Bonding & Molecular Geometry

General Chemistry · Dr. Karmach

Dr. Karmach

By the end of this unit, you can…

  • Classify a bond as ionic, polar covalent, or nonpolar covalent from the electronegativity difference
  • Write the Lewis (electron dot) symbol of an atom or a monatomic ion
  • Count valence electrons and draw valid Lewis structures for molecules and polyatomic ions
  • Draw all resonance structures of a molecule or ion and describe the blend they represent
  • Assign formal charges and use them to choose the best Lewis structure
  • Draw the octet-rule exceptions: incomplete octets, odd-electron molecules, and expanded octets
  • Apply VSEPR theory to predict electron-pair geometry and molecular shape
  • Combine bond dipoles with molecular shape to judge whether a molecule is polar
  • Assign trigonal bipyramidal and octahedral electron geometries and their lone-pair shapes, and judge the polarity of five- and six-domain molecules
Dr. Karmach

Today's route 🗺️

  1. Electronegativity & Bond Type
  2. Lewis Structures
  3. Resonance & Formal Charge
  4. Exceptions to the Octet Rule
  5. VSEPR & Molecular Shape
  6. Molecular Polarity
  7. Five & Six Electron Domains
  8. Lattice Energy Trends
  9. Bond Energies & Reaction Enthalpy
Dr. Karmach

1 · Electronegativity & Bond Type

Classify any bond as nonpolar covalent, polar covalent, or ionic from the electronegativity difference, and mark which atom carries the partial negative charge.

Dr. Karmach

Pulling on shared electrons

Two atoms pull on the same pair of electrons. Pull evenly, and it stays centered. Pull much harder, and one atom drags the pair over, or takes it.

Dr. Karmach

How a bond shares its electrons

A bond is a shared pair of electrons. Each atom pulls on that pair; the strength of the pull is its electronegativity. Equal pulls share equally; unequal pulls share unequally.

Dr. Karmach

Electronegativity and its trend

Electronegativity measures how strongly an atom pulls on shared electrons. It climbs across a row and up a column, peaking at fluorine. Metals sit low; nonmetals near fluorine sit high.

Dr. Karmach

From difference to bond type

Subtract the two electronegativities, larger minus smaller, and read the bond type off the continuum.

under 0.4: even sharing · 0.4 to 1.7: unequal sharing · past 1.7: transfer
nonpolar covalent · polar covalent · ionic · guidelines, not walls
Dr. Karmach

The method

  1. Find the electronegativity difference. Larger minus smaller.
  2. Place it on the continuum. Near zero, nonpolar covalent; moderate, polar covalent; large, ionic.
  3. Name the bond and mark the charges. δ− on the more electronegative atom, δ+ on its partner.
Dr. Karmach

Worked example 1: the Cl–Cl bond

Cl–Cl (the bond inside Cl₂ gas)
electronegativity: Cl = 3.16 · Cl = 3.16 · wanted: bond type

Chlorine gas is two chlorine atoms sharing one pair of electrons.

Classify the bond.

Dr. Karmach

Worked example 1: solution

Cl–Cl (the bond inside Cl₂ gas)
electronegativity: Cl = 3.16 · Cl = 3.16

Step 1 · Find the electronegativity difference

ΔEN = 3.16 − 3.16 = 0
Dr. Karmach

Worked example 1: solution

Cl–Cl (the bond inside Cl₂ gas)
electronegativity: Cl = 3.16 · Cl = 3.16
Step 1 · Find the electronegativity difference
ΔEN = 3.16 − 3.16 = 0
Step 2 · Place it on the continuum

A difference of zero sits at the far left: nonpolar covalent.

Dr. Karmach

Worked example 1: solution

Cl–Cl (the bond inside Cl₂ gas)
electronegativity: Cl = 3.16 · Cl = 3.16
Step 1 · Find the electronegativity difference
ΔEN = 3.16 − 3.16 = 0
Step 2 · Place it on the continuum Step 3 · Name the bond and mark the charges
Cl–Cl → nonpolar covalent
equal electronegativities · the pair sits centered · no partial charges
Dr. Karmach

Worked example 1: solution

Cl–Cl (the bond inside Cl₂ gas)
electronegativity: Cl = 3.16 · Cl = 3.16
Step 1 · Find the electronegativity difference
ΔEN = 3.16 − 3.16 = 0
Step 2 · Place it on the continuum Step 3 · Name the bond and mark the charges
Cl–Cl → nonpolar covalent
equal electronegativities · the pair sits centered · no partial charges
Two atoms of the same element always pull equally. A bond between identical atoms is nonpolar, every time.
Dr. Karmach

Worked example 1: the bond on the continuum

Cl–Cl: ΔEN = 3.16 − 3.16 = 0
electronegativity: Cl = 3.16 · Cl = 3.16 · found: nonpolar covalent

Zero sits at the far left end of the continuum. Identical atoms share the pair evenly.
Dr. Karmach

Worked example 2: the H–Cl bond

H–Cl (hydrogen chloride)
electronegativity: H = 2.20 · Cl = 3.16 · wanted: bond type and partial charges

Hydrogen and chlorine share one pair of electrons.

A common first answer marks hydrogen as δ−. Test it against the two electronegativities.

Dr. Karmach

Worked example 2: solution

H–Cl (hydrogen chloride)
electronegativity: H = 2.20 · Cl = 3.16

Step 1 · Find the electronegativity difference

ΔEN = 3.16 − 2.20 = 0.96
Dr. Karmach

Worked example 2: solution

H–Cl (hydrogen chloride)
electronegativity: H = 2.20 · Cl = 3.16
Step 1 · Find the electronegativity difference
ΔEN = 3.16 − 2.20 = 0.96
Step 2 · Place it on the continuum

A difference of 0.96 sits between the 0.4 and 1.7 guidelines: polar covalent. The pair is shared, but not equally.

Dr. Karmach

Worked example 2: solution

H–Cl (hydrogen chloride)
electronegativity: H = 2.20 · Cl = 3.16
Step 1 · Find the electronegativity difference
ΔEN = 3.16 − 2.20 = 0.96
Step 2 · Place it on the continuum Step 3 · Name the bond and mark the charges
H–Cl → polar covalent, δ− on Cl
Cl (3.16) pulls harder than H (2.20) · the shared pair shifts toward Cl · H is δ+
Dr. Karmach

Worked example 2: solution

H–Cl (hydrogen chloride)
electronegativity: H = 2.20 · Cl = 3.16
Step 1 · Find the electronegativity difference
ΔEN = 3.16 − 2.20 = 0.96
Step 2 · Place it on the continuum Step 3 · Name the bond and mark the charges
H–Cl → polar covalent, δ− on Cl
Cl (3.16) pulls harder than H (2.20) · the shared pair shifts toward Cl · H is δ+
The partial negative marks the more electronegative atom, the one that pulls the pair closer. Marking hydrogen reversed the direction the electrons shift.
Dr. Karmach

Worked example 2: the bond on the continuum

H–Cl: ΔEN = 3.16 − 2.20 = 0.96
electronegativity: H = 2.20 · Cl = 3.16 · found: polar covalent, δ− on Cl

0.96 lands inside the middle band, between the 0.4 and 1.7 guidelines: unequal sharing.
Dr. Karmach

Take-home: δ− marks the stronger pull

H–Cl → δ− on Cl
Cl = 3.16 pulls harder than H = 2.20 · the shared pair shifts toward Cl
subtract backwards: 2.20 − 3.16 = −0.96
the negative sign points from δ+ toward δ−; it never puts the partial negative on H

The partial negative sits on the more electronegative atom. The size of the difference sets how polar the bond is; the direction of the pull sets which atom is δ−.

Dr. Karmach

Your turn: the Na–Cl bond

Na–Cl (sodium chloride)
electronegativity: Na = 0.93 · Cl = 3.16
ΔEN = 3.16 − 0.93 = →

Compute the difference, place it on the continuum, and name the bond.

Dr. Karmach

Your turn: the Na–Cl bond

Na–Cl (sodium chloride)
electronegativity: Na = 0.93 · Cl = 3.16
ΔEN = 3.16 − 0.93 = →

Compute the difference, place it on the continuum, and name the bond.

ΔEN = 3.16 − 0.93 = 2.23 → a large difference: ionic
Na–Cl → ionic
a metal and a nonmetal · Cl pulls the electron off Na completely · Na⁺ and Cl⁻
Dr. Karmach

Where this goes wrong

Putting δ− on the wrong atom. Shared electrons shift toward the more electronegative atom. In H–Cl, Cl (3.16) pulls harder than H (2.20), so δ− sits on Cl. Reading the trend backwards flips the charge onto H; subtracting 2.20 − 3.16 = −0.96 and dropping the sign does the same.
Calling a real difference nonpolar. Equal sharing happens only when the electronegativities match, as in Cl–Cl. An N–H difference of 3.04 − 2.20 = 0.84 is not zero, so the sharing is unequal: polar covalent, not nonpolar.
Calling a moderate difference ionic. Two nonmetals with a difference near 1 still share the pair: polar covalent. Full transfer takes a large gap, usually a metal bonded to a nonmetal.
Reading the boundary as a wall. H–F has a difference of 1.78, past the 1.7 guideline, yet HF is a molecular gas that shares its pair: polar covalent. Two nonmetals share; the number guides, the metal-versus-nonmetal test decides at the edge.
Dr. Karmach

Practice 1: the S–O bond

S–O (a sulfur–oxygen bond)
electronegativity: S = 2.58 · O = 3.44 · wanted: bond type and δ−

How is the S–O bond best classified?

  1. Nonpolar covalent, the two atoms share the pair equally
  2. Polar covalent, with S carrying the partial negative charge (δ−)
  3. Polar covalent, with O carrying the partial negative charge (δ−)
  4. Ionic, O pulls an electron completely away from S
Dr. Karmach

Practice 1 answer: C

S–O (a sulfur–oxygen bond)
electronegativity: S = 2.58 · O = 3.44
ΔEN = 3.44 − 2.58 = 0.86 → moderate: polar covalent, δ− on O → answer C

B put δ− on the wrong atom: O (3.44) pulls harder than S (2.58), so the pair shifts toward O; subtracting backwards, 2.58 − 3.44 = −0.86, only flips the sign, not the direction. A ignored the difference: 0.86 is not zero, so the sharing is unequal, not nonpolar. D read sharing as transfer: two nonmetals 0.86 apart still share the pair, polar covalent, not ionic.

A moderate difference means unequal sharing, and the pair sits closer to the more electronegative atom. O is δ−, S is δ+.
Dr. Karmach

Worked example 3: the H–F bond

H–F (hydrogen fluoride)
electronegativity: H = 2.20 · F = 3.98 · wanted: bond type

Hydrogen fluoride is a gas that dissolves in water to make an acid.

A common first answer: the difference clears 1.7, so call the bond ionic. Test it.

Dr. Karmach

Worked example 3: solution

H–F (hydrogen fluoride)
electronegativity: H = 2.20 · F = 3.98

Step 1 · Find the electronegativity difference

ΔEN = 3.98 − 2.20 = 1.78
Dr. Karmach

Worked example 3: solution

H–F (hydrogen fluoride)
electronegativity: H = 2.20 · F = 3.98
Step 1 · Find the electronegativity difference
ΔEN = 3.98 − 2.20 = 1.78
Step 2 · Place it on the continuum

1.78 sits just past the 1.7 guideline. The boundary is not a wall: H and F are both nonmetals, and two nonmetals share.

Dr. Karmach

Worked example 3: solution

H–F (hydrogen fluoride)
electronegativity: H = 2.20 · F = 3.98
Step 1 · Find the electronegativity difference
ΔEN = 3.98 − 2.20 = 1.78
Step 2 · Place it on the continuum Step 3 · Name the bond and mark the charges
H–F → polar covalent, δ− on F
two nonmetals · the pair stays shared but pulled far toward F · H is δ+
Dr. Karmach

Worked example 3: solution

H–F (hydrogen fluoride)
electronegativity: H = 2.20 · F = 3.98
Step 1 · Find the electronegativity difference
ΔEN = 3.98 − 2.20 = 1.78
Step 2 · Place it on the continuum Step 3 · Name the bond and mark the charges
H–F → polar covalent, δ− on F
two nonmetals · the pair stays shared but pulled far toward F · H is δ+
HF is a molecular gas, not a lattice of ions. The most lopsided sharing among the common bonds is still sharing, not transfer.
Dr. Karmach

Worked example 3: the bond on the continuum

H–F: ΔEN = 3.98 − 2.20 = 1.78
electronegativity: H = 2.20 · F = 3.98 · found: polar covalent, δ− on F

Just past the 1.7 guideline, yet H and F are both nonmetals: the pair stays shared, polar covalent.
Dr. Karmach

Practice 2: the most polar bond

B–F · Si–Cl · O–F
electronegativity: B = 2.04 · F = 3.98 · Si = 1.90 · Cl = 3.16 · O = 3.44 · wanted: the most polar bond and its δ− atom

Which of these bonds is the most polar, and which atom in it carries the partial negative charge?

  1. Si–Cl, with Cl carrying δ−
  2. O–F, with F carrying δ−
  3. B–F, with B carrying δ−
  4. B–F, with F carrying δ−
Dr. Karmach

Practice 2 answer: D

B–F · Si–Cl · O–F
electronegativity: B = 2.04 · F = 3.98 · Si = 1.90 · Cl = 3.16 · O = 3.44
B–F: 3.98 − 2.04 = 1.94 · Si–Cl: 3.16 − 1.90 = 1.26 · O–F: 3.98 − 3.44 = 0.54 → B–F, δ− on F → answer D

A dropped B–F because 1.94 clears 1.7 and settled for Si–Cl at 1.26; a bigger difference only makes a bond more polar, and with no metal in it B–F still shares its pair. B picked the two most electronegative atoms; polarity comes from the difference, and 3.98 − 3.44 = 0.54 is the smallest of the three. C put δ− on the wrong atom: F (3.98) pulls harder than B (2.04); 2.04 − 3.98 = −1.94 flips only the sign.

The biggest difference makes the most polar bond, and 1.7 is a guideline, not a wall: with no metal in the bond, a big difference is still sharing. F is δ−.
Dr. Karmach

Practice 3: the Cl–F bond

Cl–F (chlorine monofluoride, ClF)
electronegativity: Cl = 3.16 · F = 3.98 · wanted: bond type and δ−

Which description fits the Cl–F bond?

  1. Nonpolar covalent: Cl and F sit in the same group, so they pull equally
  2. Polar covalent, with F carrying the partial negative charge (δ−)
  3. Polar covalent, with Cl carrying the partial negative charge (δ−)
  4. Ionic, F pulls an electron completely away from Cl
Dr. Karmach

Practice 3 answer: B

Cl–F (chlorine monofluoride, ClF)
electronegativity: Cl = 3.16 · F = 3.98
ΔEN = 3.98 − 3.16 = 0.82 → moderate: polar covalent, δ− on F → answer B

A read the shared group as an equal pull: electronegativity climbs up a group, and 0.82 is not zero, so the sharing is unequal. C gave δ− to the larger atom: Cl holds more electrons, but F (3.98) pulls the shared pair harder than Cl (3.16); 3.16 − 3.98 = −0.82 flips only the sign. D read sharing as transfer: two nonmetals 0.82 apart share the pair.

Same group does not mean same pull. F sits above Cl and pulls harder: F is δ−, Cl is δ+.
Dr. Karmach

Practice 4: the K–I and P–F bonds

K–I · P–F
electronegativity: K = 0.82 · I = 2.66 · P = 2.19 · F = 3.98 · wanted: each bond's type and δ−

How is each bond classified?

  1. K–I ionic · P–F ionic
  2. K–I polar covalent (δ− on I) · P–F polar covalent (δ− on F)
  3. K–I ionic · P–F polar covalent (δ− on F)
  4. K–I ionic · P–F polar covalent (δ− on P)
  5. K–I polar covalent (δ− on I) · P–F ionic
Dr. Karmach

Practice 4 answer: C

K–I · P–F
electronegativity: K = 0.82 · I = 2.66 · P = 2.19 · F = 3.98 · K: a metal · P, I, F: nonmetals
K–I: ΔEN = 2.66 − 0.82 = 1.84 → metal + nonmetal: ionic, K⁺ and I⁻
P–F: ΔEN = 3.98 − 2.19 = 1.79 → two nonmetals: polar covalent, δ− on F → answer C

A read 1.7 as a wall: P and F are nonmetals, so they share the pair. B ignored the metal: K gives its electron to I. D put δ− on the wrong atom: F (3.98) outpulls P (2.19); 2.19 − 3.98 = −1.79 flips only the sign. E judged by the strongest atom: the difference and the metal test set the type, not F alone.

Differences 0.05 apart, two bond types. Near 1.7 the metal test decides: K–I forms ions, P–F shares.
Dr. Karmach

Check yourself

  1. A C–O bond has electronegativities C = 2.55 and O = 3.44. Find the difference, classify the bond, and mark the atom that carries δ−.
  2. Two atoms form a bond with a difference of 0. What kind of bond is it, and where do the partial charges sit?

A bond type tells you how one shared pair of electrons is held. A whole molecule is built from several bonds arranged in space, and drawing that arrangement is the next step: Lewis structures.

Dr. Karmach

2 · Lewis Structures

Count a molecule's valence electrons and draw its Lewis structure, placing every electron as a bond or a lone pair.

Dr. Karmach

Parts with a fixed number of connectors

A model kit builds molecules. Each part has connectors: H one, O two, N three, C four. HONC 1-2-3-4. You build only what they allow.

Dr. Karmach

Every valence electron is accounted for

A molecule owns a fixed pool of valence electrons. A Lewis structure places every one of them as bonds or lone pairs. None is invented; none is lost.

H₂O: 8 valence electrons = 4 in bonds + 4 in lone pairs
2 O–H bonds (4) · 2 lone pairs on O (4) · every electron accounted for ✓
Dr. Karmach

Valence electrons come from the group number

Only the outermost electrons, the valence electrons, form bonds. For a main-group atom their count is the ones digit of the group number.

Dr. Karmach

The Lewis symbol: valence electrons as dots

A Lewis symbol writes the element with one dot per valence electron. Dots sit singly on the four sides first, then pair. Eight dots is a full shell.

Dr. Karmach

Ions in Lewis symbols

A metal atom empties its valence shell to form a cation: the dots leave with the electrons. A nonmetal gains electrons until eight dots surround it: an anion. Brackets around the symbol, charge outside.

Dr. Karmach

Your turn: the magnesium dot symbol

Mg: group 2 → 2 valence electrons
12 electrons in the atom · 10 core stay hidden · 2 valence become dots

Fill the blanks, then write the symbol.

step count
dots around Mg
paired or single
Dr. Karmach

Your turn: the magnesium dot symbol

Mg: group 2 → 2 valence electrons
12 electrons in the atom · 10 core stay hidden · 2 valence become dots

Fill the blanks, then write the symbol.

step count
dots around Mg
paired or single
·Mg·  ·  2 dots, single, on two different sides
dots sit singly on the four sides first · pairing starts only at the fifth dot
Dr. Karmach

Practice 1: the dot symbol for phosphorus

P: group 15 → 5 valence electrons
the ones digit of the group number · dots sit singly on the four sides first, then pair

Which dot symbol is correct for a phosphorus atom?

  1. P with 5 dots: one pair and three single dots
  2. P with 3 dots: one on each of three sides
  3. P with 15 dots surrounding the symbol
  4. P with 5 dots: two pairs and one single dot
Dr. Karmach

Practice 1 answer: A

P: group 15 → ones digit 5 → 5 dots → answer A
four dots fill the four sides singly · the fifth makes one pair · one pair + three single dots

B counted the period: P sits in period 3, but dots come from the group, 15 → 5. C drew the whole group number as 15 dots; only the 5 valence electrons appear. D paired too early: dots fill all four sides singly before any pair forms, so 5 dots make one pair, not two.

The three single dots mark where phosphorus bonds: three bonds and one lone pair, exactly the NF₃ pattern.
Dr. Karmach

Practice 2: the dot symbol for the sulfide ion

S²⁻: 6 + 2 = 8 electrons shown as dots
S is group 16 → 6 valence electrons · the 2− charge adds 2 more

Which drawing shows the sulfide ion correctly?

  1. [S with 8 dots]²⁻: brackets around the symbol, charge outside
  2. S with 8 dots, no brackets and no charge
  3. [S with 6 dots]²⁻: the six dots sulfur started with
  4. [S with 4 dots]²⁺: two dots removed, a positive charge
Dr. Karmach

Practice 2 answer: A

S²⁻: 6 + 2 = 8 dots · brackets, 2− outside → answer A
a nonmetal gains electrons until eight dots surround it

B drew the dots but dropped the brackets and charge; eight dots on a plain S claims a neutral atom, and neutral sulfur has 6. C pasted the charge onto the original 6 dots; the 2− exists because 2 electrons arrived, so 6 + 2 = 8 dots must show. D ran the transfer backwards: 6 − 2 = 4 dots with 2+ describes a cation, and nonmetals gain.

Charge and dot count move together: 2− means 2 extra dots, and the brackets say the whole package carries the charge.
Dr. Karmach

The electron pool

Add every atom's valence electrons. For an ion, adjust: add one electron per negative charge, subtract one per positive.

CO₂: 4 + 2(6) = 16
1 C (group 14 → 4) · 2 O (group 16 → 6) · neutral, no adjustment
OH⁻: 6 + 1 + 1 = 8  ·  NH₄⁺: 5 + 4(1) − 1 = 8
OH⁻ adds 1 for the 1− charge · NH₄⁺ subtracts 1 for the 1+ charge
Dr. Karmach

Bonds, lone pairs, and the octet

A shared pair drawn as a line is a bond: one pair single, two double, three triple. Each main-group atom aims for eight electrons, an octet. Hydrogen aims for two, a duet.

Dr. Karmach

The method

  1. Count the valence electrons.
  2. Draw the skeleton: least electronegative atom centered, never H; single bonds.
  3. Complete the outer octets: lone pairs; H a duet.
  4. Place leftovers on the center.
  5. Form multiple bonds if the center lacks an octet.
Dr. Karmach

Worked example 1: water

Step 1 · Count the valence electrons

H₂O: 2(1) + 6 = 8
2 H (group 1 → 1) · 1 O (group 16 → 6) · 8 valence electrons to place

Oxygen is less electronegative than hydrogen, and H is never central. Draw the Lewis structure.

