CHEM 205 – Dr.

Rogers – WEEK #12

LECTURE TOPICS:

THIS WEEK: Kotz Ch.7 & 9.1 (9th Ed. 9.1-9.2)

Openstax Ch.6 + Ch.8.1-8.3

NEXT: Kotz Ch.10; Openstax Ch.9

(1) No self-study slides in this note set.

Effective nuclear charge helps understand properties
“Core-shielded approx’n” of Z* = useful tool for main group elements:
 treat valence e-s as: (1) all the same (even if have both s & p e-s)
(2) shielded fully by core e-s (& not each other)

Z*approx = (nuclear charge) – (# core e-s)

Lithium nucleus
CORE e-s SHIELD Fluorine
the VALENCE e-s nucleus

EACH valence e- sees:

3+
9+
Li: +3 + (-2) ≈ +1 Core
Core
electron F: +9 + (-2) ≈ +7 !! electrons
“shell” (1s)
(1s orbital) Higher effective nuclear
charge MEANS:
Valence electron Valence e-s
Atom has stronger pull
“shell” (2s orbital) on electrons… (2s & 2p)
 e-s on average (its own, & others ! ) shielded by 1s
(2)
farther out than 1s
(K7.5/OS6.5) Periodic trends in  Atomic & ionic size
element properties  Ionization energy
 Electron affinity

EXPLAINED using effective nuclear charge, estimated by:

1.) calculating Z*approx (how much + charge do the e-s feel?) AND
2.) considering orbital size (how far from this + charge are they?)

Higher effective nuclear charge

…electrons held more tightly
Larger orbitals
…e-s held
less tightly
farther away,
so weaker
electrostatic
attraction to
nucleus…
(3)
Trends in size:  Size  going across period (L→ →R)
as Z* felt by valence electrons 
atomic radii (pm)
for main group
elements Fig.7.5

 Atom size  going

down a group
as add more shells of
core e-s…
Note: below 5th row,
changes in size are small,
because E of high-E
orbitals are very similar…

Transition metals?
• more complex trends
• whole courses
devoted to them
Ion sizes: fewer or more e-s than parent atom?
CATIONS: fewer e-s… ANIONS: more e-s…
∴ smaller than parent atoms ∴ larger than parent atoms
less total shielding more total shielding
 e-s held more tightly  e-s held more loosely

Fig. 7.11 Ionic radii (picometers)

Ions of same type: i.e., + vs -
trends in sizes same as atoms
How hard to remove e-? Ionization E: X(g) → X+(g) + e−
I.E. = quantity of E required to
Fig. 7.9
remove an e- from a gas-phase
atom (1st I.E.) or ion (2nd I.E., 3rd…)

First IE (kJ/mol) 
PERIODIC TREND: ↑ as Z*↑
↑
Across period: E  (larger - #)
•Larger Z*  greater attraction
Down group: E  (smaller - #)
•Larger size  weaker attraction

Exceptions: Easier to remove e- when…

• it relieves “pairing energy” (Gp.6A < 5A)
= small repulsion from having Easier to
2e- in same orbital remove!
• removing e- from p vs s orbital (Gp.3 < 2)
p orbitals higher in E & feel lower Z*, Group
due to less penetration to nucleus,
so p e-s held less tightly than s e-s… N:
(6) O:
It is much easier to remove valence e−s than core e−s …
Z’s

Consider magnesium’s 2nd vs. 3rd ionization:

Mg+ → Mg2+ + 1e- Mg2+ → Mg3+ + 1e-
Mg+: [Ne]3s1  10 shielding e-s Mg2+: [He]2s22p6  2 shielding e-s
Z*approx ≈ +12 – 10 ≈ +2 Z*approx ≈ +12 – 2 ≈ +10 !
(7)
Electron affinity & e- attachment enthalpy: X(g) + e− → X−(g)
∆HEA
∆EAH = enthalpy change (type of E) Fig.7.10
Fig. 7.11

∆EAH (kJ/mol) 
when one electron is added
to a gas-phase atom
E released  negative #
(atom stabilized by loss of E)

PERIODIC TREND:
Across period: E  (larger - #)
•Larger Z*  greater attraction
Down group: E  (smaller - #)
•Larger size  weaker attraction

