Ethane How many o bonds are in Ethane

7 sigma bonds
what is thehybridization of the
µ If a E H
G
carbon atom
P
3

I
S
it H S

sp3
4Y hybri
IFabonisattacted
3 Icy gp2
O CIO g p 2
Sections 8.4. Valence Bond Theory and sp2 hybridization Review of sp3. sp3
sp3
Today we will look at other hybridizations, starting with the sp2 hybrid
sp3
orbital. There are three groups of electrons around each carbon in
C2H4 and each establishes the trigonal plane geometry by forming
sp3 F H F
hybrid orbitals built from one s-orbital and two p-orbitals – making sp2 sp3 sp3
orbitals in the 3-D sketch. The energy diagram below shows that
sp3 H
there is one p-orbital left over. That orbital will be used to make the 1s
double bond. The diagram at far right shows the lobe-like structure
with the orbitals labeled. Each has one of carbon’s four valence
electrons. The single p-orbital is shown in a blue color – remember
that the p-orbital has two lobes, but is just one orbital. p

H C C H sp2
C
H H
Energy à

sp2 sp2
2p
p

2s
sp2 sp2 sp2 AB z
1s
3
 Whenever it overlaps head to hed
Its Koun at Obonds
all single bond ore
Sigma bond
Sections 8.4. Valence Bond Theory and sp2 hybridization
To use these lobe orbitals to make a sketch of orbital overlap, we start
H C C H
p
with the carbon-carbon bond. The corresponding electron dot H H
structure is given below. sp2

C C
CHy DoHybriditatio UyobondstEansfHg.i
sp2 sp2
Hey y spy
Escp p p
sp2 sp2
C C
ÉgÉ sp2 sp2 sp2 n Hybridization
sp2

4SP3 In

sp 3 C C Lewis
Mixing sandP 4
Sections 8.4. Valence Bond Theory and sp2 hybridization
Next, we add the hydrogen atoms, two on each carbon and each
H C C H
1s
overlapping with an sp2 lobe. H H

Bonds involving the direct overlap

p p of orbitals like you see here
sp2 between carbon’s sp2 orbitals and
1s H sp2 H1s hydrogen’s 1s orbitals are called
C C sigma bonds (s-bonds).
sp2 sp2 sp2 sp2
H1s H How many s-bonds are shown in
1s this diagram?

8 sigma
Pi sigma firstbond H C C H
Items H H Yh56
bonds in the
H
ft YI't
5

c IH Ie Ie molecule

H LIC H
 0
Sections 8.4. Valence Bond Theory and sp2 hybridization
H C C H
Now all that is left is to pair up the p-orbital electrons to make the

bond H Hbond
carbon-carbon double bond.

bond space
goneH Or ThruThe new bond involving the
overlap of p-orbitals is not a direct
p p
sp2 overlap. It is called a pi-bond (p-
1s H sp2 H1s bond). It looks like there are two
C C p-bonds but, like p-orbitals, the top
sp2 sp2 sp2 sp2 and bottom parts are just two
H1s H halves of one orbital.
1s
Sigma How many p-bonds are shown in
this diagram? Careful!
IT bond H C C H
Sigmabond H H 5sigmabond
F bond IN bond 6

Single bond are always

D bond
Sections 8.4. Valence Bond Theory and sp2 hybridization
Create an orbital overlap diagram for methanal, HCHO.
H C O
H 1 H
HE É
É gp2 1200

dymwnethi room comes

not
IITbond
H lobond
Should itbe
bond L 7

sigma 5
Sections 8.4. Valence Bond Theory and sp2 hybridization sp3
sp3
We’ve encountered two hybrid orbital styles so far, sp3 and sp2.
The sp3 hybrid was used when we had four electron groups around sp3
the central atom, such as for fluorine that we encountered in the
sp3 F H F
previous lecture and we used to make HF. sp3 sp3

Over the last few slides we discussed sp2 hybridization used and sp3 H
1s
sp2. The sp3 hybrid was used when we had four electron groups
around the central atom, such as for fluorine that we encountered in
the previous lecture and we used to make HF.

p p
sp2
H C C H 1s H sp2 H1s
H H C C
sp2 sp2 sp2 sp2
Now we are ready to look at sp-hybridization which we H1s H
would use in molecules such as ethyne, C2H2. 1s

H C C H 8

Ethyne Acethelyne
Sections 8.4. Valence Bond Theory and sp hybridization
p
Now we are ready to look at sp-hybridization which we
would use in molecules such as ethyne, C2H2. The two sp- sp C sp C
hybrid orbitals are 180o apart making the geometry linear.

