Solids and liquids: Bonding, Structure, Properties.

Reading: Chapter 16: all sections except: x-ray diffraction part of 16.3; p-n junctions in
16.5; 16.9, 16.10, 16.11. Refer to lecture notes on Canvas.
 Major Bond Types:

For an A-B bond the bond type depends on A- B =

= electronegativity = the ability of an atom in a bond to attract electrons to itself .

Represent using Bond Triangle

1.0 XA 4.0
1.0

Ionic
one wants e -s the other
happy to give them away
Metallic
both happy to
give away e -s
ele e XB
(s
am
m ato
Type of bond
en m
ts )
depends on
(XA-X B)

Covalent
both want e -s; 4.0
compromise by sharing
 Intra-molecular versus inter-molecular forces
Lewis Structures: description of strong covalent bonds formed between atoms within a
molecule:
INTRA-MOLECULAR bonds
(e.g. each O-H bond within an H2O molecule ~934kJ/mol)

1 Hershey bar = 210 kcal ~ 900kJ

Intra-molecular bonds measure the stability of a molecule to

decomposition/dissociation.

For solids and liquids focus on the forces between different molecules/particles:
INTER-MOLECULAR FORCES.

Stability of intermolecular forces: reflected by boiling point (and to some degree

melting point).
 Strongest Bond Types in Solid/Liquid State:
Metallic: see later



Ionic: see later



Extended covalent (Zumdahl uses the term Network Atomic Solids )

We should be clear about the difference between inter-molecular extended covalent
bonds and intra-molecular covalent bonds.
e.g. methane (CH4) and Diamond (C)

CH4 : C(sp3) & H(1s) strong intra- molecular covalent bonds.

Bonding within molecule terminated by H atoms
No covalent bonding left to interact with other CH4 groups

Diamond: replace all Hs by Cs

Covalent sp3 bonds extend throughout solid.
Extended covalent: very high m.pt./b.pt.
 Intra-molecular forces.
e.g. CH4: strength of covalent C-H bonds

INTERMOLECULAR
FORCES:
Weak Forces between CH4
molecules in solid state
 1st look at weaker types of inter-molecular forces.

If there are no strong metallic, ionic or extended covalent forces, these are all we have:
then we have a molecular solid.
Three types: (1) dipole-dipole; (2) H-bonding; (3) induced dipole-induced dipole
(London Dispersion Forces)

(1) Dipole-dipole (5-25 kJ/mol; ~1% strength ionic/covalent)

Present in polar molecules; strength varies with: 

- magnitude of dipole

- dipole-dipole separation

Factors affecting magnitude:

X of bonds



: shape (VSEPR)

e.g.s compare isoelectronic molecules: CO & N2 (10 VEs)

N2 n on-polar no dipole b.pt. 196C
CO polar (!X) d i pole b . p t. 192C
SiH4 & PH3 (8 VEs)
SiH4 sp3 tetrahedral n on-polar b.pt. 112C
PH3 sp3 trigonal pyramidal polar b . p t. -88C
 (2) Hydrogen Bonding (strength 15-40 kJ/mol)
Special case of dipole-dipole bonding: molecules with H bonded to high X atoms:
especially effective for H-N, H-O, H-F bonds
also present in other bonds but much weaker.
H-bonds considerably stronger than other dipole-dipole interactions.

Why so strong ?
(a) bonds highly polar

(b) small size of H

(i) concentrate + charge into small volume

(ii) permits very close approach of oppositely charged
end of dipole on other molecules

(c) unscreened nucleus of H: when draw e- s away, only have bare

nucleus (proton)

H-bonding leads to increases in boiling points:
e.g. consider two C2H6O molecules:

(a) ethanol: CH3CH2OH: O --H + effective for H-bonding b.pt. 78.3C

(b) dimethyl ether: CH3OCH3: C-H bonds, no H-bonding b . p t. 24.8C
 Ice - H2O(s)

- liquid to solid transition is very unusual: H2O expands when it freezes

Ice floats - lower density (higher volume per mole)

Almost every other material: solid has smaller volume and higher density

Why is H2O anomalous????

 Why is H2O anomalous????

- Specific positions for neighboring

molecules to maximize use of H-bonding
in solid state

- Each H2O has 4 other H2O s as neighbors

- Maximizes bonding even though it is not

the minimum volume

- Structure collapses when ice melts

What application does this enable?

 Very few analogs of H2O(s) that contract on melting

Acetic acid (CH3COOH)

http://commons.wikimedia.org/wiki/File:Acetic_acid_structures4.png

Solid State Crystal structure:

- specific orientations enhance inter-molecular H-bonding

Significant open space

 (3) Instantaneous dipole-instantaneous dipole forces: London Dispersion Forces.
(weak, 2-20kJ/mol)

weak interaction present in all molecules.

Instantaneous displacement/fluctuation of electron distribution by neighboring molecule or atom.

Non-permanent dipole; weak and short-lived.

Magnitude depends on ease of distortion of electron orbitals (polarizability)


- typically increases with atomic number and size


- shape also important for close approach (closer = stronger)

These are the only forces present in many non-polar molecules: e.g. Noble gases


B.Pt.(C)

He
-268.9

Ne
-245.9

Ar
-185.7
Atomic # increases

Kr
-152.3

Xe
-107.1

Ra
-61.8


 Boiling points of Hydrocarbons

C-H (& C-C) bonds no dipoles, just LDF attractions.

!"#$%"#&'() *"#$%"#&'()
+,%-./, (01 2345 2361
,%-./, (70 6 2345 248
$9:$./, (50 4 238; 217 For high molecular weights
<=%./, (10 3; 2354 2;"> forces become large enough
$,/%./, (>0 37 235; 56
to stabilize liquid, solid
phases at room T.

-,?./, (60 31 28> 68
-,$%./, (@0 36 283 84
:A%./, (40 34 2>@ 37>
/:/./, (80 7; 2>3 3>3
B,A./, (3; 0 77 25; 3@1
=/B,A./, (33 0 71 27> 386
B:B,A./, (37 0 76 23; 736
,CA:D./, (7; 0 17 5@ 515
%9C.A:/%./, (5; 0 67 66 1>;

By considering what forces are present, you should now be able to

rationalize trends in boiling points for different compounds.