Chemical reaction

A chemical reaction is a process that leads to the chemical transformation of one set of chemical
substances to another.[1] Classically, chemical reactions encompass changes that only involve the
positions of electrons in the forming and breaking of chemical bonds between atoms, with no change
to the nuclei (no change to the elements present), and can often be described by a chemical
equation. Nuclear chemistry is a sub-discipline of chemistry that involves the chemical reactions
of unstable and radioactive elements where both electronic and nuclear changes can occur.
The substance (or substances) initially involved in a chemical reaction are called reactants or
reagents. Chemical reactions are usually characterized by a chemical change, and they yield one or
more products, which usually have properties different from the reactants. Reactions often consist of
a sequence of individual sub-steps, the so-called elementary reactions, and the information on the
precise course of action is part of the reaction mechanism. Chemical reactions are described
with chemical equations, which symbolically present the starting materials, end products, and
sometimes intermediate products and reaction conditions.
Chemical reactions happen at a characteristic reaction rate at a given temperature and chemical
concentration. Typically, reaction rates increase with increasing temperature because there is
more thermal energy available to reach the activation energy necessary for breaking bonds between
atoms.
Reactions may proceed in the forward or reverse direction until they go to completion or reach
equilibrium. Reactions that proceed in the forward direction to approach equilibrium are often
described as spontaneous, requiring no input of free energy to go forward. Non-spontaneous
reactions require input of free energy to go forward (examples include charging a battery by applying
an external electrical power source, or photosynthesis driven by absorption of electromagnetic
radiation in the form of sunlight).
Different chemical reactions are used in combinations during chemical synthesis in order to obtain a
desired product. In biochemistry, a consecutive series of chemical reactions (where the product of
one reaction is the reactant of the next reaction) form metabolic pathways. These reactions are
often catalyzed by protein enzymes. Enzymes increase the rates of biochemical reactions, so
that metabolic syntheses and decompositions impossible under ordinary conditions can occur at the
temperatures and concentrations present within a cell.
The general concept of a chemical reaction has been extended to reactions between entities smaller
than atoms, including nuclear reactions, radioactive decays, and reactions between elementary
particles, as described by quantum field theory.

Contents

 1History
 2Equations
 3Elementary reactions
 4Chemical equilibrium
 5Thermodynamics
 6Kinetics
 7Reaction types
o 7.1Four basic types
 7.1.1Synthesis
  7.1.2Decomposition
 7.1.3Single replacement
 7.1.4Double replacement
o 7.2Oxidation and reduction
o 7.3Complexation
o 7.4Acid-base reactions
o 7.5Precipitation
o 7.6Solid-state reactions
o 7.7Reactions at the solid|gas interface
o 7.8Photochemical reactions
 8Catalysis
 9Reactions in organic chemistry
o 9.1Substitution
o 9.2Addition and elimination
o 9.3Other organic reaction mechanisms
 10Biochemical reactions
 11Applications
 12Monitoring
 13See also
 14References
 15Bibliography

History

Antoine Lavoisier developed the theory of combustion as a chemical reaction with oxygen.

Chemical reactions such as combustion in fire, fermentation and the reduction of ores to metals
were known since antiquity. Initial theories of transformation of materials were developed by Greek
philosophers, such as the Four-Element Theory of Empedocles stating that any substance is
composed of the four basic elements – fire, water, air and earth. In the Middle Ages, chemical
transformations were studied by Alchemists. They attempted, in particular, to convert lead into gold,
for which purpose they used reactions of lead and lead-copper alloys with sulfur.[2]
The production of chemical substances that do not normally occur in nature has long been tried,
such as the synthesis of sulfuric and nitric acids attributed to the controversial alchemist Jābir ibn
Hayyān. The process involved heating of sulfate and nitrate minerals such as copper
sulfate, alum and saltpeter. In the 17th century, Johann Rudolph Glauber produced hydrochloric
acid and sodium sulfate by reacting sulfuric acid and sodium chloride. With the development of
the lead chamber process in 1746 and the Leblanc process, allowing large-scale production of
sulfuric acid and sodium carbonate, respectively, chemical reactions became implemented into the
industry. Further optimization of sulfuric acid technology resulted in the contact process in the
1880s,[3] and the Haber process was developed in 1909–1910 for ammonia synthesis.[4]
From the 16th century, researchers including Jan Baptist van Helmont, Robert Boyle, and Isaac
Newton tried to establish theories of the experimentally observed chemical transformations.
The phlogiston theory was proposed in 1667 by Johann Joachim Becher. It postulated the existence
of a fire-like element called "phlogiston", which was contained within combustible bodies and
released during combustion. This proved to be false in 1785 by Antoine Lavoisier who found the
correct explanation of the combustion as reaction with oxygen from the air.[5]
Joseph Louis Gay-Lussac recognized in 1808 that gases always react in a certain relationship with
each other. Based on this idea and the atomic theory of John Dalton, Joseph Proust had developed
the law of definite proportions, which later resulted in the concepts of stoichiometry and chemical
equations.[6]
Regarding the organic chemistry, it was long believed that compounds obtained from living
organisms were too complex to be obtained synthetically. According to the concept of vitalism,
organic matter was endowed with a "vital force" and distinguished from inorganic materials. This
separation was ended however by the synthesis of urea from inorganic precursors by Friedrich
Wöhler in 1828. Other chemists who brought major contributions to organic chemistry
include Alexander William Williamson with his synthesis of ethers and Christopher Kelk Ingold, who,
among many discoveries, established the mechanisms of substitution reactions.