Dr. Karmach

Worked example 1: solution

H₂O: 2(1) + 6 = 8
8 valence electrons to place

Step 2 · Draw the skeleton

Oxygen in the center, one single bond to each H.

H–O–H
2 single bonds use 2 × 2 = 4 electrons · 4 of 8 placed
Dr. Karmach

Worked example 1: solution

H₂O: 2(1) + 6 = 8
8 valence electrons to place
Step 2 · Draw the skeleton
H–O–H
2 single bonds use 2 × 2 = 4 electrons · 4 of 8 placed
Step 3 · Complete the outer octets

The outer atoms are hydrogen; a single bond already fills each H's duet.

Dr. Karmach

Worked example 1: solution

H₂O: 2(1) + 6 = 8
8 valence electrons to place
Step 2 · Draw the skeleton
H–O–H
2 single bonds use 2 × 2 = 4 electrons · 4 of 8 placed
Step 3 · Complete the outer octets

The outer atoms are hydrogen; a single bond already fills each H's duet.

Four electrons fill the two O–H bonds and each hydrogen has its duet. Four remain for oxygen.
Dr. Karmach

Worked example 1: the oxygen lone pairs

Four electrons sit in the two O–H bonds; the outer hydrogens are done. Four remain.

Step 4 · Place leftovers on the center

8 − 4 = 4 electrons left → 2 lone pairs on O
O: 2 bonds (4) + 2 lone pairs (4) = 8 → octet ✓

Dr. Karmach

Worked example 1: the oxygen lone pairs

Four electrons sit in the two O–H bonds; the outer hydrogens are done. Four remain.

Step 4 · Place leftovers on the center

8 − 4 = 4 electrons left → 2 lone pairs on O
O: 2 bonds (4) + 2 lone pairs (4) = 8 → octet ✓

All 8 valence electrons placed: 4 in bonds, 4 in lone pairs. O has an octet; each H a duet.
Dr. Karmach

Worked example 1: the electron budget

H₂O: 8 valence electrons = 4 in bonds + 4 in lone pairs on O
steps 1 to 4 used · step 5 not needed

The pool is used up at step 4 and oxygen has its octet, so step 5 never runs. ✓
Dr. Karmach

Worked example 2: nitrogen trifluoride

Step 1 · Count the valence electrons

NF₃
given: 1 nitrogen, 3 fluorine · wanted: the electron pool, then the structure

A common first attempt counts one group number per element. Find the pool, then draw the structure.

Dr. Karmach

Worked example 2: solution

Step 1 · Count the valence electrons

NF₃: 5 + 3(7) = 26  ·  one-per-element 5 + 7 = 12 ✗
each F brings its own 7: multiply by the subscript · 26 to place
Dr. Karmach

Worked example 2: solution

Step 1 · Count the valence electrons

NF₃: 5 + 3(7) = 26  ·  one-per-element 5 + 7 = 12 ✗
each F brings its own 7: multiply by the subscript · 26 to place
Step 2 · Draw the skeleton

Nitrogen is least electronegative, so it takes the center, with a single bond to each F.

3 N–F single bonds: 3 × 2 = 6 electrons
6 of 26 placed

Dr. Karmach

Worked example 2: solution

Step 1 · Count the valence electrons

NF₃: 5 + 3(7) = 26  ·  one-per-element 5 + 7 = 12 ✗
each F brings its own 7: multiply by the subscript · 26 to place
Step 2 · Draw the skeleton

Nitrogen is least electronegative, so it takes the center, with a single bond to each F.

3 N–F single bonds: 3 × 2 = 6 electrons
6 of 26 placed

Six of the 26 electrons fill the three N–F bonds. Twenty remain for the fluorine octets and the center.
Dr. Karmach

Worked example 2: the fluorine octets

Six electrons sit in the three N–F bonds. Each fluorine still needs three lone pairs.

Step 3 · Complete the outer octets

each F: 3 lone pairs → 3 × 6 = 18 electrons
6 + 18 = 24 of 26 placed · every F has its octet

Dr. Karmach

Worked example 2: the fluorine octets

Six electrons sit in the three N–F bonds. Each fluorine still needs three lone pairs.

Step 3 · Complete the outer octets

each F: 3 lone pairs → 3 × 6 = 18 electrons
6 + 18 = 24 of 26 placed · every F has its octet

Twenty-four of the 26 electrons are placed and every fluorine has its octet. Two remain for the center.
Dr. Karmach

Worked example 2: the nitrogen lone pair

Six electrons sit in the three N–F bonds and eighteen fill the fluorine octets. Two remain.

Step 4 · Place leftovers on the center

26 − 6 − 18 = 2 → 1 lone pair on N
N: 3 bonds (6) + 1 lone pair (2) = 8 → octet ✓

Dr. Karmach

Worked example 2: the nitrogen lone pair

Six electrons sit in the three N–F bonds and eighteen fill the fluorine octets. Two remain.

Step 4 · Place leftovers on the center

26 − 6 − 18 = 2 → 1 lone pair on N
N: 3 bonds (6) + 1 lone pair (2) = 8 → octet ✓

All 26 valence electrons placed; every F and the N reaches an octet. One per element stops at 12 and leaves the structure short.
Dr. Karmach

Worked example 2: the electron budget

NF₃: 26 valence electrons = 6 in bonds + 18 on the F atoms + 2 on N
steps 1 to 4 used · step 5 not needed

The same four steps as water. The outer octets take the largest share: 18 of 26. ✓
Dr. Karmach

Take-home: count every atom, not every element

NF₃: 5 + 3(7) = 26 ✓  ·  5 + 7 = 12 ✗
three fluorine atoms bring 3 × 7 = 21 electrons, not 7

Each atom brings its own valence electrons. Multiply each element's group number by its subscript in the formula, then add.

Dr. Karmach

Your turn: methane, CH₄

CH₄: 4 + 4(1) = 8
1 C (group 14 → 4) · 4 H (group 1 → 1) · 8 valence electrons

Carbon is the central atom. Fill the blanks.

step count
electrons in the 4 C–H bonds
electrons left for lone pairs
Dr. Karmach

Your turn: methane, CH₄

CH₄: 4 + 4(1) = 8
1 C (group 14 → 4) · 4 H (group 1 → 1) · 8 valence electrons

Carbon is the central atom. Fill the blanks.

step count
electrons in the 4 C–H bonds
electrons left for lone pairs
4 C–H bonds: 4 × 2 = 8  ·  leftover 8 − 8 = 0
C: 4 bonds (8) = octet ✓ · every H a duet · no lone pairs

Dr. Karmach

Where this goes wrong

Counting each element once. For NF₃, adding one group number per element gives 5 + 7 = 12. Every atom brings its own: 5 + 3(7) = 26. Multiply each group number by its subscript.
Counting all the electrons. CO₂ holds 6 + 2(8) = 22 electrons in total, but only the valence electrons are drawn: 4 + 2(6) = 16. Core electrons stay out of the structure.
Ignoring the ion's charge. NH₄⁺ carries a 1+ charge, so subtract one electron: 5 + 4(1) − 1 = 8, not 9. A negative ion adds electrons; a positive ion removes them.
Leaving the center short. With only single bonds, the carbon in CO₂ has 4 electrons, not 8. When the center lacks an octet, form double or triple bonds.
Dr. Karmach

Practice 3: oxygen difluoride

OF₂
fluorine is the most electronegative atom, so oxygen is the central atom

How many valence electrons must appear in the Lewis structure of OF₂?

  1. 18
  2. 13
  3. 26
  4. 20
Dr. Karmach

Practice 3 answer: D

OF₂: 6 + 2(7) = 20 → answer D
1 O (group 16 → 6) · 2 F (group 17 → 7) · neutral, no adjustment

B counted each element once: 6 + 7 = 13. C counted every electron, core included: 8 + 2(9) = 26. A dropped a pair: 20 − 2 = 18.

20 valence electrons place as 2 O–F bonds (4) and 8 lone pairs (16): 4 + 16 = 20, every atom an octet.

Dr. Karmach

Worked example 3: carbon dioxide

Step 1 · Count the valence electrons

CO₂: 4 + 2(6) = 16
1 C (group 14 → 4) · 2 O (group 16 → 6) · 16 valence electrons to place

Carbon is least electronegative, so it takes the center. Draw the Lewis structure.

Dr. Karmach

Worked example 3: solution

Step 2 · Draw the skeleton

Carbon centered, a single bond to each oxygen.

O–C–O: 2 single bonds use 2 × 2 = 4 electrons
4 of 16 placed

Dr. Karmach

Worked example 3: solution

Step 2 · Draw the skeleton

Carbon centered, a single bond to each oxygen.

O–C–O: 2 single bonds use 2 × 2 = 4 electrons
4 of 16 placed

Four of the 16 electrons fill the two C–O bonds. Twelve remain for the outer octets.
Dr. Karmach

Worked example 3: the outer octets

Step 3 · Complete the outer octets

each O gets 3 lone pairs: 2 × 6 = 12 electrons
4 + 12 = 16: all placed, but carbon has only 4 (no octet)

Dr. Karmach

Worked example 3: the outer octets

Step 3 · Complete the outer octets

each O gets 3 lone pairs: 2 × 6 = 12 electrons
4 + 12 = 16: all placed, but carbon has only 4 (no octet)


Step 4 · Place leftovers on the center

None remain: 16 − 4 − 12 = 0. The carbon is still two pairs short of an octet.

Dr. Karmach

Worked example 3: the outer octets

Step 3 · Complete the outer octets

each O gets 3 lone pairs: 2 × 6 = 12 electrons
4 + 12 = 16: all placed, but carbon has only 4 (no octet)


Step 4 · Place leftovers on the center

None remain: 16 − 4 − 12 = 0. The carbon is still two pairs short of an octet.

Every electron is placed, yet carbon holds only 4. Single bonds cannot finish this structure.
Dr. Karmach

Worked example 3: two double bonds

Carbon sits two pairs short of an octet. Pull one lone pair from each oxygen into a bond.

Step 5 · Form multiple bonds

O=C=O
C: 2 double bonds (8) = octet ✓ · each O: 1 double bond (4) + 2 lone pairs (4) = 8 ✓

Dr. Karmach

Worked example 3: two double bonds

Carbon sits two pairs short of an octet. Pull one lone pair from each oxygen into a bond.

Step 5 · Form multiple bonds

O=C=O
C: 2 double bonds (8) = octet ✓ · each O: 1 double bond (4) + 2 lone pairs (4) = 8 ✓

All 16 valence electrons placed. Single bonds could not give carbon an octet; two double bonds can.
Dr. Karmach

Worked example 3: the electron budget

CO₂: 16 valence electrons = 8 in bonds + 8 in lone pairs on O
all five steps used · step 4 adds nothing: none left

The pool ran out with carbon at 4. Step 5 moves 2 lone pairs into bonds: 4 + 4 = 8 in bonds. No electron is added. ✓
Dr. Karmach

Practice 4: hydrogen cyanide

HCN
skeleton H–C–N

In the Lewis structure of HCN, how many electrons sit in lone pairs?

  1. 10
  2. 2
  3. 6
  4. 8
  5. 4
Dr. Karmach

Practice 4 answer: B

HCN: 1 + 4 + 5 = 10 · H–C≡N: 1 single bond (2) + 1 triple bond (6) = 8 shared · 10 − 8 = 2 in lone pairs → answer B
C: single (2) + triple (6) = 8 ✓ · N: triple (6) + 1 lone pair (2) = 8 ✓ · H: duet ✓

A reported the whole pool of 10, not the lone-pair share. D counted the shared electrons, 2 + 6 = 8, instead of the ones left over. C stopped at single bonds: 10 − 4 = 6 in lone pairs, which leaves carbon with only 4 electrons. E stopped at a double bond: 2 + 4 = 6 shared, 10 − 6 = 4 in lone pairs, which leaves carbon with only 6.

Two of nitrogen's pairs move into the bond so carbon reaches eight. One lone pair, 2 electrons, is all that stays outside a bond.
Dr. Karmach

Practice 5: hydrogen peroxide

H₂O₂
skeleton H–O–O–H

How many lone pairs does the finished Lewis structure of hydrogen peroxide carry?

  1. 4
  2. 8
  3. 10
  4. 7
Dr. Karmach

Practice 5 answer: A

H₂O₂: 2(1) + 2(6) = 14 · 3 bonds: 3 × 2 = 6 · 14 − 6 = 8 → 4 lone pairs → answer A
each O: 2 bonds (4) + 2 lone pairs (4) = 8 ✓ · each H: a duet ✓ · no multiple bond needed

B counted the lone-pair electrons, 4 × 2 = 8, not the pairs. C gave each H an octet: 4 lone pairs on the O atoms plus 3 on each H makes 10, which needs 6 + 20 = 26 electrons from a pool of 14. D counted every pair in the pool as a lone pair: 14 ÷ 2 = 7, the 3 bonding pairs included.

Each oxygen carries two bonds and two lone pairs, as in water. The O–O bond takes the place of one O–H bond.
Dr. Karmach

Practice 6: urea

CO(NH₂)₂ (urea)
skeleton: C bonded to O and to both N · each N bonded to 2 H

Urea is the most widely used nitrogen fertilizer. In its correct Lewis structure, how many single bonds are there, and how many lone pairs?

  1. single bonds 7 · lone pairs 5
  2. single bonds 8 · lone pairs 4
  3. single bonds 6 · lone pairs 8
  4. single bonds 6 · lone pairs 4
  5. single bonds 2 · lone pairs 4
Dr. Karmach

Practice 6 answer: D

CO(NH₂)₂: 4 + 6 + 2(5) + 4(1) = 24 · 7 single bonds use 7 × 2 = 14 · 24 − 14 = 10
3 lone pairs on O (6) + 1 on each N (4) = 10 · C holds only 3 × 2 = 6 · one O lone pair moves into C=O
6 single bonds + 1 C=O · lone pairs: 2 on O + 1 on each N = 4 → answer D
bonds 6(2) + 4 = 16 · lone pairs 4 × 2 = 8 · 16 + 8 = 24 ✓ · C 8 ✓ · O 8 ✓ · each N 8 ✓ · each H a duet ✓

A stopped at step 4: 7 single bonds and 5 lone pairs place all 24 electrons, but carbon holds 6. B counted each line of C=O as a single bond: 6 + 2 = 8. C counted lone-pair electrons, 4 × 2 = 8, not pairs. E left out the four N–H bonds: 6 − 4 = 2.

A double bond is one bond, not two single bonds. Every bond to H is a single bond and counts.
Dr. Karmach

Practice 7: nitrosyl chloride

NOCl
electronegativity: N = 3.04 · Cl = 3.16 · O = 3.44 · wanted: the correct Lewis structure

Which is the correct Lewis structure of NOCl?

  1. O–N–Cl: 3 lone pairs on O, 1 on N, 3 on Cl
  2. O=N–Cl: 2 lone pairs on O, 1 on N, 3 on Cl
  3. N=O–Cl: 2 lone pairs on N, 1 on O, 3 on Cl
  4. O=N–Cl: 2 lone pairs on O, none on N, 3 on Cl
Dr. Karmach

Practice 7 answer: B

NOCl: 5 + 6 + 7 = 18 · N in the center · O–N–Cl uses 2 × 2 = 4
N 3.04 < Cl 3.16 < O 3.44 · 3 lone pairs each on O, Cl: 2 × 6 = 12 · 18 − 4 − 12 = 2 → 1 lone pair on N
N holds 2 + 2 + 2 = 6 → one O lone pair moves into N=O → O=N–Cl → answer B
bonds 2 + 4 = 6 · lone pairs 4 (O) + 2 (N) + 6 (Cl) = 12 · 6 + 12 = 18 ✓ · N 8 ✓ · O 8 ✓ · Cl 8 ✓

A stopped at step 4: all 18 electrons are placed, but N holds 2 + 2 + 2 = 6. C put O in the center because it sits in the middle of the formula; O has the highest electronegativity, so it belongs outside. D dropped the 2 leftover electrons: 18 − 2 = 16 drawn, and N holds 6.

Every atom in C also has an octet, so octets alone cannot pick the skeleton. Electronegativity does: the lowest value takes the center.
Dr. Karmach

Check yourself

  1. Count the valence electrons in NH₃, and name the central atom.
  2. In CO₂, why do single bonds fail and double bonds succeed?

The octet rule builds most structures, not all: boron can settle at six electrons, and heavier central atoms can hold more than eight. Before those exceptions, every finished structure must survive a bookkeeping check: each atom's share of the electrons, counted against the pool.

Dr. Karmach

3 · Resonance & Formal Charge

Draw every resonance structure of a molecule or ion, assign formal charges, and use them to pick the best Lewis structure.

Dr. Karmach

One molecule, two correct drawings

High in the stratosphere, ozone absorbs ultraviolet light. Its Lewis structure can be drawn two equally correct ways. Measured bond lengths match neither drawing: both bonds are identical.

Dr. Karmach

Delocalized electrons defeat a single drawing

A Lewis structure pins every electron pair to one place. In ozone the fourth bonding pair belongs to both O–O links at once. No single drawing shows that, so two share the job.

O₃: 3(6) = 18 valence electrons  ·  one double bond, drawable on either side
O=O–O ↔ O–O=O · atoms fixed · only electrons move
Dr. Karmach

Resonance structures and the blend

Resonance structures differ only in where multiple bonds and lone pairs sit. The real molecule is one blend of all of them: every bond equal, between single and double.

O₃, NO₂⁻, CO₃²⁻, NO₃⁻: equivalent resonance structures
connect the drawings with a double-headed arrow ↔ · never move an atom
Dr. Karmach

Charges you already count

Na⁺: 1 − 0 = +1  ·  Cl⁻: 7 − 8 = −1
charge = valence electrons brought − electrons held · Na: 1 and 0 · Cl: 7 and 8

Monatomic ions already follow this count. Sodium gives up its one valence electron: +1. Chlorine gains one to hold eight: −1. Formal charge runs the same count on every atom inside a Lewis structure.

Dr. Karmach

Formal charge tracks electron ownership

Formal charge compares the electrons an atom holds in the structure with the electrons the free atom brings. Each atom owns its nonbonding electrons and half of every bond it makes.

FC = valence − nonbonding − ½(bonding)
valence: the free atom's count · nonbonding: lone-pair electrons · bonding: electrons in its bonds
memory hook: valence minus dots minus lines
each lone-pair electron is one dot · each bond line counts 1, half of its 2 electrons
Dr. Karmach

The formal charges sum to the overall charge

Add every atom's formal charge. A neutral molecule sums to zero; an ion sums to its charge. A different total means a miscount somewhere in the structure.

O₃: (−1) + (+1) + 0 = 0 ✓  ·  CO₃²⁻: 0 + 0 + (−1) + (−1) = −2 ✓
sum equals the overall charge, or the structure has an error
Dr. Karmach

The method

  1. Draw the full Lewis structure.
  2. Count the atom's nonbonding electrons.
  3. Count half the atom's bonding electrons.
  4. Subtract both from the valence electrons.
  5. Check the sum against the overall charge.

Dr. Karmach

Worked example 1: formal charges in ozone

Step 1 · Draw the full Lewis structure

O₃: 3(6) = 18 valence electrons, all placed
given: the structure below · wanted: the formal charge on each oxygen

Assign a formal charge to each oxygen.

Dr. Karmach

Worked example 1: solution

O–O=O · FC = valence − nonbonding − ½(bonding)

Step 2 · Count the atom's nonbonding electrons

Single-bonded O: 6. Central O: 2. Double-bonded O: 4.

Dr. Karmach

Worked example 1: solution

O–O=O · FC = valence − nonbonding − ½(bonding)
Step 2 · Count the atom's nonbonding electrons Step 3 · Count half the atom's bonding electrons

Single-bonded O: ½(2) = 1. Central O: ½(6) = 3. Double-bonded O: ½(4) = 2.

Dr. Karmach

Worked example 1: solution

O–O=O · FC = valence − nonbonding − ½(bonding)
Step 2 · Count the atom's nonbonding electrons Step 3 · Count half the atom's bonding electrons Step 4 · Subtract both from the valence electrons
6 − 6 − 1 = −1  ·  6 − 2 − 3 = +1  ·  6 − 4 − 2 = 0
single-bonded O: −1 · central O: +1 · double-bonded O: 0

Dr. Karmach

Worked example 1: solution

O–O=O · FC = valence − nonbonding − ½(bonding)
Step 2 · Count the atom's nonbonding electrons Step 3 · Count half the atom's bonding electrons Step 4 · Subtract both from the valence electrons
6 − 6 − 1 = −1  ·  6 − 2 − 3 = +1  ·  6 − 4 − 2 = 0
single-bonded O: −1 · central O: +1 · double-bonded O: 0

The negative charge sits on the oxygen holding the most lone pairs. Bonds count half; lone pairs count in full.
Dr. Karmach

Worked example 1: the sum check

O–O=O: formal charges −1, +1, 0
single-bonded O · central O · double-bonded O

Step 5 · Check the sum against the overall charge

(−1) + (+1) + 0 = 0
ozone is neutral · the formal charges sum to 0 ✓
Dr. Karmach

Worked example 1: the sum check

O–O=O: formal charges −1, +1, 0
single-bonded O · central O · double-bonded O

Step 5 · Check the sum against the overall charge

(−1) + (+1) + 0 = 0
ozone is neutral · the formal charges sum to 0 ✓
Any total other than zero would mean a dropped electron or a miscounted bond somewhere in the structure.
Dr. Karmach

Worked example 2: the carbonate ion

Step 1 · Draw the full Lewis structure

CO₃²⁻: 4 + 3(6) + 2 = 24 valence electrons
the 2− charge adds 2 electrons · one C=O double bond completes carbon's octet

The double bond can sit on any of the three oxygens. Draw every resonance structure, then assign the formal charges.

Dr. Karmach

Worked example 2: the three structures

CO₃²⁻: 24 valence electrons  ·  one double bond, three equivalent positions
atoms never move · only the double bond and lone pairs shift
Dr. Karmach

Worked example 2: the three structures

CO₃²⁻: 24 valence electrons  ·  one double bond, three equivalent positions
atoms never move · only the double bond and lone pairs shift
The double bond takes each position in turn.

