Professional Documents
Culture Documents
1
Chlorine
Chlorine
17
Cl
sulfur chlorine argonF
Cl
Br
Chlorine in the periodic table
Appearance
pale yellow-green gas
General properties
Name, symbol, number chlorine, Cl, 17
Pronunciation /klrin/ KLOHR-een
or /klrn/ KLOHR-n
Element category diatomic nonmetal
Group, period, block 17 (halogens), 3, p
Standard atomic weight 35.45(1)
Chlorine
2
Electron configuration
[Ne] 3s
2
3p
5
2, 8, 7
History
Discovery Carl Wilhelm Scheele (1774)
First isolation Carl Wilhelm Scheele (1774)
Recognized as an element by Humphry Davy (1808)
Physical properties
Phase gas
Density (0 C, 101.325 kPa)
3.2 g/L
Liquid density at b.p.
1.5625
[1]
gcm
3
Meltingpoint 171.6K, -101.5C, -150.7F
Boilingpoint 239.11K, -34.04C, -29.27F
Criticalpoint 416.9 K, 7.991 MPa
Heatoffusion
(Cl
2
) 6.406 kJmol
1
Heat of vaporization
(Cl
2
) 20.41 kJmol
1
Molar heat capacity
(Cl
2
)
33.949 Jmol
1
K
1
Vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 128 139 153 170 197 239
Atomic properties
Oxidation states 7, 6, 5, 4, 3, 2, 1, -1
(strongly acidic oxide)
Electronegativity 3.16 (Pauling scale)
Ionization energies
(more)
1st: 1251.2 kJmol
1
2nd: 2298 kJmol
1
3rd: 3822 kJmol
1
Covalent radius 1024 pm
Chlorine
3
Van der Waals radius 175 pm
Miscellanea
Crystal structure orthorhombic
Magnetic ordering
diamagnetic
[2]
Electrical resistivity (20C) > 10m
Thermal conductivity
8.910
3
Wm
1
K
1
Speed of sound
(gas, 0 C) 206 ms
1
CAS registry number 7782-50-5
Most stable isotopes
Main article: Isotopes of chlorine
iso NA half-life DM DE (MeV) DP
35
Cl
75.77% 35
Cl is stable with 18 neutrons
36
Cl
trace
3.0110
5
y
0.709 36
Ar
- 36
S
37
Cl
24.23% 37
Cl is stable with 20 neutrons
Chlorine is a chemical element with symbolCl and atomic number17. Chlorine is in the halogen group (17) and is
the second lightest halogen after fluorine. The element is a yellow-green gas under standard conditions, where it
forms diatomic molecules. It has the highest electron affinity and the third highest electronegativity of all the
elements; for this reason, chlorine is a strong oxidizing agent. Free chlorine is rare on Earth, and is usually a result of
direct or indirect oxidation by oxygen.
The most common compound of chlorine, sodium chloride (common salt), has been known since ancient times.
Around 1630 chlorine gas was first synthesized in a chemical reaction, but not recognized as a fundamentally
important substance. Characterization of chlorine gas was made in 1774 by Carl Wilhelm Scheele, who supposed it
an oxide of a new element. In 1809 chemists suggested that the gas might be a pure element, and this was confirmed
by Sir Humphry Davy in 1810, who named it from Ancient Greek: khlros"pale green".
Nearly all chlorine in the Earth's crust occurs as chloride in various ionic compounds, including table salt. It is the
second most abundant halogen and 21
st
most abundant chemical element in Earth's crust. Elemental chlorine is
commercially produced from brine by electrolysis. The high oxidizing potential of elemental chlorine led
commercially to free chlorine's bleaching and disinfectant uses, as well as its many uses of an essential reagent in the
chemical industry. Chlorine is used in the manufacture of a wide range of consumer products, about two-thirds of
them organic chemicals such as polyvinyl chloride, as well as many intermediates for production of plastics and
other end products which do not contain the element. As a common disinfectant, elemental chlorine and
chlorine-generating compounds are used more directly in swimming pools to keep them clean and sanitary.
In the form of chloride ions, chlorine is necessary to all known species of life. Other types of chlorine compounds
are rare in living organisms, and artificially produced chlorinated organics range from inert to toxic. In the upper
atmosphere, chlorine-containing organic molecules such as chlorofluorocarbons have been implicated in ozone
Chlorine
4
depletion. Small quantities of elemental chlorine are generated by oxidation of chloride to hypochlorite in
neutrophils, as part of the immune response against bacteria. Elemental chlorine at high concentrations is extremely
dangerous and poisonous for all living organisms, and was historically used in World War I as the first gaseous
chemical warfare agent.
Characteristics
Physical characteristics of chlorine and its compounds
Chlorine, liquefied under a pressure of 7.4 bar at
room temperature, displayed in a quartz ampule
embedded in acrylic glass.