2p
p p
Energy à

sp sp
2s
Sigmabond
p p

Here we’ve made the single bond (s-bond) sp C sp sp C sp C C

between the two carbon atoms by overlapping
one sp-hybrid orbital from each carbon. Now
each carbon seems to have five valence
electrons.
9
Sections 8.4. Valence Bond Theory and sp hybridization

Knowing the electron dot structure of the desired chemical, we can build in that
direction. We could add the H atoms first or make the triple bond first. We will
H C C H
do the hydrogen atoms first.

p p

H1s sp C sp sp C sp
H H C C H
1s
Ge Ge
ZITbonds
10 bond
or
3 10
 Sections 8.4. Valence Bond Theory and sp hybridization

We finish by adding the two p-bonds. The two sp-hybrid

orbitals are 180o apart making the geometry linear. Triple bond
1042T bond

H1s sp C
p

sp sp C
p

sp
H
1s
H C
I C H
30
i d ZIT
Here is what we learned along the way:
o Single bonds are always s-bonds (direct overlap between two orbitals. How many total s- and p-bonds are
o Double bonds are always one s-bond and one p-bond. in the molecule C2H2?
o Triple bonds are always one s-bond and two p-bonds.

sp3sHave y groups8 3
no pi bonds AB y
bond AB3 AB2E
ABBE ABLE2 it ÉH 11

Have a total af groups and Iit

spin bonds and 21T bond
I c
egg
Sp Have atotal of 20 ABL ABE H CE c h
Sections 8.4. Valence Bond Theory and hybridization na
C Br C
Create an orbital overlap diagram for methanal, BrCN. How many s- and p-bonds are there? N

A As Br CEN
BBC.CI D 20
ZIT
0.0.0
12
 1
s

YE
gp stPtPtP x
sp St Ptp
Sp Stp
gyp strap
EX 5225272 Dp
Ep 2PIII
pit
Dp Stp
Dp3 StPtPtPwhen usingsp3
means that allfour
are being usedwe
PIE
needto mixed stptpt

i EC

Strong weak T
LOT IT
LOT ZIT EH
CIC singlebonds
stronger than 1
but are shorter
H
12 MEH
Everysinglebondhas
10
has IT 2166
Every double bond
 252252282
SEE I IAybridorbitals
É when hybraditat
if ours then

25
2sp GQ.r
i
Examine
ICzHI

El Double bond
AT bond comesfrom
unny.br
The overlapof
P orbitals
Sections 8.4. Valence Bond Theory and hybridization
Create an orbital overlap diagram for methanal, CO2. How many s- and p-bonds are there? What is the
hybridization for each atom?

ZITbonds
0 4
0 6 2
c D I c

Paso
800.0.0003
O
13
Valence Bond
we take atomic orbitals S P mix to form hybrids
Ofatomic orbitals
Hybrid orbitals mixture of atomicsPorbitals

S top D
D
SRffbrids
Edgbfrigonalplaner
SP Of X t 8 20
At
Spt
sp Ot 8 8 tetrahedral

sp
Myriagram
H N O
HIT EI I E Tt
Look atthe central
It If
0

Éjf
Form sp3
EYED sp3
IEEE
Put tyro
F
0 80
Sigmabond D
n
 O
11
spa 8
D C I
e III or
I pi
on
electrons from
selectiongroups
Which means it A
hadto hybrid 3
2 side view 0
Orbitals so sp

_iÉÉ É
H SP tetrahedral ITbond
Down bad it
It
Triple Bond C C H
F
WgÉ
ond
H

IX I
it
 Lewis structures and identify the of
Draw
IT bonds in each
5 2 10 M D
Nz N NEMILITbonds
It

NH3 N4 5
3 1
Hint
HH My H yo bonds
3
NO N 52
6
10
NI N D 21Tbonds
0
20bonds
IN IN E
 542.5 C telectro
EX 2.5 3.0 negate
Sections 8.5. Polar Covalent Bonds and Polar Molecules
8
As we learned in Section 7.3 on Chapter 7 Day 1, bonds between two atoms are polar if there is a difference in
8
electronegativities. Molecules with these bonds may be non-polar if polar bonds cancel each other. Suppose the green
atoms are more polar than the central atom – that’s normal… The molecule on the left is polar, and the one on the right
is non-polar because it is linear.
E E We worry about whether or not a
ex molecule is polar only if it’s a molecule.
B B Ions carry a full charge so fussing about
D 2.5 O C B
polarity makes no sense.