Equations

As seen from the equation CH

4 +2O
2 → CO
2 +2H
O, a coefficient of 2 must be placed before the oxygen gas on the reactants side and before the water on the
2
products side in order for, as per the law of conservation of mass, the quantity of each element does not
change during the reaction

Main article: Chemical equation

Chemical equations are used to graphically illustrate chemical reactions. They consist
of chemical or structural formulas of the reactants on the left and those of the products on the right.
They are separated by an arrow (→) which indicates the direction and type of the reaction; the arrow
is read as the word "yields".[7] The tip of the arrow points in the direction in which the reaction
proceeds. A double arrow (⇌) pointing in opposite directions is used for equilibrium reactions.
Equations should be balanced according to the stoichiometry, the number of atoms of each species
should be the same on both sides of the equation. This is achieved by scaling the number of

involved molecules ( and in a schematic example below) by the appropriate integers a, b,

c and d.[8]

More elaborate reactions are represented by reaction schemes, which in addition to starting
materials and products show important intermediates or transition states. Also, some relatively
minor additions to the reaction can be indicated above the reaction arrow; examples of such
additions are water, heat, illumination, a catalyst, etc. Similarly, some minor products can be
placed below the arrow, often with a minus sign.

An example of organic reaction: oxidation of ketones to esters with a peroxycarboxylic acid

Retrosynthetic analysis can be applied to design a complex synthesis reaction. Here the
analysis starts from the products, for example by splitting selected chemical bonds, to arrive at
plausible initial reagents. A special arrow (⇒) is used in retro reactions.[9]

Elementary reactions
The elementary reaction is the smallest division into which a chemical reaction can be
decomposed, it has no intermediate products.[10] Most experimentally observed reactions are
built up from many elementary reactions that occur in parallel or sequentially. The actual
sequence of the individual elementary reactions is known as reaction mechanism. An
elementary reaction involves a few molecules, usually one or two, because of the low probability
for several molecules to meet at a certain time.[11]

Isomerization of azobenzene, induced by light (hν) or heat (Δ)

The most important elementary reactions are unimolecular and bimolecular reactions. Only one
molecule is involved in a unimolecular reaction; it is transformed by an isomerization or
a dissociation into one or more other molecules. Such reactions require the addition of energy in
the form of heat or light. A typical example of a unimolecular reaction is the cis–
trans isomerization, in which the cis-form of a compound converts to the trans-form or vice
versa.[12]
In a typical dissociation reaction, a bond in a molecule splits (ruptures) resulting in two
molecular fragments. The splitting can be homolytic or heterolytic. In the first case, the bond is
divided so that each product retains an electron and becomes a neutral radical. In the second
case, both electrons of the chemical bond remain with one of the products, resulting in
charged ions. Dissociation plays an important role in triggering chain reactions, such
as hydrogen–oxygen or polymerization reactions.

Dissociation of a molecule AB into fragments A and B

For bimolecular reactions, two molecules collide and react with each other. Their merger
is called chemical synthesis or an addition reaction.

Another possibility is that only a portion of one molecule is transferred to the other
molecule. This type of reaction occurs, for example, in redox and acid-base
reactions. In redox reactions, the transferred particle is an electron, whereas in acid-
base reactions it is a proton. This type of reaction is also called metathesis.

for example

Chemical equilibrium
Main article: Chemical equilibrium
Most chemical reactions are reversible, that is they can and do run in both
directions. The forward and reverse reactions are competing with each
other and differ in reaction rates. These rates depend on the concentration
and therefore change with time of the reaction: the reverse rate gradually
increases and becomes equal to the rate of the forward reaction,
establishing the so-called chemical equilibrium. The time to reach
equilibrium depends on such parameters as temperature, pressure and the
materials involved, and is determined by the minimum free energy. In
equilibrium, the Gibbs free energy must be zero. The pressure dependence
can be explained with the Le Chatelier's principle. For example, an increase
in pressure due to decreasing volume causes the reaction to shift to the
side with the fewer moles of gas.[13]
The reaction yield stabilizes at equilibrium, but can be increased by
removing the product from the reaction mixture or changed by increasing
the temperature or pressure. A change in the concentrations of the
 reactants does not affect the equilibrium constant, but does affect the
equilibrium position.