Exceptions to trend: Group

A little less favourable to add an e- when…

• e- starts new p-subshell (Gp.2)
• e- pairs with another e- in p orbital (Gp.5)
• e- repulsion high because of small atom size (2nd row vs 3rd & lower)
(8)
Combining various energies to find lattice E (flashback to 12.3)
Hypothetical “Born-Haber cycle” describing formation of ionic solid:
1. Sublimation to atomize metal
Na(s) → Na(g) [E required: ∆Hsubl = +107.3 kJ/mol]
2. Ionization of metal atoms
Na(g) → Na+(g) + e− [E required: IE = +496 kJ/mol]
3. Dissociation of nonmetal into atoms
½ Cl2(g) → Cl(g) [ E required: ½ BDE = +121.3 kJ/mol]
4. Formation of X− ions in gas phase
Cl(g) + e− → Cl−(g) [E evolved: EA or ∆HEA = -349 kJ/mol]
5. Formation of solid MX from gaseous ions (but can’t do it in high-vac. instrument!)
Na+(g) + Cl−(g) → NaCl(s) [E evolved: lattice E = ? ]
NET: Na(s) + ½ Cl2(g) → NaCl(s) [E evolved: ∆Hof = -411.1 kJ/mol]

GENERALLY: Sum of Es for hypothetical steps = E for net reaction.

THUS, to determine Lattice Energy (measuring directly would ruin instrument):
1) measure heat evolved by net reaction = “enthalpy of formation” of solid
(relatively simple, not delicate instrumentation)
2) subtract Es of steps 1-4: LE = ∆Hof – (∆
∆Hsubl + IE + BDE + ∆HEA)
(9) = -787 kJ/mol
CLICKER Q: Understanding reactivity patterns

Which of these anions should be harder to oxidize: Cl- or Br- ?

…and why? (= have higher IE)

A. Cl- – because the e- to be removed is in a smaller orbital.

B. Cl- – because the e- to be removed experiences higher Z*.

C. Br- - because the e- to be removed experiences higher Z*.

D. Br- - because the e- to be removed is in a larger orbital.

E. Two of these are correct.

NOTE: This prediction would be valid for isolated gas-phase ions;

ion-ion attractions in the solid state would complicate the energetics.
 Periodic trends & chemical properties:
Why do rxns yield atoms with noble gas e- configuration?
Once achieved, this configuration is DIFFICULT TO CHANGE.
1. To add another e- to atom/ion with noble gas config’n…
Energetically unfavourable because:
 Adding e- to next (higher) energy level
 Zeffmin for this new valence shell is very LOW (actually negative!)
 insufficient attraction to keep extra e- at this distance
A powerful oxidant, oxygen readily steals 2e-/atom, but never 3:
O2-: [He]2s22p6 “O3-”: [He]2s22p6 3s1
core valence (full) new core new valence
What do its n=2 e-s feel? What would a 3s e- feel?
 Z*approx ≈ +8 – 2 ≈ +6  Z*approx ≈ +8 – 10 ≈ -2
 strong attraction…  net repulsion! e- won’t stick!

Less unfavourable for heavier atoms (e.g., those who can exceed octet):
1. Higher energy levels closer together: easier to enter next energy level
2.(11)
Smaller repulsion: larger valence orbitals  weaker interaction with Zeffmin
Once achieved, noble gas configuration DIFFICULT TO CHANGE…

2. To remove an e- from a noble gas configuration:

= removing a core e-, requires a LOT of energy…
Main group metals: form cations with noble gas e- config.
Higher charged ions unfavourable because:
 Need to remove e- from full octet (was core, = new valence shell)
 Z*approx for this lower E level is very HIGH
 strong attraction to nucleus, requires high E to remove e-

A strong reducing agent, potassium loses 1 e-/atom, but never 2:

To remove an n=3 e− from K+: [Ne]3s23p6
 Z*approx ≈ +19 – 10 ≈ +9 strong attraction b/w each e− & nucleus
difficult to overcome  2nd e- NOT lost!

Transition metals: more complicated; common ions arise from…

a) emptying the s subshell
b) emptying or half-emptying the d subshell Not usually noble gas
config., but still stable
(12) (see advanced courses)
 WHERE DO ATOMIC ORBITALS FIT INTO BONDING?

