Physical properties and intermolecular forces

Macroscopic physical properties: melting point, boiling points, solubilities for identification of
organic compounds. The strength of intermolecular forces determines these properties

Why does methane have a lower boiling and melting point than ethyne?
Why do the constitutional isomers ethyl alcohol and ether have different physical properties?
Why do acetic acid and sodium acetate have such a high melting and boiling points? 1
 Intermolecular forces
bond dissociation energy of covalent bonds: 140-523 KJ mol-1, intramolecular force
ion-ion forces: ionic compound, strong electrostatic lattice forces that hold the ions together in the
crystalline state and act between positive and negative ions in the orderly crystalline structure.
high mp. and bp., often decompose before they boil. NaOAc: mp.: 324 °C.

Intermolecular forces of covalent compounds: <38 KJ mol-1, hydrogen bonding, dipole-dipole

interaction, van der Waals forces. They determine the physical properties like melting and boiling
points for covalent compounds.

1) Dipole-dipole forces: 0.8-12 KJ mol-1, molecules with permanent dipole moment, acetaldehyde
has a higher boiling point than propane.
H3C CH3
 O C
 C O
H3C CH3
acetone
 O 
O H O
CH3  CH3 N  
CH 3 N H C N
CH 3 CH O
O O H O
CH 3
 
N CH3
2-methylpropane nitromethane inductive effect
O
bp. - 12 °C bp. 101 °C 2
2) Hydrogen bond: very strong dipole-dipole attractions between hydrogen atoms bonded to small,
strongly electronegative atoms (O, N, or F) and nonbonding electron pairs on other such
electronegative atoms. 4-38 KJ mol-1. intermolecular and intramolecular hydrogen bonds.
H C S Br N O F
EN = 2,1 2,5 2,5 2,8 3,0 3,5 4,0

H
H    HO O
180 pm
 C H
O   O O HO
H  O
 H  H H H3C C C CH3
O 100 pm O
OH O
H H
water acetic acid salicylic acid
H H H
 
O C N H N N
O C H O C H
H H H
formamide bp.: 193 °C

H
C O H O O
H H
O O C O C O C
H H H H
O

salicylaldehyde 4-hydroxy-benzaldehyde
mp.: -7 °C mp.: 117 °C,
bp.: 197 °C, volatile bp. : high, decompose 3
intramolecular intermolecular hydrogen bonding
Hydrogen bonds hold the base pairs of double-stranded DNA together.

3) van der Waals forces: also called London forces or dispersion forces; electrons may be slightly
accumulated on one part of the molecule  temporary dipole  induce opposite dipole in
another molecule  attractive forces between nonpolar molecules
Polarizability: ability of the elecrons to respond to a changing electric field. F < Cl < Br < I

Except for molecules where strong hydrogen bonds are possible, van der Waals forces are far
4
more important than dipole-dipole interactions.
 Solubility

dissolution of a solid in a liquid: lattice energies and intermolecular or interionic attractions need to
be overcome, more disorderly arrangement of the molecules, hydration or solvation of ions.
water: great polarity, small, compact shape, strong hydrogen bonds and dipole-ion attractive force

dissolution of an
ionic solid in water

like dissolves like: polar and ionic compounds tend to dissolve in polar solvents,
polar liquids are generally miscible with each other. Nonpolar solids are soluble in nonpolar
solvents. Nonpolar liquids are usually mutually miscible, but nonpolar liquids and polar liquids like
oil and water do not mix.
methanol and water, ethanol and water, propyl alcohol and water are miscible in all proportions

5
very slightly soluble in water
Summary of attractive electric forces

6
Shape and properties: the boiling points of unbranched alkanes show a regular increase with the
increasing molecular weight.

branching of alkane chains lowers boiling point

chain branching makes the molecule more compact and
reduces the its surface area and the strength of the van
der Waals forces

hexane
bp.: 68.7 °C 2-methylpentane 3-methylpentane 2,3-dimethylbutane 2,2-dimethylbutane
bp.: 60.3 °C bp.: 63.3 °C bp.: 58.0 °C bp.: 49.7 °C

When even- and odd-numbered carbon alkanes are

plotted on separate curves, there is a smooth increase
in melting point with increasing molecular weight.

even-numbered odd-numbered
monoclynic orthorhombic
molecules pack more 7
closely in the crystalline state
odor and structure: stereoisomer discrimination in odor perception

H3C
CH
H3C
HO CH 3
OH

(-)-menthol
cooling effect in tobacco
eight possible isomers
(R)-(+)-limonene (S)-(-)-limonene
orange odor lemon odor

colour and structure: 11 conjugated double bonds, absorption maximum at 497 nm,
orange colour of carrot, light of 487 nm has a blue-green color and this is absorbed by -carotene
We perceive the complementary color of blue green which is red orange.

