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C. Structure and Properties of Matter · Structure and Properties of Matter

Predicting Molecular Polarity from Shape and Electronegativity

C2.4 C2.3 A1.10About 65 minutes
Learning goals
  • I can use electronegativity differences to identify polar bonds.
  • I can treat bond dipoles as vectors and decide whether they cancel.
  • I can predict whether a molecule is polar from its VSEPR shape.
  • I can explain how polarity affects solubility and boiling point.

Words to know

bond dipole
The separation of partial charges in a polar bond, shown by an arrow toward the δ− atom.
dipole
Two equal and opposite charges separated by a distance; a molecule with a net dipole is polar.
polar molecule
A molecule with a net dipole because its bond dipoles do not cancel.
dipole moment
A measure of the size of a molecule's net dipole, in debyes (D).
non-polar molecule
A molecule with no net dipole, either because its bonds are non-polar or because its bond dipoles cancel.

Why oil and vinegar separate

Shake a salad dressing and it soon separates into an oily layer and a watery layer. The vinegar is mostly water, made of polar molecules; the oil is made of non-polar molecules. Polarity decides what mixes with what, what boils easily, and even how a microwave oven heats your leftovers (it makes polar water molecules rotate back and forth).

In this lesson you will combine two skills: bond polarity from electronegativity (Grade 11) and molecular shape from VSEPR (this unit).

Step 1: Bond polarity (review)

Remember from Grade 11: electronegativity (EN) is an atom's ability to attract shared electrons. For a bond, find ΔEN = EN(higher) − EN(lower), using the Pauling values rounded to one decimal place:

  • 0 to 0.4: non-polar covalent (C–H, 2.6 − 2.2 = 0.4, is treated as non-polar)
  • 0.5 to 1.7: polar covalent: the more electronegative atom is δ−
  • more than 1.7: mostly ionic

A polar bond is a bond dipole, drawn as an arrow pointing toward the δ− end, with a crossed tail (+) at the δ+ end.

Step 2: Molecular polarity

A molecule is polar if it has a net dipole: one end slightly positive and the other slightly negative. Bond dipoles are vectors: they have size and direction, and they add like forces in physics.

  • If the bond dipoles cancel, the molecule is non-polar, even though its bonds are polar.
  • If they do not cancel, the molecule is polar.

Bond dipoles cancel when the molecule is symmetrical: the central atom has identical atoms in a symmetrical VSEPR shape (linear AX₂, trigonal planar AX₃, tetrahedral AX₄, trigonal bipyramidal AX₅, octahedral AX₆). Lone pairs on the central atom usually make a shape lopsided (bent, pyramidal, seesaw), so those molecules are usually polar. The exceptions are AX₂E₃ (linear, like XeF₂) and AX₄E₂ (square planar, like XeF₄), where the lone pairs are placed symmetrically.

COOCO₂: bond dipoles cancelnon-polar moleculeOHHδ−δ+δ+netdipoleH₂O: bent, so bond dipoles add uppolar molecule
Bond dipole arrows point toward the more electronegative atom (the crossed tail is the positive end). In linear CO₂ the two equal dipoles point in opposite directions and cancel. In bent H₂O they add to give a net dipole toward oxygen.
Are there polar bonds?(ΔEN of 0.5 or more)noNON-POLAR (e.g., Cl₂, CH₄)yesIs the shape symmetrical, withidentical outer atoms and nolone pairs on the centre?*yesNON-POLAR (CO₂, BF₃, CCl₄, SF₆)noPOLAR (H₂O, NH₃, CHCl₃)*exceptions: XeF₂ and XeF₄ have lone pairs placed symmetrically, so they are non-polar
A flowchart for deciding molecular polarity. (CH₄ appears in the left box because C–H bonds, with ΔEN = 0.4, are treated as non-polar.) A symmetrical shape makes equal bond dipoles cancel.

How big is a dipole?

The size of a molecule's net dipole is its dipole moment, measured in debyes (D), a unit named after the physicist Peter Debye. Some values: CO₂ 0 D, CH₄ 0 D, HCl about 1.1 D, NH₃ about 1.5 D, H₂O about 1.85 D. Water's large dipole moment is one reason it is such an excellent solvent for ionic and polar substances.

Why polarity matters

  • Solubility ("like dissolves like"): polar substances tend to dissolve in polar solvents (sugar in water) and non-polar in non-polar (grease in hexane), as you saw in the Grade 11 Solutions and Solubility unit.
  • Boiling and melting points: polar molecules attract each other with dipole-dipole forces, so they usually boil at higher temperatures than non-polar molecules of similar size (next lesson).
  • Response to electric fields: polar molecules turn to line up in an electric field. Microwave ovens use a rapidly changing field to make water molecules jostle and heat food.
Worked example

Example 1: CCl₄ versus CHCl₃

Is tetrachloromethane (CCl₄) polar? Is trichloromethane (chloroform, CHCl₃) polar?

  1. C–Cl: ΔEN = 3.2 − 2.6 = 0.6, so each C–Cl bond is polar. C–H (0.4) is treated as non-polar.
  2. CCl₄ is tetrahedral (AX₄) with four identical C–Cl dipoles, which cancel exactly.
  3. CHCl₃ is also tetrahedral, but one position holds H instead of Cl. The three C–Cl dipoles are not balanced by a fourth, so they add to a net dipole.