Thermodynamics
Chemical reactions are determined by the laws of thermodynamics.
Reactions can proceed by themselves if they are exergonic, that is if they
release energy. The associated free energy of the reaction is composed of
two different thermodynamic quantities, enthalpy and entropy:[14]

.
G: free energy, H: enthalpy, T: temperature, S: entropy, Δ: difference(change between original and product)
Reactions can be exothermic, where ΔH is negative and energy is
released. Typical examples of exothermic reactions
are precipitation and crystallization, in which ordered solids are formed
from disordered gaseous or liquid phases. In contrast,
in endothermic reactions, heat is consumed from the environment. This
can occur by increasing the entropy of the system, often through the
formation of gaseous reaction products, which have high entropy. Since
the entropy increases with temperature, many endothermic reactions
preferably take place at high temperatures. On the contrary, many
exothermic reactions such as crystallization occur at low temperatures.
Changes in temperature can sometimes reverse the sign of the
enthalpy of a reaction, as for the carbon monoxide reduction
of molybdenum dioxide:

;
This reaction to form carbon dioxide and molybdenum is
endothermic at low temperatures, becoming less so with increasing
temperature.[15] ΔH° is zero at 1855 K, and the reaction becomes
exothermic above that temperature.
Changes in temperature can also reverse the direction tendency of
a reaction. For example, the water gas shift reaction

is favored by low temperatures, but its reverse is favored by

high temperature. The shift in reaction direction tendency
occurs at 1100 K.[15]
Reactions can also be characterized by the internal
energy which takes into account changes in the entropy,
volume and chemical potential. The latter depends, among
other things, on the activities of the involved substances.[16]

U: internal energy, S: entropy, p: pressure, μ: chemical potential, n: number of molecules, d: small change
sign
Kinetics
The speed at which reactions takes place is studied
by reaction kinetics. The rate depends on various
parameters, such as:

 Reactant concentrations, which usually make the

reaction happen at a faster rate if raised through
increased collisions per unit time. Some reactions,
however, have rates that are independent of reactant
concentrations. These are called zero order reactions.
 Surface area available for contact between the
reactants, in particular solid ones in heterogeneous
systems. Larger surface areas lead to higher reaction
rates.
 Pressure – increasing the pressure decreases the
volume between molecules and therefore increases
the frequency of collisions between the molecules.
 Activation energy, which is defined as the amount of
energy required to make the reaction start and carry on
spontaneously. Higher activation energy implies that
the reactants need more energy to start than a reaction
with a lower activation energy.
 Temperature, which hastens reactions if raised, since
higher temperature increases the energy of the
molecules, creating more collisions per unit time,
 The presence or absence of a catalyst. Catalysts are
substances which change the pathway (mechanism) of
a reaction which in turn increases the speed of a
reaction by lowering the activation energy needed for
the reaction to take place. A catalyst is not destroyed
or changed during a reaction, so it can be used again.
 For some reactions, the presence of electromagnetic
radiation, most notably ultraviolet light, is needed to
promote the breaking of bonds to start the reaction.
This is particularly true for reactions involving radicals.
Several theories allow calculating the reaction rates at the
molecular level. This field is referred to as reaction
dynamics. The rate v of a first-order reaction, which could
be disintegration of a substance A, is given by:

Its integration yields:

Here k is first-order rate constant having dimension

1/time, [A](t) is concentration at a time t and [A]0 is
the initial concentration. The rate of a first-order
reaction depends only on the concentration and
the properties of the involved substance, and the
reaction itself can be described with the
characteristic half-life. More than one time constant
is needed when describing reactions of higher
order. The temperature dependence of the rate
constant usually follows the Arrhenius equation:

where Ea is the activation energy and kB is

the Boltzmann constant. One of the simplest
models of reaction rate is the collision theory.
More realistic models are tailored to a specific
problem and include the transition state theory,
the calculation of the potential energy surface,
the Marcus theory and the Rice–Ramsperger–
Kassel–Marcus (RRKM) theory.[17]

Reaction types
Four basic types

Representation of four basic chemical reactions

types: synthesis, decomposition, single
replacement and double replacement.

Synthesis
Main article: Synthesis reaction
In a synthesis reaction, two or more simple
substances combine to form a more complex
substance. These reactions are in the general
form:

Two or more reactants yielding one

product is another way to identify a
synthesis reaction. One example of a
synthesis reaction is the combination
of iron and sulfur to form iron(II) sulfide:

Another example is simple hydrogen

gas combined with simple oxygen gas
to produce a more complex
substance, such as water.[18]
Decomposition
Main article: Decomposition reaction
A decomposition reaction is when a
more complex substance breaks down
into its more simple parts. It is thus the
opposite of a synthesis reaction, and
can be written as[18][19]

One example of a decomposition

reaction is the electrolysis of water
to
make oxygen and hydrogen gas:

Single replacement
In a single replacement
reaction, a single uncombined
element replaces another in a
compound; in other words,
one element trades places
with another element in a
compound[18] These reactions
come in the general form of:

One example of a single

displacement reaction is
when magnesium replace
s hydrogen in water to
make magnesium
hydroxide and hydrogen
gas:

Double replacement
In a double
replacement reaction,
the anions and
cations of two
compounds switch
places and form two
entirely different
compounds.[18] These
reactions are in the
general form:[19]

For example,
when barium
chloride (BaCl2)
and magnesium
sulfate (MgSO4)
react, the
SO42− anion
switches places
with the
2Cl− anion, giving
the compounds
BaSO4 and
MgCl2.
Another example
of a double
displacement
reaction is the
reaction
of lead(II)
nitrate with potas
sium iodide to
form lead(II)
iodide and potass
ium nitrate:

Oxidatio
n and
reductio
n

Illustration
of a redox
reaction
 Sodium
chloride is
formed
through
the redox
reaction of
sodium
metal and
chlorine
gas

Redox reactio
ns can be
understood in
terms of
transfer of
electrons
from one
involved
species
(reducing
agent) to
another
(oxidizing
agent). In this
process, the
former
species
is oxidized an
d the latter
is reduced.
Though
sufficient for
many
purposes,
these
descriptions
are not
precisely
correct.
Oxidation is
better defined
as an
increase
in oxidation
state, and
reduction as
a decrease in
oxidation
state. In
practice, the
transfer of
electrons will
always
change the
oxidation
state, but
there are
many
reactions that
are classed
as "redox"
even though
no electron
transfer
occurs (such
as those
involving cov
alent bonds).[
20][21]

In the
following
redox
reaction,
hazardous so
dium metal
reacts with
toxic chlorine
gas to form
the ionic
compound so
dium
chloride, or
common
table salt:

In the
reaction,
sodium
metal
goes
from an
oxidation
state of 0
(as it is a
pure
element)
to +1: in
other
words,
the
sodium
lost one
electron
and is
said to
have
been
oxidized.
On the
other
hand, the
chlorine
gas goes
from an
oxidation
of 0 (it is
also a
pure
element)
to −1: the
chlorine
gains one
electron
and is
said to
have
been
reduced.
Because
the
chlorine
is the one
reduced,
it is
considere
d the
electron
acceptor,
or in
other
words,
induces
oxidation
in the
sodium –
thus the
chlorine
gas is
considere
d the
oxidizing
agent.
Converse
ly, the
sodium is
oxidized
or is the
electron
donor,
and thus
induces
reduction
in the
other
species
and is
considere
d
the reduc
ing
agent.
Which of
the
involved
reactants
would be
reducing
or
oxidizing
agent
can be
predicted
from
the electr
onegativit
y of their
elements.
Elements
with low
electrone
gativity,
such as
most
metals,
easily
donate
electrons
and
oxidize –
they are
reducing
agents.
On the
contrary,
many
ions with
high
oxidation
numbers,
such
as H
2O
−
2, MnO

4, CrO

3, Cr
2−
2O

7 , OsO
4 can
gain one
or two
extra
electrons
and are
strong
oxidizing
agents.
The
number
of
electrons
donated
or
accepted
in a
redox
reaction
can be
predicted
from
the electr
on
configura
tion of
the
reactant
element.
Elements
try to
reach the
low-
energy n
oble
gas confi
guration,
and
therefore
alkali
metals
and
halogens
will
donate
and
accept
one
electron
respectiv
ely.
Noble
gases
themselv
es are
chemicall
y
inactive.[2
2]

An
important
class of
redox
reactions
are
the electr
ochemica
l reaction
s, where
electrons
from the
power
supply
are used
as the
reducing
agent.
These
reactions
are
particularl
y
important
for the
productio
n of
chemical
elements,
such
as chlorin
e[23] or alu
minium.
The
reverse
process
in which
electrons
are
released
in redox
reactions
and can
be used
as
electrical
energy is
possible
and used
in
batteries.

Compl
exatio
n

Ferroc
ene –
an
iron
atom
sandw
iched
betwe
 en two
C5H5 li
gands

In
complexa
tion
reactions,
several li
gands re
act with a
metal
atom to
form
a coordin
ation
complex.
This is
achieved
by
providing
lone
pairs of
the ligand
into
empty or
bitals of
the metal
atom and
forming d
ipolar
bonds.
The
ligands
are Lewis
bases,
they can
be both
ions and
neutral
molecule
s, such
as
carbon
monoxide
,
ammonia
or water.
The
number
of ligands
that react
with a
central
metal
atom can
be found
using
the 18-
electron
rule,
saying
that
the valen
ce
shells of
a transitio
n
metal will
collectivel
y
accommo
date
18 electr
ons,
whereas
the
symmetry
of the
resulting
complex
can be
predicted
with
the crysta
l field
theory an
d ligand
field
theory.
Complex
ation
reactions
also
include li
gand
exchange
, in which
one or
more
ligands
are
replaced
by
another,
and
redox
processe
s which
change
the
oxidation
state of
the
central
metal
atom.[24]