At standard temperature and pressure, two chlorine atoms form the
diatomic molecule Cl
2
.
[3]
This is a yellow-green gas that has a
distinctive strong odor, familiar to most from common household
bleach.
[4]
The bonding between the two atoms is relatively weak (only
242.580 0.004kJ/mol), which makes the Cl
2
molecule highly
reactive. The boiling point at regular atmosphere is around 34 C, but
it can be liquefied at room temperature with pressures above 740
kPa.
[5]
Although elemental chlorine is yellow-green, chloride ion, in common
with other halide ions, has no color in either minerals or solutions
(example, table salt). Similarly, (again as with other halogens) chlorine
atoms impart no color to organic chlorides when they replace hydrogen
atoms in colorless organic compounds, such as tetrachloromethane.
The melting point and density of these compounds is increased by
substitution of hydrogen in place of chlorine. Compounds of chlorine with other halogens, however, as well as many
chlorine oxides, are visibly colored.
Chemical characteristics
Along with fluorine, bromine, iodine, and astatine, chlorine is a member of the halogen series that forms the group
17 (formerly VII, VIIA, or VIIB) of the periodic table. Chlorine forms compounds with almost all of the elements to
give compounds that are usually called chlorides. Chlorine gas reacts with most organic compounds, and will even
sluggishly support the combustion of hydrocarbons.
[]
Hydrolysis of free chlorine or disproportionation in water
At 25C and atmospheric pressure, one liter of water dissolves 3.26g or 1.125L of gaseous chlorine.
[6]
Solutions of
chlorine in water contain chlorine (Cl
2
), hydrochloric acid, and hypochlorous acid:
Cl
2
+ H
2
O HCl + HClO
This conversion to the right is called disproportionation, because the ingredient chlorine both increases and decreases
in formal oxidation state. The solubility of chlorine in water is increased if the water contains dissolved alkali
hydroxide, and in this way, chlorine bleach is produced.
[7]
Cl
2
+ 2 OH
ClO
+ Cl
+ H
2
O
Chlorine gas only exists in a neutral or acidic solution.
Chlorine
5
Chemistry and compounds
Chlorine exists in all odd numbered oxidation states from 1 to +7, as well as the elemental state of zero and four in
chlorine dioxide (see table below, and also structures in chlorite).
[8]
Progressing through the states, hydrochloric acid
can be oxidized using manganese dioxide, or hydrogen chloride gas oxidized catalytically by air to form elemental
chlorine gas.
[9]
Oxidation
state
Name Formula Characteristic compounds
1 chlorides
Cl
ionic chlorides, organic chlorides, hydrochloric acid
0 chlorine Cl
2
elemental chlorine
+1 hypochlorites
ClO
sodium hypochlorite, calcium hypochlorite
+3 chlorites ClO
2
sodium chlorite
+4 chlorine(IV) ClO
2
chlorine dioxide
+5 chloryl,
chlorates
ClO
3 ClO+
2
potassium chlorate, chloric acid, dichloryl trisulfate [ClO2]
2
[S
3
O
10
].
+6 chlorine(VI) Cl
2O
6
dichlorine hexoxide (gas). In liquid or solid disproportionates to mix of +5 and +7 oxidation states, as
ionic chloryl perchlorate [ClO
2]+
[ClO
4]
+7 perchlorates ClO
4
perchloric acid, perchlorate salts such as magnesium perchlorate, dichlorine heptoxide
Chlorides
Chlorine combines with almost all elements to give chlorides. Compounds with oxygen, nitrogen, xenon, and
krypton are known, but do not form by direct reaction of the elements.
[10]
Chloride is one of the most common
anions in nature. Hydrogen chloride and its aqueous solution, hydrochloric acid, are produced on megaton scale
annually both as valued intermediates but sometimes as undesirable pollutants.
Chlorine oxides
Chlorine forms a variety of oxides, as seen above: chlorine dioxide (ClO
2
), dichlorine monoxide (Cl
2
O), dichlorine
hexoxide (Cl
2
O
6
), dichlorine heptoxide (Cl
2
O
7
). The anionic derivatives of these same oxides are also well known
including chlorate (ClO
3), chlorite (ClO
2), hypochlorite (ClO
Cl
+ ClO
2
ClO
+ ClO
2 Cl
+ ClO
3
Sodium chlorate and potassium chlorate can be crystallized from solutions formed by the above reactions. If their
crystals are heated, they undergo a further, final disproportionation:
4 ClO
3 Cl
+ 3 ClO
4
This same progression from chloride to perchlorate can be accomplished by electrolysis. The anode reaction
progression is:
[]
Reaction Electrode
potential
Cl
+ 2 OH
ClO
+ H
2
O + 2 e
+0.89 volts
ClO
+ 2 OH
ClO
2 + H
2
O + 2 e
+0.67 volts
ClO
2 + 2 OH
ClO
3 + H
2
O + 2 e
+0.33 volts
ClO
3 + 2 OH
ClO
4 + H
2
O + 2 e
+0.35 volts
Each step is accompanied at the cathode by
2 H
2
O + 2 e
2 OH
+ H
2
(0.83 volts)
Interhalogen compounds
Chlorine oxidizes bromide and iodide salts to bromine and iodine, respectively. However, it cannot oxidize fluoride
salts to fluorine. It makes a variety of interhalogen compounds, such as the chlorine fluorides, chlorine monofluoride
(ClF), chlorine trifluoride (ClF
3), chlorine pentafluoride (ClF
5). Chlorides of bromine and iodine are also known.
