Dotsha J.

Raheem
Department of Chemistry
College of Science
University of Salahaddin
 Definition of b.p.
The boiling point of a liquid
is the temperature at which its
vapor pressure is equal to the
pressure of the gas above it
 In terms of intermolecular interactions the b.p.
represents the energy required to overcome the various
intermolecular attractions binding the molecules as a
liquid (e.g. dipole-dipole attraction and hydrogen
bonding) and therefore undergo a phase change into
the gaseous phase . Therefore the boiling point of a
liquid is also an indicator of the strength of the
attractive forces between the liquid’s molecules.
 The normal boiling point of a liquid is the temperature
at which its vapor pressure is equal to 1 atm
Importance of b.p.
B.p. is a physical constant used for:
1. Identification of unknown liquid compound
2. Purification
factors affecting b.p.
 Pressure
 Molecular weight
 Structure of the molecule & intermolecular
interactions
 Branching
 Polarity
 Van der Waals interactions
 H-bonding
 Impurities
Factors affecting B.P.

a. When the pressure is less than 1 atm , the boiling

point of the liquid is less than its normal b.p.
b. P = 1 atm, the b.p. of the liquid is called normal
boiling point
c. When P is greater than 1 atm, the b.p. of the liquid is
greater than its normal b.p.

The higher the altitude, the lower the

temp at which water boils
Factors affecting B.P.

CH4 and CH3Cl

H H

C C
H
H
H
H
H
Cl
 Formula IUPAC Name Boiling Point
HCO2H methanoic acid 101 oC
CH3CO2H ethanoic acid 118 oC
CH3CH2CO2H propanoic acid 141 oC
CH3(CH2)2CO2H butanoic acid 164 oC
CH3(CH2)3CO2H pentanoic acid 186 oC
CH3(CH2)4CO2H hexanoic acid 205 oC
CH3(CH2)5CO2H heptanoic acid 223 oC
Factors affecting B.P.
Within the branched series, increased symmetry leads to higher
melting point and lower boiling point
Factors affecting B.P.

 CH4 (b.p. -161.5) , CH3-O-CH3 (b.p. -24)

 Butane (-0.6 oC) , acetone (56 oC)
Factors affecting B.P.

 pentane (36), isopentane (31) and neopentane (9)

Pentane bp 36 oC 2,2-dimethylpropane bp 9.5 oC

 OH OH OH

1-butanol (118), 2-butanol (100) 2-mehtyl-2-propanol (83)

n-butanol isobutanol tert-butanol
Factors affecting B.P.

 HF higher than HCl by 100 oC

 H2O higher than H2S by 160 oC

H2O ( M.wt.=18): boiling point 100 oC

H2S ( M.wt.=34): boiling point -60 oC

 CH3OH (66), CH3SH (6)

 CH3-O-CH3 (-24), CH3-S-CH3 (38)
b.p. is supposed to increase directly
with m.wt., however, this is not the
case for H2O, NH3 and HF
 Compound Structure Boiling point

Acetamide CH3C(O)NH2 222 oC

Acetic acid CH3CO2H 118 oC

Ethanol CH3CH2-OH 78 oC

Ethylamine CH3CH2-NH2 17 oC

Ethane CH3CH3 -89 oC

Q/ Explain the reason for the difference in b.p. of the

above compounds.
Factors affecting B.P.

 A solution has a higher boiling point than a pure

solvent .
 The b.p. of pure H2O is 100 oC, but that b.p. can be
elevated by adding a solute such as a salt.
Δ Tb = Kb Cm
where Kb is called the boiling-point elevation constant
The reason for elevating b.p. is:
 the number of solvent molecules at the surface of the
solution is less than for pure solvent. The surface
molecules can be considered “diluted” by the less
volatile particles of the solute
 The rate of exchange between solvent in the solution
and the air above it is lower (vapor pressure of the
solvent is reduced)
 A lower pressure means that a higher temperature is
necessary to boil the water in the solution , hence
boiling point elevation
 Conversely, adding common salt to water will lower its
freezing point.
Ionic vs. covalent compounds
1413 oC

Na+ Cl- Na+ Cl- Cl-

Cl- Na+Na+Cl-Na+ Na+

Boiling occurs when a temp. is reached

at which the thermal energy of the
particles ix great enough to overcome
the attractive forces that hold them in
liquid
 -161.5 oC

In the liquid state of a covalent compound, the

weak intermolecular interactions are more are
more easily overcome and boiling occurs at much
lower temp.
Apparatus
A small-scale simple
distillation apparatus
(sample size ~ 10ml)
Miniscale boiling point
determination
sample size ~0.5 – 1 ml
Procedure