Acid-
base
reacti
ons
In
the Brøns
ted–
Lowry
acid–
base
theory,
an acid-
base
reaction i
nvolves a
transfer
of proton
s (H+)
from one
species
(the acid)
to
another
(the base
). When a
proton is
removed
from an
acid, the
resulting
species
is termed
that
acid's co
njugate
base.
When the
proton is
accepted
by a
base, the
resulting
species
is termed
that
base's co
njugate
acid.[25] In
other
words,
acids act
as proton
donors
and
bases act
as proton
acceptors
according
to the
following
equation:

The
rever
se
reacti
on is
possi
ble,
and
thus
the
acid/
base
and
conju
gated
base/
acid
are
alwa
ys in
equili
brium
. The
equili
brium
is
deter
mine
d by
the a
cid
and
base
disso
ciatio
n
const
ants (
Ka an
d Kb )
of the
invol
ved
subst
ance
s. A
speci
al
case
of the
acid-
base
reacti
on is
the n
eutral
izatio
n wh
ere
an
acid
and a
base,
taken
at
exact
ly
same
amou
nts,
form
a
neutr
al sal
t.
Acid-
base
reacti
ons
can
have
differ
ent
defini
tions
depe
nding
on
the
acid-
base
conc
ept
empl
oyed.
Som
e of
the
most
com
mon
are:

 A
rr
h
e
n
i
u
s

d
e
fi
n
it
i
o
n
:
A
c
i
d
s
d
i
s
s
o
c
i
a
t
e
i
n
w
a
t
e
r
r
e
l
e
a
s
i
n
g
H
3
O
+

i
o
n
s
;
b
a
s
e
s
d
i
s
s
o
c
i
a
t
e
i
n
w
a
t
e
r
r
e
l
e
 a
s
i
n
g
O
H
−

i
o
n
s
.
 B
r
ø
n
s
t
e
d
-
L
o
w
r
y

d
e
fi
n
it
i
o
n
:
A
c
i
d
s
a
r
e
p
r
o
t
o
n
(
H
+
)
d
o
n
o
r
s
,
b
a
s
e
s
a
r
e
p
r
o
t
o
n
a
c
c
e
p
t
o
r
s
;
t
h
i
s
i
n
c
l
u
d
e
s
t
h
e
A
rr
h
e
n
i
 u
s
d
e
fi
n
it
i
o
n
.
 L
e
w
i
s

d
e
fi
n
it
i
o
n
:
A
c
i
d
s
a
r
e
e
l
e
c
tr
o
n
-
p
a
ir
a
c
c
e
p
t
o
r
s
,
b
a
s
e
s
a
r
e
e
l
e
c
tr
o
n
-
p
a
ir
d
o
n
o
r
s
;
t
h
i
s
i
n
c
l
u
d
e
s
t
h
e
B
r
ø
n
s
t
e
d
-
L
 o
w
r
y
d
e
fi
n
it
i
o
n
.
Pre
cipi
tati
on

Pr
e
ci
pi
ta
ti
o
n

Preci
pitati
on is
the
form
ation
of a
solid
in a
soluti
on or
insid
e
anoth
er
solid
durin
ga
chem
ical
reacti
on. It
usual
ly
takes
place
when
the
conc
entra
tion
of
disso
lved
ions
exce
eds
the s
olubil
ity li
mit[26]
and
forms
an
insol
uble
salt.
This
proce
ss
can
be
assis
ted
by
addin
ga
preci
pitati
ng
agent
or by
remo
val of
the
solve
nt.
Rapi
d
preci
pitati
on
result
s in
an a
morp
hous
or
micro
cryst
alline
resid
ue
and
slow
proce
ss
can
yield
singl
e cry
stals.
The
latter
can
also
be
obtai
ned
by re
cryst
alliza
tion fr
om
micro
cryst
alline
salts.[
27]

Sol
id-
stat
e
rea
ctio
ns
Reac
tions
can
take
place
betw
een
two
solid
s.
How
ever,
beca
use
of the
relati
vely
small
diffu
sion r
ates
in
solid
s, the
corre
spon
ding
chem
ical
reacti
ons
are
very
slow
in
comp
ariso
n to
liquid
and
gas
phas
e
reacti
ons.
They
are
accel
erate
d by
incre
asing
the
reacti
on
temp
eratu
re
and
finely
dividi
ng
the
react
ant to
incre
ase
the
conta
cting
surfa
ce
area.[
28]

Re
acti
ons
at
the
soli
d|g
as
inte
rfa
ce
Reac
tion
can
take
place
at the
solid|
gas
interf
ace,
surfa
ces
at
very
low
press
ure
such
as ult
ra-
high
vacu
um.
Via s
canni
ng
tunne
ling
micro
scop
y, it
is
possi
ble to
obser
ve
reacti
ons
at the
solid|
gas
interf
ace
in
real
spac
e, if
the
time
scale
of the
reacti
on is
in the
corre
ct
rang
e.[29][30
]
Rea
ction
s at
the
solid|
gas
interf
ace
are in
some
case
s
relate
d to
catal
ysis.