Dr. Karmach

Worked example 2: the three structures

CO₃²⁻: 24 valence electrons  ·  one double bond, three equivalent positions
atoms never move · only the double bond and lone pairs shift
The double bond takes each position in turn.

Three drawings, one ion. The real carbonate has three equal C–O bonds, each between a single and a double.
Dr. Karmach

Worked example 2: formal charges

one structure of CO₃²⁻: C with 4 bonds · one double-bonded O · two single-bonded O

Step 2 · Count the atom's nonbonding electrons
Step 3 · Count half the atom's bonding electrons

Carbon: no lone pairs, four bonding pairs. Double-bonded O: two lone pairs. Each single-bonded O: three lone pairs.

Dr. Karmach

Worked example 2: formal charges

one structure of CO₃²⁻: C with 4 bonds · one double-bonded O · two single-bonded O
Step 2 · Count the atom's nonbonding electrons Step 3 · Count half the atom's bonding electrons Step 4 · Subtract both from the valence electrons
C: 4 − 0 − 4 = 0  ·  O(=): 6 − 4 − 2 = 0  ·  O(–): 6 − 6 − 1 = −1
the two single-bonded oxygens each carry −1

Dr. Karmach

Worked example 2: formal charges

one structure of CO₃²⁻: C with 4 bonds · one double-bonded O · two single-bonded O
Step 2 · Count the atom's nonbonding electrons Step 3 · Count half the atom's bonding electrons Step 4 · Subtract both from the valence electrons
C: 4 − 0 − 4 = 0  ·  O(=): 6 − 4 − 2 = 0  ·  O(–): 6 − 6 − 1 = −1
the two single-bonded oxygens each carry −1

Bonds count half, lone pairs in full. The negative charges land on the single-bonded oxygens.
Dr. Karmach

Worked example 2: the sum check

one structure of CO₃²⁻: C 0 · O(=) 0 · two O(–) at −1 each
formal charges from the previous step

Step 5 · Check the sum against the overall charge

0 + 0 + (−1) + (−1) = −2
matches the ion's 2− charge ✓
Dr. Karmach

Worked example 2: the sum check

one structure of CO₃²⁻: C 0 · O(=) 0 · two O(–) at −1 each
formal charges from the previous step

Step 5 · Check the sum against the overall charge

0 + 0 + (−1) + (−1) = −2
matches the ion's 2− charge ✓
Every resonance structure gives the same set of formal charges; only their positions rotate with the double bond.
Dr. Karmach

Your turn: the nitrite ion

NO₂⁻: 5 + 2(6) + 1 = 18 valence electrons
structure: O=N–O in brackets · N keeps one lone pair

atom formal charge
N: 5 − 2 − 3
single-bonded O: 6 − 6 − 1
Dr. Karmach

Your turn: the nitrite ion

NO₂⁻: 5 + 2(6) + 1 = 18 valence electrons
structure: O=N–O in brackets · N keeps one lone pair

atom formal charge
N: 5 − 2 − 3
single-bonded O: 6 − 6 − 1
N: 5 − 2 − 3 = 0  ·  O(–): 6 − 6 − 1 = −1  ·  sum: 0 + 0 + (−1) = −1 ✓
double-bonded O: 0 · the sum matches the 1− charge
Dr. Karmach

Where this goes wrong

Treating resonance as motion. The molecule does not flip between the drawings. There is one real structure: the blend, with equal intermediate bonds.
Counting all the bonding electrons. For ozone's central O: 6 − 2 − 6 = −2 ✗. An atom owns half of its bonds: 6 − 2 − 3 = +1 ✓.
Moving atoms between structures. Rearranged atoms make a different compound. Resonance structures move electrons only.
Skipping the sum check. The formal charges must add to the overall charge; any other total means a dropped electron or a miscounted bond.
Dr. Karmach

Practice 1: the ammonium ion

NH₄⁺: N bonded to 4 H, no lone pair on N
5 + 4(1) − 1 = 8 valence electrons · all four pairs sit in N–H bonds

What is the formal charge on the nitrogen atom?

  1. −3
  2. −1
  3. +1
  4. 0
Dr. Karmach

Practice 1 answer: C

N: 5 − 0 − 4 = +1 → answer C
valence 5 · nonbonding 0 · four bonding pairs hold 8, half is 4 · each H: 1 − 0 − 1 = 0 · sum +1 ✓

A counted all eight bonding electrons: 5 − 0 − 8 = −3. B gave nitrogen the lone pair it has in ammonia: 5 − 2 − 4 = −1, but here all four pairs sit in bonds. D set every atom to zero; the formal charges must add to the ion's +1, and every hydrogen is 0, so nitrogen carries it.

Dr. Karmach

Practice 1 answer: C

N: 5 − 0 − 4 = +1 → answer C
valence 5 · nonbonding 0 · four bonding pairs hold 8, half is 4 · each H: 1 − 0 − 1 = 0 · sum +1 ✓
A nitrogen with four bonds and no lone pair owns one electron fewer than its five: +1, the charge of the whole ion.

Dr. Karmach

Choosing between non-equivalent structures

When two valid structures are not equivalent, formal charge decides. Prefer the structure with charges closest to zero, and put any negative formal charge on the most electronegative atom.

best structure: smallest formal charges  ·  negative FC on the most electronegative atom
Rule 1 · size, then Rule 2 · sign, applied in that order
Dr. Karmach

Worked example 3: two structures for carbon dioxide

CO₂: 4 + 2(6) = 16 valence electrons in each structure
A: O=C=O · B: O–C≡O · every atom has an octet in both

Both structures place all 16 electrons. Which one better represents CO₂?

Dr. Karmach

Worked example 3: solution

A: O 6 − 4 − 2 = 0 · C 4 − 0 − 4 = 0
B: O(–) 6 − 6 − 1 = −1 · C 0 · O(≡) 6 − 2 − 3 = +1
both sums 0 ✓ · B's +1 lands on oxygen, the most electronegative atom
Dr. Karmach

Worked example 3: solution

A: O 6 − 4 − 2 = 0 · C 4 − 0 − 4 = 0
B: O(–) 6 − 6 − 1 = −1 · C 0 · O(≡) 6 − 2 − 3 = +1
both sums 0 ✓ · B's +1 lands on oxygen, the most electronegative atom
Rule 1 · Size: charges closest to zero
Both sums are zero, so size decides: A has no formal charge, B has ±1. A wins; CO₂ is O=C=O.

Dr. Karmach

Guided example: the thiocyanate ion

Step 1 · Draw the full Lewis structure

SCN⁻: 6 + 4 + 5 + 1 = 16 valence electrons · skeleton S–C–N
three octet structures, not equivalent · electronegativity: N 3.04 · S 2.58

Assign every formal charge in all three structures. Then choose the best structure.

Dr. Karmach

Guided example: formal charges

SCN⁻: 16 valence electrons · 1: S=C=N · 2: S–C≡N · 3: S≡C–N
wanted: the formal charge on every atom of all three

Step 2 · Count the atom's nonbonding electrons
Step 3 · Count half the atom's bonding electrons

Carbon holds four bonds and no lone pair in all three: 4 − 0 − 4 = 0 every time. Only the end atoms change.

Dr. Karmach

Guided example: formal charges

SCN⁻: 16 valence electrons · 1: S=C=N · 2: S–C≡N · 3: S≡C–N
wanted: the formal charge on every atom of all three
Step 2 · Count the atom's nonbonding electrons Step 3 · Count half the atom's bonding electrons Step 4 · Subtract both from the valence electrons Step 5 · Check the sum against the overall charge
structure S C N sum
1: S=C=N 6 − 4 − 2 = 0 0 5 − 4 − 2 = −1 0 + 0 − 1 = −1 ✓
2: S–C≡N 6 − 6 − 1 = −1 0 5 − 2 − 3 = 0 −1 + 0 + 0 = −1 ✓
3: S≡C–N 6 − 2 − 3 = +1 0 5 − 6 − 1 = −2 +1 + 0 − 2 = −1 ✓
Carbon stays at 0; the charges shift between S and N as the multiple bonds move. All three match the 1− charge.
Dr. Karmach

Guided example: the best structure

1: S=C=N (0, 0, −1) · 2: S–C≡N (−1, 0, 0) · 3: S≡C–N (+1, 0, −2)
SCN⁻ · formal charges S, C, N · all three sum to −1 ✓ · electronegativity: N 3.04 · S 2.58

Rule 1 · Size: charges closest to zero

Structure 3 carries −2 on N. Structures 1 and 2 keep every charge within ±1. Drop structure 3.

Dr. Karmach

Guided example: the best structure

1: S=C=N (0, 0, −1) · 2: S–C≡N (−1, 0, 0) · 3: S≡C–N (+1, 0, −2)
SCN⁻ · formal charges S, C, N · all three sum to −1 ✓ · electronegativity: N 3.04 · S 2.58
Rule 1 · Size: charges closest to zero Rule 2 · Sign: negative charge on the most electronegative atom
best: [S=C=N]⁻ · S 0 · C 0 · N −1
N 3.04 − S 2.58 = 0.46 · the −1 sits on N
Structures 1 and 2 tie on size, so sign decides: N is more electronegative than S, and the −1 belongs on N.

Dr. Karmach

Practice 2: two structures for N₂O

N₂O: 2(5) + 6 = 16 valence electrons · structure 1: N≡N–O · structure 2: N=N=O
every atom has an octet in both · wanted: the better structure

Which structure better represents N₂O?

  1. Structure 2: every formal charge is zero, as in O=C=O
  2. Structure 1: both carry a −1 and a +1, and this one puts the −1 on oxygen, the more electronegative atom
  3. Structure 2: its −1 sits on the end nitrogen, which holds negative charge better than oxygen does
  4. Both equally: the two are resonance structures of the same molecule, so they count the same
Dr. Karmach

Practice 2 answer: B

structure 1, N≡N–O: N 5 − 2 − 3 = 0 · N 5 − 0 − 4 = +1 · O 6 − 6 − 1 = −1
sum 0 + 1 − 1 = 0 ✓ · the −1 on oxygen
structure 2, N=N=O: N 5 − 4 − 2 = −1 · N 5 − 0 − 4 = +1 · O 6 − 4 − 2 = 0
sum −1 + 1 + 0 = 0 ✓ · the −1 on nitrogen → answer B

A miscounted: the central N holds four bonds and no lone pair in both drawings, 5 − 0 − 4 = +1, so no structure of N₂O is charge-free. C ran the tiebreaker backwards; a negative formal charge belongs on the most electronegative atom, and oxygen (3.44) beats nitrogen (3.04). D treated non-equivalent drawings as equal partners; their charges differ, so formal charge picks the better one.

Same charge sizes in both, so the second rule decides: the −1 goes to oxygen. N≡N–O is the better structure.
Dr. Karmach

Practice 3: the cyanate ion

OCN⁻
skeleton O–C–N · wanted: the formal charges in the best structure

In the best Lewis structure of OCN⁻, what is the formal charge on each atom?

  1. O 0, C 0, N −1
  2. O +1, C 0, N −2
  3. O −2, C +4, N −3
  4. O 0, C 0, N 0
  5. O −1, C 0, N 0
Dr. Karmach

Practice 3 answer: E

[O–C≡N]⁻: O 6 − 6 − 1 = −1 · C 4 − 0 − 4 = 0 · N 5 − 2 − 3 = 0 → answer E
4 + 6 + 5 + 1 = 16 electrons · sum −1 ✓ · ties [O=C=N]⁻ on size · O 3.44 > N 3.04 takes the −1

A is [O=C=N]⁻: O 6 − 4 − 2 = 0, N 5 − 4 − 2 = −1. It ties E on size but puts the −1 on N, as in [S=C=N]⁻; oxygen outranks nitrogen. B is [O≡C–N]⁻: O 6 − 2 − 3 = +1, N 5 − 6 − 1 = −2, which fails Rule 1. C gave oxidation numbers: O −2, N −3, so C is −1 + 2 + 3 = +4. D sums to 0; an ion's formal charges must sum to −1.

Same skeleton as thiocyanate, opposite answer. Rule 2 asks which end atom is more electronegative: N beats S, but O beats N.
Dr. Karmach

Extra practice 1: the sulfite ion

SO₃²⁻: 6 + 3(6) + 2 = 26 valence electrons
structure: S bonded to three O by single bonds · one lone pair on S · three on each O

What are the formal charges on sulfur and on each oxygen?

  1. S +4, each O −2
  2. S −2, each O −2
  3. S −2, each O 0
  4. S +1, each O −1
Dr. Karmach

Extra practice 1 answer: D

S: 6 − 2 − 3 = +1 · each O: 6 − 6 − 1 = −1 → answer D
S: one lone pair, three bonds · O: three lone pairs, one bond · sum +1 + 3(−1) = −2 ✓

A gave oxidation numbers: both electrons of every S–O bond go to oxygen, so O is −2 and S is −2 − 3(−2) = +4. Formal charge splits each bond evenly. B counted all the bonding electrons: S 6 − 2 − 6 = −2, O 6 − 6 − 2 = −2, a sum of −8. C put the ion's whole 2− on sulfur; each oxygen still holds three lone pairs, 6 − 6 − 1 = −1.

Dr. Karmach

Extra practice 1 answer: D

S: 6 − 2 − 3 = +1 · each O: 6 − 6 − 1 = −1 → answer D
S: one lone pair, three bonds · O: three lone pairs, one bond · sum +1 + 3(−1) = −2 ✓
A and C also sum to −2, so the sum check alone misses them. Compute every atom first; the sum only confirms.

Dr. Karmach

Extra practice 2: a student's amide ion

NH₂⁻ as drawn: H–N–H · one lone pair on N
student's formal charges: N 5 − 2 − 2 = +1 · each H 0 · sum +1

What should the student conclude?

  1. The drawing holds 6 electrons; NH₂⁻ has 8, so N needs a second lone pair
  2. The arithmetic slipped: N is 5 − 2 − 4 = −1, so the drawing is fine
  3. Nothing is wrong: the sum check applies only to neutral molecules
  4. The drawing is fine; its +1 sum shows the ion is really NH₂⁺
Dr. Karmach

Extra practice 2 answer: A

NH₂⁻: 5 + 2(1) + 1 = 8 valence electrons, drawn with 6 → answer A
drawn: 2 bonds + 1 lone pair = 6 · fixed: two lone pairs on N · N 5 − 4 − 2 = −1 · each H 0 · sum −1 ✓

The student counted 5 + 2 − 1 = 6, subtracting the 1− charge instead of adding it, and left N with 6 electrons. B counted all four of nitrogen's bonding electrons: 5 − 2 − 4 = −1 hits the right sum by accident, and the drawing still holds 6 electrons. C dropped the rule; an ion's formal charges add to its charge. D trusted the drawing over the formula; the formula sets the charge, and the sum tests the drawing.

Dr. Karmach

Extra practice 2 answer: A

NH₂⁻: 5 + 2(1) + 1 = 8 valence electrons, drawn with 6 → answer A
drawn: 2 bonds + 1 lone pair = 6 · fixed: two lone pairs on N · N 5 − 4 − 2 = −1 · each H 0 · sum −1 ✓
A negative charge adds electrons; a positive charge removes them. A sum that misses the charge points back to the electron count.

Dr. Karmach

Extra practice 3: the nitrosonium ion

NO⁺
wanted: the formal charges on N and O

In the octet-rule Lewis structure of NO⁺, what are the formal charges on nitrogen and oxygen?

  1. N +1, O 0
  2. N 0, O +1
  3. N −1, O 0
  4. N +3, O −2
  5. N −3, O −2
Dr. Karmach

Extra practice 3 answer: B

N≡O: N 5 − 2 − 3 = 0 · O 6 − 2 − 3 = +1 → answer B
NO⁺: 5 + 6 − 1 = 10 electrons · one lone pair on each atom · both octets complete · sum +1 ✓

A stopped at N=O: N 5 − 2 − 2 = +1 and O 6 − 4 − 2 = 0 sum to +1, but N holds only 6 electrons. C added an electron for the + charge: 5 + 6 + 1 = 12 gives N=O with N 5 − 4 − 2 = −1, a sum of −1. D gave oxidation numbers, O −2 and N +3. E counted all six bonding electrons: N 5 − 2 − 6 = −3, O 6 − 2 − 6 = −2.

Dr. Karmach

Extra practice 3 answer: B

N≡O: N 5 − 2 − 3 = 0 · O 6 − 2 − 3 = +1 → answer B
NO⁺: 5 + 6 − 1 = 10 electrons · one lone pair on each atom · both octets complete · sum +1 ✓
The octet rule comes first. Only N≡O completes both octets, so the +1 sits on oxygen even though oxygen is the more electronegative atom.

Dr. Karmach

Check yourself

  1. Why does a single Lewis structure fail for the carbonate ion?
  2. Compute the formal charge on the double-bonded oxygen in ozone.

Formal charge also referees the octet rule itself: some structures are best with fewer than eight electrons on an atom, and heavier central atoms can hold more. Those exceptions are the next topic.

Dr. Karmach

4 · Exceptions to the Octet Rule

Recognize and draw the three exception families: incomplete octets, odd-electron molecules, and expanded octets on period-3-or-lower central atoms.

Dr. Karmach

Three ways real molecules break the octet rule

The octet rule builds most structures, not all. Boron trifluoride stops at six electrons. Nitrogen monoxide carries an odd electron. Sulfur tetrafluoride holds ten.

Dr. Karmach

The octet is a pattern, not a law

Eight electrons fill an atom's s and p valence orbitals. Most main-group atoms reach that count. Three families do not, each for its own reason.

BF₃: six around B  ·  NO: 11 electrons, one unpaired  ·  SF₄: ten around S
incomplete octet · odd-electron molecule · expanded octet
period 3 or lower can expand · C, N, O, F stop at eight
a period-2 atom has four valence orbitals: room for eight, never more
Dr. Karmach

Incomplete octets: beryllium and boron

Boron and beryllium routinely stop short of eight. In BF₃, boron holds three bonds and six electrons, and the structure is stable as drawn.

BF₃: 3 + 3(7) = 24  ·  B: 3 bonds = 6 electrons
every F keeps its octet · boron does not reach eight
Dr. Karmach

Odd-electron molecules

An odd valence total can never pair into full octets. NO holds 11 electrons; one stays unpaired on nitrogen. The structure shows it as a single dot.

NO: 5 + 6 = 11 valence electrons
10 pair up · 1 electron remains single · no octet for N
Dr. Karmach

Expanded octets: period 3 and below

A period-2 atom has four valence orbitals, one s and three p: eight electrons at most. Atoms from period 3 down are larger, with more orbitals, so more pairs fit.

PF₅: 10 around P  ·  SF₄: 10 around S  ·  ICl₄⁻: 12 around I
only period-3-or-lower centers expand · C, N, O, F stop at eight
Dr. Karmach

The method

  1. Count the valence electrons.
  2. Build the skeleton, then the outer octets.
  3. Leftovers go on the central atom, past eight when it sits in period 3 or lower.
  4. Never expand a second-period atom.
Dr. Karmach

Worked example 1: phosphorus pentafluoride

Step 1 · Count the valence electrons

PF₅: 5 + 5(7) = 40
1 P (group 15 → 5) · 5 F (group 17 → 7) · 40 to place

Five fluorines must bond to one phosphorus. Draw the Lewis structure.

Dr. Karmach

Worked example 1: solution

PF₅: 5 + 5(7) = 40 valence electrons · skeleton: five P–F single bonds

Step 2 · Build the skeleton, then the outer octets

5 bonds: 5 × 2 = 10  ·  5 F × 3 lone pairs: 5 × 6 = 30
10 + 30 = 40 · every electron placed · every F has its octet
Dr. Karmach

Worked example 1: solution

PF₅: 5 + 5(7) = 40 valence electrons · skeleton: five P–F single bonds

Step 2 · Build the skeleton, then the outer octets

5 bonds: 5 × 2 = 10  ·  5 F × 3 lone pairs: 5 × 6 = 30
10 + 30 = 40 · every electron placed · every F has its octet
Ten electrons sit in the five P–F bonds and thirty complete the fluorines. All 40 are placed.
Dr. Karmach

Worked example 1: the expanded octet

Step 3 · Leftovers go on the central atom

40 − 10 − 30 = 0 leftover  ·  P: 5 bonds = 10 electrons
phosphorus exceeds eight through its bonds alone · period 3 → allowed

Dr. Karmach

Worked example 1: the expanded octet

Step 3 · Leftovers go on the central atom

40 − 10 − 30 = 0 leftover  ·  P: 5 bonds = 10 electrons
phosphorus exceeds eight through its bonds alone · period 3 → allowed

Ten electrons around phosphorus: an expanded octet carried by the bonds alone.
Dr. Karmach

Worked example 2: the ICl₄⁻ ion

Step 1 · Count the valence electrons

ICl₄⁻: 7 + 4(7) + 1 = 36
the 1− charge adds one electron · 36 to place

Iodine takes the center. Draw the Lewis structure.