30 3.0 AB E AB2 Non

tis 21Esbramolecue polar
2 2
Polar
For the same reasons that AB2 is non-polar no matter
what the electronegativities of A and B are, AB3 and
AB4 are also non-polar B
AB3
BABY
B B
AB2 B B B BB
E group makes it
Non Polar
14

Polar
Sections 8.5. Polar Covalent Bonds and Polar Molecules
The other three ABE formulas have at least one E group and are polar because the E groups can’t offset the polar
bonds between A and B.

E EE
E
B
B B B
AB3E AB2E2 B B AB2E B
Anything with just two atoms is polar if the atoms are different, for example, CO is polar. Two atom molecules are non-
polar if the atoms are the same, for example, O2.

Let’s think about molecules with AB2 geometries. If B and B’ have different electronegativities, b t
the molecule is technically polar even without E groups on the central atom.
I eletronegati
15
Sections 8.5. Polar Covalent Bonds and Polar Molecules
Some molecules have two or more “central atoms.” Happens all the time. A simple example is methylamine shown
below. It features a carbon atom in black bonded to a nitrogen atom in blue. Green atoms are hydrogen.

B Makesit Polar
AB4
AB3E
ON
EO.EE
So the carbon atom has no E group, so is essentially non-polar, even though it’s technically AB3B’. BUT, the nitrogen
atom has an E group, making that part of the molecule polar! Let’s take another look at the black carbon atom that we
called AB4, but is actually AB3B’.

Carbon’s electronegativity is 2.5 and hydrogen’s is 2.1. This small difference makes the bond almost non-polar. One
might even say, it’s a non-polar bond. Technically wrong, but functionally accurate.

Nitrogen’s electronegativities is 3.0, so the C-N bond is only a little more polar than the C-H bond. The reason
methylamine is polar is due to the E group on nitrogen (AB3E).

16
Sections 8.5. Polar Covalent Bonds and Polar Molecules

Which of these ABE formulas is polar?

O
AB2 AB3 AB2E

O O
AB4 AB3E AB2E2

We didn’t discuss the polarity of these geometries, but you can figure it out if you refer back to the structures (last
slide of previous lecture). With these expanded octet molecules, you can’t just look for E groups. Which of these ABE
formulas is polar?

B
In
is non Polardispute
O
AB5 B AB4E AB3E2 AB2E3

Bata
AB 6

Nonpolar
8KIAB5E AB4E2
mummify quare
Plane

B B Polar
17

BEEB
 Sections 8.5. Polar Covalent Bonds and Polar Molecules

Which of these molecules is expected to be polar (have a dipole moment)? Start by eliminating ions for which polarity is
irrelevant. Next, sketch the Lewis dot structure and thinking in terms of bond dipoles and molecular symmetry.
2.52.13.0
C H Cl 1.6 C2Cl4 C2HCl5
2 5

2.52.1 3.0 1.6

It
Polat
a Poly
NH4+ SF4 PF5

Polar Fifi nonpolar

CH3CH2CH3 CH3CH2OH So becausethereis phosphorus trichloride

guy a
IE iii wholething is polar
sia ABzepolar
hydrazine, NH2NH2
ABI PF6-
By 21090 ozone, O3

Polar Non Nonpolar Polar ABzE 18

Polar
Ini H
Ni H
H ABLE
Non Polarmolecules Polar
Nz 02 ClzFzY2 CHy GHG CHz IC Hz
He we Arne
CH y GHG CHICHI
Molecules havesymmetry
SAME Br
F
F E F TETE
Br Br
f
I Br
2 5 2.8 lessthan 0.5 is non polar
oz If it is
 Sections 8.6 Intermolecular forces (IMFs): London dispersion forces (LDF)

There are three types of intermolecular forces (forces between molecules) that we need to recognize. These do not
include ionic forces which we have discussed earlier and are much stronger – so much so that ionic materials are
usually solids at room temperature. But intermolecular forces can be significant in terms of understanding whether a
molecular covalent compound is a solid, liquid or gas.