Kotz Ch.9 / Openstax Ch.8: Orbitals & Bonding

9.1 Orbitals and Bonding Theories

Valence Bond Theory
• Orbital overlap model of bonding
• Hybridization of atomic orbitals
• Multiple bonds: σ-bonds vs. π-bonds
• Cis-trans isomerism: a consequence of π-bonding
• Benzene: a special case of π-bonding

Chapter Goals: (for us)

 Identify the hybridization of an atom in a
molecule or ion.
 Draw sketches representing the orbitals
(13) involved in forming single & multiple bonds
 (K9.1/OS8.1): Orbitals and Bonding Theories
YES! The atomic orbitals we learned ARE important!
 Atomic orbitals (wave descriptions of e-s showing where we’ll find
them) of the VALENCE ELECTRONS (e-s involved in bonding)
overlap & mix together when atoms form bonds.
 Result: new orbitals formed (interfering waves = new pattern!)

TWO THEORIES USED TO RATIONALIZE HOW THIS OCCURS:

1. Valence Bond (VB) Theory 2. Molecular Orbital (MO) Theory
(aka Localized Electron Model) (aka Delocalized Electron Model)
 Key player: Linus Pauling  Robert S. Mulliken
 Related to Lewis structure idea  Bonding e-s spread out
 Bonding e- pairs localized between over entire molecule, in
pairs of atoms MOLECULAR ORBITALS
 Lone pair e-s on single atoms  Particularly useful for:
 Mainly used for: • Quantitative views
• Visual pictures of molecular • Excited states
structure & bonding • Paramagnetic cmpds
• Molecules in ground state with even # e-s! (O2)
 Our focus in Chem 205. See in more advanced courses.
(14)
VB Theory Part (a): Orbital overlap model of bonding
IN GENERAL: two overlapping orbitals + 2e- = one bond
• single bond: greatest e- density along axis of bond
called a σ-bond “sigma bond”
For simple linear molecules involving only one single bond,
atomic orbitals in original form overlap to form bonds:
in F2, σ-bond involves 2p-2p overlap:

F 2p F 2p
in HF, σ-bond involves 1s-2p overlap:

H 1s F 2p
See Fig.9.2
RESULT: molecular geometry same as predicted by VSEPR
(15) WHAT ABOUT MORE COMPLICATED MOLECULES?
Let’s consider methane, CH4

Predicted geometry (using VSEPR)

= TETRAHEDRAL
…matches experimental observations

If we try to rationalize this starting with C’s valence e-s in

its original atomic orbitals, it won’t work:
Problems:
1.) ORBITAL ORIENTATIONS: E
2s: “points” everywhere…
3x 2p’s: at 90° to each other
2.) ORBITAL OCCUPATION:
ground-state C atom only has
2 unpaired e-s…so how can it
bond to 4 H’s (each supply 1e-)?
...even if we imagine exciting one of the
2s e-s into a 2p orbital, the orbital
orientations are still “wrong” for Td CH4
(16) See Kotz 9th p.342
VB Theory part (b): Hybridization of atomic orbitals (OS8.2)

So: methane involves 4 σ-bonds.

Each σ-bond formed by: Fat lobes of hybrid orbitals
one C sp3 hybrid used for bonding…
(can ignore the other tiny lobes)
overlapping with
 note that the 4 hybrids
one H 1s orbital
point away from nucleus in
a tetrahedral arrangement!

Figure 9.4
(17)
Hybridization of atomic orbitals: how to picture it
WHAT IS HAPPENING:
 Atoms respond as needed to make the newly forming molecules have
lowest energy possible (i.e., be as stable as possible).
 HOW TO PICTURE IT (but it’s not quite like this): As bonds begin to form…
• central atom’s own valence shell’s orbitals mix together
• to form new “hybrid” orbitals (which then overlap with outer atoms)
• permitting e- pairs to be as far away as possible in the molecule

NOTE: any orbitals from an atom’s valence SHELL can be used

• e.g., if valence e- in n=2 shell, all 2s & all 2p’s can be used
• even if they were not all occupied in the free atom
• the valence e-s are then “placed” into the hybrid orbitals…

e.g., BF3 Valence e-s… 2s 2p

3 Fs: 21 e- from:
1 B: 3 e-s from:

(18) Can use all of these orbitals

 Identifying hybrid orbitals involved in bonding
1st draw Lewis structure…then remember:
1. One hybrid orbital required per e- pair (but treat mult.bonds as single)
2. If mix 2 atomic orbitals  2 hybrid orbitals form… etc…
3. Hybrid orbitals are named after their parent atomic orbitals
 start with the s orbital + as many p & d orbitals as needed
to make enough hybrid orbitals
to hold all the σ -bonding pairs & lone pairs around the central atom

e.g., BF3 Central atom: 3 e- pairs

: :