Dr. Karmach

Worked example 2: bonds and outer octets

ICl₄⁻: 7 + 4(7) + 1 = 36 valence electrons
skeleton: four I–Cl single bonds

Step 2 · Build the skeleton, then the outer octets

4 bonds: 4 × 2 = 8  ·  4 Cl × 3 lone pairs: 4 × 6 = 24
8 + 24 = 32 of 36 placed · every Cl has its octet
Dr. Karmach

Worked example 2: bonds and outer octets

ICl₄⁻: 7 + 4(7) + 1 = 36 valence electrons
skeleton: four I–Cl single bonds

Step 2 · Build the skeleton, then the outer octets

4 bonds: 4 × 2 = 8  ·  4 Cl × 3 lone pairs: 4 × 6 = 24
8 + 24 = 32 of 36 placed · every Cl has its octet
Thirty-two of the 36 electrons are placed and every chlorine is full. Four remain, and the only atom left is iodine.
Dr. Karmach

Worked example 2: the expanded center

ICl₄⁻: 36 − 8 − 24 = 4 electrons left
every Cl full · the leftovers belong to iodine

Step 3 · Leftovers go on the central atom

4 leftover → 2 lone pairs on I  ·  I: 8 + 4 = 12 electrons
4 bonds (8) + 2 lone pairs (4) · period 5 → expansion allowed

Dr. Karmach

Worked example 2: the expanded center

ICl₄⁻: 36 − 8 − 24 = 4 electrons left
every Cl full · the leftovers belong to iodine

Step 3 · Leftovers go on the central atom

4 leftover → 2 lone pairs on I  ·  I: 8 + 4 = 12 electrons
4 bonds (8) + 2 lone pairs (4) · period 5 → expansion allowed

Twelve electrons around iodine. Period 5 has the room; a second-period atom never could.
Dr. Karmach

Your turn: sulfur tetrafluoride

SF₄: 6 + 4(7) = 34 valence electrons
skeleton: four S–F single bonds · complete the fluorine octets first

Fill the blanks: electrons in the 4 bonds plus the fluorine lone pairs · leftover for sulfur · electrons around S

Dr. Karmach

Your turn: sulfur tetrafluoride

SF₄: 6 + 4(7) = 34 valence electrons
skeleton: four S–F single bonds · complete the fluorine octets first
8 + 24 = 32  ·  34 − 32 = 2 → 1 lone pair on S  ·  S: 8 + 2 = 10
expanded octet on period-3 sulfur · every F keeps its octet

Dr. Karmach

Where this goes wrong

Expanding a second-period atom. Ten electrons around carbon or nitrogen is never right. Expansion starts in period 3; C, N, O, and F stop at eight.
Dropping the ion's charge. ICl₄⁻ counted neutral gives 7 + 4(7) = 35. The 1− charge adds the 36th electron; without it the whole structure runs one short.
Pairing the unpairable. NO holds 11 valence electrons. No structure pairs them all; one electron stays single, and the drawing must show it.
Dr. Karmach

Practice 1: sulfur hexafluoride

SF₆: 6 + 6(7) = 48 valence electrons · six S–F single bonds
each F carries 3 lone pairs · nothing is left over

How many electrons surround the sulfur atom?

  1. 48
  2. 36
  3. 18
  4. 12
Dr. Karmach

Practice 1 answer: D

S: 6 bonds × 2 = 12 electrons → answer D
period-3 sulfur holds all six bonds · an expanded octet

C added sulfur's own six valence electrons on top of the twelve in its bonds: 12 + 6 = 18; those six are already inside the bonds. A counted the whole pool: 6 + 6(7) = 48. B counted the fluorine lone pairs: 6 × 6 = 36.

Six bonds alone put 12 electrons on sulfur. The 36 lone-pair electrons live on the fluorines, not on the center.
Dr. Karmach

Worked example 3: boron trifluoride

BF₃: 3 + 3(7) = 24  ·  three B–F bonds + nine F lone pairs = 24
all placed · boron sits at six electrons

Tempting fix: move a fluorine lone pair into a B=F double bond and give boron an octet. Test the fix with formal charges.

Dr. Karmach

Worked example 3: the fix fails

candidate: one B=F double bond · boron reaches 8 · BF₃: 3 + 3(7) = 24
Dr. Karmach

Worked example 3: the fix fails

candidate: one B=F double bond · boron reaches 8 · BF₃: 3 + 3(7) = 24
Formal charge on the double-bonded F

F: 7 − 4 − 2 = +1. Fluorine, the most electronegative element, goes positive.

Dr. Karmach

Worked example 3: the fix fails

candidate: one B=F double bond · boron reaches 8 · BF₃: 3 + 3(7) = 24
Formal charge on the double-bonded F Formal charge on boron
B: 3 − 0 − 4 = −1  ·  F: 7 − 4 − 2 = +1  ·  all-single structure: every FC = 0
B: 3 − 0 − 3 = 0 · each F: 7 − 6 − 1 = 0

Dr. Karmach

Worked example 3: the fix fails

candidate: one B=F double bond · boron reaches 8 · BF₃: 3 + 3(7) = 24
Formal charge on the double-bonded F Formal charge on boron
B: 3 − 0 − 4 = −1  ·  F: 7 − 4 − 2 = +1  ·  all-single structure: every FC = 0
B: 3 − 0 − 3 = 0 · each F: 7 − 6 − 1 = 0

Negative on B, positive on F: backward. The all-single structure wins.
Dr. Karmach

Take-home: an incomplete octet can be the best structure

When completing an octet forces bad formal charges, leave the octet incomplete. Boron and beryllium accept fewer than eight; formal charge makes the call.

BF₃ best structure: three single bonds · B at 6 · every FC = 0
forcing B=F gives −1 on B and +1 on F · rejected
Dr. Karmach

Practice 2: completing ICl₂⁻

ICl₂⁻: skeleton Cl–I–Cl
given: two I–Cl single bonds · three lone pairs on each Cl · wanted: what completes the structure

A student builds the ion with two single bonds and a full octet on each chlorine, then stops. What completes the structure?

  1. Two lone pairs and one unpaired electron on iodine
  2. Two lone pairs on iodine, giving it an octet
  3. Three lone pairs on iodine, giving it 10 electrons
  4. One lone pair on iodine and one extra pair on each chlorine
Dr. Karmach

Practice 2 answer: C

ICl₂⁻: 7 + 2(7) + 1 = 22 · placed: 2 bonds (4) + 6 Cl lone pairs (12) = 16 · left: 22 − 16 = 6
6 leftover → 3 lone pairs on I · I: 4 + 6 = 10 electrons · period 5 → allowed → answer C

A dropped the 1− charge: 7 + 2(7) = 21 leaves 5, two pairs and a stray electron; the added electron makes 22, an even count that pairs fully. B subtracted the charge instead: 7 + 2(7) − 1 = 20 leaves 4, two pairs and an octet; a negative charge adds an electron. D placed the right 22 but parked the leftovers on the chlorines; every outer atom already has its octet, so leftovers go on the center.

Iodine ends with two bonds and three lone pairs, ten electrons: an expanded octet on a period-5 center.
Dr. Karmach

Practice 3: a center past eight

Which species has more than eight electrons around its central atom?

  1. SCl₂
  2. TeCl₄
  3. ICl₂⁺
  4. BBr₃
Dr. Karmach

Practice 3 answer: B

TeCl₄: 6 + 4(7) = 34 · placed: 4 bonds (8) + 4 Cl × 3 lone pairs (24) = 32 · left: 2
2 leftover → 1 lone pair on Te · Te: 8 + 2 = 10 · period 5 → allowed → answer B
SCl₂: 6 + 2(7) = 20 · ICl₂⁺: 7 + 2(7) − 1 = 20 · BBr₃: 3 + 3(7) = 24
S: 2 bonds + 2 lone pairs = 8 · I: 2 bonds + 2 lone pairs = 8 · B: 3 bonds = 6

A read period 3 as a requirement. Sulfur may expand, but SCl₂'s 20 electrons close with sulfur at eight. C added the charge instead of subtracting it: 7 + 2(7) + 1 = 22 leaves 6 for iodine, 10 electrons. D mixed up the families: boron's six is an incomplete octet.

Period 3 and below may pass eight; nothing forces it. Only electrons left after the outer octets push a center past eight. ✓
Dr. Karmach

Practice 4: the BF₄⁻ ion

BF₄⁻: boron bonded to four F
formed when BF₃ picks up a fluoride ion, F⁻

How many electrons surround boron, and what is its formal charge?

  1. electrons around B 8 · formal charge +1
  2. electrons around B 6 · formal charge 0
  3. electrons around B 9 · formal charge −2
  4. electrons around B 8 · formal charge −1
  5. electrons around B 8 · formal charge −5
Dr. Karmach

Practice 4 answer: D

BF₄⁻: 3 + 4(7) + 1 = 32 · 4 bonds (8) + 4 F × 3 lone pairs (24) = 32 · 0 left
B: 4 bonds = 8 electrons · FC(B) = 3 − 0 − 4 = −1 · each F: 7 − 6 − 1 = 0 → answer D

A reversed the subtraction: 4 bonds − 3 valence = +1. B drew BF₃ beside a separate F⁻: boron keeps six electrons and a formal charge of 0, but the ion has four B–F bonds. C counted the charge twice: all 32 are already placed, and a 33rd dot on boron gives 9 electrons and 3 − 1 − 4 = −2. E counted every bonding electron, not half: 3 − 0 − 8 = −5.

Every F stays at 0, and −1 + 4(0) = −1 matches the ion's charge. Forcing B=F in BF₃ failed because it put +1 on fluorine. ✓
Dr. Karmach

Practice 5: iodine trichloride

In the correct Lewis structure of ICl₃, how many single bonds are there, and how many lone pairs?

  1. single bonds 3 · lone pairs 11
  2. single bonds 3 · lone pairs 9
  3. single bonds 1 · lone pairs 9
  4. single bonds 3 · lone pairs 13
  5. single bonds 3 · lone pairs 10
Dr. Karmach

Practice 5 answer: A

ICl₃: 7 + 3(7) = 28 · placed: 3 bonds (6) + 3 Cl × 3 lone pairs (18) = 24 · left: 4
28 − 24 = 4 leftover → 2 lone pairs on I · 9 + 2 = 11 lone pairs · I: 6 + 4 = 10 electrons → answer A

B stopped at the outer octets and never placed the last 4 electrons. C formed two I=Cl bonds from chlorine lone pairs: 1 single bond and 7 Cl pairs + 2 on I = 9, but iodine reaches 14 at a formal charge of −2; double bonds are for a center short of eight. D counted the 4 leftover electrons as 4 pairs: 9 + 4 = 13. E gave iodine one pair to reach eight, 9 + 1 = 10, and left 2 electrons unplaced; period-5 iodine may pass eight.

Every Cl holds eight, all 28 electrons are placed, and iodine holds 10: an expanded octet on a period-5 center. ✓
Dr. Karmach

Check yourself

  1. Which periods allow an expanded octet, and which four elements never expand?
  2. Count the electrons around sulfur in SF₄ and around iodine in ICl₄⁻.

The count of bonds and lone pairs around a central atom, octet or expanded, is exactly what fixes a molecule's three-dimensional shape.

Dr. Karmach

5 · VSEPR & Molecular Shape

Predict a molecule's electron-pair geometry and its shape by counting the electron domains on the central atom and reading which corners lone pairs take.

Dr. Karmach

What sets a molecule's shape

Tie balloons at one knot and they push apart to the roomiest arrangement. Atoms bonded to a central atom spread out the very same way.

Dr. Karmach

Electron domains repel and spread apart

An electron domain is one group of electrons on the central atom: a bond or a lone pair. Like charges repel, so the domains spread as far apart as they can.

domains push to the farthest-apart arrangement
that arrangement, lone pairs included, sets the molecule's shape
Dr. Karmach

Counting the domains

Count the domains on the central atom: one for each bonded atom, plus one for each lone pair. A single, double, or triple bond counts as one domain, no matter how many pairs it holds.

CO₂: C bonded to 2 O by double bonds
2 bonded atoms + 0 lone pairs → 2 domains (each double bond counts once)
NH₃: N bonded to 3 H, plus 1 lone pair
3 bonded atoms + 1 lone pair → 4 domains
Dr. Karmach

From domain count to electron-pair geometry

The number of domains fixes how they arrange in space. Two domains sit at 180°, three at 120°, four at 109.5°. This spread is the electron-pair geometry.

Dr. Karmach

From geometry to molecular shape

Lone pairs take up domains but hold no atom. The molecular shape names only where the atoms sit. Four tetrahedral domains read as tetrahedral, trigonal pyramidal, or bent as lone pairs replace atoms.

Dr. Karmach

The common shapes side by side

memory hook: count the domains, then subtract the lone pairs from the name
2 → linear · 3 → trigonal planar, then bent · 4 → tetrahedral, then trigonal pyramidal, then bent
Dr. Karmach

The method

  1. Count the electron domains. One per bonded atom, one per lone pair; every bond counts once.
  2. Name the electron-pair geometry. 2 linear, 3 trigonal planar, 4 tetrahedral.
  3. Name the molecular shape. Keep atom positions; lone-pair corners stay empty.
Dr. Karmach

Worked example 1: methane

CH₄: C bonded to 4 H
central atom: carbon · 4 bonded H · 0 lone pairs on C

Methane's central carbon bonds to four hydrogens with no lone pairs left over. Give its electron-pair geometry and its molecular shape.

Dr. Karmach

Worked example 1: solution

CH₄: C bonded to 4 H
central atom: carbon · 4 bonded H · 0 lone pairs on C

Step 1 · Count the electron domains

Four bonded hydrogens and no lone pairs on carbon. Together that is 4 + 0 = 4 electron domains.

Dr. Karmach

Worked example 1: solution

CH₄: C bonded to 4 H
central atom: carbon · 4 bonded H · 0 lone pairs on C
Step 1 · Count the electron domains Step 2 · Name the electron-pair geometry

Four domains spread as far apart as possible, to 109.5°. The electron-pair geometry is tetrahedral.

Dr. Karmach

Worked example 1: solution

CH₄: C bonded to 4 H
central atom: carbon · 4 bonded H · 0 lone pairs on C
Step 1 · Count the electron domains Step 2 · Name the electron-pair geometry Step 3 · Name the molecular shape
CH₄ → tetrahedral
4 domains · 0 lone pairs · every corner holds an atom · 109.5°
Dr. Karmach

Worked example 1: solution

CH₄: C bonded to 4 H
central atom: carbon · 4 bonded H · 0 lone pairs on C
Step 1 · Count the electron domains Step 2 · Name the electron-pair geometry Step 3 · Name the molecular shape
CH₄ → tetrahedral
4 domains · 0 lone pairs · every corner holds an atom · 109.5°
No lone pairs, so every corner holds an atom and the shape matches the electron-pair geometry: tetrahedral.
Dr. Karmach

Worked example 1: the row in the table

CH₄: X = 4 bonded H · E = 0 lone pairs → AX₄
found: 4 domains · tetrahedral geometry · tetrahedral shape · 109.5°

Four atoms and no lone pairs: the AX₄ row. The geometry and the shape share one name. ✓
Dr. Karmach

Worked example 2: carbon dioxide

O=C=O: C bonded to 2 O by double bonds
central atom: carbon · 2 bonded O · 0 lone pairs on C

Carbon dioxide holds two carbon–oxygen double bonds. A common first attempt: two double bonds make four domains. Find the geometry and the shape.

Dr. Karmach

Worked example 2: solution

O=C=O: C bonded to 2 O by double bonds
central atom: carbon · 2 bonded O · 0 lone pairs on C

A common first attempt

2 double bonds = 4 domains?
counting each double bond as two: 2 × 2 = 4 ✗ · a bond is one domain however many pairs it holds

A double bond is one region of electrons, so it counts once. Two double bonds are two domains, not four.

Dr. Karmach

Worked example 2: solution

O=C=O: C bonded to 2 O by double bonds
central atom: carbon · 2 bonded O · 0 lone pairs on C
A common first attempt
2 double bonds = 4 domains?
counting each double bond as two: 2 × 2 = 4 ✗ · a bond is one domain however many pairs it holds
Step 1 · Count the electron domains

Two bonded oxygens and no lone pairs on carbon: 1 + 1 = 2 electron domains.

Dr. Karmach

Worked example 2: solution

O=C=O: C bonded to 2 O by double bonds
central atom: carbon · 2 bonded O · 0 lone pairs on C
A common first attempt
2 double bonds = 4 domains?
counting each double bond as two: 2 × 2 = 4 ✗ · a bond is one domain however many pairs it holds
Step 1 · Count the electron domains Step 2 · Name the electron-pair geometry

Two domains point straight apart, to 180°. The electron-pair geometry is linear.

Dr. Karmach

Worked example 2: solution

O=C=O: C bonded to 2 O by double bonds
central atom: carbon · 2 bonded O · 0 lone pairs on C
A common first attempt
2 double bonds = 4 domains?
counting each double bond as two: 2 × 2 = 4 ✗ · a bond is one domain however many pairs it holds
Step 1 · Count the electron domains Step 2 · Name the electron-pair geometry Step 3 · Name the molecular shape
CO₂ → linear
2 domains · 0 lone pairs · both corners hold an atom · 180°
Dr. Karmach

Worked example 2: solution

O=C=O: C bonded to 2 O by double bonds
central atom: carbon · 2 bonded O · 0 lone pairs on C
A common first attempt
2 double bonds = 4 domains?
counting each double bond as two: 2 × 2 = 4 ✗ · a bond is one domain however many pairs it holds
Step 1 · Count the electron domains Step 2 · Name the electron-pair geometry Step 3 · Name the molecular shape
CO₂ → linear
2 domains · 0 lone pairs · both corners hold an atom · 180°
Each double bond is one domain, so carbon has two. Two domains can only point 180° apart: a linear molecule.
Dr. Karmach

Worked example 2: the row in the table

CO₂: X = 2 bonded O · E = 0 lone pairs → AX₂
found: 2 domains · linear geometry · linear shape · 180°

Two atoms and no lone pairs: the AX₂ row. Each double bond counts once, so the row stays AX₂. ✓
Dr. Karmach

Take-home: a bond is one domain

O=C=O → 2 domains → linear (180°)
each double bond counts once: 1 + 1 = 2 ✓
counting each double bond twice → 4 domains → a tetrahedral guess
2 × 2 = 4 ✗ · the extra domains would bend a straight molecule

Bond order does not change the domain count. A single, double, or triple bond is one region of electrons, so it claims one domain.

Dr. Karmach

Your turn: ammonia

NH₃: N bonded to 3 H, with 1 lone pair on N
central atom: nitrogen · 3 bonded H · 1 lone pair
step count result
1 · domains 3 bonded + 1 lone pair domains
2 · electron-pair geometry from 4 domains
3 · molecular shape 3 atoms, 1 corner a lone pair

Fill the three results.

Dr. Karmach

Your turn: ammonia

NH₃: N bonded to 3 H, with 1 lone pair on N
central atom: nitrogen · 3 bonded H · 1 lone pair
step count result
1 · domains 3 bonded + 1 lone pair domains
2 · electron-pair geometry from 4 domains
3 · molecular shape 3 atoms, 1 corner a lone pair

Fill the three results.

NH₃ → trigonal pyramidal
3 + 1 = 4 domains · tetrahedral geometry · 1 corner empty · angle ≈ 107°
Dr. Karmach

Where this goes wrong

Reporting the electron-pair geometry as the shape. Water has four domains, a tetrahedral geometry. But two corners are lone pairs. The shape names only the atoms: bent, not tetrahedral.
Ignoring the lone pairs. Arrange only NH₃'s three bonded atoms and you get a flat trigonal planar. The lone pair takes a corner too, pressing the atoms into a trigonal pyramid.
Counting a double bond as two domains. SO₂ has two bonded oxygens plus one lone pair. Count the S=O double bond as two and you reach four domains. Each bond is one domain: 2 + 1 = 3 domains, a bent molecule.
Dr. Karmach

Practice 1

NF₃: N bonded to 3 F, with 1 lone pair on N
central atom: nitrogen · 3 bonded F · 1 lone pair

Nitrogen trifluoride has three bonded fluorines and one lone pair on nitrogen. What is its molecular shape?

  1. Trigonal pyramidal: three bonded atoms with the lone pair pressing them down
  2. Tetrahedral: the four electron domains arrange as a tetrahedron
  3. Trigonal planar: the three fluorines spread evenly around nitrogen
  4. Bent: the lone pair leaves only a bent arrangement
Dr. Karmach

Practice 1 answer: A

NF₃ → trigonal pyramidal → answer A
3 bonded F + 1 lone pair = 4 domains · tetrahedral geometry · 1 corner empty

B named the electron-pair geometry, not the shape: the lone pair takes a corner, so the atoms are not tetrahedral. C ignored the lone pair; three bonded atoms alone would be trigonal planar, but the fourth corner is filled. D miscounts: four domains, not three, so the base is a tetrahedron, not a triangle.

Four domains, one a lone pair: the three fluorines press down into a pyramid. Trigonal pyramidal.
Dr. Karmach

Worked example 3: sulfur dioxide

O=S–O: S bonded to 2 O, with 1 lone pair on S
central atom: sulfur · 2 bonded O · 1 lone pair · one bond is double

Sulfur dioxide has two bonded oxygens, one of them a double bond, and a lone pair on sulfur. Give its electron-pair geometry and its molecular shape.

Dr. Karmach

Worked example 3: solution

O=S–O: S bonded to 2 O, with 1 lone pair on S
central atom: sulfur · 2 bonded O · 1 lone pair · one bond is double

Step 1 · Count the electron domains

Two bonded oxygens count as two domains: the double bond counts once. Add the lone pair: 2 + 1 = 3 electron domains.

Dr. Karmach

Worked example 3: solution

O=S–O: S bonded to 2 O, with 1 lone pair on S
central atom: sulfur · 2 bonded O · 1 lone pair · one bond is double
Step 1 · Count the electron domains Step 2 · Name the electron-pair geometry

Three domains spread to 120°. The electron-pair geometry is trigonal planar.

Dr. Karmach

Worked example 3: solution

O=S–O: S bonded to 2 O, with 1 lone pair on S
central atom: sulfur · 2 bonded O · 1 lone pair · one bond is double
Step 1 · Count the electron domains Step 2 · Name the electron-pair geometry Step 3 · Name the molecular shape
SO₂ → bent
3 domains · trigonal planar geometry · 1 corner a lone pair · angle just under 120°
Dr. Karmach

Worked example 3: solution

O=S–O: S bonded to 2 O, with 1 lone pair on S
central atom: sulfur · 2 bonded O · 1 lone pair · one bond is double
Step 1 · Count the electron domains Step 2 · Name the electron-pair geometry Step 3 · Name the molecular shape
SO₂ → bent
3 domains · trigonal planar geometry · 1 corner a lone pair · angle just under 120°
Three domains, one a lone pair, leave two oxygens in a bent line. The lone pair squeezes the angle a little below 120°.
Dr. Karmach

Worked example 3: the row in the table

SO₂: X = 2 bonded O · E = 1 lone pair → AX₂E
found: 3 domains · trigonal planar geometry · bent shape · just under 120°

Two atoms and one lone pair: the AX₂E row, inside the trigonal planar group. ✓
Dr. Karmach

Summary: domains, geometry, shape

Count the bonded atoms (X) and lone pairs (E), then read the row across.