Ph
oto
che
mic
al
rea
ctio
ns

In
th
is
P
at
er
n
o
–
B
ü
c
hi
re
a
cti
o
n,
a
p
h
ot
o
e
xc
it
e
d
c
ar
b
o
n
yl
gr
o
u
p
is
a
d
d
e
d
to
a
n
u
n
e
xc
it
e
d
ol
ef
in
,
 yi
el
di
n
g
a
n
o
x
et
a
n
e.

In ph
otoch
emic
al
reacti
ons,
atom
s and
mole
cules
absor
b
ener
gy
(phot
ons)
of the
illumi
natio
n
light
and
conv
ert
into
an ex
cited
state.
They
can
then
relea
se
this
ener
gy by
break
ing
chem
ical
bond
s,
there
by
prod
ucing
radic
als.
Phot
oche
mical
reacti
ons
inclu
de
hydro
gen–
oxyg
en
reacti
ons, r
adica
l
poly
meriz
ation,
chai
n
reacti
ons a
nd re
arran
geme
nt
reacti
ons.[3
1]

Many
impor
tant
proce
sses
invol
ve
photo
chem
istry.
The
premi
er
exam
ple
is ph
otosy
nthes
is, in
whic
h
most
plant
s use
solar
ener
gy to
conv
ert ca
rbon
dioxi
de an
d
water
into g
lucos
e,
dispo
sing
of ox
ygen
as a
side-
prod
uct.
Hum
ans
rely
on
photo
chem
istry
for
the
form
ation
of
vitam
in D,
and v
ision
is
initiat
ed by
a
photo
chem
ical
reacti
on
of rh
odop
sin.[12]
In fir
eflies
,
an en
zyme
in
the
abdo
men
catal
yzes
a
reacti
on
that
result
s
in bio
lumin
esce
nce.[3
2]
Ma
ny
signif
icant
photo
chem
ical
reacti
ons,
such
as
ozon
e
form
ation,
occur
in the
Earth
atmo
spher
e and
const
itute
atmo
spher
ic
chem
istry.

Ca
tal
ysi
s
Main
articl
e: Ca
talysi
s
Furth
er
infor
matio
n: Re
actio
n
Progr
ess
Kineti
c
Analy
sis

S
c
h
e
m
at
ic
p
ot
e
nt
ial
e
n
er
g
y
di
a
gr
a
m
s
h
o
wi
n
g
th
e
ef
fe
ct
of
a
c
at
al
ys
t
in
a
n
e
n
d
ot
h
er
m
ic
c
h
e
m
ic
al
re
a
cti
o
n.
T
h
e
pr
e
s
e
n
c
e
of
a
c
at
al
ys
t
o
p
e
n
s
a
di
ff
er
e
nt
re
a
cti
o
n
p
at
h
w
a
y
(i
n
re
d)
wi
th
a
lo
w
er
a
cti
v
at
io
n
e
n
er
g
y.
T
h
e
fi
n
al
re
s
ul
t
a
n
d
th
e
o
v
er
all
th
er
m
o
d
y
n
a
m
ic
s
ar
e
th
e
s
a
m
e.

S
oli
d
h
et
er
o
g
e
n
e
o
u
s
c
at
al
ys
ts
ar
e
pl
at
e
d
o
n
m
e
s
h
e
s
in
c
er
a
m
ic
c
at
al
yti
c
c
o
n
v
er
te
rs
i
n
or
d
er
to
m
a
xi
m
iz
e
th
ei
r
s
ur
fa
c
e
ar
e
a.
T
hi
s
e
x
h
a
u
st
c
o
n
v
er
te
r
is
fr
o
m
a
P
e
u
g
e
ot
1
0
6
S
2
 1
1
0
0

In cat
alysis
, the
reacti
on
does
not
proce
ed
direct
ly,
but
throu
gh
reacti
on
with
a
third
subst
ance
know
n
as ca
talyst
.
Altho
ugh
the
catal
yst
takes
part
in the
reacti
on, it
is
retur
ned
to its
origin
al
state
by
the
end
of the
reacti
on
and
so is
not
cons
umed
.
How
ever,
it can
be
inhibi
ted,
deact
ivate
d or
destr
oyed
by
seco
ndary
proce
sses.
Catal
ysts
can
be
used
in a
differ
ent
phas
e
(hete
roge
neou
s) or
in the
same
phas
e
(hom
ogen
eous)
as
the
react
ants.
In
heter
ogen
eous
catal
ysis,
typic
al
seco
ndary
proce
sses
inclu
de co
king
wher
e the
catal
yst
beco
mes
cover
ed
by po
lymer
ic sid
e
prod
ucts.
Additi
onall
y,
heter
ogen
eous
catal
ysts
can
disso
lve
into
the
soluti
on in
a
solid
–
liquid
syste
m or
evap
orate
in a
solid
–gas
syste
m.
Catal
ysts
can
only
spee
d up
the
reacti
on –
chem
icals
that
slow
down
the
reacti
on
are
calle
d
inhibi
tors.[3
3][34]
S
ubsta
nces
that
incre
ase
the
activi
ty of
catal
ysts
are
calle
d
prom
oters,
and
subst
ance
s that
deact
ivate
catal
ysts
are
calle
d
catal
ytic
poiso
ns.
With
a
catal
yst, a
reacti
on
whic
h is
kineti
cally
inhibi
ted
by a
high
activ
ation
ener
gy
can
take
place
in
circu
mven
tion
of
this
activ
ation
ener
gy.
Heter
ogen
eous
catal
ysts
are
usual
ly
solid
s,
powd
ered
in
order
to
maxi
mize
their
surfa
ce
area.
Of
partic
ular
impor
tance
in
heter
ogen
eous
catal
ysis
are
the pl
atinu
m
grou
p met
als
and
other
transi
tion
metal
s,
whic
h are
used
in hy
drog
enati
ons,
catal
ytic
refor
ming
and
in the
synth
esis
of
com
modit
y
chem
icals
such
as nit
ric
acid
and a
mmo
nia.
Acids
are
an
exam
ple of
a
homo
gene
ous
catal
yst,
they
incre
ase
the
nucle
ophili
city
of car
bonyl
s,
allowi
ng a
reacti
on
that
woul
d not
other
wise
proce
ed
with
electr
ophil
es.
The
adva
ntage
of
homo
gene
ous
catal
ysts
is the
ease
of
mixin
g
them
with
the
react
ants,
but
they
may
also
be
diffic
ult to
separ
ate
from
the
prod
ucts.
Ther
efore
,
heter
ogen
eous
catal
ysts
are
prefe
rred
in
many
indus
trial
proce
sses.[
35]

