Valence,OxidationNumber,andFormalCharge

Terms such as valence, oxidation number and formal charge appear frequently in both
elementary and advanced chemistry texts.
However,, it is evident from the literature that these terms are often viewed to be
synonymous and that conclusions pertaining to such an interpretation may be misleading.

Valence
N b off electrons
Number l t th t an atom
that t uses in
i bonding.
b di
Oxidation number
The charge remaining on an atom when all ligands are removed heterolytically in their
closed form, with the electrons being transferred to the more electronegative partner
(homonuclear bonds do not contribute to the oxidation number).
Formal charge
The charge remaining on an atom when all ligands are removed homolytically.
Coordination number
The number of atoms bonded to the atom of interest.
interest
 Valence
Two of the most important factors that provide a first order evaluation of the nature of a covalent
molecule are the electron count (cf. the octet & eighteenelectron rules) and the valence of each atom.

Whereas the term electron count is selfevident (i.e., the total number electrons in the valence shell of
an atom in a molecule) and used consistently, the word valence (aka valency) has many uses:

valence electrons

valence bond theory

valence shell electron pair repulsion theory (VSEPR)

bondvalence model
the valence of a particular atom is expressed in terms of a sum of the valences of individual
bonds, which in turn are calculated using empirically parameterized equations that require
knowledge of the bond lengths from crystallography.

covalency
refers to the formation of a covalent bond.

electrovalency or ionic valency

refers to complete electron transfer to form ions, with positive electrovalency being used to
express the number of electrons released by an element, while negative electrovalency
describes the number of electrons added.)
added )
But when used on its own, to what does valence refer?
 In view of the relationship between the valence of an atom and the molecular formulae of its
compounds, the valence of an atom is often described as its combining power, a phrase that
was first introduced by Frankland (1852) with respect to his atomicity concept.

Frankland s atomicity was later named quantivalenz by Hofmann (1865) and subsequently
Franklands
abbreviated to valenz by Kekul (1867) and Wichelhaus (1868).

Sidgwicks classic 1927 book on The Electronic Theory of Valency states that Valency is a
ggeneral term used to describe the power
p which atoms p possess of combiningg with one
another to form molecules.

The valence of an atom in a covalent molecule is simply the number of electrons that an
atom has used in bonding.

Mathematically, the valence of an atom in a molecule is equal to the difference between

(i) the number of valence electrons in the free atom (i.e., the group valence) and

(ii) the number of nonbonding electrons on the atom in the molecule.

Valence=numberofelectronsinvalenceshelloffreeatom

numberofnonbondingelectronsonatominmolecule
 If the valence is less than the group valence, it indicates that there are nonbonding electrons
on the atom.

Knowledge of the valence of an atom in a molecule is important because it tells us

1. whether the atom has enough electrons to support the number of atoms attached via
2center, 2electron bonds.

2. whether any electrons remain on the atom and are available for subsequent reactivity.

e.g., the
h valence
l off nitrogen in NH3 is 3, which
h h indicates
d that
h there
h is a pair off electrons
l on
nitrogen that may be used to coordinate additional groups (such as BH3 or H+).

In transitionmetal chemistry, knowledge of the number of nonbonding electrons, i.e., the dn

configuration,
fi ti i paramountt because
is b it is
i an important
i t t componentt in i determining
d t i i th
the
magnetic properties and electronic spectroscopy of a molecule.

If the valence of the atom appears to be greater than the

group valence,
valence it indicates that either the bonding cannot be
described in terms of 2center, 2electron bonds but rather
involves 3center, 2electron bonds.

An example of such a species with 3center,

3 center 2electron
2 electron
bonds is CH5+.
 As originally employed, the valence of an atom (A) refers to its combining power relative to
that of hydrogen; as such, the valence of an atom in a molecule is explicitly and readily
indicated by the molecular formula of the hydride AHn.

e.g., the nitrogen atom in NH3 has a valence of 3.

However, valence has been taken to be synonymous with oxidation number, number of
bonds and coordination number.

The origin of this confusion can be readily seen by consideration of the neutral AHn hydrides
for which the valence, magnitude of the oxidation number, number of bonds, and
coordination number each have the same value, n.

e.g., the nitrogen atom in NH3 has a valence of 3, an oxidation number of 3, 3 bonds, and a
coordination number of 3.

