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Bond Enthalpy and Pauling Values

A concise OCR A Level Chemistry A revision guide to two numbers you must be able to read and use in 2.2.2: the average bond enthalpy as a measure of how strong a covalent bond is (2.2.2(f)), and Pauling electronegativity values as a measure of how unequally that bond is shared (2.2.2(i)).

Paper 1 and 2
2.2.2: Bonding and Structure
H432/01 and H432/02
Dr. Mohammed Al-Fatah

Written by:
Dr. Mohammed Al-Fatah

Chemistry specialist revision notes for A Level Chemistry.

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Before you start

GCSE Recap: Shared Pairs and Breaking Bonds

Before you start, check what a covalent bond is and which way the energy goes when one is broken.

1

Average Bond Enthalpy Measures Bond Strength

A covalent bond is a strong electrostatic attraction between a shared pair of electrons and the nuclei of the bonded atoms. The strength of that attraction is measured by the average bond enthalpy: the energy needed to break one mole of a particular covalent bond in gaseous molecules, averaged over many different compounds containing that bond. Values are always positive because bond breaking is endothermic, and they are quoted in kJ mol-1.

BondAverage bond enthalpy / kJ mol-1What it tells you
H-H436Strong single bond; hydrogen needs a catalyst or high temperature to react
C-H413Typical strong bond of an alkane
C-C347A single bond between carbon atoms
C=C612Stronger than C-C, but less than twice as strong
C≡C838The strongest carbon-carbon bond
N≡N945Exceptionally strong; nitrogen gas is very unreactive
O=O498Oxygen reacts readily once started
Cl-Cl243Weak single bond; easily broken by ultraviolet light
H-Cl432Strong polar bond

The higher the bar, the more energy is needed to break one mole of that bond in the gas phase.

Key idea: A larger average bond enthalpy means a stronger bond. More energy is needed to break it, so the bond is less likely to be broken during a reaction.

Check your understanding

Quick Check: Which Bond Gives Way First

Use the two bond enthalpies to explain the difference in reactivity.

2

Why the Value Is an Average

The exact energy needed to break a C-H bond depends on the molecule it sits in: the four C-H bonds in methane do not all break with the same energy, and a C-H bond in ethanol differs again. The data-book value of 413 kJ mol-1 is the mean across a wide range of compounds. Only diatomic molecules such as H2, Cl2 and HCl have a single, exact bond enthalpy, because there is only one environment for that bond.

This is why enthalpy changes calculated from average bond enthalpies rarely match the experimentally measured value: the average is a good estimate, not the exact figure for that molecule.

Exam sentence: The average bond enthalpy is the mean energy required to break one mole of a specified bond in gaseous molecules, averaged over many compounds containing that bond.

Check your understanding

Quick Check: Exact or Averaged?

Decide which of these four bonds has an exact bond enthalpy.

Check your understanding

Quick Check: Explain the Single Quoted Value

Write a short explanation, then compare it with the mark points and the model answer.

3

Comparing Bonds with Enthalpy Values

Two patterns in the table are worth remembering because they explain reactivity later in the course.

  • Multiple bonds are stronger than single bonds, but not proportionally. C=C (612 kJ mol-1) is much less than twice C-C (347 kJ mol-1). The second, π component of the double bond is therefore the weaker part, which is why alkenes react by breaking the π bond in addition reactions while the σ bond survives.
  • Weak bonds break first. The Cl-Cl bond (243 kJ mol-1) is weak enough to be split by ultraviolet light, which starts free-radical substitution. The N≡N bond (945 kJ mol-1) is so strong that nitrogen gas hardly reacts at all.

Exam focus: When asked why one molecule is more reactive than another, quote the bond enthalpies and state clearly which bond needs less energy to break.

Check your understanding

Quick Check: Single, Double and Triple

Work out what each extra bonded pair adds, then complete the account.

4

Reading Pauling Electronegativity Values

Bond enthalpy tells you how strong a bond is; electronegativity tells you how unequally the shared pair is held. Linus Pauling devised a relative scale with fluorine, the most electronegative element, set at 4.0. The values have no units because they are relative, and they increase across a period and decrease down a group.

ElementPauling valueElementPauling value
F4.0C2.5
O3.5S2.5
Cl3.0H2.1
N3.0Mg1.2
Br2.8Na0.9

The difference between the two values in a bond tells you what kind of bond to expect. A difference of about zero gives a non-polar covalent bond; a small to moderate difference gives a polar covalent bond with δ+ and δ– charges; a very large difference (about 1.7 or more) means the electrons are transferred almost completely and the bonding is best described as ionic.

The Pauling scale is relative: only the differences between two bonded atoms matter.

BondDifference in Pauling valuesType of bond
C-H2.5 – 2.1 = 0.4Almost non-polar covalent
H-Cl3.0 – 2.1 = 0.9Polar covalent, Hδ+-Clδ-
O-H3.5 – 2.1 = 1.4Strongly polar covalent
Na-Cl3.0 – 0.9 = 2.1Ionic

Exam sentence: The greater the difference in electronegativity between the bonded atoms, the more polar the bond; the more electronegative atom carries the δ– charge.

Check your understanding

Quick Check: Which Number Answers the Question

Five quick decisions: some need the bond enthalpy, some need the Pauling values.

Check your understanding

Quick Check: Strength Is Not Polarity

In each round, pick the one statement that is accurate.

5

Common Exam Mistakes

  • Giving average bond enthalpy a negative sign. Breaking bonds is endothermic, so the value is always positive.
  • Forgetting the word gaseous in the definition. Bond enthalpies refer to molecules in the gas phase.
  • Putting units on electronegativity. The Pauling scale is relative and has no units.
  • Assuming a strong bond is always non-polar, or a polar bond is always weak. Bond enthalpy and polarity are separate ideas: H-Cl is both strong (432 kJ mol-1) and polar.
  • Treating C=C as twice as strong as C-C. It is 612 compared with 347 kJ mol-1, so the extra π bond is weaker than the σ bond.

Exam sentence: Bond enthalpy measures strength; electronegativity difference measures polarity. Quote the numbers when you compare bonds.

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Copyright and author footprint: This OLS revision page was written for Online Learning System by Dr. Mohammed Al-Fatah. It is designed for A Level Chemistry revision and should not be copied or redistributed without permission.