Re
act
ion
s
in
org
ani
c
ch
em
ist
ry
Main
articl
e: Or
ganic
reacti
on
In
orga
nic
chem
istry,
in
additi
on to
oxida
tion,
reduc
tion
or
acid-
base
reacti
ons,
a
numb
er of
other
reacti
ons
can
take
place
whic
h
invol
ve co
valen
t
bond
s bet
ween
carbo
n
atom
s or
carbo
n
and h
etero
atom
s (su
ch as
oxyg
en,
nitrog
en, h
aloge
ns,
etc.).
Many
speci
fic
reacti
ons
in
orga
nic
chem
istry
are n
ame
reacti
ons d
esign
ated
after
their
disco
verer
s.

Su
bsti
tuti
on
In
a sub
stituti
on
reacti
on,
a fun
ction
al
grou
p in a
partic
ular c
hemi
cal
comp
ound
is
repla
ced
by
anoth
er
grou
p.[36]
Thes
e
reacti
ons
can
be
distin
guish
ed by
the
type
of
subst
itutin
g
speci
es
into
a nuc
leoph
ilic, el
ectro
philic
or ra
dical
subst
itutio
n.

S
N

1
m
e
c
h
a
 ni
s
m

S
N

2
m
e
c
h
a
ni
s
m

In the
first
type,
a nuc
leoph
ile,
an
atom
or
mole
cule
with
an
exce
ss of
electr
ons
and
thus
a
negat
ive
charg
e
or pa
rtial
charg
e,
repla
ces
anoth
er
atom
or
part
of the
"subs
trate"
mole
cule.
The
electr
on
pair
from
the
nucle
ophil
e
attac
ks
the
subst
rate
formi
ng a
new
bond,
while
the le
aving
grou
p dep
arts
with
an
electr
on
pair.
The
nucle
ophil
e
may
be
electr
ically
neutr
al or
negat
ively
charg
ed,
wher
eas
the
subst
rate
is
typic
ally
neutr
al or
positi
vely
charg
ed.
Exa
mple
s of
nucle
ophil
es
are h
ydrox
ide io
n, alk
oxide
s, am
ines
and h
alide
s.
This
type
of
reacti
on is
found
mainl
y
in ali
phati
c
hydro
carbo
ns,
and
rarely
in aro
matic
hydro
carbo
n.
The
latter
have
high
electr
on
densi
ty
and
enter
nucl
eophi
lic
arom
atic
subst
itutio
n onl
y
with
very
stron
g ele
ctron
withd
rawin
g
grou
ps.
Nucl
eophi
lic
subst
itutio
n can
take
place
by
two
differ
ent
mech
anis
ms,
SN1 a
nd SN
2. In
their
name
s, S
stand
s for
subst
itutio
n, N
for
nucle
ophili
c,
and
the
numb
er
repre
sents
the ki
netic
order
of
the
reacti
on,
unim
olecu
lar or
bimol
ecula
r.[37]

T
h
e
th
re
e
st
e
p
s
of
a
n
S
N

2
re
a
ct
io
n.
T
h
e
n
u
cl
e
o
p
hi
le
is
gr
e
e
n
a
n
d
th
e
le
a
vi
n
g
gr
o
u
p
is
re
d

S
N

2
re
a
ct
io
n
c
a
u
s
e
s
st
er
e
o
in
v
er
si
o
n
(
W
al
d
e
n
in
 v
er
si
o
n)