: :
: (bonds...)
:F F
2s 2p B
Need: 3 hybrid orbitals
3 Fs:
1 B:
: F: Mix: 3 atomic orbitals: s + p + p
:

available Result: 3 sp2 hybrid orbitals

atomic orbitals sp2-hybridized B atom
trigonal planar geometry!
(19) (must match VSEPR…)
 # Basic (e-) Angles Atomic orbitals Hybrid orbitals formed
pairs geometry required
2 Linear… 180° 1s&1p 2 sp hybrids

3 Trig. planar 120° 1 s & 2 p’s 3 sp2 hybrids

4 Tetrahedral 109.5° 1 s & 3 p’s 4 sp3 hybrids

5 sp3d
5 Trig. Bipyr. 120°, 90° 1 s, 3 p’s & 1 d’
hybrids

all 90° 6 sp3d2

6 Octahedral 1 s, 3 p’s & 2 d’’s
hybrids
Compare this figure (Zumdahl) to Kotz Figure 9.3
These are easier to draw, but Kotz’s shapes are more realistic
CLICKER Q: Geometry & hybridization
Consider the molecule SF4. The sulphur is surrounded by four fluorine
atoms & one lone pair (on exam, you’d need to figure this part out yourself…).
Which of the following descriptions apply to this molecule ?

Basic shape Molecular geometry Hybridization of S

(e--pair geometry)

A. trigonal bipyramidal see-saw shaped sp3d

B. trigonal bipyramidal T-shaped sp3d
C. trigonal bipyramidal T-shaped sp2d2
D. tetrahedral tetrahedral sp3
On own: Which hybrid orbitals are involved in bonding?
Species BF4- O3 CO32-

:
Representative :F: -
structure -

: :

::
O O
(not including : F B F : + O C
resonance)
: F: - -
:
# e- “pairs” on
4 3 3
central atom
Electron-pair
Tetrahedral Trigonal planar Trigonal planar
geometry
# lone pairs 0 1 0
Molecular
Tetrahedral Bent (V-shaped) Trigonal planar
geometry
Hybridization
of central atom
(22) Terminal atoms: can view as hybridized too (but is controversial…)
WHY CARE ABOUT ORBITAL HYBRIDIZATION?

1. Helps explain reactivity & geometry changes:

e.g., How do open-valence atoms accept e-s to fill their valence?
Where do they “put” the e-s when they do this?
Why do they change in geometry when this happens?

e.g., BF3 + NH3 → F3B-NH3

2. Helps explain multiple bonds !  VERY IMPORTANT!

Why can a 2nd or 3rd bond form between some atom pairs?
Where are the e-s in a multiple bond?
What orbitals are involved?
(23)
If some atomic orbitals not involved in hybridization…
3D view of whole
set of hybrids

sp2
hybrids
for 3
e- pairs

NOTE: one s & two p orbitals were used to make the sp2 hybrids…
THUS: one p orbital is left over in unhybridized atomic orbital form
• is perpendicular to plane of molecule
• in BF3, it is empty (= place where NH3’s lone pair could go!)

Kotz
Fig. 9.6 =

(24) Note - see also: text’s Figures for sp hybridization (+2 p’s)…
WHY CARE ABOUT ORBITAL HYBRIDIZATION? (OS8.3)

1. Helps explain reactivity & geometry changes:

e.g., How do open-valence atoms accept e-s to fill their valence?
Where do they “put” the e-s when they do this?
Why do they change in geometry when this happens?

e.g., BF3 + NH3 → F3B-NH3

2. Helps explain multiple bonds !  VERY IMPORTANT!

Why can a 2nd or 3rd bond form between some atom pairs?
Where are the e-s in a multiple bond?
What orbitals are involved?
(25)
Unhybridized p orbitals required for MULTIPLE BONDS
Let’s consider ethylene, C2H4 (also called ethene)