Dr. Karmach

Worked example 4: water

H–O–H: O bonded to 2 H, with 2 lone pairs on O
central atom: oxygen · 2 bonded H · 2 lone pairs on O

Water's oxygen bonds to two hydrogens and keeps two lone pairs. Count the domains, then read its row for the electron-pair geometry, the shape, and the angle.

Dr. Karmach

Worked example 4: solution

H–O–H: O bonded to 2 H, with 2 lone pairs on O
central atom: oxygen · 2 bonded H · 2 lone pairs on O

Step 1 · Count the electron domains

Two bonded hydrogens and two lone pairs on oxygen: 2 + 2 = 4 electron domains.

Dr. Karmach

Worked example 4: solution

H–O–H: O bonded to 2 H, with 2 lone pairs on O
central atom: oxygen · 2 bonded H · 2 lone pairs on O
Step 1 · Count the electron domains Step 2 · Name the electron-pair geometry

Four domains land on the AX₂E₂ row. The electron-pair geometry is tetrahedral.

Dr. Karmach

Worked example 4: solution

H–O–H: O bonded to 2 H, with 2 lone pairs on O
central atom: oxygen · 2 bonded H · 2 lone pairs on O
Step 1 · Count the electron domains Step 2 · Name the electron-pair geometry Step 3 · Name the molecular shape
H₂O → AX₂E₂ → bent
4 domains · tetrahedral geometry · 2 corners hold lone pairs · angle ≈ 104.5°
Dr. Karmach

Worked example 4: solution

H–O–H: O bonded to 2 H, with 2 lone pairs on O
central atom: oxygen · 2 bonded H · 2 lone pairs on O
Step 1 · Count the electron domains Step 2 · Name the electron-pair geometry Step 3 · Name the molecular shape
H₂O → AX₂E₂ → bent
4 domains · tetrahedral geometry · 2 corners hold lone pairs · angle ≈ 104.5°
Two of the four corners hold lone pairs. The two hydrogens are left in a bent line, near 104.5°.
Dr. Karmach

Worked example 4: the row in the table

H₂O: X = 2 bonded H · E = 2 lone pairs → AX₂E₂
found: 4 domains · tetrahedral geometry · bent shape · about 104.5°

Two atoms and two lone pairs: the AX₂E₂ row. Same shape name as SO₂, a different row and a smaller angle. ✓
Dr. Karmach

Practice 2

H₂Se: Se bonded to 2 H
a student draws two Se–H bonds, no lone pairs on Se, and names the shape linear

Evaluate the work.

  1. Correct: two bonded atoms give two domains, 180° apart
  2. Wrong: selenium keeps two lone pairs, so four domains make the shape tetrahedral
  3. Wrong: selenium keeps two lone pairs, so four domains make the shape bent
  4. Wrong: selenium keeps one lone pair, so three domains make the shape bent, near 120°
Dr. Karmach

Practice 2 answer: C

H₂Se: 2(1) + 6 = 8 valence electrons · 8 − 4 in the two bonds = 4 left → 2 lone pairs on Se
2 + 2 = 4 domains · tetrahedral geometry · 2 corners hold lone pairs · bent shape → answer C

A dropped the lone pairs: only 4 of the 8 electrons sit in the two bonds, and the other 4 stay on selenium as two more domains. B named the electron-pair geometry; two of the four corners hold lone pairs, so the atoms are bent, not tetrahedral. D miscounted the leftovers as one pair: 8 − 4 = 4 electrons make two pairs, four domains, not three.

Same count as water: two bonds, two lone pairs, four domains. The drawing must show the lone pairs before the shape can be read.
Dr. Karmach

Extra practice 1

BI₃
boron triiodide, used to cleave ethers in organic synthesis

By VSEPR, how many degrees separate two B–I bonds in BI₃?

  1. 109.5
  2. 90
  3. 120
  4. 107
Dr. Karmach

Extra practice 1 answer: C

BI₃: 3 + 3(7) = 24 · 3 bonds use 3 × 2 = 6 · each I takes 6: 3 × 6 = 18 · 24 − 6 − 18 = 0 left on B
B holds 6 electrons, an incomplete octet · X = 3 · E = 0 · 3 + 0 = 3 domains · trigonal planar, 120° → answer C

D forced boron's octet with a lone pair. No electrons remain for one, so the 3 + 1 = 4 domains of a 107° pyramid never form. A added the same lone pair and took the tetrahedral angle, 109.5°. B read the angle off the flat drawing; three domains spread to 120°, not 90°.

Boron stops at six electrons, as in BF₃. Three domains and no lone pair keep the molecule flat at 120°. ✓
Dr. Karmach

Extra practice 2

NO₂⁺
the nitronium ion, formed when nitric and sulfuric acids mix

For the nitronium ion, name the electron-pair geometry, then the molecular shape.

  1. Tetrahedral, then tetrahedral
  2. Linear, then linear
  3. Trigonal planar, then bent
  4. Tetrahedral, then bent
  5. Trigonal planar, then trigonal planar
Dr. Karmach

Extra practice 2 answer: B

NO₂⁺: 5 + 2(6) − 1 = 16 · 2 bonds use 4 · each O takes 6: 2 × 6 = 12 · 16 − 4 − 12 = 0 left on N
N has only 4 → each O shares a pair: O=N=O, N at 4 + 4 = 8 · X = 2 · E = 0 · 2 + 0 = 2 domains · AX₂, linear, then linear → answer B

C added the charge: 5 + 2(6) + 1 = 18 leaves 18 − 4 − 12 = 2, one lone pair; a 1+ ion has one electron fewer. A counted each N=O double bond as two domains: 2 × 2 = 4. D made the same count and read the two extra domains as lone pairs. E counted nitrogen itself: 2 + 1 = 3; domains surround the central atom.

One electron separates NO₂⁺ from the nitrite ion, NO₂⁻. With no lone pair on N, the two oxygens sit 180° apart. ✓
Dr. Karmach

Extra practice 3

NH₃: trigonal pyramidal
3 bonded H + 1 lone pair on N · 4 domains

Which species has the same molecular shape as ammonia?

  1. NO₃⁻
  2. SO₃
  3. NH₄⁺
  4. H₃O⁺
Dr. Karmach

Extra practice 3 answer: D

H₃O⁺: 6 + 3(1) − 1 = 8 · 3 bonds use 6 · 8 − 6 = 2 left → 1 lone pair on O
X = 3 · E = 1 · 3 + 1 = 4 domains · AX₃E, trigonal pyramidal: the same counts as NH₃ → answer D

A gave nitrogen a lone pair, as in NH₃. NO₃⁻ has 5 + 3(6) + 1 = 24 electrons, and 24 − 6 − 18 = 0 left; N at 6 → one O shares a pair, N=O: 3 domains, trigonal planar. B counted the S=O double bond twice: 3 + 1 = 4 domains around three atoms. SO₃ has 6 + 3(6) = 24, none left on S; S at 6 → one O shares a pair, S=O: 3 + 0 = 3 domains, trigonal planar. C matched the elements, not the counts. NH₄⁺ has 5 + 4(1) − 1 = 8 electrons, all in four N–H bonds: tetrahedral.

The same shape needs the same X and E, not the same central atom. H₃O⁺ and NH₃ are both AX₃E. ✓
Dr. Karmach

Check yourself

  1. PH₃ has a phosphorus bonded to three hydrogens and one lone pair. Count the domains, name the electron-pair geometry, then the shape.
  2. Both CO₂ and SO₂ have two bonded oxygens. Why is one linear and the other bent?

Shape sets polarity. Two equal bond dipoles cancel when they point exactly opposite, as in linear CO₂. A bent or pyramidal shape leaves them pointing partly the same way, so the molecule is polar. Combining these bond dipoles with the molecular shape shows whether the whole molecule is polar.

Dr. Karmach

6 · Molecular Polarity

Decide whether a whole molecule is polar by combining its bond dipoles with its shape: symmetric shapes with identical outer atoms cancel the dipoles to nonpolar, while lopsided shapes or a central lone pair leave a net dipole.

Dr. Karmach

Why the plate stays cool

A microwave heats the soup, not the dry plate under it. Water molecules are lopsided, so the oven's field keeps twisting them. That twisting is the heat.

Dr. Karmach

The shape decides, not the bonds

Each polar bond carries a dipole toward its more electronegative atom. The molecule is polar only when these dipoles do not cancel. The shape decides whether they cancel.

CO₂: polar bonds, the dipoles cancel
nonpolar molecule
H₂O: polar bonds, the dipoles add
polar molecule
Dr. Karmach

Every polar bond is an arrow

Draw each polar bond as a dipole arrow. It points to the more electronegative atom, the end that pulls the shared electrons closer. A bigger electronegativity difference means a stronger pull.

Dr. Karmach

When arrows cancel, and when they add

Identical arrows arranged evenly around the center cancel, and the molecule is nonpolar. A lopsided shape, or a central lone pair, leaves a net arrow, and the molecule is polar.

Dr. Karmach

The method

  1. Recall the shape from VSEPR.
  2. Draw the bond dipoles: one arrow per bond, toward the more electronegative atom.
  3. Add the arrows. Identical arrows in a symmetric shape cancel; a leftover arrow means polar.
Dr. Karmach

Worked example 1: carbon dioxide

CO₂: O=C=O
two C=O bonds · wanted: polar or nonpolar?

Carbon dioxide has two polar C=O bonds.

A common first answer: polar bonds, so the molecule is polar. Test it against the shape.

Dr. Karmach

Worked example 1: solution

CO₂: O=C=O
two C=O bonds · wanted: polar or nonpolar?

Step 1 · Recall the shape

Carbon has two bonding groups and no lone pairs. VSEPR gives a linear molecule: the two oxygens sit 180° apart.

Dr. Karmach

Worked example 1: solution

CO₂: O=C=O
two C=O bonds · wanted: polar or nonpolar?
Step 1 · Recall the shape Step 2 · Draw the bond dipoles
ΔEN(C=O): 3.44 − 2.55 = 0.89 · each bond polar, arrow toward O

Both arrows point outward, away from carbon, toward the oxygens.

Dr. Karmach

Worked example 1: solution

CO₂: O=C=O
two C=O bonds · wanted: polar or nonpolar?
Step 1 · Recall the shape Step 2 · Draw the bond dipoles
ΔEN(C=O): 3.44 − 2.55 = 0.89 · each bond polar, arrow toward O
Step 3 · Add the arrows
0.89 toward one O − 0.89 toward the other O = 0 net

The two arrows pull in exactly opposite directions and cancel. No net arrow. Nonpolar.

Dr. Karmach

Worked example 1: solution

CO₂: O=C=O
two C=O bonds · wanted: polar or nonpolar?
Step 1 · Recall the shape Step 2 · Draw the bond dipoles
ΔEN(C=O): 3.44 − 2.55 = 0.89 · each bond polar, arrow toward O
Step 3 · Add the arrows
0.89 toward one O − 0.89 toward the other O = 0 net
The C=O bonds are polar, yet CO₂ is nonpolar. Its linear shape aims the two equal arrows in opposite directions.
Dr. Karmach

Worked example 1: the route on the flowchart

CO₂: O=C=O, linear
no lone pair on C · C=O polar (0.89) · two identical O atoms · found: nonpolar

No lone pair on carbon, polar bonds, identical outer atoms: the two arrows cancel.
Dr. Karmach

Take-home: polar bonds do not make a polar molecule

CO₂: two polar C=O bonds, linear
symmetric: the two arrows cancel → nonpolar
H₂O: two polar O–H bonds, bent
lopsided: the two arrows add → polar

Both molecules have polar bonds. The linear shape cancels them; the bent shape does not. Polar bonds alone are not enough. The shape decides.

Dr. Karmach

Worked example 2: water

H₂O: two O–H bonds
two lone pairs on oxygen · wanted: polar or nonpolar?

Water has two polar O–H bonds and two lone pairs on its oxygen.

Apply the three steps.

Dr. Karmach

Worked example 2: solution

H₂O: two O–H bonds
two lone pairs on oxygen · wanted: polar or nonpolar?

Step 1 · Recall the shape

Oxygen has two bonding groups and two lone pairs. VSEPR gives a bent molecule; the two O–H bonds meet at about 104.5°.

Dr. Karmach

Worked example 2: solution

H₂O: two O–H bonds
two lone pairs on oxygen · wanted: polar or nonpolar?
Step 1 · Recall the shape Step 2 · Draw the bond dipoles
ΔEN(O–H): 3.44 − 2.20 = 1.24 · each bond polar, arrow toward O

Both arrows point from the hydrogens up toward the oxygen.

Dr. Karmach

Worked example 2: solution

H₂O: two O–H bonds
two lone pairs on oxygen · wanted: polar or nonpolar?
Step 1 · Recall the shape Step 2 · Draw the bond dipoles
ΔEN(O–H): 3.44 − 2.20 = 1.24 · each bond polar, arrow toward O
Step 3 · Add the arrows
arrow toward O + arrow toward O → one net arrow through O

The two arrows point the same way, so they reinforce instead of cancel. A net arrow runs through the oxygen. Polar.

Dr. Karmach

Worked example 2: solution

H₂O: two O–H bonds
two lone pairs on oxygen · wanted: polar or nonpolar?
Step 1 · Recall the shape Step 2 · Draw the bond dipoles
ΔEN(O–H): 3.44 − 2.20 = 1.24 · each bond polar, arrow toward O
Step 3 · Add the arrows
arrow toward O + arrow toward O → one net arrow through O
Both molecules have polar bonds, opposite results. Water's bent shape lets the two arrows add, and the lone pairs keep it from ever being symmetric.
Dr. Karmach

Worked example 2: the route on the flowchart

H₂O: bent, two lone pairs on O
two lone pairs on O · O–H polar (1.24) · found: polar

The first question settles it: lone pairs on the central oxygen leave the molecule lopsided. ✓
Dr. Karmach

Your turn: ammonia

NH₃: three N–H bonds, one lone pair on nitrogen
ΔEN(N–H) = 3.04 − 2.20 = 0.84 → each bond polar
shape: · three arrows toward N · they → NH₃ is

Recall the shape, draw the three arrows, then decide whether they cancel.

Dr. Karmach

Your turn: ammonia

NH₃: three N–H bonds, one lone pair on nitrogen
ΔEN(N–H) = 3.04 − 2.20 = 0.84 → each bond polar
shape: · three arrows toward N · they → NH₃ is

Recall the shape, draw the three arrows, then decide whether they cancel.

shape: trigonal pyramidal · three arrows toward N, tilted to one side · they do not cancel → NH₃ is polar

The lone pair pushes the three N–H bonds to one side, so their arrows cannot balance. A net arrow points through the nitrogen.

Dr. Karmach

Where this goes wrong

Polar bonds, so a polar molecule. CO₂ has two polar C=O bonds, and the leap to "so CO₂ is polar" skips the shape. Linear and symmetric, its two arrows cancel: nonpolar. The bonds do not decide; the shape does.
Calling a symmetric shape lopsided. SO₃ is trigonal planar with three identical S=O bonds and no lone pair on sulfur. Claiming the arrows "add up" ignores that three equal arrows 120° apart cancel exactly. Identical outer atoms in an even arrangement balance.
Nonpolar for the wrong reason. CCl₄ is nonpolar, but not because its bonds are nonpolar. Each C–Cl bond is polar. The molecule is nonpolar because the tetrahedral shape cancels the four arrows.
Missing the lone pair. Treating NH₃ as a flat, even molecule calls it nonpolar. The lone pair on nitrogen tilts the three N–H arrows to one side, and they no longer cancel: polar.
Dr. Karmach

Practice 1

BCl₃: three B–Cl bonds, trigonal planar, no lone pair on boron
ΔEN(B–Cl) = 3.16 − 2.04 = 1.12 → each bond polar

Boron trichloride has three identical polar bonds in a flat triangle. Polar or nonpolar, and why?

  1. Polar: the trigonal planar shape places the three arrows asymmetrically, so they add up
  2. Polar: it contains polar B–Cl bonds, so the whole molecule must be polar
  3. Nonpolar: the B–Cl bonds are polar, but the trigonal planar shape is symmetric, so the three arrows cancel
  4. Nonpolar: none of its B–Cl bonds are polar in the first place
Dr. Karmach

Practice 1 answer: C

BCl₃ → nonpolar → answer C
three polar B–Cl arrows, 120° apart, cancel → no net arrow
trigonal planar, symmetric · three arrows toward Cl, 120° apart → cancel: nonpolar

B took polar bonds as proof of a polar molecule and skipped the shape: the symmetric triangle cancels the three equal arrows. A called the symmetric shape lopsided, but three identical arrows 120° apart balance exactly. D denied the bonds are polar. ΔEN(B–Cl) = 3.16 − 2.04 = 1.12, so each bond is polar, and the molecule is nonpolar because of the shape, not because the bonds are nonpolar.

Three equal arrows spread evenly around the boron sum to zero. Symmetric polar bonds → nonpolar. ✓
Dr. Karmach

Worked example 3: two tetrahedral molecules

CCl₄ and CHCl₃: both tetrahedral, carbon at the center
four C–Cl bonds · CHCl₃ swaps one Cl for H · wanted: each polar or nonpolar?

Two molecules with the same tetrahedral shape. CCl₄ has four C–Cl bonds; CHCl₃ replaces one chlorine with a hydrogen.

Judge each: polar or nonpolar?

Dr. Karmach

Worked example 3: shape and dipoles

CCl₄ and CHCl₃: both tetrahedral, carbon at the center
wanted: each molecule polar or nonpolar?

Step 1 · Recall the shape

Both are tetrahedral: four bonding groups on carbon, no lone pairs, the outer atoms 109.5° apart.

Dr. Karmach

Worked example 3: shape and dipoles

CCl₄ and CHCl₃: both tetrahedral, carbon at the center
wanted: each molecule polar or nonpolar?
Step 1 · Recall the shape Step 2 · Draw the bond dipoles
ΔEN(C–Cl): 3.16 − 2.55 = 0.61 · ΔEN(C–H): 2.55 − 2.20 = 0.35 · C–Cl polar · C–H under 0.4, nearly nonpolar

Each C–Cl arrow points toward its chlorine; the weaker C–H arrow points toward carbon.

Dr. Karmach

Worked example 3: shape and dipoles

CCl₄ and CHCl₃: both tetrahedral, carbon at the center
wanted: each molecule polar or nonpolar?
Step 1 · Recall the shape Step 2 · Draw the bond dipoles
ΔEN(C–Cl): 3.16 − 2.55 = 0.61 · ΔEN(C–H): 2.55 − 2.20 = 0.35 · C–Cl polar · C–H under 0.4, nearly nonpolar
The C–Cl bonds are polar. Whether the molecule is polar now depends only on how the four arrows are arranged.
Dr. Karmach

Worked example 3: adding the arrows

same tetrahedral shape, one outer atom swapped
CCl₄ → nonpolar · CHCl₃ → polar

Step 3 · Add the arrows

CCl₄'s four identical arrows cancel; swapping one chlorine for hydrogen leaves the three chlorine arrows unbalanced, so a net arrow remains: polar. ✓
Dr. Karmach

Worked example 3: the route on the flowchart

CCl₄ and CHCl₃: tetrahedral, no lone pair on C
no lone pair on C · C–Cl polar (0.61) · CCl₄: four identical Cl → nonpolar · CHCl₃: H and Cl mixed → polar

Same shape, same first two answers. The outer atoms alone split the two molecules.
Dr. Karmach

Practice 2

SiF₄ · PCl₃ · OCS · CF₄
wanted: every nonpolar molecule in the set

Which of these molecules are nonpolar?

  1. SiF₄, OCS and CF₄
  2. SiF₄ and CF₄
  3. SiF₄, PCl₃ and CF₄
  4. None of them: every one contains polar bonds
Dr. Karmach

Practice 2 answer: B

nonpolar: SiF₄ and CF₄ → answer B
SiF₄, CF₄ tetrahedral, four identical arrows cancel · PCl₃ trigonal pyramidal, lone pair → polar · OCS linear, O and S pull unequally → polar

A read OCS as symmetric like CO₂; linear cancels only when both outer atoms are identical, and C=O out-pulls C=S. C missed the lone pair on phosphorus and treated PCl₃ as a flat triangle; three bonds plus one lone pair make it pyramidal and polar. D took polar bonds as proof of a polar molecule; SiF₄ and CF₄ have polar bonds and cancel by shape.

Nonpolar needs both: a symmetric shape and identical outer atoms. ✓
Dr. Karmach

Practice 3

CH₄ · NF₃ · SO₂ · CH₃Br
wanted: the one nonpolar molecule

Which one of these molecules is nonpolar?

  1. CH₄
  2. NF₃
  3. SO₂
  4. CH₃Br
Dr. Karmach

Practice 3 answer: A

CH₄ → nonpolar → answer A
NF₃: lone pair on N, pyramidal · SO₂: lone pair on S, bent · CH₃Br: one Br among three H
CH₄: tetrahedral, no lone pair on C · four identical C–H arrows → cancel: nonpolar → answer A

B stopped at three identical fluorines; identical outer atoms cancel only around a symmetric center, and the lone pair on nitrogen pushes all three N–F arrows to one side. C drew SO₂ straight like CO₂; the lone pair on sulfur bends it, and the two sulfur–oxygen arrows add. D stopped at the tetrahedral shape; one Br among three H leaves the C–Br arrow with no equal partner.

CH₄ and CH₃Br share the tetrahedral shape; only CH₄ keeps four identical outer atoms. ✓
Dr. Karmach

Practice 4

CH₂O: formaldehyde, C is the central atom
electronegativity: H = 2.20 · C = 2.55 · O = 3.44

Is formaldehyde polar or nonpolar, and why?