The first IMF we will discuss is London dispersion forces (LDF). Every LDF∝ MM
molecule has these, and they are proportional (in some way) to the molar mass: Range of strengths: 1 – 10 kJ/mol

Molecules must be in almost direct contact with each other for LDF to matter. This is how it works: In large molecules
electrons “slosh” from side to side creating instantaneous dipoles in otherwise non-polar molecules:

… d+
Br Br
d-
… d+
Br Br
d-
… d+
Br Br
d-
…
Then, in the next instant, the electrons“slosh” back to the other side:

… d-
Br Br
d+
… d-
Br Br
d+
… d-
Br Br
d+
…
19
i
The heavierthemolecule the strongerthey ar
B Bar
Sections 8.6 Intermolecular forces (IMFs): London dispersion forces (LDF)

Here are some empirical data for non-polar molecules. Notice how the relationship
between MM and boiling point are related? We look at boiling points because boiling
LDF∝ MM
Range of strengths: 1 – 10 kJ/mol
represents the complete breakage of all intermolecular forces.

AllNonPolarIncreasing mass
F2 MM = 38 g/mol Boiling point = 85 K Gas at room temperature.

Cl2 MM = 70.9 g/mol Boiling point = 238 K Gas at room temperature.

Br2 1 MM = 159.8 g/mol Boiling point = 332 K Liquid at room temperature.

I2 MM = 253.8 g/mol Boiling point = 457 K Solid at room temperature.

Increase 20
london
Every molecule
Dispersion
with a zoo or moreis a solid
Increasing Increase increasing
MM LDF BP
Sections 8.6 Intermolecular forces (IMFs): London dispersion forces (LDF)

More non-polar molecules. Notice how the relationship between MM and boiling LDF∝ MM
point are related? We look at boiling points because boiling represents the Range of strengths: 1 – 10 kJ/mol
complete breakage of all intermolecular forces.

Why are these molecules considered

CH4 MM = 16 g/mol Boiling point = -162 oC
non-polar?

C2H6 MM = 30 g/mol Boiling point = -89 oC

cancel
C3H8 MM = 44 g/mol Boiling point = -42 oC What is the hybridization for the
carbons in these molecules.

C4H10 MM = 58 g/mol Boiling point = -1 oC Sp3

C5H12 MM = 72 g/mol
C6H14 MM = 86 g/mol
Does every molecule exhibit LDF?
Boiling point = +36 oC
Allmolecules exhibitLDFs
Boiling point = +69 oC
21
 44242 H.ggg
a
Polarity
strangerinflhydroggy
higher Ihwebnjgaroe
Sections 8.6 Intermolecular forces (IMFs): Dipole-dipole forces

After LDF, the next important type of IMF are dipole-dipole forces. Only polar molecules exhibit dipole-dipole forces.
These three examples have the same MM. Which is/are polar, if any? (We look at boiling points because boiling
represents the complete breakage of all intermolecular forces.)

Ei at t at 8 t
84cg gl T
t
cld get
a
Boiling point = 60.2 °C
qt
Boiling point = 48.5 C
g o
É
Boiling point = 99 oC
ft

Polar due to a non Polar Mostpolar

same
on side Dipole-dipole forces typically range from 5 – 20
What is the hybridization for the kJ/mol. Note that covalent bonds are usually in the
carbons in these molecules? Molecular 200 – 400 kJ/mol range.
dipoles 22
spa Polarmolecules
Non Polar London dispersion
Polar compound to Londondispersion dipole dipole
H F H OH N LDF dip dip hydrogen
Compound with
bond bondedto N O F
Hydrogenbond lone pairs
E
MEIC
CO2 All atoms around
QCD O centralatomarethe
É non polar LDF same

Cand'tonly
if É Egfr
Sfu Poy
pure
quart

Hcl
Polat
between0.4 1.8

Ionic
H d 71.8
more electrons
than H C andH
a Makes itPolar non Polar
Hy
Sections 8.6 Intermolecular forces (IMFs): Dipole-dipole forces
The two molecules shown here are isomers of C6H4Cl2. Therefore they have the same molar mass. The hybridization
for each carbon is sp2 so the entire molecule is flat. The only difference between these two molecules is the position of
the chlorine atoms. One of these molecules is polar and the other one isn’t. One has a boiling point of 180 oC and the
other has a boiling point of 174 oC. Identify the correct boiling point with each structure.

Cl Cl

Cl IC C
f H H C
f H
C C C

C C C C
H C H H C H

H
it Cl non Polar 1748
Polar Because chlorine
canceleachother
TboilingPoint out 23

1809
Sections 8.6 Intermolecular forces (IMFs): Dipole-dipole forces

These three isomers of trichlorobenzene have boiling points of 208 oC, 214 oC and 219 oC, but not
necessarily in that order. Which one has the lowest boiling point?