The
SN1
reacti
on
proce
eds
in
two
steps
.
First,
the le
aving
grou
p is
elimi
nated
creati
ng
a car
bocat
ion.
This
is
follo
wed
by a
rapid
reacti
on
with
the
nucle
ophil
e.[38]
In the
SN2
mech
anis
m,
the
nucle
ophil
e
forms
a
transi
tion
state
with
the
attac
ked
mole
cule,
and
only
then
the
leavi
ng
grou
p is
cleav
ed.
Thes
e two
mech
anis
ms
differ
in
the st
ereoc
hemi
stry o
f the
prod
ucts.
SN1
leads
to the
non-
stere
ospe
cific
additi
on
and
does
not
result
in a
chiral
cente
r, but
rathe
r in a
set
of ge
omet
ric
isom
ers (c
is/tra
ns).
In
contr
ast, a
rever
sal
(Wal
den
inver
sion)
of the
previ
ously
existi
ng
stere
oche
mistr
y is
obser
ved
in the
SN2
mech
anis
m.[39]
Elect
rophil
ic
subst
itutio
n is
the
count
erpar
t of
the
nucle
ophili
c
subst
itutio
n in
that
the
attac
king
atom
or
mole
cule,
an el
ectro
phile,
has
low
electr
on
densi
ty
and
thus
a
positi
ve
charg
e.
Typic
al
electr
ophil
es
are
the
carbo
n
atom
of car
bonyl
grou
ps,
carbo
catio
ns
or sul
fur or
nitro
nium
catio
ns.
This
reacti
on
takes
place
almo
st
exclu
sively
in
arom
atic
hydro
carbo
ns,
wher
e it is
calle
d ele
ctrop
hilic
arom
atic
subst
itutio
n.
The
electr
ophil
e
attac
k
result
s in
the
so-
calle
d σ-
comp
lex, a
transi
tion
state
in
whic
h the
arom
atic
syste
m is
aboli
shed.
Then
, the
leavi
ng
grou
p,
usual
ly a
proto
n, is
split
off
and
the
arom
aticit
y is
resto
red.
An
altern
ative
to
arom
atic
subst
itutio
n is
electr
ophili
c
aliph
atic
subst
itutio
n. It
is
simil
ar to
the
nucle
ophili
c
aliph
atic
subst
itutio
n and
also
has
two
major
types
, SE1
and
SE2[40]
Mech
anism
of
electr
ophili
c
arom
atic
substi
tution
In the
third
type
of
subst
itutio
n
reacti
on,
radic
al
subst
itutio
n, the
attac
king
partic
le is
a radi
cal.[36]
 This
proce
ss
usual
ly
takes
the
form
of
a cha
in
reacti
on,
for
exam
ple in
the
reacti
on of
alkan
es
with
halog
ens.
In the
first
step,
light
or
heat
disint
egrat
es
the
halog
en-
conta
ining
mole
cules
prod
ucing
the
radic
als.
Then
the
reacti
on
proce
eds
as an
avala
 nche
until
two
radic
als
meet
and
reco
mbin
e.[41]

Reactions during the chain reaction of radical substitution

A
d
d
i
t
i
o
n

a
n
d

e
l
i
m
i
n
a
t
i
o
n
T
h
e
a
d
d
it
i
o
n

a
n
d
it
s
c
o
u
n
t
e
r
p
a
rt
,
t
h
e

e
li
m
i
n
a
ti
o
n
,
a
r
e
r
e
a
c
ti
o
n
s
w
h
i
c
h
c
h
a
n
g
e
t
h
e
n
u
m
b
e
r
o
f
s
u
b
s
ti
t
u
e
n
t
s
o
n
t
h
e
c
a
r
b
o
n
a
t
o
m
,
a
n
d
f
o
r
m
o
r
c
l
e
a
v
e

m
u
lt
i
p
l
e
b
o
n
d
s
.
D
o
u
b
l
e

a
n
d
t
ri
p
l
e
b
o
n
d
s

c
a
n
b
e
p
r
o
d
u
c
e
d
b
y
e
li
m
i
n
a
ti
n
g
a
s
u
it
a
b
l
e
l
e
a
v
i
n
g
g
r
o
u
p
.
S
i
m
il
a
r
t
o
t
h
e
n
u
c
l
e
o
p
h
ili
c
s
u
b
s
ti
t
u
ti
o
n
,
t
h
e
r
e
a
r
e
s
e
v
e
r
a
l
p
o
s
s
i
b
l
e
r
e
a
c
ti
o
n
m
e
c
h
a
n
i
s
m
s
w
h
i
c
h
a
r
e
n
a
m
e
d
a
ft
e
r
t
h
e
r
e
s
p
e
c
ti
v
e
r
e
a
c
ti
o
n
o
r
d
e
r.
I
n
t
h
e
E
1
m
e
c
h
a
n
i
s
m
,
t
h
e
l
e
a
v
i
n
g
g
r
o
u
p
i
s
e
j
e
c
t
e
d
fi
r
s
t,
f
o
r
m
i
n
g
a
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42

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43
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48
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52
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.[
54
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.[
56
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.[
57
]

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