CCl₄ is non-polar; CHCl₃ is polar (net dipole toward the three Cl atoms).

Worked example

Example 2: NH₃ versus BF₃

Both have one central atom bonded to three atoms. Why is NH₃ polar while BF₃ is non-polar?

  1. N–H: ΔEN = 3.0 − 2.2 = 0.8 (polar). B–F: 4.0 − 2.0 = 2.0 (very polar; boron's EN is about 2.0).
  2. BF₃ is trigonal planar with no lone pair: three equal dipoles at 120° cancel.
  3. NH₃ is trigonal pyramidal (one lone pair): the three N–H dipoles all point partly toward N, upward, and add.

Shape decides it: BF₃'s symmetrical planar shape cancels its dipoles; NH₃'s pyramidal shape does not, so NH₃ is polar.

Worked example

Example 3: Molecules with expanded octets

Predict whether SF₄ and SF₆ are polar.

  1. S–F bonds are polar (ΔEN = 4.0 − 2.6 = 1.4).
  2. SF₆ is octahedral (AX₆) with six identical dipoles in opposite pairs: they cancel → non-polar.
  3. SF₄ is seesaw (AX₄E): the equatorial lone pair makes the molecule lopsided; the dipoles do not cancel → polar.

SF₆ is non-polar; SF₄ is polar.

The most common mistake

Polar bonds are not the same as a polar molecule. Always do both steps: (1) are the bonds polar? (2) does the shape let the dipoles cancel? Draw the 3-D shape before deciding.

Just for fun

Why did the water molecule get invited to every party? Because it was so polar, everyone was attracted to it. (The oil molecules stayed in their own layer, as usual.)

Hands-on activity

Bending water with static

You need: a tap, a plastic comb or an inflated balloon, a wool sweater or dry hair, and a dry day if possible. Grown-up note: if you use a balloon, supervise young children and pick up any broken pieces at once.

  1. Turn on the tap so that a very thin, smooth stream of water runs (thinner than a pencil lead is ideal).
  2. Charge the comb or balloon by rubbing it quickly on wool or dry hair 10 to 15 times.
  3. Bring it close to the stream (about 1 to 2 cm away) without touching. Watch the stream.
  4. Try charging for longer, or bringing it closer, and record how far the stream bends each time.

What to look for: the stream bends toward the charged object. Water molecules are polar, so in the electric field near the comb they turn so that their oppositely charged ends face it and are pulled toward it. This is a classic demonstration of polarity; the full explanation also involves electric charges that collect on the surface of the stream, so treat it as good evidence of how strongly water responds to electric fields rather than as a perfect test for polarity. In a school lab, teachers sometimes compare the water stream with a stream of a non-polar liquid, which bends much less; never try that at home, because those liquids are flammable.

Your turn

1

Is HCl polar? Explain.

2

Is CO₂ polar? Explain.

3

Is H₂S polar?

4

Is CH₂Cl₂ (dichloromethane) polar?

5

Is BF₃ polar?

6

Is PCl₃ polar?

7

Is XeF₄ polar?

More practice: warm-up

1

What is electronegativity?

2

Which atom is δ− in an O–H bond?

3

Is Cl₂ polar?

4

What unit is used for dipole moments?

5

Is CH₄ polar?

More practice: on your own

1

Which is polar: SO₂ or SO₃? Explain.

2

Is ClF₃ polar?

3

Is PCl₅ polar?

4

Explain why a molecule with polar bonds can be non-polar overall.

5

Arrange in order of increasing bond polarity: C–F, N–H, C–H, O–H.

Challenge

1

cis-1,2-Dichloroethene has both Cl atoms on the same side of the C=C bond; trans-1,2-dichloroethene has them on opposite sides. Which is polar?

2

Water's dipole moment is about 1.85 D. Each O–H bond dipole is at 52.25° to the line bisecting the H–O–H angle (half of 104.5°). Estimate the dipole of one O–H bond.

3

Both CO₂ and SO₂ have two polar bonds to oxygen. Use VSEPR to explain why SO₂ dissolves much better in water than CO₂ does (about 100 g/L versus about 1.5 g/L at room temperature, although both also react with water to some extent).

Check your understanding

Quiz

1.

Which molecule is polar?

2.

Why is CO₂ non-polar even though C=O bonds are polar?

3.

Which molecule is non-polar?

4.

In a bond dipole arrow, which way does the arrow point?

5.

Which pair of molecules has the same VSEPR shape but different polarity?

6.

Which is the most polar bond, using the Pauling values H 2.2, C 2.6, N 3.0, O 3.4, F 4.0?

For parents and teachers

Big idea (C2.4): molecular polarity depends on both bond polarity (electronegativity) and shape (VSEPR). Symmetrical molecules with identical outer atoms are non-polar even if their bonds are polar.

How to help: the water-bending activity is quick and memorable. When your teen classifies a molecule, ask them to say the two steps aloud: "Are the bonds polar? Does the shape cancel them?"

Common difficulties:

  • Calling CO₂ or CCl₄ polar because their bonds are polar.
  • Ignoring lone pairs when drawing the shape.
  • Forgetting that changing one outer atom (CH₄ to CH₃Cl) can make a symmetrical shape polar.