalent bond.

Born-Haber cycles, Covalent character, StudySmarterCovalent character. Olive [Odagbu] StudySmarter Originals

Have a look at the following image:

Born-Haber cycles, covalent character and polarisation, StudySmarterCovalent character and polarisation. Olive [Odagbu] StudySmarter Originals

As you can see, not all cations have the same polarising power. Smaller cations with a high positive charge, like and , have a greater polarising power. This means the smaller a cation is, the more likely it is to distort the electron density of an anion.

Larger anions with a high negative charge, like and , are more easily polarised, since their outer shell electrons are further from the nucleus. In other words, the attraction between the nucleus and the electrons is weaker so they are more easily distorted.

We can observe greater covalent character in an ionic bond when there is more polarisation of the anion. This leads us to a trend in the periodic table: as we go from left to right the lattices become less ionic and more covalent. The differences between the theoretical and experimental values for lattice energy are greater. This trend supports an ionic model for compounds like sodium chloride.

Born-Haber Cycles Calculations, Trends in Lattices, StudySmarterTrends in lattice enthalpy. Olive [Odagbu] StudySmarter Originals

Polarisation as a result of the distortion of electron density shows us that bonding is neither purely ionic or covalent, but somewhere between the two.

Getting the hang of Born-Haber calculations takes practice! Review this article as many times as you need and use the flashcards in this section to strengthen your skills.

Born-Haber Cycles Calculations - Key takeaways

  • Lattice enthalpies calculated using Born-Haber cycles are experimental, because they use enthalpy changes that can be measured.
  • Two factors that affect lattice enthalpy are the charge and the radius of the ions.
  • Ions with large ionic charges have larger lattice dissociation enthalpies, because of stronger electrostatic attraction between the ions.
  • More energy is needed to break up the lattice. Ions with larger radii tend to have smaller lattice enthalpies, because the electrostatic attraction between larger ions is weaker.
  • Theoretical physics-style calculations for lattice enthalpy are based on the assumption that the substance is highly ionic.
  • Small differences between the theoretical and experimental values for a lattice enthalpy suggest that the substance is highly ionic.
  • Large differences between theoretical and experimental values of lattice enthalpy suggest there is a covalent character between the bonds of the ions.
  • A covalent character means that the electrons in an ionic bond behave a little like those in a covalent bond. There is not enough electronegativity between the atoms for a complete electron transfer.
  • An anion becomes polarised when its electron density is distorted by the attraction of a small highly charged cation.

Born-Haber Cycles Calculations

We can calculate lattice enthalpy by drawing a Born-Haber cycle with enthalpy changes we can measure. When we draw Born-Haber cycles we must show these enthalpy changes in the following order:


  1. The Enthalpy of formation of the compound.
  2. Enthalpy of atomisation of each element
  3. The first ionisation energy of the metal
  4. Subsequent ionisation enthalpies if appropriate
  5. First electron affinity of the non-metal
  6. Subsequent electron affinities if appropriate


Final Born-Haber Cycles Calculations Quiz

Question

Which two factors affect lattice enthalpy?

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Answer

Charge of the ion

Show question

Question

How does the charge on the ion affect lattice enthalpy?

Show answer

Answer

Ions with large ionic charges have stronger electrostatic attraction between the ions. This results in a larger lattice enthalpy.

Show question

Question

How does the radius of the ion affect lattice enthalpy? Give an example.


Show answer

Answer

Ions with larger radii tend to have smaller lattice enthalpies, because the ions are farther apart in the lattice structure. Electrostatic attraction between smaller ions is stronger, since the strength of ionic attraction depends on the closeness of the centres of the attracted ions


For example the ions in MgO are smaller than the ions in NaCl, so NaCl has a smaller lattice enthalpy.


Show question

Question

Why are physics-style calculations of lattice enthalpy theoretical?

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Answer

They are based on the assumption that a substance is highly ionic with strong electrostatic attraction between the ions.

Show question

Question

What do large differences between the theoretical and experimental values of lattice enthalpy suggest?

Show answer

Answer

Large differences between the theoretical and experimental values of lattice enthalpy suggest there is a covalent character in the ionic bond. This is as a result of polarisation due to radius of the ions and the charge on the ions.

Show question

Question

Why are lattice enthalpies calculated using Born-Haber cycles called experimental?

Show answer

Answer

Lattice enthalpies calculated using Born-Haber cycles are experimental because they use enthalpy changes that can be measured.

Show question

Question

Why is the enthalpy change of hydration of chloride ions exothermic?


Show answer

Answer

Heat energy is released when the ions form bonds with the water molecules, so hydration enthalpy is always exothermic.

Show question

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