[13]
Organochlorine compounds
Chlorine is used extensively in organic chemistry in substitution and addition reactions. Chlorine often imparts many
desired properties to an organic compound, in part owing to its electronegativity.
Like the other halides, chlorine undergoes electrophilic addition reactions, the most notable one being the
chlorination of alkenes and aromatic compounds with a Lewis acid catalyst. Organic chlorine compounds tend to be
less reactive in nucleophilic substitution reactions than the corresponding bromine or iodine derivatives, but they
tend to be cheaper. They may be activated for reaction by substituting with a tosylate group, or by the use of a
catalytic amount of sodium iodide.
[citation needed]
Chlorine
7
Occurrence
In the interstellar medium, chlorine is produced in supernovae via the r-process.
[14]
In meteorites and on Earth, chlorine is found primarily as the chloride ion which occurs in minerals. In the Earth's
crust, chlorine is present at average concentrations of about 126 parts per million,
[15]
predominantly in such minerals
as halite (sodium chloride), sylvite (potassium chloride), and carnallite (potassium magnesium chloride
hexahydrate).
Chloride is a component of the salt that is deposited in the earth or dissolved in the oceans about 1.9% of the mass
of seawater is chloride ions. Even higher concentrations of chloride are found in the Dead Sea and in underground
brine deposits. Most chloride salts are soluble in water, thus, chloride-containing minerals are usually only found in
abundance in dry climates or deep underground.
Over 2000 naturally occurring organic chlorine compounds are known.
[]
Isotopes
Chlorine has a wide range of isotopes. The two stable isotopes are
35
Cl (75.77%) and
37
Cl (24.23%).
[]
Together they
give chlorine an atomic weight of 35.4527g/mol. The half-integer value for chlorine's weight caused some confusion
in the early days of chemistry, when it had been postulated that atoms were composed of even units of hydrogen (see
Proust's law), and the existence of chemical isotopes was unsuspected.
[]
Trace amounts of radioactive
36
Cl exist in the environment, in a ratio of about 7x10
13
to 1 with stable isotopes.
36
Cl
is produced in the atmosphere by spallation of
36
Ar by interactions with cosmic ray protons. In the subsurface
environment,
36
Cl is generated primarily as a result of neutron capture by
35
Cl or muon capture by
40
Ca.
36
Cl decays
to
36
S and to
36
Ar, with a combined half-life of 308,000 years. The half-life of this hydrophilic nonreactive isotope
makes it suitable for geologic dating in the range of 60,000 to 1million years. Additionally, large amounts of
36
Cl
were produced by irradiation of seawater during atmospheric detonations of nuclear weapons between 1952 and
1958. The residence time of
36
Cl in the atmosphere is about 1 week. Thus, as an event marker of 1950s water in soil
and ground water,
36
Cl is also useful for dating waters less than 50 years before the present.
36
Cl has seen use in
other areas of the geological sciences, including dating ice and sediments.
[]
History
The most common compound of chlorine, sodium chloride, has been known since ancient times; archaeologists have
found evidence that rock salt was used as early as 3000 BC and brine as early as 6000 BC.
[16]
Around 1630, chlorine
was recognized as a gas by the Belgian chemist and physician Jan Baptist van Helmont.
[17]
Carl Wilhelm Scheele
Elemental chlorine was first prepared and studied in 1774 by Swedish chemist
Carl Wilhelm Scheele, and, therefore, he is credited for its discovery.
[]
He
called it "dephlogisticated muriatic acid air" since it is a gas (then called "airs")
and it came from hydrochloric acid (then known as "muriatic acid").
[]
However,
he failed to establish chlorine as an element, mistakenly thinking that it was the
oxide obtained from the hydrochloric acid (see phlogiston theory).
[]
He named
the new element within this oxide as muriaticum.