 - carotene

(carrot)

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 Structure elucidation of organic compounds
organic compound or mixture isolation or synthesis

Checking the purity physical constants (mp., bp.), spectroscopic

methods, chromatography (TLC)

purification
chromatographic methods (coloumn
chromatography), crystallization, extraction,
destillation, filtration.

Analysis

Qualitative analysis Quantitative analysis

chemical tests Elementary analysis

for the identification of C, H, N, S, Hlg.
elements and functional
goups, derivatization
Molecular formula
physical methods

spectroscopic methods: Molecular weight

determination of physical
constants UV, IR, NMR, MS, XRD

constitution, stereochemisty 9
 Qualitative analysis
Test for carbon and hydrogen (Liebig): the carbon and hydrogen content of organic compounds
is converted to carbondioxide and water when heated in the presence of CuO at 500-550 °C.
H2O 
oo o C, H, O  CuO 
 CO2  H2O  Cu2O
zz The evolved carbondioxide forms barium carbonate
precipitate with barium hydroxyde.
CO2
o
o
Ba(OH)2 + CO2 BaCO 3 + H2O
oo
CuO + minta oo
oo

Ba(OH)2

Test for nitrogen, sulfur and halogens

identificatin of N-content (Lassaigne-probe): The nitrogen content of organic compounds
is converted to sodium cyanide when heated with sodium which gives Berlin-blue precipitate
with ferrous sulfate and ferric chloride.

C, H, O, N, S, Hlg  NaCN  Na 2 S  NaHlg
2 NaCN  FeSO 4  Fe(CN) 2  Na 2 SO 4


Fe(CN) 2  4 NaCN  Na 4 FeCN6 
 
3 Na 4 FeCN6  4 FeCl3  Fe 4 FeCN6 3  12 NaCl
10
Berlin blue
sulfur content: lead acetate converts the water-soluble sodium sulfate to dark brown lead sulfate,
which precipitates from the solution
Na 2 S  PbOAc 2  PbS  2 NaOAc

halogen content: halogenide ions form silver halogenide precipitate with silver nitrate

NaHlg  AgNO 3  AgHlg  NaNO 3

Belstein test for halogens: samples heated on copper wire formed copper halogenide which
dye the flame of a Bunsen burner with green color. 
C, H, O, S, N, Hlg + Cu CuHlg
Quantitative analysis
determination of C, H content: Pregl method, sample is burned in oxygen flow

C, H, O, S, N, Hlg CO2 + H2O + NOx + SO3 + CuHlg2
CuO
measured removed
sample
read heat 200°C
oooooooooooooo
z oooooooooooooo
O2 Ag CuO/PbCrO4 Ag PbO2 Ag z CaCl2/P2O5 z NaOH/azbeszt
z oo o o o o o o o o o o o oo o
o o o o o o o o o o o oo o
f e d c b a A B
binds water binds CO2
binding halogens removal of SO3
as AgHlg removal of NO2 weight measurement 11
a: heated thin Ag wire to prevent the condensation of water
b: lead dioxide to chemically bind NO2 PbO 2  2 NO 2  Pb(NO 3 ) 2
c: silver ball to trap halogens and control temperature
d: copper oxide- lead chromate; oxidizing agent, trap SO3 as lead sulfate (PbSO4)
e: silver ball to trap halogens
f: 1-2 mg of sample measured in platinum wessel
A and B trap the water and CO2 content which then can be measured by scale.

Elementary or combustion analysis nowadays: separation of gases from the mixture

(CO2, H2O, N2, SO2) by gas chromatography followed by detection with thermal conductivity
detector. determination of CO2, H2O, N2 content, NO2 is reduced to N2 by CuO

Dumas method for determination of N content: When heated with CuO, organic compounds can
be burned in O2 flow.

C, H, O, N  CuO 
 CO 2  H 2 O  N 2  NO x  Cu
removed measured by volume

Cu  NO x 
 CuO  N 2

sample
zz

oo oo oo
oo oo oo
CO2 oo oo CuO oo Cu
oo oo oo

zz
oo oo oo

700 °C 800 °C

12
Azotometer for volume measurement