Both C’s have bonds to 3 atoms

Thus: trigonal planar about Cs
all H-C-X angles = 120°
sp2 hybridized C atoms…

σ -bond framework of molecule (single bonds)

formed by C 2sp2 – H 1s overlap
& C 2sp2 – C sp2 overlap

↑↓ ↑ ↑ ↑ ↑ ↑ ↑  The unhybridized p orbital on each

C atom contains an electron.
2s 2p 3 sp 2 p
orb.  This p orbital overlaps the p orbital
hybrid for š
orbitals
on the neighbouring C atom
bond
 forming a “π -bond”.
(26) See Figure 9.8 See next slide…
 SIGMA (σ) vs. PI (π π) BONDS
the way the orbitals overlap is different…
 A sigma (σσ) bond centers along
the internuclear axis
i.e., e- pair lies between nuclei
= a regular “single bond”
ORBITALS OVERLAP END-ON
efficient overlap ∴ strong bond
σ-bonds can rotate without breaking
σ

 A pi (π π) bond occupies the space

above and below internuclear axis
i.e., 1 bond, but 2 regions of overlap
ORBITALS OVERLAP SIDE-ON
less efficient overlap ∴ weaker than σ
 σ -bond must also exist between atoms
ππ-bonds can NOT rotate without
breaking ∴ they are rigid
1 double bond = 1σ + 1π
π bond
(27) See Figure 9.8, 9.9, 9.10 1 triple bond = 1σ + 2π
π bonds
The complete orbital picture of ethylene, C2H4

1 double bond = 1σ + 1π
π bond
An orbital picture of the bonding
in ethylene:

 this picture is useful because:  whereas this picture:

 shows the atomic orbitals involved  shows overlapped p-orbitals
 can easily draw it by hand…  is realistic, but hard to draw
Zumdahl’s Figure 9.13 Kotz’s Figure 9.8

IMPLICATION of π-bonding: Ethylene is a rigid molecule

 its C-C σ-bond bond cannot rotate, because the π-bond won’t let it!
(28)
 Similar approach required to understand triple bonds
- :C N: cyanide anion CN- (1σ + 2π bonds)
 sp hybridized C & sp hybridized N
180º 180º each atom has 2 unhybridized p orbitals
2sp-2sp More realistic
1st: draw σ-bond drawings:
overlap
framework using
C 2sp – N 2sp ↑↓ C ↑↓ N ↑↓ black σ -bond:
overlaps
2nd: draw the 2 ⊥
unhybridized ↑↓
p orbitals red π-bond:
on each atom ↑↓
3rd: use shading to
indicate overlap of
p orbitals to form blue π-bond:
↑↓
the two π-bonds
↑↓ C ↑↓ N ↑↓
4th: draw the complete
↑↓
picture (superimposed)
(29) Kotz Fig.9.10
So, what does “RESONANCE” really mean? See Figure 9.12
p-orbitals on many atoms overlap at once (for benzene, not NO3-)
 e-s are delocalized over many atoms
NITRATE: Central N atom: sp2 hybridized  1 unhybridized p-orbital
All O atoms: sp2 hybridized  1 unhybridized p-orbital
2
/3

:
:

:
O :O: :O:
:

:
=
N N :O N N
:O :
:O O:
:
:

O: O:
:

O : O

:
:
::

:
:

:
:
2
2 /3
/3

In the resonance hybrid:

3 localized views of NO3- simultaneous overlap of
“resonance structures” 4 unhybridized p-orbitals
 1 π-bond (orbitals shown)  1 π-bond delocalized
 3 σ –bonds (shown as lines) across 3 pairs of atoms
(30)  3 σ –bonds unchanged
On own: determine orbitals involved in bonding in…
Ozone: O3
Resonance

:
structures O O O O
(note: looking at either + - +
ONE of them lets you
answer questions below) -
Hybridization of: Central O: Terminal Os:
Total number of: σ –bonds: π-bonds:
Orbitals involved in
σ -bond framework
(draw & label)

Orbitals involved in
π-bonds
(draw & label)

(31)
 ASSIGNED READINGS

BEFORE NEXT CLASS:

Read rest of Kotz Ch.7 + 9.1; Openstax Ch.6 + 8.1-8.3

Practice: periodic trends, compare properties, explain using Z*

hybrid atomic orbitals: describe, name, draw, apply…

(32)