[]
Regardless of what he
thought, Scheele did isolate chlorine by reacting MnO
2
(as the mineral
pyrolusite) with HCl:
[17]
4 HCl + MnO
2
MnCl
2
+ 2 H
2
O + Cl
2
Scheele observed several of the properties of chlorine: the bleaching effect on
litmus, the deadly effect on insects, the yellow green color, and the smell similar
to aqua regia.
[18]
Chlorine
8
At the time, common chemical theory was: any acid is a compound that contains oxygen (still sounding in the
German and Dutch names of oxygen: sauerstoff or zuurstof, both translating into English as acid stuff), so a number
of chemists, including Claude Berthollet, suggested that Scheele's dephlogisticated muriatic acid air must be a
combination of oxygen and the yet undiscovered element, muriaticum.
[19][20][]
In 1809, Joseph Louis Gay-Lussac and Louis-Jacques Thnard tried to decompose dephlogisticated muriatic acid air
by reacting it with charcoal to release the free element muriaticum (and carbon dioxide).
[]
They did not succeed and
published a report in which they considered the possibility that dephlogisticated muriatic acid air is an element, but
were not convinced.
[21]
In 1810, Sir Humphry Davy tried the same experiment again, and concluded that it is an element, and not a
compound.
[]
He named this new element as chlorine, from the Greek word (chlros), meaning
green-yellow.
[22]
The name halogen, meaning "salt producer," was originally used for chlorine in 1811 by Johann
Salomo Christoph Schweigger. However, this term was later used as a generic term to describe all the elements in
the chlorine family (fluorine, bromine, iodine), after a suggestion by Jns Jakob Berzelius in 1842.
[23][24]
In 1823,
Michael Faraday liquefied chlorine for the first time,
[25][26]
and demonstrated that what was then known as "solid
chlorine" had a structure of chlorine hydrate (Cl
2
H
2
O).
[17]
Chlorine gas was first used by French chemist Claude Berthollet to bleach textiles in 1785.
[][]
Modern bleaches
resulted from further work by Berthollet, who first produced sodium hypochlorite in 1789 in his laboratory in the
town of Javel (now part of Paris, France), by passing chlorine gas through a solution of sodium carbonate. The
resulting liquid, known as "Eau de Javel" ("Javel water"), was a weak solution of sodium hypochlorite. However,
this process was not very efficient, and alternative production methods were sought. Scottish chemist and
industrialist Charles Tennant first produced a solution of calcium hypochlorite ("chlorinated lime"), then solid
calcium hypochlorite (bleaching powder).
[]
These compounds produced low levels of elemental chlorine, and could
be more efficiently transported than sodium hypochlorite, which remained as dilute solutions because when purified
to eliminate water, it became a dangerously powerful and unstable oxidizer. Near the end of the nineteenth century,
E. S. Smith patented a method of sodium hypochlorite production involving electrolysis of brine to produce sodium
hydroxide and chlorine gas, which then mixed to form sodium hypochlorite.
[27]
This is known as the chloralkali
process, first introduced on an industrial scale in 1892, and now the source of essentially all modern elemental
chlorine and sodium hydroxide production (a related low-temperature electrolysis reaction, the Hooker process, is
now responsible for bleach and sodium hypochlorite production).
Elemental chlorine solutions dissolved in chemically basic water (sodium and calcium hypochlorite) were first used
as anti-putrification agents and disinfectants in the 1820s, in France, long before the establishment of the germ
theory of disease. This work is mainly due to Antoine-Germain Labarraque, who adapted Berthollet's "Javel water"
bleach and other chlorine preparations for the purpose (for a more complete history, see below). Elemental chlorine
has since served a continuous function in topical antisepsis (wound irrigation solutions and the like) as well as public
sanitation (especially of swimming and drinking water).
In 1826, silver chloride was used to produce photographic images for the first time.
[]
Chloroform was first used as an
anesthetic in 1847.
[]
Polyvinyl chloride (PVC) was invented in 1912, initially without a purpose.
[]
Chlorine gas was first introduced as a weapon on April 22, 1915, at Ypres by the German Army,
[28][29]
and the
results of this weapon were disastrous because gas masks had not been mass distributed and were tricky to get on
quickly.
Chlorine
9
Production
Liquid chlorine analysis
In industry, elemental chlorine is usually produced by the electrolysis of sodium
chloride dissolved in water. This method, the chloralkali process industrialized in
1892, now provides essentially all industrial chlorine gas.
[30]
Along with
chlorine, the method yields hydrogen gas and sodium hydroxide (with sodium
hydroxide actually being the most crucial of the three industrial products
produced by the process). The process proceeds according to the following
chemical equation:
[9]
2 NaCl + 2 H
2
O Cl
2
+ H
2
+ 2 NaOH
The electrolysis of chloride solutions all proceed according to the following
equations:
Cathode: 2 H
+
(aq) + 2 e
H
2
(g)
Anode: 2 Cl
(aq) Cl
2
(g) + 2 e