However, this relationship is purely coincidental !

e.g., consider [NH4]+ for which the nitrogen atom has used all five of its valence electrons
(there are no lone pair electrons) and is pentavalent, but its oxidation number is 3, the
number of bonds is 4, and the coordination number is 4.
 Valence&OxidationNumber
The oxidation
o idation number
n mber of an atom in a molecule
molec le is based on a formalism that forces a
covalent compound to possess complete ionic character and may be defined as

Oxidationnumber=chargeoncompound chargeonligands

note: an exception are homonuclear bonds, in which case the bond is broken homolytically
and a single electron is transferred to each atom.
In manyy cases, the charges
g assigned
g to simple
p monoatomic ligands
g do not varyy from
compound to compound.
A notable exception is provided by hydrogen for which both H+ and H have permissible
closedshell configurations (1s0 and 1s2 , respectively). In this case, the charge assigned to
h d
hydrogen i determined
is d t i d by
b the
th relative
l ti electronegativity
l t ti it off the
th atom
t t which
to hi h it is
i attached.
tt h d
It is important to emphasize that the derived charge does not correspond to the charge on
the atom in the molecule, but is hypothetical.
In this regard, it is unfortunate that the oxidation number is often described as a formal
charge because this term has a very distinct and different meaning to that of oxidation
number.
 In many situations, the valence of an atom in a molecule may be coincidentally equal to its
oxidation number.
p to break down. Specifically,
There are several factors that cause this relationship p y, valence and
oxidation number are not the same when either
(i) homonuclear elementelement bonds are present
ee.g.,
g the valence of the central carbon in CMe4 is four,
four but the oxidation number is
zero because homonuclear elementelement bonds are neglected in the
determination of oxidation number.
(ii) the ligands attached to the atom of interest are dissociated with opposite charges
e.g., the valence of carbon in CH2Cl2 is four, but the oxidation number is zero because,
in terms of electronegativity differences with respect to carbon, H is viewed as H+
and Cl is viewed as Cl.
(iii) the molecule is charged and the ligand is dissociated as a cation,
e.g., H+ , the valence of nitrogen in NH4+ is five, but its oxidation number is 3.
 Comparison of the valence, oxidation number, number of bonds, and coordination number
for some simple molecules.
 Examples of situations where the equivalence of valence to the magnitude of oxidation
number, number of bonds, and coordination number break down.
 Valence&NumberofBonds
The equivalence
eq i alence between
bet een valence
alence and number
n mber of 2center,
2 center 2electron
2 electron bonds for molecules
molec les of
the type AHn breaks down when the atom in question bears a formal charge.
e.g., consider the series of isoelectronic molecules BH4 , CH4 , and NH4+ ; while each of the
molecules exhibits four bonds to the central atom, the valences of B , C , and N are 3, 4, and
5, respectively.
Valence=numberofbonds+formalcharge

As such,
h it is evident
d that,
h f neutrall molecules
for l l off theh type AHn , the
h coincidental
d l
equivalence between valence and number of bonds is a consequence of the central atom
bearing no formal charge.
 Valence&CoordinationNumber(CN)
The coordination number
n mber (CN) is simply
simpl defined as the number
n mber of atoms attached to the
atom of interest in a molecule.For neutral molecules of the type AHn the CN of A is n and is
equivalent to its valence.
The equivalence between valence and coordination number breaks down when a multiple
bond is present.
e.g., consider the series of molecules H3CCH3 , H2CCH2 , and HCCH . The valence of
carbon in each molecule is 4, but the CNs are 4, 3, and 2, respectively.
In essence, when the central atom uses more than one of its electrons to bond to another
atom, the coordination number of the central atom is reduced from the value of its valence.
Likewise, the relationship between valence and CN breaks down when the bond is a dative
covalent bond where one of the atoms provides both electrons.

e.g., the valence of B in threecoordinate BH3 and fourcoordinate H3NBH3 is each 3.

 From the opposite perspective,
perspecti e it is evident
e ident that the valence
alence of the coordinating atom of a
dative ligand increases by two units when it coordinates to a Lewis acidic site.
Thus, while the nitrogen in NH3 is trivalent, it becomes pentavalent once it uses its lone pair
upon coordinating to a Lewis acid (e.g., BH3 or H+).
 UsingValence&OxidationNumberToProvideInsight
intotheNatureofaMolecule

It is pertinent to consider whether it is the valence or oxidation number that provides the
greater insight into understanding the nature of a molecule.