  1. Nonpolar: it is trigonal planar with no lone pair on carbon, so the three arrows cancel
  2. Polar: the lone pairs on oxygen bend the molecule
  3. Polar: its C=O bond is polar, and a polar bond always makes a polar molecule
  4. Polar: H and O are not identical outer atoms, so the arrows cannot cancel
Dr. Karmach

Practice 4 answer: D

CH₂O: 4 + 2(1) + 6 = 12 valence e⁻
C–H, C–H and C=O use 8 · 12 − 8 = 4 left = 2 lone pairs on O · none on C · trigonal planar
outer atoms H, H, O · ΔEN(C=O) = 0.89 · ΔEN(C–H) = 0.35 → unbalanced: polar → answer D

A stopped at the shape; trigonal planar cancels only when all three outer atoms are identical, as in BCl₃. B let the outer atom's lone pairs set the shape; only lone pairs on the central atom do, and carbon has none. C has the right verdict for a wrong reason: CO₂ has polar bonds and is nonpolar.

Same shape as BCl₃, opposite answer: the strong C=O arrow has no equal partner. ✓
Dr. Karmach

Practice 5

I HCN · II SiCl₄ · III NCl₃
electronegativity: H = 2.20 · C = 2.55 · N = 3.04 · Si = 1.90 · Cl = 3.16

Which of these molecules are polar?

  1. I only
  2. I and III
  3. I and II
  4. III only
Dr. Karmach

Practice 5 answer: B

polar: I HCN and III NCl₃ → answer B
HCN: linear, H and N differ · SiCl₄: tetrahedral, four identical Cl · NCl₃: 5 + 3(7) = 26, 26 − 24 = 2 left: one lone pair on N, pyramidal
ΔEN: C≡N 3.04 − 2.55 = 0.49 · Si–Cl 3.16 − 1.90 = 1.26 · N–Cl 3.16 − 3.04 = 0.12

A skipped the lone-pair question for NCl₃: 0.12 is under 0.4, but the lone pair on nitrogen makes the molecule pyramidal and polar anyway. C judged by the bonds alone: SiCl₄ has the most polar bonds in the set, 1.26, yet its four identical arrows cancel. D read HCN as symmetric like CO₂; a linear shape cancels only when both outer atoms are identical.

The most polar bonds sit in the one nonpolar molecule. The shape decides. ✓
Dr. Karmach

Check yourself

  1. BeCl₂ has two polar Be–Cl bonds in a linear shape, with no lone pair on beryllium. Polar or nonpolar? Give the reason.
  2. A molecule is built from polar bonds yet turns out nonpolar. What must be true about its shape and its outer atoms?

Polar or nonpolar is now a two-step call: name the shape, then add the arrows. And the logic does not stop at four domains. Central atoms from period 3 on can hold five or six electron groups, and the same symmetry test decides their polarity too.

Dr. Karmach

7 · Five & Six Electron Domains

Predict the shapes built on five or six electron domains by seating lone pairs in the roomiest corners, and decide whether the finished molecule is polar.

Dr. Karmach

Six neighbors on one atom

High-voltage breakers quench their sparks in sulfur hexafluoride gas. Six fluorines crowd around one sulfur atom. Four corners cannot seat six neighbors.

Dr. Karmach

Four domains: the shapes you know

CH₄ 4 + 0 → tetrahedral · NH₃ 3 + 1 → trigonal pyramidal · H₂O 2 + 2 → bent
4 domains each · tetrahedral geometry each time · the lone pairs change the shape, not the geometry

Electron domains spread as far apart as they can. Count the domains, name the geometry, then read only the atoms. That routine names every four-domain shape. It works unchanged for five and six.

Dr. Karmach

Five and six domains

Electron domains spread as far apart as they can. That rule does not stop at four. Central atoms from period 3 on can hold five or six domains, an expanded octet.

5 domains → trigonal bipyramidal
3 equatorial corners + 2 axial corners
6 domains → octahedral
6 identical corners · every neighbor at 90°
Dr. Karmach

Trigonal bipyramidal: two kinds of corners

Five domains make two kinds of corners. Three equatorial corners ring the middle; two axial corners cap the ends.

equatorial: 120° from each other · 90° from the axial corners
axial: 180° from each other · 90° from all 3 equatorial corners
Dr. Karmach

Lone pairs take equatorial corners

A lone pair is held by one atom, so it spreads wider than a bonding pair. Wide pairs crowd less in an equatorial corner: two neighbors at 90°, not three.

axial lone pair: 3 close contacts at 90° ✗
equatorial lone pair: 2 close contacts at 90° ✓
Dr. Karmach

The five-domain family

Lone pairs replace equatorial atoms one at a time. Five domains read as trigonal bipyramidal, seesaw, T-shaped, or linear as the shaded corners fill with lone pairs.

Dr. Karmach

The six-domain family

An octahedron's six corners are identical, every neighbor at 90°. One lone pair leaves a square pyramid. A second lone pair sits opposite the first, leaving a square plane.

Dr. Karmach

The method

  1. Count the domains. One per bonded atom, one per lone pair.
  2. Name the geometry. 5 trigonal bipyramidal, 6 octahedral.
  3. Seat the lone pairs. Equatorial first; opposite each other in an octahedron.
  4. Name the shape. Atom positions only.

Dr. Karmach

Worked example 1: phosphorus pentafluoride

PF₅: P bonded to 5 F
central atom: phosphorus · 5 bonded F · 0 lone pairs on P

Phosphorus bonds to five fluorines with no lone pairs left over. Give the electron-pair geometry, the molecular shape, and the bond angles.

Dr. Karmach

Worked example 1: solution

PF₅: P bonded to 5 F
central atom: phosphorus · 5 bonded F · 0 lone pairs on P

Step 1 · Count the domains

Five bonded fluorines and no lone pairs on phosphorus: 5 + 0 = 5 electron domains.

Dr. Karmach

Worked example 1: solution

PF₅: P bonded to 5 F
central atom: phosphorus · 5 bonded F · 0 lone pairs on P
Step 1 · Count the domains Step 2 · Name the geometry

Five domains spread into a trigonal bipyramid: three equatorial corners at 120°, two axial corners at 90° to them.

Dr. Karmach

Worked example 1: solution

PF₅: P bonded to 5 F
central atom: phosphorus · 5 bonded F · 0 lone pairs on P
Step 1 · Count the domains Step 2 · Name the geometry Step 3 · Seat the lone pairs

There are none. Every corner holds a fluorine.

Dr. Karmach

Worked example 1: solution

PF₅: P bonded to 5 F
central atom: phosphorus · 5 bonded F · 0 lone pairs on P
Step 1 · Count the domains Step 2 · Name the geometry Step 3 · Seat the lone pairs Step 4 · Name the shape
PF₅ → trigonal bipyramidal
5 domains · 0 lone pairs · 120° equatorial · 90° axial-to-equatorial · 180° axial-to-axial
Dr. Karmach

Worked example 1: solution

PF₅: P bonded to 5 F
central atom: phosphorus · 5 bonded F · 0 lone pairs on P
Step 1 · Count the domains Step 2 · Name the geometry Step 3 · Seat the lone pairs Step 4 · Name the shape
PF₅ → trigonal bipyramidal
5 domains · 0 lone pairs · 120° equatorial · 90° axial-to-equatorial · 180° axial-to-axial
No lone pairs, so the shape is the electron-pair geometry itself. Two kinds of corners give two angles between neighboring bonds, 120° and 90°, plus 180° straight across the axis.

Dr. Karmach

Worked example 2: sulfur tetrafluoride

SF₄: S bonded to 4 F, with 1 lone pair on S
central atom: sulfur · 4 bonded F · 1 lone pair

Sulfur holds four bonded fluorines and one lone pair. A common first attempt seats the lone pair in an axial corner. Find the molecular shape.

Dr. Karmach

Worked example 2: solution

SF₄: S bonded to 4 F, with 1 lone pair on S

Step 1 · Count the domains

Four bonded fluorines plus one lone pair: 4 + 1 = 5 electron domains.

Dr. Karmach

Worked example 2: solution

SF₄: S bonded to 4 F, with 1 lone pair on S
Step 1 · Count the domains Step 2 · Name the geometry

Five domains arrange as a trigonal bipyramid.

Dr. Karmach

Worked example 2: solution

SF₄: S bonded to 4 F, with 1 lone pair on S
Step 1 · Count the domains Step 2 · Name the geometry A common first attempt
lone pair axial → 3 close contacts at 90° ✗
lone pair equatorial → 2 close contacts at 90° ✓

An axial lone pair would press on three bonding pairs at 90°. An equatorial corner has only two such neighbors, so the wide pair takes it.

Dr. Karmach

Worked example 2: solution

SF₄: S bonded to 4 F, with 1 lone pair on S
Step 1 · Count the domains Step 2 · Name the geometry A common first attempt
lone pair axial → 3 close contacts at 90° ✗
lone pair equatorial → 2 close contacts at 90° ✓
Step 3 · Seat the lone pairs

The lone pair takes an equatorial corner. Two axial fluorines and two equatorial fluorines remain.

Dr. Karmach

Worked example 2: solution

SF₄: S bonded to 4 F, with 1 lone pair on S
Step 1 · Count the domains Step 2 · Name the geometry A common first attempt
lone pair axial → 3 close contacts at 90° ✗
lone pair equatorial → 2 close contacts at 90° ✓
Step 3 · Seat the lone pairs Step 4 · Name the shape
SF₄ → seesaw
5 domains · 1 equatorial lone pair · 2 axial F + 2 equatorial F
Dr. Karmach

Worked example 2: solution

SF₄: S bonded to 4 F, with 1 lone pair on S
Step 1 · Count the domains Step 2 · Name the geometry A common first attempt
lone pair axial → 3 close contacts at 90° ✗
lone pair equatorial → 2 close contacts at 90° ✓
Step 3 · Seat the lone pairs Step 4 · Name the shape
SF₄ → seesaw
5 domains · 1 equatorial lone pair · 2 axial F + 2 equatorial F
One equatorial corner holds the lone pair. Its push squeezes the seesaw's angles slightly.

Dr. Karmach

Take-home: lone pairs sit equatorial

equatorial lone pair: 2 neighbors at 90° ✓
axial lone pair: 3 neighbors at 90° ✗ · more crowding

A lone pair spreads wider than a bonding pair. In a trigonal bipyramid every lone pair takes an equatorial corner, and the atoms fit around that choice.

Dr. Karmach

Guided example: krypton difluoride

KrF₂
only the formula · no bonds or lone pairs drawn yet

Krypton is a noble gas, yet it bonds to two fluorines. Find the lone pairs on krypton, then name the molecular shape.

Dr. Karmach

Guided example: the lone pairs

KrF₂: 8 + 2(7) = 22 valence electrons
F–Kr–F: 2 bonds use 2 × 2 = 4 · each F takes 6 more: 2 × 6 = 12 · 22 − 4 − 12 = 6 left on Kr

Step 1 · Count the domains

Every fluorine has its octet. The 6 leftover electrons stay on krypton as 3 lone pairs.

Dr. Karmach

Guided example: the lone pairs

KrF₂: 8 + 2(7) = 22 valence electrons
F–Kr–F: 2 bonds use 2 × 2 = 4 · each F takes 6 more: 2 × 6 = 12 · 22 − 4 − 12 = 6 left on Kr
Step 1 · Count the domains
KrF₂: 2 bonded F + 3 lone pairs = 5 domains
Kr holds 4 + 6 = 10 electrons · period 4, so the octet may expand
Stopping at eight would leave 2 electrons unplaced. All 22 must be placed, so krypton carries five domains.
Dr. Karmach

Guided example: the shape

KrF₂: 2 bonded F + 3 lone pairs on Kr = 5 domains
from the count: 22 − 4 − 12 = 6 left → 3 lone pairs

Step 2 · Name the geometry

Five domains spread into a trigonal bipyramid.

Dr. Karmach

Guided example: the shape

KrF₂: 2 bonded F + 3 lone pairs on Kr = 5 domains
from the count: 22 − 4 − 12 = 6 left → 3 lone pairs
Step 2 · Name the geometry Step 3 · Seat the lone pairs

Lone pairs go equatorial first. Three lone pairs fill all three equatorial corners, so both fluorines sit on the axis.

Dr. Karmach

Guided example: the shape

KrF₂: 2 bonded F + 3 lone pairs on Kr = 5 domains
from the count: 22 − 4 − 12 = 6 left → 3 lone pairs
Step 2 · Name the geometry Step 3 · Seat the lone pairs Step 4 · Name the shape
KrF₂ → linear
5 domains · 3 equatorial lone pairs · 2 axial F · F–Kr–F = 180°
Dr. Karmach

Guided example: the shape

KrF₂: 2 bonded F + 3 lone pairs on Kr = 5 domains
from the count: 22 − 4 − 12 = 6 left → 3 lone pairs
Step 2 · Name the geometry Step 3 · Seat the lone pairs Step 4 · Name the shape
KrF₂ → linear
5 domains · 3 equatorial lone pairs · 2 axial F · F–Kr–F = 180°
Three lone pairs ring the equator evenly. The two fluorines line up through the middle, 180° apart.

Dr. Karmach

Your turn: chlorine trifluoride

ClF₃: Cl bonded to 3 F, with 2 lone pairs on Cl
central atom: chlorine · 3 bonded F · 2 lone pairs
step count result
1 · domains 3 bonded + 2 lone pairs domains
2 · geometry from 5 domains
3 · seat the lone pairs 2 corners, both 1 equatorial F remains
4 · shape 2 axial F + 1 equatorial F

Fill the four results.

Dr. Karmach

Your turn: chlorine trifluoride

ClF₃: Cl bonded to 3 F, with 2 lone pairs on Cl
central atom: chlorine · 3 bonded F · 2 lone pairs
step count result
1 · domains 3 bonded + 2 lone pairs domains
2 · geometry from 5 domains
3 · seat the lone pairs 2 corners, both 1 equatorial F remains
4 · shape 2 axial F + 1 equatorial F
ClF₃ → T-shaped
3 + 2 = 5 domains · trigonal bipyramidal geometry · both lone pairs equatorial · angles ≈ 90°

Dr. Karmach

Where this goes wrong

Seating a lone pair axial. SF₄'s lone pair in an axial corner would leave three fluorines in a flat triangle with one on top: a trigonal pyramid. The wide pair takes an equatorial corner, and the shape is a seesaw.
Naming the electron-pair geometry as the shape. SF₄'s five domains sit trigonal bipyramidal, but one corner holds a lone pair. The shape names only the atoms: seesaw.
Forcing an octet. Treating XeF₂ like H₂O gives 2 + 2 = 4 domains and a bent molecule. Xenon holds 2 bonds + 3 lone pairs = 5 domains, all three lone pairs equatorial: linear.
Placing octahedral lone pairs side by side. XeF₄'s two wide pairs at 90° to each other would crowd. They sit 180° apart, and the four fluorines flatten into a square plane.
Dr. Karmach

Practice 1

BrF₃: Br bonded to 3 F, with 2 lone pairs on Br
central atom: bromine · 3 bonded F · 2 lone pairs

Bromine trifluoride has three bonded fluorines and two lone pairs on bromine. What is its molecular shape?

  1. Trigonal bipyramidal: the five electron domains spread to the five corners
  2. T-shaped: both lone pairs take equatorial corners, leaving the three fluorines in a T
  3. Trigonal planar: the three fluorines spread evenly at 120°
  4. Trigonal pyramidal: three bonds and one lone pair make four domains
Dr. Karmach

Practice 1 answer: B

BrF₃ → T-shaped → answer B
3 bonded F + 2 lone pairs = 5 domains · trigonal bipyramidal geometry · both lone pairs equatorial

A named the electron-pair geometry; two of the five corners hold lone pairs, so the atoms are not a bipyramid. C seats both lone pairs axial to leave a flat triangle, but an axial lone pair presses on three bonding pairs at 90°; the lone pairs go equatorial. D forces an octet with 3 + 1 = 4 domains; bromine holds an expanded octet, 3 + 2 = 5.

Dr. Karmach

Practice 1 answer: B

BrF₃ → T-shaped → answer B
3 bonded F + 2 lone pairs = 5 domains · trigonal bipyramidal geometry · both lone pairs equatorial
Five domains, two of them wide lone pairs in equatorial corners: the three fluorines trace a T, with angles near 90°.

Dr. Karmach

Worked example 3: xenon tetrafluoride

XeF₄: Xe bonded to 4 F, with 2 lone pairs on Xe
central atom: xenon · 4 bonded F · 2 lone pairs · every Xe–F bond polar

Xenon holds four bonded fluorines and two lone pairs. Find the molecular shape, then decide whether the molecule is polar.

Dr. Karmach

Worked example 3: the shape

XeF₄: Xe bonded to 4 F, with 2 lone pairs on Xe
central atom: xenon · 4 bonded F · 2 lone pairs

Step 1 · Count the domains

Four bonded fluorines plus two lone pairs: 4 + 2 = 6 electron domains.

Dr. Karmach

Worked example 3: the shape

XeF₄: Xe bonded to 4 F, with 2 lone pairs on Xe
central atom: xenon · 4 bonded F · 2 lone pairs
Step 1 · Count the domains Step 2 · Name the geometry

Six domains spread into an octahedron. Every corner sits at 90° to its four neighbors.

Dr. Karmach

Worked example 3: the shape

XeF₄: Xe bonded to 4 F, with 2 lone pairs on Xe
central atom: xenon · 4 bonded F · 2 lone pairs
Step 1 · Count the domains Step 2 · Name the geometry Step 3 · Seat the lone pairs

All six corners are identical, so no corner is roomier. The two wide pairs get as far from each other as possible: opposite corners, 180° apart.

Dr. Karmach

Worked example 3: the shape

XeF₄: Xe bonded to 4 F, with 2 lone pairs on Xe
central atom: xenon · 4 bonded F · 2 lone pairs
Step 1 · Count the domains Step 2 · Name the geometry Step 3 · Seat the lone pairs Step 4 · Name the shape
XeF₄ → square planar
6 domains · 2 lone pairs opposite each other · 4 F in one plane at 90°
Dr. Karmach

Worked example 3: the shape

XeF₄: Xe bonded to 4 F, with 2 lone pairs on Xe
central atom: xenon · 4 bonded F · 2 lone pairs
Step 1 · Count the domains Step 2 · Name the geometry Step 3 · Seat the lone pairs Step 4 · Name the shape
XeF₄ → square planar
6 domains · 2 lone pairs opposite each other · 4 F in one plane at 90°
Two opposite corners empty out, and the four fluorines flatten into a square around the xenon.

Dr. Karmach

Worked example 3: the polarity

XeF₄ square planar: 4 polar Xe–F bonds
4 equal arrows toward the corners of a square · 2 lone pairs at 180°

Polarity · Add the bond dipoles

Each Xe–F arrow has a partner pointing exactly the other way, so the four cancel in pairs. The two lone pairs sit opposite each other and balance as well.

Dr. Karmach

Worked example 3: the polarity

XeF₄ square planar: 4 polar Xe–F bonds
4 equal arrows toward the corners of a square · 2 lone pairs at 180°

Polarity · Add the bond dipoles

Each Xe–F arrow has a partner pointing exactly the other way, so the four cancel in pairs. The two lone pairs sit opposite each other and balance as well.

XeF₄ → nonpolar
4 equal arrows in a square cancel · 2 lone pairs at 180° cancel
Every arrow and both lone pairs have an exact opposite. Square planar with identical outer atoms is nonpolar.

Dr. Karmach

Take-home: square planar cancels, seesaw does not

XeF₄ square planar: every arrow has a partner straight across → nonpolar
the 2 lone pairs at 180° balance as well
SF₄ seesaw: the 2 equatorial arrows share a side → polar
no arrow comes from the lone pair's corner to balance them

Symmetry decides. In a square plane every dipole has an exact opposite. A seesaw leaves two equatorial arrows unanswered, so a net dipole remains.

Dr. Karmach

Practice 2

BrF₅: Br bonded to 5 F, with 1 lone pair on Br
square pyramidal · every Br–F bond polar · all outer atoms identical

Bromine pentafluoride is square pyramidal, with five identical polar bonds. Polar or nonpolar, and why?

  1. Polar: the four base arrows cancel in pairs, but the fifth arrow faces the lone pair's corner and has no partner
  2. Nonpolar: five identical polar bonds always cancel, whatever the arrangement
  3. Nonpolar: the Br–F bonds are not polar in the first place
  4. Polar: any molecule that contains polar bonds is polar
Dr. Karmach

Practice 2 answer: A

BrF₅ → polar → answer A
4 base arrows cancel in pairs · the fifth arrow faces the lone pair · net arrow along the axis

B assumes identical atoms always cancel; they cancel only when every arrow has a partner straight across, and here the fifth arrow faces a lone pair instead. C denies the bonds are polar; fluorine out-pulls bromine, so every bond is polar. D overgeneralizes; polar bonds alone decide nothing, since SF₆ holds six polar bonds and is nonpolar.

Dr. Karmach

Practice 2 answer: A

BrF₅ → polar → answer A
4 base arrows cancel in pairs · the fifth arrow faces the lone pair · net arrow along the axis
One arrow without a partner is all it takes. Square pyramidal keeps a net dipole, like seesaw and T-shaped.

Dr. Karmach

Practice 3

IF₄⁺
a cation · iodine bonded to 4 F

What is the molecular shape of the IF₄⁺ ion?

  1. Tetrahedral
  2. Trigonal bipyramidal
  3. Square planar
  4. Trigonal pyramidal
  5. Seesaw
Dr. Karmach

Practice 3 answer: E

IF₄⁺: 7 + 4(7) − 1 = 34 · 34 − 4(2) − 4(6) = 2 left on I → 1 lone pair
the 1+ charge removes one electron · 4 bonded F + 1 lone pair = 5 domains · lone pair equatorial · seesaw → answer E

A stopped after the outer octets; the 2 leftover electrons are a lone pair on iodine, so 4 + 0 = 4 undercounts. B named the electron-pair geometry; one corner holds the lone pair. C added an electron for the 1+ charge: 7 + 4(7) + 1 = 36 and 36 − 8 − 24 = 4, two lone pairs and 4 + 2 = 6 domains. A positive charge removes electrons. D seated the lone pair axial; an equatorial corner has fewer neighbors at 90°.

Dr. Karmach

Practice 3 answer: E

IF₄⁺: 7 + 4(7) − 1 = 34 · 34 − 4(2) − 4(6) = 2 left on I → 1 lone pair
the 1+ charge removes one electron · 4 bonded F + 1 lone pair = 5 domains · lone pair equatorial · seesaw → answer E
Same count as SF₄: 34 electrons, 4 bonds, 1 lone pair. The lone pair takes an equatorial corner, and the four fluorines form a seesaw.

