What To Expect When Being Asked Boiling Point Questions On Exams

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First thing to know: you'll be expected to understand trends in boiling points - not absolutes.
E.g. "which of these molecules will have the highest/lowest boiling point", or "rank these molecules in order of increasing/decreasing boiling point".
NOT - "give the boiling point of this molecule".
O O O

ONa OH
A B C D

Determining the exact boiling point of a molecule can only be done experimentally - by measurement.
Guessing trends, however - which molecule in a given set will have the highest or lowest boiling point - is very doable.
Here are three key trends that will help to answer >90% of typical boiling point questions. More details are provided on the following pages.

Trend #1: Forces Trend #2: Size Trend #3: Surface Area

stronger forces = increasing # of carbons = increasing surface area =

higher boiling point increasing boiling point increasing boiling point
(all else being equal) (among molecules with identical functional groups) (among molecules with identical functional groups
that have the same # of carbons)
With molecular weight With the types of forces constant,
roughly constant, boiling point boiling point will increase with an With the types of forces constant and
increases according to the types increasing number of carbons molecular weight constant,
of intermolecular forces present boiling point increases wtih
in the molecule. Boiling point incresaes with increased increased surface area
surface area, which increases as the
There are 4 general "types" of carbon chain is lengthened.
intermolecular forces, which are > >
determined by the functional groups Examples of the trend:
present C5H12 C5H12 C5H12
> >
NH 2 NH 2 NH 2 310 K 300 K 283 K
• ionic forces (salts) (36 °C) (27 °C) (10 °C)
butylamine propylamine ethylamine
• hydrogen bonding (alcohols, 351 K 322 K 291 K linear branched highly branched
carboxylic acids, amines) (78 °C) (49 °C) (18 °C)
(Highest (Most sphere-like:
• dipole-dipole forces (carbon
> > surface area) lowest surface area)
bound to electronegative groups like
O, N, Cl, etc.)
C8H18 C6H14 C4H10
• London (dispersion) forces - For more information, check the next page
present in all molecules, but most 398 K 341 K 272 K
prominent for hydrocarbons, since (125 °C) (68 °C) (–1 °C)
they lack the previous three
> > O
O O
KEY TREND: ionic forces are
stronger than hydrogen bonding which dipropyl ether diethyl ether dimethyl ether
is stronger than dipole-dipole forces, 363 K 307 K 249 K
which are stronger than London (90 °C) (34 °C) (–24 °C)
(disperson) forces questions, comments, corrections:
james@masterorganicchemistry.com
More details on these in the next page. Note that these all share the same functional groups. The only Twitter: @jamesashchem
variable changing here is the size of the carbon chain.
For more great “cheat
sheets”, visit the MOC
Study Guide Homepage
For more great “cheat
sheets”, visit the MOC
Study Guide Homepage