1. The oxidation numbers of C span the

range of 4 to +4.
2. Does the difference in the nature of CH4
and CCl4 warrant such a large change in
oxidation number?
g CH4 (ON = 4) is not a widely used
ee.g.,
reducing agent, and CCl4 (ON = + 4) is not
a widely used oxidizing agent.
3. CMe4 (ON = 0) has little in common with
CH2Cl2 (ON = 0).
4. As such, the large variation in oxidation
states cannot be regarded as providing
much h insight
i i ht into
i t the
th nature
t off these
th
molecules.
 A further illustration of how oxidation number may offer little insight into the chemistry of a
molecule is provided by the fact that both Me2CCl2 and :CCl2 have an oxidation number of +2,
but the chemistry of these molecules are very distinct.
distinct
Thus, whereas Me2CCl2 is a stable species, the carbene :CCl2 is only known to exist as a
reactive intermediate.
Likewise,
Lik i theth carbon
b atoms
t i both
in b th CH3CH3 andd CH3 have
h an oxidation
id ti number b off 3,
3 but
b t the
th
former compound is a stable molecule while the latter is a highly reactive radical.
 In contrast, the valence of an atom in a molecule does provide useful information. Thus,
with two exceptions, all of the compounds listed in previous table exhibit a valence of 4 for
carbon despite the fact that the oxidation numbers range from +4 to 4.
carbon, 4
The two exceptions are :CCl2 , with a valence of 2, and CH3 with a valence of 3. These
exceptions are notable because they correspond to the two compounds that are not isolable
under normal conditions.
A further example is the oxidation number of the carbon atom in a series of alcohols.
ON = 2 for CH3OH
ON = 1 for MeCH2OH
ON = 0 for Me2C(H)OH
ON = +1 for Me3COH
Each of the alcohols possess C in the same valence state and thereby reiterates the ability of
valence to provide a greater appreciation of chemical reasonableness than does oxidation
number.
The valence of an atom in a molecule provides a much more meaningful criterion for
evaluating the chemical reasonableness of a molecule than does the oxidation number.
Thus, while the concept of oxidation numbers is of use in certain situations, such as the
balancing of redox equations, it is less fundamental than the underlying concept of valence
and its use in evaluating the chemical reasonableness of a molecule is only successful when
the oxidation number and valence of an atom in a molecule are coincidentally the same.
 Knowledgeofvalenceisessentialbecauseitallowsonetoascertainwhether
theatomhasenoughelectronstosupportthenumberofatomsattachedvia2center,2
l b d
electronbonds.

Compare CH4 and CH5+.

both contain C with an identical electronic configuration, ON = 4 and both obey the
octet rule.
However, the valence of C in CH5+ is 6 even though C only has 4 valence electrons indicating
that there is something unusual about this molecule!
Indeed, CH5+ is very unstable, but how could such a species exist if the valence of C were to
be 6? Since the carbon atom in CH4 does not have any electrons available for protonation
(unlike the nitrogen atom in NH3), ) the answer is quite simply provided by the fact that it is
not the carbon atom itself that is protonated.
Rather, it is the CH bond that is protonated, thereby resulting in a 3center, 2electron
interaction.
With a 3center, 2electron interaction, CH5+ may be regarded as a dihydrogen complex of
CH3+ and so the valence of the carbon in this species remains 4.
Thus protonated the carbon atom in CH5+ contributes only
Thus, because it is the CH bond that is protonated,
4 valence electrons to bonding the 5 hydrogen atoms.
 Knowledgeofvalenceisessentialbecauseitallowsonetoascertainwhether
anyelectronsremainontheatomandareavailableforsubsequentreactivity.
any electrons remain on the atom and are available for subsequent reactivity

The use of valence to provide an indication of whether there are any electrons available on
the atom for further bonding, is provided by consideration of NH3.
Thus, the valence of nitrogen in NH3 is three, thereby indicating that there is a pair of
electrons available for subsequent reactivity, such as protonation or coordination to a Lewis
acid.
id

Calculationofformalchargesfor(XH4)q (X=B,C,N;q=1,0,+1)
 ComparisonofOxidationNumber,FormalCharge,
andActualCharge
The formal charge of an atom in a given Lewis structure is the charge it would possess if the
electrons in each covalent bond were to be distributed equally between the two bonded
atoms such that each partner receives one electron.
i.e., homolytic cleavage
The formal charge may, therefore, be defined as the difference between (i) the number of
electrons in the free atom (i.e., the g
group
p valence) and (ii) the number of electrons remainingg
on the atom in a molecule when all bonds are broken homolytically.