Dr. Karmach

Practice 4

CF₄: tetrahedral · SeF₄: seesaw
both: 4 bonded F on one central atom · carbon in period 2 · selenium in period 4

Both molecules hold four fluorines on one central atom. Why are their shapes different?

  1. Selenium is a larger atom, so its four bonds spread into a wider shape
  2. The Se–F bonds are polar, and polar bonds bend out of a tetrahedron
  3. Selenium keeps one lone pair as a fifth domain; carbon keeps none
  4. Selenium forms one double bond to fluorine, which crowds the other three bonds
Dr. Karmach

Practice 4 answer: C

CF₄: 4 + 4(7) = 32 · 32 − 8 − 24 = 0 left · SeF₄: 6 + 4(7) = 34 · 34 − 8 − 24 = 2 left
CF₄: 4 + 0 = 4 domains, tetrahedral · SeF₄: 4 + 1 = 5 domains, lone pair equatorial, seesaw → answer C

A credits atom size; a larger atom makes longer bonds, but the number of domains sets the shape. B blames bond polarity; C–F bonds are polar too, and CF₄ stays tetrahedral. D gives fluorine a double bond; fluorine forms one bond, and four Se–F single bonds are all SeF₄ has.

Dr. Karmach

Practice 4 answer: C

CF₄: 4 + 4(7) = 32 · 32 − 8 − 24 = 0 left · SeF₄: 6 + 4(7) = 34 · 34 − 8 − 24 = 2 left
CF₄: 4 + 0 = 4 domains, tetrahedral · SeF₄: 4 + 1 = 5 domains, lone pair equatorial, seesaw → answer C
Same formula type, different domain count. Selenium's 2 leftover electrons become a lone pair, and that fifth domain turns the tetrahedron into a seesaw.

Dr. Karmach

Practice 5

IF₅: iodine bonded to 5 F
central atom: iodine · 5 I–F single bonds · neutral molecule

What is the molecular shape of iodine pentafluoride?

  1. Trigonal bipyramidal
  2. Octahedral
  3. Seesaw
  4. Square pyramidal
Dr. Karmach

Practice 5 answer: D

IF₅: 7 + 5(7) = 42 · 42 − 5(2) − 5(6) = 2 left on I
5 bonds use 10 · each F takes 6, 30 in all · 5 bonded F + 1 lone pair = 6 domains · octahedral geometry · square pyramidal → answer D

A stopped after the outer octets; the 2 electrons left over sit on iodine as a lone pair, a sixth domain, so 5 + 0 = 5 undercounts. B named the electron-pair geometry; one of the six corners holds the lone pair, not an atom. C matched "one lone pair" to SF₄'s seesaw; SF₄ has 4 + 1 = 5 domains, IF₅ has 5 + 1 = 6.

Dr. Karmach

Practice 5 answer: D

IF₅: 7 + 5(7) = 42 · 42 − 5(2) − 5(6) = 2 left on I
5 bonds use 10 · each F takes 6, 30 in all · 5 bonded F + 1 lone pair = 6 domains · octahedral geometry · square pyramidal → answer D
Five fluorines and one lone pair fill the octahedron's six corners. The atoms trace a square base with one fluorine on top.

Dr. Karmach

Practice 6

SeF₆ · TeF₄ · AsF₅ · IF₃
every bond polar · the outer atoms in each molecule identical

Which of these molecules are nonpolar?

  1. SeF₆ only
  2. SeF₆ and AsF₅
  3. SeF₆, TeF₄ and AsF₅
  4. SeF₆, AsF₅ and IF₃
  5. All four
Dr. Karmach

Practice 6 answer: B

left on center: SeF₆ 48 − 12 − 36 = 0 · AsF₅ 40 − 10 − 30 = 0 · TeF₄ 34 − 8 − 24 = 2 · IF₃ 28 − 6 − 18 = 4
SeF₆ 6 + 0, octahedral · AsF₅ 5 + 0, trigonal bipyramidal · TeF₄ 4 + 1, seesaw · IF₃ 3 + 2, T-shaped → nonpolar: SeF₆ and AsF₅, answer B

A judged AsF₅ polar for its two kinds of corners; the 2 axial arrows cancel each other, and the 3 equatorial arrows at 120° cancel too. C read TeF₄'s four identical F as balanced; its lone pair empties an equatorial corner, so 2 equatorial arrows share a side. D let IF₃'s lone pairs cancel its equatorial bond; lone pairs only place the atoms, and that arrow has no partner. E assumed identical outer atoms always cancel; only a symmetric arrangement does.

Dr. Karmach

Practice 6 answer: B

left on center: SeF₆ 48 − 12 − 36 = 0 · AsF₅ 40 − 10 − 30 = 0 · TeF₄ 34 − 8 − 24 = 2 · IF₃ 28 − 6 − 18 = 4
SeF₆ 6 + 0, octahedral · AsF₅ 5 + 0, trigonal bipyramidal · TeF₄ 4 + 1, seesaw · IF₃ 3 + 2, T-shaped → nonpolar: SeF₆ and AsF₅, answer B
No lone pair on the center: every arrow is balanced, so the molecule is nonpolar. In this set, each lone pair leaves an arrow unanswered.

Dr. Karmach

Check yourself

  1. PCl₅ has five bonded chlorines and no lone pairs on phosphorus. Give the electron-pair geometry, the molecular shape, and both bond angles.
  2. XeF₂ holds two bonded fluorines and three lone pairs. Where do the lone pairs sit, and is the molecule polar or nonpolar?

Shapes and dipoles settle how molecules meet. The closing question is strength: how firmly the bonds themselves hold. That story starts with the ionic lattice, where the grip of a whole crystal can be measured, and ends at the price of breaking one covalent bond.

Dr. Karmach

8 · Lattice Energy Trends

Rank or compare ionic compounds by lattice energy using Coulomb's law (charge product first, then ion size) and connect a larger lattice energy to a higher melting point and greater hardness.

Dr. Karmach

Why some salts refuse to melt

Salt melts at 801 °C; magnesium oxide holds its shape past 2800 °C. Same ionic bond, but two levers make the lattice energy wildly different.

Dr. Karmach

Ionic solids: opposite charges attract

A metal gives electrons to a nonmetal, and the ions attract. The periodic table sets both things that control that pull: each ion's charge, from its group, and its size, which grows down a group.

group 1: Na⁺ · group 2: Mg²⁺ · group 16: O²⁻ · group 17: Cl⁻  ·  MgCl₂ is Mg²⁺ with Cl⁻
a subscript counts ions, not charge · ions grow down a group: Li⁺ < Na⁺ < K⁺ · F⁻ < Cl⁻ < Br⁻ < I⁻
Dr. Karmach

Lattice energy: ionic bond strength

Bond strength is measured twice: lattice energy for ionic solids, bond energies for covalent bonds. Lattice energy is the energy that holds one mole of an ionic solid together, reported as a positive magnitude.

MX(s) → M⁺(g) + X⁻(g)   ΔH_lattice > 0
bigger magnitude = stronger bonding · running it in reverse (ions → solid) releases the same energy
Dr. Karmach

Coulomb's law sets the pull

The attraction is electrostatic, so lattice energy follows Coulomb's law: just two knobs.

|lattice energy| ∝ (Q₁ · Q₂) / d
Q₁, Q₂ = the ion charges · d = distance between ion centers ≈ sum of the two ionic radii

The charge product sits on top; the separation d sits on the bottom. Every trend is just this equation read carefully.

Dr. Karmach

Lever 1: charge is the big jump

Charge is a product in the numerator, so it swings hardest. Go from 1+/1− to 2+/2− and the lattice energy roughly quadruples, even at similar sizes.

MgO (Q₁Q₂ = 4): 3795  ≫  NaF (Q₁Q₂ = 1): 923 kJ/mol
3795 / 923 ≈ 4.1: quadruple the charge product, quadruple the pull (d ≈ 212 vs 235 pm)
Dr. Karmach

Lever 2: size is the fine adjustment

Hold the charges equal and only d changes. Smaller ions sit closer (shorter d, larger lattice energy) while bigger ions weaken it.

NaF 923 > NaCl 787 > NaBr 747 > NaI 704  (anion grows, d ↑)
LiF 1030 > NaF 923 > KF 821: cation grows down a group, d rises · a few hundred kJ/mol, never the fourfold charge jump
Dr. Karmach

What a big lattice energy buys

A stronger lattice resists being pulled apart: by heat, by scratching, by a solvent.

higher lattice energy → higher melting point · harder · less soluble
MgO melts near 2850 °C and serves as a furnace lining; NaCl melts at 801 °C

So a lattice-energy ranking is also, roughly, a melting-point and hardness ranking.

Dr. Karmach

The method: compare two

  1. Charges first. The higher Q₁·Q₂ product usually wins.
  2. Then size. On a tie, smaller ions (shorter d) win.
  3. Read the size trend: ions grow down a group.
  4. Translate: higher lattice energy → higher melting point and hardness.

Dr. Karmach

Guided example: which melts higher

MgO  ·  CaS
wanted: the higher melting point

Both are ionic solids. Predict which one melts at the higher temperature. Run all four steps.

Dr. Karmach

Guided example: solution

MgO: Mg²⁺ with O²⁻, Q₁Q₂ = 2 × 2 = 4  ·  CaS: Ca²⁺ with S²⁻, Q₁Q₂ = 2 × 2 = 4
wanted: the higher melting point · the charge products tie

Step 1 · Charges first

Both are 2+/2−. The charge lever cannot decide.

Dr. Karmach

Guided example: solution

MgO: Mg²⁺ with O²⁻, Q₁Q₂ = 2 × 2 = 4  ·  CaS: Ca²⁺ with S²⁻, Q₁Q₂ = 2 × 2 = 4
wanted: the higher melting point · the charge products tie
Step 1 · Charges first Step 2 · Then size

On a charge tie, the shorter d wins. Compare both ions.

Dr. Karmach

Guided example: solution

MgO: Mg²⁺ with O²⁻, Q₁Q₂ = 2 × 2 = 4  ·  CaS: Ca²⁺ with S²⁻, Q₁Q₂ = 2 × 2 = 4
wanted: the higher melting point · the charge products tie
Step 1 · Charges first Step 2 · Then size Step 3 · Read the size trend

Mg sits above Ca in group 2. O sits above S in group 16. Both MgO ions are smaller.

MgO: d ≈ 72 + 140 = 212 pm  <  CaS: d ≈ 100 + 184 = 284 pm
shorter d, larger lattice energy: MgO > CaS
Dr. Karmach

Guided example: solution

MgO: Mg²⁺ with O²⁻, Q₁Q₂ = 2 × 2 = 4  ·  CaS: Ca²⁺ with S²⁻, Q₁Q₂ = 2 × 2 = 4
wanted: the higher melting point · the charge products tie
Step 1 · Charges first Step 2 · Then size Step 3 · Read the size trend
MgO: d ≈ 72 + 140 = 212 pm  <  CaS: d ≈ 100 + 184 = 284 pm
shorter d, larger lattice energy: MgO > CaS
Step 4 · Translate

The larger lattice energy holds the solid harder, so MgO melts higher.

Measured: MgO 2852 °C, CaS 2525 °C, a gap of 327 °C. Equal charges, so size moves it by hundreds of degrees, not thousands. ✓

Dr. Karmach

Worked example 1

Rank by lattice energy, largest first:  NaBr,  MgO,  NaF
then estimate how many times larger MgO's lattice energy is than NaF's

MgO is built from Mg²⁺ and O²⁻; NaF and NaBr are each 1+/1−. Apply the charge lever first, then break the tie with size.

Dr. Karmach

Worked example 1: solution

Step 1 · Charges first

MgO has Q₁Q₂ = 2 × 2 = 4; NaF and NaBr each have 1 × 1 = 1. The high charge product puts MgO far in front.

Dr. Karmach

Worked example 1: solution

Step 1 · Charges first
Step 2 · Then size

NaF and NaBr tie on charge, so compare d. F⁻ is smaller than Br⁻ (d ≈ 235 vs 298 pm), so NaF > NaBr.

MgO (3795) > NaF (923) > NaBr (747)
charge sets the leader, size orders the rest
Dr. Karmach

Worked example 1: solution

Step 1 · Charges first
Step 2 · Then size

MgO (3795) > NaF (923) > NaBr (747)
charge sets the leader, size orders the rest
Estimate the jump
|LE|(MgO) / |LE|(NaF) ≈ (4/212) / (1/235) ≈ 4.4
measured 3795 / 923 ≈ 4.1: quadrupling the charge product roughly quadruples the lattice energy
Charge moved the answer by a factor of ~4; size only reorders the two 1+/1− salts by a few percent.

Dr. Karmach

Worked example 2

LiF has the smallest ions of any alkali halide.
Does that give it a larger lattice energy than CaO?

Small ions are tempting: a short d means a strong pull. But check the other lever before deciding.

Dr. Karmach

Worked example 2: solution

Step 1 · Charges first

LiF is 1+/1−, so Q₁Q₂ = 1. CaO is 2+/2−, so Q₁Q₂ = 4: four times larger.

Dr. Karmach

Worked example 2: solution

Step 1 · Charges first
Size does not apply

LiF's ions are smaller (d ≈ 209 vs 240 pm), but size only breaks a charge tie. Here 4 beats 1 decisively, so the route stops at Step 1.

CaO (3414 kJ/mol) > LiF (1030 kJ/mol)  ≈ 3.3× larger
3414 / 1030 ≈ 3.3: the fourfold charge edge outweighs LiF's small size advantage
Smallest ions ≠ largest lattice energy. Size is the fine adjustment; charge is the main lever.

Dr. Karmach

Your turn: rank three salts

Rank KCl, CaO, KF by lattice energy, largest first. Fill each rank, using charge first and then size.

compound charge product rank (1 = largest)
CaO
KF
KCl
Dr. Karmach

Your turn: rank three salts

Rank KCl, CaO, KF by lattice energy, largest first. Fill each rank, using charge first and then size.

compound charge product rank (1 = largest)
CaO
KF
KCl
CaO (Q₁Q₂ = 4) > KF (Q₁Q₂ = 1) > KCl (Q₁Q₂ = 1)
CaO wins on charge · KF beats KCl on size, since F⁻ is smaller than Cl⁻ (shorter d)

Dr. Karmach

Where this goes wrong

Letting size beat charge. LiF has the smallest ions of the alkali halides, yet CaO (2+/2−) still crushes it: charge is the stronger lever. Check Q₁·Q₂ first.
Bigger ion, bigger energy. Backwards. A larger ion means a larger d, and d is in the denominator, so the lattice energy gets smaller, not larger.
Adding charges instead of multiplying. It is the product Q₁·Q₂, not the sum. Going 1+/1− → 2+/2− multiplies the product by 4 (1 → 4), not by 2.
Reading the sign, not the size. Whether you call it +923 or −923, compare magnitudes: the bigger number is the stronger lattice.
Dr. Karmach

Practice 1

Which of these ionic solids has the highest lattice energy?

  1. BaO
  2. Na₂O
  3. LiCl
  4. KI
Dr. Karmach

Practice 1 answer: A

BaO: 2 × 2 = 4  ·  Na₂O: 1 × 2 = 2  ·  LiCl: 1 × 1 = 1  ·  KI: 1 × 1 = 1
Q₁·Q₂ for each · only BaO has both ions doubly charged → answer A

B let one 2− ion carry it: Na₂O is Na⁺ with O²⁻, so Q₁Q₂ = 1 × 2 = 2, half of BaO's 4. C let size beat charge: LiCl's ions sit closer than BaO's (d ≈ 257 vs 275 pm), but its product is 1. D ran size backward: KI has the largest ions here, and a longer d lowers the lattice energy.

Ba²⁺ is a large ion, yet BaO still wins. Charge first, size second. ✓

Dr. Karmach

Practice 2

KBr  ·  LiBr
wanted: the greater lattice energy

Which has the greater lattice energy, KBr or LiBr?

  1. KBr: its larger cation attracts Br⁻ more strongly
  2. LiBr: Li⁺ carries a higher charge than K⁺
  3. LiBr: equal charges, and the smaller Li⁺ shortens d
  4. Equal: both are 1+/1− bromides
  5. KBr: its larger formula mass holds it together
Dr. Karmach

Practice 2 answer: C

LiBr: Q₁Q₂ = 1, d ≈ 76 + 196 = 272 pm  ·  KBr: Q₁Q₂ = 1, d ≈ 138 + 196 = 334 pm
charges tie · Li sits above K in group 1, so Li⁺ is smaller · shorter d wins → answer C

A ran size backward: a larger cation means a longer d, and d sits in the denominator. B misread the charge: every group 1 ion is 1+, whatever its row. D stopped at the tie: equal charges hand the decision to size. E credited mass: formula mass is not in Q₁Q₂/d.

A tie on charge is not a tie on lattice energy. LiBr's d is 62 pm shorter, so LiBr wins. ✓

Dr. Karmach

Practice 3

CaS: d = 284 pm  ·  KCl: d = 319 pm
wanted: |LE|(CaS) ÷ |LE|(KCl)

The lattice energy of CaS is about how many times that of KCl?

  1. 2.25
  2. 3.56
  3. 4.00
  4. 4.49
  5. 1.12
Dr. Karmach

Practice 3 answer: D

(2 × 2 / 284) ÷ (1 × 1 / 319) = 4 × 319/284 = 4.49 → answer D
CaS is Ca²⁺ S²⁻, so Q₁Q₂ = 4 · KCl is K⁺ Cl⁻, so Q₁Q₂ = 1 · charge product on top, d on the bottom

A added the charges: (2 + 2)/(1 + 1) × 319/284 = 2.25. B flipped the distance ratio: 4 × 284/319 = 3.56, which rewards the longer d. C stopped at the charge product: 4/1 = 4.00, with size never applied. E skipped the charge lever: 319/284 = 1.12, the distance ratio alone.

Charge sets a factor of 4; CaS's shorter d pushes it a little above 4, since d sits in the denominator.

Dr. Karmach

Practice 4

NaF · BaO · SrO · SrS
wanted: the highest melting point

Which of these ionic solids would you predict to have the highest melting point?

  1. SrO
  2. BaO
  3. SrS
  4. NaF
Dr. Karmach

Practice 4 answer: A

SrO (Q₁Q₂ = 4, d ≈ 258 pm) > BaO (4, 275 pm) > SrS (4, 302 pm) > NaF (1, 235 pm)
charge first, then size · largest lattice energy → highest melting point → answer A

B took the larger cation: Ba²⁺ sits below Sr²⁺, so d grows from 258 to 275 pm. C took the larger anion: S²⁻ sits below O²⁻, so d grows to 302 pm. D let size beat charge: NaF has the shortest d (235 pm), but its charge product is 1 against 4.

Three 2+/2− salts tie on charge. The one with both ions smallest, SrO, holds its lattice hardest and melts highest.

Dr. Karmach

Practice 5

LiF · MgSe · MgS · CS₂
wanted: the largest lattice energy

Which compound has the largest lattice energy?

  1. LiF
  2. MgSe
  3. MgS
  4. CS₂
Dr. Karmach

Practice 5 answer: C

MgS (Q₁Q₂ = 4, d ≈ 256 pm) > MgSe (4, 270 pm) > LiF (1, 209 pm)
CS₂: C = 2.55, S = 2.58, ΔEN = 0.03 · two nonmetals share pairs: molecules, no ions → answer C

A let size beat charge: LiF has the shortest d (209 pm), but its charge product is 1 against 4. B ran size backward: Se²⁻ is larger than S²⁻, so d grows from 256 to 270 pm. D treated CS₂ as C⁴⁺ and S²⁻ ions, giving 4 × 2 = 8. Carbon and sulfur are both nonmetals with a difference of 0.03: nonpolar covalent, no ions, no lattice energy.

Classify the bonding first. Lattice energy belongs to ionic solids; a compound of nonmetals has none.

Dr. Karmach

Practice 6

LiCl · LiF · BaSe · BaS
wanted: increasing lattice energy, smallest first

Arrange the four solids in order of increasing lattice energy.

  1. BaS < BaSe < LiF < LiCl
  2. LiCl < LiF < BaSe < BaS
  3. BaSe < BaS < LiCl < LiF
  4. LiF < LiCl < BaS < BaSe
Dr. Karmach

Practice 6 answer: B

LiCl (Q₁Q₂ = 1, d ≈ 257 pm) < LiF (1, 209 pm) < BaSe (4, 333 pm) < BaS (4, 319 pm)
charge sets the two tiers · inside each tier the shorter d wins → answer B

A is the right ranking read largest first; the question asks for increasing. C ranked by d alone: BaSe and BaS have the longest d (333 and 319 pm), yet their charge product of 4 lifts both above the 1+/1− salts. D ran size backward inside each tier: F⁻ is smaller than Cl⁻, so LiF tops LiCl, and S²⁻ is smaller than Se²⁻, so BaS tops BaSe.

Even the most spread-out 2+/2− salt here, BaSe at 333 pm, outranks the tightest 1+/1− salt, LiF at 209 pm. Charge before size.

Dr. Karmach

Check yourself

  1. Which has the larger lattice energy, KF or KI? Which lever did you use, and which melts higher?
  2. A salt's ions both change from 1+/1− to 3+/3− at the same spacing. By what factor does the lattice energy change?

Charge and size explain why ionic solids differ so widely in melting point and hardness. Lattice energy measures ionic bond strength; bond energies measure the covalent kind, and estimating a reaction's ΔH with them is the next step.

Dr. Karmach

9 · Bond Energies & Reaction Enthalpy

Estimate the enthalpy change of any balanced gas-phase reaction by counting every bond from Lewis structures and applying ΔH ≈ Σ(bond energies broken) − Σ(bond energies formed).

Dr. Karmach

Bonds broken, bonds formed

Every reaction tears old bonds apart and stitches new ones together. Breaking costs energy; forming pays it back. Compare the two totals and you know the heat before running the reaction.

