The Foundations of Chemistry

Groups other than hydrogen can be substituted by other atoms or groups of atoms.

For example, the bromine atom of an alkyl bromide can be replaced with a hydroxyl group

to form an alcohol. The mechanism of this type of reaction is often studied in introduc-

tory organic chemistry courses.

Alcohols react with common inorganic oxyacids to produce inorganic esters.For

instance, nitric acid reacts with alcohols to produce nitrates by substitution of nitrate,

XONO 2 , for hydroxyl, XOH.

CH 3 CH 2 OHHNO 3 88n CH 3 CH 2 XONO 2 H 2 O

ethanol nitric acid ethyl nitrate

The substitution reaction of nitric acid with glycerol produces the explosive nitroglyc-

erine. Alfred Nobel’s (1833–1896) discovery in 1866 that this very sensitive material could

be made into a “safe” explosive by absorbing it into diatomaceous earth or wood meal led

to his development of dynamite.

Cold, concentrated H 2 SO 4 reacts with alcohols to form alkyl hydrogen sulfates.The

reaction with lauryl alcohol is an important industrial reaction.

CH 3 (CH 2 ) 10 CH 2 XOHoHOSO 3 Ho88nCH 3 (CH 2 ) 10 CH 2 XOSO 3 HH 2 O

1-dodecanol(lauryl alcohol) sulfuric lauryl hydrogen sulfate

acid

The neutralization reaction of an alkyl hydrogen sulfate with NaOH then produces the

sodium salt of the alkyl hydrogen sulfate.

CH 3 (CH 2 ) 10 CH 2 XOSO 3 HNaOH88nCH 3 (CH 2 ) 10 CH 2 XOSO 3 NaH 2 O

sodium lauryl sulfate (a detergent)

Sodium salts of the alkyl hydrogen sulfates that contain about 12 carbon atoms are excel-

lent detergents. They are also biodegradable. (Soaps and detergents were discussed in

Section 14-18.)

ADDITION REACTIONS

An addition reactioninvolves an increasein the number of atoms or groups attached

to carbon. The molecule becomes more nearly saturated.

27-17



H 2 SO 4

3HNO 3

glycerol glyceryl trinitrate

(nitroglycerine)

H 2 C

H 2 C

OH

HC OH HC ONO 2 3H 2 O

H 2 C ONO 2

H 2 C ONO 2

OH

CH 3 CH CH 3 OH Br

Br

CH 3 CH CH 3

OH

Simple inorganic esters may be
thought of as compounds that contain
one or more alkyl groups covalently
bonded to the anion of a ternary
inorganic acid. Unless indicated, the
term “ester” refers to organic esters.

1088 CHAPTER 27: Organic Chemistry I: Formulas, Names, and Properties

Interestingly, nitroglycerine (“nitro”) is
taken by some who have heart disease.
It acts as a vasodilator (dilates the
blood vessels) to decrease arterial
tension.

Nobel’s brother had been killed and
his father physically disabled in a
nitroglycerine explosion in 1864.
Nobel willed $9.2 million to establish
a fund for annual prizes in physics,
chemistry, medicine, literature, and
peace. The prizes were first awarded
in 1901.