Formalcharge=numberofelectronsinvalenceshelloffreeatom
numberofelectronsremainingafterhomolytic
b f l t i i ft h l ti cleavageofallbonds
l f ll b d

Since each 2center, 2electron bond contributes one electron to the electron count of an
atom in a molecule, the electron count is equal to the number of electrons in the valence
shell of the free atom plus the number of covalent bonds,
bonds adjusted by the formal charge.
charge
Thus, the formal charge may also be expressed as:

g
Formalcharge=numberofelectronsinvalenceshelloffreeatom
+numberofbonds electroncount
 While the concepts of oxidation number and formal charge are closely related in the sense
that they both refer to a charge on an atom in a molecule, they have very different values
because the charges are determined by two fundamentally different formalisms that
respectively exaggerate the ionic and covalent character of the bonding.
Does the actual charge on an atom in a covalent molecule correspond more closely to the
oxidation number or the formal charge?
 ElectroneutralityPrinciple

Stablecomplexesarethosewithstructuressuchthateachatomhasonlyasmallelectric
charge.StableMLbondformationgenerallyreducesthepositivechargeonthemetalas
wellasthenegativechargeand/ore densityontheligand.Theresultisthattheactual
chargeonthemetalisnotaccuratelyreflectedinitsformaloxidationstate

Pauling;TheNatureoftheChemicalBond,3rdEd.;1960,pg.172.
g f pg

NeitherOxidationNumberorFormalChargeareaccuratedescriptionsofelectrondensityat
the metal
themetal.
Chargeonanatomistypicallyconsideredtobelessthan1
e.g.,highoxidationstate,earlyTMcomplexesarestabilizedviadonationshiftingelectron
density from donor ligands to the metal This in part accounts for the extreme oxophilicity
densityfromdonorligandstothemetal.Thisinpartaccountsfortheextremeoxophilicity
ofearlyTM.
Valence = number of electrons in valence shell of free atom
number of nonbonding electrons on atom in molecule

Valence = number of bonds + formal charge

Oxidation number = charge on compound charge on ligands

Formal charge = number of electrons in valence shell of free atom

number
number of electrons remaining after homolytic cleavage of all bonds
bonds

Formalcharge =numberofelectronsinvalenceshelloffreeatom
+ number
+ numberofbonds
of bonds electron
electroncount
count
 MOTheory
MO theory assumes that electrons are delocalized across the molecular framework where a
Linear Combination of Atomic Orbitals (LCAO) is invoked
N B
According to the Born interpretation, the probability electron density is proportional to
N2 B
bonding
The probability electron density of bond is thus proportional to
1. The probability density of the electron confined to atom A,
2. The probability density of the electron confined to atom B, B2
3. The additional probability of finding the electron intermediate between A and B, AB
N2 B2 AB
The additional contribution from AB is known as the overlap density and represents an
enhancement of finding the electron in the internuclear distance.
Thus electrons accumulate in regions of constructive orbital overlap between bonding nuclei
and lowering the overall energy.
 antibonding
The probability electron density of the antibonding orbital is thus proportional to
1. The probability density of the electron confined to atom A,
2
2. B B2
The probability density of the electron confined to atom B,
The probability of finding the electron intermediate between A and B is now AB due to
destructive interference in the internuclear region resulting in a node
N
2
B2 AB
Occupation of the antibonding orbital thus decrease electron density in the internuclear
region thus pushing the bonding nuclei apart, weakening the bond and raising the energy of
the system.
system
In fact the following relationship holds true
|E EA|>|E EA|
thus the antibonding orbital is more antibonding than the bonding orbital is bonding.
 MOsfrom1s Orbitals
HomonuclearDiatomicMolecules
Homonuclear Diatomic Molecules