Cl Cl Cl

H C H H C Cl H C Cl
C C C C C C
C C C C C C
Cl C Cl H C H H C Cl
H Cl H

nonPolar
polar Polar
Signnetrical
so cancel
eachother
out 24
Sections 8.6 Intermolecular forces (IMFs): Hydrogen bonding forces

Hydrogen bonding is a funny name for an intermolecular force. They are unusually strong dipole-dipole
forces that always involve hydrogen-oxygen bonding, hydrogen-nitrogen bonding, and hydrogen-fluorine
bonding. They range in the neighborhood of 10 – 40 kJ/mol (again compare this to covalent bonding which
is ~200 – 400 kJ/mol.

onlyoccurs if hydrogen
is hookedto
O H
… bond
Tydrogenvalent
N H bonding
F H force imf yokslmol

25
Sections 8.6 Intermolecular forces (IMFs): Hydrogen bonding forces
Sketch in additional
Here are the same hydrogen bonding
two water molecules interactions (come
shown with are missing)
maximum

…
…
participation in
hydrogen bonding.
… …
…
…
woo
…

ooo
s

26
Sections 8.6 Intermolecular forces (IMFs): Hydrogen bonding forces

In addition to water, there are countless other

compounds containing O-H that could engage in What is wrong with this picture of supposed
hydrogen-bonding interactions. Here are two methanol hydrogen bonding?
molecules with a hydrogen bond intermolecular force
joining them. Thehydrogen mustbe bondedto
F N O to make

…
H bonds
…

O
CH
I
H 27
Sections 8.6 Intermolecular forces (IMFs): Hydrogen bonding forces

Compounds containing N-H bonds also exhibit hydrogen-bonding. Here is ammonia and methylamine, both participating
in hydrogen bonding.

… …

The remaining hydrogen-bonding interaction occurs in molecules containing hydrogen-fluorine bonds. There is
only one such molecule. Sketch the hydrogen bonding interactions that occur in HF.

Hel Ho F iii
interactions
Fe
y 28
Sections 8.6 Intermolecular forces (IMFs): Hydrogen bonding forces
Interactions between different molecules also undergo hydrogen bonding. Sketch hydrogen bonding interactions
between ammonia and water.

H
HN zinteraction
H H
Some molecules cannot participate in hydrogen bonding by themselves, but can do so with
other molecules. Sketch hydrogen bonding interactions between methanal and water.
(Methanal, HCHO, is shown)

H i
Hy g
HI I
29
The last word on formal charges.
We know that formal charges can help us pick the best of several electron dot structures. We did that in Chapter 7,
Day 2. We also know that elements B, C, N, O, F, and Ne cannot expand their octet like we saw for compounds like
PF5 and SF6 and a number of other fluorine-containing compounds (Chapter 7, Day 2).
Some would say if we make a double bond between P and
This brings us to compounds like OPH3. If we used the O, we could reduce the FC to 0 for each atom. The
rules, we would come up with the structure shown below downside is that we must expand P’s octet to do so. Our
for PH3 and then with a snap-on oxygen, OPH3. This book and I both agree that it’s best not to do that. but lots
gives formal charges of -1 for O and +1 for P. of chemistry teachers do it with the same fervor and
conviction as the non-expanders. Here is what they do:
FC = -1 In the end, both structures give us
O FC = 0
O the same AB4 electron dot
H P H H P H
FC = 0 structure, so why fuss? As a
but compromise, both sides can agree
H 10 e- on P H P H
H FC = +1 to consider both structures as
H contributing forms – which is not
the same as resonance.
We cannot make such an electron dot structure (O double-
bonded to N) for ONH3. Why not?
30
Dipole Dipole Between twoPoler Dipole Dipole hydrogen
molecules bond

III
Ex g
o
CEO IO H
bond
I
É ftp.IGae 8 it
bond
H Br H Br
8 28 18128 fisherman
molecule
hydrogen is
atractedto Br

LondonDisperson Non polar

Examples non polar

TCI andH2O Hy lesstihannontpour
It
I
oooo
It
is telectoneg
C1 0ft Aging it's non polar

CO2 Polar 502 Real

5 6 3 B
C y
0 6
244
0 62
0 8 0
EE
2.5 73.5
I 05 Polar
Q c O LDandDPDP
Éppgfoms cancel becausepointopposite
ÉÉIÉzj direction
Non polar