Dr. Karmach

Hess's law, run through free atoms

(1) reactants → free gas atoms · ΔH₁ > 0: every reactant bond breaks
(2) free gas atoms → products · ΔH₂ < 0: every product bond forms
Hess's law: ΔH = ΔH₁ + ΔH₂ · any path gives the same ΔH · Lewis structures list the bonds on each leg

Hess's law lets any path stand in for the real one. Take the path through free atoms: pull every reactant apart, then build every product. The legs carry opposite signs; ΔH is their balance.

Dr. Karmach

Bond energy: the price of one bond

D is the energy to break one mole of a bond in the gas phase. Bonded atoms sit lower in energy than separated ones, so pulling them apart is always a climb.

breaking a bond → ENDOTHERMIC (+, costs energy)
forming a bond → EXOTHERMIC (−, releases energy) · same size, opposite sign
breaking H–H costs +436 kJ/mol · forming H–H releases −436 kJ/mol
memory hook: breaking costs, forming pays · one number used both ways · D itself is always positive
Dr. Karmach

The master formula

A reaction breaks every reactant bond, then forms every product bond. Sum the D values on each side.

ΔH ≈ Σ D(bonds broken) − Σ D(bonds formed)
reactant bonds cost (+) · product bonds pay (−) · negative ΔH → exothermic
O=O: D = 498 · N≡N: D = 941 (kJ/mol)
a double or triple bond is ONE bond with its own larger D · never a stack of singles

Count from the Lewis structures: a bond you did not draw is a bond you will not tally.

Dr. Karmach

The method

  1. Draw every Lewis structure. Balanced equation, gas phase.
  2. Tally bonds broken. Every reactant bond × its coefficient; sum the D values.
  3. Tally bonds formed. Every product bond × its coefficient.
  4. Subtract. ΔH = Σ broken − Σ formed.

Dr. Karmach

Worked example 1: H₂ + Cl₂ → 2 HCl

H₂(g) + Cl₂(g) → 2 HCl(g)
D: H–H = 436 · Cl–Cl = 243 · H–Cl = 431 (kJ/mol)

Reactants hold one H–H bond and one Cl–Cl bond. The products are 2 HCl: two H–Cl bonds. Break the reactant bonds, form the product bonds, and compare.

Dr. Karmach

Worked example 1: solution

H₂(g) + Cl₂(g) → 2 HCl(g)
D: H–H = 436 · Cl–Cl = 243 · H–Cl = 431 (kJ/mol)

Step 1 · Draw every Lewis structure

Three diatomic molecules, one single bond each: H–H, Cl–Cl, and H–Cl twice.

Dr. Karmach

Worked example 1: solution

H₂(g) + Cl₂(g) → 2 HCl(g)
D: H–H = 436 · Cl–Cl = 243 · H–Cl = 431 (kJ/mol)
Step 1 · Draw every Lewis structure Step 2 · Tally bonds broken

One H–H and one Cl–Cl: Σ broken = 436 + 243 = 679 kJ.

Dr. Karmach

Worked example 1: solution

H₂(g) + Cl₂(g) → 2 HCl(g)
D: H–H = 436 · Cl–Cl = 243 · H–Cl = 431 (kJ/mol)
Step 1 · Draw every Lewis structure Step 2 · Tally bonds broken Step 3 · Tally bonds formed

Two H–Cl bonds, from the coefficient 2: Σ formed = 2 × 431 = 862 kJ.

Dr. Karmach

Worked example 1: solution

H₂(g) + Cl₂(g) → 2 HCl(g)
D: H–H = 436 · Cl–Cl = 243 · H–Cl = 431 (kJ/mol)
Step 1 · Draw every Lewis structure Step 2 · Tally bonds broken Step 3 · Tally bonds formed Step 4 · Subtract
ΔH = 679 − 862 = −183 kJ
negative → exothermic · the two H–Cl bonds release more than the H–H and Cl–Cl cost
Dr. Karmach

Worked example 1: solution

H₂(g) + Cl₂(g) → 2 HCl(g)
D: H–H = 436 · Cl–Cl = 243 · H–Cl = 431 (kJ/mol)
Step 1 · Draw every Lewis structure Step 2 · Tally bonds broken Step 3 · Tally bonds formed Step 4 · Subtract
ΔH = 679 − 862 = −183 kJ
negative → exothermic · the two H–Cl bonds release more than the H–H and Cl–Cl cost
Breaking costs 679 kJ; forming pays 862 kJ back. The payback wins by 183 kJ, released as heat.

Dr. Karmach

Worked example 2: 2 H₂ + O₂ → 2 H₂O

2 H₂(g) + O₂(g) → 2 H₂O(g)
D: H–H = 436 · O=O = 498 · O–H = 467 (kJ/mol)

Two traps live here: the coefficient 2 on both H₂ and H₂O, and the O=O double bond (one bond, D = 498). Each water molecule holds two O–H bonds. Estimate ΔH.

Dr. Karmach

Worked example 2: solution

2 H₂(g) + O₂(g) → 2 H₂O(g)
D: H–H = 436 · O=O = 498 · O–H = 467 (kJ/mol)

Step 1 · Draw every Lewis structure

H–H twice, one O=O (one double bond, its own D), and two H–O–H: each water holds two O–H bonds.

Dr. Karmach

Worked example 2: solution

2 H₂(g) + O₂(g) → 2 H₂O(g)
D: H–H = 436 · O=O = 498 · O–H = 467 (kJ/mol)
Step 1 · Draw every Lewis structure Step 2 · Tally bonds broken

Two H–H (2 × 436 = 872) plus one O=O (498): Σ broken = 872 + 498 = 1370 kJ.

Dr. Karmach

Worked example 2: solution

2 H₂(g) + O₂(g) → 2 H₂O(g)
D: H–H = 436 · O=O = 498 · O–H = 467 (kJ/mol)
Step 1 · Draw every Lewis structure Step 2 · Tally bonds broken Step 3 · Tally bonds formed

Two H₂O × two O–H each = 4 O–H bonds: Σ formed = 4 × 467 = 1868 kJ.

Dr. Karmach

Worked example 2: solution

2 H₂(g) + O₂(g) → 2 H₂O(g)
D: H–H = 436 · O=O = 498 · O–H = 467 (kJ/mol)
Step 1 · Draw every Lewis structure Step 2 · Tally bonds broken Step 3 · Tally bonds formed Step 4 · Subtract
ΔH = 1370 − 1868 = −498 kJ
exothermic: this is why hydrogen burns · measured with water as a gas ≈ −484 kJ, close
Dr. Karmach

Worked example 2: solution

2 H₂(g) + O₂(g) → 2 H₂O(g)
D: H–H = 436 · O=O = 498 · O–H = 467 (kJ/mol)
Step 1 · Draw every Lewis structure Step 2 · Tally bonds broken Step 3 · Tally bonds formed Step 4 · Subtract
ΔH = 1370 − 1868 = −498 kJ
exothermic: this is why hydrogen burns · measured with water as a gas ≈ −484 kJ, close
Both traps defused: the O=O kept its own single D value, and the coefficients turned two waters into four O–H bonds.

Dr. Karmach

Take-home: coefficients multiply the bond count

2 H₂O → 2 × 2 = 4 O–H bonds formed
Σ formed = 4 × 467 = 1868 kJ ✓ · ΔH = 1370 − 1868 = −498 kJ
counting one molecule's bonds: Σ formed = 2 × 467 = 934 kJ ✗
ΔH = 1370 − 934 = +436 kJ · the estimate lands on the wrong side of zero

A coefficient multiplies every bond in its molecule. Miss one and a reaction that burns comes out endothermic on paper.

Dr. Karmach

Why the answer is an estimate

The D values are averages: the true C–H in methane differs a little from the C–H in ethanol. And they are gas-phase numbers, while real reactions may involve liquids and solids.

bond-energy ΔH ≈ measured ΔH
averages + gas-phase assumption → an estimate, usually within a few percent · plenty to call exothermic vs endothermic
Dr. Karmach

Your turn: H₂ + Br₂ → 2 HBr

H₂(g) + Br₂(g) → 2 HBr(g)
D: H–H = 436 · Br–Br = 193 · H–Br = 366 (kJ/mol)
step tally result
1 · draw every Lewis structure all single bonds H–H · Br–Br · 2 × H–Br
2 · tally bonds broken 436 + 193 kJ
3 · tally bonds formed 2 × 366 kJ
4 · subtract Σ broken − Σ formed ΔH = kJ

Fill the three results, then call it: exothermic or endothermic?

Dr. Karmach

Your turn: H₂ + Br₂ → 2 HBr

H₂(g) + Br₂(g) → 2 HBr(g)
D: H–H = 436 · Br–Br = 193 · H–Br = 366 (kJ/mol)
step tally result
1 · draw every Lewis structure all single bonds H–H · Br–Br · 2 × H–Br
2 · tally bonds broken 436 + 193 kJ
3 · tally bonds formed 2 × 366 kJ
4 · subtract Σ broken − Σ formed ΔH = kJ

Fill the three results, then call it: exothermic or endothermic?

ΔH = 629 − 732 = −103 kJ → exothermic
broken: 436 + 193 = 629 · formed: 2 × 366 = 732 · forming pays more than breaking costs
Dr. Karmach

Where this goes wrong

Flipping the formula. It is Σ broken − Σ formed, not formed − broken. Reversing it flips the sign and turns exothermic into endothermic.
Ignoring coefficients. 2 HCl means two H–Cl bonds; 2 H₂O means four O–H bonds. Multiply each bond count by its coefficient.
Using a single-bond value for a multiple bond. O=O is 498 and N≡N is 941: one bond each, with their own D. Never split them into singles.
Skipping the Lewis structures. You cannot tally bonds you did not draw. Sketch every molecule first, then count.
Dr. Karmach

Practice 1

O₂(g) + 2 F₂(g) → 2 OF₂(g)
D: O=O = 498 · F–F = 155 · O–F = 190. (kJ/mol)

Estimate ΔH, in kJ, for this reaction.

  1. −760.
  2. +48
  3. +428
  4. −48
Dr. Karmach

Practice 1 answer: B

ΔH = (498 + 2 × 155) − 2 × 2 × 190. = 808 − 760. = +48 kJ → answer B
break O=O + 2 F–F = 498 + 310 = 808 · form 2 OF₂ × 2 O–F = 4 O–F = 4 × 190. = 760.

A (−760.) summed only the bonds formed; the 808 kJ of breaking was never charged. C (+428) forgot the coefficient 2 on OF₂: 808 − 380. = 428. D (−48) reversed the formula: 760. − 808 = −48, the right size with the wrong sign.

Endothermic: the four weak O–F bonds do not repay the O=O and the two F–F. ✓

Dr. Karmach

Practice 2

C₂H₄(g) + 3 O₂(g) → 2 CO₂(g) + 2 H₂O(g)
D: C–H = 413 · C=C = 611 · O=O = 498 · C=O in CO₂ = 799 · O–H = 467 (kJ/mol)

Ethylene burns. Estimate ΔH, in kJ, for this reaction.

  1. −1307
  2. +1307
  3. +1225
  4. −5064
  5. +3757
Dr. Karmach

Practice 2 answer: A

ΔH = (1652 + 611 + 1494) − (3196 + 1868) = 3757 − 5064 = −1307 kJ → answer A
broken: 4 C–H (1652) + 1 C=C (611) + 3 O=O (3 × 498 = 1494) = 3757 · formed: 4 C=O (4 × 799 = 3196) + 4 O–H (1868) = 5064

B (+1307) reversed the formula: 5064 − 3757. C (+1225) ignored both product coefficients, one CO₂ and one H₂O: 1598 + 2 × 467 = 2532, and 3757 − 2532 = +1225. D (−5064) summed the products only. E (+3757) stopped at Σ broken and never subtracted.

Every tally carries a coefficient: 3 O=O broken, 2 CO₂ and 2 H₂O formed. Payback beats cost by 1307 kJ, which is why ethylene burns hot. ✓

Dr. Karmach

Guided example: ammonia as a fuel

NH₃(g) + O₂(g) → N₂(g) + H₂O(g)
unbalanced · D: N–H = 391 · O=O = 498 · N≡N = 941 · O–H = 467 (kJ/mol)

Cargo ships are testing ammonia as a carbon-free fuel. Estimate ΔH, in kJ per mole of NH₃, for its combustion.

Dr. Karmach

Guided example: solution

NH₃(g) + 3/4 O₂(g) → 1/2 N₂(g) + 3/2 H₂O(g)
N: 1 = 1 · H: 3 = 3 · O: 3/2 = 3/2 · D: N–H = 391 · O=O = 498 · N≡N = 941 · O–H = 467 (kJ/mol)

Step 1 · Draw every Lewis structure

Per mole of NH₃ puts a 1 in front of NH₃; fractions balance the rest. NH₃ holds three N–H, O₂ is O=O, N₂ is N≡N, and each H₂O holds two O–H.

Dr. Karmach

Guided example: solution

NH₃(g) + 3/4 O₂(g) → 1/2 N₂(g) + 3/2 H₂O(g)
N: 1 = 1 · H: 3 = 3 · O: 3/2 = 3/2 · D: N–H = 391 · O=O = 498 · N≡N = 941 · O–H = 467 (kJ/mol)
Step 1 · Draw every Lewis structure Step 2 · Tally bonds broken

Three N–H (3 × 391 = 1173) plus 3/4 mol O=O (3/4 × 498 = 373.5): Σ broken = 1546.5 kJ.

Dr. Karmach

Guided example: solution

NH₃(g) + 3/4 O₂(g) → 1/2 N₂(g) + 3/2 H₂O(g)
N: 1 = 1 · H: 3 = 3 · O: 3/2 = 3/2 · D: N–H = 391 · O=O = 498 · N≡N = 941 · O–H = 467 (kJ/mol)
Step 1 · Draw every Lewis structure Step 2 · Tally bonds broken Step 3 · Tally bonds formed

1/2 mol N≡N (1/2 × 941 = 470.5) plus 3/2 H₂O × two O–H = 3 O–H (3 × 467 = 1401): Σ formed = 1871.5 kJ.

Dr. Karmach

Guided example: solution

NH₃(g) + 3/4 O₂(g) → 1/2 N₂(g) + 3/2 H₂O(g)
N: 1 = 1 · H: 3 = 3 · O: 3/2 = 3/2 · D: N–H = 391 · O=O = 498 · N≡N = 941 · O–H = 467 (kJ/mol)
Step 1 · Draw every Lewis structure Step 2 · Tally bonds broken Step 3 · Tally bonds formed Step 4 · Subtract
ΔH = 1546.5 − 1871.5 = −325 kJ per mole of NH₃
exothermic · measured with water as a gas ≈ −317 kJ/mol, close · 4 NH₃ + 3 O₂ → 2 N₂ + 6 H₂O burns 4 mol: 4 × (−325) = −1300 kJ
Dr. Karmach

Guided example: solution

NH₃(g) + 3/4 O₂(g) → 1/2 N₂(g) + 3/2 H₂O(g)
N: 1 = 1 · H: 3 = 3 · O: 3/2 = 3/2 · D: N–H = 391 · O=O = 498 · N≡N = 941 · O–H = 467 (kJ/mol)
Step 1 · Draw every Lewis structure Step 2 · Tally bonds broken Step 3 · Tally bonds formed Step 4 · Subtract
ΔH = 1546.5 − 1871.5 = −325 kJ per mole of NH₃
exothermic · measured with water as a gas ≈ −317 kJ/mol, close · 4 NH₃ + 3 O₂ → 2 N₂ + 6 H₂O burns 4 mol: 4 × (−325) = −1300 kJ
Per mole of fuel fixes the 1 in front of NH₃. Every other coefficient, fractions included, multiplies its bonds. ✓

Dr. Karmach

Practice 3

CH₂CHCH₃(g) + O₂(g) → CO₂(g) + H₂O(g)
unbalanced · D: C–H = 413 · C–C = 347 · C=C = 611 · O=O = 498 · C=O in CO₂ = 799 · O–H = 467 (kJ/mol)

A propene leak catches fire at a refinery. What is ΔH, in kJ per mole of propene burned?

  1. −3662
  2. −3838
  3. −1919
  4. −4160.
Dr. Karmach

Practice 3 answer: C

CH₂CHCH₃ + 9/2 O₂ → 3 CO₂ + 3 H₂O · ΔH = 5677 − 7596 = −1919 kJ/mol → answer C
C: 3 = 3 · H: 6 = 6 · O: 9 = 9 · broken: 6 C–H (2478) + 1 C–C (347) + 1 C=C (611) + 9/2 O=O (2241) = 5677 · formed: 6 C=O (4794) + 6 O–H (2802) = 7596

A (−3662) left O₂ at 1, so one O=O broke: 3436 + 498 = 3934, and 3934 − 7596 = −3662. B (−3838) is ΔH for 2 CH₂CHCH₃ + 9 O₂ → 6 CO₂ + 6 H₂O, two moles of propene. D (−4160.) never broke the O=O bonds: 3436 − 7596.

Measured, with water as a gas: about −1926 kJ/mol, close. Per mole of fuel puts a 1 in front of propene; 9/2 mol of O=O still breaks. ✓

Dr. Karmach

Practice 4

CH₄(g) + Cl₂(g) → CH₃Cl(g) + HCl(g)
D: C–H = 413 · Cl–Cl = 243 · C–Cl = 339 · H–Cl = 431 (kJ/mol)

Chlorine and methane react in ultraviolet light. Estimate ΔH, in kJ, for this reaction.

  1. +1125
  2. +114
  3. +1895
  4. −114
Dr. Karmach

Practice 4 answer: D

ΔH = (4 × 413 + 243) − (3 × 413 + 339 + 431) = 1895 − 2009 = −114 kJ → answer D
broken: 4 C–H (1652) + 1 Cl–Cl (243) = 1895 · formed: 3 C–H (1239) + 1 C–Cl (339) + 1 H–Cl (431) = 2009

A (+1125) left the three C–H bonds of CH₃Cl out of Σ formed: 1895 − 770. = 1125. B (+114) reversed the formula: 2009 − 1895. C (+1895) stopped at Σ broken and never subtracted.

Three C–H bonds break and form again, so they cancel. Only one C–H and the Cl–Cl truly change: (413 + 243) − (339 + 431) = 656 − 770. = −114 kJ. ✓

Dr. Karmach

Practice 5

HCN(g) + 2 H₂(g) → CH₃NH₂(g)
D: C–H = 413 · C≡N = 891 · C–N = 305 · H–H = 436 · N–H = 391 (kJ/mol)

Hydrogen cyanide and hydrogen combine to make methylamine. Estimate ΔH, in kJ, for this reaction.

  1. −736
  2. −2326
  3. −150.
  4. −586
Dr. Karmach

Practice 5 answer: C

ΔH = (413 + 891 + 2 × 436) − (3 × 413 + 305 + 2 × 391) = 2176 − 2326 = −150. kJ → answer C
broken: H–C≡N holds 1 C–H + 1 C≡N, plus 2 H–H (872) = 2176 · formed: CH₃NH₂ holds 3 C–H (1239) + 1 C–N (305) + 2 N–H (782) = 2326

A (−736) drew HCN with a single C–N, the skeleton without its triple bond: 1590. − 2326 = −736. D (−586) broke one H–H, missing the coefficient 2: 1740. − 2326 = −586. B (−2326) summed the products only; the 2176 kJ of breaking was never charged.

The Lewis structure picks the bond. HCN needs C≡N to give C and N an octet; CH₃NH₂ needs only C–N. ✓

Dr. Karmach

Practice 6

CH₃OH(g) + O₂(g) → CO₂(g) + H₂O(g)
unbalanced · D: C–H = 413 · C–O = 358 · O–H = 467 · O=O = 498 · C=O in CO₂ = 799 (kJ/mol)

Methanol fuels some racing engines. Estimate ΔH, in kJ per mole of methanol, for its combustion.

  1. −655
  2. −1310.
  3. −904
  4. −1122
Dr. Karmach

Practice 6 answer: A

CH₃OH + 3/2 O₂ → CO₂ + 2 H₂O · ΔH = 2811 − 3466 = −655 kJ/mol → answer A
broken: 3 C–H (1239) + 1 C–O (358) + 1 O–H (467) + 3/2 O=O (747) = 2811 · formed: 2 C=O (1598) + 2 H₂O × 2 O–H (1868) = 3466

B (−1310.) is ΔH for the whole-number equation, 2 CH₃OH + 3 O₂ → 2 CO₂ + 4 H₂O: 5622 − 6932, two moles of methanol. C (−904) left O₂ at 1, so one O=O broke: 2562 − 3466. D (−1122) left methanol's O–H out of Σ broken: 2344 − 3466.

Per mole of fuel puts a 1 in front of CH₃OH, even when O₂ takes a fraction. Measured, with water as a gas: about −676 kJ/mol, close. ✓

Dr. Karmach

Check yourself

  1. For N₂(g) + 3 H₂(g) → 2 NH₃(g), which bonds break and which form, and how many of each? (You would need D(N≡N), D(H–H), D(N–H).)
  2. A reaction has Σ broken = 1500 kJ and Σ formed = 1350 kJ. Exothermic or endothermic, and what is ΔH?

One model carried this whole unit: electrons shared or transferred, counted by Lewis structures. The count set the shapes, the shapes set the polarity, and here it priced the energy: breaking costs, forming pays. Count the electrons, and the rest follows.

Dr. Karmach

Can you…?

  • ☐ classify a bond as ionic, polar covalent, or nonpolar covalent from the electronegativity difference?
  • ☐ write the Lewis (electron dot) symbol of an atom or a monatomic ion?
  • ☐ count valence electrons and draw valid Lewis structures for molecules and polyatomic ions?
  • ☐ draw all resonance structures of a molecule or ion and describe the blend they represent?
  • ☐ assign formal charges and use them to choose the best Lewis structure?
  • ☐ draw the octet-rule exceptions: incomplete octets, odd-electron molecules, and expanded octets?
  • ☐ apply VSEPR theory to predict electron-pair geometry and molecular shape?
  • ☐ combine bond dipoles with molecular shape to judge whether a molecule is polar?
  • ☐ assign trigonal bipyramidal and octahedral electron geometries and their lone-pair shapes, and judge the polarity of five- and six-domain molecules?

If any box stays empty, the practice site has a drill for it. 🧪

Dr. Karmach

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