Positive combination causes a buildup of electron density between the nuclei, resulting in a
sigma
i b di MO ().
bonding ( )
Negative combination results in a nodal plane between the nuclei, which works against
bonding, resulting in a sigma antibonding MO (*).
In general, number of MOs formed as LCAOs equals number of AOs used.

bonding MO
bondingMO antibondingMO
antibonding MO

=ab =a b
 MOEnergyLevelScheme
First Period Homonuclear Diatomic Cases
FirstPeriodHomonuclearDiatomicCases

Scheme is filled in the usual aufbau manner, following the Pauli exclusion principle and
Hund's rule of maximum multiplicity (for the ground state).
Bond order is defined as follows:

bond order = ((bondingg e's antibonding

g e's))
 H2 andHe2

H2 bond order = (2 0) = 1

He2 bondorder=(2 2)=0

(He2doesnotexist.)
 H2+ andHe2+ ions

H2+ bond order = (1 0) =

He2+ bondorder=(2 1)=

 MOsforSecondPeriod
Homonuclear Diatomic Molecules
HomonuclearDiatomicMolecules

Ingeneral,atomicorbitalsthataremostsimilarinenergyinteractmosteffectivelyinforming
MOs.
MO
MOsforsecondperioddiatomicmoleculesarecombinationsofthetype2s 2sand2p 2p.

2s bondingMO 2s antibondingMO
MOEnergyLevelSchemefor
Li2,Be
Be2,andRelatedIons
and Related Ions

Li2 bondorder=(4 2)=1 Be2 bondorder=(4 4)=0

 2p 2p MOs( and)
Singly degenerate 2p and 2p bonding and antibonding MOs from 2pz 2pz
Two degenerate 2p bonding MOs, one from 2px + 2px and one from 2py + 2py
Two degenerate *2p antibonding MOs, one from 2px 2px and one from 2py 2py

2p bondingMO 2p bondingMO

2p antibondingMO 2p antibondingMO
 MOSchemeforO2 throughNe2
and Related Ions
andRelatedIons

The core configuration levels 1s and *1s are omitted.

 MOSchemeforB2 throughN2
and Related Ions
andRelatedIons
In diatomic molecules of the lighter elements B2, C2, and N2, mixing between sigmatype MOs
causes the *2s level to move down and the 2p level to move up in energy.
The 2p level rises above that of 2p.
This results in the following scheme, in which the relative ordering 2p < 2p occurs:
 MODescriptionofO2 andItsIons
MO model predicts the observed paramagnetism, which VB theory cannot explain easily.
 SecondPeriodHeteronuclearDiatomicMolecules

MO scheme for homonuclear diatomic molecules can be adapted to describe bonding in

heteronuclear diatomic molecules.

The two atoms do not contribute equally to each MO.

More electronegative element has lower energy AOs and makes a greater contribution
to bonding MOs.

Less electronegative atom makes a greater contribution to antibonding MOs.

Ordering of MOs energies in heteronuclear cases tends to be like lighter homonuclear cases:
i.e., 2p < 2p
 HeteronuclearDiatomicMolecules
Examples
CO, CN, NO+ (10 valence electrons, like N2)

bondorder=3
NO (11electron free radical, like O2+)

bondorder=2.5
 MODescriptionofPiDelocalizedSystems
MO theory has no difficulty explaining the delocalized electron density implied by
resonance forms, which VB theory cannot easily represent.

electrondensityofO3

The three 2p orbitals perpendicular to the molecular plane combine to form three MOs:
1. bonding MO
2. n nonbonding MO
3. * antibonding MO

A nonbonding MO neither builds nor destroys bonding between the oxygen atoms.
 PiMOEnergyLevelSchemeforO3

* antibonding MO

The system has two pairs of electrons, one pair in

the MO, and the other in the n nonbonding MO.

The configuration ()2 adds a bond order of 1 across

the two OO bonds (i.e., 0.5 to each bond).

When this is added to the sigma bond between each

n nonbonding MO
oxygen pair, the OO bond order becomes 1.5.

The configuration (n)2 neither adds nor subtracts

from the overall strength of the bonds.

bonding MO
 PiMOsofBenzene,C6H6
C6H6,hasthreepairsofelectronsdelocalizedinasystemextendingaroundthehexagonal
ring.

electrondensityofC6H6

Thesix2porbitalsperpendiculartotheringonthesixcarbonatomscombinetoformthree
bonding(1,2,3)andthreeantibonding(4*,5*,6*)MOs.
 PiMOEnergyLevelSchemeforC6H6

* 6

* 4 * 5

Three pairs in bonding MOs add a total of three

bond orders over six CC linkages, or 0.5 for each. 2 3
When this is added to the sigma bond between
each carbon pair, the CC bond order becomes 1.5.

1
 WaveEquationsofMolecules

Approximate wave functions are sought by combining atomic wave functions for the bonded
atoms.
Several different approaches have been taken to constructing trial wave functions.

V l
Valence B d (VB) Heitler
Bond H itl & London
L d (1927)

bond =a b
Hybrid orbitals Pauling (1920s)

Molecular Orbital (MO) Hund, Mulliken (1920s)

MO =aA +bB

LCAOs LennardJones (1929)

( )
 NormalizationRequirement
FromtheCopenhageninterpretationweassociatetheprobabilityoffindingtheelectronina
vanishinglysmallvolumeelement(apoint)as

The electron has unit probability over all space:

P = d = 1

TToensurethatanytrialwavefunction,R,meetsthiscriterionwegenerallymustmultiplybya
th t ti l f ti R t thi it i ll t lti l b
normalizationconstant,N,suchthat

P =N2 d =1

If isasolutiontotheSchrdingerequation,thensotooisN,andEin,H( =E( is
unaffected.
 NormalizationRequirement
When two orbitals on different atoms A and B overlap, the nature and effectiveness of their
interaction is given by the Slater overlap integral

= A B d
S =

which can be evaluated precisely only for H2 .

For our purposes we only need to recognize when certain interactions of orbitals have S > 0,
S = 0, or S < 0

S > 0 bonding interaction

S = 0 nonbonding interaction
S < 0 antibonding interaction

p p
The sense of S is evident from simple pictures of interactingg orbitals.

S > 0 reinforcing overlap between nuclei

S = 0 equally reinforcing and cancelling overlaps
S < 0 cancelling overlap between nuclei
ExamplesofS>0,S=0,andS<0
 AOShapeandSymmetry
All AOs with the same value of l have the same symmetry, regardless of n.
As isolated orbitals, each type can be identified with a particular point group.
s = R3
p = C4v
d = D2h ("cloverleaf") or D4h (dz2)
Orbitals that have bonding combinations usually have the same kind of symmetry with
respect to the internuclear axis.
If a bonding combination can be identified for any pair of orbitals, there must also be an
antibonding combination.
Nonbonding orbitals are oriented relative to each other such that they do not have the same
kind of symmetry relative to the internuclear axis.
 SymmetryDefinitionofSigma,Pi,andDeltaInteractions
Sigma interactionsaresymmetricalrelativetoaC2 axiscollinearwiththeinternuclear
axis.

Pi interactionsareantisymmetric( changessign)withrespecttoC2 collinearwiththe

internuclearaxisandwithrespecttov coplanarwiththesharednodalplane.

Delta interactionsaresymmetrictoC
Delta interactions are symmetric to C2 andantisymmetrictoC
and anti symmetric to C4 .

Bondingandantibondinginteractionsofthesametypehavethesamesymmetrywith
respecttotheinternuclearaxis.

bonding antibonding bonding antibonding

 Z
3p
p
Y
X
px py pz

4s

3d

dz2 dx2-dy2 dxy dxz dyz

 Metal Carbonyl
C

Y Z Z
*
Z C O Y C O Y C O
X sp X sp X

bond bond -back-donation

Metal dz2 carbonyl Metal dx2-dy
dy2 carbonyl Metal dyz carbonyl
 Metal Alkene

Y Z Z *CR
CR2 CR2 2

Z Y Y
X X X
CR2 CR2 CR2
complex complex back-donation
Metal dz2 alkene Metal dx2-y2 alkene Metal dyz alkene
 Fischer carbene

Y Z Z
R R R
Z C Y C Y C
X sp2 R X sp2 R X R

bond bond back-donation

Metal dz2 carbene sp2 Metal dx2-dy
dy2 carbene sp2 Metal dyz carbene p